Graphene Devices Research Articles

Spatial photoinduced doping of graphene/hBN heterostructures characterized by quantum Hall transport

Abstract Doped semiconductors are a central and crucial component of all integrated circuits. By using a combination of white light and a focused laser beam, and exploiting hexagonal boron nitride (hBN) defect states, heterostructures of hBN/Graphene/hBN are photodoped in-operando, reproducibly and reversibly. We demonstrate device geometries with spatially-defined doping type and magnitude. After each optical doping procedure, magnetotransport measurements including quantum Hall measurements are performed to characterize the device performance. In the unipolar (p+–p–p+ and n–n+–n) configurations, we observe quantization of the longitudinal resistance, proving well-defined doped regions and interfaces that are further analyzed by Landauer–Buttiker modeling. Our unique measurements and modeling of these optically doped devices reveal a complete separation of the p- and n-Landau level edge states. The non-interaction of the edge states results in an observed ‘insulating’ state in devices with a bi-polar p–n–p configuration that is uncommon and has not been measured previously in graphene devices. This insulating state could be utilized in high-performance graphene electrical switches. These quantitative magnetotransport measurements confirm that these doping techniques can be applied to any two-dimensional materials encapsulated within hBN layers, enabling versatile, rewritable circuit elements for future computing and memory applications.

Understanding disorder in monolayer graphene devices with gate-defined superlattices

Engineering superlattices (SLs)-which are spatially periodic potential landscapes for electrons-is an emerging approach for the realization of exotic properties, including superconductivity and correlated insulators, in two-dimensional materials. While moiré SL engineering has been a popular approach, nanopatterning is an attractive alternative offering control over the pattern and wavelength of the SL. However, the disorder arising in the system due to imperfect nanopatterning is seldom studied. Here, by creating a square lattice of nanoholes in the SiO2dielectric layer using nanolithography, we study the SL potential and the disorder formed in hBN-graphene-hBN heterostructures. Specifically, we observe that while electrical transport shows distinct SL satellite peaks, the disorder of the device is significantly higher than graphene devices without any SL. We use finite-element simulations combined with a resistor network model to calculate the effects of this disorder on the transport properties of graphene. We consider three types of disorder: nanohole size variations, adjacent nanohole mergers, and nanohole vacancies. Comparing our experimental results with the model, we find that the disorder primarily originates from nanohole size variations rather than nanohole mergers in square SLs. We further confirm the validity of our model by comparing the results with quantum transport simulations. Our findings highlight the applicability of our simple framework to predict and engineer disorder in patterned SLs, specifically correlating variations in the resultant SL patterns to the observed disorder. Our combined experimental and theoretical results could serve as a valuable guide for optimizing nanofabrication processes to engineer disorder in nanopatterned SLs.

Highly Selective Ammonia Detection in NiO‐Functionalized Graphene Micropatterns for Beef Quality Monitoring

AbstractGraphene has emerged as one of the most promising materials for next‐generation gas sensor platforms due to its high flexibility, transparency, and hydrophobicity. However, graphene shows inherent low selectivity in gas sensing. This has led to extensive development of noble‐metal decoration on graphene to modulate its surface chemistry for enhanced selectivity. While noble metals such as Pt, Pd, and Au have widely been employed to functionalize graphene surface, non‐noble metal decoration of graphene has remained underexplored. Here, an unprecedented room‐temperature self‐activated graphene gas sensor functionalized by NiO nanoparticles and its application to wearable devices monitoring ammonia gas in daily life are demonstrated. NiO‐functionalized graphene micropatterns show ultra‐high selectivity to ammonia with a low detection limit of 2.547 ppt. Density functional theory (DFT) calculations reveal that the strong attraction between NiO and NH3 induced by charge depletion and the vertex region of NiO accelerate the adsorption of NH3 molecules. Furthermore, a wearable graphene device demonstrates the capability to detect ammonia emissions from beef, triggering an alarm call when a specific threshold is exceeded. This work proposes the functionalization of graphene with transition metal oxides, extending beyond the conventional noble metal decoration, and the potential utilization of the graphene for wearable devices.

Integration of highly sensitive large-area graphene-based biosensors in an automated sensing platform

Graphene-based biosensors, featuring exceptional electronic, mechanical, and surface properties, have emerged as frontrunners in advanced sensing technologies. However, to achieve widespread industrial adoption, advancements in the fabrication and integration of large-area graphene devices are essential. Critical parameters such as enhanced sensitivity, scalable production methods, economic viability, integration capabilities, and consistent uniformity must be meticulously addressed. In this work, we demonstrate that our ultra-clean, chemical wet transfer protocol of large-area graphene enables a scalable, smooth integration of graphene into an established assay platform for transporter protein drug discovery. Furthermore, we demonstrate sensitive detection of electrolytic buffers, varying pH, bovine serum albumin (BSA) and single-stranded DNA (ssDNA) adsorption, using our large-area graphene solution-gated field-effect transistor (SGFET) sensors, thereby proving their robust and reliable performance. The sensors’ biocompatibility and ion sensitivity, down to the picomolar range, substantiate their suitability for the investigation of electroactive transport in ion channels and membrane transporters.

Cavity-enhanced photo-thermoelectric response in graphene under cyclotron resonance

We investigated the photo-thermoelectric response of Landau-quantized graphene in an infrared optical cavity structure. High-quality graphene/h-BN heterostructure was fabricated on a TiO2/Au optical cavity. We observed a large enhancement of the photo-thermoelectric voltage when the energy of the inter-Landau-level optical absorption, so-called cyclotron resonance, was coincident with that of the cavity mode. This is due to cavity-enhanced cyclotron resonance absorption of mid-infrared light. A maximum photovoltage responsivity of ∼107 V/W was obtained at a wavelength of 9.27 μm under a magnetic field as low as ∼1 Tesla. The obtained responsivity was significantly higher than that of conventional graphene devices. Our results provide an efficient photo-thermoelectric conversion scheme that utilizes Landau-quantized graphene and an optical cavity.

Conformity Experiment on Inelastic Scattering Exponent of Electrons in Two Dimensions.

The quantum Hall (QH) effect is one of the most widely studied physical phenomenon in two dimensions. The plateau-plateau transition within this effect can be comprehensively described by the scaling theory, which encompasses three pivotal exponents: the critical exponent κ, the inelastic scattering exponent p, and the universal exponent γ. Prior studies have focused on measuring κ and estimating γ, assuming a constant p value of 2 across magnetic fields. Here, our work marks a significant advancement by measuring all three exponents within a single graphene device and a conventional two-dimensional electron system. This study uniquely determines p at low magnetic fields (weak localization region and well outside the QH regime) and high magnetic fields (in the vicinity of the QH regime). Employing a comprehensive analytical approach that includes weak localization, plateau-plateau transitions, and variable range hopping, we have directly determined κ, p, and γ. Our findings reveal a distinct variation in p, shifting from 1 in the low magnetic field regime to 2 in the QH regime in graphene.

Excimer-ultraviolet-lamp-assisted selective etching of single-layer graphene and its application in edge-contact devices

Since the discovery of graphene and its remarkable properties, researchers have actively explored advanced graphene-patterning technologies. While the etching process is pivotal in shaping graphene channels, existing etching techniques have limitations such as low speed, high cost, residue contamination, and rough edges. Therefore, the development of facile and efficient etching methods is necessary. This study entailed the development of a novel technique for patterning graphene through dry etching, utilizing selective photochemical reactions precisely targeted at single-layer graphene (SLG) surfaces. This process is facilitated by an excimer ultraviolet lamp emitting light at a wavelength of 172 nm. The effectiveness of this technique in selectively removing SLG over large areas, leaving the few-layer graphene intact and clean, was confirmed by various spectroscopic analyses. Furthermore, we explored the application of this technique to device fabrication, revealing its potential to enhance the electrical properties of SLG-based devices. One-dimensional (1D) edge contacts fabricated using this method not only exhibited enhanced electrical transport characteristics compared to two-dimensional contact devices but also demonstrated enhanced efficiency in fabricating conventional 1D-contacted devices. This study addresses the demand for advanced technologies suitable for next-generation graphene devices, providing a promising and versatile graphene-patterning approach with broad applicability and high efficiency.

(Invited) Flow of Charge and Heat in Ultra-Clean Graphene

Over the past two decades our understanding of the charge and heat transport properties of graphene has evolved progressively as the quality of graphene devices improved. In this talk, I shall present some new experimental result on the electrical and thermal transport measurements in graphene devices of unprecedented electrical mobility (> 1 million cm2/V.s). We show that the transport in such graphene devices is limited by intrinsic acoustic phonons and their scattering with electrons, rather than charged impurities – which is the case in conventional disordered graphene devices. This manifests in a rather striking violation of the Wiedemann-Franz law and density-dependent variation of the effective Lorenz number over six orders of magnitude. We find that the transport properties of ultra-clean graphene are quantitatively consistent with that of a hydrodynamic Dirac fluid.

Highly Efficient Laser Bidirectional Graphene Printing: Integration of Synthesis, Transfer and Patterning.

Graphene has tremendous potential in future electronics due to its superior force, electrical, and thermal properties. However, the development of graphene devices is limited by its complex, high-cost, and low-efficiency preparation process. This study proposes a novel laser bidirectional graphene printing (LBGP) process for the large-scale preparation of patterned graphene films. In LBGP, a sandwich sample composed of a thermoplastic elastomer (TPE) substrate, carbon precursor powder, and a glass cover is irradiated by a nanosecond pulsed laser. The laser photothermal effect converts the carbon precursor into graphene, with partial graphene sheets deposited directly on the TPE substrate and the remaining transferred to the glass cover via a laser-induced plasma plume. This method simultaneously prepares two face-to-face graphene films in a single laser irradiation, integrating synthesis, transfer, and patterning. The resulting graphene patterns demonstrate good performance in flexible pressure sensing and Joule heating, showcasing high sensitivity (7.7kPa-1), fast response (37ms), and good cycling stability (2000 cycles) for sensors, and high heating rate (1°Cs-1) and long-term stability (3000s) for heaters. It is believed that the simple, low-cost, and efficient LBGP process can promote the development of graphene electronics and laser manufacturing processes.

Momentum-Space Observation of Optically Excited Nonthermal Electrons in Graphene with Persistent Pseudospin Polarization.

The unique optical properties of graphene, with broadband absorption and ultrafast response, make it a critical component of optoelectronic and spintronic devices. Using time-resolved momentum microscopy with high data rate and high dynamic range, we report momentum-space measurements of electrons promoted to the graphene conduction band with visible light and their subsequent relaxation. We observe a pronounced nonthermal distribution of nascent photoexcited electrons with lattice pseudospin polarization in remarkable agreement with results of simple tight-binding theory. By varying the excitation fluence, we vary the relative importance of electron-electron vs electron-phonon scattering in the relaxation of the initial distribution. Increasing the excitation fluence results in increased noncollinear electron-electron scattering and reduced pseudospin polarization, although up-scattered electrons retain a degree of polarization. These detailed momentum-resolved electron dynamics in graphene demonstrate the capabilities of high-performance time-resolved momentum microscopy in the study of 2D materials and can inform the design of graphene devices.

Strong doping reduction on wafer-scale CVD graphene devices via Al2O3 ALD encapsulation

We present the electrical characterization of wafer-scale graphene devices fabricated with an industrially-relevant, contact-first integration scheme combined with Al2O3 encapsulation via atomic layer deposition. All the devices show a statistically significant reduction in the Dirac point position, Vcnp , from around +47 V to between −5 and 5 V (on 285 nm SiO2), while maintaining the mobility values. The data and methods presented are relevant for further integration of graphene devices, specifically sensors, at the back-end-of-line of a standard CMOS flow.

Study of MoS2 as an Electric Field Sensor and the Role of Layer Thickness on the Sensitivity.

In this study, we investigate the scope of molybdenum disulfide (MoS2) as an electric field sensor. We show that MoS2 sensors can be used to identify the polarity as well as to detect the magnitude of the electric field. The response of the sensor is recorded as the change in the drain current when the electric field is applied. The sensitivity, defined as the percentage change in the drain current, reveals that it has a linear relation with the magnitude of the electric field. Furthermore, the sensitivity is highly dependent on the layer thickness, with the single-layer device being highly sensitive and the sensitivity decreasing with the thickness. We have also compared the electric field sensitivity of MoS2 devices to that of previously studied graphene devices and found the former to be exceptionally sensitive than the latter for a given electric field magnitude.

Room temperature thermal rectification in suspended asymmetric graphene ribbon

Thermal rectifiers are essential in optimizing heat dissipation in solid-state devices to enhance energy efficiency, reliability, and overall performance. In this study, we experimentally investigate the thermal rectification phenomenon in suspended asymmetric graphene ribbons (GRs). The asymmetry within the graphene is introduced by incorporating periodic parallel nanoribbons on one side of the GR while maintaining the other side in a pristine form. Our findings reveal a substantial thermal rectification effect in these asymmetric graphene devices, reaching up to 45% at room temperature and increasing further at lower environmental temperatures. This effect is attributed to a significant thermal conductivity contrast between pristine graphene and nanoribbon graphene within the asymmetric structure. We observe that the incorporation of nanoribbons leads to a notable reduction in thermal conductivity, primarily due to phonon scattering and bottleneck effects near the nanoribbon edges. These findings suggest that graphene structures exhibiting asymmetry, facilitated by parallel nanoribbons, hold promise for effective heat management at the nanoscale level and the development of practical phononic devices.

Ethanol Solvation of Polymer Residues in Graphene Solution-Gated Field Effect Transistors.

The persistence of photoresist residues from microfabrication procedures causes significant obstacles in the technological advancement of graphene-based electronic devices. These residues induce undesired chemical doping effects, diminish carrier mobility, and deteriorate the signal-to-noise ratio, making them critical in certain contexts, including sensing and electrical recording applications. In graphene solution-gated field-effect transistors (gSGFETs), the presence of polymer contaminants makes it difficult to perform precise electrical measurements, introducing response variability and calibration challenges. Given the absence of viable short to midterm alternatives to polymer-intensive microfabrication techniques, a postpatterning treatment involving THF and ethanol solvents was evaluated, with ethanol being the most effective, environmentally sustainable, and safe method for residue removal. Employing a comprehensive analysis with XPS, AFM, and Raman spectroscopy, together with electrical characterization, we investigated the influence of residual polymers on graphene surface properties and transistor functionality. Ethanol treatment exhibited a pronounced enhancement in gSGFET performance, as evidenced by a shift in the charge neutrality point and reduced dispersion. This systematic cleaning methodology holds the potential to improve the reproducibility and precision in the manufacturing of graphene devices. Particularly, by using ethanol for residue removal, we align our methodology with the principles of green chemistry, minimizing environmental impact while advancing diverse graphene technology applications.

Polyacrylonitrile as an Efficient Transfer Medium for Wafer-Scale Transfer of Graphene.

The disparity between growth substrates and application-specific substrates can be mediated by reliable graphene transfer, the lack of which currently strongly hinders the graphene applications. Conventionally, the removal of soft polymers, that support the graphene during the transfer, would contaminate graphene surface, produce cracks, and leave unprotected graphene surface sensitive to airborne contaminations. In this work, it is found that polyacrylonitrile (PAN) can function as polymer medium for transferring wafer-size graphene, and encapsulating layer to deliver high-performance graphene devices. Therefore, PAN, that is compatible with device fabrication, does not need to be removed for subsequent applications. The crack-free transfer of 4 in. graphene onto SiO2/Si wafers, and the wafer-scale fabrication of graphene-based field-effect transistor arrays with no observed clear doping, uniformly high carrier mobility (≈11000 cm2 V-1 s-1), and long-term stability at room temperature, are achieved. This work presents new concept for designing the transfer process of 2D materials, in which multifunctional polymer can be retained, and offers a reliable method for fabricating wafer-scale devices of 2D materials with outstanding performance.

Laser-assisted screen-printing of graphene folded reflectarray antenna for millimeter-wave applications

Antennas operating at high frequency bands are sought after for applications in 5G, satellite, radar, and other communication systems. Graphene, a two-dimensional material known for its exceptional conductivity, mechanical strength, and chemical stability, is anticipated to serve as a viable substitute for copper in antenna applications. However, researches on graphene antennas at millimeter-wave and higher frequencies are mainly limited to theory and simulation, due to the fabrication challenges of achieving high-precision graphene patterns. Herein, we present the design and fabrication of a graphene folded reflectarray antenna (FRA) operating at millimeter-wave. The FRA is fabricated using screen-printing of graphene ink on an RT5880 substrate, followed by laser engraving for precise patterning. The main reflector has 918 patch units, and the polarizing grids have line widths and spacings of 100 μm. Measurements demonstrate that the antenna has a realized peak gain of 21.37 dBi at 37.5 GHz. The radiation patterns show a 3 dB beamwidth of 6° and 4° in the E-plane and H-plane respectively, with cross-polarization more than −18 dB. The laser-assisted screen-printing method provides a feasible strategy for the precision manufacture of graphene communication devices.

Dual-indicators machine learning assisted processing high-quality laser-induced fluorine-doped graphene and its application on droplet velocity monitoring sensor

Laser-induced graphene (LIG) is widely used in electron devices owing to its characteristics of fine patterning and high precision. Doping is a commonly used approach to improve the quality of LIG. Thanks to the excellent superhydrophobicity and high electrical conductivity of laser-induced fluorine-doped graphene (F-LIG), it shows promising potential in developing electrodes for electron devices. However, it remains a major challenge to rapidly search for the optimal laser processing parameter space that can process high-quality F-LIG. In this work, a dual-indicators predictive machine learning (ML) method for optimizing the F-LIG process was proposed, utilizing a Gaussian process regression (GPR) algorithm. The mean square error (MSE) between the actual and predicted values of the data used for the model test was 0.00814, while the mean absolute percentage error (MAPE) was 10.33 %, demonstrating a certain degree of generalization without overfitting. Importantly, the F-LIG processed using parameters predicted by the ML model achieved excellent superhydrophobicity and conductivity simultaneously. Based on this high-quality F-LIG, a self-powered droplet velocity monitoring sensor was developed. This sensor can accurately work after 20,000 cycles, showing excellent stability. The proposed dual-indicator ML model assisted the optimization of the F-LIG process, which will provide a feasible and economical way to process high-quality graphene and related electron devices.

Reliable Lift‐Off Patterning of Graphene Dispersions for Humidity Sensors

AbstractDispersion‐based graphene materials are promising candidates for various sensing applications. They offer the advantage of relatively simple and fast deposition via spin‐coating, Langmuir–Blodgett deposition, or inkjet printing. Film uniformity and reproducibility remain challenging in all of these deposition methods. Here, a scalable structuring method is demonstrated, characterized, and successfully applied for graphene dispersions. The method is based on a standard lift‐off process, is simple to implement, and increases the film uniformity of graphene devices. It is also compatible with standard semiconductor manufacturing methods. Two different graphene dispersions are investigated via Raman spectroscopy and Atomic Force Microscopy and observe no degradation of the material properties by the structuring process. Furthermore, high uniformity of the structured patterns and homogeneous graphene flake distribution is achieved. Electrical characterizations show reproducible sheet resistance values correlating with material quantity and uniformity. Finally, repeatable humidity sensing is demonstrated with van der Pauw devices, with sensing limits of less than 1% relative humidity.

Elastic and inelastic phonon scattering effects on thermal conductance across Au/graphene/Au interface

Heat dissipation from graphene devices is predominantly limited by heat conduction across the metal contacts with complex phonon scattering. In this work, the effects of elastic and inelastic phonon scattering on the interfacial thermal conductance (ITC) across the Au/graphene/Au interface are studied using both atomistic Green's function (AGF) and reverse non-equilibrium molecular dynamics methods. The results show that the contribution of inelastic phonon scattering to the ITC increases with the enhancement of interfacial bonding strength. Moreover, the overlap of the vibrational density of states across the interface shows that the coupling between the Au layer (adjacent to the Au/graphene interface) and graphene's out-of-plane modes plays the dominant role in ITC across the Au/graphene interface. By comparing the transmission functions calculated with AGF and spectral heat current decomposition methods, the inelastic phonon scattering process facilitates phonon transmission in the lower and higher frequency range but hinders phonon transmission in the intermediate frequency range. It is expected that this study can contribute to a better understanding of the thermal conduction mechanism across the metal/graphene interface, providing guidance for thermal management and heat conduction optimization of graphene in microelectronic devices.

Thermoelectric Limitations of Graphene Nanodevices at Ultrahigh Current Densities.

Graphene is atomically thin, possesses excellent thermal conductivity, and is able to withstand high current densities, making it attractive for many nanoscale applications such as field-effect transistors, interconnects, and thermal management layers. Enabling integration of graphene into such devices requires nanostructuring, which can have a drastic impact on the self-heating properties, in particular at high current densities. Here, we use a combination of scanning thermal microscopy, finite element thermal analysis, and operando scanning transmission electron microscopy techniques to observe prototype graphene devices in operation and gain a deeper understanding of the role of geometry and interfaces during high current density operation. We find that Peltier effects significantly influence the operational limit due to local electrical and thermal interfacial effects, causing asymmetric temperature distribution in the device. Thus, our results indicate that a proper understanding and design of graphene devices must include consideration of the surrounding materials, interfaces, and geometry. Leveraging these aspects provides opportunities for engineered extreme operation devices.