Crystal Films Research Articles

Engineering Thin Films of Silicon Phthalocyanines for Organic Thin Film Transistors

Metal phthalocyanines (MPc) show great promise as semiconductors due to their exceptional optoelectronic properties, high thermal and photochemical stability, and ability to be easily synthesized and functionalized for specific applications. The metal/metalloid ion in the center of the MPc ring can significantly influence the electronic, optical, and magnetic properties of the compound, as well as its solubility and stability. The majority of MPc, such as copper phthalocyanine (CuPc) are used as hole-transport materials (p-type) in organic electronics. Silicon phthalocyanines (R2-SiPc) are emerging semiconductors which predominantly moves electrons and have led to high performance n-type organic thin-film transistors (OTFTs). Their low synthetic complexity paired with their versatile axial group facilitates the finetuning of their chemical properties, solution properties and processing characteristics without significantly affecting their frontier orbital levels or their absorption properties. The crystal engineering and film forming characteristics of R2-SiPc semiconductors can be tuned through appropriate axial group functionalization, therefore facilitating their integration into both OTFTs and OPVs by solution processing or vapor deposition.Our group has developed families of R2-SiPc and integrated them into OTFTs with an emphasis on thin film processing and engineering of the interfaces for improved device performance. We have established structure property relationships of the final device performance as a function of 1) R2-SiPc axial groups and peripheral groups, 2) surface chemistry and composition and 3) thin film deposition conditions. I will also be discussing our recent work using advanced film characterization such as polarized Raman microscopy and synchrotron based scanning transmission x-ray microscopy to evaluate the resulting films and optimize the OTFT performance. Figure 1

(Invited) Self-Discharge of Layered Oxide Cathodes Induced by Carbonate-Mediated Hydrogenation

Significant efforts have been made to improve the energy and power characteristics of cathodes in Li-ion batteries, while the research into cathode self-discharge has lagged behind. Self-discharge is the voltage drop experienced by all rechargeable batteries while stored in the charged state. The voltage drop becomes more problematic with increased cathode voltage and temperature. The physicochemical nature of internal reactions leading to cathode self-discharge is hardly understood and seldom discussed.To tackle this challenge, the structure and redox evolution of commercial LiNi0.5Mn0.3Co0.2O2 electrodes and single crystal cathode thin films upon the self-discharge in carbonate-based electrolyte is revealed by surface-sensitive X-ray scattering, spectrometric and electrochemical characterizations in conjunction with thermodynamic analysis. As evidenced by the interfacial toolkits and theoretical calculations, there is an evolution and growth of cathode surface reduction layer in different types of electrolyte after self-discharged from different potentials. Structural and chemical chacterizations as well as the elemental depth profiles within cathode thin film confirms proton-insertion-induced layered cathode hydrogenation. Calculation shows that such process is both thermodynamically and kinetically favorable and is triggered by the interfacial hydrogen atom abstraction of methylene group in carbonate solvent on delithiated cathode surface. A combination of experimental and theoretical studies reveals the carbonate-mediated cathode hydrogenation mechanism accounting for the voltage drop in the self-discharge. This offers additional understanding regarding defect generation and the degradation mechanism in layered cathodes beyond the traditional behaviors of lithium-diffusion-induced self-discharge and rock-salt phase induced cathode degradation. This study offers foundational knowledge of the interfacial degradation of cathode that can be translated to the rational design of improved cathodes and electrolytes, and the self-discharge mechanism studies in other electrochemical ion insertion materials and devices.

Highly Flexible and Reversible Stimuli-Responsive Photonic Crystal Film in Anti-Counterfeit, Detector, and Coating.

Various fascinating optical characteristics in organisms encourage scientists to develop biomimetic synthesis strategies and mimic their unique microstructure. Inspired by the Chameleon's skin with tunable color and superior flexibility, this work designs the evaporated-induced self-assembly technique to synthesize the chiral photonic crystal film. Ultrasonic-intensified and additive-assisted techniques synergistically optimize the film properties, on the aspects of optic and mechanic. The film shows considerable rigidity and superior flexibility, which can undergo multiple mechanical deformations. Without destroying the chiral nematic structure, the ultimate strain approaches 50%, which exceeds most cellulose-derived film materials. It also integrates excellent optical performance. The film color can cover the total visible region by tuning the photonic bandgap and has angle-dependent properties. It can make the response to humidity and solvents, and chromaticity variation reflects the degree of stimulation. Importantly, this structural-dependent color change is reversible. Lastly, the photonic crystal materials with excellent mechanics and unique optics have been applied in the security. The anti-counterfeiting material design contains photonic crystal ink, repeatable writing paper, information-hiding film, and color-changing labels, with the features of environmentally friendly, economical, non-destructive, and convenient for authentication.

Preparation and Adsorption Photocatalytic Properties of PVA/TiO2 Colloidal Photonic Crystal Films.

Polyvinyl alcohol (PVA)/TiO2/colloidal photonic crystal (CPC) films with photocatalytic properties are presented, where TiO2 nanoparticles were introduced into the PVA gel network. Such PVA/TiO2/CPC films possess three-dimensional periodic structures that are supported with a PVA/TiO2 composite gel. The unique structural color of CPCs can indicate the process of material preparation, adsorption, and desorption. The shift of diffraction peaks of CPCs can be more accurately determined using fiber-optic spectroscopy. The effect of the PVA/TiO2/CPC catalyst films showed better properties as the degradation of methylene blue (MB) by the PVA/TiO2/CPC film catalyst in 4 h was 77~90%, while the degradation of MB by the PVA/TiO2 film was 33% in 4 h, indicating that the photonic crystal structure was 2.3~2.7 times more effective than that of the bulk structure.

Direct Solution Deposition of Large-Area Non-Solvated Fullerene Single-Crystal Films for High-Performance n-Type Field-Effect Transistors.

Fullerene (C60) crystals have attracted considerable attention in the field of optoelectronic devices owing to their excellent performance as n-type semiconductor material. However, a challenge still remains unbeaten as to the continuous crystallization of non-solvated C60 single-crystal films with high coverage and uniform alignment using low-cost solution techniques. Here, a facile bar coating method is used to prepare ribbon-shaped non-solvated C60 crystals with a large area (up to centimeters) and high coverage (>95%) by precisely controlling the crystallization process from specific solvents. Benefiting from the non-solvated crystalline structure, well-distributed thickness, uniform morphological alignment, and crystallographic orientation, organic field-effect transistors fabricated from the C60 single-crystal films exhibit a high average electron mobility of 2.28cm2V-1s-1, along with the coefficient of variance (CV) as small as 13.6%. This efficient manufacturing method will lay a strong foundation for C60 single-crystal films to fit into the future high-performance integrated optoelectronic application.

Facile Fabrication of Highly Crystallized, Air‐Stable, and Flexible Perovskite Micromesh Film Photodetector

AbstractPerovskite materials such as organic‐inorganic MAPbX3 (X = Cl, I, Br) have attracted broad interests in photoelectric applications, such as image sensors and photovoltaics. Here, a facile and general approach, called soft‐print solvent‐assisted evaporation crystallization (SSEC) is reported, for fabrication of highly crystallized, air‐stable, and flexible perovskite micromesh films, including organic–inorganic (MAPbX3) and inorganic (CsPbX3) perovskite. Scanning and transmission electron microscopy (SEM/TEM) characterization reveals their high crystallinity without obvious grain boundaries. The photodetectors constructed based on MAPbI3 micromesh films exhibit a typical responsivity of ≈352 A W−1 and detectivity of ≈5.7 × 1013 Jones (at 650 nm in wavelength). The MAPbI3 micromesh film also shows good mechanical stability when bended at different bending radius, and after 800 bending cycles, they still exhibit highly reproducible photocurrent and on/off switching ratios. Furthermore, they are also air‐stable that they can survive for >20 days in high humid environments (65–75%) with <10% reduction in photocurrent. This work provides a facile and scalable approach for fabrication of highly crystallized, stable, and flexible perovskite micromesh films for a variety of optoelectronic applications with improved performance and durability.

Optical imaging of ferroelectric domains in periodically poled lithium niobate using ferroelectric liquid crystals

Ferroelectric liquid crystals exhibiting a chiral smectic C* phase are deposited on z cut periodically poled lithium niobate substrates and investigated by polarized optical microscopy. While the pure substrates placed between crossed polarizers and observed in transmission appear dark, uniformly aligned liquid crystal films deposited on these substrates show alternating domains with varying brightness. This effect can be attributed to the well-known coupling between the direction of the spontaneous polarization and the optical axis in the birefringent ferroelectric smectic C* phase. Quantitative measurements of the tilt angle between the local optical axis and the smectic layer normal confirm antiparallel orientations of spontaneous polarization of the liquid crystal from domain to domain, as expected by the periodic poling of the lithium niobate substrate. This effect provides a valuable non-destructive method of optical inspection of the quality of periodically poled ferroelectric substrates, which plays an important role in achieving quasi-phase-matching in non-linear optical applications.

A recyclable, interchangeable optical switch with a PDLC-PVA-PSCLC structure and a low-voltage drive system

ABSTRACT Polymer dispersed liquid crystals (PDLC) and polymer stabilised cholesteric liquid crystals (PSCLC) are an indispensable class of electrically switchable materials, which have been widely applied in the fabrication of efficient and systematic smart windows. And doping nanoparticles in PDLC films can greatly improve their properties. In this study, PDLC films doped with zirconia nanoparticles were prepared by polymerisation-induced phase separation (PIPS) method, PSCLC films with nematic liquid crystals as the main part (reflecting wavelengths in the range of 400–600 nm) were prepared by UV curing method, and a novel optical switch was developed by combining these two liquid crystal films. The optimal bilayer sample was developed through a comparative analysis of properties among samples with varying formulations for each liquid crystal layer. This study represents a novel advancement in PSCLC and nanoparticle-doped PDLC bilayer structures, showcasing fully actuatable properties in the visible wavelength range. These structures exhibit excellent electro-optical properties and demonstrate stable, sustainable performance that can be regenerated. The findings underscore the potential of PDLC and PSCLC for applications in smart curtains and flexible materials, opening up new avenues for innovative technological applications.

Enhanced cation interaction in perovskites for efficient tandem solar cells with silicon.

To achieve the full potential of monolithic perovskite/silicon tandem solar cells, crystal defects and film inhomogeneities in the perovskite top cell must be minimized. We discuss the use of methylenediammonium dichloride as an additive to the perovskite precursor solution, resulting in the incorporation of in situ-formed tetrahydrotriazinium (THTZ-H+) into the perovskite lattice upon film crystallization. The cyclic nature of the THTZ-H+ cation enables a strong interaction with the lead octahedra of the perovskite lattice through the formation of hydrogen bonds with iodide in multiple directions. This structure improves the device power conversion efficiency (PCE) and phase stability of 1.68 electron volts perovskites under prolonged light and heat exposure under 1-sun illumination at 85°C. Monolithic perovskite/silicon tandems incorporating THTZ-H+ in the perovskite photo absorber reached a 33.7% independently certified PCE for a device area of 1 square centimeter.

Development of a Methodology Based on Optical Interferometry for Measuring Fibrinolytic Activity.

Fibrinolytic activity assay is particularly important for the detection, diagnosis, and treatment of cardiovascular disease and the development of fibrinolytic drugs. A novel efficacious strategy for real-time and label-free dynamic detection of fibrinolytic activity based on ordered porous layer interferometry (OPLI) was developed. Fibrin or a mixture of fibrin and plasminogen (Plg) was loaded into the highly ordered silica colloidal crystal (SCC) film scaffold to construct a fibrinolytic response interference layer to measure fibrinolytic activity with different mechanisms of action. Fibrinolytic enzyme-triggered fibrinolysis led to the migration of interference fringes in the interferogram, which could be represented by optical thickness changes (ΔOT) tracked in real time by the OPLI system. The morphology and optical property of the fibrinolytic response interference layer were characterized, and the Plg content in the fibrinolytic response interference layer and experimental parameters of the system were optimized. The method showed adequate sensitivity for the fibrinolytic activity of lumbrokinase and streptokinase, with wide linear ranges of 12-6000 and 10-2000 U/mL, respectively. Compared with the traditional fibrin plate method, it has a lower detection limit and higher linearity. The whole kinetic process of fibrinolysis by these two fibrinolytic drug models was recorded in real time, and the Michaelis constant and apparent kinetic parameters were calculated. Importantly, some other blood proteins were less interfering with this system, and it showed reliability in fibrin activity detection in real whole blood samples. This study established a better and more targeted research method of in vitro fibrinolysis and provided dynamic monitoring data for the analysis of fibrinolytic activity of whole blood.

From Chalcogen Bonding to S-π Interactions in Hybrid Perovskite Photovoltaics.

The stability of hybrid organic-inorganic halide perovskite semiconductors remains a significant obstacle to their application in photovoltaics. To this end, the use of low-dimensional (LD) perovskites, which incorporate hydrophobic organic moieties, provides an effective strategy to improve their stability, yet often at the expense of their performance. To address this limitation, supramolecular engineering of noncovalent interactions between organic and inorganic components has shown potential by relying on hydrogen bonding and conventional van der Waals interactions. Here, the capacity to access novel LDperovskite structures that uniquely assemble through unorthodox S-mediated interactions is explored by incorporating benzothiadiazole-based moieties. The formation of S-mediated LD structures is demonstrated, including one-dimensional (1D) and layered two-dimensional (2D) perovskite phases assembled via chalcogen bonding and S-π interactions. This involved a combination of techniques, such as single crystal and thin film X-ray diffraction, as well as solid-state NMR spectroscopy, complemented by molecular dynamics simulations, density functional theory calculations, and optoelectronic characterization, revealing superior conductivities of S-mediated LD perovskites. The resulting materials are applied in n-i-p and p-i-n perovskite solar cells, demonstrating enhancements in performance and operational stability that reveal a versatile supramolecular strategy in photovoltaics.

Enhancing terahertz magneto-optical effects in wafer-scale RIG single crystal thick films with anti-reflective coatings for improved transmittance

Wafer-scale rare-earth iron garnet (RIG) single crystal thick films were fabricated on 3-in. gadolinium gallium garnet (GGG) substrates using liquid phase epitaxy. The terahertz transmittance of the RIG crystals improved after removing the GGG substrate by polishing. The time-domain spectra at Terahertz (THz) frequencies indicate the existence of a magneto-optical effect in RIG samples. The results indicate that the RIG samples exhibit a high refractive index of ∼4.50 within the 0.1–1.0 THz frequency range, a transmittance of around 40%, and an absorption rate of only 10–50 cm−1. The Faraday rotation angles of the thick single-crystal films of the RIG samples were measured using a THz-TDS system. The RIG has a thickness of ∼330 μm. The Faraday rotation angles of RIG crystals at THz frequencies can reach up to 16° when an external magnetic field of 0.18 T is applied. The Verdet constants of the RIG sample were calculated to be ∼120°/mm/T. To improve the transmittance of the RIG sample, epoxy resin and polymethylpentene (TPX) were used as anti-reflective films. The transmittance of the RIG sample increased by ∼5% for the 80 μm thick epoxy and about 10% for the 320 μm thick TPX. Therefore, this RIG single crystal thick film can achieve a low loss, a high transmittance, and a strong magneto-optical effect in the terahertz region with the cooperation of a reflection-reducing film. It is expected to have wide applications in terahertz magnetic polarization conversion, non-reciprocal phase shifters, and isolators.

Scaling Up Perovskite Solar Cell Fabrication: Antisolvent‐Controlled Crystallization of Printed Perovskite Semiconductor

Scaling up perovskite solar cells stands as one of the frontiers in advancing this rapidly growing technology. Yet, controlling perovskite thin‐film crystallization during and post‐printing differs significantly from lab‐scale processes that have yielded record device efficiencies. This study investigates antisolvent treatment for slot‐die‐coated perovskite solar cells using in situ optical spectroscopy and comparing among multiple antisolvents. The antisolvent bath used in slot‐die coating affects the perovskite crystallization and film quality differently when comparing to the established spin‐coating antisolvent treatment process. A novel dynamic antisolvent method, employing either vortex or laminar flow, is developed. It outperforms steady‐bath techniques in generating high‐quality, haze‐free films. Optimization studies identify critical treatment times. Implementing this novel antisolvent treatment leads to a peak average power conversion efficiency of 15.62% and the highest device efficiency of 18.57%, an excellent performance for slot‐die‐coated MAPbI3 devices printed and tested under ambient conditions. The method is validated for an alternative perovskite composition, FA0.9Cs0.1PbI3, and printing technique, blade coating. This research highlights the importance of in situ analysis for enhancing perovskite film quality and introduces scalable approaches for controlling large‐area film crystallization kinetics, driven by the demand for efficient and scalable manufacturing processes in the field of perovskite solar cells.

Simulating Stretch-Induced Crystallization of Polyethylene Films: Strain Rate and Temperature Effect on the Kinetics and Morphology

Simulating Stretch-Induced Crystallization of Polyethylene Films: Strain Rate and Temperature Effect on the Kinetics and Morphology

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.

Simulation Study of Crystalline Al2O3 Thin Films Prepared at Low Temperatures: Effect of Deposition Temperature and Biasing Voltage

In this paper, classical molecular dynamics simulations were used to explore the impact of deposition temperature and bias voltage on the growth of Al2O3 thin films through magnetron sputtering. Ion energy distributions were derived from plasma mass spectrometer measurements. The fluxes of deposited particles (Ar+, Al+, and O−) were categorized into low, medium, and high energies, and the results show that the films are dominated by amorphous Al2O3 at low incident energies without applying bias. As the deposition temperature increased, the crystallinity of the films also increased, with the crystals predominantly consisting of γ-Al2O3. The crystal content of the deposited films increased when biased with −20 V compared to when no bias was applied. Crystalline films were successfully obtained at a deposition temperature of 773 K with a −20 V bias. When biased with −40 V, crystals could be obtained at a lower deposition temperature of 573 K. Increasing the bias enables the particles to have higher energy to overcome the nucleation barrier of the crystallization process, leading to a greater degree of film crystallization. At this stage, the average bond length between Al-O is measured to be approximately 1.89 Å to 1.91 Å, closely resembling that of the crystal.

Influence of AZO buffer layer on characteristics of ZnO film on glass substrates for Schottky UV photodetector applications

An Al-doped ZnO (AZO) thin film was introduced into the structure of Ag/ZnO schottky Photo detectors (PDs) prepared by magnetron sputtering method on glass substrates. Influences of AZO layer on characteristics of ZnO film and performances of Ag/ZnO schottky PDs were discussed in detail. Results investigated by means of the scanning electron microscopy (SEM), X-ray diffraction (XRD) and Photoluminescence (PL) spectra show that the introduction of an AZO buffer layer can effectively decrease the defects and improve the crystallization of the ZnO thin film. Compared with Ag/ZnO schottky PDs, the Ag/ZnO/AZO PDs possess more excellent rectifying characteristics, the photocurrent (Iph) to dark current (Id) ratio are improved from 6.4 to 100.7. Given the bias voltage at -2 V, the photoresponsivity R and detectivity D* are increased from 0.15 A W-1 to 4.08 × 1010 Jones to 0.69AW-1 and 3.78 × 1011 Jones, respectively. The response speed becomes faster, the response and delay times are decreased from 281 to 395 ms to 178 and 300 ms, respectively. The results provide a new idea for the preparation of high performance ZnO film UV PDs on low-cost glass substrates.

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.

Temperature-assisted crystallization and morphology for CH3NH3PbI3 perovskite solar cells using laser-induced heat treatment

In this study, perovskite solar cells (PSCs) were fabricated using a two-step solution deposition method. A laser beam was applied at the interface between lead iodide (PbI2) and methylammonium iodide to change the reaction temperature and stimulate the growth of perovskite crystals. A notable enhancement was observed in the power conversion efficiency of PSCs. The laser scanning speed was investigated to control the reaction temperature and further control the crystallization and morphology of the perovskite film. Based on the optimized laser scanning speed, the best and average PCEs obtained were 14.33 % and 13.92 ± 0.52 %, respectively, which were higher than those achieved using the conventional technique (12.18 % and 11.37 ± 0.74 %, respectively) and the conventional heating methods (14.09 % and 13.28 ± 0.56 %, respectively). The optimal reaction temperature at the interface was predicted to be 80 °C under optimized conditions using the COMSOL software. This study will help in scaling this technique for large–area PSCs, optimizing the laser parameters for different perovskite compositions, and investigating the long-term stability of enhanced PSCs, boosting their commercial viability.

Enhancing thermoelectric performance with perpendicular anisotropic magnetic domain arrays

In recent years, the incorporation of magnetic nanoparticles into thermoelectric materials has been introduced to enhance their performance. However, understanding the impact of dispersed magnetic substances in the matrix on thermoelectric properties, considering different domain directions, is crucial for performance improvement. In this study, we have designed and fabricated high-quality epitaxial single crystal thin films consisting of FePt arrays with varying magnetic domain directions embedded in an Sb2Te3 matrix. Our findings reveal that the electrical transport behavior of the films responds differently to magnetic materials with distinct domain directions, especially in the case of discontinuous arrays. The FePt array oriented perpendicular to the carrier flow direction effectively regulates the direction of carrier movement and local low-energy carriers, functioning as an "energy supplier" to enhance material performance. Simultaneously, the quantum dots formed between the Sb2Te3 and the metal film play the role of carrier channels, further regulating the carrier concentration. Therefore, the perpendicular magnetic anisotropy array synergistically modulates the electrical transport behavior through carriers, resulting in a significant improvement in the thermoelectric power factor. By increasing the S value at the measurement temperature, we achieved a maximum power factor (PFmax) of 3.35 mWm-1K-2 and an average power factor (PFave) of 3.14 mWm-1K-2.