0000000000024893
AUTHOR
Martins Rutkis
Polymorph acceptor-based triads with photoinduced TADF for UV sensing
Abstract In contrast to many donor–acceptor type organic luminophores exhibiting thermally activated delayed fluorescence (TADF), two deep blue TADF emitters designed in this work contain only typical electron accepting moieties with different electron accepting abilities. Derivatives of benzophenone and diphenylsulfone substituted with phenothiazine-5,5-dioxide donor moieties were synthesized and studied. In addition to the TADF, green to blue emission color switching and strong fluorescence intensity enhancement by more than 60 times was detected for THF solution of the derivative of phenothiazine-5,5-dioxide and benzophenone under increase of UV excitation dose. We proved by a variety of…
Triphenyl moieties as building blocks for obtaining molecular glasses with nonlinear optical activity
The incorporation of trityl and triphenylsilyl groups into low molecular weight molecules allows the formation of stable molecular glasses. A series of materials based on the N-phenyldiethanolamine core was synthesized bearing different azobenzenes and benzylydene-1,3-indandione as active chromophores. Molecular hyperpolarizability of the synthesized compounds was calculated by a restricted Hartree–Fock method with basis 6-31G(d,p) and measured in solutions by hyper-Rayleigh scattering. Non-linear optical (NLO) activity of the thin glassy films was confirmed after a corona poling procedure. Thermal sustainability of the NLO response of up to 85 °C was achieved. Quantum chemical calculations…
Determination of Contact Potential Difference by the Kelvin Probe (Part I) I. Basic Principles of Measurements
Abstract Determination of electric potential difference using the Kelvin probe, i.e. vibrating capacitor technique, is one of the most sensitive measuring procedures in surface physics. Periodic modulation of distance between electrodes leads to changes in capacitance, thereby causing current to flow through the external circuit. The procedure of contactless, non-destructive determination of contact potential difference between an electrically conductive vibrating reference electrode and an electrically conductive sample is based on precise control measurement of Kelvin current flowing through a capacitor. The present research is devoted to creation of a new low-cost miniaturised measuremen…
Review and comparison of experimental techniques used for determination of thin film electro-optic coefficients
The results of electro-optic coefficient measurements performed with three commonly applied techniques used to assess electro-optic coefficients: the Mach–Zehnder, the Teng–Man, and the attenuated total reflectance technique are reported. It is shown that the signal obtained by the Mach–Zehnder and Teng–Man techniques is strongly influenced by the multiple internal reflection and piezo- and electrostrictive thickness change effects, which in our opinion have not been addressed sufficiently in the literature. A novel approach based on using Abeles matrix formalism is implemented for the retrieval of electro-optic coefficients from experimental data. The measurement results, errors, and compa…
All-organic electro-optic waveguide modulator comprising SU-8 and nonlinear optical polymer
Institute of Solid State Physics, University of Latvia (SJZ/2016/26); Ministry of Education and Science, Republic of Latvia (MultIfunctional Materials and composItes, photonicS and nanotechnology (IMIS2)). We acknowledge Dr. Anatolijs Sarakovskis at Institute of Solid State Physics for the XPS measurements.
Asymmetrical all-organic waveguide gas sensor
An all-organic waveguide sensor for volatile solver detecting was presented. Device consists of SU-8 waveguide with novel organic material used as sensitive cladding. Created device was tested in isopropanol and N2 vapor mixture.
Matching the Directions of Electric Fields from Triboelectric and Ferroelectric Charges in Nanogenerator Devices for Boosted Performance
Summary Embedding additional ferroelectric dipoles in contacting polymer layers is known to enhance the performance of triboelectricnanogenerator (TENG) devices. However, the influence of dipoles formed between the triboelectric surface charges on two contacting ferroelectric films has been ignored in all relevant studies. We demonstrate that proper attention to the alignment of the distinct dipoles present between two contacting surfaces and in composite polymer/BaTiO3 ferroelectric films can lead to up to four times higher energy and power density output compared with cases when dipole arrangement is mismatched. For example, TENG device based on PVAc/BaTiO3 shows energy density increase f…
Thermal and optical properties of 4H-pyran-4-ylidene fragment and bis-styryl and triphenyl groups containing derivatives
Small D-π-A type organic molecules with incorporated 4H-pyan-4-ylidene (pyranylidene) fragment in their structures show potential in organic photonics - such as materials for organic light emitting diode application studies and organic solid state lasers. Additional incorporation of bulky triphenyl- groups in their structures gives them the ability to form thin amorphous solid films from volatile non-polar organic solvents. Unfortunately, there is still no clear relation between compound organic structures and their thermal and optical properties. In order to investigate the above mentioned regularities we have synthesized a series of tripheyl- group containing derivates of 2,6-bis-styryl-4…
Dendronized azochromophores with aromatic and perfluoroaromatic fragments: Synthesis and properties demonstrating Ar ArF interactions
Abstract Syntheses of four new dendronized azochromophores were performed from 2-(2-amino-5-nitrophenoxy)ethanol, 2-[methyl(phenyl)amino]ethanol, 3,5-bis(benzyloxy)benzoic acid and 3,5-bis[(pentafluorophenyl)methoxy]benzoic acid using azo coupling reaction and ester formation reaction in presence of N,Nʹ-dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine. Arene-perfluoroarene (Ar ArF) interactions are demonstrated in single crystal structure of dendronized azochromophore between pentafluorophenyl fragment and acceptor part of the azochromophore. The effect of Ar ArF interactions becomes apparent in thermal and nonlinear optical properties of the chromophores. Glass transition temperatur…
Determination of Kerr and two-photon absorption coefficients of ABI thin films
This material is based upon work supported by the ERDF 1.1.1.1 activity project Nr. 1.1.1.1/16/A/046 “Application assessment of novel organic materials by prototyping of photonic devices”
Structure–property relationship of isomeric diphenylethenyl-disubstituted dimethoxycarbazoles
Isomeric 3,6-dimethoxy- and 2,7-dimethoxycarbazoles containing diphenylethenyl moieties were synthesized by condensation of the appropriate dimethoxycarbazoles with diphenylacetaldehyde. The solid-state structures and the molecular order of the compounds were proven by X-ray crystallography. Both compounds were found to be capable of glass formation with comparable glass transition temperatures (70–71 °C). They exhibited high thermal stabilities, with the 5% weight loss temperatures exceeding 375 °C. The isomer having diphenylethenyl groups at C-3 and C-6 positions and methoxy groups at C-2 and C-7 positions (3a) exhibited aggregation-induced emission (AIE), while its counterpart having dip…
<title>All-optical poling of DMABI molecules in a polymer matrix</title>
Many organic compounds in solid state have nonlinear optical properties due to the orientation of the molecules in a polymer matrix. In this work, all-optical poling and second harmonic generation in a composition consisting of 1 mass% of N,N-dimethylaminobenzylidene 1,3-indandione (DMABI) compound in poly(methyl methacrylate) (PMMA) matrix were studied. Thin films were prepared by solvent casting. The 1.064-μm fundamental and 532-nm second harmonic wavelengths of a Nd:YAG laser were used. It is shown that DMABI molecules can be oriented by the method of all- optical poling, and that the process is related to the photoinduced switching between two equally stable states of the molecule.
Perovskite CH3NH3PbI3–XClx Solar Cells. Experimental Study of Initial Degradation Kinetics and Fill Factor Spectral Dependence
The main drawback of the methylammonium lead halide perovskite solar cells is their degradation in ambient atmosphere. To investigate ambient-air-induced cell degradation, spec-tral dependencies of open-circuit voltage (VOC), fill factor (FF) and the power conversion effi-ciency (PCE) have been acquired (for the first time reported in literature). Our custom-made measurement system allowed us to perform measurements of the above-mentioned entities in situ directly in vacuum during and after thermal deposition of the elec-trode. We also studied how these parameters in vacuum changed after cell exposure to ambient air for 85 min (50 nm top electrode) and for 180 min (100 nm top Ag electrode).…
Inspirations for EO polymer design gained from modeling of chromophore poling by Langevin dynamics
One of the possibilities to create organic molecular material for NLO applications are polymers with dispersed NLO active chromophores. These molecules must be acentrically ordered by applying an external electric poling field. The NLO efficiency depends on dipole moment, molecular hyperpolarizabilities, concentration of the chromophores and external poling field strength. Calculating, from first principles, the extent of the alignment and via this NLO efficiency has proven to be challenging. One approach to solve this problem is pure analytic statistical mechanics treatment, what could be enhanced by Monte Carlo ( MC ) statistical mechanical modelling. The chromophore molecules usually hav…
Triphenylmethyl and triphenylsilyl based molecular glasses for photonic applications
Triphenylmethyl and triphenylsilyl structural fragments can be used to obtain glass forming, solution processable materials from polar chromophore molecules. Large number of compounds has been synthesized taking advantage of this approach, making it possible to identify some structure-property relations. Regarding the non-linear optical (NLO) properties of the given materials it is evident that triphenylmethyl groups help shielding unwanted NLO efficiency limiting dipolar interactions between polar chromophores in solid films. Chromophore stacking is still observed for compounds with large dipole momentum values. The glass transition temperatures of the compounds increase with the molecular…
Simple method for measuring bilayer system optical parameters
A simple method for measuring bilayer system refractive indexes and thicknesses in the low absorbing part of spectra is demonstrated. The method is based on application of Savitzky - Golay smoothing filters and interference fringe separation in the reflected or transmitted spectra of the bilayer system. The refractive indexes and thicknesses are extracted from the wavelengths corresponding to extreme points in the spectrum. Due to the fact that wavelength difference of extreme points in the analyzed spectrum is defined by the product of both, the layer thickness and refractive index, one must generate an appropriate initial guess of these parameters. For refractive index approximation two d…
Sputtered SiOxNy thin films: improving optical efficiency of liquid crystal diffuser elements in multi-focal near-to-eye display architecture
In this work we present reactive sputtered SiOxNy films with a variable refractive index as a convienent solution for contrast improvement of liquid crystal diffuser multi stacks in near-to-eye AR/VR displays. The focus concerns minimization of light reflections between internal structures, in particular ITO, by optimizing internal layers through tailored properties of thin film coatings, as well as subsequent laser patterning of thin film stack. Inorganic thin films have been deposited on glass by physical vapor deposition. Corresponding refractive index, thickness, uniformity and dielectric characteristics and other electro-optical properties have been measured and their impact on the res…
Mach-Zehnder interferometer implementation for thermo-optical and Kerr effect study
Scientific Research Project for Students and Young Researchers Nr. SJZ/2016/10; National Research Program “Multifunctional Materials and Composites, Photonics and Nanotechnology” (IMIS2) project “Photonics and materials for photonics”.
Modular approach to obtaining organic glasses from low-molecular weight dyes using 1,1,1-triphenylpentane auxiliary groups: Nonlinear optical properties
Abstract A new modular synthetic approach to obtain organic glasses from low-molecular weight azobenzenes and stilbenes has been accomplished using 1,1,1-triphenylpentane crystallization preventing auxiliary groups. Six new structures show excellent solubility in non-polar solvents and thin films with good optical qualities have been obtained using a spin-coating technique. The glass transition temperatures of the new amorphous materials were in the range of 73–108 °C. The nonlinear optical activity in thin amorphous films was measured after a corona poling procedure.
4-(Diethylamino)salicylaldehyde-based twin compounds as NLO-active materials
Abstract 4-(Diethylamino)salicylaldehyde-based twin compounds containing 1,3-indandione and 1,3-bisdicianovinylindane moieties were synthesized and their thermal, optical, photophysical, electrochemical, photoelectrical and nonlinear optical properties were studied. The synthesized compounds form glasses with the glass transition temperatures ranging from 79 to 103 °C. Photoluminescence spectra of the solutions of compounds exhibited red-shifts with the increase of the solvent polarity that was caused by the positive solvatochromic effect. The linear dependencies between the position of the photoluminescence maxima of compounds and the empirical parameter E T (30) of the different solvents …
Hybrid silicon on insulator/polymer electro-optical intensity modulator operating at 780 nm
Currently inorganic materials prevail as the nonlinear active medium for light modulation in electro-optical (EO) device technology. A recent promising trend is to consider organic nonlinear optical materials for application in EO modulators due to their multiple advantages including low costs and high EO coefficients. In this paper, we proposed a new type of polymer EO modulator whose fabrication is compatible with the currently used silicon on insulator technology. Our numerical optimization of the proposed structure demonstrates that it is theoretically possible to achieve a half-wave voltage as low as 1.56 V for a 1 cm long modulator structure operating at 780 nm. Based on the results o…
Determination of Kerr and two-photon absorption coefficients of indandione derivatives
This material is based upon work supported by the ERDF 1.1.1.1 activity project Nr. 1.1.1.1/16/A/046 “Application assessment of novel organic materials by prototyping of photonic devices” as well as by National Research Program “Multifunctional Materials and Composites, Photonics and Nanotechnology” (IMIS2) project “Photonics and materials for photonics”.
Determination of Contact Potential Difference by the Kelvin Probe (Part II) 2. Measurement System by Involving the Composite Bucking Voltage
Abstract The present research is devoted to creation of a new low-cost miniaturised measurement system for determination of potential difference in real time and with high measurement resolution. Furthermore, using the electrode of the reference probe, Kelvin method leads to both an indirect measurement of electronic work function or contact potential of the sample and measurement of a surface potential for insulator type samples. The bucking voltage in this system is composite and comprises a periodically variable component. The necessary steps for development of signal processing and tracking are described in detail.
Synthesis, optical, and thermal properties of glassy trityl group containing luminescent derivatives of 2-tert-butyl-6-methyl-4H-pyran-4-one
In this work we present simple preparation of original trityl group containing glassy luminescent 6-styryl substituted derivatives of 2-(2-tert-butyl-4H-pyran-4-ylidene)malononitrile (DWK-1TB), 2-(2-tert-butyl-4H-pyran-4-ylidene)-2- ethyl-2-cyanoacetate (KWK-1TB), 2-(2-tert-butyl-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione (ZWK-1TB) and 5-(2-tert-butyl-4H-pyran-4-ylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (JWK-1TB). Their optical properties have been investigated. The absorption maxima of synthesized glasses is in region from 425 nm to 515 nm and emission maxima is from 470 nm to 625 nm in solution of dichloromethane. But absorption maxima of their solid films is from 425 nm to 500 nm and em…
Thermal, glass-forming, nonlinear optical and holographic properties of "push-pull" type azochromophores with triphenyl moieties containing isophorene and pyranylidene fragments
Molecular organic compounds with electron donating fragment bounded through π-conjugated system with electron acceptor fragment, as well as with incorporated triphenyl groups in their molecules show potential for creating cheap and simple solution processable materials with nonlinear optical properties. Additional insertion of azobenzene fragment in their structures makes them also possible to form holographic volume and surface relief gratings (SRG) after exposure to laser radiation, which could be useful for holographic data storage. For these purposes polymers are generally used. However, their application is complicated and challenging task as in every attempt to obtain the same polymer…
Light induced processes in thin films of indandione type organic molecules
The optically induced switching of material properties is important for investigations of opto-electronic effects and optomechanical properties. Investigated organic materials contain chromophore dipole consisting of acceptor and donor groups bridged by a delocalized p-electron system. Both calculations and experimental data show a reversible highly dipolar photoinduced intra molecular charge transfer in indandione type molecules (DMABI) accompanied by change of the sign and the value of the dipole moment. Investigations of optical properties of thin host-guest polymer films show that the photoinduced process of DMABI is related to the photoinduced switching between two equally stable state…
Bis(N-naphthyl-N-phenylamino)benzophenones as exciton-modulating materials for white TADF OLEDs with separated charge and exciton recombination zones
Abstract Organic semiconductors were employed as exciton modulators, blue emitters, hole-transporting materials and hosts with resonant-appropriate singlet and triplet energies for efficient and stable white organic light emitting diodes (OLEDs). Two 4,4'-bis(N-naphthyl-N-phenylamino)benzophenones were synthesized using isomeric N-naphthyl-N-phenylamines as the donors and benzophenone as the acceptor moiety. Molecular design of new compounds allowed to obtain required combination of properties, i.e. blue prompt fluorescence in solid state with singlet energies close to those of the selected blue emitter exhibiting thermally activated delayed fluorescence (TADF), low triplet energies of 2.32…
Poling Induced Mass Transport in Thin Polymer Films
In this study we report investigation of the polymer film morphology modifications during their corona poling for fabrication of nonlinear optically (NLO) active materials. We demonstrate that at certain poling conditions surface and spatial inhomogeneities in the poled area of the sample appear. Densities of the inhomogeinities depend on the strength of the poling field, the sample temperature during the poling, and the prepoling conditions. Optimization of the poling conditions directed toward avoiding surface modifications enables us to increase the overall observable effective nonlinearity of the sample up to 10 times. To investigate, understand, and eventually explain the formation of …
Optimized Deposition of Graphene Oxide Langmuir-Blodgett Thin Films
Abstract Single sheet graphene (SG) is an innovative transparent material with high electrical and thermal conduction the use of which in transparent electrodes instead of traditional materials improves the performance of optoelectronic devices. In this study, graphene oxide (GO) has been obtained by a modified Hummer`s method followed by an advanced technique of water removal (lyophilisation). The Langmuir-Blodgett (LB) method was applied to transfer GO from suspension to substrate. To optimize the deposition process, as suspending and spreading solvents the benzene and benzene/methanol mixtures were chosen instead of previously studied water suspensions. The number of GO layers in suspens…
Determination of third-order nonlinear optical properties of ABI derivatives
This material is based upon work supported by the ERDF 1.1.1.1 activity project Nr. 1.1.1.1/16/A/046 “Application assessment of novel organic materials by prototyping of photonic devices”.
Stereoselective synthesis and properties of 1,3-bis(dicyanomethylidene)indane-5-carboxylic acid acceptor fragment containing nonlinear optical chromophores
A series of organic push–pull type chromophores using indane-1,3-dione 5-carboxylic acid (IDCA) and novel 1,3-bis(dicyanomethylidene)indane 5-carboxylic acid (CICA) electron acceptor fragments have been synthesized and characterized. NMR and X-ray analysis revealed that condensation reactions with the CICA fragment were stereoselective and yielded benzylidenes and azomethines with E double bond configurations. Due to the non-planar geometry these compounds are chiral and were acquired as a racemic mixture. The subsequent functionalization of the carboxylic acid group with 5,5,5-triphenylpentan-1-ol yielded solution-processable glass forming materials (6, 8, 10, 13) with glass transition tem…
Synthesis of azobenzene substituted tripod-shaped bi(p-phenylene)s. Adsorption on gold and CdS quantum-dots surfaces
We report here the synthesis of several tripod-shaped oligo(p-phenylene)s with legs composed of two phenylene units. Each leg is end-capped with a thioacetate group for adhesion to metallic surfaces. An azobenzene chromophore group is present on the functional arm of the tripod. The key step in the synthesis is the Pd-catalyzed Suzuki cross-coupling reaction of the silicon derivative core molecule with substituted phenyl moieties and azobenzene derivatives. Gold surfaces prepared by thermal evaporation and CdS quantum-dots surfaces were covered by the tripod-shaped molecules. Modified surfaces were characterized by atomic force microscopy (AFM), fluorescence, and Kelvin Probe analyses.
Hyper-Rayleigh scattering and two-photon luminescence of phenylamine- indandione chromophores
Based on results of quantum chemical (QC) screening, we put under research several phenylamine indane-1,3-dione derivatives including octupolar NLO chromophore A3BI. According to these calculations, molecular first hyperpolarizability (βHRS) should be enhanced upon replacement of methyl substituents with phenyl groups. Surprisingly, βHRS values obtained in our measurements by hyper-Rayleigh scattering (HRS) are much higher than one could expect from QC. Bearing in mind that two-photon luminescence (TPL) is usual cause for overestimation of βHRS in HRS measurements, we have accomplished investigations of TPL properties of these compounds. All investigated triphenylamine derivatives exhibit s…
Origin of Kerr effect: investigation of solutions by polarization dependent Z-scan
This material is based upon work supported by the ERDF 1.1.1.1 activity project No. 1.1.1.1/16/A/046 “Application assessment of novel organic materials by prototyping of photonic devices”.
Stability of the functional NLO polymers–optically induced depoling of the DMABI molecules in sPMMA matrix
Abstract Low polar order (PO) stability is the major problem of the polymer materials for nonlinear optical (NLO) applications. In this contribution we will show the results of PO stability investigations in the corona poled 3 wt.% DMABI + sPMMA guest–host system. Influence of the poling temperature on the building and stability of the polar order in the system will be presented. To characterize the stability, PO destruction has been caused by high intensity light. Polar order stability characteristics were obtained from the sample second harmonic generation intensity (SHI) time decays. We have found that the decay signal is the best fit to the sum of two exponentials. Several physical mode…
Derivatives of indandione and differently substituted triphenylamine with charge-transporting and NLO properties
Abstract Derivatives containing electron-donaiting triphenylamino groups and electron-withdrawing indandione moieties were synthesized and their thermal, electrochemical, photoelectrical and nonlinear optical properties were studied. The synthesized compounds form glasses with the glass transition temperatures ranging from 69 to 118 °C. The ionization potentials of the solid samples of the synthesized materials were found to be in the range of 5.48–5.69 eV. Hole-drift mobilities estimated by xerographic time of flight technique in the amorphous layers of 2-({4-[(4-{[(2E)-1,3-dioxo-2,3-dihydro-1H-inden-2-ylidene]methyl}phenyl)(4-methoxyphenyl)amino]phenyl}methylidene)-2,3-dihydro-1H-indene-1…
Triphenyl group containing molecular glasses of azobenzene for photonic applications
Abstract D-π-A type organic molecules have attracted considerable attention of scientists due to their potential applications in nonlinear optics and holographic data storage as light, flexible and low-cost photonic materials. To provide a better understanding on the relation between the compound chemical structure and their physical properties necessary for the mentioned purposes, eight glassy triphenyl group containing derivatives of azobenzene with incorporated 5,5-dimethylcyclohex-2-enylidene or 4H-pyran-4-ylidene structural fragments and dicyanomethylene, indene-1,3-dione and pyrimidine-2,4,6(1H,3H,5H)-trione acceptor groups have been synthesized and investigated. Thermal stability of …
Effect of Corona Poling and Thermo Cycling Sequence on NLO Properties of The Guest-Host System
In the case of doped polymer system SHG efficiency is proportional to the concentration and orientation degree of NLO-active molecules. Unfortunately, corona poling realised at elevated temperatures causes concentration decrease of NLO-active molecules due to crystallization. On the basis of our studies of the film optical images, refractive index and SHG measurements of the dimethylaminobenzylidene 1,3-indandione and PMMA guest-host system, we have demonstrated that optical quality is improved and second order NLO efficiency is higher, when the external poling electric field is switched on from the very beginning of the sample heating process.
Rational computing of energy levels for organic electronics: the case of 2-benzylidene-1,3-indandiones
Device engineering in organic electronics, an active area of research, requires knowledge of the energy levels of organic materials (traditionally but ambiguously denoted as HOMO and LUMO). These can be effectively determined by electrochemical investigation, but yet more effective would be quantum chemical (QC) computation of these quantities. However, there is no consensus on the computational method in the research community. Ongoing discussions often focus on choosing the right density functional method, but neglect other model parameters, in particular, the basis set. This study considers comparison of various methodologies and parameters for predicting ionization energy I and electron…
Donor and acceptor substituted triphenylamines exhibiting bipolar charge-transporting and NLO properties
Donor-acceptor type triphenylamine-based malonodinitriles were synthesized and their thermal, optical, photophysical, electrochemical and nonlinear optical properties were studied. The synthesized compounds formed glasses with the glass transition temperatures ranging from 38 to 107 °C. The ionization potentials of the samples of the compounds established by cyclic voltammetry were found to be in the range of 5.50–5.57 eV, while those estimated by photoelectron emission spectrometry ranged from 5.36 to 5.74 eV. The electron affinity values of the compounds were found to be in the range of −3.41–−3.05 eV. The ambipolar charge-transporting properties were observed for the layers of triphenyla…
Thin Film Organic Thermoelectric Generator Based on Tetrathiotetracene
This is the peer reviewed version of the following article: K. Pudzs, A. Vembris, M. Rutkis, S. Woodward, Adv. Electron. Mater. 2017, 1600429, which has been published in final form at http://onlinelibrary.wi...002/aelm.201600429/full This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
Study of Structure–Third-Order Susceptibility Relation of Indandione Derivatives
By using the Z-scan method we studied the third-order nonlinear optical parameters of several aminobenziliden-1,3-indandione (ABI) derivatives that have previously been shown to own second-order nonlinear optical properties. Measurements were carried out using two 1064 nm Nd:YAG lasers with picosecond (ps) and nanosecond (ns) pulse widths, respectively. When ns laser was employed in the Z-scan setup, a strong thermal lensing took place resulting in severe overestimation of optical Kerr coefficients. Due to this reason the ps laser was employed to evaluate correct magnitude of Kerr effect. For investigated organic molecules, experimental results show that two-photon absorption at 1064 nm is …
Diphenylsulfone-based hosts for electroluminescent devices: Effect of donor substituents
DG acknowledges to the ERDF PostDoc project No. 1.1.1.2/VIAA/1/16/177. This work was supported by the project of scientific co-operation program between Latvia, Lithuania and Taiwan ?Polymeric Emitters with Controllable Thermally Activated Delayed Fluorescence for Solution-processable OLEDs? (grant No. S-LLT-19-4). Support of the Lithuanian Academy of Sciences is gratefully acknowledged; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART²
Interferometric Z-scan method for thermo-optical effect studies
We demonstrated a new approach to measuring third-order nonlinear optical effects using an experimental setup incorporating both Z-scan and Mach-Zehnder interferometer methods. This method could be especially purposive for thermo-optical effect studies as it can simultaneously probe thermal gradient profile as well as absolute temperature changes induced by an optical beam. The experimental setup was tested using chloroform. Experimental measurements were carried out using 1064 nm Nd:YAG laser with 8 ns pulse width and 40 kHz pulse repetition rate. The measured nonlinear refractive index of chloroform was mainly induced by the thermo-optical effect. As thermo-optical response depends on bea…
All-Organic Waveguide Sensor for Volatile Solvent Sensing
This work was supported by ERDF 1.1.1.1 Activity Project Nr. 1.1.1.1/16/A/046 “Application assessment of novel organic materials by prototyping of photonic devices”. We acknowledge Igors MIHAILOVS for valuable discussions.
Dielectric breakdown of fast switching LCD shutters
Fast liquid crystal optical shutters due to fast switching, vibrationless control and optical properties have found various applications: substitutes for mechanical shutters, 3D active shutter glasses, 3D volumetric displays and more. Switching speed depends not only on properties of liquid crystal, but also on applied electric field intensity. Applied field in the shutters can exceed >10 V/micron which may lead to dielectric breakdown. Therefore, a dielectric thin film is needed between transparent conductive electrodes in order to reduce breakdown probability. In this work we have compared electrical and optical properties of liquid crystal displays with dielectric thin films with thickne…
Structure-dependent tuning of electro-optic and thermoplastic properties in triphenyl groups containing molecular glasses
Abstract The series of seven molecular compounds composed of D–π–A chromophores and triphenylmethyl auxiliary groups were characterized by UV–Vis spectroscopy, differential scanning calorimetry and quantum chemical calculations. Nonlinear optical (NLO) properties of compounds were determined by second harmonic generation measurements in corona poled thin glassy films. The results show that triphenylmethyl auxiliary groups are effective at shielding undesirable dipole interactions in solid phase thus increasing NLO efficiency of materials. Thermal stability up to 108 °C was achieved for a polar order in poled samples.
Impact of aggregates on excitation dynamics in transparent polymer films doped by dipolar molecules
Abstract Optical properties of transparent polymer films of polymethylmethacrylate doped (up to 25 wt.%) by dipolar N , N -dimethylaminobenzylidene 1,3-indandione (DMABI) molecules were studied. Formation of DMABI nanocrystallites, increasing in their density and size with dopant concentration, was revealed by optical microscopy. Transformation of the fluorescence spectrum from the molecular-like emission (for the low dopant concentration below 1 wt.%) to highly red-shifted fluorescence corresponding to self-trapped excitons in the crystallites was observed. It was shown, that due to the resonant energy transfer in the blend, the DMABI nanocrystals can serve as efficient fluorescence marker…
Synthesis and thermoelectric properties of 2- and 2,8-substituted tetrathiotetracenes
Reaction of elemental sulfur with 2-R1 and 2,8-R1,R2-substituted tetracenes (2) in refluxing DMF affords 5,6,11,12 tetrathiotetracenes (1) in good yields (74–99%) for a range of substituents where R1,R2 are: H,H (a); Me,H (b); MeO,H (c); Ph,H (d); Me,Me (e), iPr,Me (f, iPr = iso-propyl, CHMe2), Me,MeO (g); MeO,MeO (h). The reaction rate is limited only by the solubility of the tetracene (2); 2g–h being both the least soluble and slowest reacting. At partial conversion recovered single crystalline 2g led to its X-ray structure determination. Vacuum deposited (substrate deposition temperature 300 K, pressure 7 × 10−6 mbar, source temperature 500 K) thin films from 1 (of initial 88–99% purity)…
An improved molecular design of obtaining NLO active molecular glasses using triphenyl moieties as amorphous phase formation enhancers
New molecular design of obtaining molecular glasses has been developed by linking triphenylmethyl moieties to chromophore core by flexible C-C bridge. Compounds capable of forming stable amorphous phase with good optical quality have been acquired with increased chemical and thermal sustainability compared to the previously reported design. NLO activity of compounds has been measured after corona discharge polling. Compared to previously synthesized trityloxy fragment containing compounds increase of d 33 coefficient by up to 17 times was achieved for the same chromophore core containing compounds.
Influence of corona poling procedures on linear and non-linear optical properties of polymer materials containing indandione derivatives as a cromophores
SHG efficiency of the poled guest - host polymer system is proportional to the concentration and orientation degree of NLO active molecules (chromophores). Corona poling realized at elevated temperatures could cause concentration decrease of NLO- active molecules due to centrosymmetric crystallization. Our studies showed that number density of crystallites is depending on orientation procedure. To obtain the best orientation procedure for guest - host systems containing four different chromophores based on dimethylaminobenzylidene 1, 3 - indandione we have compared optical images and SHG efficiency of corona poled films. According to our observations external poling electric field applied f…
Poling dynamics of an EO active material using parallel-plate electrodes
We describe the sample preparation and experimental setup for second harmonic generation measurement of electro-optical (EO) chromophore/polymer system at the time of contact-poling. Different types of spacers for avoiding electric breakdown due to avalanche multiplication are compared. Electric field threshold values for second harmonic generation are observed in all samples.
Synthesis and nonlinear optical properties of novel N,N-dihydroxyethyl-based molecular organic glasses using triaryl substitutes as amorphous phase formation enhancers
In given study a new structural design of molecular NLO materials is presented where amorphous phase formation is achieved by introduction of bulky trityl and triphenylsilyl substituents. Obtained materials formed stable organic glasses with good optical quality and glass transition temperatures notably exceeding ambient. NLO activity was successfully measured in samples that underwent corona discharge poling. The comparison of both enhancer groups revealed, that trityl group increases thermal sustainability of material, while triphenylsilyl group better promotes formation and stability of amorphous phase.
Perovskite CH3NH3PbI3–XClx Solar Cells and their Degradation (Part 1: A Short Review)
Development of hybrid organic-inorganic perovskite solar cells (PSC) has been one of the hottest research topics since 2013. Within brief literature review, we would like to achieve two objectives. Firstly, we would like to indicate that a whole set of physical properties, such as high change carrier mobility, very low recombination rates, large carrier life time and diffu-sion length, large absorption coefficients and very weak exciton binding energies, are defining high power conversion efficiency (PCE) of methyl ammonium lead trihalide SC. The second objective is to draw attention to some, in our opinion, important aspects that previously have not been satisfactory addressed in literatur…
Novel second-order nonlinear optical polymer materials containing indandione derivativatives as a chromophore
Second order non linear optical (NLO) properties of sPMMA based host-guest systems containing eight dimethylaminobenzylidene -1, 3 - indandione (DMABI) related chromophores have been investigated by means of quantum chemical calculations and SHG experimental characterization. Ab initio calculations with basis set 6-31G were used for molecular geometry determination as well as in the calculations of molecular hyperpolarizability by FF approach. Influence of the chromophore concentration on the host-guest film NLO performance was obtained by SHG Maker fringe experiments. The highest value of d53233 =80 pm/V (frequency corrected value d033 =12 pm/V) at chromophore concentration 15 %wt have bee…
Multifunctional derivatives of dimethoxy-substituted triphenylamine containing different acceptor moieties
This project has received funding from the Research Council of Lithuania (LMTLT), Agreement No. [S-LZ-19-2]. This research was funded by the Région Centre, the Tunisian ministry of research, University of Monastir and the French ministry of Higher Education and Research. J. Bouclé would like to thank the Sigma-Lim LabEx environment for financial supports, and the PLATINOM facility at XLIM laboratory regarding device fabrication and characterizations. DG acknowledges the Lithuanian Academy of Sciences for the financial support.
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