Large Third-order Optical Nonlinearity Research Articles

Synthesis and photophysical characterization of MWCNTs/poly(pyrrolyl methine) composite with large third-order optical nonlinearity

MWCNTs/poly (pyrrolyl methine) composites with the different contents of MWCNTs were synthesized by in-situ ultrasonic polymerization, and their structures and photophysical properties were also investigated. The results revealed that the third-order nonlinear optical susceptibility of MWCNTs/PHPDTBE composite showed a rapid increase with the increase of MWCNTs’ content, and obtained a maximum value of 3.41×10−7 esu, which was almost ten times larger than that of PHPDTBE of 3.49×10−8 esu. The enhanced optical nonlinearity was attributed to strong photoinduced electron transfer from PHPDTBE to MWCNTs by right of their strong noncovalent π-π interaction in the photoexcited state.

Large third-order optical nonlinearities in iron oxide thin films synthesized by reactive pulsed laser deposition

We report on a study of the third-order nonlinear optical properties of Fe2O3 thin films, grown by the method of laser deposition on silica (SiO2) substrates. The films were synthesized on substrates at different temperatures (293 K and 800 K) and under different oxygen pressures (0.1 Pa, 0.5 Pa, 1.0 Pa). The resulting films were amorphous, if grown on cold substrates (293 K), or polycrystalline otherwise. The third-order optical susceptibility χ(3) of the films was determined by the Z-scan method at the wavelengths of 1064 nm and 532 nm and the laser pulse width of 20 ns. Remarkably high χ(3) values on the order of 10−4 esu at 1064 nm are obtained. The results show that Fe2O3 thin films are promising nonlinear materials for contemporary optoelectronics.

Nonlinear optical properties and optical power limiting effect of Giemsa dye

The nonlinear optical properties of Giemsa dye in chloroform solution for different concentrations and dye mixed with poly(methylmethacrylate) (PMMA) as a dye-doped polymer film were investigated using continuous wave (CW) low power solid-state laser (SSL) operating at wavelength of 532nm as an excitation source. Using the single beam z-scan technique, the nonlinear refractive index (n2), the nonlinear absorption coefficient (β), and the third-order nonlinear optical susceptibility (χ(3)) of Giemsa dye were measured. The measurements reveal that both n2 and β are dependent on the dye concentration. The obtained results indicate that the Giemsa dye exhibits positive nonlinear saturable absorption (SA) and negative refraction nonlinearity, manifestation of self-defocusing effect. Optical power limiting characteristics of the Giemsa dye at different concentrations in solution and polymer film were studied. The observed large third-order optical nonlinearity of Giemsa dye confirms that Giemsa dye is a promising nonlinear material for the optical power limiting and photonic devices applications.

Near-UV-enhanced broad-band large third-order optical nonlinearity in aluminum nanorod array film with sub-10 nm gaps.

Plasmonic nanostructures with sub-10 nm gaps possess intense electric field enhancements, leading to their high reputation for exploring various functional applications at nanoscale. Till now, although large amounts of efforts have been devoted into investigation of such structures, few works were emphased on the nonlinear optical properties in near-ultraviolet (UV) region. Here, by combining sputtering technique and an optimized anodic aluminum oxide (AAO) template growing method, we obtain aluminum (Al) nanorod array film (NRAF) with average rod diameter and gap size of 50 and 7 nm, respectively. The Al-NRAF exhibits large third-order optical nonlinear susceptibility (χ(3)) and high figure of merit (χ(3)/α) over a broad wavelength range from 360 to 900 nm, and reaches their maximums at the shortest measured wavelength. In addition, comparisons with Au-NRAF and Ag-NRAF samples further confirm that Al-NRAF has better nonlinear optical properties in the blue and near-UV wavelength regions. These results indicate that Al nanostructures are promising candidates for nonlinear plasmonic applications at blue and near-UV wavelengths.

Third order nonlinear optical properties of organometal halide perovskite by means of the Z-scan technique

The nonlinear optical response of CH3NH3PbBr3 perovskites is investigated using Z-scan technique, employing 10ns laser pulses, at 532nm. The systems were found to exhibit strong nonlinear optical response, dominated by nonlinear refraction. The effect of organic and inorganic composition ratio on the nonlinear susceptibility is studied experimentally. In all cases, the nonlinear absorption and refraction have been determined. The corresponding third-order susceptibilities and second-order hyperpolarizability are determined to be as large as 10−6(esu) and 10−28(esu) under ns laser excitation respectively. Showing large third-order optical nonlinearity in CH3NH3PbBr3 thin films, suggesting their potential for photonics applications.

Broadband ultrafast spatial self-phase modulation for topological insulator Bi2Te3 dispersions

Ultrathin topological insulator bismuth telluride (Bi2Te3) nanosheets with uniform hexagonal nanostructure have been synthesized by cost-effective solvothermal method. Broadband spatial self-phase modulation phenomena of these topological insulator nanosheets have been observed with 400 nm, 800 nm, and 1070 nm ultrafast lasers. The experimental results suggest that this coherent light scattering is due to the broadband, ultrafast, and large third-order optical nonlinearity of Bi2Te3. With the pulsed laser excitation, the nonlinear refractive index (n2) of Bi2Te3 dispersion solution was measured to be ∼10−12 m2/W, and the third-order nonlinear susceptibility ∼10−7 esu. Our work may provide an inroad for developing the nonlinear optical applications based on topological insulators.

Nonlinear optical properties and optical power limiting behavior of Leishman dye in solution and solid polymer film using z-scan

We have studied the nonlinear optical properties of Leishman dye in chloroform solution at different concentrations and solid film mixed with polymethylmethacrylate (PMMA) polymer using a continuous wave (CW) laser at 532nm as the excitation source. We have employed the z-scan technique to evaluate the sign and magnitude of the intensity dependent nonlinear refractive index (n2), the nonlinear absorption coefficient (β), and the third-order nonlinear optical susceptibility (χ(3)). The obtained results showed that the Leishman dye exhibits a negative nonlinear refraction (self-defocusing) and saturable absorption. It was found that the values of n2, β, and χ(3) are dependent on the dye concentration, they increases when the dye concentration increases. Optical power limiting characteristics of the dye at different concentrations in solution and solid film were also studied. Our results showed that the Leishman dye has large third-order optical nonlinearity, thus it could be a potential candidate for opto-electronic and photonic devices.

Spectroscopic and Nonlinear Optical Properties of 3, (4-tert-butylphenoxy) Phthalocyanine Constitutional Isomers

Introduction Organic material with second-order nonlinear optical (NLO) material properties are useful in applications such as optical data processing or storage devices and can be easily processed and integrated into optical devices [1, 2]. Organic materials such as phthalocyanines (Pcs) exhibit large and fast nonlinearities, which can be fine-tuned by rational modification of the molecular structure [3, 4, 5]. Pc molecules are known to have large third-order optical nonlinearities which arise from the highly delocalised two dimensional 18-electron system [6, 7, 8, 5]. Pcs have been intensively investigated for their NLO properties. In most studies, NLO properties of tetra substituted Pcs have been studied as a mixture of isomers [9]. Aims In this work four constitutional isomers of unmetalated tert-butylphenoxy phthalocyanine were separated and their NLO properties measured, in order to identify which isomer contributes the most to the measured NLO response.This work presents spectroscopic and nonlinear optical properties of unmetalated 3, (4-tert-butylphenoxy) phthalocyanine constitutional isomers. Second order nonlinear polarizability, second order hyperpolarizability and third order imaginary susceptibility (Im[χ(3)]) values were determined for monomeric and aggregated constitutional isomers. Z-scan technique is employed in determining the second order NLO property. Spectroscopic and photophysical properties of the isomers, such as fluorescence lifetime and rotational correlation lifetimes are determined. Magnetic circular dichroism (MCD), time correlated single photon counting spectroscopy (TCSPC), ultra-violet visible (UV/vis) spectroscopy, Infra-red (IR) spectroscopy and density functional theory (DFT) are some of the techniques used to characterise physical properties of the isomers. References G. de la Torre, P. Va´zquez, F. Agullo´-Lo´pez, T. Torres, J. Mater. Chem., 1998, 8, 1671-1683.T. Verbiest, S. Houbrechts, M. Kauranen, K. Clays, A. Persoons, J. Mater. Chem., 1997, 7, 2175-2189J. M. Fox, T. J. Katz, S. V. Elshocht, T. Verbiest, M. Kauranen, A. Persoons, T. Thongpanchang, T. Krauss, L. Brus, J. Am. Chem. Soc.,1999, 121, 3453-3459E. M. Maya, A. W. Snow, J. S. Shirk, R. G. S. Pong, S. R. Flom, G. L. Roberts, J. Mater. Chem., 2003, 13, 1603-1613G. de la Torre, P. Vazquez, F. Agullo-Lopez and T. Torres, J. Mater. Chem., 1998, 8, 1671-1683.J. Britton, M. Durmus ̧ S. Khene, V.Chauke, T. Nyokong, J. Porphyrins Phthalocyanine, 2013, 17, 692-702.C. Mkhize, J. Britton, T. Nyokong, Polyhedron, 2014, 81, 607-613.J. Britton, M. Durmuş, V. Chauke, T. Nyokong, Journal of Molecular Structure, 2013, 1054-1055, 209-214.C. Nitschke, S. M. O’Flaherty, M. Kroll, J. J. Doyle, W. J. Blau, Chemical Physics Letters, 2004, 383, 555-560.

Plasmon resonance enhanced large third-order optical nonlinearity and ultrafast optical response in Au nanobipyramids

The third-order optical nonlinearity and response time of Au nanobipyramids have been investigated by using optical Kerr effect technique. Large third-order nonlinear optical susceptibility (χ(3)) and ultrafast optical response time have been obtained at the longitudinal surface plasmon resonance (LSPR) wavelength. As the excitation laser wavelength varies from non-resonance wavelength of 780 nm to the LSPR wavelength of 825 nm, χ(3) increases from 7.4 × 10−14 to 3.9 × 10−13 esu, the fast component of the response time decreases from 141 ± 23 to 83 ± 8 fs and the ratio of the fast component remains around 48%, while the slow response time decreases from 3200 ± 200 to 2310 ± 158 fs. The large enhancement of χ(3) is due to the large local field enhancement caused by the surface plasmon resonance, and the shortening of the response times are induced by the increased probability of the electron-electron and electron-phonon scatterings in the nanosystem. This significant ultrafast optical property in Au nanobipyramids has great application in future ultrafast information processors.

Open-shell character and second hyperpolarizabilities of one-dimensional chromium(II) chains: size dependence and bond-length alternation effect.

Using the long-range corrected spin-unrestricted density functional theory (LC-UBLYP) method, we have investigated the longitudinal third-order nonlinear optical (NLO) properties, i.e., the second hyperpolarizabilities γ of open-shell singlet one-dimensional (1D) extended metal atom chain (EMAC) systems, chromium(II) chains Cr(II)2n (n = 1-4), with different metal-metal bond lengths from the viewpoint of the open-shell character dependences of each d orbital contribution (dσ, dπ, dδ) to γ and of the chain-length dependence of γ. It turns out that the chain length dependences of the open-shell characters of dπ and dδ orbitals at any metal-metal bond length are negligible, while the dσ open-shell character decreases as a function of chain length. The systems display bell-shaped behaviors of γ as a function of the metal-metal bond length, in which the γ values attain maxima for intermediate dσ open-shell character. The maximum γ value (γmax) exhibits remarkable enhancement as a function of chain length. It is also found that the bond length alternation (BLA) significantly affects the γ values and their chain-length dependences. The present results provide the guiding principles for designing transition-metal complexes with open-shell singlet 1D metallic chains exhibiting large third-order optical nonlinearity.

Large third-order optical nonlinearity in coupled Au–Ni–Au composite nanorods

Ordered Au–Ni–Au composite nanorod arrays with rod diameter of 18nm were grown in anodic aluminum oxide (AAO) templates. Strong longitudinal surface plasmon resonance (LSPR) with peak position around 800nm was observed in the nanorods. Z-scan technique was used to investigate the third-order optical nonlinearities of the sample. Large third-order nonlinear absorption coefficient of −2.65×106cm/GW was obtained at LSPR wavelength. The excitation wavelength and incident angle dependent nonlinear absorptions in the Au–Ni–Au composite nanorods show that strong coupling of the longitudinal plasmon between nanorods can result in a large enhancement of the third-order optical nonlinearity. Comparison between the Au–Ni–Au composite nanorods and the pure Au nanorods demonstrates that further growing of a Au segment on the as-grown one separated by a Ni thin layer will lead to a large improvement of the third-order optical nonlinearities. These results are important for manipulation of the third-order optical nonlinearities in plasmonic devices.

Large third-order optical nonlinearity of ZnO–Bi2O3–B2O3 glass–ceramic containing Bi2ZnB2O7 nanocrystals

Homogeneous transparent optical glass–ceramics precipitated with unique nonlinear crystals are promising materials for photonic applications. We have utilized heat treatment method to prepare transparent ZnO–Bi 2 O 3 –B 2 O 3 glass–ceramic containing Bi 2 ZnB 2 O 7 nonlinear nanocrystals. A large third-order nonlinear susceptibility χ (3) of glass–ceramic is measured by Z-scan technique, which mainly attributed to unique [BiO 6 ] and [B 2 O 5 ] units in Bi 2 ZnB 2 O 7 crystal structure and the quantum size effect of nanoparticles. The discovery is of great potential in the application of nonlinear optical integrated devices.

Third-order optical nonlinearity at 800 and 1300 nm in bismuthate glasses doped with silver nanoparticles.

Large and ultrafast third-order optical nonlinearities in Ag-doped bismuthate glasses which are prepared by incorporating Ag ions into bismuthate glasses to form Ag nanoparticles through a consecutive melting-quenching-annealing technique are reported. Due to the high refractive index of bismuthate glass, surface plasmon resonance (SPR) of Ag nanoparticles is extendable to 1400 nm, resulting in a higher nonlinear refractive index than bismuthate glass. Femtosecond Z-scans show that the nonlinear refractive index, as high as 9.4 × 10(-17) and 5.6 × 10(-18) m(2) W(-1) at 800 and 1300 nm, respectively, can be achieved by selecting an optimized concentration of Ag nano-sized particles. And two-photon absorption at 800 nm is suppressed due to a blue shift in the band-gap of Ag-doped bismuthate glasses, as compared to pristine bismuthate glasses. Optical Kerr shutter technique reveals that these nonlinearities have a relaxation time of < 1 ps.

Surface plasmon enhanced third-order optical nonlinearity of Ag nanocomposite film

We obtain a large third-order optical nonlinearity (χ(3) ≈ 10−10esu) of silver nanoparticles dispersed in polyvinyl alcohol/tetraethyl orthosilicate matrix using single beam z-scan technique at 532 nm by Q-switched Nd:YAG laser. We have shown that mechanisms responsible for third-order optical nonlinearity of Ag nanocomposite film are reverse saturable absorption (RSA) and self-defocusing in the purlieu of surface plasmon resonance (SPR). Optical band-gap and width of SPR band of Ag nanocomposite film decrease with increasing silver concentration, which leads to enhancement of local electric field and hence third-order optical nonlinearity. Optical limiting, due to RSA has also been demonstrated at 532 nm.

Ultrafast Third-Order Optical Nonlinearity in Au Triangular Nanoprism with Strong Dipole and Quadrupole Plasmon Resonance

Au triangular nanoprisms have been prepared by the wet chemical method. By using absorption measurements and finite difference time domain (FDTD) calculations, the dipole and quadrupole plasmon resonances of Au triangular nanoprisms are investigated experimentally and theoretically. Calculations show that large electric fields are confined at the tips of the Au prisms, leading to large third-order optical nonlinearities. The Z-scan measurements show a third-order optical susceptibility of about 1.25 × 10–11 esu at 1240 nm, which is 19 times larger than that at 800 nm. The ultrafast light response time is about 482 fs measured by optical Kerr effect technique at 800 nm. The distinct third-order optical nonlinearities and the ultrafast response time enable the Au triangular prisms to be a good candidate for future all-optical switches and ultrafast optical information manipulators.

Enhanced cubic optical nonlinearity of oligoazine derivatives

We report a large positive third-order optical nonlinearity of synthesized oligoazine derivatives (OADs) using z-scan technique at 532 nm by Q-switched Nd:YAG laser. Optical band gap of OADs shrinks with increasing repeated units. Origin of large cubic nonlinearity is in the extensive π-electron delocalization. We obtained the values of \(\chi_{R}^{(3)} \approx (0.78 - 3.98) \times 10^{ - 11} \,{\text{esu}}\) and \(\chi_{I}^{(3)} \approx (0.21 - 1.95) \times 10^{ - 11} \,{\text{esu}}\) in OADs. Moreover, values of optical nonlinearity of OADs show reasonable agreement with the theoretically predicted values. We have shown OADs could be used as good reverse saturable absorber and self-focusing materials. Optical limiting, due to reverse saturable absorption, has also been successfully demonstrated at 532 nm.

Dipole plasmon resonance induced large third-order optical nonlinearity of Au triangular nanoprism in infrared region

Au triangular nanoprisms with strong dipole plasmon absorption peak at 1240 nm were prepared by wet chemical methods. Both numerical calculations and experiments were carried out to investigate the optical properties of the samples. Finite difference time domain (FDTD) and Local Density of States (LDOS) calculations demonstrate that strong electric field enhancement and large LDOS can be obtained at tip areas of the Au triangular nanoprisms. Z scan techniques were used to characterize the nonlinear absorption, nonlinear refraction, as well as one- and two-photon figures of merit (W and T, respectively) of the sample. The results show that maximum nonlinear refractive index can be obtained around the resonance absorption wavelength of 1240 nm, detuning the wavelength from the absorption peak will lead to the decrease of the nonlinear refractive index n(2), while the nonlinear absorption coefficient β doesn't change much with the wavelength. This large wavelength dependence of n(2) and small change of β enable the sample to satisfy the all-optical switching demand of W> 1 and T< 1 easily in a large wavelength range of 1200-1300 nm. These significant nonlinear properties of the sample imply that Au triangular nanoprism is a good candidate for future optical switches in infrared optical communication wavelength region.

Terahertz-field-driven sub-picosecond optical switching enabled by large third-order optical nonlinearity in a one-dimensional Mott insulator

Sub-picosecond modulation of the optical reflectivity (R) using terahertz electric-field (ETHz) pulses was achieved in a typical one-dimensional Mott insulator, the bromine-bridged nickel compound, [Ni(chxn)2Br]Br2 (chxn: cyclohexanediamine). The reflectivity change (ΔR/R) at around the Mott-gap transition peak (∼1.3 eV) was ∼1% for ETHz ∼45 kV/cm, and proportional to the square of ETHz. The relaxation time of ΔR/R was under 0.1 ps, enabling optical switching with a high repetition rate in the near-infrared region. The electric-field and probe-energy dependences of ΔR/R demonstrate that the modulation is due to large third-order optical nonlinearity of one-dimensional Mott insulators.

Aggregation-induced emission on benzothiadiazole dyads with large third-order optical nonlinearity

Two kinds of D-A molecular of (4-(4-(9H-carbazol-9-yl)phenyl))-7-nitrobenzothiadiazole (BSC) and 4-((4-(9H-carbazol-9-yl)phenyl)ethynyl)-7-nitrobenzothiadiazole (BEC) containing carbazole moieties as the donor were synthesized. X-ray crystal data elucidated the multiple intermolecular interactions. They exhibit distinctly different self-assembly behaviours. The nonlinear optical properties were studied using the top-hat Z-scan technique at 532 nm with a 21 ps pulse. The results indicate that they exhibit large third-order nonlinear absorption effects. The nonlinear absorption coefficients α2 fitting the experimental data are 6.3 × 10(-12) m W(-1) for BSC and 3.6 × 10(-11) m W(-1) for BEC. The time-resolved pump-probe results show that both nonlinear absorption and nonlinear refraction of BEC in CH2Cl2 solution have rapid optical responses, which indicate the nonlinear absorption and nonlinear refraction mechanism are excited-state nonlinear. Moreover, both of these two compounds are observed to be aggregation-induced emission (AIE) active. The aggregates of the well-formed one-dimensional microrods of BEC and BSC endow the material with potential applications in the field of optical devices.

Large resonant third-order optical nonlinearity of thin film containing J-like aggregates of a bis[4-(N-dibutylamino)phenyl]squarylium dye

The third-order optical nonlinearity and response of thin film containing J-like aggregates of a bis[4-(N-dibutylamino)phenyl]squarylium dye were measured by degenerate four-wave mixing (DFWM) technique under resonant conditions. The temporal profile of DFWM signal was obtained with a time resolution of 0·3 ps (FWHM), and was found to consist of at least two components, i.e. the coherent instantaneous nonlinear response (electronic response) and the slow response due to the excited state population grating. The effective χ (3) value of thin squarylium dye film was evaluated to be as high as 1·1 × 10 − 7 esu, and the figure of merit of third-order nonlinearity F (F = χ (3)/α), was calculated to be about 2·1 × 10 − 13 esu cm.