Second-order optical susceptibility in doped III-V piezoelectric semiconductors in the presence of a magnetostatic field

A detailed analytical investigation of second-order optical susceptibility has been made in moderately doped III-V weakly piezoelectric semiconductor crystal, viz. n-InSb, in the absence and presence of an external magnetostatic field, using the coupled mode theory. The second-order optical susceptibility arises from the nonlinear interaction of a pump beam with internally generated density and acoustic perturbations. The effect of doping concentration, magnetostatic field and pump intensity on second-order optical susceptibility of III-V semiconductors has been studied in detail. The numerical estimates are made for n-type InSb crystals duly shined by pulsed 10.6 μm CO₂ laser and efforts are made towards optimising the doping level, applied magnetostatic field and pump intensity to achieve a large value of second-order optical susceptibility and change of its sign. The enhancement in magnitude and change of sign of second-order optical susceptibility, in weakly piezoelectric III-V semiconductor under proper selection of doping concentration and externally applied magnetostatic field, confirms the chosen nonlinear medium as a potential candidate material for the fabrication of nonlinear optical devices. In particular, at B ₀ = 14.1 T, the second-order susceptibility was found to be 3.4 × 10^-7 (SI unit) near the resonance condition.     

Importance of hydrogen bonding for second harmonic generation effect: X-ray diffraction and DFT study on S-benzyl isothiouronium chloride

X-ray diffraction study of the nonlinear optical (NLO) material S-benzyl isothiouronium chloride (C₈H₁₁N₂SCl) (SBTC) is reported for the first time. The single crystal of SBTC is orthorhombic with space group Pbca. SBTC exhibits second-order NLO susceptibility, and this study shows that hydrogen bonding is, in part, responsible for this. The present work shows that C-H?Cl and N-H?Cl hydrogen bonds direct the nature of the three-dimensional lattice. Such intermolecular interactions help to extend the molecular charge transfer into the supramolecular realm, the charge transfer originating as a consequence of the high level of molecular planarity and strong donor-to-acceptor interactions. Density functional theory (DFT) calculation and atom-in-molecule (AIM) analysis has been carried out to study the nature of hydrogen involved in the SBTC complex.     

Second harmonic generation in In2O3–SiON films doped by Al and Sn

Photoinduced optical and second-order non-linear optical effects in the interfaces separating In₂O₃–SiON (O/N ratio equals 1) films doped with A1, Sn and glass substrates were investigated using the photoinduced optical second harmonic generation. The photoinduced effective second-order optical susceptibility d_eff (at λ=1.76 μm) shows a good correlation with the linear optical susceptibility, particularly with the shift of the absorption edge. The maximal response of the photoinduced optical response signal was observed for the pump–probe delaying time of 34 ps. The performed experimental measurements indicate that the observed effects are mainly caused by the interface potential gradients on the border glass–In₂O₃–SiON film and by additional polarization due to insertion of the Al and Sn atoms. The observed phenomenon may be proposed as a sensitive tool for investigation of thin semiconducting interfacial layers and simultaneously such films may be used as materials for non-linear optical devices.     

Growth,optical, mechanical,dielectric and theoretical properties of picolinium maleate NLO single crystal

Nonlinear optical single crystals of picolinium maleate (PM) were grown by slow evaporation method. The grown crystal was subjected to single crystal X-ray diffraction analysis to confirm that the crystal belongs to the monoclinic crystal structure with space group P2₁/c. The optical transmission range of the grown crystal was measured by UV–Vis–NIR region with the lower cut-off wavelength as 330 nm. The optical bandgap is found to be 3.75 eV. Mechanical strength of the grown crystal was analyzed using Vickers microhardness tester. Dielectric constant and dielectric loss of picolinium maleate are measured in the frequency range from 50 Hz to 5 MHz at different temperatures. Further, electronic properties, such as valence electron plasma energy, Penn gap, Fermi energy and electronic polarizability of the grown crystal have been estimated.     

Nature of the nonlinear second-order optical susceptibility in molecular materials with C 2v molecular symmetry

The method of second-harmonic generation at the wavelength 1.06 μm is used to study the nonlinear second-order optical susceptibility of polycrystalline molecular materials with C _2v molecular symmetry belonging to the group of 2,6-dibenzadiene substituted cyclohexanes. The magnitude of the second harmonic signal is comparable to or greater than its value for polycrystalline urea and depends on the type of substituent (the stronger the donor properties of the substituent, the stronger the signal). It is shown that in the majority of the compounds investigated the large nonlinear optical polarizability observed is associated with the octupole moment of the molecule. Fiz. Tverd. Tela (St. Petersburg) 39, 1687–1689 (September 1997)     

Infrared absorption-edges of molecular nonlinear optical crystals: an <Emphasis Type="Italic">ab initio</Emphasis> calculation

A theoretical model suitable for calculating infrared absorption-edges of molecular nonlinear optical (NLO) crystals is introduced from high-level calculations of molecular vibrational spectra. The model is useful for elucidating the relationship between the molecular vibration and macroscopic absorption edges on the IR side of organic nonlinear optical crystals. The first-principle ab initio method carries out the calculations of IR absorption-edges of several typical molecular NLO crystals. These molecular NLO crystals include urea, 2-methyl-4-nitroaniline (MNA), meta-dinotrobenzene (MDNB), 3-methyl-4-methooxy-4^′-nitrostilbene (MMONS), and 3-hydroxyl-4^′-nitrostilbene (HMONS). The calculated results are compared with the measurements and good agreement is found between them. The experimentally unknown values of IR absorption-edges of some new synthesized crystals are predicted. The theoretical analyses of the structural origins of IR absorption cut-offs are discussed. The results are helpful for the molecular simulation and design of potential infrared molecular NLO crystals. Received: 9 April 2002 / Accepted: 18 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +86-591/3714946, E-mail: wkc@ms.fjirsm.ac.cn     

非线性光学晶体HgGa2S4 和 Hg0.5Cd0.5Ga2S4的能带结构、化学键及光学性质研究

用密度泛函理论和非谐振子模型计算了晶体HgGa₂S₄和Hg_0.5Cd_0.5Ga₂S₄的能带结构、态密度、化学成键及线性、非线性光学性质。结果表明：HgGa₂S₄的价带顶部主要是Ga-S成键态的贡献，导带底部主要是Ga-S反键态的贡献; Hg_0.5Cd_0.5Ga₂S₄的价带顶部主要由S-3p轨道组成，导带底部主要是Ga-S反键态的贡献。布居分析表明Ga-S键主要是共价成分，而Hg-S和Cd-S键主要是离子成分。HgGa₂S₄的折射率计算值与实验值在低能量区很好吻合。另外，HgGa₂S₄的能隙计算值比Hg_0.5Cd_0.5Ga₂S₄小，而二阶非线性极化率比Hg_0.5Cd_0.5Ga₂S₄大。     

Spectroscopic,structural and theoretical studies of 2‐methyl‐4‐nitroaniline (MNA) crystal. Electronic transitions in IR

Polarized FT‐IR, Raman, neutron scattering (IINS), and UV‐Vis‐NIR spectra of 2‐methyl‐4‐nitroaniline (MNA) crystal plates, powder, and solutions were measured in the 10–50 000 cm⁻¹ range. The FT‐IR spectrum of deuterated MNA (DMNA) in KBr pellet, the Raman spectrum of the DMNA powder as well as the EPR spectrum of the MNA powder were also recorded. Complete assignments of bands to normal vibrations have been proposed. Density functional theory (DFT) calculations of wavenumbers and potential energy distribution (PED) have been performed to strengthen the assignments. The analysis of vibrational and electronic spectra has revealed vibronic couplings in MNA molecules in solutions and in crystals. In the polarized FT‐IR spectra of the crystal five unusually large bands are observed in MIR and NIR regions. Their origin is discussed in terms of N H···O, C H···O, C H···H N hydrogen bonds, intermolecular charge transfers, electrostatic interactions, and ion radicals formation in the crystal. The role of a methyl group introduction to 4‐nitroaniline is analyzed. The crystal structure of MNA at the room temperature was re‐investigated. Copyright © 2008 John Wiley & Sons, Ltd.     

Ultrasonic measurement of the elastic properties of benzoyl glycine single crystals

Certain organic crystals are found to possess high non-linear optical coefficients, often one to two orders of magnitude higher than those of the well-known inorganic non-linear optical materials. Benzoyl glycine is one such crystal whose optical second-harmonic generation efficiency is much higher than that of potassium dihydrogen phosphate. Single crystals of benzoyl glycine are grown by solvent evaporation technique usingN, N-dimethyl formamide as the solvent. All the nine second-order elastic stiffness constants of this orthorhombic crystal are determined from ultrasonic wave velocity measurements employing the pulse echo overlap technique. The anisotropy of elastic wave propagation in this crystal is demonstrated by plotting the phase velocity, slowness, Young’s modulus and linear compressibility surfaces along symmetry planes. The volume compressibility, bulk modulus and relevant Poisson’s ratios are also determined. Variation of the diagonal elastic stiffness constants with temperature over a limited range are measured and reported.     

Ab initio study of the linear and nonlinear optical responses in BiAlO3

The linear and non-linear optical properties of BiAlO₃ are studied by employing the density functional perturbation theory within the local density and generalized gradient approximations. The computations are based on the electronic structure obtained within density functional theory. The optical properties such as the dielectric function, refractive index, spectral reflectivity, absorption coefficient and electron energy-loss spectrum are obtained in the energy region of up to 30 eV. The calculated value of the birefringence for BiAlO₃ shows that it is a uniaxial negative crystal and has a large birefringence. We also report our studies on the second harmonic generation response coefficient over a large frequency range for BiAlO₃ crystal. The predicted second-order optical spectra indicate pronounced structures related to of 1ω and 2ω frequency resonances. Furthermore, the non-linear optic and linear electro-optic coefficients are computed by employing 2n + 1 theorem applied to an electric-field dependent energy functional. The results are compared with the available calculations.     

晶体电光和非线性光学效应的离子基团理论(Ⅲ)——利用畸变氧八面体的离子基团模型计算LiNbO3,LiTaO3,KNbO3,BNN晶体的电光和倍频系数

本文用文献[1]中所提出的(MO₆)离子基团模型,计算LiNbO₃,LiTaO₃,KNbO₃,BNN等晶体的电光和倍频系数。假设在O_h对称时,这些晶体中的氧八面体具有相同的能级和对称波函数,则通过群表示理论就可得到在C_3ν,C_2ν对称性时氧八面体的能级和对称波函数,并进而用ABDP理论计算它们的电光和倍频系数。计算结果和实验符合得相当好。本文并从理论上解释了这些晶体的倍频系数大小、符号和氧八面体畸变间的关系,由此可以得到以下两个结论:(1)畸变氧八面体的离子基团模型不但适用于钙钛矿型材料,同时也适用于钨青铜型、LiNbO₃型材料。(2)在钨青铜型、LiNbO₃型的材料中,仍是“离子键”对电光和倍频效应作出主要贡献,同时由于LiTaO₃的共价键成份比LiNbO₃大,因而LiTaO₃的非线性光学效应比LiNbO₃小。     

Photoinduced second-order optical susceptibilities of Er2O3 doped TeO2-GeO2-PbO glasses

Second-order optical susceptibilities were established in the optically poled erbium doped tellurite glasses near the melting temperature. The non-linear optical susceptibility was formed by bicolor coherent optical treatment performed by two coherent laser beams originated from 50 ps Nd-YAG laser (λ = 1.32 μm) exciting the high pressure hydrogen laser cell emitting at 1907 nm. The non-centrosymmetric grating of the medium was created by coherent superposition of the fundamental laser illumination at 1907 nm and the doubled frequency one at 953.5 nm. The maximally all-optically poled SHG occurs for 2% doped Er₂O₃ (in weighting units) TeO₂-GeO₂-PbO glass. It was found that the photoinduced SHG demonstrates a saturation during the photo-treatment of 9-10 min using the two beams polarized at angle about 45° between them. During the coherent bicolor optical treatment it was achieved the value of second-order susceptibility up to 3.6 pm/V at 1907 nm. The optimal ratio between the fundamental beam with power density about 1.1 GW/cm² and writing doubled frequency seeding beam about 0.015 GW/cm² corresponds to the maximal of photoinduced SHG. For glasses with lower concentration of Er₂O₃, the relaxation of the second-order optical susceptibility is substantially longer and achieves SHG value that corresponds to 80% of the maximal ones. It is necessary to emphasize that efficient optically-poled grating exists only within the narrow temperature range near the glassing temperature. Possible physical mechanisms of the phenomenon observed are discussed. Generally the used glasses possess better parameters than early investigated germinate glasses.     

Size effect on the SHG properties of Cu-doped CdI2 nanocrystals

Because the optically induced second harmonic generation (SHG) is prevented by symmetry in a centrosymmetric material, one needs to form noncentrosymmetric processes in order to observe the SHG. However, one of the efficient ways to enhance the noncentrosymmetricity of a material is to dope it with an appropriate impurity and amount. We grow Cu-doped CdI₂ layered nanocrystal structures from the mixture of CdI₂ and CuI using the standard Bridgman-Stockbarger method and investigate the nano-confined effects by studying the second-order optical effect via the measurements of SHG. The second-order susceptibility for the nanocrystals is calculated and the values at liquid helium temperature range from 0.38 to 0.83 pm V⁻¹ for the thicknesses of 10-0.8 nm respectively. The size dependence demonstrates the nano-sized quantum-confined effect with a clear increase in the SHG with decreasing the thickness of the nanocrystal or crystal temperature. Since the local electron-phonon anharmonicity is described by third-order rank tensors in disordered systems, the SHG is very similar to that one introduced for the third-order optical susceptibility. It has been confirmed by observing the large photoluminescent yield of the pure crystals. The Raman scattering spectra taken for thin nanocrystals confirm the phonon modes originating from interlayer phonons crucially responsible for the observed effects. The obtained results show that the Cu-doped CdI₂ layered nanocrystals are promising materials for applications in optoelectronic nano-devices.     

Time evolution of polar regions in (Sr0.65Ba0.35)2NaNb5 O 15 single crystal

The linear, second-order and third-order dielectric susceptibilities χ₁, χ₂, χ₃ of a (Sr_0.65Ba_0.35)₂NaNb₅O₁₅ (SBNN) single crystal have been measured. Strong relaxation was found in all investigated dielectric susceptibilities near the phase transition. The time dependence of linear and third-order dielectric susceptibility can be explained as the effect of polar nano-clusters evolution. Near the phase transition, the net polarization of the crystal, monitored by second-order dielectric susceptibility, changes both its value and orientation. Measurements of the pyroelectric effect indicate that the non-zero net polarization in SBNN crystals appears spontaneously. In addition, the ferroelectric phase transition in SBNN showed many features of a first-order phase transition.     

Manifestation of nano-sized effects in photoinduced nonlinear optics of CdI2–Cu layered single crystals

The infrared (IR) induced second harmonic generation in the thin CdI₂–Cu crystalline layers was discovered. With decreasing thickness of the CdI₂–Cu crystals up to several nanometers value of second-order nonlinear optical susceptibility d₁₄ (at wavelength λ=2.76 μm) for the output IR-induced SHG significantly increases. For the Cu content about 0.4% the output SHG signal achieves its maximum at the sample thickness below 2 nm. It is important that for the samples with larger film thickness the corresponding changes have substantially different properties. Limitation of the d₁₄ at the larger concentration is probably caused by formation of the Cu clusters limiting the enhancement of the hyperpolarizability for particular cluster as well as total nonlinear dielectric susceptibility.     

Enhancement of optical nonlinearity in a guest-host system by nematic ordering

Second-harmonic generation (SHG) has been studied for understanding the enhancement mechanism for the second-order optical nonlinearity by the nematic (or axial) ordering in a liquid crystal doped with one-dimensional nonlinear optical (NLO) organic molecules. An extended version of the Maier-Saupe mean-field theory for nematic liquid crystals was developed to obtain analytical expressions for the second-order NLO coefficients in terms of the axial order, the polar order and the effective nematic potential. From the SHG data in a guest-host system composed ofN,N'-dimethylaminonitrostilbene molecules (0.5% by weight) and a liquid crystal, the enhancement of the second-order NLO coefficient,d ₃₃, by nematic ordering becomes almost 3, which agrees well with our theoretical predictions.     

Linear and Nonlinear Optical Properties Of Racemic (±)2-(α-Methylbenzylamino)-5-Nitropyridine Single Crystals

Linear and nonlinear optical properties of racemic (±)2-(α-methylbenzylamino)-5-nitropyridine ((±)MBANP) single crystals have been comprehensively investigated and compared with those of the enantiomorph (–)2-(α-methylbenzylamino)-5-nitropyridine ((–)MBANP) crystals. (±)MBANP crystal exhibits very high chemical and physical stability, but relatively small nonlinear optical coefficients (d₃₁ = 6.8 pm/V, d₃₂ = 4.7 pm/V, d₃₃ = 0.84 pm/V). A comparison between the nonlinear optical coefficients of (±)MBANP and (–)MBANP demonstrates the validity of the oriented-gas model in molecular crystals that neglects all the contributions from intermolecular interaction.     

Effect of deuteration on the electronic and electron-vibrational properties of the organic conductor k-(D8-BEDT-TTF)2[Hg(SCN)2Br]

We present here for the first time polarized reflection spectra and optical conductivity spectra of single crystals of the newly deuterated organic conductor k-(D₈-BEDT-TTF)₂[Hg(SCN)₂Br] at room temperature. The spectral region investigated is 700–40 000 cm⁻¹. We examined the effect of deuteration on electronic and electron-vibrational transitions observed in the spectra. The observed shift of the electron “dimer” transition in the infrared toward lower frequencies upon deuteration is linked with an increase in the interaction between neighboring, mutually perpendicular dimers in the structure of the deuterated crystal. A lowering of the symmetry of the BEDT-TTF molecule is demonstrated in crystals similar to k-(BEDT-TTF)₂[Hg(SCN)₂Br], relative to the symmetry D _2h of the free molecule. We refine the assignment of the spectral features determined by the interaction of electrons with the fully-symmetric intramolecular vibrations of the C=C, C-S, and C-C-H bonds of the BEDT-TTF molecule. Fiz. Tverd. Tela (St. Petersburg) 40, 1595–1598 (September 1998)     

The role of water in the design of glycosidic linkage flexibility

In this paper we show how a variety of computational methods are used to understand the role that water plays in the solution conformational dynamics of carbohydrates. A comparison is made between maltose and a designed disaccharide (α-D-Glc-NAc-(1→4)-β-D-Glc-3-NH₂) in which the cross glycosidic linkage hydrogen bonds have been significantly strengthened. However, despite the stronger intramolecular hydrogen bonds in the maltose derivative, the correlation times for glycosidic dihedral angle fluctuations are approximately the same for the two sugars. Upon investigation of the water in the first hydration shells for the two disaccharides, high water probability densities were found between the functional groups straddling the glycosidic linkage that bonds the two monosaccharides together. This probability density corresponds to single water molecules forming bridging hydrogen bonds between the functional groups on either side of the linkage for periods of 3.66 ps in the case of maltose and 8.36 ps in the case of the amine derivative. Ab initio studies of saccharide structure interaction with single water molecules reveal that these intermolecular (sugar-solvent) hydrogen bonds are of similar strength to the intramolecular (sugar-sugar) hydrogen bonds. This combination of molecular dynamics and ab initio computational methods demonstrates that increasing the internal hydrogen bond strength in oligosaccharides does not lead to significantly slower internal molecular motion of these sugars in solution. The intermolecular hydrogen bonds formed with water compete equally with the intramolecular hydrogen bonds in the sugar. This result has important implications when considering hydrophobic versus hydrophilic effects in glycoproteins.     

Second-order nonlinear optical susceptibility in chalcone-group crystalline molecular compounds

A study is reported of the second-order nonlinear optical susceptibility in polycrystalline molecular materials of the chalcone group made by second-harmonic generation at a wavelength of 1.06 μm. Some of the compounds studied exhibit a high nonlinear activity and are transparent in the blue region of the spectrum. The measured macroscopic nonlinear polarizability χ ² was compared with the calculated values of β, the second-order molecular polarizability tensor. The high nonlinear optical polarizability observed in some chalcone compounds is shown to be related to crystal symmetry type. Fiz. Tverd. Tela (St. Petersburg) 41, 2084–2087 (November 1999)