Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

Third-order nonlinear optical response of Au-core CdS-shell composite nanoparticles embedded in BaTiO<Subscript>3</Subscript> thin films

Au-core CdS-shell composite nanoparticles were synthesized by a direct self-assembly process and integrated into BaTiO₃ thin films. Characterization by transmission electron microscopy showed that the average diameter of these composite nanoparticles was about 8 nm. Using the femtosecond time-resolved optical Kerr effect method, we investigated the third-order nonlinear optical response of the Au@CdS nanoparticles embedded in the BaTiO₃ thin films at a wavelength of 800 nm. An ultrafast nonlinear response and a large effective third-order nonlinear susceptibility of χ⁽³⁾=7.7×10^-11 esu were observed. We attributed the enhancement of the third-order optical nonlinearity to a localized electric field effect originating from the core-shell structure under off-surface-plasmon resonance conditions. Received: 13 May 2002 / Revised version: 23 October 2002 / Published online: 3 April 2003 RID="*" ID="*"Corresponding author. Fax: +86-21/6510-4949, E-mail: sxqian@fudan.ac.cn     

CuO薄膜的三阶非线性光学特性研究

采用脉冲激光沉积技术在Si(100)和熔石英基片上制备了单相的CuO薄膜.通过X射线衍射仪,拉曼光谱仪,场发射扫描电镜和紫外可见光光度计对薄膜的结构,表面形貌和光学性质进行了表征. 场发射扫描电镜结果表明CuO薄膜中晶粒排列致密且分布均匀,其尺寸约为45nm.结合飞秒激光(800nm,50fs)和Z扫描方法测量了薄膜的三阶非线性光学特性,结果表明CuO薄膜具有超快的非线性光学响应且非线性折射率和非线性吸收系数均为负值,其大小分别为-3.96×10^-17 m^{2< 关键词： CuO薄膜 Z-扫描')" href="#">Z-扫描 三阶光学非线性}     

Nonlinear optical characterization of LaEr(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> thin films using the <Emphasis Type="BoldItalic">Z</Emphasis> -scan technique

The nonlinear optical properties of thin films of LaEr(MoO₄)₃ were studied using a ∼30 ps Nd:YAG laser at 532 nm with a repetition rate of 250 Hz. Closed aperture Z-scan measurement revealed a negative nonlinearity in the LaEr(MoO₄)₃. The nonlinear refractive index γ=1.38×10^-10 cm²/W and nonlinear absorption coefficient β=16.8×10^-6 cm/W were calculated from the Z-scan data. The fluorescent upconversion spectra were recorded with 980 nm excitation. An optical switching mechanism based on nonlinear absorption is also presented experimentally. PACS 81.15.Fg; 77.84.Bw; 33.50.Dq; 42.70.Mp     

Study of the third order nonlinear optical properties of Zn<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>Se and Cd<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>Se crystals

Third order nonlinear optical susceptibilities χ^<3> of ternary Zn_1−xMg_xSe and Cd_1−xMg_xSe crystals have been measured using standard degenerate four-wave mixing (DFWM) method at 532 nm. The nonlinear transmission technique has been applied to check if our crystals exhibit two-photon absorption. The studied Zn_1−xMg_xSe and Cd_1−xMg_xSe solid solutions were grown from the melt by the modified high-pressure Bridgman method. For both crystals the energy gap increases with increasing Mg content. In the case of Zn_1−xMg_xSe, it was found that the value of third order nonlinear optical susceptibility χ^<3> decreases with increasing Mg content. An explanation of this behaviour results from the dependence of optical nonlinearities on the energy band gap E_g of the studied crystals. In the case of Cd_1txMg_xSe with low content of Mg, no response was observed for the studied wavelength since the energy gap in such crystals is smaller than the photon energy of the used laser radiation. It was also found that the value of third order nonlinear optical susceptibility χ^<3> for Cd_0.70Mg_0.30Se is higher than for Zn_0.67Mg_0.33Se. This behaviour can be understood if one take into consideration that the free carrier concentration in Cd_1−xMg_xSe samples is about four orders of magnitude higher than that in Zn_1txMg_xSe ones with comparable Mg content respectively. It is commonly known that when the electric conductivity increases, the values of nonlinear optical properties increase. From the performed measurements one can conclude that the incorporation of Mg as constituent into ZnSe and CdSe crystals leads to a change of the third order nonlinear optical susceptibilities.     

Optimized second-order optical nonlinearity in thermally poled GeS<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>-KI chalcohalide glass

0.56GeS₂-0.24Ga₂S₃-0.2KI (mol%) chalcohalide glass was prepared and second-harmonic generation was observed by the thermal poling process. Second-order optical nonlinearity in the glass was also investigated by different poling temperature, voltage and time to optimize the poling parameters to improve χ ⁽²⁾. The maximum χ ⁽²⁾ in our study as large as 3.74 pm/V was obtained under the optimized poling condition with 5.2 kV, 260°C and 120 minutes.     

Electro-optic properties of epitaxial Sr<Subscript>0.6</Subscript>Ba<Subscript>0.4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films grown on MgO substrates using Li<Subscript>x</Subscript>Ni<Subscript>2-x</Subscript>O buffer layer

Textured Li_xNi_2-xO (LNO) thin films have been fabricated on (001)MgO substrates by pulsed laser deposition technique. The as-deposited LNO films shows a conductivity of 2.5×10^-3 Ω m and possess a transmittance of about 35% in the visible region. Subsequent deposition of Sr_0.6Ba_0.4Nb₂O₆ (SBN60) thin film on these LNO-coated MgO substrates resulted in a textured SBN layer with a 〈001〉 orientation perpendicular to the substrate plane. Phi scans on the (221) plane of the SBN layer indicated that the films have two in-plane orientations with respect to the substrate. The SBN unit cells were rotated in the plane of the film by ± 8.2° as well as ± 45° with respect to the LNO/MgO substrate. Besides the highly (00l)-orientation, the SBN films also exhibited a dense microstructure as shown by scanning electron microscopy. The electro-optic coefficient (r₃₃) of the SBN film was measured to be 186 pm/V. On the basis of our results, we have demonstrated that the LNO film can be used as a buffer layer as well as a transparent bottom electrode for waveguide applications. The SBN/LNO heterostructure is also a suitable candidate for integrated electro-optics devices. PACS  42.79.Gn; 42.82.Et; 78.20.Ci     

Two-photon absorption of high-power picosecond pulses in PbWO<Subscript>4</Subscript>, ZnWO<Subscript>4</Subscript>, PbMoO<Subscript>4</Subscript>, and CaMoO<Subscript>4</Subscript> crystals

The nonlinear process of two-photon interband absorption is studied in tungstate and molybdate oxide crystals excited by a sequence of high-power picosecond pulses with a wavelength of 523.5 nm. The transmission of the crystals is measured for the excitation pulse intensity up to 100 GW/cm². The pulse intensity in the crystals initially transparent at a wavelength of 523.5 nm is strongly limited due to two-photon absorption (TPA), and the reciprocal transmission in PbWO₄ and ZnWO₄ crystals reaches 50–60. In all crystals, TPA induces long-lived one-photon absorption, which affects the nonlinear process dynamics and leads to a hysteresis in the dependence of the transmission on the laser excitation intensity. Absorption dichroism manifests itself in a significant difference in the transmission intensities when the principal orthogonal optical axes of the crystals are excited. The TPA coefficients are determined during the excitation of two optical axes of the crystals. TPA coefficients β for the crystals vary over a wide range, namely, from β = 2.4 cm/GW for PbMoO₄ to β = 0.14 cm/GW for CaMoO₄, and the values of β can differ almost threefold when different optical axes of a crystal are excited. Good agreement is achieved between the measured intensities limited by TPA and the estimates calculated from the measured nonlinear coefficients. Stimulated Raman scattering (SRS) upon excitation at a wavelength of 523.5 nm is only detected in two of the four crystals under study. The experimental results make it possible to explain the suppression of SRS by its competition with TPA, and the measured nonlinear coefficients are used to estimate this suppression.     

Optical nonlinearities in hyperbranched polyyne studied by?two-photon excited fluorescence and third-harmonic generation spectroscopy

The nonlinear optical properties of a hyperbranched polyyne (hb-Polyyne) have been measured at infrared wavelengths by using femtosecond and nanosecond pulsed excitation. This hyperbranched polyyne exhibited strong and intrinsic (simultaneous) two-photon absorption and upconverted blue fluorescent emission under femtosecond excitation around 800 nm. The hb-Polyyne in chloroform solution is characterized by a large two-photon absorption cross section of 9068 GM (1GM=10⁻⁵⁰ cm⁴ s) and a fluorescence quantum yield of 0.57. On the other hand, by third-harmonic generation (THG) spectroscopy with nanosecond excitation, the measured third-order nonlinear susceptibility χ ⁽³⁾ for solid films of hb-Polyyne ranged from 2.4×10⁻¹¹ to 6.1×10⁻¹¹ esu in the spectral range of 1100–1600 nm, with results comparable to the values exhibited by the well-known conjugated polymer MEH:PPV, but with a much better transparency for visible wavelengths.     

Superconductivity and electronic liquid-crystal states in twin-free YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6+x</Subscript> studied by neutron scattering

In this paper, we first give a concise overview of recent experimental and theoretical work dealing with “electronic liquid-crystal states” which spontaneously break different symmetries of the CuO₂ layers of high-T _c cuprates, with an emphasis on evidence in the spin excitation spectrum. Then we describe the importance of using twin-free samples to look for evidence for fourfold symmetry breaking in the spectrum and explain the preparation procedure to obtain such samples. We present inelastic neutron scattering results for moderately underdoped YBa₂Cu₃O_6.6(T _c = 61  K) and nearly optimally doped YBa₂Cu₃O_6.85(T _c = 89  K). In YBa₂Cu₃O_6.6, the dispersion topology changes when heating above T _c from an hourglass shape with constricted, commensurate resonance peak to a “Y”-shape without resonance anomaly. This change, and the fact that the low-energy signal above T _c can be described by an incommensurate, quasi-one-dimensional distribution, indicates a competition of superconductivity with an electronic liquid-crystal state. We then show a striking analogy between the difference signal I(5  K) − I(70  K) and the downward dispersing resonance mode in YBa₂Cu₃O_6.85. We therefore argue that a resonance mode only emerges below T _c, irrespective of the doping level. We finally discuss the implications of our results for the different scenarios invoked to explain the electronic liquid-crystal state in cuprates.     

Patterning and morphology of nonlinear optical Gd<Subscript>x</Subscript>Bi<Subscript>1-x</Subscript>BO<Subscript>3</Subscript> crystals in CuO-doped glass by YAG laser irradiation

Dots and lines consisting of nonlinear optical Gd_xBi_1-xBO₃ crystals were patterned on the surface of CuO-doped Gd₂O₃-Bi₂O₃-B₂O₃ glass by heat-assisted (200 °C) Nd:YAG laser irradiations with a wavelength of λ=1064 nm, where the laser energy absorbed by Cu²⁺ is converted to the local heating of the surrounding Cu²⁺. The surface morphology and orientation of crystals in the patterned lines were clarified from confocal scanning laser microscope observations and polarized micro-Raman scattering spectra. Crystal lines with periodic bumps (i.e., ladder-shape like lines) were patterned by laser irradiations with a power of 0.79 W and a scanning speed of 60 μm/s, and the orientation of Gd_xBi_1-xBO₃ crystals in the lines was proposed. The present study demonstrates that the combination of Cu²⁺ and continuous wave Nd:YAG laser with λ=1064 nm is effective in inducting crystallization of oxide glasses. The mechanism of laser-induced crystallization in glass has also been discussed. PACS 61.43.Fs; 42.70.Mp; 68.35.Bs; 78.30.-j; 79.20.Ds     

Evolution of a femtosecond laser-induced plasma and energy transfer processes in a SiO<Subscript>2</Subscript> microvolume detected by the third harmonic generation technique

A nonlinear optical method has been proposed for probing the evolution of a plasma and energy transfer processes in the microvolume of a transparent dielectric using the third-harmonic probe signal. The electron self-trapping time has been estimated as t = 150 ± 80 fs. A decrease in the third-harmonic probe signal has been detected at the picosecond time scale; this decrease can be attributed to a change in the third-order susceptibility χ⁽³⁾ of a fused silica sample modified by laser radiation.     

Spectroscopic properties of Er<Superscript>3+</Superscript> ions in LiNbO<Subscript>3</Subscript> crystals codoped with HfO<Subscript>2</Subscript>

The results of the spectroscopic analysis of transition strengths for Er³⁺ ions in a series of Hf:Er:LiNbO₃ crystals with variable Hf content and fixed Er content are reported. Unpolarized UV-VIS-NIR absorption spectra, upconversion fluorescence spectra excited at 800 nm, and microsecond time-resolved spectra excited at 400 nm and 800 nm by 800 nm femtosecond laser were measured at room temperature. The HfO₂ incorporation has influence on Er³⁺ radiative lifetimes, and fluorescence branching ratios. For Hf(4 mol %):Er(1 mol %):LiNbO₃, Ω₂=2.63×10^-20 cm², Ω₄=2.86×10^-20 cm², and Ω₆=0.72×10^-20 cm². Ω₂<Ω₄ is contrary to the Er³⁺ general trend of Ω₂>Ω₄>Ω₆ when the Hf content is below its threshold concentration. In addition, the sum of Ω increases with the Hf content when the HfO₂ content below 6 mol % is unfamiliar. The upconversion mechanism is discussed in this work. PACS 71.20.Eh; 77.84.Dy; 42.62.Fi; 42.65.Ky     

EPR and optical absorption studies of Cu<Superscript>2+</Superscript> ions in [ZnPd(CN)<Subscript>4</Subscript>(C<Subscript>4</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O<Subscript>2</Subscript>)] single crystals

A Cu²⁺-doped single crystal of catena-trans-bis(N-(2-hydroxyethyl)-ethylenediamine) zinc(II)-tetra-m-cyanopaladate(II) [ZnPd(CN)₄(C₄H₁₂N₂O₂)] complex has been investigated by electron paramagnetic resonance (EPR) technique at room temperature. EPR spectra indicate that Cu²⁺ ions substitute for magnetically equivalent Zn²⁺ ions and form octahedral complexes in [ZnPd(CN)₄(C₄H₁₂N₂O₂)] hosts. The crystal field affecting the Cu²⁺ ion is nearly axial. The optical absorption studies show two bands at 322 nm (30864 cm⁻¹) and 634 nm (15337 cm⁻¹) which confirm the axial symmetry. The spin Hamiltonian parameters and the relevant wave function are determined.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

Photoluminescence of fluoroacrylate polymers impregnated with Eu(bta)<Subscript>3</Subscript> using supercritical CO<Subscript>2</Subscript>

Optical properties (photoluminescence and absorption) of Eu(bta)₃(B) _n (B = H₂O or 1,10-phenanthroline) polycrystalline powders and fluoroacrylate polymers (FAPs) impregnated with these compounds using supercritical CO₂ (SC CO₂) were investigated. It was established that impregnation of Eu(bta)₃phen into the FAPs using an SC CO₂ solution was difficult to achieve. The type of B (ancillary ligand) and the polymer matrix were shown to influence the temperature quenching of photoluminescence of Eu³⁺ ions in the range 25–100°C. A comparative analysis of quantum yields (λ_ex = 300 and 380 nm) and photoluminescence decay times (λ_ex = 337.1 nm) for Eu(bta)₃B _n and for Eu(bta)₃B _n -doped FAPs was performed.     

Characterization of channel waveguides in Pr:YLiF<Subscript>4</Subscript> crystals fabricated by direct femtosecond laser writing

Single tracks and pairs of tracks are written in the volume of Pr-doped LiYF₄-crystals using tightly focused femtosecond laser radiation (λ=1045 nm, τ _p=400–500 fs, f=0.1–1 MHz). Waveguiding between the tracks is demonstrated and optimized by varying the distance between the tracks and the laser writing conditions. The stress-induced guiding mechanism is explained based on TEM, interference microscopy, near-field and far-field measurements. It is shown that the single-crystalline material is getting poly-crystalline under femtosecond laser irradiation. By measuring the lifetime of the ³P₁→³H₅ transition and the emission spectrum at excitation with λ=444 nm, no influence on these properties of the guided light is observed. This possibly enables the realization of a channel waveguide laser in the visible spectral range.     

Direct observation of the vibrational energy redistribution in (CF<Subscript>3</Subscript>)<Subscript>2</Subscript>CCO molecules resonantly excited by femtosecond infrared laser radiation

The dynamics of multiphoton excitation of (CF₃)₂CCO molecules has been investigated under the condition of resonant action of femtosecond infrared laser radiation on the ν₁ vibrational mode of the C=C=O bond. It has been shown that the mode-selective excitation of this vibration occurs up to the ν = 6 level. The kinetics of the subsequent intramolecular vibrational energy redistribution from the ν₁ mode has been measured. A value of 5 ± 0.3 ps has been obtained for the characteristic time of this process.     

Large third-order nonlinear optical susceptibility of Au-Al2O3 composite films near the resonant frequency

2 O₃ composite films with high Au concentrations (30%–60% in volume fraction) were prepared by reactive co-sputtering and post rapidly thermal annealing. The structure of the films and the size distributions of the Au nanoclusters were examined by TEM, and the third-order nonlinear optical susceptibility χ⁽³⁾ was measured by degenerated four-wave mixing using a 70-ps pulse laser at 532 nm. The maximum value of the χ⁽³⁾ was about 1.2×10^-6 esu in the annealed films and occurred at around 45% Au concentration. The figure of merit, χ⁽³⁾/α (α is the absorption coefficient), has a value of 7×10^-12 esu cm over a wide range of Au concentrations. Received: 23 July 1997     

Luminescence and selective heat radiation of Yb<Subscript>2</Subscript>O<Subscript>3</Subscript> upon the resonant and thermal laser excitation

Yb₂O₃ polycrystals with a size of up to 10 mm are synthesized using the sintering and melting of the ultrapure Yb₂O₃ powders by the CO₂-laser radiation with the power P _L ≤ 100 W at the wavelength λ = 10.6 μm at the melting point T _m = 2703 K, forming due to surface tension in melt, and crystallization in air. The analysis of the polycrystal microstructure using the methods of optical and electron microscopy and X- ray diffractometry shows that perfect oxide crystallites are formed in the course of crystallization after melting-through. The transformation of the luminescence and selective heat radiation (SHR) spectra of the Yb₂O₃ polycrystals is studied under the resonant excitation at λ ≈ 975 nm using a laser diode and the laser heating at the wavelength λ = 10.6 μm. When the resonant excitation power of the Yb³⁺ ions increases from 0.15 to 4.5 W, the Stokes luminescence of the Yb₂O₃ polycrystals is sequentially transformed into SHR and the thermal radiation of the crystal lattice. The transformation of the emission spectra of the Yb₂O₃ polycrystals with an increase in the laser heating intensity by about four orders of magnitude can be represented as the low-temperature heat radiation, spectral burst of the thermodynamically nonequilibrium SHR of the Yb³⁺ ions, and the high-temperature radiation of the crystal lattice. The temperature dependence of the luminescence spectra and SHR of the Yb₂O₃ polycrystals on the intensity of the laser and laser-thermal excitation and the concentration quenching of the Yb³⁺ luminescence in oxides indicate the key role of the interaction of the f-electron shell of the Yb³⁺ ions with the natural oscillations of the crystal lattice in the processes of the multiphonon excitation and nonradiative (multiphonon) and radiative (vibronic) relaxation.