銅銦硒及其摻雜化合物半導(dǎo)體薄膜的制備與研究
發(fā)布時(shí)間：2018-12-05 21:36
【摘要】：作為一種直接帶隙半導(dǎo)體,Cu In Se2具有光吸收效率高(105/cm)、可調(diào)節(jié)的光學(xué)能隙、穩(wěn)定性好、轉(zhuǎn)換效率高以及抗輻射能力強(qiáng)等優(yōu)點(diǎn),成為了國際上最具希望大規(guī)模應(yīng)用的太陽能電池吸收層而受到了廣泛關(guān)注。Cu In Se2的制備方法有濺射法,金屬預(yù)制層硒化法,電沉積和溶液法等。由于濺射法和預(yù)制層硒化法制備均需要較高的成本和較長(zhǎng)的時(shí)間,不利于大規(guī)模的工業(yè)化生產(chǎn),因此簡(jiǎn)單廉價(jià)的溶劑熱法制備Cu In Se2成為了研究的熱點(diǎn)。本文以氯化銅,氯化銦,氯化鋁,硫粉和硒粉為原材料,采用溶劑熱法和旋涂法制備Cu In Se2及其摻雜化合物粉體和薄膜,研究摻雜元素和摻雜量對(duì)粉體和薄膜的晶體結(jié)構(gòu)、表面形貌、禁帶寬度和光學(xué)透過率等的影響。使用X射線衍射儀(Panalytical X’Pert)測(cè)試其晶體結(jié)構(gòu),并通過謝樂公式計(jì)算出其晶粒尺寸。同時(shí),使用原位變溫X射線測(cè)試其在不同溫度下的晶體結(jié)構(gòu)與物相的變化。使用掃描電鏡(Hitachi,S-3400)表征粉體與薄膜的形貌,并觀察了摻雜元素種類與摻雜量對(duì)其顆粒大小的影響。使用EDAX(Genesis)表征樣品的元素組成。使用紅外光譜儀(Shimadzu,UV-3600)測(cè)試了樣品的波長(zhǎng)與透過率之間的關(guān)系,并通過Kubelka-Munk公式計(jì)算出不同摻雜量樣品的禁帶寬度,從而得出禁帶寬度與摻雜量之間的關(guān)系。實(shí)驗(yàn)發(fā)現(xiàn),隨著摻雜Al含量的提高,Cu(In1-x Alx)Se2的XRD衍射峰強(qiáng)度逐步增強(qiáng),半高寬逐步變小,通過謝樂公式計(jì)算得出其晶粒尺寸在逐漸增大,薄膜的AFM圖片也表明薄膜的表面粗糙度也逐漸增大。同時(shí),Cu(In1-x Alx)Se2薄膜的禁帶寬度也隨著摻雜量的提高而逐漸變大。而對(duì)于Cu(In1-x Alx)S2體系而言,隨著摻雜Al含量的提高,Cu(In1-x Alx)S2的XRD衍射峰強(qiáng)度逐步減弱,半高寬逐步變大,其晶粒尺寸在逐漸減小。薄膜的AFM圖片也表明薄膜的表面粗糙度逐漸減小。同時(shí),Cu(In1-x Alx)S2薄膜的禁帶寬度隨著Al摻雜量的提高而逐漸變大。原位變溫XRD測(cè)試表明Cu In Se2在500℃無氧環(huán)境下,其晶體結(jié)構(gòu)隨著溫度的升高幾乎沒有變化,當(dāng)溫度超過500℃之后,Cu In Se2則會(huì)分解為Cu Se和In2Se3。而Cu In S2則在溫度超過525℃的時(shí)候分解為Cu2S和In2S3,而Cu(In1-x Alx)Se2(x=0.1)在600℃下都非常穩(wěn)定。由此可見,熱穩(wěn)定性Cu(In1-x Alx)Se2(x=0.1)Cu In S2Cu In Se2。通過溶劑熱法制備出Cu In Se2及其摻雜化合物粉體與薄膜,對(duì)摻雜元素和摻雜量在樣品的晶體結(jié)構(gòu)、分解溫度、形貌、元素組成、透過率和禁帶寬度的影響進(jìn)行了研究,為CIS系列材料的開發(fā)與應(yīng)用提供了參考。
[Abstract]:As a direct bandgap semiconductor, Cu In Se2 has the advantages of high optical absorption efficiency (105/cm), adjustable optical gap, good stability, high conversion efficiency and strong radiation resistance. As the most promising absorber layer for solar cells in the world, the preparation methods of. Cu In Se2, such as sputtering, selenization of metal prefabricated layer, electrodeposition and solution method, have attracted much attention. The preparation of Cu In Se2 by sputtering method and prefabricated layer selenization method requires high cost and longer time, which is not conducive to large-scale industrial production. Therefore, solvothermal preparation of Cu In Se2 by simple and cheap solvothermal method has become a hot research topic. In this paper, Cu In Se2 and its doped powders and thin films were prepared by solvothermal and spin-coating methods using copper chloride, indium chloride, aluminum chloride, sulfur powder and selenium powder as raw materials. The influence of surface morphology, band gap and optical transmittance. The crystal structure was measured by X-ray diffractometer (Panalytical X'Pert), and the grain size was calculated by Xie Lecong formula. At the same time, the changes of crystal structure and phase at different temperatures were measured by in situ variable temperature X ray. Scanning electron microscopy (Hitachi,S-3400) was used to characterize the morphology of powders and films, and the effects of doping elements and doping amount on the particle size were observed. The elemental composition of the sample was characterized by EDAX (Genesis). The relationship between wavelength and transmittance of samples was measured by infrared spectrometer (Shimadzu,UV-3600), and the band gap of samples with different doping amounts was calculated by Kubelka-Munk formula, and the relationship between forbidden band width and doping amount was obtained. It is found that the intensity of XRD diffraction peak of, Cu (In1-x Alx) Se2 increases with the increase of doped Al content, and the half-maximum width decreases gradually, and the grain size increases gradually through the calculation of Xie Lecong formula. The AFM images of the films also show that the surface roughness of the films increases gradually. At the same time, the bandgap of, Cu (In1-x Alx) Se2 films increases with the increase of doping content. For Cu (In1-x Alx) S2 system, with the increase of Al content, the intensity of XRD diffraction peak of, Cu (In1-x Alx) S2 gradually decreases, the width of half maximum becomes larger, and the grain size decreases gradually. The AFM images of the films also show that the surface roughness of the films decreases gradually. At the same time, the band gap of, Cu (In1-x Alx) S2 thin films increases with the increase of Al doping amount. The in-situ temperature variation XRD test showed that the crystal structure of Cu In Se2 was almost unchanged with the increase of temperature at 500 鈩，
本文編號(hào)：2365505
[Abstract]:As a direct bandgap semiconductor, Cu In Se2 has the advantages of high optical absorption efficiency (105/cm), adjustable optical gap, good stability, high conversion efficiency and strong radiation resistance. As the most promising absorber layer for solar cells in the world, the preparation methods of. Cu In Se2, such as sputtering, selenization of metal prefabricated layer, electrodeposition and solution method, have attracted much attention. The preparation of Cu In Se2 by sputtering method and prefabricated layer selenization method requires high cost and longer time, which is not conducive to large-scale industrial production. Therefore, solvothermal preparation of Cu In Se2 by simple and cheap solvothermal method has become a hot research topic. In this paper, Cu In Se2 and its doped powders and thin films were prepared by solvothermal and spin-coating methods using copper chloride, indium chloride, aluminum chloride, sulfur powder and selenium powder as raw materials. The influence of surface morphology, band gap and optical transmittance. The crystal structure was measured by X-ray diffractometer (Panalytical X'Pert), and the grain size was calculated by Xie Lecong formula. At the same time, the changes of crystal structure and phase at different temperatures were measured by in situ variable temperature X ray. Scanning electron microscopy (Hitachi,S-3400) was used to characterize the morphology of powders and films, and the effects of doping elements and doping amount on the particle size were observed. The elemental composition of the sample was characterized by EDAX (Genesis). The relationship between wavelength and transmittance of samples was measured by infrared spectrometer (Shimadzu,UV-3600), and the band gap of samples with different doping amounts was calculated by Kubelka-Munk formula, and the relationship between forbidden band width and doping amount was obtained. It is found that the intensity of XRD diffraction peak of, Cu (In1-x Alx) Se2 increases with the increase of doped Al content, and the half-maximum width decreases gradually, and the grain size increases gradually through the calculation of Xie Lecong formula. The AFM images of the films also show that the surface roughness of the films increases gradually. At the same time, the bandgap of, Cu (In1-x Alx) Se2 films increases with the increase of doping content. For Cu (In1-x Alx) S2 system, with the increase of Al content, the intensity of XRD diffraction peak of, Cu (In1-x Alx) S2 gradually decreases, the width of half maximum becomes larger, and the grain size decreases gradually. The AFM images of the films also show that the surface roughness of the films decreases gradually. At the same time, the band gap of, Cu (In1-x Alx) S2 thin films increases with the increase of Al doping amount. The in-situ temperature variation XRD test showed that the crystal structure of Cu In Se2 was almost unchanged with the increase of temperature at 500 鈩，
本文編號(hào)：2365505
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