石墨烯具有优异的物理化学性质，自2004年成功分离以来，它成为继富勒 烯、碳纳米管等碳基材料之后的明星材料,在材料科学与凝聚态物理学领域获得广 泛关注，展现出丰富的物理现象及广阔应用前景。同时，石墨烯的发现也打破了 之前二维材料无法单独存在的理论预言，引领了二硫化钼、六方氮化硼、单层锡、 黑磷、硅烯、锗烯等二维材料的研究热潮。 化学气相沉积法（CVD）生长石墨烯具有生长面积大、结晶质量好、成本低 廉、容易转移到其他基底材料上等优点，而备受关注。本论文利用自制CVD系 统，以铜箔为基底生长石墨烯及掺杂（同位素掺杂、氮掺杂）石墨烯，通过同位素 标定技术研究其生长机理，并利用微区...Graphene, isolated 2004 by Andre Geim and Konstantin Novoselov, is a rising star n material and basic physics reserch community for its extraordinary properies. It has a broad applications in integrated circuits, radio frequency transistor, composite materials, transparent conducting electrodes and energy storage. This dissertation has studied the mechanism of CVD synthesis method and provides an...学位：理学博士院系专业：物理与机电工程学院_凝聚态物理学号：1982012015390

张灿坤

Xiamen University Institutional Repository

????? 10384 ??? ?? ?????19820120153901 UDC? ? ? ? ? ??????????????The study of large-area graphene growth and doping?????????: ??? ??? ? ? ?: ???????????: 2015 ? 4 ???????: 2015 ? 7 ???????: 2015 ? ????????: ????????:2015 ? 4 ?厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????? ??????????????? ?????????????????? ?????????????????????????????????????????????????????????????? ? ?厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????? ? 1. ???????????????????????? ? ??????????????? X ? 2. ???????????????????????X ????????????????????????????????????????????????????????????????????????????????????????????????????? ? ?厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库? ????????????????? 2004 ????????????????????????????????, ???????????????????????????????????????????????????????????????????????????????????????????????????????????????????CVD?????????????????????????????????????????????????????? CVD ????????????????????????????????????????????????????????????????????X ????????XPS????????????????????????????????????????????CVD ????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????I厦门大学博硕士论文摘要库????????????13C ?????????????????????????????????????????????????????????13C ??? 1% ?? 50%??????????????13C ????? 50% ?? 99%????????????????????????????????????????????????????????????????????????? 50%??iTO ???????? 15.3 ps ? 0.72 ps??????????????????????????????????????????????????? p ?? n ????????????????????????????????????????urea:CH4N2O?????CH4????????????? CVD?????????????????????????, ?????????????????????????????????????????????????????????????? 3.72atom%???????????????????XPS ??????????????????????????????????????????????????????????????????????????????????????? ID/ID0 ?? 1.2???????????????????????????? n ????????????? -52.9 V?????????? 74.1cm2/Vs??????????????? ??????????????????????????II厦门大学博硕士论文摘要库AbstractGraphene, isolated 2004 by Andre Geim and Konstantin Novoselov, is a rising starin material and basic physics reserch community for its extraordinary properies. Ithas a broad applications in integrated circuits, radio frequency transistor, compositematerials, transparent conducting electrodes and energy storage. This dissertationhas studied the mechanism of CVD synthesis method and provides an eﬀective low-cost synthesis and in-depth mechanistic study for high quality large-area nitrogen-doped graphene(NG) ﬁlms.We used Cu pockets to create diﬀerent environments between the inner sideand the outer side of a same piece of Cu foil for graphene growth. Comparingthe graphene grown on the inner side and that grown on the outer side of the Cupocket, we found that carbon atoms would diﬀuse through the 25 micrometer-thickCu foil and reach the interface between the Cu and the pre-grown graphene layer,which feeds the graphene layers growing under the top layer(s). We obtained bilayergraphene with a coverage of about 78% for the outer side of the Cu pocket with theassistance of a surface-mediated graphene growth process and a carbon penetration-based growth process.We found that with the existence of Stone-Wales defect at the graphene bound-aries, the copper foil and graphene became a galvanic cell with the copper cathodeand the graphene anode in humidity condition. As a result copper oxidized muchmore at the graphene boundaries. So in humidity condition, graphene is not goodas a oxidation-resistance for copper.We used Graphene oxide (G-O) ﬂakes to seed the growth of single crystal grapheneislands by chemical vapor deposition (CVD) on Cu foil. Such islands have the G-Oseed (which converts to a ?reduced graphene oxide?(rG-O) seed due to the CVDIII厦门大学博硕士论文摘要库????????growth conditions used) roughly in the center of the islands. The lateral growthof such single crystal graphene islands was studied by carbon isotope labeling andRaman spectroscopy, scanning and transmission electron microscopy and selectedarea electron diﬀraction. By changing the concentration of G-O in the aqueousdispersion used to deposit the G-O ﬂakes onto the Cu foil by dip-coating, the size ofthe seeded graphene islands could be precisely controlled on the Cu foil. The crystalorientation of the single crystal graphene islands was found to be identical to thatof the G-O seeds.We synthesized isotope labeled graphene with the concentration of 13C carbonatom of 1%, 25%, 50%, 75% and 99%. The isotope eﬀect on the phonon behavior ingraphene was investigated based on the micro-Raman analysis of 13C isotope labeledgraphene samples. We found that the phonon scattering was aﬀected by the isotopiccarbon atom as a point defect. Based on the experiment results, the lifetime of iTOphonons were estimated, which agreed with other theoretical calculations.We also provides an eﬀective low-cost synthesis and in-depth mechanistic studyfor high quality large-area nitrogen-doped graphene(NG) ﬁlms. These ﬁlms weresynthesized using urea as nitrogen source and methane as carbon source, andwere characterized by SEM, Raman spectroscopy and X- ray photoelectron spec-troscopy(XPS). The N doping level was 3.72 at. %, and N atoms were suggestedto mainly form a pyrrolic N conﬁguration. All distinct Raman peaks display blueshift due to the nitrogen-doping and compressive strain. And the increase of ni-trogen concentration broadens the D and 2D peak?s FWHM, due to the decreaseof mean free path of phonon. The N-doped graphene exhibited an n-type dopingbehavior with a considerably high carrier mobility of about 74.1 cm2/Vs, conﬁrmedby electrical transport measurements.Keywords: Graphene; Chemical vapor deposition; Isotope labeling; N-dopedgraphene; Raman spectraIV厦门大学博硕士论文摘要库? ?? ? I???? III? ? V???? VIIII ???????????????? 1??? ?? 21.1 ????????? . . . . . . . . . . . . . . . . . . . . . . . . . . . 21.2 ????????? . . . . . . . . . . . . . . . . . . . . . . . . . . . 31.2.1 ????????????? . . . . . . . . . . . . . . . . . . 41.2.2 ?????? . . . . . . . . . . . . . . . . . . . . . . . . . . . 61.3 ??????????? . . . . . . . . . . . . . . . . . . . . . . . . 9??? ??????????? 102.1 ???????? . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102.1.1 ????? . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102.1.2 ???????? . . . . . . . . . . . . . . . . . . . . . . . . 112.1.3 ????????? . . . . . . . . . . . . . . . . . . . . . . . 122.1.4 ??????? . . . . . . . . . . . . . . . . . . . . . . . . . 132.1.5 ?????? . . . . . . . . . . . . . . . . . . . . . . . . . . . 162.2 ?????? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192.2.1 ????? . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19V厦门大学博硕士论文摘要库????????2.2.2 ??????? . . . . . . . . . . . . . . . . . . . . . . . . . 212.2.3 ?????? . . . . . . . . . . . . . . . . . . . . . . . . . . . 222.2.4 ???????? . . . . . . . . . . . . . . . . . . . . . . . . 242.2.5 X ??????? . . . . . . . . . . . . . . . . . . . . . . . . 28II ?????????????? 31??? ?? CVD?????????? 323.1 ?? CVD?????????? . . . . . . . . . . . . . . . . . . . . 343.1.1 ???????? . . . . . . . . . . . . . . . . . . . . . . . . 343.1.2 ??????????? . . . . . . . . . . . . . . . . . . . . 353.2 ?? CVD???????? . . . . . . . . . . . . . . . . . . . . . . 383.2.1 ??????????????????????????? 383.2.2 ????????????????????????CVD???? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393.2.3 ????????????????????????????? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413.3 ?? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45??? ????????? -??????? 474.1 ???? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484.2 ?????? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 494.3 ?? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50??? ???????????? 525.1 ????????? . . . . . . . . . . . . . . . . . . . . . . . . . . . 555.2 ?? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57VI厦门大学博硕士论文摘要库? ?III ????????????? 59??? ????????????????? 606.1 ???? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606.2 ????? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616.2.1 ???????? . . . . . . . . . . . . . . . . . . . . . . . . 616.2.2 ????????? . . . . . . . . . . . . . . . . . . . . . . . 636.2.3 ???????? . . . . . . . . . . . . . . . . . . . . . . . . 666.3 ?? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72??? ??????????????? 747.1 ???????? . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777.1.1 ?????????? . . . . . . . . . . . . . . . . . . . . . 777.1.2 ????????????? . . . . . . . . . . . . . . . . . . 787.1.3 ????????? . . . . . . . . . . . . . . . . . . . . . . . 787.2 ???????????????????? . . . . . . . . . . . . . 827.2.1 ??????? . . . . . . . . . . . . . . . . . . . . . . . . . 837.2.2 ???? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837.3 ?? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95IV ????? 96??? ????? 97???? 99????????? 114? ? 116VII厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库ContentsAbstract IIIContents VIIIChapter 1 Introduction 21.1 Brief introduction of graphene . . . . . . . . . . . . . . . . . . . . 21.2 Structure and properties of graphene . . . . . . . . . . . . . . . . 31.2.1 Lattice and energy band structure of graphene . . . . . . . . . 41.2.2 The properties of graphene . . . . . . . . . . . . . . . . . . . 61.3 Significance and Content . . . . . . . . . . . . . . . . . . . . . . . 9Chapter 2 Growth and characterizations of graphene 102.1 Growth of graphene . . . . . . . . . . . . . . . . . . . . . . . . . . 102.1.1 Mechanical exfoliation . . . . . . . . . . . . . . . . . . . . . . 102.1.2 Thermal decomposition of SiC . . . . . . . . . . . . . . . . . . 112.1.3 Chemical synthesis method . . . . . . . . . . . . . . . . . . . 122.1.4 Chemical vapor deposition . . . . . . . . . . . . . . . . . . . . 132.1.5 Transfer of graphene . . . . . . . . . . . . . . . . . . . . . . . 162.2 Characterization of graphene . . . . . . . . . . . . . . . . . . . . . 192.2.1 Optical microscope (OM) . . . . . . . . . . . . . . . . . . . . 192.2.2 Scanning electron microscope (SEM) . . . . . . . . . . . . . . 212.2.3 Atomic force microscope (AFM) . . . . . . . . . . . . . . . . 222.2.4 Confocal raman spectrometer . . . . . . . . . . . . . . . . . . 242.2.5 X-ray photoelectron spectroscopy (XPS) . . . . . . . . . . . . 28Chapter 3 The study of Mechanism of CVD grpahene growthVIII厦门大学博硕士论文摘要库Contentson copper foil 323.1 Process of controlable CVD growth of graphene on coppersubstrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343.1.1 General process of graphene growth . . . . . . . . . . . . . . . 343.1.2 Process of isotopic graphene growth . . . . . . . . . . . . . . 353.2 Mechanism of CVD grpahene growth on copper foil . . . . . . . 383.2.1 Self-limited mechanism . . . . . . . . . . . . . . . . . . . . . . 383.2.2 Nano-CVD chamber mechanism . . . . . . . . . . . . . . . . . 393.2.3 Diﬀusion across copper foil mechanism . . . . . . . . . . . . . 413.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45Chapter 4 Seeding growth of graphene 474.1 Process of seeding growth . . . . . . . . . . . . . . . . . . . . . . 484.2 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . 494.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50Chapter 5 Graphene on copper and its corrosion resistanceproperty 525.1 Results and discussions . . . . . . . . . . . . . . . . . . . . . . . 555.2 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57Chapter 6 Growth and phonon behaviors of isotope labeledgraphene 606.1 Experimental process . . . . . . . . . . . . . . . . . . . . . . . . . 606.2 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . 616.2.1 Raman spectra of 13C labeled graphene . . . . . . . . . . . . . 616.2.2 FWHM mapping of graphene . . . . . . . . . . . . . . . . . . 636.2.3 Full width at half maximum of graphene raman spectra . . . . 666.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72IX厦门大学博硕士论文摘要库   Degree papers are in the “Xiamen University Electronic Theses and Dissertations Database”.  Fulltexts are available in the following ways: 1. If your library is a CALIS member libraries, please log on http://etd.calis.edu.cn/ and submit requests online, or consult the interlibrary loan department in your library. 2. For users of non-CALIS member libraries, please mail to etd@xmu.edu.cn for delivery details. 厦门大学博硕士论文摘要库

The study of large-area graphene growth and doping

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The study of large-area graphene growth and doping

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