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ABSTRACT

The present study is focused on low-cost preparation of thin film TiO2|CuInS2 nanocomposite three-dimensional (3D) solar cells. With the aid of a simple spray deposition method, we have been able to obtain 3D solar cells, with a remarkable energy conversion efficiency of 5%. The new 3D solar cell design has the potential to breakdown the price barrier and to open up new production technologies for low-cost photovoltaic solar cells. Many solar technologies have been, and continue to be, developed to harness energy from the Sun, an essentially unlimited source of free and environmentally friendly energy. One such technology—photovoltaic (PV) cells—converts sunlight into electricity without producing the harmful emissions that are a by-product of burning fossil fuels in traditional power plants. Typical PV cells are composed of several layers: two different layers of silicon, a metal backing, an antireflective coating, and metal conductor strips. As solar radiation hits the silicon, the energy knocks electrons loose from the silicon atoms; the free electrons then flow out of the cell along the metal conductor strips as electrical current. PV cells are usually packaged in modules or panels, which are then connected to one another in arrays. PV cells have a variety of applications, from personal electronic devices (such as calculators, cell phone chargers, and bicycle lights) to utility-scale electricity generation at a power plant. Spacecraft and satellites also utilize PV cells to supply energy while in space. Other common uses on the ground include powering road signs, emergency telephones, streetlamps, and driveway lights. PV panels can also be installed to produce environmentally friendly electricity for homes and buildings. In addition, PV systems can provide electricity to rural areas that do not have access to the electrical grid. The materials and manufacturing techniques used to make PV systems are expensive. High production costs, then, have kept the technology from becoming widely implemented. Despite incentives such as subsidies and tax credits, homeowners still have to pay significant initial costs. However, even though there may be higher A solar cell or photovoltaic cell is a device that converts light energy into electrical energy. Sometimes the term solar cell is reserved for devices intended specifically to capture energy from sunlight, while the term photovoltaic cell is used when the light source is unspecified. The device needs to fulfill only two functions: photo generation of charge carriers (electrons and holes) in a light-absorbing material, and separation of the charge carriers to a conductive contact that will transmit the electricity. This conversion is called the photovoltaic effect, and the field related to solar cells is known as photovoltaic‘s.

weight and mechanical complexity. which are about 100 microns tall. accidentally found that silicon doped with certain impurities was very sensitive to light. 1883: First solar cell was built by Charles Fritts.and built from arrays containing millions of vertically-aligned carbon nanotubes. A global patent application has been filed for the technology. Because the tower structures can trap and absorb light received from many different angles. The solar cell or photovoltaic cell fulfills two fundamental functions: Photogeneration of charge carriers (electrons and holes) in a light-absorbing material Separation of the charge carriers to a conductive contact to transmit electricity INTRODUCTION Unique three-dimensional solar cells that capture nearly all of the light that strikes them could boost the efficiency of photovoltaic (PV) systems while reducing their size. NewCyte Inc. that would mean less weight and less space taken up with the PV system. The GTRI photovoltaic cells trap light between their tower structures. reducing the amount of energy they absorb. the Air Force Research Laboratory.. The research has been sponsored by the Air Force Office of Scientific Research." said Jud Ready. On a satellite or other spacecraft. experimenting with semiconductors. LLC. "By capturing more of the light in our 3D structures. 1946: Russell Ohl patented the modern solar cell 1954: Modern age of solar power technology arrives . and Intellectual Property Partners. The new 3D solar cells capture photons from sunlight using an array of miniature "tower" structures that resemble high-rise buildings in a city street grid."The 3D design was described in the March 2007 issue of the journal JOM. published by The Minerals. could also change the way solar cells are designed for a broad range of applications. 40 microns by 40 microns square.Bell Laboratories."Our goal is to harvest every last photon that is available to our cells. we can use much smaller photovoltaic arrays. reducing weight and complexity – and improving reliability . and by enabling efficiency improvements in photovoltaic coating materials. The cells could find near-term applications for powering spacecraft. That could allow them to be used on spacecraft without the mechanical aiming systems that maintain a constant orientation to the sun. the new cells remain efficient even when the sun is not directly overhead. Conventional flat solar cells reflect a significant portion of the light that strikes them. 10 microns apart -. a senior research engineer in the Electro-Optical Systems Laboratory at the Georgia Tech Research Institute (GTRI). Metals and Materials Society. who coated the semiconductor selenium with an extremely thin layer of gold to form the junctions (1% efficient).HISTORY • 1839: Photovoltaic effect was first recognized by French physicist • • • • • Alexandre-Edmond Becquerel.

the more likely it is that they will recombine with a hole -reducing the electrical current. Once the carbon nanotube towers have been grown. The patterned wafer is then placed into a furnace heated to 780 degrees Celsius. their coatings can be madethinner. In the finished cells. "The efficiency of our cells increases as the sunlight goes away from perpendicular. each mobile electron leaves behind a "hole" in the atomic matrix of the coating. Because the 3D cells absorb more of the photons than conventional cells. Atop that. In a process known as chemical vapor deposition. whose energy then liberates electrons from the photovoltaic materials to create electrical current. However. the carbon grows arrays of multi-walled carbon nanotubes atop the iron patterns." Ready noted. The researchers first coat the wafer with a thin layer of iron using a photolithography process that can create a wide variety of patterns. so we may not need mechanical arrays to rotate our cells. which can also serve as the solar cell‘s bottom junction. reducing the likelihood that recombination will take place.. the carbon nanotube arrays serve both as support for the 3D arrays and as a conductor . the researchers use a process known as molecular beam epitaxy to coat them with cadmium telluride (CdTe) and cadmium sulfide (CdS) which serve as the p-type and n-type photovoltaic layers. a thin coating of indium tin oxide. a clear conducting material. allowing the electrons to exit more quickly. where the carbon and hydrogen separate. That boosts the "quantum efficiency" – the rate at which absorbed photons are converted to electrons of the 3D cells. the photovoltaic coatings must be thick enough to capture the photons. is added to serve as the cell‘s top electrode. Hydrocarbon gases are then flowed into furnace. In conventional flat solar cells. The ability of the 3D cells to absorb virtually all of the light that strikes them could also enable improvements in the efficiency with which the cells convert the photons they absorb into electrical current. Fabrication of the cells begins with a silicon wafer. The longer it takes electrons to exit the PV material.

 Free electrons flow through the material to produce electricity. "We have demonstrated that we can extract electrons using this approach. leaving another hole behind – hole can propagate through lattice. Ready also wants to study the optimal heights and spacing for the towers. "Now we need to get a good baseline to see where we compare to existing materials.  Different PV materials have different band gap energies. NewCyte. and to determine the trade-offs between spacing and the angle at which the light hits the structures. low cost technology for depositing semiconductor layers directly on individual fullerenes. The researchers chose to make their prototypes cells from the cadmium materials because they were familiar with them from other research. Flood. Testing must verify their ability to survive launch and operation in space. However. Another commercialization path is being followed by an Ohio company. ." Ready said.  Photons with less energy than the band gap energy pass through the       DOPED SEMICONDUCTOR Absorption of a photon Formation of electron-hole pair (exciton) Exciton diffusion to Junction Charge separation Charge transport to the anode (holes) and cathode (electrons) Supply a direct current for the load. and selecting the best material for specific applications will be a goal of future research. for instance.  Photons with energy equal to the band gap energy are absorbed to create free electrons. The new cells face several hurdles before they can be commercially produced." explained Dennis J. And production techniques will have to scaled up from the current two-inch laboratory prototypes. NewCyte‘s president and CTO.  Positive charges (holes) flow in opposite direction. a broad range of other photovoltaic materials could also be used. how to optimize this and what‘s needed to advance this technology. tightly bound in covalent bonds. which is partnering with GTRI to use the 3D approach for terrestrial solar cells.connecting the photovoltaic materials to the silicon wafer. The Air Force Office of Scientific Research has awarded the company a Small Business Technology Transfer (STTR) grant to develop the technology." Intellectual Property Partners of Atlanta holds the rights to the 3D solar cell design and is seeking partners to commercialize the technology. Our goal is to achieve performance and cost levels that will make solar cells using the GTRI PHOTON ABSORPTION Photon is absorbed and energy is given to an electron in the crystal lattice  Usually this electron is in valence band. "NewCyte has patent pending.  Energy given by the photon ―excites‖ it into the conduction band  Covalent bond now has one fewer electron (hole).  Bonded electrons of neighboring atoms can move into the ‗hole‘. "We are using our technology to grow the same semiconductor layers on the carbon nanotube towers that GTRI has already demonstrated.

 p-i-n and n-i-p Devices  A three-layer sandwich is created.          FIRST GENERATION Single crystal silicon wafers (c-Si) Second Generation Amorphous silicon (a-Si) Polycrystalline silicon (poly-Si) Cadmium telluride (CdTe) Copper indium gallium diselenide (CIGS) alloy Third Generation Nanocrystal solar cells Photoelectrochemical (PEC) cells • Gräetzel cells • Polymer solar cells • Dye sensitized solar cell (DSSC) . Light red zone is positively charged. Gray regions are charge neutral.  Heterojunction Device  Junction is formed by contacting two different semiconductor.  p-n junction is located so that the maximum amount of light is  absorbed near it. CELL STRUCTURES Homojunction Device  Single material altered so that one side is p-type and the other side  is n-type. Electrons and holes concentration are reported respectively with blue and red lines.low bandgap that readily absorbs light.  Bottom layer .  Light generates free electrons and holes in the intrinsic region.      Semiconductor doped to change electronic properties n-type semiconductor increase number free electrons p-type semiconductor increase number free ‗holes‘      ELECTRICITY GENERATION p-n junction in thermal equilibrium w/ zero bias voltage applied.high bandgap selected for its transparency to light. Electric field shown on the bottom.  Contains a middle intrinsic layer between n-type layer and p-type layer.  Top layer . light blue zone is negatively charged. the electrostatic force on electrons and holes and the direction in which the diffusion tends to move electrons and holes.

is wasted as heat SECOND GENERATION: OVERVIEW Thin-film Technology • Based on the use of thin-film deposits of semiconductors. • Cells are typically made using a crystalline silicon wafer.11 eV FIRST GENERATION: RESEARCH CELLS FIRST GENERATION: EVALUATION Advantages • • • • • • • • • Broad spectral absorption range High carrier mobilities Disadvantages Requires expensive manufacturing technologies Growing and sawing of ingots is a highly energy intensive process Fairly easy for an electron generated in another molecule to hit a hole left behind in a previous photoexcitation. • More recent approach which saves energy is to process discrete cells on silicon • wafers cut from multicrystalline ribbons • Band gap ~1. multiple junction photovoltaic • cells. • Contributes greatly to reduced costs for thin film solar cells. . single layer p-n junction diode. Much of the energy of higher energy photons. • Several technologies/semiconductor materials currently under investigation or • in mass production • Deposition of thin layers of non-crystalline-silicon materials on inexpensive • substrates using PECVD. • Consists of a large-area.• Fourth Generation • Hybrid . at the blue and violet end of the spectrum. • Using of thin-films reduces mass of material required for cell design.inorganic crystals within a polymer matrix FIRST GENERATION (SILICON) First generation photovoltaic cells are the dominant technology in the commercial production of solar cells. • Approaches • Ingots can be either monocrystalline or multicrystalline • Most common approach is to process discrete cells on wafers sawed from • silicon ingots. accounting for more than 86% of the solar cell market. • Devices initially designed to be high-efficiency.

to form p.Plasma Enhanced CVD Uses an ionized vapor. Often a halide or hydride of the deposited element. • Band gap ~ 1. especially in thin-film solar cell technology . Cheaper than silicon.• Thin-film deposition Technique for depositing a thin film of material onto a substrate.1 eV • Cadmium telluride (CdTe) cells deposited on glass • Crystalline compound formed from cadmium and tellurium with a zinc blende (cubic) crystal • structure (space group F43m) • Usually sandwiched with cadmium sulfide (CdS) to form a p-n junction photovoltaic solar cell. or plasma. as a precursor Relies on electromagnetic means (electric current. SECOND GENERATION: TYPES Amorphous silicon cells deposited on stainless-steel ribbon • Can be deposited over large areas by plasma-enhanced chemical vapor deposition • Can be doped in a fashion similar to c-Si.not as efficient • Band gap ~ 1.38 eV SECOND GENERATION: EVALUATION Advantages .or n-type layers • Used to produce large-area photovoltaic solar cells • Band gap ~ 1.7 eV • Polycrystalline silicon • Consists solely of crystalline silicon grains (1mm).58 eV • Copper indium gallium diselenide (CIGS) alloy cells • Deposited on either glass or stainless steel substrates • More complex heterojunction model • Band gap ~ 1. Layer thickness can be controlled to within a few tens of nanometers Single layers of atoms can be deposited SECOND GENERATION: PECVD Plasma Enhanced Chemical Vapor Deposition • Chemical vapor deposition (CVD) Chemical process using a gas-phase precursor. separated by grain boundaries • Main advantage over amorphous Si: mobility of the charge carriers can be orders or magnitude larger • Material shows greater stability under electric field and light-induced stress. microwave excitation) to produce plasma. • PECVD .

• • • • • • • • • Lower manufacturing costs Lower cost per watt can be achieved Reduced mass Less support is needed when placing panels on rooftops Allows fitting panels on light or flexible materials. DISADVANTAGES Typically. even textiles. or quantum dots • Lead selenide (PbSe) semiconductor • Cadmium telluride (CdTe) semiconductor • Quantum dot is a semiconductor nanostructure • Confines the motion of conduction band electrons. or • excitons in all three spatial directions. • Devices include: • Nanocrystal solar cells • Photo electrochemical cells • Gräetzel Cell • Dye-sensitized hybrid solar cells • Polymer solar cells THIRD GENERATION: TYPES Nanocrystal solar cells • Solar cells based on a silicon substrate with a coating of nanocrystals • Silicon substrate has small grains of nanocrystals. valence band holes. the efficiencies of thin-film solar cells are lower compared with silicon (wafer-based) solar cells Amorphous silicon is not stable Increased toxicity THIRD GENERATION: OVERVIEW Different Semiconductor Technology • Very different from the previous semiconductor devices • Do not rely on a traditional p-n junction to separate • photo generated charge carriers. • Thin film of nano crystals is obtained by a process known as ―spincoating‖ • Excess amount of solution placed onto a substrate then rotated very • quickly • Higher current potential for solar cells .

diffuse to the back electrode to receive Electrons THIRD GENERATION: TYPES Polymer solar cells • ‗Bulk heterojunctions‘ between an organic polymer and organic molecule • as electron acceptor. The oxidized ions in the electrolyte. The electrons are collected by front electrode and supplied to external load. but • works in concert with the electrolyte. • Gräetzel cells • Dye-sensitized PEC cells • Semiconductor solely used for charge separation. . Dye molecules are electrically reduced to their initial states by electrons transferred from redox couple in the electrolyte. • Photoelectrons provided from separate photosensitive dye • Overall peak power production represents a conversion efficiency of about 11% THIRD GENERATION: GRÄETZEL CELLS Dyes • • • • • • • • • • • • ruthenium metal organic complex carboxylic acid functionalized porphyrin arrays Dye molecules are hit by light Electrons in the dye are transmitted to TiO2. • K3 Fe(CN)6/K4 Fe(CN)6 • Iodide/Triiodide Fe(CN)6 4-/Fe(CN)6 • Sulphide salt/sulphur • Charge separation not solely provided by the semiconductor.THIRD GENERATION: TYPES Photoelectrochemical (PEC) cells • Separate the two functions provided by silicon in a traditional cell • design • Consists of a semiconducting photoanode and a metal cathode • immersed in an electrolyte.

low materials cost Gräetzel cells .Polyethylene Terepthalate ITO .• Fullerene embedded into conjugated polymer conductor • Lightweight. flexible. and have little potential for negative environmental • impact. disposable. polymeric conductor. • Present best efficiency of polymer solar cells lies near 5 percent • Cost is roughly one-third of that of traditional silicon solar cell technology Band gaps ≥ 2eV THIRD GENERATION: POLYMER CELL • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • After excitation in photoactive polymer.Poly(3. designable on • the molecular level.solution processable. chemically synthesized Polymer cells . Advantages Low-energy. which carries electrons from the counter electrode to the oxidized dye. such as PEDOT or PEDOT:TMA. inexpensive to fabricate. PET . high-throughput processing technologies Polymer cells .potentially rechargeable => upgradeable? Disadvantages Efficiencies are lower compared with silicon (wafer-based) solar cells Polymer solar cells: . Similar to Gräetzel cell except the electrolyte is replaced with a conductive polymer.4-ethylenedioxythiophene) Al – Aluminium Nov-21-07 22 Separate the two functions provided by silicon in a traditional cell design Semiconductor used solely for charge separation Photoelectrons provided from separate photosensitive dye Typically a ruthenium metal organic dye Cell Design: Dye-sensitized titanium dioxide Coated and sintered on a transparent semi-conducting oxide (ITO) p-type.Work even in low-light conditions DSSC . the electron is transferred to the C60 due to its higher electron affinity Photoinduced quasiparticle (polaron P+) formed on the polymer chain and fullerene ion-radical C60 The scheme of plastic solar cells.Indium Tin Oxide (In2O3/SnO2) PEDOT .attractive replacement for existing technologies in ―low density‖ applications like rooftop solar collectors Gräetzel cells .

• Layer that converts different types of light is first • Another layer for the light that passes • Lastly is an infra-red spectrum layer for the cell • Converting some of the heat for an overall solar cell composite • More efficient and cheaper • Based on polymer solar cell and multi junction technology • Future advances will rely on new nanocrystals. In. • Significant advances in hybrid solar cells have followed the development of • elongated nanocrystal rods and branched nanocrystals • More effective charge transport.nanocrystal/polymer cell FOURTH GENERATION Composite photovoltaic technology combining elements of the solid state and organic PV cells Nov-21-07 27 • Use of polymers with nanoparticles mixed together to make a single multispectrum • layer. CdSe) • Imbedded in light absorbing polymer (P3HT) • p-type. • High band gap • PEC cells suffer from degradation of the electrodes from the electrolyte Hybrid . FOURTH GENERATION: OVERVIEW P3HT PEDOT:PS • Cell Design: • Solid state nanocrystals (Si. polymeric conductor. • Coated on a transparent semi-conducting oxide (ITO) FOURTH GENERATION: FUTURE • Thin multi spectrum layers can be stacked to make multispectrum solar cells. carries ‗holes‘ to the counter electrode.• Degradation effects: efficiency is decreased over time due to environmental • effects. CuInS2. • Incorporation of larger nanostructures into polymers required optimization of blend morphology using solvent mixtures. such as cadmium telluride . such as PEDOT:PS.

• potential to enhance light absorption and further improve carge transport. that would mean less weight and less space taken up with the PV system. a senior research engineer in the Electro-Optical Systems Laboratory at the Georgia Tech Research Institute (GTRI). published by The Minerals."said Jud Ready. The GTRI photovoltaic cells trap light between their towerstructures. LLC and a global patent application has been filed for the technology. The research has been sponsored by the Air Force Office of Scientific Research. The cells could find near-term applications for powering spacecraft. Metals and Materials Society. and by enabling efficiency improvements in photovoltaic coating materials.." The 3D design was described in the March 2007 issue of the journal JOM. The new 3D solar cells capture photons from sunlight using an array of miniature "tower" structures that are similar to high-rise buildings in a city street grid. On a satellite or other spacecraft. we can use much smaller photovoltaic arrays. which are approximately 100 microns tall. "Our goal is to harvest every last photon that is available to our cells. and Intellectual Property Partners. FOURTH GENERATION: EVALUATION • • • • • • • • Advantages Solution processable Lower materials cost (polymer) Self-assembly Printable nanocrystals on a polymer film Improved conversion efficiency (potentially) Disadvantages Efficiencies are lower compared to silicon (wafer-based) solar cells Potential degradation problems similar to polymer cells Optimize matching conductive polymers and nanocrystal 3D SOLAR CELLS BOOST EFFICIENCY OF PHOTOVOLTAIC SYSTEMS Unique three-dimensional solar cells that capture nearly all of the light that strikes them could boost nthe efficiency of photovoltaic (PV) systems while reducing their size. NewCyte Inc. weight and mechanical complexity. could also change the way solar cells are designed for a wide range of applications. the Air Force Research Laboratory. 40 microns by 40 .• tetrapods. • Gains can be made by incorporating application-specific organic • components. including electroactive surfactants which control the physical and electronic interactions between nanocrystals and polymer. "By capturing more of the light in our 3D structures.

The patterned wafer is then put into a furnace heated to 780 degrees Celsius. Once the carbon nanotube towers have been grown. the more likely it is that they will recombine with a hole." Ready said. for instance. reducing weight and complexity . That boosts the "quantum efficiency". Testing must verify their ability to survive launch and operation in space. In a process known as chemical vapor deposition. "Now we need to get a good baseline to see where we compare to existing materials. On top of that. reducing the electrical current. Conventional flat solar cells reflect a substantial portion of the light that strikes them. However. and to discover the trade-offs between spacing and the angle at which the light hits the structures. "The efficiency of our cells increases as the sunlight goes away from perpendicular. 10 microns apart and built from arrays containing millions of vertically–aligned carbon nanotubes. Hydrocarbon gases are then flowed into the furnace. whose energy then frees electrons from the photovoltaic materials to create electricalcurrent. However." . In conventional flat solar cells.and improving reliability. allowing the electrons to exit more quickly. Ready also wants to study the optimal heights and spacing for the towers. reducing the chance of recombination taking place. Because the 3D cells absorb more of the photons than conventional cells. the carbon grows arrays of multiwalled carbon nanotubes atop the iron patterns. the researchers use a process called molecular beam epitaxy to coat them with cadmium telluride (CdTe) and cadmium sulfide (CdS) which work as the p-type and n-type photovoltaic layers. is added to serve as the cell's top electrode. a wide range of other photovoltaic materials could also be used. each mobile electron leaves behind a "hole" in the atomic matrix of the coating. "We have demonstrated that we can extract electrons using this approach. which can also serve as the solar cell's bottom junction. That could allow them to be used on spacecraft without the mechanical aiming systems that maintain a constant orientation to the sun. The longer it takes electrons to exit the PV material. The researchers first coat the wafer with a thin layer of iron using a photolithography process that is able to create a wide variety of patterns. reducing the amount of energy they absorb. The ability of the 3D cells to absorb practically all of the light that strikes them could also allow improvements in the efficiency with which the cells convert the photons they absorb into electrical current. And production techniques will have to be enlarged from the current two-inch laboratory prototypes. The researchers chose to make their prototypes cells from the cadmium materials as they were familiar with them from other research. so we may not need mechanical arrays to rotate our cells. a thin coating of indium tin oxide. where the carbon and hydrogen separate." Ready noted.microns square.the rate at which absorbed photons are converted to electrons – of the 3D cells. the carbon nanotube arrays serve both as support for the 3D arrays and as a conductor connecting the photovoltaic materials to the silicon wafer. Fabrication of the cells begins with a silicon wafer. how to optimize this and what's needed to advance this technology. a clear conducting material. Inthe finished cells. The new cells face several hurdles before they can be commercially produced. the photovoltaic coatings must be thick enough to capture the photons. their coatings can be made thinner. and choosing the best material for specific applications will be a goal of future research.The tower structures can trap and absorb light received from many different angles so the new cells remain efficient even when the sun is not directly overhead.

Photovoltaics (PV) or ―solar cells‖ are devices that convert solar the most cost-efficient choice for energy production in remote including rural households in developing countries. The advantage of the 3D device design is that conventional and well established battery technology can be used to construct these devices. which relates to difficulties in sealing the cell and the corrosion of electrical contacts and seals. greater mobility. consumer systems. remote radiotelephones and water pumping applications. such as in remote area power systems. ADVANTAGES With the glass fibre solar cell. NewCyte. longer life time.Intellectual Property Partners of Atlanta holds the rights to the 3D solar cell design and is looking for partners to commercialize the technology.g. Earth-orbiting satellites and space probes.e. Another commercialization path is being followed by an Ohio company. they are starting to be used in assemblies of solar modules connected to the electricity grid through an inverter. Centralized times more expensive than conventional sources of electricity. which is partnering with GTRI to use the 3D approach for terrestrial solar cells. The 3D fibre solar cells are expected to allow the remote use of solar power to generate electricity (i. often in combination with a net metering arrangement. . handheld calculators or wrist watches. The Air Force Office of Scientific Research has awarded the company a Small Business Technology Transfer (STTR) grant to develop the technology. the 3D solar cells would have advantages of smaller size. More recently. for underground and deep water applications). They have long been used in situations where electrical power from the grid is unavailable. CONCLUSION Solar cells have many applications. It is envisaged that to produce the same amount of electricity. more robust in structure and lower production cost over the conventional flat panel silicon and dye sensitized solar cells. we can solve a major problem with flat panel dye sensitized solar cells. e.