Solution-based Process Research Articles

Solution-based processing of Ge2Sb2Se4Te optical phase change materials

Phase change materials (PCMs) are important building blocks in solid-state memory and photonic devices. Solution-based processing promises large-area, cost-effective, conformal coating of optical PCMs (O-PCMs) for photonic applications. In this work, a solution processing route was developed for Ge2Sb2Se4Te1 (GSST), a target PCM of interest due to its large optical contrast, broadband transparency, and improved glass-forming capability. An alkahest solvent mixture of ethanedithiol and ethylenediamine was used as a solvent system to fabricate solution-derived GSST thin films and films from these solutions were prepared and characterized using SEM, XRD, and Raman spectroscopy.

Advanced nano-composite coatings of ZrB₂/ZrC/SiC on carbon fibers via eco-friendly precursor synthesis

This study presents a comprehensive investigation into the synthesis and characterization of ZrB2/ZrC/SiC composite coatings on carbon fiber substrates via a solution-based process followed by high-temperature pyrolysis. The precursor solution was prepared using Gum Ghatti (GG), zirconyl chloride, tetraethyl orthosilicate, and boric acid. Optimization of precursor concentration and molar ratios was performed to achieve suitable viscosity and composition. The pyrolysis process was conducted in an argon atmosphere, resulting in the formation of well-defined ZrB2, ZrC, and SiC phases. XRD analysis confirmed the phase composition, while SEM imaging revealed spheroidal particle aggregates with a uniform distribution of composite phases. TG-DTA analysis reveals the thermal decomposition behavior, highlighting distinct stages of mass loss and phase transformations. Coated carbon fibers exhibited enhanced oxidation resistance, as evidenced by TGA analysis. SEM analysis confirmed the uniform distribution and adhesion of the composite matrix on the carbon fiber substrate. This study demonstrates the successful synthesis of ZrB2/ZrC/SiC composite coatings with promising thermal properties for advanced applications.

Influence of sulfurization temperature on grain growth in Cu2ZnSnS4 thin films synthesized for solar cell applications

Copper-zinc-tin-sulfur (CZTS) thin films, prepared through a dip-coating solution method, present a highly attractive option as absorber materials for thin-film solar cells. This is due to their affordability, environmentally friendly composition, and abundant availability of raw materials. Although films processed with hydrazine-based solutions have achieved the highest efficiency of approximately 12.6%, the toxic and carcinogenic nature of hydrazine negates these advantages. In the ongoing global research on solution-based processing methods, the size of the grains has emerged as a critical factor in the fabrication of efficient solar cells. In our study, we have successfully prepared CZTS thin films with a pure kesterite phase, characterized by large micro-sized grains, using a dip-coating process with an ethanol-based precursor solution, followed by sulfurization. We investigated how the grain size evolves with varying sulfurization temperatures. Notably, we observed that increasing the temperature led to larger and more uniform grain growth. These results underscore the potential of our approach for the straightforward production of high-quality films with sizable grains, ultimately enhancing their photosensitivity and making them a promising candidate for efficient solar cell applications.

Natural Organic Honey-CNT Memristor Based Artificial Synaptic Devices for Sustainable Neuromorphic System

Neuromorphic computing is considered to have the potential to overcome the limitations of traditional von Neumann architecture due to its high efficiency, low energy consumption, and fault-tolerance. Hardware components that can emulate the synaptic plasticity of neurons, i.e. artificial synaptic devices, are required by neuromorphic systems. New devices have been examined for such components, such as phase-change artificial synapse, ferroelectric artificial synapse, and memristor synapses. Among them, memristor, a two-terminal metal-insulator-metal structure that are analogous to a biological synapse with presynaptic neuron (top electrode), postsynapticneuron (bottom electrode), and synaptic cleft (memristive film), is a promising device technology because of its tunable resistance, scalability, 3D integration compatibility, low power consumption, and relatively high speed. In contrary to inorganic materials such as metal oxides, natural organic materials have attracted interest to form the memristive layer because they are renewable, biodegradable, sustainable, biocompatible, and environmentally friendly. In this paper, honey solution embedded with carbon nanotubes (CNTs) was processed into the memristive layer by a low cost solution-based process, with synaptic plasticity of the final honey-CNT memristors characterized, including forget and relearn, spike-rate-dependent plasticity, spike-voltage-dependent plasticity, short-term to long-term memory transition, paired pulse facilitation, and spatial supra-linear summation behaviors. The successful emulation of these essential biological synaptic behaviors demonstrates the potential of honey-CNT memristors as a viable hardware component in neuromorphic computing systems.

Role of Dopant in Enabling Electrodeposition of Polymer Thin Films with High Solar Transmittance Modulation

Buildings consume approximately one-third of the energy used in developed countries, with much of this energy tied to building heating and cooling. Electrochromic “smart” windows have the potential to mitigate some of this energy use through on-demand modulation of solar energy transmission. Therefore, electrochromic window devices based on low cost and facile solution-based processing routes are sought. In this work, we describe the electropolymerization and deposition of electrochromic poly(arylamine) thin films with exceptional broadband solar transmittance modulation, reaching ΔT sol values of over 60% (Figure 1). Through high-resolution, near-field spectroscopic imaging we show that the structure of the acid dopant present in the electrodeposition solution plays a key templating role that determines the electrochromic performance of these films. Our findings indicate that polyanionic dopants are especially adept at directing polymer chain conformational order, which in turn improves charge delocalization and transport. These factors lead to films with high smoothness and optical clarity through the visible (T lum > 80%) and near-infrared ranges. Further details regarding the cycling stability of these films and their integration into full electrochromic devices will be discussed. In summary, this work demonstrates the value of polyanionic dopants for templating high quality electrochromic polymer thin films capable of energy-relevant solar transmittance modulation for smart window applications. Figure 1

Nonideality in Arrayed Carbon Nanotube Field Effect Transistors Revealed by High-Resolution Transmission Electron Microscopy.

High density and high semiconducting-purity single-walled carbon nanotube array (A-CNT) have recently been demonstrated as promising candidates for high-performance nanoelectronics. Knowledge of the structures and arrangement of CNTs within the arrays and their interfaces to neighboring CNTs, metal contacts, and dielectrics, as the key components of an A-CNT field effect transistor (FET), is essential for device mechanistic understanding and further optimization, particularly considering that the current technologies for the fabrication of A-CNT wafers are mainly laboratory-level solution-based processes. Here, we conduct a systematic investigation into the microstructures of A-CNT FETs mainly via cross-sectional high-resolution transmission electron microscopy and tentatively establish a framework consisting of up to 11 parameters which can be used for structure-side quality evaluation of the A-CNT FETs. The parameter ensemble includes the diameter, length (or terminal), and density distribution of CNTs, radial deformation of CNTs, array alignment defects, surface crystallography facets of contact metal, thickness distribution of high-k dielectrics (HfO2), and the contact ratios for the CNT-CNT, CNT-metal, CNT-dielectric, and CNT-substrate interfaces. Enriched array alignment defects, i.e., bundle, stacking, misorientation, and voids, are observed with a total ratio sometimes up to ∼90% in pristine A-CNTs and even up to ∼95% after the device fabrication process. Thus, they are suggested as the prevalent performance-limiting factors for A-CNT FETs. Complex interfacial structures are observed at the CNT-CNT, CNT-metal contact, and CNT-high-k dielectric interfaces, making the local environment and the property of each component CNT involved in an A-CNT FET distinct from others in terms of the diameters, radial deformation, and interactions with the local surroundings (mainly through van der Waals interactions). The present study suggests further improvements on the fabrication technology of A-CNT wafers and devices and mechanistic investigations into the impacts of complex array alignment defects and interface structures on the electrical performance of A-CNT FETs as well.

Quantum Dot-Based Three-Stack Tandem Near-Infrared-to-Visible Optoelectric Upconversion Devices.

Quantum dots (QDs) exhibit size-tunable optical properties, making them suitable for efficient light-sensing and light-emitting devices. Tandem devices that can convert near-infrared (NIR) to visible (Vis) signals can be fabricated by integrating an NIR-sensing QD device with a Vis electroluminescence (EL) QD device. However, these devices require delicate control of the QD layer during processing to prevent damage to the predeposited QD layers in tandem devices during the subsequent deposition of other functional layers. This has restricted attainable device structures for QD-based upconversion devices. Herein, we present a modular approach for fabricating QD-based optoelectric upconversion devices. This approach involves using NIR QD-absorbing (Abs) and Vis QD-EL units as building modules, both of which feature cross-linked functional layers that exhibit structural tolerance to dissolution during subsequent solution-based processes. Tandem devices are fabricated in both normal (EL unit on Abs unit) and inverted (Abs unit on EL unit) structures using the same set of NIR QD-Abs and Vis QD-EL units stacked in opposite sequences. The tandem device in the normal structure exhibits a high NIR photon-to-Vis-photon conversion efficiency of up to 1.9% in a practical transmissive mode. By extending our modular approach, we also demonstrate a three-stack tandem device that incorporates a single NIR-absorbing unit coupled with two EL units, achieving an even higher conversion efficiency of up to 3.2%.

The big bang of halide perovskites: The starting point of crystallization

Hybrid halide perovskites (HHPs) are very promising absorber materials for solar cells due to their high power conversion efficiency and the low-cost solution-based processing methods. We applied small angle X-ray scattering to MAPbI3, FAPbI3 and MAPbBr3 precursor solutions in different solvents (GBL, DMF, and mixtures) to gain a deeper understanding of the building blocks during the early stage of HHP formation. We present a core–shell model where the core is formed by [PbX6] octahedra surrounded by a shell of solvent molecules, which explains the arrangement of the precursors in solution and how the solvent and the halide influence such arrangement.Graphical

Enhanced optoelectrical properties and stability of solvent-based perovskite solar cells using ellagic acid additives

Perovskite solar cells (PSCs) with solution-based fabrication processes deserve a simple and controllable fabrication process to produce cost-effective new-generation solar cells. Increasing optoelectrical properties of the light-harvesting perovskite layer during the fabrication process is used to enhance photovoltaic efficiency and the stability of PSCs. Here, ellagic acid was added into the lead iodide precursor to control the reaction of lead iodide with formamidinium iodide to generate a perovskite layer with enlarged grains. The obtained results showed the ellagic acid additive reduced charge recombination losses within solar cells and prompted charge transfer from perovskite to electron transporting layer and hole transporting layer, recording a champion efficiency of 22.04 % along with an open circuit voltage of 1.095 V, short-circuit current density of 24.17 mA cm−2, and fill factor of 78.94 %. In addition, the ellagic acid-based PSCs showed considerable stability improvement against the humidity and light irradiance compared to the control PSCs. It can be concluded that the ellagic acid additive may push the PSCs further to commercialization.

Compatibility and performance study of electrohydrodynamic printing using zinc oxide inkjet ink

The demand for modern electronics and semiconductors has increased throughout the years, which has enabled the innovation and exploration of solution-processed deposition. Solution-based processes have gained a lot of interest due to the low-cost fabrication and the large fabrication areas without the need for high-vacuum equipment. In this study, we utilized the ZnO ink for inkjet printer ink to fabricate a thin film via Electrohydrodynamic printing. Three different ink solutions were prepared for experimentation. The EHD printing technique demonstrated the ink’s compatibility with and without the modifications. The outcomes of the EHD printed materials were comparable with the spin-coated thin films. The EHD-printed films demonstrated better results in comparison to spin-coated films. Ra and Rq of the EHD film measured at 3.651 nm and 4.973 nm, respectively. It improved the absorbance up to two-fold at 360 nm wavelength and electrical conductivity up to 40% compared to the spin-coated films. Furthermore, the optimization of the printing parameters can lead to the improved morphology and thickness of the EHD thin films.

Real-Time Ultraviolet Monitoring System with Low-Temperature Solution-Processed High-Transparent p-n Junction Photodiode with a Fast Responsive and High Rectification Ratio.

We introduce an enhanced performance organic-inorganic hybrid p-n junction photodiode, utilizing poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA) and ZnO, fabricated through a solution-based process at a low temperature under 100 °C. Improved interfacial electronic structure, characterized by shallower Gaussian standard deviation of the density-of-state distribution and a larger interface dipole, has resulted in a remarkable fold increase of ∼102 in signal-to-noise ratio for the device. This photodiode exhibits a high specific detectivity (2.32 × 1011 Jones, ) and exceptional rectification ratio (5.47 × 104 at ±1 V). The primary light response, concentrated in the optimal thickness of the PTAA layer, contributes to response over the entire UVA region and rapid response speed, with rise and fall times of 0.24 and 0.64 ms, respectively. Furthermore, this work demonstrates immense potential of our device for health monitoring applications by enabling real-time and continuous measurements of UV intensity.

Comprehensive investigation of material properties and operational parameters for enhancing performance and stability of FASnI3-based perovskite solar cells

Recent advancements in the efficiency of lead-based halide perovskite solar cells (PSCs), exceeding 25%, have raised concerns about their toxicity and suitability for mass commercialization. As a result, tin-based PSCs have emerged as attractive alternatives. Among diverse types of tin-based PSCs, organic–inorganic metal halide materials, particularly FASnI3 stands out for high efficiency, remarkable stability, low-cost, and straightforward solution-based fabrication process. In this work, we modelled the performance of FASnI3 PSCs with four different hole transporting materials (Spiro-OMeTAD, Cu2O, CuI, and CuSCN) using SCAPS-1D program. Compared to the initial structure of Ag/Spiro-OMeTAD/FASnI3/TiO2/FTO, analysis on current–voltage and quantum efficiency characteristics identified Cu2O as an ideal hole transport material. Optimizing device output involved exploring the thickness of the FASnI3 layer, defect density states, light reflection/transmission at the back and front metal contacts, effects of metal work function, and operational temperature. Maximum performance and high stability have been achieved, where an open-circuit voltage of 1.16 V, and a high short-circuit current density of 31.70 mA/cm2 were obtained. Further study on charge carriers capture cross-section demonstrated a PCE of 32.47% and FF of 88.53% at a selected capture cross-section of electrons and holes of 1022 cm2. This work aims to guide researchers for building and manufacturing perovskite solar cells that are more stable with moderate thickness, more effective, and economically feasible.

All-Solution-Processed Electronics with Sub-Microscale Resolution and Nanoscale Fidelity Fabricated Via a Humidity-Controlled, Surface Energy-Directed Assembly Process.

Solution-based processes have received considerable attention in the fabrication of electronics and sensors owing to their merits of being low-cost, vacuum-free, and simple in equipment. However, the current solution-based processes either lack patterning capability or have low resolution (tens of micrometers) and low pattern fidelity in terms of line edge roughness (LER, several micrometers). Here, we present a surface energy-directed assembly (SEDA) process to fabricate metal oxide patterns with up to 2 orders of magnitude improvement in resolution (800 nm) and LER (16 nm). Experiment results show that high pattern fidelity can be achieved only at low relative humidities of below 30%. The reason for this phenomenon lies in negligible water condensation on the solution droplet. Employing the SEDA process, all-solution-processed metal oxide thin film transistors (TFTs) are fabricated by using indium oxide as channel layers, indium tin oxide as source/drain electrodes and gate electrodes, and aluminum oxide as gate dielectrics. TFT-based logic gate circuits, including NOT, NOR, NAND, and AND are fabricated as well, demonstrating the applicability of the SEDA process in fabricating large area functional electronics.

Solution-Based Suspension Synthesis of Li2S-P2S5 Glass-Ceramic Systems as Solid-State Electrolytes: A Brief Review of Current Research.

All-solid-state batteries are set to be the next generation of batteries offering improved performance and safety over current conventional lithium-ion batteries. Glass-ceramic Li2S-P2S5 solid-state sulfide electrolytes are promising contenders to achieve all-solid-state batteries with exceptional ionic conductivity on the order of 10-2 S cm-1. Solid-state processing techniques for synthesizing sulfide solid electrolytes are energetically and time consumptive. However, proposed solution processing techniques offer faster and lower temperature processes rendering them scalable. The chemistries that underly solution processing of sulfide solid electrolytes are still not well understood. This brief review highlights key aspects of current research into solution-based suspension synthesis processing techniques of Li2S-P2S5 sulfide solid electrolytes discussing precursor stoichiometries, solvent selectivity, reaction conditions, chemical impurities, and particle morphology with the intent of promoting further research into solution processing of sulfide solid-state electrolytes.

Tailored Hollow Mesoporous Carbon Nanospheres from Soft Emulsions Enhance Kinetics in Sodium Batteries.

Mesoporous materials endowed with a hollow structure offer ample opportunities due to their integrated functionalities; however, current approaches mainly rely on the recruitment of solid rigid templates, and feasible strategies with better simplicity and tunability remain infertile. Here, we report a novel emulsion-driven coassembly method for constructing a highly tailored hollow architecture in mesoporous carbon, which can be completely processed on oil-water liquid interfaces instead of a solid rigid template. Such a facile and flexible methodology relies on the subtle employment of a 1,3,5-trimethylbenzene (TMB) additive, which acts as both an emulsion template and a swelling agent, leading to a compatible integration of oil droplets and composite micelles. The solution-based assembly process also shows high controllability, endowing the hollow carbon mesostructure with a uniform morphology of hundreds of nanometers and tunable cavities from 0 to 130 nm in diameter and porosities (mesopore sizes 2.5-7.7 nm; surface area 179-355 m2 g-1). Because of the unique features in permeability, diffusion, and surface access, the hollow mesoporous carbon nanospheres exhibit excellent high rate and cycling performances for sodium-ion storage. Our study reveals a cooperative assembly on the liquid interface, which could provide an alternative toolbox for constructing delicate mesostructures and complex hierarchies toward advanced technologies.

Scalable Fabrication of Quasi-One-Dimensional van der Waals Ta2Pt3Se8 Nanowire Thin Films via Solution Processing for NO2 Gas Sensing over Large Areas.

Solution-based processing of van der Waals (vdW) one- (1D) and two-dimensional (2D) materials is an effective strategy to obtain high-quality molecular chains or atomic sheets in a large area with scalability. In this work, quasi-1D vdW Ta2Pt3Se8 was exfoliated via liquid phase exfoliation (LPE) to produce a stably dispersed Ta2Pt3Se8 nanowire solution. In order to screen the optimal exfoliation solvent, nine different solvents were employed with different total surface tensions and polar/dispersive (P/D) component (P/D) ratios. The LPE behavior of Ta2Pt3Se8 was elucidated by matching the P/D ratios between Ta2Pt3Se8 and the applied solvent, resulting in N-methyl-2-pyrrolidone (NMP) as an optimal solvent owing to the well-matched total surface tension and P/D ratio. Subsequently, Ta2Pt3Se8 nanowire thin films are manufactured via vacuum filtration using a Ta2Pt3Se8/NMP dispersion. Then, gas sensing devices are fabricated onto the Ta2Pt3Se8 nanowire thin films, and gas sensing property toward NO2 is evaluated at various thin-film thicknesses. A 50 nm thick Ta2Pt3Se8 thin-film device exhibited a percent response of 25.9% at room temperature and 32.4% at 100 °C, respectively. In addition, the device showed complete recovery within 14.1 min at room temperature and 3.5 min at 100 °C, respectively.

Scattering/Fluorescence Dual-Mode Imaging in MnO2-Coated Silicon Nanospheres for Cancer Cell Detection.

A tumor microenvironment (TME)-responsive nanoprobe composed of a fluorescent dye-decorated silicon (Si) nanosphere core and a thin MnO2 shell is proposed for simple and intelligent detection of cancer cells. The Si nanosphere core with diameters of 100-200 nm provides environment-independent Mie scattering imaging, while, simultaneously, the MnO2 shell provides the capability to switch the on/off state of the dye fluorescence reacted to the glutathione (GSH) and/or H2O2 levels in a cancer cell. Si-MnO2 core-shell nanosphere probes are fabricated in a solution-based process from crystalline Si nanosphere cores. The fluorescence switching under exposure to GSH is demonstrated, and the mechanism is discussed based on detailed optical characterizations including single-particle spectroscopy. Different types of human cells are incubated with the nanoprobes, and a proof of concept experiment is performed. From the combination of the robust scattering images and GSH- and H2O2-sensitive fluorescence images, the feasibility of cancer cell detection by the multimodal nanoprobes is demonstrated.

Indeno[3,2-b]carbazole-Based Small Molecule Layer Enables Optimized Carrier Transport for PbS Quantum Dot NIR Photodetectors.

Colloidal quantum dots (CQDs) have garnered considerable attention for photodetectors (PDs), attributable to exceptional photoelectric properties and ease solution-based processing. However, the prevalent use of 1,2-ethanedithiol (EDT) as a hole transport layer (HTL) has limitations, such as energy level discrepancies, requisite oxidation, and intricate multilayer assembly. Organic p-type materials, lauded for their superior attributes and synthetic versatility, are now stepping forward as viable substitutes for conventional EDT HTLs. In this work, we introduced an organic HTL derived from indolo[3,2-b]carbazole, named ZL004, leading to a marked improvement in carrier generation and collection, facilitated by the optimized band alignment and enhanced interfacial charge dynamics. The ZL004-based PDs exhibit a photoresponsivity of 0.45 A/W, a noise current of 1.8 × 10-11 A Hz-0.5, a specific detectivity of 4.6 × 109 Jones, and an expansive linear dynamic range of 107 dB─surpassing EDT-based devices across the board, demonstrating the extraordinary property of organic p-type materials for CQD-based PDs.

Solution processed CuInS2/SnO2 heterojunction based self-powered photodetector for UV encrypted visible light communication

A photodetector (PD) featuring dual-band detection capability and self-powering attributes is crucial for various applications in sensing, communication, and imaging. Here, we present a self-powered PD based on a solution-processed CuInS2/SnO2 heterojunction capable of detecting ultraviolet (UV) and visible light spectra. The CuInS2 layer was composed of ∼2 nm-sized quantum dots (QDs) synthesized using the hot injection method, while the SnO2 layer was fabricated using a straightforward sol-gel technique. This self-powered PD displayed a significant spectral response across both UV (355 nm) and visible light (532 nm) ranges, all accomplished without the need for external bias. The PD demonstrates rapid detection, with rise and decay times of 125 ms and 156ms for visible light and 85 ms and 200 ms for UV light, respectively, at a power level of 15 mW. The PD achieved responsivity values of 10.66 μA/W and 34.56 μA/W for visible and UV light, respectively. The impressive capability for dual-band detection in both ultraviolet (UV) and visible light showcases the practical feasibility and utility of this device for self-powered photodetection and deciphering UV-encrypted visible light communication. Moreover, its straightforward solution-based processing attribute renders it valuable for the mass production of devices and technology.

Recyclable and leakage-suppressed microcellular liquid–metal composite foams for stretchable electromagnetic shielding

The metallic conductivity and high liquidity of liquid metal (LM) make LM-polymer composites exhibit high electrical conductivity, large stretchability, and excellent mechanical–electrical decoupling, which provide significant advantages in the fabrication of stretchable electromagnetic interference (EMI) shielding materials. However, problems such as undesired LM leakage, high density, and poor recyclability due to the frequent use of chemically cross-linked polymers limit the applications of LM-polymer composites. Herein, we report the fabrication of stretchable and recyclable microcellular thermoplastic polyurethane (TPU)/LM composite foams (TLFs) with controllable LM distribution through a water–vapor-induced phase separation (WVIPS) process. The sedimentation of LM droplets helps to improve the shielding effectiveness (SE) of TLF, while the microcellular structure enables TLF with more uniform LM dispersion to achieve high leakage resistance. Moreover, the stretch-activated TLF shows high electrical stability with only slight resistance changes during stretching and exhibits a strain-insensitive shielding behavior. As a stretchable joule heater, the sample has outstanding Joule-heating performance, with stable temperature dropping only slightly under large tensile strains. More importantly, the excellent solubility of TPU, combined with a solution-based WVIPS process, allows our TLFs to be easily recycled into new products with very similar structure and performance to those before recycling, indicating the ideal recyclability of such materials.