A crosslinked polymer as dopant-free hole-transport material for efficient n-i-p type perovskite solar cells

A new crosslinked polymer,called P65,with appropriate photo-electrochemical,opto-electronic,and thermal properties,has been designed and synthesized as an efficient,dopant-free,hole-transport material(HTM)for n-i-p type planar perovskite solar cells(PSCs).P65 is obtained from a low-cost and easily synthesized spiro[fluorene-9,90-xanthene]-30,60-diol(SFX-OH)-based monomer X65 through a freeradical polymerization reaction.The combination of a three-dimensional(3 D)SFX core unit,holetransport methoxydiphenylamine group,and crosslinked polyvinyl network provides P65 with good solubility and excellent film-forming properties.By employing P65 as a dopant-free hole-transport layer in conventional n-i-p type PSCs,a power conversion efficiency(PCE)of up to 17.7%is achieved.To the best of our knowledge,this is the first time a 3 D,crosslinked,polymeric dopant-free HTM has been reported for use in conventional n-i-p type PSCs.This study provides a new strategy for the future development of a 3 D crosslinked polymeric dopant-free HTM with a simple synthetic route and low-cost for commercial,large-scale applications in future PSCs.

Synthesis of Poly(p-phenyleneethynylene)s with Crosslinkable End or Side Groups and Its Solid State Structure and Optical Properties Before and after Crosslinking

Two crosslinkable poly（p-phenyleneethynylene）s（PPEs）： poly[2,5-di（2＇-ethyl-hexyloxy）-1,4-phenylenecthynylene] with end-capped vinyl（PPE1） and poly[2,5-di（allyloxy）-1,4-phenyleneethynylene-2,5-di（2＇-ethyl-hexyloxy）-1,4-phenyleneethynylene]（PPE2） were synthesized. Via the thermal addition reactions of vinyl end groups of PPE1 and allyloxy side groups of PPE2, crosslinked polymers C-PPE1 and C-PPE2 were obtained, respectively. The two polymers were characterized by wide-angle X-ray diffraction（WXRD）, ultraviolet-visible（UV-Vis） absorption, and photoluminescence（PL）. The results indicate that in the solid state, the polymer chains of PPE1 were packed with a low degree of crystallinity because of the sterically hindered（2＇-ethyl-hexyl）oxy branched side chains, but, because of the introduction of allyloxy side chains, the polymer chains of PPE2 were packed in an order fashion with a high degree of crystallinity. Because of the high crosslinking density in C-PPE2, the formation of aggregates and excimer was hampered by the formed crosslinking network more effectively in C-PPE2 film than in C-PPE1 film.

STUDY ON CASTOR OIL POLYURETHANE/POLY (METHYL METHACRYLATE) AB CROSSLINKED POLYMERS

Castor oil polyurethane/poly(methyl methacrylate) AB crosslinked polymers (ABCP) were synthesized by free radical copolymerization of MMA and vinyl-terminated castor oil polyurethane which was obtained from isocyanate-terminated castor oil polyurethane and hydroxyethyl methacrylate The mechanical properties, transition and relaxation, as well as compatibility and morphology of the ABCP were investigated by changing the component. The results show that the ABCP is a semicompatible system and the compatibility of the two components decreases with increasing content of the hard segment. The mechanical and damping properties of the ABCP are obviously superior to that of their homopolymers. The damping value is mainly controlled by cross[ink density of the ABCP but the T-g value by component.

Thermo-and photo-driven soft actuators based on crosslinked liquid crystalline polymers

Crosslinked liquid crystalline polymers（CLCPs） are a type of promising material that possess both the order of liquid crystals and the properties of polymer networks.The anisotropic deformation of the CLCPs takes place when the mesogens experience order to disorder change in response to external stimuli; therefore,they can be utilized to fabricate smart actuators,which have potential applications in artificial muscles,micro-optomechanical systems,optics,and energyharvesting fields.In this review the recent development of thermo-and photo-driven soft actuators based on the CLCPs are summarized.

SYNTHESIS AND FLUORESCENCE STUDY OF St／DVB COPOLYMERS LABELLED WITH PYRENE GROUPS

Two kinds of St/DVB copolymer beeds containing (1 - pyrenyl) formyl and(1 -pyrenyl) methyl groups respectively have been synthesized by both functionalization and copolymerization. The fluorescence spectra of the swollen polymers synthesized are similar in shape to those of the corresponding model compounds, whilethe intensity ratio of excimer to monomer shows clear dependence on the contents ofthe pyrene groups.

In-Situ Synthesized Myoglobin Imprinted Poly(N-Isopropylacrylamide)/Silica Nanocomposite Gels by Using the Molecular Imprinting Method

Temperature sensitive imprinted poly(N-isopropylacrylamide) nanocomposite gels were syntheses via in-situ, free radical crosslinking polymerization of corresponding monomer in nano-sized silica and five different concentrations of myoglobin solution by using the molecular imprinting method. Mb adsorption from five different concentrations of Mb solutions was investigated by two types of nanocomposite gel systems prepared by non-imprinted and imprinted methods. Nanocomposite gels imprinted with Mb showed higher adsorption capacity and specificity for Mb than nanocomposite gels prepared by the usual procedure. The highest Mb adsorption was observed via the imprinted nanocomposite gels with 12.5% Mb. In addition, selectivity studies were also performed by using two reference molecules as fibrinogen and hemoglobin. The imprinted nanocomposite gels had higher adsorption capacity for Mb than the non-imprinted gels and also exhibited good selectivity for Mb and high adsorption rate depending on the number of Mb sized cavities.

Method for Control of Particle Size and Morphology of Paraffin/Polystyrene-Divinylbenzene Microcapsules

Microencapsulation of phase change materials(Micro PCMs) has been paid special attention because of their extensive applications in saving and releasing energy. Micro PCMs containing paraffin with a melting point of 55 ℃ in polystyrene-divinylbenzene(P(St-DVB)) were prepared by suspension-like polymerization. The characterization of microcapsules by FTIR, DSC and TG proved that paraffin had been successfully encapsulated and the proportion of encapsulated paraffin was 49.8%—58.5%. The effects of polyvinylpyrrolidone(PVP) with different molecular weights serving as the suspension stabilizer were investigated in detail. The results illustrated that the type of PVP had a significant influence on the particle size of Micro PCMs. The average diameter of Micro PCMs decreased with an increasing molecular weight of PVP. Moreover, the crosslinker-postaddition method was adopted in this study to improve the morphology of P(St-DVB) Micro PCMs. SEM images showed that when the DVB was added at the 2nd hour of polymerization the morphology of obtained P(St-DVB) Micro PCMs exhibited good sphericity since it could avoid the influence of cross-linker agent during the nucleation period.

Supramolecular complex formation of β-cyclodextrin polymer with substituted salicylic acid or 3-hydroxy-2-naphthoic acid and their electrorheological behaviors

According to the chemical design, electrorheological properties of supramolecular complex from β-cyclodextrin polymer (β -CDP) were discussed. Six supramolecular complexes of β-cyclodextrin polymer with substituted salicylic acid and 3-hydroxy-2-naphthoic acid were synthesized by the solid-phase self-assembly method, and their component and structure were characterized by NMR, FT-IR, UV-vis and the fluorescence analysis. Then the electrorheological properties of their suspensions in silicone oil were investigated under DC electric fields. It was found that the yield stresses of these supramolecular complex ER fluids were 7.3–9.8 kPa at 4 kV/mm in DC electric field, which were enhanced by 34%–72% compared with that of pure β-CDP. Among them, that of β-CDP/3-hydroxy-2-naphthoic acid ER fluid was the highest. It was also found that the ER effect of supramolecular complexes can be controlled by changing different guests. When the substituted group is at phenyl ring, ER behavior can be slightly adjusted by the different substituted groups, their number as well as their position at phenyl ring. This can be proved by the measurement of dielectric properties.

Hybrid Dextran-gadolinium Nano-suitcases as High-relaxivity MRI Contrast Agents

Dextran-poly（glycidyl methacrylate） （Dex-PGMA） nano-suitcases were synthesized efficiently via a graft copolymerization induced self-assembly （GISA） approach. On this basis, the Dex-PGMA nano-suitcases were modified with hydrazide, and the attachment of multiple chelated Gd（III） ions to the interior of the nano-suitcases affords nanoscale MRI contrast agents with high relaxivity values. The highly fenestrated dextran shell of the nano-suitcases assures water exchange which readily occurs between the surrounding environment and the Gd（III） ions encapsulated within the hybrid nano-suitcases. The complexation between the hydrophilic hydrazide interior of the nano-suitcases and Gd（III） ions results in an impressive Gd payload at 22.6 wt% in the hybrid nano-suitcases. The longitudinal relaxivity （rl） of the hybrid nano-suitcases is reported as 44.4 L/（mmol-s）, which is 9-14 folds of that of commercial Gd-DTPA agents. In vivo MRI studies demonstrate that the hybrid nano-suitcases accumulated in the lymph node of the rat due to their nanoscale dimensions and displayed strong signals in vivo. The results indicated that the hybrid nano-suitcases provide a promising platform for the diagnosis of lymph node related diseases.