Homogeneous platinum diselenide metal/semiconductor coplanar structure fabricated by selective thickness control.

For the realization of two-dimensional material-based high-performance electronic devices, the formation of a stable, high-quality metal-semiconductor contact is a key factor. Platinum diselenide (PtSe2), a group-10 transition metal dichalcogenide, is a promising candidate owing to its unique property of layer-dependent semiconductor-to-semimetal transition. Here, a scalable and controllable method utilizing an inductively coupled plasma treatment is reported for selectively controlling the thickness of PtSe2 flakes. The PtSe2 transforms from a semimetal to a semiconductor when the thickness decreases below 3 nm. A field-effect transistor is fabricated based on the homogeneous platinum diselenide metal/semiconductor coplanar structure (metallic PtSe2 as source/drain electrodes and semiconductor PtSe2 as a channel), which demonstrates a low contact resistance of 362 Ωµm and carrier mobility of 150 cm2 V-1 s-1, outperforming the previously reported PtSe2-based devices.

HfO2/HfS2 hybrid heterostructure fabricated via controllable chemical conversion of two-dimensional HfS2.

While preparing uniform dielectric layers on two-dimensional (2D) materials is a key device architecture requirement to achieve next-generation 2D devices, conventional deposition or transfer approaches have been so far limited by their high cost, fabrication complexity, and especially poor dielectric/2D material interface quality. Here, we demonstrate that HfO2, a high-K dielectric, can be prepared on the top surface of 2D HfS2 through plasma oxidation, which results in a heterostructure composed of a 2D van der Waals semiconductor and its insulating native oxide. A highly uniform dielectric layer with a controlled thickness can be prepared; the possibility of unlimited layer-by-layer oxidation further differentiates our work from previous attempts on other 2D semiconducting materials, which exhibit self-limited oxidation up to only a few layers. High resolution transmission electron microscopy was used to show that the converted HfO2/HfS2 hybrid structure is of high quality with an atomically abrupt, impurity- and defect-free interface. Density functional theory calculations show that the unlimited layer-by-layer oxidation occurs because oxygen atoms can barrierlessly penetrate into the HfS2 surface and the extracted sulfur atoms are absorbed into the oxygen vacancy sites within HfO2 under O-rich conditions. A top-gated field-effect transistor fabricated with the converted HfO2/HfS2 hybrid structure was found to exhibit a low interface trap density Dit of 6 × 1011 cm-2 eV-1 between the HfS2 channel and the converted HfO2 dielectric, and a high on/off current ratio above 107. Our approach provides a low cost, simple, and ultraclean manufacturing technique for integrating 2D material into device applications.

Organic field-effect transistors integrated with Ti2CTx electrodes.

Recently, MXenes, which are two-dimensional early transition metal carbides and carbonitrides, have attracted wide attention because of their unique properties. In this study, the electrode applications of Ti2CTx, a member of the MXene family, in pentacene organic field-effect transistors (OFETs) are assessed. Kelvin probe force microscopy analysis was performed to determine the work function of Ti2CTx, which is estimated to be around 5.1 eV. Devices with Ti2CTx electrodes and pentacene channels were fabricated and their electronic performances were evaluated. The contact resistance between Ti2CTx and pentacene is as low as 3 kΩ cm, superior to those of other reported electrode materials. The temperature-dependent current-voltage transfer characteristics of the devices were used to extract activation energy, estimated to be 0.17 eV. This activation energy value is much lower than those of other electrode materials and demonstrates that Ti2CTx is a promising electrode for high performance OFET applications.

High performance bi-layer atomic switching devices.

Atomic switches, also known as conductive bridging random access memory devices, are resistive-switching devices that utilize the electrochemical reactions within a solid electrolyte between metal electrodes, and are considered essential components of future information storage and logic building blocks. In spite of their advantages as next generation switching components such as high density, large scalability, and low power consumption, the large deviations in their electrical properties and the instability of their switching behaviors hinder their application in information processing systems. Here, we report the fabrication of a uniform, low-power atomic switch with a bi-layer structure consisting of Ta2O5-x as the main switching layer (SL) and a relatively oxygen-deficient TaOx as an oxygen vacancy control layer (VCL). The depth profiles of the filaments in the bi-layer device were obtained by performing conductive atomic force microscopy to assess the improvements in uniformity, reliability, and electrical performance that result from the insertion of the VCL. The coefficient of variation of the high resistance state of the bi-layer device was found to be drastically reduced from 60.92% to 2.77% in the cycle-to-cycle measurements and from 82.73% to 4.85% in the device-to-device measurements when compared with the values obtained for a single-layer device. The bi-layer device also exhibits a forming-free low operation voltage of ∼0.4 V, a high on/off ratio of ∼106, and high reliability with 10 years data retention at 85 °C.

Synthesis and Characterization of Hexagonal Boron Nitride as a Gate Dielectric.

Two different growth modes of large-area hexagonal boron nitride (h-BN) film, a conventional chemical vapor deposition (CVD) growth mode and a high-pressure CVD growth mode, were compared as a function of the precursor partial pressure. Conventional self-limited CVD growth was obtained below a critical partial pressure of the borazine precursor, whereas a thick h-BN layer (thicker than a critical thickness of 10 nm) was grown beyond a critical partial pressure. An interesting coincidence of a critical thickness of 10 nm was identified in both the CVD growth behavior and in the breakdown electric field strength and leakage current mechanism, indicating that the electrical properties of the CVD h-BN film depended significantly on the film growth mode and the resultant film quality.

High-Performance 2D Rhenium Disulfide (ReS2 ) Transistors and Photodetectors by Oxygen Plasma Treatment.

A high-performance ReS2 -based thin-film transistor and photodetector with high on/off-current ratio (10(4) ), high mobility (7.6 cm(2) V(-1) s(-1) ), high photoresponsivity (2.5 × 10(7) A W(-1) ), and fast temporal response (rising and decaying time of 670 ms and 5.6 s, respectively) through O2 plasma treatment is reported.

Correction: Surface group modification and carrier transport properties of layered transition metal carbides (Ti2CT(x), T: -OH, -F and -O).

Correction for 'Surface group modification and carrier transport properties of layered transition metal carbides (Ti2CTx, T: -OH, -F and -O)' by Shen Lai, et al., Nanoscale, 2015, DOI: 10.1039/c5nr06513e.

Surface group modification and carrier transport properties of layered transition metal carbides (Ti2CT(x), T: -OH, -F and -O).

In spite of recent significant research into various two-dimensional (2D) materials after the emergence of graphene, the development of a new 2D material that provides both high mobility and an appropriate energy band gap (which are crucial for various device applications) remains elusive. In this report, we demonstrate that the carrier transport behaviour of 2D Ti2CTx, which belongs to the family of 2D transition metal carbides and nitrides, can be tuned by modifying the surface group Tx (-OH, -F, and -O). Our results show that 2D Ti2C(OH)xFy and Ti2COx films can be obtained via simple chemical treatment, thermal annealing, and mechanical exfoliation processes. For the first time, we study the carrier transport properties of 2D Ti2CTx field effect transistors (FETs), obtaining the high field effect carrier mobilities of 10(4) cm(2) V(-1) s(-1) at room temperature. The temperature dependent resistivity of the Ti2COx film exhibits semiconductor like Arrhenius behaviour at zero gate voltage, from which we estimate the energy gap of 80 meV. One interesting feature of the FETs based on transition metal carbides is that the field effect mobility at room temperature is less sensitive to the measured transport gaps, which may arise from the dominant charge transport of activated carriers over the narrow energy gaps of the transition metal carbides. Our results open up the possibility that new 2D materials with high mobilities and appropriate band gaps can be achieved, and broaden the range of electronic device applications of Ti2CTx films.

Plasma-Treated Thickness-Controlled Two-Dimensional Black Phosphorus and Its Electronic Transport Properties.

We report the preparation of thickness-controlled few-layer black phosphorus (BP) films through the modulated plasma treatment of BP flakes. Not only does the plasma treatment control the thickness of the BP film, it also removes the chemical degradation of the exposed oxidized BP surface, which results in enhanced field-effect transistor (FET) performance. Our fabricated BP FETs were passivated with poly(methyl methacrylate) (PMMA) immediately after the plasma etching process. With these techniques, a high field-effect mobility was achieved, 1150 cm(2)/(V s), with an Ion/Ioff ratio of ∼10(5) at room temperature. Furthermore, a fabricated FET with plasma-treated few-layer BP that was passivated with PMMA was found to retain its I-V characteristics and thus to exhibit excellent environmental stability over several weeks.

Correction: Controllable poly-crystalline bilayered and multilayered graphene film growth by reciprocal chemical vapor deposition.

Correction for 'Controllable poly-crystalline bilayered and multilayered graphene film growth by reciprocal chemical vapor deposition' by Qinke Wu et al., Nanoscale, 2015, 7, 10357-10361.

Controllable poly-crystalline bilayered and multilayered graphene film growth by reciprocal chemical vapor deposition.

We report the selective growth of large-area bilayered graphene film and multilayered graphene film on copper. This growth was achieved by introducing a reciprocal chemical vapor deposition (CVD) process that took advantage of an intermediate h-BN layer as a sacrificial template for graphene growth. A thin h-BN film, initially grown on the copper substrate using CVD methods, was locally etched away during the subsequent graphene growth under residual H2 and CH4 gas flows. Etching of the h-BN layer formed a channel that permitted the growth of additional graphene adlayers below the existing graphene layer. Bilayered graphene typically covers an entire Cu foil with domain sizes of 10-50 µm, whereas multilayered graphene can be epitaxially grown to form islands a few hundreds of microns in size. This new mechanism, in which graphene growth proceeded simultaneously with h-BN etching, suggests a potential approach to control graphene layers for engineering the band structures of large-area graphene for electronic device applications.

In situ synthesis of a large area boron nitride/graphene monolayer/boron nitride film by chemical vapor deposition.

We describe the successful in situ chemical vapor deposition synthesis of a graphene-based heterostructure in which a graphene monolayer is protected by top and bottom boron nitride films. The boron nitride film/graphene monolayer/boron nitride film (BGB) was found to be a mechanically robust and chemically inert heterostructure, from which the deleterious effects of mechanical transfer processes and unwanted chemical doping under air exposure were eliminated. The chemical compositions of each film layer were monitored ex situ using UV-visible absorption spectroscopy and X-ray photoelectron spectroscopy, and the crystalline structures were confirmed using transmission electron microscopy and selected-area electron diffraction measurements. The performance of the devices fabricated using the BGB film was monitored over six months and did not display large changes in the mobility or the Dirac point, unlike the conventional graphene devices prepared on a SiO2 substrate. The in situ-grown BGB film properties suggest a novel approach to the fabrication of commercial-grade graphene-based electronic devices.

Wide-range controllable n-doping of molybdenum disulfide (MoS2) through thermal and optical activation.

Despite growing interest in doping two-dimensional (2D) transition metal dichalcogenides (TMDs) for future layered semiconductor devices, controllability is currently limited to only heavy doping (degenerate regime). This causes 2D materials to act as metallic layers, and an ion implantation technique with precise doping controllability is not available for these materials (e.g., MoS2, MoSe2, WS2, WSe2, graphene). Since adjustment of the electrical and optical properties of 2D materials is possible within a light (nondegenerate) doping regime, a wide-range doping capability including nondegenerate and degenerate regimes is a critical aspect of the design and fabrication of 2D TMD-based electronic and optoelectronic devices. Here, we demonstrate a wide-range controllable n-doping method on a 2D TMD material (exfoliated trilayer and bulk MoS2) with the assistance of a phosphorus silicate glass (PSG) insulating layer, which has the broadest doping range among the results reported to date (between 3.6 × 10(10) and 8.3 × 10(12) cm(-2)) and is also applicable to other 2D semiconductors. This is achieved through (1) a three-step process consisting of, first, dopant out-diffusion between 700 and 900 °C, second, thermal activation at 500 °C, and, third, optical activation above 5 µW steps and (2) weight percentage adjustment of P atoms in PSG (2 and 5 wt %). We anticipate our widely controllable n-doping method to be a starting point for the successful integration of future layered semiconductor devices.

Controllable nondegenerate p-type doping of tungsten diselenide by octadecyltrichlorosilane.

Despite heightened interest in 2D transition-metal dichalcogenide (TMD) doping methods for future layered semiconductor devices, most doping research is currently limited to molybdenum disulfide (MoS2), which is generally used for n-channel 2D transistors. In addition, previously reported TMD doping techniques result in only high-level doping concentrations (degenerate) in which TMD materials behave as near-metallic layers. Here, we demonstrate a controllable nondegenerate p-type doping (p-doping) technique on tungsten diselenide (WSe2) for p-channel 2D transistors by adjusting the concentration of octadecyltrichlorosilane (OTS). This p-doping phenomenon originates from the methyl (-CH3) functional groups in OTS, which exhibit a positive pole and consequently reduce the electron carrier density in WSe2. The controlled p-doping levels are between 2.1 × 10(11) and 5.2 × 10(11) cm(-2) in the nondegenerate regime, where the performance parameters of WSe2-based electronic and optoelectronic devices can be properly designed or optimized (threshold voltage↑, on-/off-currents↑, field-effect mobility↑, photoresponsivity↓, and detectivity↓ as the doping level increases). The p-doping effect provided by OTS is sustained in ambient air for a long time showing small changes in the device performance (18-34% loss of ΔVTH initially achieved by OTS doping for 60 h). Furthermore, performance degradation is almost completely recovered by additional thermal annealing at 120 °C. Through Raman spectroscopy and electrical/optical measurements, we have also confirmed that the OTS doping phenomenon is independent of the thickness of the WSe2 films. We expect that our controllable p-doping method will make it possible to successfully integrate future layered semiconductor devices.

Layer-controlled CVD growth of large-area two-dimensional MoS2 films.

In spite of the recent heightened interest in molybdenum disulfide (MoS2) as a two-dimensional material with substantial bandgaps and reasonably high carrier mobility, a method for the layer-controlled and large-scale synthesis of high quality MoS2 films has not previously been established. Here, we demonstrate that layer-controlled and large-area CVD MoS2 films can be achieved by treating the surfaces of their bottom SiO2 substrates with the oxygen plasma process. Raman mapping, UV-Vis, and PL mapping are performed to show that mono, bi, and trilayer MoS2 films grown on the plasma treated substrates fully cover the centimeter scale substrates with a uniform thickness. Our TEM images also present the single crystalline nature of the monolayer MoS2 film and the formation of the layer-controlled bi- and tri-layer MoS2 films. Back-gated transistors fabricated on these MoS2 films are found to exhibit the high current on/off ratio of ∼10(6) and high mobility values of 3.6 cm(2) V(-1) s(-1) (monolayer), 8.2 cm(2) V(-1) s(-1) (bilayer), and 15.6 cm(2) V(-1) s(-1) (trilayer). Our results are expected to have a significant impact on further studies of the MoS2 growth mechanism as well as on the scaled layer-controlled production of high quality MoS2 films for a wide range of applications.

Harnessing denatured protein for controllable bipolar doping of a monolayer graphene.

In this work, we demonstrated tunable p- and/or n-type doping of chemical vapor deposition-grown graphene with the use of protein bovine serum albumin (BSA) as a dopant. BSA undergoes protonation or deprotonation reaction subject to solution pH, thereby acting as either an electron donor or an electron acceptor on the graphene surface layered with denatured BSA through π-stacking interaction. This direct annealing of graphene with denatured BSA of amphoteric nature rendered facilitated fabrication of a p- and/or n-type graphene transistor by modulating pH-dependent net charges of the single dopant. Following AFM confirmation of the BSA/graphene interface assembly, the carrier transport properties of BSA-doped graphene transistors were assessed by I-V measurement and Raman spectra to show effective charge modulation of the graphene enabled by BSA doping at various pH conditions. The protein-mediated bipolar doping of graphene demonstrated in our work is simple, scalable, and straightforward; the proposed scheme is therefore expected to provide a useful alternative for fabricating graphene transistors of novel properties and promote their implementation in practice.

n- and p-Type doping phenomenon by artificial DNA and M-DNA on two-dimensional transition metal dichalcogenides.

Deoxyribonucleic acid (DNA) and two-dimensional (2D) transition metal dichalcogenide (TMD) nanotechnology holds great potential for the development of extremely small devices with increasingly complex functionality. However, most current research related to DNA is limited to crystal growth and synthesis. In addition, since controllable doping methods like ion implantation can cause fatal crystal damage to 2D TMD materials, it is very hard to achieve a low-level doping concentration (nondegenerate regime) on TMD in the present state of technology. Here, we report a nondegenerate doping phenomenon for TMD materials (MoS2 and WSe2, which represent n- and p-channel materials, respectively) using DNA and slightly modified DNA by metal ions (Zn(2+), Ni(2+), Co(2+), and Cu(2+)), named as M-DNA. This study is an example of interdisciplinary convergence research between DNA nanotechnology and TMD-based 2D device technology. The phosphate backbone (PO4(-)) in DNA attracts and holds hole carriers in the TMD region, n-doping the TMD films. Conversely, M-DNA nanostructures, which are functionalized by intercalating metal ions, have positive dipole moments and consequently reduce the electron carrier density of TMD materials, resulting in p-doping phenomenon. N-doping by DNA occurs at ∼6.4 × 10(10) cm(-2) on MoS2 and ∼7.3 × 10(9) cm(-2) on WSe2, which is uniform across the TMD area. p-Doping which is uniformly achieved by M-DNA occurs between 2.3 × 10(10) and 5.5 × 10(10) cm(-2) on MoS2 and between 2.4 × 10(10) and 5.0 × 10(10) cm(-2) on WSe2. These doping levels are in the nondegenerate regime, allowing for the proper design of performance parameters of TMD-based electronic and optoelectronic devices (VTH, on-/off-currents, field-effect mobility, photoresponsivity, and detectivity). In addition, by controlling the metal ions used, the p-doping level of TMD materials, which also influences their performance parameters, can be controlled. This interdisciplinary convergence research will allow for the successful integration of future layered semiconductor devices requiring extremely small and very complicated structures.

Dye-sensitized MoS2 photodetector with enhanced spectral photoresponse.

We fabricated dye-sensitized MoS2 photodetectors that utilized a single-layer MoS2 treated with rhodamine 6G (R6G) organic dye molecules (with an optical band gap of 2.38 eV or 521 nm). The proposed photodetector showed an enhanced performance with a broad spectral photoresponse and a high photoresponsivity compared with the properties of the pristine MoS2 photodetectors. The R6G dye molecules deposited onto the MoS2 layer increased the photocurrent by an order of magnitude due to charge transfer of the photoexcited electrons from the R6G molecules to the MoS2 layer. Importantly, the photodetection response extended to the infrared (λ < 980 nm, which corresponded to about half the energy band gap of MoS2), thereby distinguishing the device performance from that of a pristine MoS2 device, in which detection was only possible at wavelengths shorter than the band gap of MoS2, i.e., λ < 681 nm. The resulting device exhibited a maximum photoresponsivity of 1.17 AW(­1), a photodetectivity of 1.5 × 10(7) Jones, and a total effective quantum efficiency (EQE) of 280% at 520 nm. The device design described here presents a significant step toward high-performance 2D nanomaterial-based photodetector.

A platform for large-scale graphene electronics--CVD growth of single-layer graphene on CVD-grown hexagonal boron nitride.

Direct chemical vapor deposition (CVD) growth of single-layer graphene on CVD-grown hexagonal boron nitride (h-BN) film can suggest a large-scale and high-quality graphene/h-BN film hybrid structure with a defect-free interface. This sequentially grown graphene/h-BN film shows better electronic properties than that of graphene/SiO2 or graphene transferred on h-BN film, and suggests a new promising template for graphene device fabrication.