Single Crystalline GeSe Van Der Waals Ribbons With Uniform Layer Stacking, High Carrier Mobility, and Adjustable Edge Morphology.

Performance of the group IV monochalcogenide GeSe in solar cells, electronic, and optoelectronic devices is expected to improve when high-quality single crystalline material is used rather than polycrystalline films. Crystalline flakes represent an attractive alternative to bulk single crystals as their synthesis may be developed to be scalable, faster, and with higher overall yield. However, large - and especially large and thin - single crystal flakes are notoriously hard to synthesize. Here it is demonstrated that vapor-liquid-solid growth combined with direct lateral vapor-solid incorporation produces high-quality single crystalline GeSe ribbons with tens of micrometers size and controllable thickness. Electron microscopy shows that the ribbons exhibit perfect equilibrium (AB) van der Waals stacking order without extended defects across the entire thickness, in contrast to the conventional case of substrate-supported flakes where material is added via layer-by-layer nucleation and growth on the basal plane. Electrical measurements show anisotropic transport and a high Hall mobility of 85 cm2 V-1 s-1, on par with the best single crystals to date. Growth from mixed GeSe and SnSe vapors, finally, yields ribbons with unchanged structure and composition but with jagged edges, promising for applications that rely on ample chemically active edge sites, such as catalysis or photocatalysis.

Van der Waals GeSe with Strain- and Gate-Tunable Linear Dichroism for Wearable Electronics.

The direct detection of light polarization poses a crucial challenge in the field of optoelectronics and photonics. Herein, the tunable linear dichroism (LD) in GeSe-based polarized photodetectors is presented through electronic and structural asymmetry modulation, and demonstrate their application prospects in wearable electronics. An improvement in the dichroic ratio up to 34% is achieved under a gate voltage of 20 V, and the improvement reaches 44% by applying a tensile strain along the zigzag direction. Theoretical calculations reveal that the gate regulation of barrier height between GeSe and Au electrodes is responsible for the electrical-tunable LD, while the anisotropic optical absorption in response to strains leads to the strain-tunable LD. Moreover, flexible GeSe transistors are developed for wearable applications including motion sensors and glucose monitors. This study offers viable approaches for modulating the optical anisotropy of low-dimensional materials and emphasizes the versatility of van der Waals materials for practical applications in wearable electronic devices.

Self-Assembly of Mixed-Dimensional GeS1- x Sex (1D Nanowire)-(2D Plate) Van der Waals Heterostructures.

The integration of dissimilar materials into heterostructures is a mainstay of modern materials science and technology. An alternative strategy of joining components with different electronic structure involves mixed-dimensional heterostructures, that is, architectures consisting of elements with different dimensionality, for example, 1D nanowires and 2D plates. Combining the two approaches can result in hybrid architectures in which both the dimensionality and composition vary between the components, potentially offering even larger contrast between their electronic structures. To date, realizing such heteromaterials mixed-dimensional heterostructures has required sequential multi-step growth processes. Here, it is shown that differences in precursor incorporation rates between vapor-liquid-solid growth of 1D nanowires and direct vapor-solid growth of 2D plates attached to the wires can be harnessed to synthesize heteromaterials mixed-dimensional heterostructures in a single-step growth process. Exposure to mixed GeS and GeSe vapors produces GeS1- x Sex van der Waals nanowires whose S:Se ratio is considerably larger than that of attached layered plates. Cathodoluminescence spectroscopy on single heterostructures confirms that the bandgap contrast between the components is determined by both composition and carrier confinement. These results demonstrate an avenue toward complex heteroarchitectures using single-step synthesis processes.

Germanium Diselenide Ribbons with Orthorhombic Crystal Structure.

Many materials are known to exist in several stable polymorphs, but synthesis only provides access to a subset. This situation is exemplified by the dichalcogenide semiconductor GeSe2. Besides the amorphous form, which attracted intense interest, crystalline GeSe2 in the bulk and in nanostructures such as flakes and nanobelts invariably adopts the 2D/layered monoclinic ß-phase. Hence, the properties of other polymorphs such as the orthorhombic 3D GeSe2 phase remain unknown. Here, we report the high-yield synthesis of orthorhombic GeSe2 nanoribbons by GeSe/Se vapor transport over Au catalysts. Access to air-stable monocrystalline, single-phase ribbons enabled investigating the properties of orthorhombic GeSe2 including its characteristic Raman spectrum. Optical absorption on ensembles and cathodoluminescence spectroscopy on individual ribbons show a wide bandgap and intense band-to-band emission in the visible, with a broad sub-bandgap emission tail. Our results establish orthorhombic GeSe2 ribbons as a promising wide-bandgap semiconductor nanostructure for applications in optoelectronics and energy conversion.

Controllable Edge Epitaxy of Helical GeSe/GeS Heterostructures.

Emerging twistronics based on van der Waals (vdWs) materials has attracted great interest in condensed matter physics. Recently, more neoteric three-dimensional (3D) architectures with interlayer twist are realized in germanium sulfide (GeS) crystals. Here, we further demonstrate a convenient way for tailoring the twist rate of helical GeS crystals via tuning of the growth temperature. Under higher growth temperatures, the twist angles between successive nanoplates of the GeS mesowires (MWs) are statistically smaller, which can be understood by the dynamics of the catalyst during the growth. Moreover, we fabricate self-assembled helical heterostructures by introducing germanium selenide (GeSe) onto helical GeS crystals via edge epitaxy. Besides the helical architecture, the moiré superlattices at the twisted interfaces are also inherited. Compared with GeS MWs, helical GeSe/GeS heterostructures exhibit improved electrical conductivity and photoresponse. These results manifest new opportunities in future electronics and optoelectronics by harnessing 3D twistronics based on vdWs materials.

High-Temperature Crystal Structure and Chemical Bonding in Thermoelectric Germanium Selenide (GeSe).

The discovery of the ultra-high thermoelectric figure of merit of 2.6 in SnSe has drawn attention to other lead-free IV-VI orthorhombic semiconductors. GeSe has been predicted to possess thermoelectric performances comparable to SnSe. Here, a complete structural study is reported of GeSe with temperature by means of high-resolution synchrotron powder X-ray diffraction. In the orthorhombic phase, the evolution of the bond distances with temperature is shown to deviate significantly with respect to SnSe. Analysis of the chemical bonding within the Quantum Theory of Atoms in Molecules shows that GeSe is ionic with van der Waals interlayer interactions. The signature of the N shell lone pair of Ge is also evident from both the electron density Laplacian and the ELF topologies.

In Situ Synthesis of Amorphous GeSe/CNT Composite via Defective-carbon-mediated Chemical Bonding for Ultrastable Na Ion Storage.

Herein, we report the in-situ synthesis of amorphous GeSe/CNT composite via defective-carbon-mediated chemical bonding for ultrastable Na-ion storage. Structural defects in CNTs play a crucial role in the chemical bonding and bonding strength in GeSe/CNTs composites. Specifically, the bonding strength tends to increase with increasing defect concentrations of CNTs. Remarkably, the strong chemical bonding between GeSe and CNTs significantly weakens Ge-Se bonds and promotes amorphization of GeSe, thus facilitating a reversible conversion reaction and enhancing Na-ion diffusion. Consequently, GeSe/CNTs composite exhibits outstanding cyclability of 87.9% even after 1000 cycles at 1 A g-1 and a high-rate capability of 288.3 mA h g-1 at 10 A g-1 . Our work presents a promising approach for the amorphization of electrode materials enabled by the defective-carbon-mediated strong chemical bonding for Li-, Na-, and K-ion batteries.

Large-Area GeSe Realized Using Pulsed Laser Deposition for Ultralow-Noise and Ultrafast Broadband Phototransistors.

Here, we report on the comprehensive growth, characterization, and optoelectronic application of large-area, two-dimensional germanium selenide (GeSe) layers prepared using the pulsed laser deposition (PLD) technique. Back-gated phototransistors based on few-layered 2D GeSe have been fabricated on a SiO2/Si substrate for ultrafast, low noise, and broadband light detection, showing spectral functionalities over a broad wavelength range of 0.4-1.5 µm. The broadband detection capabilities of the device have been attributed to the self-assembled GeOx/GeSe heterostructure and sub-bandgap absorption in GeSe. Besides a high photoresponsivity of 25 AW-1, the GeSe phototransistor displayed a high external quantum efficiency of the order of 6.14 × 103%, a maximum specific detectivity of 4.16 × 1010 Jones, and an ultralow noise equivalent power of 0.09 pW/Hz1/2. The detector has an ultrafast response/recovery time of 3.2/14.9 µs and can show photoresponse up to a high cut-off frequency of 150 kHz. These promising device parameters exhibited by PLD-grown GeSe layers-based detectors make it a favorable choice against present-day mainstream van der Waals semiconductors with limited scalability and optoelectronic compatibility in the visible-to-infrared spectral range.

Lateral Integration of SnS and GeSe van der Waals Semiconductors: Interface Formation, Electronic Structure, and Nanoscale Optoelectronics.

The emergence of atomically thin crystals has allowed extending materials integration to lateral heterostructures where different 2D materials are covalently connected in the plane. The concept of lateral heterostructures can be generalized to thicker layered crystals, provided that a suitably faceted seed crystal presents edges to which a compatible second van der Waals material can be attached layer by layer. Here, we examine the possibility of integrating multilayer crystals of the group IV monochalcogenides SnS and GeSe, which have the same crystal structure, small lattice mismatch, and similar bandgaps. In a two-step growth process, lateral epitaxy of GeSe on the sidewalls of multilayer SnS flakes (obtained by vapor transport of a SnS2 precursor on graphite) yields heterostructures of laterally stitched crystalline GeSe and SnS without any detectable vertical overgrowth of the SnS seeds and with sharp lateral interfaces. Combined cathodoluminescence spectroscopy and ab initio calculations show the effects of small band offsets on carrier transport and radiative recombination near the interface. The results demonstrate the possibility of forming atomically connected lateral interfaces across many van der Waals layers, which is promising for manipulating optoelectronics, photonics, and for managing charge- and thermal transport.

Femtosecond Laser Deposition of Germanium Selenide onto Silicon Platform at Different Substrate Temperatures.

Germanium selenide (GeSe) thin films were fabricated by employing femtosecond pulsed-laser deposition (fs-PLD) on silicon (100) substrates at various substrate temperatures, ranging from 25 °C to 600 °C. The thin films' surface morphology qualities and optical properties were studied by utilising transmission electron microscopy (TEM) and X-ray diffraction (XRD). The X-ray diffraction result signifies that the thin films deposited on the silicon at a substrate temperature below 400 °C were amorphous Ge-Se. In contrast, those grown at 400 °C and above exhibited crystallised peaks of Ge-Se orthorhombic and tetragonal structures. The deposition growth rate of the thin films was also found to decrease substantially with increasing substrate temperature. These results show that the fs-PLD process has great potential for fabricating good quality Ge-Se thin film. This technique could enable the manufacture of modern optoelectronic devices for applications in optical communication, sensing, and ovonic threshold switching for the high-density crossbar memory array.

Large Memory Window of van der Waals Heterostructure Devices Based on MOCVD-Grown 2D Layered Ge4 Se9.

Van der Waals (vdW) heterostructures have drawn much interest over the last decade owing to their absence of dangling bonds and their intriguing low-dimensional properties. The emergence of 2D materials has enabled the achievement of significant progress in both the discovery of physical phenomena and the realization of superior devices. In this work, the group IV metal chalcogenide 2D-layered Ge4 Se9 is introduced as a new selection of insulating vdW material. 2D-layered Ge4 Se9 is synthesized with a rectangular shape using the metalcorganic chemical vapor deposition system using a liquid germanium precursor at 240 °C. By stacking the Ge4 Se9 and MoS2 , vdW heterostructure devices are fabricated with a giant memory window of 129 V by sweeping back gate range of ±80 V. The gate-independent decay time reveals that the large hysteresis is induced by the interfacial charge transfer, which originates from the low band offset. Moreover, repeatable conductance changes are observed over the 2250 pulses with low non-linearity values of 0.26 and 0.95 for potentiation and depression curves, respectively. The energy consumption of the MoS2 /Ge4 Se9 device is about 15 fJ for operating energy and the learning accuracy of image classification reaches 88.3%, which further proves the great potential of artificial synapses.

Stacking Fault Induced Symmetry Breaking in van der Waals Nanowires.

While traditional ferroelectrics are based on polar crystals in bulk or thin film form, two-dimensional and layered materials can support mechanisms for symmetry breaking between centrosymmetric building blocks, e.g., by creating low-symmetry interfaces in van der Waals stacks. Here, we introduce an approach toward symmetry breaking in van der Waals crystals that relies on the spontaneous incorporation of stacking faults in a nonpolar bulk layer sequence. The concept is realized in nanowires consisting of Se-rich group IV monochalcogenide (GeSe1-xSx) alloys, obtained by vapor-liquid-solid growth. The single crystalline wires adopt a layered structure in which the nonpolar A-B bulk stacking along the nanowire axis is interrupted by single-layer stacking faults with local A-A' stacking. Density functional theory explains this behavior by a reduced stacking fault formation energy in GeSe (or Se-rich GeSe1-xSx alloys). Computations demonstrate that, similar to monochalcogenide monolayers, the inserted A-layers should show a spontaneous electric polarization with a switching barrier consistent with a Curie temperature above room temperature. Second-harmonic generation signals are consistent with a variable density of stacking faults along the wires. Our results point to possible routes for designing ferroelectrics via the layer stacking in van der Waals crystals.

1D/2D van der Waals Heterojunctions Composed of Carbon Nanotubes and a GeSe Monolayer.

Based on first-principles calculations, we propose van der Waals (vdW) heterojunctions composed of one-dimensional carbon nanotubes (CNTs) and two-dimensional GeSe. Our calculations show that (n,0)CNT/GeSe (n = 5-11) heterojunctions are stable through weak vdW interactions. Among these heterojunctions, (n,0)CNT/GeSe (n = 5-7) exhibit metallic properties, while (n,0)CNT/GeSe (n = 8-11) have a small bandgap, lower than 0.8 eV. The absorption coefficient of (n,0)CNT/GeSe (n = 8-11) in the ultraviolet and infrared regions is around 105 cm-1. Specifically, we found that (11,0)CNT/GeSe exhibits type-II band alignment and has a high photoelectric conversion efficiency of 17.29%, which suggests prospective applications in photoelectronics.

Liquid-Phase Exfoliated GeSe Nanoflakes for Photoelectrochemical-Type Photodetectors and Photoelectrochemical Water Splitting.

Photoelectrochemical (PEC) systems represent powerful tools to convert electromagnetic radiation into chemical fuels and electricity. In this context, two-dimensional (2D) materials are attracting enormous interest as potential advanced photo(electro)catalysts and, recently, 2D group-IVA metal monochalcogenides have been theoretically predicted to be water splitting photocatalysts. In this work, we use density functional theory calculations to theoretically investigate the photocatalytic activity of single-/few-layer GeSe nanoflakes for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in pH conditions ranging from 0 to 14. Our simulations show that GeSe nanoflakes with different thickness can be mixed in the form of nanoporous films to act as nanoscale tandem systems, in which the flakes, depending on their thickness, can operate as HER- and/or OER photocatalysts. On the basis of theoretical predictions, we report the first experimental characterization of the photo(electro)catalytic activity of single-/few-layer GeSe flakes in different aqueous media, ranging from acidic to alkaline solutions: 0.5 M H2SO4 (pH 0.3), 1 M KCl (pH 6.5), and 1 M KOH (pH 14). The films of the GeSe nanoflakes are fabricated by spray coating GeSe nanoflakes dispersion in 2-propanol obtained through liquid-phase exfoliation of synthesized orthorhombic (Pnma) GeSe bulk crystals. The PEC properties of the GeSe nanoflakes are used to design PEC-type photodetectors, reaching a responsivity of up to 0.32 AW-1 (external quantum efficiency of 86.3%) under 455 nm excitation wavelength in acidic electrolyte. The obtained performances are superior to those of several self-powered and low-voltage solution-processed photodetectors, approaching that of self-powered commercial UV-Vis photodetectors. The obtained results inspire the use of 2D GeSe in proof-of-concept water photoelectrolysis cells.

Atomic Layer Deposition of GexSe1-x Thin Films for Endurable Ovonic Threshold Selectors with a Low Threshold Voltage.

An ovonic threshold switch (OTS) based on amorphous chalcogenide materials possesses several desirable characteristics, including high selectivity and fast switching speed, enabling the fabrication of one selector-one resistor (1S-1R) crossbar array (CBA) for random access memory. Among the several chalcogenide materials, GeSe offers high selectivity and a strong glass-forming ability with environment-friendly, simple binary composition. In this report, the GeSe thin films were deposited via atomic layer deposition (ALD) using Ge(N(Si(CH3)3)2)2 and ((CH3)3Si)2Se for its envisioned application in fabricating three-dimensional vertical-type phase-change memory. Highly conformal GexSe1-x films were obtained at a substrate temperature ranging from 70 to 160 °C. The unique deposition mechanism that involves Ge intermediates provided a way to modulate the composition of the Ge-Se films from 5:5 to 7:3. Low threshold voltages ranging from 1.2 to 1.4 V were observed depending on the composition. A cycling endurance of more than 106 was achieved with the Ge0.6Se0.4 composition with 104 half-bias nonlinearity. This work presents the foundations for the future development of vertical-type 1S-1R arrays when combined with the ALD technique for Ge2Sb2Te5 phase-change materials.

Electroforming-Free Bipolar Resistive Switching in GeSe Thin Films with a Ti-Containing Electrode.

Chalcogenide materials have been regarded as strong candidates for both resistor and selector elements in passive crossbar arrays owing to their dual capabilities of undergoing threshold and resistance switching. This work describes the bipolar resistive switching (BRS) of amorphous GeSe thin films, which used to show Ovonic threshold switching (OTS) behavior. The behavior of this new functionality of the material follows filament-based resistance switching when Ti and TiN are adopted as the top and bottom electrodes, respectively. The detailed analysis revealed that the high chemical affinity of Ti to Se produces a Se-deficient GexSe1-x matrix and the interfacial Ti-Se layer. Electroforming-free BRS behavior with reliable retention and cycling endurance was achieved. The performance improvement was attributed to the Ti-Se interfacial layer, which stabilizes the composition of GeSe during the electrical switching cycles by preventing further massive Se migration to the top electrode. The conduction mechanism analysis denotes that the resistance switching originates from the formation and rupture of the high-conductance semiconducting Ge-rich GexSe1-x filament. The high-resistance state follows the modified Poole-Frenkel conduction.