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.     

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.     

Crystal engineering of high-T c and related oxide films for future electronics

Advanced technology and future prospect of oxide-based electronic materials are described with a focus on the significance of atomically controlled epitaxy of high-T _c superconductors and related oxide films. Problems in suitably forming the oxides whose power is potentially superior to silicon’s are discussed to stimulate technology development for engineering oxide film growth on an atomic scale. Our experimental results on controlled epitaxial growth of oxide films are presented with respect to pulsed laser deposition of YBa₂Cu₃O_{7 −δ} films as well as laser MBE growth of SrTiO₃ homoepitaxy and CeO₂ heteroepitaxy on Si substrates.     

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.     

Charge Transfer Modulation in Vanadium-Doped WS2/Bi2O2Se Heterostructures

The field of photovoltaics is revolutionized in recent years by the development of two–dimensional (2D) type-II heterostructures. These heterostructures are made up of two different materials with different electronic properties, which allows for the capture of a broader spectrum of solar energy than traditional photovoltaic devices. In this study, the potential of vanadium (V)-doped WS₂ is investigated, hereafter labeled V-WS₂, in combination with air-stable Bi₂O₂Se for use in high-performance photovoltaic devices. Various techniques are used to confirm the charge transfer of these heterostructures, including photoluminescence (PL) and Raman spectroscopy, along with Kelvin probe force microscopy (KPFM). The results show that the PL is quenched by 40%, 95%, and 97% for WS₂/Bi₂O₂Se, 0.4 at.% V-WS₂/Bi₂O₂Se, and 2 at.% V-WS₂/Bi₂O₂Se, respectively, indicating a superior charge transfer in V-WS₂/Bi₂O₂Se compared to pristine WS₂/Bi₂O₂Se. The exciton binding energies for WS₂/Bi₂O₂Se, 0.4 at.% V-WS₂/Bi₂O₂Se and 2 at.% V-WS₂/Bi₂O₂Se heterostructures are estimated to be ≈130, 100, and 80 meV, respectively, which is much lower than that for monolayer WS₂. These findings confirm that by incorporating V-doped WS₂, charge transfer in WS₂/Bi₂O₂Se heterostructures can be tuned, providing a novel light-harvesting technique for the development of the next generation of photovoltaic devices based on V-doped transition metal dichalcogenides (TMDCs)/Bi₂O₂Se.     

An Ultrabroadband Mid‐Infrared Pulsed Optical Switch Employing Solution‐Processed Bismuth Oxyselenide

Pulsed lasers operating in the mid‐infrared (3–25 µm) are increasingly becoming the light source of choice for a wide range of industrial and scientific applications such as spectroscopy, biomedical research, sensing, imaging, and communication. Up to now, one of the factors limiting the mid‐infrared pulsed lasers is the lack of optical switch with a capability of pulse generation, especially for those with wideband response. Here, a semiconductor material of bismuth oxyselenide (Bi₂O₂Se) with a facile processibility, constituting an ultrabroadband saturable absorber for the mid‐infrared (actually from the near‐infrared to mid‐infrared: 0.8–5.0 µm) is exhibited. Significantly, it is found that the optical response is associated with a strong nonlinear character, showing picosecond response time and response amplitude up to ≈330.1% at 5.0 µm. Combined with facile processibility and low cost, these solution‐processed Bi₂O₂Se materials may offer a scalable and printable mid‐infrared optical switch to open up the long‐sought parameter space which is crucial for the exploitation of compact and high‐performance mid‐infrared pulsed laser sources.     

Epitaxial Growth of Ternary Topological Insulator Bi2Te2Se 2D Crystals on Mica

Nanostructures of ternary topological insulator (TI) Bi₂Te₂Se are, in principle, advantageous to the manifestation of topologically nontrivial surface states, due to significantly enhanced surface‐to‐volume ratio compared with its bulk crystals counterparts. Herein, the synthesis of 2D Bi₂Te₂Se crystals on mica via the van der Waals epitaxy method is explored and systematically the growth behaviors during the synthesis process are investigated. Accordingly, 2D Bi₂Te₂Se crystals with domain size up to 50 µm large and thickness down to 2 nm are obtained. A pronounced weak antilocalization effect is clearly observed in the 2D Bi₂Te₂Se crystals at 2 K. The method for epitaxial growth of 2D ternary Bi₂Te₂Se crystals may inspire materials engineering toward enhanced manifestation of the subtle surface states of TIs and thereby facilitate their potential applications in next‐generation spintronics.     

Unveiling the Fine Structural Distortion of Atomically Thin Bi2O2Se by Third-Harmonic Generation

Bismuth oxyselenide (Bi₂O₂Se), a new type of 2D material, has recently attracted increased attention due to its robust bandgap, stability under ambient conditions, and ultrahigh electron mobility. In such complex oxides, fine structural distortion tends to play a decisive role in determining the unique physical properties, such as the ferrorotational order, ferroelectricity, and magnetoelasticity. Therefore, an in-depth investigation of the fine structural symmetry of Bi₂O₂Se is necessary to exploit its potential applications. However, conventional techniques are either time consuming or requiring tedious sample treatment. Herein, a noninvasive and high-throughput approach is reported for characterizing the fine structural distortion in 2D centrosymmetric Bi₂O₂Se by polarization-dependent third-harmonic generation (THG). Unprecedentedly, the divergence between the experimental results and the theoretical prediction of the perpendicular component of polarization-dependent THG indicates a fine structural distortion, namely, a <1.4° rotation of the oxygen square in the tetragonal (Bi₂O₂) layers. This rotation breaks the intrinsic mirror symmetry of 2D Bi₂O₂Se, eventually reducing the symmetry from the D_4h to the C_4h point group. The results demonstrate that THG is highly sensitive to even fine symmetry variations, thereby showing its potential to uncover hidden phase transitions and interacting polarized sublattices in novel 2D material systems.     

Structural and electronic impact of SrTiO3 substrate on TiO2 thin films

We demonstrate that the atomic structures, electronic states, and bonding nature of the interface between SrTiO₃ substrate and anatase TiO₂ thin films could be related and technologically manipulated at the atomic level. Applying advanced transmission electron microscopy, the grown anatase TiO₂ thin films are found to make a clean and direct contact to the SrTiO₃ substrates in an epitaxial, coherent, and atomically abrupt way. The atomic-resolution microscopic images reveal that the interface comprises SrO-terminated SrTiO₃ and Ti-terminated TiO₂ with the interfacial Ti of TiO₂ sitting above the hollow site, which is confirmed theoretically to be the most energetically favorable. Quantitatively, the first-principles calculations predict that the oxygen sublattice at the interface undergoes a notable reconstruction, i.e., the interfacial O atoms of TiO₂ are displaced largely toward the SrO plane of the SrTiO₃, flattening the originally zigzag TiO₂ atomic chains. Consequently, the interfacial layers suffer a remarkable modification in the charge accumulation and also a deviation in the density of states from their bulk counterparts, indicating that the substrate can have an impact on the deposited thin films electronically. Using several analytic methods, the SrTiO₃/TiO₂ interface is found to take on a metallic nature, and the interfacial bonding is determined to be of a mixed covalent and ionic character. This combined experimental and theoretical investigation gains insight into the complex atomic and electronic structures of the buried interface, which are fundamental for relating the atomic-scale structures to their properties on a quantum level.     

Molecular beam epitaxial growth of SrO and CaO with RHEED intensity oscillation

SrO and CaO, related compounds of BSCCO superconductor, are grown onto SrTiO₃(100) substrates with molecular beam epitaxy(MBE) technique. During growth, the specular spots of RHEED patterns show intensity oscillations, indicating two dimensional growth. The periods of oscillations are utilized to calculate the atom fluxes. It is shown that sublimation processes of both Sr and Ca metals in the effusion cells are stable under the growth condition of oxide films. The periods of oscillations during the SrO growth are independent of substrate temperature, confirming that Sr atoms are oxidized immediately and stay on the substrate surface without re-evaporation. These informations are practically available for precise control of the atomic layer controlled MBE of BSCCO superconductor thin films.On leave from Superconductiivity Research Laboratory, ISTEC.     

Bolometric Effect in Bi2O2Se Photodetectors

Bi₂O₂Se is emerging as a photosensitive functional material for optoelectronics, and its photodetection mechanism is mostly considered to be a photoconductive regime in previous reports. Here, the bolometric effect is discovered in Bi₂O₂Se photodetectors. The coexistence of photoconductive effect and bolometric effect is generally observed in multiwavelength photoresponse measurements and then confirmed with microscale local heating experiments. The unique photoresponse of Bi₂O₂Se photodetectors may arise from a change of hot electrons during temperature rises instead of photoexcited holes and electrons. Direct proof of the bolometric effect is achieved by real‐time temperature tracking of Bi₂O₂Se photodetectors under time evolution after light excitation. Moreover, the Bi₂O₂Se bolometer shows a high temperature coefficient of resistance (?1.6% K^?1), high bolometric coefficient (?31 nA K^?1), and high bolometric responsivity (>320 A W^?1). These findings offer a new approach to develop bolometric photodetectors based on Bi₂O₂Se layered materials.     

Synthesis of Large‐Area InSe Monolayers by Chemical Vapor Deposition

Recently, 2D materials of indium selenide (InSe) layers have attracted much attention from the scientific community due to their high mobility transport and fascinating physical properties. To date, reports on the synthesis of high‐quality and scalable InSe atomic films are limited. Here, a synthesis of InSe atomic layers by vapor phase selenization of In₂O₃ in a chemical vapor deposition (CVD) system, resulting in large‐area monolayer flakes or thin films, is reported. The atomic films are continuous and uniform over a large area of 1 × 1 cm², comprising of primarily InSe monolayers. Spectroscopic and microscopic measurements reveal the highly crystalline nature of the synthesized InSe monolayers. The ion‐gel‐gated field‐effect transistors based on CVD InSe monolayers exhibit n‐type channel behaviors, where the field effect electron mobility values can be up to ≈30 cm² V^?1 s^?1 along with an on/off current ratio, of >10⁴ at room temperature. In addition, the graphene can serve as a protection layer to prevent the oxidation between InSe and the ambient environment. Meanwhile, the synthesized InSe films can be transferred to arbitrary substrates, enabling the possibility of reassembly of various 2D materials into vertically stacked heterostructures, prompting research efforts to probe its characteristics and applications.     

Defect‐Tailoring Mediated Electron–Hole Separation in Single‐Unit‐Cell Bi3O4Br Nanosheets for Boosting Photocatalytic Hydrogen Evolution and Nitrogen Fixation

Solar photocatalysis is a potential solution to satisfying energy demand and its resulting environmental impact. However, the low electron–hole separation efficiency in semiconductors has slowed the development of this technology. The effect of defects on electron–hole separation is not always clear. A model atomically thin structure of single‐unit‐cell Bi₃O₄Br nanosheets with surface defects is proposed to boost photocatalytic efficiency by simultaneously promoting bulk‐ and surface‐charge separation. Defect‐rich single‐unit‐cell Bi₃O₄Br displays 4.9 and 30.9 times enhanced photocatalytic hydrogen evolution and nitrogen fixation activity, respectively, than bulk Bi₃O₄Br. After the preparation of single‐unit‐cell structure, the bismuth defects are controlled to tune the oxygen defects. Benefiting from the unique single‐unit‐cell architecture and defects, the local atomic arrangement and electronic structure are tuned so as to greatly increase the charge separation efficiency and subsequently boost photocatalytic activity. This strategy provides an accessible pathway for next‐generation photocatalysts.     

Effect of substrates on epitaxy of Bi4Ti3O12 thin films by dipping—pyrolysis process

Bismuth titanate (Bi₄Ti₃O₁₂) thin films have been prepared on various substrates by the dipping—pyrolysis process using metal naphthenates as starting materials. The crystallinity and in-plane alignment of the films are analysed by X-ray diffraction θ-2θ scans and β scans (polar diagrams), respectively. Highly c-axis-oriented Bi₄Ti₃O₁₂ thin films with smooth surfaces are obtained by heat treatment at 750°C on SrTiO₃ (100), LaAlO₃ (100) and MgO (100) substrates, while films grown on Si (100) exhibit polycrystalline characteristics. The fluctuation of in-plane alignment of epitaxially grown films depends on the lattice-misfit values between the films and the substrates used; Bi₄Ti₃O₁₂ films on MgO shows the largest full width at half maximum values in their β scans.     

Atomic Interface Engineering and Electric‐Field Effect in Ultrathin Bi2MoO6 Nanosheets for Superior Lithium Ion Storage

Ultrathin 2D materials can offer promising opportunities for exploring advanced energy storage systems, with satisfactory electrochemical performance. Engineering atomic interfaces by stacking 2D crystals holds huge potential for tuning material properties at the atomic level, owing to the strong layer–layer interactions, enabling unprecedented physical properties. In this work, atomically thin Bi₂MoO₆ sheets are acquired that exhibit remarkable high‐rate cycling performance in Li‐ion batteries, which can be ascribed to the interlayer coupling effect, as well as the 2D configuration and intrinsic structural stability. The unbalanced charge distribution occurs within the crystal and induces built‐in electric fields, significantly boosting lithium ion transfer dynamics, while the extra charge transport channels generated on the open surfaces further promote charge transport. The in situ synchrotron X‐ray powder diffraction results confirm the material's excellent structural stability. This work provides some insights for designing high‐performance electrode materials for energy storage by manipulating the interface interaction and electronic structure.     

Large‐Scale Growth and Field‐Effect Transistors Electrical Engineering of Atomic‐Layer SnS2

2D layers of metal dichalcogenides are of considerable interest for high‐performance electronic devices for their unique electronic properties and atomically thin geometry. 2D SnS₂ nanosheets with a bandgap of ≈2.6 eV have been attracting intensive attention as one potential candidate for modern electrocatalysis, electronic, and/or optoelectronic fields. However, the controllable growth of large‐size and high‐quality SnS₂ atomic layers still remains a challenge. Herein, a salt‐assisted chemical vapor deposition method is provided to synthesize atomic‐layer SnS₂ with a large crystal size up to 410 µm and good uniformity. Particularly, the as‐fabricated SnS₂ nanosheet‐based field‐effect transistors (FETs) show high mobility (2.58 cm² V^?1 s^?1) and high on/off ratio (≈10⁸), which is superior to other reported SnS₂‐based FETs. Additionally, the effects of temperature on the electrical properties are systematically investigated. It is shown that the scattering mechanism transforms from charged impurities scattering to electron–phonon scattering with the temperature. Moreover, SnS₂ can serve as an ideal material for energy storage and catalyst support. The high performance together with controllable growth of SnS₂ endow it with great potential for future applications in electrocatalysis, electronics, and optoelectronics.     

Solution-sol-gel processing of superconductors

Bulk materials and thin films of pure and homogeneous YBa₂Cu₃O_7−x and Bi₂Sr₂CaCu₂O_8+x compounds were prepared by a nanocomposite solution-sol-gel (SSG) method. The superconducting oxides of YBa₂Cu₃O_7−x and Bi₂Sr₂CaCu₂O_8+x were prepared at very low temperatures i.e. 750°C and 850°C, respectively by SSG method. Pellets sintered from these nanophasic sol powders showed sharp resistivity drops atT _c ∼ 90°K for YBa₂Cu₃O_7−x andT _c∼67°K for Bi₂Sr₂CaCu₂O_8+x . Thin films were prepared using triphasic sol of Y, Ba, Cu and tetraphasic sol of Bi, Sr, Ca and Cu on MgO and SrTiO₃ substrates. The triphasic sol coated on SrTiO₃ substrates and calcined at 800°C for 12h showed the formation of superconducting phase, YBa₂Cu₃O_7−x with preferred orientation along theC-axis. X-ray diffraction patterns of the Bi₂Sr₂CaCu₂O_8+x films on MgO substrate showed the formation of the superconducting phase with preferential orientation along the C-axis and the microwave absorption data as a function of temperature of this film revealed the onset temperature to be 90°K.     

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.     

A Chemical Route to Monolithic Integration of Crystalline Oxides on Semiconductors

This work demonstrates the growth of crystalline SrTiO₃ (STO) directly on germanium via a chemical method. After thermal deoxidation, the Ge substrate is transferred in vacuo to the deposition chamber where a thin film of STO (2 nm) is deposited by atomic layer deposition (ALD) at 225 °C. Following post‐deposition annealing at 650 °C for 5 min, the STO film becomes crystalline with epitaxial registry to the underlying Ge (001) substrate. Thicker STO films (up to 15 nm) are then grown on the crystalline STO seed layer. The crystalline structure and orientation are confirmed via reflection high‐energy electron diffraction, X‐ray diffraction, and transmission electron microscopy. Electrical measurements of a 15‐nm thick epitaxial STO film on Ge show a large dielectric constant (k ≈ 90), but relatively high leakage current of ≈10 A/cm² for an applied field of 0.7 MV/cm. To suppress the leakage current, an aluminum precursor is cycled during ALD growth to grow crystalline Al‐doped STO (SrTi_1‐x­Al_xO_3‐δ) films. With sufficient Al doping (≈13%), the leakage current decreases by two orders of magnitude for an 8‐nm thick film. The current work demonstrates the potential of ALD‐grown crystalline oxides to be explored for advanced electronic applications, including high‐mobility Ge‐based transistors.     

Epitaxial Bi2FeCrO6 Multiferroic Thin Film as a New Visible Light Absorbing Photocathode Material

Ferroelectric materials have been studied increasingly for solar energy conversion technologies due to the efficient charge separation driven by the polarization induced internal electric field. However, their insufficient conversion efficiency is still a major challenge. Here, a photocathode material of epitaxial double perovskite Bi₂FeCrO₆ multiferroic thin film is reported with a suitable conduction band position and small bandgap (1.9–2.1 eV), for visible‐light‐driven reduction of water to hydrogen. Photoelectrochemical measurements show that the highest photocurrent density up to ?1.02 mA cm^?2 at a potential of ?0.97 V versus reversible hydrogen electrode is obtained in p‐type Bi₂FeCrO₆ thin film photocathode grown on SrTiO₃ substrate under AM 1.5G simulated sunlight. In addition, a twofold enhancement of photocurrent density is obtained after negatively poling the Bi₂FeCrO₆ thin film, as a result of modulation of the band structure by suitable control of the internal electric field gradient originating from the ferroelectric polarization in the Bi₂FeCrO₆ films. The findings validate the use of multiferroic Bi₂FeCrO₆ thin films as photocathode materials, and also prove that the manipulation of internal fields through polarization in ferroelectric materials is a promising strategy for the design of improved photoelectrodes and smart devices for solar energy conversion.