SYNOPSIS OF

Electrical transport and optical studies of transition metal ion doped ZnO and synthesis of ZnO based nanostructures by chemical route, thermal evaporation and pulsed laser deposition

A THESIS to be submitted by SHUBRA SINGH For the award of the degree Of DOCTOR OF PHILOSOPHY

DEPARTMENT OF PHYSICS INDIAN INSTITUTE OF TECHNOLOGY MADRAS JANUARY 2009

1. INTRODUCTION

Modern day materials science depends largely on semiconductors which may be elemental systems such as Si and Ge, or compound semiconductors such as GaAs, ZnO and InP, or alloys such as Si-Ge or aluminium gallium arsenide. This large family also consists of a smaller sub-set of wide bandgap semiconductors (band gap ~ 2 to 3.5 eV) which have electronic band gaps larger than 1.7 eV. Wide bandgap materials are often utilized in applications in which high-temperature operation is important. One of the most important II-VI wide band gap semiconductors, which is a hot topic of research in the 21st century is ZnO. ZnO is one of the most important materials that we come across in our day-to-day lives. Zinc white is used as a pigment in paints and in coatings for paper. Chinese white is a special grade of zinc white used in artists' pigments. At ambient pressure and temperature, ZnO crystallizes in the wurtzite structure as shown in figure 1. It has a hexagonal lattice belonging to the space group P63mc and is characterized by two interconnecting sublattices of Zn2+ and O2- such that each Zn ion is surrounded by oxygen tetrahedra and vice-versa. Besides being a wide band gap (WBG) semiconductor with a bandgap of ~ 3.4 eV and exciton binding energy of 60 meV (almost three times greater than that of GaN, the most widely used WBG compound), it has several other advantages. Some of the favorable aspects of ZnO include its radiation hardness, biocompatibility and its high transparency in visible region. An important aspect of ZnO is the onedimensional ZnO nanostructures which have attracted special attention because of their unique properties and diverse hierarchical nanostructures. Different techniques such as pulsed laser deposition, sputtering, thermal evaporation, condensation, solid state reaction

and chemical methods have been employed to fabricate such nanostructures. The latter relies on the anisotropic structure of ZnO and variation of growth rate on different facets.

Figure 1. ZnO wurtzite structure showing the positions of Zinc and Oxygen atoms and axes direction.

2. MOTIVATION

ZnO is important for its multi-functional properties (semiconducting, magnetic, piezoelectric etc.) for electronic and optoelectronic devices. One of the key requirements for many of these applications is the doping of ZnO with various elements for enhancing and controlling its electrical and optical properties. As grown ZnO is an n-type semiconductor and its n-type conductivity can be controlled by growing it in an oxygen deficient atmosphere or by doping it with group III elements like Al, Ga or In [Zhong et al. 2003]. Besides these dopants, presence of 3d transition metal (TM) ions in ZnO matrix can lead to phonon scattering, thereby reducing thermal conductivity and leading to improved thermoelectric efficiency. When the doped 3d ions have a valence

state of +2, equal to that of Zn, ionic radius differences between Zn and the 3d ions are minimized and defect formation for holding charge neutrality is suppressed. Thus it is necessary to efficiently dope 3d ions in the valence state of 2+ into ZnO. This has motivated us to investigate the influence of transition metals (TMs) namely Ti, V, Mn, Cr, Fe, Co, and Ni dopants on the transport and optical properties of ZnO (bulk and thin film).

3. OBJECTIVES AND SCOPE OF PRESENT WORK High quality 3d doped ZnO samples are required to synthesize a functional DMS whose magnetic properties are controllable by changing the carrier concentration, which implies that there is a need to investigate the transport properties of TM ion doped ZnO. Hence, in the present work the electrical properties of bulk and thin films of undoped and TM ion (Ti, V, Mn, Cr, Fe, Co, and Ni) doped ZnO samples have been investigated. The valence states of these dopants have been confirmed through optical studies. The application of TM ion doped ZnO as UV absorber material has also been investigated in order to explore its applications in ointments, creams, and lotions to protect against sunburn and other damage to the skin caused by ultraviolet light. Besides this, the effect of a dopant element on the microstructure of ZnO has also been studied from the viewpoint of variations in ionic fraction. Growth of ZnO nanostructures by various synthesis routes has been explained and their multifunctional properties have been explored.

4. SUMMARY OF RESEARCH WORK 4.1 Sample synthesis 4.1.1 Synthesis of bulk samples: High pure ZnO and oxides/carbonates of dopant metals were used to prepare bulk Zn1xMxO (x=dopant concentration and M = metal ion) by conventional sol-gel technique. The powder was then made into disk-shaped pellets (~8 mm diameter and ~2 mm thickness) by uniaxial pressing and sintered at 1200C for 24 h. 4.1.2 Thin film growth: Thin films were grown using pulsed laser deposition (PLD) technique. Thin films of the above bulk samples were grown on Si (100) substrates by PLD at a different substrate temperatures and oxygen partial pressures.

4.2 Characterization techniques: The as prepared samples were characterized by PANalytical X'pert X-ray diffractometer, Ocean optics (USB 2000) spectrophotometer, Jobin Yvon spectrometer, linear four probe technique, Scanning electron microscopy (SEM) and EDX.

4.3 Results and discussion 4.3.1 Effect of TM ion doping on electrical and optical properties of ZnO: The as prepared undoped and TM ion doped samples are single phase compounds for 1 mol% doping as observed in XRD patterns. Diffuse reflectance spectra (DRS) of homogenized powder samples were recorded using BaSO4 powder compact (white in colour) as a reference sample. DRS measurements on powder samples or pellets are roughly analogous to transmission measurements on thin films [Hecht. H. (1968)]. Figure 2 shows diffuse reflectance spectra of ZnO and transition metal ion-doped ZnO bulk

samples. Doped ZnO samples exhibited absorption peaks in the visible region in addition to the absorption edge, since the samples containing TM ions will have bands from crystal-field transitions of ions in tetrahedral coordination. As an example, the absorption spectrum of Ni2+ doped ZnO shows the mid-band-gap states appearing at about 430 nm, 580 nm and 655 nm, corresponding to the d-d transition bands, which are characteristic of Ni (II) with tetrahedral symmetry [Alberto et. al (2005)]. In the case of Co doped ZnO, absorption peaks are expected to arise due to electronic transitions from the 4A 2 ground state to the 4T1(P) state for the tetrahedral Co(II). The two sharp absorption peaks of Codoped ZnO are assigned as 4A2(F) 4T1(P) (612 nm) and 4A2(F) 2A1(G) (568 nm). Upon doping Ti, V, Fe and Ni ions in ZnO, we observe a decrease in resistivity of bulk compounds as compared to the undoped compound (figure 3). The change in resistivity of isovalent doping in TM ion doped ZnO can be explained by dband splitting model proposed by Sato et al (2002). Ab initio studies on the TM ion doped ZnO compounds also show the partial overlap of antibonding d-states with the conduction band of host compound [Sato et. al (2002)]. The itinerant electrons in these antibonding states can traverse to the conduction band (CB) and may be responsible for the observed decrease in resistivity of isovalent TM ion doped ZnO systems. However, the amount of splitting leading to the proximity or overlapping of antibonding states with CB may differ for each dopant ion. Figure 4 depicts a schematic model to explain the changes in electronic structure in the case of isovalent TM ion doping at a substitutional site in a wurtzite structure.

120 100 D R (a.u.) 80 60 40 20 0

undoped ZnO Co doped ZnO 568 nm 612 nm

4

100 80 D R (a.u.) 60 40 20 0

Undoped ZnO Ni doped ZnO 580 nm 655 nm

3

T1(F)

T1(P)

A2(F)

A1(G) A2(F)
4

430 nm

T1(P)

400 500 Wavelength (nm)

600

400

500 600 Wavelength (nm)

Fig.2. Diffuse reflectance spectra of bulk undoped and Co and Ni doped ZnO samples. Absorption peaks corresponding to dopant absorption states are clearly indicative of dopant incorporation and the formation of mid band-gap states.

3
(cm)

10 0 100 150 200 T(K) 250 300

Fig.3. vs T of undoped and TM-ion doped ZnO bulk samples. Cr, Co and Mn doped samples were found to be insulating, hence not included in the plot.

(cm)

ZnO Zn0.99Fe0.01O 30 Zn0.99Ti0.01O Zn0.99V0.01O 20 Zn0.99Ni0.01O

Energy
Triplet 3d orbitals

(a)

Doublet under tetrahedral field

Energy
Antibonding states Conduction band

EF

t2g
Bonding states

eg
Valence band

(b)

Fig.4. Depiction of a model to explain the changes in electronic structure in the case of transition metal ion doping at a substitutional site in a wurtzite structure. (a) Crystal field effect of ZnO on 3d metal ion leading to doublet and triplet formation and (b) Impurity states split under the influence of crystal field of the host (ZnO in this case).

Besides this, in the case of Fe, Ti and V doped samples the presence of higher valence states cannot be completely ruled out. For example, the presence of Fe3+ ions in our samples was also corroborated by DRS spectra, which are expected to give rise to donor defects, thereby making the sample more conducting. Thin films were also found to be semiconducting in nature. Ti, V, Fe and Ni doped ZnO samples are found to have lower resistivity than the undoped film similar to the results obtained for their bulk counterparts. However as seen from our experimental results, there exists a certain deviation from the theoretical studies. Experimentally it was observed that the parent sample becomes more resistive on doping Co, Cr and Mn ions.

4.3.2 Microstructural changes in ZnO with doping and substrate effect on optical properties of ZnO film.
In this section, the effect of Cr doping on the microstructure of ZnO is explained. SEM images of bulk Cr doped ZnO calcined at 600oC exhibit a honeycomb-like structure with four branches at each node (figure 5), which was observed only for Cr doped ZnO and not for undoped sample (not shown here), prepared using the same technique as the doped sample. This result can be explained on the basis of ionic fraction of the bond in Cr doped ZnO. The morphology of a particle depends on the value of ionic fraction of a chemical bond. Takeshi et. al used the concept of electronegativity to estimate the ionic fraction of the bond [Takeshi et. al (2005)]. The PL spectra of these samples show that UV radiation peak at 385nm is suppressed for doped sample, thus making it useful for applications as a prospective sunscreen lotion.

(b)

100 m

(a)

100 m

50 m

(c)

(d)

20 m

5 m

Fig.5. SEM images of Cr doped ZnO at different magnifications. Inset shows SEM microstructure of Cr doped ZnO at much lower magnification.

In order to investigate the effect of substrates on the optical properties of ZnO films, the growth parameters were first optimized. The films were then grown at an optimum condition for about 2 h at an oxygen partial pressure of 3 mbar and a substrate temperature of 500oC, on Si as well as glass substrates. From figure 6, it can be seen that film grown on glass substrates showed well defined hexagons with an average size (as calculated from SEM pictures) ~ 1.5 m. The glass-film interface exhibits random growth of particles which can be attributed to the amorphous nature of the glass (figure 6 (iii)). Films deposited at the same condition on crystalline Si substrate show densely packed hexagons with an average diameter varying from 200 nm to 500 nm. Si-film interface (figure 6 (iv)) exhibits oriented growth (with the c-axis tilted by ~10 degrees w.r.t. substrate plane) of densely packed nanorods on the substrate surface.

(i)

(ii)

500 nm

500 nm

(iii)
500 nm

500 nm

(iv)

Fig.6. SEM micrographs: Top view (i) of film deposited on glass and (ii) on Si, both deposited at 3mbar of O2 partial pressure. Crossectional images of (iii) ZnO film-glass interface and (iv) ZnO film-Si interface (nanorods). Circle in (ii) shows hexagonal shape.

PL of ZnO film deposited on glass at 3 mbar showed a broad emission (figure 7), whereas film deposited on Si with the same parameters showed a single strong defect free ultraviolet emission (377 nm). The narrow emission from ZnO nanorods grown by this method on Si is expected to be useful for optoelectronic applications.
24 20 Intensity (a.u.) 16 12 8 4 0 350 400 450 500 550 Wavelength (nm) 600

Si Glass
ex=325nm

Fig.7. PL spectra of ZnO films deposited on Si and glass substrates. ex represents the excitation wavelength.

4.3.3 Formation of ZnO nanobrushes by thermal evaporation of Zn metal source using carbon catalyst
ZnO nanobrushes were synthesized by direct thermal evaporation technique using carbon catalyst. The brushes consist of bristles, with tilted tips (tilt angle being ~ 38o), whose width varies in width from 400 nm at the base to about 10-15 nm at the tip (figure 8(e)). Woong et al. (2004) predicted the structural compatibility of ZnO nanowires with AFM. ZnO can maintain mechanical stability during operation and ZnO nanowires are therefore promising candidates for high aspect ratio probes. This can also compensate the tilt angle of the cantilevers used for high resolution AFM imaging.

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2.5 Intensity (a.u.) 2.0 1.5 1.0 0.5

5 m

4 m
400 450 500 550 Wavelength (nm) 600

4 m

Fig.8 Fig.9 Fig.8. (a) and (b). SEM images of ZnO nanobrushes at different magnifications.
Fig.9. Deconvolution of PL emission obtained on ZnO brushes excited at 325 nm. Inset shows visible fluorescent green emission from the brushes.

The PL spectrum (figure 9) obtained on the sample was deconvoluted to find the energy levels of the intrinsic defects in the film. For ZnO brushes, the band edge emission peaked at about 395 nm and another broad band emission extended from about 420 nm to 520 nm. We attribute the visible fluorescent green emission to the interstitial Zn and oxygen vacancy defects. Inset in figure 9 shows visible fluorescent green emission from the brush. The emission around 2.94 eV and 2.74 eV was attributed to electron transition from the interstitial Zn level to the valence band. The energy interval between the VZn level (doubly charged Zn vacancy) and the top of valence band (2.42 eV) approximately conforms to the cyan emission. The evaluated values of energies corresponding to these defects are ~ 2.94 eV (Zni), 2.74 eV (VZn), 2,53 eV (Zni), 2.44 eV (VZn) and 2.32eV (VO) in agreement with some of the previous reports [Lin et al. (2001) and Oba et al. (2001)].

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5. CONCLUSIONS 1. Electrical resistivity of Ti, V, Fe and Ni doped ZnO is found to decrease as compared to undoped ZnO and this behaviour in case of isovalent doping is attributed to the d-band splitting of the TM ion in the parent ZnO lattice. 2. Microstructures of doped sample exhibit changes compared to that of undoped sample and these changes can be attributed to change in ionic fraction of a compound on doping. Substrate effect and role of oriented rods in obtaining sharp PL spectra was clearly observed. 3. ZnO hexagons were grown on glass substrates and densely packed, oriented ZnO nanorods on Si substrate by PLD. PL spectra of nanorods reflect the high purity and nearly defect free structure of nanorods. 4. ZnO nanobrushes with bristles tilted at the tip were grown by thermal evaporation technique. These nanostructures may have potential use in AFM tilted tip-imaging and green emission applications.

6. REFERENCES 1. Becerra, A. M. and A. E. Castro-Luna (2005) An investigation on the presence of NiAlO4 in a stable Ni on alumina catalyst for dry performing. J. Chil. Chem. Soc. 50 465. 2. Hecht, H. (1968) Modern Aspects of Reflectance Spectroscopy edited by W. Wendlandt (Plenum, New York) 122. 3. Lin, B., Z. Fu, and Y. Jia (2001) Green luminescent center in undoped zinc oxide films deposited on silicon substrates. Appl. Phys. Lett. 79 943. 4. Oba, S., R. Nishitani, S. Isotani, H. Adachi, and I. Tanaka (2001) Energetics of native defects in ZnO. J. Appl. Phys. 90 824.

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5. Sato, K. and H. K. Yoshida (2002) Ab initio Study on the Magnetism in ZnO-, ZnS-, ZnSe and ZnTe-Based Diluted Magnetic Semiconductors. Phys. stat. sol. (b) 229 673 680. 6. Sato, T., H. Suzuki, O. Kido, M. Kurumada, K. Kamitsuji, Y. Kimura, H. Kawasaki, S. Kaneko, Y. Saito and C. Kaito (2005) Production of transition metaldoped ZnO nanoparticles by using RF plasma field. Journal of Crystal Growth 275 e983e987. 7. Woong, L., M. C. Jeong and J. M. Myoung (2004) Fabrication and application potential of ZnO nanowires grown on GaAs(002) substrates by metalorganic chemical vapour deposition. Nanotechnology 15 254. 8. Zhong, J., S. Muthukumar, Y. Chen, Y. Lu, H. M. Ng, W. Jiang and E. L. Garfunkel (2003) Ga-doped ZnO single-crystal nanotips grown on fused silica by metalorganic chemical vapor deposition. Appl. Phys. Lett. 83 340.

7. PROPOSED CONTENTS OF THE THESIS CHAPTER 1: Introduction. CHAPTER 2: Experimental Techniques. CHAPTER 3: Electrical transport and optical characterization of transition metal (TM) ion doped ZnO compounds. CHAPTER 4: Microstructural and optical property changes with doping - Cr and V doped ZnO CHAPTER 5: Preparation and characterization of ZnO nano and/ microstructures prepared by chemical and physical routes. CHAPTER 6: Summary and conclusions.

8. LIST OF PUBLICATIONS BASED ON RESEARCH WORK Publications in Refereed Journals 1. Shubra Singh, N. Rama and M. S. R. Rao (2006) Influence of d-d interband transitions on electrical resistivity in Ni doped polycrystalline ZnO. Appl. Phys. Letts. 88 222111.

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2. Shubra Singh, N. Rama and M. S. R. Rao (2006) Transport properties of transition metal doped ZnO: bulk and thin films. Material Research Society, 0957-K10-43. 3. Shubra Singh, P. Thiyagarajan, K. Mohankant, D. Anitha, S. Thirupathiah, N. Rama, B. Tiwari, M. Kottaisamy and M. S. R. Rao (2007) Topical review Article: Structure, microstructure and physical properties of ZnO based materials in various forms: bulk, thin film and nano. J. Phys. D: Appl. Phys. 40 6312-6327. 4. Shubra Singh, N. Rama, K. Sethupathi and M. S. R. Rao (2008) Correlation between electrical transport, optical, and magnetic properties of transition metal ion doped ZnO. Journal of Applied Physics, 103, 07D108. 5. Shubra Singh, E. Senthil Kumar and M. S. R. Rao (2008) Microstructural, optical and electrical properties of Cr doped ZnO. Scripta Materialia 58 866869. 6. Shubra Singh and M. S. R. Rao (2007) Structure and Physical Properties of Undoped ZnO and Vanadium Doped ZnO Films Deposited by Pulsed Laser Deposition. Journal of Nanoscience and Nanotechnology 8 13. 7. Shubra Singh, S. B. Reddy, M. Kottaisamy and M. S. R. Rao, Formation of ZnO nanobrushes in direct atmosphere using carbon catalyst and Zn metal source. NANO (In press). 8. Shubra Singh, E. Senthil Kumar and M. S. R. Rao, Microstructural study of assorted ZnO nanostructures: nanocombs, nanocones and microspheres (under review).

Conferences [1]. Shubra Singh, N. Rama and M.S.R. Rao, Physical properties of doped ZnO thin films grown by Pulsed Laser Deposition. DAE BARNS 3rd National Symposium on

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Pulsed Laser Deposition of the thin films and nanostructured material, Tirupathi, November, (2005). [2]. Shubra Singh, N. Rama and M.S. R. Rao, Electrical and magnetic properties of Zn1xDyxO.

International conference on Electronic and Photonic Materials, Devices and

Systems, Kolkata, January, 2006. [3]. Shubra Singh and M. S. R. Rao, Structural and Physical properties of ZnO hexagons deposited by PLD. 3rd International conference on advances in thin films and surface coatings, Singapore, December, 2006. [4]. Shubra Singh, N. Rama and M. S. R. Rao, Transport studies of transition metal ion doped ZnO: Bulk and thin films. Materials Research Society Fall meetings, Boston MA, USA. November, 2006. [5]. Shubra Singh and M. S. R. Rao, Structural and electrical properties of Chromium doped ZnO: bulk and thin films. ISRS 2006, IIT Madras, India, December, 2006. [6]. Shubra Singh, N. Rama and M. S. R. Rao, Correlation between electrical transport, optical, and magnetic properties of transition metal ion doped ZnO. 52nd MMM conference, Tampa, Florida, November, 2007. [7]. T.N. Sairam, Shubra Singh, M.S. R. Rao and C.S. Sundar, Observation of LO phonon mode in the IR transmission spectra of ZnO: Ni thin films. DAE Solid State Physics Symposium, University of Mysore, December, 2007. [8]. E. Senthil Kumar, Shubra Singh and M. S. R. Rao, Optical, Electrical transport and Optoelectronic properties of bulk heterostructures and nanostructures of ZnO. Indo-NUS workshops on current trends in physics, IIT Madras, February-March, 2008. [9]. Shubra Singh, E. Senthil Kumar and M.S. R. Rao, Microstructural study of assorted

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ZnO nanostructures: nanocombs, nanocones and microspheres, 2nd International Conference on Advanced Nano Materials, Aveiro, Portugal, June, 2008. [10]. Shubra Singh and M.S. R. Rao, Synthesis of ZnO microstructures from metallic Zn. ISRS 2008, IIT Madras, December, 2008. [11]. T.N. Sairam, Shubra Singh and M.S. R. Rao, Low Temperature Behaviour of LO Phonon Mode in the Infrared Spectra of ZnO: Ni Thin Films. Proceedings of the DAE Solid State Physics Symposium, BARC, Mumbai (2008).

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