CN106374010B - 一种纳米银复合氧化锡透明导电薄膜的制备方法 - Google Patents
一种纳米银复合氧化锡透明导电薄膜的制备方法 Download PDFInfo
- Publication number
- CN106374010B CN106374010B CN201610877043.7A CN201610877043A CN106374010B CN 106374010 B CN106374010 B CN 106374010B CN 201610877043 A CN201610877043 A CN 201610877043A CN 106374010 B CN106374010 B CN 106374010B
- Authority
- CN
- China
- Prior art keywords
- tin oxide
- conductive film
- silver
- transparent conductive
- fluorine doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 99
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 28
- 239000004332 silver Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 56
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000011737 fluorine Substances 0.000 claims abstract description 53
- 108010025899 gelatin film Proteins 0.000 claims abstract description 41
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000011049 filling Methods 0.000 claims abstract description 17
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 230000007704 transition Effects 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 76
- 238000002834 transmittance Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 241000370738 Chlorion Species 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 238000001935 peptisation Methods 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 235000014121 butter Nutrition 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims description 2
- LMZURCXQQZLYNR-UHFFFAOYSA-N ethanol;silver Chemical compound [Ag].CCO LMZURCXQQZLYNR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- -1 organic acid tin salt Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NBYLLBXLDOPANK-UHFFFAOYSA-M silver 2-carboxyphenolate hydrate Chemical compound C1=CC=C(C(=C1)C(=O)O)[O-].O.[Ag+] NBYLLBXLDOPANK-UHFFFAOYSA-M 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- WPEOGXOIJDXEQY-UHFFFAOYSA-N silver;sulfamic acid Chemical compound [Ag].NS(O)(=O)=O WPEOGXOIJDXEQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- HTRJDXQPCKIFIU-UHFFFAOYSA-N silver;ethanol;nitrate Chemical compound [Ag+].CCO.[O-][N+]([O-])=O HTRJDXQPCKIFIU-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- ZMQKZSQODJUBTO-UHFFFAOYSA-M silver ethanol acetate Chemical compound C(C)O.C(C)(=O)[O-].[Ag+] ZMQKZSQODJUBTO-UHFFFAOYSA-M 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
本发明涉及一种纳米银复合氧化锡透明导电薄膜的制备方法,在溶胶‑凝胶法制备的氧化锡导电薄膜孔隙中填充可溶性银盐和亚锡盐,原位还原生成纳米银粒子,高温烧结得到纳米银复合氧化锡透明导电薄膜,纳米银复合氧化锡透明导电薄膜的化学组成为:AgxSnO2‑yFy,分子式中,x=0.01‑0.1,y=0‑0.6,采取的技术方案包括在太阳电池玻璃基体上涂覆二氧化硅过渡层、掺氟氧化锡纳米溶胶制备、掺氟氧化锡凝胶薄膜制备、多孔氧化锡凝胶薄膜孔隙填充、纳米银复合氧化锡透明导电薄膜形成五部分。本发明是降低FTO导电薄膜电阻简便易行的技术措施,具有产业化应用前景。
Description
技术领域
本发明涉及一种纳米银复合氧化锡透明导电薄膜的制备方法,特别是一种在溶胶-凝胶法制备的氧化锡导电薄膜孔隙中原位生成纳米银粒子,得到纳米银复合高透光率低方块电阻氧化锡透明导电薄膜的制备方法,属于新能源材料和节能环保领域。
技术背景
透明导电氧化物(TCO)是把光学透明性与导电性复合在一体的光电材料,目前大量用作薄膜太阳电池的透明电极,还应用于液晶显示屏、光催化和建筑节能等领域,市场需求巨大。TCO玻璃是在玻璃表面通过物理或者化学方法均匀镀上一层TCO薄膜形成的。常见的TCO材料包括氧化铟基、氧化锡基和氧化锌基三类。FTO导电玻璃透光率80%以上,原料来源广,生产成本较低,热稳定性和化学稳定性好,激光刻蚀较容易。由于FTO导电玻璃的性价比优势,已作为ITO导电玻璃的替代产品成为薄膜太阳电池的重要原料和商业化应用,钙钛矿太阳电池颠覆性技术突破刺激了FTO导电玻璃市场发展。
FTO导电薄膜和导电玻璃具有透明性和导电性两大基本特性,但其导电性能仍需改进才能满足薄膜太阳电池不断提高的技术要求。除了对制备工艺条件优化改进外,国内外研究主要从三条新途径降低FTO导电薄膜方块电阻:(1)多元素掺杂增加FTO导电薄膜的载流子浓度;(2)与低电阻金属材料形成复合透明导电膜;(3)与低电阻透明材料形成复合透明导电膜。
银、金、镍、铜等金属具有良好的导电性,其电阻率比透明氧化物低二个数量级,但只有在金属薄膜厚度小于20nm 时才具有良好的透光性能,而极薄的金属膜层往往以岛状形式存在,导致薄膜具有很高的电阻和反射率。将FTO导电薄膜与金属薄膜复合是一种降低FTO导电薄膜方块电阻的有效途径。中国专利CN103151394(2013-06-12)公开一种薄膜太阳能电池及其制作方法,在10-20nm厚度的纳米银薄膜上涂覆TCO导电薄膜,得到了低电阻的银复合透明导电薄膜,提高了薄膜太阳电池效率,但需要采用技术复杂和高成本的磁控溅射技术和热蒸镀技术。中国专利CN101515602(2009-08-26)公开一种透明导电膜玻璃,在FTO导电薄膜上印刷银栅电极,从而降低导电基底的欧姆损失,但印刷制备的银栅线一般宽度和厚度都比较大,较宽的银栅线的光遮挡使透光率降低,较厚的银栅线也不利于后续光吸收材料均匀涂覆。
采用溶胶-凝胶法制备的掺氟氧化锡透明导电薄膜因表面结构疏松和孔隙率高,导致薄膜表面方块电阻增大。若在FTO薄膜孔隙中填充银盐,原位还原生成纳米银包覆氧化锡,将得到纳米银复合高透光率低方块电阻氧化锡透明导电薄膜。
发明内容
本发明的目的是提供一种纳米银复合氧化锡透明导电薄膜的制备方法,其特征是在溶胶-凝胶法制备的氧化锡导电薄膜孔隙中填充可溶性银盐和亚锡盐,原位还原生成纳米银粒子,再高温烧结得到纳米银复合高透光率低方块电阻氧化锡透明导电薄膜,纳米银复合氧化锡透明导电薄膜的化学组成为:AgxSnO2-yFy ,其中, x=0.01-0.1,y =0-0.6,采取的技术方案包括在太阳电池玻璃基体上涂覆二氧化硅过渡层、掺氟氧化锡纳米溶胶制备、掺氟氧化锡凝胶薄膜制备、多孔氧化锡凝胶薄膜孔隙填充、纳米银复合氧化锡透明导电薄膜形成五部分。
太阳电池玻璃基体上涂覆二氧化硅过渡层在太阳电池玻璃基体表面涂覆厚度为50-100nm的纳米二氧化硅过渡层,用于阻滞高温下钠钙玻璃中钠钙离子向导电薄膜中扩散,同时作为减反射层增大玻璃基体透光率和改善掺氟氧化锡透明导电薄膜在玻璃基体上的附着力。
纳米溶胶制备方法为:(1)向四氯化锡水溶液中加入氨水使锡盐水解,将形成的沉淀洗涤至无氯离子;(2)将水合氧化锡沉淀物悬浮在去离子水中,加入含氟掺杂剂氟化铵或氢氟酸,再加入饱和草酸水溶液,使水合氧化锡沉淀在50-60℃下完全胶溶,生成掺氟氧化锡纳米溶胶pH为0.8-1.5,掺氟氧化锡纳米溶胶的组成摩尔比为Sn(OH)4:F: H2C2O4=1:0-0.6:0.1-0.4;(3)向掺氟氧化锡纳米溶胶中加入聚氨酯乳液,使其质量百分浓度为0.01%-0.2%,以改善掺氟氧化锡溶胶稳定性、涂布均匀性和防止膜层干燥时开裂,掺氟氧化锡纳米溶胶中二氧化锡质量百分浓度为4%-5%。
凝胶薄膜制备方法是在太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶2-3遍,使凝胶薄膜厚度400-800nm,在150℃下烘干得到掺氟氧化锡凝胶薄膜,掺氟氧化锡粒径为10-15nm,掺氟氧化锡凝胶薄膜孔隙率为20%-30%。
多孔氧化锡凝胶薄膜孔隙填充方法是在掺氟氧化锡多孔凝胶薄膜上涂布可溶性银盐乙醇水溶液2-3次,使可溶性银盐浸渍填充到薄膜孔隙中,再涂布亚锡盐的乙醇水溶液,使可溶性银盐原位还原为纳米银粒子,控制原料的摩尔比为(Sn4++ Sn2+):F:Ag:Sn2+ =1:0-0.6:0.01-0.1:0.01-0.1,在150℃下烘干,氧化锡凝胶薄膜孔隙率为10%-15%,所述可溶性银盐是硝酸银、氨基磺酸银、乙酸银和水杨酸银,所述亚锡盐是氯化亚锡、硝酸亚锡和有机酸亚锡盐。
纳米银复合氧化锡透明导电薄膜形成方法是将镀膜玻璃基体加热到300℃,在300-450℃时升温速度降低到3-5℃/min,使填充的可溶性银盐高温完全分解为纳米银并包覆氧化锡,最后在500℃高温下烧结30分钟,使有机物完全分解,使氟原子掺杂进入氧化锡晶格中形成掺氟氧化锡,并使掺氟氧化锡结晶长大形成透明导电薄膜,填充后纳米银包覆氧化锡薄膜孔隙率为5%-10%,导电玻璃可见光透光率为81%-85%,方块电阻为1-5Ω/□。
本发明能够降低薄膜方块电阻的原因包括几个方面:(1)原位还原生成的纳米银包覆氧化锡自身连接形成低电阻的纳米银网,从而降低了复合透明导电薄膜方块电阻;(2)原位还原生成的纳米银与氧化锡生成低电阻银锡合金,从而降低了复合透明导电薄膜方块电阻(3)氧化锡薄膜孔隙填充和高温烧结降低了掺氟氧化锡凝胶薄膜孔隙率,从而降低复合透明导电薄膜方块电阻。
本发明所用的实验原料二氧化硅溶胶、四氯化锡、氯化亚锡、氨水、氟化铵、草酸、硝酸银、乙醇、聚氨酯乳液均为市售化学纯试剂;太阳电池玻璃为市售商品。
纳米银复合氧化锡透明导电薄膜和导电玻璃的透光率用 Lambda 920 型分光光度计测试样品在400-760nm可见光范围的透过率计算;纳米银复合氧化锡透明导电薄膜和导电玻璃的方块电阻用ST2258C型四探针方阻计测试;掺杂氧化锡透明导电薄膜的孔隙率通过样品扫描电镜图像截面计算。
本发明的有益效果体现在:
(1)本发明纳米银复合氧化锡透明导电薄膜和导电玻璃透光率高和方块电阻低,适合作为大面积薄膜太阳电池透明电极应用;
(2)本发明在FTO导电薄膜中原位形成纳米银网,是降低FTO导电薄膜电阻简便易行的技术措施,具有产业化应用前景。
具体实施方式
实施例1
玻璃基体上二氧化硅过渡层涂覆:将100mm×100 mm×1mm的超白玻璃基体用清水冲洗干净,无水乙醇清洗和晾干,然后在其表面用涂布棒涂覆厚度为100nm的纳米二氧化硅镀膜溶胶,空气中晾干后形成表面均匀的镀膜玻璃过渡层,测得涂膜前后在400-760nm可见光波长范围的透光率分别为91.5%和93.5%。
纳米溶胶制备:将无水四氯化锡26.1g(0.1mol)溶于500ml去离子水中,在搅拌下加入2mol/L的氨水,直到不再有沉淀析出和溶液pH为8-9,将水解形成的沉淀过滤,用去离子水洗涤至无氯离子。将沉淀物悬浮在200ml去离子水中,加入饱和草酸水溶液37g(0.03mol),使水合氧化锡沉淀在50-60℃下完全胶溶,加入氟化铵0.37g(0.01mol)作为掺杂氟源,加入聚氨酯乳液0.5g,得到二氧化锡质量百分浓度为5%的掺氟氧化锡纳米溶胶,形成溶胶的pH为1.1。
凝胶薄膜制备:在太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶3次,使凝胶薄膜厚度为500-600nm,在150℃下烘干得到掺氟氧化锡凝胶薄膜,测得凝胶粒径为10-15nm,凝胶薄膜孔隙率为27%。
多孔氧化锡凝胶薄膜中纳米银填充:在掺氟氧化锡多孔凝胶薄膜上涂布质量百分浓度为5%的硝酸银乙醇溶液3次,使其浸渍填充到薄膜孔隙中,再涂布质量百分浓度为5%的氯化亚锡乙醇水溶液2次,使硝酸银原位还原为纳米银粒子填充薄膜孔隙, 在150℃下烘干,测得薄膜孔隙率为15%。
纳米银复合氧化锡形成:将镀膜玻璃基体加热到300℃,在300-450℃时升温速度降低到3-5℃/min,使填充的银盐高温完全分解为纳米银并包覆氧化锡,最后在500℃高温下烧结30分钟,使有机物完全分解,使氟原子掺杂进入氧化锡晶格中形成掺氟氧化锡,并使掺氟氧化锡结晶长大形成透明导电薄膜,纳米银包覆氧化锡薄膜的孔隙率为8.5%,导电玻璃可见光透光率为83.5%,方块电阻为1.8Ω/□。
实施例2
掺氟氧化锡纳米溶胶制备:将无水四氯化锡26.1g(0.1mol)溶于500ml去离子水中,在搅拌下加入2mol/L的氨水,直到不再有沉淀析出和溶液pH为8-9,将水解形成的沉淀过滤,用去离子水洗涤至无氯离子。将沉淀物悬浮在200ml去离子水中,加入饱和草酸水溶液37g(0.03mol),使水合氧化锡沉淀在50-60℃下完全胶溶,加入氟化铵0.37g(0.01mol)作为掺杂氟源,加入聚氨酯乳液0.5g,得到二氧化锡质量百分浓度为5%的掺氟氧化锡纳米溶胶,形成溶胶的pH为1.1。
凝胶薄膜制备:在太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶3次,使凝胶薄膜厚度为400-450nm,在150℃下烘干得到掺氟氧化锡凝胶薄膜,测得凝胶粒径为10-15nm,凝胶薄膜孔隙率为28%。
多孔氧化锡凝胶薄膜中纳米银填充:在掺氟氧化锡多孔凝胶薄膜上涂布质量百分浓度为1%的乙酸银乙醇溶液3次,使其浸渍填充到薄膜孔隙中,再涂布质量百分浓度为5%的氯化亚锡乙醇水溶液2次,使硝酸银原位还原为纳米银粒子填充薄膜孔隙, 在150℃下烘干,测得薄膜孔隙率为17%。
纳米银复合氧化锡形成:将镀膜玻璃基体加热到300℃,在300-450℃时升温速度降低到3-5℃/min,使填充的银盐高温完全分解为纳米银并包覆氧化锡,最后在500℃高温下烧结30分钟,使有机物完全分解,使氟化物掺杂进入氧化锡晶格中形成掺氟氧化锡,并使掺氟氧化锡结晶长大形成透明导电薄膜,纳米银包覆氧化锡薄膜孔隙率9.5%,导电玻璃可见光透光率为84.8%,方块电阻为2.8Ω/□。
实施例3
氧化锡纳米溶胶制备:将无水四氯化锡26.1g(0.1mol)溶于500ml去离子水中,在搅拌下加入2mol/L的氨水,直到不再有沉淀析出和溶液pH为8-9,将水解形成的沉淀过滤,用去离子水洗涤至无氯离子。将沉淀物悬浮在200ml去离子水中,加入饱和草酸水溶液37g(0.03mol),使水合氧化锡沉淀在50-60℃下完全胶溶,未加入掺杂氟源,只加入聚氨酯乳液0.5g,得到二氧化锡质量百分浓度为5%的掺氟氧化锡纳米溶胶,形成溶胶pH为1.1。
氧化锡凝胶薄膜制备:在太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶3遍,使凝胶薄膜厚度为500-600nm,在150℃下烘干得到掺氟氧化锡凝胶薄膜,测得凝胶粒径为10-15nm,凝胶薄膜孔隙率为29%。
多孔氧化锡凝胶薄膜中纳米银填充:在氧化锡多孔凝胶薄膜上涂布质量百分浓度为5%的硝酸银乙醇溶液3遍,使其浸渍填充到薄膜孔隙中,再涂布质量百分浓度为5%的氯化亚锡乙醇水溶液2次,使硝酸银原位还原为纳米银粒子填充薄膜孔隙, 在150℃下烘干,测得薄膜孔隙率为18%。
纳米银复合氧化锡形成:将镀膜玻璃基体加热到300℃,在300-450℃时升温速度降低到3-5℃/min,使填充的银盐高温完全分解为纳米银并包覆氧化锡,最后在500℃高温下烧结30分钟,使有机物完全分解,并使氧化锡结晶长大形成透明导电薄膜,纳米银包覆氧化锡薄膜的孔隙率为9.6%,导电玻璃可见光透光率为81.7%,方块电阻为5.8Ω/□。
对照例1
如实施例1过程操作,不同是多孔氧化锡凝胶薄膜中填充银盐的乙醇水溶液,溶胶pH为1.1,得到氧化锡透明导电薄膜,测得可见光透光率为83.5%,方块电阻为83Ω/□。
对照例2
如实施例2过程操作,不同是是多孔氧化锡凝胶薄膜中填充银盐的乙醇水溶液,溶胶pH为1.1,得到氧化锡透明导电薄膜,测得可见光透光率为85.7%,方块电阻为96Ω/□。
对照例2
如实施例3过程操作,不同的是多孔氧化锡凝胶薄膜中填充银盐的乙醇水溶液,溶胶pH为1.1,得到氧化锡透明导电薄膜,测得可见光透光率为85.7%,方块电阻825Ω/□。
Claims (5)
1.一种纳米银复合氧化锡透明导电薄膜的制备方法,其特征是在溶胶-凝胶法制备的氧化锡导电薄膜孔隙中填充可溶性银盐和亚锡盐,原位还原生成纳米银粒子,高温烧结得到纳米银复合高透光率低方块电阻氧化锡透明导电薄膜,纳米银复合氧化锡透明导电薄膜的化学组成为:AgxSnO2-yFy ,其中, x=0.01-0.1,y =0-0.6,采取的技术方案包括在太阳电池玻璃基体上涂覆二氧化硅过渡层、掺氟氧化锡纳米溶胶制备、掺氟氧化锡凝胶薄膜制备、多孔氧化锡凝胶薄膜孔隙填充、纳米银复合氧化锡透明导电薄膜形成五部分。
2.如权利要求1所述纳米银复合氧化锡透明导电薄膜的制备方法,其特征是掺氟氧化锡纳米溶胶制备方法为:
(1)向四氯化锡水溶液中加入氨水使锡盐水解,将形成的沉淀洗涤至无氯离子;
(2)将水合氧化锡沉淀物悬浮在去离子水中,加入含氟掺杂剂氟化铵或氢氟酸,再加入饱和草酸水溶液,使水合氧化锡沉淀在50-60℃下完全胶溶,生成掺氟氧化锡纳米溶胶的pH为0.8-1.5,掺氟氧化锡纳米溶胶的组成摩尔比为Sn(OH)4:F:H2C2O4=1:0-0.6:0.1-0.4;
(3)向掺氟氧化锡纳米溶胶中加入聚氨酯乳液,使其质量百分浓度为0.01%-0.2%,以改善掺氟氧化锡溶胶稳定性、涂布均匀性和防止膜层干燥时开裂,掺氟氧化锡纳米溶胶中二氧化锡质量百分浓度为4%-5%。
3.如权利要求1所述纳米银复合氧化锡透明导电薄膜的制备方法,其特征是掺氟氧化锡凝胶薄膜制备方法是在太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶2-3遍,使凝胶薄膜厚度为400-800nm,在150℃下烘干得到掺氟氧化锡凝胶薄膜,掺氟氧化锡粒径为10-15nm,掺氟氧化锡凝胶薄膜孔隙率为20%-30%。
4.如权利要求1所述纳米银复合氧化锡透明导电薄膜的制备方法,其特征是多孔氧化锡凝胶薄膜孔隙填充方法是在掺氟氧化锡多孔凝胶薄膜上涂布可溶性银盐乙醇水溶液2-3次,使可溶性银盐浸渍填充到薄膜孔隙中,再涂布亚锡盐的乙醇水溶液,使可溶性银盐原位还原为纳米银粒子,控制原料的摩尔比为(Sn4++ Sn2+):F:Ag:Sn2+ =1:0-0.6:0.01-0.1:0.01-0.1,在150℃下烘干,氧化锡凝胶薄膜孔隙率为10%-15%,所述可溶性银盐是硝酸银、氨基磺酸银、乙酸银和水杨酸银,所述亚锡盐是氯化亚锡、硝酸亚锡和有机酸亚锡盐。
5.如权利要求1所述纳米银复合氧化锡透明导电薄膜的制备方法,其特征是纳米银复合氧化锡透明导电薄膜形成方法是将镀膜玻璃基体加热到300℃,在300-450℃时升温速度降低到3-5℃/min,使填充的可溶性银盐高温完全分解为纳米银粒子,最后在500℃高温下烧结30分钟,使有机物完全分解和使氟原子掺杂形成透明导电薄膜,填充后氧化锡薄膜孔隙率为5%-10%,导电玻璃可见光透光率为81%-85%,方块电阻为1-5Ω/□。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610877043.7A CN106374010B (zh) | 2016-10-09 | 2016-10-09 | 一种纳米银复合氧化锡透明导电薄膜的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610877043.7A CN106374010B (zh) | 2016-10-09 | 2016-10-09 | 一种纳米银复合氧化锡透明导电薄膜的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106374010A CN106374010A (zh) | 2017-02-01 |
CN106374010B true CN106374010B (zh) | 2017-07-28 |
Family
ID=57896226
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610877043.7A Expired - Fee Related CN106374010B (zh) | 2016-10-09 | 2016-10-09 | 一种纳米银复合氧化锡透明导电薄膜的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106374010B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108393494B (zh) * | 2018-03-05 | 2020-01-03 | 东南大学 | 一种锡基多孔电吸附除砷材料及其制备方法和应用 |
CN108461605B (zh) * | 2018-06-13 | 2019-06-25 | 浙江西溪玻璃有限公司 | 一种led光电玻璃基板 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1331598C (zh) * | 2004-05-17 | 2007-08-15 | 中国科学院大连化学物理研究所 | 一种在硅基材料上原位组装高分散纳米银粒子的方法 |
US7655595B2 (en) * | 2006-06-02 | 2010-02-02 | United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Sol-gel based oxidation catalyst and coating system using same |
CN102683050B (zh) * | 2012-05-04 | 2014-11-19 | 温州宏丰电工合金股份有限公司 | 纳米Ag-SnO2电接触复合材料的制备方法 |
CN105036109B (zh) * | 2015-06-26 | 2017-03-22 | 上海纳旭实业有限公司 | 一种多级孔碳材料负载纳米银复合功能材料的制备方法 |
-
2016
- 2016-10-09 CN CN201610877043.7A patent/CN106374010B/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN106374010A (zh) | 2017-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106477914B (zh) | 一种复合透明导电薄膜玻璃的制备方法 | |
Qi et al. | Synthesis of NiO and NiO/TiO2 films with electrochromic and photocatalytic activities | |
Zhao et al. | Optical and electrochemical properties of Cu-doped NiO films prepared by electrochemical deposition | |
Xie et al. | Fast fabrication of a WO 3· 2H 2 O thin film with improved electrochromic properties | |
CN103227240B (zh) | 一种基于龟裂模板法制备多孔金属薄膜透明导电电极的方法 | |
CN101576695A (zh) | Wo3电致变色薄膜制备方法 | |
CN103744246B (zh) | 一种镜面反射型电致变色器件及其制备方法 | |
CN105859151B (zh) | 一种喷涂法制备大面积多孔电致变色薄膜的方法 | |
CN103186004A (zh) | 具有纳米电致变色材料结构的电致变色装置 | |
Kumara et al. | Preparation of fluoride-doped tin oxide films on soda–lime glass substrates by atomized spray pyrolysis technique and their subsequent use in dye-sensitized solar cells | |
CN112255855B (zh) | 一种安全环保高性能的电致变色薄膜及其制备方法 | |
CN106158997B (zh) | 一种掺杂氧化锡透明导电薄膜的制备方法 | |
CN203732850U (zh) | 一种镜面反射型电致变色器件 | |
Moharam et al. | Potentiostatic deposition of Cu2O films as p-type transparent conductors at room temperature | |
CN106374010B (zh) | 一种纳米银复合氧化锡透明导电薄膜的制备方法 | |
CN103172274A (zh) | 一种氧化镍/聚苯胺复合电致变色薄膜的制备方法 | |
CN102157575A (zh) | 新型多层膜结构的透明导电氧化物薄膜及其制备方法 | |
CN103614712B (zh) | 溶胶-凝胶法制备Sb、Ce共掺杂SnO2中间层的方法 | |
Gao et al. | Improved electrochromic performance of nickel oxide porous films by regulating their semiconductor type by titanium doping | |
CN1868948B (zh) | 铟锡氧化物前驱物浆料制备和ito薄膜制备方法 | |
CN202650582U (zh) | 一种新型的导电玻璃纤维材料 | |
KR20100006991A (ko) | 나노로드 층을 구비한 fto 투명 전도막 | |
CN109360691A (zh) | 一种掺杂氧化锌透明导电薄膜的制备方法 | |
CN109524170A (zh) | 一种石墨烯和氟共掺杂氧化锡透明导电薄膜的制备方法 | |
Shahizuan et al. | Influence of pH solution on the electrodeposition of tungsten oxide (WO3) films onto indium tin oxide (ITO)-glass substrate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170728 Termination date: 20191009 |