ZhongFan Liu

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Name: 刘忠范; ZhongFan Liu
Organization: Peking University
Department: Center for Nanochemistry, Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering
Title: Professor

TOPICS

Co-reporter:Xin Gao, Huaying Ren, Jingyuan Zhou, Ran Du, Chen Yin, Rong Liu, Hailin Peng, Lianming Tong, Zhongfan Liu, and Jin Zhang
Chemistry of Materials July 25, 2017 Volume 29(Issue 14) pp:5777-5777
Publication Date(Web):June 27, 2017
DOI:10.1021/acs.chemmater.7b01838
Co-reporter:Yuanchang Li;Yue Qi;Nannan Han;Zhepeng Zhang;Xiebo Zhou;Bing Deng;Qiucheng Li;Mengxi Liu;Jijun Zhao;Yanfeng Zhang
ACS Nano February 28, 2017 Volume 11(Issue 2) pp:1807-1815
Publication Date(Web):January 21, 2017
DOI:10.1021/acsnano.6b07773
Hetero-epitaxial growth of hexagonal boron nitride (h-BN) from the edges of graphene domains or vice versa has been widely observed during synthesis of in-plane heterostructures of h-BN-G on Rh(111), Ir(111), and even Cu foil. We report that on a strongly coupled Re(0001) substrate via a similar two-step sequential growth strategy, h-BN preferably nucleated on the edges of Re(0001) steps rather than on the edges of existing graphene domains. Statistically, one-third of the domain boundaries of graphene and h-BN were patched seamlessly, and the others were characterized by obvious “defect lines” when the total coverage approached a full monolayer. This imperfect merging behavior can be explained by translational misalignment and lattice mismatch of the resulting separated component domains. According to density functional theory calculations, this coexisting patching and non-patching growth behavior was radically mediated by the strong adlayer–substrate (A–S) interactions, as well as the disparate formation energies of the attachment of B–N pairs or B–N lines along the edges of the Re(0001) steps versus the graphene domains. This work will be of fundamental significance for the controllable synthesis of in-plane heterostructures constructed from two-dimensional layered materials with consideration of A–S interactions.Keywords: edges of Re steps and graphene domains; graphene and hexagonal boron nitride heterostructures; preferable nucleation; ultra-high-vacuum scanning tunneling microscopy/spectroscopy;
Co-reporter:Jingyu Sun, Zhaolong Chen, Long Yuan, Yubin Chen, Jing Ning, Shuwei Liu, Donglin Ma, Xiuju Song, Manish K. Priydarshi, Alicja Bachmatiuk, Mark H. Rümmeli, Tianbao Ma, Linjie Zhi, Libai Huang, Yanfeng Zhang, and Zhongfan Liu
ACS Nano December 27, 2016 Volume 10(Issue 12) pp:
Publication Date(Web):November 22, 2016
DOI:10.1021/acsnano.6b06066
In this work, we report the transfer-free measurement of carrier dynamics and transport of direct chemical vapor deposition (CVD) grown graphene on glass with the aid of ultrafast transient absorption microscopy (TAM) and demonstrate the use of such graphene glass for high-performance touch panel applications. The 4.5 in.-sized graphene glass was produced by an optimized CVD procedure, which can readily serve as transparent conducting electrode (TCE) without further treatment. The graphene glass exhibited an intriguing optical transmittance and electrical conductance concurrently, presenting a sheet resistance of 370–510 Ω·sq–1 at a transmittance of 82%, much improved from our previous achievements. Moreover, direct measurement of graphene carrier dynamics and transport by TAM revealed the similar biexponential decay behavior to that of CVD graphene grown on Cu, along with a carrier mobility as high as 4820 cm2·V–1·s–1. Such large-area, highly uniform, transparent conducting graphene glass was assembled to integrate resistive touch panels that demonstrated a high device performance. Briefly, this work aims to present the great feasibility of good quality graphene glass toward scalable and practical TCE applications.Keywords: carrier transport; direct CVD; graphene glass; touch panel; transparent conducting electrode;
Co-reporter:Qingqing Ji, Cong Li, Jingli Wang, Jingjing Niu, Yue Gong, Zhepeng Zhang, Qiyi Fang, Yu Zhang, Jianping Shi, Lei Liao, Xiaosong Wu, Lin Gu, Zhongfan Liu, and Yanfeng Zhang
Nano Letters August 9, 2017 Volume 17(Issue 8) pp:4908-4908
Publication Date(Web):July 27, 2017
DOI:10.1021/acs.nanolett.7b01914
Nanothick metallic transition metal dichalcogenides such as VS2 are essential building blocks for constructing next-generation electronic and energy-storage applications, as well as for exploring unique physical issues associated with the dimensionality effect. However, such two-dimensional (2D) layered materials have yet to be achieved through either mechanical exfoliation or bottom-up synthesis. Herein, we report a facile chemical vapor deposition route for direct production of crystalline VS2 nanosheets with sub-10 nm thicknesses and domain sizes of tens of micrometers. The obtained nanosheets feature spontaneous superlattice periodicities and excellent electrical conductivities (∼3 × 103 S cm–1), which has enabled a variety of applications such as contact electrodes for monolayer MoS2 with contact resistances of ∼1/4 to that of Ni/Au metals, and as supercapacitor electrodes in aqueous electrolytes showing specific capacitances as high as 8.6 × 102 F g–1. This work provides fresh insights into the delicate structure–property relationship and the broad application prospects of such metallic 2D materials.Keywords: chemical vapor deposition; contact electrode; supercapacitor; superstructure; Vanadium disulfide;
Co-reporter:Yue Qi, Zhepeng Zhang, Bing Deng, Xiebo Zhou, Qiucheng Li, Min Hong, Yuanchang Li, Zhongfan Liu, and Yanfeng Zhang
Journal of the American Chemical Society April 26, 2017 Volume 139(Issue 16) pp:5849-5849
Publication Date(Web):April 10, 2017
DOI:10.1021/jacs.7b00647
Clarifying the origin and the electronic properties of defects in materials is crucial since the mechanical, electronic and magnetic properties can be tuned by defects. Herein, we find that, for the growth of h-BN monolayer on Re(0001), the patching frontiers of different domains can be classified into three types, i.e., the patching of B- and N-terminated (B|N-terminated) frontiers, B|B-terminated frontiers and N|N-terminated frontiers, which introduce three types of defects, i.e., the “heart” shaped moiré-level defect, the nonbonded and bonded line defects, respectively. These defects were found to bring significant modulations to the electronic properties of h-BN, by introducing band gap reductions and in-gap states, comparing with perfect h-BN on Re(0001) with a band gap of ∼3.7 eV. The intrinsic binary composition nature of h-BN and the strong h-BN-Re(0001) interaction are proposed to be cooperatively responsible for the formation of these three types of defects. The former one provides different types of h-BN frontiers for domain patching. And the later one induces multinucleation but aligned growth of h-BN domains on Re(0001), thus precluding their subsequent coalescence to some extent. This work offers a deep insight into the categories of defects introduced from the patching growth of two-dimensional layered materials, as well as their electronic property modulation through the defect engineering.
Co-reporter:Zhaolong Chen;Xu-Dong Chen;Huihui Wang;Xinqi Li;Li Lin;Ke Chen;Haina Ci;Xiaosong Wu;Yingying Zhang;Yanfeng Zhang
Advanced Electronic Materials 2017 Volume 3(Issue 11) pp:
Publication Date(Web):2017/11/01
DOI:10.1002/aelm.201700212
AbstractThe direct growth of graphene on low-cost soda-lime glass has attracted widespread attention for its potential to promote the development of high-value-added graphene-based products. For its most promising application as a transparent electrode, a relatively low sheet resistance is highly desired for the derived graphene glass. However, obtaining this result is still a challenge owing to the low catalytic activity of the glass surface, the small domain size of the resultant graphene, and the limited film continuity. Carbon nanotubes (CNT), which have similar structural and electronic properties to those of graphene, have been proposed to bridge/offset the grain boundaries and defects of graphene to improve electron transfer and reduce the sheet resistance. To achieve this, the one-batch synthesis of highly conductive graphene and multiwalled CNT (MWCNT) hybrid films on soda-lime glass using a molten-bed chemical vapor deposition (CVD) method is designed. The thus-obtained glass exhibits excellent conductivity, transmittance, and outstanding thermal and chemical stability. This highly conductive hybrid material is then employed as a high-performance liquid-crystal-based switchable window. In short, this work is believed to enhance the versatile applications of highly conductive graphene/MWCNT-hybrid-coated glass as well as its mass production, considering its compatibility with current glass production techniques.
Co-reporter:Rong Liu;Jingyuan Zhou;Xin Gao;Jiaqiang Li;Ziqian Xie;Zhenzhu Li;Shuqing Zhang;Lianming Tong;Jin Zhang
Advanced Electronic Materials 2017 Volume 3(Issue 11) pp:
Publication Date(Web):2017/11/01
DOI:10.1002/aelm.201700122
AbstractThe decontamination of water polluted with heavy metal ions is of worldwide concern. Among various treatment approaches to remove metal ions from water, adsorption is regarded as an efficient method, and a variety of materials have been applied as adsorbents for the removal of metal ions from polluted water. Recently, carbon nanomaterials have been examined as alternative adsorbents due to their high specific surface areas, high removal efficiency, and strong interactions with metal ions. Graphdiyne, a new kind of carbon allotrope composed of sp- and sp2-hybridized carbon atoms, has attracted great interest due to its impressive properties. Graphdiyne is considered to be a promising candidate for the adsorption of heavy metal ions as the acetylenic links in graphdiyne strongly interact with metal ions. Herein, graphdiyne is used as an adsorbent to remove lead ions from water. The interaction between lead ions and graphdiyne is explored by X-ray photoelectron spectroscopy and Raman spectroscopy. The maximum adsorption capacity calculated by the Langmuir isotherm model is 470.5 mg g−1. Graphdiyne is also synthesized on copper foam and used as a filter to eliminate lead ions from water. The filter shows high performance with a removal efficiency of 99.6% and can be recovered through treatment with acidic solution.
Co-reporter:Qiucheng Li;Zifeng Zhao;Baoming Yan;Xiuju Song;Zhepeng Zhang;Jia Li;Xiaosong Wu;Zuqiang Bian;Xiaolong Zou;Yanfeng Zhang
Advanced Materials 2017 Volume 29(Issue 32) pp:
Publication Date(Web):2017/08/01
DOI:10.1002/adma.201701325
The direct growth of high-quality, large-area, uniform, vertically stacked Gr/h-BN heterostructures is of vital importance for applications in electronics and optoelectronics. However, the main challenge lies in the catalytically inert nature of the hexagonal boron nitride (h-BN) substrates, which usually afford a rather low decomposition rate of carbon precursors, and thus relatively low growth rate of graphene. Herein, a nickelocene-precursor-facilitated route is developed for the fast growth of Gr/h-BN vertical heterostructures on Cu foils, which shows much improved synthesis efficiency (8–10 times faster) and crystalline quality of graphene (large single-crystalline domain up to ≈20 µm). The key advantage of our synthetic route is the utilization of nickel atoms that are decomposed from nickelocene molecules as the gaseous catalyst, which can decrease the energy barrier for graphene growth and facilitate the decomposition of carbon sources, according to our density functional theory calculations. The high-quality Gr/h-BN stacks are proved to be perfect anode/protecting layers for high-performance organic light-emitting diode devices. In this regard, this work offers a brand-new route for the fast growth of Gr/h-BN heterostructures with practical scalability and high crystalline quality, thus should propel its wide applications in transparent electrodes, high-performance electronic devices, and energy harvesting/transition directions.
Co-reporter:Jiaqiang Li;Ziqian Xie;Yan Xiong;Zhenzhu Li;Qunxing Huang;Shuqing Zhang;Jingyuan Zhou;Rong Liu;Xin Gao;Changguo Chen;Lianming Tong;Jin Zhang
Advanced Materials 2017 Volume 29(Issue 19) pp:
Publication Date(Web):2017/05/01
DOI:10.1002/adma.201700421
β-Graphdiyne (β-GDY) is a member of 2D graphyne family with zero band gap, and is a promising material with potential applications in energy storage, organic electronics, etc. However, the synthesis of β-GDY has not been realized yet, and the measurement of its intrinsic properties remains elusive. In this work, β-GDY-containing thin film is successfully synthesized on copper foil using modified Glaser–Hay coupling reaction with tetraethynylethene as precursor. The as-grown carbon film has a smooth surface and is continuous and uniform. Electrical measurements reveal the conductivity of 3.47 × 10−6 S m−1 and the work function of 5.22 eV. TiO2@β-GDY nanocomposite is then prepared and presented with an enhancement of photocatalytic ability compared to pure TiO2.
Co-reporter:Huaying Ren;Huan Wang;Li Lin;Miao Tang;Shuli Zhao;Bing Deng
Nano Research 2017 Volume 10( Issue 4) pp:1189-1199
Publication Date(Web):2017 April
DOI:10.1007/s12274-017-1534-2
In the chemical vapor deposition growth of large-area graphene polycrystalline thin films, the coalescence of randomly oriented graphene domains results in a high density of uncertain grain boundaries (GBs). The structures and properties of various GBs are highly dependent on the misorientation angles between the graphene domains, which can significantly affect the performance of the graphene films and impede their industrial applications. Graphene bicrystals with a specific type of GB can be synthesized via the controllable growth of graphene domains with a predefined lattice orientation. Although the bicrystal has been widely investigated for traditional bulk materials, no successful synthesis strategy has been presented for growing two-dimensional graphene bicrystals. In this study, we demonstrate a simple approach for growing well-aligned large-domain graphene bicrystals with a confined tilt angle of 30° on a facilely recrystallized single-crystal Cu (100) substrate. Control of the density of the GBs with a misorientation angle of 30° was realized via the controllable rapid growth of subcentimeter graphene domains with the assistance of a cooperative catalytic surface-passivation treatment. The large-area production of graphene bicrystals consisting of the sole specific GBs with a tunable density provides a new material platform for fundamental studies and practical applications.
Co-reporter:Rong Liu;Xin Gao;Jingyuan Zhou;Hua Xu;Zhenzhu Li;Shuqing Zhang;Ziqian Xie;Jin Zhang
Advanced Materials 2017 Volume 29(Issue 18) pp:
Publication Date(Web):2017/05/01
DOI:10.1002/adma.201604665
Graphdiyne analogs, linked carbon monolayers with acetylenic scaffoldings, are fabricated by adopting low-temperature chemical vapor deposition which provides a route for the synthesis of two-dimensional carbon materials via molecular building blocks. The electrical conductivity of the as-grown films can reach up to 6.72 S cm−1. Moreover, the films show potential as promising substrates for fluorescence suppressing and Raman advancement.
Co-reporter:Mingzhan Wang;Miao Tang;Shulin Chen;Haina Ci;Kexin Wang;Liurong Shi;Li Lin;Huaying Ren;Jingyuan Shan;Peng Gao;Hailin Peng
Advanced Materials 2017 Volume 29(Issue 47) pp:
Publication Date(Web):2017/12/01
DOI:10.1002/adma.201703882
AbstractAluminum (Al) foil, as the most accepted cathode current collector for lithium-ion batteries (LIBs), is susceptible to local anodic corrosions during long-term operations. Such corrosions could lead to the deterioration or even premature failure of the batteries and are generally believed to be a bottleneck for next-generation 5 V LIBs. Here, it is demonstrated that Al foil armored by conformal graphene coating exhibits significantly reinforced anodic corrosion resistance in both LiPF6 and lithium bis(trifluoromethanesulphonyl) imide (LiTFSI) based electrolytes. Moreover, LiMn2O4 cells using graphene-armored Al foil as current collectors (LMO/GA) demonstrate enhanced electrochemical performance in comparison with those using pristine Al foil (LMO/PA). The long-term discharge capacity retention of LMO/GA cell after ≈950 h straight operations at low rate (0.5 C) reaches up to 91%, remarkably superior to LMO/PA cell (75%). The self-discharge propensity of LMO/GA is clearly relieved and the rate/power performance is also improved with graphene mediations. This work not only contributes to the long-term stable operations of LIBs but also might catalyze the deployment of 5 V LIBs in the future.
Co-reporter:Luzhao Sun;Li Lin;Jincan Zhang;Huan Wang;Hailin Peng
Nano Research 2017 Volume 10( Issue 2) pp:355-363
Publication Date(Web):2017 February
DOI:10.1007/s12274-016-1297-1
The fast growth of large single-crystalline graphene by chemical vapor deposition on Cu foil remains a challenge for industrial-scale applications. To achieve the fast growth of large single-crystalline graphene, understanding the detailed dynamics governing the entire growth process—including nucleation, growth, and coalescence—is important; however, these remain unexplored. In this study, by using a pulsed carbon isotope labeling technique in conjunction with micro-Raman spectroscopy identification, we visualized the growth dynamics, such as nucleation, growth, and coalescence, during the fast growth of large single-crystalline graphene domains. By tuning the supply of the carbon source, a growth rate of 320 μm/min and the growth of centimeter-sized graphene single crystals were achieved on Cu foil.
Co-reporter:Li Lin;Luzhao Sun;Jincan Zhang;Jingyu Sun;Ai Leen Koh;Hailin Peng
Advanced Materials 2016 Volume 28( Issue 23) pp:4671-4677
Publication Date(Web):
DOI:10.1002/adma.201600403
Co-reporter:Xin Gao;Jingyuan Zhou;Ran Du;Ziqian Xie;Shibin Deng;Rong Liu;Jin Zhang
Advanced Materials 2016 Volume 28( Issue 1) pp:168-173
Publication Date(Web):
DOI:10.1002/adma.201504407
Co-reporter:Lin Zhou;Lei Liao;Jinying Wang;Jingwen Yu;Denghua Li;Qin Xie;Zhirong Liu;Yanlian Yang;Xuefeng Guo
Advanced Materials 2016 Volume 28( Issue 11) pp:2148-2154
Publication Date(Web):
DOI:10.1002/adma.201505360
Co-reporter:Qingqing Ji;Yu Zhang;Jianping Shi;Jingyu Sun;Yanfeng Zhang
Advanced Materials 2016 Volume 28( Issue 29) pp:6207-6212
Publication Date(Web):
DOI:10.1002/adma.201504762

2D layered transition metal dichalcogenides (TMDCs) have emerged as new possibilites beyond conventional particulate catalysts in facilitating efficient electrochemical hydrogen evolution. This is mainly mediated by the ultrahigh surface-to-volume ratio and the effective coupling of all active sites with supporting electrodes. Especially, the facile chemical vapor deposition (CVD) method has enabled morphological engineering of monolayer TMDC catalysts toward development of abundant active edge sites within the 2D plane. Here, two pathways to achieve such purpose are highlighted, either by non-equilibrium growth of MoS2 dendrites or throughout high-density nucleation of MoS2 nanoflakes directly on the electrode materials. Furthermore, future research directions have also been proposed and discussed to further enhance the efficiency of such unique catalysts.

Co-reporter:Li Lin, Xiang Xu, Jianbo Yin, Jingyu Sun, Zhenjun Tan, Ai Leen Koh, Huan Wang, Hailin Peng, Yulin Chen, and Zhongfan Liu
Nano Letters 2016 Volume 16(Issue 7) pp:4094-4101
Publication Date(Web):June 28, 2016
DOI:10.1021/acs.nanolett.6b00803
Being atomically thin, graphene-based p–n junctions hold great promise for applications in ultrasmall high-efficiency photodetectors. It is well-known that the efficiency of such photodetectors can be improved by optimizing the chemical potential difference of the graphene p–n junction. However, to date, such tuning has been limited to a few hundred millielectronvolts. To improve this critical parameter, here we report that using a temperature-controlled chemical vapor deposition process, we successfully achieved modulation-doped growth of an alternately nitrogen- and boron-doped graphene p–n junction with a tunable chemical potential difference up to 1 eV. Furthermore, such p–n junction structure can be prepared on a large scale with stable, uniform, and substitutional doping and exhibits a single-crystalline nature. This work provides a feasible method for synthesizing low-cost, large-scale, high efficiency graphene p–n junctions, thus facilitating their applications in optoelectronic and energy conversion devices.
Co-reporter:Xiuju Song, Teng Gao, Yufeng Nie, Jianing Zhuang, Jingyu Sun, Donglin Ma, Jianping Shi, Yuanwei Lin, Feng Ding, Yanfeng Zhang, and Zhongfan Liu
Nano Letters 2016 Volume 16(Issue 10) pp:6109-6116
Publication Date(Web):August 31, 2016
DOI:10.1021/acs.nanolett.6b02279
Vertical heterostructures based on two-dimensional layered materials, such as stacked graphene and hexagonal boron nitride (G/h-BN), have stimulated wide interest in fundamental physics, material sciences and nanoelectronics. To date, it still remains challenging to obtain high quality G/h-BN heterostructures concurrently with controlled nucleation density and thickness uniformity. In this work, with the aid of the well-defined poly(methyl methacrylate) seeds, effective control over the nucleation densities and locations of graphene domains on the predeposited h-BN monolayers was realized, leading to the formation of patterned G/h-BN arrays or continuous films. Detailed spectroscopic and morphological characterizations further confirmed that ∼85.7% of such monolayer graphene domains were of single-crystalline nature with their domain sizes predetermined throughout seed interspacing. Density functional theory calculations suggested that a self-terminated growth mechanism can be applied for the related graphene growth on h-BN/Cu. In turn, as-constructed field-effect transistor arrays based on such synthesized single-crystalline G/h-BN patterning were found to be compatible with fabricating devices with nice and steady performance, hence holding great promise for the development of next-generation graphene-based electronics.Keywords: characterizations; chemical vapor deposition; controllable growth; Graphene and hexagonal boron nitride heterostructures; seed-assisted growth;
Co-reporter:Liurong Shi; Ke Chen; Ran Du; Alicja Bachmatiuk; Mark Hermann Rümmeli; Kongwei Xie; Youyuan Huang; Yanfeng Zhang
Journal of the American Chemical Society 2016 Volume 138(Issue 20) pp:6360-6363
Publication Date(Web):May 9, 2016
DOI:10.1021/jacs.6b02262
A seashell-based CVD technique for preparing three-dimensional (3D) graphene foams is reported. The graphene sheets in thus-obtained foams are seamlessly interconnected into a 3D flexible network, forming highly porous materials with negligible non-carbon impurities, ultralow density, and outstanding mechanical flexibility and electrical conductivity. These 3D graphene foams demonstrate a fast adsorption performance toward various oils and organic solvents, with adsorption capacity up to 250-fold weight gain. The present approach offers a practical route for scalable construction of 3D graphene foams for versatile applications such as energy storage and water remediation.
Co-reporter:Zhenjun Tan, Yue Wu, Hao Hong, Jianbo Yin, Jincan Zhang, Li Lin, Mingzhan Wang, Xiao Sun, Luzhao Sun, Yucheng Huang, Kaihui LiuZhongfan Liu, Hailin Peng
Journal of the American Chemical Society 2016 Volume 138(Issue 51) pp:16612-16615
Publication Date(Web):December 14, 2016
DOI:10.1021/jacs.6b11683
Two-dimensional (2D) layered hybrid perovskites of (RNH3)2PbX4 (R is an alkyl and X is a halide) have been recently synthesized and exhibited rich optical properties including fluorescence and exciton effects. However, few studies on transport and optoelectronic measurements of individual 2D perovskite crystals have been reported, presumably owing to the instability issue during electronic device fabrications. Here we report the first photodetector based on individual 2D (C4H9NH3)2PbBr4 perovskite crystals, built with the protection and top contact of graphene film. Both a high responsivity (∼2100 A/W) and extremely low dark current (∼10–10 A) are achieved with a design of interdigital graphene electrodes. Our study paves the way to build high-performance optoelectronic devices based on the emerging 2D single-crystal perovskite materials.
Co-reporter:Zhenjun Tan, Jianbo Yin, Cheng Chen, Huan Wang, Li Lin, Luzhao Sun, Jinxiong Wu, Xiao Sun, Haifeng Yang, Yulin Chen, Hailin Peng, and Zhongfan Liu
ACS Nano 2016 Volume 10(Issue 7) pp:6725
Publication Date(Web):May 10, 2016
DOI:10.1021/acsnano.6b02046
Twisted bilayer graphene (tBLG) with van Hove Singularity (VHS) has exhibited novel twist-angle-dependent chemical and physical phenomena. However, scalable production of high-quality tBLG is still in its infancy, especially lacking the angle controlled preparation methods. Here, we report a facile approach to prepare tBLG with large domain sizes (>100 μm) and controlled twist angles by a clean layer-by-layer transfer of two constituent graphene monolayers. The whole process without interfacial polymer contamination in two monolayers guarantees the interlayer interaction of the π-bond electrons, which gives rise to the existence of minigaps in electronic structures and the consequent formation of VHSs in density of state. Such perturbation on band structure was directly observed by angle-resolved photoemission spectroscopy with submicrometer spatial resolution (micro-ARPES). The VHSs lead to a strong light–matter interaction and thus introduce ∼20-fold enhanced intensity of Raman G-band, which is a characteristic of high-quality tBLG. The as-prepared tBLG with strong light–matter interaction was further fabricated into high-performance photodetectors with selectively enhanced photocurrent generation (up to ∼6 times compared with monolayer in our device).Keywords: interlayer coupling; photocurrent enhancement; twisted bilayer graphene; van Hove singularity
Co-reporter:Li Lin, Jiayu Li, Huaying Ren, Ai Leen Koh, Ning Kang, Hailin Peng, H. Q. Xu, and Zhongfan Liu
ACS Nano 2016 Volume 10(Issue 2) pp:2922
Publication Date(Web):February 1, 2016
DOI:10.1021/acsnano.6b00041
The controlled growth of high-quality graphene on a large scale is of central importance for applications in electronics and optoelectronics. To minimize the adverse impacts of grain boundaries in large-area polycrystalline graphene, the synthesis of large single crystals of monolayer graphene is one of the key challenges for graphene production. Here, we develop a facile surface-engineering method to grow large single-crystalline monolayer graphene by the passivation of the active sites and the control of graphene nucleation on copper surface using the melamine pretreatment. Centimeter-sized hexagonal single-crystal graphene domains were successfully grown, which exhibit ultrahigh carrier mobilities exceeding 25 000 cm2 V–1 s–1 and quantum Hall effects on SiO2 substrates. The underlying mechanism of melamine pretreatments were systematically investigated through elemental analyses of copper surface in the growth process of large single-crystals. This present work provides a surface design of a catalytic substrate for the controlled growth of large-area graphene single crystals.Keywords: active sites; large single-crystal graphene; passivation; surface engineering;
Co-reporter:Zhaolong Chen;Baolu Guan;Xu-dong Chen;Qing Zeng;Li Lin;Ruoyu Wang
Nano Research 2016 Volume 9( Issue 10) pp:3048-3055
Publication Date(Web):2016 October
DOI:10.1007/s12274-016-1187-6
Fast and uniform growth of high-quality graphene on conventional glass is of great importance for practical applications of graphene glass. We report herein a confined-flow chemical vapor deposition (CVD) approach for the high-efficiency fabrication of graphene glass. The key feature of our approach is the fabrication of a 2–4 μm wide gap above the glass substrate, with plenty of stumbling blocks; this gap was found to significantly increase the collision probability of the carbon precursors and reactive fragments between one another and with the glass surface. As a result, the growth rate of graphene glass increased remarkably, together with an improvement in the growth quality and uniformity as compared to those in the conventional gas flow CVD technique. These high-quality graphene glasses exhibited an excellent defogging performance with much higher defogging speed and higher stability compared to those previously reported. The graphene sapphire glass was found to be an ideal substrate for growing uniform and ultra-smooth aluminum nitride thin films without the tedious pre-deposition of a buffer layer. The presented confined-flow CVD approach offers a simple and low-cost route for the mass production of graphene glass, which is believed to promote the practical applications of various graphene glasses.
Co-reporter:Yao Guo;Jianbo Yin;Xianlong Wei;Zhenjun Tan;Jiapei Shu;Bo Liu;Yi Zeng;Song Gao;Hailin Peng;Qing Chen
Advanced Electronic Materials 2016 Volume 2( Issue 8) pp:
Publication Date(Web):
DOI:10.1002/aelm.201600048
Co-reporter:Xiebo Zhou, Jianping Shi, Yue Qi, Mengxi Liu, Donglin Ma, Yu Zhang, Qingqing Ji, Zhepeng Zhang, Cong Li, Zhongfan Liu, and Yanfeng Zhang
ACS Nano 2016 Volume 10(Issue 3) pp:3461
Publication Date(Web):February 25, 2016
DOI:10.1021/acsnano.5b07545
Although the recently discovered monolayer transition metal dichalcogenides exhibit novel electronic and optical properties, fundamental physical issues such as the quasiparticle bandgap tunability and the substrate effects remain undefined. Herein, we present the report of a quasi-one-dimensional periodically striped superstructure for monolayer MoS2 on Au(100). The formation of the unique striped superstructure is found to be mainly modulated by the symmetry difference between MoS2 and Au(100) and their lattice mismatch. More intriguingly, we find that the monolayer MoS2 is heavily n-doped on the Au(100) facet with a bandgap of 1.3 eV, and the Fermi level is upshifted by ∼0.10 eV on the ridge (∼0.2 eV below the conduction band) in contrast to the valley regions (∼0.3 eV below the conduction band) of the striped patterns after high-temperature sample annealing process. This tunable doping effect is considered to be caused by the different defect densities over the ridge/valley regions of the superstructure. Additionally, an obvious bandgap reduction is observed in the vicinity of the domain boundary for monolayer MoS2 on Au(100). This work should therefore inspire intensive explorations of adlayer–substrate interactions, the defects, and their effects on band-structure engineering of monolayer MoS2.Keywords: atomic structure; Au(100); doping level; molybdenum disulfide; scanning tunneling microscope/spectroscopy
Co-reporter:Ke Chen, Zhigang Chai, Cong Li, Liurong Shi, Mengxi Liu, Qin Xie, Yanfeng Zhang, Dongsheng Xu, Ayyakkannu Manivannan, and Zhongfan Liu
ACS Nano 2016 Volume 10(Issue 3) pp:3665
Publication Date(Web):February 26, 2016
DOI:10.1021/acsnano.6b00113
Mass production of high-quality graphene flakes is important for commercial applications. Graphene microsheets have been produced on an industrial scale by chemical and liquid-phase exfoliation of graphite. However, strong-interaction-induced interlayer aggregation usually leads to the degradation of their intrinsic properties. Moreover, the crystallinity or layer-thickness controllability is not so perfect to fulfill the requirement for advanced technologies. Herein, we report a quartz-powder-derived chemical vapor deposition growth of three-dimensional (3D) high-quality graphene flakes and demonstrate the fabrication and application of graphene/g-C3N4 composites. The graphene flakes obtained after the removal of growth substrates exhibit the 3D curved microstructure, controllable layer thickness, good crystallinity, as well as weak interlayer interactions suitable for preventing the interlayer stacking. Benefiting from this, we achieved the direct synthesis of g-C3N4 on purified graphene flakes to form the uniform graphene/g-C3N4 composite, which provides efficient electron transfer interfaces to boost its catalytic oxidation activity of cycloalkane with relatively high yield, good selectivity, and reliable stability.Keywords: chemical vapor deposition; g-C3N4; graphene; powder; three-dimensional
Co-reporter:Manish Chhowalla, Zhongfan Liu and Hua Zhang  
Chemical Society Reviews 2015 vol. 44(Issue 9) pp:2584-2586
Publication Date(Web):17 Apr 2015
DOI:10.1039/C5CS90037A
A graphical abstract is available for this content
Co-reporter:Qingqing Ji, Yu Zhang, Yanfeng Zhang and Zhongfan Liu  
Chemical Society Reviews 2015 vol. 44(Issue 9) pp:2587-2602
Publication Date(Web):26 Sep 2014
DOI:10.1039/C4CS00258J
As structural analogues of graphene but with a sizeable band gap, monolayers of group-VIB transition metal dichalcogenides (MX2, M = Mo, W; X = S, Se, Te, etc.) have emerged as the ideal two dimensional prototype for exploring fundamental issues in physics such as valley polarization, and for engineering a wide range of nanoelectronic, optoelectronic and photocatalytic applications. Recently, chemical vapour deposition (CVD) was introduced as a more efficient preparation method than traditional chemical or physical exfoliation options, and has allowed for the successful synthesis of large-area MX2 monolayers possessing a large domain size, high thickness uniformity and continuity, and satisfactory crystal quality. This tutorial review therefore focuses on introducing the more recent advances in the CVD growth of MX2 (MoS2, WS2, MoS2(1−x)Se2xetc.) monolayers via the sulphurisation/decomposition of pre-deposited metal-based precursors, or the one-step reaction and deposition of gaseous metal and chalcogen feedstocks. Differences in growth behaviour caused by commonly used amorphous SiO2/Si, and newly adopted insulating single crystal substrates such as sapphire, mica and SrTiO3, are also comparatively presented. Also discussed are the essential parameters that influence the growth of MX2, such as the temperature, the source–substrate distance and the composition of the carrier gas (Ar/H2). Finally, an assessment is provided for viable future pathways for fine-tuning of the domain size and orientation, thickness uniformity, and the bandgap of MX2 and its alloys.
Co-reporter:Lei Liao;Qin Xie;Xuefeng Guo
Advanced Materials 2015 Volume 27( Issue 27) pp:4093-4096
Publication Date(Web):
DOI:10.1002/adma.201501788
Co-reporter:Yubin Chen;Jingyu Sun;Junfeng Gao;Feng Du;Qi Han;Yufeng Nie;Zhaolong Chen;Alicja Bachmatiuk;Manish Kr. Priydarshi;Donglin Ma;Xiuju Song;Xiaosong Wu;Chunyang Xiong;Mark H. Rümmeli;Feng Ding;Yanfeng Zhang
Advanced Materials 2015 Volume 27( Issue 47) pp:7839-7846
Publication Date(Web):
DOI:10.1002/adma.201504229
Co-reporter:Bananakere Nanjegowda Chrashekar;Bing Deng;Ankanahalli Shankaregowda Smitha;Yubin Chen;Congwei Tan;Haixia Zhang;Hailin Peng
Advanced Materials 2015 Volume 27( Issue 35) pp:5210-5216
Publication Date(Web):
DOI:10.1002/adma.201502560
Co-reporter:Yunfan Guo;Li Lin;Shuli Zhao;Bing Deng;Hongliang Chen;Bangjun Ma;Jinxiong Wu;Jianbo Yin;Hailin Peng
Advanced Materials 2015 Volume 27( Issue 29) pp:4315-4321
Publication Date(Web):
DOI:10.1002/adma.201501912
Co-reporter:Qiucheng Li, Xiaolong Zou, Mengxi Liu, Jingyu Sun, Yabo Gao, Yue Qi, Xiebo Zhou, Boris I. Yakobson, Yanfeng Zhang, and Zhongfan Liu
Nano Letters 2015 Volume 15(Issue 9) pp:5804-5810
Publication Date(Web):August 5, 2015
DOI:10.1021/acs.nanolett.5b01852
Grain boundaries (GBs) of hexagonal boron nitride (h-BN) grown on Cu(111) were investigated by scanning tunneling microscopy/spectroscopy (STM/STS). The first experimental evidence of the GBs composed of square-octagon pairs (4|8 GBs) was given, together with those containing pentagon-heptagon pairs (5|7 GBs). Two types of GBs were found to exhibit significantly different electronic properties, where the band gap of the 5|7 GB was dramatically decreased as compared with that of the 4|8 GB, consistent with our obtained result from density functional theory (DFT) calculations. Moreover, the present work may provide a possibility of tuning the inert electronic property of h-BN via grain boundary engineering.
Co-reporter:Lei Liao, Huan Wang, Han Peng, Jianbo Yin, Ai Leen Koh, Yulin Chen, Qin Xie, Hailin Peng, and Zhongfan Liu
Nano Letters 2015 Volume 15(Issue 8) pp:5585-5589
Publication Date(Web):July 7, 2015
DOI:10.1021/acs.nanolett.5b02240
Twisted bilayer graphene (tBLG) exhibits van Hove singularities (VHSs) in the density of states that can be tuned by changing the twist angle (θ), sparking various novel physical phenomena. Much effort has been devoted to investigate the θ-dependent physical properties of tBLG. Yet, the chemical properties of tBLG with VHSs, especially the chemical reactivity, remain unexplored. Here we report the first systematic study on the chemistry of tBLG through the photochemical reaction between graphene and benzoyl peroxide. Twisted bilayer graphene exhibits θ-dependent reactivity, and remarkably enhanced reactivity is obtained when the energy of incident laser matches with the energy interval of the VHSs of tBLG. This work provides an insight on the chemistry of tBLG, and the successful enhancement of chemical reactivity derived from VHS is highly beneficial for the controllable chemical modification of tBLG as well as the development of tBLG based devices.
Co-reporter:Bing Deng, Po-Chun Hsu, Guanchu Chen, B. N. Chandrashekar, Lei Liao, Zhawulie Ayitimuda, Jinxiong Wu, Yunfan Guo, Li Lin, Yu Zhou, Mahaya Aisijiang, Qin Xie, Yi Cui, Zhongfan Liu, and Hailin Peng
Nano Letters 2015 Volume 15(Issue 6) pp:4206-4213
Publication Date(Web):May 28, 2015
DOI:10.1021/acs.nanolett.5b01531
Transparent conductive film on plastic substrate is a critical component in low-cost, flexible, and lightweight optoelectronics. Industrial-scale manufacturing of high-performance transparent conductive flexible plastic is needed to enable wide-ranging applications. Here, we demonstrate a continuous roll-to-roll (R2R) production of transparent conductive flexible plastic based on a metal nanowire network fully encapsulated between graphene monolayer and plastic substrate. Large-area graphene film grown on Cu foil via a R2R chemical vapor deposition process was hot-laminated onto nanowires precoated EVA/PET film, followed by a R2R electrochemical delamination that preserves the Cu foil for reuse. The encapsulated structure minimized the resistance of both wire-to-wire junctions and graphene grain boundaries and strengthened adhesion of nanowires and graphene to plastic substrate, resulting in superior optoelectronic properties (sheet resistance of ∼8 Ω sq–1 at 94% transmittance), remarkable corrosion resistance, and excellent mechanical flexibility. With these advantages, long-cycle life flexible electrochromic devices are demonstrated, showing up to 10000 cycles.
Co-reporter:Qingqing Ji, Min Kan, Yu Zhang, Yao Guo, Donglin Ma, Jianping Shi, Qiang Sun, Qing Chen, Yanfeng Zhang, and Zhongfan Liu
Nano Letters 2015 Volume 15(Issue 1) pp:198-205
Publication Date(Web):November 29, 2014
DOI:10.1021/nl503373x
Monolayer MoS2 prepared by chemical vapor deposition (CVD) has a highly polycrystalline nature largely because of the coalescence of misoriented domains, which severely hinders its future applications. Identifying and even controlling the orientations of individual domains and understanding their merging behavior therefore hold fundamental significance. In this work, by using single-crystalline sapphire (0001) substrates, we designed the CVD growth of monolayer MoS2 triangles and their polycrystalline aggregates for such purposes. The obtained triangular MoS2 domains on sapphire were found to distributively align in two directions, which, as supported by density functional theory calculations, should be attributed to the relatively small fluctuations of the interface binding energy around the two primary orientations. Using dark-field transmission electron microscopy, we further imaged the grain boundaries of the aggregating domains and determined their prevalent armchair crystallographic orientations with respect to the adjacent MoS2 lattice. The coalescence of individual triangular flakes governed by unique kinetic processes is proposed for the polycrystal formation. These findings are expected to shed light on the controlled MoS2 growth toward predefined domain orientation and large domain size, thus enabling its versatile applications in next-generation nanoelectronics and optoelectronics.
Co-reporter:Jingyu Sun, Yubin Chen, Manish Kr. Priydarshi, Zhang Chen, Alicja Bachmatiuk, Zhiyu Zou, Zhaolong Chen, Xiuju Song, Yanfeng Gao, Mark H. Rümmeli, Yanfeng Zhang, and Zhongfan Liu
Nano Letters 2015 Volume 15(Issue 9) pp:5846-5854
Publication Date(Web):August 25, 2015
DOI:10.1021/acs.nanolett.5b01936
Direct growth of graphene on traditional glasses is of great importance for various daily life applications. We report herein the catalyst-free atmospheric-pressure chemical vapor deposition approach to directly synthesizing large-area, uniform graphene films on solid glasses. The optical transparency and sheet resistance of such kinds of graphene glasses can be readily adjusted together with the experimentally tunable layer thickness of graphene. More significantly, these graphene glasses find a broad range of real applications by enabling the low-cost construction of heating devices, transparent electrodes, photocatalytic plates, and smart windows. With a practical scalability, the present work will stimulate various applications of transparent, electrically and thermally conductive graphene glasses in real-life scenarios.
Co-reporter:Jingyuan Zhou; Xin Gao; Rong Liu; Ziqian Xie; Jin Yang; Shuqing Zhang; Gengmin Zhang; Huibiao Liu; Yuliang Li; Jin Zhang
Journal of the American Chemical Society 2015 Volume 137(Issue 24) pp:7596-7599
Publication Date(Web):June 5, 2015
DOI:10.1021/jacs.5b04057
Synthesizing graphdiyne with a well-defined structure is a great challenge. We reported herein a rational approach to synthesize graphdiyne nanowalls using a modified Glaser–Hay coupling reaction. Hexaethynylbenzene and copper plate were selected as monomer and substrate, respectively. By adjusting the ratio of added organic alkali along with the amount of monomer, the proper amount of copper ions was dissolved into the solution, thus forming catalytic reaction sites. With a rapid reaction rate of Glaser–Hay coupling, graphdiyne grew vertically at these sites first, and then with more copper ions dissolved, uniform graphdiyne nanowalls formed on the surface of copper substrate. Raman spectra, UV–vis spectra, and HRTEM results confirmed the features of graphdiyne. These graphdiyne nanowalls also exhibited excellent and stable field-emission properties.
Co-reporter:Yue Qi, Xiebo Zhou, Mengxi Liu, Qiucheng Li, Donglin Ma, Yanfeng Zhang and Zhongfan Liu  
RSC Advances 2015 vol. 5(Issue 93) pp:76620-76625
Publication Date(Web):04 Sep 2015
DOI:10.1039/C5RA12848J
Selecting distinctive carbon precursors can mediate graphene synthesis towards versatile targets, for example, using C60 to produce graphene quantum dots or hexabromobenzene to achieve graphene at rather low temperature. Herein, 1,3,5-triethynylbenzene (TEB) is selected for the first time as the carbon precursor for graphene synthesis on Rh(111). Considering the characteristic π–d orbital hybridization between TEB and Rh(111), room-temperature adsorption followed by a temperature-programmed annealing or direct annealing to target growth temperature under ultrahigh vacuum conditions is designed to be the two synthesis pathways. In the former growth pathway, the benzene ring of the TEB unit is expected to be maintained throughout the whole annealing process, leading to a high yield of graphene at relatively low temperature as compared with existing synthesis via gaseous precursors. Several-molecule oligomers and graphene nanoclusters are detected to be the crucial intermediates through stepwise annealing (150 °C and 430 °C), as evidenced by scanning tunneling microscopy (STM) characterizations. Interestingly, graphene synthesized via the latter pathway usually possesses fewer domain boundaries and defects than the former one, probably due to sufficient diffusion and rearrangement of carbon precursors. Briefly, this work should contribute greatly to understanding the growth intermediates and the synthesis of high-quality graphene using large aromatic precursor molecules.
Co-reporter:Xiuju Song;Junfeng Gao;Yufeng Nie;Teng Gao;Jingyu Sun;Donglin Ma
Nano Research 2015 Volume 8( Issue 10) pp:3164-3176
Publication Date(Web):2015 October
DOI:10.1007/s12274-015-0816-9
Chemical vapor deposition (CVD) synthesis of large-domain hexagonal boron nitride (h-BN) with a uniform thickness is very challenging, mainly due to the extremely high nucleation density of this material. Herein, we report the successful growth of wafer-scale, high-quality h-BN monolayer films that have large single-crystalline domain sizes, up to ~72 µm in edge length, prepared using a folded Cu-foil enclosure. The highly confined growth space and the smooth Cu surface inside the enclosure effectively reduced the precursor feeding rate together and induced a drastic decrease in the nucleation density. The orientation of the as-grown h-BN monolayer was found to be strongly correlated to the crystallographic orientation of the Cu substrate: the Cu (111) face being the best substrate for growing aligned h-BN domains and even single-crystalline monolayers. This is consistent with our density functional theory calculations. The present study offers a practical pathway for growing high-quality h-BN films by deepening our fundamental understanding of the process of their growth by CVD.
Co-reporter:Jingyu Sun;Yubin Chen;Xin Cai;Bangjun Ma;Zhaolong Chen
Nano Research 2015 Volume 8( Issue 11) pp:3496-3504
Publication Date(Web):2015 November
DOI:10.1007/s12274-015-0849-0
Catalyst-free and scalable synthesis of graphene on various glass substrates at low temperatures is of paramount significance to numerous applications such as low-cost transparent electronics and state-of-the-art displays. However, systematic study within this promising research field has remained scarce thus far. Herein, we report the direct growth of graphene on various glasses using a low-temperature plasma-enhanced chemical vapor deposition method. Such a facile and scalable approach guarantees the growth of uniform, transfer-free graphene films on various glass substrates at a growth temperature range of 400–600 °C. The morphological, surface wetting, optical, and electrical properties of the obtained graphene can be tailored by controlling the growth parameters. Our uniform and high-quality graphene films directly integrated with low-cost, commonly used glasses show great potential in the fabrication of multi-functional electrodes for versatile applications in solar cells, transparent electronics, and smart windows.
Co-reporter:Chaohua Zhang;Lei Fu;Shuli Zhao;Yu Zhou;Hailin Peng
Advanced Materials 2014 Volume 26( Issue 11) pp:1776-1781
Publication Date(Web):
DOI:10.1002/adma.201304301
Co-reporter:Zhiyu Zou, Lei Fu, Xiuju Song, Yanfeng Zhang, and Zhongfan Liu
Nano Letters 2014 Volume 14(Issue 7) pp:3832-3839
Publication Date(Web):May 29, 2014
DOI:10.1021/nl500994m
Early transition metals, especially groups IVB-VIB metals, can form stable carbides, which are known to exhibit excellent “noble-metal-like” catalytic activities. We demonstrate herein the applications of groups IVB-VIB metals in graphene growth using atmospheric pressure chemical vapor deposition technique. Similar to the extensively studied Cu, Ni, and noble metals, these transition-metal foils facilitate the catalytic growth of single- to few-layer graphene. The most attractive advantage over the existing catalysts is their perfect control of layer thickness and uniformity with highly flexible experimental conditions by in situ converting the dissolved carbons into stable carbides to fully suppress the upward segregation/precipitation effect. The growth performance of graphene on these transition metals can be well explained by the periodic physicochemical properties of elements. Our work has disclosed a new territory of catalysts in the periodic table for graphene growth and is expected to trigger more interest in graphene research.
Co-reporter:Mengxi Liu, Yuanchang Li, Pengcheng Chen, Jingyu Sun, Donglin Ma, Qiucheng Li, Teng Gao, Yabo Gao, Zhihai Cheng, Xiaohui Qiu, Ying Fang, Yanfeng Zhang, and Zhongfan Liu
Nano Letters 2014 Volume 14(Issue 11) pp:6342-6347
Publication Date(Web):September 30, 2014
DOI:10.1021/nl502780u
In-plane heterostructure of hexagonal boron nitride and graphene (h-BN-G) has become a focus of graphene research owing to its tunable bandgap and intriguing properties. We report herein the synthesis of a quasi-freestanding h-BN-G monolayer heterostructure on a weakly coupled Ir(111) substrate, where graphene and h-BN possess distinctly different heights and surface corrugations. An atomically sharp zigzag type boundary has been found to dominate the patching interface between graphene and h-BN, as evidenced by high-resolution Scanning tunneling microscopy investigation as well as density functional theory calculation. Scanning tunneling spectroscopy studies indicate that the graphene and h-BN tend to exhibit their own intrinsic electronic features near the patching boundary. The present work offers a deep insight into the h-BN-graphene boundary structures both geometrically and electronically together with the effect of adlayer-substrate coupling.
Co-reporter:Lei Liao ; Hailin Peng
Journal of the American Chemical Society 2014 Volume 136(Issue 35) pp:12194-12200
Publication Date(Web):August 15, 2014
DOI:10.1021/ja5048297
Although graphene is extremely inert in chemistry because of the giant delocalized π electron system, various methods have been developed to achieve its efficient chemical modification. Covalent chemistry is effective to modulate the physical properties of graphene. By converting the sp2 hybridized carbon atoms to sp3 ones, new two-dimensional (2D) materials and 2D superlattices with fascinating features beyond mother graphene could be built from the graphene scaffold, greatly expanding the graphene family and its attraction. In this Perspective, the power of covalent chemistry is demonstrated from the viewpoint of tailoring graphene’s energy band structure as well as creating new 2D materials and 2D superlattices. A specific focus is laid on the general consideration and understanding of covalent graphene chemistry toward electronic devices and material science.
Co-reporter:Jingyu Sun ; Teng Gao ; Xiuju Song ; Yanfei Zhao ; Yuanwei Lin ; Huichao Wang ; Donglin Ma ; Yubin Chen ; Wenfeng Xiang ; Jian Wang ; Yanfeng Zhang
Journal of the American Chemical Society 2014 Volume 136(Issue 18) pp:6574-6577
Publication Date(Web):April 18, 2014
DOI:10.1021/ja5022602
High-quality monolayer graphene was synthesized on high-κ dielectric single crystal SrTiO3 (STO) substrates by a facile metal-catalyst-free chemical vapor deposition process. The as-grown graphene sample was suitable for fabricating a high performance field-effect transistor (FET), followed by a far lower operation voltage compared to that of a SiO2-gated FET and carrier motilities of approximately 870–1050 cm2·V–1·s–1 in air at rt. The directly grown high-quality graphene on STO makes it a perfect candidate for designing transfer-free, energy-saving, and batch production of FET arrays.
Co-reporter:Jinying Wang, Shuqing Zhang, Jingyuan Zhou, Rong Liu, Ran Du, Hua Xu, Zhongfan Liu, Jin Zhang and Zhirong Liu  
Physical Chemistry Chemical Physics 2014 vol. 16(Issue 23) pp:11303-11309
Publication Date(Web):23 Apr 2014
DOI:10.1039/C4CP00539B
Two-dimensional (2D) materials composed of sp and sp2 carbon atoms (e.g., graphyne and graphdiyne) show many interesting properties. These materials can be constructed through alkyne homocoupling; however, the occurrence of various side reactions increases the difficulty of their synthesis and structural characterization. Here, we investigate the thermodynamic properties and vibrational spectra of several aryl-alkynes. Both homocoupling and side reactions are found to occur spontaneously at room temperature in terms of thermodynamics. The calculated Raman spectra of the homocoupling products show regular changes with increasing polymerization degree. By rationalizing the vibrational modes of various oligomers, the Raman spectrum of a 2D sp–sp2 carbon sheet is predicted; it exhibits three sharp peaks at 2241, 1560, and 1444 cm−1. Although the target and byproducts display similar vibrational modes, a combination of Raman and infrared spectroscopies can be used to differentiate them. The theoretical results are then used to analyze the structure of a synthesized sample and provide useful information.
Co-reporter:Yubing Zhou, Yufeng Nie, Yujing Liu, Kai Yan, Jinhua Hong, Chuanhong Jin, Yu Zhou, Jianbo Yin, Zhongfan Liu, and Hailin Peng
ACS Nano 2014 Volume 8(Issue 2) pp:1485
Publication Date(Web):January 6, 2014
DOI:10.1021/nn405529r
We present the controlled synthesis of high-quality two-dimensional (2D) GaSe crystals on flexible transparent mica substrates via a facile van der Waals epitaxy method. Single- and few-layer GaSe nanoplates with the lateral size of up to tens of micrometers were produced. The orientation and nucleation sites of GaSe nanoplates were well-controlled. The 2D GaSe crystal-based photodetectors were demonstrated on both mechanically rigid SiO2/Si and flexible mica substrates. Efficient photoresponse was observed in 2D GaSe crystal devices on transparent flexible mica substrates, regardless of repeated bending with different radii. The controlled growth of 2D GaSe crystals with efficient photoresponsivity opens up opportunities for both fundamental aspects and new applications in photodetectors.Keywords: gallium selenide; optoelectronics; two-dimensional layered crystals; van der Waals epitaxy
Co-reporter:Yunfan Guo;Mahaya Aisijiang;Kai Zhang;Wei Jiang;Yulin Chen;Wenshan Zheng;Zehao Song;Jie Cao;Hailin Peng
Advanced Materials 2013 Volume 25( Issue 41) pp:5959-5964
Publication Date(Web):
DOI:10.1002/adma.201302661
Co-reporter:Yabo Gao, Yanfeng Zhang, Pengcheng Chen, Yuanchang Li, Mengxi Liu, Teng Gao, Donglin Ma, Yubin Chen, Zhihai Cheng, Xiaohui Qiu, Wenhui Duan, and Zhongfan Liu
Nano Letters 2013 Volume 13(Issue 7) pp:3439-3443
Publication Date(Web):June 12, 2013
DOI:10.1021/nl4021123
The atomic layer of hybridized hexagonal boron nitride (h-BN) and graphene has attracted a great deal of attention after the pioneering work of P. M. Ajayan et al. on Cu foils because of their unusual electronic properties (Ci, L. J.; et al. Nat. Mater. 2010, 9, 430−435). However, many fundamental issues are still not clear, including the in-plane atomic continuity as well as the edge type at the boundary of hybridized h-BN and graphene domains. To clarify these issues, we have successfully grown a perfect single-layer h-BN-graphene (BNC) patchwork on a selected Rh(111) substrate, via a two-step patching growth approach. With the ideal sample, we convinced that at the in-plane linking interface, graphene and h-BN can be linked perfectly at an atomic scale. More importantly, we found that zigzag linking edges were preferably formed, as demonstrated by atomic-scale scanning tunneling microscopy images, which was also theoretically verified using density functional theory calculations. We believe the experimental and theoretical works are of particular importance to obtain a fundamental understanding of the BNC hybrid and to establish a deliberate structural control targeting high-performance electronic and spintronic devices.
Co-reporter:Qingqing Ji, Yanfeng Zhang, Teng Gao, Yu Zhang, Donglin Ma, Mengxi Liu, Yubin Chen, Xiaofen Qiao, Ping-Heng Tan, Min Kan, Ji Feng, Qiang Sun, and Zhongfan Liu
Nano Letters 2013 Volume 13(Issue 8) pp:3870-3877
Publication Date(Web):July 30, 2013
DOI:10.1021/nl401938t
Molybdenum disulfide (MoS2) is back in the spotlight because of the indirect-to-direct bandgap tunability and valley related physics emerging in the monolayer regime. However, rigorous control of the monolayer thickness is still a huge challenge for commonly utilized physical exfoliation and chemical synthesis methods. Herein, we have successfully grown predominantly monolayer MoS2 on an inert and nearly lattice-matching mica substrate by using a low-pressure chemical vapor deposition method. The growth is proposed to be mediated by an epitaxial mechanism, and the epitaxial monolayer MoS2 is intrinsically strained on mica due to a small adlayer-substrate lattice mismatch (∼2.7%). Photoluminescence (PL) measurements indicate strong single-exciton emission in as-grown MoS2 and room-temperature PL helicity (circular polarization ∼0.35) on transferred samples, providing straightforward proof of the high quality of the prepared monolayer crystals. The homogeneously strained high-quality monolayer MoS2 prepared in this study could competitively be exploited for a variety of future applications.
Co-reporter:Min Lin ; Di Wu ; Yu Zhou ; Wei Huang ; Wei Jiang ; Wenshan Zheng ; Shuli Zhao ; Chuanhong Jin ; Yunfan Guo ; Hailin Peng
Journal of the American Chemical Society 2013 Volume 135(Issue 36) pp:13274-13277
Publication Date(Web):August 26, 2013
DOI:10.1021/ja406351u
The controlled production of high-quality atomically thin III–VI semiconductors poses a challenge for practical applications in electronics, optoelectronics, and energy science. Here, we exploit a controlled synthesis of single- and few-layer In2Se3 flakes on different substrates, such as graphene and mica, by van der Waals epitaxy. The thickness, orientation, nucleation site, and crystal phase of In2Se3 flakes were well-controlled by tuning the growth condition. The obtained In2Se3 flakes exhibit either semiconducting or metallic behavior depending on the crystal structures. Meanwhile, field-effect transistors based on the semiconducting In2Se3 flakes showed an efficient photoresponse. The controlled growth of atomically thin In2Se3 flakes with diverse conductivity and efficient photoresponsivity could lead to new applications in photodetectors and phase change memory devices.
Co-reporter:Di Wu ; Kai Yan ; Yu Zhou ; Huan Wang ; Li Lin ; Hailin Peng
Journal of the American Chemical Society 2013 Volume 135(Issue 30) pp:10926-10929
Publication Date(Web):July 12, 2013
DOI:10.1021/ja404890n
Graphene p–n junctions grown by chemical vapor deposition hold great promise for the applications in high-speed, broadband photodetectors and energy conversion devices, where efficient photoelectric conversion can be realized by a hot-carrier-assisted photothermoelectric (PTE) effect and hot-carrier multiplication. However, the overall quantum efficiency is restricted by the low light absorption of single-layer graphene. Here, we present the first experimental demonstration of a plasmon-enhanced PTE conversion in chemical vapor deposited graphene p–n junctions. Surface plasmons of metallic nanostructures placed near the graphene p–n junctions were found to significantly enhance the optical field in the active layer and allow for a 4-fold increase in the photocurrent. Moreover, the utilization of localized plasmon enhancement facilitates the realization of efficient PTE conversion of graphene p–n junction devices under global illumination, which may offer an avenue for practical applications of graphene-based photodetectors and solar cells.
Co-reporter:Ruiqi Zhao, Jinying Wang, Mingmei Yang, Zhongfan Liu and Zhirong Liu  
Physical Chemistry Chemical Physics 2013 vol. 15(Issue 3) pp:803-806
Publication Date(Web):12 Nov 2012
DOI:10.1039/C2CP42994B
Various graphene quantum dots (GQDs) embedded in a hexagonal BN sheet were studied theoretically using the tight binding model. The effective mass was analyzed as a function of the distance between neighboring GQDs. It was found that the effective mass increases exponentially as the distance increases, indicating that the confined states of GQDs are well conserved in these hybrid systems. Further studies revealed that a ubiquitous gap of 0.3–3 eV exists, the size of which is mainly governed by the GQD's dimensions whereas it is insensitive to edge structures. These results show that GQDs in BN are promising candidates for optoelectronics.
Co-reporter:Xiwen Yang, Hailin Peng, Qin Xie, Yu Zhou, Zhongfan Liu
Journal of Electroanalytical Chemistry 2013 Volume 688() pp:243-248
Publication Date(Web):1 January 2013
DOI:10.1016/j.jelechem.2012.09.025
An electrochemical etching technique was developed to achieve a clean and efficient transfer of large-area graphene films grown on copper foils by chemical vapor deposition without degrading the quality of graphene. Clean transfer for continuous graphene films with fewer impurities and unintentional p-type doping in comparison with conventional wet-etching in oxidant solutions was confirmed by optical microscopy, scanning electron microscopy, atomic force microscopy, ultraviolet–visible spectroscopy, and Raman spectroscopy. This electrochemical transfer technique can be scaled up for industrial use and generalized to various substrates by selecting suitable oxidation voltage and electrolytes, which opens the door for the fabrication of large-scale graphene devices with enhanced performance.Graphical abstractHighlights► A clean and efficient transfer of graphene by electrochemical etching is reported. ► We compare the quality of transferred graphene with and without our method. ► Our method suppresses the p-type of doping and metal contamination of graphene. ► High-quality graphene can be transferred under a wide potential window.
Co-reporter:Chuancheng Jia;Jinying Wang;Changjiang Yao;Yang Cao; Yuwu Zhong; Zhirong Liu; Zhongfan Liu; Xuefeng Guo
Angewandte Chemie International Edition 2013 Volume 52( Issue 33) pp:8666-8670
Publication Date(Web):
DOI:10.1002/anie.201304301
Co-reporter:Chuancheng Jia;Jinying Wang;Changjiang Yao;Yang Cao; Yuwu Zhong; Zhirong Liu; Zhongfan Liu; Xuefeng Guo
Angewandte Chemie 2013 Volume 125( Issue 33) pp:8828-8832
Publication Date(Web):
DOI:10.1002/ange.201304301
Co-reporter:Yu Zhang;Yanfeng Zhang;Donglin Ma;Qingqing Ji;Wei Fang;Jianping Shi
Nano Research 2013 Volume 6( Issue 12) pp:887-896
Publication Date(Web):2013 December
DOI:10.1007/s12274-013-0365-z
Co-reporter:Donglin Ma;Yanfeng Zhang;Mengxi Liu;Qingqing Ji;Teng Gao;Yu Zhang
Nano Research 2013 Volume 6( Issue 9) pp:671-678
Publication Date(Web):2013 September
DOI:10.1007/s12274-013-0342-6
Co-reporter:Hui Li ; Jie Cao ; Wenshan Zheng ; Yulin Chen ; Di Wu ; Wenhui Dang ; Kai Wang ; Hailin Peng
Journal of the American Chemical Society 2012 Volume 134(Issue 14) pp:6132-6135
Publication Date(Web):March 28, 2012
DOI:10.1021/ja3021395
The orientation- and position-controlled synthesis of single-crystal topological insulator (Bi2Se3 and Bi2Te3) nanoplate arrays on mica substrates was achieved using van der Waals epitaxy. Individual ultrathin nanoplates with the lateral dimension up to ∼0.1 mm or uniform thickness down to 1–2 nm were produced. Single-Dirac-cone surface states of nanoplate aggregates were confirmed by angle-resolved photoemission spectroscopy measurements. The large-grain-size, single-crystal nanoplate arrays grown on mica can act as facile platforms for a combination of spectroscopy and in situ transport measurements, which may open up new avenues for studying exotic physical phenomena, surface chemical reactions, and modification in topological insulators.
Co-reporter:Ruiqi Zhao, Jinying Wang, Mingmei Yang, Zhongfan Liu, and Zhirong Liu
The Journal of Physical Chemistry C 2012 Volume 116(Issue 39) pp:21098-21103
Publication Date(Web):August 10, 2012
DOI:10.1021/jp306660x
The electronic structures of BN-embedded graphene (BNG) were theoretically studied. A nonzero gap was found to exist in BNG regardless of the edge structures (zigzag/armchair) and the symmetries of the superlattice and BN quantum dots (QDs). The size of the gap is mainly determined by the width of the carbon wall between neighboring BN QDs. It is insensitive to the size of BN QDs, and thus obeys a universal scaling law. This significant and stable energy gap renders BNG as a promising way to control the electronic properties of graphene. The comparison with graphene antidot lattices and nanoribbons was also provided.
Co-reporter:Yanfeng Zhang;Teng Gao;Shubao Xie;Boya Dai;Lei Fu;Yabo Gao
Nano Research 2012 Volume 5( Issue 6) pp:402-411
Publication Date(Web):2012 June
DOI:10.1007/s12274-012-0221-6
Co-reporter:Mingmei Yang ; Lin Zhou ; Jinying Wang ; Zhongfan Liu ;Zhirong Liu
The Journal of Physical Chemistry C 2012 Volume 116(Issue 1) pp:844-850
Publication Date(Web):December 1, 2011
DOI:10.1021/jp2088143
Density functional theory (DFT) studies were performed to investigate the chlorination of graphene. Unlike hydrogenation and fluorination, where the adsorption of H and F is always by covalent C–H/C–F bonding, Cl atoms generate various states when single-sided graphene exposed. In the initial reaction stage, it forms Cl–graphene charge-transfer complex, where the C orbitals keep sp2 hybridization and the graphene is p-type doped. Further chlorination may form two adsorption configurations: one is covalent bonding Cl pairs, where the structure of the C atom is close to sp3 hybridization. With the Cl coverage increases, this configuration may further cluster into hexagonal rings, and the resulting coverage is less than 25%. The other configuration is nonbonding. This configuration is energy preferable, while Cl atoms will form Cl2 molecules and escaped. When both sides of the graphene are exposed, the most stable adsorption configuration is a homogeneous ordered pattern with a Cl coverage of 25% (C4Cl) rather than collective clusters. The electronic properties of various chlorinated forms were also obtained; these showed that it is possible to tune the graphene bandgap by chlorination in a range of 0–1.3 eV.
Co-reporter:Yabo Gao;Yanfeng Zhang;Jun Ren;Denghua Li;Teng Gao;Ruiqi Zhao
Nano Research 2012 Volume 5( Issue 8) pp:543-549
Publication Date(Web):2012 August
DOI:10.1007/s12274-012-0239-9
Co-reporter:Mengxi Liu, Yanfeng Zhang, Yubin Chen, Yabo Gao, Teng Gao, Donglin Ma, Qingqing Ji, Yu Zhang, Cong Li, and Zhongfan Liu
ACS Nano 2012 Volume 6(Issue 12) pp:10581
Publication Date(Web):November 17, 2012
DOI:10.1021/nn3047154
We report the synthesis of large-scale uniform graphene films on high carbon solubility substrates of Rh foils for the first time using an ambient-pressure chemical vapor deposition method. We find that, by increasing the cooling rate in the growth process, the thickness of graphene can be tuned from multilayer to monolayer, resulting from the different segregation amount of carbon atoms from bulk to surface. The growth feature was characterized with scanning electron microscopy, Raman spectra, transmission electron microscopy, and scanning tunneling microscopy. We also find that bilayer or few-layer graphene prefers to stack deviating from the Bernal stacking geometry, with the formation of versatile moiré patterns. On the basis of these results, we put forward a segregation growth mechanism for graphene growth on Rh foils. Of particular importance, we propose that this randomly stacked few-layer graphene can be a model system for exploring some fantastic physical properties such as van Hove singularities.Keywords: APCVD; graphene; moiré pattern; STM; wrinkle
Co-reporter:Teng Gao, Yabo Gao, Cuizu Chang, Yubin Chen, Mengxi Liu, Shubao Xie, Ke He, Xucun Ma, Yanfeng Zhang, and Zhongfan Liu
ACS Nano 2012 Volume 6(Issue 8) pp:6562
Publication Date(Web):August 3, 2012
DOI:10.1021/nn302303n
We report the fabrication of a novel epitaxial graphene(EG)/Mn/SiC(0001) sandwiched structure through the intercalation of as-deposited Mn atoms on graphene surfaces, with the aid of scanning tunneling microscope, low energy electron diffraction, and X-ray photoelectron spectroscopy. We found that Mn can intercalate below both sp3-hybridized carbon-rich interface layer and monolayer graphene, along with the formation of various embedded Mn islands showing different surface morphologies. The unique trait of the sandwiched system is that the strong interaction between the carbon-rich interface layer and SiC(0001) can be decoupled to some degrees, and contemporaneous, an n-doping effect is observed by mapping the energy band of the system using angle-resolved photoemission spectroscopy. Moreover, what deserves our special attention is that the intercalated islands can only evolve below monolayer graphene when a bilayer coexists, accounting for an intriguing graphene thickness-dependent intercalation effect. In the long run, we believe that the construction of graphene/Mn/SiC(0001) systems offers ideal candidates for exploring some intriguing physical properties such as the magnetic property of two-dimensional transition metal systems.Keywords: ARPES; epitaxial graphene; intercalation; manganese; STM
Co-reporter:Lianming Tong, Tao Zhu and Zhongfan Liu  
Chemical Society Reviews 2011 vol. 40(Issue 3) pp:1296-1304
Publication Date(Web):01 Dec 2010
DOI:10.1039/C001054P
Surface-enhanced Raman scattering (SERS) has been intensively explored both in theory and applications and has been widely used in chemistry, physics and biology for decades. A variety of SERS substrates have been developed in order to investigate the mechanisms behind, which give rise to the enormous enhancement even enabling single molecule detection. The Raman enhancement, which involves an electromagnetic enhancement (EM) and a chemical enhancement (CM), reflects both the physical principle of light/metal interactions and the molecule/metal interactions. In this tutorial review, we focus on the EM enhancement of SERS active substrates made of colloidal gold nanoparticles (GNPs), varying from self-assembled arrays down to single particles, for the purpose of investigating the EM coupling effect and probing the distribution of the induced electric field of single GNPs.
Co-reporter:Chaohua Zhang;Lei Fu;Nan Liu;Minhao Liu;Yayu Wang
Advanced Materials 2011 Volume 23( Issue 8) pp:1020-1024
Publication Date(Web):
DOI:10.1002/adma.201004110
Co-reporter:Nan Liu, Lei Fu, Boya Dai, Kai Yan, Xun Liu, Ruiqi Zhao, Yanfeng Zhang, and Zhongfan Liu
Nano Letters 2011 Volume 11(Issue 1) pp:297-303
Publication Date(Web):December 3, 2010
DOI:10.1021/nl103962a
Graphene has been attracting wide interests owing to its excellent electronic, thermal, and mechanical performances. Despite the availability of several production techniques, it is still a great challenge to achieve wafer-size graphene with acceptable uniformity and low cost, which would determine the future of graphene electronics. Here we report a universal segregation growth technique for batch production of high-quality wafer-scale graphene from non-noble metal films. Without any extraneous carbon sources, 4 in. graphene wafers have been obtained from Ni, Co, Cu−Ni alloy, and so forth via thermal annealing with over 82% being 1−3 layers and excellent reproducibility. We demonstrate the first example of monolayer and bilayer graphene wafers using Cu−Ni alloy by combining the distinct segregation behaviors of Cu and Ni. Together with the easy detachment from growth substrates, we believe this facile segregation technique will offer a great driving force for graphene research.
Co-reporter:Kai Yan, Hailin Peng, Yu Zhou, Hui Li, and Zhongfan Liu
Nano Letters 2011 Volume 11(Issue 3) pp:1106-1110
Publication Date(Web):February 15, 2011
DOI:10.1021/nl104000b
We report the epitaxial formation of bilayer Bernal graphene on copper foil via chemical vapor deposition. The self-limit effect of graphene growth on copper is broken through the introduction of a second growth process. The coverage of bilayer regions with Bernal stacking can be as high as 67% before further optimization. Facilitated with the transfer process to silicon/silicon oxide substrates, dual-gated graphene transistors of the as-grown bilayer Bernal graphene were fabricated, showing typical tunable transfer characteristics under varying gate voltages. The high-yield layer-by-layer epitaxy scheme will not only make this material easily accessible but reveal the fundamental mechanism of graphene growth on copper.
Co-reporter:Xingcai Qin, Quanzi Yuan, Yapu Zhao, Shubao Xie, and Zhongfan Liu
Nano Letters 2011 Volume 11(Issue 5) pp:2173-2177
Publication Date(Web):April 4, 2011
DOI:10.1021/nl200843g
We present an approach for measuring the water flow rate through individual ultralong carbon nanotubes (CNTs) using field effect transistors array defined on individual tubes. Our work exhibits a rate enhancement of 882−51 and a slip length of 53−8 nm for CNTs with diameters of 0.81−1.59 nm. We also found that the enhancement factor does not increase monotonically with shrinking tube diameter and there exists a discontinuous region around 0.98−1.10 nm. We believe that these single-tube level results would help understand the intrinsic nanofluidics of water in CNTs.
Co-reporter:Zhonghuai Pan ; Nan Liu ; Lei Fu
Journal of the American Chemical Society 2011 Volume 133(Issue 44) pp:17578-17581
Publication Date(Web):October 7, 2011
DOI:10.1021/ja207517u
Wrinkles are often formed on CVD-graphene in an uncontrollable way. By designing the surface morphology of growth substrate together with a suitable transfer technique, we are able to engineer the dimension, density, and orientation of wrinkles on transferred CVD-graphene. Such kind of wrinkle engineering is employed to fabricate highly aligned graphene nanoribbon (GNR) arrays by self-masked plasma-etching. Strictly consistent with the designed wrinkles, the density of GNR arrays varied from ∼0.5 to 5 GNRs/μm, and over 88% GNRs are less than 10 nm in width. Electrical transport measurements of these GNR-based FETs exhibit an on/off ratio of ∼30, suggesting an opened bandgap. Our wrinkle engineering approach allows very easily for a massive production of GNR arrays with bandgap-required widths, which opens a practical pathway for large-scale integrated graphene devices.
Co-reporter:Liming Zhang ; Shuo Diao ; Yufeng Nie ; Kai Yan ; Nan Liu ; Boya Dai ; Qin Xie ; Alfonso Reina ; Jing Kong
Journal of the American Chemical Society 2011 Volume 133(Issue 8) pp:2706-2713
Publication Date(Web):February 3, 2011
DOI:10.1021/ja109934b
TiO2-based photocatalysis has been widely used to decompose various organic pollutants for the purpose of environmental protection. Such a “green” photochemical process can ultimately degrade organic compounds into CO2 and H2O under ambient conditions. We demonstrate here its extended application on the engineering of single- or few-layer graphene. Using a patterned TiO2 photomask, we have achieved various photochemical tailorings of graphene, including ribbon cutting, arbitrary patterning on any substrate, layer-by-layer thinning, and localized graphene to graphene oxide conversion. UV−visible spectroscopic studies indicate that the photogenerated, highly reactive ·OH radicals work as sharp chemical scissors. Being a solution-free, cost-effective, scalable, and easy handling technique, the presented photocatalytic patterning and modification approach allows for the versatile design and fabrication of graphene-based devices and circuits, compatible with current microelectronic technology, as demonstrated by this fabricated all-carbon field effect transistor (FET) array.
Co-reporter:Boya Dai;Lei Fu;Lei Liao;Nan Liu;Kai Yan;Yongsheng Chen
Nano Research 2011 Volume 4( Issue 5) pp:434-439
Publication Date(Web):2011 May
DOI:10.1007/s12274-011-0099-8
Reduction of graphene oxide (GO) is a promising low-cost synthetic approach to bulk graphene, which offers an accessible route to transparent conducting films and flexible electronics. Unfortunately, the release of oxygen-containing functional groups inevitably leaves behind vacancies and topological defects on the reduced GO sheet, and its low electrical conductivity hinders the development of practical applications. Here, we present a strategy for real-time repair of the newborn vacancies with carbon radicals produced by thermal decomposition of a suitable precursor. The sheet conductivity of thus-obtained single-layer graphene was raised more than six-fold to 350–410 S/cm (whilst retaining >96% transparency). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy revealed that the conductivity enhancement can be attributed to the formation of additional sp2-C structures. This method provides a simple and efficient process for obtaining highly conductive transparent graphene films.
Co-reporter:Fangping Ouyang, Shenglin Peng, Zhongfan Liu, and Zhirong Liu
ACS Nano 2011 Volume 5(Issue 5) pp:4023
Publication Date(Web):April 22, 2011
DOI:10.1021/nn200580w
The electronic structure of graphene antidot lattices (GALs) with zigzag hole edges was studied with first-principles calculations. It was revealed that half of the possible GAL patterns were unintentionally missed in the usual construction models used in earlier studies. With the complete models, the bandgap of the GALs was sensitive to the width W of the wall between the neighboring holes. A nonzero bandgap was opened in hexagonal GALs with even W, while the bandgap remained closed in those with odd W. Similar alternating gap opening/closing with W was also demonstrated in rhombohedral GALs. Moreover, analytical solutions of single-walled GALs were derived based on a tight-binding model to determine the location of the Dirac points and the energy dispersion, which confirmed the unique effect in GALs.Keywords: antidot lattices; bandgap; electronic structure; first-principles calculations; graphene; tight-binding model
Co-reporter:Yanfeng Zhang, Teng Gao, Yabo Gao, Shubao Xie, Qingqing Ji, Kai Yan, Hailin Peng, and Zhongfan Liu
ACS Nano 2011 Volume 5(Issue 5) pp:4014
Publication Date(Web):April 18, 2011
DOI:10.1021/nn200573v
Understanding of the continuity and the microscopic structure of as-grown graphene on Cu foils through the chemical vapor deposition (CVD) method is of fundamental significance for optimizing the growth parameters toward high-quality graphene. Because of the corrugated nature of the Cu foil surface, few experimental efforts on this issue have been made so far. We present here a high-resolution scanning tunneling microscopy (STM) study of CVD graphene directly on Cu foils. Our work indicates that graphene can be grown with a perfect continuity extending over both crystalline and noncrystalline regions, highly suggestive of weak graphene–substrate interactions. Due to thermal expansion mismatch, defect-like wrinkles and ripples tend to evolve either along the boundaries of crystalline terraces or on noncrystalline areas for strain relief. Furthermore, the strain effect arising from the conforming of perfect two-dimensional graphene to the highly corrugated surface of Cu foils is found to induce local bonding configuration change of carbon from sp2 to sp3, evidenced by the formation of “three-for-six” lattices.Keywords: Cu foil; CVD; graphene; growth; STM
Co-reporter:Xiaojun Xian, Liying Jiao, Teng Xue, Zhongyun Wu, and Zhongfan Liu
ACS Nano 2011 Volume 5(Issue 5) pp:4000
Publication Date(Web):April 7, 2011
DOI:10.1021/nn200566q
We report herein a facile electrochemical approach to synthesizing various layered composite films of nanomaterials and conducting polymers, called nanoveneers. Layered structures of polypyrrole film with single-walled carbon nanotubes (SWNTs), graphene, and Au nanoparticles have been obtained by electropolymerization of pyrrole molecules on a heavily doped silicon wafer preloaded with target conductive nanomaterials. A free-standing, transparent, and highly conductive composite film was achieved after peeling off from a silicon wafer. Different from traditional homogeneous composite materials, such kinds of nanoveneers combined to the best extent the structural continuity and processability of conducting polymers with the high conductivity and functionality of discontinuous SWNTs, graphene, and other nanomaterials. The layered electrochemical deposition provides a great freedom for constructing various nanostructures with well-controlled geometry and thus physicochemical properties, as demonstrated by SWNT/polypyrrole nanoveneers. These nanoveneers are particularly attractive in areas of chemical sensors, labels, transparent electronics, and optoelectronics.Keywords: electropolymerization; graphene; nanoparticles; nanoveneer; SWNTs
Co-reporter:Nan Liu;Zhonghuai Pan;Lei Fu;Chaohua Zhang;Boya Dai
Nano Research 2011 Volume 4( Issue 10) pp:
Publication Date(Web):2011 October
DOI:10.1007/s12274-011-0156-3
When two-dimensional graphene is exfoliated from three-dimensional highly oriented pyrolytic graphite (HOPG), ripples or corrugations always exist due to the intrinsic thermal fluctuations. Surface-grown graphenes also exhibit wrinkles, which are larger in dimension and are thought to be caused by the difference in thermal expansion coefficients between graphene and the underlying substrate in the cooling process after high temperature growth. For further characterization and applications, it is necessary to transfer the surface-grown graphenes onto dielectric substrates, and other wrinkles are generated during this process. Here, we focus on the wrinkles of transferred graphene and demonstrate that the surface morphology of the growth substrate is the origin of the new wrinkles which arise in the surface-to-surface transfer process; we call these morphology-induced wrinkles. Based on a careful statistical analysis of thousands of atomic force microscopy (AFM) topographic data, we have concluded that these wrinkles on transferred few-layer graphene (typically 1–3 layers) are determined by both the growth substrate morphology and the transfer process. Depending on the transfer medium and conditions, most of the wrinkles can be either erased or preserved. Our work suggests a new route for graphene engineering involving structuring the growth substrate and tailoring the transfer process. Open image in new window
Co-reporter:Ruiqi Zhao;Yanfeng Zhang;Teng Gao;Yabo Gao;Nan Liu;Lei Fu
Nano Research 2011 Volume 4( Issue 7) pp:712-721
Publication Date(Web):2011 July
DOI:10.1007/s12274-011-0127-8
Microscopic features of graphene segregated on Ni films prior to chemical transfer—including atomic structures of monolayers and bilayers, Moiré patterns due to non-AB stacking, as well as wrinkles and ripples caused by strain effects-have been characterized in detail by high-resolution scanning tunneling microscopy (STM). We found that the stacking geometry of the bilayer graphene usually deviates from the traditional Bernal stacking (or so-called AB stacking), resulting in the formation of a variety of Moiré patterns. The relative rotations inside the bilayer were then qualitatively deduced from the relationship between Moiré patterns and carbon lattices. Moreover, we found that typical defects such as wrinkles and ripples tend to evolve around multi-step boundaries of Ni, thus reflecting strong perturbations from substrate corrugations. These investigations of the morphology and the mechanism of formation of wrinkles and ripples are fundamental topics in graphene research. This work is expected to contribute to the exploration of electronic and transport properties of wrinkles and ripples. Open image in new window
Co-reporter:Teng Gao, Shubao Xie, Yabo Gao, Mengxi Liu, Yubin Chen, Yanfeng Zhang, and Zhongfan Liu
ACS Nano 2011 Volume 5(Issue 11) pp:9194
Publication Date(Web):October 24, 2011
DOI:10.1021/nn203440r
The synthesis of centimeter-scale uniform graphene on Pt foils was accomplished via a traditional ambient pressure chemical vapor deposition (CVD) method. Using scanning electron microscopy (SEM) and Raman spectroscopy, we reveal the macroscopic continuity, the thickness, as well as the defect state of as-grown graphene. Of particular importance is that the Pt foils after CVD growth have multifaceted texture, which allows us to explore the substrate crystallography effect on the growth rate and the continuity of graphene. By virtue of atomically resolved scanning tunneling microscopy (STM), we conclude that graphene grows mainly in registry with the symmetries of Pt(111), Pt(110), and Pt(100) facets, leading to hexagonal lattices and striped superstructures. Nevertheless, the carbon lattices on interweaving facets with different identities are connected seamlessly, which ensure the graphene growth from nanometer to micrometer levels. With these results, another prototype for clarifying the preliminary growth mechanism of the CVD process is demonstrated as an analogue of graphene on Cu foils.Keywords: chemical vapor deposition (CVD); graphene; growth; Pt foils; STM
Co-reporter:Bo Li, Lin Zhou, Di Wu, Hailin Peng, Kai Yan, Yu Zhou, and Zhongfan Liu
ACS Nano 2011 Volume 5(Issue 7) pp:5957
Publication Date(Web):June 9, 2011
DOI:10.1021/nn201731t
We report the covalent functionalization of graphene by photochemical chlorination. The gas-phase photochlorination of graphene, followed by the structural transformation of the C–C bonds from sp2 to sp3 configuration, could remove the conducting π-bands and open up a band gap in graphene. X-ray photoelectron spectroscopy revealed that chlorine is grafted to the basal plane of graphene, with about 8 atom % chlorine coverage. Raman spectroscopy, atomic force microscopy, and transmission electron microscopy all indicated that the photochlorinated graphene is homogeneous and nondestructive. The resistance increases over 4 orders of magnitude and a band gap appears upon photochlorination, confirmed by electrical measurements. Moreover, localized photochlorination of graphene can facilitate chemical patterning, which may offer a feasible approach to the realization of all-graphene circuits.Keywords: band gap opening; covalent functionalization; graphene; photochemical chlorination
Co-reporter:Xun Liu ; Lei Fu ; Nan Liu ; Teng Gao ; Yanfeng Zhang ; Lei Liao
The Journal of Physical Chemistry C 2011 Volume 115(Issue 24) pp:11976-11982
Publication Date(Web):May 17, 2011
DOI:10.1021/jp202933u
A facile way to segregate wafer-size graphene with controllable layer number using Cu–Ni binary alloy under vacuum annealing condition is presented here. Increasing atomic percentage of Ni in Cu–Ni alloy was found to segregate thicker uniform graphene. To date, over 95% monolayer and 91% bilayer graphene films have been prepared by only changing atomic percentage of Ni in Cu–Ni alloy, respectively. The synergetic combination of the distinct carbon solubilities of Cu and Ni and the well-known segregation phenomenon is believed to be responsible for the formation of high-quality uniform few layer graphene. Together with the easy detachment from growth substrates, we believe this facile segregation technique will offer a great driving force for graphene research.
Co-reporter:Zhongfan Liu;Liying Jiao;Yagang Yao;Xiaojun Xian ;Jin Zhang
Advanced Materials 2010 Volume 22( Issue 21) pp:2285-2310
Publication Date(Web):
DOI:10.1002/adma.200904167

Abstract

Aligned, ultralong single-walled carbon nanotubes (SWNTs) represent attractive building blocks for nanoelectronics. The structural uniformity along their tube axis and well-ordered two-dimensional architectures on wafer surfaces may provide a straightforward platform for fabricating high-performance SWNT-based integrated circuits. On the way towards future nanoelectronic devices, many challenges for such a specific system also exist. This Review summarizes the recent advances in the synthesis, identification and sorting, transfer printing and manipulation, device fabrication and integration of aligned, ultralong SWNTs in detail together with discussion on their major challenges and opportunities for their practical application.

Co-reporter:Peng Diao
Advanced Materials 2010 Volume 22( Issue 13) pp:1430-1449
Publication Date(Web):
DOI:10.1002/adma.200903592

Abstract

Single-walled carbon nanotubes (SWNTs), as one of the most promising one-dimension nanomaterials due to its unique structure, peculiar chemical, mechanical, thermal, and electronic properties, have long been considered as an important building block to construct ordered alignments. Vertically aligned SWNTs (v-SWNTs) have been successfully prepared by using direct growth and chemical assembly strategies. In this review, we focus explicitly on the v-SWNTs fabricated via chemical assembly strategy. We provide the readers with a full and systematic summary covering the advances in all aspects of this area, including various approaches for the preparation of v-SWNTs using chemical assembly techniques, characterization, assembly kinetics, and electrochemical properties of v-SWNTs. We also review the applications of v-SWNTs in electrochemical and bioelectrochemical sensors, photoelectric conversion, and scanning probe microscopy.

Co-reporter:Peng Diao
Advanced Materials 2010 Volume 22( Issue 13) pp:
Publication Date(Web):
DOI:10.1002/adma.201090039
Co-reporter:Xi Ling, Liming Xie, Yuan Fang, Hua Xu, Haoli Zhang, Jing Kong, Mildred S. Dresselhaus, Jin Zhang and Zhongfan Liu
Nano Letters 2010 Volume 10(Issue 2) pp:553-561
Publication Date(Web):December 29, 2009
DOI:10.1021/nl903414x
Graphene is a monolayer of carbon atoms packed into a two-dimensional (2D) honeycomb crystal structure, which is a special material with many excellent properties. In the present study, we will discuss the possibility that graphene can be used as a substrate for enhancing Raman signals of adsorbed molecules. Here, phthalocyanine (Pc), rhodamine 6G (R6G), protoporphyin IX (PPP), and crystal violet (CV), which are popular molecules widely used as a Raman probe, are deposited equally on graphene and a SiO2/Si substrate using vacuum evaporation or solution soaking. By comparing the Raman signals of molecules on monolayer graphene and on a SiO2/Si substrate, we observed that the intensities of the Raman signals on monolayer graphene are much stronger than on a SiO2/Si substrate, indicating a clear Raman enhancement effect on the surface of monolayer graphene. For solution soaking, the Raman signals of the molecules are visible even though the concentration is low to 10−8 mol/L or less. What’s more interesting, the enhanced efficiencies are quite different on monolayer, few-layer, multilayer graphene, graphite, and highly ordered pyrolytic graphite (HOPG). The Raman signals of molecules on multilayer graphene are even weaker than on a SiO2/Si substrate, and the signals are even invisible on graphite and HOPG. Taking the Raman signals on the SiO2/Si substrate as a reference, Raman enhancement factors on the surface of monolayer graphene can be obtained using Raman intensity ratios. The Raman enhancement factors are quite different for different peaks, changing from 2 to 17. Furthermore, we found that the Raman enhancement factors can be distinguished through three classes that correspond to the symmetry of vibrations of the molecule. We attribute this enhancement to the charge transfer between graphene and the molecules, which result in a chemical enhancement. This is a new phenomenon for graphene that will expand the application of graphene to microanalysis and is good for studying the basic properties of both graphene and SERS.
Co-reporter:Wenhui Dang, Hailin Peng, Hui Li, Pu Wang and Zhongfan Liu
Nano Letters 2010 Volume 10(Issue 8) pp:2870-2876
Publication Date(Web):July 12, 2010
DOI:10.1021/nl100938e
The authors present a van der Waals epitaxy of high-quality ultrathin nanoplates of topological insulator Bi2Se3 on a pristine graphene substrate using a simple vapor-phase deposition method. Sub-10-nm-thick nanoplates of layered Bi2Se3 with defined orientations can be epitaxially grown on a few-layer pristine graphene substrate. We show the evolution of Raman spectra with the number of Bi2Se3 layers on few-layer graphene. Bi2Se3 nanoplates with a thickness of three quintuple-layers (3-QL) exhibit the strongest Raman intensity. Strain effects in the Bi2Se3/graphene nanoplate heterostructures is also studied by Raman spectroscopy. 1-QL and 2-QL Bi2Se3 nanoplates experience tensile stress, consistent with compressive stress in single-layer and bilayer graphene substrates. Our results suggest an approach for the synthesis of epitaxial heterostructures that consist of an ultrathin topological insulator and graphene, which may be a new direction for electronic and spintronic applications.
Co-reporter:Quan Qing, Daniel A. Nezich, Jing Kong, Zhongyun Wu, and Zhongfan Liu
Nano Letters 2010 Volume 10(Issue 11) pp:4715-4720
Publication Date(Web):October 14, 2010
DOI:10.1021/nl103084j
In this work, we have demonstrated that the local deformation at the crossed carbon nanotube (CNT) junctions can introduce significant tunable local gate effect under ambient environment. Atomic force microscope (AFM) manipulation of the local deformation yielded a variation in transconductance that was retained after removing the AFM tip. Application of a large source−drain voltage and pressing the CNT junction above a threshold pressure can respectively erase and recover the transconductance modulation reversibly. The local gate effect is found to be independent of the length of the crossed CNT and attributed to the charges residing at the deformed junctions due to formation of localized states. The number of localized charges is estimated to be in the range of 102 to 103. These results may find potential applications in electromechanical sensors and could have important implications for designing nonvolatile devices based on crossed CNT junctions.
Co-reporter:Hailin Peng, Zhongfan Liu
Coordination Chemistry Reviews 2010 Volume 254(9–10) pp:1151-1168
Publication Date(Web):May 2010
DOI:10.1016/j.ccr.2010.02.016
Data storage using scanning probe microscopy (SPM) has attracted great attention because of its nanometer-scale storage capacity. We present an overview of the recent advances and representative achievements of SPM-based data storage from the viewpoints of recording techniques including electrical bistability, photoelectrochemical conversion, field-induced charge storage, atomic manipulation or deposition, local oxidation, magneto-optical or magnetic recording, thermally induced physical deformation or phase change, and so forth. Among new SPM-based data storage schemes, a thermochemical-hole-burning (THB) technique was developed in our group. This review also summarizes our recent achievements in design and synthesis of organic charge-transfer (CT) complexes towards thermochemical-hole-burning memory, the correlation between hole-burning performances and physicochemical properties of CT complexes, the STM tip design and its effects on the hole-burning performance, as well as studies on the data storage mechanism.
Co-reporter:Liang Ren;Xiaojun Xian;Kai Yan;Lei Fu;Yuwen Liu;Shengli Chen
Advanced Functional Materials 2010 Volume 20( Issue 8) pp:1209-1223
Publication Date(Web):
DOI:10.1002/adfm.200902187

Abstract

Universal strategies for synthesizing one-dimensional organic nanomaterials are of fundamental importance in the development of more flexible, cheaper and lighter electronics. Charge-transfer (CT) complexes, the major kind of organic conductors, are in the long-term attractive materials owing to their unique crystal structures and conductive properties. In this article, a general strategy for the synthesis of CT complex micro/nanowires based on the localized nanoelectrochemistry using tiny carbon nanotube (CNT) electrodes is presented. This strategy is successfully demonstrated over 12 typical CT complexes, and a general rule for the preparation of various kinds of CT complex micro/nanowires is summarized. The CT complex micro/nanowires thus synthesized have high aspect ratios and long lengths as compared with traditional macroscopic planar electrodes, originating from the one-dimensional structural feature with fewer or no defects and the ultrasmall surface area of the CNT. This work provides a more versatile material basis for the fundamental and application studies of low-dimensional organic conductor materials.

Co-reporter:Liang Ren;Xiaojun Xian;Kai Yan;Lei Fu;Yuwen Liu;Shengli Chen
Advanced Functional Materials 2010 Volume 20( Issue 8) pp:
Publication Date(Web):
DOI:10.1002/adfm.201090028
Co-reporter:Yang Cao;Zhongming Wei;Song Liu;Lin Gan;Xuefeng Guo ;Wei Xu ;MichaelL. Steigerwald ;Daoben Zhu
Angewandte Chemie International Edition 2010 Volume 49( Issue 36) pp:6319-6323
Publication Date(Web):
DOI:10.1002/anie.201001683
Co-reporter:Liang Ren;Lei Fu;Yuwen Liu;Shengli Chen
Advanced Materials 2009 Volume 21( Issue 46) pp:4742-4746
Publication Date(Web):
DOI:10.1002/adma.200901019
Co-reporter:Liying Jiao, Xiaojun Xian, Zhongyun Wu, Jin Zhang and Zhongfan Liu
Nano Letters 2009 Volume 9(Issue 1) pp:205-209
Publication Date(Web):December 1, 2008
DOI:10.1021/nl802779t
We present a general selective positioning and integration technique for fabricating single-walled carbon nanotube (SWNT) circuits with preselected individual SWNTs as building blocks by utilizing poly(methyl methacrylate) (PMMA) thin film as a macroscopically handlable mediator. The transparency and marker-replicating capability of PMMA mediator allow the selective placement of chirality-specific nanotubes onto predesigned patterned surfaces with a resolution of ca. 1 μm. This technique is compatible with multiple operations and p−n conversion by chemical doping, which enables the construction of complex and logic circuits. As demonstrations of building SWNTs circuits, we fabricated a field effect inverter, a 2 × 2 all-SWNT crossbar field effect transistor (FET), and flexible FETs on plastic with this technique. This selective positioning approach can also be extended to construct purpose-directed architecture with various nanoscale building blocks.
Co-reporter:Yang Cao;Song Liu;Qian Shen;Kai Yan;Pingjian Li;Jun Xu;Dapeng Yu;Michael L. Steigerwald;Colin Nuckolls;Xuefeng Guo
Advanced Functional Materials 2009 Volume 19( Issue 17) pp:2743-2748
Publication Date(Web):
DOI:10.1002/adfm.200900408

Abstract

Graphene behaves as a robust semimetal with the high electrical conductivity stemming from its high-quality tight two-dimensional crystallographic lattice. It is therefore a promising electrode material. Here, a general methodology for making stable photoresponsive field effect transistors, whose device geometries are comparable to traditional macroscopic semiconducting devices at the nanometer scale, using cut graphene sheets as 2D contacts is detailed. These contacts are produced through oxidative cutting of individual 2D planar graphene by electron beam lithography and oxygen plasma etching. Nanoscale organic transistors based on graphene contacts show high-performance FET behavior with bulk-like carrier mobility, high on/off current ratio, and high reproducibility. Due to the presence of photoactive molecules, the devices display reversible changes in current when they are exposed to visible light. The calculated responsivity of the devices is found to be as high as ∼8.3 A W−1. This study forms the basis for making new types of ultrasensitive molecular devices, thus initiating broad research interest in the field of nanoscale/molecular electronics.

Co-reporter:Xiaojun Xian, Liying Jiao, Zhongyun Wu and Zhongfan Liu  
Chemical Communications 2009 (Issue 18) pp:2550-2552
Publication Date(Web):16 Mar 2009
DOI:10.1039/B900379G
By fabricating aPMMA control strip at the SWNTs-electrode contact area to screen off the water gate effect, metallic and semiconducting SWNTs were easily identified during the conventional electropolymerization process.
Co-reporter:Zhongfan Liu, Jin Zhang and Bo Gao  
Chemical Communications 2009 (Issue 45) pp:6902-6918
Publication Date(Web):07 Oct 2009
DOI:10.1039/B914588E
Due to remarkable rolling structure and distinct rolling direction, the chirality-dependent Raman spectra of single-walled carbon nanotubes (SWNTs) show two characteristic features: the radial breathing mode (RBM) and the G-band. Rich information about SWNTs presented by these Raman features makes Raman spectroscopy a general and common tool for characterizing structures and properties of SWNTs and their changes. When exerted by external forces, the geometrical structures of SWNTs will change, which further affects the electronic structures and phonon properties of SWNTs. In this article, emphasis is given to how Raman frequency and resonant-Raman intensity evolve under distinct strains, including uniaxial strain, torsional strain, radial deformation and bending deformation. It is found that depending on different structural variations, Raman spectra of SWNTs have different responses to each strain, showing that resonant-Raman spectroscopy is a suitable tool to characterize and study strains in SWNTs.
Co-reporter:Chaoqun Feng;Yagang Yao;Jin Zhang
Nano Research 2009 Volume 2( Issue 10) pp:
Publication Date(Web):2009 October
DOI:10.1007/s12274-009-9054-3
Using carbon nanotubes as nanobarriers, the growth of single-walled carbon nanotubes (SWNTs) on a quartz surface can be terminated. First, carbon nanotube nanobarriers were grown on a quartz surface by the gas flow-directed growth mode. Then, the SWNTs were grown on the quartz surface via the lattice-oriented growth mode, in which growth of SWNTs can be terminated by hitting the nanotube nanobarriers. Moreover, using the carbon nanotube nanobarrier as a marker, the mechanism of the growth of SWNTs on the quartz surface can be studied; a base-growth mechanism is indicated. Based on this termination process and the base-growth mechanism, SWNT arrays with controlled lengths can be grown on a quartz surface by fixing the sites of both catalysts and nanobarriers.
Co-reporter:GuoYong Xie;Jin Zhang;YongYi Zhang
Science China Technological Sciences 2009 Volume 52( Issue 5) pp:1181-1186
Publication Date(Web):2009 May
DOI:10.1007/s11431-008-0290-7
We report herein a rational approach for fabricating metal suspending nanostructures by nanoimprint lithography (NIL) and isotropic reactive ion etching (RIE). The approach comprises three principal steps: (1) mold fabrication, (2) structure replication by NIL, and (3) suspending nanostructures creation by isotropic RIE. Using this approach, suspending nanostructures with Au, Au/Ti or Ti/Au bilayers, and Au/Ti/Au sandwiched structures are demonstrated. For Au nanostructures, straight suspending nanostructures can be obtained when the thickness of Au film is up to 50 nm for nano-bridge and 90 nm for nano-finger patterns. When the thickness of Au is below 50 nm for nano-bridge and 90 nm for nano-finger, the Au suspending nanostructures bend upward as a result of the mismatch of thermal expansion between the thin Au films and Si substrate. This leads to residual stresses in the thin Au films. For Au/Ti or Ti/Au bilayers nanostructures, the cantilevers bend toward Au film, since Au has a larger thermal expansion coefficient than that of Ti. While in the case of sandwich structures, straight suspending nanostructures are obtained, this may be due to the balance of residual stress between the thin films.
Co-reporter:Manhong Liu, Tao Zhu, Zichen Li and Zhongfan Liu
The Journal of Physical Chemistry C 2009 Volume 113(Issue 22) pp:9670-9675
Publication Date(Web):May 11, 2009
DOI:10.1021/jp902234v
An efficient synthesis of poly(methyl methacrylate)-grafted SWCNT composites (PMMA-SWCNTs) were developed by using in situ atom transfer radical polymerization of methyl methacrylate onto SWCNTs sonicated in o-dichlorobenzene (ODCB) in one step. Morphology studies with HRTEM and AFM and solubility changes of the PMMA-SWCNTs in CHCl3 and DMF suggest the existence of PMMA in the nanocomposites. The sonochemical reaction of ODCB and SWCNTs is critical for the formation of PMMA-SWCNTs. Systematic characterization shows that PMMA was covalently attached to the SWCNTs in PMMA-SWCNTs.
Co-reporter:Liying Jiao ; Xiaojun Xian ; Ben Fan ; Zhongyun Wu ; Jin Zhang
The Journal of Physical Chemistry C 2008 Volume 112(Issue 20) pp:7544-7546
Publication Date(Web):April 11, 2008
DOI:10.1021/jp8020744
We presented a controllable yet simple approach for fabricating an air-stable single-walled carbon nanotube (SWNT) diode with the atomic force microscopy (AFM) manipulation technique. The AFM tip was utilized to create an asymmetric Schottky barrier at the two contacts of the SWNTs field effect transistors (FETs) by selectively modifying the tube−metal interaction or the contact length. Air-stable SWNTs diodes with rectification ratios of up to 104 were generated with this approach. We also demonstrated that the tube−metal interaction and the tube−metal contact length played an important role in determining the Schottky barrier at the tube−metal interface.
Co-reporter:Liying Jiao ; Xiaojun Xian
The Journal of Physical Chemistry C 2008 Volume 112(Issue 27) pp:9963-9965
Publication Date(Web):June 14, 2008
DOI:10.1021/jp802713j
A parallel, controllable yet simple approach was developed to manipulate single-walled carbon nanotubes (SWNTs) and create complex architectures of SWNTs. This approach was based on the utilization of flexible poly(methyl methacrylate) (PMMA) film as a mediator for indirectly manipulating the SWNTs. With this PMMA-mediated manipulation approach, SWNTs were bended at controlled bending angles without degrading their pristine properties. Meanwhile, crossbar arrays with controlled crossing angle were created. Moreover, complex two-dimensional (2D) architectures, such as steplike and zigzag structures of SWNTs were obtained without complicated lithographic processes. Our manipulation technique paves the way to fabricate novel 2D configuration of SWNTs, induce controllable strain in SWNTs and then build new devices based on them.
Co-reporter:Alfonso Reina, Hyungbin Son, Liying Jiao, Ben Fan, Mildred S. Dresselhaus, ZhongFan Liu and Jing Kong
The Journal of Physical Chemistry C 2008 Volume 112(Issue 46) pp:17741-17744
Publication Date(Web):2017-2-22
DOI:10.1021/jp807380s
The transferring and identification of single- and few- layer graphene sheets from SiO2/Si substrates to other types of substrates is presented. Features across large areas (∼cm2) having single and few-layer graphene flakes, obtained by the microcleaving of highly oriented pyrolytic graphite (HOPG), can be transferred reliably. This method enables the fast localization of graphene sheets on substrates on which optical microscopy does not allow direct and fast visualization of the thin graphene sheets. No major morphological deformations, corrugations, or defects are induced on the graphene films when transferred to the target surface. Moreover, the differentiation between single and bilayer graphene via the G′ (∼2700 cm−1) Raman peak is demonstrated on various substrates. This approach opens up possibilities for the fabrication of graphene devices on a substrate material other than SiO2/Si.
Co-reporter:Peng Qian, Zhongyun Wu, Peng Diao, Guoming Zhang, Jin Zhang and Zhongfan Liu
The Journal of Physical Chemistry C 2008 Volume 112(Issue 35) pp:13346-13348
Publication Date(Web):2017-2-22
DOI:10.1021/jp806043j
Single-walled carbon nanotubes (SWNTs) are promising building blocks for nanoelectronics. However, because of the mixture of metallic and semiconducting single-walled carbon nanotubes (m-SWNTs and s-SWNTs), it is necessary to identify them for nanodevice integerations. In this work, we have observed obvious electrodeposition differences of ultralong m-SWNTs and s-SWNTs. Using high-resolution atomic force microscopy (AFM) and field emission scanning electron microscopy (FE-SEM), particle densities along different carbon nanotubes were examined. Interestingly, m-SWNTs and s-SWNTs showed obviously different deposition behaviors, i.e., exponential decay of particle densities with different decay coefficients. This electrochemical approach can be used for a simple identification of m-SWNTs and s-SWNTs.
Co-reporter:Quan Qing Dr.;Fang Chen Dr.;Peigang Li Dr.;Weihua Tang ;Zhongyun Wu Dr.
Angewandte Chemie 2005 Volume 117(Issue 47) pp:
Publication Date(Web):3 NOV 2005
DOI:10.1002/ange.200502680

Positives Feedback: Aus einem hohen elektrischen Feld zwischen den Elektroden eines rückkopplungsgesteuerten Elektroabscheidungssystems ergibt sich eine Veränderung der Impedanz, die in reproduzierbarer Weise die Herstellung relativ großer Spalten ermöglicht. Die Größe der Spalten kann auf ca. 1 nm eingestellt werden, indem man einfach die Abscheidungszeit variiert (siehe REM-Aufnahmen).

Co-reporter:Quan Qing, Fang Chen, Peigang Li, Weihua Tang, Zhongyun Wu,Zhongfan Liu
Angewandte Chemie International Edition 2005 44(47) pp:7771-7775
Publication Date(Web):
DOI:10.1002/anie.200502680
Co-reporter:Xiaojun Xian, Liying Jiao, Zhongyun Wu and Zhongfan Liu
Chemical Communications 2009(Issue 18) pp:NaN2552-2552
Publication Date(Web):2009/03/16
DOI:10.1039/B900379G
By fabricating aPMMA control strip at the SWNTs-electrode contact area to screen off the water gate effect, metallic and semiconducting SWNTs were easily identified during the conventional electropolymerization process.
Co-reporter:Manish Chhowalla, Zhongfan Liu and Hua Zhang
Chemical Society Reviews 2015 - vol. 44(Issue 9) pp:NaN2586-2586
Publication Date(Web):2015/04/17
DOI:10.1039/C5CS90037A
A graphical abstract is available for this content
Co-reporter:Ruiqi Zhao, Jinying Wang, Mingmei Yang, Zhongfan Liu and Zhirong Liu
Physical Chemistry Chemical Physics 2013 - vol. 15(Issue 3) pp:NaN806-806
Publication Date(Web):2012/11/12
DOI:10.1039/C2CP42994B
Various graphene quantum dots (GQDs) embedded in a hexagonal BN sheet were studied theoretically using the tight binding model. The effective mass was analyzed as a function of the distance between neighboring GQDs. It was found that the effective mass increases exponentially as the distance increases, indicating that the confined states of GQDs are well conserved in these hybrid systems. Further studies revealed that a ubiquitous gap of 0.3–3 eV exists, the size of which is mainly governed by the GQD's dimensions whereas it is insensitive to edge structures. These results show that GQDs in BN are promising candidates for optoelectronics.
Co-reporter:Lianming Tong, Tao Zhu and Zhongfan Liu
Chemical Society Reviews 2011 - vol. 40(Issue 3) pp:NaN1304-1304
Publication Date(Web):2010/12/01
DOI:10.1039/C001054P
Surface-enhanced Raman scattering (SERS) has been intensively explored both in theory and applications and has been widely used in chemistry, physics and biology for decades. A variety of SERS substrates have been developed in order to investigate the mechanisms behind, which give rise to the enormous enhancement even enabling single molecule detection. The Raman enhancement, which involves an electromagnetic enhancement (EM) and a chemical enhancement (CM), reflects both the physical principle of light/metal interactions and the molecule/metal interactions. In this tutorial review, we focus on the EM enhancement of SERS active substrates made of colloidal gold nanoparticles (GNPs), varying from self-assembled arrays down to single particles, for the purpose of investigating the EM coupling effect and probing the distribution of the induced electric field of single GNPs.
Co-reporter:Qingqing Ji, Yu Zhang, Yanfeng Zhang and Zhongfan Liu
Chemical Society Reviews 2015 - vol. 44(Issue 9) pp:NaN2602-2602
Publication Date(Web):2014/09/26
DOI:10.1039/C4CS00258J
As structural analogues of graphene but with a sizeable band gap, monolayers of group-VIB transition metal dichalcogenides (MX2, M = Mo, W; X = S, Se, Te, etc.) have emerged as the ideal two dimensional prototype for exploring fundamental issues in physics such as valley polarization, and for engineering a wide range of nanoelectronic, optoelectronic and photocatalytic applications. Recently, chemical vapour deposition (CVD) was introduced as a more efficient preparation method than traditional chemical or physical exfoliation options, and has allowed for the successful synthesis of large-area MX2 monolayers possessing a large domain size, high thickness uniformity and continuity, and satisfactory crystal quality. This tutorial review therefore focuses on introducing the more recent advances in the CVD growth of MX2 (MoS2, WS2, MoS2(1−x)Se2xetc.) monolayers via the sulphurisation/decomposition of pre-deposited metal-based precursors, or the one-step reaction and deposition of gaseous metal and chalcogen feedstocks. Differences in growth behaviour caused by commonly used amorphous SiO2/Si, and newly adopted insulating single crystal substrates such as sapphire, mica and SrTiO3, are also comparatively presented. Also discussed are the essential parameters that influence the growth of MX2, such as the temperature, the source–substrate distance and the composition of the carrier gas (Ar/H2). Finally, an assessment is provided for viable future pathways for fine-tuning of the domain size and orientation, thickness uniformity, and the bandgap of MX2 and its alloys.
Co-reporter:Jinying Wang, Shuqing Zhang, Jingyuan Zhou, Rong Liu, Ran Du, Hua Xu, Zhongfan Liu, Jin Zhang and Zhirong Liu
Physical Chemistry Chemical Physics 2014 - vol. 16(Issue 23) pp:NaN11309-11309
Publication Date(Web):2014/04/23
DOI:10.1039/C4CP00539B
Two-dimensional (2D) materials composed of sp and sp2 carbon atoms (e.g., graphyne and graphdiyne) show many interesting properties. These materials can be constructed through alkyne homocoupling; however, the occurrence of various side reactions increases the difficulty of their synthesis and structural characterization. Here, we investigate the thermodynamic properties and vibrational spectra of several aryl-alkynes. Both homocoupling and side reactions are found to occur spontaneously at room temperature in terms of thermodynamics. The calculated Raman spectra of the homocoupling products show regular changes with increasing polymerization degree. By rationalizing the vibrational modes of various oligomers, the Raman spectrum of a 2D sp–sp2 carbon sheet is predicted; it exhibits three sharp peaks at 2241, 1560, and 1444 cm−1. Although the target and byproducts display similar vibrational modes, a combination of Raman and infrared spectroscopies can be used to differentiate them. The theoretical results are then used to analyze the structure of a synthesized sample and provide useful information.
Co-reporter:Zhongfan Liu, Jin Zhang and Bo Gao
Chemical Communications 2009(Issue 45) pp:NaN6918-6918
Publication Date(Web):2009/10/07
DOI:10.1039/B914588E
Due to remarkable rolling structure and distinct rolling direction, the chirality-dependent Raman spectra of single-walled carbon nanotubes (SWNTs) show two characteristic features: the radial breathing mode (RBM) and the G-band. Rich information about SWNTs presented by these Raman features makes Raman spectroscopy a general and common tool for characterizing structures and properties of SWNTs and their changes. When exerted by external forces, the geometrical structures of SWNTs will change, which further affects the electronic structures and phonon properties of SWNTs. In this article, emphasis is given to how Raman frequency and resonant-Raman intensity evolve under distinct strains, including uniaxial strain, torsional strain, radial deformation and bending deformation. It is found that depending on different structural variations, Raman spectra of SWNTs have different responses to each strain, showing that resonant-Raman spectroscopy is a suitable tool to characterize and study strains in SWNTs.
Silane, 1,1'-[3,4-bis[2-(trimethylsilyl)ethynyl]-3-hexene-2,5-diyne-1,6-diyl]bis[1,1,1-trimethyl-
Ethynyl, (trimethylsilyl)-
C N
CHLOROZINC(1+);ETHYNYL(TRIMETHYL)SILANE
Phosphoric acid, cobalt salt
butan-1-aminium bromide
Tantalum carbide (Ta2C)
Niobium carbide (Nb2C)