Ultraflat single-crystal hexagonal boron nitride for wafer-scale integration of a 2D-compatible high-κ metal gate.

Hexagonal boron nitride (hBN) has emerged as a promising protection layer for dielectric integration in the next-generation large-scale integrated electronics. Although numerous efforts have been devoted to growing single-crystal hBN film, wafer-scale ultraflat hBN has still not been achieved. Here, we report the epitaxial growth of 4 in. ultraflat single-crystal hBN on Cu0.8Ni0.2(111)/sapphire wafers. The strong coupling between hBN and Cu0.8Ni0.2(111) suppresses the formation of wrinkles and ensures the seamless stitching of parallelly aligned hBN domains, resulting in an ultraflat single-crystal hBN film on a wafer scale. Using the ultraflat hBN as a protective layer, we integrate the wafer-scale ultrathin high-κ dielectrics onto two-dimensional (2D) materials with a damage-free interface. The obtained hBN/HfO2 composite dielectric exhibits an ultralow current leakage (2.36 × 10-6 A cm-2) and an ultrathin equivalent oxide thickness of 0.52 nm, which meets the targets of the International Roadmap for Devices and Systems. Our findings pave the way to the synthesis of ultraflat 2D materials and integration of future 2D electronics.

Graphene/Cholesteric Liquid-Crystal-Based Electro-Driven Thermochromic Light Modulators toward Wide-Gamut Dynamic Light Color-Tuning-Related Applications.

Light filters are ubiquitous in projection and display techniques, illumination engineering, image sensing, photography, etc., while those enabling wide-gamut dynamic light color tuning are still lacking. Herein, by combining the electro-heating capability of graphene and unique optical properties (thermochromism and circular dichroism) of small-molecule-weight cholesteric liquid crystal (ChLC), a brand-new thermochromic light modulator is constructed as actively tunable color filter. Transparent graphene/glass hybrid with reasonably high conductivity serves both as a high-performance heater for actuating the thermochromism of temperature-responsive ChLC and as neutral light attenuator for brightness control. Thanks to the temperature- and polarization-dependent spectral properties of the ChLC, widely tunable hue and saturation properties of transmission light color are achieved, respectively. Several intriguing applications, e.g., color-variable smart windows for backlight color tuning and color-variable filters for photography, are also demonstrated. This work hereby provides new paradigms for promoting the applications of graphene/ChLC-based light modulators in next-generation light-management-related scenarios.

High Moisture-Barrier Performance of Double-Layer Graphene Enabled by Conformal and Clean Transfer.

Graphene films that can theoretically block almost all molecules have emerged as promising candidate materials for moisture barrier films in the applications of organic photonic devices and gas storage. However, the current barrier performance of graphene films does not reach the ideal value. Here, we reveal that the interlayer distance of the large-area stacked multilayer graphene is the key factor that suppresses water permeation. We show that by minimizing the gap between the two monolayers, the water vapor transmission rate of double-layer graphene can be as low as 5 × 10-3 g/(m2 d) over an A4-sized region. The high barrier performance was achieved by the absence of interfacial contamination and conformal contact between graphene layers during layer-by-layer transfer. Our work reveals the moisture permeation mechanism through graphene layers, and with this approach, we can tailor the interlayer coupling of manually stacked two-dimensional materials for new physics and applications.

Atomic Mechanism of Strain Alleviation and Dislocation Reduction in Highly Mismatched Remote Heteroepitaxy Using a Graphene Interlayer.

Remote heteroepitaxy is known to yield semiconductor films with better quality. However, the atomic mechanisms in systems with large mismatches are still unclear. Herein, low-strain single-crystalline nitride films are achieved on highly mismatched (∼16.3%) sapphire via graphene-assisted remote heteroepitaxy. Because of a weaker interface potential, the in-plane compressive strain at the interface releases by 30%, and dislocations are prevented. Meanwhile, the lattice distortions in the epilayer disappear when the structure climbs over the atomic steps on substrates because graphene renders the steps smooth. In this way, the density of edge dislocations in as-grown nitride films reduces to the same level as that of the screw dislocations, which is rarely observed in heteroepitaxy. Further, the indium composition in InxGa1-xN/GaN multiquantum wells increases to ∼32%, enabling the fabrication of a yellow light-emitting diode. This study demonstrates the advantages of remote heteroepitaxy for bandgap tuning and opens opportunities for photoelectronic and electronic applications.

Graphene Infrared Radiation Management Targeting Photothermal Conversion for Electric-Energy-Free Crude Oil Collection.

Graphene has been widely used as a solar absorber for its broad-band absorption. However, targeting a higher photothermal efficiency, the intrinsic infrared radiation loss of graphene requires to be further reduced. Herein, band structure engineering is performed to modulate graphene infrared radiation. Nitrogen-doped vertical graphene is grown on quartz foam (NVGQF) by the plasma-enhanced chemical vapor deposition method. Under the premise of keeping high solar absorption (250-2500 nm), graphitic nitrogen doping effectively modulates the infrared emissivity (2.5-25 µm) of NVGQF from 0.96 to 0.68, reducing the radiation loss by ∼31%. Based on the excellent photothermal properties of NVGQF, a temperature-gradient-driven crude oil collecting raft is designed, where the crude oil flows along the collecting path driven by the viscosity gradient without any external electric energy input. Compared with a nondoped vertical graphene quartz foam raft, the NVGQF raft with a superior photothermal efficiency shows a significantly enhanced crude oil collecting efficiency by three times. The advances in this work suggest broad radiation-managed application platforms for graphene materials, such as seawater desalination and personal or building thermal management.

Continuous Single-Crystalline GaN Film Grown on WS2 -Glass Wafer.

Use of 2D materials as buffer layers has prospects in nitride epitaxy on symmetry mismatched substrates. However, the control of lattice arrangement via 2D materials at the heterointerface presents certain challenges. In this study, the epitaxy of single-crystalline GaN film on WS2 -glass wafer is successfully performed by using the strong polarity of WS2 buffer layer and its perfectly matching lattice geometry with GaN. Furthermore, this study reveals that the first interfacial nitrogen layer plays a crucial role in the well-constructed interface by sharing electrons with both Ga and S atoms, enabling the single-crystalline stress-free GaN, as well as a violet light-emitting diode. This study paves a way for the heterogeneous integration of semiconductors and creates opportunities to break through the design and performance limitations, which are induced by substrate restriction, of the devices.

High-Performance 3D Vertically Oriented Graphene Photodetector Using a Floating Indium Tin Oxide Channel.

Vertically oriented graphene (VG), owing to its sharp edges, non-stacking morphology, and high surface-to-volume ratio structure, is promising as a consummate material for the application of photoelectric detection. However, owing to high defect and fast photocarrier recombination, VG-absorption-based detectors inherently suffer from poor responsivity, severely limiting their viability for light detection. Herein, we report a high-performance photodetector based on a VG/indium tin oxide (ITO) composite structure, where the VG layer serves as the light absorption layer while ITO works as the carrier conduction channel, thus achieving the broadband and high response nature of a photodetector. Under the illumination of infrared light, photoinduced carriers generated in VG could transfer to the floating ITO layer, which makes them separate and diffuse to electrodes quickly, finally realizing large photocurrent detectivity. This kind of composite structure photodetector possesses a room temperature photoresponsivity as high as ~0.7 A/W at a wavelength of 980 nm, and it still maintains an acceptable performance at temperatures as low as 87 K. In addition, a response time of 5.8 s is observed, ~10 s faster than VG photodetectors. Owing to the unique three-dimensional morphology structure of the as-prepared VG, the photoresponsivity of the VG/ITO composite photodetector also presented selectivity of incidence angles. These findings demonstrate that our novel composite structure VG device is attractive and promising in highly sensitive, fast, and broadband photodetection technology.

Hydrophilic, Clean Graphene for Cell Culture and Cryo-EM Imaging.

The wettability of graphene is critical for numerous applications but is very sensitive to its surface cleanness. Herein, by clarifying the impact of intrinsic contamination, i.e., amorphous carbon, which is formed on the graphene surface during the high-temperature chemical vapor deposition (CVD) process, the hydrophilic nature of clean graphene grown on single-crystal Cu(111) substrate was confirmed by both experimental and theoretical studies, with an average water contact angle of ∼23°. Furthermore, the wettability of as-transferred graphene was proven to be highly dependent on its intrinsic cleanness, because of which the hydrophilic, clean graphene exhibited improved performance when utilized for cell culture and cryoelectron microscopy imaging. This work not only validates the intrinsic hydrophilic nature of graphene but also provides a new insight in developing advanced bioapplications using CVD-grown clean graphene films.

Controllable Synthesis of Wafer-Scale Graphene Films: Challenges, Status, and Perspectives.

The availability of high-quality, large-scale, and single-crystal wafer-scale graphene films is fundamental for key device applications in the field of electronics, optics, and sensors. Synthesis determines the future: unleashing the full potentials of such emerging materials relies heavily upon their tailored synthesis in a scalable fashion, which is by no means an easy task to date. This review covers the state-of-the-art progress in the synthesis of wafer-scale graphene films by virtue of chemical vapor deposition (CVD), with a focus on main challenges and present status. Particularly, prevailing synthetic strategies are highlighted on a basis of the discussion in the reaction kinetics and gas-phase dynamics during CVD process. Perspectives with respect to key opportunities and promising research directions are proposed to guide the future development of wafer-scale graphene films.

Graphene Transfer: Paving the Road for Applications of Chemical Vapor Deposition Graphene.

Owing to the fascinating properties of graphene, fulfilling the promising characteristics of graphene in applications has ignited enormous scientific and industrial interest. Chemical vapor deposition (CVD) growth of graphene on metal substrates provides tantalizing opportunities for the large-area synthesis of graphene in a controllable manner. However, the tedious transfer of graphene from metal substrates onto desired substrates remains inevitable, and cracks of graphene membrane, transfer-induced doping, wrinkles as well as surface contamination can be incurred during the transfer, which highly degrade the performance of graphene. Furthermore, new issues can arise when moving to large-scale transfer at an industrial scale, thus cost-efficient and environment-friendly transfer techniques also become imperative. The aim of this review is to provide a comprehensive understanding of transfer-related issues and the corresponding experimental solutions and to provide an outlook for future transfer techniques of CVD graphene films on an industrial scale.

Graphene-Nanorod Enhanced Quasi-Van Der Waals Epitaxy for High Indium Composition Nitride Films.

The nitride films with high indium (In) composition play a crucial role in the fabrication of In-rich InGaN-based optoelectronic devices. However, a major limitation is In incorporation requiring a low temperature during growth at the expense of nitride dissociation. Here, to overcome this limitation, a strain-modulated growth method, namely the graphene (Gr)-nanorod (NR) enhanced quasi-van der Waals epitaxy, is proposed to increase the In composition in InGaN alloy. The lattice transparency of Gr enables constraint of in-plane orientation of nitride film and epitaxial relationships at the heterointerface. The Gr interlayer together with NRs buffer layer substantially reduces the stress of the GaN film by 74.4%, from 0.9 to 0.23 GPa, and thus increases the In incorporation by 30.7%. The first principles calculations confirm that the release of strain accounts for the dramatic improvement. The photoluminescence peak of multiple quantum wells shifts from 461 to 497 nm and the functionally small-sized cyan light-emitting diodes of 7 × 9 mil2 are demonstrated. These findings provide an efficient approach for the growth of In-rich InGaN film and extend the applications of nitrides in advanced optoelectronic, photovoltaic, and thermoelectric devices.

Enhancing the Heat-Dissipation Efficiency in Ultrasonic Transducers via Embedding Vertically Oriented Graphene-Based Porcelain Radiators.

Ultrasonic transducers with large output power have attracted extensive attentions due to their widespread applications in sonar, acoustic levitation, ultrasonic focusing, and so forth. However, the traditional transducer has almost no heat-dissipation capability itself, strictly relying on the assistant coolant system. Introducing high-performance heat-dissipation component is thus highly necessary. Herein, an embedded porcelain radiator component was designed by combining the excellent thermal conductivity of vertically oriented graphene (VG) with the outstanding heat-dissipation characteristics of thermosensitive ceramics, and a new-type transducer with an embedded VG/ceramic-hybrid radiator was constructed to show high heat-dissipation efficiency (up to ∼5 °C/min). Remarkably, prominent heat-dissipation effectiveness (temperature decline of ∼12 °C), enhanced amplitude and vibration uniformity were also achieved for the new-type transducer along with stabilized operating states. This research should pave ways for extending the applications of VG/ceramic hybrids to heat-dissipation scenarios and provide newfangled thoughts for the performance upgrade of multitudinous high-power devices.

Growth of Ultraflat Graphene with Greatly Enhanced Mechanical Properties.

Graphene grown on Cu by chemical vapor deposition is rough due to the surface roughening of Cu for releasing interfacial thermal stress and/or graphene bending energy. The roughness degrades the electrical conductance and mechanical strength of graphene. Here, by using vicinal Cu(111) and flat Cu(111) as model substrates, we investigated the critical role of original surface topography on the surface deformation of Cu covered by graphene. We demonstrated that terrace steps on vicinal Cu(111) dominate the formation of step bunches (SBs). Atomically flat graphene with roughness down to 0.2 nm was grown on flat Cu(111) films. When SB-induced ripples were avoided, as-grown ultraflat graphene maintained its flat feature after transfer. The ultraflat graphene exhibited extraordinary mechanical properties with Young's modulus ≈ 940 GPa and strength ≈ 117 GPa, comparable to mechanical exfoliated ones. Molecular dynamics simulation revealed the mechanism of softened elastic response and weakened strength of graphene with rippled structures.

Quantitative Analyses of the Interfacial Properties of Current Collectors at the Mesoscopic Level in Lithium Ion Batteries by Using Hierarchical Graphene.

At the mesoscopic level of commercial lithium ion battery (LIB), it is widely believed that the poor contacts between current collector (CC) and electrode materials (EM) lead to weak adhesions and large interfacial electric resistances. However, systematic quantitative analyses of the influence of the interfacial properties of CC are still scarce. Here, we built a model interface between CC and electrode materials by directly growing hierarchical graphene films on commercial Al foil CC, and we performed systematic quantitative studies of the interfacial properties therein. Our results show that the interfacial electric resistance dominates, i.e. ∼2 orders of magnitude higher than that of electrode materials. The interfacial resistance could be eliminated by hierarchical graphene interlayer. Cathode on CC with eliminated interfacial resistance could deliver much improved power density outputs. Our work quantifies the mesoscopic factors influencing the battery performance and offers practical guidelines of boosting the performance of LIBs and beyond.

H2 O-Etchant-Promoted Synthesis of High-Quality Graphene on Glass and Its Application in See-Through Thermochromic Displays.

Direct growth of graphene on glass can bring an innovative revolution by coupling the complementary properties of traditional glass and modern graphene (such as transparency and conductivity), offering brand new daily-life related applications. However, preparation of high-quality graphene on nonmetallic glass is still challenging. Herein, the direct route of low sheet resistance graphene on glass is reported by using in situ-introduced water as a mild etchant and methane as a carbon precursor via chemical vapor deposition. The derived graphene features with large domain sizes and few amorphous carbon impurities. Intriguingly, the sheet resistance of graphene on glass is dramatically lowered down to ≈1170 Ω sq-1 at the optical transmittance ≈93%, ≈20% of that derived without the water etchant. Based on the highly conductive and optical transparent graphene on glass, a see-through thermochromic display is thus fabricated with transparent graphene glass as a heater. This work can motivate further investigations of the direct synthesis of high-quality graphene on functional glass and its versatile applications in transparent electronic devices or displays.

Understanding Interlayer Contact Conductance in Twisted Bilayer Graphene.

Bilayer or few-layer 2D materials showing novel electrical properties in electronic device applications have aroused increasing interest in recent years. Obtaining a comprehensive understanding of interlayer contact conductance still remains a challenge, but is significant for improving the performance of bilayer or few-layer 2D electronic devices. Here, conductive atomic force microscope (C-AFM) experiments are reported to explore the interlayer contact conductance between bilayer graphene (BLG) with various twisted stacking structures fabricated by the chemical vapor deposition (CVD) method. The current maps show that the interlayer contact conductance between BLG strongly depends on the twist angle. The interlayer contact conductance of 0° AB-stacking bilayer graphene (AB-BLG) is ≈4 times as large as that of 30° twisted bilayer graphene (t-BLG), which indicates that the twist angle-dependent interlayer contact conductance originates from the coupling-decoupling transitions. Moreover, the moiré superlattice-level current images of t-BLG show modulations of local interlayer contact conductance. Density functional theory calculations together with a theoretical model reproduce the C-AFM current map and show that the modulation is mainly attributed to the overall contribution of local interfacial carrier density and tunneling barrier.

In Situ N-Doped Graphene and Mo Nanoribbon Formation from Mo2 Ti2 C3 MXene Monolayers.

Since the advent of monolayered 2D transition metal carbide and nitrides (MXenes) in 2011, the number of different monolayer systems and the study thereof have been on the rise. Mo2 Ti2 C3 is one of the least studied MXenes and new insights to this material are of value to the field. Here, the stability of Mo2 Ti2 C3 under electron irradiation is investigated. A transmission electron microscope (TEM) is used to study the structural and elemental changes in situ. It is found that Mo2 Ti2 C3 is reasonably stable for the first 2 min of irradiation. However, structural changes occur thereafter, which trigger increasingly rapid and significant rearrangement. This results in the formation of pores and two new nanomaterials, namely, N-doped graphene membranes and Mo nanoribbons. The study provides insight into the stability of Mo2 Ti2 C3 monolayers against electron irradiation, which will allow for reliable future study of the material using TEM. Furthermore, these findings will facilitate further research in the rapidly growing field of electron beam driven chemistry and engineering of nanomaterials.

Bridging the Gap between Reality and Ideal in Chemical Vapor Deposition Growth of Graphene.

Graphene, in its ideal form, is a two-dimensional (2D) material consisting of a single layer of carbon atoms arranged in a hexagonal lattice. The richness in morphological, physical, mechanical, and optical properties of ideal graphene has stimulated enormous scientific and industrial interest, since its first exfoliation in 2004. In turn, the production of graphene in a reliable, controllable, and scalable manner has become significantly important to bring us closer to practical applications of graphene. To this end, chemical vapor deposition (CVD) offers tantalizing opportunities for the synthesis of large-area, uniform, and high-quality graphene films. However, quite different from the ideal 2D structure of graphene, in reality, the currently available CVD-grown graphene films are still suffering from intrinsic defective grain boundaries, surface contaminations, and wrinkles, together with low growth rate and the requirement of inevitable transfer. Clearly, a gap still exits between the reality of CVD-derived graphene, especially in industrial production, and ideal graphene with outstanding properties. This Review will emphasize the recent advances and strategies in CVD production of graphene for settling these issues to bridge the giant gap. We begin with brief background information about the synthesis of nanoscale carbon allotropes, followed by the discussion of fundamental growth mechanism and kinetics of CVD growth of graphene. We then discuss the strategies for perfecting the quality of CVD-derived graphene with regard to domain size, cleanness, flatness, growth rate, scalability, and direct growth of graphene on functional substrate. Finally, a perspective on future development in the research relevant to scalable growth of high-quality graphene is presented.

Applications of 2D MXenes in energy conversion and storage systems.

Transition metal carbides and nitrides (MXenes), a family of two-dimensional (2D) inorganic compounds, are materials composed of a few atomic layers of transition metal carbides, nitrides, or carbonitrides. Ti3C2, the first 2D layered MXene, was isolated in 2011. This material, which is a layered bulk material analogous to graphite, was derived from its 3D phase, Ti3AlC2 MAX. Since then, material scientists have either determined or predicted the stable phases of >200 different MXenes based on combinations of various transition metals such as Ti, Mo, V, Cr, and their alloys with C and N. Extensive experimental and theoretical studies have shown their exciting potential for energy conversion and electrochemical storage. To this end, we comprehensively summarize the current advances in MXene research. We begin by reviewing the structure types and morphologies and their fabrication routes. The review then discusses the mechanical, electrical, optical, and electrochemical properties of MXenes. The focus then turns to their exciting potential in energy storage and conversion. Energy storage applications include electrodes in rechargeable lithium- and sodium-ion batteries, lithium-sulfur batteries, and supercapacitors. In terms of energy conversion, photocatalytic fuel production, such as hydrogen evolution from water splitting, and carbon dioxide reduction are presented. The potential of MXenes for the photocatalytic degradation of organic pollutants in water, such as dye waste, is also addressed, along with their promise as catalysts for ammonium synthesis from nitrogen. Finally, their application potential is summarized.

Superclean Growth of Graphene Using a Cold-Wall Chemical Vapor Deposition Approach.

Chemical vapor deposition (CVD) has become a promising approach for the industrial production of graphene films with appealing controllability and uniformity. However, in the conventional hot-wall CVD system, CVD-derived graphene films suffer from surface contamination originating from the gas-phase reaction during the high-temperature growth. Shown here is that the cold-wall CVD system is capable of suppressing the gas-phase reaction, and achieves the superclean growth of graphene films in a controllable manner. The as-received superclean graphene film, exhibiting improved optical and electrical properties, was proven to be an ideal candidate material used as transparent electrodes and substrate for epitaxial growth. This study provides a new promising choice for industrial production of high-quality graphene films, and the finding about the engineering of the gas-phase reaction, which is usually overlooked, will be instructive for future research on CVD growth of graphene.