Low-energy Optical Phonons Research Articles

Deciphering Pauling's Third Rule: Uncovering Strong Anharmonicity and Exceptionally Low Thermal Conductivity in TlAgSe for Thermoelectrics.

The elucidation of chemical bonding, coupled with an exploration of the correlated dynamics of constituent atoms, is essential for unravelling the underlying mechanism responsible for low lattice thermal conductivity (κL) exhibited by a crystalline solid, which is essential for thermoelectrics and thermal barrier coatings. In this regard, Pauling's third empirical rule, which deals with the cationic repulsion due to proximity in the face or edge shared polyhedra in a crystal structure, can bring about the lattice instability required to suppress the κL. Here, we demonstrate the presence of such instability in a ternary selenide, TlAgSe, leading to a ultra-low κL of 0.17 W/m.K at 573 K. Our study reveals the instability arising from Ag-Ag repulsion within edge-shared AgSe4 tetrahedra through investigation of the local structure using synchrotron X-ray pair distribution function (PDF) analysis and supported by first-principles density functional theory calculations. We observe correlation between weakening in the Ag and the Tl-sublattice, providing direct experimental evidence of Pauling's third empirical rule. The correlated rattling of Ag and Tl induces a highly anharmonic lattice and low energy optical phonons, resulting in suppressed sound velocity and ultralow κL in TlAgSe. The electronic origin of soft and anharmonic lattice is the presence of filled antibonding states in the valence band near the Fermi level constructed by Ag(4d)-Se(4p) and Tl(6s)-Se(4p) interactions. This work demonstrates that the evidence of dynamic distortion in a crystal lattice is governed by the third empirical rule given by Pauling, which can act as a potential new strategy for diminishing κL in crystalline solids.

Deciphering Pauling's Third Rule: Uncovering Strong Anharmonicity and Exceptionally Low Thermal Conductivity in TlAgSe for Thermoelectrics

AbstractThe elucidation of chemical bonding, coupled with an exploration of the correlated dynamics of constituent atoms, is essential for unravelling the underlying mechanism responsible for low lattice thermal conductivity (κL) exhibited by a crystalline solid, which is essential for thermoelectrics and thermal barrier coatings. In this regard, Pauling's third empirical rule, which deals with the cationic repulsion due to proximity in the face or edge shared polyhedra in a crystal structure, can bring about the lattice instability required to suppress the κL. Here, we demonstrate the presence of such instability in a ternary selenide, TlAgSe, leading to a ultra‐low κL of 0.17 W/m.K at 573 K. Our study reveals the instability arising from Ag−Ag repulsion within edge‐shared AgSe4 tetrahedra through investigation of the local structure using synchrotron X‐ray pair distribution function (PDF) analysis and supported by first‐principles density functional theory calculations. We observe correlation between weakening in the Ag and the Tl‐sublattice, providing direct experimental evidence of Pauling's third empirical rule. The correlated rattling of Ag and Tl induces a highly anharmonic lattice and low energy optical phonons, resulting in suppressed sound velocity and ultralow κL in TlAgSe. The electronic origin of soft and anharmonic lattice is the presence of filled antibonding states in the valence band near the Fermi level constructed by Ag(4d)−Se(4p) and Tl(6s)−Se(4p) interactions. This work demonstrates that the evidence of dynamic distortion in a crystal lattice is governed by the third empirical rule given by Pauling, which can act as a potential new strategy for diminishing κL in crystalline solids.

New Lead-free Hybrid Layered Double Perovskite Halides: Synthesis, Structural Transition and Ultralow Thermal Conductivity.

Hybrid layered double perovskites (HLDPs), representing the two-dimensional manifestation of halide double perovskites, have elicited considerable interest owing to their intricate chemical bonding hierarchy and structural diversity. This intensified interest stems from the diverse options available for selecting alternating octahedral coordinated trivalent [M(III)] and monovalent metal centers [M(I)], along with the distinctive nature of the cationic organic amine located between the layers. Here, we have synthesized three new compounds with general formula (R'/R'')4/2M(III)M(I)Cl8; where R'=C3H7NH3 (i.e. 3N) and R''=NH3C4H8NH3 (i.e. 4N4); M(III)=In3+ or Ru3+; M(I)=Cu+ by simple solution-based acid precipitation method. The structural analysis reveals that (4N4)2CuInCl8 and (4N4)2CuRuCl8 adopt the layered Dion Jacobson (DJ) structure, whereas (3N)4CuInCl8 exhibits layered Ruddlesden Popper (RP) structure. The alternative octahedra within the inorganic layer display distortions and tilting. Three compounds show temperature-dependent structural phase transitions where changes in the staking of inorganic layer, extent of octahedral tilting and reorientation of organic spacers with temperature have been noticed. We have achieved ultralow lattice thermal conductivity (κL) in the HLDPs in the 2 to 300 K range, marking a distinctive feature within the realm of HLDP systems. The RP-HLDP compound, (3N)4CuInCl8, demonstrates anisotropy in κL while measured parallel and perpendicular to layer stacking, showcasing ultralow κL of 0.15 Wm-1K-1 at room temperature, which is one of the lowest values obtained among Pb-free metal halide perovskite. The observed ultralow κL in three new HLDPs is attributed to significant lattice anharmonicity arising from the chemical bonding heterogeneity and soft crystal structure, which resulted in low-energy localized optical phonon modes that suppress heat-carrying acoustic phonons.

Amorphous-Like Ultralow Thermal Transport in Crystalline Argyrodite Cu7PS6.

Due to their amorphous-like ultralow lattice thermal conductivity both below and above the superionic phase transition, crystalline Cu- and Ag-based superionic argyrodites have garnered widespread attention as promising thermoelectric materials. However, despite their intriguing properties, quantifying their lattice thermal conductivities and a comprehensive understanding of the microscopic dynamics that drive these extraordinary properties are still lacking. Here, an integrated experimental and theoretical approach is adopted to reveal the presence of Cu-dominated low-energy optical phonons in the Cu-based argyrodite Cu7PS6. These phonons yield strong acoustic-optical phonon scattering through avoided crossing, enabling ultralow lattice thermal conductivity. The Unified Theory of thermal transport is employed to analyze heat conduction and successfully reproduce the experimental amorphous-like ultralow lattice thermal conductivities, ranging from 0.43 to 0.58Wm-1 K-1, in the temperature range of 100-400 K. The study reveals that the amorphous-like ultralow thermal conductivity of Cu7PS6 stems from a significantly dominant wave-like conduction mechanism. Moreover, the simulations elucidate the wave-like thermal transport mainly results from the contribution of Cu-associated low-energy overlapping optical phonons. This study highlights the crucial role of low-energy and overlapping optical modes in facilitating amorphous-like ultralow thermal transport, providing a thorough understanding of the underlying complex dynamics of argyrodites.

Coupling to octahedral tilts in halide perovskite nanocrystals induces phonon-mediated attractive interactions between excitons

Understanding the origin of electron–phonon coupling in lead halide perovskites is key to interpreting and leveraging their optical and electronic properties. Here we show that photoexcitation drives a reduction of the lead–halide–lead bond angles, a result of deformation potential coupling to low-energy optical phonons. We accomplish this by performing femtosecond-resolved, optical-pump–electron-diffraction-probe measurements to quantify the lattice reorganization occurring as a result of photoexcitation in nanocrystals of FAPbBr3. Our results indicate a stronger coupling in FAPbBr3 than CsPbBr3. We attribute the enhanced coupling in FAPbBr3 to its disordered crystal structure, which persists down to cryogenic temperatures. We find the reorganizations induced by each exciton in a multi-excitonic state constructively interfere, giving rise to a coupling strength that scales quadratically with the exciton number. This superlinear scaling induces phonon-mediated attractive interactions between excitations in lead halide perovskites.

Non-magnetic regenerator material of silver oxide for 4 K cryocoolers

In regenerative cryocoolers, magnetic specific heat is often utilized for heat regeneration at cryogenic temperature, such as below 20 K. Magnetic regenerator materials of rare earth compound which have sufficient specific heat enabled cryocooler to reach below 4 K. However, the magnetic noise emitted from the magnetic materials during the refrigeration cycle affects the performance of noise-sensitive devices. In this study, we propose a non-magnetic regenerator material having “optical phonon degree of freedom” even at cryogenic temperatures, in which silver oxide (Ag2O) is selected. Ag2O decomposes at temperature above 410 K in ambient atmosphere, whereas we succeeded in fabricating a sintered Ag2O bulk and small particles of the size of 0.5 mm with high-density more than 90%. Specific heat measurement down to 100 mK was performed for the sintered bulk sample of Ag2O. Below 10 K, a non-Debye behavior was observed, suggesting the contribution from optical phonon modes. Calculation of the phonon density of state (phDOS) performed by the Evolution Strategy algorithm in addition to the first-principles calculation reveals that phDOS has several distinct peaks at low energies, and the low-energy optical phonons contribute to the non-Debye behavior. The low temperature specific heat of Ag2O enhanced by the optical phonons is larger than conventional non-magnetic regenerator materials when compared in terms of specific heat per volume. Moreover, the calculation of cooling performance of cryocooler using Ag2O particles is found to be reached below 4.2 K. This study shows that non-magnetic material with low temperature specific heat enhanced by optical phonon mode can be used as a regenerator material for regenerative cryocoolers.

Dephasing by optical phonons in GaN defect single-photon emitters

Single-photon defect emitters (SPEs), especially those with magnetically and optically addressable spin states, in technologically mature wide bandgap semiconductors are attractive for realizing integrated platforms for quantum applications. Broadening of the zero phonon line (ZPL) caused by dephasing in solid state SPEs limits the indistinguishability of the emitted photons. Dephasing also limits the use of defect states in quantum information processing, sensing, and metrology. In most defect emitters, such as those in SiC and diamond, interaction with low-energy acoustic phonons determines the temperature dependence of the dephasing rate and the resulting broadening of the ZPL with the temperature obeys a power law. GaN hosts bright and stable single-photon emitters in the 600–700 nm wavelength range with strong ZPLs even at room temperature. In this work, we study the temperature dependence of the ZPL spectra of GaN SPEs integrated with solid immersion lenses with the goal of understanding the relevant dephasing mechanisms. At temperatures below ~ 50 K, the ZPL lineshape is found to be Gaussian and the ZPL linewidth is temperature independent and dominated by spectral diffusion. Above ~ 50 K, the linewidth increases monotonically with the temperature and the lineshape evolves into a Lorentzian. Quite remarkably, the temperature dependence of the linewidth does not follow a power law. We propose a model in which dephasing caused by absorption/emission of optical phonons in an elastic Raman process determines the temperature dependence of the lineshape and the linewidth. Our model explains the temperature dependence of the ZPL linewidth and lineshape in the entire 10–270 K temperature range explored in this work. The ~ 19 meV optical phonon energy extracted by fitting the model to the data matches remarkably well the ~ 18 meV zone center energy of the lowest optical phonon band (E_{2}(low)) in GaN. Our work sheds light on the mechanisms responsible for linewidth broadening in GaN SPEs. Since a low energy optical phonon band (E_{2}(low)) is a feature of most group III–V nitrides with a wurtzite crystal structure, including hBN and AlN, we expect our proposed mechanism to play an important role in defect emitters in these materials as well.

Anharmonic lattice dynamics and the origin of intrinsic ultralow thermal conductivity in AgI materials

Ionic conductors such as AgI with ultralow thermal conductivities $({\ensuremath{\kappa}}_{l})$ are of increasing interest because of their excellent thermoelectric properties. However, the origin of their intrinsic low ${\ensuremath{\kappa}}_{l}$ values remain elusive. In this study, comprehensive theoretical calculations of the lattice dynamics and the thermal transport properties of $\ensuremath{\gamma}\text{\ensuremath{-}}\mathrm{AgI}$ (zinc-blende structure) and $\ensuremath{\beta}\text{\ensuremath{-}}\mathrm{AgI}$ (wurtzite structure) as functions of temperature were carried out based on many-body perturbation theory and phonon Boltzmann transport theory. First, the mean-squared displacements (MSDs) of ${\mathrm{Ag}}^{+}$ were significantly larger than those of ${\mathrm{I}}^{\ensuremath{-}}$ in both $\ensuremath{\gamma}\text{\ensuremath{-}}$ and \ensuremath{\beta}-phases below the order-disorder phase transition temperature $({T}_{\mathrm{c}})$, which led to a characteristic ``rattling'' feature and low-frequency, nearly flat local phonon vibrations. According to our previous work [Xie et al., Phys. Rev. Lett. 125, 245901 (2020)], such nondispersive flat phonon band structures are expected to give rise to four-phonon resonance and result in a dramatic increase in the four-phonon scattering over the conventional three-phonon scattering. For $\ensuremath{\gamma}\text{\ensuremath{-}}\mathrm{AgI}$, similar four-phonon resonance behavior was also discovered for the low-lying transverse acoustic phonon branches, and it was found that their four-phonon scattering rates were an order of magnitude larger than the corresponding three-phonon scattering rates. Considering the four-phonon scattering, the theoretical ${\ensuremath{\kappa}}_{l}$ of $\ensuremath{\gamma}\text{\ensuremath{-}}\mathrm{AgI}$ was predicted to be $\ensuremath{\sim}0.32$ W/m K at 300 K, which was in good agreement with the value deduced from our experiments ($\ensuremath{\sim}0.36$ W/m K at 300 K). Compared to $\ensuremath{\gamma}\text{\ensuremath{-}}\mathrm{AgI}$, the acoustic phonons in $\ensuremath{\beta}\text{\ensuremath{-}}\mathrm{AgI}$ were more dispersive, and they intertwined with low-energy optical phonons at the zone boundaries. It was found that three-phonon resonance became as important as four-phonon resonance for the nearly flat longitudinal phonon band. The theoretical ${\ensuremath{\kappa}}_{l}$ for $\ensuremath{\beta}\text{\ensuremath{-}}\mathrm{AgI}$ was determined to be around $\ensuremath{\sim}0.32$ W/m K at room temperature, closely reproducing our measurement value $\ensuremath{\sim}0.29$ W/m K. Our results for AgI demonstrate the strong quartic anharmonicity in materials characterized by the rattling of weak bonding atoms as well as dispersionless phonon band structures. It is believed that this intimate relationship between the low-${\ensuremath{\kappa}}_{l}$ and flat phonon dispersion can be employed as a good indicator when searching for material systems with ultralow ${\ensuremath{\kappa}}_{l}$ values, e.g., cagelike rattling structures, quasi-two-dimensional structures, and chainlike structures.

Strong Antibonding I (p)-Cu (d) States Lead to Intrinsically Low Thermal Conductivity in CuBiI4.

Chemical bonding present in crystalline solids has a significant impact on how heat moves through a lattice, and with the right chemical tuning, one can achieve extremely low thermal conductivity. The desire for intrinsically low lattice thermal conductivity (κlat) has gained widespread attention in thermoelectrics, in refractories, and nowadays in photovoltaics and optoelectronics. Here we have synthesized a high-quality crystalline ingot of cubic metal halide CuBiI4 and explored its chemical bonding and thermal transport properties. It exhibits an intrinsically ultralow κlat of ∼0.34-0.28 W m-1 K-1 in the temperature range 4-423 K with an Umklapp crystalline peak of 1.82 W m-1 K-1 at 20 K, which is surprisingly lower than other copper-based halide or chalcogenide materials. The crystal orbital Hamilton population analysis shows that antibonding states generated just below the Fermi level (Ef), which arise from robust copper 3d and iodine 5p interactions, cause copper-iodide bond weakening, which leads to reduction of the elastic moduli and softens the lattice, finally to produce extremely low κlat in CuBiI4. The chemical bonding hierarchy with mixed covalent and ionic interactions present in the complex crystal structure generates significant lattice anharmonicity and a low participation ratio in low-lying optical phonon modes originating mostly from localized copper-iodide bond vibrations. We have obtained experimental evidence of these low-lying modes by low-temperature specific heat capacity measurement as well as Raman spectroscopy. The presence of strong p-d antibonding interactions between copper and iodine leads to anharmonic soft crystal lattice which gives rise to low-energy localized optical phonon bands, suppressing the heat-carrying acoustic phonons to steer intrinsically ultralow κlat in CuBiI4.

Soft-Phonon and Charge-Density-Wave Formation in Nematic BaNi2As2

We use diffuse and inelastic x-ray scattering to study the formation of an incommensurate charge-density-wave (I-CDW) in BaNi_{2}As_{2}, a candidate system for charge-driven electronic nematicity. Intense diffuse scattering is observed around the modulation vector of the I-CDW, Q_{I-CDW}. It is already visible at room temperature and collapses into superstructure reflections in the long-range ordered state where a small orthorhombic distortion occurs. A clear dip in the dispersion of a low-energy transverse optical phonon mode is observed around Q_{I-CDW}. The phonon continuously softens upon cooling, ultimately driving the transition to the I-CDW state. The transverse character of the soft-phonon branch elucidates the complex pattern of the I-CDW satellites observed in the current and earlier studies and settles the debated unidirectional nature of the I-CDW. The phonon instability and its reciprocal space position are well captured by our abinitio calculations. These, however, indicate that neither Fermi surface nesting, nor enhanced momentum-dependent electron-phonon coupling can account for the I-CDW formation, demonstrating its unconventional nature.

Crystalline-liquid duality of specific heat in halide perovskite semiconductor

Crystalline-liquid duality in specific heat is observed in lead-free bismuth halide perovskite A3Bi2×9 [A= FA, MA, Cs, and X = I, Br, Cl] semiconductor. All crystals exhibit unusual liquid-like behavior and show substantial deviation from the classical Dulong-Petit law at room temperature. This unusual liquid-like behavior of specific heat is attributed to the dynamic disorder and strong anharmonicity in the soft crystal lattice. The low-temperature specific heat was modeled using the combined Debye-Einstein model and obtained Einstein modes demonstrate strong anharmonic coupling of the low-energy optical modes with acoustic modes resulting in ultrasoft frequency dampening of acoustic phonons. The combination of strong acoustic−optical phonon coupling, soft elastic layered structure, and abundance of low-energy optical phonons results in anomalous thermodynamic specific heat duality in these bismuth-based phonon glass electron crystals. Our study is of fundamental interest in thermodynamics and will help to design novel thermoelectric materials.

Strong Anharmonicity‐Induced Low Thermal Conductivity and High n‐type Mobility in the Topological Insulator Bi1.1Sb0.9Te2S

AbstractIntrinsically low lattice thermal conductivity (κlat) while maintaining the high carrier mobility (μ) is of the utmost importance for thermoelectrics. Topological insulators (TI) can possess high μ due to the metallic surface states. TIs with heavy constituents and layered structure can give rise to high anharmonicity and are expected to show low κlat. Here, we demonstrate that Bi1.1Sb0.9Te2S (BSTS), which is a 3D bulk TI, exhibits ultra‐low κlat of 0.46 Wm−1 K−1 along with high μ of ≈401 cm2 V−1 s−1. Sound velocity measurements and theoretical calculations suggest that chemical bonding hierarchy and high anharmonicity play a crucial role behind such ultra‐low κlat. BSTS possesses low energy optical phonons which strongly couple with the heat carrying acoustic phonons leading to ultra‐low κlat. Further, Cl has been doped at the S site of BSTS which increases the electron concentration and reduces the κlat resulting in a promising n‐type thermoelectric figure of merit (zT) of ≈0.6 at 573 K.

Strong Anharmonicity-Induced Low Thermal Conductivity and High n-type Mobility in the Topological Insulator Bi1.1 Sb0.9 Te2 S.

Intrinsically low lattice thermal conductivity (κlat ) while maintaining the high carrier mobility (μ) is of the utmost importance for thermoelectrics. Topological insulators (TI) can possess high μ due to the metallic surface states. TIs with heavy constituents and layered structure can give rise to high anharmonicity and are expected to show low κlat . Here, we demonstrate that Bi1.1 Sb0.9 Te2 S (BSTS), which is a 3D bulk TI, exhibits ultra-low κlat of 0.46 Wm-1 K-1 along with high μ of ≈401 cm2 V-1 s-1 . Sound velocity measurements and theoretical calculations suggest that chemical bonding hierarchy and high anharmonicity play a crucial role behind such ultra-low κlat . BSTS possesses low energy optical phonons which strongly couple with the heat carrying acoustic phonons leading to ultra-low κlat . Further, Cl has been doped at the S site of BSTS which increases the electron concentration and reduces the κlat resulting in a promising n-type thermoelectric figure of merit (zT) of ≈0.6 at 573 K.

Phonon-assisted carrier cooling in h -BN/graphene van der Waals heterostructures

Being used in optoelectronic devices as ultra-thin conductor-insulator junctions, detailed investigations are needed about how exactly h-BN and graphene hybridize. Here, we present a comprehensive ab initio study of hot carrier dynamics governed by electron-phonon scattering at the h-BN/graphene interface, using graphite (bulk), monolayer and bilayer graphene as benchmark materials. In contrast to monolayer graphene, all multilayer structures possess low-energy optical phonon modes that facilitate carrier thermalization. We find that the h-BN/graphene interface represents an exception with comparatively weak coupling between low-energy optical phonons and electrons. As a consequence, the thermalization bottleneck effect, known from graphene, survives hybridization with h-BN but is substantially reduced in all other bilayer and multilayer cases considered. In addition, we show that the quantum confinement in bilayer graphene does not have a significant influence on the thermalization time compared to graphite and that bilayer graphene can hence serve as a minimal model for the bulk counterpart.

Flat phonon modes driven ultralow thermal conductivities in Sr3AlSb3 and Ba3AlSb3 Zintl compounds

Searching for compounds with intrinsic low lattice thermal conductivity has been proven a successful strategy for achieving high thermoelectric performance. Herein, employing density functional theory calculations combined with electron and phonon Boltzmann transport theories, we report that Sr3AlSb3 and Ba3AlSb3 within the Zintl 3–1–3 compositional family exhibit record low thermal conductivities of 0.78 and 0.55 W/mK at room temperature, respectively. These low thermal conductivities are rooted in low-energy optical phonon modes with strong anharmonicity and the emergence of high-energy flat optical phonon modes with zero contribution to the lattice thermal conductivity. Heavier cationic atoms are found to soften low-lying optical phonon modes, which enhance phonon scattering and, therefore, favor a lower thermal conductivity. These combined characteristics lead to high and balanced figure of merit values around 2.3 for Zintl Ba3AlSb3 at both optimal p-type and n-type doping and high temperature. Our work highlights the important role of flat optical phonon modes on designing promising thermoelectric materials with intrinsic low thermal conductivity.

Anomalous suppressed thermal conductivity in CuInTe2 under pressure

Pressure is an effective way to improve the thermoelectric performance by optimizing the electronic transport property. However, the increase in the thermal conductivity under pressure limits the improvement of thermoelectric properties. Here, based on the first-principles calculation and phonon Boltzmann transport equations, we find the unusual negative relation between the thermal conductivity and pressure in CuInTe2, i.e., its thermal conductivity along the c direction surprisingly decreases by 49% with applying the pressure from 0 to 7.7 GPa. This anomalous phenomenon mainly originates from remarkably enhanced phonon scattering rates under pressure due to dramatically softened transverse acoustic phonons and low energy optical phonons, which provide more phonon–phonon scattering channels. Our findings reveal the mechanism of decrease in the lattice thermal conductivity under pressure, which could be used for further improvement in the thermoelectric performance synergetically in the presence of pressure.

Significant phase-space-driven thermal transport suppression in BC8 silicon

The BC8 silicon allotrope has a lattice thermal conductivity 1–2 orders of magnitude lower than that of diamond-cubic silicon. In the current work, the phonon density of states, phonon dispersion, and lattice thermal conductivity are investigated by inelastic neutron scattering measurements and first-principles calculations. Flat phonon bands are found to play a critical role in the reduction of lattice thermal conductivity in BC8–Si. Such bands in the low-energy range enhance the phonon scattering between acoustic and low-energy optical phonons, while bands in the intermediate-energy range act as a scattering bridge between the high- and low-energy optical phonons. They significantly enlarge the phonon-phonon scattering phase space and reduces the lattice thermal conductivity in this novel silicon allotrope. This work provides insights into the significant reduction of the lattice thermal conductivity in BC8–Si, thus expanding the understanding of novel silicon allotropes and their development for electronic devices.

Ultrafast photo-induced phonon hardening due to Pauli blocking in MAPbI3 single-crystal and polycrystalline perovskites

Metal-halide perovskite semiconductors have attracted intense interest over the past decade, particularly for applications in photovoltaics. Low-energy optical phonons combined with significant crystal anharmonicity play an important role in charge-carrier cooling and scattering in these materials, strongly affecting their optoelectronic properties. We have observed optical phonons associated with Pb–I stretching in both MAPbI3 single crystals and polycrystalline thin films as a function of temperature by measuring their terahertz conductivity spectra with and without photoexcitation. An anomalous bond hardening was observed under above-bandgap illumination for both single-crystal and polycrystalline MAPbI3. First-principles calculations reproduced this photo-induced bond hardening and identified a related lattice contraction (photostriction), with the mechanism revealed as Pauli blocking. For single-crystal MAPbI3, phonon lifetimes were significantly longer and phonon frequencies shifted less with temperature, compared with polycrystalline MAPbI3. We attribute these differences to increased crystalline disorder, associated with grain boundaries and strain in the polycrystalline MAPbI3. Thus we provide fundamental insight into the photoexcitation and electron–phonon coupling in MAPbI3.

Impact of dimensional crossover on phonon transport in van der Waals materials: A case study of graphite and graphene

Using first-principles modeling we investigate how phonon transport evolves in layered/van der Waals materials when going from 3D to 2D, or vice versa, by gradually pulling apart the atomic layers in graphite to form graphene. Focus is placed on identifying the features impacting thermal conductivity that are likely shared with other layered materials. The thermal conductivity $\ensuremath{\kappa}$ of graphite is found to be lower than that of graphene in large part due to changes in the phonon dispersion driven by van der Waals coupling. Specifically, as the atomic layers are brought closer together, the acoustic flexural phonons in graphene form low-energy optical flexural phonons in graphite that possess lower in-plane velocities, density of states, and phonon occupation, thus reducing $\ensuremath{\kappa}$. Similar dispersion changes, and impact on thermal conductivity, can be expected in other van der Waals materials when transitioning from 2D to 3D. Our findings also indicate that the selection rules in graphene, which reduce phonon-phonon scattering and contribute to its large $\ensuremath{\kappa}$, effectively hold as the atomic layers are brought together to form graphite. While the selection rules do not strictly apply to graphite, in practice reduced scattering is observed due in part to the weak interlayer coupling. This suggests that some bulk van der Waals materials may have lower phonon-phonon scattering rates than other nonlayered bulk materials.

Reinvestigation of crystal symmetry and fluctuations in La2CuO4

New surprises continue to be revealed about La$_2$CuO$_4$, the parent compound of the original cuprate superconductor. Here we present neutron scattering evidence that the structural symmetry is lower than commonly assumed. The static distortion results in anisotropic Cu-O bonds within the CuO$_2$ planes; such anisotropy is relevant to pinning charge stripes in hole-doped samples. Associated with the extra structural modulation is a soft phonon mode. If this phonon were to soften completely, the resulting change in CuO$_6$ octahedral tilts would lead to weak ferromagnetism. Hence, we suggest that this mode may be the "chiral" phonon inferred from recent studies of the thermal Hall effect. We also note the absence of interaction between the antiferromagnetic spin waves and low-energy optical phonons, in contrast to what is observed in hole-doped samples.