無鎘的銅銦鎵硒太陽能電池制備與性能研究
發(fā)布時間：2018-07-15 19:43
【摘要】：黃銅礦型銅銦鎵硒(CuIn1-xGaxSe2, CIGS)薄膜太陽能電池具有光電轉(zhuǎn)換效率高、成本低、穩(wěn)定性好等優(yōu)點,是最有發(fā)展前景的薄膜太陽能電池之一,但其多層薄膜制作工藝復(fù)雜,包括鉬(Mo)背電極層、CIGS光吸收層、硫化鎘(CdS)緩沖層、本征氧化鋅(i-ZnO)和摻鋁氧化鋅(AZO)窗口層,任何一層薄膜質(zhì)量不好都將影響太陽能電池的的光電性能,因此工藝控制至關(guān)重要,本論文重點在CIGS吸收層和無鎘緩沖層制備工藝控制研究。 CIGS薄膜是太陽能電池的核心材料。本論文研究了一種工藝簡單、可控的CIGS薄膜制備技術(shù)：首先,在鈉鈣玻璃襯底上濺射制備厚度約1微米的鉬電極,然后采用雙室多靶位磁控濺射沉積系統(tǒng),通過交替直流濺射CuGa靶(原子比3：1；純度99.999%)和純In靶(純度99.999%),選擇不同的疊層方式在鉬電極上制備銅銦鎵前驅(qū)膜；再將前驅(qū)膜放入特制的真空爐中選擇不同的升溫方式進行硒化退火,得到四元化合物銅銦鎵硒半導(dǎo)體納米薄膜,對薄膜進行各項表征(SEM、AFM、XPS、XRD等),分析了前驅(qū)膜疊層及硒化升溫方式對銅銦鎵硒薄膜性能的影響,優(yōu)化了制備條件：In/CuGa/In多層前驅(qū)膜先在250℃恒溫20分鐘加熱預(yù)處理,再升溫至560℃硒化溫度30分鐘,制備出致密的黃銅礦結(jié)構(gòu)的多晶銅銦鎵硒薄膜,薄膜顆粒直徑約1μm,有較好的結(jié)晶質(zhì)量,膜厚2μm,方塊電阻為0.11Ω/□,薄膜在波長500-1100nm之間,對可見光及近紅外線有很好的吸收。 緩沖層是位于CIGS吸收層和透明導(dǎo)電窗口層之間的薄膜,用以緩沖吸收層和透明導(dǎo)電層之間的帶隙差。傳統(tǒng)采用的緩沖層CdS對人體有害,而且?guī)镀?造成太陽光的短波損失,且CdS的傳統(tǒng)化學(xué)浴制備方法都是濕法工藝,破壞了濺射后硒化或共蒸發(fā)中的真空和干法制造流程,因而無鎘緩沖層的干法制備具有重要意義。在CIGS電池中的緩沖層材料很薄,原子層沉積方式是最理想的選擇,本文采用原子層沉積ZnO(ALD-ZnO)代替CdS做緩沖層,它是沒有采用等離子體的軟沉積法,可以避免采用磁控濺射的方法制備ZnO時對CIGS膜的損傷；還可以方便地避免現(xiàn)有CIGS工藝流程中唯一的液相化學(xué)浴(CBD)工藝,ALD設(shè)備可以與現(xiàn)有CIGS生產(chǎn)線其它真空工藝無縫對接,基底在大氣中的暴露將很少；ALD-ZnO還提高了短波和近紅外范圍的量子效率,具有工業(yè)化應(yīng)用價值。 本文研究了ALD制備ZnO緩沖層時薄膜厚度與鋅源(DEZn)脈沖時間的關(guān)系、薄膜表面粗糙度與鋅源脈沖時間的關(guān)系和溫度對薄膜質(zhì)量的影響、攜帶DEZn氣體流量與平均生長的薄膜厚度關(guān)系、不同鋅源脈沖時間下ZnO薄膜的光學(xué)特性等,在我們的實驗范圍得出了最佳工藝條件為：DEZn脈沖時間0.1秒,清洗時間3秒；H2O脈沖時間0.1秒,清洗時間4秒,攜帶氣體為高純N2,DEZn的攜帶氣體流量為150sccm, H2O的攜帶氣體流量為200sccm,襯底溫度為250℃,真空度為20hPa時沉積開始,薄膜生長200個周期。 用原子層沉積法在鈉鈣玻璃上沉積厚度僅為56.8nm的氧化鋅薄膜,利用場發(fā)射掃描電鏡、AFM和X射線衍射(XRD)、XPS等對樣品表面形貌和物相進行分析,得到的ZnO納米顆粒為六角纖鋅礦結(jié)構(gòu),顆粒的大小約在30-60nm之間；薄膜在波長400-900nm可見光區(qū)域透射率達90%以上；使用該原子層沉積氧化鋅薄膜做銅銦鎵硒太陽能電池的緩沖層,透射電鏡TEM顯示氧化鋅層致密地覆蓋在CIGS薄膜上,得到的電池的光電轉(zhuǎn)換效率較高,完全可以替代有毒的CdS做緩沖層。本工藝技術(shù)路線環(huán)保,簡單可控,將有助于無鎘的CIGS太陽電池的產(chǎn)業(yè)化。 研究制備了的結(jié)構(gòu)為Glass/Mo/CIGS/ALD-ZnO/i-ZnO/n-ZnO:Al無鎘的銅銦鎵硒太陽能電池。該電池的開路電壓為Voc=0.46V,短路電流密度Jsc=13.8mA/cm2,填充因子FF=0.59,樣品在沒減反射膜情況下的光電轉(zhuǎn)換效率達到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 % .
【學(xué)位授予單位】：廣東工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TM914.4
本文編號：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 % .
【學(xué)位授予單位】：廣東工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TM914.4
【引證文獻】
相關(guān)期刊論文 前1條
1 劉洋;;銅銦鎵硒薄膜太陽電池吸收層制備方法及性能分析[J];科技創(chuàng)新與應(yīng)用;2015年14期
相關(guān)博士學(xué)位論文 前1條
1 羅派峰;銅銦鎵硒薄膜太陽能電池關(guān)鍵材料與原理型器件制備與研究[D];中國科學(xué)技術(shù)大學(xué);2008年
，本文編號：2125178
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