Work Function Of Graphene Research Articles

Inert Liquid Exfoliation and Langmuir-Type Thin Film Deposition of Semimetallic Metal Diborides.

Graphite is one of only a few layered materials that can be exfoliated into nanosheets with semimetallic properties, which limits the applications of nanosheet-based electrodes to material combinations compatible with the work function of graphene. It is therefore important to identify additional metallic or semimetallic two-dimensional (2D) nanomaterials that can be processed in solution for scalable fabrication of printed electronic devices. Metal diborides represent a family of layered non-van der Waals crystals with semimetallic properties for all nanosheet thicknesses. While previous reports show that the exfoliated nanomaterial is prone to oxidation, we demonstrate a readily accessible inert exfoliation process to produce quasi-2D nanoplatelets with intrinsic material properties. For this purpose, we demonstrate the exfoliation of three representative metal diborides (MgB2, CrB2, and ZrB2) under inert conditions. Nanomaterial is characterized using a combination of transmission electron microscopy, scanning electron microscopy, atomic force microscopy, IR, and UV-vis measurements, with only minimal oxidation indicated postprocessing. By depositing the pristine metal diboride nanoplatelets as thin films using a Langmuir-type deposition technique, the ohmic behavior of the networks is validated. Furthermore, the material decomposition is studied by using a combination of electrical and optical measurements after controlled exposure to ambient conditions. Finally, we report an efficient, low-cost approach for sample encapsulation to protect the nanomaterials from oxidation. This is used to demonstrate low-gauge factor strain sensors, confirming metal diboride nanosheets as a suitable alternative to graphene for electrode materials in printed electronics.

Spatial and Bidirectional Work Function Modulation of Monolayer Graphene with Patterned Polymer "Fluorozwitterists".

Understanding the electronic properties resulting from soft-hard material interfacial contact has elevated the utility of functional polymers in advanced materials and nanoscale structures, such as in work function engineering of two-dimensional (2D) materials to produce new types of high-performance devices. In this paper, we describe the electronic impact of functional polymers, containing both zwitterionic and fluorocarbon components in their side chains, on the work function of monolayer graphene through the preparation of negative-tone photoresists, which we term "fluorozwitterists." The zwitterionic and fluorinated groups each represent dipole-containing moieties capable of producing distinct surface energies as thin films. Kelvin probe force microscopy revealed these polymers to have a p-doping effect on graphene, which contrasts the work function decrease typically associated with polymer-to-graphene contact. Copolymerization of fluorinated zwitterionic monomers with methyl methacrylate and a benzophenone-substituted methacrylate produced copolymers that were amenable to photolithographic fabrication of fluorozwitterist structures. Consequently, spatial alteration of zwitterion coverage across graphene yielded stripes that resemble a lateral p-i-n diode configuration, with local increase or decrease of work function. Overall, this polymeric fluorozwitterist design is suitable for enabling simple, solution-based surface patterning and is anticipated to be useful for spatial work function modulation of 2D materials integrated into electronic devices.

Data-driven deep learning prediction of boron-doped graphene work function

The atomic-scale doping plays a crucial role in determining the work function of doped graphene. However, it is a challenge to comprehensively investigate its work function due to the large range of possible molecular configurations. In this study, more than 30,000 pieces of data of the work functions from boron-doped graphene with different doping concentrations and positions is calculated via DFT, and the dataset is further expanded to 115,000 based on the molecular structural symmetry. Then, a simple structural descriptor-based method is developed to characterize the surface of the doped graphene. Finally, a deep learning model is proposed to predict the work function. The results show that the proposed model can accurately predict the work function with the R2 > 0.95 and MSE < 0.0013 for a 3×3 supercell. In addition, this study also provides the possibility to quickly investigate the work function of other heteroatom 2D materials.

Work function-tunable graphene/WO3 heterojunctions for high-performance photoelectrochemical cell: UV-treatment effect and defective graphene

Designing hybrid photoelectrodes with graphene capable of efficient charge-carrier transfer and excellent chemical stability is an effective strategy for developing high-performance photoelectrochemical (PEC) cells. However, it remains unclear how the PEC properties are enhanced and how to control the junction properties in graphene/metal oxide heterojunction-based photoelectrodes. Here, we develop a deterministic junction to enhance PEC performance in graphene/tungsten trioxide (WO3)-based photoelectrodes by tuning the work function of graphene. It reveals that the band structure of graphene/WO3 heterojunctions can be modified by ultraviolet (UV) treatment on WO3 thin films. This modification is supported by the observation that a single-layer graphene/UV-treated WO3 photoelectrode exhibits significantly enhanced PEC activities toward the oxygen evolution reaction (OER) (evidenced by features like a threefold increase in photocurrent, an onset potential shift, and improved stability), whereas the single-layer graphene/untreated WO3 electrode demonstrates improved properties for the hydrogen evolution reaction (HER). Additionally, defects in the graphene layer formed during PEC water splitting contribute to high catalytic activities of the graphene/WO3 photoelectrode due to a decrease in the Gibbs free energy for OER and HER. These results emphasize that band structure engineering via work function tuning in graphene/WO3 heterostructures can provide multiple benefits for high PEC performance and long-term stability.

Mechanical Control of Quantum Transport in Graphene.

2D materials (2DMs) are fundamentally electro-mechanical systems. Their environment unavoidably strains them and modifies their quantum transport properties. For instance, a simple uniaxial strain can completely turn off the conductance of ballistic graphene or switch on/off the superconducting phase of magic-angle bilayer graphene. This article reports measurements of quantum transport in strained graphene transistors which agree quantitatively with models based on mechanically-induced gauge potentials. A scalar potential is mechanically induced in situ to modify graphene's work function by up to 25 meV. Mechanically generated vector potentials suppress the ballistic conductance of graphene by up to 30% and control its quantum interferences. The data are measured with a custom experimental platform able to precisely tune both the mechanics and electrostatics of suspended graphene transistors at low-temperature over a broad range of strain (up to 2.6%). This work opens many opportunities to harness quantitative strain effects in 2DM quantum transport andtechnologies.

Work Function Prediction by Graph Neural Networks for Configurationally Hybridized Boron-Doped Graphene.

Graphene, serving as electrodes, is widely applied in electronic and optoelectronic devices. Work function as one of the fundamental intrinsic characteristics of graphene directly affects the interfacial properties of the electrodes, thereby affecting the performance of the devices. Much work has been done to regulate the work function of graphene to expand its application fields, and doping has been demonstrated as an effective method. However, the numerous types of doped graphene make the investigation of its work function time-consuming and labor-intensive. In order to quickly obtain the relationship between the structure and property, a deep learning method is employed to predict the work function in this study. Specifically, a data set of over 30,000 compositions with the work function on boron-doped graphene at different concentrations and doping positions via density functional theory simulations was established through ab initio calculations. Then, a novel fusion model (GT-Net) combining transformers and graph neural networks (GNNs) was proposed. After that, improved effective GNN-based descriptors were developed. Finally, three different GNN methods were compared, and the results show that the proposed method could accurately predicate the work function with the R2 = 0.975 and RMSE = 0.027. This study not only provides the possibility of designing materials with specific properties at the atomic level but also demonstrates the performance of GNNs on graph-level tasks with the same graph structure and atomic number.

Graphene on quartz modified with rhenium oxide as a semitransparent electrode for organic electronics

Our research shows that commercially available graphene on quartz modified with rhenium oxide meets the requirements for its use as a conductive and transparent anode in optoelectronic devices. The cluster growth of rhenium oxide enables an increase in the work function of graphene by 1.3 eV up to 5.2 eV, which guarantees an appropriate adjustment to the energy levels of the organic semiconductors used in OLED devices.

Calculation of Graphene Work Function Variations Due to Alkali Metal + Oxygen Adsorption

Graphene has a high work function of 4.6 eV, and it can't be directly used as thermionic emission material. The graphene work function shows a decreasing trend in alkali metal/oxygen (AM/O) coadsorption experiments. Anderson–Newns (AN) model is a classical theoretical model for calculating the work function of adsorption surface. The present study, aiming at AM/O adsorption system, modifies and optimizes the AN model by redefining the calculation method of adsorption bond length λ and establishes the relationship between material work function, thermionic emission performance, and surface coverage. Based on the modified model, the influence of work function decline and thermionic emission performance of cesium/oxygen, potassium/oxygen, and sodium/oxygen graphene adsorption systems is studied. The results show that the work function of graphene affected by the three AM/O adsorbents is basically the same with the increase of coverage, and all of them quickly decrease to the lowest value and then increase slightly. The maximum work function declines are 3.51, 3.30, and 2.83 eV, respectively. At 1000 K, the maximum output current densities are 340, 36, and 0.15 A cm−2, respectively.

Direct Electrochemical Functionalization of Graphene Grown on Cu Including the Reaction Rate Dependence on the Cu Facet Type.

We present an electrochemical method to functionalize single-crystal graphene grown on copper foils with a (111) surface orientation by chemical vapor deposition (CVD). Graphene on Cu(111) is functionalized with 4-iodoaniline by applying a constant negative potential, and the degree of functionalization depends on the applied potential and reaction time. Our approach stands out from previous methods due to its transfer-free method, which enables more precise and efficient functionalization of single-crystal graphene. We report the suggested effects of the Cu substrate facet by comparing the reactivity of graphene on Cu(111) and Cu(115). The electrochemical reaction rate changes dramatically at the potential threshold for each facet. Kelvin probe force microscopy was used to measure the work function, and the difference in onset potentials of the electrochemical reaction on these two different facets are explained in terms of the difference in work function values. Density functional theory and Monte Carlo calculations were used to calculate the work function of graphene and the thermodynamic stability of the aniline functionalized graphene on these two facets. This study provides a deeper understanding of the electrochemical behavior of graphene (including single-crystal graphene) on Cu(111) and Cu(115). It also serves as a basis for further study of a broad range of reagents and thus functional groups and of the role of metal substrate beneath graphene.

Development and Analysis of Graphene-Sheet-Based GaAs Schottky Solar Cell for Enriched Efficiency.

Comparative studies of the 2D numerical modelling and simulation of graphene-based gallium arsenide and silicon Schottky junction solar cell are studied using TCAD tools. The performance of photovoltaic cells was examined while taking parameters, such as substrate thickness, relationship between transmittance and work function of graphene, and n-type doing concentration of substrate semiconduction. The area with the highest efficiency for photogenerated carriers was found to be located near the interface region under light illumination. The significant enhancement of power conversion efficiency was shown in the cell with a thicker carrier absorption Si substrate layer, larger graphene work function, and average doping in a silicon substrate. Thus, for improved cell structure, the maximum JSC = 4.7 mA/cm2, VOC = 0.19 V, and fill factor = 59.73% are found under AM1.5G, exhibiting maximum efficiency of 6.5% (1 sun). The EQE of the cell is well above 60%. This work reports the influence of different substrate thickness, work function, and N-type doping on the efficiency and characteristics of graphene-based Schottky solar cells.

Carrier Transport Regulation of Pixel Graphene Transparent Electrodes for Active-Matrix Organic Light-Emitting Diode Display.

Integrating a graphene transparent electrode (TE) matrix with driving circuits is essential for the practical use of graphene in optoelectronics such as active-matrix organic light-emitting diode (OLED) display, however it is disabled by the transport of carriers between graphene pixels after deposition of a semiconductor functional layer caused by the atomic thickness of graphene. Here, the carrier transport regulation of a graphene TE matrix by using an insulating polyethyleneimine (PEIE) layer isreported. The PEIE forms an ultrathin uniform film (≤10nm) to fill the gap of the graphene matrix, blocking horizontal electron transport between graphene pixels. Meanwhile, it can reduce the work function of graphene, improving the vertical electron injection through electron tunneling. This enables the fabrication of inverted OLED pixels with record high current and power efficiencies of 90.7cd A-1 and 89.1lm W-1 , respectively. By integrating these inverted OLED pixels with a carbon nanotube-based thin-film transistor (CNT-TFT)-driven circuit, an inch-size flexible active-matrix OLED display isdemonstrated, in which all OLED pixels are independently controlled by CNT-TFTs. This research paves a way for the application of graphene-like atomically thin TE pixels in flexible optoelectronics such as displays, smart wearables, and free-form surface lighting.

Effective Passivation of Anisotropic 2D GeAs via Graphene Encapsulation for Highly Stable Near-Infrared Photodetectors.

Germanium arsenic (GeAs) as a promising two-dimensional (2D) semiconducting material has attracted extensive attention. The high carrier mobility and tunable bandgap of GeAs offer broad prospects in electronic and optoelectronic device-related applications. The unique intrinsic anisotropy arising from the low-symmetry structure can be applied in the design of new devices. However, the rapid degradation of mechanically exfoliated GeAs in the environment poses a challenge to its practical development in scalable devices. Here, an approach to stabilize the sensitive material without isolation from the ambient environment is reported. The graphene capping layer effectively suppresses environmental degradation, enabling the encapsulated GeAs photodetectors to maintain the key electronic properties for more than 3 months under ambient conditions. In addition, the regulation of the work function of graphene significantly improves the device performance. An improved responsivity of 965.07 A/W is 20 times higher than that of pure GeAs. This work provides opportunities for the practical application of GeAs and other environmentally sensitive 2D materials.

Advances in solar energy harvesting integrated by van der Waals graphene heterojunctions.

Graphene has garnered increasing attention for solar energy harvesting owing to its unique features. However, limitations hinder its widespread adoption in solar energy harvesting, comprising the band gapless in the molecular orbital of graphene lattice, its vulnerability to oxidation in oxidative environments, and specific toxic properties that require careful consideration during development. Beyond current challenges, researchers have explored doping graphene with ionic liquids to raise the lifespan of solar cells (SCs). Additionally, they have paid attention to optimizing graphene/Si Schottky junction or Schottky barrier SCs by enhancing the conductivity and work function of graphene, improving silicon's reflectivity, and addressing passivation issues at the surface/interface of graphene/Si, resulting in significant advancements in their power conversion efficiency. Increasing the functional area of graphene-based SCs and designing efficient grid electrodes are also crucial for enhancing carrier collection efficiency. Flaws and contaminants present at the interface between graphene and silicon pose significant challenges. Despite the progress of graphene/Si-based photovoltaic cells still needs to catch up to the efficiency achieved by commercially available Si p-n junction SCs. The low Schottky barrier height, design-related challenges associated with transfer techniques, and high lateral resistivity of graphene contribute to this performance gap. To maximize the effectiveness and robustness of graphene/Si-based photovoltaic cells, appropriate interlayers have been utilized to tune the interface and modulate graphene's functionality. This mini-review will address ongoing research and development endeavors using van der Waals graphene heterojunctions, aiming to overcome the existing limitations and unlock graphene's full potential in solar energy harvesting and smart storage systems.

Work Function of Layered Graphene Prepared by Chemical Vapor Deposition in High Vacuum

Work Function of Layered Graphene Prepared by Chemical Vapor Deposition in High Vacuum

Molecular Doping of CVD-Graphene Surfaces by Perfluoroalkyl-Substituted Perylene Diimides Derivatives.

Non-covalent π-π and dipolar interactions with small aromatic molecules have been widely demonstrated to be a valid option to tune graphene work functions without adding extrinsic scattering centers for charge carriers. In this work, we investigated the interaction between a CVD-graphene monolayer and a thermally evaporated sub-monolayer and the following few-layer thin films of similar perylene diimide derivatives: PDI8-CN2 and PDIF-CN2. The molecular influence on the graphene work function was estimated by XPS and UPS analysis and by investigating the surface potentials via scanning Kelvin probe force microscopy. The perfluorinated decoration and the steric interaction in the early stages of the film growth determined a positive work function shift as high as 0.7 eV in the case of PDIF-CN2, with respect to the value of 4.41 eV for the intrinsic graphene. Our results unambiguously highlight the absence of valence band shifts in the UPS analysis, indicating the prevalence of dipolar interactions between the graphene surface and the organic species enhanced by the presence of the fluorine-enriched moieties.

First-principles study of adsorption and migration of alkali and alkaline earth metals (Rb, Cs, and Ba) on graphene

The adsorption and migration characteristics of Rb, Cs, and Ba on pristine and defective graphene have been systematically investigated by utilizing the density functional theory (DFT) method, which could help address the challenges of developing novel anode materials of thermionic energy converters (TECs). In this work, we found that the work function of the adsorption system is lower as Cs is adsorbed on graphene compared with Rb and Ba, which indicates that the electron emission capability has been greatly improved. Computational results of defective graphene demonstrate that defect sites act as traps for metals. The diffusion near the Stone-Wales defect and vacancy is severely hindered and the migration barrier on the surface of B/O doped graphene is also slightly increased. Particularly, the work functions of all defective graphenes are significantly increased, which is attributed to the decrease in the probability of electric dipole formation and the increase of the absolute cohesive energy. O-containing defects are ubiquitous in graphene due to their low formation energies, and the lowest work function of defective graphene is 2.74 eV, which is reached after Cs adsorption at 2OC defect sites, whereas this is still expected to have detrimental effects on graphene-based anode materials.

Probing Nanoscale Schottky Barrier Characteristics at WSe2/Graphene Heterostructures via Electrostatic Doping (Adv. Electron. Mater. 9/2022)

Nanoscale Schottky Barrier Characteristics The local Schottky–Mott characteristics determine the quality of electronic interfaces in metal–semiconductor van der Waals heterostructures. In the article number 2200196, Sebastian Wood and co-workers demonstrate how advanced scanning probe microscopy can probe the interface characteristics of monolayer tungsten diselenide on graphene transistors, distinguishing contributions from interface dipoles and graphene work function, and providing evidence for unpinned Fermi levels through electrostatic doping.

Toward Graphene‐Enhanced Spectroelectrochemical Sensors

AbstractSpectroelectrochemical sensors (SPECSs) sensitive to the least amount of sample are crucial for widespread applications, including early‐stage detection of fatal diseases and other biomedical applications. However, despite the major disadvantage of biomolecule instability on noble metal nanoparticle‐assisted surface‐enhanced SPECSs, designing a suitable alternative remains a great challenge. The authors report a proof‐of‐concept graphene‐enhanced spectroelectrochemical sensors (GE‐SPECSs) employing graphene‐enhanced Raman spectroscopy (GERS). Pristine (p‐) and hydrogenated (h‐) single‐layer graphene (SLG) are utilized to study the oxidized and reduced states of a probe molecule, methylene blue (MB). The hole‐doped h‐SLG possesses efficient GERS signals compared with p‐SLG, resulting in a limit of detection (LOD) &lt; 10−7 m. By taking advantage of the tunable work function of graphene, the authors demonstrate that the GERS signal from the probe molecule can be varied and different oxidation states of the molecule can be studied by applying suitable external potentials. The LOD obtained in an aqueous system (≈10−7 m) is comparable with standard surface‐enhanced SPECSs. The authors’ design thus creates a novel pathway for developing highly efficient, biofriendly, and cost‐effective SPECSs.

The Graphene Structure's Effects on the Current-Voltage and Photovoltaic Characteristics of Directly Synthesized Graphene/n-Si(100) Diodes.

Graphene was synthesized directly on Si(100) substrates by microwave plasma-enhanced chemical vapor deposition (MW-PECVD). The effects of the graphene structure on the electrical and photovoltaic properties of graphene/n-Si(100) were studied. The samples were investigated using Raman spectroscopy, atomic force microscopy, and by measuring current–voltage (I-V) graphs. The temperature of the hydrogen plasma annealing prior to graphene synthesis was an essential parameter regarding the graphene/Si contact I-V characteristics and photovoltaic parameters. Graphene n-type self-doping was found to occur due to the native SiO2 interlayer at the graphene/Si junction. It was the prevalent cause of the significant decrease in the reverse current and short-circuit current. No photovoltaic effect dependence on the graphene roughness and work function could be observed.

Variations in the Effective Work Function of Graphene in a Sliding Electrical Contact Interface under Ambient Conditions.

Control of work function (WF) in graphene is crucial for graphene application in electrode material replacement and electrode surface protection in optoelectronic devices. Although efforts have been made to manipulate the effective WF of graphene to optimize its application, most studies have focused on graphene employed in static electrical contact interfaces. In this work, we investigated WF variations of supported single-layer graphene (SLG) in sliding electrical contact under ambient conditions, which was achieved by sliding an electrically biased conductive atomic force microscopy (cAFM) probe on the SLG surface. The effective WF, structural properties, and chemical compositions of rubbed SLG were subsequently measured by Kelvin probe force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, respectively. We found that the effective WF of the rubbed SLG was governed by both the tunneling triboelectric effect (TTE) and tribochemical-induced surface functionalization. The TTE charges generated by the sliding cAFM probe tunneled through the structural defects of the SLG and were trapped underneath the SLG. The SLG will be either p-doped or n-doped depending on the type of TTE charges and the polarity of electric bias applied to the cAFM probe during the rubbing process. However, the applied electric bias also led to the electrolysis of a water meniscus formed at the cAFM probe-SLG contact, resulting in surface oxidation and the increase of SLG WF. Further absorption of ambient water molecules on the oxygenated functional groups gradually reduced the SLG WF. The influence of TTE and surface functionalization on the SLG WF depends on the magnitude and polarity of applied electric biases, relative humidity, and physical properties of the supporting substrates. Our results demonstrate that the effective WF of SLG in a sliding electrical contact interface will vary with time and might need to be considered for related applications.