As-transferred Graphene Research Articles

Integrated wafer-scale ultra-flat graphene by gradient surface energy modulation

The integration of large-scale two-dimensional (2D) materials onto semiconductor wafers is highly desirable for advanced electronic devices, but challenges such as transfer-related crack, contamination, wrinkle and doping remain. Here, we developed a generic method by gradient surface energy modulation, leading to a reliable adhesion and release of graphene onto target wafers. The as-obtained wafer-scale graphene exhibited a damage-free, clean, and ultra-flat surface with negligible doping, resulting in uniform sheet resistance with only ~6% deviation. The as-transferred graphene on SiO2/Si exhibited high carrier mobility reaching up ~10,000 cm2 V−1 s−1, with quantum Hall effect (QHE) observed at room temperature. Fractional quantum Hall effect (FQHE) appeared at 1.7 K after encapsulation by h-BN, yielding ultra-high mobility of ~280,000 cm2 V−1 s−1. Integrated wafer-scale graphene thermal emitters exhibited significant broadband emission in near-infrared (NIR) spectrum. Overall, the proposed methodology is promising for future integration of wafer-scale 2D materials in advanced electronics and optoelectronics.

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.

Effects of Different Ion Irradiation on the Contact Resistance of Pd/Graphene Contacts.

The effect of ion-induced defects on graphene was studied to investigate the contact resistance of 40 nm palladium (Pd) contacting on graphene. The defect development was considered and analyzed by irradiating boron (B), carbon (C), nitrogen (N2), and argon (Ar) ions on as-transferred graphene before metallization. The bombardment energy was set at 1.5 keV and ion dose at 1 × 1014 ions/cm2. The defect yields under different ion irradiation conditions were examined by Raman spectroscopy. Although, dissolution process occurs spontaneously upon metal deposition, chemical reaction between metal and graphene is more pronounced at higher temperatures. The rapid thermal annealing (RTA) treatment was performed to improve the Pd/graphene contact after annealing at 450 °C, 500 °C, 550 °C, and 600 °C. The lowest contact resistance of 95.2 Ω-µm was achieved at 550 °C RTA with Ar ion irradiation. We have proved that ion irradiation significantly enhance the Pd/graphene contact instead of pd/pristine graphene contact. Therefore, in view of the contention of results ion induced defects before metallization plus the RTA served an excellent purpose to reduce the contact resistance.

Effect of interfacial Ni between graphene and Pt/Au on reducing specific contact resistivity

Low contact resistance between graphene and metals is of critical importance to fabricate high-performance graphene-based devices. In this work, the effect of interfacial Ni of different thicknesses, i.e. 0 nm, 1 nm, 2 nm, 4 nm and 5 nm, on the contact resistance of graphene and Pt/Au was investigated systematically. As-transferred graphene grown on Cu foil using a PMMA-assisted process was characterized by optical, Raman and atomic force microscopy. As to the extraction of contact resistance, conventional transmission line method structures were fabricated and measured sophisticatedly. Rapid thermal annealing at different temperatures, i.e. 400 °C, 450 °C, 500 °C, 550 °C and 600 °C, was also performed to determine the optimum temperature and thickness of Ni as an interfacial layer. It was found that an interfacial Ni with proper thickness and thermal treatment is beneficial in reducing contact resistance between graphene and Pt/Au. The role of interfacial Ni is also discussed.

Influences of Polymer Residues on the Growth Properties of Pentacene Thin Film on Graphene Substrates

Understanding of the growth properties of organic thin film (OTF) on graphene surface is beneficial to develop high-performance organic electronic devices based on OTF and graphene electrodes. In this work, we investigated the growth behaviors of pentacene on the poly(methyl methacrylate) (PMMA)-assisted wet-transfer graphene substrates. Especially, the influence of PMMA residues and graphene wrinkles on the initial nucleation behavior and subsequent aggregation of pentacene were studied in detail. Pentacene adopts standing-up geometry on the as-transferred graphene substrates. The molecules prefer to initially reside beside graphene wrinkles where the density of PMMA residues is found to be larger than the flat regions of graphene and then the subsequent deposited pentacene was packed face-to-face and developed into one-dimensional fiberlike domains with a fiber length of few micrometers. Controlled experiments and detailed surface analysis of graphene reveal that the hydroxyl groups of polymer residues ...

Study of copper-phthalocyanine and pentacene film growth on transferred graphene: The influence of polymer residues

Wet transferring of chemical vapor deposition (CVD) graphene with the assistance of poly(methyl methacrylate) (PMMA) usually leaves polymer contaminations onto graphene surface. Knowledge about the influence of PMMA residues on organic film growth properties is crucial for graphene-related organic electronic devices. In this study, we investigate growth properties of coper-phthalocyanine (CuPc) and pentacene on PMMA contaminated graphene substrate. Grain size and morphologies of CuPc and pentacene films were found to be governed by the density of PMMA residues on graphene. Nevertheless, the molecular packing structures of CuPc and pentacene respond differently with the density with PMMA residues. CuPc molecules tend to nucleated into grains with molecular π-π stacking parallel to graphene surface, which is irrespective of the PMMA residues. Whereas the packing behavior of pentacene on PMMA-transferred CVD graphene is sensitive to the density of PMMA residues. Molecular π-π stacking perpendicular to graphene is observed when pentacene was deposited onto as-transferred graphene. Parallel mode was observed only on the substrates without PMMA residues.

Improved topological conformity enhances heat conduction across metal contacts on transferred graphene

Thermal conductance of metal contacts on transferred graphene (trG) could be significantly reduced from the intrinsic value due to additional resistance by increased roughness, residues, oxides and voids. In this paper, we compare the thermal conductance (G) of Al/trG/Cu interfaces with that of Al/grG/Cu interfaces. We find that for the Al/grG/Cu interfaces of as-grown CVD graphene, G = 31 MW m−2 K−1 at room temperature, two orders of magnitude lower than that of Al/Cu interfaces. For most as-transferred graphene on Cu films, G ≈ 20 MW m−2 K−1, ≈35 % lower than that of as-grown CVD graphene. We rule out the contributions of residues, native oxides and interfaces roughness, and attribute the difference to different degrees of conformity of graphene to the Cu substrates. We find that a contact area of ≈50 % only reduces the thermal conductance by ≈35 %, suggesting that a small amount of heat transfer occurs across “voids” at graphene interfaces. We improve the conformity of the as-transferred graphene by annealing the samples at 300 °C, and thus enhancing the thermal conductance to the intrinsic value. From the temperature dependence measurements, we also confirm that phonons are the dominant heat carries across the metal/graphene/metal interfaces despite a substantial carrier concentration of ≈3 × 1012 cm−2 induced in the graphene.

Effect of water layer at the SiO2/graphene interface on pentacene morphology.

Atomic force microscopy has been used to examine early stages of pentacene growth on exfoliated single-layer graphene transferred to SiO2 substrates. We have observed 2D growth with mean height of 1.5 ± 0.2 nm on as-transferred graphene. Three-dimensional islands of pentacene with an average height of 11 ± 2 nm were observed on graphene that was annealed at 350 °C prior to pentacene growth. Compellingly similar 3D morphology has been observed on graphene transferred onto SiO2 that was treated with hexamethyldisilazane prior to the transfer of graphene. On multilayer graphene we have observed 2D growth, regardless of the treatment of SiO2. We interpret this behavior of pentacene molecules in terms of the influence of the dipolar field that emerges from the water monolayer at the graphene/SiO2 interface on the surface energy of graphene.

Synergy between graphene and Au nanoparticles (heterojunction) towards quenching, improving Raman signal, and UV light sensing.

Here, we developed a simple method for obtaining a heterojunction composed of graphene (G) and surfactant-coated Au nanoparticles (NPs) to measure film conductivity and surface enhanced Raman scattering (SERS). Monolayer G is obtained by chemical vapor deposition (CVD) and transferred via poly(methyl methacrylate) (PMMA) to microfabricated Au electrodes, glass, and silicon. Post-synthesis treatments of G with PMMA and ozone (O3) showed 1 and 6 orders of magnitude decrease in film conductivity, respectively. The heterojunction formation with Au NPs had no major effect on G conductivity. In this work is demonstrated that G quenches more than 90% of the combined photoluminescence and fluorescence of Au NPs and Rhodamine B (RhB), respectively. Signal quenching permitted quantitative analysis of SERS of RhB on various substrates including as-transferred graphene, oxidized graphene (OG), and the heterojunction. While G is mainly responsible for quenching photoluminescence and fluorescence, ∼3 orders of magnitude increase SERS activity for RhB was accomplished by the heterojunction. Finally, we wanted to correlate changes in film current during UV light sensing experiments. We found striking differences in the sensing profiles at different UV energies.

A Direct and Polymer-Free Method for Transferring Graphene Grown by Chemical Vapor Deposition to Any Substrate

We demonstrate a polymer-free method that can routinely transfer relatively large-area graphene to any substrate with advanced electrical properties and superior atomic and chemical structures as compared to the graphene sheets transferred with conventional polymer-assisted methods. The graphene films that are transferred with polymer-free method show high electrical conductance and excellent optical transmittance. Raman spectroscopy and X-ray/ultraviolet photoelectron spectroscopy also confirm the presence of high quality graphene sheets with little contamination after transfer. Atom-resolved images can be obtained using scanning tunneling microscope on as-transferred graphene sheets without additional cleaning process. The mobility of the polymer-free graphene monolayer is as high as 63,000 cm(2) V(-1) s(-1), which is 50% higher than the similar sample transferred with the conventional method. More importantly, this method allows us to place graphene directly on top of devices made of soft materials, such as organic and polymeric thin films, which widens the applications of graphene in soft electronics.

Interfacial bonding characteristics between graphene and dielectric substrates

Achieving strong adhesion between graphene and SiOx/Si substrates is crucial to make reliable graphene based electronics and electro-optic devices. We report the enhanced adhesion energy by vacuum annealing and the quantification of graphene-SiOx/Si substrate adhesion energy by using the nano-scratch technique coupled with Raman spectroscopy and x-ray photoelectron spectroscopy (XPS). We found that the adhesion energy of as-transferred graphene on SiOx/Si substrates is ∼2.978 J m−2. By applying different annealing protocols of rapid thermal annealing and vacuum annealing, the adhesion energy of graphene-SiOx/Si is increased to 10.09 and 20.64 J m−2, respectively. The increase in adhesion energy is due to the formation of chemical bonds between the graphene and SiOx at high temperatures. The XPS depth profiling confirms that C–O and C=O chemical bond formation occurs at the graphene/SiOx interface. These results could be adapted for graphene/Si nanoelectronics device fabrication and they open up a pathway towards producing reliable solid state devices.

Self-organizing properties of triethylsilylethynyl-anthradithiophene on monolayer graphene electrodes in solution-processed transistors

Graphene has shown great potential as an electrode material for organic electronic devices such as organic field-effect transistors (FETs) because of its high conductivity, thinness, and good compatibility with organic semiconductor materials. To achieve high performance in graphene-based organic FETs, favorable molecular orientation and good crystallinity of organic semiconductors on graphene are desired. This strongly depends on the surface properties of graphene. Here, we investigate the effects of polymer residues that remain on graphene source/drain electrodes after the transfer/patterning processes on the self-organizing properties and field-effect characteristics of the overlying solution-processed triethylsilylethynyl-anthradithiophene (TES-ADT). A solvent-assisted polymer residue removal process was introduced to effectively remove residues or impurities on the graphene surface. Unlike vacuum-deposited small molecules, TES-ADT displayed a standing-up molecular assembly, which facilitates lateral charge transport, on both the residue-removed clean graphene and as-transferred graphene with polymer residues. However, TES-ADT films grown on the cleaned graphene showed a higher crystallinity and larger grain size than those on the as-transferred graphene. The resulting TES-ADT FETs using cleaned graphene source/drain electrodes therefore exhibited a superior device performance compared to devices using as-transferred graphene electrodes, with mobilities as high as 1.38 cm(2) V(-1) s(-1).

Fast and controllable fabrication of suspended graphene nanopore devices

A poly(methyl methacrylate) assisted dry transfer method was developed to transfer graphene microflake onto a suspended SiN chip in an effective and efficient way for further graphene nanopore drilling for DNA analysis. Graphene microflakes can be patterned by e-beam lithography to a designed shape and size on a large scale of a few thousands simultaneously. Subsequently, individual graphene microflakes can be picked up and transferred to a target hole on a suspended SiN membrane with 1 µm precision via a site-specific transfer-printing method. Nanopores with different diameters from 3 to 20 nm were drilled on the as-transferred graphene membrane in a transmission electron microscope. This method offers a fast and controllable way to fabricate graphene nanopores for DNA analyses.

Annealing Temperature and Substrate Effects on the Raman Spectra of Transferred CVD Graphene

ABSTRACTThis work explores the influence of the post-transfer anneal temperature and the substrate on transferred graphene and its Raman properties. Graphene grown by low pressure chemical vapor deposition on copper foils was transferred to SiO2/Si, fused silica, and silicon substrates via a process that involves coating the graphene with PMMA as a protective handling layer during the wet chemical etching of the copper and then placing the PMMA/graphene onto the substrate. The PMMA layer was then removed by heating in a hydrogen/argon atmosphere at temperatures ranging from 350 to 550 °C or by exposing the PMMA to heated acetone vapor/liquid. Raman spectroscopy measurements, taken before and after PMMA removal, reveal differences in the prominent Raman features, the G and G’ peaks, upon annealing. These changes include (1) a shift in the average G and G’ peak positions when comparing Raman spectra before and after PMMA removal and (2) a decrease in the G’:G peak intensity ratio (IG’/IG), which is typically used as a measure of the number of graphene layers. For both the as-transferred graphene and graphene removed by the heated acetone, the IG’/IG peak ratio was approximately 2, indicating single layer graphene. However, when the graphene was annealed at temperatures above 350 °C, the IG’/IG intensity ratio varied from 0.5 to 1.5. These changes in the Raman spectra are similar to those observed in exfoliated single layer graphene supported on SiO2/Si substrates and are indicative of graphene-substrate interaction effects that lead to hole doping of the graphene [1,2]. These trends were observed for graphene transferred to all three substrates, regardless of the substrate surface roughness and/or composition.