The secular variation in the global geomagnetic field was analyzed in terms of the annual differences in monthly means by using the hourly mean data from 18 foreign(outside China)observatories of the World Data Center...The secular variation in the global geomagnetic field was analyzed in terms of the annual differences in monthly means by using the hourly mean data from 18 foreign(outside China)observatories of the World Data Center(WDC)for Geomagnetism from January 2010 to January 2020 as well as 9 observatories in the Geomagnetic Network of China from January 2015 to April 2021.In addition,according to the correlation of noisy components from the observatories,a covariance matrix was constructed based on residuals between observations and the CHAOS-7.4 model to remove external contamination.Through a comparison before and after denoising,we found that the overall average standard deviations were reduced by 29.97%in China and by 41.4%outside China.Results showed the correlation coefficient between external noise(mainly the magnetosphere ring current)and the Dst index was 0.82,and the correlation coefficient between external noise and the Ring Current(RC)index reached 0.94.A geomagnetic jerk was globally discovered around 2018.0 on the geomagnetic eastward component Y.The jerk timing in China was around 2020.0,and the earliest one was in2018.75,whereas the timing outside China was around 2018.0,and the earliest one was in 2017.67.This 2-year lag may have been caused by the higher electrical conductivity of the deep mantle.After more data were added,this jerk event was found to occur in an orderly manner in the northern hemisphere as the longitude increased and the intensity gradually increased as well.The variations in location of the jerk center were analyzed according to the CHAOS-7.4 model.Results revealed six extreme points distributed nearby the equator.The strongest was near the equator,at 170°E,and the strength gradually decreased as it extended to the northern and southern hemispheres.Another extreme point with the opposite sign was located at the equator,at 20°W,in the south-central part of the Atlantic,and the strength gradually decreased as it extended into Europe.The covariance matrix method can be used to analyze data from the Macao Science Satellite-1 mission in the future,and this method is expected to play a positive role in modeling and separating the large-scale external field.展开更多
It is generally accepted that the uniaxial compressive strength(UCS)and P-wave velocity of rocks tend to decrease simultaneously with increasing temperature.However,based on a great number of statistical data and syst...It is generally accepted that the uniaxial compressive strength(UCS)and P-wave velocity of rocks tend to decrease simultaneously with increasing temperature.However,based on a great number of statistical data and systematic analysis of the microstructure variation of rocks with temperature rising and corresponding propagation mechanism of elastic wave,the results show that(1)There are three different trends for the changes of UCS and P-wave velocity of sandstone when heated from room temperature(20C or 25C)to 800C:(i)Both the UCS and P-wave velocity decrease simultaneously;(ii)The UCS increases initially and then decreases,while the P-wave velocity decreases continuously;and(iii)The UCS increases initially and then fluctuates,while the P-wave velocity continuously decreases.(2)The UCS changes at room temperaturee400C,400Ce600C,and 600Ce800C are mainly attributed to the discrepancy of microstructure characteristics and quartz content,the transformation plasticity of clay minerals,and the balance between the thermal cementation and thermal damage,respectively.(3)The inconsistency in the trends of UCS and P-wave velocity changes is caused by the change of quartz content,phase transition of water and certain minerals.展开更多
The sufficient bond between concrete and rock is an important prerequisite to ensure the effect of shotcrete support. However, in cold regions engineering protection system, the bond condition of rock and concrete sur...The sufficient bond between concrete and rock is an important prerequisite to ensure the effect of shotcrete support. However, in cold regions engineering protection system, the bond condition of rock and concrete surface is easily affected by freeze-thaw cycles, resulting in interface damage, debonding and even supporting failure. Understanding the micromechanisms of the damage and debonding of the rock-concrete interface is essential for improving the interface protection.Therefore, the micromorphology, micromechanical properties, and microdebonding evolution of the sandstone-concrete interface transition zone(ITZ) under varying freeze-thaw cycles(0, 5, 10, 15, 20) were studied using scanning electron microscope, stereoscopic microscope, and nano-indentation. Furthermore, the distribution range and evolution process of ITZ affected by freeze-thaw cycles were defined. Major findings of this study are as follows:(1) The microdamage evolution law of the ITZ under increasing freeze-thaw cycles is clarified, and the relationship between the number of cracks in the ITZ and freeze-thaw cycles is established;(2) As the number of freeze-thaw cycles increases, the ITZ's micromechanical strength decreases, and its development width tends to increase;(3) The damage and debonding evolution mechanisms of sandstone-concrete ITZ under freeze-thaw cycles is revealed, and its micromechanical evolution model induced by freeze-thaw cycles is proposed.展开更多
The development of A-DA′D-A type small molecule acceptors(SMAs)has promoted the rapid progress of polymer solar cells(PSCs)in recent years.The outer side chains on the terminal thiophene ring and inner side chains on...The development of A-DA′D-A type small molecule acceptors(SMAs)has promoted the rapid progress of polymer solar cells(PSCs)in recent years.The outer side chains on the terminal thiophene ring and inner side chains on nitrogen atoms of the pyrrole ring of the DA′D fused ring play important roles in the photovoltaic performance of the SMAs.Here,we synthesized two new SMAs,2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-bis(4-(2-ethylhexyl)thiophen-2-yl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(T2EH)and 2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-bis(3-(2-ethylhexyl)phenyl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)(P2EH),with 2-ethylhexylβ-substituted thienyl or phenyl as the outer side chains,respectively,to improve the photovoltaic properties of the SMAs.Compared with P2EH,T2EH exhibits closerπ−πstacking,slightly red-shifted absorption,and higher electron mobility.Moreover,the active layer of T2EH blended with the low-cost polymer donor poly[(thiophene)-alt-(6,7-difluoro-2-(2-hexyldecyloxy)quinoxaline)](PTQ10)possesses higher mobilities,a longer lifetime,and less recombination of the charge carriers in comparison with that of the PTQ10:P2EH active layer.Eventually,the PTQ10:T2EH-based PSCs showed an outstanding power conversion efficiency(PCE)of 18.55%,while the PSC based on PTQ10:P2EH displayed a PCE of 17.50%.Importantly,18.55%is the highest PCE in the PTQ10-based binary PSCs so far.The results indicate that T2EH is one of the best SMAs for the PTQ10-based PSCs and is a promising SMA for the application of PSCs.展开更多
Side chain engineering with fluorine substitution is widely used to enhance photovoltaic performance of polymer donors in the research field of polymer solar cells(PSCs).However,fluorine substitution has disadvantages...Side chain engineering with fluorine substitution is widely used to enhance photovoltaic performance of polymer donors in the research field of polymer solar cells(PSCs).However,fluorine substitution has disadvantages of complicated synthesis and high cost.Herein,we synthesized a novel D-A copolymer donor PBQ9 based on difluoroquinoxaline A-unit with chlorine substitution on its alkyl-thiophene side chains instead of fluorine substitution in the polymer donor PBQ6,which greatly shortens the synthetic route and reduces the cost.Interestingly,the optimized binary PSC with PBQ9 as polymer donor and m-TEH as acceptor demonstrated a high power conversion efficiency(PCE)of 18.81%(certified PCE of 18.33%by National Institute of Metrology,China)with a high fill factor of 80.59%,and the photovoltaic performance of the PSCs is insensitive to the different batches of the polymer donor.The results indicate that PBQ9 is a high-performance polymer donor and that chlorine substitution is an effective strategy to improve photovoltaic performance and reduce the cost of polymer donors.展开更多
The power conversion efficiency(PCE)of polymer solar cells(PSCs)has recently increased quickly,propelling PSCs closer to large-scale commercialization.However,several critical issues,such as the cost of materials and ...The power conversion efficiency(PCE)of polymer solar cells(PSCs)has recently increased quickly,propelling PSCs closer to large-scale commercialization.However,several critical issues,such as the cost of materials and the sensitivity of the PCE to active-layer thickness,must be addressed before industrial application can be realized on a large scale.Here,we fabricated a high-performance ternary PSC based on a low-cost polymer donor PTQ10 and an A-DA’D-A-type small molecule acceptor(SMA)2,2'-((2Z,2'Z)-((12,13-bis(2-butyloctyl)-3,9-bis(4-(2-ethylhexyl)thiophen-2-yl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(m-TEH)with a newA-DA’D-A-type SMA 2,2'-((2Z,2'Z)-((12,13-bis(2-butyloctyl)-3,9-bis(3-(2-ethylhexyl)phenyl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(m-PEH)(with phenyl outer side chains)as the third component.Benefitting from the good compatibility and the unique alignment of the energy levels between PTQ10 and the two SMAs,the ternary system showed favorable phase separation and dominant face-on orientation,exhibiting suitable film morphology and enhanced charge transport.Therefore,the optimized ternary PSCs based on PTQ10∶m-TEH∶m-PEH(1.0∶0.9∶0.3,w/w/w)demonstrated an outstanding PCE of 19.34%,which is one of the highest PCEs reported for the single junction PSCs to date.More importantly,the ternary PSCs demonstrated superior tolerance to the active-layer thickness and showed a high PCE of 18.02% with a high fill factor(FF)of 76.56% for the devices with the active-layer thickness even reaching 300 nm.These results indicate that the ternary devices based on PTQ10∶m-TEH∶m-PEH are highly promising for future large-area fabrication and commercial application of PSCs.展开更多
Recently,all-polymer solar cells(all-PSCs) based on polymerized small molecule acceptors(PSMAs) have achieved significant progress.Ternary blending has proven to be an effective strategy to further boost the power con...Recently,all-polymer solar cells(all-PSCs) based on polymerized small molecule acceptors(PSMAs) have achieved significant progress.Ternary blending has proven to be an effective strategy to further boost the power conversion efficiency(PCE) of the all-PSCs.Herein,a new A-DA′D-A small-molecule acceptor-based PSMA(named as PYCl-T) was designed and synthesized,which possesses similar polymer backbone with the widely used PY-IT,but with chlorine substitution on the A-end groups in the A-DA′D-A structure.PYCl-T was then employed as the third component into the PM6:PY-IT system and the ternary all-PSCs based on PM6:PY-IT:PYCl-T demonstrated a high PCE of 16.62%(certified value of 16.3%).Moreover,the PCE of 15.52% was realized in the enlarged ternary all-PSCs with effective area of 1 cm^(2),indicating the great potential in large-scale applications.Moreover,the optimized ternary blend films of PM6:PY-IT:PYCl-T show excellent thermal stability at 150 ℃.This work demonstrates that the utilization of a ternary blend system involving two well-compatible PSMA polymer acceptors is an effective strategy to boost the performance of the all-PSCs.展开更多
Poor stability of spiro-OMe TAD hole transport materials(HTMs)with dopant is a major obstacle for the commercialization of perovskite solar cells(pero-SCs).Herein,we demonstrate a series of quinoxaline-based D-A copol...Poor stability of spiro-OMe TAD hole transport materials(HTMs)with dopant is a major obstacle for the commercialization of perovskite solar cells(pero-SCs).Herein,we demonstrate a series of quinoxaline-based D-A copolymers PBQ5,PBQ6 and PBQ10 as the dopant-free polymer HTMs for high performance pero-SCs.The D-A copolymers are composed of fluorothienyl benzodithiophene(BDTT)as D-unit,difluoroquinoxaline(DFQ)with different side chains as A-unit,and thiophene asπ-bridge,where the side chains on the DFQ unit are bi-alkyl for PBQ5,bi-alkyl-fluorothienyl for PBQ6,and alkoxyl for PBQ10.All the three copolymers are adopted as the dopant-free HTM in the pero-SCs.The planar n-i-p structured pero-SCs based on(FAPb I_(3))_(0.98)(MAPb Br_(3))_(0.02)with PBQ6 HTM demonstrated the high power conversion efficiency(PCE)of 22.6%with Vocof1.13 V and FF of 80.8%,which is benefitted from the suitable energy level and high hole mobility of PBQ6.The PCE of 22.6%is the highest efficiency reported in the n-i-p structured pero-SCs based on dopant-free D-A copolymer HTM.In addition,the peroSCs show significantly enhanced ambient,thermal and light-soaking stability compared with the devices with traditional spiroOMe TAD HTM.展开更多
D-A copolymerization is a broadly utilized molecular design strategy to construct high efficiency photovoltaic materials for polymer solar cells(PSCs),and all the D-A copolymer donors reported till now are the alterna...D-A copolymerization is a broadly utilized molecular design strategy to construct high efficiency photovoltaic materials for polymer solar cells(PSCs),and all the D-A copolymer donors reported till now are the alternate D-A copolymers with equal D-and A-units.Here,we first propose a non-equivalent D-A copolymerization strategy with unequal D-and A-units,and develop three novel non-equivalent D-A copolymer donors(PM6-D1,PM6-D2 and PM6-D3 with D/A unit ratio of 1.1:0.9,1.2:0.8 and1.3:0.7,respectively)by inserting more D units into the alternate D-A copolymer PM6 backbone to finely tune the physicochemical and photovoltaic properties of the polymers.The three non-equivalent D-A copolymers show the down-shifted highest occupied molecular orbital(HOMO)energy levels,higher hole mobility,higher degree of molecular self-assembly and higher molecular crystallinity with the increase of D-unit ratio in comparison with the alternate D-A copolymer PM6.As a result,all the three non-equivalent D-A copolymer-based PSCs with Y6 as acceptor achieve improved power conversion efficiency(PCE)with higher V_(oc),larger J_(sc)and higher FF simultaneously.Particularly,the PM6-D1:Y6 based PSC achieved a high PCE of17.71%,which is significantly higher than that(15.82%)of the PM6:Y6 based PSC and is one of the highest performances in the binary PSCs.展开更多
基金the support of the National Natural Science Foundation of China(Nos.42030203,41974073,41404053)the Macao Foundation and the pre-research project of Civil Aerospace Technologies(Nos.D020308 and D020303)+3 种基金which is funded by the China National Space Administrationsupport from the opening fund of the State Key Laboratory of Lunar and Planetary Sciences(Macao University of Science and Technology,Macao Science and Technology Development Fund[FDCT]No.119/2017/A3)the Specialized Research Fund for State Key Laboratoriesthe NUIST-Uo R International Research Institute。
文摘The secular variation in the global geomagnetic field was analyzed in terms of the annual differences in monthly means by using the hourly mean data from 18 foreign(outside China)observatories of the World Data Center(WDC)for Geomagnetism from January 2010 to January 2020 as well as 9 observatories in the Geomagnetic Network of China from January 2015 to April 2021.In addition,according to the correlation of noisy components from the observatories,a covariance matrix was constructed based on residuals between observations and the CHAOS-7.4 model to remove external contamination.Through a comparison before and after denoising,we found that the overall average standard deviations were reduced by 29.97%in China and by 41.4%outside China.Results showed the correlation coefficient between external noise(mainly the magnetosphere ring current)and the Dst index was 0.82,and the correlation coefficient between external noise and the Ring Current(RC)index reached 0.94.A geomagnetic jerk was globally discovered around 2018.0 on the geomagnetic eastward component Y.The jerk timing in China was around 2020.0,and the earliest one was in2018.75,whereas the timing outside China was around 2018.0,and the earliest one was in 2017.67.This 2-year lag may have been caused by the higher electrical conductivity of the deep mantle.After more data were added,this jerk event was found to occur in an orderly manner in the northern hemisphere as the longitude increased and the intensity gradually increased as well.The variations in location of the jerk center were analyzed according to the CHAOS-7.4 model.Results revealed six extreme points distributed nearby the equator.The strongest was near the equator,at 170°E,and the strength gradually decreased as it extended to the northern and southern hemispheres.Another extreme point with the opposite sign was located at the equator,at 20°W,in the south-central part of the Atlantic,and the strength gradually decreased as it extended into Europe.The covariance matrix method can be used to analyze data from the Macao Science Satellite-1 mission in the future,and this method is expected to play a positive role in modeling and separating the large-scale external field.
基金This work was supported by the National Natural Science Foundation of China(Grant No.41772333)the program of State Key Laboratory of Frozen Soil Engineering(Grant No.SKLFSE201713)the Shaanxi Province New-Star Talents Promotion Project of Science and Technology(Grant No.2019KJXX-049).
文摘It is generally accepted that the uniaxial compressive strength(UCS)and P-wave velocity of rocks tend to decrease simultaneously with increasing temperature.However,based on a great number of statistical data and systematic analysis of the microstructure variation of rocks with temperature rising and corresponding propagation mechanism of elastic wave,the results show that(1)There are three different trends for the changes of UCS and P-wave velocity of sandstone when heated from room temperature(20C or 25C)to 800C:(i)Both the UCS and P-wave velocity decrease simultaneously;(ii)The UCS increases initially and then decreases,while the P-wave velocity decreases continuously;and(iii)The UCS increases initially and then fluctuates,while the P-wave velocity continuously decreases.(2)The UCS changes at room temperaturee400C,400Ce600C,and 600Ce800C are mainly attributed to the discrepancy of microstructure characteristics and quartz content,the transformation plasticity of clay minerals,and the balance between the thermal cementation and thermal damage,respectively.(3)The inconsistency in the trends of UCS and P-wave velocity changes is caused by the change of quartz content,phase transition of water and certain minerals.
基金supported by the National Natural Science Foundation of China (Grant No.41772333)the National Natural Science Foundation of Shaanxi Province, China (Grant No.2018JQ5124)the New-Star Talents Promotion Project of Science and Technology of Shaanxi Province, China (Grant No.2019KJXX049)。
文摘The sufficient bond between concrete and rock is an important prerequisite to ensure the effect of shotcrete support. However, in cold regions engineering protection system, the bond condition of rock and concrete surface is easily affected by freeze-thaw cycles, resulting in interface damage, debonding and even supporting failure. Understanding the micromechanisms of the damage and debonding of the rock-concrete interface is essential for improving the interface protection.Therefore, the micromorphology, micromechanical properties, and microdebonding evolution of the sandstone-concrete interface transition zone(ITZ) under varying freeze-thaw cycles(0, 5, 10, 15, 20) were studied using scanning electron microscope, stereoscopic microscope, and nano-indentation. Furthermore, the distribution range and evolution process of ITZ affected by freeze-thaw cycles were defined. Major findings of this study are as follows:(1) The microdamage evolution law of the ITZ under increasing freeze-thaw cycles is clarified, and the relationship between the number of cracks in the ITZ and freeze-thaw cycles is established;(2) As the number of freeze-thaw cycles increases, the ITZ's micromechanical strength decreases, and its development width tends to increase;(3) The damage and debonding evolution mechanisms of sandstone-concrete ITZ under freeze-thaw cycles is revealed, and its micromechanical evolution model induced by freeze-thaw cycles is proposed.
基金support from the National Key Research and Development Program of China(no.2019YFA0705900)the NSFC(nos.51820105003,61904181,and 52173188)the Basic and Applied Basic Research Major Program of Guangdong Province(no.2019B030302007).
文摘The development of A-DA′D-A type small molecule acceptors(SMAs)has promoted the rapid progress of polymer solar cells(PSCs)in recent years.The outer side chains on the terminal thiophene ring and inner side chains on nitrogen atoms of the pyrrole ring of the DA′D fused ring play important roles in the photovoltaic performance of the SMAs.Here,we synthesized two new SMAs,2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-bis(4-(2-ethylhexyl)thiophen-2-yl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(T2EH)and 2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-bis(3-(2-ethylhexyl)phenyl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)(P2EH),with 2-ethylhexylβ-substituted thienyl or phenyl as the outer side chains,respectively,to improve the photovoltaic properties of the SMAs.Compared with P2EH,T2EH exhibits closerπ−πstacking,slightly red-shifted absorption,and higher electron mobility.Moreover,the active layer of T2EH blended with the low-cost polymer donor poly[(thiophene)-alt-(6,7-difluoro-2-(2-hexyldecyloxy)quinoxaline)](PTQ10)possesses higher mobilities,a longer lifetime,and less recombination of the charge carriers in comparison with that of the PTQ10:P2EH active layer.Eventually,the PTQ10:T2EH-based PSCs showed an outstanding power conversion efficiency(PCE)of 18.55%,while the PSC based on PTQ10:P2EH displayed a PCE of 17.50%.Importantly,18.55%is the highest PCE in the PTQ10-based binary PSCs so far.The results indicate that T2EH is one of the best SMAs for the PTQ10-based PSCs and is a promising SMA for the application of PSCs.
基金supported by National Key Research and Development Program of China(grant no.2019YFA0705900)funded by MOST,the National Natural Science Foundation of China(grant nos.51820105003,21734008,61904181,and 52173188)the Key Research Program of the Chinese Academy of Sciences(grant no.XDPB13)+2 种基金the Basic and Applied Basic Research Major Program of Guangdong Province(grant no.2019B030302007)Y.W.acknowledges financial support from the Office of Naval Research(award no.N00014-19-1-2453)the use of the Stanford Synchrotron Radiation Light-source,SLAC National Accelerator Laboratory,which is supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences(contract no.DE-AC02-76SF00515).
文摘Side chain engineering with fluorine substitution is widely used to enhance photovoltaic performance of polymer donors in the research field of polymer solar cells(PSCs).However,fluorine substitution has disadvantages of complicated synthesis and high cost.Herein,we synthesized a novel D-A copolymer donor PBQ9 based on difluoroquinoxaline A-unit with chlorine substitution on its alkyl-thiophene side chains instead of fluorine substitution in the polymer donor PBQ6,which greatly shortens the synthetic route and reduces the cost.Interestingly,the optimized binary PSC with PBQ9 as polymer donor and m-TEH as acceptor demonstrated a high power conversion efficiency(PCE)of 18.81%(certified PCE of 18.33%by National Institute of Metrology,China)with a high fill factor of 80.59%,and the photovoltaic performance of the PSCs is insensitive to the different batches of the polymer donor.The results indicate that PBQ9 is a high-performance polymer donor and that chlorine substitution is an effective strategy to improve photovoltaic performance and reduce the cost of polymer donors.
基金funded by the National Key Research and Development Program of China(grant no.2019YFA0705900)by Ministry Of Science and Technology(MOST)the National Natural Science Foundation of China(grant nos.51820105003,61904181,52173188,52103243,and 52203248)the Basic and Applied Basic Research Major Program of Guangdong Province(grant no.2019B030302007).
文摘The power conversion efficiency(PCE)of polymer solar cells(PSCs)has recently increased quickly,propelling PSCs closer to large-scale commercialization.However,several critical issues,such as the cost of materials and the sensitivity of the PCE to active-layer thickness,must be addressed before industrial application can be realized on a large scale.Here,we fabricated a high-performance ternary PSC based on a low-cost polymer donor PTQ10 and an A-DA’D-A-type small molecule acceptor(SMA)2,2'-((2Z,2'Z)-((12,13-bis(2-butyloctyl)-3,9-bis(4-(2-ethylhexyl)thiophen-2-yl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(m-TEH)with a newA-DA’D-A-type SMA 2,2'-((2Z,2'Z)-((12,13-bis(2-butyloctyl)-3,9-bis(3-(2-ethylhexyl)phenyl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(m-PEH)(with phenyl outer side chains)as the third component.Benefitting from the good compatibility and the unique alignment of the energy levels between PTQ10 and the two SMAs,the ternary system showed favorable phase separation and dominant face-on orientation,exhibiting suitable film morphology and enhanced charge transport.Therefore,the optimized ternary PSCs based on PTQ10∶m-TEH∶m-PEH(1.0∶0.9∶0.3,w/w/w)demonstrated an outstanding PCE of 19.34%,which is one of the highest PCEs reported for the single junction PSCs to date.More importantly,the ternary PSCs demonstrated superior tolerance to the active-layer thickness and showed a high PCE of 18.02% with a high fill factor(FF)of 76.56% for the devices with the active-layer thickness even reaching 300 nm.These results indicate that the ternary devices based on PTQ10∶m-TEH∶m-PEH are highly promising for future large-area fabrication and commercial application of PSCs.
基金supported by the National Key Research and Development Program of China (2019YFA0705900)funded by MOST+3 种基金the National Natural Science Foundation of China (51820105003, 21734008, 61904181, 52173188, 21704082, 21875182)the Basic and Applied Basic Research Major Program of Guangdong Province (2019B030302007)Key Scientific and Technological Innovation Team Project of Shaanxi Province (2020TD-002)111 Project 2.0 (BP2018008)。
文摘Recently,all-polymer solar cells(all-PSCs) based on polymerized small molecule acceptors(PSMAs) have achieved significant progress.Ternary blending has proven to be an effective strategy to further boost the power conversion efficiency(PCE) of the all-PSCs.Herein,a new A-DA′D-A small-molecule acceptor-based PSMA(named as PYCl-T) was designed and synthesized,which possesses similar polymer backbone with the widely used PY-IT,but with chlorine substitution on the A-end groups in the A-DA′D-A structure.PYCl-T was then employed as the third component into the PM6:PY-IT system and the ternary all-PSCs based on PM6:PY-IT:PYCl-T demonstrated a high PCE of 16.62%(certified value of 16.3%).Moreover,the PCE of 15.52% was realized in the enlarged ternary all-PSCs with effective area of 1 cm^(2),indicating the great potential in large-scale applications.Moreover,the optimized ternary blend films of PM6:PY-IT:PYCl-T show excellent thermal stability at 150 ℃.This work demonstrates that the utilization of a ternary blend system involving two well-compatible PSMA polymer acceptors is an effective strategy to boost the performance of the all-PSCs.
基金supported by the National Key Research and Development Program of China(2019YFA0705900)the National Natural Science Foundation of China(51820105003,21734008,61904181)the Guangdong Major Project of Basic and Applied Basic Research(2019B030302007)。
文摘Poor stability of spiro-OMe TAD hole transport materials(HTMs)with dopant is a major obstacle for the commercialization of perovskite solar cells(pero-SCs).Herein,we demonstrate a series of quinoxaline-based D-A copolymers PBQ5,PBQ6 and PBQ10 as the dopant-free polymer HTMs for high performance pero-SCs.The D-A copolymers are composed of fluorothienyl benzodithiophene(BDTT)as D-unit,difluoroquinoxaline(DFQ)with different side chains as A-unit,and thiophene asπ-bridge,where the side chains on the DFQ unit are bi-alkyl for PBQ5,bi-alkyl-fluorothienyl for PBQ6,and alkoxyl for PBQ10.All the three copolymers are adopted as the dopant-free HTM in the pero-SCs.The planar n-i-p structured pero-SCs based on(FAPb I_(3))_(0.98)(MAPb Br_(3))_(0.02)with PBQ6 HTM demonstrated the high power conversion efficiency(PCE)of 22.6%with Vocof1.13 V and FF of 80.8%,which is benefitted from the suitable energy level and high hole mobility of PBQ6.The PCE of 22.6%is the highest efficiency reported in the n-i-p structured pero-SCs based on dopant-free D-A copolymer HTM.In addition,the peroSCs show significantly enhanced ambient,thermal and light-soaking stability compared with the devices with traditional spiroOMe TAD HTM.
基金the National Key Research and Development Program of China(2019YFA0705900)the National Natural Science Foundation of China(51820105003,21734008,61904181,52173188 and 52103243)+1 种基金the Key Research Program of the Chinese Academy of Sciences(XDPB13)the Basic and Applied Basic Research Major Program of Guangdong Province(2019B030302007).
文摘降低电压损失(V_(loss))是有机光伏电池未来商业化应用面临的关键挑战之一.V_(loss)一般由活性层材料的光学带隙和器件的开路电压(V_(oc))之差定义,而V_(oc)则由给受体之间的最低未占据分子轨(LUMO)和最高占据分子轨道(HOMO)之间的能级差决定.本文通过引入苯并三唑(BTz)π-桥单元,利用末端调控策略合成了两种A-π-D-π-A型小分子给体SMBTz-1和SM-BTz-2.结果显示,BTzπ-桥单位显著降低了小分子给体的HOMO能级,使其具有较高的Voc和载流子迁移率,实现了高效率与低能量损失(小于0.5 eV)之间的平衡.最终,以SM-BTz-2为给体,Y6为受体的全小分子有机太阳能电池V_(o c)为0.91 V,短路电流密度(J_(sc))为22.8 mA cm^(−2),填充因子为68%,能量转化效率为14.12%.此外,该工作也进一步说明了苯并三唑π-桥单元是提高载流子迁移率,降低能量损失的有效构建单元.
基金This work was supported by the National Key Research and Development Program of China(2019YFA0705900)funded by MOSTthe National Natural Science Foundation of China(51820105003,21734008,61904181)the Guangdong Major Project of Basic and Applied Basic Research(2019B030302007).
文摘D-A copolymerization is a broadly utilized molecular design strategy to construct high efficiency photovoltaic materials for polymer solar cells(PSCs),and all the D-A copolymer donors reported till now are the alternate D-A copolymers with equal D-and A-units.Here,we first propose a non-equivalent D-A copolymerization strategy with unequal D-and A-units,and develop three novel non-equivalent D-A copolymer donors(PM6-D1,PM6-D2 and PM6-D3 with D/A unit ratio of 1.1:0.9,1.2:0.8 and1.3:0.7,respectively)by inserting more D units into the alternate D-A copolymer PM6 backbone to finely tune the physicochemical and photovoltaic properties of the polymers.The three non-equivalent D-A copolymers show the down-shifted highest occupied molecular orbital(HOMO)energy levels,higher hole mobility,higher degree of molecular self-assembly and higher molecular crystallinity with the increase of D-unit ratio in comparison with the alternate D-A copolymer PM6.As a result,all the three non-equivalent D-A copolymer-based PSCs with Y6 as acceptor achieve improved power conversion efficiency(PCE)with higher V_(oc),larger J_(sc)and higher FF simultaneously.Particularly,the PM6-D1:Y6 based PSC achieved a high PCE of17.71%,which is significantly higher than that(15.82%)of the PM6:Y6 based PSC and is one of the highest performances in the binary PSCs.