以常壓式有機金屬化學氣相法沉積硒化銅鋅三元化合物特性分析

Analysis and characterization of Cu-Zn-Se ternary compound by AP-MOCVD

陳宗旻(Tsung-Ming Chen)

指導教授 ： 籃山明

中原大學/工學院/電子工程研究所/碩士(2013年)

https://doi.org/10.6840/cycu201300400

摘要

Cu1-xZn1-ySe2-δ 的I-II-VI 黃銅礦結構三元化合物半導體第一次成功的利用常壓式金屬有機氣相沉積法合成。四種主要的XRD峰值(112), (220)/(204),(312)/(116), and (400), 與伴隨著的三種次要的峰值(103), (211) and (301) 在我們XRD 的實驗中發現了。特別是那些低強度的次峰值的存在，區別了閃鋅礦與黃銅礦結構的差異，形成了黃銅礦型的Cu-Zn-Se 的化合物為特色。我們也可以發現生產出的薄膜，在可見光光譜範圍中其吸收係數普遍高於3x10^4 cm-1，而在相同的光譜中可以計算出材料的能隙為2.02eV。此外，在室溫的情形下所量測的光激螢光實驗中，可以發現強大的橘光波長在1.94eV，更可以進一步說明Cu-Zn-Se 三元化合物已製備。再者，我們利用
SEM 來看剖面圖以及俯視圖，知道此化合物的膜厚為1 – 1.3μm，晶粒的大小為1 - 2.5μm，還使用了穿隧式電子顯微鏡結合能譜散佈分析儀來確認硒化銅鋅化合物的晶粒邊界情形與化學當量比，利用聚焦式電子束來製備穿
隧式電子顯微鏡的剖面圖樣品，我們把樣品做成70-80nm 的多晶膜來觀察，也利用繞射圖形來觀察其薄膜生長的情形與X 光繞射實驗來做比較，其Cu-Zn-Se三元化合物的化學當量比為Cu:Zn:(Se+O)=0.92:1.44:2.，所以黃銅礦結構的三元化合物Cu-Zn-Se在這篇論文中已經被建立了。

關鍵字

硒化銅鋅 ； 光激螢光 ； 吸收係數 ； 常壓式金屬有機氣相沉積法 ； 硒化法 ； 穿隧式電子顯微鏡 ； 能譜散佈分析儀

並列摘要

I-II-VI ternary chalcopyrite semiconductors of Cu1-xZn1-ySe2-δ(Cu-Zn-Se) were successfully fabricated by atmospheric pressure metal-organic
chemical vapor deposition method for the first time. Four major peaks of (112),(220)/(204), (312)/(116), and (400), accompanied by three minor peaks of (103),(211) and (301) were observable in the X-ray diffraction spectra. In particular,the presence of those latter low-intensity peaks featured the formation of the
chalcopyrite type Cu-Zn-Se compound. Typical absorption coefficients of the films produced were found to be higher than 3x104 cm-1 over all visible light range and from the same optical absorption spectra the energy gap of the
material was extracted to be 2.02 eV. Moreover, the photoluminescence measurement conducted at room temperature also exhibited a strong
orange-colored emission line at 1.94 eV, which further confirmed that the Cu-Zn-Se ternary compound has been prepared. In addition, the cross-sectional and top-view scanning electron microscopy images characterized the fabricated
Cu-Zn-Se compound as a polycrystalline film of thickness about 1 – 1.3μm and consisting of 1 - 2.5μm sized grains. We were used the transmission electron microscopy (TEM) to recognized the boundary condition of the grain Cu-Zn-Se and combined the Energy Dispersive Spectrometer (EDS) to analysis the stoichiometric of grain Cu-Zn-Se. A focused-ion-beam (FIB) microsampling technique was used for preparing cross-sectional TEM specimens from a TEM specimen. In addition, the cross-sectional of TEM images characterized the fabricated compound as a polycrystalline film of about 70-80nm thick. The chalcopyrite structure of CZSe is set up from TEM. The chemical composition of CZSe is about Cu:Zn:(Se+O)=0.92:1.44:2.

並列關鍵字

selenization ； EDS ； TEM ； absorption ； atmospheric pressure metal-organic chemical vapor deposition ； Cu-Zn-Se ； photoluminescence

參考文獻

[2] T. Wada, H. Kinoshita, S. Kawata, Thin Solid Films, 431-432 (2003), 11-15.

[6] D.P. Joseph and C. Venkateswaran, Phys. Status Solidi A, 207 (2010), 2549-2552.

[7] D.P. Joseph, S. Ganesan, M. Kovendhan, S.A. Suthanthiraraj, P. Maruthamuthu, and C. Venkateswaran, Phys. Status Solidi A, 208 (2011), 2215-2219.

[9] D.A. Neamen, Semiconductor Physics And Devices, third ed., McGraw-Hill, New York, 2002.

[11] Q. Peng, Y. Dong, and Y. Li, Angew. Chem. Int. Edit., 42 (2003), 3027-3030.