Substituent effects on the electronic characteristics of pentacene derivatives for organic electronic devices: dioxolane-substituted pentacene derivatives with triisopropylsilylethynyl functional groups

The intramolecular electronic structures and intermolecular electronic interactions of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene), 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]-pentacene (TP-5 pentacene), and 2,2,10,10-tetraethyl-6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5 pentacene) have been investigated by the combination of gas-phase and solid-phase photoelectron spectroscopy measurements. Further insight has been provided by electrochemical measurements in solution, and the principles that emerge are supported by electronic structure calculations. The measurements show that the energies of electron transfer such as the reorganization energies, ionization energies, charge-injection barriers, polarization energies, and HOMO-LUMO energy gaps are strongly dependent on the particular functionalization of the pentacene core. The ionization energy trends as a function of the substitution observed for molecules in the gas phase are not reproduced in measurements of the molecules in the condensed phase due to polarization effects in the solid. The electronic behavior of these materials is impacted less by the direct substituent electronic effects on the individual molecules than by the indirect consequences of substituent effects on the intermolecular interactions. The ionization energies as a function of film thickness give information on the relative electrical conductivity of the films, and all three molecules show different material behavior. The stronger intermolecular interactions in TP-5 pentacene films lead to better charge transfer properties versus those in TIPS pentacene films, and EtTP-5 pentacene films have very weak intermolecular interactions and the poorest charge transfer properties of these molecules.     

Dynamics of energy transfer of a dioxolane-substituted pentacene dispersed in 4,4-bis[N-1-naphthyl-N-phenylamino]biphenyl

We examine the steady-state and time-resolved photoluminescence of guest-host films featuring a dioxolane-substituted pentacene derivative (2,2,10,10-tetraethyl-6,14-bis(triisopropylsilylethynyl)-1,3,9,11-tetraoxadicyclopenta[b,m]pentacene, EtTP-5) dispersed in the hole transporting material (4,4-bis[N-1-naphthyl-N-phenylamino]biphenyl, alpha-NPD). The films show bright red emission (lambda(max) = 640 nm) as a result of efficient F?rster energy transfer from alpha-NPD host molecules to EtTP-5 guest molecules. High absolute photoluminescence (PL) quantum yield (phi(PL) = 76% +/- 4%) and fluorescence lifetime (tau = 18.6 +/- 0.8 ns) were measured at low concentration (0.28 mol % EtTP-5), with moderate PL quenching observed upon increasing the EtTP-5 concentration. The concentrated films (> or = 1.50 mol % EtTP-5) show less evidence of aggregation than previously seen when EtTP-5 was dispersed in tris(quinolin-8-olato)aluminum(III), making alpha-NPD a superior host for the red-emitting EtTP-5.     

Excitation energy transfer in tris(8-hydroxyquinolinato)aluminum doped with a pentacene derivative

We investigate the excitation energy transfer in a guest-host molecular system consisting of a pentacene derivative, namely 6,13-bis(2,6-dimethylphenyl)pentacene (DMPP), doped into tris(8-hydroxyquinolinato)aluminum (Alq(3)) using steady-state and time-resolved photoluminescence (PL) spectroscopy. The concentration dependent energy transfer rate and efficiency are calculated and analyzed in terms of the F?rster resonance energy transfer model. A relatively long excitation transfer time ( approximately 0.6-3.4 ns depending on the DMPP concentration) and a large transfer radius (31-36 A) are obtained. The F?rster radius calculated directly from the Alq(3) PL-DMPP absorption spectral overlap (26 A) is smaller than the transfer radii obtained from the PL studies, which suggests that excitation energy migration within Alq(3) plays an important role in the energy transfer process, effectively elongating the transfer radius and increasing the transfer rate and efficiency.     

Effects of systematic methyl substitution of metal (III) tris(n-methyl-8-quinolinolato) chelates on material properties for optimum electroluminescence device performance.

We relate the chemical structure of a series of methyl (Me) substituted group III metal tris(8-quinolinolato) chelates (nMeq(3)M: n = 0, 3, 4, 5; M = Al(3+), Ga(3+)) to their photoluminescence (PL), electroluminescence, and thermal properties. Methylation of the 8-quinolinol ligand at the 3 or 4 position (pyridyl ring) results in a factor of 1.4 and 3.0 enhancement of PL quantum efficiency (phi(PL)), respectively, whereas methylation at the 5 position (phenoxide ring) results in a factor of approximately 3.0 decrease in phi(PL) relative to the unsubstituted analogue. Electroluminescent quantum efficiencies of undoped organic light-emitting devices using the aluminum tris(8-quinolinolato) chelates are 1, 0.45, 1.4, and 0.80% for unsubstituted 5-, 4-, and 3-methyl-8-quinolinol ligands, respectively. Devices made with the latter two ligands have a higher operating voltage to generate the same current density. Similar trends were observed for methylation of gallium tris(8-quinolinolato) chelates. We relate these results to the thermal properties of the compounds measured by simultaneous differential scanning calorimetry and thermal gravimetric analysis. The C-4 methylated derivatives exhibit approximately 60 degrees C lower crystalline melting points than all other derivatives, indicating the weakest cohesive forces between molecules. Unlike Alq(3), both the C-4 and C-5 methylated derivatives show no recrystallization of the glassy state below 500 degrees C and exhibit approximately 20-25 degrees C higher glass transition temperatures. We infer that methylation of the 8-quinolinol ligand reduces intermolecular interactions and consequently impedes charge transport through the film.     

Supramolecular structures and assembly and luminescent properties of quinacridone derivatives

The synthesis and single-crystal X-ray structures of two quinacridone derivatives, N,N'-di(n-butyl)quinacridone (1) and N,N'-di(n-butyl)-1,3,8,10-tetramethylquinacridone (2), are reported, and the 1H NMR, absorption, photoluminescent (PL), and electroluminescent (EL) characteristics are presented. Both these crystal structures are characterized by intermolecular pi...pi and hydrogen bonding interactions. The intermolecular pi...pi interactions lead to the formation of molecular columns in the solids of 1 and 2, and the interplanar contact distances between two adjacent molecules are 3.48 and 3.55 angstroms, respectively. Crystals of 1 display shorter intermolecular pi...pi contacts and higher density than 2. These results suggest that tighter intermolecular interactions exist in 1. The 1H NMR, absorption, and PL spectra of 1 and 2 in solutions exhibit concentration-dependent properties. The PL quantum yields of 1 in solutions decrease more quickly with the increase of concentration compared to that of 2 in solutions. For solid thin films of Alq3:1 (Alq3 = tris(8-hydroxyquinolinato)aluminum), emission intensities dramatically decrease and obvious red shifts are observed when the dopant concentration is above 4.2%, while for films of Alq3:2, a similar phenomenon occurs when the concentration is above 6.7%. EL devices with Alq3:1 as emitting layer only show high efficiencies (20.3-14.5 cd/A) within the narrow dopant concentration range of 0.5-1.0%. In contrast, high efficiencies (21.5-12.0 cd/A) are achieved for a wider dopant concentration range of 0.5-5.0% when Alq3:2 films are employed as emitting layer. The different PL and EL concentration-dependent properties of the solid thin films Alq3:1 and Alq3:2 are attributed to their different molecular packing characteristics in the solid state.     

八-羟基喹啉铝薄膜光致发光的厚度依赖性质

In situ thickness dependent photoluminescence (PL) measurements of tris(8-hydroxyquinoline) aluminum(Alq3) film were performed. At the beginning of Alq3 deposition on the glass substrate, the Alq3 emission showed a sharp red-shift. Further deposition of Alq3 resulted slight red-shift, and finally tended to saturated value. The total red-shift of about 12 nm was observed for the Alq3 film thickness range from 2 to 500 nm.This red-shift was attributed to the change from the 2D to 3D exciton state with increasing Alq3 film thickness. Meanwhile, the PL intensity of Alq3 emission increased continuously, and showed a rate change at the initial deposition of Alq3 due to non-rediative decay of excitons arised from the interaction between excitons and the substrate, and finally tended to saturation with the Alq3 thickness.     

Structurally integrated organic light emitting device-based sensors for gas phase and dissolved oxygen

A compact photoluminescence (PL)-based O2 sensor utilizing an organic light emitting device (OLED) as the light source is described. The sensor device is structurally integrated. That is, the sensing element and the light source, both typically thin films that are fabricated on separate glass substrates, are attached back-to-back. The sensing elements are based on the oxygen-sensitive dyes Pt- or Pd-octaethylporphyrin (PtOEP or PdOEP, respectively), which are embedded in a polystyrene (PS) matrix, or dissolved in solution. Their performance is compared to that of a sensing element based on tris(4,7-diphenyl-l,10-phenanthroline) Ru II (Ru(dpp)) embedded in a sol-gel film. A green OLED light source, based on tris(8-hydroxy quinoline Al (Alq3), was used to excite the porphyrin dyes; a blue OLED, based on 4,4'-bis(2,2'-diphenylviny1)-1,1'-biphenyl, was used to excite the Ru(dpp)-based sensing element. The O2 level was monitored in the gas phase and in water, ethanol, and toluene solutions by measuring changes in the PL lifetime tau of the O2-sensitive dyes. The sensor performance was evaluated in terms of the detection sensitivity, dynamic range, gas flow rate, and temperature effect, including the temperature dependence of tau in pure Ar and O2 atmospheres. The dependence of the sensitivity on the preparation procedure of the sensing film and on the PS and dye concentrations in the sensing element, whether a solid matrix or solution, were also evaluated. Typical values of the detection sensitivity in the gas phase, S(g) identical with tau(0% O2)/tau(100% O2), at 23 degrees C, were approximately 35 to approximately 50 for the [Alq3 OLED[/[PtOEP dye] pair; S(g) exceeded 200 for the Alq3/PdOEP sensor. For dissolved oxygen (DO) in water and ethanol, S(DO) (defined as the ratio of tau in de-oxygenated and oxygen-saturated solutions) was approximately 9.5 and approximately 11, respectively, using the PtOEP-based film sensor. The oxygen level in toluene was measured with PtOEP dissolved directly in the solution. That sensor exhibited a high sensitivity, but a limited dynamic range. Effects of aggregation of dye molecules, sensing film porosity, and the use of the OLED-based sensor arrays for O2 and multianalyte detection are also discussed.     

Competition between singlet fission and charge separation in solution-processed blend films of 6,13-bis(triisopropylsilylethynyl)pentacene with sterically-encumbered perylene-3,4:9,10-bis(dicarboximide)s

The photophysics and morphology of thin films of N,N-bis(2,6-diisopropylphenyl)perylene-3,4:9,10-bis(dicarboximide) (1) and the 1,7-diphenyl (2) and 1,7-bis(3,5-di-tert-butylphenyl) (3) derivatives blended with 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) were studied for their potential use as photoactive layers in organic photovoltaic (OPV) devices. Increasing the steric bulk of the 1,7-substituents of the perylene-3,4:9,10-bis(dicarboximide) (PDI) impedes aggregation in the solid state. Film characterization data using both atomic force microscopy and X-ray diffraction showed that decreasing the PDI aggregation by increasing the steric bulk in the order 1 < 2 < 3 correlates with a decrease in the density/size of crystalline TIPS-Pn domains. Transient absorption spectroscopy was performed on ~100 nm solution-processed TIPS-Pn:PDI blend films to characterize the charge separation dynamics. These results showed that selective excitation of the TIPS-Pn results in competition between ultrafast singlet fission ((1*)TIPS-Pn + TIPS-Pn → 2 (3*)TIPS-Pn) and charge transfer from (1*)TIPS-Pn to PDIs 1-3. As the blend films become more homogeneous across the series TIPS-Pn:PDI 1 → 2 → 3, charge separation becomes competitive with singlet fission. Ultrafast charge separation forms the geminate radical ion pair state (1)(TIPS-Pn(+?)-PDI(-?)) that undergoes radical pair intersystem crossing to form (3)(TIPS-Pn(+?)-PDI(-?)), which then undergoes charge recombination to yield either (3*)PDI or (3*)TIPS-Pn. Energy transfer from (3*)PDI to TIPS-Pn also yields (3*)TIPS-Pn. These results show that multiple pathways produce the (3*)TIPS-Pn state, so that OPV design strategies based on this system must utilize this triplet state for charge separation.     

Electrical properties of 1,4-bis(4-(phenylethynyl)phenylethynyl)benzene and its application for organic light emitting diodes

We found that a phenylene ethynylene derivative, 1,4-bis(4-(phenylethynyl)phenylethynyl)benzene (BPPB), provides very high photoluminescence efficiency both in solution (Phi(PL) = 95 +/- 3%) and thin films (Phi(PL) = 71 +/- 3%); further, we observed blue electroluminescence (EL) of lambda(EL(max)) approximately 470 and 510 nm with an external EL efficiency of eta(EL) approximately 0.53% and maximum luminance of approximately 70000 cd m(-2) at current density of approximately 2 A cm(-2) with BPPB as an emitter; also we identified that BPPB functions as a hole transport layer in organic light emitting diodes.     

Double diels-alder strategies to soluble 2,9- and 2,9,6,13-tetraethynylpentacenes, photolytic [4 + 4] cycloadditions, and pentacene crystal packing

Four new classes of organic solvent soluble ethynylpentacene derivatives (2,9-, 2,10-, 2,6,9,13-, 2,6,10,13-) have been prepared by complementary, versatile, double Diels-Alder strategies. Functional groups on the A, C, and E rings can be manipulated to increase the solubility, modulate the electronics, and alter the solid-state packing. Cycloaddition reactions with diene 2 and 1,4,5,8-anthradiquinone (3) or ortho-quinodimethane 19 with 1-butyl-3-methylimidazolim iodide (18) as the iodide source (a significant improvement over NaI) and benzoquinone (20) followed by in situ aromatization afforded the quinones 4, 5, 21, and 22, respectively. For the 2,9- and 2,10- families, a one-pot desilylation/triflation was developed. Palladium(0) coupling and reductive aromatization afforded 2,9-di(triisopropylsilylethynyl)pentacene (10) and 2,10-di(triisopropylsilylethynyl)pentacene (11), respectively. Photodimerization of these pentacenes afforded the air-stable [4 + 4] cycloaddition pentacene precursors (tetrakisnaphthotricyclo[4.2.2.22,5]dodecanes, 12-15). Thermal cycloreversion of the dimers ( approximately 13 J/g, approximately 4 kcal/mol) produces the parent pentacenes (10 or 11). The tetrasubstituted family utilized a parallel route with extra versatility as the timing of the Grignard and palladium(0) coupling step may be varied depending upon the functional group combinations desired. The subsequent reactions provided the tetraethynylpentacenes 28-30, 33-35 (para-isomers), and 38 (meta-isomer). X-ray crystallography analysis of 28, 29, and 33 revealed various pi-pi stacked packing motifs that differ from the unfavorable herringbone pattern of pentacene.     

Temperature-dependent photoluminescence of organic light-emitting materials: Types and characteristics of excitons involved in the emitting process

Based on experimental measurement and theoretical analysis, the temperature dependence of the photoluminescence (PL) of amorphous thin films of tris-(8-hydroxyquinoline) aluminum (Alq) and 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) has been studied. It is proposed that three types of excitons with different charge separations are involved in the steady state PL process. It is found that all three types of excitons participate in the PL process of Alq, whereas, only the first two types of radiative excitons dominate the PL process of DCJTB in the temperature range covered by the present work. The blue shift of the DCJTB PL spectra with increasing temperature has been observed and analyzed. It is suggested that the temperature-dependence of PL could be used to evaluate the radiative and conductive characteristics of organic emitters and to distinguish whether a given material would tend to be of molecular or semiconductor properties.     

Thermally induced solid-state phase transition of bis(triisopropylsilylethynyl) pentacene crystals

Bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) is a functionalized pentacene derivative designed to enhance both the solution solubility and solid-state packing of pentacene. In this paper, we report our observations of a solid-state phase transition in TIPS pentacene crystals upon heating or cooling. Evidence from differential scanning calorimetry (DSC), hot-stage optical microscopy, as well as high-temperature X-ray and electron diffraction are presented. A reasonable match with experimental data is obtained with molecular modeling. Our results reveal that the transition is associated with a conformational reorganization of the TIPS side groups, accompanied by a slight decrease in the acene-to-acene spacing and a shift of the overlap between the neighboring pentacene units. The observed cracking should be avoided or minimized in TIPS pentacene-based thin film transistors to maintain their relatively high charge carrier mobility.     

Simulating charge transport in tris(8-hydroxyquinoline) aluminium (Alq(3))

We present a model of charge transport in organic solids which explicitly considers the packing and electronic structure of individual molecules. We simulate the time-of-flight mobility measurement in crystalline and disordered films of tris(8-hydroxyquinoline) aluminium (Alq(3)). The morphology of disordered Alq(3) is modelled on a molecular scale, and density functional theory is used to determine the electronic couplings between molecules. Without any fitting parameters we predict electron mobilities in the crystalline and disordered phases of approximately 1 and approximately 10(-4) cm(2) V(-1) s(-1), respectively. In good agreement with experiment we find that electron mobilities are two orders of magnitude greater than those of holes. We explain this difference in terms of the spatial extent of the frontier orbitals. Our results suggest that charge transport in disordered Alq(3) is dominated by a few highly conducting pathways.     

CP/MAS 13C NMR characterization of the isomeric states and intermolecular packing in tris(8-hydroxyquinoline) aluminum(III) (Alq3)

The isomeric states and intermolecular packing of tris(8-hydroxyquinoline) aluminum(III) (Alq(3)) in the alpha-, gamma-, and delta-crystalline forms and in the amorphous state, which are important for understanding the light-emitting and electron-transport properties, have been analyzed by CP/MAS (13)C NMR. This simple NMR experiment shows that the isomeric state of alpha- and amorphous Alq(3) is meridional, whereas that of gamma- and delta-Alq(3) is facial. In the amorphous Alq(3), the inclusion of facial isomers has been under debate. Our experiments show that meridional isomers are dominant in the amorphous Alq(3), although the existence of facial isomers cannot be completely denied. The local structure of amorphous Alq(3) is similar to that of alpha-Alq(3) and is significantly different from those of gamma- and delta-Alq(3). Among these Alq(3) samples, the effect of intermolecular interaction is not found only for gamma-Alq(3). This finding can explain the good solvent solubility of gamma-Alq(3), compared with the other crystalline forms. It is also shown that the structures are locally disordered not only for amorphous Alq(3) but also for alpha-Alq(3), although clear X-ray diffraction peaks are observed for alpha-Alq(3). In contrast, the local structures of gamma- and delta-Alq(3) are well defined. A clear relation is found between the spectral patterns of CP/MAS (13)C NMR and the fluorescence wavelengths; the samples, which consist of facial isomers, show blue-shifted fluorescence compared with those of meridionals.     

Structural and Optical Properties of ZnO Films with Different Thicknesses Grown on Sapphire by MOCVD

IntroductionZnOis one of the most promising materials for pro-ducing ultraviolet laser at room temperature because ofits wide direct band gap(Eg=3.37eV)and large ex-citonic binding energy of60meV.Recently,much at-tention has been paid to short-wavelength …     

Photoluminescence spectroscopy of pure pentacene, perfluoropentacene, and mixed thin films

We report detailed temperature dependent photoluminescence (PL) spectra of pentacene (PEN), perfluoropentacene (PFP), and PEN:PFP mixed thin films grown on SiO(2). PEN and PFP are particularly suitable for this study, since they are structurally compatible for good intermixing and form a model donor/acceptor system. The PL spectra of PEN are discussed in the context of existing literature and compared to the new findings for PFP. We analyze the optical transitions observed in the spectra of PEN and PFP using time-dependent density functional theory calculations. Importantly, for the mixed PEN:PFP film we observe an optical transition in PL at 1.4 eV providing evidence for coupling effects in the blend. We discuss a possible charge-transfer (CT) and provide a tentative scheme of the optical transitions in the blended films.     

Crystal-plane-dependent photoluminescence of pentacene 1D wire and 2D disk crystals

Down to the wire: Pentacene exhibits crystal-plane-dependent photoluminescence (PL) activity, as demonstrated in highly crystalline 1D?wires and 2D?disks, which were selectively synthesized using the vaporization-condensation-recrystallization (VCR) process. Although pentacene 1D?wires and 2D?disks have identical triclinic crystal structures, PL?activity is observed only from pentacene 1D?wires owing to the presence of "PL-active" (010) planes.     

Enhanced visible photoluminescence in ultrathin poly(3-hexylthiophene) films by incorporation of Au nanoparticles

Incorporation of non-luminescent dodecanethiolate-protected gold clusters into regioregular poly(3-hexylthiophene) films results in a 6-fold increase in the visible photoluminescence (PL) of the polymer, which arises predominantly from NP-induced structural changes in the composite films.     

Highly photoluminescent multilayer QD-glass films prepared by LbL self-assembly

A novel and facile preparation method for layer-by-layer (LbL) self-assembled films incorporating quantum dots (QDs) and having intense photoluminescence (PL) from blue to red is presented. Functional sol-gel-derived glass layers prepared by the hydrolysis of 3-aminopropyltrimethoxysilane (APS) or 3-mercaptopropyltrimethoxysilane (MPS) have been used as a linkage between QD layers. Absorption, PL spectroscopy, transmission electron microscopy, and atomic force microscopy were employed for characterization, which revealed that the QDs in the prepared films had a nearly close-packed coverage and were not aggregated. The PL efficiencies of the QDs (CdTe or ZnSe, both are thioglycolic acid-stabilized) dispersed in the films were roughly half that of the initial colloidal solutions but reached 24% before a refractive index correction. The thickness of the red-emitting film with 10 CdTe QD layers was approximately 50 nm. The concentration of QDs in the film derived from the first absorption peak was approximately 0.01 M. Because the PL starts to show a red shift, the obtained concentration is practically the ultimate one in the glass matrix. The mercapto, amino, and carboxyl groups play important roles in LbL self-assembling processes.     

Synthesis and characterization of new copolymers of thiophene and vinylene: Poly(thienylenevinylene)s and poly(terthienylenevinylene)s with thioether side chains

Poly[3,4-bis(3-methylbutylthio)thienylenevinylene], poly[3,4-bis-(S)-(2-methylbutylthio)thienylenevinylene], poly[3′,4′-bis(3-methylbutylthio)-2,2′:5′,2″-terthienylene-5,5″-vinylene], and poly{3′,4′-bis-(S)-[2-methylbutylthio]-2,2′:5′,2″-terthienylene-5,5″-vinylene} have been synthesized. The synthesis starts from the thiophene monomers and trimers, which are formylated to give the corresponding dialdehydes. The dialdehydes are reductively polymerized using a McMurry coupling. The polymers are characterized by GPC, optical spectroscopy (FT-IR, UV-vis, circular dichroism spectroscopy and photoluminescence) and by proton and carbon NMR spectroscopy. The polymers are soluble in common organic solvents, such as THF, chloroform, toluene, benzene and 1,2-dichlorobenzene. The solvatochromism and thermochromism of the polymers in solution are investigated, while the optical activity of the polymers is used to investigate the supramolecular aggregation. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4629–4639, 1999