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博碩士論文 etd-0721117-105123 詳細資訊
Title page for etd-0721117-105123
論文名稱
Title
電化學技術製備石墨烯(石墨烯氧化物)材料應用於電子場發射發光元件特性之研究
Electrochemical preparation of graphene (graphene oxide) materials applied to electron field emission on characteristics of luminous device
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
167
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2017-07-22
繳交日期
Date of Submission
2017-09-09
關鍵字
Keywords
表面形態、坑反射層、氧化石墨烯、電化學剝離、電泳、屏蔽效應、場發射
anti-reflective layer, electrophoretic, screening effect, field emission, surface morphology, graphene oxide, electrochemical exfoliation
統計
Statistics
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The thesis/dissertation has been browsed 5772 times, has been downloaded 25 times.
中文摘要
石墨烯由於具有輕薄、導電性佳與獨特性能帶結構的神奇材質,加上僅有單層原子的厚度,因此這種材料自2004年被A.K. Geim 等人發現之後,便因而引起許多研究團隊熱衷熱門材料,並將其廣泛應用在電晶體、透明電極、觸控面板、複合材料、儲能材料、感測器等研究領域上。本論文主要有三大部分,第一個主題利用電化學剝離法製備石墨烯(石墨烯氧化物)材料及其材料特性的分析和探討。同時改進低缺陷結構的石墨烯氧化物,使石墨烯氧化物能由完美晶格的石墨塊所剝離下來,在劇烈的氧化過程中,能降低嚴重的破壞其晶格結構。第二部分以還原石墨烯氧化物材料作為發射源以平面滴塗和透過網印等兩種方式將還原石墨烯氧化物製成平面和矩形島狀的電子場發射元件之電子場發射,分析這兩種方法並比較其優劣,並探討各種場發射特性和發光照度與光譜量測。第三部分利用電泳在不同基板上沉積石墨烯薄膜並探討其特性與光學性質。以下介紹三個主題之製程與結果。
第一個主題,電化學製備石墨烯(石墨烯氧化物)材料及降低缺陷比ID/IG值
本實驗以高定向熱解石墨 (highly oriented pyrolytic graphite) 為材料,利用快速、簡單的電化學剝離方式製備石墨烯(石墨氧化物)。改變不同參數電解溶液濃度及嵌入電壓,以求高品質低缺陷比(ID/IG) 石墨烯(石墨氧化物和還原石墨氧化物)。製備完成後的石墨烯材料以拉曼光譜儀、X光繞射儀和X光電子能譜儀進行材料分析,拉曼光譜可迅速分析碳材料之缺陷和結構且不破壞材料晶體結構,X光繞射儀和X光電子能譜儀則分別檢測材料的晶格結構及化學鍵結、成分,以確認製備出之石墨烯(石墨氧化物和還原石墨氧化物)品質,並成功製備出最低缺陷的石墨烯,其缺陷比ID/IG值為0.5.
第二部分,電子場發射元件製作和特性量測
在進行場發射量測之前,將透過光學顯微鏡與掃描式電子顯微鏡檢視與觀測各樣品的表面形態,發現使用較低的插入電壓和1:18的電解質OH-:H+減少了缺陷的數量,而製備出的樣品有較明顯奈米結構,而加入氫氧化鉀樣品的深寬比 (aspect ratio) 、表面皺褶更為明顯。最終發現以較低缺陷比參數電化學剝離的石墨烯氧化物,在經過摻雜氫氧化鉀溶液製備後的還原石墨烯氧化物樣品所製備的樣品以平面滴塗方式的元件結構有最佳的場發射特性,其起始電場和場增強因β分別為1.95 V⁄μm及 8150。此場發射元件之光通量和光照度分別為6.02流明、180.6勒克斯。另以繪圖軟體設計不同直徑大小圖形的遮罩,進行還原石墨烯氧化物的網版印刷,發現網印後的氧化石墨烯呈島狀型態,並營造出利於場發射的垂直邊緣,具有極佳的深寬比 (Aspect ratio),整體形成矩形陣列的場發射源。在進行量測不同直徑大小的氧化石墨烯之場發射特性時,發現氧化石墨烯圖形在直徑150μm條件下有最佳的場發射特性,其起始電場 (Turn-on field)為1.53 V⁄μm,最大場發射電流為74.2μA/cm2,場增強因子β為9150,唯直徑100μm之氧化石墨烯圖形受到屏蔽效應 (Screening effect)的作用,未能有較好的場發射特性。以上兩種電子場發射元件之場發射性能相比較,以網印矩形島狀還原石墨烯氧化物陰極性能較佳。
第三部分,電泳沉積製備石墨烯簿膜摻雜金屬在不同基板上組成結構及特性影響
利用電泳在的不同基板上參雜不同金屬(銅、鋁)進行沉積非晶質銅/石墨烯(Cu-rGO),和鋁/石墨烯(Al-rGO)複合薄膜,電解液為混合醋酸或硫酸和去離子水的電解液,通過實驗分析生長的石墨烯複合膜的均勻性和表面結構,以形成具有最高質量的石墨烯簿膜。根據實驗結果,創建了最高品質的石墨烯薄膜。可以獲得最大量的石墨烯和最少的石墨烯缺陷。結果表明,沉積溫度為30℃,電壓為2.5V,電解液濃度為0.8%,反射指數降低了94.91%,理論匹配折射率為1.32。使用n&k分析儀測量薄膜。結果得出的膜的Eg值表明銅複合離子摻雜有利於膜中高度導電的Cu金屬的形成。此外,Cu-rGO共沉積過程有助於石墨化薄膜,從而產生具有低的Eg = 2.56eV的薄膜。此兩種薄膜都具有比未摻雜的簿膜更高的折射率和均勻性,其效果類似於摻雜的n型半導體中的效果。因此,非常適用於抗反射層。
Abstract
Graphene is a light material that has favorable electrical conductivity, a unique energy band structure, and minimal thickness (i.e., single atomic layer thickness). Since its discovery by Geim et al. in 2004, it has been widely studied by research teams and used in various devices such as transistors, transparent electrodes, touchscreens, composite materials, energy storage materials, and sensors. This study was divided into three parts. The first part details how graphene (graphene oxide) materials were fabricated using electrochemical stripping, further investigating and analyzing the properties of the materials. Graphene oxides with fewer defects were fabricated, so that they could be stripped off graphite blocks with a perfect crystal lattice while preventing the lattice structures from sustaining serious damage during intense oxidation. Second, reduced graphene oxide materials were utilized as emission sources, and the plane dripping and coating method and screen printing method were employed to fabricate reduced graphene oxides into rectangular island-shaped electron field emission components. The two methods were compared to identify their advantages and disadvantages, and the field emission characteristics, illuminances, and spectra of the components were investigated. Third, electrophoresis was used to deposit graphene thin films on different substrates and evaluate the general and optical properties of the substrates. Details of the three study parts are now given.
The First Subject, Preparing Graphene Materials (Using Electrochemical Stripping) and Decreasing Their Defect Ratio
In this experiment, highly oriented pyrolytic graphite was used as the material and a fast, simple electrochemical stripping method was employed to prepare graphene (graphene oxides). Two parameters (electrolytic solution concentration and embedded voltage) were adjusted to produce high-quality, low-defect-ratio (ID/IG) graphene (i.e., graphene oxides and reduced graphene oxides). Material analyses of the graphene materials were performed using Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Raman spectroscopy enabled quick analyses of carbon material defects and structures without damaging the crystal structure of the materials. X-ray diffraction enabled detections of the crystal lattice structures and chemical bonding of the material, whereas X-ray photoelectron spectroscopy facilitated analyzing the components of the material. These analyses were conducted to ensure the quality of the prepared graphene (i.e., graphene oxides and reduced graphene oxides). Finally, minimum-defect graphene with a defect ratio of 0.5 was produced.
The Second Part, Preparing Electron Field Emission Components and Measuring Their Properties
Prior to measuring field emissions, the surface morphology of each sample was examined using an optical microscope and a scanning electron microscope. The results demonstrated that the use of a low insert voltage and electrolytes with a 1:18 OH−: H+ ratio produced fewer defects and samples with a relatively more crystalline nanostructure. Adding potassium hydroxide was found to produce samples with relatively higher aspect ratios and more noticeable surface wrinkles. Graphene oxides with lower defect ratios were fabricated using electrochemical stripping. The materials were then processed to reduced graphene oxide samples using potassium hydroxide solution. The sample component structure prepared by plane dripping and coating was determined to have the optimal field emission properties. The turn-on field and field enhancement factor β of the optimal graphene oxide were 1.95 V/μm and 8150, respectively, whereas the corresponding field emission component had a luminous flux and illuminance of 6.02 lumens and 180.6 lux, respectively. Graphics software was used to design masks of varying diameters, which were used to screen print the reduced graphene oxides. The screen printed graphene oxides were island-shaped, had excellent aspect ratios and vertical edges that were conducive to field emissions, and formed a rectangular array of field emission sources. Measurements of the field emission properties of the graphene oxides with different diameters revealed that those with a diameter of 150 μm yielded the most superior field emission properties (turn-on field, maximum field emission current, and field enhancement factor β of 1.53 V/μm, 74.2 μA/cm2, and 9150, respectively). By contrast, graphene oxide components with a diameter of 100 μm had relatively poorer field emission properties because they were affected by the screening effect. A comparison of the field emission performance of these two types of electron field emission component demonstrated that the rectangular island-shaped reduced graphene oxide components (produced using screen printing) had superior cathode performance.
The Third Part, Compositions, Structures, and Properties of Graphene Thin Films (Doped with Metals and Fabricated Using Electrophoresis) on Different Substrates
Electrophoresis was used to dope two metals (copper and aluminum) on different substrates in order to deposit amorphous copper–graphene (Cu–rGO) and aluminum–graphene (Al–rGO) composite thin films. The electrolyte solutions used were deionized water mixed with acetic or sulfuric acid, and experiments were performed to analyze the homogeneity and surface structures of the graphene composite films as grown. According to the experimental results, graphene thin films of the highest quality were created. The highest amount of graphene and the lowest number of graphene defects can be obtained. The results demonstrate that a deposition temperature of 30℃, a voltage of 2.5V, and a 0.8 % electrolytic solution concentration reduced the reflection index by 94.91%, and yielded a theoretical matching refractive index of 1.32. An n&k Analyzer was used to measure the thin films. The results derived Eg values of the films indicated that copper complex ion doping are conducive to the formation of highly conductive Cu metals in the films. Furthermore, the Cu–rGO codeposition process facilitated graphitizing the thin films, thus yielding thin films with low values of Eg=2.53eV. Both thin film types had higher refractive indices and homogeneity than those of the undoped thin film and had a similar effect to that of doped n-type semiconductors. Thus, the two thin film types are excellent antireflective layers.
目次 Table of Contents
CONTNETS
論文審定書 i
ACKNOWLEDGEMNT ii
摘要 iii
Abstract v
CONTNETS ix
LIST OF FIGURES xiii
LIST OF TABLES xx
Chapter 1 Introduction and research objectives 1
1.1 Historical background of graphene 2
1.2 The preparation method of graphene 4
1.3 Application of graphene in electron field emitter devices 18
1.4 Motivation and objective of the research 28
Chapter 2 Basic principle of graphene (graphene oxide) materials 30
2.1 Graphene physical characteristic 30
2.1.1 Single graphene theory 30
2.1.2 The electronic properties of graphene 32
2.1.3 Graphene optical properties 33
2.1.4 Graphene stack structure 35
2.2 Vacuum electron emission theory 36
2.2.1 Vacuum electron emission patterns 36
2.2.2 Fowler-Nordheim theory 37
2.2.3 Major Factors Affecting Field Emission 38
2.3 Growth mechanisms of graphene thin films 39
2.3.1 Thin film deposition 39
2.3.2 Cluster growth 40
2.3.3 Grain growth 42
2.3.4. Grain clolescence 42
2.3.5. Groove filling and thin film growth 43
2.4. Electrophoretic deposition principles and methods 44
Chapter 3 Experiment 46
3.1 Preparation of graphene oxide 46
3.1.1 The pretreatment of the substrate 46
3.1.2 Electrochemical preparation of graphene oxide materials 47
3.2 Characteristic analysis of graphene (graphene oxide) and electrophoretic thin-film 48
3.2.1 Raman spectrum measurement 48
3.2.2 X-ray diffraction measurement 49
3.2.3 X-ray photoelectron spectroscopy 49
3.3 Device production process 49
3.3.1 Upper plate production (electron receiving) 49
3.3.2 Lower plate production (Emitter) 50
3.4 Field emission device measurement 53
3.4.1 Device electrical measurement 53
3.4.2 Device optical measurement 54
3.5 The experiment of field emission 54
Chapter 4 Reducing Electrochemical Exfoliated Graphene Defects by Changing the Insert Voltage and Electrolyte Composition 57
4.1. Introduction 57
4.2 Experimental 58
4.2.1 Highly oriented pyrolytic graphite electrochemical exfoliation while varying which insert voltage 58
4.2.2 Conducting HOPG electrochemical exfoliation while changing volume of KOH 59
4.3 Results and Discussion 60
4.3.1 Raman spectra of HOPG electrochemical exfoliation 61
4.3.2 XPS analysis 66
4.3.3 XRD analysis 67
4.3.4 SEM analysis 68
4.4 Summary 72
Chapter 5 Light-Emitting Illumination and Field Emission Device of potassium hydroxide-doped Electrochemically Reduced Graphene Oxide 73
5.1. Introduction 73
5.2 Experimental 75
5.2.1 Producing GO and Reduced Products 75
5.2.2 Material Analysis 75
5.2.3 Screen printing of graphene oxide 76
5.2.4 Field emission device measurement 76
5.3 Results and Discussion 79
5.3.1 Rheological viscosity analysis of GO 79
5.3.2 Raman analysis 80
5.3.3 XRD analysis 81
5.3.4 XPS analysis 81
5.3.5 Scanning electron microscopy analysis 85
5.3.6 Field Emission, Light Flux, and Illumination of the Fabricated Device 85
5.4 Summary 96
Chapter 6 Electrophoretic Deposition of Graphene Growth in Different Substrates 97
6.1. Introduction 98
6.2 Experimental 98
6.2.1 Production of Graphene 98
6.2.2 Electrophoresis 99
6.3 Results and Discussion 100
6.3.1. Electrophoretic deposition of r-GO films on the Si substrate surface morphology 100
6.3.2 Electrophoretic deposition of r-GO films on the ITO substrate surface morphology 105
6.3.3 FTIR spectra 110
6.3.4 XPS C1s spectra 111
6.3.5 Raman spectra 111
6.3.6 Reflection spectra 113
6.3.7 Mechanisms chemical reaction spectra 119
6.4 Summary 121
Chapter 7 Conclusions and future prospect 123
7.1 Conclusiouns 123
7.2 Future prospect 125
References 127
Publications 144
參考文獻 References
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