本文選題：銅鋅錫硫 + 微觀形貌��； 參考：《吉林大學(xué)》2017年博士論文

【摘要】：太陽能被認(rèn)為是最經(jīng)濟(jì)和環(huán)保的可再生能源,基于光伏效應(yīng)的太陽能電池由于能夠直接將光照轉(zhuǎn)換成電能,因而受到了廣泛的關(guān)注。薄膜太陽能電池具有制備工藝簡單,所需原材料少,便于攜帶等優(yōu)點(diǎn)而被廣泛研究。銅銦鎵硒(Cu In Ga Se2,CIGS)和碲化鎘(Cd Te)薄膜太陽能電池已經(jīng)實(shí)現(xiàn)了產(chǎn)業(yè)化生產(chǎn),但是生產(chǎn)這兩種電池需要消耗大量的稀有金屬和有毒重金屬元素。鋅黃錫礦結(jié)構(gòu)的銅鋅錫硫(Cu_2Zn Sn S_4,CZTS)基材料具有合適的光學(xué)帶隙和超過104 cm-1的高吸收系數(shù),其組成元素都是地殼含量豐富且無毒的,理論預(yù)測CZTS太陽能電池轉(zhuǎn)換效率超過30%,因此,被認(rèn)為是替代CIGS制備薄膜太陽能電池的理想吸收層材料。CZTS基太陽能電池的效率在短短二十年內(nèi)就從0.66%提升到12.6%,但與CIGS電池效率相比還有很大差距。除了材料單一相范圍小、存在較多雜相和缺陷等問題外,薄膜的晶體質(zhì)量以及p-n結(jié)能帶匹配問題也是導(dǎo)致其效率較低的主要原因。針對(duì)這兩個(gè)問題,我們?cè)诒疚闹刑岢隽烁纳票∧の⒔Y(jié)構(gòu)、提高晶體質(zhì)量的技術(shù)途徑,并在此基礎(chǔ)上對(duì)界面能帶排列和相關(guān)CZTS基光電器件應(yīng)用進(jìn)行了研究,取得了如下結(jié)果:1、通過磁控濺射單一CZTS靶材、調(diào)節(jié)快速熱處理氣氛中S/Se元素比例,制備了大晶粒、高致密的CZTSSe薄膜。我們采取高壓固態(tài)反應(yīng)技術(shù)制備四元單一相CZTS靶材,然后通過磁控濺射技術(shù)和快速熱處理技術(shù)制備CZTSSe吸收層薄膜。通過優(yōu)化快速熱處理的升溫速率,得到了平整致密的吸收層薄膜;通過調(diào)節(jié)退火氣氛中S粉和Se粉的比例,可以實(shí)現(xiàn)對(duì)薄膜中S/Se元素含量、結(jié)構(gòu)以及光電性質(zhì)的控制。研究結(jié)果表明貧S富Se的薄膜晶粒尺寸比較均勻,其縱向貫穿的晶粒尺寸能達(dá)到2μm,并且薄膜具有1.13 e V的光學(xué)帶隙和較高的遷移率,適合作為高效率電池的吸收層。用這種薄膜制備了標(biāo)準(zhǔn)結(jié)構(gòu)的電池器件,其光電轉(zhuǎn)換效率為3.38%。進(jìn)一步的分析表明,晶體質(zhì)量的提高減少了光生載流子在CZTSSe吸收層內(nèi)部的復(fù)合,但嚴(yán)重的界面復(fù)合導(dǎo)致了器件的理想因子和反向飽和電流較大,進(jìn)而影響了器件的開路電壓和填充因子。2、通過向CZTS前軀體溶液中添加適量的高分子聚合物,提高了薄膜晶體質(zhì)量,改善了吸收層與緩沖層和背電極之間的界面性能。研究了聚乙烯吡咯烷酮(PVP)添加量對(duì)溶液法制備CZTSSe薄膜形貌及電池器件性能的影響。發(fā)現(xiàn)添加劑對(duì)薄膜的組分和晶體結(jié)構(gòu)沒有太大影響,但是能明顯提高CZTSSe薄膜的致密性和晶粒尺寸。PVP添加量為5 wt%時(shí)晶粒尺寸能達(dá)到5μm以上,但是過量添加會(huì)使薄膜中出現(xiàn)小晶粒層,而添加比例為1 wt%時(shí)得到的薄膜表面和斷面形貌都比較好。用這種薄膜制備的CZTSSe電池效率為4.34%。相比于未添加PVP的標(biāo)準(zhǔn)電池(效率為2.24%)提高了很多。電池器件界面的優(yōu)化減少了光生載流子在界面處的復(fù)合。因此電池的開路電壓,短路電流以及填充因子都有所提升。3、利用XPS實(shí)驗(yàn)測量結(jié)合第一性原理計(jì)算闡明了CZTS/Zn O異質(zhì)結(jié)界面能帶排列結(jié)構(gòu)及其物理機(jī)制。利用磁控濺射制備了CZTS/Zn O異質(zhì)結(jié),通過X射線光電子能譜實(shí)驗(yàn)測量和第一性原理計(jì)算分別得到了CZTS/Zn O異質(zhì)結(jié)的能帶偏移。發(fā)現(xiàn)該異質(zhì)結(jié)的能帶排列為I型對(duì)齊,而且導(dǎo)帶偏移值很小。這種能帶對(duì)齊方式能夠減少光生載流子的界面復(fù)合,并且不會(huì)阻礙載流子的輸運(yùn)。從能帶排列角度說明Zn O是一種潛在的無毒緩沖層材料。4、通過調(diào)節(jié)施加偏壓,實(shí)現(xiàn)了對(duì)p?CZTS/n?Ga N異質(zhì)結(jié)光電二極管在紫外和可見區(qū)光響應(yīng)的調(diào)控,并闡明了響應(yīng)機(jī)制。由于寬禁帶半導(dǎo)體Ga N和Zn O具有相似的結(jié)構(gòu)和性質(zhì),我們采用射頻磁控濺射方法在n-Ga N基底上沉積一層p-CZTS薄膜,制備出p-CZTS/n-Ga N異質(zhì)結(jié)光電二極管,并研究了它的光響應(yīng)特性。發(fā)現(xiàn)通過調(diào)節(jié)施加偏壓可以調(diào)制其光譜響應(yīng),不加偏壓和加上反向偏壓時(shí)其響應(yīng)波長分別位于紫外光區(qū)和可見光區(qū),用異質(zhì)結(jié)能帶排列可以很好的解釋觀察到的實(shí)驗(yàn)現(xiàn)象。5、采用凝膠技術(shù)制備了新型的Cu_2Mg Sn S_4薄膜,闡明了硫化溫度對(duì)薄膜結(jié)構(gòu)及光電性質(zhì)的影響規(guī)律。發(fā)現(xiàn)Cu+、Mg2+、Sn4+三種陽離子在晶格中的占位是隨機(jī)的。由于晶體結(jié)構(gòu)對(duì)稱性的提高,X射線衍射結(jié)果中只出現(xiàn)了閃鋅礦結(jié)構(gòu)的特征衍射峰。CMTS薄膜具有良好的電學(xué)性質(zhì)和合適的光學(xué)帶隙,適合作為薄膜太陽能電池的吸收層材料。
[Abstract]:Solar energy is considered to be the most economical and environmentally friendly renewable energy. Solar cells based on photovoltaic effect are widely concerned because they can directly convert light into electrical energy. Thin film solar cells have been widely studied with the advantages of simple preparation technology, less raw materials and easy to carry. Cu In Ga Se2, CIGS) and cadmium telluride (Cd Te) thin film solar cells have achieved industrial production, but the production of these two kinds of batteries requires a large number of rare metals and toxic heavy metals. The copper zinc tin sulfur (Cu_2Zn Sn S_4, CZTS) base material of the zine tin structure has the appropriate optical band gap and the high absorption coefficient of over 104 cm-1, and its constituent element All the elements are rich and nontoxic in the earth's crust. It is predicted that the conversion efficiency of CZTS solar cells is more than 30%. Therefore, it is considered that the efficiency of.CZTS based solar cells, which is an ideal absorbing layer for preparing thin film solar cells by CIGS, has been raised from 0.66% to 12.6% in just twenty years, but there is a big gap compared with the efficiency of CIGS battery. In addition to the small phase range and a large number of impurities and defects, the crystal quality of the film and the matching of the p-n junction band are also the main reasons for the low efficiency. In this paper, we put forward a technical approach to improve the microstructure of the thin film and improve the quality of the crystalline body in this paper, and on this basis, the interface is on the interface. The results are as follows: 1, by sputtering a single CZTS target by magnetron sputtering and adjusting the proportion of S/Se elements in the fast heat treatment atmosphere, the large and dense CZTSSe thin films are prepared. The high pressure solid-state reaction technology is used to prepare a single phase CZTS target of four yuan and then through magnetic control. CZTSSe absorption layer films are prepared by sputtering and rapid heat treatment. By optimizing the heating rate of rapid heat treatment, a smooth and compact absorption layer film is obtained. By adjusting the proportion of S powder and Se powder in the annealing atmosphere, the content of S/Se elements in the thin film can be realized, the structure and the photoelectric properties are controlled. The results show that the poor S is rich in Se. The grain size of the film is more uniform, its longitudinal grain size can reach 2 m, and the film has the optical band gap and high mobility of 1.13 e V. It is suitable to be used as the absorption layer of the high efficiency battery. The increase of the quantity reduces the composition of the optical carrier in the CZTSSe absorption layer, but the serious interface recombination leads to the ideal factor and the reverse saturation current of the device, which affects the open circuit voltage and the filling factor.2. By adding a proper amount of polymer to the body solution before CZTS, the quality of the film is improved. The effect of the addition of polyvinylpyrrolidone (PVP) on the morphology of CZTSSe film and the performance of the battery devices was studied. It was found that the additives had no great influence on the composition and crystal structure of the thin film, but it could obviously improve the density and grain size of the CZTSSe film. The grain size can reach more than 5 m when the amount of inch.PVP is 5 wt%, but a small grain layer will appear in the film with excessive addition, and the surface and section morphology of the film are better when the addition ratio is 1 wt%. The efficiency of the CZTSSe battery prepared with this film is higher than that of the standard battery without PVP (efficiency 2.24%). The optimization of the interface of the battery device reduces the recombination at the interface between the optical carrier and the carrier. So the open circuit voltage, the short circuit current and the filling factor of the battery have been improved by.3. Using the XPS experimental measurement and the first principle, the arrangement structure and physical mechanism of the CZTS/Zn O heterojunction interface band are clarified. The CZTS/Zn O heterojunction is obtained by X ray photoelectron spectroscopy and the first principle calculation. The energy band migration of CZTS/Zn O heterojunction is obtained. It is found that the band alignment of the heterojunction is I aligned, and the guide band offset value is very small. This band alignment method can reduce the interface recombination of the optical carrier and will not hinder the load. Zn O is a potential nontoxic buffer layer material.4. By adjusting the bias voltage, the p? CZTS/n? Ga N heterojunction photodiode is regulated by the ultraviolet and visible light response, and the response mechanism is clarified. The structure and properties of the wide band gap semiconductor Ga N and Zn O are similar. We deposited a layer of p-CZTS thin film on the n-Ga N substrate by RF magnetron sputtering. The p-CZTS/n-Ga N heterojunction photodiode was prepared and its light response characteristics were studied. It was found that the spectral response could be modulated by adjusting the bias voltage. The response wavelengths were located in the UV light region and visible respectively without bias voltage and the reverse bias voltage. The optical region, using the heterojunction band arrangement, can explain the observed experimental phenomenon.5. The new Cu_2Mg Sn S_4 film is prepared by the gel technique. The influence of the vulcanization temperature on the structure and photoelectric properties of the film is clarified. It is found that the occupying position of three kinds of cations of Cu+, Mg2+ and Sn4+ in the lattice is random. In the results of X ray diffraction, only the characteristic diffraction peak of sphalerite structure is found in the.CMTS film, which has good electrical properties and suitable optical band gap, which is suitable for the absorption layer of thin film solar cells.

【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB383.2;TM914.4

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