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研究生：	艾淑華 Pancorowati, Dhita Azzahra
論文名稱：	無聚合物轉印法以提升石墨烯品質 Increasing Quality of Graphene by Improved Polymer-Free Transfer
指導教授：	謝馬利歐 Mario Hofmann
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2017
畢業學年度：	105
語文別：	英文
論文頁數：	80
外文關鍵詞：	CVD graphene, graphene transfer, polymer-free transfer, cleaning first method, cleaning after method, mobility
相關次數：	點閱：74 下載：2
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We have been work with Chemical Vapor Deposition (CVD) graphene. We have carried out the different method to transfer graphene from copper foil to target substrate with improved transfer polymer-free method. In this thesis we explain in two different method; cleaning first method and cleaning after method. Both of two methods we do it polymer-free, it is mean that we do transfer process without polymer support. The purpose of polymer-free transfer is because due to previous study about transfer graphene they have said that PMMA is kind of hard to remove from graphene, and the residue of PMMA may change the electrical and electrochemical properties of the graphene. In these thesis we will explain about the transfer method and the result from several characterization. The result is, even we do polymer-free transfer it seems that the graphene still have some contamination from the etchant such as Cu, Cl, O and S. Cleaning after method can decrease the residue on graphene but the residue not completely removed from there. We have been analyze the electrical properties of PMMA transfer graphene and polymer-free transfer graphene, and the result is the mobility of hole and electron from polymer-free transfer graphene higher than from PMMA transfer graphene. We do etching process with several etchant and the best etchant is CuSO4 with cleaning after method, it is show us continuous and cleaner graphene layer compare with the other etchants, Raman spectra with no D band, have less residue and highest C content, also have highest electron and hole mobility.

TABLE OF CONTENTS

ABSTRACT………………………………………………………………………………..…...…I
ACKNOWLEDGEMENTS………………………………………………………………….…...II
TABLE OF CONTENTS………………………………………………………………………...III
LIST OF TABLES……………………………………………………………………...………...V
LIST OF FIGURES………………………………………………………………………………VI
CHAPTER ONE INTRODUCTION……………………………………………………………...1
	1.1 Overview of Graphene………………………………………………………………1
	1.2 Motivation of Research………………………………………………………...........2
CHAPTER TWO LITERATURE REVIEW………………………………………………………4
	2.1 Graphene Synthesis…………………………………………………………………4
	2.1.1 Liquid Phase and Thermal Exfoliation Graphene…………………………………5
	2.1.2 Chemical Vapor Deposition……………………………………………………….6
	2.1.3 Graphene Synthesis on Silicon Carbide……………………………………...........8
	2.1.4 Mechanical Exfoliation Graphene………………………………………………...9
	2.2 Graphene Transfer Process…………………………………………………...........12
	2.3 Raman Spectra of Graphene……………………………………………………….14
	2.4 Electrical and Mechanical Properties………………………………………………17
CHAPTER THREE EXPERIMENTAL METHOD……………………………………..............20
	3.1 Preparation………………………………………………………………………...20
	3.2 Polymer-Free Transfer……………………………………………………………..20
	3.2.1 Cleaning First Method…………………………………………………………...20
	3.2.2 Cleaning After Method…………………………………………………………..23
	3.3 PMMA Transfer…………………………………………………………………...24
	3.4 Materials Characterization…………………………………………………………25
	3.4.1 Optical Microscope (OM)………………………………………………………..25
	3.4.2 Raman Spectroscopy…………………………………………………………….26
	3.4.3 Secondary Ion Mass Spectrometry (SIMS)………………………………………27
	3.4.4 I-V Measurement…………………………………………………………...........28
CHAPTER FOUR THE ETCHING BEHAVIOR………………………………………………..30
	4.1 Transfer Graphene with PMMA Support…………………………………………..30
	4.2 Etching Behavior…………………………………………………………………..31
CHAPTER FIVE CLEANING FIRST METHOD……………………………………………….39
	5.1 Optical Microscope Analyze………………………………………………………39
	5.2 Raman Spectra Analyze……………………………………………………………43
	5.3 Secondary Ion Mass Spectroscopy Analyze……………………………………….45
	5.4 Result of Cleaning First Method……………………………………………...........50
CHAPTER SIX CLEANING AFTER METHOD………………………………………………..51
	6.1 Optical Microscope Analyze………………………………………………………51
	6.2 Raman Spectra Analyze……………………………………………………………57
	6.3 Secondary Ion Mass Spectroscopy Analyze………………………………………60
	6.4 Comparison Cleaning First Method and Cleaning After Method…………………64
	6.5 Result of Cleaning After Method………………………………………………….66
CHAPTER SEVEN FIELD EFFECT TRANSISTOR (FET) DEVICE…………………………..67
	7.1 I-V Measurement for Field Effect Transistor (FET) Device………………………67
	7.2 Best Condition for Transfer Process……………………………………………….71
CHAPTER EIGHT CONCLUSION……………………………………………………………..73
REFERENCES…………………………………………………………………………..............75
 
LIST OF TABLES

Table 2.1 Properties of graphene obtained by different method…………………………….11
Table 4.1 Result of several etchant………………………………………………………….31
Table 7.1 Data of electron and hole mobility from FET device……………………………..69
 
LIST OF FIGURES

Figure 1.1 The structure of monolayer graphene, multilayer graphene, carbon nanotube and buckyball………………………………………………………………………………2
Figure 2.1 Several method of mass-production of graphene, which allow a wide choice in term of size, quality and price………………………………………………………………….5
Figure 2.2 Diagram of CVD growth on copper……………………………………………………7
Figure 2.3 Adhesive “Scotch” tape after being pressed to the HOPG and folded over several times upon itself…………………………………………………………………………….11
Figure 2.4 Schematic diagram for graphene transfer process…………………………………….14
Figure 2.5 Example spectra of a graphene flake. (a) A pristine flake showing only G, 2D and 2D’ bands. (b) A damagedflake, which shows the D and D’ bands as well as their combination D+D’…………………………………………………………………...16
Figure 2.6 Spectra of the Raman 2D band (a) Single layer graphene (b) Bilayer graphene (c) Graphite…………………………………………………………………....................17
Figure 2.7 π bonds and sp2 hybridized orbitals in graphene………………………………………18
Figure 3.1 Process of cleaning first method………………………………………………………22
Figure 3.2 Robot transfer (1) Sample holder (2) Robot’s arms (3) Circuit of the robot………….23
Figure 3.3 Scheme process of cleaning after method…………………………………………….24
Figure 3.4 Principle of SIMS measurement………………………………………………………27
Figure 3.5 Structure of FET sample, left side is before gold deposition process and the right is after gold deposition process………………………………………………………………29
Figure 4.1 Relation between concentration of etchant and etching time…………………………38
Figure 5.1 Optical microscope (OM) picture of graphene etching by FeCl3 + DI water…………39
Figure 5.2 Optical microscope (OM) picture of graphene etching by APS………………………40
Figure 5.3 Optical microscope (OM) picture of graphene etching by CuCl + HCl………………41
Figure 5.4 Optical Microscope (OM) picture of graphene etching by CuSO4 + HCl…………….42
Figure 5.5 Graphic of Raman spectrum (a) Raman spectrum of graphene etching by FeCl3. (b) Raman spectrum of graphene etching by CuCl. (c) Raman spectrum of graphene etching by CuSO4…………………………………………………………………….45
Figure 5.6 SIMS result of graphene etch by CuCl + HCl on cleaning first method………………47
Figure 5.7 (a) Cu residue for each etchant (b) Cl residue for each etchant (c) S residue for each etchant (d) C contents for each etchant on cleaning first method…………………….49
Figure 5.8 Sample structure according to SIMS result……………………………………………50
Figure 6.1 (a) Optical miscroscope image of graphene etching by CuSO4 + HCl 2M before cleaning (b) Optical microscope image of graphene etching by CuCl + HCl 2M after cleaning with H2O2 + HCl……………………………………………………………………...52
Figure 6.2 (a) Optical microscope image of graphene etching by CuCl + HCl 2M before cleaning (b) Optical microscope image of graphene etching by CuCl + HCl 2M after cleaning with H2O2…………………………………………………..………………………...53
Figure 6.3 (a) Optical microscope image of graphene etching by CuCl + HCl 2M before cleaning (b) Optical microscope image of graphene etching by CuCl + HCl 2M after cleaning with HCl 3M for 3 hours…………………………………………………………….. 54
Figure 6.4 (a) Optical microscope image of graphene etching by FeCl3 before cleaning (b) Optical microscope image of graphene etching by FeCl3 after cleaning with HCl 3M for 2 hours………………………………………………………..………………………...55
Figure 6.5 (a) Optical microscope image of graphene etching by FeCl3 before cleaning (b) Optical microscope image of graphene etching by FeCl3 after cleaning with APS for 1 hour (c) Optical microscope image of graphene etching by CuCl + HCl 2M before cleaning (d) Optical microscope image of graphene etching by CuCl + HCL 2M after cleaning with APS for 1 hour………………………………………………………………………..56
Figure 6.6 (a) Optical microscope image of graphene etching by CuCl + HCl 2M before cleaning (b) Optical microscope image of graphene etching by CuCl + HCl 2M after cleaning with aqua regia (HCl + HNO3 3:1) for 1 hour…………………………………………58
Figure 6.7 Graph of Raman spectra (a) Graphene etch with CuCl + HCl and then clean with H2O2 (b) Graphene etch with CuCl + HCl and then clean with H2O2 + HCl……………….59
Figure 6.8 Graph of Raman spectra (a) Graphene etch with CuSO4 + HCl and then clean with H2O2 (b) Graphene etch with CuSO4 + HCl and then clean with H2O2 + HCl…………………………………………………………………………...............60
Figure 6.9 (a) Cu resdue for each etchant (b) Cl residue each etchant (c) S residue for each etchant (d) C contents for each etchant on cleaning after method…………………………….63
Figure 6.10 Comparison of residue on graphene etch by CuSO4 with cleaning firs method and cleaning after method (a) Cl residue (b) Cu residue (c) C contents…………………..65
Figure 7.1 (a) FET result from graphene etch by CuCl + HCl (b) FET result from graphene etch by CuSO4 + HCl (c) FET result from graphene PMMA transfer method………………………………………………………………………………..69
Figure 7.2 The difference of O content on graphene from different etchant……………………..70
Figure 7.3 The difference of Cu content on graphene from different etchant…………………….71 
                                    

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