BST Deposition Integrated Ferroelectrics 2000, Vol. 30, pp.

183-192

DEPOSITION OF THIN BST FILMS IN A MULTI-WAFER PLANETARY REACTOR

P. Ehrhart1, F. Fitsilis1, S. Regnery1,2, R. Waser1 F. Schienle2, M. Schumacher2, M. Dauelsberg2, P. Strzyzewski2, and H. Juergensen2

1 2

IFF, Forschungszentrum Jlich GmbH, D-52425 Jlich, Germany AIXTRON AG, Kackertstr. 15 - 17, D-52072 Aachen, Germany

We report on the performance of a planetary multi-wafer reactor offering extremely high throughput due to the batch mode processing and a low cost of ownership. This reactor is combined with a liquid delivery system which mixes the liquid precursors from three different sources: 0.35 molar solutions of Ba(thd)2 and Sr(thd)2 and a 0.4 molar solution of Ti(O-iPr)2(thd)2. The composition and microstructure of the films were routinely investigated by X-ray diffraction and X-ray fluorescence analysis. As a direct consequence of the reactor design we obtain high efficiencies for the precursor incorporation in the order of 40%. Furthermore, we obtain a high uniformity of the films over 6 inch wafers. Details of the chemistry and microstructure were investigated by secondary neutral mass spectroscopy and scanning electron microscopy. The electrical film properties are discussed in relation to microstructural properties.

Keywords MOCVD; (Ba,Sr)TiO3; multi-wafer reactor, liquid delivery;

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1. INTRODUCTION (BaxSr1-x)TiO3, (BST), is one of the prime candidates as a high-kdielectric in integrated high-density capacitors for future (multi-GBit) DRAM memory cells[1] and remarkable progress has been achieved in the metal-organic chemical vapor deposition (MOCVD) of thin BST films[2-7]. Most of the experimental reactors used for the development of mass production tools presently are conventional single wafer showerhead designs[5-7] and we report as a comparison on the performance of a planetary multi-wafer reactor offering extremely high throughput due to possible batch mode processing resulting in low cost of ownership. We first give a short description of the reactor followed by some characteristics of its performance within a complex process parameter field. In the second part we report on the first results on the properties of the obtained BST films which were deposited on SiO2/Si and on Pt/SiO2/TiO2/Si wafers with different texture of the Pt metallization film. The composition and microstructure of the films were routinely investigated by X-ray diffraction (XRD) and X-ray fluorescence (XRF) analysis, using different calibration standards prepared by chemical solution deposition. Substrates without Ti adhesion layer were used additionally for the XRF analysis since the penetration depth of the xray beam is too large to distinguish the Ti in the BST from the Ti of the adhesion layer. The chemistry of the interface was investigated by secondary neutral mass spectroscopy (SNMS), and details of the microstructure were investigated by scanning electron microscopy (SEM). The electrical properties were investigated after sputterdeposition and structuring of a Pt top electrode by standard techniques. 2. REACTOR DESIGN An AIXTRON 2600G3 Planetary Reactor was used which can handle five 6-inch wafers simultaneously. As shown in Fig.1 the wafers are placed on a coated graphite susceptor which rotates typically at 8 rpm and carries five smaller plates (satellites) which rotate by gas foil rotation. The gas inlet is in the center of the reactor providing a pure horizontal gas flow direction which makes this reactor a radial flow
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FIGURE 1: The planetary reactor loaded with 5 wafers.

system. A liquid precursor delivery system, ATMI-300B[8], mixes the liquid precursors of three different sources: 0.35 molar solutions of Ba(thd)2 and Sr(thd)2 and a 0.4 molar solution of Ti(O-iPr)2(thd)2. The liquid mixture is delivered by a micro-pump to the vaporizer on top of the reactor. Hot Argon gas at the evaporation temperature of 235C carries the evaporated solution through a quartz nozzle to the substrate. All MOCVD experiments were carried out at reduced pressure (below 3 mbar) in order to increase the gas diffusivity and prevent prereactions. The deposition temperatures varied between 500-700C. The process conditions are summarized in table 1. TABLE 1: Typical deposition conditions for BST films Substrate temperature Reactor pressure O2 flow rate N2O flow rate Liquid source feeding rate Vaporization temperature Film thickness 500 750C 1-3 mbar 50-500 sccm 50-500 sccm 0.08ml/s 225 245C 15-75 nm

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3. REACTOR PERFORMANCE In a first step an appropriate window of process parameters was established for a given liquid precursor solution. In further iterations, the liquid source solution, e.g. the (Ba+Sr)/Tiliquid ratio was altered in order to investigate the film composition control mechanism and hence extrapolate the solution for producing Ba0.7Sr0.3TiO3 thin films. As shown in Fig. 2 we observed a linear dependency between these parameters, which indicates a very stable and non-critical behavior of the reactor and allows a precise optimization of the further parameters of the process window.
Stoichiometry change
2

Film GII/Ti ratio

1,5 1 0,5 0 0 1 2 3 4 5 6

LDS GII/Ti ratio

FIGURE 2: Relationship between the stoichiometry of the source liquid, ((Ba+Sr)/Ti)L, and that of the deposited film, ((Ba+Sr)/Ti)F, for BST thin films grown at various temperatures on SiO2 substrates

The efficiency of the precursor use, defined as the ratio of the molar concentration of the individual precursor elements and the quantity deposited on all 5 wafers, is an important parameter for the costs of ownership and is plotted in fig.3. The observed value of 40% for Ti is extraordinarily high as compared to values reported for conventional showerhead reactors[5] and the same is also true for the values of Ba and Sr which are around 20%. The reasons for this difference are under investigation and there are indications that these values can also be increased.
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50 Efficiency [%] 40 30 20 10 0 600

Precursor efficiency

Sr

Ba

Ti

620

640

660

680

700

720

Temperature [C]

FIGURE 3: Efficiency of the precursor deposition for Ba, Sr, and Ti.

Finally, due to the gas-foil rotation principle we expect from the beginning a good homogeneity of the stoichiometry and film thickness. In order to check the deposition uniformity a 6-inch wafer was divided into 21 one square inch samples after deposition. Each sample was analyzed by XRF. The average thickness was 62.9nm with a standard deviation variation of 0.65% and the distribution, which indicates a depletion in the middle of the wafer is shown in Fig.4. Ba and Sr concentrations remained constant all over the wafer within these uncertainties, which are determined by the precision of the XRF for these elements. For Ti, however, we observed a depletion from the wafer edge to the middle which correlates to the thickness map of Fig.4. This depletion may be caused by the better thermal coupling of the wafer edge to the rotating satellite.

0,61

0,38

1,05

1,20

-0,75 -0,89

-0,36

-0,46

0,45

-0,08

-0,81

0,24

0,04

0,5

-0,72

-0,52

-0,78

0,29

0,72

0,57

0,92

FIGURE 4: Mapping the thickness over a 6 wafer. The deviations from the average value are given in %
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4. PROPERTIES OF THE BST THIN FILMS The growth mechanisms where studied within a wide range of parameters and the growth rates varied between 0.5 to 2.5 nm/min, which resulted in film thickness between 14 to 75 nm. Comparing to single wafer reactors this is equivalent to depositions of 70 to 375 nm under those conditions. Finally, our standard growth temperature was set at 655C for the susceptor temperature and reactor pressure was kept at 2.1 mbar. Considering this low reactor pressure and the gas foil rotation of the satellites it should be considered that the real surface temperature is well known in the order of 50C below this nominal susceptor temperature. Crystallinity For a wide range of parameters a variety of films was grown on different substrates. X-ray diffraction analysis shows for different temperatures very different microstructures ranging from totally amorphous BST films to polycrystalline growth and finally to almost epitaxial growth of the films on (111)-Pt. For temperatures above 600C we, generally, obtained good crystalline growth for Ti-rich films on SiO2/Si substrates. In contrast, the crystallinity on Pt/TiO2/SiO2/Si substrates was very poor for high Ti content but became better as the ((Ba+Sr)/Ti)F ratio was moved towards and beyond 1. Near the ideal stoichiometry ratio of 1 only (100)-oriented BST peaks where detected on a (111)-oriented Pt electrode which is similar to earlier observations[6]. As shown in fig.5a the Bragg peaks were one order of magnitude higher than the peaks obtained for BST of the same stoichiometry on less perfectly textured Pt electrodes. Figure 5b depicts the rocking curves of the (100)-oriented BST film, which has a width of 3.7 degrees and agrees quite well with that of the (111) peak of the Pt bottom electrode. Hence, we observe an almost epitaxial growth of the BST layer on this substrate. As the films became Ba- and Sr-rich they were more randomly oriented and second phase formation, BaCO3, could be observed.

BST deposition in a multi-wafer reactor

XRD of BST on Pt-coated surfaces 1500 BST 100 Pt 111 random-oriented BST (100)-textured BST Pt 200

Rocking curve for BST (200) 10000 Intensity (CPS) 8000 6000 4000 2000 0 15 17 19 21 23 25 27 29 BST 200 - 0 BST 200 - 90

Intensity [CPS]

500

0 20 30 40 2*Theta [] 50 60

BST 101

BST 200

1000

Theta []

(a)

(b)

FIGURE 5: XRD of BST on Pt. a) theta-2-theta scan indicating the preferred (100)-orientation of film 1; film 2 is nearly random oriented and the Pt-(200) reflection is also visible. b) rocking curves of film 1 for = 0 and = 90.

Pt-BST interface The microstructure of the BST-Pt interface was investigated by SEM. Fig. 6a shows as an example the columnar grain growth of the (100)oriented BST on Pt-(111). The grain size is of the order of 30nm for both films. On the weakly textured Pt substrate, Fig.6b, the grains are differently tilted which results in a more rough surface. Hence, the texture and surface roughness of the Pt bottom electrode has a major impact on the film quality.

200 nm

200 nm

(b) (a) FIGURE 6: SEM micrographs of the Pt-BST interface a) Pt-(111) and b) Pt with weak (111)-texture.
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Additionally, SNMS analysis was performed on samples from all types of substrates in order to determine the in-depth homogeneity of the films and the interdiffusion at the interface. Figures 7a,b show a good in-depth deposition homogeneity and indicate that all elements diffuse into the SiO2/Si substrate, Ba much stronger than Ti. There is also indication for inter-diffusion in the Pt-coated Si substrates, especially for Ba. The Ti increase at larger depth is due to the TiO2 adhesion layer used for this film.

BST on Si 1000 Ti 100 Si

10000
Ti

BST on Pt-coated Si
Pt

1000
Intensity
Intensity

Ba Sr

Ba

Sr
100

10

10

Si

1 0 500 1000 1500 2000 2500

1 0 500
Sputter time

Sputter Tim e

1000

1500

(a)

(b)

FIGURE 7: SNMS spectra showing homogeneity along the film thickness of 50nm and indications of inter-diffusion. a) BSTSiO2 interface showing strong Ba diffusion and b) BST-Pt

Electrical characterization For the electrical characterization Pt top electrodes were deposited by magnetron sputtering using shadow masks. An additional postannealing was performed ex-situ. The diameter of the electrodes varied from 0.1 to 1.13 mm. The characterization included the dielectric permittivity, , and its frequency dependence as well as the loss tangent and the dielectric relaxation. In addition, the response to DRAM pulses was investigated using an AIXACCT TF Analyser 2000. Fig.8a shows as an example the frequency dependence of the relative permittivity for two differently textured BST films; these films had a Ba/Sr ratio of 70/30 and were slightly off-stoichiometric, GrII/(GrII+Ti) = 0.48. There is an almost constant dispersion over the whole frequency range from
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1Hz to 1 MHz. We obtain a typical value for 300 for 50nm thick films at a frequency of 1kHz, which corresponds to specific capacitance of 64.1 fF/m. The (100)-textured films generally show 15-20% lower values for , however, the measured dielectric losses are lower, tan 0.005, as compared to values of tan 0.01 for the random oriented films. Fig.8b shows the DRAM pulse response, for a perfectly (100)textured film. Up to a field of 400kV/cm we observe only slight loss of the charge, e.g., at 100kV/cm 4.5% within the first second after pulse load. In addition, we observe always symmetrical behavior after polarization reversal.
Dispersion of relative permittivity 400 350 relative Permittivity 300 250 200 150 100 50 0 1 10 100 1000 Frequency [Hz] 10000 100000 random oriented BST (100)-textured BST

400 300 200

E [kV/cm]

100 0 -100 0 -200 -300 -400

t [s]

0.2

0.4

0.6

0.8

(a)

(b)

FIGURE 8: a) frequency dependence of the relative permittivity for differently textured films and b) relaxation response to DRAM pulses.

5. CONCLUSION
BST thin films were deposited in a planetary multi-wafer reactor for 5 wafers of 6 inch diameter. The expected high efficiency of the precursor incorporation and the high lateral uniformity of the films were demonstrated and therefore highly recommend this reactor type as a production tool for batch processing. BST thin films were grown on different substrates and the influence of the substrate morphology was investigated. By comparing the rocking curves of perfectly (111)-oriented Pt bottom electrodes with those of the (100) oriented BST-films we could demonstrate that BST films can grow epitaxially on Pt. 191

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Acknowledgments The authors greatly acknowledge the help of W. Krumpen in the course of the XRF analyses.
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