CN109559977A - 一种化学液相法制备硫化铅薄膜的方法 - Google Patents
一种化学液相法制备硫化铅薄膜的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 229940056932 lead sulfide Drugs 0.000 title claims abstract description 18
- 229910052981 lead sulfide Inorganic materials 0.000 title claims abstract description 18
- 239000007791 liquid phase Substances 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 title claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 7
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims abstract description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 6
- 229940074439 potassium sodium tartrate Drugs 0.000 claims abstract description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims abstract description 4
- 229940046892 lead acetate Drugs 0.000 claims abstract description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical compound [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 5
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005202 decontamination Methods 0.000 claims description 3
- 230000003588 decontaminative effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- UKTDQTGMXUHPIF-UHFFFAOYSA-N [Na].S(O)(O)=O Chemical compound [Na].S(O)(O)=O UKTDQTGMXUHPIF-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 24
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000008139 complexing agent Substances 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- 229910001868 water Inorganic materials 0.000 abstract description 3
- 239000013049 sediment Substances 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000004500 asepsis Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005088 metallography Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种化学液相法制备硫化铅薄膜的方法,属于半导体材料的制备领域。本发明采用的是醋酸铅和硫粉,分别为铅源和硫源,以硫粉和亚硫酸钠为原料制备硫代硫酸钠,以酒石酸钾钠为络合剂,通过氢氧化钾调节pH值,将沉积液放置水浴锅中,在75℃下加热3~4小时,干燥后得到的硫化铅薄膜。本发明合成方法中所用的原料易得,工艺简便,成本低、收率高和能大规模生产薄膜的优点,因此该方法具有非常广阔的应用前景。
Description
技术领域
本发明涉及一种制备硫化铅薄膜的方法,该方法简便易行,无毒环保,具有普适性,能够在实验室中进行快速有效的制备,属于半导体材料的制备领域。
背景技术
硫化铅薄膜是一类重要的半导体材料,窄禁带(0.41eV)较并且激发玻尔半径(18nm)较大,因为其介电常数较大,折射率高,可以制成具有高折射率的红外光学薄膜,并且广泛的应用于制造红外探测器、激光发射器、热电转换器、太阳能电池、发光二极管、超离子材料、薄膜晶体管等半导体器件。该材料在国防及工、农业建设中得到了大规模应用,近几十年来受到了科学界的广泛重视。
制备硫化铅薄膜的方法有很多,如低温水热法、化学反应法(CRM)、电化学沉积法( ECD )、连续离子反应法、溶胶-凝胶法(SGM)等。与这些制备方法比较,化学液相法从性能价格比上来说具有明显的优势,是广泛应用的一种方法。在相对较低的温度下,不需要任何特殊的设置和任何复杂的仪器,且制备的薄膜晶粒更加紧密,表面更加光滑。化学液相法具有成本低、收率高和能大规模生产薄膜等特点,在合成金属硫族化物晶体时有很大前景。
对比论文文献:刘峰.化学液相法制备PbS红外光电薄膜及其性能研究[D].成都:电子科技大学, 2012:17-21.与本专利相似,但也有很大的区别,在此特地指出。首先,原料的不同,论文文献采用在氢氧化钠溶液体系中制备PbS薄膜,而本发明中采用酒石酸钾钠作为制备原料,酒石酸钾钠是作为络合剂使用的,具有很好的络合性能,被广泛应用于电镀工业,得到的薄膜更加细致,可见附图2;其次,本专利的实验顺序、过程是要按照严格地络合过程来实现的,这是通过大量实验验证得到的。
发明内容
本发明是针对现有技术的不足,发明了一种化学液相法制备硫化铅薄膜的方法。
本发明采用的是化学液相法,其中醋酸铅和硫粉,分别为铅源和硫源,以硫粉和亚硫酸钠为原料制备硫代硫酸钠,以酒石酸钾钠为络合剂,通过氢氧化钾调节pH值,将沉积液放置水浴锅中,在85℃下加热4~5小时,干燥后得到的硫化铅薄膜。本发明合成方法中所用的原料易得,工艺简便,成本低、收率高和能大规模生产薄膜的优点,因此该方法具有非常广阔的应用前景。
化学液相法制备硫化铅薄膜的实验原理如下:
S + Na2SO3 → Na2S2O3
(S2O3)2- + 2OH- →S2- + SO4 2- + H2O
Pb2+ + S2- → PbS↓
此种硫化铅半导体薄膜的制备方法的步骤是:
(1)制备前对衬底进行去油、去污清洗,放入无水乙醇中经过超声波清洗25~30min,再放入无水乙醇中浸泡;
(2)配制出0.2mol/L的醋酸铅溶液、1 mol/L酒石酸钾钠溶液,将5g硫粉和12g亚硫酸钠放入烧杯中,加蒸馏水至100mL,在90℃下边搅拌边加热24h,过滤除去未反应的硫粉和硫酸盐后制备出0.2 mol/L硫代硫酸钠溶液;
(3)边搅拌边将20mL的酒石酸钾钠溶液缓慢地倒入30mL的醋酸铅溶液中,再将6~8mL的硫代硫酸钠倒入二者的混合溶液中,以沉积液的颜色变化,由浅棕色变至棕色再变至咖啡色最后至黑色,来判断硫代硫酸钠的具体用量;并使用氢氧化钾溶液调节pH值至11.0~12.0,加入去离子水至100mL;
(4)将衬底吹干后,放入75℃沉积液中, 3~4小时后取出,风干,得到硫化铅薄膜。
利用X射线衍射分析了所得硫化铅薄膜的相结构,结果如图1所示;利用金相显微镜分析了所得硫化铅薄膜的形貌图,结果如图2所示。
所得结果表明晶核分布比较均匀,薄膜较为致密且外观平整,已稳定成完全多晶结构,其密度得到改善。
与现有技术相比,本发明中所使用的化学液相法具有成本低、收率高和能大规模生产薄膜等特点,该方法简便易行,无毒环保,能够在实验室中进行快速有效的制备,具有普适性。
附图说明
图1是硫化铅薄膜的XRD衍射图谱。
图2是硫化铅薄膜的金相显微镜图:(a) 沉积时间3.0h,(b) 沉积时间3.5h,(c)沉积时间4.0h。
具体实施方式
制备前对衬底进行去油、去污清洗,放入无水乙醇中经过超声波清洗后,再放入无水乙醇中浸泡,沉积时使用;配制出0.2mol/L的醋酸铅溶液,1mol/L的酒石酸钾钠溶液和0.2mol/L硫代硫酸钠溶液;边搅拌边将30mL的醋酸铅溶液、20mL的酒石酸钾钠和6~8mL混合,再使用氢氧化钾溶液调节pH值至11.0~12.0,加入去离子水至100mL;准备三个沉底,吹干后放入75℃恒温水浴锅中的沉积液中,分别在3小时后,3.5小时后,4小时后取出沉底,得到硫化铅薄膜。
Claims (1)
1.一种化学液相法制备硫化铅薄膜的方法,其包括醋酸铅、酒石酸钾钠、硫粉、亚硫酸钠、氢氧化钾,沉积液在使用时pH控制在11.0~12.0,其特征在于步骤如下:
a.制备前对衬底进行去油、去污清洗,放入无水乙醇中经过超声波清洗25~30min,再放入无水乙醇中浸泡;
b.配制出0.2mol/L的醋酸铅溶液、1 mol/L酒石酸钾钠溶液,将5g硫粉和12g亚硫酸钠放入烧杯中,加蒸馏水至100mL,在90℃下边搅拌边加热24h,过滤除去未反应的硫粉和硫酸盐后制备出0.2 mol/L硫代硫酸钠溶液;
c.边搅拌边将20mL的酒石酸钾钠溶液缓慢地倒入30mL的醋酸铅溶液中,再将6~8mL的硫代硫酸钠倒入二者的混合溶液中,以沉积液的颜色变化,由浅棕色变至棕色再变至咖啡色最后至黑色,来判断硫代硫酸钠的具体用量;并使用氢氧化钾溶液调节pH值至11.0~12.0,加入去离子水至100mL;
d.将衬底吹干后,放入75℃沉积液中,3~4小时后取出,风干。
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