Tailoring Stress-Relieved Structure for SnSe Toward High Performance Potassium Ion Batteries.

Metal chalcogenides as an ideal family of anode materials demonstrate a high theoretical specific capacity for potassium ion batteries (PIBs), but the huge volume variance and poor cyclic stability hinder their practical applications. In this study, a design of a stress self-adaptive structure with ultrafine SnSe nanoparticles embedded in carbon nanofiber (SnSe@CNF) via the electrospinning technology is presented. Such an architecture delivers a record high specific capacity (272 mAh g-1 at 50 mA g-1) and high-rate performance (125 mAh g-1 at 1 A g-1) as a PIB anode. It is decoded that the fundamental understanding for this great performance is that the ultrafine SnSe particles enhance the full utilization of the active material and achieve stress relief as the stored strain energy from cycling is insufficient to drive crack propagation and thus alleviates the intrinsic chemo-mechanical degradation of metal chalcogenides.

Solution phase growth and analysis of super-thin zigzag tin selenide nanoribbons.

Tin selenide (SnSe), a highly promising layered material, has been garnering particular interest in recent times due to its significant promise for future energy devices. Herein we report a simple solution-phase approach for growing highly crystalline layered SnSe nanoribbons. Polyvinylpyrrolidone (PVP) was used as a templating agent to selectively passivates the (100) and (001) facets of the SnSe nanoribbons resulting in the unique growth of nanoribbons along theirb-axis with a defined zigzag edge state along the sidewalls. The SnSe nanoribbons are few layers thick (∼20 layers), with mean widths of ∼40 nm, and achievable length of >1µm. Nanoribbons could be produced in relatively high quantities (>150 mg) in a single batch experiment. The PVP coating also offers some resistance to oxidation, with the removal of the PVP seen to lead to the formation of a SnSe/SnOxcore-shell structure. The use of non-toxic PVP to replace toxic amines that are typically employed for other 1D forms of SnSe is a significant advantage for sustainable and environmentally friendly applications. Heat transport properties of the SnSe nanoribbons, derived from power-dependent Raman spectroscopy, demonstrate the potential of SnSe nanoribbons as thermoelectric material.

Microscopic Manipulation of Ferroelectric Domains in SnSe Monolayers at Room Temperature.

Two-dimensional (2D) van der Waals ferroelectrics provide an unprecedented architectural freedom for the creation of artificial multiferroics and nonvolatile electronic devices based on vertical and coplanar heterojunctions of 2D ferroic materials. Nevertheless, controlled microscopic manipulation of ferroelectric domains is still rare in monolayer-thick 2D ferroelectrics with in-plane polarization. Here we report the discovery of robust ferroelectricity with a critical temperature close to 400 K in SnSe monolayer plates grown on graphene and the demonstration of controlled room-temperature ferroelectric domain manipulation by applying appropriate bias voltage pulses to the tip of a scanning tunneling microscope (STM). This study shows that STM is a powerful tool for detecting and manipulating the microscopic domain structures in 2D ferroelectric monolayers, which are difficult for conventional approaches such as piezoresponse force microscopy, thus facilitating the hunt for other 2D ferroelectric monolayers with in-plane polarization with important technological applications.

Ultrathin Layered SnSe Nanoplates for Low Voltage, High-Rate, and Long-Life Alkali-Ion Batteries.

2D electrode materials with layered structures have shown huge potential in the fields of lithium- and sodium-ion batteries. However, their poor conductivity limits the rate performance and cycle stability of batteries. Herein a new colloid chemistry strategy is reported for making 2D ultrathin layered SnSe nanoplates (SnSe NPs) for achieving more efficient alkali-ion batteries. Due to the effect of weak Van der Waals forces, each semiconductive SnSe nanoplate stacks on top of each other, which can facilitate the ion transfer and accommodate volume expansion during the charge and discharge process. This unique structure as well as the narrow-bandgap semiconductor property of SnSe simultaneously meets the requirements of achieving fast ionic and electronic conductivities for alkali-ion batteries. They exhibit high capacity of 463.6 mAh g-1 at 0.05 A g-1 for Na-ion batteries and 787.9 mAh g-1 at 0.2 A g-1 for Li-ion batteries over 300 cycles, and also high stability for alkali-ion batteries.

High-Concentration Aqueous Dispersions of Nanoscale 2D Materials Using Nonionic, Biocompatible Block Copolymers.

Conditions for the dispersion of molybdenum disulfide (MoS2) in aqueous solution at concentrations up to 0.12 mg mL(-1) using a range of nonionic, biocompatible block copolymers (i.e., Pluronics and Tetronics) are identified. Furthermore, the optimal Pluronic dispersant for MoS2 is found to be effective for a range of other 2D materials such as molybdenum diselenide, tungsten diselenide, tungsten disulfide, tin selenide, and boron nitride.

Facile Surfactant-Free Synthesis of p-Type SnSe Nanoplates with Exceptional Thermoelectric Power Factors.

A surfactant-free solution methodology, simply using water as a solvent, has been developed for the straightforward synthesis of single-phase orthorhombic SnSe nanoplates in gram quantities. Individual nanoplates are composed of {100} surfaces with {011} edge facets. Hot-pressed nanostructured compacts (Eg ≈0.85 eV) exhibit excellent electrical conductivity and thermoelectric power factors (S(2) σ) at 550 K. S(2) σ values are 8-fold higher than equivalent materials prepared using citric acid as a structure-directing agent, and electrical properties are comparable to the best-performing, extrinsically doped p-type polycrystalline tin selenides. The method offers an energy-efficient, rapid route to p-type SnSe nanostructures.

Influence of Sputtering Power on the Properties of Magnetron Sputtered Tin Selenide Films.

The ecofriendly tin selenide (SnSe) is expected to find multiple applications in optoelectronic, photovoltaic, and thermoelectric systems. This work is focused on the thermoelectric properties of thin films. SnSe single crystals exhibit excellent thermoelectric properties, but it is not so in the case of polycrystalline bulk materials. The investigations were motivated by the fact that nanostructuring may lead to an improvement in thermoelectric efficiency, which is evaluated through a dimensionless figure of merit, ZT = S2 σ T/λ, where S is the Seebeck coefficient (V/K), σ is the electrical conductivity (S/m), λ is the thermal conductivity (W/mK), and T is the absolute temperature (K). The main objective of this work was to obtain SnSe films via magnetron sputtering of a single target. Instead of common radiofrequency (RF) magnetron sputtering with a high voltage alternating current (AC) power source, a modified direct current (DC) power supply was employed. This technique in the classical version is not suitable for sputtering targets with relatively low thermal and electrical conductivity, such as SnSe. The proposed solution enabled stable sputtering of this target without detrimental cracking and arcing and resulted in high-quality polycrystalline SnSe films with unprecedented high values of ZT equal to 0.5 at a relatively low temperature of 530 K. All parameters included in ZT were measured in one setup, i.e., Linseis Thin Film Analyzer (TFA). The SnSe films were deposited at sputtering powers of 120, 140, and 170 W. They had the same orthorhombic structure, as determined by X-ray diffraction (XRD), but the thickness and microstructure examined by scanning electron microscopy (SEM) were dependent on the sputtering power. It was demonstrated that thermoelectric efficiency improved with increasing sputtering power and stable values were attained after two heating-cooling cycles. This research additionally provides further insights into the DC sputtering process and opens up new possibilities for magnetron sputtering technology.

Defect-Free Nanowelding of Bilayer SnSe Nanoplates.

Nanowelding is a bottom-up technique to create custom-designed nanostructures and devices beyond the precision of lithographic methods. Here, a new technique is reported based on anisotropic lubricity at the van der Waals interface between monolayer and bilayer SnSe nanoplates and a graphene substrate to achieve precise control of the crystal orientation and the interface during the welding process. As-grown SnSe monolayer and bilayer nanoplates are commensurate with graphene's armchair direction but lack commensuration along graphene's zigzag direction, resulting in a reduced friction along that direction and a rail-like, 1D movement that permits joining nanoplates with high precision. This way, molecular beam epitaxially grown SnSe nanoplates of lateral sizes 30-100 nm are manipulated by the tip of a scanning tunneling microscope at room temperature. In situ annealing is applied afterward to weld contacting nanoplates without atomic defects at the interface. This technique can be generalized to any van der Waals interfaces with anisotropic lubricity and is highly promising for the construction of complex quantum devices, such as field effect transistors, quantum interference devices, lateral tunneling junctions, and solid-state qubits.

Femtosecond Electron Diffraction Reveals Local Disorder and Local Anharmonicity in Thermoelectric SnSe.

In addition to long-range periodicity, local disorder, with local structures deviating from the average lattice structure, dominates the physical properties of phonons, electrons, and spin subsystems in crystalline functional materials. Experimentally characterizing the 3D atomic configuration of such a local disorder and correlating it with advanced functions remains challenging. Using a combination of femtosecond electron diffraction, structure factor calculations, and time-dependent density functional theory molecular dynamics simulations, the static local disorder and its local anharmonicity in thermoelectric SnSe are identified exclusively. The ultrafast structural dynamics reveal that the crystalline SnSe is composed of multiple locally correlated configurations dominated by the static off-symmetry displacements of Sn (≈0.4 Å) and such a set of locally correlated structures is termed local disorder. Moreover, the anharmonicity of this local disorder induces an ultrafast atomic displacement within 100 fs, indicating the signature of probable THz Einstein oscillators. The identified local disorder and local anharmonicity suggest a glass-like thermal transport channel, which updates the fundamental insight into the long-debated ultralow thermal conductivity of SnSe. The method of revealing the 3D local disorder and the locally correlated interactions by ultrafast structural dynamics will inspire broad interest in the construction of structure-property relationships in material science.

Copper Functionalized SnSe Nanoflakes Enabling Nonlinear Optical Features for Ultrafast Photonics.

This study enhances the ultrafast photonics application of tin selenide (SnSe) nanoflakes via copper (Cu) functionalization to overcome challenges such as low conductivity and weak near-infrared (NIR) absorption. Cu functionalization enhances concentration, induces strain, and reduces the bandgap through Sn substitution and Sn vacancy filling with Cu ions. Demonstrated by density functional theory calculations and experimental analyses, Cu-functionalized SnSe exhibits improved NIR optical absorption and superior third-order nonlinear optical properties. Z-scan measurements and femtosecond transient absorption spectroscopy reveal better performance of Cu-functionalized SnSe in terms of nonlinear optical properties and shorter carrier relaxation times compared to pristine SnSe. Furthermore, saturable absorbers based on both SnSe types, when integrated into an erbium-doped fiber laser, show that Cu functionalization leads to a decrease in pulse duration to 798 fs and an increase in 3 dB spectral bandwidth to 3.44 nm. Additionally, it enables stable harmonic mode-locking of bound-state solitons. This work suggests a new direction for improving wide bandgap 2D materials by highlighting the enhanced nonlinear optical properties and potential of Cu-functionalized SnSe in ultrafast photonics.

Rapid Printing of Pseudo-3D Printed SnSe Thermoelectric Generators Utilizing an Inorganic Binder.

There has been much interest in tin selenide (SnSe) in the thermoelectric community since the discovery of the record zT in the material in 2014. Manufacturing techniques used to produce SnSe are largely energy-intensive (e.g., spark plasma sintering); however, recently, in previous work, SnSe has been shown to be produced via a low embodied energy printing technique, resulting in 3D samples with high zT values (up to 1.7). Due to the additive manufacturing technique, the manufacturing time required was substantial. In this work, 3D samples were printed using the inorganic binder sodium metasilicate and reusable molds. This facilitated a single-step printing process that substantially reduced the manufacturing time. The printed samples were thermally stable through multiple thermal cycles, and a peak zT of 0.751 at 823 K was observed with the optimum binder concentration. A proof-of-concept thermoelectric generator produced the highest power output of any reported printed Se-based TEG to date.

A Comparative Study of Electronic, Optical, and Thermoelectric Properties of Zn-Doped Bulk and Monolayer SnSe Using Ab Initio Calculations.

In this study, we explore the effects of Zn doping on the electronic, optical, and thermoelectric properties of α-SnSe in bulk and monolayer forms, employing density functional theory calculations. By varying the doping concentrations, we aim to understand the characteristics of Zn-doped SnSe in both systems. Our analysis of the electronic band structure using (PBE), (SCAN), and (HSE06) functionals reveals that all doped systems exhibit semiconductor-like behavior, making them suitable for applications in optoelectronics and photovoltaics. Notably, the conduction bands in SnSe monolayers undergo changes depending on the Zn concentration. Furthermore, the optical analysis indicates a decrease in the dielectric constant when transitioning from bulk to monolayer forms, which is advantageous for capacitor production. Moreover, heavily doped SnSe monolayers hold promise for deep ultraviolet applications. Examining the thermoelectric transport properties, we observe that Zn doping enhances the electrical conductivity in bulk SnSe at temperatures below 500 K. However, the electronic thermal conductivity of monolayer samples is lower compared to bulk samples, and it decreases consistently with increasing Zn concentrations. Additionally, the Zn-doped 2D samples exhibit high Seebeck coefficients across most of the temperature ranges investigated.

Constructing quasi-layered and self-hole doped SnSe oriented films to achieve excellent thermoelectric power factor and output power density.

Thermoelectric (TE) technology can achieve the mutual conversion between electric energy and waste heat, and it has exhibited great prospects in multifunctional energy applications to alleviate the energy crisis. In the recent decade, SnSe has been explored widely because of its potentially high energy harvesting efficiency, green nature, and low cost. However, the relatively poor power factor (PF) derived from the intrinsic low carrier concentration (∼1017 cm-3) limits the output power density of the stoichiometric SnSe devices. Therefore, the advancement of novel optimization strategies for controlling carrier concentration is of utmost importance. Besides, compared with 3D bulks, 2D thin films are more compatible with modern semiconductor technology and have unique advantages in the construction and application of TE micro- and nano-devices. In this study, post-selenization technology were applied to increase the carrier concentration of the a-axis oriented SnSe epitaxial films utilizing the charge transfer and self-hole doped effects. The quasi-layered and self-hole doped films exhibited a high power factor of ∼5.9 µW cm-1 K-2 at 600 K along the in-plane direction when the carrier concentration is enhanced to ∼1018 cm-3 by increasing the selenization time to ∼20 min. The TE generator composed of four P-type film legs demonstrated the ultrahigh maximum power density of ∼83, ∼838 µW cm-2 at the temperature difference of ∼50 and ∼90 K, respectively. Post-selenization can effectively optimize the carrier concentration of SnSe-based materials, which is also feasible to other anion deficient TE films.

Large-Scale Colloidal Synthesis of Chalcogenides for Thermoelectric Applications.

A simple and effective preparation of solution-processed chalcogenide thermoelectric materials is described. First, PbTe, PbSe, and SnSe were prepared by gram-scale colloidal synthesis relying on the reaction between metal acetates and diphenyl dichalcogenides in hexadecylamine solvent. The resultant phase-pure chalcogenides consist of highly crystalline and defect-free particles with distinct cubic-, tetrapod-, and rod-like morphologies. The powdered PbTe, PbSe, and SnSe products were subjected to densification by spark plasma sintering (SPS), affording dense pellets of the respective chalcogenides. Scanning electron microscopy shows that the SPS-derived pellets exhibit fine nano-/micro-structures dictated by the original morphology of the key constituting particles, while the powder X-ray diffraction and electron microscopy analyses confirm that the SPS-derived pellets are phase-pure materials, preserving the structure of the colloidal synthesis products. The resultant solution-processed PbTe, PbSe, and SnSe exhibit low thermal conductivity, which might be due to the enhanced phonon scattering developed over fine microstructures. For undoped n-type PbTe and p-type SnSe samples, an expected moderate thermoelectric performance is achieved. In contrast, an outstanding figure-of-merit of 0.73 at 673 K was achieved for undoped n-type PbSe outperforming, the majority of the optimized PbSe-based thermoelectric materials. Overall, our findings facilitate the design of efficient solution-processed chalcogenide thermoelectrics.

Tuning and Sensitivity Improvement of Bi-Metallic Structure-Based Surface Plasmon Resonance Biosensor with 2-D ε -Tin Selenide Nanosheets.

This manuscript aims to analyze the effect of tin selenide (SnSe) on the sensing application of SPR biosensors. Tin selenide is the 2-dimensional transition metal dichalcogenide material. The proposed multilayer structure has a BK7 prism, a bimetallic layer of Au, tin selenide, and a graphene layer. Tin selenide is used to improve the performance parameters of the biosensor. The ε - SnSe nanosheet is placed in between two layers of gold (Au) in the Kretschmann configuration. The proposed configuration has a maximum sensitivity of 214 deg/RIU, 93.81% higher than the conventional sensor. The performance parameters like full width half maximum, detection accuracy, and quality factor have been analyzed. The ε - SnSe material is an air-stable 2-D. The proposed sensor is suitable for the analysis of chemical, medical, and biological analytes.

Defect Engineering in Solution-Processed Polycrystalline SnSe Leads to High Thermoelectric Performance.

SnSe has emerged as one of the most promising materials for thermoelectric energy conversion due to its extraordinary performance in its single-crystal form and its low-cost constituent elements. However, to achieve an economic impact, the polycrystalline counterpart needs to replicate the performance of the single crystal. Herein, we optimize the thermoelectric performance of polycrystalline SnSe produced by consolidating solution-processed and surface-engineered SnSe particles. In particular, the SnSe particles are coated with CdSe molecular complexes that crystallize during the sintering process, forming CdSe nanoparticles. The presence of CdSe nanoparticles inhibits SnSe grain growth during the consolidation step due to Zener pinning, yielding a material with a high density of grain boundaries. Moreover, the resulting SnSe-CdSe nanocomposites present a large number of defects at different length scales, which significantly reduce the thermal conductivity. The produced SnSe-CdSe nanocomposites exhibit thermoelectric figures of merit up to 2.2 at 786 K, which is among the highest reported for solution-processed SnSe.

SnSe-Coated Microfiber Resonator for All-Optical Modulation.

In this study, a tin monoselenide (SnSe)-based all-optical modulator is firstly demonstrated with high tuning efficiency, broad bandwidth, and fast response time. The SnSe nanoplates are deposited in the microfiber knot resonator (MKR) on MgF2 substrate and change its transmission spectra by the external laser irradiation. The SnSe nanoplates and the microfiber are fabricated using the liquid-phase exfoliation method and the heat-flame taper-drawing method, respectively. Due to the strong absorption and enhanced light-matter interaction of the SnSe nanoplates, the largest transmitted power tunability is approximately 0.29 dB/mW with the response time of less than 2 ms. The broad tuning bandwidth is confirmed by four external pump lights ranging from ultraviolet to near-infrared. The proposed SnSe-coated microfiber resonator holds promising potential for wide application in the fields of all-optical tuning and fiber sensors.

High-Mobility Metastable Rock-Salt Type (Sn,Ca)Se Thin Film Stabilized by Direct Epitaxial Growth on a YSZ (111) Single-Crystal Substrate.

Metastable cubic (Sn1-xPbx)Se with x ≥ 0.5 is expected to be a high mobility semiconductor due to its Dirac-like electronic state, but it has an excessively high carrier concentration of ∼1019 cm-3 and is not suitable for semiconductor device applications such as thin film transistors and solar cells. Further, thin films of (Sn1-xPbx)Se require a complicated synthesis process because of the high vapor pressure of Pb. We herein report the direct growth of metastable cubic (Sn1-xCax)Se films alloyed with CaSe, which has a wider bandgap and lower vapor pressure than PbSe. The cubic (Sn1-xCax)Se epitaxial films with x = 0.4-0.8 are stabilized on YSZ (111) single crystalline substrates by pulsed laser deposition. (Sn1-xCax)Se has a direct-transition-type bandgap, and the bandgap energy can be varied from 1.4 eV (x = 0.4) to 2.0 eV (x = 0.8) by changing x. These films with x = 0.4-0.6 show p-type conduction with low hole carrier concentrations of ∼1017 cm-3. Hall mobility analysis suggests that the hole transport would be dominated by 180° rotational domain structures, which is specific to (111) oriented epitaxial films. However, it, in turn, clarifies that the in-grain carrier mobility in the (Sn0.6Ca0.4)Se film is as high as 322 cm2/(Vs), which is much higher than those in thermodynamically stable layered SnSe and other Sn-based layered semiconductor films at room temperature. Therefore, the present results prove the potential of high mobility (Sn1-xCax)Se films for semiconductor device applications via a simple thin-film deposition process.

Measuring and Then Eliminating Twin Domains in SnSe Thin Films Using Fast Optical Metrology and Molecular Beam Epitaxy.

van der Waals (vdW) layered chalcogenides have strongly direction-dependent (i.e., anisotropic) properties that make them interesting for photonic and optoelectronic applications. Orthorhombic tin selenide (α-SnSe) is a triaxial vdW material with strong optical anisotropy within layer planes, which has motivated studies of optical phase and domain switching. As with every vdW material, controlling the orientation of crystal domains during growth is key to reliably making wafer-scale, high-quality thin films, free from twin boundaries. Here, we demonstrate a fast optical method to quantify domain orientation in SnSe thin films made by molecular beam epitaxy (MBE). The in-plane optical anisotropy results in white-light being reflected into distinct colors for certain optical polarization angles and the color depends on domain orientation. We use our method to confirm a high density of twin boundaries in SnSe epitaxial films on MgO substrates, with square symmetry that results in degeneracy between SnSe 90° domain orientations. We then demonstrate that growing on a-plane sapphire, with rectangular lattice-matched symmetry that breaks the SnSe domain degeneracy, results in single-crystalline films with one preferred orientation. Our SnSe bottom-up film synthesis by MBE enables future applications of this vdW material that is particularly difficult to process by top-down methods. Our optical metrology is fast and can apply to all triaxial vdW materials.

An Overview of the Strategies for Tin Selenide Advancement in Thermoelectric Application.

Chalcogenide, tin selenide-based thermoelectric (TE) materials are Earth-abundant, non-toxic, and are proven to be highly stable intrinsically with ultralow thermal conductivity. This work presented an updated review regarding the extraordinary performance of tin selenide in TE applications, focusing on the crystal structures and their commonly used fabrication methods. Besides, various optimization strategies were recorded to improve the performance of tin selenide as a mid-temperature TE material. The analyses and reviews over the methodologies showed a noticeable improvement in the electrical conductivity and Seebeck coefficient, with a noticeable decrement in the thermal conductivity, thereby enhancing the tin selenide figure of merit value. The applications of SnSe in the TE fields such as microgenerators, and flexible and wearable devices are also discussed. In the future, research in low-dimensional TE materials focusing on nanostructures and nanocomposites can be conducted with the advancements in material science technology as well as microtechnology and nanotechnology.