Investigation of photoluminescence and amplified spontaneous emission properties of cyanoacetic acid derivative (KTB) in PVK amorphous thin films
This work was supported by European Regional Development Fund within the Project No. 1.1.1.1/16/A/046 and A.Riekstins SIA “Mikrotīkls” donation, administered by University of Latvia Foundation.
Thermal and optical properties of red luminescent glass forming symmetric and non symmetric styryl-4H-pyran-4-ylidene fragment containing derivatives
Abstract Dyes with amorphous structure deposited from organic solvents and having good fluorescence properties show potential for photonic device applications. Organic glass-forming symmetric and non symmetric styryl- derivatives of 2(2,6-substituted-4H-pyran-4-ylidene)-malononitrile (it has backbone of known laser dye 4-(dicyanomethylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran), 2(2,6-substituted-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione and 2(2,6-substituted-4H-pyran-4-ylidene)-pyrimidine-2,4,6(1H,3H,5H)-trione were synthesized and investigated. Glass transition temperatures higher than 110 °C were achieved. The absorption bands in dichloromethane solution cover the spectral regi…
Optical properties of the low-molecular amorphous azochromophores and their application in holography
The films based on the low-molecular amorphous azochromophore 2-(3-(4-((4- (Ethyl(2-(trityloxy)ethyl)amino)phenyl)diazenyl)styryl)-5,5-dimethylcyclohex-2-enylidene) malononitrile (IWK-2M) were prepared. The optical properties of the material, such as transmittance and reflection spectra of the film, sensitivity to polarization holographic recording by two wavelengths (405 and 532 nm) were studied. The direct relief formation during the polarization holographic recording was explored, relief depth dependence on exposure and record beam intensity was investigated. The holographic matrix on this material base was produced without chemical etching process; the replication of holographic image w…
Impact of the molecular structure of an indandione fragment containing azobenzene derivatives on the morphology and electrical properties of thin films
Abstract The solution casting method is low-cost processing method. Moreover, it is possible to prepare amorphous thin films by using this method, and thus, both optical quality and electrical properties could be improved in compare to polycrystalline films made by thermal evaporation in vacuum. Therefore, low-molecular-weight compounds that form amorphous structure from solution could be promising in organic electronics. In this work film morphology, molecule energy levels, and charge carrier mobility in thin films of indandione fragment containing azobenzene derivatives were studied. Deep charge carrier trapping states that drastically influenced charge carrier mobility were observed for …
Stimulated emission and optical properties of pyranyliden fragment containing compounds in PVK matrix
This work has been supported by National Research program “Multifunctional materials and composites, photonics and nanotechnology (IMIS2)”. Financial support provided by Scientific Research Project for Students and Young Researchers No. SJZ2015/12 realised at the Institute of Solid State Physics, University of Latvia is greatly acknowledged.
Pyranylidene indene-1,3-dione derivatives as an amorphous red electroluminescence material
The organic light-emitting diode (OLED) has promising applications in flat-panel displays and novel light sources. Thus far, OLED structures have mostly been made by thermal evaporation in vacuum. An alternative approach is to use small molecules that form amorphous (glassy) structures from solutions. Such compounds can be used in ink-jet printing technologies and result in reduced OLED prices. We present an original red fluorescent organic compo- und 2-(2-(4-(bis(2-(trityloxy)ethyl)amino)styryl)-6-methyl-4H-pyran-4-ylidene)-1H-indene-1, 3(2H)-dione (ZWK1), and its derivative 2-(2,6-bis(4-(bis(2-(trityloxy)ethyl) amino)styryl)-4H- pyran-4-ylidene)-1H-indene-1,3(2H)-dione (ZWK2), where the m…
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…
Solid state solvation effect and reduced amplified spontaneous emission threshold value of glass forming DCM derivative in PMMA films
Abstract Molecule crystallization is one of the limitations for obtaining high-gain organic laser systems. One of the examples is well known red laser dye 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM). The lowest threshold value of amplified spontaneous emission was achieved by doping 2 wt% of DCM molecule in tris-(8-hydroxy quinoline) aluminum (Alq3) matrix. Further increase of the DCM dye concentration makes the system less efficient as its threshold value increases. It is due to large intermolecular interaction, which induces photoluminescence quenching. Compounds with reduced intermolecular interaction could be prospective in organic laser systems due to higher …
Glass-Forming Nonsymmetric DWKdyes with 5,5,5-Triphenylpentyl and Piparazine Moieties for Lightamplification Studies
This work has been supported by the European Regional Development Fund within the Activity 1.1.1.2 “Post-doctoral Research Aid” of the Specific Aid Objective 1.1.1 “To increase the research and innovative capacity of scientific institutions of Latvia and the ability to attract external financing, investing in human resources and infrastructure” of the Operational Programme “Growth and Employment” (No. 1.1.1.2/VIAA/1/16/035). Financial support provided by A. Riekstins SIA “Mikrotīkls” donation, administered by the University of Latvia is greatly appreciated. There are no conflicts of interest to declare.
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…
Glass-forming derivatives of 2-cyano-2-(4H-pyran-4-ylidene) acetate for light-amplification systems
Abstract A series of 2-cyano-2-(4H-pyran-4-ylidene) acetate derivatives with triphenyl and 9H-carbazole moieties were synthesized and investigated, mostly for potential applications in organic solid state lasers. Synthesized compounds show remarkable amorphous film formation ability, tunable thermal properties (thermal stability varies from 190 °C to 387 °C and glass transition temperature from 94 °C up to 141 °C) with light absorption from 400 nm to 600 nm and photoluminescence from 600 nm up to 800 nm. Dyes with incorporated mono-styryl- electron donating fragment (KTB, KTBC and KTB3K) showed higher photoluminescence quantum yield (PLQY) (from 16% up to 23%), significantly lower amplified…
Optical and amplified spontaneous emission of neat films containing 2-cyanoacetic derivatives
During the last two decades, small organic molecules have been widely studied for potential applications in organic solid-state lasers due to low-cost production, simple processing possibility and physical property tuning ability through chemical structure synthetic modifications. One of the most investigated and applied compound in dye lasers is 4- (dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM). It has shown remarkable properties as a dye in solid-state lasers. One of the drawbacks of this compound is high intermolecular interactions which reduce emission efficiency. Therefore it can be applied only in doped systems in low concentration (around 2 wt%). Recently we hav…
Several Derivatives of 6-(Tert-Butyl)-4H-Pyran-4-Ylidene Malononitrile with Different Amorphous Phase Promoting Substituents for Light-Amplification Systems
A series of glassy 6-(tert-butyl)-4H-pyran-4-ylidene malononitrile (DCM) derivatives with covalently attached amorphous state promoting bulky 1,1,1-triphenylmethyl (trityl) moieties through several chemical design approaches have been synthesized and investigated for suitability in organic solid state laser applications. Results showed that the bonding type of such functional groups had a considerable influence on glass structure forming dye thermal properties and a slight influence on their optical properties. Thermal stability up to 346 °C was achieved with glass transitions in the range from 39 to 138 °C. Incorporation of bulky triphenyl substituents via ester groups showed remarkable am…
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 …
Glassy 2-(1-benzyl-2-styryl-6-methylpyridin-4(1H)-ylidene) fragment containing 1H-indene-1,3(2H)-dione and pyrimidine-2,4,6(1H,3H,5H)-trione derivatives with light-emitting and amplified spontaneous emission properties
A series of 2-(1-benzyl-2-(styryl)-6-methylpyridin-4(1H)-ylidene) fragment containing glassy organic compounds have been synthesized from relevant luminescent 4H-pyran-4-ylidene derivatives and investigated as potential solution processable emitters. Glass transition temperatures of synthesized 1H-pyridine compounds are above 100°C with thermal stabilities higher than 260°C. In the solutions of dichloromethane their absorption bands are in the range from 350 nm to 500 nm with photoluminescence from 500 nm to 650 nm. In a contrary to the 4H-pyran-4-ylidene derivatives, the incorporation of various electron acceptor fragments within the 1H-pyridine fragment containing molecules only slightly …
HAPPY Dyes as Light Amplification Media in Thin Films
A series of 1Hamorphous tri-phenyl pyridine (HAPPY) dyes have been synthesized from luminescent triphenyl-group-containing 2-methyl-6-styryl-substituted-4H-pyran-4-ylidene derivatives in reactions with benzylamine and investigated for suitability as solution-processable light-emitting medium components in thin films for amplified spontaneous emission (ASE). Conversion of a 4H-pyrane ring into a 1H-pyridine fragment enables aggregation-induced emission enhancement (AIEE) behavior in the target products and slightly increases thermal stability, glass transition temperatures, and ASE efficiency with PLQY up to 15% and ASE thresholds as low as 46 μJ/cm2 in neat spin-cast films, although thermal…
Nonlinear optical properties of low molecular organic glasses formed by triphenyl modified chromophores
The series of organic molecular glasses have been studied as possible candidates for nonlinear optical (NLO) applications. Amorphous phase formation of investigated materials is ensured by the presence of bulky triphenyl substituents in molecular structure of NLO chromophores. Linear optical properties as well as NLO coefficients and thermal stability of NLO activity for the 13 molecular materials in glassy thin solid films have been determined. For the benzylidene-1,3-indandione chromophore containing compound the highest d33 value equal to 280 pm/V was measured under the 1064 nm excitation. Among the investigated compounds uppermost achieved thermal sustainability of NLO response was 108 …
Glass-forming non-symmetric bis-styryl-DWK-type dyes for infra-red radiation amplification systems
Abstract A series of D-π-A type organic dyes with bulky triphenylmethyl moiety containing 2,6-bis-(4-substituted)styryl-4H-pyran-4-ylidene donor (D) fragments and different electron acceptors (A) were synthesized and investigated, mostly for potential applications in organic solid-state lasers as infra-red (IR) radiation amplification medium. Dye glass transition temperature is above 99 °C with thermal stability in the region from 173 °C to 326 °C which was slightly influenced by the electron acceptor fragment attached to the 4H-pyrane ring in 4-position. Introducing substituents in 4-position within one of the styryl-fragments with stronger electron withdrawing properties decreased ASE exc…
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.
Solution processable piperazine and triphenyl moiety containing non-symmetric bis-styryl-DWK type molecular glasses with light-emitting and amplified spontaneous emission properties
A series of 2,6-bis-styryl-4H-pyran-4-ylidene fragment containing glassy organic compounds with chemically stable bonding of amorphous phase promoting bulky triphenyl moieties through piperazine structural fragment (DWK-T dyes) in a form of 2-(5,5,5-triphenylpentyl)piperazin-1-yl)styryl)-substituent have been synthesized and investigated as the potential gain medium component for organic solid state laser applications. Physical properties of the dyes vary and are mostly depending from the other styryl-substituent attached to the 4H-pyran-4-ylidene backbone fragment in 6-position. Thermal stability of synthesized dyes is above 312°C with the glass transitions from 97°C to 109°C. Obtained nea…
Solution processable 2-(trityloxy)ethyl and tert-butyl group containing amorphous molecular glasses of pyranylidene derivatives with light-emitting and amplified spontaneous emission properties
Abstract Small organic molecules with incorporated 4 H -pyran-4-ylidene (pyranylidene) fragment as the π-conjugation system which bonds the electron acceptor fragment (A) with electron donor part (D) in the molecule – also well known as derivatives of 4-(dicyano-methylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran ( DCM ) laser dye-have attracted considerable attention of scientists as potential new generation materials for organic photonics and molecular electronics due to their low-cost fabrication possibility, flexibility and low-weight. Six glassy derivatives of 4 H -pyran-4-ylidene (pyranylidene) with attached bulky 2-(trityloxy)ethyl and tert -butyl groups are described in this re…