Singular Temperatures Connected to Charge Transport Mechanism Transitions in Perylene Bisimides from Steady-State Photocurrent Measurements

Perylene bisimides (PBIs) are n-type semiconducting and photogenerating materials widely used in a variety of optoelectronic devices. Particularly interesting are PBIs that are simultaneously water-soluble and liquid-crystalline (PBI-W+LC) and, thus, attractive for the development of high-performing easily processable applications in biology and “green” organic electronics. In this work, singular temperatures connected to charge transport mechanism transitions in a PBI-W+LC derivative are determined with high accuracy by means of temperature-dependent photocurrent studies. These singular temperatures include not only the ones observed at 60 and 110 °C, corresponding to phase transition temperatures from crystalline to liquid-crystalline (LC) and from LC to the isotropic phase, respectively, as confirmed by differential scanning calorimetry (DSC), but also a transition at 45 °C, not observed by DSC. By analyzing the photocurrent dependence simultaneously on temperature and on light intensity, this transition is interpreted as a change from monomolecular to bimolecular recombination. These results might be useful for other semiconducting photogenerating materials, not necessarily PBIs or even organic semiconductors, which also show transport behavior changes at singular temperatures not connected with structural or phase transitions.We appreciate support from the Spanish government (MINECO) and the European Community (FEDER) through Grant MAT-2011-28167-C02-01, as well as the University of Alicante. We gratefully acknowledge financial support from MINECO (MAT2014-52305-P) and the UCM-BSCH joint project (GR3/14-910759). A. de la Peña thanks Universidad Complutense for a predoctoral fellowship

Distributed feedback lasers based on dichromated poly(vinyl alcohol) reusable surface-relief gratings

A simple, low-cost and versatile holographic method to produce reusable surface-relief gratings on dichromated poly(vinyl alcohol) (DCPVA) films, with periods Λ ≥ 270 nm and modulation depths up to 300 nm, is reported. DCPVA presents processing advantages with respect to other photoresists, such as dichromated gelatine, i.e. higher light sensitivity, simpler fabrication process and better batch to batch reproducibility. The successful use of these DCPVA relief gratings as distributed feedback (DFB) laser resonators is demonstrated. Second-order DFB devices emitting in the wavelength range 577-614 nm have been easily prepared by coating a dye-doped polymer film on top of the resonators.We thank the Spanish Government (MINECO) and the European Union (FEDER) for grant no. MAT2011-28167-C02

Sub-400 nm film thickness determination from transmission spectra in organic distributed feedback lasers fabrication

The design and fabrication of thin-film based organic optoelectronic devices require knowledge of the film optical properties. A low-cost and non-destructive method often used for optical characterization of films is the well-established spectrophotometric envelope method. However, this method is typically limited to thickness above 400 nm, a value often higher than that of the films involved in these devices. This paper studies a procedure to obtain the thickness of sub-400 nm active films from their spectrophotometric trace when the refractive index is previously known. The proposed procedure is based on comparing the experimental transmission spectrum in the transparent spectral window with that obtained by simulation. The capabilities of the proposed method are demonstrated here by its application in the fabrication of organic distributed feedback lasers, for which a fine control of film thickness is important to obtain an optimized and reproducible response. Results are verified with other techniques, such as ellipsometry and profilometry. Thus, with the proposed method, film thickness can be easily determined down to 40 nm maintaining an accuracy of about 5 nm even for films with low refractive index (1.5–1.7). Different methods to determine refractive index of these films are also discussed.Spanish Ministry of Economy and Competitivity (MINECO) and European Community (FEDER) through grant no. MAT2015-66586-R

Perylenediimide-based distributed feedback lasers with holographic relief gratings on dichromated gelatine

One dimensional second-order distributed feedback (DFB) lasers consisting of polystyrene (PS) films doped with a perylenediimide laser dye, deposited over dichromated gelatine (DCG) photoresist layers with solvent resistant relief gratings recorded by holographic lithography, are reported. The advantage of using the grating on DCG in the final device is that the fabrication process is simplified and the grating pattern better preserved, since no etching methods to transfer the grating to another substrate are needed. A very simple model, proposed to explain the experimental waveguide properties, has allowed identifying the waveguide mode at which DFB emission appears, which was the key to optimize the device performance. In the frame of this model, the thickness of the PS and DCG films could be adjusted in order to minimize the laser threshold and to control its wavelength tuneability. The performance of these lasers is comparable to that of recently reported devices based on the same active material, but deposited over high-quality DFB gratings engraved on SiO2 by nanoimprint lithography.We thank support from the Spanish Government (MINECO) and the European Community (FEDER) through Grant Nos. MAT2008-06648-C02 and MAT-2011-28167-C02, as well as to the University of Alicante. M.G.R. was supported by a CSIC fellowship within the program JAE

Distributed feedback lasers based on perylenediimide dyes for label-free refractive index sensing

The refractive index sensing capabilitity of distributed feedback (DFB) lasers based on highly photostable (under ambient conditions) perylenediimide-based active films, are reported. The sensor bulk sensitivity is determined from changes in the laser emission wavelength upon exposure to different liquids. The role of the active film thickness (hf) on the sensor sensitivity and on the laser parameters is studied. Sensors based on very thin films (hf = 160 nm) show the highest sensitivities, but their laser thresholds are relatively high and their operational durabilities moderate. The use of thicker films (hf = 850 nm) allows reducing the laser threshold and increasing the durability by two orders of magnitude. In this case, a higher sensitivity is achieved when the sensor operates at the wavelength corresponding to the first-order TE1 mode, instead of at the TE0 one. Finally, it is also shown that the inclusion of a high refractive index TiO2 layer on top of the sensor structure improves the sensitivity by around two times.This work was supported by the Spanish Government (MINECO) and the European Community (FEDER) through grant no. MAT-2011–28167-C02. This work was partially funded by the Basque Government within the framework of the Etortek Program (Grant No. IE13-360). M. Morales-Vidal has been partly supported by a MINECO FPI fellowship (no. BES-2009-020747)

Performance Characterization of ESA's Tropospheric Delay Calibration System for Advanced Radio Science Experiments

Media propagation noises are amongst the main error sources of radiometric observables for deep space missions, with fluctuations of the tropospheric excess path length representing a relevant contributor to the Doppler noise budget. Microwave radiometers currently represent the most accurate instruments for the estimation of the tropospheric delay and delay rate along a slant direction. A prototype of a tropospheric delay calibration system (TDCS), using a 14 channel Ka/V band microwave radiometer, has been developed under a European Space Agency contract and installed at the deep space ground station in Malargüe, Argentina, in February 2019. After its commissioning, the TDCS has been involved in an extensive testbed campaign by recording a total of 44 tracking passes of the Gaia spacecraft, which were used to perform an orbit determination analysis. This work presents the first statistical characterization of the end-to-end performance of the TDCS prototype in an operational scenario. The results show that using TDCS-based calibrations instead of the standard GNSS-based calibrations leads to a significant reduction of the residual Doppler noise and instability

1,7-Bay-Substituted Perylenediimide Derivative with Outstanding Laser Performance

Efficient ASE at wavelengths >620 nm from PS films doped with a bay-substituted perylenediimide (PDI) derivative is reported. The maximum PDI content is around 40 times larger than in prior studies. The ability to introduce large dye amounts into the film without photoluminescence (PL) quenching allows very high PL and ASE efficiencies with low thresholds. A distributed feedback (DFB) laser device using one of the best-performing films is fabricated and characterized.We thank support from the Spanish Government (MINECO), the European Community (FEDER) and the Generalitat Valenciana through MAT-2011–28167-C02, CTQ2011–26455, PROMETEO 2012/010 and ISIC/2012/008, as well as to the University of Alicante and the University Miguel Hernández de Elche

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.The research performed at the University of Alicante was funded by the “Ministerio de Ciencia e Innovación” (MCIN) of Spain and the European Regional Development Fund (grant No. PID2020-119124RB-I00) and from the Generalitat Valenciana through grant No. AICO/2021/093. This study is part of the Advanced Materials program supported by the Spanish MCIN with funding from European Union NextGenerationEU and by Generalitat Valenciana (grant no. MFA/2022/045). The research performed at Universidad Miguel Hernández de Elche was funded by the European Regional Development Fund “A way to make Europe” and the Spanish Ministerio de Ciencia e Innovación/Agencia Estatal de Investigación (project PID2019-109200GB-I00)

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.We thank support from the Spanish Government (MECC) and the European Community (FEDER) through grants MAT2008-06648-C02 and MAT-2011-28167-C02, as well as from the University of Alicante. MGR and MM are supported respectively by a CSIC fellowship within the program JAE and by MEC through a FPI fellowship

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.We thank support from the Spanish Government (MINECO) and the European Community (FEDER) through Grants MAT2011-28167-C02 and MAT2015-66586-R, as well as to the University of Alicante. M.M-V. has been partly supported by a MINECO FPI fellowship (no. BES-2009-020747) and by a Junta de Castilla y León grant (no. SA046U16)