本文選題：硫族化合物　切入點(diǎn)：半導(dǎo)體納米材料　出處：《中國(guó)科學(xué)技術(shù)大學(xué)》2015年碩士論文

【摘要】：進(jìn)入21世紀(jì)以來(lái),全球范圍內(nèi)對(duì)太陽(yáng)能電池的需求,每年以40%以上的速度增長(zhǎng)。太陽(yáng)能電池的應(yīng)用是目前可再生能源研究的重點(diǎn),太陽(yáng)能吸收層作為太陽(yáng)能電池的核心器件,其吸收層材料的種類(lèi)也有很多,然而,大多數(shù)現(xiàn)有的高性能材料的應(yīng)用因其利用率低,成本高,環(huán)境不相容性而受到限制。硫族化合物半導(dǎo)體納米材料窄的直接帶隙使其具有光學(xué)特性、電學(xué)特性、光電轉(zhuǎn)化特性、光電催化特性,引起了人們極大的興趣和關(guān)注。目前研究最多的是Ⅱ-Ⅵ(CdS,HgSe), Ⅳ-Ⅵ (PbS, PbSe)及多元硫化物半導(dǎo)體納米材料如CuxS1-x, CIGS(CuInGaSe2), CZTS (Cu2ZnSnS4)�？紤]到Cd和Hg有毒,銦和稼元素是稀土元素且價(jià)格昂貴,從而限制了其發(fā)展。S、 Cu、 Zn、 Ge元素年產(chǎn)量高、價(jià)格低并且低毒,在太陽(yáng)能吸收層材料方面有著潛在的應(yīng)用,適用于大規(guī)模、低成本的太陽(yáng)能電池生產(chǎn)。本文在此背景下,圍繞GeS、 GeSe和CZTS納米材料的制備、表征及其在太陽(yáng)能吸收層材料方面的應(yīng)用開(kāi)展了一系列工作,主要內(nèi)容如下： 一、介紹了一種簡(jiǎn)單的溶劑熱法可控的合成GeSe單晶納米結(jié)構(gòu)。通過(guò)改變反應(yīng)溶劑和反應(yīng)物的量選擇性的制備了GeSe納米片和納米帶材料。通過(guò)XRD、EDX確定了產(chǎn)物的相與成分。并利用SEM、 TEM對(duì)他們的形貌、微結(jié)構(gòu)以及生長(zhǎng)方向等進(jìn)行了表征與分析。對(duì)生成產(chǎn)物的反應(yīng)條件和反應(yīng)機(jī)理進(jìn)行了探討。 二、采用簡(jiǎn)單的一步溶液法可控制備了GeS納米片和GeS納米線,研究了反應(yīng)溫度和反應(yīng)時(shí)間對(duì)其形貌的影響,最后提出了納米線的生長(zhǎng)機(jī)理。利用XRD與EDX確定所合成的樣品為GeS材料；利用SEM、TEM等表征手段研究了GeS納米片、GeS納米線的微結(jié)構(gòu)以及形成機(jī)理。利用紫外-可見(jiàn)分光光度計(jì)測(cè)定了GeS納米結(jié)構(gòu)的光電性能,通過(guò)線性擬合得出了它們的帶隙值。在反應(yīng)過(guò)程中OLA作為活性劑和包覆劑,在GeS的生長(zhǎng)過(guò)程中起了重要作用；通過(guò)控制反應(yīng)溫度和加熱時(shí)間,可以得到納米片和納米線2種不同形貌的材料。最后對(duì)GeS納米線提出了一種卷曲過(guò)程的生長(zhǎng)機(jī)理：在溫度升高的過(guò)程中,由于GeS納米片和OLA的相互作用,使得GeS納米片產(chǎn)生較強(qiáng)的表面張力,在這種驅(qū)動(dòng)力下,使得GeS納米片發(fā)生彎曲,最終形成納米線結(jié)構(gòu)。因此,制備不同形貌和尺寸的GeS納米材料的研究推進(jìn)了光伏吸收材料的進(jìn)步,在光電材料領(lǐng)域中還有更大的研究空間。 三、探討了一步水熱法合成二維結(jié)構(gòu)的CZTS納米片,使用CuCl2、 SnCl4、 ZnCl2作為金屬前驅(qū)體,硫脲作為硫源,聚乙烯吡咯烷酮(PVP)作為表面活性劑。通過(guò)XRD、 EDX、 HRTEM和拉曼光譜對(duì)其物相、結(jié)構(gòu)、形貌和光電性能進(jìn)行了表征,結(jié)果顯示制備的CZTS納米片是半透明狀且平均厚度在10nm左右。此外,文章討論了PVP對(duì)CZTS結(jié)構(gòu)和形態(tài)的影響；光電性能分析結(jié)果表明CZTS納米晶體的帶隙寬度約為1.48eV,是理想的薄膜太陽(yáng)能電池材料；最后探討了可能的生長(zhǎng)機(jī)理。在這里,我們使用水作為溶劑,綠色無(wú)污染；制備方法簡(jiǎn)單、成本低,使其廣泛應(yīng)用于薄膜光伏電池的生產(chǎn)。
[Abstract]:Since twenty-first Century, global demand for solar cells, the annual growth rate of more than 40%. The application of solar cells is the focus of the current research on renewable energy, the solar energy absorbing layer as the core component of solar cells, the absorption type layer material also has a lot of application, however, most of the existing high performance materials for the low utilization rate, high cost, environmental compatibility is limited. Chalcogenide semiconductor nanomaterials narrow direct band gap which has optical properties, electrical properties, photoelectric conversion characteristics, photoelectric catalytic properties, has aroused great interest and attention. At present, most of the research is (CdS, II - VI HgSe), IV - VI (PbS, PbSe) and multiple sulfide semiconductor nano materials such as CuxS1-x, CIGS (CuInGaSe2), CZTS (Cu2ZnSnS4). Considering the Cd and Hg elements are toxic, indium and rare earth elements and the price of corn Expensive, which limits the development of.S, Cu, Zn, Ge elements with high yield, low price and low toxicity, have potential applications in solar energy absorption layer, suitable for mass production of solar cells, low cost. Based on this background, around GeS, GeSe and CZTS nanostructures characterization and application layer in solar absorption materials has carried out a series of work, the main contents are as follows:
First, introduces the synthesis of single crystal GeSe nano structure of a simple solvothermal method. Controlled by changing the reaction solvent and the reaction amount of selective preparation of GeSe nano film and nano belt materials. Through XRD, EDX to determine the phase components of the product. And the use of SEM and TEM on their morphology, micro the structure and growth direction were characterized and analyzed. The reaction conditions and reaction mechanism of the formation of the product were discussed.
The two step, using a simple solution method can control the synthesis of GeS nano films and GeS nanowires, studied the influence of reaction temperature and reaction time on the morphology, finally proposed the growth mechanism of nanowires. The synthesis using XRD and EDX samples for GeS materials; using SEM, TEM were used to study the micro structure of nano GeS, GeS nanowires and formation mechanism. By using UV visible spectrophotometry and optical properties of GeS nanostructures were determined by linear fitting, the value of their band gaps. In the reaction process of OLA as an active agent and coating agent, played an important role in the growth process of GeS in; by controlling the reaction temperature and heating time, can get nanosheets and nanowires of 2 different morphologies of materials. Finally, a curling process on the growth mechanism of GeS nanowires is proposed: in the process of temperature rise, due to nano GeS The interaction of OLA and GeS, the nano produced strong surface tension, the driving force, making GeS nano sheet bending, and ultimately the formation of nanowire structure. Therefore, study on Preparation of GeS nano materials with different morphologies and sizes of the advanced photovoltaic step absorbing materials, in the field of photoelectric material and greater research space.
Three, discusses the CZTS nanosheets, one-step hydrothermal synthesis of two-dimensional structure using CuCl2, SnCl4, ZnCl2 as a metal precursor, thiourea as sulfur source, polyvinylpyrrolidone (PVP) as a surfactant. Through XRD, EDX, HRTEM and Raman spectra of phase structure on the matter, and photoelectric properties the morphology was characterized, the results showed that CZTS nano film preparation is translucent and the average thickness is about 10nm. In addition, the article discusses the influence of PVP on the structure and morphology of CZTS; the analysis results show that the CZTS photoelectric properties of nano crystal band gap width is about 1.48eV, is the ideal material for thin film solar cell is discussed; the possible growth mechanism. Here, we use water as a solvent, no pollution to the environment; the preparation method is simple, low cost, it is widely used in solar cell production.

【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TM914.4;TB383.1

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