CN104319298B - 柔性衬底CdTe薄膜太阳能电池及其制备方法 - Google Patents
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
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- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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Abstract
本发明公开一种柔性衬底CdTe薄膜太阳能电池及其制备方法,其由以下7个部分组合而成:1)、透明的柔性衬底薄膜材料层;2)、在所述柔性衬底薄膜材料层上低温沉积有ZnxCd1‑xO形成的透明导电薄膜层;3)、在所述透明导电薄膜层的部分位置上形成负极;4)、设置在所述透明导电薄膜层上的CdS薄膜窗口层,5)、设置在所述CdS薄膜窗口层上的CdTe薄膜吸收层;6)、设置在所述CdTe薄膜吸收层上的背电极金属接触层;7)、设置在所述背电极金属接触层上的柔性薄膜材料封装层。本发明具有成本低,效率高和满足不同领域需求的优点,且可以应用于低温工艺的柔性衬底薄膜CdTe薄膜太阳能电池的大批量制备。
Description
技术领域
本发明涉及纳米无机化合物能源材料制造工艺技术领域,尤其涉及一种柔性衬底CdTe(碲化镉)薄膜太阳能电池及其制备方法。
背景技术
太阳能作为一种清洁、无污染、取之不尽用之不竭的自然能源,越来越受到人们的重视。太阳能电池可以直接将太阳能转换为电能,在太阳能的直接利用中有很大的优势。人们对太阳能电池的研究,可以分为体太阳能电池和薄膜太阳能电池的研究。体太阳能电池是指用化合物半导体的单晶、多晶锭切片为材料基础制备的太阳能电池。它的致命弱点是材料消耗大,制备工艺复杂,生产成本高。所以,人们更加倾向于薄膜太阳能电池的研究。
在各种类型的薄膜电池中,CdTe薄膜电池由于结构简单,材料易得,制造成本低等优点,发展速度较快。CdTe是一种化合物半导体,在太阳电池中一般作吸收层。由于它的直接带隙为1.45eV左右,与太阳光谱非常匹配,最适合于光电能量转换,是一种良好的PV材料,具有很高的理论效率(28%),性能很稳定,一直被光伏业界看重。
因此,研究本申请人致力于开发一种低成本,高效率的新型柔性衬底CdTe薄膜太阳能电池及其制备方法。
发明内容
本发明的目的,就是提出一种低成本,高效率的柔性衬底CdTe薄膜太阳能电池及其制备方法。
本发明为解决上述技术问题,提供了一种柔性衬底CdTe薄膜太阳能电池,由以下7个部分组合而成:1)、透明的柔性衬底薄膜材料层;2)、在所述柔性衬底薄膜材料层上低温沉积有ZnxCd1-xO形成的透明导电薄膜层;3)、在所述透明导电薄膜层的部分位置上丝网印刷银浆,形成的用于汇集电流的负极;4)、设置在所述透明导电薄膜层未印刷银浆的位置上的CdS薄膜窗口层,5)、设置在所述CdS薄膜窗口层上的CdTe薄膜吸收层;6)、设置在所述CdTe薄膜吸收层上的背电极金属接触层;7)、设置在所述背电极金属接触层上的柔性薄膜材料封装层,用于对背电极进行密封保护。
较佳的,所述ZnxCd1-xO中的x的值为0.45~0.5。
较佳的,所述透明导电薄膜层的电阻率为2.3×10-3(Ω·cm)。
较佳的,所述CdS薄膜窗口层的厚度为90~110nm的CdS薄膜。
较佳的,所述背电极金属接触层为镍电极或者铝电极或者铜电极或者金电极。
一种上述的柔性衬底CdTe薄膜太阳能电池的制备方法,采用如下的制备步骤:
a、制备透明的柔性衬底薄膜材料层;
b、在所述柔性衬底薄膜材料层上低温沉积ZnxCd1-xO,制备形成透明导电薄膜层;
c、在所述透明导电薄膜层的部分位置上丝网印刷银浆,制备形成用于汇集电流的负极;
d、在所述透明导电薄膜层的部分位置上制备CdS薄膜窗口层,所述CdS薄膜窗口层与所述负极不直接接触;
e、在所述CdS薄膜窗口层上制备CdTe薄膜吸收层;
f、在所述CdTe薄膜吸收层上制备背电极金属接触层;
g、在所述背电极金属接触层上制备柔性薄膜材料封装层,用于对背电极进行密封保护;
h、获得柔性衬底CdTe薄膜太阳能电池。
较佳的,所述步骤b中所述透明导电薄膜层采用ZnxCd1-xO低温沉积工艺,所述透明导电薄膜层采用反应式磁控溅射方法制备,靶材为Zn/Cd按照一定比例组成的合金,Zn和Cd的纯度分别达到99.99%以上。
在沉积形成透明导电薄膜层之前,先将所述柔性衬底薄膜材料层用超声波乙醇清洗10min,再用去离子水超声清洗10min,最后用氮气吹干;沉积时,所述柔性衬底薄膜材料层的温度为200℃,沉积室背景压强小于5×10-3Pa,溅射电压400V,沉积时间15min。
较佳的,所述步骤d中的所述CdS薄膜窗口层采用化学沉积法制备工艺,制作CdS薄膜采用的化学药品包括醋酸氨、醋酸镉、氨水和硫脲,控制化学反应时间、温度,使所述透明导电薄膜层上面均匀淀积一层厚度约为90~110nm的CdS薄膜,并用CdCl2涂覆在CdS上,并加热到350℃~400℃进行退火处理。
较佳的,所述步骤e中所述的CdTe薄膜吸收层采用电解淀积工艺,将含有Cd2+及HTeO2+的电解液进行化学还原反应,从而得到Cd和Te并淀积形成CdTe薄膜;在电解淀积过程中,得到厚度为3μm的薄膜,并用CdCl2涂覆在CdTe上,并加热到350℃~400℃进行退火处理。
较佳的,所述步骤f中首先对所述CdTe薄膜吸收层的表面进行化学刻蚀,再高浓度掺杂背接触材料,所述背接触材料是CdS/CdTe/ZnTe:Cu,所述CdS/CdTe/ZnTe:Cu的成膜厚度为45~55nm:45~55nm,形成欧姆接触,提高太阳能薄膜电池性能。
综上所述,本发明柔性衬底CdTe薄膜太阳能电池及其制备方法具有如下有益效果:
1、本发明所开发的新型柔性衬底CdTe薄膜太阳能电池,具有成本低,效率高和满足不同领域需求的优点。
2、本发明采用柔性衬底,实现太阳能电池可以在一定的角度内弯折,以此满足不同场合的需求,适用范围广。
3、本发明所开发的新型柔性衬底CdTe薄膜太阳能电池制备方法,有效的降低了工艺的复杂度和制造成本,具有成膜质量好、工艺简单和价格低廉的优点,是一种制备高质量柔性衬底CdTe薄膜太阳电池的有效的方法。
4、本发明具体的通过采用ZnxCd1-xO低温沉积工艺,降低工艺的复杂度;CdS薄膜窗口层采用化学沉积法(CBD)制备工艺,成本低廉;CdTe薄膜吸收层采用电解淀积工艺,制作CdTe背电极金属接触时,形成欧姆接触,进一步有效提高太阳能薄膜电池的性能。
附图说明
下面结合附图和具体实施方式对本发明作进一步详细说明:
图1为具体实施例柔性衬底CdTe薄膜太阳能电池的结构示意图。
附图标号说明:
柔性衬底薄膜材料层1,透明导电薄膜层2,负极3,CdS薄膜窗口层4,CdTe薄膜吸收层5,背电极金属接触层6,柔性薄膜材料封装层7。
具体实施方式
本实施例公开了一种柔性衬底CdTe薄膜太阳能电池,其由7个部分组合而成,这7个部分分别为柔性衬底薄膜材料层1、透明导电薄膜层2、负极3、CdS薄膜窗口层4、CdTe薄膜吸收层5、背电极金属接触层6和柔性薄膜材料封装层7。
如图1所示,本实施例具体为底层设置透明的柔性衬底薄膜材料层1;在柔性衬底薄膜材料层1上低温沉积有ZnxCd1-xO形成的透明导电薄膜层2;在透明导电薄膜层2的部分位置上丝网印刷银浆,形成的用于汇集电流的负极3;4)、设置在透明导电薄膜层2未印刷银浆的位置上的CdS薄膜窗口层4;设置在CdS薄膜窗口层4上的CdTe薄膜吸收层5;设置在CdTe薄膜吸收层5上的背电极金属接触层6;设置在背电极金属接触层6上的柔性薄膜材料封装层7,用于对背电极进行密封保护。
具体的,本实施例选用的ZnxCd1-xO中的x的值为0.45~0.5,如x选用0.5,则形成Zn0.5Cd0.5O,形成的透明导电薄膜层2的电阻率为2.3×10-3(Ω·cm)。CdS薄膜窗口层4的厚度为90~110nm的CdS薄膜。背电极金属接触层6为镍电极或者铝电极或者铜电极或者金电极。
当然了,技术人员还可以根据实际情况进行适当调整,如形成的所述透明导电薄膜层的电阻率调整了2.3×10-3(Ω·cm)左右的其他数值等,此处不再赘述。
本实施例还提出了一种上述的柔性衬底CdTe薄膜太阳能电池的制备方法,具体采用如下的制备步骤:
a、制备透明的柔性衬底薄膜材料层;
b、在所述柔性衬底薄膜材料层上低温沉积ZnxCd1-xO,制备形成透明导电薄膜层;
c、在所述透明导电薄膜层的部分位置上丝网印刷银浆,制备形成用于汇集电流的负极;
d)、在所述透明导电薄膜层的部分位置上制备CdS薄膜窗口层,所述CdS薄膜窗口层与所述负极不直接接触;
e)、在所述CdS薄膜窗口层上制备CdTe薄膜吸收层;
f)、在所述CdTe薄膜吸收层上制备背电极金属接触层;
g)、在所述背电极金属接触层上制备柔性薄膜材料封装层,用于对背电极进行密封保护;
h)、获得柔性衬底CdTe薄膜太阳能电池。
具体的,本实施例所述步骤b中所述透明导电薄膜层采用ZnxCd1-xO低温沉积工艺,所述透明导电薄膜层采用反应式磁控溅射方法制备,靶材为Zn/Cd按照一定比例组成的合金,Zn和Cd的纯度分别达到99.99%以上。
在沉积形成透明导电薄膜层之前,先将所述柔性衬底薄膜材料层用超声波乙醇清洗10min,再用去离子水超声清洗10min,最后用氮气吹干;沉积时,所述柔性衬底薄膜材料层的温度为200℃,沉积室背景压强小于5×10-3Pa,溅射电压400V,沉积时间15min。
本实施例所述步骤d中的所述CdS薄膜窗口层采用化学沉积法制备工艺,制作CdS薄膜采用的化学药品包括醋酸氨、醋酸镉、氨水和硫脲,控制化学反应时间、温度,使所述透明导电薄膜层上面均匀淀积一层厚度约为90~110nm的CdS薄膜,并用CdCl2涂覆在CdS上,并加热到350℃~400℃进行退火处理。
本实施例的所述步骤e中所述的CdTe薄膜吸收层采用电解淀积工艺,将含有Cd2+及HTeO2+的电解液进行化学还原反应,从而得到Cd和Te并淀积形成CdTe薄膜;在电解淀积过程中,得到厚度为3μm的薄膜,并用CdCl2涂覆在CdTe上,并加热到350℃~400℃进行退火处理。
本实施例的所述步骤f中首先对所述CdTe薄膜吸收层的表面进行化学刻蚀,再高浓度掺杂背接触材料,所述背接触材料是CdS/CdTe/ZnTe:Cu,所述CdS/CdTe/ZnTe:Cu的成膜厚度为45~55nm:45~55nm,形成欧姆接触,提高太阳能薄膜电池性能。
示例性的,本实施例所述步骤d中的CdS薄膜窗口层采用化学沉积法(CBD)制备工艺,制作CdS薄膜采用的化学药品为醋酸氨、醋酸镉、氨水、硫脲等。控制化学反应时间、温度等,使ZnxCd1-xO组成的导电膜上面均匀淀积一层厚度约为90~110nm的CdS薄膜,并用CdCl2涂覆在CdS上,并加热到350℃~400℃进行退火处理。
上述化学沉积总的化学反应式为:
Cd(NH3)4 2++SC(NH2)2+2OH-→CdS+CH2N2+2H2O+4NH3;
由于CdS溶度积很小,极易产生CdS沉淀。因此,只有控制好Cd2+,S2-的分解速度,才能生成均匀、致密的薄膜。
下面为通过试验得到的不同温度下的成膜速度对比表:
温度(℃) | 成膜速度(nm/min) | 出现沉淀时间(min) |
55 | 0.28 | 15 |
65 | 2.5 | 10 |
75 | 2.9 | 7 |
85 | 7 | 4 |
通过试验,得到当温度较低时,化学反应速度较慢,在沉积时间一定的情况下,生产的薄膜稀疏,不够致密,有较多的针孔缺陷存在;当温度偏高时,反应速度快,溶液中存在大量的CdS粒子,并形成沉淀物,导致薄膜形貌很差,颗粒不均匀。
综上,本实施例我们优选CdS薄膜窗口层成膜的工艺温度为65℃左右。
示例性的,本实施例的所述步骤e的CdTe薄膜吸收层采用电解淀积工艺,将含有Cd2+及HTeO2+的电解液进行化学还原反应,从而得到Cd和Te并淀积形成CdTe薄膜。电解淀积过程中,控制电解时间、温度、溶液浓度等,得到厚度为3μm左右的薄膜,并用CdCl2涂覆在CdTe上,并加热到350℃~400℃进行退火处理。
电解淀积工艺是电解还原及淀积反应,可以由以下三个化学反应式表示:
HTeO2++3H++4e-→Te+2H2O
Cd2++2e-→Cd
Te+Cd→CdTe
退火处理的过程实际上是CdTe再结晶的过程,通过退火处理,CdTe的小晶粒消失,连带着CdTe与CdS的界面结构也变得比较有秩序。
退火过程的化学反应式为:
CdTe(s)+CdCl2(s)→2Cd(g)+Cl2(s)→CdTe(s)+CdCl2(s)
CdCl2在化学反应中起到了催化剂的作用。
示例性的,本实施例在所述步骤f制作CdTe背电极金属接触时,首先对CdTe薄膜表面进行化学刻蚀,再高浓度掺杂背接触材料。本发明采用的背接触材料是CdS/CdTe/ZnTe:Cu,他们的成膜厚度分别为45~55nm:45~55nm,形成欧姆接触,提高太阳能薄膜电池性能。
综上所述,本实施例的柔性衬底CdTe薄膜太阳能电池,采用柔性衬底制作薄膜太阳能电池,透明导电膜采用ZnxCd1-xO低温沉积工艺,CdS薄膜窗口层采用化学沉积法(CBD)制备工艺,CdTe薄膜吸收层采用电解淀积工艺,具有成本低廉,设备投入低、效率高、应用范围广的特点。本实施例的制备方法可以应用于低温工艺的柔性衬底薄膜CdTe薄膜太阳能电池的大批量制备。
以上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 (4)
1.一种柔性衬底CdTe薄膜太阳能电池的制备方法,其特征在于,采用如下的制备步骤:
a、制备透明的柔性衬底薄膜材料层;
b、在所述柔性衬底薄膜材料层上低温沉积ZnxCd1-xO,制备形成透明导电薄膜层;所述透明导电薄膜层采用ZnxCd1-xO低温沉积工艺,所述透明导电薄膜层采用反应式磁控溅射方法制备,靶材为Zn/Cd组成的合金,Zn和Cd的纯度分别达到99.99%以上;
在沉积形成透明导电薄膜层之前,先将所述柔性衬底薄膜材料层用超声波乙醇清洗10min,再用去离子水超声清洗10min,最后用氮气吹干;
沉积时,所述柔性衬底薄膜材料层的温度为200℃,沉积室背景压强小于5×10-3Pa,溅射电压400V,沉积时间15min;
c、在所述透明导电薄膜层的部分位置上丝网印刷银浆,制备形成用于汇集电流的负极;
d、在所述透明导电薄膜层未印刷银浆的位置上制备CdS薄膜窗口层;
e、在所述CdS薄膜窗口层上制备CdTe薄膜吸收层;
f、在所述CdTe薄膜吸收层上制备背电极金属接触层;
g、在所述背电极金属接触层上制备柔性薄膜材料封装层,用于对背电极进行密封保护;
h、获得柔性衬底CdTe薄膜太阳能电池。
2.如权利要求1所述的制备方法,其特征在于:所述步骤d中的所述CdS薄膜窗口层采用化学沉积法制备工艺,制作CdS薄膜采用的化学药品包括醋酸氨、醋酸镉、氨水和硫脲,控制化学反应时间、温度,使所述透明导电薄膜层上面均匀淀积一层厚度为90~110nm的CdS薄膜,并用CdCl2涂覆在CdS上,并加热到350℃~400℃进行退火处理。
3.如权利要求2所述的制备方法,其特征在于:所述步骤e中所述的CdTe薄膜吸收层采用电解淀积工艺,将含有Cd2+及HTeO2+的电解液进行化学还原反应,从而得到Cd和Te并淀积形成CdTe薄膜;在电解淀积过程中,得到厚度为3μm的薄膜,并用CdCl2涂覆在CdTe上,并加热到350℃~400℃进行退火处理。
4.如权利要求1或3所述的制备方法,其特征在于:所述步骤f中首先对所述CdTe薄膜吸收层的表面进行化学刻蚀,再高浓度掺杂背接触材料,所述背接触材料是CdS/CdTe/ZnTe:Cu,所述CdS/CdTe/ZnTe:Cu的成膜厚度为45~55nm,形成欧姆接触,提高太阳能薄膜电池性能。
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