Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Analysis of Er3+ incorporation in SnO2 by optical investigation

Er3+ emission in the wide bandgap matrix SnO2 is observed either through a direct Er ion excitation process as well as by an indirect process, through energy transfer in samples codoped with Yb3+ ions. Electron-hole generation in the tin dioxide matrix is also used to promote rare-earth ion excitation. Photoluminescence spectra as function of temperature indicate a slight decrease in the emission intensity with temperature increase, yielding low activation energy, about 3.8meV, since the emission even at room temperature is rather considerable.

Electro-optical properties of Er-doped SnO2 thin films

Photoconductivity of SnO2 sol-gel films is excited, at low temperature, by using a 266 nm line-fourth harmonic-of a Nd:YAG laser. This line has above bandgap energy and promotes generation of electron-hole pairs, which recombines with oxygen adsorbed at grain boundary. The conductivity increases up to 40 times. After removing the illumination on an undoped SnO2 film, the conductivity remains unchanged, as long as the temperature is kept constant. Adsorbed oxygen ions recombine with photogenerated holes and are continuously evacuated from the system, leaving a net concentration of free electrons into the material, responsible for the increase in the conductivity. For Er doped SnO2, the excitation of conductivity by the laser line has similar behavior, however after removing illumination, the conductivity decreases with exponential-like decay. (C) 2003 Elsevier Ltd. All rights reserved.

Above bandgap induced photoexpansion and photobleaching in Ga-Ge-S based glasses

Photoexpansion and photobleaching effects have been examined in glass compositions Ga10Ge25S65 and Ga5Ge25As5S65. Such compositions are promising for optical storage and planar waveguide applications. To evaluate the photoinduced effect, samples were exposed to 351 nm light, varying power density (3-10 W/cm(2)) and exposure time (0-120 min). The exposed areas have been analyzed using atomic force microscopy (AFM) and an expansion of 800 nm is observed for composition Ga10Ge25S65 exposed during 120 min and 5 W/cm(2) power density. The optical absorption edge measured by a spectrophotometer indicates a blue shift (80 nm) after illumination in the composition Ga10Ge25S65. The morphology was examined using a scanning electron microscopy (SEM). The chemical compositions measured using a energy dispersive analyzer (EDX) indicate an increase of the number of sulfur atoms in the irradiated area. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Optical and structural properties of InAlN/GaN Bragg reflectors examined by transmission electron microscopy and electron energy loss spectroscopy

Molecular beam epitaxy growth of ten-period lattice-matched InAlN/GaN distributed Bragg reflectors (DBRs) with peak reflectivity centered around 400nm is reported including optical and transmission electron microscopy (TEM) measurements [1]. Good periodicity heterostructures with crack-free surfaces were confirmed, but, also a significant residual optical absorption below the bandgap was measured. The TEM characterization ascribes the origin of this problem to polymorfism and planar defects in the GaN layers and to the existence of an In-rich layer at the InAlN/GaN interfaces. In this work, several TEM based techniques have been combined.

Electronic, structural, and optical properties of the host and Cr-doped cadmium thioindate

The cadmium thioindate spinel CdIn2S4 semiconductor has potential applications for optoelectronic devices. We present a theoretical study of the structural and optoelectronic properties of the host and of the Cr-doped ternary spinel. For the host spinel, we analyze the direct or indirect character of the energy bandgap, the change of the energy bandgap with the anion displacement parameter and with the site cation distribution, and the optical properties. The main effect of the Cr doping is the creation of an intermediate band within the energy bandgap. The character and the occupation of this band are analyzed for two substitutions: Cr by In and Cr by Cd. This band permits more channels for the photon absorption. The optical properties are obtained and analyzed. The absorption coefficients are decomposed into contributions from the different absorption channels and from the inter-and intra-atomic components.

Electronic and optical properties of substitutional V, Cr and Ir impurities in Cu2ZnSnS4

The substitution of cation atoms by V, Cr and It in the natural and synthetic quaternary Cu2ZnSnS4 semiconductor is analyzed using first-principles methods. In most of the substitutions, the electronic structure of these modified CZTS is characterized for intermediate bands with different occupation and position within of the energy band gap. A study of the symmetry and composition of these intermediate bands is carried out for all substitutions. These bands permit additional photon absorption and emission channels depending on their occupation. The optical properties are obtained and analyzed. The absorption coefficients are split into contributions from the different absorption channels and from the inter- and intra-atomic components. The sub bandgap transitions are significant in many cases because the anion states contribute to the valence, conduction and intermediates bands. These properties could therefore be used for novel optoelectronic devices.

Optical properties of ZnMgO films grown by spray pyrolysis and their application to UV photodetection

This work presents a comprehensive optical characterization of Zn1−xMgxO thin films grown by spray pyrolysis (SP). Absorption measurements show the high potential of this technique to tune the bandgap from 3.30 to 4.11 eV by changing the Mg acetate content in the precursor solution, leading to a change of the Mg-content ranging from 0 up to 35%, as measured by transmission electron microscopy-energy dispersive x-ray spectroscopy. The optical emission of the films obtained by cathodoluminescence and photoluminescence spectroscopy shows a blue shift of the peak position from 3.26 to 3.89 eV with increasing Mg incorporation, with a clear excitonic contribution even at high Mg contents. The linewidth broadening of the absorption and emission spectra as well as the magnitude of the observed Stokes shift are found to significantly increase with the Mg content. This is shown to be related to both potential fluctuations induced by pure statistical alloy disorder and the presence of a tail of band states, the latter dominating for medium Mg contents. Finally, metal–semiconductor–metal photodiodes were fabricated showing a high sensitivity and a blue shift in the cut-off energy from 3.32 to 4.02 eV, i.e., down to 308 nm. The photodiodes present large UV/dark contrast ratios (102 − 107), indicating the viability of SP as a growth technique to fabricate low cost (Zn, Mg)O-based UV photodetectors reaching short wavelengths.

Photoconductivity and Electro-Optical Properties of Wide Band Gap Metal Oxides

The PhD activity described in this Thesis was focused on the study of metal-oxide wide-bandgap materials, aiming at fabricating new optoelectronic devices such as solar-blind UV photodetectors, high power electronics, and gas sensors. Photocurrent spectroscopy and DC photocurrent time evolution were used to investigate the performance of prototypes under different atmospheres, temperatures and excitation wavelengths (or dark conditions). Cathodoluminescence, absorption spectroscopy, XRD and SEM were used to assess structural, morphologic, electrical and optical properties of materials. This thesis is divided into two main sections, each describing the work done on a different metal-oxide semiconductor. 1) MOVPE-grown Ga2O3 thin films for UV solar-blind photodetectors and high power devices The semiconducting oxides, among them Ga2O3, have been employed for several decades as transparent conducting oxide (TCO) electrodes for fabrication of solar cells, displays, electronic, and opto-electronic devices. The interest was mainly confined to such applications, as these materials tend to grow intrinsically n-type, and attempts to get an effective p-type doping has consistently failed. The key requirements of TCO electrodes are indeed high electrical conductivity and good transparency, while crystallographic perfection is a minor issue. Furthermore, for a long period no high-quality substrates and epi-layers were available, which in turn impeded the development of a truly full-oxide electronics. Recently, Ga2O3 has attracted renewed interest, as large single crystals and high-quality homo- and hetero-epitaxial layers became available, which paved the way to novel application areas. Our research group spent the last two years in developing a low temperature (500-700°C) MOVPE growth procedure to obtain thin films of Ga2O3 on different substrates (Dept. of Physics and IMEM-CNR at UNIPR). We obtained a significant result growing on oriented sapphire epitaxial films of high crystalline, undoped, pure phase -Ga2O3 (hexagonal). The crystallographic properties of this phase were investigated by XRD, in order to clarify the lattice parameters of the hexagonal cell. First design and development of solar blind UV photodetectors based on -phase was carried out and the optoelectronic performance is evaluated by means of photocurrent spectroscopy. The UV-response is adequately fast and reliable to render this unusual phase a subject of great interest for future applications. The availability of a hexagonal phase of Ga2O3 stable up to 700°C, belonging to the same space group of gallium nitride, with high crystallinity and tunable electrical properties, is intriguing in view of the development of nitride-based devices, by taking advantage of the more favorable symmetry and epitaxial relationships with respect to the monoclinic β-phase. In addition, annealing at temperatures higher than 700°C demonstrate that the hexagonal phase converts totally in the monoclinic one. 2) ZnO nano-tetrapods: charge transport mechanisms and time-response in optoelectronic devices and sensors Size and morphology of ZnO at the nanometer scale play a key role in tailoring its physical and chemical properties. Thanks to the possibility of growing zinc oxide in a variety of different nanostructures, there is a great variety of applications, among which gas sensors, light emitting diodes, transparent conducting oxides, solar cells. Even if the operation of ZnO nanostructure-based devices has been recently demonstrated, the mechanisms of charge transport in these assembly is still under debate. The candidate performed an accurate investigation by photocurrent spectroscopy and DC-photocurrent time evolution of electrical response of both single-tetrapod and tetrapod-assembly devices. During the research done for this thesis, a thermal activation energy enables the performance of samples at high temperatures (above about 300°C). The energy barrier is related to the leg-to-leg interconnection in the assembly of nanotetrapods. Percolation mechanisms are responsible for both the very slow photo-response (minutes to hours or days) and the significant persistent photocurrent. Below the bandgap energy, electronic states were investigated but their contribution to the photocurrent are two-three order of magnitude lower than the band edge. Such devices are suitable for employ in photodetectors as well as in gas sensors, provided that the mechanism by which the photo-current is generated and gas adsorption on the surface modify the conductivity of the material are known.

First demonstration of 2μm data transmission in a low-loss hollow core photonic Bandgap fiber

The first demonstration of a hollow core photonic bandgap fiber suitable for high-rate data transmission at 2µm is presented. Using a custom built Thulium doped fiber amplifier, error-free 8Gbit/s transmission in an optically amplified data channel at 2008nm is reported for the first time.

Demonstration of amplified data transmission at 2 µm in a low-loss wide bandwidth hollow core photonic bandgap fiber

The first demonstration of a hollow core photonic bandgap fiber (HC-PBGF) suitable for high-rate data transmission in the 2 μm waveband is presented. The fiber has a record low loss for this wavelength region (4.5 dB/km at 1980 nm) and a >150 nm wide surface-mode-free transmission window at the center of the bandgap. Detailed analysis of the optical modes and their propagation along the fiber, carried out using a time-of-flight technique in conjunction with spatially and spectrally resolved (S) imaging, provides clear evidence that the HC-PBGF can be operated as quasi-single mode even though it supports up to four mode groups. Through the use of a custom built Thulium doped fiber amplifier with gain bandwidth closely matched to the fiber's low loss window, error-free 8 Gbit/s transmission in an optically amplified data channel at 2008 nm over 290 m of 19 cell HC-PBGF is reported. © 2013 Optical Society of America.

WDM transmission at 2μm over low-loss hollow core photonic bandgap fiber

World's first demonstration of WDM transmission in a HC-PBGF at the predicted low loss region of 2m is presented. A total capacity of 16 Gbit/s is achieved using 1×8.5 Gbit/s and 3×2.5 Gbit/s channels modulated using NRZ OOK over 290 meters of hollow core fiber. © 2013 OSA.

Tunable coaxial resonators based on silicon optical fibers

Thermal tuning of a coaxial fiber resonator with a silica cladding surrounding an inner silicon core is investigated. By pumping the silicon with below bandgap light, it is possible to redshift the WGM resonances. © 2014 OSA.