Strong Electron-phonon Coupling Research Articles

Enhanced UV Light Responsivity in -Oriented 2D Perovskites Realized by Pressure-induced Ultrafast Exciton Transport.

Two-dimensional (2D) <100>-oriented perovskites exhibit superior optoelectronic properties, offering significant potential in photovoltaic, light-emitting, and photodetection applications. Nevertheless, their enlarged interlayer spacing restricts longitudinal carrier transport, thereby limiting its potential applications. While <110>-oriented 2D perovskites provide a prospective solution with their compact interlayer spacing, their inherent structure, characterized by octahedra tilting, indirectly hinders carrier transport due to the generation of self-trapped excitons (STEs) caused by strong electron-phonon coupling. Here, we adeptly regulate the photoluminescence (PL) from STEs to free excitons (FEs) emission within the 2D <110>-oriented (API)PbBr4 single crystal through structure optimization under pressure treatment. Besides, we observed anisotropic FE transport with an anisotropy ratio of 4.97. The exciton mobility reaches a peak of 93.6 cm2V-1s-1 at 2.7 GPa, a value comparable to those of their three-dimensional (3D) counterparts, which is attributed to a reduction in electron-phonon coupling and exciton reduced mass. Additionally, this ultrafast exciton transport significantly enhances UV light responsivity, exhibiting an increase of approximately 5000 times at 2.7 GPa in comparison to ambient conditions. These findings highlight the prospective application of 2D <110>-oriented perovskites in high-performance optoelectronic devices through intrinsic structural modulation.

Realizing Near-Unity Photoluminescence Efficiency in Antimony-Doped Indium-Based Halides Induced by Strong Electron-Phonon Coupling.

Exploring a zero-dimensional (0D) hybrid halide with a large Stokes shift and efficient broad-band emission is highly desirable due to its enormous potential for solid-state lighting (SSL) application. However, it is still challenging to develop a highly emissive 0D hybrid halide with low toxicity and remarkable stability. Herein, we developed a novel indium-based metal halide A5In2Cl16·4H2O (A = doubly protonated 1,4-diaminobutane) whose inorganic octahedrons are completely isolated by the organic cations to form the 0D structure. Experimental and theoretical studies confirmed that Sb-doped A5In2Cl16·4H2O exhibits broad yellow emission with a photoluminescence quantum yield (PLQY) of up to 98%. The intense yellow emission can be attributed to the radiative recombination of triplet self-trapped excitons (STEs) in [SbCl6]3- octahedrons caused by the strong electron-phonon coupling. Benefiting from the excellent stability and photoluminescence performance, A5In2Cl16·4H2O:15%Sb was used as the yellow phosphor to prepare a white-light-emitting diode (WLED) device with a color rendering index of 87.8 and a luminous efficiency of up to 36.18 lm/W, demonstrating its potential in SSL applications. This work provides a guidance for developing environmentally friendly, efficient, and stable ultraviolet (UV)-excited broad-band emission materials.

Enhancement of NIR-II Emission of Er3+ by Doping Fe3+ in Double Perovskites: Multimode Luminescence for Versatile Optoelectronic Applications.

Erbium ions are commonly used to extend the photoelectric properties of metal halide perovskites from visible to near-infrared (NIR) range. However, achieving high-efficiency multi-mode luminescence in a single system is difficult due to the weak absorption associated with forbidden 4f-4f transitions. In this study, a unique strategy is proposed to adjust multi-mode luminescence and enhance NIR-II emission in Cs2NaBiCl6 by incorporating Fe3+ ions. The as-prepared material demonstrates reversible thermochromism, driven by strong electron-phonon coupling effect, and exhibits tunable luminescence that can be adjusted by altering excitation energy and temperature. Notably, benefitting from the charge transfer transition of Fe3+-Cl- along with the influence of Fe3+ doping on the geometrical and electronic structures, the blue-excitable (450 nm) NIR-II emission around 1541 nm from Er3+ is realized for the first time, achieving an intensity 16.7 times higher and a maximum photoluminescence quantum yield of 22.5%. This enhancement enables innovative applications such as two-dimensional information encryption by the multi-channel cooperative responses and improved NIR imaging. The study highlights the potential of Fe3+ doping in optimizing absorption and multi-mode luminescence in perovskites, opening avenues for advanced applications in blue-excitable NIR light emitting diodes, thermometer, anti-counterfeiting, and NIR imaging.

In-Situ comparative study of photo-induced charge behavior in single-perovskite Cs3Bi2Br9 and double-perovskite Cs2AgBiBr6

While organic-inorganic lead halide perovskites excel in optoelectronic applications, their use is limited by toxicity and degradation. Consequently, lead-free alternatives like Cs2AgBiBr6, offering greater stability and diverse applications, have been investigated. However, the fundamental structural, optical, and electronic properties of Cs2AgBiBr6 remain insufficiently understood. In this study, we compared the exciton dynamics and photo-induced charge separation in Cs3Bi2Br9 and Cs2AgBiBr6 films using in-situ surface techniques. Both materials display similar surface photovoltage (SPV) peaks in the 450–500 nm range, supporting the hypothesis of Bi 6s-6p orbital transitions in distorted [BiBr6]3− structures. Although many theories propose the presence of self-trapped excitons (STE) in bismuth-based perovskites, sufficient evidence has been lacking. Our observation of a significant redshift in the SPV peak compared to the band edge absorption peak supports STE hypothesis, with Cs2AgBiBr6 showing a more pronounced redshift due to its more complex electronic structure and stronger electron-phonon coupling. Additionally, we observed that Cs2AgBiBr6 exhibits superior charge separation efficiency compared to Cs3Bi2Br9. Notably, Cs2AgBiBr6 shows significantly shorter rise times, indicating more rapid photogenerated charge separation. However, both materials exhibit similar fall times, suggesting comparable charge recombination rates. Light-chopping-frequency dependent SPV measurements further reveal that Cs2AgBiBr6 has a higher charge separation rate than Cs3Bi2Br9. These findings underscore the potential of bismuth-based perovskites for optoelectronic applications and highlight the importance of a comprehensive understanding of their structure-property relationships.

Three-gap superconductivity with Tc above 80 K in hydrogenated 2D monolayer LiBC

Although the metallization of semiconductor bulk LiBC has been experimentally achieved, various flaws, including the strong lattice distortion, the uncontrollability of phase transition under pressure, usually appear. In this work, based on the first-principles calculations, we propose a new way of hydrogenation to realize metallization. Using the fully anisotropic Migdal-Eliashberg theory, we investigate the superconducting behaviors in the stable monolayers LiBCH and LiCBH, in which C and B atoms are hydrogenated, respectively. Our findings indicate that the monolayers possess the high Tc of 82.0 and 82.5 K, respectively, along with the interesting three-gap superconducting natures. The Fermi sheets showing the obvious three-region distribution characteristics and the abnormally strong electron-phonon coupling are responsible for the high-Tc three-gap superconductivity. Furthermore, the Tc can be dramatically boosted up to 120.0 K under 3.5% tensile strain. To a great extent, the high Tc is beyond the liquid nitrogen temperature (77 K), which is beneficial for the applications in future experiments. This study not only explores the superconducting properties of the monolayers LiBCH and LiCBH, but also offers practical insights into the search for high-Tc superconductors. Published by the American Physical Society 2024

Prediction of novel layered indium halide superconductors

Abstract We design two new layered indium halide compounds LaOInF2 and LaOInCl2 by means of first-principles calculations and evolutionary crystal structure prediction. We find both compounds crystallize in a tetragonal structure with P4/nmm space group and have indirect band gaps of 2.58 eV and 3.21 eV, respectively. By substituting O with F, both of them become metallic and superconducting at low temperature. The F-doping leads to strong electron–phonon coupling in the low-energy acoustic phonon modes which is mainly responsible for the induced superconductivity. The total electron–phonon coupling strength are 1.86 and 1.48, while the superconducting transition temperature (T c) are about 7.2 K and 6.5 K with 10% and 5% F doping for LaOInF2 and LaOInCl2, respectively.

Half-metallization Atom-Fingerprints Achieved at Ultrafast Oxygen-Evaporated Pyrochlores for Acidic Water Oxidation.

The stability and catalytic activity of acidic oxygen evolution reaction (OER) are strongly determined by the coordination states and spatial symmetry among metal sites at catalysts. Herein, an ultrafast oxygen evaporation technology to rapidly soften the intrinsic covalent bonds using ultrahigh electrical pulses is suggested, in which prospective charged excited states at this extreme avalanche condition can generate a strong electron-phonon coupling to rapidly evaporate some coordinated oxygen (O) atoms, finally leading to a controllable half-metallization feature. Simultaneously, the relative metal (M) site arrays can be orderly locked to delineate some intriguing atom-fingerprints at pyrochlore catalysts, where the coexistence of metallic bonds (M─M) and covalent bonds (M─O) at this symmetry-breaking configuration can partially restrain crystal field effect to generate a particular high-spin occupied state. This half-metallization catalyst can effectively optimize the spin-related reaction kinetics in acidic OER, giving rise to 10.3 times (at 188mV overpotential) reactive activity than pristine pyrochlores. This work provides a new understanding of half-metallization atom-fingerprints at catalyst surfaces to accelerate acidic water oxidation.

Ligand Controls Excited Charge Carrier Dynamics in Metal-Rich CdSe Quantum Dots: Computational Insights.

Small metal-rich semiconducting quantum dots (QDs) are promising for solid-state lighting and single-photon emission due to their highly tunable yet narrow emission line widths. Nonetheless, the anionic ligands commonly employed to passivate these QDs exert a substantial influence on the optoelectronic characteristics, primarily owing to strong electron-phonon interactions. In this work, we combine time-domain density functional theory and nonadiabatic molecular dynamics to investigate the excited charge carrier dynamics of Cd28Se17X22 QDs (X = HCOO-, OH-, Cl-, and SH-) at ambient conditions. These chemically distinct but regularly used molecular groups influence the dynamic surface-ligand interfacial interactions in Cd-rich QDs, drastically modifying their vibrational characteristics. The strong electron-phonon coupling leads to substantial transient variations at the band edge states. The strength of these interactions closely depends on the physicochemical characteristics of passivating ligands. Consequently, the ligands largely control the nonradiative recombination rates and emission characteristics in these QDs. Our simulations indicate that Cd28Se17(OH)22 has the fastest nonradiative recombination rate due to the strongest electron-phonon interactions. Conversely, QDs passivated with thiolate or chloride exhibit considerably longer carrier lifetimes and suppressed nonradiative processes. The ligand-controlled electron-phonon interactions further give rise to the broadest and narrowest intrinsic optical line widths for OH and Cl-passivated single QDs, respectively. Obtained computational insights lay the groundwork for designing appropriate passivating ligands on metal-rich QDs, making them suitable for a wide range of applications, from blue LEDs to quantum emitters.

Small Polaron Dynamics in Transition Metal Oxide Photoelectrodes

The transition metal oxides are widely used in many optoelectronic applications, such as working as charge-transporting layers in solar cells and photoelectrodes in light-driven water-splitting. Considering the ionic bonding nature, the lattice of these oxides can be polarized by the charge carriers due to the strong electron-phonon coupling, giving rise to lattice distortion that fosters a local potential well. This lattice distortion together with the trapped carrier is regarded as a quasi-particle, i.e., a polaron. Here, the photocarrier dynamics in transition metal oxides were investigated using the transient absorption and time-resolved terahertz spectroscopies. We identified the spectral features of small polarons, self-trapped excitons, and free carriers and extracted their dynamics independently. We proposed a molecular model that could successfully explain the non-barrier self-trapping and quantitatively describe the temperature-dependent recombination of self-trapped excitons and the dopant effect on the photocarrier dynamics. Our model also suggested that the recombination of self-trapped excitons at room temperature was dominated by nuclear quantum tunneling. This model also predicted the micro-heterogeneity of the self-trapped species, and thus be able to quantitatively describe the Auger annihilation dynamics of self-trapped excitons.

High- Tc superconductivity in doped molecular superconductors of K4B8−xMxH32 (M = C, N) under high pressure

Stabilized and metallic light elements hydrides have provided a potential route to achieve the goal of room-temperature superconductors at moderate or ambient pressures. Here, we have performed systematic DFT theoretical calculations to examine the effects of different light elements C and N atoms doped in cubic K4B8H32 hydrides on the superconductivity at low pressures. As a result of various atoms substituting, we have found that metallic K4B _{8-x} M x H32 (M = C, N) hydrides are dynamically stable at 50 GPa, band structures and density of states (DOS) indicate that sizeable Tc correlates with a high B–H DOS at the Fermi level. With the increasing of B atoms in K4B _{8-x} M x H32 hydrides, the DOS values at Fermi level have been improved due to the delocalized electrons in B–H bonds, which result in strong electron–phonon coupling (EPC) interaction and increase the Tc from 19.04 to 77.07 K for KC2H8 and KB2H8 at 50 GPa. The NH4 unit in stable K4B7NH32 hydrides has weakened the EPC and led to low Tc value of 21.47 K. Our results suggest the light elements hydrides KB2H8 and K4B7CH32 could estimate high Tc values at 50 GPa, and the boron hydrides would be potential candidates to design or modulate hydrides superconductors with high Tc at moderate or ambient pressures.

Prediction of Room-Temperature Superconductivity in Quasi-Atomic H2-Type Hydrides at High Pressure.

Achieving superconductivity at room temperature (RT) is a holy grail in physics. Recent discoveries on high-Tc superconductivity in binary hydrides H3S and LaH10 at high pressure have directed the search for RT superconductors to compress hydrides with conventional electron-phonon mechanisms. Here, an exceptional family of superhydrides is predicated under high pressures, MH12 (M = Mg, Sc, Zr, Hf, Lu), all exhibiting RT superconductivity with calculated Tcs ranging from 313 to 398 K. In contrast to H3S and LaH10, the hydrogen sublattice in MH12 is arranged as quasi-atomic H2 units. This unique configuration is closely associated with high Tc, attributed to the high electronic density of states derived from H2 antibonding states at the Fermi level and the strong electron-phonon coupling related to the bending vibration of H2 and H-M-H. Notably, MgH12 and ScH12 remain dynamically stable even at pressure below 100 GPa. The findings offer crucial insights into achieving RT superconductivity and pave the way for innovative directions in experimental research.

Quantification of the strong, phonon-induced Urbach tails in β-Ga2O3 and their implications on electrical breakdown

In ultrawide bandgap (UWBG) nitride and oxide semiconductors, increased bandgap (Eg) correlates with greater ionicity and strong electron–phonon coupling. This limits mobility through phonon scattering, localizes carriers via polarons and self-trapping, broadens optical transitions via dynamic disorder, and modifies the breakdown field. Herein, we use polarized optical transmission spectroscopy from 77 to 633 K to investigate the Urbach energy (Eu) for many orientations of Fe- and Sn-doped β-Ga2O3 bulk crystals. We find Eu values ranging from 60 to 140 meV at 293 K and that static (structural defects plus zero-point phonons) disorder contributes more to Eu than dynamic (finite temperature phonon-induced) disorder. This is evidenced by lack of systematic Eu anisotropy, and Eu correlating more with x-ray diffraction rocking-curve broadening than with Sn-doping. The lowest measured Eu are ∼10× larger than for traditional semiconductors, pointing out that band tail effects need to be carefully considered in these materials for high field electronics. We demonstrate that, because optical transmission through thick samples is sensitive to sub-gap absorption, the commonly used Tauc extraction of a bandgap from transmission through Ga2O3 &amp;gt;1–3 μm thick is subject to errors. Combining our Eu(T) from Fe-doped samples with Eg(T) from ellipsometry, we extract a measure of an effective electron–phonon coupling that increases in weighted second order deformation potential with temperature and a larger value for E||b than E||c. The large electron–phonon coupling in β-Ga2O3 suggests that theories of electrical breakdown for traditional semiconductors need expansion to account not just for lower scattering time but also for impact ionization thresholds fluctuating in both time and space.

Temperature- and pressure-responsive photoluminescence in a 1D hybrid lead halide

Low-dimensional hybrid lead halides with responsive emissions have attracted considerable attention due to their potential applications in sensing. Herein, a new one-dimensional hybrid lead bromide CyPbBr3 (Cy = cytosine cation) was synthesized to explore its emission evolution in response to temperature and pressure. The compound possesses an edge-sharing 1D double-chain structure and emits warm white light across nearly the entire visible spectrum upon ultraviolet excitation. This emission arises from the self-trapped excitons and its broadband feature is attributed to the strong electron-phonon coupling as revealed by the variable-temperature photoluminescence experiments. Moreover, a 4.5-fold pressure-induced emission enhancement was observed at 2.7 GPa which is caused by the pressure suppressed non-radiative energy loss. Furthermore, in-situ powder X-ray diffraction and Raman experiments reveal the maxima of the emission enhancement is associated with a phase transition at the same pressure. Our work demonstrates that low-dimensional metal halides are a promising class of stimuli-responsive materials which could have potential applications in temperature and pressure sensing.

Strong electron-phonon coupling and multigap superconductivity in 2H/1T Janus MoSLi monolayer.

Two-dimensional (2D) Janus transition metal dichalcogenides MXY manifest novel physical properties owing to the breaking of out-of-plane mirror symmetry. Recently, the 2H phase of MoSH has been demonstrated to possess intrinsic superconductivity, whereas the 1T phase exhibits a charge density waves state. In this paper, we have systematically studied the stability and electron-phonon interaction characteristics of MoSLi. Our results have shown that both the 2H and 1T phases of MoSLi are stable, as indicated by the phonon spectrum and the abinitio molecular dynamics. However, the 1T phase exhibits an electron-phonon coupling constant that is twice as large as that of the 2H phase. In contrast to MoSH, the 1T phase of MoSLi exhibits intrinsic superconductivity. By employing the abinitio anisotropic Migdal-Eliashberg formalism, we have revealed the two-gap superconducting nature of 1T-MoSLi, with a transition temperature (Tc) of 14.8K. The detailed analysis indicates that the superconductivity in 1T-MoSLi primarily originates from the interplay between the vibration of the phonon modes in the low-frequency region and the dz2 orbital. These findings provide a fresh perspective on superconductivity within Janus structures.

Optical manipulation of the charge-density-wave state in RbV3Sb5.

Broken time-reversal symmetry in the absence of spin order indicates the presence of unusual phases such as orbital magnetism and loop currents1-4. The recently discovered kagome superconductors AV3Sb5 (where A is K, Rb or Cs)5,6 display an exotic charge-density-wave (CDW) state andhave emerged as astrong candidate for materialshosting a loop currentphase. The idea that the CDW breaks time-reversal symmetry7-14 is, however, being intensely debated due to conflicting experimental data15-17. Here we use laser-coupled scanning tunnelling microscopy to study RbV3Sb5. By applying linearly polarized light along high-symmetry directions, we show that the relative intensities of the CDW peaks can be reversibly switched, implying a substantial electro-striction response, indicative of strong nonlinear electron-phonon coupling. A similar CDW intensity switching is observed with perpendicular magnetic fields, which implies an unusual piezo-magnetic response that, in turn, requires time-reversal symmetry breaking. We show that the simplest CDW that satisfies these constraints is an out-of-phase combination of bond charge order and loop currents that we dub a congruent CDW flux phase. Our laser scanning tunnelling microscopy data open the door to the possibility of dynamic optical control of complex quantum phenomenon in correlated materials.

Pressure-induced novel phases with the high-Tc superconductivity in zirconium dihydride

The unprecedented structures in hydrides could be uncovered under high pressure, which probably possess unusual properties, such as high-Tc superconductivity. Here, the structural transition of ZrH2 at 0−500 GPa are comprehensively explored by using the evolutionary algorithm in the universal structure predictor combined with first-principles calculations. Three new phases are found: Pnma-ZrH2, P-3m1-ZrH2 and R-3m-ZrH2, with dynamic stability. Moreover, the sequence of phases of ZrH2 under pressure is I4/mmm → P4/nmm → Pnma → P-3m1 → R-3m with the zero-point energy effects. Structural feature, electronic properties, bonding characters and superconductivity of all the ZrH2 are analyzed in detail. More importantly, the superconducting critical temperature Tc values for P-3m1 at 440 GPa and R-3m at 500 GPa are 17.70–20.14 K and 26.68–30.03 K, respectively, which stems from the strong electron-phonon coupling.

First-principles study of two-dimensional transition metal carbide M n+1 C n O2 (M = Nb,Ta)

In the present work, the three stable MXenes M n+1 C n O2 (M = Nb,Ta) are explored based on first-principles calculations. These materials are important derivatives of 2D materials and exhibit distinctive properties, holding vast potential in nanodevices. All these M n+1 C n O2 (M = Nb,Ta) materials exhibit outstanding superconducting performance, with corresponding superconducting transition temperatures of 23.00 K, 25.00 K, and 29.00 K. Analysis reveals that the high superconducting transition temperatures of MXenes M n+1 C n O2 (M = Nb,Ta) are closely associated with the high value of the logarithmic average of phonon frequencies, ωlog , and the strong electron–phonon coupling, attributed to the crucial contribution of low-frequency phonons. Additionally, we applied strain treatments of 2% and 4% to M n+1 C n O2 (M = Nb,Ta), resulting in varying changes in superconducting transition temperatures under different strains.

Tuning Electron–Phonon Coupling Interaction for the Efficient Wide Blue Emission of Pb2+‐Doped Cs2InCl5·H2O

AbstractLead‐free perovskites exhibit unique crystal structures and optical properties due to their low‐dimensional structure. However, the 0D structure of Cs2InCl5·H2O usually demonstrates poor optical properties at room temperature due to their extremely strong electron–phonon coupling interaction. In this study, a doping strategy is employed by introducing Pb2+ into Cs2InCl5·H2O, resulting in the achievement of an efficient broadband blue emission, with a photoluminescence quantum yield (PLQY) of 58%. The temperature‐dependent PL spectra reveal that the efficient emission is attributed to the weakening of the electron–phonon coupling strength in the lattice and the inhibition of the phonon‐assisted non‐radiative recombination process through Pb2+ doping. The validity of this deduction is further corroborated by the results of the Raman spectra. The results of the first‐principle calculation demonstrate that the broadband emission originates from multiple emission paths in In3+ and Pb2+ polyhedrons. In addition, Pb2+‐doped Cs2InCl5·H2O can realize the transformation from sky‐blue emission to deep‐blue emission by absorbing water in the air. Remarkably, this change is reversible during the heating–cooling cycles, demonstrating excellent optical stability with repeatable recyclability.

Magnetothermal properties of CoO2 monolayer from first-principles and Monte Carlo simulations

Cobalt oxides are known for their excellent heat transfer properties. The main component of cobalt oxides is the CoO2 monolayer, which exhibits high-temperature superconductivity caused by strong electron–phonon coupling (EPC). We here systematically investigate the structural stability, electronic structure, and magnetism of the CoO2 monolayer using first-principles and Monte Carlo simulations. On this basis, we further study the changes in the spin energy gap, magnetic axis direction, and other properties of the CoO2 monolayer with the changes in carrier concentration. By appropriately doping the CoO2 monolayer with holes, the magnetic axis direction of the CoO2 monolayer can be reversed, thereby enhancing its potential application in the field of spin electronic devices. Monte Carlo simulation is used to study the regulation of different factors on the magnetothermal properties of the CoO2 monolayer. Through the analysis of physical parameters such as Curie temperature (TC) and bandgap, we find that the appropriate carrier concentration and magnetic field can not only regulate the magnetothermal properties of materials but also further improve the efficiency of materials in low-temperature environments.

Unusual Lattice Dilation and Strong Electron–Phonon Coupling in Erbium Ferrite Perovskite

Unusual Lattice Dilation and Strong Electron–Phonon Coupling in Erbium Ferrite Perovskite