Femtosecond Transient Absorption Spectroscopy Research Articles

Study of rutile TiO2(110) single crystal by transient absorption spectroscopy in the presence of Ce4+ cations in aqueous environment. Implication on water splitting

Ce4+ cations are commonly used as electron acceptors during the water oxidation to O2 reaction over Ir- and Ru-based catalysts. They can also be reduced to Ce3+ cations by excited electrons from the conduction band of an oxide semiconductor with a suitable energy level. In this work, we have studied their interaction with a rutile TiO2(110) single crystal upon band gap excitation by femtosecond transient absorption spectroscopy (TAS) in solution in the 350–900 nm range and up to 3.5 ns. Unlike excitation in the presence of water alone the addition of Ce4+ resulted in a clear ground-state bleaching (GSB) signal at the band gap energy of TiO2 (ca. 400 nm) with a time constant t = 4–5 ps. This indicated that the Ce4+ cations presence has quenched the e-h recombination rate when compared to water alone. In addition to GSB, two positive signals are observed and are attributed to trapped holes (in the visible region, 450–550 nm) and trapped electrons in the IR region (>700 nm). Contrary to expectation, the lifetime of the positive signal between 450 and 550 nm decreased with increasing concentrations of Ce4+. We attribute the decrease in the lifetime of this signal to electrostatic repulsion between Ce4+ at the surface of TiO2(110) and positively charged trapped holes. It was also found that at the very short time scale (<2–3 ps) the fast decaying TAS signal of excited electrons in the conduction band is suppressed because of the presence of Ce4+ cations. Results point out that the presence of Ce4+ cations increases the residence time (mobility) of excited electrons and holes at the conduction band and valence band energy levels (instead of being trapped). This might provide further explanations for the enhanced reaction rate of water oxidation to O2 in the presence of Ce4+ cations.

Elucidating photocycle in large Stokes shift red fluorescent proteins: Focus on mKeima.

Large Stokes shift red fluorescent proteins (LSS-RFPs) are genetically encoded and exhibit a significant difference of a few hundreds of nanometers between their excitation and emission peak maxima (i.e., the Stokes shift). These LSS-RFPs (absorbing blue light and emitting red light) feature a unique photocycle responsible for their significant Stokes shift. The photocycle associated with this LSS characteristic in certain RFPs is quite perplexing, hinting at the complex nature of excited-state photophysics. This article provides a brief review on the fundamental mechanisms governing the photocycle of various LSS-RFPs, followed by a discussion on experimental results on mKeima emphasizing its relaxation pathways which garnered attention due to its >200 nm Stokes shift. Corroborating steady-state spectroscopy with computational studies, four different forms of chromophore of mKeima contributing to the cis-trans conformers of the neutral and anionic forms were identified in a recent study. Furthering these findings, in this account a detailed discussion on the photocycle of mKeima, which encompasses sequential excited-state isomerization, proton transfer, and subsequent structural reorganization involving three isomers, leading to an intriguing temperature and pH-dependent dual fluorescence, is explored using broadband femtosecond transient absorption spectroscopy.

Elucidating Structural Disorder in Ultra-Thin Bi-Rich Bismuth Oxyhalide Photocatalysts.

Advancing the field of photocatalysis requires the elucidation of structural properties that underpin the photocatalytic properties of promising materials. The focus of the present study is layered, Bi-rich bismuth oxyhalides, which are widely studied for photocatalytic applications yet poorly structurally understood, due to high levels of disorder, nano-sized domains, and the large number of structurally similar compounds. By connecting insights from multiple scattering techniques, utilizing electron-, X-ray- and neutron probes, the crystal phase of the synthesized materials is allocated as layered Bi24O31X10 (X = Cl, Br), albeit with significant deviation from the reported 3Dcrystalline model. The materials comprise anisotropic platelet-shaped crystalline domains, exhibiting significant in-plane ordering in two dimensionsbut disorder and an ultra-thin morphology in the layer stacking direction. Increased synthesis pH tailored larger, more ordered crystalline domains, leading to longer excited state lifetimes determined via femtosecond transient absorption spectroscopy (fs-TAS). Although this likely contributes to improved photocatalytic properties, assessed via the photooxidation of benzylamine, increasing the overall surface area facilitated the most significant improvement in photocatalytic performance. This study, therefore, enabled both phase allocation and a nuanced discussion of the structure-property relationship for complicated, ultra-thin photocatalysts.

Oxygen Vacancies Trigger Rapid Charge Transport Channels at the Engineered Interface of S-scheme Heterojunction for Boosting Photocatalytic Performance.

Although oxygen vacancies (Ovs) have been intensively studied in single semiconductor photocatalysts, exploration of intrinsic mechanisms and in-depth understanding of Ovs in S-scheme heterojunction photocatalysts are still limited. Herein, a novel S-scheme photocatalyst made from WO3-Ov/In2S3 with Ovs at the heterointerface is rationally designed. The microscopic environment and local electronic structure of the S-scheme heterointerface are well optimized by Ovs. Femtosecond transient absorption spectroscopy (fs-TAS) reveals that Ovs trigger additional charge movement routes and therefore increase charge separation efficiency. In addition, Ovs have a synergistic effect on the thermodynamic and kinetic parameters of S-scheme photocatalysts. As a result, the optimal photocatalytic performance is significantly improved, surpassing that of single component WO3-Ov and In2S3 (by 35.5 and 3.9 times, respectively), as well as WO3/In2S3 heterojunction. This work provides new insight into regulating the photogenerated carrier dynamics at the heterointerface and also helps design highly efficient S-scheme photocatalysts.

Oxygen Vacancies Trigger Rapid Charge Transport Channels at the Engineered Interface of S‐scheme Heterojunction for Boosting Photocatalytic Performance

Although oxygen vacancies (Ovs) have been intensively studied in single semiconductor photocatalysts, exploration of intrinsic mechanisms and in‐depth understanding of Ovs in S‐scheme heterojunction photocatalysts are still limited. Herein, a novel S‐scheme photocatalyst made from WO3‐Ov/In2S3 with Ovs at the heterointerface is rationally designed. The microscopic environment and local electronic structure of the S‐scheme heterointerface are well optimized by Ovs. Femtosecond transient absorption spectroscopy (fs‐TAS) reveals that Ovs trigger additional charge movement routes and therefore increase charge separation efficiency. In addition, Ovs have a synergistic effect on the thermodynamic and kinetic parameters of S‐scheme photocatalysts. As a result, the optimal photocatalytic performance is significantly improved, surpassing that of single component WO3‐Ov and In2S3 (by 35.5 and 3.9 times, respectively), as well as WO3/In2S3 heterojunction. This work provides new insight into regulating the photogenerated carrier dynamics at the heterointerface and also helps design highly efficient S‐scheme photocatalysts.

Ultrafast Exciton Dynamics of CH3NH3PbBr3 Perovskite Nanoclusters.

Exciton dynamics of perovskite nanoclusters has been investigated for the first time using femtosecond transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopy. The TA results show two photoinduced absorption signals at 420 and 461 nm and a photoinduced bleach (PB) signal at 448 nm. The analysis of the PB recovery kinetic decay and kinetic model uncovered multiple processes contributing to electron-hole recombination. The fast component (∼8 ps) is attributed to vibrational relaxation within the initial excited state, and the medium component (∼60 ps) is attributed to shallow carrier trapping. The slow component is attributed to deep carrier trapping from the initial conduction band edge (∼666 ps) and the shallow trap state (∼40 ps). The TRPL reveals longer time dynamics, with modeled lifetimes of 6.6 and 93 ns attributed to recombination through the deep trap state and direct band edge recombination, respectively. The significant role of exciton trapping processes in the dynamics indicates that these highly confined nanoclusters have defect-rich surfaces.

Plasmon-Induced Ultrafast Hot Hole Transfer in Nonstoichiometric CuxInyS/CdS Heteronanocrystals.

Plasmonic semiconductors are promising candidates for developing energy conversion devices due to their tunable band gap, cost-effectiveness, and nontoxicity. Such materials exhibit remarkable capabilities for harvesting infrared photons, which constitute half of the solar energy spectrum. Herein, we have synthesized near-infrared (NIR) active CuxInyS nanocrystals and CuxInyS/CdS heterostructure nanocrystals (HNCs) to investigate plasmon-induced charge transfer dynamics on an ultrafast time scale. Employing femtosecond transient absorption spectroscopy, we demonstrate that upon exciting the HNCs with sub-band gap NIR photons (λ = 840 nm), the hot holes are generated in the valence band of plasmonic CuxInyS and transferred to the adjacent semiconductor. The decreased signal intensity and accelerated hole phonon relaxation dynamics for HNCs reveal efficient transfer of plasmon-induced hot carriers from CuxInyS to CdS under both 840 and 350 nm laser excitations, providing a pathway for enhanced carrier utilization. These findings shed light on the potential of ternary chalcogenides in plasmonic applications, highlighting efficient hot carrier extraction to adjacent semiconductors.

Axial coordinated manganeseporphyrin/tetraazaporphyrin-4-(10-phenylanthracen-9-yl)pyridine dyads: self-assembly, structure and spectral properties in ground and excited states.

Self-assembly of new donor-acceptor systems based on (5,10,15,20-tetraphenylporphinato)manganese(III)/(5,10,15,20-tetra-4-tert-butylphenylporphinato)manganese(III)/(octakis(4-tert-butylphenyl)tetraazaporphinato)manganese(III) acetate ((AcO)MnTPP/(AcO)MnTBPP/(AcO)MnTAP) and 4-(10-phenylanthracen-9-yl)pyridine (PyAn) was studied using fluorescence spectroscopy and mass spectrometry. It was found that the coordination complexes of 1:1 composition (dyads) are formed in toluene. The spectral properties, the chemical structures and redox behavior of the dyads were described using 1H NMR, IR, EPR spectroscopy and cyclic voltammetry, respectively. The dynamic processes and the characteristics in the excited state of the dyads were obtained using the femtosecond transient absorption spectroscopy method. Density functional theory (DFT), time-dependent DFT methods were used to elucidate the dyad electronic structures and to establish the differences in their frontier molecular orbitals. The analysis of the lambda parameter and the distance of hole-pair interaction was indicated more favorable charge transfer between the macrocycle and the axial PyAn fragment in (AcO)(PyAn)MnTAP. The calculated values of the zero-field splitting parameters D and E/D, together with the g tensors of the lowest spin-orbit state for (AcO)MnTPP and (AcO)(PyAn)MnTPP were obtained using the combination of DFT and Multireference Perturbation Theory (CASSCF/NEVPT2) simulations. The data obtained develop the fundamental basis in the field of photovoltaics and show the prospects for the study of molecular systems of this class.

Cypate-sensitized upconversion nanoprobes for intracellular and in-vivo ATP ratiometric detection

As energy currency of life, adenosine triphosphate (ATP) is highly dynamic in living organisms. It is crucial yet challenging to probe intracellular or in-vivo ATP precisely without destruction of the living biological systems. Herein, we have designed novel ATP-responsive ratiometric nanoprobes by employing upconversion nanoparticles (UCNPs) with cypate as antennas. Nuclear magnetic resonance spectroscopy was used to analyze the interfacial interactions among lanthanide nanocrystal, cypate and adenosine phosphates, disclosing the origin of detection specificity. ATP induced interruption of energy transfer pathway in cypate-sensitized UCNPs was further investigated by femtosecond transient absorption and time-resolved photoluminescence spectroscopy. The nanoprobes with dual near-infrared (NIR)-excited ratiometric UCL were successfully applied for quantification of ATP level in living cells under vegetatively growing, starving, and glycolysis-inhibiting states, respectively. Furthermore, the increase of available energy by feeding for zebrafish larvae was confirmed through monitoring the in-vivo ATP variation with the nanoprobes. Such nanoprobes showed great potential in ATP-associated biological research and clinical applications. These findings may gain deep insights into the surface science and photophysics in dye-lanthanide nanocomposites, and open new avenues for the design and bioapplications of lanthanide nanoprobes.

Effect of Mixture Composition on the Photophysics of Indoline Dyes in Imidazolium Ionic Liquid-Molecular Solvent Mixtures: A Femtosecond Transient Absorption Study.

We conducted a study on the photophysics of three indoline dyes, D102, D149, and D205, in binary mixtures of ionic liquids (IL) and polar aprotic molecular solvents (MS). Specifically, we examined the behavior of these dyes in IL-MS mixtures containing four different imidazolium-based ILs and three different polar aprotic MSs. Our investigation involved several techniques, including stationary absorption and emission measurements, as well as femtosecond transient absorption (TA) spectroscopy. Through our analysis, we discovered a peculiar behavior of several photophysical properties at low IL mole fractions (0 < XIL < 0.2). Indeed, in this range of mixture composition, the absorption maximum wavelength decreases noticeably, while the emission maximum wavelength and the Stokes shift, expressed in wavenumbers, reach a maximum. while a minimum occurs in the relative quantum yield and the excited state lifetime. These results indicate that the solvation of dye undergoes a large change in this range of mixture composition. We found that, at high ionic liquid content, the excited relaxation times are correlated with the high viscosity, while at low content, it is the polarity of the solvent that influences the behavior of the excited relaxation times. At a mixture composition of around 0.10, the behavior of the photophysical properties of the studied IL-MS mixtures indicates a crossover between situations where the solvation is dominated by that of ions and that dominated by the solvent.

Modulation of Photoinduced Phase Segregation and Stress-Driven Nanoscale Cracking in Hybrid Halide Perovskite Solar Cells.

The negative effect of photoinduced halide segregation (PIHS) on the properties of hybrid halide perovskites poses a major obstacle for its future commercial application. Therefore, the in-depth understanding of halide-ion segregation and its causes is an urgent and intractable problem. When PIHS reaches a certain threshold, it will aggravate the deterioration of the film surface morphology and form nanoscale cracks. Herein, the formation mechanism and types of cracks are revealed by exploring the stress distribution in the film. Using the femtosecond time-resolved transient absorption spectroscopy, the ultrafast formation of the iodine rich phase is observed, which appears earlier than the bromine rich phase. In addition, the introduction of organic ligand didodecyldimethylammonium bromide can significantly inhibit PIHS and improve the surface morphology of the film, which can promote the device efficiency from 9.63 to 11.20%. This work provides a novel perspective for the exploration of the PIHS.

Influence of donor-acceptor interactions on MLCT hole reconfiguration in {Ru(bpy)} chromophores.

In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2'-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.

Photogenerated carrier dynamics of Mn2+ doped CsPbBr3 assembled with TiO2 systems: Effect of Mn doping content.

In recent years, all-inorganic perovskite materials have become an ideal choice for new thin film solar cells due to their excellent photophysical properties and have become a research hotspot. Studying the ultrafast dynamics of photo-generated carriers is of great significance for further improving the performance of such devices. In this work, we focus on the transient dynamic process of CsPbBr3/TiO2 composite systems with different Mn2+ doping contents using femtosecond transient absorption spectroscopy technology. We used singular value decomposition and global fitting to analyze the transient absorption spectra and obtained three components, which are classified as hot carrier cooling, charge transfer, and charge recombination processes, respectively. We found that the doping concentration of Mn2+ has an impact on all three processes. We think that the following two factors are responsible: one is the density of defect states and the other is the bandgap width of perovskite. As the concentration of doped Mn2+ increases, the charge transfer time constant shows a trend of initially increasing, followed by a subsequent decrease, reaching a turning point. This indicates that an appropriate amount of Mn2+ doping can effectively improve the photoelectric performance of solar cell systems. We proposed a possible charge transfer mechanism model and further elucidated the microscopic mechanism of the effect of Mn2+ doping on the interface charge transfer process of the CsPbBr3/TiO2 solar cell system.

Poly(triphenylamine-thiazolo[5,4-d]thiazole) copolymer dyes with different anchoring end groups: Synthesis, dye-sensitized solar cell (DSSC) performance and femtosecond excited state absorption spectroscopy

In this study, the poly(triphenylaminethiazolo[5,4-d]thiazole) copolymer dyes having the different anchoring end groups of aldehyde (poly-TPATT-CHO; P5), sulfonic acid (poly-TPATT-SO3H; P5S) and cyanoacrylic acid (poly-TPATT-COOH; P5C) have been synthesized and used as sensitizers in dye-sensitized solar cells (DSSCs). The effects of the anchoring end groups of the P5, P5S and P5C copolymer dyes on the DSSC performance were examined. The synthesized copolymer dyes were characterized using 1H NMR, UV–vis. absorption and fluorescence (FL) emission spectroscopy, cyclic voltammetry (CV), MALDI-TOF-MS and FE-SEM-EDS methods. Among the studied polymers, the P5C polymer dye exhibited the best photovoltaic performance with a JSC of 6.46 mA cm−2, a VOC of 0.667 V, a FF of 0.70, and an overall power conversion efficiency (PCE) of 3.02 % under standard AM 1.5 G solar light conditions. These results are attributed to the strong binding ability of cyanoacrylic acid to the TiO2, leading to a greater photocurrent and hindered charge recombination. The effect of electron transfer mechanisms of the polymers on the DSSC performance have been investigated using the femtosecond transient absorption (fs TA) spectroscopy. The DSSC performance of the poly(triphenylaminethiazolo[5,4-d]thiazole) increased greatly by the presence of the cyanoacrylic acid anchoring end group in P5C polymer dye. The fs TA spectroscopy results revealed the presence of singlet–triplet transition for the P5C copolymer dye, while the P5 and P5S copolymers showed only singlet–singlet transitions. The observed triplet state transition in the P5C polymer increased the yield of the DSSC system.

Construction of an Electron Capture and Transfer Center for Highly Efficient and Selective Solar-Light-Driven CO2 Conversion.

Exploring high-efficiency photocatalysts for selective CO2 reduction is still challenging because of the limited charge separation and surface reactions. In this study, a noble-metal-free metallic VSe2 nanosheet was incorporated on g-C3N4 to serve as an electron capture and transfer center, activating surface active sites for highly efficient and selective CO2 photoreduction. Quasi in situ X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and femtosecond transient absorption spectroscopy (fs-TAS) unveiled that VSe2 could capture electrons, which are further transferred to the surface for activating active sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations revealed a kinetically feasible process for the formation of a key intermediate and confirmed the favorable production of CO on the VSe2/PCN (protonated C3N4) photocatalyst. As an outcome, the optimized VSe2/PCN composite achieved 97% selectivity for solar-light-driven CO2 conversion to CO with a high rate of 16.3 μmol·g-1·h-1, without any sacrificial reagent or photosensitizer. This work offers new insights into the photocatalyst design toward highly efficient and selective CO2 conversion.

Revealing photoluminescence and nonlinear optical absorption characteristics of PbMo0.75W0.25O4 single crystal for optical limiting applications

Nonlinear absorption properties of PbMo0.75W0.25O4 single crystal fabricated by the Czochralski method were studied. The band gap energy of the crystal was determined as 3.12 eV. Urbach energy which represents the defect states inside the band gap was found to be 0.106 eV. PbMo0.75W0.25O4 single crystal has a broad photoluminescence emission band between 376 and 700 nm, with the highest emission intensity occurring at 486 nm and the lowest intensity peak at 547 nm, depending on the defect states. Femtosecond transient absorption measurements reveal that the lifetime of localized defect states is found to be higher than the 4 ns pulse duration. Open aperture (OA) Z-scan results demonstrate that the PbMo0.75W0.25O4 single crystal exhibits nonlinear absorption (NA) that includes two-photon absorption (TPA) as the dominant mechanism at the 532 nm excitations corresponding to 2.32 eV energy. NA coefficient (β eff ) increased from 7.24 × 10−10 m W−1 to 8.81 × 10−10 m W−1 with increasing pump intensity. At higher intensities β eff tends to decrease with intensity increase. This decrease is an indication that saturable absorption (SA) occurred along with the TPA, called saturation of TPA. The lifetime of the defect states was measured by femtosecond transient absorption spectroscopy. Saturable absorption behavior was observed due to the long lifetime of the localized defect states. Closed aperture (CA) Z-scan trace shows the sign of a nonlinear refractive index. The optical limiting threshold of PbMo0.75W0.25O4 single crystal at the lowest intensity was determined as 3.45 mJ/cm2. Results show that the PbMo0.75W0.25O4 single crystal can be a suitable semiconductor material for optical limiting applications in the visible region.

Shedding light on imaging safety: Decoding the origin of photocytotoxicity in RhB-assisted fluorescence imaging.

Photocytotoxicity represents a significant limitation in the application of dye-assisted fluorescence imaging (FI), often resulting in undesirable cellular damage or even cell death, thereby restricting their practical utility. The prevalence of Rhodamine B (RhB) in FI underscores the importance of elucidating its photocytotoxicity effects to minimize photodamage. This study identifies the primary cause of photocytotoxicity stems from the generation of cytotoxic singlet oxygen in RhB, utilizing femtosecond transient absorption spectroscopy coupled with quantum chemical calculations. The Laser power-dependent cellular viability reveals a threshold at about 50 mW cm-2, surpassing which produces pronounced photocytotoxicity in vitro and in vivo. Notably, this threshold significantly falls below the safety limits (<200 mW cm-2) for laser use in health care, implying a huge risk of photodamage. This study provides valuable insights into the photocytotoxicity and offers essential guidelines for developing safer imaging protocols.

Breaking the Activity-Selectivity Trade-off for CH4-to-C2H6 Photoconversion.

Photocatalytic conversion of methane (CH4) to ethane (C2H6) has attracted extensive attention from academia and industry. Typically, the traditional oxidative coupling of CH4 (OCM) reaches a high C2H6 productivity, yet the inevitable overoxidation limits the target product selectivity. Although the traditional nonoxidative coupling of CH4 (NOCM) can improve the product selectivity, it still encounters unsatisfied activity, arising from being thermodynamically unfavorable. To break the activity-selectivity trade-off, we propose a conceptually new mechanism of H2O2-triggered CH4 coupling, where the H2O2-derived ·OH radicals are rapidly consumed for activating CH4 into ·CH3 radicals exothermically, which bypasses the endothermic steps of the direct CH4 activation by photoholes and the interaction between ·CH3 and ·OH radicals, affirmed by in situ characterization techniques, femtosecond transient absorption spectroscopy, and density-functional theory calculation. By this pathway, the designed Au-WO3 nanosheets achieve unprecedented C2H6 productivity of 76.3 mol molAu-1 h-1 with 95.2% selectivity, and TON of 1542.7 (TOF = 77.1 h-1) in a self-designed flow reactor, outperforming previously reported photocatalysts regardless of OCM and NOCM pathways. Also, under outdoor natural sunlight irradiation, the Au-WO3 nanosheets exhibit similar activity and selectivity toward C2H6 production, showing the possibility for practical applications. Interestingly, this strategy can be applied to other various photocatalysts (Au-WO3, Au-TiO2, Au-CeO2, Pd-WO3, and Ag-WO3), showing a certain universality. It is expected that the proposed mechanism adds another layer to our understanding of CH4-to-C2H6 conversion.

Ultrafast restricted intramolecular rotation in molecules with aggregation induced emission.

In this work, the ultrafast intramolecular rotation behavior of 1,1,2,3,4,5-hexaphenylsilole has been investigated in several solutions with different viscosities using femtosecond transient absorption spectroscopy combined with density functional theory and time-dependent density functional theory calculations. It is demonstrated that the nonradiative process, which competes with radiative decay, involves two main stages, namely the restricted intramolecular rotation and internal conversion processes. The intramolecular rotation depends on viscosity and presents a significant restriction. The restricted rotational rate is determined to be dozens of picoseconds. The following nonradiative process is strongly dominated by intramolecular rotation. The nonradiative decay rate will decrease with the increase in viscosity, leading to a rise in the radiative probability and photoluminous yield. These results have borne out the mechanism of ultrafast restricted intramolecular rotation of aggregation induced emission and provided a detailed photophysical picture of nonradiative processes.

Excited-State Dynamics of Carbazole and tert-Butyl-Carbazole in Thin Films

Thin films of carbazole (Cz) derivatives are frequently used in organic electronics, such as organic light-emitting diodes (OLEDs). Because of the proximity of the Cz units, the excited-state relaxation in such films is complicated, as intermolecular pathways, such as singlet–singlet annihilation (SSA), kinetically compete with the emission. Here, we provide an investigation of two benchmark systems employing neat carbazole and 3,6-di-tert-butylcarbazole (t-Bu-Cz) films and also their thin film blends with poly(methyl methacrylate) (PMMA). These are investigated by a combination of atomic force microscopy (AFM), femtosecond and nanosecond transient absorption spectroscopy (fs-TA and ns-TA) and time-resolved fluorescence. Excitonic J-aggregate-type features are observed in the steady-state absorption and emission spectra of the neat films. The S1 state shows a broad excited-state absorption (ESA) spanning the entire UV–Vis–NIR range. At high S1 exciton number densities of about 4 × 1018 cm−3, bimolecular diffusive S1–S1 annihilation is found to be the dominant SSA process in the neat films with a rate constant in the range of 1–2 × 10−8 cm3 s−1. SSA produces highly vibrationally excited molecules in the electronic ground state (S0*), which cool down slowly by heat transfer to the quartz substrate. The results provide relevant photophysical insight for a better microscopic understanding of carbazole relaxation in thin-film environments.