Zn doped MAPbBr3 single crystal with advanced structural and optical stability achieved by strain compensation.

A mechanistic understanding of perovskite degradation is one of the most urgent issues to push perovskite devices toward commercial applications. Surface coverings will lower the electrical injection and light extraction efficiency of perovskites. Therefore, structural modification of Zn doped perovskites has been proposed herein. The Zn doping will induce local lattice strain due to smaller ionic radius. It is interesting that the lattice structure at atomic resolution has been observed directly through cryo-TEM. Under light illumination, the photostriction will compensate for the local lattice strain, which leads to structural stability as evidence suggests no phase transition in temperature ranges of the temperature-dependent photoluminescence spectra. In addition, MPZB also shows less than 3% decrease in PL intensity after 60 days. This is because the Zn doping induced the lowest defect density in the MPZB SC (density of trap-states ntrp = 6.33 × 108 cm-3), which has been confirmed by the high performance of the photodetector. Such strain compensation is expected to fundamentally improve the stability of photoelectric devices.

Large-Scale Ultrathin 2D Wide-Bandgap BiOBr Nanoflakes for Gate-Controlled Deep-Ultraviolet Phototransistors.

Ternary two-dimensional (2D) semiconductors with controllable wide bandgap, high ultraviolet (UV) absorption coefficient, and critical tuning freedom degree of stoichiometry variation have a great application prospect for UV detection. However, as-reported ternary 2D semiconductors often possess a bandgap below 3.0 eV, which must be further enlarged to achieve comprehensively improved UV, especially deep-UV (DUV), detection capacity. Herein, sub-one-unit-cell 2D monolayer BiOBr nanoflakes (≈0.57 nm) with a large size of 70 µm are synthesized for high-performance DUV detection due to the large bandgap of 3.69 eV. Phototransistors based on the 2D ultrathin BiOBr nanoflakes deliver remarkable DUV detection performance including ultrahigh photoresponsivity (Rλ , 12739.13 A W-1 ), ultrahigh external quantum efficiency (EQE, 6.46 × 106 %), and excellent detectivity (D*, 8.37 × 1012 Jones) at 245 nm with a gate voltage (Vg ) of 35 V attributed to the photogating effects. The ultrafast response (τrise = 102 µs) can be achieved by utilizing photoconduction effects at Vg of -40 V. The combination of photocurrent generation mechanisms for BiOBr-based phototransistors controlled by Vg can pave a way for designing novel 2D optoelectronic materials to achieve optimal device performance.

Ultrahigh-Sensitive Broadband Photodetectors Based on Dielectric Shielded MoTe2 /Graphene/SnS2 p-g-n Junctions.

2D atomic sheets of transition metal dichalcogenides (TMDs) have a tremendous potential for next-generation optoelectronics since they can be stacked layer-by-layer to form van der Waals (vdW) heterostructures. This allows not only bypassing difficulties in heteroepitaxy of lattice-mismatched semiconductors of desired functionalities but also providing a scheme to design new optoelectronics that can surpass the fundamental limitations on their conventional semiconductor counterparts. Herein, a novel 2D h-BN/p-MoTe2 /graphene/n-SnS2 /h-BN p-g-n junction, fabricated by a layer-by-layer dry transfer, demonstrates high-sensitivity, broadband photodetection at room temperature. The combination of the MoTe2 and SnS2 of complementary bandgaps, and the graphene interlayer provides a unique vdW heterostructure with a vertical built-in electric field for high-efficiency broadband light absorption, exciton dissociation, and carrier transfer. The graphene interlayer plays a critical role in enhancing sensitivity and broadening the spectral range. An optimized device containing 5-7-layer graphene has been achieved and shows an extraordinary responsivity exceeding 2600 A W-1 with fast photoresponse and specific detectivity up to ≈1013 Jones in the ultraviolet-visible-near-infrared spectrum. This result suggests that the vdW p-g-n junctions containing multiple photoactive TMDs can provide a viable approach toward future ultrahigh-sensitivity and broadband photonic detectors.

Fabrication and Characterization of ZnO Nano-Clips by the Polyol-Mediated Process.

ZnO nano-clips with better monodispersion were prepared successfully using zinc acetate hydrate (Zn(OAc)2·nH2O) as Zn source and ethylene glycol (EG) as solvent by a simple solution-based route-polyol process. The effect of solution concentration on the formation of ZnO nano-clips has been investigated deeply. We first prove that the 0.01 M Zn(OAc)2·nH2O can react with EG without added water or alkaline, producing ZnO nano-clips with polycrystalline wurtzite structure at 170 °C. As-synthesized ZnO nano-clips contain a lot of aggregated nanocrystals (~ 5 to 15 nm) with high specific surface area of 88 m2/g. The shapes of ZnO nano-clips basically keep constant with improved crystallinity after annealing at 400-600 °C. The lower solution concentration and slight amount of H2O play a decisive role in ZnO nano-clip formation. When the solution concentration is ≤ 0.0125 M, the complexing and polymerization reactions between Zn(OAc)2·nH2O and EG predominate, mainly elaborating ZnO nano-clips. When the solution concentration is ≥ 0.015 M, the alcoholysis and polycondensation reactions of Zn(OAc)2·nH2O and EG become dominant, leading to ZnO particle formation with spherical and elliptical shapes. The possible growth mechanism based on a competition between complexing and alcoholysis of Zn(OAc)2·nH2O and EG has been proposed.

Designing the Interface of Carbon Nanotube/Biomaterials for High-Performance Ultra-Broadband Photodetection.

Inorganic/biomolecule nanohybrids can combine superior electronic and optical properties of inorganic nanostructures and biomolecules for optoelectronics with performance far surpassing that achievable in conventional materials. The key toward a high-performance inorganic/biomolecule nanohybrid is to design their interface based on the electronic structures of the constituents. A major challenge is the lack of knowledge of most biomolecules due to their complex structures and composition. Here, we first calculated the electronic structure and optical properties of one of the cytochrome c (Cyt c) macromolecules (PDB ID: 1HRC ) using ab initio OLCAO method, which was followed by experimental confirmation using ultraviolet photoemission spectroscopy. For the first time, the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of Cyt c, a well-known electron transport chain in biological systems, were obtained. On the basis of the result, pairing the Cyt c with semiconductor single-wall carbon nanotubes (s-SWCNT) was predicted to have a favorable band alignment and built-in electrical field for exciton dissociation and charge transfer across the s-SWCNT/Cyt c heterojunction interface. Excitingly, photodetectors based on the s-SWCNT/Cyt c heterojunction nanohybrids demonstrated extraordinary ultra-broadband (visible light to infrared) responsivity (46-188 A W-1) and figure-of-merit detectivity D* (1-6 × 1010 cm Hz1/2 W-1). Moreover, these devices can be fabricated on transparent flexible substrates by a low-lost nonvacuum method and are stable in air. These results suggest that the s-SWCNT/biomolecule nanohybrids may be promising for the development of CNT-based ultra-broadband photodetectors.

Printable Transfer-Free and Wafer-Size MoS2/Graphene van der Waals Heterostructures for High-Performance Photodetection.

Two-dimensional (2D) MoS2/graphene van der Waals heterostructures integrate the superior light-solid interaction in MoS2 and charge mobility in graphene for high-performance optoelectronic devices. Key to the device performance lies in a clean MoS2/graphene interface to facilitate efficient transfer of photogenerated charges. Here, we report a printable and transfer-free process for fabrication of wafer-size MoS2/graphene van der Waals heterostructures obtained using a metal-free-grown graphene, followed by low-temperature growth of MoS2 from the printed thin film of ammonium thiomolybdate on graphene. The photodetectors based on the transfer-free MoS2/graphene heterostructures exhibit extraordinary short photoresponse rise/decay times of 20/30 ms, which are significantly faster than those of the previously reported MoS2/transferred-graphene photodetectors (0.28-1.5 s). In addition, a high photoresponsivity of up to 835 mA/W was observed in the visible spectrum on such transfer-free MoS2/graphene heterostructures, which is much higher than that of the reported photodetectors based on the exfoliated layered MoS2 (0.42 mA/W), the graphene (6.1 mA/W), and transfer-free MoS2/graphene/SiC heterostructures (∼40 mA/W). The enhanced performance is attributed to the clean interface on the transfer-free MoS2/graphene heterostructures. This printable and transfer-free process paves the way for large-scale commercial applications of the emerging 2D heterostructures in optoelectronics and sensors.

Wrapping cytochrome c around single-wall carbon nanotube: engineered nanohybrid building blocks for infrared detection at high quantum efficiency.

Biomolecule cytochrome c (Cty c), a small molecule of a chain of amino acids with extraordinary electron transport, was helically wrapped around a semiconductive single-wall carbon nanotube (s-SWCNT) to form a molecular building block for uncooled infrared detection with two uniquely designed functionalities: exciton dissociation to free charge carriers at the heterojunction formed on the s-SWCNT/Cty c interface and charge transport along the electron conducting chain of Cty c (acceptor) and hole conducting channel through s-SWCNT (donor). Such a design aims at addressing the long-standing challenges in exciton dissociation and charge transport in an SWCNT network, which have bottlenecked development of photonic SWCNT-based infrared detectors. Using these building blocks, uncooled s-SWCNT/Cyt c thin film infrared detectors were synthesized and shown to have extraordinary photoresponsivity up to 0.77 A W(-1) due to a high external quantum efficiency (EQE) in exceeding 90%, which represents a more than two orders of magnitude enhancement than the best previously reported on CNT-based infrared detectors with EQE of only 1.72%. From a broad perspective, this work on novel s-SWCNT/Cyt c nanohybrid infrared detectors has developed a successful platform of engineered carbon nanotube/biomolecule building blocks with superior properties for optoelectronic applications.

Detangling extrinsic and intrinsic hysteresis for detecting dynamic switch of electric dipoles using graphene field-effect transistors on ferroelectric gates.

A transition in source-drain current vs. back gate voltage (ID-VBG) characteristics from extrinsic polar molecule dominant hysteresis to anti-hysteresis induced by an oxygen deficient surface layer that is intrinsic to the ferroelectric thin films has been observed on graphene field-effect transistors on Pb0.92La0.08Zr0.52Ti0.48O3 gates (GFET/PLZT-Gate) during a vacuum annealing process developed to systematically remove the polar molecules adsorbed on the GFET channel surface. This allows the extrinsic and intrinsic hysteresis on GFET/PLZT-gate devices to detangle and the detection of the dynamic switch of electric dipoles using GFETs, taking advantage of their high gating efficiency on ferroelectric gate. A model of the charge trapping and pinning mechanism is proposed to successfully explain the transition. In response to pulsed VBG trains of positive, negative, as well as alternating polarities, respectively, the source-drain current ID variation is instantaneous with the response amplitude following the ID-VBG loops measured by DC VBG with consideration of the remnant polarization after a given VBG pulse when the gate electric field exceeds the coercive field of the PLZT. A detection sensitivity of around 212 dipole per µm(2) has been demonstrated at room temperature, suggesting the GFET/ferroelectric-gate devices provide a promising high-sensitivity scheme for uncooled detection of electrical dipole dynamic switch.

Interlayer catalytic exfoliation realizing scalable production of large-size pristine few-layer graphene.

Mass production of reduced graphene oxide and graphene nanoplatelets has recently been achieved. However, a great challenge still remains in realizing large-quantity and high-quality production of large-size thin few-layer graphene (FLG). Here, we create a novel route to solve the issue by employing one-time-only interlayer catalytic exfoliation (ICE) of salt-intercalated graphite. The typical FLG with a large lateral size of tens of microns and a thickness less than 2 nm have been obtained by a mild and durative ICE. The high-quality graphene layers preserve intact basal crystal planes owing to avoidance of the degradation reaction during both intercalation and ICE. Furthermore, we reveal that the high-quality FLG ensures a remarkable lithium-storage stability (>1,000 cycles) and a large reversible specific capacity (>600 mAh g(-1)). This simple and scalable technique acquiring high-quality FLG offers considerable potential for future realistic applications.

High-density three-dimension graphene macroscopic objects for high-capacity removal of heavy metal ions.

The chemical vapor deposition (CVD) fabrication of high-density three-dimension graphene macroscopic objects (3D-GMOs) with a relatively low porosity has not yet been realized, although they are desirable for applications in which high mechanical and electrical properties are required. Here, we explore a method to rapidly prepare the high-density 3D-GMOs using nickel chloride hexahydrate (NiCl2·6H2O) as a catalyst precursor by CVD process at atmospheric pressure. Further, the free-standing 3D-GMOs are employed as electrolytic electrodes to remove various heavy metal ions. The robust 3D structure, high conductivity (~12 S/cm) and large specific surface area (~560 m²/g) enable ultra-high electrical adsorption capacities (Cd²âº ~ 434 mg/g, Pb²âº~ 882 mg/g, Ni²âº ~ 1,683 mg/g, Cu²âº ~ 3,820 mg/g) from aqueous solutions and fast desorption. The current work has significance in the studies of both the fabrication of high-density 3D-GMOs and the removal of heavy metal ions.

Can graphene make better HgCdTe infrared detectors?

We develop a simple and low-cost technique based on chemical vapor deposition from which large-size graphene films with 5-10 graphene layers can be produced reliably and the graphene films can be transferred easily onto HgCdTe (MCT) thin wafers at room temperature. The proposed technique does not cause any thermal and mechanical damages to the MCT wafers. It is found that the averaged light transmittance of the graphene film on MCT thin wafer is about 80% in the mid-infrared bandwidth at room temperature and 77 K. Moreover, we find that the electrical conductance of the graphene film on the MCT substrate is about 25 times larger than that of the MCT substrate at room temperature and 77 K. These experimental findings suggest that, from a physics point of view, graphene can be utilized as transparent electrodes as a replacement for metal electrodes while producing better and cheaper MCT infrared detectors.

Reduced graphene oxide electrically contacted graphene sensor for highly sensitive nitric oxide detection.

We develop graphene-based devices fabricated by alternating current dielectrophoresis (ac-DEP) for highly sensitive nitric oxide (NO) gas detection. The novel device comprises the sensitive channels of palladium-decorated reduced graphene oxide (Pd-RGO) and the electrodes covered with chemical vapor deposition (CVD)-grown graphene. The highly sensitive, recoverable, and reliable detection of NO gas ranging from 2 to 420 ppb with response time of several hundred seconds has been achieved at room temperature. The facile and scalable route for high performance suggests a promising application of graphene devices toward the human exhaled NO and environmental pollutant detections.