Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-depen...Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-dependent optoelectronic properties and the nanocrystal assembling process,but its detection is still a bit challenging.In this study,we demonstrate that femtosecond sum frequency generation(SFG)vibrational spectroscopy can provide a highly sensitive tool for probing the molecular structures of nanocrystals with a size comparable to the Bohr diameter(∼10 nm)at the single-nanocrystal level.The SFG signals are monitored using the spectral features of the phenyl group in(RMBA)PbBr_(3) and(R-MBA)_(2)PbI_(4) nanocrystals(MBA:methyl-benzyl-ammonium).It is found that the SFG spectra exhibit a strong resonant peak at 3067±3 cm^(−1)(ν2 mode)and a weak shoulder peak at 3045±4 cm^(−1)(ν_(7a) mode)at the ensemble level,whereas a peak of theν2 mode and a peak at 3025±3 cm^(−1)(ν20b mode)at the single-nanocrystal level.The nanocrystals at the single-nanocrystal level tend to lie down on the surface,but stand up as the ensemble number and the averaged sizes increase.This finding may provide valuable information on the structural origins for size-dependent photo-physical properties and photoluminescence blinking dynamics in nanocrystals.展开更多
As the large single-crystalline silicon wafers have revolutionized many industries including electronics and solar cells, it is envisioned that the availability of large single-crystalline perovskite crystals and wafe...As the large single-crystalline silicon wafers have revolutionized many industries including electronics and solar cells, it is envisioned that the availability of large single-crystalline perovskite crystals and wafers will revolutionize its broad applications in photovoltaics, optoelectronics, lasers, photodetectors, light emitting diodes(LEDs), etc. Here we report a method to grow large single-crystalline perovskites including single-halide crystals: CH3NH3PbX3(X=I, Br, Cl), and dual-halide ones:CH3NH3Pb(ClxBr1.x)3 and CH3NH3Pb(BrxI1.x)3, with the largest crystal being 120 mm in length. Meanwhile, we have advanced a process to slice the large perovskite crystals into thin wafers. It is found that the wafers exhibit remarkable features:(1)its trap-state density is a million times smaller than that in the microcrystalline perovskite thin films(MPTF);(2) its carrier mobility is 410 times higher than its most popular organic counterpart P3HT;(3) its optical absorption is expanded to as high as910 nm comparing to 797 nm for the MPTF;(4) while MPTF decomposes at 150 °C, the wafer is stable at high temperature up to270 °C;(5) when exposed to high humidity(75% RH), MPTF decomposes in 5 h while the wafer shows no change for overnight;(6) its photocurrent response is 250 times higher than its MPTF counterpart. A few electronic devices have been fabricated using the crystalline wafers. Among them, the Hall test gives low carrier concentration with high mobility. The trap-state density is measured much lower than common semiconductors. Moreover, the large SC-wafer is found particularly useful for mass production of integrated circuits. By adjusting the halide composition, both the optical absorption and the light emission can be fine-tuned across the entire visible spectrum from 400 nm to 800 nm. It is envisioned that a range of visible lasers and LEDs may be developed using the dual-halide perovskites. With fewer trap states, high mobility, broader absorption, and humidity resistance, it is expected that solar cells with high stable efficiency maybe attainable using the crystalline wafers.展开更多
As a new generation of solution-processable optoelectronic materials, organic-inorganic hybrid halide perovskites have attracted a great deal of interest due to their high and balanced carrier mobility, long carrier d...As a new generation of solution-processable optoelectronic materials, organic-inorganic hybrid halide perovskites have attracted a great deal of interest due to their high and balanced carrier mobility, long carrier dif- fusion length and large light absorption coefficient. These materials have demonstrated wide applications in solar cell, light-emitting diode, laser, photodetector, catalysis and other fields. Comparing with their polycrystalline film counter- part, perovskite single crystals have low trap density and no grain boundaries and thus are anticipated to possess much better optoelectronic performances. Herein, we review the key progress in the development of organic-inorganic halide perovskite single crystals. Particularly, the crystal growth techniques and applications of these advanced materials are highlighted.展开更多
Well-aligned single-crystal nanowire arrays of CH3NH3PbIs have shown potentials in laser sources and photovoltaic applications.Here we developed a solution based epitaxial method to grow CH3NH3PbI3nanowire arrays.By c...Well-aligned single-crystal nanowire arrays of CH3NH3PbIs have shown potentials in laser sources and photovoltaic applications.Here we developed a solution based epitaxial method to grow CH3NH3PbI3nanowire arrays.By confining the precursor solution between a silicon wafer and ST-cut quartz,the evaporation rate of the solvent was slowed down which brings a more stable and controllable solution environment.Relying on the lattice match between CH3NH3PbI3 and ST-cut quartz,arrays of single-crystal nanowires of CH3NH3PbI3have been grown epitaxially.The densities and lengths of CH3NH3PbI3 nanowires can be tuned. The lengths of the resultant crystals range from several microns to over one millimeter.Such CH3NH3PbI3arrays with good alignment and crystallinity were then applied to fabricate photovoltaic devices with good performances.展开更多
Large-scale single crystals have potential applications in many fields,such as in ferroelectric and photoelectric energy conversion devices.Perovskite oxynitrides have also attracted attention in photoelectrochemical ...Large-scale single crystals have potential applications in many fields,such as in ferroelectric and photoelectric energy conversion devices.Perovskite oxynitrides have also attracted attention in photoelectrochemical water splitting systems because of their high theoretical solar-to-hydrogen efficiencies.Nevertheless,the synthesis of perovskite oxynitride single crystals requires the coupling of cation exchange and ammonization processes,which is exceptionally challenging.The present study demonstrates an inorganic vapor method that provides,for the first time ever,high-quality epitaxial perovskite SrTaO_(2)N single crystals on the centimeter scale.Assessments using Raman spectroscopy,crystal structure analysis and density functional theory determined that the conversion mechanism followed a topotactic transition mode.Compared with conventional SrTaO_(2)N particle-assembled films,the SrTaO_(2)N single crystals made in this work were free of interparticle interfaces and grain boundaries,which exhibited extremely high performance during photoelectrochemical water oxidation.In particular,these SrTaO_(2)N single crystals showed the highest photocurrent density at 0.6 V vs.RHE(1.20 mA cm^(−2)) and the highest photocurrent filling factor(47.6%)reported to date,together with a low onset potential(0.35 V vs.RHE).This onset potential was 200 mV less than that of the reported in situ SrTaO_(2)N film,and the photocurrent fill factor was improved by 2 to 3 times.展开更多
Understanding the correlation between the life- time, mobility and diffusion length of photoinduced charge carriers in organolead halide perovskite is essential to suc- cessful perovskite-based solar cells. In this pa...Understanding the correlation between the life- time, mobility and diffusion length of photoinduced charge carriers in organolead halide perovskite is essential to suc- cessful perovskite-based solar cells. In this paper, through mapping the local photoluminescence （PL） dynamics using laser/PL-scanned confocal imaging microscopy and simu- lating the carrier diffusion process in an individual CH3NH3PbI3 single-crystalline particle, we report that the rapid diffusion of charge carriers can produce a fast local PL kinetics when the perovskite is partially excited. This result indicates that using PL kinetics to estimate the carrier life- time in perovskite single crystals needs to exclude the effect of carrier diffusion.展开更多
As the technological development of large single-crystalline wafers have revolutionized many industries including electronics and photovoltaics,one can predict that the availability of large single-crystalline perovsk...As the technological development of large single-crystalline wafers have revolutionized many industries including electronics and photovoltaics,one can predict that the availability of large single-crystalline perovskite crystals and wafers can revolutionize its broad applications in photodetectors,solar cells,LEDs,lasers,etc.In 2015,Liu et al.展开更多
基金supported by the National Key Research and Development Program of China(No.2017YFA0303500,No.2018YFA0208702)the National Natural Science Foundation of China(No.21925302,No.21873090,and No.21633007)Anhui Initiative in Quantum Information Technologies(No.AHY090000)。
文摘Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-dependent optoelectronic properties and the nanocrystal assembling process,but its detection is still a bit challenging.In this study,we demonstrate that femtosecond sum frequency generation(SFG)vibrational spectroscopy can provide a highly sensitive tool for probing the molecular structures of nanocrystals with a size comparable to the Bohr diameter(∼10 nm)at the single-nanocrystal level.The SFG signals are monitored using the spectral features of the phenyl group in(RMBA)PbBr_(3) and(R-MBA)_(2)PbI_(4) nanocrystals(MBA:methyl-benzyl-ammonium).It is found that the SFG spectra exhibit a strong resonant peak at 3067±3 cm^(−1)(ν2 mode)and a weak shoulder peak at 3045±4 cm^(−1)(ν_(7a) mode)at the ensemble level,whereas a peak of theν2 mode and a peak at 3025±3 cm^(−1)(ν20b mode)at the single-nanocrystal level.The nanocrystals at the single-nanocrystal level tend to lie down on the surface,but stand up as the ensemble number and the averaged sizes increase.This finding may provide valuable information on the structural origins for size-dependent photo-physical properties and photoluminescence blinking dynamics in nanocrystals.
基金supported by the National Key Research Project MOST (2016YFA0202400)the National Natural Science Foundation of China (61604090, 61604091, 61674098)+4 种基金National University Research Fund (GK261001009, GK201603107)the Changjiang Scholar and Innovative Research Team (IRT_14R33)the 111 Project (B14041)the Chinese National 1000-talent-plan Program (1110010341)the Innovation Funds of Graduate Programs, SNNU (2015CXS047)
文摘As the large single-crystalline silicon wafers have revolutionized many industries including electronics and solar cells, it is envisioned that the availability of large single-crystalline perovskite crystals and wafers will revolutionize its broad applications in photovoltaics, optoelectronics, lasers, photodetectors, light emitting diodes(LEDs), etc. Here we report a method to grow large single-crystalline perovskites including single-halide crystals: CH3NH3PbX3(X=I, Br, Cl), and dual-halide ones:CH3NH3Pb(ClxBr1.x)3 and CH3NH3Pb(BrxI1.x)3, with the largest crystal being 120 mm in length. Meanwhile, we have advanced a process to slice the large perovskite crystals into thin wafers. It is found that the wafers exhibit remarkable features:(1)its trap-state density is a million times smaller than that in the microcrystalline perovskite thin films(MPTF);(2) its carrier mobility is 410 times higher than its most popular organic counterpart P3HT;(3) its optical absorption is expanded to as high as910 nm comparing to 797 nm for the MPTF;(4) while MPTF decomposes at 150 °C, the wafer is stable at high temperature up to270 °C;(5) when exposed to high humidity(75% RH), MPTF decomposes in 5 h while the wafer shows no change for overnight;(6) its photocurrent response is 250 times higher than its MPTF counterpart. A few electronic devices have been fabricated using the crystalline wafers. Among them, the Hall test gives low carrier concentration with high mobility. The trap-state density is measured much lower than common semiconductors. Moreover, the large SC-wafer is found particularly useful for mass production of integrated circuits. By adjusting the halide composition, both the optical absorption and the light emission can be fine-tuned across the entire visible spectrum from 400 nm to 800 nm. It is envisioned that a range of visible lasers and LEDs may be developed using the dual-halide perovskites. With fewer trap states, high mobility, broader absorption, and humidity resistance, it is expected that solar cells with high stable efficiency maybe attainable using the crystalline wafers.
基金supported by the National Natural Science Foundation of China (91333109 and 21671115) Tsinghua University Initiative Scientific Research Program (20131089202 and 20161080165)Open Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics (KF201516)
文摘As a new generation of solution-processable optoelectronic materials, organic-inorganic hybrid halide perovskites have attracted a great deal of interest due to their high and balanced carrier mobility, long carrier dif- fusion length and large light absorption coefficient. These materials have demonstrated wide applications in solar cell, light-emitting diode, laser, photodetector, catalysis and other fields. Comparing with their polycrystalline film counter- part, perovskite single crystals have low trap density and no grain boundaries and thus are anticipated to possess much better optoelectronic performances. Herein, we review the key progress in the development of organic-inorganic halide perovskite single crystals. Particularly, the crystal growth techniques and applications of these advanced materials are highlighted.
基金supported by the National Natural Science Foundation of China (21631002, U1632119, 21621061, and 91633301) Ministry of Science and Technology of the People’s Republic of China (2016YFA0201904)
文摘Well-aligned single-crystal nanowire arrays of CH3NH3PbIs have shown potentials in laser sources and photovoltaic applications.Here we developed a solution based epitaxial method to grow CH3NH3PbI3nanowire arrays.By confining the precursor solution between a silicon wafer and ST-cut quartz,the evaporation rate of the solvent was slowed down which brings a more stable and controllable solution environment.Relying on the lattice match between CH3NH3PbI3 and ST-cut quartz,arrays of single-crystal nanowires of CH3NH3PbI3have been grown epitaxially.The densities and lengths of CH3NH3PbI3 nanowires can be tuned. The lengths of the resultant crystals range from several microns to over one millimeter.Such CH3NH3PbI3arrays with good alignment and crystallinity were then applied to fabricate photovoltaic devices with good performances.
基金supported by the National Key Research and Development Program of China(2018YFA0209303)the National Natural Science Foundation of China(22025202 and 51972165)Natural Science Foundation of Jiangsu Province(BK20202003)。
文摘Large-scale single crystals have potential applications in many fields,such as in ferroelectric and photoelectric energy conversion devices.Perovskite oxynitrides have also attracted attention in photoelectrochemical water splitting systems because of their high theoretical solar-to-hydrogen efficiencies.Nevertheless,the synthesis of perovskite oxynitride single crystals requires the coupling of cation exchange and ammonization processes,which is exceptionally challenging.The present study demonstrates an inorganic vapor method that provides,for the first time ever,high-quality epitaxial perovskite SrTaO_(2)N single crystals on the centimeter scale.Assessments using Raman spectroscopy,crystal structure analysis and density functional theory determined that the conversion mechanism followed a topotactic transition mode.Compared with conventional SrTaO_(2)N particle-assembled films,the SrTaO_(2)N single crystals made in this work were free of interparticle interfaces and grain boundaries,which exhibited extremely high performance during photoelectrochemical water oxidation.In particular,these SrTaO_(2)N single crystals showed the highest photocurrent density at 0.6 V vs.RHE(1.20 mA cm^(−2)) and the highest photocurrent filling factor(47.6%)reported to date,together with a low onset potential(0.35 V vs.RHE).This onset potential was 200 mV less than that of the reported in situ SrTaO_(2)N film,and the photocurrent fill factor was improved by 2 to 3 times.
基金supported by the State Key Laboratory of Molecular Reaction Dynamics at Dalian Institute of Chemical Physics of Chinese Academy of Sciencesthe National Natural Science Foundation of China(21473192)the National Basic Research Program of China(2013CB834604)
文摘Understanding the correlation between the life- time, mobility and diffusion length of photoinduced charge carriers in organolead halide perovskite is essential to suc- cessful perovskite-based solar cells. In this paper, through mapping the local photoluminescence （PL） dynamics using laser/PL-scanned confocal imaging microscopy and simu- lating the carrier diffusion process in an individual CH3NH3PbI3 single-crystalline particle, we report that the rapid diffusion of charge carriers can produce a fast local PL kinetics when the perovskite is partially excited. This result indicates that using PL kinetics to estimate the carrier life- time in perovskite single crystals needs to exclude the effect of carrier diffusion.
文摘As the technological development of large single-crystalline wafers have revolutionized many industries including electronics and photovoltaics,one can predict that the availability of large single-crystalline perovskite crystals and wafers can revolutionize its broad applications in photodetectors,solar cells,LEDs,lasers,etc.In 2015,Liu et al.
