CN115432939A - 高性能三氧化钨/钨酸铋薄膜及其制备方法 - Google Patents
高性能三氧化钨/钨酸铋薄膜及其制备方法 Download PDFInfo
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- tungsten trioxide
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 167
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 135
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000005540 biological transmission Effects 0.000 claims abstract description 7
- 230000031700 light absorption Effects 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 26
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 239000010937 tungsten Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
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- 230000008021 deposition Effects 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
本发明涉及一种高性能三氧化钨/钨酸铋薄膜及其制备方法,高性能三氧化钨/钨酸铋薄膜,包括钨酸铋薄膜,所述钨酸铋薄膜下依次为三氧化钨层和氟掺杂二氧化锡FTO导电玻璃,所述钨酸铋薄膜厚度为50‑500纳米,所述三氧化钨层厚度为10‑100纳米;所述钨酸铋薄膜为吸光材料,所述三氧化钨层为电子传输层。本发明采用刮涂法制备三氧化钨层结合电化学沉积法沉积铋,经退火后得到的高性能三氧化钨/钨酸铋薄膜,制备过程简单且有较高的光电转换性能。本发明方法简便环保,制备的高性能钨酸铋薄膜结构有效地促进了电荷分离与传输,并具有良好的可见光电转换性能。
Description
技术领域
本发明涉及无机非金属材料制造技术领域,更具体地说,涉及一种高性能三氧化钨/钨酸铋薄膜及其制备方法。
背景技术
全球能源危机和环境污染问题是可持续性发展面临的一个极大挑战。随着科技的发展,太阳能光电分解水制氢技术有望成为解决这些问题的一个重要的技术手段。光电分解水制氢可选择的材料有很多,例如常见的半导体金属氧化物、氮化物或硫化物。在可见光照射下,半导体能够激发、分离电荷,进一步发生氧化还原反应来制备氢气。钨酸铋(Bi2WO6)作为良好的可见光响应材料,它具有无毒、价廉、带隙合适(~2.8eV)、性质稳定等优点,通常可以作为分解水制氢***中的光阳极材料。此外,钨酸铋材料在降解污染物、太阳能电池等领域也有广泛应用。光电化学应用时对薄膜材料需求较多。
目前钨酸铋薄膜制备方法有水热法、磁控溅射法、溶胶-凝胶法、电化学沉积法、旋涂法、低温等离子体法等。专利CN202011604122.3以硝酸铋的乙二醇溶液与钨酸钠溶液混合、搅拌后用水热法制备得到钨酸铋粉末。专利CN201910672860.2以钨酸钠和草酸铵为前驱体,通过水热法在FTO导电玻璃基底上原位生长得到纳米板状三氧化钨薄膜,进一步滴加硝酸铋酸性水溶液、高温煅烧得到六角柱型三氧化钨/钨酸铋薄膜。专利CN201410834880.2以钨层为基底与含铋离子的酸性溶液通过水热沉积形成钨酸铋薄膜。专利201510241945.7先以钨酸钠溶液和硝酸铋溶液在弱酸性下(pH 5-7)水热反应得到钨酸铋粉末,并用干法压制、高温烧结制得靶材,经磁控溅射可在石英基底上制得钨酸铋薄膜。专利CN201710113896.8将钨酸钠和硝酸铋分别溶于乙二醇,经过混合、陈化后得到无色澄清溶液,用旋涂法和逐层退火工艺在FTO上制备钨酸铋薄膜。专利CN201510201504.4用硝酸调节pH并以碘化钾和硝酸铋粉末制得溶液为电解液,用三电极电化学沉积得到碘氧铋纳米片薄膜,进一步在钨酸钠水溶液中经100-140摄氏度水热反应2-12小时,并在500-600摄氏度的空气氛围焙烧1-3小时,最终得到钨酸铋纳米薄膜。专利CN201711021098.9以钨酸钠溶液、铋板和石墨分别作为电解质、阳极和阴极,常温恒电压下在铋板上生长钨酸铋薄膜。专利CN201811097688.4采用钨酸铵,硝酸铋,去离子水,乙酰丙酮,硝酸为原料制备出稳定的前驱体溶液,用旋涂法将其旋涂到普通玻璃基底上,制备得到钨酸铋薄膜。专利CN201910672865.5通过水热法在FTO上生长三氧化钨纳米板,随后滴加硝酸铋的水溶液,经过干燥、高温煅烧得到钨酸铋纳米片。最后以空气、氧气、氮气或者氢气为反应气体,采用低温等离子体技术进行处理得到含氧缺陷型的钨酸铋薄膜。
上述制备钨酸铋的方法中水热法往往需要较长时间处理过程,所用电沉积法通常施加电压过高,浪费能量;而所制备的钨酸铋光阳极薄膜由于掺杂程度低、电荷分离和转移速度低,表面催化氧化的性能低。
发明内容
本发明要解决的技术问题在于,提供一种高性能三氧化钨/钨酸铋薄膜及其制备方法,该薄膜结晶质量高、与衬底附着性好、光电性能优异,制备过程简单且有较高的光电转换性能。
本发明解决其技术问题所采用的技术方案是:构造一种高性能三氧化钨/钨酸铋薄膜,包括钨酸铋薄膜,所述钨酸铋薄膜下依次为三氧化钨层和氟掺杂二氧化锡FTO导电玻璃,所述钨酸铋薄膜厚度为50-500纳米,所述三氧化钨层厚度为10-100纳米;所述钨酸铋薄膜为吸光材料,所述三氧化钨层为电子传输层。
本发明还提供了一种高性能三氧化钨/钨酸铋薄膜的制备方法,包括以下步骤:
S1、采用电化学沉积的方法在在清洗干净、干燥的FTO导电衬底上恒电压沉积一层铋膜,并在铋膜上刮涂一层均匀的钨酸溶液,得到三氧化钨/铋薄膜;
S2、将钨酸溶液先刮涂到FTO导电玻璃衬底上,并在160-240摄氏度的恒温加热台上进行加热10-20分钟,冷却至室温后得到非晶三氧化钨层,再用电化学恒电位法在上述三氧化钨薄膜上沉积一层多晶铋膜,得到三氧化钨/铋薄膜;
所述步骤S1和S2可相互替换,择一即可;
S3、将所述三氧化钨/铋薄膜在空气中自然干燥后,在500-700摄氏度下高温退火2-12小时,得到氧化物薄膜,自然冷却后,所述氧化物薄膜置于0.2-3摩尔/升的氢氧化钾溶液中浸泡4-16小时,蒸馏水冲洗、自然晾干后,得到三氧化钨/钨酸铋薄膜。
按上述方案,在所述步骤S2中,以所述附着有非晶三氧化钨的导电玻璃作为阴极,5-10毫摩尔/升的硝酸铋溶液作为电解液,铂片作为对电极,饱和甘汞电极作为参比电极,在三氧化钨膜的导电玻璃上以-0.3V到-0.6V下恒电压电化学沉积一层金属铋,控制铋与钨的元素比例1:1到2:1,经过电沉积得到三氧化钨/铋薄膜。
按上述方案,所述步骤S1中,所述FTO导电玻璃基片的清洗具体过程为:双氧水-氨水-蒸馏水,三者体积比:1:1:1,蒸馏水分别超声洗涤2-3小时,然后在空气中自然干燥。
按上述方案,所述步骤S2中,所述金属铋制备过程中的沉积电压为-0.4V,所述金属铋的电荷量为0.33库仑,控制铋/钨的元素比例6/4。
按上述方案,采用刮涂7.5微升,0.1摩尔/升的钨酸溶液。
本发明所使用的化学试剂都为分析纯,购自上海国药化学试剂有限公司。本发明所用的表征手段:X-射线衍射仪(XRD,布鲁克D8 Advance,铜靶)证实薄膜的晶体结构为钨酸铋或三氧化钨/钨酸铋,用扫描电镜(SEM,SU 8200,Hitachi)检测薄膜表面的平整度和厚度,用紫外漫反射光谱(UV-vis,SolidSpec-2600,Shimadzu)表征薄膜的可见光吸收性能,用X射线光电子能谱(XPS,Thermo Fisher Scientific K-Alpha)研究组成薄膜的各元素电子特性,用瞬态表面光电压曲线(TSPV)研究光生电荷的分离和复合,同时用光电流-电压极化曲线证明光电极的性能。
实施本发明的高性能三氧化钨/钨酸铋薄膜及其制备方法,具有以下有益效果:
1、本发明采用刮涂法结合电化学沉积法,操作简单,成本低廉,所沉积的金属铋膜厚度可控、均匀,并能大面积制备;
2、本发明采用刮涂法在FTO导电玻璃上刮涂钨酸溶液经200摄氏度恒温加热后制备的底层三氧化钨层起到改变上层钨酸铋晶面取向和电子传输的作用,制备方法简单,又能保证电荷的高效分离与传输,相较于一步法制备的钨酸铋薄膜光电性能提高5倍左右。
附图说明
下面将结合附图及实施例对本发明作进一步说明,附图中:
图1是本发明实施例1非晶钨酸薄膜的XRD图;
图2是本发明实施例1高性能三氧化钨/钨酸铋薄膜的XRD图;
图3是本发明实例1高性能三氧化钨/钨酸铋薄膜的SEM图;
图4是本发明实施例1、4的UV-vis图;
图5是本发明实施例1、4的XPS能谱图;
图6是本发明实施例2金属铋薄膜的XRD图;
图7是本发明实施例4钨酸铋薄膜的XRD图;
图8是本发明实施例4钨酸铋薄膜的SEM图;
图9是本发明实施例1、4的瞬态表面光电压图;
图10是本发明实施例1以铋/钨为6/4得到不同退火温度的J-V图;
图11是本发明实施例1以不同钨酸量、控制铋/钨为5/4、经过600摄氏度退火得到薄膜的J-V图;
图12是本发明实施例1以不同钨酸量、控制铋/钨为6/4、经过600摄氏度退火得到薄膜的J-V图;
图13是本发明实施例1以不同钨酸量、控制铋/钨为7/4、经过600摄氏度退火得到薄膜的J-V图;
图14是实施例1、4的J-V对比图;
图15是本发明三氧化钨/钨酸铋薄膜的层结构图。
具体实施方式
为了对本发明的技术特征、目的和效果有更加清楚的理解,现对照附图详细说明本发明的具体实施方式。
实施例1
如图15所示,本发明的高性能三氧化钨/钨酸铋薄膜,包括钨酸铋薄膜,钨酸铋薄膜下依次为一层三氧化钨层和氟掺杂二氧化锡(FTO)导电玻璃,钨酸铋薄膜厚度为50-500纳米的平面结构,三氧化钨层厚度为10-100纳米。钨酸铋薄膜为主要吸光材料,三氧化钨层为电子传输层。
溶胶-凝胶制备三氧化钨薄膜步骤如下:
S1、制备非晶的钨酸层,方法如下:
首先FTO导电玻璃基片的清洗具体过程为:双氧水-氨水-蒸馏水(1/1/1,V/V/V)、蒸馏水分别超声洗涤2-3小时,然后在空气中自然干燥。将钨酸粉末溶于过氧化氢溶液,经过超声分散30-60分钟得到浓度为0.1摩尔/升的透明钨酸溶液。将7.5微升钨酸溶液刮涂到干燥、干净的FTO导电玻璃基片(1厘米x3厘米)上,常温烘干得到薄膜。XRD衍射图如图1所示,仅在20-35度显示弥散的衍射峰,表明得到非晶的钨酸层。
S2、制备三氧化钨/铋薄膜,方法如下:
采用3电极方法电化学沉积金属铋,其中工作电极为步骤S1中得到的附有三氧化钨的FTO玻璃片,对电极为铂片,参比电极为饱和甘汞电极,电解液为5-10毫摩尔/升硝酸铋溶液(调节至pH~1),通过电化学工作站(辰华CHI-760E)在工作电极上施加一恒定电压为-0.4V(在-0.3~-0.6V内),三氧化钨衬底上逐渐出现黑色的金属铋,通过控制沉积时间,控制净电荷0.1-0.3库仑/平方厘米,如0.16库仑/平方厘米。
S3、制备三氧化钨/钨酸铋薄膜,方法如下:
将室温干燥后的三氧化钨/铋薄膜,置于马弗炉中,控制升温速率为每分钟10摄氏度至600摄氏度(范围为500-700摄氏度)退火6小时(范围为2-12小时),待其自然冷却至室温后,浸入0.2-3摩尔/升的氢氧化钾溶液中去除多余的三氧化钨杂质。
经过XRD如图2所示,表明主要衍射峰来自FTO(氟掺杂SnO2)和钨酸铋(Bi2WO6,卡片号:39-0256),且(200)衍射峰较强,说明有一定取向。而三氧化钨衍射峰(200)(~24度)虽然弱仍然存在,说明三氧化钨应该位于钨酸铋层下方被保护免于氢氧化钾腐蚀。SEM图(图3)表面所制备的三氧化钨/钨酸铋薄膜为平面结构,表面具有一些40-140纳米左右小颗粒;横截面图说明上层主要由钨酸铋、三氧化钨沉积在FTO基底上。图4中为薄膜的紫外可见吸收光谱图,其中入射光从FTO面进入,紫外部分先被FTO吸收,因此三氧化钨/钨酸铋的吸收主要位于300-450纳米之间,最大吸收强度为60%,薄膜的带隙约为2.78eV。图5中的三氧化钨/钨酸铋薄膜的XPS能谱说明薄膜中主要由Bi、W和O元素组成。
实施例2
与实施例1类似,采用3电极方法恒电位电沉积沉积金属铋薄膜,差别在于直接选择洁净的FTO导电玻璃为衬底作为工作电极。对电极为铂片,参比电极为饱和甘汞电极,电解液为5-10毫摩尔/升硝酸铋溶液(调节至pH~1),通过电化学工作站(辰华CHI-760E)在工作电极上施加一恒定电压为-0.4V(在-0.3~-0.6V内),FTO衬底上逐渐出现黑色的金属铋,通过控制沉积时间,控制净电荷0.16库仑/平方厘米。图6为FTO上所沉积的金属铋的XRD图,所有的衍射峰都可以归为金属铋(卡片号:85-1330)和FTO衬底。
实施例3
与实施例1类似,差别在于基底选择FTO/铋,溶胶凝胶法制备FTO/金属铋/三氧化钨薄膜。在铋膜上刮涂一层0.1摩尔/升的钨酸溶液,其体积为7.5微升。
实施例4
与实施例1类似,差别在于基底选择FTO/铋/三氧化钨,退火制备FTO/钨酸铋薄膜。实施例3中的薄膜经过室温干燥,放入升温速率为每分钟10摄氏度的马弗炉中500-700摄氏度退火2-12小时,马弗炉的升温速率为每分钟10摄氏度。待其自然冷却至室温后,浸入0.2-3摩尔/升的氢氧化钾溶液中去除多余的三氧化钨。最终得到钨酸铋薄膜。
XRD图(图7)中所有的衍射峰都来自FTO和钨酸铋(PDF卡片号为39-0526),并且不含三氧化钨。图4中Bi2WO6薄膜的紫外-可见图比三氧化钨/钨酸铋略低,可能是薄膜的厚度低;另外吸收峰也分布在300-450纳米之间,对应带隙约为2.80eV。图5中的钨酸铋的XPS能谱说明薄膜中主要含有Bi、W和O元素,而Sn元素源自未被薄膜覆盖部分的FTO基底。另外,图8为钨酸铋薄膜的SEM照片,其中表面仍然为平面结构,含有部分小颗粒尺寸约30-80纳米;横截面由钨酸铋和底层的FTO基底。
测试1
高性能FTO/三氧化钨/钨酸铋薄膜和FTO/钨酸铋薄膜的瞬态表面光电压测试。选择FTO/三氧化钨/钨酸铋薄膜,清除薄膜边缘部分氧化物作为连接导线部分,选择20-30微米厚度云母片作为绝缘层、另外一片FTO导电玻璃作为对电极。以4-6纳米的紫外激光(355纳米、60微焦/脉冲)脉冲激发所制备的薄膜,利用电压前置放大器和泰克4通道示波器(500兆赫兹)收集表面光电压信号。同样的方法可以测得FTO/钨酸铋薄膜的瞬态光电压信号。
图9中三氧化钨/钨酸铋的表面光电压曲线在激光脉冲之后,32微秒内迅速上升至2.7毫伏,然后逐渐衰减到零;而钨酸铋表面光电压先有一个负峰,可能源自界面缺陷或能级不匹配。钨酸铋表面光电压曲线,其光生电压约为0.4毫伏,响应时间为120微秒出现峰值。这说明三氧化钨/钨酸铋薄膜的光电响应更高。
测试2
系列高性能FTO/三氧化钨/钨酸铋薄膜和FTO/钨酸铋薄膜电极的光电化学性能。将两种薄膜制作成光电极,仅留测试部分暴露,其他部分通过绝缘硅橡胶密封保护。测试方法为三电极法,其中光电极为工作电极,铂丝为对电极,参比电极为汞/***,0.2-3摩尔/升氢氧化钾溶液为电解液,光源选择标准太阳光(AM 1.5,100毫瓦/平方厘米)。工作电极施加的电势通过公式E=E(参比)+0.059×pH转换为相对于可逆氢电极电势。通过线性伏安法,在电极上施加合适的电压,测试得到电极的极化曲线。
图10为实施例1中,铋/钨元素比为6/4时,得到三氧化钨/钨酸铋薄膜,经过不同的退火温度后,制成电极的极化曲线。其中600摄氏度为较好的退火温度。图11为实施例1中,铋/钨元素比为5/4时得到的极化曲线图,说明7.5微升量的光电活性较好;图12为实施例1中,铋/钨元素比为6/4时得到的极化曲线图,差异较为明显,说明7.5微升量的光电活性较好;图13为实施例1中,铋/钨元素比为7/4时得到的极化曲线图,说明7.5微升量的光电活性较好,但是电流密度显著降低。图14为实施例1中,铋/钨元素比为6/4时得到的三氧化钨/钨酸铋薄膜和实施例1和2中,铋/钨元素比为6/4得到的钨酸铋薄膜的极化曲线,说明三氧化钨/钨酸铋薄膜具有更好的光电活性。
上面结合附图对本发明的实施例进行了描述,但是本发明并不局限于上述的具体实施方式,上述的具体实施方式仅仅是示意性的,而不是限制性的,本领域的普通技术人员在本发明的启示下,在不脱离本发明宗旨和权利要求所保护的范围情况下,还可做出很多形式,这些均属于本发明的保护之内。
Claims (6)
1.一种高性能三氧化钨/钨酸铋薄膜,其特征在于,包括钨酸铋薄膜,所述钨酸铋薄膜下依次为三氧化钨层和氟掺杂二氧化锡FTO导电玻璃,所述钨酸铋薄膜厚度为50-500纳米,所述三氧化钨层厚度为10-100纳米,所述钨酸铋薄膜为吸光材料,所述三氧化钨层为电子传输层。
2.一种权利要求1所述的高性能三氧化钨/钨酸铋薄膜的制备方法,其特征在于,包括以下步骤:
S1、采用电化学沉积的方法在在清洗干净、干燥的FTO导电衬底上恒电压沉积一层铋膜,并在铋膜上刮涂一层均匀的钨酸溶液,得到三氧化钨/铋薄膜;
S2、将钨酸溶液先刮涂到FTO导电玻璃衬底上,并在160-240摄氏度的恒温加热台上进行加热10-20分钟,冷却至室温后得到非晶三氧化钨层,再用电化学恒电位法在上述三氧化钨薄膜上沉积一层多晶铋膜,得到三氧化钨/铋薄膜;
所述步骤S1和S2可相互替换,择一即可;
S3、将所述三氧化钨/铋薄膜在空气中自然干燥后,在500-700摄氏度下高温退火2-12小时,得到氧化物薄膜,自然冷却后,所述氧化物薄膜置于0.2-3摩尔/升的氢氧化钾溶液中浸泡4-16小时,蒸馏水冲洗、自然晾干后,得到三氧化钨/钨酸铋薄膜。
3.根据权利要求2所述的高性能三氧化钨/钨酸铋薄膜的制备方法,其特征在于,在所述步骤S2中,以所述附着有非晶三氧化钨的导电玻璃作为阴极,5-10毫摩尔/升的硝酸铋溶液作为电解液,铂片作为对电极,饱和甘汞电极作为参比电极,在三氧化钨膜的导电玻璃上以-0.3V到-0.6V下恒电压电化学沉积一层金属铋,控制铋与钨的元素比例1:1到2:1,经过电沉积得到三氧化钨/铋薄膜。
4.根据权利要求2所述的高性能三氧化钨/钨酸铋薄膜的制备方法,其特征在于,所述步骤S1中,所述FTO导电玻璃基片的清洗具体过程为:双氧水-氨水-蒸馏水,三者比例为体积比:1:1:1,蒸馏水分别超声洗涤2-3小时,然后在空气中自然干燥。
5.根据权利要求3所述的高性能三氧化钨/钨酸铋薄膜的制备方法,其特征在于,所述步骤S2中,所述金属铋制备过程中的沉积电压为-0.4V,所述金属铋的电荷量为0.33库仑,控制铋/钨的元素比例6/4。
6.根据权利要求2所述的高性能三氧化钨/钨酸铋薄膜的制备方法,其特征在于,所述步骤S2中,采用刮涂7.5微升,0.1摩尔/升的钨酸溶液。
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