Controlled growth of carbon nanotubes for electronic and photovoltaic applications

Carbon nanotubes (CNTs), experimentally observed for the first time twenty years ago, have triggered an unprecedented research effort, on the account of their astonishing structural, mechanical and electronic properties. Unfortunately, the current inability in predicting the CNTs’ properties and the difficulty in controlling their position on a substrate are often limiting factors for the application of this material in actual devices. This research aims at the creation of specific methodologies for controlled synthesis of CNTs, leading to effectively employ them in various fields of electronics, e.g. photovoltaics. Focused Ion Beam (FIB) patterning of Si surfaces is here proposed as a means for ordering the assembly of vertical-aligned CNTs. With this technique, substrates with specific nano-structured morphologies have been prepared, enabling a high degree of control over CNTs’ position and size. On these nano-structured substrates, the growth of CNTs has been realized by chemical vapor deposition (CVD), i.e. thermal decomposition of hydrocarbon gases over a heated catalyst. The most common materials used as catalysts in CVD are transition metals like Fe and Ni; however, their presence in the CNT products often results in shortcomings for electronic applications, especially for those based on silicon, being the metallic impurities incompatible with very-large-scale integration (VLSI) technology. In the present work the role of Ge dots as an alternative catalysts for CNTs synthesis on Si substrates has been thoroughly assessed, finding a close connection between the catalytic activity of such material and the CVD conditions, which can affect both size and morphology of the dots. Successful CNT growths from Ge dots have been obtained by CVD at temperatures ranging from 750 to 1000°C, with mixtures of acetylene and hydrogen in an argon carrier gas. The morphology of the Si surface is observed to play a crucial role for the outcome of the CNT synthesis: natural (i.e. chemical etching) and artificial (i.e. FIB patterning, nanoindentation) means of altering this morphology in a controlled way have been then explored to optimize the CNTs yield. All the knowledge acquired in this study has been finally applied to synthesize CNTs on transparent conductive electrodes (indium-tin oxide, ITO, coated glasses), for the creation of a new class of anodes for organic photovoltaics. An accurate procedure has been established which guarantees a controlled inclusion of CNTs on ITO films, preserving their optical and electrical properties. By using this set of conditions, a CNTenhanced electrode has been built, contributing to improve the power conversion efficiency of polymeric solar cells.

Voltage unbalance improvement in low voltage residential feeders with rooftop PVs using custom power devices

Voltage unbalance is a major power quality problem in low voltage residential feeders due to the random location and rating of single-phase rooftop photovoltaic cells (PV). In this paper, two different improvement methods based on the application of series (DVR) and parallel (DSTATCOM) custom power devices are investigated to improve the voltage unbalance problem in these feeders. First, based on the load flow analysis carried out in MATLAB, the effectiveness of these two custom power devices is studied vis-à-vis the voltage unbalance reduction in urban and semi-urban/rural feeders containing rooftop PVs. Their effectiveness is studied from the installation location and rating points of view. Later, a Monte Carlo based stochastic analysis is carried out to investigate their efficacy for different uncertainties of load and PV rating and location in the network. After the numerical analyses, a converter topology and control algorithm is proposed for the DSTATCOM and DVR for balancing the network voltage at their point of common coupling. A state feedback control, based on pole-shift technique, is developed to regulate the voltage in the output of the DSTATCOM and DVR converters such that the voltage balancing is achieved in the network. The dynamic feasibility of voltage unbalance and profile improvement in LV feeders, by the proposed structure and control algorithm for the DSTATCOM and DVR, is verified through detailed PSCAD/EMTDC simulations.

High penetration of rooftop photovoltaic cells in low voltage distribution networks : voltage imbalance and improvement

Installation of domestic rooftop photovoltaic cells (PVs) is increasing due to feed–in tariff and motivation driven by environmental concerns. Even though the increase in the PV installation is gradual, their locations and ratings are often random. Therefore, such single–phase bi–directional power flow caused by the residential customers can have adverse effect on the voltage imbalance of a three–phase distribution network. In this chapter, a voltage imbalance sensitivity analysis and stochastic evaluation are carried out based on the ratings and locations of single–phase grid–connected rooftop PVs in a residential low voltage distribution network. The stochastic evaluation, based on Monte Carlo method, predicts a failure index of non–standard voltage imbalance in the network in presence of PVs. Later, the application of series and parallel custom power devices are investigated to improve voltage imbalance problem in these feeders. In this regard, first, the effectiveness of these two custom power devices is demonstrated vis–à–vis the voltage imbalance reduction in feeders containing rooftop PVs. Their effectiveness is investigated from the installation location and rating points of view. Later, a Monte Carlo based stochastic analysis is utilized to investigate their efficacy for different uncertainties of load and PV rating and location in the network. This is followed by demonstrating the dynamic feasibility and stability issues of applying these devices in the network.

Thiophene-benzothiadiazole-thiophene (D-A-D) based polymers : Effect of donor/acceptor moieties adjacent to D-A-D segment on photophysical and photovoltaic properties

New push-pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co- thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31100 and 8400 g mol-1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10-4 cm2 V-1 s -1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1:4 ratio, exhibiting a short-circuit current of 7.27 mA cm-2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm-2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm -2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

Design and fabrication of linear pixel arrays for organic photovoltaic modules to achieve scalable power output

We describe a design and fabrication method to enable simpler manufacturing of more efficient organic solar cell modules using a modified flat panel deposition technique. Many mini-cell pixels are individually connected to each other in parallel forming a macro-scale solar cell array. The pixel size of each array is optimized through experimentation to maximize the efficiency of the whole array. We demonstrate that integrated organic solar cell modules with a scalable current output can be fabricated in this fashion and can also be connected in series to generate a scalable voltage output.

Spectroscopic studies of In2O3 nanostructures; photovoltaic demonstration of In2O3/p-Si heterojunction

The thermal oxidation process of the indium nitride (InN) nanorods (NRs) was studied. The SEM studies reveal that the cracked and burst mechanism for the formation of indium oxide (In2O3) nanostructures by oxidizing the InN NRs at higher temperatures. XRD results confirm the bcc crystal structure of the as prepared In2O3 nanostructures. Strong and broad photoluminescence spectrum located at the green to red region with maximum intensity at 566 nm along with a weak ultraviolet emission at 338 nm were observed due to oxygen vacancy levels and free excitonic transitions, respectively. The valence band onset energy of 2.1 eV was observed from the XPS valence band spectrum, clearly justifies the alignment of Fermi level to the donor level created due to the presence of oxygen vacancies which were observed in the PL spectrum. The elemental ratio In:O in as prepared In2O3 was found to be 42:58 which is in close agreement with the stoichiometric value of 40:60. A downward shift was observed in the Raman peak positions due to a possible phonon confinement effect in the nanoparticles formed in bursting mechanism. Such single junction devices exhibit promising photovoltaic performance with fill factor and conversion efficiency of 21% and 0.2%, respectively, under concentrated AM1.5 illumination.

Impact of substrate nitridation on the photoluminescence and photovoltaic characteristics of GaN grown on p-Si (100) by molecular beam epitaxy

This report focuses on the structural and optical properties of the GaN films grown on p-Si (100) substrates along with photovoltaic characteristics of GaN/p-Si heterojunctions fabricated with substrate nitridation and in absence of substrate nitridation. The high resolution X-ray diffraction (HRXRD), atomic force microscopy (AFM), Raman and photoluminescence (PL) spectroscopic studies reveal that the significant enhancement in the structural as well as in the optical properties of GaN epifilms grown with silicon nitride buffer layer when compared with the sample grown without silicon nitride buffer layer. The low temperature PL shows a free excitonic (FX) emission peak at 3.51 eV at the temperature of 5 K with a very narrow line width of 35 meV. Temperature dependent PL spectra follow the Varshni equation well and peak energy blue shifts by similar to 63 meV from 300 to 5 K. Raman data confirms the strain free nature and reasonably good crystallinity of the films. The GaN/p-Si heterojunctions fabricated without substrate nitridation show a superior photovoltaic performance compared to the devices fabricated in presence of substrate nitridation. The discussions have been carried out on the junction properties. Such single junction devices exhibit a promising fill factor and conversion efficiency of 23.36 and 0.12 %, respectively, under concentrated AM1.5 illumination.

Facile synthesis of Cu2CoSnS4 nanoparticles exhibiting red-edge-effect: Application in hybrid photonic devices

Cu2CoSnS4 (CCTS) quaternary semiconducting nanoparticles with size distribution from 20 nm to 60 nm were synthesized by one-pot low temperature time and surfactant dependent hydrothermal route. Nanoparticles were characterized structurally and optically. Excitation dependent fluorescence exhibited a dynamic stoke shift referring to the Red-Edge-Effect with peak shifting by a greater magnitude (>100 nm) towards red side, in all the samples. Hybrid devices, fabricated from CCTS nanoparticle inorganic counterparts benefitting from the conjugation of organic P3HT polymer matrix, were demonstrated for photodetection under infra-red and A. M 1.5 solar light illuminations. Faster rise and decay constants of 37 ms and 166 ms, with one order photocurrent amplification from 1.6 x 10(-6) A in the dark to 6.55 x 10(-5) A, upon the 18.50 mW cm(-2) IR lamp illumination, make CCTS a potential candidate for photodetector and photovoltaic applications. (C) 2013 AIP Publishing LLC.

Design and synthesis of new low band gap organic semiconductors for photovoltaic applications

Donor-acceptor (D-A) conjugated polymers have attracted a good deal of attention in recent years. In D-A systems, the introduction of electron withdrawing groups reduces E-g by lowering the LUMO levels whereas, the introduction of electron donating groups reduces E-g by raising the HOMO levels. Also, conjugated polymers with desired HOMO and LUMO energy levels could be obtained by the proper selection of donor and acceptor units. Because of this reason, D-A conjugated polymers are emerging as promising materials particularly for polymer light emitting diodes (PLEDs) and polymer solar cells (PSCs). We report the design and synthesis of four new narrow band gap donor-acceptor (D-A) conjugated polymers, PTCNN, PTCNF, PTCNV and PTCNO, containing electron donating 3,4-didodecyloxythiophene and electron accepting cyanovinylene units. The effects of further addition of electron donating and electron withdrawing groups to the repeating unit of a D-A conjugated polymer (PTCNN) on its optical and electrochemical properties are discussed. The studies revealed that the nature of D and A units as well as the extent of alternate D-A structure influences the optical and the electrochemical properties of the polymers. All the polymers are thermally stable up to a temperature of 300 degrees C under nitrogen atmosphere. The electrochemical studies revealed that the polymers possess low-lying HOMO energy levels and low-lying LUMO energy levels. In the UV-Vis absorption study, the polymer films displayed broad absorption in the wavelength region of 400-700 nm. The polymers exhibited low optical band gaps in the range 1.70 - 1.77 eV.

Solution Processed Cu2CoSnS4 Thin Films for Photovoltaic Applications

Earth abundant alternative chalcopyrite Cu2CoSnS4 (CCTS) thin films were deposited by a facile sol-gel process onto larger substrates. Temperature dependence of the process control of deposition and desired phase formations was studied in detail. Films were analyzed for complete transformation from amorphous to polycrystalline, with textured structures for stannite phase, as reflected from the X-ray diffraction and with nearly stoichiometric compositions of Cu:Co:Sn:S = 2:0:1:0:1:0:4:0 from EDAX analysis. Morphological investigations revealed that the CCTS films with larger grains, on the order of its thickness, were synthesized at higher temperature of 500 degrees C. The optimal band gap for application in photovoltaics was estimated to be 1.4 eV. Devices with SLG/CCTS/Al geometry were fabricated for real time demonstration of photoconductivity under A.M 1.5 G solar and 1064 rim infrared laser illuminations. A photodetector showed one order current amplification from similar to 1.9 X 10(-6) A in the dark to 2.2 x 10(-5) A and 9.8 X 10(-6) A under A.M 1.5 G illumination and 50 mW cm(-2) IR laser, respectively. Detector sensitivity, responsivity, external quantum efficiency, and gain were estimated as 4.2, 0.12 A/W, 14.74% and 14.77%, respectively, at 50 mW cm(-2) laser illuminations. An ON and OFF ratio of 2.5 proved that CCTS can be considered as a potential absorber in low cost photovoltaics applications.

Reactive interlayer based ultra-low moisture permeable membranes for organic photovoltaic encapsulation

Reactive interlayers consisting of zero valent iron and copper nanoparticles have been successfully incorporated into Surlyn films to fabricate moisture barrier materials with reduced water vapor permeabilities. The reactive nanoparticles dispersed in stearic acid were employed as the interlayers due to their ability to react with moisture. The water vapor transmission rates through the fabricated barrier films with reactive iron and copper interlayers decreased by over 4 orders of magnitude when compared to neat Surlyn. The flexibility and transparency of the barrier films have been evaluated by tensile and UV-visible experiments. Moreover, the accelerated aging studies conducted in accordance with the ISOS-III protocol confirmed the increased lifetimes of the organic photovoltaic (OPV) devices encapsulated with these reactive barrier films.

Heteroepitaxy of Group IV and Group III-V semiconductor alloys for photovoltaic applications

Photovoltaic energy conversion represents a economically viable technology for realizing collection of the largest energy resource known to the Earth -- the sun. Energy conversion efficiency is the most leveraging factor in the price of energy derived from this process. This thesis focuses on two routes for high efficiency, low cost devices: first, to use Group IV semiconductor alloy wire array bottom cells and epitaxially grown Group III-V compound semiconductor alloy top cells in a tandem configuration, and second, GaP growth on planar Si for heterojunction and tandem cell applications.

Metal catalyzed vapor-liquid-solid grown microwire arrays are an intriguing alternative for wafer-free Si and SiGe materials which can be removed as flexible membranes. Selected area Cu-catalyzed vapor-liquid solid growth of SiGe microwires is achieved using chlorosilane and chlorogermane precursors. The composition can be tuned up to 12% Ge with a simultaneous decrease in the growth rate from 7 to 1 μm/min^-1. Significant changes to the morphology were observed, including tapering and faceting on the sidewalls and along the lengths of the wires. Characterization of axial and radial cross sections with transmission electron microscopy revealed no evidence of defects at facet corners and edges, and the tapering is shown to be due to in-situ removal of catalyst material during growth. X-ray diffraction and transmission electron microscopy reveal a Ge-rich crystal at the tip of the wires, strongly suggesting that the Ge incorporation is limited by the crystallization rate.

Tandem Ga_1-xIn_xP/Si microwire array solar cells are a route towards a high efficiency, low cost, flexible, wafer-free solar technology. Realizing tandem Group III-V compound semiconductor/Si wire array devices requires optimization of materials growth and device performance. GaP and Ga_1-xIn_xP layers were grown heteroepitaxially with metalorganic chemical vapor deposition on Si microwire array substrates. The layer morphology and crystalline quality have been studied with scanning electron microscopy and transmission electron microscopy, and they provide a baseline for the growth and characterization of a full device stack. Ultimately, the complexity of the substrates and the prevalence of defects resulted in material without detectable photoluminescence, unsuitable for optoelectronic applications.

Coupled full-field optical and device physics simulations of a Ga_0.51In_0.49P/Si wire array tandem are used to predict device performance. A 500 nm thick, highly doped "buffer" layer between the bottom cell and tunnel junction is assumed to harbor a high density of lattice mismatch and heteroepitaxial defects. Under simulated AM1.5G illumination, the device structure explored in this work has a simulated efficiency of 23.84% with realistic top cell SRH lifetimes and surface recombination velocities. The relative insensitivity to surface recombination is likely due to optical generation further away from the free surfaces and interfaces of the device structure.

Finally, GaP has been grown free of antiphase domains on Si (112) oriented substrates using metalorganic chemical vapor deposition. Low temperature pulsed nucleation is followed by high temperature continuous growth, yielding smooth, specular thin films. Atomic force microscopy topography mapping showed very smooth surfaces (4-6 Å RMS roughness) with small depressions in the surface. Thin films (~ 50 nm) were pseudomorphic, as confirmed by high resolution x-ray diffraction reciprocal space mapping, and 200 nm thick films showed full relaxation. Transmission electron microscopy showed no evidence of antiphase domain formation, but there is a population of microtwin and stacking fault defects.

Direct temperature mapping of nanoscale plasmonic devices.

Side by side with the great advantages of plasmonics in nanoscale light confinement, the inevitable ohmic loss results in significant joule heating in plasmonic devices. Therefore, understanding optical-induced heat generation and heat transport in integrated on-chip plasmonic devices is of major importance. Specifically, there is a need for in situ visualization of electromagnetic induced thermal energy distribution with high spatial resolution. This paper studies the heat distribution in silicon plasmonic nanotips. Light is coupled to the plasmonic nanotips from a silicon nanowaveguide that is integrated with the tip on chip. Heat is generated by light absorption in the metal surrounding the silicon nanotip. The steady-state thermal distribution is studied numerically and measured experimentally using the approach of scanning thermal microscopy. It is shown that following the nanoscale heat generation by a 10 mW light source within a silicon photonic waveguide the temperature in the region of the nanotip is increased by ∼ 15 °C compared with the ambient temperature. Furthermore, we also perform a numerical study of the dynamics of the heat transport. Given the nanoscale dimensions of the structure, significant heating is expected to occur within the time frame of picoseconds. The capability of measuring temperature distribution of plasmonic structures at the nanoscale is shown to be a powerful tool and may be used in future applications related to thermal plasmonic applications such as control heating of liquids, thermal photovoltaic, nanochemistry, medicine, heat-assisted magnetic memories, and nanolithography.

Organic photovoltaic cell employing organic heterojunction as buffer layer

Hexadecafluorophthalocyaninatocopper (F16CuPc)/zine phthalocyanine (ZnPc) heterojunction layer has been used as buffer layer in organic photovoltaic (OPV) cells based on ZnPc and C-60. The F16CuPc/ZnPc heterojunction with highly conductive property decreased the contact resistance between the indium-tin-oxide anode and the organic layer. As a result, the short-circuit current density and fill factor were increased, and the power-conversion efficiency was improved by over 60%. Therefore, the method provides an effective path to improve the performance of OPV cells.

Preparation and photovoltaic property of a new polyfluorene derivative/ZnO nanoparticles hybrid composites

A new kind of polyfluorene copolymers, poly(2,7-(9,9-dioctyl-fluorene)-alt-5,5 -(4',7'-di-2-thienyl-2',1',3',-benzothiadiazole) (PFDTBT), was prepared. The introduction of ZnO nanoparticles with perfect wurtzite crystal character into PFDTBT makes the resulted single-layer photovoltaic device to perform a significant photovoltaic response. Among the tested devices, the best performance is observed for that containing 60 wt% of ZnO nanoparticles, which has a photocurrent density of 1.17 mu A/cm(2), an open circuit voltage of 0.81 V. a fill factor of 0.09 and a power conversion efficiency of 0.009%. The results show that the polyfluorene derivatives/ZnO nanoparticles hybrid composites are excellent fluorescence and photovoltaic materials. (C) 2009 Elsevier B.V. All rights reserved.