Light-induced charge transport in BaTiO3 via three charge states of rhodium

By combined studies of electron spin resonance and optical absorption at low temperatures, the charge-transfer bands of Rh⁵⁺ and Rh⁴⁺ are identified to be peaked near 1.6 and 1.9 eV, respectively. On this basis, the light-induced charge-transfer processes in BaTiO₃:Rh are unraveled at room temperature. It is shown that three charge states of Rh are involved, leading to two levels: the shallow Rh^4+/5+ and the deeper Rh^3+/4+ level. The optical behaviour of these two levels corresponds to those expected from a two-center model. The present paper represents the first atomic-scale identification of three charge states of one element leading to optical two-level response.     

Light-induced charge transport processes in photorefractive barium titanate doped with rhodium and iron

Absorption, light-induced absorption changes, photo and dark conductivities, bulk photovoltaic currents and two-beam coupling gain coefficients are measured for oxidized, as grown and reduced BaTiO₃:Rh,Fe crystals. Theoxidized sample shows hole conductivity and three photorefractive levels are present: Rh^4+/5+ Fe^4+/5+ and Rh^3+/4+. The measurements indicate that Rh^3+/4+ is responsible for the photo conductivity and that its energy level is located (0.9 ± 0.1) eV above the valence band edge. Theas grown sample also shows hole conductivity and two photorefractive levels are involved: Rh^3+/4+ and Fe 3+/4+. The results yield that the Fe^3+/4+ level is located (0.95 ± 0.05) eV above the valence band edge. In thereduced sample electrons are the dominant charge carriers and two levels are of importance. The shallow one is located (0.39 ± 0.05) eV below the conduction band edge. Here the performance of this crystal is strongly impaired by a pronounced sublinear photo conductivity.Dedicated to O. F. Schirmer on the occasion of his 60th birthday     

Spectroscopic analysis and laser parameters of Nd3+ in Ca3Sc2Ge3O12 garnet crystals

3 Sc₂Ge₃O₁₂ (CaSGG) single crystals with the garnet structure have been grown by means of the flux growth technique. The doping with Nd³⁺ and Mg²⁺ (as charge compensator) yields samples suitable for optical spectroscopy experiments. The absorption and emission properties have been measured at temperatures ranging from 10 to 298 K. The emission spectra give evidence of the presence of non-equivalent Nd³⁺ sites. The decay time of the 1.06-μm emission band has been measured as a function of temperature and incident power. The intensities of the 298 K absorption transitions have been analyzed by means of the Judd–Ofelt theory. The radiative lifetimes, the branching ratios (β), and the spontaneous emission probabilities have been evaluated for the ⁴F_3/2 excited state using the calculated intensity parameters. The stimulated-emission cross sections and the branching ratios have been estimated from the experimental data for the most important laser transitions indicating that this crystal can be considered an interesting material for solid-state laser applications. Received: 2 June 1998 / Revised version: 28 October 1998 / Published online: 24 February 1999     

Charge states of transition metal in “Cr, Co and Ni” doped Ln0.5Ca0.5MnO3 CMR manganites

The XAS study at Cr, Co, Ni and Mn K-edges was performed for the doped CMR manganites Ln_0.5Ca_0.5Mn_1-xB_xO₃ with Ln=La, Nd, Sm and B= Cr, Co, Ni (), on the samples that were studied previously for their ferromagnetic-metallic to antiferromagnetic-insulator transition. We observed that the formal charges of the doping elements are Ni²⁺, Co²⁺ and Cr³⁺. It is also evidenced that the average formal charge of the manganese is increased after doping, in agreement with the charge compensation keeping “O₃” stoichiometry. These results suggest that the doping elements participate directly to the band structure. Received: 9 January 1998 / Received in final form: 6 April 1998 / Accepted: 7 April 1998     

Light–induced charge transport processes in photorefractive barium titanate crystals doped with iron

3 ) are annealed in a hydrogen atmosphere at various temperatures. After these reducing treatments, absorption, light–induced absorption changes, two–beam coupling direction, photo electron paramagnetic resonance (photo EPR), dark and photoconductivity as well as bulk photovoltaic current density are investigated. The samples are electron conductive and the charge transport is governed by only one level, which is identified by photo EPR as Fe²⁺/Fe³⁺. The photoconductivity exceeds the dark conductivity for intensities above 1 kWm^-2. A relation between the absorption constant and the Fe²⁺ concentration is derived. From the known charge transport parameters the advantageous photorefractive properties of optimized reduced BaTiO₃:Fe are deduced; possible response times in the millisecond range at an intensity of 10 kWm^-2 are estimated. Received: 22 January 1997/Accepted: 23 January 1997     

Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

4 )₂ single crystals doped with Er³⁺ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) Å, β=130.80(2)°. The refractive index dispersion of the host has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er³⁺ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet splittings expected for the C₂ symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the ⁴F_7/2 multiplet. The Judd–Ofelt (JO) parameters of Er³⁺ in KGW have been calculated: Ω₂=8.90×10^-20 cm², Ω₄=0.96×10^-20 cm², Ω₆=0.82×10^-20 cm². Lifetimes of the ⁴S_3/2, ⁴F_9/2, and ⁴I_11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory. A reduction of the ⁴S_3/2 and ⁴I_11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative processes is inferred from the temperature dependence of the lifetimes. Received: 15 December 1997/Revised version: 10 July 1998     

Dielectric breakdown of rubber materials by femtosecond irradiation

We report the reversible micro-structuring of a synthetic rubber polymer (cis1,4-polybutadiene (PB)) by femtosecond laser illumination. Visco-elastic relaxation of the optically damaged region was observed. The recovery time, typically 10²–10⁴ ms, can be varied by changing the irradiation pulse energy. Multi-shot-induced damage recovers on the much longer scale of 10¹–10² s. It was found that the doping of PB by 4 wt. % of pentazadiene ([4-NO₂]–phenyl–N=N–N(C₃H₇)–N=N–phenyl–[4-NO₂]) reduces the threshold of light-induced photo-modification by 20%. This is explained by photo-induced (homolytic) cleavage of the pentazadiene bonds and formation of gaseous N₂, which facilitates material failure at the irradiated spot. The recovery of optical transmission can be applied to optical memory, optical and micro-mechanical applications. The underlying mechanism of the phenomenon is discussed in terms of anelastic α- and β-relaxation (polymer backbone and chains/coils relaxation, respectively). Received: 11 October 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +81-88/656-7598, E-mail: misawa@eco.tokushima-u.ac.jp     

Growth and characterization of cerium-substituted yttrium iron garnet single crystals for magneto-optical applications

This paper is concerned with the preparation and characterization of cerium-substituted yttrium iron garnets, which are known to be oxides having a large Faraday rotation effect. Using the improved flux method we successfully grew bulk single crystals of iron garnet doped with Ce³⁺ ions with maximum substitutions up to 0.349. Here we investigate different solution compositions for maximum Ce³⁺ substitution. The Faraday rotation and optical absorption spectra were measured in the near infrared region for different Ce³⁺ ion substituted iron garnets. The specific Faraday rotation of Ce_0.349Eu_0.195Y_2.456Fe₅O₁₂ was found to be 1430 deg/cm at a wavelength of 780 nm and –1280 deg/cm at 1150 nm. The Ce substitution prominently enhances the Faraday rotation effect, and Yb³⁺ and Eu³⁺ ions substituted for Y³⁺ in the dodecahedral sites of YIG can increase the concentration of Ce³⁺ ions, depressing the formation of nonmagnetic Ce⁴⁺ ions by charge compensation. Received: 24 January 2001 / Accepted: 2 March 2001 / Published online: 27 June 2001     

Performance of a diode-pumped 5 W Nd3+:GdVO4 microchip laser at 1.06 μm

4 as a host for neodymium has several advantages for diode pumping in comparison with other crystals. The absorption cross section of neodymium in GdVO₄ is considerably stronger and broader than in YAG. This allows for the construction of very compact monolithical microchip lasers. In our paper, we report for the first time on a diode-pumped monolithical Nd³⁺([%at.]1.3):GdVO₄ microchip laser at 1.06 μm. A maximum output power of 5 W is achieved. The temporal and the spectral emission properties are described. The beam propagation properties are studied in detail. Received: 23 July 1998 / Revised version: 9 November 1998 / Published online: 24 February 1999     

Dynamics of the Yb3+ to Er3+ energy transfer in LiNbO3

The energy transfer dynamics between Yb³⁺ and Er³⁺ ions in lithium niobate is investigated after ytterbium-pulsed excitation at 920 nm. The sensitisation of the LiNbO₃:Er³⁺ system with Yb³⁺ ions does not modify the lifetime of the ⁴I_13/2 erbium level (1.5-μm emission), whereas it induces a marked, concentration-dependent change in the lifetime of the ²F_5/2 (Yb³⁺) and ⁴S_3/2 (Er³⁺) multiplets (1060-nm and 550-nm emissions, respectively). The results are analysed by using the rate-equation formalism and cross-relaxation model for the energy transfer. Received: 15 October 1998 / Revised version: 24 November 1998 / Published online: 24 February 1999     

Strong permanent reversible diffraction gratings in copper-doped lithium niobate crystals caused by a zero-electric-field photorefractive effect

Permanent reversible diffraction gratings with refractive-index modulations of up to 10^-4 and with a grating vector perpendicular to the polar axis are realized in LiNbO₃:Cu crystals by making use of high temperature recording and charge compensation. The index changes do not result from light-induced space-charge fields and the linear electro-optic effect. They are linked to fixed high-contrast narrow-band absorption gratings of Cu⁺/Cu²⁺ ions via the Kramers–Kronig relations. PACS 42.65; 42.70; 72.40; 78.20     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part I: Y3Al5O12, YAlO3, and Y2O3

4 F_3/2 excited state of the Nd³⁺ ion in Y₃Al₅O₁₂, YAlO₃, and Y₂O₃ were measured in a continuous wave pump- and probe experiment in a wide spectral range from 850 nm (780 nm for Y₃Al₅O₁₂) to 1500 nm. The cross sections were determined from a comparison with the emission spectra and the simultaneously measured ground state absorption bleaching. The strongest excited state absorption transitions were found in the 1220–1400 nm spectral region due to transitions to the ²G_9/2 and ⁴G_7/2 levels. The spectral positions of the measured transitions are in good agreement with the theoretically expected transitions calculated from the known Stark-level splittings. Received: 4 December 1997/Revised version: 8 May 1998     

Nonlinear absorption properties of Co2+:MgAl2O4 crystal

The differential absorption spectra of Co²⁺: MgAl₂O₄ (MALO) crystal were studied with a picosecond pump-probe technique under excitation of the ⁴A₂→⁴T₁(⁴P) and ⁴A₂→⁴T₁(⁴F) transitions of the tetrahedral Co²⁺ ion. The difference spectra of stimulated emission (SE) and excited state absorption (ESA) were derived from the measured differential absorption spectra. The ⁴T₁(⁴P)→⁴A₂ SE band around 660 nm was observed. The ESA bands were assigned to the ⁴T₂→⁴T₁(⁴P) transition and to transitions from the thermally populated ²E(²G) excited state to doublet levels arising from the ²F free-ion level of the tetrahedrally coordinated Co²⁺ ion. Absorption saturation measurements were performed at 1.34 μm and 1.54 μm. Passive Q-switching of 1.34-μm Nd³⁺:YAlO₃ and 1.54-μm Er³⁺:glass lasers was realized using the Co²⁺:MALO crystal as saturable absorber. The Q-switched laser pulses of 38 ns (110 ns) in duration and up to 2.7 mJ (10 mJ) in energy at 1.54 μm (1.34 μm) were obtained. Received: 3 March 1999 / Revised version: 30 June 1999 / Published online: 30 November 1999     

Light-induced absorption in reduced congruent and near-stoichiometric Er:LiNbO3 crystals

Light-induced absorption (LIA) in thermally reduced congruent and near-stoichiometric Er:LiNbO₃ crystals, which have different cuts of crystal (X- and Y-cut) and different doping levels of Er³⁺ (0.2, 0.4, 0.6 and 1.0 mol %), has been studied within continuous-wave light intensity by using polarized 632.8 nm beam as probe light and polarized 488 nm beam as pump light. Effects of thermal reduction condition, pump intensity, Li/Nb ratio and Er-doping level on the LIA are summarized and discussed. Studies on spectral characteristics of both linear absorption and light-induced absorption show that photo-ionization of bipolarons into small polarons plays a predominant role in the LIA process. The role of the Er³⁺ ion in the LIA is investigated by studying the doping level and the thermal reduction effects on the absorption and emission properties of Er³⁺. The results show the possibility that the Er³⁺ ion directly participates in the light-induced charge transport is small. It affects the LIA only via the bypassing part of pump intensity to excite near-infrared emissions of Er³⁺. The thermaleffect on the LIA is demonstrated. A two-center model with inclusion of the thermal contribution can qualitatively explain two major LIA characteristics that include the appearance of a slow stage in the LIA procedure and the unsaturation behavior of the LIA coefficient in high pump intensity regime. In addition, the pump depletion effect on the LIA characteristics is discussed. The possibility of pump beam fanning arising from light-induced scattering is ruled out experimentally. PACS 42.70.Hj; 42.70.Ln; 42.70.Mp; 42.65.Hw; 81.05.-t     

Evolution of charge ordering in manganites

Charge ordering phenomena in the manganites Ca_1-xSm_xMnO₃ have been studied for , using electron diffraction and lattice imaging, completed by magnetic and transport measurements. Three domains can be distinguished, depending on the nature of the structural transitions with temperature. For , the structural transition from a pseudo-tetragonal to a monoclinic form, with decreasing temperature, coincides with the competition between ferromagnetism and antiferromagnetism that is characterized by the temperature T_peak on the M ( T ) curves; short-range charge ordering is observed for manganites. For the second domain, , a structural transition from an orthorhombic to a long-range charge ordered state is clearly observed with decreasing temperature. The corresponding temperature T_CO coincides with the temperature T_peak deduced from magnetic measurements. This long range charge ordering, which appears along a, is either commensurate or incommensurate depending on the x value, with a modulation vector, q being close to x. These modulated superstructures correspond to a stacking of single Mn³⁺ stripes with multiple Mn⁴⁺ stripes along a, either in a commensurate or in an incommensurate manner. The third domain , is characterized by a transition to a charge ordered state with commensurate superstructure at low temperature. The latter can be described as a “partially” charge ordered state in which single “Mn³⁺” stripes alternate with mixed “Mn³⁺/Mn⁴⁺” stripes. Received 17 June 1998     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part 2: YVO4, GdVO4, and Sr5(PO4)3F

3+ ion in the crystals YVO₄, GdVO₄, and Sr₅(PO₄)₃F. The measurements were performed in the spectral region of the main laser transitions ⁴F_3/2→⁴I_9/2, ⁴F_3/2→⁴I_11/2, and ⁴F_3/2→⁴I_13/2by a continuous wave pump and probe technique. The calibrated gain and ESA spectra are presented and possible implications of ESA on the laser performance are estimated. It is shown that ESA can be a small loss factor to the laser emission near 1060 nm but does considerably diminish the effective emission cross sections near 1340 nm especially in Nd:YVO₄ and Nd:GdVO₄. Received: 29 January 1998/Revised version: 8 May 1998     

Light-induced charge transfer and kinetics of the NIR absorption of Nb4+ polarons in SBN crystals at low temperatures

Sr_1-xBa_xNb₂O₆ (SBN) crystals with open tungsten-bronze structure show enhanced photorefractive properties with doping of impurities such as Ce, Cr, Rh etc. Under illumination with Kr⁺ laser (647 nm) or Ar⁺ laser light (488 nm or 514 nm) or UV light at low temperature, pure and doped SBN crystals show a broad polaron absorption band around 0.7 eV (6000 cm^-1). The first step of a theoretical model involves the excitation of electrons by illumination from Cr³⁺/Ce³⁺ to higher excited states or the conduction band. The excited electrons can then be trapped by Nb⁵⁺ to form Nb⁴⁺ polarons and further on can directly tunnel through or hop over the potential barrier (with a value Δ≈0.15±0.02 eV) to recombine with Cr⁴⁺/Ce⁴⁺ ions. The experimental intensity dependence, temperature dependence, and decay process of the light-induced Nb⁴⁺ polarons can be fitted with the help of this model. Small, but systematic, differences lead to the additional assumption of different recombination rates of polarons at distinct distances from the Cr⁴⁺/Ce⁴⁺ recombination centers and therefore many parallel decay channels are active where each decay channel obeys a monoexponential decay law. A stretched exponential decay function is employed to fit in this case the decay process of the Nb⁴⁺ polarons at different temperatures and under illumination with different intensities. Due to the high dielectric constant value (ε₃₃ and ε₁₁ have values in the 10²-10³ range) at low temperature, the long range Coulomb attraction (to Ce³⁺ _Sr/Ba) or repulsion (from Cr³⁺ _Nb) of the electronic polaron is suppressed. The leading role in the attraction and the following trapping of the electronic Jahn–Teller polaron, both on Cr³⁺ _Nb and Ce³⁺ _Sr/Ba centers, is played by the indirect dipole–dipole interaction via the soft TO-mode. Received: 27 November 1998 / Revised version: 22 January 1999 / Published online: 7 April 1999     

Studies of impurity levels in Rh-doped and Ce-doped photorefractive BaTiO3

Impurity levels, light-induced and thermo-induced charge transfer processes in Rh-doped and Ce-doped photorefractive BaTiO₃ were studied. The thermal depths and optical transitions of these impurity levels in the crystals were determined by using such methods as light-induced absorption, thermo-induced absorption, and grating dark decay. The origins of these impurity levels were discussed. We demonstrated, for the first time to our knowledge, that thermo-induced absorption spectroscopy is a useful and complementary technique for investigating the impurity levels in photorefractive crystals. With this technique, the deep impurity level generated by Ce in BaTiO₃:Ce was revealed and identified. Received: 7 July 1999 / Revised version: 24 September 19999 / Published online: 2 February 2000     

Towards new lasers in Ti:Er:LiNbO3 waveguides: a study of the excited Er3+ states

Detailed excited state absorption measurements under pumping at 980 nm and 1.5 μm together with conventional absorption and emission spectroscopy is employed to investigate optical transitions of Er³⁺ in Ti:LiNbO₃ channel-waveguides. The experimental data were evaluated using the Judd–Ofelt method giving parameters close to those in the bulk. The good agreement between theoretical prediction and measurements allows us to calculate cross section, lifetimes, and branching ratios. Based on these results we developed and tested a model which is able to predict the conditions for which laser operation at 550 nm and 2.7 μm will be possible under 980 nm pumping. Received: 9 December 1998 / Revised version: 8 January 1999 / Published online: 24 March 1999     

Emission properties of a Tm30.1mm+:GdVO4 microchip laser at 1.9 μm

4 as a host for thulium has several advantages for diode pumping in comparison with other crystals. The absorption cross section of thulium in GdVO₄ is considerably stronger and broader than in YAG and YLF and the spectrum is shifted closer to the emission wavelength of commercially available AlGaAs laser diodes. In our paper, we report on the temporal and spectral emission properties of a monolithical Tm^30.01mm+([%at.]6.9):GdVO₄ microchip laser at 1.9 μm. The laser can be adjusted to emit either cw or in an oscillating regime. Slope efficiencies up to 47% are achieved. This value exceeds the Stokes limit of 42%. Received: 31 March 1998/Revised version: 02 June 1998