Vincent Rodriguez

• Full Professor, PhD
• Managing Director at University of Bordeaux

Differently substituted pyrrole‐azo–benzene molecular photoswitches were prepared in a straightforward synthetic way. Their fundamental properties were investigated by XRD analysis, differential scanning calorimetry, thermogravimetric analysis, cyclic voltammetry, UV–Vis absorption spectroscopy, Hyper‐Rayleigh Scattering, and NMR spectroscopy; the...

Molecular symmetry controlling NLO-response directionality.

The solvent effects on the linear and second-order nonlinear optical properties of an aminonaphtylethenylpyridinium (ANEP) dye are investigated by combining experimental and theoretical chemistry methods. On the one hand, deep near infrared (NIR) hyper-Rayleigh scattering (HRS) measurements (1840–1950 nm) are performed on solutions of di-8-ANEPPS i...

We report on direct femtosecond laser writing in zinc barium gallo-germanate glasses. A combination of spectroscopic techniques allows to progress in the understanding of the mechanisms taking place depending on the energy. In the first regime (type I, isotropic local index change) up to 0.5 µJ, the main occurrence is the generation of charge traps...

This work combines hyper-Rayleigh scattering (HRS) experiments performed in the NIR range (1.30 and 1.60 μm) and quantum chemical calculations to provide a comprehensive description of the second harmonic generation (SHG) responses of donor-acceptor Stenhouse adducts (DASAs). Representative derivatives of the three generations of DASAs, which diffe...

We report Raman spectra in the sub-anodic region after electro-thermal poling of the 46S4 bioglass and show a correlation between structural changes and the induced second harmonic generation (SHG). The Raman peak at ca. 625 cm−1, due to the symmetric stretching-bending vibration of Si-O-Si bridges, was employed to quantify the poling-induced struc...

The structural and spectroscopic properties of three Ce³⁺-doped A3InF6 compounds (with A⁺ = Rb⁺, K⁺, Na⁺) are investigated. Containing indium, they all exhibit 2Ce³⁺ + In³⁺ ⇔ In⁺ + 2Ce⁴⁺ redox processes induced by UV irradiation between Ce³⁺ and In³⁺ cations. The photochromo-luminescent behaviour and associated kinetics, with the Ce³⁺ and In⁺ ion e...

We propose an innovative approach to program the alignment of liquid crystal (LC) assemblies allowing for the formation of multi-domain alignments whose orientation axis and sizes are controlled at the micrometer scale by an electrically patterned glass surface. The glass surface preparation is based on a thermo-electrical imprinting process to ind...

This contribution employs quantum chemistry methods to describe the variations of the second nonlinear optical responses of molecular switches based on benzazolo-oxazolidine (BOX) units, connected by π-linkers, along their successive opening/closing. Under the fully closed forms, all of them display negligible first hyperpolarizability (β) values....

Magneto-optical properties are wide and span various applications such as magnetic field sensing, imaging technologies, security encoding... In this work, we have revisited the all-optical Inverse Faraday effect method to measure the Faraday rotation angle and determine the Verdet constant of diamagnetic/paramagnetic liquid solutions. We show that...

There have been many great advances in the field of biomedical imaging in recent years, with supramolecular chemistry playing a key role in the evolution of modern imaging techniques. Non-covalent supramolecular interactions are fundamental to countless biological processes, from host–guest binding to the stabilisation of complex structures. Supram...

Sodium tantalum germanate glasses were thermally poled using microstructured metallic anodes of two distinct geometries. Topological, structural and optical characterizations of the micro-imprinted structures revealed an accurate reproducibility of the...

This study evaluates the impact and stability behavior of a candidate protective shell of Al2O3 which aims to hinder the dissolution of ZnSe in As-S-Se glass systems during the so-called ‘grinding-remelt’ process. Atomic Layer Deposition (ALD) was chosen as the route to conformal shell coating and the role of resulting film attributes on powder and...

Owing to their intense emission, low toxicity and solubility in aqueous medium, fluorescent organic nanoparticles (FONs) have emerged as promising alternatives to inorganic ones for the realization of exogenous probes for bioimaging applications. However, the intimate structure of FONs in solution, as well as the role played by intermolecular inter...

Multiplex coherent anti-stokes Raman scattering (M-CARS) and second harmonic generation (SHG) techniques are used to map the real part of the nonresonant third order nonlinear optical susceptibility and the second order nonlinear optical susceptibility of a thermally microimprinted niobium borophosphate glass. In particular, such bimodal nonlinear...

Complex sequential crystallization mechanisms were investigated in the glass composition 70GeO2-10Na2O-20Ta2O5 prepared by melt-quenching. In a first stage, a classical volume-nucleated crystallization of sodium tantalate perovskite Na2Ta8O21 is induced under short time heat-treatments whereas longer annealing treatments promote the formation of su...

Molecular switches are chemical compounds exhibiting the possibility of reversible transformations between their different forms accompanied by a modification in their properties. Among these, switching of multi-addressable Benzazolo-OXazolidines (BOXs) from a closed form to an open form results in drastic modifications in their linear and nonlinea...

Herein, our attention is focused on the second‐order optical properties of thermally poled sodo‐niobate amorphous thin films through an original methodology that combines both macroscopic and microscopic second harmonic generation techniques. By probing the geometry and the magnitude of the second‐order nonlinear (SONL) optical response at differen...

Optical composite fibers based on active transition metal (TM)-doped semiconductor crystals are being investigated for use in mid-infrared (mid-IR) fiber laser systems. This study evaluates a candidate glass matrix system assessing its key physical properties and suitability for optical fiber drawing and examines the stability of TM-doped ZnSe crys...

The linear and nonlinear optical (NLO) properties of a series of Λ-shaped derivatives containing a 4,5-dicyanopyrazine acceptor unit, N,N-dimethylamino donor groups and systematically enlarged π-conjugated linkers are investigated by means of UV/Visible and Hyper-Rayleigh scattering spectroscopies. Density functional theory calculations are also ca...

A microstructured SHG pattern on Sm 2 O 3-doped sodium borophosphate niobium (SmBPN) glasses was obtained by laser-induced thermal poling. The optical properties of SmBPN glasses were recorded by UV/Vis/NIR transmission spectra. In situ laser-induced heating of the SmBPN glasses without and with preheating was characterized by an infrared thermal c...

Six niobium rich glasses presenting different sodium contents were synthetized. On the basis of complementary infrared and Raman analysis, the influence of the sodium content and its role on the structure of the glasses prior to and following poling was examined. Correlative second harmonic generation (SHG)/Raman microscopy on the poled glasses cro...

The design of active optical devices integrating second‐order nonlinear (SONL) optical responses typically relies on the use of dielectric crystalline materials such as lithium niobate (LN) or semiconductors such as GaAs. Despite high SONL susceptibilities, these materials present important geometry constrains inherent to their crystalline nature l...

We present a 2D spatial mapping of the χ ⁽³⁾ susceptibility of a niobium borophosphate glass after thermal microprinting of a second order nonlinearity. χ ⁽³⁾ reduction is evidenced in the poled areas using coherent Raman imaging.

Molecular helices based on self-organized aromatic oligoamide foldamers have been designed and prepared in their two enantiomeric forms in order to probe their second-order nonlinear chiroptical properties in solution. The quinoline oligoamides were rationally functionalized by electron-donating and electron-withdrawing groups to afford a gradual i...

The technological interest in developing novel functional nano-objects which exhibit new properties arising from their nanoscopic nature is undoubtful. Although bulk ZnO is considered to be non-ferroelectric, herein the ferroelectric behavior of un-doped and self-standing ZnO nanoparticles is reported for the first time. The nanoparticles (NPs) und...

Structure, linear and nonlinear optical properties of glasses in the ternary system (90-x)GeO2-10Na2O-xTa2O5 have been investigated. These glasses exhibit a wide transparency window from 350nm to 5500nm and refractive index ranging from 1.78 to 1.93. Upon a thermal poling treatment under nitrogen atmosphere using increasing poling voltages, SHG qua...

Several glass compositions of the Ge-As-S ternary system were prepared and their thermal and physical properties were investigated as T g , T d , theoretical drawing temperature T s , viscous flow activation energy, density, visible and IR absorption coefficients. The measured values, which are in excellent agreement with the literature, were used...

The two room-temperature NaNbO3 polymorphs crystallizing with orthorhombic symmetry have been successfully isolated at using a new preparative method. The pure polar phase, annealed at 600 °C under air after hydrothermal treatment at 200 °C, adopts the P21ma space group, whereas the well-known and thermodynamically stable form with the Pbma structu...

From a dual experimental-theoretical vibrational analysis we propose a new rationalized structural description of Ge-S-I chalcogenides glasses at the nanoscale. A vibrational multipolar approach based on a simultaneous desummation of IR and polarized Raman spectra (RS-VV and RS-HV) has been applied on these glasses. According to recent results on t...

Second-order optical susceptibility, χ⁽²⁾, has been induced in thermally poled chalcogenide glasses, doped with varying levels of sodium. Using alkali-doped chalcogenide glasses, the second harmonic generation (SHG) capability is retained for over a year whereas in alkali-free glasses it disappears in days. The enhanced stability is attributed to a...

The (a,b) plane angular dependence of the third-order nonlinear optical susceptibility, χ(3), of a c-cut paratellurite (α-TeO2) single crystal was quantitatively evaluated here by the Z-scan technique, using a Ti:sapphire femtosecond laser operated at 800 nm. In particular, the mean value Re(⟨χ(3)⟩a,b)(α-TeO2) of the optical tensor has been extract...

The potential for realizing robust, monolithic, near-surface refractive micro-optic elements with long-lived stability is demonstrated in visible and infrared transmitting glasses capable of use in dual band applications. Employing an enhanced understanding of glass chemistry and geometric control of mobile ion migration made possible with electrod...

In a glassy material, a thermal poling treatment allows to induce a space charge within the glass structure which can reach the gigavolt per meter. By playing with the material composition and notably its concentration in mobile cations, additional variations of the glass structure can be induced which can modify its physical and chemical propertie...

Our research deals with the evolution of wall surfaces in prehistoric caves. The focus of this paper is dedicated to the structural and chemical characterization of a white concretion partially covering some walls in caves. In one of the caves, a non-ornate one which became a laboratory-cave (the Leye cave at Marquay, Dordogne, France) located in t...

In the present work, series of Ge-S-I glass samples with 5, 10 and 15% of iodine and a concentration of germanium varying between 25 and 35% were prepared and their physical properties such as Tg, density, Visible and infrared light absorption were investigated. From the analysis of the properties close to the stoichiometric composition (GeS2)xI100...

We show that high-quality pentacene (P5) thin films of high crystallinity and low surface roughness can be produced by pulsed laser deposition (PLD) without inducing chemical degradation of the molecules. By using Raman spectroscopy and X-ray diffraction measurements, we also demonstrate that the deposition of P5 on Au layers result in highly disor...

Third-harmonic scattering (THS) is an unexplored third-order nonlinear optical process despite the fact that it is quite an easy technique to handle that quantifies the molecular second-order hyperpolarizability γ(−3ω;ω,ω,ω). In a liquid, light interaction is subject to isotropic averaging of the local symmetry (multipolar activity), and the mutual...

The linear and nonlinear optical properties of two indolino-oxazolidine derivatives acting as multiaddressable switches are reported. The second-order hyperpolarizability contrasts upon commutation between their closed and open forms are characterized using Hyper-Rayleigh Scattering measurements, and rationalized by means of density functional theo...

Objective Molar Incisor Hypomineralisation (MIH) is a structural anomaly that affects the quality of tooth enamel and has important consequences for oral health. The developmentally hypomineralised enamel has normal thickness and can range in colour from white to yellow or brown with or without surface breakdown. The possibility of finding MIH in ‘...

Thermal poling was proven successful to induce second order nonlinear properties and concurrent modification of composition, structure and chemical reactivity in glasses. With current efforts to reduce devices sizes in components employing such attributes, means to control changes at the micrometer scale are needed. We present a micro-imprinting po...

A new multimodal approach that combines linear and nonlinear vibrational spectroscopies and hyper-Rayleigh scattering has been applied in the TeO2-TaO5/2-ZnO glass system to assess and quantify the relation between Raman gain and optical responses within the glass' network arrangement. The level of polymerization of the TeO4 chain-like structure in...

A combined experimental-theoretical investigation has revealed that oxazine-based compounds are multi-addressable, multi-state, and multi-functional molecular switches exhibiting contrasts of both linear and second-order nonlinear optical properties. The switching properties are particularly large when the substituent is a donor group. In this stud...

We report on the ability of a thermal poling treatment to be considered as an imprinting process modifying both linear and nonlinear optical properties as well as surface morphology of glassy materials.

Mobile charges and lattice polarization interact in ferroelectric materials because of the Coulomb interaction between the mobile free charges and the fixed lattice dipoles. Using SHG microscopy, we have investigated this mutual screening in KTiOPO4, a ferroelectric/superionic single crystal in which the mobile charges are K⁺ ions. The ionic accumu...

The nonlinear optical (NLO) properties of a double photochrome molecular switch are reported for the first time by considering the four trans forms of a dithienylethene-indolinooxazolidine hybrid. The four forms are characterized by means of hyper-Rayleigh scattering (HRS) experiments and quantum chemical calculations. Experimental measurements pro...

The ability to control glass surface reactivity at different length enables key properties required for future "smart substrates". Employing a thermal poling process on a specific borosilicate glass composition can yield a surface with tailored physical and chemical properties. This work shows that during poling, alkali contained in the glass matri...

We have undertaken polarization-resolved SHS experiments to investigate a series of two fluorescent organic nanoparticles (FONs) made from dipolar dyes bearing a triphenylamine-donating end-group and a slightly hydrophilic acceptor end-group. The FONs, which show very large negative surface potentials, responsible for their good colloidal stability...

Two room temperature ionic liquids (ILs) bearing coumarin and p-hydroxycinnamic acid moieties are synthesized, and their photochemistry is studied in solution and neat conditions. Irradiation at absorption maxima leads to photochemical transformations and results in changes of their rheological properties which are evaluated by rotational rheometry...

In this work, linear and nonlinear optical properties of electro-/acido-/photo-switchable indolino[2,1-b]oxazolidine derivatives were investigated. The linear optical properties of the closed and open forms have been characterized by UV-Visible and IR spectroscopies associated with DFT calculations. Nonlinear optical properties of the compounds hav...

A spherulitic crystallization of the crystalline phase LaBGeO5 is generated in the 25La2O3-25B2O3-50 GeO2 glass system. Linear and nonlinear optical properties of lanthanum borogermanate glass-ceramic have been investigated at both macroscopic and microscopic scales. Polarized μ-Raman analysis has evidenced a radial distribution of the crystallites...

Mobile charges and lattice polarization interact in ferroelectric materials because of the Coulomb interaction between the mobile free charges and the fixed lattice dipoles. We have investigated this mutual screening in KTiOPO4, a ferroelectric/superionic single crystal in which the mobile charges are K+ ions. The ionic accumulation close to the cr...

Micro-structured second harmonic generation responses have been achieved on borophosphate niobium glasses by thermal poling using micro-patterned silicon substrates. The poling imprinting process has created sub-micrometer sized patterns of both surface relief and second order optical responses on the anode glass surface. Field enhancement effects...

Optical, spectroscopic and thermo-mechanical properties of monoclinic Li6Eu1-xGdx(BO3)3 (x = 0,0.25,0.35) bulk single crystals, grown to be used in the design of heat-scintillation cryogenic bolometers (HSCBs), were investigated. The linear thermal expansion was determined along the a, b, c and c* directions over the temperature range 303–873 K, an...

Hyper-Rayleigh scattering experiments and quantum chemical calculations are combined to investigate the second-order nonlinear optical responses of a series of three-arm merocyanine derivatives. They exhibit an octupolar hyperpolarizability response with lower amplitude than crystal violet due to a lower extent of the photoinduced charge transfer a...

By using hyper-Rayleigh scattering experiments and quantum-chemical calculations, we demonstrate that nonlinear optics can be used to probe unequivocally, within a non-destructive process, the multiple electronic states that are activated upon pH- and light-triggered transformations of the 4a-hydroxyflavylium ion. These results open new perspective...

We depict a new approach for the localized creation in three dimensions (3D) of a highly demanded nonlinear optical function for integrated optics, namely second harmonic generation. We report on the nonlinear optical characteristics induced by single-beam femtosecond direct laser writing in a tailored silver-containing phosphate glass. The origina...

Molecular and ionic species of nitrogen oxides have been injected, formed, and then trapped within a borosilicate glass during a thermal poling process. This original observation denotes a new aspect of poling mechanisms for ionic glasses. For each poled borosilicate glasses studied, compositional, structural, and second harmonic generation profile...

Characterizations of linear spectroscopic properties in polarized light have been performed for the highly-concentrated Yb-doped borate family Li6Ln(BO3)3 (with Ln: Gd, Y, and labeled Yb:LLnB), in order to start to evaluate their potentiality for high-power laser applications. Modifications in spectral distributions and intensities are reported wit...

Double-stranded (ds) DNA of a λ-phage virus are combed on octadecyltrichlorosilane (OTS)-modified borosilicate glass substrates and investigated by means of tip-enhanced Raman spectroscopy (TERS) using tips coated with an Ag/Au bilayer. Owing to an enhancement factor higher than 6 ×102 and a lateral spatial resolution better than 9 nm (which is bel...

A study of the glass properties with two opposite levels of hydroxyl content is presented for two different tellurite glass families with molar composition 70TeO2-10Bi2O3-20ZnO and 80TeO2-20Nb2O5. We show that melting tellurite-based glasses in a dried-oxidant atmosphere (relative humidity <1%) reduces drastically the OH impurities. The effect of r...

*yannick.petit@u-bordeaux1.fr For the last decade, direct laser writing (DLW) has kept on providing impressive achievements in material processing, with a very broad range of both fundamental phenomena and subsequent applications. Among the numerous advantages of femtoseconde DLW, one can list its large versatility with respect to the irradiated ma...

*yannick.petit@u-bordeaux1.fr An endless increasing number of laser/material interaction studies above laser-induced modification thresholds have been carried out over the past decade, either for undesirable laser-induced damages, for example in high power laser systems in relation with material ageing and material optical quality, or for profitabl...

We report on fluorescence and second-harmonic generation correlative microscopy of femtosecond direct laser-induced structures in a tailored silver-containing phosphate glass. We compare the spatial distributions of the related permanent electric field and silver clusters. The latter appear to be co-localized where the associated electric potential...

Nanoscale structures, including molecules, supramolecules, polymers, functionalized surfaces, and crystalline/amorphous solids, can commute between two or more forms, displaying contrasts in their nonlinear optical (NLO) properties. Because of this property, they have high potential for applications in data storage, signal processing, and sensing....

We report on Raman and fluorescence microscopy in polarized light in the oriented Eu3+-doped LYB monoclinic crystal after femtosecond laser irradiation. Differential spectra denote large bands typically centered on the pristine glass Raman and fluorescence lines, proving the crystal structure alteration and the significant existence of a laser-indu...

Raman-active vibrational modes of (6,5) chirality-enriched single-walled carbon nanotubes (SWNTs), helically wrapped by semiconducting poly[2,6-{1,5-bis(3-propoxysulfonic acid sodium salt)}naphthylene]ethynylene (PNES), are described in great detail. At an irradiation wavelength of 568.2 nm, the extent to which the environment impacts the nanotube...

Raman spectra of the tetragonal D44 structure of paratellurite TeO2 have been revisited avoiding anomalous polarization-selection-rules violations previously observed and due to optical activity. We present a complementary hyper-Raman scattering study of paratellurite. Wavenumber and symmetry assignments are given for all expected 21 Raman active o...

A crystallization study of lithium niobium silicate glass with the molar composition 35Li2O.25Nb2O5.40SiO2 is reported using in situ techniques (x-ray diffraction, Raman spectroscopy and environmental electron microscopy) at high temperatures. Those techniques reveal that the surface crystallization begins at T g with c-axis crystallites oriented p...

Various attempts to combine magnetic and nonlinear optical (NLO) properties in a molecule are reviewed, with a special focus on the possibility of interplay between the magnetic component and the quadratic ([prop] E2) NLO response. This multidisciplinary research leads to the idea of spin-crossover-induced (SCO-induced) NLO switching and is evaluat...

We report on fluorescence and second-harmonic generation correlative microscopy of femtosecond direct laser-induced structures in a tailored silver-containing phosphate glass. We compare the spatial distributions of the related permanent electric field and silver clusters. The latter appear to be co-localized where the associated electric potential...

The objective to induce reproducible, efficient, and stable second-order nonlinear optical properties (SONL) in an isotropic material remains a challenge in photonics. Thermal poling allows inducing SONL properties in glasses by the formation of an axial symmetry because of the implementation of a static electric field within the glassy matrix. A d...

Raman gain efficiency and structure of tellurite glasses in the TeO2–TaO5/2–ZnO system have been investigated by Raman and IR spectroscopies. It has been found that replacement of TaO5/2 by ZnO does not significantly modify the respective proportion of TeO4, TeO3 and TeO3+1 entities but induces an important decrease of the TeO4 structural units Ram...

We present a joint experimental and quantum chemical investigation on the first hyperpolarizability of the acetonitrile molecule, which is used as an external reference in Hyper-Rayleigh scattering (HRS) experiments. The measured HRS response is compared with calculations using the Finite Field (FF) procedure in combination with the Hartree-Fock an...

We introduce combined vibrational multipolar decompositions of IR, polarized Raman and hyper-Raman spectra as a powerful way to study isotropic materials. This new procedure has been applied to the molecular liquid HCCl3 and to silica glass, which are made of elementary structural units (ESU) weakly interacting and covalently 3Dlinked, respectively...

In a study of the v-P2O5 glassy structure, we discuss the complementarity of experimental and combined vibrational spectroscopies, namely infrared and polarized Raman scattering, using vibrational multipolar decomposition (VMD) analysis and ab initio calculations of local structures and vibrational spectra. VMD is a rigorous method that relates mul...

A study of bulk second harmonic generation (SHG) response of lithium niobium silicate glass-ceramics is presented. The observed macroscopic SHG signals have an isotropic 3D nature. To interpret this particular nonlinear optical response, a multiscale approach is used in which clear correlations between structure and optical response are characteriz...

We have investigated structural rearrangements induced by poling on oxide glasses. Combined Raman/SHG micro-imaging technique has highlighted strong correlations between NLO properties and poling mechanisms.