Efficient Carrier Transport in 2D Bi2O2Se/CsBi3I10 Perovskite Heterojunction Enables Highly-Sensitive Broadband Photodetection.

2D Bi2O2Se has recently garnered significant attention in the electronics and optoelectronics fields due to its remarkable photosensitivity, broad spectral absorption, and excellent long-term environmental stability. However, the development of integrated Bi2O2Se photodetector with high performance and low-power consumption is limited by material synthesis method and the inherent high carrier concentration of Bi2O2Se. Here, a type-I heterojunction is presented, comprising 2D Bi2O2Se and lead-free bismuth perovskite CsBi3I10, for fast response and broadband detection. Through effective charge transfer and strong coupling effect at the interfaces of Bi2O2Se and CsBi3I10, the response time is accelerated to 4.1 µs, and the detection range is expanded from ultraviolet to near-infrared spectral regions (365-1500 nm). The as-fabricated photodetector exhibits a responsivity of 48.63 AW-1 and a detectivity of 1.22×1012 Jones at 808 nm. Moreover, efficient modulation of the dominant photocurrent generation mechanism from photoconductive to photogating effect leads to sensitive response exceeding 103 AW-1 for heterojunction-based photo field effect transistor (photo-FETs). Utilizing the large-scale growth of both Bi2O2Se and CsBi3I10, the as-fabricated integrated photodetector array demonstrates outstanding homogeneity and stability of photo-response performance. The proposed 2D Bi2O2Se/CsBi3I10 perovskite heterojunction holds promising prospects for the future-generation photodetector arrays and integrated optoelectronic systems.

Controlled Growth of Large-Sized and Phase-Selectivity 2D GaTe Crystals.

GaTe has recently attracted significant interest due to its direct bandgap and unique phase structure, which makes it a good candidate for optoelectronics. However, the controllable growth of large-sized monolayer and few-layer GaTe with tunable phase structures remains a great challenge. Here the controlled growth of large-sized GaTe with high quality, chemical uniformity, and good reproducibility is achieved through liquid-metal-assisted chemical vapor deposition method. By using liquid Ga, the rapid growth of 2D GaTe flakes with high phase-selectivity can be obtained due to its reduced reaction temperature. In addition, the method is used to synthesize many Ga-based 2D materials and their alloys, showing good universality. Raman spectra suggest that the as-grown GaTe own a relatively weak van der Waals interaction, where monoclinic GaTe displays highly-anisotropic optical properties. Furthermore, a p-n junction photodetector is fabricated using GaTe as a p-type semiconductor and 2D MoSe2 as a typical n-type semiconductor. The GaTe/MoSe2 heterostructure photodetector exhibits large photoresponsivity of 671.52 A W-1 and high photo-detectivity of 1.48 × 1010 Jones under illumination, owing to the enhanced light absorption and good quality of as-grown GaTe. These results indicate that 2D GaTe is a promising candidate for electronic and photoelectronic devices.

Self-templated formation of (NiCo)9S8 yolk-shelled spheres for high-performance hybrid supercapacitors.

Rational materials design for the synthesis of desirable hollow micro- and nanostructures has recently revealed the remarkable potential for high-performance energy storage and conversion devices. Owing to their unique "core-void-shell" structural configurations, yolk-shell-structured electrode materials can achieve intimate contact with the electrolyte and alleviate the volume expansion issue during electrochemical cycling, which is therefore poised to further boost the electrochemical properties of hybrid supercapacitors. Herein, a facile self-templated strategy, consisting of a hydrothermal step and a high-temperature sulfurization process, has been developed for the construction of yolk-shell (NiCo)9S8 spheres in situ coated by graphite carbon ((NiCo)9S8/GC) due to the non-equilibrium thermal treatment of alkali metal alkoxides. The as-synthesized yolk-shelled sphere exhibits a high specific capacitance of 1434.4 F g-1 (179.3 mA h g-1) at a current density of 1 A g-1, and good rate capability and cycling stability with 83.1% capacitance retention at 8 A g-1 over 5000 cycles. To further demonstrate its practical application, a hybrid supercapacitor device was assembled using (NiCo)9S8/GC as the battery-type positive electrode and activated carbon (AC) as the capacitive-type electrode. The as-fabricated device can reach a wide voltage window of up to 1.6 V, deliver a high energy density of 55.6 W h kg-1 at a power density of 800.3 W kg-1 and maintain 90.2% of specific capacitance after 3000 cycles.

High-performance mesoporous γ-Fe2O3 sphere/graphene aerogel composites towards enhanced lithium storage.

Transition metal oxides have recently been demonstrated as highly attractive anodes for high-capacity lithium ion batteries, whose electrochemical properties could be further improved through rational architecture design and incorporating reliable conductive network. Herein, mesoporous γ-Fe2O3 spheres/graphene aerogel composites were synthesized via a solvothermal pathway followed by suitable annealing. Experimental results reveal the uniform mesoporous structure and well-dispersed γ-Fe2O3 spheres with the size of 300-400 nm embedded in the mesopores of the graphene aerogel network. Compared with α-Fe2O3/graphene aerogel and pure γ-Fe2O3, the as-synthesized composite delivers, at the first cycle, a high discharging capacity of 1080 mAh g-1 at current density of 200 mA g-1. Even at much higher current density of 8000 mA g-1, satisfactory discharging capacities of 421.5 mAh g-1 can still be achieved. Upon 100 charging-discharging cycles, the specific capacity of as high as 890.5 mAh g-1 at 200 mA g-1 is maintained. The enhanced electrochemical properties could be attributed to their favorable three-dimensional graphene aerogel network, which accounts for the improved structural stability and electronic conductivity of γ-Fe2O3 during the lithiation/delithiation process.

Selenium-rich nickel cobalt bimetallic selenides with core-shell architecture enable superior hybrid energy storage devices.

The continuous exploration of advanced electrode materials is of remarkable significance to revolutionize next-generation high-performance energy storage devices towards a green future. Benefiting from their electrochemically active sites and abundant redox centers, bimetallic selenides with desirable nanostructures recently have emerged as promising electrode alternatives for battery-supercapacitor hybrid (BSH) devices which demonstrate enormous potential in bridging the gap between electrochemical properties with high power densities (supercapacitors) and energy densities (batteries). Herein, employing the hydrothermal approach with solid Ni-Co spheres as precursors followed by the selenization process, selenide-rich bimetallic selenide spheres with a core-shell nanostructure were rationally designed and synthesized for use as the cathode electrode in superior BSH devices. The as-obtained (NiCo)9Se8/(NiCo)0.85Se (Ni-Co-Se) exhibits a high specific capacity of 164.44 mA h g-1 at a current density of 1 A g-1 with 85.72% capacity retention even after 5000 cycles at a current density of as high as 8 A g-1, suggesting its great promise in practical applications for BSH devices. By integrating activated carbon as the anode with the as-obtained bimetallic selenides as the cathode, an alkaline aqueous BSH device is fabricated and delivers a high energy density of 37.54 W h kg-1 at a high power density of 842.7 W kg-1. It is found that the excellent electrochemical performances can be ascribed to facile ion and electron transport pathways, high electrical conductivity and reliable structural robustness of the prepared selenides. Moreover, the synthetic strategy presented in this paper opens up an avenue to guide the synthesis of various anion doped bimetallic compounds towards high-performance energy conversion and storage devices.

Achieving Ultrahigh Capacity with Self-Assembled Ni(OH)2 Nanosheet-Decorated Hierarchical Flower-like MnCo2O4.5 Nanoneedles as Advanced Electrodes of Battery-Supercapacitor Hybrid Devices.

Self-assembled Ni(OH)2 nanosheet-decorated hierarchical flower-like MnCo2O4.5 nanoneedles were synthesized via a cost-effective and facile hydrothermal strategy, aiming to realize a high-capacity advanced electrode of a battery-supercapacitor hybrid (BSH) device. It is demonstrated that the as-synthesized hierarchical flower-like MnCo2O4.5@Ni(OH)2-nanosheet electrode exhibits a high specific capacity of 318 mAh g-1 at a current density of 3 A g-1 and still maintains a capacity of 263.5 mAh g-1 at a higher current density of 20 A g-1, with an extremely long cycle lifespan of 87.7% capacity retention after 5000 cycles. Moreover, using the unique core-shell structure as the cathode and hollow Fe2O3 nanoparticles/reduced graphene oxide as the anode, the BSH device delivers a high energy density of 56.53 Wh kg-1 when the power density reaches 1.9 kW kg-1, and there is an extraordinarily good cycling stability with the capacity retention rate of 90.4% after 3000 cycles. It is believed that the superior properties originate from desirable core-shell structures alleviating the impact of volume changes as well as the existence of two-dimensional Ni(OH)2 nanosheets with more active sites, thereby improving the cycle stability and achieving ultrahigh capacity. These results will provide more access to the rational material design of diverse nanostructures toward high-performance energy storage devices.

Enhanced Transmission and Self-Cleaning of Patterned Sapphire Substrates Prepared by Wet Chemical Etching Using Silica Masks.

Highly transparent and superhydrophilic sapphire with surface antireflective subwavelength structures were prepared by wet etching using colloidal monolayer silica masks. The film thicknesses of the silica masks were adjusted by the volume concentrations of polystyrene spheres. The evolution of etching morphologies of sapphire was studied, and antireflective concave pyramid nanoarrays on sapphire substrates were designed by calculation and were then prepared. The transmission and wettability of as-obtained patterned sapphire substrates were also investigated. As for sapphire with optimum surface concave micropyramid arrays, average visible transmittance can reach 91.7%, which is apparently higher than that of flat sapphire (85.5%). Moreover, the concave pyramid arrays can significantly increase the surface hydrophilicity of sapphire, exhibiting a water contact angle of 12.6° compared with 62.7° of flat sapphire. The proposed method can be an excellent strategy for preparing antireflective and self-cleaning concave micropyramid subwavelength structures on sapphire without complicated equipment and expensive raw materials.

Broad-band anti-reflective pore-like sub-wavelength surface nanostructures on sapphire for optical windows.

Compared with conventional anti-reflective film, an anti-reflective sub-wavelength surface structure provides an ideal choice for a sapphire optical window especially in harsh environments. However, it is still a challenge to obtain a sapphire anti-reflective surface microstructure because of its high hardness and chemical inertness. In this paper, combined with optical simulation, we proposed a facile method based on the anodic oxidation of aluminum film and following epitaxial annealing. Al thin film was deposited on a sapphire substrate by magnetron sputtering, and anodic oxidation was then performed to prepare surface pore-like structures on the Al film. Followed by two-step annealing, both the anodic oxidized coating and underlying unoxidized Al film were transformed totally into alumina. The parameters of anodic oxidation were analyzed to obtain the optimal pore-like structures for the antireflection in the mid-infrared and visible spectrum regions, respectively. Finally, the optimized surface sub-wavelength nanostructure on sapphire can increase the transmittance by 7% in the wavelength range of 3000-5000 nm and can increase 13.2% significantly for visible spectrum region, respectively. Meanwhile, the surface wettability can be also manipulated effectively. The preparation of surface pore-like sub-wavelength structure by the annealing of anodic oxidized aluminum film on sapphire is a feasible, economical and convenient approach and can find the applications for various optoelectronic fields.

Helical growth of aluminum nitride: new insights into its growth habit from nanostructures to single crystals.

By understanding the growth mechanism of nanomaterials, the morphological features of nanostructures can be rationally controlled, thereby achieving the desired physical properties for specific applications. Herein, the growth habits of aluminum nitride (AlN) nanostructures and single crystals synthesized by an ultrahigh-temperature, catalyst-free, physical vapor transport process were investigated by transmission electron microscopy. The detailed structural characterizations strongly suggested that the growth of AlN nanostructures including AlN nanowires and nanohelixes follow a sequential and periodic rotation in the growth direction, which is independent of the size and shape of the material. Based on these experimental observations, an helical growth mechanism that may originate from the coeffect of the polar-surface and dislocation-driven growth is proposed, which offers a new insight into the related growth kinetics of low-dimensional AlN structures and will enable the rational design and synthesis of novel AlN nanostructures. Further, with the increase of temperature, the growth process of AlN grains followed the helical growth model.

Large-scale fabrication of nanopatterned sapphire substrates by annealing of patterned Al thin films by soft UV-nanoimprint lithography.

Large-scale nanopatterned sapphire substrates were fabricated by annealing of patterned Al thin films. Patterned Al thin films were obtained by soft UV-nanoimprint lithography and reactive ion etching. The soft mold with 550-nm-wide lines separated by 250-nm space was composed of the toluene-diluted polydimethylsiloxane (PDMS) layer supported by the soft PDMS. Patterned Al thin films were subsequently subjected to dual-stage annealing due to the melting temperature of Al thin films (660°C). The first comprised a low-temperature oxidation anneal at 450°C for 24 h. This was followed by a high-temperature annealing in the range of 1,000°C and 1,200°C for 1 h to induce growth of the underlying sapphire single crystal to consume the oxide layer. The SEM results indicate that the patterns were retained on sapphire substrates after high-temperature annealing at less than 1,200°C. Finally, large-scale nanopatterned sapphire substrates were successfully fabricated by annealing of patterned Al thin films for 24 h at 450°C and 1 h at 1,000°C by soft UV-nanoimprint lithography.

[Effect of technological parameters of sputtering on the microstructure of silicon film investigated by Raman analysis].

In order to facilitate optical polishing of silicon carbide space telescope, in the present paper, silicon film, which has similar coefficient of thermal expansion with silicon carbide, was fabricated on SiC substrate by radio frequency magnetron sputtering. The effect of substrate temperature, radio frequency power, and substrate bias voltage was investigated by Raman scattering. The results indicate that at lower substrate temperature, the crystalline volume fraction of Si films increases with the increase in deposition temperature. Exceeding a certain temperature, the crystalline volume fraction decreases with further increasing deposition temperature; the increase in substrate bias voltage is bad for forming crystalline structure; the effect of radio power on microstructure of silicon film is comparatively complicated. As the rf power increases, the cluster size and crystallite volume fraction decrease, and both of them increase with further increasing the rf power. But when the rf power is too high, the crystallite volume fraction of the silicon film will decrease slightly.

Neutron irradiation and post annealing effect on sapphire by positron annihilation.

Sapphire single crystals grown by an improved Kyropoulos-like method are irradiated by fast neutron flux. The irradiated doses of neutron are 10(18) and 10(19)n/cm(2). The infrared transmission spectra of sapphire were studied before and after irradiation. The irradiated samples were annealed at 200, 400, 600, 800 and 1000 degrees C for 10min in ambient atmosphere. Positron annihilation studies have been carried out before and after neutron irradiation. The experimentally measured positron lifetime in the pristine specimen is 143ps. There were aluminum vacancies produced in sapphire crystals after neutron irradiation. The positron lifetime increased with the dose of neutron flux. A longer value tau(2) was found after annealing at 600 degrees C, which indicated vacancies were aggregated with each other. The second long-time component tau(2) has been found to increase with the annealing temperature. There was almost no change in peak position of the CDB spectra after neutron irradiation and isothermal annealing. The chemical environment of core in sapphire did not change greatly after neutron irradiation.

[XPS and Raman spectral analysis of nitrogenated tetrahedral amorphous carbon (ta-C : N) films with different nitrogen content].

Nitrogenated tetrahedral amorphous carbon (ta-C : N) films were prepared on the polished C--Si substrates by introducing highly pure nitrogen gas into the cathode region and the depositing chamber synchronously using filtered cathodic vacuum arc (FCVA) technology. The nitrogen content in the films was controlled by changing the flow rate of nitrogen gas. The configuration of ta-C : N films was investigated by means of X-ray photoelectron spectroscopy (XPS) and visible Raman spectroscopy. It was shown that the nitrogen content in the films increased from 0.84 at% to 5.37 at% monotonously when the nitrogen flow rate was varied from 2 seem to 20 sccm. The peak position of C (1s) core level moved towards higher binding energy with the increase in nitrogen content. The shift of C (1s) peak position could be ascribed to the chemical bonding between carbon and nitrogen atoms even though more three-fold coordinated sp2 configuration as in graphite was formed when the films were doped with more nitrogen atoms. Additionally, the half width of C(1s) peak gradually was also broadened with increasing nitrogen content. In order to discover clearly the changing regularities of the microstructure of the films, the XPS C(1s) spectra and Raman spectra were deconvoluted using a Gaussian-Lorentzian mixed lineshape. It was shown that the tetrahedral hybridization component was still dominant even though the ratio of sp2/sp3 obtained from C(1s) spectra rose with the increase in nitrogen content. The Raman measurements demonstrated that the G peak position shifted towards higher frequency from 1,561 to 1,578 cm(-1) and the ratio of ID/IG also rose with the increase in nitrogen content. Both results indicated that the graphitizing tendency could occur with the increase in nitrogen content in the films.

[Spectroscopic ellipsometry investigations of amorphous diamond films deposited with filtered arc].

In order to investigate thoroughly the optical properties of amorphous diamond (alpha-D) films deposited by the filtered vacuum arc technology, the optical constants of the films were measured by spectroscopic ellipsometry. Moreover, the dispersion relations of the optical constants, and the correlations among refractive index, extinction coefficient, optical gap and the substrate bias were also analyzed. It has been shown that the refractive index of alpha-D films is higher than that of diamond crystal, and the absorption edge corresponding to the interband transformation can be described with the parabolic line shape. With increasing the wavelength, the extinction coefficient gradually declines and approaches nearly to zero in the infrared band. In addition, the adjustable amplitudes of the optical constants owing to the changing bias also reduce strikingly with the extension of the wavelength. With raising the bias, the refractive index and the optical gap firstly augment, then minish, and there is a maximal value when the substrate bias is -80 V. However, the extinction coefficient firstly minishes, then augments, and there is a minimal value when the bias is -80 V.