Carrier Recombination Dynamics Research Articles

Positional Isomerism of Aromatic Heterocyclic Spacer Cations in Two-Dimensional Dion-Jacobson Hybrid Perovskites.

Ligand engineering of aromatic heterocyclic cations in two-dimensional (2D) Dion-Jacobson (DJ) perovskites has been widely explored in recent years. In this study, how the positional isomers of aromatic heterocyclic cations tune the lattice of 2D perovskites, thereby influencing the transport and recombination dynamics of charge carriers, has been investigated through nonadiabatic molecular dynamics simulations. We demonstrate that the meta-substituted 3-(aminomethyl)pyridinium (3AMPY) cations greatly reduce the strength of electron-vibration coupling since the strong hydrogen-bonding network introduced by the changes in the arrangement of spacer cations significantly suppresses the structural thermal fluctuations. Compared to the para-substituted 4-(aminomethyl)pyridinium (4AMPY) cation, using the asymmetric 3AMPY as a spacer cation can achieve improved in-plane transport performance, enhanced thermal stability, and suppressed charge carrier recombination through weakening electron-vibration interactions. Our results explain the observed lifetime difference between the two types of DJ-phase perovskites in experiments and provide new guidance for optimizing the performance of perovskite devices.

Coexistence of the Band Filling Effect and Trap-State Filling in the Size-Dependent Photoluminescence Blue Shift of MAPbBr3 Nanoparticles.

The size-dependent photoluminescence (PL) blue shift in organometal halide perovskite nanoparticles has traditionally been attributed to quantum confinement effects (QCEs), irrespective of nanoparticle size. However, this interpretation lacks rigor for nanoparticles with diameters exceeding the exciton Bohr radius (rB). To address this, we investigated the PL of MAPbBr3 nanoparticles (MNPs) with diameters ranging from ~2 to 20 nm. By applying the Brus equation and Burstein-Moss theory to fit the PL and absorption blue shifts, we found that for MNPs larger than rB, the blue shift is not predominantly governed by QCEs but aligns closely with the band filling effect. This was further corroborated by a pronounced excitation-density-dependent PL blue shift (Burstein-Moss shift) at high photoexcitation densities. Additionally, trap-state filling was also found to be not a negligible origin of the PL blue shift, especially for the smaller MNPs. The time-resolved PL spectra (TRPL) and excitation-density-dependent TRPL are collected to support the coexistence of both filling effects by the high initial carrier density (~1017-1018 cm-3) and the recombination dynamics of localized excitons and free carriers in the excited state. These findings underscore the combined role of the band filling and trap-state filling effects in the size-dependent PL blue shift for solution-prepared MNPs with diameters larger than rB, offering new insights into the intrinsic PL blue shift in organometal halide perovskite nanoparticles.

Reduced-Dimensional Perovskites: Quantum Well Thickness Distribution and Optoelectronic Properties.

Reduced-dimensional perovskites (RDPs), a large category of metal halide perovskites, have attracted considerable attention and shown high potential in the fields of solid-state displays and lighting. RDPs feature a quantum-well-based structure and energy funneling effects. The multiple quantum well (QW) structure endows RDPs with superior energy transfer and high luminescence efficiency. The effect of QW confinement directly depends on the number of inorganic octahedral layers (QW thickness, i.e., n value), so the distribution of n values determines the optoelectronic properties of RDPs. Here, it is focused on the QW thickness distribution of RDPs, detailing its effect on the structural characteristics, carrier recombination dynamics, optoelectronic properties, and applications in light-emitting diodes. The reported distribution control strategies is also summarized and discuss the current challenges and future trends of RDPs. This review aims to provide deep insight into RDPs, with the hope of advancing their further development and applications.

Investigation into the carrier recombination in Sb2Se3: Photo thermal effect, trapped carrier absorption and hot carrier cooling

Understanding the carrier recombination processes in Sb2Se3 is essential for its optoelectronic applications. In this work, carrier recombination dynamics in Sb2Se3 were studied by broad band transient absorption spectroscopy. Firstly, the contribution of photothermal effect to the transient absorption spectrum was thoroughly discussed. It is confirmed that the excited state absorption (ESA) band with lifetime of several nanoseconds results from co-contribution of photo thermal effect and deep trapped carrier absorption. Secondly, the features of transient absorption spectrum on picosecond time scale were interpreted. The short-lived ESA band around 1000 nm was assigned to shallow trapped carrier absorption, while not band gap renormalization (BGR) or free carrier absorption. By globally fitting the transient absorption spectrum, the hot carrier cooling time and time constant for free carrier relax into deep trap state were determined to be 0.25∼0.45 ps and 3.1∼8.7 ps, respectively. Finally, we built up the carrier recombination model of Sb2Se3. The experimental results in this work will improve the understanding on the carrier recombination in Sb2Se3.

Achieving Inkjet‐Printed 2D Tin Iodide Perovskites: Excitonic and Electro‐Optical Properties

AbstractCurrently, there is a great demand for non‐toxic lead‐free halide perovskites as active materials for solar cells, light‐emitting diodes and other optoelectronic devices. Although an essential progress has been made using tin(II) halide perovskites, still greater efforts are needed to improve their stability and manufacture films and devices under a scalable technology. The first goal of the work is to achieve suitable physical properties of 2D Sn(II) polycrystalline perovskite films obtained by the industrially scalable inkjet printing deposition technique. In the present work, inks of 2D tin(II) halide perovskite 2‐thiopheneethylammonium tin(II) iodide, TEA2SnI4, have been successfully formulated in DMF (toxic) and DMSO (non‐toxic) solutions and using appropriate additives (SnF2 and reducing agents) for improving the stability of the inks and the resulting films. Room‐ and low‐temperature excitonic photoluminescence (PL), charge carrier recombination dynamics and µ‐PL is used to explain the observed two excitonic bands, which are associated to the bulk and edges of perovskite grains nanoplatelet‐like composing the polycrystalline films. Promising electro‐optical properties are also obtained in the TEA2SnI4 films inkjet‐printed from DMSO formulations onto ITO‐interdigitated electrodes, such as low dark currents, ≈10 – 20 nA at 10 V of bias voltage, and high responsivities ≈1–20 A/W.

Introducing Ag Dopants into CdSe Nanoplatelets (NPLs) Leads to Effective Charge Separation for Better Photodetector Performance.

Solution-processed colloidal cadmium chalcogenide nanoplatelets (NPLs)-based photodetectors (PD) are promising materials for next-generation optoelectronic devices due to their excellent optical properties. Here, we report on ultrafast carrier relaxation dynamics of four monolayer (4 ML) Ag-doped CdSe (Ag: CdSe) NPLs using ultrafast transient absorption spectroscopy and their photodetectors applications. A broad dopant emission is observed at around 650 nm with a large FWHM of ~431 meV and band edge emission at 515 nm. The intragap dopant state acts as a hole acceptor, which leads to better charge separation. The ultrafast transient absorption spectroscopy study shows faster carrier recombination dynamics with a hole transfer time scale of ~10 ps in Ag-doped CdSe NPLs. This supports the excited hole capture phenomenon at the dopant state. Ag-doped CdSe NPLs-based PD performed better than undoped CdSe NPLs with detectivity and responsivity values of 1.3×1010 Jones and 2.4 mA/W, respectively.

Dual surface defects induced efficient interfacial electron transfer in S-scheme hollow ZnO@ZnS heterojunction for uranium (VI) removal

Photocatalytic reduction is a promising way to remove radioactive uranium U(VI) in wastewater. Herein, an S-scheme ZnO@ZnS heterojunction with hollow structure and dual-vacancies of Zn and S (ZnV, SV) is developed. The hollow confined space enhances light trapping ability through multiple light scattering and reflection, while the existence of vacancies extends light absorption, further enhancing the utilization of solar spectrum. Furthermore, the density function theory (DFT) calculations demonstrate that co-sharing of metal atoms at the interface and the ZnV and SV dual-vacancies induce enhanced internal electric field (IEF), leading to facilitated S-scheme charge transfer, thereby resulting in improved retention of redox potential and suppressed carrier recombination dynamics. ZnO@ZnS shows a highest U(VI) removal rate of 96.48% along with a highest U enrichment of 514.33 mg/g, which is 3.6 and 2.7-folds enhanced compared to pristine ZnO and ZnS, respectively. Through various quenching experiments, a potential new mechanism for the catalytic reduction of U(VI) is proposed. Our findings reveal the involvement of h+ in the reaction, highlighting its significant catalytic role in the reduction process. Moreover, ZnO@ZnS performs excellent U(VI) extraction ability in open-air conditions without any sacrificial agents, revealing the great significance for practical applications.

Defect Engineering and Emission Tuning of Wide-Bandgap MAPbCl3 Perovskite.

Lead-chloride perovskites are promising candidates for optoelectronic applications, such as visible-blind UV photodetection. It remains unclear how the deep defects in this wide-bandgap material impact the carrier recombination dynamics. In this work, we study the defect properties of MAPbCl3 (MA = CH3NH3) based on photoluminescence (PL) measurements. Our investigations show that apart from the intrinsic emission, four sub-bandgap emissions emerge, which are very likely to originate from the radiative recombination of excitons bound to several intrinsic vacancy and interstitial defects. The intensity of various emission features can be tuned by adjusting the type and ratio of precursors used during synthesis. Our study not only provides important insights into the defect property and carrier recombination mechanism in this class of material but also demonstrates efficient strategies for defect passivation and engineering, paving the way for further development of lead-chloride perovskite-based optoelectronic devices.

Impacts of vacancy complexes on the room-temperature photoluminescence lifetimes of state-of-the-art GaN substrates, epitaxial layers, and Mg-implanted layers

For rooting the development of GaN-based optoelectronic devices, understanding the roles of midgap recombination centers (MGRCs), namely, nonradiative recombination centers and deep-state radiative recombination centers, on the carrier recombination dynamics is an essential task. By using the combination of time-resolved photoluminescence and positron annihilation spectroscopy (PAS) measurements, the origins of major MGRCs in the state-of-the-art GaN epilayers, bulk crystals, and Mg-implanted layers were identified, and their concentrations were quantified for deriving the capture coefficients of minority carriers. In this article, potential standardization of the room-temperature photoluminescence lifetime for the near-band-edge emission (τPLRT) as the concentration of major MGRCs well below the detection limit of PAS is proposed. For n-GaN substrates and epilayers grown from the vapor phase, τPLRT was limited by the concentration of carbon on N sites or divacancies comprising a Ga vacancy (VGa) and a N vacancy (VN), [VGaVN], when carbon concentration was higher or lower, respectively, than approximately 1016 cm−3. Here, carbon and VGaVN act as major deep-state radiative and nonradiative recombination centers, respectively, while major MGRCs in bulk GaN crystals were identified as VGa(VN)3 vacancy clusters in Na-flux GaN and VGa or VGaVN buried by a hydrogen and/or VGa decorated with oxygen on N sites, VGa(ON)3–4, in ammonothermal GaN. The values of τPLRT in n-GaN samples are compared with those of p-GaN, in which τPLRT was limited by the concentration of VGa(VN)2 in Mg-doped epilayers and by the concentrations of VGaVN and (VGaVN)3 in Mg-implanted GaN right after the implantation and after appropriate activation annealing, respectively.

Interfacial Heterojunction Enables High Efficient PbS Quantum Dot Solar Cells.

Colloidal quantum dots (CQDs) are promising optoelectronic materials for solution-processed thin film optoelectronic devices. However, the large surface area with abundant surface defects of CQDs and trap-assisted non-radiative recombination losses at the interface between CQDs and charge-transport layer limit their optoelectronic performance. To address this issue, an interface heterojunction strategy is proposed to protect the CQDs interface by incorporating a thin layer of polyethyleneimine (PEIE) to suppress trap-assisted non-radiative recombination losses. This thin layer not only acts as a protective barrier but also modulates carrier recombination and extraction dynamics by forming heterojunctions at the buried interface between CQDs and charge-transport layer, thereby enhancing the interface charge extraction efficiency. This enhancement is demonstrated by the shortened lifetime of carrier extraction from 0.72 to 0.46ps. As a result, the resultant PbS CQD solar cells achieve a power-conversion-efficiency (PCE) of 13.4% compared to 12.2% without the heterojunction.

Investigation of the third-order optical nonlinear enhancement properties of Ag doped chalcogenide glass films

Chalcogenide glass is widely recognized as an excellent nonlinear optical material. Enhancing its nonlinear optical properties through metal doping has emerged as a prominent research avenue in the field of chalcogenide glass. In this paper, silver (Ag) doped Ge28Sb12Se60 (GSS) chalcogenide glass films with different concentrations were prepared by co-evaporation method. The nonlinear absorption coefficients (β) of different samples were investigated by open-aperture top-hat Z-scan experiments and pump-probe experiments, and the nonlinear refractive index (γ) values were determined using the Tichy-Ticha relation. The results showed that the nonlinear absorption of GSS thin films can be improved by Ag doping. The nonlinear absorption coefficient β exhibits the maximum enhancement of about 2.5 times at 8.3% concentration, with the maximum β reaching 1.83×10−6 m/W. The nonlinear absorption mechanism observed in the thin films can be attributed to free carrier absorption, and the free carrier lifetime is positively correlated with the Ag doping concentration. Within the selected Ag concentration range, the nonlinear refractive index (γ) of Ag doped chalcogenide glass films continues to increase, reaching about 3 times at 30.7% concentration, with the maximum γ being 4.643×10−17 m2/W. Additionally, the third-order nonlinear polarizability (χ(3)) values can be increased from 1.014×10−11 esu to 3.314×10−11 esu with increasing Ag concentration. The research results in present paper are of great significance for further exploration of the optical nonlinear enhancement properties and carrier recombination dynamics in chalcogenide glass.

Effect of Connectivity on the Carrier Transport and Recombination Dynamics of Perovskite Quantum-Dot Networks.

Quantum-dot (QD) solids are being widely exploited as a solution-processable technology to develop photovoltaic, light-emission, and photodetection devices. Charge transport in these materials is the result of a compromise between confinement at the individual QD level and electronic coupling among the different nanocrystals in the ensemble. While this is commonly achieved by ligand engineering in colloidal-based systems, ligand-free QD assemblies have recently emerged as an exciting alternative where nanostructures can be directly grown into porous matrices with optical quality as well as control over their connectivity and, hence, charge transport properties. In this context, we present a complete photophysical study comprising fluence- and temperature-dependent time-resolved spectroscopy to study carrier dynamics in ligand-free QD networks with gradually varying degrees of interconnectivity, which we achieve by changing the average distance between the QDs. Analysis of the photoluminescence and absorption properties of the QD assemblies, involving both static and time-resolved measurements, allows us to identify the weight of the different recombination mechanisms, both radiative and nonradiative, as a function of QD connectivity. We propose a picture where carrier diffusion, which is needed for any optoelectronic application and implies interparticle transport, gives rise to the exposure of carriers to a larger defect landscape than in the case of isolated QDs. The use of a broad range of fluences permits extracting valuable information for applications demanding either low- or high-carrier-injection levels and highlighting the relevance of a judicious design to balance recombination and diffusion.

The effective prolongation of the excited-state carrier lifetime of CsPbI2Br with applying strain.

In recent years, all-inorganic perovskites CsPbX3 (X = Cl, Br, I) have emerged as excellent candidates for solar cells due to their remarkable thermal stability and suitable bandgaps. Among them, CsPbI2Br is a hotspot in perovskite material research currently. Non-radiative electron-hole recombination often leads to significant energy losses, impacting the efficiency of solar cells, so a thorough understanding of carrier recombination mechanisms is crucial. Our work investigated the carrier recombination dynamics in detail and proved that strains can effectively reduce nonradiative recombination. In this study, using first-principles calculations combined with nonadiabatic (NA) molecular dynamics (MD), we demonstrate that applying 2% tensile and 2% compressive strains to CsPbI2Br can modify the bandgap, induce moderate disorder, reduce the overlap of electron-hole wavefunctions, decrease NA coupling, and shorten decoherence time, thereby minimizing non-radiative recombination and extending the carrier lifetime. Especially the 2% tensile strain exhibits more effective control performance, significantly reducing non-radiative electron-hole recombination and extending the charge carrier lifetime to 14.59 ns, nearly five times that of the pristine CsPbI2Br system (3.12 ns). This study reveals the impact mechanism of strain on carrier behavior in perovskite solar cells, providing a new non-chemical strategy for modulating the lifetime of photo-generated carriers and enhancing the efficiency of all-inorganic perovskite solar cells.

Improving the photocatalytic activity of graphitic carbon nitride through ionic liquid-mediated thermal annealing

Graphitic carbon nitride (g-C3N4) has shown a great promise in photocatalytic hydrogen evolution. However, the catalytic activity of g-C3N4 derived from nitrogen-rich compounds is still limited by fast charge carrier recombination and slow surface reaction dynamics. Herein, a series of primary g-C3N4 materials were prepared by thermal polymerization of melamine and/or urea, and then thermally treated with the involvement of different ionic liquids under altering heat conditions. Imidazole-containing ionic liquids, such as 1-propyl-3-methylimidazolium chloride ([PMIm]Cl), acted as an effective additive to mediate the thermal annealing behavior of primary g-C3N4, leading to the dissociation of aggregates into porous nanosheets with varying element compositions and with increased surface area. Regardless of little change in optical absorption and electronic structure, the resulting porous g-C3N4 nanosheets promoted the separation and transfer of photogenerated charges and modified surface hydrogen desorption. Hydrogen evolution tests confirmed that the catalytic activity of g-C3N4 from the co-polymerization of melamine and urea was enhanced by ∼3.4 and ∼7.4 times upon [PMIm]Cl-free and -mediated thermal annealing, respectively. This work suggests the potential effect of the additive involvement in the thermal annealing on the photocatalytic activity of g-C3N4.

Tuning Structure and Excitonic Properties of 2D Ruddlesden-Popper Germanium, Tin, and Lead Iodide Perovskites via Interplay between Cations.

The compositional tunability of 2D metal halide perovskites enables exploration of diverse semiconducting materials with different structural features. However, rationally tuning the 2D perovskite structures to target physical properties for specific applications remains challenging, especially for lead-free perovskites. Here, we study the effect of the interplay of the B-site (Ge, Sn, and Pb), A-site (cesium, methylammonium, and formamidinium), and spacer cations on the structure and optical properties of a new series of 2D Ruddlesden-Popper perovskites using the previously unreported spacer cation 4-bromo-2-fluorobenzylammonium (4Br2FBZ). We report eight new crystal structures and study the consequence of varying the B-site (Pb, Sn, Ge) and dimension (n = 1, 2, vs 3D). Dimension strongly influences local distortion and structural symmetry, and the increased octahedral tilting and lone pair effects in Ge perovskites lead to a polar n = 2 perovskite that exhibits second harmonic generation, (4Br2FBZ)2(Cs)Ge2I7. In contrast, the analogous Sn and Pb perovskites remain centrosymmetric, but the B-site metal influences the photoluminescence properties. The Pb perovskites exhibit broad, defect-mediated emission at low temperature, whereas the Sn perovskites show purely excitonic emission over the entire temperature range, but the carrier recombination dynamics depend on dimensionality and dark excitonic states. Wholistic understanding of these differences that arise based on cations and dimensionality can guide the rational materials design of 2D perovskites for targeting physical properties for optoelectronic applications based on the interplay of cations and the connectivity of the inorganic framework.

Optical Absorption, Photocarrier Recombination Dynamics and Terahertz Dielectric Properties of Electron-Irradiated GaSe Crystals

Optical absorption spectra of 9 MeV electron-irradiated GaSe crystals were studied. Two absorption bands with the low-photon-energy threshold at 1.35 and 1.73 eV (T = 300 K) appeared in the transparency region of GaSe after the high-energy-electron irradiation. The observed absorption bands were attributed to the defect states induced by Ga vacancies in two charge states, having the energy positions at 0.23 and 0.61 eV above the valence band maximum at T = 300 K. The optical pump-terahertz probe technique (OPTP) was employed to study the dark and photoexcited terahertz conductivity and charge carrier recombination dynamics at two-photon excitation of as-grown and 9 MeV electron-irradiated GaSe crystals. The measured values of the differential terahertz transmission at a specified photoexcitation condition were used to extract the terahertz charge carrier mobilities. The determined terahertz charge carrier mobility values were ~46 cm2/V·s and ~14 cm2/V·s for as-grown and heavily electron-irradiated GaSe crystals, respectively. These are quite close to the values determined from the Lorentz–Drude–Smith fitting of the measured dielectric constant spectra. The photo-injection-level-dependent charge carrier lifetimes were determined from the measured OPTP data, bearing in mind the model injection-level dependencies of the recombination rates governed by interband and trap-assisted Auger recombination, bulk and surface Shockley–Read–Hall (SRH) recombination and interband radiative transitions in the limit of a high injection level. It was found that GaSe possesses a long charge carrier lifetime (a~1.9 × 10−6 ps−1, b~2.7 × 10−21 cm3ps−1 and c~1.3 × 10−37 cm6ps−1), i.e., τ~0.53 μs in the limit of a relatively low injection, when the contribution from SRH recombination is dominant. The electron irradiation of as-grown GaSe crystals reduced the charge carrier lifetime at a high injection level due to Auger recombination through radiation-induced defects. It was found that the terahertz spectra of the dielectric constants of as-grown and electron-irradiated GaSe crystals can be fitted with acceptable accuracy using the Lorentz model with the Drude–Smith term accounting for the free-carrier conductivity.

High-Efficiency and Emission-Tunable Inorganic Blue Perovskite Light-Emitting Diodes Based on Vacuum Deposition.

The fabrication of perovskite light-emitting diodes (PeLEDs) with vacuum deposition shows great potential and commercial value in realizing large-area display panel manufacturing. However, the electroluminescence (EL) performance of vacuum-deposited PeLEDs still lags behind the counterparts fabricated by solution process, especially in the field of blue PeLEDs. Here, the fabrication of high-quality CsPbBr3- x Clx film through tri-source co-evaporation is reported to achieve high photoluminescence quantum yield (PLQY). Compared with the conventional traditional dual-source co-evaporation, the tri-source co-evaporation method allows for freely adjustable elemental ratios, enabling the introduction of the lattice-matched Cs4 Pb(Br/Cl)6 phase with the quantum-limited effect into the inorganic CsPb(Br/Cl)3 emitter. By adjusting the phase distribution, the surface defects of the emitter can be effectively reduced, leading to better blue emission and film quality. Further, the effects of Cs/Pb ratio and Br/Cl ratio on the PLQY and carrier recombination dynamics of perovskite films are investigated. By optimizing the deposition rate of each precursor source, spectrally stable blue PeLEDs are achieved with tunable emission ranging from 468 to 488nm. Particularly, the PeLEDs with an EL peak at 488nm show an external quantum efficiency (EQE) of 4.56%, which is the highest EQE value for mixed-halide PeLEDs fabricated by vacuum deposition.

(Invited) Charge Carrier Relaxation, Recombination and Extraction Dynamics in Metal Halide Perovskite Nanocrystals

Charge Carrier Relaxation, Recombination and Extraction Dynamics in Metal Halide Perovskite Nanocrystals Anunay Samanta School of Chemistry, University of Hyderabad, Hyderabad 500046 (anunay@uohyd.ac.in)The lead halide-based all-inorganic and hybrid perovskites are under intense investigation due to their immense potential in solar photovoltaic and light emitting applications.1,2 As realization of the full potential of these materials in various applications requires a clear understanding of the relaxation pathways and dynamics of the photo-generated charge carriers, we have been studying these key photo-processes in a wide range of perovskite nanocrystals.3-10 In this talk, we would like to present some of our recent results highlighting how a combination of femtosecond pump-probe and single-particle fluorescence techniques can be used to obtain valuable information on the nature and energy states of the photogenerated species, pathways and dynamics of relaxation of the charge carriers, location and nature of the trap states and their role in fluctuation of the photoluminescence of different caesium lead halide (CsPbX3) perovskite nanocrystals. References Dey, A. et. al. ACS Nano 2021, 15, 10775.Green, M.A.; Ho-Baillie, A.; Snaith, H.J. Nature Photonics 2014, 8, 506.Mondal, N; De, A.; Das, S.; Paul, S.; Samanta, A. Nanoscale 2019, 4, 9796.Mondal, N; De, A.; Samanta, A. ACS Energy Letts. 2019, 4, 32.Seth, S.; Ahmed, T.; Samanta, A. J. Phys. Chem. Lett. 2018, 9, 7007.Mondal, N; De, A.; Samanta, A. J. Phys. Chem. Lett. 2018, 9, 3673.Ahmed, T; Seth. S.; Samanta, A. ACS Nano 2019, 13, 13537.De, A.; Das, A.; Samanta, A. ACS Energy Letts. 2020, 5, 2246.Ahmed, T.; Paul, S.; Samanta, A. J. Phys. Chem. C 2022, 126, 9109.Paul, S.; Samanta, A. J. Phys. Chem. Lett. 2022, 13, 5742.

Ultrafast Electronic Relaxation Dynamics of Atomically Thin MoS2 Is Accelerated by Wrinkling.

Strain engineering is an attractive approach for tuning the local optoelectronic properties of transition metal dichalcogenides (TMDs). While strain has been shown to affect the nanosecond carrier recombination dynamics of TMDs, its influence on the sub-picosecond electronic relaxation dynamics is still unexplored. Here, we employ a combination of time-resolved photoemission electron microscopy (TR-PEEM) and nonadiabatic ab initio molecular dynamics (NAMD) to investigate the ultrafast dynamics of wrinkled multilayer (ML) MoS2 comprising 17 layers. Following 2.41 eV photoexcitation, electronic relaxation at the Γ valley occurs with a time constant of 97 ± 2 fs for wrinkled ML-MoS2 and 120 ± 2 fs for flat ML-MoS2. NAMD shows that wrinkling permits larger amplitude motions of MoS2 layers, relaxes electron-phonon coupling selection rules, perturbs chemical bonding, and increases the electronic density of states. As a result, the nonadiabatic coupling grows and electronic relaxation becomes faster compared to flat ML-MoS2. Our study suggests that the sub-picosecond electronic relaxation dynamics of TMDs is amenable to strain engineering and that applications which require long-lived hot carriers, such as hot-electron-driven light harvesting and photocatalysis, should employ wrinkle-free TMDs.

Resolving the Ultrafast Charge Carrier Dynamics of 2D and 3D Domains within a Mixed 2D/3D Lead‐Tin Perovskite

AbstractMixed 2D/3D perovskite materials are of particular interest to the photovoltaics and light‐ emitting diode (LED) communities due to their impressive opto‐electronic properties alongside improved moisture stability compared to conventional 3D perovskite absorbers. Here, a mixed lead‐tin perovskite containing distinct, self‐assembled domains of either 3D structures or highly phase‐pure Ruddlesden–Popper 2D structures is studied. The complex energy landscape of the material is revealed with ultrafast optical transient absorption measurements. It is shown that charge transfer between these microscale domains only occurs on nanosecond timescales, consistent with the large size of the domains. Using optical pump‐terahertz probe spectroscopy, the effective charge‐carrier mobility is shown to be an intermediary between analogous pure 2D and 3D perovskites. Furthermore, detailed analysis of the free carrier recombination dynamics is presented. By combining results from a range of excitation wavelengths within a full dynamic model of the photoexcited carrier population, it is shown that the 2D domains in the film exhibit remarkably similar carrier dynamics to the 3D domains, suggesting that long‐range charge‐transport should not be impeded by the heterogeneous structure of the material.