Direct large-area growth of graphene on silicon for potential ultra-low-friction applications and silicon-based technologies.

Deposition of layers of graphene on silicon has the potential for a wide range of optoelectronic and mechanical applications. However, direct growth of graphene on silicon has been difficult due to the inert, oxidized silicon surfaces. Transferring graphene from metallic growth substrates to silicon is not a good solution either, because most transfer methods involve multiple steps that often lead to polymer residues or degradation of sample quality. Here we report a single-step method for large-area direct growth of continuous horizontal graphene sheets and vertical graphene nano-walls on silicon substrates by plasma-enhanced chemical vapor deposition (PECVD) without active heating. Comprehensive studies utilizing Raman spectroscopy, x-ray/ultraviolet photoelectron spectroscopy (XPS/UPS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and optical transmission are carried out to characterize the quality and properties of these samples. Data gathered by the residual gas analyzer (RGA) during the growth process further provide information about the synthesis mechanism. Additionally, ultra-low friction (with a frictional coefficient ∼0.015) on multilayer graphene-covered silicon surface is achieved, which is approaching the superlubricity limit (for frictional coefficients <0.01). Our growth method therefore opens up a new pathway towards scalable and direct integration of graphene into silicon technology for potential applications ranging from structural superlubricity to nanoelectronics, optoelectronics, and even the next-generation lithium-ion batteries.

Interfacial States and Fano-Feshbach Resonance in Graphene-Silicon Vertical Junction.

Interfacial quantum states are drawing tremendous attention recently because of their importance in design of low-dimensional quantum heterostructures with desired charge, spin, or topological properties. Although most studies of the interfacial exchange interactions were mainly performed across the interface vertically, the lateral transport nowadays is still a major experimental method to probe these interactions indirectly. In this Letter, we fabricated a graphene and hydrogen passivated silicon interface to study the interfacial exchange processes. For the first time we found and confirmed a novel interfacial quantum state, which is specific to the 2D-3D interface. The vertically propagating electrons from silicon to graphene result in electron oscillation states at the 2D-3D interface. A harmonic oscillator model is used to explain this interfacial state. In addition, the interaction between this interfacial state (discrete energy spectrum) and the lateral band structure of graphene (continuous energy spectrum) results in Fano-Feshbach resonance. Our results show that the conventional description of the interfacial interaction in low-dimensional systems is valid only in considering the lateral band structure and its density-of-states and is incomplete for the ease of vertical transport. Our experimental observation and theoretical explanation provide more insightful understanding of various interfacial effects in low-dimensional materials, such as proximity effect, quantum tunneling, etc. More important, the Fano-Feshbach resonance may be used to realize all solid-state and scalable quantum interferometers.

Single-step growth of graphene and graphene-based nanostructures by plasma-enhanced chemical vapor deposition.

The realization of many promising technological applications of graphene and graphene-based nanostructures depends on the availability of reliable, scalable, high-yield and low-cost synthesis methods. Plasma enhanced chemical vapor deposition (PECVD) has been a versatile technique for synthesizing many carbon-based materials, because PECVD provides a rich chemical environment, including a mixture of radicals, molecules and ions from hydrocarbon precursors, which enables graphene growth on a variety of material surfaces at lower temperatures and faster growth than typical thermal chemical vapor deposition. Here we review recent advances in the PECVD techniques for synthesis of various graphene and graphene-based nanostructures, including horizontal growth of monolayer and multilayer graphene sheets, vertical growth of graphene nanostructures such as graphene nanostripes with large aspect ratios, direct and selective deposition of monolayer and multi-layer graphene on nanostructured substrates, and growth of multi-wall carbon nanotubes. By properly controlling the gas environment of the plasma, it is found that no active heating is necessary for the PECVD growth processes, and that high-yield growth can take place in a single step on a variety of surfaces, including metallic, semiconducting and insulating materials. Phenomenological understanding of the growth mechanisms are described. Finally, challenges and promising outlook for further development in the PECVD techniques for graphene-based applications are discussed.

Vertically-aligned graphene nanowalls grown via plasma-enhanced chemical vapor deposition as a binder-free cathode in Li-O2 batteries.

In the present report, vertically-aligned graphene nanowalls are grown on Ni foam (VA-G/NF) using plasma-enhanced chemical vapor deposition method at room temperature. Optimization of the growth conditions provides graphene sheets with controlled defect sites. The unique architecture of the vertically-aligned graphene sheets allows sufficient space for the ionic movement within the sheets and hence enhancing the catalytic activity. Further modification with ruthenium nanoparticles (Ru NPs) drop-casted on VA-G/NF improves the charge overpotential for lithium-oxygen (Li-O2) battery cycles. Such reduction we believe is due to the easier passage of ions between the perpendicularly standing graphene sheets thereby providing ionic channels.

Competing weak localization and weak antilocalization in ultrathin topological insulators.

We demonstrate evidence of a surface gap opening in topological insulator (TI) thin films of (Bi(0.57)Sb(0.43))(2)Te(3) below six quintuple layers through transport and scanning tunneling spectroscopy measurements. By effective tuning the Fermi level via gate-voltage control, we unveil a striking competition between weak localization and weak antilocalization at low magnetic fields in nonmagnetic ultrathin films, possibly owing to the change of the net Berry phase. Furthermore, when the Fermi level is swept into the surface gap of ultrathin samples, the overall unitary behaviors are revealed at higher magnetic fields, which are in contrast to the pure WAL signals obtained in thicker films. Our findings show an exotic phenomenon characterizing the gapped TI surface states and point to the future realization of quantum spin Hall effect and dissipationless TI-based applications.

Dramatically Enhanced Valley-Polarized Emission by Alloying and Electrical Tuning of Monolayer WTe2 x S2(1- x ) Alloys at Room Temperature with 1T'-WTe2 -Contact.

Monolayer ternary tellurides based on alloying different transition metal dichalcogenides (TMDs) can result in new two-dimensional (2D) materials ranging from semiconductors to metals and superconductors with tunable optical and electrical properties. Semiconducting WTe2 x S2(1- x ) monolayer possesses two inequivalent valleys in the Brillouin zone, each valley coupling selectively with circularly polarized light (CPL). The degree of valley polarization (DVP) under the excitation of CPL represents the purity of valley polarized photoluminescence (PL), a critical parameter for opto-valleytronic applications. Here, new strategies to efficiently tailor the valley-polarized PL from semiconducting monolayer WTe2 x S2(1- x ) at room temperature (RT) through alloying and back-gating are presented. The DVP at RT is found to increase drastically from < 5% in WS2 to 40% in WTe0.12 S1.88 by Te-alloying to enhance the spin-orbit coupling. Further enhancement and control of the DVP from 40% up to 75% is demonstrated by electrostatically doping the monolayer WTe0.12 S1.88 via metallic 1T'-WTe2 electrodes, where the use of 1T'-WTe2 substantially lowers the Schottky barrier height (SBH) and weakens the Fermi-level pinning of the electrical contacts. The demonstration of drastically enhanced DVP and electrical tunability in the valley-polarized emission from 1T'-WTe2 /WTe0.12 S1.88 heterostructures paves new pathways towards harnessing valley excitons in ultrathin valleytronic devices for RT applications.

Surface-dominated conduction in a 6 nm thick Bi2Se3 thin film.

We report a direct observation of surface dominated conduction in an intrinsic Bi(2)Se(3) thin film with a thickness of six quintuple layers grown on lattice-matched CdS (0001) substrates by molecular beam epitaxy. Shubnikov-de Haas oscillations from the topological surface states suggest that the Fermi level falls inside the bulk band gap and is 53 ± 5 meV above the Dirac point, which is in agreement with 70 ± 20 meV obtained from scanning tunneling spectroscopies. Our results demonstrate a great potential of producing genuine topological insulator devices using Dirac Fermions of the surface states, when the film thickness is pushed to nanometer range.

Low-Temperature Direct Growth of Nanocrystalline Multilayer Graphene on Silver with Long-Term Surface Passivation.

A wide variety of transition metals, including copper and gold, have been successfully used as substrates for graphene growth. On the other hand, it has been challenging to grow graphene on silver, so realistic applications by combining graphene and silver for improved electrode stability and enhanced surface plasmon resonance in organic light-emitting diodes and biosensing have not been realized to date. Here, we demonstrate the surface passivation of silver through the single-step rapid growth of nanocrystalline multilayer graphene on silver via low-temperature plasma-enhanced chemical vapor deposition (PECVD). The effect of the growth time on the graphene quality and the underlying silver characteristics is investigated by Raman spectroscopy, X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), and cross-sectional annular dark-field scanning transmission electron microscopy (ADF-STEM). These results reveal nanocrystalline graphene structures with turbostratic layer stacking. Based on the XPS and ADF-STEM results, a PECVD growth mechanism of graphene on silver is proposed. The multilayer graphene also provides excellent long-term protection of the underlying silver surface from oxidation after 5 months of air exposure. This development thus paves the way toward realizing technological applications based on graphene-protected silver surfaces and electrodes as well as hybrid graphene-silver plasmonics.

Control of trion-to-exciton conversion in monolayer WS2 by orbital angular momentum of light.

Controlling the density of exciton and trion quasiparticles in monolayer two-dimensional (2D) materials at room temperature by nondestructive techniques is highly desired for the development of future optoelectronic devices. Here, the effects of different orbital angular momentum (OAM) lights on monolayer tungsten disulfide at both room temperature and low temperatures are investigated, which reveal simultaneously enhanced exciton intensity and suppressed trion intensity in the photoluminescence spectra with increasing topological charge of the OAM light. In addition, the trion-to-exciton conversion efficiency is found to increase rapidly with the OAM light at low laser power and decrease with increasing power. Moreover, the trion binding energy and the concentration of unbound electrons are estimated, which shed light on how these quantities depend on OAM. A phenomenological model is proposed to account for the experimental data. These findings pave a way toward manipulating the exciton emission in 2D materials with OAM light for optoelectronic applications.

Electrically Tunable and Dramatically Enhanced Valley-Polarized Emission of Monolayer WS2 at Room Temperature with Plasmonic Archimedes Spiral Nanostructures.

Monolayer transition metal dichalcogenides (TMDs) have intrinsic valley degrees of freedom, making them appealing for exploiting valleytronic applications in information storage and processing. WS2 monolayer possesses two inequivalent valleys in the Brillouin zone, each valley coupling selectively with a circular polarization of light. The degree of valley polarization (DVP) under the excitation of circularly polarized light (CPL) is a parameter that determines the purity of valley polarized photoluminescence (PL) of monolayer WS2 . Here efficient tailoring of valley-polarized PL from monolayer WS2 at room temperature (RT) through surface plasmon-exciton interactions with plasmonic Archimedes spiral (PAS) nanostructures is reported. The DVP of WS2 at RT can be enhanced from <5% to 40% and 50% by using 2 turns (2T) and 4 turns (4T) of PAS, respectively. Further enhancement and control of excitonic valley polarization is demonstrated by electrostatically doping monolayer WS2 . For CPL on WS2 -2TPAS heterostructures, the 40% valley polarization is enhanced to 70% by modulating the carrier doping via a backgate, which may be attributed to the screening of momentum-dependent long-range electron-hole exchange interactions. The manifestation of electrically tunable valley-polarized emission from WS2 -PAS heterostructures presents a new strategy toward harnessing valley excitons for application in ultrathin valleytronic devices.

Single-Step Direct Growth of Graphene on Cu Ink toward Flexible Hybrid Electronic Applications by Plasma-Enhanced Chemical Vapor Deposition.

Highly customized and free-formed products in flexible hybrid electronics (FHE) require direct pattern creation such as inkjet printing (IJP) to accelerate product development. In this work, we demonstrate the direct growth of graphene on Cu ink deposited on polyimide (PI) by means of plasma-enhanced chemical vapor deposition (PECVD), which provides simultaneous reduction, sintering, and passivation of the Cu ink and further reduces its resistivity. We investigate the PECVD growth conditions for optimizing the graphene quality on Cu ink and find that the defect characteristics of graphene are sensitive to the H2/CH4 ratio at higher total gas pressure during the growth. The morphology of Cu ink after the PECVD process and the dependence of the graphene quality on the H2/CH4 ratio may be attributed to the difference in the corresponding electron temperature. Therefore, this study paves a new pathway toward efficient growth of high-quality graphene on Cu ink for applications in flexible electronics and Internet of Things (IoT).

Polymer-Compatible Low-Temperature Plasma-Enhanced Chemical Vapor Deposition of Graphene on Electroplated Cu for Flexible Hybrid Electronics.

Flexible hybrid electronics and fan-out redistribution layers rely on electroplating Cu on polymers. In this work, direct low-temperature plasma-enhanced chemical vapor deposition (PECVD) of graphene on electroplated Cu over polyimide substrates is demonstrated, and the deposition of graphene is found to passivate and strengthen the electroplated Cu circuit. The effect of the H2/CH4 ratio on the PECVD graphene growth is also investigated, which is shown to affect not only the quality of graphene but also the durability of Cu. 100,000 cycles of folding with a bending radius of 2.5 mm and the corresponding resistance tests are carried out, revealing that Cu circuits covered by graphene grown with a higher H2/CH4 ratio can sustain many more bending cycles. Additionally, graphene coverage is shown to suppress the formation of copper oxides in ambient environment for at least 8 weeks after the PECVD process.

Significant Capacitance Enhancement via In Situ Exfoliation of Quasi-One-Dimensional Graphene Nanostripes in Supercapacitor Electrodes.

Graphene has received much attention as a supercapacitor electrode material due to its chemical inertness in preventing reaction with electrolytes and the large surface area due to its two-dimensional nature. However, when graphene sheets are processed into electrodes, they tend to stack together and form a turbostratic graphite material with a much reduced surface area relative to the total surface area of individual graphene sheets. Separately, electrochemical exfoliation of graphite is one method of producing single-layer graphene, which is often used to produce graphene for supercapacitor electrodes, although such exfoliated graphene still leads to reduced surface areas due to stacking during electrode fabrication. To utilize the large surface area of graphene, graphene must be exfoliated in situ within a supercapacitor device after the device fabrication. However, graphitic electrodes are typically destroyed upon exfoliation, which is largely due to the loss of electrical connectivity among small exfoliated graphene flakes. Here, we report successful in situ exfoliation of graphene nanostripes, a type of quasi-one-dimensional graphene nanomaterial with large length-to-width aspect ratios, as the anode material in supercapacitors. We find that the in situ exfoliation leads to over 400% enhancement in capacitance as the result of retaining the electrical connectivity among exfoliated quasi-one-dimensional graphene nanostripes in addition to increasing the total surface area, paving ways to fully realizing the benefit of graphene electrodes in supercapacitor applications.

Selective formation of pyridinic-type nitrogen-doped graphene and its application in lithium-ion battery anodes.

We report a high-yield single-step method for synthesizing nitrogen-doped graphene nanostripes (N-GNSPs) with an unprecedentedly high percentage of pyridinic-type doping (>86% of the nitrogen sites), and investigate the performance of the resulting N-GNSPs as a lithium-ion battery (LIB) anode material. The as-grown N-GNSPs are compared with undoped GNSPs using scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), helium ion-beam microscopy (HIM), and electrochemical methods. As an anode material we find that pyridinic-type N-GNSPs perform similarly to undoped GNSPs, suggesting that pyridinic sites alone are not responsible for the enhanced performance of nitrogen-doped graphene observed in previous studies, which contradicts common conjectures. In addition, post-mortem XPS measurements of nitrogen-doped graphene cycled as a lithium-ion battery anode are conducted for the first time, which reveal direct evidence for irreversible chemical changes at the nitrogen sites during cycling. These findings therefore provide new insights into the mechanistic models of doped graphene as LIB anodes, which are important in improving the anode designs for better LIB performance.

Nearly 90% Circularly Polarized Emission in Monolayer WS2 Single Crystals by Chemical Vapor Deposition.

Monolayer transition-metal dichalcogenides (TMDCs) in the 2H-phase are promising semiconductors for opto-valleytronic and opto-spintronic applications because of their strong spin-valley coupling. Here, we report detailed studies of opto-valleytronic properties of heterogeneous domains in CVD-grown monolayer WS2 single crystals. By illuminating WS2 with off-resonance circularly polarized light and measuring the resulting spatially resolved circularly polarized emission (Pcirc), we find significantly large circular polarization (Pcirc up to 60% and 45% for α- and ß-domains, respectively) already at 300 K, which increases to nearly 90% in the α-domains at 80 K. Studies of spatially resolved photoluminescence (PL) spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, Kelvin-probe force microscopy, and conductive atomic force microscopy reveal direct correlation among the PL intensity, defect densities, and chemical potential, with the α-domains showing lower defect densities and a smaller work function by 0.13 eV than the ß-domains. This work function difference indicates the occurrence of type-two band alignments between the α- and ß-domains. We adapt a classical model to explain how electronically active defects may serve as nonradiative recombination centers and find good agreement between experiments and the model. Scanning tunneling microscopic/spectroscopic (STM/STS) studies provide further evidence for tungsten vacancies (WVs) being the primary defects responsible for the suppressed PL and circular polarization in WS2. These results therefore suggest a pathway to control the opto-valleytronic properties of TMDCs by means of defect engineering.

A journey of no return and no regrets.

This article describes the author's personal journey from childhood to a career in physics. The beauty and truth that the author finds in physics has been the primary driving force and inspiration for her relentless pursuit of knowledge and her constant push for cutting-edge research, despite all obstacles and odds against her as a "double minority" (an Asian woman) in a predominantly white male profession. Based on her 20 years of research and teaching at one of the world's leading academic institutions, the California Institute of Technology, the author observes no differences between men and women in their scientific talents, thereby dispelling the misconception of possible inferiority of women as scientists. She further stresses the urgent societal needs for more talent in various sciences to address many of the important issues facing the planet. In this context, society must promote gender equality in science so that one half of the talent does not go to waste. Finally, the author shares her thoughts with young people about how to be better prepared to face the challenges in life and fulfill their dreams.