Although covalent organic frameworks(COFs)with highπ-conjugation have recently exhibited great prospects in perovskite solar cells(PSCs),their further application in PSCs is still hindered by face-to-face stacking an...Although covalent organic frameworks(COFs)with highπ-conjugation have recently exhibited great prospects in perovskite solar cells(PSCs),their further application in PSCs is still hindered by face-to-face stacking and aggregation issues.Herein,metal-organic framework(MOF-808)is selected as an ideal platform for the in situ homogeneous growth of a COF to construct a core-shell MOF@COF nanoparticle,which could effectively inhibit COF stacking and aggregation.The synergistic intrinsic mechanisms induced by the MOF@COF nanoparticles for reinforcing intrinsic stability and mitigating lead leakage in PSCs have been explored.The complementary utilization ofπ-conjugated skeletons and nanopores could optimize the crystallization of large-grained perovskite films and eliminate defects.The resulting PSCs achieve an impressive power conversion efficiency of 23.61%with superior open circuit voltage(1.20 V)and maintained approximately 90%of the original power conversion efficiency after 2000 h(30-50%RH and 25-30℃).Benefiting from the synergistic effects of the in situ chemical fixation and adsorption abilities of the MOF@COF nanoparticles,the amount of lead leakage from unpackaged PSCs soaked in water(<5 ppm)satisfies the laboratory assessment required for the Resource Conservation and Recovery Act Regulation.展开更多
Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal...Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal-organic frameworks(MOFs)with tunable Lewis-base passivation sites have been constructed(Cd-Httb and Cd-Httb-BDC,Httb=5-(4-(1H-1,2,4-triazole-1-yl)benzyl)-1h-tetrazole,BDC=1,4-dicarboxybenzene)to eliminate deep-level defects and simultaneously as nanostructured heterogeneous nucleation seed to assist the growth of large-grained perovskite films.Compared with the control and Cd-Httb,Cd-Httb-BDC designed with mix-ligands strategy exhibited the enhanced inducted effect on the crystallization and nucleation of high-quality perovskite films during annealing process.Consequently,the resultant Cd-Httb-BDC-modified device achieved higher power conversion efficiency(PCE)(22.18%)than the control(20.89%)and Cd-Httb(21.56%).Meanwhile,the unencapsulated Cd-Httb-BDC-modified device still maintained 90%of initial PCE after 1500 h in ambient conditions and exhibited enhanced thermal stability(85℃ in N_(2) atmosphere).This work presented a successful example of mixligands strategy on construction of high-quality MOF-assisted perovskite films for high-efficient and stable PSCs.展开更多
In this work,a blue emitter with a 3 D rigid structure composed of multiple spirobifluorene(3-Spiro) has been synthesized and characterized.Through a detailed study of the electrochemical and photophysical properties ...In this work,a blue emitter with a 3 D rigid structure composed of multiple spirobifluorene(3-Spiro) has been synthesized and characterized.Through a detailed study of the electrochemical and photophysical properties of 3-Spiro,we have evidenced that 3-Spiro can be applied as an active component of organic light-emitting diodes(OLEDs).The device with 5% doping rate of 4 CzPNPh exhibits high external quantum efficiency(EQE) of 11%,which proves the potential of 3 D rigid structure emitters for OLEDs.展开更多
Heat accumulation inside perovskite solar cells causes the decomposition of the perovskite layer and hole transport materials(HTMs)under working conditions,yielding a decrease in long-term stability.Here,we present a ...Heat accumulation inside perovskite solar cells causes the decomposition of the perovskite layer and hole transport materials(HTMs)under working conditions,yielding a decrease in long-term stability.Here,we present a zeolite-assisted heat conduction strategy by introducing economic zeolite crystals(e.g.,NaX,NaY,and ZSM-5)as a cooling filter to induce heat diffusion.The fitted thermal diffusion kinetic equation from real-time infrared thermal imaging technology reveals the zeolite skeleton assisted thermal co nduction mechanism of internal lattice vibration.Additionally,the nearly twofold improved conductivity of the modified HTM film is benefited from Na^(+)hopping on the supercages of the zeolite,therefore,the best-performed device with a rapid heat diffusion and defect inhibition obtains a remarkable power conversion efficiency of 23.42%.Both of NaX modified sprio-OMeTAD and PTAA based devices exhibit excellent operational stability after heating 1000 h at 85℃under N_(2)condition.This work demonstrates the potential application of economical porous zeolite materials in improving the thermal stability of PSCs.展开更多
A novel electron acceptor, namely, tetra-phthalimide end-fused bifluorenylidene(3 D-imide) was designed and synthesized. In comparison to its framework analogue 12,12'-bidibenzo[b,h]fluorenylidene(BF-3), the elect...A novel electron acceptor, namely, tetra-phthalimide end-fused bifluorenylidene(3 D-imide) was designed and synthesized. In comparison to its framework analogue 12,12'-bidibenzo[b,h]fluorenylidene(BF-3), the electron withdrawing capability and optical absorption were strengthened and enlarged,respectively. Moreover, photoluminescence quenching experiments were carried out, which confirmed 3D-imide could be a good candidate for nonfullene organic photovoltaics. Finally, we gained more insight into its electronic properties through density functional theory calculation.展开更多
The interfacial nonradiative recombination loss caused by the deep traps and mismatched band alignment restrained the commercial viability of perovskite solar cells(PSCs). Herein, we have constructed ferrocene carboxy...The interfacial nonradiative recombination loss caused by the deep traps and mismatched band alignment restrained the commercial viability of perovskite solar cells(PSCs). Herein, we have constructed ferrocene carboxylic acid(FcA) and octafluoropentyl-ferrocenyl-carboxylate(OFFcA) interstitial conductive mediums to modulate the integral heterointerface properties and the photovoltaic performances of PSCs.By comparing the passivation strengths of the two molecules, we found that the synergistic effects among Fc/Fc^(+)redox shuttle, C=O group, and F substituents realize the optimal elimination of interfacial trap sources. Electron-withdrawing F groups reinforce the capacity of the Fc/Fc^(+)redox shuttle for the healing of metallic Pb defects and provide extensive anchoring sites to stabilize the organic components.Additionally, the homogeneity of the OFFcA layer as well as the humidity stability of perovskite film are facilitated through the introduction of F substituents, which reduce the contact resistance and improve the interfacial charge transfer. The champion OFFcA-modified device delivers an exceptional PCE of 23.62%, exceeding those of the control(PCE=22.32%) and FcA-modified(PCE=23.06%) devices.Moreover, the unencapsulated OFFcA-modified device retains 82.7% of the primary efficiency at 60%RH for more than 50 d and only loses less than 10% of the primary efficiency when stored in a glove box for more than 2000 h.展开更多
A novel air-stable n-type benzothiaphene endcapped azaarene(BTPQ) and its sulfonated derivative(BSPQ) were prepared via two pathways and characterized by NMR, UV–vis, fluorescence and cyclic voltammetry spectroscopy....A novel air-stable n-type benzothiaphene endcapped azaarene(BTPQ) and its sulfonated derivative(BSPQ) were prepared via two pathways and characterized by NMR, UV–vis, fluorescence and cyclic voltammetry spectroscopy. Symmetrically introducing four nitrogen atoms into acenes, the semiconductor properties could be changed from p-type to n-type detected through the space charge limited current(SCLC) method. After sulfonation of BTPQ, BSPQ is with deeper frontier orbital energy levels and enhanced the electron mobility.展开更多
The severe interfacial charge recombination as well as the stability issues brought by the Li-TFSI still hinder the commercialization of high-performance perovskite solar cells(PSCs).Here,a polyoxometalates(POMs)-base...The severe interfacial charge recombination as well as the stability issues brought by the Li-TFSI still hinder the commercialization of high-performance perovskite solar cells(PSCs).Here,a polyoxometalates(POMs)-based complex,POM@ionic liquid(IL),is synthesized and applied as an effective additive that simultaneously enhances the performance and stability of PSCs.The interactions between POM@IL complex and Li-TFSI inhibit the aggregation of Li-TFSI.The synergistic oxidation of POM@IL complex and Li-TFSI towards 2,2,7,7-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene(Spiro-OMeTAD)effectively enhances the electrical properties of hole transport layer film and the photovoltaic performances of PSCs.The champion device modified with the POM@IL complex yields an excellent power conversion efficiency(PCE)of 22.73%.Moreover,the incorporation of POM@IL improves the humidity stability of PSCs.After storing under high humidity conditions(25℃,60%RH)for 1200 h,the POM@IL modified device retained a remarkable 81.2%of its initial PCE.This work provides new insight into constructing POMs-based materials for high-performance photovoltaic devices.展开更多
Here,a novel strategy is proposed targeting the volatility of A-site cations and the disordered arrangement of perovskite grains through employing Cs~+contained metal-organic frameworks In-aip(Cs)obtained by ion-excha...Here,a novel strategy is proposed targeting the volatility of A-site cations and the disordered arrangement of perovskite grains through employing Cs~+contained metal-organic frameworks In-aip(Cs)obtained by ion-exchange and crystalline transform.Interatomic forces between Cs-O atoms split the pore channels of the pristine In-aip,endowing In-aip(Cs)with multidimensional charge transport channels,In addition,the partially freed Cs~+in the interlayer compensates for the vacancy of A-site cations during the perovskite preparation process.The In-aip(Cs)modified perovskite films have a flat morphology,large grains and excellent optoelectronic properties.Benefiting from the high-quality perovskite films and faster charge extraction,the In-aip(Cs)-modified PSCs achieved a champion PCE of 23.03%,superior to the In-aip-modified(22.29%)and control device(21.13%),More importantly,the unencapsulated PSCs modified with In-aip(Cs)exhibited outstanding humidity and thermal stability.Over a period of almost 1000 h,the unencapsulated In-aip(Cs)-modified device retained 85%of its initial PCE after storing in a glove box at 85℃,and retained 87%of the primary PCE upon storage in ambient condition at 25℃under a humidity of 40%.展开更多
基金supported by the National Natural Science Foundation of China(22072034,and 22001050)the China Postdoctoral Science Foundation(2022M710949,2020T130147,and 2020M681084)+2 种基金the Postdoctoral Foundation of Heilongjiang Province(LBH-Z22106,and LBH-Z19059)the Natural Science Foundation of Heilongjiang Youth Fund(YQ2021B002)Education Department of Heilongjiang Province(LJYXL2022-038).
文摘Although covalent organic frameworks(COFs)with highπ-conjugation have recently exhibited great prospects in perovskite solar cells(PSCs),their further application in PSCs is still hindered by face-to-face stacking and aggregation issues.Herein,metal-organic framework(MOF-808)is selected as an ideal platform for the in situ homogeneous growth of a COF to construct a core-shell MOF@COF nanoparticle,which could effectively inhibit COF stacking and aggregation.The synergistic intrinsic mechanisms induced by the MOF@COF nanoparticles for reinforcing intrinsic stability and mitigating lead leakage in PSCs have been explored.The complementary utilization ofπ-conjugated skeletons and nanopores could optimize the crystallization of large-grained perovskite films and eliminate defects.The resulting PSCs achieve an impressive power conversion efficiency of 23.61%with superior open circuit voltage(1.20 V)and maintained approximately 90%of the original power conversion efficiency after 2000 h(30-50%RH and 25-30℃).Benefiting from the synergistic effects of the in situ chemical fixation and adsorption abilities of the MOF@COF nanoparticles,the amount of lead leakage from unpackaged PSCs soaked in water(<5 ppm)satisfies the laboratory assessment required for the Resource Conservation and Recovery Act Regulation.
基金supported by the National Natural Science Foundation of China(22072034,22001050,and 21873025)the China Postdoctoral Science Foundation(2020T130147,2020M681084,and 2022M710949)+1 种基金the Postdoctoral Foundation of Heilongjiang Province(LBH-Z19059)the Natural Science Foundation of Heilongjiang Youth Fund(YQ2021B002).
文摘Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal-organic frameworks(MOFs)with tunable Lewis-base passivation sites have been constructed(Cd-Httb and Cd-Httb-BDC,Httb=5-(4-(1H-1,2,4-triazole-1-yl)benzyl)-1h-tetrazole,BDC=1,4-dicarboxybenzene)to eliminate deep-level defects and simultaneously as nanostructured heterogeneous nucleation seed to assist the growth of large-grained perovskite films.Compared with the control and Cd-Httb,Cd-Httb-BDC designed with mix-ligands strategy exhibited the enhanced inducted effect on the crystallization and nucleation of high-quality perovskite films during annealing process.Consequently,the resultant Cd-Httb-BDC-modified device achieved higher power conversion efficiency(PCE)(22.18%)than the control(20.89%)and Cd-Httb(21.56%).Meanwhile,the unencapsulated Cd-Httb-BDC-modified device still maintained 90%of initial PCE after 1500 h in ambient conditions and exhibited enhanced thermal stability(85℃ in N_(2) atmosphere).This work presented a successful example of mixligands strategy on construction of high-quality MOF-assisted perovskite films for high-efficient and stable PSCs.
基金supported by the National Natural Science Foundation of China(No.51603055)the Natural Science Foundation of Heilongjiang Province(No.QC2017055)+1 种基金the China Postdoctoral Science Foundation(Nos.2016M601424,2017T100236)the Postdoctoral Foundation of Heilongjiang Province(Nos.LBH-Z16059,LBH-TZ10)。
文摘In this work,a blue emitter with a 3 D rigid structure composed of multiple spirobifluorene(3-Spiro) has been synthesized and characterized.Through a detailed study of the electrochemical and photophysical properties of 3-Spiro,we have evidenced that 3-Spiro can be applied as an active component of organic light-emitting diodes(OLEDs).The device with 5% doping rate of 4 CzPNPh exhibits high external quantum efficiency(EQE) of 11%,which proves the potential of 3 D rigid structure emitters for OLEDs.
基金supported by the National Natural Science Foundation of China(22001050,22072034,21873025)the China Postdoctoral Science Foundation(2020T130147,2020M681084)+1 种基金the Postdoctoral Foundation of Heilongjiang Province(LBH-Z19059)the Natural Science Foundation of Heilongjiang Youth Fund(YQ2021B002)。
文摘Heat accumulation inside perovskite solar cells causes the decomposition of the perovskite layer and hole transport materials(HTMs)under working conditions,yielding a decrease in long-term stability.Here,we present a zeolite-assisted heat conduction strategy by introducing economic zeolite crystals(e.g.,NaX,NaY,and ZSM-5)as a cooling filter to induce heat diffusion.The fitted thermal diffusion kinetic equation from real-time infrared thermal imaging technology reveals the zeolite skeleton assisted thermal co nduction mechanism of internal lattice vibration.Additionally,the nearly twofold improved conductivity of the modified HTM film is benefited from Na^(+)hopping on the supercages of the zeolite,therefore,the best-performed device with a rapid heat diffusion and defect inhibition obtains a remarkable power conversion efficiency of 23.42%.Both of NaX modified sprio-OMeTAD and PTAA based devices exhibit excellent operational stability after heating 1000 h at 85℃under N_(2)condition.This work demonstrates the potential application of economical porous zeolite materials in improving the thermal stability of PSCs.
基金supported by National Natural Science Foundation of China (No. 51603055)
文摘A novel electron acceptor, namely, tetra-phthalimide end-fused bifluorenylidene(3 D-imide) was designed and synthesized. In comparison to its framework analogue 12,12'-bidibenzo[b,h]fluorenylidene(BF-3), the electron withdrawing capability and optical absorption were strengthened and enlarged,respectively. Moreover, photoluminescence quenching experiments were carried out, which confirmed 3D-imide could be a good candidate for nonfullene organic photovoltaics. Finally, we gained more insight into its electronic properties through density functional theory calculation.
基金National Natural Science Foundation of China (22072034)China Postdoctoral Science Foundation (2020T130147, 2020M681084, and 2022M710949)+1 种基金Postdoctoral Foundation of Heilongjiang Province (LBH-Z19059 and LBH-Z22106)Natural Science Foundation of Heilongjiang Youth Fund (YQ2021B002)。
文摘The interfacial nonradiative recombination loss caused by the deep traps and mismatched band alignment restrained the commercial viability of perovskite solar cells(PSCs). Herein, we have constructed ferrocene carboxylic acid(FcA) and octafluoropentyl-ferrocenyl-carboxylate(OFFcA) interstitial conductive mediums to modulate the integral heterointerface properties and the photovoltaic performances of PSCs.By comparing the passivation strengths of the two molecules, we found that the synergistic effects among Fc/Fc^(+)redox shuttle, C=O group, and F substituents realize the optimal elimination of interfacial trap sources. Electron-withdrawing F groups reinforce the capacity of the Fc/Fc^(+)redox shuttle for the healing of metallic Pb defects and provide extensive anchoring sites to stabilize the organic components.Additionally, the homogeneity of the OFFcA layer as well as the humidity stability of perovskite film are facilitated through the introduction of F substituents, which reduce the contact resistance and improve the interfacial charge transfer. The champion OFFcA-modified device delivers an exceptional PCE of 23.62%, exceeding those of the control(PCE=22.32%) and FcA-modified(PCE=23.06%) devices.Moreover, the unencapsulated OFFcA-modified device retains 82.7% of the primary efficiency at 60%RH for more than 50 d and only loses less than 10% of the primary efficiency when stored in a glove box for more than 2000 h.
基金supported by Natural Science Foundation of Heilongjiang Youth Fund (No. YQ2021B002)Heilongjiang Postdoctoral Scientific Research Developmental Fund (No. LBH-Q20018)State Key Laboratory of Urban Water Resource and Environment (Harbin Institute of Technology)。
文摘A novel air-stable n-type benzothiaphene endcapped azaarene(BTPQ) and its sulfonated derivative(BSPQ) were prepared via two pathways and characterized by NMR, UV–vis, fluorescence and cyclic voltammetry spectroscopy. Symmetrically introducing four nitrogen atoms into acenes, the semiconductor properties could be changed from p-type to n-type detected through the space charge limited current(SCLC) method. After sulfonation of BTPQ, BSPQ is with deeper frontier orbital energy levels and enhanced the electron mobility.
基金supported by the National Natural Science Foundation of China(Nos.22072034 and 22001050)the China Postdoctoral Science Foundation(Nos.2020T130147,2020M681084,and 2022M710949)+1 种基金the Postdoctoral Foundation of Heilongjiang Province(Nos.LBH-Z19059,and LBH-Z22106)the Natural Science Foundation of Heilongjiang Youth Fund(No.YQ2021B002)。
文摘The severe interfacial charge recombination as well as the stability issues brought by the Li-TFSI still hinder the commercialization of high-performance perovskite solar cells(PSCs).Here,a polyoxometalates(POMs)-based complex,POM@ionic liquid(IL),is synthesized and applied as an effective additive that simultaneously enhances the performance and stability of PSCs.The interactions between POM@IL complex and Li-TFSI inhibit the aggregation of Li-TFSI.The synergistic oxidation of POM@IL complex and Li-TFSI towards 2,2,7,7-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene(Spiro-OMeTAD)effectively enhances the electrical properties of hole transport layer film and the photovoltaic performances of PSCs.The champion device modified with the POM@IL complex yields an excellent power conversion efficiency(PCE)of 22.73%.Moreover,the incorporation of POM@IL improves the humidity stability of PSCs.After storing under high humidity conditions(25℃,60%RH)for 1200 h,the POM@IL modified device retained a remarkable 81.2%of its initial PCE.This work provides new insight into constructing POMs-based materials for high-performance photovoltaic devices.
基金supported by National Natural Science Foundation of China(Grant No.22001050,22072034)the China Postdoctoral Science Foundation(Grant No.2020T130147,2020M681084)+1 种基金the Postdoctoral Foundation of Heilongjiang Province(Grant No.LBH-Z19059)the Natural Science Foundation of Heilongjiang Youth Fund(Grant No.YQ2021B002)。
文摘Here,a novel strategy is proposed targeting the volatility of A-site cations and the disordered arrangement of perovskite grains through employing Cs~+contained metal-organic frameworks In-aip(Cs)obtained by ion-exchange and crystalline transform.Interatomic forces between Cs-O atoms split the pore channels of the pristine In-aip,endowing In-aip(Cs)with multidimensional charge transport channels,In addition,the partially freed Cs~+in the interlayer compensates for the vacancy of A-site cations during the perovskite preparation process.The In-aip(Cs)modified perovskite films have a flat morphology,large grains and excellent optoelectronic properties.Benefiting from the high-quality perovskite films and faster charge extraction,the In-aip(Cs)-modified PSCs achieved a champion PCE of 23.03%,superior to the In-aip-modified(22.29%)and control device(21.13%),More importantly,the unencapsulated PSCs modified with In-aip(Cs)exhibited outstanding humidity and thermal stability.Over a period of almost 1000 h,the unencapsulated In-aip(Cs)-modified device retained 85%of its initial PCE after storing in a glove box at 85℃,and retained 87%of the primary PCE upon storage in ambient condition at 25℃under a humidity of 40%.
