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.     

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.     

Broadband MoS2 Field‐Effect Phototransistors: Ultrasensitive Visible‐Light Photoresponse and Negative Infrared Photoresponse

Inverse photoresponse is discovered from phototransistors based on molybdenum disulfide (MoS₂). The devices are capable of detecting photons with energy below the bandgap of MoS₂. Under the illumination of near‐infrared (NIR) light at 980 and 1550 nm, negative photoresponses with short response time (50 ms) are observed for the first time. Upon visible‐light illumination, the phototransistors exhibit positive photoresponse with ultrahigh responsivity on the order of 10⁴–10⁵ A W^?1 owing to the photogating effect and charge trapping mechanism. Besides, the phototransistors can detect a weak visible‐light signal with effective optical power as low as 17 picowatts (pW). A thermally induced photoresponse mechanism, the bolometric effect, is proposed as the cause of the negative photocurrent in the NIR regime. The thermal energy of the NIR radiation is transferred to the MoS₂ crystal lattice, inducing lattice heating and resistance increase. This model is experimentally confirmed by low‐temperature electrical measurements. The bolometric coefficient calculated from the measured transport current change with temperature is ?33 nA K^?1. These findings offer a new approach to develop sub‐bandgap photodetectors and other novel optoelectronic devices based on 2D layered materials.     

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.     

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.     

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.     

High Detectivity Solar‐Blind High‐Temperature Deep‐Ultraviolet Photodetector Based on Multi‐Layered (l00) Facet‐Oriented β‐Ga2O3 Nanobelts

Fabrication of a high‐temperature deep‐ultraviolet photodetector working in the solar‐blind spectrum range (190–280 nm) is a challenge due to the degradation in the dark current and photoresponse properties. Herein, β‐Ga₂O₃ multi‐layered nanobelts with (l00) facet‐oriented were synthesized, and were demonstrated for the first time to possess excellent mechanical, electrical properties and stability at a high temperature inside a TEM studies. As‐fabricated DUV solar‐blind photodetectors using (l00) facet‐oriented β‐Ga₂O₃ multi‐layered nanobelts demonstrated enhanced photodetective performances, that is, high sensitivity, high signal‐to‐noise ratio, high spectral selectivity, high speed, and high stability, importantly, at a temperature as high as 433 K, which are comparable to other reported semiconducting nanomaterial photodetectors. In particular, the characteristics of the photoresponsivity of the β‐Ga₂O₃ nanobelt devices include a high photoexcited current (>21 nA), an ultralow dark current (below the detection limit of 10^?14 A), a fast time response (<0.3 s), a high R_λ (≈851 A/W), and a high EQE (～4.2 × 10³). The present fabricated facet‐oriented β‐Ga₂O₃ multi‐layered nanobelt based devices will find practical applications in photodetectors or optical switches for high‐temperature environment.     

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.     

Near‐Infrared Photodetectors Based on MoTe2/Graphene Heterostructure with High Responsivity and Flexibility

2D transition metal dichalcogenides (TMDCs) have attracted considerable attention due to their impressively high performance in optoelectronic devices. However, efficient infrared (IR) photodetection has been significantly hampered because the absorption wavelength range of most TMDCs lies in the visible spectrum. In this regard, semiconducting 2D MoTe₂ can be an alternative choice owing to its smaller band gap ≈1 eV from bulk to monolayer and high carrier mobility. Here, a MoTe₂/graphene heterostructure photodetector is demonstrated for efficient near‐infrared (NIR) light detection. The devices achieve a high responsivity of ≈970.82 A W^?1 (at 1064 nm) and broadband photodetection (visible‐1064 nm). Because of the effective photogating effect induced by electrons trapped in the localized states of MoTe₂, the devices demonstrate an extremely high photoconductive gain of 4.69 × 10⁸ and detectivity of 1.55 × 10¹¹ cm Hz^1/2 W^?1. Moreover, flexible devices based on the MoTe₂/graphene heterostructure on flexible substrate also retains a good photodetection ability after thousands of times bending test (1.2% tensile strain), with a high responsivity of ≈60 A W^?1 at 1064 nm at V _DS = 1 V, which provides a promising platform for highly efficient, flexible, and low cost broadband NIR photodetectors.     

Thermoelectric properties of Bi2O2Se

Bi₂O₂Se was synthesized from Bi₂Se₃ and Bi₂O₃ by solid state reaction in an evacuated quartz ampoule. The product crystallizes in the tetragonal type lattice and X-ray pattern displays lines of the Bi₂O₂Se only. Samples for thermoelectric property measurements were prepared using hot pressing in rectangular graphite dies. The samples were characterized by the measurements of Seebeck coefficient, electrical conductivity and thermal conductivity as a function of temperature. From the experimental data we calculate the dimensionless figure of merit ZT that for a non-optimized material approaches the value 0.2 at 800 K.     

Suppression of Persistent Photoconductivity of Rubrene Crystals using Gate‐Tunable Rubrene/Bi2Se3 Diodes with Photoinduced Negative Differential Resistance

Organic single‐crystalline semiconductors show great potential in high‐performance photodetectors. However, they suffer from persistent photoconductivity (PPC) due to the charge trapping, which has severely hindered high‐speed imaging applications. Here, a universal strategy of solving the PPC by integrating with topological insulator Bi₂Se₃ is provided. The rubrene/Bi₂Se₃ heterojunctions are selected as an example for general demonstration due to the reproducibly high mobility and broad optoelectronic applications of rubrene crystals. By virtue of high carrier concentration on Bi₂Se₃ surface and the strong built‐in electrical field, the photoresponse of the heterotransistor is significantly reduced for more than two orders (from over 10 s to 54 ms), meanwhile the photoresponsivity can reach 124 A W^?1. To the best of knowledge, this operating speed is among the fastest responses in organic–inorganic heterojunctions. The heterotransistor also shows unique negative differential resistance under positive gate bias, which can be explained by photoinduced de‐trapping of electron trap states in the bulk rubrene crystals. Besides, the rubrene/Bi₂Se₃ heterojunction behaves as a gate‐tunable backward‐like diode due to the inhomogenous carrier distribution in the thick rubrene crystal and inversion of relative Fermi level positions. The findings demonstrate versatile functionalities of the rubrene/Bi₂Se₃ heterojunctions for various emerging optoelectronic applications.     

Ultrabroadband Photodetectors up to 10.6 µm Based on 2D Fe3O4 Nanosheets

The ultrabroadband spectrum detection from ultraviolet (UV) to long-wavelength infrared (LWIR) is promising for diversified optoelectronic applications of imaging, sensing, and communication. However, the current LWIR-detecting devices suffer from low photoresponsivity, high cost, and cryogenic environment. Herein, a high-performance ultrabroadband photodetector is demonstrated with detecting range from UV to LWIR based on air-stable nonlayered ultrathin Fe₃O₄ nanosheets synthesized via a space-confined chemical vapor deposition (CVD) method. Ultrahigh photoresponsivity (R) of 561.2 A W⁻¹, external quantum efficiency (EQE) of 6.6 × 10³%, and detectivity (D*) of 7.42 × 10⁸ Jones are achieved at the wavelength of 10.6 µm. The multimechanism synergistic effect of photoconductive effect and bolometric effect demonstrates the high sensitivity for light with any light intensities. The outstanding device performance and complementary mixing photoresponse mechanisms open up new potential applications of nonlayered 2D materials for future infrared optoelectronic devices.     

Influence of Bi2O3 addition on structure and dielectric properties of Ag(Nb0.8Ta0.2)O3 ceramics

The structure and dielectric properties of perovskite Ag(Nb_0.8Ta_0.2)O₃ ceramics were explored. A small amount of Bi₂O₃ was used to modify the dielectric properties of the ceramics. The addition of Bi₂O₃ led the ceramics to a high densification and optimal dielectric properties. With the addition of 4.5 wt% Bi₂O₃, the permittivity of Ag(Nb_0.8Ta_0.2)O₃ ceramics increased from 470 to 733, the dielectric loss decreased from 62×10^?4 to 6.7×10^?4, and the temperature coefficient of capacitance, TCC, decreased from 2004 ppm/°C to ?50 ppm/°C. The high permittivity obtained was due to the high densification and weak Ta-O or Nb-O bond strength in the oxygen octahedron that results from the addition of Bi₂O₃.     

Multifunctional MoS2 Transistors with Electrolyte Gel Gating

MoS₂, one of the most valued 2D materials beyond graphene, shows potential for future applications in postsilicon digital electronics and optoelectronics. However, achieving hole transport in MoS₂, which is dominated by electron transport, is always a challenge. Here, MoS₂ transistors gated by electrolyte gel exhibit the characteristics of hole and electron transport, a high on/off ratio over 10⁵, and a low subthreshold swing below 50 mV per decade. Due to the electrolyte gel, the density of electrons and holes in the MoS₂ channel reaches ≈9 × 10¹³ and 8.85 × 10¹³ cm^?2, respectively. The electrolyte gel‐assisted MoS₂ phototransistor exhibits adjustable positive and negative photoconductive effects. Additionally, the MoS₂ p–n homojunction diode affected by electrolyte gel shows high performance and a rectification ratio over 10⁷. These results demonstrate that modifying the conductance of MoS₂ through electrolyte gel has great potential in highly integrated electronics and optoelectronic photodetectors.     

Lateral Graphene‐Contacted Vertically Stacked WS2/MoS2 Hybrid Photodetectors with Large Gain

A demonstration is presented of how significant improvements in all‐2D photodetectors can be achieved by exploiting the type‐II band alignment of vertically stacked WS₂/MoS₂ semiconducting heterobilayers and finite density of states of graphene electrodes. The photoresponsivity of WS₂/MoS₂ heterobilayer devices is increased by more than an order of magnitude compared to homobilayer devices and two orders of magnitude compared to monolayer devices of WS₂ and MoS₂, reaching 10³ A W^?1 under an illumination power density of 1.7 × 10² mW cm^?2. The massive improvement in performance is due to the strong Coulomb interaction between WS₂ and MoS₂ layers. The efficient charge transfer at the WS₂/MoS₂ heterointerface and long trapping time of photogenerated charges contribute to the observed large photoconductive gain of ≈3 × 10⁴. Laterally spaced graphene electrodes with vertically stacked 2D van der Waals heterostructures are employed for making high‐performing ultrathin photodetectors.     

2D Lead Dihalides for High‐Performance Ultraviolet Photodetectors and their Detection Mechanism Investigation

2D halide semiconductors, a new family of 2D materials in addition to transition metal dichalcogenides, present ultralow dark current and high light conversion yield, which hold great potential in photoconductive detectors. Herein, a facile aqueous solution method is developed for the preparation of large‐scale 2D lead dihalide nanosheets (PbF_2‐xI_x). High‐performance UV photodetectors are successfully implemented based on 2D PbF_2‐xI_x nanosheets. By modulating the components of halogens, the bandgap of PbF_2‐xI_x nanosheets can be tuned to meet varied detection spectra. The photoresponse dependence on incident power density, wavelength, detection environment, and temperature are systematically studied to investigate their detection mechanism. For PbI₂ photodetectors, they are dominantly driven by a photoconduction mechanism and show a fast response speed and a low noise current density. A high normalized detectivity of 1.5 × 10¹² Jones and an I_ON/I_OFF ratio up to 10³ are reached. On the other hand, PbFI photodetectors demonstrate a photogating mechanism mediated by trap states showing high responsivity. The novel 2D halide materials with wide bandgaps, superior detection performance, and facile synthesis process can enrich the Van der Waals solids family and hold great potential for a wide variety of applications in advanced optoelectronics.     

Intrinsic carrier multiplication in layered Bi2O2Se avalanche photodiodes with gain bandwidth product exceeding 1 GHz

Emerging layered semiconductors present multiple advantages for optoelectronic technologies including high carrier mobilities, strong light-matter interactions, and tunable optical absorption and emission. Here, metal-semiconductor-metal avalanche photodiodes (APDs) are fabricated from Bi₂O₂Se crystals, which consist of electrostatically bound [Bi₂O₂]²⁺ and [Se]²⁻ layers. The resulting APDs possess an intrinsic carrier multiplication factor up to 400 at 7 K with a responsivity gain exceeding 3,000 A/W and bandwidth of ~ 400 kHz at a visible wavelength of 515.6 nm, ultimately resulting in a gain bandwidth product exceeding 1 GHz. Due to exceptionally low dark currents, Bi₂O₂Se APDs also yield high detectivities up to 4.6 × 10¹⁴ Jones. A systematic analysis of the photocurrent temperature and bias dependence reveals that the carrier multiplication process in Bi₂O₂Se APDs is consistent with a reverse biased Schottky diode model with a barrier height of ~ 44 meV, in contrast to the charge trapping extrinsic gain mechanism that dominates most layered semiconductor phototransistors. In this manner, layered Bi₂O₂Se APDs provide a unique platform that can be exploited in a diverse range of high-performance photodetector applications.

     

Sol–gel derived Ag-doped ZnO thin film for UV photodetector with enhanced response

Ultraviolet (UV) photodetectors based on pure zinc oxide (ZnO) and Ag-doped ZnO (Ag:ZnO) thin films with different Ag doping contents (0.05, 0.15, 0.65, 1.30 and 2.20 %) have been prepared by sol–gel technique. Photoresponse characteristics of the prepared detectors have been studied for UV radiation of λ = 365 nm and intensity = 24 μW/cm². The Ag:ZnO thin film-based photodetector having an optimum amount of 0.15 at. wt% Ag dopant exhibits a high photoconductive gain (K = 1.32 × 10³) with relatively fast recovery (T _37 % = 600 ms) and minimal persistence in comparison to other prepared photodetectors. The incorporation of Ag dopant (≤0.15 %) at Zn lattice sites (Ag_zn) in ZnO creates acceptor levels in the forbidden gap, thereby reducing the value of dark current. Upon illumination with UV radiation, the photogenerated holes recombine with the captured electrons at the Ag_zn sites. The photogenerated electrons increase the concentration of conduction electrons, thereby giving an enhanced photoresponse for Ag:ZnO photodetector (0.15 % Ag). At higher dopant concentration (≥0.65 %), Ag incorporated at the interstitial sites of ZnO leads to the formation of deep energy levels below the conduction band along with increase in oxygen-related defects, thereby giving higher values of dark current. The incorporation of Ag at interstitial sites results in degradation of photoresponse along with the appearance of persistence in recovery of the photodetector in the absence of UV radiation.     

The effect of substitution of Bi2O3 for alkali oxides on thermal properties, structure and wetting behavior of the borosilicate glass

The effect of substitution of Bi₂O₃ for alkali oxides in the borosilicate sealing glass on thermal properties, structure and wetting behavior of the borosilicate glass was studied. The thermal expansion coefficient (TEC) decreased with the substitution, however, the TEC varied little while the alkali oxides were completely consumed. The variation in glass transition temperature (T_g) and the FTIR results of the glasses indicated significant effect of Bi₂O₃ substitution on the glass structure, which caused a progressive conversion of BO₃ to BO₄ unit in the glass. The appropriate amount of Bi₂O₃ obviously improved the wetting performance of the borosilicate glass on Al₂O₃ substrate due to the high polarizability of Bi³⁺ ion.     

Bi2MoO6 dielectric thin films fabricated by thermal oxidation of Bi/Mo thin films at ultra-low temperature

Bi/Mo multilayer thin films are deposited on Si/SiO₂/Pt substrates by direct current magnetron sputtering. The effect of annealing temperature on the microstructure, dielectric and electrical properties of the as-sputtered films is characterized systematically. X-ray diffraction data indicate that the films annealed at 450–600 °C are a mixture of diphase with the main phase Bi₂MoO₆ and secondary phase Bi₂Mo₂O₉. Results of scanning electron microscope observation show that the films annealed at 500–550 °C are dense and uniform, in particular the films annealed at 500 °C exhibit optimal dielectric and electrical properties with dielectric constant as high as 37.5, dielectric loss 1.06 %, temperature coefficient of dielectric constant ?10.86 ppm °C^?1 at 1 kHz, and leakage current density of 1.46 × 10^?7 A mm^?2 at an electric field of 18.2 kV mm^?1. With the advantages of ultralow densification temperature (500 °C) and very high sputtering deposition rate (76 nm min^?1), it is anticipated that thermal oxidation method of the sputtered Bi/Mo thin films could be a promising technique for fabrication of Bi₂MoO₆ ceramic thin film embedded-capacitors.