Thermal Annealing Research Articles

Investigations for the heat treatment effects on permeability of some semi-permeable membranes

The current study aims to devise a mechanism that can regulate the permeability of semi-permeable membranes, either by enhancing or reducing it, based on their intended application. This approach seeks to offer a straightforward and efficient method for controlling membrane permeability. Cellulose acetate (CA) and cellulose triacetate (CTA) membranes were subjected to two different heat treatment processes. One method involved thermal annealing at relatively high temperatures, while the other method involved freezing the membranes when they were saturated with water. A special osmosis cell was designed and utilized to quantify the flow rates across the treated CA and CTA membranes. Our findings indicate that subjecting the membranes to high-temperature annealing decreased the flow rate. Conversely, the freezing treatment boosted the flow rate, thereby enhancing membrane permeability. This approach could pave the way for numerous applications across various fields.

Enhanced Performance of Polymer Solar Cells by Ultraviolet-Ozone Treatment of MoOX Films with non-Thermal Annealing Treatment of MoOX Films

Molybdenum oxide (MoOX) is a commonly used hole extraction material (HEL) in polymer solar cells (PSCs). Here, we perform ultraviolet ozone treatment (UVO, non-thermal annealing treatment) on MoOX film (by spin-coated (NH4)6Mo7O24-4H2O solution on the ITO top) prepared by solution processing to develop hole extraction materials for efficient PSC. After UVO treatment of MoOX films (US-MoOX), the (NH4)6Mo7O24-4H2O molecules decompose to form a denser and higher energy levels MoOX film. Compared with E-MoOX films (vacuum evaporated MoO3 powder), US-MoOX films have similar square resistance and electrical conductivity to E-MoOX films, and the photovoltaic performance of US-MoOX-based PSCs is comparable to that of E-MoOX-based PSCs and higher than that of PEDOT:PSS-based PSCs. Therefore, US-MoOX-based PSCs show the advantages of combining high photovoltaic performance with solution processing. In addition, US-MoOX-based PSCs have the advantage of not requiring thermal annealing treatment. The results indicate that US-MoOX films are promising HEL materials for the practical production of PSCs.

Crystallinity Control and Strain Release in Wide-Bandgap Perovskite Film via Seed-Induced Growth for Efficient Photovoltaics.

The seed method stands out as a straightforward and efficient approach for fabricating high-performance perovskite solar cells (PSCs). In this study, we propose the utilization of an antisolvent as an additive to induce crystal seeding, thereby facilitating the growth of wide-bandgap perovskite grains. Specifically, we introduce three commonly used antisolvents─ethyl acetate (EA), isopropanol (IPA), and chlorobenzene (CB)─directly into the perovskite precursor solution to generate perovskite seeds, which serve to promote subsequent nucleation. This antisolvent-crystal seeding method (ACSM) results in increased grain sizes, reduced film defects, and overall improved film quality. Consequently, the power conversion efficiencies (PCEs) of 1.647 eV PSCs with EA, IPA, and CB additives are recorded at 19.86%, 20.61%, and 20.45%, respectively, surpassing that of the reference device with a PCE of 18.83%. Furthermore, the stability of the PSCs prepared through ACSM is notably enhanced. Notably, PSCs optimized with IPA retain 75% of the original PCE after being stored in ambient air conditions (25 °C, RH ∼ 15%) for 30 days, better than the CB-added (64%) and the EA-added devices (53%), while the reference devices only retain 31% of the initial PCE. Moreover, even after continuous thermal annealing at 50 °C for 200 h, IPA-assisted devices demonstrate the best stability, followed by those with CB and EA, with the reference exhibiting the poorest stability.

Optimizing the Performance of the Atomic-Layer-Deposited Zinc–Tin-Oxide Thin Film Transistor by Ozone Treatment and Thermal Annealing

Optimizing the Performance of the Atomic-Layer-Deposited Zinc–Tin-Oxide Thin Film Transistor by Ozone Treatment and Thermal Annealing

Coffee-Ring Mediated Thinning and Thickness-Dependent Dewetting Modes in Printed Polymer Droplets Coupled with Assembly of Quantum Dots for Anti-Counterfeiting.

Molecular transport processes in printed polymer droplets hold enormous importance for understanding wetting phenomena and designing systems in applications such as encoding, electronics, photonics, and sensing. This paper studies thickness-dependent dewetting modes that are activated by thermal annealing and driven by interfacial interactions within microscopically confined polymeric features. The printing of poly(2-vinylpyridine) is performed in a regime where coffee-ring effects lead to strong thinning of the central region of the deposit. Thermal annealing leads to two different modes of dewetting that depend on the thickness of the central region. Mode I refers to the formation of randomly positioned small features surrounded by large hemispherical ones located along the periphery of the printed features and occurs when the central regions are thin. Observed at large central thicknesses, Mode II mediates significant molecular transport from edges toward the center of the printed droplet with thermal annealing and forms a hemispherical feature from the initial ring-like deposit. The selective adsorption of red, green, and blue emitting quantum dots over the poly(2-vinylpyridine) results in photoluminescent patterns. The selective assembly of photoluminescent quantum dots over patterned surfaces leads to deterministic and stochastic features beneficial to creating security labels for anti-counterfeiting applications.

Acoustically driven ferromagnetic resonance in YIG thin films

Acoustically driven ferromagnetic resonance (ADFMR) is a platform that enables efficient generation and detection of spin waves via magnetoelastic coupling with surface acoustic waves (SAWs). While previous studies successfully achieved ADFMR in ferromagnetic metals, there are only few reports on ADFMR in magnetic insulators such as yttrium iron garnet (Y3Fe5O12, YIG) despite more favorable spin wave properties, including low damping and long coherence length. The growth of high-quality YIG films for ADFMR devices is a major challenge due to poor lattice-matching and thermal degradation of the piezoelectric substrates during film crystallization. In this work, we demonstrate ADFMR of YIG thin films on LiNbO3 (LNO) substrates. We employed a SiOx buffer layer and rapid thermal annealing for crystallization of YIG films with minimal thermal degradation of LNO substrates. Optimized ADFMR device designs and time-gating measurements were used to enhance the ADFMR signal and overcome the intrinsically low magnetoelastic coupling of YIG. YIG films have a polycrystalline structure with an in-plane easy direction due to biaxial stresses induced during cooling after crystallization. The YIG device shows clear ADFMR patterns with maximum absorption for H ≈ 160 mT parallel to SAW propagation, which is consistent with our simulation results based on existing theoretical models. These results expand possibilities for developing efficient spin wave devices with magnetic insulators.

Hyperdoping of germanium with argon toward strain-doping-induced indirect-to-direct bandgap transition in Ge

The first-principles calculations have recently shown that implanting sufficient noble gas atoms into germanium (Ge) can expand its lattice to achieve the desired tensile strain for indirect-to-direct bandgap transition to develop the on-chip high-efficient light emitter. Here, to experimentally prove this strain-doping concept, we implant argon (Ar) ions into Ge and then recrystallize the Ar-doped amorphous Ge (a-Ge) layer using nanosecond laser annealing (NLA) and furnace thermal annealing (FTA), respectively. The NLA effectively recrystallizes the 12 nm thick a-Ge layer with minimal loss of Ar dopants, while FTA fails to fully recrystallize it and results in significant loss of Ar dopants. The regrown Ge layer with Ar concentration above the critical value (0.8%) for bandgap transition is 3.8 nm thick, making it a challenge to distinguish the photoluminescence signal of strain-doped layer from the substrate. To overcome this, increasing the implantation energy and adding a capping layer may be necessary to further prevent Ar loss and achieve a strain-doped layer with sufficient depth. These findings provide promising view of the strain-doping concept for direct-bandgap emission from Ge.

Phase change composite based on lignin carbon aerogel/nickel foam dual-network for multisource energy harvesting and superb EMI shielding

With the increasingly rapid pace of updates and iterations in electronic devices, electronic equipment/systems are becoming progressively intricate, aiming to achieve swift responsiveness through higher packaging density, which leads to electromagnetic interference and brings along with it heat accumulation, the creation of new composite phase change materials with efficient thermal management capabilities integrated with excellent electromagnetic interference shielding capabilities is imminent. In this study, nickel foam/lignin/rGO dual network scaffolds (LGN) with high electrical conductivity were prepared by vacuum-assisted adsorption, freeze-drying, and thermal annealing, and then PEG was encapsulated in LGN by vacuum impregnation to obtain shape-stabilized PEG/NiF/LN-rGO (PLGN) composite phase change material. The results demonstrate that the prepared PLGNs exhibit robust stability, exceptional thermal management capabilities, and commendable electromagnetic interference (EMI) shielding effectiveness (SE). Among these composites, PLGN-3 stands out with a notably high energy storage density, featuring a melting enthalpy of 140.95 J/g and a relative enthalpy efficiency of 98.72%. Benefiting from its outstanding electrical conductivity (1597.5 S/cm for PLGN-3) and superior light absorption, the PLGN composite phase change material also demonstrates highly effective photothermal and electrothermal conversion capabilities. In addition, the EMI shielding effectiveness reaches up to 69.9 dB at 8.2–12.4 GHz. In conclusion, the synthesized PLGN composite phase change material demonstrates considerable promise for mitigating electromagnetic interference and facilitating thermal energy management in electronic devices.

Discovery of Crystallizable Organic Semiconductors with Machine Learning.

Crystalline organic semiconductors are known to have improved charge carrier mobility and exciton diffusion length in comparison to their amorphous counterparts. Certain organic molecular thin films can be transitioned from initially prepared amorphous layers to large-scale crystalline films via abrupt thermal annealing. Ideally, these films crystallize as platelets with long-range-ordered domains on the scale of tens to hundreds of microns. However, other organic molecular thin films may instead crystallize as spherulites or resist crystallization entirely. Organic molecules that have the capability of transforming into a platelet morphology feature both high melting point (Tm) and crystallization driving force (ΔGc). In this work, we employed machine learning (ML) to identify candidate organic materials with the potential to crystallize into platelets by estimating the aforementioned thermal properties. Six organic molecules identified by the ML algorithm were experimentally evaluated; three crystallized as platelets, one crystallized as a spherulite, and two resisted thin film crystallization. These results demonstrate a successful application of ML in the scope of predicting thermal properties of organic molecules and reinforce the principles of Tm and ΔGc as metrics that aid in predicting the crystallization behavior of organic thin films.

In Situ Characterization of Metastable Pb3O5 and Pb2O3 Phases During Thermal Decomposition of PbO2 to PbO.

Nonstoichiometric lead oxides play a key role in the formation and cycling of the positive electrodes in a lead acid battery. These phases have been linked to the underutilization of the positive active material but also play a key role in the battery's cycle life, providing interparticle adhesion and the connection to the underlying lead grid. Similar phases have previously been identified by mass loss or color change during thermal annealing of PbO2 to PbO, suggesting that at least two intermediate PbOx phases exist. Using multiple, in situ analysis techniques (powder diffraction, X-ray absorption, X-ray photoelectron spectroscopy) and ex situ nuclear magnetic resonance measurements, the structural conversion and changes in the lead oxidation state were identified during this process. Isolation of the PbOx phases enabled confirmation of Pb3O5 and Pb2O3 by diffraction and the first 207Pb NMR measurement of these intermediates. The thermodynamic and kinetic stability of these intermediates and other reported polymorphs were determined by density functional theory, providing key insight into their origins and variation of PbOx structures found in previous studies.

Influence of high-temperature thermal annealing on paramagnetic point defects in silicon-rich silicon nitride films formed in a single-wafer-type low-pressure chemical vapor deposition reactor

The influence of high-temperature thermal annealing on silicon dangling bonds called K centers in Si-rich silicon nitride films grown in a single-wafer-type low-pressure chemical vapor deposition reactor with the SiH2Cl2-NH3 system at 750 °C has been investigated by combining thermal desorption spectroscopy (TDS), Fourier transform infrared spectroscopy-attenuated total reflection, spectroscopic ellipsometry, and electron spin resonance. In the TDS analysis, H2 desorption from the nitride films was detected above about 600 °C. It is found that thermal annealing at 750 and 900 °C caused a slight decrease in the K center density and a change in the g value of K centers, which are considered to be caused by changes in the atomic structure of the nitride films. On the other hand, thermal annealing at 1050 °C resulted in a substantial decrease in the K center density and the generation of paramagnetic defects with unprecedented characteristics. The findings in this study are expected to provide important guidelines for the design of manufacturing processes of nonvolatile memories.

Preparation of the superhydrophobic polytetrafluoroethylene (PTFE) surface by doped copper to alter microtexture characteristics

A novel method for preparing the superhydrophobic polytetrafluoroethylene (PTFE) surface by doped copper (Cu) to alter microtexture (microscale warts) characteristics is proposed. Microscale warts are generated on the PTFE surface by thermal annealing. The present method achieves superhydrophobicity by adjusting Cu content to alter the morphology and distribution of microscale warts on the PTFE surface. As Cu content increases, the average area and percentage of microscale warts increase, but the density of microscale warts on the PTFE surface first increases and then decreases. An appropriate amount and size of microscale warts are obtained at 2.5 vol% Cu content. PTFE surface doped with 2.5 vol% Cu also has the best superhydrophobicity performance (water contact angle is 162.54°, water sliding angle is 5.90°).

Microsecond-Scale Transient Thermal Sensing Enabled by Flexible Mo1-xWxS2 Alloys.

Real-time thermal sensing through flexible temperature sensors in extreme environments is critically essential for precisely monitoring chemical reactions, propellant combustions, and metallurgy processes. However, despite their low response speed, most existing thermal sensors and related sensing materials will degrade or even lose their sensing performances at either high or low temperatures. Achieving a microsecond response time over an ultrawide temperature range remains challenging. Here, we design a flexible temperature sensor that employs ultrathin and consecutive Mo1-x W x S2 alloy films constructed via inkjet printing and a thermal annealing strategy. The sensing elements exhibit a broad work range (20 to 823 K on polyimide and 1,073 K on flexible mica) and a record-low response time (about 30 μs). These properties enable the sensors to detect instantaneous temperature variations induced by contact with liquid nitrogen, water droplets, and flames. Furthermore, a thermal sensing array offers the spatial mapping of arbitrary shapes, heat conduction, and cold traces even under bending deformation. This approach paves the way for designing unique sensitive materials and flexible sensors for transient sensing under harsh conditions.

Pentaerythritol-DOPA (PE-DOPA): A tetra-catechol derivative for versatile hydrophilic nanocoatings

Pentaerythritol (PE) was modified with 3,4-dihydroxy-L-phenylalanine (L-DOPA) to produce a tetra(catecholamine) tetra-ester derivative (PE-DOPA). Subsequently, PE-DOPA was used to dip-coat glass, stainless steel (SS) and various plastics under alkaline conditions and formed a poly(PE-DOPA) surface coating ranging in thickness between 1.0–3.0 nm on glass and 9.0–12.0 nm on SS, as estimated by X-ray photoelectron spectroscopy (XPS). The as-coated poly(PE-DOPA) showed increased hydrophilicity compared to the bare substrate, as demonstrated by water contact angle (WCA) measurements, whilst subsequent thermal annealing of poly(PE-DOPA) coatings on glass and SS at 120 °C for 6 h reversed the as-coated hydrophilicity through an indole ring formation reaction. The molecular structure of the poly(PE-DOPA) coating was investigated by adsorption studies, suggesting monolayer formation on glass and multilayer on SS. Surface modification of plastic substrates (e.g. Nylon, polyester, polyolefines, PTFE) was also confirmed at the molecular level by XPS and at bulk properties level by WCA. PTFE was the only plastic substrate that didn’t show any altering of its bulk hydrophilicity. Lastly, the fabrication of multilayer structures where poly(PE-DOPA) was coated by bovine serum albumin (BSA) allowed for a first assessment of poly(PE-DOPA) affinity for BSA and the associated possibility of tailoring poly(PE-DOPA) response.

Thermoluminescence and ATR-FTIR study of UVC-irradiated low-density polyethylene (LDPE) food packaging

This research aims to study the effects of ultraviolet C (UVC) radiation on low-density polyethylene (LDPE) food packaging. Main objectives include evaluating LDPE degradation and detecting UVC radiation using thermoluminescent dosimeters (TLDs) placed under LDPE samples. Results confirm accurate UVC detection after one hour of exposure, providing a useful tool for optimize food treatment procedures.ATR-FTIR spectroscopy analysis revealed subtle alterations (<8 % transmittance relative) in UVC-irradiated LDPE samples, including possible CH breakage (2910 and 2848 cm−1) and potential CC bond vibrations (1470 cm−1), among others. However, observed variations may stem from LDPE properties rather than entirely from UVC radiation. A comparative study of UVC-induced thermoluminescence (TL) emissions provided insights into various TLDs materials. TL kinetic analysis, using computerised glow curve deconvolution (CGCD) method, unveiled trap charge activation due to UVC exposure, including partial ionization, bleaching effect and photo-transfer (PTTL) processes. LDPE samples amplified UVC-TL responses, revealing intensity differences between the TLDs attributed to the PTTL process, accentuated by the lack of an annealing treatment. Additionally, chemical composition of the TL detectors such as, type, concentration, number, oxidation states and ionic radii of their dopants may influence UVC-TL response. Consequently, TL intensity ratios follow as: GR-200 (LiF: Mg, Cu, P) > TLD-100 (LiF: Ti, Mg) > TLD-400 (CaF2: Mn) > TLD-200 (CaF2: Dy). Thus, GR-200 detects ionizing radiation but cannot distinguish between ionizing and non-ionizing UVC radiation, while TLD-100 has limited effectiveness as a UVC radiation detector. In contrast, TLD-400 is suitable for detecting UVC radiation and TLD-200 emerges as the most favorable UVC detector, showing consistent response levels and minimal PTTL effect placed under the LDPE samples without the need of a thermal annealing treatment that makes the TLD-200 to be reusable in a low-cost measurement protocol.

Infrared Spectroscopic and Physical Properties of Methanol Ices—Reconciling the Conflicting Published Band Strengths of an Important Interstellar Solid

Infrared spectroscopic observations have established the presence of solid methanol (CH3OH) in the interstellar medium and in solar system ices, but the abundance of frozen CH3OH cannot be deduced without accurate band strengths, optical constants, and reference spectra. In this paper we identify disagreements, omissions, and gaps in the literature on infrared (IR) intensities of methanol ices, including unaddressed concerns that reach back several decades. New spectra are presented with intensity measurements aided by new data on the index of refraction and density of solid CH3OH. The result is that the large discordant results from different laboratory groups can now be reconciled. Multiple ices have been used to determine, apparently for the first time, IR intensities of H2O + CH3OH mixtures of accurately known composition for use with observations of interstellar ices. Also for the first time, measurements on CH3OH ices with different thicknesses have allowed us to report both near-IR band strengths and optical constants for two near-IR features used by planetary scientists. We have used our new IR results to determine vapor pressures of solid CH3OH and have compared them to measurements made with a quartz-crystal microbalance. Thermal annealings of methanol ices have been carried out and phase changes in the solid state examined. Comparisons of our results to earlier work are presented where possible, and electronic versions of our new results are made available.

Energy-Dispersive X-Ray Microanalysis – as a Method for Study the Aluminium-Polysilicon Interface after Exposure with Long-Term and Rapid Thermal Annealing

Energy dispersive X-ray microanalysis is one of the main methods for determining the elemental composition of matter. Possessing high locality and a relatively shallow penetration depth of the electron beam (&lt; 1 μm), this method has found wide application in the field of microelectronics, as the main method for analyzing the elemental composition of matter. The method allows to study the surface of a substance both pointwise and over an area with the construction of element distribution maps. In the paper we investigated the influence of long-term and rapid heat treatments on the formation of the aluminum-polysilicon interface in order to study the formation of ohmic contacts in the element base of integrated circuits. The aluminumpolysilicon interface was studied using energy-dispersive X-ray microanalysis. It has been established that during long-term thermal annealing (450 °C, 20 min) polysilicon is completely dissolved in aluminum followed by its segregation in the form of separate agglomerates in the aluminum film, which can lead to a complete failure of the integrated circuit. During rapid thermal annealing (450 °C, 7 s) such a phenomenon was not detected. Thus it is advisable to use rapid thermal annealing as an alternative to traditional long-term thermal annealing in microelectronics. This makes it possible to significantly reduce the dissolution of polysilicon in aluminum, avoid the destruction of ohmic contacts and increase the percentage of yield of workable 0products in the process of integrated circuits' manufacturing.

Impact of post-ion implantation annealing on Se-hyperdoped Ge

Hyperdoped germanium (Ge) has demonstrated increased sub-bandgap absorption, offering potential applications in the short-wavelength-infrared spectrum (1.0–3.0 μm). This study employs ion implantation to introduce a high concentration of selenium (Se) into Ge and investigates the effects of post-implantation annealing techniques on the recovery of implantation damage and alterations in optical properties. We identify optimal conditions for two distinct annealing techniques: rapid thermal annealing (RTA) at a temperature of 650 °C and ultrafast laser heating (ULH) at a fluence of 6 mJ/cm2. The optimized ULH process outperforms the RTA method in preserving high doping profiles and achieving a fourfold increase in sub-bandgap absorption. However, RTA leads to regrowth of single crystalline Ge, while ULH most likely leads to polycrystalline Ge. The study offers valuable insights into the hyperdoping processes in Ge for the development of advanced optoelectronic devices.

Effect of temperature on the stability and performance of III-nitride HEMT magnetic field sensors

The study aimed to investigate the underlying physics limiting the temperature stability and performance of non-surface passivated Al0.34Ga0.66N/GaN Hall effect sensors, including contacts, under atmospheric conditions. The results obtained from analyzing the microstructural evolution in the Al0.34Ga0.66N/GaN Hall sensor heterostructure were found to correlate with the electrical performance of the Hall effect sensor. High-resolution x-ray photoelectron spectroscopy studies revealed the signature of surface oxidation in the GaN cap layer, as well as a slight out-diffusion of “Al” from the AlGaN barrier layer. To prevent the formation of a bumpy surface morphology at the Ohmic contact, we investigated the impact of “Pt” top Ohmic contacts. The application of a top “Pt” contact stack resulted in a smooth Ohmic contact surface and provided evidence that the bumpy surface morphology in Au-based Ohmic contacts is due to the formation of an Al-Au viscous alloy during rapid thermal annealing. In the early stages of thermal aging, the small drop in contact resistivity stabilized with subsequent thermal aging past the initial 550 h at 200 °C. The outcome is that the Al0.34Ga0.66N/GaN Hall effect sensors, even without surface passivation, exhibited a stable response to applied magnetic fields with no sign of significant degradation after 2800 h of thermal aging at 200 °C under atmospheric conditions. This observed stability in the Hall sensor without surface passivation can be attributed to a self-imposed surface oxidation of the cap layer during the early stages of aging, which serves as a protective layer for the device during subsequent extended periods of thermal aging at 200 °C.

The Influence of Annealing on the Compositional and Crystallographic Properties of Sputtered Li–Al–O Thin Films

Li–Al–O materials are interesting for several applications. Herein, a Li–Al–O thin‐film materials library, deposited by inert magnetron sputtering and postdeposition annealing in O2 atmosphere, is used to study the effects of different annealing temperatures (300–850 °C) and durations (1 min to 7 h) on crystallinity and composition of the films. X‐ray photoelectron spectroscopy depth profiling reveals inhomogeneous compositional depth profiles of conventionally annealed films (300–650 °C, 3–7 h) with increased Li contents toward the film surface and increased Al contents toward the film–substrate interface, as confirmed by a combination of Rutherford backscattering spectrometry and deuteron‐induced nuclear reaction analysis. The minimum temperature for the formation of crystalline LiAlO2 in the otherwise amorphous films is 550 °C. The undesired inhomogeneous depth profiles are transformed into homogeneous ones by rapid thermal annealing (750–850 °C, 1–10 min), while simultaneously causing the formation of crystalline LiAlO2. Therefore, rapid thermal annealing is shown to be more suitable than conventional annealing for the thermal processing of Li–Al–O thin films. Moreover, this conclusion is expected to have broader relevance beyond Li–Al–O materials, as it is likely to apply to other Li metal oxides, of which there are many technologically relevant ones.