CN104269450B - 一种叠层薄膜太阳电池及其制造方法 - Google Patents
一种叠层薄膜太阳电池及其制造方法 Download PDFInfo
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Abstract
本发明属高效低成本薄膜太阳电池领域，具体为一种叠层薄膜太阳电池及其制造方法(a‑Si:H/a‑SiGe:H/CIGS或CZTS叠层太阳电池及其制造方法)。本发明以玻璃为基底，按照Mo、CIGS或CZTS底电池吸收层、ZnS(O,OH)底电池缓冲层、ZnO底电池窗口层、n型重掺杂a‑SiOx:H中电池预沉积过渡层、p型重掺杂a‑SiOx:H中电池背电极层、a‑SiGe:H中电池本征层、n型重掺杂a‑SiOx:H中电池窗口层、p型重掺杂a‑SiOx:H顶电池背电极、a‑Si:H顶电池本征层、n型a‑SiOx:H顶电池窗口层、n型重掺杂a‑SiOx:H顶电池窗口层、透明导电ITO薄膜和Ag/Al金属栅线前电极的先后顺序制备各层薄膜。构成铜铟镓硒或铜锌锡硫/非晶锗硅/非晶硅三结叠层薄膜太阳电池。
Description
技术领域
本发明涉及一种叠层薄膜太阳电池及其制造方法，具体涉及一种以铜铟镓硒(CIGS)或铜锌锡硫(CZTS)多晶化合物异质结薄膜太阳电池为底电池，p-i-n非晶锗硅(a-SiGe:H)和非晶硅(a-Si:H)分别为中电池和顶电池的双结/三结叠层薄膜太阳电池及其制造方法，属高效低成本薄膜太阳电池领域。
背景技术
太阳电池是利用光伏效应将太阳能直接转换为电能的一种装置。从二十世纪70年代中期开始地面用太阳电池商品化以来，晶体硅就作为基本的电池材料占据着主导地位，晶硅太阳电池及其制造技术几乎发展到了极致，其效率的提高和成本的降低再没有太多的空间，并且制造过程中的污染和能耗问题影响了其应用范围。因此，高效薄膜器件是光伏技术的主要发展方向。
铜铟镓硒(CIGS)或铜锌锡硫(CZTS)均为直接带隙半导体，吸收系数大，是理想的薄膜太阳电池吸收层材料。但是，其光学带隙较窄(约1.1eV)，与太阳光谱不是十分匹配。另一方面，非晶硅基薄膜又难以通过能带工程(如Ge合金化)的方法同时兼得更窄的禁带宽度和较高的吸收系数。此外，铜铟镓硒(CIGS)或铜锌锡硫(CZTS)单结太阳电池目前的光电转换效率世界纪录也只有21.7％(德国Manz集团及其研发伙伴ZSW)和12.6％(日本SolarFrontier)，非晶硅三结(a-Si:H/a-SiGe:H/nc-Si:H)叠层薄膜太阳电池的最高光电转换效率不过16.3％(南开大学)。基于铜铟镓硒(CIGS)或铜锌锡硫(CZTS)、非晶锗硅(a-SiGe:H)和非晶硅(a-Si:H)优良的能带匹配等特点，本发明的太阳电池理论上可实现更高的光电转换效率。
发明目的：以窄带隙的铜铟镓硒(CIGS)或铜锌锡硫(CZTS)拓展长波段光谱吸收，进而实现单一材质结构的CIGS(或CZTS)和非晶硅基(a-Si:H Based)薄膜太阳电池所不能达到的更高光电转换效率。
发明内容
以光吸收带隙为1.1eV、1.4eV和1.72eV左右的铜铟镓硒(CIGS)或铜锌锡硫(CZTS)、非晶锗硅(a-SiGe:H)和非晶硅(a-Si:H)分别作为底电池、中电池和顶电池，以硼(B)和磷(P)掺杂的a-SiOx:H作为硅基薄膜电池的掺杂层，相互叠联形成隧道结。通过带隙可调的a-SiOx:H掺杂层替代传统非晶硅基薄膜太阳电池中普遍采用的a-SiCx:H或nc-Si:H掺杂层，实现了非晶锗硅(a-SiGe:H)和非晶硅(a-Si:H)中电池和顶电池采用n型a-SiOx:H层迎光的p-i-n结构，进而实现了与n型层迎光的铜铟镓硒(CIGS)或铜锌锡硫(CZTS)底电池的串联叠层。
本发明采用图1、图2、图3和图4的太阳电池结构，分别为a-Si:H/CIGS、a-Si:H/a-SiGe:H/CIGS、a-Si:H/CZTS和a-Si:H/a-SiGe:H/CZTS双结、三结叠层薄膜太阳电池。
以玻璃为基底，按照Mo(热蒸发或溅射沉积)、CIGS或CZTS底电池吸收层(共蒸发或溅射沉积)、ZnS(O,OH)底电池缓冲层(MOCVD或化学水浴法)、ZnO底电池窗口层(MOCVD或溅射法)、n型重掺杂a-SiOx:H中电池预沉积过渡层(SiH4，PH3，CO2，H2气氛下的PECVD工艺)、p型重掺杂a-SiOx:H中电池背电极层(SiH4，BF3，CO2，H2气氛下的PECVD工艺)、a-SiGe:H中电池本征层(SiH4，GeH4，H2气氛下的PECVD工艺)、n型重掺杂a-SiOx:H中电池窗口层(SiH4，PH3，CO2，H2气氛下的PECVD工艺)、p型重掺杂a-SiOx:H顶电池背电极(SiH4，BF3，CO2，H2气氛下的PECVD工艺)、a-Si:H顶电池本征层(SiH4，H2气氛下的PECVD工艺)、n型a-SiOx:H顶电池窗口层(SiH4，PH3，CO2，H2气氛下的PECVD工艺)、n型重掺杂a-SiOx:H顶电池窗口层(SiH4，PH3，CO2，H2气氛下的PECVD工艺)、透明导电ITO薄膜(溅射)和Ag/Al金属栅线前电极的先后顺序制备各层薄膜。本发明与公知技术相比具有的优点：
1、本发明与现有技术相比可获得更高光电转换效率；
2、本发明通过带隙可调的a-SiOx:H掺杂层替代传统非晶硅基薄膜太阳电池中普遍采用的a-SiCx:H或nc-Si:H掺杂层，实现了非晶锗硅(a-SiGe:H)和非晶硅(a-Si:H)中电池和顶电池采用n型a-SiOx:H层迎光的p-i-n结构，进而实现了与n型层迎光的铜铟镓硒(CIGS)或铜锌锡硫(CZTS)底电池的真正意义上的双电极串联叠层。
附图说明
图1为本发明提供的一种铜铟镓硒(CIGS)为底电池、非晶硅(a-Si:H)为顶电池的双结叠层薄膜太阳电池结构图。
图2为本发明提供的一种铜铟镓硒(CIGS)为底电池、非晶锗硅(a-SiGe:H)为中电池和非晶硅(a-Si:H)为顶电池的三结叠层薄膜太阳电池结构图。
图3为本发明提供的一种铜锌锡硫(CZTS)为底电池、非晶硅(a-Si:H)为顶电池的双结叠层薄膜太阳电池结构图。
图4为本发明提供的一种铜锌锡硫(CZTS)为底电池、非晶锗硅(a-SiGe:H)为中电池和非晶硅(a-Si:H)为顶电池的三结叠层薄膜太阳电池结构图。
实施例
实施例一
在玻璃衬底上，采用直流磁控溅射技术(气压～1.2-1.5pa、温度～400℃)沉积厚～10nm的Mo薄层；
随后线性降低气压到～0.2-0.5pa，溅射～1μm厚的Mo薄层；
沉积～3μm厚的CIGS(原子比例Cu/(In+Ga)～0.88、Ga/(In+Ga)～0.3)吸收层；采用化学浴沉积(ZnSO4(0.16M)、氨水(7.5M)、硫脲(0.6M))制备～10μm厚的ZnS缓冲层；
采用溅射方法制备～50nm厚的致密ZnO薄膜；
对ZnO薄膜进行450℃退火30min；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型重掺杂a-SiOx:H过渡层；
采用PECVD工艺，在SiH4，BF3，CO2，H2气氛下沉积厚～10nm的p型重掺杂a-SiOx:H背电极层；
采用PECVD工艺，在SiH4，H2气氛下沉积厚～250nm的a-Si:H本征层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型a-SiOx:H窗口层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的重掺杂n型a-SiOx:H窗口层；
采用溅射方法制备透明导电ITO薄膜和Ag/Al金属栅线前电极。
实施例二
在玻璃衬底上，采用直流磁控溅射技术(气压～1.2-1.5pa、温度～400℃)沉积～10nm厚的Mo薄层；
随后线性降低气压到～0.2-0.5pa，溅射～1μm厚的Mo薄层；
沉积～3μm厚的CIGS(原子比例Cu/(In+Ga)～0.88、Ga/(In+Ga)～0.3)吸收层；采用化学浴沉积(ZnSO4(0.16M)、氨水(7.5M)、硫脲(0.6M))制备～10μm厚的ZnS缓冲层；
采用溅射方法制备～50nm厚的致密ZnO薄膜；
对ZnO薄膜进行450℃退火30min；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型重掺杂a-SiOx:H中电池过渡层；
采用PECVD工艺，在SiH4，BF3，CO2，H2气氛下沉积厚～10nm的p型重掺杂a-SiOx:H中电池背电极层；
采用PECVD工艺，在SiH4，GeH4，H2气氛下沉积厚～200nm的a-SiGe:H中电池本征层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型重掺杂a-SiOx:H中电池窗口层；
采用PECVD工艺，在SiH4，BF3，CO2，H2气氛下沉积厚～10nm的p型重掺杂a-SiOx:H顶电池背电极层；
采用PECVD工艺，在SiH4，H2气氛下沉积厚～125nm的a-Si:H顶电池本征层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型a-SiOx:H顶电池窗口层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的重掺杂n型a-SiOx:H顶电池窗口层；
采用溅射方法制备透明导电ITO薄膜和Ag/Al金属栅线前电极。
实施例三
在玻璃衬底上，采用直流磁控溅射技术(气压～1.2-1.5pa、温度～400℃)沉积～10nm厚的Mo薄层；
随后线性降低气压到～0.2-0.5pa，溅射～1μm厚的Mo薄层；
采用共蒸发技术制备厚～3μm的CZTS吸收层；采用化学浴沉积(ZnSO4(0.16M)、氨水(7.5M)、硫脲(0.6M))制备～10μm厚的ZnS缓冲层；
采用溅射方法制备～50nm厚的致密ZnO薄膜；
对ZnO薄膜进行450℃退火30min；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型重掺杂a-SiOx:H过渡层；
采用PECVD工艺，在SiH4，BF3，CO2，H2气氛下沉积厚～10nm的p型重掺杂a-SiOx:H背电极层；
采用PECVD工艺，在SiH4，H2气氛下沉积厚～250nm的a-Si:H本征层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型a-SiOx:H窗口层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的重掺杂n型a-SiOx:H窗口层；
采用溅射方法制备透明导电ITO薄膜和Ag/Al金属栅线前电极。
实施例四
在玻璃衬底上，采用直流磁控溅射技术(气压～1.2-1.5pa、温度～400℃)沉积～10nm厚的Mo薄层；
随后线性降低气压到～0.2-0.5pa，溅射～1μm厚的Mo薄层；
采用共蒸发技术制备厚～3μm的CZTS吸收层；
采用化学浴沉积(ZnSO4(0.16M)、氨水(7.5M)、硫脲(0.6M))制备～10μm厚的ZnS缓冲层；
采用溅射方法制备～50nm厚的致密ZnO薄膜；
对ZnO薄膜进行450℃退火30min；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型重掺杂a-SiOx:H中电池过渡层；
采用PECVD工艺，在SiH4，BF3，CO2，H2气氛下沉积厚～10nm的p型重掺杂a-SiOx:H中电池背电极层；
采用PECVD工艺，在SiH4，GeH4，H2气氛下沉积厚～200nm的a-SiGe:H中电池本征层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型重掺杂a-SiOx:H中电池窗口层；
采用PECVD工艺，在SiH4，BF3，CO2，H2气氛下沉积厚～10nm的p型重掺杂a-SiOx:H顶电池背电极层；
采用PECVD工艺，在SiH4，H2气氛下沉积厚～125nm的a-Si:H顶电池本征层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的n型a-SiOx:H顶电池窗口层；
采用PECVD工艺，在SiH4，PH3，CO2，H2气氛下沉积厚～10nm的重掺杂n型a-SiOx:H顶电池窗口层；
采用溅射方法制备透明导电ITO薄膜和Ag/Al金属栅线前电极。
Claims (2)
1.一种叠层薄膜太阳电池的制造方法，其特征是：“以窄带隙的铜铟镓硒CIGS或铜锌锡硫CZTS拓展长波段光谱吸收，进而实现单一材质结构的CIGS或CZTS和非晶硅基薄膜太阳电池所不能达到的更高光电转换效率，并通过带隙可调的a-SiOx:H掺杂层替代传统非晶硅基薄膜太阳电池中普遍采用的a-SiCx:H或nc-Si:H掺杂层，实现了非晶锗硅和非晶硅中电池和顶电池采用n型a-SiOx:H层迎光的p-i-n结构，进而实现了与n型层迎光的铜铟镓硒CIGS或铜锌锡硫CZTS底电池的真正意义上的双电极串联叠层”。
2.根据权利要求1中所述的制造方法，其特征在于，铜铟镓硒CIGS或铜锌锡硫CZTS与非晶硅基薄膜太阳电池构成双电极串联叠层，拓展长波段光谱吸收，从而达到更高光电转换效率。
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