CN111599881B - 一种单晶氧化亚铜复合半导体纳米发电机及其制造方法 - Google Patents

一种单晶氧化亚铜复合半导体纳米发电机及其制造方法 Download PDF

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CN111599881B
CN111599881B CN201910982818.0A CN201910982818A CN111599881B CN 111599881 B CN111599881 B CN 111599881B CN 201910982818 A CN201910982818 A CN 201910982818A CN 111599881 B CN111599881 B CN 111599881B
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李阳
王志勇
陶冉
罗凯
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Jiangsu University of Science and Technology
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Abstract

本发明涉及维纳能源技术领域，具体地说，是一种单晶氧化亚铜复合半导体纳米发电机及其制造方法，能够应用于半导体领域、光伏发电领域，以及热电转换领域，包括透明基底、底部电极层、p型半导体层、单晶氧化亚铜层、n型半导体层、顶部电极层，其中，单晶氧化亚铜层为定向生长所得，使其与p型半导体层接触部分为{111}晶面，且与n型半导体层接触部分为{100}晶面，本发明具有结构简单、生产成本低，经济环保等诸多优点与特点。

Description

一种单晶氧化亚铜复合半导体纳米发电机及其制造方法
技术领域
本发明涉及维纳能源技术领域，具体地说，是一种单晶氧化亚铜复合半导体纳米发电机及其制造方法，能够应用于半导体领域、光伏发电领域，以及热电转换领域。
背景技术
太阳能电池是直接把光能转化成电能的装置。目前研发以及商用的太阳能电池主要依赖于p-n结。太阳光照射在半导体p-n结上，形成新的空穴-电子对。在p-n结电场的作用下，空穴由n区流向p区，电子由p区流向n区，连接外电路后就形成电流。
氧化亚铜（Cu2O）是一种直接带隙半导体材料，具有原料丰富、制备简单、价格便宜、环境友好等特点。其禁带宽度与薄膜制备条件有关，一般为1.7~2.1 eV，其太阳能电池的理论光电转换效率可以超过20％。
目前公开的Cu2O太阳能电池，一般需要形成异质结来辅助载流子分离，如p-Cu2O/n-ZnO（氧化锌），不但结构复杂、制造工艺要求高，成本较高，而且异质结电池的界面缺陷密度大，从而造成较大的界面复合电流，实际发电效率低。
虽然已有报道公开了Cu2O同质结太阳能电池，p-Cu2O/n-Cu2O（CN 102376783 A），但目前仍然缺少理论依据与检测分析，转换效率仍然偏低。
发明内容
本发明的第一个目的是为了开发一种不同于传统p-n结的载流子分离结构，提供了一种全新的“晶面结”载流子分离结构。
本发明的第二个目的是优化“晶面结”载流子分离结构，提出了一种全新的复合半导体结构。
本发明的第三个目的是提供了一种基于晶面结的单晶氧化亚铜复合半导体纳米发电机的制备方法。
为了实现第一和第二个目的，本发明的技术方案是：一种单晶氧化亚铜复合半导体纳米发电机，包括透明基底层，透明基底层上设置有底部电极层，底部电极层上设置有n型半导体层，n型半导体层上设置有单晶氧化亚铜层，单晶氧化亚铜层的表面设置有p型半导体层，p型半导体层上设置有顶部电极层。
在上述技术方案中，透明基底层由为玻璃、石英或塑料薄膜材料制成；底部电极层为透明导电层，透明导电层为ITO层或FTO层；顶部电极层由导体材料制成，导体材料为金属或导电类有机物、无机物或氧化物薄膜；单晶氧化亚铜层为定向生长所得，其与n型半导体层（3）接触部分为{111}晶面（A），且与p型半导体层（5）接触部分为{100}晶面（B）。
为实现第三个发明目的，所采用的技术方案是：一种单晶氧化亚铜复合半导体纳米发电机的制造方法，包括如下步骤：步骤一：透明基底的清洗与底部电极层的制备：透明基底清洗吹干，利用磁控溅射法生长底部电极层；步骤二：n型半导体层的制备：采用旋涂法、刮涂法、浸渍提拉法、物理气相沉积法、化学气相沉积法生长n型半导体；步骤三：单晶氧化亚铜的制备：利用电沉积法生长氧化亚铜单晶薄膜；步骤四：p型半导体层的制备：采用旋涂法、刮涂法、浸渍提拉法、物理气相沉积法、化学气相沉积法生长p型半导体；步骤五：顶部电极层的制备：采用物理气相沉积法、匀胶法、刮涂法，在氧化亚铜{100}晶面上覆盖一层导体层。
本发明利用电沉积生长的Cu2O在底部电极层一侧为{111}晶面，在顶部电极层一侧为{100}晶面，由于两种晶面间的能带结构不一致形成了天然的能量差异，致使在Cu2O内部产生的电子自发流向{100}晶面，空穴流向{111}晶面，从而达到载流子的分离。此外，p型半导体层和n型半导体层分别作为空穴传输层和电子传输层，加快了载流子的分离和传输，底部电极与顶部电极分别作为电池的负极与正极。当连接外电路时，底部电极层作为负极（阳极），顶部电极层作为正极（阴极），向外输送电能。
本发明的有益效果：本发明基于氧化亚铜各晶面存在各相异性，即同时存在{100}和{111}晶面，{100}晶面与{111}晶面会分别表现出还原性与氧化性，采用不同晶面间的各相异性，来实现载流子的自动分离，从而向外输出电能。此外，p型半导体层和n型半导体层分别作为空穴传输层和电子传输层，加快了载流子的分离和传输，底部电极与顶部电极分别作为电池的负极与正极。
附图说明
图1是本发明的结构示意图。
图中，1-透明基底层，2-底部电极层，3- n型半导体层，4-单晶氧化亚铜层，5- p型半导体层，6-顶部电极层。
具体实施方式
为了加深对本发明的理解，下面将结合附图和实施例对本发明做进一步详细描述，该实施例仅用于解释本发明，并不对本发明的保护范围构成限定。
实施例：如图1所示，一种单晶氧化亚铜复合半导体纳米发电机，包括透明基底层1，透明基底层1上设置有底部电极层2，底部电极层2上设置有n型半导体层3，n型半导体层3上设置有单晶氧化亚铜层4，单晶氧化亚铜层4的上表面呈纳米立方体，单晶氧化亚铜层4的纳米立方体表面设置有p型半导体层5，p型半导体层5上设置有顶部电极层6。
在本实施中，透明基底层1由为玻璃、石英或塑料薄膜材料制成；底部电极层2为透明导电层，透明导电层为ITO层或FTO层；顶部电极层6由导体材料制成，导体材料为金属或导电类有机物、无机物或氧化物薄膜；单晶氧化亚铜层4为定向生长所得，其与n型半导体层3（3）接触部分为{111}晶面（A），且与p型半导体层5（5）接触部分为{100}晶面（B）。
在上述实施例中，透明基底层采用康宁玻璃，厚度1.1mm。依次采用去污粉、去离子水、异丙醇、乙醇盐酸、丙酮对衬底进行10min超声清洗，除去表面有机及无机杂质，最后用氮气吹干待用。采用射频磁控溅射法，在透明基底上生长FTO透明导电层，厚度300nm。将一定比例的四水醋酸镍，PEG6000溶于无水乙醇中，在60摄氏度下恒温磁力搅拌1h。采用匀胶旋涂法，将所得溶液滴涂在FTO导电层上，以3000rmp的速度匀胶1min。在马弗炉中以1摄氏度/min的升温速率升温至500摄氏度，并保持1h，获得p型NiO层，厚度50nm。将无水硫酸铜1.2g，溶解于40mL去离子水中，磁力搅拌直至充分溶解，得到澄清透明的淡蓝色溶液。加入10mL乳酸钠，磁力搅拌后得到澄清透明的深蓝色溶液。逐步滴加浓度为1M的NaOH溶液直至pH为12。以导电玻璃为负极，金属铂电极为正极，施加恒电压2V，使氧化亚铜在导电玻璃表面沉积，直至薄膜厚度生长到3000nm后切断电源。取出氧化亚铜单晶电极，用去离子水反复冲洗，并用氮气吹干。采用反应磁控溅射法，在氧化亚铜{100}晶面上生长一层n-TiO2层，厚度50nm。用掩模板遮挡暴露的FTO区域，在氧化亚铜单晶{100}面上蒸镀一层铜电极，厚度100nm。
本实施例的工作原理：将所得纳米发电机的导电玻璃端和铝电极分别与台式万用表的正极与负极连接。在黑暗状况（20℃）下，测得开路电压67.5mV，短路电流150.2μA/cm2。在标准光照条件(AM1.5，100mW/cm2，20℃)下，开路电压为0.97V，短路电流密度为6.13mA/cm2，填充因子为68％，光电转换效率为4.0％。
不仅如此，该纳米发电机还可以自发地将热能转换为电能。在200℃的黑暗状态下，单晶氧化亚铜纳米发电机可以产生的开路电压高达1.75V，短路电流密度达到了12.1mA/cm2。
以上显示和描述了本发明的基本原理、主要特征及优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (7)

1.一种单晶氧化亚铜复合半导体纳米发电机，其特征在于，包括透明基底层，所述透明基底层上设置有底部电极层，所述底部电极层上设置有n型半导体层，所述n型半导体层上设置有单晶氧化亚铜层，所述单晶氧化亚铜层的上表面为完全暴露{100}晶面的纳米立方体，所述单晶氧化亚铜层的{100}晶面表面设置有p型半导体层，所述p型半导体层上设置有顶部电极层，所述的单晶氧化亚铜层为定向生长所得，其与n型半导体层接触部分为{111}晶面，且与p型半导体层接触部分为{100}晶面。
2.根据权利要求1所述的单晶氧化亚铜复合半导体纳米发电机，其特征在于，所述透明基底层由为玻璃、石英或塑料薄膜材料制成。
3.根据权利要求1所述的单晶氧化亚铜复合半导体纳米发电机，其特征在于，所述底部电极层为透明导电层。
4.根据权利要求3所述的单晶氧化亚铜复合半导体纳米发电机，其特征在于，所述透明导电层为ITO层或FTO层。
5.根据权利要求1所述的单晶氧化亚铜复合半导体纳米发电机，其特征在于，所述顶部电极层由导体材料制成。
6.根据权利要求5所述的单晶氧化亚铜复合半导体纳米发电机，其特征在于，所述导体材料为金属或导电类有机物、无机物。
7.一种如权利要求1-6任一项所述的单晶氧化亚铜复合半导体纳米发电机的制造方法，其特征在于，包括以下步骤：
步骤一：透明基底的清洗与底部电极层的制备：透明基底清洗吹干，利用磁控溅射法生长底部电极层；
步骤二：n型半导体层的制备：采用旋涂法、刮涂法、浸渍提拉法、物理气相沉积法、化学气相沉积法生长n型半导体；
步骤三：单晶氧化亚铜的制备：利用电沉积法生长氧化亚铜单晶薄膜；
步骤四：p型半导体层的制备：采用旋涂法、刮涂法、浸渍提拉法、物理气相沉积法、化学气相沉积法生长p型半导体；
步骤五：顶部电极层的制备：采用物理气相沉积法、匀胶法、刮涂法，在氧化亚铜{100}晶面上覆盖一层导体层。
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