Method and structure for tiling industrial thin-film solar devices

Information

  • Patent Grant
  • 8859880
  • Patent Number
    8,859,880
  • Date Filed
    Friday, January 14, 2011
    13 years ago
  • Date Issued
    Tuesday, October 14, 2014
    9 years ago
Abstract
A method for integrating photovoltaic module includes providing a cover plate having a first surface and a second surface opposed to the first surface and supplying photovoltaic devices respectively formed on substrates. The photovoltaic devices include photovoltaic cells electrically coupled to each other, and each cell is characterized by a thin-film photovoltaic layer sandwiched between a first electrode material and a second electrode material. The first electrode material overlies the substrate and the second electrode material overlies the thin-film photovoltaic layer. The method further includes disposing the solar devices side by side to laminate with the cover plate by means of a first organic material filled between the second electrode material and the second surface. Each of the solar devices has a peripheral edge region being sealed by a second organic material. The method further includes electrically coupling the solar devices to each other.
Description
BACKGROUND OF THE INVENTION

The present invention relates generally to photovoltaic techniques. More particularly, the present invention provides a method and structure for tiling solar devices to a transparent cover plate. Merely by example, embodiments of the present invention are applied to laminate two or more industrial-sized solar panels based on thin-film photovoltaic materials including copper indium diselenide species (CIS), copper indium gallium diselenide species (CIGS), and/or others.


From the beginning of time, mankind has been challenged to find way of harnessing energy. Energy comes in the forms such as petrochemical, hydroelectric, nuclear, wind, biomass, solar, and more primitive forms such as wood and coal. Over the past century, modern civilization has relied upon petrochemical energy as an important energy source. Petrochemical energy includes gas and oil. Gas includes lighter forms such as butane and propane, commonly used to heat homes and serve as fuel for cooking Gas also includes gasoline, diesel, and jet fuel, commonly used for transportation purposes. Heavier forms of petrochemicals can also be used to heat homes in some places. Unfortunately, the supply of petrochemical fuel is limited and essentially fixed based upon the amount available on the planet Earth. Additionally, as more people use petroleum products in growing amounts, it is rapidly becoming a scarce resource, which will eventually become depleted over time.


More recently, environmentally clean and renewable sources of energy have been desired. An example of a clean source of energy is hydroelectric power. Hydroelectric power is derived from electric generators driven by the flow of water produced by dams such as the Hoover Dam in Nevada. The electric power generated is used to power a large portion of the city of Los Angeles in California. Clean and renewable sources of energy also include wind, waves, biomass, and the like. That is, windmills convert wind energy into more useful forms of energy such as electricity. Still other types of clean energy include solar energy. Specific details of solar energy can be found throughout the present background and more particularly below.


Solar energy technology generally converts electromagnetic radiation from the sun to other useful forms of energy. These other forms of energy include thermal energy and electrical power. For electrical power applications, solar cells are often used. Although solar energy is environmentally clean and has been successful to a point, many limitations remain to be resolved before it becomes widely used throughout the world. As an example, one type of solar cell uses crystalline materials, which are derived from semiconductor material ingots. These crystalline materials can be used to fabricate optoelectronic devices that include photovoltaic and photodiode devices that convert electromagnetic radiation into electrical power. However, crystalline materials are often costly and difficult to make on a large scale. Other types of solar cells use “thin film” technology to form a thin film of photosensitive material to be used to convert electromagnetic radiation into electrical power. Similar limitations exist with the use of thin film technology in making solar cells. That is, efficiencies are often poor. Additionally, film reliability is often poor and cannot be used for extensive periods of time in conventional environmental applications. Often, thin films are difficult to mechanically integrate with each other. These and other limitations of these conventional technologies can be found throughout the present specification and more particularly below.


BRIEF SUMMARY OF THE INVENTION

The present invention relates generally to photovoltaic techniques. More particularly, the present invention provides a method and structure for tiling two or more solar devices to a transparent cover plate. Merely by example, the present invention is applied to laminate two or more thin-film solar devices having sizes of about 165 cm or greater.


According to an embodiment, the present invention provides a method for integrating photovoltaic module. The method includes providing a cover plate having a first surface and a second surface opposed to the first surface. The method further includes supplying two or more solar devices respectively formed on substrates. Each of the two or more photovoltaic devices includes a plurality of photovoltaic cells electrically coupled to each other. Each cell is characterized by a thin-film photovoltaic layer sandwiched between a first electrode material and a second electrode material. The first electrode material overlies the substrate and the second electrode material overlies the thin-film photovoltaic layer. Additionally, the method includes disposing the two or more solar devices side by side to laminate with the cover plate by means of a first organic material filled between the second electrode material and the second surface. Each of the two or more solar devices has a peripheral edge region being sealed by a second organic material. Furthermore, the method includes electrically coupling the two or more solar devices to each other.


In an alternative embodiment, the present invention provides a structure for tiling thin-film solar devices. The structure includes a cover plate with at least a dimension of about 165 cm and greater in one direction including a front surface and a rear surface opposed to the front surface. Additionally, the structure includes two or more solar devices laminated side by side to the rear surface and electrically coupled to each other by a ribbon connector. Each of the two or more solar devices includes a plurality of thin-film photovoltaic cells overlying a substrate. Each of the thin-film photovoltaic cells has a stripe shaped pattern in parallel to each other.


It is to be appreciated that the present invention provides numerous benefits over conventional techniques. Among other things, the method and structure provided in the present invention are compatible but scaled to very large industrial panels from conventional modules, which allow cost effective implementation of new generation integrated thin-film photovoltaic modules into large scale commercial applications. The integrated solar module laminates two or more thin-film photovoltaic devices to a common cover plate. This effective enhances the power capacity of the solar module by extending either circuit current delivered from the entire module or the voltage level for coupling with outside electric contacts. Physically, each of the two or more thin-film solar devices can have a dimension of 65 cm times 165 cm and be disposed side by side onto a hardened glass plate having a dimension of 165 cm or greater in one direction. The encapsulation of the integrated module is compatible with stand alone module, so that additional cost saving in packaging process and material can be achieved by implementation of current invention. Additionally, scale up the stand alone thin-film solar device and their integration provide high quality with reduced cost but enhanced overall efficiency over 11%. There are other benefits as well.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a perspective view of a method and structure for tiling solar devices according to an embodiment of the present invention.



FIG. 2 illustrates a side view (A) and a bottom view (B) of a cover plate laminated to two solar devices according to an embodiment of the present invention.



FIG. 3 is a schematic cross-section view of a thin-film solar device according to an embodiment of the present invention.



FIG. 4 is a schematic top view of a thin-film solar device with stripe shaped cell patterns according to the embodiment of the present invention.



FIG. 5 illustrates a cross-section view (A) and a top view (B) of laminated solar devices including ribbon electric conductors according to an embodiment of the present invention.



FIG. 6 illustrates a cross-section view (A) and a top view (B) of laminated solar devices including ribbon electric conductors according to another embodiment of the present invention.





DETAILED DESCRIPTION OF THE INVENTION


FIG. 1 is a perspective view of a method and structure for tiling solar devices according to an embodiment of the present invention. This diagram is merely an example, which should not limit the scope of the claims herein. As shown, a structure 1000 for tiling solar devices on to a cover plate is schematically broken down to a group of basic elements. In an embodiment, the structure 1000 includes a cover plate 100, two or more solar devices 301 and 303 respectively formed on a substrate 311 and 313, a sealant material 320, a fill material 200, a common conductor 400, and a plurality of ribbon conductor 402. The cover plate is typically flat with a front surface on light-receiving side and a rear surface for attaching one or more solar devices. The cover plate 100 has a thickness in the range of 0.5-10 mm, preferably 1-5 mm, and can be of any material that has sufficient transparency above the photovoltaic layer. Suitably the cover plate is a cover glass, preferably hardened glass. In a specific embodiment, the cover plate 100 can be a polymeric material bearing an optical transparency characteristic. In another specific embodiment, the cover plate 100 has a large physical dimension capable of allowing two or more industrial sized solar devices together to be laminated thereon. For example, the dimension of the cover plate 100 may be at least 165 cm or greater in one direction. Of course the cover plate 100 can have various other shapes, including a rectangular shape.


Referring to FIG. 1, the two or more solar devices 301 and 303 are attached to the rear surface of the cover plate 100. Normally, the two or more solar devices are not covering all area of the cover plate 100. In an embodiment, the two or more solar devices 301 and 303 are disposed side by side having some additional gaps in between. Each of the solar devices 301 and 303 is substantially a kind of thin-film solar devices having a rectangular shape with its length substantially fitted to the cover plate 100 in one direction and total width of all solar devices plus the addition gaps substantially fitted with the cover plate 100 in another direction. In a specific embodiment, the thin-film solar device 301 or 303 is made from a chalcopyrite semiconductor thin film photovoltaic active layer sandwiched by two electrode layers, an upper electrode and a lower electrode. In an implementation, the chalcopyrite semiconductor thin film photovoltaic active layer includes copper indium diselenide absorber overlapped by an optical transparent cadmium sulfide window layer. The upper-electrode overlying the window layer is also optical transparent allowing photons to be absorbed by the photovoltaic layer below and converted into electrons.


As shown in FIG. 1, each cell has a strip shape in parallel to all other cells. For example, the strip shape of each cell is about 6 millimeters in width and has a length up to the substrate except some border region at two ends. Within the border region of the thin-film solar device 301 or 303, a polymeric sealant material 320, such as a polymer tape, is applied to protect the solar device from ingress of moisture. Corresponding to the border region of each solar device 301 on the cover plate 100 an opaque frame region 105 is formed on the rear surface for block light and in particular UV irradiation to the polymer material of the photovoltaic cells. The rest portion, or the major area, of the cover plate 100 is substantially transparent for full spectrum of the sun light overlying the plurality of thin-film photovoltaic cells in stripe shape. Finally, each of the two or more solar devices is laminated its upper-electrode surface to the rear surface of the cover plate by means of the fill material 200. In a specific embodiment, the fill material is an organic polymer material bearing both characteristics of mechanical bonding and optical transparency. For example, the fill material 200 is a transparent polymer selected from ethylene vinyl acetate (EVA) and polyvinyl butyral (PVB), which fills the intermediate space and provides a seal at the circumference of each module for coupling with the sealant material 311 and 313. Of course, there can be many alternatives, variations, and modifications.


Additionally, the two or more solar devices 301 and 303 are inter-coupled electrically while being laminated together to the cover plate 100 to form an integrated thin-film photovoltaic module. The electric coupling between any two neighboring solar devices attached to the cover plate can be electrical in parallel or in series, allowing the integrated thin-film photovoltaic module to support higher electric current capacity or voltage power level. In an embodiment, these electric coupling is achieved by means of a common conductor 400 disposed along an edge of the integrated thin-film photovoltaic module and a plurality of ribbon conductor 402 to connect from the two or more solar devices 301 and 303 to the common conductor 400. In particular, one ribbon conductor 402 may couple to the upper-electrode of a solar device while another ribbon conductor 403 may couple to the lower-electrode of the same solar device. In another embodiment, one ribbon conductor may connect from the upper-electrode of a first solar device 301 to pass a hole through it including the substrate to couple with the lower-electrode of a second solar device 303 next to device 301. Respectively, another ribbon conductor coupled to the upper-electrode of the first solar device 301 or the lower-electrode of the second device 303 may be linkable to an external electric contact for collecting the current from the entire integrated thin-film module.



FIG. 2-A is side view of a cover plate laminated to two solar devices according to an embodiment of the present invention. This diagram is merely an example, which should not limit the scope of the claims herein. As shown, the cover plate 100 includes a transparent and flat plate having a front surface 101 and a rear surface 103. The front surface 101 may be applied as a light-receiving side and the rear surface 103 is utilized for attaching two (or more) solar devices 301. In an embodiment, the two solar devices 301 are encapsulated to the rear surface 103 by means of a transparent organic material 200. The transparent organic material 200 fills the intermediate space region between the rear surface 103 of the cover plate 100 and a top surface of the solar device 301. In a specific embodiment, a circumferential border region of the solar device 301, including the applied encapsulating transparent organic material 200, has been protected by a polymeric material 320, which is a sealant mainly for protecting the solar device against ingress of moisture through the border region. As shown, the cover plate 100 has its width in a desired dimension large enough to fit total widths of two solar devices 301 plus some extra device-device spacing when the two solar devices are disposed side by side. In an implementation, the width of a single solar device 301 may be as large as 65 cm for some industrial sized thin-film photovoltaic module. Therefore, the cover plate 100 for the integrated solar module may be twice that size or even larger.


Referring to FIG. 2-B, a bottom view of the cover plate according to the embodiment of the present invention is shown. This is the bottom view of the cover plate 100 shown in FIG. 2-A. In accordance with the invention the cover plate 100 has its partial area made as opaque. This is achieved by a coating material 305 on the cover plate within the as-mentioned area. The coating can be painted, screen printed and heated, but can also e.g. be a polymeric tape. For example, a ceramic paste can be screen-printed and tempered. Instead of coating, also the body of the cover plate 100 can be modified in the area so as to be opaque, for example by adding a pigment or by inclusion of an opaque layer or substance. The coating is preferably non-conducting. In an embodiment, the as-mentioned opaque area is located properly on the rear surface 103 and in a framed region located just above a border area of a solar device 301 when the cover plate 101 is laminated with the solar device 301. Because the border area of the solar device does not have photovoltaic active material, the opaque area on the cover plate includes substantially all area that can receive light and under which area no photovoltaic layer is present. However, if no such opaque area is used, the photovoltaic layer edges of the solar device will be easily subjected to heating by sun light irradiation different from area having photovoltaic layer, which leads to thermal stress and eventually macroscopic cracking to the solar device. Additionally, the UV degradation of the polymeric material along the solar device edge will be a problem. Therefore, adding the opaque coating 305 characterized by color suitably dark, preferably black, and capable of substantially blocking UV radiation becomes a solution for preventing from the UV degradation and undesired thermal stress. The details of adding proper opaque area to the cover plate when packaging thin-film photovoltaic module can be found in a U.S. patent application Ser. No. 12/158,239 titled “PHOTOVOLTAIC DEVICE AND METHOD FOR ENCAPSULATING” filed by Hermann Calwer etc. on Dec. 20, 2006, incorporated by reference. In an specific embodiment, for a cover plate 100 designed to fit two solar devices side by side, the opaque coating 305 is applied with two such framed regions side by side, as shown in FIG. 2-B. Additionally, the non-opaque region shown is projected just above the thin-film photovoltaic cells of the laminated solar devices 301. The length dimension L of the cover plate 100 is properly selected to fit the length of each of the two or more solar devices 301, which are disposed side by side when encapsulated with the cover plate 100. In an implementation for integrating large scale industrial thin-film solar panel, the length L can be as large as 165 cm and greater.



FIG. 3 is a schematic cross-section view of a thin-film solar device according to an embodiment of the present invention. This diagram is merely an example, which should not limit the scope of the claims herein. In an embodiment, the thin-film solar device 2000 is supported on a substrate 2010 which is typically glass of about 1 to 3 millimeters thickness. A back contact or lower electrode comprises a metal layer 2031 deposited upon substrate 2010. Layer 2031, in the preferred embodiment, typically comprises molybdenum which has been deposited by sputtering to a thickness of about 0.2 to 2 microns. On top of the lower electrode 2031 a p-type chalkopyrite semiconductor layer 2020 is arranged, having a thickness of about 0.2 to 2 microns.


In a specific embodiment, a particular class of thin-film solar devices has an absorber layer formed of a group I-III-VI semiconductor, also referred to as a chalkopyrite semiconductor. Such a semiconductor is generally of the copper indium diselenide (“CIS”) type, wherein this expression is to be understood such that indium can be partly or fully replaced by gallium and/or aluminum, and selenium can be partly or fully replaced by sulphur. The CIS type layer can further comprise a low concentration, trace, or a doping concentration of one or more further elements or compounds, in particular alkali such as sodium, potassium, rubidium, cesium, and/or francium, or alkali compounds. The concentration of such further constituents is typically 5 wt % or less, preferably 3 wt % or less. The CIS layer 2020 can be formed by sputter deposition of a sequence of layers comprising the metal constituents of the CIS layer, followed by a programmed thermal annealing processing with an environment containing Selenium vapor species and/or additionally sulfide species. A preferred process has been described in U.S. Patent Application No. 61/178,459 titled “Method and System for Selenization in Fabricating CIGS/CIS Solar Cells” filed on May 14, 2009, commonly assigned to Stion Corporation, incorporated for all purpose by reference.


On top of the CIS type layer commonly a buffer layer or window 2025 is arranged. The buffer layer can include CdS. A Cd-free inorganic layer such as Zn(O,S) possibly also including hydroxide may be used, but the buffer layer can also be omitted. It is also possible to arrange a layer of intrinsic ZnO, i.e. a ZnO layer that having a bulk resistivity higher than 1 Ohm.cm, preferably higher than 100 Ohm.cm, such as between 1 and 10×103 Ohm.cm. Preferably the layer is between 10 nm and 150 nm thick. The solar device 2000 further comprises an upper-electrode 2032 overlying the buffer layer 2025. In an example, the upper electrode layer is n-type ZnO layer appropriately doped to provide relatively low resistivity, for example, better than about 2.0×10−3 Ohm.cm, and preferably better than 1.0×10−3 Ohm.cm. The thickness of the layer 2032 ranges from 0.5 to 2 microns. In an embodiment, the thin-film solar device 2000 described above is a same class of the two or more solar devices 301 that are laminated to the cover plate for forming an integrated photovoltaic module.



FIG. 4 is a schematic top view of a thin-film solar device with stripe shaped cells according to the embodiment of the present invention. This diagram is merely an example, which should not limit the scope of the claims herein. In a specific embodiment, manufacturing the CIS based thin-film solar device includes a cell patterning process for creating a plurality of stripe shaped cells divided by line patterns in one or more layers. For example, a first plurality of patterns in the lower electrode layer 2031 and a second plurality of patterns in the CIS absorber layer 2020 and partially in the lower-electrode layer 2031 are formed using either laser or mechanical scribe device. The first plurality of patterns and the second plurality of patterns (and any additional series of patterns on buffer layer or upper electrode layer) are utilized for forming electric links from cell to cell and to the electric contact for the thin-film solar device. As shown in FIG. 4, a portion of the thin-film solar device 2000 includes a plurality of photovoltaic cells 2001 each having a width w (spacing between two neighboring line patterns) extending from one end of the substrate to another end (there may be no photovoltaic layers on 1-2 cm border regions of the substrate). In a specific embodiment, the width w of each of these cells 2001 is about 6 mm. The length of these cells 2001 can ranges from 20 cm to 165 cm or greater depending on the physical dimension of the substrate overlying which the solar device is formed. Of course, there can be many variations, alternatives, and modifications.



FIG. 5-A and 5-B illustrate a cross-section view and a top view of laminated solar devices electrically coupled by one or more ribbon conductors between the cover plate and the solar devices according to an embodiment of the present invention. As shown in FIG. 5-A, an integrated photovoltaic module includes at least a solar device 510 laminated to a cover plate 500 by means of a transparent polymeric material 520. In an embodiment, near one side of peripheral border region of the integrated module a common conductor 560 is disposed and a pair of ribbon conductors 565 is used for making electric coupling between the solar device 510 and the common conductor 560. The ribbon conductor 565 is buried within the polymeric material 520. In FIG. 5B, a top view of two solar devices disposed side by side for laminating to the cover plate is shown. From this angle, each ribbon conductor 565 is seen to directly connect each solar device 510 to the common conductor 560. A specific ribbon conductor 565 couples to an upper-electrode or lower-electrode of the solar device 510. The common conductor is arranged to collect the current from the entire integrated module and is connected or connectable to an electrical contact outside the module.



FIG. 6-A and 6-B are a cross-section view and a top view of laminated solar devices including ribbon electric conductors according to another embodiment of the present invention. This diagram is merely an example, which should not limit the scope of the claims herein. As shown, in another embodiment of the invention an integrated photovoltaic module includes a thin-film solar device 610 and at least another thin-film solar device 611 disposed next to the solar device 610 both laminated to a rear surface of a cover plate 600 by means of a transparent polymeric material 620. The solar device 610 or 611 includes a thin-film based photovoltaic absorber layer overlying a metal electrode layer formed on a substrate. For each of the two thin-film solar devices, an upper electrode layer (not shown explicitly), which is a transparent oxide material coupled directly to the transparent polymeric material 620 in this encapsulated structure. In a specific embodiment, the solar device 610 including its supporting substrate includes one or more through-holes 660 prepared before the lamination. A ribbon conductor 665, which coupled to the upper electrode layer of the solar device 611, can pass through the through-hole 660 to the back side of the substrate of the solar device 610 to be connectable with an electric contact mounted there or outside the entire integrated module. The ribbon conductor 665 completes the inter-device electric coupling between the two thin-film solar device 610 and 611 so that the integrated module can provide doubled power capacity. Additionally, each thin-film solar device includes other ribbon conductors 663 respectively attached to either upper or lower electrode layer of either the solar device 610 or solar device 611 to complete the electric coupling either in series or in parallel.


It is to be appreciated that the present invention provides numerous benefits over conventional techniques. Among other things, the method and structure provided in the present invention are compatible, but scaled to very large industrial panels from conventional modules, which allow cost effective implementation of new generation integrated thin-film photovoltaic modules into large scale commercial applications. The integrated solar module laminates two or more thin-film photovoltaic devices to a common cover plate. This effective enhances the power capacity of the solar module by extending either circuit current delivered from the entire module or the voltage level for coupling with outside electric contacts. Physically, each of the two or more thin-film solar devices can have a dimension of 65 cm times 165 cm and be disposed side by side onto a hardened glass plate having a dimension of 165 cm or greater in one direction. The encapsulation of the integrated module is compatible with stand alone module, so that additional cost saving in packaging process and material can be achieved by implementation of current invention. Additionally, scale up the stand alone thin-film solar device and their integration provide high quality with reduced cost but enhanced overall efficiency over 11%.


It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggest to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims.

Claims
  • 1. A method for integrating a photovoltaic module, the method comprising: providing a cover plate having a first surface and a second surface opposed to the first surface;supplying at least two solar devices respectively formed on substrates, each of the at least two photovoltaic devices including a plurality of photovoltaic cells electrically coupled to each other, each cell being characterized by a thin-film photovoltaic layer sandwiched between a first electrode material and a second electrode material, the first electrode material overlying the substrate and the second electrode material overlying the thin-film photovoltaic layer;disposing the at least two solar devices side by side to laminate with the cover plate by means of a first organic material filled between the second electrode material and the second surface, each of the solar devices having a peripheral edge region being sealed by a second organic material; andelectrically coupling the solar devices to each other.
  • 2. The method of claim 1 wherein the first organic material is a transparent polymer selected from ethylene vinyl acetate and polyvinyl butyral.
  • 3. The method of claim 1 wherein the second organic material comprises a polymeric sealant material selected from butyl rubber, urethane and polyurethane materials, polyisobutylene materials, epoxide materials, polysulfamide materials, and cyanoacrylates.
  • 4. The method of claim 1 wherein each of the solar devices comprises a dimension of about 65 cm by 165 cm including the plurality of photovoltaic cells each having a stripe shaped pattern of about 5 mm by about 160 cm.
  • 5. The method of claim 1 wherein the thin-film photovoltaic layer comprises a chalcopyrite compound semiconductor material selected from copper indium diselenide, copper indium disulfide, copper indium gallium diselenide, and copper indium disulfide.
  • 6. The method of claim 1 wherein the electrically coupling comprises using a ribbon conductor embedded within the first organic material to connect to an electric contact disposed along an edge of the cover plate.
  • 7. The method of claim 1 wherein the electrically coupling comprises using a ribbon conductor passed through the solar device and the substrate to an electrical contact disposed at rear side of the substrate.
  • 8. The method of claim 1 wherein the cover plate comprises a hardened glass having a transparent region over main areas of the solar devices and an opaque region over the peripheral edge regions of the solar devices.
  • 9. The method of claim 1 wherein the cover plate comprises a transparent polymer.
CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Patent Application No. 61/297,661, filed Jan. 22, 2010, entitled “Method and Structure for Tiling Industrial Thin-Film Solar Devices” by inventor Robert D. Wieting, commonly assigned and incorporated by reference herein for all purposes

US Referenced Citations (303)
Number Name Date Kind
3520732 Nakayama et al. Jul 1970 A
3828722 Reuter et al. Aug 1974 A
3975211 Shirland Aug 1976 A
4062038 Cuomo et al. Dec 1977 A
4204933 Barlow et al. May 1980 A
4213781 Noreika et al. Jul 1980 A
4239553 Barnett et al. Dec 1980 A
4263336 Thompson et al. Apr 1981 A
4287382 French Sep 1981 A
4332974 Fraas Jun 1982 A
4335266 Mickelsen et al. Jun 1982 A
4347436 Fukuda et al. Aug 1982 A
4441113 Madan Apr 1984 A
4442310 Carlson et al. Apr 1984 A
4461922 Gay et al. Jul 1984 A
4465575 Love et al. Aug 1984 A
4471155 Mohr et al. Sep 1984 A
4499658 Lewis Feb 1985 A
4502225 Lin Mar 1985 A
4507181 Nath et al. Mar 1985 A
4517403 Morel et al. May 1985 A
4518855 Malak May 1985 A
4542255 Tanner et al. Sep 1985 A
4581108 Kapur et al. Apr 1986 A
4589194 Roy May 1986 A
4598306 Nath et al. Jul 1986 A
4599154 Bender et al. Jul 1986 A
4611091 Choudary et al. Sep 1986 A
4612411 Wieting et al. Sep 1986 A
4623601 Lewis et al. Nov 1986 A
4625070 Berman et al. Nov 1986 A
4638111 Gay Jan 1987 A
4661370 Tarrant Apr 1987 A
4663495 Berman et al. May 1987 A
4705912 Nakashima et al. Nov 1987 A
4724011 Turner et al. Feb 1988 A
4727047 Bozler et al. Feb 1988 A
4751149 Vijayakumar et al. Jun 1988 A
4775425 Guha et al. Oct 1988 A
4793283 Sarkozy Dec 1988 A
4798660 Ermer et al. Jan 1989 A
4816082 Guha et al. Mar 1989 A
4816420 Bozler et al. Mar 1989 A
4865999 Xi et al. Sep 1989 A
4873118 Elias et al. Oct 1989 A
4915745 Pollock et al. Apr 1990 A
4950615 Basol et al. Aug 1990 A
4968354 Nishiura et al. Nov 1990 A
4996108 Divigalpitiya et al. Feb 1991 A
5008062 Anderson et al. Apr 1991 A
5011565 Dube et al. Apr 1991 A
5028274 Basol et al. Jul 1991 A
5039353 Schmitt Aug 1991 A
5045409 Eberspacher et al. Sep 1991 A
5069727 Kouzuma et al. Dec 1991 A
5078803 Pier et al. Jan 1992 A
5125984 Kruehler et al. Jun 1992 A
5133809 Sichanugrist et al. Jul 1992 A
5137835 Karg Aug 1992 A
5154777 Blackmon et al. Oct 1992 A
5180686 Banerjee et al. Jan 1993 A
5211824 Knapp May 1993 A
5217564 Bozler et al. Jun 1993 A
5231047 Ovshinsky et al. Jul 1993 A
5248345 Sichanugrist et al. Sep 1993 A
5259883 Yamabe et al. Nov 1993 A
5261968 Jordan Nov 1993 A
5298086 Guha et al. Mar 1994 A
5336381 Dalzell, Jr. et al. Aug 1994 A
5336623 Sichanugrist et al. Aug 1994 A
5346853 Guha et al. Sep 1994 A
5397401 Toma et al. Mar 1995 A
5399504 Ohsawa Mar 1995 A
5421909 Ishikawa et al. Jun 1995 A
5436204 Albin et al. Jul 1995 A
5445847 Wada Aug 1995 A
5474939 Pollock et al. Dec 1995 A
5482571 Yamada et al. Jan 1996 A
5501744 Albright et al. Mar 1996 A
5512107 van den Berg Apr 1996 A
5528397 Zavracky et al. Jun 1996 A
5536333 Foote et al. Jul 1996 A
5578103 Araujo et al. Nov 1996 A
5578503 Karg et al. Nov 1996 A
5589006 Itoyama et al. Dec 1996 A
5622634 Noma et al. Apr 1997 A
5626688 Probst et al. May 1997 A
5665175 Safir Sep 1997 A
5676766 Probst et al. Oct 1997 A
5698496 Fastnacht et al. Dec 1997 A
5726065 Szlufcik et al. Mar 1998 A
5738731 Shindo et al. Apr 1998 A
5855974 Wu et al. Jan 1999 A
5858819 Miyasaka Jan 1999 A
5868869 Albright et al. Feb 1999 A
5925228 Panitz et al. Jul 1999 A
5948176 Ramanathan et al. Sep 1999 A
5977476 Guha et al. Nov 1999 A
5981868 Kushiya et al. Nov 1999 A
5985691 Basol et al. Nov 1999 A
6001744 Doi Dec 1999 A
6040521 Kushiya et al. Mar 2000 A
6048442 Kushiya et al. Apr 2000 A
6077722 Jansen et al. Jun 2000 A
6092669 Kushiya et al. Jul 2000 A
6107562 Hashimoto et al. Aug 2000 A
6127202 Kapur et al. Oct 2000 A
6134049 Spiller et al. Oct 2000 A
6160215 Curtin Dec 2000 A
6166319 Matsuyama Dec 2000 A
6169246 Wu et al. Jan 2001 B1
6172297 Hezel et al. Jan 2001 B1
6258620 Morel et al. Jul 2001 B1
6288325 Jansen et al. Sep 2001 B1
6294274 Kawazoe et al. Sep 2001 B1
6307148 Takeuchi et al. Oct 2001 B1
6310281 Wendt et al. Oct 2001 B1
6323417 Gillespie et al. Nov 2001 B1
6328871 Ding et al. Dec 2001 B1
RE37512 Szlufcik et al. Jan 2002 E
6335479 Yamada et al. Jan 2002 B1
6361718 Shinmo et al. Mar 2002 B1
6372538 Wendt et al. Apr 2002 B1
6380480 Norimatsu et al. Apr 2002 B1
6423565 Barth et al. Jul 2002 B1
6537845 McCandless et al. Mar 2003 B1
6632113 Noma et al. Oct 2003 B1
6635307 Huang et al. Oct 2003 B2
6653701 Yamazaki et al. Nov 2003 B1
6667492 Kendall Dec 2003 B1
6690041 Armstrong et al. Feb 2004 B2
6692820 Forrest et al. Feb 2004 B2
6784492 Morishita Aug 2004 B1
6852920 Sager et al. Feb 2005 B2
6878871 Scher et al. Apr 2005 B2
6974976 Hollars Dec 2005 B2
7122398 Pichler Oct 2006 B1
7179677 Ramanathan et al. Feb 2007 B2
7194197 Wendt et al. Mar 2007 B1
7220321 Barth et al. May 2007 B2
7235736 Buller et al. Jun 2007 B1
7252923 Kobayashi Aug 2007 B2
7265037 Yang et al. Sep 2007 B2
7303788 Kataoka et al. Dec 2007 B2
7319190 Tuttle Jan 2008 B2
7364808 Sato et al. Apr 2008 B2
7441413 Bae et al. Oct 2008 B2
7442413 Zwaap et al. Oct 2008 B2
7544884 Hollars Jun 2009 B2
7576017 Tuttle Aug 2009 B2
7736755 Igarashi et al. Jun 2010 B2
7741560 Yonezawa Jun 2010 B2
7846750 Boyer Dec 2010 B2
7855089 Farris, III et al. Dec 2010 B2
7863074 Wieting Jan 2011 B2
7863518 Terakawa et al. Jan 2011 B2
7875945 Krasnov et al. Jan 2011 B2
7910399 Wieting Mar 2011 B1
7955891 Wieting Jun 2011 B2
7960204 Lee Jun 2011 B2
7993954 Wieting Aug 2011 B2
7993955 Wieting Aug 2011 B2
7998762 Lee et al. Aug 2011 B1
8003430 Lee Aug 2011 B1
8008110 Lee Aug 2011 B1
8008111 Lee Aug 2011 B1
8008112 Lee Aug 2011 B1
8017860 Lee Sep 2011 B2
8026122 Lee Sep 2011 B1
8142521 Wieting Mar 2012 B2
8168463 Wieting May 2012 B2
8178370 Lee et al. May 2012 B2
8183066 Lee et al. May 2012 B2
8217261 Wieting Jul 2012 B2
8263494 Patterson Sep 2012 B2
8287942 Huang et al. Oct 2012 B1
20020002992 Kariya et al. Jan 2002 A1
20020004302 Fukumoto Jan 2002 A1
20020061361 Nakahara May 2002 A1
20020063065 Sonoda et al. May 2002 A1
20030075717 Kondo et al. Apr 2003 A1
20030089899 Lieber et al. May 2003 A1
20030188777 Gaudiana et al. Oct 2003 A1
20030230338 Menezes Dec 2003 A1
20040063320 Hollars Apr 2004 A1
20040084080 Sager et al. May 2004 A1
20040095658 Buretea et al. May 2004 A1
20040110393 Munzer et al. Jun 2004 A1
20040161539 Miyakawa Aug 2004 A1
20040187917 Pichler Sep 2004 A1
20040191949 Iwata et al. Sep 2004 A1
20040191950 Nakamura et al. Sep 2004 A1
20040245912 Thurk et al. Dec 2004 A1
20040252488 Thurk Dec 2004 A1
20040256001 Mitra et al. Dec 2004 A1
20050074915 Tuttle et al. Apr 2005 A1
20050098205 Roscheisen et al. May 2005 A1
20050109392 Hollars May 2005 A1
20050164432 Lieber et al. Jul 2005 A1
20050194036 Basol Sep 2005 A1
20050223570 Yonezawa et al. Oct 2005 A1
20050287717 Heald et al. Dec 2005 A1
20060034065 Thurk Feb 2006 A1
20060040103 Whiteford et al. Feb 2006 A1
20060051505 Kortshagen et al. Mar 2006 A1
20060096536 Tuttle May 2006 A1
20060096537 Tuttle May 2006 A1
20060096635 Tuttle May 2006 A1
20060102230 Tuttle May 2006 A1
20060112983 Parce et al. Jun 2006 A1
20060130890 Hantschel et al. Jun 2006 A1
20060160261 Sheats et al. Jul 2006 A1
20060173113 Yabuta et al. Aug 2006 A1
20060174932 Usui et al. Aug 2006 A1
20060219288 Tuttle Oct 2006 A1
20060219547 Tuttle Oct 2006 A1
20060220059 Satoh et al. Oct 2006 A1
20060249202 Yoo et al. Nov 2006 A1
20060267054 Martin et al. Nov 2006 A1
20070004078 Alberts Jan 2007 A1
20070006914 Lee Jan 2007 A1
20070089782 Scheuten et al. Apr 2007 A1
20070116892 Zwaap et al. May 2007 A1
20070116893 Zwaap May 2007 A1
20070151596 Nasuno et al. Jul 2007 A1
20070163643 Van Duren et al. Jul 2007 A1
20070169810 Van Duern et al. Jul 2007 A1
20070193623 Krasnov Aug 2007 A1
20070209700 Yonezawa et al. Sep 2007 A1
20070243657 Basol et al. Oct 2007 A1
20070264488 Lee Nov 2007 A1
20070283998 Kuriyagawa et al. Dec 2007 A1
20070289624 Kuriyagawa et al. Dec 2007 A1
20080029154 Milshtein et al. Feb 2008 A1
20080032044 Kuriyagawa et al. Feb 2008 A1
20080041446 Wu et al. Feb 2008 A1
20080057616 Robinson et al. Mar 2008 A1
20080092945 Munteanu et al. Apr 2008 A1
20080092953 Lee Apr 2008 A1
20080092954 Choi Apr 2008 A1
20080105294 Kushiya et al. May 2008 A1
20080110491 Buller et al. May 2008 A1
20080110495 Onodera et al. May 2008 A1
20080115827 Woods et al. May 2008 A1
20080121264 Chen et al. May 2008 A1
20080121277 Robinson et al. May 2008 A1
20080204696 Kamijima Aug 2008 A1
20080210303 Lu et al. Sep 2008 A1
20080216886 Iwakura Sep 2008 A1
20080280030 Van Duren et al. Nov 2008 A1
20080283389 Aoki Nov 2008 A1
20090021157 Kim et al. Jan 2009 A1
20090058295 Auday et al. Mar 2009 A1
20090084438 den Boer et al. Apr 2009 A1
20090087940 Kushiya Apr 2009 A1
20090087942 Meyers Apr 2009 A1
20090145746 Hollars Jun 2009 A1
20090217969 Matsushima et al. Sep 2009 A1
20090234987 Lee et al. Sep 2009 A1
20090235983 Girt et al. Sep 2009 A1
20090235987 Akhtar et al. Sep 2009 A1
20090293945 Peter Dec 2009 A1
20100081230 Lee Apr 2010 A1
20100087016 Britt et al. Apr 2010 A1
20100087026 Winkeler et al. Apr 2010 A1
20100087027 Wieting Apr 2010 A1
20100096007 Mattmann et al. Apr 2010 A1
20100101648 Morooka et al. Apr 2010 A1
20100101649 Huignard et al. Apr 2010 A1
20100122726 Lee May 2010 A1
20100197051 Schlezinger et al. Aug 2010 A1
20100210064 Hakuma et al. Aug 2010 A1
20100224247 Bartholomeusz et al. Sep 2010 A1
20100233386 Krause et al. Sep 2010 A1
20100258179 Wieting Oct 2010 A1
20100267189 Yu et al. Oct 2010 A1
20100267190 Hakuma et al. Oct 2010 A1
20100297798 Adriani et al. Nov 2010 A1
20110018103 Wieting Jan 2011 A1
20110020980 Wieting Jan 2011 A1
20110070682 Wieting Mar 2011 A1
20110070683 Wieting Mar 2011 A1
20110070684 Wieting Mar 2011 A1
20110070685 Wieting Mar 2011 A1
20110070686 Wieting Mar 2011 A1
20110070687 Wieting Mar 2011 A1
20110070688 Wieting Mar 2011 A1
20110070689 Wieting Mar 2011 A1
20110070690 Wieting Mar 2011 A1
20110071659 Farris, III et al. Mar 2011 A1
20110073181 Wieting Mar 2011 A1
20110212565 Wieting Sep 2011 A1
20110259395 Wieting et al. Oct 2011 A1
20110259413 Wieting et al. Oct 2011 A1
20110269260 Buquing Nov 2011 A1
20110277836 Lee Nov 2011 A1
20120003789 Doering et al. Jan 2012 A1
20120018828 Shao Jan 2012 A1
20120021552 Alexander et al. Jan 2012 A1
20120094432 Wieting Apr 2012 A1
20120122304 Wieting May 2012 A1
20120186975 Lee et al. Jul 2012 A1
20120270341 Lee et al. Oct 2012 A1
Foreign Referenced Citations (20)
Number Date Country
199878651 Feb 1999 AU
200140599 Aug 2001 AU
3314197 Nov 1983 DE
10104726 Aug 2002 DE
102005062977 Sep 2007 DE
2646560 Nov 1990 FR
2124826 Feb 1984 GB
2000173969 Jun 2000 JP
2000219512 Aug 2000 JP
2002167695 Jun 2002 JP
2002270871 Sep 2002 JP
2002299670 Oct 2002 JP
2004332043 Nov 2004 JP
2005311292 Nov 2005 JP
0157932 Aug 2001 WO
2005011002 Feb 2005 WO
2006126598 Nov 2006 WO
2007022221 Feb 2007 WO
2007077171 Jul 2007 WO
2008025326 Mar 2008 WO
Non-Patent Literature Citations (24)
Entry
Baumann, A., et al., Photovoltaic Technology Review, presentation Dec. 6, 2004, 18 pages.
Chopra et al., “Thin-Film Solar Cells: An Overview”, 2004, Progress in Photovoltaics: Research and Applications, 2004, vol. 12, pp. 69-92.
Guillen C., “CulnS2 Thin Films Grown Sequentially from Binary Sulfides as Compared to Layers Evaporated Directly from the Elements”, Semiconductor Science and Technology, vol. 21, No. 5, May 2006, pp. 709-712.
Huang et al., Photoluminescence and Electroluminescence of ZnS:Cu Nanocrystals in Polymeric Networks, Applied Physics, Lett. 70 (18), May 5, 1997, pp. 2335-2337.
Huang et al., Preparation of ZnxCd1-xS Nanocomposites in Polymer Matrices and their Photophysical Properties, Langmuir 1998, 14, pp. 4342-4344.
International Solar Electric Technology, Inc. (ISET) “Thin Film CIGS”, Retrieved from http://www.isetinc.com/cigs.html on Oct. 1, 2008, 4 pages.
Kapur et al., “Fabrication of CIGS Solar Cells via Printing of Nanoparticle Precursor Inks”, DOE Solar Program Review Meeting 2004, DOE/GO-102005-2067, p. 135-136.
Kapur et al., “Non-Vacuum Printing Process for CIGS Solar Cells on Rigid and Flexible Substrates”, 29th IEEE Photovoltaic Specialists Conf., New Orleans, LA, IEEE, 2002, pp. 688-691.
Kapur et al., “Non-Vacuum Processing of CIGS Solar Cells on Flexible Polymer Substrates”, Proceedings of the Third World Conference on Photovoltaic Energy Conversion, Osaka, Japan, 2P-D3-43, 2003.
Kapur et al., “Non-Vacuum Processing of Culn1-xGaxSe2 Solar Cells on Rigid and Flexible Substrates using Nanoparticle Precursor Inks”, Thin Solid Films, 2003, vol. 431-432, pp. 53-57.
Kapur et al., “Fabrication of Light Weight Flexible CIGS Solar Cells for Space Power Applications”, Materials Research Society, Proceedings vol. 668, (2001) pp. H3.5.1-H3.5.6.
Kapur et al., “Nanoparticle Oxides Precursor Inks for Thin Film Copper Indium Gallium Selenide (CIGS) Solar Cells”, Materials Research Society Proceedings, vol. 668, (2001) pp. H2.6.1-H2.6.7.
Mehta et al., “A graded diameter and oriented nanorod-thin film structure for solar cell application: a device proposal”, Solar Energy Materials & Solar Cells, 2005, vol. 85, pp. 107-113.
Salvador, “Hole diffusion length in n-TiO2 single crystals and sintered electrodes: photoelectrochemical determination and comparative analysis,” Journal of Applied Physics, vol. 55, No. 8, pp. 2977-2985, Apr. 15, 1984.
Srikant V., et al., “On the Optical Band Gap of Zinc Oxide”, Journal of Applied Physics, vol. 83, No. 10, May 15, 1998, pp. 5447-5451.
Yang et al., “Preparation, Characterization and Electroluminescence of ZnS Nanocrystals in a Polymer Matrix”, Journal Material Chem., 1997, vol. 7, No. 1, pp. 131-133.
Yang et al., “Electroluminescence from ZnS/CdS Nanocrystals/Polymer Composite”, Synthetic Metals 1997, vol. 91, pp. 347-349.
Yang et al., “Fabrication and Characteristics of ZnS Nanocrystals/Polymer Composite Doped with Tetraphenylbenzidine Single Layer Structure Light-emitting Diode”, Applied Physics Letters, vol. 69, No. 3, Jul. 15, 1996, pp. 377-379.
Ellmer et al., Copper Indium Disulfide Solar Cell Absorbers Prepared in a One-Step Process by Reactive Magnetron Sputtering from Copper and Indium Targets; Elsevier Science B.V; Thin Solid Films 413 (2002) pp. 92-97.
Gordillo et al. “Electrical and morphological properties of low resistivity Mo thin films prepared by magnetron sputtering,” 9Brazilian Journal of Physics 36:982-985 (Sep. 2006).
Grecu et al. “Spectroscopic Characterization of Chemical Bath Deposited Cadmium Sulphide Layers”, Journal of Optoelectronics and Advanced Matenals 6:127-132 (Mar. 2004).
Onuma et al., Preparation and Characterization of CuInS Thin Films Solar Cells with Large Grain, Elsevier Science B.V; Solar Energy Materials & Solar Cells 69 (2001) pp. 261-269.
Palm et al. “Second generation CIS solar modules,” Solar Energy 77:757-765 (Dec. 2004).
Scofield “Sodium diffusion, selenization, and microstructural effects associated with various molybdenum back contact layers for CIS-based solar cells” , Proceedings of the 24th IEEE Photovoltaic Specialists Conference, pp. 164-167 (1995).
Related Publications (1)
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20110203634 A1 Aug 2011 US
Provisional Applications (1)
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61297661 Jan 2010 US