Single-Crystal Perovskite for Solar Cell Applications.

The advent of organic-inorganic hybrid metal halide perovskites has revolutionized photovoltaics, with polycrystalline thin films reaching over 26% efficiency and single-crystal perovskite solar cells (IC-PSCs) demonstrating ≈24%. However, research on single-crystal perovskites remains limited, leaving a crucial gap in optimizing solar energy conversion. Unlike polycrystalline films, which suffer from high defect densities and instability, single-crystal perovskites offer minimal defects, extended carrier lifetimes, and longer diffusion lengths, making them ideal for high-performance optoelectronics and essential for understanding perovskite material behavior. This review explores the advancements and potential of IC-PSCs, focusing on their superior efficiency, stability, and role in overcoming the limitations of polycrystalline counterparts. It covers device architecture, material composition, preparation methodologies, and recent breakthroughs, emphasizing the importance of further research to propel IC-PSCs toward commercial viability and future dominance in photovoltaic technology.

3D printing assisted surface patterning process on acrylated hydrogels for contact guidance of fibroblasts.

Generating stable and customizable topography on hydrogel surfaces with contact guidance potential is critical as it can direct/influence cell growth. This necessitates the development of new techniques for surface patterning of the hydrogels. We report on the design of a square grid template for surface patterning hydrogels. The template was 3-D printed and has the diameter of a well in a 24-well plate. Hyaluronic acid methacrylate (HA) hydrogel precursor solutions were cast on the 3D printed template's surface, which generated 3D square shape topographies on the HA hydrogel surface upon demolding. The 3D Laser Microscopy has shown the formation of a periodic array of 3D topographies on hydrogel surfaces. 3D Laser and Electron Microscopy Imaging have revealed that this new method has increased the surface area and exposed the underlying pore structure of the HA hydrogels. To demonstrate the method's versatility, we have successfully applied this technique to generate 3D topography on two more acrylate hydrogel formulations, gelatin Methacrylate and polyethylene glycol dimethacrylate. Human neonatal dermal fibroblast cells were used as a model cell line to evaluate the cell guidance potential of patterned HA hydrogel. Confocal fluorescence microscopy imaging has revealed that the 3D surface topographies on HA hydrogels can guide and align the actin filaments of the fibroblasts presumably due to the contact guidance mechanism. The newly developed methodology of 3D topography generation in acrylate hydrogels may influence the cell responses on hydrogel surfaces which can impact biomedical applications such as tissue engineering, wound healing, and disease modeling.

Sequentially photocatalytic degradation of mussel-inspired polydopamine: From nanoscale disassembly to effective mineralization.

Mussel-inspired polydopamine (PDA) coating has been utilized extensively as versatile deposition strategies that can functionalize surfaces of virtually all substrates. However, the strong adhesion, stability and intermolecular interaction of PDA make it inefficient in certain applications. Herein, a green and efficient photocatalytic method was reported to remove adhesion and degrade PDA by using TiO2-H2O2 as photocatalyst. The photodegradation process of the PDA spheres was first undergone nanoscale disassembly to form soluble PDA oligomers or well-dispersed nanoparticles. Most of the disassembled PDA can be photodegraded and finally mineralized to CO2 and H2O. Various PDA coated templates and PDA hollow structures can be photodegraded by this strategy. Such process provides a practical strategy for constructing the patterned and gradient surfaces by the "top-down" method under the control of light scope and intensity. This sequential degradation strategy is beneficial to achieve the decomposition of highly crosslinked polymers.

Surface Patterning of Metal Zinc Electrode with an In-Region Zincophilic Interface for High-Rate and Long-Cycle-Life Zinc Metal Anode.

The undesirable dendrite growth induced by non-planar zinc (Zn) deposition and low Coulombic efficiency resulting from severe side reactions have been long-standing challenges for metallic Zn anodes and substantially impede the practical application of rechargeable aqueous Zn metal batteries (ZMBs). Herein, we present a strategy for achieving a high-rate and long-cycle-life Zn metal anode by patterning Zn foil surfaces and endowing a Zn-Indium (Zn-In) interface in the microchannels. The accumulation of electrons in the microchannel and the zincophilicity of the Zn-In interface promote preferential heteroepitaxial Zn deposition in the microchannel region and enhance the tolerance of the electrode at high current densities. Meanwhile, electron aggregation accelerates the dissolution of non-(002) plane Zn atoms on the array surface, thereby directing the subsequent homoepitaxial Zn deposition on the array surface. Consequently, the planar dendrite-free Zn deposition and long-term cycling stability are achieved (5,050 h at 10.0 mA cm-2 and 27,000 cycles at 20.0 mA cm-2). Furthermore, a Zn/I2 full cell assembled by pairing with such an anode can maintain good stability for 3,500 cycles at 5.0 C, demonstrating the application potential of the as-prepared ZnIn anode for high-performance aqueous ZMBs.

High-Temperature Melt Stamping of Polymers Using Polymer/Nanoporous Gold Composite Stamps.

Parallel lithographic deposition of polymers onto counterpart substrates is a widely applied surface manufacturing operation. However, polymers may only be soluble in organic solvents or are insoluble at all. Solvent evaporation during stamping may trigger hardly controllable capillarity-driven flow processes or phase separation, and polymer solutions may spread on the counterpart substrates. Solvent-free stamping of melts prevents these drawbacks. Here, a stamp design for the deposition of melts is devised, which intrinsically circumvents ink depletion. The stamps' topographically patterned contact surfaces with protruding contact elements contacting the counterpart substrates consist of a nanoporous gold layer with a thickness of a few micrometers. The nanoporous gold layer is attached to a molten polymer layer, which is support for the nanoporous gold layer and ink reservoir at the same time. The nanoporous gold layer in turn stabilizes the topography of the stamps' contact surfaces. As examples, arrays of submicron microdots of polystyrene and poly(vinylidenefluoride-trifluoroethylene) (PVDF-TrFE) are manufactured. The P(VDF-TrFE) microdots are partially crystalline, ferroelectric, and can be locally poled. It is envisioned that the methodology reported here can be automatized and may be extended to functional low-molecular-mass compounds, such as active pharmaceutical ingredients.

Modular Bicyclophane-Based Molecular Platforms.

The modular synthesis of a series of nanoscale phenylene bicyclophanes with an intraannular orthogonal pillar is described. The compounds are obtained by a Suzuki cross-coupling condensation and are characterized by mass spectrometry and NMR spectroscopy as well as in situ scanning tunneling microscopy at the solid/liquid interface of highly ordered pyrolytic graphite. In addition, their structures and conformations are supported by quantum chemical calculations, also after adsorption to the substrate. A set of two alkyl chain substitution patterns as well as a combination of both were investigated with respect to their ability to form extended 2D-crystalline superstructures on graphite. It shows that not the most densely packed surface coverage gives the most stable structure, but the largest number of alkyl chains per molecule determines the structural robustness to alterations at the pillar functionality.

Effect of valve leaflet surface patterning on valve hydrodynamic performance.

OBJECTIVE: We aimed to elucidate the effects of the micro-structure of the pyrolytic carbon for artificial heart valves on its hydrodynamic performance. METHODS: Bileaflet mechanical valves of GKS 23 and 29 A were randomly selected. According to ISO5840, mean transvalvular pressure (MPG), regurgitation fraction (RF), and effective orifice area (EOA) of valve were assessed. Then, parallel-groove pattern was constructed by laser etching on leaflet surface, and the valves were subjected again to the same test. RESULTS: Compared with before patterning at 2, 3.5, 5, and 7 L/min, the MPG of the valves in two specifications were higher, the EOA was larger in 23 A, but smaller in 29 A, and the RF was contrary to EOA. At 5 L/min, the RF in both specifications was lower after etching at 45 bpm. At 70 bpm however, the RF in 23 A decreased, in 29 A increased. CONCLUSION: The parallel-groove pattern on leaflet surface affected the hemodynamic performance of the valve prostheses.

Locking Patterned Carbon Nanotube Cages by Nanofibrous Mats to Construct Cucurbituril[n]-Based Ultrapermselective Dye/Salt Separation Membranes.

Surface patterning is a promising strategy to overcome the trade-off effect of separation membranes. Herein, a bottom-up patterning strategy of locking micron-sized carbon nanotube cages (CNCs) onto a nanofibrous substrate is developed. The strongly enhanced capillary force triggered by the abundant narrow channels in CNCs endows the precisely patterned substrate with excellent wettability and antigravity water transport. Both are crucial for the preloading of cucurbit[n]uril (CB6)-embeded amine solution to form an ultrathin (∼20 nm) polyamide selective layer clinging to CNCs-patterned substrate. The CNCs-patterning and CB6 modification result in a 40.2% increased transmission area, a reduced thickness, and a lowered cross-linking degree of selective layer, leading to a high water permeability of 124.9 L·m-2 h-1 bar-1 and a rejection of 99.9% for Janus Green B (511.07 Da), an order of magnitude higher than that of commercial membranes. The new patterning strategy provides technical and theoretical guidance for designing next-generation dye/salt separation membranes.

Solid-State Surface Patterning on Polymer Using the Microcellular Foaming Process.

This study proposes a novel process that integrates the molding and patterning of solid-state polymers with the force generated from the volume expansion of the microcellular-foaming process (MCP) and the softening of solid-state polymers due to gas adsorption. The batch-foaming process, which is one of the MCPs, is a useful process that can cause thermal, acoustic, and electrical characteristic changes in polymer materials. However, its development is limited due to low productivity. A pattern was imprinted on the surface using a polymer gas mixture with a 3D-printed polymer mold. The process was controlled with changing weight gain by controlling saturation time. A scanning electron microscope (SEM) and confocal laser scanning microscopy were used to obtain the results. The maximum depth could be formed in the same manner as the mold geometry (sample depth: 208.7 µm; mold depth: 200 µm). Furthermore, the same pattern could be imprinted as a layer thickness of 3D printing (sample pattern gap and mold layer gap: 0.4 mm), and surface roughness was increased according to increase in the foaming ratio. This process can be used as a novel method to expand the limited applications of the batch-foaming process considering that MCPs can impart various high-value-added characteristics to polymers.

Maskless, Reusable Visible-Light Direct-Write Stamp for Microscale Surface Patterning.

We report a straightforward method for creating large-area, microscale resolution patterns of functional amines on self-assembled monolayers by the photoinduced local acidification of a flat elastomeric stamp enriched with photoacid. The limited diffusivity of the photoactivated merocyanine acid in poly(dimethylsiloxane) (PDMS) enabled to confine efficient deprotection of N-tert-butyloxycarbonyl amino group (N-Boc) to line widths below 10 µm. The experimental setup is very simple and is built around the conventional HD-DVD optical pickup. The method allows cost-efficient, maskless, large-area chemical patterning while avoiding potentially cytotoxic photochemical reaction products. The activation of the embedded photoacid occurs within the stamp upon illumination with the laser beam and the process is fully reversible. Preliminary positive results highlight the possibility of repeatable use of the same stamp for the creation of different patterns.

Wrinkled Interfaces: Taking Advantage of Anisotropic Wrinkling to Periodically Pattern Polymer Surfaces.

Periodically patterned surfaces can cause special surface properties and are employed as functional building blocks in many devices, yet remaining challenges in fabrication. Advancements in fabricating structured polymer surfaces for obtaining periodic patterns are accomplished by adopting "top-down" strategies based on self-assembly or physico-chemical growth of atoms, molecules, or particles or "bottom-up" strategies ranging from traditional micromolding (embossing) or micro/nanoimprinting to novel laser-induced periodic surface structure, soft lithography, or direct laser interference patterning among others. Thus, technological advances directly promote higher resolution capabilities. Contrasted with the above techniques requiring highly sophisticated tools, surface instabilities taking advantage of the intrinsic properties of polymers induce surface wrinkling in order to fabricate periodically oriented wrinkled patterns. Such abundant and elaborate patterns are obtained as a result of self-organizing processes that are rather difficult if not impossible to fabricate through conventional patterning techniques. Focusing on oriented wrinkles, this review thoroughly describes the formation mechanisms and fabrication approaches for oriented wrinkles, as well as their fine-tuning in the wavelength, amplitude, and orientation control. Finally, the major applications in which oriented wrinkled interfaces are already in use or may be prospective in the near future are overviewed.

Gap-directed chemical lift-off lithographic nanoarchitectonics for arbitrary sub-micrometer patterning.

We introduce a unique soft lithographic operation that exploits stamp roof collapse-induced gaps to selectively remove an alkanethiol self-assembled monolayer (SAM) on Au to generate surface patterns that are orders of magnitude smaller than structures on the original elastomer stamp. The smallest achieved feature dimension is 5 nm using a micrometer-scale structured stamp in a chemical lift-off lithography (CLL) process. Molecular patterns retained in the gaps between stamp features and their circumscribed or inscribed circles follow mathematical predictions, and their sizes can be tuned by altering the stamp structure dimensions, including height, pitch, and shape. These generated surface molecular patterns can function as biorecognition arrays or be transferred to the underneath Au layer for metallic structure creation. By combining CLL process with this gap phenomenon, soft material properties that are previously thought as demerits can be used to achieve sub-10 nm features in a straightforward sketch.

Self-Assembled Asperities for Pressure-Tunable Adhesion.

Control of adhesion is important in a host of applications including soft robotics, pick-and-place manufacturing, wearable devices, and transfer printing. While there are adhesive systems with discrete switchability between states of high and low adhesion, achieving continuously variable adhesion strength remains a challenge. In this work, a pressure-tunable adhesive (PTA) that is based on the self-assembly of stiff microscale asperities on an elastomeric substrate is presented. It is demonstrated that the adhesion strength of the PTA increases with the applied compressive preload due to the unique contact formation mechanism caused by the asperities. Additionally, a contact mechanics model is developed to explain the resulting trends. For a specific PTA design, the critical pull-off force can be increased from 0.4 to 30 mN by increasing the applied preload from 1 to 30 mN. Finally, the applicability of precision control of adhesion strength is demonstrated by utilizing the PTA for pick-and-place material handling. The approach in pressure-tunable adhesive design based on self-assembly of asperities presents a scalable and versatile approach that is applicable to a variety of material systems having different mechanical or surface properties.

Surface alignment of nematic liquid crystals by direct laser writing of photopolymer alignment layers.

We demonstrate the fabrication of good quality surface alignment layers on glass by Direct Laser Writing method using a 2-photon polymerisation technique. We use commercially available photosensitive resins to print alignment layers by scanning the focal point of a femtosecond laser near the resin-glass interface. This results in down to ~ 100 nm thin alignment layers that provide good planar anchoring of 5CB and MLC13300, with the easy axis of alignment along the scanning direction. The azimuthal anchoring strength is ~ 5 × 10-6 J/m2 and is an order of magnitude weaker compared to commercial rubbed polyimide alignment layer. The threshold voltage for Fréedericksz transition in a 90° twisted nematic cell is slightly increased compared to conventional rubbed polyimide for printed alignment layers. The turn-on switching time is longer for printed layers compared to polyimide alignment layers, whereas the turn-off time is shorter for printed alignment layers. The advantage of this new method is in its flexibility, as we demonstrate printing of complex surface alignment patterns with alignment layer thickness below 100 nm.

Superrepellent Porous Polymer Surfaces by Replication from Wrinkled Polydimethylsiloxane/Parylene F.

Superrepellent surfaces, such as micro/nanostructured surfaces, are of key importance in both academia and industry for emerging applications in areas such as self-cleaning, drag reduction, and oil repellence. Engineering these surfaces is achieved through the combination of the required surface topography, such as porosity, with low-surface-energy materials. The surface topography is crucial for achieving high liquid repellence and low roll-off angles. In general, the combination of micro- and nanostructures is most promising in achieving high repellence. In this work, we report the enhancement of wetting properties of porous polymers by replication from wrinkled Parylene F (PF)-coated polydimethylsiloxane (PDMS). Fluorinated polymer foam "Fluoropor" serves as the low-surface-energy polymer. The wrinkled molds are achieved via the deposition of a thin PF layer onto the soft PDMS substrates. Through consecutive supercritical drying, superrepellent surfaces with a high surface porosity and a high water contact angle (CA) of >165° are achieved. The replicated surfaces show low roll-off angles (ROA) <10° for water and <21° for ethylene glycol. Moreover, the introduction of the micro-wrinkles to Fluoropor not only enhances its liquid repellence for water and ethylene glycol but also for liquids with low surface tension, such as n-hexadecane.

Patterned Aluminum/Polydimethylsiloxane-Laminated Film for a Solvent-Driven Soft Actuator with Programmable and Multistable Shape Morphing.

Recently, soft actuators capable of deforming in predictable ways under external stimuli have attracted increasing attention by showing great potential in emerging industries. However, limited efforts are being spent on the untethered actuators with multistable deformations. Also, there is a lack of mechanically guiding design principles for multistable structures. Here, the patterned aluminum/polydimethylsiloxane (Al/PDMS)-laminated films with surface wrinkles are fabricated by magnetron sputtering the Al layer on the PDMS substrate. By tuning the geometric parameters and surface constraints of the patterned Al/PDMS-laminated films, a series of solvent-driven actuators with multiform stable configurations (such as monostable arc, multistable cylinder, and monostable/bistable spiral) are proposed. The deformation mechanism is revealed using a linear elastic theory. Combined with the finite element analysis method, the deformations of Al/PDMS-laminated films with different surface constraints and geometric configurations are visually predicted. Besides, we modulate the deformation of different parts of the Z-shaped actuators by tuning the surface constraints in different regions of the Z-shaped Al/PDMS bilayer films to achieve multiple stable deformations in a single actuator. The concept offers a huge design scope for reconfigurable soft robots. Finally, two bionic applications are proposed to demonstrate the practical applications of the soft solvent-driven actuator based on the patterned Al/PDMS films in artificial muscles and bionic robotics. This work provides a strategy for the design and fabrication of programmable and controllable soft actuators, laying the foundation for a wide range of applications in smart materials.

Rapid Printing and Patterning of Tough, Self-Healable, and Recyclable Hydrogel Thin-Films toward Flexible Sensing Devices.

Direct and rapid printing and surface patterning of hydrogel thin films are of great significance in the construction of advanced electronic devices, yet they are greatly underdeveloped due to the intrinsic contradiction between mechanical strength and self-healability as well as recyclability. Here, we present a universal and rapid slipping-directed route with a newly developed water-soluble star polymer hydrogel for direct and reproducible printing and patterning of freestanding functional thin films with precisely controlled thicknesses, components, and surface structures on a large scale. The resulting thin films combine the features of large transmittance (93%), tough mechanical strength (114 MPa), multiresponsive self-healability, recyclability, and remarkable multifunctionality. With the unique humidity-sensitive properties as motivation, diverse humidity-sensing devices including an actuating switch, a supercapacitive sensor, and a noncontact electronic skin are facilely constructed through the humidity-induced transverse, longitudinal, and patterning assembly techniques, respectively. The method presented here is universal and efficient in the fabrication and assembly of thin films with controlled configuration and functionality for advanced flexible electronics.

RGD Nanoarrays with Nanospacing Gradient Selectively Induce Orientation and Directed Migration of Endothelial and Smooth Muscle Cells.

Directed migration of cells through cell-surface interactions is a paramount prerequisite in biomaterial-induced tissue regeneration. However, whether and how the nanoscale spatial gradient of adhesion molecules on a material surface can induce directed migration of cells is not sufficiently known. Herein, we employed block copolymer micelle nanolithography to prepare gold nanoarrays with a nanospacing gradient, which were prepared by continuously changing the dipping velocity. Then, a self-assembly monolayer technique was applied to graft arginine-glycine-aspartate (RGD) peptides on the nanodots and poly(ethylene glycol) (PEG) on the glass background. Since RGD can trigger specific cell adhesion via conjugating with integrin (its receptor in the cell membrane) and PEG can resist protein adsorption and nonspecific cell adhesion, a nanopattern with cell-adhesion contrast and a gradient of RGD nanospacing was eventually prepared. In vitro cell behaviors were examined using endothelial cells (ECs) and smooth muscle cells (SMCs) as a demonstration. We found that SMCs exhibited significant orientation and directed migration along the nanospacing gradient, while ECs exhibited only a weak spontaneously anisotropic migration. The gradient response was also dependent upon the RGD nanospacing ranges, namely, the start and end nanospacings under a given distance and gradient. The different responses of these two cell types to the RGD nanospacing gradient provide new insights for designing cell-selective nanomaterials potentially used in cell screening, wound healing, etc.

Versatile Surface Patterning with Low Molecular Weight Photoswitches.

Surface patterning of functional materials is a key technology in various fields such as microelectronics, optics, and photonics. In micro- and nanofabrication, polymers are frequently employed either as photoreactive or thermoresponsive resists that enable further fabrication steps, or as functional adlayers in electronic and optical devices. In this article, a method is presented for imprint lithography using low molecular weight arylazoisoxazoles photoswitches instead of polymer resists. These photoswitches exhibit a rapid and reversible solid-to-liquid phase transition upon photo-isomerization at room temperature, making them highly suitable for reversible surface functionalization at ambient conditions. Beyond photo-induced imprint lithography with multiple write-and-erase cycles, prospective applications as patterned matrix for nanoparticles and etch resist on gold surfaces are demonstrated.

DNA-POINT: DNA Patterning of Optical Imprint for Nanomaterials Topography.

Engineering well-defined scale-spanning structures through transfer of diverse biomolecules and materials to a surface is of tremendous interest in life sciences research yet remains profoundly challenging. Here, we report a novel method, termed as DNA patterning of optical imprint for nanomaterials topography (DNA-POINT), for rapid photopatterning of large area, geometrically complex surfaces via light-responsive DNA. Our method employs top-down multiphoton-driven patterning of azobenzene-modified DNA strands, offering precise position control of molecules and nanoparticles along the axial plane and a template for bottom-up self-assembly of multiple layers of different chemical composition along the vertical plane. We demonstrate the surface patterning of plasmonic gold nanoparticles, fluorophore-labeled oligonucleotides, and multiple layers consisting of molecule-nanoparticle hybrid patterns into preconceived shapes without compromising on the functionality of the biomolecules. Furthermore, we exhibit scanning mode operation of DNA-POINT, thereby paving the way for maskless and cleanroom-free fast fabrication of biochips for high-throughput diagnostics and biosensing applications.