High- Dielectric MIM Capacitors for Silicon RF and Analog Applications

HU HANG (M. Sc., Jilin University)

A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy

Electrical and Computer Engineering Department National University of Singapore Singapore

December, 2003

Abstract

ABSTRACT

Metal-insulator-metal (MIM) capacitors in silicon integrated circuits have attracted great attention due to their high conductive electrodes and low parasitic capacitance. The conventional MIM capacitors using SiO2 and Si3N4 usually provide low capacitance density, which is far from the requirement predicted by ITRS roadmap. Therefore, to adopt high- materials is an unavoidable choice to improve the overall electrical performance by using physically thicker dielectric films. In this thesis, a thorough research has been done for high- MIM capacitors using HfO2 based dielectrics for the first time. Various fabrication methods such as pulsed-laser deposition, sputtering, and atomic-layer-deposition have been employed to prepare high- dielectrics, and different dielectric structures like laminate, stack, sandwich, etc, have also been explored as well. Extensive electrical characterization was conducted to evaluate HfO2 based high- MIM capacitors. DC properties in terms of leakage, voltage coefficients, reliability etc, have been analyzed which are strongly correlated to the preparation methods and material properties. In addition, well behaved RF characteristics of these dielectrics have been demonstrated showing the almost invariable dielectric constants of HfO2 based dielectrics in RF regime. As a result, all the experimental results justify the suitability of HfO2 based dielectrics for MIM capacitors application. Mechanisms with regard to the electronic conduction in high- dielectrics, voltage coefficients of capacitance (VCCs) dependency, oxide degradation etc., have been discussed and clarified. A good understanding of process-structure-property

Abstract correlation is thus been achieved for high- dielectrics fabrication in back-end of line process, and the information obtained in this thesis is paramount for the operation of MIM capacitor devices. Finally, a free carrier injection model has been employed to understand VCCs mechanism of MIM capacitors. The results reveal that, the thickness (t) dependence of quadratic VCCs is an intrinsic problem due to electrical field enhancement in the scaled dielectric film, which exhibits a relation of tn (n~2). Besides, the frequency dependence of VCCs, and the stress modified VCCs could also been well interpreted using this model.

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Table of Contents

TABLE OF CONTENTS
Page No.

CHPATER 1 INTRODUCTION OF HIGH- MIM TECHNOLOGY 1.1. 1.2. Capacitors in Si technology.....1 Review of the literature...4

1.2.1. Motivation of metal-insulator-metal (MIM) technology.4 1.2.2. Current status of MIM technology..5 1.2.3. High- dielectrics for MIM capacitors application.7 1.2.4. Challenges and unsolved problems...12 1.3. 1.4. Contribution of this thesis.12 Thesis outline..13

References.15

CHAPTER 2 HFO2 MIM CAPACITORS BY PULSED-LASER DEPOSITION (PLD) 2.1. 2.2. 2.3. Introduction...22 Experiments...24 Results and discussion25

2.3.1. Physical characterization of PLD processed HfO2..25 2.3.2. Electrical characterization of HfO2 MIM capacitor.35 2.4. Limitations of PLD for thin film fabrication.43

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Table of Contents 2.5. Conclusion.46

References.48

CHAPTER 3 CHARACTERIZATION APPLICATION 3.1. 3.2. Introduction...53 Experiments...54 OF HFO2 MIM CAPACITORS FOR RF

3.2.1. RF MIM capacitor fabrication54 3.2.2. S-parameters for RF characterization57 3.3. Results and discussion58

3.3.1. RF characterization58 3.3.2. DC and low frequency measurements...63 3.4. Conclusion.70

References.72

CHAPTER 4 HFALOX MIM CAPACITORS BY ATOMIC-LAYER-DEPOSITION (ALD) 4.1. Introduction...76

4.1.1. ALD method for thin films fabrication76 4.1.2. Characteristics of ALD processed HfO2 and Al2O3..77 4.2. 4.3. Experiments...80 Electrical characterization of HfO2-Al2O3 laminated MIM capacitors81

4.3.1. RF characteristics of laminated MIM capacitors.82 4.3.2. Leakage and breakdown characteristics of laminated MIM capacitors84

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Table of Contents 4.3.3. VCCs dependence and reliability of laminated MIM capacitors93 4.4. 4.5. Effects of dielectric structures on the electrical properties.100 Conclusion...105

Reference.106

CHPATER 5 UNDERSTANDING CAPACITORS 5.1. 5.2. 5.3. Introduction.112 Theory..113 Results and discussion.115 VOLTAGE COEFFICIENTS OF HIGH- MIM

5.3.1. Thickness dependence of VCCs for HfO2 MIM capacitor..115 5.3.2. Frequency dependence of VCCs..123 5.3.3. Electrical stress modified VCCs..125 5.3.4. Prediction of VCCs..126 5.4. Conclusion...129

References.130

CHAPTER 6 Summary and future works134 6.1. 6.2. Summary..134 Future works135

List of Figures

LIST OF FIGURES

Figure 1.1 Figure 2.1

Dielectric constant versus band gap for oxides...8 Experimental configuration of pulsed-laser deposition system in this work...23

Figure 2.2

XRD patterns of HfO2 thin films deposited on Si(100) substrates at various substrate temperatures..26

Figure 2.3

Deposition rates of HfO2 thin films deposited on Si substrates at various substrate temperatures...27

Figure 2.4

Three dimensional AFM images of HfO2 thin films deposited on Si substrates at various substrate temperatures of (a). 25, (b). 200, (c). 300, and (d). 500oC respectively...28

Figure 2.5

Spectral dependence of refractive indexes of HfO2 films deposited at (a) various substrate temperatures (oxygen pressure: 50 mTorr) and (b) various deposition pressures (all deposited at room temperature)32

Figure 2.6

Spectral dependence of extinction coefficients of HfO2 films deposited at (a) various substrate temperatures (oxygen pressure: 50 mTorr) and (b) various deposition pressures (all deposited at room temperature)...34

Figure 2.7 Figure 2.8

TEM photos of 56 nm HfO2 MIM capacitor fabricated at 200oC.36 Current-voltage characteristic of HfO2 MIM capacitors prepared at 200, 300, and 400oC respectively..37

Figure 2.9

Capacitance versus frequency at zero bias for HfO2 MIM capacitors prepared at 200, 300, and 400oC respectively...38

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List of Figures Figure 2.10 Normalized capacitance of HfO2 MIM capacitors prepared at (a) 200, (b) 300, and (c) 400oC as a function of voltage applied at a frequency of 1 kHz, 10 kHz, 100 kHz, and 1 MHz respectively39 Figure 2.11 Normalized capacitance of HfO2 MIM capacitor prepared at 200oC as a function of temperature.....42 Figure 2.12 SEM top views of HfO2 film surfaces prepared with the laser fluence of (a) 4.0 and (b) 7.0 J/cm 2 respectively (fabricated at room temperature)...44 Figure 3.1 Major fabrication steps and schematic top views of RF HfO2 MIM capacitor and open dummy structure.56 Figure 3.2 Figure 3.3 Figure 3.4 The definition of S-parameters for a two-port network.57 The equivalent circuit model for capacitor simulation at RF regime59 The measured and simulated S-parameters for (a) HfO-1 and (b) HfO-2. (Simulation and parameter extractions were done by ICCAP.)60 Figure 3.5 High frequency response of PVD HfO2 MIM capacitors from 50 MHz to 20 GHz for HfO-1 and HfO-2..62 Figure 3.6 The frequency dependence of capacitance density for PVD HfO2 MIM capacitors HfO-1 and HfO-262 Figure 3.7 Stress induced leakage currents (SILCs) characteristics of (a) HfO-1 and (b) HfO-2 under the constant voltage stress at 1.5 V.64 Figure 3.8 Stress time dependence of (a) the quadratic voltage coefficients and (b) the linear voltage coefficients for HfO-1 under the constant voltage stress at 1.5 V66

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List of Figures Figure 3.9 Stress time dependence of (a) the quadratic voltage coefficients and (b) the linear voltage coefficients for HfO-2 under the constant voltage stress at 1.5 V68 Figure 3.10 The equivalent circuit for HfO2 MIM capacitors after stress. The added branch stands for the generated trapped states in MIM capacitor after stress..69 Figure 4.1 The growth rates dependence on deposition cycles for ALD processed (a) HfO2 and (b) Al2O379 Figure 4.2 Figure 4.3 TEM cross section of 13 nm HfO2-Al2O3 laminated dielectric.81 Measured and simulated S-parameters for (a) 13 nm, (b) 31 nm and (c) 43 nm laminated MIM capacitors83 Figure 4.4 The capacitance density dependence on frequency for laminate capacitors with three thicknesses, the inset shows high frequency response of laminate MIM capacitors from 50 MHz to 20 GHz...84 Figure 4.5 J-V characteristics of 13, 31 and 43 nm laminated capacitors measured at 125oC....85 Figure 4.6 J-V characteristics of 13 nm laminated MIM capacitor as a function of temperature....85 Figure 4.7 Conduction mechanisms for the 13 nm laminated MIM capacitor: (a) Poole-Frenkel mechanism occurring at high electric field, exhibiting a shift to lower electric field with increasing the temperature, (b) Schottky emission fitting at low electric field...87 Figure 4.8 The characteristics of leakage current versus stress time under 4V stress for the 13 nm laminated MIM capacitor. Square and round symbols

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List of Figures represent the 1st stress and the 2nd stress after an interruption of 10 hours, respectively....90 Figure 4.9 I-V measurements showing the hysteresis loop of 13 nm laminated MIM capacitor......90 Figure 4.10 (a) The typical breakdown characteristics of 13 nm laminate under different constant voltage stress; (b) the cumulative probability dependence on breakdown voltage for the laminated MIM capacitors with different thicknesses..92 Figure 4.11 (a) The voltage-dependent normalized capacitance (C/C0) at 1 MHz for 13, 31 and 43 nm laminated capacitors, fitted by a second order polynomial equation; and (b) the corresponding plot of C/C0 versus electric field (E).....94 Figure 4.12 Frequency dependences of for 13, 31 and 43 nm laminated capacitors, showing a linear fitting in log-log scale....95 Figure 4.13 Thickness dependence of quadratic VCC ( ) for laminated MIM capacitors...95 Figure 4.14 Temperature dependences of and at 100 kHz for 13, 31 and 43 nm laminated capacitors....96 Figure 4.15 The dependence of /0 on stress time at 10 kHz, 100 kHz and 1 MHz. The inset shows stress time dependence of /0 at the same frequencies. 0 and 0 represent the data before voltage stress (0 is of negative sign.), and denote the data after different time stress.97 Figure 4.16 (a) Cumulative TDDB curves under various constant voltages stress for 13 nm laminated MIM capacitor measured at room temperature, (b)

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List of Figures lifetime projection of 13 nm laminated MIM capacitor, using 50% failure time as the criteria........99 Figure 4.17 Illustrations of five different HfO 2 -Al 2 O 3 material structures for electrical characteristics comparison...101 Figure 4.18 Typical J-V characteristics for MIM capacitors with different dielectric structures at 125oC. The inset shows the corresponding breakdown characteristics obtained at the same temperature. (Device area: 10-4 m2)...101 Figure 4.19 TEM photos of (a) 13 nm HfO2-Al2O3 laminate, (b) 10 nm HfO2 and (3) 30 nm HfO2 films, illustrating the amorphous structure of laminate film and improved crystallinity with the increase of HfO 2 thicknesses...102 Figure 4.20 Evolution of C0 at zero DC bias with stress time, illustrating the highest stability for the laminated capacitor compared to other dielectric structures..104 Figure 5.1 Schottky plot of 30 nm HfO2 MIM capacitor. The inset shows the typical J-V curve..116 Figure 5.2 Measured and simulated normalized capacitance as a function of voltage. n0 and are extracted by fitting the measured data...117 Figure 5.3 Figure 5.4 Carrier concentration pre-factor (n0) dependence on thickness...118 Simulated normalized capacitance as a function of voltage for different thickness of 20, 30, 40, 50, and 60 nm....119 Figure 5.5 The simulated VCCs as a function of thickness with and without taking account of the change of pre-factor (n0) with thickness..120

List of Figures Figure 5.6 Linear voltage coefficients versus the capacitance density for HfO2 based high- dielectrics at 100 kHz.....121 Figure 5.7 Normalized capacitance versus DC bias measured at 100 kHz, showing good symmetrical CV characteristics (small linear coefficients ) for sandwich and laminate structures122 Figure 5.8 The measured VCCs for 30 nm HfO2 MIM capacitor together with the extracted carrier mobility at frequencies of 10k, 100k, 500k, 1 MHz.124 Figure 5.9 Simulated normalized capacitance as a function of voltage for 30 nm HfO 2 MIM capacitors at frequencies of 10k, 100k, 500k, and 1MHz...124 Figure 5.10 (a) The simulated VCCs of HfO2 MIM capacitors as a function of thickness with different carrier concentration pre-factor (n0), and (b) the simulated VCCs as a function of thickness with different carrier mobility in dielectric film....127

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List of Tables

LIST OF TABLES

Table 1.1 Table 1.2 Table 1.3 Table 1.4 Table 2.1

Mixed-signal capacitor technology requirements Short-term....2 Mixed-signal capacitor technology requirements Long-term....2 Integration of MIM capacitors into Al BEOL Current status..6 Integration of MIM capacitors into Cu BEOL Current status........6 The ratios of SIMS intensities O/Hf for HfO2 thin films prepared at various substrate temperatures (oxygen pressure: 50 mTorr)...30

Table 2.2

The ratios of SIMS intensities O/Hf for HfO2 thin films prepared at various oxygen pressures (All samples are prepared at room temperature 25oC.).....30

Table 2.3

Voltage linearity coefficients as a function of frequency for HfO2 MIM capacitors prepared at 200, 300, and 400oC respectively..41

Table 4.1 Table 4.2

ALD process conditions for the deposition of HfO2 and Al2O3....77 Variations of VCCs and leakage current under different condition (frequency: 100 kHz; stress voltage: 4V; area: 110-4 cm-2)98

Table 4.3

Comparison of various high capacitance density MIM capacitors using high- dielectrics (year 2002-2003)100

Table 5.1

Different structural HfO2-Al2O3 high- MIM capacitors prepared by ALD method....122

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Acknowledgments

ACKNOWLEDGMENTS

I would like to take this opportunity to express my gratitude to all the people who make it possible to complete this thesis work. First and foremost, I would like to give my great thanks to my principle supervisor, Dr. Zhu Chunxiang, who provides me with an interesting project, constant direction, valuable advice, and most of all, for providing me with opportunity. He has my tremendous appreciation and respect. I am deeply indebted to my co-supervisors, Dr. Lu Yongfeng currently in University of Nebraska Lincoln and Dr. Subhash Chander Rustagi from Institute of Microelectronics, Singapore, for being a constant source of help and advice; I truly appreciate the time, support and encouragement they have given me during the course of my PhD study. I owe most thanks to Prof. Li Ming-Fu, A/P Cho Byung Jin, A/P Yoo Won Jong, Prof. Albert Chin from National Chiao Tung University, Taiwan, and Prof. LeeDim Kwong from UT at Austin, for their always available helping hands, many great conversations. My special thanks go to Dr. Ding Shi-Jin, I feel privileged to have had the opportunity to work with him during my time in the PhD program, lots of collaboration work and fruitful discussions contribute to my thesis development. I would like to thank my peers with Silicon Nano Device Laboratory in alphabetical sequence: Chen Jingde, Chen Jinghao, Chen Xiaoyu, Joo Moon Sig, Kim Sun Jung, Loh Wei Yip, Park Chang Seo, Poon Chyiu Hyia, Debora, Ren Chi, Tan Kian Ming, Wang Yingqian, Wu Nan, Yang Tian, Yeo Chia Ching, Yu Xiongfei, and

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Acknowledgments Zhang Qingchun. I have benefited the collaboration work with them, and their friendship makes my stay in NUS more enjoyable. Last, and certainly the most, I would like to thank my parents for their love and support. I can never forget their inspiration and encouragement during my education years, their constant love and support made the long hours and frustrations bearable.

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Chapter 1 Introduction of High- MIM Technology

Chapter 1 Introduction of High- MIM Technology

1.1.

Capacitors in Si technology

Basic passive devices including capacitor, inductor, and resistor are indispensable elements in Si integrated circuits (ICs). Intuitively, passive devices can only consume or store energy, where active device like metal-oxide-semiconductor field effect transistor (MOSFET) can also provide amplification. A precise definition of passive elements was given by Desoer et. al [1]. Given a one-port with port voltage

v(t ) and port current i (t ) , the one-port is said to be passive if

t0

v(t ' )i (t ' )dt '+ (t 0 ) 0

(1.1)

where (t 0 ) is the energy stored by the one-port at time t 0 . Similarly, with the aid of the scattering matrix usually used for high frequency measurement, one could also deduce that the definition of passivity implies
0 S ij 1 (1.2) [2].

Compared to active devices such as MOSFET in the ultra large scale integrated circuit (ULSI) technology, passive devices played a relatively minor role. However, the recent advances in wired and wireless communication trigger demands for high quality passive devices for radio frequency (RF) and mixed signal applications, and

Chapter 1 Introduction of High- MIM Technology therefore spawned a revival interest in passive devices. A good introduction of passive component technology could be found elsewhere given by R. K. Ulrich [3]. Among the basic passive devices, capacitor is one of the essential elements, which may find its wide applications in RF circuits for oscillators and phase-shift networks, in various configurations of analog ICs such as the converters and filters, and decoupling capacitance in microprocessor units (MPUs), and so on. Table 1.1 Mixed-signal capacitor technology requirements Short-term [4]
Year of Production Density (fF/m2) Q (1/KQ2/m2GHz) Analog capacitor Voltage linearity (ppm/V2) Leakage (fA[pFV]) 3 Matching (%m2) Density (fF/m2) Q (1/KQ2/m2GHz) Voltage linearity (ppm/V) 2001 2 200 100 7 4.5 7 22 1000 2002 3 300 100 7 3 7.5 25 1000 2003 3 300 100 7 3 8 25 1000 2004 3 300 100 7 3 9 29 1000 2005 4 450 100 7 2.5 10 30 1000 2006 4 450 100 7 2.5 11 30 1000 2007 4 450 100 7 2.5 12 30 1000

RF bypass capacitor

Table 1.2 Mixed-signal capacitor technology requirements Long-term [4]

Year of Production Density (fF/m2) Q (1/KQ2/m2GHz) Analog capacitor Voltage linearity (ppm/V2) Leakage (fA[pFV]) 3 Matching (%m2) Density (fF/m2) Q (1/KQ2/m2GHz) Voltage linearity (ppm/V) 2010 7 700 100 7 2 17 35 1000 2013 10 1000 100 7 1.5 20 40 1000 2016 15 1500 100 7 1 23 40 1000

RF bypass capacitor

Manufacturable Solutions Exist, and Are Being Optimized Manufacturable Solutions are Known Manufacturable Solutions are Not Known

Based on the international technology roadmap for semiconductors (ITRS roadmap) [4], the main requirements and specifications for capacitors are summarized 2

Chapter 1 Introduction of High- MIM Technology in Table 1.1 and Table 1.2, where aggressive projections have been extent to year 2016 with ever increasing performance requirements. According to Table 1.1 and 1.2, capacitors are categorized into analog and RF bypass capacitors by ITRS roadmap, and it is believed that the requirements of analog capacitor are more difficult to be achieved compared to RF bypass capacitor. Here, we may detail generally the above technique specifications as follows: 1. Capacitance density One of the main issues for capacitors is to increase the capacitance per unit area in order to improve the integration level and reduce the system cost. 2. Leakage current The requirement of low leakage is obvious. However, it may be relaxed to some extent at very high clock frequency [4]. 3. Quality (Q) factor Q factor is a measure for parasitic effects including the distributed resistance and inductance, which could be computed by Q = imag ( Z Cap ) / real ( Z Cap ) [5]

4. Voltage coefficients of capacitance (VCCs) VCC can be approximated by C(V) = C0 (V2+V+1) [6], where C0 is the capacitance at zero volt and , are the quadratic and linear voltage coefficients of the capacitance respectively. 5. Temperature coefficients of capacitance (TCCs) TCC can be usually defined as: TCC = 10 6 dC ppm / oC [3, 7] T dT

6. Compatibility to back end of line (BEOL) integration

Chapter 1 Introduction of High- MIM Technology The capacitors fabrication needs to be compatible to existing ULSI backend technology. Thus, high quality dielectric must be formed at a very low temperature of ~400oC limited by backend process.

1.2.

Review of the literature

1.2.1. Motivation of metal-insulator-metal (MIM) technology

Traditionally, metal-insulator-silicon (MIS) [8, 9] structure has been used in Si ICs. However, this structure was replaced by polysilicon-oxide-polysilicon (doublepoly) capacitor since the electrical performance of double-poly structure was superior in terms of small VCCs and stray capacitance [10], where the capacitors precision is paramount for those of applications such as A/D converter. Accordingly, double-poly structure was established as a mature analog component. In addition, the improved capacitor structures like metal-ploy have also been reported [11, 12]. Though the polysilicon structure could be tailored in many ways to yield good electrical properties making it suitable for many analog applications, it suffered from limited RF capability in multi-GHz range [13]. The limitations in the quality factor are primarily due to the large resistive loss from the electrodes, and the parasitic capacitance because of the proximity to the lossy silicon substrate [14]. Therefore, metal-insulator-metal (MIM) structures have been proposed as the next generation capacitor structure due to their high conductive electrodes and low parasitic capacitances. In addition, the intrinsic depletion free MIM structures would provide better voltage linearity property [15].

Chapter 1 Introduction of High- MIM Technology Except the applications in Si ULSI circuits, MIM capacitor is also a key element in GaAs based monolithic microwave integrated circuits (MMICs) [16, 17]. In addition, the above mentioned problems are also anticipated by dynamic random access memories (DRAM) that use MIS structure as the charge storage cell. Therefore, advanced DRAM cell with MIM structures have also been studied [18, 19, 20]. It is possible to implement MIM for DRAM application beyond the 90 nm node in 2004, according to ITRS roadmap [4]. In this work, our focus is on high- MIM capacitors integrated into BEOL process for Si RF and analog applications, which is much different with the requirements of MIM capacitors in MMICs and DRAM cells in terms of materials, structures, process flow, and other aspects.

1.2.2. Current status of MIM technology

As an emerging technology, MIM capacitors draw great attentions among semiconductor industry companies in the very recent years. Based on the literature survey, we summarize the reported MIM capacitors technology from several major semiconductor companies, which are presented in Table 1.3 and Table 1.4 for Al and Cu BEOL integration respectively. As can be seen, SiO2 and Si3N4 are usually chosen as the dielectric materials for MIM capacitors fabrication in the current technology node. In comparison, Si3N4 has a higher dielectric constant () of 7 compared to SiO2 (~3.9), which usually provides relatively higher capacitance density than SiO2 MIM capacitors. In addition, Si3N4 could also be used to serve as a good Cu diffusion barrier [21], therefore eliminating Cu barrier metal stacks usually required in Cu BEOL process [21, 22]. However, the frequency dependence of capacitance and voltage linearity for Si3N4 capacitors may degrade the capacitors accuracy, which was

Chapter 1 Introduction of High- MIM Technology proposed to be originated from bulk traps in nitride films [23]. Low temperature deposited Si3N4 was reported to show higher relaxation recovery voltage than oxide [24]. When compared to LPCVD SiO2, the breakdown field strength of Si3N4 is lower, and both its voltage and temperature coefficients are usually higher. Therefore, schemes such as nitrous oxide plasma treatment [25], silicon oxynitride [26], SiO2Si3N4 stacks [27] have also been explored to combine the merits of SiO2 and Si3N4. Though SiO2 and Si3N4 MIM capacitors with excellent electrical performance have been successfully demonstrated in Al and Cu BEOL process; the capacitance density is still low, usually 2 fF/m2. Table 1.3 Integration of MIM capacitors into Al BEOL Current status
Conexant system [15] PECVD Nitride (30~60 nm) Ti/TiN/AlCu/Ti/TiN 1.0-1.9 for 30-60 nm thick film Life time: 106 and 103 years for 60 and 30 nm films.Q >80 at 2 GHz IBM [28] Single/multi layers (SiO2/Si3N4, 50-125 nm) TiN/AlCu/TiN 0.44-1.40 Toshiba [29] (Ta2O5, 50 nm) (Si3N4, 50 nm) WSi2 4.36 1.01 ~1E-10 A/mm2 for 50 nm Ta2O5 Good leakage property obtained after 300oC furnace annealing

Dielectric Bottom electrode C (fF/m2) Leakage (A/cm2) Remark

T50> 10-7 hours, phase improved by 2 compared with MOS

Table 1.4 Integration of MIM capacitors into Cu BEOL Current status

Dielectric Bottom plate C (fF/m ) VCC (ppm/V) Leakage (A/cm2) Leakage on temperature EBD (MV/cm) TDDB Remarks Si3N4 as both dielectric and diffusion barrier 150 10-10 at 5V Weak (25-200oC) 10 10 T50>1000 pwr-onhrs Leakage sensitivity to Tox
2

Lucent [21] Si3N4 (30 nm) Direct on Cu

IBM [22] SiO2 (48 nm) A conductive metal stack 0.72 TTC= -40 ppm/oC 10-6 A at 30 V

Motorola [30] Si3N4 (40 nm) Sputtering-TaN 1.6 <15 10-10 at 5V Weak (25-125oC) 9-10 Beyong 10 years Q2GHz= 30-200 at 3-0.1 pf

TSMC [31] Si3N4 1 VCC= 60 ppm/V TCC= 50 ppm/oC

Q=100 (2.4 GHz) and 40 (5.3 GHz) at 1.1 pf

Chapter 1 Introduction of High- MIM Technology Furthermore, it was noted that these of SiO2 and Si3N4 works are focused on the integration of MIM capacitors, and the process related issues have thus been well addressed. Planar structures were usually implemented for MIM capacitors integrated in BEOL process, and positioning the capacitors beneath the final metal level could further minimize the loss to the substrate. At or below 0.18 m technology, Cu metallization is used instead of Al metallization due to coppers low resistivity and feasibility of thick and fine pattern through damascene process [4]. However the introduction of Cu interconnects will create unique challenges for fabricating high reliability MIM capacitors, such as surface roughness of Cu on the reliability of MIM capacitors [21], the proper choice of Cu barrier metal stack [22], and the compatibility of capacitor dielectric with inter-level dielectric [22], etc.

1.2.3. High- dielectrics for MIM capacitors application

As described above, SiO2 and Si3N4 are dielectrics that are commonly used in conventional MIM capacitors [6-31]. Although these SiO2 and Si3N4 MIM capacitors could provide excellent electrical properties, their capacitance densities are limited due to their low dielectric constants (~3.9 for SiO2, ~7 for Si3N4). This is far from the requirement on capacitance density projected by the 2002 ITRS roadmap [4]. Further reduction in dielectric thicknesses of SiO2 and Si3N4 can increase the capacitance density, but it may offset leakage current, breakdown voltage, and voltage linearity property [22, 29]. For instance, it was reported that a 30-nm-thick SiO2 MIM capacitor has a voltage linearity of ~ 20 ppm/V2 [27]. From the 1/t2 (t: thickness) dependence [32], the voltage linearity of 14-nm-thick SiO2 MIM capacitor is supposed

Chapter 1 Introduction of High- MIM Technology to reach an upper limit of 100 ppm/V2 according to ITRS roadmap [4]. However, the capacitance density of 2.5 fF/m2 is low.

Figure 1.1: Dielectric constant versus band gap for oxides [34].

Therefore, the adoption of high- materials is imperative to meet the requirements of MIM capacitors in Si RF and analog IC applications. This is because of the fact that using physical thicker high- dielectric films may potentially improve the overall electrical performance. In the search to find suitable high- dielectrics, Figure 1.1 presents a compilation of a few potential high- dielectric candidates indicating the relationship of dielectric constant versus band gap. This provides a simple criterion of selecting suitable high- materials as the dielectrics for MIM capacitors. It is important to note that the general band gap reduction with the increase of value for dielectrics is a limitation that must be considered when selecting a

Chapter 1 Introduction of High- MIM Technology suitable high- material for MIM capacitor application [33, 34]. The decrease in band gap is usually coupled with the reduction of breakdown voltage for the dielectric materials [35]. Among various high- candidates for MIM capacitors application, Ta2O5, Al2O3, and HfO2 high- dielectrics are of great interests among researchers due to their relatively good materials properties and industrys familiarity. Ta2O5 based high- dielectrics have drawn a great attention, which may be inspired by memory capacitor applications and the resultant semiconductor manufacturing tool infrastructure [18, 36]. T. Yoshitomi et. al demonstrated pure Ta2O5 MIM capacitors by reactive sputtering [29]. With an O2 annealing at 300oC, the Ta2O5 MIM capacitor exhibit superior electrical performance when compared to its Si3N4 counterpart at the same equivalent oxide thickness (EOT) in terms of leakage property. T. Ishikawa et. al integrated Ta2O5 MIM capacitors into Cu BEOL process, and insertion of thin Al2O3 layer between Ta2O5. The bottom electrode was designed to improve the interface quality and the resulting electrical performance [37]. Y. L. Tu et. al achieved a very good voltage linearity (25 ppm/V2 and 13 ppm/V) for 4 fF/m2 Ta2O5 MIM capacitor when compared to TaOxNy, HfO2, Al2O3 and Ta2O5/Al2O3 stacks MIM capacitors in their work [38]. However, the electrical properties of those Ta2O5 MIM capacitors have been reported to be strongly dependent on the fabrication methods and the following thermal treatments [36, 38]. Therefore, a good understanding of process-structure-property correlation is of great importance before selecting Ta2O5 thin films for MIM capacitors application. Compared with other high- candidates, Al2O3 has a moderate dielectric constant of ~9, making it to be only a short term solution for industry need. However, the low oxygen diffusivity of Al2O3 [34, 39] may improve the interface quality by

Chapter 1 Introduction of High- MIM Technology reducing the chemical reaction with metal electrode. A large band gap of 8.9 eV is also beneficial for the improvement of leakage and breakdown characteristics. For MIM capacitors application, Al2O3 based high- materials including pure Al2O3 [39], Ti doped Al2O3 [39], and Ta doped Al2O3 [40, 41] have been investigated using an evaporation/oxidation method, and a high capacitance density of 17 fF/m2 has been achieved for AlTaOx MIM capacitor [41]. In particular, the RF performance of high- MIM capacitors have been studied for Al2O3 based dielectrics up to 20 GHz. A mathematical method was recently proposed for the computation of VCCs in RF regime for Al2O3 based dielectrics [40]. However, the low thermal budget in the fabrication of those Al2O3 based high- materials is probably responsible for their marginal electrical performance. HfO2 has the advantages of high dielectric constant (~25), high heat of formation (271 Kcal/mol), and large band gap (5.68 eV), etc. [34]. Most important of all, HfO2 based high- materials are well established as the next generation gate dielectric in MOSFETs [42] and DRAM [20]. HfO2 MIM capacitor was first reported using a pulsed-laser deposition (PLD) method [43]. Following that, other fabrication techniques including PVD [44], atomic-layer deposition (ALD) [45] have also been demonstrated. These techniques are more favourable for the mass production compared to PLD method. In addition, materials engineering of HfO2 dielectric such as Tb doping [44], Al alloying [45], and novel structures of HfO2-Al2O3 laminate [46] and stacks [47] have been further explored to improve the leakage and voltage linearity properties of HfO2 MIM capacitors. In summary, compared to the reported Ta2O5 and Al2O3 MIM capacitors, HfO2 based high- MIM capacitors exhibited nearly the best overall electrical properties, indicating that they are very promising for the next generation MIM capacitors application.

10

Chapter 1 Introduction of High- MIM Technology It was also noticed that some novel oxide systems have been explored for MIM capacitors application, such as Zr-Sn-Ti oxide with a high dielectric constant of 62 [32], Nb stabilized Ta2O5 [48], etc. However, the final justification of these oxide systems for MIM capacitors application needs more study, especially on their capacitance characteristics. Finally, it is worthwhile to point out that there are very few systematic reports on high- MIM capacitors reliability and mechanism study. The possible reason is that high- MIM capacitor is an immerging technology. This is in sharp contrast with the extensive and thorough investigation of high- materials for gate oxides applications. The reliability assessments for high- MIM capacitors could be found for HfO2 based high- dielectrics in [46, 47] and for Ta2O5 in [49]. Among them, HfO2Al2O3 laminate and pure Ta2O5 MIM capacitors both show promising reliability characteristics for 10-year lifetime under optimized process conditions [46, 49]. The conduction mechanism in dielectric insulating films is another subject with extensive theoretical and experimental investigation. A good understanding of electronic transport phenomena is paramount for the operation and leakage improvement of practical devices. To be specific, Poole-Frenkel effect [44, 46, 50], Shottky emission [46, 50], trap assisted tunnelling [50] are found to be prevalent in the leakage components in thick high- films used in MIM capacitors. Other major issues related to MIM capacitors, such as VCCs dependency [27, 28, 32, 37-41, 43-46], the dielectric relaxation [24, 51, 52], etc. have also been frequently observed. These phenomena are worthwhile for further investigations considering the poor knowledge thus far.

11

Chapter 1 Introduction of High- MIM Technology

1.2.4. Challenges and unsolved problems

Though the implementation of MIM structure and high- dielectrics appears to be straightforward, putting high- MIM capacitors into practical use may be problematic until a clear understanding and thorough research have been done. The main challenges and problems for high- materials to be used in MIM capacitors are as follows: 1. Suitable high- systems for MIM capacitors need to be identified. 2. The effects of fabrication techniques, structures, thermal treatment on high- MIM capacitors need to be studied. 3. Knowledge on electrical characteristics of high- MIM capacitors such as DC characteristics, RF performance, reliability, etc must be obtained. 4. The mechanisms with regard to high- MIM capacitors, such as conduction, voltage linearity dependency (parameters including thickness, frequency, and electrical stress), dielectric relaxation, etc must be understood.

1.3.

Contribution of this thesis

The followings are the research contribution of this project: 1. A thorough research has been done for HfO2 based high- dielectrics using various fabrication methods for the first time. The electrical performance has been demonstrated to be superior to SiO2 and Si3N4 counterparts in many aspects. 2. The RF characteristics of HfO2 based MIM capacitors have been reported for the first time. The good capacitance-frequency dependency indicate the usefulness of HfO2 based dielectrics for Si RF and mixed signal applications. 12

Chapter 1 Introduction of High- MIM Technology 3. We firstly observed that the voltage linearity of high- HfO2 based MIM capacitors could be modified after the electrical stress, and a possible explanation was given with the aid of a phenomenological circuit model. 4. For the first time, a free carrier injection model has been employed to understand voltage coefficients of capacitance (VCCs) of MIM capacitors. The thickness (t) dependence of quadratic VCCs, which exhibits a relation of

tn (n~2), is an intrinsic property due to electrical field enhancement in the

scaled dielectric film.

1. 4.

Thesis outline

In Chapter 2, HfO2 high- dielectrics prepared by PLD have been employed for MIM capacitors application with systematic material characterization, and excellent electrical properties had been demonstrated as well. In Chapter 3, RF characteristics of HfO2 MIM capacitors were investigated. In addition, thickness dependence of stress induced leakage currents and the evolution of voltage linearity with stress time for HfO2 MIM capacitors had been discussed with the help of proposed circuit model. In Chapter 4, high performance HfO2-Al2O3 laminate MIM capacitors have been developed using ALD method. The conduction mechanism, voltage linearity dependency, reliability issue have been investigated for these laminate films. In addition, the laminate structure has also been compared with other material structures such as stack, sandwich, etc.

13

Chapter 1 Introduction of High- MIM Technology In Chapter 5, the free carrier injection model was employed successfully to explain VCCs dependence on dielectric thickness, frequency, and electrical stress for high- MIM capacitors. A unified understanding of VCC is achieved for the first time. Finally, Chapter 6 concludes with suggestions for future work.

14

Chapter 1 Introduction of High- MIM Technology

References:

[1] C. A. Desoer, and E. S. Kuh, Basic circuit theory (McGraw-Hill, New York, 1969) [2] H. J. Carlin, and A. B. Giordano, Network theory: an introduction to reciprocal and non-reciprocal circuits (Prentice-Hall, Englewood Cliffs, New York, 1964) [3] R. K. Ulrich and L. W. schaper, Integrated passive component technology (Wiley, New York., 1993) [4] The international Technology Roadmap for Semiconductors, Semiconductor Industry Association, 2002. [5] T. H. Lee, The design of CMOS radio-frequency integrated circuits (Cambridge university press, 1998) [6] K. -S. Tan, S. Kiriake, M. de Wit, J. W. Fattaruso, C. -Y. Tsay, W. E. Matthews, and R. K. Hester, Error correction techniques for high-performance differential A/D converters, IEEE J. Solid-State Circuits, Vol. 25, pp. 13181327, 1990. [7] S. A. St Onge, S. G. Franz, A. F. Puttlitz, A. Kalinoski, B. E. Johnson, and B. ElKareh, Design of precision capacitors for analog applications, IEEE Trans. on Components, Packaging, and Manufacturing Technology, Vol. 15, pp. 1064-1071, Dec. 1992. [8] R. Singh and A. B. Bhattacharyya, Matching properties of linear MOS capacitors, IEEE Trans. Circuits and Systems, Vol. 36, pp. 465-467, 1989. [9] J. L. McCreary, Matching properties, and voltage and temperature dependence of MOS capacitors, IEEE J. Solid-State Circuits, Vol. 16, pp. 608-616, 1981. [10] T. Iida, M. Nakahara, S. Gotoh, and H. Akiba, Precise capacitor structure suitable for submicron mixed analog/digital ASICs, pp. 18.5/1-18.5/4, Custom Integrated Circuits Conference, 1990.

15

Chapter 1 Introduction of High- MIM Technology [11] C. Kaya, H. Tigelaar, J. Paterson, M. de Wit, J. Fattaruso, S. Kiriakai, K. S. Tan, and F. Tsay, Ploycide/metal capacitors for high precision A/D converters, in Proc. of IEDM, pp. 782-785, 1988. [12] A. Yin, J. White, A. Karroy and C. Hu, Integration of polycide/metal capacitors in advanced device fabrication, in Proc. of 5th ICSICT, pp. 131-134, 1998. [13] S. Jenei, S. Decoutere, S. V. Huylembroeck, G. Vanhorebeek, and B. Nauwelaers, High Q inductors and capacitors on Si substrate, Silicon Monolithic Integrated Circuits in RF Systems, pp. 64-70, 2001. [14] A. M. Niknejad, and R. G. Meyer, Design, simulation and applications of inductors and transformers for Si RF ICs (Kluwer Academic Publishers, 2000) [15] A. Kar-Roy, C. Hu, M. Racanelli, C. A. Compton, P. Kempf, G. Jolly, P. N. Sherman, J. Zheng, Z. Zhang, and A. Yin, High density metal insulator metal capacitor using PECVD nitride for mixed signal and RF circuits, Int. Interconnect Tech. Conference, pp. 245-247, 1999. [16] J. H. Lee, D. H. Kim, Y. S. Park, M. K. Sohn, and K. S. Seo, DC and RF characteristics of advanced MIM capacitors for MMIC's using ultra-thin remotePECVD Si3N4 dielectric layers, IEEE Microwave and Guided Wave Lett., Vol. 9, pp. 345-347, 1999. [17] J. Scarpulla, D. C. Eng, S. R. Olson, and C. S. Wu, A TDDB model of Si3N4based capacitors in GaAs MMICs, in Proc. Symp. Reliability Physics, pp. 128137, 1999. [18] J. W. Kim, S. D. Nam, S. H. Lee, S. J. Won, W. D. Kim, C. Y. Yoo, Y. W. Park, S. I. Lee and M. Y. Lee, Development of Ru/Ta2O5/Ru capacitor technology for Giga-scale Drams, in Proc. of IEDM, pp. 793-796, 1999.

16

Chapter 1 Introduction of High- MIM Technology [19] M. Takeuchi, K. Inoue, M. Sakao, T. Sakoh, T. Kitamura, S. Arai, T. Iizuka, T. Yamamoto, H. Shirai, Y. Aoki, M. Hamada, R. Kubota, and S. Kishi, A 0.15 m logic based embedded DRAM technology featuring 0.425 m2 stacked cell using MIM (metal-insulator-metal) capacitor, in Proc. Symp. VLSI Technology, pp. 2930, 2001. [20] S. H. Oh, J. H. Chung, J. H. Choi, C. Y. Yoo, Y. S. Kim, S. T. Kim, U. I. Chung, and J. T. Moon, TiN/HfO2/TiN capacitor technology applicable to 70 nm generation DRAMs, in Proc. Symp. VLSI Technology, pp. 73-74, 2003. [21] R. Liu, C.-Y. Lin, E. Harris, S. Merchant, S.W. Downey, G. Weber, N.A. Ciampa, W. Tai, W. Y. C. Lai, M. D. Morris, J. E. Bower, J. F. Miner, J. Frackoviak, W. Mansfield, D. Barr, R. Keller, C. P. Chang, C. S. Pai, and S. N. Rogers, Single mask metal-insulator-metal (MIM) capacitor with copper damascene metallization for sub-0.18 m mixed mode signal and system-on-a-chip (SoC) applications, in Proc. Interconnect Technology Conference, pp. 111-113, 2000. [22] M. Armacost, A. Augustin, P. Felsner, Y. Feng, G. Friese, J. Heidenreich, G. Hueckel, O. Prigge, and K. Stein, A high reliability metal insulator metal capacitor for 0.18 m copper technology, in Proc. of IEDM, pp. 157-160, 2000. [23] J. A. Babcock, S. G. Balster, A. Pinto, C. Dirnecker, P. Steinmann, R. Jumpertz, and B. El-Kareh, Analog characterisitics of metal-insulator-metal capacitors using PECVD nitride dielectrics, IEEE Electron Device Lett., Vol. 22, No. 5, pp. 230-232, 2001. [24] J. W. Fattaruso, M. De Wit, G. Warwar, K.-S. Tan, and R. K. Hester, The effect of dielectric relaxation on charge-redistribution A/D converters, IEEE J. SolidState Circuits, Vol. 25, pp. 1550-1561, 1990.

17

Chapter 1 Introduction of High- MIM Technology [25] C. H. Ng and S. F. Chu, Effect of the nitrous oxide plasma treatment on the MIM capacitor, IEEE Electron Device Letters, Vol. 23, No. 9, pp. 529-531, 2002. [26] C. H. Ng, K. W. Chew and S. F. Chu, Characterization and comparison of PECVD silicon nitride and silicon oxynitride dielectrics for MIM capacitors, IEEE Electron Device Lett., Vol. 24, No. 8, pp. 506-508, 2003. [27] S. Van Huylenbroeck, S. Decoutere, R. Venegas, S. Jenei, and G. Winderickx, Investigation of PECVD dielectrics for nondispersive metal-insulator-metal capacitors, IEEE Electron Device Lett., Vol. 23, No. 4, pp. 191-193, 2002. [28] K. Stein, J. Kocis, G. Hueckel, E. Eld, T. Bartush, R. Groves, N. Greco, D. Harame, and T. Tewksbury, High reliability metal insulator metal capacitors for silicon germanium analog applications, in Proc. of BCTM, pp. 191-194, 1997. [29] T. Yoshitomi, Y. Ebuchi, H. Kimijama, T. Ohguro, E. Morifuji, H. S. Momose, K. Kasai, K. Ishimaru, F. Matsuoka, Y. Katsumata, M. Kinugawa, and H. Iwai, High performance MIM capacitor for RF BiCMOS LSIs, in Proc. of BCTM, pp. 133-166, 1999. [30] P. Zurcher, P. Alluri, P. Chu, P. Duvallet, C. Happ, R. Henderson, J. Mendonca, M. Kim, M. Petras, M. Raymond, T. Remmel, D. Roberts, B. Steimle, J. Stipanuk, S. Straub, T. Sparks, M. Tarabbia, H. Thibieroz, and M. Miller, Integration of thin film MIM capacitors and resistors into copper metallization based RF-CMOS and Bi-CMOS technologies, in Proc. of IEDM, pp. 153-156, 2000. [31] C. C. Lin, H. M. Hsu, Y. H. Chen, T. Shih, S. M. Jang, C. H. Yu, and M. S. Liang, A full Cu damascene metallization process for sub-0.18 m RF CMOS SoC high Q inductor and MIM capacitor application at 2.4 GHz and 5.3 GHz, Int. Interconnect Tech. Conference, pp. 113-115, 2001.

18

Chapter 1 Introduction of High- MIM Technology [32] R. B. van Dover, R. M. Flemming, L. F. Schneemeyer, G. B. Alers, and D. J. Werder, Advanced dielectrics for gate oxide, DRAM and rf capacitors, in Proc. of IEDM, pp. 823-826, 1998. [33] J. Robertson, Electronic structure and band offsets of high-dielectric-constant gate oxides, MRS Bulletin, pp. 217-221, 2002. [34] G. D. Wilk, R. M. Wallace, and J. M. Anthony, High- gate dielectrics: current status and material properties considerations, J. Appl. Phys., Vol. 89, No. 10, pp. 5243-5275, 2001. [35] J. McPherson, J. Kim, A. Shanware, H. Mogul and J. Rodriguez, Proposed universal relationship between dielectric breakdown and dielectric constant, in Proc. of IEDM, pp. 633-636, 2002. [36] C. Chaneliere, J. L. Autran, R. A. B. Devine, and B. Balland, Tantalum pentoxide (Ta2O5) thin films for advanced dielectric applications, Materials Science and Engineering, R22, pp. 269-322 1998. [37] T. Ishikawa, D. Kodama, Y. Matsui, M. Hiratani, T. Furusawa, and D. Hisamoto, High-capacitance Cu/Ta2O5/Cu MIM structure for SoC applications featuring a single-mask add-on process, in Proc. of IEDM, pp. 940-942, 2002. [38] Y. L. Tu, H. L. Lin, L. L. Chao, D. Wu, C. S. Tsai, C. Wang, C. F. Huang, C. H. Lin, and J. Sun, Characterization and comparison of high- metal-insulator-metal (MIM) capacitors in 0.13m Cu BEOL for mixed-mode and RF applications, in Proc. Symp. VLSI Technology, pp. 79-80, 2003. [39] S. B. Chen, C. H. Lai, A. Chin, J. C. Hsieh, and J. Liu, High-density MIM capacitors using Al2O3 and AlTiOx dielectrics, IEEE Electron Device Lett., Vol. 23, No. 4, pp. 185-187, 2002.

19

Chapter 1 Introduction of High- MIM Technology [40] M. Y. Yang, C. H. Huang, A. Chin, C. Zhu, M. F. Li, and D. -L. Kwong, Highdensity MIM capacitors using AlTaOx dielectrics, IEEE Electron Device Lett., Vol. 24, No.5, pp.306-308, 2003. [41] M. Y. Yang, C. H. Huang, A. Chin, .C. Zhu, B. J. Cho, M. F. Li, and D. -L. Kwong, Very high density RF MIM capacitors (17 fF/m2) using High- Al2O3 doped Ta2O5 Dielectrics, IEEE Microwave and wireless components Letts., Vol. 13, pp. 431-433, 2003. [42] J. C. Lee, H. J. Cho, C. S. Kang, S. J. Rhee, Y. H. Kim, R. Choi, C. Y. Kang, C. H. Choi, and M. Abkar, High- dielectrics and MOSFET characteristics, in Proc. of IEDM, pp. 95-98, 2003. [43] H. Hu, C. Zhu, Y. F. Lu, M. F. Li, B. J. Cho, and W. K. Choi, A High Performance MIM Capacitor Using HfO2 Dielectrics, IEEE Electron Device Lett., Vol. 23, No. 9, pp. 514-516, 2002. [44] S. J. Kim, B. J. Cho, M. F. Li, C. Zhu, A. Chin, and D.-L. Kwong, HfO2 and lanthanide-doped HfO2 MIM capacitors for RF/mixed IC applications, in Proc. Symp. VLSI Technology, pp.77-78, 2003. [45] H. Hu, C. Zhu, X. Yu, A. Chin, M. F. Li, B. J. Cho, D. L. Kwong, P. D. Foo, M. B. Yu, X. Liu, and J. Winkler, MIM capacitors using atomic-layer-deposited high- (HfO2)1-x(Al2O3)x Dielectrics, IEEE Electron Device Lett., Vol. 24, No. 2, pp. 60-62, 2003. [46] H. Hu, S. -J. Ding, H. Lim, C. Zhu, M. F. Li, S. J. Kim, X. Yu, J. H. Chen, Y. F. Yong, B. J. Cho, D. S. H. Chan, Subhash C Rustagi, M. B. Yu, C. H. Tung, A. Y. Du, D. My, P. D. Foo, A. Chin, and D. -L. Kwong, High performance ALD HfO2-Al2O3 laminate MIM capacitors for RF and mixed signal IC applications, in Proc. of IEDM, pp. 379-382, 2003.

20

Chapter 1 Introduction of High- MIM Technology [47] F. Mondon, and S. Blonkowski, Electrical characterization and reliability of HfO2 and Al2O3-HfO2 MIM capacitors, Microelectronics Reliability, Vol. 43, pp. 1259-1266, 2003. [48] Y. Matsui, M. Hiratani, I. Asano, and S. Kimura, Niobia-stabilized tantalum pentoxide (NST)-novel high- dielectrics for low-temperature process of MIM capacitors, in Proc. of IEDM, pp. 225-228, 2002. [49] T. Remmel, R. Ramprasad, and J. Walls, Leakage behavior and reliability assessment of tantalum oxide dielectric mim capacitors, IEEE International Reliability Physics Symposium Proceedings, pp. 277-281, 2003. [50] R. Ramprasad, Phenomenological theory to model leakage currents in metalinsulator-metal capacitor systems, Phys Status Solidi, B 239 (1), pp. 59-70, 2003. [51] M. Kiyotoshi, K. Hieda, Y. Fukuzumi, Y. Kohyama, T. Suzuki, D. Matsunaga, and K. Hashimoto, Control of two types of dielectrics relaxation current for Ta2O5 metal-insulator-metal capacitors, Jpn. J. Appl. Phys., Vol. 42, pp. 19431948, 2003. [52] H. Reisinger, G. Steinlesberger, S. Jakschik, M. Gutsche, T. Hecht, M. Leonhard, U. Schrder, H. Seidl, and D. Schumann, A comparative study of dielectric relaxation losses in alternative dielectrics, in Proc. of IEDM, pp. 267-270, 2001.

21

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD)

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD)

2.1. Introduction

Although remained little known until the late 1980s, pulsed-laser deposition (PLD) has emerged as a simple, reliable and fast technique that offers a great experimental versatility. The setup of PLD system used in this work is shown in Fig. 2.1. A pulsed laser is used as the light source to ablate a target, and the material ablated from the target is condensed on a substrate and forms a thin film. Over the past few years, PLD is increasingly being used to prepare a wide variety of materials in thin film forms [1, 2]. Its low start-up cost, laser energy source independent of the deposition system, the stoichiometric removal of constituent species from the target during ablation, and the relatively small number of control parameters appeal more and more attention. More importantly, the PLD technique is well known for the quality of the layers grown at relatively lower substrate temperatures than other thin film deposition methods [1, 2]. This is desirable for MIM capacitors integrated into back-end of line (BEOL) process where a low thermal budget (~400oC) is needed.

22

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD)

Figure 2.1: Experimental configuration of pulsed-laser deposition system in this work. For successful integration of MIM capacitors, extremely reliable and high quality HfO2 thin films are needed. Several thin film growth techniques such as atomic-layer-deposition (ALD) [3, 4], evaporation with ion-assisted deposition (IAD) [5], sol-gel [6], sputtering [7, 8], in-situ rapid thermal CVD (RTCVD) [9, 10], and metallorganic chemical vapor deposition (MOCVD) [11, 12] have been employed to fabricate good quality HfO2 thin films. The properties of HfO2 thin films have been reported to be strongly dependent on the fabrication method. Therefore, an understanding of process-structure-property correlation is of great importance to exploit HfO2 for thin film devices application. In this chapter, HfO2 thin films were fabricated using PLD at various substrate temperatures and oxygen pressures, in order to study physical properties dependence on process parameters. In addition, excellent electrical performance of HfO2 MIM

23

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) capacitor had been demonstrated for the first time [13, 14], suggesting the great potential of HfO2 for MIM capacitors application.

2.2. Experiments

The deposition was accomplished in a stainless-steel vacuum chamber of the PLD system that was evacuated by a turbo-molecular pump to 110-5 Torr, the oxygen pressure was measured by a convectron vacuum gauge (1 mTorr-1000 Torr) and a single gauge TM (< 1 mTorr) respectively, and it was controlled and adjusted by a gate valve. The purity of Hf target is 99.5%; it was placed on the target holder that rotated constantly by an external motor to prevent surface craters. The target was irradiated by a focused KrF excimer laser beam ( = 248 nm, = 30 ns) at an incidence angle of 45o with a repetition rate of 5-10 Hz. The laser fluence was set between 3.0 and 7.0 J/cm2. In this experiment, for physical properties characterization, silicon substrates were used for HfO2 thin films deposition at various substrate temperatures ranging from room temperature (25oC) to 750oC and at various oxygen pressures varying from 10 to 200 mTorr. For electrical and dielectrical measurement, MIM capacitors with HfO2 high- dielectric films were fabricated on a layer of 500 nm SiO2 deposited on silicon substrate. The SiO2 is for isolation purpose. A layer of Ta film (~1000 ) was then deposited ex situ by sputtering on the SiO2 layer as the bottom electrode. Following that, high- HfO2 dielectric films were deposited in an oxygen ambient of 50 mTorr at 200, 300, and 400oC. It is noted that the deposition temperature was kept at or below 400oC for MIM capacitor fabrication in order to meet the thermal budget requirement of BEOL process. Finally, Al was deposited by evaporation and patterned as top electrode by wet etching with the device area being 2.54104 m2.

24

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) The crystal structures of HfO2 thin films deposited on Si substrates were investigated by X-ray diffraction (Phillips PW 1729 X-Ray diffractometer, Cu K radiation, = 0.5418 nm). The surface morphology was obtained using an Au-toProbe CP atomic force microscope (AFM) in the contact mode. The film thicknesses were measured by an Alpha-step 500 surface profiler (Tencor Instruments) and further confirmed by cross-sectional transmission electron microscopy (TEM) analyses. Scanning electron microscopy (SEM) was also used to inspect particulates generation on the surfaces of HfO2 films. Time of Flight Secondary Ion Mass Spectroscopy IV (TOF-SIMS IV) was employed to characterize the change of the relative stoichiometry of the HfO2 films prepared at various deposition conditions. The optical constants, i.e. refractive index and extinction coefficient, of HfO2 thin films were evaluated by a variable angle spectroscopic ellipsometer (VASE). For electrical measurements, the leakage current was measured using an HP4155A parameter analyzer, and the capacitance was characterized using an HP4284A precision LCR meter at frequencies varied from 500 Hz to 1 MHz.

2.3. Results and discussion

2.3.1. Physical characterization of PLD processed HfO2

HfO2 is a material forming several polymorphs, although pure HfO2 tends to appear in the monoclinic phase at room temperature and atmospheric pressure, orthorhombic and tetragonal phases could be formed at high pressures and/or high temperatures [15, 16], which is generally thought to be metastable if present at room temperature and atmospheric pressure. Figure 2.2 shows the XRD patterns of HfO2

25

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) thin films deposited at various temperatures with oxygen pressure of 50 mTorr. For comparison, spectrum (a) of the bare Si substrate is shown. Spectra (b) and (c) show no apparent diffraction peaks of HfO2, indicating that the films deposited at 200oC or below are amorphous. Spectrum (d) shows some weak diffraction peaks, which are identified from monoclinic phase of HfO2. Spectrum (e) exhibits intense diffraction peaks indicating the improved crystallinity at high temperature; and no tetragonal or orthorhombic phase was found to be present. In addition, different orientations of crystallites in the thin film are observed compared to HfO2 prepared at 300oC, which suggest a polycrystalline structure change at a temperature above 300oC.

(111)

4000

(200) (002)

HfO2 peaks
(112)

Si peaks e. HfO2 (500 C)

(202) (220)

(221) (122)
o

Intensity (A.U.)

(020)

3000 2000 1000 0 30

(211)

d. HfO2 (300 C)

c. HfO2 (200 C)
o

b. HfO2 (25 C) a. Si substrate

35

40

45

50

2 , deg
Figure 2.2: XRD patterns of HfO2 thin films deposited on Si(100) substrates at various substrate temperatures.

The substrate temperature also influences the surface mobility of ablated species and therefore affects the deposition rates of the deposited films. Figure 2.3 26

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) shows the deposition rate as a function of the substrate temperature with different laser fluence. It is found that the deposition rates are of the order of 102 nm per pulse, and the highest deposition rate was at 25oC. As the substrate temperature increases, the sticking coefficient of Hf-bearing species drops, this may result in a decrease in the deposition rate. In addition, the as-deposited films become more densified with the increase of substrate temperature, which is believed to be another factor affecting the deposition rates. The similar trend could also be found elsewhere [17, 18]. In Fig.2.3, it is also found that a higher deposition rate can be achieved by using a higher laser energy density, due to a higher ablation rate on the target.

Deposition Rate (10 nm)/Pulse

7 6 5 4 3 2 10 Hz, 60 min 50 mTorr 25 300 500 200 o Substrate Temperature ( C) Laser Energy Density 2 4.0 J/cm 2 7.0 J/cm

Figure 2.3: Deposition rates of HfO2 thin films deposited on Si substrates at various substrate temperatures

Surface morphology is another important physical property which may affect the electrical properties of dielectric thin films. Figure 2.4 shows the three-dimensional AFM images of HfO2 samples used for XRD measurement in Fig. 2.2, and it is in

-2

27

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD)

(a)

(b)

(c)

(d)

Figure 2.4: Three dimensional AFM images of HfO2 thin films deposited on Si substrates at various substrate temperatures of (a). 25, (b). 200, (c). 300, and (d). 500oC respectively.

28

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) agreement with XRD experimental result. In Fig. 2.4(a) and Fig. 2.4(b), the film deposited at or below 200oC shows no obvious crystallization. In contrast, the film deposited at 500oC exhibits an apparent polycrystalline structure. In addition, it is further shown by AFM measurement that the average surface roughness of HfO2 thin films changes with substrate temperature, with approximately 7.8, 2.7, and 3.2, and 4.6 for HfO2 prepared at 25, 200, 300, and 500oC, respectively. It is found that HfO2 thin film prepared at 200oC can effectively improve the surface roughness. In amorphous phase, it is believed that thin film prepared at 200oC could enhance the surface diffusion during deposition and thus minimize the microstructure, and resulting in a smoother surface. However, when HfO2 was prepared at or above the crystallization temperature of 300oC, the film surface again became rough which is believed to be due to crystallization induced large grain size. Grain formation at or above 300oC and the evolution of surface roughness of HfO2, confirmed by XRD and AFM measurements, may affect the electrical properties, as will be shown later. In this work, in order to characterize the change of the stoichiometry of HfO2 films, we used secondary ion mass spectrometry (SIMS) with time-of-flight (TOF) detection of secondary ions for analysis. Depth profiles were obtained using dual beam technique with 25 kV Ga+ primary ions for analysis and 3 kV Ar+ ions for sputtering. A low energy electron gun was used to compensate static electric charge on the oxide. To avoid surface and interface transients, the signals of secondary ions used for characterization of the film were measured only in the range of depth, where the signals are constant. The mass spectrum of HfO2 film consists of O+, Hf+ and various HfxOy+ clusters. While intensities of the clusters depend on composition, ionization and fragmentation probabilities, the intensities of the elements depend on composition and ionization yield only. Thus we take the ratio
16

O/180Hf as a measure of relative

29

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) composition of the elements. Though the ionization yield also depends on composition (so called matrix effect [19]), by taking the ratio of the signals, we were able to minimize this effect. Hence higher O/Hf ratio corresponds to higher oxygen content in the sample, and equal ratio for different samples indicates equal composition.

Table 2.1: The ratios of SIMS intensities O/Hf for HfO2 thin films prepared at various substrate temperatures (oxygen pressure: 50 mTorr). Temperatures (oC) 25 200 300 500 750

O/Hf 0.18 0.17 0.18 0.21 0.18

Table 2.2: The ratios of SIMS intensities O/Hf for HfO2 thin films prepared at various oxygen pressures (All samples are prepared at room temperature 25oC.).

Pressure (mTorr) 10 50 200

O/Hf 0.10 0.18 0.21

Table 2.1 presents the O/Hf ratio for HfO2 films deposited at various substrate temperatures. This ratio remains almost constant indicating that the deposition

30

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) temperature up to 750oC has little effect on the stoichiometry of HfO2 films. However, the fluctuations of O/Hf ratio in the whole temperature range can be attributed most likely to the change of surface roughness of the films, which is evidenced from Fig. 2.3. Table 2.2 shows the O/Hf ratio for HfO2 films deposited at room temperature and various oxygen pressures. At the pressure 50 mTorr and above, the composition of the oxide remains essentially the same. However at lower pressure, the content of oxygen falls significantly; at 10 mTorr, it drops down to a half of 50 mTorr. It is thus concluded that deposition pressure affects the stoichiometry of the as-deposited thin films whereas deposition temperature does not. In order to further study the effects of deposition temperature and oxygen pressure on the physical properties of HfO2 thin films, the optical constants, i.e. refractive index and extinction coefficient, of HfO2 thin films deposited at various parameters were determined with a variable angle spectroscopic ellipsometer, and compared with that of the bulk material HfO2. Figure 2.5(a) shows refractive indexes of HfO2 films deposited at various substrate temperatures. It can be seen that, with the increase of deposition temperatures, the refractive indexes increase steadily, and the curves of spectral dependence of the refractive indexes at 300 and 500oC are nearly overlapped with each other. It is noticed that when the deposition temperature increases to 200oC, the refractive index at 600 nm is 1.98, which is close to the bulk refractive index 2.08 at 600 nm [20]. For the film prepared at 300 and 500oC, the refractive indexes at 600 nm are 2.11 and 2.12 respectively, which are almost same as that of bulk material. From the above SIMS measurement, it is concluded that the change of deposition temperatures has little effect on the stoichiometry of HfO2 thin film prepared by PLD, which means that the change of refractive index could not be

31

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD)

2.3 2.2

Refractive index

2.1 2.0 1.9 1.8 1.7 1.6 200 400 600

25 200 300 500

o o

C C o C o C

800 1000 1200 1400 1600 1800

(a)

Wavelength (nm)
2.1 2.0

Refractive index

1.9 1.8 1.7 1.6 1.5 1.4 1.3 200 400 600 800 1000 1200 1400 1600 1800
(b)

10 mTorr 50 mTorr 200 mTorr

Wavelength (nm)

Figure 2.5: Spectral dependence of refractive indexes of HfO2 films deposited at (a) various substrate temperatures (oxygen pressure: 50 mTorr) and (b) various deposition pressures (all deposited at room temperature).

32

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) due to the variation of oxygen concentration of HfO2 thin films prepared at various deposition temperatures. However, it is believed that usually for the films deposited at lower temperature, the as-deposited film has a lower packing density because of a loose arrangement. A higher deposition temperature increases the mobility of the film atoms or molecules and therefore favours the formation of more closely packed thin films, which leads to a higher refractive index. Figure 2.5(b) shows the refractive indexes of HfO2 films deposited at various oxygen pressures. Since all the samples were prepared at room temperature, the influence of deposition temperature on the packing densities of thin films deposited at various oxygen pressures is assumed to be the same. The change of refractive indexes at various deposition pressures is mainly attributed by the change of oxygen concentration in HfO2 thin films from SIMS measurements. It can be seen from Fig. 2.5(b) that, for the film deposited at a low pressure of 10 mTorr, the refractive index is 1.92 at 600 nm, the highest among all the films prepared at various oxygen pressures. However, such a high refractive index may be due to oxygen vacancies formed during film preparation [21]. As for the film deposited at a high pressure of 200 mTorr, the refractive index is only 1.41 at 600 nm. This could be attributed to the incorporation of excessive oxygen during deposition, which may create voids and absorb water vapor upon venting the vacuum chamber. Also the reduction of the kinetic energy of the ablated Hf-bearing species, which undergo more collisions with the background O2 molecules before reaching the growing film surface, will result in a little lower density film [22]. All the above effects are believed to be responsible for the reduction of the refractive index of HfO2 thin film deposited at high pressure. In addition, Figures 2.6(a) and 2.6(b) show the extinction coefficient (K factor) dependence of wavelength for HfO2 thin films prepared at various deposition

33

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD)

0.01

Extinction coefficient K

1E-4 1E-6 1E-8

1E-10 1E-12 200

25 C o 200 C o 300 C o 500 C

400 600 800 1000 1200 1400 1600 1800
(a)

Wavelength (nm)
0.1

Extinction Factor K

0.01

1E-3

10 mTorr 50 mTorr 200 mTorr

1E-4

1E-5 200

400

600

800 1000 1200 1400 1600 1800

(b)

Wavelength (nm)

Figure 2.6: Spectral dependence of extinction coefficients of HfO2 films deposited at (a) various substrate temperatures (oxygen pressure: 50 mTorr) and (b) various deposition pressures (all deposited at room temperature).

34

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) conditions. As shown in Fig. 2.6(a), the extinction factors (K values) decrease for the samples prepared from room temperature to 300oC. The K value for the sample prepared at 300oC is quite low in the visible region (380-770 nm) and near infrared region (770-1400 nm), which indicate that a good quality HfO2 film is obtained in terms of optical properties. As for the sample deposited at 500oC, due to the measured wavelength limitation of the instrument, no obvious absorption could be detected in the ultraviolet region, and the K values are well above those of all other samples in visible and near infrared regions after simulation. Figure 2.6(b) shows the extinction factor dependence of wavelength of HfO2 thin films deposited at various oxygen pressures. It is shown that the extinction factor of the film deposited at low pressure 10 mTorr is well above those of the films deposited at relative high pressures (50 and 200 mTorr), which could be due to large amount of defects in the film, such as oxygen vacancies [23].

2.3.2. Electrical characterization of HfO2 MIM capacitor

Following the physical properties characterization, HfO2 MIM capacitors are fabricated at 200, 300, and 400oC in oxygen ambient of 50 mTorr, with the thickness of 56, 57, and 54 nm for each deposition temperature, to evaluate the electrical properties. Figure 2.7 presented the TEM photo of 56 nm HfO2 MIM structure prepared at 200oC, and there is no evidence of interfacial layers formation as demonstrated by TEM showing an in-depth homogeneous dielectric material. Here it needs to be mentioned that, we keep the maximum temperature at or below 400oC for compatibility with the BEOL process. Among various requirements for analog MIM capacitor, leakage characteristic is a critical issue for MIM capacitor application.

35

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) Figure 2.8 shows the current-voltage (I-V) characteristics of three samples of HfO2 MIM capacitors. The HfO2 thin film prepared at 200oC shows the lowest leakage current of 210-9 A/cm2 at 3 V. The HfO2 samples deposited

Figure 2.7: TEM photos of 56 nm HfO2 MIM capacitor fabricated at 200oC

at 300oC, however, show the worst leakage property. This is believed to be due to the formation of grain boundaries after crystallization (Figure 2.2). At an even higher substrate deposition temperature of 400oC, the leakage property improves though it is still inferior to the samples prepared at 200oC. This may be due to possible oxidation of the bottom electrode (Ta) before HfO2 thin films deposition [24]. In addition, as evidenced from Fig. 2.2, for HfO2 films prepared above 300oC, the crystallinity is improved and the crystallographic orientation is changed. This implies a change of the polycrystalline HfO2 structure, and it may alter the electrical properties to some extent. From previous discussion, it is desirable to prepare HfO2 thin film at a high temperature such as 300oC in terms of optical properties [25]. However, in order to obtain good insulating properties, it is desirable to keep the HfO2 thin film to be in a

36

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) glassy (amorphous) phase, since grain boundaries are detrimental to serve as leakage paths. In addition, increased surface roughness of HfO2 after crystallization could be interpreted as an image force which lowers the barrier height for electron transport. This appears to be another factor which may degrade the leakage property [26].

Leakage current (A/cm )

10 10 10 10 10 10

-5

-6

200 C o 300 C o 400 C

-7

-8

-9

Vg + GND Al dot HfO2 Ta

-10

DC bias on top electrode (V)

Figure 2.8: Current-voltage characteristic of HfO2 MIM capacitors prepared at 200, 300, and 400oC respectively.

Figure 2.9 shows the dielectric constants () and dissipation factors ( tan ) of HfO2 thin films as a function of the deposition temperature. For HfO2 thin film deposited at 200oC, the dielectric constant is less dependent on frequency and remains relatively constant in the whole frequency range (500 kHz-1 MHz). In addition, a low dissipation factor (below 0.02) is observed at up to 1 MHz. This suggests that the HfO2 MIM capacitor prepared at 200oC has very low dielectric loss with a capacitance density of 3 fF/m2. However, for HfO2 films prepared at substrate temperatures of

37

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) 300 and 400oC, the dielectric constants decrease at high frequencies with an obvious increase in the dissipation factor. This may be related to the higher leakage current observed.

30

Dielectric constant ()

20 15

0.4 0.3 0.2

10 5 0 1k 10k 100k 1M

0.1 0.0 -0.1

Frequency (Hz)

Figure 2.9: Capacitance versus frequency at zero bias for HfO2 MIM capacitors prepared at 200, 300, and 400oC respectively.

As already known, capacitor voltage linearity is another very important parameter for MIM capacitors in silicon analog circuit applications. Figure 2.10 shows the normalized capacitance of the MIM capacitor prepared at 200, 300, and 400oC with applied voltage at different frequencies. At each measured frequency, the normalized capacitance of the MIM capacitor can be fitted by dC/C0=(C(V)C0)/C0 = V2 + V

Dissipation factor
38

25

200 C o 300 C o 400 C

0.6 0.5

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD)

5000 4000 3000 2000 1000 0 -1000 12000

(a)
1 kHz 10 kHz 100 kHz 1MHz

200 C deposition

C/C0 [ppm]

10000 8000 6000 4000 2000 0 -2000 10000 8000 6000 4000 2000 0 -2000 -1

(b)

300 C deposition

(c)

400 C deposition
0 1 2 3 4 5 6

DC bias on top electrode (V)

Figure 2.10: Normalized capacitance of HfO2 MIM capacitors prepared at (a) 200, (b) 300, and (c) 400oC as a function of voltage applied at a frequency of 1 kHz, 10 kHz, 100 kHz, and 1 MHz respectively.

39

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) where, C0 is the zero biased capacitance at each frequency, and are the quadratic and linear voltage coefficient, respectively. The capacitances were measured with the voltage changed from 0 V to 5 V at 1 kHz, 10 kHz, 100 kHz, and 1 MHz respectively. The and values obtained are shown in Table 2.3. The results indicate that the voltage coefficients of capacitance (VCCs) strongly depend on the frequency and increase with decreasing the frequency (Figure 2.10 and Table 2.3). This dispersive behaviour of MIM capacitors with HfO2 dielectric is temporarily attributed to the existence of traps within high- films. Different traps will induce charges with different time constants and strongly modulate capacitor charges at certain frequencies. When the frequency is decreased, the induced charges will be easier to follow the ac signal, and therefore result in higher VCCs. For the mechanism of the frequency dependence of voltage coefficients, we will further discuss this in Chapter 5. From Table 2.3, it is noticed that, HfO2 MIM capacitor prepared at 200oC shows both low quadratic and linear voltage coefficients, which are comparable to MIM capacitor with Si3N4 [27]. For the HfO2 thin films prepared at 300 and 400oC, the capacitance variation C/Co turns out to be larger than that of HfO2 thin films deposited at 200oC, due to their poorer leakage property. Thus, we conclude that the relative capacitance variation at a certain voltage is correlated to the insulating properties of HfO2 thin films prepared at various deposition conditions. This kind of behaviour and relation has also been observed in Ta2O5 MIM capacitors [28]. For comparison, it is also noted that, HfO2 samples prepared at 300 and 400oC have linear voltage coefficients that are much larger than those prepared at 200oC. However, their quadratic coefficients are smaller when compared to those amorphous HfO2 prepared at 200oC. When we consider the voltage linearity requirements for analog MIM capacitor, the decrease of quadratic coefficients is significant. Since

40

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) according to the 2001 ITRS roadmap [29], quadratic voltage coefficients are more critical for the dynamic range of analog capacitor. On the other hand, linear voltage coefficients can be cancelled out by differential techniques. However, the correlation between materials properties and the variation of and values remains unclear.

Table 2.3: Voltage linearity coefficients as a function of frequency for HfO2 MIM capacitors prepared at 200, 300, and 400oC respectively.

200oC Deposition Frequency (ppm/V2) 1 kHz 10 kHz 100 kHz 1 MHz 134.3 89.0 64.9 44.3 (ppm/V) 176.6 181.9 156.5 125.2

300oC Deposition (ppm/V2) -20.2 31.9 -10.5 32.8 (ppm/V) 2189.7 1255.9 1048.9 461.6

400oC Deposition (ppm/V2) -53.1 -22.4 3.2 8.3 (ppm/V) 1797.9 802.7 377.4 207.6

Following VCCs characterization, temperature coefficients of capacitance (TCCs) were evaluated for 200oC prepared HfO2 MIM capacitors, which could be defined as: 10 6 dC TCC = ppm / oC T dT It should be noted that the capacitance variation with temperature is mainly caused by the temperature dependence of the dielectric properties. The capacitance change due to thermal expansion of capacitor area is believed to have negligible effect [30].

41

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) Figure 2.11 shows the normalized capacitance of the MIM capacitor fabricated at 200oC as a function of temperatures at a frequency of 10 kHz, 100 kHz, and 1 MHz, respectively. The results show that the capacitance increases with the increase of the temperature. The temperature coefficients of capacitance (TCCs) are 196 ppm/oC, 196 ppm/oC, and 147 ppm/oC for the frequency at 10 kHz, 100 kHz, and 1 MHz, respectively. The TCC at 1 MHz is the lowest for HfO2 MIM capacitor. Compared to the TCCs of 127 ppm/oC at 1 MHz and 187 ppm/oC at 1 kHz for Si3N4 MIM capacitor [27], HfO2 MIM capacitor shows comparable TCCs.

Normalized capacitance [ppm]

35000 30000 25000 20000 15000 10000 5000 0 0

TCC = 147 ppm/ C (1 MHz) o TCC = 196 ppm/ C (100 kHz) o TCC = 196 ppm/ C (10 kHz)

25

50 75 100 o Temperature ( C)

125

150

Figure 2.11: Normalized capacitance of HfO2 MIM capacitor prepared at 200oC as a function of temperature.

Considering the leakage characteristics and the capacitance performance at various deposition temperatures, it is desirable to select the optimum substrate temperature of 200oC for HfO2 thin film deposition using PLD. In addition, recent 42

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) progress in Cu and low- interconnect technology requires much lower temperature than 400C which is traditionally accepted for BEOL process. The maximum allowed temperature for low- dielectric decreases with the decrease of value [31]. To get a value of around 2, we need to keep the maximum process temperature as low as 200C [31]. Furthermore, Cu diffusion will be much reduced at a lower temperature. Comparing to 400C, Cu diffusivity in low- dielectric at 200C is 4 orders lower [32]. In summary, according to the ITRS roadmap [29], the typical requirements of analog capacitor are capacitance density of 3 fF/m2, voltage linearity of 100 ppm/V2, and leakage current of 7 fA/[PFV] in the current technology node. For the 56 nm HfO2 MIM capacitor prepared at 200oC, the obtained parameters are comparable with an even lower leakage of ~2.8 fA/[PFV], which can meet the strict specifications of analog capacitor.

2.4. Limitations of PLD for thin film fabrication

Even though PLD has been proved to be an effective method for the fabrication of high quality films, like HfO2 as a dielectric in MIM capacitors, some intrinsic drawbacks severely limited PLDs application for thin film deposition in the current Si ULSI technology. Among them, particulate splashing and non-uniformity are of the most serious concerns which we like to point out as follows: 1. Particulate splashing Particulate splashing is an intrinsic problem of PLD method for many thin film fabrications [1, 2], which is particularly problematic for semiconductor films when

43

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD)

(a)

(b) Figure 2.12: SEM top views of HfO2 film surfaces prepared with the laser fluence of (a) 4.0 and (b) 7.0 J/cm2 respectively (fabricated at room temperature).

44

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) considering small feature sized electronic devices. In the PLD processing of HfO2 films, particulates were observed to be present on the surface of HfO2 thin films. Figure 2.12(a) and Figure 2.12(b) illustrated the top views of PLD processed HfO2 films with the laser fluence of 4.0 and 7.0 J/cm2 respectively. The feature sizes of the particulates were in the sub-micron regime. As expected, the number of generated particulates decreases with laser fluence. Therefore, in our work, we keep the laser energy low to minimize the particulates density on the surfaces of HfO2 films. However, it would be very difficult in most cases to completely avoid the particular splashing during the PLD processing of thin films using the conventional configuration of PLD system as shown in Fig. 2.1. With regard to the particulate occurrence, the following mechanisms were believed to be responsible, like subsurface boiling, the shock wave recoil pressure induced liquid layer expulsion, and splashing can be one or a combination of those mechanisms. To avoid splashing, numerous attempts have been made, such as the manipulation of plume and target, and mechanical filter, etc. However we do not intend to further investigate the particulates splashing on HfO2 films in this work. 2. Non-uniformity for thin film deposition Another major drawback is the lack of uniformity over the substrate area due to the narrow angular distribution of the plume [1, 2], which makes the PLD method unfeasible for the current Si wafer processing. In practice, several methods have been employed to alleviate this problem, including the rastering of the laser, the substrate rotation, and so on. In our work, we used small pieces of Si wafers with the area being ~11 cm2. In a word, even though PLD is a good tool for materials study and research purpose, it remains to be difficult to find its wide acceptance in industry for thin film

45

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) fabrications. In the following chapters, sputtering and atomic-layer deposition (ALD) methods will be used to further explore HfO2 based high- dielectrics for MIM capacitors application which are free from the drawbacks mentioned above.

2.5. Conclusion

In this chapter, HfO2 thin films have been prepared by PLD at various deposition conditions. For the physical properties characterization, the influence of the substrate temperature and pressure on film properties, including crystallinity, surface morphology, relative stoichiometry, and optical properties, were investigated. It can be concluded that substrate temperature has little effect on the stoichiometry, whereas deposition pressure plays an important role in determining the ratio of Hf and O. The result also shows that the optical properties of HfO2 thin films have a strong dependence on both the deposition temperature and pressure. Thus, the appropriate choice of substrate temperature and deposition pressure in PLD processing of HfO2 thin films is of great importance. Based on the physical characterization, MIM capacitors using HfO2 dielectric were fabricated. The electrical properties of HfO2 MIM capacitors were evaluated as a function of deposition temperature. It is also shown to have strong correlation to the material properties. For the first time, a high performance MIM capacitor using high- HfO2 dielectric was demonstrated with a low thermal budget of 200oC. It showed an overall high electrical performance such as a high capacitance density of ~3.0 fF/m2, a low leakage current of 2x10-9 A/cm2 at 3 V, low voltage coefficients of capacitance, and good frequency dispersion property. Compared with Si3N4 MIM capacitors currently used in the industry, the capacitance density is high. In summary, all these

46

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) indicate that HfO2 is a very good high- dielectric used in MIM capacitors for Si analog circuit applications.

47

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) References: [1] D. B. Chrisey and G. K. Hubler, Pulsed Laser Deposition of Thin Films (Wiley, New York, 1994) [2] E. Fogarassy and S. Lazare, Laser ablation of electronic materials: basic mechanisms and applications (Amsterdam: North-Holland, 1992) [3] M. Y. Ho, H. Gong, G. D. Wilk, B.W. Busch, M. L. Green, P. M. Voyles, D. A. Muller, M. Bude, W. H. Lin, A. See, M. E. Loomans, S. K. Lahiri, and P. I. Raisanen, Morphology and crystallization kinetics in HfO2 thin films grown by atomic layer deposition, J. Appl. Phys., Vol. 93, No. 10, pp. 1477-1481, 2003. [4] J. Aarik, A. Aidla, H. Mndar, T. Uustare, K. Kukli, and M. Schuisky, Phase transformations in hafnium dioxide thin films grown by atomic layer deposition at high temperatures, Applied Surface Science, Vol. 173, pp. 15-21, 2001. [5] M, Gilo and N, Croitoru, Study of HfO2 films prepared by ion-assisted deposition using a gridless end-hall ion source, Thin Solid Films, Vol. 350, pp. 203-208, 1999. [6] T. Nishide, S. Honda, M. Matsuura, and M. Ide, Surface, structural and optical properties of sol-gel derived HfO2 films, Thin Solid Films, Vol. 371, 61-65, 2000. [7] B. H. Lee, L. Kang, R. Nieh, W. -J. Qi, and J. C. Lee, Thermal stability and electrical characteristics of ultrathin hafnium oxide gate dielectric reoxidized with rapid thermal annealing, Appl. Phys. Lett., Vol. 76, pp. 1926-1928, 2000. [8] R. Choi, K. Onishi, C. S. Kang, S. Gopalan, R. Nieh, Y. H. Kim, J. H. Han, S. Krishnan, H. -J Cho, A. Shahriar, and J. C. Lee, Fabrication of high quality ultrathin HfO2 gate dielectric MOSFETs using deuterium anneal, in Proc. of IEDM, pp. 613-616, 2002.

48

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) [9] S. J. Lee, H. F. Luan, W. P. Bai, C. H. Lee, T. S. Jeon, Y. Senzaki, D. Roberts, and D. -L. Kwong, High quality ultra thin CVD HfO2 gate stack with poly-Si gate electrode, in Proc. of IEDM, pp. 31-34, 2000. [10] S. J. Lee, C. H. Lee, Y. H. Kim, H. F.Luan, W. P. Bai, T. S.Jeon, and D. -L. Kwong, Dual-poly CVD HfO2 gate stack for sub-100 nm CMOS technology, IWGI, pp. 80-85, 2001. [11] C. C. Yeo, B. J. Cho, M. S. Joo, S. J. Whoang, D. L. Kwong, L. K. Bera, S. Mathew, and N. Balasubramanian, Improvement of electrical properties of MOCVD HfO2 by multi-step deposition process, Electrochemical and SolidState Lett., Vol. 6 (11), pp. F42-F44, 2003. [12] M. S. Joo, B. J. Cho, C. C. Yeo, D. S. H. Chan, S. J. Whoang, S. Mathew, L. K. Bera, N. Bala, and D.-L. Kwong, Formation of hafnium-aluminium-oxide gate dielectric using single cocktail liquid source in MOCVD process, IEEE Trans. on Electron Devices, Vol. 50, pp. 2088-2094, 2003. [13] H. Hu, C. Zhu, Y. F. Lu, M. F. Li, B. J. Cho, and W. K. Choi, A High Performance MIM Capacitor Using HfO2 Dielectrics, IEEE Electron Device Lett., Vol. 23, No. 9, pp. 514-516, 2002. [14] H. Hu, C Zhu, Y. F. Lu, Y. H. Wu, T. Liew, M. F. Li, B.J. Cho, W. K. Choi, and N. Yakovlev, Physical and Electrical Characterization of HfO2 Metal-InsulatorMetal Capacitors for Si Analog Circuit Applications, J. Appl. Phys., Vol. 94, No. 1, pp. 551-557, 2003. [15] J. M. Lger, J. Haines, and B. Blanzat, Materials potentially harder than diamond quenchable high-pressure phases of transition-metal dioxides, J. Mater. Sci. Lett., Vol. 13, pp. 1688-1690, 1994.

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Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) [16] J. M. Lger, A. Atouf, P. E. Tomaszewski, and A. S. Pereira, Pressure-induced phase-transitions and volume changes in HfO2 up to 50 GPA, Phys. Rev. B 48, pp. 93-98, 1993. [17] M. Tabbal, P. Merel and M. Chaker, Pulsed laser deposition of C-Axis oriented aluminium nitride thin films on silicon, Eur. Phys. J. Appl. Phys., Vol. 14, pp. 115-119, 2001. [18] D. K. Fork, F.A. Ponce, J.C. Tramontana and T.H. Geballe, Epitaxial MgO on Si(001) for Y-Ba-Cu-O thin-film growth by pulsed laser deposition, Appl. Phys. Lett., Vol. 58, pp. 2294-2296, 1991. [19] J. C. Vickerman, Secondary Ion Mass Spectrometry: Principles and Applications (Clarendon, Oxford, 1989) [20] Specifying HfO2 material file: (J.A. Woollam Co.Inc., Lincoln, NE 68508, USA, 2000) [21] G. Reie, B. Keiper, S. Weimantel, H. Johansen, R. Scholz, and T. Martini, Properties of laser-pulse deposited oxide-films, Thin Solid Films, Vol. 241, pp. 119-125, 1994. [22] S. Boughaba and M. U. Islam, Optical properties of tantalum oxide films deposited on BK7 substrates by Excimer laser ablation, Mat. Res. Soc. Symp., Vol. 617, pp. J3.7.1-J3.7.6, 2000. [23] Y. J. Cho, N. V. Nguyen, C. A. Richter, J. R Ehrstein, B. H. Lee, and J. C. Lee, Spectroscopic ellipsometry characterization of high- dielectric HfO2 thin films and the high-temperature annealing effects on their optical properties, Appl. Phys. Lett., Vol. 80, pp. 1249-1251, 2002.

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Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) [24] C. Chaneliere, J. L. Autran, R. A. B. Devine, and B. Balland, Tantalum pentoxide (Ta2O5) thin films for advanced dielectric applications, Materials Science and Engineering, R22, pp. 269-322, 1998. [25] J. Aarik, A. Aidla, A. -A. Kiisler, T. Uustare and V. Sammelselg, Influence of substrate temperature on atomic layer growth and properties of HfO2 thin films, Thin Solid Films, Vol. 340, pp. 110-116, 1999. [26] B. C. M. Lai, and J. Y. M. Lee, Leakage current mechanism of metal-Ta2O5metal capacitors for memory device applications, J. Electrochem. Soc., Vol. 146 (1), pp. 266-269, 1999. [27] J. A. Babcock, S. G. Balster, A. Pinto, C. Dirnecker, P. Steinmann, R. Jumpertz, and B. El-Kareh, Analog characterisitics of metal-insulator-metal capacitors using PECVD nitride dielectrics, IEEE Electron Device Lett., Vol. 22, No. 5, pp. 230-232, 2001. [28] S. Blonkowski, M. Regache, and A. Halimaoui, Investigation and modeling of the electrical properties of metal-insulator-metal structures formed from chemical vapor deposited Ta2O5 films, J. Appl. Phy., Vol. 90, pp. 1501-1508, 2002. [29] The international Technology Roadmap for Semiconductors, Semiconductor Industry Association, 2002. [30] J. L. McCreary, Matching properties, and voltage and temperature dependence of MOS capacitors, IEEE J. Solid-State Circuits, Vol. 16, pp. 608-616, 1981. [31] S. Sivoththaman, R. Jeyakumar, L. Ren and A. Nathan, Characterization of low permittivity (low-) polymeric dielectric films for low temperature device integration, J. Vac. Sci. Technol., A 20, pp. 1149-1153, 2002. [32] A. L. S. Loke, T. J. T. Wetzel, P. H. Townsend, T. Tanabe, R. N. Vrtis, M. P. Zussman, D. Kumar, C. Ryu, and S. S. Wong, Kinetics of copper drift in low-

51

Chapter 2 HfO2 MIM Capacitors by Pulsed-Laser Deposition (PLD) polymer interlevel dielectrics, IEEE Trans. Electron Devices, Vol. 46, pp. 21782187, 1999.

52

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

3.1. Introduction

As known in Chapter 1, MIM capacitor is spawned by wireless communication revolution. For instance, the mobile phone works at 0.9 and 1.9 GHz, Bluetooth at 2.4 and direct satellite TV operation at 10 GHz. With continuing improvement of Si CMOS technology, low-cost Si circuits could operate well in the 1-10 GHz range or even higher frequency [1, 2]. As one of the passive elements, MIM capacitors integrated into Si ICs need to provide well behaved and predictable capacitance characteristics in RF regime. SiO2 and Si3N4 are traditionally employed for Si RF applications with well behaved capacitance characteristics in the RF regime [3-6]. According to the ITRS roadmap, a high capacitance density of 9 fF/m2 will be needed at or beyond year 2004 [7] for RF bypass capacitors. This will necessitate the dielectric thicknesses of 4.3 and 7.8 nm for SiO2 and Si3N4, respectively. However, such thin SiO2 or Si3N4 layers can not be put into practical use due to the anticipated poor electrical performance as detailed in Chapter 1. Though multiple-layer MIM capacitors intended to increase the capacitance density have been reported using the conventional dielectrics of SiO2 and Si3N4 [8, 9], it is not favourable in terms of process complexity and cost. Therefore, selecting high- dielectric will benefit for RF MIM capacitors

53

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application application to a great extent. However, if high- materials were to be considered for the replacement of SiO2 and Si3N4, their RF performances have to be evaluated. With regard to high- HfO2 dielectric, no RF performance of HfO2 MIM capacitors has been reported so far. In particular, the dielectric constant dependence on frequency in RF regime is paramount because preserving high- even at high frequency is a fundamental requirement. In this chapter, we investigated the RF characteristics of HfO2 MIM capacitors prepared by physical vapor deposition (PVD) [10]. Compared to pulsed-laser deposition (PLD) technique [11], PVD is much superior in terms of particulate splashing and film non-uniformity [12]. PVD also has the advantage of high throughput which is beneficial for mass production. Recently, PVD has been successfully employed for fabrication of high- dielectrics such as HfO2 [13] and Ta2O5 [14] for high performance MIM capacitors application in back-end line (BEOL) integration. In addition, our results show that HfO2 MIM capacitors with various thicknesses exhibit different stress induced leakage currents (SILCs) characteristics are functions of the stress time under constant stress voltage. The variation of voltage coefficients of capacitance (VCCs) with stress time has also been investigated under prolonged electrical stress. Generation of traps under the stress has been proposed as a plausible mechanism for explanation of SILCs and stress related variation of VCCs.

54

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application 3.2. Experiments

3.2.1. RF MIM capacitor fabrication

The MIM capacitors with RF test structures were fabricated on standard p-type Si substrates with a resistivity of 4-8 cm. Before defining the bottom electrode of the HfO2 MIM capacitors, 500 nm SiO2 was deposited on silicon substrate for isolation purpose. In order for RF characterization, coplanar transmission lines were fabricated on SiO2 to serve as the top and bottom electrodes of MIM capacitors. High- HfO2 dielectric films were deposited by reactive sputtering on 0.6-m-thick patterned bottom Ta transmission line at room temperature in a gas mixture of Ar (27 sccm) and O2 (3 sccm). The chamber pressure was maintained at 5 mtorr during sputtering, and a DC power of 250 W was applied to the Hf target. Two HfO2 samples were fabricated with the physical thicknesses of 22 and 47 nm, measured by ellipsometer; and they are denoted as HfO-1 and HfO-2, respectively. Finally, a layer of 0.6-m-thick Al was deposited to define both the top electrode and the transmission line. MIM capacitors with different area were prepared. Figure 3.1 illustrates major fabrication steps and schematic top views of RF HfO2 MIM capacitor together with open dummy structure, where the open dummy device was used to de-embed the parasitic from the bond-pads and transmission lines [15, 16]. The leakage current was measured using an HP4155B semiconductor parameter analyzer, and the capacitance voltage characteristics were acquired with the help of an HP4284A precision LCR meter with frequencies varying from 10 kHz to 1 MHz. On-wafer scattering (S) parameters were measured using HP 8510C network analyzer with the GGB's air coplanar probes (ACP) in ground-signal-ground (GSG)

55

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

Mask 1: Transmission line patterning after bottom electrode deposition

Mask 2: Contact hole etching after high- HfO2 deposition

Transmission lines

RF capacitor structure

Open dummy structure

Mask 3: RF MIM structures patterning after top electrode deposition

Figure 3.1: Major fabrication steps and schematic top views of RF HfO2 MIM capacitor and open dummy structure.

56

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application configuration for RF characterization, and a precise calibration procedure including open, short, through, 50 load has been implemented using impedance standard substrate before devices measurement.

3.2.2. S-parameters for RF characterization

For RF characterization and circuit modelling of HfO2 MIM capacitors, S parameter is essential for the practical system characterization in RF regime, since measuring most other parameters like ABCD, Y, Z etc. calls for the input and output of the device to be successively opened and short circuited. This can be hard to do, especially at RF frequencies where lead inductance and capacitance make short and open circuits difficult to obtain. In addition, short or open circuits will induce oscillations which could make the measurement invalid and even destroy the device [17, 18].

Figure 3.2: The definition of S-parameters for a two-port network

The wave functions used to define S-parameters for a two-port network are presented in Fig. 3.2, where n and bn (n = 1, 2) are the normalized incident and

57

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application reflected power waves used in S-parameter definitions shown in (3.1) and (3.2), and Z 0 is the characteristic line impedance.
a n = (1 / 2 Z 0 ) (Vn + Z 0 I n ) bn = (1 / 2 Z 0 ) (Vn Z 0 I n )

(3.1) (3.2)

The S-parameters could then be defined as:

b1 b 2 S 11 S 12 = S S 21 22 a 1 a 2

(3.3)

S11 = in =

Z in Z 0 Z in + Z 0

(3.4)

Simply speaking, S-parameters can be directly related to the reflection coefficients ( in ) at the input and output of the two-port network as defined in (3.4). As a result, the measurement of S11 and S21 could be achieved by matching the line impedance Z 0 at port 2 as shown in Fig. 3.2 through a corresponding load impedance ZL = Z 0 , where Z 0 is 50 in our measurement system.

3.3. Results and discussion

3.3.1. RF characterization

To investigate the capacitance characteristics of HfO2 MIM capacitors in RF regime, we use a network based equivalent circuit model for the MIM capacitor as shown in Fig. 3.3. The Rp and C describe the basic electrical model of high- HfO2 MIM capacitors, where Rp is proposed to have its origin in the dielectric loss of the high- material and Rs, Ls1 and Ls2 represent the parasitic resistance and inductance

58

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application from the coplanar transmission lines used for RF measurements. The elements (Cox1, R1, C1 and Cox2, R2, C2) in the shunt branches in Fig. 3.3 represent the coupling of the top and bottom electrodes to ground through SiO2 and Si substrate. Standard procedures were used to de-embed the parasitic from the probe-pads [19]. One can refer to [17, 18] for S parameters conversion into Y parameters. [SDUT/dummy] [YDUT/dummy] Ycapacitor = YDUT-Ydummy (3.5) (3.6)

Here SDUT (YDUT) denote the S-(Y-) parameters of the MIM capacitors along with the probe pads and transmission lines while Sdummy(Ydummy) denote the S-(Y-) parameters of probe pads and transmission lines alone. It is important to point out here that shunt elements (Cox1, R1, C1 and Cox2, R2, C2) and series elements Rs, Ls1 and Ls2 are used to account for the transmission lines. The shunt elements are de-embedded as described above and the part of circuits within the dotted enclosure in Fig. 3.3 has been used to simulate the S-parameters of the MIM capacitor.

Figure 3.3: The equivalent circuit model for capacitor simulation at RF regime.

The de-embedded and simulated S-parameters were computed by Agilent Technologies ICCAP [20] modelling software using SPICE3 as the circuit simulator.

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

(a)

(b)

Figure 3.4: The measured and simulated S-parameters for (a) HfO-1 and (b) HfO-2. (Simulation and parameter extractions were done by ICCAP.)

60

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application Fig. 3.4(a) and 3.4(b) show the measured and simulated two-ports S-parameters (S11 and S21) for HfO-1 and HfO-2 from 50 MHz to 20 GHz. As can be seen, the measured and simulated data over the entire frequency range from 50 MHz to 20 GHz are in excellent agreement. This suggests that the equivalent circuit model shown in Fig. 3.3 is suitable and reliable for the capacitor modelling and parameters extraction. With regards to the lumped equivalent circuit model for capacitor simulation, it is noticed that other similar approaches have been used. There appears to be slightly difference when considering the capacitor geometry and physical topology [21, 22]. In addition, Ls1+Ls2 is ~110 pH, Rs is ~12 , and Rp is in the range of ~10 M for HfO-1 and HfO-2. Large value of Rs can be mainly ascribed to the relatively highly resistive Ta transmission line and thin metal layers. The use of high conductivity metals like Cu and/or increasing the metal layer thickness will reduce Rs and hence higher quality factor. In comparison, the high value of Rp indicates the good insulating property of the HfO2 RF MIM capacitors. The overall effective capacitance (including the impedance due to Ls1, Ls2 and Rs) versus frequency for HfO-1 and HfO-2 is as presented in Fig. 3.5. This was calculated from the 1-port admittance (Y11) using equations (3.5) and (3.6):
Z in = 1 / Y11 = Reff + 1 j * C eff

(3.5)

C eff =

1 (imag ( Z in )

(3.6)

It is noticed that the transition from capacitive to inductive behaviours are due to the above mentioned parasitic inductances. These are believed to be associated with the interconnect and are extrinsic to the MIM structure. The self-resonance frequency including the transmission line parasitic for HfO-1 is 9.4 GHz in comparison with HfO-2 positioned at 14.3 GHz. This is mainly due to the smaller capacitance value of

61

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

600.0p Single efftive capacitance

HfO-1 HfO-2

400.0p

200.0p

0.0

-200.0p

0.0

5.0G

10.0G 15.0G Frequency

20.0G

Figure 3.5: High frequency response of PVD HfO2 MIM capacitors from 50 MHz to 20 GHz for HfO-1 and HfO-2.
12

Capacitor density (fF/m )

10 8 6 4 2 0 1k

HfO-1 HfO-2

Low frequency 1MHz RF analysis up to 20 GHz

100k

10M

1G

100G

Frequency (Hz)
Figure 3.6: The frequency dependence of capacitance density for PVD HfO2 MIM capacitors HfO-1 and HfO-2.

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application HfO-2 [23]. The useful operating frequency range for MIM capacitor could be further extended by minimizing the parasitic from the interconnect. In order to further study the capacitance-frequency characteristics of HfO2 MIM capacitors, we have plotted the capacitance measured at low frequency (10 kHz1MHz) and the extracted capacitance from RF measurements in Fig. 3.6. It is straightforward to conclude from Fig. 3.6 that the PVD HfO2 shows good capacitancefrequency dependency for MIM capacitors, which is in agreement with the conclusions of Dong et al. who investigated HfO2 thin film for RF-MOSFET applications [24]. In addition, HfO2 MIM capacitors with different thicknesses show high capacitance densities of 7.3 and 3.5 fF/m2 for HfO-1 and HfO-2 respectively. The dielectric constant was calculated to be approximately 18. It is worthwhile to point out that PVD high- HfO2 could still preserve its high value in RF regime (up to 20 GHz) for MIM capacitor applications within the thermal budget limitation of the back-end integration. In contrast, the dielectrics constants of some high- materials like TiSiOx and AlTiOx have been reported to have strong frequency dependence with the dielectric constant dropping as the frequency increase [15, 25]. Therefore, those types of capacitors are unsuitable for MIM capacitors application from the circuit design perspective. In addition, no area dependency was found for these two HfO2 MIM capacitors. A small device area (2525 m2) were selected for characterization in this work, since RF circuit applications in GHz range would need typical capacitance values of a few pico-farads only.

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

10 10 J (A/cm ) 10 10 10 10 10

-3

-4

-5

Fresh 2000 s @1.5 V 4000 s @1.5 V 6000 s @1.5 V

-6

-7

-8

-9

0.0

0.5

1.0 1.5 Voltage (V)

(a)

2.0

10 10 J (A/cm ) 10 10 10 10 10
2

-3

-4

-5

Fresh 2000 s @1.5 V 4000 s @1.5 V 6000 s @1.5 V

-6

-7

-8

-9

0.0

0.5

1.0 1.5 Voltage (V)

(b)

2.0

Figure 3.7: Stress induced leakage currents (SILCs) characteristics of (a) HfO-1 and (b) HfO-2 under the constant voltage stress at 1.5 V .

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

3.3.2. DC and low frequency measurements

Figures.3.7(a) and 3.7(b) show the J-V characteristics of HfO-1 and HfO-2 at room temperature (~25oC) before and after the stress, respectively. As shown in Fig. 3.7(a), HfO2 MIM capacitor with thin film (HfO-1) shows large SILCs, the observation is similar to what has been found in SiO2 system. The large SILCs are believed to be due to the neutral traps generation during the stress [26], since the generated trap sites under stress will act as stepping stones for tunnelling carriers and give rise to excess leakage. Comparing with measurement of fresh capacitors, the leakage current density increased by nearly one order of magnitude after 4000 s stress at 1.5 V. With the stress time increased up to 6000 s, the SILC nearly saturated, which is believed to be due to the saturation of created trap sites under certain stress conditions [27]. In contrast, the leakage of HfO-2 showed minimal increase for the same amount of stress up to 6000 s. The different characteristics of SILCs for HfO2 MIM capacitors may be due to the smaller amount of traps generated during the prolonged stress for thick oxide with a lower electric field [28]. However, for high capacitance density capacitor (like bypass RF capacitor), thinner dielectric film becomes imperative. However, excessive leakage is undesirable under prolonged bias condition. This becomes a limiting factor for the scaling of dielectric films [29]. In order to improve the leakage property of PVD HfO2 dielectric, the methods including novel plasma treatment [30, 31], and new structures like HfO2-Al2O3 laminate [32] may need to be implemented. However, the challenge is to achieve high quality dielectric films while complying with the thermal budget of back-end-of line integration ( 400oC) and maintaining the high throughput.

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

Quadratic coefficients (ppm/V )

2400

100 kHz 500 kHz 1 MHz

2100

1800

1500

1000 2000 3000 4000 5000 6000 Stress time (s) @ 1.5 V
(a)

2100 Linear coefficient (ppm/V)

1800

100 kHz 500 kHz 1 MHz

1500

1200

900 0 1000 2000 3000 4000 5000 6000 Stress time (s) @ 1.5 V
(b) Figure 3.8: Stress time dependence of (a) the quadratic voltage coefficients and (b) the linear voltage coefficients for HfO-1 under the constant voltage stress at 1.5 V.

66

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application The voltage linearity property of HfO2 MIM capacitors under stress has also been investigated and the evolution of voltage linearity has been studied. The capacitance-voltage characteristics of the MIM capacitors were measured from 2 V to 2 V at 100 kHz, 500 kHz, and 1 MHz before and after the stress. At each frequency, the measured capacitance of the MIM capacitor can be fitted by C(V) = C0 (V2+V+1) (3.7)

where, C0 is the zero biased capacitance at each frequency, V is the bias voltage; and are the quadratic and linear voltage coefficients which have different implications for analog and RF MIM capacitor applications according to ITRS roadmap [7]. Figs. 3.8(a) and 3.8(b) depict both the quadratic and the linear coefficients as a function of stress time for HfO-1. It is interesting to note that both and values decrease with stress time at 1.5 V for each measured frequency, which is contrary to the observed SILCs in Fig. 7(a) showing that the SILCs increase with the stress time. Figures.3.8(a) and 3.8(b) present the voltage coefficients of HfO-2. It could be also seen that both and coefficients decrease with the stress time. However, thick HfO2 film showed less stress dependence in comparison with HfO-1, which is in accordance with SILCs characteristics of HfO-2. In addition, the reduction of linear coefficient seems slightly more obvious than that of quadratic coefficient under stress for HfO-1 and HfO-2. It needs to be mentioned here that the mechanism for stress-time evolution of VCCs is under investigation and is still not clear. However, the reduction of voltage coefficients after stress should not be construed to suggest the improvement of the film quality. Rather, the film quality degrades under stress as indicated by SILCs. Further, it seems plausible that the different characteristics of SILCs and evolution of voltage linearity under stress have the same physical origin. For the CV characteristics of HfO2 MIM capacitors, which could be fitted by the polynomial equation, the distortion of

67

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

800 Quadratic coefficients (ppm/V ) 700 600 500 400 300 200
100 kHz 500 kHz 1 MHz
2

1000 2000 3000 4000 5000 6000 Stress time (s) @ 1.5 V
(a)

600 Linear coefficient (ppm/V) 500 400 300 200 100

100 kHz 500 kHz 1 MHz

1000 2000 3000 4000 5000 6000 Stress time (s) @ 1.5 V
(b)

Figure 3.9: Stress time dependence of (a) the quadratic voltage coefficients and (b) the linear voltage coefficients for HfO-2 under the constant voltage stress at 1.5 V.

68

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application CV curve for the device after stress was reflected by the reduction of quadratic coefficients. The flattening-out of the characteristic (CV curve bent downward after stress.) is similar to the stretch-out of the CV curve in MOS device when interface states are present [33]. The variation of linear coefficients is manifested in the parallel shift of CV curve towards the positive side of the voltage axis akin to a positive shift of flat band voltage due to the negative charges seen in the MOS capacitors [33]. This suggests the plausibility of the trap generation under stress explaining both the SILCs and the evolution of VCCs after application of stress.

Figure 3.10: The equivalent circuit for HfO2 MIM capacitors after stress. The added branch stands for the generated trapped states in MIM capacitor after stress.

69

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application An equivalent circuit shown in Fig. 3.10 may help to develop a phenomenological model for the variation of quadratic and linear coefficients after stress, where C and Rp have the same physical meanings as described in Fig.3.3 for the fresh device. After stress, the additional branch comprising C1 and R1 was introduced, where C1 and R1 account for the traps generated after the DC stress in the dielectric, with energy levels distributed within the oxide band gap. From this circuit diagram in Fig. 3.10, C1 in the added branch equals to Q1/V1, where Q1 stands for the charges stored in the added branch and V1 is the voltage on C1. It may be surmised that if Q1 is of negative sign, it could account for the flattening-out of the CV curves after stress corresponding to a net charge loss in the dielectric. The voltage dependence of C1 and R1 can thus effectively model both linear and quadratic coefficients. Though more works are needed for a clear physical understanding, it appears plausible that the generated traps after stress in high- dielectric are responsible for the reduction of the quadratic and linear coefficients. It may be of interest to note that even though the oxide quality deteriorates during stress, the reduced voltage coefficients seem beneficial from the perspective of MIM capacitors applications. In addition, it may also be noticed that the frequency dependence of voltage linearity (Fig.3.8 and Fig.3.9) is almost unchanged after the stress, even though both quadratic and linear coefficients improve at higher frequency.

3.4. Conclusion

In this chapter, we investigated the electrical characteristics of high- PVD HfO2 MIM capacitors from IF (10 kHz) to RF (20 GHz) frequency range for the first time. High- HfO2 dielectric has been demonstrated to exhibit good capacitance-

70

Chapter 3 Characterization of HfO2 MIM capacitors for RF Application frequency dependency, i.e. the dielectric constant of HfO2 remains almost constant in the entire frequency range up to 20 GHz. This suggests that HfO2 is a good high- candidate for RF MIM capacitors applications. In addition, HfO2 MIM capacitor with thin dielectric film showed large SILCs compared to thick HfO2 film, which is believed to be due to the reduced amount of traps generated in thick oxide film on account of the smaller electric field in the thicker film. The evolution of voltage linearity under stress reveal that both the quadratic and the linear coefficient reduce in magnitude with stress time, and correlate to the variation of SILCs in HfO2 MIM capacitors. It has been proposed that the reduced voltage coefficients originate from the generated traps in high- HfO2 films after the electrical stress.

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application [9] Z. Chen, L. Guo, M Yu, and Y. Zhang, A study of MIMIM on-chip capacitor using Cu/SiO2 interconnect technology, IEEE Microwave and Wireless Components Lett., Vol. 12, pp. 246-248, 2002. [10] H. Hu, S. J. Ding, C. Zhu, Y. F. Lu, M. F. Li, B. J. Cho, D. S. H. Chan, S. C. Rustagi, M. B. Yu, A. Chin, and D. -L. Kwong, Investigation of PVD HfO2 MIM capacitors for Si RF and mixed signal ICs application, International Semiconductor Device Research Symposium (ISDRS), pp. 328-329, 2003. [11] H. Hu, C. Zhu, Y. F. Lu, M. F. Li, B. J. Cho, and W. K. Choi, A high performance MIM capacitor using HfO2 dielectrics, IEEE Electron Device Lett., Vol. 23, No. 9, pp. 514-516, 2002. [12] D. B. Chrisey and G. K. Hubler, Pulsed Laser Deposition of Thin Films (Wiley, New York, 1994) [13] S. J. Kim, B. J. Cho, M. F. Li, C. Zhu, A. Chin, and D. -L. Kwong, HfO2 and lanthanide-doped HfO2 MIM capacitors for RF/mixed IC applications, in Proc. Symp. VLSI Technology, pp. 77-78, 2003. [14] T. Yoshitomi, Y. Ebuchi, H. Kimijima, T. Ohguro, E. Morifuji, H. S. Momose, K. Kasai, K. Ishimaru, F. Matsuoka, Y. Katsumata, M. Kinugawa, and H. Iwai, High performance MIM capacitor for RF BiCMOS/CMOS LSIs, in Proc. of BCTM, pp. 133-136, 1999. [15] S. B. Chen, J. H. Chou, A. Chin, J. C. Hsieh, and J. Liu, RF MIM capacitors using high- Al2O3 and AlTiOx dielectrics, in Proc. of IEEE MTT-S Intl. Microwave Symp., pp. 201-204, 2002. [16] C. H. Huang, M.Y. Yang, A. Chin, C. X. Zhu, M. F. Li, and D. L. Kwong, High density RF MIM capacitors using high- AlTaOx dielectrics, in Proc. of IEEE MTT-S International Microwave Symp., pp. 507-510, 2003.

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application [17] D. M. Pozar, Microwave Engineering (John Wiley & Sons, 1998) [18] Thomas H. Lee, The design of CMOS radio-frequency integrated circuits (Cambridge press, 1998) [19] P.J.van Wijnen, H. R. Claessen, and E. A. Wolsheimer, A new straightforward calibration and correction procedure for On Wafer high frequency S-parameters measurement (45MHz-18GHz), in Proc. of BCTM, pp. 70-73, 1987. [20] IC-CAP manual, Hewlett Packard, 1998. [21] C. Geng, K. W. Chew, K. S. Yeo, M. A. Do, J. Ma, C. T. Chua, and K. Shao, Physically-based RF model for metal-oxide-metal capacitors, Electronics lett. Vol. 36, No. 5, pp. 425-427, 2000. [22] S. S. Song, S. W. Lee, J. Gil, and H. Shin, A simple wide-band MIM capacitor model for RF applications and the effect of substrate grounded shields, in Proc. of SSDM, pp. 438-439, 2003. [23] J.H. Lee, D.H. Kim, Y.S. Park, M.-K. Sohn, and K.-S. Seo, DC and RF characteristics of advanced MIM capacitors for MMICs using ultra-thin remotePECVD Si3N4 dielectric layers, IEEE Microwave Guided Wave Lett., Vol. 9, pp. 345347, 1999. [24] Dong Barlage, Reza Arghzvani, Gilbert Dewey, Mark Doczy, Brian Doyle, Jack Kavalieros, Anand Murthy, Brian Roberds, Pat Stokley and Robert Chau, High frequency response of 100 nm integrated CMOS transistors with high- gate dielectrics, in Proc. of IEDM, pp. 231-234, 2001. [25] D. K. Sarkar, E. Desbiens, and M. A. El Khakani, High- titanium silicate dielectric thin films grown by pulsed-laser deposition, Appl. Phys. Lett., Vol. 80, pp. 294-296, 2002.

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Chapter 3 Characterization of HfO2 MIM capacitors for RF Application [26] D. J. Dimaria, and E. Cartier, Mechanism for stress-induced currents in thin silicon dioxide films, J. Appl. Phy., Vol. 78, pp. 3883-3894, 1995. [27] Q. Lu, K. P. Cheung, N. A. Ciampa, C. T. Liu, C. -P. Chang, J. I. Colonell, W.Y.-C. Lai, R. Liu, J. F. Miner, H. Vaidya, C. -S. Pai, and J. T. Clemensz,A model of the stress time dependence of SILC, in Proc. IEEE Intl. Reliability Physics Symp., pp. 396399, 1999. [28] E. F. Runnion, S. M. Gladstone, IV, R. S. Scott, Jr., Member, D. J. Dumin, L. Lie, and J. C. Mitros, Thickness Dependence of Stress-Induced Leakage Currents in Silicon Oxide, IEEE Trans. Electron Devices, Vol. 44, p. 993-1001, 1997. [29] H. Satake and A. Toriumi, Common origin for stress-induced leakage current and electron trap generation in SiO2, Appl. Phys. Lett., Vol. 67, p. 3489, 1995. [30] G. B. Alers, R. M. Fleming, Y. H. Wong, B. Dennis and A. Pinczuk, Nitrogen plasma annealing for low temperature Ta2O5 films, Appl. Phys. Lett., Vol. 72, No. 11, pp. 1308-1310, 1998. [31] S. J. Chang, J. S. Lee, J. F. Chen, S. C. Sun, C. H. Liu, U. H. Liaw and B. R. Huang, Improvement of electrical and reliability properties of tantalum pentoxide by high-density plasma (HDP) annealing in N2O, IEEE Electron Device Lett., Vol. 23, No. 11, pp. 643-645, 2002. [32] K. Kukli, J. Ihanus, M. Ritala, and M. Leskela, Tailoring the dielectric properties of HfO2-Ta2O5 nanolaminates, Appl. Phys. Lett., Vol. 68, No. 26, pp. 3737-3739, 1996. [33] E H Nicollian and J R Brews, MOS (Metal Oxide Semiconductor Physics and Technology (Wiley, New York, 1982)

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Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

4.1. Introduction

4.1.1. ALD method for thin films fabrication

The concept of atomic-layer-deposition (ALD) was first introduced by T. Suntola, et. al in 1977 as a variant of physical vapor deposition named as atomic layer epitaxy (ALE) [1]. This technique is limited to very few material systems and required stringent process conditions due to the PVD implementation of ALD. Nowadays, the implementation of basic ALD concepts using chemically reactive molecular precursors is capable of preparing insulating dielectric films, metal electrodes and interconnect barriers as well [2]. The foundation of ALD is the self-limiting characteristics of the process steps in which a chemical vapor reacts with a surface until a monolayer has been chemisorbed. The reaction then stops, so the process is called self-limiting. A second vapor then reacts with this surface in a second self-limiting reaction depositing a second of atoms onto the films. The second reaction must return the surface to a state in which it is ready to react with the first reactant. The cycle of reactions can then be repeated to build up a compound atomic layer by atomic layer.

76

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) Due to the self-limiting nature of ALD allowing for atomic scale control, it has the promises of unprecedented control of film thickness, uniformity, quality and materials properties. In particular, ALD has the exclusive advantage of manipulating the physical and electronic properties of thin films by changing their composition, which is practiced by layering nanolaminate stacks of films as well as by deposition of mixed component alloys. Though ALD has been criticized for its low deposition rates, some novel schemes have recently been proposed to address this concern [3, 4]. Currently, the silicon semiconductor industry is devoting a large amount of research to ALD, as it is considered to be a likely future method for the production of thin dielectric films. ALD is already used to grow gate oxides [4, 5] and DRAM dielectrics [6, 7]. In this chapter, ALD was chosen as an alternative method to fabricate HfO2-Al2O3 dielectrics using various dielectric structures.

4.1.2. Characteristics of ALD processed HfO2 and Al2O3

In this work, the precursors for HfO2 deposition are HfCl4 and H2O, and those for Al2O3 are Al(CH3)3 (TMA) and H2O. N2 was used as both carrier gas and purge gas. Table 4.1 summarizes ALD process conditions for pure HfO2 and Al2O3 films growth Table 4.1: ALD process conditions for the deposition of HfO2 and Al2O3
Pressure [mtorr] 125 Pressure [mtorr] 200 HfCl4 pulse [ms] 2000 TMA pulse [ms] 200 HfCl4 purge [ms] 6000 TMA purge [ms] 1500 H2O pulse [ms] 400 H2O pulse [ms] 500 H2O purge [ms] 3000 H2O purge [ms] 3000 Temperature [oC] 320 Temperature [oC] 340

HfO2 deposition Al2O3 deposition

77

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) using GENUS LYNX2 system. The deposition cycle is broken up into a sequence of discrete process steps, and the low thermal budget (~300oC) of ALD method is compatible with back-end of line (BEOL) integration for MIM capacitor fabrication. In comparison, it was noticed that HfCl4 necessitate much longer pulse and purge time compared to TMA. Figures 4.1(a) and 4.1(b) present the growth rates as a function of growth cycles for HfO2 and Al2O3. The film thickness was measured by ellipsometry and the underlayer thickness was deducted using recipes calibrated by SiO2. Those films were grown on 6-inch Si (100) substrates, and the films uniformity on wafer is less than 2%. It is straightforward to note that the linear growth rates dependence on the growth cycle is characteristic of ALD processed HfO2 and Al2O3 deposition. The intercepts of -1.8 and 0.1 is observed for zero HfO2 and Al2O3 thicknesses respectively, where the relatively large negative intercept implies that the growth of HfO2 must be nonlinear for the initial several cycles, which is in agreement with [8]. In comparison, HfO2 has a slightly lower deposition rate of 0.6 /cycle than that for Al2O3 at 0.76 /cycle. It is believed that the high sticking coefficient of HfCl4 precursor due to its strong ionic bonding is responsible for long purge/pulse time and the low growth rate of HfO2 [6]. Recently, it is reported that using the liquid precursors such as Hf(NEtMe)4 for HfO2 growth could alleviate this problem [6]. In this chapter, the motivation of adding Al2O3 into HfO2 is that, Al2O3 is an high- material with the merits of high energy band gap of ~8.9, middle dielectric constant (9~10), immunity to oxygen diffusion, etc [9]. In practice, Al alloyed TiO2, Ta2O5, and HfO2 MIM capacitors have been demonstrated to provide the overall better electrical performance than using each dielectric alone [10-12]. Besides, HfO2-Al2O3 laminate has been studied as DRAM dielectrics [6]. In the following section,

78

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

(a)

(b) Figure 4.1: The growth rates dependence on deposition cycles for ALD processed (a) HfO2 and (b) Al2O3.

79

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) we will focus on the investigation of HfO2-Al2O3 laminated dielectric. In addition, the electrical characteristics of HfO2-Al2O3 MIM capacitors using different material structures will be studied and compared.

4.2. Experiments

The MIM capacitors were fabricated on SiO2 deposited on Si substrate. The bottom electrode of Ta/TaN was formed by sputtering, where Ta was used to reduce the parasitic resistance of the electrode and TaN was acted as an oxidation-resistant barrier layer [13]. After that, the laminated dielectrics with alternate Al2O3 (1 nm) and HfO2 (5 nm) layers were deposited using ALD technique, and the beginning and end layers were 1 nm Al2O3, respectively. The insertion of 1 nm Al2O3 as the contacting layer to the top and bottom electrodes is to improve the metal/dielectric interface quality [14]. Three thicknesses of laminated dielectrics (i.e. 13, 31 and 43 nm) were deposited for electrical evaluation. Figure 4.2 illustrates the fabricated laminate structure and the TEM photo of 13 nm laminated film. TaN was then sputtered as the top electrode, followed by the post deposition annealing in N2 at 420oC for 30 min. Finally, a photolithography step and dry etching were used to define the MIM capacitors. In consideration of RF characterization for laminate dielectrics, the coplanar transmission lines were also fabricated, which also served as the top and bottom electrodes; and Al was used as the contact pads after TaN top electrode formation. For more details with regard to the RF structure fabrication, one can refer to Chapter 3. The maximum temperature in the device fabrication was 420C, which is compatible with Si back-end of line process. In addition, HfO2-Al2O3 dielectrics using

80

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) different material structures have been fabricated for electrical evaluation and comparison using the same fabrication procedures as described above.

Figure 4.2: TEM cross section of 13 nm HfO2-Al2O3 laminated dielectric.

For electrical characterization, capacitances from 10 kHz to 1 MHz were measured using a HP4284A precision LCR meter. For RF characterization, the scattering (S) parameters were measured on wafer using HP 8510C network analyzer with the GGB's air coplanar probes (ACP) for ground-signal-ground (GSG) configuration. The measured S-parameters were de-embedded using the same procedures as described in Chapter 3. Leakage currents were measured using a HP4155B semiconductor parameter analyzer. To study dependence of voltage coefficients of capacitance (VCCs) on constant voltage stress (CVS), C-V characteristics were measured with an interruption of stress after different stress time. The breakdown of the dielectric was characterized by monitoring the change of leakage current during CVS.

81

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) 4.3. Electrical characterization of HfO2-Al2O3 laminated MIM capacitors

4.3.1. RF Characteristics of laminated MIM capacitors

Using the method and equivalent circuit model described in Chapter 3, the measured two-port S parameters (S11 and S21) after de-embedding the shunt elements are obtained for the laminate MIM capacitors with three thicknesses. In comparison, the simulated two-port S parameters are also obtained using the aforementioned equivalent circuit. The respective two-port S parameters are depicted in Figs. 4.3(a, b, c) for all three laminated capacitors. Again, it can be found that the measured and simulated data over the entire frequency range from 50 MHz to 20 GHz are in very good agreement, suggesting the equivalent circuit model is suitable and reliable for the capacitor modeling and parameters extraction. In addition, the transition from capacitive to inductive behavior was evidenced from the inset of Fig. 4.4, which are believed to be associated with the interconnect and are extrinsic to the MIM structure. The resonance frequencies are 5.5, 7.7, 9.3 GHz for the 13, 31, 43 nm laminate MIM capacitors, respectively. The different resonance points result from the different capacitance values are due to different dielectric thicknesses. Figure 4.4 again presents the capacitance densities measured at low frequency (10 kHz ~ 1MHz) and those extracted in RF regime. It is revealed that all of the laminate MIM capacitors can offer nearly constant capacitance densities of 4.3, 6.1 and 12.8 fF/m2 from 10 kHz to 20 GHz for 43, 31 and 13 nm thick laminates respectively. The calculated dielectric constant of the laminate is around 19. This indicates that the incorporation of a small quantity of Al2O3 can still preserve a high enough dielectric constant. Considering the 13 nm laminated MIM capacitor,

82

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

(a)

(b)

(c)

Figure 4.3: Measured and simulated S-parameters for (a) 13 nm, (b) 31 nm and (c) 43 nm laminated MIM capacitors

83

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) the capacitance density of 12.8 fF/m2 can fulfill the requirement of RF capacitor up to year 2007 according to ITRS roadmap [15]. In addition, the well-behaved and predictable RF characteristics could also be observed for HfO2-Al2O3 dielectrics using other material structures like stack and sandwich. Based on all the experimental RF data, it is concluded that pure HfO2 and HfO2-Al2O3 dielectrics are good materials for RF MIM capacitor applications.

Capacitance density (fF/m )

Single ended effective capacitance

28 24 20 16 12 8 4 0 1k 100k
13 nm 31 nm 43 nm

200p Capacitive 100p 0 -100p -200p -300p 0.0 Inductive 13 nm 31 nm 43 nm 5.0G 10.0G 15.0G Frequency (GHz) 20.0G

Low frequency 1 MHz RF analysis up to 20 GHz

10M 1G Frequency (Hz)

100G

Figure 4.4: The capacitance density dependence on frequency for laminate capacitors with three thicknesses, the inset shows high frequency response of laminate MIM capacitors from 50 MHz to 20 GHz.

4.3.2. Leakage and breakdown characteristics of laminated MIM capacitors

Figure 4.5 shows the dependence of leakage current density (J) on biasing voltage at 125oC for MIM capacitors with different thicknesses of laminate.

84

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

10

-2

measured at 125 C area: 100m*100m

Leakage current (A/cm2)

10

-4

13 nm 31 nm 43 nm

10

-6

10

-8

10

-10

-4

-2

Voltage (V)
Figure 4.5: J-V characteristics of 13, 31 and 43 nm laminated capacitors measured at 125oC.

10

-4

Leakage Current (A/cm2)

10

-6

22 C o 50 C o 75 C o 100 C o 125 C

10

-8

13 nm laminate 10
-10

-4

-2

Voltage (V)
Figure 4.6: J-V characteristics of 13 nm laminated MIM capacitor as a function of temperature.

85

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) It is noticed from Fig. 4.5 that the leakage current density decreases with the increase of the laminate thickness at the same voltage. It can be found that the 13 nm HfO2Al2O3 laminated MIM capacitor can provide much smaller leakage current than the reported HfO2 [16] and Tb-doped HfO2 [17] MIM capacitors while maintaining similar capacitance density. Such a small leakage current density for the laminated MIM capacitor is attributed to the incorporation of 1 nm Al2O3 layers. This exploits the merits of large band gap of Al2O3 which helps to reduce leakage current and slow oxygen diffusion through Al-O matrix resulting in improved interface properties [9, 10]. The intermediate amorphous Al2O3 layers inhibit the continuous crystal growth of HfO2. Therefore, this eliminates the grain boundary channels extending from one electrode to the other, and further contributes to the reduction in conductivity [18]. Figure 4.6 presents the J-V curves for the 13 nm laminated MIM capacitor measured at several different temperatures. It is found that the leakage current density at low voltages exhibits weak temperature dependence in comparison with that at high voltages, i.e. compared to the leakage current at 50oC, the leakage currents at 125oC increase by 1.6 and 24.8 times at 1 and 3V, respectively. In addition, the J-V characteristics exhibit two distinct regions. One is the low bias region (typically at < 2V), where the leakage current increases slowly with the applied voltage; the other is the high bias region (> 2V), where the leakage current increases quickly with the applied voltage. These phenomena reflect different current transport mechanisms in the laminated films. Before we proceed to discuss the electron conduction mechanism in the laminated dielectric, we should introduce two major conduction mechanisms frequently observed in high- dielectric films, i.e. Schottky emission and PooleFrenkel (P-F) emission [19-21]. This can be categorized into electrode limited and

86

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

-22 -24 -26 -28 -30 -32 -34 1200 1400 1600 1800 2000
em is si on Po ol eFr en ke l

Ln (J/E)

o 22 C S=0.0167 o 50 C S=0.0179 o 75 C S=0.0178 o 100 C S=0.0183 o 125 C S=0.0182

E1/2 (V/cm)1/2
-16
-16 22 oC -17

(a)

-18

LnJ

-19

=0.00167

LnJ

-18

-20

-21 400 800 1200 1600

22 C 50 C 75 C
o o o o

E1/2 (V/cm)1/2

-20

100 C 125 C

400

800

1200

1600

E1/2 (V/cm)1/2
(b) Figure 4.7: Conduction mechanisms for the 13 nm laminated MIM capacitor: (a) Poole-Frenkel mechanism occurring at high electric field, exhibiting a shift to lower electric field with increasing the temperature, (b) Schottky emission fitting at low electric field.

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Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

bulk limited processes. For Schottky effect, the electrode limited current obeys the Richardson-Schottky law and can be expressed as follows:

J = A * T 2 exp(

eb E ) exp( S ) 2 KT KT

(4.1)

where 0 is the barrier height, T is the temperature, and s is the Schottky slope:

s = (

e3 )1 / 2 * 4K 0

(4.2)

Here K*=n2, is the optical dielectric constant, n is the refractive index. If we plot d log s vs. E1/2, the resulting slope will be:

d log J 0.434 = s log e = s 1/ 2 KT KT dE

(4.3)

As for P-F emission, it is due to the field-enhanced thermal excitation of trapped electrons, which could be regarded as the bulk analog of the Schottky emission. The effect yields a field-dependent conductivity of the form:

= 0 E exp(

b
KT

) exp(

PF E 1 / 2
KT

(4.4)

where 0 is a constant. This equation can also be written in the form: J = 0 E exp(

b
KT

) exp(

PF E 1 / 2
KT

(4.5)

When plot log(J/E) vs. E1/2, the resulting slope will be:

d log J PF 0.434 = PF log e = 1/ 2 KT KT dE where

(4.6)

PF = (

e3 1/ 2 ) K * 0

(4.7)

is the P-F coefficient. Note that PF = 2 S . By analysis of the J-V curves, the conduction mechanism in the dielectric could be determined, and we find that both
88

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) Schottky emission and P-F are involved in the electronic conduction process in the laminate films. To further verify the possible effect shown in Fig. 4.6, Figure 4.7 (a) shows the dependence of ln(J/E) on E1/2 at high bias for each temperature, together with extracted slope (S) by linear fitting. As a result, we can deduce that the refractive index of the laminate is close to 1.8 in the case of 22oC, which is in good agreement with the refractive index (~2.0) of ALD HfO2, suggesting that P-F emission is satisfactorily followed at high electric field. Moreover, it is noticed that the transition to P-F emission shifts from 2.4 to 1.6MV/cm with increasing the temperature from 22oC to 125oC. In comparison, the J-V curves at low bias could only be well fitted with the Schottky emission taken into consideration. Figure 4.7(b) shows ln(J) dependence on E1/2, and the inset of Fig. 4.7(b) presents the resultant slope by a linear fitting for J-V curve measured at 22oC. However, the calculated refractive index is about 9, which is much larger than that of HfO2. Therefore, it is considered that the Schottky emission is not a unique conduction mechanism at low bias. Recently, it has been reported that trap-assisted-tunneling (TAT) current at low voltage (field) for Ta2O5 MIM capacitors is characterized by weak temperature dependence, weaker electric-field-dependence than P-F current, and a very prominent knee feature due to a significant change of JV slope in the case of the transition from TAT to P-F emission [22, 23]. The aforementioned features can also be observed in Fig. 4.6 in the case of HfO2-Al2O3 laminated films, suggesting that the leakage current at low voltages probably includes the TAT component as well. Figure 4.8 shows the evolution of leakage current during constant voltage

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Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

2x10

-5

2 Area=1E-4 cm As-stressed Stressed @4V

J (A/cm2)

1.6x10

-5

Remeasured after 10hurs

1.2x10

-5

10

100

1000

Stress time (sec)

Figure 4.8: The characteristics of leakage current versus stress time under 4V stress for the 13 nm laminated MIM capacitor. Square and round symbols represent the 1st stress and the 2nd stress after an interruption of 10 hours, respectively.

Leakage current (A/cm2)

10

-4

10

-5

10 10

-6

0 to 4 4 to -4 -4 to 4 4 to -4 -4 to 4

-7

10

-8

10

-9

-4

-3

-2

-1

Voltage (V)
Figure 4.9: I-V measurements showing the hysteresis loop of 13 nm laminated MIM capacitor.

90

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) stress for 13 nm laminate. It can be found that the leakage current reduces swiftly at the beginning of stress, followed by a gentle decrease with stress time. For fresh capacitors, the leakage current density decreases by about 38% with increasing stress time to 1500 sec under 4V, suggesting the electron charge trapping. Subsequently, the stress voltage is removed and the device is kept at zero-bias for 10 hours, and then the leakage current density is re-measured under the same voltage stress. As shown in Fig. 4.8, the leakage current density at the starting point is remarkably recovered after 10 hours interruption, i.e. to 94% of the original. This indicates that electron charge trapping process occurs mostly at the dielectric/electrode interface, not at the bulk of the dielectric [24]. To measure the current dependence on voltage bias and time, we varied the applied voltage from the negative extreme to the positive extreme and back, and recorded the corresponding currents (see Figure 4.9). It is noticed that IV curves exhibit a good symmetry for positive and negative polarities, which is ascribed to a symmetrical structure of laminated MIM capacitor different from MOS capacitor with SiO2/Al2O3 gate stacks [25]. Furthermore, the laminated MIM capacitor exhibits very small hysteresis for both polarities. Here it also needs to mention that CV curves of MIM capacitors exhibit negligible hysteresis, which is simply due to its symmetrical metal-dielectric-metal structures. Compared with that of MOS capacitors using doped Si as the substrate, different types of charges trapping and defect generation can occur depending on the voltage sweep polarity [25], this could possibly lead to an obvious hysteresis behavior. In addition, breakdown characteristics of the laminate MIM capacitors are demonstrated in Figs. 4.10(a, b). The typical evolutions of leakage current versus stress time under different CVS are presented in Fig. 4.10(a) for the 13 nm laminate.

91

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

10 J (A/cm2)

stressed @ 6V stressed @ 5.8V stressed @ 5.5V

10

-1

10

-4

10

10

10
(a)

10

Stress Time (sec)

100 Cumulative probability (%) 80 60 40 20 0

13 nm 33 nm 43 nm -5 2 Area = 2.5x10 cm

10

15

20
(b)

25

30

35

40

Breakdown voltage (V)

Figure 4.10: (a) The typical breakdown characteristics of 13 nm laminate under different constant voltage stress; (b) the cumulative probability dependence on breakdown voltage for the laminated MIM capacitors with different thicknesses.

92

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) When the stress time surpasses a critical point, the leakage current exhibits a sudden rise, which is indicative of hard breakdown characteristic. The cumulative probability plot of breakdown voltage is presented in Fig. 4.10(b). In the case of 50% probability of failure, the breakdown voltages corresponding to 13, 31 and 43 nm laminate MIM capacitors are equal to 7.6, 17.8 and 25.6 V respectively, which corresponds to the breakdown field of ~ 6 MV/cm.

4.3.3. VCCs dependence and reliability of laminated MIM capacitors

Voltage coefficients of capacitance (VCCs) were again analyzed by fitting the measured data with the second order polynomial equation of

C (V ) = C0 (V 2 + V + 1) , where C0 is the zero-biased capacitance, and represent the quadratic and linear voltage coefficients of capacitance, respectively. Figure 4.11(a) shows bias-dependent normalized capacitance (C/C0) fitted by the above-mentioned equation and the resulting VCCs as well. Obviously, decreases with increasing the laminate thickness. In the case of the 13 nm laminated MIM capacitor, is equal to 211ppm/V at 1MHz, which can easily meet RF capacitor requirement (1000 ppm/V) [15]. Moreover, the electric field (E) dependence of C/C0 is also presented in Fig. 4.11(b), showing a similar dependence of C/C0 on E regardless of the dielectric thickness. On the other hand, the effect of the applied frequency on is also demonstrated in Fig. 4.12. It can be noticed that logarithmic (log) decreases linearly with a logarithmic increase in frequency, while maintaining a similar slope in spite of the laminate thickness, i.e. decreases by about 30% when the applied

93

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

0.015

measured @1MHz
2 13nm = 1990ppm/V ; = 211ppm/V 31nm = 405ppm/V2; = -95ppm/V 2 43nm =207ppm/V ; = -65ppm/V

C/Co

0.010

0.005

0.000 -2 -1 0 1 2

Voltage (V)
(a)

0.020

voltage scan: -4V~+4V measurement frequency: 1MHz

13nm 31nm 43nm

0.015
C/C0

0.010

0.005

0.000 -2 -1 0 1 2

Electric field (MV/cm)

(b) Figure 4.11: (a) The voltage-dependent normalized capacitance (C/C0) at 1 MHz for 13, 31 and 43 nm laminated capacitors, fitted by a second order polynomial equation; and (b) the corresponding plot of C/C0 versus electric field (E).

94

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

10000
13nm 31nm 43nm

(ppm/V )

1000

100

10k

100k Frequency (kHz)

1M

Figure 4.12: Frequency dependences of for 13, 31 and 43 nm laminated capacitors, showing a linear fitting in log-log scale.

10

(ppm/V )

10 kHz 100 kHz 1 MHz

10

10

10

20 30 Thickness (nm)

40

50

60

Figure 4.13: Thickness dependence of quadratic VCC () for laminated MIM capacitors.

95

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) frequency increases from 10 kHz to 1 MHz. Furthermore, we plot versus thickness as well as capacitance density, as shown in Fig. 4.13. It is found that decreases linearly with increasing the laminate thickness in the log-log scale, exhibiting a similar slope despite of the operating frequency. However, does not exhibit the aforementioned frequency and thickness dependences. The foregoing results reveal that of laminated capacitors is affected by the operating frequency and dielectric thickness as well. The frequency dependence of can be explained as the change of relaxation time with different carrier mobility in insulator. The thickness dependence of is an intrinsic property due to electric field polarization [25]. We will further discuss these phenomena in Chapter 5. For temperature coefficient of capacitance (TCC), we have measured C-V characteristics of the laminated MIM capacitors at 100 kHz as a function of temperature. It is observed that the TCCs are 182, 196, 199 ppm/oC for 13, 31, and 43
400 13nm 31nm 43nm 300 Y =3.30+10.4E-4 X
(ppm/V2) || (ppm/V)

(a)

(b) Y =2.59-22.8E-4 X

10

200 Y =2.37-10.7E-4 X

Y =2.62+9.62E-4 X Y =2.34+9.32E-4 X

Y =2.12-3.38E-4 X 100 30 60 90 120

10

30

Temperature (oC)

60

90

120

Temperature (oC)

Figure 4.14: Temperature dependences of and at 100 kHz for 13, 31 and 43 nm laminated capacitors.

96

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) nm laminated capacitor, and it is nearly independent high- laminate thicknesses. Meanwhile, temperature dependence of VCCs are also analyzed, as presented in Figs.4.14(a, b). It is indicated that the log increases linearly as a function of the temperature, and the slope becomes smaller with increasing the laminate thickness. This suggests that the temperature has a bigger influence on the thinner laminate. On the other hand, logarithmic absolute value of (log||) reduces with the temperature. Similarly, the variation of with temperature is more remarkable for thinner laminated films.

1.00 0.98

Stressed @ 4V
1.3 1.2
/0

/0

0.96 0.94 0.92 0.90 0.88 0 1000

10 kHz 100 kHz 1 MHz

1.1 1.0 0 1000 2000 3000 Stress Time (sec) 4000

2000

3000

4000

Stress Time (sec)

Figure 4.15: The dependence of /0 on stress time at 10 kHz, 100 kHz and 1 MHz. The inset shows stress time dependence of /0 at the same frequencies. 0 and 0 represent the data before voltage stress (0 is of negative sign.), and denote the data after different time stress.

In the case of 13 nm laminate, the VCCs dependent on CVS have been investigated. Figure 4.15 shows stress time dependence of normalized VCCs (/0 and

97

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) /0) under constant voltage stress and different frequencies. Noticeably, decreases and increases with a rise in stress time at each frequency, and the variation of and || values corresponds to the flatten-out and the positive shift along the voltage axis of CV curves, respectively. The trend observed for the change of and with stress is as the same as what we observed for pure HfO2 in Chapter 3, and could be explained using the same method. Additionally, it is noted that the variations of and at the beginning of stress are rapid, which agrees with the variation of leakage current under constant voltage stress (see Figure 4.8). Table 4.2 summarizes variations of VCCs and leakage current density under different measuring conditions. In comparison with the pre-stressed device, the resulting VCCs and leakage current density reduce after voltage stressing for 1500 sec. After interruption of voltage stress for 1 hour, the device is re-measured, and the resultant VCCs and leakage current density nearly recover to the pre-stress level, even though slightly lower than those of the fresh device. The consistent variations of VCCs and leakage current density reveal that the VCCs may correlate with the leakage current. This is significant for interpreting the origin of VCCs despite incomprehension so far. It is likely related to the trapping and detrapping in the dielectric under and after stress. Table 4.2: Variations of VCCs and leakage current under different condition (frequency: 100 kHz; stress voltage: 4V; area: 110-4 cm-2)

Parameters Pre-stress After 1500 sec stress After 1hr stress interruption

(ppm/V2)
2212 2132 2194

(ppm/V)
-285 -338 -306

J (ppmA/cm2) 20.60 13.97 19.63

98

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

Cumulative Failure (%)

100 80 60 40 20 0

Stressed @-6V Stressed @-5.8V Stressed @-5.5V

2 Area=1E-4cm

10

Time (sec)
(a)

10

10

E (MV/cm)
0 1 2
10 years
8

Time to 50% Failure (sec)

10

10

-4 2 Area=1x10 cm

10 10 10 10 10

0.0

1.3

2.6

3.9
(b)

5.2

6.5

7.8

Voltage (V)
Figure 4.16: (a) Cumulative TDDB curves under various constant voltages stress for 13 nm laminated MIM capacitor measured at room temperature, (b) lifetime projection of 13 nm laminated MIM capacitor, using 50% failure time as the criteria.

99

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) Finally, the lifetime of the 13 nm laminated MIM capacitor has been accessed using 110-4 cm2 size devices at room temperature. Time to breakdown characteristics of the 13 nm laminated MIM capacitors were evaluated under different constant voltage stress, as shown in Fig. 16(a). The projection of the operating voltage for a 10year lifetime is 3.3 V by taking the T50 as the failure criterion, as illustrated in Fig. 16(b). It indicates that the HfO2-Al2O3 laminate MIM capacitors are of promising reliability for practical applications. Finally, Table 4.3 compares our results on HfO2Al2O3 laminated MIM capacitors with other high capacitance density MIM capacitors reported recently [2-4], [6], it is shown that the laminated MIM capacitors exhibit nearly the best electrical performance as well as promising device reliability, suggesting it a good candidate for next generation MIM capacitors application. Table 4.3: Comparison of various high capacitance density MIM capacitors using high- dielectrics (year 2002-2003)
Reference Dielectric Capacitance density (fF/m2) Leakage (A/cm2) (ppm/V) (ppm/V2) TCC (ppm/oC) [13] Ta2O5 (PVD) 9.2 210 @1.5V 2060 3580 ~200
-8

[16] Tb-doped HfO2 (PVD) 13.3 110 @2V 332 2667 123
-7

[27] Ta2O5 (CVD) 9 2050 475

[28] HfO2 (ALD) 13 5.710 @2V 607 853

-7

This work [29] HfO2-Al2O3 laminate (ALD) 12.8 7.4510-9@2V 211 1990 182

4.4. Effects of dielectric structures on the electrical properties

As evidenced from Table 4.3, it was believed that the good quality high- films prepared by ALD method and the incorporation of Al2O3 are two main factors contributing to the superior electrical properties of laminated films. In reality, various dielectric structures have been employed for MIM capacitors application including

100

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

Figure 4.17: Illustrations of five different HfO2-Al2O3 material structures for electrical characteristics comparison.

10

-2
100

Leakage current (A/cm2)

10 10 10 10 10 10 10

-3

Cumulative probability (%)

80 60 40 20 0 3.0
H A/H H/A A/H/A L

-4

-5

-6

3.5

4.0

4.5

5.0

5.5

-7

Breakdown voltage (V)

-8

-9

10

-10

H A/H H/A A/H/A L

-4

-3

-2

-1

Voltage (V)
Figure 4.18: Typical J-V characteristics for MIM capacitors with different dielectric structures at 125oC. The inset shows the corresponding breakdown characteristics obtained at the same temperature. (Device area: 10-4 m2)

101

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) stacks, sandwich, laminate, and so on [14, 27, 29]. However, little study has been conducted to compare the electrical characteristics of different structural MIM capacitors. In this work, it was found that the proper selection of material structure also plays an important role for HfO2-Al2O3 high- systems. As depicted in Fig. 4.17, five structures were used for comparison in this work, i.e. pure HfO2, two stacks structures, sandwich, and laminate. For fair comparison, the nominal thicknesses of all the five samples were kept the same of 13 nm. Figure 4.18 presents the typical J-V curves of all the five samples obtained at 125oC. At low voltage level, stacks and laminated MIM capacitors exhibit the advantage of small leakage current density in comparison with sandwich and pure

(a)

(b)

(c)

Figure 4.19: TEM photos of (a) 13 nm HfO2-Al2O3 laminate, (b) 10 nm HfO2 and (3) 30 nm HfO2 films, illustrating the amorphous structure of laminated film and improved crystallinity with the increase of HfO2 thicknesses

102

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) HfO2 counterparts. As for stack structures, the relatively thick Al2O3 layer (3 nm) in direct contact with the electrode contributes to the small leakage current. In comparison, 1.5 nm Al2O3 in the sandwich structure may not be thick enough to effectively block the oxygen diffusion during HfO2 growth and therefore worsen the interface quality. With regard to the laminated structure, the alternate insertion of 1 nm Al2O3 between 5 nm HfO2 inhibit the grain growth extending from bottom electrode to top electrode. A similar concept of using multiple annealing for HfO2 treatment to offset the grain boundary has also been reported elsewhere [30]. To confirm this, TEM photos of laminated (13 nm) and pure HfO2 (10 nm and 30 nm) films are illustrated in Figs. 4.19(a, b, c). As seen from Fig. 4.19(a) (also shown in Fig 4.2), HfO2 layer in the laminate film is amorphous. In comparison, some crystallites could be observed in the case of 10 nm HfO2 illustrated in Fig. 4.19(b), and the crystallinity improves when the dielectric thickness increases to 30 nm. Considering the temperature for HfO2 growth by ALD is ~340oC in this work, the crystallization of thick HfO2 is expected and in agreement with the conclusion obtained in Chapter 2. Besides, the TEM results suggest that the crystallization of thin film is closely dependent on the dielectric thickness. As the film thickness increases, the growth of polycrystalline structure dominates, and thinner dielectric film probably has relatively higher crystallization temperature [31]. Therefore, the alternate insertion of Al2O3 can effectively suppress the crystallization of HfO2 and inhibit the grain growth. The oxygen diffusion could be reduced as well due to the alternate Al2O3 layers. To conclude, laminate dielectric exhibit the unique advantage in terms of material structure which could be further evidenced from the breakdown characteristics of all five samples as illustrated in the inset of Fig. 4.18 with the similar

103

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) trend as the J-V characteristics. The laminated film is of the highest breakdown strength of ~5.0 V at 125oC by taking 50% probability of failure as the criteria. In addition, the evolution of AC capacitance with stress time has been evaluated for different structural MIM capacitors as shown in Fig. 4.20. It was noted that, with increase of stress time, the capacitance values of all five samples increase steadily showing the similar trend. This phenomenon was recently reported for SiO2 MIM capacitor [32], and it was proposed to be due to the dipole generation which is directly correlated to the amounts of trapped charges in the dielectric films [32]. In comparison, the laminated MIM capacitor shows the smallest capacitance variation, which is probably attributed to slight charge trapping in the laminated film as discussed before. When considering that the drift of capacitance value is detrimental to the accuracy of circuit operation, the laminated MIM capacitor exhibits the highest

0.0015

(C-C0)/C0@0V

CVS@4V A/H H/A A/H/A L

0.0010

0.0005

0.0000 0 10 20 30 40 50 60

Stress time (min)

Figure 4.20: Evolution of C0 at zero DC bias with stress time, illustrating the highest stability for the laminated capacitor compared to other dielectric structures.

104

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) capacitance stability when subject to electrical stress. In addition, the variation of and under stress was also found to be the smallest in the case of laminated MIM capacitor (not shown). Though it is conceptually clear that the laminated dielectric is in possession of many unique advantages, further electrical characterization and material analyses are needed for better understanding. In Chapter 5, we will further present the CV characteristics of various structural HfO2-Al2O3 MIM capacitors, showing the advantage of symmetrical material structure.

4.5. Conclusion

In summary, MIM capacitors using atomic layer deposited HfO2-Al2O3 laminate are fabricated and characterized. The laminated capacitor can offer high capacitance density (12.8 fF/m2) up to 20 GHz, low leakage current (4.910-8 A/cm2 at 125oC), breakdown field of ~6 MV/cm, small linear VCC and TCC values. In addition, the HfO2-Al2O3 laminate exhibits Poole-Frenkel emission at high electric field, and the leakage current density at low electric field likely results from both Schottky emission and TAT contributions. A decrease and recovery of the leakage current density under and after CVS are observed in the laminated film, which is ascribed to trapping and detraping in the dielectric. It is also found that may have a logarithmic relationship with dielectric thickness and frequency as well. In addition, the VCCs also depend on CVS, which is attributed to electron charge trapping thereby modifying the electric field profile within the MIM capacitor. Finally, different dielectric structures including laminate, stack, and sandwich are compared, and the HfO2-Al2O3 laminated MIM capacitor exhibits the advantages in terms of leakage,

105

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) reliability, and capacitance stability owing to its unique merits in terms of material structure.

106

Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD)

Reference:

[1] H. Kattelus, M. Ylilammi, and J. Saarilahti, Layered tantalum-aluminium oxidefilms deposited by atomic layer epitaxy, Thin Solid Films, Vol. 205, pp. 296-298, 1993. [2] O. Sneh, R. B. Clark-Phelps, A. R. Londergan, J. Winkler, and T. E. Seidel, Thin film atomic layer deposition equipment for semiconductor processing, Thin Solid Films, Vol. 402, pp. 248-261, 2002. [3] D. Hausmann, J. Becker, S. L. Wang, and R. G. Gordon, Rapid vapor deposition of highly conformal silica nanolaminates, Science, Vol. 298 (5592), pp. 402-406, 2002. [4] S. J. Won, Y. K. Jeong, D. J. Kwon, M. H. Park, H. K. Kang, K. P. Suh, H. K. Kim, J. H. Ka, K. Y. Yun, D. H. Lee, D. Y. Kim, Y. M. Yoo, and C. S. Lee, Novel plasma enhanced atomic layer deposition technology for high- capacitor with EOT of 8 on conventional metal electrode, in Proc. Symp. VLSI Technology, pp. 23-24, 2003. [5] H. Iwai, S. Ohmi, S. Akama, C. Ohshima, A. Kikuchi, I. Kashiwagi, J. Taguchi, H. Yamamoto, J. Tonotani, Y. Kim, I. Ueda, A. Kuriyama, and Y. Yoshihara, Advanced gate dielectric materials for sub-100 nm CMOS, in Proc. of IEDM, pp. 625-628, 2002. [6] J. H. Lee, J. P. Kim, J. H. Lee, Y. S. Kim, H. S. Jung, N.-I. Lee, H. K. Kang, K. P. Suh, M. M. Jeong, K. T. Hyun, H. S. Baik, Y. S. Chung, X. Liu, S. Ramanathan, T. Seidel, J. Winkler, A. Londergan, H. Kan, J. M. Ha, and N. K. Lee, Mass production worthy HfO2-Al2O3 laminate capacitor technology using Hf liquid precursor for sub-100 nm DRAMs, in Proc. of IEDM, pp. 221-224, 2002.

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Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) [7] H. Seidl, M. Gutsche, U. Schroeder, A. Birner, T. Hecht, S. Jakschik, J. Luetzen, M. Kerber, S. Kudelka, T. Popp, A. Orth, H. Reisinger, A. Saenger, K. Schupke, and B. Sell, A fully integrated Al2O3 trench capacitor DRAM for sub-100 nm technology, in Proc. of IEDM, pp. 839-842, 2002. [8] M. L. Green, M. Y. Ho, B. Busch, G. D. Wilk, T. Sorsch, T. Conard, B. Brijs, W. Vandervorst, and P. I. Risnen, D. Muller, M. Bude, and J. Grazul, Nucleation and growth of atomic layer deposited HfO2 gate dielectric layers on chemical oxide (Si-O-H) and thermal oxide (SiO2 or Si-O-N) underlayers, J. Appl. Phy., Vol. 92, No. 12, pp. 7168-7174, 2002. [9] G. D. Wilk, R. M. Wallace, and J. M. Anthony, High- gate dielectrics: current status and material properties considerations, J. Appl. Phy., Vol. 89, No. 10, pp. 5243-5275, 2001. [10] S. B. Chen, C. H. Lai, A. Chin, J. C. Hsieh, and J. Liu, High-density MIM capacitors using Al2O3 and AlTiOx dielectrics, IEEE Electron Device Lett., Vol. 23, No. 4, pp. 185-187, 2002. [11] M. Y. Yang, C. H. Huang, A. Chin, C. Zhu, M. F. Li, and D.-L. Kwong, Highdensity MIM capacitors using AlTaOx dielectrics, IEEE Electron Device Lett., Vol. 24, No. 5, pp. 306-308, 2003. [12] H. Hu, C. Zhu, X. Yu, A. Chin, M. F. Li, B. J. Cho, and D. -L. Kwong, MIM capacitors using atomic-layer-deposited high- (HfO2)1-x(Al2O3)x dielectrics, IEEE Electron Device Lett., Vol. 24, pp. 60-62, 2003. [13] Y. Nakamura, I. Asano, M. Hiratani, T. Saito, and H. Goto, Oxidation-resistant amorphous TaN barrier for MIM-Ta2O5 capacitors in giga-bit DRAMs, in Proc. Symp. VLSI Technology, pp.39-40, 2001.

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Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) [14] T. Ishikawa, D. Kodama, Y. Matsui, M. Hiratani, T. Furusawa, and D. Hisamoto, High-capacitance Cu/Ta2O5/Cu MIM structure for SoC applications featuring a single-mask add-on process, in IEDM Tech. Dig., pp. 940-942, 2002. [15] The international Technology Roadmap for Semiconductors, Semiconductor Industry Association, 2002. [16] S. J. Kim, B. J. Cho, M. F. Li, X. Yu, C. Zhu, A. Chin, and D.-L. Kwong, PVD HfO2 for high-precision MIM capacitor applications, IEEE Electron Device Lett, Vol. 24, No. 6, pp. 387-389, 2002. [17] S. J. Kim, B. J. Cho, M. F. Li, C. Zhu, A. Chin, and D.-L. Kwong, HfO2 and lanthanide-doped HfO2 MIM capacitors for RF/mixed IC applications, in Proc. Symp. VLSI Technology, pp.77-78, 2003. [18] K. Kukli, J. Ihanus, M. Ritala, and M. Leskela, Tailoring the dielectric properties of HfO2-Ta2O5 nanolaminates, Appl. Phys. Lett., Vol. 68, No. 26, pp. 3737-3739, 1996. [19] C. Chaneliere, J. L. Autran, R. A. B. Devine, and B. Balland, Tantalum pentoxide (Ta2O5) thin films for advanced dielectric applications, Materials Science and Engineering, R22., pp. 269-322 1998. [20] W. Zhu, T. P. Ma, T. Tamagawa, Y. Di, J. Kim, R. Carruthers, M. Gibson, and K. Furukawa, HfO2 and HfAlO for CMOS: thermal stability and current transport, in Proc. of IEDM, pp. 463-466, 2001. [21] W. K. Chim, T. H. Ng, B. H. Koh, W. K. Choi, J. X. Zheng, C. H. Tung, and A. Y. Du, Interfacial and bulk properties of zirconium dioxide as a gate dielectric in metal-insulator-semiconductor structures and current transport mechanisms, J. Appl. Phy., Vol. 93, pp. 4788-4793, 2003.

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Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) [22] T. Remmel, R. Ramprasad, and J. Walls, Leakage behavior and reliability assessment of tantalum oxide dielectric mim capacitors, IEEE International Reliability Physics Symposium Proceedings, pp. 277-281, 2003. [23] R. Ramprasad, Phenomenological theory to model leakage currents in metalinsulator-metal capacitor systems, Phys Status Solidi, B 239 (1), pp. 59-70, 2003. [24] E. F. Runnion, S. M. Gladstone, R. S. Scott, D. J. Dumin, L. Lie, and J. C. Mitros, Thickness dependence of stress-induced leakage currents in silicon oxide, IEEE Trans. Electron Devices, Vol. 44, pp.993-1001, 1997. [25] A. Kerber, E. Cartier, R. Degraeve, L. Pantisano, Ph. Roussel, and G. Groeseneken, Strong correlation between dielectric reliability and charge trapping in SiO2/Al2O3 gate stacks with TiN electrodes, in Proc. Symp. VLSI Technology, pp.76-77, 2002. [26] C. Zhu, H. Hu, X. Yu, A. Chin, M. F. Li, and D. -L. Kwong, Voltage and temperature dependence of capacitance of high- HfO2 MIM capacitors: a unified understanding and prediction, in Proc. of IEDM, pp. 879-882, 2003. [27] Y. L. Tu, H. L. Lin, L. L. Chao, D. Wu, C. S. Tsai, C. Wang, C. F. Huang, C. H. Lin, and J. sun, Characterization and comparison of high- metal-insulator-metal (MiM) capacitors in 0.13m Cu BEOL for mixed-mode and RF applications, in Proc. Symp. VLSI Technology, pp.79-80, 2003. [28] X. Yu, C. Zhu, H. Hu, A. Chin, M. F. Li, B. J. Cho, D. -L. Kwong, P. D. Foo, and M. B. Yu, A high-density MIM capacitor (13 fF/m2) using ALD HfO2 dielectrics, IEEE Electron Device Lett., Vol. 24, No. 2, pp.63-65, 2003. [29] H. Hu, S. -J. Ding, H. Lim, C. Zhu, M. F. Li, S. J. Kim, X. Yu, J. H. Chen, Y. F. Yong, B. J. Cho, D. S. H. Chan, Subhash C Rustagi, M. B. Yu, C. H. Tung, A. Y. Du, D. My, P. D. Foo, A. Chin, and D. -L. Kwong, High performance ALD

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Chapter 4 HfAlOx MIM Capacitors by Atomic-Layer-Deposition (ALD) HfO2-Al2O3 laminate MIM capacitors for RF and mixed signal IC applications, in Proc. of IEDM, pp. 379-382, 2003. [30] C. C. Yeo, B. J. Cho, M. S. Joo, S. J. Whoang, D. L. Kwong, L. K. Bera, S. Mathew, and N. Balasubramanian, Improvement of electrical properties of MOCVD HfO2 by multistep deposition, Electrochemical and Solid-State Lett., Vol. 6 (11): F42-F44, 2003. [31] M. H. Cho, Y. S. Roh, C. N. Whang, K. Jeong, S. W. Nahm, D. H. Ko, J. H. Lee, N. I. Lee, and K. Fujihara, Thermal stability and structural characteristics of HfO2 films on Si (100) grown by atomic-layer deposition, Appl. Phys. Lett., Vol. 81, No. 3, pp. 472-474, 2002. [32] C. Besset, S. Bruyre, S. Blonkowski, S. Crmer, and E. Vincent, MIM capacitance variation under electrical stress, Microelectronics Reliability, Vol. 43, pp. 1237-1240, 2003.

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

Chapter 5

Understanding Voltage Coefficients of High- MIM Capacitors

5.1. Introduction

In the previous chapters, we thoroughly investigate the electrical characteristics of HfO2 based high- dielectrics; the results indicate those dielectrics are very promising for both RF and analog MIM capacitors application in the future technology node. Among the technical specifications of MIM capacitors prescribed by ITRS roadmap [1], voltage coefficients of capacitance (VCCs) are of great importance, however the parameters dependence of VCCs such as thickness [2-6], frequency [5, 79], etc has been less understood up to now for high- MIM capacitors. Among the parameters affecting the VCCs, the dielectric thickness was widely documented to have a strong non-linear relationship with the quadratic VCCs (). This will increase rapidly with the scaling of high- dielectric thickness. Therefore, it poses a great limitation to meet the strict voltage linearity specifications especially for analog MIM capacitors when high- dielectrics were scaled to achieve higher capacitance density. However, the so-called thickness effect has only been observed experimentally, no theoretical analysis has been done to clarify this phenomena to our best knowledge. In this chapter, for the first time, we present a unified understanding of the quadratic VCCs dependence on thickness based on the free carrier injection model using HfO2 MIM capacitors [10]. It is revealed that the thickness (t) dependence of the quadratic 112

Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors VCCs exhibits a relation of t n (n~2), which is an intrinsic problem due to electrons injection under the enhanced electrical field in the scaled dielectric film. The obtained information is paramount for high- dielectric MIM capacitors application in every aspect and is very useful for the design purpose. In addition, this model has been extended to interpret the frequency dependence of the quadratic VCCs, and the stress modified quadratic VCCs. It is proposed that the quadratic VCCs variation could be attributed to the change of relaxation time, which was modulated through the change of carrier mobility and/or concentration in the dielectric films. In a word, this model could also be applied to other high- dielectric MIM capacitors, predicting their voltage linearity characteristics and help to establish the process-property relationship.

5.2. Theory

To be more specific, the VCCs are differentiated into the quadratic () and linear () coefficients, which could be obtained by fitting the C-V curves using a polynomial equation (C(V) = C0(V2+V+1)) [11]. Among them, the quadratic VCCs are more critical for analog capacitors according to ITRS roadmap [1]. Especially, it was reported extensively that the quadratic VCCs have a nonlinear dependence on thickness, namely thickness effect. In this work, we mainly discuss the quadratic VCCs mechanism; and to be simple, the VCCs were referred to the quadratic VCCs unless otherwise specified. When considering the C-V characteristics of MIM capacitors, it is known that the carriers transport is responsible for the capacitance variation [12]. Based on this understanding, the free carrier injection model was employed in this work, which correlates the dielectric property change (capacitance variation) to the injected carriers

113

Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors (electrons). According to Coelho [13, 14], the complex dielectric constant is given by

* = ' j ' ' =

1 + j tanh( A) j + A

5.1),

where is the frequency of 2f , is dielectric constant defined as the sum of the optical part ( op ) and the low frequency (non-optical) part, and is the relaxation time of the free carriers which is given by

=
A in (1) is given by

qn0

(5.2).

A=
where D in (5.3) was described as

1 + j t ( ) D 2

(5.3),

D = kT / q

(5.4).

From the above equations, numerically computed by (5.1) could finally be correlated to the measured capacitance value by

C=

'
t

(5.5),

where t is the dielectric thickness. According to this model, the charge excess in the insulator could follow the alternating (AC) signal with a relaxation time of that depends on the mobility of carrier, carrier density, and dielectric constant; and a higher relaxation time means that the carriers are more difficult to follow the alternating signal. As noted from (5.2), n0 is defined as the uniform free-electron concentration at the equilibrium. However, when the capacitor was subject to DC bias, the free carrier concentration in the dielectric is modified accordingly due to the electron injection 114

Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

from the cathode. Therefore, n which stands for the modified free-carrier concentration under DC bias is intended to replace n0 when simulating the C-V characteristics of MIM capacitors. This can be obtained by taking account of the conduction mechanism in the dielectric film by analysis of J-V characteristics according to the various proposed theoretical models [15, 16].

5.3. Results and discussion 5.3.1. Thickness dependence of VCCs for HfO2 MIM capacitor

Figure 5.1 showed the typical J-V characteristic of 30 nm HfO2 MIM capacitor prepared by atomic-layer-deposition (ALD) with Ta serving as the electrodes; the detailed fabrication procedures of HfO2 MIM capacitors could be found elsewhere [5]. In order to identify the conduction mechanisms, the J-V curve was fitted by possible electronic conduction models; including Schottky emission, Poole-Frenkel conduction, space charge limited conduction, tunneling, hopping, etc. As a result, the J-V curve shown in the inset of Fig. 5.1 could be well fitted by the Schottky conduction mechanism as evidenced in Fig. 5.1, indicating the electrode limited current transport in 30 nm HfO2 MIM capacitor. For the Schottky emission conduction, the leakage current density as a function of the electric field, could be expressed by

J = A * T 2 exp(

E eb ) exp( S ) KT 2 KT

(5.6),

where A is the Richardson constant, b is the potential barrier height, s is given by

s =

e3

op 0

5.7).

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

Here, op is the optical part of the dielectric constant given by

op = nr 2
while n r is the refractive index of the dielectric.

(5.8),

-10
10
Current density (A/cm 2)
-4

10 10 10 10 10

-5

-12 -14
Ln(J)

-6

-7

-8

-9

2 3 4 Voltage (V)

-16 -18
30 nm HfO2 MIM Capacitor

-20

200 400 600 800 1000 1200 1400 1600

Sqrt(E)

Figure 5.1: Schottky plot of 30 nm HfO2 MIM capacitor. The inset shows the typical JV curve.

In consideration of the Schottky dominated leakage current transport in ALD HfO2 dielectric film, the free electrons concentration as a function of electrical field (or voltage) could be given by
n = n0 exp( eb E ) exp( S ) 2 KT KT (5.9).

Accordingly, the capacitance variation could be modeled as a function of DC bias. Figure 5.2 presented both the measured and simulated C-V data using the above free

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors carrier injection model, and all the fitting parameters have also been stated as well. Among them, a barrier height b of 1.28 eV was used [17, 18].

Normallized capacitance (ppm)

14000 12000 10000 8000 6000 4000 2000 0 -6 -4

Measured CV (30 nm, 1 MHz) Calculated CV (30 nm, 1 MHz)

T=300K b=1.28 eV
S=3.2x10
-24

J/(V/m) 14 cm

1/2

n0=1.636x10
=6.6x10

-3

-5

2 cm /vs

-2

0 2 Voltage (V)

Figure 5.2: Measured and simulated normalized capacitance as a function of voltage. n0 and are extracted by fitting the measured data.

Beside, s is of 3.210-24 J/(V/cm)1/2, and n r is 2.0 extracting from the Schokkty emission fitting, which is similar with the value of 1.97 obtained by ellipsometer. Finally, the best fitting corresponded to the fitting parameters of n0 = 1.6361014 cm-3 and = 6.610-5 cm2/V*s, respectively. The good agreement between the measured and simulated data suggested the free carrier injection model could predict the C-V characteristics of MIM capacitors quite well. However, the small discrepancy is reflected by the non-zero linear coefficient for the measured C-V curve, which corresponded to the parallel shift of the C-V curve along the voltage axis.

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

cm )

-3

3.5 3.0 2.5 2.0 1.5 1.0 20 30 40 50 60

q n 0 (V/t)=A*T2 exp(-q b /kT) so, n 0 /t ~ constant

Carrier conc. pre-factor (x10

14

Thickness (nm)

Figure 5.3: Carrier concentration pre-factor (n0) dependence on thickness.

Before we proceeded to discuss the thickness dependence of the VCCs, the change of n0 (the pre-factor in (5.9)) with dielectric thickness had to be taken into account. Considering the fact that only the AC signal (V0 = 25 mV) is applied on the dielectric with zero DC bias, it is reasonable to believe that the thermal movement is dominant over the electronic diffusion according to [12, 18]. Therefore, the current density is given by

en0 E 0 = A T 2 exp(

e b ) kT

(10),

where E0 = V0/t is the electrical field of the applied AC signal. Figure 5.3 shows the linear dependence of carrier concentration pre-factor n0 on thickness. As a result, the simulated normalized capacitances (C/C0) as a function of voltage with different

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

Normallized capacitance (ppm)

35000 30000 25000 20000 15000 10000 5000 0 -5000 -6 -4 -2 0 2 4 6

normallized capacitance decreases as thickness increased from 20 to 60 nm by step of 10 nm

Voltage (V)

Figure 5.4: Simulated normalized capacitance as a function of voltage for different thickness of 20, 30, 40, 50, and 60 nm.

thicknesses is shown in Fig. 5.4 after taking the change of pre-factor n0 with thickness into account. It was noticed that the C-V curves bent more upwards with the decrease of the dielectric thickness, suggesting a fast increase of VCCs. In comparison, Figure 5.5 presents the VCCs dependence on thickness in log-log scale with and without considering the change of pre-factor n0. A nearly linear thickness dependence of VCCs (in log-log scale) was revealed which may be valid with certain range of thicknesses, indicating a relation of tn . Further, after taking the effect of thickness on the prefactor into account, the VCCs changes more gently with the thickness. Besides, the exponential factor n is 2.1 after extraction, which is consistent with the report on PVD HfO2 where n is 1.93 [6]. In addition, R. B. van Dover et al also proposed that VCCs was inversely proportional to the square of the dielectric thickness (n=2) based on their

119

Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors experimental results on Ta2O5 MIM capacitor [2]. The recent data on HfO2-Al2O3 laminate MIM capacitors also supported our finding with n of 1.97 [19]. According to the above discussion, the implication of tn (n~2) is significant that the exponential increases of VCCs are unavoidable when the dielectric thickness was scaled to achieve higher capacitance density. The requirement for achieving high capacitance density and preserving small VCCs appears to be a fundamental problem for high- MIM capacitors.

10
Quadratic VCC (ppm/V )
2

Without accounting thickness depedence of carrier concentration pre-factor

10

Accounting thickness depedence of carrier concentration pre-factor

10

10

20

30

40

50

60 70

Thickness (nm)

Figure 5.5: The simulated VCCs as a function of thickness with and without taking account of the change of pre-factor (n0) with thickness.

Furthermore, in the modeling of thickness effect on the C-V characteristics, it relied on the leakage characteristics of HfO2 MIM capacitor. It was implicitly assumed in this work that the conduction mechanism was dominated by Schottky emission

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

which was valid within certain thicknesses and voltage ranges. With regard to other possible conduction mechanisms, Poole-Frenkel conduction mechanism had been widely observed for high- dielectrics [12, 19-22], which could be considered as the internal Schottky emission of the trapped electrons from the defects levels to the conduction band of the dielectric [14, 15]. Thus, the similar conclusion is anticipated for the thickness dependence of VCCs.

10 Linear coefficients (ppm/V)

10

10

ALD HfO2 [5] PLD HfO2 [7]

2

10

HfO2-Al2O3 laminate [19] HfO2-Al2O3 composite [23] PVD HfO2 [6, 24] Tb doped HfO2 [24]

10

2 4 6 8 10 12 2 Capacitance density (fF/m )

14

16

Figure 5.6: Linear voltage coefficients versus the capacitance density for HfO2 based high- dielectrics at 100 kHz.

With regard to the linear VCCs, the available literature data for high- MIM capacitors doesnt indicate that it has a direct relationship with dielectric thickness (or capacitance density). To be clear, we have summarized the linear voltage coefficients versus the capacitance density (or dielectric thickness) for HfO2 based MIM capacitors in Fig. 5.6, where the weak linear VCCs dependence on the dielectric thickness could be observed. It was concluded that the linear VCCs could be affected by many

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

Table 5.1: Different structural HfO2-Al2O3 high- MIM capacitors prepared by ALD method Samples Hf-Al-1 Hf-Al-2 Hf-Al-3 Hf-Al-4 Dielectric structures Pure HfO2 Al2O3/HfO2 HfO2/Al2O3 Al2O3/HfO2/Al2O3 Thickness (nm) 13 3/10 10/3 1.5/10/1.5 1/5/1/5/1 Deposition technique: ALD Top electrode: Ta/TaN Bottom electrode: TaN/Ta Experimental

Hf-Al-5 Al2O3/HfO2/Al2O3

1.020 1.015
Hf-Al-1 Hf-Al-2 Hf-Al-3 Hf-Al-4 Hf-Al-5

C/C0

1.010

1.005

1.000 -3 -2 -1 0 1 2 3

Voltage (V)
Figure 5.7: Normalized capacitance versus DC bias measured at 100 kHz, showing good symmetrical CV characteristics (small linear coefficients ) for sandwich and laminate structures.

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

factors such as fabrication techniques, electrodes in contact, dielectric structures, the bulk property of the dielectric film, and so on. Therefore, chances exist for the optimization of the linear voltage coefficients for MIM capacitors. In our work, we further investigate the effects of different HfO2-Al2O3 dielectric structures on the linear VCCs with the sample details summarized in Table 5.1. Accordingly, Figure 5.7 presents the CV curves for various HfO2-Al2O3 dielectric structures measured at 100 kHz. It is noted that sandwich and laminate structures both show very good symmetrical CV characteristics suggesting the small linear coefficients in comparison with pure HfO2 and stacks MIM capacitors. As known in chapter 4, insertion of Al2O3 layer in contact with bottom electrode improves the interface quality by reducing the reaction between dielectric and bottom electrode in ALD deposition. As a result, sandwich and laminate structures exhibit the great advantages of small linear VCCs which are probably attributed to their symmetrical material structures [25] as well as good interface properties. In comparison, the quadratic VCCs for all the structures are relatively the same at ~1500 ppm/V2 measured at 1 MHz. This is expected since the nominal thicknesses of all the samples are the same at 13 nm. However, the detailed mechanism of linear VCCs dependency still need more study and under development.

5.3.2. Frequency dependence of VCCs

From the model itself, the VCCs are nearly independent of frequency from numerically computation when keeping the remaining fitting parameters unchanged. However, the frequency dependence of VCCs has been observed for many high- dielectric materials, and the VCCs virtually decreased with frequency, which was

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

10
Quadratic VCC (ppm/V )
Measured quadratic VCC at different frequency
2

-3

10

10 10
2

-4

Fitted carrier mobility based on the measured quadratic VCC 30 nm HfO2 MIM Capacitor

10

10k

100k Frequency (Hz)

1M

10

-5

Figure 5.8: The measured VCCs for 30 nm HfO2 MIM capacitor together with the extracted carrier mobility at frequencies of 10k, 100k, 500k, 1 MHz.

Normallized capacitnace (ppm)

40000 30000 20000 10000 0 -6 -4 -2 0 2 4 6

Normallized capacitance decreases as the frequency increasing from 10 kHz, 100 kHz, 500 kHz, and 1MHz

Voltage (V)

Figure 5.9: Simulated normalized capacitance as a function of voltage for 30 nm HfO2 MIM capacitors at frequencies of 10k, 100k, 500k, and 1MHz.

Carrier mobility (cm /vs)

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

simply attributed to the traps with the different time constants in the dielectric [8, 26]. In this work, according to the free carrier injection model, we noticed that the frequency dependence of VCCs could be interpreted when considering the change of the carriers mobility at different frequencies. As shown in Fig. 5.8, the measured quadratic VCCs for 30 nm HfO2 at different operating frequencies was shown; together with the extracted carrier mobility at various operating frequency. It was found that the reduced VCCs corresponded to the decreased free carrier mobility in the dielectric film. Further, the simulated normalized capacitances as a function of voltage at different frequencies are shown in Fig.5.9. Recently, it was reported by C. H. Huang

et al that VCCs of high- AlTaOx MIM capacitor continued to decrease from IF to RF

frequency regime using a newly developed mathematical method [9]. According to Coelho [14], the free carriers mobility () accounts for all the inelastic collisions between electrons and the lattice and/or defects in the dielectrics. As a result, the electrons moving from the cathode to anode will become much more affected with the increase of frequency, causing the carrier mobility to decrease with frequency; therefore the capacitance variation become weak with DC bias. According to (5.2), the decreased carrier mobility will lead to higher relaxation time which was generally used to interpret the frequency dependence of VCCs for high- MIM capacitors.

5.3.3. Electrical stress modified VCCs

In Chapter 3, we observed that the quadratic VCCs will reduce monotonously with stress time for PVD HfO2, and a physical circuit model was employed to explain

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

the underlying mechanism. Similarly, the same trend could be found in HfO2-Al2O3 laminate MIM capacitors [19]. Based on the free carrier model, we are able to further interpret these phenomena. As we know, the relaxation time () could be regarded as the approach of free carrier distribution to the steady state. In other words, certain amounts of relatively immobile species may result in much longer relaxation time. Considering the traps generation in the dielectric film after electrical stress (see Figure 3.7 in Chapter 3), the injected electrons could be captured in the trap sites to become immobilized. Therefore, an increase of average relaxation time was anticipated, and it could be explained as the carrier mobility change to some extent in the case of the traps generation [27]. As a result, the capacitance will change more slowly with bias due to traps generation after stress. The very similar case as seen in the distortion (stretch-out) of C-V curve in MOS device could also been found when the interface states are present [28]. With the continuously increased stress time, more electrons trapping probably renders the VCCs decrease monotonously. In addition, the different amounts of the reduced VCCs may correlate to the different amounts of traps created in oxide films.

5.3.4. Prediction of VCCs

According to the above discussion, it is concluded that the effect of dielectric thickness, frequency, and stress on the VCCs could be either due to the change of free carrier mobility, and/or carrier concentration in high- dielectric film. In conclusion, Figure 5.10(a) and 5.10(b) summarize the VCCs of HfO2 MIM capacitors as a function of thickness, using different pre-factor n0 and carrier mobility values. The results

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

10
Quadratic VCC (ppm/V )
2

10 10 10 10 10

Capacitance density=5fF/m n0=1.636x10 cm

15 -3

Quadratic VCC=100 ppm/V

3

n0=1.636x10 cm

15

-3

n0=1.636x10 cm

14

-3

20

30 40 50 Thickness (nm)
(a)

60

10
Quadratic VCC (ppm/V )
2

Capacitance density=5fF/m

10

=1.1x10 cm /vs

-4

Quadratic VCC=100 ppm/V

=6.6x10 cm /vs
-5 2

10

10

=1.1x10 cm /vs

-5

10

20

30

40 50 Thickness (nm)
(b)

60

Figure 5.10: (a) The simulated VCCs of HfO2 MIM capacitors as a function of thickness with different carrier concentration pre-factor (n0), and (b) the simulated VCCs as a function of thickness with different carrier mobility in dielectric film.

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

showed that the VCCs will drop monotonously with thickness when the pre-factor and carrier mobility values are pre-defined. In addition, the VCCs drop by nearly one order of magnitude when the pre-factor or the carrier mobility decreases by the same order at certain thickness. For a specific instance, in order to meet the specifications for analog MIM capacitor beyond 2007 (VCCs 100 ppm/V2, capacitance density of 5 fF/m2), the hatched areas in Figs. 5.10(a) and 5.10(b) are the regions where the capacitance density and VCCs meet the ITRS roadmap requirements [1]. Comparing with the dielectric thickness, the carrier mobility and pre-factor n0 are mainly affected and determined by certain process conditions for high- dielectrics fabrication. Thus, the effective way to reduce VCCs is to increase the dielectric thickness. However, it severely limits the scaling of high- dielectric for improving capacitance density of MIM capacitors. In order to meet the continuously increased capacitance density requirement as well as small VCCs, dielectrics with much higher dielectric constants than HfO2 needs to be researched and implemented in order for future applications. Besides, it is believed that carrier mobility and pre-factor n0 are strongly affected by the fabrication methods and process conditions [3, 12, 29-31], which directly correlates to the quality of the high- materials. In particular, Y. L. Tu observed that the deposition temperature could affect the VCCs of Ta2O5 MIM capacitor to some extent [3]. However, low thermal budget in back-end line integration severely limits the improvement of high- dielectrics quality, which impedes the successfully wide implementation of high- dielectrics for MIM capacitors application. Recently, several plasma treatment schemes prove to be effective for the leakage property improvement for some high- films at low temperature compatible with BEOL process [30, 31], which may also be promising for the improvement of C-V characteristics for high- MIM capacitors.

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

5.4. Conclusion

In this chapter, a free carrier injection model has been established successfully to explore the VCCs mechanism for high- MIM capacitors using HfO2 as the dielectric. For the first time, it has been revealed that the thickness dependence of VCCs, which exhibits a relation of tn (n~2), is an intrinsic problem due to the electrical field increment when the dielectric film is scaled down. This finding is of great implication for high- MIM capacitors application in many aspects and is also useful for the design purpose. In addition, the frequency dependences of VCCs, and the stress modified VCCs have also been discussed. For both cases, the C-V curves bent downwards with the increase of frequency and/or under electrical stress, i.e. the VCCs will decrease with frequency and/or after electrical stress. Based on the free carrier model, it is proposed that the VCCs variations are attributed to the change of relaxation time, which is in the origin of carrier mobility and/or pre-factor n0 change in the dielectric film. In conclusion, this model could be also easily applied to other high MIM capacitors predicting the C-V characteristics, and help to understand the process-property correlationship of high- dielectrics.

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

References:

[1] The international Technology Roadmap for Semiconductors, Semiconductor Industry Association, 2002. [2] R. B. van Dover, R. M. Flemming, L. F. Schneemeyer, G. B. Alers, and D. J. Werder, Advanced dielectrics for gate oxide, DRAM and rf capacitors, in Proc.

of IEDM, pp. 823-826, 1998.

[3] Y. L. Tu, H. L. Lin, L. L. Chao, D. Wu, C. S. Tsai, C. Wang, C. F. Huang, C. H. Lin, and J. Sun, Characterization and comparison of high- metal-insulator-metal (MIM) capacitors in 0.13m Cu BEOL for mixed-mode and RF applications, in

Proc. Symp. VLSI Technology, pp. 79-80, 2003.

[4] A. Kar-Roy, C. Hu, M. Racanelli, C. A. Compton, P. Kempf, G. Jolly, P. N. Sherman, J. Zheng, Z. Zhang, and A. Yin, High density metal insulator metal capacitors using PECVD nitride for mixed signal and RF circuits, IITC, pp. 245247, 1999. [5] X. Yu, C. Zhu, H. Hu, A. Chin, M. F. Li, B. J. Cho, D.-L. Kwong, P.D. Foo, and M. B. Yu, A high-density MIM capacitor (13 fF/m2) using ALD HfO2 dielectrics,

IEEE Electron Device Lett., Vol. 24, No. 2, pp.63-65, 2003.

[6] S. J. Kim, B. J. Cho, M. F. Li, X. Yu, C. Zhu, A. Chin, and D.-L. Kwong, PVD HfO2 for high-precision MIM capacitor applications, IEEE Electron Device Lett, Vol. 24, No. 6, pp.387-389, 2002. [7] H. Hu, C. Zhu, Y. F. Lu, M. F. Li, B. J. Cho, and W. K. Choi, A high performance MIM capacitor using HfO2 dielectrics, IEEE Electron Device Lett., Vol. 23, No. 9, pp.514-516, 2002. [8] S. B. Chen, C. H. Lai, A. Chin, J. C. Hsieh, and J. Liu, High-density MIM capacitors using Al2O3 and AlTiOx dielectrics, IEEE Electron Device Lett, Vol. 23,

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Chapter 5 Understanding Voltage Coefficients of High- MIM Capacitors

No. 4, pp.185-187, 2002. [9] M. Y. Yang, C. H. Huang, A. Chin, C. Zhu, M. F. Li, and D.-L. Kwong, Highdensity MIM capacitors using AlTaOx dielectrics, IEEE Electron Device Lett., Vol. 24, No.5, pp.306-308, 2003. [10] C. Zhu, H. Hu, X Yu, A. Chin, M. F. Li, and D. -L. Kwong, Voltage and temperature dependence of capacitance of high- HfO2 MIM capacitors: A unified understanding and prediction, in Proc. of IEDM, pp. 879-882, 2003. [11] K.-S. Tan, S. Kiriake, M. de Wit, J. W. Fattaruso, C.-Y. Tsay, W. E. Matthews, and R. K. Hester, Error correction techniques for high-performance differential A/D converters, IEEE J. Solid-State Circuits, Vol. 25, pp. 1318-1327, 1990. [12] S. Blonkowski, M. Regache, and A. Halimaoui, Investigation and modeling of the electrical properties of metal-insulator-metal structures formed from chemical vapor deposited Ta2O5 films, J. Appl. Phy., Vol. 90, pp. 1501-1508, 2002. [13] R. Coelho, Sur ia relaxation dune charge despace, Rev. Phys. Appl., Vol. 18, pp. 137-146, 1983. [14] R. Coelho, Physics of dielectrics for the engineer (Elsevier, 1979.) [15] J. J. Odwyer, The theory of electrical conduction and breakdown in solid

dielectric (Oxford university Press, 1973.)

[16] L. I. Maissel and R. Glang, Handbook of thin film technology (McGraw-Hill Book Company, 1983) [17] W. Zhu, T. P. Ma, T. Tamagawa and Y. Di, HfO2 and HfAlO for CMOS: thermal stability and current transport, in Proc. of IEDM, pp. 463-466, 2001. [18] S. M. Sze, Physics of Semiconductor Devices, 2nd ed. (Wiley, New York, 1981.) [19] H. Hu, S. -J. Ding, H. Lim, C. Zhu, M. F. Li, S. J. Kim, X. Yu, J. H. Chen, Y. F. Yong, B. J. Cho, D. S. H. Chan, Subhash C Rustagi, M. B. Yu, C. H. Tung, A. Y.

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Du, D. My, P. D. Foo, A. Chin, and D.-L. Kwong, High performance ALD HfO2-Al2O3 laminate MIM capacitors for RF and mixed signal IC applications, in Proc. of IEDM, pp. 379-382, 2003. [20] H. Zhang, R. Solanki, B. Roberds, G. Bai and I. Banerjee, High permittivity thin film nanolaminates, J. Appl. Phy., Vol. 87, pp. 1921-1924, 2000. [21] W. K. Chim, T. H. Ng, B. H. Koh, W. K. Choi, J. X. Zheng, C. H. Tung, and A. Y. Du, Interfacial and bulk properties of zirconium dioxide as a gate dielectric in metal-insulator-semiconductor structures and current transport mechanisms, J.

Appl. Phy., Vol. 93, pp. 4788-4793, 2003.

[22] T. Yoshitomi, Y. Ebuchi, H. Kimijama, T. Ohguro, E. Morifuji,. H.S. Momose, K. Kasai, K. Ishimaru, F..Matsuoka, Y. Katsumata, M. Kinugawa, and H. Iwai, High performance MIM capacitor for RF BiCMOS/CMOS LSIs, in Proc. of

BCTM, pp. 133-136, 1999.

[23] H. Hu, C. Zhu, X. Yu, A. Chin, M. F. Li, B. J. Cho, and D. -L. Kwong, MIM capacitors using atomic-layer-deposited high- (HfO2)1-x(Al2O3)x dielectrics,

IEEE Electron Device Lett., Vol. 24, pp. 60-62, 2003.

[24] S. J. Kim, B. J. Cho, M. F. Li, C. Zhu, A. Chin, and D. -L. Kwong, HfO2 and lanthanide-doped HfO2 MIM capacitors for RF/mixed IC applications, in Proc.

Symp. VLSI Technology, pp.77-78, 2003.

[25] S. Van Huylenbroeck, S. Decoutere, R. Venegas, S. Jenei, and G. Winderickx, Investigation of PECVD dielectrics for nondispersive metal-insulator-metal capacitors, IEEE Electron Device Lett., Vol. 23, No. 4, pp. 191-193, 2002. [26] J. A. Babcock, S. G. Balster, A. Pinto, C. Dirnecker, P. Steinmann, R. Jumpertz, and B. El-Kareh, Analog characteristics of metal-insulator-metal capacitors

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using PECVD nitride dielectrics, IEEE Electron Device Letters, Vol. 22, No. 5, pp. 230-232, 2001. [27] B. Gross, Dose rate dependence of carrier mobility, Solid State Commun., Vol. 15, pp. 1655-1657, 1974. [28] E H Nicollian and J R Brews, MOS (Metal Oxide Semiconductor) Physics and

technology (Wiley, 1982)

[29] H. Hu, C. Zhu, X. F. Lu, Y. H. Wu, T. Liew, M. F. Li, B. J. Cho, W. K. Choi and N. Yakovlev, Physical and electrical characterization of HfO2 metal-insulatormetal capacitors for Si analog circuit applications, J. Appl. Phy., Vol. 94, pp. 551-557, 2003. [30] G. B. Alers, R. M. Fleming, Y. H. Wong, B. Dennis and A. Pinczuk, Nitrogen plasma annealing for low temperature Ta2O5 films, Appl. Phys. Lett., Vol. 72, No. 11, pp. 1308-1310, 1998. [31] S. J. Chang, J. S. Lee, J. F. Chen, S. C. Sun, C. H. Liu, U. H. Liaw and B. R. Huang, Improvement of electrical and reliability properties of tantalum pentoxide by high-density plasma (HDP) annealing in N2O, IEEE Electron

Device Lett., Vol. 23, No. 11, pp. 643-645, 2002.

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Chapter 6 Summary and Future Works

Chapter 6 Summary and Future Works

6.1. Summary

In this thesis, HfO2 based high- MIM capacitors have been thoroughly investigated. These have been accomplished by preparing HfO2 based high- films using various preparation methods such as pulsed-laser deposition (PLD), sputtering, atomic-layer-deposition (ALD) and studying the material and electrical properties of these high- films. The important findings and conclusions obtained in the course of the studies can be summarized as the following: 1) HfO2 high- dielectrics prepared by PLD have been fabricated for MIM capacitors application for the first time with superior electrical performance; a good understanding of process-structure-property correlation for HfO2 film processing has been achieved. 2) RF characteristics of HfO2 based high- MIM capacitors were investigated; the results indicate that HfO2 based high- materials exhibit good capacitancefrequency dependency, i.e. the dielectric constant of HfO2 remains almost constant in the entire frequency range up to 20 GHz. In addition, thickness dependence of stress induced leakage currents and voltage linearity for HfO2 MIM capacitors have been discussed with the help of an equivalent circuit model, which are proposed to be in the origin of traps generation in the dielectric films.

134

Chapter 6 Summary and Future Works 3) ALD prepared high- HfO2-Al2O3 MIM capacitors using laminate, stack and sandwich structures were characterized. The electronic conduction mechanism, voltage coefficients of capacitance (VCCs) dependence, etc have been investigated in detail. In comparison with stack and sandwich structures, the laminate structure is superior in terms of electrical performance. In addition, ALD technique shows the advantages of film quality, uniformity, and the ease of dielectric structure engineering over PLD and PVD methods. 4) Finally, a free carrier injection model has been established successfully to explore the VCCs mechanism for high- MIM capacitors using HfO2 as the dielectric. It has been revealed that the thickness dependence of VCCs, which exhibits a relation of tn (n~2), is an intrinsic problem due to the electrical field increment when the dielectric film is scaled down. In addition, the frequency dependences of VCCs, and the stress modified VCCs have been also discussed using the free carrier model. It is proposed that the VCCs variations are attributed to the change of relaxation time, which is in the origin of carrier mobility and carrier concentration change in the dielectric film.

6.2. Future works

There are a few aspects the author thinks would be worth for further investigation: 1) HfO2 films processing In this work, HfO2 films are in their as-deposited states without any postdeposition treatment, traditional furnace annealing in this work was found to be less effective for the quality improvement of thick HfO2 films which might be due

135

Chapter 6 Summary and Future Works

to the allowable thermal budget in back-end of line (BEOL) integration. Therefore, it is worthwhile to develop some novel thermal treatment schemes, such as multideposition and multi-annealing method, high density plasma annealing process, and so on. 2) Dielectrics properties engineering The reported VCCs and temperature coefficient of capacitance (TCCs) for high- dielectrics are much larger than those of SiO2 and Si3N4. Considering the positive VCC and TCC values of most high- dielectrics, it would be nice to search alternative dielectrics in possession of negative VCCs and TCCs values, and incorporating those dielectrics into current high- systems to achieve low TCCs and VCCs values. 3) VCCs mechanism study In this work, our current results indicate that the VCCs dependence on many parameters such as thickness, frequency, and electrical stress is mainly a bulk effect. However, it is believed that the metal/dielectric interface may also play a role affecting the VCCs. The effects of the interface properties on the VCCs needs more study. In addition, the extent of capacitance variation is shown to be dependent on the bias polarity, how could this by affected by each leakage component (like Schottky emission, Poole-Frenkel conduction and so on.) need further investigation. 4) Integration of HfO2 based dielectrics In the current technology node, HfO2 based dielectrics needs to be put into Cu/low BEOL process for their real use, the process related issues like the proper choice of metal stacks, the compatibility with low- material, the effects of plasma

136

Chapter 6 Summary and Future Works

etching on high- dielectrics, and so on, are useful topics for integration of HfO2 based materials.

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List of Publications

LIST OF PUBLICATIONS
1. H. Hu, C. Zhu, Y. F. Lu, M. F. Li, B. J. Cho, and W. K. Choi, A high performance MIM capacitor using HfO2 dielectrics, IEEE Electron Device Lett., Vol. 23, pp. 514-516, 2002. 2. H. Hu, C Zhu, Y. F. Lu, Y. H. Wu, T. Liew, M. F. Li, B.J. Cho, W. K. Choi, and N. Yakovlev, Physical and electrical characterization of HfO2 metal-insulatormetal capacitors for Si analog circuit applications, J. Appl. Phys., Vol. 94, No. 1, pp. 551-557, 2003. 3. H. Hu, C. Zhu, X. Yu, A. Chin, M. F. Li, B. J. Cho, and D. -L. Kwong, MIM capacitors using atomic-layer-deposited high- (HfO2)1-x(Al2O3)x dielectrics, IEEE Electron Device Lett., Vol. 24, pp. 60-62, 2003. 4. X. Yu, C. Zhu, H. Hu, A. Chin, M. F. Li, B. J. Cho, D. -L. Kwong, F. D. Foo, and M. B. Yu, A high density MIM capacitor (13 fF/m2) using ALD HfO2 dielectrics, IEEE Electron Device Lett., Vol. 24, pp. 63-65, 2003. 5. H. Hu, C. Zhu, Y. F. Lu, J. N. Zeng, Y. H. Wu, T. Liew, M. F. Li, and W. K. Choi, Material and electrical characterization of HfO2 films for MIM capacitors application, Mat. Res. Soc. Symp. Proc. Vol. 766, E.3.3.1, 2003. 6. X. Yu, C. Zhu, H. Hu, A. Chin, M. F. Li, B. J. Cho, D. -L. Kwong, P. D. Foo, and M. B. Yu, MIM capacitors with HfO2 and HfAlOx for Si RF and analog applications, Mat. Res. Soc. Symp. Proc. Vol. 766, E.5.9.1, 2003. 7. H. Hu, S. J. Ding, H. F. Lim, C. Zhu, M. F. Li, S. J. Kim, X. Yu, J. H. Chen, Y. F. Yong, B. J. Cho, D. S. H. Chan, Subhash C Rustagi, M. B Yu, C. H Tung, A. Y. Du, D. My, P. D. Foo, A. Chin, and D.-L. Kwong, High performance ALD HfO2138

List of Publications Al2O3 laminate MIM capacitors for RF and mixed signal IC applications, in Proc. of IEDM, pp. 379-382, 2003. 8. C. Zhu, H. Hu, X Yu, S. J. Kim, A. Chin, M. F. Li, B. J. Cho, and D. -L. Kwong, Voltage and temperature dependence of capacitance of high- HfO2 MIM capacitors: A unified understanding and prediction, in Proc. of IEDM, pp. 879882, 2003. 9. H. Hu, S. J. Ding, C. Zhu, Y. F. Lu, M. F. Li, B. J. Cho, and D. S. H. Chan, S. C. Rustagi, M. B. Yu, A. Chin, and D. -L. Kwong, Investigation of PVD HfO2 MIM capacitors for Si RF and mixed signal ICs application, International Semiconductor Device Research Symposium (ISDRS), pp. 328-329, 2003. 10. S. J. Ding, H. Hu, S. J. Kim, H. F. Lim, C. Zhu, M. F. Li, B. J. Cho, D. S. H. Chan, S. C. Rustagi, M. B. Yu, A. Chin, D. L. Kwong, High performance MIM capacitor using ALD high- HfO2-Al2O3 laminate dielectrics, IEEE Electron Device Lett., Vol. 24, pp. 730-732, 2003. 11. S. J. Ding, H. Hu, H. F. Lim, S. J. Kim, X. F. Yu, C. Zhu, M. F. Li, B. J. Cho, D. S. H. Chan, S. C. Rustagi, M. B. Yu, A. Chin, D. L. Kwong, DC, RF, and reliability characteristics of atomic layer deposited HfO2-Al2O3 laminate MIM capacitors for Si RF IC applications, IEEE Trans. on Electron Devices Vol. 51, pp. 886-894, 2004. 12. S. J. Ding, H. Hu,, C. Zhu, M. F. Li, S. J. Kim, B. J. Cho, S. H. Chan, M. B. Yu, A. Y. Du, A. Chin, D. L. Kwong, Evidence and understanding of atomic-layerdeposited HfO2-Al2O3 laminate MIM capacitors outperforming sandwich counterparts, accepted by IEEE Electron Device Lett.

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