CN111560583B - 一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法 - Google Patents
一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法 Download PDFInfo
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- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 title claims abstract description 88
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- 238000000137 annealing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明是一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法，包括衬底薄膜，其特点是，还包括掺杂剂，在衬底薄膜与掺杂剂制备出掺杂的衬底薄膜之后，使得(Sb4Se6)n分子链能够与衬底薄膜形成共价键，(Sb4Se6)n分子链沿着垂直于衬底薄膜方向的纵向生长，最终诱导出纵向择优的硒化锑光电薄膜。通过对衬底薄膜掺杂能够有效提高制品的电学特性，使得衬底薄膜和硒化锑薄膜的特性同步提高，最终使得硒化锑光电器件的载流子传输性能有效提升，光电性能显著提高。具有方法科学合理，制备流程简单实用，适于产业化生产，成本低，应用价值高等优点。
Description
技术领域
本发明属于光电薄膜材料及器件制备领域，是一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法。
背景技术
硒化锑是一种很有潜力的光电材料，它不仅具有较窄的禁带宽度1 ~ 1 .2eV，能够有效吸收波长小于1100nm的太阳光谱，还具有较高吸收系数，非常适宜作为太阳电池和可见光-近红外光探测器的光吸收层。硒化锑是一种一维链状结构，其中一维(Sb4Se6)n分子链以范德华力结合在一起，载流子沿(Sb4Se6)n分子链的迁移能力远远大于链间的传输速率，因此保证硒化锑光电薄膜的纵向生长是高性能太阳电池和光电探测器的关键。现有技术一般通过对硒化锑制备条件的调控以获得纵向生长的(Sb4Se6)n分子链，但这种方法工艺窗口较窄，不适用于产业化生产。
发明内容
针对现有技术存在的不足，以及对硒化锑光电器件性能提高的需求，本发明的目的是，提供一种科学合理，制备流程简单实用，适于产业化生产，成本低，且能够明显提高制备成品电学特性的诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法。
本发明的目的是通过以下技术方案来实现的：一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法，它包括衬底薄膜，其特征是，还包括掺杂剂，在衬底薄膜与掺杂剂制备出掺杂的衬底薄膜之后，使得(Sb4Se6)n分子链能够与衬底薄膜形成共价键，(Sb4Se6)n分子链沿着垂直于衬底薄膜方向的纵向生长，最终诱导出纵向择优的硒化锑光电薄膜。
采用一步法制备硒化锑光电薄膜：将掺杂剂直接掺入衬底薄膜之中，掺杂剂为化合物CdCl2、SnCl3和ZnCl2中至少一种，或者单质元素Cd、Zn和B中至少一种，掺杂浓度为0.01%-20%制备得到所述掺杂的衬底薄膜；应用制备得到所述掺杂的衬底薄膜，采用热蒸发法，真空度为0.1-10 Pa，衬底薄膜温度为200-400℃，蒸发源温度为400-600℃；蒸发时间为30-120s，制备得到(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜。
采用二步法制备硒化锑光电薄膜：将掺杂剂旋涂在衬底薄膜表面，所述掺杂剂为化合物CdCl2、SnCl3和ZnCl2中的至少一种，或者单质元素如Cd、Zn和B中的至少一种，掺杂浓度为0.01%-20%，通过退火处理完成掺杂过程形成掺杂的衬底薄膜，退火温度为300-600℃，退火时间为2-100 min；应用制备得到所述掺杂的衬底薄膜，采用热蒸发法，真空度为0.1-10Pa；衬底薄膜温度为200-400℃，蒸发源温度为400-600℃，蒸发时间为30-120s，制备得到(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜。
本发明的一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法是利用掺杂技术调节衬底薄膜表面化学键，使硒化锑的(Sb4Se6)n分子链能够与掺杂元素形成共价键，并沿垂直与衬底薄膜表面的方向生长。此外，通过对衬底薄膜掺杂还能够有效提高制品的电学特性，使得衬底薄膜和硒化锑薄膜的特性同步提高，达到一举两得的效果。最终使得硒化锑光电器件的载流子传输性能有效提升，光电性能显著提高。本发明的方法科学合理，制备流程简单实用，适于产业化生产，成本低，具有较高的应用价值。
附图说明
图1是不同掺杂衬底薄膜上生长硒化锑光电薄膜的XRD图；
图2是掺杂前与掺杂后SnO2电子传输层的电导率示意图；
图3是掺杂前与掺杂后硒化锑薄膜的XRD图；
图4是未掺杂衬底薄膜上生长硒化锑薄膜的表面形貌示意图；
图5是掺杂衬底薄膜上生长硒化锑薄膜的表面形貌示意图；
图6是衬底薄膜掺杂对硒化锑薄太阳电池性能的影响示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例及附图，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明的一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法，它包括衬底薄膜，还包括掺杂剂，在衬底薄膜与掺杂剂制备出掺杂的衬底薄膜之后，使得(Sb4Se6)n分子链能够与衬底薄膜形成共价键，形成沿着垂直于衬底薄膜方向的纵向生长，最终诱导出纵向择优的硒化锑光电薄膜。
采用一步法制备硒化锑光电薄膜：将掺杂剂直接掺入衬底薄膜之中，掺杂剂为化合物CdCl2、SnCl3和ZnCl2中至少一种，或者单质元素Cd、Zn和B中至少一种，掺杂浓度为0.01%-20%制备得到所述掺杂的衬底薄膜；应用制备得到所述掺杂的衬底薄膜，采用热蒸发法，真空度为0.1-10Pa，衬底薄膜温度为200-400℃，蒸发源温度为400-600℃；蒸发时间为30-120s，制备得到(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜。
采用二步法制备硒化锑光电薄膜：将掺杂剂旋涂在衬底薄膜表面，所述掺杂剂为化合物CdCl2、SnCl3和ZnCl2中的至少一种，或者单质元素如Cd、Zn和B中的至少一种，掺杂浓度为0.01%-20%，通过退火处理完成掺杂过程形成掺杂的衬底薄膜，退火温度为300-600℃，退火时间为2-100min；应用制备得到所述掺杂的衬底薄膜，采用热蒸发法，真空度为0.1-10Pa；衬底薄膜温度为200-400℃，蒸发源温度为400-600℃，蒸发时间为30-120s，制备得到(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜。
所述的衬底薄膜是电子传输层和空穴传输层，电子传输层为ZnO、TiO2、SnO2、Sb2O3和CdS中至少一种；空穴传输层为NiO、CuO、聚乙撑二氧噻吩-聚(苯乙烯磺酸盐) （PEDOT:PSS）、聚-3 已基噻吩（P3HT）和硫氰酸亚铜（CuSCN）中至少一种；
所述的一步法是指在衬底薄膜的制备过程中进行掺杂，采用的方法可以为低压化学气相沉积技术、热蒸发技术、磁控溅射技术、超声喷雾技术或旋涂技术。
所述的二步法是指在制备衬底薄膜的以后通过后处理进行掺杂，采用的方法可以为超声喷雾技术或旋涂技术，然后通过退火处理完成掺杂过程。
制备得到(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜可制作硒化锑光电器件，例如：太阳电池或光电探测器。
硒化锑光电器件结构可以为玻璃/透明导电膜/电子传输层/硒化锑/空穴传输层/金属电极、玻璃/透明导电膜/空穴传输层/硒化锑/电子传输层/金属电极、玻璃/透明导电膜/硒化锑/电子传输层/金属电极、玻璃/透明导电膜/硒化锑/空穴传输层/金属电极。
实施例1：采用一步法制备硒化锑光电薄膜：
（1）通过低压化学气相沉积技术在制备氧化锌薄膜，其中二乙基锌和水的流量分别为300sccm 和 350sccm，采用氢气稀释的硼烷（B2H6）做掺杂源，流量为150sccm，沉积温度为200℃，沉积压力为150 Pa，沉积时间为800s，形成氧化锌掺硼（BZO）衬底薄膜；
（2）采用快速热蒸发法在BZO衬底薄膜上制备硒化锑薄膜，真空度为5Pa；衬底薄膜温度为300℃；蒸发源温度为450℃；蒸发时间为90s，制备厚度为1000 nm的硒化锑光吸收层；
（3）在硒化锑层之上，采用2500rpm，持续时间60s，旋涂PEDOT:PSS薄膜以制备空穴传输层；
（4）在空穴传输层之上通过刮涂制备碳电极，获得了肖特基结硒化锑薄膜太阳电池；
（5）将在BZO衬底薄膜之上生长的硒化锑薄膜与市售的氧化铟锡（ITO）衬底薄膜和二氧化锡掺氟（FTO）衬底薄膜上生长硒化锑薄膜的生长取向进行对比，结果如图1所示。ITO衬底薄膜上生长的硒化锑薄膜以（141）和（061）等横向择优峰为主，说明(Sb4Se6)n分子链是以横向生长为主；而FTO上生长的硒化锑薄膜以（211）和（221）等纵向择优峰为主，说明(Sb4Se6)n分子链纵向生长的比例增加。而BZO衬底薄膜上生长的硒化锑薄膜显示单（002）择优取向，表明(Sb4Se6)n分子链都是垂直于衬底薄膜生长，这时硒化锑薄膜具有最高的纵向载流子迁移能力。以上实例说明通过掺杂能够有效调节硒化锑薄膜(Sb4Se6)n分子链的生长取向，采用掺杂BZO衬底薄膜能够有效诱导出单（002）择优峰的硒化锑薄膜。
采用低压化学气相沉积技术、热蒸发技术、磁控溅射技术、超声喷雾技术或旋涂技术均可以通过一步法制备掺杂的衬底薄膜，并在此基础上制备出(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜。
实施例2：采用两步法制备硒化锑光电薄膜：
（1）将FTO导电玻璃依次用洗涤剂、丙酮、异丙醇、乙醇和去离子水浸泡超声各30分钟，然后用氮气吹干；
（2）在FTO导电玻璃上采用旋涂技术，转速为2500rpm，持续时间30s，旋涂商用SnO2纳米颗粒溶液, 之后放在加热台上150℃加热干燥，制备20nm厚SnO2电子传输层作为衬底薄膜；
（3）在SnO2电子传输层上采用旋涂技术，转速为2500 rpm，持续时间60s，旋涂20mg/ml的CdCl2甲醇溶液进行掺杂处理，之后在加热台上400℃退火60min已完成衬底薄膜的掺杂处理；
（4）采用快速热蒸发法制备硒化锑薄膜，真空度为0.1Pa；衬底薄膜温度为200℃；蒸发源温度为400℃；蒸发时间为120s，制备厚度为800 nm的硒化锑光吸收层；
（5）在硒化锑光吸收层上采用旋涂技术，转速为2000rpm，持续时间60s，制备P3HT衬底薄膜作为空穴传输层；
（6）在P3HT空穴传输层之上通过刮涂制备碳电极，获得硒化锑薄膜太阳电池，并对其进行标准太阳光下光电性能测试。
图2为SnO2电子传输层的电导率测试，CdCl2掺杂以后衬底薄膜的导电能力有效提高。图3为掺杂前与掺杂后硒化锑薄膜的XRD图，掺杂前硒化锑薄膜的生长为(Sb4Se6)n分子链纯横向生长模式。掺杂后硒化锑薄膜的横向择优峰基本消失，转而变为（211）、（221）与（002）为主的纵向择优峰，说明掺杂有效的调制了(Sb4Se6)n分子链的纵向生长。图4和图5为掺杂前与掺杂后硒化锑薄膜的SEM图，表面形貌的变化也表明经过处理后硒化锑的生长取向从横向转为纵向，使得硒化锑传输载流子能力增强。通过图6掺杂前与掺杂后的硒化锑太阳电池的电流-电压曲线可以看到，通过(Sb4Se6)n分子链纵向生长的调制，使得硒化锑太阳电池的光电性能得到了显著提高。
实施例3：采用两步法制备硒化锑光电薄膜：
（1）将ITO导电玻璃依次用洗涤剂、丙酮、异丙醇、乙醇和去离子水浸泡超声各30分钟，然后用氮气吹干；
（2）在ITO导电玻璃上应用超声喷雾技术，采用SnCl3溶液进行喷涂，喷液距离为15cm，衬底薄膜温度为400℃，生长时间为20min，制备出厚度为30nm的SnO2电子传输层作为衬底薄膜；
（3）在SnO2电子传输层上采用旋涂技术，转速3000 rpm，持续时间50s，旋涂15 mg/ml的ZnCl2溶液，之后在加热板上进行600℃退火10 min已完成衬底薄膜掺杂处理；
（4）采用快速热蒸发法制备硒化锑薄膜，真空度为10Pa；衬底薄膜温度为400℃；蒸发源温度为600℃；蒸发时间为30s，制备厚度为1200 nm的硒化锑光吸收层；
（5）在硒化锑光吸收层上，通过高真空热蒸发制备金电极，获得硒化锑近红外光电探测器。
以上所述仅是本发明的优选方式，应当指出的是，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应该视为本发明的保护范围。
Claims (3)
1.一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法，它包括衬底薄膜，其特征是，还包括掺杂剂，在衬底薄膜与掺杂剂制备出掺杂的衬底薄膜之后，使得(Sb4Se6)n分子链能够与衬底薄膜形成共价键，形成沿着垂直于衬底薄膜方向的纵向生长，最终诱导出纵向择优的硒化锑光电薄膜，
（1）通过低压化学气相沉积技术在制备氧化锌薄膜，其中二乙基锌和水的流量分别为300sccm 和 350sccm，采用氢气稀释的硼烷（B2H6）做掺杂源，流量为150sccm，沉积温度为200℃，沉积压力为150 Pa，沉积时间为800s，形成氧化锌掺硼（BZO）衬底薄膜；
（2）采用快速热蒸发法在BZO衬底薄膜上制备硒化锑薄膜；真空度为0.1-10Pa，衬底薄膜温度为200-400℃，蒸发源温度为400-600℃，蒸发时间为30-120s；所制备的硒化锑薄膜具有沿单一（002）方向择优生长的特点，表明硒化锑薄膜内部的(Sb4Se6)n分子链形成了沿垂直于衬底薄膜方向的纵向排列结构，最终诱导出强纵向择优的硒化锑光电薄膜。
2.一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法，它包括衬底薄膜，其特征是，还包括掺杂剂，在衬底薄膜与掺杂剂制备出掺杂的衬底薄膜之后，使得(Sb4Se6)n分子链能够与衬底薄膜形成共价键，形成沿着垂直于衬底薄膜方向的纵向生长，最终诱导出纵向择优的硒化锑光电薄膜，
（1）将FTO导电玻璃依次用洗涤剂、丙酮、异丙醇、乙醇和去离子水浸泡超声各30分钟，然后用氮气吹干；
（2）在FTO导电玻璃上采用旋涂技术，转速为2500rpm，持续时间30s，旋涂商用SnO2纳米颗粒溶液, 之后放在加热台上150℃加热干燥，制备20nm厚SnO2电子传输层作为衬底薄膜；
（3）在SnO2电子传输层上采用旋涂技术，转速为2500 rpm，持续时间60s，旋涂20 mg/ml的CdCl2甲醇溶液进行掺杂处理，之后在加热台上400℃退火60min已完成衬底薄膜的掺杂处理；
（4）采用快速热蒸发法制备硒化锑薄膜，真空度为0.1-10Pa，衬底薄膜温度为200-400℃，蒸发源温度为400-600℃，蒸发时间为30-120s；所制备的硒化锑薄膜相比于未掺杂的SnO2电子传输层上制备的硒化锑薄膜，代表(Sb4Se6)n分子链横向生长的（hk0）择优取向得到有效抑制，代表(Sb4Se6)n分子链纵向生长的（002）择优取向得到显著增强，通过衬底掺杂有效的诱导出纵向生长的硒化锑光电薄膜。
3.一种诱导(Sb4Se6)n分子链纵向生长的硒化锑光电薄膜制备方法，它包括衬底薄膜，其特征是，还包括掺杂剂，在衬底薄膜与掺杂剂制备出掺杂的衬底薄膜之后，使得(Sb4Se6)n分子链能够与衬底薄膜形成共价键，形成沿着垂直于衬底薄膜方向的纵向生长，最终诱导出纵向择优的硒化锑光电薄膜，
（1）将ITO导电玻璃依次用洗涤剂、丙酮、异丙醇、乙醇和去离子水浸泡超声各30分钟，然后用氮气吹干；
（2）在ITO导电玻璃上应用超声喷雾技术，采用SnCl3溶液进行喷涂，喷液距离为15cm，衬底薄膜温度为400℃，生长时间为20min，制备出厚度为30nm的SnO2电子传输层作为衬底薄膜；
（3）在SnO2电子传输层上采用旋涂技术，转速3000 rpm，持续时间50s，旋涂15 mg/ml的ZnCl2溶液，之后在加热板上进行600℃退火10 min已完成衬底薄膜掺杂处理；
（4）采用快速热蒸发法制备硒化锑薄膜，真空度为0.1-10Pa，衬底薄膜温度为200-400℃，蒸发源温度为400-600℃，蒸发时间为30-120s；所制备的硒化锑薄膜相比于未掺杂的SnO2电子传输层上制备的硒化锑薄膜，代表(Sb4Se6)n分子链横向生长的（hk0）择优取向得到有效抑制，代表(Sb4Se6)n分子链纵向生长的（002）择优取向得到显著增强，通过衬底掺杂有效的诱导出纵向生长的硒化锑光电薄膜。
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