Patent Application
20120006398
The field of photovoltaics generally relates to multi-layer materials that convert sunlight directly into DC electrical power. The basic mechanism for this conversion is the photovoltaic effect, first observed by Antoine-César Becquerel in 1839, and first correctly described by Einstein in a seminal 1905 scientific paper for which he was awarded a Nobel Prize for physics. In the United States, photovoltaic (PV) devices are popularly known as solar cells or PV cells. Solar cells are typically configured as a cooperating sandwich of p-type and n-type semiconductors, in which the n-type semiconductor material (on one “side” of the sandwich) exhibits an excess of electrons, and the p-type semiconductor material (on the other “side” of the sandwich) exhibits an excess of holes, each of which signifies the absence of an electron. Near the p-n junction between the two materials, valence electrons from the n-type layer move into neighboring holes in the p-type layer, creating a small electrical imbalance inside the solar cell. This results in an electric field in the vicinity of the metallurgical junction that forms the electronic p-n junction.
When an incident photon excites an electron in the cell into the conduction band, the excited electron becomes unbound from the atoms of the semiconductor, creating a free electron/hole pair. Because, as described above, the p-n junction creates an electric field in the vicinity of the junction, electron/hole pairs created in this manner near the junction tend to separate and move away from junction, with the electron moving toward the electrode on the n-type side, and the hole moving toward the electrode on the p-type side of the junction. This creates an overall charge imbalance in the cell, so that if an external conductive path is provided between the two sides of the cell, electrons will move from the n-type side back to the p-type side along the external path, creating an electric current. In practice, electrons may be collected from at or near the surface of the n-type side by a conducting grid that covers a portion of the surface, while still allowing sufficient access into the cell by incident photons.
Such a photovoltaic structure, when appropriately located electrical contacts are included and the cell (or a series of cells) is incorporated into a closed electrical circuit, forms a working PV device. As a standalone device, a single conventional solar cell is not sufficient to power most applications. As a result, solar cells are commonly arranged into PV modules, or “strings,” by connecting the front of one cell to the back of another, thereby adding the voltages of the individual cells together in electrical series. Typically, a significant number of cells are connected in series to achieve a usable voltage. The resulting DC current then may be fed through an inverter, where it is transformed into AC current at an appropriate frequency, which is chosen to match the frequency of AC current supplied by a conventional power grid. In the United States, this frequency is 60 Hertz (Hz), and most other countries provide AC power at either 50 Hz or 60 Hz.
One particular type of solar cell that has been developed for commercial use is a “thin-film” PV cell. In comparison to other types of PV cells, such as crystalline silicon PV cells, thin-film PV cells require less light-absorbing semiconductor material to create a working cell, and thus can reduce processing costs. Thin-film based PV cells also offer reduced cost by employing previously developed deposition techniques for the electrode layers, where similar materials are widely used in the thin-film industries for protective, decorative, and functional coatings. Common examples of low cost commercial thin-film products include water impermeable coatings on polymer-based food packaging, decorative coatings on architectural glass, low emissivity thermal control coatings on residential and commercial glass, and scratch and anti-reflective coatings on eyewear. Adopting or modifying techniques that have been developed in these other fields has allowed a reduction in development costs for PV cell thin-film deposition techniques.
Furthermore, thin-film cells have exhibited efficiencies approaching 20%, which rivals or exceeds the efficiencies of the most efficient crystalline cells. In particular, the semiconductor material copper indium gallium diselenide (CIGS) is stable, has low toxicity, and is truly a thin film, requiring a thickness of less than two microns in a working PV cell. As a result, to date CIGS appears to have demonstrated the greatest potential for high performance, low cost thin-film PV products, and thus for penetrating bulk power generation markets. Other semiconductor variants for thin-film PV technology include copper indium diselenide, copper indium disulfide, copper indium aluminum diselenide, and cadmium telluride.
Thin-film PV cells using either rigid or flexible substrates generally include a conductive layer, which serves as the lower electrode of the cell, disposed between the underlying substrate and the active PV material. When cells are interconnected by monolithic integration techniques (i.e., when the electrical connections between the cells are created in situ on the continuous substrate), the so-called P2 patterning step is used to divide the continuously formed PV material into cells for subsequent interconnection.
A thin film photovoltaic cell includes a support substrate; a contact layer disposed adjacent a first side of the substrate; a p-type semiconductor layer disposed on the first side of the substrate; an n-type semiconductor layer disposed on the first side of the substrate; and a protective back side layer structure disposed adjacent a second side of the substrate, wherein the protective back side layer structure may include a corrosion resistant material. In some embodiments, the back side layer includes at least a first layer and a second layer. Additionally and/or alternatively, the back side layer may include a molybdenum alloy, wherein the molybdenum alloy may include an alloy partner selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Al, and Si.
A method of producing a flexible, thin-film photovoltaic (PV) structure includes steps of providing a support substrate; applying a layer of a photovoltaic layer structure on a first side of the substrate; and applying a protective back side layer structure on a second side of the substrate, wherein the protective back side layer structure includes a corrosion resistant material. In some embodiments, applying the protective back side layer structure includes applying at least two layers, and/or applying a protective back side layer structure includes applying a first layer and a second layer having a thickness ratio of 1:2, wherein the first layer includes chromium and the second layer includes molybdeunum. Additionally and/or alternatively, applying the protective back side layer structure includes applying a molybdenum-alloy layer, wherein the molybdenum alloy includes an alloy partner selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Al, and Si.
An additional aspect of the present disclosure is directed towards a method of producing an elongate, flexible, photovoltaic (PV)-material strip comprising providing an elongate, flexible-strip support substrate, placing that substrate, in time succession, into different, self-isolated processing chambers; and within each chamber, performing different, time-successive sublayer-creation operations which collectively result in the making of an elongate, roll-contained, flexible, PV-material strip. The PV-material strip may include, on a first side, plural-layer, thin-film PV-cell layer structure and, on a second side, a protective back side layer structure, wherein the protective back side layer structure includes a corrosion resistant material. The protective back side layer structure may include a first layer including chromium and a second layer including molybdenum. Additionally and/or alternatively, the protective back side layer structure may include a molybdenum alloy layer, wherein the molybdenum alloy includes an alloy partner selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Al, and Si.
The advantages of the present disclosure will be understood more readily after a consideration of the drawings and the Detailed Description.
PV cells may be susceptible to damaging environmental conditions, for example during the application of a PV absorber layer by vacuum evaporation, during damp heat integrity testing, or due to environmental heat, humidity and/or moisture reaching a supporting substrate from the back side after installation of the PV cell or module. Molybdenum (Mo) coatings or layers disposed on either side of a supporting substrate may be susceptible to corrosion after periods of exposure to heat and moisture. A thin-film PV cell in accordance with the present disclosure includes an improved corrosion resistance over a substrate having a Mo layer alone.
Additionally and/or alternatively, a thin-film PV cell in accordance with the present disclosure may include a support substrate having photovoltaic layer structure disposed on a first side of the substrate and a protective back side layer structure disposed adjacent a second side of the substrate, wherein the protective back side layer structure improves the corrosion resistance of the substrate and/or protects the substrate from damaging environmental conditions. In accordance with one embodiment of the present disclosure, a protective back side layer structure may include a corrosion resistant material, such as a Mo—X alloy. Additionally and/or alternatively, in accordance with the present disclosure, a PV cell may include a protective back side layer structure having more than one layer, also referred to as a bi-layer, wherein one or more of the layers includes a corrosion resistant material, for example Chromium (Cr).
A PV cell in accordance with the present disclosure may be created by starting with a substrate, and then sequentially depositing multiple thin layers of different materials onto the substrate. When the substrate is flexible, this assembly may be accomplished through a roll-to-roll process whereby the substrate travels from a pay-out roll to a take-up roll, traveling through a series of deposition regions between the two rolls. Regardless of whether the PV material is manufactured in a roll-to-roll process or by some other technique, the material then may be cut to cells of any desired size and subsequently interconnected. Alternatively, various layers of the deposited material may be etched or otherwise divided during manufacture. Further details relating to the composition and manufacture of thin-film PV cells of a type suitable for use with the presently disclosed methods and apparatus may be found, for example, in U.S. Pat. No. 7,194,197 to Wendt et al., Ser. No. 12/424,497 filed Apr. 15, 2009 and Ser. No. 12/397,846 filed Mar. 4, 2009. These references are hereby incorporated into the present disclosure by reference for all purposes.
A stretched-out, flat portion of an elongate strip of thin, flexible, substrate material 14 is shown extending between rolls 10, 12. This substrate strip has different amounts of applied (deposited) PV-cell layer structure at different positions between the rolls. The strip has opposite end winds that are distributed as turns on pay-out roll 10 and take-up roll 12. The direction of travel of the strip material during processing is indicated generally by arrow 16. Curved arrows 18, 20 indicate, symbolically, the related, associated directions of rotation of rolls 10, 12 about axes 10a, 12a, respectively, which are generally normal to the plane of
Reference herein to the substrate strip material 14 should be understood to be reference to a strip of material whose overall structural character changes as the material travels, in accordance with processing steps, between rolls 10 and 12. Through the processing steps, layers of various components that go into the fabrication of the type of PV-module are added.
Nine separate individual processing chambers 22, 24, 2623, 25, 27, 28, 30, 29 are illustrated as rectangular blocks in
Processing begins with a bare starter roll, or strip, of elongate thin-film, flexible substrate material supplied from pay-out roll 10. The uncoated material may have a width of about 33-cm, a thickness of about 0.005-cm, and a length of up to about 300-meters. The width, thickness and length dimensions are, of course, matters of choice, depending on the ultimate intended application for finished PV modules. The substrate material may include PI, any high-temperature polymer, or a thin metal such as stainless steel, titanium, covar, invar, tantalum, brass and niobium etc
A stress-compliant metal interlayer, for example Ni—V, chosen to have intermediate thermal expansion characteristics between the substrate and subsequently-applied layers can be optionally utilized as the first layer deposited onto the substrate. This step is not illustrated in
Within chamber 22, two or more layers may be formed on the opposite sides, or faces, of substrate 32. These two layers are shown on the opposite faces (top and bottom in
Layer 36 forms a protective back side layer structure in accordance with the present disclosure. Protective back side layer structure 36 may include a corrosion resistant material, such as a Mo—X alloy. Additionally and/or alternatively, in accordance with the present disclosure, protective back side layer structure 36 may include more than one layer, also referred to as a bi-layer, wherein one or more of the layers includes a corrosion resistant material. For example, protective back side layer structure 36 may include a Cr/Mo bilayer.
Back contact layer 34 and protective back side layer structure 36 may be applied via sputter deposition and/or may be applied, in the same chamber 22 within separate processing zones and/or may be applied in separate chambers. Notable characteristics of layers 34, 36 include: (a) that each of these layers bonds strongly to its associated substrate strip face; and (b) that these layers are able to tolerate temperature changes that occur in subsequent processing without suffering temperature-induced cracking and fracturing. Additionally, layers 34, 36, disposed as they are on the opposite faces of the substrate strip material, mechanically “balance” one another to inhibit product curling, or “bending out of plane.” Such bending could be a problem and/or an inconvenience if only a single layer on one side were used. By way of example, the induced internal compression in a single Mo layer would be sufficient to curl the substrate to the diameter of a pencil without the balancing effect of the opposite layer.
Material emerging from chamber 22 is ready for introduction into chamber 24, wherein an absorber layer 38, such as a p-type semiconductor in the form of copper-indium-gallium-diselenide (CIGS), or its readily acceptable counterpart, copper-indium-diselenide (CIS), is created, for example via co-deposition events that take place in the fog environment that exists in chamber 24.
In chamber 26, a window or buffer layer in the form of cadmium-sulfide (CdS) is applied as a layer 40 extending over the CIGS or CIS layer that was formed in chamber 24. The CdS layer is preferably applied in a non-wet manner by radio-frequency (RF) sputtering. This results in an overall multiple-layer structure such as pictured generally above chamber 26.
After deposition of the Mo, CIGS, and CdS, the strip proceeds through a sequence of operations, 23, 25, 27 designed to first divide, then subsequently, serially connect adjacent ‘divided’ areas. The first operation is to scribe through all deposited layers exposing bare, uncoated substrate. This first scribe functionally divides the elongate strip of deposited layers into plural individual segments and thereby isolates each segment electrically. These segments are held together by the substrate, which remains intact. The scribing technique used is a matter of choice, with the preferred method herein accomplished using a high power density laser.
Directly adjacent to the first scribe operation, a second selective scribe is conducted removing the CdS and CIGS layers but leaving the Mo intact in the as-deposited conditions. This selective scribe forms a via, or channel, that will be later filled in with a conductive oxide.
To prevent the conductive oxide in the top contact layer from ‘filling in’ the first scribe, Mo/CIGS/CdS, and in effect reconnecting adjacent divided Mo regions, the scribe must be filled in with an insulator. Preferably, this is accomplished with a UV curable ink deposited in operation 27 with a commercially adapted ink jet dispense head that is coincident with the high power density laser.
If the optional, electrically insulating, intrinsic-zinc-oxide i-ZnO layer is employed, this is prepared in processing chamber 28 to create a layer arrangement such as that pictured above chamber 28. In this layer arrangement, the i-ZnO layer is shown at 42, overlying the CdS layer.
A top contact layer in the form of a transparent, conductive-oxide overlayer 44, such as ITO or ZnO:Al layer, is formed in processing chamber 30, either directly upon CdS layer 40 if no i-ZnO layer is used, or directly on i-ZnO layer 42 where it is present. The resulting composite layer structure is indicated generally above chamber 30 in
Where an insulating i-ZnO layer, such as layer 42, is created, the resulting overall layer structure includes what is referred to later herein as a sandwich substructure, indicated generally by arrows 46 in
Generally, thin-film PV cells in accordance with the present disclosure may be based on either rigid or flexible substrates. Rigid glass substrates are relatively inexpensive, generally have a coefficient of thermal expansion that is a relatively close match with the CIGS or other absorber layers, and allow for the use of vacuum deposition systems. However, when comparing technology options applicable during the deposition process, rigid substrates suffer from various shortcomings during processing, such as a need for substantial floor space for processing equipment and material storage, expensive and specialized equipment for heating glass uniformly to elevated temperatures at or near the glass annealing temperature, a high potential for substrate fracture with resultant yield loss, and higher heat capacity with resultant higher electricity cost for heating the glass. Furthermore, rigid substrates require increased shipping costs due to the weight and fragile nature of the glass. As a result, the use of glass substrates for the deposition of thin films may not be the best choice for low-cost, large-volume, high-yield, commercial manufacturing of multi-layer functional thin-film materials such as photovoltaics.
Suitable flexible substrate materials include, for example, a high temperature polymer such as polyimide, or a flexible metallic foil (stainless steel foil, titanium foil, aluminum foil or others) or thin metal such as stainless steel, aluminum or titanium, among others. For example, a substrate including a flexible stainless steel may have thickness on the order of 0.025 mm (25 microns), whereas all of the other layers of the cell may have a combined thickness on the order of 0.002 mm (2 microns) or less. In the case of flexible substrates, manufacture of the PV cells may proceed by a roll-to-roll process. Aside from the ability to perform roll-to-roll manufacturing, flexible substrates may have certain advantages over rigid substrates. For example, roll-to-roll processing of thin flexible substrates allows for the use of relatively compact, less expensive vacuum systems, and of some non-specialized equipment that already has been developed for other thin-film industries. Furthermore, flexible substrate materials inherently have lower heat capacity than glass, so that the amount of energy required to elevate the temperature is minimized. Flexible substrates also exhibit a relatively high tolerance to rapid heating and cooling and to large thermal gradients, resulting in a low likelihood of fracture or failure during processing.
Additionally, once active PV materials are deposited onto flexible substrate materials, the resulting unlaminated cells or strings of cells may be shipped to another facility for lamination and/or assembly into flexible or rigid solar modules. This strategic option both reduces the cost of shipping (lightweight flexible substrates vs. glass, for example), and enables the creation of partner-businesses for finishing and marketing PV modules throughout the world. Notwithstanding the potential advantages of using flexible substrates for thin-film PV cells, the present disclosure relates to improving the corrosion resistance of PV cells based upon both flexible and rigid substrates.
A photovoltaic layer structure in accordance with the present disclosure may include sequential layers including at least a contact layer disposed adjacent a first side of the substrate, a p-type semiconductor layer disposed on the first side of the substrate and/or an n-type semiconductor layer disposed on the first side of the substrate. The photovoltaic layer structure may be deposited onto the substrate of a PV cell in individual processing chambers by various processes such as sputtering, evaporation, vacuum deposition, and/or printing. The precise thickness of each layer depends on the exact choice of materials and on the particular application process chosen for forming each layer. Further details regarding these layers, including possible specific layering materials, layer thicknesses, and suitable application processes for each layer are described, for example, in U.S. Pat. No. 7,194,197.
In particular, the semiconductor material copper indium gallium diselenide (CIGS) is stable, has low toxicity, and is truly a thin film, requiring a thickness of less than two microns in a working PV cell. Other semiconductor variants for thin-film PV technology include copper indium diselenide, copper indium disulfide, copper indium aluminum diselenide, and cadmium telluride.
An active PV layer 212, typically including a p-n or similar semiconductor junction, is then deposited on top of the bottom electrode layer and within patterning P1. Patterning P2 then provides an interconnect path, or via, between the electrodes. A top electrode layer 214 is then disposed above active PV layer 212 and also within patterning P2. Top electrode 214 is then patterned as indicated at P3, by selectively removing material from the top electrode to divide it into discrete sections. This isolates the cells and completes their fabrication into a series interconnected structure.
The connection between top electrode 214 and bottom electrode 210 within patterning P2 may be compromised by corrosion at the interface of the two electrodes. According to the present teachings, this corrosion may be reduced through the use of a corrosion resistant molybdenum alloy (Mo—X) to construct bottom electrode 210, or at least those portions of the bottom electrode in the vicinity of patterning P2. As described below, the use of Mo—X alloys has been found to resist corrosion more than molybdenum alone or other non-alloy metals that have been used previously for the bottom electrode.
Referring to back to
The photovoltaic layer structure deposited on the first side of the substrate may include one or more of a back contact layer 64 such as Mo or Cr/Mo; an absorber layer 66 or layers of material such as copper indium diselenide, copper indium disulfide, copper indium aluminum diselenide, or copper indium gallium diselenide (CIGS); a buffer layer 68 or layers such as a layer of cadmium sulfide (CdS); an i-ZnO layer 70 and a top electrode layer 72 such as transparent conducting oxide (TCO). In addition, a conductive current collection grid (not shown), which may be constructed primarily from silver (Ag) or some other conductive metal, is typically applied over the TCO layer.
As described earlier, a PV cell including a protective back side layer deposited adjacent the second side of the substrate may include a corrosion resistant material and may provide corrosion protection for the PV cell. In accordance the present disclosure, PV cell 50 includes protective back side layer structure 60. Protective back side layer structure 60 may include a layer 62 including a corrosion resistant material. Layer 62 may be disposed directly adjacent second side 56 of substrate 52. Alternatively, there may be an intervening layer, not shown, between layer 62 and the second side of the substrate.
Layer 62 may include a corrosion resistant material, such as a Mo—X alloy. Various Mo—X alloys, or a combination of several different Mo—X alloys, may be used to resist corrosion. For example, binary, ternary, or multicomponent films may be used as Molybdenum alloy Mo—X. The additional element (or elements) X may be selected from groups IVb, Vb, IIIA and/or IVA of the periodic system of elements (PSE), and Ti, Zr, Hf, V, Nb, Ta, Al, and Si may be particularly suitable. In some embodiments, it may be desirable that the alloy partner forms a solid solution with the Molybdenum matrix, for reasons of production process integration and feasibility. Further, in some embodiments it may be preferable that the free reaction enthalpy for the formation of oxide species of the alloy partner or partners will be higher than the free reaction enthalpy of Molybdenum itself, so that the alloy partner will preferentially corrode.
The alloy may be chosen to be low in overall resistivity, so that the increase of electrical resistivity due to alloying may be kept at a minimum by choosing a low amount of the alloying element. For example, the content of the alloyed element (i.e. the atomic concentration) may be chosen to be lower than 25%, or even lower than 10%. The Mo—X alloy may be formed by any suitable means of thin film deposition processes, such as sputtering, evaporation, chemical vapor deposition, pulsed laser deposition, chemical solution deposition, spray deposition, thin film reaction processes, implanting an alloy partner, or other combined methods for thin film fabrication.
The back side of the substrate may be relatively easily corroded when exposed to humidity if coated with a single back side layer including only pure Mo. A protective back side layer deposited on the second side of the substrate in accordance with the present disclosure may offer improved corrosion resistance over a back side layer of Mo alone and, therefore, better protection for the second side of the substrate.
As another indication of the corrosion resistance of Mo—X alloys, the chart below compares the optical appearance of sputtered samples of Mo and MoTa after various times of exposure to damp heat (DH), according to aspects of the present disclosure.
As can be seen by a comparison of
Additionally and/or alternatively, referring back to
Photovoltaic layer structure 108 deposited on first side 104 of the substrate may include one or more of a back contact layer 114 such as Mo or Cr/Mo (114a/114b); an absorber layer 116 or layers of material such as copper indium diselenide, copper indium disulfide, copper indium aluminum diselenide, or copper indium gallium diselenide (CIGS); a buffer layer 218 or layers such as a layer of cadmium sulfide (CdS); a i-ZnO layer 219 and a top electrode layer 220 such as transparent conducting oxide (TCO). In addition, a conductive current collection grid (not shown), which may be constructed primarily from silver (Ag) or some other conductive metal, is typically applied over the TCO layer.
A protective layer structure having two layers may have a thickness ranging from approximately 70 nm-1300 nm, where a first layer, such as a Cr layer, may range in thickness from approximately 20 nm-300 nm and a second layer, such as a Mo layer, may range in thickness from approximately 50 nm-1000 nm.
Back contact layer generally may have a thickness ranging from approximately 220 nm-1300 nm, where a chromium layer may range in thickness from approximately 20 nm-300 nm and a molybdenum layer ranges in thickness from approximately 200 nm-1000 nm. Sputtering powers may range from 5.5 kW to 8.5 kW, and/or operating pressures may range from 4 mT to 8 mT. For example, a second layer including Mo may be sputtered at 7.5 kW and at an operating pressure of 6 mTorr.
Although the precise thickness of each layer of a thin-film PV cell depends on the exact choice of materials and on the particular application process chosen for forming each layer, exemplary materials, thicknesses and methods of application of each layer described above for PV cell 100 are as follows, proceeding in typical order of application of each layer onto substrate 102:
Accordingly, a Cr/Mo bi-layer applied as a protective back layer coating may provide greater corrosion resistance to the back side of the substrate than a pure Mo back layer. Corrosion testing of substrate panels coated with Cr/Mo back side protective bi-layers of various thicknesses supports this inference.
The various structural members disclosed herein may be constructed from any suitable material, or combination of materials, such as metal, plastic, nylon, rubber, or any other materials with sufficient structural strength to withstand the loads incurred during use. Materials may be selected based on their durability, flexibility, weight, and/or aesthetic qualities.
It is believed that the following claims particularly point out certain combinations and subcombinations that are directed to one of the disclosed inventions and are novel and non-obvious. Inventions embodied in other combinations and subcombinations of features, functions, elements and/or properties may be claimed through amendment of the present claims or presentation of new claims in this or a related application. Such amended or new claims, whether they are directed to a different invention or directed to the same invention, whether different, broader, narrower or equal in scope to the original claims, are also regarded as included within the subject matter of the inventions of the present disclosure.
This application claims priority to U.S. Provisional Patent Application Ser. No. 61/284,923 filed Dec. 28, 2009, Ser. No. 61/351,245 filed Jun. 3, 2010, and Ser. No. 61/425,641 filed Dec. 21, 2010, all of which are incorporated herein by reference in their entirety for all purposes. Also incorporated by reference in their entireties are the following patents and patent applications: U.S. Pat. No. 7,194,197, Ser. No. 12/424,497 filed Apr. 15, 2009 and Ser. No. 12/397,846 filed Mar. 4, 2009.
| Number | Date | Country | |
|---|---|---|---|
| 61284923 | Dec 2009 | US | |
| 61351245 | Jun 2010 | US | |
| 61425641 | Dec 2010 | US |
