Optical Phonon Research Articles

Quantitative Defect Analysis in CVD‐Grown Monolayer MoS2 via In‐Plane Raman Vibration

ABSTRACTThe synthesis of two‐dimensional transition metal dichalcogenide (2D‐TMD) materials gives rise to inherent defects, specifically chalcogen vacancies, due to thermodynamic equilibrium. Techniques such as chemical vapor deposition (CVD), metal‐organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), flux growth method, and mechanical exfoliation produce large‐scale, uniform 2D TMD films, either in bulk or monolayers. However, defects on the film surface impact its quality, and it is necessary to measure defect density. The phonon confinement model indicates that the first‐order Raman band frequency shift depends on defect density. Monolayer Molybdenum disulfide (MoS2) exhibits three phonon dispersions at the Brillouin zone edge (M point): out‐of‐plane optical phonon vibration (ZO), in‐plane longitudinal optical phonon vibration (LO), and in‐plane transverse optical phonon vibration (TO). The LO and ZO modes overlap with Raman in‐plane vibration (𝐸12g) and Raman out‐of‐plane vibration (𝐴1g), respectively, causing peak broadening. In the presence of defects, the Raman 𝐸12g vibration energy decreases due to a reduced restoring force constant. The Raman 𝐴1g vibration trend is random, influenced by both restoring force constant and mass. The study introduces a quantitative defect measurement technique for CVD‐grown monolayer MoS2 using Raman 𝐸12g mode, employing sequential data processing algorithms to reveal defect density on the film surface.

Deep Ultraviolet Excitation Photoluminescence Characteristics and Correlative Investigation of Al-Rich AlGaN Films on Sapphire.

AlGaN is attractive for fabricating deep ultraviolet (DUV) optoelectronic and electronic devices of light-emitting diodes (LEDs), photodetectors, high-electron-mobility field-effect transistors (HEMTs), etc. We investigated the quality and optical properties of AlxGa1-xN films with high Al fractions (60-87%) grown on sapphire substrates, including AlN nucleation and buffer layers, by metal-organic chemical vapor deposition (MOCVD). They were initially investigated by high-resolution X-ray diffraction (HR-XRD) and Raman scattering (RS). A set of formulas was deduced to precisely determine x(Al) from HR-XRD data. Screw dislocation densities in AlGaN and AlN layers were deduced. DUV (266 nm) excitation RS clearly exhibits AlGaN Raman features far superior to visible RS. The simulation on the AlGaN longitudinal optical (LO) phonon modes determined the carrier concentrations in the AlGaN layers. The spatial correlation model (SCM) analyses on E2(high) modes examined the AlGaN and AlN layer properties. These high-x(Al) AlxGa1-xN films possess large energy gaps Eg in the range of 5.0-5.6 eV and are excited by a DUV 213 nm (5.8 eV) laser for room temperature (RT) photoluminescence (PL) and temperature-dependent photoluminescence (TDPL) studies. The obtained RTPL bands were deconvoluted with two Gaussian bands, indicating cross-bandgap emission, phonon replicas, and variation with x(Al). TDPL spectra at 20-300 K of Al0.87Ga0.13N exhibit the T-dependences of the band-edge luminescence near 5.6 eV and the phonon replicas. According to the Arrhenius fitting diagram of the TDPL spectra, the activation energy (19.6 meV) associated with the luminescence process is acquired. In addition, the combined PL and time-resolved photoluminescence (TRPL) spectroscopic system with DUV 213 nm pulse excitation was applied to measure a typical AlGaN multiple-quantum well (MQW). The RT TRPL decay spectra were obtained at four wavelengths and fitted by two exponentials with fast and slow decay times of ~0.2 ns and 1-2 ns, respectively. Comprehensive studies on these Al-rich AlGaN epi-films and a typical AlGaN MQW are achieved with unique and significant results, which are useful to researchers in the field.

Ultrafast carrier dynamics and transient nonlinear absorption in chalcogenide perovskite BaZrS3

The unique combination of excellent semiconducting properties in halide perovskites and the high stability and nontoxicity of oxide perovskites has led to a recent surge in interest in chalcogenide perovskite BaZrS3 for optoelectronic applications. However, to realize its potential in future device technologies, a comprehensive understanding of photoexcited carrier dynamics and transient optical response is imperative, yet it remains largely unexplored for BaZrS3. In this work, employing transient absorption spectroscopy, we have revealed that photoexcited carriers in epitaxial BaZrS3 nanofilms exhibit two exponential decay components relating to optical phonon cooling and interband recombinations. Meanwhile, our investigation unveils an intriguing transient nonlinear absorption phenomenon in BaZrS3, characterized by the ultrafast switching of the pump-induced transparency (i.e., the saturable absorption) to the absorption enhancement within a timescale commensurate with the measurement resolution (hundreds of femtosecond). This study provides crucial dynamic insights essential for leveraging chalcogenide perovskites, such as BaZrS3, in the development of advanced optoelectronic devices.

Kinetics of optical phonons and DP depolarization of spins in drift transport: Hot carrier spin effect in semiconductors

<p>Spin-<strong>c</strong>onserving transport of carriers is an essential requirement for the practical semiconductor-based spintronic devices. Kinetics of optical phonons and Dyakonov-Perel (DP) depolarization of spins in drift transport in semiconductor gallium arsenide (GaAs) is theoretically investigated<strong>. </strong>We consider electrons in <em>n</em>-type bulk GaAs subjected to a strong electric field, where the electron distribution is assumed to be drifted Maxwellian. The momentum drift of this distribution results in the enhanced drift velocity, and electrons with the corresponding energy emit optical hot phonons in the drifting process. The hot phonons are incorporated via the longitudinal polar optical phonon (POP) mechanism in the momentum relaxation. It is found that a finite phonon lifetime can reduce the momentum relaxation rate, which results in a delay in the runaway to higher fields, where the effect increases with the electron density. The electron spin is found to relax with the DP relaxation frequencies, and the DP spin lifetimes are found to decrease with increasing the drift field. However, a high field completely depolarizes the electron spin due to an increase of the DP spin precession frequency of the hot electrons in the POP scattering process. It is also found that the DP spin precession frequency decreases with decreasing electron temperature or increasing electron density in the moderate range. However, the findings resulting from this investigation demonstrate the hot carrier effect in the spin transport in semiconductors. The results are discussed in comparison with those obtained in earlier experimental and theoretical studies with different approaches.</p>

Analysis of the high-temperature transport property in GaN-based single and double heterostructures

GaN-based heterostructures have been proved to be excellent candidates for high-voltage, large-power, high-frequency and high-temperature application fields, thanks to their superior material properties. To further improve the carriers’ confinement, using InGaN channel layer or introducing AlGaN back barrier layer is promoted. These structures are also proved to be favorable for the robust electron mobility at high temperature. However, the reason solely rests on the longitudinal optical (LO) phonon scattering and the behind mechanism is still absent. This work compares the temperature-dependent electronic transport properties in three groups of GaN-based heterostructures, including GaN-based single heterostructure (SH) with/without AlN interlayer, GaN-based SH and double heterostructure (DH), and GaN-based DH with AlGaN or GaN channel layer. The advantageous high-temperature mobility is attributed to the enhanced LO phonon energy in heterostructures. By self-consistent calculations of the Schrödinger–Poisson equations, a close relation between the narrow electron distribution in the quantum well with the high LO phonon energy, and consequently superior mobility at high temperature is implied. The results provide a simple strategy for the optimized design of the GaN-based heterostructures outperforming at high temperature.

Measurement of temporal evolution of antiferromagnetic domain change in nickel oxide driven by 2TO phonon mode excitation via pump-probe experiment

The temporal evolution of antiferromagnetic domain pattern changes under resonant excitation of the second-order transverse optical phonon mode in nickel oxide was investigated using mid-infrared free electron laser (MIR-FEL) pulses and visible nanosecond probe laser pulses at room temperature. We visualized the domain patterns through magneto-optical polarized microscopy in transmission and observed their temporal variation after the phonon excitation via MIR-FEL. We evaluated the differences throughout the timeline using the structural similarity index measure technique from domain images with and without MIR-FEL irradiation. We found that the MIR-FEL irradiation induces significant structural changes in the domain patterns. The maximum difference was observed at the timing of the MIR-FEL irradiation and exponentially recovered with the time constant of 1.4 ± 0.2 ms. This rather long-time constant could be owing to the spin relaxation, whilst further investigation is needed to confirm the underlying mechanism.

Mixed (NH4)2Mn0.47Cu0.53(SO4)2(H2O)6 Tutton salt: A novel optical material for solar-blind technology

In this paper, a novel mixed Tutton salt (NH4)2Mn0.47Cu0.53(SO4)2(H2O)6 obtained in single crystal form is described. Their structural, thermal, electrical, and spectroscopic properties have been examined, and their possible uses are discussed. The salt crystallizes in a monoclinic symmetry (P21/c) and exhibits thermal stability between 300-333 K. Above this temperature, the crystal undergoes phase changes associated with dehydration and crystallization processes. 231 optical phonons distributed between 50 and 4000 cm–1, calculated through density functional perturbation theory, were used to accurately assign vibrational modes in experimental FT-IR and Raman spectra. Additional computational studies using Hirshfeld surfaces have revealed that H···O/O···H and H···H intermolecular contacts are crucial interactions for stabilizing the crystal lattice. Electrical characteristics (resistivity = 1160 MΩ·cm; capacitance = 3.6 pF) and optical data (bandgap = 4.27 eV) depict a typical behavior of nonpolar dielectric materials. UV-Vis-NIR transmittance spectrum has shown deep light blocking in the UV-C and Vis/NIR spectral regions and high transmittance levels (reaching 98.5%) in the UV-B/-A/Vis range. The photoresponse findings point out that (NH4)2Mn0.47Cu0.53(SO4)2(H2O)6 is a promising light-absorbing material for solar-blind photodetection devices operating in the 200-280 nm interval. The crystal as a bandpass filter (280-615 nm) or a cut-off filter (615-1000 nm) are also excellent prospects for application.

High-Temperature Characterization of AlGaN Channel High Electron Mobility Transistor Based on Silicon Substrate

In this paper, it is demonstrated that the AlGaN high electron mobility transistor (HEMT) based on silicon wafer exhibits excellent high-temperature performance. First, the output characteristics show that the ratio of on-resistance (RON) only reaches 1.55 when the working temperature increases from 25 °C to 150 °C. This increase in RON is caused by a reduction in optical phonon scattering-limited mobility (μOP) in the AlGaN material. Moreover, the device also displays great high-performance stability in that the variation of the threshold voltage (ΔVTH) is only 0.1 V, and the off-state leakage current (ID,off-state) is simply increased from 2.87 × 10−5 to 1.85 × 10−4 mA/mm, under the operating temperature variation from 25 °C to 200 °C. It is found that the two trap states are induced at high temperatures, and the trap state densities (DT) of 4.09 × 1012~5.95 × 1012 and 7.58 × 1012~1.53 × 1013 cm−2 eV−1 are located at ET in a range of 0.46~0.48 eV and 0.57~0.61 eV, respectively, which lead to the slight performance degeneration of AlGaN HEMT. Therefore, this work provides experimental and theoretical evidence of AlGaN HEMT for high-temperature applications, pushing the development of ultra-wide gap semiconductors greatly.

Softening of the optical phonon by reduced interatomic bonding strength without depolarization.

Softening of the transverse optical (TO) phonon, which could trigger ferroelectric phase transition, can usually be achieved by enhancing the long-range Coulomb interaction over the short-range bonding force1, for example, by increasing the Born effective charges2. However, it suffers from depolarization effects3,4 as the induced ferroelectricity is suppressed on size reduction of the host materials towards high-density nanoscale electronics. Here, we present an alternative route to drive the TO phonon softening by showing that the abnormal soft TO phonon in rocksalt-structured ultrawide-bandgap BeO (ref. 5) is mainly induced by a substantial reduction in the short-range bonding interaction due to the Be-O bond stretching caused by an electron cloud-overlap-induced Coulomb repulsion between two adjacent oxygen ions that are arranged octahedrally around an extremely small Be ion. We further demonstrate the emergence of robust ferroelectricity in strain-induced perovskite BaZrO3 and ultrathin HfO2 and ZrO2 films6,7 grown epitaxially on lattice-mismatched SiO2/Si substrate arising from the softening of the TO phonon driven by a reduction in the short-range bonding strength of biaxial strain-induced stretching bonds. These findings shed light on developing a unified theory for ferroelectricity enhancement in ultrathin films free from depolarization fields by tailoring chemical bonds using ionic radius differences, strains, doping and lattice distortions.

Phonon modes and electron-phonon coupling at the FeSe/SrTiO3 interface.

The remarkable increase in superconducting transition temperature (Tc) observed at the interface of one-unit-cell FeSe films on SrTiO3 substrates (1 uc FeSe/STO)1 has attracted considerable research into the interface effects2-6. Although this high Tc is thought to be associated with electron-phonon coupling (EPC)2, the microscopic coupling mechanism and its role in the superconductivity remain elusive. Here we use momentum-selective high-resolution electron energy loss spectroscopy to atomically resolve the phonons at the FeSe/STO interface. We uncover new optical phonon modes, coupling strongly with electrons, in the energy range of 75-99 meV. These modes are characterized by out-of-plane vibrations of oxygen atoms in the interfacial double-TiOx layer and the apical oxygens in STO. Our results also demonstrate that the EPC strength and superconducting gap of 1 uc FeSe/STO are closely related to the interlayer spacing between FeSe and the TiOx terminated STO. These findings shed light on the microscopic origin of the interfacial EPC and provide insights into achieving large and consistent Tc enhancement in FeSe/STO and potentially other superconducting systems.

Tl2XY (X, Y = S, Se) monolayers with low lattice thermal conductivity and high thermoelectric performance by full-band approach with four scattering mechanisms

Abstract The low lattice thermal conductivity and high thermoelectric performance of the Janus Tl2SSe monolayer in the temperature region of 300~700 K are identified based on the thermoelectric properties of the Tl2S2, Tl2SSe, and Tl2Se2 monolayers. The transport coefficients for carrier concentrations and temperatures are obtained by solving the linearized Boltzmann transport equation in a full-band electronic structure. Four scattering mechanisms of acoustic deformation potential, optical deformation potential, polar optical phonon, and ionized impurity scatterings are considered. The ionized impurity scattering is recognized as the most important. The lattice thermal conductivity of the Janus Tl2SSe monolayer is substantially smaller than those of the Tl2SSe, Tl2Se2 monolayers with higher symmetry. Moreover, we find that the Janus structures of the Tl2SSe monolayer increase the dielectronic constants and enhance the polar optical phonon scattering, then reduce the power factor to some extent. Therefore, the lattice thermal conductivity actually couples with the transport coefficient and cannot be individually regulated as is usually assumed. However, the ZT value of the Tl2SSe monolayer can still reach 1.77 at 700 K even if the intrinsic concentration and the bipolar effect are included. Therefore, the Tl2SSe monolayer is expected to be a promising candidate for thermoelectric materials.

Generation of a coherent longitudinal optical phonon plasmon coupled mode in an n-type InSb single crystal in the absence and/or strong suppression of the photo-Dember effect confirmed with the use of terahertz time-domain spectroscopy

We explored the feasibility of generating a coherent longitudinal optical (LO) phonon–plasmon coupled mode in an n-type InSb single crystal with the condition that the photo-Dember effect is strongly suppressed and/or eliminated. We systematically performed terahertz time-domain spectroscopic measurements of the n-type InSb single crystal and undoped InSb crystal. The terahertz electromagnetic wave originating from the photo-Dember effect was extinguished in the n-type InSb single crystal, while the clear signal from the photo-Dember effect was detected in the undoped InSb single crystal. Meanwhile we detected the clear signal of the terahertz wave from the coherent LO-phonon–plasmon coupled mode in the n-type InSb single crystal, indicating that the photo-Dember effect is not dominant in the generation of the coherent LO-phonon–plasmon coupled mode although the photo-Dember effect has been attributed to the dominant generation mechanism of the coherent LO-phonon–plasmon coupled mode so far. We explain the present phenomenon, taking account of the fact that the impulsive stimulated Raman scattering process has a possibility of generating coherent LO-phonon–plasmon coupled modes in light-absorbing solids [Nakamura et al., Phys. Rev. B 99, 180301(R) (2019)].

Analytical insight into caffeine extraction from typica coffee leaves based on crystallinity enhancement, optical phonon vibration upshift, and morphological evolution.

Caffeine extracted from callus cultures by in vitro technique induced from typica coffee (Coffea arabica L. var. typica) leaves was successfully carried out by a simple Soxhlet method. Analysis of X-ray diffraction patterns showed an increase in crystallinity fraction from leaves (13.56%) to callus (14.46%) and then to caffeine (39.18%). Crystallite size also varied, with average sizes of 18±6, 69±51, and 32.5±17 nm for leaves, callus, and caffeine, respectively. Fourier transmission infrared absorption data confirmed the presence of hydroxyl (OH) groups bound to carbon (C─COH), indicating caffeine content. The high stability of the C─COH is indicated by the broad optical phonon vibrations of the leaves: 247cm-1 to caffeine: 963cm-1. Quantitative analysis of dielectric function and electron loss function intensity peaks of each sample showed that leaves efficiently capture and store light energy while caffeine has less potency. Scanning electron microscopy analysis showed irregular shapes of leaves, oval round shapes for callus, and rectangular crystals for caffeine due to crystal orientation during transformation and had a strong correlation with crystallinity fraction. Finally, the structure-based identification, chemistry, optical-dielectric function, and micro-surface properties have been fully studied, thus unmasking the phenomenon of slow transformation from leaves to caffeine form. PRACTICAL APPLICATION: The result of this study can be applied to uncover new methodologies related to the classification, and biotechnological utilization of callus culture based on structural properties, optical-dielectric function, and micro-surface analysis. Methodologically, the resulting callus culture provides a sustainable and controllable supply of plant material for caffeine extraction, thereby reducing traditional methods involving field-grown plants and avoiding the use of pesticides.

Near-infrared-terahertz hyper-Raman spectroscopy of an excited silicon surface.

We recorded the hyper-Raman spectra resulting from the interaction of a near-infrared (near-IR) picosecond pulse and a terahertz (THz) ultrashort pulse at the surface of a (111) silicon sample. A simple model is proposed to analyze the evolution of the hyper-Raman spectra vs the time delay between the near-IR and THz pulses. It links the hyper-Raman spectra to the multi-phonon absorption in silicon. This approach makes it possible to demonstrate that, during carrier generation by the near-IR pulse, the two-phonon and three-phonon absorption bands are enhanced in modes involving optical phonons. This process results from the very rapid and strong population of the optical phonons induced by the photo-generated hot carriers. It occurs over a few hundreds of femtoseconds and lasts throughout the duration of the near-IR pulse.

Phonon-polariton Bragg generation at the surface of silicon carbide

Phonon-polaritons are known to emerge at the surface of solids under infrared (IR) irradiation at frequencies close to the optical phonon resonance. Metal, patterned on the top of the polariton-active surface, locally blocks the excitation of surface waves due to plasmonic screening and can be used for the design of wave patterns. We excite polaritonic waves at the surface of SiC under the irradiation of a CO2 laser (λ∼10μm) and visualize them using apertureless near-field interference scanning probe microscopy. From the near-field scans in the vicinity of gold film periodical strip structures, we identify the Bragg scattering (diffraction) outside the grating with the contribution from separate strips coherently summed up, provided that the wavelength matching condition is fulfilled. The observed phenomena agree with wavefield calculations. Our observations demonstrate the potential of metal-patterned silicon carbide for the fabrication of on-chip polaritonic IR circuits.

Element-Specific Ultrafast Lattice Dynamics in Monolayer WSe2.

We study monolayer WSe2 using ultrafast electron diffraction. We introduce an approach to quantitatively extract atomic-site-specific information, providing an element-specific view of incoherent atomic vibrations following femtosecond excitation. Via differences between W and Se vibrations, we identify stages in the nonthermal evolution of the phonon population. Combined with a calculated phonon dispersion, this element specificity enables us to identify a long-lasting overpopulation of specific optical phonons and to interpret the stages as energy transfer processes between specific phonon groups. These results demonstrate the appeal of resolving element-specific vibrational information in the ultrafast time domain.

Dual-gate AlGaN channel HEMTs: advancements in E-mode performance with N-shaped graded composite barriers

Abstract This work evaluates the performance of dual gate AlGaN channel HEMTs on SiC substrate. The study analyzes two HEMT structures that differ only in barrier design, one design consists of fixed composite barriers (FCB-HEMT) i.e. there is fixed Aluminum composition x = 0.48 in the first Al x Ga1−x N barrier and x = 0.42 in the second Al x Ga1−xN barrier while the other design comprises N-shaped graded composite barriers (NGCB-HEMT) i.e. the Aluminum content varies gradually from 0.4 to 0.48 in the first AlGaN barrier and from 0.34 to 0.42 in the second AlGaN barrier. The paper concentrates on energy band diagrams, electron concentration profile, electric field distribution, drain and transfer characteristics, and the effects of high temperature on drain characteristics and mobility of the NGCB-HEMT. It has been reported that at zero gate bias, the FCB-HEMT has a drain current density of 0.137 A mm−1 while it decreases to 0.0058 A mm−1 in the case of NGCB-HEMT, thus presenting a novel approach towards enhancement-mode AlGaN HEMTs. Hence, grading can be optimized in the composite barriers to achieve enhancement mode operation of AlGaN channel HEMTs. Furthermore, the study reveals that the critical electric field of FCB-HEMT is 6.9975 M V cm−1, while that of NGCB-HEMT is 5.3124 M V cm−1, demonstrating their usefulness in electronic devices that operate at high voltages and harsh temperatures. Moreover, at higher temperatures, the phenomenon of optical phonon scattering leads to decreased mobilities, which in turn causes low drain currents relative to the drain voltage.

Effects of heavy alkali metals (Rb, Cs) post-deposition treatments on CuInGaSe2 using a spin-coating technique

Abstract This study used a controlled environment to explore the post-deposition treatment (PDT) effects on CuInGaSe2 (CIGSe2) semiconducting thin films using a non-vacuum spin-coating technique for doping the CIGSe layers with Cs and Rb. The structural characterization confirmed the successful deposition of chalcopyrite structures with no phases belonging to any alkali metals after the PDT, with crystallite sizes in the range between 40-67 nm, and with a slight change in the X Ray Diffraction (XRD) peak positions indicating a change from copper-rich to copper-poor phases. The morphological studies confirmed the increase in grain sizes after the PDT. The EDS chemical studies showed that there is a reduction in the copper content after PDT. The topographical studies showed a change in the surface morphology with modifications of the grain parameters. In addition, the electrical characterization showed a significant increase of the effective carrier mobility after the treatments, consistent with the grain size increase observed by both microscopic (SEM and AFM) studies. Raman characterization of the CIGSe2 films showed the A1 optical phonon mode of CIGS chalcopyrite structures and peaks at lower frequencies belonging to ordered vacancy compounds (OVCs). The deconvolution of the Raman spectroscopy broad peaks for the CIGSe2 films after their PDT confirmed the formation of alk-InSe2 OVC phases on top of the absorber layer.

Dynamical Manipulation of Polar Topologies from Acoustic Phonon Excitations.

Since the recent discovery of polar topologies, a recurrent question has been how to remotely tune them. Many efforts have focused on the pumping of polar optical phonons from optical methods, but with limited success, as only switching between specific phases has been achieved so far. Additionally, the correlation between optical pulse characteristics and the resulting phase is poorly understood. Here, we propose an alternative approach and demonstrate the deterministic and dynamical tailoring of polar topologies using acoustic phonon excitations. Our second-principles simulations reveal that by pumping specific longitudinal and transverse acoustic phonons, various topological textures can be induced in materials like BaTiO3 or PbTiO3. This method leverages the strong coupling between polarization and strain in these materials, enabling predictable and dynamic control of polar patterns. Our findings open up an alternative possibility for the manipulation of polar textures, suggesting a promising research direction.

Photohole-induced strong σ−π scattering driven by out-of-plane phonons in graphene

A theoretical study of the phonon-induced linewidths of the occupied electronic bands and the electron-phonon coupling (EPC) constant in graphene is presented. We propose an approximation in the spirit of the rigid ion approximation which considerably simplifies calculations of the EPC in metallic systems. We apply a tight-binding approach for the electrons and a force-constant model for the phonons with parameters obtained from . A simple procedure is presented in order to estimate the influence of the graphene-substrate interaction on the phonon dispersion and thereby also on, e.g., the linewidths. The EPC is the strongest in the energy region where π and σ bands overlap. We find that the electron scattering is predominantly driven by the out-of-plane acoustic ZA and optical ZO phonon modes, while in general the high-energy optical phonon modes LO and TO are of secondary importance. Published by the American Physical Society 2024