Comparative study of GeO2/Ge and SiO2/Si structures on anomalous charging of oxide films upon water adsorption revealed by ambient-pressure X-ray photoelectron spectroscopy

Mori, Daichi; Oka, Hiroshi; Hosoi, Takuji; Kawai, Kentaro; Morita, Mizuho; Crumlin, Ethan J.; Liu, Zhi; Watanabe, Heiji; Arima, Kenta

doi:10.1063/1.4962202

Comparative study of GeO₂/Ge and SiO₂/Si structures on anomalous charging of oxide films upon water adsorption revealed by ambient-pressure X-ray photoelectron spectroscopy

Journal Article · Fri Sep 02 00:00:00 EDT 2016 · Journal of Applied Physics

DOI:https://doi.org/10.1063/1.4962202· OSTI ID:1377479

Mori, Daichi ^[1]; Oka, Hiroshi ^[2]; Hosoi, Takuji ^[2]; Kawai, Kentaro ^[1]; Morita, Mizuho ^[1]; Crumlin, Ethan J. ^[3]; Liu, Zhi ^[3]; Watanabe, Heiji ^[2]; ^[1]

Osaka Univ. (Japan). Graduate School of Engineering. Dept. of Precision Science and Technology
Osaka Univ. (Japan). Graduate School of Engineering. Dept. of Material and Life Science
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source

The energy difference between the oxide and bulk peaks in X-ray photoelectron spectroscopy (XPS) spectra was investigated in this paper for both GeO₂/Ge and SiO₂/Si structures with thickness-controlled water films. This was achieved by obtaining XPS spectra at various values of relative humidity (RH) of up to ~15%. The increase in the energy shift is more significant for thermal GeO₂ on Ge than for thermal SiO₂ on Si above ~10^-4% RH, which is due to the larger amount of water molecules that infiltrate into the GeO₂ film to form hydroxyls. Analyzing the origins of this energy shift, we propose that the positive charging of a partially hydroxylated GeO₂ film, which is unrelated to X-ray irradiation, causes the larger energy shift for GeO₂/Ge than for SiO₂/Si. A possible microscopic mechanism of this intrinsic positive charging is the emission of electrons from adsorbed water species in the suboxide layer of the GeO₂ film to the Ge bulk, leaving immobile cations or positively charged states in the oxide. Finally, this may be related to the reported negative shift of flat band voltages in metal-oxide-semiconductor diodes with an air-exposed GeO₂ layer.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Japan Society for the Promotion of Science (JSPS) (Japan); Mikiya Science and Technology Foundation (Japan); Murata Science Foundation (Japan); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1377479

Alternate ID(s):: OSTI ID: 22598818

Journal Information:: Journal of Applied Physics, Journal Name: Journal of Applied Physics Journal Issue: 9 Vol. 120; ISSN 0021-8979

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

Interaction of water vapors with germanium coated with an oxide film Enikeev, �. Kh.; Loginov, A. Yu.; Golovanova, G. F. Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, Vol. 24, Issue 10 https://doi.org/10.1007/BF00929720	journal	October 1975
Surface oxidation states of germanium Schmeisser, D.; Schnell, R. D.; Bogen, A. Surface Science, Vol. 172, Issue 2 https://doi.org/10.1016/0039-6028(86)90767-3	journal	July 1986
Oxidation of Ge(100) and Ge(111) surfaces: an UPS and XPS study Prabhakaran, K.; Ogino, T. Surface Science, Vol. 325, Issue 3 https://doi.org/10.1016/0039-6028(94)00746-2	journal	March 1995
Structures chimique et electronique de l'interface SiO2-Si Hollinger, G. Applications of Surface Science, Vol. 8, Issue 3 https://doi.org/10.1016/0378-5963(81)90126-4	journal	July 1981
Recommended Auger parameters for 42 elemental solids Powell, C. J. Journal of Electron Spectroscopy and Related Phenomena, Vol. 185, Issue 1-2 https://doi.org/10.1016/j.elspec.2011.12.001	journal	March 2012
Characterization of chemical bonding features at metal/GeO2 Interfaces by X-ray photoelectron spectroscopy Matsui, Masafumi; Murakami, Hideki; Fujioka, Tomohiro Microelectronic Engineering, Vol. 88, Issue 7 https://doi.org/10.1016/j.mee.2011.03.032	journal	July 2011
Ambient pressure photoelectron spectroscopy: A new tool for surface science and nanotechnology Salmeron, M.; Schlogl, R. Surface Science Reports, Vol. 63, Issue 4 https://doi.org/10.1016/j.surfrep.2008.01.001	journal	April 2008
Evolution of the Adsorbed Water Layer Structure on Silicon Oxide at Room Temperature Asay, David B.; Kim, Seong H. The Journal of Physical Chemistry B, Vol. 109, Issue 35 https://doi.org/10.1021/jp053042o	journal	September 2005
The Nature of Water Nucleation Sites on TiO ₂ (110) Surfaces Revealed by Ambient Pressure X-ray Photoelectron Spectroscopy Ketteler, Guido; Yamamoto, Susumu; Bluhm, Hendrik The Journal of Physical Chemistry C, Vol. 111, Issue 23 https://doi.org/10.1021/jp068606i	journal	June 2007
Hydroxyl-Induced Wetting of Metals by Water at Near-Ambient Conditions Yamamoto, Susumu; Andersson, Klas; Bluhm, Hendrik The Journal of Physical Chemistry C, Vol. 111, Issue 22 https://doi.org/10.1021/jp0731654	journal	June 2007
Water Adsorption, Solvation, and Deliquescence of Potassium Bromide Thin Films on SiO ₂ Studied by Ambient-Pressure X-ray Photoelectron Spectroscopy Arima, Kenta; Jiang, Peng; Deng, Xingyi The Journal of Physical Chemistry C, Vol. 114, Issue 35 https://doi.org/10.1021/jp101683z	journal	August 2010
Autocatalytic Surface Hydroxylation of MgO(100) Terrace Sites Observed under Ambient Conditions Newberg, John T.; Starr, David E.; Yamamoto, Susumu The Journal of Physical Chemistry C, Vol. 115, Issue 26 https://doi.org/10.1021/jp200235v	journal	June 2011
Water Growth on GeO ₂ /Ge(100) Stack and Its Effect on the Electronic Properties of GeO ₂ Mura, Atsushi; Hideshima, Iori; Liu, Zhi The Journal of Physical Chemistry C, Vol. 117, Issue 1 https://doi.org/10.1021/jp304331c	journal	December 2012
Adsorption of Water on Cu ₂ O and Al ₂ O ₃ Thin Films Deng, Xingyi; Herranz, Tirma; Weis, Christoph The Journal of Physical Chemistry C, Vol. 112, Issue 26 https://doi.org/10.1021/jp800944r	journal	June 2008
Water Adsorption on α-Fe ₂ O ₃ (0001) at near Ambient Conditions Yamamoto, Susumu; Kendelewicz, Tom; Newberg, John T. The Journal of Physical Chemistry C, Vol. 114, Issue 5 https://doi.org/10.1021/jp909876t	journal	January 2010
Growth and Structure of Water on SiO ₂ Films on Si Investigated by Kelvin Probe Microscopy and in Situ X-ray Spectroscopies Verdaguer, Albert; Weis, Christoph; Oncins, Gerard Langmuir, Vol. 23, Issue 19 https://doi.org/10.1021/la700893w	journal	September 2007
The nature of water on surfaces of laboratory systems and implications for heterogeneous chemistry in the troposphere Sumner, Ann Louise; Menke, Erik J.; Dubowski, Yael Physical Chemistry Chemical Physics, Vol. 6, Issue 3 https://doi.org/10.1039/b308125g	journal	January 2004
Oxide thickness dependence of energy shifts in the Si 2p levels for the SiO2/Si structure, and its elimination by a palladium overlayer Kobayashi, Hikaru; Kubota, Tomohiro; Kawa, Hidefumi Applied Physics Letters, Vol. 73, Issue 7 https://doi.org/10.1063/1.122042	journal	August 1998
A differentially pumped electrostatic lens system for photoemission studies in the millibar range Ogletree, D. Frank; Bluhm, Hendrik; Lebedev, Gennadi Review of Scientific Instruments, Vol. 73, Issue 11 https://doi.org/10.1063/1.1512336	journal	November 2002
Effective electrical passivation of Ge(100) for high-k gate dielectric layers using germanium oxide Delabie, Annelies; Bellenger, Florence; Houssa, Michel Applied Physics Letters, Vol. 91, Issue 8 https://doi.org/10.1063/1.2773759	journal	August 2007
Evidence of low interface trap density in GeO2∕Ge metal-oxide-semiconductor structures fabricated by thermal oxidation Matsubara, Hiroshi; Sasada, Takashi; Takenaka, Mitsuru Applied Physics Letters, Vol. 93, Issue 3 https://doi.org/10.1063/1.2959731	journal	July 2008
Origin of flatband voltage shift and unusual minority carrier generation in thermally grown GeO2/Ge metal-oxide-semiconductor devices Hosoi, Takuji; Kutsuki, Katsuhiro; Okamoto, Gaku Applied Physics Letters, Vol. 94, Issue 20 https://doi.org/10.1063/1.3143627	journal	May 2009
Germanium oxynitride gate dielectrics formed by plasma nitridation of ultrathin thermal oxides on Ge(100) Kutsuki, Katsuhiro; Okamoto, Gaku; Hosoi, Takuji Applied Physics Letters, Vol. 95, Issue 2 https://doi.org/10.1063/1.3171938	journal	July 2009
New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2 Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda Review of Scientific Instruments, Vol. 81, Issue 5 https://doi.org/10.1063/1.3427218	journal	May 2010
Evaluation of GeO desorption behavior in the metal/GeO2/Ge structure and its improvement of the electrical characteristics Oniki, Yusuke; Koumo, Hideo; Iwazaki, Yoshitaka Journal of Applied Physics, Vol. 107, Issue 12 https://doi.org/10.1063/1.3452367	journal	June 2010
Electron spectroscopic analysis of the SiO2/Si system and correlation with metal–oxide–semiconductor device characteristics Iwata, Seiichi; Ishizaka, Akitoshi Journal of Applied Physics, Vol. 79, Issue 9 https://doi.org/10.1063/1.362676	journal	May 1996
Insight into unusual impurity absorbability of GeO ₂ in GeO ₂ /Ge stacks Ogawa, Shingo; Suda, Taichi; Yamamoto, Takashi Applied Physics Letters, Vol. 99, Issue 14 https://doi.org/10.1063/1.3644393	journal	October 2011
The role of extra-atomic relaxation in determining Si 2p binding energy shifts at silicon/silicon oxide interfaces Zhang, K. Z.; Greeley, J. N.; Banaszak Holl, Mark M. Journal of Applied Physics, Vol. 82, Issue 5 https://doi.org/10.1063/1.366037	journal	September 1997
Conduction band offset at GeO ₂ /Ge interface determined by internal photoemission and charge-corrected x-ray photoelectron spectroscopies Zhang, W. F.; Nishimula, T.; Nagashio, K. Applied Physics Letters, Vol. 102, Issue 10 https://doi.org/10.1063/1.4794417	journal	March 2013
Enhancement of thermal stability and water resistance in yttrium-doped GeO ₂ /Ge gate stack Lu, Cimang; Hyun Lee, Choong; Zhang, Wenfeng Applied Physics Letters, Vol. 104, Issue 9 https://doi.org/10.1063/1.4868032	journal	March 2014
Structural and thermodynamic consideration of metal oxide doped GeO ₂ for gate stack formation on germanium Lu, Cimang; Lee, Choong Hyun; Zhang, Wenfeng Journal of Applied Physics, Vol. 116, Issue 17 https://doi.org/10.1063/1.4901205	journal	November 2014
High dielectric constant gate oxides for metal oxide Si transistors Robertson, John Reports on Progress in Physics, Vol. 69, Issue 2 https://doi.org/10.1088/0034-4885/69/2/R02	journal	December 2005
Microscopic structure of the SiO 2 /Si interface Himpsel, F. J.; McFeely, F. R.; Taleb-Ibrahimi, A. Physical Review B, Vol. 38, Issue 9 https://doi.org/10.1103/PhysRevB.38.6084	journal	September 1988
Electron cyclotron resonance plasma and thermal oxidation mechanisms of germanium Wang, Y.; Hu, Y. Z.; Irene, E. A. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 12, Issue 4 https://doi.org/10.1116/1.579313	journal	July 1994
Structure of ultrathin SiO2/Si(111) interfaces studied by photoelectron spectroscopy Keister, J. W.; Rowe, J. E.; Kolodziej, J. J. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 17, Issue 4 https://doi.org/10.1116/1.581805	journal	July 1999
Generation and Controlling the Trap in Absorbent Germanium Oxide Film Oniki, Yusuke; Ueno, Tomo Applied Physics Express, Vol. 4, Issue 8 https://doi.org/10.1143/APEX.4.081101	journal	July 2011
Tunneling Current through Ultrathin Silicon Dioxide Films under Light Exposure Morita, Satoru; Shinozaki, Akihito; Morita, Yuuki Japanese Journal of Applied Physics, Vol. 43, Issue 11B https://doi.org/10.1143/JJAP.43.7857	journal	November 2004
Direct Evidence of GeO Volatilization from GeO ₂ /Ge and Impact of Its Suppression on GeO ₂ /Ge Metal–Insulator–Semiconductor Characteristics Kita, Koji; Suzuki, Sho; Nomura, Hideyuki Japanese Journal of Applied Physics, Vol. 47, Issue 4 https://doi.org/10.1143/JJAP.47.2349	journal	April 2008
Germanium channel MOSFETs: Opportunities and challenges Shang, H.; Frank, M. M.; Gusev, E. P. IBM Journal of Research and Development, Vol. 50, Issue 4.5 https://doi.org/10.1147/rd.504.0377	journal	July 2006
Dramatic Improvement of GeO2/Ge MIS Characteristics by Suppression of GeO Volatilization Kita, Koji; Suzuki, Sho; Nomura, Hideyuki 212th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.2779582	conference	January 2007
Passivation of Ge(100)∕GeO[sub 2]∕high-κ Gate Stacks Using Thermal Oxide Treatments Bellenger, F.; Houssa, M.; Delabie, A. Journal of The Electrochemical Society, Vol. 155, Issue 2 https://doi.org/10.1149/1.2819626	journal	January 2008
Water-Related Hole Traps at Thermally Grown GeO ₂ –Ge Interface Oniki, Yusuke; Ueno, Tomo Japanese Journal of Applied Physics, Vol. 51, Issue 4S https://doi.org/10.7567/JJAP.51.04DA01	journal	April 2012

Cited By (1)

GeO ₂ Encapsulated Ge Nanostructure with Enhanced Lithium-Storage Properties Yan, Shancheng; Song, Haizeng; Lin, Shuren Advanced Functional Materials, Vol. 29, Issue 8 https://doi.org/10.1002/adfm.201807946	journal	January 2019

Similar Records

Comparative study of GeO{sub 2}/Ge and SiO{sub 2}/Si structures on anomalous charging of oxide films upon water adsorption revealed by ambient-pressure X-ray photoelectron spectroscopy

Journal Article · Wed Sep 07 00:00:00 EDT 2016 · Journal of Applied Physics · OSTI ID:22598818

GeO{sub 2}-doped SiO{sub 2} sputtered thin films: Microstructure, stoichiometry, and optical properties

Journal Article · Sun Oct 31 23:00:00 EST 2004 · Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films · OSTI ID:20636763

Nature of the paramagnetic states in SiO/sub 2/-GeO/sub 2/-sol-gel glasses

Technical Report · Tue Dec 31 23:00:00 EST 1985 · OSTI ID:6775482

Related Subjects

36 MATERIALS SCIENCE
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
Adsorption
Elemental semiconductors
Germanium
Water vapor
X-ray photoelectron spectroscopy