Tailoring Metal/TiO2 Interface to Influence Motion of Light‐Activated Janus Micromotors

Catalytic light‐powered micromotors have become a major focus in current autonomous self‐propelled micromotors research. The attractiveness of such machines stems from the fact that these motors are “fuel‐free,” with their motion modulated by light irradiation. In order to study how different metals affect the velocities of metal/TiO₂ micromachines in the presence of UV irradiation in pure water, Pt/TiO₂, Cu/TiO₂, Fe/TiO₂, Ag/TiO₂, and Au/TiO₂ Janus micromotors are prepared. The metals have different chemical potentials and catalytic effects toward water splitting reaction, with both the effects expected to alter the photoelectrochemically‐induced reaction and propulsion rates. Analysis of structures, elemental compositions, motion patterns, velocities, and overall performances of different metals (Pt, Au, Ag, Fe, Cu) on TiO₂ are observed by scanning electron microscopy, energy dispersive X‐ray spectroscopy, and optical microscopy. Electrochemical Tafel analysis is performed for the different metal/TiO₂ structures and it is concluded that the effective velocity is a result of the synergistic effect of chemical potential and catalysis. It is found that the Pt/TiO₂ Janus micromotors exhibit the fastest motion compared to the rest of the prepared materials. Furthermore, after exposure to UV light, every fabricated micromotor shows high possibility of forming assembled chains which influence their velocity.     

Controlling the Functional Properties of Oligothiophene Crystalline Nano/Microfibers via Tailoring of the Self‐Assembling Molecular Precursors

Oligothiophenes are π‐conjugated semiconducting and fluorescent molecules whose self‐assembly properties are widely investigated for application in organic electronics, optoelectronics, biophotonics, and sensing. Here an approach to the preparation of crystalline oligothiophene nano/microfibers is reported based on the use of a “sulfur overrich” quaterthiophene building block, ? T4S4 ? , containing in its covalent network all the information needed to promote the directional, π–π stacking‐driven, self‐assembly of Y‐T4S4‐Y oligomers into fibers with hierarchical supramolecular arrangement from nano‐ to microscale. It is shown that when Y varies from unsubstituted thiophene to thiophene substituted with electron‐withdrawing groups, a wide redistribution of the molecular electronic charge takes place without substantially affecting the aggregation modalities of the oligomer. In this way, a structurally comparable series of fibers is obtained having progressively varying optical properties, redox potentials, photoconductivity, and type of prevailing charge carriers (from p‐ to n‐type). With the aid of density functional theory (DFT) calculations, combined with powder X‐ray diffraction data, a model accounting for the growth of the fibers from molecular to nano‐ and microscale is proposed.     

Wavelength‐Emission Tuning of ZnO Nanowire‐Based Light‐Emitting Diodes by Cu Doping: Experimental and Computational Insights

The band‐gap engineering of doped ZnO nanowires is of the utmost importance for tunable light‐emitting‐diode (LED) applications. A combined experimental and density‐functional theory (DFT) study of ZnO doping by copper (Zn²⁺ substitution by Cu²⁺) is presented. ZnO:Cu nanowires are epitaxially grown on magnesium‐doped p‐GaN by electrochemical deposition. The heterojunction is integrated into a LED structure. Efficient charge injection and radiative recombination in the Cu‐doped ZnO nanowires are demonstrated. In the devices, the nanowires act as the light emitters. At room temperature, Cu‐doped ZnO LEDs exhibit low‐threshold emission voltage and electroluminescence emission shifted from the ultraviolet to violet–blue spectral region compared to pure ZnO LEDs. The emission wavelength can be tuned by changing the copper content in the ZnO nanoemitters. The shift is explained by DFT calculations with the appearance of copper d states in the ZnO band‐gap and subsequent gap reduction upon doping. The presented data demonstrate the possibility to tune the band‐gap of ZnO nanowire emitters by copper doping for nano‐LEDs.     

Substantial Cyano‐Substituted Fully sp2‐Carbon‐Linked Framework: Metal‐Free Approach and Visible‐Light‐Driven Hydrogen Evolution

Polymeric semiconductors are emerging as a kind of competitive photocatalysts for hydrogen evolution due to their well‐tunable structures, versatile functionalization, and low‐cost processibility. In this work, a series of conjugated porous polymers with substantial cyano‐substituted fully sp²‐carbon frameworks are efficiently synthesized by using electron‐deficient tricyanomesitylene as a key building block to promote an organic base‐catalyzed Knoevenagel condensation with various aldehyde‐substituted arenes. The resulting porous polymers feature donor‐acceptor structures with π‐extended conjugation, rendering them with distinct semiconducting properties. They possess hierarchically porous structures, nanoscale morphologies, and intriguing wettability. These promising physical characters, finely tailorable by varying the arene units, are essentially relevant to the abundant cynao substituents over the whole frameworks. The as‐prepared porous polymers exhibit excellent visible‐light‐driven photocatalytic activity for water‐splitting hydrogen evolution with apparent quantum yield up to 2.0% at 420 nm or 1.9% at 470 nm, among the highest values yet reported for porous polymer‐based photocatalysts, also representing the first example of such kinds of catalysts formed through a metal‐free‐catalyzed carbon–carbon coupling reaction.     

Structure‐Dependent Optical Modulation of Propulsion and Collective Behavior of Acoustic/Light‐Driven Hybrid Microbowls

Hybrid light/acoustic‐powered microbowl motors, composed of gold (Au) and titanium dioxide (TiO₂) with a structure‐dependent optical modulation of both their movement and collective behavior are reported by reversing the inner and outer positions of Au and TiO₂. The microbowl propels in an acoustic field toward its exterior side. UV light activates the photochemical reaction on the TiO₂ surface in the presence of hydrogen peroxide and the Au/TiO₂ system moves toward its TiO₂ side by self‐electrophoresis. Controlling the light intensity allows switching of the dominant propulsion mode and provides braking or reversal of motion direction when TiO₂ is on the interior, or accelerated motion when the TiO₂ is on its exterior. Theoretical simulations offer an understanding of the acoustic streaming flow and self‐electrophoretic fluid flow induced by the asymmetric distribution of ions around the microbowl. The light‐modulation behavior along with the tunable structure also leads to the control of the swarm behaviors under the acoustic field, including expansion or compaction of ensembles of microbowls with interior and exterior TiO₂, respectively. Such structure‐dependent motion control thus paves the way for a variety of complex microscale operations, ranging from cargo transport to drug delivery in biomedical and environmental applications.     

Ideal Energy‐Level Alignment at the ZnO/P3HT Photovoltaic Interface

Hybrid semiconductor‐polymer nanostructured solar cells hold the promise of photovoltaic energy conversion based on abundant and nontoxic materials and scalable manufacturing processes. After a decade of intense research activity, hybrid solar cells still exhibit low short‐circuit currents and moderate open‐circuit voltages. These bottlenecks call for a detailed understanding of the physics underlying the device operation at the nanoscale. Using first‐principles calculations the ideal energy‐level alignment of hybrid solar cell interfaces based on the wide bandgap semiconductor ZnO and the polymer poly(3‐hexylthiophene) (P3HT) is investigated. The interfacial charge transfer is quantified and it is shown that this effect increases the ideal open‐circuit voltage with respect to the electron‐affinity rule by as much as 0.5 V. The results of this work suggests that there is significant room for optimizing this class of excitonic solar cells by tailoring the semiconductor/polymer interface at the nanoscale.     

Self‐Sacrifice Template Fabrication of Hierarchical Mesoporous Bi‐Component‐Active ZnO/ZnFe2O4 Sub‐Microcubes as Superior Anode Towards High‐Performance Lithium‐Ion Battery

In the work, a facile yet efficient self‐sacrifice strategy is smartly developed to scalably fabricate hierarchical mesoporous bi‐component‐active ZnO/ZnFe₂O₄ (ZZFO) sub‐microcubes (SMCs) by calcination of single‐resource Prussian blue analogue of Zn₃[Fe(CN)₆]₂ cubes. The hybrid ZZFO SCMs are homogeneously constructed from well‐dispersed nanocrstalline ZnO and ZnFe₂O₄ (ZFO) subunites at the nanoscale. After selectively etching of ZnO nanodomains from the hybrid, porously assembled ZFO SMCs with integrate architecture are obtained accordingly. When evaluated as anodes for LIBs, both hybrid ZZFO and ZFO samples exhibit appealing electrochemical performance. However, the as‐synthesized ZZFO SMCs demonstrate even better electrochemical Li‐storage performance, including even larger initial discharge capacity and reversible capacity, higher rate behavior and better cycling performance, particularly at high rates, compared with the single ZFO, which should be attributed to its unique microstructure characteristics and striking synergistic effect between the bi‐component‐active, well‐dispersed ZnO and ZFO nanophases. Of great significance, light is shed upon the insights into the correlation between the electrochemical Li‐storage property and the structure/component of the hybrid ZZFO SMCs, thus, it is strongly envisioned that the elegant design concept of the hybrid holds great promise for the efficient synthesis of advanced yet low‐cost anodes for next‐generation rechargeable Li‐ion batteries.     

A Nano‐in‐Nano Vector: Merging the Best of Polymeric Nanoparticles and Drug Nanocrystals

An advanced approach that can prepare narrowly size distributed nanomaterials with ultrahigh mass fraction of therapeutics, superior colloidal stability, minimal off‐target effects, as well as precisely controlled drug‐release profiles, is strongly desirable. Here, an optimal nano‐in‐nano vector, consisting of a drug (sorafenib, SFN, or itraconazole, ICZ) nanocrystal core and a polymer (folic acid conjugated spermine‐functionalized acetalated dextran, ADS‐FA) shell on a 1:1 ratio (HSFN@ADS‐FA or ICZ@ADS‐FA) is successfully fabricated. With the help of computational fluid dynamics, the concentration and velocity field are computed in the microfluidic domain, as well as the mixing time between the solvent and nonsolvent for nanovector precursors. The favorable features of both polymer nanoparticles and drug nanocrystals are inherited by the obtained nano‐in‐nano vector, showing ultrahigh drug‐loading degree, biodegradability, pH‐responsive fast dissolution, high stability in serum, and ease of surface functionalization. Furthermore, the half‐maximal inhibitory concentration value of the nano‐in‐nano HSFN@ADS‐FA is ≈54 times lower than the conventional nanovector (LSFN@ADS‐FA) with a low drug‐loading degree. Overall, this nano‐in‐nano vector merges the best of polymeric nanoparticles and drug nanocrystals.     

Organic Light‐Emitting Diodes: Organic Light‐Emitting Diodes with a White‐Emitting Molecule: Emission Mechanism and Device Characteristics (Adv. Funct. Mater. 4/2011)

The unique and unprecedented electroluminescence behavior of the white‐emitting molecule 3‐(1‐(4‐(4‐(2‐(2‐hydroxyphenyl)‐4,5‐diphenyl‐1H‐imidazol‐1‐yl)phenoxy)phenyl)‐4,5‐diphenyl‐1H‐imidazol‐2‐yl)naphthalen‐2‐ol (W1), fluorescence emission from which is controlled by the excited‐state intramolecular proton transfer (ESIPT) is investigated. W1 is composed of covalently linked blue‐ and yellow‐color emitting ESIPT moieties between which energy transfer is entirely frustrated. It is demonstrated that different emission colors (blue, yellow, and white) can be generated from the identical emitter W1 in organic light‐emitting diode (OLED) devices. Charge trapping mechanism is proposed to explain such a unique color‐tuned emission from W1. Finally, the device structure to create a color‐stable, color reproducible, and simple‐structured white organic light‐emitting diode (WOLED) using W1 is investigated. The maximum luminance efficiency, power efficiency, and luminance of the WOLED were 3.10 cd A^?1, 2.20 lm W^?1, 1 092 cd m^?2, respectively. The WOLED shows white‐light emission with the Commission Internationale de l′Eclairage (CIE) chromaticity coordinates (0.343, 0.291) at a current level of 10 mA cm^?2. The emission color is high stability, with a change of the CIE chromaticity coordinates as small as (0.028, 0.028) when the current level is varied from 10 to 100 mA cm^?2.     

Degradation Mechanism of Perovskite Light‐Emitting Diodes: An In Situ Investigation via Electroabsorption Spectroscopy and Device Modelling

The past few years have seen a significant improvement in the efficiency of organometal halide‐perovskite‐based light‐emitting diodes (PeLEDs). However, poor operation stability of the devices still hinders the commercialization of this technology for practical applications. Despite extensive studies on the degradation mechanisms of perovskite thin films, it remains unclear where and how degradation occurs in a PeLED. Electroabsorption (EA) spectroscopy is applied to study the degradation process of PeLEDs during operation and directly evaluates the stability of each functional layer (i.e., charge transporting layers and light‐emitting layer) by monitoring their unique optical signatures. The EA measurements unambiguously reveal that the degradation of the PeLEDs occurs predominantly in the perovskite layer. With finite‐element method‐based device modeling, it is further revealed that the degradation may initiate from the interface between the perovskite and hole transporting layers and that vacancy, antisite, or interstitial defects can further accelerate this degradation. Inspired by these observations, a surface‐treatment step is introduced to passivate the perovskite surface with phenethylammonium iodide. The passivation leads to a drastic enhancement of the PeLED stability, with the operation lifetime increased from 1.5 to 11.3 h under a current density of 100 mA cm^?2.     

Mechanism of charge recombination and IPCE in ZnO dye‐sensitized solar cells having I−/I and Br−/Br redox couple

The influence of intensity and wavelength variation on the solar cell parameters of two different ZnO‐based liquid state DSSCs named as Cell (A) ZnO/EosinY/LiI and Cell (B) ZnO/EosinY/LiBr was studied. It was found that V_oc and I_sc depend logarithmically and linearly on light flux, respectively, which indicates that light absorption and carrier diffusion do not limit the solar cell efficiency. The data was analyzed to ascertain the charge recombination mechanism between conduction band electrons and the electrolytes. The regeneration of dye due to I⁻/I₃ and Br⁻/Br redox couple was examined by studying the wavelength dependence of IPCE. An estimation of series and shunt resistance is made using two methods: (i) different illumination method (ii) single I–V curve, for the two cells in order to understand the role of the electrolyte in controlling the solar cell parameters. Copyright © 2010 John Wiley & Sons, Ltd.     

Tuning the Emitting Color of Organic Light‐Emitting Diodes Through Photochemically Induced Transformations: Towards Single‐Layer,Patterned, Full‐Color Displays and White‐Lighting Applications

Photochemically induced emission tuning for the definition of pixels emitting the three primary colors, red, green, blue (RGB), in a single conducting polymeric layer is investigated. The approach proposed is based on an acid‐induced emission shift of the (1‐[4‐(dimethylamino)phenyl]‐6‐phenylhexatriene) (DMA‐DPH) green emitter and acid‐induced quenching of the red fluorescent emitter (4‐dimethylamino‐4′‐nitrostilbene) (DANS). The two emitters are dispersed in the wide bandgap conducting polymer poly(9‐vinylcarbazole) (PVK), along with a photoacid generator (PAG). In the unexposed film areas, red emission is observed because of efficient energy transfer from PVK and DMA‐DPH to DANS. Exposure of selected areas of the film at different doses results in quenching of the red emitter's fluorescence and the formation of green, blue, or even other color‐emitting pixels, depending on the exposure dose and the relative concentrations of the different compounds in the film. Organic light‐emitting diodes having the PVK polymer containing the appropriate amounts of DMA‐DPH, DANS, and PAG as the emitting layer are fabricated and electroluminescence spectra are recorded. The time stability of induced emission spectrum changes and the color stability during device operation are also examined, and the first encouraging results are obtained.     

UV nanoimprint for the replication of etched ZnO:Al textures applied in thin‐film silicon solar cells

In this work, we present a technology for a high precision nanostructure replication process based on ultraviolet nanoimprint lithography for the application in the field of thin‐film photovoltaics. The potential of the technology is demonstrated by the fabrication of microcrystalline silicon thin‐film prototype solar cells. The high accuracy replication of random microstructures made from sputtered and etched ZnO:Al, used to scatter the incident light in thin solar cells, is shown by local topography investigations of the same 7.5 × 7.5 µm² area on the master and the replica. Different types of imprint resists and imprint moulds were investigated to find the optimal, high precision replication technology. Two types of thin‐film silicon solar cells, in p‐i‐n and n‐i‐p configuration, were fabricated to study the potential of the imprint technology for different applications. It is shown that solar cells deposited on an imprinted glass hold similar performances compared with reference solar cells fabricated with a standard process on textured ZnO:Al. Thus, it is demonstrated that the replication of light scattering structures by using an imprint process is an attractive method to decouple the scattering properties from the layer forming the electrical front contact. Because a simple and cheap high throughput process is used, this study additionally proves the relevance for the industrial mass production in the field of photovoltaics. Copyright © 2013 John Wiley & Sons, Ltd.     

Photoquantum Hall Effect and Light‐Induced Charge Transfer at the Interface of Graphene/InSe Heterostructures

The transfer of electronic charge across the interface of two van der Waals crystals can underpin the operation of a new class of functional devices. Among van der Waals semiconductors, an exciting and rapidly growing development involves the “post‐transition” metal chalcogenide InSe. Here, field effect phototransistors are reported where single layer graphene is capped with n‐type InSe. These device structures combine the photosensitivity of InSe with the unique electrical properties of graphene. It is shown that the light‐induced transfer of charge between InSe and graphene offers an effective method to increase or decrease the carrier density in graphene, causing a change in its resistance that is gate‐controllable and only weakly dependent on temperature. The charge transfer at the InSe/graphene interface is probed by Hall effect and photoconductivity measurmentes and it is demonstrated that light can induce a sign reversal of the quantum Hall voltage and photovoltaic effects in the graphene layer. These findings demonstrate the potential of light‐induced charge transfer in gate‐tunable InSe/graphene phototransistors for optoelectronics and quantum metrology.