Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-gro...Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-group py-razolinones have the advantages of simple synthesis steps,low cost and environmental friendliness,compared to the classical end-group dicyanomethyleneindianone.The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation,UV-vis absorption,cyclic voltammetry,X-ray diffraction and space charge limited current.It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm,with a moderate band gap of nearly 1.7 eV.At the same time,the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored.It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.展开更多
The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells(OSCs) based on non-fused ring electron acceptors(NFREAs).However,research on the impac...The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells(OSCs) based on non-fused ring electron acceptors(NFREAs).However,research on the impact of fluorination positions at side chains on NFREAs device performance remains scant.In this study,we introduce two isomeric NFREAs,designated as GA-2F-E and GA-2F,distinguished by their fluorination positions at the side chains.Both NFREAs share a thiophene[3,2-b]thiophene core,but their side chains differ:GA-2F-E features two(4-butylphenyl)-N-(4-fluorophenyl) amino groups,whereas GA-2F's side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core.To delve into the influence of fluorination positions on the optoelectronic properties,aggregation behavior,and overall efficiency of the acceptor molecules,a comprehensive investigation was conducted.The findings reveal that,despite similar photophysical properties and comparable absorption bandwidths,GA-2F-E,with fluorine atoms positioned on both sides of the molecular framework,demonstrates more compact π-π stacking,reduced bimolecular recombination,superior exciton transport,and a more balanced,higher mobility.As a result of these advantages,OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency(PCE) of 16.45 %,surpassing the 15.83 %PCE of devices utilizing D18:GA-2F.This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance,paving the way for the development of more efficient NFREAs.展开更多
Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have be...Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have been developed with A-π_A-π_D-D-π_D-π_A-A non-fused structures. It is revealed that the introduction of electron deficient π-bridge(π_A) and multiple intramolecular noncovalent interactions effectively retained the structural planarity and intramolecular charge transfer of NFRAs, extending strong NIR photon absorption up to 950 nm. Further, the chlorinated acceptor, with the enlarged π-surface compared to the fluorinated counterpart, promoted not only molecular stacking in solid, but also the desirable photochemical stability in ambient, which are helpful to thereby improve the exciton and charge dynamics for the corresponding OPVs. Overall, this work provides valuable insights into the design of NIR organic semiconductors.展开更多
Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement come...Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement comes from fused ring electron acceptors(FREAs)with complex structures,leading to high cost.Hence,it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells.Recently,great progress has been made in fully non-fused ring electron acceptors(NFREAs)with only single-aromatic ring in the electron-donating core,which might achieve a fine balance between the efficiency and cost,thus accelerating the commercial application of organic solar cells.Therefore,this article summarizes the recent advances of fully NFREAs with efficiency over 10%,which may provide a guidance for developing the cost-effective solar cells.展开更多
To develop photovoltaics embracing the both features of high performance and low cost has drawn attentions of researchers,yet representing the significant challenges.In this work,two non-fused ring acceptors(NFRAs),na...To develop photovoltaics embracing the both features of high performance and low cost has drawn attentions of researchers,yet representing the significant challenges.In this work,two non-fused ring acceptors(NFRAs),namely p-PTIC4Cl and t-PTIC4Cl,were developed via a short synthetic route.By tethering unaxisymmetric aromatic chains to thienyl bridge of NFRAs,we revealed that the tuning of aromatic chains allows modulating the self-assembly and stacking of NFRAs in solid,hence influencing their optoelectronic and photovoltaic properties.As results,p-PTIC4Cl,consisting of 3-hexylbenzene with large axial angle to backbone,can achieve superior PCE of 11.30%than that of t-PTIC4Cl with 2-hexylthiophene chains(PCE of 6.49%),when pairing with polymer donor PBDB-TF.Despite of the only subtle structural difference,the p-PTIC4Cl based blend films possess better exciton dissociation and charge transfer rates,as well as photostability,to those of t-PTIC4Cl based blends.展开更多
Non-fused ring electron acceptors(NFREAs)have a broad application prospect in the commercialization of organic solar cells(OSCs)due to the advantages of simple synthesis and low cost.The selection of intermediate bloc...Non-fused ring electron acceptors(NFREAs)have a broad application prospect in the commercialization of organic solar cells(OSCs)due to the advantages of simple synthesis and low cost.The selection of intermediate block cores of non-fused frameworks and the establishment of the relationship between molecular structure and device performance are crucial for the realization of high-performance OSCs.Herein,two A-D-A’-D-A type NFREAs namely CBTBO-4F and CBTBO-4Cl,constructed with a novel electron-deficient block unit N-(2-butyloctyl)-carbazole[3,4-c:5,6-c]bis[1,2,5]thiadiazole(CBT)and bridging unit 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene(DTC)coupling with different terminals(IC-2F/2Cl),were designed and synthesized.The two NFREAs feature broad and strong photoresponse from 500 nm to 900 nm due to the strong intramolecular charge transfer characteristics.Compared with CBTBO-4F,CBTBO-4Cl shows better molecular planarity,stronger crystallinity,more ordered molecular stacking,larger van der Waals surface,lower energy level and better active layer morphology,contributing to much better charge separation and transport behaviors in its based devices.As a result,the CBTBO-4Cl based device obtains a higher power conversion efficiency of 10.18%with an open-circuit voltage of 0.80 V and a short-circuit current density of 21.20 mA/cm^(2).These results not only demonstrate the great potential of CBT,a new building block of the benzothiazole family,in the construction of high-performance organic conjugated semiconductors,but also suggest that the terminal chlorination is an effective strategy to improve device performance.展开更多
Low-cost photovoltaic materials are essential for realizing large-scale commercial applications of organic solar cells(OSCs).However,highly efficient OSCs based on low-cost photovoltaic materials are scarce due to a d...Low-cost photovoltaic materials are essential for realizing large-scale commercial applications of organic solar cells(OSCs).However,highly efficient OSCs based on low-cost photovoltaic materials are scarce due to a deficiency in understanding the structure-property relationship.Herein,we investigated two low-cost terthiophene-based electron acceptors,namely,3TC8 and 3TEH,with 3,4-bis(octan-3-yloxy)thiophene,differing only in the alkylated thiophene-bridges.Both acceptors exhibit low optical gaps(∼1.43 eV)and possess deep highest occupied molecular orbital(HOMO)levels(∼−5.8 eV).Notably,the single-crystal structure of 3TEH demonstrates highly planar conjugated backbone and strongπ-πstacking between intermolecular terminal groups,attributed to the presence of the bulky alkylated noncovalently conformational locks.Upon utilizing both acceptors to fabricate OSCs,the 3TC8-based device exhibited a power conversion efficiency(PCE)of 11.1%,while the 3TEH-based OSC demonstrated an excellent PCE of 14.4%.This PCE is the highest among OSCs based on terthiophene-containing electron acceptors.These results offer a new strategy for designing low-cost electron acceptors for highly efficient OSCs.展开更多
文摘Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-group py-razolinones have the advantages of simple synthesis steps,low cost and environmental friendliness,compared to the classical end-group dicyanomethyleneindianone.The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation,UV-vis absorption,cyclic voltammetry,X-ray diffraction and space charge limited current.It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm,with a moderate band gap of nearly 1.7 eV.At the same time,the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored.It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.
基金financially supported by the National Natural Science Foundation of China (Nos.22375024,21975031,51933001,and 21734009)。
文摘The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells(OSCs) based on non-fused ring electron acceptors(NFREAs).However,research on the impact of fluorination positions at side chains on NFREAs device performance remains scant.In this study,we introduce two isomeric NFREAs,designated as GA-2F-E and GA-2F,distinguished by their fluorination positions at the side chains.Both NFREAs share a thiophene[3,2-b]thiophene core,but their side chains differ:GA-2F-E features two(4-butylphenyl)-N-(4-fluorophenyl) amino groups,whereas GA-2F's side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core.To delve into the influence of fluorination positions on the optoelectronic properties,aggregation behavior,and overall efficiency of the acceptor molecules,a comprehensive investigation was conducted.The findings reveal that,despite similar photophysical properties and comparable absorption bandwidths,GA-2F-E,with fluorine atoms positioned on both sides of the molecular framework,demonstrates more compact π-π stacking,reduced bimolecular recombination,superior exciton transport,and a more balanced,higher mobility.As a result of these advantages,OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency(PCE) of 16.45 %,surpassing the 15.83 %PCE of devices utilizing D18:GA-2F.This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance,paving the way for the development of more efficient NFREAs.
基金funded by National Natural Science Foundation of China (No.22125901)the National Key Research and Development Program of China (No.2019YFA0705900)the Fundamental Research Funds for the Central Universities (No.226–2023–00113)。
文摘Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have been developed with A-π_A-π_D-D-π_D-π_A-A non-fused structures. It is revealed that the introduction of electron deficient π-bridge(π_A) and multiple intramolecular noncovalent interactions effectively retained the structural planarity and intramolecular charge transfer of NFRAs, extending strong NIR photon absorption up to 950 nm. Further, the chlorinated acceptor, with the enlarged π-surface compared to the fluorinated counterpart, promoted not only molecular stacking in solid, but also the desirable photochemical stability in ambient, which are helpful to thereby improve the exciton and charge dynamics for the corresponding OPVs. Overall, this work provides valuable insights into the design of NIR organic semiconductors.
基金The authors gratefully acknowledge the financial support from National Natural Science Foundation of China(NSFC,Nos.51973169 and 52003209)the Open Project Program of Wuhan National Laboratory for Optoelectronics(No.2020WNLOKF015)the Science Foundation of Wuhan Institute of Technology(Nos.K202023 and K202025).
文摘Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement comes from fused ring electron acceptors(FREAs)with complex structures,leading to high cost.Hence,it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells.Recently,great progress has been made in fully non-fused ring electron acceptors(NFREAs)with only single-aromatic ring in the electron-donating core,which might achieve a fine balance between the efficiency and cost,thus accelerating the commercial application of organic solar cells.Therefore,this article summarizes the recent advances of fully NFREAs with efficiency over 10%,which may provide a guidance for developing the cost-effective solar cells.
基金This work was financially supported by the National Natural Science Foundation of China(No.22125901)National Key Research and Development Program of China(No.2019YFA0705900).
文摘To develop photovoltaics embracing the both features of high performance and low cost has drawn attentions of researchers,yet representing the significant challenges.In this work,two non-fused ring acceptors(NFRAs),namely p-PTIC4Cl and t-PTIC4Cl,were developed via a short synthetic route.By tethering unaxisymmetric aromatic chains to thienyl bridge of NFRAs,we revealed that the tuning of aromatic chains allows modulating the self-assembly and stacking of NFRAs in solid,hence influencing their optoelectronic and photovoltaic properties.As results,p-PTIC4Cl,consisting of 3-hexylbenzene with large axial angle to backbone,can achieve superior PCE of 11.30%than that of t-PTIC4Cl with 2-hexylthiophene chains(PCE of 6.49%),when pairing with polymer donor PBDB-TF.Despite of the only subtle structural difference,the p-PTIC4Cl based blend films possess better exciton dissociation and charge transfer rates,as well as photostability,to those of t-PTIC4Cl based blends.
基金This work was financially supported by the National Natural Science Foundation of China(NSFC,Nos.51973032,21905043 and 51833004)the“Chenguang Program”supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(No.19CG36)+4 种基金the Jiangxi Provincial Natural Science Foundation(Nos.20212ACB203005 and 20212BAB213018)the Thousand Talents Plan of Jiangxi Province(No.jxsq2019101051)the Jiangxi Provincial Education Department Science and Technology Research Foundation(No.GJJ210310)X.Xia and X.Lu acknowledge the financial support from Research Grants Council(RGC)of Hong Kong(General Research Fund No.14303519)Y.Chen expresses thanks for the support from the Fundamental Research Funds for the Central Universities and Graduate Student Innovation Fund of Donghua University(No.CUSF-DH-D-2021008).
文摘Non-fused ring electron acceptors(NFREAs)have a broad application prospect in the commercialization of organic solar cells(OSCs)due to the advantages of simple synthesis and low cost.The selection of intermediate block cores of non-fused frameworks and the establishment of the relationship between molecular structure and device performance are crucial for the realization of high-performance OSCs.Herein,two A-D-A’-D-A type NFREAs namely CBTBO-4F and CBTBO-4Cl,constructed with a novel electron-deficient block unit N-(2-butyloctyl)-carbazole[3,4-c:5,6-c]bis[1,2,5]thiadiazole(CBT)and bridging unit 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene(DTC)coupling with different terminals(IC-2F/2Cl),were designed and synthesized.The two NFREAs feature broad and strong photoresponse from 500 nm to 900 nm due to the strong intramolecular charge transfer characteristics.Compared with CBTBO-4F,CBTBO-4Cl shows better molecular planarity,stronger crystallinity,more ordered molecular stacking,larger van der Waals surface,lower energy level and better active layer morphology,contributing to much better charge separation and transport behaviors in its based devices.As a result,the CBTBO-4Cl based device obtains a higher power conversion efficiency of 10.18%with an open-circuit voltage of 0.80 V and a short-circuit current density of 21.20 mA/cm^(2).These results not only demonstrate the great potential of CBT,a new building block of the benzothiazole family,in the construction of high-performance organic conjugated semiconductors,but also suggest that the terminal chlorination is an effective strategy to improve device performance.
基金supported by the Beijing Natural Science Foundation of China(Z230019,2212005)the National Natural Science Foundation of China(NSFC 22173062,21833005,22090022 and 22275125).
文摘Low-cost photovoltaic materials are essential for realizing large-scale commercial applications of organic solar cells(OSCs).However,highly efficient OSCs based on low-cost photovoltaic materials are scarce due to a deficiency in understanding the structure-property relationship.Herein,we investigated two low-cost terthiophene-based electron acceptors,namely,3TC8 and 3TEH,with 3,4-bis(octan-3-yloxy)thiophene,differing only in the alkylated thiophene-bridges.Both acceptors exhibit low optical gaps(∼1.43 eV)and possess deep highest occupied molecular orbital(HOMO)levels(∼−5.8 eV).Notably,the single-crystal structure of 3TEH demonstrates highly planar conjugated backbone and strongπ-πstacking between intermolecular terminal groups,attributed to the presence of the bulky alkylated noncovalently conformational locks.Upon utilizing both acceptors to fabricate OSCs,the 3TC8-based device exhibited a power conversion efficiency(PCE)of 11.1%,while the 3TEH-based OSC demonstrated an excellent PCE of 14.4%.This PCE is the highest among OSCs based on terthiophene-containing electron acceptors.These results offer a new strategy for designing low-cost electron acceptors for highly efficient OSCs.
