CN104183663B - 光伏器件及其制备方法 - Google Patents

光伏器件及其制备方法 Download PDF

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CN104183663B
CN104183663B CN201310190090.0A CN201310190090A CN104183663B CN 104183663 B CN104183663 B CN 104183663B CN 201310190090 A CN201310190090 A CN 201310190090A CN 104183663 B CN104183663 B CN 104183663B
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tellurium
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CN104183663A (zh
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巴斯提安.柯雷法尔
黄群健
金益腾
辛骞骞
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First Solar Malaysia Sdn Bhd
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Priority to MYPI2015704226A priority patent/MY178458A/en
Priority to US14/892,349 priority patent/US10141463B2/en
Priority to EP14800780.0A priority patent/EP3001881B1/en
Priority to PCT/US2014/041256 priority patent/WO2014190362A1/en
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Abstract

本发明涉及光伏器件，其包括：支撑层；含有镉、碲、铜，且为n‑型的第一层；含有镉、碲、铜，且为p‑型的第二层；以及透明导电氧化物层。本发明也涉及制备光伏器件的方法，其包括：提供具有含镉和碲的层以及在含镉和碲的层上的含铜层的元件；以及将元件加温退火形成分别含有镉、碲、铜的第一层和第二层，第一层为n‑型，第二层为p‑型。

Description

光伏器件及其制备方法
技术领域
本发明涉及一种光伏器件及其制备方法。具体而言，本发明涉及一种包含碲和镉的光伏器件及其制备方法。
背景技术
光伏器件,例如薄膜太阳能电池，通常包括碲化镉层和硫化镉层。位于碲化镉-硫化镉接触面的混合区域对光伏器件的性能可能产生不良影响。
因此，需要改进的光伏器件及其制备方法。
发明内容
本发明的实施例可以满足上述及其它需求。一个实施例是一种光伏器件。该光伏器件包括：支撑层；含有镉、碲、铜，且为n-型的第一层；含有镉、碲、铜，且为p-型的第二层；以及透明导电氧化物层。
一个实施例是一种制备光伏器件的方法。该方法包括：提供具有含镉和碲的层以及在含镉和碲的层上的含铜层的元件；以及将元件加温退火形成分别含有镉、碲、铜的第一层和第二层，第一层为n-型，第二层为p-型。
附图说明
当参考附图阅读下面的详细描述时，本发明的这些和其它特征、方面及优点将会变得更好理解，在附图中：
图1是根据本发明的第一实施例的光伏器件的剖面示意图；
图2是根据本发明的第二实施例的光伏器件的剖面示意图；
图3所示为比较示例1-3和示例1中制备的光伏器件样品在距离碲化镉层与背电极的界面不同距离处的电压。
具体实施方式
除非本发明中清楚另行定义，用到的技术和科学术语的含义为本发明所属技术领域的技术人员所通常理解的含义。本发明中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。本发明中使用的“包括”、“包含”、“含有”或“具有”以及类似的词语是指除了列于其后的项目及其等同物外，其他的项目也可在范围以内。
说明书和权利要求中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的、可接受的、不会导致相关基本功能的改变的修正的部分。相应的，用“大约”、“约”等修饰一个数值，意为本发明不限于该精确数值。在某些实施例中，近似用语可能对应于测量数值的仪器的精度。说明书和权利要求中的范围可以合并及/或互换，除非另行清楚说明，范围包括其所涵盖的所有子范围。
在说明书和权利要求中，除非清楚地另外指出，单复数不加以限制。除非上下文另外清楚地说明，术语“或”并不意味着排他，而是指存在提及部件（例如层）中的至少一个，并且包括提及部件的组合可以存在的情况。
本发明所提及的“可”和“可能”表示在一定环境下发生的可能性；具有指定的性质，特征或者功能的可能性；和/或通过显示一个或者多个能力、性能而适合于另一种动作，或者与该适合的动作相关的可能性。因此，用于“可”、和“可能”表示修饰的术语显然适合、能够或者适于所表示的能力，功能，或者用途，同时考虑在一些情况下，所修饰的术语可能有时不适合、不能或者不合适。例如，在一些情况下，事件或者能力可能是所期望的，而在其它情况下，该事件或者能力不能发生。这些情形通过术语“可”和“可能”描述。
本发明说明书中提及“一个实施例”、“另一个实施例”、“一些实施例”等等，表示所述与本发明相关的一种特定要素（例如特征、结构和/或特点）被包含在本说明书所述的至少一个实施例中，可能或不可能出现于其他实施例中。另外，需要理解的是，所述发明特征可与各种实施例和构造以任何适合的方式结合。
在下文中，将参照附图说明本发明的实施方式，但不会详细描述众所周知的功能和结构以及不必要的细节。如下详细所述，本发明的实施例包括光伏器件和其制备方法。
光伏器件可为其应用环境所需的任何结构。在一些实施例中，光伏器件包括以背电极为衬底的结构。图1所示为根据本发明的第一实施例的光伏器件1。参考图1，光伏器件1包括支撑层2；含有镉、碲、铜，且为n-型的第一层3；含有镉、碲、铜，且为p-型的第二层4；以及透明导电氧化物层5。
在这样的实施例中，太阳光（未图示）从透明导电氧化物层5进入，在通过第一层3之后，进入第二层4。入射光（例如，太阳光）的电磁能在第一层3和第二层4转化为电子-空穴对（即，自由电荷）。
在另一些实施例中，如图2所示，示例光伏器件10包括以透明氧化物为衬底的结构。光伏器件10包括支撑层20；含有镉、碲、铜，且为n-型的第一层30；含有镉、碲、铜，且为p-型的第二层40；以及透明导电氧化物层50。
在这样的实施例中，太阳光（未图示）从支撑层20进入，在通过透明导电氧化物层50和第一层30之后，进入第二层40。入射光（例如，太阳光）的电磁能在第一层30和第二层40转化为电子-空穴对（即，自由电荷）。
本发明中使用的术语“层”或“区域”指以连续或不连续的方式，设置在下层表面的至少一部分上的材料。此外，“层”或“区域”并非必然意味着所设置的材料的厚度均匀，所设置的材料可具有均匀或可变的厚度。
在本发明中，当层被描述为“在另一个层上“或者被描述为“在其他层之间”时，应当理解的是，所述层可彼此直接接触或在所述层之间具有一个（或多个）层或特征。此外，术语“在…上”表示层彼此之间的相对位置，而并非必然意味着“在…顶部”，因为相对位置上面或下面取决于器件相对于观察者的方位。术语“邻近”意味着两个层接触地设置，并彼此直接接触。
在一些实施例中，支撑层2，20在期望透过支撑层2，20的波长的范围内是透明的。在一些实施例中，支撑层2，20包括二氧化硅、硼硅酸盐玻璃、钠钙玻璃、聚酰亚胺或它们的任意组合。
在一些实施例中，光伏器件（未图示）的支撑层包括可导电物质，充当背电极，从而不具有其他单独的背电极。可导电物质包括但不限于，金，铂，钼，钨，钽，钛，钯，铝，铬，镍，银，石墨，或上述物质的任意组合。
在一些实施例中，特定其他层，例如减反层（未图示），可置于透明导电氧化物层或支撑层上太阳光入射的一侧。
在一些实施例中，特定其他层，例如阻挡层（未图示），可置于支撑层上，位于透明导电氧化物层和支撑层之间、或者背电极和支撑层之间。
本发明使用的术语“透明导电氧化物层”指的是能够用作前集流体的基本透明的层或区域。在一些实施例中，当入射光的波长在350纳米到850纳米之间的时候，透明导电氧化物层5，50的平均透过率至少大于70%。
在一些实施例中，透明导电氧化物层5，50包括透明导电氧化物。透明导电氧化物的非限制性示例包括锡酸镉（Cd2SnO4或CTO），氧化铟锡（ITO），掺氟氧化锡（SnO:F或FTO），掺铟氧化镉，掺铝氧化锌（ZnO:Al或AZO）、氧化铟锌（IZO）和氧化锌锡（ZnSnOx）等掺杂氧化锌，或它们的任意组合。根据采用的具体透明导电氧化物及其薄层电阻，在一些实施例中，透明导电氧化物层5，50的厚度可在约50nm至约600nm的范围内。
在一些实施例中，光伏器件1，10具有背电极6，60。在一些实施例中，背电极6，60包括金，铂，钼，钨，钽，钛，钯，铝，铬，镍，银，石墨，或上述物质的任意组合。背电极6，60可包括一起起接触作用的许多层。
在一些实施例中，其他金属层（未图示），例如铝，可设置在背电极6，60上以提供与外部电路的连接。在一些实施例中，多个金属层（未图示），例如铝和铬，可设置在背电极6，60上以提供与外部电路的连接。在一些实施例中，背电极6，60可包括一层碳，例如石墨，设置在第二层4，40之上，然后再设置其他金属层，例如前述中的金属。
在一些实施例中，光伏器件1，10包括位于透明导电氧化物层5，50与第一层3，30之间的缓冲层（未图示）。缓冲层的薄层电阻比透明导电氧化物层5，50高。缓冲层有时也被称为“高电阻透明导电氧化物层”或“HRT层”。缓冲层的合适材料包括但不限于含有锌、锡、钛或铟的氧化物，即二氧化锡,锌锡氧化物(锡酸锌(ZTO)),掺锌二氧化锡(SnO2:Zn),氧化锌(ZnO),氧化铟(In2O3),二氧化钛(TiO2),或前述物质的任意组合。在一些实施例中，缓冲层的厚度范围为大约20nm至大约200nm。
在一些实施例中，光伏器件1，10包括位于第二层4，40和背电极6，60之间、含有如以等离子增强化学气相沉积(PECVD)或溅射等任何适当方式设置的p+-型材料的p+-型半导体层（未图示）。在另一实施例中，p+-型半导体区可在第二层4，40中形成，通过（例如，使用碘和铜）化学处理第二层4，40，提高第二层4，40背面（与金属层相接触而与第一层3，30相反的面）的载流子浓度。在一些实施例（未图示）中，背电极6，60，例如石墨层，可设置在p+-型半导体层上，或者直接设置在第二层4，40上。多个金属层可进一步设置在背电极6，60上。在一些实施例中，p+-型透明导电氧化物可设置在背电极上，第二层可与p+-型透明导电氧化物层邻接。
本发明使用的术语“p+-型半导体层”指的是与第二层4，40中的p型载流子或空穴浓度相比具有额外可移动的p型载流子或空穴的半导体层。在一些实施例中，p+-型半导体层的p型载流子浓度在高于每立方厘米约1×1016的范围内。在一些实施例中，p+-型半导体层可用作第二层4，40和背电极6，60之间的界面。
在一些实施例中，p+-型半导体层包括重掺杂的p型材料，该重掺杂的p型材料包括非晶Si:H、非晶SiC:H、晶体Si、微晶Si:H、微晶SiGe:H、非晶SiGe:H、非晶Ge、微晶Ge、GaAs、BaCuSF、BaCuSeF、BaCuTeF、LaCuOS、LaCuOSe、LaCuOTe、LaSrCuOS、LaCuOSe0.6Te0.4、BiCuOSe、BiCaCuOSe、PrCuOSe、NdCuOS、Sr2Cu2ZnO2S2、Sr2CuGaO3S、（Zn,Co,Ni）Ox或它们的任意组合。在另一个实施例中，p+-型半导体层包括p+-掺杂材料，该p+-掺杂材料包括碲化锌、碲化镁、碲化锰、碲化铍、碲化汞、碲化砷、碲化锑、碲化铜或它们的任意组合。在一些实施例中，p+-杂质还具有包括铜、金、氮、磷、锑、砷、银、铋、硫、钠或它们的任意组合的掺杂剂。
如本领域技术人员所了解，光伏器件各层的设置顺序可取决于所期望的光伏器件结构，例如取决于光伏器件是采用以背电极为衬底的结构还是以透明氧化物为衬底的结构。在一些实施例中，制备光伏器件1，10的方法包括：提供具有含镉和碲的层（未图示）以及在含镉和碲的层上的含铜层（未图示）的元件（未图示）；以及将元件加温退火形成分别含有镉、碲、铜的第一层3，30和第二层4，40，第一层为n-型，第二层为p-型。
在一些实施例中，元件包括支撑层2和设置在支撑层2上的背电极6。含镉和碲的层设置在背电极6上。
除非另外明确地说明，本发明使用的术语“设置在…上”指的是层直接彼此接触地设置或通过在层之间具有中间层而间接地设置。
在一些实施例中，在元件退火后，透明导电氧化物层5通过任何适当的方式设置在第一层3上，例如溅射，化学气相沉积，旋转涂覆，或浸渍涂覆。
在一些实施例中，透明导电氧化物层50可通过任何适当的方式设置在支撑层20上，例如溅射，化学气相沉积，旋转涂覆，或浸渍涂覆。
在一些实施例中，缓冲层（未图示）可通过溅射方式设置在透明导电氧化物层5，50上。
在一些实施例中，碲化镉层设置在透明导电氧化物层上。
用于沉积含镉和碲的层的方法的非限制性示例包括近空间升华（CSS）、气相输运沉积（VTD）、溅射（例如，直流脉冲溅射（DCP））、电化学沉积（ECD）、离子辅助物理气相沉积（IAPVD）、射频或脉冲磁控溅射（RFS或PMS）、等离子增强化学气相沉积（PEVCD）以及化学浴沉积（CBD）中的一种或多种。
在一些实施例中，含铜层包括金属铜、CuS、CuSe、ZnTe:Cu、或上述物质的任意组合。含铜层可用适当方法沉积，或通过把元件浸入铜溶液中形成。在一些实施例中，铜溶液含有乙酸铜，或者氯化铜。
在一些实施例中，含铜层直接沉积在含镉和碲的层上。在一些实施例中，含镉和碲的层直接沉积在含铜层上。
在元件退火后，含镉和碲的层和含铜层形成分别包括镉，碲，铜的第一层3，30和第二层4，40。在一些实施例中，含镉和碲的层包括第一区和第二区。在结构或化学组分方面，第二区与第一区可相同，也可不同。在元件退火后，铜进入第一区和第二区，第一区形成n-型的第一层3，30，而第二区形成p-型的第二层4，40。
在一些实施例中，在温度和时间等条件适合的情况下，含镉和碲的层的沉积与含镉和碲的层和含铜层的退火可在同一个步骤中进行。
在一些实施例中，退火的温度为大约250°C，时间为多于约12分钟但少于约30分钟。
含镉和碲的层包括镉、碲，以及，在一些实施例中，锌、硒、汞、铅、硫，或者前述物质的任意组合。
在一些实施例中，第一层或第二层包括锌，硒，汞，铅，硫，或者前述物质的任意组合。在第一层或第二层中的锌，硒，汞，铅，硫，或者前述物质的任意组合的原子百分比共计低于或等于大约百分之十。
镉，碲，铜，或者可选的锌，硒，汞，铅，硫，或者前述物质的任意组合在第一层3，30或者第二层4，40的浓度可恒定或者在不同的层，不同的方向有一定的梯度。
在一些实施例中，一系列的后处理可进一步施加到第一层3或第二层40的表面。这些处理可改变第一层3或第二层40的功能，并为把第一层3或第二层40粘合到透明导电氧化物层5，背电极60，或其他层做准备。例如，可在高温下对第二层40进行足够时间的退火，以产生高质量的p-型层。而且，可使用钝化剂（例如，氯化镉）和选择性腐蚀剂（例如，碘或碘化物）来处理第二层40，以在第二层40中形成富碲区域。
在一些实施例中，形成钝化层来钝化第一层的表面。钝化层使用的材料示例包括但不限于CdMnTe或CdMgTe。
第一层3，第二层40，背电极6，60，或者p+-型层(可选)中的一层或者多层，可在生成后进一步加热或进一步处理（例如退火），以制造光伏器件1，10。
本发明涉及的光伏器件可因省略硫化镉（CdS）层而降低成本，此外，省略的CdS层的吸收损失也不再存在，光伏器件的效率因此可以得到提高。
示例
下述示例为本技术领域内的技术人员实施本发明提供进一步的指导。示例并不限定权利要求书中界定的本发明的范围。
比较示例1：
通过将几个层沉积在支撑层上而制成光伏器件。支撑层是1.4毫米厚的PVN++玻璃，涂覆有锡酸镉（CTO）透明导电氧化物层和高电阻透明氧化锌锡（ZTO）缓冲层。硫化镉层（CdS:O，在硫化镉层中有5摩尔百分比的氧）随后通过直流溅射而沉积在ZTO层上，然后在550℃沉积碲化镉（CdTe）层以提供元件。在元件的CdTe层上沉积一层金作为光伏器件的背电极。
比较示例2：
通过类似于比较示例1的方法制备光伏器件，但对元件的CdTe层采用“氯化镉处理”工艺，即，在制备背电极之前，在400°C于氯化镉和空气中高温退火。
比较示例3
通过类似于比较示例2的方法制备四个光伏器件，但四个分别包括支撑层，透明导电氧化物层，缓冲层，硫化镉层，和碲化镉层的元件在氯化镉处理后、制备背电极前，浸入乙酸铜溶液中，然后各自在170°C，210°C或250°C的温度退火12分钟，或者250°C的温度退火30分钟。
示例1
通过类似于比较示例3的方法制备光伏器件，但在退火过程中，温度为250°C而时间为18分钟。
示例2
对比较示例1-3和示例1所得光伏器件样品进行扫描电容显微镜(SCM)线扫描。图3所示为从距离碲化镉层和背电极间的界面不同距离之处所得的光伏器件的电压。
图3显示氯化镉处理不影响载流子浓度，在170°C温度退火12分钟所得样品在接近界面的位置形成了p-型碲化镉，并且铜在210°C和250°C退火12分钟的样品的碲化镉层上的分布更均匀。250°C退火18分钟制备的样品在分别接近和远离含碲化镉层和背电极间的界面的位置上，分别形成了n-型碲化镉层和p-型碲化镉层。
尽管在具体实施方式中对本发明的部分特征进行了详细的说明和描述，但在不脱离本发明精神的前提下，可以对本发明进行各种改变和替换。同样的，本领域技术人员也可以根据常规实验获得本发明公开的其它改变和等同物。所有这些改变，替换和等同物都在本发明所定义的权利要求的构思和范围之内。

Claims (10)

1.一种光伏器件，其包括：
支撑层；
含有镉、碲、铜且为n-型的第一层；
含有镉、碲、铜且为p-型的第二层；以及
透明导电氧化物层，
其中，第一层和第二层通过如下步骤形成：
提供包括含镉和碲的层以及在含镉和碲的层上的含铜层的层叠；以及
将该层叠加温退火形成分别含有镉、碲、铜的第一层和第二层，第一层为n-型，第二层为p-型。
2.如权利要求1所述的光伏器件，其中第一层或第二层含有锌、硒、汞、铅、硫或其任意组合。
3.如权利要求2所述的光伏器件，其中锌、硒、汞、铅、硫或其任意组合在第一层或第二层的原子百分比小于、等于百分之十。
4.如权利要求1所述的光伏器件，其中支撑层为背电极。
5.如权利要求1所述的光伏器件，包括背电极。
6.如权利要求5所述的光伏器件，其中第一层位于透明氧化物层和第二层之间，第二层位于第一层和背电极之间。
7.如权利要求1-6中任意一项所述的光伏器件，包括含有锌、锡、钛或铟的氧化物的缓冲层。
8.一种制备光伏器件的方法，其包括：
提供具有含镉和碲的层以及在含镉和碲的层上的含铜层的元件；以及
将元件加温退火形成分别含有镉、碲、铜的第一层和第二层，第一层为n-型，第二层为p-型。
9.如权利要求8所述的方法，其包括提供支撑层和透明导电氧化物层。
10.如权利要求8或9所述的方法，其中加温退火在250℃进行超过12分钟但短于30分钟的时间。
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