During decomposition of copper formate, a volatile intermediate is formed, that can be utilized to fabricate conductive copper lines for electrical interconnections. By the method called Reactive Transfer Printing (RTP), a pattern of copper (II) formate was printed, and placed adjacent to a second surface; decomposition of the printed pattern led to a transfer of copper to the second substrate. It was found that the yield of the transfer process improved due to presence of several carboxylic acids which are liquid with a high boiling point. Furthermore we found that the transport of copper starts at a lower temperature than previously reported, indicating that the first decomposition step of copper formate is related to the catalytic decomposition of formic acid on a copper surface. The findings enable printing of conductive copper patterns onto the interior surface of a glass vessel.

Liquid drop evaporation on surfaces is present in many industrial and medical applications, e.g., printed electronics, spraying of pesticides, DNA mapping, etc. Despite this strong interest, a theoretical description of the dynamic of the evaporation of complex liquid mixtures and nanosuspensions is still lacking. Indeed, one of the aspects that have not been included in the current theoretical descriptions is the competition between the kinetics of evaporation and the adsorption of surfactants and/or particles at the liquid/vapor and liquid/solid interfaces. Materials formed by an electrically isolating solid on which a patterned conducting layer was formed by the deposits left after drop evaporation have been considered as very promising for building electrical circuits on flexible plastic substrates. In this work, we have done an exhaustive study of the evaporation of nanosuspensions of latex and hydrophobized silver nanoparticles on four substrates of different hydrophobicity. The advancing and receding contact angles as well as the time dependence of the volume of the droplets have been measured over a broad range of particle concentrations. Also, mixtures of silver particles and a surfactant, commonly used in industrial printing, have been examined. Furthermore, the adsorption kinetics at both the air/liquid and solid/liquid interfaces have been measured. Whereas the latex particles do not adsorb at the solid/liquid and only slightly reduce the surface tension, the silver particles strongly adsorb at both interfaces. The experimental results of the evaporation process were compared with the predictions of the theory of Semenov et al. (Evaporation of Sessile Water Droplets: Universal Behavior in the Presence of Contact Angle Hysteresis. Colloids Surf. Physicochem. Eng. Asp. 2011, 391 (1-3), 135-144) and showed surprisingly good agreement despite that the theory was developed for pure liquids. The morphology of the deposits left by the droplets after total evaporation was studied by scanning electronic microscopy, and the effects of the substrate, the particle nature, and their concentrations on these patterns are discussed.

We report on new material compositions enabling fully printed mechanoluminescent 3D devices by using a one-step direct write 3D printing technology. The ink is composed of PDMS, transition metal ion-doped ZnS particles, and a platinum curing retarder that enables a long open time for the printing process. 3D printed mechanoluminescent multi-material objects with complex structures were fabricated, in which light emission results from stretching or wind blowing. The multi-material printing yielded anisotropic light emission upon compression from different directions, enabling its use as a directional strain and pressure sensor. The mechanoluminescent light emission peak was tailored to match that of a perovskite material, and therefore, enabled the direct conversion of wind power in the dark into electricity, by linking the printed device to perovskite-based solar cells.

A printable hybrid hydrogel is fabricated by embedding poly(N-isopropylacrylamide) (PNIPAm) microparticles within a water-rich silica-alumina(Si/Al)-based gel matrix. The hybrid gel holds water content of up to 70 wt%, due to its unique Si/Al matrix. The hybrid hydrogel can respond to both heat and electrical stimuli, and can be directly printed layer-by-layer using a commercial 3-dimensional printer, without requiring any curing. The hybrid ink is printed onto a transparent, flexible conductive electrode composed of silver nanoparticles and sustains bending angles of up to 180°, which enables patterning of various flexible devices such as smart windows and a 3D optical waveguide valve.

We report a method to prepare highly stretchable and UV curable hydrogels for high resolution DLP based 3D printing. Hydrogel solutions were prepared by mixing self-developed high-efficiency water-soluble TPO nanoparticles as the photoinitiator with an acrylamide-PEGDA (AP) based hydrogel precursor. The TPO nanoparticles make AP hydrogels UV curable, and thus compatible with the DLP based 3D printing technology for the fabrication of complex hydrogel 3D structures with high-resolution and high-fidelity (up to 7 μm). The AP hydrogel system ensures high stretchability, and the printed hydrogel sample can be stretched by more than 1300%, which is the most stretchable 3D printed hydrogel. The printed stretchable hydrogels show an excellent biocompatibility, which allows us to directly 3D print biostructures and tissues. The great optical clarity of the AP hydrogels offers the possibility of 3D printing contact lenses. More importantly, the AP hydrogels are capable of forming strong interfacial bonding with commercial 3D printing elastomers, which allows us to directly 3D print hydrogel-elastomer hybrid structures such as a flexible electronic board with a conductive hydrogel circuit printed on an elastomer matrix.

Perovskite solar cells have emerged as a new semi-transparent PV technology for urban infrastructures that demands an explicit trade-off between power conversion efficiency (PCE) and average visible transparency (AVT) which can be adjusted by various modifications in the absorber layer. Here, we introduce a scalable and facile ``one and a half'' step deposition route for mixed cation perovskites patterned in a sub-micron sized grid structure for semi-transparent solar cells. The initial perovskite phase is formed in one step using a grid pattern, while the additional step involves dipping of the pre-deposited perovskite grid in a hot solution of formamidinium iodide (FAI) in isopropanol (IPA). Detailed analysis suggests that the additional step increases pore filling, crystal quality, and grain size and lowers the content of residual PbI2 as well as reveals improved photo physical properties. An average PCE ∼10% with an AVT of 28% is attained with a gold contact for the champion semi-transparent solar cell. The proposed deposition route can be generalized for all other types of perovskite based devices to yield better efficiency.

Metal–organic frameworks (MOFs) are a well-developed field of materials, having a high potential for various applications such as gas storage, water purification, and catalysis. Despite the continuous discoveries of new MOFs, so far there are only a limited number of industrial applications, partially due to their low chemical stability and limited mechanical properties, as well as difficulties in integration within functional devices, Herein, a new approach is presented toward the fabrication of MOF-based devices, utilizing direct 3D printing. By this method, 3D, flexible, and hydrolytically stable MOF-embedded polymeric structures are fabricated. It is found that the adsorption capacity of the 3D-printed MOF is retained, with significantly improved hydrolytic stability of the printed MOFs (copper benzene-1,3,5-tricarboxylate) compared to the MOF only. It is expected that applying 3D printing technologies, for the fabrication of functional MOF objects such as filters and matrices for columns and flow reactors, will open the way for utilization of this important class of materials.

Vanadium dioxide (VO2) nanoparticles with reversible semiconductor-metal phase transition holds the tremendous potential as a thermochromic material for the energy-saving smart glazing. However, the trade-off between improving the luminous transmittance (Tlum) while sacrificing the solar modulation ability (ΔTsol) hampers its bench-to-market translation. Previous studies of anti-reflection coatings (ARCs) focused primarily on increasing Tlum while neglecting ΔTsol, which is a key energy-saving determinant. The intrinsically low ΔTsol (<16%) is due to the fact that VO2 has a higher refractive index (RI) from 500 nm to 2200 nm wavelength (λ) below its critical transition temperature (τc), which causes excessive reflection at a lower temperature. This study aims to investigate ARCs with tunable RI (1.47–1.92 at λ = 550 nm) to improve the antireflection effect at a lower temperature, thereby maximizing ΔTsol for various VO2 nanosubstrates, e.g. continuous thin films, nanocomposites, and periodic micro-patterning films. We showed that the best performing coatings could maximize ΔTsol (from 15.7% to 18.9%) and increase Tlum(avg) (from 39% to 44%) simultaneously, which surpasses the current bench-mark specifications ever reported for ARC-coated VO2 smart glazing. In addition, the cytotoxicity analyses evidence that ARCs are feasible to improve the cyto-compatibility of VO2 nanoparticles-based nanocomposites. The presented RI-tunable ARC, which circumvents the complex materials selection and optical design, not only paves the way for practical applications of VO2-based smart windows but also has extensive applications in the field of solar cells, optical lenses, smart display, etc.

The trend of developing electrochemical sensors toward cellular level detection put forward higher requirements of the electrodes in the detection performance. However, common disk electrodes or conventional screen printing electrodes meet up with some limitations in the electrocatalytic activity and electron transfer capability. In this work, we applied inkjet printing technology to fabricate electrodes to make some improvements. Highly conductive Ag nanoparticles based electrodes were obtained on plastic substrate by inkjet printing technology followed by a sintering process at room temperature. The resistivity of IPAgE is determined to be 64.0 $\pm$ 5.3 μΩ cm. With better conductivity and the nanoparticle-based interface, superb electrochemical response of IPAgE for H2O2 was obtained, nearly 300-fold higher than the conventional screen printed Ag electrode. Moreover, high sensitivity of 287 μA mM−1 cm−2 with a LOD of 5.0 μM was obtained under the optimized 20 printed layers. The inkjet printed Ag electrodes were also credibly applied in the detection of H2O2 release from living cells. This work demonstrates inkjet printing is a promising method for the high performance electrochemical sensors.

The field of printed electronics is continually trying to reduce the dimensions of the elec. components. Here, a method of printing metallic lines with widths as small as 15 nm and up to a few micrometers using fountain pen nanolithog. (FPN) is shown. The FPN technique is based on a bent nanopipette with at. force feedback that acts similar to a nanopen. The geometry of the nanopen allows for rapid placement accuracy of the printing tip, on any desired location, with the highest of optical sub-micrometer resoln. Using this nanopen, investigations of various inks are undertaken together with instrumental and script-tool development that allows accurate printing of multiple layers. This has led to the printing of conductive lines using inks composed of silver nanoparticles and salt solns. of silver and copper. In addn., it is shown that the method can be applied to substrates of various materials with minimal effect on the dimension of the line. The line widths are varied by using nanopens with different orifices or by tailoring the wetting properties of the ink on the substrate. Metallic interconnections of conducting lines are reported. [on SciFinder(R)]

Bioelectronics platforms are gaining widespread attention as they provide a template to study the interactions between biological species and electronics. Decoding the effect of the electrical signals on the cells and tissues holds the promise for treating the malignant tissue growth, regenerating organs and engineering new-age medical devices. This work is a step forward in this direction, where bio- and electronic materials co-exist on one platform without any need for post processing. We fabricate a freestanding and flexible hydrogel based platform using 3D bioprinting. The fabrication process is simple, easy and provides a flexible route to print materials with preferred shapes, size and spatial orientation. Through the design of interdigitated electrodes and heating coil, the platform can be tailored to print various circuits for different functionalities. The biocompatibility of the printed platform is tested using C2C12 murine myoblasts cell line. Furthermore, normal human dermal fibroblasts (primary cells) are also seeded on the platform to ascertain the compatibility.

The field of 3D printing, also known as additive manufacturing (AM), is developing rapidly in both academic and industrial research environments. New materials and printing technologies, which enable rapid and multimaterial printing, have given rise to new applications and utilizations. However, the main bottleneck for achieving many more applications is the lack of materials with new physical properties. Here, some of the recent reports on novel materials in this field, such as ceramics, glass, shape-memory polymers, and electronics, are reviewed. Although new materials have been reported for all three main printing approaches–-fused deposition modeling, binder jetting or laser sintering/melting, and photopolymerization-based approaches, apparently, most of the novel physicochemical properties are associated with materials printed by photopolymerization approaches. Furthermore, the high resolution that can be achieved using this type of 3D printing, together with the new properties, has resulted in new implementations such as microfluidic, biomedical devices, and soft robotics. Therefore, the focus here is on photopolymerization-based additive manufacturing including the recent development of new methods, novel monomers, and photoinitiators, which result in previously inaccessible applications such as complex ceramic structures, embedded electronics, and responsive 3D objects.

Background: Iatrogenic ureteral injury is an increasing concern in the laparoscopic era, affecting both patient morbidity and costs. Current techniques enabling intraoperative ureteral identification require invasive procedures or radiations. Our aim was to develop a real-time, non-invasive, radiation-free method to visualize ureters, based on near-infrared (NIR) imaging. For this purpose, we interfered with the biliary excretion pathway of the indocyanine green (ICG) fluorophore by loading it into liposomes, enabling renal excretion. In this work, we studied various parameters influencing ureteral imaging. Methods: Fluorescence intensity (FI) of various liposomal ICG sizes and doses were characterized in vitro and subsequently tested in vivo in mice and pigs. Quantification was performed by measuring FI in multiple points and applying the ureteral/retroperitoneum ratio (U/R). Results: The optimal liposomal ICG loading dose was 20%, for the different liposomes' sizes tested (30, 60, 100 nm). Higher concentration of ICG decreased FI. In vivo, the optimal liposome size for ureteral imaging was 60 nm, which yielded a U/R of 5.2 $\pm$ 1.7 (p < 0.001 vs. free ICG). The optimal ICG dose was 8 mg/kg (U/R = 2.1 $\pm$ 0.4, p < 0.05 vs. 4 mg/kg). Only urine after liposomal ICG injection had a measurable FI, and not after free ICG injection. Using a NIR-optimized laparoscopic camera, ureters could be effectively imaged in pigs, from 10 min after injection and persisting for at least 90 min. Ureteral peristaltic waves could be clearly identified only after liposomal ICG injection. Conclusions: Optimization of liposomal ICG allowed to visualize enhanced ureters in animal models and seems a promising fluorophore engineering, which calls for further developments.

Solution-based thin-film semiconductors offer a promising path for the mass production of low-cost solar cells prepared at low temperatures. Thin-film Cu-based chalcogenides such as Cu(In,Ga)(S,Se)2 (CIGSSe) and Cu2ZnSn(S,Se)4 (CZTSSe) hold great promise and have been regarded as viable candidates because of the abundance of their constituent elements and environmentally nontoxic nature. This Review summarizes the recent progress in solution-processed Cu chalcogenides (CuInSe2, Cu(In,Ga)(S,Se)2, Cu2ZnSnS4, Cu2ZnSn(S,Se)4) for thin-film solar cells, with emphasis on the precursor solution deposited by spray pyrolysis and spin coating. The general aspects, current status, and recent research highlights are introduced and analyzed in detail. Finally, the challenges and future prospects of these solar cells are also discussed.

Surface engineering is an effective method to improve the thermochromic performance of VO2. In this paper, an acid-etching top down method was proposed to tailor the VO2 surface morphology from the continuous dense-packed surface to patterned structure, which exhibited the enhanced integrated visible transmittance (Tlum) and the enlarged solar modulating abilities (ΔTsol). Moreover, a self-patterning approach was also illustrated to improve the thermochromic properties. The proposed surface engineering methods represent a facile and cost-effective approach for enhancing thermochromic properties that could promote the application of VO2 thin films in smart windows.

More than 50% of solar energy comes from the infrared region (as radiant heat) of the solar spectrum. Electrochromic (EC) materials, which can dynamically modulate the transmittance of infrared (IR) radiation, can be effectively applied in smart windows for thermal management in buildings. In this work, a core-shell TiO2-WO3 inverse opal (IO) structure was fabricated through the electrodeposition of WO3 onto TiO2 IO templates. The TiO2 IO templates were synthesized by introducing TiO2 into the voids of a polystyrene (PS) colloidal crystal template, followed by calcination to remove the PS microspheres. It was found that the TiO2-WO3 IO core-shell structure can modulate NIR transmittance at wavelengths from 700 to 1600 nm in the NIR range when potential is applied in LiClO4/PC electrolyte. When −-0.3 V is applied, up to 60% of NIR radiation in this range can be blocked. The NIR transmittance can be modulated by tuning the applied potential. This study focuses on comparing the novel TiO2-WO3 IO structure with electrodeposited WO3 thin film to fully elucidate the effect of the inverse opal morphology and the TiO2-WO3 hybrid system on the optical properties. Results show that the NIR blockage can be sustained up to 90% after 1200 reversible cycles for TiO2-WO3 IO structure. The greater surface area of the IO structure increases the number of active sites available for the redox reactions by providing a larger contact area with the electrolyte. The more electroactive area with improved charge transfer enhances the overall NIR transmittance contrast as compared to bulk WO3 thin film. Furthermore, the addition of WO3 to TiO2 to form a composite has been shown to enhance cycling performance and device lifespan.

Vanadium dioxide (VO2) is one of the most widely studied inorganic phase change material for energy storage and energy conservation applications. Monoclinic VO2 [VO2(M)] changes from semiconducting phase to metallic rutile phase at near room temperature and the resultant abrupt suppressed infrared transmittance at high temperature makes it a potential candidate for thermochromic smart window application to cut the air-condition usage. Meanwhile proper electrical potential, stable structure and good interaction with lithium ions make metastable VO2 [VO2(B)] an attractive material for fabrication of electrodes for batteries and supercapacitors. However, some long-standing issues have plagued its usage. In thermochromic application, high transition temperature (τc), low luminous transmittance (Tlum) and undesirable solar modulation ability (△Tsol) are the key problems, while in energy storage applications, short cycling lifetime and complex three-dimension microstructure are the major challenges. The common methods to produce VO2 polymorph are physical vapour deposition (PVD), chemical vapour deposition (CVD), sol-gel synthesis, and hydrothermal method. CVD is an intensively studied method due to its ability to produce uniform films with precise stoichiometry, phase and morphology control. This paper reviews the various CVD techniques to produce VO2 with controlled phases and the ternary diagram shows the relationship between film stoichiometry and various process conditions. The difference between the various CVD systems are commented and the process window to produce VO2 are tabulated. Some strategies to improve VO2′s performance in both energy conservation and energy storage applications are discussed.

The authors describe a general and facile method based on 3D printing methacrylated macromonomers to fabricate shape memory objects that can be used in flexible and responsive elec. circuits. Such responsive objects can be used in fabrication of soft robotics, minimal invasive medical devices, sensors, and wearable electronics. The use of 3D printing overcomes the poor processing characteristics of thermosets and enables complex geometries that are not easily accessible by other techniques. [on SciFinder(R)]

A platform of mechanotactic hybrids is established by projecting lateral gradients of apparent interfacial stiffness onto the planar surface of a compliant hydrogel layer using an underlying rigid substrate with microstructures inherited from 3D printed molds. Using this platform, the mechanistic coupling of epithelial migration with the stiffness of the extracellular matrix (ECM) is found to be independent of the interfacial compositional and topog. cues. [on SciFinder(R)]

Silver grids are attractive for replacing indium tin oxide as flexible transparent conductors. This work aims to improve the electrochem. stability of silver-based transparent conductors. A silver grid/PEDOT:PSS hybrid film with high cond. and excellent stability is successfully fabricated. Its functionality for flexible electrochromic applications is demonstrated by coating one layer of WO3 nanoparticles on the silver grid/PEDOT:PSS hybrid film. This hybrid structure presents a large optical modulation of 81.9% at 633 nm, fast switching, and high coloration efficiency (124.5 cm2 C-1). More importantly, an excellent electrochem. cycling stability (sustaining 79.1% of their initial transmittance modulation after 1000 cycles) and remarkable mech. flexibility (optical modulation decay of only 7.5% after 1200 compressive bending cycles) is achieved. A novel smart supercapacitor is presented that functions as a regular energy-storage device and simultaneously monitors the level of stored energy by a rapid and reversible color variation even at high current charge/discharge conditions. The film sustains an optical modulation of 87.7% and a specific capacitance of 67.2% at 10 A g-1 compared to their initial value at a c.d. of 1 A g-1. The high-performance silver grid/PEDOT:PSS hybrid transparent films exhibit promising features for various emerging flexible electronics and optoelectronic devices. [on SciFinder(R)]