本文選題：太陽(yáng)能　切入點(diǎn)：硒化物半導(dǎo)體　出處：《浙江大學(xué)》2017年博士論文　論文類(lèi)型：學(xué)位論文

【摘要】：隨著全球工業(yè)化進(jìn)程的加快,能源短缺和環(huán)境污染已經(jīng)成為世界范圍內(nèi)不容忽視的兩大問(wèn)題,嚴(yán)重制約著社會(huì)長(zhǎng)期穩(wěn)定發(fā)展。研究和開(kāi)發(fā)新能源已經(jīng)成為全球能源發(fā)展的趨勢(shì)。其中太陽(yáng)能以其取之不盡用之不竭的廣泛性及無(wú)噪音無(wú)污染的清潔性獲得了巨大關(guān)注,并成為最為理想的綠色能源；然而太陽(yáng)輻射還具有分散性與間歇性等特點(diǎn),通常無(wú)法直接利用,而是需要被有效轉(zhuǎn)化與存儲(chǔ)方可加以利用。本文總結(jié)和概括了太陽(yáng)能的主要轉(zhuǎn)化方式,對(duì)太陽(yáng)能光熱轉(zhuǎn)換、光化學(xué)轉(zhuǎn)換、光電轉(zhuǎn)換以及熱電轉(zhuǎn)換進(jìn)行了詳細(xì)的原理介紹與現(xiàn)狀分析。在此基礎(chǔ)上,分別采用熔融-冷卻(Melt-quenching)方法和熱注入(Hot injection)方法制備了金屬硒化物陶瓷和納米顆粒,研究了組成與制備工藝等對(duì)硒化物陶瓷物相組成、微觀(guān)結(jié)構(gòu)及光電性能,以及反應(yīng)物組成、反應(yīng)溫度、反應(yīng)時(shí)間等對(duì)硒化物納米顆粒微觀(guān)結(jié)構(gòu)及性能的影響規(guī)律。論文主要研究結(jié)果如下：1、以多晶鍺、銻、硒及銅等為原料,采用melt-quenching方法,制備了Cu2GeSe3-Sb2Se3體系陶瓷。研究了組成及制備工藝對(duì)陶瓷物相組成、微觀(guān)結(jié)構(gòu)及光電性能的影響。研究發(fā)現(xiàn),原料配比并不影響陶瓷材料晶體類(lèi)型,陶瓷體系中只存在Cu2GeSe3與Sb2Se3晶體,但對(duì)陶瓷中兩種晶體比例及微觀(guān)結(jié)構(gòu)有顯著影響,隨著原料中Cu(Ge)/Sb配比增加,陶瓷材料中Cu2GeSe3/Sb2Se3比例隨之上升,微觀(guān)結(jié)構(gòu)中Sb2Se3棒狀結(jié)構(gòu)逐漸淹沒(méi)于致密的Cu2GeSe3晶體當(dāng)中。Cu2GeSe3與Sb2Se3晶體比例的不同對(duì)于材料光電性能沒(méi)有顯著影響,該體系陶瓷都具有類(lèi)似的電導(dǎo)率、電流-電壓(I-V)曲線(xiàn)變化規(guī)律,且僅顯示出P型半導(dǎo)體光電流增強(qiáng)現(xiàn)象。在光密度400 W·m-2條件下,-0.6 V偏壓下的最高光電流密度達(dá)到了50 μA·cm-2。研究了CuI取代Cu對(duì)陶瓷材料結(jié)構(gòu)與性能的影響,由于I元素的引入,陶瓷中產(chǎn)生了新的SbSeI晶相,而且新相的產(chǎn)生打斷了原本貫通的Cu2GeSe3導(dǎo)電通道,不僅使材料孔隙增多,更使得陶瓷材料同時(shí)具有了P型與N型半導(dǎo)體光電效應(yīng)。初步分析了這類(lèi)陶瓷材料可能的導(dǎo)電機(jī)制,為進(jìn)一步將該體系新材料用于太陽(yáng)能電池器件奠定了基礎(chǔ)。2、以銻、硒、銅及CuI等為原料,采用melt-quenching方法,制備了不含稀有元素鍺(Ge)的Cu3SbSe4-Sb2Se3體系陶瓷。研究了組成及制備工藝對(duì)陶瓷物相組成、微觀(guān)結(jié)構(gòu)及光電性能的影響。研究發(fā)現(xiàn),原料配比并不影響陶瓷材料晶體類(lèi)型,陶瓷體系中只存在Cu3SbSe4與Sb2Se3晶體,但對(duì)陶瓷中兩種晶體比例及微觀(guān)結(jié)構(gòu)有顯著影響,隨著原料中Cu含量的增加,陶瓷材料中Cu3SbSe4/Sb2Se3比例隨之上升,微觀(guān)結(jié)構(gòu)中Sb2Se3棒狀結(jié)構(gòu)逐漸淹沒(méi)于致密的Cu3SbSe4晶體當(dāng)中。Cu3SbSe4與Sb2Se3晶體比例的不同對(duì)于材料光電性能沒(méi)有顯著影響,該體系陶瓷都具有類(lèi)似的電導(dǎo)率、Ⅰ-Ⅴ曲線(xiàn)變化規(guī)律,并同時(shí)顯示P型半導(dǎo)體與N型半導(dǎo)體光電流增強(qiáng)現(xiàn)象,在光密度400 W·m-2條件下,-0.6 V偏壓下最高光電流密度也達(dá)到了50 μA·cm-2。利用Cu3SbSe4取代Cu2GeSe3與Sb2Se3構(gòu)建微觀(guān)PN異質(zhì)結(jié)共同組成了Cu3SbSe4-Sb2Se3體系陶瓷,在成功取代了稀有元素Ge的同時(shí),保留了陶瓷優(yōu)異的光電性能。研究了Ⅰ元素?fù)诫s對(duì)Sb2Se3電阻率的影響,在不引起雜質(zhì)晶相的情況下,少量Ⅰ元素?fù)诫s即可將Sb2Se3電阻率降低105倍,這對(duì)于改善具有優(yōu)異的光吸收和熱電性能卻一直被其高電阻限制的Sb2Se3具有重大意義。Ⅰ元素?fù)诫s對(duì)于Cu3SbSe4-Sb2Se3體系陶瓷性能的影響與對(duì)Cu2GeSe3-Sb2Se3體系陶瓷的影響類(lèi)似,Ⅰ摻雜Sb2Se3也打斷了原本貫通的Cu3SbSe4導(dǎo)電通道,但由于Ⅰ摻雜顯著提高了Sb2Se3導(dǎo)電性,光生載流子不僅通過(guò)Cu3SbSe4也可通過(guò)Sb2Se3晶體,從而同時(shí)顯示出P型與N型半導(dǎo)體光電效應(yīng)。3、采用熱注入法,將室溫硒源前驅(qū)物Se-ODE注射到熱的陽(yáng)離子溶液中,通過(guò)控制反應(yīng)溫度和時(shí)間,成功制備了CuSe納米顆粒和高質(zhì)量單晶二維六方晶納米片,該合成過(guò)程避免了使用有毒的不穩(wěn)定的烷基膦類(lèi)化合物作為有機(jī)溶液,具有綠色環(huán)保,產(chǎn)率高等優(yōu)點(diǎn)。研究了反應(yīng)溫度、反應(yīng)時(shí)間及添加A13+對(duì)于CuSe晶體物相、形貌尺寸及禁帶寬度的影響。研究發(fā)現(xiàn),隨反應(yīng)時(shí)間延長(zhǎng),初始納米顆粒逐漸增大最終形成二維納米片。用定向附著理論解釋了二維納米片的生長(zhǎng)過(guò)程,硒化銅納米片通過(guò)納米晶粒之間晶面匹配、定向聚集生長(zhǎng)而成。反應(yīng)過(guò)程中,A13+離子可以通過(guò)吸附硒離子延緩納米片的生長(zhǎng)速率,無(wú)A13+離子參與條件下硒化銅納米顆粒在180℃反應(yīng)溫度下僅需10分鐘即可生長(zhǎng)為二維納米片。通過(guò)控制反應(yīng)時(shí)間可以制備近紅外光學(xué)吸收可調(diào)的硒化銅納米材料,可以根據(jù)目標(biāo)應(yīng)用對(duì)半導(dǎo)體禁帶寬度的要求進(jìn)行合成制備,極大地拓寬了硒化銅在近紅外光譜范圍的應(yīng)用。4、采用熱注入法制備了Cu3SbSe4納米顆粒。研究發(fā)現(xiàn),納米顆粒具有單晶并呈現(xiàn)單分散的類(lèi)球型結(jié)構(gòu)。通過(guò)控制反應(yīng)溫度和時(shí)間,納米顆粒平均尺寸可以在15 nm(0分鐘)到110 nm(60分鐘)之間調(diào)節(jié)。將Cu3SbSe4納米顆粒作原料用于制備塊體熱電材料,與常規(guī)固相反應(yīng)制備的Cu3SbSe熱電材料相比,用Cu3SbSe4納米顆粒制備的熱電材料可有效減少晶粒尺寸,增加晶界散射,從而有效降低材料熱導(dǎo)率。研究了Sn元素?fù)诫s對(duì)Cu3SbSe4熱電材料性能的影響,摻雜Sn元素可顯著提高材料電導(dǎo)率,結(jié)合納米顆粒制備的Cu3SbSe4熱電材料較低的熱導(dǎo)率,兩者共同提高了材料的功率因子,以Cu3Sb0.98Sn0.02Se4納米顆粒為原料,采用熱壓燒結(jié)制備的塊體熱電材料,在575 K時(shí)的熱電優(yōu)值達(dá)到了0.50。
[Abstract]:With the rapid development of industrialization, energy shortage and environmental pollution have become the two major issues in the world can not be ignored, seriously restricting the long-term stable development of the society. The research and development of new energy has become a global trend of development. The solar energy to clean its inexhaustible inexhaustible wide and no noise and no pollution the obtained great attention, and become the most ideal green energy; however, solar radiation has dispersion and intermittent characteristics, usually cannot be used directly, but to be effective conversion and storage can be used. This paper summarizes the main mode of transformation of solar energy, solar thermal, photochemical conversion, photoelectric conversion and thermoelectric conversion are introduced and analyzed in detail. The principle and status quo on the basis of this, using melt cooling method (Melt-quenching) Injection (Hot injection) and hot metal selenide ceramic nano particles and the preparation method, the composition and preparation process on the phase composition of selenide ceramic material, and photoelectric properties of microstructure, composition, and reaction temperature, influence of reaction time on the microstructure of selenide nanoparticles and performance. The main results are as follows: 1, in polycrystalline germanium, antimony, selenium and copper as raw materials, using the method of melt-quenching, Cu2GeSe3-Sb2Se3 ceramics were prepared. The composition and preparation process on the phase composition of ceramic material, influence of microstructure and photoelectric properties. The study found that does not affect the ratio of raw materials of ceramic materials Cu2GeSe3 and Sb2Se3 crystal type, crystal ceramic exists only in the system, but has significant influence on the microstructure of two kinds of ceramics and crystals in proportion with the raw material of Cu (Ge) /Sb ratio increased, Cu2GeSe3/Sb2Se ceramic material The proportion of 3 rise, Cu2GeSe3 crystal rod like structure of Sb2Se3 microstructure gradually submerged in the dense.Cu2GeSe3 and Sb2Se3 crystals with different proportion for photoelectric properties of materials had no significant effect on the ceramic has similar electrical conductivity, current voltage (I-V) variation curve, and only shows the P type semiconductor photocurrent enhancement the phenomenon. In the optical density of 400 W under the condition of m-2, the highest photoelectric -0.6 V bias current density reached 50 A - cm-2. of CuI to replace the effect of Cu on the structure and properties of ceramic materials, due to the introduction of the I element, ceramic produced a new SbSeI crystal phase, and the new phase generated interrupt the original Cu2GeSe3 conductive channel through, not only makes the material porosity increase, the ceramic material has the photoelectric effect of P type and N type semiconductor. Preliminary analysis of the conduction mechanism of the ceramic material, into a This step will be new material system for solar cell devices has laid the foundation to.2, antimony, selenium, copper and CuI as raw materials, using the method of melt-quenching, the preparation does not contain rare elements germanium (Ge) Cu3SbSe4-Sb2Se3 ceramics was studied. The composition and preparation process on the phase composition of ceramic material, and photoelectric properties the microstructure. It is found that does not affect the ratio of raw materials of ceramic materials Cu3SbSe4 and Sb2Se3 crystal type, crystal ceramic exists only in the system, but has significant influence on the microstructure of two kinds of ceramics and crystals in proportion, with the increase of Cu content in raw material, ceramic material in the proportion of Cu3SbSe4/Sb2Se3 increased, Cu3SbSe4 crystal microstructure of Sb2Se3 rod structure gradually submerged in the dense.Cu3SbSe4 and Sb2Se3 crystals with different proportion for photoelectric properties of materials had no significant effect on the ceramic has similar conductivity, I-V The change curve, and at the same time that the P type semiconductor and N type semiconductor photocurrent enhancement, optical density at 400 W under the condition of m-2, -0.6 V under the high light bias current density reached 50 A - cm-2. by Cu3SbSe4 to replace Cu2GeSe3 and Sb2Se3 to build micro PN heterojunction composed of Cu3SbSe4-Sb2Se3 ceramics. In successfully replaced the rare element Ge and retains the excellent optical and electrical properties of ceramic was studied. Effect of element doping on the resistivity of Sb2Se3, in which the impurity crystal phase under the condition of a small amount of 1 element doped Sb2Se3 can be 105 times lower resistivity, it has to improve the light absorption and excellent thermoelectric properties are has been of great significance to its high resistance limit. I Sb2Se3 doping affects the performance of Cu3SbSe4-Sb2Se3 system for ceramics and influence on ceramic Cu2GeSe3-Sb2Se3 system similar to that of doped Sb2Se3 Cu3SbSe4 originally interrupted conducting channel through, but because of doping enhances the conductivity of Sb2Se3, the photogenerated carriers not only through Cu3SbSe4 can also pass through the Sb2Se3 crystal, which also shows the photoelectric effect of P type and N type semiconductor.3 by hot injection method, the temperature of selenium source precursor Se-ODE injected into cationic hot solution, by controlling the reaction temperature and time, high quality single crystal CuSe nanoparticles and six dimensional nano films were prepared successfully, the synthesis process avoids the use of toxic volatile alkyl phosphonic compounds as organic solution, green environmental protection, high yield. The effects of reaction temperature, reaction time and addition of A13+ for the CuSe crystal phase, morphology and size effect of the band gap. The study found that with the prolonging of reaction time, initial nanoparticles increased gradually formed nanosheets with oriented attachment theory. The theory explains the growth process of two-dimensional nanosheets, copper selenide nanoplates through nano grain crystal surface matching, and directional aggregation. In the reaction process, the growth rate of A13+ ions by adsorption of selenium ion delay nanosheets, A13+ ion in the condition of copper selenide nano particles in the reaction temperature 180 DEG C only needs 10 minutes for the growth of nanosheets. Through the preparation of near infrared optical absorption adjustable copper selenide nano materials can control the reaction time can be prepared according to the target application of semiconductor band gap, greatly expanded the application of.4 copper selenide in the near infrared spectral range, using Cu3SbSe4 nanoparticles were prepared into nano particles. The study found that having a single crystal and presents a spherical structure of monodisperse. By controlling the reaction temperature and time, the average size of nano particles in the 15 nm (0 Minutes) to 110 nm (60 minutes). The adjustment between Cu3SbSe4 nanoparticles as raw materials for the preparation of bulk thermoelectric materials, compared with conventional Cu3SbSe thermoelectric materials prepared by solid state reaction, thermoelectric materials with Cu3SbSe4 nano particle preparation can effectively reduce the increase of grain size, grain boundary scattering, thus effectively reducing the thermal conductivity. Study on the effect of Sn doping on properties of Cu3SbSe4 thermoelectric materials, Sn doping can significantly improve the electrical conductivity, thermal conductivity of Cu3SbSe4 thermoelectric materials with nano particles were prepared by a low rate, both increase the power factor, using Cu3Sb0.98Sn0.02Se4 nano particles as raw material, prepared by hot pressing sintering bulk thermoelectric materials in 575 K, ZT value reached 0.50.

【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：TN304

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