Stretchable ionic-electronic bilayer hydrogel electronics enable in situ detection of solid-state epidermal biomarkers.

Continuous and in situ detection of biomarkers in biofluids (for example, sweat) can provide critical health data but is limited by biofluid accessibility. Here we report a sensor design that enables in situ detection of solid-state biomarkers ubiquitously present on human skin. We deploy an ionic-electronic bilayer hydrogel to facilitate the sequential dissolution, diffusion and electrochemical reaction of solid-state analytes. We demonstrate continuous monitoring of water-soluble analytes (for example, solid lactate) and water-insoluble analytes (for example, solid cholesterol) with ultralow detection limits of 0.51 and 0.26 nmol cm-2, respectively. Additionally, the bilayer hydrogel electrochemical interface reduces motion artefacts by a factor of three compared with conventional liquid-sensing electrochemical interfaces. In a clinical study, solid-state epidermal biomarkers measured by our stretchable wearable sensors showed a high correlation with biomarkers in human blood and dynamically correlated with physiological activities. These results present routes to universal platforms for biomarker monitoring without the need for biofluid acquisition.

N-annulated perylene as an efficient electron donor for porphyrin-based dyes: enhanced light-harvesting ability and high-efficiency Co(II/III)-based dye-sensitized solar cells.

Porphyrin-based dyes recently have become good candidates for dye-sensitized solar cells (DSCs). However, the bottleneck is how to further improve their light-harvesting ability. In this work, N-annulated perylene (NP) was used to functionalize the Zn-porphyrin, and four "push-pull"-type NP-substituted and fused porphyrin dyes with intense absorption in the visible and even in the near-infrared (NIR) region were synthesized. Co(II/III)-based DSC device characterizations revealed that dyes WW-5 and WW-6, in which an ethynylene spacer is incorporated between the NP and porphyrin core, showed pantochromatic photon-to-current conversion efficiency action spectra in the visible and NIR region, with a further red-shift of about 90 and 60 nm, respectively, compared to the benchmark molecule YD2-o-C8. As a result, the short-circuit current density was largely increased, and the devices displayed power conversion efficiencies as high as 10.3% and 10.5%, respectively, which is comparable to that of the YD2-o-C8 cell (η = 10.5%) under the same conditions. On the other hand, the dye WW-3 in which the NP unit is directly attached to the porphyrin core showed a moderate power conversion efficiency (η = 5.6%) due to the inefficient π-conjugation, and the NP-fused dye WW-4 exhibited even poorer performance due to its low-lying LUMO energy level and nondisjointed HOMO/LUMO profile. Our detailed physical measurements (optical and electrochemical), density functional theory calculations, and photovoltaic characterizations disclosed that the energy level alignment, the molecular orbital profile, and dye aggregation all played very important roles on the interface electron transfer and charge recombination kinetics.

Skin-Attachable Ink-Dispenser-Printed Paper Fluidic Sensor Patch for Colorimetric Sweat Analysis.

In situ analysis of sweat biomarkers potentially provides noninvasive lifestyle monitoring and early diagnosis. Quantitative detection of sweat rate is crucial for thermoregulation and preventing heat injuries. Here, a skin-attachable paper fluidic patch is reported for in situ colorimetric sensing of multiple sweat markers (pH, glucose, lactate, and uric acid) with concurrent sweat rate tracking. Two sets of fluidic patterns-multiplexed detection zones and a longitudinal sweat rate channel-are directly printed by an automated ink dispenser from a specially developed ceramic-based ink. The ceramic ink thermal-cures into an impervious barrier, confining sweat within the channels. The ceramic-ink-printed boundary achieves higher pattern resolution, prevents fluid leakage, attains pattern thermal stability, and resistant to organic solvents. The cellulose matrix of the detection zones is modified with nanoparticles to improve the color homogeneity and sweat sensor sensitivity. The sweat rate channel is made moisture sensitive by incorporating a metal-salt-based dye. The change in saturation/color of the detection zones and/or channels upon sweat addition can be visually detected or quantified by a smartphone camera. A cost-effective way is provided to fabricate paper fluidic sensor patches, successfully demonstrating on-body multiplexed evaluation of sweat analytes. Such skin wearables offer on-site analysis, meaningful to an increasingly health-conscious population.

High-efficiency si/polymer hybrid solar cells based on synergistic surface texturing of Si nanowires on pyramids.

An efficient Si/PEDOT:PSS hybrid solar cell using synergistic surface texturing of Si nanowires (SiNWs) on pyramids is demonstrated. A power conversion efficiency (PCE) of 9.9% is achieved from the cells using the SiNW/pyramid binary structure, which is much higher than similar cells based on planar Si, pyramid-textured Si, and SiNWs. The PCE is the highest reported to-date for hybrid cells based on Si nanostructures and PEDOT.

Concave Array Ultrasonic Transducer From Multilayer Piezoelectric Ceramic for Photoacoustic Imaging.

Implementation of piezoelectric multilayer ceramic (MLC) is an effective way to reduce impedance and improve the performance of linear-array transducer for ultrasonic system applications. However, the ultrasonic image derived from a planar linear-array transducer generally suffers from degradation of lateral resolution and contrast. In this article, we designed and fabricated a focused 5-MHz 128-element linear-array ultrasonic transducer with concave structure using five-layered 0.1Pb (Ni1/3Nb2/3)O3 -0.35Pb(Zn1/3Nb2/3)O3 -0.15Pb(Mg1/3Nb2/3)O3-0.1PbZrO3-0.3PbTiO3 (PNN-PZN-PMN-PZ-PT) piezo- electric ceramic. The transducer showed a bandwidth of 63% at -6 dB and the lateral resolution up to 0.33 mm. An improved transmission signal of 90% higher than a commercial single-layer ceramic transducer was also achieved. We further demonstrated high-resolution photoacoustic imaging with the obtained concave linear-array transducer.

Broadband Ultrasonic Array Transducer From Multilayer Piezoelectric Ceramic With Lowered Co-Firing Temperature.

Increasing array transducer bandwidth (BW) and signal-to-noise ratio (SNR) is a critical issue for producing a high-quality medical ultrasound image. However, array elements with small size tend to have poor sensitivity due to a much higher impedance compared with the electrical impedance of the transmitter and receiver circuit. Implementation of multilayer ceramic (MLC) is an effective way of reducing impedance, and thus, with a potential for improving SNR for an ultrasonic probe. In this work, we fabricated multilayer piezoelectric ceramic with a composition of 0.1Pb(Ni1/3Nb2/3)O3-0.35Pb(Zn1/3Nb2/3)O3-0.15Pb(Mg1/3Nb2/3)O3-0.1PbZrO3-0.3PbTiO3-4mol% excess NiO (PNN-PZN-PMN-PZ-PT), by a roll to roll tape casting process and co-fired with 90Ag/10Pd electrode at a low temperature of 950 °C. Using five-layer MLC (5L-MLC) as obtained, we designed and demonstrated a 5 MHz 32-element array transducer for ultrasonic and photoacoustic imaging. The five-layer transducer element exhibited a BW of 87% at -6 dB, substantially higher than 62% for single-layer ceramic (SLC) element. In addition, the insertion loss was improved by 16.2 dB over the SLC element with an external impedance of 50 Ω . Both the experimental results and theoretical analysis showed that our array transducer made of the PNN-PZN-PMN-PZ-PT MLC is promising for acquiring high-quality ultrasonic and photoacoustic images.

Improvement of CH3NH3PbI3 Formation for Efficient and Better Reproducible Mesoscopic Perovskite Solar Cells.

High-performance perovskite solar cells (PSCs) are obtained through optimization of the formation of CH3NH3PbI3 nanocrystals on mesoporous TiO2 film, using a two-step sequential deposition process by first spin-coating a PbI2 film and then submerging it into CH3NH3I solution for perovskite conversion (PbI2 + CH3NH3I → CH3NH3PbI3). It is found that the PbI2 morphology from different film formation process (thermal drying, solvent extraction, and as-deposited) has a profound effect on the CH3NH3PbI3 active layer formation and its nanocrystalline composition. The residual PbI2 in the active layer contributes to substantial photocurrent losses, thus resulting in low and inconsistent PSC performances. The PbI2 film dried by solvent extraction shows enhanced CH3NH3PbI3 conversion as the loosely packed disk-like PbI2 crystals allow better CH3NH3I penetration and reaction in comparison to the multicrystal aggregates that are commonly obtained in the thermally dried PbI2 film. The as-deposited PbI2 wet film, without any further drying, exhibits complete conversion to CH3NH3PbI3 in MAI solution. The resulting PSCs reveal high power conversion efficiency of 15.60% with a batch-to-batch consistency of 14.60 ± 0.55%, whereas a lower efficiency of 13.80% with a poorer consistency of 11.20 ± 3.10% are obtained from the PSCs using thermally dried PbI2 films.

High efficiency silicon nanowire/organic hybrid solar cells with two-step surface treatment.

A simple two-step surface treatment process is proposed to boost the efficiency of silicon nanowire/PEDOT:PSS hybrid solar cells. The Si nanowires (SiNWs) are first subjected to a low temperature ozone treatment to form a surface sacrificial oxide, followed by a HF etching process to partially remove the oxide. TEM investigation demonstrates that a clean SiNW surface is achieved after the treatment, in contrast to untreated SiNWs that have Ag nanoparticles left on the surface from the metal-catalyzed etching process that is used to form the SiNWs. The cleaner SiNW surface achieved and the thin layer of residual SiO2 on the SiNWs have been found to improve the performance of the hybrid solar cells. Overall, the surface recombination of the hybrid SiNW solar cells is greatly suppressed, resulting in a remarkably improved open circuit voltage of 0.58 V. The power conversion efficiency has also increased from about 10% to 12.4%. The two-step surface treatment method is promising in enhancing the photovoltaic performance of the hybrid silicon solar cells, and can also be applied to other silicon nanostructure based solar cells.

Improve the operational stability of the inverted organic solar cells using bilayer metal oxide structure.

Operational stability is a big obstacle for the application of inverted organic solar cells (OSCs), however, less talked about in the research reports. Due to photoinduced degradation of the metal oxide interlayer, which can cause shunts generation and degeneration in ZnO interlayer, a significant degradation of open circuit voltage (Voc) and fill factor (FF) has been observed by in situ periodic measurements of the device current density-voltage (J-V) curves with light illumination. By combining TiOx and ZnO to form bilayer structures on ITO, the photovoltaic performance is improved and the photoinduced degradation is reduced. It was found that the device based on ZnO/TiOx bilayer structure achieved better operational stability as compared to that with ZnO or TiOx interlayer.

Development of inverted organic solar cells with TiO2 interface layer by using low-temperature atomic layer deposition.

Organic solar cells (OSCs) with inverted structure have attracted much attention in recent years because of their improved device air stability due to the use of stable materials for electrodes and interface layers. In this work, TiO(2) films, fabricated using low temperature (e.g., 130-170 °C) atomic layer deposition (ALD) on ITO substrates, are used as electron selective interface layers to investigate inverted OSCs. It is found that though the as-deposited TiO(2) films are high resistive due to the presence of oxygen defects, the defects can be significantly reduced by light soaking. PV cells with 15-nm-thick amorphous-TiO(2) layers fabricated at low temperature show better performance than those with poly crystal TiO(2) with same thickness deposited at 250 °C. The low temperature ALD-grown TiO(2) films are dense, stable and robust with capability of conformal coating on nanostructural surfaces, showing a promising interface layer for achieving air-stable plastic OSCs with roll-to-roll mass production potential.

Si nanowires organic semiconductor hybrid heterojunction solar cells toward 10% efficiency.

High-efficiency hybrid solar cells are fabricated using a simple approach of spin coating a transparent hole transporting organic small molecule, 2,2',7,7'-Tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (Spiro-OMeTAD) on silicon nanowires (SiNWs) arrays prepared by electroless chemical etching. The characteristics of the hybrid cells are investigated as a function of SiNWs length from 0.15 to 5 µm. A maximum average power conversion efficiency of 9.92% has been achieved from 0.35 µm length SiNWs cells, despite a 12% shadowing loss and the absence of antireflective coating and back surface field enhancement. It is found that enhanced aggregations in longer SiNWs limit the cell performance due to increased series resistance and higher carrier recombination in the shorter wavelength region. The effects of the Si substrate doping concentrations on the performance of the cells are also investigated. Cells with higher substrate doping concentration exhibit a significant drop in the incident photons-to-current conversion efficiency (IPCE) in the near infrared region. Nevertheless, a promising short circuit current density of 19 mA/cm(2) and IPCE peak of 57% have been achieved for a 0.9 µm length SiNWs cell fabricated on a highly doped substrate with a minority-carrier diffusion length of only 15 µm. The results suggest that such hybrid cells can potentially be realized using Si thin films instead of bulk substrates. This is promising towards realizing low-cost and high-efficiency SiNWs/organic hybrid solar cells.

Synthesis and properties of electrophosphorescent chelating polymers with iridium complexes in the conjugated backbone.

The synthesis of electrophosphorescent chelating polymers by Suzuki polycondensation of A-A- and B-B-type monomers is described, in which the fluorene-alt-carbazole (PFCz) segment is used as polymer backbone. By using alkyl-substituted ligands of iridium complex monomers, chelating copolymers with higher contents of iridium complex can be synthesized. Chemical and photophysical characterization confirm that the Ir complex is incorporated into the polymer backbone as one of the monomer repeat units by means of two 5-bromotolylpyridine ligands. Chelating polymers with Ir complexes in the conjugated polymer backbone show highly efficient energy transfer of excitons from the PFCz host segment to the Ir complex by an intramolecular trapping mechanism. The external quantum and luminous efficiencies of a device made with PFCzMppyIrhm4 copolymer reach 4.1 % ph/el (photons/electron) and 5.4 cd A(-1), respectively, at a current density of 32.2 mA cm(-2), an emission peak of 577 nm, and a luminance of 1730 cd cm(-2). Most important, the devices made from the chelating copolymers show no notable efficiency decay with increasing current density due to reduced concentration quenching and triplet-triplet (T-T) annihilation. This indicates that incorporation of the phosphorescent complex into the rigid conjugated polymer main chain is a new way to simultaneously realize high efficiency, long-term stability, and simple processing of phosphorescent polymer light-emitting diodes.