CN106409934A - 一种cigs太阳电池吸收层的制备方法 - Google Patents
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Abstract
一种CIGS太阳电池吸收层的制备方法，涉及一种薄膜太阳电池吸收层的制备方法，在柔性衬底上依次制备钼背接触层、铜铟镓硒吸收层、硫化镉缓冲层、透明窗口层高阻本征氧化锌薄膜、透明窗口层低阻氧化锌铝薄膜和银上电极，其制备方法是：采用吸收层制备工艺完成后再通过蒸发NaF进行后掺Na，然后依次在其表面依次制备各层薄膜。本发明的优点是：不仅吸收层晶体质量不受影响，吸收层薄膜晶粒尺寸不变，改善了吸收层的电学性能，能够有效提高薄膜太阳电池的电学性能，与目前同类电池比，采用该吸收层制备电池的光电转换效率可提高20％～30％，其制备方法是以钢性衬底制备柔性电池，易于实施，有利于大规模的推广应用。
Description
技术领域
本发明涉及柔性铜铟镓硒薄膜太阳电池技术领域，是一种薄膜太阳电池吸收层的制备方法。
背景技术
铜铟镓硒材料(CIGS)属于I-III-Ⅵ族四元化合物半导体，具有黄铜矿的晶体结构。铜铟镓硒薄膜太能电池自20世纪70年代出现以来，得到非常迅速的发展，并将逐步实现产业化。此电池有以下特点：1)铜铟镓硒的禁带宽度可以在1.04eV-1.67eV范围内调整；2)铜铟镓硒是一种直接带隙半导体，对可见光的吸收系数高达105cm-1，铜铟镓硒吸收层厚度只需1.5-2.5μm，整个电池的厚度为3-4μm；3)抗辐照能力强，比较适合作为空间电源；4)转换效率高，2014年德国太阳能和氢能研究中心(ZSW)研制的小面积铜铟镓硒太阳电池转换效率已高达21.7％；5)弱光特性好。因此铜铟镓硒多晶薄膜太阳电池有望成为下一代太阳电池的主流产品之一。
CIGS薄膜中掺入0.1％的Na可使CIGS太阳电池性能提高30～50％，在传统Na-Ca玻璃(SLG)衬底CIGS太阳电池制备中，Na可由衬底向CIGS吸收层自发扩散而实现Na的掺入。但是，由于PI衬底不含Na，因此在制备中必须加入Na掺入工艺，改善CIGS薄膜的性能，进一步提高柔性PI衬底CIGS薄膜太阳电池的光电转换效率。
目前，制备铜铟镓硒薄膜太阳电池过程中，掺入Na的方法有很多种，包括：在制备Mo背电极之前先在衬底上沉积一层NaF的预置层；在Mo背电极表面沉积含Na预置层；在制备铜铟镓硒吸收层过程中共沉积Na元素(对于目前普遍采用的三步法制备铜铟镓硒，又可分为第一步掺、第二部共掺、第三步共掺)等方法。采用这些方法掺杂Na元素虽然都可以改善薄膜太阳电池的电学性能，但是通过观察其吸收层晶体结构发现，吸收层薄膜晶粒尺寸相比未掺Na的样品都有所减小，晶界增多，这在一定程度上又会对铜铟镓硒薄膜太阳电池的性能带来负面的影响。
发明内容
本发明针对上述存在问题，提供了一种后掺钠铜铟镓硒太阳电池器件及其制备方法，其结晶质量好，晶粒大，缺陷少，可提高薄膜太阳电池开路电压、短路电流、填充因子和光电转换效率。。
本发明的技术方案：
所述掺钠铜铟镓硒吸收层薄膜的制备方法，采用硒化炉薄膜制备系统和改进的共蒸发三步法制备工艺，步骤如下：
1)将待制备样品置于共蒸发系统中在本底真空为3.0×10-4Pa、衬底温度为550-595℃下，共蒸发In、Ga、Se预置层，其中In蒸发源温度为860-875℃，Ga蒸发源温度为920-935℃，Se蒸发源温度为520-535℃，蒸发时间为5-15min；
2)在衬底温度为550-595℃下，共蒸发In、Ga、Cu、Se，其中In蒸发源温度为860-875℃，Ga蒸发源温度为920-935℃，Cu蒸发源温度为1160-1175℃，Se蒸发源温度为520-535℃，蒸发时间为15-20min；
3)在衬底温度保持步骤2)的温度不变条件下，蒸发Cu、Se，其中Cu蒸发源温度为1160-1175℃，Se蒸发源温度为520-535℃，蒸发时间为3-6min，得到稍微富Cu的铜铟镓硒p型黄铜矿结构；
4)保持衬底温度同2)、3)不变，共蒸发In、Ga、Se，其中In蒸发源温度为860-875℃，Ga蒸发源温度为920-940℃，Se蒸发源温度为520-535℃，蒸发时间为3-15min，控制Cu/(In+Ga)的原子比例为0.88-0.92；
5)将衬底温度降至450℃，蒸发NaF、Se，NaF蒸发源温度为770-820℃，蒸发时间为2-15min；
6)将衬底冷却至18-25℃即可。
附图说明
图1为本发明用真空室侧视示意图。
图2为本发明用真空室俯视示意图
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，下面结合附图和实施方式对本发明作进一步的详细说明。
实施例1：
所述铜铟镓硒吸收层薄膜的制备方法，采用硒化炉薄膜制备系统和改进后的共蒸发三步法制备工艺，步骤如下：
1)将待制备样品置于共蒸发系统中，在本底真空为3.0×10-4Pa、衬底温度为550℃下，共蒸发In、Ga、Se预置层，其中In蒸发源温度为860℃，Ga蒸发源温度为920℃，Se蒸发源温度为520℃，蒸发时间为10min；
2)在衬底温度为550℃下，共蒸发In、Ga、Cu、Se，其中In蒸发源温度为860℃，Ga蒸发源温度为920℃，Cu蒸发源温度为1160℃，Se蒸发源温度为520℃，蒸发时间为18min；
3)在衬底温度保持步骤2)的温度不变条件下，蒸发Cu、Se，其中Cu蒸发源温度为1160℃，Se蒸发源温度为520℃，蒸发时间为6min，得到稍微富Cu的铜铟镓硒p型黄铜矿结构；
4)保持衬底温度同2)、3)不变，共蒸发In、Ga、Se，其中In蒸发源温度为860℃，Ga蒸发源温度为920℃，Se蒸发源温度为520℃，蒸发时间为15min，控制Cu/(In+Ga)的原子比例为0.88-0.92；
5)将衬底温度降至450℃，蒸发NaF、Se，NaF蒸发源温度为770℃，蒸发时间为15min；
6)将衬底冷却至18-25℃即可。
实施例2：
所述铜铟镓硒太阳电池吸收层的制备方法，与实施例1相同。
所述铜铟镓硒吸收层的制备方法，采用硒化炉薄膜制备系统和改进的共蒸发三步法制备工艺，步骤如下：
1)将待制备样品置于共蒸发系统中，在本底真空为3.0×10-4Pa、衬底温度为580℃下，共蒸发In、Ga、Se预置层，其中In蒸发源温度为875℃，Ga蒸发源温度为935℃，Se蒸发源温度为530℃，蒸发时间为5min；
2)在衬底温度为580℃下，共蒸发In、Ga、Cu、Se，其中In蒸发源温度为875℃，Ga蒸发源温度为935℃，Cu蒸发源温度为1170℃，Se蒸发源温度为530℃，蒸发时间为18min；
3)在衬底温度保持步骤2)的温度不变条件下，蒸发Cu、Se，其中Cu蒸发源温度为1170℃，Se蒸发源温度为530℃，蒸发时间为6min，得到稍微富Cu的铜铟镓硒p型黄铜矿结构；
4)保持衬底温度同2)、3)不变，共蒸发In、Ga、Se，其中In蒸发源温度为875℃，Ga蒸发源温度为935℃，Se蒸发源温度为530℃，蒸发时间为7min，控制Cu/(In+Ga)的原子比例为0.88-0.92；
5)将衬底温度降至450℃，蒸发NaF、Se，NaF蒸发源温度为770℃，蒸发时间为15min；
6)将衬底冷却至18-25℃即可。
采用本发明制备的薄膜太阳电池吸收层制成柔性铜铟镓硒薄膜太阳电池，其载流子浓度达到2.8×1017cm-3，开路电压和短路电流均可以提高3％～5％、填充因子则可以增加大约10％～20％，光电转换效率可提高约20％～30％。
本发明针对前掺、共掺Na等方法造成吸收层薄膜晶粒变细碎的问题，将掺Na的工艺改为在吸收层沉积完成后。经过研究发现，Na元素在铜铟镓硒中分布于晶粒边界的位置，其扩散过程也是沿晶界进行的。对于前掺、共掺Na方法，在沉积铜铟镓硒吸收层的过程中薄膜已经有Na元素存在，这些Na会在晶界处形成扩散势垒，对元素在晶粒之间的扩散起到抑制作用，从而阻碍了细碎铜铟镓硒晶粒之间的进一步融合，这就是晶粒变小的原因。本发明中后掺Na的方法，Na元素没有参与铜铟镓硒沉积过程，在掺杂之前已经形成较大的晶粒，Na元素沿晶界向吸收层内部扩散，不会破坏晶粒结构。同其它方法相比，后掺Na方法结晶质量更好，缺陷较少，可以有效的抑制界面复合，增加载流子浓度。实验证明，本发明后掺Na制备的铜铟镓硒薄膜太阳电池的开路电压(VOC)、短路电流(JSC)、填充因子(FF)和光电转换效率(η)都比目前公知的前掺、共掺Na制备的电池有所提高。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (3)
1.本发明涉及一种薄膜太阳电池吸收层的制备方法，在柔性衬底上依次制备钼背接触层、铜铟镓硒吸收层、硫化镉缓冲层、透明窗口层高阻本征氧化锌薄膜、透明窗口层低阻氧化锌铝薄膜和银上电极，其制备方法是：采用吸收层制备工艺完成后再通过蒸发NaF进行后掺Na，然后依次在其表面依次制备各层薄膜。本发明的优点是：不仅吸收层晶体质量不受影响，吸收层薄膜晶粒尺寸不变，改善了吸收层的电学性能，能够有效提高薄膜太阳电池的电学性能，与目前同类电池比，采用该吸收层制备电池的光电转换效率可提高20％～30％。
2.根据权利要求1所述后掺钠铜铟镓硒吸收层的制备方法，其特征在于：所述铜铟镓硒吸收层薄膜的制备方法，采用硒化炉薄膜制备系统和改进的共蒸发三步法制备工艺，步骤如下：
1)将待制备样品置于共蒸发系统中，在本底真空为3.0×10-4Pa、衬底温度为550-595℃下，共蒸发In、Ga、Se预置层，其中In蒸发源温度为860-875℃，Ga蒸发源温度为920-935℃，Se蒸发源温度为520-535℃，蒸发时间为5-15min；
2)在衬底温度为550-595℃下，共蒸发In、Ga、Cu、Se，其中In蒸发源温度为860-875℃，Ga蒸发源温度为920-935℃，Cu蒸发源温度为1160-1175℃，Se蒸发源温度为520-535℃，蒸发时间为15-20min；
3)在衬底温度保持步骤2)的温度不变条件下，蒸发Cu、Se，其中Cu蒸发源温度为1160-1175℃，Se蒸发源温度为520-535℃，蒸发时间为3-6min，得到稍微富Cu的铜铟镓硒p型黄铜矿结构；
4)保持衬底温度同2)、3)不变，共蒸发In、Ga、Se，其中In蒸发源温度为860-875℃，Ga蒸发源温度为920-940℃，Se蒸发源温度为520-535℃，蒸发时间为3-15min，控制Cu/(In+Ga)的原子比例为0.88-0.92；
5)将衬底温度降至450℃，蒸发NaF、Se，NaF蒸发源温度为770-820℃，蒸发时间为2-15min；
6)将衬底冷却至18-25℃即可。
3.根据权利要求1所述的薄膜太阳电池吸收层的制备方法，其特征在于：所述步骤1中温度可控的加热装置为内周围盘绕有加热电阻丝的氮化硼坩埚，坩埚外壁贴附有测量并控制加热温度的热偶。
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| WO2019144565A1 (zh) * | 2018-01-29 | 2019-08-01 | 北京铂阳顶荣光伏科技有限公司 | 薄膜太阳能电池 |
| CN111223758A (zh) * | 2018-11-27 | 2020-06-02 | 北京铂阳顶荣光伏科技有限公司 | 铜铟镓硒薄膜太阳能电池及其制备方法 |
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| WO2018152728A1 (zh) * | 2017-02-23 | 2018-08-30 | 海门黄海创业园服务有限公司 | 一种cigs薄膜太阳能电池 |
| WO2019144565A1 (zh) * | 2018-01-29 | 2019-08-01 | 北京铂阳顶荣光伏科技有限公司 | 薄膜太阳能电池 |
| CN111223758A (zh) * | 2018-11-27 | 2020-06-02 | 北京铂阳顶荣光伏科技有限公司 | 铜铟镓硒薄膜太阳能电池及其制备方法 |
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