The deformation measurement of electrosynthesized polythiophene(Pth)thin films is difficultbecause of the small thickness and high flexibility of the specimen.An electronic speckle pattern interferom-etry(ESPI)method ...The deformation measurement of electrosynthesized polythiophene(Pth)thin films is difficultbecause of the small thickness and high flexibility of the specimen.An electronic speckle pattern interferom-etry(ESPI)method is used to measure the deformation of Pth films of thicknesses in the range of 4-65 μmTheir stress-strain curves are obtained.It is found that the mechanical properties of Pth films are sensitiveto the specimen thickness.The tensile strength increases with decreasing thickness of thin film from 10 μm.The influence of the electrochemical synthesis conditions on the mechanical properties of Pth films is also dis-cussed.展开更多
The complexation of thiophene with a Lewis acid with moderate acidity as a solvent, such as BF<sub>3</sub>-ethyl ether （BFEE） remarkedly lowered the electrochemical polymerization potential. The positive...The complexation of thiophene with a Lewis acid with moderate acidity as a solvent, such as BF<sub>3</sub>-ethyl ether （BFEE） remarkedly lowered the electrochemical polymerization potential. The positively chargedmetal surface of electrode in the process of electrochemical deposition enhanced the coordination interactionbetween π-electrons of thiophene unit and the metal, which makes thiophene rings lie parallel to the surfaceof electrode, resulting in a highly ordered polymeric structure. Because of the large intra-chain transferintegrals, the transport of charge is believed to be principally along the conjugated chains, which is muchgreater than the inter-chain hopping. The specific electrical resistance across the polythiophene film thicknessis more than 10<sup>4</sup> times than that along the surface plane of the film. In this paper we review the recentdevelopment of polymerization technique by low potential electrochemical method performed in our lab andseveral electrical devices in which the compact polythiophene films, such as anionic and cationic sieves, andlaminate film junction of undoped polythiophene derivatives were used.展开更多
Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes givespolymers with relatively high molecular weights and good processibility. Investigationof these polymers by means of GPC indicates that...Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes givespolymers with relatively high molecular weights and good processibility. Investigationof these polymers by means of GPC indicates that an increase in the number of fluorineatoms in the fluorinated group results in a decrease in degree of polymerization of thepolymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluo-rinated group substituted polythiophenes have regular 2, 5-coupling in their main chains.The SEM micrographs of the polymer films exhibit that polymer (1)-poly [3-2, 2, 3, 3-tetrafluoro-propoxy) thiophene] possesses more regular structure than the other polymersdo. Substitution of polythiophenes by fluorinated groups leads to the polymers with highelectric, electrochemical and thermal stability.展开更多
Three series of polythiophenes containing fluoroalkoxy and fluoroether substituentswere prepared by electrochemical polymerization. The effect of substituents with fluoro-alkoxy or ether functional groups on the elect...Three series of polythiophenes containing fluoroalkoxy and fluoroether substituentswere prepared by electrochemical polymerization. The effect of substituents with fluoro-alkoxy or ether functional groups on the electrochemical polymerization of thiophene mono-mers and properties of the obtained polymers were analyzed. The introduction of a flu-oroether functional group at the 3-position of the thiophene ring leads to an increase ofthe oxidation potential of the monomer and to a decrease of the conductivity of the re-sulting polymers, even with the use of a CH<sub>2</sub> group as spacer. Conversely, the presenceof an oxygen atom directly at the 3-position of the thiophene ring, which offsets the nega-tive withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conductingpolythiophenes.展开更多
A polythiophene film was electrochemically deposited on a Pt micro plate electrode and investigated by cyclic voltammetry and in situ reflection microscopic FTIR spectroscopy. The FTIR analysis showed that the electro...A polythiophene film was electrochemically deposited on a Pt micro plate electrode and investigated by cyclic voltammetry and in situ reflection microscopic FTIR spectroscopy. The FTIR analysis showed that the electropolymerization of thiophene on the Pt surface was affected by the surface adsorption processes of thiophene molecules. Two adsorption modes were identified. Two structure models of the polythiophene chain were observed simultaneously. It was proposed that the good conductibility of the polythiophene film was originated from a co vibratory equilibrium of the link part of model Ⅰ and model Ⅱ.展开更多
Polythiophene and its derivatives are getting more andmore attention as a new kind of conducting polymers.Their conductivity,application,possible processingmethods and development are discussed in this article.
In polymers, the electronic activation energy depends on the fragmentation, crosslinking, dopants, moisture and in general on the structure-environment interaction. This has a special importance in plasma polymers bec...In polymers, the electronic activation energy depends on the fragmentation, crosslinking, dopants, moisture and in general on the structure-environment interaction. This has a special importance in plasma polymers because fragmentation and crosslinking are usually higher than in other polymers. In this work, DC electrical conductivity of polythiophene thin films prepared by plasma (pPTh) was studied using the Meyer-Neldel (MN) rule to calculate the characteristic MN energy and temperature as a function of moisture and metallic dopants. The experimental data for pPTh synthesized in different conditions indicated that EM = 32 meV and TM = 373 K, suggesting a thermally activated conduction mechanism;however, in polymer-metal matrices with metal concentration higher than the percolation threshold, the conduction mechanism is different causing that the MN rule was only partially fulfilled. The congruence of the experimental data with the multiexcitation entropy model is discussed.展开更多
A novel poly(quinquethiophene) partially containing 3,4-ethylenedioxythiophene (EDOT) and 3-hexylthiophene, poly(3,3 ''''-dihexyl-3',4',3''',4'''-diethylenedioxy-2,2'...A novel poly(quinquethiophene) partially containing 3,4-ethylenedioxythiophene (EDOT) and 3-hexylthiophene, poly(3,3 ''''-dihexyl-3',4',3''',4'''-diethylenedioxy-2,2':5',2'':5'',2''':5''',2''''-quinquethiophene), was synthesized by three types of polycondensations. Among them, direct C-H coupling reaction gave the polymer with the highest molecular weight. The resulting polymer was soluble in common organic solvents. Absorption and fluorescence spectra of the polymer showed a remarkable red-shift compared with the corresponding monomer due to the expansion of effective π-conjugation length.展开更多
This work presents a study about the structure and morphology of thin plasma composite films of polythiophene (PTh) with metallic particles of Ti (PTh-Ti). The objective was to study the water affinity and electric co...This work presents a study about the structure and morphology of thin plasma composite films of polythiophene (PTh) with metallic particles of Ti (PTh-Ti). The objective was to study the water affinity and electric conductivity in PTh with the addition of metallic phases. The hydrophilicity was studied with the contact angles formed between water and surfaces, and the electric conductivity was calculated with the resistance measured in a two-probe device. The structure and morphology of the composites were studied with X-ray diffraction and scanning electron microscopy. The results indicated that PTh-Ti formed thin films of hybrid composites with oxidized Ti and Fe additional particles released from the electrodes used in the syntheses. The metallic fraction resulted in 2 diffraction angles at 31.6° and 66.1° product of the complex interaction among Ti, resembling orthorhombic TiO2 structures, and PTh. The metallic particles and iodine, added as a dopant to the composites to increase conductivity, reduced the hydrophilicity with water in a competition between roughness and chemical composition. In these conditions, the contact angles resulted between 46° and 75°. The electric conductivity was about 10-6 S/m increasing one order of magnitude with the metallic fraction. However, the high resistance of the polymeric fraction apparently dominates the transference of charges.展开更多
Polythiophenes(PTs)are prospective polymer donors for large-scale manufacturing and industrialization owing to their simple structures and low synthetic cost.However,the fabrication of PT solar cells depends on highly...Polythiophenes(PTs)are prospective polymer donors for large-scale manufacturing and industrialization owing to their simple structures and low synthetic cost.However,the fabrication of PT solar cells depends on highly toxic chlorinated solvents,and less research has been done on the use of more environmentally friendly non-halogenated solvents.Herein,highly efficient PT solar cells based on top-performance polythiophene,P5TCN-F25,processed from a non-halogenated solvent are reported by delicate aggregation control.A power conversion efficiency of up to 15.68%was achieved by depositing the active layer from a hot o-xylene solution,which is the record efficiency of non-halogenated processed PT solar cells up to date.The appropriate solution temperature is beneficial to the formation of ordered polymer stacking and desirable phase separation size,which thereby contributes to enhanced charge transfer efficiency,more balanced hole/electron mobility,and reduced trap-assisted recombination.These results provide valuable implications for improving the efficiency of PT solar cells via environmentallyfriendly processing.展开更多
Chemosensor arrays have a great potential for on-site applications in real-world scenarios.However,to fabricate on chemosensor array a number of chemosensors are required to obtain various optical patterns for multian...Chemosensor arrays have a great potential for on-site applications in real-world scenarios.However,to fabricate on chemosensor array a number of chemosensors are required to obtain various optical patterns for multianalyte detection.Herein,we propose a minimized chemosensor array composed of only two types of carboxylate-functionalized polythiophene derivatives for the detection of eight types of metal ions.Upon recognition of the metal ions,the polythiophenes exhibited changes in their fluorescence intensity and various spectral shifts.Although both chemosensors have the same polymer backbone and recognition moiety,only the difference in the number of methylene groups contributed to the difference in the fluorescence response patterns.Consequently,the metal ions in aqueous media were successfully discriminated qualitatively and quantitatively by the chemosensor microarray on the glass chip.This study offers an approach for achieving a minimized chemosensor array just by changing the alkyl chain lengths without the necessity for many receptors and reporters.展开更多
Polythiophenes,with merits of low cost and high scalability of synthesis,have received growing interest in organic solar cells.To date,the best-performing polythiophene:nonfullerene solar cells exhibit typical power c...Polythiophenes,with merits of low cost and high scalability of synthesis,have received growing interest in organic solar cells.To date,the best-performing polythiophene:nonfullerene solar cells exhibit typical power conversion efficiencies (PCEs) of 10%–12%,which is much lower than those employing PM6-and D18-type polymers.This inferior performance is mostly limited by the improper miscibility between polythiophene and acceptors.Efforts on engineering the molecular structure to systematically tune the miscibility are required.With the aid of group contribution calculations,the miscibility of polythiophene:nonfullerene blend system was finely tuned by varying the ratios of siloxane-terminated chains and alkyl chains in ester-substituted polythiophenes through random copolymerization.Based on a series of the polythiophene and nonfullerene acceptors,the detailed analysis of blend miscibility and performance reveals a surprising anticorrelation between the Flory-Huggins interaction parameter (χ_(aa)) and the optimal time of solvent vapor annealing for device performance across these systems.Primarily due to the slightly higher χ_(aa),the blend of PDCBT-Cl-Si5 and ITIC-Th1 results in a record-high PCE of 12.85%in polythiophene:nonfullerene solar cells.The results not only provide a calculation-guided approach for molecular design but also prove that precise control of the miscibility is an effective way to design high-performance polythiophene:nonfullerene blends and beyond.展开更多
Electrical and magnetic properties are two crucial factors for the designing of broadband electromagnetic wave absorption(EWA)materials.In this work,we synthesized various magnetic metal sulfides/carbon(M_(x)S_(y)/C)n...Electrical and magnetic properties are two crucial factors for the designing of broadband electromagnetic wave absorption(EWA)materials.In this work,we synthesized various magnetic metal sulfides/carbon(M_(x)S_(y)/C)nanocomposites from the precursor complex of metal in microporous polythiophene(MPT),and systematically investigated their EWA properties and mechanism.The characterization results indicate that M_(x)S_(y) were determined to be Fe_(7)S_(8)/C,Co_(9)S_(8)/C and Ni_(4)S_(3)/C,respectively.It is observed that M_(x)S_(y)/C nanocomposites exhibit remarkable EWA performances,where the maximal absorption gets to-51.3 dB,and efficient absorption can be realized in 10.32-18 GHz(7.68 GHz),which is superior to most reported magnetic carbonaceous EWA composites.Beside,the efficient absorption can be tuned to cover Ku band X band,demonstrating their great potential in practical applications.Improved conductance loss,obvious polarization relaxation,and apparent eddy current loss are deemed to make the predominant contributions to the high-performance EWA.This research opens up the exploration of novel nanocomposite coupling dielectric loss and magnetic loss using MPT-metal complex precursor for EWA applications.展开更多
At present,most of state-of-the-art power conversion efficiencies(PCEs)of organic solar cells(OSCs)are achieved from the photoactive materials involving donor–acceptor(D–A)copolymer donors.It is well known that the ...At present,most of state-of-the-art power conversion efficiencies(PCEs)of organic solar cells(OSCs)are achieved from the photoactive materials involving donor–acceptor(D–A)copolymer donors.It is well known that the complicated molecular structure of D–A copolymers means the tedious synthesis,which brings about severe cost issue and poor scalability for the industrial production.Therefore,to develop application-oriented OSCs,considerable attention should be paid on simplifying the chemical structures of polymer donors.Polythiophene(PT)and poly(thiophene vinylene)(PTV)derivatives should be among the simplest polymer donors,and OSCs based on them have made some breakthroughs in past 2 years.Here,we briefly introduce the recent advances of OSCs based on low-cost polymers including poly(3-hexylthiophene)(P3HT),PT derivatives,and PTV derivatives,respectively,and emphasize the importance of modulating energy levels,preaggregation effect,and D/A miscibility for the past progress as well as the future development.At last,we also propose some challenges demanding prompt solution for realizing practical application of OSCs,aiming at providing guidance and stimulating new ideas for further research.展开更多
A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structure...A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.展开更多
In this study, we demonstrate a novel method for fabricating polythiophene patterns, i.e., cylindrical holes and cylinders, through blending of a thermally curable polythiophene carrying with tertiary ester groups(PT-...In this study, we demonstrate a novel method for fabricating polythiophene patterns, i.e., cylindrical holes and cylinders, through blending of a thermally curable polythiophene carrying with tertiary ester groups(PT-tert-ESTER) and poly(methyl methacrylate)(PMMA), followed by thermal conversion of the PT-tert-ESTER to an insoluble polythiophene via low-temperature cleavage of the tertiary ester groups and removal of the PMMA component via ultraviolet degradation. We show that the surface polarity of substrates, the mass ratio of PT-tert-ESTER to PMMA in the blend solutions as well as the concentration of the blend solutions strongly influence the formation of the polythiophene patterns. Cylindrical holes are more readily formed on less polar substrates when a PT-tert-ESTER dominated blend solution is used, while cylinders are more readily formed on more polar substrates when a PMMA dominated blend solution is used. Moreover, the diameters of both the cylindrical holes and the cylinders decrease as the PT-tert-ESTER concentration is increased in the respective ranges of the PT-tert-ESTER/PMMA ratios where the patterns are formed. Grazing incident X-ray diffraction data have indicated that the patterning of the PT-tert-ESTER component in the blend films improves the crystallinity of PT-tert-ESTER as well as the molecular packing of the insoluble polythiophene in the resultant patterned polythiophene films.展开更多
The power conversion efficiencies(PCEs)of organic solar cells(OSCs)have reached 18%recently,which have already met the demand of practical application.However,these outstanding results were generally achieved with don...The power conversion efficiencies(PCEs)of organic solar cells(OSCs)have reached 18%recently,which have already met the demand of practical application.However,these outstanding results were generally achieved with donor-acceptor(D-A)type copolymer donors,which can hardly fulfill the low-cost largescale production due to their complicated synthesis processes.Therefore,developing polymer donors with simple chemical structures is urgent for realizing low-cost OSCs.Polythiophene(PT)derivatives are currently regarded as promising candidates for such kind of donor materials,which has been illustrated in many works.In this work,two new alkylthio substituted PT derivatives,P301 and P302,were synthesized and tested as donors in the OSCs using Y5 as the accepto r.In comparison,the introduction of fluorine atoms on the backbone of P302 can not only downshift the energy levels,but also greatly improve the phase separation morphologies of the active layers,which is ascribed to the enhanced aggregation effect and the reduced miscibility with the non-fullerene acceptor.As a result,the P302:Y5-based OSC exhibits a significantly improved PCE of 9.65%than that of P301:Y5-based one,indicating the important role of fluorination in the construction of efficient PT derivative donors.展开更多
A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The appro...A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The approach relies on the formation of supramolecular polythiophene assemblies in the presence of PA through electrostatic,charge transfer and π-π stacking interactions.This probe could be utilized for the rapid and visual detection of PA both in aqueous solution and solid support with high specificity and sensitivity.The detection limit of this sensor is as low as 5.0 × 10^-8 mol/L.展开更多
Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to...Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to-tail unit,the p-doping occurs at a similar rate.The reaction between poly(3-dodecylthiophene),P3DodTh,and the acid takes place more rapidly.P3OBuTh with a butoxy substituent undergoes more facile p-doping and receives photochemical reaction with CHCl3,and this reaction obeys a pseudo-first-order rate law with a rate constant kobs of 1.42×10-5s-1at room tempera- ture.展开更多
One conjugated polymer consisting of carbazole and 3-hexylthiophene moiety, poly(N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole)(PNDC), has been synthesized by ferric chloride oxidative polymerization. The monomer N-Hex...One conjugated polymer consisting of carbazole and 3-hexylthiophene moiety, poly(N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole)(PNDC), has been synthesized by ferric chloride oxidative polymerization. The monomer N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole was synthesized and characterized by IR, 1H-NMR, 13C-NMR and MS. UV-vis absorption spectrum, fluorescence spectrum, photoluminescence spectrum and electrochemical properties of the polymer were investigated. Polymer PNDC shows maximum peak appearing at 394 nm in UV-vis absorption spectrum, strongest fluorescence-emission at 482 nm in fluorescence spectrum and maximum emission peak at 492 nm in photoluminescence spectrum. The band-gap(Eg), HOMO energy(EHOMO), and LUMO energy(ELUMO) of the polymer were obtained as 2.58,-5.32, and-2.74 e V, respectively.展开更多
基金the Basic-Research Foundation of Tsinghua University(JC2000057)the Visiting Scholar Foundation of Solid Mechanical Key Lab in Tongji University of the Ministry of Education of China
文摘The deformation measurement of electrosynthesized polythiophene(Pth)thin films is difficultbecause of the small thickness and high flexibility of the specimen.An electronic speckle pattern interferom-etry(ESPI)method is used to measure the deformation of Pth films of thicknesses in the range of 4-65 μmTheir stress-strain curves are obtained.It is found that the mechanical properties of Pth films are sensitiveto the specimen thickness.The tensile strength increases with decreasing thickness of thin film from 10 μm.The influence of the electrochemical synthesis conditions on the mechanical properties of Pth films is also dis-cussed.
文摘The complexation of thiophene with a Lewis acid with moderate acidity as a solvent, such as BF<sub>3</sub>-ethyl ether （BFEE） remarkedly lowered the electrochemical polymerization potential. The positively chargedmetal surface of electrode in the process of electrochemical deposition enhanced the coordination interactionbetween π-electrons of thiophene unit and the metal, which makes thiophene rings lie parallel to the surfaceof electrode, resulting in a highly ordered polymeric structure. Because of the large intra-chain transferintegrals, the transport of charge is believed to be principally along the conjugated chains, which is muchgreater than the inter-chain hopping. The specific electrical resistance across the polythiophene film thicknessis more than 10<sup>4</sup> times than that along the surface plane of the film. In this paper we review the recentdevelopment of polymerization technique by low potential electrochemical method performed in our lab andseveral electrical devices in which the compact polythiophene films, such as anionic and cationic sieves, andlaminate film junction of undoped polythiophene derivatives were used.
基金This work was supported by the National Natural Science Foundation of China.
文摘Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes givespolymers with relatively high molecular weights and good processibility. Investigationof these polymers by means of GPC indicates that an increase in the number of fluorineatoms in the fluorinated group results in a decrease in degree of polymerization of thepolymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluo-rinated group substituted polythiophenes have regular 2, 5-coupling in their main chains.The SEM micrographs of the polymer films exhibit that polymer (1)-poly [3-2, 2, 3, 3-tetrafluoro-propoxy) thiophene] possesses more regular structure than the other polymersdo. Substitution of polythiophenes by fluorinated groups leads to the polymers with highelectric, electrochemical and thermal stability.
基金This work was supported by the National Natural Science Foundation of China.
文摘Three series of polythiophenes containing fluoroalkoxy and fluoroether substituentswere prepared by electrochemical polymerization. The effect of substituents with fluoro-alkoxy or ether functional groups on the electrochemical polymerization of thiophene mono-mers and properties of the obtained polymers were analyzed. The introduction of a flu-oroether functional group at the 3-position of the thiophene ring leads to an increase ofthe oxidation potential of the monomer and to a decrease of the conductivity of the re-sulting polymers, even with the use of a CH<sub>2</sub> group as spacer. Conversely, the presenceof an oxygen atom directly at the 3-position of the thiophene ring, which offsets the nega-tive withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conductingpolythiophenes.
文摘A polythiophene film was electrochemically deposited on a Pt micro plate electrode and investigated by cyclic voltammetry and in situ reflection microscopic FTIR spectroscopy. The FTIR analysis showed that the electropolymerization of thiophene on the Pt surface was affected by the surface adsorption processes of thiophene molecules. Two adsorption modes were identified. Two structure models of the polythiophene chain were observed simultaneously. It was proposed that the good conductibility of the polythiophene film was originated from a co vibratory equilibrium of the link part of model Ⅰ and model Ⅱ.
文摘Polythiophene and its derivatives are getting more andmore attention as a new kind of conducting polymers.Their conductivity,application,possible processingmethods and development are discussed in this article.
文摘In polymers, the electronic activation energy depends on the fragmentation, crosslinking, dopants, moisture and in general on the structure-environment interaction. This has a special importance in plasma polymers because fragmentation and crosslinking are usually higher than in other polymers. In this work, DC electrical conductivity of polythiophene thin films prepared by plasma (pPTh) was studied using the Meyer-Neldel (MN) rule to calculate the characteristic MN energy and temperature as a function of moisture and metallic dopants. The experimental data for pPTh synthesized in different conditions indicated that EM = 32 meV and TM = 373 K, suggesting a thermally activated conduction mechanism;however, in polymer-metal matrices with metal concentration higher than the percolation threshold, the conduction mechanism is different causing that the MN rule was only partially fulfilled. The congruence of the experimental data with the multiexcitation entropy model is discussed.
文摘A novel poly(quinquethiophene) partially containing 3,4-ethylenedioxythiophene (EDOT) and 3-hexylthiophene, poly(3,3 ''''-dihexyl-3',4',3''',4'''-diethylenedioxy-2,2':5',2'':5'',2''':5''',2''''-quinquethiophene), was synthesized by three types of polycondensations. Among them, direct C-H coupling reaction gave the polymer with the highest molecular weight. The resulting polymer was soluble in common organic solvents. Absorption and fluorescence spectra of the polymer showed a remarkable red-shift compared with the corresponding monomer due to the expansion of effective π-conjugation length.
文摘This work presents a study about the structure and morphology of thin plasma composite films of polythiophene (PTh) with metallic particles of Ti (PTh-Ti). The objective was to study the water affinity and electric conductivity in PTh with the addition of metallic phases. The hydrophilicity was studied with the contact angles formed between water and surfaces, and the electric conductivity was calculated with the resistance measured in a two-probe device. The structure and morphology of the composites were studied with X-ray diffraction and scanning electron microscopy. The results indicated that PTh-Ti formed thin films of hybrid composites with oxidized Ti and Fe additional particles released from the electrodes used in the syntheses. The metallic fraction resulted in 2 diffraction angles at 31.6° and 66.1° product of the complex interaction among Ti, resembling orthorhombic TiO2 structures, and PTh. The metallic particles and iodine, added as a dopant to the composites to increase conductivity, reduced the hydrophilicity with water in a competition between roughness and chemical composition. In these conditions, the contact angles resulted between 46° and 75°. The electric conductivity was about 10-6 S/m increasing one order of magnitude with the metallic fraction. However, the high resistance of the polymeric fraction apparently dominates the transference of charges.
基金supported by the Guangdong Basic and Applied Basic Research Foundation(2022B1515120008)the Guangdong Innovative and Entrepreneurial Research Team Program(2019ZT08L075)+1 种基金the National Natural Science Foundation of China(22275058,U20A6002)supported by the National Research Foundation of the Republic of Korea(NRF)grant funded by the Republic of Korea Government(MSIP)(2021R1A2C3004202)。
文摘Polythiophenes(PTs)are prospective polymer donors for large-scale manufacturing and industrialization owing to their simple structures and low synthetic cost.However,the fabrication of PT solar cells depends on highly toxic chlorinated solvents,and less research has been done on the use of more environmentally friendly non-halogenated solvents.Herein,highly efficient PT solar cells based on top-performance polythiophene,P5TCN-F25,processed from a non-halogenated solvent are reported by delicate aggregation control.A power conversion efficiency of up to 15.68%was achieved by depositing the active layer from a hot o-xylene solution,which is the record efficiency of non-halogenated processed PT solar cells up to date.The appropriate solution temperature is beneficial to the formation of ordered polymer stacking and desirable phase separation size,which thereby contributes to enhanced charge transfer efficiency,more balanced hole/electron mobility,and reduced trap-assisted recombination.These results provide valuable implications for improving the efficiency of PT solar cells via environmentallyfriendly processing.
文摘Chemosensor arrays have a great potential for on-site applications in real-world scenarios.However,to fabricate on chemosensor array a number of chemosensors are required to obtain various optical patterns for multianalyte detection.Herein,we propose a minimized chemosensor array composed of only two types of carboxylate-functionalized polythiophene derivatives for the detection of eight types of metal ions.Upon recognition of the metal ions,the polythiophenes exhibited changes in their fluorescence intensity and various spectral shifts.Although both chemosensors have the same polymer backbone and recognition moiety,only the difference in the number of methylene groups contributed to the difference in the fluorescence response patterns.Consequently,the metal ions in aqueous media were successfully discriminated qualitatively and quantitatively by the chemosensor microarray on the glass chip.This study offers an approach for achieving a minimized chemosensor array just by changing the alkyl chain lengths without the necessity for many receptors and reporters.
基金supported by the National Natural Science Foundation of China(52073207,22075200,51703158,51933008)supported by the Peiyang Scholar Program of Tianjin University+2 种基金the Open Fund of the State Key Laboratory of Luminescent Materials and Devices(South China University of Technology,2020skllmd-11)Peiyang Young Junior Faculty Program of Tianjin University(2019XRG-0021)Independent Innovation Fund of Tianjin University(2020XZC-0105)。
文摘Polythiophenes,with merits of low cost and high scalability of synthesis,have received growing interest in organic solar cells.To date,the best-performing polythiophene:nonfullerene solar cells exhibit typical power conversion efficiencies (PCEs) of 10%–12%,which is much lower than those employing PM6-and D18-type polymers.This inferior performance is mostly limited by the improper miscibility between polythiophene and acceptors.Efforts on engineering the molecular structure to systematically tune the miscibility are required.With the aid of group contribution calculations,the miscibility of polythiophene:nonfullerene blend system was finely tuned by varying the ratios of siloxane-terminated chains and alkyl chains in ester-substituted polythiophenes through random copolymerization.Based on a series of the polythiophene and nonfullerene acceptors,the detailed analysis of blend miscibility and performance reveals a surprising anticorrelation between the Flory-Huggins interaction parameter (χ_(aa)) and the optimal time of solvent vapor annealing for device performance across these systems.Primarily due to the slightly higher χ_(aa),the blend of PDCBT-Cl-Si5 and ITIC-Th1 results in a record-high PCE of 12.85%in polythiophene:nonfullerene solar cells.The results not only provide a calculation-guided approach for molecular design but also prove that precise control of the miscibility is an effective way to design high-performance polythiophene:nonfullerene blends and beyond.
基金financially supported by the Fundamental Research Funds for the Central Universities(No.30920021107)the National Natural Science Foundation of China(No.51702161)。
文摘Electrical and magnetic properties are two crucial factors for the designing of broadband electromagnetic wave absorption(EWA)materials.In this work,we synthesized various magnetic metal sulfides/carbon(M_(x)S_(y)/C)nanocomposites from the precursor complex of metal in microporous polythiophene(MPT),and systematically investigated their EWA properties and mechanism.The characterization results indicate that M_(x)S_(y) were determined to be Fe_(7)S_(8)/C,Co_(9)S_(8)/C and Ni_(4)S_(3)/C,respectively.It is observed that M_(x)S_(y)/C nanocomposites exhibit remarkable EWA performances,where the maximal absorption gets to-51.3 dB,and efficient absorption can be realized in 10.32-18 GHz(7.68 GHz),which is superior to most reported magnetic carbonaceous EWA composites.Beside,the efficient absorption can be tuned to cover Ku band X band,demonstrating their great potential in practical applications.Improved conductance loss,obvious polarization relaxation,and apparent eddy current loss are deemed to make the predominant contributions to the high-performance EWA.This research opens up the exploration of novel nanocomposite coupling dielectric loss and magnetic loss using MPT-metal complex precursor for EWA applications.
基金National Key Research and Development Program of China,Grant/Award Number:2019YFE0116700Basic and Applied Basic Research Major Program of Guangdong Province,Grant/Award Number:2019B030302007National Natural Science Foundation of China,Grant/Award Numbers:21835006,91633301,22075017。
文摘At present,most of state-of-the-art power conversion efficiencies(PCEs)of organic solar cells(OSCs)are achieved from the photoactive materials involving donor–acceptor(D–A)copolymer donors.It is well known that the complicated molecular structure of D–A copolymers means the tedious synthesis,which brings about severe cost issue and poor scalability for the industrial production.Therefore,to develop application-oriented OSCs,considerable attention should be paid on simplifying the chemical structures of polymer donors.Polythiophene(PT)and poly(thiophene vinylene)(PTV)derivatives should be among the simplest polymer donors,and OSCs based on them have made some breakthroughs in past 2 years.Here,we briefly introduce the recent advances of OSCs based on low-cost polymers including poly(3-hexylthiophene)(P3HT),PT derivatives,and PTV derivatives,respectively,and emphasize the importance of modulating energy levels,preaggregation effect,and D/A miscibility for the past progress as well as the future development.At last,we also propose some challenges demanding prompt solution for realizing practical application of OSCs,aiming at providing guidance and stimulating new ideas for further research.
基金supported by the National Natural Science Foundation of China.
文摘A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.
基金financially supported by the National Natural Science Foundation of China(Nos.21274158 and 91333114)the National Research Laboratory Program of the Korea Science and Engineering Foundation(KOSEF)+1 种基金the World Class University Program(No.R32-2008-000-10142-0)the Center for Nanoscale Mechatronics&Manufacturing(08K140100414,CNMM)
文摘In this study, we demonstrate a novel method for fabricating polythiophene patterns, i.e., cylindrical holes and cylinders, through blending of a thermally curable polythiophene carrying with tertiary ester groups(PT-tert-ESTER) and poly(methyl methacrylate)(PMMA), followed by thermal conversion of the PT-tert-ESTER to an insoluble polythiophene via low-temperature cleavage of the tertiary ester groups and removal of the PMMA component via ultraviolet degradation. We show that the surface polarity of substrates, the mass ratio of PT-tert-ESTER to PMMA in the blend solutions as well as the concentration of the blend solutions strongly influence the formation of the polythiophene patterns. Cylindrical holes are more readily formed on less polar substrates when a PT-tert-ESTER dominated blend solution is used, while cylinders are more readily formed on more polar substrates when a PMMA dominated blend solution is used. Moreover, the diameters of both the cylindrical holes and the cylinders decrease as the PT-tert-ESTER concentration is increased in the respective ranges of the PT-tert-ESTER/PMMA ratios where the patterns are formed. Grazing incident X-ray diffraction data have indicated that the patterning of the PT-tert-ESTER component in the blend films improves the crystallinity of PT-tert-ESTER as well as the molecular packing of the insoluble polythiophene in the resultant patterned polythiophene films.
基金the financial support from the Basic and Applied Basic Research Major Program of Guangdong Province(No.2019B030302007)the National Natural Science Foundation of China(Nos.21835006,91633301 and 22075017)+1 种基金the Fundamental Research Funds for the Central Universities,China(No.FRF-TP-19-047A2)Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-201903)。
文摘The power conversion efficiencies(PCEs)of organic solar cells(OSCs)have reached 18%recently,which have already met the demand of practical application.However,these outstanding results were generally achieved with donor-acceptor(D-A)type copolymer donors,which can hardly fulfill the low-cost largescale production due to their complicated synthesis processes.Therefore,developing polymer donors with simple chemical structures is urgent for realizing low-cost OSCs.Polythiophene(PT)derivatives are currently regarded as promising candidates for such kind of donor materials,which has been illustrated in many works.In this work,two new alkylthio substituted PT derivatives,P301 and P302,were synthesized and tested as donors in the OSCs using Y5 as the accepto r.In comparison,the introduction of fluorine atoms on the backbone of P302 can not only downshift the energy levels,but also greatly improve the phase separation morphologies of the active layers,which is ascribed to the enhanced aggregation effect and the reduced miscibility with the non-fullerene acceptor.As a result,the P302:Y5-based OSC exhibits a significantly improved PCE of 9.65%than that of P301:Y5-based one,indicating the important role of fluorination in the construction of efficient PT derivative donors.
基金financially supported by the National Natural Science Foundation of China(No.31871877)Chinese Universities Scientific Fund(Nos.2018QC151,2019TC036)+1 种基金the"Talents Scheme"Program of Beijing(No.31050003)the Research Fund Program of Guangdong Provincial Key Laboratory of Radionuclides Pollution Control and Resources(No.2017B030314182)。
文摘A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The approach relies on the formation of supramolecular polythiophene assemblies in the presence of PA through electrostatic,charge transfer and π-π stacking interactions.This probe could be utilized for the rapid and visual detection of PA both in aqueous solution and solid support with high specificity and sensitivity.The detection limit of this sensor is as low as 5.0 × 10^-8 mol/L.
文摘Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to-tail unit,the p-doping occurs at a similar rate.The reaction between poly(3-dodecylthiophene),P3DodTh,and the acid takes place more rapidly.P3OBuTh with a butoxy substituent undergoes more facile p-doping and receives photochemical reaction with CHCl3,and this reaction obeys a pseudo-first-order rate law with a rate constant kobs of 1.42×10-5s-1at room tempera- ture.
基金Supported by the National Nature Science Foundation of China(No.21176193)
文摘One conjugated polymer consisting of carbazole and 3-hexylthiophene moiety, poly(N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole)(PNDC), has been synthesized by ferric chloride oxidative polymerization. The monomer N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole was synthesized and characterized by IR, 1H-NMR, 13C-NMR and MS. UV-vis absorption spectrum, fluorescence spectrum, photoluminescence spectrum and electrochemical properties of the polymer were investigated. Polymer PNDC shows maximum peak appearing at 394 nm in UV-vis absorption spectrum, strongest fluorescence-emission at 482 nm in fluorescence spectrum and maximum emission peak at 492 nm in photoluminescence spectrum. The band-gap(Eg), HOMO energy(EHOMO), and LUMO energy(ELUMO) of the polymer were obtained as 2.58,-5.32, and-2.74 e V, respectively.
