CN102237417B - 串联型光电装置及其制造方法 - Google Patents

串联型光电装置及其制造方法 Download PDF

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CN102237417B
CN102237417B CN201010614094.3A CN201010614094A CN102237417B CN 102237417 B CN102237417 B CN 102237417B CN 201010614094 A CN201010614094 A CN 201010614094A CN 102237417 B CN102237417 B CN 102237417B
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明承烨
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Neo Lab Convergence Inc.
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Abstract

本发明涉及一种串联型光电装置及其制造方法，该串联型光电装置包括：第一电极，包括透明导电性氧化物层；第一单元电池，位于所述第一电极上，且包括依次层压的p型半导体层、纯半导体层和n型半导体层；第二单元电池，位于所述第一单元电池上，且包括依次层压的p型半导体层、纯半导体层和n型半导体层；第二电极，位于所述第二单元电池上；其中，所述第一单元电池的纯半导体层由氢化非晶硅或氢化非晶硅系物质构成，所述第二单元电池的纯半导体层由氢化微晶硅或氢化微晶硅系物质构成，相对于形成在所述第一电极表面上的凹凸的平均节距的均方根粗糙度为0.05～0.13。

Description

串联型光电装置及其制造方法
技术领域
本发明涉及串联型光电装置及其制造方法。
背景技术
目前，伴随着现有能源如石油、煤炭等将会枯竭的预测，人们越来越关注替代这些现有能源的可替代能源。其中，太阳能因其资源丰富且不污染环境而特别受到瞩目。
直接将太阳能转换为电能的装置是光电装置，即太阳能电池。光电装置主要利用了半导体接合的光电现象。即，如果光入射到分别掺杂了P型和n型杂质的半导体p-i-n接合面并被吸收，则光能在半导体内部产生电子和空穴，所产生的电子和空穴通过内部电场发生分离，由此使光电产生在p-i-n接合两端上。此时，如果在接合两端上形成电极，并由导线将其连接，则电流通过电极和导线而流向外部。
为了由太阳能替代现有能源(例如，石油等)，必须提供具有高光电转换效率的光电装置。
发明内容
本发明的目的在于，减少串联p-i-n型光电装置中第一电极的表面凹凸对第二单元电池的影响。
本发明的光电装置包括：第一电极，包括透明导电性氧化物层；第一单元电池，位于所述第一电极上，且包括依次层压的p型半导体层、纯半导体层和n型半导体层；第二单元电池，位于所述第一单元电池上，且包括依次层压的p型半导体层、纯半导体层和n型半导体层；第二电极，位于所述第二单元电池上；其中，所述第一单元电池的纯半导体层由氢化非晶硅或氢化非晶硅系物质构成，所述第二单元电池的纯半导体层由氢化微晶硅或氢化微晶硅系物质构成，相对于形成在所述第一电极表面上的凹凸的平均节距的均方根粗糙度为0.05～0.13。
本发明光电装置的制造方法包括以下步骤：在基板上沉积透明导电性氧化物层，并通过对所述透明导电性氧化物层表面的蚀刻形成第一电极；形成包括依次层压在所述第一电极上的p型半导体层、纯半导体层和n型半导体层的第一单元电池；形成包括依次层压在所述第一单元电池上的p型半导体层、纯半导体层和n型半导体层的第二单元电池；以及在所述第二单元电池上形成第二电极；其中，所述第一单元电池的纯半导体层由氢化非晶硅或氢化非晶硅系物质构成，所述第二单元电池的纯半导体层由氢化微晶硅或氢化微晶硅系物质构成，相对于形成在所述第一电极表面上的凹凸的平均节距的均方根粗糙度为0.05～0.13。
在本发明中，由于在形成第一电极时进行蚀刻工序，因此能够减少第一电极对由微晶硅或微晶硅系物质构成的第二单元电池的影响。
附图说明
图1a～图1e表示根据本发明实施例的串联型光电装置的制造过程；
图2表示未进行蚀刻工序时的、由氢化非晶硅或氢化非晶硅系物质构成的第一导电性半导体层和纯半导体层；
图3表示根据本发明实施例的光电装置的第一电极凹凸之间的节距。
符号说明
100  基板
200  第一电极
300  第一单元电池
400  第二单元电池
500  第二电极
具体实施方式
以下，参照附图详细说明本实施例。
图1a～图1e表示根据本发明实施例的串联型光电装置的制造过程。在本发明实施例中，为了便于说明省略激光刻槽工序等单元电池的串联连接过程。
如图1a所示，在基板100上沉积透明导电性氧化物层。当沉积有ZnO或ITO等透明导电性氧化物层时，在透明导电性氧化物层的表面形成有凹凸。即，通过化学气相沉积法(CVD：Chemical Vapor Deposition)沉积透明导电性氧化物层时，在透明导电性氧化物层的表面形成如图1a所示的、金字塔形状的锋利的表面凹凸。此时，基板100可以由透明绝缘性材质构成，以便具有良好的光透射率且能够防止薄膜太阳能电池中的内部短路。
如图1b所示，透明导电性氧化物层的表面凹凸被湿式蚀刻。由此形成具有平缓的表面凹凸的第一电极200。湿式蚀刻能够缩短用来形成平缓的表面凹凸的工序时间。即，湿式蚀刻的蚀刻速度与干式蚀刻相比较快，因此能够缩短第一电极200的形成时间。湿式蚀刻按照将沉积有第一电极200的基板在浓度为0.5％～5％的酸性水溶液中浸泡5～20秒的方式进行。如果酸性水溶液的浓度低于0.5％，则因蚀刻率过低而花费较长时间，如果酸性水溶液的浓度高于5％，则因蚀刻率过高而难以控制蚀刻，因此存在表面凹凸不匀的问题。即，当酸性水溶液的浓度处于0.5％～5％时，既能够控制蚀刻也能够实现充分的蚀刻。
另外，如果酸性水溶液中的蚀刻时间低于5秒，则无法进行充分的蚀刻，如果蚀刻时间超过20秒，则表面凹凸会过于平缓，由此引起光捕捉效果降低而使短路电流减少，或氧化锌过于变薄而使导电率降低，且填充因子也减小而可能使转换效率降低。因此，当利用酸性水溶液进行蚀刻的蚀刻时间为5～20秒时，能够在短时间内形成平缓的表面凹凸，且不会降低光捕捉效果或短路电流，且可以防止因导电率和填充因子减少而引起的光电效率的降低。
此时，用于湿式蚀刻工序的酸的种类为盐酸(HCl)、偏磷酸(HPO3)、硝酸(HNO3)、乙酸(CH3COOH)中的至少一个。
对于透明导电性氧化物层的蚀刻，后述中参照附图进行详细说明。
如图1c所示，在第一电极200上形成第一单元电池300。第一单元电池300包括依次层压的第一导电性半导体层310、纯半导体层330和第二导电性半导体层350。本发明实施例的第一导电性半导体层310、纯半导体层330和第二导电性半导体层350可以分别为p型半导体层、纯半导体层和n型半导体层。
此时，位于第一电极200上的第一单元电池300的纯半导体层330可以由氢化非晶硅或氢化非晶硅系物质来构成。本发明实施例中的非晶硅系物质可以包括氧、碳或氮等非硅系元素。例如，当纯半导体层330包括氧、碳或氮时，纯半导体层330可以包括氢化非晶氧化硅(a-SiO:H)、氢化非晶硅碳(a-SiC:H)或氢化非晶氮化硅(a-SiN:H)。
如图1d所示，在第一单元电池300上形成第二单元电池400。第二单元电池400包括依次层压的第一导电性半导体层410、纯半导体层430和第二导电性半导体层450。在本发明的实施例中，第一导电性半导体层410、纯半导体层430和第二导电性半导体层450可以分别为p型半导体层、纯半导体层和n型半导体层。
此时，第二单元电池400的纯半导体层430可由氢化微晶硅或氢化微晶硅系物质构成。本发明实施例中的微晶硅系物质可包括锗等非硅系元素。例如，当纯半导体层430包括锗元素时，纯半导体层430可以包括氢化微晶硅锗(μc-SiGe:H)。
本发明实施例中，第一单元电池300和第二单元电池400为p-i-n型单元电池，因此光可通过基板100入射。另外，第一单元电池300包括氢化非晶硅或氢化非晶硅系物质，第二单元电池400包括氢化微晶硅或氢化微晶硅系物质。
如图1e所示，在第二单元电池400上形成第二电极500。
如上所述，在本发明实施例中进行透明导电性氧化物层的沉积和蚀刻。在未进行蚀刻工序时，如图2所示，包括由氢化非晶硅或氢化非晶硅系物质构成的纯半导体层330的第一单元电池300形成在具有金字塔形状的第一电极200的表面。由此，在位于第一电极200上的、第一单元电池300和第二单元电池400的表面上也形成锋利的凹凸。
此时，第二单元电池400的凹凸中，具有‘V’字型溪谷形状的部分600起到龟裂的作用，妨碍氢化微晶硅或氢化微晶硅系物质的形成，且形成非晶质的孵化层(incubation layer)700和大体积的晶粒界800。孵化层700和晶粒界800作用在从氢化微晶硅或氢化微晶硅系物质中光生成的电子-空穴对(electron-hole pair)再结合的中心部分，因此降低光电装置的整体特性。
由此，在本发明的实施例中，于第一电极200的表面上形成凹凸后进行蚀刻工序。对电极表面的凹凸进行蚀刻后形成如图3所示的光电装置。即，如图3所示，金字塔形状的表面凹凸通过蚀刻工序而变得平缓。由此，具有锋利的金字塔形状的表面凹凸变成‘U’字形的平缓的表面凹凸。在具有这种平缓的表面凹凸的第一电极200上形成第一单元电池300，在第一单元电池300上沉积第二单元电池400的微晶硅系或微晶硅系物质时，更加顺利地形成第二单元电池40的微晶硅或微晶硅系物质，且减少非晶质的孵化层700和大体积的晶粒界800，因此光电装置的特性得到提高。
相对于通过上述蚀刻工序形成在第一电极200表面上的凹凸之间的平均节距(pitch)的均方根粗糙度(Root Mean Square roughness)可以为0.05～0.13。如图3所示，凹凸之间的节距是指两个相邻突出部之间的距离(L)，凹凸之间的平均节距是指这些每个节距的平均值。均方根粗糙度是可以在利用原子力显微镜(AFM，Atomic Force Microscope)测量规定面积的表面段差后，通过下述式求出。
Figure BSA00000403593300051
此时，Xi为所测量的段差，
Figure BSA00000403593300052
是平均段差。
如果相对于平均节距的均方根粗糙度小于0.05，则透明导电性氧化物层变得过于平坦，因此会减少通过第一电极200来进行的光散射效果。另外，如果相对于平均节距(pitch)的均方根粗糙度大于0.13，则凹凸变得过于粗糙，有可能形成大体积的晶粒界800。
如此地，相对于凹凸平均节距的均方根粗糙度为0.05～0.13时，透明导电性氧化物层的厚度可以为1μm～2μm。
测量通过蚀刻工序而形成的第一电极200的XRD(X-Ray Diffraction)θ-2θgeometry时，平面的峰值大于对(0002)平面和
Figure BSA00000403593300054
平面的峰值时，形成金字塔形状的凹凸，因此被蚀刻的、相对于凹凸的平均节距的均方根粗糙度可以为0.05～0.13。
通过蚀刻工序形成的第一电极200由ZnO构成时，通过X射线光电子能谱(XPS，X-ray Photoelectron Spectroscopy)或俄歇电子能谱(Auger ElectronSpectroscopy)、二次离子质谱(SIMS，Secondary Ion Mass Spectrometer)，对ZnO深度的结构和组成进行分析时，Zn/O的比例可以为1.1～1.3。如果Zn/O的比例为1.3以下，则能够防止光透射率的急剧下降，如果Zn/O的比例为1.1以上，则由于具有化学计量结构(stoichiometric structure)，因此可以防止导电率的急剧下降。
当通过蚀刻所形成的第一电极200由ZnO来构成时，第一电极200中所含有的氢浓度可以为1019/cm3～1021/cm3。如上所述，氢作为ZnO的较低的施主能级提高ZnO的导电率，且能够钝化如氧空位(oxygen vacancy)等的缺陷。如果所含有的氢浓度低于1019/cm3，则有可能降低导电率且降低钝化作用。如果所含有的氢浓度大于1021/cm3，则所产生的杂质散射(impurity scattering)会造成移动度的下降，且有可能减少因自由载流子吸收的在1000nm以上的长波段区域的光透射率。
进行沉积和蚀刻工序时，第一电极200的比电阻可以为2×10-3Ωcm以下，移动度可以为25cm2/Vsec以上。另外，在波长为60nm的光中，通过蚀刻所形成的第一电极200的雾度(haze ratio)为5％～20％。另外，在波长为400nm～800nm的光中，第一电极200的透射率可以为80％以上。
另一方面，本发明实施例可以为p-i-n型光电装置，第一单元电池300与第二单元电池400相比，能够更好地吸收短波长区域光，第二单元电池400与第一单元电池300相比，能够更好地吸收长波长区域光。
即，如本发明实施例，当光电装置为p-i-n型串联光电装置时，由于光通过基板100入射，因此第一电极200可以由透明导电性氧化物层构成，第一单元电池300可以由氢化非晶硅或氢化非晶硅系物质构成以便更好地吸收短波长区域的光。此时，在透明导电性氧化物层的表面形成凹凸，通过表面凹凸而形成的第二单元电池400的氢化微晶硅或氢化微晶硅系物质中有可能形成非晶质的孵化层700和大体积的晶粒界800。为此，在本发明实施例的光电装置中，由于先沉积透明导电性氧化物层后再进行蚀刻工序，因此能够提高p-i-n型串联光电装置的特性。
以下，对本发明实施例的光电装置进行说明。
根据本发明实施例的光电装置包括基板100、第一电极200、第一单元电池300、第二单元电池400和第二电极500。
第一电极200包括透明导电性氧化物层，相对于形成在第一电极200表面上的凹凸的平均节距的均方根粗糙度可以为0.05～0.13。
第一单元电池300包括位于第一电极200上，包括依次层压的p型半导体层、纯半导体层和n型半导体层。第一单元电池300的纯半导体层由氢化非晶硅或氢化非晶硅系物质构成。
第二单元电池400位于第一单元电池300上，且包括依次层压的p型半导体层、纯半导体层和n型半导体层。第二单元电池400的纯半导体层是由氢化微晶硅或氢化微晶硅系物质构成。
第二电极500位于第二单元电池400上。
根据本发明实施例的光电装置的特性已在上述记载中进行了说明，因此省略该说明。
如上所述，参照附图对本发明的实施例进行了说明，本领域的技术人员应该可以理解在不变更本发明的技术思想或必要特征的条件下可以采用其它具体实施方式。因此，上述的实施例只是举例而已，本发明并不仅限定于上述实施例。从等同概念出发的所有变更或者变更的方式应解释为包含在本发明的范围。

Claims (16)

1.一种光电装置，其特征在于：所述光电装置包括：
第一电极，包括透明导电性氧化物层；
第一单元电池，位于所述第一电极上，且包括依次层压的p型半导体层、纯半导体层和n型半导体层；
第二单元电池，位于所述第一单元电池上，且包括依次层压的p型半导体层、纯半导体层和n型半导体层；
第二电极，位于所述第二单元电池上；其中
所述第一单元电池的纯半导体层由氢化非晶硅或氢化非晶硅系物质构成，
所述第二单元电池的纯半导体层由氢化微晶硅或氢化微晶硅系物质构成，
相对于形成在所述第一电极表面上的凹凸的平均节距的均方根粗糙度为0.05～0.13，所述凹凸具有“U”字形的谷状凹陷，
其中所述第一单元电池具有“U”字形的谷状凹陷，且所述第二单元电池具有“U”字形的谷状凹陷。
2.如权利要求1所述的光电装置，其特征在于：所述透明导电性氧化物层的厚度为1μm～2μm。
3.如权利要求1所述的光电装置，其特征在于：测量所述第一电极的XRDθ-2θgeometry时，
Figure FDA0000370559020000011
平面的峰值大于（0002）平面和
Figure FDA0000370559020000012
平面的峰值。
4.如权利要求1所述的光电装置，其特征在于：所述第一电极包括由ZnO构成的透明导电性氧化物层，且Zn/O的比例为1.1～1.3。
5.如权利要求1所述的光电装置，其特征在于：所述第一电极包括由ZnO构成的透明导电性氧化物层，所述透明导电性氧化物层所含有的氢浓度为1019/cm3～1021/cm3。
6.如权利要求1所述的光电装置，其特征在于：所述透明导电性氧化物层的比电阻为2×10-3Ωcm以下，移动度为25cm2/Vsec以上。
7.如权利要求1所述的光电装置，其特征在于：在600nm波长的光中，所述透明导电性氧化物层的雾度为5%～～20%，在波长为400nm～800nm的光中，所述透明导电性氧化物层的透射率为80%以上。
8.一种光电装置的制造方法，其特征在于：所述光电装置的制造方法包括以下步骤：
在基板上沉积透明导电性氧化物层，并对所述透明导电性氧化物层的表面进行蚀刻以形成第一电极；
形成包括依次层压在所述第一电极上的p型半导体层、纯半导体层和n型半导体层的第一单元电池；
形成包括依次层压在所述第一单元电池上的p型半导体层、纯半导体层和n型半导体层的第二单元电池；以及
在所述第二单元电池上形成第二电极；其中
所述第一单元电池的纯半导体层由氢化非晶硅或氢化非晶硅系物质构成，
所述第二单元电池的纯半导体层由氢化微晶硅或氢化微晶硅系物质构成，
相对于形成在所述第一电极表面上的凹凸的平均节距的均方根粗糙度为0.05～0.13，所述凹凸具有“U”字形的谷状凹陷，
其中所述第一单元电池具有“U”字形的谷状凹陷，且所述第二单元电池具有“U”字形的谷状凹陷。
9.如权利要求8所述的光电装置的制造方法，其特征在于：
所述透明导电性氧化物层通过化学气相沉积法以1μm～2μm的厚度被沉积。
10.如权利要求8所述的光电装置的制造方法，其特征在于：
测量所述第一电极的XRDθ-2θgeometry时，
Figure FDA0000370559020000021
平面的峰值大于（0002）平面和
Figure FDA0000370559020000031
平面的峰值。
11.如权利要求8所述的光电装置的制造方法，其特征在于：
在沉积所述透明导电性氧化物层的步骤中，包括沉积由ZnO构成的透明导电性氧化物层的步骤，且Zn/O的比例为1.1～1.3。
12.如权利要求8所述的光电装置的制造方法，其特征在于：
在沉积所述透明导电性氧化物层的步骤中，包括沉积由ZnO构成的透明导电性氧化物层的步骤，且
所述透明导电性氧化物层所含有的氢浓度为1019/cm3～1021/cm3。
13.如权利要求8所述的光电装置的制造方法，其特征在于：
所述透明导电性氧化物层的比电阻为2×10-3Ωcm以下，移动度为25cm2/Vsec以上。
14.如权利要求8所述的光电装置的制造方法，其特征在于：
在600nm波长的光中，所述透明导电性氧化物层的雾度为5%～20%，在波长为400nm～800nm的光中，所述透明导电性氧化物层的透射率为80%以上。
15.如权利要求8所述的光电装置的制造方法，其特征在于：所述蚀刻通过湿式蚀刻工序来进行。
16.如权利要求8所述的光电装置的制造方法，其特征在于：所述蚀刻按照将沉积有所述透明导电性氧化物层的基板在0.5%～5%的酸性水溶液中浸泡5～20秒的方式进行。
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