Coupled oscillation and spinning of photothermal particles in Marangoni optical traps.

Cyclic actuation is critical for driving motion and transport in living systems, ranging from oscillatory motion of bacterial flagella to the rhythmic gait of terrestrial animals. These processes often rely on dynamic and responsive networks of oscillators-a regulatory control system that is challenging to replicate in synthetic active matter. Here, we describe a versatile platform of light-driven active particles with interaction geometries that can be reconfigured on demand, enabling the construction of oscillator and spinner networks. We employ optically induced Marangoni trapping of particles confined to an air-water interface and subjected to patterned illumination. Thermal interactions among multiple particles give rise to complex coupled oscillatory and rotational motions, thus opening frontiers in the design of reconfigurable, multiparticle networks exhibiting collective behavior.

Triplet-Triplet Annihilation Photopolymerization for High-Resolution 3D Printing.

Two-photon polymerization (TPP) currently offers the highest resolution available in 3D printing (∼100 nm) but requires femtosecond laser pulses at very high peak intensity (∼1 TW/cm2). Here, we demonstrate 3D printing based on triplet-triplet-annihilation photopolymerization (TTAP), which achieves submicron resolution while using a continuous visible LED light source with comparatively low light intensity (∼10 W/cm2). TTAP enables submicrometer feature sizes with exposure times of ∼0.1 s/voxel without requiring a coherent or pulsed light source, opening the door to low-cost fabrication with submicron resolution. This approach enables 3D printing of a diverse array of designs with high resolution and is amenable to future parallelization efforts.

Robust folding of elastic origami.

Self-folding origami, structures that are engineered flat to fold into targeted, three-dimensional shapes, have many potential engineering applications. Though significant effort in recent years has been devoted to designing fold patterns that can achieve a variety of target shapes, recent work has also made clear that many origami structures exhibit multiple folding pathways, with a proliferation of geometric folding pathways as the origami structure becomes complex. The competition between these pathways can lead to structures that are programmed for one shape, yet fold incorrectly. To disentangle the features that lead to misfolding, we introduce a model of self-folding origami that accounts for the finite stretching rigidity of the origami faces and allows the computation of energy landscapes that lead to misfolding. We find that, in addition to the geometrical features of the origami, the finite elasticity of the nearly-flat origami configurations regulates the proliferation of potential misfolded states through a series of saddle-node bifurcations. We apply our model to one of the most common origami motifs, the symmetric "bird's foot," a single vertex with four folds. We show that though even a small error in programmed fold angles induces metastability in rigid origami, elasticity allows one to tune resilience to misfolding. In a more complex design, the "Randlett flapping bird," which has thousands of potential competing states, we further show that the number of actual observed minima is strongly determined by the structure's elasticity. In general, we show that elastic origami with both stiffer folds and less bendable faces self-folds better.

Polymer Zwitterions for Stabilization of CsPbBr3 Perovskite Nanoparticles and Nanocomposite Films.

Functional polymers with sulfobetaine or phosphorylcholine zwitterions as pendent groups are demonstrated as both ligands and host matrices for CsPbBr3 perovskite nanoparticles (PNPs). These polymers produce nanocomposite films with excellent NP dispersion, optical transparency, and impressive resistance to NP degradation upon exposure to water. Multidentate interactions of the zwitterion-containing copolymers with the PNPs induce dispersed or weakly aggregated nanocomposite morphologies, depending on the extent of zwitterionic functionality in the polymer. Incorporating additional functionality into the polymers, such as benzophenone pendent groups, yields lithographically patternable films, while time-resolved photoluminescence measurements provide insight into the electronic impact of PNPs in zwitterionic polymer matrices.

Amplified Photon Upconversion by Photonic Shell of Cholesteric Liquid Crystals.

As an effective platform to exploit triplet-triplet-annihilation-based photon upconversion (TTA-UC), microcapsules composed of a fluidic UC core and photonic shell are microfluidically prepared using a triple emulsion as the template. The photonic shell consists of cholesteric liquid crystals (CLCs) with a periodic helical structure, exhibiting a photonic band gap. Combined with planar anchoring at the boundaries, the shell serves as a resonance cavity for TTA-UC emission and enables spectral tuning of the UC under low-power-density excitation. The CLC shell can be stabilized by introducing a polymerizable mesogen in the LC host. Because of the microcapsule spherical symmetry, spontaneous emission of the delayed fluorescence is omnidirectionally amplified at the edge of the stop band. These results demonstrate the range of opportunities provided by TTA-UC systems for the future design of low-threshold photonic devices.

Development of a Novel Leak-Free Constant-Pressure Cylinder for Certified Reference Materials of Liquid Hydrocarbon Mixtures.

Liquid hydrocarbon mixtures such as liquefied petroleum gas and liquefied natural gas are becoming integral parts of the world's energy system. Certified reference materials (CRMs) of liquid hydrocarbon mixtures are necessary to allow assessment of the accuracy and traceability of the compositions of such materials. A piston-type constant-pressure cylinder (PCPC) comprising chambers for a pressurizing gas (helium) and liquid (hydrocarbons) separated by a piston can be used to develop accurate and traceable liquid hydrocarbon mixture CRMs. The development of accurate CRMs relies on the maintenance of their composition. However, a PCPC might allow hydrocarbons to leak owing to the imperfect seal of the piston. In this study, a novel leak-free bellows-type constant-pressure cylinder (BCPC) is designed and evaluated by comparison with PCPCs. Liquid hydrocarbon mixtures consisting of ethane, propane, propene, isobutane, n-butane, 1-butene, and isopentane were prepared in both types of constant pressure cylinders and then monitored to check leakages between the gas and liquid chambers. Overall, notable leakage occurred from and into both chambers in the PCPCs, whereas no leakage occurred in the BCPCs in the three months after their gravimetric preparation. The BCPCs maintained no leakage even 10 months after their preparation, whereas the PCPCs showed significantly increasing leakage during the same period.

Synthesis of porous carbon balls from spherical colloidal crystal templates.

Spherical inverse opal (IO) porous carbon was produced utilizing silica colloidal crystal spheres as templates. The spherical colloidal crystals were obtained through the self-assembly of monodisperse particles inside an emulsion droplet with confined geometry. The templates were inverted using a carbon precursor, phenol-formaldehyde (PF) resol. We demonstrated a two-step synthesis involving the subsequent infiltration of the PF resol precursor into the spherical colloidal crystal template and a one-step synthesis using a silica colloidal solution containing dissolved PF resol. In the former case, the sizes of the IO carbon balls were controlled by the size of the colloidal crystal templates, and diameters of a few micrometers up to 50 µm were obtained. The average diameter of the macropores created by the silica particles was 230 nm. Moreover, meso-/macroporous IO carbon balls were created using block-copolymer templates in the PF resol. In the one-step synthesis, the concentration of PF resol in the colloidal solution controlled the diameter of the IO carbon balls. IO balls smaller than 3 µm were obtained from the direct addition of 5% PF resol. The one-step synthesis produced rather irregular porous structures reflecting the less ordered crystallization processes inside the spherical colloidal crystals. Nitrogen adsorption and cyclic voltammetry measurements were conducted to measure the specific area and electroactive surface area of the IO carbon balls. The specific area of the mesopores-incorporated IO carbon balls was 1.3 times higher than that of bare IO carbon balls. Accordingly, the meso-/macroporous porous carbon balls exhibited higher electrocatalytic properties than the macroporous carbon balls.

Facile synthesis of TiO2 inverse opal electrodes for dye-sensitized solar cells.

Engineering of TiO(2) electrode layers is critical to guaranteeing the photoconversion efficiency of dye-sensitized solar cells (DSSCs). Recently, a novel approach has been introduced for producing TiO(2) electrodes using the inverted structures of colloidal crystals. This paper describes a facile route to producing ordered macroporous electrodes from colloidal crystal templates for DSSCs. Using concentrated colloids dispersed in a volatile medium, the colloidal crystal templates were obtained within a few minutes, and the thickness of the template was easily controlled by changing the quantity of colloidal solution deposited. Here, the effects of the structural properties of the inverse opal TiO(2) electrodes on the photovoltaic parameters of DSSCs were investigated. The photovoltaic parameters were measured as a function of pore ordering and electrode film thickness. Moreover, DSSC applications that used either liquid or viscous polymer electrolyte solutions were investigated to reveal the effects of pore size on performance of an inverse opal TiO(2) electrode.

Dual-sensitized upconversion-assisted, triple-band absorbing luminescent solar concentrators.

Luminescent solar concentrator-photovoltaic systems (LSC-PV) harvest solar light by using transparent photoluminescent plates, which is expected to be particularly useful for building-integrated PV applications. LSC panels that absorb multiple wavelength bands are required to achieve high power conversion efficiency (PCE). In this study, we demonstrate a pair of downshift LSC and photon upconversion (UC) LSC, absorbing triple bands (violet, green, and red light). The UC is obtained by energy transfer and triplet-triplet annihilation between sensitizer and emitter dyes. In particular, we exploit the dual sensitizer to obtain absorption of the dual wavelength band. The couple with the UC LSC obtains photoluminescence of a single visible wavelength band from the LSC, which enables the use of wide bandgap solar cells to absorb it. Here, we apply mixed-cation perovskite solar cells (PSCs) with high absorption coefficients, especially at visible wavelengths. In our triple-band-absorbing LSC-PSC, we achieve a maximum PCE of 8.99%.

Enabling Robust Self-Folding Origami by Pre-Biasing Vertex Buckling Direction.

Self-folding is a powerful approach to fabricate materials with complex 3D forms and advanced properties using planar patterning steps, but suffers from intrinsic limitations in robustness due to the highly bifurcated nature of configuration space around the flat state. Here, a simple mechanism is introduced to achieve robust self-folding of microscale origami by separating actuation into two discrete steps using different thermally responsive hydrogels. First, the vertices are pre-biased to move in the desired direction from the flat state by selectively swelling one of the two hydrogels at high temperature. Subsequently, the creases are folded toward their target angles by activating swelling of the second hydrogel upon cooling to room temperature. Since each vertex can be individually programmed to move upward or downward, it is possible to robustly select the desired branch even in multi-vertex structures with reasonably high complexity. This strategy provides key new principles for designing shaping-morphing materials that avoid undesired distractor states, expanding their potential applications in areas such as soft robotics, sensors, mechanical metamaterials, and deployable devices.

Light-Driven Shape Morphing, Assembly, and Motion of Nanocomposite Gel Surfers.

Patterning of nanoparticles (NPs) via photochemical reduction within thermally responsive hydrogel films is demonstrated as a versatile platform for programming light-driven shape morphing and materials assembly. Responsive hydrogel disks, containing patterned metal NPs, form characteristic wrinkled structures when illuminated at an air/water interface. The resulting distortion of the three-phase (air/water/hydrogel) contact lines induces capillary interactions between two or more disks, which are either attractive or repulsive depending on the selected pattern of light. By programming the shapes of the NP-rich regions, as well as of the hydrogel objects themselves, the number and location of attractive interactions are specified, and the assembly geometry is controlled. Remarkably, appropriately patterned illumination enables sustained rotation and motion of the hydrogel disks. Overall, these results offer insight into a wide variety of shape-programmable materials and capillary assemblies, simply by controlling the NP patterns and illumination of these soft materials.

Ultrathin Double-Shell Capsules for High Performance Photon Upconversion.

Triplet-fusion-based photon upconversion capsules with ultrathin double shells are developed through a single dripping instability in a microfluidic flow-focusing device. An inner separation layer allows use of a brominated hydrocarbon oil-based fluidic core, demonstrating significantly enhanced upconversion quantum yield. Furthermore, a perfluorinated photocurable monomer serves as a transparent shell phase with remote motion control through magnetic nanoparticle incorporation.

Development of traceable precision dynamic dilution method to generate dimethyl sulphide gas mixtures at sub-nanomole per mole levels for ambient measurement.

Dimethyl sulphide (DMS) is an important compound in global atmospheric chemistry and climate change. Traceable international standards are essential for measuring accurately the long-term global trend in ambient DMS. However, developing accurate gas standards for sub-nanomole per mole (nmol/mol) mole fractions of DMS in a cylinder is challenging, because DMS is reactive and unstable. In this study, a dynamic dilution method that is traceable and precise was developed to generate sub-nmol/mol DMS gas mixtures with a dynamic dilution system based on sonic nozzles and a long-term (>5 years) stable 10 µmol/mol parent DMS primary standard gas mixtures (PSMs). The dynamic dilution system was calibrated with traceable methane PSMs, and its estimated dilution factors were used to calculate the mole fractions of the dynamically generated DMS gas mixtures. A dynamically generated DMS gas mixture and a 6 nmol/mol DMS PSM were analysed against each other by gas chromatography with flame-ionisation detection (GC/FID) to evaluate the dilution system. The mole fractions of the dynamically generated DMS gas mixture determined against a DMS PSM and calculated with the dilution factor agreed within 1% at 6 nmol/mol. In addition, the dynamically generated DMS gas mixtures at various mole fractions between 0.4 and 11.7 nmol/mol were analysed by GC/FID and evaluated for their linearity. The analytically determined mole fractions showed good linearity with the mole fractions calculated with the dilution factors. Results showed that the dynamic dilution method generates DMS gas mixtures ranging between 0.4 nmol/mol and 12 nmol/mol with relative expanded uncertainties of less than 2%. Therefore, the newly developed dynamic dilution method is a promising reference method for generating sub-nmol/mol DMS gas standards for accurate ambient measurements.

Fabrication of 3D copper oxide structure by holographic lithography for photoelectrochemical electrodes.

We fabricated three-dimensional copper oxide structure by holographic lithography and electroless deposition. A five-beam interference pattern defined a woodpile structure of SU-8. The surface modification of SU-8 structure was achieved by multilayer coating of polyelectrolyte, which is critical for activating the surface for the reduction of copper. Copper was deposited onto the surface of the structure by electroless deposition, and subsequent calcinations removed the SU-8 structure and simultaneously oxidized the copper into copper oxide. The porous copper oxide structure was used as a photoelectrochemical electrode. Because of the highly porous structure, our structure showed higher photocurrent efficiency.

Holographically defined TiO2 electrodes for dye-sensitized solar cells.

We describe a multibeam interference lithography for creating 3D polymeric porous structures. The coating of a TiO(2) shell and subsequent removal of the template produce holographically defined TiO(2) (h-TiO(2)) electrodes. We analyze the morphological features of the h-TiO(2) electrodes and consider their applicability to dye-sensitized solar cells (DSSCs). Specifically, the performance of the h-TiO(2) electrode was evaluated by comparison with a macroporous TiO(2) electrode produced from colloidal crystals. The h-TiO(2) structure possesses a larger specific area than the inverted colloidal crystals because of a bicontinuous air network with the TiO(2) shell. Consequently, the h-TiO(2) electrode can produce a 30% higher photogenerated electron current.