CN1204419A - 采用电淀积方法制备用于生产高效太阳能电池的Cu In Ga Se (x=0－2,y=0－2,z=0－2,n=0－3) - Google Patents

采用电淀积方法制备用于生产高效太阳能电池的Cu In Ga Se (x=0－2,y=0－2,z=0－2,n=0－3) Download PDF

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CN1204419A
CN1204419A CN96199008A CN96199008A CN1204419A CN 1204419 A CN1204419 A CN 1204419A CN 96199008 A CN96199008 A CN 96199008A CN 96199008 A CN96199008 A CN 96199008A CN 1204419 A CN1204419 A CN 1204419A
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R·N·比哈塔查亚
M·A·科特里拉斯
J·科尼
A·L·坦纳特
J·R·图特利
K·拉曼纳塞
R·诺非
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Abstract

可用于生产太阳能电池的高质量铜—铟—镓—联硒的薄膜是通过在玻璃/Mo基材(12、14)上电淀积至少一种构成金属(18),接着通过物理气相淀积铜和硒或铟和硒来调整该薄膜的最终化学计量为接近Cu(In,Ga)Se2来制备的。在电淀积中采用1～100千赫的交流电和直流电可提高淀积薄膜的形态和生长速度。可以采用含有至少一部分有机溶剂的电淀积溶液,同时提高阴极电位来提高该电淀积薄膜的镓含量。

Description

采用电淀积方法制备用于生产高效太阳能电池的 CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3) 前体薄膜的方法
相关申请
本申请是1995年9月25日提交的No．60／004269号临时申请的部分继续。
本发明涉及薄膜半导体器件的制备方法。更具体地说，本发明涉及用于太阳能电池的铜-铟-镓-硒化物薄膜的电淀积方法。
铜-铟-联硒化物(CuInSe2)和铜-铟-镓-联硒化物(CuIn1-xGaxSe2)的黄铜矿三元薄膜通常是指Cu(In、Ga)Se2、CIGS或简单的CIS，近年来它们已经成为人们关注和对半导体器件的研究的重点。硫也可以并且有时代替硒，这样该化合物有时甚至通常是指Cu(In、Ga)(Se，S)2，以便包括所有可能的组合。这些装置也可以根据它们的组成元素族称I-III-VI2装置。
这些器件用作光电设备的器件或者太阳能电池吸收器是特别有利的。对于光电设备来说，p-型CIGS层与n-型CdS层结合，形成一个p-n异质结的CdS／CIGS器件。CIGS的直接禁带宽度产生一个大的光学吸收常数，反过来允许采用厚度1～2微米左右的薄层。CIGS器件的其它优点是它们的长期稳定性。
用于制备CIGS薄膜的各种方法已有报道。一些早期的技术包括在含硒气体包括H2Se存在情况下，在基材上加热铜和铟。在含硒气体存在情况下加热铜和铟膜已知称为硒化。采用H2Se进行硒化的一个缺点是H2Se气体的毒性大，因此对大规模生产环境中的人们非常危险。
Eberspacher等的US5045409公开了通过磁控管溅射淀积铜和铟膜，和通过热蒸发，接着通过在不同气体存在情况下加热淀积硒膜的方法。其它制备CIS膜的方法包括分子束外延，以一个步骤或多个步骤电淀积，和单晶和多晶膜的气相淀积。
尽管气相淀积技术已用于生产效率高至百分之十七(17％)的太阳能电池，气相淀积仍是昂贵的。因此，通过气相淀积生产的太阳能电池一般限于用在试验室试验的设备上，并且不适于进行大规模的生产。另一方面，采用电淀积技术制备的薄膜太阳能电池通常要便宜的多。但是，通过电淀积生产的太阳能电池通常效率低。例如，在Solar Cells with ImprovedEfficiency Based on Electrodeposited Copper Indium Diselenide ThinFilms，ADVANCED MATERIALS，Vol．6，No．5(1994)，Guillemoles等指出通过电淀积生产的太阳能电池的效率为5．6％左右。
本发明的目的在于提供一种改进的方法，用于生产高质量的薄膜Cu(In，Ga)Se2太阳能电池。
本发明的另一个目的在于提供低成本高质量的并具有高转化效率的薄膜太阳能电池。
本发明还有一个目的是提供了一种方法，用于生产用于太阳能的和非太阳能的电池的Cu-In、Cu-Se、Cu-In-Se和Cu-In-Ga-Se金属薄膜。
本发明还有一个目的是提供一种方法，用于电淀积含镓金属薄膜太阳能电池前体。
为了达到与本发明有关的上述目的和其它目的以及有利效果，正如在此所作的具体的和概括的描述，本发明的方法包括电淀积一个CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3)层，优选地采用直流电结合交流电，接着通过气相淀积另外的铜和硒或铟和硒，来调整使最终的组合物非常接近化学计量Cu(In，Ga)Se2。这种独特的两步薄膜淀积方法是使前体金属膜通过廉价的电淀积方法进行淀积，再采用更加昂贵但是技术更加精确的物理气相淀积方法调节最终的膜，使其在所需的化学计量范围内。太阳能电池也可以通过例如在CdS的化学浴淀积(CBD)之后溅射ZnO，并且加上双层金属接触器和任选地防反射层来完成。根据本发明方法生产的太阳能电池是一个效率为9．44％的装置。
本发明的其它目的、优点和新的特征一部分将在下面的说明书中说明，并且一部分对本领域的技术人员来说通过对下面说明和附图的研究是清楚的。
图1是根据本发明制备的CIGS光电设备的截面图。
图2是图1所示的导电氧化锌层28的截面图。
图3是根据本发明实施例3生产的CdS／CuInSe2太阳能电池的电流与电压的特性曲线图。
图4是实施例3的CdS／CuInSe2太阳能电池的相对量子效率与波长的曲线图。
本发明包括一个基本上是两个步骤的方法，用于生产高质量低成本的薄膜CIGS半导体器件，该器件具有光电特性并特别适合用于太阳能电池。在第一个步骤中，在基材上电淀积CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3)的前体膜，该基材是例如用钼涂敷的玻璃。第一个步骤包括一个特定的方法和用于电淀积镓和其它元素的电淀积电解浴，以及交流电和直流电的特定用法。
第二个步骤是单独的或与Ga结合的Cu+Se或In+Se的物理气相淀积。在第二步中，精确控制整个膜的组成，以使生成的薄膜与化学计量Cu(In，Ga)Se2非常接近。这两个步骤都可在具有大表面积的基材上进行。因此本发明的方法可以有效地生产具有大面积、高效率的太阳能电池。
参考图1，CdS／CIGS光电设备10包括基材12，它可以是例如钠钙硅玻璃或者无定形7059玻璃。基材12还含有一个厚度约为1～2微米的钼的背面接触层14。钼可以采用直流电溅射方法从转筒磁控管对电极(CMAG)淀积。为了提高Mo层14和要被淀积的前体膜之间的粘着性，也可以通过电淀积淀积另一个粘合层16。在淀积Mo层14和任选地铜粘合层16之后，该基材可采用例如丙醇脱脂并在氮气流中干燥。
再通过电淀积淀积金属前体膜18。该前体膜含有一种或多种元素铜、铟、镓和硒。淀积这些金属，电淀积是比气相淀积更廉价的方法。但是，它不能在电淀积过程中根据需要控制被淀积金属的比例。因此，现有的完全通过电淀积方法淀积的CIGS层的转化效率低。在本发明中，结合电淀积步骤和其后的气相淀积步骤。这就使要被淀积的前体金属大部分采用廉价的电淀积步骤，接着进行气相淀积步骤，以精确控制最终的金属比例。这就是生产高效电池的廉价方法。金属前体膜18的组成通常被表示为CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3)。金属前体膜18应淀积约1～3微米厚，厚度可通过库仑测定来控制。
已经发现采用交流电压和直流电压来电淀积膜产生改进的结果。交流电压改进了膜的形态。也可以认为交流电压通过产生其它成核中心来提高薄膜的成核(生长)。对于完全是水基的电镀溶液来说，可利用的直流电压范围是约1～5V，优选地电压约为2V。通过重叠1～100千赫的频率的0．2～5．0V的交流电压，优选的10～30千赫的频率的0．3～1．0V的交流电压可以获得改进的结果。发现约0．45V的交流电在约18．1千赫的频率会产生良好的结果。将电解溶液的pH调节至约为1．0～4．0，更优选地是约1．4～2．4。电解溶液优选地约为10℃～80℃，更优选地是约24℃。往电解槽中加入支持电解质可以再提高该电解溶液的导电性，进一步提高电淀积的速度。已经发现盐，例如NaCl、LiCl或者Na2SO4是可用于本发明某些实施方案的合适的支持电解质。
在整个水基溶液中，水分子的电解在约2～3伏时开始发生至不期望的程度。生成的O2-和OH-离子与淀积金属离子或淀积的金属结合，在前体膜18上形成不需要的金属氧化物和氢氧化物。为了克服上述缺陷，电解溶液中的水可以部分地或者全部被一种或多种有机溶剂，如二甲亚砜(DMSO)代替。提高电淀积溶液中的有机溶剂含量会提高阴极电位，而不会不利地提高金属氧化物和氢氧化物形成的速度。提高的阴极电位会增大前体膜的淀积速度。另一个优点是提高阴极电位会提高镓相对于其它淀积金属的淀积速度。因此，采用含有一种或多种有机溶剂的溶液会使阴极电位可以在宽范围内选择，以便使已淀积前体膜18具有所需的化学计量。当采用有机溶剂时，优选阴极电位约为3～10V的直流电和频率约为1～100千赫的0．2～5．0V交流电。约5V的直流电压和频率约18．1千赫的0．45V交流电压会产生良好的结果。
根据需要第二种电解溶液可用于在气相淀积阶段之前调节电淀积膜的化学计量。例如第一个电淀积步骤可以生成含有少于所需量的镓的CIGS前体膜。尽管在气相淀积阶段可以提高镓的含量，但采用第二种电淀积溶液淀积一定量的镓，以便在气相淀积步骤精确按化学计量调整之前粗略按化学计量调整，这样会使成本更低。另一种采用第二种电淀积溶液的可行方法是在淀积膜上形成一个组分梯度，这是Michelsen等在US4335266中提出的，其关于用于太阳能电池和其它用途的组成分级的CIGS薄膜的说明在此结合可作为参考。还有另一个在电淀积过程中使得组成分级的方法，即随着电淀积的进行改变工艺参数，如阴极电位、阳离子浓度、pH或者温度。
下面给出几个根据本发明生产的电淀积金属前体膜的实施例。这些实施例包括In-Se、Cu-Se和Cu-In-Se前体膜。对于这些前体膜，加入Ga以增加禁带宽度。可以通过分步电淀积来加入Ga，而优选地是在气相淀积步骤中通过蒸发元素镓来加入。还给出一个新溶液和方法的例子，即连同其它前体金属一起电淀积Ga，以便在一个步骤淀积Cu-In-Ga-Se前体膜。该溶液含有铜、铟、镓和硒各元素的离子。这些离子可以以可溶金属盐的形式采用。
在电淀积前体膜18之后，应将其清洗。适用的方法是采用去离子水清洗前体膜18，并在氮气流中将其干燥。在清洗前体膜18之后，通过物理气相淀积法淀积一个带有或者不带有镓的In+Se或Cu+Se的附加层20，以便将最终的膜组分调节为比例约为Cu=1～1．2∶(In，Ga)=1～1．2∶Se=2～2．5，最优选地是约为1∶1∶2。通过控制In／Ga的比例，CdS和CIGS之间的禁带宽度可以被调整到理想值或者接近理想值。约为1．45eV的禁带宽度被认为对地球上的太阳能转化是理想的，并且其是通过In／Ga比例约为3∶1达到的。基材(前体膜)的温度在PVD过程中为300～600℃，优选地约550℃。
在PVD之后，应对膜进行退火。退火改进了膜的均匀性和质量。高质量的CIGS膜在膜中没有会降低转化率的多余的铜核、空隙或者空位。在250～500℃的真空中对膜进行退火，接着以约3℃／分钟的速度冷却，以避免温度骤降，这样会产生良好的结果。因为硒具有比铜、铟或者镓更高的蒸汽压，硒在气相淀积和退火的高温步骤过程中会从膜中流失。作为补偿，这些步骤过程中的气体可以含有中等过压的硒。在优选的实施方案中，该膜在从PVD温度冷却到退火温度过程中以5～100埃／秒的速度进行硒化。
一旦CIGS层18和20共同淀积并退火，接下来淀积含有硫化镉的n-型半导体的薄层22。CdS层22优选地通过化学浴淀积(CBD)淀积，厚度为200～1000埃。CBD浴可以由0．08gmCdSO4、2．5gm硫脲和27．5gm NH4OH溶解在200毫升水中制备。淀积温度约为40～80℃。
接着淀积导电宽禁带n-型半导体材料的层28。在优选实施方案中，层28包括两个氧化锌层24和26，如图2所示。首先，采用RF溅射以约0．62瓦／cm2在压力为10毫乇的氩气等离子体中淀积氧化锌层24。其次，也采用RF溅射以约1．45瓦／cm2在压力为10毫乇的氩气等离子体中淀积含有约1～5％的掺有Al2O3的氧化锌的第二氧化锌层26。在典型实施方案中，第一层的电阻率为50～200欧姆／cm2的，第二层的电阻率为15～20欧姆／cm2。整体ZnO层的透射率为80～85％。
双层金属接点30可以采用电子束系统或其它技术制备。在典型实施方案中，第一个金属接点层是500～1000埃厚的Ni，第二个金属接点层是1～3微米厚的Al。金属接点30一般形成遍布器件的集电面的细格线，并与合适的电流集电极(未表示出)连接。制成器件的效率通过电子束加上抗反射涂层32，例如600～1000埃的MgF2的层而进一步提高。根据下面实施例3生产的器件的转化效率为9．44％。
实施例1
将In1-2Se1-3的金属前体膜电淀积在涂敷有厚度约为500埃的Mo或Mo／Cu层的玻璃基材上。采用含有溶解在200毫升水中的2．25gmInCl3和0．41gmH2SeO3的电镀溶液淀积该前体膜。采用稀HCl(10％体积)将溶液的pH调节到1．4～2．4。采用2～5伏直流电压和频率为18．1千赫的0．45伏交流电压淀积该膜。该膜的厚度为1～3微米并附着在基材上。
实施例2
采用含有溶解在300毫升水中的6．21gmCu(NO3)2·6H2O和1．6gmH2SeO3的电镀溶液，将Cu1-2Se1-3的金属前体膜电淀积在基材上。采用稀HCl(10％体积)将pH调节到1．4～2．4。采用2～5伏直流电压和频率为18．1千赫的0．45伏交流电压淀积该膜。该淀积层的厚度为1～3微米并附着在基材上。
实施例3
采用含有溶解在1050毫升水中的4．47gmCuCl2、5．67gmInCl3和3．39gmH2SeSO3的电镀溶液，将Cu1-2In1-2Se1-3的金属前体膜电淀积在基材上。采用稀HCl(10％体积)将pH调节到1．4～2．4，采用2～5伏直流电压和频率为18．1千赫的0．45伏交流电压淀积该膜。淀积层的厚度为1～3微米并附着在基材上。该电淀积膜含铟稍有不足。接着通过气相淀积来加入铟，将最终的含量调整至约CuInSe2。接着加入CdS和ZnO以制成太阳能电池。使制成的太阳能电池在25℃受到ASTM E892-87Global(1000Wm-2)标准放射光谱的作用。完成的太阳能电池的面积为0．4285cm2，其性能参数测定如下：
Voc=0．4138V        VPmax=0．3121V
Isc=15．40mA        IPmax=12．96mA
Jsc=35．94mAcm-2    Pmax=4．045mW
填充系数=63．47％   效率=9．44％
图3是该器件的I-V图。图4是该器件的相对量子效率图。该器件只含有Cu-In-Se，不含镓。该器件的效率没有抗反射层时为8．76％，加上抗反射层时效率是9．44％。可以认为通过加入镓，将生成电池的效率提高到百分之十四(14％)左右。
实施例4
采用含有溶解在450毫升水中的1．12gmCu(NO3)2·6H2O、12．0gmInCl3、4．60gmGa(NO3)3·xH2O和1．80gmH2SeO3的电镀溶液，将Cu1-2In1-2Ga0．01-1Se1-3的金属前体膜电淀积在基材上。这相当于约2．49gm／lCu(NO3)2·6H2O、26．7gm／lInCl3、10．2gm／lGa(NO3)3·xH2O和4．0gm／lH2SeO3和分别为大约0．0084、0．12、0．28和0．31摩尔浓度的铜、铟、镓和硒离子。采用稀HCl(10％体积)将pH调节到1．4～2．4。采用2～5伏的直流电压和频率为18．1千赫的0．45伏交流电压淀积该膜。该淀积层厚度为1～3微米并附着在基材上。
实施例5
采用含有溶解在450毫升DMSO中的1．496gmCu(NO3)·5H2O、14．929gmInCl3、1．523gmH2SeO3和7．192gmGa(NO3)3的电镀溶液，将Cu1-2In1-2Ga0．01-1Se1-3的金属前体膜电淀积在基材上。采用电压为5V的直流电在25℃和在50℃淀积该膜。
实施例6
采用含有溶解在400毫升DMSO和50毫升水的混合物中的1．496gmCu(NO3)·5H2O、14．929gmInCl3、1．523gmH2SeO3和7．192gmGa(NO3)3的电镀溶液，将Cu1-2In1-2Ga0．01-1Se1-3的金属前体膜电淀积在基材上。采用电压为5V的直流电在25℃和在50℃淀积该膜。
实施例7
采用含有溶解在400毫升DMSO和50毫升水的混合物中的1．496gmCu(NO3)·5H2O、14．929gmInCl3、1．523gmH2SeO3、7．192gmGa(NO3)3和10gmNa2SO4和20gmLiCl的电镀溶液，将Cu1-2In1-2Ga0．01-1Se1-3的金属前体膜电淀积在基材上。采用电压为5V的直流电在25℃和在50℃淀积该膜。
如上所述的本发明可以结合到各种用途中，例如将太阳能转变成电能用于基线发电。其它用途包括用于太阳能计算机、电池充电器，如高速公路紧急呼叫箱、光电眼、夜间安全灯活化剂、用于照相和其它用途的光源等等。
尽管本发明参照优选实施方案和附图以及实施例进行了详细说明，对本领域的技术人员来说，本发明的各种用途和变形可以不偏离本发明的实质和范围完成。因此，可以认为在此的详细说明书和附图不是对本发明范围的限定，它可以从下面的权利要求书推导出来，并且它们在法律上是等效的。

Claims (28)

1．一种制备金属薄膜的方法，该方法包括步骤：
在基材上电淀积CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3)的层；
通过气相淀积在所说的CuxInyGazSen层上淀积足量的In+Se或Cu+Se，以在基材上生成Cu(In，Ga)Se2薄膜，其中所说的薄膜具有约为Cu=1～1．2∶(In，Ga)=1～1．2∶Se=2～2．5的化学计量比例。
2．权利要求1记载的方法，其中所说的CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3)层含有In1-2Se1-3。
3．权利要求1记载的方法，其中所说的CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3)层含有Cu1-2Se1-3。
4．权利要求1记载的方法，其中所说的CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3)层含有Cu1-2In1-2Se1-3。
5．权利要求1记载的方法，其中所说的CuxInyGazSen(x=0～2，y=0～2，z=0～2，n=0～3)层含有Cu1-2In1-2Ga0．01-1Se1-3(x=1～2，y=1～2，z=0．01～1，n=1～3)。
6．权利要求1记载的方法，其中气相淀积包括物理气相淀积。
7．权利要求6记载的方法，其中物理气相淀积在约550℃的温度下进行。
8．权利要求1的方法，其中电淀积是在约1-10伏的直流电压下进行。
9．权利要求8记载的方法，其中电淀积是在频率为1～100千赫约0．2～5．0伏的的交流电压进行。
10．权利要求9记载的方法，其中电淀积在水基电淀积溶液中进行，所说的直流电压约为1～5伏，所说的交流电压约为0．3～1．0伏，频率为10～30千赫。
11．权利要求10记载的方法，其中直流电压约为2伏，交流电压约为0．45伏，频率为18．1千赫。
12．权利要求8记载的方法，其中直流电压约为3～10伏，电淀积在含有至少一种有机溶剂的电淀积溶液中进行，并且电淀积进一步采用频率为1～100千赫的约0．2～5．0伏的交流电压进行。
13．权利要求12记载的方法，其中所说的交流电压约为0．45伏，频率约为18．1千赫。
14．权利要求1记载的方法，其中电淀积步骤是在含有至少一种用于提高电淀积溶液导电性并提高CuxInyGazSen层的淀积速度的支持电解质的电淀积溶液中进行。
15．权利要求14记载的方法，其中所说的支持电解质含有至少一种选自NaCl、LiCl和Na2SO4的化合物。
16．权利要求1记载的方法进一步包括下面的步骤：
通过化学浴淀积在基材上淀积CdS；和
通过RF溅射在基材上淀积ZnO。
17．一种设备，包括：
采用按照权利要求1记载的方法制备的金属薄膜制成的太阳能电池，该太阳能电池受到光作用时产生电能；
利用该太阳能电池的电势的电路。
18．用于电淀积太阳能电池前体薄膜的方法，该方法包括：
在基材上电淀积含有铜、铟、镓和硒的薄膜，该电淀积是在含有铜、铟、镓和硒离子的电淀积溶液中进行。
19．权利要求18记载的方法，其中所述的电淀积溶液含有浓度分别约为0．0084、0．12、0．28和0．31摩尔浓度的铜、铟、镓和硒离子。
20．权利要求19记载的方法，其中所说的电淀积溶液含有约2．49gm／l的Cu(NO3)2·6H2O，26．7gm／l的InCl3，10．2gm／l的Ga(NO3)3和4．0gm／l的H2SeO3。
21．权利要求18记载的方法，其中电淀积溶液的pH约为1．0～4．0。
22．权利要求18记载的方法，其中电淀积在直流电压为1～10伏下进行。
23．权利要求22记载的方法，其中电淀积在交流电压约为0．2～5．0伏，频率为1～100千赫下进行。
24．权利要求23记载的方法，其中所说的交流电压的电压约为0．45伏，频率为18．1千赫。
25．权利要求18记载的方法，其中电淀积溶液进一步含有至少一种有机溶剂，电淀积的直流电压约为3～10伏。
26．一种制备太阳能电池前体薄膜的方法，该方法包括下面的步骤：
采用直流电压和约为0．1～5．0的交流电压在基材上电淀积金属前体薄膜。
27．权利要求26的方法，其中交流电压约为0．3～1．0伏，频率为10～30千赫。
28．权利要求27的方法，其中交流电压约为0．45伏，频率为18．1千赫。
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JP2000501232A (ja) 2000-02-02
US5871630A (en) 1999-02-16
JP3753739B2 (ja) 2006-03-08
WO1997022152A1 (en) 1997-06-19
CN1155111C (zh) 2004-06-23
KR19990071500A (ko) 1999-09-27
BR9612022A (pt) 1999-06-15
DE69621467T2 (de) 2002-11-07
EP0956600B1 (en) 2002-05-29
CA2239786A1 (en) 1997-06-19
US5804054A (en) 1998-09-08
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EP0956600A1 (en) 1999-11-17
NO982699L (no) 1998-08-11
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CA2239786C (en) 2006-03-14
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