CN103824898A - 基于溶液法实现的自组装无电沉积制备铜铟镓硒三维纳米结构阵列 - Google Patents
基于溶液法实现的自组装无电沉积制备铜铟镓硒三维纳米结构阵列 Download PDFInfo
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- 239000011733 molybdenum Substances 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 230000003647 oxidation Effects 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 238000009415 formwork Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- SJVIFVURCJFNAV-UHFFFAOYSA-M P(=O)([O-])(O)O.[O-2].[Al+3] Chemical compound P(=O)([O-])(O)O.[O-2].[Al+3] SJVIFVURCJFNAV-UHFFFAOYSA-M 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001338 self-assembly Methods 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 2
- -1 gallium ions Chemical class 0.000 abstract 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- 229910001449 indium ion Inorganic materials 0.000 abstract 1
- 150000003346 selenoethers Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical class [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002789 length control Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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Abstract
一种自组装无电沉积制备铜铟镓硒三维纳米结构阵列的制备方法,通过将背面溅射有金属钼四周带铝支撑的多孔氧化铝模板作为CIGS生长基底,浸入以铜、铟、镓和硒离子的混合液作为铜铟镓硒生长液中使得铜铟镓硒在CIGS生长基底上自组装生长,经退火后得到三维纳米结构的CIGS材料。本发明丰富了纳米结构CIGS的制备方法,为以后进一步制备高效率,大面积,低功耗,低成本的纳米太阳能电池和p-n结器件研究提供了材料支持。制备方法相对简单,不需要需昂贵的真空设备,对周围环境没有特殊要求,适宜工业普及。
Description
技术领域
本发明涉及的是一种太阳能电池材料技术领域的纳米材料,具体是一种适用于纳米结构的p-n结太阳能电池的基于溶液法实现的自组装无电沉积制备铜铟镓硒三维纳米结构阵列。
背景技术
化合物半导体黄铜矿铜铟镓硒是制备薄膜太阳能电池的理想材料。它有较高的可见光光吸收系数,可调的带隙宽度,长期的稳定性、可靠性、高温特性和弱光特性。铜铟镓硒目前-实验室最高转换效率记录超过了20%。然而,高转换效率的CIGS薄膜电池是由真空技术-共蒸发方法制备的CIGS多晶薄膜作为吸收层来实现的,但由于共蒸发工艺所需要昂贵的设备系统、材料利用率不高等特点不适合做大规模的推广。
近二三十年来,铜铟镓硒的研究者们一直在追求探索高效、低成本、可控的方法合成铜铟镓硒材料,并研究其相应物理化学性质,以此推动铜铟镓硒材料电池的发展。金属预制层硒化法、电化学沉积技术、喷雾热解方法、量子点丝网印刷及旋涂法,微粒沉积技术、气相输运技术、机械化学等方法都被用来合成CIGS(铜铟镓硒)材料。但是,许多非真空工艺在降低成本的可以合成CIGS材料,其对应光伏器件转换效率不是很高
由于共蒸发法设备及制备成本高制约了铜铟镓硒薄膜太阳能电池的广泛应用,因此,寻找低成本、低功耗、环境友好的制备铜铟镓硒薄膜电池一直是研究的热点。在制备铜铟镓硒材料的多种方法中,溶液法被普遍认为是一种极具潜力的制备铜铟镓硒的方法,最有可能代替以真空设备为基础的共蒸发法,相对于共蒸发法,溶液法具有环境要求少,简单易操作性,高效的沉积速率,设备及材料成本低,具有大规模制备的商业潜力和可行性。
同时,近年来,研究过程中纳米结构的太阳能电池对比平板薄膜太阳能电池有着巨大的优势,比如更高的光吸收光俘获特性,少的能量损失,好的载流子输运特性等,都吸引着研究者的广泛关注和研究。
经过对现有技术的检索发现,中国专利文献号CN101700872A,公开日2010.05.05,公开了一种铜铟镓硒纳米线阵列及其制备方法。该技术是在玻璃或硅片基底上制备金属电极层后,利用有序纳米模板做生长掩膜在衬底上的金属电极上电沉积制备有序的纳米线结构铜铟镓硒P型吸收层材料阵列。并通过化学腐蚀或物理刻蚀的方法从上至下部分去除模板,露出纳米线阵列,该阵列可用于与N型窗口层及金属电极组成具有光电转换性能的异质结。但该技术去除模板相对复杂,采用电沉积成本高,对制备的CIGS阵列形貌不能很好的控制。
发明内容
本发明针对现有技术存在的上述不足,提出一种基于溶液法实现的自组装无电沉积制备铜铟镓硒三维纳米结构阵列,其形貌可根据氧化铝模板的孔径大小和溅射金属钼层的厚度来实现可调。本发明丰富了纳米结构CIGS的制备方法,为以后进一步制备高效率,大面积,低功耗,低成本的纳米太阳能电池和p-n结器件研究提供了材料支持。制备方法相对简单,不需要需昂贵的真空设备,对周围环境没有特殊要求,适宜工业普及。
本发明是通过以下技术方案实现的:
本发明涉及一种自组装无电沉积制备铜铟镓硒三维纳米结构阵列的制备方法,将背面溅射有金属钼四周带铝支撑的多孔氧化铝模板作为CIGS生长基底,浸入以铜、铟、镓和硒离子的混合液作为铜铟镓硒生长液中使得铜铟镓硒在CIGS生长基底上自组装生长,经退火去除模板后得到三维纳米结构的CIGS材料。
所述的金属钼四周带铝支撑的多孔氧化铝模板包括:低场草酸氧化铝模板和高场磷酸氧化铝模板。
所述的铜铟镓硒生长液是指:按Cu2+:SeO3 2-=3:10~1:2,In3+:Ga3+=1:5~4:5,Cu2+:(In3++Ga3+)=7:10~5:6,的摩尔比例,将CuCl2,InCl3,CaCl3,H2SeO2溶液加入到电阻率为18MΩ·cm的去离子水中,经充分搅拌,并用NaOH溶液调节pH值至2.0~2.3,配置成铜铟镓硒生长液。
所述的CIGS生长基底是指:通过两步阳极氧化法制备出四周带铝支撑的多孔的纳米氧化铝模板,接着利用磁控溅射方法,在阳极氧化铝的背面溅射一层金属钼。
所述的两步阳极氧化法的具体过程为:将经过电化学抛光的铝片进行一次阳极氧化后去除凹坑,并重复进行一次阳极氧化,最后去除阻碍层后得到低场草酸氧化铝模板或高场磷酸氧化铝模板。
所述的铝片是指:剪裁成直径为2cm的纯铝圆片,该铝片放入丙酮浸泡半小时以去除表面的油脂,并经过超声清洗5分钟,最后用去离子水冲洗并干燥。
所述的电化学抛光是指:将铝片放入含有体积比为1:4的高氯酸和乙醇混合溶液的夹具中,在10V恒压下电化学抛光3-5分钟,抛光后的铝片表面粗糙度降低。
所述的夹具为圆柱形结构,直径为2cm,上端的开口直径为1.7cm,下端封闭。
所述的阳极氧化是指:草酸模板的低场氧化或磷酸模板的高场氧化,其中:草酸模板的低场氧化是指:在15℃环境下采用40V的阳极电压在0.3M/L浓度的草酸溶液中一次腐蚀2小时;磷酸模板的高场氧化在-5℃环境下采用195V的阳极电压在0.25M/L浓度的磷酸溶液一次腐蚀100秒。
所述的去除凹坑是指:采用混合溶液浸泡以消除铝片表面上的周期性凹坑,具体为:采用含有6wt.%的磷酸和1.8wt.%的铬酸的混合溶液,在60℃环境下浸泡4小时。
所述的去除阻碍层是指:将完成两次阳极氧化后的铝片置于磷酸溶液中,在35-45℃环境下浸泡40分钟,具体为:对于低场草酸氧化铝模板需要在35℃下浸泡40分钟;对于高场磷酸氧化铝模板需要在45℃下浸泡40分钟。
所述的磷酸溶液的浓度为5wt.%。
所述的完成两次氧化后的铝片优选为在其背面滴加体积比为3:1的饱和硫酸铜和盐酸的混合溶液以去除背面剩余的铝。
所述的磁控溅射方法的具体过程为:将本底真空抽到10-3pa.以下,功率调至30-100w,溅射2-20分钟,靶材采用高纯的钼,溅射的钼在多孔氧化铝模板上形成了一层多孔的金属钼层,可以根据溅射时间的长短调控金属钼层的孔径。
所述的退火是指:将自组装生长后的CIGS生长基底放入真空炉中,在450-600℃,1.0-3Pa以下退火30分钟。
所述的去除模板的方法具体过程为:将退火后的样品放入5wt%的磷酸溶液中浸泡50分钟,去除模板,获得独立的纳米结构阵列。
本发明涉及上述方法制备得到的铜铟镓硒三维纳米结构阵列,其中:基于低场草酸氧化铝模板制备的铜铟镓硒三维纳米结构阵列的外孔径为70-120nm,内孔径为可调控的0-70nm;基于高场磷酸氧化铝模板制备的铜铟镓硒三维纳米结构阵列的外孔径200-275nm,内孔径为可调控的0-200nm。
技术效果
与现有技术相比,本发明的优点是:1)生长过程中不引进其它不利元素杂质,对铜铟镓硒的制备不产生不利影响;2)无需特殊气氛环境,工艺简单,操作方便,长短可根据时间的长短控制,30分钟就可以生长到1μm-1.5μm;3)在周围气环境下生长铜铟镓硒可以有更高的生长速度,因此适用于大面积、低成本的制备高性能铜铟镓硒材料。4)生长的纳米结构的铜铟镓硒成分可以根据配置溶液的摩尔配比来调节,这样可以制备出不同能带宽度的铜铟镓硒材料。5)制备的纳米结构铜铟镓硒阵列的参数可以根据采用不同孔径的氧化铝模板和溅射钼层的时间来控制。6)去除模板简单容易。7)采用无电沉积,成本低。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
本实施例包括以下步骤:
1、用CuCl2,InCl3,CaCl3,和H2SeO2溶液按照Cu2+:In3+:Ga3+:SeO3 2=1:3:4:2的摩尔比例配制原始混合溶液。
2、将原始混合溶液充分均匀搅拌,用NaOH溶液调节溶液的pH值至2.0,得到铜铟镓硒的生长液。
3、用两步阳极氧化制备的高场磷酸氧化铝模板作为基底,直径为20nm,用磁控溅射的方法溅射一层金属钼,本底真空为4×1.0-4Pa,工作气压为12Mtorr,功率为30w,溅射时间4分钟,这样作为生长铜铟镓硒纳米阵列的基底。
4、室温下,将步骤三做好的基底放入,pH值为2.0的铜铟镓硒生长液中。生长30分钟。接着将生长后的样品,取出后用去离子水冲洗并用一定流速的氮气吹干。
5、将得到的样品,放入管式炉中,450℃退火半小时。这样就得到了致密的纳米结构的铜铟镓硒阵列。
将样品放入5wt%的磷酸溶液中浸泡50分钟,去除模板,获得独立的纳米结构阵列。
实施例2
1、将CuCl2,InCl3,CaCl3,和H2SeO2溶液按照Cu2+:In3+:Ga3+:SeO3 2=1:2:4:2的摩尔比例配制原始混合溶液。
2、将原始混合溶液充分均匀搅拌,用NaOH溶液调节溶液的pH值至2.1,得到铜铟镓硒的生长液。
3、用两步阳极氧化制备的高场磷酸氧化铝模板作为基底,直径为250nm,用磁控溅射的方法溅射一层金属钼,本底真空为3×1.0-4Pa,工作气压为8mtorr,功率为50w,溅射时间20分钟,这样作为生长铜铟镓硒纳米阵列的基底。
4、室温下,将步骤三做好的基底放入,pH值为2.1的铜铟镓硒生长液中。生长40分钟。接着将生长后的样品,取出后用去离子水冲洗并用一定流速的氮气吹干。
5、将得到的样品,放入管式炉中,500℃退火20分钟。这样就得到了致密的纳米结构的铜铟镓硒阵列。
6、将样品放入5wt%的磷酸溶液中浸泡50分钟,去除模板,获得独立的纳米结构阵列。实施例3
1、用CuCl2,InCl3,CaCl3,和H2SeO2溶液按照Cu2+:In3+:Ga3+:SeO3 2=1:3:4:3的摩尔比例配制原始混合溶液。
2、将原始混合溶液充分均匀搅拌,用NaOH溶液调节溶液的pH值至2.2,得到铜铟镓硒的生长液。
3、用两步阳极氧化制备的高场磷酸氧化铝模板作为基底,直径为190nm,用磁控溅射的方法溅射一层金属钼,本底真空为6×1.0-4Pa,工作气压为10mtorr,功率为80w,溅射时间10分钟,这样作为生长铜铟镓硒纳米阵列的基底。
4、室温下,将步骤三做好的基底放入,pH值为2.2的铜铟镓硒生长液中。生长5分钟。接着将生长后的样品,取出后用去离子水冲洗并用一定流速的氮气吹干。
5、将得到的样品,放入管式炉中,550℃退火半小时。这样就得到了致密的纳米结构的铜铟镓硒阵列。
将样品放入5wt%的磷酸溶液中浸泡50分钟,去除模板,获得独立的纳米结构阵列。
实施例4
1、用CuCl2,InCl3,CaCl3,和H2SeO2溶液按照Cu2+:In3+:Ga3+:SeO3 2=1:2:3:2的摩尔比例配制原始混合溶液。
2、将原始混合溶液充分均匀搅拌,用NaOH溶液调节溶液的pH值至2.2,得到铜铟镓硒的生长液。
3、用两步阳极氧化制备的低场草酸氧化铝模板作为基底,直径为70nm,用磁控溅射的方法溅射一层金属钼,本底真空为8×1.0-4Pa,工作气压为12mtorr,功率为100w,溅射时间3分钟,这样作为生长铜铟镓硒纳米阵列的基底。
4、室温下,将步骤三做好的基底放入,pH值为2.3的铜铟镓硒生长液中。生长30分钟。接着将生长后的样品,取出后用去离子水冲洗并用一定流速的氮气吹干。
5、将得到的样品,放入管式炉中,600℃退火30分钟。这样就得到了致密的纳米结构的铜铟镓硒阵列。
将样品放入5wt%的磷酸溶液中浸泡50分钟,去除模板,获得独立的纳米结构阵列。
Claims (9)
1.一种自组装无电沉积制备铜铟镓硒三维纳米结构阵列的制备方法,其特征在于,将背面溅射有金属钼四周带铝支撑的多孔氧化铝模板作为CIGS生长基底,浸入以铜、铟、镓和硒离子的混合液作为铜铟镓硒生长液中使得铜铟镓硒在CIGS生长基底上自组装生长,经退火后得到三维纳米结构的CIGS材料;
所述的金属钼四周带铝支撑的多孔氧化铝模板包括:低场草酸氧化铝模板和高场磷酸氧化铝模板。
2.根据权利要求1所述的方法,其特征是,所述的铜铟镓硒生长液是指:按Cu2+:SeO3 2-=3:10~1:2,In3+:Ga3+=1:5~4:5,Cu2+:(In3++Ga3+)=7:10~5:6,的摩尔比例,将CuCl2,InCl3,CaCl3,H2SeO2溶液加入到电阻率为18MΩ·cm的去离子水中,经充分搅拌,并用NaOH溶液调节pH值至2.0~2.3,配置成铜铟镓硒生长液。
3.根据权利要求1所述的方法,其特征是,所述的CIGS生长基底是指:通过两步阳极氧化法制备出四周带铝支撑的多孔的纳米氧化铝模板,接着利用磁控溅射方法,在阳极氧化铝的背面溅射一层金属钼。
4.根据权利要求3所述的方法,其特征是,所述的两步阳极氧化法的具体过程为:将经过电化学抛光的铝片进行一次阳极氧化后去除凹坑,并重复进行一次阳极氧化,最后去除阻碍层后得到低场草酸氧化铝模板或高场磷酸氧化铝模板;
所述的阳极氧化是指:草酸模板的低场氧化或磷酸模板的高场氧化,其中:草酸模板的低场氧化是指:在15℃环境下采用40V的阳极电压在0.3M/L浓度的草酸溶液中一次腐蚀2小时;磷酸模板的高场氧化在-5℃环境下采用195V的阳极电压在0.25M/L浓度的磷酸溶液一次腐蚀100秒。
5.根据权利要求4所述的方法,其特征是,所述的去除凹坑是指:采用混合溶液浸泡以消除铝片表面上的周期性凹坑,具体为:采用含有6wt.%的磷酸和1.8wt.%的铬酸的混合溶液,在60℃环境下浸泡4小时。
6.根据权利要求4所述的方法,其特征是,所述的去除阻碍层是指:将完成两次阳极氧化后的铝片置于磷酸溶液中,在35-45℃环境下浸泡40分钟,具体为:对于低场草酸氧化铝模板需要在35℃下浸泡40分钟;对于高场磷酸氧化铝模板需要在45℃下浸泡40分钟。
7.根据权利要求3所述的方法,其特征是,所述的磁控溅射方法的具体过程为:将本底真空抽到10-3pa以下,功率调至30-100w,溅射2-20分钟,靶材采用高纯的钼,溅射的钼在多孔氧化铝模板上形成了一层多孔的金属钼层,可以根据溅射时间的长短调控金属钼层的孔径。
8.根据权利要求1所述的方法,其特征是,所述的退火是指:将自组装生长后的CIGS生长基底放入真空炉中,在450-600℃,1.0-3Pa的条件下退火30分钟。
9.一种根据上述任一权利要求所述方法制备得到的铜铟镓硒三维纳米结构阵列,其阵列外孔径为70-120nm以及200-275nm,内孔径为0-200nm。
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