Poly(arylene piperidinium) Hydroxide Ion Exchange Membranes: Synthesis,Alkaline Stability,and Conductivity

A series of poly(arylene piperidinium)s (PAPipQs) devoid of any alkali‐sensitive aryl ether bonds or benzylic sites are prepared and studied as anion exchange membranes (AEMs) for alkaline fuel cells. First, the excellent alkaline stability of the model compound 4,4‐diarylpiperidinium is confirmed. Medium molecular weight poly(arylene piperidine)s are then synthesized in polycondensations of N‐methyl‐4‐piperidone and either bi‐ or terphenyl via superelectrophilic activation in triflic acid. Film‐forming PAPipQs are subsequently prepared in Menshutkin reactions with methyl, butyl, hexyl, and octyl halides, respectively. AEMs based on poly(terphenyl dimethylpiperidinium) show the best performance with no structural degradation detectable by ¹H NMR spectroscopy after storage in 2 m aq. NaOH at 60 °C after 15 d, and a mere 5% ionic loss at 90 °C. In the fully hydrated state these AEMs reach an OH^? conductivity of 89 mS cm^?1 at 80 °C. The presence of longer pendant N‐alkyl chains (butyl to octyl) is found to significantly promote Hofmann ring‐opening elimination reactions and the degradation rate increases with increasing alkyl chain length. The results of the present study demonstrate that PAPipQs are efficiently prepared from readily available monomers and show excellent alkaline stability and OH^? conductivity when devoid of pendant N‐alkyl chains.     

A Quantum‐Chemical Study on Understanding the Dehydrogenation Mechanisms of Metal (Na,K, or Mg) Cation Substitution in Lithium Amide Nanoclusters

The hydrogen‐releasing activity of (LiNH₂)₆–LiH nanoclusters and metal (Na, K, or Mg)‐cation substituted nanoclusters (denoted as (NaNH₂)(LiNH₂)₅, (KNH₂)(LiNH₂)₅, and (MgNH)(LiNH₂)₅) are studied using ab initio molecular orbital theory. Kinetics results show that the rate‐determining step for the dehydrogenation of the (LiNH₂)₆–LiH nanocluster is the ammonia liberation from the amide with a high activation energy of 167.0 kJ mol^?1 (at B3LYP/6‐31 + G(d,p) level). However, metal (Na, K, Mg)‐cation substitution in amide–hydride nanosystems reduces the activation energies for the rate‐determining step to 156.8, 149.6, and 144.1 kJ mol^?1 (at B3LYP/6‐31 + G(d,p) level) for (NaNH₂)(LiNH₂)₅, (KNH₂)(LiNH₂)₅, and (MgNH)(LiNH₂)₅, respectively. Furthermore, only the ?NH₂ group bound to the Na/K cation is destabilized after Na/K cation substitution, indicating that the improving effect from Na/K‐cation substitution is due to a short‐range interaction. On the other hand, Mg‐cation substitution affects all –NH₂ groups in the nanocluster, resulting in weakened N–H covalent bonding together with stronger ionic interactions between Li and the –NH₂ group. The present results shed light on the dehydrogenation mechanisms of metal‐cation substitution in lithium amide–hydride nanoclusters and the application of (MgNH)(LiNH₂)₅ nanoclusters as promising hydrogen‐storage media.     

Li+附着CH3-nFnO2过氧自由基:络合物Li+-CH3-nFnO2(n=0～3)结构与性质的研究

采用了从头算分子轨道理论（MP2,非限性的二级微扰理论）和密度泛涵理论（B3LYP）,分别在6-31G（d,p）,6-311G（d,p）,6-311＋G（d,p）,6-311G（2d,p）,和6-311＋G（2df,2p）基组上优化CH3-nFnO2-Li^＋（n=0～3）的几何结构,计算出了相关的NBO电荷分布和锂离子相对于自由基CH3-nFnO2的亲和能。并在同一水平上计算了自由基CH3-nFnO2和络合物CH3-nFnO2-Li^＋的相关伸缩振动频率。CH3-nFnO2在UB3LYP／6-311G（d,P）得到的振动频率与实验值符合得很好．根据相关的文献报道,我们运用从头算分子轨道理论和密度泛涵理论计算出的锂离子相对于CH3-nFnO2的亲和能都能够表明络合物CH3-nFnO2-Li^＋在气态下能以一种稳定的物种形态被离子附着质谱检测．     

Conformation Locking on Fused‐Ring Electron Acceptor for High‐Performance Nonfullerene Organic Solar Cells

In this work, sidechain engineering on conjugated fused‐ring acceptors for conformation locking is demonstrated as an effective molecular design strategy for high‐performance nonfullerene organic solar cells (OSCs). A novel nonfullerene acceptor (ITC6‐IC) is designed and developed by introducing long alkyl chains into the terminal electron‐donating building blocks. ITC6‐IC has achieved definite conformation with a planar structure and better solubility in common organic solvents. The weak electron‐donating hexyl upshifts the lowest unoccupied molecular orbital level of ITC6‐IC, resulting in a higher V_OC in comparison to the widely used ITIC. The OSCs based on PBDB‐T:ITC6‐IC reveal a promising power conversion efficiency of 11.61% and an expected high V_OC of 0.97 V. The weaker π–π stacking induced by steric hindrance affords ITC6‐IC with enhanced compatibility with polymer donors. The blend film treated with suitable thermal annealing exhibits a fibril crystallization feature with a good bicontinuous network morphology. The results indicate that the molecular design approach of ITC6‐IC can be inspirational for future development of nonfullerene acceptors for high efficiency OSCs.     

N‐Doped CsTaWO6 as a New Photocatalyst for Hydrogen Production from Water Splitting Under Solar Irradiation

Photocatalysts for efficient solar hydrogen production are highly sought after. Here a new type of nitrogen‐doped tantalum tungstenate (CsTaWO₆) material, which demonstrates excellent visible light absorption and improved photocatalytic activity, is demonstrated. X‐ray diffraction (XRD) patterns reveal that the defect pyrochlore‐type structure of CsTaWO₆ remained intact upon nitrogen doping. UV‐vis spectra indicate that nitrogen doping in the compound results in a red‐shift of the absorption edge from 358 nm to 580 nm, thus offering significantly increased visible light absorption. X‐ray photoelectron spectroscopy (XPS) further indicates that [Ta/W]–N bonds were formed by inducing nitrogen to replace a small amount of oxygen in the material, resulting in a compound of CsTaWO_6‐xN_x. The explanation of the experimental results is supported by density functional theory calculations. The density of states (DOS) and the projected DOS after substitutional doping of nitrogen in CsTaWO₆ indicated that N‐doping reduces the bandgap significantly from 3.8 to 2.3 eV due to N 2p and O 2p orbital mixing. The role of the new N 2p states is also investigated by studying the production of the ?OH radicals in the visible light region (>420 nm). In CsTaWO_6‐xN_x, the N 2p orbitals are the main contributors to the top of the valence band, causing bandgap narrowing while the bottom of conduction band, due to Ta 4d orbitals, remains almost unchanged. Compared with its undoped counterpart, nitrogen‐doped CsTaWO_6‐xN_x exhibits a nearly 100% increase in solar hydrogen production efficiency.     

Doping Molecular Monolayers: Effects on Electrical Transport Through Alkyl Chains on Silicon

n‐Si/C_nH_{2n + 1}/Hg junctions (n = 12, 14, 16 and 18) can be prepared with sufficient quality to assure that the transport characteristics are not anymore dominated by defects in the molecular monolayers. With such organic monolayers we can, using electron, UV and X‐ray irradiation, alter the charge transport through the molecular junctions on n‐ as well as on p‐type Si. Remarkably, the quality of the self‐assembled molecular monolayers following irradiation remains sufficiently high to provide the same very good protection of Si from oxidation in ambient atmosphere as provided by the pristine films. Combining spectroscopic (UV photoemission spectroscopy (UPS), X‐ray photoelectron spectroscopy (XPS), Auger, near edge‐X‐ray absorption fine structure (NEXAFS)) and electrical transport measurements, we show that irradiation induces defects in the alkyl films, most likely C?C bonds and C? C crosslinks, and that the density of defects can be controlled by irradiation dose. These altered intra‐ and intermolecular bonds introduce new electronic states in the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the alkyl chains and, in the process, dope the organic film. We demonstrate an enhancement of 1–2 orders of magnitude in current. This change is clearly distinguishable from the previous observed difference between transport through high quality and defective monolayers. A detailed analysis of the electrical transport at different temperatures shows that the dopants modify the transport mechanism from tunnelling to hopping. This study suggests a way to extend significantly the use of monolayers in molecular electronics.     

From Bonding Asymmetry to Anharmonic Rattling in Cu12Sb4S13 Tetrahedrites: When Lone‐Pair Electrons Are Not So Lonely

Some of the best thermoelectrics are complex materials with rattling guests inside oversized atomic cages. Understanding the chemical and structural origins of the rattling behavior is essential to the design of thermoelectric materials. In this work, a clear connection is established between the local bonding asymmetry and anharmonic rattling modes in tetrahedrite thermoelectrics, enabled by the chemically active electron lone pairs. The studies reveal a five‐atom atomic cage Sb[CuS₃]Sb in Cu₁₂Sb₄S₁₃ tetrahedrites that exhibits strong local bonding asymmetry: covalent bonding inside the CuS₃ trigonal plane and weak out‐of‐plane bonding induced by the lone‐pair electrons of Sb. This bonding asymmetry leads to out‐of‐plane rattling modes that are quasilocalized and anharmonic with low frequency and large amplitude, and are likely the origin of low thermal conductivity in tetrahedrites. Such knowledge highlights the importance of local structure asymmetry and lone‐pair atoms in driving anharmonic rattling, providing a stepping stone to the discovery and design of next‐generation thermoelectrics.     

Synthesis,Characterization, and Application of Mesoporous Silica Functionalized with Alkyl‐Hydroperoxides

A variety of alkyl hydroperoxides such as tert‐butyl‐, tert‐octyl‐, 1‐cyclopentyl‐, 1‐cyclohexyl‐, 3,4‐disubstituted‐1‐cyclohexyl‐, n‐propyl, and n‐undecyl‐hydroperoxides have been functionalized onto ordered mesoporous silica, SBA‐15, from the corresponding covalently anchored synthons. All the tert‐hydroperoxides are prepared by autoxidation using molecular O₂ and an initiator, whereas other hydroperoxides are obtained by reaction with H₂O₂. For autoxidation, the use of a combination of an azoinitiator (AIBN) and N‐hydroxyphthalimide increased the hydroperoxide yield compared with using the azoinitiator alone. Synthons containing two or more tert‐ and sec‐hydrogens lead to higher peroxide yield compared to synthons with a single reactive site. Oxidation of Si–OH (silanol groups) with acidic H₂O₂ at low temperature produces Si–OOH. Reusability of these alkyl hydroperoxides is carried out by oxidation of alcohols obtained from the corresponding alkyl hydroperoxides using H₂O₂. Both the covalently anchored synthons and the resulting hydroperoxides are thoroughly characterized by powder X‐ray diffraction, ¹³C cross‐polarized magic angle spinning NMR, TG/DTA, Fourier transform IR spectroscopy, sorption, and surface area measurements. The quantification of the amount of alkyl hydroperoxide was carried out by iodometric titration using a thio solution. The hydroperoxides exhibit high activity for the epoxidation of styrene to styrene oxide and exhibit reasonably high efficiency for oxygen transfer.     

氯溴双卤代烷烃分子构型和光谱对烷基链长依赖关系的研究

氯溴双卤代烷烃在太阳紫外光辐射下解离生成游离态的氯和溴自由基,它们是破坏臭氧的主要元凶之一。利用B3LYP/6-311++G(d,p)方法对氯溴双卤代烷烃分子CnH2nBrCl(n=1~16)进行分子构型优化以及红外光谱的计算。根据数据进行分析比较,得到了氯溴双卤代烷烃C-Br键和C-Cl键的键长、键角等构型参数随烷基支链长度增加(n为1~16)的变化趋势图。研究讨论了氯溴双卤代烷烃的红外光谱相关振动随烷基支链长度增加的重要变化规律。     

Thieno[3,2‐b]thiophene Flanked Isoindigo Polymers for High Performance Ambipolar OFET Applications

The synthesis of a new thieno[3,2‐b]thiophene isoindigo (iITT) based monomer unit, and its subsequent incorporation into a series of alternating copolymers is reported. Copolymerisation with benzothiadiazole, bithiophene and thiophene comonomer units by palladium catalysed cross coupling gives three new narrow band gap semiconducting polymers for OFET applications. Extending the fused nature of the isoindigo core serves to further enhance molecular orbital overlap along the polymer backbones and facilitate good charge transport characteristics thus demonstrating the potential of extending the fused ring system that is attached to the isoindigo core. When used as the semiconducting channel in top‐gate/bottom‐contact OFET devices, good ambipolar properties are observed, with hole and electron mobilities up to 0.4 cm²/Vs and 0.7 cm²/Vs respectively. The three new polymers show good stability, with high temperature annealing showing an increase in the crystallinity of the polymers which corresponds directly to charge carrier mobility improvement as shown by X‐ray diffraction, atomic force microscopy and photothermal deflection spectroscopy.     

Passivation of Molecular n‐Doping: Exploring the Limits of Air Stability

Molecular doping is a key technique for flexible and low‐cost organic complementary semiconductor technologies that requires both efficient and stable p‐ and n‐type doping. However, in contrast to molecular p‐dopants, highly efficient n‐type dopants are commonly sensitive to rapid degradation in air due to their low ionization energies (IEs) required for electron donation, e.g., IE = 2.4 eV for tetrakis(1,3,4,6,7,8‐hexahydro‐2H‐pyrimido[1,2‐a]pyrimidinato)ditungsten(II) (W₂(hpp)₄). Here, the air stability of various host:W₂(hpp)₄ combinations is compared by conductivity measurements and photoemission spectroscopy. A partial passivation of the n‐doping against degradation is found, with this effect identified to depend on the specific energy levels of the host material. Since host‐W₂(hpp)₄ electronic wavefunction hybridization is unlikely due to confinement of the dopant highest occupied molecular orbital (HOMO) to its molecular center, this finding is explained via stabilization of the dopant by single‐electron transfer to a host material whose energy levels are sufficiently low for avoiding further charge transfer to oxygen–water complexes. Our results show the feasibility of temporarily handling n‐doped organic thin films in air, e.g., during structuring of organic field effect transistors (OFETs) by lithography.     

Structure–Property Relationship of Pyridine‐Containing Triphenyl Benzene Electron‐Transport Materials for Highly Efficient Blue Phosphorescent OLEDs

Three triphenyl benzene derivatives of 1,3,5‐tri(m‐pyrid‐2‐yl‐phenyl)benzene (Tm2PyPB), 1,3,5‐tri(m‐pyrid‐3‐yl‐phenyl)benzene (Tm3PyPB) and 1,3,5‐tri(m‐pyrid‐4‐yl‐phenyl)benzene (Tm4PyPB), containing pyridine rings at the periphery, are developed as electron‐transport and hole/exciton‐blocking materials for iridium(III) bis(4,6‐(di‐fluorophenyl)pyridinato‐N,C^2′)picolinate (FIrpic)‐based blue phosphorescent organic light‐emitting devices. Their highest occupied molecular orbital and lowest unoccupied molecular orbital (LUMO) energy levels decrease as the nitrogen atom of the pyridine ring moves from position 2 to 3 and 4; this is supported by both experimental results and density functional theory calculations, and gives improved electron‐injection and hole‐blocking properties. They exhibit a high electron mobility of 10^?4–10^?3 cm² V^?1 s^?1 and a high triplet energy level of 2.75 eV. Confinement of FIrpic triplet excitons is strongly dependent on the nitrogen atom position of the pyridine ring. The second exponential decay component in the transient photoluminescence decays of Firpic‐doped films also decreases when the position of the nitrogen atom in the pyridine ring changes. Reduced driving voltages are obtained when the nitrogen atom position changes because of improved electron injection as a result of the reduced LUMO level, but a better carrier balance is achieved for the Tm3PyPB‐based device. An external quantum efficiency (EQE) over 93% of maximum EQE was achieved for the Tm4PyPB‐based device at an illumination‐relevant luminance of 1000 cd m^?2, indicating reduced efficiency roll‐off due to better confinement of FIrpic triplet excitons by Tm4PyPB in contrast to Tm2PyPB and Tm3PyPB.     

Investigation of the High Electron Affinity Molecular Dopant F6‐TCNNQ for Hole‐Transport Materials

2,2′‐(perfluoronaphthalene‐2,6‐diylidene)dimalononitrile (F6‐TCNNQ) is investigated as a molecular p‐type dopant in two hole‐transport materials, 2,2′,7,7′‐tetrakis(N,N‐diphenylamino)‐9,9‐spirobifluorene (Spiro‐TAD) and tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA). The electron affinity of F6‐TCNNQ is determined to be 5.60 eV, one of the strongest organic molecular oxidizing agents used to date in organic electronics. p‐Doping is found to be effective in Spiro‐TAD (ionization energy = 5.46 eV) but not in TCTA (ionization energy = 5.85 eV). Optical absorption measurements demonstrate that charge transfer is the predominant doping mechanism in Spiro‐TAD:F6‐TCNNQ. The host–dopant interaction also leads to a significant alteration of the host film morphology. Finally, transport measurements done on Spiro‐TAD:F6‐TCNNQ as a function of dopant concentration and temperature, and using a highly doped contact layer to ensure negligible hole injection barrier, lead to an accurate measurement of the film conductivity and hole‐hopping activation energy.     

Lone‐Pair‐Induced Covalency as the Cause of Temperature‐ and Field‐Induced Instabilities in Bismuth Sodium Titanate

Bismuth sodium titanate (BNT)‐derived materials have seen a flurry of research interest in recent years because of the existence of extended strain under applied electric fields, surpassing that of lead zirconate titanate (PZT), the most commonly used piezoelectric. The underlying physical and chemical mechanisms responsible for such extraordinary strain levels in BNT are still poorly understood, as is the nature of the successive phase transitions. A comprehensive explanation is proposed here, combining the short‐range chemical and structural sensitivity of in situ Raman spectroscopy (under an applied electric field and temperature) with macroscopic electrical measurements. The results presented clarify the causes for the extended strain, as well as the peculiar temperature‐dependent properties encountered in this system. The underlying cause is determined to be mediated by the complex‐like bonding of the octahedra at the center of the perovskite: a loss of hybridization of the 6s² bismuth lone pair interacting with the oxygen p‐orbitals occurs, which triggers both the field‐induced phase transition and the loss of macroscopic ferroelectric order at the depolarization temperature.     

Alternating Copolymers of Cyclopenta[2,1‐b;3,4‐b′]dithiophene and Thieno[3,4‐c]pyrrole‐4,6‐dione for High‐Performance Polymer Solar Cells

A series of alternating copolymers of cyclopenta[2,1‐b;3,4‐b′]dithiophene (CPDT) and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) have been prepared and characterized for polymer solar cell (PSC) applications. Different alkyl side chains, including butyl (Bu), hexyl (He), octyl (Oc), and 2‐ethylhexyl (EH), are introduced to the TPD unit in order to adjust the packing of the polymer chain in the solid state, while the hexyl side chain on the CPDT unit remains unchanged to simplify discussion. The polymers in this series have a simple main chain structure and can be synthesized easily, have a narrow band gap and a broad light absorption. The different alkyl chains on the TPD unit not only significantly influence the solubility and chain packing, but also fine tune the energy levels of the polymers. The polymers with Oc or EH group have lower HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy levels, resulting higher open circuit voltages (V_oc) of the PSC devices. Power conversion efficiencies (PCEs) up to 5.5% and 6.4% are obtained from the devices of the Oc substituted polymer (PCPDTTPD‐Oc) with PC₆₁BM and PC₇₁BM, respectively. This side chain effect on the PSC performance is related to the formation of a fine bulk heterojunction structure of polymer and PCBM domains, as observed with atomic force microscopy.     

Quasi‐One Dimensional in‐Plane Conductivity in Filamentary Films of PEDOT:PSS

The mechanism and magnitude of the in‐plane conductivity of poly(3,4‐ethy‐lenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films is determined using temperature dependent conductivity measurements for various PEDOT:PSS weight ratios with and without a high boiling solvent (HBS). Without the HBS the in‐plane conductivity of PEDOT:PSS is lower and for all studied weight ratios well described by the relation $ \sigma = \sigma _0 {\rm exp}[- \left({{{{T_0}}\over{T}}} \right)^{0.5}] $ with T₀ a characteristic temperature. The exponent 0.5 indicates quasi‐one dimensional (quasi‐1D) variable range hopping (VRH). The conductivity prefactor σ₀ varies over three orders of magnitudes and follows a power law σ₀∝c^3.5_PEDOT with c_PEDOT the weight fraction of PEDOT in PEDOT:PSS. The field dependent conductivity is consistent with quasi‐1D VRH. Combined, these observations suggest that conductance takes place via a percolating network of quasi‐1D filaments. Using transmission electron microscopy (TEM) filamentary structures are observed in vitrified dispersions and dried films. For PEDOT:PSS films with HBS, the conductivity also exhibits quasi‐1D VRH behavior when the temperature is less than 200 K. The low characteristic temperature T₀ indicates that HBS‐treated films are close to the critical regime between a metal and an insulator. In this case, the conductivity prefactor scales linearly with c_PEDOT, indicating the conduction is no longer limited by a percolation of filaments. The lack of observable changes in TEM upon processing with the HBS suggests that the changes in conductivity are due to a smaller spread in the conductivities of individual filaments, or a higher probability for neighboring filaments to be connected rather than being caused by major morphological modification of the material.     

n‐Doping of a Low‐Electron‐Affinity Polymer Used as an Electron‐Transport Layer in Organic Light‐Emitting Diodes

n‐Doping electron‐transport layers (ETLs) increases their conductivity and improves electron injection into organic light‐emitting diodes (OLEDs). Because of the low electron affinity and large bandgaps of ETLs used in green and blue OLEDs, n‐doping has been notoriously more difficult for these materials. In this work, n‐doping of the polymer poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)] (F8BT) is demonstrated via solution processing, using the air‐stable n‐dopant (pentamethylcyclopentadienyl)(1,3,5‐trimethylbenzene)ruthenium dimer [RuCp*Mes]₂. Undoped and doped F8BT films are characterized using ultraviolet and inverse photoelectron spectroscopy. The ionization energy and electron affinity of the undoped F8BT are found to be 5.8 and 2.8 eV, respectively. Upon doping F8BT with [RuCp*Mes]₂, the Fermi level shifts to within 0.25 eV of the F8BT lowest unoccupied molecular orbital, which is indicative of n‐doping. Conductivity measurements reveal a four orders of magnitude increase in the conductivity upon doping and irradiation with ultraviolet light. The [RuCp*Mes]₂‐doped F8BT films are incorporated as an ETL into phosphorescent green OLEDs, and the luminance is improved by three orders of magnitude when compared to identical devices with an undoped F8BT ETL.     

Ambient‐Stable,Annealing‐Free,and Ambipolar Organic Field‐Effect Transistors Based on Solution‐Processable Poly(2,2′‐bis(trifluoromethyl)biphenyl‐alt‐2,5‐divinylthiophene) without Long Alkyl Side Chains

An ambipolar conjugated polymer CF₃‐PBTV, poly(2,2′‐bis(trifluoromethyl)biphenyl‐alt‐2,5‐divinylthiophene), consisting of thienylenevinylene as the donor and trifluoromethyl‐substituted biphenyl as the acceptor has been successfully synthesized. CF₃‐PBTV shows solution‐processability without electrically insulating long alkyl side chains. Grazing incidence X‐ray diffraction results suggest a nearly equal population of flat‐on and end‐on domains in CF₃‐PBTV thin film. The excellent ambipolarity of CF₃‐PBTV is demonstrated by well‐equivalent charge mobilities of 0.065 and 0.078 cm² V^?1 s^?1 for p‐ and n‐channel, respectively. The organic field‐effect transistors (OFET) also shows very high on/off ratio (≈10⁷) which is attributed to the relatively large bandgap and low‐lying highest occupied molecular orbital (HOMO) of CF₃‐PBTV. The OFET performance barely changes after the device is stored in ambient conditions for 90 days. The ambient‐stability is attributed to the enhanced oxidative stability from its low‐lying HOMO and the better moisture resistance from its fluorine contents. The performance of CF₃‐PBTV based OFET is annealing independent. It is noteworthy that the solution‐processable, ambipolar, and thienylenevinylene‐containing conjugated polymer without any long alkyl side chains is reported for the first time. And to the best of our knowledge, it is the first ambient‐stable, annealing‐free OFET with well‐equivalent ambipolarity.     

Efficiency Enhancement of Single‐Walled Carbon Nanotube‐Silicon Heterojunction Solar Cells Using Microwave‐Exfoliated Few‐Layer Black Phosphorus

Carbon nanotube‐silicon (CNT‐Si)‐based heterojunction solar cells (HJSCs) are a promising photovoltaic (PV) system. Herein, few‐layer black phosphorus (FL‐BP) sheets are produced in N‐methyl‐2‐pyrrolidone (NMP) using microwave‐assisted liquid‐phase exfoliation and introduced into the CNTs‐Si‐based HJSCs for the first time. The NMP‐based FL‐BP sheets remain stable after mixing with aqueous CNT dispersion for device fabrication. Due to their unique 2D structure and p‐type dominated conduction, the FL‐BP/NMP incorporated CNT‐Si devices show an impressive improvement in the power conversion efficiency from 7.52% (control CNT‐Si cell) to 9.37%. Our density‐functional theory calculation reveals that lowest unoccupied molecular orbital (LUMO) of FL‐BP is higher in energy than that of single‐walled CNT. Therefore, we observed a reduction in the orbitals localized on FL‐BP upon highest occupied molecular orbital to LUMO transition, which corresponds to an improved charge transport. This study opens a new avenue in utilizing 2D phosphorene nanosheets for next‐generation PVs.