Perylene Orange Research Articles

White Lasing and White Fluorescence from the Simplified Two‐Dyes Organic System

AbstractThe invention of lasers, which took place a few decades ago, marks a milestone in the past, present, and future technologies in optoelectronics. In particular, the colorful and white tones produced by lasers are appealing from a utilization standpoint and align well with human eye perception. In this paper, an idea for a white laser based on the attractive perylene family of luminescent dyes is introduced. This concept provides multicolor emission and brilliant photostability upon external optical pumping. The main advantage of the approach is the construction of a fully organic and two‐component white laser. The versatility of the system is demonstrated by assembling multicolor, tunable, and efficient fluorescent systems using a liquid crystalline matrix, which is supported by comprehensive experimental studies. Additionally, by utilizing laser spectroscopy techniques, it is able to narrow the emission bandwidth and enhance the light in a typical synthetic polymeric matrix. This leads to the realization of white lasing emission with just two luminescent dyes: perylene blue and perylene orange.

Strong quenching of dye fluorescence in monomeric perylene orange/TMDC hybrid structures.

Hybrid structures with an interface between two different materials with properly aligned energy levels facilitate photo-induced charge separation to be exploited in optoelectronic applications. Particularly, the combination of 2D transition metal dichalcogenides (TMDCs) and dye molecules offers strong light-matter interaction, tailorable band level alignments, and high fluorescence quantum yields. In this work, we aim at the charge or energy transfer-related quenching of the fluorescence of the dye perylene orange (PO) when isolated molecules are brought onto monolayer TMDCs via thermal vapor deposition. Here, micro-photoluminescence spectroscopy revealed a strong intensity drop of the PO fluorescence. For the TMDC emission, in contrast, we observed a relative growth of the trion versus exciton contribution. In addition, fluorescence imaging lifetime microscopy quantified the intensity quenching to a factor of about 103 and demonstrated a drastic lifetime reduction from 3 ns to values much shorter than the 100 ps width of the instrument response function. From the ratio of the intensity quenching that is attributed to hole or energy transfer from dye to semiconductor, we deduce a time constant of several picoseconds at most, pointing to an efficient charge separation suitable for optoelectronic devices.

Energy transfer in supramolecular calix[4]arene—Perylene bisimide dye light harvesting building blocks: Resolving loss processes with simultaneous target analysis

By the application of simultaneous target analysis of multiple femtosecond transient absorption data sets we have identified two loss channels within multi-chromophoric light harvesting arrays. Perylene bisimide-calix[4]arene arrays composed of up to three different types of perylene bisimide (PBI) chromophores, orange (o), red (r), and green (g) PBIs (named after their colors as solids), have previously been studied by transient absorption spectroscopy (Hippius et al., J. Phys. Chem C 112:2476, 2008) and here we present a simultaneous target analysis of those data matrices. A covalent system containing the red chromophore (r) and calix[4]arene (c), the rc system, shows extensive spectral evolution that can be described with four excited states (r1*→r2*→r3*→r4*→ground state). In the Perylene Orange calix[4]arene system (oc), a radical pair (ocRP) can be formed by photoinduced electron transfer (Hippius et al., J. Phys. Chem C 111:13988, 2007). In a simultaneous target analysis of the multichromophoric systems ocr, rcocr and ocrco the properties of rc and oc are integrated, and excitation energy transfer (EET) from o* to r* occurs. In addition, we demonstrate that the final Species Associated Difference Spectrum (SADS) also contains o bleach features that indicate an excitonic interaction, for ocr, rcocr and ocrco. In a simultaneous target analysis of rcg and gcrcg the properties of rc are integrated, and next to EET to g* we can resolve the formation of a new rcgRP that is formed from r1* or r2*, and represents a loss of 7 and 12%, respectively. In a simultaneous target analysis of ocrcg the properties of ocr and rcg are integrated, arriving at a consistent picture with an energy transfer quantum yield of formation of the excited state of the green PBI (g*) of 80%.

Influence of Blending Ratio and Polymer Matrix on the Lasing Properties of Perylenediimide Dyes

Perylenediimide (PDI) dyes dispersed in polymer films have demonstrated great success as active materials in thin-film organic lasers (TFOLs). The type of matrix used to host the dye and the dye doping rate are both crucial parameters to optimize laser performance. This work reports the study of two soluble PDIs, the comercial derivative perylene orange (PDI-O) emitting at around 580 nm, and a new dye (b-PDI-A) with substituents at the 1,7 bay positions of the PDI core emitting at around 620 nm, dispersed at different doping levels (up to 8 and 50 wt %, for PDI-O and b-PDI-A, respectively) in two widely used polymers for optoelectronics, polystyrene (PS) and poly(methyl methacrylate) (PMMA). The main goal is to determine which of these two polymers, and at which dye concentration, provides the best results for their use in TFOLs. The assessment of the active materials has been carried out through the analysis of their absorption, photoluminescence, and amplified spontaneous emission (ASE) properties. Thei...

An Efficient and Color‐Tunable Solution‐Processed Organic Thin‐Film Laser with a Polymeric Top‐Layer Resonator

Thin film organic lasers represent attractive light sources for numerous applications. Currently, efforts are devoted to the development of low‐cost high‐performance and color‐tunable devices, whereby both the resonator and the active layer should consist of solution‐processable organic materials. Herein, solution‐processed distributed‐feedback lasers are reported with polymeric resonators on top of active films of perylene orange or carbon‐bridged oligo(p‐phenylenevinylene) dispersed in polystyrene, which combine these properties. These lasers emit in the 520–595 nm range and show low thresholds (≈1 kW cm−2) and long operational lifetimes (7 × 105 pump pulses), which are comparable to other state‐of‐the‐art lasers that contain the same active materials but resonators made on inorganic substrates. Due to this top‐layer resonator configuration, the laser slope efficiencies of the present devices are remarkably superior. A centimeter‐size device emitting at different wavelengths within a broad spectral range, based on a perylene‐based film of uniform thickness that contributes to preserve a low threshold, is demonstrated.

Two-dimensional distributed feedback lasers with thermally-nanoimprinted perylenediimide-containing films

Two-dimensional (2D) distributed feedback (DFB) lasers with gratings imprinted by thermal nanoimprint lithography on the active film are reported. They show thresholds for lasing of ∼10 kW/cm2, similar to the most efficient imprinted DFB lasers reported; and long operational lifetimes (under ambient conditions) of ∼12 × 104 pump pulses. The key for their successful operation has been the selection of a highly efficient and stable dye, perylene orange (PDI-O), and a proper matrix to host it, the fluoro-modified thermoplastic resist mr-I7030R, which has enabled 2D imprinting while preserving the dye optical properties. The use of the UV-curable resist SU8 as an alternative matrix for PDI-O to be imprinted by combined nanoimprint and photolithography was also investigated, and was concluded to be unsuccessful due to severe photoluminescence quenching. By replacing PDI-O with Rhodamine 6G, lasers with reasonable thresholds, but with significantly inferior operational lifetimes in comparison to PDI-O/mr-I7030R devices, were obtained.

Improved performance of perylenediimide-based lasers

The aim of this work was to improve the laser performance, in terms of threshold and operational lifetime, of lasers based on polymer films doped with perylenediimide (PDI) derivatives as active media. For such purpose, we first investigated the amplified spontaneous emission (ASE) properties of perylene orange (PDI-O), when doped into polystyrene (PS) films. Lower ASE thresholds and larger photostabilities than those of similar films containing another PDI derivative (PDI-C6), recently reported in the literature, have been measured. Results have been interpreted in terms of the photoluminescence efficiency of the films, which depends on the type of molecular arrangement, inferred with the help of nuclear magnetic resonance experiments. We also show that PS films have a better ASE performance, i.e. lower thresholds and larger photostabilities, than those based on poly(methyl methacrylate), which was recently highlighted as one of the best matrixes for PDI-O. Finally, a one-dimensional second-order distributed feedback laser using PS doped with PDI-O was fabricated and characterized. This device has shown a threshold significantly lower (by around one order of magnitude) than that of a similar laser based on PDI-C6-doped PS.

New perylene-doped polymeric thin films for efficient and long-lasting lasers

We establish an efficient strategy to optimize the performance of dye-doped host materials consisting of analyzing in a systematic way the dependence of their Amplified Spontaneous Emission (ASE) efficiency and photostability on the composition and structure of the matrices, selected to specifically avoid the thermal and/or chemical (photooxidation) processes, main mechanisms of dye photodegradation. For this study, a number of experimental polyimides have been chosen as a host matrix and their behavior has been compared with that of poly(methyl methacrylate) (PMMA). We correlate the optical properties with the oxygen permeation and thermal properties of the different polymeric hosts doped with perylene dyes to deepen the understanding of the photodegradation mechanism predominant in these dyes and to minimize its influence. We demonstrate high efficiency and photostable ASE from waveguides based on polymeric materials doped with Perylene Orange (PO), Perylene Red (PR), and mixtures of both. This enhancement in the optical properties allows reaching high gain and long-lasting distributed feedback (DFB) laser emission based on PO doped polymer matrices, even when operating in an unoptimised resonator.

Efficient fluorescence from perylene orange encapsulated in AlPO4 mesoporous glass

AlPO4 mesoporous glass doped with perylene orange (PO) is prepared using two steps. The effects of dipping time and PO concentration on the fluorescent properties and molecular formation are investigated through absorption spectra, excitation spectra, and emission spectra. A slight increase in the intensity of excitation bands formed at 499 and 468 nm is ascribed to PO J-dimers aggregates as the dipping time increased from 2 to 24 h at high PO concentration (4×10 -3 mol/L). This is also the reason behind the concentration increase from 4×10 -6 to 4×10 -3 mol/L for the 16 h dipping. The excitation spectra, and the emission spectra of samples doped with PO show a slight red shift as the dipping time and the PO concentration increase. AlPO4 mesoporous glass is suitable to host the PO at high concentration.

Calculated spectral properties of perylene orange, perylene red, and their complex with sodium azide

AbstractUsing the method of density functional theory in approximating B3LYP with the basis set 6‐31G(d) the computations of structures of the following dyes 2,2′‐N‐N′‐di(1,3‐diisopropylbenzene)‐diimide 3,4,9,10‐perylenetethracarbon acid (Perylene Orange‐PO) and 1,6,7,12‐tethraphenyl ether 2,2′‐N,N′‐di(1,3‐diisopropylbenzene)‐diimide 3,4,9,10‐perylenetethracarbon acid (Perylene Red‐PR) were performed. It was revealed that PO and PR have nonplanar structures. On the basis of the predicted geometrical structures and molecular orbitals of S0 ground state their theoretical UV‐vis spectra, which are in good agreement with experiment, were obtained by applying time‐dependent DFT (TDDFT) method. In addition, the calculations of complex [PR … NaN3] and its UV‐vis spectrum, which was compared with the observed electron spectrum of PR ethanol solution in the presence of NaN3 under the laser irradiation at 532 nm, were carried out. By using DFT method at B3LYP level the calculations of the assumed complex were made where the reaction coordinate was the distance between Na+ and carbonyl group O atom. It was suggested that [PR … NaN3] complex formation involves transition of PR to the triplet state which brings about formation of PR anion. New peak at 793 nm in UV‐vis spectrum of this solution under the laser irradiation at 532 nm is supposed to be a PR anion band. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007

Energy transfer and photodegradation of a Perylene Orange:LDS821 system in poly(methyl methacrylate)

The luminescence of Perylene Orange and LDS821 in poly(methyl methacrylate) (PMMA) following a 532 nm irradiation yielded information on photodegradation and energy transfer. The irradiation of the Perylene Orange/LDS821/PMMA films resulted in (i) a maximum in the Perylene Orange fluorescence photodegradation profile and (ii) an enhancement of the LDS821 fluorescence relative to the LDS821/PMMA films. These results are attributed to an energy transfer from the Perylene Orange to the LDS821 with an energy transfer rate constant of 5.1+/- 0.75 (2sigma) x 10(11) M(-1) s(-1) and a Förster critical radius of 65.7 A. Fluorescence half-quenching and time-resolved fluorescence measurements attributed energy transfer to the Förster energy transfer with minor contributions of radiative energy transfer.

Exciton Migration by Ultrafast Förster Transfer in Highly Doped Matrixes

The energy transfer between dye molecules and the mobility of the corresponding excitons are investigated in polymethyl methacrylate films highly doped with perylene bisimide dyes. The dynamics is measured by group delay corrected, femtosecond broad-band spectroscopy revealing the transfer route via absorption changes that are specific for the participating species. In films doped with 0.14 M perylene orange an ultrafast homotransfer between the dye molecules is found by analyzing the loss of the excitation-induced anisotropy. The process exhibits a stretched exponential time dependence which is characteristic for Förster energy transfer between immobilized molecules. The transfer time is 1.5 ps for an average transfer distance of 2.3 nm and results in a high mobility of the optically generated excitons. In addition, we find that the excitons move to perylene orange dimers, which have formed in low concentration during the sample preparation. The observed energy transfer time is slightly shorter than expected for a direct Förster transfer and indicates that exciton migration by multistep transfer between the monomers speeds up the transport to the dimers. In samples doped with perylene orange and perylene red heterotransfer to perylene red takes place with transfer times down to 600 fs. The mechanism is Förster transfer as demonstrated by the agreement with calculations assuming electric dipole interaction between immobilized and statistically distributed donor and acceptor units. The model predicts the correct time dependence and concentration scaling for highly doped as well as diluted samples. The results show that ultrafast exciton migration between dye molecules in highly doped matrixes is an attractive and efficient mechanism to transport and collect energy in molecular systems and organic electronic devices. Further optimization should lead to a loss-free transport over distances typical for the thickness of active layers in these systems.

Existence of Conformers Revealed by Spectral Analysis of Single Molecules of Perylene Orange in Thin Sol−Gel Films

This paper reports on the spectral dynamics of perylene orange in thin sol-gel films. The studies are performed at the single molecule level to retrieve local information on such samples. The fluorescence spectrum of a molecule depends on the properties of the molecule itself and especially on its conformation in the ground state and in the state reached after excitation. Studies have been performed at room temperature and at a lower temperature, around 173 K. A large number of the recorded spectra reflect dual fluorescence. It is the rule at room temperature. However, at low temperature, single molecules either are relatively free to change conformation or are caught in a rigid environment. In the latter case, they present the spectrum of a rigid dye and we have identified the signature of several conformers of perylene orange in the ground state.

The photophysical properties of chromophores at high (100 mM and above) concentrations in polymers and as neat solids

The absorption, fluorescence, and photostability of five conjugated chromophores: perylene, 2,5,8,11-tetra-t-butyl perylene (TTBP), perylene orange (PO), perylene red (PR), and a zwitterionic Meisenheimer complex (MHC), are studied as a function of concentration in poly(methyl methacrylate) (PMMA). At 1 mM concentrations, all five molecules exhibit properties consistent with unaggregated chromophores. At higher concentrations, perylene and PO both exhibit excimer formation, while TTBP, PR, and the MHC retain their monomeric fluorescent lineshapes. In these three molecules, however, the fluorescence decay times decrease by 10% (TTBP) to 50% (MHC) at concentrations of 100 mM in PMMA. The fluorescence properties of these highly concentrated samples are sensitive to the sample preparation conditions. In the neat solid where the effective concentration is on the order of 1 M, all three molecules exhibit very fast fluorescence decays, on the order of 150 ps or less, despite the fact that they retain their basic monomeric fluorescence lineshape. In addition to the enhanced nonradiative decay at high concentrations, these three molecules also undergo a concentration-dependent photobleaching. The combined effects of intermolecular nonradiative decay channels and photobleaching appear to be a general obstacle to achieving highly concentrated dye-doped solids.

Single Molecule Study of Perylene Orange Photobleaching in Thin Sol−Gel Films

The paper reports on photobleaching mechanisms of perylene orange embedded in thin sol-gel films, derived from single molecule studies. The experimental configuration uses wide-field illumination and one photon excitation of the molecules. Measurements have been performed both at ambient conditions and under vacuum in order to get information on the influence of oxygen on photobleaching in such porous samples. We have also recorded the evolution of photobleaching with respect to the excitation intensity. The results demonstrate that photobleaching from excited states higher than the first singlet and triplet states has a nonnegligible contribution as soon as the excitation energy exceeds a few hundred W/cm2 and that this process is favored in the presence of air. The study also demonstrates that perylene orange in sol-gel films is not a very efficient emitter but that photobleaching can be slow, which explains the interest for perylene orange as a good candidate to produce long lifetime solid-state lasers when embedded in monoliths of sol-gel.

Energy transfer mechanism between laser dyes doped in ORMOSILs

Laser dyes perylene orange (p-orange) or perylene red (p-red) or pyrromethene 567 (p567) were co-doped with coumarin 440 (C440) or coumarin 500 (C500) into MTES- and VTES-derived organically modified silicates (ORMOSILs) by sol–gel process. Energy transfer from both C440 and C500, energy donors, to p-red, p-orange and p567, acceptor, respectively, has been observed and studied by steady-state emission measurement. The effect of donor concentration on energy transfer and its mechanism were studied. The potential application as an energy transfer dye laser (ETDL) was also discussed. At least 1-fold increase in the slope efficiency of p-red and 3-fold increase in the photostability of p567 was observed in such ETDLs.

Simple and Easy Solid-State Dye Laser

Perylene orange is a kind of pigment that is not easily photobleached. We doped perylene orange into a 2-mm-thick acrylic plastic monolith as a laser-active medium. Commercially available metalized film tape was affixed to both sides of the acrylic monolith and served as mirrors for a Fabry–Perot resonator. The pump source was a Q-switched frequency-doubled Nd:YAG laser. We obtained a yellow laser beam whose center wavelength was 578.6 nm.

Laser properties and photostabilities of laser dyes doped in ORMOSILs

Laser dyes such as rhodamine B, rhodamine 6G, pyrromethene 567, perylene orange and perylene red were doped into GPTMS-, MTES- and VTES-derived organically modified silicates (ORMOSILs) by sol–gel process. A longitudinal pumped solid-state dye laser was established with a Q-switched Nd:YAG laser source. The lifetimes of these dyes in various ORMOSILs were investigated by using such an experimental setup at a pump repetition rate of 2 Hz and pump intensity of 0.1 or 1.4 J/cm 2 . The lifetime of 60 000 pulses, 50 GJ/mol in normalized photostability, was obtained for the pyrromethene 567 doped in MTES-derived ORMOSIL with the net sample thickness of 4 mm when its output energy declined to 50% of its initial value. The slope efficiencies of pyrromethene 567 and perylene orange in various host media were also measured. � 2003 Elsevier B.V. All rights reserved.

Photostability of perylene orange, perylene red and pyrromethene 567 laser dyes in various precursors derived gel glasses

Three laser dyes (perylene orange, perylene red and pyrromethene 567) were dispersed in TEOS-, TEOS/GPTMS-, MTES- and VTES-gel glasses, respectively. The surroundings and fluorescence photostability of the dyes in gel glasses were studied. Due to the formation of a hydrogen bond between the dye and the residual Si–OH attached on the surface of the cages and pores, spectral red shifts of perylene orange at 10 K in TEOS- and TEOS/GPTMS-gel glasses with respect to that in MTES- and VTES-gel glasses were observed. Perylene dyes are more likely to trap in the cages of MTES- and VTES-gel glasses and show high-fluorescence photostability, while ionic and polar pyrromethene 567 tend to appear in the polar pores of gel glasses, which leave pyrromethene 567 vulnerable to photochemical reactions with singlet oxygen and low-fluorescence photostability.

Efficient energy transfer in organic thin films—implications for organic lasers

We show that efficient nonradiative (Förster) energy transfer between solid films of two highly luminescent perylene dyes blended in a solid film can be used to control the amplified spontaneous emission (ASE) emitted from the films under pulsed optical excitation. Perylene orange, which acts as the donor, and perylene red, which is the acceptor, are doped into a host matrix of poly(methylmethacrylate) (PMMA). We report the ASE behavior as a function of acceptor concentration, and observe a sudden change in the spectral position of the ASE at an acceptor:donor concentration of 1:9 by weight. Below this concentration, emission is at 590 nm, which is characteristic of ASE from undoped perylene orange:PMMA blends, whereas films with higher acceptor concentrations produced ASE spectra centered at 620 nm, which is characteristic of perylene red:PMMA blends. In order to understand this behavior, the rate constant for energy transfer between the dyes was measured and found to be 5.0±0.2×1011 s−1 (mol/dm3)−1. We used this to deduce an upper limit for the stimulated emission rate of 4.9±0.2×108 s−1.