Conditions of Formation of α- and β-Modifications of Ge3N4 and Preparation of Germanium Oxynitride Dielectric Films

Authors

  • Zurab V. Wardosanidze Institute of Cybernetics of Georgian Technical University, Tbilisi, Georgia
  • Irakli Nakhutsrishvili Institute of Cybernetics of Georgian Technical University, Tbilisi, Georgia https://orcid.org/0000-0002-7961-3437
  • Revaz Kokhreidze Institute of Cybernetics of Georgian Technical University, Tbilisi, Georgia

DOI:

https://doi.org/10.6000/2369-3355.2024.11.01

Keywords:

Germanium nitride, crystalline modifications, oxynitride films

Abstract

The binary compound of germanium with nitrogen (Ge3N4) is used in various fields of science and technology. Among the experimentally discovered and theoretically predicted crystal modifications of Ge3N4 at ordinary pressures and temperatures, only the α- and β-phases of the nitride are stable. There are conflicting data in the literature on the conditions for the formation of these phases. The main methods for obtaining Ge3N4 are the nitridation of elemental germanium and its dioxide with ammonia. The present work studied the influence of the degree of humidity of ammonia on the possibility of the formation of pure α- and β-phases and their mixtures. It is shown that it is possible to obtain nitride with practically any ratio of these phases by varying degrees of humidity and the temperature of the process. During the process, the formation of germanium nitride is accompanied by its simultaneous evaporation. Oxidation with water vapors also produces volatile monoxide. Simultaneous evaporation of germanium nitride and oxide results in the deposition of a film of germanium oxynitride in the cold zone of the reactor. This film is a germanium oxynitride used in microelectronics as a dielectric layer in Metal-Insulator-Semiconductor systems.

References

Lin Y, Zhang Sh. Reactive DC magnetron sputtering induced the formation of amorphous CuN films embedded nanocrystalline WC phase. Journal of Coating Science and Technology 2016; 3: 23-28. https://doi.org/10.6000/2369-3355.2016.03.01.3 DOI: https://doi.org/10.6000/2369-3355.2016.03.01.3

Hsu Ch-H, Liu H-T, Huang W-Ch, Lin M-R. Effect of post-heated TiN coating on pitting corrosion of austenitic stainless steel. Journal of Coating Science and Technology 2015; 2: 93-99. https://doi.org/10.6000/2369-3355.2015.02.03.4 DOI: https://doi.org/10.6000/2369-3355.2015.02.03.4

AK, Savin SS, Poklonskaya ON, Trofimov NS. Growth of Si-doped polycrystalline diamond films on AlN substrates by microwave plasma chemical vapor deposition. Journal of Coating Science and Technology 2015; 2: 38-45. https://doi.org/10.6000/2369-3355.2015.02.02.1 DOI: https://doi.org/10.6000/2369-3355.2015.02.02.1

Mallem K, Jagadeesh Chandra, SV, Ju M, Dutta S, Ramana CHVV, Hussain Sh. Q, Park J, Kim Y, Cho Y-H, Cho E-Ch, Yi J. Influence of ultra-thin Ge3N4 passivation layer on structural, interfacial, and electrical properties of HfO2/Ge Metal-Oxide–Semiconductor devices. Nanosciience Nanotechnology 2020; 20: 1039-1045. https://doi.org/10.1166/jnn.2020.16934 DOI: https://doi.org/10.1166/jnn.2020.16934

Ma Y, Wang M, Zhou X. First-principles investigation of β-Ge3N4 loaded with RuO2 cocatalyst for photocatalytic overall water splitting. Energy Chemistry 2020; 44: 24-32. https://doi.org/10.1016/j.jechem.2019.09.013 DOI: https://doi.org/10.1016/j.jechem.2019.09.013

Huang Z, Su R, Yuan H, Zhang J, Chen F, Shen Q, Zhang L. Synthesis and photoluminescence of ultra-pure α-Ge3N4 nanowires. Ceramics International 2018; 4: 10858-10862. https://doi.org/10.1016/j.ceramint.2018.03.137 DOI: https://doi.org/10.1016/j.ceramint.2018.03.137

Kim Sh, Hwang G, Jung J-W, Cho S-H, Cheong JY, Shin S, Park S, Kim I-D. Fast, scalable synthesis of micronized Ge3N4 @C with a high tap density for excellent lithium storage. Advanced Functional Materials 2017; 7: 1605975. https://doi.org/10.1002/adfm.201605975 DOI: https://doi.org/10.1002/adfm.201605975

Maggoini G, Carturan S, Fiorese L, Pinto N, Caproli F, Napoli DR, Giarola M, Mariotto G. Germanium nitride and oxynitride films for surface passivation of Ge radiation detectors. Applied Surface Science 2017; 393: 119-126. https://doi.org/10.1016/j.apsusc.2016.10.006 DOI: https://doi.org/10.1016/j.apsusc.2016.10.006

Yayak YO, Sozen Y, Tan F, Gungen D, Gao Q, Kang J, Yagmurcukardes M, Sahin H. First-principles investigation of structural, Raman and electronic characteristics of single layer Ge3N4. Applied Surface Science 2022; 572: 15136. https://doi.org/10.1016/j.apsusc.2021.151361 DOI: https://doi.org/10.1016/j.apsusc.2021.151361

Soignard E, McMillan PF, Hejny C, Leinenweber K. Pressure-induced transformations in α- and β-Ge3N4: In situ studies by synchrotron X-ray diffraction. Solid State Chemistry 2004; 177: 299-311. https://doi.org/10.1016/j.jssc.2003.08.021 DOI: https://doi.org/10.1016/j.jssc.2003.08.021

LuoY, Cang Y, Chen D. Determination of the finite-temperature anisotropic elastic and thermal properties of Ge3N4. Computat Condens Matter 2014; 1: 1-7. https://doi.org/10.1016/j.cocom.2014.08.001 DOI: https://doi.org/10.1016/j.cocom.2014.08.001

Feldbach F. et al. Electronic band transitions in γ-Ge3N4. Electronic Mater Lett 2021; 17: 315-323. https://doi.org/10.1007/s13391-021-00291-y DOI: https://doi.org/10.1007/s13391-021-00291-y

Cang Y, Yao X, Chen D, Yang F, Yang H. First-principles study on the electronic, elastic, and thermodynamic properties of three novel germanium nitrides. Semiconductors 2016; 37(7): 072002. https://doi.org/10.1088/1674-4926/37/7/072002 DOI: https://doi.org/10.1088/1674-4926/37/7/072002

Cang Y, Chen D, Yang F, Yang H. Theoretical studies of tetragonal, monoclinic, and orthorhombic distortions of germanium nitride polymorphs. Chem Chinese Universities 2016; 37(4): 674-681.

Paszkowicz W, et al. High-pressure study of α and β polymorphs of germanium nitride. Synchrotr Rad Natural Sci 2007; 6(1/2): 28-29.

Samsonov GV, Kulyk OP, Polyshchuk VS. 1978. Obtain and methods of analysis of nitrides. Kiev, Naukova Dumka 320.

Remy JC, Pauleau Y. Conditions of formation of alpha and beta phases of germanic nitride. Inorg Chem 1976; 15(9): 2308-2310. https://doi.org/10.1021/ic50163a068 DOI: https://doi.org/10.1021/ic50163a068

Nakhutsrishvili I. Study of growth and sublimation of germanium nitride using the concept of Tedmon's kinetic model. Oriental J Chem 2020; 36(5): 850-854. https://doi.org/10.13005/ojc/360508 DOI: https://doi.org/10.13005/ojc/360508

Billy M, Labbe JC. Sur la thermolyse du nitrure de germanium. Compt Rend Acad Sci Paris ser C 1971; 813-816.

Bayraktaroglu B, Johnson RL, Langer DW, Mier MG. Germanium (oxy) nitride-based surface passivation technique as applied to GaAs &InP. Phys. MOS Insulators, Nort. Carolina, USA 1980; 301. https://doi.org/10.1016/B978-0-08-025969-7.50043-9 DOI: https://doi.org/10.1016/B978-0-08-025969-7.50043-9

Bagratishvili GD, Dzhanelidze RB, Kurdiani NI, Saksaganskii OV. MIS structure GaAs-Ge3N4-Al. Phys Stat Sol (a) 1976; 36: 73-79. https://doi.org/10.1002/pssa.2210360107 DOI: https://doi.org/10.1002/pssa.2210360107

Pinto N, et al. Thermally induced irreversibility in the conductivity of germanium nitride and oxynitride films. Materials Sci in Semiconductor Process, 2018; 74: 57-63. https://doi.org/10.1016/j.mssp.2017.10.006 DOI: https://doi.org/10.1016/j.mssp.2017.10.006

Sze SM, Li Y, Ng KK. Physics of Semiconductor Devices. Wiley & S., N.-Y., USA 2021; 944.

Audrieth LF, Mohr PH. The chemistry of hydrazine. Chem Eng 2010; 26(51): 3746-3749. https://doi.org/10.1021/cen-v026n051.p3746 DOI: https://doi.org/10.1021/cen-v026n051.p3746

Sato J, Saito N, Yasmada Y, Maeda K, Takata T, et al. RuO2 –loaded β-Ge3N4 as a non-oxide photocatalyst for overall water splitting. J Am Chem Soc 2005; 127(12): 4150-4151. https://doi.org/10.1021/ja042973v DOI: https://doi.org/10.1021/ja042973v

Lee Y, Watanabe T, Takata T, Hara M, Yoshimura M, Domen K. Effect of high-pressure ammonia treatment on the activity of Ge3N4 photocatalyst for overall water splitting. J Phys Chem B 2006; 110(35): 17563-17569. https://doi.org/10.1021/jp063068v DOI: https://doi.org/10.1021/jp063068v

Maeda K, Domen K. New non-oxide photocatalysts designed for overall water splitting under visible light. J Phys Chem C 2007; 111: 7851-7861. https://doi.org/10.1021/jp070911w DOI: https://doi.org/10.1021/jp070911w

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Published

2024-09-04

How to Cite

Wardosanidze, Z. V. ., Nakhutsrishvili, I. ., & Kokhreidze, R. . (2024). Conditions of Formation of α- and β-Modifications of Ge3N4 and Preparation of Germanium Oxynitride Dielectric Films. Journal of Coating Science and Technology, 11, 1–5. https://doi.org/10.6000/2369-3355.2024.11.01

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