Multiphonon Processes Research Articles

Enhanced the quantum efficiency of Tm3+ ∼2 μm laser in crystal through an energy transfer process of 3H5 level

The concentration dependence of the fluorescence and lifetime evolutions of states relevant to three near-infrared emission bands were measured and analyzed for Tm:SrF2 crystals. The fast quenching of ∼1.2 μm fluorescence (3H5) was observed as the Tm concentration increased. The cross-relaxation and multi-phonon relaxation processes between Tm3+ ions cannot explain this phenomenon. Through spectral and rate-equation analysis, two possible energy transfer mechanisms, cross-relaxation from the 3H5 level and cooperative energy transfer within Tm3+ clusters, are proposed. And based on the new modified model, the quantum efficiency of the Tm ∼2 μm lasers could surpass the traditional 200% limit. This new energy transfer has the potential for exceptionally high efficiency excitation of Tm-doped laser materials.

Two stage decoherence of optical phonons in long oligomers.

Molecular vibrations are generally responsible for chemical energy transport and dissipation in molecular systems. This transport is fast and efficient if energy is transferred by optical phonons in periodic oligomers, but its efficiency is limited by decoherence emerging due to anharmonic interactions with acoustic phonons. Using a general theoretical model, we show that in the most common case of the optical phonon band being narrower than the acoustic bands, decoherence takes place in two stages. The faster stage involves optical phonon multiple forward scattering due to absorption and emission of transverse acoustic phonons, i.e., collective bending modes with a quadratic spectrum; the transport remains ballistic and the speed can be altered. The subsequent slower stage involves phonon backscattering in multiphonon processes involving two or more acoustic phonons resulting in a switch to diffusive transport. If the initially excited optical phonon possesses a relatively small group velocity, then it is accelerated in the first stage due to its transitions to states propagating faster. This theoretical expectation is consistent with the recent measurements of optical phonon transport velocity in alkane chains, increasing with increasing the chain length.

Prediction of Shockley–Read–Hall lifetimes in strained layer superlattices for mid-wave and long-wave infrared photodetectors

We have calculated carrier nonradiative recombination lifetimes limited by Shockley–Read–Hall (SRH) centers in strained layer superlattices (SLSs) for mid-wave and long-wave infrared applications. The capture rate of an electron (hole) in the SLS's conduction (valence) band by the defect level is dominated by a multi-phonon process, which is orders-of-magnitude more efficient than the radiative process. Long-range polar coupling between electrons and optical phonons can account for the observed SRH lifetimes in a variety of SLSs reported in the literature. The capture rate depends on temperature rather weakly, consistent with experimental observations. The efficient capture is caused by the comparable electronic difference and lattice relaxation energy, Ect∼Sℏω, with S and ℏω being the Huang–Rhys factor and optical photon energy in the SLSs. A weaker polar coupling would give rise to a smaller capture cross section, which, for InAs/InAsSb SLSs, can be achieved by increasing Sb in the alloy region.

Investigation of structural and optoelectronic integrity of Sm3+ doped CaWO4 for LED applications

In this study we illustrate the structural, electronic and optical integrity of Ca1-xSm(2/3)xWO4 (x = 0.00, 0.02, 0.04, 0.06 and 0.08) crystals for optoelectronic applications via experimental and first principles approach. According to our experimental outcomes, CaWO4 crystallizes in scheelite type tetragonal structure devoid of impurity which depends on the A-site cationic radius and dopant-host compatibility. As a result, the dopant induced lattice distortion occur due to symmetric and asymmetric stretching of (Ca, Sm)—O and W–O bonds within [CaO8] and [WO4] cluster. According to our FT-IR and Raman spectral analysis, the non-centrosymmetric vibration within the [WO4]2- complex gives rise to internal modes while the Ca2+/Sm3+ cationic displacement and rigid molecular ionic group constitutes the external modes which equally impacts the electronic and optical characteristics of the host material. While the forbidden gap extends due to Sm3+ substitution, the delocalization of W-5d orbitals on the other hand occur due to rising distortions within the WO4 cluster. As a result, the polarization between [WO4] and [CaO8] cluster and difference in the electronic transitions controls the optical characteristics of the host material. According to our experimental and theoretical predictions, a noticeable decrease in the optical band gap (5.96–5.83 eV) occurs due to heterovalent cationic substitution (Sm3+), difference in structural order-disorder and charge carrier density. As a result, a broad photoluminescence (PL) spectrum among acceptor doped samples verifies the impact of multi-phonon or multi-level processes on the luminosity of the host material.

Carrier Recombination in Nitride-Based Light-Emitting Devices: Multiphonon Processes, Excited Defects, and Disordered Heterointerfaces.

We study recombination processes in nitride LEDs emitting from 270 to 540 nm with EQE ranging from 4% to 70%. We found a significant correlation between the LEDs' electro-optical properties and the degree of nanomaterial disorder (DND) in quantum wells (QWs) and heterointerfaces. DND depends on the nanoarrangement of domain structure, random alloy fluctuations, and the presence of local regions with disrupted alloy stoichiometry. The decrease in EQE values is attributed to increased DND and excited defect (ED) concentrations, which can exceed those of Shockley-Read-Hall defects. We identify two mechanisms of interaction between EDs and charge carriers that lead to a narrowing or broadening of electroluminescence spectra and increase or decrease EQE, respectively. Both mechanisms involve multiphonon carrier capture and ionization, impacting EQE reduction and efficiency droop. The losses caused by these mechanisms directly affect EQE dependencies on current density and the maximum EQE values for LEDs, regardless of the emission wavelength. Another manifestation of these mechanisms is the reversibility of LED degradation. Recombination processes vary depending on whether QWs are within or outside the space charge region of the p-n junction.

The impact of high pressure on the number of photons involved in upconversion luminescence of NaYF4:Er3+@NaYF4 and NaYF4:Yb3+,Er3+@NaYF4 core@shell nanoparticles and application as contactless pressure sensor

Inorganic nanomaterials doped with lanthanide ions and exhibiting upconversion (UC) luminescence are leading in research of nonlinear optical materials. Extreme conditions, such as high-pressure compression (in the GPa range), may influence the physicochemical properties of various compounds. In this work, we investigated the optical properties of upconverting NaYF4:Er3+@NaYF4 and NaYF4:Yb3+,Er3+@NaYF4 core@shell nanoparticles (NPs), focusing on the impact of high pressure on the number of photons involved in the UC mechanism. We measured the UC emission spectra of the synthesized NPs under high-pressure conditions, which allowed us to observe the pressure-induced intensity changes, band centroids spectral shifts, and band intensity ratios alterations. Importantly, by measuring the power-dependent UC emission spectra as a function of pressure, we determined and analyzed the number of photons (n) involved in the UC processes for the first time. It turned out that the n value changes with pressure as a result of diverse multi-phonon relaxation processes enhanced under high-pressure conditions. The results show potential adjustment of UC mechanisms with the use of high-pressure. The calculated band intensity ratios were also used for pressure sensing applications, resulting in the relative sensitivity reaching almost ≈20 % GPa−1 for the Er3+-doped core@shell NPs.

Why are the luminescent properties of the mononuclear and binuclear Eu/Tb-2-hydroxybenzoate complexes with 1,10-phenanthroline so different? An experimental-theoretical study

This study presents a comprehensive investigation into the structural and luminescent properties of lanthanide 2-hydroxybenzoate compounds, focusing on Eu3+ and Tb3+ ions in both single and mixed systems. The X-ray structures of (Hphen)2[Eu2(2-OHBz)8(H2O)2]·2H2O (1a·2H2O) and [Eu(2-OHBz)3(phen)2]·PhMe (2a·PhMe) were determined, where 2-OHBz: 2-hydroxybenzoate and phen: 1,10-phenantroline, revealing triclinic crystal structures with distinct coordination geometries. Compound 1a·2H2O displayed a centrosymmetric dinuclear anion with a coordination number of eight for each Eu3+ center, while compound 2a·PhMe exhibited a neutral mononuclear complex with a decacoordinated Eu3+ center. A comparative analysis of luminescent properties between these compounds unveiled significant differences in the nonradiative decay rates of the 5D0 level of Eu3+ ions, suggesting potential luminescence-quenching channels. The investigation is extended to mixed Eu3+-Tb3+ systems, demonstrating efficient Tb3+ to Eu3+ energy transfer, especially at room temperature. Three models, including two novel ones proposed in this study, were considered to rationalize energy transfer in the mixed systems. Our theoretical-experimental investigation reveals that variations in lifetimes of the emitting level 5D0 of Eu-2-OHBz mononuclear and binuclear complexes, or mixed Eu/Tb-2-OHBz complexes, with 1,10-phenanthrolines, primarily result from multiphonon decay processes; however, low-energy ligand-to-metal charge transfer (LMCT) states play a key role in suppressing luminescence in the binuclear complex compare to the mononuclear ones.

Dy3+,Mn4+ co-doped phosphors for synergistic luminescent dual-mode thermometer and high-resolution imaging

Fluorescent temperature measurement has become a research hotspot due to its characteristics of non-contact, miniaturization, and fast response. However, it remains a key challenge to realize excellent sensitivity and high resolution. Herein, a series of La2MgTiO6:Dy3+,Mn4+ phosphors are developed and the related energy transfer between Dy3+→Mn4+ is discovered. The coupling distance between Mn4+ and adjacent ligands is greatly affected by temperature. However, the energy differences between the emission energy levels and lower energy levels of Dy3+ hinder the multi-phonon relaxation process, which moderates the thermal quenching rate of Dy3+. Therefore, highly sensitive FIR thermometers are built according to the significant discrimination temperature dependence of Dy3+ and Mn4+. The maximum Sa and Sr reach 0.022 K−1(@563 K) and 2.622 %K−1(@544 K). In contrast, a thermometer based on the emission lifetime of Mn4+ is fabricated, which is extremely sensitive to temperature. Interestingly, Dy3+ can effectively promote the quenching of Mn4+, and then improve the sensitivity. The maximum Sr enhances from 1.621 %K−1(@503 K) to 2.305 %K−1 (@480 K). The high sensitivity and resolution of the dual-mode fluorescence thermometry have exceeded most of the current optical thermal measurement materials. Besides, the thermochromic properties presented by the designed phosphors can be combined with PDMS films to qualitatively evaluate the ambient temperature.

Raman Spectra of PbTe- and GeTe-Based Monocrystalline Epitaxial Layers

Lead telluride and germanium telluride are well-known IV-VI semiconductors, which is now the focus of research due to the perspective of application as thermoelectrics for midrange temperatures. Solid solutions and heterostructures on this basis, obtained by molecular beam epitaxy, are a promising direction for the development of these materials. In this paper, we have focused on the Raman spectra excited by the 514.5 nm laser line (out of resonance) of PbTe, GeTe, (Pb, Ge)Te, and (Pb, Ge, Eu)Te layers grown on BaF2 (111) monocrystalline substrates. The obtained phonon properties are related to the properties of the corresponding bulk materials or can be explained by a model that takes into account the difference in the masses of the constituent elements only, as is the case with the local mode of Ge in PbTe (registered at about 181 cm−1). Multiphonon processes registered for this phonon are a consequence of the change in the electronic structure of PbTe and electron-phonon interaction. An improvement in the quality of thin films due to doping with Eu ions was also registered.

Tailoring Carbon Tails of Ligands on Au52(SR)32 Nanoclusters Enhances the Near-Infrared Photoluminescence Quantum Yield from 3.8 to 18.3.

One of the important factors that determine the photoluminescence (PL) properties of gold nanoclusters pertain to the surface. In this study, four Au52(SR)32 nanoclusters that feature a series of aromatic thiolate ligands (-SR) with different bulkiness at the para-position are synthesized and investigated. The near-infrared (NIR) photoluminescence (peaks at 900-940 nm) quantum yield (QY) is largely enhanced with a decrease in the ligand's para-bulkiness. Specifically, the Au52(SR)32 capped with the least bulky p-methylbenzenethiolate (p-MBT) exhibits the highest PLQY (18.3% at room temperature in non-degassed dichloromethane), while Au52 with the bulkiest tert-butylbenzenethiolate (TBBT) only gives 3.8%. The large enhancement of QY with fewer methyl groups on the ligands implies a nonradiative decay via the multiphonon process mediated by C-H bonds. Furthermore, single-crystal X-ray diffraction (SCXRD) comparison of Au52(p-MBT)32 and Au52(TBBT)32 reveals that fewer methyl groups at the para-position lead to a stronger interligand π···π stacking on the Au52 core, thus restricting ligand vibrations and rotations. The emission nature is identified to be phosphorescence and thermally activated delayed fluorescence (TADF) based on the PL lifetime, 3O2 quenching, and temperature-dependent PL and absorption studies. The 1O2 generation efficiencies for the four Au52(SR)32 NCs follow the same trend as the observed PL performance. Overall, the highly NIR-luminescent Au52(p-MBT)32 nanocluster and the revealed mechanisms are expected to find future applications.

Enthalpy-entropy compensation in the slow Arrhenius process.

The Meyer-Neldel compensation law, observed in a wide variety of chemical reactions and other thermally activated processes, provides a proportionality between the entropic and the enthalpic components of an energy barrier. By analyzing 31 different polymer systems, we show that such an intriguing behavior is encountered also in the slow Arrhenius process, a recently discovered microscopic relaxation mode, responsible for several equilibration mechanisms both in the liquid and the glassy state. We interpret this behavior in terms of the multiexcitation entropy model, indicating that overcoming large energy barriers can require a high number of low-energy local excitations, providing a multiphonon relaxation process.

Quantum Phase Transitions of Interlayer Excitons in van der Waals Heterostructures

Quantum phases of interlayer excitons (IXs) in van der Waals heterostructures (vdWHs) play a critical role in determining the fundamental properties of these structures. However, quantum phase transitions between free state and self‐trapped state of IXs remain poorly understood. Herein, the physical pictures for quantum transitions of IXs stemming from the IX–interface optical phonon coupling are explored. The critical boundaries of the phase transitions among free, light, and heavy self‐trapped states are given and the dependence of boundaries on the structural parameters of vdWHs is discussed, implying the controllability of these IXs states in vdWHs. In order to distinguish different quantum phases further, a strategy that multiphonon Raman scattering mediated by these exciton states is proposed. It is found find that multiphonon overtones appear in Raman spectra for the self‐trapped states and not for free states, which clarifies the long‐standing puzzle that free exciton can induce multiphonon Raman processes. The results lay the significant theoretical foundation for understanding the quantum phases of IX and their modulation in vdWHs.

Revisiting the luminescence properties of Er3+, Tm3+ and Ho3+ doped Bi4Ge3O12 rod-type crystal fibers for the laser application

BGO single crystals doped with Er3+, Tm3+ and Ho3+ rare-earth ions were prepared in the form of rod-type crystal fibers via the micro-pulling down technique to perform an extensive investigation of their visible, near- and mid-infrared luminescence properties and to really decide on their interest as solid-state laser media in the various spectral domains. Revisiting and completing the absorption spectra already available in the literature led to the derivation of more reliable “effective” radiative lifetimes and branching ratios. Registration of the fluorescence decays of the most important emitting levels versus dopant concentrations led for the first time to an unambiguous determination of “intrinsic” emission lifetimes – corresponding to negligible contributions from inter-ionic energy-transfers - and non-radiative multiphonon relaxation rates. Such data also allowed for the determination of the dominant phonon energy which comes into play in the electron-phonon coupling responsible for these multiphonon relaxation processes and for its lattice vibration origin, i.e. a high phonon energy of the order of 820 cm−1 corresponding to the coupling between bending vibrations of (GeO4)4- tetrahedra and vibrations corresponding to motions of these (GeO4)4- tetrahedra against the Bi3+ ions for which the rare-earth dopant ions substitute. Using the above data and different methods for the calibration of the registered emission spectra in cross section unit and for the derivation of gain cross section curves finally show that mid-infrared emissions of Er:BGO, Tm:BGO and Ho:BGO around 1.55 μm, 1.9 μm and 2 μm, respectively, occur with comparable gain cross sections as in the most important reference mid-infrared laser materials, although over slightly shifted thus complementary spectral domains. It is shown that potentialities also exist with Tm:BGO in the blue, deep-red and near-infrared spectral domains around 470 nm, 800 nm and 1.45 μm, by pumping the crystals with conventional pump sources and using some suitable co-dopants to avoid detrimental self-terminating processes.

Correlated insulator collapse due to quantum avalanche via in-gap ladder states

The significant discrepancy observed between the predicted and experimental switching fields in correlated insulators under a DC electric field far-from-equilibrium necessitates a reevaluation of current microscopic understanding. Here we show that an electron avalanche can occur in the bulk limit of such insulators at arbitrarily small electric field by introducing a generic model of electrons coupled to an inelastic medium of phonons. The quantum avalanche arises by the generation of a ladder of in-gap states, created by a multi-phonon emission process. Hot-phonons in the avalanche trigger a premature and partial collapse of the correlated gap. The phonon spectrum dictates the existence of two-stage versus single-stage switching events which we associate with charge-density-wave and Mott resistive phase transitions, respectively. The behavior of electron and phonon temperatures, as well as the temperature dependence of the threshold fields, demonstrates how a crossover between the thermal and quantum switching scenarios emerges within a unified framework of the quantum avalanche.

Electric-dipole and magnetic absorption in TbFeO3 single crystals in the THz–IR range

Various mechanisms of absorption including both electric-dipole excitations and magnetic ones in a broadband (5–5000 cm−1) polarized transmission and reflection spectra were studied in orthoferrite TbFeO3 using a coherent submillimeter, pulsed THz, and IR Fourier transform spectroscopy. The classical oscillator model and generalized four-parameter model were used to analyze the spectra obtained, and the parameters of the models were determined. We analyzed main absorption processes, which include contributions of both phonons and multi-phonon processes as well as electron transitions in Tb3+ ions and two antiferromagnetic resonance modes in the Fe subsystem. As a result, the spectra of real and imaginary parts of permeability and permittivity were obtained. A distinctive feature of the studied electrodynamic response in TbFeO3 is a significant absorption in the THz range due to multi-phonon processes, which exceeds optical phonon contribution by an order of magnitude at room temperature.

Concept and strategy of SuperSUN: A new ultracold neutron converter

A new source of ultracold neutrons (UCNs), developed at the Institut Laue-Langevin (ILL) and named SuperSUN, is currently being commissioned. Its operational principle is the conversion of cold neutrons, delivered by ILL’s existing beam H523, to UCNs in a vessel filled with superfluid helium-4, wherein the neutron’s energy and momentum are transferred by inelastic scattering to phonons in the superfluid. The inverse Boltzmann-suppressed process is negligible at temperatures below 0.6 K, enabling long storage times and high in-situ UCN densities as demonstrated at the ILL for two prototype sources. These two prototypes are installed at secondary beams behind crystal monochromators, whereas a primary beam with a white cold spectrum illuminates the SuperSUN conversion volume. This provides not only higher intensity around the wavelength 0.89 nm where the dominant single-phonon process for UCN production takes place, but also a contribution to UCN production by multi-phonon processes. In the first phase of the project, material walls will trap the UCNs, while in the second phase an octupole magnet will generate a 2.1 T magnetic field at the edge of the conversion volume. For low-field-seeking UCNs, this field increases the trapping potential and reduces wall losses so that the accumulated UCNs are spin-polarized as a result. SuperSUN aims to deliver the highest possible UCN densities to external storage experiments, the first of which will be the PanEDM experiment measuring the neutron’s permanent electric dipole moment.

Growth and characterization of PbMo0.75W0.25O4 single crystal: A promising material for optical applications

The present paper reports the structural and optical properties of PbMo0.75W0.25O4 single crystals grown by Czochralski method. XRD pattern of the crystal indicated well-defined two diffraction peaks associated with tetragonal crystalline structure. Raman and infrared spectra of the grown single crystals were presented to get information about the vibrational characteristics. Observed Raman modes were associated with modes of PbMoO4 and PbWO4. Eight bands were revealed in the infrared spectrum. The bands observed in the spectrum were attributed to multiphonon absorption processes. Transmission spectrum was measured in the 375–700 nm spectral region. The analyses of the spectrum resulted in direct band gap energy of 3.12 ± 0.03 eV. The compositional dependent band gap energy plot was drawn considering the reported band gap energies of PbMoO4, PbWO4 and revealed band gap of PbMo0.75W0.25O4 single crystal. An almost linear behavior of composition-band gap energy was seen for PbMo1-xWxO4 compounds. Urbach energy was also found from the absorption coefficient analysis as 0.082 ± 0.002 eV.

Determination of the phonon sidebands in the photoluminescence spectrum of semiconductor nanoclusters from ab initio calculations

We propose a theoretical approach based on (constrained) density functional theory and the Franck-Condon approximation for the calculation of the temperature dependent photoluminescence of nanostructures. The method is computationally advantageous and only slightly more demanding than a standard density functional theory calculation and includes transitions into multiphonon final states (higher class transitions). We use the approach for Si and CdSe colloidal nanoclusters with up to 693 atoms and obtain very good agreement with experiment which allows us to identify specific peaks and explain their origin. Generally, breathing type modes are shown to dominate the phonon replicas, while optical modes have significant contributions for CdSe nanoclusters (NCs) and play a lesser role in Si NCs. We obtain significant anti-Stokes peak starting at 140 K for Si NC explaining the broadening observed in the corresponding experiment. We also apply the method to small molecular-like carbon structures (diamondoids), where electron-phonon coupling is typically large, and find that multiphonon processes (up to class 4) are very relevant and necessary to compare favorably with experiment. While it is crucial to include these multiphonon states in the small diamondoids with few tens of atoms, neglecting them in only marginally larger ${\mathrm{Si}}_{87}{\mathrm{H}}_{76}$ and ${\mathrm{Cd}}_{43}{\mathrm{Se}}_{44}{\mathrm{H}}_{76}^{*}$ (and larger) quantum dots represents a good approximation.

Charge Carriers Trapping by the Full-Configuration Defects in Metal Halide Perovskites Quantum Dots

Metal halide perovskites quantum dots (MHPQDs) have aroused enormous interest in the photovoltaic and photoelectric disciplines because of their marvelous properties and size characteristics. However, one of the key problems of how to systematically analyze charge carriers trapped by defects is still a challenging task. Here, we study multiphonon processes of the charge carrier trapping by various defects in MHPQDs based on the well-known Huang-Rhys model, in which a method of a full-configuration defect, including different defect species with variable depth and lattice relaxation strength, is developed by introducing a localization parameter in the quantum defect model. With the help of this method, these fast trapping channels for charge carriers transferring from the quantum dot ground state to different defects are found. Furthermore, the dependence of the trapping time on the radius of quantum dot, the defect depth, and temperature is given. These results not only enrich the knowledge of charge carrier trapping processes by defects, but also bring light to the designs of MHPQDs-based photovoltaic and photoelectric devices.

Dark matter direct detection from the single phonon to the nuclear recoil regime

In most direct detection experiments, the free nuclear recoil description of dark matter scattering breaks down for masses $\lesssim$ 100 MeV, or when the recoil energy is comparable to a few times the typical phonon energy. For dark matter lighter than 1 MeV, scattering via excitation of a single phonon dominates and has been computed previously, but for the intermediate mass range or higher detector thresholds, multiphonon processes dominate. We perform the first calculation of the scattering rate via multiphonon production for the entire keV-GeV dark matter mass range, assuming a harmonic crystal target. We provide an analytic description that connects the single phonon, multiphonon, and the nuclear recoil regimes. Our results are implemented in the public package $\texttt{DarkELF}$.