何祖东等：一步纳米银催化刻蚀法制备多孔硅纳米线阵列 .927· 9g99 沉积 基底氧化 基底溶解， 银颗粒下路 5基底 Ag形核于上 纳米线 图5采用HF/AgNO体系一步金属辅助化学刻蚀制备多孔硅纳米线的形成机理 Fig.5 Formation mechanism of porous SiNWs through one-step metal-assisted chemical etching in HF/AgNO:solution (丁朝，马文会，魏奎先，等.造渣氧化精炼提纯冶金级硅研 3结论 究进展.真空科学与技术学报，2013,33(2)：185) (1)较高的参杂浓度更有利于刻蚀反应的发生 [6]Liao M J,Qiao L,Xiao P,et al.Preparation of silicon nanowires 和硅纳米线阵列的形成. array by chemistry methods and photoelectrochemical hydrogen generation performance analysis.Chin J Inorg Chem,2015,31 (2)当AgNO3浓度过低或过高时，硅片表面会 (3):439 形成腐蚀凹坑或坍塌的纳米线簇：当AgNO3浓度为 (廖明佳，乔雷.肖鹏，等.湿化学法制备硅纳米线阵列及其 0.02molL-1时，硅纳米线会生长变长，最终形成纳 光电化学产氢性能分析.无机化学学报，2015,31(3)：439) 米线阵列 [7]NiZ F.Liu LG.Wang YG.Synthesis and characterization of sil- (3)HF溶液浓度超过4.6mol·L-时，随着HF ica nanowires catalysted by tin.Chin J Mater Res,2011,25(2): 酸浓度的增加，硅纳米线的长度和孔隙率都随之 183 增加 (倪自丰，刘利国，王永光.锡催化生长氧化硅纳米线的制备 和表征.材料研究学报，2011,25(2)：183) [8]Ahmed N,Bhargav P B.Rayerfrancis A,et al.Study the effect of 参考文献 plasma power density and gold catalyst thickness on silicon nanowires growth by plasma enhanced chemical vapour deposition. [1]Priolo F,Gregorkiewicz T,Galli M,et al.Silicon nanostructures Mater Lett,2018,219:127 for photonics and photovoltaics.Nat Nanotechnol,2014,9(1): [9]Liu L,Li Z S,Hu H D,et al.Insight into macroscopic metal-as- 19 sisted chemical etching for silicon nanowires.Acta Phys-Chim Sin, [2]Wu D,Lou Z H.Wang YG.et al.Photovoltaic high-performance 2016,32(4):1019 broadband photodetector based on MoS,/Si nanowire array hetero- [10]He X,Li S Y,Ma W H,et al.A simple and low-cost chemical junction.Sol Energy Mater Sol Cells,2018,182:272 etching method for controllable fabrication of large-scale kinked [3]Liu L,Cao Y,He J H,et al.Preparation and optoelectronic ap- silicon nanowires.Mater Lett,2017,196:269 plication of silicon nanowire arrays.Prog Chem,2013,25(2-3): [11]Li X,Bohn P W.Metal-assisted chemical etching in F/H202 248 produces porous silicon.Appl Phys Lett,2000,77(16):2572 (刘莉，曹阳，贺军辉，等.硅纳米线阵列的制备及其光电应 [12]He X,Zou Y X,Sheng G Z,et al.Research on controllable 用.化学进展，2013,25(2-3)：248) preparation and antireflection properties of zigag SiNWs arrays. [4]Shang Y D,Chen X H,Li S Y,et al.Performance limiting fac- Integr Ferroelectr,2017,182(1):65 tors and efficiency improvement methods of graphene/n-Si Schott- [13]Zhang C,Li S Y,Ma W H,et al.Fabrication of ultra-low an- ky junction solar cell.Mater Rev,2017,31(2):123 tireflection SiNWs arrays from me-Si using one step MACE.J (尚钰东，陈秀华，李绍元，等.石墨烯/-Si肖特基结太阳能 Mater Sci Mater Electron,2017,28(12):8510 电池的性能限制因素及效率提升方法.材料导报，2017,31 [14]Li S Y,Ma W H,Chen X H,et al.Structure and antireflection (2):123) properties of SiNWs arrays form me-Si wafer through Ag-catalyzed [5]Ding Z,Ma W H.Wei K X,et al.Latest progress in purification chemical etching.Appl Surf Sci,2016,369:232 of metallurgical grade silicon by slag oxidation refining.Chin I Vac [15]Yeom J,Ratchford D.Field C R,et al.Decoupling diameter Sci Technol,2013,33(2):185 and pitch in silicon nanowire arrays made by metal-assisted chem-何祖东等: 一步纳米银催化刻蚀法制备多孔硅纳米线阵列 图 5 采用 HF / AgNO3 体系一步金属辅助化学刻蚀制备多孔硅纳米线的形成机理 Fig. 5 Formation mechanism of porous SiNWs through one鄄step metal鄄assisted chemical etching in HF / AgNO3 solution 3 结论 (1)较高的掺杂浓度更有利于刻蚀反应的发生 和硅纳米线阵列的形成. (2)当 AgNO3 浓度过低或过高时,硅片表面会 形成腐蚀凹坑或坍塌的纳米线簇;当 AgNO3 浓度为 0郾 02 mol·L - 1时,硅纳米线会生长变长,最终形成纳 米线阵列. (3)HF 溶液浓度超过 4郾 6 mol·L - 1时,随着 HF 酸浓度的增加,硅纳米线的长度和孔隙率都随之 增加. 参 考 文 献 [1] Priolo F, Gregorkiewicz T, Galli M, et al. Silicon nanostructures for photonics and photovoltaics. Nat Nanotechnol, 2014, 9 (1): 19 [2] Wu D, Lou Z H, Wang Y G, et al. Photovoltaic high鄄performance broadband photodetector based on MoS2 / Si nanowire array hetero鄄 junction. Sol Energy Mater Sol Cells, 2018, 182: 272 [3] Liu L, Cao Y, He J H, et al. Preparation and optoelectronic ap鄄 plication of silicon nanowire arrays. Prog Chem, 2013, 25(2鄄3): 248 (刘莉, 曹阳, 贺军辉, 等. 硅纳米线阵列的制备及其光电应 用. 化学进展, 2013, 25(2鄄3): 248) [4] Shang Y D, Chen X H, Li S Y, et al. Performance limiting fac鄄 tors and efficiency improvement methods of graphene / n鄄鄄Si Schott鄄 ky junction solar cell. Mater Rev, 2017, 31(2): 123 (尚钰东, 陈秀华, 李绍元, 等. 石墨烯/ n鄄鄄Si 肖特基结太阳能 电池的性能限制因素及效率提升方法. 材料导报, 2017, 31 (2): 123) [5] Ding Z, Ma W H, Wei K X, et al. Latest progress in purification of metallurgical grade silicon by slag oxidation refining. Chin J Vac Sci Technol, 2013, 33(2): 185 (丁朝, 马文会, 魏奎先, 等. 造渣氧化精炼提纯冶金级硅研 究进展. 真空科学与技术学报, 2013, 33(2): 185) [6] Liao M J, Qiao L, Xiao P, et al. Preparation of silicon nanowires array by chemistry methods and photoelectrochemical hydrogen generation performance analysis. Chin J Inorg Chem, 2015, 31 (3): 439 (廖明佳, 乔雷, 肖鹏, 等. 湿化学法制备硅纳米线阵列及其 光电化学产氢性能分析. 无机化学学报, 2015, 31(3): 439) [7] Ni Z F, Liu L G, Wang Y G. Synthesis and characterization of sil鄄 ica nanowires catalysted by tin. Chin J Mater Res, 2011, 25(2): 183 (倪自丰,刘利国, 王永光. 锡催化生长氧化硅纳米线的制备 和表征. 材料研究学报, 2011, 25(2): 183) [8] Ahmed N, Bhargav P B, Rayerfrancis A, et al. Study the effect of plasma power density and gold catalyst thickness on silicon nanowires growth by plasma enhanced chemical vapour deposition. Mater Lett, 2018, 219: 127 [9] Liu L, Li Z S, Hu H D, et al. Insight into macroscopic metal鄄as鄄 sisted chemical etching for silicon nanowires. Acta Phys鄄Chim Sin, 2016, 32(4): 1019 [10] He X, Li S Y, Ma W H, et al. A simple and low鄄cost chemical etching method for controllable fabrication of large鄄scale kinked silicon nanowires. Mater Lett, 2017, 196: 269 [11] Li X, Bohn P W. Metal鄄assisted chemical etching in F / H2O2 produces porous silicon. Appl Phys Lett, 2000, 77(16): 2572 [12] He X, Zou Y X, Sheng G Z, et al. Research on controllable preparation and antireflection properties of zigzag SiNWs arrays. Integr Ferroelectr,2017,182(1):65 [13] Zhang C, Li S Y, Ma W H, et al. Fabrication of ultra鄄low an鄄 tireflection SiNWs arrays from mc鄄Si using one step MACE. J Mater Sci Mater Electron, 2017, 28(12): 8510 [14] Li S Y, Ma W H, Chen X H, et al. Structure and antireflection properties of SiNWs arrays form mc鄄Si wafer through Ag鄄catalyzed chemical etching. Appl Surf Sci, 2016, 369: 232 [15] Yeom J, Ratchford D, Field C R, et al. Decoupling diameter and pitch in silicon nanowire arrays made by metal鄄assisted chem鄄 ·927·