CN103348488A - 具有金属硫氧化物窗口层的光伏装置 - Google Patents

具有金属硫氧化物窗口层的光伏装置 Download PDF

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CN103348488A
CN103348488A CN2011800560756A CN201180056075A CN103348488A CN 103348488 A CN103348488 A CN 103348488A CN 2011800560756 A CN2011800560756 A CN 2011800560756A CN 201180056075 A CN201180056075 A CN 201180056075A CN 103348488 A CN103348488 A CN 103348488A
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邵锐
马库思·格鲁克勒尔
本雅明·布勒
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Abstract

本发明描述了光伏装置和基底结构的装置和方法。在一个实施例中，光伏装置包括基底和形成在基底上方的MS1-XOX窗口层，其中，M是由Zn、Sn和In组成的组中的元素。另一实施例意在一种制造光伏装置的工艺，所述制造光伏装置的工艺包括通过溅射、蒸发沉积、CVD、化学浴沉积工艺和气相传输沉积工艺中的至少一种在基底上方形成MS1-XOX窗口层，其中，M是由Zn、Sn和In组成的组中的元素。

Description

具有金属硫氧化物窗口层的光伏装置
本申请要求于2010年9月22日提交的第61/385,420号临时申请的优先权，该申请通过引用全部包含于此。
技术领域
本发明的实施例涉及半导体装置和制造方法，更具体地讲，涉及光伏（PV）装置领域。
背景技术
光伏装置通常包括沉积在基底（例如，玻璃）上的多层材料。图1描述了传统的光伏装置。光伏装置100可采用玻璃基底105、沉积在基底105上的透明导电氧化物（TCO）层110、由n型半导体材料制成的窗口层115、金属背面接触125以及由半导体材料制成的吸收层120。传统的装置用碲化镉（CdTe）作为吸收层120，并包括玻璃基底105、作为TCO层110的氧化锡（SnO2）或氧化镉锡（Cd2SnO4）以及作为窗口层115的硫化镉（CdS）。通过示例的方式，传统的光伏装置在基板105上的沉积工艺的顺序可以为：TCO层110，包括掺杂有SnO2和Cd2SnO4中的一种的n型材料；CdS窗口层115；CdTe吸收层120；金属背面接触125。CdTe吸收层120可沉积在窗口层115的顶部上。
图2中描绘了诸如CdTe装置的传统薄膜光伏装置的示例性能带图。作为TCO层的F掺杂的SnO2的带隙能量被描绘为205，作为缓冲层的未掺杂的SnO2的带隙能量被描绘为210，作为窗口层的CdS的带隙能量被描绘为215，作为吸收层的CdTe的带隙能量被描绘为220。通常，CdS相对于CdTe的导带边缘偏移Δ一般为-0.2eV，其中，实验不确定度为+/-0.1eV。
如图2中所描绘的，Δ是导带边缘Ec在窗口层与吸收之间的偏移。在CdS/CdTe堆叠的情况下，Δ为大约-0.2eV。理论上的模型已经示出，由于光生载流子在窗口/吸收界面处复合的速率增加，所以更大的负值Δ导致Voc和FF损耗更大。当Δ是微小的正数（0至0.4eV）时，可使复合速率最小化，这使得Voc和FF得到改善。
CdS是许多类型的薄膜光伏装置中的常见的窗口层，所述薄膜光伏装置包括将CdTe和Cu(In,Ga)Se2中的一种用作吸收层的光伏装置。然而，如图2中所描绘的，CdS的光学带隙仅为2.4eV。
附图说明
图1描绘了传统的光伏装置。
图2描绘了传统的薄膜光伏装置的示例性能带图。
图3A描绘了根据一个实施例的基底结构。
图3B描绘了根据另一实施例的基底结构。
图4描绘了根据另一实施例的基底结构。
图5A描绘了根据一个实施例的薄膜光伏装置。
图5B描绘了根据另一实施例的薄膜光伏装置。
图6描绘了根据另一实施例的薄膜光伏装置。
图7描绘了根据一个实施例的薄膜光伏装置的能带图。
具体实施方式
本公开意在光伏装置和生产方法。在一个实施例中，金属硫氧化物（MS1-XOX）化合物用作基底结构的窗口层。图3A描绘了根据一个实施例的基底结构300。基底结构300包括基底305、透明导电氧化物（TCO）层310、缓冲层315和窗口层320。TCO层310可通常用于允许太阳辐射进入光伏装置，并可进一步作为电极。TCO层310可包括掺杂有SnO2和Cd2SnO4中的一种的n型材料。窗口层320可用于减轻装置中光生载流子（例如，电子和空穴）的内部损耗，并且可以强有力地影响包括开路电压（Voc）、短路电流（Isc）和填充因子（FF）的装置参数。在一个实施例中，窗口层320可允许入射光穿过吸收材料来吸收光。根据一个实施例，为了改善窗口层320的整体光发射效率，基底结构300包括MS1-XOX化合物。如这里所述的金属硫氧化物（MS1-XOX）化合物材料可包括一种或多种材料，其中，金属（M）可包括锌（Zn）、锡（Sn）和铟（In）中的一种。
在一个实施例中，基底结构300可包括玻璃基底305和TCO层310，其中，可省略缓冲层315。窗口层320（例如，MS1-XOX层）可直接位于TCO层310的顶部上，TCO层涉及Cd2SnO4、F掺杂的SnO2和未掺杂的SnO2中的一种或多种。当TCO层310是未掺杂的Cd2SnO4时，TCO层没有外在的掺杂，然而，所述层可因氧空位而是高度的n型。
根据另一实施例，可提供基底结构300来制造光伏装置。如图3A中所描绘的，基底结构包括基底305、TCO层310、低导电缓冲层315和MS1-XOX窗口层320。图3A的基底结构包括MS1-XOX窗口层320，其中，在MS1-XOX窗口层320上可以沉积装置的其他必须的层（例如，吸收层、金属背面接触）。在一个实施例中，MS1-XOX窗口层320可沉积到F-SnO2基基底结构（比如TEC10）上。同样地，这样的基底结构300可以是锡酸镉（CdSn）基底结构。缓冲层315可用于使在半导体窗口层形成的过程中出现不规则的可能性减小。缓冲层315可由诸如未掺杂的氧化锡、氧化锌锡、氧化镉锌或其他透明导电氧化物或它们的组合的导电性比TCO层310导电性小的材料制成。在某些实施例中，如4中所描绘的，基底结构300可以不包括缓冲层。当基底结构300包括低导电缓冲层315时，缓冲层布置在基底305（例如，玻璃）与MS1-XOX窗口层之间。
在一个实施例中，MS1-XOX窗口层320的厚度的范围为从2nm至2000nm。在另一实施例中，MS1-XOX中X的组成大于0小于1。窗口层320可以是相对于传统的窗口层材料（例如，CdS）更导电的材料。另外，窗口层320可包括能够在蓝光不足的环境下大大减少填充因子（FF）损耗的窗口层材料。MS1-XOX窗口层可使蓝色区域（例如，400nm至475nm）中更多的太阳辐射可到达吸收层，这导致短路电流（Isc）更高。
在供选择的实施例中，如图3B所述，诸如基底结构300的光伏装置可包括：MS1-XOX化合物材料，作为窗口层320；阻挡层和CdS窗口层中的一个或多个。基底结构350的阻挡层355可以是氧化硅、氧化硅铝、氧化锡或其他合适的材料或者它们的组合。CdS窗口层360可沉积在MS1-XOX窗口层320上，其中，CdS窗口层360涉及一种用于沉积吸收层的表面。在一个实施例中，光伏装置包括除基底结构（例如，基底结构300）以外的MS1-XOX窗口层。例如，基底结构300可包括包含基底305、TCO层310以及一种或多种附加元件的TCO堆叠件。在另一实施例中，基底结构300可包括缓冲层315。
在光伏装置的窗口层中采用MS1-XOX的优点可包括相对于具有CdS窗口层的装置改善了开路电压（Voc）。与具有CdS窗口层的装置相比，采用MS1-XOX窗口层的装置Voc方面的改进，例如，可以将开路电压从810mV提高到826mV。相对于具有CdS窗口层的光伏装置，从400nm至475nm，具有MS1-XOX窗口层的CdTe装置可额外地利用较高的量子效率。由于可能难于测量特定的改进△，因此这里描述的Voc改进的值是示例性的。源电流可以提高到2mA/cm2，其中，与具有CdS窗口层的光伏装置相比的改进可能依赖于采用的CdS的厚度。
参照图4，根据另一实施例描绘了图3A的基底结构。基底结构400包括基底405、TCO层410和MS1-XOX窗口层415。与图3A的基底结构300相比，基底结构400可以以较低的成本来制造。
根据另一实施例，MS1-XOX可用作薄膜光伏装置的窗口层。图5A和图5B描绘了根据一个或多个实施例的薄膜光伏装置。首先参照图5A，薄膜光伏装置500包括基底505、透明导电氧化物（TCO）层510、缓冲层515、窗口层520、吸收层525和金属背面接触530。吸收层525可根据太阳辐射的吸收用于产生光生载流子。金属背面接触530可用于当作电极。金属背面接触530可由钼、铝、铜或任何其他高导电性材料制成。薄膜光伏装置500的窗口层520可包括MS1-XOX化合物。
更具体地讲，薄膜光伏装置500可包括玻璃基底505、缓冲层515、MS1-XOX窗口层520、CdTe吸收层525、金属背面接触530以及由SnO2或Cd2SnO4制成的TCO层510中的一种或多种。缓冲层515可以是低导电性的缓冲层，例如，未掺杂的SnO2。缓冲层515可用于使在半导体窗口层形成的过程中出现不规则的可能性减小。吸收层525可以是CdTe层。层的厚度和材料不受图5A和图5B中描绘的厚度限制。在一个实施例中，图5A的装置可采用图3A中的基底。
薄膜光伏装置500可包括作为吸收层525的碲化镉（CdTe）、铜铟镓（二）硒化物（CIGS）和无定形硅（Si）中的一种或多种。在一个实施例中，薄膜光伏装置可设置成包括基底结构和吸收层525之间的MS1-XOX窗口层520，其中，基底结构可以包括或者可以不包括低导电缓冲层515。在某些实施例中，装置可以除MS1-XOX窗口层520外还包括CdS窗口层。
在可选择的实施例中，如图5B中所描绘的，薄膜光伏装置550可包括：MS1-XOX化合物材料，作为窗口层520；阻挡层和CdS窗口层中的一个或多个。阻挡层555可以是氧化硅、氧化硅铝、氧化锡或其他合适的材料或它们的组合。CdS窗口层560可沉积在MS1-XOX层520上，其中，CdS窗口层560提供用于沉积吸收层的表面。
在某些实施例中，薄膜光伏装置500可以不包括缓冲层。图6描绘了包括玻璃基底605、由SnO2或Cd2SnO4制成的TCO层610、MS1-XOX窗口层615、CdTe吸收层620和金属背面接触625的薄膜光伏装置600。
图7描绘了根据一个实施例的诸如采用CdTe吸收层的光伏装置的薄膜光伏装置的带结构。在图7中，描绘为作为TCO层的F掺杂的SnO2的带隙能被描绘为705，作为缓冲层的未掺杂的SnO2被描绘为710，作为窗口层的MS1-XOX被描绘为715，作为吸收层的CdTe被描绘为720。正如进一步所描绘的，MS1-XOX相对于CdTe的导带边缘偏移Δ可调整为0至0.4eV。与CdS相比，图3的薄膜光伏装置的另一优点可以是较宽的带隙。
锌、锡或铟（例如，MS1-XOX中的M）的所有氧和硫化合物具有与CdS的带隙相似或者比CdS的带隙大的带隙，CdS的带隙为2.4eV。当适当地选择X时，三元化合物MS1-XOX可具有较宽的带隙（例如，大于2.4eV）。因此，就蓝光而言，MS1-XOX化合物可允许较大的透明度。另一方面，M所有的氧化物相对于CdTe导带边缘具有负性的Δ，而所有的硫化物具有正性的Δ。因此，如图4中所示，三元化合物MS1-XOX的组合物可以证明Δ是略微正性的，其中，ZnS1-XOX示出为示例。
在另一方面，提供了制造光伏装置和基底以包括如图2和图3中描绘的MS1-XOX窗口层的工艺。可通过一种或多种工艺来制造包含MS1-XOX窗口层的基底结构200，其中，可以通过溅射、蒸发沉积和化学气相沉积（CVD）中的一种或多种来制造所述结构中的一层或多层。同样的，可通过下面的工艺（包括溅射、蒸发沉积、CVD、化学浴沉积和气相传输沉积（vapor transportdeposition））中的一种或多种来制造包含MS1-XOX窗口层的薄膜光伏装置300。
在另一实施例中，制造光伏装置的工艺可包括MS1-XOX窗口层的通过DC脉冲溅射、RF溅射、AC溅射以及其他通常制造工艺中的一种的溅射工艺。用于溅射的源材料可以是MS1-XOX三元化合物的一种或多种陶瓷靶，其中，X在0至1的范围内。在一个实施例中，用于溅射的源材料可以是MS1-XOX合金的一种或多种靶，其中，X在0至1的范围内。在另一实施例中，用于溅射的源材料可以是两种或更多种陶瓷靶，其中，一种或多种陶瓷靶由M的氧化物制成，一种或多种陶瓷靶由M的硫化物制成。用于溅射MS1-XOX的工艺气体可以是利用不同混合比例的氩气和氧气的混合物。
在一个实施例中，可以通过大气压化学气相沉积（APCVD）用前驱体来沉积MS1-XOX窗口层，所述前驱体包括但不限于诸如H2O/H2S或臭氧/H2S的试剂的组合与二乙基锌、二乙基锡和三甲基铟。
根据另一实施例，制造光伏装置的工艺可以导致相对于吸收层导带偏移。例如，通过选择X的值可以调节窗口（MS1-XOX）层相对于吸收层的导带偏移使之处于0与+0.4eV之间。此外，可以通过用价位比金属阳离子（M）的价位更高的阳离子杂质掺杂MS1-XOX（例如，用铝（Al）、铬（Cr）、铌（Nb）和锰（Mn）掺杂ZnS1-XOX）或者用诸如氟（F）的单价阴离子杂质掺杂MS1-XOX以及通过引入氧空位（例如，在溅射过程中使氧分压降低）来实现使导电性提高。在一个实施例中，掺杂浓度从大约1×1014cm3至大约1×1019cm3。在一个实施例中，利用具有1×1017cm3至大约1×1018cm3的掺杂浓度的溅射靶来形成窗口层。

Claims (28)

1.一种光伏装置，所述光伏装置包括：
基底；
MS1-XOX窗口层，形成在基底上方，其中，M是Zn；以及
吸收层，形成在基底上方。
2.如权利要求1所述的光伏装置，其中，吸收层是CdTe。
3.如权利要求1所述的光伏装置，其中，吸收层是CIGS。
4.如权利要求1所述的光伏装置，其中，吸收层是无定形Si。
5.如权利要求1所述的光伏装置，其中，MS1-XOX窗口层形成在基底与吸收层之间。
6.如权利要求1所述的光伏装置，所述光伏装置还包括设置在MS1-XOX窗口层与吸收层之间的CdS窗口层。
7.如权利要求1所述的光伏装置，其中，MS1-XOX层相对于吸收层的导带偏移处于从大约0eV至大约+0.4eV的范围内。
8.一种光伏装置，所述光伏装置包括：
基底；
MS1-XOX窗口层，形成在基底上方，其中，M是Sn；以及
吸收层，形成在基底上方。
9.如权利要求8所述的光伏装置，其中，吸收层是CdTe。
10.如权利要求8所述的光伏装置，其中，吸收层是CIGS。
11.如权利要求8所述的光伏装置，其中，吸收层是无定形Si。
12.如权利要求8所述的光伏装置，其中，MS1-XOX层相对于吸收层的导带偏移处于从大约0eV至大约+0.4eV的范围内。
13.一种光伏装置，所述光伏装置包括：
基底；
MS1-XOX窗口层，形成在基底上方，其中，M是In；以及
吸收层，形成在基底上方。
14.如权利要求13所述的光伏装置，其中，吸收层是CdTe。
15.如权利要求13所述的光伏装置，其中，吸收层是CIGS。
16.如权利要求13所述的光伏装置，其中，吸收层是无定形Si。
17.如权利要求13所述的光伏装置，其中，MS1-XOX层相对于吸收层的导带偏移处于从大约0eV至大约+0.4eV的范围内。
18.一种制造光伏装置的工艺，所述工艺包括：
在基底上方形成MS1-XOX窗口层，其中，M是Zn、Sn和In中的一种；
在基底上方形成吸收层。
19.如权利要求18所述的工艺，其中，通过溅射、蒸发沉积、CVD、化学浴沉积工艺和气相传输沉积工艺中的至少一种来形成MS1-XOX层。
20.如权利要求18所述的工艺，其中，MS1-XOX层相对于吸收层的导带偏移处于从大约0eV至大约+0.4eV的范围内。
21.一种光伏装置，所述光伏装置包括：
基底；
MS1-XOX窗口层，通过溅射工艺、蒸发沉积工艺、CVD工艺、化学浴沉积工艺和气相传输沉积工艺中的至少一种形成在基底上方，其中，M是由Zn、Sn和In组成的组中的元素；以及
吸收层，形成在基底上，其中，吸收层由CdTe、CIGS和无定形Si中的一种形成。
22.如权利要求21所述的光伏装置，其中，MS1-XOX窗口层的溅射工艺是DC脉冲溅射、RF溅射和AC溅射中的一种。
23.如权利要求21所述的光伏装置，其中，用于溅射的源材料是两种或更多种陶瓷靶，其中，一种或多种由M的氧化物制成，一种或多种由M的硫化物制成。
24.如权利要求21所述的光伏装置，其中，用于溅射MS1-XOX的工艺气体是氩气和氧气的混合物。
25.如权利要求21所述的光伏装置，其中，MS1-XOX层通过APCVD沉积前驱体来形成，所述前驱体包括但不限于诸如H2O/H2S或臭氧/H2S的试剂的组合以及二乙基锌、二乙基锡和三甲基铟。
26.如权利要求21所述的光伏装置，其中，MS1-XOX层相对于吸收层的导带偏移处于从大约0eV至大约+0.4eV的范围内。
27.如权利要求21所述的光伏装置，其中，MS1-XOX层的导电率处于1mOhm/cm至10Ohm/cm的范围内。
28.如权利要求21所述的光伏装置，其中，用价位比M的价位高的阳离子掺杂MS1-XOX层，或者用诸如F的一价阴离子掺杂MS1-XOX层，或者用氧空位掺杂MS1-XOX层。
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