Photoswitching of Ferroelectric Liquid Crystals Using Unsymmetrical Chiral Thioindigo Dopants: Photoinduced Inversion of the Sign of Spontaneous Polarization

A new unsymmetrical chiral thioindigo dopant 6‐[(R,R)‐2,3‐difluorooct‐1‐yloxy]‐5′‐nitro‐6′‐[(R)‐2‐octyloxy]thioindigo ( 4 ) designed to photoinvert the sign of spontaneous polarization (P_S) in a ferroelectric chiral smectic C (SmC*) liquid crystal was prepared using a synthetic approach previously developed in our laboratory. In this new “ambidextrous” design, the (R)‐2‐octyloxy side‐chain is sterically coupled to the thioindigo core and induces a positive P_S, whereas the (R,R)‐2,3‐difluorooctyloxy side‐chain is decoupled from the core and induces a larger negative P_S. In the trans form, this dopant induces a negative polarization in the SmC host (+)‐4‐(4‐methylhexyloxy)phenyl 4‐decyloxybenzoate ( PhB ). Irradiation of a 1 mol‐% mixture of 4 in PhB at λ = 510 nm caused a sign inversion of P_S, from –0.88 to +0.42 nC cm^–2 at T – T_C = –5 °C, which is consistent with an increase in the polarization power of the coupled 2‐octyloxy/thioindigo unit over that of the 2,3‐difluorooctyloxy unit, due to the increase in transverse dipole moment of the thioindigo core upon trans–cis photoisomerization. The P_S sign inversion was confirmed by a surface‐stabilized ferroelectric liquid crystal photoswitching experiment. Spectroscopic measurements on films of the doped liquid crystal mixtures showed that trans–cis photoisomerization is gradually suppressed with increasing dopant mole fraction, possibly as a result of increased dopant aggregation.     

A Europium Complex With Excellent Two‐Photon‐Sensitized Luminescence Properties

We report the synthesis and excellent two‐photon‐sensitized luminescence properties of a new complex [Eu(tta)₃dmbpt] (tta = henoyltrifluoroacetonate; dmbpt = 2‐(N,N‐diethyl‐2,6‐dimethylanilin‐4‐yl)‐4,6‐bis(3,5‐dimethylpyrazol‐1‐yl)‐1,3,5‐triazine) that exhibits the highest efficiency of lanthanide luminescence when excited by near‐infrared (NIR) laser pulses (action cross section of two‐photon‐excited fluorescence δ × Φ_F: 85 GM at 812 nm and 56 GM at 842 nm; 1 GM = 10^–50 cm⁴ s photon^–1 molecule^–1). Compared to a previously reported [Eu(tta)₃dpbt] complex, (dpbt = 2‐(N,N‐diethylanilin‐4‐yl)‐4,6‐bis(3,5‐dimethylpyrazol‐1‐yl)‐1,3,5‐triazine), [Eu(tta)₃dmbpt] has two excess methyl groups at the 2,6‐positions of the phenyl ring. Crystallographic data of dmbpt show that the 2,6‐dimethyl substitutes bring about a significant twist in the conformation of the diethylamino group compared to that in dpbt, which severely influences the conjugation in the ground state between the electron lone pair of N in the –N(CH₂–)₂ moiety and the aromatic electron system in dmbpt. The large two‐photon absorption (TPA) cross section of dmbpt is mainly derived from its large static dipole moment difference between the S₀ and the S₁ states, which is partly responsible for the high capability of two‐photon‐sensitized luminescence of [Eu(tta)₃dmbpt]. The broader two‐ and single‐photon excitation windows and the superior two‐photon‐sensitized luminescent properties in the long‐wavelength NIR region of [Eu(tta)₃dmbpt] compared to [Eu(tta)₃dpbt] are also explained according to the calculated results and twisted structure.     

Cobalt‐Doping in Molybdenum‐Carbide Nanowires Toward Efficient Electrocatalytic Hydrogen Evolution

Efficient hydrogen evolution reaction (HER) over noble‐metal‐free electrocatalysts provides one of the most promising pathways to face the energy crisis. Herein, facile cobalt‐doping based on Co‐modified MoO_x–amine precursors is developed to optimize the electrochemical HER over Mo₂C nanowires. The effective Co‐doping into Mo₂C crystal structure increases the electron density around Fermi level, resulting in the reduced strength of Mo–H for facilitated HER kinetics. As expected, the Co‐Mo₂C nanowires with an optimal Co/Mo ratio of 0.020 display a low overpotential (η₁₀ = 140 and 118 mV for reaching a current density of –10 mA cm^?2; η₁₀₀ = 200 and 195 mV for reaching a current density of –100 mA cm^?2), a small Tafel slope (39 and 44 mV dec^?1), and a low onset overpotential (40 and 25 mV) in 0.5 m H₂SO₄ and 1.0 m KOH, respectively. This work highlights a feasible strategy to explore efficient electrocatalysts via engineering on composition and nanostructure.     

High‐Purity‐Blue and High‐Efficiency Electroluminescent Devices Based on Anthracene

Novel blue‐light‐emitting materials, 9,10‐bis(1,2‐diphenyl styryl)anthracene (BDSA) and 9,10‐bis(4′‐triphenylsilylphenyl)anthracene (BTSA), which are composed of an anthracene molecule as the main unit and a rigid and bulky 1,2‐diphenylstyryl or triphenylsilylphenyl side unit, have been designed and synthesized. Theoretical calculations on the three‐dimensional structures of BDSA and BTSA show that they have a non‐coplanar structure and inhibited intermolecular interactions, resulting in a high luminescence efficiency and good color purity. By incorporating these new, non‐doped, blue‐light‐emitting materials into a multilayer device structure, it is possible to achieve luminance efficiencies of 1.43 lm W^–1 (3.0 cd A^–1 at 6.6 V) for BDSA and 0.61 lm W^–1 (1.3 cd A^–1 at 6.7 V) for BTSA at 10 mA cm^–2. The electroluminescence spectrum of the indium tin oxide (ITO)/copper phthalocyanine (CuPc)/1,4‐bis[(1‐naphthylphenyl)‐amino]biphenyl (α‐NPD)/BDSA/tris(9‐hydroxyquinolinato)aluminum (Alq₃)/LiF/Al device shows a narrow emission band with a full width at half maximum (FWHM) of 55 nm and a λ_max = 453 nm. The FWHM of the ITO/CuPc/α‐NPD/BTSA/Alq₃/LiF/Al device is 53 nm, with a λ_max = 436 nm. Regarding color, the devices showed highly pure blue emission ((x,y) = (0.15,0.09) for BTSA, (x,y) = (0.14,0.10) for BDSA) at 10 mA cm^–2 in Commission Internationale de l'Eclairage (CIE) chromaticity coordinates.     

A Novel Room‐Temperature Multiferroic System of Hexagonal Lu1−xInxFeO3

In the present work, h‐RFeO₃ multiferroic ceramics are designed and created by introducing chemical pressure (In‐substitution for Lu) in LuFeO₃. Lu_1?xIn_xFeO₃ (x = 0‐0.75) ceramics are prepared by the standard solid‐state reaction process. The crystal structure of the present ceramics is tuned from centrosymmetric Pbnm (x = 0) to non‐centrosymmetric P6₃cm (x = 0.4–0.6), and subsequently to centrosymmetric P6₃/mmc (x = 0.75), while the Pbnm and P6₃cm biphase structure is detected for x = 0.25. The Curie temperature for the polar P6₃cm (x = 0.4–0.6) phase decreases from >1000 to ≈550 K with increasing x. Cloverleaf ferroelectric domain structures are determined in polar Lu_0.5In_0.5FeO₃ samples, and the ferroelectric domain walls at atomic scale are evaluated by the aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy (HAADF STEM), where the spontaneous polarization of 1.73 µC cm^?2 is determined for x = 0.5. The spontaneous polarization is also confirmed by calculating the site displacement from the centrosymmetric phase based on the X‐ray diffraction (XRD) data. Meanwhile, two magnetic transitions are determined for all compositions, that is, paramagnetic to antiferromagnetic transition at Néel temperature T_N (≈350 K for x = 0.4–0.6), and antiferromagnetic to weak‐ferromagnetic transition at spin‐reorientation temperature T_SR. The co‐presence of ferroelectric and antiferromagnetic orders confirms the present ceramics as promising room‐temperature multiferroic materials.     

Stereo-Active Lone Pairs Induced Giant Polarization in a 2D Ge-Based Halide Perovskite Antiferroelectric

Antiferroelectrics, characterized by electrically controlled antipolar-polar phase transformation, have attracted tremendous attention as a class of promising electroactive materials for assembling electronic devices. The emerging two-dimensional (2D) halide perovskites with superior compositional diversity offer an ideal platform for exploring electroactive materials, whereas lead-free antiferroelectric counterparts are still scarcely reported. Herein, for the first time, a new lead-free 2D germanium iodide perovskite antiferroelectric (i-BA)₂CsGe₂I₇ ( 1 , i-BA is iso-butylammonium) has been presented, which exhibits a high Curie temperature (T_c) up to 403 K. Remarkably, benefiting from the lone pair stereochemical activity in Ge²⁺ induced large structural distortion and Cs⁺ ion off-center displacement, 1 shows well-defined double P–E hysteresis loops in a wide temperature range with a giant maximum polarization up to 18.8 µC cm⁻², which achieves a new high record among molecular antiferroelectrics. Moreover, under a low external electric field of 22.5 kV cm⁻¹, the antipolar-polar phase transformation in 1 affords a recoverable energy storage density W_rec of 0.27 J cm⁻³ and high storage efficiency up to 79.76%. Such lead-free halide perovskite antiferroelectric with intriguing antiferroelectric behaviors, including high T_c, large polarization and remarkable energy storage properties, is exciting, which provides an alternative candidate for high-performance antiferroelectrics for environmentally friendly electronic devices.     

UV‐vis‐Induced Vitrification of a Molecular Crystal

A charge‐transfer complex of 2,5‐dimethyl‐N,N′‐dicyanoquinonediimine (DM) with silver (crystalline Ag(DM)₂, defined as α) is irreversibly transformed by UV‐vis illumination. Depending on the illumination conditions, three new types of solids (defined as γ, δ, and ?) with different structural and physical properties are obtained and examined by a variety of analytical techniques, including solid‐state, high‐resolution, cross‐polarization magic angle spinning (CP‐MAS) ¹³C NMR, elemental analysis (EA), mass spectrometry (MS), X‐ray absorption fine structure (XAFS), and powder X‐ray diffraction (XRD). The CP‐MAS, EA, MS, and XAFS results indicate that compound γ is a glass state of Ag(DM)₂. The transformation from crystalline (α) to amorphous (γ) solid Ag(DM)₂ is an irreversible exothermic glass transition (glass‐transition temperature 155.2 °C; ΔH = –126.8 kJ mol^–1), which implies that the glass form is thermodynamically more stable than the crystalline form. Compound δ (Ag(DM)_1.5) consists of silver nanoparticles (diameter (7 ± 2) nm ) dispersed in a glassy matrix of neutral DM molecules. The ?N–CN–Ag coordination bonds of the α form are not maintained in the δ form. Decomposition of α by intense illumination results in a white solid (?), identified as being composed of silver nanoparticles (diameter (60 ± 10) nm). Physical and spectroscopic (XAFS) measurements, together with XRD analysis, indicate that the silver nanoparticles in both δ and ? are crystalline with lattice parameters similar to bulk silver; however, the magnetic susceptibilities differ from bulk silver.     

Photoinduced Magnetization with a High Curie Temperature and a Large Coercive Field in a Co‐W Bimetallic Assembly

The crystal structure, magnetic properties, and temperature‐ and photoinduced phase transition of [{Co^II(4‐methylpyridine)(pyrimidine)}₂{Co^II(H₂O)₂}{W^V(CN)₈}₂]·4H₂O are described. In this compound, a temperature‐induced phase transition from the Co^II (S = 3/2)‐NC‐W^V(S = 1/2) [high‐temperature (HT)] phase to the Co^III(S = 0)‐NC‐W^IV(S = 0) [low temperature (LT)] phase is observed due to a charge‐transfer‐induced spin transition. When the LT phase is irradiated with 785 nm light, ferromagnetism with a high Curie temperature (T_C) of 48 K and a gigantic magnetic coercive field (H_c) of 27 000 Oe are observed. These T_C and H_c values are the highest in photoinduced magnetization systems. The LT phase is optically converted to the photoinduced phase, which has a similar valence state as the HT phase due to the optically induced charge‐transfer‐induced spin transition.     

Efficient Deep‐Blue Organic Light‐Emitting Diodes: Arylamine‐Substituted Oligofluorenes

Novel deep‐blue‐light‐emitting diphenylamino and triphenylamino end‐capped oligofluorenes were synthesized by double palladium‐catalyzed Suzuki cross‐coupling of dibromo‐oligofluorene with the corresponding boronic acid as a key step. These oligofluorenes exhibit deep‐blue emission (λ^em_max = 429–432 nm), low and reversible electrochemical oxidation (highest occupied molecular orbital = 5.15–5.20 eV), high fluorescence quantum yield (Φ_FL = 0.61–0.93), and good thermal properties (glass‐transition temperature, T_g = 99–195 °C and decomposition temperature, T_dec > 450 °C). Remarkably, saturated deep‐blue organic light‐emitting diodes, made from these oligofluorenes as dopant emitters, have been achieved with excellent performance and maximum efficiencies up to 2.9 cd A^–1 at 2 mA cm^–2 (external quantum efficiency of 4.1 %) and with Commission Internationale de l'Éclairage (x,y) coordinates of (0.152,0.08), which is very close to the National Television System Committee standard blue.     

Optoelectronic Properties of Quasi‐Linear,Self‐Assembled Platinum Complexes: Pt–Pt Distance Dependence

Charge‐carrier mobilities of various self‐assembled platinum complexes were measured by time‐resolved microwave conductivity techniques in the temperature range –80 to +100 °C. Eight compounds were investigated in the present study, including the original Magnus' green salt ([Pt(NH₃)₄][PtCl₄]) and derivatives with the general structure [Pt(NH₂R)₄][PtCl₄], where R denotes an alkyl side chain. In one instance, the chlorines were substituted with bromines. For these complexes, which all consist of a linear backbone of platinum atoms with Pt–Pt distances, d, varying from 3.1 to ≥ 3.6 Å, a strong, inverse correlation was found between d and the one‐dimensional charge‐carrier mobility, Σμ_1D. The highest value of Σμ_1D at room temperature was observed for R = (S)‐3,7‐dimethyloctyl (dmoc) with Σμ_1D ≥ 0.06 cm² V^–1 s^–1. Almost all materials exhibited a charge‐carrier mobility that was relatively independent of the temperature over the range studied. One exceptional compound (R = (R)‐2‐ethylhexyl) showed a pronounced negative temperature dependence of the charge‐carrier mobility; upon decreasing the temperature from +100 °C to –80 °C the charge‐carrier mobility increased by a factor of about ten.     

Layer‐Structured Photoconducting Polymers: A New Class of Photorefractive Materials

We study the photorefractive (PR) properties of a new kind of low glass‐transition temperature (T_g) polymer composite based on layered photoconductive polymers, poly(p‐phenylene terephthalate) carbazoles (PPT‐CZs). These photoconductors consist of the rigid backbone of PPT with pendant oxyalkyl CZ groups. The compounds are doped with the photosensitizer C₆₀ and nonlinear optical chromophores diethylaminodicyanostyrene (DDCST), and no plasticizers are added. When the host polymers are mixed with various PR ingredients, the layers are preserved and their layer distance increases, indicating that all the guest molecules are confined to the nanoscale interlayer space. These composites showed very low T_g values (< ? °C). Despite the absence of a plasticizer and the lower concentration of the carbazole photoconductive moieties as compared to poly(N‐vinylcarbazole) systems, these materials show excellent PR properties, i.e., a PR gain of Γ = 250 cm^–1 under an external electric field of 60 V μm^–1, and diffraction efficiency and PR sensitivity of 93 % and 24 ± 7 cm² kJ^–1 at E = 100 V μm^–1, respectively.     

Effect of pulsed laser irradiation on the optical characteristics and photoconductivity of the solid solutions CdHgTe

The melting threshold of Cd_0.2Hg_0.8Te has been determined by numerical modeling of the irradiation of the material with nanosecond ruby-laser radiation pulses: W _n =40–50 mJ/cm² with initial crystal temperature T ₀=100 K and W _m =30–40 mJ/cm² at T ₀=300 K. Laserinduced modification of the surface of the sample under irradiation with energy density W<W _m was found; it was manifested as a quenching of the stationary photoconductivity and an increase in the reflection coefficient. For laser irradiation with W above the melting threshold, the reflection coefficient increases further in the region up to W≳100 mJ/cm² and decreases for W>110 mJ/cm². For above-threshold irradiation, the photoconductivity signal was found to decrease monotonically with increasing energy density in the laser pulse; this can be explained by defect formation caused by laser-induced variation of the composition in the surface region. Fiz. Tekh. Poluprovodn. 31, 931–935 (August 1997)     

Ag‐Functionalized Carbon Molecular‐Sieve Membranes Based on Polyelectrolyte/Polyimide Blend Precursors

We prepared dense flat‐sheet Ag‐functionalized carbon molecular‐sieve (CMS) membranes from blends of P84 co‐polyimide and a sulfonated poly(ether ether ketone) with a Ag⁺ counterion (AgSPEEK). These blends offer the possibility of producing new functionalized precursor structures, which were previously not possible, such as integrally skinned asymmetric hollow fibers. Membranes prepared at a pyrolysis end temperature of 800 °C showed a maximum permeability for all tested gases at a Ag content of approximately 2.5 wt.‐% (He permeability P_He = 465 Barrer (1 Barrer = 7.5 × 10^–18 m² s^–1 Pa^–1), Pequation/tex2gif-inf-2.gif = 366 Barrer, Pequation/tex2gif-inf-4.gif = 91.8 Barrer, Pequation/tex2gif-inf-6.gif = 10.3 Barrer). The maximum achieved selectivity for O₂ over N₂ with CMS membranes based on these blends was αequation/tex2gif-inf-10.gif = 13.5 (Ag content: 4.5 wt.‐%, Pequation/tex2gif-inf-14.gif = 52.7 Barrer). The CO₂ over N₂ selectivity reached a value of 48.9 (Ag content: 4.5 wt.‐%, Pequation/tex2gif-inf-18.gif = 191 Barrer). These observations are explained by the formation of selective bypasses around Ag nanoclusters in the CMS matrix.     

Fabrication of Large‐Scale Single‐Crystalline PrB6 Nanorods and Their Temperature‐Dependent Electron Field Emission

A simple catalysis‐free approach that utilises a gas–solid reaction for the synthesis of large‐scale single‐crystalline PrB₆ nanorods using Pr and BCl₃ as starting materials is demonstrated. The nanorods exhibit a low turn‐on electric field (2.80 V µ‐b;m^?1 at 10 µ‐b;A cm^?2), a low threshold electric field (6.99 V µ‐b;m^?1 at 1 mA cm^?2), and a high current density (1.2 mA cm^?2 at 7.35 V µ‐b;m^?1) at room temperature (RT). The turn‐on and threshold electric field are found to decrease clearly from 2.80 to 0.95 and 6.99 to 3.55 V µ‐b;m^?1, respectively, while the emission current density increases significantly from 1.2 to 13.8 mA cm^?2 (at 7.35 V µ‐b;m^?1) with an increase in the ambient temperature from RT to 623 K. The field enhancement factor, emission current density, and the dependence of the effective work function with temperature are investigated. The possible mechanism of the temperature‐dependent emission from PrB₆ nanorods is discussed.     

[Cp*W(dmit)2]•: An Organometallic 15‐Electron Neutral Radical (d1) with Optical Limiting Properties in Solution and an Antiferromagnetic Ground State in the Solid State

The synthesis of the organometallic d² [Cp*W(dmit)₂]^1– complex (where Cp* is pentamethylcyclopentadienyl and dmit is 1,3‐dithiole‐2‐thione‐4,5‐dithiolate), and its oxidation to the paramagnetic d¹ [Cp*W(dmit)₂]^• species, is described and their X‐ray crystal structures given. Geometrical evolutions upon oxidation, characterized by a variable folding of the WS₂C₂ metallacycles along the S–S hinge, are rationalized by density functional theory (DFT) calculations and by comparison with the molybdenum analogs; as is also the evolution in the UV‐vis‐NIR absorption spectra. In solution, only the d¹ complexes exhibit positive optical density variations in transitory nanosecond spectroscopy after 10 ns laser pulses. A weak optical limiting effect was observed on these d¹ species, stronger in the W than in the Mo complex. In the solid state, the interacting, paramagnetic [Cp*W(dmit)₂]^• species (θ_{Curie–Weiss} = –20 K) orders antiferromagnetically below T_Néel = 4.5 K with a spin‐flop field, B_SF(W) of 8000 G. Compared with the molybdenum analog, the weaker θ_{Curie–Weiss}(W) and T_Néel(W) values, and larger B_SF(W) values reflect weaker intermolecular interactions due to a decreased spin density on the dithiolene ligands and stronger spin–orbit coupling with the W atom, as confirmed by DFT calculations on the d² and d¹ Mo and W complexes.     

Nonlinear Absorption Applications of CH3NH3PbBr3 Perovskite Crystals

Researchers have recently revealed that hybrid lead halide perovskites exhibit ferroelectricity, which is often associated with other physical characteristics, such as a large nonlinear optical response. In this work, the nonlinear optical properties of single crystal inorganic–organic hybrid perovskite CH₃NH₃PbBr₃ are studied. By exciting the material with a 1044 nm laser, strong two‐photon absorption‐induced photoluminescence in the green spectral region is observed. Using the transmission open‐aperture Z‐scan technique, the values of the two‐photon absorption coefficient are observed to be 8.5 cm GW^?1, which is much higher than that of standard two‐photon absorbing materials that are industrially used in nonlinear optical applications, such as lithium niobate (LiNbO₃), LiTaO₃, KTiOPO₄, and KH₂PO₄. Such a strong two‐photon absorption effect in CH₃NH₃PbBr₃ can be used to modulate the spectral and spatial profiles of laser pulses, as well as to reduce noise, and can be used to strongly control the intensity of incident light. In this study, the superior optical limiting, pulse reshaping, and stabilization properties of CH₃NH₃PbBr₃ are demonstrated, opening new applications for perovskites in nonlinear optics.     

Red Phosphorescent Iridium Complex Containing Carbazole‐Functionalized β‐Diketonate for Highly Efficient Nondoped Organic Light‐Emitting Diodes

A novel red phosphorescent iridium complex containing a carbazole‐functionalized β‐diketonate, Ir(DBQ)₂(CBDK) (bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(carbazol‐9‐yl)‐5,5‐dimethylhexane‐2,4‐diketonate)) is designed, synthesized, and characterized. The electrophosphorescence properties of a nondoped device using the title complex as an emitter with a device configuration of indium tin oxide (ITO)/N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)‐1,1′‐diphenyl‐4,4′‐diamine (NPB; 20 nm)/iridium complex (20 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 5 nm)/tris(8‐hydroxyquinoline) (AlQ; 30 nm)/Mg_0.9Ag_0.1 (200 nm)/Ag (80 nm) are examined. The results show that the nondoped device achieves a maximum lumen efficiency as high as 3.49 lm W^–1. To understand this excellent result observed, two reference complexes Ir(DBQ)₂(acac), where acac is the acetyl acetonate anion, and Ir(DBQ)₂(FBDK), [bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(9‐methyl‐fluoren‐9‐yl)‐6,6‐dimethylheptane‐3,5‐diketonate)], have also been synthesized, and as emitters they were examined under the same device configuration. The maximum lumen efficiency of the former compound is found to be 0.26 lm W^–1 while that for the latter is 0.37 lm W^–1, suggesting that the excellent performance of Ir(DBQ)₂(CBDK) can be attributed mainly to an improved hole‐transporting property that benefits the exciton transport. In addition, a bulky diketonate group separates the emitter centers from each other, which is also important for organic light‐emitting diodes.     

Diphenylamine‐Substituted Cruciform Oligo(phenylene vinylene): Enhanced One‐ and Two‐Photon Excited Fluorescence in the Solid State

1,4‐di(4′‐N,N‐diphenylaminostyryl)benzene (DPA‐DSB) is a well known compound with a large two‐photon absorption (TPA) section and strong fluorescence in solution. However, the ease with which it crystallizes results in the formation of discontinuous crystalline phases during vacuum deposition processes, thereby greatly limiting its applicability in solid‐state devices. A cruciform dimer of DPA‐DSB, 2,5,2′,5′‐tetra(4′‐N,N‐diphenylaminostyryl)biphenyl (DPA‐TSB) is reported, wherein two DPA‐DSB molecules are linked through a central biphenyl bond. The DPA‐TSB molecules take on a cruciform configuration because of the steric crowding around the central biphenyl core, which has the effect of efficiently suppressing crystalline and intermolecular interactions. The neat DPA‐TSB solid shows strong green–blue fluorescence because of both steady‐state absorption as well as TPA. The DPA‐TSB solid exhibits a photoluminescence (PL) efficiency (η_solid) of 29 % and a solid‐state two‐photon action cross section (δη_solid) of 954 GM (1 GM = 1 × 10^–50 cm⁴ s photon^–1 molecule^–1), which is much greater than for the model compound DPA‐DSB (η_solid = 16 % and δη_solid = 150 GM, where δ is the TPA cross section and η is the fluorescence quantum yield). Based on its high PL efficiency, good film‐forming ability, and strong TPA, DPA‐TSB seems to be a good candidate for applications in solid‐state optical devices.     

Monolayer WxMo1−xS2 Grown by Atmospheric Pressure Chemical Vapor Deposition: Bandgap Engineering and Field Effect Transistors

Monolayer W_x Mo_1?x S₂‐based field effect transistors are demonstrated for the first time on the monolayer W_x Mo_1?x S₂ flake, which is grown by the chemical vapor deposition method under an atmospheric pressure. Detailed material studies using Raman and photoluminescence measurements have been carried out on the as‐grown monolayer W_x Mo_1?x S₂. Electronic band structure of monolayer W_x Mo_1?x S₂ has been calculated using first‐principle theory. The thermal stability of monolayer W_x Mo_1?x S₂ has been evaluated using Raman‐temperature measurement. Carrier transport study on the fabricated W_x Mo_1?x S₂ FETs has been analyzed using temperature‐dependent current measurement, and a field effect mobility of ≈30 cm² V^?1 s^?1 at 300 K is obtained.     

Impact of Morphology on Charge Carrier Transport and Thermoelectric Properties of N‐Type FBDOPV‐Based Polymers

The impact of the chemical structure and molecular order on the charge transport properties of two donor–acceptor copolymers in their neutral and doped states is investigated. Both polymers comprise 3,7‐bis((E)‐7‐fluoro‐1‐(2‐octyl‐dodecyl)‐2‐oxoindolin‐3‐ylidene)‐3,7‐dihydrobenzo[1,2‐b:4,5‐b′]difuran‐2,6‐dione (FBDOPV) as electron‐accepting unit, copolymerized with 9,9‐dioctyl‐fluorene (P(FBDOPV‐F)) or with 3‐dodecyl‐2,2′‐bithiophene (P(FBDOPV‐2T‐C₁₂)). These copolymers possess an amorphous and semi‐crystalline nature, respectively, and exhibit remarkable electron mobilities of 0.065 and 0.25 cm² V^–1 s^–1 in field effect transistors. However, after chemical n‐doping with 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)phenyl)dimethylamine (N‐DMBI), electrical conductivities four orders of magnitude higher can be achieved for P(FBDOPV‐2T‐C₁₂) (σ = 0.042 S cm^?1). More charge‐transfer complexes are formed between P(FBDOPV‐F) and N‐DMBI, but the highly localized polaronic states poorly contribute to the charge transport. Doped P(FBDOPV‐2T‐C₁₂) exhibits a negative Seebeck coefficient of –265 µV K^?1 and a thermoelectric power factor (PF) of 0.30 µW m^?1 K^?2 at 303 K which increases to 0.72 µW m^?1 K^?2 at 388 K. The in‐plane thermal conductivity (κ_|| = 0.53 W m^?1 K^?1) on the same micrometer‐thick solution‐processed film is measured, resulting in a figure of merit (ZT) of 5.0 × 10^?4 at 388 K. The results provide important design guidelines to improve the doping efficiency and thermoelectric properties of n‐type organic semiconductors.