LiF-Rich Solid Electrolyte Interphase Formation by Establishing Sacrificial Layer on the Separator.

The formation of a stable solid electrolyte interphase (SEI) layer is crucial for enhancing the safety and lifespan of Li metal batteries. Fundamentally, a homogeneous Li+ behavior by controlling the chemical reaction at the anode/electrolyte interface is the key to establishing a stable SEI layer. However, due to the highly reactive nature of Li metal anodes (LMAs), controlling the movement of Li+ at the anode/electrolyte interface remains challenging. Here, an advanced approach is proposed for coating a sacrificial layer called fluorinated self-assembled monolayer (FSL) on a boehmite-coated polyethylene (BPE) separator to form a stable SEI layer. By leveraging the strong affinity between the fluorine functional group and Li+, the rapid formation of a LiF-rich SEI layer in the cell production and early cycling stage is facilitated. This initial stable SEI formation promotes the subsequent homogeneous Li+ flux, thereby improving the LMA stability and yielding an enhanced battery lifespan. Further, the mechanism behind the stable SEI layer generation by controlling the Li+ dynamics through the FSL-treated BPE separator is comprehensively verified. Overall, this research offers significant contributions to the energy storage field by addressing challenges associated with LMAs, thus highlighting the importance of interfacial control in achieving a stable SEI layer.

Metal nanoparticle arrays via a water-based lift-off scheme using a block copolymer template.

Metalnanoparticles(NPs) can exhibit unique electronic, magnetic, optical, and catalytic properties. Highly ordered, dense arrays of non-close-packed, surface-supported metal NPs are thus of potential use in a wide range of applications. Implementing such arrays over large surfaces can, however, be both technologically challenging and prohibitively expensive using conventional top-down nanofabrication techniques. Moreover, many existing patterning methods are too harsh for sensitive substrate surfaces and their applications. To address this, we here investigate a fabrication protocol involving a water-based lift-off scheme in which the template pattern generation is rapidly and inexpensively achieved throughblock copolymer(BCP) self-assembly. A three-layer lift-off stack consisting of, from top to bottom, a poly(styrene-block-2-vinyl pyridine) template, a SiOxintermediate hardmask, and a water-soluble poly(vinyl alcohol) sacrificial layer is employed in this endeavor.Solvent-induced surface reconstruction(SISR) is used to generate an initial surface topography in the BCP template which is subsequently transferred to the layers beneath in a sequence of reactive ion etching steps. Through judicious selection of stack materials and dry etch chemistries, a layered, high-aspect-ratio, nanoporous mask is thus implemented. After metal deposition, the mask and excess material are simply removed in a lift-off step by dissolving the bottommost sacrificial layer in water. The incorporation of an intermediate hardmask and a water-soluble sacrificial layer obviates the need for harmful and/or corrosive lift-off solvents and decouples the BCP self-assembly process from the influence of substrate properties. We demonstrate the generation of well-ordered arrays of Au NPs capable of supporting sharp, localized surface plasmon resonances. We also investigate improvements to large-scale uniformity, as this is found sensitive to the SISR termination step in the original protocol. Extensions of the technique to other BCP morphologies and materials deposited ought to be straightforward.

Cantilever Type Acceleration Sensors Made by Roll-to-Roll Slot-Die Coating.

This paper presents the fabrication by means of roll-to-roll slot-die coating and characterization of air gap-based cantilever type capacitive acceleration sensors. As the mass of the sensor moves in the opposite direction of the acceleration, a capacitance change occurs. The sensor is designed to have a six layers structure with an air gap. Fabrication of the air gap and cantilever was enabled by coating and removing water-soluble PVA. The bottom electrode, the dielectric layer, and the sacrificial layer were formed using the roll-to-roll slot-die coating technique. The spacer, the top electrode, and the structural layer were formed by spin coating. Several kinds of experiments were conducted for characterization of the fabricated sensor samples. Experimental results show that accelerations of up to 3.6 g can be sensed with an average sensitivity of 0.00856 %/g.

Multi-Electrode Array with a Planar Surface for Cell Patterning by Microprinting.

Multielectrode arrays (MEAs) are devices for non-invasive electrophysiological measurements of cell populations. This paper describes a novel fabrication method of MEAs with a fully planar surface. The surface of the insulation layer and the surface of the electrodes were on one plane; we named this device the planar MEA (pMEA). The main advantage of the pMEA is that it allows uniform contact between the pMEA surface and a substrate for positioning of microfluidic channels or microprinting of a cell adhesive layer. The fabrication of the pMEA is based on a low adhesive Au sacrificial peel-off layer. In divergence from conventional MEAs with recessed electrodes, the electrodes of the pMEA lead across the sloped edge of the insulation layer. To make this, the profile of the edge of the insulation layer was measured and the impedance of the planar electrodes was characterized. The impedance of the pMEA was comparable with the impedance of conventional MEA electrodes. The pMEA was tested for patterning HL-1 cells with a combination of imprinting fibronectin and coating by antifouling poly (l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG). The HL-1 cells remained patterned even at full confluency and presented spontaneous and synchronous beating activity.

Sr4Al2O7: A New Sacrificial Layer with High Water Dissolution Rate for the Synthesis of Freestanding Oxide Membranes.

Freestanding perovskite oxide membranes have drawn great attention recently since they offer exceptional structural tunability and stacking ability, providing new opportunities in fundamental research and potential device applications in silicon-based semiconductor technology. Among different types of sacrificial layers, the (Ca, Sr, Ba)3Al2O6 compounds are most widely used since they can be dissolved in water and prepare high-quality perovskite oxide membranes with clean and sharp surfaces and interfaces; However, the typical transfer process takes a long time (up to hours) in obtaining millimeter-size freestanding membranes, let alone realize wafer-scale samples with high yield. Here, a new member of the SrO-Al2O3 family, Sr4Al2O7 is introduced, and its high dissolution rate, ≈10 times higher than that of Sr3Al2O6 is demonstrated. The high-dissolution-rate of Sr4Al2O7 is most likely related to the more discrete Al-O networks and higher concentration of water-soluble Sr-O species in this compound. This work significantly facilitates the preparation of freestanding membranes and sheds light on the integration of multifunctional perovskite oxides in practical electronic devices.

Unfolding the Challenges To Prepare Single Crystalline Complex Oxide Membranes by Solution Processing.

The ability to prepare single crystalline complex oxide freestanding membranes has opened a new playground to access new phases and functionalities not available when they are epitaxially bound to the substrates. The water-soluble Sr3Al2O6 (SAO) sacrificial layer approach has proven to be one of the most promising pathways to prepare a wide variety of single crystalline complex oxide membranes, typically by high vacuum deposition techniques. Here, we present solution processing, also named chemical solution deposition (CSD), as a cost-effective alternative deposition technique to prepare freestanding membranes identifying the main processing challenges and how to overcome them. In particular, we compare three different strategies based on interface and cation engineering to prepare CSD (00l)-oriented BiFeO3 (BFO) membranes. First, BFO is deposited directly on SAO but forms a nanocomposite of Sr-Al-O rich nanoparticles embedded in an epitaxial BFO matrix because the Sr-O bonds react with the solvents of the BFO precursor solution. Second, the incorporation of a pulsed laser deposited La0.7Sr0.3MnO3 (LSMO) buffer layer on SAO prior to the BFO deposition prevents the massive interface reaction and subsequent formation of a nanocomposite but migration of cations from the upper layers to SAO occurs, making the sacrificial layer insoluble in water and withholding the membrane release. Finally, in the third scenario, a combination of LSMO with a more robust sacrificial layer composition, SrCa2Al2O6 (SC2AO), offers an ideal building block to obtain (001)-oriented BFO/LSMO bilayer membranes with a high-quality interface that can be successfully transferred to both flexible and rigid host substrates. Ferroelectric fingerprints are identified in the BFO film prior and after membrane release. These results show the feasibility to use CSD as alternative deposition technique to prepare single crystalline complex oxide membranes widening the range of available phases and functionalities for next-generation electronic devices.

The Use of Sacrificial Graphite-like Coating to Improve Fusion Efficiency of Copper in Selective Laser Melting.

Thin and ultrathin carbon films reduce the laser energy required for copper powder fusion in selective laser melting (SLM). The low absorption of infrared (IR) radiation and its excellent thermal conductivity leads to an intricate combination of processing parameters to obtain high-quality printed parts in SLM. Two carbon-based sacrificial thin films were deposited onto copper to facilitate light absorption into the copper substrates. Graphite-like (3.5 µm) and ultra-thin (25 nm) amorphous carbon films were deposited by aerosol spraying and direct current magnetron sputtering, respectively. The melting was analyzed for several IR (1.06 µm) laser powers in order to observe the coating influence on the energy absorption. Scanning electron microscopy showed the topography and cross-section of the thermally affected area, electron backscatter diffraction provided the surface chemical composition of the films, and glow-discharge optical emission spectroscopy (GDOES) allowed the tracking of the in-deep chemical composition of the 3D printed parts using carbon film-covered copper. Ultra-thin films of a few tens of nanometers could reduce fusion energy by about 40%, enhanced by interferences phenomena. Despite the lower energy required, the melting maintained good quality and high wettability when using top carbon coatings. A copper part was SLM printed and associated with 25 nm of carbon deposition between two copper layers. The chemical composition analysis demonstrated that the carbon was intrinsically removed during the fusion process, preserving the high purity of the copper part.

Ultra-Smooth Polishing of Single-Crystal Silicon Carbide by Pulsed-Ion-Beam Sputtering of Quantum-Dot Sacrificial Layers.

Single-crystal silicon carbide has excellent electrical, mechanical, and chemical properties. However, due to its high hardness material properties, achieving high-precision manufacturing of single-crystal silicon carbide with an ultra-smooth surface is difficult. In this work, quantum dots were introduced as a sacrificial layer in polishing for pulsed-ion-beam sputtering of single-crystal SiC. The surface of single-crystal silicon carbide with a quantum-dot sacrificial layer was sputtered using a pulsed-ion beam and compared with the surface of single-crystal silicon carbide sputtered directly. The surface roughness evolution of single-crystal silicon carbide etched using a pulsed ion beam was studied, and the mechanism of sacrificial layer sputtering was analyzed theoretically. The results show that direct sputtering of single-crystal silicon carbide will deteriorate the surface quality. On the contrary, the surface roughness of single-crystal silicon carbide with a quantum-dot sacrificial layer added using pulsed-ion-beam sputtering was effectively suppressed, the surface shape accuracy of the Ø120 mm sample was converged to 7.63 nm RMS, and the roughness was reduced to 0.21 nm RMS. Therefore, the single-crystal silicon carbide with the quantum-dot sacrificial layer added via pulsed-ion-beam sputtering can effectively reduce the micro-morphology roughness phenomenon caused by ion-beam sputtering, and it is expected to realize the manufacture of a high-precision ultra-smooth surface of single-crystal silicon carbide.

Research on Processing Technology of Multi-Layer Heterogeneous Material Composite Micron Cantilever Beam Structure.

In order to overcome the simplicity and instability of micron cantilever membrane structure, sacrificial layer technology and multi-layer heterogeneous material composite stacking technology were designated. Based on the research with respect to a multi-layer heterogeneous cantilever beam structure, multi-layer heterogeneous material composite, and sacrificial layer release craft, different characteristics of sacrificial layer material and film preparation craft were analyzed. According to these results, the suitable film preparation craft was generated to reduce the stress between materials and to improve the reliability and percentage of finished products. Our work put multi-layer material composite micro-cantilever beam structure into practice, and accelerated the manufacturing of a micro-acceleration sensor and vibration sensor in the future.

A Novel Synthesis of ZnO Nanoflower Arrays Using a Lift-Off Technique with Different Thicknesses of Al Sacrificial Layers on a Patterned Sapphire Substrate.

A novel method to synthesize large-scale ZnO nanoflower arrays using a protrusion patterned ZnO seed layer was investigated. Different thicknesses of aluminum (Al) film were deposited on the concave patterned sapphire substrate as a sacrificial layer. ZnO gel was layered onto the Al film as a seed layer and OE-6370HF AB optical glue was used as the adhesive material. A lift-off technique was used to transfer the protrusion patterned ZnO/AB glue seed layer to a P-type Si <100> wafer. The hydrothermal method using Zn(CH3COO)2 and C6H12N4 solutions as liquid precursors was used to synthesize ZnO nanoflower arrays on the patterned seed layer. X-ray diffraction spectra, field-effect scanning electron microscopy, focused ion beam milling (for obtaining cross-sectional views), and photoluminescence (PL) spectrometry were used to analyze the effects that different synthesis times and different thicknesses of Al sacrificial layer had on the properties of ZnO nanoflower arrays. These effects included an increased diameter, and a decreased height, density (i.e., number of nanorods in µm-2), total surface area, total volume, and maximum emission intensity of PL spectrum. We showed that when the synthesis time and the thickness of the Al sacrificial layer were increased, the emission intensities of the ultraviolet light and visible light had different variations.

Bendable Polycrystalline and Magnetic CoFe2O4 Membranes by Chemical Methods.

The preparation and manipulation of crystalline yet bendable functional complex oxide membranes has been a long-standing issue for a myriad of applications, in particular, for flexible electronics. Here, we investigate the viability to prepare magnetic and crystalline CoFe2O4 (CFO) membranes by means of the Sr3Al2O6 (SAO) sacrificial layer approach using chemical deposition techniques. Meticulous chemical and structural study of the SAO surface and SAO/CFO interface properties have allowed us to identify the formation of an amorphous SAO capping layer and carbonates upon air exposure, which dictate the crystalline quality of the subsequent CFO film growth. Vacuum annealing at 800 °C of SAO films promotes the elimination of the surface carbonates and the reconstruction of the SAO surface crystallinity. Ex-situ atomic layer deposition of CFO films at 250 °C on air-exposed SAO offers the opportunity to avoid high-temperature growth while achieving polycrystalline CFO films that can be successfully transferred to a polymer support preserving the magnetic properties under bending. Float on and transfer provides an alternative route to prepare freestanding and wrinkle-free CFO membrane films. The advances and challenges presented in this work are expected to help increase the capabilities to grow different oxide compositions and heterostructures of freestanding films and their range of functional properties.

Optimization of Sacrificial Layer Etching in Single-Crystal Silicon Nano-Films Transfer Printing for Heterogeneous Integration Application.

As one of the important technologies in the field of heterogeneous integration, transfer technology has broad application prospects and unique technical advantages. This transfer technology includes the wet chemical etching of a sacrificial layer, such that silicon nano-film devices are released from the donor substrate and can be transferred. However, in the process of wet etching the SiO2 sacrificial layer present underneath the single-crystal silicon nano-film by using the transfer technology, the etching is often incomplete, which seriously affects the efficiency and quality of the transfer and makes the device preparation impossible. This article analyzes the principle of incomplete etching, and compares the four factors that affect the etching process, including the size of Si nano-film on top of the sacrificial layer, the location of the anchor point, the shape of Si nano-film on top of the sacrificial layer, and the thickness of the sacrificial layer. Finally, the etching conditions are obtained to avoid the phenomenon of incomplete etching of the sacrificial layer, so that the transfer technology can be better applied in the field of heterogeneous integration. Additionally, Si MOSFETs (Metal-Oxide-Semiconductor Field Effect Transistors) on sapphire substrate were fabricated by using the optimized transfer technology.

Infinite Selectivity of Wet SiO2 Etching in Respect to Al.

We propose and demonstrate an unconventional method suitable for releasing microelectromechanical systems devices containing an Al layer by wet etching using SiO2 as a sacrificial layer. We used 48% HF solution in combination with 20% oleum to keep the HF solution water-free and thus to prevent attack of the Al layer, achieving an outstanding etch rate of thermally grown SiO2 of ≈1 µm·min-1. We also verified that this etching solution only minimally affected the Al layer, as the chip immersion for ≈9 min increased the Al layer sheet resistance by only ≈7.6%. The proposed etching method was performed in an ordinary fume hood in a polytetrafluorethylene beaker at elevated temperature of ≈70 °C using water bath on a hotplate. It allowed removal of the SiO2 sacrificial layer in the presence of Al without the necessity of handling highly toxic HF gas.

Transfer of Epitaxial SrTiO3 Nanothick Layers Using Water-Soluble Sacrificial Perovskite Oxides.

The integration of functional thin film materials with adaptable properties is essential for the development of new paradigms in information technology. Among them, complex oxides with perovskite structures have huge potential based on the particularly vast diversity of physical properties. Here, we demonstrate the possibility of transferring perovskite oxide materials like SrTiO3 onto a silicon substrate using an environmentally friendly process at the nanoscale by means of a water-soluble perovskite sacrificial layer, SrVO3. Based on in situ monitoring atomic force microscopy and photoemission studies, we reveal that the dissolution is initiated from a strontium-rich phase at the extreme surface of SrVO3. The nanothick SrTiO3-transferred layer onto silicon presents appropriate morphology and monocrystalline quality, providing a proof of concept for the integration and development of all-perovskite-oxide electronics or "oxitronics" onto any Si-based substrate.

A Fast Route Towards Freestanding Single-Crystalline Oxide Thin Films by Using YBa2Cu3O7-x as a Sacrificial Layer.

Researchers have long been seeking multifunctional materials that can be adopted for next-generation nanoelectronics, and which, hopefully, are compatible with current semiconductor processing for further integration. Along this vein, complex oxides have gained numerous attention due to their versatile functionalities. Despite the fact that unbounded potential of complex oxides has been examined over the past years, one of the major challenges lies in the direct integration of these functional oxides onto existing devices or targeted substrates that are inherently incompatible in terms of oxide growth. To fulfill this goal, freestanding processes have been proposed, in which wet etching of inserted sacrificial layers is regarded as one of the most efficient ways to obtain epitaxial high-quality thin films. In this study, we propose using an alternative oxide, YBa2Cu3O7 (YCBO), as a sacrificial layer, which can be easily dissolved in light hydrochloric acid in a more efficient way, while protecting selected complex oxides intact. The high epitaxial quality of the selected complex oxide before and after freestanding process using YBCO as a sacrificial layer is comprehensively studied via a combination of atomic force microscopy, X-ray diffraction, transmission electron microscopy, and electrical transports. This approach enables direct integration of complex oxides with arbitrary substrates and devices and is expected to offer a faster route towards the development of low-dimensional quantum materials.

Fabrication and Characterization of Roll-to-Roll-Coated Cantilever-Structured Touch Sensors.

It is common in the field of printed electronics that polydimethylsiloxane (PDMS) be used as a dielectric layer for capacitive sensors because of its high elasticity and restoration force. However, capacitive sensors with the PDMS dielectric layer have a lower sensitivity than those with an air-gap structure that has been fabricated by the conventional micro-electromechanical system (MEMS) process. This paper presents a productive method for fabricating air-gap structures for touch sensors by roll-to-roll slot-die coating. The air-gap is formed by coating and removing a sacrificial layer. Cantilever-structured capacitive touch sensors with an air-gap are fabricated as follows: First, the bottom electrode, the dielectric layer, and the poly(vinyl alcohol) (PVA) sacrificial layer are roll-to-roll slot-die-coated on a flexible substrate. In addition, the spacer layer is spin-coated. On the sacrificial and spacer layers, the top electrode and structural layer are formed by spin-coating. Then, the air-gap and cantilever structure are made by removing the sacrificial layer in water. The cantilever-structured sensor samples are examined in terms of sensitivity, hysteresis, and repeatability. In particular, the electrical performance of the samples is compared to those with the PDMS dielectric layer. Experimental results show that the cantilever-structured sensor samples have significantly higher sensitivity compared to those with the PDMS dielectric layer.

Fabricating High-Resolution Metal Pattern with Inkjet Printed Water-Soluble Sacrificial Layer.

The metal pattern plays a crucial role in various optoelectronic devices. However, fabrication of high-resolution metal patterns has serious problems including complicated techniques and high cost. Herein, an inkjet printed water-soluble sacrificial layer was proposed to fabricate a high-resolution metal pattern. The water-soluble sacrificial layer was inkjet printed on a polyethylene glycol terephthalate (PET) surface, and then the printed surface was deposited with a metal layer by evaporating deposition. When the deposited surface was rinsed by water, the metal layer deposited on the water-soluble sacrificial layer could be removed. Various high-resolution metal patterns were prepared, which could be used in electroluminescent displays, strain sensors, and 3D switches. This facile method could be a promising approach for fabricating high-resolution metal patterns.

Porous Membranes as Sacrificial Layers Enabling Conformal Chemical Vapor Deposition Involving Multiple Film-Forming Species.

We propose a new, concise method for conformal chemical vapor deposition (CVD) using sacrificial layers (SLs) to fill three-dimensional features with microscopic pores. SLs are porous membranes (e.g., ceramic felts) that filter film-forming species having high sticking-probability (η). CVD processes with multiple film-forming species generally suffer from poor conformality due to preferential film deposition at the inlets of features by the high-η species, such as reactive intermediates. An SL traps such high-η species before they reach the target features and selectively supplies film-forming species with lower η (e.g., source precursors or stable intermediates) that enables conformal film deposition. Here the trapping efficiency of an SL was predicted and a procedure for designing an optimal SL was established. The procedure was demonstrated by CVD of silicon carbide (SiC) with multiple film-forming species of high-η species (η = 8.0 × 10-3) and lower-η species (η = 5.9 × 10-5 and 2.2 × 10-7). The trapping of 99.2% of incident high-η species was achieved with an optimized SL, wherein the deposition rate (m/s) contribution by high-η species declined from 0.546 at the SL inlet to 0.014 at its outlet. Finally, using these optimized SLs, SiC-CVD filling of micron-scale trenches was demonstrated with an aspect-ratio of 16:1.

Ultrafast and Chemically Stable Transfer of Au Nanomembrane Using a Water-Soluble NaCl Sacrificial Layer for Flexible Solar Cells.

Large-scale industrial application of flexible device has called for development of transfer methods that deliver high yield and stability. Here, we show an ultrafast and chemically stable transfer method by using a water-soluble NaCl sacrificial layer. Extremely thin (10 nm) and large-area (4 in. wafer) free-standing Au nanomembranes (NMs) prepared on silicon substrate were successfully transferred to flexible PDMS substrate by dissolving the NaCl sacrificial layer. This transfer method enables highly transparent and electrically conductive Au NMs on PDMS substrate. To transfer a multilayered optoelectronic device, we fabricated flexible hydrogenated amorphous silicon (a-Si:H) solar cell on a glass substrate and transferred it to a PDMS substrate. There was no degradation of the electrical characteristic of the solar cell after the transfer. This approach enables the integration of high-temperature-processed a-Si:H solar cell onto low-temperature tolerant flexible polymer substrate without chemical contamination or damage.

Fabrication and Characterization of Roll-to-Roll Printed Air-Gap Touch Sensors.

Although printed electronics technology has been recently employed in the production of various devices, its use for the fabrication of electronic devices with air-gap structures remains challenging. This paper presents a productive roll-to-roll printed electronics method for the fabrication of capacitive touch sensors with air-gap structures. Each layer of the sensor was fabricated by printing or coating. The bottom electrode, and the dielectric and sacrificial layers were roll-to-roll slot-die coated on a flexible substrate. The top electrode was formed by roll-to-roll gravure printing, while the structural layer was formed by spin-coating. In particular, the sacrificial layer was coated with polyvinyl alcohol (PVA) and removed in water to form an air-gap. The successful formation of the air-gap was verified by field emission scanning electron microscopy (FE-SEM). Electrical characteristics of the air-gap touch sensor samples were analyzed in terms of sensitivity, hysteresis, and repeatability. Experimental results showed that the proposed method can be suitable for the fabrication of air-gap sensors by using the roll-to-roll printed electronics technology.