Single graphene derivative layer as a hole transport in organic solar cells based on PBDB-T:ITIC.

A layer of fluorinated reduced graphene oxide (FrGO), as an alternative hole transport (HTL) in organic solar cells (OSCs) based on a PBDB-T:ITIC active layer, is reported. OSC configuration is ITO/HTL/PBDB-T:ITIC/PFN/FM; FM is Field's metal, a eutectic alloy deposited at room atmosphere. PEDOT:PSS, FrGO/PEDOT:PSS, and FrGO are tested as HTLs; the average efficiencies of 8.8, 8.2, and 5.3%, respectively, are reached. Inhomogeneity of the FrGO layer is determined as the main factor that affects the photovoltaic behavior and stability. Device stability is very acceptable, sometimes with a superior behavior than data previously reported; FM also could potentially contribute to this enhanced stability.

Scanning Probe Microscopy Analysis of Nonfullerene Organic Solar Cells.

In this work, scanning probe microscopies (SPMs) are used for the analysis of PBDB-T, ITIC, and PBDB-T:ITIC layers of solar cells (OSCs). Scanning tunneling microscopy (STM) images of PBDB-T reveal that thin films (<1 nm) tend to form worm-like pattern (amorphous type) domains with an average chain-to-chain distance of 950 pm; likewise, STM images of ITIC show that side arms form chain-like patterns. STM images of PBDB-T:ITIC blend suggest why PBDB-T domains could facilitate charge dissociation. Further, a strong interchain π-π interaction of the ITIC molecules could promote self-organization, and under the mutual interaction with the PBDB-T polymer, it could influence the pathway formation for electron transport. Moreover, when correlating electrostatic force microscopy (EFM) and photoconductive atomic force microscopy (pc-AFM), the blend morphology and its electrical/electronic properties are determined; the ideal domain size of PBDB-T:ITIC blend phases for maximizing the generated photocurrent is 15-35 nm. Furthermore, phase contrast and surface electric potential characteristics with Kelvin probe force microscopy (KPFM) are measured to examine additional details about the surface and potential changes due to the domain differences in the active layer. OSCs based on the nonfullerene PBDB-T:ITIC active layer reach an average power conversion efficiency (PCE) of 9.1% (best 9.2%).

Core carbo-mer of an Extended Tetrathiafulvalene: Redox-Controlled Reversible Conversion to a carbo-Benzenic Dication.

carbo-Benzene is an aromatic molecule devised by inserting C2 units within each C-C bond of the benzene molecule. By integrating the corresponding carbo-quinoid core as bridging unit in a π-extended tetrathiafulvalene (exTTF), it is shown that a carbo-benzene ring can be reversibly formed by electrochemical reduction or oxidation. The so-called carbo-exTTF molecule was thus experimentally prepared and studied by UV-visible absorption spectroscopy and cyclic voltammetry, as well as by X-ray crystallography and by scanning tunneling microscopy (STM) on a surface of highly oriented pyrolytic graphite (HOPG). The molecule and its oxidized and reduced forms were subjected to a computational study at the density functional theory (DFT) level, supporting carbo-aromaticity as a driving force for the formation of the dication, radical cation, and radical anion. By allowing co-planarity of the dithiolylidene rings and carbo-quinoidal core, carbo-exTTFs present a promising new class of redox-active systems.

Interfacial Energetic Level Mapping and Nano-Ordering of Small Molecule/Fullerene Organic Solar Cells by Scanning Tunneling Microscopy and Spectroscopy.

Using scanning tunneling microscopy (STM) and spectroscopy (STS) at the liquid/solid interface, morphology evolution process and energetic level alignment of very thin solid films (thickness: <700 pm), of the low molecular weight molecule DRCN5T and DRCN5T:[70]PCBM blend are analyzed after applying thermal annealing at different temperatures. These films exhibit a worm-like pattern without thermal annealing (amorphous shape); however, after applying thermal annealing at 120 °C, the small molecule film domains crystallize verified by X-ray diffraction: structural geometry becomes a well-defined organized array. By using STS, the energy band diagrams of the semiconductor bulk heterojunction (blended film) at the donor-acceptor interface are determined; morphology and energy characteristics can be correlated with the organic solar cells (OSC) performance. When combining thermal treatment and solvent vapor annealing processes as described in previous literature by using other techniques, OSC devices based on DRCN5T show a very acceptable power conversion efficiency of 9.0%.

Nontoxic pyrite iron sulfide nanocrystals as second electron acceptor in PTB7:PC71BM-based organic photovoltaic cells.

Herein, we report the synthesis of nontoxic pyrite iron sulfide (FeS2) nanocrystals (NCs) using a two-pot method. Moreover, we study the influence of these NCs incorporated into the PTB7:PC71BM active layer of bulk-heterojunction ternary organic photovoltaic (OPV) cells. The OPV devices are fabricated with the direct configuration glass/ITO/PEDOT:PSS/PTB7:PC71BM:FeS2/PFN/FM. The Field's metal (FM) is a eutectic alloy composed of 32.5% Bi, 51% In and 16.5% Sn by weight that melts at 62 °C. It is deposited on the active layer/PFN under atmospheric conditions. Ternary active layers are prepared by adding small amounts of the semiconducting FeS2 NCs at different weight ratios of 0.0, 0.25, 0.5, and 1.0 wt % with respect to the electron donor PTB7. With respect to the reference device (without FeS2), a 21% increase in the power conversion efficiency (PCE) is observed for OPVs with 0.5 wt % FeS2, such that the PCE of the OPVs is enhanced from 5.69 to 6.47%. According to the Kruskal-Wallis and Mann-Whitney statistical tests, all OPV devices follow the same trend.

A novel coordination mode of κ1-N-Br-pyridylbenz-(imida, oxa or othia)-zole to Pt(ii): synthesis, characterization, electrochemical and structural analysis.

Herein, three novel Pt(ii) complexes with formula [trans-Pt(Br-PyBenz-X)(Cl)2(DMSO)] (1-3) having Br-pyridylbenz-(imida, oxa or othia)-zole (L1-3) derivatives as potential bidentate ligands, under an unusual κ1-N-coordination mode are reported. All compounds were obtained straightforwardly via reaction of corresponding LPB1-3 and [Pt(Cl)2(DMSO)2] (DMSO = dimethyl sulfoxide), at 100 °C in acetonitrile, respectively. 1-3 complexes were characterized by analytical and spectroscopic data: melting point, FT-IR, Raman, UV/Vis and NMR experiments. Cyclic voltammetry studies show an irreversible two-electron process at -0.50 and -0.51 V, which was ascribed to the Pt(ii)/Pt(iv) couple, for complexes 2 and 3. The crystal structure of complex 2 was elucidated by single-crystal X-ray diffraction, where the platinum atom exhibits a square plane geometry, where LPB2 adopts an unusual mono-coordinated mode via an N-κ1-benzoxazole ring. According to DFT calculations the first N-coordination exchanging one DMSO molecule is favourable, while the second N-coordination is highly impeded.

Efficient OLEDs Fabricated by Solution Process Based on Carbazole and Thienopyrrolediones Derivatives.

Four low molecular weight compounds-three of them new, two of them with carbazole (Cz) as functional group and the other two with thienopyrroledione (TPD) group-were used as emitting materials in organic light emitting diodes (OLEDs). Devices were fabricated with the configuration ITO/PEDOT:PSS/emitting material/LiF/Al. The hole injector layer (HIL) and the emitting sheet were deposited by spin coating; LiF and Al were thermally evaporated. OLEDs based on carbazole derivatives show luminances up to 4130 cd/m², large current efficiencies about 20 cd/A and, cautiously, a very impressive External Quantum Efficiency (EQE) up to 9.5%, with electroluminescence peaks located around 490 nm (greenish blue region). Whereas, devices manufactured with TPD derivatives, present luminance up to 1729 cd/m², current efficiencies about 4.5 cd/A and EQE of 1.5%. These results are very competitive regarding previous reported materials/devices.

[Trends in the level of control of patients with type 2 diabetes from 2010 to 2015]. / Tendencias sobre los parámetros del grado de control de los pacientes con diabetes tipo 2 desde el año 2010 al año 2015.

INTRODUCTION: Aim: To examine the trend in the level of control of glycated haemoglobin (HbA1c), blood pressure (BP), and LDL-cholesterol (LDL) in patients with type 2 diabetes mellitus between 2010 and 2015. METHODS: Setting: 3 cut-offs in the years 2010, 2013, and 2015. Southeast area of Madrid. DESIGN: Descriptive and cross-sectional epidemiological study. PARTICIPANTS: Patients diagnosed and registered with type 2 diabetes. N=41,096 (2010), n=49,658 (2013), n=6,674 (2015) MAIN MEASUREMENTS: Measurement or not in the last year of HbA1c, BP, and LDL. Control of HbA1c (<7% individual targeting), BP (<140/90mmHg), and LDL (<100mg/dL, if cardiovascular disease <70mg/dL). Data were collected from electronic records of clinical history. The Chi-square test was used. RESULTS: The percentages of patients with each parameter measured in 2010, 2013 and 2015 were: HbA1c: 36.4%, 37.0%, 62.0% (P<.001); BP: 33.2%, 43.3%, 65.0% (P<.001); LDL: 32.9%, 33.2%, 43.5% (P<.001). The percentages of patients with each parameter measured and controlled in 2010, 2013, and 2015 were: HbA1c: 59.6%, 59.1%, 79.6% (P<.001); BP: 74.9%, 67.4%, 79.2% (P<.001); LDL: 41.8%, 58.3%, 58.8% (P<.001) CONCLUSION: In the 2010-2015 period, a sustained but insufficient trend of better control of HbA1c, BP and LDL was observed in patients with diabetes. The frequency of the measurements of these parameters improved more than the control of them. It seems that efforts to improve care for the patient with diabetes pay off, but they still have to be maintained.

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

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%.

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 Field's 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.

Light Emission Properties of a Cross-Conjugated Fluorene Polymer: Demonstration of Its Use in Electro-Luminescence and Lasing Devices.

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.

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 Planck's 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.

Photophysical Study of Polymer-Based Solar Cells with an Organo-Boron Molecule in the Active Layer.

Our group previously reported the synthesis of four polythiophene derivatives (P1-P4) used for solar cells. The cells were prepared under room conditions by spin coating, leading to low efficiencies. However, after the addition of 6-nitro-3-(E)-3-(4-dimethylaminophenyl)allylidene)-2,3-dihydrobenzo[d]-[1,3,2] oxazaborole (M1) to their active layers, the efficiencies of the cells showed approximately a two-fold improvement. In this paper, we study this enhancement mechanism by performing ultrafast transient absorption (TA) experiments on the active layer of the different cells. Our samples consisted of thin films of a mixture of PC61BM with the polythiophenes derivatives P1-P4. We prepared two versions of each sample, one including the molecule M1 and another without it. The TA data suggests that the efficiency improvement after addition of M1 is due not only to an extended absorption spectrum towards the infrared region causing a larger population of excitons but also to the possible creation of additional channels for transport of excitons and/or electrons to the PC61BM interface.

Two-photon excited fluorescence of silica nanoparticles loaded with a fluorene-based monomer and its cross-conjugated polymer: their application to cell imaging.

In this work the two-photon activity of nanoparticles obtained from a fluorene monomer (M1) and its cross-conjugated polymer (P1) is reported. Aqueous suspensions of M1 and P1 nanoparticles prepared through the reprecipitation method exhibited maximum two-photon absorption (TPA) cross-sections of 84 and 9860 GM (1 GM = 10(-50) cm(4) s) at 740 nm, respectively, and a fluorescence quantum yield of ~1. Such a two-photon activity was practically equal with respect to that for molecular solutions of M1 and P1. These materials were then successfully encapsulated into silica nanoparticles to provide bio-compatibly. A lung cancer cell line (A549) and a human cervical cancer cell line (HeLa cells) were incubated with our fluorescent silica nanoparticles to carry out two-photon imaging. By means of these studies we demonstrate that optimized nonlinear optical polymers loaded in silica nanoparticles can be used as efficient probes with low cytotoxicity and good photostability for two-photon fluorescence microscopy. To the best of our knowledge, studies concerning polymer-doped silica nanoparticles exhibiting large two-photon activity have not been reported in the literature.

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.

Structural, thermal and optical characterization of a Schiff base as a new organic material for nonlinear optical crystals and films with reversible noncentrosymmetry.

Macroscopic single crystals of (E)-5-(diethylamino)-2-((3,5-dinitrophenylimino)methyl)phenol (DNP) were obtained from slow cooling of chloroform or dichlorometane saturated solutions at controlled temperature. X-ray diffraction analysis showed that this compound crystallizes in a noncentrosymmetric space group (P2(1)2(1)2(1)). Thermal analysis was performed and indicated that the crystals are stable until 260 °C. Second-order nonlinear optical properties of DNP were experimentally investigated in solution through EFISH technique and in solid state through the Kurtz-Perry powder technique. Crystals of compound DNP exhibited a second-harmonic signals 39 times larger than of the technologically useful potassium dihydrogenphosphate (KDP) under excitation at infrared wavelengths. In addition, the second-order nonlinear optical properties of DNP were also studied at visible wavelengths through the photorefractive effect and applied to demonstrate dynamic holographic reconstruction.

High hole mobility of 1,2-bis[4'-(diphenylamino)biphenyl-4-yl]-1,2-diphenylethene in field effect transistor.

Triphenylamine-functionalized tetraphenylethene shows aggregation-induced emission feature with unity solid-state fluorescence efficiency. Its amorphous film can function in a p-type FET device with field effect mobility up to 2.6 × 10(-3) cm(2)/Vs.

Synthesis, Characterization and Photophysical Properties of Pyridine-Carbazole Acrylonitrile Derivatives.

We synthesized three novel highly fluorescent compounds, 2-(2'-pyridyl)-3-(N-ethyl-(3'-carbazolyl))acrylonitrile, 2-(3"-pyridyl)-3-(N-ethyl-(3'-carbazolyl))acrylonitrile, and 2-(4-pyridyl)-3-(N-ethyl-(3'-carbazolyl))acrylonitrile by Knoevenagel condensation. The first two were synthesized without solvent in the presence of piperidine as a catalyst; the third was synthesized without a catalyst and with N,N-dimethylformamide as a solvent. In solution, the molar absorption coefficients showed absorptions at 380, 378, and 396 nm, respectively; in solid state, absorptions were at 398, 390, and 442 nm, respectively. The fluorescence emission was at 540, 540 and 604 nm, respectively, the 2-(4-pyridyl)-3-(N-ethyl-(3'-carbazolyl))acrylonitrile showed a red shift in the emission of 64 nm compared to the other two compounds. The fluorescence quantum yield for the compounds in powder form showed values of 0.05, 0.14, and 0.006, respectively; compared with the value measured for the Alq3 reference, 2-(3"-pyridyl)-3-(N-ethyl-(3'-carbazolyl))acrylonitrile had a lightly higher value. The third harmonic generation measurement for 2-(2'-pyridyl)-3-(N-ethyl-(3'-carbazolyl))acrylonitrile yielded a χ(3) value of 5.5 × 10-12 esu, similar to that reported for commercial polymers.

Gigantic two-photon absorption cross sections and strong two-photon excited fluorescence in pyrene core dendrimers with fluorene/carbazole as dendrons and acetylene as linkages.

We report a series of stiff dendrimers (referred to as T1, T2, T3, and T4) that have both gigantic two-photon absorption (TPA) cross sections up to 25,000 GM and strong two-photon excited fluorescence (TPEF) with fluorescence quantum yield of ∼0.5. The large TPA cross sections and high quantum yields of these dendrimers are directly related to their geometrical structures, where the polycyclic aromatic pyrene is chosen as the chromophoric core because of its planar and highly π-conjugated structure, fluorene moieties as dendrons extend the conjugation length through the planar structure, and carbazole moieties are modified at three-, six-, and nine-positions as electron donor. All of these groups are linked with acetylene linkage for effective π-electron delocalization, leading to large TPA cross section and high fluorescence quantum yield. The spectral properties of all dendrimers are investigated by one- and two-photon excitations. Furthermore, steady-state fluorescence excitation anisotropy and quantum chemical calculation are also employed to determine the structure-related mechanism of these dendrimers with gigantic TPA cross sections and high TPEF efficiency. We then show that the improvement of branched chains in the T-series dendrimers enhances the light-harvesting ability. The core emission spectra, fluorescence quantum yield, and fluorescence lifetime are almost invariable by directly exciting the dendrons. These results will provide a guideline for the design of useful two-photon materials with structural motifs that can enhance the TPA cross-section and fluorescence quantum yield of a molecule without causing a red shift of the one- and two-photon excitation wavelengths for specific applications.