本文關(guān)鍵詞：用于太陽電池的硫化物半導(dǎo)體薄膜的溶液法制備及其性能研究　出處：《南京航空航天大學(xué)》2011年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 硫化物薄膜 太陽電池材料 化學(xué)浴 連續(xù)離子層吸附沉積 薄膜沉積機(jī)理

【摘要】：能源短缺和環(huán)境污染是當(dāng)前人類面對(duì)的兩大問題。為維持社會(huì)和經(jīng)濟(jì)的發(fā)展，人類必須開發(fā)清潔的可再生能源。光伏發(fā)電是一種非常有前景的可再生能源技術(shù)，有望解決能源和環(huán)境這兩大問題。但目前光伏發(fā)電的成本過高，極大地限制了其大規(guī)模應(yīng)用。解決這一問題的可能途徑是開發(fā)低成本的太陽電池材料及低成本的制備工藝以降低太陽電池的制造成本，從而降低光伏發(fā)電的成本。本論文使用低成本的溶液方法（連續(xù)離子層吸附沉積和化學(xué)浴沉積）制備出幾種可應(yīng)用于 太陽電池的薄膜材料（SnS、Bi_2S_3、CdS、Cu_xS、ZnS和Cu_2ZnSnS_4），詳細(xì)研究了制備工藝參數(shù)對(duì)薄膜材料結(jié)構(gòu)、形貌及性能的影響并對(duì)薄膜的制備機(jī)理進(jìn)行了探討。在此基礎(chǔ)之上制備了幾種結(jié)構(gòu)的異質(zhì)結(jié)薄膜電池原型器件，為利用溶液方法制備低成本的太陽電池打下基礎(chǔ)。以連續(xù)離子層吸附沉積工藝制備了新穎的閃鋅礦結(jié)構(gòu)SnS薄膜。發(fā)現(xiàn)當(dāng)在陽離子前驅(qū)溶液 中加入氯離子時(shí)，薄膜的生長速率提高、結(jié)晶性變好、表面形貌變粗糙。對(duì)以上結(jié)果進(jìn)行了分析：認(rèn)為在陽離子溶液中可能會(huì)存在金屬配合離子聚合形成的多聚體，在這種多聚體中錫的配位結(jié)構(gòu)與閃鋅礦SnS中錫的配位結(jié)構(gòu)類似。這些前驅(qū)物質(zhì)吸附在襯底表面并隨后與硫離子發(fā)生反應(yīng)，在反應(yīng)過程中錫離子的配位結(jié)構(gòu)保持不變從而得到了閃鋅礦結(jié)構(gòu)SnS。當(dāng)氯離子添加到陽離子溶液中時(shí)，氯離子促進(jìn)了金屬配合離子的聚合過程使得更大結(jié)構(gòu)的聚合體的形成成為可能，因此加入氯離子會(huì)提高薄膜的生長速率和結(jié)晶性。使用一種新的化學(xué)浴制備體系制備了閃鋅礦結(jié)構(gòu)及正交結(jié)構(gòu)兩種結(jié)構(gòu)的SnS薄膜。發(fā)現(xiàn)沉積溫度和pH值是決定最終制備的SnS薄膜晶體結(jié)構(gòu)的主要因素。對(duì)由同一制備體系可制備不同結(jié)構(gòu)SnS薄膜的機(jī)理進(jìn)行了探討：認(rèn)為最終得到的SnS薄膜的晶體結(jié)構(gòu)由在化學(xué)浴過程中出現(xiàn)的中間產(chǎn)物中錫離子的配位結(jié)構(gòu)決定，即薄膜晶體結(jié)構(gòu)的不同來源于沉積過程中錫源和硫源 之間不同的反應(yīng)路徑。所制備的閃鋅礦及正交結(jié)構(gòu)SnS薄膜的電阻率最低分別為3300·cm及140·cm，均低于之前文獻(xiàn)中報(bào)道的相應(yīng)結(jié)構(gòu)SnS薄膜的電阻率。研究了制備參數(shù)對(duì)正交結(jié)構(gòu)SnS薄膜結(jié)構(gòu)、形貌、電學(xué)及光學(xué)性能的影響，根據(jù)正交結(jié)構(gòu)SnS薄膜的形成機(jī)理討論了制備參數(shù)影響薄膜結(jié)構(gòu)及性能的具體途徑。以正交結(jié)構(gòu)SnS為吸收層，制備了FTO/SnS/Bi_2S_3/Ag、FTO/CdS/SnS/Ag兩種結(jié)構(gòu)的異質(zhì)結(jié)電池。所制備的異質(zhì)結(jié)電池有明顯的二極管特性，但光電轉(zhuǎn)換效率較低，，尚需進(jìn)一步優(yōu)化。 對(duì)Bi_2S_3薄膜的化學(xué)浴制備工藝進(jìn)行了系統(tǒng)研究，研究了制備體系、制備參數(shù)、緩沖層、添加劑等對(duì)Bi_2S_3薄膜結(jié)構(gòu)、形貌、光學(xué)及電學(xué)性能的影響。發(fā)現(xiàn)當(dāng)在襯底表面先沉積一層SnS緩沖層再用化學(xué)浴沉積Bi_2S_3薄膜時(shí)，所制備薄膜的均勻性及粘附性有明顯提高。使用由Bi(NO3)3、乙二胺四乙酸（EDTA）和硫代乙酰胺（TA）組成的化學(xué)浴制備體系沉積Bi_2S_3薄膜時(shí)，可得到由納米棒狀顆粒組成的薄膜，薄膜的表面較為疏松且與襯底的粘附性不好。當(dāng)在化學(xué)浴制備體系中使用Bi(NO_3)_3及Na_2S_2O_3分別作為鉍源及硫源時(shí)（配位劑使用檸檬酸銨或乙二胺四乙酸），容易得到表面呈樹枝狀的Bi_2S_3薄膜，薄膜的表面較為疏松且與襯底粘附不好。使用由Bi(NO_3)_3、檸檬酸銨（AC）和硫代乙酰胺（TA）組成的化學(xué)浴制備體系可沉積得到結(jié)構(gòu)致密的Bi_2S_3薄膜。在此體系下通過提高硫代乙酰胺濃度、降低Bi(NO_3)_3濃度及在反應(yīng)溶液中添加NH_4Cl等可提高薄膜表面的平整度。通過優(yōu)化制備條件最終得到了致密、平整且與襯底粘附良好的Bi_2S_3薄膜。另外使用由Bi(NO3)3、檸檬酸銨（AC）和硫代乙酰胺（TA）組成的化學(xué)浴制備體系制備得到了二維納米片狀結(jié)構(gòu)的Bi_2S_3薄膜。發(fā)現(xiàn)pH值及沉積溫度是制備二維納米片狀結(jié)構(gòu)Bi_2S_3薄膜的決定因素。以化學(xué)浴制備的Bi_2S_3薄膜為吸收層制備了FTO/SnS/Bi_2S_3/Ag結(jié)構(gòu)的異質(zhì)結(jié)電池。 使用氯化鎘體系及乙酸鎘體系制備了六方結(jié)構(gòu)且有明顯的（002）擇優(yōu)取向的CdS薄膜，對(duì)其形貌及性能進(jìn)行了對(duì)比。發(fā)現(xiàn)使用乙酸鎘體系制備的CdS薄膜組成顆粒較小，表面更為平滑。由乙酸鎘體系制備的CdS薄膜的電阻率小于由氯化鎘體系制備的CdS薄膜的電阻率。乙酸鎘體系制備的CdS薄膜的光學(xué)帶隙略大于氯化鎘體系制備的CdS薄膜的光學(xué)帶隙。以CuCl2為銅源、硫脲為硫源，三乙醇胺或檸檬酸銨為配位劑制備了Cu_xS薄膜，薄膜經(jīng)200℃退火后結(jié)構(gòu)均為輝銅礦結(jié)構(gòu)。當(dāng)使用不同配位劑（三乙醇胺及檸檬酸銨）制備Cu_xS薄膜時(shí)，所制備的Cu_xS薄膜在結(jié)構(gòu)、形貌及性能上的差異較小。Cu_xS薄膜退火后電阻率約在10-3·cm數(shù)量級(jí)，薄膜可見光波段透過率約50%。由化學(xué)浴工藝制備了均勻、致密且粘附良好的ZnS薄膜。所制備的ZnS薄膜光學(xué)帶隙約3.9eV，其在350-1950nm波段的平均透過率約為85.6%。化學(xué)浴制備的ZnS薄膜可作為一種價(jià)格低廉的減反射膜，將ZnS薄膜沉積在制絨的硅片表面可使硅片表面反射率從14%降至7%。由溶液法制備硫化物前驅(qū)薄膜后退火的方法制備了Cu_2ZnSnS_4(CZTS)薄膜，研究了前驅(qū)薄膜結(jié)構(gòu)對(duì)CZTS薄膜制備的影響。發(fā)現(xiàn)先使用連續(xù)離子層吸附沉積制備Cu_xS與SnS的混合層后化學(xué)浴沉積ZnS層制備前驅(qū)薄膜的工藝較有利于CZTS的形成。利用該工藝制備了均勻致密的CZTS薄膜，薄膜光學(xué)帶隙為1.53eV。
[Abstract]:Energy shortage and environmental pollution are two major problems in the current human face. In order to maintain the development of society and economy, human beings must develop clean and renewable energy. Photovoltaic power generation is one of the most promising renewable energy technologies, is expected to solve the two major problems of energy and environment. But the high cost of photovoltaic power generation, greatly may limit its large-scale application. The solution to this problem is the cost of manufacturing process for preparation of solar cell materials the development of low cost and low to reduce the cost of solar cells, thereby reducing the cost of photovoltaic power generation. This paper makes the solution with low cost method (successive ionic layer adsorption and deposition and chemical bath deposition) system prepared several can be applied to
Thin film solar cells (SnS, Bi_2S_3, CdS, Cu_xS, ZnS and Cu_2ZnSnS_4), a detailed study of the process parameters of the preparation of thin film structure, influence the morphology and properties of thin film preparation mechanism was discussed. On the basis of preparation of the heterogeneous structure of several node prototype device for thin film solar cells. The solution method for preparing solar cells with low cost. In order to lay the foundation for the successive ionic layer adsorption and deposition process of zinc blende SnS thin film was prepared. When the novel found in cationic precursor solution
Chlorine ion, the growth rate of the film increased, better crystallinity, surface morphology becomes rough. The above results were analyzed: in cation solutions may exist in metal coordination polymer ionic polymerization to form, similar in this multimeric tin coordination structure and tin in zinc blende SnS the coordination structure. These precursor substances adsorbed on the substrate surface and then reacts with sulfur ions, maintaining tin ion coordination structure during the reaction constant to obtain zinc blende SnS. when chloride ions added to the cationic solution, chloride ion promoted metal ion polymerization process so as to form a larger structure the polymer becomes possible, so the chlorine ion will increase the growth rate and crystallinity of the films. The use of a new chemical bath preparation system was prepared with zinc blende structure and orthogonal structure of two kinds of structure SnS thin film deposition temperature and pH value. That is the main factor to determine the crystal structure of SnS films. The final prepared by the same preparation system of the preparation mechanism of SnS thin films with different structure are discussed that the SnS film of the final crystal structure determined by the tin ion intermediate is in coordination a structure in the chemical bath process, which is different from the crystal structure of film deposition process of tin and sulfur sources
Between the different reaction paths. The sphalerite and orthogonal structure of SnS thin films prepared by the lowest resistivity were 3300 cm and 140 cm, the resistivity was lower than the corresponding structure of SnS films previously reported in the literature. The effects of preparation parameters on the morphology structure of SnS thin films, orthogonal structure, electrical and optical properties of the influence according to the formation mechanism, discussed the preparation ways of the structure and properties of thin film parameters affect the orthogonal structure of SnS thin films. The absorption layer with orthogonal structure SnS, FTO/SnS/Bi_2S_3/Ag prepared FTO/CdS/SnS/Ag two structure heterojunction battery. The heterojunction solar cells prepared with diode characteristics obviously, but the photoelectric conversion efficiency is low that needs to be further improved.
Process of chemical bath deposition of Bi_2S_3 thin films were studied. The research of the preparation system and preparation parameters, buffer layer, morphology of additive on the structure of Bi_2S_3 thin films, and influence the electrical and optical properties. When the surface of the substrate to deposit a layer of SnS buffer layer by chemical bath deposition of Bi_2S_3 thin film, uniform and the adhesion of the films is obviously improved. By the use of Bi (NO3) 3, EDTA (EDTA) and thioacetamide (TA) composed of chemical bath deposition of Bi_2S_3 thin film preparation system, obtained films composed of nanorods, adhesion of the film and the substrate surface is loose and not good. When in the chemical bath preparation using Bi system (NO_3) _3 and Na_2S_2O_3 respectively as bismuth source and sulfur source (complexing agent using ammonium citrate or EDTA), easy to get the Bi_2S_3 film surface was dendritic, film surface Loose and substrate adhesion is not good. By the use of Bi _3 (NO_3), ammonium citrate (AC) and thioacetamide (TA) chemical bath preparation system composed of Bi_2S_3 thin films can be deposited dense structure. Under this system by increasing the concentration of thioacetamide, reducing Bi (NO_3) concentration and _3 in the reaction solution adding NH_4Cl can improve the flatness of the film surface. By optimizing the preparation conditions finally got a dense, smooth and good adhesion with substrate Bi_2S_3 film. Also used by the Bi (NO3) 3, ammonium citrate (AC) and thioacetamide (TA) composed of chemical bath preparation system Bi_2S_3 thin films were prepared two-dimensional nano lamellar structure. It was found that pH value and deposition temperature is the decisive factor of the two-dimensional Bi_2S_3 nanosheet structure. Bi_2S_3 thin films were prepared by chemical bath preparation for absorption layer prepared heterojunction FTO/SnS/Bi_2S_3/Ag cell structure.
The use of cadmium chloride and cadmium acetate system was prepared by the six party system structure and has obvious (002) preferred orientation of CdS films, the morphology and properties were compared. Found that the use of CdS thin films prepared by cadmium acetate system composed of smaller particles, the surface is smoother. The resistivity of CdS thin films by cadmium acetate system the preparation of less than CdS thin films prepared by cadmium chloride system. The optical system of CdS thin film cadmium acetate prepared the optical band gap is slightly larger than the CdS thin film cadmium chloride system for preparation of the bandgap. Using CuCl2 as the copper source, thiourea as sulfur source, triethanolamine or ammonium citrate as complexing agent preparation Cu_xS thin film was annealed at 200 C after structure are chalcocite structure. When using different complexing agent (triethanolamine and ammonium citrate) for the preparation of Cu_xS films, Cu_xS films prepared in structure, small differences in morphology and properties of.Cu_xS films on the resistance The rate of about 10-3, the level of CM, visible light transmittance of thin films is about 50%. by chemical bath process to prepare the uniform, dense ZnS films and good adhesion. ZnS films have been prepared by optical band gap of about 3.9eV, the average 350-1950nm transmittance is about ZnS 85.6%. thin films prepared by chemical bath can anti reflection film as a low price, the ZnS thin films deposited on silicon wafer surface texturing of the surface reflectance from 14% to 7%. by sulfide films by annealing precursor solution method of the preparation method of Cu_2ZnSnS_4 (CZTS) thin film, thin film of precursor structure effect on the preparation of CZTS thin films. That first using successive ionic layer adsorption and deposition of Cu_xS and SnS mixed layer after chemical bath deposition of ZnS thin film precursor process system is conducive to the formation of CZTS. CZTS films are uniform and dense in the preparation process, the optical band gap is 1.53 EV.

【學(xué)位授予單位】：南京航空航天大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2011
【分類號(hào)】：O484.4;TM914.4

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