Exchange Bias Effect in Ferro-/Antiferromagnetic van der Waals Heterostructures.

The recent discovery of magnetic van der Waals (vdW) materials provides a platform to answer fundamental questions on the two-dimensional (2D) limit of magnetic phenomena and applications. An important question in magnetism is the ultimate limit of the antiferromagnetic layer thickness in ferromagnetic (FM)/antiferromagnetic (AFM) heterostructures to observe the exchange bias (EB) effect, of which origin has been subject to a long-standing debate. Here, we report that the EB effect is maintained down to the atomic bilayer of AFM in the FM (Fe3GeTe2)/AFM (CrPS4) vdW heterostructure, but it vanishes at the single-layer limit. Given that CrPS4 is of A-type AFM and, thus, the bilayer is the smallest unit to form an AFM, this result clearly demonstrates the 2D limit of EB; only one unit of AFM ordering is sufficient for a finite EB effect. Moreover, the semiconducting property of AFM CrPS4 allows us to electrically control the exchange bias, providing an energy-efficient knob for spintronic devices.

Bionanoelectronic platform with a lipid bilayer/CVD-grown MoS2 hybrid.

We demonstrate a bionanoelectronic platform for a supported lipid bilayer formed on an MoS2 film for biosensing, biomolecule recognition, and bioelectronic applications. A large-area MoS2 film was synthesized on a sapphire substrate and treated with O2 plasma or Al2O3 deposition to change the surface from hydrophobic to hydrophilic. Measurements of fluorescence and fluorescence recovery after photobleaching confirmed the physical properties of the lipid bilayer on the treated surfaces. We fabricated an electronic device using the treated MoS2 film and characterized the influence of the lipid bilayer on its electrical properties. Furthermore, transmembrane ion channels peptide (gramicidin A) were incorporated into the lipid bilayer and modulations of the electrical properties of the device under various pH conditions and calcium ion were observed. This sensitive and stable platform has strong potential for housing artificial channels and transmembrane ion channels for advanced bioapplications.

Selectively Metallized 2D Materials for Simple Logic Devices.

We herein demonstrate, for the first time, transparent, flexible, and large-area monolithic MoS2 transistors and logic gates. Each single transistor consists of only two components: a monolithic chemical vapor deposition-grown MoS2 and an ion gel. Additional electrode materials are not required. The uniqueness of the device configuration is attributed to two factors. One is that a MoS2 layer is a semiconductor, but it can be doped degenerately; monolithic MoS2 can thus serve as both the electrodes and the channel of a transistor via selective doping of the material at certain positions. The other is the use of an electrolyte gate dielectric that permits effective gating (<3 V) even from an electrode coplanar with the channel. The resulting monolithic MoS2 transistors yield excellent device performance, including a maximum mobility of 1.5 cm2/V s, an on-off ratio of 105, and a turn-on voltage of -0.69 V. This unique transistor architecture was successfully applied to various semiconductors such as ReS2 and indium-gallium-zinc oxide. Furthermore, the presented devices exhibit excellent mechanical, operational, and environmental stabilities. Fabrication of complex logic circuits (NOT, NAND, and NOR gates) by integration of the monolithic MoS2 transistors is demonstrated. Finally, the monolithic MoS2 transistor was connected to drive red, green, and blue light-emitting diode pixels, which yielded high luminance at a low voltage (<3 V). We believe that the unique architecture of the devices provides a facile way for low-cost, flexible, and high-performance two-dimensional electronics.

Wafer-Scale Substitutional Doping of Monolayer MoS2 Films for High-Performance Optoelectronic Devices.

The substitutional doping method is ideally suited to generating doped two-dimensional (2D) materials for practical device applications as it does not damage or destabilize such materials. However, recently reported substitutional doping techniques for 2D materials have given rise to discontinuities and low uniformities, which hamper the extension of such techniques to large-scale production. In the current work, we demonstrated uniform substitutional doping of monolayer MoS2 in a 2 in. wafer of area >13 cm2. The devices based on doped MoS2 showed extremely high uniformity and stability in electrical properties in ambient conditions for 30 days. The photodetectors based on the doped MoS2 samples showed an ultrahigh photoresponsivity of 5 × 105 A/W, a detectivity of 5 × 1012 Jones, and a fast response rate of 5 ms than did those based on undoped MoS2. This work showed the feasibility of real-life applications based on functionalized 2D semiconductors for next-generation electronic and optoelectronic devices.

Multifunctional van der Waals Broken-Gap Heterojunction.

The finite energy band-offset that appears between band structures of employed materials in a broken-gap heterojunction exhibits several interesting phenomena. Here, by employing a black phosphorus (BP)/rhenium disulfide (ReS2 ) heterojunction, the tunability of the BP work function (Φ BP ) with variation in flake thickness is exploited in order to demonstrate that a BP-based broken-gap heterojunction can manifest diverse current-transport characteristics such as gate tunable rectifying p-n junction diodes, Esaki diodes, backward-rectifying diodes, and nonrectifying devices as a consequence of diverse band-bending at the heterojunction. Diversity in band-bending near heterojunction is attributed to change in the Fermi level difference (Δ) between BP and ReS2 sides as a consequence of Φ BP modulation. No change in the current transport characteristics in several devices with fixed Δ also provides further evidence that current-transport is substantially impacted by band-bending at the heterojunction. Optoelectronic experiments on the Esaki diode and the p-n junction diode provide experimental evidence of band-bending diversity. Additionally, the p+ -n-p junction comprising BP (38 nm)/ReS2 /BP(5.8 nm) demonstrates multifunctionality of binary and ternary inverters as well as exhibiting the behavior of a bipolar junction transistor with common-emitter current gain up to 50.

Van der Waals Broken-Gap p-n Heterojunction Tunnel Diode Based on Black Phosphorus and Rhenium Disulfide.

The broken-gap (type III) van der Waals heterojunction is of particular interest, as there is no overlap between energy bands of its two stacked materials. Despite several studies on straddling-gap (type I) and staggered-gap (type II) vdW heterojunctions, comprehensive understanding of current transport and optoelectronic effects in a type-III heterojunction remains elusive. Here, we report gate-tunable current rectifying characteristics in a black phosphorus (BP)/rhenium disulfide (ReS2) type-III p-n heterojunction diode. Current transport in this heterojunction was modeled using the Simmons approximation through direct tunneling and Fowler-Nordheim tunneling in lower- and higher-bias regimes, respectively. We showed that a p-n diode based on a type-III heterojunction is mainly governed by tunneling-mediated transport, but that transport in a type-I p-n heterojunction is dominated by majority carrier diffusion in the higher-bias regime. Upon illumination with a 532 nm wavelength laser, the BP/ReS2 type-III p-n heterojunction showed a photo responsivity of 8 mA/W at a laser power as high as 100 µW and photovoltaic energy conversion with an external peak quantum efficiency of 0.3%. Finally, we demonstrated a binary inverter consisting of BP p-channel and ReS2 n-channel thin film transistors for logic applications.

Ultrahigh Photoresponsive Device Based on ReS2 /Graphene Heterostructure.

Heterostructures that combine graphene and transition metal dichalcogenides, such as MoS2 , MoTe2 , and WS2 , have attracted attention due to their high performances in optoelectronic devices compared to homogeneous systems. Here, a photodevice based on a hybrid van der Waals heterostructure of rhenium disulfide (ReS2 ) and graphene is fabricated using the stacking method. The device presents a remarkable ultrahigh photoresponsivity of 7 × 105 A W-1 and a detectivity of 1.9 × 1013 Jones, along with a fast response time of less than 30 ms. Tremendous photocurrents are generated in the heterostructure due to the direct bandgap, high quantum efficiency, and strong light absorption by the multilayer ReS2 and the high carrier mobility of graphene. The ReS2 /graphene heterostructured device displays a high photocurrent under the applied gate voltages due to the photogating effect induced by the junction between graphene and ReS2 . The ReS2 /graphene heterostructure may find promising applications in future optoelectronic devices, providing a high sensitivity, flexibility, and transparency.

Structural and Optical Properties of Single- and Few-Layer Magnetic Semiconductor CrPS4.

Atomically thin binary two-dimensional (2D) semiconductors exhibit diverse physical properties depending on their composition, structure, and thickness. By adding another element in these materials, which will lead to formation of ternary 2D materials, the property and structure would greatly change and significantly expanded applications could be explored. In this work, we report structural and optical properties of atomically thin chromium thiophosphate (CrPS4), a ternary antiferromagnetic semiconductor. Its structural details were revealed by X-ray and electron diffraction. Transmission electron microscopy showed that preferentially cleaved edges are parallel to diagonal Cr atom rows, which readily identified their crystallographic orientations. Strong in-plane optical anisotropy induced birefringence that also enabled efficient determination of crystallographic orientation using polarized microscopy. The lattice vibrations were probed by Raman spectroscopy and exhibited significant dependence on thickness of crystals exfoliated down to a single layer. Optical absorption determined by reflectance contrast was dominated by d-d-type transitions localized at Cr3+ ions, which was also responsible for the major photoluminescence peak at 1.31 eV. The spectral features in the absorption and emission spectra exhibited noticeable thickness dependence and hinted at a high photochemical activity for single-layer CrPS4. The current structural and optical investigation will provide a firm basis for future study and application of this kind of atomically thin magnetic semiconductors.

Direct exfoliation and dispersion of two-dimensional materials in pure water via temperature control.

The high-volume synthesis of two-dimensional (2D) materials in the form of platelets is desirable for various applications. While water is considered an ideal dispersion medium, due to its abundance and low cost, the hydrophobicity of platelet surfaces has prohibited its widespread use. Here we exfoliate 2D materials directly in pure water without using any chemicals or surfactants. In order to exfoliate and disperse the materials in water, we elevate the temperature of the sonication bath, and introduce energy via the dissipation of sonic waves. Storage stability greater than one month is achieved through the maintenance of high temperatures, and through atomic and molecular level simulations, we further discover that good solubility in water is maintained due to the presence of platelet surface charges as a result of edge functionalization or intrinsic polarity. Finally, we demonstrate inkjet printing on hard and flexible substrates as a potential application of water-dispersed 2D materials.