Optimizing Ultrathin 2D Transistors for Monolithic 3D Integration: A Study on Directly Grown Nanocrystalline Interconnects and Buried Contacts.

The potential of monolithic 3D integration technology is largely dependent on the enhancement of interconnect characteristics which can lead to thinner stacks, better heat dissipation, and reduced signal delays. Carbon materials such as graphene, characterized by sp2 hybridized carbons, are promising candidates for future interconnects due to their exceptional electrical, thermal conductivity and resistance to electromigration. However, a significant challenge lies in achieving low contact resistance between extremely thin semiconductor channels and graphitic materials. To address this issue, an innovative wafer-scale synthesis approach is proposed that enables low contact resistance between dry-transferred 2D semiconductors and the as-grown nanocrystalline graphitic interconnects. A hybrid graphitic interconnect with metal doping reduces the sheet resistance by 84% compared to an equivalent thickness metal film. Furthermore, the introduction of a buried graphitic contact results in a contact resistance that is 17 times lower than that of bulk metal contacts (>40 nm). Transistors with this optimal structure are used to successfully demonstrate a simple logic function. The thickness of active layer is maintained within sub-7 nm range, encompassing both channels and contacts. The ultrathin transistor and interconnect stack developed here, characterized by a readily etchable interlayer and low parasitic resistance, leads to heterogeneous integration of future 3D integrated circuits (ICs).

Ultraclean Interface of Metal Chalcogenides with Metal through Confined Interfacial Chalcogenization.

Acquisition of defect-free transition metal dichalcogenides (TMDs) channels with clean heterojunctions is a critical issue in the production of TMD-based functional electronic devices. Conventional approaches have transferred TMD onto a target substrate, and then apply the typical device fabrication processes. Unfortunately, those processes cause physical and chemical defects in the TMD channels. Here, a novel synthetic process of TMD thin films, named confined interfacial chalcogenization (CIC) is proposed. In the proposed synthesis, a uniform TMDlayer is created at the Au/transition metal (TM) interface by diffusion of chalcogen through the upper Au layer and the reaction of chalcogen with the underlying TM. CIC allows for ultraclean heterojunctions with the metals, synthesis of various homo- and hetero-structured TMDs, and in situ TMD channel formation in the last stage of device fabrication. The mechanism of TMD growth is revealed by the TM-accelerated chalcogen diffusion, epitaxial growth of TMD on Au(111). We demonstrated a wafer-scale TMD-based vertical memristors which exhibit excellent statistical concordance in device performance enabled by the ultraclean heterojunctions and superior uniformity in thickness. CIC proposed in this study represents a breakthrough in in TMD-based electronic device fabrication and marking a substantial step toward practical next-generation integrated electronics.

Spiral-Driven Vertical Conductivity in Nanocrystalline Graphene.

The structure of graphene grown in chemical vapor deposition (CVD) is sensitive to the growth condition, particularly the substrate. The conventional growth of high-quality graphene via the Cu-catalyzed cracking of hydrocarbon species has been extensively studied; however, the direct growth on noncatalytic substrates, for practical applications of graphene such as current Si technologies, remains unexplored. In this study, nanocrystalline graphene (nc-G) spirals are produced on noncatalytic substrates by inductively coupled plasma CVD. The enhanced out-of-plane electrical conductivity is achieved by a spiral-driven continuous current pathway from bottom to top layer. Furthermore, some neighboring nc-G spirals exhibit a homogeneous electrical conductance, which is not common for stacked graphene structure. Klein-edge structure developed at the edge of nc-Gs, which can easily form covalent bonding, is thought to be responsible for the uniform conductance of nc-G aggregates. These results have important implications for practical applications of graphene with vertical conductivity realized through spiral structure.

Amorphous Carbon Films for Electronic Applications.

While various crystalline carbon allotropes, including graphene, have been actively investigated, amorphous carbon (a-C) thin films have received relatively little attention. The a-C is a disordered form of carbon bonding with a broad range of the CC bond length and bond angle. Although accurate structural analysis and theoretical approaches are still insufficient, reproducible structure-property relationships have been accumulated. As the a-C thin film is now adapted as a hardmask in the semiconductor industry and new properties are reported continuously, expectations are growing that it can be practically used as active materials beyond as a simple sacrificial layer. In this perspective review article, after a brief introduction to the synthesis and properties of the a-C thin films, their potential practical applications are proposed, including hardmasks, extreme ultraviolet (EUV) pellicles, diffusion barriers, deformable electrodes and interconnects, sensors, active layers, electrodes for energy, micro-supercapacitors, batteries, nanogenerators, electromagnetic interference (EMI) shielding, and nanomembranes. The article ends with a discussion on the technological challenges in a-C thin films.

Modulation Doping of Single-Layer Semiconductors for Improved Contact at Metal Interfaces.

Single layers of two-dimensional (2D) materials hold the promise for further miniaturization of semiconductor electronic devices. However, the metal-semiconductor contact resistance limits device performance. To mitigate this problem, we propose modulation doping, specifically a doping layer placed on the opposite side of a metal-semiconductor interface. Using first-principles calculations to obtain the band alignment, we show that the Schottky barrier height and, consequently, the contact resistance at the metal-semiconductor interface can be reduced by modulation doping. We demonstrate the feasibility of this approach for a single-layer tungsten diselenide (WSe2) channel and 2D MXene modulation doping layers, interfaced with several different metal contacts. Our results indicate that the Fermi level of the metal can be shifted across the entire band gap. This approach can be straight-forwardly generalized for other 2D semiconductors and a wide variety of doping layers.

Precise Layer Control and Electronic State Modulation of a Transition Metal Dichalcogenide via Phase-Transition-Induced Growth.

Wafer-scale growth of transition metal dichalcogenides with precise control over the number of layers, and hence the electronic state is an essential technology for expanding the practical application of 2D materials. Herein, a new growth method, phase-transition-induced growth (PTG), is proposed for the precisely controlled growth of molybdenum disulfide (MoS2 ) films consisting of one to eleven layers with spatial uniformity on a 2 in. wafer. In this method, an energetically unstable amorphous MoSx Oy (a-MoSx Oy ) phase is effectively converted to a thermodynamically stable crystalline MoS2 film. The number of MoS2 layers is readily controlled layer-by-layer by controlling the amount of Mo atoms in a-MoSx Oy , which is also applicable for the growth of heteroatom-inserted MoS2 . The electronic states of intrinsic and Nb-inserted MoS2 with one and four layers grown by PTGare are analyzed based on their work functions. The work function of monolayer MoS2 effectively increases with the substitution of Nb for Mo. As the number of layers increases to four, charge screening becomes weaker, dopant ionization becomes easier, and ultimately the work function increases further. Thus, better electronic state modulation is achieved in a thicker layer, and in this respect, PTG has the advantage of enabling precise control over the film thickness.

Triboelectric Series of 2D Layered Materials.

Recently, as applications based on triboelectricity have expanded, understanding the triboelectric charging behavior of various materials has become essential. This study investigates the triboelectric charging behaviors of various 2D layered materials, including MoS2 , MoSe2 , WS2 , WSe2 , graphene, and graphene oxide in a triboelectric series using the concept of a triboelectric nanogenerator, and confirms the position of 2D materials in the triboelectric series. It is also demonstrated that the results are obviously related to the effective work functions. The charging polarity indicates the similar behavior regardless of the synthetic method and film thickness ranging from a few hundred nanometers (for chemically exfoliated and restacked films) to a few nanometers (for chemical vapor deposited films). Further, the triboelectric charging characteristics could be successfully modified via chemical doping. This study provides new insights to utilize 2D materials in triboelectric devices, allowing thin and flexible device fabrication.

Two-Dimensional Materials Inserted at the Metal/Semiconductor Interface: Attractive Candidates for Semiconductor Device Contacts.

Metal-semiconductor junctions are indispensable in semiconductor devices, but they have recently become a major limiting factor precluding device performance improvement. Here, we report the modification of a metal/n-type Si Schottky contact barrier by the introduction of two-dimensional (2D) materials of either graphene or hexagonal boron nitride (h-BN) at the interface. We realized the lowest specific contact resistivities (ρc) of 3.30 nΩ cm2 (lightly doped n-type Si, ∼ 1015/cm3) and 1.47 nΩ cm2 (heavily doped n-type Si, ∼ 1021/cm3) via 2D material insertion are approaching the theoretical limit of 1.3 nΩ cm2. We demonstrated the role of the 2D materials at the interface in achieving a low ρc value by the following mechanisms: (a) 2D materials effectively form dipoles at the metal-2D material (M/2D) interface, thereby reducing the metal work function and changing the pinning point, and (b) the fully metalized M/2D system shifts the pinning point toward the Si conduction band, thus decreasing the Schottky barrier. As a result, the fully metalized M/2D system using atomically thin and well-defined 2D materials shows a significantly reduced ρc. The proposed 2D material insertion technique can be used to obtain extremely low contact resistivities in metal/n-type Si systems and will help to achieve major performance improvements in semiconductor technologies.

Control of Triboelectrification by Engineering Surface Dipole and Surface Electronic State.

Although triboelectrification is a well-known phenomenon, fundamental understanding of its principle on a material surface has not been studied systematically. Here, we demonstrated that the surface potential, especially the surface dipoles and surface electronic states, governed the triboelectrification by controlling the surface with various electron-donating and -withdrawing functional groups. The functional groups critically affected the surface dipoles and surface electronic states followed by controlling the amount of and even the polarity of triboelectric charges. As a result, only one monolayer with a thickness of less than 1 nm significantly changed the conventional triboelectric series. First-principles simulations confirmed the atomistic origins of triboelectric charges and helped elucidate the triboelectrification mechanism. The simulation also revealed for the first time where charges are retained after triboelectrification. This study provides new insights to understand triboelectrification.

Polythiophene nanofibril bundles surface-embedded in elastomer: a route to a highly stretchable active channel layer.

A stretchable polymer channel layer for organic field-effect transistors is obtained by spin-coating a blend solution of polythiophene and rubber polymer. A network of the polythiophene nanofibril bundles surface-embedded in the rubber matrix allows large stretchability of the polythiophene film layer.

Highly stretchable resistive pressure sensors using a conductive elastomeric composite on a micropyramid array.

A stretchable resistive pressure sensor is achieved by coating a compressible substrate with a highly stretchable electrode. The substrate contains an array of microscale pyramidal features, and the electrode comprises a polymer composite. When the pressure-induced geometrical change experienced by the electrode is maximized at 40% elongation, a sensitivity of 10.3 kPa(-1) is achieved.

A flexible bimodal sensor array for simultaneous sensing of pressure and temperature.

Diverse signals generated from the sensing elements embedded in flexible electronic skins (e-skins) are typically interfered by strain energy generated through processes such as touching, bending, stretching or twisting. Herein, we demonstrate a flexible bimodal sensor that can separate a target signal from the signal by mechanical strain through the integration of a multi-stimuli responsive gate dielectric and semiconductor channel into the single field-effect transistor (FET) platform.

Graphene and thin-film semiconductor heterojunction transistors integrated on wafer scale for low-power electronics.

Graphene heterostructures in which graphene is combined with semiconductors or other layered 2D materials are of considerable interest, as a new class of electronic devices has been realized. Here we propose a technology platform based on graphene-thin-film-semiconductor-metal (GSM) junctions, which can be applied to large-scale and power-efficient electronics compatible with a variety of substrates. We demonstrate wafer-scale integration of vertical field-effect transistors (VFETs) based on graphene-In-Ga-Zn-O (IGZO)-metal asymmetric junctions on a transparent 150 × 150 mm(2) glass. In this system, a triangular energy barrier between the graphene and metal is designed by selecting a metal with a proper work function. We obtain a maximum current on/off ratio (Ion/Ioff) up to 10(6) with an average of 3010 over 2000 devices under ambient conditions. For low-power logic applications, an inverter that combines complementary n-type (IGZO) and p-type (Ge) devices is demonstrated to operate at a bias of only 0.5 V.

Graphene nanonet for biological sensing applications.

We report a simple but efficient method to fabricate versatile graphene nanonet (GNN)-devices. In this method, networks of V2O5 nanowires (NWs) were prepared in specific regions of single-layer graphene, and the graphene layer was selectively etched via a reactive ion etching method using the V2O5 NWs as a shadow mask. The process allowed us to prepare large scale patterns of GNN structures which were comprised of continuous networks of graphene nanoribbons (GNRs) with chemical functional groups on their edges. The GNN can be easily functionalized with biomolecules for fluorescent biochip applications. Furthermore, electrical channels based on GNN exhibited a rather high mobility and low noise compared with other network structures based on nanostructures such as carbon nanotubes, which was attributed to the continuous connection of nanoribbons in GNN structures. As a proof of concept, we built DNA sensors based on GNN channels and demonstrated the selective detection of DNA. Since our method allows us to prepare high-performance networks of GNRs over a large surface area, it should open up various practical biosensing applications.

Graphene for true Ohmic contact at metal-semiconductor junctions.

The rectifying Schottky characteristics of the metal-semiconductor junction with high contact resistance have been a serious issue in modern electronic devices. Herein, we demonstrated the conversion of the Schottky nature of the Ni-Si junction, one of the most commonly used metal-semiconductor junctions, into an Ohmic contact with low contact resistance by inserting a single layer of graphene. The contact resistance achieved from the junction incorporating graphene was about 10(-8) ~ 10(-9) Ω cm(2) at a Si doping concentration of 10(17) cm(-3).

Electrical control of kinesin-microtubule motility using a transparent functionalized-graphene substrate.

We report a new strategy to selectively localize and control microtubule translocation via electrical control of microtubules using a microfabricated channel on a functionalized-graphene electrode with high transparency and conductivity. A patterned SU-8 film acts as an insulation layer which shields the electrical field generated by the graphene underneath while the localized electric field on the exposed graphene surface guides the negatively charged microtubules. This is the first report showing that functionalized graphene can support and control microtubule motility.

Graphene barristor, a triode device with a gate-controlled Schottky barrier.

Despite several years of research into graphene electronics, sufficient on/off current ratio I(on)/I(off) in graphene transistors with conventional device structures has been impossible to obtain. We report on a three-terminal active device, a graphene variable-barrier "barristor" (GB), in which the key is an atomically sharp interface between graphene and hydrogenated silicon. Large modulation on the device current (on/off ratio of 10(5)) is achieved by adjusting the gate voltage to control the graphene-silicon Schottky barrier. The absence of Fermi-level pinning at the interface allows the barrier's height to be tuned to 0.2 electron volt by adjusting graphene's work function, which results in large shifts of diode threshold voltages. Fabricating GBs on respective 150-mm wafers and combining complementary p- and n-type GBs, we demonstrate inverter and half-adder logic circuits.

Graphene-polymer hybrid nanostructure-based bioenergy storage device for real-time control of biological motor activity.

We report a graphene-polymer hybrid nanostructure-based bioenergy storage device to turn on and off biomotor activity in real-time. In this strategy, graphene was functionalized with amine groups and utilized as a transparent electrode supporting the motility of biomotors. Conducting polymer patterns doped with adenosine triphosphate (ATP) were fabricated on the graphene and utilized for the fast release of ATP by electrical stimuli through the graphene. The controlled release of biomotor fuel, ATP, allowed us to control the actin filament transportation propelled by the biomotor in real-time. This strategy should enable the integrated nanodevices for the real-time control of biological motors, which can be a significant stepping stone toward hybrid nanomechanical systems based on motor proteins.

Scanning noise microscopy on graphene devices.

We developed a scanning noise microscopy (SNM) method and demonstrated the nanoscale noise analysis of a graphene strip-based device. Here, a Pt tip made a direct contact on the surface of a nanodevice to measure the current noise spectrum through it. Then, the measured noise spectrum was analyzed by an empirical model to extract the noise characteristics only from the device channel. As a proof of concept, we demonstrated the scaling behavior analysis of the noise in graphene strips. Furthermore, we performed the nanoscale noise mapping on a graphene channel, allowing us to study the effect of structural defects on the noise of the graphene channel. The SNM method is a powerful tool for nanoscale noise analysis and should play a significant role in basic research on nanoscale devices.