The defects from electron transport layer,perovskite layer and their interface would result in carrier nonradiative recombination losses.Poor buried interfacial contact is detrimental to charge extraction and device s...The defects from electron transport layer,perovskite layer and their interface would result in carrier nonradiative recombination losses.Poor buried interfacial contact is detrimental to charge extraction and device stability.Here,we report a bottom-up holistic carrier management strategy induced synergistically by multiple chemical bonds to minimize bulk and interfacial energy losses for high-performance perovskite photovoltaics.4-trifluoromethyl-benzamidine hydrochloride(TBHCl)containing–CF_(3),amidine cation and Cl^(-)is in advance incorporated into SnO_(2)colloid solution to realize bottom-up modification.The synergistic effect of multiple functional groups and multiple-bond-induced chemical interaction are revealed theoretically and experimentally.F and Cl^(-)can passivate oxygen vacancy and/or undercoordinated Sn^(4+)defects by coordinating with Sn^(4+).The F can suppress cation migration and modulate crystallization via hydrogen bond with FA^(+),and can passivate lead defects by coordinating with Pb^(2+).The–NH_(2)–C=NH^(+)_(2)and Cl^(-)can passivate cation and anion vacancy defects through ionic bonds with perovskites,respectively.Through TBHCl modification,the suppression of agglomeration of SnO_(2)nanoparticles,bulk and interfacial defect passivation,and release of tensile strains of perovskite films are demonstrated,which resulted in a PCE enhancement from 21.28%to 23.40%and improved stability.With post-treatment,the efficiency is further improved to 23.63%.展开更多
The interfacial defects and energy barrier are main reasons for interfacial nonradiative recombination.In addition,poor perovskite crystallization and incomplete conversion of PbI_(2) to perovskite restrict further en...The interfacial defects and energy barrier are main reasons for interfacial nonradiative recombination.In addition,poor perovskite crystallization and incomplete conversion of PbI_(2) to perovskite restrict further enhancement of the photovoltaic performance of the devices using sequential deposition.Herein,a buried interface stabilization strategy that relies on the synergy of fluorine(F)and sulfonyl(S=O)functional groups is proposed.A series of potassium salts containing halide and non-halogen anions are employed to modify SnO_(2)/perovskite buried interface.Multiple chemical bonds including hydrogen bond,coordination bond and ionic bond are realized,which strengthens interfacial contact and defect passivation effect.The chemical interaction between modification molecules and perovskite along with SnO_(2) heightens incessantly as the number of S=O and F augments.The chemical interaction strength between modifiers and perovskite as well as SnO_(2) gradually increases with the increase in the number of S=O and F.The defect passivation effect is positively correlated with the chemical interaction strength.The crystallization kinetics is regulated through the compromise between chemical interaction strength and wettability of substrates.Compared with Cl−,all non-halogen anions perform better in crystallization optimization,energy band regulation and defect passivation.The device with potassium bis(fluorosulfonyl)imide achieves a tempting efficiency of 24.17%.展开更多
Bulk and interface carrier nonradiative recombination losses impede the further improvement of power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs).It is highly necessary to develop multifunct...Bulk and interface carrier nonradiative recombination losses impede the further improvement of power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs).It is highly necessary to develop multifunctional strategy to minimize surface and interface nonradiative recombination losses.Herein,we report a bulk and interface defect passivation strategy via the synergistic effect of anions and cations,where multifunctional potassium sulphate(K_(2)SO_(4))is incorporated at SnO_(2)/perovskite interface.We find that K^(+)ions in K_(2)SO_(4)diffuse into perovskite layer and suppress the formation of bulk defects in perovskite films,and the SO_(4)^(2-)ions remain located at interface via the strong chemical interaction with SnO_(2)layer and perovskite layer,respectively.Through this synergistic modification strategy,effective defect passivation and improved energy band alignment are achieved simultaneously.These beneficial effects are translated into an efficiency increase from 19.45%to 21.18%with a low voltage deficit of0.53 V mainly as a result of boosted open-circuit voltage(V_(oc))after K_(2)SO_(4)modification.In addition,the K_(2)SO_(4)modification contributes to ameliorated stability.The present work provides a route to minimize bulk and interface nonradiative recombination losses for the simultaneous realization of PCE and stability enhancement by rational anion and cation synergistic engineering.展开更多
To explore the influence of substituent groups on thermally induced curing,eight new bio-based benzoxazines containing different substituent groups with different electron negativity and volumes were synthesized.The t...To explore the influence of substituent groups on thermally induced curing,eight new bio-based benzoxazines containing different substituent groups with different electron negativity and volumes were synthesized.The thermal curing of these bio-based benzoxazines was studied in detail.Combined with the curing reaction kinetics,simulation and calculation of Highest Occupied Molecular and Lowest Unoccupied Molecular values,the spatial and electronic effects of different substituent groups on the curing of benzoxazine was explored.It was found that when the substituent was located at the position directly connected to the N atom,the steric hindrance effect of the group was dominant.When the substituent group was located on the benzene ring connected to the O atom,both the electronic effect and the spatial effect influenced the curing of benzoxazine.When an electron-withdrawing group was connected ortho position to the O atom,the curing reaction was promoted due to the decreased electron cloud density of O-on the oxazine ring,making the C-O bond easier to break.When an electron-donating group was connected to the meta position of the O atom it also promoted the curing reaction,possibly because it increased the electron cloud density of the+CH2 reaction site and thereby facilitated electrophilic substitution via attack of+CH2 on the cross linking reaction centre.This work provides a deeper understanding of how spatial and electronic effects of substituents affect the curing of benzoxazine.展开更多
A novel series of polybenzazoles with rigid-rod benzoxazole cycle and soft methylene segment was designed and synthesized via solution condensation poly-merizations from 4,6-diamino-l,3-benzenediol dipho-sphate,tereph...A novel series of polybenzazoles with rigid-rod benzoxazole cycle and soft methylene segment was designed and synthesized via solution condensation poly-merizations from 4,6-diamino-l,3-benzenediol dipho-sphate,terephthalic acid and aliphatic dicarboxylic acid.The structures of polybenzazoles were characterized by means of FT-IR,1H NMR and Wide-angle X-ray diffrac-tion(WAXRD).All the polymers show excellent thermal stability and the TdS was above 471℃,The intrinsic vis-cosities[η]of the polymers ranged from 0.8 to 0.9.The UV-Vis absorption peaks of the polymers in MSA were blue-shifted from 429 nm for PBO to 291 nm for PBOC7,and the Stokes shifts in PL spectra enlarged.展开更多
The perovskite layer,electron transport layer(ETL)and their interface are closely associated with carrier transport and extraction,which possess a pronounced effect on current density.Consequently,the dissatisfactory ...The perovskite layer,electron transport layer(ETL)and their interface are closely associated with carrier transport and extraction,which possess a pronounced effect on current density.Consequently,the dissatisfactory electric properties of functional layers pose a serious challenge for maximizing the thermodynamic potential of current density of perovskite solar cells(PSCs).Herein,we report an ion diffusion-induced double layer doping strategy for efficient and stable PSCs,where LiOH is directly added into SnO_(2)colloidal dispersion solution.It is uncovered that a small amount of Li+ions remain in the ETL and doped SnO2 while a large amount of Li+ions diffuse to SnO_(2)/perovskite interface and into perovskite layer and gradient concentration distribution is spontaneously formed.The Li+ion doping endows both perovskite and SnO_(2)layers improved electric properties,which contributes to facilitated carrier transport and extraction.Moreover,the crystallinity and grain size of perovskite films are enhanced after doping.The doped device delivers a higher power conversion efficiency(PCE)of 21.31%together with improved ambient stability in comparison with the control device(PCE=19.26%).This work demonstrates a simple and effective ion diffusion-induced double layer by chemical doping strategy to advance the development of perovskite photovoltaics.展开更多
基金financially supported by the Support Plan for Overseas Students to Return to China for Entrepreneurship and Innovation(cx2020003)the Fundamental Research Funds for the Central Universities(2020CDJ-LHZZ-074)the Natural Science Foundation of Chongqing(cstc2020jcyj-msxm X0629)。
文摘The defects from electron transport layer,perovskite layer and their interface would result in carrier nonradiative recombination losses.Poor buried interfacial contact is detrimental to charge extraction and device stability.Here,we report a bottom-up holistic carrier management strategy induced synergistically by multiple chemical bonds to minimize bulk and interfacial energy losses for high-performance perovskite photovoltaics.4-trifluoromethyl-benzamidine hydrochloride(TBHCl)containing–CF_(3),amidine cation and Cl^(-)is in advance incorporated into SnO_(2)colloid solution to realize bottom-up modification.The synergistic effect of multiple functional groups and multiple-bond-induced chemical interaction are revealed theoretically and experimentally.F and Cl^(-)can passivate oxygen vacancy and/or undercoordinated Sn^(4+)defects by coordinating with Sn^(4+).The F can suppress cation migration and modulate crystallization via hydrogen bond with FA^(+),and can passivate lead defects by coordinating with Pb^(2+).The–NH_(2)–C=NH^(+)_(2)and Cl^(-)can passivate cation and anion vacancy defects through ionic bonds with perovskites,respectively.Through TBHCl modification,the suppression of agglomeration of SnO_(2)nanoparticles,bulk and interfacial defect passivation,and release of tensile strains of perovskite films are demonstrated,which resulted in a PCE enhancement from 21.28%to 23.40%and improved stability.With post-treatment,the efficiency is further improved to 23.63%.
基金supported by the Defense Industrial Technology Development Program(JCKY2017110C0654)National Natural Science Foundation of China(11974063,61904023,62274018)+1 种基金Chongqing Special Postdoctoral Science Foundation(cstc2019jcyj-bsh0026)Fundamental Research Funds for the Central Universities(2021CDJQY-022).
文摘The interfacial defects and energy barrier are main reasons for interfacial nonradiative recombination.In addition,poor perovskite crystallization and incomplete conversion of PbI_(2) to perovskite restrict further enhancement of the photovoltaic performance of the devices using sequential deposition.Herein,a buried interface stabilization strategy that relies on the synergy of fluorine(F)and sulfonyl(S=O)functional groups is proposed.A series of potassium salts containing halide and non-halogen anions are employed to modify SnO_(2)/perovskite buried interface.Multiple chemical bonds including hydrogen bond,coordination bond and ionic bond are realized,which strengthens interfacial contact and defect passivation effect.The chemical interaction between modification molecules and perovskite along with SnO_(2) heightens incessantly as the number of S=O and F augments.The chemical interaction strength between modifiers and perovskite as well as SnO_(2) gradually increases with the increase in the number of S=O and F.The defect passivation effect is positively correlated with the chemical interaction strength.The crystallization kinetics is regulated through the compromise between chemical interaction strength and wettability of substrates.Compared with Cl−,all non-halogen anions perform better in crystallization optimization,energy band regulation and defect passivation.The device with potassium bis(fluorosulfonyl)imide achieves a tempting efficiency of 24.17%.
基金financially supported by the Defense Industrial Technology Development Program(JCKY2017110C0654)the National Natural Science Foundation of China(11974063,61904023)the Chongqing Special Postdoctoral Science Foundation(cstc2019jcyj-bsh0026)。
文摘Bulk and interface carrier nonradiative recombination losses impede the further improvement of power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs).It is highly necessary to develop multifunctional strategy to minimize surface and interface nonradiative recombination losses.Herein,we report a bulk and interface defect passivation strategy via the synergistic effect of anions and cations,where multifunctional potassium sulphate(K_(2)SO_(4))is incorporated at SnO_(2)/perovskite interface.We find that K^(+)ions in K_(2)SO_(4)diffuse into perovskite layer and suppress the formation of bulk defects in perovskite films,and the SO_(4)^(2-)ions remain located at interface via the strong chemical interaction with SnO_(2)layer and perovskite layer,respectively.Through this synergistic modification strategy,effective defect passivation and improved energy band alignment are achieved simultaneously.These beneficial effects are translated into an efficiency increase from 19.45%to 21.18%with a low voltage deficit of0.53 V mainly as a result of boosted open-circuit voltage(V_(oc))after K_(2)SO_(4)modification.In addition,the K_(2)SO_(4)modification contributes to ameliorated stability.The present work provides a route to minimize bulk and interface nonradiative recombination losses for the simultaneous realization of PCE and stability enhancement by rational anion and cation synergistic engineering.
基金This work was partially supported by the National Natural Science Foundation of China(51773060,and 52073091)Shanghai Natural Science Foundation(20ZR1414600)+1 种基金Shanghai Aerospace Science and Technology Innovation Fund(SAST2020-087)the Fundamental Research Funds for the Central Universities(50321042017001).
文摘To explore the influence of substituent groups on thermally induced curing,eight new bio-based benzoxazines containing different substituent groups with different electron negativity and volumes were synthesized.The thermal curing of these bio-based benzoxazines was studied in detail.Combined with the curing reaction kinetics,simulation and calculation of Highest Occupied Molecular and Lowest Unoccupied Molecular values,the spatial and electronic effects of different substituent groups on the curing of benzoxazine was explored.It was found that when the substituent was located at the position directly connected to the N atom,the steric hindrance effect of the group was dominant.When the substituent group was located on the benzene ring connected to the O atom,both the electronic effect and the spatial effect influenced the curing of benzoxazine.When an electron-withdrawing group was connected ortho position to the O atom,the curing reaction was promoted due to the decreased electron cloud density of O-on the oxazine ring,making the C-O bond easier to break.When an electron-donating group was connected to the meta position of the O atom it also promoted the curing reaction,possibly because it increased the electron cloud density of the+CH2 reaction site and thereby facilitated electrophilic substitution via attack of+CH2 on the cross linking reaction centre.This work provides a deeper understanding of how spatial and electronic effects of substituents affect the curing of benzoxazine.
文摘A novel series of polybenzazoles with rigid-rod benzoxazole cycle and soft methylene segment was designed and synthesized via solution condensation poly-merizations from 4,6-diamino-l,3-benzenediol dipho-sphate,terephthalic acid and aliphatic dicarboxylic acid.The structures of polybenzazoles were characterized by means of FT-IR,1H NMR and Wide-angle X-ray diffrac-tion(WAXRD).All the polymers show excellent thermal stability and the TdS was above 471℃,The intrinsic vis-cosities[η]of the polymers ranged from 0.8 to 0.9.The UV-Vis absorption peaks of the polymers in MSA were blue-shifted from 429 nm for PBO to 291 nm for PBOC7,and the Stokes shifts in PL spectra enlarged.
基金supported by the Defense Industrial Technology Development Program(No.JCKY2017110C0654)the National Natural Science Foundation of China(Nos.11974063 and 61904023)。
文摘The perovskite layer,electron transport layer(ETL)and their interface are closely associated with carrier transport and extraction,which possess a pronounced effect on current density.Consequently,the dissatisfactory electric properties of functional layers pose a serious challenge for maximizing the thermodynamic potential of current density of perovskite solar cells(PSCs).Herein,we report an ion diffusion-induced double layer doping strategy for efficient and stable PSCs,where LiOH is directly added into SnO_(2)colloidal dispersion solution.It is uncovered that a small amount of Li+ions remain in the ETL and doped SnO2 while a large amount of Li+ions diffuse to SnO_(2)/perovskite interface and into perovskite layer and gradient concentration distribution is spontaneously formed.The Li+ion doping endows both perovskite and SnO_(2)layers improved electric properties,which contributes to facilitated carrier transport and extraction.Moreover,the crystallinity and grain size of perovskite films are enhanced after doping.The doped device delivers a higher power conversion efficiency(PCE)of 21.31%together with improved ambient stability in comparison with the control device(PCE=19.26%).This work demonstrates a simple and effective ion diffusion-induced double layer by chemical doping strategy to advance the development of perovskite photovoltaics.