José-Luis Maldonado

Luminogenic materials constructed from tetraphenylethene building blocks: Synthesis, aggregation-induced emission, two-photon absorption, light refraction, and explosive detection

Luminogenic molecules [(TPE)3 (1), TPE-C = C-TPE-C = C-TPE (2), and TPE-C≡C-TPE-C≡C-TPE (3)] and their polymers P1–P3 are constructed from tetraphenylethene (TPE) building blocks in high yields by Suzuki, Witting, and Sonogashira coupling reactions. All the compounds are soluble and enjoy high thermal stability, losing little of their weights when they are heated to 290–528 °C under nitrogen or 288–436 °C in air. Analyses by UV spectroscopy and cyclic voltammetry as well as theoretical calculations show that the conjugation of the luminophores is in the order of 2 > 3 > 1, P2 > P3 > P1, and P1–P3 > 1–3. All the molecules and polymers are weakly emissive in solutions. They, however, become strong emitters in the aggregate state with fluorescence quantum yields up to 90%. Both 1–3 and P1–P3 exhibit the feature of aggregation-enhanced two-photon excited fluorescence. Large two-photon absorption cross sections (up to ∼900 GM) are observed in the nanoaggregates of the polymers. Thin solid films of the polymers show high refractive indices (RI = 1.7649 − 1.6873) in a wide wavelength region of 400–1700 nm, high modified Abbe numbers (vD′ up to 3436), and low optical dispersions (D′ down to 2.9 × 10−4). The light emissions of the polymers can be quenched exponentially by picric acid with large quenching constants, suggesting that they can be utilized as efficient chemosensors for explosive detection.

Optical Design of Transparent Thin Metal Electrodes to Enhance In‐Coupling and Trapping of Light in Flexible Polymer Solar Cells

ITO-free polymer solar cells with efficiencies as high as 6.6% and 5.8% are fabricated on glass and polyethylene naphthalate (PEN) by using TeO(2) to enhance the in-coupling of light in an Ag-Ag microcavity. These cells exhibit higher performance, selective microcavity resonance as a function of the thickness of TeO(2) , and better bending stability than flexible devices made with ITO.

Stereoselective Synthesis, Efficient Light Emission, and High Bipolar Charge Mobility of Chiasmatic Luminogens

Stereoregular tetraphenylethene derivatives (Z)-o-BCaPTPE and (Z)-o-BTPATPE featured with chiasmatic conformations and aggregation-enhanced emission characteristics are synthesized using a McMurry reaction. Both luminogens exhibit high hole and electron mobilities. Organic light-emitting diodes (OLEDs) using (Z)-o-BCaPTPE and (Z)-o-BTPATPE as both the light-emitting and electron-transporting layers show high efficiencies.

Difluorenyl carbo-Benzenes: Synthesis, Electronic Structure, and Two-Photon Absorption Properties of Hydrocarbon Quadrupolar Chromophores

The synthesis, crystal and electronic structures, and one- and two-photon absorption properties of two quadrupolar fluorenyl-substituted tetraphenyl carbo-benzenes are described. These all-hydrocarbon chromophores, differing in the nature of the linkers between the fluorenyl substituents and the carbo-benzene core (C-C bonds for 3 a, C-C=C-C expanders for 3 b), exhibit quasi-superimposable one-photon absorption (1PA) spectra but different two-photon absorption (2PA) cross-sections σ2PA. Z-scan measurements (under NIR femtosecond excitation) indeed showed that the C≡C expansion results in an approximately twofold increase in the σ2PA value, from 336 to 656 GM (1 GM = 10(-50) cm(4) s molecule(-1) photon(-1)) at λ = 800 nm. The first excited states of Au and Ag symmetry accounting for 1PA and 2PA, respectively, were calculated at the TDDFT level of theory and used for sum-over-state estimations of σ2PA(λi), in which λi = 2 hc/Ei, h is Plancks constant, c is the speed of light, and Ei is the energy of the 2PA-allowed transition. The calculated σ2PA values of 227 GM at 687 nm for 3 a and 349 GM at 708 nm for 3 b are in agreement with the Z-scan results.

High diffraction efficiency at low electric field in photorefractive polymers doped with arylimine chromophores

We report on the high photorefractive performance of organic polymers doped with arylimine chromophore (diethylaminosalicylaldiminato)nitrobenzene (H1) and its derivative (diethylaminophenylaldiminato)nitrophenol (H2). Polymer blends of H1 and H2 with PVK : ECZ : C60 at 25 : 49 : 25 : 1 wt% and H2 : PVK : ECZ : PC61BM at the same concentration were fabricated. The electric field (E) steady-state diffraction efficiency dependence and the optical gain were measured through holographic experiments at room temperature. For polymers based on chromophore H2, overmodulation of the diffraction efficiency was measured at just E = 32 V µm−1 obtaining 75%, and for polymers based on H1, diffraction of 87% (overmodulation) at E = 48 V µm−1 was observed. Holographic recording imaging was demonstrated at an electric field of just 10–14 V µm−1.

SEMICONDUCTOR POLYMER/TOP ELECTRODE INTERFACE GENERATED BY TWO DEPOSITION METHODS AND ITS INFLUENCE ON ORGANIC SOLAR CELL PERFORMANCE

In this Research Article, the effect of two techniques for top-electrode deposition in organic photovoltaics (OPVs) cells with the configuration ITO/PEDOT:PSS/PTB7-Th:PC71BM/PFN/top-electrode is analyzed. One deposition was made by evaporation under high vacuum, meanwhile the other was carried out at normal room atmosphere; for the former, a double layer of Ca and the eutectic alloy Fields metal (FM) was thermally evaporated, while for the latter FM was deposited just by melting and dropping it on top of the delimited active area at temperatures about 90 °C. The average short-circuit photocurrent density, open circuit voltage and fill factor for devices with either Ca/FM (evaporated) or FM (by dripping) cathode, were very similar: around 13.20 mA/cm2, 840 mV, and 0.6, respectively. Average efficiency for devices with the mentioned evaporated cathode was of 6.4% (largest value 7.0%), meanwhile for devices with the cathode deposited by dripping, it was of 6.1% (largest value 6.5%). Morphological analysis, by atomic force microscopy on the surface of a FM electrode, detached from an OPV device, shows inhomogeneities and pinholes in its surface with an average roughness of 16 nm. OPV photocurrent was studied by means of laser beam induced current (LBIC), it showed that OPVs devices with FM top electrode exhibits an inhomogeneous response. An impedance analysis was also carried out and results were correlated with defects observed at the studied interface. In spite of the mentioned deficiencies at FM interface, overall PV performance of devices with this electrode highlights the convenience of using FM because of its easy, fast, and low-cost deposition (vacuum free) characteristics.

PTB7:PC

In this work, we study the performance of organic photovoltaic (OPV) cells based on the PTB7:PC71BM blend and the use of an alternative metal cathode called fields metal (FM) (Bi/In/Sn: 32.5%, 51%, 16.5%), which can be easily deposited through a vacuum-free process at regular atmosphere and low temperature (90 °C). The charge extraction and losses involved with the use of FM, in combination with an electron extraction layer, in this case the widely used polymer PFN, were fully analyzed using equivalent circuit models for the architecture ITO/PEDOT:PSS/PTB7:PC71BM/PFN/FM. Power conversion efficiencies (PCEs) higher than 6% were reached with this architecture, which exhibited Jsc of 14.3 mA/cm2, Voc of 0.76 V, and FF of 0.6. The single-diode equivalent circuit model demonstrates that devices comprising FM as counterelectrode are characterized by a low series resistance (1.0 Ω · cm2), large shunt resistance (1.1 × 105 Ω · cm2), and low saturation current (1.4 × 10-7 mA/cm2). Additional electrical characterization, through impedance spectroscopy, was also carried out. The obtained PV parameters are similar to those exhibited by devices comprising standard counterelectrodes, i.e., Al, deposited through a high-vacuum evaporation process. Thus, FM, as nonconventional and alternative counterelectrode, in combination with an electron extraction layer, can be used to fabricate OPVs cells with very acceptable performance through a vacuum-free process.

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In this work, microwave synthesis, chemical, optical and electrochemical characterization of three small organic molecules, TPA-TPD, TPA-PT-TPD and TPA-TT-TPD with donor-acceptor structure and their use in organic photovoltaic cells are reported. For the synthesis, 5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione was used as electron withdrawing fragment while the triphenylamine was used as electron donating fragment. Molecular electronic geometry and electronic distribution density were established by density functional theory (DFT) calculations and confirmed by optical and chemical characterization. These molecules were employed as electron-donors in the active layer for manufacturing bulk heterojunction organic solar cells, where [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) was used as electron-acceptor. As cathode, Field′s metal (FM), an eutectic alloy (Bi/In/Sn: 32.5%, 51%, and 16.5%, respectively) with a melting point above 62 °C, was easily deposited by drop casting under vacuum-free process and at air atmosphere. Prepared devices based on TPA-TPD:PC71BM (1:4 w/w ratio) presented a large VOC = 0.97 V, with JSC = 7.9 mA/cm2, a FF = 0.34, then, a power conversion efficiency (PCE) of 2.6%.

BM-Based Solar Cells Fabricated With the Eutectic Alloy Field's Metal as an Alternative Cathode and the Influence of an Electron Extraction Layer

Light emission properties of a fluorene cross-conjugated polymer (PF–1) based on the monomer 4,7-bis[2-(9,9-dimethyl)fluorenyl] benzo[1,2,5]thiadiazole are reported. This polymer exhibits solubility at high concentrations, good processability into thin solid films of good quality and a broad emission band with a fluorescence quantum yield of approximately 1. Based on these features, in this paper we implemented the use of PF–1 as an active layer in polymer light-emitting diodes (PLEDs) and as a laser gain medium in solution. To get insight on the conducting properties of PF–1, two different electron injectors, poly [(9,9-bis(3′-(N,N-dimethylamino) propyl)-2,7-fluorene)-alt-2,7-(9,9–dioctylfluorene)] (PFN) and lithium fluoride (LiF), were used in a simple PLED architecture. PLEDs with the PFN film were found to exhibit better performance with a maximum luminous efficiency of 40 cd/A, a turn-on voltage (Von) of approximately 4.5 V and a luminance maximum of 878 cd/m2 at 5.5 V, with a current density of 20 A/m2. For the lasing properties of PF–1, we found a lasing threshold of around 75 μJ and a tunability of 20 nm. These values are comparable with those of rhodamine 6G, a well-known laser dye.

Small Molecules Derived from Thieno[3,4-c]pyrrole-4,6-dione (TPD) and Their Use in Solution Processed Organic Solar Cells

Two copolymers of 3-alkylthiophene (alkyl = hexyl, octyl) and a thiophene functionalized with disperse red 19 (TDR19) as chromophore side chain were synthesized by oxidative polymerization. The synthetic procedure was easy to perform, cost-effective, and highly versatile. The molecular structure, molecular weight distribution, film morphology, and optical and thermal properties of these polythiophene derivatives were determined by NMR, FT-IR, UV-Vis GPC, DSC-TGA, and AFM. The third-order nonlinear optical response of these materials was performed with nanosecond and femtosecond laser pulses by using the third-harmonic generation (THG) and Z-scan techniques at infrared wavelengths of 1300 and 800 nm, respectively. From these experiments it was observed that although the TRD19 incorporation into the side chain of the copolymers was lower than 5%, it was sufficient to increase their nonlinear response in solid state. For instance, the third-order nonlinear electric susceptibility () of solid thin films made of these copolymers exhibited an increment of nearly 60% when TDR19 incorporation increased from 3% to 5%. In solution, the copolymers exhibited similar two-photon absorption cross sections with a maximum value of 8545 GM and 233 GM (1 GM = 10−50 cm4 s) per repeated monomeric unit.