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  本文選題：液相法　切入點：Cu2ZnSnS4(CZTS)　出處：《河南大學(xué)》2014年碩士論文　論文類型：學(xué)位論文

【摘要】：硫族半導(dǎo)體是一種重要的半導(dǎo)體材料。近年來科研工作者對硫族半導(dǎo)體納米晶的合成、物理性質(zhì)和其在很多方面的應(yīng)用都進(jìn)行了深入的研究。而銅鋅錫硫（Cu2ZnSnS4，CZTS）作為一種四元硫族化合物半導(dǎo)體，可以看作是鋅和錫以1:1的比例取代CuInS2中的In而得到的。 CZTS材料的合成方法大致可分為：真空法和液相法。真空法主要是通過濺射或蒸發(fā)的方法來制備CZTS薄膜。這些方法大多需要較苛刻的實驗條件：如高溫高壓。這就導(dǎo)致該方法對設(shè)備的要求較高，能耗也較高。為了降低成本，液相法得到了發(fā)展。因為納米晶墨水可以通過旋涂、滴涂、噴墨打印等方法直接成膜，不需要依賴大型的真空設(shè)備，從而降低了成本，有利于大規(guī)模生產(chǎn)。所以不同形貌和結(jié)晶度的CZTS納米晶陸續(xù)被合成出來。 在本論文中我們用簡單的液相法合成了纖維鋅礦CZTS納米梭和球狀鋅黃錫礦CZTS納米顆粒。納米梭的長度為100-150nm，寬度為30-40nm，并研究了納米梭的光電性質(zhì)，并將其鋪成薄膜嘗試應(yīng)用于薄膜太陽電池中。球狀CZTS納米顆粒的尺寸為300-500nm，，并將其應(yīng)用作鋰離子電池其負(fù)極材料。本論文的工作主要包括以下幾個部分: （1）我們用簡單的一鍋法在不需惰性氣體保護(hù)的條件下合成了亞穩(wěn)態(tài)的纖維鋅礦CZTS納米梭。用XRD，TEM和SEM對合成的CZTS納米梭的結(jié)構(gòu)和形貌進(jìn)行了表征。通過UV-vis吸收和反射光譜對納米梭的光學(xué)特性進(jìn)行了表征，發(fā)現(xiàn)與CZTS納米晶相比CZTS納米梭在可見光區(qū)有較強(qiáng)的吸收。這可能是由于納米梭薄膜具有較強(qiáng)的光陷阱效應(yīng)，導(dǎo)致其對光的吸收更有效。我們還對CZTS的光電性質(zhì)進(jìn)行了探究。通過I-V測試和Hall效應(yīng)測試，我們發(fā)現(xiàn)與CZTS納米晶相比CZTS納米梭的載流子濃度較高，電阻率較小。這些結(jié)果表明，CZTS納米梭有利于增加載流子濃度和提高電子傳輸。 (2)將CZTS納米梭配制成納米墨水，并用滴涂法鋪膜。將CZTS納米梭薄膜硒化得到CZTSe薄膜，并將其組裝成CZTSe薄膜太陽電池，并對電池的性能進(jìn)行了I-V測試。由于無法精確控制組裝過程中的工藝條件，致使電池的性能結(jié)果并不理想。所以想要制造低價高性能的光伏器件還有很長的路要走。 (3)我們用溶劑熱法合成了球狀300-500nm的Cu2ZnSnS4(CZTS)納米顆粒。從SEM和TEM圖中我們發(fā)現(xiàn)較大的球狀CZTS納米顆粒是由更小的CZTS納米晶堆積而成的。CZTS納米顆粒作為鋰離子電池的負(fù)極材料時，在經(jīng)過多次循環(huán)后仍能夠保持較穩(wěn)定的Li+的插入/脫出過程。其電化學(xué)性能可以歸因于納米顆粒的分級納米結(jié)構(gòu)和銅/鋅誘導(dǎo)產(chǎn)生的有效的電荷傳輸。這些性質(zhì)表明CZTS納米材料在鋰離子電池負(fù)極材料中的潛在應(yīng)用價值。
[Abstract]:Sulfur semiconductor is an important semiconductor material. The physical properties and their applications in many fields have been studied in depth. As a quaternary sulfur compound, copper, zinc, tin sulfide Cu2ZnSnS4CZTSS can be regarded as the substitution of zinc and tin for in in in CuInS2 at 1:1. The synthesis methods of CZTS materials can be roughly divided into vacuum method and liquid phase method. The vacuum method is mainly by sputtering or evaporation to prepare CZTS thin films. Most of these methods require harsh experimental conditions, such as high temperature and high pressure. This leads to a higher demand for equipment, In order to reduce the cost, the liquid phase method has been developed, because nanocrystalline ink can be directly coated by spin-coating, droplet coating, inkjet printing and so on, without the need to rely on large vacuum equipment, thus reducing the cost. Therefore, CZTS nanocrystals with different morphology and crystallinity were synthesized one after another. In this paper, we have synthesized CZTS nanoparticles of wurtzite CZTS and CZTS nanoparticles of spherical zinc-yellow tin ore by simple liquid phase method. The length and width of the shuttle are 100-150 nm and 30-40 nm, and the photoelectric properties of the shuttle are studied. The spherical CZTS nanocrystalline is 300-500nm in size and is used as the anode material of lithium ion battery. The work of this thesis mainly includes the following parts:. (1) the metastable wurtzite CZTS nanoshuttles were synthesized by a simple one-pot method without inert gas protection. The structure and morphology of the synthesized CZTS nanoshuttles were characterized by XRD-TEM and SEM. The structure and morphology of the synthesized CZTS nanoshuttles were characterized by UV-vis absorption and inversion. The optical properties of the nano-shuttle were characterized by emission spectra. It is found that compared with CZTS nanocrystals, CZTS nanoparticles have strong absorption in the visible region, which may be due to the strong light trap effect of the nano-shuttle films. We also investigated the optoelectronic properties of CZTS. By I-V test and Hall effect test, we found that the carrier concentration of CZTS nanoparticles was higher than that of CZTS nanocrystals. These results indicate that the CZTS nanoparticles can increase the carrier concentration and increase the electron transport. (2) the CZTS nano-shuttle was prepared into nano-ink and coated with dripping method. The CZTSe film was prepared by selenization of the CZTS nano-shuttle film and assembled into a CZTSe thin film solar cell. The performance of the battery is tested by I-V. The performance of the battery is not satisfactory because the process conditions in the assembly process can not be controlled accurately, so there is still a long way to go to make the photovoltaic device with low cost and high performance. (3) the spherical 300-500nm nanocrystalline Cu2ZnSnSS4CZTS was synthesized by solvothermal method. From the SEM and TEM diagrams, we found that the larger spherical CZTS nanoparticles were formed from smaller CZTS nanocrystals, which were used as negative electrode materials for lithium-ion batteries. The electrochemical properties of Li can be attributed to the graded nanostructures of nanoparticles and the effective charge transport induced by copper / zinc. The potential application value of CZTS nanomaterials in cathode materials of lithium ion batteries is indicated.
【學(xué)位授予單位】：河南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2014
【分類號】：O611.4;TM912

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本文編號：1647049