Interband Recombination Research Articles

Polymorphic two-dimensional (2D) transition metal dichalcogenides (TMDCs) exhibit diverse properties for optoelectronic applications. Here, utilizing phase-engineered MoTe2 as a prototypical platform, we comprehensively explored its ultrafast and nonlinear optical properties to complete the fundamental framework of phase-dependent optical phenomena in 2D TMDCs. Starting with the phase-selective synthesis of 2H- and 1T'-MoTe2 with tailored thicknesses, we revealed their distinct photocarrier relaxation mechanisms using intensive power-/temperature-/thickness-dependent transient absorption spectra (TAS). Rapid electron-electron scattering and interband recombination dominated in the metallic 1T' phase, while slower defect trapping and phonon-mediated processes prevailed in the 2H phase, attributed to intrinsic differences in carrier concentration and band structure. Furthermore, we correlated the observed relaxation characteristics with nonlinear saturable absorption (SA) performance by integrating TAS and micro-Z-scan on identical flakes and revealed that prolonged photocarrier lifetimes and high linear absorbance contributed to SA enhancement via excited-state population regulation. Guided by this principle, an obvious MoTe2 SA improvement in the underperforming near-infrared region was achieved simply by increasing its thickness. Surprisingly, both phases exhibited high nonlinear coefficients of 103-105 cm GW-1 (400-1100 nm), superior to most 2D materials. Our findings enrich phase-tunable photophysics in 2D TMDCs and deliver effective optimization strategies for ultrafast photonics and optoelectronics.

Inorganic semiconductors are composed of heavy elements whose vibrational motions are well described by classical mechanics. Heavy elements, such as Pb and I, support charge carriers in metal halide perovskites. Nevertheless, the soft structure and strong coupling between the organic and inorganic components create conditions in which nuclear quantum effects (NQEs) can play important roles. By combining ab initio, ring-polymer, and nonadiabatic molecular dynamics approaches with time-domain density functional theory, we demonstrate how NQEs influence structural and electronic properties and electron-vibrational dynamics in hybrid organic-inorganic (MAPbI3) and all-inorganic (CsPbI3) perovskites. Quantum zero-point fluctuations enhance structural disorder, reduce the band gap, and accelerate elastic electron-vibrational scattering responsible for coherence loss. NQEs have opposite influences on intraband carrier relaxation and interband recombination. These inelastic scattering events are governed by the product of the overlap-like electron-phonon matrix element and atomic velocity. NQEs reduce the overlap and increases the velocity. The intraband carrier relaxation involves many states. Reduction of overlap between some states is offset by other pathways, while an increased velocity makes intraband relaxation faster. Electron-hole overlap in band-edge states plays a key role in the recombination, and its reduction by NQEs-enhanced disorder makes the recombination slower. This phenomenon is seen with both MAPbI3 and CsPbI3 and is much more pronounced when a light organic component is present. This study offers a detailed understanding of the role of NQEs in the carrier relaxation processes of perovskites, offering important theoretical insights into hot carriers and carrier recombination that govern the performance of solar cells and other optoelectronic devices.

It has been found that hetero layers of typical β-ZnSe and atypical α-ZnSe modifications can be obtained by the isovalent substitution method. Isovalent impurities are formed which predetermine the formation of dominant radiation with a quantum yield of η = 12–15% in the short wavelength edge region. Low-temperature studies and λ-modulation techniques allowed us to identify the radiation components. This radiation is generated by interband recombination and exciton annihilation. The high temperature stability of the radiation was confirmed over temperature variations including 77, 300, and 480 K.

Noble-metal-free Bi-OZIS nanohybrids for sacrificial-agent-free photocatalytic water splitting: With long-lived photogenerated electrons

Non-adiabatic (NA) molecular dynamics (MD) is a powerful approach for studying far-from-equilibrium quantum dynamics in photophysical and photochemical systems. Most NA-MD methods are developed and tested with few-state models, and their validity with complex systems involving many states is not well studied. By modeling intraband equilibration and interband recombination of charge carriers in MoS2, we investigate the convergence of three popular NA-MD algorithms, fewest switches surface hopping (FSSH), global flux surface hopping (GFSH), and decoherence induced surface hopping (DISH) with the number of states. Only the standard DISH algorithm converges with the number of states and produces Boltzmann equilibrium. Unitary propagation of the wave function in FSSH and GFSH violates the Boltzmann distribution, leads to internal inconsistency between time-dependent Schrödinger equation state populations and trajectory counts, and produces non-convergent results. Introducing decoherence in FSSH and GFSH by collapsing the wave function fixes these problems. The simplified version of DISH that omits projecting out the occupied state and is applicable to few-state systems also causes problems when the number of states is increased. We discuss the algorithmic application of wave function collapse and Boltzmann detailed balance and provide detailed FSSH, GFSH, and DISH flow charts. The use of convergent NA-MD methods is highly important for modeling complicated quantum processes involving multiple states. Our findings provide the basis for investigating quantum dynamics in realistic complex systems.

PdSe2 is a puckered transition metal dichalcogenide that has been reported to undergo a two-dimensional to three-dimensional structural transition under pressure. Here, we investigated the electronic and phononic evolution of PdSe2 under high pressure using pump-probe spectroscopy. We observed the electronic intraband and interband transitions occurring in the d orbitals of Pd, revealing the disappearance of the Jahn-Teller effect under high pressure. Furthermore, we found that the decay rates of interband recombination and intraband relaxation lifetimes change at 3 and 7 GPa, respectively. First-principles calculations suggest that the bandgap closure slows the decay rate of interband recombination after 3 GPa, while the saturation of phonon-phonon scattering is the main reason for the relatively constant intraband relaxation lifetime. Our work provides a novel perspective for understanding the evolution of the electron and modulation of the carrier dynamics by phonons under pressure.

The article discusses the preparation of epitaxial layers and GaN crystals, as well as the results of studies of their optical and luminescent properties. The parameters of the band structure of the resulting hexagonal modification materials ΔCR ≈ 10 meV and ΔSO ≈ 48 meV were determined. The mechanisms of the main recombination processes that determine the formation of radiation from undoped and Zn-doped materials have been established. The role of interband recombination and annihilation of excitons in the formation of radiation in the high-energy region and transitions of carriers through energy states that are formed and created by intrinsic point defects of the crystal lattice and dopant has been established. The role of response recombination processes in the formation of short-wave radiation spectra is analyzed.

Energetic disorder dominates optical properties and recombination dynamics in tin-lead perovskite nanocrystals

Pentagonal palladium diselenide (PdSe2) stands out for its exceptional optoelectronic properties, including high carrier mobility, tunable bandgap, and anisotropic electronic and optical responses. Herein, we systematically investigate photocarrier dynamics in PdSe2 ribbons using polarization-resolved optical pump-probe spectroscopy. In thin PdSe2 ribbons with a semiconductor phase, the photocarrier dynamics are found to be dominated by intraband hot-carrier cooling, interband recombination, and the exciton effect, showing weak crystalline orientation dependences. Conversely, in thick semimetal-phase PdSe2 ribbons, the photocarrier relaxations governed by the electron-optical/acoustic phonon scattering strongly depend on the sample orientation, albeit with a degradation in in-plane anisotropy following hot-carrier cooling. Furthermore, we analyze the correlations between photocarrier dynamics and anisotropic energy dispersions of electronic structures across a wide range in k space, as well as the contributions from the anisotropic electron-phonon couplings. Our study provides crucial insights for developing polarization-sensitive photoelectronic devices based on PdSe2.

Interband recombination in bulk indium-rich InGaN is studied via both spontaneous and stimulated emissions. Based on the low-temperature luminescence and absorption data, the magnitude of the edge tails in conduction and valence bands is determined, and the non-thermal energy distribution of excess holes localized in the fluctuating band potential is revealed. We show that the combination of carrier localization effects and Auger-determined interband rates fully accounts for the experimentally observed stimulated emission thresholds and gain values (∼20–30 kW/cm2 and >100 cm−1, respectively) at low temperatures (T < 100 K). It is suggested that exploiting structural disorder to keep injected holes below the mobility edge, thus suppressing defect-related recombination, is a prerequisite for high-temperature infrared lasing from degenerate InGaN with relatively temperature-stable threshold intensities of some 100 kW/cm2.

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.

We study photoluminescence temperature quenching in HgTe/CdHgTe quantum wells (QWs) emitting at 3–4 μm wavelengths and recover temperature-dependent interband recombination rates. Recombination coefficients are determined for the process that we identify as a non-threshold ehh Auger process involving valence band continuum states in barriers. With the effective Auger coefficient CA reaching ∼10−13 cm4/s under resonant conditions, such a process is shown to determine stimulated emission thresholds in a wide temperature interval, while the contribution of conventional, activated Auger processes is presumably rather limited. Thus, threshold energy considerations should be used with caution for the optimization of HgCdTe QW lasers operating around 3 μm, and relatively low-barrier QWs may provide better performance than the high-barrier ones despite lower energy thresholds for thermally activated eeh-Auger recombination. It holds as long as the conduction band offset is detuned from the bandgap energy to avoid additional non-threshold eeh-processes and sufficient hole localization at elevated temperatures is maintained.

Nanoscale light sources with high speed of electrical modulation and low energy consumption are key components for nanophotonics and optoelectronics. The record-high carrier mobility and ultrafast carrier dynamics of graphene make it promising as an atomically thin light emitter, which can be further integrated into arbitrary platforms by van der Waals forces. However, due to the zero bandgap, graphene is difficult to emit light through the interband recombination of carriers like conventional semiconductors. Here, we demonstrate ultrafast thermal light emitters based on suspended graphene/hexagonal boron nitride (Gr/hBN) heterostructures. Electrons in biased graphene are significantly heated up to 2800 K at modest electric fields, emitting bright photons from the near-infrared to the visible spectral range. By eliminating the heat dissipation channel of the substrate, the radiation efficiency of the suspended Gr/hBN device is about two orders of magnitude greater than that of graphene devices supported on SiO2 or hBN. We further demonstrate that hot electrons and low-energy acoustic phonons in graphene are weakly coupled to each other and are not in full thermal equilibrium. Direct cooling of high-temperature hot electrons to low-temperature acoustic phonons is enabled by the significant near-field heat transfer at the highly localized Gr/hBN interface, resulting in ultrafast thermal emission with up to 1 GHz bandwidth under electrical excitation. It is found that suspending the Gr/hBN heterostructures on the SiO2 trenches significantly modifies the light emission due to the formation of the optical cavity and showed a ∼440% enhancement in intensity at the peak wavelength of 940 nm compared to the black-body thermal radiation. The demonstration of electrically driven ultrafast light emission from suspended Gr/hBN heterostructures sheds the light on applications of graphene heterostructures in photonic integrated circuits, such as broadband light sources and ultrafast thermo-optic phase modulators.

Preparation of 1T′- and 2H–MoTe2 films and investigation of their photoelectric properties and ultrafast photocarrier dynamics

Low power silicon based light source and detector are attractive for on-chip photonic circuits given their ease of process integration. However, conventional silicon light emitting diodes emit photons with energies near the band edge where the corresponding silicon photodetectors lack responsivity. On the other hand, previously reported hot carrier electroluminescent silicon devices utilizing a reverse biased diode require high operating voltages. Here, we investigate hot carrier electroluminescence in silicon metal–oxide–semiconductor capacitors operating under transient voltage conditions. During each voltage transient, large energy band bending is created at the edge of the source contact, much larger than what is achievable at a steady state. As a result, electrons and holes are injected efficiently from a single source contact into the silicon channel at the corresponding voltage transient, where they subsequently undergo impact ionization and phonon-assisted interband recombination. Notably, we show low voltage operation down to 2.8 V by using a 20 nm thick high-κ gate dielectric. We show further voltage scaling is possible by reducing the gate dielectric thickness, thus presenting a low voltage platform for silicon optoelectronic integrated circuits.

ZnPSe3 was identified as a two-dimensional material wherein valley and spin can be optically controlled in technologically relevant timescales. We report an optical characterization of ZnPSe3 crystals that show indirect band-gap characteristics in combination with unusually strong photoluminescence. We found evidence of interband recombination from photoexcited electron-hole states with lifetimes in a microsecond timescale. Through a comparative analysis of photoluminescence and photoluminescence excitation spectra, we reconstructed the electronic band scheme relevant to fundamental processes of light absorption, carrier relaxation, and radiative recombination through interband pathways and annihilation of defect-bound excitons. The investigation of the radiative processes in the presence of a magnetic field revealed spin splitting of electronic states contributing to the ground excitonic states. Consequently, the magnetic field induces an imbalance in the number of excitons with the opposite angular momentum according to the thermal equilibrium as seen in the photoluminescence decay profiles resolved by circular polarization.

Inter-Landau level transfer in valence band of In0.53Ga0.47As/InP quantum well

The problems of developing light-emitting structures based on CdTe with an extended range of operating temperatures and radiation-resistant parameters are studied. A technique for obtaining heterostructures has been mastered, technological modes of isovalent substitution have been determined, and radiation sources with a high quantum efficiency η = 7–20% at 300 K in a wide spectral region have been obtained. The design of devices has been developed and light emitters based on CdTe, whose radiation is determined by the interband recombination of free charge carriers and the dominant annihilation of bound excitons, have been fabricated by doping with isovalent impurities Mg, Ca.

We demonstrate an all optical approach that can surprisingly offer the possibility of yielding much more information than one would expect, pertinent to the carrier recombination dynamics via both radiative and nonradiative processes when only one dominant deep defect level is present in a semiconductor material. By applying a band-defect state coupling model that explicitly treats the inter-band radiative recombination and Shockley–Read–Hall (SRH) recombination via the deep defect states on an equal footing for any defect center occupation fraction, and analyzing photoluminescence (PL) as a function of excitation density over a wide range of the excitation density (e.g., 5–6 orders in magnitude), in conjunction with Raman measurements of the LO-phonon plasmon (LOPP) coupled mode, nearly all of the key parameters relevant to the recombination processes can be obtained. They include internal quantum efficiency (IQE), minority and majority carrier density, inter-band radiative recombination rate (Wr), minority carrier nonradiative recombination rate (Wnr), defect center occupation fraction (f), defect center density (Nt), and minority and majority carrier capture cross-sections (σt and σtM). While some of this information is thought to be obtainable optically, such as IQE and the Wr/Wnr ratio, most of the other parameters are generally considered to be attainable only through electrical techniques, such as current-voltage (I-V) characteristics and deep level transient spectroscopy (DLTS). Following a procedure developed herein, this approach has been successfully applied to three GaAs double-heterostructures that exhibit two distinctly different nonradiative recombination characteristics. The method greatly enhances the usefulness of the simple PL technique to an unprecedented level, facilitating comprehensive material and device characterization without the need for any device processing.

Direct Z-scheme photocatalytic systems are very promising composite photocatalysts, and their photocatalytic performance is highly associated with the quality of the interface within them. Herein, a novel direct Z-scheme heterojunction with a coherent interface has been presented for the first time. Specifically, the heterojunction was constructed by dispersing pre-prepared BiVO4 crystals into the reaction system to synthesize Cu3SnS4, followed by a hydrothermal reaction. It is shown that Cu3SnS4 was deposited on the surface of each pre-prepared BiVO4 crystal as a thin layer via heterogeneous nucleation to acquire a core-shell heterojunction. The BiVO4@Cu3SnS4 heterojunction was found to possess an atomic coherent interface, which is formed through the bonding between the (121) plane of BiVO4 and the (112) plane of Cu3SnS4, originating from the matching in the crystalline lattice between the two planes. The coherent interface facilitated the charge transfer from Cu3SnS4 to BiVO4 owing to the difference in their Fermi levels, thereby forming a built-in electric field pointing from Cu3SnS4 to BiVO4. Reduced fluorescence emission and a shortened carrier lifetime reveal an obvious reduction in the inter-band charge recombination for the optimal BVO@CTS-0.19 sample. Consequently, BVO@CTS-0.19 shows remarkably enhanced photocatalytic performance in MO degradation, Cr6+ reduction and oxygen evolution. The Z-scheme charge transfer mechanism for BVO@CTS-0.19 was verified by a suite of techniques. This work provides a universal strategy for building a coherent interface to develop high-performance direct Z-scheme heterojunctions.