Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years,the influence of temperature and the type of the employed ho...Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years,the influence of temperature and the type of the employed hole transport layer(HTL)on the charge carrier dynamics and recombination processes in perovskite photovoltaic devices is still largely unexplored.In particular,significant knowledge is missing on how these crucial parameters for radiative and non-radiative recombinations,as well as for efficient charge extraction vary among different perovskite crystalline phases that are induced by temperature variation.Herein,we perform micro photoluminescence(pPL)and ultrafast time resolved transient absorption spectroscopy(TAS)in Glass/Perovskite and two dierent Glass/ITO/HTL/Perovskite configurations at temperatures below room temperature,in order to probe the charge carrier dynamics of different perovskite crystalline phases,while considering also the effect of the employed HTL polymer.Namely,CH_(3)NH_(3)Pbb films were deposited on Glass,PEDOT:PSS and PTAA polymers,and the developed Glass/CH_(3)NH_(3)PbI_(3)and Glass/ITO/HTL/CH_(3)NH_(3)PbI_(3)architectures were studied from 85 K up to 215 K in order to explore the charge extraction dynamics of the CH_(3)NH_(3)PbI_(3)orthorhombic and tetragonal crystalline phases.It is observed an unusual blueshift of the bandgap with temperature and the dual emission at temperature below of 100 K and also,that the charge carrier dynamics,as expressed by hole injection times and free carrier recombination rates,are strongly depended on the actual pervoskite crystal phase,as well as,from the selected hole transport material.展开更多
In this work, we demonstrated the successful construction of metal-free zero- dimensional/two-dimensional carbon nanodot （CND）-hybridized protonatedg=C3N4 （pCN） （CND/pCN） heterojunction photocatalysts b; means o...In this work, we demonstrated the successful construction of metal-free zero- dimensional/two-dimensional carbon nanodot （CND）-hybridized protonatedg=C3N4 （pCN） （CND/pCN） heterojunction photocatalysts b; means of electrostatic attraction. We experimentally found that CNDs with an average diameter of 4.4 nm were uniformly distributed on the surface of pCN using electron microscopy analysis. The CND/pCN-3 sample with a CND content of 3 wt.% showed thehighest catalytic activity in the CO2 photoreduction process under visible and simulated solar light. This process results in the evolution of CH4 and CO. Thetotal amounts of CH4 and CO generated by the CND/pCN-3 photocatalyst after 10 h of visible-light activity were found to be 29.23 and 58.82 molgcatalyst-1, respectively. These values were 3.6 and 2.28 times higher, respectively, than thearn＊ounts generated when using pCN alone. The corresponding apparent quantum efficiency （AQE） was calculated to be 0.076%. Furthermore, the CND/pCN-3 sample demonstrated high stability and durability after four consecutive photoreaction cycles, with no significant decrease in the catalytic activity.展开更多
Broadband(1.6–18 THz) terahertz time-domain spectroscopy(THz-TDS) and time-resolved terahertz spectroscopy(TRTS) were performed on a 54 μm thick chalcogenide glass(As_(30)Se_(30)Te_(40)) sample with a two-color lase...Broadband(1.6–18 THz) terahertz time-domain spectroscopy(THz-TDS) and time-resolved terahertz spectroscopy(TRTS) were performed on a 54 μm thick chalcogenide glass(As_(30)Se_(30)Te_(40)) sample with a two-color laser-induced air plasma THz system in transmission and reflection modes, respectively. Two absorption bands at 2–3 and 5–8 THz were observed. TRTS reveals an ultrafast relaxation process of the photoinduced carrier response, well described by a rate equation model with a finite concentration of mid-bandgap trap states for self-trapped excitons.The photoinduced conductivity can be well described by the Drude–Smith conductivity model with a carrier scattering time of 12–17 fs, and we observe significant carrier localization effects. A fast refractive index change was observed 100 fs before the conductivity reached its maximum, with 2 orders of magnitude larger amplitude than expected for the optically induced THz Kerr effect, indicating that free carriers are responsible for the transient index change.展开更多
Organic photovoltaics(OPVs)need to overcome limitations such as insufficient thermal stability to be commercialized.The reported approaches to improve stability either rely on the development of new materials or on ta...Organic photovoltaics(OPVs)need to overcome limitations such as insufficient thermal stability to be commercialized.The reported approaches to improve stability either rely on the development of new materials or on tailoring the donor/acceptor morphology,however,exhibiting limited applicability.Therefore,it is timely to develop an easy method to enhance thermal stability without having to develop new donor/acceptor materials or donor–acceptor compatibilizers,or by introducing another third component.Herein,a unique approach is presented,based on constructing a polymer fiber rigid network with a high glass transition temperature(T_(g))to impede the movement of acceptor and donor molecules,to immobilize the active layer morphology,and thereby to improve thermal stability.A high-T_(g) one-dimensional aramid nanofiber(ANF)is utilized for network construction.Inverted OPVs with ANF network yield superior thermal stability compared to the ANF-free counterpart.The ANF network-incorporated active layer demonstrates significantly more stable morphology than the ANF-free counterpart,thereby leaving fundamental processes such as charge separation,transport,and collection,determining the device efficiency,largely unaltered.This strategy is also successfully applied to other photovoltaic systems.The strategy of incorporating a polymer fiber rigid network with high T_(g) offers a distinct perspective addressing the challenge of thermal instability with simplicity and universality.展开更多
Van der Waals(VDW)heterojunctions in a 2D/2D contact provide the highest area for the separation and transfer of charge carriers.In this work,a top-down strategy with a gas erosion process was employed to fabricate a ...Van der Waals(VDW)heterojunctions in a 2D/2D contact provide the highest area for the separation and transfer of charge carriers.In this work,a top-down strategy with a gas erosion process was employed to fabricate a 2D/2D carbon nitride VDW heterojunction in carbon nitride(g-C_(3)N_(4))with carbon-rich carbon nitride.The created 2D semiconducting channel in the VDW structure exhibits enhanced electric field exposure and radiation absorption,which facilitates the separation of the charge carriers and their mobility.Consequently,compared with bulk g-C_(3)N_(4)and its nanosheets,the photocatalytic performance of the fabricated carbon nitride VDW heterojunction in the water splitting reaction to hydrogen is improved by 8.6 and 3.3 times,respectively,while maintaining satisfactory photo-stability.Mechanistically,the finite element method(FEM)was employed to evaluate and clarify the contributions of the formation of VDW heterojunction to enhanced photocatalysis,in agreement quantitatively with experimental ones.This study provides a new and effective strategy for the modification and more insights to performance improvement on polymeric semiconductors in photocatalysis and energy conversion.展开更多
Interfacial engineering for the regulation of the charge carrier dynamics in solar cells is a critical factor in the fabrication of high-efficiency devices.Based on the successful preparation of highly dispersible gra...Interfacial engineering for the regulation of the charge carrier dynamics in solar cells is a critical factor in the fabrication of high-efficiency devices.Based on the successful preparation of highly dispersible graphdiyne oxide(GDYO)with a large number of functional groups,we fabricated organic solar cells employing GDYO-modified poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate)(PEDOT:PSS)as hole transport materials.Results show that theπ±πinteraction between GDYO and PEDOT:PSS is beneficial to the formation of an optimized charge carrier transfer channel and improves the conductivity and charge carrier mobility in the hole transport layer.Moreover,the improved interfacial contact contributes to the suppression of charge carrier recombination and the elevation of charge carrier extraction between the hole transport layer and the active layer.More importantly,the occurrence of charge carrier separation benefits from the optimized morphology of the active layer,which efficiently improves the performance,as proven by the results of transient absorption measurements.Therefore,with the holistic management approach to the multiobjective optimization of the charge carrier dynamics,a photoelectric conversion efficiency of 17.5%(with the certified value of 17.2%)is obtained for binary organic solar cells.All of these results indicate the potential application of the functionalized graphdiyne in the field of organic optoelectronic devices.展开更多
Lead-free double perovskite Cs_(2)AgBiBr_(6) has gained increasing attention recently.However,the power conversion efficiency(PCE)of Cs_(2)AgBiBr_(6) perovskite solar cells(PSCs)is still low compared with their lead-b...Lead-free double perovskite Cs_(2)AgBiBr_(6) has gained increasing attention recently.However,the power conversion efficiency(PCE)of Cs_(2)AgBiBr_(6) perovskite solar cells(PSCs)is still low compared with their lead-based counterparts.Here,by using photoluminescence(PL),time-resolved photoluminescence(TRPL),and ultrafast transient absorption(TA)measurements,the unbalance between the electron and hole in diffusion and transfer,which limits the performance of the Cs_(2)AgBiBr_(6) PSCs,was further revealed.Considering this issue,a strategy of using the mesoporous TiO_(2) electron transport layer(ETL)to construct a bulk heterojunction in Cs_(2)AgBiBr_(6) PSCs was proposed.Consequently,the PCE had improved by over 24%comparing with that only used compact TiO_(2) ETL.Moreover,based on mesoporous TiO_(2),the unencapsulated Cs_(2)AgBiBr_(6) PSCs maintained 90%of their initial performance after approximately 1200 h of storage in a desiccator(humidity~30%).This work gives further understanding of Cs_(2)AgBiBr_(6) perovskite and demonstrates that a proper design of balancing the electron and hole diffusion can improve device performance.展开更多
Heterogeneous photocatalysis has long been considered to be one of the most promising approaches to tackling the myriad environmental issues.However,there are still many challenges for designing efficient and cost-eff...Heterogeneous photocatalysis has long been considered to be one of the most promising approaches to tackling the myriad environmental issues.However,there are still many challenges for designing efficient and cost-effective photocatalysts and photocatalytic degradation systems for application in practical environmental remediation.In this review,we first systematically introduced the fundamental principles on the photocatalytic pollutant degradation.Then,the important considerations in the design of photocatalytic degradation systems are carefully addressed,including charge carrier dynamics,catalytic selectivity,photocatalyst stability,pollutant adsorption and photodegradation kinetics.Especially,the underlying mechanisms are thoroughly reviewed,including investigation of oxygen reduction properties and identification of reactive oxygen species and key intermediates.This review in environmental photocatalysis may inspire exciting new directions and methods for designing,fabricating and evaluating photocatalytic degradation systems for better environmental remediation and possibly other relevant fields,such as photocatalytic disinfection,water oxidation,and selective organic transformations.展开更多
文摘Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years,the influence of temperature and the type of the employed hole transport layer(HTL)on the charge carrier dynamics and recombination processes in perovskite photovoltaic devices is still largely unexplored.In particular,significant knowledge is missing on how these crucial parameters for radiative and non-radiative recombinations,as well as for efficient charge extraction vary among different perovskite crystalline phases that are induced by temperature variation.Herein,we perform micro photoluminescence(pPL)and ultrafast time resolved transient absorption spectroscopy(TAS)in Glass/Perovskite and two dierent Glass/ITO/HTL/Perovskite configurations at temperatures below room temperature,in order to probe the charge carrier dynamics of different perovskite crystalline phases,while considering also the effect of the employed HTL polymer.Namely,CH_(3)NH_(3)Pbb films were deposited on Glass,PEDOT:PSS and PTAA polymers,and the developed Glass/CH_(3)NH_(3)PbI_(3)and Glass/ITO/HTL/CH_(3)NH_(3)PbI_(3)architectures were studied from 85 K up to 215 K in order to explore the charge extraction dynamics of the CH_(3)NH_(3)PbI_(3)orthorhombic and tetragonal crystalline phases.It is observed an unusual blueshift of the bandgap with temperature and the dual emission at temperature below of 100 K and also,that the charge carrier dynamics,as expressed by hole injection times and free carrier recombination rates,are strongly depended on the actual pervoskite crystal phase,as well as,from the selected hole transport material.
文摘In this work, we demonstrated the successful construction of metal-free zero- dimensional/two-dimensional carbon nanodot （CND）-hybridized protonatedg=C3N4 （pCN） （CND/pCN） heterojunction photocatalysts b; means of electrostatic attraction. We experimentally found that CNDs with an average diameter of 4.4 nm were uniformly distributed on the surface of pCN using electron microscopy analysis. The CND/pCN-3 sample with a CND content of 3 wt.% showed thehighest catalytic activity in the CO2 photoreduction process under visible and simulated solar light. This process results in the evolution of CH4 and CO. Thetotal amounts of CH4 and CO generated by the CND/pCN-3 photocatalyst after 10 h of visible-light activity were found to be 29.23 and 58.82 molgcatalyst-1, respectively. These values were 3.6 and 2.28 times higher, respectively, than thearn＊ounts generated when using pCN alone. The corresponding apparent quantum efficiency （AQE） was calculated to be 0.076%. Furthermore, the CND/pCN-3 sample demonstrated high stability and durability after four consecutive photoreaction cycles, with no significant decrease in the catalytic activity.
基金financial support from the Danish Research Council for Independent Research (FNU Project THz-BREW)
文摘Broadband(1.6–18 THz) terahertz time-domain spectroscopy(THz-TDS) and time-resolved terahertz spectroscopy(TRTS) were performed on a 54 μm thick chalcogenide glass(As_(30)Se_(30)Te_(40)) sample with a two-color laser-induced air plasma THz system in transmission and reflection modes, respectively. Two absorption bands at 2–3 and 5–8 THz were observed. TRTS reveals an ultrafast relaxation process of the photoinduced carrier response, well described by a rate equation model with a finite concentration of mid-bandgap trap states for self-trapped excitons.The photoinduced conductivity can be well described by the Drude–Smith conductivity model with a carrier scattering time of 12–17 fs, and we observe significant carrier localization effects. A fast refractive index change was observed 100 fs before the conductivity reached its maximum, with 2 orders of magnitude larger amplitude than expected for the optically induced THz Kerr effect, indicating that free carriers are responsible for the transient index change.
基金financially supported by the Sichuan Science and Technology Program(Grant Nos.2023YFH0087,2023YFH0085,2023YFH0086,and 2023NSFSC0990)State Key Laboratory of Polymer Materials Engineering(Grant Nos.sklpme2022-3-02 and sklpme2023-2-11)+1 种基金Tibet Foreign Experts Program(Grant No.2022wz002)supported by the King Abdullah University of Science and Technology(KAUST)Office of Research Administration(ORA)under Award Nos.OSR-CARF/CCF-3079 and OSR-2021-CRG10-4701.
文摘Organic photovoltaics(OPVs)need to overcome limitations such as insufficient thermal stability to be commercialized.The reported approaches to improve stability either rely on the development of new materials or on tailoring the donor/acceptor morphology,however,exhibiting limited applicability.Therefore,it is timely to develop an easy method to enhance thermal stability without having to develop new donor/acceptor materials or donor–acceptor compatibilizers,or by introducing another third component.Herein,a unique approach is presented,based on constructing a polymer fiber rigid network with a high glass transition temperature(T_(g))to impede the movement of acceptor and donor molecules,to immobilize the active layer morphology,and thereby to improve thermal stability.A high-T_(g) one-dimensional aramid nanofiber(ANF)is utilized for network construction.Inverted OPVs with ANF network yield superior thermal stability compared to the ANF-free counterpart.The ANF network-incorporated active layer demonstrates significantly more stable morphology than the ANF-free counterpart,thereby leaving fundamental processes such as charge separation,transport,and collection,determining the device efficiency,largely unaltered.This strategy is also successfully applied to other photovoltaic systems.The strategy of incorporating a polymer fiber rigid network with high T_(g) offers a distinct perspective addressing the challenge of thermal instability with simplicity and universality.
基金the National Natural Science Foundation of China(51676096)supported by the Australian Research Council(DP170104264 and DP190103548).
文摘Van der Waals(VDW)heterojunctions in a 2D/2D contact provide the highest area for the separation and transfer of charge carriers.In this work,a top-down strategy with a gas erosion process was employed to fabricate a 2D/2D carbon nitride VDW heterojunction in carbon nitride(g-C_(3)N_(4))with carbon-rich carbon nitride.The created 2D semiconducting channel in the VDW structure exhibits enhanced electric field exposure and radiation absorption,which facilitates the separation of the charge carriers and their mobility.Consequently,compared with bulk g-C_(3)N_(4)and its nanosheets,the photocatalytic performance of the fabricated carbon nitride VDW heterojunction in the water splitting reaction to hydrogen is improved by 8.6 and 3.3 times,respectively,while maintaining satisfactory photo-stability.Mechanistically,the finite element method(FEM)was employed to evaluate and clarify the contributions of the formation of VDW heterojunction to enhanced photocatalysis,in agreement quantitatively with experimental ones.This study provides a new and effective strategy for the modification and more insights to performance improvement on polymeric semiconductors in photocatalysis and energy conversion.
基金supported by the National Natural Science Foundation of China(21975273,21801014,21773012,and U2032112)Shandong Provincial Natural Science Foundation(ZR2021QE191)+3 种基金the Scientific Research Starting Foundation of Outstanding Young Scholar of Shandong Universitythe Future Young Scholars Program of Shandong Universitythe Fundamental Research Funds of Shandong Universitysupported by the Analysis&Testing Center of Beijing Institute of Technology。
文摘Interfacial engineering for the regulation of the charge carrier dynamics in solar cells is a critical factor in the fabrication of high-efficiency devices.Based on the successful preparation of highly dispersible graphdiyne oxide(GDYO)with a large number of functional groups,we fabricated organic solar cells employing GDYO-modified poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate)(PEDOT:PSS)as hole transport materials.Results show that theπ±πinteraction between GDYO and PEDOT:PSS is beneficial to the formation of an optimized charge carrier transfer channel and improves the conductivity and charge carrier mobility in the hole transport layer.Moreover,the improved interfacial contact contributes to the suppression of charge carrier recombination and the elevation of charge carrier extraction between the hole transport layer and the active layer.More importantly,the occurrence of charge carrier separation benefits from the optimized morphology of the active layer,which efficiently improves the performance,as proven by the results of transient absorption measurements.Therefore,with the holistic management approach to the multiobjective optimization of the charge carrier dynamics,a photoelectric conversion efficiency of 17.5%(with the certified value of 17.2%)is obtained for binary organic solar cells.All of these results indicate the potential application of the functionalized graphdiyne in the field of organic optoelectronic devices.
基金financial support from Macao Science and Technology Development Fund,China(FDCT-0044/2020/A1,FDCT-091/2017/A2,FDCT-014/2017/AMJ)University of Macao Research Grant,China(MYRG2018-00148-IAPME,MYRG2018-00142-IAPME)from University of Macao+2 种基金the Natural Science Foundation of China,China(91733302,61935017)Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials(2019B121205002)Natural Science Foundation of Guangdong Province,China(2019A1515012186).
文摘Lead-free double perovskite Cs_(2)AgBiBr_(6) has gained increasing attention recently.However,the power conversion efficiency(PCE)of Cs_(2)AgBiBr_(6) perovskite solar cells(PSCs)is still low compared with their lead-based counterparts.Here,by using photoluminescence(PL),time-resolved photoluminescence(TRPL),and ultrafast transient absorption(TA)measurements,the unbalance between the electron and hole in diffusion and transfer,which limits the performance of the Cs_(2)AgBiBr_(6) PSCs,was further revealed.Considering this issue,a strategy of using the mesoporous TiO_(2) electron transport layer(ETL)to construct a bulk heterojunction in Cs_(2)AgBiBr_(6) PSCs was proposed.Consequently,the PCE had improved by over 24%comparing with that only used compact TiO_(2) ETL.Moreover,based on mesoporous TiO_(2),the unencapsulated Cs_(2)AgBiBr_(6) PSCs maintained 90%of their initial performance after approximately 1200 h of storage in a desiccator(humidity~30%).This work gives further understanding of Cs_(2)AgBiBr_(6) perovskite and demonstrates that a proper design of balancing the electron and hole diffusion can improve device performance.
基金partially supported by the National Natural Science Foundation of China(22272019)Sichuan Science and Technology Program(2022ZYD0039,2022NSFSC1213,2023NSFSC1069)。
基金supported by Shanghai Pujiang Program(21PJ1400400)Shanghai Municipal Science and Technology Commission(22511103900)+1 种基金the Fundamental Research Funds for the Central Universities(2232023A-02)the National Natural Science Foundation of China(22173017).
基金the National Natural Science Foundation of China(Grant No.51672089)Special funding on Applied Science and Technology in Guangdong(No.2017B020238005)+3 种基金the State Key Laboratory of Advanced Technology for Material Synthesis and Processing(Wuhan University of Technology)(No.2015-KF-7)the NSFC(Nos.51320105001,U1705251 and 21433007)Natural Science Foundation of Hubei Province(No.2015CFA001)Innovative Research Funds of SKLWUT(No.2017-ZD-4).
文摘Heterogeneous photocatalysis has long been considered to be one of the most promising approaches to tackling the myriad environmental issues.However,there are still many challenges for designing efficient and cost-effective photocatalysts and photocatalytic degradation systems for application in practical environmental remediation.In this review,we first systematically introduced the fundamental principles on the photocatalytic pollutant degradation.Then,the important considerations in the design of photocatalytic degradation systems are carefully addressed,including charge carrier dynamics,catalytic selectivity,photocatalyst stability,pollutant adsorption and photodegradation kinetics.Especially,the underlying mechanisms are thoroughly reviewed,including investigation of oxygen reduction properties and identification of reactive oxygen species and key intermediates.This review in environmental photocatalysis may inspire exciting new directions and methods for designing,fabricating and evaluating photocatalytic degradation systems for better environmental remediation and possibly other relevant fields,such as photocatalytic disinfection,water oxidation,and selective organic transformations.
