Heterogeneous Solid Carbon Source‐Assisted Growth of High‐Quality Graphene via CVD at Low Temperatures

Polycyclic aromatic hydrocarbons (PAH) have been widely used as solid carbon sources for the synthesis of graphene at low temperatures. The inevitable formation of structural defects, however, has significantly limited the quality of the synthesized graphene. This article describes a low‐temperature chemical vapor deposition method that effectively mitigates defect formation in graphene by heterogeneous solid carbon sources containing a mixture of aromatic and aliphatic carbon on a Cu substrate. The addition of small amount of aliphatic carbon sources to the PAH significantly decreases the defect density of graphene synthesized at 400 ≤ T ≤ 600 °C by incorporating small aliphatic carbon fragments into defect sites. The carrier mobility of graphene grown using this heterogeneous solid carbon source is more than five times that of graphene synthesized using only PAH. Two mechanisms are also proposed by which vacancies can be generated during graphene growth using PAH sources on Cu, defect generation due to the disordered packing and the geometric limitation of PAH molecules. This low‐temperature method of synthesizing graphene reduces the degree of defect density using heterogeneous solid carbon sources promises to provide wide utility in electronics applications.     

Autonomously Controlled Homogenous Growth of Wafer‐Sized High‐Quality Graphene via a Smart Janus Substrate

The work reports a new method for large‐area growth of graphene films, which have been predicted to have novel and broad applications in the future. While chemical vapor deposition (CVD) is currently the preferred method, it suffers from a rather narrow processing window, and there is also much to be desired in the electrical properties of the CVD films. A new method for large‐area growth of graphene films is reported to overcome the narrow processing window of the CVD method. A composite substrate made of a C‐dissolving top (Ni) layer and a C‐rejecting bottom (Cu) layer is designed, which evolves into a C‐rejecting mixture, to autonomously regulate the C content at an elevated yet stable level at and near the surface over an extended duration. This “smart” substrate promotes graphene formation over a wide temperature‐gas composition window, leading to reliable growth of wafer‐sized graphene films of defined layer‐thickness and superior electrical–optical properties. This “smart”‐substrate strategy can also be implemented on Si and SiO₂ supports, paving the way toward the direct fabrication of large area, graphene‐enabled electronic and photonic devices.     

Wetting‐Assisted Crack‐ and Wrinkle‐Free Transfer of Wafer‐Scale Graphene onto Arbitrary Substrates over a Wide Range of Surface Energies

The polymer‐supported wet transfer of chemical vapor deposition‐grown graphene provides high‐quality large‐area graphene on a target substrate. The transfer‐induced defects that result from these processes, such as micrometer‐scale folds and cracks, have been regarded as an inevitable problem. Here, the transfer processes are thoroughly examined stage‐by‐stage and it is found that lamination wrinkles, which cause defects in the graphene, are generated as a result of the high contact angles of the trapped transfer medium liquids. Systematic theoretical and experimental studies demonstrate that a liquid droplet with a low surface tension trapped between the polymer/graphene film and the substrate minimizes lamination wrinkles during the transfer process by completely wetting the target substrate, regardless of the surface energy. In connection with these results, a simple and broadly applicable transfer method is developed using an organic liquid with a low surface tension to uniformly transfer high‐quality graphene onto arbitrary substrates, even onto superhydrophobic substrate. The graphene obtained using the proposed organic liquid transfer method displays better electrical and mechanical properties than the graphene transferred by the conventional method using water. This effective and practical transfer method provides an approach to obtaining high‐quality graphene for use in graphene‐based devices.     

Layer‐Controlled and Wafer‐Scale Synthesis of Uniform and High‐Quality Graphene Films on a Polycrystalline Nickel Catalyst

Chemical vapor deposition (CVD) provides a synthesis route for large‐area and high‐quality graphene films. However, layer‐controlled synthesis remains a great challenge on polycrystalline metallic films. Here, a facile and viable synthesis of layer‐controlled and high‐quality graphene films on wafer‐scale Ni surface by the sequentially separated steps of gas carburization, hydrogen exposure, and segregation is developed. The layer numbers of graphene films with large domain sizes are controlled precisely at ambient pressure by modulating the simplified CVD process conditions and hydrogen exposure. The hydrogen exposure assisted with a Ni catalyst plays a critical role in promoting the preferential segregation through removing the carbon layers on the Ni surface and reducing carbon content in the Ni. Excellent electrical and transparent conductive performance, with a room‐temperature mobility of ≈3000 cm² V^?1 s^?1 and a sheet resistance as low as ≈100 Ω per square at ≈90% transmittance, of the twisted few‐layer grapheme films grown on the Ni catalyst is demonstrated.     

Direct Growth of Edge‐Rich Graphene with Tunable Dielectric Properties in Porous Si3N4 Ceramic for Broadband High‐Performance Microwave Absorption

High‐performance graphene microwave absorption materials are highly desirable in daily life and some extreme situations. A simple technique for the direct growth of graphene as absorption fillers in wave‐transmitting matrices is of paramount importance to bring it to real‐world application. Herein, a simple chemical vapor deposition (CVD) route for the direct growth of edge‐rich graphene (ERG) with tailored structures and tunable dielectric properties in porous Si₃N₄ ceramics using only methyl alcohol (CH₃OH) as precursor is reported. The large O/C atomic ratio of CH₃OH helps to build a mild oxidizing atmosphere and leads to a unique structure featuring open graphite nanosteps and freestanding nanoplanes, endowing the ERG/Si₃N₄ hybrid with an appropriate balance between good impedance matching and strong loss capacity. Accordingly, the prepared materials exhibit superior electromagnetic wave absorption, far surpassing that of traditional CVD graphene and reduced graphene oxide‐based materials, achieving an effective absorption bandwidth of 4.2 GHz covering the entire X band, with a thickness of 3.75 mm and a negligibly low loading content of absorbents. The results provide new insights for developing novel microwave absorption materials with strong reflection loss and wide absorption frequency range.     

Triggering the Continuous Growth of Graphene Toward Millimeter‐Sized Grains

A simple but efficient strategy to synthesize millimeter‐sized graphene single crystal grains by regulating the supply of reactants in the chemical vapor deposition (CVD) process is demonstrated. Polystyrene is used as a carbon source. Pulse heating on the carbon source is utilized to minimize the nucleation density of graphene on copper foil, while a gradual increase in the temperature of the carbon source and the flow rate of hydrogen is adapted to drive the continuous growth of the graphene grains. As a result, the nucleation density of graphene grain can be controlled to as low as ≈100 nuclei/cm², and a single crystal grain can grow up to dimensions of ≈1.2 mm. Raman spectroscopy, transmission electron microscopy (TEM), and electrical‐transport measurements show that the graphene grains obtained are of high quality. The strategy presented provides very good controllability and enables the possibility of large graphene single crystals, which is of vital importance for practical applications.     

Homogeneous Optical and Electronic Properties of Graphene Due to the Suppression of Multilayer Patches During CVD on Copper Foils

A synthesis method of strictly monolayer and fully homogeneous graphene across tens of centimeter squares, by chemical vapour deposition onto standard copper foils, is presented. The growth technique involves cyclic injection of a carbon precursor separated by idle times with constant hydrogen exposure. The formation of spurious multilayer patches, which accompanies the standard growth techniques based on continuous exposure to methane, is inhibited here, in a broad range of pressure and gas composition, including in two pressure regimes which are known to yield distinctive grain morphologies (dendritic versus hexagonal). Raman spectra confirm the absence of defects within the graphene films. A mechanism for growth/suppression of the multilayer patches based on the carbon storage at defective regions is proposed. The importance of multilayer suppression is highlighted in a comparative study showing the detrimental effect of patches on the performances of graphene transistors and on the optical transparency of stacked layers. The full‐layer graphene sheets are superiorly homogeneous in terms of their optical and electronic properties, and are thus suited for applications for high‐density integration as well as transparent electrodes with spatially continuous optical absorbance. Graphene transistors fabricated by the pulsed CVD method exhibit room‐temperature mobilities with a mean value of 5000 cm² V^?1 s^?1.     

Direct Synthesis of Large‐Scale WTe2 Thin Films with Low Thermal Conductivity

Large‐scale, polycrystalline WTe₂ thin films are synthesized by atmospheric chemical vapor reaction of W metal films with Te vapor catalyzed by H₂Te intermediates, paving a way to understanding the synthesis mechanism for low bonding energy tellurides and toward synthesis of single‐crystalline telluride nanoflakes. Through‐plane and in‐plane thermal conductivities of single‐crystal WTe₂ flakes and polycrystalline WTe₂ thin films are measured for the first time. Nanoscale grains and disorder in WTe₂ thin films suppress the in‐plane thermal conductivity of WTe₂ greatly, which is at least 7.5 times lower than that of the single‐crystalline flakes.     

Growth and Isolation of Large Area Boron‐Doped Nanocrystalline Diamond Sheets: A Route toward Diamond‐on‐Graphene Heterojunction

Many material device applications would benefit from thin diamond coatings, but current growth techniques, such as chemical vapor deposition (CVD) or atomic layer deposition require high substrate and gas‐phase temperatures that would destroy the device being coated. The development of freestanding, thin boron‐doped diamond nanosheets grown on tantalum foil substrates via microwave plasma‐assisted CVD is reported. These diamond sheets (measuring up to 4 × 5 mm in planar area, and 300–600 nm in thickness) are removed from the substrate using mechanical exfoliation and then transferred to other substrates, including Si/SiO₂ and graphene. The electronic properties of the resulting diamond nanosheets and their dependence on the free‐standing growth, the mechanical exfoliation and transfer processes, and ultimately on their composition are characterized. To validate this, a prototypical diamond nanosheet–graphene field effect transistor‐like (DNGfet) device is developed and its electronic transport properties are studied as a function of temperature. The resulting DNGfet device exhibits thermally activated transport (thermionic conductance) above 50 K. Below 50 K a transition to variable range hopping is observed. These findings demonstrate the first step towards a low‐temperature diamond‐based transistor.     

Large‐Scale Growth of Two‐Dimensional SnS2 Crystals Driven by Screw Dislocations and Application to Photodetectors

2D SnS₂ crystals are attracting increasing attention owning to the huge potential for electronic and optoelectronic applications. However, batch production of 2D SnS₂ crystals via a simple vapor process remains challenging by far. Moreover, the growth mechanism for vapor growth of 2D SnS₂ is not well documented as well. Herein, a simple approach is presented for preparation of large‐scale 2D SnS₂ crystals on mica sheets and it is demonstrated that these 2D crystals follow a screw‐dislocation‐driven (SDD) spiral growth process. The synthesized 2D crystals show hexagonal and truncated triangular shapes with the lateral size ranging from a few micrometers to dozens of micrometers. Observations of key features for screw dislocations, such as helical fringes, dislocation hillocks, and herringbone contours, solidly confirm the SDD spiral growth behavior of the SnS₂. Possible mechanism is proposed in this work to show the generation and propagation of screw dislocations. Furthermore, in order to explore the optoelectronic property of the SnS₂, photodetectors based on 2D SnS₂ crystals are fabricated. The resulting device shows excellent operating characteristics, including good photo‐stability and reproducibility as well as a fast photoresponse time (≈42 ms), which enable the SnS₂ a promising candidate for photodetectors.