Excited Carrier Density Research Articles

Ultrafast reversible phase engineering in MoTe2 thin film via polaron formation

The emergence of various polymorphs in two-dimensional transition metal dichalcogenides provides an opportunity for robust phase engineering by temperature, strain, laser irradiation, and external charge doping (Keum in Nat. Phys. 11:482, 2015; Song in Nano Lett. 16:188, 2016; Cho in Science 349:625, 2015; Kim in Nano Lett. 17:3363, 2017). This provides means to develop homojunction of metal–semiconductor, enhance mobility, reduce contact resistance, and observe novel quantum critical phenomena in mesoscopic systems. The rich physics paves the way for ultrafast light-induced switching/memory devices and optical data processing in optoelectronics. However, the fundamental temporal evolution of the laser-driven phase transformation, in particular regarding heat and charge carriers, remains elusive. We report an ultrafast reversible structural transformation in MoTe2 by coherent phonon dynamics through polaron formation at room temperature. At a high photon density, the generated coherent phonons are coupled with excitons to form polarons. The strong exciton–phonon coupling disturbs and dephases the coherent phonons of the semiconducting 2H phase in MoTe2, and generates lattice distortions to further stabilize new coherent phonons of the metallic 1T’-phase, manifested by the emergence of the corresponding phonons in each phase. This structural transformation is fully reversible within a few picoseconds by switching on/off the laser. The nonlinear response of the phonon intensity to the excited carrier density in the intermediate region indicates a gradual structural transformation through coexisting 2H and 1T’ phases.

Lasing emission from ZnO hierarchical spherical microcavity

We investigated lasing characteristics of ZnO hierarchical micro-spherical particles with diameters of 1–5 μm . The lasing emission consists of a small number of discrete laser peaks unlike conventional random lasing from ZnO nanopowder-assembly. Theoretical calculations based on a many-body theory reveal that the optical gain is achieved at the observed lowest lasing threshold value, 4 mJ⋅cm−2⋅pulse−1 , which corresponds to the excited carrier density ∼2.4×1025 m−3 . Because the carrier density is much higher than the Mott density, the gain origin for lasing is electron-hole plasma recombination. The lasing frequency mode shift ( ∼1.2 meV ) is due to the refractive index change induced by exciting high carrier density up to 6.1×1025 m−3 . By changing hierarchical structures via controlling growth condition and performing the annealing treatment and performing the calculation of scattering efficiency of ZnO particles, we found that the hierarchy of the micro-spherical particle plays a crucial role of the lasing feedback: the strong light scattering at the interface between outer nanoparticles with the sizes of 100–200 nm and smaller ones with the sizes of 10–60 nm consisting in the micro-spherical particle results in a light confinement. Furthermore, it has been confirmed that each discrete lasing mode shows strong gain competition with each other probably due to spatial overlap between the modes. These results suggest that both random scattering and microcavity modes contribute to the lasing oscillation.

Size‐Dependent Multi‐Electron Donation in Metal‐Complex Quantum Dots Hybrid Catalyst for Photocatalytic Carbon Dioxide Reduction

AbstractThe effective conversion of carbon dioxide (CO2) into valuable chemical fuels relies significantly on the donation of multiple electrons. Its efficiency is closely linked to both the density and lifetime of excited charge carriers. In this study, a hybrid catalyst system comprising covalently bonded InP/ZnS quantum dots (QDs) and Re‐complexes is showcased. The electronic band alignment between the QDs and the Re‐complexes is revealed to dominate the multi‐electron transfer process for photocatalytic conversion to methane (CH4). Notably, the size of the QDs is found to be a determining parameter. Among the three QD sizes investigated, transient absorption spectroscopy studies unveil that rapid multi‐electron transfer from the QDs to the Re‐catalyst occurs in smaller QDs (2.3 nm) due to the substantial driving force. Consequently, the photocatalytic conversion of CO2 to CH4 is significantly enhanced with a turnover number of 6, corresponding to the overall apparent quantum yield of ≈1%. This research underscores the possibilities of engineering multi‐electron transfer by manipulating the electronic band alignment within a catalytic system. This can serve as a guide for optimizing photocatalytic CO2 reduction.

Diffusion-Dominated Luminescence Dynamics of CsPbBr3 Studied Using Cathodoluminescence and Microphotoluminescence Spectroscopy.

Time-resolved or time-correlation measurements using cathodoluminescence (CL) reveal the electronic and optical properties of semiconductors, such as their carrier lifetimes, at the nanoscale. However, halide perovskites, which are promising optoelectronic materials, exhibit significantly different decay dynamics in their CL and photoluminescence (PL). We conducted time-correlation CL measurements of CsPbBr3 using Hanbury Brown-Twiss interferometry and compared them with time-resolved PL. The measured CL decay time was on the order of subnanoseconds and was faster than PL decay at an excited carrier density of 2.1 × 1018 cm-3. Our experiment and analytical model revealed the CL dynamics induced by individual electron incidences, which are characterized by highly localized carrier generation followed by a rapid decrease in carrier density due to diffusion. This carrier diffusion can play a dominant role in the CL decay time for undoped semiconductors, in general, when the diffusion dynamics are faster than the carrier recombination.

Direct Observation of Ultrafast Lattice Distortions during Exciton-Polaron Formation in Lead Halide Perovskite Nanocrystals.

The microscopic origin of slow hot-carrier cooling in lead halide perovskites remains debated and has direct implications for applications. Slow hot-carrier cooling of several picoseconds has been attributed to either polaron formation or a hot-phonon bottleneck effect at high excited carrier densities (>1018 cm-3). These effects cannot be unambiguously disentangled with optical experiments alone. However, they can be distinguished by direct observations of ultrafast lattice dynamics, as these effects are expected to create qualitatively distinct fingerprints. To this end, we employ femtosecond electron diffraction and directly measure the sub-picosecond lattice dynamics of weakly confined CsPbBr3 nanocrystals following above-gap photoexcitation. While we do not observe signatures of a hot-phonon bottleneck lasting several picoseconds, the data reveal a light-induced structural distortion appearing on a time scale varying between 380 and 1200 fs depending on the excitation fluence. We attribute these dynamics to the effect of exciton-polarons on the lattice and the slower dynamics at high fluences to slower sub-picosecond hot-carrier cooling, which slows down the establishment of the exciton-polaron population. Further analysis and simulations show that the distortion is consistent with motions of the [PbBr3]- octahedral ionic cage, and closest agreement with the data is obtained for Pb-Br bond lengthening. Our work demonstrates how direct studies of lattice dynamics on the sub-picosecond time scale can discriminate between competing scenarios proposed in the literature to explain the origin of slow hot-carrier cooling in lead halide perovskites.

Optical nonlinearities in the excited carrier density of atomically thin transition metal dichalcogenides

In atomically thin semiconductors based on transition metal dichalcogenides, photoexcitation can be used to generate high densities of electron-hole pairs. Due to optical nonlinearities, which originate from Pauli blocking and many-body effects of the excited carriers, the generated carrier density will deviate from a linear increase in pump fluence. In this paper, we describe nonlinear absorption properties and excited carrier dynamics using a theoretical approach that combines results from ab initio electronic-state calculations with a many-body treatment of optical excitation. We determine the validity range of a linear approximation for the excited carrier density vs pump power and identify the role and magnitude of optical nonlinearities at elevated excitation carrier densities for ${\mathrm{MoS}}_{2}, {\mathrm{MoSe}}_{2}, {\mathrm{WS}}_{2}$, and ${\mathrm{WSe}}_{2}$ considering various excitation conditions. For photoexcitation at the bandgap, we find that the use of a linear absorption coefficient of the unexcited system can strongly underestimate the achievable carrier density in ${\mathrm{MoS}}_{2}$ due to many-body renormalizations of the two-particle density of states. The same holds for excitation of the high-energy band continuum in W-based materials.

Few-cycle optical field breakdown and damage of gallium oxide and gallium nitride

Both gallium oxide and gallium nitride have great potential for use as high power transparent conducting oxide materials for a wide range of optoelectronic applications. It is, therefore, important to determine the dynamic optical field breakdown for these materials. Here, we report laser damage thresholds for Ga2O3 and GaN using 9 fs few-cycle pulses with a center wavelength near 760 nm. We determine laser-induced damage thresholds (LIDTs) for both single pulse and multi-pulse exposures, with multi-pulse LIDT showing significant reduction compared to single pulse LIDT (in some cases, >50%), possibly due to laser-induced defects. We show that Ga2O3 and GaN have an ultrafast optical field breakdown of 23 and 18 GV/m when nearly polarized along their [010] and [111] planes, respectively, extending their suitability for high power applications to the ultrashort pulse regime. To accurately characterize the excited carrier density criteria in which apparent laser damage occurs, carrier excitation dynamics for the entire laser pulse interaction were simulated using a modified Keldysh ionization model. For the measured single-shot threshold fluences, the plasma critical density was surpassed by 2 orders of magnitude and 2D finite-difference time-domain simulations were employed to understand the pulse interaction near the surface.

Photo-induced enhancement of lattice fluctuations in metal-halide perovskites

The optoelectronic properties of metal-halide perovskites (MHPs) are affected by lattice fluctuations. Using ultrafast pump-probe spectroscopy, we demonstrate that in state-of-the-art mixed-cation MHPs ultrafast photo-induced bandgap narrowing occurs with a linear to super-linear dependence on the excited carrier density ranging from 1017 cm−3 to above 1018 cm−3. Time-domain terahertz spectroscopy reveals carrier localization increases with carrier density. Both observations, the anomalous dependence of the bandgap narrowing and the increased carrier localization can be rationalized by photo-induced lattice fluctuations. The magnitude of the photo-induced lattice fluctuations depends on the intrinsic instability of the MHP lattice. Our findings provide insight into ultrafast processes in MHPs following photoexcitation and thus help to develop a concise picture of the ultrafast photophysics of this important class of emerging semiconductors.

Photoinduced Ultrafast Symmetry Switch in SnSe.

Layered tin selenide (SnSe) has recently emerged as a high-performance thermoelectric material with the current record for the figure of merit (ZT) observed in the high-temperature Cmcm phase. So far, access to the Cmcm phase has been mainly obtained via thermal equilibrium methods based on sample heating or application of external pressure, thus restricting the current understanding only to ground-state conditions. Here, we investigate the ultrafast carrier and phononic dynamics in SnSe. Our results demonstrate that optical excitations can transiently switch the point-group symmetry of the crystal from Pnma to Cmcm at room temperature in a few hundreds of femtoseconds with an ultralow threshold for the excitation carrier density. This nonequilibrium Cmcm phase is found to be driven by the displacive excitation of coherent Ag phonons and, given the absence of low-energy thermal phonons, exists in SnSe with the status of 'cold lattice with hot carriers'. Our findings provide an important insight for understanding the nonequilibrium thermoelectric properties of SnSe.

Analyzing random lasing spectra of the zinc oxide bulk and the multiple quantum wells by empirical mode decomposition and fast Fourier transform

Empirical mode decomposition (EMD) was used to efficiently distinguish weak random-cavity emission from large broad spontaneous emission of the ZnO bulk and the multiple quantum wells (MQWs) structures. By fast Fourier transforming (FFT) the EMD results, we obtained the optical cavity lengths of random lasing and their corresponding emission intensity. With increasing pumping power, the EMD-FFT method confirms that the nonlinear trend of the random lasing emission in ZnO bulk and the change in optical cavity length is a result of change in refractive index dispersion due to the bandgap renormalization with high excited carrier density in nonpolar a-plane ZnO MQWs.

Hot carrier transport limits the displacive excitation of coherent phonons in bismuth

We performed femtosecond transient reflectivity measurements on epitaxially grown bismuth (Bi) films in the weak photoexcitation regime. Single crystalline ultrathin Bi films down to a thickness of 7 nm enabled us to determine a clear correspondence between the amplitude of the coherent A1g phonon and the photoexcitation level. We were able to empirically measure the effective hot carrier penetration length that determines the excited carrier density governing the magnitude of the coherent A1g phonon in Bi. Our findings suggest that the transport behavior of hot carriers is to be taken into consideration in order to provide insights into the mechanism for the displacive excitation of coherent phonons.

Low Barrier for Exciton Self-Trapping Enables High Photoluminescence Quantum Yield in Cs3Cu2I5.

The metal halide Cs3Cu2I5 displays anomalous optical properties: an optical absorption onset in the ultraviolet region (∼ 330 nm) with highly efficient luminescence in the blue region (∼ 445 nm). Although self-trapped exciton formation has been proposed as the origin of giant Stokes shift, its connection to the photoluminescence quantum yield exceeding 90% remains unknown. Here, we explore the photochemistry of Cs3Cu2I5 from first-principles and reveal a low energy barrier for exciton self-trapping associated with Cu-Cu dimerization. Kinetic analysis shows that the quantum yield of blue emission in Cs3Cu2I5 is sensitive to the excited carrier density due to the competition between exciton self-trapping and band-to-band radiative recombination.

Single-Atom-Based Heterojunction Coupling with Ion-Exchange Reaction for Sensitive Photoelectrochemical Immunoassay.

Benefiting from the maximum atom-utilization efficiency and distinct structural features, single-atom catalysts open a new avenue for the design of more functional catalysts, whereas their bioapplications are still in their infancy. Due to the advantages, platinum single atoms supported by cadmium sulfide nanorods (Pt SAs-CdS) are synthesized to build an ultrasensitive photoelectrochemical (PEC) biosensing platform. With the decoration of Pt SAs, the PEC signal of CdS is significantly boosted. Furthermore, theory calculations indicate the positively charged Pt SAs could change the charge distribution and increase the excited carrier density of CdS. Meanwhile, it also suggests that Cu2+ can severely hinder the photoexcitation and electron-hole separation of CdS. As a proof of concept, prostate-specific antigen is chosen as the target analyte to demonstrate the superiority of the Pt SAs-CdS-based PEC sensing system. As a result, the PEC biosensor based on Pt SAs-CdS exhibits outstanding detection sensitivity and promising applicability.

Multiphoton-excited exciton molecules in diamond

In this paper we report on observation of exciton molecules in the low-temperature photoluminescence spectra of diamond. The charge carriers are excited using multiphoton absorption of few-cycle near-infrared laser pulses. We observe that peaks corresponding to exciton molecules are well resolved and the formation of electron hole droplets is suppressed due to the initial carrier dynamics and low excited carrier densities.

A combined model for formation mechanism of ripples induced by femtosecond laser on silicon carbide

In this article, a comparative study is performed to explore the formation mechanism of laser-induced periodic surface structures (LIPSS) using femtosecond laser on silicon carbide (SiC). The optical properties of SiC transformed to a metal-like state when the excited carrier density exceeds 2e22 cm−3 under laser irradiation and significantly altered the laser energy deposition. The laser-induced carrier density coupled with the optical properties and the incident laser intensity profile were calculated. The two-temperature model was used to describe the energy transformation from electron to lattice and guided to select appropriate laser conditions for producing ripples. The spatial period of laser-induced periodic nanostructures was calculated in frequency domain based on the Drude-Sipe model that comprised the estimation of free carrier density. The calculated range of the spatial period of LIPSS was about from 776 to 544 nm. Additionally, the experimental value was about 719–483 nm, which contained a good consistency with the theoretical results. This work provides a new approach for the prediction and fabrication of the LIPSS on SiC.

Sub-picosecond photo-induced displacive phase transition in two-dimensional MoTe2

Photo-induced phase transitions (PIPTs) provide an ultrafast, energy-efficient way for precisely manipulating the topological properties of transition-metal ditellurides and can be used to stabilize a topological phase in an otherwise semiconducting material. Using first-principles calculations, we demonstrate that the PIPT in monolayer MoTe2 from the semiconducting 2H phase to the topological 1T′ phase can be triggered purely by electronic excitations that soften multiple lattice vibrational modes. These softenings, driven by a Peierls-like mechanism within the conduction bands, lead to structural symmetry breaking within sub-picosecond timescales, which is shorter than the timescale of a thermally driven phase transition. The transition is predicted to be triggered by photons with energies over 1.96 eV, with an associated excited carrier density of 3.4 × 1014 cm−2, which enables a controllable phase transformation by varying the laser wavelength. Our results provide insight into the underlying physics of the phase transition in 2D transition-metal ditellurides and show an ultrafast phase-transition mechanism for manipulation of the topological properties of 2D systems.

Carrier Multiplication in PbS Quantum Dots Anchored on a Au Tip using Conductive Atomic Force Microscopy

Carrier multiplication (CM) is the amplification of the excited carrier density by two times or more when the incident photon energy is larger than twice the bandgap of semiconductors. A practical approach to demonstrate the CM involves the direct measurement of photocurrent in the device. Specifically, photocurrent measurement in quantum dots (QDs) is typically limited by high contact resistance and long carrier-transfer length, which yields a low CM conversion efficiency and high CM threshold energy. Here, the local photocurrent is measured to evaluate the CM quantum efficiency from a QD-attached Au tip of a conductive atomic force microscope (CAFM) system. The photocurrent is efficiently measured between the PbS QDs anchored on a Au tip and a graphene layer on a SiO2 /Si substrate as a counter electrode, yielding an extremely short channel length that reduces the contact resistance. The quantum efficiency extracted from the local photocurrent data with an incident photon energy exhibits a step-like behavior. More importantly, the CM threshold energy is as low as twice the bandgap, which is the lowest threshold energy of optically observed QDs to date. This enables the CAFM-based photocurrent technique to directly evaluate the CM conversion efficiency in low-dimensional materials.

Impact of alloy disorder on Auger recombination in single InGaN/GaN core-shell microrods

We study the influence of local inhomogeneities on carrier recombination dynamics in single InGaN/GaN core-shell microrods (MRs) by means of time-resolved microphotoluminescence (TRPL) at 10 K. At low carrier density ($\ensuremath{\sim}{10}^{11}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}2}$), the carrier recombination in the $m$-plane quantum well is dominated by radiative processes and the recorded decay times along the MR equally amount to about 400 ps, corresponding to a bimolecular coefficient of $1.1\ifmmode\pm\else\textpm\fi{}0.2\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}2}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{2}\phantom{\rule{0.16em}{0ex}}{\mathrm{s}}^{\ensuremath{-}1}$. When the excited carrier density exceeds ${10}^{12}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}2}$, both the efficiency and the decay time of the PL in the quantum well drop significantly, which indicates the onset of Auger recombination. Based on a modified ABC model, we estimate a C coefficient varying from $0.5\ifmmode\pm\else\textpm\fi{}0.2$ to $2.2\ifmmode\pm\else\textpm\fi{}0.9\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}16}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{4}\phantom{\rule{0.16em}{0ex}}{\mathrm{s}}^{\ensuremath{-}1}$ from the lower to the upper part of the MR. This increase is accompanied by a rise of PL linewidth in the low excitation regime, indicating an increase of alloy disorder. Relaxation of the $k$-selection rule by alloy disorder is expected to play an important role in the observed increase of Auger coefficient. These results confirm that Auger recombination is sensitive to disorder and can be significantly enhanced in strongly disordered systems. We conclude that it is therefore crucial to minimize the degree of disorder in the active layer for high power LEDs based on core-shell MRs.

Optical gain of inelastic exciton-exciton scattering in CdS nanowires

We have performed a variable stripe length method at 5 K to measure the optical gain of CdS nanowires. When the excited carrier density is lower than the Mott density, we found that various inelastic scatterings of excitons and LO-phonons are involved. As a consequence of inelastic exciton-exciton scattering, the excitons scattered down to the low polariton branch cause P-emission lasing, and the excited excitons also result in a population inversion through intra-relaxation. When LO-phonon scatterings are involved, a broad optical gain spectrum is observed resulting from exciton-LO and P-LO scatterings.

Ultrafast electron hole plasma dynamics in chemically pristine and Ag-doped ZnO nanorods

The ultrafast dynamics of femotosecond laser excited carriers in the assembly of chemically pristine and Ag-doped ZnO nanorods is studied using the two-color pump-probe spectroscopy technique with the central photon energy of the pump pulse equal to the bandgap of the nanorods ensemble (∼3.14 eV) and the central photon energy of the probe pulse kept at 1.57 eV. On photo-excitation at 3.14 eV with an excited carrier density of ∼1020cm−3, about an order higher than the Mott density of bulk ZnO, the time delayed probe transmission displays tri-exponential decay exhibiting three decay mechanisms: (i) ultrafast electron-phonon thermalization of the order of ∼0.40 ps, (ii) trap mediated decay with a time constant of ∼9 ps, and (iii) e-h recombination with a time constant of ∼650 ps. It is observed that as the carrier density increases, the first two decay processes get longer on contrary to the recombination time which gets shorter. A detailed analysis of the faster decay process through the Two Temperature Model of ultrafast carrier relaxation supports our observation. Doping of Ag in these nanorods is found to introduce new defect states which alter the carrier dynamics significantly.