Lithium Tin Sulfide—a High‐Refractive‐Index 2D Material for Humidity‐Responsive Photonic Crystals

Extending the portfolio of novel stimuli‐responsive, high‐refractive‐index (RI) materials besides titania is key to improve the optical quality and sensing performance of existing photonic devices. Herein, lithium tin sulfide (LTS) nanosheets are introduced as a novel solution processable ultrahigh RI material (n = 2.50), which can be casted into homogeneous thin films using wet‐chemical deposition methods. Owing to its 2D morphology, thin films of LTS nanosheets are able to swell in response to changes of relative humidity. Integration of LTS nanosheets into Bragg stacks (BSs) based on TiO₂, SiO₂, nanoparticles or H₃Sb₃P₂O₁₄ nanosheets affords multilayer systems with high optical quality at an extremely low device thickness of below 1 µm. Owing to the ultrahigh RI of LTS nanosheets and the high transparency of the thin films, BSs based on porous titania as the low‐RI material are realized for the first time, showing potential application in light‐managing devices. Moreover, the highest RI contrast ever realized in BSs based on SiO₂ and LTS nanosheets is reported. Finally, exceptional swelling capability of an all‐nanosheet BS based on LTS and H₃Sb₃P₂O₁₄ nanosheets is demonstrated, which bodes well for a new generation of humidity sensors with extremely high sensitivity.     

Built‐In Haze Glass‐Fabric Reinforced Siloxane Hybrid Film for Efficient Organic Light‐Emitting Diodes (OLEDs)

Substrates with high transmittance and high haze are desired for increasing the light outcoupling efficiency of organic light‐emitting diodes (OLEDs). However, most of the polymer films used as substrate have high transmittance and low haze. Herein, a facile route to fabricate a built‐in haze glass‐fabric reinforced siloxane hybrid (GFRH) film having high total transmittance (≈89%) and high haze (≈89%) is reported using the scattering effect induced by refractive index contrast between the glass fabric and the siloxane hybrid (hybrimer). The hybrimer exhibiting large refractive index contrast with the glass fabric is synthesized by removing the phenyl substituents. Besides its optical properties, the hazy GFRH films exhibit smooth surface (R_sq = 0.2 nm), low thermal expansion (13 ppm °C⁻¹), high chemical stability, and dimensional stability. Owing to the outstanding properties of the GFRH film, OLED is successfully fabricated onto the film exhibiting 74% external quantum efficiency enhancement. The hazy GFRH's unique optical properties, excellent thermal stability, outstanding dimensional stability, and the ability to perform as a transparent electrode enable them as a wide ranging substrate for the flexible optoelectronic devices.     

Nanoscale Refractive Index Tuning of Siloxane‐Based Self‐Assembled Electro‐Optic Superlattices

The refractive indices of self‐assembled organic electro‐optic superlattices can be tuned by intercalating high‐Z optically transparent group 13 metal oxide sheets into the structures during the self‐assembly process. Microstructurally regular acentricity and sizable electro‐optic responses are retained in this straightforward synthetic procedure. This “one‐pot” all wet‐chemistry approach involves: i) layer‐by‐layer covalent self‐assembly of intrinsically acentric multilayers of high‐hyperpolarizability chromophores on inorganic oxide substrates, ii) protecting group cleavage to generate a large density of reactive surface hydroxyl sites, iii) self‐limiting capping of each chromophore layer with octachlorotrisiloxane, iv) deposition of metal oxide sheets derived from THF solutions of Ga(OⁱC₃H₇)₃ or In(OⁱC₃H₇)₃, and v) covalent capping of the resulting superlattices.     

Enhanced Omnidirectional Photovoltaic Performance of Solar Cells Using Multiple‐Discrete‐Layer Tailored‐ and Low‐Refractive Index Anti‐Reflection Coatings

An optimized four‐layer tailored‐ and low‐refractive index anti‐reflection (AR) coating on an inverted metamorphic (IMM) triple‐junction solar cell device is demonstrated. Due to an excellent refractive index matching with the ambient air by using tailored‐ and low‐refractive index nanoporous SiO₂ layers and owing to a multiple‐discrete‐layer design of the AR coating optimized by a genetic algorithm, such a four‐layer AR coating shows excellent broadband and omnidirectional AR characteristics and significantly enhances the omnidirectional photovoltaic performance of IMM solar cell devices. Comparing the photovoltaic performance of an IMM solar cell device with the four‐layer AR coating and an IMM solar cell with the conventional SiO₂/TiO₂ double layer AR coating, the four‐layer AR coating achieves an angle‐of‐incidence (AOI) averaged short‐circuit current density, J_SC, enhancement of 34.4%, whereas the conventional double layer AR coating only achieves an AOI‐averaged J_SC enhancement of 25.3%. The measured reflectance reduction and omnidirectional photovoltaic performance enhancement of the four‐layer AR coating are to our knowledge, the largest ever reported in the literature of solar cell devices.     

OMNIDIRECTIONAL HIGH REFLECTOR FOR INFRARED WAVELENGTH

We have purposed the design of omnidirectional high reflectors with wide bandwidth (nearly 6300A⁰) for the infrared wavelength. Using translational matrix method for numerical calculation, it is found that a complete photonic band gap high reflector covering the wavelength region 11500A⁰ to 17800A⁰ is obtained for the quarter wave stack air / (n_L n_H)⁷ / air by using the tellurium (n=4.60) and TiO₂ (n=2.35) as material of high reflective index and SiO₂(n=1.45) low refractive index. Due to high refractive index of contrast of the structure i.e. SiO₂/tellurium, a large complete photonic band gap, omnidirectional high reflector, has been observed for the infrared wavelengths. This type of omnidirectional high reflector can be used in telecommunication. Besides this, we have studied the effective refractive indices (phase and group) of the proposed structures. It is observed that the effective refractive indices (phase and group) of the high omnidirectional reflector band are largely changed near the band edges due to the high refractive index of contrast, and the reflections from the internal interfaces of the structure.     

Plasmonic Nanoparticles as a Physically Unclonable Function for Responsive Anti‐Counterfeit Nanofingerprints

Far‐field scattering of randomly deposited Au nanoparticles (NPs) is demonstrated as a physically unclonable optical function for anti‐counterfeit applications in which the scattering patterns are easily produced yet impractical to replicate. Colloidal metal NPs are superb components for nanoscale labels owing to their small dimensions and intense far‐field scattering visible at wavelengths that depend on colloidal size, shape, composition, and their local environment. The feasibility of Au NP depositions as nanofingerprints is presented using a simple pattern matching algorithm. These NPs offer extended functionality as environmental sensors. Taking advantage of the local refractive index dependent scattering wavelengths of metal NPs, a detectable color change is also demonstrated from a nanofingerprint comprised of Au and Ag NPs when placed in media with different refractive index. The facile deposition method coupled with the intense scattering and optical response of metal NPs provides physically unclonable tags (nanofingerprints) with the ability to serve as tamper‐evident and aging labels.     

LaPO4 Mineral Liquid Crystalline Suspensions with Outstanding Colloidal Stability for Electro‐Optical Applications

Mineral liquid crystals are materials in which mineral's intrinsic properties are combined with the self‐organization behavior of colloids. However, the use of such a system for practical application, such as optical switching, has rarely been demonstrated due to the fundamental drawbacks of colloidal systems such as limited dispersion stability. Studying colloidal suspensions of LaPO₄ nanorods, it is found that drastic improvement of colloidal stability can be obtained through a transfer of particles from water towards ethylene glycol, thus enabling the investigation of liquid crystalline properties of these concentrated suspensions. Using polarization microscopy and small‐angle x‐ray scattering (SAXS), self‐organization into nematic and columnar mesophases is observed enabling the determination of the whole phase diagram as a function of ionic strength and rod volume fraction. When an external alternative electric field is applied, a very efficient orientation of the nanorods in the liquid‐crystalline suspension is obtained, which is associated with a significant optical birefringence. These properties, combined with the high colloidal stability, are promising for the use of such high transparent and athermal material in electro‐optical devices.     

Remote‐Controllable Molecular Knob in the Mesomorphic Helical Superstructures

A programed light‐responsive chiral liquid crystal (LC) containing four photochromic azobenzene moieties covalently connected to a central bicyclic chiral core (abbreviated as AZ₄ICD) is newly designed, precisely synthesized, and efficiently applied as a remote‐controllable molecular knob for the optically tunable thin film. First of all, phase evolutions and ordered structures of AZ₄ICD are systematically investigated by a combination of thermal, microscopic, scattering, and simulation techniques. Wide‐angle X‐ray diffractions of oriented AZ₄ICD samples indicate that the AZ₄ICD molecule itself basically forms layer structures: one is a low‐ordered chiral smectic A LC phase (SmA*) with 5.61 nm layer periodicity at high temperatures, and two highly ordered smectic crystal (SmCr₁ and SmCr₂) phases are subsequently formed at lower temperatures with the anticlinically tilted molecular packing structures. The helical superstructures of chiral nematic LC phase (N*) can be spontaneously constructed by doping AZ₄ICD chiral agents into the achiral nematic molecules. Due to the bent conformational geometry of AZ₄ICD, the thermal window of blue LC phase (BP) is expanded by stabilizing the double twisted cylindrical building blocks. Remote‐controllable phase transformations in the mesomorphic helical superstructures are demonstrated by tuning the wavelength of light.     

Hyperbranched Polymers with High Transparency and Inherent High Refractive Index for Application in Organic Light‐Emitting Diodes

Hyperbranched polyvinylsulfides have been prepared through a facile, metal‐free, radical induced “A₂+B₃” thiol‐yne polymerization of 1,3,5‐tris(naphthalylethynyl) benzene and 1,4‐dithiolbenzene with three different input ratios. The resulting polymers exhibit excellent optical properties like high transparency and very high refractive index (RI) of up to 1.7839, combined with high thermal stability (T_d5% up to 420 °C) and excellent solution processability. These properties make them ideal candidates as high RI polymeric materials (HRIP) in connection with light out‐coupling schemes for organic light‐emitting diodes (OLEDs). A series of hyperbranched HRIPs with varying monomer compositions have been compared in their optical properties. Finally, phosphorescent monochrome OLEDs are fabricated on top of HRIP layers to test the compatibility of HRIPs with state‐of‐the‐art OLEDs. The results show that the HRIPs do not deteriorate the performance of the OLEDs while maintaining external quantum efficiencies of over 20% for phosphorescent red OLEDs. These results open a pathway toward alternative, low‐cost, and scalable out‐coupling concepts through refractive index matching of the OLED materials and the HRIPs presented.     

Ultra‐Flexible Boron‐Oxygen 3D Solid‐State Networks

The existence of ultra‐flexible low‐energy forms of boron oxides (B₂O₃ and BO) is demonstrated, in particular structures in which B₃O₃ or B₄O₂ six‐membered rings are linked by single B‐O‐B bridges. The minima in the energy landscapes are remarkably broad; the variation in the internal energies is very small over a very large range of volumes. Such volume changes may even exceed 200%. This remarkable behavior is attributed predominantly to the pronounced angular flexibility of the B‐O‐B bridges linking the rings, which is unusual for a covalent bond. At larger volumes, the structures are nanoporous; the pores collapse upon compression with negligible change in energy, making these suitable as guest‐host materials. In marked contrast, in other materials where low density frameworks have been reported or predicted, such low‐density phases are considerably higher in energy. The flexibility of the structures also offers a resolution of the long‐standing controversy reconciling the structure and density of vitreous B₂O₃.     

A New Family of Ultralow Loss Reversible Phase‐Change Materials for Photonic Integrated Circuits: Sb2S3 and Sb2Se3

Phase‐change materials (PCMs) are seeing tremendous interest for their use in reconfigurable photonic devices; however, the most common PCMs exhibit a large absorption loss in one or both states. Here, Sb₂S₃ and Sb₂Se₃ are demonstrated as a class of low loss, reversible alternatives to the standard commercially available chalcogenide PCMs. A contrast of refractive index of Δn = 0.60 for Sb₂S₃ and Δn = 0.77 for Sb₂Se₃ is reported, while maintaining very low losses (k < 10^?5) in the telecommunications C‐band at 1550 nm. With a stronger absorption in the visible spectrum, Sb₂Se₃ allows for reversible optical switching using conventional visible wavelength lasers. Here, a stable switching endurance of better than 4000 cycles is demonstrated. To deal with the essentially zero intrinsic absorption losses, a new figure of merit (FOM) is introduced taking into account the measured waveguide losses when integrating these materials onto a standard silicon photonics platform. The FOM of 29 rad phase shift per dB of loss for Sb₂Se₃ outperforms Ge₂Sb₂Te₅ by two orders of magnitude and paves the way for on‐chip programmable phase control. These truly low‐loss switchable materials open up new directions in programmable integrated photonic circuits, switchable metasurfaces, and nanophotonic devices.     

Electrostatic Self‐Assembly Conjugated Polyelectrolyte‐Surfactant Complex as an Interlayer for High Performance Polymer Solar Cells

A simple method is demonstrated to improve the film‐forming properties and air stability of a conjugated polyelectrolyte (CPE) without complicated synthesis of new chemical structures. An anionic surfactant, sodium dodecybenzenesulfonate (SDS), is mixed with cationic CPEs. The electrostatic attraction between these two oppositely‐charged materials provides the driving force to form a stable CPE‐surfactant complex. Compared with a pure CPE, this electrostatic complex is not only compatible with highly hydrophobic bulk‐heterojunction (BHJ) films, e.g. poly(3‐hexylthiophene):[6,6]‐phenyl C₆₁ butyric acid methyl ester (P3HT:PCBM), but also works well with other low bandgap polymer‐based BHJ films. Using this complex as a cathode interface layer, a high power conversion efficiency of 4% can be obtained in P3HT:PCBM solar cells together with improved stability in air. Moreover, ～20% performance enhancement can also be achieved when the complex is used as an interlayer to replace calcium metal for low bandgap polymer‐based BHJ systems.     

High‐Performance,Air‐Stable,Top‐Gate,p‐Channel WSe2 Field‐Effect Transistor with Fluoropolymer Buffer Layer

High‐performance, air‐stable, p‐channel WSe₂ top‐gate field‐effect transistors (FETs) using a bilayer gate dielectric composed of high‐ and low‐k dielectrics are reported. Using only a high‐k Al₂O₃ as the top‐gate dielectric generally degrades the electrical properties of p‐channel WSe₂, therefore, a thin fluoropolymer (Cytop) as a buffer layer to protect the 2D channel from high‐k oxide forming is deposited. As a result, a top‐gate‐patterned 2D WSe₂ FET is realized. The top‐gate p‐channel WSe₂ FET demonstrates a high hole mobility of 100 cm²_­ V^?1 s^?1 and a I_ON/I_OFF ratio > 10⁷ at low gate voltages (V_GS ca. ?4 V) and a drain voltage (V_DS) of ?1 V on a glass substrate. Furthermore, the top‐gate FET shows a very good stability in ambient air with a relative humidity of 45% for 7 days after device fabrication. Our approach of creating a high‐k oxide/low‐k organic bilayer dielectric is advantageous over single‐layer high‐k dielectrics for top‐gate p‐channel WSe₂ FETs, which will lead the way toward future electronic nanodevices and their integration.     

Modifying the Output Characteristics of an Organic Light‐Emitting Device by Refractive‐Index Modulation

In order to modify the output characteristics of organic light‐emitting devices (OLEDs), the optical properties of an active layer within the device are patterned without introducing any thickness modulation. For this purpose a new conjugated copolymer, which serves as a hole‐transporting material and at the same time can be index patterned using UV techniques, is synthesized. Poly(VC‐co‐VBT) (VC: N‐vinylcarbazole; VBT: 4‐vinylbenzyl thiocyanate) is prepared by free‐radical copolymerization of VC and VBT. The material contains photoreactive thiocyanate groups that enable altering of the material's refractive index under UV illumination. This copolymer is employed as a patternable hole‐transporting layer in multilayer OLEDs. Refractive‐index gratings in poly(VC‐co‐VBT) are inscribed using a holographic setup based upon a Lloyd mirror configuration. The fourth harmonic of a Nd:YAG (YAG: yttrium aluminum garnet) laser (266 nm) serves as the UV source. In this way 1D photonic structures are integrated in an OLED containing AlQ₃ (tris(8‐hydroxyquinoline) aluminum) as the emitting species. It is assured that only a periodical change of the refractive index (Δn = 0.006 at λ = 540 nm) is generated in the active material but no surface‐relief gratings are generated. The patterned devices show more forward‐directed out‐coupling behavior than unstructured devices (increase in luminosity by a factor of five for a perpendicular viewing direction). This effect is most likely due to Bragg scattering. For these multilayer structures, optimum outcoupling was observed for grating periods Λ ～ 390 nm.     

Bio‐inspired Highly Scattering Networks via Polymer Phase Separation

A common strategy to optimize whiteness in living organisms consists in using 3D random networks with dense and polydisperse scattering elements constituted by relatively low refractive index materials. Inspired by these natural architectures, a fast and scalable method to produce highly scattering porous polymer films via phase separation is developed. By varying the molecular weight of the polymer, the morphology of the porous films is modified, and therefore their scattering properties are tuned. The achieved transport mean free paths are in the micrometer range, improving the scattering strength of analogous low refractive index systems, e.g., standard white paper, by an order of magnitude. The produced porous films show a broadband reflectivity of ≈75% while only 4 µm thick. In addition, the films are flexible and can be readily index‐matched with water (i.e., they become transparent when wet), allowing for various applications such as coatings with tunable transmittance and responsive paints.     

Metamaterial Demonstrates Both a High Refractive Index and Extremely Low Reflection in the 0.3-THz Band

Communication and imaging in the terahertz waveband have advanced rapidly in offering industrial applications. However, optical elements such as collimated lenses in the terahertz waveband are bulky compared with the wavelength due to the lack of naturally occurring substances with a high refractive index and low loss. It is essential to miniaturize optical elements in the terahertz waveband for industrial application. Metamaterials consisting of subwavelength structures can arbitrarily control permittivity and permeability and provide a range of refractive indices. Here, we demonstrate a metamaterial with both a high refractive index and extremely low reflection consisting of symmetrically aligned paired cut metal wires with 18,800 units on the front and back surfaces of a dielectric substrate. Measurements by terahertz time-domain spectroscopy (THz-TDS) confirm a high effective refractive index of 6.66 + j0.123, extremely low reflection power of 1.16%, and the unprecedented high figure of merit (FOM = |n _real/n _imag|) of above 300 in the 0.3-THz band. Components with such specifications would enable miniature, high-performance optical elements in the terahertz waveband such as ultrathin flat antennas with high directivity. Further, the concept of the metamaterial with both a high refractive index and extremely low reflection potentially offers a wide range of attractive applications such as solid immersion lenses and cloaking devices.     

Sacrificial‐Layer Atomic Layer Deposition for Fabrication of Non‐Close‐Packed Inverse‐Opal Photonic Crystals

A method is presented for predicting and precisely controlling the structure of photonic crystals fabricated using sacrificial‐layer atomic layer deposition. This technique provides a reliable method for fabrication of high‐quality non‐close‐packed inverse shell opals with large static tunability and precise structural control. By using a sacrificial layer during opal infiltration, the inverse‐opal pore size can be increased with sub‐nanometer resolution and without distorting the lattice to allow for a high degree of dielectric backfilling and increased optical tunability. For a 10 % sacrificial layer, static tunability of 80 % is predicted for the inverse opal. To illustrate this technique, SiO₂ opal templates were infiltrated using atomic layer deposition of ZnS, Al₂O₃, and TiO₂. Experimentally, a static tunability of over 600 nm, or 58 %, was achieved and is well described by both a geometrical model and a numerical‐simulation algorithm. When extended to materials of higher refractive index, this method will allow the facile fabrication of 3D photonic crystals with optimized photonic bandgaps.     

Integration of a Rib Waveguide Distributed Feedback Structure into a Light‐Emitting Polymer Field‐Effect Transistor

Ambipolar light‐emitting organic field‐effect transistors (LEFETs) possess the ability to efficiently emit light due to charge recombination in the channel. Since the emission can be made to occur far from the metal electrodes, the LEFET structure has been proposed as a potential architecture for electrically pumped organic lasers. Here, a rib waveguide distributed feedback structure consisting of tantalum pentoxide (Ta₂O₅) integrated within the channel of a top gate/bottom contact LEFET based on poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) is demonstrated. The emitted light is coupled efficiently into the resonant mode of the DFB waveguide when the recombination zone of the LEFET is placed directly above the waveguide ridge. This architecture provides strong mode confinement in two dimensions. Mode simulations are used to optimize the dielectric thickness and gate electrode material. It is shown that electrode absorption losses within the device can be eliminated and that the lasing threshold for optical pumping of the LEFET structure with all electrodes (4.5 µJ cm^?2) is as low as that of reference devices without electrodes. These results enable quantitative judgement of the prospects for realizing an electrically pumped organic laser based on ambipolar LEFETs. The proposed device provides a powerful, low‐loss architecture for integrating high‐performance ambipolar organic semiconductor materials into electrically pumped lasing structures.     

High Thermoelectric Performance in Supersaturated Solid Solutions and Nanostructured n‐Type PbTe–GeTe

Sb‐doped and GeTe‐alloyed n‐type thermoelectric materials that show an excellent figure of merit ZT in the intermediate temperature range (400–800 K) are reported. The synergistic effect of favorable changes to the band structure resulting in high Seebeck coefficient and enhanced phonon scattering by point defects and nanoscale precipitates resulting in reduction of thermal conductivity are demonstrated. The samples can be tuned as single‐phase solid solution (SS) or two‐phase system with nanoscale precipitates (Nano) based on the annealing processes. The GeTe alloying results in band structure modification by widening the bandgap and increasing the density‐of‐states effective mass of PbTe, resulting in significantly enhanced Seebeck coefficients. The nanoscale precipitates can improve the power factor in the low temperature range and further reduce the lattice thermal conductivity (κ_lat). Specifically, the Seebeck coefficient of Pb_0.988Sb_0.012Te–13%GeTe–Nano approaches ?280 µV K^?1 at 673 K with a low κ_lat of 0.56 W m^?1 K^?1 at 573 K. Consequently, a peak ZT value of 1.38 is achieved at 623 K. Moreover, a high average ZT_avg value of ≈1.04 is obtained in the temperature range from 300 to 773 K for n‐type Pb_0.988Sb_0.012Te–13%GeTe–Nano.     

Evaporation‐Induced Coating and Self‐Assembly of Ordered Mesoporous Carbon‐Silica Composite Monoliths with Macroporous Architecture on Polyurethane Foams

A facile approach of solvent‐evaporation‐induced coating and self‐assembly is demonstrated for the mass preparation of ordered mesoporous carbon‐silica composite monoliths by using a polyether polyol‐based polyurethane (PU) foam as a sacrificial scaffold. The preparation is carried out using resol as a carbon precursor, tetraethyl orthosilicate (TEOS) as a silica source and Pluronic F127 triblock copolymer as a template. The PU foam with its macrostructure provides a large, 3D, interconnecting interface for evaporation‐induced coating of the phenolic resin‐silica block‐copolymer composites and self‐assembly of the mesostructure, and endows the composite monoliths with a diversity of macroporous architectures. Small‐angle X‐ray scattering, X‐ray diffraction and transmission electron microscopy results indicate that the obtained composite monoliths have an ordered mesostructure with 2D hexagonal symmetry (p6m) and good thermal stability. By simply changing the mass ratio of the resol to TEOS over a wide range (10–90%), a series of ordered, mesoporous composite foams with different compositions can be obtained. The composite monoliths with hierarchical macro/mesopores exhibit large pore volumes (0.3–0.8 cm³ g^?1), uniform pore sizes (4.2–9.0 nm), and surface areas (230–610 m² g^?1). A formation process for the hierarchical porous composite monoliths on the struts of the PU foam through the evaporation‐induced coating and self‐assembly method is described in detail. This simple strategy performed on commercial PU foam is a good candidate for mass production of interface‐assembly materials.