Acoustic probing of two-temperature relaxation initiated by action of ultrashort laser pulse

Ultrashort laser pulse transfers metal into a two-temperature warm dense matter state and triggers a chain of hydrodynamic and kinetic processes—melting, expansion, stretching, creation of tensile stress and transition into metastable state. We study the response of aluminum film deposited on a glass substrate to irradiation by a pump laser pulse transmitted through glass. Several films with thicknesses from 350 to 1200 nm have been investigated. The smallest thickness is of the order of the heating depth d _T∼100 nm in Al. The d _T-layer and the free rear side of the film are coupled through pressure waves propagating between them. Therefore, the processes within d _T-layer affects the time dependent displacement Δ x _rear(t) of the rear surface. We compare simulated and experimental dependencies Δ x _rear(t) obtained by the pump–probe technique. It allows us to define a thickness of molten Al layer and explore the two-temperature processes occurring inside the heated layer.     

Electron‐Ion Relaxation,Phase Transitions,and Surface Nano‐Structuring Produced by Ultrashort Laser Pulses in Metals

Fundamental physical phenomena in metals irradiated by ultrashort laser pulses with absorbed fluences higher than few tens of mJ/cm² are investigated. For those fluences, laser‐produced electron distribution function relaxes to equilibrium Fermi distribution with electron temperature T_e within a short time of 10‐100 fs. Because the electron subsystem has T_e highly exceeding much the ion subsystem temperature T_i the well‐known twotemperature hydrodynamic model (2T‐HD) is used to evaluate heat propagation associated with hot conductive electron diffusion and electron‐ion energy exchange. The model coefficients of electron heat conductivity κ (?, T_e, T_i) and electron‐ion coupling parameter α (?, T_e) together with 2T equation of state E (?, T_e, T_i) and P (?, T_e, T_i) are calculated. Modeling with 2T‐HD code shows transition of electron heat wave from supersonic to subsonic regime of prop‐agation. At the moment of transition the heat wave emits a compression wave moving into the bulk of met al. Nonlinear evolution of the compression wave after its separation from the subsonic heat wave till spallation of rear‐side layer of a film is traced in both 2T‐HD modeling and molecular dynamics (MD) simulation. For fluences above some threshold the nucleation of voids in frontal surface layer is initiated by strong tensile wave following the compression wave. If the absorbed fluence is ～30 % above the ablation threshold than void nucleation develops quickly to heavily foam the molten met al. Long‐term evolution of the metal foam including foam breaking and freezing is simulated. It is shown that surface nano‐structures observed in experiments are produced by very fast cooling of surface molten layer followed by recrystallization of supercooled liquid in disintegrating foam having complex geometry. Characteristic lengths of such surface nanostructures, including frozen pikes and bubbles, are of the order of thickness of molten layer formed right after laser irradiation. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microstructure,dielectric, and piezoelectric properties of 0.38Bi(Gax Sc1–x )O3–0.62PbTiO3 high temperature piezoelectric ceramics

0.38Bi(Ga_x Sc_1–x )O₃–0.62PbTiO₃ (BGSPTx) ceramics have been prepared by using the conventional mixed oxide method. X‐ray diffraction analysis revealed that BGSPTx has a pure perovskite structure, and the crystal symmetry of BGSPTx changed from rhombohedral to tetragonal with increasing Ga content (x). The Curie temperature (T_C) of BGSPTx ceramics is in the range of 448–467 °C for different x. The ferroelectric phase transition of BGSPTx was found to be of the first order type according to the Curie–Weiss law. For x = 0.125, BGSPTx ceramics show enhanced piezoelectric properties: piezoelectric constant d₃₃ = 420 pC/N and d₃₁ = –142 pC/N, planar and thickness electromechanical coupling factors k_p = 56.27% and k_t = 56.00%, respectively. The high‐T_C of BGSPTx coupled with its excellent piezoelectric properties suggests those future high‐temperature applications. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Large enhancement of the thermoelectric Seebeck coefficient for amorphous oxide semiconductor superlattices with extremely thin conductive layers

Herein we demonstrate that amorphous oxide semiconductor (AOS) superlattices composed of a‐In–Zn–O (well) and a‐In–Ga–Zn–O (barrier) layers, fabricated on SiO₂ glass substrate by pulsed laser deposition at room temperature, exhibited an enhanced Seebeck coefficient |S |. The |S | value increases drastically with decreasing a‐In–Zn–O thickness (d_IZO) when d_IZO < ∼5 nm, and reached 73 µV K^–1 (d_IZO = 0.3 nm), which is ∼4 times larger than that of bulk |S |_3D (19 µV K^–1), while it kept its high electrical conductivity, clearly demonstrating that the quantum size effect can be utilized in AOS superlattices. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Piezoelectric and ferroelectric properties of [(K0.4725Na0.4725)Li0.055]NbO3–(Ag0.5Li0.5)TaO3 lead‐free ceramics

New lead‐free piezoelectric (1 – x)[(K_0.4725Na_0.4725)Li_0.055]NbO₃– x (Ag_0.5Li_0.5)TaO₃ [(1 – x)KNNL–x ALT] ceramics were prepared by conventional sintering. Piezoelectric and ferroelectric properties and Curie temperature of the ceramics were studied. The (1 – x)KNNL–x ALT (x = 0.04) ceramics exhibit good properties (d₃₃ ～ 252 pC/N, k_p ～ 41%, T_C ～ 471 °C, T_o–t = 47 °C, P_r = 33.1 μC/cm², E_c = 10.6 kV/cm). These results show that (1 – x)KNNL–x ALT (x = 0.04) ceramic is a promising lead‐free piezoelectric material for high temperature application. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of fill factor losses on 20.2% efficient n‐type mono‐like silicon solar cells with laser contact opening

Large area (243.36 cm²) back‐junction passivated emitter, rear totally diffused (PERT) solar cells with laser contact opening (LCO) on n‐type mono‐like crystalline Si with efficiencies of 20.2% are presented. Boron emitters with high electrical quality (implied open circuit voltage iV_OC up to 700 mV) are formed during a co‐diffusion step using SiO_x:B layers. Increasing the rear metal contact coverage, we observed a decrease in fill factor (FF) instead of the expected increase due to the decrease of the back side series resistance. We show that it can be attributed to recombination centers (RCs) in the space charge region underneath the contact spots inducing an increasing second diode contribution. The presented empirical model for the RCs implemented in Synopsys Sentaurus TCAD allows for a successful reproduction of the FF, pseudo FF and V_OC behaviour with contact coverage. According to this model, the RCs induced by laser ablation and subsequently evaporation of Al have a shallow exponential distribution with a characteristic length of L_T = 0.2 µm and an effective surface density of N *_T0 = 25 cm^–1. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Size resonances in penetration of intense femtosecond laser pulses through ultra-thin foils

An analytic expression for the transmission coefficient as a function of the foil thickness d describing penetration of intense femtosecond laser pulses through ultra-thin foils with a thickness of the order of 30–100 nm is derived using the Vlasov-Boltzmann equation. It is found that the transmission of laser radiation stops at the skin depth c/ω _p , but sharp and narrow resonances occur for the foil thickness d > c/ω _p with the transmission coefficient T = 1. The article is published in the original.     

Interphase boundaries and high piezoelectric activity of xPbTiO3-(1−x)Pb(Zn1/3Nb2/3)O3 crystals

Model concepts of the interphase boundaries whose displacements are capable of substantially affecting the piezoelectric properties of xPbTiO₃-(1?x)Pb(Zn_1/3Nb_2/3)O₃ multidomain crystals in the R3m-P4mm morphotropic region are developed. The contributions of the interphase boundaries Δd ₃₃ to the piezoelectric modulus d ₃₃ are determined, and the factors responsible for the large ratios Δd ₃₃/d ₃₃≈0.5–0.9 are analyzed.     

Behaviour of transmittance and phase change on transmission with film thickness at intermediate thicknesses

The behaviour of the optical functions T (transmittance) and X_t (phase change on transmission) for an absorbing film have been investigated as the film thickness was increased from a small fraction of a wavelength up to a thick solid. When plotted against thickness, the values of T oscillated at a frequency related to the quantity, x=2πd/λ which is equal to the phase thickness divided by the refractive index. Ultimately, for real materials, the oscillations were damped to zero due to the absorption term in the complex dielectric constant of the film material. In the case of X_t, the most notable feature was the sudden phase changes of ±π which occurred repeatedly as the thickness increased and the values of x at which this occurred could be related to the conditions for constructive or destructive interference between light rays coming from the top and bottom of the film.     

Combined effects of Li content and sintering temperature on?polymorphic phase boundary and electrical properties of Li/Ta co-doped (Na, K)NbO3 lead-free piezoceramics

Crystallographic structure, phase transition and electrical properties of lead-free (Na_0.535K_0.485)_1−x Li _x (Nb_0.942Ta_0.058)O₃ (x=0.042–0.098) (NKL _x NT) piezoelectric ceramics were investigated. The experimental results show that both Li content and sintering temperature strongly affect the orthorhombic–tetragonal polymorphic phase boundary (PPB), which results in remarkable differences of the piezoelectric property and its temperature stability in the NKL _x NT ceramics. Chemical analysis indicates that sodium volatilizes more seriously than potassium and lithium with increasing sintering temperature. Due to the comprehensively optimized effects of Li content and sintering temperature, an enhanced piezoelectric constant d ₃₃ (276 pC/N) was obtained at room temperature in the ceramics with x=0.074 sintered at 1000°C. In the same composition, a further high d ₃₃ up to 354 pC/N was obtained at 43°C, which is close to its T _o−t temperature. Furthermore, better temperature stability can be obtained when x=0.082 sintered at 1000°C, whose piezoelectric constant d ₃₃ (236 pC/N) keeps almost constant from room temperature to 100°C. Such a temperature-independent piezoelectric property is available in the NKL _x NT ceramics with high Li content because its T _o−t was moved below room temperature.     

Fast electron energy deposition in aluminium foils: Resistive vs. drag heating

The high current electron beam losses have been studied experimentally with 0.7 J, 40 fs, 6 10¹⁹ Wcm^-2 laser pulses interacting with Al foils of thicknesses 10-200 μm. The fast electron beam characteristics and the foil temperature were measured by recording the intensity of the electromagnetic emission from the foils rear side at two different wavelengths in the optical domain, ≈407 nm (the second harmonic of the laser light) and ≈500 nm. The experimentally observed fast electron distribution contains two components: one relativistic tail made of very energetic (T _h ^tail ≈ 10 MeV) and highly collimated (7° ± 3°) electrons, carrying a small amount of energy (less than 1% of the laser energy), and another, the bulk of the accelerated electrons, containing lower-energy (T _h ^bulk=500 ± 100 keV) more divergent electrons (35 ± 5°), which transports about 35% of the laser energy. The relativistic component manifests itself by the coherent 2ω₀ emission due to the modulation of the electron density in the interaction zone. The bulk component induces a strong target heating producing measurable yields of thermal emission from the foils rear side. Our data and modeling demonstrate two mechanisms of fast electron energy deposition: resistive heating due to the neutralizing return current and collisions of fast electrons with plasma electrons. The resistive mechanism is more important at shallow target depths, representing an heating rate of 100 eV per Joule of laser energy at 15 μm. Beyond that depth, because of the beam divergence, the incident current goes under 10¹² Acm^-2 and the collisional heating becomes more important than the resistive heating. The heating rate is of only 1.5 eV per Joule at 50 μm depth.     

On the oscillons in the signum-Gordon model

New periodic solutions of signum-Gordon equation are presented. We first find solutions φ₀(x, t) defined for (x, t) ∈ ? × [0, T ] and satisfying the condition φ₀(x, 0) = φ₀(x, T ) = 0. Then these solutions are extended to the whole spacetime by using (2.4).     

Photochromism of dihydroindolizines Part XIX. Efficient one‐pot solid‐state synthesis,kinetic, and computational studies based on dihydroindolizine photochromes

For the first time, one‐pot solid‐state synthesis of 12 photochromic materials based on photochromic dihydroindolizine system substituted in both fluorene part (region A) and the heterocyclic part (region C) has been established. This method has immense advantages, which are short‐time reaction, high‐yield and low‐yield by‐products, and easily purification and separation processes. In addition, this method will help in getting over the tremendously purification and low‐yield problems faced since the worth‐finding of this family of photochromic materials. The absorption maxima (λ_max) and the half‐lives (t_1/2) of the colored betaines were detected in all cases using multichannel UV/Vis spectrophotometric measurements. The rate constants of the thermal back reaction of the betaines were determined at constant temperature by measuring the decrease in the maximum absorption intensity (λ_max) with time. The half‐lives (t_1/2) and rate constants (k) of betaines under examination were calculated by plotting lnA against time (t). The kinetic measurements could be detected by both spectra scan and time‐dependent decay measurements. Examination of the Arrhenius parameters reveals an underlying compensation between E_a and log A, whereby an increase in E_a is opposed by an increase in log A. The compensation appears in the corresponding Eyring parameters, ΔH^≠ and ΔS^≠; betaine structural changes that lead to lower, more favorable enthalpies of activation engender opposing entropic changes. At the isokinetic temperature T_iso = β, structural changes do not affect the rate constant of a reaction series because the changes of ΔH^≠ are counterbalanced by changes of ΔS^≠. The existence of an isokinetic relationship indicates a common structure of the transition state of all thermal back reaction of betaine under investigation. The computational results suggest that the decoloration reaction is a two‐step mechanism. The first step corresponds to the transoid–cisoid isomerization with an activation barrier of 10.3 kJ mol^?1, and the second step is the ring closure from the cisoid intermediate with a barrier 71.3 kJ mol^?1, which represent the rate determining step for thermal decoloration. The photochemical ring opening of DHIs to betaines is a disrotatory 1,5‐electrocyclic reaction, whereas the thermal ring‐closing occurs in the conrotatory mode. Copyright © 2016 John Wiley & Sons, Ltd.     

Propagation of electromagnetic waves generated by moving sources in dispersive media

The propagation of electromagnetic waves issued by modulated moving sources of the form j( t,x ) = a( t )e ^{- iw₀ t} [(x)\dot]₀ ( t )d( x - x₀ ( t ) )j\left( {t,x} \right) = a\left( t \right)e^{ - i\omega _0 t} \dot x_0 \left( t \right)\delta \left( {x - x_0 \left( t \right)} \right) is considered, where j(t, x) stands for the current density vector, x = (x ₁, x ₂, x ₃) ∈ ℝ³ for the space variables, t ∈ ℝ for time, t → x ₀(t) ∈ ℝ³ for the vector function defining the motion of the source, ω ₀ for the eigenfrequency of the source, a(t) for a narrow-band amplitude, and δ for the standard δ function. Suppose that the media under consideration are dispersive. This means that the electric and magnetic permittivity ɛ(ω), μ(ω) depends on the frequency ω. We obtain a representation of electromagnetic fields in the form of time-frequency oscillating integrals whose phase contains a large parameter λ > 0 characterizing the slowness of the change of the amplitude a(t) and the velocity [(x)\dot]₀ ( t )\dot x_0 \left( t \right) and a large distance between positions of the source and the receiver. Applying the two-dimensional stationary phase method to the integrals, we obtain explicit formulas for the electromagnetic field and for the Doppler effects. As an application of our approach, we consider the propagation of electromagnetic waves produced by moving source in a cold nonmagnetized plasma and the Cherenkov radiation in dispersive media.     

Vibrational spectroscopy study of hydrothermally produced scorodite (FeAsO4·2H2O), ferric arsenate sub‐hydrate (FAsH; FeAsO4·0.75H2O) and basic ferric arsenate sulfate (BFAS; Fe[(AsO4)1−x(SO4)x(OH)x]·wH2O)

Three crystalline ferric arsenate phases: (1) scorodite; FeAsO₄·2H₂O, (2) ferric arsenate sub‐hydrate (FAsH; FeAsO₄·0.75H₂O) and (3) basic ferric arsenate sulfate (BFAS; Fe[(AsO₄)_1−x(SO₄)_x(OH)_x]·wH₂O) synthesized by hydrothermal precipitation (175–225 °C) from Fe(III)‐AsO₄³⁻–SO₄²⁻ solutions have been investigated via Raman and infrared spectroscopies. The spectroscopic nature of these high‐temperature Fe(III)‐ AsO₄³⁻–SO₄²⁻ phases has not been extensively studied despite their importance to the hydrometallurgical industrial processing of precious metal (Au and Cu) arsenic sulfidic ores. It was found that scorodite, FAsH and BFAS all gave rise to very distinct arsenate, sulfate and hydroxyl vibrations. In scorodite and FAsH, the distribution of the internal arsenate modes was found to be distinct, with the factor effect being more predominant in the crystal system. For the crystallographically unknown BFAS phase, vibrational spectroscopy was used to monitor the arsenate ↔ sulfate solid solution behavior that occurs in this phase where the molecular symmetry of arsenate and sulfate in the crystal structure is reduced from an ideal T_d to a distorted T_d or C₂/C_2v symmetry. With the new collected vibrational data of the pure phases, the use of attenuated total reflectance infrared (ATR‐IR) spectroscopy was finally extended to investigate the nature of the arsenate in an industrial residue generated by pressure oxidation of a gold ore, where it was found that the arsenate was present in the form of BFAS. Copyright © 2009 John Wiley & Sons, Ltd.     

In situ Raman and optical microscopy of the relaxation behavior of amorphous ices under pressure

The transformation of low‐density amorphous (LDA) ice produced from high‐density amorphous (HDA) ice was studied up to 400 MPa as a function of temperature by in situ Raman spectroscopy and optical microscopy. Changes in these amorphous states of H₂O were directly tracked without using emulsions to just above the crystallization temperature T_x. The spectra show significant changes occurring above ∼125 K. The results are compared with data reported for the relaxation behavior of HDA, to form what we call relaxed HDA, or rHDA. We find a close connection with expanded HDA (eHDA), which is reported to exist as another metastable form in this P–T region. The observation of this temperature‐induced LDA transition under pressure complements the previously observed pressure‐induced reversible transition between LDA and HDA at 120–140 K. Copyright © 2009 John Wiley & Sons, Ltd.     

Conductivity of heavily doped Si:P under uniaxial stress

Barely insulating, uncompensated Si:P samples have been tuned through the metal‐insulator transition applying uniaxial stress along the [100] direction. We find a critical exponent μ ≈︂ 1 of the electrical conductivity extrapolated to temperature T = 0, i.e. σ(T → 0,S) ∼ |S — S_c|^μ, in disagreement with earlier stress tuning studies along [123‐] where μ ≈︂ 0.5 was reported. Varying the stress or the concentration leads to a different T dependence of σ(T). Our stress‐tuning measurements obey finite‐T scaling with a dynamic exponent z = 3.     

Investigation of the effect of plasma waves excitation on target normal sheath ion acceleration using fs laser‐irradiating hydrogenated structures

Measurements of ion acceleration in polymethylmethacrylate foils covered by a thin copper film irradiated by fs laser in target normal sheath acceleration regime are presented. The ion acceleration depends on the laser parameters, such as the pulse energy; depends on the irradiation conditions, such as the focal point position of the laser with respect to the target surface; and depends on the target properties, such as the metallic film thickness. The proton acceleration increases in the presence of the metallic film enhancing the plasma electron density, reaching about 1.6 MeV energy for a focal position on the target surface. The plasma diagnostics uses SiC detectors, absorber foils, Faraday cups, and gafchromic films. Employing p‐polarized laser light and a suitable oblique incidence, it is possible to increase the proton acceleration up to about 2.0 MeV thanks to the effects of laser absorption resonance due to plasma waves excitation.     

Electrical resistivity of liquid Sb–Zn alloys

Using the DC four-probe method, temperature dependence of the electrical resistivity (ρ???T) of Sb_{100? x} Zn _x (x?=?25,?40,?50,?57,?61,?80 at%) alloys was investigated in the temperature range of 500–860°C. The results showed that resistivity of each liquid alloy decreased non-linearly with temperature increasing above their liquidus (T _L) until reaching critical temperature, at which the resistivity–temperature coefficients dρ/dT–T converts from negative into positive. The phenomena of liquid phase transformation might relate with the dissociation of covalent bonds, chemical orders and associations in Sb–Zn melts.     

Relation between the critical magnetic field and energy gap of a superconductor

A dynamical model is used to derive a relationship between the slope of the reduced critical magnetic field for T = T_c and the energy gap Δ_o of a superconductor. Good agreement with the relation |dh/dt|_t=1 = Δ_o/ k T_c proposed by Toxen is found up to Δ_o/k T_c = 4.