CN115101610B - 一种硒薄膜/碲薄膜室内光伏器件及其制备方法 - Google Patents
一种硒薄膜/碲薄膜室内光伏器件及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种硒薄膜/碲薄膜室内光伏器件，结构为导电玻璃/电子传输层/碲薄膜/硒薄膜/金电极。所述碲薄膜的厚度0.5‑5nm，硒薄膜的厚度为0.5‑3μm。本发明成功的展示了硒薄膜在室内光伏领域的应用，制备的硒薄膜室内光伏器件具有较高的能量转化效率，在室内光下表现出了较好的稳定性。有利的推动了硒薄膜在室内光伏的发展，并且在物联网领域的应用表现出了巨大的发展前景。
Description
技术领域
本发明属于光电材料及薄膜太阳能电池制备领域，具体涉及一种硒薄膜/碲薄膜室内光伏器件及其制备方法。
背景技术
物联网(Internet of Things，IoT)技术是实现智慧建筑、智慧工厂、智慧城市的重要支撑技术。这类产品通常在室内使用，具有低功耗、分布广等特点。室内光伏器件(Indoor photovoltaics，IPV)为物联网器件供能表现出了巨大的潜力，可提供连续、离线型能源，大大减少了电池的使用。常见的人工照明设备包括白炽灯、荧光灯和发光二极管灯等，其光谱范围较窄，主要集中在400-700nm之间，与标准太阳光光谱(300-1000nm)相差较大，这就要求合适的室内光伏器件吸收层材料具有较宽的带隙(～1.9eV)；此外，室内光的强度通常小于1mW/cm2，而标准太阳光强为100mW/cm2。目前，商业化的硅太阳能电池在太阳能光下拥有较高的效率，但在室内光下光生载流子密度较低，器件中的缺陷态导致复合效应显著，性能较差。此外，由于室内光伏器件是在室内使用，其毒性也是不得不考虑的问题。
现有技术中多以成熟的钙钛矿作为室内光伏器件，比如CN114583063A，CN113346025A中报道。钙钛矿光伏器件带隙可调，结构简单，大面积，柔性的特性都适合作为室内光伏器件。但是一般钙钛矿光伏器件都含有铅这种毒性物质，极大限制了其进入室内光伏器件市场。考虑到室内光伏器件除了光电性能，对安全性的考量也非常重要。此外，还有复杂的有机分子合成的室内光伏器件，但是其合成复杂，原料成本高昂，距离产业化的生产和应用还有很远的距离。
硒具有较宽的带隙(～1.9eV)，室内光理论转换效率达到55％；此外还具有较大的吸收系数、低毒、价格低廉等特点，非常适合作为室内光伏器件吸收层材料。硒太阳能电池是最早的太阳能电池，随着硅太阳能电池的迅速发展硒太阳能电池发展趋于缓慢。室内光伏的集中研究近几年刚刚开始，大部分研究主要是基于钙钛矿，也有少部分是基于光敏染料。室内光伏本身属于小众方向，而硒在标准太阳光中的研究就相对少很多，目前缺乏对硒在室内光伏领域的机理、应用进行系统的研究。
发明内容
硒太阳电池是首次报道的太阳电池，但是较宽的带隙(1.9eV)导致单结电池在太阳光下的最高理论效率仅为23％。常用的室内光源如发光二极管(LED)和荧光灯(FL)的发射光谱范围为400至700nm，因此确定室内光吸收材料的最佳带隙为1.8-1.9eV。因此较宽的带隙限制了硒在太阳能电池中的应用，而在室内光源最高理论效率达到55％。此外，硒材料的室内光伏器件还有一点在于其安全性。硒已被公认为对人体免疫系统有益的必需元素。这满足了室内光伏(IPV)应用的要求，其中用于制造物联网产品的材料其中有害物质会受到严格管制。随着IPV的发展，申请人重新审视了硒这种古老材料，认为其实有潜力的室内光伏器件。
本发明的目的在于提供一种硒薄膜室内光伏器件及其制备方法，特别是为硒薄膜室内光伏器件提供了一套完整的制备策略，解决了目前室内光伏器件含有有毒元素、稳定性差或生产复杂等问题，为高性能硒薄膜室内光伏器件提供了技术指导。
本发明提供了以下的技术方案：
一种硒薄膜/碲薄膜室内光伏器件，结构为导电玻璃/电子传输层/碲薄膜/硒薄膜/金电极。
优选地，所述导电玻璃为FTO(氟掺杂二氧化锡)玻璃。更优选地，所述FTO玻璃平均透过率为75-85％，耐高温500-550℃，方阻6-14Ωsq-1，雾度0.6-11％。
优选地，所述电子传输层为TiO2层，选择环境友好的TiO2作为电子传输层，实现了无毒光伏器件的制备，对于室内环境是极为重要的。
进一步地，所述碲薄膜的厚度0.5-5nm，硒薄膜的厚度为0.5-3μm；优选地，所述碲薄膜的厚度为0.5-2.5nm。
硒和碲薄膜均为采用热蒸发蒸镀，通过膜厚仪测量薄膜厚度，到达需要的厚度即停止蒸镀，即得所需要的厚度。
更进一步地，所述电子传输层的厚度为5-80nm，金电极为厚度为50-120nm。
本发明还提供了上述硒薄膜室内光伏器件的制备方法，包括以下步骤：
(1)将导电玻璃进行紫外臭氧处理，用喷涂法在导电玻璃上制备电子传输层，退火，自然冷却后取出备用；
(2)碲薄膜的制备：在步骤(1)得到的电子传输层上采用热蒸发法蒸镀碲薄膜；
(3)硒薄膜的制备：在步骤(2)得到的碲薄膜上采用热蒸发法蒸镀硒薄膜；
(4)电极的制备：在步骤(3)得到的硒薄膜上采用热蒸发法蒸镀电极；
(5)器件退火：步骤(4)得到的器件在热台上退火，自然冷却后取出备用。
优选地，步骤(2)至步骤(4)中，热蒸发的真空度控制在5×10－4Pa以下。
优选地，步骤(2)所述的碲薄膜以碲粉或碲丸作为蒸发源，碲的纯度为99.999％，厚度为0.5-5nm，热蒸发法蒸镀速率为0.05-0.1nm s－1，衬底的温度为常温。
优选地，步骤(3)所述的硒薄膜以硒粉或硒丸作为蒸发源，硒的纯度为99.999％，厚度为500-3000nm，热蒸发法蒸镀速率为0.1-1nm s－1，衬底的温度为常温。
优选地，步骤(4)所述的金电极为厚度为50-120nm，电极的面积为0.09-2.25cm2，热蒸发法蒸镀速率为0.05-0.1nm s－1，衬底的温度为常温。
优选地，步骤(5)热台的退火温度为180-220℃，退火时间为1-30min，优选2-5min。
本发明所述的制备方法制得的高性能硒薄膜室内光伏器件。
总体而言，通过本发明构思的以上技术方案，能够取得下列有益效果：
本发明采用喷涂法制备了二氧化钛电子传输层，调控碲薄膜的厚度、硒薄膜的厚度、器件退火的时间与温度，最终成功得到了一套硒薄膜室内光伏器件的其制备方法，该方法制备简单，器件整体不含有毒物质，并且有利于大面积器件的制备。
本发明成功了制备了硒薄膜室内光伏器件，成功的展示了硒薄膜在室内光伏领域的应用，制备的硒薄膜室内光伏器件具有较高的能量转化效率，在室内光下表现出了较好的稳定性。有利的推动了硒薄膜在室内光伏的发展，并且在物联网领域的应用表现出了巨大的发展前景。
附图说明
图1为分别在标准太阳光、发光二极管(LED，1000lux)以及荧光灯(FL，1000lux)下带隙和SQ极限的关系；
图2为硒薄膜的吸收系数；
图3为本发明硒薄膜室内光伏器件的结构示意图；
图4为本发明是实施例2得到的硒薄膜室内光伏器件的电流-电压曲线；
图5是碲修饰的Se/TiO2界面离域表面缺陷的密度泛函模型图；
图6是0.5nm厚度的碲在二氧化钛衬底的AFM图；
图7是2.5nm厚度的碲在二氧化钛衬底的AFM图；
图8是5nm厚度的碲在二氧化钛衬底的AFM图；
图9是0.5nm和2.5nm厚度的碲器件的C-V和DLCP测试结果图。
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，以下结合图例及实施例，对本发明进一步详细说明。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，应该理解，在阅读了本发明所记载的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本发明所限定的范围。
随着物联网技术的快速发展，设备所需的功耗逐渐减少，可由室内光伏持续供能的节点和数量不断增加。室内人工光源主要有发光二极管(LED)以及荧光灯(FL)等，光源光谱强度集中在400-700nm，而太阳光光谱范围为300-1000nm，相差较大。图2可以看到在标准太阳光、发光二极管和荧光灯下带隙和SQ极限的关系，室内光下最高理论效率超过50％，最佳带隙为1.8-1.9eV。硒薄膜带隙在1.9eV左右，是制备室内光伏器件吸收层的理想材料。图3为硒薄膜的吸收系数，可以看到硒薄膜拥有较大的吸收系数，达到105cm-1。碲是硒太阳能能电池中必不可少的，通常认为碲起到粘附层的作用，防止退火时硒膜脱落，但过量的碲会导致泄露电流增大，效率降低。室内光源光强也远远小于太阳光光强，通常认为室内光源光强为太阳光光强的千分之一，室内光下光生载流子密度较低，复合效应显著。硒太阳能电池最高效率的最优条件在室内光伏并不为最高效率，探究在室内光下的最优条件尤为重要。
以下实施例中FTO玻璃平均透过率>80％，耐高温550℃，方阻＜10Ωsq－1，雾度>7％；双(乙酰丙酮基)二异丙氧基钛(75％的异丙醇溶液)购自阿拉丁，以1:9的体积比配制成乙醇溶液，采用喷涂法制备二氧化钛薄膜；碲粉购自Alfa Aesar，纯度为99.999％，将碲粉装在石英坩埚采用热蒸发法蒸镀碲薄膜；硒丸购自Alfa Aesar，纯度为99.999％，将硒丸装在石英坩埚采用热蒸发法蒸镀硒薄膜；金的纯度为99.999％，采用热蒸发法蒸镀金电极。器件的结构为FTO/TiO2/Te/Se/Au，如图3所示。
制备例光伏器件的制备
制备例1
(1)用去离子水，丙酮和异丙醇分别超声清洗FTO玻璃10分钟，用氮气枪吹干，将清洁的玻璃用紫外抽样处理；
(2)双(乙酰丙酮基)二异丙氧基钛(75％的异丙醇溶液)配制成10％的乙醇溶液，FTO玻璃在400℃热台预热，喷涂制备二氧化钛薄膜，随后将温度提高的500℃保温30分钟；
(3)采用热蒸发法蒸镀碲薄膜，热蒸发的真空度控制在5×10-4Pa以下；厚度为0.5nm，热蒸发法蒸镀速率为0.05nm s－1，衬底的温度为常温。
(4)采用热蒸发法蒸镀硒薄膜，热蒸发的真空度控制在5×10-4Pa以下；厚度为1000nm，热蒸发法蒸镀速率为0.1nm s－1，衬底的温度为常温。
(5)采用热蒸发法蒸镀金电极，热蒸发的真空度控制在5×10-4Pa以下；厚度为70nm，电极的面积为0.09cm2，热蒸发法蒸镀速率为0.1nm s－1，衬底的温度为常温。
(6)器件在热台上退火，温度为200℃，退火时间为2min。
测试条件：2700K LED,1000lux；所得到的硒薄膜室内光伏器件的效率为12.5％，开路电压为0.71V，短路电流为0.101mA cm-2，填充因子为53.9％。
制备例2
其他条件和方法与制备例1相同，区别在于步骤(3)中控制碲薄膜的厚度为2.5nm。
制备例3
其他条件和方法与制备例1相同，区别在于步骤(3)中控制碲薄膜的厚度为5nm。
实施例1
对制备例三个器件在模拟阳光下进行性能测试。测试条件：太阳能电池的J-V测试采用的是Newport公司AM 1.5G太阳光模拟器(型号:94023A，Sol3A Class AAA，450W)作为光源，并配备Keithley 2420数字源表收集信号。使用前用购买的经过NREL认证的标准硅电池(VLSI Standards公司，型号SRC-1000-TC-QZ，面积4cm2)进行光强校正。在空气中室温测量。测试时，扫描范围为-1～1V，扫速为100mV/s(步长20mV，间隔时间200ms)。结果如下表1所示：
表1
实施例2
对制备例三个器件进行室内光伏的性能测试。室内光伏光源为2700K LED，光强为1000lux，通过高精度光纤光谱仪测量光照强度和发光光谱。在空气中室温测量。测试时，扫描范围为-1～1V，扫速为100mV/s(步长20mV，间隔时间200ms)。结果如下表2所示：
表2
碲在硒膜和二氧化钛之间起到桥梁作用。硒碲为同族元素，具有相同的一维晶体结构，容易形成硒碲合金。硒碲原子在单螺旋连上通过共价键连接，如图5所示。由于硒(2.55)、碲(2.01)、氧(3.44)的电负性不同，更容易形成Te-O键，而Se-O键难以形成。器件中含有碲时可以形成Se-Te-O键，退火过程器件正常；当无碲时，硒膜难以和二氧化钛中的氧成键，在退火过程中容易脱膜。这就是硒电池需要加入碲的原因。
除此以外，我们认为碲还起到了钝化硒/二氧化钛界面缺陷的作用。室内光伏条件强度通常为标准太阳光下的千分之一，载流子密度较低，器件中的缺陷态导致复合效应显著。碲在表面的覆盖率决定了钝化程度。图6-图8分别为碲的厚度为0.5nm、2.5nm和5.0nm在二氧化钛衬底的AFM图。可以看出，当碲的厚度为0.5nm时，覆盖率为6.9％，呈现为不连续的孤岛状；当碲的厚度增加到2.5nm时，覆盖率为70.4％，相比于厚度为0.5nm时覆盖率提高一个数量级；当碲的厚度增加到5.0nm时，覆盖率为75.8％，但是过多的碲会导致并联电阻减小，器件的性能显著下降。
随后我们采用电容-电压(C-V)和驱动器级别的电容性能分析(DLCP)探究不同碲的厚度(0.5nm和2.5nm)对Se/TiO2界面的钝化程度，如图9所示。C-V测试结果包括自由载流子、材料体缺陷以及界面缺陷的响应；而DLCP只是对自由载流子以及材料的体缺陷有响应。因此，根据C-V和DLCP测试的差值我们可以得到材料的界面缺陷浓度。图9表明碲的厚度为2.5nm器件界面缺陷密度为6.5×1011cm-2，而碲的厚度为0.5nm器件界面缺陷密度为3.9×1012cm-2，更高的覆盖率导致了更好的钝化效果，这也解释了室内光伏下碲的厚度为2.5nm器件具有最佳性能原因。
应用例
采用碲的厚度为2.5nm下制备了大面积的电池(2.25cm2)，并将三块电池进行串联，在室内光下进行了测试(2700K LED,1000lux,310.4μW cm-2)，单个大面积的电池效率达到了14.0％，串联后(3×2.25cm2)的光电转换效率为11.1％。将电池组和用于定位的RFID标签连接，检测到射频信号，设备成功工作，表明硒电池在物联网领域的应用具有较大的潜力。
Claims (7)
1.一种硒薄膜/碲薄膜器件在室内光伏器件中的应用，其特征在于，所述硒薄膜/碲薄膜器件的结构为导电玻璃/电子传输层/碲薄膜/硒薄膜/金电极；所述碲薄膜的厚度为2.5nm，硒薄膜的厚度为1000nm；所述导电玻璃为FTO玻璃；所述电子传输层为TiO2层所述电子传输层的厚度为5-80 nm，金电极为厚度为50-120 nm；室内光伏光源为2700K LED，光强为1000lux。
2.根据权利要求1所述的应用，其特征在于，所述FTO玻璃平均透过率为75-85%，耐高温500-550℃，方阻6-14 Ω sq-1，雾度0.6-11%。
3.根据权利要求1所述的应用，其特征在于，硒薄膜/碲薄膜器件的制备方法包括以下步骤：
（1）将导电玻璃进行清洗、紫外臭氧处理，采用喷涂法在导电玻璃上制备电子传输层，退火，自然冷却后取出备用；
（2）碲薄膜的制备：在步骤（1）得到的电子传输层上采用热蒸发法蒸镀碲薄膜；
（3）硒薄膜的制备：在步骤（2）得到的碲薄膜上采用热蒸发法蒸镀硒薄膜；
（4）电极的制备：在步骤（3）得到的硒薄膜上采用热蒸发法蒸镀电极；
（5）器件退火：步骤（4）得到的器件在热台上退火，自然冷却后取出备用。
4.根据权利要求3所述的应用，其特征在于，步骤(2)至步骤(4)中，热蒸发的真空度控制在5×10－4 Pa以下。
5. 根据权利要求3所述的应用，其特征在于，步骤（2）所述的碲薄膜以碲粉或碲丸作为蒸发源，碲的纯度为99%以上，厚度为0.5-5 nm，热蒸发法蒸镀速率为0.05-0.1 nm s-1；和/或
步骤（3）所述的硒薄膜以硒粉或硒丸作为蒸发源，硒的纯度为99%以上，厚度为1000nm，热蒸发法蒸镀速率为0.1-1 nm s-1；和/或
步骤（4）所述的金电极为厚度为50-120 nm，电极的面积为0.09-2.25 cm2，热蒸发法蒸镀速率为0.05-0.1 nm s-1。
6. 根据权利要求3所述的应用，其特征在于，步骤（5）热台的退火温度为180-220℃，退火时间为1-30 min。
7.根据权利要求6所述的应用，其特征在于，退火时间为2-5 min。
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