CN104538492A - 一种铜铟镓硒薄膜太阳电池光吸收层薄膜的制备方法 - Google Patents
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Abstract
本发明公开了一种铜铟镓硒薄膜太阳电池光吸收层薄膜的制备方法。使用本发明能够降低沉积温度、简化工艺。本发明首先将基底加热至250℃~350℃并保温,然后采用磁控溅射或多元共蒸发法制备CIGS光吸收层薄膜,同时对基底照射光子能量范围为1.2eV~6.2eV的光束,最终生成铜铟镓硒薄膜太阳电池光吸收层薄膜。本发明实现了CIGS薄膜的一步低温沉积,简化工艺,适合工业化生产,特别适合用于卷绕制备柔性CIGS薄膜太阳电池。
Description
技术领域
本发明涉及表面工程技术领域,具体涉及一种铜铟镓硒(CIGS)薄膜太阳电池光吸收层薄膜的制备方法。
背景技术
随着空间、近空间飞行器以及地面军事智能化装备的发展,其能源供给系统对太阳电池提出了诸多新的要求,如:轻质、高效、强的抗辐射能力等。柔性CIGS薄膜太阳电池以其高效、强的空间抗辐射性与整体的稳定性成为最有潜力应用于空间技术的电池之一。
CIGS吸收层的制备技术在整个电池的制备过程中起着决定性的作用。CIGS吸收层的制备有多种工艺技术和方法,最常用的有Cu、In、Ga、Se多元三步共蒸发法、CuInGa合金薄膜预溅射后硒化法。其中多元三步共蒸发法要求在薄膜沉积过程中必需保持硒量充足,同时基底温度必需保持在400℃~600℃。后硒化法制备CIGS薄膜必需经过硒化工艺,硒化温度在550℃左右。以上两类方法制备CIGS薄膜时基底都要承受400℃~600℃的高温,以保证薄膜中完整的硒化,使薄膜具有好的成分和组织结构,因此,多用于硬性基底而不适用于柔性基底,400℃~600℃的高温要高于聚酰亚胺等柔性基底的耐受温度,因此低温生长CIGS薄膜成为必要的发展方向。另外,造成聚酰亚胺基底CIGS薄膜电池效率较低原因中最重要的一点是聚酰亚胺限制基底温度,过低的温度无法提供足够的能量给沉积原子,使得原子的运动能力受到影响,进而无法得到高质量的CIGS薄膜。研究表明,在其他生长条件相同的情况下,低温制备的CIGS晶粒较小,较多的晶界造成电子与空穴的再复合现象,因而影响电荷的扩散距离, 造成电池效率的降低。
发明内容
有鉴于此,本发明提供了一种铜铟镓硒薄膜太阳电池光吸收层薄膜的制备方法,能够降低沉积温度、简化工艺。
本发明的铜铟镓硒薄膜太阳电池光吸收层薄膜制备方法,首先将基底加热至250℃~350℃并保温,然后采用磁控溅射或多元共蒸发法制备CIGS光吸收层薄膜,同时对基底照射光子能量范围为1.2eV~6.2eV的光束,最终生成铜铟镓硒薄膜太阳电池光吸收层薄膜。
进一步地,在加热基底前,采用氩离子束轰击基底,对基底进行活化清洗。
进一步地,所述氩离子束活化清洗中,氩气流量为15~20sccm,离子束放电电压为280V,离子束电流为1A。
进一步地,所述基底为聚酰亚胺膜,膜厚为25~125微米。
有益效果:
本发明实现了CIGS薄膜的一步低温沉积,简化工艺,适合工业化生产,特别适合用于卷绕制备柔性CIGS薄膜太阳电池。此外,低温过程也能降低能源的需求,从而降低生产成本。
具体实施方式
下面结合实施例,对本发明进行详细描述。
本发明提供了一种铜铟镓硒薄膜太阳电池光吸收层薄膜的制备方法,在传统磁控溅射或多元共蒸发Cu、In、Ga、Se金属制备CIGS光吸收层薄膜过程的同时加以光束辅助给基底提供额外能量,利用光子能量提供足够沉积原子运动的能量,使之合成较大晶粒,反应生成CIGS分子,实现柔性聚酰亚胺基底上 CIGS薄膜低温沉积,温度可控制在360℃以内,且能耗少,薄膜质量高,均匀性好,工艺简单。具体实现步骤如下:
步骤1,将柔性聚合物薄膜基底放在真空室内,对真空室抽真空至2.0×10-3Pa以下。优选基底为膜厚为25~125微米的聚酰亚胺膜。
步骤2,用离子源对基底进行氩离子轰击处理,提高镀制膜层的附着力。
在镀膜前用阳极膜线性离子源对基底进行氩离子轰击处理,其目的有两个:首先,通过离子轰击,将吸附在基底表面的水分、有机污染物、杂质气体等溅射掉,由于高分子聚合物多是多孔结构,置于大气中可能吸收大量水气等杂质,镀膜后会降低基底与膜之间的结合力,同时会因夹杂水气造成折射率不同而影响到整体的光学性能;其次,可通过离子轰击改善聚合物基底表面活性,进而加强膜与基底键结强度,因高能量的离子与基底间的交互作用,破坏基底表面键结、产生高活性的悬空键,有助于促进薄膜与基底间的化学键结生成。
较高的离子束能量有助于提高清洗活化的效果,但离子束能量过大会造成基底的辐射损伤,因此,需要对离子束能量进行控制,寻找到最优的离子束能量;本发明优选氩气流量为15~20sccm,离子束放电电压为280V,离子束电流为1A。
步骤3,光束辅助化合反应:将基底加热到250℃~350℃并保温,在Se的饱和蒸汽压中,通过磁控溅射CuGa合金靶和In靶、或CuGa合金靶和CuIn合金靶、或CuInGa合金靶,或者通过多元共蒸发Cu、In、Ga金属,获得CIGS薄膜的反应前躯体,同时以一定波长的光束辐照基底,最终化合生成CIGS薄膜太阳电池的光吸收层。其中,所述的一定能量的光指光子能量范围为1.2eV~6.2eV的光。
其中,CIGS薄膜的反应前躯体的具体获取方法为:在真空中将固态单质Se源加热到180℃~450℃,形成Se的饱和蒸汽压,将基底加热到250℃~350℃ 并保温,通过磁控溅射CuGa合金靶和In靶,或CuGa合金靶和CuIn合金靶,或CuInGa合金靶,或通过多元共蒸发Cu、In、Ga金属,获得CIGS薄膜的反应前躯体。
步骤4,镀膜完成后,维持Se饱和蒸汽压,待基底温度降至200℃,关闭Se源,放气,将样品取出。
下面给出一个具体实施例。
步骤1,将聚酰亚胺薄膜基底放在真空室内,对真空室抽真空至真空室内压强为2.0×10-4Pa;
步骤2,用离子源对基底进行氩离子轰击处理,提高镀制膜层的附着力;其中氩气流量为15sccm,离子束放电电压为280V,离子束电流为1A;
步骤3,采用光束辅助多元共蒸发技术低温沉积CIGS薄膜,过程和工艺参数如下:
系统中包含Cu、In、Ga、Se四个蒸发源,升高蒸发源温度,Cu源为990℃、In源在810~830℃之间、Ga源907℃、Se源195℃;将基底加热到250℃~350℃并保温;待蒸发源温度达到预期温度后10分钟,开启蒸发源各挡板,控制各蒸发源的分子流率,同时将200W的汞灯光源对焦至基底位置,进行CIGS薄膜光辅助镀制;镀制完后,将Cu、In、Ga蒸发源的挡板关闭,进行降温,降温过程中,Se源的挡板仍然开启,维持Se饱和蒸汽压,避免Se原子从过热的基底上逸散;待基底温度降至200℃,关闭Se源挡板,放气,将样品取出。
本发明也可应用于硬性基底,实现太阳电池吸收层的一步制备,并降低了传统制备过程中的基底温度。
综上所述,以上仅为本发明的较佳实施例而已,并非用于限定本发明的保护范围。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (4)
1.一种铜铟镓硒薄膜太阳电池光吸收层薄膜制备方法,其特征在于,将基底加热至250℃~350℃并保温,然后采用磁控溅射或多元共蒸发法制备CIGS光吸收层薄膜,同时对基底照射光子能量范围为1.2eV~6.2eV的光束,最终生成铜铟镓硒薄膜太阳电池光吸收层薄膜。
2.如权利要求1所述的铜铟镓硒薄膜太阳电池光吸收层薄膜制备方法,其特征在于,在加热基底前,采用氩离子束轰击基底,对基底进行活化清洗。
3.如权利要求2所述的铜铟镓硒薄膜太阳电池光吸收层薄膜制备方法,其特征在于,所述氩离子束活化清洗中,氩气流量为15~20sccm,离子束放电电压为280V,离子束电流为1A。
4.如权利要求1~3任意一项所述的铜铟镓硒薄膜太阳电池光吸收层薄膜制备方法,其特征在于,所述基底为聚酰亚胺膜,膜厚为25~125微米。
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US20050006221A1 (en) * | 2001-07-06 | 2005-01-13 | Nobuyoshi Takeuchi | Method for forming light-absorbing layer |
CN1719625A (zh) * | 2005-06-03 | 2006-01-11 | 清华大学 | 铜铟镓硒或铜铟镓硫薄膜太阳能电池吸收层的制备方法 |
CN101768729A (zh) * | 2010-03-05 | 2010-07-07 | 中国科学院上海硅酸盐研究所 | 磁控溅射法制备铜铟镓硒薄膜太阳电池光吸收层的方法 |
CN101814553A (zh) * | 2010-03-05 | 2010-08-25 | 中国科学院上海硅酸盐研究所 | 光辅助方法制备铜铟镓硒薄膜太阳电池光吸收层 |
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CN108198892A (zh) * | 2017-12-22 | 2018-06-22 | 兰州空间技术物理研究所 | 一种掺钾柔性铜铟镓硒薄膜太阳能电池的制备方法 |
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