Phonon-assisted Recombination Research Articles

Monolayer indium selenide: an indirect bandgap material exhibits efficient brightening of dark excitons

Atomically thin indium selenide (InSe) exhibits a sombrero-like valence band, leading to distinctive excitonic behaviors. It is known that the indirect band gap of atomically thin InSe leads to a weak emission from the lowest-energy excitonic state (A peak). However, the A peak emission of monolayer (ML) InSe was observed to be either absent or very weak, rendering the nature of its excitonic states largely unknown. Intriguingly, we demonstrate that ML InSe exhibits pronounced PL emission because of the efficient brightening of the momentum-indirect dark excitons. The mechanism is attributed to acoustic phonon-assisted radiative recombination facilitated by strong exciton-acoustic phonon coupling and extended wavefunction in momentum space. Systematic analysis of layer-, power-, and temperature-dependent PL demonstrates that a carrier localization model can account for the asymmetric line shape of the lowest-energy excitonic emission for atomically thin InSe. Our work reveals that atomically thin InSe is a promising platform for manipulating the tightly bound dark excitons in two-dimensional semiconductor-based optoelectronic devices.

Unraveling the Origin of Long-Lifetime Emission in Low-Dimensional Copper Halides via a Magneto-optical Study.

The origin of the long lifetime of self-trapped exciton emission in low-dimensional copper halides is currently the subject of extensive debate. In this study, we address this issue in a prototypical zero-dimensional copper halide, Cs2(C18)2Cu2I4-DMSO, through magneto-optical studies at low temperatures down to 0.2 K. Our results exclude spin-forbidden dark states and indirect phonon-assisted recombination as the origin of the long photoluminescence lifetime. Instead, we propose that the minimal Franck-Condon factor of the radiative transition from excited states to the ground state is the decisive factor, based on the transition probability analysis. Our findings offer insights into the electronic processes in low-dimensional copper halides and have the potential to advance the application of these distinctive materials in optoelectronics.

Octahedral Distortions Generate a Thermally Activated Phonon-Assisted Radiative Recombination Pathway in Cubic CsPbBr3 Perovskite Quantum Dots.

Exciton-phonon interactions elucidate structure-function relationships that aid in the control of color purity and carrier diffusion, which is necessary for the performance-driven design of solid-state optical emitters. Temperature-dependent steady-state photoluminescence (PL) and time-resolved PL (TRPL) reveal that thermally activated exciton-phonon interactions originate from structural distortions related to vibrations in cubic CsPbBr3 perovskite quantum dots (PQDs) at room temperature. Exciton-phonon interactions cause performance-degrading PL line width broadening and slower electron-hole recombination. Structural distortions in cubic PQDs at room temperature exist as the bending and stretching of the PbBr6 octahedra subunit. The PbBr6 octahedral distortions cause symmetry breaking, resulting in thermally activated longitudinal optical (LO) phonon coupling to the photoexcited electron-hole pair that manifests as inhomogeneous PL line width broadening. At cryogenic temperatures, the line width broadening is minimized due to a decrease in phonon-assisted recombination through shallow traps. A fundamental understanding of these intrinsic exciton-phonon interactions gives insight into the polymorphic nature of the cubic phase and the origins of performance degradation in PQD optical emitters.

Phonon-Assisted Auger-Meitner Recombination in Silicon from First Principles.

We present a consistent first-principles methodology to study both direct and phonon-assisted Auger-Meitner recombination (AMR) in indirect-gap semiconductors that we apply to investigate the microscopic origin of AMR processes in silicon. Our results are in excellent agreement with experimental measurements and show that phonon-assisted contributions dominate the recombination rate in both n-type and p-type silicon, demonstrating the critical role of phonons in enabling AMR. We also decompose the overall rates into contributions from specific phonons and electronic valleys to further elucidate the microscopic origins of AMR. Our results highlight potential pathways to modify the AMR rate in silicon via strain engineering.

Low voltage AC electroluminescence in silicon MOS capacitors

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.

Phonon-Assisted Nonradiative Recombination Tuned by Organic Cations in Ruddlesden-Popper Hybrid Perovskites

Significant efforts have been devoted to further increasing the photoconversion efficiency of two-dimensional (2D) organic-inorganic halide perovskites, which are promising photovoltaic materials with superior stability but lower efficiency compared to their three-dimensional counterparts. One of the main factors that limit their photoconversion efficiency is the nonradiative recombination of photoexcited carriers. A widely used strategy for tuning the photoconversion efficiency of 2D perovskites is exchanging various organic cations. However, due to mixed effects contributed to by extrinsic factors, such as defect concentration and sample morphology, experiments alone are insufficient to explain the role of organic cations in phonon-assisted carrier recombination. With time-domain simulations based on first-principles nonadiabatic molecular dynamics, we investigate six prototypical 2D Ruddlesden-Popper perovskites to reveal the impact of organic cations on tuning the nonradiative recombination time through displacing inorganic ions and affecting electron-phonon coupling. The phonon-assisted band-to-band nonradiative recombination time is on the order of a few hundred nanoseconds and can be tuned up to 5 times by modifying organic cations. A distinct correlation between the pure-dephasing time and inorganic atom distortions induced by the motion of organic parts is revealed. Compared to the pure-dephasing time, nonadiabatic coupling (NAC) associated with the strength of electron-phonon coupling plays a more important role in determining the nonradiative carrier recombination time. Notably, fluorinated organic spacers increase the NAC between frontier electronic states and speed up the nonradiative recombination process.

Quasi-two-dimensional van der Waals ferromagnetic semiconductor CrGeTe<sub>3</sub> studied by THz spectroscopy

The quasi-two-dimensional van der Waals intrinsic ferromagnetic semiconductor CrGeTe<sub>3</sub> possesses both a narrow semiconductor band gap and ferromagnetic properties, which makes it have a broad application prospect in the fields of spintronics and optoelectronics. In recent years, CrGeTe<sub>3</sub> has received extensive attention from researchers. To the best of our knowledge, so far, these studies have mainly focused on the optical response in near infrared and visible light range, but little has been done in THz frequency range. Therefore, it is upmost importance to obtain the complex dielectric constant as well as the photocarrier dynamics of the CrGeTe<sub>3</sub> at the THz frequency. Herewith, we use time-domain THz spectroscopy and time-resolved THz spectroscopy to investigate the fundamental properties of the CrGeTe<sub>3</sub> crystal in the THz range, including refractive index and absorption coefficient in THz frequency, as well as the THz photocarrier dynamics under 780-nm optical excitation. The fundamental characterizations are carried out on a 33-μm-thick CrGeTe<sub>3</sub> wafer by Fourier infrared spectroscopy, X-ray diffraction and Raman scattering. It is concluded that the CrGeTe<sub>3</sub> wafer shows an indirect band gap of 0.38 eV and good crystalline quality. The THz time domain spectroscopy presents that the CrGeTe<sub>3</sub> wafer has a refractive index and an absorption coefficient of 3.2 and 380 cm<sup>–1</sup>, respectively, both of which show almost negligible dispersion in the investigated THz frequency. Under the optical excitation of 780 nm, the subsequent photocarrier relaxation can be well reproduced by a double exponential function: the fast relaxation shows a lifetime of 1–2 ps, depending on pump fluence, which is contributed by electron-phonon coupling; the slow relaxation has a typical lifetime of 7–8 ps, which is due to phonon-assisted electron-phonon recombination. The Pump fluence and delay time dependence of THz photoconductivity dispersion can be well fitted with Drude-Smith model, and the fitted results demonstrate that the plasma frequency increases with pump fluence in a fixed delay time, and then decreases with delay time increasing at a fixed pump fluence. The momentum scattering time shows that it decreases with pump fluence increasing, and increases with delay time increasing. These pump fluence and delay time dependent fitting microscopic parameters show similar tendencies to those of a conventional semiconductor. In a word, the experimental study here demonstrates that the narrow band-gap CrGeTe<sub>3</sub> wafer is well transparent and disperionless in a THz frequency range. From the above bandgap photoexcitation it follows that the wafer shows fast response and high modulation depth in THz radiation, providing a useful reference for the application of CrGeTe<sub>3</sub> in optoelectronics and related fields.

Low temperature-promoted surface plasmon resonance effect and ultrasensitive surface-enhanced Raman scattering detection of creatinine

Creatinine is a key biomarker for diagnosing and monitoring kidney disease, so rapid and sensitive testing is very important. Raman spectroscopy is particularly suitable for quantitatively detecting the creatinine in the human environment because it is sensitive to subtle changes in the concentration of the analyte. In this work an effective strategy is provided to promote the activity of surface-enhanced Raman scattering spectroscopy by enhancing the photon-induced charge transfer efficiency at low temperature. The nano-gold icosahedron (Au<sub>20</sub>) is obtained by the seed-growing method, which is used as an active substrate for SERS. The ultra-low temperature (98 K) SERS detection technology is used to realize the rapid and sensitive detection of the dye molecule crystal violet (CV) and creatinine in normal saline. The experimental results show that at room temperature of 296 K, the detection limit of Au<sub>20</sub> substrate for CV molecules is as low as 10<sup>–12</sup> mol/L, and the signals are uniform; at a low temperature of 98 K, the detection limit of CV molecules can reach 10<sup>–14</sup> mol/L, which is two orders of magnitude lower than that at 296 K. As a result, the adopted cryogenic temperature can effectively weaken the lattice thermal vibration and reduce the release of phonons, then suppress phonon-assisted non-radiative recombination. So, it will increase the number of photo-induced electrons to participate in the photo-induced charge transfer efficiency. Finally, we perform the label-free detection of creatinine in saline by using an Au<sub>20</sub> substrate. The results show that the detection limit of the SERS substrate for creatinine is 10<sup>–6</sup> mol/L at 296 K, and the linear correlation coefficient of the 1619 cm<sup>–1</sup> peak is 0.9839. At a low temperature of 98 K, the detection limit of creatinine concentration is as low as 10<sup>–8</sup> mol/L, and the linear correlation coefficient of the 1619 cm<sup>–1</sup> peak becomes 0.9973. It can be seen that low temperature may further improve the detection limit of creatinine concentration and the linearity of characteristic peak. In summary, the current work provides a new idea for accurately detecting the creatinine concentration in the field of biomedicine.

Anisotropic Optical and Vibrational Properties of GeS

The optical response of bulk germanium sulfide (GeS) is investigated systematically using different polarization-resolved experimental techniques, such as photoluminescence (PL), reflectance contrast (RC), and Raman scattering (RS). It is shown that while the low-temperature (T = 5 K) optical band-gap absorption is governed by a single resonance related to the neutral exciton, the corresponding emission is dominated by the disorder/impurity- and/or phonon-assisted recombination processes. Both the RC and PL spectra are found to be linearly polarized along the armchair direction. The measured RS spectra over a broad range from 5 to 300 K consist of six Raman peaks identified with the help of Density Functional Theory (DFT) calculations: A, A, A, A, B, and B, which polarization properties are studied under four different excitation energies. We found that the polarization orientations of the A and A modes under specific excitation energy can be useful tools to determine the GeS crystallographic directions: armchair and zigzag.

Spectral asymmetry of phonon sideband luminescence in monolayer and bilayer WSe2

We report an experimental study of temperature-dependent spectral line shapes of phonon sideband emission stemming from dark excitons in monolayer and bilayer WSe2. Using photoluminescence spectroscopy in the range from 4 to 100 K, we observe a pronounced asymmetry in the phonon-assisted luminescence from momentum-indirect exciton reservoirs. We demonstrate that the corresponding spectral profiles are distinct from those of bright excitons with direct radiative decay pathways. The line-shape asymmetry reflects thermal distribution of exciton states with finite center-of-mass momenta, characteristic for phonon sideband emission. The extracted temperature of the exciton reservoirs is found to generally follow that of the crystal lattice, with deviations reflecting overheated populations. The latter are most pronounced in the bilayer case and at lowest temperatures. Our results add to the understanding of phonon-assisted recombination of momentum-dark excitons and, more generally, establish means to access the thermal distribution of finite-momentum excitons in atomically thin semiconductors with indirect band gaps.Received 21 May 2021Revised 28 September 2021Accepted 30 September 2021DOI:https://doi.org/10.1103/PhysRevResearch.3.L042019Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasExcitonsPhysical SystemsTransition metal dichalcogenidesTechniquesPhotoluminescenceCondensed Matter, Materials & Applied Physics

Nonclassical Exciton Diffusion in Monolayer WSe_{2}.

We experimentally demonstrate time-resolved exciton propagation in a monolayer semiconductor at cryogenic temperatures. Monitoring phonon-assisted recombination of dark states, we find a highly unusual case of exciton diffusion. While at 5K the diffusivity is intrinsically limited by acoustic phonon scattering, we observe a pronounced decrease of the diffusion coefficient with increasing temperature, far below the activation threshold of higher-energy phonon modes. This behavior corresponds neither to well-known regimes of semiclassical free-particle transport nor to the thermally activated hopping in systems with strong localization. Its origin is discussed in the framework of both microscopic numerical and semiphenomenological analytical models illustrating the observed characteristics of nonclassical propagation. Challenging the established description of mobile excitons in monolayer semiconductors, these results open up avenues to study quantum transport phenomena for excitonic quasiparticles in atomically thin van der Waals materials and their heterostructures.

Ultrafast charge dynamics and photoluminescence in bilayer MoS2

Our examination of the interplay of ultrafast charge dynamics and electron–phonon interaction in the AA′ stacked bilayer MoS2 provides a microscopic basis for understanding the features (two peaks) in the emission spectrum. We demonstrate that while the initial accumulation of excited charge occurs at and near the Q point of the two-dimensional Brillioun zone, emission takes place predominantly through two pathways: direct charge recombination at the K point and indirect phonon-assisted recombination of electrons at the valley and holes at the hill of the Brillouin zone. Analysis of the wave vector dependencies of the electron–phonon interaction traces the higher energy peak to phonon-assisted relaxation of the excited electrons from the Q to the K valley in the conduction band. Our results thus reveal the importance of ultrafast charge dynamics in understanding photoemissive properties of a few-layer transition-metal dichalcogenide. These calculations are based on time dependent density functional theory in the density matrix formulation.

Polarized emission of CdSe nanocrystals in magnetic field: the role of phonon-assisted recombination of the dark exciton.

The recombination dynamics and spin polarization of excitons in CdSe nanocrystals synthesized in a glass matrix are investigated using polarized photoluminescence in high magnetic fields up to 30 Tesla. The dynamics are accelerated by increasing temperature and magnetic field, confirming the dark exciton nature of low-temperature photoluminescence (PL). The circularly polarized PL in magnetic fields reveals several unusual appearances: (i) a spectral dependence of the polarization degree, (ii) its low saturation value, and (iii) a stronger intensity of the Zeeman component which is higher in energy. The latter feature is the most surprising being in contradiction with the thermal population of the exciton spin sublevels. The same contradiction was previously observed in the ensemble of wet-chemically synthesized CdSe nanocrystals but was not understood. We present a theory which explains all the observed features and shows that the inverted ordering of the circularly polarized PL maxima from the ensemble of nanocrystals is a result of competition between the zero phonon (ZPL) and one optical phonon-assisted (1PL) emission of the dark excitons. The essential aspects of the theoretical model are different polarization properties of the dark exciton emission via ZPL and 1PL recombination channels and the inhomogeneous broadening of the PL spectrum from the ensemble of nanocrystals exceeding the optical phonon energy.

Use of carrier injection engineering to increase the light intensity of a polycrystalline silicon avalanche mode light-emitting device

This paper demonstrates a polycrystalline silicon avalanche mode light-emitting device. The unique N+PN+PN+ cascade structure is designed to enhance light intensity via carrier injection engineering, in which the minority carriers are injected from the forward-biased junction to the light emission junction. Visible light can be observed at the reverse-biased PN junctions when the device operating voltage exceeds 20 V. In particular, the phonon-assisted indirect interband recombination of carriers with excess energy may be the main mechanism of photon emission. A specific junction model is proposed to explain that the light intensity peaks are generated primarily via carrier injection. Comparing the spectral measurements of a single polysilicon N+P junction device and the proposed cascade device shows that the strategy of improving the luminous intensity via carrier injection engineering is feasible and effective.

Computing the Effect of Metal Substitution in Metal–Organic Frameworks on the Recombination Times of Charge Carriers

Metal–organic frameworks (MOFs) have been attracting increasing attention in the fields of photoactive applications, for which understanding the factors governing their excited-state properties is critical. One of the major challenges includes reducing the energy losses due to the phonon-assisted nonradiative recombination and extending charge-carrier lifetimes. Metal substitution constitutes a way to modify the electronic structure of MOFs. Among different options, Ce-MOFs are often considered; however, from the theoretical perspective, little is known about the charge-carrier dynamics and recombination pathways in such systems. Therefore, in this work, the electron–hole recombination in a prototype Ce-based MOF is investigated. The limit of a radiative charge-carrier lifetime is estimated theoretically. The nonradiative recombination process is simulated using nonadiabatic molecular dynamics within the decoherence-induced surface-hopping approach and the corresponding electron–hole recombination rates are calculated, demonstrating that the charge-carrier lifetimes in Ce-MOFs are in excellent agreement with the experimental data. Importantly, the vibrational modes, which are the main contributors to the nonradiative decay, are analyzed. In particular, the role of the soft phonon modes in the charge-carrier recombination process is highlighted. Based on this data, the routes for modulating electron–hole lifetimes are suggested.

Electrochemical Charging Effect on the Optical Properties of InP/ZnSe/ZnS Quantum Dots.

Semiconductor quantum dots (QDs) are spotlighted as a key type of emissive material for the next generation of light-emitting diodes (LEDs). This work presents the investigation of the electrochemical charging effect on the absorption and emission of the InP/ZnSe/ZnS QDs with different mid-shell thicknesses. The excitonic peak is gradually bleached during electrochemical charging, which is caused by 1Se (or 1Sh ) state filling when the electron (or hole) is injected into the InP core. Additional charges also lead to photoluminescence (PL) intensity reduction, however, it is greatly mitigated as the mid-shell thickness increases. Various PL measurements reveal that the PL reduction under electrochemical charging is attributed to the acoustic phonon-assisted Auger recombination. Here, the Auger recombination in QDs with a thick mid-shell is reduced under the electrochemically charged condition, indicating that QDs with larger volume are more stable emitters in charge-injecting devices such as LEDs. Furthermore, the negative and positive trion Auger recombination rate constants are estimated, respectively, via electrochemical charging. The negative trion Auger rate constants decrease with an increase in the mid-shell thickness increases, whereas the positive trion Auger rate constants are not heavily reliant on the mid-shell thickness.

Anomalous Auger Recombination in PbSe.

Using first-principles approaches we find that the Auger recombination in PbSe is anomalous in three distinct ways. First, the direct Auger coefficient is 4 orders of magnitude lower than that of other semiconductors with similar band gaps, a result that can be attributed to the lack of involvement of a heavy-hole band. Second, phonon-assisted indirect Auger recombination prevails, contrary to the common belief that direct Auger is dominant in narrow-gap semiconductors. Third, an unexpectedly weak temperature dependence of the Auger coefficient is observed, which we can now attribute to the indirect nature of the Auger process. The widely accepted explanation of this behavior in terms of an unusual temperature dependence of the band gap is only a secondary effect. Our results elucidate the mechanisms underlying the anomalous Auger recombination in IV-VI semiconductors in general, which is critical for understanding and engineering carrier transport.

Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening.

Organic-inorganic hybrid halide perovskites are promising semiconductors with tailorable optical and electronic properties. The choice of A-site cation to support a three-dimensional (3D) perovskite structure AMX3 (where M is a metal and X is a halide) is limited by the geometric Goldschmidt tolerance factor. However, this geometric constraint can be relaxed in two-dimensional (2D) perovskites, providing us an opportunity to understand how various A-site cations modulate the structural properties and thereby the optoelectronic properties. Here, we report the synthesis and structures of single-crystal (BA)2(A)Pb2I7 where BA = butylammonium and A = methylammonium (MA), formamidinium (FA), dimethylammonium (DMA), or guanidinium (GA), with a series of A-site cations varying in size. Single-crystal X-ray diffraction reveals that the MA, FA, and GA structures crystallize in the same Cmcm space group, while the DMA imposes the Ccmb space group. We observe that as the A-site cation becomes larger, the Pb-I bond continuously elongates, expanding the volume of the perovskite cage, equivalent to exerting "negative pressure" on the perovskite structures. Optical studies and DFT calculations show that the Pb-I bond length elongation reduces the overlap of the Pb s- and I p-orbitals and increases the optical bandgap, while Pb-I-Pb tilting angles play a secondary role. Raman spectra show lattice softening with increasing size of the A-site cation. These structural changes with enlarged A cations result in significant decreases in photoluminescence intensity and lifetime, consistent with a more pronounced nonradiative decay. Transient absorption microscopy results suggest that the PL drop may derive from a higher concentration of traps or phonon-assisted nonradiative recombination. The results highlight that extending the range of Goldschmidt tolerance factors for 2D perovskites is achievable, enabling further tuning of the structure-property relationships in 2D perovskites.

Relevance of collinear processes to the ultrafast dynamics of photoexcited carriers in graphene

Abstract The importance of interband transitions on the ultrafast relaxation process in photoexcited pristine graphene is evaluated by means of an ensemble Monte Carlo simulator. Impact ionization and Auger recombination in the collinear limit are considered, together with phonon-induced generation and recombination and intraband scattering mechanisms. The results show that collinear impact ionization is dominant in the first 100 femtoseconds, creating an important excess carrier population that is finally eliminated in the picosecond scale, together with the photoexcited population, by Auger and optical phonon-assisted recombination. The hot phonon effect is also important, stimulating phonon absorption and indirectly reducing the net collinear recombination in the hundreds of femtosecond range. The substrate type is an important factor, appeasing collinear impact ionization via screening and creating additional cooling channels that speed up the relaxation process. The results evidence that interband collinear generation processes are critical to explain the fastest stages of the relaxation process in graphene.

Phonon-Assisted Photoluminescence from Indirect Excitons in Monolayers of Transition-Metal Dichalcogenides.

The photoluminescence (PL) spectrum of transition-metal dichalcogenides (TMDs) shows a multitude of emission peaks below the bright exciton line, and not all of them have been explained yet. Here, we study the emission traces of phonon-assisted recombinations of indirect excitons. To this end, we develop a microscopic theory describing simultaneous exciton, phonon, and photon interaction and including consistent many-particle dephasing. We explain the drastically different PL below the bright exciton in tungsten- and molybdenum-based materials as the result of different configurations of bright and momentum-dark states. In good agreement with experiments, our calculations predict that WSe2 exhibits clearly visible low-temperature PL signals stemming from the phonon-assisted recombination of momentum-dark K–K′ excitons.