CN114031310A - 一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法 - Google Patents
一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法 Download PDFInfo
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Abstract
本发明的目的意在改善钙钛矿薄膜结晶性和室温相稳定性，提供一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，属于光电薄膜技术领域，以二维钙钛矿作为衬底，通过溶液旋涂的方法将全无机钙钛矿前驱液旋涂于二维钙钛矿上，经退火沉积得到梯度相变型高质量钙钛矿薄膜。在沉积的过程中，二维衬底中的有机铵盐离子经扩散后呈现出自薄膜底部至表面浓度逐渐增大的梯度分布，晶界处的有机铵盐对钙钛矿晶格结构施加分子力作用，导致钙钛矿形成梯度相分布的结构。该方法制备的全无机钙钛矿薄膜晶粒尺寸较大，表面粗糙度低，结晶质量高，室温黑相稳定性高。
Description
技术领域
本发明属于光电薄膜技术领域，具体涉及一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法。
背景技术
有机-无机杂化钙钛矿具有吸光性强、载流子迁移率高、器件性能高等优良特性，相应的太阳能电池最大光电效率已达到25.5%，接近商业晶硅太阳能电池的效率。但是，由于有机组分易挥发的性质，有机-无机杂化钙钛矿的光热稳定性较差，目前难以实现其商业化应用。全无机钙钛矿由于组分稳定，可以保持很好的光热稳定性，解决杂化钙钛矿光热易降解的问题，最有可能实现商业化推广应用。但全无机钙钛矿受限于无机阳离子较小的尺寸，在室温下光学活性相（黑相，包括α、β、γ相）结构并不稳定，极易在外界环境的干扰下从黑相转变为非钙钛矿相（黄相，δ相）。另外，相比有机-无机杂化钙钛矿而言，全无机钙钛矿结晶性相对较差，因此其光电器件效率相对较低。因此，全无机钙钛矿材料亟待解决的问题是：如何提高室温黑相稳定性，如何改善薄膜结晶质量。
在提高全无机钙钛矿的室温黑相稳定性这一方面，目前的技术主要通过改善钙钛矿的维度，将三维钙钛矿变为二维钙钛矿或者量子点形态，通过增大晶粒表面积降低表面活性来提高相稳定性。但是低维钙钛矿应用到器件中，会阻碍载流子的传输，从而限制器件的效率。
在解决全无机钙钛矿结晶性差的问题这一方面，目前一种有效的方法提供特定的基底，利用基底合适的粗糙度和湿润性，调控钙钛矿的结晶过程。但是这种方法会引入插入层，从而产生能级不匹配或增大电阻等情况，因此对基底材料选定较为苛刻，难以推广应用。
发明内容
本发明的目的意在改善钙钛矿薄膜结晶性和室温相稳定性，提供一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法。利用二维钙钛矿衬底合适的湿润性以及较低的表面粗糙度，促进钙钛矿在此衬底上结晶生长；更重要地，二维衬底中的有机铵盐离子在全无机钙钛矿成膜过程中向上扩散，对钙钛矿晶格挤压，从而得到梯度相变型的致密、无孔洞的高质量全无机钙钛矿薄膜。
本发明采用如下技术方案：
一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，包括如下步骤：
第一步，预热基底；
第二步，旋涂有机铵盐与铅卤酸的有机溶剂混合液；
第三步，预退火、退火，得到二维钙钛矿衬底；
第四步，预热二维钙钛矿衬底；
第五步，旋涂全无机钙钛矿前驱液；
第六步，预退火、退火，得到梯度相变型全无机钙钛矿薄膜。
进一步地，第一步中所述基底包括涂有TiO2层或SnO2层的氟掺杂氧化锡导电玻璃（FTO）或铟锡氧化物导电玻璃（ITO）基底，预热温度为90~120℃。
进一步地，第二步中所述有机铵盐包括苯乙基碘化铵、二乙基苯铵、苯基铵醋酸盐和环己基铵盐中的一种或多种的混合物，所述铅卤酸包括铅碘酸和铅溴酸中的一种或多种的混合物，所述有机溶剂包括甲酰胺、二甲基亚砜和N,N-二甲基甲酰胺中的一种或者多种的混合物，有机铵盐与铅卤酸的摩尔比为1:1~1:1.3，有机铵盐与有机溶剂的配比为0.5mg:1mL~2mg:1mL，二维钙钛矿混合溶液搅拌时间为5-10min。
进一步地，第二步中所述旋涂方式为动态旋涂，旋涂转速为5500~6000rpm，旋涂时间为25~35s。
进一步地，第三步中所述预退火温度为90~120℃，预退火时间为1~3min，退火温度为150~180℃，退火时间为5~10min。
进一步地，第四步中所述二维衬底预热的温度为25~70℃。
进一步地，第五步中所述全无机钙钛矿前驱液为碘化铯、卤化铅与有机溶剂的混合物，卤化铅包括碘化铅或溴化铅，有机溶剂包括甲酰胺、二甲基亚砜和N,N-二甲基甲酰胺中的一种或者多种混合物，碘化铯与有机溶剂的配比为156mg:1mL~182mg:1mL，碘化铯与卤化铅的摩尔比为1:1~1:1.1。
进一步地，第五步中所述旋涂方式为静态旋涂，转速为2500~3000rpm，转速加速度为1500~2000rpm/min，旋转时间为25~35s。
进一步地，第六步中预退火温度为50-80℃，预退火时间为1-3min，退火温度为170~190℃，退火时间为15-20min。
本发明利用二维衬底独特的性质，调控钙钛矿薄膜高结晶质量；利用二维衬底中有机铵盐的扩散性质，以及有机铵盐离子在钙钛矿中体现的稳定相结构的位阻效应，得到高稳定性的γ-β-α梯度相变型钙钛矿薄膜。梯度相分布致使钙钛矿能级结构发生梯度渐变，在器件设计中更加便于得到能级匹配的相邻传输层，提高相应器件载流子的抽取和迁移能力，大幅提升器件的光电性能。在未来的钙钛矿推广应用中，这种新颖且便捷的二维衬底调控生长方法不仅可以应用在全无机钙钛矿光电器件制备中，还可以应用在杂化钙钛矿器件中，具有极大的研究和使用价值。
本发明的有益效果如下：
本发明通过引入良好湿润性以及粗糙度的二维钙钛矿作为衬底生长全无机钙钛矿晶体，有利于改善钙钛矿结晶性。由于在钙钛矿层生长过程中二维钙钛矿中有机铵盐离子的扩散，使得钙钛矿层呈现自下而上浓度逐渐减小的梯度分布。由于晶界中的有机铵盐离子与钙钛矿晶笼之间有分子力的作用，导致钙钛矿晶体结构发生一定程度的扭曲，钙钛矿逐渐发生相变，因此得到γ-β-α梯度相变的全无机钙钛矿。钙钛矿的能级随相变发生变化，所以梯度相变能够同时调节钙钛矿与相邻两个传输层能级的匹配程度。另外，由于有机铵盐的位阻效应，以及渐变相本身更强的室温稳定性，二维钙钛矿衬底调控生长得到的梯度相变型钙钛矿薄膜相比于传统的薄膜体现出非常优越的环境稳定性。
附图说明
图1为二维衬底PH100（100mg/ml PEAAc+HPbI3制备的二维PEA2PbI4）的SEM图；
图2为二维衬底PH100的XRD图；
图3为常规生长（control）与PH1（1mg/ml PEAAc+HPbI3制备的二维PEA2PbI4）衬底生长（PVK-PH1）的钙钛矿薄膜SEM表面图；
图4为常规生长（control）与PH1衬底生长（PVK-PH1）的钙钛矿薄膜XRD图；
图5为二维衬底生长的梯度相变型钙钛矿薄膜示意图；
图6 为本发明实施例1中钙钛矿太阳能电池的电压-电流图；
图7为本发明实施例1中钙钛矿太阳能电池PCE随时间的稳定性（湿度10~20%RH）测试图；
图8为本发明实施例2中钙钛矿太阳能电池的电压-电流图。
具体实施方式
现在结合具体实施例对本发明作进一步的说明。具体实施例中钙钛矿太阳能电池的器件结构从下至上分别为：FTO透明导电玻璃、电子传输层、钙钛矿活性层、空穴传输层和金属电极层。
实施例1
一种二维钙钛矿基底调控生长梯度相变型的高质量全无机钙钛矿薄膜及其器件的制备方法，包括以下步骤：
前处理：选择方块电阻15Ω、透光率90%的FTO作为导电玻璃衬底材料，然后依次用乙醇、丙酮、异丙醇超声清洗15min，然后吹干。
制备TiO2电子传输层：将70μL的7-10%二异丙氧二(乙氧乙酰乙酰)合酞的正丁醇溶液旋涂在洗净吹干后的FTO导电玻璃上，转速加速度为1500rpm/min，转速为3000rpm，旋涂时间为30s。随后，使用加热台将旋涂好的电子传输层的样本在125℃下预加热5min，待冷却后放入马弗炉中，加热至450℃并持续一小时。
旋涂二维钙钛矿层：将1mg PEAAc（醋酸苯乙铵）与HPbI3按照摩尔比1：1混合溶于1ml DMF溶液中，将35μL的二维钙钛矿前驱液动态旋涂于沉积好的TiO2电子传输层上，转速为6000rpm，旋涂时间为30s。随后，使用加热台将旋涂好的二维钙钛矿层的样本在120℃下预加热2min，然后将样本在180℃下加热5min。
制备钙钛矿层：将45μL的0.6M CsPbI3的DMF溶液旋涂于二维钙钛矿层上，转速加速度为1500rpm/min，转速为3000rpm，旋转时间为30s。随后，使用加热台将旋涂好的钙钛矿层的样本在70℃下预加热2min，然后在180℃下加热18min。
制备空穴传输层：将70μL的10mg/ml P3HT的氯苯溶液旋涂于钙钛矿层上，转速加速度为1500rpm/min，转速为3000rpm，旋转时间为30s。随后，使用加热台将旋涂好的空穴传输层的样本在120℃下预加热5min。
热蒸镀金属电极层：采用热蒸发镀膜机，在~6×10-4Pa真空下，热蒸镀850nm的银，形成金属电极层。
本实施案例中得到的钙钛矿太阳能电池的性能参数如图6所示，该电池的能量转换效率高，开路电压、短路电流和填充因子都得到了改善。根据图7湿度稳定性测试，可知该电池可在湿度为10~20%RH的空气中保存9天后，效率依然维持70%以上，相较与传统器件，使用稳定性大幅增加。
实施例2
一种二维钙钛矿基底调控生长梯度相变型的高质量全无机钙钛矿薄膜及其器件的制备方法，包括以下步骤：
前处理：选择方块电阻15Ω、透光率90%的FTO作为导电玻璃衬底材料，然后依次用乙醇、丙酮、异丙醇超声清洗15min，然后吹干。
制备TiO2电子传输层：将70μL的7-10%二异丙氧二(乙氧乙酰乙酰)合酞的正丁醇溶液旋涂在洗净吹干后的FTO导电玻璃上，转速加速度为1500rpm/min，转速为3000rpm，旋涂时间为30s。随后，使用加热台将旋涂好的电子传输层的样本在125℃下预加热5min，待冷却后放入马弗炉中，加热至450℃并持续一小时。
旋涂二维钙钛矿层：将1mg PBAAc（醋酸苯丁铵）与HPbI3按照摩尔比1：1混合溶于1ml DMF溶液中，将40μL的二维钙钛矿前驱液动态旋涂于沉积好的TiO2电子传输层上，转速为6000rpm，旋涂时间为30s。随后，使用加热台将旋涂好的二维钙钛矿层的样本在120℃下预加热2min，然后将样本在180℃下加热5min。
制备钙钛矿层：将45μL的0.6M CsPbI3的DMF溶液旋涂于二维钙钛矿层上，转速加速度为1500rpm/min，转速为3000rpm，旋转时间为30s。随后，使用加热台将旋涂好的钙钛矿层的样本在70℃下预加热2min，然后在180℃下加热18min。
制备空穴传输层：将70μL的10mg/ml P3HT的氯苯溶液旋涂于钙钛矿层上，转速加速度为1500rpm/min，转速为3000rpm，旋转时间为30s。随后，使用加热台将旋涂好的空穴传输层的样本在120℃下预加热5min。
热蒸镀金属电极层：采用热蒸发镀膜机，在~6×10-4Pa真空下，热蒸镀850nm的银，形成金属电极层。
本实施案例中得到的钙钛矿太阳能电池的性能参数如图8所示，该电池的能量转换效率高，开路电压、短路电流和填充因子都得到了改善。
Claims (9)
1.一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：包括如下步骤：
第一步，预热基底；
第二步，旋涂有机铵盐与铅卤酸的有机溶剂混合液；
第三步，预退火、退火，得到二维钙钛矿衬底；
第四步，预热二维钙钛矿衬底；
第五步，旋涂全无机钙钛矿前驱液；
第六步，预退火、退火，得到梯度相变型全无机钙钛矿薄膜。
2.根据权利要求1所述的一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：第一步中所述基底包括涂有TiO2层或SnO2层的氟掺杂氧化锡导电玻璃或铟锡氧化物导电玻璃基底，预热温度为90~120℃。
3.根据权利要求1所述的一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：第二步中所述有机铵盐包括苯乙基碘化铵、二乙基苯铵、苯基铵醋酸盐和环己基铵盐中的一种或多种的混合物，所述铅卤酸包括铅碘酸和铅溴酸中的一种或多种的混合物，所述有机溶剂包括甲酰胺、二甲基亚砜和N,N-二甲基甲酰胺中的一种或者多种的混合物，有机铵盐与铅卤酸的摩尔比为1:1~1:1.3，有机铵盐与有机溶剂的配比为0.5mg:1mL~2mg:1mL，二维钙钛矿混合溶液搅拌时间为5-10min。
4.根据权利要求1所述的一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：第二步中所述旋涂方式为动态旋涂，旋涂转速为5500~6000rpm，旋涂时间为25~35s。
5.根据权利要求1所述的一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：第三步中所述预退火温度为90~120℃，预退火时间为1~3min，退火温度为150~180℃，退火时间为5~10min。
6.根据权利要求1所述的一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：第四步中所述二维衬底预热的温度为25~70℃。
7.根据权利要求1所述的一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：第五步中所述全无机钙钛矿前驱液为碘化铯、卤化铅与有机溶剂的混合物，卤化铅包括碘化铅或溴化铅，有机溶剂包括甲酰胺、二甲基亚砜和N,N-二甲基甲酰胺中的一种或者多种混合物，碘化铯与有机溶剂的配比为156mg:1mL~182mg:1mL，碘化铯与卤化铅的摩尔比为1:1~1:1.1。
8.根据权利要求1所述的一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：第五步中所述旋涂方式为静态旋涂，转速为2500~3000rpm，转速加速度为1500~2000rpm/min，旋转时间为25~35s。
9.根据权利要求1所述的一种二维钙钛矿衬底调控生长梯度相变型全无机钙钛矿薄膜的方法，其特征在于：第六步中预退火温度为50-80℃，预退火时间为1-3min，退火温度为170~190℃，退火时间为15-20min。
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