Phonon Coupling Research Articles

Novel electrical properties of moiré graphene systems

In this review, we discuss the electronic structures, topological properties, correlated states, nonlinear optical responses, as well as phonon and electron-phonon coupling effects of moiré graphene superlattices. First, we illustrate that topologically non-trivial flat bands and moiré orbital magnetism are ubiquitous in various twisted graphene systems. In particular, the topological flat bands of magic-angle twisted bilayer graphene can be explained from a zeroth pseudo-Landau-level picture, which can naturally explain the experimentally observed quantum anomalous Hall effect and some of the other correlated states. These topologically nontrivial flat bands may lead to nearly quantized piezoelectric response, which can be used to directly probe the valley Chern numbers in these moiré graphene systems. A simple and general chiral decomposition rule is reviewed and discussed, which can be used to predict the low-energy band dispersions of generic twisted multilayer graphene system and alternating twisted multilayer graphene system. This review further discusses nontrivial interaction effects of magic-angle TBG such as the correlated insulator states, density wave states, cascade transitions, and nematic states, and proposes nonlinear optical measurement as an experimental probe to distinguish the different “featureless” correlated states. The phonon properties and electron-phonon coupling effects are also briefly reviewed. The novel physics emerging from band-aligned graphene-insulator heterostructres is also discussed in this review. In the end, we make a summary and an outlook about the novel physical properties of moiré superlattices based on two-dimensional materials.

Soft phonon modes lead to suppressed thermal conductivity in Ag-based chalcopyrites under high pressure.

Pressure is a powerful way to modulate physical properties. Understanding the effect of pressure on the thermal transport properties of thermoelectric materials is of great importance for the efficient design and optimization of thermoelectric performance. In this work, based on first-principles calculations and phonon Boltzmann transport theory, we find that the lattice thermal conductivities of Ag-based chalcopyrites AgXY2 (X = Al, Ga, and In; Y = S, Se, and Te) are dramatically suppressed by applying pressure. The inherent distorted tetrahedral configuration together with highly delocalized p-orbital electrons promotes the formation of metavalent bonding. The fact of metavalent bonding with a single bonding electron and small electron transfer between neighboring atoms leads to soft low-frequency optical phonons. With the increase of pressure, the softening of acoustic and low-frequency optical phonons induces enhanced anharmonicity and scattering channels. Such strong acoustic-optical phonon coupling results in larger phonon scattering rates and thus lowers the lattice thermal conductivity. These findings not only help unveil the underlying physical mechanisms for the anomalous thermal transport behaviors under high pressure, but also pave the way for the pressure tuning of high-performance Ag-based thermoelectric materials.

Transforming exciton dynamics in perovskite nanocrystal through Mn doping.

Zn-alloyed CsPb(Cl/Br)3 perovskite nanocrystals (PNCs) have been synthesized and used as a model system for Mn doping in order to understand the effect of Mn doping on exciton dynamics. While keeping the PL emission maximum and PLQY of both PNC samples nearly the same, the radiative decay rate of the host band decreases ∼6.5 times and the non-radiative decay rate increases ∼2.5 times upon Mn doping. Unlike reports in the literature in which the dopant emission decreases to near-zero, in the present case we observe ∼5.5-fold enhancement of the integrated PL intensity of the dopant emission when the temperature decreases from 290 K to 190 K. Interestingly, the FWHM of the host PL emission band increases with a decrease in temperature from 290 K to 190 K. A higher value of phonon energy in PNC2 (58 ± 2 meV) in comparison to CsPbBr3 has been noted. The low magnitude of the Huang-Rhys factor indicates less electron phonon coupling for the Mn-doped PNC system. Temperature-dependent dopant PL decay exhibits biexponential decay behaviour with time constants τ1 = 450-540 μs and τ2 = 1.1-1.2 ms. With a decrease in temperature from 290 K to 190 K, the amplitude of the faster component decreases from 80% to 60%; concomitantly, the amplitude of the slower component increases from 20% to 40%. Ultrasensitive single-particle spectroscopic analyses reveal that, although the probability density distributions (PDDs) of the durations of both ON and OFF events of PNC1 could be fitted with a truncated inverse power law (TIPL), however, for PNC2, both PDDs could be fitted with an inverse power law (IPL). A comparatively lower value of the power law exponent mON indicates a higher probability of longer ON events for PNC1 than for PNC2. Truncation in the PDDs of both ON and OFF events has been observed for PNC1, but not in the PDDs of either ON or OFF events for PNC2. The presence of shallow trap states is responsible for the truncation for PNC1, whereas the presence of deep dopant states does not allow truncation in the host PL emission of PNC2. All these observations clearly demonstrate that Mn doping transforms the host PL exciton dynamics for Zn-alloyed Mn-doped CsPb(Cl/Br)3 PNCs very significantly.

Predicted superconductivity in one-dimensional A3Hf2B3-type electrides.

Inorganic electrides are considered potential superconductors due to the unique properties of their anionic electrons. However, most electrides require external high-pressure conditions to exhibit considerable superconducting transition temperatures (Tc). Therefore, searching for superconducting electrides under low or moderate external pressures is of significant research interest and importance. In this work, a series of A3Hf2B3-type compounds (A = Mg, Ca, Sr, Ba; B = Si, Ge, Sn, Pb) were constructed and systematically studied based on density functional theory calculations. According to the analysis of the electronic structures and phonon dispersion spectrums, stable one-dimensional electrides Ca3Hf2Ge3, Ca3Hf2Sn3, and Sr3Hf2Pb3, were screened out. Interestingly, the superconductivity of these electrides were predicted from electron phonon coupling calculations. It is highlighted that Sr3Hf2Pb3 showed the highest Tc, reaching 4.02 K, while the Tc values of Ca3Hf2Ge3 and Ca3Hf2Sn3 were 1.16 K and 1.04 K, respectively. Moreover, the Tc value of Ca3Hf2Ge3 can be increased to 1.96 K under 20 GPa due to the effect of phonon softening. This work enriches the types of superconducting electrides and has important guiding significance for the research on constructing electrides and related superconducting materials.

Influence of ligands on the optical properties of rod-shaped Au25 nanoclusters.

In this study, we successfully synthesized rod-shaped [Au25(PPh3)10(S-Adm)5Cl2]2+ nanoclusters using kinetic controls. The complete molecular structure was determined by single-crystal X-ray crystallography and electrospray ionization mass spectrometry. In comparison with the previously reported [Au25(PPh3)10(PET)5Cl2]2+ clusters, both nanoclusters have an icosahedral composition of Au13 linked by Au atoms that share a vertex, but [Au25(PPh3)10(S-Adm)5Cl2]2+ clusters appear elongated due to the rigidity of adamantane. We conducted ultraviolet-visible spectrophotometry (UV-vis) measurements of [Au25(PPh3)10(PET)5Cl2]2+ and [Au25(PPh3)10(S-Adm)5Cl2]2+ in dichloromethane solvent to elucidate the modulation of the cluster properties of different ligands. The lowest energy absorption peak of [Au25(PPh3)10(S-Adm)5Cl2]2+ shifted to lower energies compared to the [Au25(PPh3)10(PET)5Cl2]2+ clusters in UV-vis measurements. Temperature-dependent absorption measurements revealed that [Au25(PPh3)10(S-Adm)5Cl2]2+ clusters were less affected by temperature compared to [Au25(PPh3)10(PET)5Cl2]2+. This result is attributed to the exciton phonon coupling of [Au25(PPh3)10(S-Adm)5Cl2]2+ clusters being weaker than [Au25(PPh3)10(PET)5Cl2]2+ clusters. Furthermore, the absorption spectra of [Au25(PPh3)10(PET)5Cl2]2+ and [Au25(PPh3)10(S-Adm)5Cl2]2+ clusters were measured using different types of solutions, and it was found that the lowest energy absorption peaks of [Au25(PPh3)10(S-Adm)5Cl2]2+ were shifted and affected by the solution at room temperature, which suggested that the [Au25(PPh3)10(S-Adm)5Cl2]2+ clusters with solution hydrogen bonds also interacted strongly at room temperature. Theoretical calculations show that changes in ligands affect the differences in the molecular orbitals and structures of the clusters, which cause changes in the optical properties.

Nuclear response to dark matter signals in Ge and Xe odd-mass targets

The interaction of dark matter particles (weakly interacting massive particles (WIMPs)) with the odd-mass [Formula: see text]Ge and [Formula: see text]Xe target nuclei, that is, the recoil rates corresponding to the elastic scattering of WIMPs by these nuclei, is analyzed in the context of the minimal extensions of the supersymmetry model. The BCS+QRPA technique plus the quasiparticle–phonon coupling scheme is used to describe the nuclear structure part of the calculations. The resulting values for the nuclear spin content of both nuclei are compared to values previously reported in the literature.

Study on the optical properties and electronic structures of Ba-doped KH2PO4 crystals

Electronic structure and one-dimensional configurational coordinate diagrams considering the electron–phonon coupling are derived to calculate the spectra.

Carrier mobility of two-dimensional Dirac materials: the influence of optical phonon scattering.

We developed an analytical formula to calculate the influence of optical phonons on the mobility of two-dimensional Dirac materials at arbitrary temperature and arbitrary doping concentration. The method was combined with first-principles calculations to show that the effect of optical phonons on mobility is not negligible for typical Dirac materials such as graphene even though the occupation number of optical phonons is relatively small. Unlike the treatment of electron-acoustic phonon coupling, the energy change of electrons in the scattering process with optical phonons is crucial, which leads to a non-power temperature dependence of mobility under weak doping. The formalism was applied to calculate and analyze the mobility of two well-known Dirac materials, α-graphyne and the VCl3 monolayer, which differs by one to two orders of magnitude.

Factors influencing self-trapped exciton emission of low-dimensional metal halides

In this review, we mainly summarized the structure distortion, molecular engineering, electron–phonon coupling effect, external temperature and pressure, and metal ion doping that influence the self-trapped exciton emission of low-dimensional metal halides (LDMHs).

High carrier mobility and strong electron–phonon coupling in graphene–WS2 heterobilayers under pressure

Graphene-TMD heterojunctions with strong electron–phonon coupling are expected in nano-photodetectors, yet the chemical doping hinders the performance of graphene, and the limited photoelectric conversion and lack of effective regulation of interlayer interactions hinder further research on heterostructures.

Exciton-phonon coupling in two-dimensional layered (BA)2PbI4 perovskite microplates.

Two-dimensional layered (BA)2PbI4 (BA = C4H9NH3) perovskites are emerging as a new class of layered materials and show great potential in optoelectronic applications. Elucidating how exciton-phonon interaction affects the excitonic emission is of great importance for a better knowledge of their optoelectronic properties. In this letter, we synthesized high-quality (BA)2PbI4 microplates via solution methods, and dual-excitonic emission peaks (surface-emission and interior-emission) were detected from the as-grown samples at low temperatures. Furthermore, we determine the energies for the longitudinal optical phonon modes to be ∼27 and ∼18 meV, and the exciton-phonon coupling strengths to be ∼177 and ∼21 meV for the surface-emission and interior-emission bands, respectively. Compared to the interior-emission band, the stronger exciton-phonon interaction results in a considerable degree of spectral broadening and red-shift for the surface-emission with increasing temperature. In contrast, the (OA)2PbI4 (OA = C8H17NH2) microplates with longer alkyl chains between Pb-I layers, exhibit only one excitonic emission peak, as well as a large exciton-phonon coupling strength. Our work clarifies the influence of exciton-phonon coupling on the excitonic emission of (BA)2PbI4 microplates, and also suggests the intrinsic relationship between the exciton-phonon coupling and the length of organic carbon chain ligands.

A quantitative model of multi-scale single quantum dot blinking

We present a fundamentally new model of colloidal semiconductor quantum dot blinking. The blinking is caused by fluctuations of the non-radiative exciton relaxation rate, induced by variations of the electron–phonon coupling value.

Direct observation of magnetoelastic coupling in a molecular spin qubit: new insights from crystal field neutron scattering data.

Single-molecule magnets are promising candidates for data storage and quantum computing applications. A major barrier to their use is rapid magnetic relaxation and quantum decoherence due to thermal vibrations. Here we report a reanalysis of inelastic neutron scattering (INS) data of the candidate qubit Na9[Ho(W5O18)2]·35D2O, wherein we demonstrate for the first time that magnetic relaxation times and mechanisms can be directly observed as crystal field (CF) peak broadening in INS spectra of a lanthanoid molecular system. The magnetoelastic coupling between the lower energy CF states and phonons (lattice vibrations) is determined by the simultaneous measurement of CF excitations and the phonon density of states, encoded within the same INS experiment. This directly results in the determination of relaxation coupling pathways that occur in this molecule. Such information is invaluable for the further advancement of SMMs and to date has only been obtained from techniques performed in external magnetic fields. Additionally, we determine a relaxation rate of quantum-tunnelling of magnetisation that is consistent with previously measured EPR spectroscopy data.

In-depth understanding the temperature-dependent reversible phase transition in CsPbI3−xBrx perovskites and its associated photophysical properties

Temperature-dependent phase transition of CsPbI3−x Brx perovskite is synchronously observed in a reciprocal space, and its photophysical properties are systematically studied by exploring the carrier–phonon coupling and excitons transport.

Phase segregation affects electron–phonon coupling in perovskite solar cell materials

Phase segregation has been described as a significant factor that limits solar cell efficiency and long-term stability in mixed organic–inorganic halide perovskite materials.

EXAFS evidence for the spin–phonon coupling in the monoclinic PrNiO3 nickelate perovskite

The structural changes in PrNiO3 around the Ni atoms are studied by XAS. The spin–phonon coupling and the softening of the lattice vibrations are observed. EXAFS is suitable for exploring the coupling between the spins and phonons.

First-principles study of the bandgap renormalization and optical property of β-LiGaO2

The β-LiGaO2 with an orthorhombic wurtzite-derived structure is a candidate ultrawide direct-bandgap semiconductor. In this work, using the non-adiabatic Allen–Heine–Cardona approach, we investigate the bandgap renormalization arising from electron–phonon coupling. We find a sizable zero-point motion correction of –0.362 eV to the gap at Γ, which is dominated by the contributions of long-wavelength longitudinal optical phonons. The bandgap of β-LiGaO2 decreases monotonically with increasing temperature. We investigate the optical spectra by comparing the model Bethe–Salpether equation method with the independent-particle approximation. The calculated optical spectra including electron–hole interactions exhibit strong excitonic effects, in qualitative agreement with the experiment. The contributing interband transitions and the binding energy for the excitonic states are analyzed.

Electronic Spin Qubit Candidates Arrayed within Layered Two-Dimensional Polymers

Molecular electronic spin qubits are promising candidates for quantum information science applications because they can be reliably produced and engineered via chemical design. Embedding electronic spin qubits within two-dimensional polymers (2DPs) offers the possibility to systematically engineer inter-qubit interactions while maintaining long coherence times, both of which are prerequisites to their technological utility. Here, we introduce electronic spin qubits into a diamagnetic 2DP by n-doping naphthalene diimide subunits with varying amounts of CoCp2 and analyze their spin densities by quantitative electronic paramagnetic resonance spectroscopy. Low spin densities (e.g., 6.0 × 1012 spins mm-3) enable lengthy spin-lattice (T1) and spin-spin relaxation (T2) times across a range of temperatures, ranging from T1 values of 164 ms at 10 K to 30.2 μs at 296 K and T2 values of 2.36 μs at 10 K to 0.49 μs at 296 K for the lowest spin density sample examined. Higher spin densities and temperatures were both found to diminish T1 times, which we attribute to detrimental cross-relaxation from spin-spin dipolar interactions and spin-phonon coupling, respectively. Higher spin densities decreased T2 times and modulated the T2 temperature dependence. We attribute these differences to the competition between hyperfine and dipolar interactions for electron spin decoherence, with the dominant interaction transitioning from the former to the latter as spin density and temperature increase. Overall, this investigation demonstrates that dispersing electronic spin qubits within layered 2DPs enables chemical control of their inter-qubit interactions and spin decoherence times.

Theoretical Prediction of Superconductivity in Boron Kagome Monolayer: MB3 (M = Be, Ca, Sr) and the Hydrogenated CaB3

Using first-principles calculations, we predict a new type of two-dimensional (2D) boride MB3 (M = Be, Ca, Sr), constituted by boron kagome monolayer and the metal atoms adsorbed above the center of the boron hexagons. The band structures show that the three MB3 compounds are metallic, thus the possible phonon-mediated superconductivity is explored. Based on the Eliashberg equation, for BeB3, CaB3, and SrB3, the calculated electron–phonon coupling constants λ are 0.46, 1.09, and 1.33, and the corresponding superconducting transition temperatures T c are 3.2, 22.4, and 20.9 K, respectively. To explore superconductivity with higher transition temperature, hydrogenation and charge doping are further considered. The hydrogenated CaB3, i.e., HCaB3, is stable, with the enhanced λ of 1.39 and a higher T c of 39.3 K. Moreover, with further hole doping at the concentration of 5.8 × 1011 hole/cm2, the T c of HCaB3 can be further increased to 44.2 K, exceeding the McMillan limit. The predicted MB3 and HCaB3 provide new platforms for investigating 2D superconductivity in boron kagome lattice since superconductivity based on monolayer boron kagome lattice has not been studied before.

Ternary superconducting hydrides stabilized via Th and Ce elements at mild pressures

The discovery of covalent H3S and clathrate structure LaH10 with excellent superconducting critical temperatures at high pressures has facilitated a multitude of research on compressed hydrides. However, their superconducting pressures are too high (generally above 150 GPa), thereby hindering their application. In addition, making room-temperature superconductivity close to ambient pressure in hydrogen-based superconductors is challenging. In this work, we calculated the chemically “pre-compressed” Be-H by heavy metals Th and Ce to stabilize the superconducting phase near ambient pressure. An unprecedented ThBeH8 (CeBeH8) with a “fluorite-type” structure was predicted to be thermodynamically stable above 69 GPa (76 GPa), yielding a Tc of 113 K (28 K) decompressed to 7 GPa (13 GPa) by solving the anisotropic Migdal–Eliashberg equations. Be-H vibrations play a vital role in electron–phonon coupling and structural stability of these ternary hydrides. Our results will guide further experiments toward synthesizing ternary hydride superconductors at mild pressures.