Z-Scan studies of KYW, KYbW, KGW, and Ba(NO3)2 crystals

We present the studies of nonlinear refraction and nonlinear absorption in promising crystals which are extensively used in Raman lasers or as solid-state laser host materials: Ba(NO₃)₂, KGW, KYW, and KYbW. The single-beam z-scan technique with 1 ps laser pulses at 790 and 395 nm has been applied for the study. Nonlinear refraction-index intensity-coefficients and two-photon absorption coefficients have been determined for the crystals. The considerable enhancement of nonlinear refraction is observed in the crystals at 395 nm.     

Third order optical nonlinearities in ZnFe2O4 nanocrystals

Using Z-scan method with picosecond laser at 532 nm, the third order optical nonlinearities of ZnFe₂O₄ were investigated. The nonlinear refractive index is positive for all ZnFe₂O₄ samples and decrease with the nanocrystal size. The nonlinear absorption dominated by saturable absorption for 19 nm and 11 nm ZnFe₂O₄ but by two photon absorption for 5 nm ZnFe₂O₄ organosol. Origin of the optical nonlinearities and the size effect has been discussed.     

The nonlinear refraction and absorption dependence on the thermal effect for 4 ns pulse duration in binuclear Zn(II) phthalocyanine solution

The influence of thermal effect on the third-order nonlinear optical properties of binuclear Zn(II) phthalocyanine in chloroform solution was studied. The nonlinear refraction and absorption of the sample was measured by using Z-scan technique with 4 ns laser pulses at 532 nm wavelength. The opposite signs of the effective nonlinear refraction index were observed by changing the focal length of focusing lens from 10 cm to 20 cm in the experimental setup. Changing the focusing lens increased the beam waist radius from 7 μm to 20 μm. The nonlinear absorption coefficient was reduced about 200 times based on changing the fluence or beam waist radius. The drastic changes in the third-order nonlinear optical parameters were attributed to thermal effect. To investigate the role of thermal effects even further the effective nonlinear refraction and absorption coefficients were studied by using different repetition rates, input powers and concentrations.     

Third-order optical nonlinearity of (Ba0.7Sr0.3)TiO3 ferroelectric thin films fabricated by soft solution processing

(Ba_0.7Sr_0.3)TiO₃ (BST) ferroelectric thin films with perovskite crystal structure were fabricated by soft solution processing on a quartz substrate. The third-order nonlinear optical properties were investigated by using Z-scan technique. Positive nonlinear refractive index and nonlinear absorption coefficient were determined to be 4×10⁻⁷ esu and 1.2×10⁻⁶ m/w, respectively. The real part and imaginary part of third-order optical nonlinear susceptibility were calculated and the values were 6.43×10⁻⁸ and 5.14×10⁻⁸ esu, respectively. All of these results show ferroelectric BST thin film is promising for applications in nonlinear optical devices.     

Nonlinear optical properties in SrTiO3 thin films by pulsed laser deposition

Well-crystallized 250 nm-thick SrTiO₃ thin films on fused-quartz substrate were prepared by pulsed laser deposition. The band-gap of SrTiO₃ thin film by transmittance spectra is equal to 3.50 eV, larger than 3.22 eV for the bulk crystal. The nonlinear optical properties of the films were examined with picosecond pulses at 1.064 μm excitation. A large two-photon absorption (TPA) with absorption coefficient of 87.7 cm/GW was obtained, larger than 51.7 cm/GW for BaTiO₃ thin films. The nonlinear refractive index n₂ is equal to 5.7×10⁻¹⁰ esu with a negative sign, larger than 0.267×10⁻¹¹ esu for bulk SrTiO₃. The large TPA is attributed to intermediate energy levels introduced by the grain boundaries, and the optical limiting behaviors stemming from both TPA and negative nonlinear refraction were also discussed.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

Absorption and emission characteristics of Er3NbO7 phosphor: A comparison with ErNbO4 phosphor and Er:LiNbO3 single crystal

Er₃NbO₇ phosphor was synthesized by sintering a mixture of Er₂O₃ and Nb₂O₅ powder in a molar ratio of 3:1 at 1600 °C over 55 h. Optical absorption and emission characteristics of Er³⁺ ions in the calcined Er₃NbO₇ powder were investigated and discussed compared with ErNbO₄ phosphor and a Z-cut congruent Er (2 mol%):LiNbO₃ single crystal. The absorption and emission studies show that, due to different crystal structures, the spectroscopic properties of these niobates have some differences in spectral shape, peak position, and relative intensity, especially at 1.5 μm. The most obvious spectral feature of the Er₃NbO₇ is that the spectral structure of band instead of peak is observed in its absorption or emission spectrum due to the existence of local structural disorder and multiple Er³⁺ sites. The Er₃NbO₄ shows stronger upconversion emission than the single crystal but weaker than the ErNbO₄. Experimental results show that energy transfer upconversion and/or excited state absorption play a dominant role in the upconversion emissions, and, at higher pump level (>200 mW), the thermal effect becomes significant and results in drop of the upconversion intensity. The 1.5 μm lifetimes of Er³⁺ ion in the Er₃NbO₇, ErNbO₄ phosphor, and in the Er:LiNbO₃ crystal are measured to be ∼5.3, 2.0, and 2.4 ms, respectively. In combination with the measured Raman spectra, the quantum efficiency, multiphonon nonradiative decay rate, and theoretical radiative lifetime of the 1.5 μm emission of the two powder materials are expected. The differences in upconversion intensity and measured 1.5 μm lifetime between the three materials are explained qualitatively.     

Third-order optical nonlinearities of lead-free (Na1−xKx)0.5Bi0.5TiO3 thin films

(Na_1−xK_x)_0.5Bi_0.5TiO₃ (NKBT) (x = 0.1, 0.2, and 0.3) thin films with good surface morphology and rhombohedral perovskite structure were fabricated on quartz substrates by a sol-gel process. The fundamental optical constants (the band gaps, linear refractive indices and absorption coefficients) of the films were obtained through optical transmittance measurements. The nonlinear optical properties were investigated by Z-scan technique performed at 532 nm with a picosecond laser. A two-photon absorption effect closely related with potassium-doping content was found in thin films, and the nonlinear refractive index n₂ increases evidently with potassium-doping. The real part of the third-order nonlinear susceptibility χ⁽³⁾ is much larger than its imaginary part, indicating that the third-order optical nonlinear response of the NKBT films is dominated by the optical nonlinear refractive behavior. These results show that NKBT thin films have potential applications in nonlinear optics.     

Detailed infrared spectroscopic study of thermal transitions in new hybrid [(CH3)2CHNH3]4Cd3Cl10 crystal

Phase transitions of tetra(isopropylammonium)decachlorotricadmate(II) [(CH₃)₂CHNH₃]₄Cd₃Cl₁₀ crystal have been studied by infrared, far infrared and Raman measurements in wide temperature range, between 11 K and 388 K. The temperature changes of wavenumber, center of gravity, width and intensity of the bands were analyzed to clarify cationic and anionic contributions to the phase transitions mechanism. The results of investigation showed earlier by differential scanning calorimetry (DSC), thermal expansion and dielectric measurements clearly confirmed the sequence of phase transitions at T₁=353 K, T₂=294 K and T₃=260 K. The current results derived from DSC and infrared measurements revealed additional phase transition at T₄=120 K.     

Preparation and properties of spray-deposited ZnIn2Se4 nanocrystalline thin films

Zinc indium selenide (ZnIn₂Se₄) thin films have been deposited onto amorphous and fluorine doped tin oxide (FTO)-coated glass substrates using a spray pyrolysis technique. Aqueous solution containing precursors of Zn, In, and Se has been used to obtain good quality deposits at different substrate temperatures. The preparative parameters such as substrate temperature and concentration of precursors solution have been optimized by photoelectrochemical technique and are found to be 325 °C and 0.025 M, respectively. The X-ray diffraction patterns show that the films are nanocrystalline with rhombohedral crystal structure having lattice parameter a=4.05 Å. The scanning electron microscopy (SEM) studies reveal the compact morphology with large number of single crystals on the surface. From optical absorption data the indirect band gap energy of ZnIn₂Se₄ thin film is found to be 1.41 eV.     

Photocontrol of magnetization in Al-substituted Fe3O4 thin films

Thin films of (111)-oriented spinel ferrite Al_0.5Fe_2.5O₄ have been prepared by a pulsed-laser deposition (PLD) technique on α-Al₂O₃ (0001) substrates. The films exhibit cluster-glass behaviors with a spin-freezing temperature, T_g, near or above room temperature. The magnetization was found to increase following light irradiation below T_g, which indicates the photoinduced melting of cluster-glass states. An analysis comparing the dynamic behavior of magnetic response to light irradiation between zero-field-cooled (ZFC) states and field-cooled (FC) states at 10 K under various light intensities, I, revealed that the direct photoexcitation of spins occurs when I≤0.78 mW/mm², while the thermal heating effect following the light absorption of the samples also contributes to the enhancement of magnetization when I≥1.22 mW/mm². The magnetization of the films could be controlled by light irradiation even at room temperature. This suggests the possibility of utilizing these films in the development of novel magneto-optical memory devices.     

Immiscibility in the NiFe2O4-NiCr2O4 spinel binary

The solid solution behavior of the Ni(Fe_1−nCr_n)₂O₄ spinel binary is investigated in the temperature range 400-1200 °C. Non-ideal solution behavior, as exhibited by non-linear changes in lattice parameter with changes in n, is observed in a series of single-phase solids air-cooled from 1200 °C. Air-annealing for 1 year at 600 °C resulted in partial phase separation in a spinel binary having n=0.5. Spinel crystals grown from NiO, Fe₂O₃ and Cr₂O₃ reactants, mixed to give NiCrFeO₄, by Ostwald ripening in a molten salt solvent, exhibited single-phase stability down to about 750 °C (the estimated consolute solution temperature, T_cs). A solvus exists below T_cs. The solvus becomes increasingly asymmetric at lower temperatures and extrapolates to n values of 0.2 and 0.7 at 300 °C. The extrapolated solvus is shown to be consistent with that predicted using a primitive regular solution model in which free energies of mixing are determined entirely from changes in configurational entropy at room temperature.     

Investigation of Nd:YVO4/YVO4 composite crystal and its laser performance pumped by a fiber coupled diode laser

Thermal effect control is critical to scale the output power of diode end-pumping solid lasers to several watts up and beyond. Diffusion bonding crystal has been demonstrated to be an effective method to relieve the thermal lens for the end-pumping laser crystal. The temperature distribution and thermal lens in Nd:YVO₄/YVO₄ composite crystal was numerically analyzed and compared with that of Nd:YVO4 crystal in this paper. The end-pumping Nd:YVO₄/YVO₄ composite crystal laser was set up and tested with z cavity. The maximum output power of 9.87 W at 1064 nm and 6.14 W at 532 nm were obtained at the pumping power of 16.5 W. The highest optical-optical conversion efficiencies were up to 60% at 1064 nm and 40% at 532 nm, respectively.     

Synthesis and nonlinear optical characterization of SnO2 quantum dots

The present paper demonstrates the preparation and characterization of SnO₂ semiconductor quantum dots. Extremely small ∼1.1 and ∼1.4 nm SnO₂ samples were prepared by microwave assisted technique with a frequency of 2450 MHz. Based on XRD analysis, the phase, crystal structure and purity of the SnO₂ samples are determined. UV-vis measurements showed that, for the both size of SnO₂ samples, excitonic peaks are obtained at ∼238 and ∼245 nm corresponding to ∼1.1 nm (sample 1) and ∼1.4 nm (sample 2) sizes, respectively. STM analysis showed that, the quantum dots are spherical shaped and highly monodispersed. At first, the linear absorption coefficients for two different sizes of SnO₂ quantum dots were measured by employing a CW He-Ne laser at 632.8 nm and were obtained about 1.385 and 4.175 cm⁻¹, respectively. Furthermore, the nonlinear refractive index, n₂, and nonlinear absorption coefficient, β, were measured using close and open aperture Z-scan respectively using the same laser. As quantum dots have strong absorption coefficient to obtain purely effective n₂, we divided the closed aperture transmittance by the corresponding open aperture in the same incident beam intensity. The nonlinear refraction indices of these quantum dots were measured in order of 10⁻⁷ (cm²/W) with negative sign and the nonlinear absorption coefficients were obtained for both in order of 10⁻³ (cm/W) with positive sign.     

Raman scattering and optical absorption studies of an orbital ordered Ca2RuO4

We have reported the Raman scattering and infrared absorption results on a t_2g orbital ordered Ca₂RuO₄. At 10 K, a strong and clear peak was observed in Raman scattering near 1360 cm⁻¹ with x′x′ geometry. In contrast to optic phonon modes, the peak does not show any frequency shift but rapidly decreases with increasing temperature. In addition, the peak is not observed in infrared absorption measurement. By comparing the previous Raman scattering results for several transition metal oxides, we have discussed the possible origins and ambiguities of the intriguing peak in Ca₂RuO₄.     

β-BaB2O4 deep UV monolithic walk-off compensating tandem

The generation of watt-level cw narrow-linewidth sources at specific deep-UV wavelengths corresponding to atomic cooling transitions usually employs external cavity-enhanced second-harmonic generation (SHG) of moderate-power visible lasers in birefringent materials. Among the oxo-borate materials, barium borate (β-BaB₂O₄ or BBO) combines the highest UV band edge and largest nonlinearity but suffers from large walk-off angles that limits the nonlinear interaction length. Alternative quasi-phase-matched (QPM) ferroelectrics are hardly suited for cavity-enhanced operation due to their much larger UV absorption and associated photo-refractive and thermal lensing effects, in addition to the difficult fabrication of fine-pitch domain gratings for short UV coherence lengths. In this work, we investigate an alternative approach to cw deep-UV generation by employing the low-loss BBO in a monolithic walk-off compensating structure [J.-J. Zondy, Ch. Bonnin, D. Lupinski, J. Opt. Soc. Am. B 20 (2003) 1675] to simultaneously enhance the effective nonlinear coefficient while minimizing the UV beam ellipticity under tight focusing. As a preliminary step to cavity-enhanced operation, and in order to apprehend the design difficulties stemming from the extremely low acceptance angle of BBO, we investigate and analyze the single-pass performance of a L_c = 8 mm monolithic walk-off compensating structure made of 2 optically-contacted BBO plates cut for type-I critically phase-matched SHG of a cw λ = 570.4 nm dye laser. As compared with a bulk crystal of identical length, a sharp UV efficiency enhancement factor of 1.65 has been evidenced with the tandem structure, but at ∼−1 nm from the targeted fundamental wavelength, highlighting the sensitivity of this technique when applied to a highly birefringent material such as BBO. Solutions to angle cut residual errors are identified so as to match accurately more complex periodic-tandem structure performance to any target UV wavelength, opening the prospect for high-power, good beam quality deep-UV cw laser sources for atom cooling and trapping.     

Theoretical investigation on thermal lensing effects of Yb:KY(WO4)2 in diode-pumped lasers

Based on the features of laser diode end-pumped lasers, a thermal model of Yb:KY(WO₄)₂(Yb:KYW) with square cross-section was established. Considering the heat transfer on side faces, the anisotropic of thermal conductivity and the latest reports about thermo-optic coefficient, thermal expansion coefficient and thermal conductivity, temperature distribution, end-pumped face distortion and thermal lens focal length of Yb:KYW were more precisely obtained using finite difference method to solve Poisson equation in a rectangular Cartesian coordinate for the first time. At the pump power of 14 W, the highest temperature located at the center of end-pumped face was 243.8 °C, the highest distortion was 0.28 μm, and the thermal lens focal length was 5.4 cm along z-axis and −4.9 cm along x-axis. The results show that thermal lensing effects in the b-cut Yb:KYW were mainly determined by the anisotropic thermal expansion of Yb:KYW, and further present thermal lensing effects become weaker after considering the heat transfer. This work is significant for compensating the thermal lensing effect and improving the resonator stability of diode-pumped anisotropy crystal lasers.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Antiferromagnetic resonance in ferroborate NdFe3(BO3)4

The AFMR spectra of the NdFe₃(BO₃)₄ crystal are measured in a wide range of frequencies and temperatures. It is found that by the type of its magnetic anisotropy the compound is an “easy-plane” antiferromagnet with a weak anisotropy in the basal plane. The effective magnetic parameters are determined: anisotropy fields H_a1=1.14 kOe and H_a2=60 kOe and magnetic excitation gaps Δν₁=101.9 GHz and Δν₂=23.8 GHz. It is shown that commensurate-incommensurate phase transition causes a shift in resonance field and a considerable change in absorption line width.At temperatures below 4.2 K nonlinear regimes of AFMR excitation at low microwave power levels are observed.     

Optical investigation of charge-transfer transitions in spinel Co3O4

Optical transitions in normal-spinel Co₃O₄ have been identified by investigating the variation of its optical absorption spectrum with the replacement of Co by Zn. Three optical-transition structures were located at about 1.65, 2.4, and 2.8 eV from the measured dielectric function of Co₃O₄ by spectroscopic ellipsometry. The variation of the absorption structures with the Zn substitution (Zn_xCo_3−xO₄) can be explained in terms of charge-transfer transitions involving d states of Co ions. The 1.65 eV structure is assigned to a d-d charge-transfer transition between the t_2g states of octahedral Co³⁺ ion and t₂ states of tetrahedral Co²⁺ ion, t_2g(Co³⁺)→t₂(Co²⁺). The 2.4 and 2.8 eV structures are interpreted as due to charge-transfer transitions involving the p states of O²⁻ ion: p(O²⁻)→t₂(Co²⁺) for the 2.4 eV absorption and p(O²⁻)→e_g(Co³⁺) for the 2.8 eV absorption. The observed gradual reduction of the 1.65 and 2.4 eV absorption strength with the increase of the Zn composition for Zn_xCo_3−xO₄ can be explained in terms of the substitution of the tetrahedral Co²⁺ sites by Zn²⁺ ions. The crystal-field splitting Δ_Oh between the e_g and the t_2g states of the octahedral Co³⁺ ion is estimated to be 2 eV.