Effect of Different Substitutions at the 1,7-Bay Positions of Perylenediimide Dyes on Their Optical and Laser Properties.

Perylenediimide (PDI) compounds are widely used as the active units of thin-film organic lasers. Lately, PDIs bearing two sterically hindering diphenylphenoxy groups at the 1,7-bay positions have received attention because they provide a way to red-shift the emission with respect to bay-unsubstituted PDIs, while maintaining a good amplified spontaneous emission (ASE) performance at high doping rates. Here, we report the synthesis of a series of six PDI derivatives with different aryloxy groups (PDI 6 to PDI 10) or ethoxy groups (PDI 11) at the 1,7 positions of the PDI core, together with a complete characterization of their optical properties, including absorption, photoluminescence, and ASE. We aim to stablish structure-property relationships that help designing compounds with optimized ASE performance. Film experiments were accomplished at low PDI concentrations in the film, to resemble the isolated molecule behaviour, and at a range of increasing doping rates, to investigate concentration quenching effects. Compounds PDI 10 and PDI 7, bearing substituents in the 2' positions of the benzene ring (the one contiguous to the linking oxygen atom) attached to the 1,7 positions of the PDI core, have shown a better threshold performance, which is attributed to conformational (steric) effects. Films containing PDI 11 show dual ASE.

Fused Triangulene Dimers: Facile Synthesis by Intramolecular Radical-Radical Coupling and Application for Near-Infrared Lasers.

Large graphene-like molecules with four zigzag edges are ideal gain medium materials for organic near-infrared (NIR) lasers. However, synthesizing them becomes increasingly challenging as the molecular size increases. In this study, we introduce a new intramolecular radical-radical coupling approach and successfully synthesize two fused triangulene dimers (1 a/1 b) efficiently. X-ray crystallographic analysis of 1 a indicates that there is no intermolecular π-π stacking in the solid state. When the more soluble derivative 1 b is dispersed in polystyrene thin films, amplified spontaneous emission in the NIR region is observed. Using 1 b as the active gain material, we fabricate solution-processed distributed feedback lasers that exhibit a narrow emission linewidth at around 790 nm. The laser devices also exhibit low thresholds with high photostability. Our study provides a new synthetic strategy for extended nanographenes, which have diverse applications in electronics and photonics.

Perylene-Fused, Aggregation-Free Polycyclic Aromatic Hydrocarbons for Solution-Processed Distributed Feedback Lasers.

Perylene-fused, aggregation-free polycyclic aromatic hydrocarbons with partial zigzag periphery (ZY-01, ZY-02, and ZY-03) were synthesized. X-ray crystallographic analysis reveals that there is no intermolecular π-π stacking in any of the three molecules, and as a result, they show moderate-to-high photoluminescence quantum yield in both solution and in the solid state. They also display the characteristic absorption and emission spectra of perylene dyes. ZY-01 and ZY-02 with a nearly planar π-conjugated skeleton exhibit amplified spontaneous emission (ASE) when dispersed in polystyrene thin films. Solution-processed distributed feedback lasers have been fabricated using ZY-01 and ZY-02 as active gain materials, both showing narrow emission linewidth (<0.4 nm) at wavelengths around 515 and 570 nm, respectively. In contrast, ZY-03 did not show ASE and lasing, presumably due to its highly twisted backbone, which facilitates nonradiative internal conversion and intersystem crossing.

Bis(aminoaryl) Carbon-Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings.

Carbon-bridged bis(aminoaryl) oligo(para-phenylenevinylene)s have been prepared and their optical, electrochemical, and structural properties analyzed. Their radical cations are class III and class II mixed-valence systems, depending on the molecular size, and they show electronic couplings which are among the largest for the self-exchange reaction of purely organic molecules. In their dication states, the antiferromagnetic coupling is progressively tuned with size from quinoidal closed-shell to open-shell biradicals. The data prove that the electronic coupling in the radical cations and the singlet-triplet gap in the dications show similar small attenuation factors, thus allowing charge/spin transfer over rather large distances.

Thickness dependence of amplified spontaneous emission in low-absorbing organic waveguides.

The effect of varying film thickness (h) on the amplified spontaneous emission (ASE) properties of 0.5 wt.% perylenediimide-doped polystyrene waveguides is reported. The threshold dependence on h, not previously investigated in detail, is analyzed in terms of the film absorption and photoluminescence, the confinement of the fundamental waveguide mode (TE0), and the presence of high-order modes. For h<400 nm and down to 150 nm, the ASE wavelength blueshifts, while the linewidth and threshold increase. The detrimental ASE operation in very thin films is due to the low absorption as well as to the poor confinement of the TE0 mode.

Synthesis of zigzag- and fjord-edged nanographene with dual amplified spontaneous emission.

We report the synthesis of a dibenzodinaphthocoronene (DBDNC) derivative as a novel nanographene with armchair, zigzag, and fjord edges, which was characterized by NMR and X-ray crystallography as well as infrared (IR) and Raman spectroscopies. Ultrafast transient absorption (TA) spectroscopy revealed the presence of stimulated emission signals at 655 nm and 710 nm with a relatively long lifetime, which resulted in dual amplified spontaneous emission (ASE) bands under ns-pulsed excitation, indicating the promise of DBNDC as a near-infrared (NIR) fluorophore for photonics. Our results provide new insight into the design of nanographene with intriguing optical properties by incorporating fjord edges.

Excited states engineering enables efficient near-infrared lasing in nanographenes.

The spectral overlap between stimulated emission (SE) and absorption from dark states (i.e. charges and triplets) especially in the near-infrared (NIR), represents one of the most effective gain loss channels in organic semiconductors. Recently, bottom-up synthesis of atomically precise graphene nanostructures, or nanographenes (NGs), has opened a new route for the development of environmentally and chemically stable materials with optical gain properties. However, also in this case, the interplay between gain and absorption losses has hindered the attainment of efficient lasing action in the NIR. Here, we demonstrate that the introduction of two fluoranthene imide groups to the NG core leads to a more red-shifted emission than the precursor NG molecule (685 vs. 615 nm) and also with a larger Stokes shift (45 nm vs. 2 nm, 1026 cm-1vs. 53 cm-1, respectively). Photophysical results indicate that, besides the minimisation of ground state absorption losses, such substitution permits to suppress the detrimental excited state absorption in the NIR, which likely arises from a dark state with charge-transfer character and triplets. This has enabled NIR lasing (720 nm) from all-solution processed distributed feedback devices with one order of magnitude lower thresholds than those of previously reported NIR-emitting NGs. This study represents an advance in the field of NGs and, in general, organic semiconductor photonics, towards the development of cheap and stable NIR lasers.

Efficient organic distributed feedback lasers with imprinted active films.

We report on the fabrication of efficient organic distributed feedback (DFB) lasers with thermally-nanoimprinted active films, emitting between 565 and 580 nm. The use of thermal-NIL has allowed, as opposed to room temperature or solvent-assisted techniques, high grating quality and excellent modulation depth. The 155°C heat exposure of the NIL process, does not significantly affect the thermal and optical properties of the active material (polystyrene films doped with a perylenediimide derivative). These devices combine a simple and low-cost preparation method with good laser characteristics, i.e. thresholds of 1 µJ/pulse, single-mode emission with linewidths below 0.2 nm and photostability half-lives of ~ 105 pump pulses under ambient conditions. In comparison to more standard DFBs with gratings on the substrate, their fabrication is much easier, while they show a similar laser performance.

N,N'-Bis(3-methylphenyl)-N,N'-dyphenylbenzidine Based Distributed Feedback Lasers with Holographically Fabricated Polymeric Resonators.

The molecule N,N'-bis(3-methylphenyl)-N,N'-dyphenylbenzidine (TPD) has been widely used in optoelectronic applications, mainly for its hole-transporting properties, but also for its capability to emit blue light and amplified spontaneous emission, which is important for the development of organic lasers. Here, we report deep-blue-emitting distributed feedback (DFB) lasers based on TPD dispersed in polystyrene (PS), as active media, and dichromated gelatin layers with holographically engraved relief gratings, as laser resonators. The effect of the device architecture (with the resonator located below or on top of the active layer) is investigated with a dye (TPD) that can be doped into PS at higher rates (up to 60 wt%), than with previously used dyes (<5 wt%). This has enabled changing the index contrast between film and resonator, which has an important effect on the laser performance. With regards to thresholds, both architectures behave similarly for TPD concentrations above 20 wt%, while for lower concentrations, top-layer resonator devices show lower values (around half). Remarkably, the operational durability of top-layer resonator devices is larger (in a factor of around 2), independently of the TPD concentration. This is a consequence of the protection offered by the resonator against dye photo-oxidation when the device is illuminated with pulsed UV light.

Simultaneous Determination of Refractive Index and Thickness of Submicron Optical Polymer Films from Transmission Spectra.

High-transparency polymers, called optical polymers (OPs), are used in many thin-film devices, for which the knowledge of film thickness (h) and refractive index (n) is generally required. Spectrophotometry is a cost-effective, simple and fast non-destructive method often used to determine these parameters simultaneously, but its application is limited to films where h > 500 nm. Here, a simple spectrophotometric method is reported to obtain simultaneously the n and h of a sub-micron OP film (down to values of a few tenths of a nm) from its transmission spectrum. The method is valid for any OP where the n dispersion curve follows a two-coefficient Cauchy function and complies with a certain equation involving n at two different wavelengths. Remarkably, such an equation is determined through the analysis of n data for a wide set of commercial OPs, and its general validity is demonstrated. Films of various OPs (pristine or doped with fluorescent compounds), typically used in applications such as thin-film organic lasers, are prepared, and n and h are simultaneously determined with the proposed procedure. The success of the method is confirmed with variable-angle spectroscopic ellipsometry.

Blue surface-emitting distributed feedback lasers based on TPD-doped films.

Single-mode second-order distributed feedback (DFB) lasers with low threshold, based on polystyrene films doped with 30 wt. % of the hole-transporting organic molecule N,N'-bis (3-methylphenyl)-N,N'-diphenylbenzidine (TPD) are reported. The laser emission wavelength was tuned between 415 and 427 nm by film thickness variation. The effectiveness of the DFB grating in improving the laser performance is evidenced by the observation of linewidths and laser thresholds lower than those of the amplified spontaneous emission characteristics shown by films without gratings. The use of holographic lithography as the technique for grating recording has allowed us to prepare large samples in a fast, versatile, and simple manner.

Amplified spontaneous emission properties of semiconducting organic materials.

This paper aims to review the recent advances achieved in the field of organic solid-state lasers with respect to the usage of semiconducting organic molecules and oligomers in the form of thin films as active laser media. We mainly focus on the work performed in the last few years by our research group. The amplified spontaneous emission (ASE) properties, by optical pump, of various types of molecules doped into polystyrene films in waveguide configuration, are described. The various systems investigated include N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD), several perilenediimide derivatives (PDIs), as well as two oligo-phenylenevinylene derivatives. The ASE characteristics, i.e., threshold, emission wavelength, linewidth, and photostability are compared with that of other molecular materials investigated in the literature.

Dual Amplified Spontaneous Emission and Lasing from Nanographene Films.

Chemically synthesized zigzag-edged nanographenes (NG) have recently demonstrated great success as the active laser units in solution-processed organic distributed feedback (DFB) lasers. Here, we report the first observation of dual amplified spontaneous emission (ASE) from a large-size NG derivative (with 12 benzenoid rings) dispersed in a polystyrene film. ASE is observed simultaneously at the 685 and 739 nm wavelengths, which correspond to different transitions of the photoluminescence spectrum. Ultrafast pump-probe spectroscopy has been used to ascertain the underlying photophysical processes taking place in the films. DFB lasers, based on these materials and top-layer nanostructured polymeric resonators (i.e., one or two-dimensional surface relief gratings), have been fabricated and characterized. Lasers emitting close to either one of the two possible ASE wavelengths, or simultaneously at both of them, have been prepared by proper selection of the resonator parameters.

Controlling the emission properties of solution-processed organic distributed feedback lasers through resonator design.

Surface-emitting distributed feedback (DFB) lasers with both, resonator and active material based on solution-processable polymers, are attractive light sources for a variety of low-cost applications. Besides, the lasers should have competitive characteristics compared to devices based on high-quality inorganic resonators. Here, we report high performing all-solution-processed organic DFB lasers, consisting of water-processed photoresist layers with surface relief gratings located over the active films, whose emission properties can be finely tuned through resonator design. Their laser threshold and efficiency are simultaneously optimized by proper selection of residual resist thickness and grating depth, d. Lowest thresholds and largest efficiencies are obtained when there is no residual layer, while a trade-off between threshold and efficiency is found in relation to d, because both parameters decrease with decreasing d. This behaviour is successfully explained in terms of an overlap factor r, defined to quantify the interaction strength between the grating and the light emitted by the active film and traveling along it, via the evanescent field. It is found that optimal grating depths are in the range 100-130 nm (r ~ 0.5-0.4). Overall, this study provides comprehensive design rules towards an accurate control of the emission properties of the reported lasers.

Solution-processed nanographene distributed feedback lasers.

The chemical synthesis of nanographene molecules constitutes the bottom-up approach toward graphene, simultaneously providing rational chemical design, structure-property control and exploitation of their semiconducting and luminescence properties. Here, we report nanographene-based lasers from three zigzag-edged polycyclic aromatics. The devices consist of a passive polymer film hosting the nanographenes and a top-layer polymeric distributed feedback resonator. Both the active material and the laser resonator are processed from solution, key for the purpose of obtaining low-cost devices with mechanical flexibility. The prepared lasers show narrow linewidth ( < 0.13 nm) emission at different spectral regions covering a large segment of the visible spectrum, and up to the vicinity of the near-infrared. They show outstandingly long operational lifetimes (above 105 pump pulses) and very low thresholds. These results represent a significant step forward in the field of graphene and broaden its versatility in low-cost devices implying light emission, such as lasers.

Carbon-bridged oligo(p-phenylenevinylene)s for photostable and broadly tunable, solution-processable thin film organic lasers.

Thin film organic lasers represent a new generation of inexpensive, mechanically flexible devices for spectroscopy, optical communications and sensing. For this purpose, it is desired to develop highly efficient, stable, wavelength-tunable and solution-processable organic laser materials. Here we report that carbon-bridged oligo(p-phenylenevinylene)s serve as optimal materials combining all these properties simultaneously at the level required for applications by demonstrating amplified spontaneous emission and distributed feedback laser devices. A series of six compounds, with the repeating unit from 1 to 6, doped into polystyrene films undergo amplified spontaneous emission from 385 to 585 nm with remarkably low threshold and high net gain coefficients, as well as high photostability. The fabricated lasers show narrow linewidth (<0.13 nm) single mode emission at very low thresholds (0.7 kW cm(-2)), long operational lifetimes (>10(5) pump pulses for oligomers with three to six repeating units) and wavelength tunability across the visible spectrum (408-591 nm).

Stimulated resonance Raman scattering and laser oscillation in highly emissive distyrylbenzene-based molecular crystals.

Three-in-one: A novel distyrylbenzene-based material forms J-type aggregates in single crystals with highly polarized and bright red emission, giving rise to optical gain narrowing, for which different mechanisms (amplified spontaneous emission, laser emission and stimulated resonance Raman scattering) are observed. These are correlated with the favorable intrinsic and macroscopic properties of the crystal, in particular to the orientation of the molecules to the crystal surface.

Amplified spontaneous emission in polymer films doped with a perylenediimide derivative.

The presence of amplified spontaneous emission (ASE) by optical pump in polystyrene films doped with N,N'-di(10-nonadecyl)perylene-3,4:9,10-tetracarboxylic diimide (PDI-N) in a range of PDI-N concentrations between 0.25 and 5 wt. % is reported. Gain coefficients up to 10 cm(-1), at a pump intensity of 74 kW/cm2, were obtained. The lowest thresholds (approximately 15 kW/cm2) and largest photostabilities measured at 50% (approximately 50 min, i.e., 30,000 pump pulses) were obtained for concentrations up to 1 wt. %. The observation of an increase in the ASE threshold and a decrease in the photostability for larger concentrations is attributed to the presence of aggregated species.