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Symmetry controlled photo-selection and charge separation in butadiyne-bridged donora??bridgea??acceptor compounds
摘要： Electron transfer (ET) in donor-bridge-acceptor (DBA) compounds depends strongly on the structural and electronic properties of the bridge. Among the bridges that support donor - acceptor conjugation, alkyne bridges have attractive and unique properties: they are compact, possess linear structure permitting access to high symmetry DBA structures, and allow torsional motion of D and A, especially for longer bridges. We report conformation dependent electron transfer dynamics in a set of novel DBA compounds featuring butadiyne (C4) bridge, N-isopropyl-1,8-napthalimide (NAP) acceptors, and donors that span a range of reduction potentials (trimethyl silane (Si-C4-NAP), phenyl (Ph-C4-NAP), and dimethyl aniline (D-C4-NAP)). Transient mid-IR absorption spectra of the C≡C bridge stretching modes, transient spectra in the visible range and TD-DFT calculations were used to decipher the ET mechanisms. We found that the electronic excited state energies and, especially, the transition dipoles (S0→Sn) depend strongly on the dihedral angle (θ) between D and A and the frontier orbital symmetry, offering an opportunity to photo-select particular excited states with specific ranges of dihedral angles by exciting at chosen wavelengths. For example, excitation of D-C4-NAP at 400 nm predominantly prepares an S1 excited state in the planar conformations (θ ~ 0) but selects an S2 state with θ ~ 90o, indicating the dominant role of the molecular symmetry in the photophysics. Moreover, the symmetry of the frontier orbitals of such DBA compounds not only defines the photo-selection outcome, but also determines the rate of the S2→S1 charge separation reaction. Unprecedented variation of the S2-S1 electronic coupling with θ by over four orders of magnitude results in slow ET at θ ca. 0o and 90o but extremely fast ET at θ of 20-60o. The unique features of high-symmetry alkyne bridged DBA structures enable frequency dependent ET rate selection and make this family of compounds promising targets for the vibrational excitation control of ET kinetics.
关键词： transient absorption spectroscopy,electron transfer,donor-bridge-acceptor,TD-DFT calculations,butadiyne bridge
更新于2025-09-23 15:19:57
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Investigating ultrafast carrier dynamics in perovskite solar cells with an extended ??-conjugated polymeric diketopyrrolopyrrole layer for hole transportation
摘要： Here, we show a new diketopyrrole based polymeric hole-transport material (PBDTP-DTDPP, (poly[[2,5-bis(2-hexyldecyl)-2,3,5,6-tetrahydro-3,6-dioxopyrrolo[3,4-c]pyrrole-1,4-diyl]-alt-[[2,20-(4,8-bis(4-ethylhexyl-1-phenyl)-benzo[1,2-b:4,5-b0]dithiophene)bis-thieno[3,2-b]thiophen]-5,50-diyl]])) in perovskite solar cells. The material performance was tested in a solar cell with an optimized configuration, FTO/SnO2/perovskite/PBDTP-DTDPP/Au, and the device showed a power conversion efficiency of 14.78%. The device charge carrier dynamics were investigated using transient absorption spectroscopy. The charge separation and recombination kinetics were determined in a device with PBDTP-DTDPP and the obtained results were compared to a reference device. We find that PBDTP-DTDPP enables similar charge separation time (<4.8 ps) to the spiro-OMeTAD but the amount of nongeminate recombination is different. Specifically, we find that the polymeric PBDTP-DTDPP hole-transport layer (HTL) slows-down the second-order recombination much less than spiro-OMeTAD. This effect is of particular importance in studying the charge transportation in optimized solar cell devices with diketopyrrole based HTL materials.
关键词： perovskite solar cells,transient absorption spectroscopy,PBDTP-DTDPP,charge carrier dynamics,hole-transport material
更新于2025-09-23 15:19:57
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Size- and Composition-Dependent Exciton Spin Relaxation in Lead Halide Perovskite Quantum Dots
摘要： The strong spin-orbital coupling in lead halide perovskites allows for facile spin injection for spintronics applications, but on the other hand also limits the lifetime of the injected spins. Full-dimensional confinement of the carriers using quantum dots (QDs) has been envisioned as an effective means to prolong the spin relaxation lifetime and has been explored for II-VI and III-V group QDs. Here we applied this idea to colloidal lead halide perovskite QDs and measured the exciton spin dynamics of QDs of varying sizes and compositions using circularly polarized transient absorption spectroscopy at room temperature. Interestingly, the spin lifetimes of CsPbI3 and CsPbBr3 QDs were prolonged and shortened, respectively, as compared to their bulk counterparts. Both CsPbI3 and CsPbBr3 QDs showed decreasing spin lifetime with decreasing QD size. Possible spin relaxation mechanisms, including those that are unique to these quantum-confined systems, were proposed, with important ramifications for the use of these perovskite QDs in spin-related applications.
关键词： lead halide perovskites,spin-orbital coupling,exciton spin dynamics,circularly polarized transient absorption spectroscopy,quantum dots
更新于2025-09-23 15:19:57
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Photocarrier relaxation pathway in selenium quantum dots and its application for UV-Vis photodetecting
摘要： Chain-like materials have recently attracted significant attention due to their unique structure and outstanding electro-optical properties. However, the photocarrier dynamics and pathways in these materials that determine the electro-optical performances of the prepared devices have barely been touched. Herein, one typical chain-like materials e quantum dots (Se QDs) were prepared via a facile liquid phase exfoliation approach. The photocarrier dynamics in selenium quantum dots were systematically investigated via ultrafast transient absorption spectroscopy in the ultraviolet-visible regime. Four photocarrier decay pathways with different lifetime times were firstly detected, endues the elucidation and reconstruction of the energy schematic diagram of Se QDs. Thanks to the broadband photo-response and fast recovery time of Se QDs, a photoelectrochemical (PEC)-typed photodetector was proposed for the first time to our knowledge, demonstrating excellent photodetection properties. Considering the feasible fabrication method and clear photocarrier pathways, the excellent photocurrent density and stability of this photodetector undoubtedly guarantee the promising of selenium for advanced photonics devices.
关键词： broadband photo-response,photocarrier dynamics,ultrafast transient absorption spectroscopy,selenium quantum dots,photoelectrochemical photodetector
更新于2025-09-23 15:19:57
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Size- and Surface-Dependent Photoresponses of Solution-Processed Aluminum Nanoparticles
摘要： Plasmonic aluminum nanoparticles have emerged as an exciting new materials platform due to the high natural abundance of aluminum, their ability to be synthesized in the solution phase, and the potential of these materials to be used for photocatalysis and sensing. However, the photothermal properties of solution-processed aluminum nanoparticles, in particular, how phonon energy transfer depends on the particle size and surface properties, are critical for practical applications and are currently unexplored. Here we use transient absorption spectroscopy, in combination with simulations of phonon and thermal energy dissipation, to investigate the photoresponses of aluminum nanoparticles of various diameters (54, 85, 121, and 144 nm) suspended in 2-propanol. Fast thermal-transfer rates to the solvent (170?280 ps) are observed for particles of all sizes and are facilitated by native oxide coverage, as veri?ed by a two-interface thermal energy-transfer model. Size-dependent phonon “breathing”/vibrational modes are also observed as oscillations in the total cross-section. We ?nd that both the oscillation frequency and the damping rate increase as the diameter of the particles decreases. On the basis of the results of ?nite element calculations, we attribute the damping strength and oscillation period observed to a combination of the noncrystalline nature of the native oxide shell and the presence of surface-bound ligands, both of which increase the vibrational mode damping rates relative to bare Al and Al particles with a bare crystalline oxide shell. These insights should guide future work on controlling energy transfer through the use of size and surface tuning in sustainable aluminum nanomaterial systems for applications in catalysis and sensing.
关键词： aluminum,phonons,surface effects,transient absorption,heat transfer,localized surface plasmon resonances
更新于2025-09-23 15:19:57
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Coherent Exciton Dynamics in Ensembles of Size-Dispersed CdSe Quantum Dot Dimers Probed via Ultrafast Spectroscopy: A Quantum Computational Study
摘要： Interdot coherent excitonic dynamics in nanometric colloidal CdSe quantum dots (QD) dimers lead to interdot charge migration and energy transfer. We show by electronic quantum dynamical simulations that the interdot coherent response to ultrashort fs laser pulses can be characterized by pump-probe transient absorption spectroscopy in spite of the inevitable inherent size dispersion of colloidal QDs. The latter, leading to a broadening of the excitonic bands, induce accidental resonances that actually increase the efficiency of the interdot coupling. The optical electronic response is computed by solving the time-dependent Schrodinger equation including the interaction with the oscillating electric field of the pulses for an ensemble of dimers that differ by their size. The excitonic Hamiltonian of each dimer is parameterized by the QD size and interdot distance, using an effective mass approximation. Local and charge transfer excitons are included in the dimer basis set. By tailoring the QD size, the excitonic bands can be tuned to overlap and thus favor interdot coupling. Computed pump-probe transient absorption maps averaged over the ensemble show that the coherence of excitons in QD dimers that lead to interdot charge migration can survive size disorder and could be observed in fs pump-probe, four-wave mixing, or covariance spectroscopy.
关键词： coherent electronic dynamics,pump-probe transient absorption spectroscopy,CdSe quantum dots dimers,exciton dynamics,size dispersion effects
更新于2025-09-23 15:19:57
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The role of self-trapped excitons in polaronic recombination processes in lithium niobate
摘要： Transient absorption and photoluminescence are experimentally investigated in the polaronic reference system lithium niobate, LiNbO3 (LN), with the aim to refine the microscopic model of small polaron dynamics in materials with strong electron-phonon coupling. As a unique feature, our study is performed by using two different spectroscopic methods, in crystals with dopants enhancing photorefraction or damage resistance, and over a broad temperature range from 15?400 K. Although being self-consistent for particular experimental conditions, the hitherto used microscopic polaronic models reveal inconsistencies when applied to this larger data set. We show that comprehensive modeling is unlocked by the inclusion of an additional type of polaronic state with the following characteristics: (i) strongly temperature- and dopant-dependent relaxation times, (ii) an absorption feature in the blue-green spectral range, and (iii) a Kohlrausch-Williams-Watts decay shape with a temperature-dependent stretching factor β(T ) showing a behavior contrary to that of small, strong-coupling polarons. The hypothesis of self-trapped excitons (STEs, i.e., bound electron-hole pairs strongly coupled to Nb5+ and O2? within a niobium-oxygen octahedron) and their pinning on defects as the microscopic origin of these characteristics is supported by a spectroscopic linkage of photoluminescence at low (15 K) and elevated (300 K) temperatures and explains the long-lifetime components in transient absorption as due to pinned STEs.
关键词： self-trapped excitons,lithium niobate,photoluminescence,transient absorption,polaronic recombination
更新于2025-09-23 15:19:57
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Localized Nanoscale Heating Leads to Ultrafast Hydrogel Volume-Phase Transition
摘要： The rate of the volume-phase transition for stimuli-responsive hydrogel particles ranging in size from millimeters to nanometers is limited by the rate of water transport, which is proportional to the surface area of the particle. Here, we hypothesized that the rate of volume-phase transition could be accelerated if the stimulus is geometrically controlled from the inside-out, thus facilitating outward water ejection. To test this concept, we applied transient absorption spectroscopy, laser temperature-jump spectroscopy and finite-element analysis modeling to characterize the dynamics of the volume-phase transition of hydrogel particles with a gold nanorod core. Our results demonstrate that nanoscale heating of the hydrogel particle core led to an ultrafast, 60 ns particle collapse, which is 2-3 orders of magnitude faster than the response generated from conventional heating. This is the fastest recorded response time of a hydrogel material, thus opening potential applications for such stimuli-responsive materials.
关键词： infrared spectroscopy,dynamic light scattering,nanorods,volume-phase transition,hydrogel,transient absorption
更新于2025-09-23 15:19:57
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Ultrafast Protein Response in Channelrhodopsin-2 Studied by Time-Resolved IR Spectroscopy
摘要： Ultrafast IR transient absorption in the carbonyl vibrational region of protonated aspartate and glutamate residues in Channelrhodopsin-2 from Chlamydomonas reinhardtii shows immediate protein response to retinal excitation. The observed difference bands are formed directly after the excitation on the sub-ps time scale and were assigned to side chains in the retinal vicinity, such as D156 and E90. This finding implies an ultrafast and effective energy transfer from the retinal to its environment via hydrogen-bonded networks and reveals extraordinary strong chromophore-protein coupling and intense interaction within the protein. Relevance on the protein function as optically gated ion channel are discussed.
关键词： Channelrhodopsin-2,protein response,ion channel,Ultrafast IR transient absorption,hydrogen-bonded networks,chromophore-protein coupling,retinal excitation
更新于2025-09-23 15:19:57
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Determination of size dependent carrier capture in InGaN/GaN quantum nanowires by femto-second transient absorption spectroscopy: effect of optical phonon, electron-electron scattering and diffusion
摘要： Understanding the ultrafast processes corresponding to carrier capture, thermalization and relaxation is essential to design high-speed optoelectronic devices. Here, we have investigated size dependent carrier capture process in InGaN/GaN 20 nm, 50 nm nanowires and quantum well systems. Femto-second transient absorption spectroscopy reveals that the carrier capture is a two-step process. The carriers are captured in the barrier by polar optical phonon scattering. They further scatter into the active region by electron-electron and polar optical phonon scatterings. The capture is found to slow down for quantum confined structures. A significant number of carriers are found to disappear from the barrier during the diffusion process. All the experimental observations are explained in a simulation framework depicting various scattering mechanisms.
关键词： nanowire,polar optical phonon scattering,electron-electron scattering,transient absorption spectroscopy,carrier capture,electron and phonon dynamics
更新于2025-09-19 17:15:36