Optical designs for improved solar cell performance

The solar resource is the most abundant renewable resource on earth, yet it is currently exploited with relatively low efficiencies. To make solar energy more affordable, we can either reduce the cost of the cell or increase the efficiency with a similar cost cell. In this thesis, we consider several different optical approaches to achieve these goals. First, we consider a ray optical model for light trapping in silicon microwires. With this approach, much less material can be used, allowing for a cost savings. We next focus on reducing the escape of radiatively emitted and scattered light from the solar cell. With this angle restriction approach, light can only enter and escape the cell near normal incidence, allowing for thinner cells and higher efficiencies. In Auger-limited GaAs, we find that efficiencies greater than 38% may be achievable, a significant improvement over the current world record. To experimentally validate these results, we use a Bragg stack to restrict the angles of emitted light. Our measurements show an increase in voltage and a decrease in dark current, as less radiatively emitted light escapes. While the results in GaAs are interesting as a proof of concept, GaAs solar cells are not currently made on the production scale for terrestrial photovoltaic applications. We therefore explore the application of angle restriction to silicon solar cells. While our calculations show that Auger-limited cells give efficiency increases of up to 3% absolute, we also find that current amorphous silicion-crystalline silicon heterojunction with intrinsic thin layer (HIT) cells give significant efficiency gains with angle restriction of up to 1% absolute. Thus, angle restriction has the potential for unprecedented one sun efficiencies in GaAs, but also may be applicable to current silicon solar cell technology. Finally, we consider spectrum splitting, where optics direct light in different wavelength bands to solar cells with band gaps tuned to those wavelengths. This approach has the potential for very high efficiencies, and excellent annual power production. Using a light-trapping filtered concentrator approach, we design filter elements and find an optimal design. Thus, this thesis explores silicon microwires, angle restriction, and spectral splitting as different optical approaches for improving the cost and efficiency of solar cells.

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.

The effect of interposing nanocrystalline Si(B) P plus layer on the photovoltaic properties of a-Si: H tandem solar cells

Tandem amorphous silicon solar cells have attracted extensive interest because of better performance than single junction counterpart. As n/p junctions play an important role in the current transportation of tandem solar cells, it is important to design and fabricate good n/p junctions.The properties of the n/p junction of amorphous silicon (a-Si) were studied. We investigate the effect of interposing a nanocrystalline p(+) layer between n (top cell) and p (bottom cell) layers of a tandem solar cell. The crystalline volume fraction, the band gap, the conductivity and the grain size of the nanocrystalline silicon (nc-Si) p(+) layer could be modulated by changing the deposition parameters.Current transport in a-Si based n/p ("tunnel") junctions was investigated by current-voltage measurements. The voltage dependence on the resistance (V/J) of the tandem cells was examined to see if n/p junction was ohmic contact. To study the affection of different doping concentration to the properties of the nc-Si p(+) layers which varied the properties of the tunnel junctions, three nc-Si p(+) film samples were grown, measured and analyzed.

Influence of interface modification on the performance of polymer/Bi2S3 nanorods bulk heterojunction solar cells

In this paper, bulk heterojunction photovoltaic devices based on the poly[2-methoxy-5-(3',7'-dimethyloctyloxy)- 1,4-phenylenevinylene] (MDMO-PPV):Bi2S3 nanorods hybrid material were present. To optimize the performance of the devices, the interface modification of the hybrid material that has a significant impact on the exciton dissociation efficiency was studied. An improvement in the device performance was achieved by modifying the Bi2S3 surface with a thin dye layer. Moreover, modifying the Bi2S3 surface with anthracene-9-carboxylic acid can enhance the performance further. Compared with the solar cells with Bi2S3 nanorods hybrid with the MDMO-PPV as the active layer, the anthracene-9carboxylic acid modified devices are better in performance, with the power conversion efficiency higher by about one order in magnitude.

High-performance dye-sensitized solar cells based on solvent-free electrolytes produced from eutectic melts

Low-cost excitonic solar cells based on organic optoelectronic materials are receiving an ever-increasing amount of attention as potential alternatives to traditional inorganic photovoltaic devices. In this rapidly developing field, the dye-sensitized solar cell(1) (DSC) has achieved so far the highest validated efficiency of 11.1% (ref. 2) and remarkable stability(3).

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.

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.

Novel NIR-absorbing conjugated polymers for efficient polymer solar cells: effect of alkyl chain length on device performance

Three low bandgap conjugated polymers, i.e., PDTPBT-C8, PDTPBT-C6 and PDTPBT-C5, which consist of alternating N-alkyl dithieno[3,2-b: 2',3'-d] pyrrole and 2,1,3-benzothiadiazole units and carry 1-octylnonyl, 1-hexylheptyl and 1-pentylhexyl as side chains, respectively, were synthesized. These polymers show strong absorption in the wavelength range of 600-900 nm with enhanced absorption coefficient as the length of alkyl chain decreases. The film morphology of the polymers and 1-(3-methoxycarbonyl) propyl-1-phenyl-[6,6]-C-61 (PCBM) blends is also dependent on the alkyl chain length. As the length decreases, the film becomes more uniform and the domian size decreases from 400-900 nm for PDTPBT-C8 to similar to 50 nm for PDTPBT-C5.

Enhanced charge collection in polymer photovoltaic cells by using an ethanol-soluble conjugated polyfluorene as cathode buffer layer

We report enhanced polymer photovoltaic (PV) cells by utilizing ethanol-soluble conjugated poly (9, 9-bis (6'-diethoxylphosphorylhexyl) fluorene) (PF-EP) as a buffer layer between the active layer consisting of poly(3-hexylthiophene)/[6, 6]-phenyl C61-butyric acid methyl ester blend and the Al cathode. Compared to the control PV cell with Al cathode, the introduction of PF-EP effectively increases the shunt resistance and improves the photo-generated charge collection since the slightly thicker semi-conducting PF-EP layer may restrain the penetration of Al atoms into the active layer that may result in increased leakage current and quench photo-generated excitons. The power conversion efficiency is increased ca. 8% compared to the post-annealed cell with Al cathode.

Solvent Vapor-Induced Self Assembly and its Influence on Optoelectronic Conversion of Poly(3-hexylthiophene): Methanofullerene Bulk Heterojunction Photovoltaic Cells

Nanoscale-phase separation of electron donor/acceptor blends is crucial for efficient charge generation and collection in Polymer bulk heterojunction photovoltaic cells. We investigated solvent vapor annealing effect of poly(3-hexylthiophene) (P3HT)/methanofullerene (PCBM) blend oil its morphology and optoelectronic properties. The organic solvents of choice for the treatment have a major effect oil the morphology of P3HT/PCBM blend and the device performance. Ultraviolet-visible absorption spectro,;copy shows that specific solvent vapor annealing can induce P3HT self-assembling to form well-ordered structure; and hence, file absorption in the red region and the hole transport are enhanced. The solvent that has a poor Solubility to PCBM Would cause large PCBM Clusters and result in a rough blend film. By combining an appropriate solvent vapor treatment and post-thermal annealing of the devices, the power conversion efficiency is enhanced.

Performance Enhancement of Polymer Light-Emitting Diodes by Using Ultrathin Fluorinated Polyimide Modifying the Surface of Poly(3,4-ethylene dioxythiophene):Poly(styrenesulfonate)

Herein, an insulating fluorinated polyimide (F-PI) is utilized as an ultrathin buffer layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) in polymer light-emitting diodes to enhance the device performance. The selective solubility of F-PI in common solvents avoids typical intermixing interfacial problems during the sequential multilayer spin-coating process. Compared to the control device, the F-PI modification causes the luminous and power efficiencies of the devices to be increased by a factor of 1.1 and 4.7, respectively, along with almost 3-fold device lifetime enhancement. Photovoltaic measurement, single-hole devices, and X-ray photoelectron spectroscopy, are utilized to investigate the underlying, mechanisms, and it is found that the hole injection barrier is lowered owing to the interactions between the PEDOT:PSS and F-PI. The F-PI modified PEDOT:PSS layer demonstrates step-up ionization potential profiles from the intrinsic bulk PEDOT:PSS side toward the F-PI-modified PEDOT:PSS surface, which facilitate the hole injection.

Effect of Poly (3-hexylthiophene) Nanofibrils on Charge Separation and Transport in Polymer Bulk Heterojunction Photovoltaic Cells

Crystalline poly (3-hexylthiophene) (P3HT) nanofibrils are introduced into the P3HT: [6, 6]-phenyl C61-butyric acid methyl ester (PCBM) composite films via P3HT preaggregation in solution by adding a small amount of acetone, and the correlation of P3HT nanofibrils and the optoelectronic properties of P3HT:PCBM bulk heterojunction photovoltaic cells is investigated. It is found that the optical absorption and the hole transport or the resulted P3HT:PCBM composite films increase with the increase of the amount of P3HT nanofibrils due to the increased P3HT crystallinity and highly interconnected nanofibrillar P3HT networks. However, it is also found that high contents of crystalline P3HT nanofibrils may restrain PCBM molecules from demixing with the P3HT component that forms electron traps in the active layer. and hence reduce the charge collection efficiency. Small contents of P3HT nanofibrils not only improve the demixing between P3HT and PCBM components, but also enhance the hole transport via crystalline P3HT nanofibrillar networks, resulting in efficient charge collection.

Toward high-performance polymer solar cells: The importance of morphology control

Polymer solar cells have the potential to become a major electrical power generating tool in the 21st century. R&D endeavors are focusing on continuous roll-to-roll printing of polymeric or organic compounds from solution-like newspapers-to produce flexible and lightweight devices at low cost. It is recognized, though, that besides the functional properties of the compounds the organization of structures on the nanometer level-forced and controlled mainly by the processing conditions applied-determines the performance of state-of-the-art polymer solar cells. In such devices the photoactive layer is composed of at least two functional materials that form nanoscale interpenetrating phases with specific functionalities, a so-called bulk heterojunction. In this perspective article, our current knowledge on the main factors determining the morphology formation and evolution is introduced, and gaps of our understanding on nanoscale structure-property relations in the field of high-performance polymer solar cells are addressed. Finally, promising routes toward formation of tailored morphologies are presented.