New design concept for stable α-silicon nitride based on the initial oxidation evolution at the atomic and molecular levels

doi:10.1016/j.jmst.2022.01.016

Abstract

Abstract:

As the dominated composition of Si₃N₄ ceramics, α-silicon nitride (α-Si₃N₄) can satisfy the strength and fracture toughness demand in the applications. However, α-Si₃N₄ is oxygen-sensitive at high temperatures, which limits its high-temperature performance. To improve the oxidation resistance of α-Si₃N₄ ceramics, it is necessary to shed light on the oxidation mechanism. Herein, the initial oxidation of α-Si₃N₄ was systematically studied at the atomic and molecular levels. The density functional theory (DFT) calculation denotes that the (001) surface of α-Si₃N₄ has the best stability at both room temperature and high temperature. Besides, the oxidation process of the α-Si₃N₄ (001) surface consists of O adsorption and N desorption, and the consequent formation of nitrogen-vacancy (V_N) is the key step for further oxidation. Moreover, the molecular dynamics (MD) simulation indicates that the oxidation rate of α-Si₃N₄ (100) surface is slower than that of α-Si₃N₄ (001) surface due to the lower N concentration at the outermost layer. Therefore, the oxidation resistance of α-Si₃N₄ can be improved by regulating the (100) surface as the dominant exposure surface. In addition, reducing the concentration of N on the final exposed surface of α-Si₃N₄ by mean of constructing the homojunction of the Si-terminal (100) surface and other N-containing surfaces (such as (001) surface) should be also a feasible approach.

Key words: α-Si₃N₄, Surface oxidation, Nitrogen vacancy, DFT, MD

Chunyu Guo, Enhui Wang, Zhi Fang, Yapeng Zheng, Tao Yang, Zhijun He, Xinmei Hou. New design concept for stable α-silicon nitride based on the initial oxidation evolution at the atomic and molecular levels[J]. J. Mater. Sci. Technol., 2022, 122: 156-164.

Figures/Tables 9

Fig. 1. Configuration of α-Si3N4 (001) surface and the possible adsorption sites. (a) α-Si3N4 (001) surface model. (b) Top view of α-Si3N4 (001) surface and the possible adsorption sites.

Fig. 2. Configurations of single O adsorbed at different sites of α-Si3N4 (001) surface and PDOS before and after O adsorption. (a) Optimized structures of single O adsorbed at NI, NⅡ, SiI, bridge-I, and bridge-Ⅱ sites. (b) PDOS of α-Si3N4 (001) pristine surface. (c) PDOS of α-Si3N4 (001) surface with single O adsorbed at the bridge-Ⅰ site. (d) PDOS of α-Si3N4 (001) surface with single O adsorbed at the bridge-Ⅱ site.

Fig. 3. $\text{ }\!\!\Delta\!\!\text{ }G_{n}^{\text{O}}$ as a function of ΔμO. The lower side of X-axis is the corresponding oxygen partial pressure value at 300 K, 800 K, 1300 K, and 1800 K, respectively.

Fig. 4. Optimized structures of NO2, NO, and N2 emission at different oxygen coverages and the corresponding formation energies. (a) Configuration of optimized structures (VN are labeled by the blue dotted circle). (b) Gas formation energies.

Fig. 5. PDOS of α-Si3N4 (001) surface with N2 emission at 0 ML and 1/3 ML O coverage (Fermi energy is set to zero). (a) 0 ML O coverage; (b) 1/3 ML O coverage.

Fig. 6. Oxidation process of α-Si3N4 (001) surface. (a) Initial and final configurations of α-Si3N4 (001) surface oxidation. N in different chemical environments is represented by different colors. (b) Optimized structures of each step during oxidation. The O adsorption is marked with “+O”, and the N desorption is marked with “-N”. (O adsorption sites are labeled by dashed red circles and VN is labeled by the dashed blue circles.)

Fig. 7. Interfacial reaction models of α-Si3N4 with different surfaces. (a) (001) surface in contact with O2 and (b) (100) surface in contact with O2.

Fig. 8. Structure evolution of α-Si3N4 oxidation at 1673 K. Each frame is 250 ps apart. (a) (001) surface in contact with O2; (b) (100) surface in contact with O2. (c) Partially enlarged view of the interface between Si3N4 and O2 at a certain time.

Fig. 9. Evolution of Na for Si-O, N-N, and ξ for Si-N during the oxidation of different α-Si3N4 surface at 1673 K. The red dotted line represents the (001) surface while the blue dotted line represents the (100) surface.

References 57

[1]	X.F. Lu, X. Gao, X. Guo, P.Q. La, Q.Z. Dong, X.Q. Zhang, J. Phys. Chem. Lett. 7 (2016) 3766-3769. DOI URL
[2]	C. Wang, M. Chen, H.J. Wang, X.Y. Fan, H.Y. Xia, J. Eur. Ceram. Soc. 36 (2016) 689-695. DOI URL
[3]	W. Chen, H.X. Shi, H. Xin, N.R. He, W.L. Yang, H.Z. Gao, Ceram. Int. 44 (2018) 16799-16808. DOI URL
[4]	X.M. Li, L.T. Zhang, X.W. Yin, J. Mater. Sci. Technol. 28 (2012) 1151-1156. DOI URL
[5]	C.K. Ande, H.C. Knoops, K. de Peuter, M. van Drunen, S.D. Elliott, W.M. Kessels, J. Phys. Chem. Lett. 6 (2015) 3610-3614. DOI URL
[6]	N. Nishiyama, K. Fujii, E. Kulik, M. Shiraiwa, N.A. Gaida, Y. Higo, Y. Tange, A. Holzheid, M. Yashima, F. Wakai, J. Eur. Ceram. Soc. 39 (2019) 3627-3633. DOI URL
[7]	W. Zhou, L. Long, Y. Li, J. Mater. Sci. Technol. 35 (2019) 2809-2813. DOI URL
[8]	G.H. Hou, B.L. Cheng, F. Ding, M.S. Yao, P. Hu, F.L. Yuan, ACS Appl. Mater. Inter- faces 7 (2015) 2873-2881. DOI URL
[9]	L.B. Sun, C.F. Liu, S.S. Guo, J. Fang, D.B. Wang, J. Zhang, Appl. Surf. Sci. 517 (2020) 146178.
[10]	C.X. Zhang, Y.P. Zeng, D.X. Yao, J.W. Yin, K.H. Zuo, Y.F. Xia, H.Q. Liang, J. Mater. Sci. Technol. 35 (2019) 1345-1353. DOI URL
[11]	H. Huang, L. Yin, L.B. Zhou, J. Mater. Process. Technol. 141 (2003) 329-336. DOI URL
[12]	J.E. Sheehan, J. Am. Ceram. Soc. 65 (1982) c111-c113.
[13]	T. Otani, M. Hirata, Thin Solid Films 442 (2003) 44-47.
[14]	S. Ogata, N. Hirosaki, C. Kocer, Y. Shibutani, Acta Mater. 52 (2004) 233-238. DOI URL
[15]	S.P. Taguchi, S. Ribeiro, J. Mater, Process. Technol. 147 (2004) 336-342. DOI URL
[16]	X.M. Hou, E.H. Wang, B. Li, J.H. Chen, K.C. Chou, Ceram. Int. 43 (2017) 4344-4352. DOI URL
[17]	E.H. Wang, B. Li, Z.F. Yuan, J.H. Chen, K.C. Chou, X.M. Hou, J. Alloy Compd. 725 (2017) 840-847. DOI URL
[18]	C. Kawai, A. Yamakawa, J. Am. Ceram. Soc. 80 (2005) 2705-2708. DOI URL
[19]	B. Li, Y.Y. Feng, G.Q. Li, H.Y. Chen, J.H. Chen, X.M. Hou, Ceram. Int. 45 (2019) 6335-6339. DOI URL
[20]	X.L. Zheng, P. Wu, L. Wang, Ind. Eng. Chem. Res. 58 (2019) 23005-23013. DOI URL
[21]	F.F. Lange, J. Am. Ceram. Soc. 56 (1973) 518-522. DOI URL
[22]	Y. Ukyo, A. Suda, H. Masaki, J. Ceram. Soc. Jpn. 105 (1997) 85-87. DOI URL
[23]	H. Klemm, J. Am. Ceram. Soc. 93 (2010) 1501-1522. DOI URL
[24]	W.C. Tripp, H.C. Graham, J. Am. Ceram. Soc. 59 (1976) 399-403. DOI URL
[25]	X.M. Hou, K.C. Chou, X.J. Hu, H.L. Zhao, J. Alloy Compd. 459 (2008) 123-129. DOI URL
[26]	E.H. Wang, J.H. Chen, X.J. Hu, K.C. Chou, X.M. Hou, J. Am. Ceram. Soc. 99 (2016) 2699-2705. DOI URL
[27]	R. Flammini, A. Bellucci, F. Wiame, R. Belkhou, M. Carbone, D.M. Trucchi, S. Colonna, F. Ronci, M. Hajlaoui, M.G. Silly, F. Sirotti, Appl. Surf. Sci. 355 (2015) 93-97. DOI URL
[28]	S.C. Singhal, J. Mater. Sci. 11 (1976) 500-509. DOI URL
[29]	D.A. Newsome, D. Sengupta, H. Foroutan, M.F. Russo, A.C.T. van Duin, J. Phys. Chem. C 116 (2012) 16111-16121.
[30]	W. Walkosz, J.C. Idrobo, R.F. Klie, S. Öğüt, Phys. Rev. B 78 (2008) 165322.
[31]	J.P. Cai, X.M. Hou, Z. Fang, E.H. Wang, J. Feng, J.H. Chen, T.X. Liang, G.P. Bei, J. Am. Ceram. Soc. 103 (2019) 2808-2816. DOI URL
[32]	M.C. Payne, M.P. Teter, D.C. Allan, T.A. Arias, J.D. Joannopoulos, Rev. Mod. Phys. 64 (1992) 1045-1097. DOI URL
[33]	G. Kresse, J. Furthmuller, Phys. Rev. B Condens. Matter 54 (1996) 11169-11186.
[34]	J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865-3868. DOI URL PMID
[35]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 132 (2010) 154104.
[36]	G.X. Zhang, A. Tkatchenko, J. Paier, H. Appel, M. Scheﬄer,Phys. Rev. Lett. 107 (2011) 245501.
[37]	S. Ehrlich, J. Moellmann, W. Reckien, T. Bredow, S. Grimme, Chemphyschem 12 (2011) 3414-3420.
[38]	Z.S. Luo, C.Z. Hu, L. Xie, H.B. Nie, C.Y. Xiang, X.F. Gu, J.Q. He, W.Q. Zhang, Z.Y. Yu, J. Luo, Mater. Horiz. 7 (2020) 173-180. DOI URL
[39]	D. Vanderbilt, Phys. Rev. B 41 (1990) 7892-7895. DOI URL
[40]	S. Plimpton, J. Comput. Phys. 117 (1995) 1-19.
[41]	A.D. Kulkarni, D.G. Truhlar, S. Goverapet Srinivasan, A.C.T. van Duin, P. Norman, T.E. Schwartzentruber, J. Phys. Chem. C 117 (2012) 258-269. DOI URL
[42]	I. Kohatsu, J.W. McCauley, Mater. Res. Bull. 9 (1974) 917-920. DOI URL
[43]	E. Heifets, W.A. Goddard, E.A. Kotomin, R.I. Eglitis, G. Borstel, Phys. Rev. B 69 (2004) 035408.
[44]	Q. Li, M. Rellán-Piñeiro, N. Almora-Barrios, M. Garcia-Ratés, I.N. Remediakis, N. López, Nanoscale 9 (2017) 13089-13094.
[45]	L. Wang, T. Maxisch, G. Ceder, Phys. Rev. B 73 (2006) 195107.
[46]	L. Wang, T. Maxisch, G. Ceder, Chem. Mater. 19 (2006) 543-552. DOI URL
[47]	K. Reuter, M. Scheﬄer, Phys. Rev. B 65 (2001) 035406.
[48]	Q.Y. Ruan, J.C. Ye, D.J. Shu, M. Wang, Phys. Rev. B 96 (2017) 115412.
[49]	A. Soon, M. Todorova, B. Delley, C. Stampfl, Phys. Rev. B 75 (2007) 125420.
[50]	M.W. Chase Jr, J. Phys. Chem. Ref. Data Monogr. 9 (1998) 1-1951.
[51]	J.D. Cox, D.D. Wagman, V.A. Medvedev, CODATA Key Values for Thermodynam- ics, Hemisphere Publishing Corp., New York, 1989.
[52]	S.H. Zou, Y.S. Liu, J.H. Li, C.P. Liu, R. Feng, F.L. Jiang, Y.X. Li, J.Z. Song, H.B. Zeng, M. C. Hong, X.Y. Chen, J. Am. Chem. Soc. 139 (2017) 11443-11450. DOI URL
[53]	A. Swarnkar, W.J. Mir, A. Nag, ACS Energy Lett. 3 (2018) 286-289. DOI URL
[54]	Z. Fang, X.M. Hou, Y.P. Zheng, Z.B. Yang, K.C. Chou, G. Shao, M.H. Shang, W.Y. Yang, T. Wu, Adv. Funct. Mater. 31 (2021) 2102330.
[55]	F.L. Riley, J. Am. Ceram. Soc. 83 (2004) 245-265. DOI URL
[56]	Z. Fang, E.H. Wang, Y.F. Chen, X.M. Hou, K.C. Chou, W.Y. Yang, J.H. Chen, M. H. Shang, ACS Appl. Mater. Interfaces 10 (2018) 30811-30818. DOI URL
[57]	R.T. Sanderson, J. Am. Chem. Soc. 105 (1983) 2259-2261. DOI URL