Layer-structured Ruddlesden–Popper(RP)perovskites(RPPs)with decent stability have captured the imagination of the photovoltaic research community and bring hope for boosting the development of perovskite solar cell(P...Layer-structured Ruddlesden–Popper(RP)perovskites(RPPs)with decent stability have captured the imagination of the photovoltaic research community and bring hope for boosting the development of perovskite solar cell(PSC)technology.However,two-dimensional(2D)or quasi-2D RP PSCs are encountered with some challenges of the large exciton binding energy,blocked charge transport and poor film quality,which restrict their photovoltaic performance.Fortunately,these issues can be readily resolved by rationally designing spacer cations of RPPs.This review mainly focuses on how to design the molecular structures of organic spacers and aims to endow RPPs with outstanding photovoltaic applications.We firstly elucidated the important roles of organic spacers in impacting crystallization kinetics,charge transporting ability and stability of RPPs.Then we brought three aspects to attention for designing organic spacers.Finally,we presented the specific molecular structure design strategies for organic spacers of RPPs aiming to improve photovoltaic performance of RP PSCs.These proposed strategies in this review will provide new avenues to develop novel organic spacers for RPPs and advance the development of RPP photovoltaic technology for future applications.展开更多
In recent years,great progress has been achieved for organicinorganic halide perovskites due to their excellent optoelectronic properties and stability for photovoltaics,light emitting diodes,and high-energy radiation...In recent years,great progress has been achieved for organicinorganic halide perovskites due to their excellent optoelectronic properties and stability for photovoltaics,light emitting diodes,and high-energy radiation detection[1-5].One-dimensional(1D)perovskites,as an important derivative of three-dimensional(3D)perovskites,exhibit low exciton dissociation efficiency,which can produce strong quantum confinement and form self-trapping excited state[6],In addition,the hydrophobic properties and the inhibition of ion migration from large organic cations improve the moisture and thermal stability for optoelectronic devices.展开更多
Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the the...Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the thermal decomposition of ammonium perchlorate(NH_(4)ClO_(4),AP)-based energetic molecular perovskites(AP-based energetic molecular perovskites).The morphology and structure of the MgCo_(2)O_(4) nanosheets were characterized.And their catalytic effect on the thermal decomposition of AP-based energetic molecular perovskites(H_2pz)[NH_(4)(ClO_(4))_(3)](PAP-4),(H_2dabco)[NH_(4)(ClO_(4))_(3)](DAP-4),(H_2mpz)[NH_(4)(ClO_(4))_(3)](PAP-M_(4)),and (H_2hpz)[NH_(4)(ClO_(4))_(3)](PAP-H_(4)) was analyzed.The results showed that MgCo_(2)O_(4) nanosheets had excellent intrinsically catalytic performance towards enhancing the thermal decomposition of AP-based energetic molecular perovskites.After adding MgCo_(2)O_(4) nanosheets,the thermal decomposition peak temperatures of PAP-4,DAP-4,PAP-M_(4),and PAP-H_(4) had been reduced by35.7℃,48.4℃,37.9℃,and 43.6℃,respectively.And the activation energy(Ea)of the thermal decomposition of AP-based energetic molecular perovskites had been reduced,the Eaof PAP-H_(4) decreased by 46.4 kJ/mol at most among them.The catalytic mechanism of MgCo_(2)O_(4) nanosheets for AP-based energetic molecular perovskites is analyzed.This work provides a reference for the future application of AP-based energetic molecular perovskites.展开更多
Perovskite solar cells(PSCs)are becoming a promising candidate for next-generation photovoltaic cells due to their attractive power conversion efficiency(PCE).Plasmonic enhancement is regarded as an optical tuning app...Perovskite solar cells(PSCs)are becoming a promising candidate for next-generation photovoltaic cells due to their attractive power conversion efficiency(PCE).Plasmonic enhancement is regarded as an optical tuning approach for further improving the PCE of single-junction PSCs toward Shockley-Queisser limit.Herein,we introduce molecularly isolated gold nanorods(Au NRs),bearing relatively stronger scattering ability and localized surface plasmonic resonance(LSPR)effect,in the rear side of perovskites in PSCs,for promoting light harvesting and for electrical enhancement.Owing to the larger refractive index and better matched energy level alignment,the 4-mercaptobenzoic acid molecules coated on Au NRs prove to play important dual roles:isolating the metallic Au NRs from contacting with perovskite,and facilitating more efficient charge separation and transport across the interface under the synergetic LSPR effect of Au NRs.Our work highlights the capability of the plasmonic approach by nanorods and by molecular isolation,extending nanoparticle-based plasmonic approaches,toward highly efficient plasmon-enhanced PSCs.展开更多
High-pressure behaviour of orthorhombic MgSiO3 perovskite crystal is simulated by using the density functional theory and plane-wave pseudopotentials approach up to 120 GPa pressure at zero temperature. The lattice co...High-pressure behaviour of orthorhombic MgSiO3 perovskite crystal is simulated by using the density functional theory and plane-wave pseudopotentials approach up to 120 GPa pressure at zero temperature. The lattice constants and mass density of the MgSiO3 crystal as functions of pressure are computed, and the corresponding bulk modulus and bulk velocity are evaluated. Our theoretical results agree well with the high-pressure experimental data. A thermodynamic method is introduced to correct the temperature effect on the O-K first-principles results of bulk wave velocity, bulk modulus and mass density in lower mantle PIT range. Taking into account the temperature corrections, the corrected mass density, bulk modulus and bulk wave velocity of MgSiO3-perovskite are estimated from the first-principles results to be 2%, 4%, and 1% lower than the preliminary reference Earth model （PREM） profile, respectively, supporting the possibility of a pure perovskite lower mantle model.展开更多
Recent experiments report the rotation of FA(FA=HC[NH2]2+)cations significantly influence the excited-state lifetime of FAPbI3.However,the underlying mechanism remains unclear.Using ab initio nonadiabatic(NA)molecular...Recent experiments report the rotation of FA(FA=HC[NH2]2+)cations significantly influence the excited-state lifetime of FAPbI3.However,the underlying mechanism remains unclear.Using ab initio nonadiabatic(NA)molecular dynamics combined with time-domain density functional simulations,we have demonstrated that reorientation of partial FA cations significantly inhibits nonradiative electron-hole recombination with respect to the pristine FAPbI3 due to the decreased NA coupling by localizing electron and hole in different positions and the suppressed atomic motions.Slow nuclear motions simultaneously increase the decoherence time,which is overcome by the reduced NA coupling,extending electron-hole recombination time scales to several nanoseconds and being about 3.9 times longer than that in pristine FAPbI3,which occurs within sub-nanosecond and agrees with experiment.Our study established the mechanism for the experimentally reported prolonged excited-state lifetime,providing a rational strategy for design of high performance of perovskite solar cells and optoelectronic devices.展开更多
We present an optical and photoelectron spectroscopic study to elucidate the interfacial electronic properties of organic-inorganic semiconductor heterojunctions formed in a kinetically blocked heptazethrene triisopro...We present an optical and photoelectron spectroscopic study to elucidate the interfacial electronic properties of organic-inorganic semiconductor heterojunctions formed in a kinetically blocked heptazethrene triisopropylsilyl ethynylene (HZ-TIPS) and its homologue,octazethrene (OZ-TIPS) on an all-inorganic perovskite cesium lead bromide (CsPbBr3) surface.The photoluminescence behavior of the underlying perovskites upon differing molecular doping conditions was examined.It turns out that the charge transfer dynamics of thermally-evaporated OZ-TIPS molecule exhibited a faster average lifetime than that of the HZ-TIPS case suggesting the importance of the biradical state in the former molecule.An interfacial dipole was formed at the interface due to the competing interaction between the dispersion force of the bulky TIPS-substituent group and the attractive van der Waals interaction at the first few layers.Photoemission spectroscopy of the physisorbed HZ-TIPS shows chemical shifts,which indicates electron transfer from HZ-TIPS molecules to the CsPbBr3 perovskite single crystal.In contrast,the adsorbed OZ-TIPS molecular layer on CsPbBr3 demonstrates the opposite trend indicating a hole transfer process.The average molecular orientation as determined by near edge X-ray absorption fine structure (NEXAFS) suggests that the HZ-TIPS molecular plane is generally lifted with respect to the perovskite surface.We suggest that the nature of the closed-shell electronic ground state of HZ-TIPS could contribute to the formation of interfacial dipole at the molecule/perovskite interface.展开更多
钙钛矿太阳能电池(perovskite solar cells,PVSCs)因长期稳定性差和制造成本高难以实现工业化生产。其制备中最常用的空穴传输材料(hole-transporting materials,HTMs)为2,2′,7,7′-四[N,N-二(4-甲氧基苯基)氨基]-9,9′-螺二芴,需一定...钙钛矿太阳能电池(perovskite solar cells,PVSCs)因长期稳定性差和制造成本高难以实现工业化生产。其制备中最常用的空穴传输材料(hole-transporting materials,HTMs)为2,2′,7,7′-四[N,N-二(4-甲氧基苯基)氨基]-9,9′-螺二芴,需一定量吸湿添加剂以实现高效的空穴提取,导致对水敏感的钙钛矿层受到破坏。无掺杂HTMs避免了吸湿添加剂的使用,且成本低、合成步骤简单。综述了应用于n-i-p型PVSCs的YT5、M7-TFSI、P3HT、PBDB-Cz等高效率无掺杂有机小分子以及聚合物HTMs,提出了理想HTMs在器件性能、分子结构、合成条件、经济成本等方面的设计原则,并展望了无掺杂HTMs在PVSCs商业化过程中的应用前景。展开更多
基金funding from National Science Foundation of China(52202337 and 22178015)the Young Taishan Scholars Program of Shandong Province(tsqn202211082)+1 种基金Natural Science Foundation of Shandong Province(ZR2023MB051)Independent Innovation Research Project of China University of Petroleum(East China)(22CX06023A).
文摘Layer-structured Ruddlesden–Popper(RP)perovskites(RPPs)with decent stability have captured the imagination of the photovoltaic research community and bring hope for boosting the development of perovskite solar cell(PSC)technology.However,two-dimensional(2D)or quasi-2D RP PSCs are encountered with some challenges of the large exciton binding energy,blocked charge transport and poor film quality,which restrict their photovoltaic performance.Fortunately,these issues can be readily resolved by rationally designing spacer cations of RPPs.This review mainly focuses on how to design the molecular structures of organic spacers and aims to endow RPPs with outstanding photovoltaic applications.We firstly elucidated the important roles of organic spacers in impacting crystallization kinetics,charge transporting ability and stability of RPPs.Then we brought three aspects to attention for designing organic spacers.Finally,we presented the specific molecular structure design strategies for organic spacers of RPPs aiming to improve photovoltaic performance of RP PSCs.These proposed strategies in this review will provide new avenues to develop novel organic spacers for RPPs and advance the development of RPP photovoltaic technology for future applications.
基金supported by the National Key Research and Development Program of China (2016YFA0202403, 2017YFA0204800)the National Natural Science Foundation of China (61974085)+2 种基金the 111 Project (Grant No. B21005)National 1000-talent-plan program (1110010341)the National University Research Fund (Grant No. GK202103104).
文摘In recent years,great progress has been achieved for organicinorganic halide perovskites due to their excellent optoelectronic properties and stability for photovoltaics,light emitting diodes,and high-energy radiation detection[1-5].One-dimensional(1D)perovskites,as an important derivative of three-dimensional(3D)perovskites,exhibit low exciton dissociation efficiency,which can produce strong quantum confinement and form self-trapping excited state[6],In addition,the hydrophobic properties and the inhibition of ion migration from large organic cations improve the moisture and thermal stability for optoelectronic devices.
基金the National Natural Science Foundation of China(Grant No.21975227)the Found of National defence Sci&Tech Laboratory(Grant No.6142602210306)。
文摘Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the thermal decomposition of ammonium perchlorate(NH_(4)ClO_(4),AP)-based energetic molecular perovskites(AP-based energetic molecular perovskites).The morphology and structure of the MgCo_(2)O_(4) nanosheets were characterized.And their catalytic effect on the thermal decomposition of AP-based energetic molecular perovskites(H_2pz)[NH_(4)(ClO_(4))_(3)](PAP-4),(H_2dabco)[NH_(4)(ClO_(4))_(3)](DAP-4),(H_2mpz)[NH_(4)(ClO_(4))_(3)](PAP-M_(4)),and (H_2hpz)[NH_(4)(ClO_(4))_(3)](PAP-H_(4)) was analyzed.The results showed that MgCo_(2)O_(4) nanosheets had excellent intrinsically catalytic performance towards enhancing the thermal decomposition of AP-based energetic molecular perovskites.After adding MgCo_(2)O_(4) nanosheets,the thermal decomposition peak temperatures of PAP-4,DAP-4,PAP-M_(4),and PAP-H_(4) had been reduced by35.7℃,48.4℃,37.9℃,and 43.6℃,respectively.And the activation energy(Ea)of the thermal decomposition of AP-based energetic molecular perovskites had been reduced,the Eaof PAP-H_(4) decreased by 46.4 kJ/mol at most among them.The catalytic mechanism of MgCo_(2)O_(4) nanosheets for AP-based energetic molecular perovskites is analyzed.This work provides a reference for the future application of AP-based energetic molecular perovskites.
基金supported by the Ministry of Science and Technology of China(2016YFA0200703)the National Natural Science Foundation of China(21931009)。
文摘Perovskite solar cells(PSCs)are becoming a promising candidate for next-generation photovoltaic cells due to their attractive power conversion efficiency(PCE).Plasmonic enhancement is regarded as an optical tuning approach for further improving the PCE of single-junction PSCs toward Shockley-Queisser limit.Herein,we introduce molecularly isolated gold nanorods(Au NRs),bearing relatively stronger scattering ability and localized surface plasmonic resonance(LSPR)effect,in the rear side of perovskites in PSCs,for promoting light harvesting and for electrical enhancement.Owing to the larger refractive index and better matched energy level alignment,the 4-mercaptobenzoic acid molecules coated on Au NRs prove to play important dual roles:isolating the metallic Au NRs from contacting with perovskite,and facilitating more efficient charge separation and transport across the interface under the synergetic LSPR effect of Au NRs.Our work highlights the capability of the plasmonic approach by nanorods and by molecular isolation,extending nanoparticle-based plasmonic approaches,toward highly efficient plasmon-enhanced PSCs.
基金Supported by the National Natural Science Foundation of China under Grant Nos 40474033 and 10376024, and the Specialized Research Fund for the Doctoral Program of Higher Education of China under Grant No 20050613017.
文摘High-pressure behaviour of orthorhombic MgSiO3 perovskite crystal is simulated by using the density functional theory and plane-wave pseudopotentials approach up to 120 GPa pressure at zero temperature. The lattice constants and mass density of the MgSiO3 crystal as functions of pressure are computed, and the corresponding bulk modulus and bulk velocity are evaluated. Our theoretical results agree well with the high-pressure experimental data. A thermodynamic method is introduced to correct the temperature effect on the O-K first-principles results of bulk wave velocity, bulk modulus and mass density in lower mantle PIT range. Taking into account the temperature corrections, the corrected mass density, bulk modulus and bulk wave velocity of MgSiO3-perovskite are estimated from the first-principles results to be 2%, 4%, and 1% lower than the preliminary reference Earth model （PREM） profile, respectively, supporting the possibility of a pure perovskite lower mantle model.
基金supported by the National Natural Science Foundation of China(No.21573022 and No.51861135101)the Recruitment Program of Global Youth Experts of Chinathe Beijing Normal University Startup。
文摘Recent experiments report the rotation of FA(FA=HC[NH2]2+)cations significantly influence the excited-state lifetime of FAPbI3.However,the underlying mechanism remains unclear.Using ab initio nonadiabatic(NA)molecular dynamics combined with time-domain density functional simulations,we have demonstrated that reorientation of partial FA cations significantly inhibits nonradiative electron-hole recombination with respect to the pristine FAPbI3 due to the decreased NA coupling by localizing electron and hole in different positions and the suppressed atomic motions.Slow nuclear motions simultaneously increase the decoherence time,which is overcome by the reduced NA coupling,extending electron-hole recombination time scales to several nanoseconds and being about 3.9 times longer than that in pristine FAPbI3,which occurs within sub-nanosecond and agrees with experiment.Our study established the mechanism for the experimentally reported prolonged excited-state lifetime,providing a rational strategy for design of high performance of perovskite solar cells and optoelectronic devices.
文摘We present an optical and photoelectron spectroscopic study to elucidate the interfacial electronic properties of organic-inorganic semiconductor heterojunctions formed in a kinetically blocked heptazethrene triisopropylsilyl ethynylene (HZ-TIPS) and its homologue,octazethrene (OZ-TIPS) on an all-inorganic perovskite cesium lead bromide (CsPbBr3) surface.The photoluminescence behavior of the underlying perovskites upon differing molecular doping conditions was examined.It turns out that the charge transfer dynamics of thermally-evaporated OZ-TIPS molecule exhibited a faster average lifetime than that of the HZ-TIPS case suggesting the importance of the biradical state in the former molecule.An interfacial dipole was formed at the interface due to the competing interaction between the dispersion force of the bulky TIPS-substituent group and the attractive van der Waals interaction at the first few layers.Photoemission spectroscopy of the physisorbed HZ-TIPS shows chemical shifts,which indicates electron transfer from HZ-TIPS molecules to the CsPbBr3 perovskite single crystal.In contrast,the adsorbed OZ-TIPS molecular layer on CsPbBr3 demonstrates the opposite trend indicating a hole transfer process.The average molecular orientation as determined by near edge X-ray absorption fine structure (NEXAFS) suggests that the HZ-TIPS molecular plane is generally lifted with respect to the perovskite surface.We suggest that the nature of the closed-shell electronic ground state of HZ-TIPS could contribute to the formation of interfacial dipole at the molecule/perovskite interface.
文摘钙钛矿太阳能电池(perovskite solar cells,PVSCs)因长期稳定性差和制造成本高难以实现工业化生产。其制备中最常用的空穴传输材料(hole-transporting materials,HTMs)为2,2′,7,7′-四[N,N-二(4-甲氧基苯基)氨基]-9,9′-螺二芴,需一定量吸湿添加剂以实现高效的空穴提取,导致对水敏感的钙钛矿层受到破坏。无掺杂HTMs避免了吸湿添加剂的使用,且成本低、合成步骤简单。综述了应用于n-i-p型PVSCs的YT5、M7-TFSI、P3HT、PBDB-Cz等高效率无掺杂有机小分子以及聚合物HTMs,提出了理想HTMs在器件性能、分子结构、合成条件、经济成本等方面的设计原则,并展望了无掺杂HTMs在PVSCs商业化过程中的应用前景。
