AlN的MOCVD生长中表面吸附的量子化学研究
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摘要
利用量子化学的密度泛函理论(DFT),对AlN的MOCVD生长中表面反应前体MMAl、DMAlNH_2分别在理想、NH_2覆盖AlN(0001)-Al面的吸附进行研究。通过分析表面吸附位、吸附能、分波态密度图等,确定可能的稳定吸附结构和吸附倾向。研究发现:在理想和NH_2覆盖的AlN(0001)-Al面,MMAl吸附在T4位和H_3位,吸附概率相近,MMAl与表面形成3个Al-Als键(理想AlN表面)或3个Al-Ns键(NH_2覆盖的AlN表面)。在理想AlN表面,DMAlNH_2吸附在Top-Top位,与表面形成N-Als键和Al-Als键;在NH_2覆盖的AlN表面,DMAlNH_2吸附在Top位,与表面形成Al-Ns键。对比两种粒子在理想和NH_2覆盖表面的吸附能,发现在理想表面DMAlNH_2的吸附能大于MMAl,即DMAlNH_2优先吸附;在NH_2覆盖表面,MMAl的吸附能明显大于DMAlNH_2,即MMAl优先吸附。
Quantum chemistry study with DFT method on surface adsorption of precursors MMAl and DMAlNH_2 on the ideal and NH_2-covered AlN( 0001)-Al surface in AlN-MOCVD were conducted. By comparing the surface adsorption sites,adsorption energies and partial density of states( PDOS),the possible adsorption structure and adsorption tendency were determined. It is found that MMAl is adsorbed at T4 and H_3 sites on both ideal and NH_2-covered AlN( 0001)-Al surfaces.The adsorption energies are similar,with three Al-Alsbonds( ideal surface) or Al-Nsbonds( NH_2-covered surface).DMAlNH_2 is adsorbed at the Top-Top site( ideal surface) with both N-Alsbond and Al-Alsbond formed,and at the Top site( NH_2-covered surface) with an Al-Nsbond. Comparing the adsorption energies of two precursors,on the ideal surface,the adsorption energy of DMAlNH_2 is greater than that of MMAl,and thus DMAlNH_2 is preferentially adsorbed; on NH_2-covered surface,the adsorption energy of MMAl is much greater than that of DMAlNH_2,and thus MMAl adsorption is preferred.
Quantum chemistry study with DFT method on surface adsorption of precursors MMAl and DMAlNH_2 on the ideal and NH_2-covered AlN( 0001)-Al surface in AlN-MOCVD were conducted. By comparing the surface adsorption sites,adsorption energies and partial density of states( PDOS),the possible adsorption structure and adsorption tendency were determined. It is found that MMAl is adsorbed at T4 and H_3 sites on both ideal and NH_2-covered AlN( 0001)-Al surfaces.The adsorption energies are similar,with three Al-Alsbonds( ideal surface) or Al-Nsbonds( NH_2-covered surface).DMAlNH_2 is adsorbed at the Top-Top site( ideal surface) with both N-Alsbond and Al-Alsbond formed,and at the Top site( NH_2-covered surface) with an Al-Nsbond. Comparing the adsorption energies of two precursors,on the ideal surface,the adsorption energy of DMAlNH_2 is greater than that of MMAl,and thus DMAlNH_2 is preferentially adsorbed; on NH_2-covered surface,the adsorption energy of MMAl is much greater than that of DMAlNH_2,and thus MMAl adsorption is preferred.
引文
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[3] Doi K,Maida N,Kimura K,et al. First-principle Study on Crystal Growth of Ga and N Layers on Ga N Substrate[J]. Physica Status Solidi,2007,4(7):2293-2296.
[4] Kempisty P,Strak P,Sakowski K,et al. Adsorption of Ammonia on Hydrogen Covered Ga N(0001)Surface-Density Functional Theory study[J]. Journal of Crystal Growth,2014,401:514-517.
[5] Kempisty P,Krukowski S. Adsorption of Ammonia at Ga N(0001)Surface in the Mixed Ammonia/hydrogen Ambient-a Summary of Ab Initio Data[J]. Aip Advances,2014,4(11):054901.
[6] Van de Walle C G,Neugebauer J. Structure and Energetics of Nitride Surfaces under MOCVD Growth Conditions[J]. Journal of Crystal Growth,2003,248(none):8-13.
[7]唐斌龙,张红,左然. MOVPE生长Ga N薄膜的表面吸附和扩散研究[J].人工晶体学报,2017,46(5):19-24.
[8] Jindala V. Shahedipour-Sandvik F. Density Functional Theoretical Study of Surface Structure and Adatom Kinetics for Wurtzite Al N[J]. Applied Physics,2009,105(8):084902.
[9] Akiyama T,Nakamura K,T. Ito,Ab initio-based Study for Adatom Kinetics on Al N(0001)Surfaces during Metal-organic Vapor-phase Epitaxy Growth[J]. Applied Physics Letters,2012,100:251601.
[10] Kangawa Y,Akiyama T,Ito T,et al. Surface Stability and Growth Kinetics of Compound Semiconductors:An Ab Initio-Based Approach[J].Materials 2013,6:3309-3360.
[11] Inagaki Y,Kozawa T,Chemical Reaction Pathways for MOCVD Growth of Aluminum Nitride[J]. ECS J. Solid State Sci. and Tech,2016,5(2):73-75.
[12] Suzuki H,R. Ogash,H. Murakami et al,Theoretical Analysis for Surface Reconstruction of Al N and InN in the Presence of Hydrogen[J].Japanese J. Applied Physics,2007,46(8):5112-5115.
[13] Suzuki H,Murakami H,Kumagai Y,et al. Theoretical Study on the Influence of Surface Hydrogen Coverage on the Initial Growth Process of Al N(0001)Surfaces[J]. Physica Status Solidi,2011,8(5):1577-1580.
[14]庄芹芹,林伟,王元樟,等. Al和N极性Al N生长特性的第一性原理[J].厦门理工学院学报,2013,21(3):30-34.
[15] Yongnian X U,CHING,W. Y,Electronic,Optical,and Structural Properties of Some Wurtzite Crystals[J]. Physical Review B Condensed Matter,1993,48(7):4335.
[16]萧.密度泛函理论[M].北京:国防工业出版社,2014.
[17] Hu C L,Chen Y,Li J Q. First-principles Calculations of H2O Adsorption Reaction on the Ga N(0001)Surface[J]. Chinese Journal of Structural Chemistry,2009,28(2):240-244.
[18] Ikeda Y,Ohmori N,Maida N,et al. Theoretical Study of Gallium Nitride Crystal Growth Reaction Mechanism[J]. Japanese Journal of Applied Physics,2011,50(50):943-949.
[19] Lin T T,Xiang Y L,He C. A DFT Study on Poly(lactic acid)Polymorphs[J]. Polymer,2010,51(12):2779-2785.
[20] Jordaan M,Helden P V,Sittert C,et al. Experimental and DFT Investigation of the 1-octene Metathesis Reaction Mechanism with the Grubbs 1Precatalyst[J]. Journal of Molecular Catalysis A:Chemical,2006,254(1):145-154.
[21]李炜,陈俊芳,王腾,等. Si表面吸附Ga N的第一性原理研究[J].材料导报,2009,23(16):71-73.