Energy Transfer Dynamics between Carbon Quantum Dots and Molybdenum Disulfide Revealed by Transient Absorption Spectroscopy

Zero-dimensional environmentally friendly carbon quantum dots(CQDs)combined with two-di-mensional materials have a wide range of applications in optoelec-tronic devices.We combined steady-state and transient absorp-tion spectroscopies to study the energy transfer dynamics between CQDs and molybdenum disulfide(MoS_(2)).Transient absorption plots showed photoinduced absorption and stimulated emission features,which involved the intrinsic and defect states of CQDs.Adding MoS_(2)to CQDs solution,the lowest unoccupied molecular orbital of CQDs transferred energy to MoS_(2),which quenched the intrinsic emission at 390 nm.With addition of MoS_(2),CQD-MoS_(2)composites quenched defect emission at 490 nm and upward absorption,which originated from another energy transfer from the defect state.Two energy transfer paths between CQDs and MoS_(2)were efficiently manipulated by changing the concentration of MoS_(2),which laid a foundation for improving device performance.

Observation of Refractive Index Line Shape in Ultrafast XUV Transient Absorption Spectroscopy

Ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy measures the time- and frequencydependent light losses after light–matter interactions. In the linear region, the matter response to an XUV light field is usually determined by the complex refractive index ̃n. The absorption signal is directly related to the imaginary part of ̃n, namely, the absorption index. The real part of ̃n refers to the real refractive index, which describes the chromatic dispersion of an optical material. However, the real refractive index information is usually not available in conventional absorption experiments. Here, we investigate the refractive index line shape in ultrafast XUV transient absorption spectroscopy by using a scheme that the XUV pulse traverses the target gas jet off-center. The jet has a density gradient in the direction perpendicular to the gas injection direction, which induces deflection on the XUV radiation. Our experimental and theoretical results show that the shape of the frequency-dependent XUV deflection spectra reproduces the refractive index line profile. A typical dispersive refractive index line shape is measured for a single-peak absorption;an additional shoulder structure appears for a doublet absorption.Moreover, the refractive index line shape is controlled by introducing a later-arrived near-infrared pulse to modify the phase of the XUV free induction decay, resulting in different XUV deflection spectra. The results promote our understanding of matter-induced absorption and deflection in ultrafast XUV spectroscopy.

Investigation of charge transfer between donor and acceptor for small-molecule organic solar cells by scanning tunneling microscopy and ultrafast transient absorption spectroscopy

Small-molecule organic solar cell is a category of clean energy potential device since charge transfers between donor and acceptor.The morphologies,co-assembly behavior,interaction sites,and charge transfer of BTID-nF(n=1,2)/PC71BM donor-acceptor system in the active layer of organic solar cell have been studied employing scanning tunneling microscopy(STM),scanning tunneling spectroscopy(STS),density functional theory(DFT)calculations,and transient absorption(TA)spectroscopy.The results show that BTID-1F and BTID-2F form bright strip structures,whereas BTID-nF(n=1,2)/PC71BM form ridge-like structures with each complex composed of one BTID-nF(n=1,2)molecule and four PC71BM molecules which adsorbed around the BTID-nF(n=1,2)molecule by S···πinteraction.With the assistance of S···πinteraction between BTID-nF(n=1,2)and PC71BM,BTID-nF(n=1,2)/PC71BM co-assembled ridge-like structures are more stable than the BTID-nF(n=1,2)ridge structures.To investigate the charge transfer of BTID-nF(n=1,2)/PC71BM system,STS measurements,DFT calculation,and TA spectroscopy are further performed.The results show that charge transfer occurs in BTID-nF(n=1,2)/PC71BM system with the electron transferring from BTID-nF(n=1,2)molecules to PC71BM.

Probing molecular orientation at bulk heterojunctions by polarization-selective transient absorption spectroscopy

A bulk heterojunction in organic solar cells is where charge separation and recombination occur.Molecular orientation at the interface is one of the key factors that dictate solar cell efficiency.Although X-ray scattering-based methods can determine donor/acceptor domain orientations between an anisotropic phase and an isotropic fullerene-based phase,the rise of nonfullerene solar cells presents a new challenge in delineating local molecular directions at the interface between two anisotropic donor/acceptor domains.Here,we determine interfacial molecular orientations of three high-efficiency small molecule solar cells(ZR1:Y6,B1:BO-4 Cl,and BTR:BO-4 Cl)using polarization-selective transient absorption spectroscopy.The polarization anisotropy of charge separation dynamics indicates an angle of~90°between ZR1 and Y6 molecules at the interface,an angle close to 0°between B1 and BO-4 Cl,and random orientations between BTR and BO-4 Cl.These observations provide complementary information to X-ray scattering measurements and highlight polarization-selective transient absorption spectroscopy as a tool to probe interfacial structure and dynamics of key photophysical steps in energy conversion.

Probing the ultrafast dynamics in nanomaterial complex systems by femtosecond transient absorption spectroscopy

Over the past decade the integration of ultrafast spectroscopy with nanoscience has greatly propelled the development of nanoscience, as the key information gleaned from the mechanistic studies with the assistance of ultrafast spectroscopy enables a deeper understanding of the structure–function interplay and various interactions involved in the nanosystems.This mini-review presents an overview of the recent advances achieved in our ultrafast spectroscopy laboratory that address the ultrafast dynamics and related mechanisms in several representative nanomaterial complex systems by means of femtosecond time-resolved transient absorption spectroscopy. We attempt to convey instructive, consistent information regarding the important processes, pathways, dynamics, and interactions involved in the nanomaterial complex systems,most of which exhibit excellent performance in photocatalysis.

Unraveling the influence of interface defects on antimony trisulfide solar cells

Antimony trisulfide(Sb_(2)S_(3)) solar cells suffer from large open circuit voltage deficits due to their intrinsic defects which limit the power conversion efficiency.Thus,it is important to elucidate these defects’ origin and defects at the interface.Here,we discover that sulfide radical defects have a significant impact on the performance of Sb_(2)S_(3)solar cells.Moreover,it has been illustrated that these defects at the CdS/Sb_(2)S_(3)interface can be reduced by optimizing the deposition process.A trap distribution model is used to quantify the defect density at the CdS/Sb_(2)S_(3)interface.It shows that the interface defects can be reduced by24% by improving the deposition process.This work reveals the importance of interface defects and guides the future optimization of Sb_(2)S_(3)solar cells.

Charge carrier dynamics in different crystal phases of CH_(3)NH_(3)PbI_(3)perovskite

Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years,the influence of temperature and the type of the employed hole transport layer(HTL)on the charge carrier dynamics and recombination processes in perovskite photovoltaic devices is still largely unexplored.In particular,significant knowledge is missing on how these crucial parameters for radiative and non-radiative recombinations,as well as for efficient charge extraction vary among different perovskite crystalline phases that are induced by temperature variation.Herein,we perform micro photoluminescence(pPL)and ultrafast time resolved transient absorption spectroscopy(TAS)in Glass/Perovskite and two dierent Glass/ITO/HTL/Perovskite configurations at temperatures below room temperature,in order to probe the charge carrier dynamics of different perovskite crystalline phases,while considering also the effect of the employed HTL polymer.Namely,CH_(3)NH_(3)Pbb films were deposited on Glass,PEDOT:PSS and PTAA polymers,and the developed Glass/CH_(3)NH_(3)PbI_(3)and Glass/ITO/HTL/CH_(3)NH_(3)PbI_(3)architectures were studied from 85 K up to 215 K in order to explore the charge extraction dynamics of the CH_(3)NH_(3)PbI_(3)orthorhombic and tetragonal crystalline phases.It is observed an unusual blueshift of the bandgap with temperature and the dual emission at temperature below of 100 K and also,that the charge carrier dynamics,as expressed by hole injection times and free carrier recombination rates,are strongly depended on the actual pervoskite crystal phase,as well as,from the selected hole transport material.

In-plane oriented CH_(3)NH_(3)PbI_(3) nanowire suppression of the interface electron transfer to PCBM

One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance. In this research,we carried out a detailed study on electron transfer process at the interface of nanowire CH_(3) NH_(3) PbI_(3)(N-MAPbI_(3))/Phenyl C61 butyric acid methyl-ester synonym(PCBM), as well as the interface of compact CH_(3) NH_(3) PbI_(3)(C-MAPbI_(3))/PCBM by transient absorption spectroscopy. By comparing the carrier recombination dynamics of N-MAPbI_(3), N-MAPbI_(3)/PCBM,C-MAPbI_(3), and C-MAPbI_(3)/PCBM from picosecond(ps) to hundred nanosecond(ns) time scale, it is demonstrated that electron transfer at N-MAPbI_(3)/PCBM interface is less efficient than that at C-MAPbI_(3)/PCBM interface. In addition, electron transfer efficiency at C-MAPbI_(3)/PCBM interface was found to be excitation density-dependent, and it reduces with photo-generation carrier concentration increasing in a range from 1.0 × 1018 cm^(-3)–4.0 × 1018 cm^(-3). Hot electron transfer,which leads to acceleration of electron transfer between the interfaces, was also visualized as carrier concentration increases from 1.0 × 10^(18) cm^(-3)–2.2 × 10^(18) cm^(-3).

Ultrafast proton transfer dynamics of 2-(2'-hydroxyphenyl)benzoxazole dye in different solvents

The excited-state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzoxazole dye in different solvents is investigated using ultrafast femtosecond transient absorption spectroscopy combined with quantum chemical calculations.Conformational conversion from the syn-enol configuration to the keto configuration is proposed as the mechanism of excited-state intramolecular proton transfer.The duration of excited-state intramolecular proton transfer is measured to range from 50 fs to 200 fs in different solvents.This time is strongly dependent on the calculated energy gap between the N-S;and T-S;structures in the S;state.Along the proton transfer reaction coordinate,the vibrational relaxation process on the S;state potential surface is observed.The duration of the vibrational relaxation process is determined to be from8.7 ps to 35 ps dependent on the excess vibrational energy.

Electron transfer dynamics in Schottky junction photocatalyst during electron donor-assisted hydrogen production

Electron donors(EDs)are widely used to improve the H 2 production performance of Schottky junction photocatalysts,but the functions of EDs are still unknown from the perspective of electron transfer dy-namics.Herein,Pt nanocluster-decorated CdS nanorod is successfully prepared to construct a typical CdS/Pt Schottky junction.Pt nanoclusters with a diameter of∼2 nm are deposited on the surface of CdS nanorods by in situ photoreduction at sub-zero temperature.The CdS/Pt photocatalyst using lactic acid shows a higher H_(2)production rate of 4762μmol g^(-1)h^(-1)compared to that using methanol,tri-ethanolamine,and glycerol.To understand the cause,the dynamics of photogenerated carriers in CdS/Pt photocatalysts during ED-assisted H_(2)production are revealed by femtosecond transient absorption spec-troscopy.Among the four organic EDs,lactic acid enables the fastest electron transfer rate of 1.8×10^(9)s^(-1)and the highest electron transfer efficiency of 76%at the CdS/Pt interface due to the most efficient hole consumption.This work sheds light on the importance of efficient interfacial electron transfer for im-proving the photocatalytic performance of Schottky junction photocatalysts.

Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals Special Issue:Emerging Investigators

Singlet fission(SF)is an appealing process where one photoexcited singlet transforms to two triplets,which can overcome thermalization energy loss and improve solar cell efficiency.However,it remains unclear how intermolecular coupling,which is subject to molecular stacking,controls SF pathways and dynamics.Here,we prepared polymorph rubrene single crystals with different stacking geometries,including orthorhombic(Orth.),triclinic(Tri.),and monoclinic(Mono.)phases.By micro-area ultrafast spectroscopy,we find that Orth.and Tri.phases with closerπ-πstacking exhibit co-existing coherent and incoherent SF channels while loosely stacked Mono.phase shows only incoherent SF.Furthermore,incoherent SF is thermally activated in Orth.but barrierless in Mono.and Tri.phases.Quantum mechanical calculation reveals that different electronic coupling strength in different phases leads to different SF dynamics.This study demonstrates that molecular stacking governs SF dynamics through electronic coupling,providing guidance for designing efficient SF materials via crystal structural engineering.

Photoinduced excimer generation in perylene diimide dimer:effects of solvent polarity[Invited]

The aggregation and photoinduced excited state dynamics of organic π-conjugated molecules play a vital role in solar energy conversion and applications.This work investigates how solvent polarity affects the aggregation behavior and the photophysical process of perylene diimide dimer(PDI-II).The results show that the conjugations between PDI intramolecular chromophores are more likely to generate excimer,and the conjugations between PDI intermolecular chromophores are more likely to experience symmetry-breaking charge separation.Our study can provide a reference for the design of high-efficiency solar energy conversion materials.

Dynamics of exciton energy renormalization in monolayer transition metal disulfides

Fundamental understandings on the dynamics of charge carriers and excitonic quasiparticles in semiconductors are of central importance for both many-body physics and promising optoelectronic and photonic applications.Here,we investigated the carrier dynamics and many-body interactions in two-dimensional(2D)transition metal dichalcogenides(TMDs),using monolayer WS2 as an example,by employing femtosecond broadband pump-probe spectroscopy.Three time regimes for the exciton energy renormalization are unambiguously revealed with a distinct red-blue-red shift upon above-bandgap optical excitations.We attribute the dominant physical process in the three typical regimes to free carrier screening effect,Coulombic exciton-exciton interactions and Auger photocarrier generation,respectively,which show distinct dependence on the optical excitation wavelength,pump fluences and/or lattice temperature.An intrinsic exciton radiative lifetime of about 1.2 picoseconds(ps)in monolayer WS2 is unraveled at low temperature,and surprisingly the efficient Auger nonradiative decay of both bright and dark excitons puts the system in a nonequilibrium state at the nanosecond timescale.In addition,the dynamics of trions at low temperature is observed to be significantly different from that of excitons,e.g.,a long radiative lifetime of^108.7 ps at low excitation densities and the evolution of trion energy as a function of delay times.Our findings elucidate the dynamics of excitonic quasiparticles and the intricate many-body physics in 2D semiconductors,underpinning the future development of photonics,valleytronics and optoelectronics based on 2D semiconductors.

CsPbBr_(3)纳米晶微观形貌非依赖的线性吸收截面

胶体钙钛矿纳米晶的形貌变化赋予其不同的光学和电子特性,其中,线性吸收截面是决定材料本征光物理特性及其应用潜力的主要参数.本文研究了三种不同形貌的全无机钙钛矿CsPbBr3纳米晶(纳米立方体、纳米片和纳米线),通过飞秒瞬态吸收光谱分析了它们的线性吸收截面值σ.在高于带隙的能量激发下,单个CsPbBr_(3)纳米晶的吸收截面值与形貌无关,且随着粒子的体积(VNC)呈σ400=9.45×10^(4)cm^(−1)×VNC(cm^(2))趋势变化.密度泛函理论证实了形貌对光学选择规则基本没有影响,同时,根据吸收截面值也计算得到了定义本征辐射复合率的爱因斯坦自发辐射系数.然而,当激发能接近带隙(460 nm)时,吸收截面值对纳米晶尺寸的依赖关系变弱,取值满足σ460=2.82×10^(8)cm0.65×(VNC)0.45(cm^(2)),这主要归因于钙钛矿纳米晶的离散能级及靠近带边的较低的态密度.本文的研究结果为洞悉钙钛矿纳米晶的光学特性提供了深入的见解.

Dynamic Mechanism of Relaxation Paths Occurring in TPA-DCPP： Roles of Solvent and Temperature

The relaxation paths for triphenylamine（TPA）-2,3-dicyanopyrazino phenanthrene（DCPP）, which has a pull-push structure, were investigated via steady-state, time-resolved spectroscopy involving transient absorption and time-correlated single photon counting. By changing the solvent polarity we found that an intramolecular charge transfer（ICT） state acting as a ＂bright＂ state was responsible for the fluorescence character of TPA-DCPP. Meanwhile, a ＂dark＂ state gradually appeared and competed with the ICT state. This was likely to be responsible for the polarity-dependent evolution of fluorescence intensity and fluorescence lifetime. The temperature-dependent fluorescence character of the TPA-DCPP in toluene exhibited ICT processes at high temperatures prior to the relaxation path from the initial excited state to the ground state. Our results provide useful insight into the optoelectronic properties of these kinds of molecules.