0000000000012102
AUTHOR
Aivars Vembris
Carbene-metal complexes as molecular scaffolds for construction of through-space TADF emitters
Through-space charge transfer (CT) process is observed in Cu(I) carbene-metal-amide complexes, where conventional imidazole or imidazoline N-heterocyclic (NHC) carbene fragments act as inert linkers and CT proceeds between a metal-bound carbazole donor and a distantly situated carbene-bound phenylsulfonyl acceptor. The resulting electron transfer gives a rise to efficient thermally activated delayed fluorescence (TADF), characterized with high photoluminescence quantum yields (ΦPL up to 90 %) and radiative rates (kr) up to 3.32×105 s-1. TADF process is aided by fast reverse intersystem crossing (rISC) rates of up to 2.56×107 s-1. Such emitters can be considered as hybrids of two existing TA…
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…
Relation between molecule ionization energy, film thickness and morphology of two indandione derivatives thin films
Abstract Nowadays most organic devices consist of thin (below 100 nm) layers. Information about the morphology and energy levels of thin films at such thickness is essential for the high efficiency devices. In this work we have investigated thin films of 2-(4-[N,N-dimethylamino]-benzylidene)-indene-1,3-dione (DMABI) and 2-(4-(bis(2-(trityloxy)ethyl)amino)benzylidene)-2H-indene-1,3-dione (DMABI-6Ph). DMABI-6Ph is the same DMABI molecule with attached bulky groups which assist formation of amorphous films from solutions. Polycrystalline structure was obtained for the DMABI thin films prepared by thermal evaporation in vacuum and amorphous structure for the DMABI-6Ph films prepared by spin-coa…
Tetrathiotetracene thin film morphology and electrical properties
The electrical properties of organic thin films are determined by their chemical constituents and the morphology of the films deposited. In this paper the morphology of vacuum sublimed (7?10-6 mbar) tetrathiotetracene (TTT) thin films is shown to be strongly affected by the thermal deposition temperature (222-350 K) and rate of deposition. Mostly needle-like morphologies are identified by scanning electron microscopy. Optimal TTT purity (a pre-requisite for device preparation via subsequent oxidation) is evidenced by their initially low electrical conductivity. Altering the TTT morphology, by variation of the evaporation parameters, strongly affects this base electrical conductivity. Four p…
Influence of organic material and sample parameters on the surface potential in Kelvin probe measurements
Financial support provided 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” as well as Scientific Research Project for Students and Young Researchers Nr. SJZ2016/20 realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged.
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 …
Energy level determination in bulk heterojunction systems using photoemission yield spectroscopy: case of P3HT:PCBM
Financial support provided by Scientific Research Project for Students and Young Researchers Nr. SJZ2015/20 realized at the Institute of Solid State Physics, University of Latvia, is greatly acknowledged. This work has been supported by the Latvian State Research Program on Multifunctional Materials IMIS2. Jennifer Mann from Physical Electronics is greatly acknowledged for providing UPS data.
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 …
Light-emitting thin films of glassy forming organic compounds containing 2-tert-butyl-6-methyl-4H-pyran-4-ylidene
Low molecular mass organic compounds which make thin films from volatile organic solutions would be great benefit in future organic light emitting systems. Two most important advantages could be mentioned. First - the repetition of synthesis of small molecules is better than for polymers. Second - wet casting methods could be used. In this work we are presenting optical, electroluminescence and amplified spontaneous emission properties of four original glassy forming compounds containing 2-tert-butyl-6-methyl-4H-pyran-4-ylidene fragment as backbone of the molecule. They has the same N,N-dialkylamino electron donating group with incorporated bulky trityloxy ethyl groups. The difference of th…
Photoinduced mass transport in low molecular organic glasses and its practical application in holography
Abstract In this paper we present the synthesis and optical properties of amorphous low molecular compound 4-((4-(bis(5,5,5-Triphenylpentyl)amino)phenyl)diazenyl)benzoic acid. The surface relief gratings formation by polarization holography method on these thin films (thicknesses are 200–1700 nm) was shown. The dependence of the surface relief modulation on various parameters: recording exposure dose, the polarization state of the recording beams, the grating period and the film thickness of the material was demonstrated. Values of surface tension at the air-film before and after irradiation of the substance by polarized radiation were measured. The efficiency of surface relief formation in…
Energy structure and electro-optical properties of organic layers with carbazole derivative
Abstract Phosphorescent organic light emitting diodes are perspective in lighting technologies due to high efficient electroluminescence. Not only phosphorescent dyes but also host materials are important aspect to be considered in the devices where they are a problem for blue light emitting phosphorescent molecules. Carbazole derivative 3,6-di(9-carbazolyl)-9-(2-ethylhexyl)carbazole (TCz1) is a good candidate and has shown excellent results in thermally evaporated films. This paper presents the studies of electrical properties and energy structure in thin films of spin-coated TCz1 and thermally evaporated tris[2-(2,4-difluorophenyl)pyridine]iridium(III) (Ir(Fppy)3). The 0.46 eV difference …
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.
<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.
Photovoltaic effect in bulk heterojunction system with glass forming indandione derivative DMABI-6Ph
The aim of the work is to evaluate possible use of 2-[[4-(bis(2-trityloxyethyl)amino)phenyl]methylene]indane-1,3-dione (DMABI-6Ph) as light absorbing material for solar cells. DMABI-6Ph is a perspective material due to its good photoelectrical, thermal and chemical properties. The main advantage of DMABI-6Ph is its ability to form amorphous films by wet-casting methods thus allowing using the compound in organic solar cells made from solution. For now most popular materials for solution processable solar cells are polymer P3HT and fullerene derivative PCBM, but lot of investigations are in the field of new low molecular weight materials to replace the polymer. Photoelectrical measurements w…
Synthesis and Spectroscopic Characteristics of Ligands Based on Quinolin-8-Ol as Useful Precursors for Alq3 Type Complexes
In order to develop reliable methods for the synthesis of various 5-substituted-8-oxyquinoline derivatives for the preparation of Alq3-type complexes, we have improved the reaction conditions on some syntheses described in the literature, successfully synthesized new ligands based on quinolin-8-ol and characterized their chemical structures by NMR. Some of the synthesized quinolin-8-ol derivatives containing incorporated bulky triphenyl or tert-butyl groups showed blue luminescence in the solid state due to the possible aggregation induced emission enhancement (AIEE) with a maximum wavelength around 510 nm. More detailed light-emission property investigation of the mentioned bulky group con…
All-organic fast intersystem crossing assisted exciplexes exhibiting sub-microsecond thermally activated delayed fluorescence
A novel strategy is presented towards acquisition of exciplex systems exhibiting thermally activated delayed fluorescence (TADF) with a high reverse intersystem crossing (RISC) rate (exceeding 107 s−1). This approach involves constructing exciplex donor–acceptor molecular pairs, where the acceptor molecule possesses the ability to undergo fast and efficient intersystem crossing (ISC). With the use of 6-cyano-9-phenylpurine (PCP) acceptor and carbazole-based donor molecules, exciplexes were obtained, where the excitation is contained on PCP and undergoes fast ISC to form a local excited triplet state (3LEA). The controlled excitation transfer to the 3LEA level provides an optimal reverse int…
Light emitting and electrical properties of pure amorphous thin films of organic compounds containing 2-tert-butyl-6-methyl-4H-pyran-4-ylidene
Abstract Low molecular weight organic compounds which make thin films from organic solutions would be a great benefit in future organic light emitting systems. Two most important advantages should be mentioned. First – repeatability of synthesis of small molecules is better than of polymers. Second – wet casting methods can be applied. In this paper we present optical and opto-electrical properties of three glassy forming compounds containing 2-tert-butyl-6-methyl-4H-pyran-4-ylidene fragment as a backbone. They have the same N,N-dialkylamino electron donating group with attached bulky trityloxyethyl groups. The difference between these compounds is in an electron acceptor group. One has ind…
On the development of a new approach to the design of lanthanide-based materials for solution-processed OLEDs
The targeted design of lanthanide-based emitters for solution-processed organic light-emitting diodes (OLEDs) resulted in obtaining an NIR OLED with one of the highest efficiencies among ytterbium-based solution-processed OLEDs (30 μW W-1). The design was aimed at the combination of high luminescence efficiency with solubility and charge carrier mobility. The latter was achieved thanks to the introduction of the purposefully selected neutral ligands, which combine electron mobility and the ability to sensitize lanthanide luminescence. Besides, the HOMO and LUMO energies and charge carrier mobility of solution-processed thin films of coordination compounds were measured experimentally for th…
New Figure of Merit for Tailoring Optimal Structure of the Second Order NLO Chromophore for Guest-Host Polymers
Reliability to forecast SHG efficiency using two sets of non linear optical (NLO) chromophore figures of merit (FOM) was tested. One of them predicts that SHG efficiency d 33 of the poled guest-host polymer is proportional to ground state dipole ∼ μg, another to ∼ 1/μg. Correlation of maximal achieved second order NLO efficiency of the PMMA based systems containing eight dimethylaminobenzylidene-1, 3-indandione (DMABI) related chromophores with proposed FOM have been analyzed. The best correlations were obtained with second set of FOM, especially if high dipole moment (μg > 7D) chromophores are included in analysis.
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…
Solution-processable green phosphorescent iridium(III) complexes bearing 3,3,3-triphenylpropionic acid fragment for use in OLEDs
New solution-processable materials based on well-known green iridium(III) heteroleptic complexes (ppy) 2 Ir(acac) and (ppy) 2 Ir(pic) were acquired by chemical modification of ppy ligand with functionable hydroxyl groups and subsequent esterification with 3,3,3-triphenylpropionic acid fragment. Photoluminescence quantum efficiencies up to 0.90 were measured for the compounds in solution. Emission characteristics in pure solid films and different guest-host systems with hole transporting materials were investigated. Green light emitting OLEDs (organic light emitting devices) was prepared and characterized.
Effects of steric encumbrance of iridium( iii ) complex core on performance of solution-processed organic light emitting diodes
Iridium(iii) complexes are the most frequently applied commercialized green and red emitters for organic light emitting diode (OLED) displays. Throughout years a significant research effort has been devoted to modify these compounds, in order to make them suitable for cost-effective solution-processing techniques, such as inkjet printing. To achieve this, the inherent tendency of the complex molecules to form poorly emissive aggregates needs to be suppressed. In many cases this has been achieved by an encapsulation of the iridium(iii) complex core with dendritic structures, composed of either passive or charge-transporting fragments. In order to validate this approach, we acquired three str…
Energy level determination of purine containing blue light emitting organic compounds
Organic light emitting diodes (OLED) have found their applications in the mobile and TV screens. Till now the commercially available diodes are made by expensive thermal evaporation in a vacuum. The costs of OLED fabrication could be decreased by applying low-cost wet casting methods, for example, spin-coating. In this work, we have studied a group of blue light emitting purine derivatives which could potentially be used in OLEDs. The advantage of these compounds is their ability to form amorphous thin films from solutions. All the thin films were prepared by the spincoating method from chloroform solution on ITO glass. The position of hole and electron transport energy levels is important …
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…
Study of the P3HT/PCBM interface using photoemission yield spectroscopy
Photogeneration efficiency and charge carrier extraction from active layer are the parameters that determine the efficiency of organic photovoltaics (OPVs). Devices made of organic materials often consist of thin (up to 100nm) layers. At this thickness different interface effects become more pronounced. The electron affinity and ionization energy shift can affect the charge carrier transport across metal-organic interface which can affect the performance of the entire device. In the case of multilayer OPVs, energy level compatibility at the organic-organic interface is as important. Photoemission yield spectroscopy was used for organic-organic interface study by ionization energy measuremen…
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…
Fluorescence and amplified spontaneous emission of glass forming compounds containing styryl-4H-pyran-4-ylidene fragment
Potential of glassy films of newly synthesised low molecular weight organic molecules for light amplification and lasing applications has been investigated by analysing fluorescence, transient differential absorption and amplified spontaneous emission properties. These non-symmetric and symmetric molecules contain styryl-4H-pyran-4-ylidene fragment with three different electron acceptor groups: dicyanomethylene, barbituric acid, indene-1,3-dione. Fluorescence quantum yields of the investigated compounds in solutions are between 0.32 and 0.54, while they drop down by an order of magnitude in thin solid films. Incorporation of bulky side groups reduced excitonic interactions enabling manifest…
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…
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.
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…
Photoelectrical properties of indandione fragment containing azobenzene compounds
Organic materials are becoming more popular due to their potential application in electronics. Low molecular weight materials possible produce from solution are in special consideration. It gives the possibility to avoid both thermal evaporation in vacuum, and use of polymers in thin film preparation process. Indandione fragment containing azobenzene compounds are one of such materials. These compounds are good candidates for use in design of novel molecular electronic devices due to their possibility to form amorphous structure from solution thus allowing developing flexible, small size systems with low production costs. In this work three indandione fragment containing azobenzene compound…
Piraniliden fragmentu saturošu krāsvielu optiskās un optoelektriskās īpašības
Anotācija. Promocijas darbs ir par oriģināliem piraniliden fragmentu saturošiem organiskajiem savienojumiem, kuri pateicoties tritiloksietil grupai spēj veidot amorfu plānu kārtiņu no šķīduma. Darba mērķis ir izpētīt šo amorfu struktūru veidojošu vielu optiskās un elektriskās īpašības un noskaidrot vielu iespējamo pielietojumu organiskajos cietvielu lāzeros un gaismu emitējošās diodēs. Darbā tika pierādīts, ka tritiloksietil grupām ir maza ietekme uz elektronu pārejām pētītajās molekulās. Tai pašā laikā šī grupas efektīvi ekranē molekulas hromoforo daļu no apkārtējās vides, tādejādi nodrošinot iespēju novērot fotoluminiscenci neatšķaidītās plānā kārtiņās (kārtiņas, kuras sastāv tikai no pēt…
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.
Eu3+ ternary and tetrakis complexes with carbazole and methyl group substituted dibenzoylmethane derivatives: Induction of aggregation enhanced emission
Abstract Two dibenzoylmethane (DBM) derivatives with methyl (Me-DBM) or carbazole (CBZ-DBM) substituents at the para-position of the phenyl ring and their four novel ternary and tetrakis Eu3+ complexes with 1,10-phenanthroline (PHEN) as a secondary ligand or tetraethylamonium ion (N+(Et)4) as the counter-cation were synthesized and characterized. The investigation of the optical properties of the complexes revealed that Me-DBM based compounds exhibit aggregation enhanced emission (AEE), while in the case of CBZ-DBM this effect is not observed. At the same time, the introduction of a carbazole substituent reduces the emission quantum yield of the complexes. The decrease in luminescence effic…
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…
Amplified spontaneous emission of pyranyliden derivatives in PVK matrix
One of the well-known red light emitting laser dyes is 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4Hpyran ( DCM ). Amplified spontaneous emission (ASE) has been widely investigated of DCM molecules or its derivatives in polymer or low molecular weight matrix. The main issue for these molecules is aggregation which limits doping concentration in matrix. Lowest ASE threshold values within concentration range of 2 and 4 wt% were obtained. In this work ASE properties of two original DCM derivatives in poly(N-vinylcarbazole) ( PVK ) at various concentrations will be discussed. One of the derivatives is the same DCM dye with replaced butyl groups at electron donor part with bulky try…
Sb2S3 solar cells with a cost-effective and dopant- free fluorene-based enamine as a hole transport material
The “Development of Semi-Transparent Bifacial Thin Film Solar Cells for Innovative Applications” benefits from a 999372 € grant from Iceland, Liechtenstein and Norway through the EEA Grants. The aim of the project is to develop a new approach based on novel materials and structures and production technologies, which are the key to further increase the share, and range of applications of PV in areas with sub-average sunlight, including Baltic and Nordic countries. Therefore, development of resource saving, cost-effective and efficient PV devices is a primary challenge of this project. Project contract with the Research Council of Lithuania (LMTLT) No is S-BMT-21-1(LT08-2-LMT-K-01-003). The D…
Amplified spontaneous emission of glass forming DCM derivatives in PMMA films
4-(dicyanomethylene)-2-methyl- 6-(p-dimethylaminostyryl)-4H-pyran ( DCM ) is well known red laser dye which can be used also in solid state organic lasers. The lowest threshold value of amplified spontaneous emission was achieved by doping 2wt% of DCM molecule in tris-(8-hydroxy quinoline) aluminium (Alq
Toward device applicable second order NLO polymer materials: definition of the chromophore figure of merit
Maximal achieved second order non linear optical (NLO) efficiency of the PMMA based host – guest systems containing eight dimethylaminobenzylidene -1, 3 - indandione (DMABI) related chromophores have been analysed. Two contradicting sets of NLO chromophore figure of merit (FOM) equations were tested. One of them predicts that NLO efficiency of the poled polymer host -guest film is proportional to ground state dipole d33 ~ 1/μg, another to d33 ~ 1/μg. The best correlations for the maximal achieved nonlinearity were obtained with second set of FOM, especially if high ground state dipole (μg > 7D) chromofores are included in analysis.
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…
Synthesis and investigation of charge transport properties in adducts of hole transporting carbazole derivatives and push-pull azobenzenes
Abstract In order to investigate the viability of a material design for bulk heterojunction (BHJ) organic solar cells, where hole transporting group is bound to the donor moiety, we report the synthesis and charge transport characteristics of 3-(diphenylamino)carbazolyl-functionalized derivatives of 2-(4-((4-(dimethylamino)phenyl)diazenyl)benzylidene)-1H-indene-1,3-dione (DMAAzi) chromophore. Three different bounding configurations were examined in these adducts. Additionally, a trityl-functionalized derivative of DMAAzi was prepared and used for comparison purposes. All of the synthesized materials form thin amorphous films from volatile organic solvents and exhibit glass transition temper…
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…
3,3'-Bicarbazole structural derivatives as charge transporting materials for use in OLED devices
In this study we report novel 3,3′-bicarbazole based charge transporting materials mainly designed for a use in systems containing phosphorescent iridium (III) complex emitters. A low-cost oxidative coupling reaction using FeCl3 was employed in the synthesis of 3,3′-bicarbazole compounds. Different derivatives of 3,3′-bicarbazole with 4-ethoxyphenyland ethyl- substituents at 9,9′- positions and (2,2-diphenylhydrazono)methyl- and 4-(dimethylamino)styryl- substituents at 6,6′- positions were synthesized. Obtained (2,2-diphenylhydrazono)methyl- derivatives exhibit glass transition temperatures that are sufficient for applications in electronic devices. Thin amorphous films of good optical qual…
New Electroactive Polymers with Electronically Isolated 4,7-Diarylfluorene Chromophores as Positive Charge Transporting Layer Materials for OLEDs
The OLED materials were developed in the frame of project funded by the Research Council of Lithuania (grant No. S-LLT-19-2). B.Z. is thankful to the National Natural Science Foundation of China (No. 51773195), and the Research & Development Projects in Key Areas of Guangdong Province, China (No. 2019B010933001). We are also obliged to D. Volyniuk for measurements of the ionization potentials.
Emission Enhancement by Intramolecular Stacking between Heteroleptic Iridium(III) Complex and Flexibly Bridged Aromatic Pendant Group
Phosphorescent iridium(III) complexes suffer from a strong aggregation quenching, limiting their use in solution-processed or crystalline organic light-emitting diodes. Here we report how an intramolecular stacking between a flexibly bridged bulky aromatic pendant group and the core of nonionic heteroleptic complex can be exploited to minimize the negative effects of this drawback. The stacked conformation provides a rigid sterical shielding of the polar molecular surface, improving photoluminescence quantum yield of the complex both in solution and crystalline state.
Photophysical and Electrical Properties of Highly Luminescent 2/6-Triazolyl-Substituted Push-Pull Purines.
This work is supported by the ERDF 1.1.1.1. activity project No. 1.1.1.1/16/A/131. The authors thank Dr. sc. ing. Jānis Zicāns and Dr. sc. ing. Remo Merijs Meri for DSC analyses.
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…
Thiphenylmethane based structural fragments as building blocks towards solution-processable heteroleptic iridium(iii) complexes for OLED use
A novel structural approach to solution-processable heteroleptic iridium(III) complexes is presented. On the basis of 2-arylbenzo[d]thiazole cyclometalating main ligands and picolinic acid (pic) and acetylacetone (acac) ancillary ligands six new yellow or orange emitting materials were obtained using attached 1,1,1-triphenylmethylpentane substituents as aggregation preventing and solubility enhancing functional fragments. The obtained compounds show high photoluminescence quantum yield values in the range of 0.64 to 0.90. OLEDs with a spin-coated emissive layer were successfully prepared, with the highest achieved external quantum efficiency of 7.9%, current efficiency of 12.4 cd A−1 and po…
CCDC 1988182: Experimental Crystal Structure Determination
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CCDC 1845861: Experimental Crystal Structure Determination
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