CN101443929A - 使用含碱层的过程和光电装置 - Google Patents

使用含碱层的过程和光电装置 Download PDF

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CN101443929A
CN101443929A CNA2005800451823A CN200580045182A CN101443929A CN 101443929 A CN101443929 A CN 101443929A CN A2005800451823 A CNA2005800451823 A CN A2005800451823A CN 200580045182 A CN200580045182 A CN 200580045182A CN 101443929 A CN101443929 A CN 101443929A
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约翰·R·塔特尔
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Abstract

本发明描述开发光电装置的产品和方法，其使用含碱混合相半导体源层来增强电池效率和最小化分子结构缺陷。

Description

使用含碱层的过程和光电装置
相关申请案的交叉参考
本申请案主张2004年11月10日申请的序列号为60/626,843美国临时专利申请案的优先权。
技术领域
本发明涉及使用含碱混合相半导体源层来形成薄膜光电装置。
背景技术
替代性能量源(例如光电(PV)电池、模块和电力系统)为全世界对电力日益膨胀的需求提供清洁、可靠、可更新的能量。然而，在很大程度上，高于期望的产品成本和低于期望的生产能力仅使光电装置用于特殊市场。随着能量需求的增加，对当前能量源的替代物的世界性需求也随之增加。
PV技术提供一种取代传统的非可更新能量源的清洁的非碳基替代物。按照将光能转化为电能的效率来测量PV电池的性能。尽管能在实验室中制造出相对有效的PV电池，但已证实难以在对于商业可行性较为关键的适当成本基础上以商业规模来生产PV电池。这个问题在若干因素中具有其根源，其最重要的是优化电力输出的同时最小化成本和重量。此外，任何PV产品必需充分有效以便可适用于现实的能量市场。
为试图降低成本，二十多年来一直在追求降低太阳能电池的总厚度。当今的主要太阳能电池技术由晶体硅(Si)制成。典型的Si电池厚度在150微米到300微米的范围内。由于Si是“间接的”带隙半导体，因而其厚度不能过分降低到150微米以下，否则将降低电池效率。另一方面，存在其它适用于太阳能电池应用的半导体材料，所述材料是“直接的”带隙半导体且可因此用小得多的太阳能电池材料厚度来吸收太阳光谱。此材料族通常被称为“薄膜”太阳能电池。薄膜太阳能电池通常为1-5微米厚，且因此相对于Si太阳能电池来说提供极大的原料节约的潜力。
在薄膜太阳能电池中，p-n结通常由不同材料——p型吸收体和n型窗口产生。此类p型吸收体曾包含由来自元素周期表的列I、III和VI的元素组成的材料族。
这些成分的最有效形式之一是由包含各种比率的元素铜、铟、镓和硒的化合物制成的吸收体。使用此合成物已变得非常普遍，而使得具有此组成的PV电池现被称为CIGS(Cu:In:Ga:Se)光电电池。
最好的CIGS太阳能电池是在碱石灰玻璃上制造的，且在实验室设置中展示大于19％的转换效率。已根据经验确定，高效率部分是碱金属(特别是钠)在沉积过程期间扩散离开玻璃而进入CIGS吸收体层的结果。碱金属从玻璃向外扩散并进入CIGS吸收体层的程度部分与沉积过程的热平衡相关。热平衡与处理温度的量值和持续时间两者相关。将CIGS吸收体中的最终碱金属含量与在沉积期间的处理条件耦合不会有助于所期望的可再生性和制造控制。因此，在碱石灰玻璃衬底上制造CIGS PV电池的领域的技术人员已尝试通过以下方法来控制碱含量：首先在衬底与金属背部接触之间引入碱性阻挡层以防止碱性物质向外扩散，且随后在背部接触与CIGS半导体之间沉积已知厚度的含碱化合物。
如果选择衬底不含有碱性物质(例如金属或塑料)，那么所属领域的技术人员认为需要添加可控量的碱性金属以便获得最高可能的太阳能电池性能。明确地说，添加碱金属使得CIGS膜能够获得较大晶粒大小、较强定向结构、增大的载流子浓度和较高导电性。由于所有这些性质都有利于生产增强的PV电池，因而此项技术需要向CIGS层添加碱金属(例如钠)。
直到现在，由于沉积过程的某些特殊性的缘故，在实际操作中还难以将碱金属并入到CIGS吸收体中。特定问题包括：确定应当在沉积过程中的哪个时间点添加碱金属才不会负面影响CIGS膜到金属背部接触的粘附；应使用那些化合物来传递碱金属，因为元素碱金属具有高度反应性且需要考虑特殊处理；和在沉积过程中需要那种环境条件来实现将一定量的碱金属成功并入到半导体材料中。为解决这些问题，此项技术需要一种用于将碱金属(例如钠)并入在CIGS吸收体层中的可行过程。
尽管已在其它参考中涵盖了钠的添加，但尚未教示一种用以在形成过程期间添加钠基碱性材料的实用方法。举例来说，2005年4月19日授予Stanbery的第6,881,647号美国专利(“Stanbery”)揭示在研制CIGSS(Cu:In:Ga:S:Se)装置中使用钠前体层作为表面活化剂来粘附两个层。然而，Stanbery未揭示在沉积半导体层之前沉积碱性材料且使用后续热处理的原理。
2001年11月27日授予Gillespie等人的第6,323,417号美国专利(“Gillespie”)揭示使用沉积方法来研制CIGS型PV电池，并发现可添加钠来改变吸收体性质。然而，Gillespie未揭示一种用于实现此设计的方法或一种用以形成掺杂钠的CIGS型吸收体的过程。因此，必需一种用以形成掺杂钠的CIGS型吸收体的可行过程来实现此项技术中的全部方法。
Negami等人的第10/942,682号美国专利申请案(“Negami”)揭示在前体之前、前体之后或进行混合来溅镀NaP或NaN。然而，Negami的过程涉及高达800℃的温度，所述温度会使得制造存在问题和困难。因此，此项技术需要一种较安全且提供较低制造成本的替代过程。
另外，在现存技术中不存在一种用于将碱性材料引入到CIGS吸收体层且同时改进CIGS层到金属背部接触的粘附的方法，也不存在一种包括电子“镜”来降低CIGS吸收体中的少数载流子再组合从而导致性能增强的装置。
发明内容
本发明在光电装置(PV)中包含混合相半导体层或源层，其中所述混合相半导体层包含碱性材料与I-III-VI2化合物的混合物或合金。结合导电背部接触层和另一I-III-VI2化合物吸收体层来使用此层。用于此类半导体的最常见I-III-VI2化合物包含铜、铟、镓和硒的某组合，从而形成所属领域的技术人员通常已知的化合物CIGS。最常见的碱性材料包含钠、钾、氟、硒和硫的某些组合。更具体地说，用于此目的的最常见碱性材料为NaF、Na2Se和Na2S。然而，不同于其它参考，本发明包括一种过程，其中碱性材料与I-III-VI2半导体材料(与CIGS吸收体层相比，其优选具有较高带隙)组合以形成引入在导电背部接触层与CIGS吸收体层之间的混合相半导体源材料。
在一种形式中，本发明是一种混合相半导体源层，其包含碱性材料与预先反应的I-III-VI前体金属的混合物以形成混合相半导体源层。
在另一形式中，本发明是一种混合相半导体源层，其包含碱性材料与未反应的I、III和VI前体金属的混合物，所述I、III和VI前体金属随后反应生成I-VII:I-III-VI或(I)2VI:I-III-VI合金。所述反应步骤可与用于形成CIGS吸收体层的反应步骤分离或同时进行。
在一种形式中，本发明是一种用以产生用于光电装置的混合相半导体源层的方法，其中所述源层是部分通过沉积混合相半导体层或沉积从包含碱金属的源材料得到的合金结合I-III-VI半导体化合物而制得的。
在另一形式中，本发明是一种用以产生用于光电装置的混合相半导体源层的方法，其中所述源层是部分通过共同沉积两种源材料而制得的，所述两种源材料中的一者包含碱金属，而另一者包含反应过的I-III-VI化合物或未反应的前体(其包含I、III和VI元素)或其合金或其反应过的二元化合物。
在又一形式中，本发明是一种用以产生用于光电装置的混合相半导体源层的方法，其中所述源层是部分地通过循序沉积两种源材料而制得的，所述两种源材料中的第一者包含反应过的I-III-VI化合物或未反应的前体(其包含I、III和VI元素)或其合金或其反应过的二元化合物，且其第二者包含碱金属。所述两个离散层随后单独地或结合CIGS吸收体层的形成进行反应，以形成混合相半导体源层。
上面沉积所述层的衬底可选自包含金属、塑料、玻璃和各种聚合物材料的材料群组。
如多种参考文献中展示，CIGS半导体是通过在衬底上循序或共同沉积I-III-VI金属的各种合成物而形成的。一些实例包括CuGaS2、CuInS2、CuInTe2、CuAlS2、CuInGa、CuGaS2、AgInS2、AgGaSe2、AgGaTe2、AgInSe2和AgInTe2。然而，如上文提到的，最常见的合成物是铜铟二硒(CuInSe2)变体或CIGS。沉积方法包括溅镀、蒸镀或所属领域的技术人员已知的其它此类工艺。在形成CIGS半导体之前以类似方式沉积碱性材料。为完成将碱金属并入到半导体层中，必须在沉积过程期间和某稍后时间点在约400℃到约600℃的温度下进行热处理。
当混合相半导体源层形成到(通常)约150nm到约500nm的厚度时，碱金属构成5.0到约15.0重量％之间。当在高温下进行热处理时，通过钠与其它I-III-VI元素的原子交换，含碱混合相半导体源层接着与另一p型I-III-VI半导体层合并。
附图说明
通过结合附图来参考以下对本发明实施例的描述，将明了并更好理解本发明的上述和其它特征和优点以及获得所述特征和优点的方式，在附图中：
图1A展示由本发明生产技术生产的薄膜太阳能电池的实施例；
图1B展示合成碱金属与I-III-VI化合物以形成混合相半导体层的实例。
图1C展示合成碱金属与I-III-VI化合物以形成混合相半导体层的另一实例。
图1D展示合成碱金属与I-III-VI化合物以形成混合相半导体层的另一实例。
图1E展示合成碱金属与I-III-VI化合物以形成混合相半导体层的另一实例。
图1F展示合成碱金属与I-III-VI化合物以形成混合相半导体层的另一实例。
在所述若干视图中，相应参考元件符号指示相应部分。本文阐述的实例说明本发明的六个实施例，但不应解释为以任何方式限制本发明范围。
具体实施方式
本发明详细说明光电(PV)装置生产中的一个方面，其目的在于增加能量效率且使装置生产最大化。较先进的PV技术已利用由元素周期表I、III和VI族元素组成的合金来获得更高级的光能量吸收。具体地说，本发明通过集成碱金属(例如钠)和半导体层来增强光电装置中Cu:In:Ga:Se p型吸收体(CIGS)的品质。类似于许多相关实施例，通过循序沉积离散层来制造此实施例中的PV电池。沉积方法可包含例如溅镀、蒸镀的技术或所属领域的技术人员已知的其它相关沉积方法。
观看图1A，所有层沉积在衬底105上，所述衬底105可包含多种功能材料中的一种，例如玻璃、金属、陶瓷或塑料。直接沉积在衬底105上的是阻挡层110。所述阻挡层110包含薄导体或非常薄的绝缘材料，且用以阻断不需要的元素或化合物从衬底向外扩散到电池的其它部分。此阻挡层110可包含铬、钛、氧化硅、氮化钛和具有必要导电性和耐用性的相关材料。下一沉积层是背部接触层120，其包含非反应性金属(例如钼)。沉积在背部接触层120上的下一层是半导体层130，其用以改进吸收体层与背部接触之间的粘附。此半导体层130可为I-IIIa，b-VI同型半导体，但优选的成份为Cu:Ga:Se、Cu:Al:Se或Cu:Tn:Se与前述化合物中的任一者的合金。
在此实施例中，通过许多离散层的互相扩散来产生含碱混合相半导体源层155。最后，如图1A中所见，第一半导体层130与第二半导体层150组合以形成单个复合p型吸收体层155，所述吸收体层155充当太阳能的主要吸收体。然而，不同于其它实施例，添加碱性材料140以用于为后续层的生长播种以及增加p型吸收体层155的载流子浓度和晶粒大小的目的，从而增加PV装置的转换效率。
碱性材料140通常是基于钠的，且通常以Na-VII(VII＝F、Cl、Br)或Na2-VI(VI＝S、Se、Te)的形式沉积。当沉积时，碱性材料140可采用Na-A:I-III-VI合金(A＝VI或VII)的形式，以允许与半导体层150交换元素。
如图1A所示，碱性材料140是离散的，且半导体层150沉积在上面。然而，碱性材料并不会保持离散，而是与半导体层130和150集成为最终p型吸收体层形成的一部分(如155所示)。当沉积时，碱性材料通过蒸镀、溅镀或所属领域的技术人员已知的其它沉积方法而沉积到半导体层130或其它预先存在的层上。在优选实施例中，碱性材料140在环境温度下且在适度真空中(优选为10-6-10-2托)经溅镀。
在一个实施例中，一旦沉积了半导体层130和碱性材料140，便在约400℃-600℃的温度下对所述层进行热处理，以形成混合相半导体源层。
在热处理之后，通过沉积n型结缓冲层160来继续进行光电生产过程。此层160将最终与半导体层150进行相互作用，以形成必需的p-n结165。接下来沉积透明的本征氧化层170，以充当具有CIGS吸收体的异质结。最后，沉积导电透明氧化层180，以充当电池电极的顶部。此最后层是导电的，且可将电流载运到栅格载流子，所述栅格载流子允许带走所产生的电流。
图1A中所说明的过程可具有与上述实施例不同的实施例。观看图1B，展示产生上述混合相半导体源层的另一实例。在图1B中，分别合成I-III-VI半导体131和碱性材料141，接着将其混合并接着沉积在衬底上，以形成Na:I-III-VI混合相半导体源层151。如上所讨论，添加这些碱性材料以用于为后续层的生长播种，且首先沉积半导体层来产生对背部接触金属的良好粘附。当这些实施例中的I-III-VI前体金属经沉积并硒化——且消耗所述碱性层——所得混合相半导体源层发生反应以形成最终p型吸收体层。
观看图1C，分别合成I-III-VI化合物131和碱性材料141，接着将其共同沉积在衬底上，以形成Na:I-III-VI层151。如上所讨论，添加碱性材料以用于为后续层的生长播种，以及增加吸收体层的载流子浓度和晶粒大小，从而增加太阳能电池的转换效率。
观看图1D，共同沉积I-III-VI前体材料132和碱性材料141。接下来，将I-III-VI前体材料132和碱性材料141合成为合金混合物，以形成Na:I-III-VI混合相半导体源层151。
观看图1E，循序沉积I-III-VI前体材料132和碱性材料141，且接着将其合成为合金混合物以形成Na:I-III-VI混合相半导体源层151。碱性材料141可与前体材料132中的一者、所有者或任何组合一起沉积(以任何顺序)以形成Na:I-II-VI层151。这些可能组合中的两者由图1E说明。
观看图1F，首先分别合成I-III-VI前体材料131和碱性材料141。接下来，循序将I-III-VI前体材料131和碱性材料141沉积在衬底上。接着，在约400℃-600℃的温度下用热处理来将I-III-VI前体材料131和碱性材料141形成合金，以形成Na:I-III-VI混合相半导体源层151。
尽管已参考特定实施例描述了本发明，但所属领域的技术人员将了解，可在不偏离本发明范围的情况下作出各种改变且可用等效物来取代其元素。另外，可在不偏离本发明范围的情况下，作出多种修改以使特定情形或材料适合本发明的教示。
因此，希望本发明不限于揭示为期望用于进行本发明的最佳模式的特定实施例，而是希望本发明将包括属于所附权利要求书的范围和精神的所有实施例。

Claims (77)

1.一种用于光电装置的混合相半导体源层，其包含半导体层和碱性材料，其中所述半导体层和所述碱性材料分别被合成再混合，接着沉积在衬底上。
2.根据权利要求1所述的混合相半导体源层，其中所述半导体层是通过传递I、III和VI型前体金属而形成的。
3.根据权利要求1所述的混合相半导体源层，其中所述碱性材料是Na-VII或Na2-VII。
4.根据权利要求1所述的混合相半导体源层，其中所述混合物是在环境温度和10-6-10-2托的压力下沉积的。
5.根据权利要求1所述的混合相半导体源层，其中所述混合物被热处理到400℃-600℃的温度。
6.根据权利要求1所述的混合相半导体源层，其中所述混合相半导体源层的厚度在150nm与500nm之间。
7.根据权利要求1所述的混合相半导体源层，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
8.一种用于光电装置的混合相半导体源层，其包含半导体层和碱性材料，其中所述半导体层和所述碱性材料分别被合成再被共同沉积在衬底上。
9.根据权利要求8所述的混合相半导体源层，其中所述半导体层是通过传递I、III和VI型前体金属而形成的。
10.根据权利要求8所述的混合相半导体源层，其中所述碱性材料是Na-VII或Na2-VII。
11.根据权利要求8所述的混合相半导体源层，其中所述半导体层和所述碱性材料是在环境温度和10-6-10-2托的压力下沉积的。
12.根据权利要求8所述的混合相半导体源层，其中所述半导体层和所述碱性材料在400℃-600℃的温度下被热处理。
13.根据权利要求8所述的混合相半导体源层，其中所述混合相半导体源层的厚度在150nm与500nm之间。
14.根据权利要求8所述的混合相半导体源层，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
15.一种用于光电装置的混合相半导体源层，其包含半导体层和碱性材料，其中所述半导体层和所述碱性材料被共同沉积在衬底上且接着被合成为合金混合物。
16.根据权利要求15所述的混合相半导体源层，其中所述半导体层是通过传递I、III和VI型前体金属而形成的。
17.根据权利要求15所述的混合相半导体源层，其中所述碱性材料是Na-VII或Na2-VII。
18.根据权利要求15所述的混合相半导体源层，其中所述半导体层和所述碱性材料是在环境温度和10-6-10-2托的压力下沉积的。
19.根据权利要求15所述的混合相半导体源层，其中所述半导体层和所述碱性材料在400℃-600℃的温度下被热处理。
20.根据权利要求15所述的混合相半导体源层，其中所述混合相半导体源层的厚度在150nm与500nm之间。
21.根据权利要求15所述的混合相半导体源层，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
22.一种用于光电装置的混合相半导体源层，其包含半导体层和碱性材料，其中所述半导体层和所述碱性材料经循序沉积，接着被合成为合金混合物。
23.根据权利要求22所述的混合相半导体源层，其中所述半导体层是通过传递I、III和VI型前体金属而形成的。
24.根据权利要求22所述的混合相半导体源层，其中所述碱性材料是Na-VII或Na2-VII。
25.根据权利要求22所述的混合相半导体源层，其中所述半导体层和所述碱性材料是在环境温度和10-6-10-2托的压力下沉积的。
26.根据权利要求22所述的混合相半导体源层，其中所述半导体层和所述碱性材料在400℃-600℃的温度下被热处理。
27.根据权利要求22所述的混合相半导体源层，其中所述混合相半导体源层的厚度在150nm与500nm之间。
28.根据权利要求22所述的混合相半导体源层，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
29.一种用于光电装置的混合相半导体源层，其包含半导体层和碱性材料，其中所述半导体层和所述碱性材料分别被合成，被循序沉积在衬底上，且接着通过热处理形成合金。
30.根据权利要求29所述的混合相半导体源层，其中所述半导体层是通过传递I、III和VI型前体金属而形成的。
31.根据权利要求29所述的混合相半导体源层，其中所述碱性材料是Na-VII或Na2-VII。
32.根据权利要求29所述的混合相半导体源层，其中所述半导体层和所述碱性材料是在环境温度和10-6-10-2托的压力下沉积的。
33.根据权利要求29所述的混合相半导体源层，其中所述半导体层和所述碱性材料在400℃-600℃的温度下被热处理。
34.根据权利要求29所述的混合相半导体源层，其中所述混合相半导体源层的厚度在150nm与500nm之间。
35.根据权利要求29所述的混合相半导体源层，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
36.一种用于产生用于光电装置的混合相半导体源层的方法，所述混合相半导体源层是通过沉积化学合金层来形成的，所述化学合金层包含碱性材料和半导体层，所述半导体层是通过传递I、III和VI型金属而形成的，其中所述碱性材料和所述半导体层被沉积在衬底上。
37.根据权利要求36所述的方法，其中从包含金属、不锈钢、塑料、玻璃和聚合物材料的材料群组中选出所述衬底。
38.根据权利要求36所述的方法，其中所述衬底是透磁的。
39.根据权利要求36所述的方法，其中所述衬底是镀有镍的钛。
40.根据权利要求36所述的方法，其中所述衬底是镀有钛和进一步镀有镍的不锈钢。
41.根据权利要求36所述的方法，其中所述衬底是具有钼涂层的塑料。
42.一种光电装置，其是通过将不锈钢薄片衬底提供到用于处理所述衬底的装置而制得的，其中所述处理是沉积多个薄层，所述多个薄层包含背部接触层、混合相半导体源层、前体p型吸收体层、n型结层、本征透明氧化层和导电透明氧化层。
43.根据权利要求42所述的光电装置，其中所述混合相半导体源层是通过沉积化学合金层而形成的，所述化学合金层包含碱性材料和半导体层，所述半导体层是通过传递I、III和VI型金属而形成的。
44.一种用于产生混合相半导体源层的方法，其中分别合成碱性材料和半导体层再混合，接着沉积在衬底上。
45.根据权利要求44所述的方法，其中通过传递I、III和VI型前体金属来形成所述半导体层。
46.根据权利要求44所述的方法，其中所述碱性材料是Na-VII或Na2-VII。
47.根据权利要求44所述的方法，其中在环境温度和10-6-10-2托的压力下沉积所述混合物。
48.根据权利要求44所述的方法，其中在400℃-600℃的温度下对所述半导体层和所述碱性材料进行热处理。
49.根据权利要求44所述的方法，其中所述混合相半导体源层的厚度在150nm与500nm之间。
50.根据权利要求44所述的方法，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
51.一种用于产生混合相半导体源层的方法，其中单独合成碱性材料和半导体层且接着将其共同沉积在衬底上。
52.根据权利要求51所述的方法，其中通过传递I、III和VI型前体金属来形成所述半导体层。
53.根据权利要求51所述的方法，其中所述碱性材料是Na-VII或Na2-VII。54.根据权利要求51所述的方法，其中在环境温度和10-6-10-2托的压力下沉积所述碱性材料和半导体层。
55.根据权利要求51所述的方法，其中在400℃-600℃的温度下对所述半导体层和所述碱性材料进行热处理。
56.根据权利要求51所述的方法，其中所述混合相半导体源层的厚度在150nm与500nm之间。
57.根据权利要求51所述的方法，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
58.一种用于产生混合相半导体源层的方法，其中将碱性材料和半导体层共同沉积在衬底上且接着将其合成为合金混合物。
59.根据权利要求58所述的方法，其中通过传递I、III和VI型前体金属来形成所述半导体层。
60.根据权利要求58所述的方法，其中所述碱性材料是Na-VII或Na2-VII。
61.根据权利要求58所述的方法，其中在环境温度和10-6-10-2托的压力下沉积所述碱性材料和半导体层。
62.根据权利要求58所述的方法，其中在400℃-600℃的温度下对所述半导体层和所述碱性材料进行热处理。
63.根据权利要求58所述的方法，其中所述混合相半导体源层的厚度在150nm与500nm之间。
64.根据权利要求58所述的方法，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
65.一种用于产生混合相半导体源层的方法，其中循序沉积碱性材料和半导体层且接着将其合成为合金混合物。
66.根据权利要求65所述的方法，其中通过传递I、III和VI型前体金属来形成所述半导体层。
67.根据权利要求65所述的方法，其中所述碱性材料是Na-VII或Na2-VII。
68.根据权利要求65所述的方法，其中在环境温度和10-6-10-2托的压力下沉积所述碱性材料和半导体层。
69.根据权利要求65所述的方法，其中在400℃-600℃的温度下对所述半导体层和所述碱性材料进行热处理。
70.根据权利要求65所述的方法，其中所述混合相半导体源层的厚度在150nm与500nm之间。
71.根据权利要求65所述的方法，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
72.一种用于产生混合相半导体源层的方法，其中单独合成碱性材料和半导体层，将其循序沉积在衬底上，且接着通过热处理形成合金。
73.根据权利要求72所述的方法，其中通过传递I、III和VI型前体金属来形成所述半导体层。
74.根据权利要求72所述的方法，其中所述碱性材料是Na-VII或Na2-VII。
75.根据权利要求72所述的方法，其中在环境温度和10-6-10-2托的压力下沉积所述碱性材料和半导体层。
76.根据权利要求72所述的方法，其中在400℃-600℃的温度下对所述半导体层和所述碱性材料进行热处理。
77.根据权利要求72所述的方法，其中所述混合相半导体源层的厚度在150nm与500nm之间。
78.根据权利要求72所述的方法，其中所述混合相半导体源层含有5.0到约15.0重量％的碱金属含量。
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