Sunday , November 30, 2003

High-resolution photoemission electron spectroscopy study on the oxynitridation of 6H-SiC(0001)- 3x 3R30o surface

J. Labis,+ J. Oh, H. Namatame, M. Taniguchi, M. Hirai*, M. Kusaka*, M. Iwami* Hiroshima Synchrotron Radiation Center, Hiroshima University

2-213 Kagamiyama, Higashi-Hiroshima 739-0046 Japan

*Research Laboratory for Surface Science, Faculty of Science, Okayama University, 3-1-1 Tsushima Naka, 700-8530, Okayama, Japan

Corresponding author:

Tel: +81 824 24 6293 FAX: +81 824 24 6294

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E-mail: jlabis@hiroshima-u.ac.jp, joselitolabis@yahoo.com

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Keywords: 6H-SiC, oxynitridation, oxidation, photoemission spectroscopy Abstract The 3x 3R30o reconstructed surface of 6H-SiC(0001) was exposed to N2O from 10L to ~106L at sample temperatures ranging from 500 to 800oC. The Si 2p emission spectra showed fast oxide formation for the first 10L of N2O exposure and thicker oxide layer were formed at higher sample temperature. The valence band spectra at different exposures did not change much, which may denote saturation of the formed oxide layer. The deconvolution of the Si 2p spectra revealed four oxidation states; Si4+, Si3+, Si2+, and Si+.

The application of SiC to MOS technology for high power and high temperature devices has been hindered by a higher number of interface traps in the SiO2/SiC interface which were attributed to the formations of carbon clusters and silicon sub-oxide bonds [1-3]. The excess carbon released during thermal oxidation remains near the SiO2-SiC interface and the inherent defects in the oxide with energy levels within the SiC bandgap were thought to be the main problems in SiO2-SiC interface [4]. Recent results have indicated that carbon may not be the main reason for the interface defects on SiO2/SiC samples [5]. To solve these problems of high density of interface traps, the use of crystals faces such (1120) and (0338) instead of the usual (0001)

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1. Introduction

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have been shown to decrease these traps and improved the channel mobilities of SiC- MOSFETs [6-7]. Another is the use of reconstructed surfaces of SiC such as 3x3 and 3x 3R30o as the starting surface for oxidation. Amy, et al. [8], have shown that gentle initial oxidation on 3x3 surface at low temperature and low oxygen exposures allow high-quality SiO2/SiC interfaces. The surface/interface related carbons were observed to decrease dramatically although not eliminated in oxidation of 3x 3R30o surface [9]. Recently, oxidation using NO and N2O has been shown to reduce significantly the interface trap density and improves the channel mobility of SiC-MOSFETs [1,4,5,10,11], although the interface trap density is still comparatively higher to warrant a practical application.

and study the resulting surface using high-resolution photoemission spectroscopy (HR-PES). This is to provide more insights to the nature of oxynitridation of this reconstructed surface. No photoemission studies yet have been conducted on this surface using N2O as the oxidizing gas. The

formation. N2O is not hazardous to human and is preferred by industry since it does not pose a threat to the environment.

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3x 3R30o surfaces are relatively easy to prepare and do not require Si flux for their

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Combining these improvements we have tried to expose the 3x 3R30o surface using N2O

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2. Experimental method 6H-SiC(0001)Si face (Cree Research) sample was used. The sample was bath ultrasonically in ethanol, chemically treated with HNO3, and etched with HF(10%). A sacrificial oxide layer was grown on the surface using NH4OH+H2O2 +H2O. The sacrificial oxide layer was later removed by flashing the sample up to ~1100oC for a few seconds under ultra-high- vacuum (UHV) in the order of ~10-9 Torr. An oxide layer was made by exposing the fresh surface to ~106L (1L = 1x10-6Torr-s) of an ultra high-purity O2 gas and subsequently degassed and flashed at 800-1000oC to generate the 3x 3R30o surface. The surface reconstructions were monitored by low energy electron diffractometry (LEED) and PES. The oxide layers were grown on

ohmically-heated sample were varied from 500 to 800oC. After the oxynitridation process, the pressure of the N2O gas was reduced prior to reducing the sample temperature to ensure that no absorption of remaining gases into the surface. To prevent carbon contamination due to emissions from hot filament of the pressure gauges, a cold cathode gauge was used in monitoring the pressure.

valence band spectra of the oxynitrided 3x 3R30o surface. The photons were calibrated against 4f and Fermi edge of Au. This high-resolution photoemission spectroscopy (HR-PES) study was

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Photons with energies ranging from 120 to 380 eV were used to derive the Si 2p and

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3x 3R30o surfaces at N2O exposures from 10 to ~106L. The temperatures of the

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conducted in beamline BL-7 at Hiroshima Synchrotron Radiation Center (HiSOR), Hiroshima, Japan [12]. The resolution is estimated to be ~30 meV for 150 eV photon energy.

3. Results and discussion

The 3x 3R30o surface was exposed to 106L of N2O to grow an oxide layer. Similarly, for comparison, an oxide layer was grown using 106L of O2 and exposed to 106L of N2. Fig 1

shows the Si 2p emission spectra of 6H-SiC(0001)- 3x 3R30o (solid line), after 106L exposures to N2O (dashed line), and O2(+N2) (x-line) at sample temperature of 700oC. The inset shows a sharp LEED pattern of the 6H-SiC(0001)- 3x 3R30o surface. The Si 2p spectra were induced by

relative binding energy (as shown with broken line). The spectra were taken at a take-off-angle (TOA) of 30o with respect to the plane of the sample surface. As shown in Fig. 1, the main oxide (SiO2) (shown in broken line at ~46.6eV) grew at ~ 2.0 eV relative to the bulk SiC for both exposures. Not much effect can be observed when the oxide layer was exposed to N2 at 700oC. The oxide layer grown using O2 was observed to be thicker (estimated using the relative ratio algorithm [13] to be ~27.8 than the oxide grown in N2O(~12.2. Fig. 2 shows the Si 2p emission spectra of 6H-SiC(0001)- 3x 3R30o surface (solid line)

and after exposures to N2O at 10L (bold dashed line), 102L(hollow diamond), 103L(x-line), and

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150 eV-photons. The peaks were normalized to the unexposed SiC peak and positioned at zero

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106L(hollow circle) at sample temperature of 500oC. The oxide layer were observed to grow faster after 10L exposure although the FWHM of ~1.3 eV did not vary much even after103L exposure. This shows that the oxidation in N2O progressed faster during the first 10L exposure and seems to saturate at higher exposure. At 106 L exposure, the FWHM(=~2 eV) was observed

to increase. Moreover, the change in this peak was from the topmost down to the base line, which could denote formation of sub-oxides aside from SiO2. It will be shown in Fig. 5 that sub-oxides were formed through deconvolution of the Si 2p spectrum.

Fig. 3 shows the valence band spectra of 6H-SiC(0001)- 3 x 3R30o after N2O exposure to 10, 102, 103, and 106L at 500oC taken at TOA=30o. Using the same sample cleaning process,

spectra even after high thermal annealing of the exposed surface resulting back to the 3x 3R30o structure. It was shown that the main peak at ~6 eV became sharp when the surface was exposed to N2O even at 10L. The same valence band spectral features were observed even after large exposures. This shows that the same surfaces could have been produced and that the formation of oxide seems to saturate after 10L exposure as observed in the Si 2p spectra in Fig. 2. We would expect then that the valence band structure would be different at different exposures due to the accumulation of C and/or other silicon oxycarbon bonds as the oxidation progresses. This may imply that the interstitials carbons, as well as carbon from already formed clusters atoms, have

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different samples of 3x 3R30o surfaces at 0L were observed to yield the same valence band

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been take out from the interface with the formation of highly diffusing CO molecules and/or passivated by N forming Si N and C-N bonds [11]. This could have resulted to the same valence band spectra up to 106L exposure. Fig. 4 shows the Si 2p emission spectra of 3x 3R30o exposed to 106L of N2O at

different sample temperatures. The TOA was also varied from 90o to 30o to vary the surface sensitivity of the generated spectra. At lower TOA, the spectra were expected more surface sensitive. It was shown that a thicker oxide layer was formed at higher thermal annealing. This is due to the faster dissociation of Si and C atoms and higher reactivity for the formation of the oxide layer. The shoulder peak SiO2 (Si4+) (denoted by broken line at ~46.6 eV) has been clearly

been noted, which could be attributed to the formation of sub-oxide species. The sub-oxides could be located near the interface since changes have been noted even at TOA=90o(bulk)(see Fig. 4(a)). However due to the presence of C and N atoms within the oxide layer, the sub-oxides could have existed throughout the formed oxide layer.

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reported four oxidation states namely; Si4+, Si3+, Si2+, and Si1+ although Virojanadara, et al. [5, 8], only reported two states namely; Si4+and Si2+ or Si1+ for oxidation using O2 gas and 3 oxidation states for oxidation in NO gas. Although their studies involved oxidation with O2, it is interesting to know whether all oxidation states were formed also when 3x 3R30o surface is exposed to

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observed to form and increased near the surface. Also increases between 46.6 to ~48.6 eV have

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Amy, et al. [8], and Hoshino, et al. [13] have

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N2O. Fig. 5 shows the Si 2p emission spectrum of the surface annealed at 800oC and exposed to N2O at 106L. The spectrum was taken at TOA=30o. The inset in Fig. 5 shows the spectrum of SiC and the result from curve fit using two peaks with a spin orbit splitting of 0.61 eV and a branching ratio of 0.50. Assuming the parameters obtained by Hoshino, et al. [14], such as oxide peak positions and Gaussian widths, as the initial starting parameters and slightly varying these parameters, the spectrum can only be deconvoluted when one assumes four oxidation states. The result from curve fitting and the components used were also shown in Fig. 5, where the Si0 (bulk) comprises of two peaks as shown in inset. The spectrum would not be generated when only two

Si1+ in the formed oxide layer, as reported also by Amy, et al.[8] and Hoshino, et al. [13]. The existence of the 4 oxide states could signify a formation of a perfect oxide. Whether the formation of 4 oxidation states using N2O directly affects the interface trap density remains to be understood. And further studies on N1s and O1s have to be undertaken to fully elucidate this issue.

4. Summary and conclusion

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This study involves the use of high-resolution photoemission spectroscopy (HR-PES) to

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oxide states are considered. This may denote four-oxidation states namely; Si4+, Si3+, Si2+, and

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examine the 3x 3R30o reconstructed surface of 6H-SiC(0001) after exposure to N2O from 10 to ~106L at sample temperatures ranging from 500 to 800oC. The following conclusions can be derived from this study: (1) The formation of oxides saturates after 10L exposure to N2O.

(2) The valence band spectra after different exposures did not change much. This may be attributed to the reduction and/or passivation of C and C-related bonds near the interface. (3) The deconvoluted Si 2p spectra revealed four oxidation states; Si4+, Si3+, Si2+, and Si+. Further Si 2p, C 1s, N 1s, and O 1s studies on the initial growth of oxide grown using N2O at very low exposures will be undertaken.

Acknowledgement

This study was performed under the Cooperative Research Program of HiSOR, Hiroshima Synchrotron Radiation Center, Hiroshima University. (Accept #03-A-32)

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References [1] K. McDonald, L.C. Feldman, R.A. Weller, G.Y. Chung, C.C. Tin, and J.R. Williams, J. Appl. Phys., 93(2003) 2257. [2] V.V. Afanasev, A Stesmans, C. J. Harris, Appl. Phys. Lett., 68 (1999) 2141. [3] B. Hornets, H.-J. Michel, J. Halbritter, J. Mater. Res. 9(1994) 3088. [4] S. Dimitrijev, P. Jamet, Microelectronics Reliability, 43(2003) 225. [5] C. Virojanadara, and L.I. Johansson, Surf. Scie., 530(2003) 17.

[6] T. Hirao, H. Yano. T. Kimoto, H. Matsunami, H. Shiomi, Mater. Sci. For. 389-393(2002) 1065 [7] J. Sensaki, et al., IEEE Electron. Dev. Lett., 23(2002) 13.

[9] C. Virojanadara, L.I. Johansson, Surf. Sci. 505(2002) 358. [10] V.V. Afanasev, A. Stesmans, F. Ciobanu, G. Pensi, K.Y. Cheong, S. D. Dimitrijev, Appl. Phys. Lett., 82(2003) 568.

[11] P. Jamet, S. Dimitrijev, P. Tanner, J. Appl. Phys. 90(2001) 5058. [12] M. Taniguchi, H. Namatame, J. Electron. Spectros. Rel. Phenom., 124(2002)107. [13] C. Onneby, C.G. Pantano, J. Vac. Sci. Technol. A, 15(1997) 1597l. [14] Y. Hoshino, T. Nishimura, T. Yoneda, K. Ogawa, H. Namba, Y. Kido, Surf. Sci. 505(2002) 234.

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[8] F. Amy, P. Soukiannsian, Y. K. Hwu, and C. Brylinski, Phys. Rev. B 65 (2002) 165323.

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Figure captions: Figure 1. Si 2p emission spectra of 6H-SiC(0001)- 3x 3R30o (solid line) and after 106L exposures to N2O (dashed line) and O2(+N2) (x-line) at sample temperature of 700oC. The inset shows a sharp LEED pattern of the 6H-SiC(0001)- 3x 3R30o surface.

Figure 2. Si2p emission spectra of 6H-SiC(0001)- 3x 3R30o surface (solid line) and after exposures to N2O at 10L (bold dashed line), 102L(hollow diamond), 103L(x-line), and 106L(hollow circle) at sample temperature of 500oC. The spectra were induced by 150 eV-photons. The take-off-angle (TOA) is 30o with respect to the plane of the sample surface.

Figure 3. Valence band spectra of 6H-SiC(0001)- 3x 3R30o after N2O exposure to 10, 102, 103, and 106L at 500oC taken at TOA=30o.(1L=10-6Torr-s)

Figure 4. Si 2p emission spectra of 3x 3R30o exposed to ~106L of N2O at different sample temperatures. The TOA was also varied from 90o to 30o to vary the surface sensitivity of the generated spectra. At lower TOA, the spectra were expected to be more surface sensitive.

Figure 5. Si 2p emission spectrum of the surface annealed at 800oC and exposed to N2O at 106L.

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The spectrum was taken at TOA=30o. The results of curve fitting and four oxidation states are also shown. The inset shows the spectrum of bulk SiC and the result from curve fit when using a spin orbit splitting of 0.61 eV and a branching ratio of 0.50.

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Si 2p
Ep=150 eV TOA=30o

Intensity (arb. units)

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LEED pattern 3x 3R30o ~1000oC. after

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showing annealing the to

SiC N2O, 700oC O2, 700oC and o N2, 500 C

Kinetic Energy (eV)

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Si 2p Ep=150 eV
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SiC 106L 103L 102L 101L

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Valence Band Ep=150 eV o TOA=30

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Si 2p
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SiC 500oC o 700 C 800oC

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Figure 4.

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