摘要
以TiO_2为光阳极,CuInSe_2为无机敏化层的NPC太阳能电池造价低、易制造、大气稳定。本文采用连续离子层吸附反应(SILAR)法和电沉积法研究了CuInSe_2薄膜制备,同时采用溶胶-凝胶法研究了TiO_2薄膜制备,最后在TiO_2基底上采用电沉积法制备CuInSe_2薄膜,研究了CuInSe_2敏化TiO_2异质结构的特性。
利用SILAR法制备CuInSe_2薄膜时,首次采用三乙醇胺络合Cu~(2+)离子和柠檬酸钠络合In~(3+)离子的双络合法制备了混合阳离子前驱体溶液,调整阳离子前躯体溶液pH值至8。结果表明,该混合阳离子溶液制备的薄膜容易实现Cu、In、Se三种元素的均匀分布。前躯体溶液水浴温度的提高可以显著加快薄膜的生长速度。当溶液中Cu/In比为1.5时,CuInSe_2薄膜中的元素比在400℃下热处理30min后比较接近1:1:2的化学计量。适当提高热处理温度和延长热处理时间均有利于改善CuInSe_2薄膜的晶化。
利用电沉积法制备CuInSe_2时,采用柠檬酸钠络合Cu、In、Se元素,将溶液pH值调制6~7之后,Se成为最难沉积的元素,由于三种元素沉积电位相差大,首次提出了采用双阶跃恒电位(DPSED)法沉积CuInSe_2薄膜,双电位参数分别为V1=-800mV,V2=-1400mV。阶跃时间的变化对沉积薄膜的组分和形貌有一定影响,阶跃时间t1=30s,t2=60s最合适。当电解液CuCl_2/InCl_3/SeO_2摩尔比为2/0.4/4~5时,DPSED法制备的薄膜接近1:1:2的化学计量,所制备的薄膜的禁带宽度为1.05eV。
溶胶-凝胶法制备介孔TiO_2时,采用钛酸异丙脂(Ti(O~iPr)_4)为钛源,乙醛肟(CH_3CH=NOH)为络合剂,分别利用表面活性剂F127和Brij56作为成孔剂,350~400℃下热分解。研究表明,采用CH_3CH=NOH络合修饰的Ti(O~iPr)_4制备的TiO_2在较高焙烧温度时,仍然可以得到具有高比表面积,小的粒径和窄的孔径分布的TiO_2材料。在350℃下煅烧之后利用F127作为成孔剂的样品的最高比表面积可达219m~2/g,利用Brij56作为成孔剂的样品的最高比表面积可达283m~2/g。
以TiO_2为基底制备CuInSe_2时其沉积电位要比在ITO玻璃上沉积时负移近200mV,阶跃参数为V1=-1000mV, t1=30s, V2=-1600mV, t2=60s时制备CuInSe_2薄膜最接近Cu: In: Se=1:1:2的化学计量,循环6次后所制备的CuInSe_2薄膜的厚度约为300nm。ITO/TiO_2/CuInSe_2/电解液/Pt电池的最大开路电压出现在贫Cu富Se的样品,为446 mV,最大短路电流为0.0054 mA/cm~2。
The NPC solar cell is a very promising kind of solar cells as it is cheap, easy to manufacture and high air stability. Here TiO_2 was used as photo-anode, and CuInSe_2 as inorganic sensitizer. CuInSe_2 films were prepared both by successive ionic layers adsorption and reaction (SILAR) method and electrodeposition method on glass substrate, and TiO_2 films were prepared by Sol-Gel method. Subsequently, the CuInSe_2 films were electrodeposited on TiO_2 films to form TiO_2/CuInSe_2 heterogeneous structure.
In the CuInSe_2 preparation by SILAR method, triethanolamine and sodium citrate were used to complex Cu~(2+) and In~(3+), respectively, to form the Cu and In mixed cationic precursor solutions. The results indicitated that the Cu and In mixed cationic precursor solutions resulted in more uniform distribution for Cu, In and Se elements than the separated cationic precursors. The temperature elevation of precursor solutions could accelerate the growth of CuInSe_2 films. Chalcopyrite CuInSe_2 thin film with near stoichiometry was obtained from Cu/In mol ratio =1.5 in mixed cationic precursor solution after annealed at 400℃for 30min. The suitable rise of annealing temperature and time is beneficial for improvement of CuInSe_2 crystallization.
In the process of CuInSe_2 electrodeposition, sodium citrate were used to complex Cu, In and Se elements in order to tune the pH value to 6~7. In this mild solution conditions, the deposition potentials for Cu, In, and Se elements had a big difference with each other, and Se element required the most negative potential to be deposited. Thus, one step electrodepostion with an alternating double-potentiostatic (DPSED) program was used to prepare CuInSe_2 thin films in the nearly neutral aqueous electrolytes, and the double potential parameters were V1=-800mV and V2=-1400mV. The step time had influences on the morphology and components of CuInSe_2 films, and the appropriate time were t1=30s and t2=60s. When the Cu/In/Se mol ratio was 2/0.4/4~5 in the electrolytes, the deposited CuInSe_2 films were near to Cu: In: Se = 1:1:2 stoichiometry, and the band gap is 1.05eV.
In TiO_2 Sol-Gel preparation, acetaldoxime (CH_3CH=NOH) was used as a new ligand, and F127 and Brij56 were used as pore-forming agent. The organic parts were decomposed at 350~400℃. The results showed that the TiO_2 prepared by CH_3CH=NOH-modified Ti(OiPr)4 could preserve high BET surface, small particle size and narrow pore distribution even at higher calcinating temperature. The highest BET surface is 219m~2/g for TiO_2 sample with F127 and 283m~2/g for sample with Brij56, respectively, after calcinated at 350℃.
For the CuInSe_2 electrodeposition on TiO_2 substrate, the deposition potentials had nearly 200mV negative shift compared with the deposition potentials on ITO substrate. Thus the best deposition parameters were changed to V1=-1000mV, t1=30s, V2=-1600mV, t2=60s, under which the prepared CuInSe_2 films were near 1:1:2 stoichiometry. After 6 cycles, the thickness of prepared CuInSe_2 films was about 300nm. The heterogeneous solar cell was designed as ITO/TiO_2/CuInSe_2/electrolyte/Pt structure. The biggest open-circuit voltage was 446mV, and the biggest short-circuit current was 0.0054 mA/cm~2.
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