化學鍍浴沉積法製備ZnO與ZnMnO透明導電氧化物薄膜之研究

Preparation and Properties of the Zinc Oxide and Manganese-Doped Zinc Oxide by Chemical Bath Deposition

駱煒翔(Wei-Hsiang Luo)

指導教授 ： 方昭訓

國立虎尾科技大學/工程學院/材料科學與綠色能源工程研究所/碩士(2009年)

摘要

本研究主要分為兩個部分，第一部份是探討ZnO透明導電薄膜，第二部分是探討在最佳化條件的ZnO透明導電薄膜中，摻雜Mn，合成稀磁性半導體ZnMnO薄膜。

第一部份：
本研究以化學鍍浴沉積法(Chemical Bath Deposition, CBD)在康寧玻璃Eagle2000玻璃基材上製備低電阻率和高穿透率的氧化鋅(ZnO)薄膜，並探討在不同析鍍條件下對薄膜的晶體結構、導電特性、光學性質與表面形貌的影響。實驗利用霍爾量測系統(HMS)量測電性、X光繞射儀(XRD)分析晶體結構、場發射掃描式電子顯微鏡(FE-SEM)觀察表面形貌、原子力顯微鏡(AFM)分析表面粗糙度與可見光分光光譜儀(UV-Vis)量測穿透率。最佳製程參數在Ar+H2氣氛下以600oC熱處理後之薄膜，所得的最佳電阻率為2.91×10-2 Ω cm，載子濃度為7.43×1018 cm-3，電子遷移率為2.97×101 cm2/ V•sec，平均穿透率可達81.2%和能隙值為3.23 eV。研究顯示利用化學水浴沉積法，藉由仔細的調整析鍍參數，成功製備出具有低電阻和高穿透率的氧化鋅薄膜，且有潛力應用在連續式製程。

第二部份：
本研究以最佳化條件的ZnO透明導電薄膜中，摻雜Mn，合成稀磁性半導體ZnMnO薄膜，探討對ZnMnO薄膜之成分組成、晶體結構、導電特性、光學性質、表面形貌與磁性質之影響。實驗利用電子微探儀(EPMA)分析成分組成、霍爾量測系統(HMS)量測電性、X光繞射儀(XRD)分析晶體結構、場發射掃描式電子顯微鏡(FE-SEM)觀察表面形貌、原子力顯微鏡(AFM)分析表面粗糙度、可見光分光光譜儀(UV-Vis)量測穿透率與振動試樣磁力計(VSM)量測磁滯曲線。最佳製程參數摻雜Mn含量為4.02 at.%，在Ar+H2氣氛下以600oC熱處理後之薄膜，所得的最佳電阻率為5.84×10-2 Ω cm，載子濃度為1.12×1019 cm-3，電子遷移率為9.52 cm2/ V•sec，平均穿透率可達75.6%和能隙值為3.30 eV，飽和磁化量為21 emu/c.c.，剩餘磁化量為2.605 emu/c.c.，矯頑磁力為45.6979 Oe。研究顯示利用化學鍍浴沉積法，藉由摻雜Mn，成功製備出具有低電阻、高穿透率與磁性的ZnMnO薄膜，以期未來能應用於奈米尺寸自旋電子元件。

關鍵字

氧化鋅 ； 錳 ； 化學鍍浴沉積法 ； 透明導電薄膜 ； 稀磁半導體

並列摘要

The first part of this study is to discuss the properties of CBD-prepared zinc oxide films. The second part is to elucidate the properties of manganese-doped zinc oxide prepared by an optimum deposition parameter.

Zinc oxide thin films with low resistivity and high transparency were prepared on cleaned Corning Eagle2000 glass substrates by chemical bath deposition (CBD); and the effects of deposition parameters on the structural, electrical and optical properties of the films were investigated. The changes in structure, resistivity, and transmittance were studied using Hall measure system (HMS), x-ray diffraction (XRD), Field emission scanning electron mictoscope (FE-SEM), Atomic Force Microscope(AFM), and spectrophotometer (UV-Vis), respectively. The electrical and optical properties of the thin film had a resistivity of 2.91×10-2 Ωcm, transmittance of 81.2％, and bandgap energy of 3.23 eV in the visible range when the film was annealed in Ar+H2.

Manganese-Doped Zinc Oxide was prepared by an optimum deposition parameter using Chemical Bath Deposition (CBD); and the effect of manganese-doped content on the structural, electrical, optical, and magnetic properties of the film were also investigated. The electrical, optical and magnetic properties of the thin film had a resistivity of 5.84×10-2 Ωcm, transmittance of 75.6％, bandgap energy of 3.30 eV in the visible range, saturation magnetization of 21 emu/c.c., remanent magnetization of 2.605 emu/c.c., and coercivity of 45.6979 Oe when the film (Mn=4.02 at.%) was annealed in Ar+H2. The results revealed that a superior zinc-based oxide film can be prepared using chemical bath deposition by carefully adjusting the manganese-doped content, which make the process potential to be used on a roll-to-roll-process.

並列關鍵字

zinc oxide ； manganese ； chemical bath deposition ； transparent conducting oxide ； diluted magnetic semiconductor

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