无镉的铜铟镓硒太阳能电池制备与性能研究
发布时间：2018-07-15 19:43
【摘要】：黄铜矿型铜铟镓硒(CuIn1-xGaxSe2, CIGS)薄膜太阳能电池具有光电转换效率高、成本低、稳定性好等优点,是最有发展前景的薄膜太阳能电池之一,但其多层薄膜制作工艺复杂,包括钼(Mo)背电极层、CIGS光吸收层、硫化镉(CdS)缓冲层、本征氧化锌(i-ZnO)和掺铝氧化锌(AZO)窗口层,任何一层薄膜质量不好都将影响太阳能电池的的光电性能,因此工艺控制至关重要,本论文重点在CIGS吸收层和无镉缓冲层制备工艺控制研究。 CIGS薄膜是太阳能电池的核心材料。本论文研究了一种工艺简单、可控的CIGS薄膜制备技术：首先,在钠钙玻璃衬底上溅射制备厚度约1微米的钼电极,然后采用双室多靶位磁控溅射沉积系统,通过交替直流溅射CuGa靶(原子比3：1；纯度99.999%)和纯In靶(纯度99.999%),选择不同的叠层方式在钼电极上制备铜铟镓前驱膜；再将前驱膜放入特制的真空炉中选择不同的升温方式进行硒化退火,得到四元化合物铜铟镓硒半导体纳米薄膜,对薄膜进行各项表征(SEM、AFM、XPS、XRD等),分析了前驱膜叠层及硒化升温方式对铜铟镓硒薄膜性能的影响,优化了制备条件：In/CuGa/In多层前驱膜先在250℃恒温20分钟加热预处理,再升温至560℃硒化温度30分钟,制备出致密的黄铜矿结构的多晶铜铟镓硒薄膜,薄膜颗粒直径约1μm,有较好的结晶质量,膜厚2μm,方块电阻为0.11Ω/□,薄膜在波长500-1100nm之间,对可见光及近红外线有很好的吸收。 缓冲层是位于CIGS吸收层和透明导电窗口层之间的薄膜,用以缓冲吸收层和透明导电层之间的带隙差。传统采用的缓冲层CdS对人体有害,而且带隙偏窄,造成太阳光的短波损失,且CdS的传统化学浴制备方法都是湿法工艺,破坏了溅射后硒化或共蒸发中的真空和干法制造流程,因而无镉缓冲层的干法制备具有重要意义。在CIGS电池中的缓冲层材料很薄,原子层沉积方式是最理想的选择,本文采用原子层沉积ZnO(ALD-ZnO)代替CdS做缓冲层,它是没有采用等离子体的软沉积法,可以避免采用磁控溅射的方法制备ZnO时对CIGS膜的损伤；还可以方便地避免现有CIGS工艺流程中唯一的液相化学浴(CBD)工艺,ALD设备可以与现有CIGS生产线其它真空工艺无缝对接,基底在大气中的暴露将很少；ALD-ZnO还提高了短波和近红外范围的量子效率,具有工业化应用价值。 本文研究了ALD制备ZnO缓冲层时薄膜厚度与锌源(DEZn)脉冲时间的关系、薄膜表面粗糙度与锌源脉冲时间的关系和温度对薄膜质量的影响、携带DEZn气体流量与平均生长的薄膜厚度关系、不同锌源脉冲时间下ZnO薄膜的光学特性等,在我们的实验范围得出了最佳工艺条件为：DEZn脉冲时间0.1秒,清洗时间3秒；H2O脉冲时间0.1秒,清洗时间4秒,携带气体为高纯N2,DEZn的携带气体流量为150sccm, H2O的携带气体流量为200sccm,衬底温度为250℃,真空度为20hPa时沉积开始,薄膜生长200个周期。 用原子层沉积法在钠钙玻璃上沉积厚度仅为56.8nm的氧化锌薄膜,利用场发射扫描电镜、AFM和X射线衍射(XRD)、XPS等对样品表面形貌和物相进行分析,得到的ZnO纳米颗粒为六角纤锌矿结构,颗粒的大小约在30-60nm之间；薄膜在波长400-900nm可见光区域透射率达90%以上；使用该原子层沉积氧化锌薄膜做铜铟镓硒太阳能电池的缓冲层,透射电镜TEM显示氧化锌层致密地覆盖在CIGS薄膜上,得到的电池的光电转换效率较高,完全可以替代有毒的CdS做缓冲层。本工艺技术路线环保,简单可控,将有助于无镉的CIGS太阳电池的产业化。 研究制备了的结构为Glass/Mo/CIGS/ALD-ZnO/i-ZnO/n-ZnO:Al无镉的铜铟镓硒太阳能电池。该电池的开路电压为Voc=0.46V,短路电流密度Jsc=13.8mA/cm2,填充因子FF=0.59,样品在没减反射膜情况下的光电转换效率达到3.84%。
[Abstract]:The copper indium gallium selenide ( CuIn1 - xGaxSe2 , cigs ) thin film solar cell has the advantages of high photoelectric conversion efficiency , low cost , good stability and the like , and is one of the most promising thin film solar cells .
cigs thin films are the core materials of solar cells . A simple and controllable technology for the preparation of cigs films is studied . Firstly , a molybdenum electrode with a thickness of about 1 micron is prepared by sputtering on a sodium - lime glass substrate , and then a dual - chamber multi - target magnetron sputtering deposition system is adopted , and the CuGa target ( atomic ratio 3 : 1 ) is sputtered by alternating current sputtering .
a purity of 99.999 percent ) and a pure In target ( purity of 99.999 percent ) are selected , different lamination modes are selected to prepare the copper indium gallium precursor film on the molybdenum electrode ;
The precursor film is put into a special vacuum furnace to carry out selenization annealing to obtain the quaternary compound copper indium gallium selenide semiconductor nano film , and the influence of the precursor film stack and the selenization temperature raising mode on the performance of the copper indium gallium selenium film is analyzed .
A buffer layer is a thin film between the cigs absorption layer and the transparent conductive window layer to buffer the gap difference between the absorption layer and the transparent conductive layer .
the unique liquid phase chemical bath ( CBD ) process in the prior cigs process flow can also be conveniently avoided , and the ALD equipment can be seamlessly butted with other vacuum processes of the prior cigs production line , and the exposure of the substrate in the atmosphere will be little ;
ALD - ZnO also improves the quantum efficiency of short wave and near infrared range , and has industrial application value .
In this paper , the relationship between the film thickness and the pulse time of zinc source ( DEZn ) , the relationship between the surface roughness of the film and the pulse time of zinc source , the influence of temperature on the film quality , the relationship between the film thickness and the film thickness , the optical characteristics of ZnO thin films under different zinc source pulse time are studied . The optimum conditions are as follows : DEZn pulse time 0.1 second , cleaning time 3 seconds ;
H2O pulse time is 0.1 second , the cleaning time is 4 seconds , the carrying gas is high - purity N2 , the carrying gas flow rate of DEZn is 150 sccm , the carrying gas flow rate of H2O is 200 sccm , the substrate temperature is 250 DEG C , and the vacuum degree is 20 hPa , and the film grows 200 cycles .
Zinc oxide films with a thickness of only 56.8 nm were deposited on soda - lime glass by atomic layer deposition . The morphology and phase of samples were analyzed by means of field emission scanning electron microscopy , AFM and X - ray diffraction ( XRD ) and XPS .
the transmittance of the thin film in the visible light region at the wavelength of 400 - 900 nm is over 90 % ;
By using the atomic layer to deposit the zinc oxide thin film as the buffer layer of the copper indium gallium selenide solar cell , the transmission electron microscope TEM shows that the zinc oxide layer is compactly covered on the cigs film , the photoelectric conversion efficiency of the obtained cell is high , and the toxic CdS buffer layer can be completely replaced .
The open - circuit voltage of the battery is Voc = 0.46 V , the short - circuit current density Jsc = 13.8 mA / cm2 , the filling factor FF = 0.59 , and the photoelectric conversion efficiency of the sample under the condition of no antireflection film reaches 3.84 % .
【学位授予单位】：广东工业大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM914.4
本文编号：2125178
[Abstract]:The copper indium gallium selenide ( CuIn1 - xGaxSe2 , cigs ) thin film solar cell has the advantages of high photoelectric conversion efficiency , low cost , good stability and the like , and is one of the most promising thin film solar cells .
cigs thin films are the core materials of solar cells . A simple and controllable technology for the preparation of cigs films is studied . Firstly , a molybdenum electrode with a thickness of about 1 micron is prepared by sputtering on a sodium - lime glass substrate , and then a dual - chamber multi - target magnetron sputtering deposition system is adopted , and the CuGa target ( atomic ratio 3 : 1 ) is sputtered by alternating current sputtering .
a purity of 99.999 percent ) and a pure In target ( purity of 99.999 percent ) are selected , different lamination modes are selected to prepare the copper indium gallium precursor film on the molybdenum electrode ;
The precursor film is put into a special vacuum furnace to carry out selenization annealing to obtain the quaternary compound copper indium gallium selenide semiconductor nano film , and the influence of the precursor film stack and the selenization temperature raising mode on the performance of the copper indium gallium selenium film is analyzed .
A buffer layer is a thin film between the cigs absorption layer and the transparent conductive window layer to buffer the gap difference between the absorption layer and the transparent conductive layer .
the unique liquid phase chemical bath ( CBD ) process in the prior cigs process flow can also be conveniently avoided , and the ALD equipment can be seamlessly butted with other vacuum processes of the prior cigs production line , and the exposure of the substrate in the atmosphere will be little ;
ALD - ZnO also improves the quantum efficiency of short wave and near infrared range , and has industrial application value .
In this paper , the relationship between the film thickness and the pulse time of zinc source ( DEZn ) , the relationship between the surface roughness of the film and the pulse time of zinc source , the influence of temperature on the film quality , the relationship between the film thickness and the film thickness , the optical characteristics of ZnO thin films under different zinc source pulse time are studied . The optimum conditions are as follows : DEZn pulse time 0.1 second , cleaning time 3 seconds ;
H2O pulse time is 0.1 second , the cleaning time is 4 seconds , the carrying gas is high - purity N2 , the carrying gas flow rate of DEZn is 150 sccm , the carrying gas flow rate of H2O is 200 sccm , the substrate temperature is 250 DEG C , and the vacuum degree is 20 hPa , and the film grows 200 cycles .
Zinc oxide films with a thickness of only 56.8 nm were deposited on soda - lime glass by atomic layer deposition . The morphology and phase of samples were analyzed by means of field emission scanning electron microscopy , AFM and X - ray diffraction ( XRD ) and XPS .
the transmittance of the thin film in the visible light region at the wavelength of 400 - 900 nm is over 90 % ;
By using the atomic layer to deposit the zinc oxide thin film as the buffer layer of the copper indium gallium selenide solar cell , the transmission electron microscope TEM shows that the zinc oxide layer is compactly covered on the cigs film , the photoelectric conversion efficiency of the obtained cell is high , and the toxic CdS buffer layer can be completely replaced .
The open - circuit voltage of the battery is Voc = 0.46 V , the short - circuit current density Jsc = 13.8 mA / cm2 , the filling factor FF = 0.59 , and the photoelectric conversion efficiency of the sample under the condition of no antireflection film reaches 3.84 % .
【学位授予单位】：广东工业大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM914.4
【引证文献】
相关期刊论文 前1条
1 刘洋;;铜铟镓硒薄膜太阳电池吸收层制备方法及性能分析[J];科技创新与应用;2015年14期
相关博士学位论文 前1条
1 罗派峰;铜铟镓硒薄膜太阳能电池关键材料与原理型器件制备与研究[D];中国科学技术大学;2008年
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