Synthesis of High Quality Monolayer Graphene at Reduced Temperature on Hydrogen-Enriched Evaporated Copper (111) Films

We report new findings on the chemical vapor deposition (CVD) of monolayer graphene with negligible defects (≥95% negligible defect-peak over 200 μm × 200 μm areas) on evaporated copper films. Compared to copper foils used in the CVD of graphene, several new unexpected results have been observed including high-quality monolayer synthesis at temperatures <900 °C, a new growth window using a hydrogen-free methane precursor for low-defects, and electron microscope evidence of commensurate growth of graphene grains on underlying copper grains. These thermal, chemical, and physical growth characteristics of graphene on copper films can be attributed to the distinct differences in the dominant crystal orientation of copper films (111) versus foils (100), and consequent dissimilar interplay with the precursor gas. This study suggests that reduced temperature, hydrogen-free synthesis of defect-negligible monolayer graphene is feasible, with the potential to shape and scale graphene grains by controlling the size and crystal orientation of the underlying copper grains

Direct Observation of Poly(Methyl Methacrylate) Removal from a Graphene Surface

Poly­(methyl methacrylate) (PMMA) is commonly used as a temporary support layer for chemical vapor deposition (CVD) graphene transfer; it is then removed by a chemical or thermal treatment. Regardless of the method used for PMMA removal, polymer residues are left on the graphene surface, which alter its intrinsic properties. A method based on isotope labeling of PMMA and time-of-flight secondary ion mass spectrometry (ToF-SIMS) has now been developed to identify, locate, and quantify these residues. It is shown that vacuum annealing does not completely remove the PMMA residues but, instead, transforms them into amorphous carbon. In contrast, air annealing under optimized conditions generates a PMMA-free surface with limited damage to the graphene structure. This cleaned graphene surface demonstrates low friction which is comparable with that of pristine graphene film

Enhancement of the Electrical Properties of Graphene Grown by Chemical Vapor Deposition via Controlling the Effects of Polymer Residue

Residual polymer (here, poly­(methyl methacrylate), PMMA) left on graphene from transfer from metals or device fabrication processes affects its electrical and thermal properties. We have found that the amount of polymer residue left after the transfer of chemical vapor deposited (CVD) graphene varies depending on the initial concentration of the polymer solution, and this residue influences the electrical performance of graphene field-effect transistors fabricated on SiO₂/Si. A PMMA solution with lower concentration gave less residue after exposure to acetone, resulting in less p-type doping in graphene and higher charge carrier mobility. The electrical properties of the weakly p-doped graphene could be further enhanced by exposure to formamide with the Dirac point at nearly zero gate voltage and a more than 50% increase of the room-temperature charge carrier mobility in air. This can be attributed to electron donation to graphene by the −NH₂ functional group in formamide that is absorbed in the polymer residue. This work provides a route to enhancing the electrical properties of CVD-grown graphene even when it has a thin polymer coating

Selective-Area Fluorination of Graphene with Fluoropolymer and Laser Irradiation

We have devised a method to selectively fluorinate graphene by irradiating fluoropolymer-covered graphene with a laser. This fluoropolymer produces active fluorine radicals under laser irradiation that react with graphene but only in the laser-irradiated region. The kinetics of C–F bond formation is dependent on both the laser power and fluoropolymer thickness, proving that fluorination occurs by the decomposition of the fluoropolymer. Fluorination leads to a dramatic increase in the resistance of the graphene while the basic skeletal structure of the carbon bonding network is maintained. Considering the simplicity of the fluorination process and that it allows patterning with a nontoxic fluoropolymer as a solid source, this method could find application to generate fluorinated graphene in graphene-based electronic devices such as for the electrical isolation of graphene

Growth Mechanism and Controlled Synthesis of AB-Stacked Bilayer Graphene on Cu–Ni Alloy Foils

Strongly coupled bilayer graphene (<i>i.e.</i>, AB stacked) grows particularly well on commercial “90–10” Cu–Ni alloy foil. However, the mechanism of growth of bilayer graphene on Cu–Ni alloy foils had not been discovered. Carbon isotope labeling (sequential dosing of ¹²CH₄ and ¹³CH₄) and Raman spectroscopic mapping were used to study the growth process. It was learned that the mechanism of graphene growth on Cu–Ni alloy is by precipitation at the surface from carbon dissolved in the bulk of the alloy foil that diffuses to the surface. The growth parameters were varied to investigate their effect on graphene coverage and isotopic composition. It was found that higher temperature, longer exposure time, higher rate of bulk diffusion for ¹²C <i>vs</i> ¹³C, and slower cooling rate all produced higher graphene coverage on this type of Cu–Ni alloy foil. The isotopic composition of the graphene layer(s) could also be modified by adjusting the cooling rate. In addition, large-area, AB-stacked bilayer graphene transferrable onto Si/SiO₂ substrates was controllably synthesized

Flexible and Transparent Dielectric Film with a High Dielectric Constant Using Chemical Vapor Deposition-Grown Graphene Interlayer

We have devised a dielectric film with a chemical vapor deposited graphene interlayer and studied the effect of the graphene interlayer on the dielectric performance. The highly transparent and flexible film was a polymer/graphene/polymer ‘sandwich-structure’ fabricated by a one-step transfer method that had a dielectric constant of 51, with a dielectric loss of 0.05 at 1 kHz. The graphene interlayer in the film forms a space charge layer, <i>i.e.</i>, an accumulation of polarized charge carriers near the graphene, resulting in an induced space charge polarization and enhanced dielectric constant. The characteristic of the space charge layer for the graphene dielectric film, the sheet resistance of the graphene interlayer, was adjusted through thermal annealing that caused partial oxidation. The dielectric film with higher sheet resistance due to the oxidized graphene interlayer had a significantly lower dielectric constant compared to that with the graphene with lower interlayer sheet resistance. Oxidizing the graphene interlayer yields a smaller and thinner space charge density in the dielectric film, ultimately leading to decreased capacitance. Considering the simplicity of the fabrication process and high dielectric performance, as well as the high transparency and flexibility, this film is promising for applications in plastic electronics

Uniform Wafer-Scale Chemical Vapor Deposition of Graphene on Evaporated Cu (111) Film with Quality Comparable to Exfoliated Monolayer

This article demonstrated monolayer graphene grown on annealed Cu (111) films on standard oxidized 100-mm Si wafers with higher quality than existing reports. Large area Raman mapping indicated high uniformity (>97% coverage) of monolayer graphene with immeasurable defects (>95% defect-negligible) across the entire wafer. Key to these results is the phase transition of evaporated copper films from amorphous to (111) preferred crystalline, which resulted in subsequent growth of high quality graphene, as corroborated by X-ray diffraction and electron backscatter diffraction. Noticeably, such phase transition of the copper film was observed on a technologically ubiquitous Si wafer with a standard amorphous thermal oxide. A modified two-step etching transfer process was introduced to preserve the clean surface and electrical property of transferred monolayer graphene. The fabricated graphene field effect transistor on a flexible polyimide film achieved peak mobility over 4900 cm²/(V s) at ambient condition

<i>In Situ</i> Observation of Initial Stage in Dielectric Growth and Deposition of Ultrahigh Nucleation Density Dielectric on Two-Dimensional Surfaces

Several proposed beyond-CMOS devices based on two-dimensional (2D) heterostructures require the deposition of thin dielectrics between 2D layers. However, the direct deposition of dielectrics on 2D materials is challenging due to their inert surface chemistry. To deposit high-quality, thin dielectrics on 2D materials, a flat lying titanyl phthalocyanine (TiOPc) monolayer, deposited via the molecular beam epitaxy, was employed to create a seed layer for atomic layer deposition (ALD) on 2D materials, and the initial stage of growth was probed using <i>in situ</i> STM. ALD pulses of trimethyl aluminum (TMA) and H₂O resulted in the uniform deposition of AlO_<i>x</i> on the TiOPc/HOPG. The uniformity of the dielectric is consistent with DFT calculations showing multiple reaction sites are available on the TiOPc molecule for reaction with TMA. Capacitors prepared with 50 cycles of AlO_<i>x</i> on TiOPc/graphene display a capacitance greater than 1000 nF/cm², and dual-gated devices have current densities of 10^–7A/cm² with 40 cycles

Simultaneous Transfer and Doping of CVD-Grown Graphene by Fluoropolymer for Transparent Conductive Films on Plastic

Chemical doping can decrease sheet resistance of graphene while maintaining its high transparency. We report a new method to simultaneously transfer and dope chemical vapor deposition grown graphene onto a target substrate using a fluoropolymer as both the supporting and doping layer. Solvent was used to remove a significant fraction of the supporting fluoropolymer, but residual polymer remained that doped the graphene significantly. This contrasts with a more widely used supporting layer, polymethylmethacrylate, which does not induce significant doping during transfer. The fluoropolymer doping mechanism can be explained by the rearrangement of fluorine atoms on the graphene basal plane caused by either thermal annealing or soaking in solvent, which induces ordered dipole moments near the graphene surface. This simultaneous transfer and doping of the graphene with a fluoropolymer increases the carrier density significantly, and the resulting monolayer graphene film exhibits a sheet resistance of ∼320 Ω/sq. Finally, the method presented here was used to fabricate flexible and a transparent graphene electrode on a plastic substrate

Toward the Controlled Synthesis of Hexagonal Boron Nitride Films

Atomically smooth hexagonal boron nitride (h-BN) layers have very useful properties and thus potential applications for protective coatings, deep ultraviolet (DUV) emitters, and as a dielectric for nanoelectronics devices. In this paper, we report on the growth of h-BN by a low-pressure chemical vapor deposition (LPCVD) process using diborane and ammonia as the gas precursors. The use of LPCVD allows synthesis of h-BN with a controlled number of layers defined by the growth conditions, temperature, time, and gas partial pressure. Furthermore, few-layer h-BN was also grown by a sequential growth method, and insights into the growth mechanism are described, thus forming the basis of future growth of h-BN by atomic layer epitaxy