Imaging the Magnetic Anisotropy in Ultrathin Fe4GeTe2 with a Nitrogen-Vacancy Magnetometer.

Two-dimensional (2D) FenGeTe2, with n = 3, 4, and 5, has been realized in experiments, showing strong magnetic anisotropy with enhanced critical temperature (Tc). The understanding of its magnetic anisotropy is crucial for the exploration of more stable 2D magnets and its spintronic applications. Here, we report a quantitative reconstruction of the magnetization magnitude and its direction in ultrathin Fe4GeTe2 using nitrogen vacancy centers. Through imaging stray magnetic fields, we identified the spin-flop transition at approximately 80 K, resulting in a change of the easy axis from the out-of-plane direction to the in-plane direction. Moreover, by analyzing the thermally activated escape behavior of the magnetization near Tc in terms of the Ginzburg-Landau model, we observed the in-plane magnetic anisotropy effect and the formation capability of magnetic domains at ∼0.4 µm2 µT-1. Our findings contribute to the quantitative understanding of the magnetic anisotropy effect in a vast range of 2D van der Waals magnets.

Reliable wafer-scale integration of two-dimensional materials and metal electrodes with van der Waals contacts.

Since the first report on single-layer MoS2 based transistor, rapid progress has been achieved in two-dimensional (2D) material-based atomically thin electronics, providing an alternative approach to solve the bottleneck in silicon device miniaturization. In this scenario, reliable contact between the metal electrodes and the subnanometer-thick 2D materials becomes crucial in determining the device performance. Here, utilizing the quasi-van der Waals (vdW) epitaxy of metals on fluorophlogopite mica, we demonstrate an all-stacking method for the fabrication of 2D devices with high-quality vdW contacts by mechanically transferring pre-deposited metal electrodes. This technique is applicable for complex device integration with sizes up to the wafer scale and is also capable of tuning the electric characteristics of the interfacial junctions by transferring selective metals. Our results provide an efficient, scalable, and low-cost technique for 2D electronics, allowing high-density device integration as well as a handy tool for fundamental research in vdW materials.

Reversible flexoelectric domain engineering at the nanoscale in van der Waals ferroelectrics.

The universal flexoelectric effect in solids provides a mechanical pathway for controlling electric polarization in ultrathin ferroelectrics, eliminating potential material breakdown from a giant electric field at the nanoscale. One challenge of this approach is arbitrary implementation, which is strongly hindered by one-way switching capability. Here, utilizing the innate flexibility of van der Waals materials, we demonstrate that ferroelectric polarization and domain structures can be mechanically, reversibly, and arbitrarily switched in two-dimensional CuInP2S6 via the nano-tip imprinting technique. The bidirectional flexoelectric control is attributed to the extended tip-induced deformation in two-dimensional systems with innate flexibility at the atomic scale. By employing an elastic substrate, artificial ferroelectric nanodomains with lateral sizes as small as ~80 nm are noninvasively generated in an area of 1 µm2, equal to a density of 31.4 Gbit/in2. Our results highlight the potential applications of van der Waals ferroelectrics in data storage and flexoelectronics.

Synthesis of stable γ-phase MnS1-xSex nanoflakes with inversion symmetry breaking.

Inversion symmetry breaking plays a critical role in the formation of magnetic skyrmions. Therefore, for the application of skyrmion-based devices, it is important to develop novel engineering techniques and explore new non-centrosymmetric lattices. In this paper, we report the rational synthesis of stable γ-phase MnS1-xSex (0 ≤ x ≤ 0.45) nanoflakes with an asymmetric distribution of the elemental content, which persists on inversion symmetry breaking. The temperature dependence of resonant second-harmonic generation characterization reveals that a non-centrosymmetric crystal structure exists in our as-grown γ-phase MnS1-xSex with spatial-inversion symmetry breaking. By tuning the parameters of nucleation temperature and growth time, we produced a detailed growth phase diagram, revealing a controllable as-grown structure evolution from γ-phase wurtzite-type to α-phase rock-salt type structure of MnS1-xSex nanoflakes. Our work provides a new playground to explore novel materials that have broken inversion symmetry.

Large-Scale Domain Engineering in Two-Dimensional Ferroelectric CuInP2S6 via Giant Flexoelectric Effect.

Room-temperature ferroelectricity in two-dimensional (2D) materials is a potential for developing atomic-scale functional devices. However, as a key step for the technology implementations of 2D ferroelectrics in electronics, the controllable generation of uniform domains remains challenging at the current stage because domain engineering through an external electric field at the 2D limit inevitably leads to large leakage currents and material breakdown. Here, we demonstrate a voltage-free method, the flexoelectric effect, to artificially generate large-scale stripe domains in 2D ferroelectric CuInP2S6 with single domain lateral size at the scale of several hundred microns. With giant strain gradients (∼106 m-1), we mechanically switch the out-of-plane polarization in ultrathin CuInP2S6. The flexoelectric control of polarization is understood with a distorted Landau-Ginzburg-Devonshire double well model. Through substrate strain engineering, the stripe domain density is controllable. Our results highlight the potential of developing van der Waals ferroelectrics-based flexible electronics.

Room-Temperature Ferroelectricity in 1T

van der Waals materials possess an innate layer degree of freedom and thus are excellent candidates for exploring emergent two-dimensional ferroelectricity induced by interlayer translation. However, despite being theoretically predicted, experimental realization of this type of ferroelectricity is scarce at the current stage. Here, we demonstrate robust sliding ferroelectricity in semiconducting 1T^{'}-ReS_{2} multilayers via a combined study of theory and experiment. Room-temperature vertical ferroelectricity is observed in two-dimensional 1T^{'}-ReS_{2} with layer number N≥2. The electric polarization stems from the uncompensated charge transfer between layers and can be switched by interlayer sliding. For bilayer 1T^{'}-ReS_{2}, the ferroelectric transition temperature is estimated to be ∼405 K from the second harmonic generation measurements. Our results highlight the importance of interlayer engineering in the realization of atomic-scale ferroelectricity.

Enhanced bulk photovoltaic effect in two-dimensional ferroelectric CuInP2S6.

The photocurrent generation in photovoltaics relies essentially on the interface of p-n junction or Schottky barrier with the photoelectric efficiency constrained by the Shockley-Queisser limit. The recent progress has shown a promising route to surpass this limit via the bulk photovoltaic effect for crystals without inversion symmetry. Here we report the bulk photovoltaic effect in two-dimensional ferroelectric CuInP2S6 with enhanced photocurrent density by two orders of magnitude higher than conventional bulk ferroelectric perovskite oxides. The bulk photovoltaic effect is inherently associated to the room-temperature polar ordering in two-dimensional CuInP2S6. We also demonstrate a crossover from two-dimensional to three-dimensional bulk photovoltaic effect with the observation of a dramatic decrease in photocurrent density when the thickness of the two-dimensional material exceeds the free path length at around 40 nm. This work spotlights the potential application of ultrathin two-dimensional ferroelectric materials for the third-generation photovoltaic cells.

Strain-Induced Bandgap Enhancement of InSe Ultrathin Films with Self-Formed Two-Dimensional Electron Gas.

Atomically thin indium selenide (InSe) is a representative two-dimensional (2D) family that have recently attracted extensive interest for their intriguing emerging physics and potential optoelectronic applications with high-performance. Here, by utilizing molecular beam epitaxy and scanning tunneling microscopy, we report a controlled synthesis of InSe thin films down to the monolayer limit and characterization of their electronic properties at atomic scale. Highly versatile growth conditions are developed to fabricate well crystalline InSe films, with a reversible and controllable phase transformation between InSe and In2Se3. The band gap size of InSe films, as enhanced by quantum confinement, increases with decreasing film thickness. Near various categories of lattice imperfections, the band gap becomes significantly enlarged, resulting in a type-I band alignments for lateral heterojunctions. Such band gap enhancement, as unveiled from our first-principles calculations, is ascribed to the local compressive strain imposed by the lattice imperfections. Moreover, InSe films host highly conductive 2D electron gas, manifesting prominent quasiparticle scattering signatures. The 2D electron gas is self-formed via substrate doping of electrons, which shift the Fermi level above the confinement-quantized conduction band. Our study identifies InSe ultrathin film as an appealing system for both fundamental research and potential applications in nanoelectrics and optoelectronics.

Single-Layer MoS2 Grown on Atomically Flat SrTiO3 Single Crystal for Enhanced Trionic Luminescence.

The elaborate interface interactions can be critical in determining the achievable functionality of a semiconductor heterojunction (SH), particularly when two-dimensional material is enclosed in the system and its thickness is at an atomic extreme. In this work, we have successfully constructed a SH model system composed of typical transition-metal chalcogenide (TMDs) and transition metal oxides (TMO) by directly growing molybdenum sulfide (MoS2) nanosheets on atomically flat strontium titanate (SrTiO3) single crystal substrates through a conventional chemical vapor deposition (CVD) synthetic method. Multiple measurements have demonstrated the uniform monolayer thickness and single crystallinity of the MoS2 nanosheets as well as the atomic flatness of the heterojunction surface, both characterizing an extremely high quality of the interface. Clear evidence have been obtained for the electron transfer from the MoS2 adlayer to the SrTiO3 substrate which varies against the interface conditions. More importantly, the photoluminescence of MoS2 is significantly tailored, which is correlated with both the cleanness of the interface and the crystal orientation of the SrTiO3 substrate. These results not only shed fresh lights on the structure-property relationship of the TMDs/TMO heterostructures but also manifest the importance of the ideal interface structure for a hybridized system.

Nonvolatile Electric Control of Exciton Complexes in Monolayer MoSe2 with Two-Dimensional Ferroelectric CuInP2S6.

Monolayer transition-metal dichalcogenides (TMDs) have provided a platform to investigate the excitonic states at the two-dimensional (2D) limit. The inherent properties of excitons in TMDs, such as the photoluminescence quantum yield, the charge states, and even the binding energy, can be effectively controlled via electrostatic gating, selective carrier doping, or substrate dielectric engineering. Here, aiming for the nonvolatile electrical tunability of excitonic states and thereby the optical property of TMDs, we demonstrate a 2D ferroelectric heterostructure with monolayer MoSe2 and ultrathin CuInP2S6 (CIPS). In the heterostructure, the electric polarization of CIPS results in continuous, global, and large electronic modulation in monolayer MoSe2. With the saturated ferroelectric polarization of CIPS, electron-doped or hole-doped MoSe2 is realized in a single device. The carrier density tunability in the heterostructure is as high as 5 × 1012 cm-2. The nonvolatile behavior of these devices up to 3 months is also characterized. Our results provide a new and practical strategy for low-power consumption and agelong tunable optoelectronic devices.

Possible Topological Hall Effect above Room Temperature in Layered Cr1.2Te2 Ferromagnet.

Topological Hall effect (THE) has been used as a powerful tool to unlock spin chirality in novel magnetic materials. Recent focus has been widely paid to THE and possible chiral spin textures in two-dimensional (2D) layered magnetic materials. However, the room-temperature THE has been barely reported in 2D materials, which hinders its practical applications in 2D spintronics. In this paper, we report a possible THE signal featuring antisymmetric peaks in a wide temperature window up to 320 K in Cr1.2Te2, a new quasi-2D ferromagnetic material. The temperature, thickness, and magnetic field dependences of the THE lead to potential spin chirality origin that is associated with the spin canting under external magnetic fields. Our work holds promise for practical applications in future chiral spin-based vdW spintronic devices.

Bright and Near-Unity Polarized Light Emission Enabled by Highly Luminescent Cu2I2-Dimer Cluster-Based Hybrid Materials.

As one fundamental property of light, polarization has a huge impact in quantum optics and optoelectronics through light-matter interactions. However, the bright and near-unity polarized light emissions in the visible range by solid crystalline materials are scantly realized. Here, we report well-defined quasi two-dimensional (2D) hybrid crystals based on the linear alignment of Cu2I2-dimer/bidentate ligand hybrid clusters for achieving bright and near-unity linearly polarized light emissions. Using first-principle calculations, we demonstrate that the superaligned transition dipole moments are the key for the observed excellent polarized light emissions. To further enhance the photoluminescence (PL) polarization degree, we fabricate Cu2I2-dimer-based hybrid nanobelts, which display high PL quantum yield (up to 64%) and ultrahigh PL polarization degree (∼0.99). Our reported copper iodine cluster-based luminescent hybrid materials for bright and highly polarized light emissions will have great potential for future quantum optics applications.

Mo Doping Assisting the CVD Synthesis of Size-Controlled, Uniformly Distributed Single-Layer MoS2 on Rutile TiO2(110).

Molybdenum disulfide (MoS2) has attracted considerable interest due to its superior electronic and optical properties, which have seen promising applications in optoelectronics and catalysis. Chemical vapor deposition (CVD) has been successfully applied in synthesizing MoS2 on various substrates. However, it remains a great challenge to fabricate high-quality MoS2 sheets with well-controlled micro/nano size and homogeneous distribution over the functional substrates such as active metal oxides. Herein, we have developed a two-step synthetic strategy via depositing MoO3 first followed by subsequent vulcanization, to grow single-layer MoS2 on an atomically flat rutile TiO2(110) (r-TiO2(110)) substrate. This method not only very well controls the size as well as the spatial distribution of MoS2 nanosheets over the TiO2 surface but also averts the formation of contaminative species at the heterojunction while maintaining the atomic structure of the substrate surface. The extensive characterizations reveal that the formation of MoS2 derives from the sulfurization of the singly dispersed Mo6+ and Mo5+ species in the surface/subsurface region instead of the aggregated MoO3 patches on top of the TiO2 surface. Such a mechanism may dictate a general way for synthesizing high-quality transition-metal dichalcogenides (TMDs) over a variety of functional substrates.

Large-Scale Ligand-Free Synthesis of Homogeneous Core-Shell Quantum-Dot-Modified Cs4PbBr6 Microcrystals.

An organic ligand-free solution method is developed for preparing homogeneous core-shell quantum-dot (QD)-modified pure Cs4PbBr6 microcrystals on a large scale (∼12 g) at room temperature. The ligand-free Cs4PbBr6 microcrystals show a high green photoluminescence quantum yield of 76% with 360 nm of excitation light, which is attributed to their unique microarchitecture, with several features including quantum confinement of the outer QDs, stability of the inner Cs4PbBr6 microcrystals, improved light trapping, and interfacial recombination. UV-vis-near-IR and photoluminescence analyses provide valued evidence to support the ligand-free Cs4PbBr6 with synergy between the QDs and microcrystals.

Single-Layered MoS2 Directly Grown on Rutile TiO2(110) for Enhanced Interfacial Charge Transfer.

Interfacial charge transfer is critical for the photocatalytic activities of compositional photocatalysts. In this work, we have developed a strategy of growing single-layer MoS2 sheets on the rutile TiO2(110) single-crystal surface using a chemical vapor deposition method. Both on-site and off-site characterizations confirmed the monolayer thickness and single crystallinity of the MoS2 adlayer as well as the atomic flatness of the composite surface. Without the presence of contamination, the charge flow across the interface of MoS2 and TiO2 is greatly enhanced, which hence favors the charge separation under excitations and boots up the catalytic activity of the composite system. Moreover, we found the luminescing property of MoS2 is significantly tailored upon coupling with the TiO2 surface. Our work has established a method for revealing the interface properties of the transition-metal dichalcogenides and oxide semiconductors at the atomic level.

Effect of layer and stacking sequence in simultaneously grown 2H and 3R WS2 atomic layers.

In two-dimensional layered materials, layer number and stacking order have strong effects on the optical and electronic properties. Tungsten disulfide (WS2) crystal, as one important member among transition metal dichalcogenides, has been usually prepared in a layered 2H prototype structure with space group P63/mmc ([Formula: see text]) in spite of many other expected ones such as 3R. Here, we report simultaneous growth of 2H and 3R stacked multilayer (ML) WS2 crystals in large scale by chemical vapor deposition and effects of layer number and stacking order on optical and electronic properties. As revealed in Raman and photoluminescence (PL) measurements, with an increase in layer number, 2H and 3R stacked ML WS2 crystals show similar variation of PL and Raman peaks in position and intensity. Compared to 2H stacked ML WS2, however, 3R stacked one always exhibits the larger red (blue) shift of Raman [Formula: see text] (A1g) peak and the appearance of PL A, B and I peaks at lower energies. Thereby, PL and Raman features depend on not only layer number but also stacking order. In addition, circularly polarized luminescence from two prototype WS2 crystals under circularly polarized excitation has also been investigated, showing obvious spin or valley polarization of these CVD-grown multilayer WS2 crystals.

Microconcave MAPbBr3 Single Crystal for High-Performance Photodetector.

We present the first report of a new suspension method for obtaining cubic MAPbBr3 single crystal with a concave surface. The cubic MAPbBr3 crystal with microconcavity possesses good crystallinity and carrier lifetime. Excellent photoelectric performance was provided by the concavity-based MAPbBr3 photodetectors because of the good light trapping and shortened carrier pathway. As a result, the concavity-based photodetector exhibits superior responsivity of 62.9 and 5.43 A W-1 and EQE of 1.50 × 104% and 1.30 × 103% under low-power and high-power 520 nm irradiation of 3.67 µW cm-2 and 35.4 mW cm-2 at 3 V, respectively, which are more than 500% higher than those of the plane-based photodetector. In particular, the concavity-based photodetector has an ultrahigh detectivity of 6.5 × 1012 Jones at ultralow power of 3.67 µW cm-2, which is 6.5 times higher than that of the planar device.

Low-Temperature In Situ Amino Functionalization of TiO2 Nanoparticles Sharpens Electron Management Achieving over 21% Efficient Planar Perovskite Solar Cells.

Titanium oxide (TiO2 ) has been commonly used as an electron transport layer (ETL) of regular-structure perovskite solar cells (PSCs), and so far the reported PSC devices with power conversion efficiencies (PCEs) over 21% are mostly based on mesoporous structures containing an indispensable mesoporous TiO2 layer. However, a high temperature annealing (over 450 °C) treatment is mandatory, which is incompatible with low-cost fabrication and flexible devices. Herein, a facile one-step, low-temperature, nonhydrolytic approach to in situ synthesizing amino-functionalized TiO2 nanoparticles (abbreviated as NH2 -TiO2 NPs) is developed by chemical bonding of amino (-NH2 ) groups, via TiN bonds, onto the surface of TiO2 NPs. NH2 -TiO2 NPs are then incorporated as an efficient ETL in n-i-p planar heterojunction (PHJ) PSCs, affording PCE over 21%. Cs0.05 FA0.83 MA0.12 PbI2.55 Br0.45 (abbreviated as CsFAMA) PHJ PSC devices based on NH2 -TiO2 ETL exhibit the best PCE of 21.33%, which is significantly higher than that of the devices based on the pristine TiO2 ETL (19.82%) and is close to the record PCE for devices with similar structures and fabrication procedures. Besides, due to the passivation of the surface trap states of perovskite film, the hysteresis of current-voltage response is significantly suppressed, and the ambient stability of devices is improved upon amino functionalization.

Anchoring Fullerene onto Perovskite Film via Grafting Pyridine toward Enhanced Electron Transport in High-Efficiency Solar Cells.

Fullerene derivatives have been popularly applied as electron transport layers (ETLs) of inverted (p-i-n) planar heterojunction perovskite solar cells (iPSCs) due to their strong electron-accepting abilities, and so far, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has been the most commonly used ETL, which suffers, however, from high cost due to the complicated synthetic route. Herein, novel pyridine-functionalized fullerene derivatives (abbreviated as C60-Py) were synthesized facilely via a one-step 1,3-dipolar cycloaddition reaction and applied as ETLs superior to PCBM in iPSC devices. Three pyridine-functionalized fullerene derivatives with different alkyl groups, including methyl, n-butyl, and n-hexyl, grafted onto the pyrrolidine moiety (abbreviated as C60-MPy, C60-BPy, and C60-HPy, respectively) were synthesized. According to cyclic voltammogram study, the chain length of the N-alkyl group has negligible influence on the molecular energy level of C60-Py. However, the ETL performance of C60-Py is sensitively dependent on the chain length of the N-alkyl group, with C60-BPy exhibiting the highest power conversion efficiency (PCE) of 16.83%, which surpasses that based on PCBM ETL (15.87%). The PCE enhancement of C60-BPy device is attributed to the coordination interactions between the pyridine moiety with the Pb2+ ion of CH3NH3PbI3 perovskite, which anchor C60-BPy onto perovskite film and reinforce the passivation of the trap state within the CH3NH3PbI3 perovskite film and suppress the nonradiative electron-hole recombinations, leading to enhanced electron transport reflected by the increase of short-circuit current density ( Jsc). The ambient stability of C60-HPy-based device is much better than that based on PCBM ETL since its long N-alkyl group can function as a superior encapsulating layer protecting the CH3NH3PbI3 layer from contact with the ambient moisture.

Room-temperature ferroelectricity and a switchable diode effect in two-dimensional α-In2Se3 thin layers.

Nanoscale room-temperature ferroelectricity is ideal for developing advanced non-volatile high-density memories. However, reaching the thin film limit in conventional ferroelectrics is a long-standing challenge due to the presence of the critical thickness effect. van der Waals materials, thanks to their stable layered structure, saturated interfacial bonding and weak interlayer couplings, are promising for exploring ultra-thin two-dimensional (2D) ferroelectrics and device applications. Here, we demonstrate a switchable room-temperature ferroelectric diode built upon a 2D ferroelectric α-In2Se3 layer as thin as 5 nm in the form of a graphene/α-In2Se3 heterojunction. The intrinsic out-of-plane ferroelectricity of the α-In2Se3 thin layers is evidenced by the observation of reversible spontaneous electric polarization with a relatively low coercive electric field of ∼2 × 105 V cm-1 and a typical ferroelectric domain size of around tens µm2. Owing to the out-of-plane ferroelectricity of the α-In2Se3 layer, the Schottky barrier at the graphene/α-In2Se3 interface can be effectively tuned by switching the electric polarization with an applied voltage, leading to a pronounced switchable double diode effect with an on/off ratio of ∼105. Our results offer a new way for developing novel nanoelectronic devices based on 2D ferroelectrics.