Film Processing Research Articles

Investigation of thermal stress effects during annealing of hafnia-made thin film using molecular dynamics simulations

Hafnia or hafnium oxide is a high-κ dielectric material with paramount importance in the realm of semiconductor devices. Recent advancements in 3D device structures require a few nanometer-thick conformal films on non-planar substrates. During the fabrication stage, the annealing process of thin films has been discovered to mitigate delamination issues at the film-substrate interface. However, it has been observed that the residual stress, which emerges as the film cools to room temperature, may lead to delamination. In this study, we propose an idealized atomistic model to mimic the critical region of a 3D-NAND structure, to get insights into the effect of thermal stress and delamination during the annealing of hafnia-made thin film. We employ molecular dynamics simulation using charge-optimized many-body potential (COMB) to perform heating and cooling simulations for different thicknesses of the hafnia layer. Our results suggest that, during heating, as the annealing temperature increases, the severity of delamination decreases. At extremely low thickness of the hafnia layer, delamination does not occur. However, significant delamination is observed during the cooling process, especially when the high temperature gradient is high.

Surface Crystallization Modulation toward Highly-Oriented and Phase-Pure 2D Perovskite Solar Cells.

2D perovskites have shown great potential toward stable and efficient photovoltaic devices. However, the crystal orientation and phase impurity issues of 2D perovskite films originating from the anisotropic crystal structure and specific growth mechanism have demoted their optoelectronic performances. Here, the surface crystallization modulation technique is introduced to fabricate the high-quality 2D perovskite films with both vertical crystal orientation and high phase purity by regulating the crystallization dynamics. The solvent atmosphere condition is instituted during film processing, which promotes the formation of an oriented 2D perovskite layer in stoichiometric composition at the vapor-liquid interface and templates the subsequent film growth. The solar cells based on the optimized 2D perovskite films exhibit a power conversion efficiency of 15.04%, the record for 2D perovskites (with the perovskite slab thickness n ≤ 3 and high phase purity). The solar cells based on the highly-oriented and phase-pure 2D perovskite films also demonstrate excellent thermal and humidity stabilities.

17.2% Efficient CdSexTe1−x solar cell with (InxGa1−x)2O3 emitter on lightweight and flexible glass

High-efficiency, lightweight, and flexible solar cells are sought for a variety of applications particularly when high power density and flexible form factors are desired. Development of solar cells on flexible substrates may also offer production advantages in roll-to-roll or sheet-to-sheet processes. Here, we report device efficiencies of 17.2% and 14.6%, under AM1.5G and AM0 irradiances, respectively, for a flexible, lightweight, CdTe-based solar cell. To advance the efficiency relative to the highest previously reported AM1.5G value of 16.4%, we used an indium gallium oxide (IGO) emitter layer on a cadmium stannate (CTO) transparent conductor, which was deposited on 100-μm thick Corning® Willow® Glass. A sputtered CdSe layer was employed to incorporate Se into a CdTe absorber that was deposited by close-space sublimation, and CuSCN was used as a hole transport layer between the CdTe and the back metal electrode. The IGO and CTO layers remained intact during the high temperature film processing as seen in cross-sectional imaging and elemental mapping. This device configuration offers great promise for building-integrated photovoltaics, space applications, and higher rate manufacturing.

Mesoscale self-organization of polydisperse magnetic nanoparticles at the water surface.

In this study, we investigated the self-ordering process in Langmuir films of polydisperse iron oxide nanoparticles on a water surface, employing in situ x-ray scattering, surface pressure-area isotherm analysis, and Brewster angle microscopy. X-ray reflectometry confirmed the formation of a monolayer, while grazing incidence small-angle x-ray scattering revealed short-range lateral correlations with a characteristic length equal to the mean particle size. Remarkably, our findings indicated that at zero surface pressure, the particles organized into submicrometer clusters, merging upon compression to form a homogeneous layer. These layers were subsequently transferred to a solid substrate using the Langmuir-Schaefer technique and further characterized via scanning electron microscopy and polarized neutron reflectometry. Notably, our measurements revealed a second characteristic length in the lateral correlations, orders of magnitude longer than the mean particle diameter, with polydisperse particles forming circular clusters densely packed in a hexagonal lattice. Furthermore, our evidence suggests that the lattice constant of this mesocrystal depends on the characteristics of the particle size distribution, specifically the mean particle size and the width of the size distribution. In addition, we observed internal size separation within these clusters, where larger particles were positioned closer to the center of the cluster. Finally, polarized neutron reflectometry measurements provided valuable insights into the magnetization profile across the layer.

Solid Electrolyte Interphase on Lithium Metal Anodes.

Lithium metal batteries (LMBs) represent the most promising next-generation high-energy density batteries. The solid electrolyte interphase (SEI) film on the lithium metal anode plays a crucial role in regulating lithium deposition and improving the cycling performance of LMBs. In this review, we comprehensively present the formation process of the SEI film, while elucidating the key properties such as electronic conductivity, ionic conductivity, and mechanical performance. Furthermore, various approaches for constructing the SEI film are discussed from both electrolyte regulation and artificial coating design perspectives. Lastly, future research directions along with development recommendations are also provided. This review aims to provide possible strategies for the further improvement of SEI film in LMBs and highlight their inspiration for future research directions.

Deposition processes of superhard diamond-like carbon films co-adjusted by ion energy and ion flux in arc discharges

As a kind of protective material, Diamond-Like Carbon (DLC) film can effectively improve the mechanical and tribological properties of the substrate surface. In DLC family, tetrahedral amorphous carbon (ta-C) with ultra-high hardness and excellent protective properties has been widely concerned in the field of hard protective materials. It is well known that the structure and properties of ta-C are strongly dependent on carbon plasma characteristics in the plasma environment. Therefore, it is extremely crucial to obtain the optimal process window of ta-C described by plasma micro-parameters with general significance. This paper proposed the Langmuir probe was used to diagnose the carbon plasma of the afterglow generated by arc evaporation, aiming to investigate the characteristics of carbon plasma and sheath. The effect of ion energy and ion flux adjusted by the pulse bias voltage and arc current on the sp3 hybrid bonds and hardness of DLC films was studied, aiming to find out which conditions satisfied the formation of ta-C. The results showed the microstructure and properties of DLC films were co-adjusted by ion energy and ion flux. When the carbon ions met the appropriate ion energy range (50–300 eV) and low ion flux (<8.99 × 1010 cm−2 s−1), the films tended to form ta-C structures with high sp3 bonds. However, under the condition of high ion energy and high ion flux, the structure of the films changed from sp3 bonds to sp2 bonds, resulting in the graphitization and formation of DLC films with high sp2 bonds. This work will provide new solutions to guide the design and acquisition of high-performance DLC films.

Dual Buried Interface Engineering for Improving Air-Processed Inverted FAPbI3 Perovskite Solar Cells.

Fabricating perovskite solar cells (PSCs) in an ambient environment provides low-cost preparation routes for solar cells that are suitable for large-scale production. Compared with methylammonium (MA)- based perovskite materials, formamidinium lead iodide (FAPbI3) possesses a more favorable bandgap for light harvesting and better thermostability. However, the phase transition from the α-phase to the δ-phase easily occurs, making it challenging for ambient-air processing. Herein, we develop a buried interface engineering strategy via two molecules including 1,4-bis(diphenylphosphino)butane (DPPB) as well as [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl] phosphonic acid (Me-4PACz) to optimize air-processed inverted FAPbI3 PSCs. This strategy regulates the crystallization process of the air-fabricated FAPbI3 perovskite film, leading to a purer α-phase with significantly enhanced crystallinity and enlarged grain sizes. Apart from improving the bulk perovskite film, the defects at the NiOx/perovskite interface are passivated, and the energy levels are better matched in the modified device, which facilitates efficient carrier extraction. Resultantly, the target device processed in the open air achieves a dramatically improved power conversion efficiency from 11.37% to 18.45%, in association with an enhanced device stability.

Iodide manipulation using zinc additives for efficient perovskite solar minimodules

Interstitial iodides are the most critical type of defects in perovskite solar cells that limits efficiency and stability. They can be generated during solution, film, and device processing, further accelerating degradation. Herein, we find that introducing a small amount of a zinc salt- zinc trifluoromethane sulfonate (Zn(OOSCF3)2) in the perovskite solution can control the iodide defects in resultant perovskites ink and films. CF3SOO̶ vigorously suppresses molecular iodine formation in the perovskites by reducing it to iodide. At the same time, zinc cations can precipitate excess iodide by forming a Zn-Amine complex so that the iodide interstitials in the resultant perovskite films can be suppressed. The perovskite films using these additives show improved photoluminescence quantum efficiency and reduce deep trap density, despite zinc cations reducing the perovskite grain size and iodide interstitials. The zinc additives facilitate the formation of more uniform perovskite films on large-area substrates (78-108 cm2) in the blade-coating process. Fabricated minimodules show power conversion efficiencies of 19.60% and 19.21% with aperture areas of 84 and 108 cm2, respectively, as certified by National Renewable Energy Laboratory (NREL), the highest efficiency certified for minimodules of these sizes.

Unveiling the Role of Ge in CZTSSe Solar Cells by Advanced Micro-To-Atom Scale Characterizations.

Kesterite is an earth-abundant energy material with high predicted power conversion efficiency, making it a sustainable and promising option for photovoltaics. However, a large open circuit voltage Voc deficit due to non-radiative recombination at intrinsic defects remains a major hurdle, limiting device performance. Incorporating Ge into the kesterite structure emerges as an effective approach for enhancing performance by manipulating defects and morphology. Herein, how different amounts of Ge affect the kesterite growth pathways through the combination of advanced microscopy characterization techniques are systematically investigated. The results demonstrate the significance of incorporating Ge during the selenization process of the CZTSSe thin film. At high temperature, the Ge incorporation effectively delays the selenization process due to the formation of a ZnSe layer on top of the metal alloys through decomposition of the Cu-Zn alloy and formation of Cu-Sn alloy, subsequently forming of Cu-Sn-Se phase. Such an effect is compounded by more Ge incorporation that further postpones kesterite formation. Furthermore, introducing Ge mitigates detrimental "horizontal" grain boundaries by increasing the grain size on upper layer. The Ge incorporation strategy discussed in this study holds great promise for improving device performance and grain quality in CZTSSe and other polycrystalline chalcogenide solar cells.

FMRI BOLD responses to film stimuli and their association with exhaled nitric oxide in asthma and health.

Little is known about central nervous system (CNS) responses to emotional stimuli in asthma. Nitric oxide in exhaled breath (FENO) is elevated in asthma due to allergic immune processes, but endogenous nitric oxide is also known to modulate CNS activity. We measured fMRI blood oxygen-dependent (BOLD) brain activation to negative (blood-injection-injury themes) and neutral films in 31 participants (15 with asthma). Regions-of-interest analysis was performed on key areas relevant to central adaptive control, threat processing, or salience networks, with dorsolateral prefrontal cortex (PFC), anterior insula, dorsal anterior cingulate cortex (dACC), amygdala, ventral striatum, ventral tegmentum, and periaqueductal gray, as well as top-down modulation of emotion, with ventrolateral and ventromedial PFC. Both groups showed less BOLD deactivation from fixation cross-baseline in the left anterior insula and bilateral ventromedial PFC for negative than neutral films, and for an additional number of areas, including the fusiform gyrus, for film versus recovery phases. Less deactivation during films followed by less recovery from deactivation was found in asthma compared to healthy controls. Changes in PCO2 did not explain these findings. FENO was positively related to BOLD activation in general, but more pronounced in healthy controls and more likely in neutral film processing. Thus, asthma is associated with altered processing of film stimuli across brain regions not limited to central adaptive control, threat processing, or salience networks. Higher levels of NO appear to facilitate CNS activity, but only in healthy controls, possibly due to allergy's masking effects on FENO.

Dimethylamine oxalate manipulating CsPbI3 perovskite film crystallization process for high efficiency carbon electrode based perovskite solar cells

Crystallization process determines the quality of perovskite films and the performances of resultant perovskite solar cells (PSCs). Dimethylamine oxalate has been proven as a multifunctional modulator, and is explored as an efficient additive in manipulating the crystallization process of CsPbI3 perovskite films. On one hand, oxalate serves as the precipitator that facilitates the nucleation process of intermediate. The larger size of intermediate is conductive to the larger size and smaller grain boundaries of resultant perovskite. On the other hand, in subsequent annealing process, the phase conversion and growth process of transient perovskite can be decelerated due to the strong interactions of oxalate with both dimethylamine cation (DMA+) and Pb2+. Due to the optimized crystallization kinetics, the morphology and quality of CsPbI3 perovskite films are comprehensively improved with lower defect concentrations, and charge recombination loss is effectively suppressed. Benefiting from the optimized crystal quality of perovskite films, the carbon electrode-based CsPbI3 PSCs exhibit a champion efficiency of 18.48%. This represents one of the highest levels among all hole transport layer-free inorganic perovskite solar cells.

Recent advances and challenges in thermal stability of PVA‐based film: A review

AbstractFood packaging film is being developed using biodegradable polymers to prolong the shelf life of foods and address the environmental damage caused by non‐biodegradable plastics. Poly(vinyl alcohol) (PVA) is a biodegradable polymer with outstanding characteristics and can be easily shaped into a film. However, PVA‐based film still faces several obstacles that seriously restrict its practical application in the food packaging industry, particularly its low thermal stability limits the film process method. The growing preference demand for PVA‐based films with enhanced thermal stability in food packaging can be attributed to their advantageous characteristics, including commendable temperature resistance, safety, versatile processing capabilities, and prolonged shelf life. It is critical to comprehend the difficulties with PVA thermal degradation behavior and mechanism, and how to address this problem. In this review, we provide strategies for improving the thermal stability of PVA film including modification with environmentally friendly polymers, nanoparticles, and crosslinking agents. Also, the current challenges, and the potential for future advancements in the thermal stability of PVA and its composites are proposed. The new insight into the relationship between PVA based film processing and thermal properties of materials are expected to provide a valuable guide for developing PVA films with high thermal stability.

A fabrication process of soft magnetic Ni films electroplated from gel electrolyte

We have already reported some electroplated magnetic films using aqueous solutions. In the present study, we proposed a fabrication process for electroplated soft magnetic films (Ni films) using gel electrolytes. We added gelatin to the plating baths and confirmed that adding 22 g/L of gelatin enabled us to obtain gel electrolytes. Using the gel electrolytes, we electroplated Ni films and evaluated their structural and magnetic properties. From the evaluation of magnetic properties, we confirmed spontaneous magnetization of the Ni films prepared from the gel electrolyte. For obtaining thick Ni films (&amp;gt;1 μm), we investigated stirring the gel electrolyte during plating. As a result, we found that stirring increased the thickness, and our result suggests that stirring the gel electrolyte is useful to increase the deposition rate. In our experimental conditions, the deposition rate of the plating process was ∼0.25 μm/min. From XRD analysis, the structure of Ni films for gel electrolytes was oriented in the fcc (220) plane and slightly different from that for liquid electrolytes. From these results, we found that soft magnetic films could be obtained from the gel electrolyte and that gel plating is one of the attractive fabrication processes of the thick films.

Enhanced Biodegradation Rate of Poly(butylene adipate-co-terephthalate) Composites Using Reed Fiber.

To enhance the degradability of poly(butylene adipate-co-terephthalate) (PBAT), reed fiber (RF) was blended with PBAT to create composite materials. In this study, a fifteen day degradation experiment was conducted using four different enzyme solutions containing lipase, cellulase, Proteinase K, and esterase, respectively. The degradation process of the sample films was analyzed using an analytical balance, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The PBAT/RF composites exhibited an increased surface hydrophilicity, which enhanced their degradation capacity. Among all the enzymes tested, lipase had the most significant impact on the degradation rate. The weight loss of PBAT and PBAT/RF, caused by lipase, was approximately 5.63% and 8.17%, respectively. DSC analysis revealed an increase in the melting temperature and crystallinity over time, especially in the film containing reed fibers. FTIR results indicated a significant weakening of the ester bond peak in the samples. Moreover, this article describes a biodegradation study conducted for three months under controlled composting conditions of PBAT and PBAT/RF samples. The results showed that PBAT/RF degraded more easily in compost as compared to PBAT. The lag phase of PBAT/RF was observed to decrease by 23.8%, while the biodegradation rate exhibited an increase of 11.8% over a period of 91 days. SEM analysis demonstrated the formation of more cracks and pores on the surface of PBAT/RF composites during the degradation process. This leads to an increased contact area between the composites and microorganisms, thereby accelerating the degradation of PBAT/RF. This research is significant for preparing highly degradable PBAT composites and improving the application prospects of biodegradable green materials. PBAT/RF composites are devoted to replacing petroleum-based polymer materials with sustainable, natural materials in advanced applications such as constructional design, biomedical application, and eco-environmental packaging.

Preparation and characterization of pH-sensitive intelligent packaging films based on cassava starch/polyvinyl alcohol matrices containing Aronia melanocarpa anthocyanins

Intelligent packaging films have sparked interest due to their capacity to indicate food freshness. In this study, a pH-sensitive packaging film was developed using the cast film process, with cassava starch and polyvinyl alcohol (PVA) as substrates. Aronia melanocarpa anthocyanins (AMA) were incorporated as visual indicators of pH changes. The study assessed the impact of the cassava starch/PVA ratio and AMA content on the films' physical, structural, and pH-sensitive properties. It evaluated their potential for monitoring milk freshness. The results revealed that films with a starch/PVA ratio 3/7 achieved optimal tensile strength (TS) and elongation at break (EAB). The incorporation of AMA into the films enhanced their UV barrier properties. Notably, the compatibility between starch and PVA was improved when the film contained 1 g of AMA per hectogram (hg) of the total mass of starch and PVA. Specifically, the enhanced compatibility was evident through differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) analysis. Furthermore, the films demonstrated notable color changes within a pH range of 2–11, indicating their potential for monitoring milk freshness. These findings suggested that the films containing AMA hold great promise for applications in intelligent packaging within the food industry.

Bridging two worlds: (DABCO-H)CuKI3 a hybrid copper iodide phosphor with a perovskite structure

Abstract A novel copper iodide hybrid compound, (DABCO-H)CuKI3, featuring a perovskite structure is here reported. Characterization techniques, including single crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and photoluminescence studies, elucidate the structural and luminescent properties. The compound exhibits blue phosphorescence, attributed to mixed metal-to-ligand and halide-to-ligand charge transfer transitions, as supported by density functional theory (DFT) calculations and XPS valence band analysis. Furthermore, (DABCO-H)CuKI3 displays a remarkable adsorption capacity towards methylene blue dye. Kinetic modelling reveals that both film and intra-particle diffusion processes contribute to the adsorption rate.

Facile Hydrogen‐Bonding Assisted Crystallization Modulation for Large‐area High‐quality CsPbI2Br Films and Efficient Solar Cells

AbstractThe thermally stable inorganic cesium‐based perovskites promise efficient and stable photovoltaics. Unfortunately, the strong ionic bonds lead to uncontrollable rapid crystallization, making it difficult in fabricating large‐area black‐phase film for photovoltaics. Herein, we developed a facile hydrogen‐bonding assisted strategy for modulating the crystallization of CsPbI2Br to achieve uniform large‐area phase‐pure films with much‐reduced defects. The simple addition of methylamine acetate in precursors not only promotes the formation of intermediate phase via hydrogen bonding to circumvent the direct crystallization of CsPbI2Br from ionic precursors but also widens the film processing window, thus enabling to fabricate large‐area high‐quality phase‐pure CsPbI2Br film under benign conditions. Combining with stable dopant‐free poly(3‐hexylthiophene), the CsPbI2Br solar cells achieve the record‐high efficiencies of 18.14 % and 16.46 % for 0.1 cm2 and 1 cm2 active area, respectively. The obtained high efficiency of 38.24 % under 1000 lux illumination suggests its potential in indoor photovoltaics for powering the Internet of Things, etc.

Facile Hydrogen-Bonding Assisted Crystallization Modulation for Large-area High-quality CsPbI2 Br Films and Efficient Solar Cells.

The thermally stable inorganic cesium-based perovskites promise efficient and stable photovoltaics. Unfortunately, the strong ionic bonds lead to uncontrollable rapid crystallization, making it difficult in fabricating large-area black-phase film for photovoltaics. Herein, we developed a facile hydrogen-bonding assisted strategy for modulating the crystallization of CsPbI2 Br to achieve uniform large-area phase-pure films with much-reduced defects. The simple addition of methylamine acetate in precursors not only promotes the formation of intermediate phase via hydrogen bonding to circumvent the direct crystallization of CsPbI2 Br from ionic precursors but also widens the film processing window, thus enabling to fabricate large-area high-quality phase-pure CsPbI2 Br film under benign conditions. Combining with stable dopant-free poly(3-hexylthiophene), the CsPbI2 Br solar cells achieve the record-high efficiencies of 18.14 % and 16.46 % for 0.1 cm2 and 1 cm2 active area, respectively. The obtained high efficiency of 38.24 % under 1000 lux illumination suggests its potential in indoor photovoltaics for powering the Internet of Things, etc.

Exciton dynamics in two-dimensional metal halide perovskite: The impact of film processing.

We investigate the hot carrier and exciton dynamics in two-dimensional (2D) metal halide perovskites using time-resolved spectroscopy. 2D perovskite films were prepared with and without dimethyl sulfoxide treatment to elucidate the effect of film processing techniques on optoelectronic properties. Femtosecond transient absorption measurements reveal that the charge carrier dynamics are different in the two samples, and excitons survive for a longer time in the treated sample than the untreated one. While the early-time carrier dynamics in the untreated sample are dominated by charges trapped by defect states, the hot free carriers govern the dynamics in the treated sample due to fewer defects in it. Morphological and other spectroscopic studies, including time-resolved photoluminescence, further suggest the formation of more defects in the untreated sample. These results can guide the future development of efficient 2D perovskite-based optoelectronic devices.

Spontaneous adsorption effect of graphitic carbon nitride nanosheets to improve sintering behavior of yttria-stabilized zirconia microbeads

Yttria-stabilized zirconia (YSZ) is a ceramic material in which the zirconium dioxide structure is stabilized at room temperature by adding yttrium oxide. However, the YSZ formed by the thick film process on a pre-sintered dense substrate suffers from sintering problems such as different sintering shrinkage rates due to phase transitions and thermal conductivity. This in turn can lead to de-bonding, cracking, delamination, and abnormal growth. We prepared a spherical YSZ green body of approximately 38 μm diameter formed by an organic binder based on a sintered YSZ seed with 15 to 20 μm diameter. In addition, the application of two-dimensional g-C3N4 nanosheets that can be adsorbed on the surface and pores of the green body before the sintering process was evaluated. The YSZ green body with adsorbed surface-modified g-C3N4 nanosheets could be synthesized by stable spontaneous adsorption due to zeta-potential attraction onto the surface of zirconia particles in an aqueous solution. Consequentially, the formation of large grains due to abnormal grain growth was reduced as g-C3N4 was adsorbed. The spontaneous adsorption of nanosheets controls the surface diffusion mechanism by sequentially lowering the energy from a high surface energy in the initial stage of sintering. Uniform grain growth thus can be induced according to the activation energy level of the controlled surface diffusion.