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題名: 以溶膠凝膠法製作ZnO:Me (Me=Al and Cu)透明薄膜特性之研究
Investigation on the characteristics of ZnO:Me (Me=Al and Cu) transparent films fabricated by Sol-Gel method
作者: 林弘軒
貢獻者: 電機工程研究所
關鍵詞: 氧化鋅
溶膠凝膠法
X-ray繞射
紫外光-可見光-近紅外線分光光譜
螢光光譜
可變範圍躍遷
日期: 2013-06
上傳時間: 2013-11-18T08:19:40Z
摘要: 本篇論文主要是研究利用溶膠凝膠法(Sol-gel method)加上旋轉塗佈技術在玻璃基板上製作摻雜鋁氧化鋅(Zn1-xAlxO)與摻雜銅氧化鋅(Zn1-xCuxO)的透明導電薄膜，分別探討薄膜在不同的燒結溫度以及不同摻雜比例元素的情況下，對氧化鋅薄膜特性的影響。
製備的薄膜利用X-ray繞射的結果來分析其晶格結構及其晶粒大小，結果顯示製作的Zn1-xAlxO、Zn1-xCuxO的透明薄膜皆為六角纖鋅礦結構，且薄膜結晶成相皆有很高的c軸取向，並且沒有二次相的產生。接著利用Debye-Scherrer’s 方程式代入X-ray繞射的數值以計算其晶粒的大小來做比較。由結果來看，晶粒尺寸隨鋁與銅的摻雜濃度與燒結溫度的增加而增加，同時也會影響其後續所量測之特性。製備的薄膜利用掃描式電子顯微鏡來觀察其表面特性，樣品表面為多孔性的奈米結晶型態，其晶粒尺寸變化的結果能與X-ray互相呼應。
製備的薄膜利用紫外光-可見光-近紅外線分光光譜儀(UV-VIS-NIR spectrometers)量測穿透率，結果顯示製作的Zn1-xAlxO與Zn1-xCuxO薄膜在可見光波長範圍的穿透率皆可到達80%以上。再利用(αhv)2對光子能量圖利用外插法來求出能隙，結果發現能隙皆隨燒結溫度增加而增加，隨鋁摻雜濃度增加而增加，但隨銅摻雜摻雜濃度增加而減小。利用螢光光譜量測，在紫外光區段皆可以觀察到一個明顯的繞射峰，且有摻雜的樣品會在可見光區觀察到一個由薄膜缺陷造成的微弱放射峰。結果顯示鋁摻雜會減少缺陷螢光光譜量測，且有摻雜的樣品會在綠光區(約520nm)及橘光區(約600nm)可觀察到一個明顯的放射峰，但銅摻雜會增加缺陷濃度。
最後對薄膜進行變溫電性量測，所有薄膜皆呈現半導體特性。藉由Arrhenius plot，在室溫時顯示樣品主要的載子傳導機制是熱活化形式(activation type)，而在低溫時載子的傳導機制主要為可變範圍躍遷(variable range hopping，VRH)。
In the thesis, the Zn1-xAlxO and Zn1-xCuxO transparent nanocrystalline thin films had been grown on glass substrates by sol-gel method with spin coating technique. The structural morphology, optical and electrical properties of the transparent thin films annealed at various temperatures and doping concentrations had been investigated.
Examined by X-ray diffraction measurement, all transparent thin films exhibits the wurtzite structure with a preferential orientation along the c-axis, and on secondary phase has been found. The grain size and the corresponding characteristics of the films are affected by the doping of Al and Cu. By the Debye-Scherrer’s equation, the grain size of the films decreases with the increase of doping concentration and annealing temperature. By the observation of scanning electron microscopy images, the morphology of the films reveals porous granular surface for all sample. There increase of grain size with the increase of doping concentration and annealing temperature in consistent with the results of X-ray diffraction measurement.
The optical transmittance spectra of the films have been measured by using the UV-VIS-NIR spectrometers. The average optical transmittance value of Zn1-xAlxO and Zn1-xCuxO thin films were above 80% in the visible range. From the plot of (αhυ)2 versus photon energy of the films, the energy gap of the films increase with the increase of annealing temperature and Al doping concentration, but decrease with increase of Cu doping concentration. Photoluminescence spectra of the films deposited with various doped concentration and annealing temperature had been measured. All samples have two modes of emission peaks at UV and visible light emissions. For the undoped ZnO thin film, the UV emission peak is equal to the ZnO energy gap, which intensity decrease with the increase of doped concentration. And the visible light emission peak intensity was increase with the increase of Cu doping concentration, but increase with the increase of Cu doping concentration.
Temperature dependence of resistance of all samples reveals the semiconductor transport behavior. At room temperature region, the carrier transport mechanism can be fitted well with the behavior of activation type. At low temperature region, the resistance can be fitted well with the behavior of variable range hopping, ρ(T)= ρnexp[(T*/T)n].
描述: 指導教授:楊尚霖
顯示於類別:[電機工程系(含碩士班)] 學位論文

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