Gerardo Hernandez-Sosa

Plasmonic Photosensitization of a Wide Band Gap Semiconductor: Converting Plasmons to Charge Carriers

A fruitful paradigm in the development of low-cost and efficient photovoltaics is to dope or otherwise photosensitize wide band gap semiconductors in order to improve their light harvesting ability for light with sub-band-gap photon energies.(1-8) Here, we report significant photosensitization of TiO2 due to the direct injection by quantum tunneling of hot electrons produced in the decay of localized surface-plasmon polaritons excited in gold nanoparticles (AuNPs) embedded in the semiconductor (TiO2). Surface plasmon decay produces electron-hole pairs in the gold.(9-15) We propose that a significant fraction of these electrons tunnel into the semiconductors conduction band resulting in a significant electron current in the TiO2 even when the device is illuminated with light with photon energies well below the semiconductors band gap. Devices fabricated with (nonpercolating) multilayers of AuNPs in a TiO2 film produced over 1000-fold increase in photoconductance when illuminated at 600 nm over what TiO2 films devoid of AuNPs produced. The overall current resulting from illumination with visible light is ∼50% of the device current measured with UV (ℏω>Eg band gap) illumination. The above observations suggest that plasmonic nanostructures (which can be fabricated with absorption properties that cover the full solar spectrum) can function as a viable alternative to organic photosensitizers for photovoltaic and photodetection applications.

Epitaxy of Rodlike Organic Molecules on Sheet Silicates—A Growth Model Based on Experiments and Simulations

During the last years, self-assembled organic nanostructures have been recognized as a proper fundament for several electrical and optical applications. In particular, phenylenes deposited on muscovite mica have turned out to be an outstanding material combination. They tend to align parallel to each other forming needlelike structures. In that way, they provide the key for macroscopic highly polarized emission, waveguiding, and lasing. The resulting anisotropy has been interpreted so far by an induced dipole originating from the muscovite mica substrate. Based on a combined experimental and theoretical approach, we present an alternative growth model being able to explain molecular adsorption on sheet silicates in terms of molecule−surface interactions only. By a comprehensive comparison between experiments and simulations, we demonstrate that geometrical changes in the substrate surface or molecule lead to different molecular adsorption geometries and needle directions which can be predicted by our growth model.

The Compromises of Printing Organic Electronics: A Case Study of Gravure‐Printed Light‐Emitting Electrochemical Cells

Light-emitting electrochemical cells (LECs) are fabricated by gravure printing. The compromise between device performance and printing quality is correlated to the ink formulation and the printing process. It is shown that the rheological properties of the ink formulations of LECs can be tailored without changing the chemical composition of the material blend.

Organic-organic heteroepitaxy of red-, green-, and blue-emitting nanofibers.

Self-assembly processes and organic-organic heteroepitaxy are powerful techniques to obtain highly ordered molecular aggregates. Here we demonstrate that combining both methods allows not only to fabricate highly crystalline and uniaxially oriented self-assembled nanofibers but also to tune their polarized emission. We show that submonolayer coverage of sexithiophene on top of para-sexiphenyl nanofibers is sufficient to change their emission color from blue to green. Triband emission in the red, green, and blue is generated in nanofibers with thicker sexithiophene coverage, where layers of co-oriented crystals are separated by green-emitting molecular sheets.

Investigation of Solution-Processed Ultrathin Electron Injection Layers for Organic Light-Emitting Diodes

We study two types of water/alcohol-soluble aliphatic amines, polyethylenimine (PEI) and polyethylenimine-ethoxylated (PEIE), for their suitability as electron injection layers in solution-processed blue fluorescent organic light-emitting diodes (OLEDs). X-ray photoelectron spectroscopy is used to determine the nominal thickness of the polymer layers while ultraviolet photoelectron spectroscopy is carried out to determine the induced work-function change of the silver cathode. The determined work-function shifts are as high as 1.5 eV for PEI and 1.3 eV for PEIE. Furthermore, atomic force microscopy images reveal that homogeneous PEI and PEIE layers are present at nominal thicknesses of about 11 nm. Finally, we solution prepare blue emitting polymer-based OLEDs using PEI/PEIE in combination with Ag as cathode layers. Luminous efficiency reaches 3 and 2.2 cd A(-1), whereas maximum luminance values are as high as 8000 and 3000 cd m(-2) for PEI and PEIE injection layers, respectively. The prepared devices show a comparable performance to Ca/Ag OLEDs and an improved shelf lifetime.

Color tuning of nanofibers by periodic organic-organic hetero-epitaxy.

We report on the epitaxial growth of periodic para-hexaphenyl (p-6P)/α-sexi-thiophene (6T) multilayer heterostructures on top of p-6P nanotemplates. By the chosen approach, 6T molecules are forced to align parallel to the p-6P template molecules, which yields highly polarized photoluminescence (PL)-emission of both species. The PL spectra show that the fabricated multilayer structures provide optical emission from two different 6T phases, interfacial 6T molecules, and 3-dimensional crystallites. By a periodical deposition of 6T monolayers and p-6P spacers it is demonstrated that the strongly polarized spectral contribution of interfacial 6T can be precisely controlled and amplified. By analyzing the PL emission of both 6T phases as a function of p-6P spacer thickness (Δdp–6P) we have determined a critical value of Δdp–6P ≈ 2.73 nm where interfacial 6T runs into saturation and the surplus of 6T starts to cluster in 3-dimensional crystallites. These results are further substantiated by UPS and XRD measurements. Moreover, it is demonstrated by morphological investigations, provided by scanning force microscopy and fluorescence microscopy, that periodical deposition of 6T and p-6P leads to a significant improvement of homogeneity in PL-emission and morphology of nanofibers. Photoluminescence excitation experiments in combination with time-resolved photoluminescence demonstrate that the spectral emission of the organic multilayer nanofibers is dominated by a resonant energy transfer from p-6P host- to 6T guest-molecules. The sensitization time of the 6T emission in the 6T/p-6P multilayer structures depends on the p-6P spacer thickness, and can be explained by well separated layers of host–guest molecules obtained by organic–organic heteroepitaxy. The spectral emission and consequently the fluorescent color of the nanofibers can be efficiently tuned from the blue via white to the yellow-green spectral range.

High-efficiency panchromatic hybrid Schottky solar cells.

Nanostructured Schottky inorganic-organic solar cells provide overall power conversion efficiencies exceeding 3%, with extremely large short-circuit photocurrents. The device EQE faithfully tracks the absorptance of the CdSe nanorods, and the IQE is approximately constant over the entire visible spectrum as opposed to a p-n junction hybrid solar cell fabricated with a highly absorbing organic polymer.

Manifestation of Carrier Relaxation Through the Manifold of Localized States in PCDTBT:PC60BM Bulk Heterojunction Material: The Role of PC84BM Traps on the Carrier Transport

The transport and relaxation of photogenerated carriers in a bulk heterojunction (BHJ) material made of a blend of PCDTBT and PC(60) BM are studied as a function of the concentration of PC(84)BM impurities. For low concentrations of PC(84)BM, the increasing activation energy with delay time indicates transport dominated by trap-limited carrier drift while the photocarriers relax through a manifold of disorder-induced localized states near the band edge. In the BHJ material with high concentration of PC(84)BM, transport is dominated by carrier hopping within the PC(84)BM impurity band.

Biodegradable Polycaprolactone as Ion Solvating Polymer for Solution-Processed Light-Emitting Electrochemical Cells.

In this work, we demonstrate the use of the biodegradable polymer polycaprolactone (PCL) as the ion solvating polymer in solution-processed light-emitting electrochemical cells (LEC). We show that the inclusion of PCL in the active layer yields higher ionic conductivities and thus contributes to a rapid formation of the dynamic p-i-n junction and reduction of operating voltages. PCL shows no phase separation with the emitter polymer and reduces film roughness. The devices show light-emission at voltages as low as 3.2 V and lifetimes on the order of 30 h operating above 150 cd m−2 with turn-on times <20 s and current and luminous efficacies of 3.2 Cd A−1 and 1.5 lm W−1 respectively.

Degradation Mechanisms in Organic Light-Emitting Diodes with Polyethylenimine as a Solution-Processed Electron Injection Layer

In this work, we investigate the performance and operational stability of solution-processed organic light-emitting diodes (OLEDs), which comprise polyethylenimine (PEI) as an electron injection layer (EIL). We show that the primary degradation mechanism in these OLEDs depends on the cathode metal that is used in contact with the EIL. In the case of Al, the deterioration in OLED performance during electrical driving is mainly caused by excitons which reach and subsequently degrade the emitter/PEI interface. In contrast, in the case of Ag, device performance degradation occurs due to an additional mechanism: hole accumulation at the emitter/PEI interface and a consequent drop in the emitter quantum yield. As a result, the operational lifetime of OLEDs that use PEI as EIL can vary significantly with the cathode material, and at a current density of 20 mA cm-2, LT50 lifetimes of ∼200 h and <10 h are obtained for Al and Ag, respectively. Finally, we show that the first degradation mechanism can be significantly slowed by using a mixture of PEI and ZnO nanoparticles as EIL. As a result, the operational lifetime of OLEDs with an Al cathode is increased to more than 1000 h, without adversely affecting device performance. This lifetime is significantly longer than that of a LiF/Al reference OLED.