Dynamics Of Photoexcited Carriers Research Articles

Photoexcited Carrier Dynamics in Iodine-Doped CH3NH3PbBr3 Single Crystals.

Iodine-doped bromide perovskite single crystals (IBPSCs) have important applications in optoelectronic fields, such as in solar cells. Currently, much research has aimed to study the phase separation phenomenon and device performance improvements in IBPSCs. However, important intrinsic photoexcited carrier dynamics are often overlooked in IBPSCs. Here, we explored the photoexcited carrier dynamics in typical iodine-doped MAPbBr3 single crystals using the excitation intensity-dependent steady-state photoluminescence (PL) and time-resolved photoluminescence (TRPL) technique. We found that the trap state density changes with an increase in the amount of doped iodine. Further, we noticed that there is an influence of carrier diffusion on the photoexcited carrier dynamics, and then, we evaluated the carrier diffusion coefficients and recombination constants via numerical simulations of the PL kinetics. Consequently, we found that the electron shallow trap-related carrier behaviors substantially impacted the PL kinetics. Our results greatly facilitate a deeper understanding of the fundamental characteristics of mixed halide perovskite material.

Hot Carrier Controlled Nitrogen Fixation Reaction in Metal-Free Boron-Anchored Aza-COF: Insight from Nonadiabatic Molecular Dynamics Simulation.

Designing highly efficient photocatalysts for the production of renewable energy is a challenging task that necessitates simultaneous control of chemical activity and photocarrier dynamics for a particular reaction. To this end, we have investigated the catalytic mechanism and real-time photocarrier dynamics of the nitrogen reduction reaction (NRR) at the metal-free boron-functionalized 2D aza-COF (B-aza-COF), an inexpensive and environmentally friendly semiconductor. By employing density functional theory (DFT) and time-dependent ab initio nonadiabatic molecular dynamics simulation, we have investigated the electronic structure, light harvesting ability, free energy change, and dynamics of photoexcited carriers. Our calculated results reveal that the gas phase N2 molecule can be effectively reduced into NH3 on B-aza-COF under UV-visible light. Therefore, our investigation on the design of efficient photocatalysts for the nitrogen reduction reaction (NRR) provides a cost-effective opportunity for the sustainable production of NH3.

Comprehensive study of the ultrafast photoexcited carrier dynamics in Sb2Te3-GeTe superlattices

Abstract Chalcogenide superlattices Sb2Te3-GeTe is a candidate for interfacial phase-change memory (iPCM) data storage devices. By employing terahertz emission spectroscopy and the transient reflectance spectroscopy together, we investigate the ultrafast photoexcited carrier dynamics and current transients in Sb2Te3-GeTe superlattices. Sample orientation and excitation polarization dependences of the THz emission confirm that ultrafast thermo-electric, shift and injection currents contribute to the THz generation in Sb2Te3-GeTe superlattices. By decreasing the thickness and increasing the number of GeTe and Sb2Te3 layer, the interlayer coupling can be enhanced, which significantly reduces the contribution from circular photo-galvanic effect (CPGE). A photo-induced bleaching in the transient reflectance spectroscopy probed in the range of ~1100 nm to ~1400 nm further demonstrates a gapped state resulting from the interlayer coupling. These demonstrates play an important role in the development of iPCM-based high-speed optoelectronic devices.

Ultrafast Carrier Dynamics in Ba6Cr2S10 Modified by Toroidal Magnetic Phase Transition

Ba6Cr2S10 is a recently discovered magnetic material, in which the spins are aligned ferromagnetically in the ab-plane and anti-parallelly in a paired form along the c-axis. It is characterized as a quasi-one dimensional (1D) dimerized structure with a ferrotoroidic order, forming the simplest candidate toroidal magnetic (TM) order and exhibiting an anti-ferromagnetic-like transition at around 10 K. Time-resolved ultrafast dynamics investigation of the novel A–Cr–S (A: metal elements) family of quantum materials has rarely been reported. Here, we investigate the time-resolved pump-probe ultrafast dynamics of a Ba6Cr2S10 single crystal. A prominent change in the photo-excited carrier dynamics is observed at T c = 10 K, corresponding to the reported TM-paramagnetic phase transition. A potential unknown magnetic transition is also found at T * = 29 K. Our results provide new evidence for the TM magnetic transition in Ba6Cr2S10, and shed light on phase transitions in TM quantum materials.

High-performance terahertz modulators induced by substrate field in Te-based all-2D heterojunctions

High-performance active terahertz modulators as the indispensable core components are of great importance for the next generation communication technology. However, they currently suffer from the tradeoff between modulation depth and speed. Here, we introduce two-dimensional (2D) tellurium (Te) nanofilms with the unique structure as a new class of optically controlled terahertz modulators and demonstrate their integrated heterojunctions can successfully improve the device performances to the optimal and applicable levels among the existing all-2D broadband modulators. Further photoresponse measurements confirm the significant impact of the stacking order. We first clarify the direction of the substrate-induced electric field through first-principles calculations and uncover the unusual interaction mechanism in the photoexcited carrier dynamics associated with the charge transfer and interlayer exciton recombination. This advances the fundamental and applicative research of Te nanomaterials in high-performance terahertz optoelectronics.

Tunable Interfacial Electronic and Photoexcited Carrier Dynamics of an S-Scheme MoSi2N4/SnS2 Heterojunction.

Exploring and designing an efficient S-scheme heterojunction photocatalyst for water splitting are crucial. Herein, we report the interfacial electronics, photoexcited carrier dynamics, and photocatalytic performance for water splitting of the MoSi2N4/SnS2 van der Waals heterojunction under the modulation of an electric field and biaxial strain. Our results show that the MoSi2N4/SnS2 heterojunction has a direct band gap of 0.41 eV and obeys the S-scheme charge transfer mechanism. Further calculations of the photoexcited carrier dynamics demonstrate that the interfacial carrier recombination time is 7.22 ps, which is shorter than the electron (hole) transfer time of 39.5 ps (566 ps). Moreover, under the effect of a positive electric field and tensile strain, the S-scheme MoSi2N4/SnS2 heterojunction exhibits excellent visible-light absorption, satisfactory band-edge potentials, tunable interfacial charge transfer, and spontaneous hydrogen evolution reaction activity. The calculated STH efficiency indicates that a tensile strain of 2% is the most effective means of improving the photocatalytic performance of the S-scheme MoSi2N4/SnS2 heterojunction.

Selective Interfacial Excited-State Carrier Dynamics and Efficient Charge Separation in Borophene-Based Heterostructures.

Borophene-based van der Waals heterostructures have demonstrated enormous potential in the realm of optoelectronic and photovoltaic devices, which has sparked a wide range of interest. However, a thorough understanding of the microscopic excited-state electronic dynamics at interfaces is lacking, which is essential for determining the macroscopic optoelectronic and photovoltaic performance of borophene-based devices. In this study, photoexcited carrier dynamics of β12 , χ3 , and α΄ borophene/MoS2 heterostructures are systematically studied based on time-domain nonadiabatic molecular dynamics simulations. Different Schottky contacts are found in borophene/semiconductor heterostructures. The interplay between Schottky barriers, electronic coupling, and the involvement of different phonon modes collectively contribute to the unique carrier dynamics in borophene-based heterostructures. The diverse borophene allotropes within the heterostructures exhibit distinct and selective carrier transfer behaviors on an ultrafast timescale: electrons tunnel into α΄ borophene with an ultrafast transfer rate (≈29fs) in α΄/MoS2 heterostructures, whereas β12 borophene only allows holes to migrate with a lifetime of 176fs. The feature enables efficient charge separation and offers promising avenues for applications in optoelectronic and photovoltaic devices. This study provides insight into the interfacial carrier dynamics in borophene-based heterostructures, which is helpful in further design of advanced 2D boron-based optoelectronic and photovoltaic devices.

A New Metal-Free Molecular Perovskite-Related Single Crystal with Quantum Wire Structure for High-Performance X-Ray Detection.

The family of metal-free molecular perovskites, an emerging novel class of eco-friendly semiconductor, welcomes a new member with a unique 1D hexagonal perovskite structure. Lowering dimensionality at molecular level is a facile strategy for crystal structure conversion, optoelectronic property regulation, and device performance optimization. Herein, the study reports the design, synthesis, packing structure, and photophysical properties of the 1D metal-free molecular perovskite-related single crystal, rac-3APD-NH4I3(rac-3APD= racemic-3-Aminopiperidinium), that features a quantum wire structure formed by infinite chains of face-sharing NH4I6 octahedra, enabling strong quantum confinement with strongly self-trapped excited (STE) states to give efficient warm orange emission with a photoluminescence quantum yield (PLQY) as high as ≈41.6%. The study accordingly unveils its photoexcited carrier dynamics: rac-3APD-NH4I3 relaxes to STE state with a short lifetime of 10ps but decays to ground state by emitting photons with a relatively longer lifetime of 560ps. Additionally, strong quantum confinement effect is conducive to charge transport along the octahedral channels that enables the co-planar single-crystal X-ray detectors to achieve a sensitivity as high as 1556 µC Gyair -1 cm-2. This work demonstrates the first case of photoluminescence mechanism and photophysical dynamics of 1D metal-free perovskite-related semiconductor, as well as the promise for high-performance X-ray detector.

Probing Carrier Dynamics in Large-Scale MBE-Grown PtSe2 Films by Terahertz Spectroscopy.

Atomically thin platinum diselenide (PtSe2) films are promising for applications in the fields of electronics, spintronics, and photodetectors owing to their tunable electronic structure and high carrier mobility. Using terahertz (THz) spectroscopy techniques, we investigated the layer-dependent semiconducting-to-metallic phase transition and associated intrinsic carrier dynamics in large-scale PtSe2 films grown by molecular beam epitaxy. The uniformity of large-scale PtSe2 films was characterized by spatially and frequency-resolved THz-based sheet conductivity mapping. Furthermore, we use an optical-pump-THz-probe technique to study the transport dynamics of photoexcited carriers and explore light-induced intergrain carrier transport in PtSe2 films. We demonstrate large-scale THz-based mapping of the electrical properties of transition metal dichalcogenide films and show that the two noncontact THz-based approaches provide insight in the spatial and temporal properties of PtSe2 films.

(Invited) Enhanced Photocatalysis on TiO2-Passivated III-V Compound Semiconductors and 2D Material Heterostructures for Water Splitting and CO2 Reduction

We report enhanced photocatalysis for H2 evolution and CO2 reduction using TiO2-passivated InP and GaAs photocathodes.1-4 The TiO2 layer makes the InP semiconductor photochemically stable. This represents a major step forward in photocatalysis, which has typically been limited to metal oxide materials. In addition to making these surfaces stable, the TiO2 film, deposited by atomic layer deposition (ALD), also provides a substantial enhancement in the efficiency of H2 evolution. We find that passivating GaAs with just a few nm of TiO2 produces a shift in the onset potential of H2 evolution by +0.35 V at 1 mA/cm2 and enhances the photocurrent by 32-fold over bare GaAs (at 0 V vs. RHE). Here, thinner TiO2 films produce a larger enhancement than thicker films, which correlates with the higher density of O-vacancies (i.e., Ti3+ surface states) observed in these thinner films using X-ray photoemission spectroscopy (XPS). While TiO2 films 1-5nm thick produce large enhancements, no enhancement is observed for TiO2 thicknesses above 10 nm, which are crystalline and, therefore, considerably more insulating than thinner amorphous TiO2 films.Using transient reflectance spectroscopy (TRS), we measure the photoexcited carrier dynamics in a GaP/TiO2 photoelectrode, as well as the electrostatic field dynamics at this semiconductor-liquid interfaces in situ under various electrochemical potentials.5 Here, the electrostatic fields at the surface of the semiconductor are measured via Franz−Keldysh oscillations (FKO). These spectra reveal that the nanoscale TiO2 protection layer enhances the built-in field and charge separation performance of GaP photoelectrodes.We also demonstrated plasmon-resonant enhancement of photocatalysis on monolayer WSe2.6 In addition, we measured the stacking dependence and resonant interlayer excitation of monolayer WSe2/MoSe2 heterostructures for photocatalytic energy conversion.7 Qiu, J., G. Zeng, M. Ge, S. Arab, M. Mecklenburg, B. Hou, C. Shen, A.V. Benderskii and S.B. Cronin, Correlation of Ti3+ states with photocatalytic enhancement in TiO2-passivated p-GaAs. Journal of Catalysis, 337, 133 (2016).Qiu, J., G.T. Zeng, M.A. Ha, M.Y. Ge, Y.J. Lin, M. Hettick, B.Y. Hou, A.N. Alexandrova, A. Javey and S.B. Cronin, Artificial Photosynthesis on TiO2-Passivated InP Nanopillars. Nano Letters, 15, 6177-6181 (2015).Qiu, J., G.T. Zeng, M.A. Ha, B.Y. Hou, M. Mecklenburg, H.T. Shi, A.N. Alexandrova and S.B. Cronin, Microscopic Study of Atomic Layer Deposition of TiO2 on GaAs and Its Photocatalytic Application. Chemistry of Materials, 27, 7977-7981 (2015).Wang, Y. and S.B. Cronin, Performance Enhancement of TiO2-encapsulated Photoelectrodes Based on III–V Compound Semiconductors, in Ultrathin Oxide Layers for Solar and Electrocatalytic Systems. 2022, Royal Society of Chemistry. p. 103-134.Xu, Z.H., B.Y. Hou, F.Y. Zhao, Z. Cai, H.T. Shi, Y.W. Liu, C.L. Hill, D.G. Musaev, M. Mecklenburg, S.B. Cronin and T.Q. Lian, Nanoscale TiO2 Protection Layer Enhances the Built-In Field and Charge Separation Performance of GaP Photoelectrodes. Nano Letters, 21, 8017-8024 (2021).Chen, J., C.S. Bailey, Y. Hong, L. Wang, Z. Cai, L. Shen, B. Hou, Y. Wang, H. Shi, J. Sambur, W. Ren, E. Pop, and S.B. Cronin., Plasmon-Resonant Enhancement of Photocatalysis on Monolayer WSe2. ACS Photonics, 6, 787 (2019).Chen, J., C.S. Bailey, D. Cui, Y. Wang, B. Wang, H. Shi, Z. Cai, E. Pop, C. Zhou and S.B. Cronin, Stacking Independence and Resonant Interlayer Excitation of Monolayer WSe2/MoSe2 Heterostructures for Photocatalytic Energy Conversion. ACS Applied Nano Materials, DOI:10.1021/acsanm.9b01898 (2020).

(Invited) In Situ Spectroscopy of Electrocatalytic and Photocatalytic Interfaces

We report various aspects of electrochemistry and photoelectrochemistry using in situ spectroscopy of electrode (metal) and photoelectrode (semiconductor) interfaces in situ under electrochemical working conditions. These spectroscopies include sum frequency generation (SFG), transient reflectance/absorption spectroscopy (TAS/TRS), and surface enhanced Raman spectroscopy (SERS). Using surface enhanced Raman scattering (SERS) spectroscopy, we monitor local electric fields using Stark-shifts of nitrile-functionalized silicon photoelectrodes.6 Using Graphene-enhanced Raman spectroscopy (GERS)-based Stark-shifts, we measure local electric fields and local charge densities at monolayer graphene electrode surfaces.1 We also measured the stacking dependence and Resonant interlayer excitation of monolayer WSe2/MoSe2 heterostructures for photocatalytic energy conversion.2 Using sum frequency generation (SFG) spectroscopy, we measure the voltage dependence of the orientation of D2O molecules at a graphene electrode surface, which is related back to the “stiffness of the ensemble”.3 In particular, we measured the “free OD” feature in the spectra, which corresponds to the topmost water molecule that is rotated up out of the bulk water solution and is, therefore, not hydrogen bonded. Using transient absorption spectroscopy (TAS), we measure the lifetime of hot electrons photoexcited in plasmon resonant nanostructures.5 Using transient reflectance spectroscopy (TRS), we measure the photoexcited carrier dynamics in a GaP/TiO2 photoelectrode, as well as the electrostatic field dynamics at this semiconductor-liquid interfaces in situ under various electrochemical potentials.4 Here, the electrostatic fields at the surface of the semiconductor are measured via Franz−Keldysh oscillations (FKO). These spectra reveal that the nanoscale TiO2 protection layer enhances the built-in field and charge separation performance of GaP photoelectrodes. Shi, H.T., B.F. Zhao, J. Ma, M.J. Bronson, Z. Cai, J.H. Chen, Y. Wang, M. Cronin, L. Jensen and S.B. Cronin, Measuring Local Electric Fields and Local Charge Densities at Electrode Surfaces Using Graphene-Enhanced Raman Spectroscopy (GERS)-Based Stark-Shifts. ACS Applied Materials & Interfaces, 11, 36252-36258 (2019).Chen, J., C.S. Bailey, D. Cui, Y. Wang, B. Wang, H. Shi, Z. Cai, E. Pop, C. Zhou and S.B. Cronin, Stacking Independence and Resonant Interlayer Excitation of Monolayer WSe2/MoSe2 Heterostructures for Photocatalytic Energy Conversion. ACS Applied Nano Materials, DOI:10.1021/acsanm.9b01898 (2020).Montenegro, A., C. Dutta, M. Mammetkuliev, H.T. Shi, B.Y. Hou, D. Bhattacharyya, B.F. Zhao, S.B. Cronin and A.V. Benderskii, Asymmetric response of interfacial water to applied electric fields. Nature, 594, 62 (2021).Xu, Z.H., B.Y. Hou, F.Y. Zhao, Z. Cai, H.T. Shi, Y.W. Liu, C.L. Hill, D.G. Musaev, M. Mecklenburg, S.B. Cronin and T.Q. Lian, Nanoscale TiO2 Protection Layer Enhances the Built-In Field and Charge Separation Performance of GaP Photoelectrodes. Nano Letters, 21, 8017-8024 (2021).Yu Wang, Yi Wang, Indu Aravind, Zhi Cai, Lang Shen, Boxin Zhang, Bo Wang, Jihan Chen, Bofan Zhao, Haotian Shi, Jahan M. Dawlaty, and Stephen B. Cronin. In Situ Investigation of Ultrafast Dynamics of Hot Electron-Driven Photocatalysis in Plasmon-Resonant Grating Structures. Journal of the American Chemical Society. DOI: 10.1021/jacs.1c12069 (2022).Haotian Shi, Ryan T. Pekarek, Ran Chen, Boxin Zhang, Yu Wang, Indu Aravind, Zhi Cai, Lasse Jensen, Nathan R. Neale, and Stephen B. Cronin. Monitoring Local Electric Fields using Stark Shifts on Napthyl Nitrile-Functionalized Silicon Photoelectrodes. The Journal of Physical Chemistry C, 124, 17000-17005 (2020).

Photoexcited Carrier Transfer in CuInS2 Nanocrystal Assembly by Suppressing Resonant-Energy Transfer.

High-density assemblies or superlattice structures composed of colloidal semiconductor nanocrystals have attracted attention as key materials for next-generation photoelectric conversion devices such as quantum-dot solar cells. In these nanocrystal solids, unique transport and optical phenomena occur due to quantum coupling of localized energy states, charge-carrier hopping, and electromagnetic interactions among closely arranged nanocrystals. In particular, the photoexcited carrier dynamics in nanocrystal solids is important because it significantly affects various device parameters. In this study, we report the photoexcited carrier dynamics in a solid film of CuInS2 nanocrystals, which is one of the potential nontoxic substitutes with Cd- and Pb-free compositions. Meanwhile, these subjects have been extensively studied in nanocrystal solids formed by CdSe and PbS systems. A carrier-hopping mechanism was confirmed using temperature-dependent photoluminescence spectroscopy, which yielded a typical value of the photoexcited carrier-transfer rate of (2.2±0.6)×107 s-1 by suppressing the influence of the excitation-energy transfer.

Long‐Lived Charges in Y6:PM6 Bulk‐Heterojunction Photoanodes with a Polymer Overlayer Improve Photoelectrocatalytic Performance

AbstractPhotogenerating charges with long lifetimes to drive catalysis is challenging in organic semiconductors. Here, the role of a PM6 polymer overlayer on the photoexcited carrier dynamics is investigated in a Y6:PM6 bulk‐heterojunction (BHJ) photoanode undergoing ascorbic acid oxidation. With the additional polymer layer, the hole lifetime is increased in the solid state BHJ film. When the photoanode is electrically coupled to a hydrogen‐evolving platinum cathode, remarkably long‐lived hole polaron states are observed on the timescale of seconds under operational conditions. It is demonstrated that these long‐lived holes enable the organic photoanode with the polymer overlayer to show enhanced ascorbic acid oxidation performance, reaching ≈7 mA cm−2 at 1.23 VRHE without a co‐catalyst. An external quantum efficiency of 18% is observed using 850 nm excitation. It is proposed that the use of an organic overlayer can be an effective design strategy for generating longer charge carrier lifetimes in organic photoanodes for efficient oxidation catalysis.

Ultrafast Graphene-Plasmonic Hybrid Metasurface Saturable Absorber with Low Saturation Fluence.

Exploring emerging materials with enhanced optical nonlinearities at low power levels with ultrafast response and small footprints is of great interest for information processing, communication, sensing, and quantum systems. Recent progress on nonlinear metamaterials and metasurfaces suggests promising solutions to overcome the limitations of nonlinear materials in nature. Here we present a design concept for highly enhanced saturable absorption effect based on subwavelength-thick (<1/5λ0) hybrid graphene-plasmonic metasurface structures in infrared wavelengths. Our theoretical and experimental results demonstrated that, by exciting nonequilibrium carriers inside nanoscale hotspots, one could not only enhance the saturable absorption in graphene, but also reduce the saturation fluence by over 3 orders of magnitude (from ∼1 mJ/cm2 to ∼100 nJ/cm2). Our pump-probe measurement results suggested an ultrashort saturable absorption recovery time (<60 fs), which is ultimately determined by the relaxation dynamics of photoexcited carriers in graphene. We also observed pulse narrowing effects in our devices based on the autocorrelation measurement results. Such design concepts can be tailored via structure engineering to operate in broader wavelength ranges up to mid- and far- infrared spectral regions. These ultrafast low-saturation fluence saturable absorber designs can enable low-threshold, compact, self-starting mode-locked lasers, laser pulse shaping, and high-speed optical information processing.

Anomalous photoluminescence enhancement and resonance charge transfer in type-II 2D lateral heterostructures

Type-II band alignment can realize the efficient charge transfer and separation at the semiconductor heterointerface, which results in photoluminescence (PL) quenching. Recently, several researches demonstrated great enhancement of localized PL at the interface of type-II two-dimensional (2D) heterostructure. However, the dominant physical mechanism of this enhanced PL emission has not been well understood. In this work, we symmetrically study the exciton dynamics of type-II lateral heterostructures of monolayer MoS2 and WS2 at room temperatures. The strong PL enhancement along the one-dimensional (1D) heterointerface is associated with the trion emission of the WS2 shell, while a dramatic PL quenching of neutral exciton is observed on the MoS2 core. The enhanced quantum yield of WS2 trion emission can be explained by charge-transfer-enhanced photoexcited carrier dynamics, which is facilitated by resonance hole transfer from MoS2 side to WS2 side. This work sheds light on the 1D exciton photophysics in lateral heterostructures, which has the potential to lead to new concepts and applications of optoelectronic device.

Excitation-Wavelength-Dependent Charge-Carrier Lifetime in Hematite: An Insight from Nonadiabatic Molecular Dynamics.

Experiments have reported that the photoexcited carrier lifetime in α-Fe2O3 has a significant excitation-wavelength dependence but leave the physical mechanism unresolved. In this work, we rationalize the puzzling excitation-wavelength dependence of the photoexcited carrier dynamics in Fe2O3 by performing nonadiabatic molecular dynamics simulation based on the strongly constrained and appropriately normed functional, which accurately describes the electronic structure of Fe2O3. Photogenerated electrons with lower-energy excitation relax fast in the t2g conduction band within about 100 fs, while the photogenerated electrons with higher-energy excitation undergo first a slower interband relaxation from the eg lower state to the t2g upper state on a time scale of 135 ps, followed by the much faster t2g intraband relaxation. This study provides insight into the experimentally reported excitation-wavelength dependence of the carrier lifetime in Fe2O3 and a reference for regulating photogenerated carrier dynamics in transition-metal oxides through the light excitation wavelength.

Investigation of self-trapped excitonic dynamics in hematite nanoforms through non-degenerate pump–probe transmission spectroscopy

Non-degenerate pump–probe transmission spectroscopy is used to examine the ultrafast dynamics of photo-excited carriers in hematite nanoforms at various pump fluences. Using coupled rate equations, the kinetics of self-trapped exciton (STE) formation and its interaction with free excitons resulting in exciton annihilation were studied. It is shown from this model that the majority of the excitons were trapped by polaronic trap states to form self-trapped excitons within ∼3.5 ps. The findings indicate that free excitons and STEs interact non-linearly, similar to trap-assisted bi-molecular Auger recombination to annihilate one another. It is observed that there is substantial dependence of kinetics of STE formation and exciton decay on photo-excited exciton density, and the nature of this dependence indicates the reduced screening of electron–phonon interaction. Using the screening model applied to the rate constants of STE formation and decay, we estimate the saturation exciton density to be ∼3.3 × 1017 cm−3 and the average STE density to be ∼3.8 × 1018 cm−3 in the hematite nanoforms. We also noticed that doping K and Ni to hematite nanoforms up to 5% did not remarkably change the nature of the exciton dynamics.

(Invited) In Situ spectroscopy of Electrochemical and Photoelectrochemical Interfaces

We explore various aspects of electrochemistry and photoelectrochemistry using in situ spectroscopy of electrode (metal) and photoelectrode (semiconductor) interfaces under electrochemical working conditions. Using sum frequency generation (SFG) spectroscopy, we measure the voltage dependence of the orientation of D2O molecules at a graphene electrode surface, which enables us to extract the free energy orienting potential of interfacial water.1 In particular, we measure the “free OD” feature in the spectra, which corresponds to the topmost water molecule that is rotated up out of the bulk water solution and is, therefore, not hydrogen bonded. Using transient absorption spectroscopy (TAS), we measure the lifetime of hot electrons photoexcited in plasmon resonant nanostructures.5 In a similar study, we use transient reflectance spectroscopy (TRS) to measure the photoexcited carrier dynamics in a GaP/TiO2 photoelectrode, as well as the electrostatic field dynamics at this semiconductor-liquid interface in situ under various electrochemical potentials.2 Here, the electrostatic fields at the surface of the semiconductor are measured via Franz−Keldysh oscillations (FKO). These spectra reveal that the nanoscale TiO2 protection layer enhances the built-in field and charge separation performance of GaP photoelectrodes. Using surface enhanced Raman scattering (SERS) spectroscopy, we monitor local electric fields via Stark-shifts of nitrile-functionalized silicon photoelectrodes.6 By monitoring Stark shifts in graphene-enhanced Raman spectroscopy (GERS), we measure local electric fields and local charge densities at monolayer graphene electrode surfaces.3 Lastly, we measure the stacking dependence of monolayer WSe2/MoSe2 heterostructures and observe resonant excitation of interlayer excitons for photocatalytic energy conversion.4 Montenegro, A., C. Dutta, M. Mammetkuliev, H.T. Shi, B.Y. Hou, D. Bhattacharyya, B.F. Zhao, S.B. Cronin and A.V. Benderskii, Asymmetric response of interfacial water to applied electric fields. Nature, 594, 62 (2021).Xu, Z.H., B.Y. Hou, F.Y. Zhao, Z. Cai, H.T. Shi, Y.W. Liu, C.L. Hill, D.G. Musaev, M. Mecklenburg, S.B. Cronin and T.Q. Lian, Nanoscale TiO2 Protection Layer Enhances the Built-In Field and Charge Separation Performance of GaP Photoelectrodes. Nano Letters, 21, 8017-8024 (2021).Shi, H.T., B.F. Zhao, J. Ma, M.J. Bronson, Z. Cai, J.H. Chen, Y. Wang, M. Cronin, L. Jensen and S.B. Cronin, Measuring Local Electric Fields and Local Charge Densities at Electrode Surfaces Using Graphene-Enhanced Raman Spectroscopy (GERS)-Based Stark-Shifts. ACS Applied Materials & Interfaces, 11, 36252-36258 (2019).Chen, J., C.S. Bailey, D. Cui, Y. Wang, B. Wang, H. Shi, Z. Cai, E. Pop, C. Zhou and S.B. Cronin, Stacking Independence and Resonant Interlayer Excitation of Monolayer WSe2/MoSe2 Heterostructures for Photocatalytic Energy Conversion. ACS Applied Nano Materials, DOI:10.1021/acsanm.9b01898 (2020).Yu Wang, Yi Wang, Indu Aravind, Zhi Cai, Lang Shen, Boxin Zhang, Bo Wang, Jihan Chen, Bofan Zhao, Haotian Shi, Jahan M. Dawlaty, and Stephen B. Cronin. In Situ Investigation of Ultrafast Dynamics of Hot Electron-Driven Photocatalysis in Plasmon-Resonant Grating Structures. Journal of the American Chemical Society. DOI: 10.1021/jacs.1c12069 (2022).Haotian Shi, Ryan T. Pekarek, Ran Chen, Boxin Zhang, Yu Wang, Indu Aravind, Zhi Cai, Lasse Jensen, Nathan R. Neale, and Stephen B. Cronin. Monitoring Local Electric Fields using Stark Shifts on Napthyl Nitrile-Functionalized Silicon Photoelectrodes. The Journal of Physical Chemistry C, 124, 17000-17005 (2020).

Photoexcited carrier dynamics in semi-insulating 4H-SiC by Raman spectroscopy

The photoexcited carrier dynamics of high-purity (HPSI) and vanadium-doped semi-insulating (VDSI) 4H-SiC irradiated by lasers with different wavelengths and powers were investigated. Raman spectra were measured at room temperature and the photoexcited carrier concentrations were extracted from the Raman line shape analysis of longitudinal optical phonon–plasmon coupled mode. It was found that the longitudinal optical (LO) peaks of HPSI and VDSI did not shift with laser power variations, due to a low concentration of photoexcited carriers, when a 532- nm laser was used. However, when a 355- nm laser was adapted, the relationship between the photoexcited carrier concentrations and the laser power was found to be nonlinear because of the dominance of trap-assisted Auger (TAA) recombination. The coefficient of TAA recombination was laser power–dependent. The proposed carrier dynamic model deepens the understanding of the physical mechanism of semi-insulating SiC irradiated by nanosecond laser and provides an insight into the interpretation of experimental phenomena related to laser energy in optoelectronic devices.

Nonlinear optical properties and photoexcited carrier dynamics of MnPS3 nanosheets.

Here, we systematically report on the preparation of high-quality few-layered MnPS3 nanosheets (NSs) by chemical vapor transport (CVT) and mechanical stripping method, and its carrier dynamics and third-order nonlinear optical properties were studied. Using the classical technique of open aperture Z-scan, a typical phenomenon of saturable absorption (SA) was observed at 475 nm, which indicates that the material is expected to be used as a saturable absorber in ultrafast lasers. The typical phenomenon of reverse saturation absorption (RSA) is observed at 800 and 1550 nm, which shows its potential in the field of broadband optical limiting. Compared with graphene, BP, MXene, MoS2 and other typical two-dimensional materials, MnPS3 NSs has a higher modulation depth. Using the non-degenerate transient absorption spectroscopy technology at room temperature, a slower cooling process of thermal carrier of MnPS3 was observed. Moreover, the carrier lifetime can be tuned according to the wavelength. This work is of great significance to the improvement of MnPS3 based devices, and lays a foundation for the application of MnPS3 in short-wavelength photovoltaic cell, photoelectric detection and other fields.