The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging.In...The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging.In this work,we report a facile and convenient solvothermal method to synthesize metal halides Cs_(2)Zn X_(4)(X=Cl,Br) that however is PL innert at room temperature.Upon composition engineering utilizing Sn^(2+) as the dopant,the resulting Cs_(2)Zn Cl_(4):Sn not only emits strong deep-red PL peaked at700 nm with the highest 99.4%PLQY among the similar materials so far,but also exhibits excellent structure stability in air (PLQY remains 96%after one year exposure to the atmosphere).Detailed experimental characterizations and theoretical calculations reveal that the deep-red emission stems from self-trapped excitons induced by the Sn^(2+) dopant.Particularly,triplet emission (^(3)P_(2)→^(1)S_(0)) from Sn-5s^(2) orbitals has been observed at low temperature due to the break of parity-forbidden transition.This work provides an important guidance for the development of deep-red light-emitting materials with low price,high efficiency and excellent stability.展开更多
Organic solid-state luminescent materials with high-efficiency deep-red emission have attracted considerable interest in recent years.Constructing donor-acceptor(D-A)type molecules has been one of most commonly used s...Organic solid-state luminescent materials with high-efficiency deep-red emission have attracted considerable interest in recent years.Constructing donor-acceptor(D-A)type molecules has been one of most commonly used strategies to achieve deep-red emission,but it is always difficult to achieve high photoluminescence(PL)quantum yield(ηPL)due to forbidden charge-transfer state.Herein,we report a new D-A type molecule 4-(7-(4-(diphenylamino)phenyl)-9-oxo-9H-fluoren-2-yl)benzonitrile(TPAFOCN),deriving from donor-acceptor-donor(D-A-D)type 2,7-bis(4-(diphenylamino)phenyl)-9H-fluoren-9-one(DTPA-FO)with a fluorescence maximum of 627 nm in solids.This molecular design enables a transformation of acceptor from fluorenone(FO)itself to 4-(9-oxo-9H-fluoren-2-yl)benzonitrile(FOCN).Compared with DTPA-FO,the introduction of cyanophenyl not only shifts the emission of TPA-FOCN to deep red with a fluorescence maximum of 668 nm in solids,but also maintains the highηPL of 10%.Additionally,a solution-processed non-doped organic light-emitting diode(OLED)was fabricated with TPA-FOCN as emitter.TPA-FOCN device showed a maximum luminous efficiency of 0.13 cd/A and a maximum external quantum efficiency(EQE)of 0.22%with CIE coordinates of(0.64,0.35).This work provides a valuable strategy for the rational design of high-efficiency deep-red emission materials using cyanophenyl as an ancillary acceptor.展开更多
Visible femtosecond lasers,especially within the deep-red wavelengths,are critical for applications such as bioimaging,biomedicine,and material processing.Traditional visible ultrafast lasers,such as Ti:sapphire laser...Visible femtosecond lasers,especially within the deep-red wavelengths,are critical for applications such as bioimaging,biomedicine,and material processing.Traditional visible ultrafast lasers,such as Ti:sapphire lasers or nonlinear frequency-converted lasers,face limitations in size,cost,stability,and efficiency.Here,we demonstrate a Pr^(3+)-doped mode-locked fiber laser(MLFL),directly generating sub-100-fs pulses at deep-red wavelength.This approach involves theoretical optimization and experimental validation using a ring cavity with Pr^(3+):ZBLAN fiber and nonlinear polarization rotation.The resulting ultrafast laser operates at 716.6 nm,delivering pulses with an~13-nm bandwidth and 83-fs duration at an~73.7-MHz repetition rate.To showcase the feasibility of this 717-nm MLFL for practical applications,twophoton microscopy is demonstrated with outstanding and unique performance regarding the simultaneous multicolor excitation of blue,green,and red dyes,enhanced resolution by 33%,and approximately four times higher excitation efficiency,compared with the conventional excitation wavelength at~1064 nm.These advantages confirm its versatility and reliability in biophotonic imaging.Our findings pave the way for compact,efficient sub-100-fs visible fiber lasers for multicolor bioimaging applications.展开更多
Deep-red and near-infrared emissive carbon dots(CDs)are highly desired for bioimaging,especially in deep tissue imaging,but they are extremely rare and the known ones usually suffer from low-efficient fluorescence in ...Deep-red and near-infrared emissive carbon dots(CDs)are highly desired for bioimaging,especially in deep tissue imaging,but they are extremely rare and the known ones usually suffer from low-efficient fluorescence in water and aggregation-induced fluorescence quenching in solid state.In this work,CDs with intriguing solvent-dependent and two-photon fluorescence emissions have been prepared by a facile solvothermal method.Detailed characterizations reveal that there is an n→π*interaction between the carboxyl functional groups on CDs and the electron donor groups in solvent,which leads to the increase of energy density of CDs and the decrease of energy level,resulting in the red shift of luminescence with enhanced electron donating ability of solvent.Inspired by this finding,mesoporous silica nanoparticles(MSNs)with suitable pore size and low biological toxicity are modified by amino groups to confine CDs,thus the deep-red fluorescence emission is achieved both in solid state and in water facilitated by the n→π*interaction of host-vip.The as-prepared CDs@EDA-MSN composite exhibits high-efficient fluorescence with 650 nm wavelength,low toxicity,and good biocompatibility,which endow them a promising application in bio-imaging.展开更多
Deep-red/near-infrared fluorescence is highly suitable for bioimaging owing to its ability to deeply penetrate tissues,organs,and live animals.However,developing organic fluorophores with high deep-red/near-infrared f...Deep-red/near-infrared fluorescence is highly suitable for bioimaging owing to its ability to deeply penetrate tissues,organs,and live animals.However,developing organic fluorophores with high deep-red/near-infrared fluorescence quantum yield(Φ_(FL))and fluorescent brightness remain a significant challenge owing to the energy gap law.Herein,we developed a straightforward and effective chalcogen-annulation strategy by introducing O,S and Se into the bay region of TDI and QDI fluorophores,realizing the increase ofΦFLand fluorescent brightness up to 10 times.To our best knowledge,this study potentially stands as the pioneering instance showcasing the anti-heavy-atom effect of chalcogens,and the absoluteΦFL(93%)and fluorescent brightness(128,200 cm^(-1)mol^(-1)L)of Se-TDI is among top deep-red/near-infrared organic fluorophores currently available.The femtosecond transient absorption(fs-TA)measurements show the absence of obvious changes of the excited state lifetime after the introduction of chalcogens in TDI and QDI fluorophores,indicating that intersystem crossing(ISC)can be neglected in TDI and QDI fluorophores.Theoretical calculations further reveal the chalcogen-annulation strategy increase the radiative rates and reduce the reorganization energy of several accepting modes at the ground state in TDI fluorophores,leading to the suppression of internal conversion(IC)processes.Our chalcogen-annulation strategy,which effectively increases the Φ_(FL)and restricts the IC processes,while remaining unaffected by the heavy-atom effect,offers novel insights and theoretical support for the design and synthesis of deep-red/near-infrared organic fluorophores with high Φ_(FL)and fluorescent brightness.展开更多
基金the financial supports from National Natural Science Foundation of China (Nos. 91741105, 22109130)Chongqing Municipal Natural Science Foundation (Nos. cstc2018jcyj AX0625, cstc2021jcyj-msxm X1180)Program for Innovation Team Building at Institutions of Higher Education in Chongqing (No. CXTDX201601011)。
文摘The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging.In this work,we report a facile and convenient solvothermal method to synthesize metal halides Cs_(2)Zn X_(4)(X=Cl,Br) that however is PL innert at room temperature.Upon composition engineering utilizing Sn^(2+) as the dopant,the resulting Cs_(2)Zn Cl_(4):Sn not only emits strong deep-red PL peaked at700 nm with the highest 99.4%PLQY among the similar materials so far,but also exhibits excellent structure stability in air (PLQY remains 96%after one year exposure to the atmosphere).Detailed experimental characterizations and theoretical calculations reveal that the deep-red emission stems from self-trapped excitons induced by the Sn^(2+) dopant.Particularly,triplet emission (^(3)P_(2)→^(1)S_(0)) from Sn-5s^(2) orbitals has been observed at low temperature due to the break of parity-forbidden transition.This work provides an important guidance for the development of deep-red light-emitting materials with low price,high efficiency and excellent stability.
基金supported by the National Natural Science Foundation of China(Nos.91833304,51873077,51803071 and51673083)the National Basic Research Program of China(Nos.2015CB655003 and 2016YFB0401001)+2 种基金the Postdoctoral Innovation Talent Support Project(Nos.BX201700097 and BX20180121)the China Postdoctoral Science Foundation(Nos.2017M620108 and2018M641767)JLUSTIRT(No.2019TD-33)
文摘Organic solid-state luminescent materials with high-efficiency deep-red emission have attracted considerable interest in recent years.Constructing donor-acceptor(D-A)type molecules has been one of most commonly used strategies to achieve deep-red emission,but it is always difficult to achieve high photoluminescence(PL)quantum yield(ηPL)due to forbidden charge-transfer state.Herein,we report a new D-A type molecule 4-(7-(4-(diphenylamino)phenyl)-9-oxo-9H-fluoren-2-yl)benzonitrile(TPAFOCN),deriving from donor-acceptor-donor(D-A-D)type 2,7-bis(4-(diphenylamino)phenyl)-9H-fluoren-9-one(DTPA-FO)with a fluorescence maximum of 627 nm in solids.This molecular design enables a transformation of acceptor from fluorenone(FO)itself to 4-(9-oxo-9H-fluoren-2-yl)benzonitrile(FOCN).Compared with DTPA-FO,the introduction of cyanophenyl not only shifts the emission of TPA-FOCN to deep red with a fluorescence maximum of 668 nm in solids,but also maintains the highηPL of 10%.Additionally,a solution-processed non-doped organic light-emitting diode(OLED)was fabricated with TPA-FOCN as emitter.TPA-FOCN device showed a maximum luminous efficiency of 0.13 cd/A and a maximum external quantum efficiency(EQE)of 0.22%with CIE coordinates of(0.64,0.35).This work provides a valuable strategy for the rational design of high-efficiency deep-red emission materials using cyanophenyl as an ancillary acceptor.
基金supported by the National Natural Science Foundation of China(Grant Nos.62235014,62305275,62022069,and 62305274)the Shenzhen Science and Technology Projects(Grant No.JCYJ20210324115813037)the Youth Independent Innovation Science Foundation of the National University of Defense Technology(Grant No.ZK24-20)。
文摘Visible femtosecond lasers,especially within the deep-red wavelengths,are critical for applications such as bioimaging,biomedicine,and material processing.Traditional visible ultrafast lasers,such as Ti:sapphire lasers or nonlinear frequency-converted lasers,face limitations in size,cost,stability,and efficiency.Here,we demonstrate a Pr^(3+)-doped mode-locked fiber laser(MLFL),directly generating sub-100-fs pulses at deep-red wavelength.This approach involves theoretical optimization and experimental validation using a ring cavity with Pr^(3+):ZBLAN fiber and nonlinear polarization rotation.The resulting ultrafast laser operates at 716.6 nm,delivering pulses with an~13-nm bandwidth and 83-fs duration at an~73.7-MHz repetition rate.To showcase the feasibility of this 717-nm MLFL for practical applications,twophoton microscopy is demonstrated with outstanding and unique performance regarding the simultaneous multicolor excitation of blue,green,and red dyes,enhanced resolution by 33%,and approximately four times higher excitation efficiency,compared with the conventional excitation wavelength at~1064 nm.These advantages confirm its versatility and reliability in biophotonic imaging.Our findings pave the way for compact,efficient sub-100-fs visible fiber lasers for multicolor bioimaging applications.
基金the financial supports by the National Natural Science Foundation of China(Nos.21920102005,21835002,and 21621001)the 111 Project of China(No.B17020).
文摘Deep-red and near-infrared emissive carbon dots(CDs)are highly desired for bioimaging,especially in deep tissue imaging,but they are extremely rare and the known ones usually suffer from low-efficient fluorescence in water and aggregation-induced fluorescence quenching in solid state.In this work,CDs with intriguing solvent-dependent and two-photon fluorescence emissions have been prepared by a facile solvothermal method.Detailed characterizations reveal that there is an n→π*interaction between the carboxyl functional groups on CDs and the electron donor groups in solvent,which leads to the increase of energy density of CDs and the decrease of energy level,resulting in the red shift of luminescence with enhanced electron donating ability of solvent.Inspired by this finding,mesoporous silica nanoparticles(MSNs)with suitable pore size and low biological toxicity are modified by amino groups to confine CDs,thus the deep-red fluorescence emission is achieved both in solid state and in water facilitated by the n→π*interaction of host-vip.The as-prepared CDs@EDA-MSN composite exhibits high-efficient fluorescence with 650 nm wavelength,low toxicity,and good biocompatibility,which endow them a promising application in bio-imaging.
基金financially supported by the National Natural Science Foundation of China(NSFC)(22235005)the National Postdoctoral Program for Innovative Talents(BX20200128)+3 种基金the 69th batch of Chinese postdoctoral general support(2021M691004)Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)the Fundamental Research Funds for the Central Universitiesthe Programme of Introducing Talents of Discipline to Universities(B16017)。
文摘Deep-red/near-infrared fluorescence is highly suitable for bioimaging owing to its ability to deeply penetrate tissues,organs,and live animals.However,developing organic fluorophores with high deep-red/near-infrared fluorescence quantum yield(Φ_(FL))and fluorescent brightness remain a significant challenge owing to the energy gap law.Herein,we developed a straightforward and effective chalcogen-annulation strategy by introducing O,S and Se into the bay region of TDI and QDI fluorophores,realizing the increase ofΦFLand fluorescent brightness up to 10 times.To our best knowledge,this study potentially stands as the pioneering instance showcasing the anti-heavy-atom effect of chalcogens,and the absoluteΦFL(93%)and fluorescent brightness(128,200 cm^(-1)mol^(-1)L)of Se-TDI is among top deep-red/near-infrared organic fluorophores currently available.The femtosecond transient absorption(fs-TA)measurements show the absence of obvious changes of the excited state lifetime after the introduction of chalcogens in TDI and QDI fluorophores,indicating that intersystem crossing(ISC)can be neglected in TDI and QDI fluorophores.Theoretical calculations further reveal the chalcogen-annulation strategy increase the radiative rates and reduce the reorganization energy of several accepting modes at the ground state in TDI fluorophores,leading to the suppression of internal conversion(IC)processes.Our chalcogen-annulation strategy,which effectively increases the Φ_(FL)and restricts the IC processes,while remaining unaffected by the heavy-atom effect,offers novel insights and theoretical support for the design and synthesis of deep-red/near-infrared organic fluorophores with high Φ_(FL)and fluorescent brightness.
