graphene-assisted-quasi-van-der-waals-epitaxy-aln-film-on-nano

Graphene-Assisted Quasi-van der Waals Epitaxy of AlN Film on Nano-Patterned Sapphire Substrate for Ultraviolet Light Emitting Diodes

This protocol demonstrates a method for graphene-assisted quick growth and coalescence of AlN on nano-pattened sapphire substrate (NPSS). Graphene layers ...

Peking University

The direct growth of uniform graphene disks and their continuous film is achieved by exploiting the molten state of glass. The use of molten glass enables highly uniform nucleation and an enhanced growth rate (tenfold) of graphene, as compared to those scenarios on commonly used insulating solids. The obtained graphene glasses show promising application potentials in daily-life scenarios such as smart heating devices and biocompatible cell-culture mediums. 

Growing Uniform Graphene Disks and Films on Molten Glass for Heating Devices and Cell Culture.

A unique ethanol-precursor-based LPCVD route is developed for the fast (4 min, improved 20 times) and scalable (25 inch, improved six times) growth of high-quality graphene glass. The obtained graphene glass presents high uniformity across large areas and is demonstrated to be an excellent material for constructing switchable windows and biosensor devices, owing to its excellent transparency and conductivity.

Fast Growth and Broad Applications of 25-Inch Uniform Graphene Glass.

Efficient solar-thermal energy conversion is essential for the harvesting and transformation of abundant solar energy, leading to the exploration and design of efficient solar-thermal materials. Carbon-based materials, especially graphene, have the advantages of broadband absorption and excellent photothermal properties, and hold promise for solar-thermal energy conversion. However, to date, graphene-based solar-thermal materials with superior omnidirectional light harvesting performances remain elusive. Herein, hierarchical graphene foam (h-G foam) with continuous porosity grown via plasma-enhanced chemical vapor deposition is reported, showing dramatic enhancement of broadband and omnidirectional absorption of sunlight, which thereby can enable a considerable elevation of temperature. Used as a heating material, the external solar-thermal energy conversion efficiency of the h-G foam impressively reaches up to ≈93.4%, and the solar-vapor conversion efficiency exceeds 90% for seawater desalination with high endurance.

Hierarchical Graphene Foam for Efficient Omnidirectional Solar-Thermal Energy Conversion.

Plasma-enhanced chemical vapor deposition (PECVD) is an applicable route to achieve low-temperature growth of graphene, typically shaped like vertical nanowalls. However, for transparent electronic applications, the rich exposed edges and high specific surface area of vertical graphene (VG) nanowalls can enhance the carrier scattering and light absorption, resulting in high sheet resistance and low transmittance. Thus, the synthesis of laid-down graphene (LG) is imperative. Here, a Faraday cage is designed to switch graphene growth in PECVD from the vertical to the horizontal direction by weakening ion bombardment and shielding electric field. Consequently, laid-down graphene is synthesized on low-softening-point soda-lime glass (6 cm × 10 cm) at ≈580 °C. This is hardly realized through the conventional PECVD or the thermal chemical vapor deposition methods with the necessity of high growth temperature (1000 °C-1600 °C). Laid-down graphene glass has higher transparency, lower sheet resistance, and much improved macroscopic uniformity when compare to its vertical graphene counterpart and it performs better in transparent heating devices. This will inspire the next-generation applications in low-cost transparent electronics.

Switching Vertical to Horizontal Graphene Growth Using Faraday Cage-Assisted PECVD Approach for High-Performance Transparent Heating Device.

The photonic reflection of a cholesteric liquid crystal (ChLC) device depends on the spatial distribution of the orientations of their helical axes, and many orientation techniques have been developed so far. In this study, we select the hybrids of graphene directly grown on quartz glass as platforms to construct ChLC-based devices. This special design makes graphene serve as both an alignment layer and a conductive layer, thus affording a more simplified device fabrication route. We reveal that multidomain structures can be evolved for ChLCs on polycrystalline monolayer graphene on quartz glass, as evidenced by polarized optical microscope characterizations. The disparate orientations of the helical axes of ChLCs and the formation of multidomain structures are proposed to be induced by the different domain orientations of graphene, leading to a wide viewing angle of the ChLC-based devices. Moreover, the pitch of ChLCs is also observed to play a key role in the relative orientations of ChLCs. A wide viewing angle of the ChLC-based device is also detected especially in the infrared spectrum region. Briefly, this work should provoke the application of graphene glass as a perfect transparent electrode in the fabrication of liquid-crystal-based devices showing broad application potentials in intelligent laser protection and energy-saving smart windows.

Graphene Glass Inducing Multidomain Orientations in Cholesteric Liquid Crystal Devices toward Wide Viewing Angles.

Single-crystalline GaN-based light-emitting diodes (LEDs) with high efficiency and long lifetime are the most promising solid-state lighting source compared with conventional incandescent and fluorescent lamps. However, the lattice and thermal mismatch between GaN and sapphire substrate always induces high stress and high density of dislocations and thus degrades the performance of LEDs. Here, the growth of high-quality GaN with low stress and a low density of dislocations on graphene (Gr) buffered sapphire substrate is reported for high-brightness blue LEDs. Gr films are directly grown on sapphire substrate to avoid the tedious transfer process and GaN is grown by metal-organic chemical vapor deposition (MOCVD). The introduced Gr buffer layer greatly releases biaxial stress and reduces the density of dislocations in GaN film and In Ga N/GaN multiple quantum well structures. The as-fabricated LED devices therefore deliver much higher light output power compared to that on a bare sapphire substrate, which even outperforms the mature process derived counterpart. The GaN growth on Gr buffered sapphire only requires one-step growth, which largely shortens the MOCVD growth time. This facile strategy may pave a new way for applications of Gr films and bring several disruptive technologies for epitaxial growth of GaN film and its applications in high-brightness LEDs.

High-Brightness Blue Light-Emitting Diodes Enabled by a Directly Grown Graphene Buffer Layer.

Visual electrophysiology measurements are important for ophthalmic diagnostic testing. Electrodes with combined optical transparency and softness are highly desirable, and sometimes indispensable for many ocular electrophysiology measurements. Here we report the fabrication of soft graphene contact lens electrodes (GRACEs) with broad-spectrum optical transparency, and their application in conformal, full-cornea recording of electroretinography (ERG) from cynomolgus monkeys. The GRACEs give higher signal amplitude than conventional ERG electrodes in recordings of various full-field ERG responses. High-quality topographic mapping of multifocal ERG under simultaneous fundus monitoring is realized. A conformal and tight interface between the GRACEs and cornea is revealed. Neither corneal irritation nor abnormal behavior of the animals is observed after ERG measurements with GRACEs. Furthermore, spatially resolved ERG recordings on rabbits with graphene multi-electrode array reveal a stronger signal at the central cornea than the periphery. These results demonstrate the unique capabilities of the graphene-based electrodes for in vivo visual electrophysiology studies.

Soft transparent graphene contact lens electrodes for conformal full-cornea recording of electroretinogram.

Heterostructures based on graphene and other 2D atomic crystals exhibit fascinating properties and intriguing potential in flexible optoelectronics, where graphene films function as transparent electrodes and other building blocks are used as photoactive materials. However, large-scale production of such heterostructures with superior performance is still in early stages. Herein, for the first time, the preparation of a submeter-sized, vertically stacked heterojunction of lead iodide (PbI )/graphene on a flexible polyethylene terephthalate (PET) film by vapor deposition of PbI on graphene/PET substrate at a temperature lower than 200 °C is demonstrated. This film is subsequently used to fabricate bendable graphene/PbI /graphene sandwiched photodetectors, which exhibit high responsivity (45 A W cm ), fast response (35 µs rise, 20 µs decay), and high-resolution imaging capability (1 µm). This study may pave a facile pathway for scalable production of high-performance flexible devices.

Low-Temperature Heteroepitaxy of 2D PbI /Graphene for Large-Area Flexible Photodetectors.

Chemical vapor deposition (CVD) on catalytic metal surfaces is considered to be the most effective way to obtain large-area, high-quality graphene films. For practical applications, a transfer process from metal catalysts to target substrates (e.g., poly(ethylene terephthalate) (PET), glass, and SiO /Si) is unavoidable and severely degrades the quality of graphene. In particular, the direct growth of graphene on glass can avoid the tedious transfer process and endow traditional glass with prominent electrical and thermal conductivities. Such a combination of graphene and glass creates a new type of glass, the so-called "super graphene glass," which has attracted great interest from the viewpoints of both fundamental research and daily-life applications. In the last few years, great progress has been achieved in pursuit of this goal. Here, these growth methods as well as the specific growth mechanisms of graphene on glass surfaces are summarized. The typical techniques developed include direct thermal CVD growth, molten-bed CVD growth, metal-catalyst-assisted growth, and plasma-enhanced growth. Emphasis is placed on the strategy of growth corresponding to the different natures of glass substrates. A comprehensive understanding of graphene growth on nonmetal glass substrates and the latest status of "super graphene glass" production are provided.

Direct CVD Growth of Graphene on Traditional Glass: Methods and Mechanisms.

The growth of single-crystal III-nitride films with a low stress and dislocation density is crucial for the semiconductor industry. In particular, AlN-derived deep-ultraviolet light-emitting diodes (DUV-LEDs) have important applications in microelectronic technologies and environmental sciences but are still limited by large lattice and thermal mismatches between the epilayer and substrate. Here, the quasi-van der Waals epitaxial (QvdWE) growth of high-quality AlN films on graphene/sapphire substrates is reported and their application in high-performance DUV-LEDs is demonstrated. Guided by density functional theory calculations, it is found that pyrrolic nitrogen in graphene introduced by a plasma treatment greatly facilitates the AlN nucleation and enables fast growth of a mirror-smooth single-crystal film in a very short time of ≈0.5 h (≈50% decrease compared with the conventional process), thus leading to a largely reduced cost. Additionally, graphene effectively releases the biaxial stress (0.11 GPa) and reduces the dislocation density in the epilayer. The as-fabricated DUV-LED shows a low turn-on voltage, good reliability, and high output power. This study may provide a revolutionary technology for the epitaxial growth of AlN films and provide opportunities for scalable applications of graphene films.

Improved Epitaxy of AlN Film for Deep-Ultraviolet Light-Emitting Diodes Enabled by Graphene.

For III-nitride-based devices, such as high-brightness light-emitting diodes (LEDs), the poor heat dissipation of the sapphire substrate is deleterious to the energy efficiency and restricts many of their applications. Herein, the role of vertically oriented graphene (VG) nanowalls as a buffer layer for improving the heat dissipation in AlN films on sapphire substrates is studied. It is found that VG nanowalls can effectively enhance the heat dissipation between an AlN film and a sapphire substrate in the longitudinal direction because of their unique vertical structure and good thermal conductivity. Thus, an LED fabricated on a VG-sapphire substrate shows a 37% improved light output power under a high injection current (350 mA) with an effective 3.8% temperature reduction. Moreover, the introduction of VG nanowalls does not degrade the quality of the AlN film, but instead promotes AlN nucleation and significantly reduces the epilayer strain that is generated during the cooling process. These findings suggest that the VG nanowalls can be a good buffer layer candidate in III-nitride semiconductor devices, especially for improving the heat dissipation in high-brightness LEDs.

Enhancement of Heat Dissipation in Ultraviolet Light-Emitting Diodes by a Vertically Oriented Graphene Nanowall Buffer Layer.

High-quality graphene film grown on dielectric substrates by a direct chemical vapor deposition (CVD) method promotes the application of high-performance graphene-based devices in large scale. However, due to the noncatalytic feature of insulating substrates, the production of graphene film on them always has a low growth rate and is time-consuming (typically hours to days), which restricts real potential applications. Here, by employing a local-fluorine-supply method, we have pushed the massive fabrication of a graphene film on a wafer-scale insulating substrate to a short time of just 5 min without involving any metal catalyst. The highly enhanced domain growth rate (∼37 nm min) and the quick nucleation rate (∼1200 nuclei min cm) both account for this high productivity of graphene film. Further first-principles calculation demonstrates that the released fluorine from the fluoride substrate at high temperature can rapidly react with CH to form a more active carbon feedstock, CHF, and the presence of CHF molecules in the gas phase much lowers the barrier of carbon attachment, providing sufficient carbon feedstock for graphene CVD growth. Our approach presents a potential route to accomplish exceptionally large-scale and high-quality graphene films on insulating substrates, .., SiO, SiO/Si, fiber, , at low cost for industry-level applications.

Ultrafast Catalyst-Free Graphene Growth on Glass Assisted by Local Fluorine Supply.

Directly incorporating heteroatoms into the hexagonal lattice of graphene during growth has been widely used to tune its electrical properties with superior doping stability, uniformity, and scalability. However the introduction of scattering centers limits this technique because of reduced carrier mobilities and conductivities of the resulting material. Here, we demonstrate a rapid growth of graphitic nitrogen cluster-doped monolayer graphene single crystals on Cu foil with remarkable carrier mobility of 13,000 cm V s and a greatly reduced sheet resistance of only 130 ohms square. The exceedingly large carrier mobility with high n-doping level was realized by (i) incorporation of nitrogen-terminated carbon clusters to suppress the carrier scattering and (ii) elimination of all defective pyridinic nitrogen centers by oxygen etching. Our study opens up an avenue for the growth of high-mobility/conductivity doped graphene with tunable work functions for scalable graphene-based electronic and device applications.

Nitrogen cluster doping for high-mobility/conductivity graphene films with millimeter-sized domains.

For atomically thin two-dimensional materials, interfacial effects may dominate the entire response of devices, because most of the atoms are in the interface/surface. Graphene/sapphire has great application in electronic devices and semiconductor thin-film growth, but the nature of this interface is largely unknown. Here we find that the sapphire surface has a strong interaction with some of the carbon atoms in graphene to form a C-O-Al configuration, indicating that the interface interaction is no longer a simple van der Waals interaction. In addition, the structural relaxation of sapphire near the interface is significantly suppressed and very different from that of a bare sapphire surface. Such an interfacial C-O-Al bond is formed during graphene growth at high temperature. Our study provides valuable insights into understanding the electronic structures of graphene on sapphire and remote control of epitaxy growth of thin films by using a graphene-sapphire substrate.

Atomic mechanism of strong interactions at the graphene/sapphire interface.

Photoacoustic microscopy (PAM) and optical coherence tomography (OCT) are sensitive to optical absorption and scattering characteristics, respectively. As such, the integration of these two modalities in order to combine important complementary information has garnered much attention. Due to the relatively low axial resolution of PAM, PAM and OCT dual modality systems generally have a large resolution gap, especially for reflection mode systems. In this study, based on a wide-band transparent pure-optical ultrasonic detector, we developed a dual modality system (PAM-OCT system) in which PAM has a similar spatial resolution ( several micrometers in both the lateral and axial directions) to OCT. In addition, due to the optical transparency advantage, the integrated system works in reflection mode, which is ideal for  biomedical imaging. We successfully imaged the skin of a mouse hindlimb, which cannot be done by a transmission mode dual modality system. Our work demonstrates this dual modality system has potential in biomedical studies with complementary imaging contrasts.

Article	Year
Growing Uniform Graphene Disks and Films on Molten Glass for Heating Devices and Cell Culture. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 26485212	2015
Fast Growth and Broad Applications of 25-Inch Uniform Graphene Glass. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 27805741	2017
Hierarchical Graphene Foam for Efficient Omnidirectional Solar-Thermal Energy Conversion. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 28833544	2017
Switching Vertical to Horizontal Graphene Growth Using Faraday Cage-Assisted PECVD Approach for High-Performance Transparent Heating Device. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 29318672	2018
Graphene Glass Inducing Multidomain Orientations in Cholesteric Liquid Crystal Devices toward Wide Viewing Angles. ACS nano\| PubMed ID: 29787229	2018
High-Brightness Blue Light-Emitting Diodes Enabled by a Directly Grown Graphene Buffer Layer. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 29883036	2018
Soft transparent graphene contact lens electrodes for conformal full-cornea recording of electroretinogram. Nature communications\| PubMed ID: 29899545	2018
Low-Temperature Heteroepitaxy of 2D PbI /Graphene for Large-Area Flexible Photodetectors. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 30015990	2018
Direct CVD Growth of Graphene on Traditional Glass: Methods and Mechanisms. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 30443937	2019
Improved Epitaxy of AlN Film for Deep-Ultraviolet Light-Emitting Diodes Enabled by Graphene. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 30993771	2019
Enhancement of Heat Dissipation in Ultraviolet Light-Emitting Diodes by a Vertically Oriented Graphene Nanowall Buffer Layer. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 31140651	2019
Ultrafast Catalyst-Free Graphene Growth on Glass Assisted by Local Fluorine Supply. ACS nano\| PubMed ID: 31430126	2019
Nitrogen cluster doping for high-mobility/conductivity graphene films with millimeter-sized domains. Science advances\| PubMed ID: 31448331	2019
Atomic mechanism of strong interactions at the graphene/sapphire interface. Nature communications\| PubMed ID: 31676774	2019
Resolution-matched reflection mode photoacoustic microscopy and optical coherence tomography dual modality system. Photoacoustics\| PubMed ID: 32577377	2020

Zhaolong Chen

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