Light-induced ultrafast phase transitions in VO2 thin film

Vanadium dioxide shows a passive and reversible change from a monoclinic insulator phase to a metallic tetragonal rutile structure when the sample temperature is close to and over 68 °C. As a kind of functional material, VO₂ thin films deposited on fused quartz substrates were successfully prepared by the pulsed laser deposition (PLD) technique. With laser illumination at 400 nm on the obtained films, the phase transition (PT) occurred. The observed light-induced PT was as fast as the laser pulse duration of 100 fs. Using a femtosecond laser system, the relaxation processes in VO₂ were studied by optical pump-probe spectroscopy. Upon a laser excitation an instantaneous response in the transient reflectivity and transmission was observed followed by a relatively longer relaxation process. The alteration is dependent on pump power. The change in reflectance reached a maximum value at a pump pulse energy between 7 and 14 mJ/cm². The observed PT is associated with the optical interband transition in VO₂ thin film. It suggests that with a pump laser illuminating on the film, excitation from the d_θ,? - state of valence band to the unoccupied excited mixed d_θ,?-π* - state of the conduction band in the insulator phase occurs, followed by a resonant transition to an unoccupied excited mixed d_θ,?-π* - state of the metallic phase band.     

Optical investigations of polycrystalline Mg1−xB2 near metal-insulator transition

We measured reflectivity spectra of polycrystalline Mg_1−xB₂ samples, which show a metal-insulator transition with x. After performing the Kramers-Kronig analysis, the obtained optical conductivity spectra σ(ω) of MgB₂ show a narrow Drude peak in the far-infrared region and a broad peak in the mid-infrared region. As x increases, the spectral weight of the Drude peak is strongly suppressed and that of the broad peak becomes enhanced a little. The existence of the broad mid-infrared peak in the insulating sample suggests that this peak might not be related to the free carriers in MgB₂. In the far-infrared region, we also observe that the low energy dielectric constant of Mg_1−xB₂ diverges near the metal-insulator phase boundary (i.e. x=0.08). This result implies the possibility of a phase separation and a percolative metal-insulator transition in Mg_1−xB₂.     

Evolution of the d∥ band across the metal-insulator transition in VO2

We studied the evolution of the electronic structure of VO₂ across the metal-insulator transition. The electronic structure was calculated using the standard TB-LMTO-ASA method. The calculated DOS was compared to previous photoemission and X-ray absorption spectra. The electronic structure is discussed in terms of the usual molecular-orbital scheme. In the metallic phase, the d_∥ band appears at the bottom of the V 3d bands and crosses the Fermi level. In the insulating phase, the d_∥ band is split around 2 eV opening a pseudo band gap at the Fermi level. The largest effect of the splitting appears in the unoccupied part of the d_∥ band. The calculated value of the splitting accounts for 77% of the experimental value, 2.6 eV. The results suggest that electron-lattice interaction seems to be the dominant factor in the splitting of the d_∥ band.     

Study of photo-induced phenomena in VO2 by terahertz pump-probe spectroscopy

The ultrafast terahertz response to the photoexcitation in vanadium dioxide was investigated using the optical-pump terahertz-probe technique at room temperature. The optical excitation at 790 nm induced an ultrafast decrease of the transmittance of the terahertz pulses corresponding to the increase of the electronic conductivity within 0.7 ps, and then the transmittance decreases gradually up to 100 ps. This two-step behavior is very similar to the previous reports of the time resolved X-ray and electron diffractions. This fact indicates that the increase of the electronic conductivity and the change of the lattice structure proceed in parallel, and the photo-induced insulator-metal phase transition is of the Peierls type.     

Phase diagram of electron-hole systems: Interplay between exciton Mott transition and quantum pair condensation

Quasi-thermal-equilibrium states of electron-hole (e-h) systems in photoexcited insulators are studied from a theoretical viewpoint, stressing the exciton Bose-Einstein condensation (BEC), the e-h BCS-type pair-condensed state, and the exciton Mott transition between an insulating exciton/biexciton gas phase and a metallic e-h plasma phase. We determine the quasi-equilibrium phase diagram of the e-h system at zero and finite temperatures with applying the dynamical mean-field theory (DMFT) to the e-h Hubbard model with both repulsive and attractive on-site interactions. Effects of inter-site interactions on the exciton Mott transition are also clarified with applying the extended DMFT to the extended e-h Hubbard model.     

Epitaxial strain effects on the metal-insulator transition in V2O3 thin films

Effects of epitaxial stress on the metal-insulator transition of V₂O₃ have been studied for in the form of epitaxial thin films grown on α-Al₂O₃ (0001) and LiTaO₃ (0001) substrates. A metallic phase is stabilized down to 2 K in the V₂O₃ thin film on α-Al₂O₃ (0001), where the a-axis is compressed by 4% owing to large epitaxial stress. On the other hand, the transition temperature T_MI is raised by 20 K from the value of 170 K in bulk samples in the film on LiTaO₃ (0001), where the a-axis is expanded. These results suggest an intimate relationship between the a-axis length and T_MI in V₂O₃. The conductivity of the metallic ultrathin films shows logarithmic temperature dependence below 20 K, probably due to the Anderson localization in two-dimensional systems.     

Thickness dependence of electroresistance in La0.67Ca0.33MnO3 epitaxial films

The electroresistance (ER) of La_0.67Ca_0.33MnO₃ (LCMO) epitaxial thin films with different thicknesses was studied. For the 110 nm thick LCMO film, its ER shows a maximum at T_p, where the resistance shows a peak, and decreases to zero at lower temperatures. While for the 30 nm thick LCMO film, its ER is remarkable in a wide temperature range. Another interesting observation in this work is that the electric current can tune the magnetoresistance of the ultrathin LCMO thin film. The results were discussed by considering the coexistence of ferromagnetic metallic phase with the charge ordered phase, and the variation of the phase separation with film thickness and electric current. This work also demonstrates that electric current can tune the magnetoresistance of the manganites, which is helpful for their applications.     

Electric current-induced giant electroresistance in epitaxial La0.67Sr0.33MnO3 thin films

The electronic transport behavior of La_0.67Sr_0.33MnO₃ epitaxial thin films with different thicknesses has been investigated under various applied DC currents. The 20 and 70 nm thick films show a giant negative electroresistance (ER). In contrast, the films with 100 nm thickness show unusual giant positive ER, which can reach 30% with the current density of 1.8×10⁸ A/cm² at room temperature. It is interesting that the electric current can also change the magnetoresistance of the films. The results were explained by considering the spin polarized current induced increase of ferromagnetic metallic phase and current-induced lattice distortion via electron wind force under high current density.     

Scintillation and anomalous emission in elpasolite Cs2LiLuCl6:Ce

The luminescence and scintillation properties of Cs₂LiLuCl₆:0.5%Ce³⁺ are presented. Special attention is devoted to a 9.4 ns fast emission at 275 nm that can only be excited via the highest cubic field 5d_e state of Ce. Contrary to Cs₃LuCl₆ and Cs₂LiYCl₆, where the same type of fast emission was observed, the emission in Cs₂LiLuCl₆ is still observed at room temperature. Assuming that the 5d_e state is located inside the host conduction band (CB), we propose that the emission originates from a mixed state at or just below the bottom of the CB and ends at the 4f ground state of Ce³⁺. To proof this model we studied the thermal quenching of the anomalous luminescence and performed X-ray photoelectron spectroscopy. A model for a temperature-activated energy transfer from the anomalous state to the lowest 5d_t excited state of Ce³⁺ explains most of the results. Besides the 275 nm emission, the material shows 5d_t-4f Ce³⁺ emission at 370 and 406 nm and 2 ns fast core-valence luminescence when excited with 16-22 eV photons. The scintillation properties of Cs₂LiLuCl₆:Ce are briefly discussed.     

Infrared optical properties of Ba(Zr0.20Ti0.80)O3 and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.20 and 0.30) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate by sol-gel method. X-ray diffraction patterns show that the thin films have a good crystallinity. Optical properties of the films in the wavelength range of 2.5-12 μm are studied by infrared spectroscopic ellipsometry (IRSE). The optical constants of the BZT thin films are determined by fitting the IRSE data using a classical dispersion formula. As the wavelength increases, the refractive index decreases, while the extinction coefficients increase. The effective static ionic charges are derived, which are smaller than that in a purely ionic material for the BZT thin films.     

Cr-doping effect on the structural, magnetic, transport properties and Raman spectroscopy of La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 perovskites

A series of the double-doping samples La_(2+x)/3Sr_(1−4x)/3Mn_1−xCr_xO₃ (0?x?0.25) with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 have been fabricated. The structural, magnetic, transport properties and Raman spectroscopy have been investigated, and no apparent crystal structure change is introduced by Cr doping up to x=0.25. But the Curie temperature T_C and metal-insulator transition temperature T_MI are strongly affected by Cr substitution. The room temperature Raman spectra start exhibiting some new features following the increasing concentration of Cr substitutions. Moreover, it is worth noting that the frequency of the A_1g phonon mode can also be well correlated with the A-site mismatch effect (σ²), which is influenced mainly by the variety of the Sr content.     

A Brillouin study of the temperature-dependence of the acoustic modes across the insulator-metal transitions in V2O3 and Cr-doped V2O3

Brillouin scattering studies have been carried out on high-quality single crystals of undoped and 0.9% Cr-doped V₂O₃. The observed modes in both the samples at ∼12 and ∼60 GHz are associated with the surface Rayleigh wave (SRW) and bulk acoustic wave (BAW), respectively. In the undoped sample, the mode frequencies of the SRW and BAW modes decrease as the temperature is lowered from room temperature to the insulator-metal transition temperature (T_IM=T_N=∼130 K). Below the transition, the modes show hardening. In the doped sample, the SRW mode shows a similar temperature-dependence as the undoped one, but the BAW mode shows hardening from room temperature down to the lowest temperature (50 K). This is the first measurement of the sound velocity below T_IM in the V₂O₃ system. The softening of the SRW frequency from 330 K to T_IM can be qualitatively understood on the basis of the temperature-dependence of C₄₄, which, in turn, is related to the orbital fluctuations in the paramagnetic metallic phase. The hardening of the mode frequencies below T_IM suggests that C₄₄ must increase in the antiferromagnetic insulating phase, possibly due to the orbital ordering.     

Study of the magnetization and transport properties of the La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 (0≤x≤0.2) system

The samples with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 La_(2+x)/3Sr_(1−x)/3Mn_1−xCr_xO₃ (0≤x≤0.20) have been prepared. The magnetic, electrical transport, and magnetoresistance properties have been investigated. Remarkable transport and colossal magnetoresistance (CMR) effect, as well as cluster glass (CG) behaviors have been clearly observed in the samples studied. It was found that the Curie temperature T_c and insulator−metal transition temperature T_p1 are strongly affected by Cr substitution. The experiment observations are discussed by taking into account the variety of tolerance factors t; the effects of A-site radius 〈r_A〉 and the A-site mismatch effect (σ²).     

Strongly enhanced free-exciton luminescence in microcrystalline CsPbCl3 films produced via the amorphous phase

High-quality CsPbCl₃ films composed of crystallites with narrow size distributions are achieved for various size levels, from microcrystalline to polycrystalline, by a novel heat-treatment method applied to the same amorphous films. Their photoluminescence is dominated by free-exciton emission at every size level without showing trapped-exciton emission in great contrast to the case for single crystals. The microcrystalline state shows more than an order of magnitude stronger free-exciton emission than the polycrystalline state, and exhibits intense stimulated emission under high-power excitation.     

Surface acoustic wave propagation and inhomogeneities in low-density two-dimensional electron systems near the metal-insulator transition

We have measured the surface acoustic wave velocity shift in a GaAs/AlGaAs heterostructure containing a two-dimensional electron system (2DES) in a low-density regime (<10¹⁰ cm⁻²) at zero magnetic field. The interaction of the surface acoustic wave with the 2DES is not well described by a simple model using low-frequency conductivity measurements. We speculate that this conflict is a result of inhomogeneities in the 2DES, which become very important at low density. This has implications for the putative metal-insulator transition in two dimensions.     

Theoretical investigation of the O2 adsorption effect in the electron transport of single Fe-porphyrin molecule

The effect of O₂ adsorption on the electron transport behavior of Fe-porphyrin molecule is investigated by the first-principles computational approach. The current-voltage characteristics of Fe-porphyrin and O₂ adsorbed Fe-porphyrin between gold electrodes are calculated. We find that the conductance of the Fe-porphyrin decreases dramatically upon the adsorption of O₂, which suggests that this system has potential application as a molecular sensor or a switch. This switching-behavior is analyzed from the evolutions of the transmission spectra and the molecular projected self-consistent Hamiltonian states of the molecular systems.     

Anomalous paramagnetic behavior in the paramagnetic phase of La2/3−xYxCa1/3MnO3 studied through EPR and its relation to colossal magnetoresistance

Electron paramagnetic resonance on La_2/3−xY_xCa_1/3MnO₃ in the paramagnetic (PM) regime is presented for 0≤x≤0.133. The resonance linewidth (ΔH_pp) decreases with cooling, reaches the minimum at T_min, and then anomalously increases with further cooling toward T_c. Our analysis on ΔH_pp(T) below T_min shows that the anomalous PM behavior below T_min is due to the appearance of a ferromagnetic (FM) phase within the PM matrix caused by the applied magnetic fields. The correlation between the anomalous PM and the colossal magnetoresistance is discussed. We argue that both are caused by the phase segregation in which the compound is phase-separated into a mixture of FM and PM regions.     

Decay pathway and high-temperature luminescence of Eu in Ca2Gd8Si6O26

The temperature-dependent luminescence of Eu:Ca₂Gd₈Si₆O₂₆ and its decay pathways are investigated in order to assess the utility of the material as a thermometric phosphor. Non-radiative decays are found to compete with radiative processes even at room temperature. A decay pathway involving decay through charge-transfer states is proposed based on the decay profiles of emissions from ⁵D₁ and ⁵D₀ levels and on the temperature sensitivity of the spectra as observed after excitation by several wavelengths. The implications of this on solid-state lighting are also discussed.     

Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)4N[FeFe(dto)3] (dto=C2O2S2)

(n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] shows a new type of first order phase transition called charge-transfer phase transition around 120 K, where the charge transfer between Fe^II and Fe^III occurs reversibly. Recently, we have succeeded in obtaining single crystals of the title complex and determined the crystal structure at room temperature. Crystal data: space group P6₃, Z=2. Moreover, we have investigated the structural transition caused by the charge-transfer phase transition by means of powder X-ray diffraction measurement. When the temperature is decreased, the a-axis, which corresponds to the hexagonal ring size in two-dimensional honeycomb network structure of [Fe^IIFe^III(dto)₃]_∞, contracts by 0.1 Å at the charge-transfer transition temperature (T_CT), while the c-axis, perpendicular to the honeycomb network layer, elongates by 0.1 Å at T_CT. Consequently, when the temperature is decreased, the unit cell volume decreases without noticeable anomaly around T_CT, which is responsible for the quite small vibrational contribution to the entropy change, compared with usual spin crossover transition. Thus, the charge-transfer phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] is regarded as spin entropy driven phase transition.