类球形氧化铈的制备及抛光性能
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摘要
采用溶剂热法合成了粒径为200 nm左右的类球形Ce O2前驱体,在一定温度下煅烧得到抛光粉,采用X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)、电子衍射、激光粒度分析仪等对其进行了表征和观察;同时考察了溶剂热温度、分散剂种类和用量等因素对合成类球形Ce O2前驱体的影响,以及不同煅烧温度和煅烧时间对单晶硅片抛光性能的影响。结果表明:以氯化铈为铈源,以0.75 mol·L-1NH3·H2O为沉淀剂,乙二醇为溶剂,聚乙烯吡咯烷酮(PVP)为分散剂,搅拌30 min后得到浑浊液转移至50 ml内衬聚四氟乙烯(PTFE)反应罐中,在烘箱中于180℃反应24 h,沉淀分别用去离子水,无水乙醇各洗3次,放于60℃烘箱中烘干,得到氧化铈前驱体,经500℃煅烧2 h为D50=203 nm的类球形Ce O2粉体,粉体分散性好,配成质量分数为0.2%的抛光浆料对n(111)型单晶硅片抛光,得到较高抛光速率和超平整的抛光表面。
The roundish Ce O2 precursors with diameters of 200 nm were synthesized by solvothermal method. And the polishing powder was obtained by calcining the precursor at different temperatures and characterized by X-ray diffraction( XRD),scanning electron microscopy( SEM),transmission electron microscopy( TEM),electron diffraction,and laser particle size analyzer. The effect of solvothermal temperatures,the kind and amount of dispersant on the Ce O2 precursors and the effect of the different calcining temperatures and time on the performance of monocrystalline silicon polishing were studied. The results showed that the roundish precursors could be obtained using cerium chloride as the source,0. 75 mol·L- 1NH3·H2O as the precipitator,ethylene glycol as the solvent and polyvinyl pyrrolidone( PVP) as the dispersant,a turbid liquid was obtained after stirring for 30 min,then transferred into a 50 ml autoclave lined with polytetrafluoro ethylene( PTFE),put into the oven under 180 ℃ to react for 24 h. The product was precipitated,washed with deionized water and anhydrous ethanol each 3 times,then dried at about 60 ℃ to get the Ce O2 precursors. The precursors transformed into the roundish Ce O2 powders with D50 of 203 nm by calcining at 500 ℃,it had excellent dispersibility,and with the mass fraction of 0. 2% polishing slurry,the higher polishing rate and the ultra-smooth surface of n( 111)-type silicon wafer could be acquired after polished.
The roundish Ce O2 precursors with diameters of 200 nm were synthesized by solvothermal method. And the polishing powder was obtained by calcining the precursor at different temperatures and characterized by X-ray diffraction( XRD),scanning electron microscopy( SEM),transmission electron microscopy( TEM),electron diffraction,and laser particle size analyzer. The effect of solvothermal temperatures,the kind and amount of dispersant on the Ce O2 precursors and the effect of the different calcining temperatures and time on the performance of monocrystalline silicon polishing were studied. The results showed that the roundish precursors could be obtained using cerium chloride as the source,0. 75 mol·L- 1NH3·H2O as the precipitator,ethylene glycol as the solvent and polyvinyl pyrrolidone( PVP) as the dispersant,a turbid liquid was obtained after stirring for 30 min,then transferred into a 50 ml autoclave lined with polytetrafluoro ethylene( PTFE),put into the oven under 180 ℃ to react for 24 h. The product was precipitated,washed with deionized water and anhydrous ethanol each 3 times,then dried at about 60 ℃ to get the Ce O2 precursors. The precursors transformed into the roundish Ce O2 powders with D50 of 203 nm by calcining at 500 ℃,it had excellent dispersibility,and with the mass fraction of 0. 2% polishing slurry,the higher polishing rate and the ultra-smooth surface of n( 111)-type silicon wafer could be acquired after polished.
引文
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[15]Yang M M,Tu H L,Zhang X Q,Xiong Y H,Wang X N,Du J.Influence of Ce O2-doping on electrical properties[J].Chinese Journal of Rare Metals,2012,36(2):292.(杨萌萌,屠海令,张心强,熊玉华,王小娜,杜军.Ce O2掺杂对Hf O2介质电学特性的影响[J].稀有金属,2012,36(2):292.)
[2]Zhou X M,Cen Z J,Li J,Peng H,Li Y X.Preparation of fluorine-doped composite abrasives by using different fluorine sources and their polishing behaviors on single crystal silicon[J].Chinese Rare Earths,2012,33(6):1.(周新木,岑志军,李静,彭欢,李永绣.掺氟复合磨料的制备及对单晶硅抛光性能的影响[J].稀土,2012,33(6):1.)
[3]Xu G Q,Zheng Z X,Tang W M,Wu Y C.Effect of sulfur ion doping on the luminescence properties of cerium ion-doped silica[J].Journal of the Chinese Ceramic Society,2007,35(1):10.(徐光青,郑治祥,汤文明,吴玉程.S2-掺杂对Ce3+-Si O2材料发光性能的影响[J].硅酸盐学报,2007,35(1):10.)
[4]Li M,Zhang X W,Liu Z G,Hu Y H,Du C S,Shao H L.Application of Ce O2in glass[J].Chinese Rare Earths,2011,32(3):80.(李梅,张晓伟,柳召刚,胡艳宏,杜长顺,邵海丽.氧化铈在玻璃中的应用[J].稀土,2011,32(3):80.)
[5]Zhou X M,Chen H Q,Dong X P.Synthesis and characteristics of mesoporous ceria oxide using an inorganic template approach[J].Chinese Rare Earths,2009,30(6):31.(周新木,陈慧勤,董雪平.无机盐模板剂法合成介孔Ce O2[J].稀土,2009,30(6):31.)
[6]Yang S W,Gao L.Controlled synthesis and self-assembly of Ce O2nanocubes[J].J.Am.Chem.Soc.,2006,128:9330.
[7]Cao C Y,Cui Z M,Chen C Q,Song W U,Cai W.Ceria hollow nanospheres produced by a template-free microwave-assisted hydrothermal method for heavy metal ion removal and catalysis[J].J.Phys.Chem.C,2010,114:9865.
[8]Pan Z C,Yang W X,Zhang H H,Xiao C M.Electrochemical synthesis and characterization of Ce O2nanoparticles[J].New Chemical Materials,2004,32(10):31.(潘湛昌,杨文霞,张环华,肖楚民.纳米二氧化铈的电化学制备与表征[J].化工新型材料,2004,32(10):31.)
[9]Mai H X,Sun L D,Zhang Y W,Si R,Feng W,Zhang H P,Liu H C,Yan C H.Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra,nanorods,and nanocubes[J].J.Phys.Chem.B,2005,109:24380.
[10]Peng H,Zhou X M,Li J,Huang X F,Zhou X Z,Li Y X.The synthesis of Ce O2nanowires and the influencing factors[J].Chinese Rare Earths,2013,34(4):7.(彭欢,周新木,李静,黄肖凤,周雪珍,李永绣.Ce O2纳米线的合成及影响因素的探讨[J].稀土,2013,34(4):7.)
[11]Zhao X B,You J,Lu X W,Chen Z G.Hydrothermal synthesis,characterization and property of Ce O2nanotube[J].Journal of Inorganic Materials,2011,26(2):159.(赵晓兵,游静,陆晓旺,陈志刚.Ce O2纳米管的水热合成、表征及性能研究[J].无机材料学报,2011,26(2):159.)
[12]Chen T L,Mullins D R.Ethylene glycol adsorption and reaction over Ce OX(111)thin films[J].J.Phys.Chem.C,2011,115:13725.
[13]Yang S W,Gao L.Controlled synthesis and self-assembly of Ce O2nanocubes[J].J.Am.Chem.Soc.,2006,128:9330.
[14]Wen C,Zhu Y,Ye Y C,Zhang S,Cheng F,Liu Y,Wang P,Tao F K.Water gas shift reaction on metal nanoclusters encapsulated in mesoporous ceria studied with ambient-pressure X-ray photoelectron spectroscopy[J].ACS Nano.,2012,6(10):9305.
[15]Yang M M,Tu H L,Zhang X Q,Xiong Y H,Wang X N,Du J.Influence of Ce O2-doping on electrical properties[J].Chinese Journal of Rare Metals,2012,36(2):292.(杨萌萌,屠海令,张心强,熊玉华,王小娜,杜军.Ce O2掺杂对Hf O2介质电学特性的影响[J].稀有金属,2012,36(2):292.)