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CONSPECTUS: Two-dimensional (2D) compound materials are promising materials for use in electronics, optoelectronics, flexible devices, etc. because they are ultrathin and cover a wide range of properties. Among all methods to prepare 2D materials, chemical vapor deposition (CVD) is promising because it produces materials with a high quality and reasonable cost. So far, much efforts have been made to produce 2D compound materials with large domain size, controllable number of layers, fast-growth rate, and high quality features, etc. However, due to the complicated growth mechanism like sublimation and diffusion processes of multiple precursors, maintaining the controllability, repeatability, and high quality of CVD grown 2D binary and ternary materials is still a big challenge, which prevents their widespread use. Here, taking 2D transition metal dichalcogenides (TMDCs) as examples, we review current progress and highlight some promising growth strategies for the growth of 2D compound materials. The key technology issues which affect the CVD process, including non-metal precursor, metal precursor, substrate engineering, temperature, and gas flow, are discussed. Also, methods in improving the quality of CVD-grown 2D materials and current understanding on their growth mechanism are highlighted. Finally, challenges and opportunities in this field are proposed. We believe this review will guide the future design of controllable CVD systems for the growth of 2D compound materials with good controllability and high quality, laying the foundations for their potential applications.

Two-dimensional (2D) materials are promising candidates in wide applications including energy storage and conversion, sensors, flexible devices, etc. The low-cost production of 2D materials with large quantities and demanded quality is the precondition for their commercial uses. For graphene and its derivatives, relatively mature techniques have been established for their scalable preparation and industrial applications. Whereas the mass production of 2D materials beyond graphene is still in its early age and it lacks a summary on this topic. This review systematically describes the state-of-the-art approaches for high-yield preparation of 2D materials beyond graphene, including “top-down” exfoliation and “bottom-up” synthetic approaches. In particular, each method is discussed from the perspectives of its principle, optimization attempts, characteristics of the obtained 2D materials, and its scalability potential. The applications that require massively-produced 2D materials are highlighted, including electrocatalysis, batteries, supercapacitors, mechanical and chemical sensors, as well as electromagnetic interference shielding and microwave absorption devices. Finally, we propose the challenges and opportunities for scalable preparation and commercial applications of 2D materials.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted great attention due to their physical and chemical properties that make them promising in electronics and optoelectronics. Because of the difficulties in controlling concentrations of solid precursors and spatially nonuniform growth dynamics, it is challenging to grow 2D TMDCs over large areas with good uniformity and reproducibility so far, which significantly hinders their practical use. Here we report a vertical chemical vapor deposition (VCVD) design with gaseous precursors to grow monolayer TMDCs with a uniform density and high quality over the whole substrate and with excellent reproducibility. Such a gaseous VCVD design can well control the three key parameters in TMDC growth, including precursor concentration, gas flow, and temperature, which cannot be done in a currently widely used horizontal CVD system with solid precursors. Statistical results show that VCVD-grown monolayer TMDCs including MoS

The scalable and high-efficiency production of 2D materials is a prerequisite to their commercial use. Currently, only graphene and graphene oxide can be produced on a ton scale, and the inability to produce other 2D materials on such a large scale hinders their technological applications. Here we report a grinding exfoliation method that uses micro-particles as force intermediates to resolve applied compressive forces into a multitude of small shear forces, inducing the highly efficient exfoliation of layer materials. The method, referred to as intermediate-assisted grinding exfoliation (iMAGE), can be used for the large-scale production of many 2D materials. As an example, we have exfoliated bulk h-BN into 2D h-BN with large flake sizes, high quality and structural integrity, with a high exfoliation yield of 67%, a high production rate of 0.3 g h−1 and a low energy consumption of 3.01 × 106 J g−1. The production rate and energy consumption are one to two orders of magnitude better than previous results. Besides h-BN, this iMAGE technology has been used to exfoliate various layer materials such as graphite, black phosphorus, transition metal dichalcogenides, and metal oxides, proving its universality. Molybdenite concentrate, a natural low-cost and abundant mineral, was used as a demo for the large-scale exfoliation production of 2D MoS2 flakes. Our work indicates the huge potential of the iMAGE method to produce large amounts of various 2D materials, which paves the way for their commercial application.

Electrochemical energy conversion between electricity and chemicals through electrocatalysis is a promising strategy for the development of clean and sustainable energy sources. This is because efficient electrocatalysts can greatly reduce energy loss during the conversion process. However, poor catalytic performances and a shortage in catalyst material resources have greatly restricted the widespread applications of electrocatalysts in these energy conversion processes. To address this issue, earth-abundant two-dimensional (2D) materials with large specific surface areas and easily tunable electronic structures have emerged in recent years as promising high-performance electrocatalysts in various reactions, and because of this, this review will comprehensively discuss the engineering of these novel 2D material-based electrocatalysts and their associated heterostructures. In this review, the fundamental principles of electrocatalysis and important electrocatalytic reactions are introduced. Following this, the unique advantages of 2D material-based electrocatalysts are discussed and catalytic performance enhancement strategies are presented, including the tuning of electronic structures through various methods such as heteroatom doping, defect engineering, strain engineering, phase conversion and ion intercalation, as well as the construction of heterostructures based on 2D materials to capitalize on individual advantages. Finally, key challenges and opportunities for the future development of these electrocatalysts in practical energy conversion applications are presented.

The high-throughput scalable production of cheap, efficient and durable electrocatalysts that work well at high current densities demanded by industry is a great challenge for the large-scale implementation of electrochemical technologies. Here we report the production of a two-dimensional molybdenum disulfide-based ink-type electrocatalyst by a scalable exfoliation technique followed by a thermal treatment. The catalyst delivers a high current density of 1000 mA cm−2 at an overpotential of 412 mV for the hydrogen evolution. Using the same method, we produce a cheap mineral-based catalyst possessing excellent performance for high-current-density hydrogen evolution. Noteworthy, production rate of this catalyst is one to two orders of magnitude higher than those previously reported, and price of the mineral is five orders of magnitude lower than commercial Pt electrocatalysts. These advantages indicate the huge potentials of this method and of mineral-based cheap and abundant natural resources as catalysts in the electrochemical industry., The large-scale implementation of electrochemical technologies will require the high-throughput production of high-performance, inexpensive catalysts. Here, authors demonstrate earth abundant molybdenite as raw materials to produce efficient MoS2 catalysts for high current density H2 evolution.

Currently, massive preparation of boron nitride nanosheets (BNNSs) towards large-size and good structural integrity via ball milling remains a key challenge, limiting its extensive applications in thermal management and energy storage. Low-cost and recyclable BaTiO3 nanoparticles with good piezoelectric effect can concurrently act as collision buffers and strong reductants to suppress the in-plane crystal structure damage and surface oxidation triggered by high-energy mechanical impact. Herein, an environmentally friendly, simple to operate and easy to realize industrial production method, referred to as BaTiO3-assisted ball milling (BTABM), is demonstrated to prepare high quality few-layered BNNSs with an average lateral size of 0.56 μm and a high yield of 91.2%. This milling process involves the synergetic effects of mechanical shear and mechanochemical peeling provided by deformed BaTiO3. The incorporation of the prepared BNNSs into the P(VDF-CTFE) matrix by BTABM effectively improved simultaneously the dielectric properties and breakdown strength of the ternary P(VDF-CTFE)/BaTiO3/BNNS nanocomposites as well as their thermal management capability, due to the formation of 3D BNNS networks. This novel method provides a guidance for not only scalable exfoliation of other layered 2D materials but also massive fabrication of polymeric nanocomposites applied in high-temperature energy storage devices.

Hollow micro-/nanostructures of metal oxides have attracted tremendous research attention in energy storage due to their unique structural advantages. Although fabrication of spherical hollow architectures have been intensively reported, rational design and facile synthesis of anisotropic hollow structures are still quite challenging, especially for those complex mixed metal oxides with well-controlled interior structures. Herein, through facile citrate-assisted hydrothermal synthesis and subsequent controlled annealing, well-defined octahedral ZnCo2O4 solid, hollow and yolk-shell micro-/nanostructures were constructed for the first time. When used as anode materials for lithium ion batteries (LIBs), the hollow ZnCo2O4 octahedron exhibits the best lithium storage properties, delivering high discharge capacities of 880 mA h g−1 over 160 cycles at 0.2 A g−1, and 650 mA h g−1 over 300 cycles at 1 A g−1. Moreover, it shows a superior high-rate performance with 60% of the specific capacity maintained even at a high current density of 5 A g−1. These features render the hollow octahedral ZnCo2O4 micro-/nanostructure a promising anode for next generation LIBs.

Two-dimensional (2D) materials have attracted increasing research interest because of the abundant choice of materials with diverse and tunable electronic, optical, and chemical properties. Moreover, 2D material based heterostructures combining several individual 2D materials provide unique platforms to create an almost infinite number of materials and show exotic physical phenomena as well as new properties and applications. To achieve these high expectations, methods for the scalable preparation of 2D materials and 2D heterostructures of high quality and low cost must be developed. Chemical vapor deposition (CVD) is a powerful method which may meet the above requirements, and has been extensively used to grow 2D materials and their heterostructures in recent years, despite several challenges remaining. In this review of the challenges in the CVD growth of 2D materials, we highlight recent advances in the controlled growth of single crystal 2D materials, with an emphasis on semiconducting transition metal dichalcogenides. We provide insight into the growth mechanisms of single crystal 2D domains and the key technologies used to realize wafer-scale growth of continuous and homogeneous 2D films which are important for practical applications. Meanwhile, strategies to design and grow various kinds of 2D material based heterostructures are thoroughly discussed. The applications of CVD-grown 2D materials and their heterostructures in electronics, optoelectronics, sensors, flexible devices, and electrocatalysis are also discussed. Finally, we suggest solutions to these challenges and ideas concerning future developments in this emerging field.

Extensive research on two-dimensional (2D) materials has triggered the renaissance of an old topic, that is, the intercalation and exfoliation of layer materials. Such top-down exfoliation produced 2D materials and their dispersions have several advantages including low cost, scalable production capability, solution processability, and versatile functionalities stemming from the large number of species of layer materials, and show promising potential in many applications. In recent years, many new methods have been developed for exfoliating layer materials to 2D materials for different application purposes. In this review the different exfoliation approaches are first systematically analyzed from the viewpoint of methodology, and the advantages and disadvantages of each method are compared. Second, the assembly of exfoliated 2D materials into macrostructures by solution-based techniques is summarized. Third, the state-of-the-art applications of 2D material dispersions and their assemblies in electronics and optoelectronics, electrocatalysis, energy storage, etc., are discussed. Finally, insights and perspectives on current research challenges and future opportunities regarding the exfoliation and applications of 2D materials in dispersions are considered.

Preparation of chirality-defined single-wall carbon nanotubes (SWCNTs) is the top challenge in the nanotube field. In recent years, great progress has been made toward preparing single-chirality SWCNTs through both direct controlled synthesis and postsynthesis separation approaches. Accordingly, the uses of single-chirality-dominated SWCNTs for various applications have emerged as a new front in nanotube research. In this Review, we review recent progress made in the chirality-controlled synthesis of SWCNTs, including metal-catalyst-free SWCNT cloning by vapor-phase epitaxy elongation of purified single-chirality nanotube seeds, chirality-specific growth of SWCNTs on bimetallic solid alloy catalysts, chirality-controlled synthesis of SWCNTs using bottom-up synthetic strategy from carbonaceous molecular end-cap precursors, etc. Recent major progresses in postsynthesis separation of single-chirality SWCNT species, as well as methods for chirality characterization of SWCNTs, are also highlighted. Moreover, we discuss some examples where single-chirality SWCNTs have shown clear advantages over SWCNTs with broad chirality distributions. We hope this review could inspire more research on the chirality-controlled preparation of SWCNTs and equally important inspire the use of single-chirality SWCNT samples for more fundamental studies and practical applications.

The practical use of lithium–sulfur (Li–S) batteries is largely hindered by their poor cycling stability because of the shuttling of soluble lithium polysulfides (LiPSs) in a slow redox reaction. Physical and chemical confinement by carbon or noncarbon hosts has been used to block LiPS shuttling, but this may only be a complete solution to the problem if it combines with LiPS fast conversion into an insoluble sulfide. Here we report a twinborn TiO2–TiN heterostructure that combines the merits of highly adsorptive TiO2 with conducting TiN and achieves smooth trapping–diffusion–conversion of LiPSs across the interface. TiO2 has high adsorption for LiPSs while TiN promotes their conversion into insoluble Li2S. The fast diffusion of LiPSs from TiO2 to TiN helps achieve both high trapping efficiency and fast conversion. By loading such a heterostructure onto graphene, which acts as a physical barrier, a compact and thin coating is fabricated on the separator, and LiPS shuttling is greatly restrained even with a high sulfur loading. A capacity of 927 mA h g−1 after 300 cycles is obtained under a low current density of 0.3C. Over 2000 cycles, capacity retentions of 73% and 67% at 1C are achieved for sulfur loadings of 3.1 and 4.3 mg cm−2. Such an interlayer is expected to promote the practical use of Li–S batteries because of the simple processing and the resulting outstanding capacity and cyclic performance. Such a heterostructure suggests a new way to produce multifunctional interlayers that improve the performance of energy storage devices.

Monolayer WSe2 is a two-dimensional (2D) semiconductor with a direct band gap, and it has been recently explored as a promising material for electronics and optoelectronics. Low field-effect mobility is the main constraint preventing WSe2 from becoming one of the competing channel materials for field-effect transistors (FETs). Recent results have demonstrated that chemical treatments can modify the electrical properties of transition metal dichalcogenides (TMDCs), including MoS2 and WSe2. Here, we report that controlled heating in air significantly improves device performance of WSe2 FETs in terms of on-state currents and field-effect mobilities. Specifically, after being heated at optimized conditions, chemical vapor deposition grown monolayer WSe2 FETs showed an average FET mobility of 31 cm(2)·V(-1)·s(-1) and on/off current ratios up to 5 × 10(8). For few-layer WSe2 FETs, after the same treatment applied, we achieved a high mobility up to 92 cm(2)·V(-1)·s(-1). These values are significantly higher than FETs fabricated using as-grown WSe2 flakes without heating treatment, demonstrating the effectiveness of air heating on the performance improvements of WSe2 FETs. The underlying chemical processes involved during air heating and the formation of in-plane heterojunctions of WSe2 and WO3-x, which is believed to be the reason for the improved FET performance, were studied by spectroscopy and transmission electron microscopy. We further demonstrated that, by combining the air heating method developed in this work with supporting 2D materials on the BN substrate, we achieved a noteworthy field-effect mobility of 83 cm(2)·V(-1)·s(-1) for monolayer WSe2 FETs. This work is a step toward controlled modification of the properties of WSe2 and potentially other TMDCs and may greatly improve device performance for future applications of 2D materials in electronics and optoelectronics.

Semiconducting single-wall carbon nanotubes (SWCNTs) with long lengths are highly desirable for many applications such as thin-film transistors and circuits. Previously reported length sorting techniques usually require sophisticated instrumentation and are hard to scale up. In this paper, we report for the first time a general phenomenon of a length-dependent precipitation of surfactant-dispersed carbon nanotubes by polymers, salts, and their combinations. Polyelectrolytes such as polymethacrylate (PMAA) and polystyrene sulfonate (PSS) are found to be especially effective on cholate and deoxycholate dispersed SWCNTs. By adding PMAA to these nanotube dispersions in a stepwise fashion, we have achieved nanotube precipitation in a length-dependent order: first nanotubes with an average length of 650 nm, and then successively of 450 nm, 350 nm, and 250 nm. A similar effect of nanotube length sorting has also been observed for PSS. To demonstrate the utility of the length fractionation, the 650 nm-long nanotube fraction was subjected to an aqueous two-phase separation to obtain semiconducting enriched nanotubes. Thin-film transistors fabricated with the resulting semiconducting SWCNTs showed a carrier mobility up to 18 cm(2) (V s)(-1) and an on/off ratio up to 10(7). Our result sheds new light on the phase behavior of aqueous nanotube dispersions under high concentrations of polymers and salts, and offers a facile, low-cost, and scalable method to produce length sorted semiconducting nanotubes for macroelectronics applications.

As new 2D layered nanomaterials, Bi2 O2 Se nanoplates have unique semiconducting properties that can benefit biomedical applications. Herein, a facile top-down approach for the synthesis of Bi2 O2 Se quantum dots (QDs) in a solution is described. The Bi2 O2 Se QDs with a size of 3.8 nm and thickness of 1.9 nm exhibit a high photothermal conversion coefficient of 35.7% and good photothermal stability. In vitro and in vivo assessments demonstrate that the Bi2 O2 Se QDs possess excellent photoacoustic (PA) performance and photothermal therapy (PTT) efficiency. After systemic administration, the Bi2 O2 Se QDs accumulate passively in tumors enabling efficient PA imaging of the entire tumors to facilitate imaging-guided PTT without obvious toxicity. Furthermore, the Bi2 O2 Se QDs which exhibit degradability in aqueous media not only have sufficient stability during in vivo circulation to perform the designed therapeutic functions, but also can be discharged harmlessly from the body afterward. The results reveal the great potential of Bi2 O2 Se QDs as a biodegradable multifunctional agent in medical applications.

Two-dimensional (2D) semiconducting monolayer transition metal dichalcogenides (TMDCs) have stimulated lots of interest because they are direct bandgap materials that have reasonably good mobility values. However, contact between most metals and semiconducting TMDCs like 2H phase WSe2 are highly resistive, thus degrading the performance of field effect transistors (FETs) fabricated with WSe2 as active channel materials. Recently, a phase engineering concept of 2D MoS2 materials was developed, with improved device performance. Here, we applied this method to chemical vapor deposition (CVD) grown monolayer 2H-WSe2 and demonstrated semiconducting-to-metallic phase transition in atomically thin WSe2. We have also shown that metallic phase WSe2 can be converted back to semiconducting phase, demonstrating the reversibility of this phase transition. In addition, we fabricated FETs based on these CVD-grown WSe2 flakes with phase-engineered metallic 1T-WSe2 as contact regions and intact semiconducting 2H-WSe2 as active channel materials. The device performance is substantially improved with metallic phase source/drain electrodes, showing on/off current ratios of 10(7) and mobilities up to 66 cm(2)/V·s for monolayer WSe2. These results further suggest that phase engineering can be a generic strategy to improve device performance for many kinds of 2D TMDC materials.

Semiconducting single-wall carbon nanotubes are very promising materials in printed electronics due to their excellent mechanical and electrical property, outstanding printability, and great potential for flexible electronics. Nonetheless, developing scalable and low-cost approaches for manufacturing fully printed high-performance single-wall carbon nanotube thin-film transistors remains a major challenge. Here we report that screen printing, which is a simple, scalable, and cost-effective technique, can be used to produce both rigid and flexible thin-film transistors using separated single-wall carbon nanotubes. Our fully printed top-gated nanotube thin-film transistors on rigid and flexible substrates exhibit decent performance, with mobility up to 7.67 cm2 V(-1) s(-1), on/off ratio of 10(4)∼10(5), minimal hysteresis, and low operation voltage (10 V). In addition, outstanding mechanical flexibility of printed nanotube thin-film transistors (bent with radius of curvature down to 3 mm) and driving capability for organic light-emitting diode have been demonstrated. Given the high performance of the fully screen-printed single-wall carbon nanotube thin-film transistors, we believe screen printing stands as a low-cost, scalable, and reliable approach to manufacture high-performance nanotube thin-film transistors for application in display electronics. Moreover, this technique may be used to fabricate thin-film transistors based on other materials for large-area flexible macroelectronics, and low-cost display electronics.

Titanium carbide MXene quantum dots (QDs) were synthesized using an effective fluorine-free method as a biocompatible and highly efficient nanoagent for photothermal therapy (PTT) applications. In contrast to the traditional, hazardous and time-consuming process of HF pretreatment, our fluorine-free method is safe and simple. More importantly, abundant Al oxoanions were found to be modified on the MXene QD surface by the fluorine-free method, which endowed the QDs with strong and broad absorption in the NIR region. As a result, the as-prepared MXene QDs exhibited an extinction coefficient as large as 52.8 Lg-1 cm-1 at 808 nm and a photothermal conversion efficiency as high as 52.2%. Both the values are among the best reported so far. The as-prepared MXene QDs achieved simultaneous photoacoustic (PA) imaging and the remarkable PTT effect of tumors. Moreover, MXene QDs showed great biocompatibility without causing noticeable toxicity in vitro and in vivo, indicating their high potential for clinical applications.

Carbon nanotubes (CNTs) have emerged as an important material for printed macroelectronics. However, achieving printed complementary macroelectronics solely based on CNTs is difficult because it is still challenging to make reliable n-type CNT transistors. In this study, we report threshold voltage (V th) tuning and printing of complementary transistors and inverters composed of thin films of CNTs and indium zinc oxide (IZO) as p-type and n-type transistors, respectively. We have optimized the V th of p-type transistors by comparing Ti/Au and Ti/Pd as source/drain electrodes, and observed that CNT transistors with Ti/Au electrodes exhibited enhancement mode operation (V th < 0). In addition, the optimized In:Zn ratio offers good n-type transistors with high on-state current (I on) and enhancement mode operation (V th > 0). For example, an In:Zn ratio of 2:1 yielded an enhancement mode n-type transistor with V th ∼ 1 V and I on of 5.2 μA. Furthermore, by printing a CNT thin film and an IZO thin film on the same substrate, we have fabricated a complementary inverter with an output swing of 99.6% of the supply voltage and a voltage gain of 16.9. This work shows the promise of the hybrid integration of p-type CNT and n-type IZO for complementary transistors and circuits.

The conductivity enhancement of single-walled carbon nanotube (SWCNT) films was achieved by increasing the bundle length in an aerosol CVD synthesis method with the help of two carbon sources. Carbon monoxide provides carbon at temperatures below 900 °C, while ethylene takes over at higher temperatures. The significant decrease in the sheet resistance at the 90% transmittance was observed from 3500 to 7500 Ω/sq. for pure CO system via 1909 and 1709 Ω/sq. for CO–H2 system to 291 and 358 Ω/sq. in the presence of C2H4 at 900 and 1100 °C, respectively. Doping the film with a gold chloride solution in acetonitrile allowed us to create the transparent conductive films with the sheet resistance as low as 73 Ω/sq. at a transmittance of 90%.

Due to their excellent electrical properties and compatibility with room-temperature deposition/printing processing, high-purity single-walled semiconducting carbon nanotubes hold great potential for macroelectronic applications such as in thin-film transistors and display back-panel electronics. However, the relative advantages and disadvantages of various nanotubes for macroelectronics remains an open issue, despite the great significance. Here in this paper, we report a comparative and systematic study of three kinds of mainstream carbon nanotubes (arc-discharge, HiPCO, CoMoCAT) separated using low-cost gel-based column chromatography for thin-film transistor applications, and high performance transistors-which satisfy the requirements for transistors used in active matrix organic light-emitting diode displays-have been achieved. We observe a trade-off between transistor mobility and on/off ratio depending on the nanotube diameter. While arc-discharge nanotubes with larger diameters lead to high device mobility, HiPCO and CoMoCAT nanotubes with smaller diameters can provide high on/off ratios (> 106) for transistors with comparable dimensions. Furthermore, we have also compared gel-based separated nanotubes with nanotubes separated using the density gradient ultracentrifuge (DGU) method, and find that gel-separated nanotubes can offer purity and thin-film transistor performance as good as DGU-separated nanotubes. Our approach can serve as the critical foundation for future carbon nanotube-based thin-film macroelectronics. Open image in new window

Structurally uniform and chirality-pure single-wall carbon nanotubes are highly desired for both fundamental study and many of their technological applications, such as electronics, optoelectronics, and biomedical imaging. Considerable efforts have been invested in the synthesis of nanotubes with defined chiralities by tuning the growth recipes but the approach has only limited success. Recently, we have shown that chirality-pure short nanotubes can be used as seeds for vapor-phase epitaxial cloning growth, opening up a new route toward chirality-controlled carbon nanotube synthesis. Nevertheless, the yield of vapor-phase epitaxial growth is rather limited at the present stage, due in large part to the lack of mechanistic understanding of the process. Here we report chirality-dependent growth kinetics and termination mechanism for the vapor-phase epitaxial growth of seven single-chirality nanotubes of (9, 1), (6, 5), (8, 3), (7, 6), (10, 2), (6, 6), and (7, 7), covering near zigzag, medium chiral angle, and near armchair semiconductors, as well as armchair metallic nanotubes. Our results reveal that the growth rates of nanotubes increase with their chiral angles while the active lifetimes of the growth hold opposite trend. Consequently, the chirality distribution of a nanotube ensemble is jointly determined by both growth rates and lifetimes. These results correlate nanotube structures and properties with their growth behaviors and deepen our understanding of chirality-controlled growth of nanotubes.

Tadpole-like carbon nanotubes (CNTs) were synthesized by chemical vapor deposition from ethanol using TiO2 nanoparticles (NPs) as catalyst. The CNTs have a cup-stacked structure are typically less than 500 nm in length, and have a non-uniform diameter with a big "head" and a smaller diameter "tail", inside which a catalyst NP is usually encapsulated. Transmission electron microscopy (TEM) characterisation reveals that the TiO2 catalyst NPs are oxygen-deficient, which is considered to be responsible for the gradually diminishing diameter of the CNTs. In situ TEM study further confirms that the effective catalytic species is solid oxygen-deficient titanium oxide. A tip growth mode combined with vapor-solid-solid mechanism is proposed for the growth of the CNTs. (C) 2012 Elsevier Ltd. All rights reserved.

Graphene nanoribbons (GNRs), quasi-one-dimensional graphene strips, have shown great potential for nanoscale electronics, optoelectronics, and photonics. Atomically precise GNRs can be "bottom-up" synthesized by surface-assisted assembly of molecular building blocks under ultra-high-vacuum conditions. However, large-scale and efficient synthesis of such GNRs at low cost remains a significant challenge. Here we report an efficient "bottom-up" chemical vapor deposition (CVD) process for inexpensive and high-throughput growth of structurally defined GNRs with varying structures under ambient-pressure conditions. The high quality of our CVD-grown GNRs is validated by a combination of different spectroscopic and microscopic characterizations. Facile, large-area transfer of GNRs onto insulating substrates and subsequent device fabrication demonstrate their promising potential as semiconducting materials, exhibiting high current on/off ratios up to 6000 in field-effect transistor devices. This value is 3 orders of magnitude higher than values reported so far for other thin-film transistors of structurally defined GNRs. Notably, on-surface mass spectrometry analyses of polymer precursors provide unprecedented evidence for the chemical structures of the resulting GNRs, especially the heteroatom doping and heterojunctions. These results pave the way toward the scalable and controllable growth of GNRs for future applications.

Chiralities of single-walled carbon nanotubes grown on an atomic layer deposition prepared bimetallic FeCu/MgO catalyst were evaluated quantitatively using nanobeam electron diffraction. The results reveal that the growth yields nearly 90% semiconducting tubes, 45% of which are of the (6,5) type. The growth mechanisms as well as the roles of different components in the catalyst were studied in situ using environmental transmission electron microscopy and infrared spectroscopy. On the basis of the understanding of carbon nanotube growth mechanisms, an MgO-supported FeCu catalyst was prepared by impregnation, showing similar catalytic performance as the atomic layer deposition-prepared catalyst, yielding single-walled carbon nanotubes with a similar narrow chirality distribution.

Integration of individual two-dimensional graphene sheets into macroscopic structures is essential for the application of graphene. A series of graphene-based composites and macroscopic structures have been recently fabricated using chemically derived graphene sheets. However, these composites and structures suffer from poor electrical conductivity because of the low quality and/or high inter-sheet junction contact resistance of the chemically derived graphene sheets. Here we report the direct synthesis of three-dimensional foam-like graphene macrostructures, which we call graphene foams (GFs), by template-directed chemical vapour deposition. A GF consists of an interconnected flexible network of graphene as the fast transport channel of charge carriers for high electrical conductivity. Even with a GF loading as low as ∼0.5 wt%, GF/poly(dimethyl siloxane) composites show a very high electrical conductivity of ∼10 S cm(-1), which is ∼6 orders of magnitude higher than chemically derived graphene-based composites. Using this unique network structure and the outstanding electrical and mechanical properties of GFs, as an example, we demonstrate the great potential of GF/poly(dimethyl siloxane) composites for flexible, foldable and stretchable conductors.

In order to achieve high energy and power densities, we developed a high-voltage asymmetric electrochemical capacitor (EC) based on graphene as negative electrode and a MnO(2) nanowire/graphene composite (MGC) as positive electrode in a neutral aqueous Na(2)SO(4) solution as electrolyte. MGC was prepared by solution-phase assembly of graphene sheets and α-MnO(2) nanowires. Such aqueous electrolyte-based asymmetric ECs can be cycled reversibly in the high-voltage region of 0-2.0 V and exhibit a superior energy density of 30.4 Wh kg(-1), which is much higher than those of symmetric ECs based on graphene//graphene (2.8 Wh kg(-1)) and MGC//MGC (5.2 Wh kg(-1)). Moreover, they present a high power density (5000 W kg(-1) at 7.0 Wh kg(-1)) and acceptable cycling performance of ∼79% retention after 1000 cycles. These findings open up the possibility of graphene-based composites for applications in safe aqueous electrolyte-based high-voltage asymmetric ECs with high energy and power densities.

A combined in situ and post-synthesis gas phase oxidation approach for selective removal of metallic single-walled carbon nanotubes (m-SWCNTs) is reported. The in situ oxidation is performed by introducing a small amount of oxygen during the synthesis of SWCNTs by floating catalyst chemical vapor deposition, and the post-synthesis oxidation is conducted by heat-treating the synthesized SWCNTs in air at 400 C. A combination of characterization techniques shows that m-SWCNTs were selectively removed as a result of their higher reactive activity to oxygen compared to semiconducting SWCNTs, and the diameter distribution of the SWCNTs is narrowed to a range of 1.5‐2.0 nm. The mechanism of the combined in situ and post-synthesis oxidation approach is discussed.

The carbon nanotube (CNT) is a model system of one-dimensional nanomaterials, which shows numerous unique properties and vast potential applications. The synthesis and assembly of high-quality CNTs are the basis for studies of their properties and applications. In this contribution, we briefly review our works on the controlled synthesis of single-walled CNTs (SWCNTs) and double-walled CNTs via floating catalyst chemical vapor deposition and arc-discharge methods. The in situ assembly of such CNTs into ordered macrostructures with various dimensions including ropes, films, and buckybooks are also presented. Finally, we introduced our recent findings on metal-catalyst-free growth of SWCNTs. (C) 2010 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

We report on the observation of a very low growth velocity of single-walled carbon nanotubes (SWNTs) and consequently the direct length-sorted growth and patterned growth of SWNTs by using a metal-catalyst-free chemical vapor deposition (CVD) process proposed recently by our group, in which SiO(2) serves as catalyst. We found that the growth velocity of the SWNTs from SiO(2) catalyst is only 8.3 nm/s, which is about 300 times slower than that of the commonly used iron group catalysts (Co as a counterpart catalyst in this study). Such a slow growth velocity renders direct length-sorted growth of SWNTs, especially for short SWNTs with hundreds of nanometers in length. By simply adjusting the growth duration, SWNTs with average lengths of 149, 342, and 483 nm were selectively obtained and SWNTs as short as approximately 20 nm in length can be grown directly. Moreover, comparative studies indicate that the SiO(2) catalyst possesses a much longer catalytic active time, showing sharp contrast with the commonly used Co catalyst which quickly loses its catalytic activity. Taking advantage of the very slow growth velocity of the SiO(2) catalyst, patterned growth of SWNT networks confined in a narrow region of

A simple method is demonstrated to synthesize high-quality cup-stacked carbon nanotubes (CSCNTs) with short length. The as-synthesized CSCNTs are 0.2-3.2 microm in length, even shorter than the ball-milled long CSCNTs (approximately 7 microm). These CSCNTs have a diameter of 80-120 nm and a hollow channel of 60-100 nm along the nanotube axis. Moreover, a simple purification method is developed to remove iron particles and obtain short CSCNTs with two open ends. Such CSCNTs are very easily suspended in distilled water and tetrahydrofuran, which makes such material greatly promising as a candidate in many applications such as heterogeneous catalysis and photoelectrochemical cell.

Homogeneous single-layer graphene films are fabricated using an electrophoretic deposition technique, and their field-emission properties are investigated. The graphene films show high density, uniform thickness, numerous edges normal to the film surface, and good interface contact and adhesion with the substrate, and consequently show excellent field-emission properties.

We developed a hydrogen arc discharge exfoliation method for the synthesis of graphene sheets (GSs) with excellent electrical conductivity and good thermal stability from graphite oxide (GO), in combination with solution-phase dispersion and centrifugation techniques. It was found that efficient exfoliation and considerable deoxygenation of GO, and defect elimination and healing of exfoliated graphite can be simultaneously achieved during the hydrogen arc discharge exfoliation process. The GSs obtained by hydrogen arc discharge exfoliation exhibit a high electrical conductivity of approximately 2 x 10(3) S/cm and high thermal stability with oxidization resistance temperature of 601 degrees C, which are much better than those prepared by argon arc discharge exfoliation (approximately 2 x 10(2) S/cm, 525 degrees C) and by conventional thermal exfoliation (approximately 80 S/cm, 507 degrees C) with the same starting GO. These results demonstrate that this hydrogen arc discharge exfoliation method is a good approach for the preparation of GSs with a good quality.

[Wu, Zhong-Shuai; Ren, Wencai; Gao, Libo; Liu, Bilu; Jiang, Chuanbin; Cheng, Hui-Ming] Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China.;Ren, WC (reprint author), Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, 72 Wenhua Rd, Shenyang 110016, Peoples R China;wcren@imr.ac.cn cheng@imr.ac.cn

Various magnetic nanostructures such as Fe nanoparticles (Fe-NPs) adhering to single-walled carbon nanotubes, carbon-encapsulated Fe-NPs, Fe-NP decorated multi-walled carbon nanotubes (MWCNTs), and Fe-filled MWCNTs have been synthesized by the pyrolysis of pure ferrocene. It is found that the formation of the nanostructures can be selectively controlled by simply adjusting the sublimation temperature of ferrocene, while keeping all other experimental parameters unchanged. Magnetic characterization reveals that these nanostructures have an enhanced coercivity, higher than that of bulk Fe at room temperature. Based on the experimental results, the formation mechanism of the nanostructures is discussed in detail.

Semiconducting transition metal dichalcogenides (TMDCs) have attracted a lot of attention recently, because of their interesting electronic, optical, and mechanical properties. Among large numbers of TMDCs, monolayer of tungsten diselenides (WSe2) is of particular interest since it possesses a direct band gap and tunable charge transport behaviors, which make it suitable for a variety of electronic and optoelectronic applications. Direct synthesis of large domains of monolayer WSe2 and their growth mechanism studies are important steps toward applications of WSe2. Here, we report systematical studies on ambient pressure chemical vapor deposition (CVD) growth of monolayer and few layer WSe2 flakes directly on silica substrates. The WSe2 flakes were characterized using optical microscopy, atomic force microscopy, Raman spectroscopy, and photoluminescence spectroscopy. We investigated how growth parameters, with emphases on growth temperatures and durations, affect the sizes, layer numbers, and shapes of as-grown WSe2 flakes. We also demonstrated that transport properties of CVD-grown monolayer WSe2, similar to mechanically exfoliated samples, can be tuned into either p-type or ambipolar electrical behavior, depending on the types of metal contacts. These results deepen our understandings on the vapor phase growth mechanism of WSe2, and may benefit the uses of these CVD-grown monolayer materials in electronic and optoelectronics.

Two-dimensional (2D) materials are layered materials featuring strong in-plane covalent bonding and weak intra-plane bonding, which allow them to be easily cleaved into atomically thin materials, and be stable in such thin forms. Initiated by graphene, there has been increasing research interest in the past few years in studying growth, electronic and optoelectronic applications, and many other applications of 2D materials. In this review, recent achievements in the controlled preparation of monolayer and few-layer 2D semiconductors are summarized, with an emphasis on transition metal dichalcogenides (TMDCs). General understanding for TMDC growth as well as approaches to grow large single crystalline TMDCs and wafer-scale manufacturing of continuous TMDC films are discussed. In the second part, the focus is on applications of 2D semiconductors in electronics, where several key issues—including how to form good electrical contacts between electrodes and 2D semiconductors, charge carrier scattering mechanisms, and short-channel effects—are discussed in detail. In the last section, the authors' perspective on the challenges and opportunities in the growth and electronic applications of 2D semiconductors is presented.

Bandgap engineering of graphene is an essential step toward employing graphene in electronic and sensing applications. Recently, graphene nanoribbons (GNRs) were used to create a bandgap in graphene and function as a semiconducting switch. Although GNRs with widths of10 nm have been achieved, problems like GNR alignment, width control, uniformity, high aspect ratios, and edge roughness must be resolved in order to introduce GNRs as a robust alternative technology. Here we report patterning, characterization, and superior chemical sensing of ultranarrow aligned GNR arrays down to 5 nm width using helium ion beam lithography (HIBL) for the first time. The patterned GNR arrays possess narrow and adjustable widths, high aspect ratios, and relatively high quality. Field-effect transistors were fabricated on such GNR arrays and temperature-dependent transport measurements show the thermally activated carrier transport in the GNR array structure. Furthermore, we have demonstrated exceptional NO2 gas sensitivity of the 5 nm GNR array devices down to parts per billion (ppb) levels. The results show the potential of HIBL fabricated GNRs for the electronic and sensing applications.

Chirality-controlled synthesis of single-wall carbon nanotubes with predefined chiralities has been an important but elusive goal for almost two decades. Here we demonstrate a general strategy for producing carbon nanotubes with predefined chiralities by using purified single-chirality nanotubes as seeds for subsequent metal catalyst free growth, resembling vapour-phase epitaxy commonly used for semiconductor films. In particular, we have successfully synthesized (7, 6), (6, 5) and (7, 7) nanotubes, and used Raman spectroscopy to show unambiguously that the original chiralities of the nanotube seeds are preserved. Furthermore, we have performed electrical measurements on synthesized individual (7, 6) and (6, 5) nanotubes, confirming their semiconducting nature. The vapour-phase epitaxy approach is found to be highly robust and should enable a wide range of fundamental studies and technological developments.

Electronic characteristics of a single-walled carbon nanotube (SWCNT) strongly depend on minor variations in its atomic arrangement, specifically chirality. Therefore, precise control over nanotube chirality is highly desired for their application. Theoretically, SWCNTs with different structures have different chemical reactivities, which can be further used for their chirality selection. Here, an approach is developed to examine the relationship between the chirality of SWCNTs and their intrinsic chemical reactivity. By oxidizing individual, high-quality, suspended SWCNTs and using the nanobeam electron diffraction technique, it is shown that the reactivity of SWCNTs to O2 is intricately related to their diameters, metallicity, and chiral angles. In particular, even minor differences in chiral angles lead to big differences in their reactivity, which concords with first-principles calculations. Based on the experimental observations, a chirality-dependent reactivity sequence is constructed for SWCNTs. These findings shed light on effective chiral separation of SWCNTs for their practical application in many fields.

The development of guided chemical vapor deposition (CVD) growth of single-walled carbon nanotubes provides a great platform for wafer-scale integration of aligned nanotubes into circuits and functional electronic systems. However, the coexistence of metallic and semiconducting nanotubes is still a major obstacle for the development of carbon-nanotube-based nanoelectronics. To address this problem, we have developed a method to obtain predominantly semiconducting nanotubes from direct CVD growth. By using isopropyl alcohol (IPA) as the carbon feedstock, a semiconducting nanotube purity of above 90% is achieved, which is unambiguously confirmed by both electrical and micro-Raman measurements. Mass spectrometric study was performed to elucidate the underlying chemical mechanism. Furthermore, high performance thin-film transistors with an on/off ratio above 10(4) and mobility up to 116 cm(2)/(V·s) have been achieved using the IPA-synthesized nanotube networks grown on silicon substrate. The method reported in this contribution is easy to operate and the results are highly reproducible. Therefore, such semiconducting predominated single-walled carbon nanotubes could serve as an important building block for future practical and scalable carbon nanotube electronics.

Chirality-controlled synthesis of single-walled carbon nanotubes (SWCNTs) is a prerequisite for their practical applications in electronic and optoelectronic devices. We report here a novel bimetallic CoPt catalyst for the selective growth of high quality SWCNTs with a narrow chirality distribution at relatively high temperatures of 800 °C and 850 °C using atmospheric pressure alcohol chemical vapor deposition. The addition of Pt into a Co catalyst forms a CoPt alloy and significantly reduces the diameters of the as-grown SWCNTs and narrows their chirality distributions.

To understand in-depth the nature of the catalyst and the growth mechanism of single-walled carbon nanotubes (SWCNTs) on a newly developed silica catalyst, we performed this combined experimental and theoretical study. In situ transmission electron microscopy (TEM) observations revealed that the active catalyst for the SWCNT growth is solid and amorphous SiO(x) nanoparticles (NPs), suggesting a vapor-solid-solid growth mechanism. From in situ TEM and chemical vapor deposition growth experiments, we found that oxygen plays a crucial role in SWCNT growth in addition to the well-known catalyst size effect. Density functional theory calculations showed that oxygen atoms can enhance the capture of -CH(x) and consequently facilitate the growth of SWCNTs on oxygen-containing SiO(x) NPs.

We report a simple approach for the direct and nondestructive assembly of multi-sheeted single-walled carbon nanotube book-like macrostructures (buckybooks) with good control of the nanotube diameter, the sheet packing density, and the book thickness during the floating catalytic growth process. The promise of such buckybooks is highlighted by demonstrating their high capacitance and high-efficiency molecular separation by directly using them as a binder-free electrode and as a filter, respectively. Our approach also provides a flexible and reliable way to easily assemble various other types of nanotubes into book-like or even more sophisticated sandwich-like hybrid macrostructures, realizing the shape-engineering of one-dimensional nanostructures to macroscopic well-defined architectures for various applications.

High-quality single-walled carbon nanotubes (SWNTs) with tunable diameters were synthesized by an improved H(2)/CH(4)-based floating catalyst method. Transmission electron microscopy observations and Raman results demonstrated the overall quality of the as-synthesized samples with finely tailored large diameters at 1.28, 1.62, 1.72, 1.91, and 2.13 nm, depending on the experimental conditions. In addition, Raman analysis revealed that the abundance of specific (n, m) SWNTs could be selectively enriched simultaneously along with the diameter modulation. It was found that the selective etching effects of high hydrogen flow stabilized the decomposition of ultralow CH(4) flow and considerably suppressed the deposition of amorphous carbon and small nanotubes, leading to very pure samples with high structural homogeneity suitable for further applications in practical electronic systems.

We present a metal-catalyst-free CVD process for the high-efficiency growth of single-walled carbon nanotubes (SWNTs) on surface. By applying a 30-nm-thick SiO(2) sputtering deposited Si or Si/SiO(2) wafer as substrate and CH(4) as a carbon source, dense and uniform SWNT networks with high quality can be obtained without the presence of any metal species. Moreover, a simple patterned growth approach, using a scratched Si/SiO(2) wafer as substrate, is also presented for the growth of SWNTs with good position controllability. Our finding of the growth of SWNTs via a metal-catalyst-free process will provide valuable information for understanding the growth mechanism of SWNTs in-depth, which accordingly will facilitate the controllable synthesis and applications of carbon nanotubes.

Carbon nanotubes have the potential to spur future development in electronics due to their unequalled electrical properties. In this article, we present a review on carbon nanotube-based circuits in terms of their electrical performance in two major directions: nanoelectronics and macroelectronics. In the nanoelectronics direction, we direct our discussion to the performance of aligned carbon nanotubes for digital circuits and circuits designed for radio-frequency applications. In the macroelectronics direction, we focus our attention on the performance of thin films of carbon nanotube random networks in digital circuits, display applications, and printed electronics. In the last part, we discuss the existing challenges and future directions of nanotube-based nano- and microelectronics.

Single-wall carbon nanotubes (SWNTs) possess superior geometrical, electronic, chemical, thermal, and mechanical properties and are very attractive for applications in electronic devices and circuits. To make this a reality, the nanotube orientation, density, diameter, electronic property, and even chirality should be well controlled. This Feature article focuses on recent achievements researchers have made on the controlled growth of horizontally aligned SWNTs and SWNT arrays on substrates and their electronic applications. Principles and strategies to control the morphology, structure, and properties of SWNTs are reviewed in detail. Furthermore, electrical properties of field-effect transistors fabricated on both individual SWNTs and aligned SWNT arrays are discussed. State-of-the-art electronic devices and circuits based on aligned SWNTs and SWNT arrays are also highlighted.