Chemical Patterning of High‐Mobility Semiconducting 2D Bi2O2Se Crystals for Integrated Optoelectronic Devices

Patterning of high‐mobility 2D semiconducting materials with unique layered structures and superb electronic properties offers great potential for batch fabrication and integration of next‐generation electronic and optoelectronic devices. Here, a facile approach is used to achieve accurate patterning of 2D high‐mobility semiconducting Bi₂O₂Se crystals using dilute H₂O₂ and protonic mixture acid as efficient etchants. The 2D Bi₂O₂Se crystal after chemical etching maintains a high Hall mobility of over 200 cm² V^?1 s^?1 at room temperature. Centimeter‐scale well‐ordered arrays of 2D Bi₂O₂Se with tailorable configurations are readily obtained. Furthermore, integrated photodetectors based on 2D Bi₂O₂Se arrays are fabricated, exhibiting excellent air stability and high photoresponsivity of ≈2000 A W^?1 at 532 nm. These results are one step towards the practical application of ultrathin 2D integrated digital and optoelectronic circuits.     

In Situ Repair of 2D Chalcogenides under Electron Beam Irradiation

Molybdenum disulfide (MoS₂) and bismuth telluride (Bi₂Te₃) are the two most common types of structures adopted by 2D chalcogenides. In view of their unique physical properties and structure, 2D chalcogenides have potential applications in various fields. However, the excellent properties of these 2D crystals depend critically on their crystal structures, where defects, cracks, holes, or even greater damage can be inevitably introduced during the preparation and transferring processes. Such defects adversely impact the performance of devices made from 2D chalcogenides and, hence, it is important to develop ways to intuitively and precisely repair these 2D crystals on the atomic scale, so as to realize high‐reliability devices from these structures. Here, an in situ study of the repair of the nanopores in MoS₂ and Bi₂Te₃ is carried out under electron beam irradiation by transmission electron microscopy. The experimental conditions allow visualization of the structural dynamics of MoS₂ and Bi₂Te₃ crystals with unprecedented resolution. Real‐time observation of the healing of defects at atomic resolution can potentially help to reproducibly fabricate and simultaneously image single‐crystalline free‐standing 2D chalcogenides. Thus, these findings demonstrate the viability of using an electron beam as an effective tool to precisely engineer materials to suit desired applications in the future.     

Physical properties of Bi2 (Te,Se)3 and Bi2Se1.2Te1.8 prepared using solid-state microwave synthesis

Bi₂(Te, Se)₃ and Bi₂Se_1.2Te_1.8 bulk products were synthesised using standard solid-state microwave synthesis. The Bi₂(Te, Se)₃ and Bi₂Se_1.2Te_1.8 were then deposited thermally onto glass substrates at a pressure of 10^? 6 Torr. The structure of the samples was analysed using X-ray diffraction (XRD), and the powders and thin films were observed to be polycrystalline and rhombohedral in structure. The surface morphology of the samples was determined using scanning electron microscopy (SEM). From the measurements of optical properties, the energy gap values for the Bi₂Te₃, Bi₂Se₃, and Bi₂Se_1.2Te_1.8 thin films were 0.43, 0.73, and 0.65 eV, respectively.     

Flexible and High‐Performance All‐2D Photodetector for Wearable Devices

Emerging novel applications at the forefront of innovation horizon raise new requirements including good flexibility and unprecedented properties for the photoelectronic industry. On account of diversity in transport and photoelectric properties, 2D layered materials have proven as competent building blocks toward next‐generation photodetectors. Herein, an all‐2D Bi₂Te₃‐SnS‐Bi₂Te₃ photodetector is fabricated with pulsed‐laser deposition. It is sensitive to broadband wavelength from ultraviolet (370 nm) to near‐infrared (808 nm). In addition, it exhibits great durability to bend, with intact photoresponse after 100 bend cycles. Upon 370 nm illumination, it achieves a high responsivity of 115 A W^?1, a large external quantum efficiency of 3.9 × 10⁴%, and a superior detectivity of 4.1 × 10¹¹ Jones. They are among the best figures‐of‐merit of state‐of‐the‐art 2D photodetectors. The synergistic effect of SnS's strong light–matter interaction, efficient carrier separation of Bi₂Te₃–SnS interface, expedite carrier injection across Bi₂Te₃–SnS interface, and excellent carrier collection of Bi₂Te₃ topological insulator electrodes accounts for the superior photodetection properties. In summary, this work depicts a facile all‐in‐one fabrication strategy toward a Bi₂Te₃‐SnS‐Bi₂Te₃ photodetector. More importantly, it reveals a novel all‐2D concept for construction of flexible, broadband, and high‐performance photoelectronic devices by integrating 2D layered metallic electrodes and 2D layered semiconducting channels.     

Molecular Beam Epitaxy and Electronic Structure of Atomically Thin Oxyselenide Films

Atomically thin oxychalcogenides have been attracting intensive attention for their fascinating fundamental properties and application prospects. Bi₂O₂Se, a representative of layered oxychalcogenides, has emerged as an air‐stable high‐mobility 2D semiconductor that holds great promise for next‐generation electronics. The preparation and device fabrication of high‐quality Bi₂O₂Se crystals down to a few atomic layers remains a great challenge at present. Here, molecular beam epitaxy (MBE) of atomically thin Bi₂O₂Se films down to monolayer on SrTiO₃ (001) substrate is achieved by co‐evaporating Bi and Se precursors in oxygen atmosphere. The interfacial atomic arrangements of MBE‐grown Bi₂O₂Se/SrTiO₃ are unambiguously revealed, showing an atomically sharp interface and atom‐to‐atom alignment. Importantly, the electronic band structures of one‐unit‐cell (1‐UC) thick Bi₂O₂Se films are observed by angle‐resolved photoemission spectroscopy (ARPES), showing low effective mass of ≈0.15 m₀ and bandgap of ≈0.8 eV. These results may be constructive to the synthesis of other 2D oxychalcogenides and investigation of novel physical properties.     

Density-Dependence of Surface Transport in Tellurium-Enriched Nanograined Bulk Bi2Te3

Three-dimensional topological insulators (3D TI) exhibit conventional parabolic bulk bands and protected Dirac surface states. A thorough investigation of the different transport channels provided by the bulk and surface carriers using macroscopic samples may provide a path toward accessing superior surface transport properties. Bi₂Te₃ materials make promising 3D TI models; however, due to their complicated defect chemistry, these materials have a high number of charge carriers in the bulk that dominate the transport, even as nanograined structures. To partially control the bulk charge carrier density, herein the synthesis of Te-enriched Bi₂Te₃ nanoparticles is reported. The resulting nanoparticles are compacted into nanograined pellets of varying porosity to tailor the surface-to-volume ratio, thereby emphasizing the surface transport channels. The nanograined pellets are characterized by a combination of resistivity, Hall- and magneto-conductance measurements together with (THz) time-domain reflectivity measurements. Using the Hikami-Larkin-Nagaoka (HLN) model, a characteristic coherence length of ≈200 nm is reported that is considerably larger than the diameter of the nanograins. The different contributions from the bulk and surface carriers are disentangled by THz spectroscopy, thus emphasizing the dominant role of the surface carriers. The results strongly suggest that the surface transport carriers have overcome the hindrance imposed by nanoparticle boundaries.     

Biodegradable Bi2O2Se Quantum Dots for Photoacoustic Imaging‐Guided Cancer Photothermal Therapy

As new 2D layered nanomaterials, Bi₂O₂Se nanoplates have unique semiconducting properties that can benefit biomedical applications. Herein, a facile top‐down approach for the synthesis of Bi₂O₂Se quantum dots (QDs) in a solution is described. The Bi₂O₂Se QDs with a size of 3.8 nm and thickness of 1.9 nm exhibit a high photothermal conversion coefficient of 35.7% and good photothermal stability. In vitro and in vivo assessments demonstrate that the Bi₂O₂Se QDs possess excellent photoacoustic (PA) performance and photothermal therapy (PTT) efficiency. After systemic administration, the Bi₂O₂Se QDs accumulate passively in tumors enabling efficient PA imaging of the entire tumors to facilitate imaging‐guided PTT without obvious toxicity. Furthermore, the Bi₂O₂Se QDs which exhibit degradability in aqueous media not only have sufficient stability during in vivo circulation to perform the designed therapeutic functions, but also can be discharged harmlessly from the body afterward. The results reveal the great potential of Bi₂O₂Se QDs as a biodegradable multifunctional agent in medical applications.     

Thermoelectric materials based on Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> solid solutions with optimal performance in the range 100–400 K

We have optimized the compositions of thermoelectric materials based on Sb₂Te₃-Bi₂Te₃ solid solutions using Czochralski-grown single crystals. The thermoelectric performance of Sb₂Te₃-Bi₂Te₃ solid solutions containing 0–100 mol % Bi₂Te₃ and Bi₂Te₃-Sb₂Te₃-Bi₂-Bi₂Se₃ solid solutions containing 2, 4, or 7 mol % Bi₂Se₃ has been investigated. The Bi₂Se₃-doped crystals are found to have higher thermoelectric figures of merit compared to the undoped crystals. The optimal crystal compositions are selected for different temperatures in the range 100–400 K.     

Structural and Transport Properties of Sn-Doped Bi2Te3 – x Se x Single Crystals

The transport properties of Bi_{2 – y} Sn _y Te_{3 – x} Se _x solid solutions are studied. The results demonstrate that doping with Sn has a strong effect on the temperature dependences of the thermoelectric power and electrical conductivity of the crystals. This suggests that the valence band of the crystals contains Sn-related resonance states. The point defects and dislocation system in Bi₂Te₃ and Bi_{2 – y} Sn _y Te_{3 – x} Se _x solid solutions are studied by transmission electron microscopy. It is shown that the predominant defects in the crystals studied, grown by the Czochralski technique, are dislocations lying in the (0001) plane. The estimated dislocation density is 10⁸ to 10⁹ cm^–2, and the primary slip plane is (0001). Electron-microscopic examination indicates the presence of stacking faults and very small dislocation loops in both Bi₂Te₃ and Bi_{2 – y} Sn _y Te_{3 – x} Se _x single crystals. Since all of the crystals are highly degenerate semiconductors, it is reasonable to assume that structural defects have an insignificant effect on their electrical properties.     

The growth and properties of (Sbx Bi1–x)2Te3 crystals

Abstract

Vertical Bridgman systems with programmable temperature control are used to grow (Sb_xBi_1:x)₂Te₃ crystals. High purity Bi, Sb and Te are used as sources and the diameter of 1.1 cm, little soft bulk crystals of (Sb_xBi_1–x)₂ Te₃ can be obtained. Scanning electron microscope (SEM) and electron probe microanalysis (EPMA) are used to analyze the micro‐structure and the compositions of the crystal. From the X‐ray diffraction patterns it appears that the grown crystal is single crystal or directive polycrystal. If the uniformity of the source solution and grown temperature are under control, then the high quality of single crystals can be obtained. The dependence of crystal structure and the thermoelectric characteristics on the changed compositions of grown crystals are discussed. The optimum composition for the thermoelectric properties is Sb_1.00 Bi_1.04Te_2.96. When the DC current, 3A, is applied to the Sb_1.00 Bi_1.04 Te_2.96 crystal with suitable electrodes, the temperature difference (△T) between two sides of the crystal can be as high as 60°C. It is 2 times larger than that ever obtained by Sb₂Te₃ crystal. It appeared that the grown (Sb_xBi_1‐x)₂Te₃ crystals have the potential on the fabrication of thermoelectric devices and electronic cooling system.     

Phase relations and thermoelectric properties of alloys in the Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> system

Using differential thermal analysis and x-ray diffraction, we have shown that the Bi₂Te₃-Bi₂Se₃ system contains a continuous series of solid solutions in a narrow temperature range and a compound of composition Bi₂Te₂Se below the solidus line. The liquidus and solidus lines determined using zone-melted samples differ little from those reported in the literature for equilibrium samples. The Bi₂Te_3?x Se _x solid-solution phase extends to ～-14 mol % Bi₂Se₃ (Bi₂Te_2.58Se_0.42). The thermoelectric power of the alloys drops sharply near the boundary of the two-phase region. Within the homogeneity range of Bi₂Te₂Se (33.3 mol % Bi₂Se₃), the thermoelectric power factor has a minimum, while the thermoelectric power has a small maximum.     

Salt-Assisted Low-Temperature Growth of 2D Bi2O2Se with Controlled Thickness for Electronics

Bi₂O₂Se is the most promising 2D material due to its semiconducting feature and high mobility, making it propitious channel material for high-performance electronics that demands highly crystalline Bi₂O₂Se at low-growth temperature. Here, a low-temperature salt-assisted chemical vapor deposition approach for growing single-domain Bi₂O₂Se on a millimeter scale with thicknesses of multilayer to monolayer is presented. Because of the advantage of thickness-dependent growth, systematical scrutiny of layer-dependent Raman spectroscopy of Bi₂O₂Se from monolayer to bulk is investigated, revealing a redshift of the A_1g mode at 162.4 cm⁻¹. Moreover, the long-term environmental stability of ≈2.4 nm thick Bi₂O₂Se is confirmed after exposing the sample for 1.5 years to air. The backgated field effect transistor (FET) based on a few-layered Bi₂O₂Se flake represents decent carrier mobility (≈287 cm² V⁻¹s⁻¹) and an ON/OFF ratio of up to 10⁷. This report indicates a technique to grow large-domain thickness controlled Bi₂O₂Se single crystals for electronics.     

Properties of Bi2Te3 single crystals doped with Sn

The effect of doping with Sn on the properties of Czochralski-grown Bi₂Te₃ crystals was studied. The effective segregation coefficient for Sn was determined to be 0.6. The thermoelectric power, electrical conductivity, and Hall coefficient of the doped crystals were measured at room temperature. Doping with low Sn concentrations (0.2-0.5 at. %) was found to have only a weak effect on the electrical properties ofp- type Bi₂Te₃. Doping with 0.7-1 at. % Sn reduces the thermoelectric power and increases the electrical conductivity and hole concentration. Lattice thermal conductivity is a nonmonotonic function of Sn concentration. The thermoelectric figure of merit of Bi₂Te₃ doped with less than 0.6 at. % Sn exceeds that of undoped Bi₂Te₃.     

Understanding the Structure and Properties of Sesqui‐Chalcogenides (i.e., V2VI3 or Pn2Ch3 (Pn = Pnictogen,Ch = Chalcogen) Compounds) from a Bonding Perspective

A number of sesqui‐chalcogenides show remarkable properties, which make them attractive for applications as thermoelectrics, topological insulators, and phase‐change materials. To see if these properties can be related to a special bonding mechanism, seven sesqui‐chalcogenides (Bi₂Te₃, Bi₂Se₃, Bi₂S₃, Sb₂Te₃, Sb₂Se₃, Sb₂S₃, and β‐As₂Te₃) and GaSe are investigated. Atom probe tomography studies reveal that four of the seven sesqui‐chalcogenides (Bi₂Te₃, Bi₂Se₃, Sb₂Te₃, and β‐As₂Te₃) show an unconventional bond‐breaking mechanism. The same four compounds evidence a remarkable property portfolio in density functional theory calculations including large Born effective charges, high optical dielectric constants, low Debye temperatures and an almost metal‐like electrical conductivity. These results are indicative for unconventional bonding leading to physical properties distinctively different from those caused by covalent, metallic, or ionic bonding. The experiments reveal that this bonding mechanism prevails in four sesqui‐chalcogenides, characterized by rather short interlayer distances at the van der Waals like gaps, suggestive of significant interlayer coupling. These conclusions are further supported by a subsequent quantum‐chemistry‐based bonding analysis employing charge partitioning, which reveals that the four sesqui‐chalcogenides with unconventional properties are characterized by modest levels of charge transfer and sharing of about one electron between adjacent atoms. Finally, the 3D maps for different properties reveal discernible property trends and enable material design.     

Properties of Sn-doped Bi2Te3 − x Sex single crystals

The effect of Sn doping (0.2 and 0.4 at %) on the properties of Czochralski-grown single crystals of n-type Bi₂Te_2.85Se_0.15 solid solutions is studied. Thermoelectric power, electrical conductivity, thermal conductivity, and Hall effect measurements in the range 77–400 K demonstrate that Sn doping has a significant effect on the transport properties of the solid solutions. Between 300 and 370 K, the thermoelectric figure of merit of Bi_1.996Sn_0.004Te_2.85Se_0.15 single crystals is higher than that of the Sn-free solid solution. In addition, hot-microprobe thermoelectric power measurements, highly sensitive to variations in carrier concentration, indicate that the Sn-doped single crystals are very uniform in electrical properties, both along the growth direction and radially.     

Growth and self-organization of nanostructures on interlayer surfaces of A<Stack><Subscript>2</Subscript><Superscript>V</Superscript></Stack>B<Stack><Subscript>3</Subscript><Superscript>VI</Superscript></Stack> layered crystals

This paper examines the formation of arrays of interlayer nanostructures in layered crystals grown by directional solidification and the Bridgman method. Sb₂Te₃ and Bi₂Te₃ layers are shown to contain steplayered structures with nanostructured islands on them. Atomic force microscope images of interlayer nanostructures in such crystals are analyzed in terms of the physics of fractals and self-organization processes.     

Ultrasensitive 2D Bi2O2Se Phototransistors on Silicon Substrates

2D materials are considered as intriguing building blocks for next‐generation optoelectronic devices. However, their photoresponse performance still needs to be improved for practical applications. Here, ultrasensitive 2D phototransistors are reported employing chemical vapor deposition (CVD)‐grown 2D Bi₂O₂Se transferred onto silicon substrates with a noncorrosive transfer method. The as‐transferred Bi₂O₂Se preserves high quality in contrast to the serious quality degradation in hydrofluoric‐acid‐assisted transfer. The phototransistors show a responsivity of 3.5 × 10⁴ A W^?1, a photoconductive gain of more than 10⁴, and a time response in the order of sub‐millisecond. With back gating of the silicon substrate, the dark current can be reduced to several pA. This yields an ultrahigh sensitivity with a specific detectivity of 9.0 × 10¹³ Jones, which is one of the highest values among 2D material photodetectors and two orders of magnitude higher than that of other CVD‐grown 2D materials. The high performance of the phototransistor shown here together with the developed unique transfer technique are promising for the development of novel 2D‐material‐based optoelectronic applications as well as integrating with state‐of‐the‐art silicon photonic and electronic technologies.     

Elastic wave propagation in Bi1⋅60Sb0⋅40Te3 and Bi2Te3

The six independent elastic constants of the monocrystalline, pseudo-binary alloy Bi_1·60Sb_0·40Te₃ have been measured by the ultrasonic pulse-echo technique. The elastic behaviour is compared and contrasted with those of Bi₂Te₃ and the group V semimetals with crystal structures belonging to the same point group, ¯3m. Elastic wave-velocity surface cross-sections, particle displacement and energy flux vectors are presented and discussed; the pure mode axes — knowledge of which is most useful in experimental ultrasonic studies — are given. Elastic wave propagation in Bi_1.60Sb_0.40Te₃ and Bi₂Te₃ shows characteristics expected for layer-type crystals with weak interlayer binding, i.e., comparatively large ultrasonic velocities in thexy plane and lower velocities along the direction (z) of weakest binding.     

Hydrothermal synthesis and thermoelectric properties of nanostructured Bi0.5Sb1.5Te3 compounds

Single-phase Bi_0.5Sb_1.5Te₃ compounds have been prepared by hydrothermal synthesis at 150 °C for 24 h using SbCl₃, BiCl₃ and tellurium powder as precursors. X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) have been applied to analyze the phase distributions, microstructures and grain sizes of the as-grown Bi_0.5Sb_1.5Te₃ products. It is found that the hydrothermally synthesized Bi_0.5Sb_1.5Te₃ nanopowders have a morphology dominated by irregular hexagonal sheets due to the anisotropic growth of the crystals. The Bi_0.5Sb_1.5Te₃ nanosheets are parallelly stacked in certain direction to form sheet-agglomerates attribute to the temperature gradients in the solution.     

Possible Mechanism of a New Type of Three-Dimensional Quantized Hall Effect in Layered Semiconductors Bi2−xSnxTe3

We have found a new type of three-dimensional quantized Hall effect (QHE) in layered semiconductors Bi₂–xSn_xTe₃ (x0.0125) single crystals. The Hall resistivity is not expressed in a universal relation applicable for a conventional QHE and depends appreciably on the doped Sn concentration x. The flat Hall plateaus are visible at higher Landau levels but are rather suppressed at lower regions. The calculated Landau levels of the upper valence band (UVB) with the best-fit band parameters are in excellent agreement with the experiments, including spin splitting. For Bi₂–xSn_xTe₃, the Sn-originated impurity band (IB) has resonant nature and enhances the density of states at the Fermi level of UVB. The charge transfer occurs between the quantized UVB and the resonant IB or the lower valence band (LVB) for Bi₂–xSn_xTe₃ or Bi₂Te₃, respectively, and the Landau levels are enhanced appreciably. We have revealed that the quasi-localized states are formed in quantized three-dimensional density of state spectra. We have proposed a possible model for the present QHE, which is a modification of Mani's model, where the quasi-localized state is formed at the disorder-originated tail of each Landau level. In the quasi-localized regime, the IB or LVB are responsible for the carrier reservoir to regulate the Hall resistivity.