A New Donor–Acceptor–Donor Polyfluorene Copolymer with Balanced Electron and Hole Mobility

A new alternating polyfluorene copolymer poly[2,7‐(9,9‐dioctylfluoren)‐alt‐5,5‐(5′,8′‐di‐2‐thienyl‐(2′,3′‐bis‐(3′′‐octyloxyphenyl)‐quinoxaline))] (APFO‐15), which has electron donor–acceptor–donor units in between the fluorene units, is synthesized and characterized. This polymer has a strong absorption and emission in the visible range of the solar spectrum. Its electroluminescence and photoluminescence emissions extend from about 560 to 900 nm. Moreover, solar cells with efficiencies in excess of 3.5 % have been realized from blends of APFO‐15 and an electron acceptor molecule, a methanofullerene [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM). It has also been observed that electron and hole transport is balanced both in the pure polymer phase and in polymer/PCBM bulk heterojunction films, which makes this material quite attractive for applications in opto‐electronic devices.     

Bulk Heterojunction Solar Cells: Impact of Minor Structural Modifications to the Polymer Backbone on the Polymer–Fullerene Mixing and Packing and on the Fullerene–Fullerene Connecting Network

The morphology of the active layer of a bulk heterojunction solar cell, made of a blend of an electron‐donating polymer and an electron‐accepting fullerene derivative, is known to play a determining role in device performance. Here, a combination of molecular dynamics simulations and long‐range corrected density functional theory calculations is used to elucidate the molecular‐scale effects that even minor structural changes to the polymer backbone can have on the “local” morphology; this study focuses on the extent of polymer–fullerene mixing, on their packing, and on the characteristics of the fullerene–fullerene connecting network in the mixed regions, aspects that are difficult to access experimentally. Three representative polymer donors are investigated: (i) poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PffBT4T‐2OD); (ii) poly[(2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PBT4T‐2OD), where the fluorine atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with hydrogen atoms; and (iii) poly[(2,2′‐bithiophene)‐alt‐(4,7‐bis((2‐decyltetradecyl)thiophen‐2‐yl)‐5,6‐difluoro‐2‐propyl‐2H‐benzo[d][1,2,3]triazole)] (PT2‐FTAZ), where the sulfur atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with nitrogen atoms carrying a linear C₃H₇ side‐chain; these polymers are mixed with the phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) acceptor. This study also discusses the nature of the charge‐transfer electronic states appearing at the donor–acceptor interfaces, the electronic couplings relevant for the charge‐recombination process, and the electron‐transfer features between neighboring PC₇₁BM molecules.     

An Electron Acceptor with Broad Visible–NIR Absorption and Unique Solid State Packing for As‐Cast High Performance Binary Organic Solar Cells

A novel acceptor–donor–acceptor (A–D–A) type electron acceptor 6TIC‐4F with terthieno[3,2‐b]thiophene (6T) as the core unit is rationally designed and synthesized, which exhibits an extraordinarily narrow bandgap (≈1.24 eV) and strong absorption between 650 and 1000 nm. X‐ray crystallographic analysis reveals that it has unique intermolecular π–π stacking. The solar cells based on the as‐cast poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(5,5‐(1′,3′‐di‐2‐thienyl‐5′,7′‐bis(2‐ethylhexyl)benzo[1′,2′‐c:4′,5′‐c′]dithiophene‐4,8‐dione))]) (PBDB‐T): 6TIC‐4F binary blends exhibit an excellent power conversion efficiency (PCE) of 11.14% with a high J_SC of 23.00 mA cm^?2, and a high fill factor of 0.67, which represents one of the best PCE values for low bandgap (E_g < 1.3 eV)–based organic solar cells.     

Size‐Specific Interactions Between Single‐ and Double‐Stranded Oligonucleotides and Cationic Water‐Soluble Oligofluorenes

An improved synthetic approach was developed for the synthesis of 1,4‐bis[9′,9′‐bis(6″‐(N,N,N‐trimethylammonium)‐hexyl)‐fluoren‐2′‐yl]benzene tetrabromide ( 1a ), 1,4‐bis[9′,9′;9″,9″‐tetra(6″′‐(N,N,N‐trimethylammonium)‐hexyl)‐7′,2″‐bisfluoren‐2′‐yl] benzene octabromide ( 1b ) and 1,4‐bis[9′,9′;9″,9″;9″′,9″′‐hexakis(6″″‐(N,N,N‐trimethylammonium)‐hexyl)‐7′,2″,7″,2″′‐trifluoren‐2′‐yl] benzene dodecabromide ( 1c ). These molecules provide a size‐specific series of water‐soluble oligofluorene molecules with increasing numbers of repeat units to model the interactions between cationic conjugated polymers and DNA. Fluorescence quenching and energy‐transfer measurements were performed with 1a – c and single‐stranded (ss) DNA and double‐stranded (ds) DNA, with and without fluorescein (Fl). These studies show that, on a per‐negative‐charge basis, ssDNA quenches the emission of 1a – c more effectively than dsDNA. Furthermore, we show that the energy‐transfer ratios dsDNA–Fl/ssDNA–Fl are dependent on the number of repeat units in 1a – c .     

Synthesis and Properties of a Water‐Soluble Single‐Walled Carbon Nanotube–Poly(m‐aminobenzene sulfonic acid) Graft Copolymer

Poly(m‐aminobenzene sulfonic acid) (PABS), was covalently bonded to single‐walled carbon nanotubes (SWNTs) to form a water‐soluble nanotube–polymer compound (SWNT–PABS). The conductivity of the SWNT–PABS graft copolymer was about 5.6 × 10^–3 S cm^–1, which is much higher than that of neat PABS (5.4 × 10^–7 S cm^–1). The mid‐IR spectrum confirmed the formation of an amide bond between the SWNTs and PABS. The ¹H NMR spectrum of SWNT–PABS showed the absence of free PABS, while the UV/VIS/NIR spectrum of SWNT–PABS showed the presence of the interband transitions of the semiconducting SWNTs and an absorption at 17 750 cm^–1 due to the PABS addend.     

Polymer–Aptamer Hybrid Emulsion Templating Yields Bioresponsive Nanocapsules

This article describes the synthesis of a DNA–polymer, being the nucleotide sequence an aptamer selected in vitro to target specifically the immunoglobulin E (IgE) protein, an allergy biomarker. Subsequent to coupling to poly(2‐alkyl‐2‐oxazoline) with N‐Boc protected amino acid side chains, the resulting amphiphilic DNA–polymer hybrid composed of the water‐soluble DNA fragment grafted to the hydrophobic polymer segment can be regarded as a high molecular weight analogue of a surfactant. It is demonstrated that the copolymer–aptamer stabilizes efficiently submicrometer size oil‐in‐water and water‐in‐oil emulsions, by dynamic light scattering, microscopy, and reflectometry. Particularly interesting is that the aptamer remains functional after coupling to a polymer backbone, stabilization of the emulsion droplets, and locking of the structure subsequent to cross‐linking polymerization. The resulting nanocapsules still target specifically the IgE protein. The biological‐stimulus responsiveness of the structures is of high potential for future developments of carriers for sustained and targeted delivery.     

Identifying a Threshold Impurity Level for Organic Solar Cells: Enhanced First‐Order Recombination Via Well‐Defined PC84BM Traps in Organic Bulk Heterojunction Solar Cells

Small amounts of impurity, even one part in one thousand, in polymer bulk heterojunction solar cells can alter the electronic properties of the device, including reducing the open circuit voltage, the short circuit current and the fill factor. Steady state studies show a dramatic increase in the trap‐assisted recombination rate when [6,6]‐phenyl C₈₄ butyric acid methyl ester (PC₈₄BM) is introduced as a trap site in polymer bulk heterojunction solar cells made of a blend of the copolymer poly[N‐9″‐hepta‐decanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PCDTBT) and the fullerene derivative [6,6]‐phenyl C₆₁ butyric acid methyl ester (PC₆₀BM). The trap density dependent recombination studied here can be described as a combination of bimolecular and Shockley–Read–Hall recombination; the latter is dramatically enhanced by the addition of the PC₈₄BM traps. This study reveals the importance of impurities in limiting the efficiency of organic solar cell devices and gives insight into the mechanism of the trap‐induced recombination loss.     

Original Fuel‐Cell Membranes from Crosslinked Terpolymers via a “Sol–gel” Strategy

Hybrid organic/inorganic membranes that include a functionalized (‐SO₃H), interconnected silica network, a non‐porogenic organic matrix, and a ‐SO₃H‐functionalized terpolymer are synthesized through a sol–gel‐based strategy. The use of a novel crosslinkable poly(vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene sulfonyl fluoride)‐ter‐vinyltriethoxysilane) (poly(VDF‐ter‐PFSVE‐ter‐VTEOS)) terpolymer allows a multiple tuning of the different interfaces to produce original hybrid membranes with improved properties. The synthesized terpolymer and the composite membranes are characterized, and the proton conductivity of a hybrid membrane in the absence of the terpolymer is promising, since 8 mS cm^?1 is reached at room temperature, immersed in water, with an experimental ion‐exchange‐capacity (IEC_exp) value of 0.4 meq g^?1. Furthermore, when the composite membranes contain the interfaced terpolymer, they exhibit both a higher proton conductivity (43 mS cm^?1 at 65 °C under 100% relative humidity) and better stability than the standard hybrid membrane, arising from the occurrence of a better interface between the inorganic silica and the poly[(vinylidene fluoride)‐co‐hexafluoropropylene] (poly(VDF‐co‐HFP)) copolymer network. Accordingly, the hybrid SiO₂‐SO₃H/terpolymer/poly(VDF‐co‐HFP) copolymer membrane has potential use as an electrolyte in a polymer‐electrolyte‐membrane fuel cell operating at intermediate temperatures.     

Ambipolar Charge Transport in Films of Methanofullerene and Poly(phenylenevinylene)/Methanofullerene Blends

Herein, we report experimental studies of electron and hole transport in thin films of [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) and in blends of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene] (MDMO‐PPV) with PCBM. The low‐field hole mobility in pristine MDMO‐PPV is of the order of 10^–7 cm² V^–1 s^–1, in agreement with previous studies, whereas the electron mobility in pristine PCBM was found by current‐density–voltage (J–V) measurements to be of the order of 10^–2 cm² V^–1 s^–1, which is about one order of magnitude greater than previously reported. Adding PCBM to the blend increases both electron and hole mobilities, compared to the pristine polymer, and results in less dispersive hole transport. The hole mobility in a blend containing 67 wt.‐% PCBM is at least two orders of magnitude greater than in the pristine polymer. This result is independent of measurement technique and film thickness, indicating a true bulk property of the material. We therefore propose that PCBM may assist hole transport in the blend, either by participating in hole transport or by changing the polymer‐chain packing to enhance hole mobility. Time‐of‐flight mobility measurements of PCBM dispersed in a polystyrene matrix yield electron and hole mobilities of similar magnitude and relatively non‐dispersive transport. To the best of our knowledge, this is the first report of hole transport in a methanofullerene. We discuss the conditions under which hole transport in the fullerene phase of a polymer/fullerene blend may be expected. The relevance to photovoltaic device function is also discussed.     

2,5‐Functionalized Spiro‐Bisiloles as Highly Efficient Yellow‐Light Emitters in Electroluminescent Devices

New spiro‐bisilole molecules functionalized with nitrogen‐containing heterocyclic groups including 7‐azaindolyl, indolyl, and 2,2′‐dipyridylamino have been synthesized. These molecules are found to display good chemical and thermal stability. They are luminescent in solution and in the solid state with an emission color ranging from blue–green to yellow, depending on the functional group. In the solid state, they display high photoluminescence quantum efficiency (32–40 %). The electroluminescence properties for one of the new molecules, 2,3,3′,4,4′,5‐hexaphenyl‐2′,5′‐bis(p‐2,2′‐dipyridylaminophenyl)spiro‐bisilole, have been investigated by fabricating single‐layer and double‐layer electroluminescent devices. The double‐layer device, in which N,N′‐bis(1‐naphthyl)‐N,N′‐diphenylbenzidine acts as the hole‐transport layer and the functionalized spiro‐bisilole functions as the emitter (emission wavelength = 566 nm) and the electron‐transport layer, displays a brightness of 8440 cd m^–2 at 9 V with a current efficiency of 1.71 cd A^–1. No evidence of exiplex emission is observed.     

Fluorene‐Based Copolymers for Red‐Light‐Emitting Diodes

The syntheses of new fluorene‐based π‐conjugated copolymers; namely, poly((5,5″‐(3′,4′‐dihexyl‐2,2′;5′,2″‐terthiophene 1′,1′‐dioxide))‐alt‐2,7‐(9,9‐dihexylfluorene)) (PFTORT), poly((5,5″″‐(3″,4″‐dihexyl‐2,2′:5′,2′:5″,2‴:5‴,2″″‐quinquethiophene 1″,1″‐dioxide))‐alt‐2,7‐(9,9‐dihexylfluorene)) (PFTTORTT), and poly((5,5‐E‐α‐(2‐thienyl)methylene)‐2‐thiopheneacetonitrile)‐alt‐2,7‐(9,9‐dihexylfluorene)) (PFTCNVT), are reported. In the solid state, PFTORT and PFTCNVT present red–orange emission (with a maximum at 610 nm) while PFTTORTT shows a red emission with a maximum at 666 nm. In all cases, electrochemical measurements have revealed p‐ and n‐dopable copolymers. All these copolymers have been successfully tested in simple light‐emitting diodes and show promising results for orange‐ and red‐light‐emitting devices.     

Correlating Structure with Function in Thermally Annealed PCDTBT:PC70BM Photovoltaic Blends

A range of optical probes are used to study the nanoscale‐structure and electronic‐functionality of a photovoltaic‐applicable blend of the carbazole co‐polymer poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PCDTBT) and the electronic accepting fullerene derivative (6,6)‐phenyl C₇₀‐butyric acid methyl ester (PC₇₀BM). In particular, it is shown that the glass transition temperature of a PCDTBT:PC₇₀BM blend thin‐film is not sensitive to the relative blend‐ratio or film thickness (at 1:4 blending ratio), but is sensitive to casting solvent and the type of substrate on which it is deposited. It is found that the glass transition temperature of the blend reduces on annealing; an observation consistent with disruption of π–π stacking between PCDTBT molecules. Reduced π–π stacking is correlated with reduced hole‐mobility in thermally annealed films. It is suggested that this explains the failure of such annealing protocols to substantially improve device‐efficiency. The annealing studies demonstrate that the blend only undergoes coarse phase‐separation when annealed at or above 155 °C, suggesting a promising degree of morphological stability of PCDTBT:PC₇₀BM blends.     

Stable and Efficient White Electroluminescent Devices Based on a Single Emitting Layer of Polymer Blends

An efficient orange‐light‐emitting polymer (PFTO‐BSeD5) has been developed through the incorporation of low‐bandgap benzoselenadiazole (BSeD) moieties into the backbone of a blue‐light‐emitting polyfluorene copolymer (PFTO poly{[9,9‐bis(4‐(5‐(4‐tert‐butylphenyl)‐[1,3,4]‐oxadiazol‐2‐yl)phenyl)‐9′,9′‐di‐n‐octyl‐[2,2′]‐bifluoren‐7,7′‐diyl]‐stat‐[9,9‐bis(4‐(N,N‐di(4‐n‐butylphenyl)amino)phenyl)‐9′,9′‐di‐n‐octyl‐[2,2′]‐bifluoren‐7,7′‐diyl]}) that contains hole‐transporting triphenylamine and electron‐transporting oxadiazole pendent groups. A polymer light‐emitting device based on this copolymer exhibits a strong, bright‐orange emission with Commission Internationale de L'Eclairage (CIE) color coordinates (0.45,0.52). The maximum brightness is 13 716 cd m^–2 and the maximum luminance efficiency is 5.53 cd A^–1. The use of blends of PFTO‐BSeD5 in PFTO leads to efficient and stable white‐light‐emitting diodes—at a doping concentration of 9 wt %, the device reaches its maximum external quantum efficiency of 1.64 % (4.08 cd A^–1). The emission color remains almost unchanged under different bias conditions: the CIE coordinates are (0.32,0.33) at 11.0 V (2.54 mA cm^–2, 102 cd m^–2) and (0.31,0.33) at 21.0 V (281 mA cm^–2, 7328 cd m^–2). These values are very close to the ideal CIE chromaticity coordinates for a pure white color (0.33,0.33).     

A Micellar Route to Ordered Arrays of Magnetic Nanoparticles: From Size‐Selected Pure Cobalt Dots to Cobalt–Cobalt Oxide Core–Shell Systems

Starting with Co‐salt‐loaded inverse micelles, which form if the diblock copolymer polystyrene‐block‐poly(2‐vinylpyridine) is dissolved in a selective solvent like toluene and CoCl₂ is added to the solution, monomicellar arrays of such micelles exhibiting a significant hexagonal order can be prepared on top of various substrates with tailored intermicellar distances and structure heights. In order to remove the polymer matrix and to finally obtain arrays of pure Co nanoparticles, the micelles are first exposed to an oxygen plasma, followed by a treatment in a hydrogen plasma. Applying in‐situ X‐ray photoelectron spectroscopy, it is demonstrated that: 1) The oxygen plasma completely removes the polymer, though conserving the original order of the micellar array. Furthermore, the resulting nanoparticles are entirely oxidized with a chemical shift of the Co 2p_3/2 line pointing to the formation of Co₃O₄. 2) By the subsequent hydrogen plasma treatment the nanoparticles are fully reduced to metallic Co. 3) By exposing the pure Co nanoparticles for 100 s to various oxygen partial pressures pequation/tex2gif-inf-5.gif, a stepwise oxidation is observed with a still metallic Co core surrounded by an oxide shell. The data allow the extraction of the thickness of the oxide shell as a function of the total exposure to oxygen (pequation/tex2gif-inf-7.gif × time), thus giving the opportunity to control the ferromagnetic–antiferromagnetic composition of an exchange‐biased magnetic system.     

Dopant‐Free Spiro‐Triphenylamine/Fluorene as Hole‐Transporting Material for Perovskite Solar Cells with Enhanced Efficiency and Stability

Chemical doping is often used to enhance electric conductivity of the conjugated molecule as hole‐transporting material (HTM) for the application in optoelectronics. However, chemical dopants can promote ion migration at the electrical field, which deteriorates the device efficiency as well as increases the fabrication cost. Here, two star HTMs, namely 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenyl‐amine) 9,9′‐spirobifluorene (Spiro‐OMeTAD) and poly(triarylamine) are subjeted to chemical combination to yield dopant‐free N2,N2,N2′,N2′,N7,N7,N7′,N7′‐octakis(4‐methoxyphenyl)‐10‐phenyl‐10H‐spiro[acridine‐9,9′‐fluorene]‐2,2′,7,7′‐tetraamine (SAF‐OMe). The power conversion efficiencies (PCEs) of 12.39% achieved by solar cells based on pristine, dopant‐free SAF‐OMe are among the highest reported for perovskite solar cells and are even comparable to devices based on chemically doped Spiro‐OMeTAD (14.84%). Moreover, using a HTM comprised of SAF‐OMe with an additional dopant results in a record PCE of 16.73%. Compared to Spiro‐OMeTAD‐based devices, SAF‐OMe significantly improves stability.     

Starburst DCM‐Type Red‐Light‐Emitting Materials for Electroluminescence Applications

Three new starburst DCM (4‐(dicyanomethylene)‐2‐methyl‐6‐[4‐(dimethylaminostyryl)‐4H‐pyran]) derivatives, 4,4′,4′′‐tris[2‐(4‐dicyanomethylene‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (TDCM), 4,4′,′′‐tris[2‐(4‐(1′,3′‐indandione)‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (TIN), and 4‐methoxy‐4′,4′′‐bis[2‐(4‐(1′,3′‐indandione)‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (MBIN), have been designed and synthesized for application as red‐light emitters in organic light‐emitting diodes (OLEDs). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) reveal their extremely high glass‐transition temperatures and decomposition temperatures, as well as their low tendency to crystallize. Photoluminescence and electroluminescence measurements show that they exhibit a greatly restricted concentration‐quenching effect compared to DCM1 (4‐(dicyanomethylene)‐2‐methyl‐6‐[p‐(N,N‐dimethylamino)‐styryl]‐4H‐pyran), a simple but typical DCM‐type dye, as a result of their non‐planar, three‐dimensional structures that result from their unique propeller‐like triphenylamine electron‐donating cores. The peripheral electron‐withdrawing moieties also play a key role in the restriction of concentration quenching. That is, TIN and MBIN, bearing 1,3‐indandione acceptors, emit more efficiently than TDCM and DCM1, which have dicyanomethylene as acceptors at a high doping concentration of 10 wt.‐% in poly(9‐vinylcarbazole) (PVK) film, irrespective of whether they are photoexcited or electroexcited, though their fluorescence quantum yields in dilute solutions are much lower than that of DCM1. By way of the co‐doping approach, the electroluminescence device with the configuration indium tin oxide (ITO)/PVK:MBIN(10 wt.‐%):tris(4‐(2‐phenylethynyl)‐phenyl)amine (TPA; 30 wt.‐%) (70 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 20 nm)/tris(8‐quinolinolato) aluminum (Alq₃;15 nm)/LiF (0.3 nm)/Al (150 nm) exhibits a turn‐on voltage of 5.1 V, a maximum luminance of 6971 cd m^–2, a maximum efficiency of 6.14 cd A^–1 (405 cd m^–2), and chromaticity coordinates of (0.66,0.33). The encouraging electroluminescence performance suggests potential applications of the starburst DCM red‐light emitters in OLEDs.     

High‐Efficiency Red Phosphorescent Iridium Dendrimers with Charge‐ Transporting Dendrons: Synthesis and Electroluminescent Properties

A series of 1‐phenylisoquinoline derivatives encapsulated with peripheral arylamines as dendrons are synthesized by using the Ullmann reaction and palladium‐catalyzed aromatic carbon–carbon Suzuki‐coupling reactions. Red‐emitting dendritic iridium complexes (called G1‐1 , G1‐2 , and G2 ) are synthesized using the following derivatives: N,N‐diphenyl‐3′‐isoquinolin‐4‐biphenylaniline, N,N‐di(9,9‐dimethylfluorenyl‐3′‐isoquinolin‐4‐biphenylaniline, N,N‐di(4′‐di(2′‐(9′,9′‐dimethylfluorenyl)amine)biphenyl‐3′‐isoquinolin‐4‐biphenylaniline as the first ligands and 5‐methyl‐3‐(pyridin‐2′‐yl)‐1H‐1,2,4‐triazole as an ancillary ligand. The obtained dendrimers are soluble in common organic solvents, and uniform thin films can be spin‐coated from such solutions. Devices fabricated from dendritic iridium complexes G1‐2 and G2 with a small molecule host are fabricated by spin‐coating from chloroform solution in different device configurations. G1‐2 and G2 show similar device performances with maximum external quantum efficiencies (EQEs) of 12.8 % and 11.8 % (photons/electron) and luminous efficiency of 9.2 cd A^–1 and 8.5 cd A^–1 at 0.1 mA cm^–2, respectively. Devices based on polymer host poly(9,9‐dioctylfluorene)(PFO) (30 % PBD (2‐(4‐biphenyl)‐5‐(4‐tert‐butylphenyl‐1,3,4‐oxadiazole)) show a slightly higher efficiency for G1‐2 , with a maximum EQE of 13.9 % at a much higher current density of 6.4 mA cm^–2 and luminance of 601 cd m^–2.     

Alkylsilyl Functionalized Copolymer Donor for Annealing‐Free High Performance Solar Cells with over 11% Efficiency: Crystallinity Induced Small Driving Force

The contradiction between enlarging the offset between energy levels of donor/acceptor and the required driving force for exciton split leads to a trade‐off between open circuit voltage (V_OC) and short circuit current density (J_SC), which is a big challenge for development of high performance polymer solar cells (PSCs). Some advanced works reported the PSCs with low photon energy loss (E_loss) and small driving force, but the correlation of molecular structures of light‐harvesting system and driving force is still unclear. In this work, a new alkylsilyl functionalized copolymer donor PBDS‐T (PBDST: poly[(2,6trialkylsilyl thiophen2yl)benzo[1,2b:4,5b′]dithiophene))alt(5,5(1′,3′di2thienyl5′,7′bis(2ethylhexyl)benzo[1′,2′c:4′,5′c′]dithiophene4,8dione))]) with low‐lying energy levels was designed for efficient PSCs. By monitoring the Photoluminescence quenching of the bulk and bilayer heterojunctions, small driving forces, ?E_HOMO of 0.15 eV and ?E_LUMO of 0.22 eV were founded to allow for efficient charge transfer, which were observed to correlate with the crystalline PBDS‐T and the optimal morphology in PBDS‐T:ITIC (ITIC: 3,9bis(2methylene(3(1,1dicyanomethylene)indanone))5,5,11,11tetrakis(4hexylphenyl)dithieno[2,3d:2′,3′d′]sindaceno[1,2b:5,6b′]dithiophene). Simultaneously improved V_OC, J_SC and small Eloss boosted the PCE over 11%, which is one of the highest values for annealing‐free device. These results shield a light on precise design of a light‐harvesting system with small driving force to simultaneously improve the V_OC and J_SC for highly efficient PSCs.     

Temperature Responsive Solution Partition of Organic–Inorganic Hybrid Poly(N‐isopropylacrylamide)‐Coated Mesoporous Silica Nanospheres

A series of poly(N‐isopropylacrylamide)‐coated mesoporous silica nanoparticle materials (PNiPAm‐MSNs) has been synthesized by a surface‐initiated living radical polymerization with a reversible addition–fragmentation chain transfer (RAFT) reaction. The structure and the degree of polymerization of the PNiPAm‐MSNs has been characterized by a variety of techniques, including nitrogen sorption analysis, ²⁹Si and ¹³C solid‐state NMR spectroscopy, transmission electron microscopy (TEM), and powder X‐ray diffraction (XRD). The thermally induced changes of the surface properties of these polymer‐coated core–shell nanoparticles have been determined by examining their partition activities in a biphasic solution (water/toluene) at different temperatures.     

Collective Response from a Cationic Tetrahedral Fluorene for Label‐Free DNA Detection

A cationic water‐soluble tetrahedral molecule bearing four phenylene‐bis(fluorene) optical units, namely tetrakis[4‐(2‐(9,9,9′,9′‐tetrakis(N,N,N‐trimethylammoniumhexyl)‐7,2′‐bifluorenyl))‐phenyl]methane hexadecanebromide, was designed and synthesized. Fluorescence resonance energy transfer (FRET) experiments between the tetrahedral molecule and fluorescein‐labeled double stranded DNA (dsDNA‐Fl) or single stranded DNA (ssDNA‐Fl) were undertaken. Due to its specific shape and spatial registry, the tetrahedral molecule shows improved FRET efficiencies to dsDNA‐Fl as well as improved selectivity between dsDNA and ssDNA, when compared to a cationic conjugated polymer with similar repeat units. 30‐Fold signal amplification for dsDNA/ethidium bromide (EB) and selective response between complementary and non‐complementary DNA indicates that tetrahedral molecules could be useful to amplify the optical response from EB‐based DNA protocols.