Band-gap Renormalization Effects Research Articles

Exciton-Exciton Interaction in Monolayer MoSe2 from Mutual Screening of Coulomb Binding.

Excitons in two-dimensional (2D) semiconductors are particularly exciting, as reduced screening and dimensional confinement foster their pronounced many-body interactions. Optical pumping is typically used to create excitons so as to study their properties, but at the same time such pumping can also create unbound charge carriers. This makes experimental determination of the exciton-exciton interactions difficult. Most importantly, the two effects of band gap renormalization and Coulomb screening on the individual exciton resonance energy counteract each other. Here by comparing the influences of exciton and electron density on the exciton ground and excited states energies of monolayer MoSe2 using photoluminescence spectroscopy, we are able to distinctly identify the screening of Coulomb binding by the neutral excitons and by charge carriers. The energy difference between exciton ground state (A-1s) and excited state (A-2s) red-shifts by 5.5 meV when the neutral exciton density increases from 0 to 4 × 1011 cm-2, in contrast to the blue shifts with the increase of either electron or hole density. This energy difference change is attributed to the mutual screening of Coulomb binding of neutral excitons, a many-body effect that is over 5 times magnitude stronger than the conventional estimate of exciton-exciton interactions. From this mutual Coulomb screening we extract an exciton polarizability of α2Dexciton = 2.5 × 10-17 eV(m/V)2. Our finding uncovers a mechanism that dominates the repulsive part of many-body interaction between neutral excitons.

Spin-dependent bandgap renormalization and state-filling effect in Bi2Se3 observed by ultrafast Kerr rotation

Spin-dependent bandgap renormalization and state-filling effect in Bi2Se3 observed by ultrafast Kerr rotation

Heavy Ge Doping in GaN via Pulsed Sputtering to Tailor the Optical Bandgap Energy

The epitaxial growth of heavily Ge‐doped GaN films using pulsed sputtering deposition (PSD) on AlN (0001)/sapphire substrates is presented and the correlations among their structural, electrical, and optical properties are investigated. High‐quality Ge‐doped PSD‐GaN films are grown with electron concentrations of 0.33–4.4 × 1020 cm−3. Notably, cathode luminescence spectra reveal the absence of defect‐induced emissions associated with Ga vacancies (2.3–2.4 eV), consistent with the high electron mobilities of the films. As the electron concentration increases, the optical bandgap also increases. This correlation can be explained by combining the theoretical formulas for the Burstein–Moss shift and the bandgap renormalization effects. Remarkably, the optical bandgap reaches 3.84 eV at 4.4 × 1020 cm−3 carrier concentration, marking the highest value reported for the optical bandgap of GaN. These results indicate the potential of heavy Ge doping in GaN via PSD for applications in highly transparent conductive layers and tunneling junctions within GaN‐based optoelectronic devices.

Revealing Unusual Bandgap Shifts with Temperature and Bandgap Renormalization Effect in Phase‐Stabilized Metal Halide Perovskite Thin Films

AbstractHybrid organic–inorganic metal halide perovskites are emerging materials in photovoltaics, whose bandgap is one of the most crucial parameters governing their light‐harvesting performance. This work presents the temperature and photocarrier density dependence of the bandgap in two phase‐stabilized perovskite thin films (MA0.3FA0.7PbI3 and MA0.3FA0.7Pb0.5Sn0.5I3) using photoluminescence and absorption spectroscopy. Contrasting bandgap shifts with temperature are observed between the two perovskites. Using X‐ray diffraction and in situ high‐pressure photoluminescence spectroscopy, it is shown that thermal expansion plays only a minor role in the large bandgap blueshift, which is attributed to the enhanced structural stability of the samples. The first‐principles calculations further demonstrate the significant impact of thermally induced lattice distortions on the bandgap widening. It is proposed that the anomalous trends are caused by the competition between static and dynamic distortions. Additionally, both the bandgap renormalization and band‐filling effects are directly observed for the first time in fluence‐dependent photoluminescence measurements and are employed to estimate the exciton effective mass. The results provide new insights into the basic understanding of thermal and charge‐accumulation effects on the band structure of hybrid perovskite thin films.

Optical gain and lasing from bulk cadmium sulfide nanocrystals through bandgap renormalization.

Strongly confined colloidal quantum dots have been investigated for low-cost light emission and lasing for nearly two decades. However, known materials struggle to combine technologically relevant metrics of low-threshold and long inverted-state lifetime with a material gain coefficient fit to match cavity losses, particularly under electrical excitation. Here we show that bulk nanocrystals of CdS combine an exceptionally large material gain of 50,000 cm-1 with best-in-class gain thresholds below a single exciton per nanocrystal and 3 ns gain lifetimes not limited by non-radiative Auger processes. We quantitatively account for these findings by invoking a strong bandgap renormalization effect, unobserved in nanocrystals to date, to the best of our knowledge. Next, we demonstrate broadband amplified spontaneous emission and lasing under quasi-continuous-wave conditions. Our results highlight the prospects of bulk nanocrystals for lasing from solution-processable materials.

Efficient hydrogen storage in LiMgF3: A first principle study

The utilization of hydrogen energy as a sustainable and renewable energy carrier has sparked considerable interest, but effective storage remains a challenge. To address this, researchers have turned their attention to hydride materials, which offer safe and efficient hydrogen storage capacity. In this study, we employed density functional theory calculations to investigate the structural and optoelectronic properties of LiMgF3-xHx (x = 0, 1, 2, and 3) hydrides, aiming to gain insights into their potential role in hydrogen storage. The optimized lattice parameter decreases from 3.95 to 3.86 Å with the inclusion of hydrogen. Further, we analyzed the density of states and band structure of each LiMgF3-xHx (x = 0, 1, 2, and 3) perovskite hydride, which depicts the decreasing trend in the bandgap due to increasing concentration of H. The Burstein-Moss shift and bandgap renormalization effects have been determined to assess the shifting of the absorption edge, which results in the narrowing of the bandgap. Furthermore, optical parameters were examined within the range of 0–10 eV, demonstrating a significant redshift in the absorption spectra in the UV region. The alteration in the optical properties and bandgap reduction are discussed in detail. Among the various hydrogen insertions, LiMgH3 displayed the highest static refractive index [n (0) = 2.01] and dielectric function, exhibiting minimal losses in absorption. These results emphasize that LiMgH3 is a promising candidate for hydrogen storage applications. Interestingly, the gravimetric and volumetric hydrogen storage capacities improved significantly from 1.4 to 8.8 wt% and 26.93–86.59 g.H2/l, respectively, which is a consequence of the increasing concentration of hydrogen in the host compound. This work might provide a significant contribution to both present and future research on practical hydrogen storage applications.

Direct Observation of Photon Induced Giant Band Renormalization in 2D PdSe2 Dichalcogenide by Transient Absorption Spectroscopy.

Insight into fundamental light-matter interaction as well as underlying photo-physical processes is crucial for the development of novel optoelectronic devices. Palladium diselenide (PdSe2 ), an important representative of emerging 2D noble metal dichalcogenides, has gain considerable attention owing to its unique optical, physical, and chemical properties. In this study, 2D PdSe2 nanosheets (NSs) are prepared using the liquid-phase exfoliation method. A broadband carrier relaxation dynamics from visible to near-infrared bands are revealed using a time-resolved transient absorption spectrometer, giving results that indicate band filling and bandgap renormalization (BGR) effects in the 2D PdSe2 NSs. The observed blue-shift of the transient absorption spectra at the primary stage and the subsequent red-shift can be ascribed to this BGR effect. These findings reveal the many-body character of the 2D TMDs material and may hold keys for applications in the field of optoelectronics and ultrafast photonics.

Reversible Diode with Tunable Band Alignment for Photoelectricity-Induced Artificial Synapse.

The advent of big data era has put forward higher requirements for electronic nanodevices that have low energy consumption for their application in analog computing with memory and logic circuit to address attendant energy efficiency issues. Here, a miniaturized diode with a reversible switching state based on N-n MoS2 homojunction used a bandgap renormalization effect through the band alignment type regulated by both dielectric and polarization, controllably switched between type-I and type-II, which can be simulated as artificial synapse for sensing memory processing because of its rectification, nonvolatile characteristic and high optical responsiveness. The device demonstrates a rectification ratio of 103 . When served as memory retention time, it can attain at least 7000s. For the synapse simulation, it has an ultralow-level energy consumption because of the pA-level operation current with 5pJ for long-term potentiation and 7.8fJ for long-term depression. Furthermore, the paired pulse facilitation index reaches up to 230%, and it realizes the function of optical storage that can be applied to simulate visual cells.

Electronic Structure of Colloidal 2H-MoS2 Mono and Bilayers Determined by Spectroelectrochemistry.

The electronic structure of mono and bilayers of colloidal 2H-MoS2 nanosheets synthesized by wet-chemistry using potential-modulated absorption spectroscopy (EMAS), differential pulse voltammetry, and electrochemical gating measurements is investigated. The energetic positions of the conduction and valence band edges of the direct and indirect bandgap are reported and observe strong bandgap renormalization effects, charge screening of the exciton, as well as intrinsic n-doping of the as-synthesized material. Two distinct transitions in the spectral regime associated with the C exciton are found, which overlap into a broad signal upon filling the conduction band. In contrast to oxidation, the reduction of the nanosheets is largely reversible, enabling potential applications for reductive electrocatalysis. This work demonstrates that EMAS is a highly sensitive tool for determining the electronic structure of thin films with a few nanometer thicknesses and that colloidal chemistry affords high-quality transition metal dichalcogenide nanosheets with an electronic structure comparable to that of exfoliated samples.

Role of dopants and defects on the photocatalytic performance of g-C3N4 under visible light and sub-band gap excitation

Here, we report the photocatalytic (PC) activity of graphitic carbon nitride (g-C3N4) doped with potassium (K), magnesium (Mg), and boron (B) under visible (>390 nm), green (532 nm), and red (660 nm) light. Doped g-C3N4 has an improved band structure, high carrier density, and tunable band-edge absorption as compared to pure g-C3N4. An atomic force microscope shows a decrease in layer thickness that follows the order: g-C3N4 > K/g-C3N4 > Mg/g-C3N4 > B/g-C3N4. The evolution of nitrogen vacancies in doped g-C3N4 was identified via x-ray photoelectron spectroscopy (XPS) and CHNS/O analyses. The red-shift in the absorption spectrum of K/g-C3N4 and the emission spectrum of B/g-C3N4 is caused by the band gap renormalization (BGR) effect. Quantum confinement and a possible Burstein–Moss (BM) effect both contribute to the spectral blue shift in the absorption spectra of Mg/g-C3N4 and B/g-C3N4. The BM effect, quantum confinement, and dopant-induced lattice strain might all alter the band structure and move the conduction band edge away from the valence band zone centre, causing an above band gap emission in K/g-C3N4 and Mg/g-C3N4. All samples degraded methylene blue (MB) under visible light with outstanding results, but they responded poorly to methyl orange (MO) and rhodamine B (RhB). With 83.59% MB degradation at a rate constant of 1.1 × 10−2 min−1, Mg/g-C3N4 recorded the best PC, which was three times quicker than g-C3N4 (3.7 × 10−3 min−1). When compared to g-C3N4, the doped samples’ current density (both anodic and cathodic) and carrier density were almost two times greater. The mechanism demonstrated how active edge sites, defects, and dopants contributed to the remarkable PC activity in the doped samples.

Wavelength dependence of laser-induced excitation dynamics in silicon

Effect of laser wavelength on the carrier-phonon dynamics and damage threshold of silicon is studied numerically. Laser excitation dynamics in silicon is studied using Three-Temperature Model (3TM). We consider the evolution of electron, hole, and lattice temperatures separately and including band-gap re-normalization effect on optical properties of silicon. Finite Difference Time Domain method is used to model the laser field. Damage threshold calculated using the 3TM is in reasonable agreement with the experiments. Our results indicate that the competition of inter-band excitation, plasma heating, and electron–phonon relaxation process defines the damage threshold for various wavelengths and pulse durations.

A consistent picture of excitations in cubic BaSnO3 revealed by combining theory and experiment

Among the transparent conducting oxides, the perovskite barium stannate is most promising for various electronic applications due to its outstanding carrier mobility achieved at room temperature. However, most of its important characteristics, such as band gaps, effective masses, and absorption edge, remain controversial. Here, we provide a fully consistent picture by combining state-of-the-art ab initio methodology with forefront electron energy-loss spectroscopy and optical absorption measurements. Valence electron energy-loss spectra, featuring signals originating from band gap transitions, are acquired on defect-free sample regions of a BaSnO3 single crystal. These high-energy-resolution measurements are able to capture also very weak excitations below the optical gap, attributed to indirect transitions. By temperature-dependent optical absorption measurements, we assess band-gap renormalization effects induced by electron-phonon coupling. Overall, we find for the effective electronic mass, the direct and the indirect gap, the optical gap, as well as the absorption onsets and spectra, excellent agreement between both experimental techniques and the theoretical many-body results, supporting also the picture of a phonon-mediated mechanism where indirect transitions are activated by phonon-induced symmetry lowering. This work demonstrates a fruitful connection between different high-level theoretical and experimental methods for exploring the characteristics of advanced materials.

Band Gap Tuning of Films of Undoped ZnO Nanocrystals by Removal of Surface Groups.

Transparent conductive oxides (TCOs) are widely used in optoelectronic devices such as flat-panel displays and solar cells. A significant optical property of TCOs is their band gap, which determines the spectral range of the transparency of the material. In this study, a tunable band gap range from 3.35 eV to 3.53 eV is achieved for zinc oxide (ZnO) nanocrystals (NCs) films synthesized by nonthermal plasmas through the removal of surface groups using atomic layer deposition (ALD) coating of Al2O3 and intense pulsed light (IPL) photo-doping. The Al2O3 coating is found to be necessary for band gap tuning, as it protects ZnO NCs from interactions with the ambient and prevents the formation of electron traps. With respect to the solar spectrum, the 0.18 eV band gap shift would allow ~4.1% more photons to pass through the transparent layer, for instance, into a CH3NH3PbX3 solar cell beneath. The mechanism of band gap tuning via photo-doping appears to be related to a combination of the Burstein–Moss (BM) and band gap renormalization (BGN) effects due to the significant number of electrons released from trap states after the removal of hydroxyl groups. The BM effect shifts the conduction band edge and enlarges the band gap, while the BGN effect narrows the band gap.

Effects of many-body interactions on the transient optical properties of lead halide perovskites

Lead halide perovskites (LHPs) are emerging as promising candidates for use in various high-performance optoelectronic applications, yet their photophysics remains a topic of debate. Here, we theoretically investigated how the ultrafast optical properties of a few prototype LHPs are affected by many-body interactions, including the bandgap renormalization (BGR) effect, the band-filling (BF) effect, the free-carrier absorption effect, and the exciton effect, at carrier densities ranging from 1016 to 1019 cm−3. The results show that the exciton absorption becomes more obvious near the bandgap with increasing exciton energy (as the halogen component of the LHP is varied from I to Cl). Transient reflectivity results indicate that the signal has one peak below the bandgap as a result of the BGR effect at low carrier densities and one valley above the bandgap originating from the BF effect at high carrier densities. In addition, the absorbance decreases with increasing the carrier density as a result of the BF effect because the filled energy levels are observed at 2 meV above the bottom of the conduction band. The results of the present work are expected to promote the application of LHPs in solar cells, light-emitting diodes, and other photoelectric devices.

Distinct ultrafast carrier dynamics of α-In2Se3 and β-In2Se3: contributions from band filling and bandgap renormalization.

As an intrigued layered 2D semiconductor material, indium selenide (In2Se3) has attracted widespread attention due to its excellent properties. So far, the carrier dynamics of α-In2Se3 and β-In2Se3 are still lacking a comprehensive understanding, which is essential to enhancing the performance of In2Se3-based optoelectronic devices. In this study, we explored the ultrafast carrier dynamics in thin α-In2Se3 and β-In2Se3via transient absorption microscopy. For α-In2Se3 with a narrower bandgap, band filling and bandgap renormalization jointly governed the time evolution of the differential reflectivity signal, whose magnitude and sign at different delays were determined by the weights between the band filling and bandgap renormalization, depending on the carrier density. For β-In2Se3, whose bandgap is close to the probe photon energy, only positive differential reflectivity was detected, which was attributed to strong band filling effect. In both materials, the lifetime decreased and the relative amplitude of the Auger process increased, when the pump fluence was increased. These findings could provide further insights into the optical and optoelectronic properties of In2Se3-based devices.

Influence of the excitation density and temperature on the optical properties of type I InAs/GaAsSb quantum dots

In this study, the optical properties of InAs quantum dots (QDs) were characterized using photoluminescence (PL) measurements. The QDs, capped with GaAs and GaAs1−xSbx (x = 6%) strain-reducing layer (SRL), were grown by Molecular Beam Epitaxy. Temperature-dependent photoluminescence (TDPL) of both ground state (GS) and first excited state (ES) was carried out through the analysis of the PL peak position as well as the integrated PL intensity. The temperature dependence of the integrated PL intensity shows the carrier trapping in the potential barrier at the interface between the capping layer and QDs in both samples at low temperatures for the GS and ES. The Excitation density dependent photoluminescence (EDPL) showed a redshift of the GS and ES PL peak energies with increasing excitation density. We attribute this variation to the bandgap renormalization (BGR) effect. The potential barrier reduction for the GaAsSb-capped QDs increases carrier injection efficiency inside the QDs, giving rise to a larger BGR effect compared to the QDs capped with GaAs. With increasing temperature, BGR redshift varies considerably for the GaAs- capped QDs but less for the Q with GaAsSb SRL. This effect was explained using the population rate of carriers inside the QDs while taking into account the nonradiative recombination process for the two samples. Furthermore, the variation of the integrated intensity with the excitation power density grows superlinearly for the two samples for a temperature range from 10 K to 220 K. This behavior was explained by the random capture of carriers in the dots. The sample with GaAsSb SRL having a smaller potential barrier has reduced superlinear dependence at low temperatures. Losses mechanism has a significant impact on increasing the superlinear dependence at high temperatures. The ES showed a stronger superlinearity compared to the GS. This study helps to understand the optical mechanisms in some devices, such as QD lasers.

Femtosecond Pump Probe Reflectivity Spectra in CdTe and GaAs Crystals at Room Temperature.

Ultrafast pump probe reflectivity (PPR) signal near band edge is modeled by taking into account band filling (BF) and band gap renormalization (BGR) effects with the carrier density of ~1017/cm3 in GaAs crystal at room temperature. The calculated results indicate that the transient reflectivity ΔR/R is determined by BF and BGR effects. The most interesting feature is that ΔR/R signal experiences a sign change from photo-bleaching (PB) to photo-absorption (PA) due to the competition between BF and BGR effects. We experimentally measured ΔR as a function of photon energy across band edge with carrier density of ~1017/cm3 in GaAs and CdTe crystals, which has a similar trend as that calculated according to our model. In addition, the reflectivity is very sensitive to electron spin orientation, which is well confirmed by the corresponding experiments with 100 fs pump probe reflectivity spectroscopy in bulk CdTe. Our research in this work provides a method to study optoelectronic properties of conventional semiconductors at moderate carrier density excited by ultrafast laser pulse. Importantly, this model can be used for other novel semiconductor materials beyond GaAs and will provide new insights into the underlying spin dependent photophysics properties for new materials.

Observation of bandgap renormalization in mesoscopic zinc oxide particles

Deep UV photoluminescence (PL) spectroscopy was employed to study the optical properties of mesoscopic zinc oxide (ZnO) particles using the third harmonic laser (λ ~ 260 nm) generated from a Ti: sapphire pulse laser for optical excitation. PL spectrum measured at 15 K exhibits excitonic emissions at 3.362 and 3.375 eV due to the donor bound exciton (DoX) and free exciton (FX) transitions, respectively. The dominant emission peak is observed at around 3.308 eV due to the recombination of free electrons from the conduction band to the holes bound to an acceptor state (FA) along with longitudinal optical (LO) phonon replicas. From the power dependent PL measurement, we observed a redshift of FX and DoX emission peaks with increasing excitation laser power, showing a bandgap renormalization effect. Temperature dependent PL measurements were also performed to explore the bandgap renormalization effect. Fitting of our power dependent PL data with Vashishta, and Kalia model shows the clear trend in a good agreement with the model.

Ultrafast dynamics of pure many-body effect and its competition with bandgap widening via electron–phonon coupling in PbTe thin films

Bandgap renormalization (BGR), or bandgap narrowing effect, is one of the many-body effects predicted by many-body theory in semiconductor physics. However, pure BGR effect has never been observed experimentally although the mixed effect of BGR with lattice-heating induced bandgap narrowing was reported in GaAs and CdTe semiconductors. PbTe has a positive temperature coefficient of bandgap. Its lattice-heating induced bandgap narrowing can be eliminated so that the pure BGR effect is possibly observed. However, that has never been reported so far because the BGR effect is weak in PbTe due to its huge dielectric screening. We study the ultrafast dynamics of photo-excited carriers in PbTe films using near-infrared femtosecond-resolved transient differential transmission (TDT) spectroscopy. A complex oscillation-like damped decay dynamics is observed. A negative dip, a fingerprint signature of BGR effect, occurs immediately after the thermalization process of the photo-excited carriers. As such, we have observed a pure BGR effect in PbTe for the first time, strongly supporting the many-body theory. Meanwhile, we have also observed a dynamic transition from a transient absorption enhancement to absorption saturation, revealing the emergence of a slow lattice-heating induced bandgap widening via carrier-phonon couplings. Based on a two-temperature model, a simulation computation is carried out, supporting the lattice-heating induced bandgap widening leads to the dynamic transition. A phenomenological dynamic model is developed, including three dynamic components: the thermalization of the photo-excited carriers, recombination of the thermalized carriers and lattice-heating induced bandgap widening, and used to best fit the excitation-power dependent TDT dynamics. Time constants and strengths of the three dynamic components are obtained for different excitation powers. Time constant variation with the excitation power reveals different roles of the carrier–carrier and carrier-phonon scattering in the thermalizing process, as well as of free carrier and exciton recombination in the decaying process of hot carriers.

Exciton Polarization and Renormalization Effect for Optical Modulation in Monolayer Semiconductors

The ideal quantum confinement structure of monolayer semiconductors offers prominent optical modulation capabilities that are mediated by enhanced many-body interactions. Herein, we establish an electrolyte-gating method for tuning the luminescence properties that are in transition metal dichalcogenide (TMDC) monolayers. We fabricate electric double-layer capacitors on TMDC/graphite heterostructures to investigate electric-field- and carrier-density-dependent photoluminescence. The exciton peak energy initially shows a slight quadratic red shift of ∼1 meV without carrier accumulations, which is caused by the quantum-confined Stark effect. In contrast, the exciton resonance exhibits a larger red shift up to 10 meV with the accumulated carrier density above 1013 cm-2. These results indicate that the optical transitions can be largely modulated by the carrier density control in S- and Se-based TMDCs, as triggered by the doping-induced band gap renormalization effect. To further inspire this modulation capability, we also apply our method to electrolyte-based TMDC light-emitting devices. Biasing solely in electrolyte-induced p-i-n junctions yields pronounced red shifts up to 40 meV for exciton and trion electroluminescence. Consequently, our approach reveals that the doping effects in the high-carrier-density regimes are potentially significant for efficient optical modulation in monolayer semiconductors.