CN108428753B - 半透明薄膜太阳电池及其制备方法 - Google Patents
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- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
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Abstract
本发明公开了一种半透明薄膜太阳电池及其制备方法，其中，该半透明薄膜太阳电池包括依次层叠的玻璃衬底、透明导电层、电子传输层、Sb2S3光吸收层、V2O5空穴传输层和背电极。本发明利用V2O5替代有机物作为薄膜太阳电池的空穴传输层，其能与Sb2S3光吸收层形成良好的能级匹配，而且在V2O5空穴传输层的制备过程中，可以有效去除Sb2S3光吸收层中的氧化物等杂质，进而提高基于Sb2S3材料为吸收层的半透明薄膜太阳电池的稳定性和器件效率。
Description
技术领域
本发明涉及光电材料与器件领域，尤其涉及一种半透明薄膜太阳电池及其制备方法。
背景技术
Sb2S3是一种V-Ⅵ族硫化物半导体，地壳中含量丰富、安全无毒，在光电转换器件、光催化等领域中应用广泛。我国锑矿储量和产量均居世界首位，而且分布范围很广，遍及湘、黔、云、桂等省，尤以湖南为盛。锑矿石是硫化物，其中主要以辉锑矿(Sb2S3)形式存在。Sb2S3较容易从锑矿石中得到，属正交晶系，空间群为Pbnm62，具有高度各向异性，带隙宽度适中(1.5-2.2eV)，覆盖了大部分可见光光谱，吸光系数较高(α＞105cm-1)，在弱光照明条件下具有很好的光电性能，因此在阴天或者室内可得到较好的光电转换效率，因此被视为最有希望得到广泛应用的太阳电池材料之一。
基于Sb2S3为吸收层的半透明太阳电池可以吸收光能转化为电能，为建筑物提供电能的同时能够让部分的可见光透过，保证室内采光；或与硅基、钙钛矿等电池进行叠层作顶电池，因此Sb2S3太阳电池逐渐被科研人员注意。Sb2S3薄膜的制备方法很多，主要集中在水浴法和热蒸发。水浴法制备方法简单，低温，但是其制备时间很长(几个小时)，还有很多参数需要设定(温度、时间、PH值和添加剂等)，导致重复性差，而且成膜不均匀、存在较多氧化物杂质；热蒸发制备的薄膜致密，成分均匀，但是各种方法制备的Sb2S3薄膜表面都会产生氧化物等杂质，使得电池电阻变大，载流子迁移率降低，进而严重恶化Sb2S3薄膜电池的性能。并且Sb2S3薄膜电池大都采用有机物作为空穴传输层，导致电池的稳定性较差，有些器件结构为了避免使用有机物，直接不使用空穴传输层而直接与电极相连，由于高背接触势垒问题，导致界面能级的不匹配，器件串联电阻大，短路电流低，从而转换效率不高。
发明内容
本发明旨在至少解决上述技术问题之一。
为此，本发明的目的在于提出一种半透明薄膜太阳电池及其制备方法，以提升阳极的功函数，降低阳极的方阻，形成良好的能级匹配，提升整体器件的空穴迁移率和稳定性。
为了实现上述目的，本发明实施例提出的一种半透明薄膜太阳电池包括依次层叠的玻璃衬底、透明导电层、电子传输层、Sb2S3光吸收层、V2O5空穴传输层和背电极。
优选地，所述透明导电层为ITO、FTO或AZO中的任一种。
优选地，所述电子传输层为TiO2、ZnO、CdS、In2S3或SnO2中的任一种。
优选地，所述电子传输层的厚度为10-80nm。
优选地，所述背电极为ITO或FTO。
优选地，所述背电极的厚度为100-1000nm。
优选地，所述Sb2S3光吸收层的厚度为100-2000nm，所述V2O5空穴传输层的厚度为1-50nm。
为了实现上述目的，本发明实施例提出的一种半透明薄膜太阳电池的制备方法包括以下步骤：
1)清洗导电玻璃，所述导电玻璃为ITO、FTO或AZO玻璃中的任一种；
2)在导电玻璃上沉积10-80nm的电子传输层，所述电子传输层为TiO2、ZnO、CdS、In2S3或SnO2中的任一种；
3)利用磁控溅射法、热蒸发法或化学水浴法在电子传输层上沉积100-2000nm的Sb2S3光吸收层，并将Sb2S3光吸收层在200-400℃下退火10-50min；
4)在退火处理后的Sb2S3光吸收层上依次旋涂H2O2和氨水，旋涂结束后将样品在50-200℃的加热平台上烘烤3-20min，随后转移至50-80℃的真空保温箱中保温10-60min；
5)将样品从真空保温箱中取出，在Sb2S3光吸收层上旋涂溶解有偏钒酸铵的稀氨水溶液，制得10-50nm的V2O5空穴传输层；
6)利用磁控溅射法在V2O5空穴传输层上沉积100-1000nm的背电极，所述背电极为ITO或FTO。
优选地，所述步骤4)中H2O2的浓度为20-30％，氨水的浓度为5-15％。
优选地，所述步骤5)中稀氨水的浓度为2-10％。
本发明提出的技术方案中，V2O5替代有机物作为薄膜太阳电池的空穴传输层，其能与Sb2S3光吸收层形成良好的能级匹配，而且在V2O5空穴传输层的制备过程中，可以有效去除Sb2S3光吸收层中的氧化物等杂质，进而提高基于Sb2S3材料为吸收层的半透明薄膜太阳电池的稳定性和器件效率。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图示出的结构获得其他的附图。
图1为本发明半透明薄膜太阳电池中各物质的真空能级匹配情况图；
图2为本发明实施例1的半透明透明太阳电池和没有空穴传输层的太阳电池的电流密度-电压特性曲线；
图3为本发明实施例1的半透明透明太阳电池和利用有机空穴传输层的太阳电池的电流密度-电压特性曲线；
图4为本发明中利用热蒸发法制备的光吸收层薄膜的紫外-可见吸收光谱图；
图5为本发明实施例2的半透明薄膜太阳电池的结构示意图。
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
(1)将方阻≤7Ω/□、透光率≥84％的ITO导电玻璃(深圳华南湘城科技有限公司)，预先切割成15mm×20mm的长方形薄片。将长方形薄片依次用去离子水、玻璃清洗剂、丙酮、酒精、去离子水超声清洗15分钟，然后用空气压缩机吹干待用。
(2)在待用的ITO导电玻璃上用KW-4A型号的旋涂仪旋涂电子传输层，如TiO2、ZnO、CdS、In2S3和SnO2中的任一种，请参照图1，这些电子传输层的能带均与Sb2S3光吸收层的能带匹配。
具体地，本实施例中，旋涂TiO2作为电子传输层，厚度为40nm。
(3)采用中国科学院沈阳科学仪器股份有限公司生产的JGP450型高真空磁控溅射系统，在电子传输层上反应溅射制备Sb2S3光吸收层。
具体地，将旋涂二氧化钛的ITO导电玻璃片作为基底装入可以旋转的基片固定装置上。溅射时，以4转/分钟的速率旋转基片固定装置，将溅射室抽真空至6×10-4帕，并通入氩气作为工作气体，流量为30标准毫升/分钟，硫化氢作为反应气体，流量为10标准毫升/分钟。采用硫化锑作为靶材，靶材的直径为60毫米，厚度为5毫米；采用射频(RF)溅射，工作气压为0.5帕，基底温度为300℃，开始沉积Sb2S3光吸收层前先预溅射5分钟，然后打开挡板向基底上溅射，直至Sb2S3光吸收层的厚度为800纳米。
(4)将沉积有Sb2S3光吸收层的样品放入管式退火炉中进行硫化退火处理，退火气氛为氩气气氛，退火温度为300℃，退火时间为30分钟。
(5)退火结束后，对Sb2S3光吸收层依次用浓度为20％的H2O2和浓度为10％的氨水进行旋涂预处理，然后在100℃的加热平台上烘烤5分钟后转移到60℃的真空保温箱中保温30分钟。
H2O2的目的是将低价的氧化物氧化成高价，有利于后续氨水及溶有偏钒酸铵的氨水溶液的处理；氨水的目的有二:一是可以先去除一部分氧化物杂质，二是可以对薄膜表面进行改性，利于接下来更好地附着溶有偏钒酸铵的氨水溶液。
(6)在处理后的Sb2S3光吸收层上利用溶液涂覆法制备V2O5空穴传输层。
具体地，溶液涂覆法中使用的溶液为溶入偏钒酸铵的稀氨水溶液，稀氨水浓度为5％。通过调整偏钒酸铵的浓度和旋涂仪的转速得到厚度为15纳米的薄膜，然后在100℃的加热平台上烘烤10分钟后，转移到500℃的加热平台上加热15分钟，得到厚度约为12纳米的V2O5薄膜，即空穴传输层。
锑氧化物与碱性物质作用，表现为酸性，可以与之反应，生成锑酸盐，由于硫化退火会造成薄膜表面富硫，锑酸盐与硫综合作用生成硫化锑。由于强碱物质可溶解硫化锑，所以选择弱碱物质稀氨水。通过这种制备V2O5空穴传输层的方法可以有效去除Sb2S3光吸收层中的氧化物等杂质，进而提高基于Sb2S3材料为吸收层的半透明薄膜太阳电池的稳定性和器件效率。
(7)在空穴传输层上采用磁控溅射法沉积一层300nm的ITO，即得到完整的具有无机空穴传输层的硫化锑半透明薄膜太阳电池器件，器件结构为Glass/ITO/TiO2/Sb2S3/V2O5/ITO。
请参照图2，图2为对比样1与实施例1制得的太阳器件的电流密度-电压特性曲线，对比样1中没有加入V2O5空穴传输层，其他每层的制备方法与实施例1一样。从图2中可知，加入V2O5空穴传输层后，太阳器件的效率明显提高，是因为V2O5作为空穴提取、传输的介质，提高了光生载流子的分离，降低了光生载流子的复合。
请参照图3，图3为对比样2与实施例1制得的太阳器件的电流密度-电压特性曲线，对比样2中加入的是Spiro-OMeTAD有机空穴传输层，而非V2O5空穴传输层，其他每层的制备方法与实施例1一样。从图3可知，本发明制得的太阳器件的效率衰减幅度小，稳定性好；对比样2的效率衰减幅度大，稳定性差。
实施例2
(1)将厚度为2.2mm、电阻≤14Ω/□、透光率≥90％的FTO导电玻璃(武汉晶格太阳能科技有限公司)，预先切割成15mm×20mm的长方形薄片。将长方形薄片依次用去离子水、玻璃清洗剂、丙酮、酒精、去离子水超声清洗15分钟，然后用空气压缩机吹干待用。
(2)采用化学水浴法在待用的FTO导电玻璃片上沉积50纳米的CdS电子传输层。
具体地，将160毫升的去离子水加入250毫升的烧杯中，然后再分别加入0.03摩尔/升的硫化镉溶液、1.5摩尔/升的硫脲和14.5毫升浓度为25％的氨水到烧杯中，再将烧杯放入集热式恒温加热磁力搅拌器中以80℃进行水浴，3-6分钟后溶液变成橙色，8分钟后在FTO导电玻璃片上沉积得到50纳米的硫化镉薄膜。
(3)采用泰科诺科技有限公司的ZHD-300M2电阻蒸发镀膜机，在电子传输层上制备硫化锑薄膜。
具体地，调节蒸发工艺(硫化锑蒸发料0.25克，电流70安培，电压1伏特，蒸发时间15分钟)，得到致密的550纳米厚的Sb2S3薄膜。对热蒸发法制备的硫化锑薄膜作紫外-可见吸收光谱分析，得到了紫外-可见吸收光谱图，如图4所示，由图可见，在250℃或350℃下蒸发获得的Sb2S3薄膜在大部分可见光范围的吸收系数大于105，是很好的半透明薄膜太阳电池光吸收材料和叠层电池材料。
(4)将Sb2S3薄膜置于管式退火炉中进行硫化退火处理，退火气氛为氩气气氛，退火温度为350℃，退火时间为30分钟。
(5)对退火后的Sb2S3薄膜依次用浓度为25％的H2O2和浓度为8％的氨水进行旋涂预处理，再在150℃的加热平台上烘烤3分钟后转移到70℃的真空保温箱中保温20分钟，即得Sb2S3光吸收层。
(6)在Sb2S3光吸收层上利用溶液涂覆法制备V2O5空穴传输层。
具体地，溶液涂覆法中使用的溶液为溶入偏钒酸铵的稀氨水溶液，稀氨水浓度为8％。通过调整偏钒酸铵的浓度和旋涂仪的转速得到厚度为38纳米的薄膜，然后在120℃的加热平台上烘烤8分钟后，转移到480℃的加热平台上加热20分钟，得到厚度约为30纳米的V2O5薄膜，即空穴传输层。
(7)在空穴传输层上采用磁控溅射法沉积一层450nm的FTO，即得到完整的具有无机空穴传输层的硫化锑半透明薄膜太阳电池器件，器件结构为Glass/FTO/CdS/Sb2S3/V2O5/FTO，请参照图5。
以上所述仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是在本发明的构思下，利用本发明说明书及附图内容所作的等效结构变换，或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。
Claims (3)
1.一种半透明薄膜太阳电池的制备方法，其特征在于，包括以下步骤：
1)清洗导电玻璃，所述导电玻璃为ITO、FTO或AZO玻璃中的任一种；
2)在导电玻璃上沉积10-80nm的电子传输层，所述电子传输层为TiO2、ZnO、CdS、In2S3或SnO2中的任一种；
3)利用磁控溅射法、热蒸发法或化学水浴法在电子传输层上沉积100-2000nm的Sb2S3光吸收层，并将Sb2S3光吸收层在200-400℃下退火10-50min；
4)在退火处理后的Sb2S3光吸收层上依次旋涂H2O2和氨水，旋涂结束后将样品在50-200℃的加热平台上烘烤3-20min，随后转移至50-80℃的真空保温箱中保温10-60min；
5)将样品从真空保温箱中取出，在Sb2S3光吸收层上旋涂溶解有偏钒酸铵的稀氨水溶液，制得1-50nm的V2O5空穴传输层；
6)利用磁控溅射法在V2O5空穴传输层上沉积100-1000nm的背电极，所述背电极为ITO或FTO；
所述步骤5)具体为：
将样品从真空保温箱中取出，在Sb2S3光吸收层上旋涂溶解有偏钒酸铵的稀氨水溶液制得薄膜，然后将其在80或100℃加热平台上烘烤后，转移到480或500℃的加热平台上加热，从而制得1-50nm的V2O5空穴传输层。
2.如权利要求1所述的半透明薄膜太阳电池的制备方法，其特征在于，所述步骤4)中H2O2的浓度为20-30％，氨水的浓度为5-15％。
3.如权利要求1所述的半透明薄膜太阳电池的制备方法，其特征在于，所述步骤5)中稀氨水的浓度为2-10％。
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