Organic materials are actively researched for their potential application in the manufacturing of solar cells. The possibility to vary the structure of the molecules and the possibility of using wet casting methods such as spin-coating or inkjet printing are the main advantages of these materials. In recent years the research has shifted away from fullerenes as electron acceptor materials due to their disadvantages. Additionally, the introduction of a third component in the active layer of organic solar cells allows the expansion of the absorption spectrum of the cell thus increasing the solar cell efficiency compared to the two-component bulk heterojunctions. The manufacturing of ternary organic solar cells (TOSC) is easier than tandem cells, thus reducing the potential costs upon their commercialization.
In this work, we have studied the application of novel dicyanomethylene-functionalized s-indacene-tetraone based non-fullerene acceptors IC-1 and IC-2 as the third component in TOSCs. The chromophores IC-1 and IC-2 with donor-acceptor-donor (D-A-D) molecular composition were acquired by condensation reactions between s-indacene-tetraone derivative acceptor fragment and aniline- or indoline-based electron-donating fragments. Electron donor polymer PM6 and electron acceptor material Y7 were used as the base materials for the TOSCs. The energy levels of IC-1 and IC-2 are located between the levels of PM6 and Y7 creating the cascade effect. IC-2 absorption has an additional shoulder between 650 nm and 800 nm which helps to increase the power conversion efficiency and reduce the losses shown by the external quantum efficiency (EQE) measurements.
KEYWORDS: Temperature metrology, Quantum efficiency, Metals, Thin films, Luminescence, Copper, Chemical species, System on a chip, Scattering, Phosphorescence
Materials for organic light-emitting diodes could be divided into several generations were last 3rd generation organic compounds exhibiting TADF which exhibit up to 100% singlet and triplet state conversation to light without the presence of heavy metal. Organometallic complexes consisting of Cu metal atom is a conceptually different class of low-cost TADF emitters. While this element does not exhibit fast room-temperature phosphorescence, it still can promote a rapid TADF, despite the considerable ΔEST gaps met in such compounds (< 0.05 eV). In this work, we present a novel approach towards TADF emitters where charge transfer through-space and metal-assisted take place. Cu complexes bearing carbazolide and carbene ligands were synthesized. Imidazole-based N-heterocyclic carbenes (NHCs) were used, with electron-accepting sulphonyl groups introduced at 4-position of the N-bound 2,6-diisopropylphenyl (Dipp) substituents. Photoluminescence bands, decays and quantum yields of complexes in various solutions, as well as PMMA-doped films with emitter concentration 5 wt%, were taken. Emission properties of thin films in the temperature diapason from 10 to 300 K were measured to estimate the charge transfer mechanism. For PL bands at room temperature excitation wavelength was either 300 or 375 nm. For temperature-induced CT emission band shifts in vacuum 345 nm excitation wavelength was used, delay 50 ns and width 10 μs. To get PL decays at room temperature a laser with a wavelength of 375 nm was used and decay was measured at the peak wavelength. For temperature-induced decays in vacuum used excitation was 345 nm, time range 50 µs. To get quantum yields at room temperature, emission and scattering ranges of the sample were measured separately with 375 nm excitation. Photoluminescence quantum yield from 0.2 to 0.3 was obtained in solutions but in thin films, it increased up to 0.9 due to the decreased torsional degree of freedom. Emission decays could be described by three exponential functions in all temperature intervals. One featuring a prompt and two delayed emission components. For both delayed emissions, the fastest and slowest emission rate decrease is observed throughout the cooling range, designating a thermally activated nature of the emissive process. The corresponding ΔEST values were estimated from Arrhenius plots and are in the range of 0.0062−0.0075 eV. By combining through-space CT architecture, giving compounds the characteristic low ΔEST values, with the presence of a heavy metal atom, which provides small, but still present SOC.
The synthesis of a novel imidazolidine type N-heterocyclic carbene (NHC) Cu (I) complex with asymmetrically attached phenylsulfonyl- acceptor group is presented. The asymmetrical ligand was used for the preparation two Cu(I) carbene-metal-amide (CMA) complexes with carbazolide (complex 1) or 1,8-dimethylcarbazolide (complex 2) as the amide donors. Obtained complexes exhibit efficient thermally activated delayed fluorescence (TADF) with luminescence quantum yields (QY) reaching 0.80 in PMMA matrix. Metal promoted through-space charge transfer approach in the emitter design lowers the ΔΕST gap and the small spin-orbit coupling (SOC) provided by metal atom enables high radiative rates (kr = 2.21×105 s-1 for complex 2). The photophysical properties of the asymmetrical (1-2) and previously reported symmetrical (3-6) molecular designs are compared. Obtained results suggest a closely similar photophysical behavior for both the asymmetrical and symmetrical CMA complexes.
The impact of metal atom on the photophysical properties of luminescent organometallic carbene-metal-amide complexes exhibiting through-space charge transfer is investigated. The substitution of copper atom with gold alters the excited state energy level configuration of the emitter. While in the copper-based emitters the lowest triplet excited state (T1) is related to a through-space charge transfer between the carbazolide donor and carbene-bound phenylsulphonyl acceptor, in the gold-bearing structural analogue T1 level is accompanied by an additional closely situated triplet state T2, which features a charge transfer between the carbazolide donor and imidazolidine carbene acceptor. Because of a significant spin-orbit coupling provided by Au atom T2 state exhibits relatively fast phosphorescence rate of 8×104 s-1. Consequently, the emissive process for the gold-functionalized compound can be characterized with a co-occurring thermally activated delayed fluorescence (TADF) and phosphorescence, in contrast to the copper-based structural analogues, where only TADF is observed.
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 quality can be produced from synthesized materials using spin-coating method. The effect of (2,2-diphenylhydrazono)methylsubstituents at 6,6′- and 4-ethoxyphenyl- substituents at 9,9′- positions on the charge transport properties of the 3,3′-bicarbazole derivatives was investigated. With the introduction of both electron acceptor and donor moieties to 3,3′-bicarbazole structure material electron and hole drift mobilities reach approximately 1·10-5 cm2/V·s. Molecule ionization (If) levels and electron affinity (EAf) levels in thin films were determined using photoelectric effect experiment. Depending on the nature of substituents at 6,6′- and 9,9′- positions If levels range from -5.19 to -5.13 eV and EAf levels are from -2.44 to -2.38 eV.
New solution-processable materials based on well-known green iridium(III) heteroleptic complexes (ppy)2Ir(acac) and (ppy)2Ir(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.
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 weight for the studied material class, reaching values up to 130°C.
Scalar and vectorial degenerate four-wave-mixing (DFWM) in azobenzene molecular K-RJ-4-3 [N,N-bis(5,5,5- tryphenylpentyl)-4-((4-tritylphenyl)diazenyl)aniline] and in chalcogenide a-As2S3 glassy films is experimentally investigated. A coherent self-enhancement (CSE) of holographic gratings (HG) in this geometry was experimentally confirmed, for the first time to our knowledge, thus establishing a new method of HG recording, the DFWM CSE recording. Scalar linear s-s, p-p and circular R-R(right) polarizations and orthogonal linear s-p and circular L(left)-R polarizations were used for HG recording with 2 μm period at 532 nm. In the case of K-RJ-4-3 film L-R polarizations were the most efficient enabling the maximum DFWM efficiency ρmax=14.5% whereas in the case of a-As2S3 film s-s polarizations were the best with ρmax=6.0%. DFWM CSE recording has exhibited a different polarization dependence compared to normal DWFM recording. CSE factor ρ/ρ0 (ρ0 being the initial ρ) was the highest for K-RJ-4-3 film (6.8) with s-s polarizations compared to 3 for a-As2S3 film with p-p polarizations. Two-wave HG recording was also studied for comparison.
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 d33 coefficient by up to 17 times was achieved for the
same chromophore core containing compounds.
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.
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