CN108305906B - 太阳能电池吸收层的制备方法和太阳能电池的制备方法 - Google Patents

太阳能电池吸收层的制备方法和太阳能电池的制备方法 Download PDF

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CN108305906B
CN108305906B CN201810128936.0A CN201810128936A CN108305906B CN 108305906 B CN108305906 B CN 108305906B CN 201810128936 A CN201810128936 A CN 201810128936A CN 108305906 B CN108305906 B CN 108305906B
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solar battery
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copper
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CN108305906A (zh
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叶亚宽
赵树利
郭逦达
杨立红
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Shanghai zuqiang Energy Co.,Ltd.
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Beijing Apollo Ding Rong Solar Technology Co Ltd
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Priority to PCT/CN2018/098106 priority patent/WO2019153668A1/zh
Priority to CN201880002666.7A priority patent/CN110352499A/zh
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Abstract

本发明公开了一种太阳能电池吸收层的制备方法和太阳能电池的制备方法，其中该吸收层的制备方法包括在沉积有背电极的基底上依次溅射铜镓合金层和铟层；将铜铟镓预制膜放入具有第一温度阈的反应腔中，并在反应腔中通入第一载气流量值的硒气氛，使铜铟镓预制膜在第一时长内持续反应；向反应腔内通入第二载气流量值的硒气氛，使铜铟镓预制膜在第二时长内持续反应；在预设的第二温度阈和第三时长内对基底进行退火处理。本发明提供的太阳能电池吸收层的制备方法，通过控制通入的硒气氛的载气流量、反应温度及反应时间，使硒元素可以穿过不饱和In‑Se、Cu‑Se二元相向预制膜底部扩散，避免了镓元素向底部富集的问题。

Description

太阳能电池吸收层的制备方法和太阳能电池的制备方法
技术领域
本发明涉及太阳能电池制造技术领域，尤其涉及一种太阳能电池吸收层的制备方法和太阳能电池的制备方法。
背景技术
铜铟镓硒(简称CIGS)薄膜太阳能电池是新一代最具发展前景的太阳能电池。它具有转换效率高、成本低、寿命长、弱光性能好、抗辐射能力强等优点。自20世纪90年代以来一直是实验室转换效率最高的薄膜太阳能电池。2016年德国ZSW将CIGS实验室效率提升至22.6％，与晶硅电池的转换效率较为接近，发展前景巨大。
CIGS吸收层的制备方法主要有共蒸发法、溅射后硒化法(简称两步法)以及电化学法等。其中，共蒸发法是通过蒸发Cu、In、Ga、Se四种元素，使其同时在基底沉积反应得到CIGS吸收层；两步法是首先通过溅射In2Se3、Ga2Se3、Cu2Se等化合物靶材得到铜铟镓硒预制膜，然后在H2Se或者Se蒸气气氛下进行高温热处理获得CIGS吸收层。
共蒸发法制备CIGS吸收层能够使小面积电池获得较高的转换效率，但对于大面积电池而言，由于大面积电池加工均匀性难以控制，产业化应用受到一定局限，无法获得高转换效率。对于两步法制备CIGS，由于Se与Cu、In、Ga元素的反应速率存在差异，导致热处理后形成底部富集Ga元素的细小晶粒，无法形成良好Ga元素分布的高性能CIGS吸收层。电化学法目前在大面积电池的稳定性以及CIGS电池的最高效率等方面仍与共蒸发法及两步法制备CIGS电池存在一定差距，产业化进程较慢。
发明内容
本发明的目的是提供一种太阳能电池吸收层的制备方法和太阳能电池的制备方法，以提高大面积CIGS薄膜制备工艺的稳定性，以及提高CIGS薄膜太阳能电池的光电转换效率。
本发明提供了一种太阳能电池吸收层的制备方法，其中，包括如下步骤：
在沉积有背电极的基底上依次溅射铜镓合金层和铟层，以形成铜铟镓预制膜；
将所述铜铟镓预制膜放入具有预设的第一温度阈的反应腔中，并在所述反应腔中通入预设的第一载气流量值的硒气氛，使所述铜铟镓预制膜在所述第一载气流量值的硒气氛中反应第一预设时长；
向所述反应腔内通入预设的第二载气流量值的硒气氛，使所述铜铟镓预制膜在所述第二载气流量值的硒气氛中反应第二预设时长；
在预设的第二温度阈和第三预设时长内对所述基底进行退火处理。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，所述第一载气流量值与所述第二载气流量值的比大于5。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，在将所述铜铟镓预制膜放入具有预设的第一温度阈的反应腔中之前还包括：
在真空或设定气压的惰性气体中，将固态硒源加热至预设的第三温度阈内，以在所述反应腔中形成硒气氛。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，所述预设的第一温度阈为550℃～580℃，所述预设的第二温度阈为500℃～600℃，所述预设的第三温度阈为250℃～470℃，所述设定气压为1Pa～1atm。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，所述第一预设时长为25s～35s，所述第二预设时长为260s～275s，所述第三预设时长为5min～30min。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，所述预设的第一温度阈为620℃～700℃，所述预设的第二温度阈为500℃～600℃，所述预设的第三温度阈为380℃～500℃。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，所述第一预设时长为15s～25s，所述第二预设时长为15s～35s，所述第三预设时长为5min～30min。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，所述铜铟镓预制膜组成元素的原子比例满足：0.8≤Cu/(In+Ga)≤0.96，0.25≤Ga/(In+Ga)≤0.35。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，所述反应腔为石墨反应腔。
如上所述的太阳能电池吸收层的制备方法，其中，优选的是，所述硒气氛包括：硒蒸气或硒化氢气体。
本发明还提供了一种太阳能电池的制备方法，其中，包括上述任一项所述的本发明提供的太阳能电池吸收层的制备方法。
本发明提供的太阳能电池吸收层的制备方法和太阳能电池的制备方法，通过控制通入的硒气氛的载气流量、反应温度及反应时间，使硒元素可以穿过不饱和In-Se、Cu-Se二元相向预制膜底部扩散，避免了镓元素向底部富集的问题，提高了CIGS薄膜晶粒尺寸。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1为本发明一种实施例提供的太阳能电池吸收层的制备方法的流程图。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能解释为对本发明的限制。
如图1所示，本发明实施例提供了一种太阳能电池吸收层的制备方法，其包括如下步骤：
S100、在沉积有背电极的基底上依次溅射铜镓合金层和铟层，以形成铜铟镓预制膜(CIG预制膜)。
其中，基底采用2～3.2mm厚度的钠钙玻璃，同时采用金属钼作为背电极，金属钼层的厚度为300～1000nm。铜镓合金层中铜原子和镓原子所占的百分比分别为75％和25％；铜镓合金层的厚度可以为300nm，铟层的厚度可以为250nm。此外，对铜镓合金层和铟层的溅射采用磁控溅射，具体可以为直流溅射或中频溅射。
S200、将铜铟镓预制膜放入具有预设的第一温度阈的反应腔中，并在反应腔中通入预设的第一载气流量值的硒气氛，使铜铟镓预制膜在第一载气流量值的硒气氛中反应第一预设时长。其中，上述反应腔为石墨反应腔。
S300、向所述反应腔内通入预设的第二载气流量值的硒气氛，使铜铟镓预制膜在第二载气流量值的硒气氛中反应第二预设时长。
S400、在预设的第二温度阈和第三预设时长内对基底进行退火处理。
需要说明的是，传统的两步硒化法采用在饱和的硒气氛下反应生成铜铟镓硒(CIGS)吸收层，但是，此方法无法精确控制Cu、In、Ga几种金属原子与Se分子的反应过程，由于In、Cu与Se的反应生成焓较低，反应速率较快，由此导致通过传统两步法制备的CIGS吸收层的底部出现Ga富集现象，并形成了底部细小晶粒。
如果采用传统的两步硒化法，会在本申请中的CIG预制膜表面形成稳定浓度的Se蒸气，Se首先与In、Cu分别反应形成相对稳定的In2Se3和Cu2Se二元相，在CIG预制膜表面覆盖了稳定的In2Se3和Cu2Se二元相后，此二元相会成为Se元素的扩散阻碍，导致Se元素向CIG预制膜底部扩散能力下降，进而又进一步导致In、Cu元素向CIG预制膜表面扩散而与Se反应形成二元相，最终形成了具有Ga元素富集于CIGS底部的细晶粒的CIGS吸收层，而无法获得具有良好的Ga元素分布的高性能CIGS吸收层。
而为了解决上述问题，在本申请实施例中，先形成CIG预制膜，在CIG预制膜进入反应腔后，通入高浓度的硒气氛，并维持一定时间，在此阶段，CIG预制膜表面可以形成非饱和的In-Se、Cu-Se二元相，该非饱和的二元相由于部分化学键未饱和，从而不会成为Se元素扩散的阻碍，使得Se元素可通过此不饱和的化学键向CIG预制膜底部进行扩散。
在高浓度硒气氛中完成反应后，将硒气氛的浓度降低，从而不会使得CIG预制膜表面的不饱和In-Se、Cu-Se二元相快速形成饱和的In2Se3和Cu2Se而阻挡了Se元素向CIG预制膜底部扩散；在低浓度硒气氛条件下，Se原子通过不饱和键向底部快速扩散，从而避免了Ga元素向底部富集的现象，同时提高了CIGS薄膜晶粒尺寸；同时，低浓度的硒气氛能够补足CIG预制膜反应生成CIGS四元相时所需的硒。最后，将反应腔温度升高至一定温度范围内后，使CIG预制膜在高温以及一定浓度硒气氛环境下进行退火处理，以提高CIGS薄膜的晶粒尺寸及进一步改善Ga元素的扩散，从而可以获得具有良好的Ga元素分布的高性能CIGS吸收层，同时解决了现有技术中大面积电池稳定性及加工均匀性难以控制的问题。
需要说明的是，铜铟镓预制膜组成元素的原子比例满足：0.8≤Cu/(In+Ga)≤0.96，0.25≤Ga/(In+Ga)≤0.35。
其中，当Cu/(In+Ga)高于0.96时，易于形成富Cu的CuxSe相，导致CIGS薄膜性能显著下降，从而无法获得高性能电池；而当Cu/(In+Ga)低于0.80时，易于在CIGS膜层中形成富余的In-Se、Ga-Se二元相，当In-Se、Ga-Se二元相较多时，无法获得性能优异的黄铜矿CIGS相，导致电池性能下降。
另外，第一载气流量值与第二载气流量值的比大于5。可选的，第一载气流量值可以大于等于5slm且小于等于15slm，由此可以提供高浓度的硒气氛，使得CIG预制膜表面可以形成非饱和的In-Se、Cu-Se二元相，而第二载气流量值可以大于0且小于等于2slm，由此可以使Se原子通过不饱和键向底部快速扩散，从而避免了Ga元素向底部富集的现象，此外，在上述载气流量下，硒气氛可以充分参与反应，避免了硒元素反应过剩而浪费。其中，向反应腔中通入的硒气氛可以为硒蒸气或硒化氢(H2Se)气体。
进一步地，在步骤S200之前还包括：
S110、在真空或设定气压的惰性气体中，将固态硒源加热至预设的第三温度阈内，以在所述反应腔中形成硒气氛，以便于后续向反应腔中通入硒气氛的载气流量的控制。其中，该惰性气体可以为氮气。
在本申请提供的一具体实施例中，预设的第一温度阈可以为550℃～580℃，在该温度范围下，CIG预制膜可以与硒气氛充分反应，以获得具有良好的Ga元素分布的高性能CIGS吸收层；预设的第二温度阈可以为500℃～600℃，预设的第三温度阈可以为250℃～470℃，以形成高温硒气氛，便于后续与CIG预制膜的反应。另外，上述设定气压可以为1Pa～1atm。
其中，第一预设时长可以为25s～35s，本实施例中第一预设时长优选为30s，以在较短的时间内使CIG预制膜表面形成非饱和的In-Se、Cu-Se二元相，而第二预设时长可以为260s～275s，本实施例中第二预设时长优选为270s，从而可以提供较长的时间以使Se元素向CIG预制膜底部扩散，避免Ga元素向底部富集的现象，同时，能够在充分的反应时间内补足CIG预制膜反应生成CIGS四元相时所需的硒；另外，第三预设时长可以为5min～30min，以充分进行退火处理。在此实施例中，加热升温的速度相对较慢，反应速率较慢，利于控制硒气氛流量；此方法工艺窗口较大，利于工艺控制。
在本申请提供的又一实施例中，预设的第一温度阈可以为620℃～700℃，在该温度范围下，在较高反应温度下的CIG预制膜可以与硒气氛充分反应，以获得具有良好的Ga元素分布的高性能CIGS吸收层；预设的第二温度阈可以为500℃～600℃；预设的第三温度阈可以为380℃～500℃，以形成高温硒气氛，便于后续与CIG预制膜的反应。
由于硒气氛获得了较高的温度，从而可以使第一预设时长为15s～25s，第二预设时长为15s～35s，以缩短CIG预制膜的反应时间，提高反应效率；
其中，第二预设时长大于第一预设时长，从而可以在较短的时间内使CIG预制膜表面形成非饱和的In-Se、Cu-Se二元相，并提供较长的时间以使Se元素向CIG预制膜底部扩散，避免Ga元素向底部富集的现象，同时，能够在充分的反应时间内补足CIG预制膜反应生成CIGS四元相时所需的硒。在此实施例中，加热升温的速率较快，利于Se元素的快速扩散从而优化Ga元素的分布，提高了CIGS的膜层性能。
需要说明的是，为了改善镓元素的扩散，以获得高性能的CIGS吸收层，在本实施例中，第二温度阈优选为580℃，第三预设时长为5min～30min。
上述硒气氛可以为硒蒸气或硒化氢气体。当然不限于所列举的这两种。
本发明实施例还提供了一种太阳能电池的制备方法，包括上述任一项所述的太阳能吸收层的制备方法。
本发明实施例提供的太阳能电池吸收层的制备方法及太阳能电池的制备方法，通过控制通入的硒气氛的载气流量、反应温度及反应时间，使硒元素可以穿过不饱和In-Se、Cu-Se二元相向预制膜底部扩散，避免了镓元素向底部富集的问题，提高了CIGS薄膜晶粒尺寸。
以上依据图式所示的实施例详细说明了本发明的构造、特征及作用效果，以上所述仅为本发明的较佳实施例，但本发明不以图面所示限定实施范围，凡是依照本发明的构想所作的改变，或修改为等同变化的等效实施例，仍未超出说明书与图示所涵盖的精神时，均应在本发明的保护范围内。

Claims (10)

1.一种太阳能电池吸收层的制备方法，其特征在于，包括如下步骤：
在沉积有背电极的基底上依次溅射铜镓合金层和铟层，以形成铜铟镓预制膜；
将所述铜铟镓预制膜放入具有预设的第一温度阈的反应腔中，并在所述反应腔中通入预设的第一载气流量值的硒气氛，使所述铜铟镓预制膜在所述第一载气流量值的硒气氛中反应第一预设时长；
向所述反应腔内通入预设的第二载气流量值的硒气氛，使所述铜铟镓预制膜在所述第二载气流量值的硒气氛中反应第二预设时长；所述第一载气流量值与所述第二载气流量值的比大于5；
在预设的第二温度阈和第三预设时长内对所述基底进行退火处理。
2.根据权利要求1所述的太阳能电池吸收层的制备方法，其特征在于，在将所述铜铟镓预制膜放入具有预设的第一温度阈的反应腔中之前还包括：
在真空或设定气压的惰性气体中，将固态硒源加热至预设的第三温度阈内，以在所述反应腔中形成硒气氛。
3.根据权利要求2所述的太阳能电池吸收层的制备方法，其特征在于，所述预设的第一温度阈为550℃～580℃，所述预设的第二温度阈为500℃～600℃，所述预设的第三温度阈为250℃～470℃，所述设定气压为1Pa～1atm。
4.根据权利要求3所述的太阳能电池吸收层的制备方法，其特征在于，所述第一预设时长为25s～35s，所述第二预设时长为260s～275s，所述第三预设时长为5min～30min。
5.根据权利要求2所述的太阳能电池吸收层的制备方法，其特征在于，所述预设的第一温度阈为620℃～700℃，所述预设的第二温度阈为500℃～600℃，所述预设的第三温度阈为380℃～500℃。
6.根据权利要求5所述的太阳能电池吸收层的制备方法，其特征在于，所述第一预设时长为15s～25s，所述第二预设时长为15s～35s，所述第三预设时长为5min～30min。
7.根据权利要求1-6任一项所述的太阳能电池吸收层的制备方法，其特征在于，所述铜铟镓预制膜组成元素的原子比例满足：0.8≤Cu/(In+Ga)≤0.96，0.25≤Ga/(In+Ga)≤0.35。
8.根据权利要求7所述的太阳能电池吸收层的制备方法，其特征在于，所述反应腔为石墨反应腔。
9.根据权利要求1-6任一项所述的太阳能电池吸收层的制备方法，其特征在于，所述硒气氛包括：硒蒸气或硒化氢气体。
10.一种太阳能电池的制备方法，其特征在于，包括如权利要求1～9任一项所述的太阳能电池吸收层的制备方法。
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