Low-dimensional materials hold great promises for exploring emergent physical phenomena, nanoelectronics, and quantum technologies. Their synthesis often depends on catalytic metal films, from which the synthesized materials must be transferred to insulating substrates to enable device functionality and minimize interfacial interactions during quantum investigations. Conventional transfer methods, such as chemical etching or electrochemical delamination, degrade material quality, limit scalability, or prove incompatible with complex device architectures. Here, a scalable, etch-free transfer technique is presented, employing Field's metal (51% In, 32.5% Bi, and 16.5% Sn by weight) as a low-melting-point mechanical support to gently delaminate low-dimensional materials from metal films without causing damage. Anchoring the metal film during separation prevents tearing and preserves material integrity. As a proof of concept, atomically precise graphene nanoribbons (GNRs) are transferred from Au(111)/mica to dielectric substrates, including silicon dioxide (SiO_2) and single-crystalline lanthanum oxychloride (LaOCl). Comprehensive characterization confirms the preservation of structural and chemical integrity throughout the transfer process. Wafer-scale compatibility and device integration are demonstrated by fabricating GNR-based field-effect transistors (GNRFETs) that exhibit room-temperature switching with on/off current ratios exceeding 10^3. This method provides a scalable and versatile platform for integrating low-dimensional materials into advanced low-dimensional materials-based technologies.
Materials and devices used in space and advanced energy systems are continuously exposed to high-energy photons and particles, leading to gradual changes in their structural and electronic properties. Gamma-ray exposure is particularly critical because their strong penetrating power allows them to traverse conventional shielding and device packaging. Real-time monitoring of exposure-induced changes in compact, chip-integrated devices remain limited despite the availability of external radiation detectors. Atomically precise graphene nanoribbons (GNRs) present an attractive platform for probing such effects due to their structural uniformity, tunable electronic properties, and exceptional sensitivity of charge transport to even subtle lattice modifications, a capability not yet demonstrated in other low-dimensional materials. Here, we investigate the structural and electronic response of atomically precise GNRs to gamma irradiation. Nine-atom-wide armchair GNRs (9-AGNRs) were synthesized via a bottom-up on-surface approach, integrated into field-effect transistors (FETs), and characterized before and after exposure using Raman spectroscopy and electrical transport measurements. Raman spectroscopy indicates preservation of the primary GNR lattice structure, accompanied by subtle spectral changes suggestive of irradiation-induced oxidation or local lattice perturbations. While these measurements do not indicate severe structural damage, electrical transport measurements reveal a pronounced degradation in device performance, demonstrating the strong susceptibility of GNR FETs to gamma irradiation. This pronounced response may be attributed to Anderson localization of charge carriers, potentially arising from enhanced quantum interference in atomically narrow, quasi-one-dimensional (1D) GNRs. These results suggest the potential of GNR-based nanoelectronic devices for sensing and monitoring under extreme operational conditions.
ChalcopyriteChalcopyrite (CuFeS2) is a common copper oreCopper ore mineral that displays variable but often poor leachingLeaching behavior under typical heap leachHeap leach conditions. Ongoing research has provided inconsistent magnitudes of activation energy and dissolutionDissolution mechanisms, even for chalcopyriteChalcopyrite leached in the same chemical systems. This is possibly due to variations in crystallography, impuritiesImpurity such as Zn, Ag, Co, and Se, which natural chalcopyriteChalcopyrite readily accommodates, or interference from additional sulfidesSulfide, like cubanite, haycockite, mooihoekite, putoranite, or talnakhite, which have similar crystallographic signatures and optical properties. Additional contributors to these observations are unconstrained variations in chalcopyriteChalcopyrite semiconducting properties, such as charge carrier type, density, and resistivityResistivity. Little is known about these in natural chalcopyritesChalcopyrite. Currently, most natural chalcopyritesChalcopyrite are considered n-type semiconductorsSemiconductors, while an estimated 3–5
We investigated the formation of Schottky barriers at the interface between rare-earth tritelluride (RTe3) crystals and n-type silicon (n-Si) substrates. This study explores the rectifying characteristics of RTe3/n-Si junctions (R = Dy, Ho, Er) and their relation to the charge density wave (CDW) transition. Using the thermionic emission model, we analyzed current–voltage (I–V) measurements to obtain the Schottky barrier height (ϕSBH) and the ideality factor (η). The temperature dependence of the extracted ϕSBH and η reveals kink features near the CDW transition temperature. The Schottky–Mott model is employed to explain these kink features in the derivatives of ϕSBH and 1/η and attributes them to changes in the work function of RTe3 during the CDW transition. Our findings suggest that Schottky junctions can be utilized to probe the electronic states of RTe3, enabling potential RTe3 device applications in electronics and optoelectronics.
Nitrogen core-doping of graphene nanoribbons (GNRs) allows trigonal planar carbon atoms along the backbone of GNRs to be substituted by higher-valency nitrogen atoms. The excess valence electrons are injected into the π-orbital system of the GNR, thereby changing not only its electronic occupation but also its topological properties. We have observed this topological change by synthesizing dilute nitrogen core-doped armchair GNRs with a width of five atoms (N2-5-AGNRs). The incorporation of pairs of trigonal planar nitrogen atoms results in the emergence of topological boundary states at the interface between doped and undoped segments of the GNR. These topological boundary states are offset in energy by approximately ΔE = 300 meV relative to the topological end states at the termini of finite 5-AGNRs. Scanning tunneling microscopy (STM) and spectroscopy (STS) reveal that for finite GNRs the two types of topological states can interact through a linear combination of orbitals, resulting in a pair of asymmetric hybridized states. This behavior is captured by an effective Hamiltonian of nondegenerate diatomic molecules, where the analogous interatomic hybridization interaction strength is tuned by the distance between GNR topological modes.
Atomically precise graphene nanoribbons (GNRs) synthesized from the bottom-up exhibit promising electronic properties for high-performance field-effect transistors (FETs). The feasibility of fabricating FETs with GNRs (GNRFETs) has been demonstrated, with ongoing efforts aimed at further improving their performance. However, their long-term stability and reliability remain unexplored, which is as important as their performance for practical applications. In this work, we fabricated short-channel FETs with nine-atom-wide armchair GNRs (9-AGNRFETs). We revealed that the on-state (I-ON) current performance of the 9-AGNRFETs deteriorates significantly over consecutive full transistor on and off logic cycles, which has neither been demonstrated nor previously considered. To address this issue, we deposited a thin similar to 10 nm thick atomic layer deposition (ALD) layer of aluminum oxide (Al2O3) directly on these devices. The integrity, compatibility, electrical performance, stability, and reliability, of the GNRFETs before and/or after Al2O3 deposition were comprehensively studied. The results indicate that the observed decline in electrical device performance is most likely due to the degradation of contact resistance over multiple measurement cycles. We successfully demonstrated that the devices with the Al2O3 layer operate well up to several thousand continuous full cycles without any degradation. Our study offers valuable insights into the stability and reliability of GNR transistors, which could facilitate their large-scale integration into practical applications.
Graphene nanoribbons (GNRs), when synthesized with atomic precision by bottom–up chemical approaches, possess tunable electronic structure, and high theoretical mobility, conductivity, and heat dissipation capabilities, which makes them an excellent candidate for channel material in post-silicon transistors. Despite their immense potential, achieving highly transparent contacts for efficient charge transport—which requires proper contact selection and a deep understanding of the complex one-dimensional GNR channel-three-dimensional metal contact interface—remains a challenge. In this study, we investigated the impact of different electron-beam deposited contact metals—the commonly used palladium (Pd) and softer metal indium (In)—on the structural properties and field-effect transistor performance of semiconducting nine-atom wide armchair GNRs. The performance and integrity of the GNR channel material were studied by means of a comprehensive Raman spectroscopy analysis, scanning tunneling microscopy (STM) imaging, optical absorption calculations, and transport measurements. We found that, compared to Pd, In contacts facilitate favorable Ohmic-like transport because of the reduction of interface defects, while the edge structure quality of GNR channel plays a more dominant role in determining the overall device performance. Our study provides a blueprint for improving device performance through contact engineering and material quality enhancements in emerging GNR-based technology.
Bottom-up assembled nanomaterials and nanostructures allow for the studies of rich and unprecedented quantum-related and mesoscopic transport phenomena. However, it can be difficult to quantify the correlations between the geometrical or structural parameters obtained from advanced microscopy and measured electrical characteristics when they are made into macroscopic devices. Here, we propose a strategy to connect the nanomaterial morphologies and the device performance through a Monte Carlo device model and apply it to understand the scaling trends of bottom-up synthesized armchair graphene nanoribbon (GNR) transistors. A new nanofabrication process is developed for GNR transistors with channel length down to 7 nm. The impacts of the GNR spatial distributions and the device geometries on the device performance are investigated systematically through comparison of experimental data with the model. Through this study, challenges and opportunities of transistor technologies based on bottom-up synthesized GNRs are pinpointed, paving the way to the further improvement of the GNR device performance for future transistor technology nodes.
The electronic, optical, and magnetic properties of graphene nanoribbons (GNRs) can be engineered by controlling their edge structure and width with atomic precision through bottom-up fabrication based on molecular precursors. This approach offers a unique platform for all-carbon electronic devices but requires careful optimization of the growth conditions to match structural requirements for successful device integration, with GNR length being the most critical parameter. In this work, the growth, characterization, and device integration of 5-atom wide armchair GNRs (5-AGNRs) are studied, which are expected to have an optimal bandgap as active material in switching devices. 5-AGNRs are obtained via on-surface synthesis under ultrahigh vacuum conditions from Br- and I-substituted precursors. It is shown that the use of I-substituted precursors and the optimization of the initial precursor coverage quintupled the average 5-AGNR length. This significant length increase allowed the integration of 5-AGNRs into devices and the realization of the first field-effect transistor based on narrow bandgap AGNRs that shows switching behavior at room temperature. The study highlights that the optimized growth protocols can successfully bridge between the sub-nanometer scale, where atomic precision is needed to control the electronic properties, and the scale of tens of nanometers relevant for successful device integration of GNRs.
Bottom-up synthesized graphene nanoribbons (GNRs) exhibit promising electronic properties for post-silicon transistor technologies. However, several challenges remain, such as the synthesis of long length GNRs, their rational placement and alignment on dielectric surface, and achieving low GNR-contacts and uniform high-κ gate dielectrics. This invited talk presents recent progress in integrating GNRs into field-effect transistors (FETs) and discusses the synthesis and integration improvements that may enable the fabrication of GNR devices with the performance needed for the post-silicon era.
The rational bottom-up synthesis of graphene nanoribbons (GNRs) provides atomically precise control of widths and edges that give rise to a wide range of electronic properties promising for electronic devices such as field-effect transistors (FETs). Since the bottom-up synthesis commonly takes place on catalytic metallic surfaces, the integration of GNRs into such devices requires their transfer onto insulating substrates, which remains one of the bottlenecks in the development of GNR-based electronics. Herein, we report on a method for the transfer-free placement of GNRs on insulators. This involves growing GNRs on a gold film deposited onto an insulating layer followed by gentle wet etching of the gold, which leaves the nanoribbons to settle in place on the underlying insulating substrate. Scanning tunneling microscopy and Raman spectroscopy confirm that atomically precise GNRs of high density uniformly grow on the gold films deposited onto SiO2/Si substrates and remain structurally intact after the etching process. We have also demonstrated transfer-free fabrication of ultrashort channel GNR FETs using this process. A very important aspect of the present work is that the method can scale up well to 12 in. wafers, which is extremely difficult for previous techniques. Our work here thus represents an important step toward large-scale integration of GNRs into electronic devices.
Nanoporous graphene (NPG) can exhibit a uniform electronic band gap and rationally‐engineered emergent electronic properties, promising for electronic devices such as field‐effect transistors (FETs), when synthesized with atomic precision. Bottom‐up, on‐surface synthetic approaches developed for graphene nanoribbons (GNRs) now provide the necessary atomic precision in NPG formation to access these desirable properties. However, the potential of bottom‐up synthesized NPG for electronic devices has remained largely unexplored to date. Here, FETs based on bottom‐up synthesized chevron‐type NPG (C‐NPG), consisting of ordered arrays of nanopores defined by laterally connected chevron GNRs, are demonstrated. C‐NPG FETs show excellent switching performance with on–off ratios exceeding 10 4 , which are tightly linked to the structural quality of C‐NPG. The devices operate as p‐type transistors in the air, while n‐type transport is observed when measured under vacuum, which is associated with reversible adsorption of gases or moisture. Theoretical analysis of charge transport in C‐NPG is also performed through electronic structure and transport calculations, which reveal strong conductance anisotropy effects in C‐NPG. The present study provides important insights into the design of high‐performance graphene‐based electronic devices where ballistic conductance and conduction anisotropy are achieved, which could be used in logic applications, and ultra‐sensitive sensors for chemical or biological detection.
The scope of graphene nanoribbon (GNR) structures accessible through bottom-up approaches is defined by the intrinsic limitations of either all-on-surface or all-solution-based synthesis. Here, we report a hybrid bottom-up synthesis of GNRs based on a Matrix-Assisted Direct (MAD) transfer technique that successfully leverages technical advantages inherent to both solution-based and on-surface synthesis while sidestepping their drawbacks. Critical structural parameters tightly controlled in solution-based polymerization reactions can seamlessly be translated into the structure of the corresponding GNRs. The transformative potential of the synergetic bottom-up approaches facilitated by the MAD transfer techniques is highlighted by the synthesis of chevron-type GNRs (cGNRs) featuring narrow length distributions and a nitrogen core-doped armchair GNR (N4-7-ANGR) that remains inaccessible using either a solution-based or an on-surface bottom-up approach alone.
nanoporous graphene with atomically precise pores and consequent uniform band gap. In article number 2103798, Jeffrey Bokor and co-workers use this strategy to turn molecules into nanoporous graphene, which is subsequently transferred to devices and turned into field-effect transistors. The switching performance is high and correlates with the degree of structural perfection. NANOPOROUS GRAPHENE TRANSISTORS
High performance graphene nanoribbon (GNR) transistors require seamless integration of GNRs with high-k dielectrics, which remains unexplored. This work evaluates performance of bottom-up synthesized 9-atom armchair GNRs (9-AGNRs) in short channel back-gate (BG) and double-gate (DG) FETs. Top-gate (TG) dielectric bilayers consisting of 1-1.25 nm Al 2 O 3 and 2.5 nm HfO 2 are deposited on 9-AGNRFETs with a 5.5 nm HfO 2 BG dielectric. Devices exhibit excellent I ON /I OFF up to ~10 5 and I ON up to ~60 µA/µm (~2.4 µA per GNR). DG enables improved subthreshold swing (SS) and low hysteresis owing to its superior electrostatic control. We also identify and quantify through numerical simulations the improvements in materials and process that would enable GNRs with performance close to outstanding theoretically predicted metrics.
Lithium-sulfur (Li-S) is one of the most promising next-generation lithium-ion battery systems due to its high theoretical specific capacity. However, Li-S batteries suffer from a short cycling life, poor mechanical stability and low coulombic efficiency. Developing a robust solid electrolyte interphase (SEI) plays a critical role in alleviating these issues. Current approaches for a robust SEI are mostly based on using additives, which negatively impact the energy density. Herein, newly developed electrochemical conditioning techniques were applied to study their effects on the formation of the SEI in Li-S batteries. The dynamic mechanisms in the battery associated with each conditioning technique were investigated using city and highway models based on real world driving conditions. City and highway models incorporated various electrochemical characterization techniques while introducing varying levels of cycling stress. As an additive free approach, the novel plateau targeted conditioning method improves Li-S SEI formation that increases battery capacity and cycling stability. This work will pave the way for the realization of additive free approaches to improving the performance of Li-S batteries.
Chemical vapor deposition and phase stability of pyrite crystals on SiO2at temperatures up to 600 °C have been studied.
Light-weight graphite foam decorated with carbon nanotubes (dia. 20-50 nm) is utilized as an effective electrode without binders, conductive additives, or metallic current collectors for supercapacitors in aqueous electrolyte. Facile nitric acid treatment renders wide operating potentials, high specific capacitances and energy densities, and long lifespan over 10 000 cycles manifested as 164.5 and 111.8 F g-1 , 22.85 and 12.58 Wh kg-1 , 74.6% and 95.6% capacitance retention for 2 and 1.8 V, respectively. Overcharge protection is demonstrated by repetitive cycling between 2 and 2.5 V for 2000 cycles without catastrophic structural demolition or severe capacity fading. Graphite foam without metallic strut possessing low density (≈0.4-0.45 g cm-3 ) further reduces the total weight of the electrode. The thorough investigation of the specific capacitances and coulombic efficiencies versus potential windows and current densities provides insights into the selection of operation conditions for future practical devices.