Infrared-active Phonon Modes Research Articles

Revealing lattice and photocarrier dynamics of high-quality MAPbBr3 single crystals by far infrared reflection and surface photovoltage spectroscopy

Hybrid organic-inorganic lead halide perovskite materials show great promise in a number of optoelectronic applications, including solar cells, light emitting diodes, and photodetectors. Understanding their intrinsic material properties is critical to enhancing device performance and enabling innovative material and device designs. Here, we study lattice dynamics using far-infrared (FIR) reflectance and photogenerated carrier dynamics using surface photovoltage (SPV) measurements on high-quality methylammonium lead bromide (MAPbBr3) single crystals. FIR reflectance shows three coherent infrared-active phonon modes between 40 and 200 cm−1 that result in reststrahlen bands with much higher peak reflectance than has been previously reported. The phonon mode strength and damping are comparable to classical oxide perovskite single crystals. However, the effects of defects on photogenerated carrier recombination are still evident in SPV measurements. By performing SPV over different spectral ranges, we are able to separate the effects of surface and bulk defects on the recombination dynamics of photogenerated charge carriers. We further apply SPV measurements to obtain the minority carrier (electron) diffusion length for the MAPbBr3 crystal. This study demonstrates that both FIR reflectance and SPV measurements provide useful information on the electromagnetic response properties of halide perovskite single crystals.

Drude and Kukharskii mobility of doped semiconductors extracted from Fourier-transform infrared ellipsometry spectra

The factorized plasmon-phonon polariton description of the infrared dielectric function is generalized to include an additional factor to account for the effects of interband electronic transitions. This new formalism is superior to the usual Drude–Lorentz summation of independent oscillators, especially in materials with large transverse-longitudinal optical phonon splittings, multiple infrared-active phonon modes, or high concentrations of free carriers, if a broadband description of the dielectric function from the far-infrared to the vacuum-ultraviolet spectral region is desired. After a careful comparison of both approaches, the factorized description is applied to the dielectric function of undoped and doped semiconductors (GaAs, GaSb, and InAs) and metal oxides from 0.03 to 9.0 eV. Specifically, the authors find that both descriptions of the far-infrared dielectric function yield the same carrier density and mobility, at least for a single species of carriers. To achieve valid results for moderately high doping concentrations, measurements to lower energies would be helpful.

Quantum nonlinear phononics route towards nonequilibrium materials engineering: Melting dynamics of a ferrielectric charge density wave

Negative nonlinear electron-phonon coupling involving an infrared-active phonon mode can lead to an instability towards the formation of a polar lattice distortion with ferrielectric (FE) moments accompanied by an electronic charge-density wave (CDW). Analyzing a small model system in and out of thermal equilibrium, we investigate the FE-CDW and its melting dynamics following an ultrashort laser pulse that drives the ionic dipoles. We observe nonequilibrium coherent phonon amplitude mode oscillations that soften towards the transition to the normal phase. Our case study serves as a first step towards a microscopic understanding of quantum nonlinear phononics as a basis for nonequilibrium control in quantum materials.

Narrowband terahertz radiation by impulsive stimulated Raman scattering in an above-room-temperature organic ferroelectric benzimidazole

We observe a terahertz radiation from a hydrogen-bonded organic molecular ferroelectric 5,6-dichloro-2-methylbenzimidazole excited by a femtosecond laser pulse at room temperature. The emitted terahertz wave consists of three oscillatory components, the frequencies of which agree with those of Raman- and infrared-active phonon modes. This suggests that the terahertz radiation is attributed to polarization modulations by infrared-active phonons excited via the impulsive stimulated Raman scattering processes. By taking into account the Raman polarizability tensor and dipole-moment for each phonon, we succeeded in reproducing not only the spectrum of the terahertz radiation, but also its time characteristic. The analysis method is discussed in detail. Our result provides a new way for the light-induced terahertz radiation in organic ferroelectrics.

Nonlinear phononic control and emergent magnetism in Mott insulating titanates

Optical control of structure-driven magnetic order offers a platform for magneto-optical terahertz devices. We control the magnetic phases of $d^1$ Mott insulating titanates using nonlinear phononics to transiently perturb the atomic structure based on density functional theory (DFT) simulations and solutions to a lattice Hamiltonian including nonlinear multi-mode interactions. We show that magnetism is tuned by indirect excitation of a Raman-active phonon mode, which affects the amplitude of the TiO$_6$ octahedral rotations that couple to static Ti--O Jahn-Teller distortions, through infrared-active phonon modes of LaTiO$_3$ and YTiO$_3$. The mode excitation reduces the rotational angle, driving a magnetic phase transition from ferromagnetic (FM) to $A$-type antiferromagnetic (AFM), and finally a $G$-type AFM state. This novel $A$-AFM state arises from a change in the exchange interactions and is absent in the bulk equilibrium phase diagram, but it emerges as a dynamically accessible optically induced state under multi-mode excitations. Our work shows nonlinear phononic coupling is able to stabilize phases inaccessible to static chemical pressure or epitaxial strain.

Terahertz transmittance and metal-insulator phase transition properties of M2 phase VO2 films induced by Cr doping

In this work, we investigate the terahertz transmittance and metal-insulator phase transition properties of M2 phase VO2 films induced by Cr doping. Firstly, Cr-doped VO2 films were successfully produced on silicon substrates using DC reactive magnetron sputtering and then fully characterized by XRD, XPS, Raman shift and SEM tests. These results demonstrate the formation of M2 phase and the effect of Cr doping on composition, crystal structure and surface morphology of VO2 films. Compared with undoped VO2, Cr doping significantly enhances the amplitude modulation in the frequency of phonon-absorption peaks by the suppression of infrared-active phonon modes. More concretely, the amplitude modulation is largely increased from 29.6% to 39.0% at 8.25 THz and from 24.1% to 37.1% at 9.33 THz, respectively. This enhancement strongly contributes to the development of VO2-based devices in high THz range. In addition, Cr doped VO2 films exhibit outstanding metal-insulator phase transition properties with very narrower hysteresis width (8.0 °C) as well as smaller transition sharpness (3.4 °C) than undoped film, which is ascribed to the increase of heterogeneous nucleation site density and the transformation of crystal structure from M1 phase to M2 phase, respectively. This work indicates that VO2 films with suitable Cr doping concentration have great potential for THz modulation applications.

Optical study of Dirac fermions and related phonon anomalies in the antiferromagnetic compound CaFeAsF

We performed optical studies on CaFeAsF single crystals, a parent compound of the 1111-type iron-based superconductors that undergoes a structural phase transition from tetragonal to orthorhombic at $T_s$ = 121 K and a magnetic one to a spin density wave (SDW) state at $T_N$ = 110 K. In the low temperature optical conductivity spectrum, after the subtraction of a narrow Drude peak, we observe a pronounced singularity around 300 cm$^{-1}$ that separates two regions of quasilinear conductivity. We outline that these characteristic absorption features are signatures of Dirac fermions, similar to what was previously reported for the BaFe$_2$As$_2$ system [1]. In support of this interpretation, we show that for the latter system this singular feature disappears rapidly upon electron and hole doping, as expected if it arises from a van Hove singularity in-between two Dirac cones. Finally, we show that one of the infrared-active phonon modes (the Fe-As mode at 250 cm$^{-1}$) develops a strongly asymmetric line shape in the SDW state and note that this behaviour can be explained in terms of a strong coupling with the Dirac fermions.

Ordinary dielectric function of corundumlike α−Ga2O3 from 40 meV to 20 eV

The linear optical response of metastable $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ is investigated by spectroscopic ellipsometry. We determine the ordinary dielectric function from lattice vibrations up to the vacuum ultraviolet spectral range at room temperature for a sample with a $(0001)$ surface. Three out of four ${E}_{\mathrm{u}}$ infrared-active phonon modes are unambiguously determined, and their frequencies are in good agreement with density functional theory calculations. The dispersion of the refractive index in the visible and ultraviolet part of the spectrum is determined. High-energy interband transitions are characterized up to $20\phantom{\rule{0.222222em}{0ex}}\mathrm{eV}$. By comparison with the optical response of $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Al}}_{2}{\mathrm{O}}_{3}$ and with theoretical results, a tentative assignment of interband transitions is proposed.

Optical conductivity in multiferroic GaV4S8 and GeV4S8 : Phonons and electronic transitions

We report on optical spectroscopy on the lacunar spinels GaV$_4$S$_8$ and GeV$_4$S$_8$ in the spectral range from 100 to 23000 cm$^{-1}$ and for temperatures from 5 to 300 K. These multiferroic spinel systems reveal Jahn-Teller driven ferroelectricity and complex magnetic order at low temperatures. We study the infrared-active phonon modes and the low-lying electronic excitations in the cubic high-temperature phase, as well as in the orbitally and in the magnetically ordered low-temperature phases. We compare the phonon modes in these two compounds, which undergo different symmetry-lowering Jahn-Teller transitions into ferroelectric and orbitally ordered phases, and exhibit different magnetic ground states. We follow the splitting of the phonon modes at the structural phase transition and detect additional splittings at the onset of antiferromagnetic order in GeV$_4$S$_8$. We observe electronic transitions within the $d$-derived bands of the V$_4$ clusters and document a significant influence of the structural and magnetic phase transitions on the narrow electronic band gaps.

Light-enhanced electron-phonon coupling from nonlinear electron-phonon coupling

We investigate an exact nonequilibrium solution of a two-site electron-phonon model, where an infrared-active phonon that is nonlinearly coupled to the electrons is driven by a laser field. The time-resolved electronic spectrum shows coherence-incoherence spectral weight transfer, a clear signature of light-enhanced electron-phonon coupling. The present study is motivated by recent evidence for enhanced electron-phonon coupling in pump-probe TeraHertz and angle-resolved photoemission spectroscopy in bilayer graphene when driven near resonance with an infrared-active phonon mode [E.~Pomarico et al., Phys.~Rev.~B 95, 024304 (2017)], and by a theoretical study suggesting that transient electronic attraction arises from nonlinear electron-phonon coupling [D.~M.~Kennes et al., Nature Physics (2017), 10.1038/nphys4024]. We show that a linear scaling of light-enhanced electron-phonon coupling with the pump field intensity emerges, in accordance with a time-nonlocal self-energy based on a mean-field decoupling using quasi-classical phonon coherent states. Finally we demonstrate that this leads to enhanced double occupancies in accordance with an effective electron-electron attraction. Our results suggest that materials with strong phonon nonlinearities provide an ideal playground to achieve light-enhanced electron-phonon coupling and possibly light-induced superconductivity.

Midinfrared-light-induced ferroelectricity in oxide paraelectrics via nonlinear phononics

I show that a nonequilibrium paraelectric to ferroelectric transition can be induced using midinfrared pulses. This relies on a quartic $lQ_{\textrm{l$_z$}}^2Q_{\textrm{h$_x$}}^2$ coupling between the lowest ($Q_{\textrm{l$_z$}}$) and highest ($Q_{\textrm{h$_x$}}$) frequency infrared-active phonon modes of a paraelectric material. Density functional calculations show that the coupling constant $l$ is negative, which causes a softening of the $Q_{\textrm{l$_z$}}$ mode when the $Q_{\textrm{h$_x$}}$ mode is externally pumped. A rectification along the $Q_{\textrm{l$_z$}}$ coordinate that stabilizes the nonequilibrium ferroelectric state occurs only above a critical threshold for the electric field of the pump pulse, demonstrating that this is a nonperturbative phenomenon. A first principles calculation of the coupling between light and the $Q_{\textrm{h$_x$}}$ mode shows that ferroelectricity can be induced in the representative case of strained KTaO$_3$ by a midinfrared pulse with a peak electric field of 17 MV cm$^{-1}$ and duration of 2 ps. Furthermore, other odd-order nonlinear couplings make it possible to arbitrarily switch off the light-induced ferroelectric state, making this technique feasible for all-optic devices.

Phonon and Defect Induced Transparencies in the Mid-Infrared Spectrum of Grafted Single Layer Graphene

The Drude-like response of graphene in the terahertz and infrared region of the spectrum has made it attractive for optoelectronic applications in this range, because the response can be controlled by gating and doping. [1] Graphene infrared response can further be tailored for photonics and plasmonics, as the patterned material harbors low energy plasmon modes. [2] However, the infrared spectrum of pristine single layer graphene (SLG) is monotonous; in contrast to Raman, there are no infrared-active phonon modes, while bilayer graphene displays a Fano resonance in the infrared at ~1600 cm-1. [3] In a first time, we show experimentally that grafting SLG with halogenophenyl moieties induces optical transparencies at two specific energies: 1250 and 1600 cm-1 [4], in close similarity to the bands that can also be observed in carbon nanotubes as Fano resonances. [5] Unlike bands caused by the absorption of light by vibrational modes, these antiresonances show a decrease of the absorbance, an optical transparency effect. Moreover, we show that the amplitude of the transparencies can be modulated by changing the charge carrier density through doping, and by the defect density through controlled grafting. In as second time, we will present a theory based on quantum mechanics to calculate the optical conductivity of grafted SLG. [4] The model puts into play phonon modes with momenta different from Γ that can be addressed through scattering on defects. Numerical simulations reproduce the experimental data with good agreement. The theory also captures the dependence of the signal on charge carrier density and defect density. Our findings bring a new understanding for the physics behind the infrared activity of nanostructures, while opening new capabilities for tailoring the optical spectrum of nanomaterials.

Chemical pressure effect in Sm and La substituted ferroelectric BiFeO3 thin films: Insights from infrared spectroscopy

We investigate the effects of Sm and La substitution in ferroelectric BiFeO3 thin films on the lattice dynamics by infrared reflection measurements at room temperature. The frequencies of the infrared-active phonon modes are studied as a function of Sm and La content in Bi1–x(Sm,La)xFeO3 composition spread films in the range from x = 0 up to x = 0.25, grown on SrTiO3 substrates by pulsed laser deposition. Substitution of the Bi3+ ions with small Sm3+ ions leads to the appearance of a new phase above x ≈ 0.09 coexisting with the ferroelectric BiFeO3 phase up to x ≈ 0.19. In contrast, for the substitution of Bi3+ ions with La3+ ions of similar size a continuous transition from the original BiFeO3 phase to a new phase takes place. In both cases, we assign the new phase to the paraelectric, orthorhombic phase. These findings are discussed in terms of the morphotropic phase boundary in Sm-doped BiFeO3 around x = 0.14 with a phase coexistence, which was suggested as the origin for enhanced piezoelectric properties.

Ideal strength, phonon stability and thermodynamics of the CrB-type CaX IV (X IV = Si, Ge, and Sn) binary compounds

Abstract We reported a theoretical investigation of the ideal strengths, dynamical and thermodynamic properties of the CrB-type CaXIV (XIV = Si, Ge, and Sn) alkaline-earth metal compounds by employing density functional theory (DFT) and density functional perturbation theory (DFPT). The calculated ideal tensile strengths have the sequence of CaSi > CaGe > CaSn for these intermetallic compounds along the [100], [010], and [001] high-symmetry lines. The present results mean the tensile and shear abilities of CaSi are best, followed by CaGe and CaSn calcium-based compounds. Based on the linear response method within DFPT, the full phonon dispersion curves and the phonon densities of state of the CaXIV (XIV = Si, Ge, and Sn) intermetallic compounds are investigated systematically. Furthermore, the Raman-active and Infrared-active phonon modes at Г point of Brillouin Zone (BZ) center are assigned combining with the point group theory. Our calculated results indicate that three calcium-based compounds are all dynamically stable at ambient conditions. Additionally, within the calculated vibration phonon densities of states, the thermo-physical properties of three calcium-based compounds such as the vibration internal energy, Helmholtz free energy, the lattice entropy and the lattice heat capacity have been also obtained. These investigations serve for new references for further synthesis of various calcium-based alkaline-earth metal compounds.

Al4SiC4 vibrational properties: density functional theory calculations compared to Raman and infrared spectroscopy measurements

Al4SiC4 is a new semiconductor with numerous potential technological applications. We report here the first thorough experimental Raman and Infrared (IR) investigation of vibrational properties of Al4SiC4 single crystals grown by high temperature solution growth method. The experimental results are compared with the full theoretical analysis of vibrational properties based on Density Functional Theory calculations that are revisited here. We have obtained a good agreement between the experimental and calculated Raman phonon modes, and this allowed the symmetry assignment of all the measured Raman modes. We have revisited the Density Functional Theory calculation of the IR active phonon modes and our results for LO‐TO splitting indicate a substantial decrease of ΔωLO − TO compared with the previous reported calculation. Moreover, most of the IR modes have been symmetry assigned from the comparison of the experimental IR spectra with the corresponding Raman spectra and the Al4SiC4 calculated phonon modes. Copyright © 2017 John Wiley & Sons, Ltd.

Anisotropy of infrared-active phonon modes in the monodomain state of tetragonal SrTiO3 (110)

With infrared and terahertz ellipsometry we investigated the anisotropy of the infrared active phonon modes in SrTiO3 (110) single crystals in the tetragonal state below the so-called antiferrodistortive transition at T* = 105 K. In particular, we show that the anisotropy of the oscillator strength of the so-called R-mode, which becomes weakly infrared active below T*, is a valuable indicator for the orientation of the structural domains. Our results reveal that a mono-domain state with the tetragonal axis (c-axis) parallel to the [001] direction can be created by applying a moderate uniaxial stress of about 2.3 MPa along the [1-10] direction (with a mechanical clamp). The resulting, intrinsic splitting of the infrared-active phonon modes is reported.

Vibrational and dielectric properties of AlN: A first-principles study

The vibrational and dielectric properties of zinc-blende aluminum nitride (B3-AlN) were investigated within the framework of density functional perturbation theory. The phonon frequencies at the Brillouin zone center, the static dielectric constant, and the electronic dielectric constant were reported. The results of our studies were analyzed and discussed with respect to the available experimental and theoretical data. We found that the generalized gradient approximation potential resulted in more accurate phonon frequencies than those obtained using the local density approximation potential. The contributions to the static dielectric tensor due to purely electronic screening and infrared-active phonon modes were analyzed. The phonon, dielectric, refractive index, extinction coefficient and infrared reflectance spectra of B3-AlN were reported, and their values suggest that B3-AlN has good transmission properties in the spectral range above 1000cm−1 and below 400cm−1.

THz Transmittance and Electrical Properties Tuning across IMT in Vanadium Dioxide Films by Al Doping.

Due to the insulator-metal transition (IMT) performance covering the full terahertz (THz) band, VO2 films were extensively investigated as an excellent candidate for modulating, switching, and memory devices. However, some remarkable absorption peaks owing to the infrared-active phonon modes suppressed the films' modulation ability and restricted the films' application in high THz frequency. Here we prepared Al-doped VO2 films on (111) directional silicon substrate, which rapidly counteracted the absorption peak and exhibited widely modulating properties. Al dopants introduced into the films brought a significant shift to high frequency in Raman spectra. The result was attributed to the effect of modifying VO2 crystal, leading the V-O bond to be strained more intensively, contracting the distance of the V-V dimers. All the Raman results indicated an oxidation effect by Al doping. However, the XPS results showed a valence reduction of the vanadium element, which was caused by the valence difference between V and Al atoms. In addition to the surface morphology characterization, the IMT properties of the shrinkage of hysteresis width and resistance variations in both electrical and THz optical aspects have been systemically analyzed. An additional difference is that the temperature of the optical transition behaves lower than the electrical transition observed, which resulted from the mechanism of transition propagation and boundary barriers.

Piezoelectricity of Functionalized Graphene: A Quantum-Mechanical Rationalization

A large out-of-plane piezoelectricity can be induced in graphene by carbon substitution. Several simple substitutions are considered where C atoms are replaced by heavier group-IV elements (Si, Ge, and Sn). A more complex functionalization (namely, pyrrolic N-doped graphene) is also investigated where different functional groups, such as F, Cl, H3C, and H2N, are studied. Piezoelectric and elastic response properties of all systems are determined quantum mechanically at the ab initio level of theory. A rationalization of the physical and chemical parameters which most affect the out-of-plane piezoelectricity of functionalized graphene is reported, which reveals the dominant character of the nuclear over electronic contribution. The combination of an out-of-plane symmetry-breaking defect and a soft infrared-active phonon mode, with a large cell-deformation coupling, is shown to constitute the necessary prerequisite to induce a large out-of-plane piezoelectric response into functionalized graphene.

Infrared probe of spin-phonon coupling in antiferromagnetic honeycomb lattice compound Li2MnO3

We investigated temperature-dependent infrared-active phonon modes of honeycomb Li2MnO3 which shows an antiferromagnetic transition at TN = 36 K. In the far-infrared frequency region, we observed fourteen phonon modes. We obtained the temperature dependence of each phonon mode from the analysis of optical conductivity spectra by using the Lorentz and the Fano-type oscillator models. We found that the resonance frequencies of nine phonon modes showed an anomalous behavior near TN that should be attributed to the spin-phonon coupling. We calculated the magnitude of the spin-phonon coupling constant from the shift in the resonance frequencies of the phonon modes below TN. Our results suggest that Li2MnO3 is weakly frustrated and that spin-phonon coupling plays a role in antiferromagnetic ordering.