Thermally Annealed High-Aspect-Ratio ZIF-8 Nanoplates-Incorporated Mixed Matrix Membranes for Improved H2/CO2 Selectivity.

The main challenge in the preparation of MOF-based mixed matrix membranes is to construct a good interface morphology to improve the gas separation performance and stability of the membranes. Herein, high-aspect-ratio ZIF-8 nanoplates for H2/CO2 separation membranes were synthesized by direct template conversion. The ZIF-8 nanoplates were prepared with the commercial Matrimid polymer to form MMMs by the flat scraping method. The homogeneous dispersion of high-aspect-ratio nanoplates in the membrane and the good compatibility between the filler and the matrix caused by the thermal annealing operation improve the gas separation performance and mechanical properties of MMMs. The H2/CO2 selectivity of MMMs loaded with 30 wt % ZIF-8 nanoplates increased to 10.3, and the H2 permeability was 330.1 Barrer. This synthesis method can be extended to prepare various ZIF nanoplates with elevated aspect ratios to obtain excellent performance fillers for gas separation of MMMs. In addition, the thermal annealing operation allows more efficient gas separation in polymer membranes and is a feasible way to design excellent and stable MMMs.

Effect of repeating hydrothermal growth processes and rapid thermal annealing on CuO thin film properties.

This paper presents an investigation into the influence of repeating cycles of hydrothermal growth processes and rapid thermal annealing (HT+RTA) on the properties of CuO thin films. An innovative hydrothermal method ensures homogeneous single-phase films initially. However, their electrical instability and susceptibility to cracking under the influence of temperature have posed a challenge to their utilization in electronic devices. To address this limitation, the HT+RTA procedure has been developed, which effectively eliminated the issue. Comprehensive surface analysis confirmed the procedure's ability to yield continuous films in which the content of organic compounds responsible for the formation of cracks significantly decreases. Structural analysis underscored the achieved improvements in the crystalline quality of the films. The implementation of the HT+RTA procedure significantly enhances the potential of CuO films for electronic applications. Key findings from Kelvin probe force microscopy analysis demonstrate the possibility of modulating the work function of the material. In addition, scanning capacitance microscopy measurements provided information on the changes in the local carrier concentration with each repetition. These studies indicate the increased usefulness of CuO thin films obtained from the HT+RTA procedure, which expands the possibilities of their applications in electronic devices.

P-Type ZnO Films Made by Atomic Layer Deposition and Ion Implantation.

Zinc oxide (ZnO) is a wide bandgap semiconductor that holds significant potential for various applications. However, most of the native point defects in ZnO like Zn interstitials typically cause an n-type conductivity. Consequently, achieving p-type doping in ZnO is challenging but crucial for comprehensive applications in the field of optoelectronics. In this work, we investigated the electrical and optical properties of ex situ doped p-type ZnO films. The p-type conductivity has been realized by ion implantation of group V elements followed by rapid thermal annealing (RTA) for 60 s or flash lamp annealing (FLA) on the millisecond time scale in nitrogen or oxygen ambience. The phosphorus (P)-doped ZnO films exhibit stable p-type doping with a hole concentration in the range of 1014 to 1018 cm-3, while antimony (Sb) implantation produces only n-type layers independently of the annealing procedure. Microstructural studies of Sb-doped ZnO show the formation of metallic clusters after ms range annealing and SbZn-oxides after RTA.

Heat: A powerful tool for colloidal particle shaping.

Colloidal particles of spherical shape are important building blocks for nanotechnological applications. Materials with tailored physical properties can be directly synthesized from self-assembled particles, as is the case for colloidal photonic crystals. In addition, colloidal monolayers and multilayers can be exploited as a mask for the fabrication of complex nanostructures via a colloidal lithography process for applications ranging from optoelectronics to sensing. Several techniques have been adopted to modify the shape of both individual colloidal particles and colloidal masks. Thermal treatment of colloidal particles is an effective route to introduce colloidal particle deformation or to manipulate colloidal masks (i.e. to tune the size of the interstices between colloidal particles) by heating them at elevated temperatures above a certain critical temperature for the particle material. In particular, this type of morphological manipulation based on thermal treatments has been extensively applied to polymer particles. Nonetheless, interesting shaping effects have been observed also in inorganic materials, in particular silica particles. Due to their much less complex implementation and distinctive shaping effects in comparison to dry etching or high energy ion beam irradiation, thermal treatments turn out to be a powerful and competitive tool to induce colloidal particle deformation. In this review, we examine the physicochemical principles and mechanisms of heat-induced shaping as well as its experimental implementation. We also explore its applications, going from tailored masks for colloidal lithography to the fabrication of colloidal assemblies directly useful for their intrinsic optical, thermal and mechanical properties (e.g. thermal switches) and even to the synthesis of supraparticles and anisotropic particles, such as doublets.

Research on Evolution of Relevant Defects in Heavily Mg-Doped GaN by H Ion Implantation Followed by Thermal Annealing.

This study focuses on the heavily Mg-doped GaN in which the passivation effect of hydrogen and the compensation effect of nitrogen vacancies (VN) impede its further development. To investigate those two factors, H ion implantation followed by thermal annealing was performed on the material. The evolution of relevant defects (H and VN) was revealed, and their distinct behaviors during thermal annealing were compared between different atmospheres (N2/NH3). The concentration of H and its associated yellow luminescence (YL) band intensity decrease as the thermal annealing temperature rises, regardless of the atmosphere being N2 or NH3. However, during thermal annealing in NH3, the decrease in H concentration is notably faster compared to N2. Furthermore, a distinct trend is observed in the behavior of the blue luminescence (BL) band under N2 and NH3. Through a comprehensive analysis of surface properties, we deduce that the decomposition of NH3 during thermal annealing not only promotes the out-diffusion of H ions from the material, but also facilitates the repair of VN on the surface of heavily Mg-doped GaN. This research could provide crucial insights into the post-growth process of heavily Mg-doped GaN.

Single-Phase L10-Ordered High Entropy Thin Films with High Magnetic Anisotropy.

The vast high entropy alloy (HEA) composition space is promising for discovery of new material phases with unique properties. This study explores the potential to achieve rare-earth-free high magnetic anisotropy materials in single-phase HEA thin films. Thin films of FeCoNiMnCu sputtered on thermally oxidized Si/SiO2 substrates at room temperature are magnetically soft, with a coercivity on the order of 10 Oe. After post-deposition rapid thermal annealing (RTA), the films exhibit a single face-centered-cubic phase, with an almost 40-fold increase in coercivity. Inclusion of 50 at.% Pt in the film leads to ordering of a single L10 high entropy intermetallic phase after RTA, along with high magnetic anisotropy and 3 orders of magnitude coercivity increase. These results demonstrate a promising HEA approach to achieve high magnetic anisotropy materials using RTA.

Effect of Post-Implantation Heat Treatment Conditions on Photoluminescent Properties of Ion-Synthesized Gallium Oxide Nanocrystals.

A novel and promising way for creating nanomaterials based on gallium oxide is the ion synthesis of Ga2O3 nanocrystals in a SiO2/Si dielectric matrix. The properties of nanocrystals are determined by the conditions of ion synthesis-the parameters of ion irradiation and post-implantation heat treatment. In this work, the light-emitting properties of Ga2O3 nanocrystals were studied depending on the temperature and annealing atmosphere. It was found that annealing at a temperature of 900 °C leads to the appearance of intense luminescence with a maximum at ~480 nm caused by the recombination of donor-acceptor pairs. An increase in luminescence intensity upon annealing in an oxidizing atmosphere is shown. Based on data from photoluminescence excitation spectroscopy and high-resolution transmission electron microscopy, a hypothesis about the possibility of the participation of a quantum-size effect during radiative recombination is proposed. A mechanism for the formation of Ga2O3 nanocrystals during ion synthesis is suggested, which makes it possible to describe the change in the luminescent properties of the synthesized samples with varying conditions of post-implantation heat treatment.

Heat-Annealed Zinc Oxide on Flexible Carbon Nanotube Paper and Exposed to Gradient Light to Enhance Its Photoelectric Response.

Buckypaper (BP), a flexible and porous material, exhibits photovoltaic properties when exposed to light. In this study, we employed radio frequency (RF) sputtering of zinc oxide (ZnO) followed by rapid thermal annealing to enhance the photovoltaic response of BP. We investigated the impact of various sputtering parameters, such as the gas flow ratio of argon to oxygen and deposition time, on the morphology, composition, resistivity, and photovoltaic characteristics of ZnO-modified BP. Additionally, the photovoltaic performance of the samples under different illumination modes and wavelengths was compared. It was found that optimal sputtering conditions-argon to oxygen flow ratio of 1:2, deposition time of 20 min, and power of 100 watts-resulted in a ZnO film thickness of approximately 45 nanometers. After annealing at 400 °C for 10 min, the ZnO-modified BP demonstrated a significant increase in photocurrent and photovoltage, along with a reduction in resistivity, compared to unmodified BP. Moreover, under gradient illumination, the ZnO-modified BP exhibited a photovoltage enhancement of 14.70-fold and a photocurrent increase of 13.86-fold, compared to uniform illumination. Under blue light, it showed a higher photovoltaic response than under other colors. The enhancement in photovoltaic response is attributed to the formation of a Schottky junction between ZnO and BP, an increased carrier concentration gradient, and an expanded light absorption spectrum. Our results validate that ZnO sputtering followed by annealing is an effective method for modifying BP for photovoltaic applications such as solar cells and photodetectors.

Post-synthesis Oxidation of Superparamagnetic Iron Oxide Nanoparticles to Enhance Magnetic Particle Imaging Performance.

This study investigates the impact of post-synthesis oxidation on the performance of superparamagnetic iron oxide nanoparticles (SPIONs) in magnetic particle imaging (MPI), an emerging technology with applications in diagnostic imaging and theranostics. SPIONs synthesized from iron oleate were subjected to a post-synthesis oxidation treatment with a 1% Oxygen in Argon mixture. MPI performance, gauged via signal intensity and resolution using a MOMENTUM™ scanner, was correlated to the nanoparticles' physical and magnetic properties. Post-synthesis oxidation did not alter physical attributes like size and shape, but significantly enhanced magnetic properties. Saturation magnetization increased from 52% to 93% of the bulk value for magnetite, leading to better MPI performance in terms of signal intensity and resolution. However, the observed MPI performance did not fully align with predictions based on the ideal Langevin model, indicating the need for considering factors like relaxation and shape anisotropy. The findings underscore the potential of post-synthesis oxidation as a method to fine-tune magnetic properties of SPIONs and improve MPI performance, and the need for reproducible synthesis methods that afford finely tuned control of nanoparticle size, shape, and magnetic properties.

Transient Interfacial Pattern Formation in Block Copolymer Thin Films via Sequential Thermal and Solvent Immersion Annealing.

A variety of structures encountered in nature only arise in materials under highly nonequilibrium conditions, suggesting to us that the scope for creating new functional block copolymer (BCP) structures might be significantly enlarged by embracing complex processing histories that allow for the fabrication of structures quite unlike those created under "near-equilibrium" conditions. The present work examines the creation of polymer film structures in which highly nonequilibrium processing conditions allow for the creation of entirely new types of transient BCP morphologies achieved by transitioning between different ordered states. Most previous studies of BCP materials have emphasized ordering them from their disordered state obtained from a solution film casting process, followed by a slow thermal annealing (TA) process at elevated temperatures normally well above room temperature. We have previously shown that achieving the equilibrium TA state can be accelerated by a direct solvent immersion annealing (DIA) preordering step that creates nascent ordered microstructures, followed by TA. In the present work, we examine the reverse nonequilibrium sequential processing in which we first thermally anneal the BCP film to different levels of partial (lamellar) order and then subject it to DIA to swell the lamellae. This sequential processing rapidly leads to a swelling-induced wrinkle pattern that initially grows with immersion time and can be quenched by solvent evaporation into its corresponding glassy state morphology. The article demonstrates the formation of wrinkling "defect" patterns in entangled BCP films by this sequential annealing that does not form under ordinary TA conditions. At long DIA times, these highly "defective" film structures evolve in favor of the equilibrium morphology of parallel lamellae observed with DIA alone. In conjunction with our previous study of sequential DIA + TA, the present TA + DIA study demonstrates that switching the order of these processing methods for block copolymer films gives the same final state morphology in the limit of long time as any one method alone, but with drastically different intermediate transient state morphologies. These transient morphologies could have many applications.

Mesoporous Single Atom-Cluster Fe-N/C Oxygen Evolution Electrocatalysts Synthesized with Bottlebrush Block Copolymer-Templated Rapid Thermal Annealing.

Current electrocatalysts for oxygen evolution reaction (OER) are either expensive (such as IrO2, RuO2) or/and exhibit high overpotential as well as sluggish kinetics. This article reports mesoporous earth-abundant iron (Fe)-nitrogen (N) doped carbon electrocatalysts with iron clusters and closely surrounding Fe-N4 active sites. Unique to this work is that the mechanically stable mesoporous carbon-matrix structure (79 nm in pore size) with well-dispersed nitrogen-coordinated Fe single atom-cluster is synthesized via rapid thermal annealing (RTA) within only minutes using a self-assembled bottlebrush block copolymer (BBCP) melamine-formaldehyde resin composite template. The resulting porous structure and domain size can be tuned with the degree of polymerization of the BBCP backbone, which increases the electrochemically active surface area and improves electron transfer and mass transport for an effective OER process. The optimized electrocatalyst shows a required potential of 1.48 V (versus RHE) to obtain the current density of 10 mA/cm2 in 1 M KOH aqueous electrolyte and a small Tafel slope of 55 mV/decade at a given overpotential of 250 mV, which is significantly lower than recently reported earth-abundant electrocatalysts. Importantly, the Fe single-atom nitrogen coordination environment facilitates the surface reconstruction into a highly active oxyhydroxide under OER conditions, as revealed by X-ray photoelectron spectroscopy and in situ Raman spectroscopy, while the atomic clusters boost the single atoms reactive sites to prevent demetalation during the OER process. Density functional theory (DFT) calculations support that the iron nitrogen environment and reconstructed oxyhydroxides are electrocatalytically active sites as the kinetics barrier is largely reduced. This work has opened a new avenue for simple, rapid synthesis of inexpensive, earth-abundant, tailorable, mechanically stable, mesoporous carbon-coordinated single-atom electrocatalysts that can be used for renewable energy production.

Selective CW Laser Synthesis of MoS2 and Mixture of MoS2 and MoO2 from (NH4)2MoS4 Film.

Very recently, the synthesis of 2D MoS2 and WS2 through pulsed laser-directed thermolysis can achieve wafer-scale and large-area structures, in ambient conditions. In this paper, we report the synthesis of MoS2 and MoS2 oxides from (NH4)2MoS4 film using a visible continuous-wave (CW) laser at 532 nm, instead of the infrared pulsed laser for the laser-directed thermolysis. The (NH4)2MoS4 film is prepared by dissolving its crystal powder in DI water, sonicating the solution, and dip-coating onto a glass slide. We observed a laser intensity threshold for the laser synthesis of MoS2, however, it occurred in a narrow laser intensity range. Above that range, a mixture of MoS2 and MoO2 is formed, which can be used for a memristor device, as demonstrated by other research groups. We did not observe a mixture of MoS2 and MoO3 in the laser thermolysis of (NH4)2MoS4. The laser synthesis of MoS2 in a line pattern is also achieved through laser scanning. Due to of the ease of CW beam steering and the fine control of laser intensities, this study can lead toward the CW laser-directed thermolysis of (NH4)2MoS4 film for the fast, non-vacuum, patternable, and wafer-scale synthesis of 2D MoS2.

Influence of Thermal Annealing on Mechanical and Optical Property of SiO2 Film Produced by ALD.

The application range of fused silica optical components can be expanded and the cost of fused silica components can be reduced by depositing the same material film on fused silica substrate. However, due to the different manufacturing process, the performance of ALD SiO2 film is lower than that of fused silica substrate, which also limits the use of this process. In this paper, ALD SiO2 film with different thicknesses were deposited, and then the structure and properties were tested. Finally, the ALD SiO2 film was treated via the annealing process. Transmission electron microscopy (TEM) showed that the ALD SiO2 film had good compactness and substrate adhesion. The Raman spectra showed that the ALD SiO2 film and substrate had the same structure, with only slight differences. The XRD pattern showed that ALD-fused silica did not crystallize before or after annealing. The infrared spectra showed that there was an obvious Si-OH defect in the ALD SiO2 film. The laser damage showed that the ALD SiO2 film had a much lower damage threshold than the fused silica substrate. The nanoindentation showed that the mechanical properties of the ALD SiO2 film were much lower than those of the fused silica substrate. After a low-temperature annealing treatment, the ALD SiO2 film Si-OH defect was reduced, the ALD SiO2 film four-member ring content was increased, the elastic modulus of the ALD SiO2 film was increased from 45.025 GPa to 68.025 GPa, the hardness was increased from 5.240 GPa to 9.528 GPa, and the ALD SiO2 film damage threshold was decreased from 5.5 J/cm2 to 1.3 J/cm2.

Tuning the Inter-Nanoplatelet Distance and Coupling Strength by Thermally Induced Ligand Decomposition.

CdSe nanoplatelets (NPLs) are promising 2D semiconductors for optoelectronic applications, in which efficient charge transport properties are desirable. It is reported that thermal annealing constitutes an effective strategy to control the optical absorption and electrical properties of CdSe NPLs by tuning the inter-NPL distance. Combining optical absorption, transmission electron microscopy, and thermogravimetric analysis, it is revealed that the thermal decomposition of ligands (e.g., cadmium myristate) governs the inter-NPL distance and thus the inter-NPL electronic coupling strength. Employing ultrafast terahertz spectroscopy, it is shown that this enhanced electronic coupling increases both the free carrier generation efficiency and the short-range mobility in NPL solids. The results show a straightforward method of controlling the interfacial electronic coupling strength for developing functional optoelectronic devices through thermal treatments.

Grain-size adjustment in Hf0.5Zr0.5O2ferroelectric film to improve the switching time in Hf0.5Zr0.5O2-based ferroelectric capacitor.

By adjusting the rising time in annealing ferroelectric HfO2-based films, the grain size of the film can be controlled. In this study, we found that increasing the rising time from 10 to 30 s at an annealing temperature of 700 °C in N2atmosphere resulted in improved ferroelectric switching speed. This is because the larger grain size reduces the internal resistance components, such as the grain bulk resistance and grain boundary resistance, of the HZO film. This in turn lowers the overall equivalent resistance. By minimizing the RC time constants, increasing the grain size plays a key role in improving the polarization switching speed of ferroelectric films.

Wetting state and mechanical property alteration for the Fe3Si films using rapid thermal annealing under various temperatures.

The current research demonstrates the modification of the wetting behavior and mechanical features as well as structure and morphology of Fe3Si films created via facing target sputtering by the rapid thermal annealing (RTA) with the set RTA temperatures (TRTA) of 200, 400, 600, and 800 °C. Following the RTA process, the crystallinity of Fe3Si developed under 400 °C or below. At the 600 °C and 800 °C TRTA, new crystal orientations emerged for FeSi and then ß-FeSi2, respectively. Together with composition results, the Fe3Si films were proven to change into FeSi and then FeSi2 under a high TRTA regime. At temperatures of 600 °C and 800 °C, large crystallites, including the scraggly interface, were observed. The root-mean-square roughness roughened slightly according to the RTA process at TRTA of 600 °C or above. The hydrophobic properties of the Fe3Si film surfaces became hydrophilic after the RTA procedure at a TRTA value above 400 °C. The hardness value of the Fe3Si films evidently increased through RTA at 600 °C and 800 °C. Thus, above 400 °C, the RTA process significantly alters the physical features of as-created Fe3Si films.

Hot-Pressed Super-Elastic Graphene Aerogel with Bidirectional Thermal Conduction Properties as Thermal Interface Materials.

Traditional graphene-based films normally possess high thermal conductivity (TC) only along a single direction, which is not suitable for thermal interface materials (TIMs). Here, a graphene film with excellent bidirectional TC and mechanical properties was prepared by hot-pressing super-elastic graphene aerogel (SEGA). Thermal annealing at 1800 °C improves the further restacking of graphene sheets, bringing high structure stability to SEGA for enduring the hot-pressing process. The junctions and nodes between the graphene layers in the hot-pressed SEGA (HPSEGA) film provide bidirectional heat transport paths. The in-plane TC and through-plane TC of HPSEGA film with a thickness of 101 µm reach 740 Wm-1K-1 and 42.5 Wm-1K-1, respectively. In addition, HPSEGA film with higher thickness still maintains excellent thermal transport properties due to the interconnected structure reducing the effect of the defects. The infrared thermal images visually manifest the excellent thermal-transfer capability and thermal-dissipation efficiency of the HPSEGA films, indicating the great potential as advanced bidirectional TIMs.

Tunable Ga2O3solar-blind photosensing performance via thermal reorder engineering and energy-band modulation.

As an ultra-wide bandgap semiconductor, gallium oxide (Ga2O3) has been extensively applied in solar-blind photodetectors (PDs) owing to the absorbance cut-off wavelength of shorter than 280 nm, and the optimized technologies of detection performance is seriously essential for its further usages. Herein, a feasible thermal reorder engineering method was performed through annealing Ga2O3films in vacuum, O2and oxygen plasma atmospheres, realizing to tune solar-blind photosensing performance of Ga2O3PDs. Thermal treatment, in fact a crystal reorder process, significantly suppressed the noise in Ga2O3-based PDs and enhanced the photo-sensitivity, with the dark current decreasing from 154.63 pA to 269 fA and photo-to-dark current ratio magically raising from 288 to 2.85 × 104. This achievement is dependent of energy-band modulation in Ga2O3semiconductor, that is certified by first-principles calculation. Additionally, annealing in oxygen atmospheres notably reduces the concentration of oxygen vacancies in the surface of films, thereby improving the performance of the PDs; the oxygen vacancy is extremely concerned in oxide semiconductors in the view of physics of surface defects. In all, this work could display a promising guidance for modulating the performance of PDs based on wide bandgap oxide semiconductor, especially for hot Ga2O3issue.

High photoresponsivity MoS2phototransistor through enhanced hole trapping HfO2gate dielectric.

Phototransistor using 2D semiconductor as the channel material has shown promising potential for high sensitivity photo detection. The high photoresponsivity is often attributed to the photogating effect, where photo excited holes are trapped at the gate dielectric interface that provides additional gate electric field to enhance channel charge carrier density. Gate dielectric material and its deposition processing conditions can have great effect on the interface states. Here, we use HfO2gate dielectric with proper thermal annealing to demonstrate a high photoresponsivity MoS2phototransistor. When HfO2is annealed in H2atmosphere, the photoresponsivity is enhanced by an order of magnitude as compared with that of a phototransistor using HfO2without annealing or annealed in Ar atmosphere. The enhancement is attributed to the hole trapping states introduced at HfO2interface through H2annealing process, which greatly enhances photogating effect. The phototransistor exhibits a very large photoresponsivity of 1.1 × 107A W-1and photogain of 3.3 × 107under low light illumination intensity. This study provides a processing technique to fabricate highly sensitive phototransistor for low optical power detection.

Thermal annealing promoted room temperature phosphorescence: motion models and internal mechanism.

Thermal annealing has been proven to be an efficient method to optimize the device performance of organic and polymeric opto-electronic materials. However, no detailed information of aggregate structures was obtained for a deeper understanding of what happens during thermal annealing. Herein, through modulation of molecular configurations by tunable linkage positions, and the amplified amplitudes of molecular motions by incorporation of additional methylene units, accurate changes of aggregated structures upon thermal annealing have been achieved, accompanying with the 'turn-on' room temperature phosphorescence (RTP) response by about 4800- and 177-fold increase of lifetimes. The stretching and swing motion models have been proposed, which afforded an efficient way to investigate the science of dynamic aggregation in depth.