CN104037269A - 一种基于激光诱导晶化的非晶硅薄膜太阳能电池器件的制备方法 - Google Patents

一种基于激光诱导晶化的非晶硅薄膜太阳能电池器件的制备方法 Download PDF

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CN104037269A
CN104037269A CN201410254559.7A CN201410254559A CN104037269A CN 104037269 A CN104037269 A CN 104037269A CN 201410254559 A CN201410254559 A CN 201410254559A CN 104037269 A CN104037269 A CN 104037269A
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史伟民
匡华慧
黄璐
金晶
陆舒逸
杨伟光
刘进
明秀春
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Abstract

本发明涉及一种基于激光诱导晶化的新型非晶硅薄膜太阳能电池器件，属无机材料太阳能器件制备的工艺技术领域。光学薄膜包括减反膜、增透膜、增反膜等，本发明主要通过控制晶粒大小，来达到调制光学薄膜层的增反和增透功能。本发明方法特征在于通过等离子体化学气相沉积法（PECVD）在氧化铟锡（ITO）导电玻璃上沉积三层分别为p型、i型和n型的非晶硅（a-Si）薄膜，然后使用波长为532nm的倍频掺钕钇铝石榴石（Nd:YAG）激光辐照样品表面，来实现n型和p型层由非晶硅转变为多晶硅(poly-Si)光学薄膜层。通过变化激光能量密度，来控制晶化光学薄膜层多晶硅晶粒大小，以调节光电转换效率。本发明的无机材料硅薄膜可应用于太阳能汽车玻璃上和建筑物玻璃幕墙上。

Description

一种基于激光诱导晶化的非晶硅薄膜太阳能电池器件的制备方法
技术领域
本发明涉及一种基于激光诱导晶化的非晶硅薄膜太阳能电池器件的制备工艺，属无机材料太阳能电池技术领域。
背景技术
受到高纯度的硅原料极度短缺的影响，发展新一代的非晶硅（a-Si）薄膜太阳电池在当今世界太阳能光伏产业中显得相当重要。由于a-Si多缺陷的特点，掺杂往往使缺陷密度进一步增加，a-Si太阳电池的基本结构不是pn结，而是pin结。重掺杂的p、n区在电池内部形成内建势，以收集电荷。i区是光敏区，它对光子的吸收系数很高，对敏感谱域的光吸收殆尽。所以，p/i/n结构的a-Si电池的厚度取500nm左右，而作为死光吸收区的p、n层的厚度限制在10nm量级。
非晶硅薄膜太阳电池比起晶体硅太阳电池有诸多优势：首先成本低廉，a-Si可以沉积在普通玻璃上，通过低温（100~300℃）工艺，生产的耗电量小，能量回收时间短；其次它易于形成大规模生产能力，生产可全流程自动化。但是同时，a-Si的缺点也是很明显的，主要就是光电转换效率较低，稳定性较差。为此，在a-Si薄膜的基础上引入再结晶技术，利用激光诱导晶化的方法将沉积好的a-Si薄膜通过退火转变为长程有序的多晶硅（poly-Si）薄膜。同时poly-Si薄膜太阳电池的电子迁移率也接近单晶硅薄膜太阳电池，比非晶硅薄膜太阳电池要高1~2个数量级。
另外，激光诱导晶化法主要是利用瞬间激光脉冲产生的高能量入射非晶硅薄膜表面，仅在薄膜表层产生热能效应，使非晶硅薄膜在瞬间达到1000℃左右，从而实现非晶硅向多晶硅的转变。在此过程中，激光脉冲的瞬间能量被非晶硅薄膜吸收并转化为相变能，因此不会有过多的热能传导到薄膜衬底。合理选择激光的波长和功率，使用激光加热就能够使非晶硅薄膜达到熔化的温度且保证基片的温度低于450℃。因此激光晶化技术已成为一种具有良好应用前景的微晶硅薄膜制备技术。
发明内容
本发明目的在于提供一种基于激光诱导晶化的非晶硅薄膜太阳能电池器件的制备方法。
为达到上述目的，本发明采用如下技术方案：
一种基于激光诱导晶化的非晶硅薄膜太阳能电池器件的制备方法，其特征在于具有以下的过程和步骤：
A. 采用等离子体化学气相沉积法，在射频功率为35W，功率源电容耦合为13.56MHz，衬底氧化铟锡（ITO）导电玻璃的温度范围为180～300℃，气体辉光气压范围为90Pa以下，制备各层非晶硅；其具体工艺参数为：
a. p型层非晶硅的制备：硼烷B2H6与硅烷SiH4质量流量比为0.28%，厚度为20～50nm；
b. i型层非晶硅制备：硅烷SiH4与氢气H2质量流量比为10%，厚度为300～600nm；
c. n型层非晶硅的制备：磷烷PH3与硅烷SiH4质量流量比为0.55%，厚度为30～50nm；
B. 光学薄膜层多晶硅的制备：使用波长为532nm的倍频掺钕钇铝石榴石（Nd:YAG）激光辐照样品表面，经蝇眼技术整形为平顶绿色激光后晶化n型和p型层非晶硅，实现n型和p型层由非晶硅转变为多晶硅光学薄膜层，调节激光能量密度为600～1200mJ/cm2；
C. 阴极导电电极层的制备：使用磁控溅射制备掺铝氧化锌导电电极，厚度为15～30nm；
D. 环氧树脂层封装层的制备：配制环氧树脂的透明溶液，浇注薄膜玻璃四周，盖上上层玻璃盖子，就得到非晶硅薄膜太阳能电池器件。
同现有的技术相比，本发明具有如下显著优点：
1．非晶硅（a-Si）可以沉积在普通玻璃上，通过低温（100~300℃）工艺条件来制备。
2．成本低，生产的耗电量小，能量回收时间短。
3．载流子迁移率高，利用激光诱导晶化后的多晶硅（poly-Si）迁移率明显高于非晶硅（a-Si）两个数量级。
4．易于形成大规模生产能力，生产可全流程自动化。
通过控制晶化光学薄膜层多晶硅晶粒大小，可调节光学薄膜层为增反膜或增透膜，来调整器件的光电转换效率。
附图说明
图1 本发明中激光诱导晶化后多晶硅光学薄膜层的拉曼（Raman）表征图谱和金相显微镜表面形貌表征。
图2 本发明中不同功率激光诱导晶化光学薄膜层的非晶硅太阳能电池电流-电压（I-V）曲线图谱电学性能表征。
图3 本发明中基于激光诱导晶化光学薄膜层的非晶硅薄膜太阳能电池器件结构图。
具体实施方式
本发明的优选实施例结合附图详述如下：
本实施例的具体工艺步骤如下：
A. 采用等离子体化学气相沉积法，在射频功率为35W，功率源电容耦合为13.56MHz，衬底氧化铟锡（ITO）导电玻璃的温度范围为180～300℃，气体辉光气压范围为90Pa以下，制备各层非晶硅；其具体工艺参数为：
a. p型层非晶硅的制备：硼烷B2H6与硅烷SiH4质量流量比为0.28%，厚度为30nm；
b. i型层（本征层）非晶硅制备：硅烷SiH4与氢气H2质量流量比为10%，厚度为500nm；
c. n型层非晶硅的制备：磷烷PH3与硅烷SiH4质量流量比为0.55%，厚度为30nm；
B. 光学薄膜层多晶硅的制备：使用波长为532nm的倍频掺钕钇铝石榴石（Nd:YAG）激光辐照样品表面，经蝇眼技术整形为平顶绿色激光后晶化n型和p型层非晶硅，实现n型和p型层由非晶硅转变为多晶硅光学薄膜层，调节激光能量密度为1000mJ/cm2；
C. 阴极导电电极层的制备：使用磁控溅射制备掺铝氧化锌导电电极，厚度为25nm；
D. 环氧树脂层封装层的制备：配制环氧树脂的透明溶液，浇注薄膜玻璃四周，盖上上层玻璃盖子，就得到非晶硅薄膜太阳能电池器件。
本实施例与上述实施例基本相同，所不同之处在于：
光学薄膜层多晶硅的制备：使用波长为532nm的倍频Nd:YAG激光辐照样品表面，经蝇眼技术整形为平顶绿色激光后，晶化n型和p型层非晶硅，实现n型和p型层由非晶硅转变为多晶硅光学薄膜层。主要通过调节激光能量密度，以控制晶粒大小，来达到调制光学薄膜层的增反和增透功能，现调节激光能量密度为1200mJ/cm2。
本发明方法制得的多晶硅光学薄膜层的非晶硅薄膜太阳能电池器件完全适合于光电太阳能电池的光电转换效率的要求，可用于太阳能汽车薄膜玻璃和建筑物薄膜玻璃幕墙上，降低加工成本，提高光电转换效率。
通过Raman图谱表征光学薄膜层的晶化程度，金相显微镜表征光学薄膜层的表面形貌，I-V曲线表征太阳能电池器件的光电转换性能。本发明方法制备太阳能电池器件检测结果表明：
如图1 Raman图所示，特征峰位在520cm-1左右；如金相显微镜图1插图所示，激光诱导晶化晶粒阵列整齐，晶粒大小统一。
如图2 I-V曲线所示，不同激光功率处理后的非晶硅薄膜太阳能电池器件电学性能与光电转换效率变化明显，激光能量密度在1000mJ/cm2处开路电压和短路电流达到较大值，光电转换性能较明显。
如器件结构图3所示，先通过PECVD在导电玻璃上沉积三层p型、i型和n型的非晶硅，接着使用波长为532nm的倍频掺钕钇铝石榴石激光晶化n型和p型层非晶硅为多晶硅光学薄膜层，然后磁控溅射掺铝氧化锌导电电极，最后在薄膜四周浇注环氧树脂透明溶液并盖上上层玻璃，就得到非晶硅薄膜太阳能电池器件。

Claims (1)

1.一种基于激光诱导晶化的非晶硅薄膜太阳能电池器件的制备方法，其特征在于具有以下的过程和步骤：
A. 采用等离子体化学气相沉积法，在射频功率为35W，功率源电容耦合为13.56MHz，衬底氧化铟锡（ITO）导电玻璃的温度范围为180～300℃，气体辉光气压范围为90Pa以下，制备各层非晶硅；其具体工艺参数为：
a. p型层非晶硅的制备：硼烷B2H6与硅烷SiH4质量流量比为0.28%，厚度为20～50nm；
b. i型层非晶硅制备：硅烷SiH4与氢气H2质量流量比为10%，厚度为300～600nm；
c. n型层非晶硅的制备：磷烷PH3与硅烷SiH4质量流量比为0.55%，厚度为30～50nm；
B. 光学薄膜层多晶硅的制备：使用波长为532nm的倍频掺钕钇铝石榴石（Nd:YAG）激光辐照样品表面，经蝇眼技术整形为平顶绿色激光后晶化n型和p型层非晶硅，实现n型和p型层由非晶硅转变为多晶硅光学薄膜层，调节激光能量密度为600～1200mJ/cm2；
C. 阴极导电电极层的制备：使用磁控溅射制备掺铝氧化锌导电电极，厚度为15～30nm；
D. 环氧树脂层封装层的制备：配制环氧树脂的透明溶液，浇注薄膜玻璃四周，盖上上层玻璃盖子，就得到非晶硅薄膜太阳能电池器件。
CN201410254559.7A 2014-06-10 2014-06-10 一种基于激光诱导晶化的非晶硅薄膜太阳能电池器件的制备方法 Pending CN104037269A (zh)

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