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Publication numberUS20060096635 A1
Publication typeApplication
Application numberUS 11/271,203
Publication date11 May 2006
Filing date10 Nov 2005
Priority date10 Nov 2004
Also published asCA2586965A1, CA2586966A1, CN101080511A, CN101087899A, CN101094726A, CN101233260A, CN101410547A, CN101443929A, EP1809786A2, EP1810344A2, US7319190, US20060102230, WO2006053128A2, WO2006053128A3, WO2006053128A8, WO2006053129A2, WO2006053129A3
Publication number11271203, 271203, US 2006/0096635 A1, US 2006/096635 A1, US 20060096635 A1, US 20060096635A1, US 2006096635 A1, US 2006096635A1, US-A1-20060096635, US-A1-2006096635, US2006/0096635A1, US2006/096635A1, US20060096635 A1, US20060096635A1, US2006096635 A1, US2006096635A1
InventorsJohn Tuttle
Original AssigneeDaystar Technologies, Inc.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Pallet based system for forming thin-film solar cells
US 20060096635 A1
Abstract
The present invention provides a photovoltaic thin-film solar cell produced by a providing a pallet based substrate to a series of reaction chambers layers can be sequentially formed on the pallet based substrate.
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Claims(50)
1. An apparatus for manufacturing a photovoltaic device comprising a means for providing a plurality of pallets holding multiple substrate pieces in sequence to a plurality of reaction zones including at least:
a zone capable of providing an environment for deposition of a semiconductor layer; and a zone capable of providing an environment for depositing a p-type absorber layer.
2. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a means for providing in sequence a substrate to a plurality of reactor zones for preparing said substrate.
3. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a first processing zone capable of providing an environment for transition of the substrate from an ambient environment to the processing environment.
4. The apparatus of claim 3 wherein the substrate transitions, in part or whole, from atmospheric pressure to reduced pressure consistent with the subsequent processing environment.
5. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for deposition of a barrier layer.
6. The apparatus of claim 5 wherein the barrier layer comprises a thin conductor or very thin insulating material.
7. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for deposition of a conductive back contact layer.
8. The apparatus of claim 7 wherein the deposition of a conductive back contact layer comprises a metallic layer.
9. The apparatus of claim 8 wherein the metallic layer is comprise conductive metals chosen from the group consisting of molybdenum, titanium, tantalum, or other acceptable metals or alloys.
10. The apparatus of claim 9 wherein the metallic layer is molybdenum.
11. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for deposition of alkali materials.
12. The apparatus of claim 11 wherein the alkali materials are Na-VII or Na2-VII.
13. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for deposition of a semiconductor layer.
14. The apparatus of claim 13 wherein the semiconductor layer comprises Group I, III, VI elements.
15. The apparatus of claim 14 wherein the semiconductor layer comprises CuGaSe2, CuAlSe2, or CuInSe2 alloyed with one or more of the I, III, VI elements.
16. The apparatus of claim 15 wherein the semiconductor layer comprises CuGaSe2.
17. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for deposition of a semiconductor layer wherein the layer comprises precursor materials.
18. The apparatus of claim 17 wherein the precursor materials comprise Group I, III, VI elements.
19. The apparatus of claim 18 wherein the precursor materials comprise a I-(IIIa,IIIb)-VI2 layer.
20. The apparatus of claim 19 wherein the precursor materials comprise one or more of the elements of a I-(IIIa,IIIb)-VI2 layer where the 0.0<IIIb/(IIIa+IIIb)<0.4.
21. The apparatus of claim 19 wherein the precursor materials comprise one or more of the alloys of a I-(IIIa,IIIb)-VI2 layer where the 0.0<IIIb/(IIIa+IIIb)<0.4.
22. The apparatus of claim 19 wherein the semiconductor layer comprises a CIGS absorber layer comprising In1-x:Gax:Se2 where x ranges between 0.2 to 0.3 wherein the thickness ranges from about 1 μm to about 3 μm.
23. The apparatus of claim 22 where the CIGS absorber layer is formed by the delivery of type I, III and VI precursor metals where Cu, In1-x, Gax, and Se2 layers are sequentially deposited on the substrate.
24. The apparatus of claim 22 where the CIGS absorber layer is formed by the delivery of the type I, III and VI precursor metals where Cu, In1-x, Gax, and Se2 layers are sequentially deposited on the substrate and then synthesized into an alloy mixture with a thermal treatment.
25. The apparatus of claim 22 where the CIGS absorber layer is formed by the delivery of type I, III and VI precursor metals where an Cu:Gax layer is separately synthesized, and then co-deposited with an Inx-1 layer and Se2 layer on a substrate.
26. The apparatus of claim 22 where the CIGS absorber layer is formed by the delivery of type I, III and VI precursor metals where a Cu:Gax layer is separately synthesized, and then co-deposited with an In1-x layer and Se2 layer on a substrate; and then synthesized into an alloy mixture with a thermal treatment.
27. The apparatus of claim 22 where the CIGS absorber layer is formed by the delivery of type I, III and VI precursor metals where an Cu:Gax:Inx-1 layer is separately synthesized, and then co-deposited with an Se2 layer on a substrate.
28. The apparatus of claim 22 where the CIGS absorber layer is formed by the delivery of type I, III and VI precursor metals where a Cu:Gax:Inx-1 layer is separately synthesized, and then co-deposited with an Se2 layer on a substrate; and then synthesized into an alloy mixture with a thermal treatment.
29. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for thermal treatment of one or more layers.
30. The apparatus of claim 29 wherein the treatment occurs in the pressure range of 10−6 torr up to atmospheric pressure and temperature range of 300 C. to 700 C.
31. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for deposition of an n-type semiconductor layer.
32. The apparatus of claim 31 wherein the n-type semiconductor layer is discrete.
33. The apparatus of claim 32 wherein the discrete layer comprises one or more of Group II-VI, III-VI elements.
34. The apparatus of claim 32 wherein the discrete layer materials comprise one or more of the following groups (In,Ga)y(Se,S,O) and (Zn,Cd) (Se,S,O).
35. The apparatus of claim 32 wherein the discrete layer materials comprise one or more of the following materials chosen from the group consisting of (In,Ga)2Se3, (In,Ga)2S3, ZnSe, ZnS, and ZnO.
36. The apparatus of claim 32 wherein the n-type semiconductor layer is formed by diffusion of a dopant species into the p-type absorber layer.
37. The apparatus of claim 36 wherein the dopant species is chosen from the group consisting of one or more Group II or III elements.
38. The apparatus of claim 37 wherein the dopant species comprises either Zn or Cd.
39. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for deposition of an insulating transparent oxide layer.
40. The apparatus of claim 39 wherein the insulating transparent oxide layer comprises one or more materials from Group II-VI or II-IV-VI.
41. The apparatus of claim 39 wherein the insulating transparent oxide layer comprises one or more materials ZnO or ITO.
42. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a processing zone capable of providing an environment for deposition of a conducting transparent layer.
43. The apparatus of claim 42 wherein the conducting transparent layer comprises one or more materials from Group II-VI or II-IV-VI.
44. The apparatus of claim 42 wherein the conducting transparent layer comprises one or more materials ZnO, Cd2SnO4 or ITO.
45. The apparatus for manufacturing a photovoltaic device of claim 1 further comprising a first processing zone capable of providing an environment for transition of the substrate from the processing environment back to the ambient environment.
46. The apparatus of claim 45 wherein the substrate transitions, in part or whole, from atmospheric pressure to the reduced pressure consistent with the subsequent processing environment.
47. A method for manufacturing a photovoltaic device comprising providing a pallet, capable of holding a substrate, in sequence to a plurality of reactor zones wherein said plurality of zones includes at least one zone capable of providing an environment for depositing a p-type absorber layer.
48. A method for manufacturing a photovoltaic cell comprising:
a. providing a plurality of substrate pieces affixed to a pallet carrier means;
b. depositing a conductive film on the surface of said plurality of substrate pieces;
c. wherein the conductive film includes a plurality of discrete layers of conductive materials;
d. depositing at least one p-type semiconductor layer on the conductive film, wherein the p-type semiconductor layer includes a copper indium diselenide based alloy material;
e. depositing an n-type semiconductor layer on the p-type absorber layer forming a p-n junction.
49. A pallet system for production of photovoltaic devices comprising:
a. a pallet base with a first side and a second side where disposed on said first side of said pallet base is a plurality of regularly disposed target areas; wherein each of said plurality of disposed target areas has means for fixing a work substrate in a removable fashion;
b. indexing means disposed on said pallet base allowing control of the positioning of said pallet base;
c. fixing means is magnetic means;
d. magnetic means have thermal reservoir capacity disposed evenly over said designated target areas;
e. work substrate is a magnetic material such as stainless steel;
f. fixable means is mechanical.
50. A pallet system for production of photovoltaic devices comprising:
a. a pallet base with a first side and a second side where said first side has a plurality of regularly disposed target areas disposed on said first side of said pallet base;
b. a plurality of regularly disposed target areas disposed on said second side of said pallet base; wherein each of said plurality of disposed target areas has means for fixing a work substrate in a removable fashion;
c. indexing means disposed on said pallet base allowing control of the positioning of said pallet base.
Description
    CROSS-REFERENCE TO RELATED APPLICATIONS
  • [0001]
    This application claims priority from U.S. Provisional Patent Application Ser. No. 60/626,843, filed Nov. 10, 2004.
  • FIELD OF THE INVENTION
  • [0002]
    The invention disclosed herein relates generally to the field of photovoltaics and more specifically to the product and method of manufacturing thin-film solar cells using a pallet based system to prevent the formation of defects during deposition.
  • BACKGROUND OF THE INVENTION
  • [0003]
    The benefits of renewable energy are not fully reflected in the market price. While alternative energy sources such as photovoltaic (PV) cells offer clean, reliable, and renewable energy, high product costs and lack of production reliability have kept these devices from being a viable commercial product. With the demand for energy going up, the world demand for alternatives to present energy sources is increasing.
  • [0004]
    Although relatively efficient thin-film PV cells can be manufactured in the laboratory, it has proven difficult to commercially scale manufacturing processes with the consistent repeatability and efficiency critical for commercial viability. Moreover, the cost associated with manufacturing is an important factor preventing the broader commercialization of thin-film solar cells. The lack of an efficient thin-film manufacturing process has contributed to the failure of PV cells to effectively replace alternate energy sources in the market.
  • [0005]
    Thin-film PV cells can be manufactured according to varied designs. In a thin-film PV cell, a thin semiconductor layer of PV materials is deposited on a supporting layer such as glass, metal, or plastic foil. Since thin-film materials have higher light absorptivity than crystalline materials, thin-film PV materials are deposited in extremely thin consecutive layers of atoms, molecules, or ions. The typical active area of thin-film PV cells is only a few micrometers thick. The basic photovoltaic stack design exemplifies the typical structure of a PV cell. In that design, the thin-film solar cell comprises a substrate, a barrier layer, a back contact layer, a mixed type semiconductor source layer, an absorber layer, an n-type junction buffer layer, an intrinsic transparent oxide layer, and a conductive transparent oxide layer. Compounds of copper indium gallium diselenide (CIGS) have the most promise for use in absorber layers in thin-film cells and fit within the classification of copper-indium selenium class, called CIS materials. CIGS films are typically deposited by vacuum-based techniques.
  • [0006]
    Thin-film manufacturing processes suffer from low yield due to defects in the product that occur during the course of deposition. Specifically, these defects are caused by contamination occurring during processing and materials handling, and the breakage of glass, metal, or plastic substrates. Thus, a process for manufacturing thin-film solar cells that both limits potential contamination during processing and concurrently minimizes substrate breakage is desired in the art.
  • [0007]
    Currently, cells are manufactured using a multi-step batch process wherein each product piece is transferred between reaction steps. This transfer is bulky and requires the reaction in chambers to be cycled. A typical process consists of a series of individual batch processing chambers, each specifically designed for the formation of various layers in the cell. Problematically, the substrate is transferred from vacuum to air—and back again—several times. Such vacuum breaks may result in contamination of the product. Thus, a process that minimizes vacuum breaks is desired in the art.
  • [0008]
    While an alternate system uses a series of individual batch processing chambers coupled with a roll-to-roll continuous process for each chamber, the discontinuity of the system and the need to break vacuum continues to be a major drawback. Additionally, the roll-to-roll process may impose flexing stress on substrates, resulting in fracturing and breakage. Such defects compromise layer cohesiveness and may result in a zero yield.
  • [0009]
    Also contributing to the low yield in PV cell manufacturing is the requirement of high-temperature deposition processes. High temperatures are generally incompatible with all presently known flexible polyimide or other polymer substrate materials.
  • [0010]
    For example, U.S. Patent Application 2004/0063320, published by Hollars on Apr. 1, 2004, discloses a general methodology for continuously producing photovoltaic stacks using a roll-to-roll system. As discussed above, this process requires the application of flexing stress to the substrate. This stress potentially results in fractures and breakage. Fractures or breakage reduce high quality stack structures and lower manufacturing yield. Thus, to be a commercially viable process, the disclosed system requires a flexible substrate for the production of the stack. However, no currently known flexible polymer materials can withstand the high-temperature deposition process. Therefore, a process that does not impose flexing stress on the substrates, where the substrates can withstand the high-temperature deposition process, is desired in the art. So a process for manufacturing PV work pieces effectively, and capable of large scale production are needed.
  • SUMMARY OF THE INVENTION
  • [0011]
    The present invention provides a photovoltaic device produced by providing a pallet-based substrate to a series of reaction chambers where sequentially a barrier layer, a back contact layer, a semiconductor layer or layers, alkali materials, an n-type junction buffer layer, an intrinsic transparent oxide layer, a transparent conducting oxide layer and a top metal grid can be formed on the pallet.
  • [0012]
    A method is further disclosed for forming a photovoltaic device in a continuous fashion by employing a train of the pallet based holders loaded with work pieces. In this embodiment, a series of pallets are passed at a defined rate through a reactor having a plurality of processing zones, wherein each zone is dedicated to one production step stage of device manufacture.
  • [0013]
    These production steps may include: a load or isolation zone for substrate preparation; environments for depositing a barrier layer, a back contact layer, semiconductor layer or layer and alkali materials; an environment for the thermal treatment of one or more of the previous layers; and an environment for the deposition of: an n-type compound semiconductor wherein this layer serves as a junction buffer layer, an intrinsic transparent oxide layer, and a conducting transparent oxide layer. In a further embodiment, the process may be adjusted to comprise greater or fewer zones in order to fabricate a thin film solar cell having more or fewer layers.
  • [0014]
    A pallet type system may be employed where a plurality of work pieces are held as a pallet and a plurality of pallets are processed though a continuous reactor step apparatus. This pallet based system allows continuous processing of smaller work pieces and alternative materials handling steps, such as pallet stacking in intermediate or final steps.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0015]
    FIG. 1 shows an embodiment of a thin-film solar cell produced by the production technology of the present invention.
  • [0016]
    FIG. 2 schematically represents a reactor for forming solar cells.
  • [0017]
    FIG. 3 shows a plurality of work piece substrates on a device capable of affixing the substrates onto a carrier that also has means that allow the pieces to be advanced in a precise fashion through the production apparatus.
  • [0018]
    FIG. 4 illustrates one embodiment of a substrate being fed from left to right through a process in accordance with the present invention.
  • [0019]
    FIG. 5A shows an embodiment of the processing method wherein two substrates are fed and processed simultaneously by a sequential sputter-evaporate in accordance with the present invention.
  • [0020]
    FIG. 5B shows a top view of an embodiment of the processing method wherein two substrates are fed and processed simultaneously by a sequential sputter-evaporate/sputter-evaporate process.
  • [0021]
    FIG. 6 illustrates another embodiment of a process in accordance with the invention wherein zones further comprise one or more sub-zones.
  • [0022]
    FIG. 7 shows a schematic of the pallet used in the present invention populated with a plurality of substrate work pieces.
  • [0023]
    FIG. 8 shows a schematic of a cartridge used to stack a plurality of substrates in a controlled environment.
  • [0024]
    FIG. 9 shows a schematic production technique employing the cartridge system to allow discontinuations in a photovoltaic manufacturing process.
  • DETAILED DESCRIPTION OF THE INVENTION General Photovoltaic Stack Designs
  • [0025]
    The present invention employs a new production apparatus to produce photovoltaic devices. Of course, the particular apparatus will depend upon the specific photovoltaic device design, which can be varied. However, the base premise is that each photovoltaic device has a photovoltaic device or thin-film solar cell 100 comprises a substrate 105, a barrier layer 110, a back contact layer 120, a semiconductor layer 130, an alkali materials 140, another semiconductor layer 150, an n-type junction buffer layer 160, an intrinsic transparent oxide layer 170, and a transparent conducting oxide layer 180. This stack of layers, according to the present invention, will be made on a plurality of substrates arrayed on a pallet 700, shown in FIG. 7. The individual substrate pieces 710 will be arrayed on the pallet, fixed by a fixture means.
  • General Apparatus Configurations
  • [0026]
    A first embodiment of the invention is an apparatus for manufacturing a photovoltaic device comprising a means for providing a plurality of pallets holding multiple substrate pieces, in sequence, to a plurality of reaction zones. These reaction zones include at least a zone capable of providing an environment for deposition of a semiconductor layer, and a zone capable of providing an environment for depositing a precursor p-type absorber layer.
  • [0027]
    FIG. 7 shows a schematic top view of a pallet. The pallet provides a holding basis 700 for a plurality of small PV work piece substrates 710, or working substrates fixedly attached to the pallet in a pre-determined manner so that the individual work pieces are presented in each treatment chamber in a precise and controllable fashion. The pallet itself is engineered so that the position of the pallet can be precisely determined. The pallet also has a means for allowing attachment to a drive means to advance the pallet through the treatment chamber. Materials of the body of the pallet are chosen so that they are thermally stable and do not interact with the treatment or deposition materials used in the reaction or deposition chamber.
  • Fixturing Means
  • [0028]
    Furthermore, the means for securing the work pieces to the pallet are releasable. In some instances the means for affixing the work piece is magnetic, either because the substrate of the work piece is itself ferro-magnetic, or with an overlay that hold the individual pieces to the body of the pallet. A mask may be employed to hold each piece where there is a frame and a plurality of panes that allow deposition through said pane on the work piece substrates.
  • [0029]
    FIG. 4 shows as the plurality of pallets are processed through the series of treatment chambers 420, 430 used to deposit the multiple required layers for a photovoltaic device, the train of reaction/deposition chambers may be fed by loaded cartridges containing a plurality of pallets 440 (see also FIG. 8), and after the desired layers are deposited and processed the finished work pieces are collected in a cartridge 450 and stored for further processing or manufacturing steps (see also FIG. 9).
  • [0030]
    In an alternative method, the starting piece cartridge 440 feeds a system that might provide surface treatment of the substrate, deposition of the junction layer, deposition of the alkali-containing semiconductor source layer, deposition of a p-type absorber layer, and then formation of the junction and n-type layer, and a buffer so that the worked-on pieces can be taken from the controlled reaction train and inventories for further processing.
  • Method of Thin Film Manufacturing
  • [0031]
    One form of the invention provides a method for manufacturing a photovoltaic device comprising the step of providing a pallet, capable of holding a substrate, in sequence to a plurality of reactor zones wherein the plurality of zones includes at least one zone depositing a precursor p-type absorber layer.
  • [0032]
    In another form, the invention provides a method for manufacturing a photovoltaic cell comprising the steps of providing a plurality of substrate pieces affixed to a pallet carrier means, depositing a conductive film on the surface of said plurality of substrate pieces, wherein the conductive film includes a plurality of discrete layers of conductive materials, depositing at least one p-type absorber layer on the conductive film, wherein the p-type semiconductor absorber layer includes a metal based alloy material, e.g., alloys of Cu, In, Ga, and possibly Se or S, and depositing an n-type semiconductor layer on the p-type semiconductor layer forming a p-n junction.
  • [0033]
    A series of treatment chambers are provided where each chamber provides a specific treatment environment, as well as the means for depositing specified materials onto the working surface, or interface of the work pieces being processed in order to produce a specific layer deposition or layer treatment. Each of these treatment chambers allow a means to transport the work pieces (marked on the pallet being made into the photovoltaic device) to be transported from the first designed chamber, through the sequential plurality of chambers, until the work piece has been made into the designed photovoltaic stack.
  • [0034]
    This plurality of reaction or treatment chambers provided with a transport mechanism may also include one or more isolation chambers that ensure effective reactants are maintained in specifically desired chambers and do not contaminate downstream processes. This isolation system is particularly important in the formation of the semiconductor layers of the photovoltaic device, where relatively small amounts of material determine whether a layer is a p-type or n-type semiconductor. This carrier may be configured with referencing means to ensure the work pieces are positioned within the production apparatus at defined positions.
  • [0035]
    FIG. 3 shows a plurality of work piece substrates 310 on a device capable of affixing the substrates onto a carrier 320, that also has means that allow the pieces to be advanced in a precise fashion through the production apparatus. These pallets are generally flat and have means for holding a plurality of work pieces on a surface of the pallet so as to present each of the work piece surfaces to a deposition source or treatment source.
  • General Photovoltaic Stack Designs
  • [0036]
    The present invention employs a new production apparatus to produce photovoltaic devices. Of course, the particular apparatus will depend upon the specific photovoltaic device design, which can be varied.
  • [0037]
    Viewing FIG. 1, all layers are deposited on a substrate 105 which may comprise one of a plurality of functional materials, for example, glass, metal, ceramic, or plastic. Deposited directly on the substrate 105 is a barrier layer 110. The barrier layer 110 comprises a thin conductor or very thin insulating material and serves to block the out diffusion of undesirable elements or compounds from the substrate to the rest of the cell. This barrier layer 110 may comprise chromium, titanium, silicon oxide, titanium nitride and related materials that have the requisite conductivity and durability. The next deposited layer is the back contact layer 120 comprising non-reactive metals such as molybdenum. The next layer is deposited upon the back contact layer 120 and is a p-type semiconductor layer 130 to improve adhesion between an absorber layer and the back contact layer. The p-type semiconductor layer 130 may be a I-IIIa,b-VI isotype semiconductor, but the preferred composition is Cu:Ga:Se; Cu:Al:Se or Cu:In:Se alloyed with either of the previous compounds.
  • [0038]
    In this embodiment, the formation of a p-type absorber layer involves the interdiffusion of a number of discrete layers. Ultimately, as seen in FIG. 1, the p-type semiconductor layers 130 and 150 combine into a single composite layer 155 which serves as the prime absorber of solar energy. In this embodiment, however, alkali materials 140 are added for the purpose of seeding the growth of subsequent layers as well as increasing the carrier concentration and grain size of the absorber layer 155, thereby increasing the conversion efficiency of the solar cell. The layers are then thermally treated at a temperature of about 400 C.-600 C.
  • [0039]
    After the thermal treatment, the photovoltaic production process is continued by the deposition of an n-type junction buffer layer 160. This layer 160 will ultimately interact with the absorber layer 155 to form the necessary p-n junction 165. A transparent intrinsic oxide layer 170 is deposited next to serve as a hetero-junction with the CIGS absorber. Finally, a conducting transparent oxide layer 180 is deposited to function as the top of the electrode of the cell. This final layer is conductive and may carry current to a grid carrier that allows the current generated to be carried away.
  • Alternative Pallet Based Manufacturing Schemes
  • [0040]
    FIG. 2 schematically represents a reactor 200 for forming solar cells. A substrate 205 is fed left to right through the reactor. The reactor 200 includes one or more processing zones, referred to in FIG. 2 as 220, 230, 240 and 250, wherein each processing zone comprises an environment for depositing materials on a substrate 205. The zones are mechanically or operatively linked together within the reactor 200. As used herein, the term environment refers to a profile of conditions for depositing or reacting a material layer or mixture of materials on the substrate 205 while the substrate 205 is in a particular zone.
  • [0041]
    Each zone is configured according to which layer of the solar cell is being processed. For example, a zone may be configured to perform a sputtering operation, including heat sources and one or more source targets.
  • [0042]
    Preferably, an elongated substrate 205 is passed through the various processing zones at a controllable rate. It is further contemplated that the substrate 205 may have a translational speed of 0.5 m/min to about 2 m/min. Accordingly, the process internal to each of the zones is preferably tuned to form the desired cross-section given the residence time the material is proximate to a particular source material, given the desired transport speed. Thus, the characteristics of each process, such as material and process choice, temperature, pressure, or sputtering delivery rate, etc., may be chosen to insure that constituent materials are properly delivered given the stack's residence time as determined by the transport or translation speed.
  • [0043]
    According to the invention, the substrate 205 may be transported continually through the process in a palletized fashion in a “picture frame” type mount for indexing and transportation through the process, the latter of which is illustrated in FIG. 3. Referring to FIG. 3 one substrate or group of substrates 310 are mounted on a pallet 320 that translates through one or more zones 330 and 340 on track 350. In alternate embodiments the process may further comprise a second substrate or set of substrates placed in a back to back configuration with substrate 310.
  • [0044]
    It is contemplated that the background pressure within the various zones will range from 10−6 torr to 10−3 torr. Pressures above base-vacuum (10−6 torr) may be achieved by the addition of a pure gas such as Argon, Nitrogen or Oxygen. Preferably, the rate R is constant resulting in the substrate 205 passing through the reactor 200 from entrance to exit without stopping. It will be appreciated by those of ordinary skill in the art that a solar cell stack may thus be formed in a continuous fashion on the substrate 205, without the need for the substrate 205 to ever stop within the reactor 200.
  • [0045]
    The reactor in FIG. 2 may further comprise vacuum isolation sub-zones or slit valves configured to isolate adjacent process zones. The vacuum isolation sub-zones or slit valves are provided to facilitate the continuous transport of the substrate between different pressure environments.
  • [0046]
    The reactor shown in FIG. 2 is a plurality of N-processing zones 220, 230, 240 and 250. However, it should be recognized by one skilled in the art that the reactor may comprise zones 220, 230, 240, 250 . . . N zones. The load/unload zones 210/211 comprise zones that can be isolated from the rest of the reactor and can be open to atmosphere.
  • [0047]
    In a preferred embodiment, the process may further comprise a substrate 206 that runs back-to-back with substrate 205. In this embodiment substrates 206 and 205 are oriented in a back-to-back configuration and run through zones 220, 230, 240, and 250 performing identical process operations 222/221, 232/231, 242/241 and 252/251.
  • [0048]
    FIG. 5A shows a top illustration of a portion of a reactor 500 processing substrates 501 and 502 in a back-to-back fashion and also illustrates a sequential sputter-evaporate process isolated by zone 511. To achieve back-to-back processing, heat sources 503 for substrate 501 are mirrored as heat sources 507 for substrate 502. Likewise, sputtering source 504, heat sources 505, and evaporative sources 506 for substrate 501 are mirrored for substrate 502 as sputtering source 508, heat sources 509, and evaporative sources 510.
  • [0049]
    FIG. 5B shows a top illustration of a portion of a reactor 512 processing substrates 521 and 522 in a back-to-back fashion with a sequential sputter-evaporate/sputter-evaporate process. As in FIG, 5A, sputter sources 534 for substrate 521 are mirrored as sputter sources 528 for substrate 522. Likewise, heat sources 523 and 526, evaporative sources 524 and 527, and sputtering source 525 for substrate 521 are mirrored for substrate 522 as heat sources 529 and 532, evaporative sources 530 and 533, and sputtering source 531. Hence, with the simple duplication of heat and material sources, solar cell production may be effectively doubled within the same machine.
  • Specific Processing Steps
  • [0050]
    Of course, the method steps for producing a particular PV article depends upon the specific design of that article. CIGS based PVs will have a different production method than Si based systems. The present invention is not so limited to one PV type and in general any PV could be made with the technology of the invention.
  • [0051]
    In cases of CIGS, the specific steps might include: loading a pallet based substrate through an isolated loading zone or like unit 210. In various embodiments, the isolation zone 210 is contained within the reactor 200. Alternatively, the isolation zone 210 may be attached to the outer portion of the reactor 200. The first processing zone 210 may further comprise a substrate preparation environment to remove any residual imperfections at the atomic level of the surface. The substrate preparation may include: ion beam, deposition, heating, or sputter-etching. These methods are known in the art and will not be discussed further.
  • [0052]
    A second processing zone may be an environment for depositing a barrier layer for substrate impurity isolation, wherein the barrier layer provides an electrically conductive path between the substrate and subsequent layers. In a preferred embodiment, the barrier layer comprises an element such as chromium or titanium delivered by a sputtering process. Preferably, the environment comprises a pressure in the range of about 10−6 torr to about 10−2 torr at ambient temperature.
  • [0053]
    A third processing zone downstream from the previous zones comprises an environment for the deposition of a metallic layer to serve as a back contact layer. The back contact layer comprises a thickness that provides a conductive path for electrical current. In addition, the back contact layer serves as the first conducting layer of the solar cell stack. The layer may further serve to prevent the diffusion of chemical compounds such as impurities from the substrate to the remainder of the solar cell structure or as a thermal expansion buffer between the substrate layer and the remainder of the solar cell structure. Preferably, the back contact layer comprises molybdenum, however, the back contact layer may comprise other conductive metals such as aluminum, copper or silver.
  • [0054]
    A fourth zone provides an environment for deposition of a p-type semiconductor layer. As used herein, this layer may serve as an epitaxial template for absorber growth. Preferably, the p-type semiconductor layer is an isotype I-IIIVI2 material, wherein the optical band gap of this material is higher than the average optical band gap of the p-type absorber layer. For example, a semiconductor layer may comprise Cu:Ga:Se; Cu:AI:Se or alloys of Cu:In:Se with either of the previous compounds. Preferably, the materials are delivered by a sputtering process at a background pressure of 10−6 to 10−2 torr and at temperatures ranging from ambient up to about 300 C. More preferably, temperatures range from ambient to about 200 C.
  • [0055]
    A fifth zone, downstream from the previous zones, provides an environment for the deposition of alkali materials to enhance the growth and the electrical performance of a p-type absorber. Preferably, the alkali materials are sputtered, at ambient temperature and a pressure range of about 10−6 torr to 10−2 torr. Preferably, the material comprises NaF, Na2Se, Na2S or KCl or like compounds wherein the thickness ranges from about 150 nm to about 500 nm.
  • [0056]
    A sixth zone, also downstream from the previous zones, may comprise an environment for the deposition of another semiconductor layer comprising p-type absorber precursor materials. In a preferred embodiment, the sixth zone may further comprise one or more sub-zones for the deposition of the precursor materials. In one embodiment, the semiconductor layer is formed by first delivering precursor materials in one or more contiguous sub-zones, then reacting the precursor materials into the final p-type absorber in a downstream thermal treatment zone. Thus, especially for CIGS Systems, there may be two material deposition steps and a third thermal treatment step in the format of the layer.
  • [0057]
    In the precursor delivery zones, the layer of precursor materials is deposited in a wide variety of ways, including evaporation, sputtering, and chemical vapor deposition or combinations thereof preferably, the precursor material may be delivered at temperatures ranging from about 200 C.-300 C. It is desired that the precursor materials react to form the p-type absorber as rapidly as possible. As previously discussed, to this end, the precursor layer or layers may be formed as a mixture or a series of thin layers.
  • [0058]
    A manufacturing device may also have seventh processing zone downstream from previous processing zones for the thermal treatment of one or more of the previous layers. The term multinaries includes binaries, ternaries, and the like. Preferably, thermal treatment reacts previously unreacted elements or multinaries. For example, in one embodiment it is preferred to have Cu, In, Se, and Ga in various combinations and ratios of multinary compounds of elements as the source for deposition on the work piece. The reactive environment includes selenium and sulfur in varying proportions and ranges in temperature from about 400 C. to about 600 C. with or without a background inert gas environment. In various embodiments, processing time may be minimized to one minute or less by optimizing mixing of the precursors. Optimal pressures within the environment depend on whether the environment is reactive or inert. According to the invention, within the thermal treatment zone, the pressures range from about 10−5 to about 10−2 torr. However, it should be noted that these ranges depend very much on the reactor design for the stage, the designer of the photovoltaic device and the operational variables of the apparatus as a whole.
  • [0059]
    The reactor may have an eighth processing zone for the formation of an n-type semiconductor layer or junction partner. The junction layer is selected from the family II-VI, or IIIx VI. For example, the junction layer may comprise ZnO, ZnSe, ZnS, In, Se or InNS deposited by evaporation, sublimation or chemical vapor deposition methodologies. The temperatures range from about 200 C. to about 400 C.
  • [0060]
    Additionally, the process may also have a ninth zone having an environment for deposition of an intrinsic layer of a transparent oxide, for example ZnO. According to the invention, the intrinsic transparent oxide layer may be deposited by a variety of methods including for example, RF sputtering, CVD or MOCVD.
  • [0061]
    In various embodiments, the process further has a tenth zone with an environment for the deposition of a transparent conductive oxide layer to serve as the top electrode for the solar cell. In one embodiment for example, aluminum doped ZnO is sputter deposited. Preferably, the environment comprises a temperature of about 200 C. and a pressure of about 5 millitorr. Alternatively, ITO (Indium Tin Oxide) or similar may be used.
  • [0062]
    In one embodiment, as described above, the reactor may comprise discrete zones wherein each zone corresponds to one layer of photovoltaic device formation. In a preferred embodiment however, zones comprising similar constituents and or environment conditions may be combined thereby reducing the total number of zones in the reactor.
  • [0063]
    For example, in FIG. 6, zone 610 comprises sub-zones 611 and 612, zone 615 comprises sub-zones 616 and 617, and zone 620 comprises one zone, wherein each zone and sub-zone comprises a predetermined environment. In this example, a material A may be deposited in sub-zone 611 and a different material B may be deposited in sub-zone 612, wherein the environment of sub-zone 612 downstream from material A differs from the environment in sub-zone 611. Thus, the substrate 605 may be subjected to a different temperature or other process profiles while in different regions of the same zone 610. According to this embodiment, the zone may be defined as having a predetermined pressure, and a zone may include one or more regions, sub-zones, or phases therein, with each sub-zone configured to deposit or react a desired material or materials within the same pressure environment.
  • [0064]
    The substrate 605 may then be passed to chamber 615, where material C is deposited within sub-zone 616, and material D is deposited in sub-zone 617. Finally, the substrate 605 reaches a zone 620, where a single material E is deposited.
  • [0065]
    As will be appreciated by those of ordinary skill in the art, the reactor 600 may be described as having a series of zones disposed between the entrance and exit of the reactor along a path defined by the translation of the substrate. Within each zone, one or more constituent environments or sub-zones may be provided to deposit or react a selected target material or materials, resulting in a continuous process for forming a solar cell stack. Once the substrate enters the reactor, the various layers of a solar stack are deposited and formed in a sequential fashion, with each downstream process in succession contributing to the formation of the solar cell stack until a finished thin film solar cell is presented at the exit of the reactor.
  • [0066]
    While the present technique has been couched in terms of CIGS based photovoltaic stack designs, it must be understood that the technique may also be employed for the production of other photovoltaic designs including production of silicon based systems such as those discussed in state of the art. For instance, it would be possible to use or include carbon or germanium atoms in hydrogenated amorphous silicon alloys in order to adjust their optical bandgap. For example, carbon has a larger bandgap than silicon and thus inclusion of carbon in a hydrogenated amorphous silicon alloy increases the alloy's bandgap. Conversely, germanium has a smaller bandgap than silicon and thus inclusion of germanium in a hydrogenated amorphous silicon alloy decreases the alloy's bandgap.
  • [0067]
    Similarly one could incorporate boron or phosphorus atoms in hydrogenated amorphous silicon alloys in order to adjust their conductive properties. Including boron in a hydrogenated amorphous silicon alloy creates a positively doped conductive region. Conversely, including phosphorus in a hydrogenated amorphous silicon alloy creates a negatively doped conductive region.
  • [0068]
    Hydrogenated amorphous silicon alloy films are prepared by deposition in a deposition chamber. Heretofore, in preparing hydrogenated amorphous silicon alloys by deposition in a deposition chamber, carbon, germanium, boron or phosphorus have been incorporated into the alloys by including in the deposition gas mixture carbon, germanium, boron or phosphorus containing gases such as methane (CH4), germane (GeH4), germanium tetrafluoride (GeF4), higher order germanes such as digermane (Ge2 H6), diborane (B2 H6) or phosphine (PH3). See for example, U.S. Pat. Nos. 4,491,626, 4,142,195, 4,363,828, 4,504,518, 4,344,984, 4,435,445, and 4,394,400. A drawback of this practice, however, is that the way in which the carbon, germanium, boron or phosphorus atoms are incorporated into the hydrogenated amorphous silicon alloy is not controlled. That is, these elements are incorporated into the resulting alloy in a highly random manner thereby increasing the likelihood of undesirable chemical bonds.
  • [0069]
    Thus, in cases where PV devices are manufactured, and specific and controlled reaction and or deposition conditions are required to produce the films of the PV, the present invention technology will be useful.
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4335266 *31 Dec 198015 Jun 1982The Boeing CompanyMethods for forming thin-film heterojunction solar cells from I-III-VI.sub.2
US4392451 *2 Jul 198112 Jul 1983The Boeing CompanyApparatus for forming thin-film heterojunction solar cells employing materials selected from the class of I-III-VI2 chalcopyrite compounds
US4423701 *29 Mar 19823 Jan 1984Energy Conversion Devices, Inc.Glow discharge deposition apparatus including a non-horizontally disposed cathode
US4438723 *28 Sep 198127 Mar 1984Energy Conversion Devices, Inc.Multiple chamber deposition and isolation system and method
US4438724 *13 Aug 198227 Mar 1984Energy Conversion Devices, Inc.Grooved gas gate
US4440107 *12 Jul 19823 Apr 1984Energy Conversion Devices, Inc.Magnetic apparatus for reducing substrate warpage
US4450786 *16 Feb 198329 May 1984Energy Conversion Devices, Inc.Grooved gas gate
US4462332 *29 Apr 198231 Jul 1984Energy Conversion Devices, Inc.Magnetic gas gate
US4462333 *27 Oct 198231 Jul 1984Energy Conversion Devices, Inc.Process gas introduction, confinement and evacuation system for glow discharge deposition apparatus
US4465575 *28 Feb 198314 Aug 1984Atlantic Richfield CompanyMethod for forming photovoltaic cells employing multinary semiconductor films
US4479455 *14 Mar 198330 Oct 1984Energy Conversion Devices, Inc.Process gas introduction and channeling system to produce a profiled semiconductor layer
US4480585 *23 Jun 19836 Nov 1984Energy Conversion Devices, Inc.External isolation module
US4483883 *7 Nov 198320 Nov 1984Energy Conversion Devices, Inc.Upstream cathode assembly
US4492181 *19 Mar 19828 Jan 1985Sovonics Solar SystemsApparatus for continuously producing tandem amorphous photovoltaic cells
US4520757 *23 Dec 19834 Jun 1985Energy Conversion Devices, Inc.Process gas introduction, confinement and evacuation system for glow discharge deposition apparatus
US4576830 *5 Nov 198418 Mar 1986Chronar Corp.Deposition of materials
US4663828 *11 Oct 198512 May 1987Energy Conversion Devices, Inc.Process and apparatus for continuous production of lightweight arrays of photovoltaic cells
US4889609 *6 Sep 198826 Dec 1989Ovonic Imaging Systems, Inc.Continuous dry etching system
US5045409 *17 Nov 19883 Sep 1991Atlantic Richfield CompanyProcess for making thin film solar cell
US5078803 *22 Sep 19897 Jan 1992Siemens Solar Industries L.P.Solar cells incorporating transparent electrodes comprising hazy zinc oxide
US5090356 *28 Jun 199125 Feb 1992United Solar Systems CorporationChemically active isolation passageway for deposition chambers
US5244509 *7 Aug 199114 Sep 1993Canon Kabushiki KaishaSubstrate having an uneven surface for solar cell and a solar cell provided with said substrate
US5258075 *23 Apr 19922 Nov 1993Canon Kabushiki KaishaProcess for producing photoconductive member and apparatus for producing the same
US5366554 *10 Aug 199322 Nov 1994Canon Kabushiki KaishaDevice for forming a deposited film
US5374313 *14 Apr 199320 Dec 1994Energy Conversion Devices, Inc.Magnetic roller gas gate employing transonic sweep gas flow to isolate regions of differing gaseous composition or pressure
US5436204 *22 Aug 199425 Jul 1995Midwest Research InstituteRecrystallization method to selenization of thin-film Cu(In,Ga)Se2 for semiconductor device applications
US5474611 *22 Aug 199412 Dec 1995Yoichi Murayama, Shincron Co., Ltd.Plasma vapor deposition apparatus
US5514217 *7 Jun 19947 May 1996Canon Kabushiki KaishaMicrowave plasma CVD apparatus with a deposition chamber having a circumferential wall comprising a curved moving substrate web and a microwave applicator means having a specific dielectric member on the exterior thereof
US5626688 *1 Dec 19956 May 1997Siemens AktiengesellschaftSolar cell with chalcopyrite absorber layer
US5728231 *15 May 199617 Mar 1998Matsushita Electric Industrial Co., Ltd.Precursor for semiconductor thin films and method for producing semiconductor thin films
US5919310 *29 Feb 19966 Jul 1999Canon Kabushiki KaishaContinuously film-forming apparatus provided with improved gas gate means
US6214120 *27 Aug 199910 Apr 2001Innovac CorporationHigh throughput multi-vacuum chamber system for processing wafers and method of processing wafers using the same
US6488824 *14 Jul 20003 Dec 2002Raycom Technologies, Inc.Sputtering apparatus and process for high rate coatings
US7047903 *21 Jan 200223 May 2006Ishikawajima-Harima Heavy Industries Co., Ltd.Method and device for plasma CVD
US7319190 *10 Nov 200515 Jan 2008Daystar Technologies, Inc.Thermal process for creation of an in-situ junction layer in CIGS
US7576017 *10 Nov 200518 Aug 2009Daystar Technologies, Inc.Method and apparatus for forming a thin-film solar cell using a continuous process
US20020129476 *20 May 200219 Sep 2002Matsushita Electric Industrial Co., Ltd.Device for manufacturing semiconductor device and method of manufacturing the same
US20020189665 *10 Apr 200119 Dec 2002Davis, Joseph & NegleyPreparation of CIGS-based solar cells using a buffered electrodeposition bath
US20040094196 *27 Apr 200120 May 2004Sean ShaheenPhotovoltaic cell
US20050186342 *18 Sep 200425 Aug 2005Nanosolar, Inc.Formation of CIGS absorber layer materials using atomic layer deposition and high throughput surface treatment
US20060040475 *18 Aug 200423 Feb 2006Emerson David TMulti-chamber MOCVD growth apparatus for high performance/high throughput
US20060096536 *10 Nov 200511 May 2006Daystar Technologies, Inc.Pressure control system in a photovoltaic substrate deposition apparatus
US20060096537 *10 Nov 200511 May 2006Daystar Technologies, Inc.Method and apparatus for forming a thin-film solar cell using a continuous process
US20060219288 *10 Nov 20055 Oct 2006Daystar Technologies, Inc.Process and photovoltaic device using an akali-containing layer
US20060219547 *10 Nov 20055 Oct 2006Daystar Technologies, Inc.Vertical production of photovoltaic devices
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US7763535 *29 Aug 200827 Jul 2010Applied Materials, Inc.Method for producing a metal backside contact of a semiconductor component, in particular, a solar cell
US791940027 Jun 20085 Apr 2011Stion CorporationMethods for doping nanostructured materials and nanostructured thin films
US801786015 May 200713 Sep 2011Stion CorporationMethod and structure for thin film photovoltaic materials using bulk semiconductor materials
US802190530 Apr 201020 Sep 2011Ascent Solar Technologies, Inc.Machine and process for sequential multi-sublayer deposition of copper indium gallium diselenide compound semiconductors
US805809212 Sep 200815 Nov 2011Stion CorporationMethod and material for processing iron disilicide for photovoltaic application
US806726324 Nov 201029 Nov 2011Stion CorporationThermal management and method for large scale processing of CIS and/or CIGS based thin films overlying glass substrates
US807117927 Jun 20086 Dec 2011Stion CorporationMethods for infusing one or more materials into nano-voids if nanoporous or nanostructured materials
US807142124 Nov 20106 Dec 2011Stion CorporationThermal management and method for large scale processing of CIS and/or CIGS based thin films overlying glass substrates
US807617624 Nov 201013 Dec 2011Stion CorporationThermal management and method for large scale processing of CIS and/or CIGS based thin films overlying glass substrates
US808429124 Nov 201027 Dec 2011Stion CorporationThermal management and method for large scale processing of CIS and/or CIGS based thin films overlying glass substrates
US808429224 Nov 201027 Dec 2011Stion CorporationThermal management and method for large scale processing of CIS and/or CIGS based thin films overlying glass substrates
US808864024 Nov 20103 Jan 2012Stion CorporationThermal management and method for large scale processing of CIS and/or CIGS based thin films overlying glass substrates
US810543711 Jul 201131 Jan 2012Stion CorporationMethod and system for large scale manufacture of thin film photovoltaic devices using multi-chamber configuration
US8134069 *13 Apr 200913 Mar 2012MiasoleMethod and apparatus for controllable sodium delivery for thin film photovoltaic materials
US813807025 Nov 200920 Mar 2012Innovalight, Inc.Methods of using a set of silicon nanoparticle fluids to control in situ a set of dopant diffusion profiles
US816358721 Jul 200924 Apr 2012Innovalight, Inc.Methods of using a silicon nanoparticle fluid to control in situ a set of dopant diffusion profiles
US81684639 Oct 20091 May 2012Stion CorporationZinc oxide film method and structure for CIGS cell
US817837011 Jul 201115 May 2012Stion CorporationMethod and system for large scale manufacture of thin film photovoltaic devices using multi-chamber configuration
US818306611 Jul 201122 May 2012Stion CorporationMethod and system for large scale manufacture of thin film photovoltaic devices using multi-chamber configuration
US81930282 Aug 20115 Jun 2012Stion CorporationSulfide species treatment of thin film photovoltaic cell and manufacturing method
US819812226 Jul 201112 Jun 2012Stion CorporationBulk chloride species treatment of thin film photovoltaic cell and manufacturing method
US8207444 *1 Jul 200826 Jun 2012Sunpower CorporationFront contact solar cell with formed electrically conducting layers on the front side and backside
US821637923 Apr 200910 Jul 2012Applied Materials, Inc.Non-circular substrate holders
US823659725 Sep 20097 Aug 2012Stion CorporationBulk metal species treatment of thin film photovoltaic cell and manufacturing method
US82580002 Aug 20114 Sep 2012Stion CorporationBulk sodium species treatment of thin film photovoltaic cell and manufacturing method
US826349414 Jan 201111 Sep 2012Stion CorporationMethod for improved patterning accuracy for thin film photovoltaic panels
US828794224 Sep 200816 Oct 2012Stion CorporationMethod for manufacture of semiconductor bearing thin film material
US831432616 Aug 201120 Nov 2012Stion CorporationMethod and structure for thin film photovoltaic materials using bulk semiconductor materials
US83185319 Nov 201127 Nov 2012Stion CorporationThermal management and method for large scale processing of CIS and/or CIGS based thin films overlying glass substrates
US834424318 Nov 20091 Jan 2013Stion CorporationMethod and structure for thin film photovoltaic cell using similar material junction
US83777364 Jan 201219 Feb 2013Stion CorporationSystem and method for transferring substrates in large scale processing of CIGS and/or CIS devices
US838345029 Sep 200926 Feb 2013Stion CorporationLarge scale chemical bath system and method for cadmium sulfide processing of thin film photovoltaic materials
US839465821 Sep 201112 Mar 2013Innovalight, Inc.Methods of using a silicon nanoparticle fluid to control in situ a set of dopant diffusion profiles
US839466222 Sep 200912 Mar 2013Stion CorporationChloride species surface treatment of thin film photovoltaic cell and manufacturing method
US839877217 Aug 201019 Mar 2013Stion CorporationMethod and structure for processing thin film PV cells with improved temperature uniformity
US842051712 Feb 201016 Apr 2013Innovalight, Inc.Methods of forming a multi-doped junction with silicon-containing particles
US842573923 Sep 200923 Apr 2013Stion CorporationIn chamber sodium doping process and system for large scale cigs based thin film photovoltaic materials
US84358227 Dec 20107 May 2013Stion CorporationPatterning electrode materials free from berm structures for thin film photovoltaic cells
US843582625 Sep 20097 May 2013Stion CorporationBulk sulfide species treatment of thin film photovoltaic cell and manufacturing method
US843644530 Nov 20117 May 2013Stion CorporationMethod of manufacture of sodium doped CIGS/CIGSS absorber layers for high efficiency photovoltaic devices
US846106128 Jun 201111 Jun 2013Stion CorporationQuartz boat method and apparatus for thin film thermal treatment
US84655895 Feb 201018 Jun 2013Ascent Solar Technologies, Inc.Machine and process for sequential multi-sublayer deposition of copper indium gallium diselenide compound semiconductors
US847610418 Sep 20092 Jul 2013Stion CorporationSodium species surface treatment of thin film photovoltaic cell and manufacturing method
US849027110 Dec 200723 Jul 2013Universal Instruments CorporationFlexible substrate tensioner
US850150724 Jan 20126 Aug 2013Stion CorporationMethod for large scale manufacture of thin film photovoltaic devices using multi-chamber configuration
US850152121 Sep 20096 Aug 2013Stion CorporationCopper species surface treatment of thin film photovoltaic cell and manufacturing method
US850778618 Jun 201013 Aug 2013Stion CorporationManufacturing method for patterning CIGS/CIS solar cells
US851252825 Apr 201220 Aug 2013Stion CorporationMethod and system for large scale manufacture of thin film photovoltaic devices using single-chamber configuration
US851310429 Jun 201120 Aug 2013Innovalight, Inc.Methods of forming a floating junction on a solar cell with a particle masking layer
US855762510 Feb 201215 Oct 2013Stion CorporationZinc oxide film method and structure for cigs cell
US861439612 Sep 200824 Dec 2013Stion CorporationMethod and material for purifying iron disilicide for photovoltaic application
US861791714 Jul 201131 Dec 2013Stion CorporationConsumable adhesive layer for thin film photovoltaic material
US862367725 Apr 20127 Jan 2014Stion CorporationMethod and system for large scale manufacture of thin film photovoltaic devices using multi-chamber configuration
US862899719 Sep 201114 Jan 2014Stion CorporationMethod and device for cadmium-free solar cells
US86421381 Jun 20094 Feb 2014Stion CorporationProcessing method for cleaning sulfur entities of contact regions
US864236125 Apr 20124 Feb 2014Stion CorporationMethod and system for large scale manufacture of thin film photovoltaic devices using multi-chamber configuration
US8647995 *21 Jul 201011 Feb 2014Corsam Technologies LlcFusion formable silica and sodium containing glasses
US867367512 May 201118 Mar 2014Stion CorporationHumidity control and method for thin film photovoltaic materials
US869161831 Aug 20118 Apr 2014Stion CorporationMetal species surface treatment of thin film photovoltaic cell and manufacturing method
US8703527 *20 Nov 200922 Apr 2014First Solar, Inc.Photovoltaic devices including copper indium gallium selenide
US87282004 Jan 201220 May 2014Stion CorporationMethod and system for recycling processing gas for selenization of thin film photovoltaic materials
US874168929 Sep 20093 Jun 2014Stion CorporationThermal pre-treatment process for soda lime glass substrate for thin film photovoltaic materials
US8759669 *16 Jan 201224 Jun 2014Hanergy Hi-Tech Power (Hk) LimitedBarrier and planarization layer for thin-film photovoltaic cell
US875967124 Sep 200824 Jun 2014Stion CorporationThin film metal oxide bearing semiconductor material for single junction solar cell devices
US880909621 Oct 201019 Aug 2014Stion CorporationBell jar extraction tool method and apparatus for thin film photovoltaic materials
US8841545 *10 Feb 200923 Sep 2014Tohoku UniversitySolar cell wherein solar photovolatic thin film is directly formed on base
US885988014 Jan 201114 Oct 2014Stion CorporationMethod and structure for tiling industrial thin-film solar devices
US88713051 Nov 201128 Oct 2014Stion CorporationMethods for infusing one or more materials into nano-voids of nanoporous or nanostructured materials
US887805313 Jun 20124 Nov 2014Sunpower CorporationFront contact solar cell with formed emitter
US89411321 Dec 201027 Jan 2015Stion CorporationApplication specific solar cell and method for manufacture using thin film photovoltaic materials
US899215330 Jun 200931 Mar 2015Intevac, Inc.System and method for substrate transport
US89986064 Jan 20127 Apr 2015Stion CorporationApparatus and method utilizing forced convection for uniform thermal treatment of thin film devices
US90879435 Jun 200921 Jul 2015Stion CorporationHigh efficiency photovoltaic cell and manufacturing method free of metal disulfide barrier material
US909358219 Sep 201228 Jul 2015Opterra Energy Services, Inc.Solar canopy assembly
US909358319 Sep 201228 Jul 2015Opterra Energy Services, Inc.Folding solar canopy assembly
US909693018 Jul 20114 Aug 2015Stion CorporationApparatus for manufacturing thin film photovoltaic devices
US910577614 May 200711 Aug 2015Stion CorporationMethod and structure for thin film photovoltaic materials using semiconductor materials
US9117965 *22 Oct 201225 Aug 2015Dow Global Technologies LlcMethod of manufacture of chalcogenide-based photovoltaic cells
US915714529 Jul 200913 Oct 2015Intevac, Inc.Processing tool with combined sputter and evaporation deposition sources
US9166077 *10 Jun 201120 Oct 2015Solar Frontier K. K.Thin film solar cell
US931240619 Dec 201212 Apr 2016Sunpower CorporationHybrid emitter all back contact solar cell
US932158320 May 201126 Apr 2016Opterra Energy Services, Inc.Pallet assembly for transport of solar module array pre-assembly
US943775530 May 20126 Sep 2016Sunpower CorporationFront contact solar cell with formed electrically conducting layers on the front side and backside
US953091010 Feb 201427 Dec 2016Corsam Technologies LlcFusion formable silica and sodium containing glasses
US956890015 Mar 201314 Feb 2017Opterra Energy Services, Inc.Systems and methods for regulating an alternative energy source that is decoupled from a power grid
US970156724 Apr 201411 Jul 2017Corning IncorporatedPhotovoltaic module package
US20060219288 *10 Nov 20055 Oct 2006Daystar Technologies, Inc.Process and photovoltaic device using an akali-containing layer
US20070264488 *14 May 200715 Nov 2007Stion CorporationMethod and structure for thin film photovoltaic materials using semiconductor materials
US20080092953 *15 May 200724 Apr 2008Stion CorporationMethod and structure for thin film photovoltaic materials using bulk semiconductor materials
US20080169025 *10 Sep 200717 Jul 2008Basol Bulent MDoping techniques for group ibiiiavia compound layers
US20080300918 *29 May 20084 Dec 2008Commercenet Consortium, Inc.System and method for facilitating hospital scheduling and support
US20090017605 *27 Jun 200815 Jan 2009Stion CorporationMethods for doping nanostructured materials and nanostructured thin films
US20090061627 *29 Aug 20085 Mar 2009Applied Materials, Inc.Method for producing a metal backside contact of a semiconductor component, in particular, a solar cell
US20090087370 *12 Sep 20082 Apr 2009Stion CorporationMethod and material for purifying iron disilicide for photovoltaic application
US20090087939 *24 Sep 20082 Apr 2009Stion CorporationColumn structure thin film material using metal oxide bearing semiconductor material for solar cell devices
US20090089917 *16 May 20089 Apr 2009Hon Hai Precision Industry Co., Ltd.Multifunctional helmet
US20090117718 *27 Jun 20087 May 2009Stion CorporationMethods for infusing one or more materials into nano-voids if nanoporous or nanostructured materials
US20090250105 *24 Sep 20088 Oct 2009Stion CorporationThin film metal oxide bearing semiconductor material for single junction solar cell devices
US20090272422 *27 Apr 20095 Nov 2009Delin LiSolar Cell Design and Methods of Manufacture
US20090320920 *5 Jun 200931 Dec 2009Stion CorporationHigh efficiency photovoltaic cell and manufacturing method free of metal disulfide barrier material
US20090324369 *30 Jun 200931 Dec 2009Intevac, Inc.System and method for substrate transport
US20100000597 *1 Jul 20087 Jan 2010Peter John CousinsFront Contact Solar Cell With Formed Electrically Conducting Layers On the Front Side And Backside
US20100024731 *29 Jul 20094 Feb 2010Eristoff D GuyProcessing tool with combined sputter and evaporation deposition sources
US20100101624 *20 Jun 200729 Apr 2010Emanuela FiorettiPhotovoltaic module and modular panel made with it to collect radiant solar energy
US20100122726 *18 Nov 200920 May 2010Stion CorporationMethod and structure for thin film photovoltaic cell using similar material junction
US20100163406 *30 Dec 20081 Jul 2010Applied Materials, Inc.Substrate support in a reactive sputter chamber
US20100167510 *25 Nov 20091 Jul 2010Innovalight, Inc.Methods of using a set of silicon nanoparticle fluids to control in situ a set of dopant diffusion profiles
US20100186812 *20 Nov 200929 Jul 2010First Solar, Inc.Photovoltaic devices including copper indium gallium selenide
US20100258191 *13 Apr 200914 Oct 2010MiasoleMethod and apparatus for controllable sodium delivery for thin film photovoltaic materials
US20100273314 *23 Apr 200928 Oct 2010Tetsuya IshikawaNon-circular substrate holders
US20100326511 *10 Feb 200930 Dec 2010Tokyo Electron LimitedSolar cell wherein solar photovolatic thin film is directly formed on base
US20110003464 *21 Jul 20096 Jan 2011Giuseppe ScarderaMethods of using a silicon nanoparticle fluid to control in situ a set of dopant diffusion profiles
US20110003465 *12 Feb 20106 Jan 2011Innovalight, Inc.Methods of forming a multi-doped junction with silicon-containing particles
US20110003466 *4 Jun 20106 Jan 2011Innovalight, Inc.Methods of forming a multi-doped junction with porous silicon
US20110017297 *21 Jul 201027 Jan 2011Bruce Gardiner AitkenFusion formable silica and sodium containing glasses
US20110067998 *20 Sep 200924 Mar 2011MiasoleMethod of making an electrically conductive cadmium sulfide sputtering target for photovoltaic manufacturing
US20110070685 *24 Nov 201024 Mar 2011Stion CorporationThermal management and method for large scale processing of cis and/or cigs based thin films overlying glass substrates
US20110070686 *24 Nov 201024 Mar 2011Stion CorporationThermal management and method for large scale processing of cis and/or cigs based thin films overlying glass substrates
US20110070687 *24 Nov 201024 Mar 2011Stion CorporationThermal management and method for large scale processing of cis and/or cigs based thin films overlying glass substrates
US20110070690 *24 Nov 201024 Mar 2011Stion CorporationThermal management and method for large scale processing of cis and/or cigs based thin films overlying glass substrates
US20110183504 *25 Jan 201028 Jul 2011Innovalight, Inc.Methods of forming a dual-doped emitter on a substrate with an inline diffusion apparatus
US20120132282 *28 Nov 201131 May 2012Bruce Gardiner AitkenAlkali-free high strain point glass
US20120192941 *16 Jan 20122 Aug 2012Global Solar Energy, Inc.Barrier and planarization layer for thin-film photovoltaic cell
US20130074925 *10 Jun 201128 Mar 2013Showa Shell Sekiyu K.K.Thin film solar cell
US20130112273 *7 Jun 20119 May 2013Panasonic CorporationSolar cell
US20130269780 *20 Dec 201117 Oct 2013NexcisInterface between a i-iii-vi2 material layer and a molybdenum substrate
US20130319502 *31 May 20125 Dec 2013Aqt Solar, Inc.Bifacial Stack Structures for Thin-Film Photovoltaic Cells
US20140166107 *13 Dec 201219 Jun 2014Intermolecular, Inc.Back-Contact Electron Reflectors Enhancing Thin Film Solar Cell Efficiency
USD62569514 Oct 200819 Oct 2010Stion CorporationPatterned thin film photovoltaic module
USD6276961 Jul 200923 Nov 2010Stion CorporationPin striped thin film solar module for recreational vehicle
USD62833212 Jun 200930 Nov 2010Stion CorporationPin striped thin film solar module for street lamp
USD63241513 Jun 20098 Feb 2011Stion CorporationPin striped thin film solar module for cluster lamp
USD65226223 Jun 200917 Jan 2012Stion CorporationPin striped thin film solar module for cooler
USD66204012 Jun 200919 Jun 2012Stion CorporationPin striped thin film solar module for garden lamp
USD66204123 Jun 200919 Jun 2012Stion CorporationPin striped thin film solar module for laptop personal computer
CN103003959A *7 Jun 201127 Mar 2013松下电器产业株式会社Semiconductor film, and solar cell
EP2031659A1 *30 Aug 20074 Mar 2009Applied Materials, Inc.Method for creating a metal backing pin for a semiconductor element, in particular a solar cell
WO2008127449A2 *3 Dec 200723 Oct 2008Solopower, Inc.Doping techniques for group ibiiiavia compound layers
WO2008127449A3 *3 Dec 200715 Jan 2009Solopower IncDoping techniques for group ibiiiavia compound layers
WO2009030374A1 *20 Aug 200812 Mar 2009Applied Materials, Inc.Method for producing a metal rear contact of a semiconductor element, particularly a solar cell
WO2010014761A1 *29 Jul 20094 Feb 2010Intevac, Inc.Processing tool with combined sputter and evaporation deposition sources
WO2011066272A1 *23 Nov 20103 Jun 2011Innovalight, Inc.Methods of using a set of silicon nanoparticle fluids to control in situ a set of dopant diffusion profiles
Classifications
U.S. Classification136/262, 438/95, 136/264, 136/265
International ClassificationH01L31/00
Cooperative ClassificationC23C14/568, H01L31/0749, H01L31/1876, Y02E10/541, H01L31/072, H01L31/0322, Y02P70/521
European ClassificationH01L31/0749, H01L31/032C, H01L31/18H, H01L31/072, C23C14/56F
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24 Jan 2006ASAssignment
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Effective date: 20060111
26 Jun 2007ASAssignment
Owner name: LAMPE, CONWAY & CO., LLC, NEW YORK
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Effective date: 20070615
22 Sep 2009ASAssignment
Owner name: DAYSTAR TECHNOLOGIES, INC., CALIFORNIA
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