Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
  • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
  • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
  • H01L31/076—Multiple junction or tandem solar cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/02—Details
  • H01L31/0216—Coatings
  • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
  • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
  • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
  • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
  • H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
  • H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
  • H01L31/206—Particular processes or apparatus for continuous treatment of the devices, e.g. roll-to roll processes, multi-chamber deposition
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/52—PV systems with concentrators
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/548—Amorphous silicon PV cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention is in the field of silicon photovoltaic cells and more particularly relatively thin, mass-produced, flexible, multi-layer silicon alloy solar cells having an enhanced efficiency and method and apparatus for producing same.
• Silicon is a quite brittle material which is quite difficult to slice thinner than approximately 250 microns. Since the minority electrical carrier dif ⁇ fusion length through single-crystal silicon material averages about 200 microns at an intensity of one sun through air mass one (AMI) , only a relatively small proportion of the electrical carriers generated by incident solar radiation can be collected in a silicon cell having such a thickness as 250 microns. Therefore, the overall conversion efficiency of such thick silicon solar cells is low.
• AMI air mass one
• ⁇ OI_E_C plagued by defects and have occasionally, but not consistently, exhibited conversion efficiencies in laboratory-produced (not commerically produced) units up to approximately 16% at one sun at AMI, with a ribbon thickness of aproximately 100 microns.
• the rate at which each such ribbon has been pulled from a melt is very slow, being of the order of one to twenty square centimeters of ribbon per minute at a thickness of less than 150 microns.
• one sun means the intensity of solar radiation as actually received from the sun without augmentation.
• air mass one or “AMI” means the average maximum solar radiation received at the earth's surface at sea level resulting from solar radiation passing vertically through one thickness of atmosphere.
• the present invention overcomes or substantially eliminates the shortcomings of the prior art as applied to thin silicon solar cells.
• This invention enables thin-film silicon- solar cells to be produced relatively rapidly and at significantly lower costs as compared with the prior art.
• a multi-layer, thin-film, flexible silicon alloy solar cell is described in which the multiple layers extend perpendicularly to the incident light.
• the flexible cell is mass-produced by rolling and laminating two thin ribbons of silicon alloy having thicknesses of the order of 10 to 50 microns with each ribbon passing through multiple rolling stages employ ⁇ ing a ceramic metallic glass semi-conductor alloy of silicon having approximately a zero coefficient of thermal expansion/contraction. The rolling pressure
• This ceramic metallic glass alloy of silicon melts at a relatively low temperature in the range from approximately 800° C. to 1,150° C. (1,472° F. to 2,102° F.). In contrast, the liquidus temperature of silicon is 1,410° C. (2,570° F.).
• the rolling and doping of each moving ribbon can be carried out at a correspondingly relatively low temperature, thereby considerably diminishing the tendency of this molten alloy to pick up contaminants from surfaces of the extruding and rolling processing apparatus. This diminished dissolving tendency is an advantage compared with the normal tendency of molten silicon to dissolve and absorb materials from surfaces with which it comes into contact. ⁇
• the two silicon alloy ribbons are laminated together with a very thin lattice matching layer of less than 60 Angstroms thickness between, and the resultant laminate serves as a substrate on which other layers are deposited. This laminate forms the two main active layers of the photovoltaic cell.
• the very thin lattice matching layer of less than 60 Angstroms thickness serves to match the crystal lattice structure of these two active layers.
• This lattice matching layer may be an insulating layer less than 20 Angstroms thick or a semi-conducting oxide layer less than 60 Angstroms thick.
• this laminate On the front of this laminate, i.e. facing the incident radiation, are six additional layers.
• the lowermost of these six additional layers that is, the closest to the laminate (called the "sixth" of these six layers) is a semi-insulating layer less than 10 Ang ⁇ stroms thick (preferably 6 to 9 Angstroms thick) con ⁇ taining cobalt and tin applied by metal organic chemical vapor deposition.
• This thin semi-insulating layer acts as a passivating layer for lowering surface recombinat- ion and for helping to minimize the crystal lattice mismatch.
• this sixth layer has a bright green-to-blue color and acts as a spectral filter for excluding incident radiation having a wave-length longer than the middle of the near infra-red range, i.e. having a wavelength longer than approxmately 12,000 Angstroms (visible light is in the range of from about 4,000 Angstroms to about 7,200 Angstroms) for keeping the cell operating relatively cool by filtering out the longer near infra-red and the far infra-red wavelengths which ' o not contribute to electrical output of the cell.
• the next lowermost (fifth) of these six layers is a semi-conductive "window" layer containing wet-chemical- vapor-deposited tin oxide having a thickness in the range from 300 to 850 Angstroms (preferably 650 to 750 Angstroms).
• This fifth layer serves as the primary protective layer for protecting the cell from degradat ⁇ ion due to attack from oxidizing agents or atmospheric pollution, such as sulphur-containing compounds.
• This semi-conductive "window” layer is transparent for incoming radiation, but it acts as an optical mirror for internal light rays which have been reflected from the back for preventing escape of these internal light rays.
• this semi-conductive window layer advantageously operates as a collection layer in cooperat ⁇ ion with the layers beneath.
• the next lowermost (fourth) of these six layers is a chemical-vapor-deposited, thin insulating layer less than 15 Angstroms thick for electrically insulat- ing a front electrical collection grid from the semi- conductive window layer described immediately above.
• This thin insulating layer acts as a tunneling layer for allowing the electrical current carriers to reach the collection grid.
• the front three-layer assembly of the -six com ⁇ prises a triple-layer, anti-reflection coating (ARC) covering the front face of the cell.
• ARC anti-reflection coating
• the middle (second) layer serves to bond the other two ARC layers together and advantageous- ly acts as a secondary, protective glass-like layer for protecting the photovoltaic cell from degradation due to attack from oxidizing agents or pollutants in the atmosphere.
• this three-layer ARC assembly there is a reflective rear (third) layer which cooperates with the transparent mirror-like "window” layer decribed above for advantageously acting as an internal mirror.
• This internal mirror advantageously causes radiation in the visible range of the electro-magnetic spectrum ("light rays") to be reflected back and forth within the cell between the rear and front of the cell for travers ⁇ ing the light rays multiple times back and forth through the cell for improving the likelihood of photovoltaic interaction between the photons of light and the active photovoltaic regions of this cell.
• a top (first) layer mainly comprised of silicon dioxide having a thickness in the range from 200 to 650 Ang ⁇ stroms.
• This top layer is on the front face of the solar cell.
• the six layers described above which are on the front of the ribbon laminate effectively adapt the overall cell to be receptive to incident solar radiation in the range from about 4,000 to about 12,000 Angstroms and effectively to exclude radiation outside of this range. This range comprises approximately 68 percent of the solar radiant energy reaching the earth's surface vertically through the thickness of one atmosphere.
• the rear of the laminate which forms the rear of the cell, preferably has an undulating configuration for redirecting the reflected light rays along random ⁇ ized paths for further improving the likelihood of inter-action of the photons with these active regions.
• FIGURE 1 is an enlarged cross section of a portion of a solar cell embodying the present invention.
• FIG. 2 is a plan view of the front face of the solar cell drawn approximately one and a half times actual size.
• FIG. 3 is an enlargement of a portion of FIG.
• FIG. 4 is a partial perspective view of a portion of FIG. 3 shown further enlarged.
• FIG. 5 is an enlarged partial sectional view of a main bus taken along the line 5-5 in FIG. 2 ,
• FIG. 6 is an enlarged partial sectional view of one of the front contact members taken along the line 6 in FIG. 2.
• FIG. 6 also corresponds to an enlarge ⁇ ment of the front contact seen in FIG. 1 and an enlarge- ment of this same front contact seen at the left in FIG. 5.
• FIG. 7 is an enlarged partial sectional view of an intermediate bus taken along the line 7-7 in FIG. 2.
• FIG. 8 is an enlarged partial sectional view of a side rail bus, being a section taken along the line 8-8 in FIG. 2.
• FIG. 9 is a diagrammatic illustration of the ribbon laminate production method and apparatus.
• FIG. 10 is a diagrammatic illustration of further production method and apparatus continuing from the right of FIG. 9.
• FIG. 11 is an enlarged view of a portion of FIG. 9.
• FIGURE 1 is a partial cross-sectional elevational view of a multi-layer, thin-film, flexible photovoltaic cell 20 embodying the . present invention.
• the various layers of this cell are not drawn to scale whether vertically or horizontally, but rather are drawn to illustrate clearly the principles of this invention.
• the front (top) is indicated at 21 and is intended to face the incident solar radiation.
• This front 21 is generally planar except for the regions in which are located the front contact members 27 (FIG. 4) , the intermediate bus bars 28 (best seen in FIGS. 3 and 4), the main bus bars 29 (FIGS. 3 and 4), and the side rail buses 26 (FIGS. 2 and 8), which will be described in detail further below.
• the rear (bottom) is indicated at 22, and it preferably has a non-planar configuration, being defined by a sequence of pairs of sloping planes 23 and 24 with rear contact members 25 extending along the lowermost regions between these sloping planes 23 and 24, as will be described in detail further below.
• the first step is formation of a substrate ribbon laminate 100 by the method and appara ⁇ tus shown in FIGS. 9, 10 and 11.
• a first extruder 101 for extruding a molten viscous ceramic metallic glass silicon alloy forming a pre-ribbon 51A (FIGS. 9 and 11) passing through a sequence of rolling stations 102, 104, 106, respectively, including pairs of opposed rollers 111 and 112, 113 and 114, 115 and 116 located in a sequence of heated chambers 117, 118 and 119, respectively.
• These chambers are separated from each other by partitions 120.
• Each such partition 120 includes a baffled port 121 for enabling the moving ribbon to travel through this port while preventing any significant flow of the gaseous content of a chamber into a neighboring chamber. It is to be understood that each port 121 may include a plurality of baffles extend ⁇ ing close to the travelling ribbon for preventing the gaseous content of one chamber from entering the next chamber.
• gaseous diffusion tubes 131 and 132, 133 and 134, 135 and 136 extending into the respective chambers 117, 118 and 119.
• These gaseous diffusion tubes disperse gaseous dopants onto the opposite surfaces of the hot moving ribbon of silicon alloy.
• This hot silicon alloy ribbon 51A is reduced in thick ⁇ ness as it passes between the opposed pairs of rollers in the rolling stations 102, 104 and 106.
• the ribbon after reduction in thickness is shown at 51 in FIG. 9 exiting from the roller station 106 and entering an ion implant station 107.
• the substrate ribbon 51 has a planar front surface 47 and preferably an undulating rear surface 22.. This undulating rear surface 22
• OMPI includes a repetitive sequence of pairs of sloping planes 23 and 24 each of which slopes at an acute angle in the range from approximately 10° to 15° to the horizontal.
• planar areas 64 located between and contiguous with the lower limits 63 (FIG. 1) of the downwardly sloping planes 24 and the lower limits 65 of the next successive upwardly sloping planes 23.
• This ribbon 51 has a nominal thickness of approximately 35 microns plus or minus 5%, i.e. +_ 1.75 microns. In other words, this ribbon 51 has a thickness of approximately fourteen ten thousandths of an inch (0.0014) inch.
• This substrate ribbon 51 varies in thickness due to the presence of the sloping planes 23 and 24.
• the minimum thickness occurs in the vicinity of the peaks 68 of the pairs of sloping planes 23 and 24 and is in the range from approximately 18 microns to 26 mi ⁇ crons, depending upon the tolerances and depending upon whether the slope angle is nearer 15° to 10°.
• the peak-to-peak distance between the successive peaks 68 is approximately 150 microns (six thousandths of an inch).
• This ribbon 51 is formed as shown in FIG. 11 by extruding viscous molten silicon alloy material 70 from the extruder 101.
• This alloy 70 is a ceramic metallic glass alloy of silicon which melts at a rela ⁇ tively low temperature in the range of approximately 800° C. to 1,150° C.
• the alloy 70 is in a semi-liquidus condition as it enters the nip region (FIG. 11) between the first pair of rollers 111, 112.
• An example of this alloy compositon 70 for forming the rear ceramic metallic glass silicon alloy semiconductor ribbon 51 is characterized by the indicated weight percent of the following elements: Range in Weight Percent
• the nip region 122 is between cooled circular cylindrical rollers 111 and 112.
• the surfaces of these opposed counter-rotating rollers 111 and 112 are micro-roughened by selectively etching their surfaces for providing a grip (traction) on the viscous alloy 70.
• These rollers 111, 112 are adjustably spaced apart for producing the first ribbon stage 51A. It is to be noted that these rollers have a diameter of at least 15 centimeters and are formed of a machineable ceramic glass alloy which is cast and then machined and ground to tolerance, fol ⁇ lowed by the etching step for producing traction as discussed.
• the ceramic glass alloy composition of the rollers 111, 112 is made as follows: Silica is dry mixed as a powder with alumina powder and with lithium dioxide powder. This lithium dioxide comes in the form of the naturally occurring mineral Petalite or Spodu- mene, preferably using the latter mineral, because it is more readily obtained in the United States.
• the dry mixture is heated in a crucible made of alumina or SIALON or SION, or fused quartz or silicon nitride. When molten, the composition is purified to remove substantially all oxygen and other trace elements which would contaminate the ribbon being rolled.
• the purified roller composition is characterized by the indicated weight percent of the following elements:
• this machineable ceramic glass alloy composition is cast to shape, machined and ground to tolerance and then selectively etched for providing surface traction of the rollers 111, 112 on the molten alloy 70.
• the molten alloy 70 entering the nip 122 is formed by extrusion through a wide slot orifice 78 in the nozzle 80 of the extruder 101.
• the vertical dimen ⁇ sion of the slot orifice 78 is considerably greater than the spacing between the pair of opposed rolls 111, 112.
• the extruder and its interchangeable nozzle 80 are formed of a machineable ceramic glass composition including the above ingredients.
• the machineable ceramic glass for the extruder and its nozzle is more
• the width of the wide slot orifice 78 is at least 4 centi ⁇ meters, and the slot has a height of at least 100 microns for forming an extrudate ribbon mass 70 of approximately these dimensions.
• the rollers 111, 112 are adjustably spaced apart, thereby producing the first stage ribbon 5lA with a thickness reduction of at least 30% from the entering mass.
• gaseous diffusion tubes 131, 132 are shown between the nozzle 80 and this first pair of rollers, respectively, aimed at the opposite surfaces of the material 70 for dispersing gaseous dopants onto these surfaces.
• the gaseous dopants are being released from these tubes 131, 132 at a pressure exeeding one atmos- phere. These gaseous dopants are attracted to the hot upper and lower surfaces of the semi-liquidus alloy material 70.
• the advantage of the rolling action and pressure in the various rolling stations 102, 104, 106 enhancing the diffusion of the dopants into the ribbon 51A is discussed above. After the first stage ribbon 51A has passed between the cooled rollers 111 and 112, it is in a semi-solidus condition.
• this silicon alloy material 70 between these rollers enables- the alloy to be very rapidly cooled from its semi-liquidus to its semi-solidus condition, thereby advantageously causing plastic deformation with quick cooling for orienting the multi-crystalline structure in the direction of rolling, i.e. parallel with the front and rear surfaces of the ribbon 51 being formed.
• the gaseous dopant which may be supplied through the tube 131 is a phosphorus-containing gas, for example, phosphine (PH3).
• PH3 phosphine
• This same gaseous dopant is supplied through the other tubes 133 and 135 which face the same "front" surface of the ribbon 51 being formed. De- pending upon desired dopant density and gaseous distri ⁇ bution, any one, or more, or all of these tubes 131, 133 and 135 may be utilized.
• front or “top” is intended to indicate a region in the completed cell 20 facing toward the incident light radiation
• rear or “bottom” is intended to mean a region in the cell facing away from the incident light
• the gaseous dopant being supplied through the tubes 132, 134 and 136 to the "rear" surface of the ribbon 51 being formed is a boron-containing gas, for example, boron trifluoride (BF3).
• boron-containing gas for example, boron trifluoride (BF3).
• BF3 boron trifluoride
• any one, or more, or all of these tubes 132, 134 and 136 may be utilized.
• the second pair of adjustably spaced circular cylindrical rollers 113 and 114 in station 104 are
• rollers 113 and 114 are adjusted to produce a reduction in thickness in the travelling ribbon of at least 30%.
• the third pair of rollers 115 and 116 are adjust ⁇ ably spaced and are arranged to produce the exiting ribbon 51 having the thickness dimensions described above.
• This exiting ribbon has a width of at least 11 centimeters.
• the rollers 115 and 116 are constructed of the same material as the first and second pairs 111, 112 and 113, 114.
• the roller 115 is at least 20 cm in diameter and has a ground micro-smooth circular cylind ⁇ rical surface.
• the circular cylindrical surface of the roller 116 which has a diameter of at least 20 cm is preferably machined to have a textured pattern which is the negative of the desired rear pattern 22 (FIG.
• the surface of the roller 116 may be micro-smooth for producing a planar rear surface 22 on the ribbon 51.
• the planar areas 64 and peaks 68 in the rear surface 22 extend parallel with each other and are oriented at an angle of approximately 60° with the length of the ribbon. They are arranged in a chevron pattern similar to the chevron pattern of the front contact members 27 (FIG. 3).
• the chevron pattern on the rear 22 is shifted laterally relative to the chevron pattern on the front 21 by an amount equal to the spacing between the intermediate bus bars 28 (FIG. 3), so that the planar areas 64 with their contact members 25 are oriented at an angle with respect to the front contact members 27.
• the ion implant station 107 there is an evacuated chamber 123 containing ion guns 137, 138 which are preferably aimed at an acute angle, as shown, toward opposite surfaces of the advancing ribbon 51.
• the ion gun 137 is supplied with a gas containing phosphorous, for example, a mixture of phosphine and hydrogen.
• the other ion gun 138 is supplied with a gas containing boron, for example, a mixture of boron trifluoride and hydrogen.
• the ribbon 51 passes a guide roller 124 and enters a laminating station 108.
• this laminating station 108 there is a chamber 124a containing a plural ⁇ ity of electric heaters 140 for raising the temperature of the front surface 47 (FIG. 9) of the ribbon 51.
• a tube 142 feeds oxygen onto the heated front surface 47 for causing diffusion of the oxygen into this surface for forming the thin lattice matching layer 46 (FIG.
• This lattice matching layer 46 may be an insulating oxide layer less than 20 Angstroms thick or a semi ⁇ conducting oxide layer less than 60-Angstroms thick.
• Another tube 144 for aiding in forming this lattice matching layer 46 feeds oxygen into the region where the heated ribbon 51 is pressed by opposed adjustably spaced rollers 145, 146 against another heated ribbon 49 for forming the laminated ribbon 100.
• These laminating- pressure rollers 145 and 146 are constructed of the same material as the rollers 111 and 112. The laminating- pressure rollers 145 and 146 have micro-smooth surfaces and a dia ⁇ ieter of at least 15 cm.
• roller 116 is textured
• roller 146 is similarly textured and is synchronized in motion with the existing pattern on the rear of the ribbon 51 for engaging this existing pattern without unduly distorting it.
• the roller 146 will then have the same diameter as the roller 116, and the roller 145 will have the same diameter as its opposed roller 146.
• the ribbon 49 is formed as shown in FIG. 9 by extrusion of an extrudate 270 plus rolling, utilizing an extruder 201 followed by rolling stations 202, 204, 206 in which there are chambers 217, 218, 219, contain ⁇ ing pairs of adjustably spaced rollers 211 and 212, 213 and 214, 215 and 216, respectively.
• the extruder 201 is identical to the extruder 101, and the rollers 211, 212, 213 and 214 are identical to the rollers 111, 112, 113 and 114.
• the rollers 215 and 216 are identical to the roller 115, and each has a micro-smooth surface for forming the planar front and rear surfaces 71 and 72 (FIG. 9) of the ribbon 49.
• the ribbon 49 has a thickness in the range from 15 to 20 microns and is at least 11 cm wide.
• the ceramic metallic glass semiconductor silicon alloy composition of the extrudate 270 for forming the ribbon 49 is characterized by the indicated weight percent of the
• This ceramic metallic glass semiconductor silicon alloy material 270 is characterized by the indicated weight percent of the following elements:
• each rolling station 202, 204, 206 may be included, depending upon the initial thickness of the extrudate 270 (FIG. 9) and the percent- age reduction in each station. Also, it is to be understood that these stations 202, 204 and 206 and an ion implant station 207 may be arranged in a vertical line for causing the ribbon being rolled to travel vertically in the earth's gravitational field.
• the laminating station 108 may be arranged for travelling the two ribbons 49 and 51 essentially vertically as they are directed along converging paths and laminated.
• tubes 231, 233, 235 and 232, 234, 236 for feeding gaseous dopants onto the front and rear surfaces, respectively, of the ribbon being rolled.
• the gaseous dopant supplied for the front surface of the ribbon 49 is phosphine, and that supplied for the rear surface is boron trifluoride.
• any one, or more, or all of these tubes 231 through 236 may be utilized.
• the ribbon 49 passes through an ion implant station 207 in which there is an evacuated chamber 223 containing ion guns 237, 238 which are preferably aimed at an acute angle, as shown, toward opposite surfaces
• the ion gun 237 is supplied with a gas containing phosphorous, for example a mixture of phosphine and hydrogen.
• a gas containing phosphorous for example a mixture of phosphine and hydrogen.
• boron 238 is supplied with a gas containing boron, for example, a mixture of boron trifluoride and hydrogen.
• the ribbon 49 passes a guide roller 224 and enters the laminating station 108 in which the electric heaters 240 raise the temperature of the rear surface
• a series of tubes 242 and 142 and 144 feeds oxygen or nitrogen onto the heated rear surface 72 for causing diffusion of oxygen or nitrogen into this surface for forming the thin lattice matching layer 46 (FIG. 1) described above.
• the laminating-pressure rollers 145, 146 press the rear surface 72 of ribbon 49 against the front surface 47 of ribbon 51 for laminating them together to form the laminated ribbon 100.
• the thin lattice matching layer 46 (FIG. 1) formed in the laminated ribbon 100 includes thin portions of the rear and front surfaces 72 and 47, respectively, of the ribbons 49 and 51.
• the laminated ribbon 100 passes between other pairs of opposed adjustably spaced rollers 147 and 148 in a heated bonding chamber 125 for causing the laminat ⁇ ed ribbon to bond securely together. If the roller 116 is textured, then the rollers 148 and 147 preferably meet the same criteria as discussed above for rollers 146 and 145.
• the ribbon 51 being formed is heated preferably to be at a level of approximately 20° C. to 60° C. below the semi-liquidus condition.
• the ribbon 49 being formed is heated preferably to be at said temperature level.
• the ribbons 49, 51 and the laminated ribbon 100 are heated preferably to a level of approximately 20° C. to 60° C. below their semi-liquidus temperature. This temperature level is the preferred temperature for promoting crystal growth and orientation of crystals in the ribbons while rolling.
• each pair is inter- connected for causing them to rotate in opposite direct ⁇ ions at the same speed.
• Each pair of rollers is driven independently of the other pairs.
• Means are provided, for example, optical sensors, for sensing any deflection or sag in the moving ribbons or in the laminate.
• the successive pairs of rollers are driven at appropriate speeds for minimizing any deflection or sag of the travelling ribbon or laminate away from the desired path.
• the walls 90 of the chambers 117, 118, 119, 123, 124, 125, 217, 218 and 219 are formed of or lined with the same machineable ceramic glass alloy as the rollers therein.
• there are numerous vents 94 leading into the respective chambers which are normally closed by shut-off valves, as indicated in FIG. 11, but which may be opened for removing and changing the gaseous content of any chamber.
• the gaseous diffusion and ion implant of dopant produce an n+ type layer 40 and a p+ type layer 44, while the main body 42 of the region 49 of the cell 20 is p type.
• the gaseous diffusion and ion implant of dopant produce an n+ type layer 48 and a p+ type layer 52, while the main body 50 of the region 51 of the cell 20 is p type.
• the laminated ribbon passes a guide roller 150 and travels through baffled ports 121 in a series of partitions 120 and passes a guide roller 151, entering etching chamber 126.
• the etchant 152 is maintained at a temperature of 90° C. and comprises a one normal solution of hydrogen fluoride in water. The purpose of this etching step is to thoroughly clean the front and rear surfaces of the laminate ribbon 100.
• the temperature levels in the rolling, laminating and' bonding staions as decribed promote crystal growth and orientation of the crystals.
• the relativively cool etchant 152 at a temperature of 90° C. produces a rapid quench, thereby supercooling the laminate 100 and immediately stopping further crystal growth when the
• ⁇ __/__ crystals are at their optimum crystalline size.
• the guide roller 151 is formed of material not dissolvable in the etchant 152. After the etching is completed, the travelling ribbon 100 passes another guide roller at the opposite end of the etching bath 152 from the guide roller 151 and exits from this bath.
• the etched ribbon 100 is introduced into a rinse bath 154 (FIG. 10) in a rinse chamber 128.
• the rinse bath 154 is methanol.
• the travelling laminate ribbon 100 passes a guide roller 156 and exits from the rinse bath 154.
• the rinsed travelling ribbon 100 passes through a series of baffled ports 121 in a sequence of partitions 120 and passes a guide roller 158 in readiness for further processing steps to be described.
• the layer 38 (FIG. 1) is a semi-insulating layer less than 10 Angstroms thick and preferably in the range from 6 to 9 Angstroms thick. This thin, semi- insulating layer acts as a passivating layer for lower- ing surface recombination and for helping to minimize crystal lattice mismatch.
• This layer 38 is formed by metal organic chemical vapor deposition of cobalt nitride (CoN) together with tin oxide (Sn ⁇ 2) onto the front surface of the laminate 100, at a ratio of approxi- mately 58% cobalt nitride and approximately 42% tin oxide by weight at a temperature of approximately 460° C.
• This layer 38 containing cobalt and tin has a bright green-to-blue color and also advantageously acts as a spectral filter for excluding incident radiation having a wavelength longer than the middle of the near infra-red range. In other words, this layer 38 excludes
• incident radiation having a wavelength longer than approximately 12,000 Angstroms for keeping the cell operating relatively cool by filtering out the longer near infra-red, i.e. wavelengths longer than approxi ⁇ mately 12,000 Angstroms, and the far infra-red wave- lengths, all of which do not contribute to electrical output of the cell.
• the layer 38 also filters out ultraviolet radiation and thus prevents cell degradation by ultraviolet radiation damage.
• the layer 36 is a semi-conductive "window" layer formed by wet chemical deposition spray of a tin-containing compound in solution, for example of tin fluoride (SnF3) in alcohol in a 75% molar solution or tin chloride (SnCl4) in ethyl acetate in an 80% molar solution.
• This wet chemical spray deposition is carried out at a temperature in the range from 380° C. to 430° C.
• This layer 36 has a thickness in the range from 300 to 850 Angstroms (preferably 650 to 750 Angstroms). It acts as the primary protective layer for protecting the cell 20 from degradation due to attack from oxidizing agents or from atmospheric pollution, such as sulphur- containing compounds.
• This semi-conductive “window” layer 36 advantageously acts as a one-way optical mirror. It is transparent for incoming radiation, but it acts as an optical mirror for internal light rays which have been reflected from the back 22 (FIG. 1) for preventing escape of these internal light rays.
• this semi-conductive layer 36 advantageously serves as a collection layer in cooperation with the layers beneath it. photo litho resist is applied to the rear 22 (FIG. 1) of the cell for masking the regions 54B. Then, the interdigitated n+ type narrow stripes 54A are doped by chemical vapor deposition of phosphorous- containing dopant to a depth of approximately 1.5 microns.
• This resist is removed and is applied to the doped stripes 54A, and then the interdigitated p+ type narrow stripes 54B are doped by chemical vapor deposit ⁇ ion of a boron-containing dopant to a depth of approxi ⁇ mately 1.5 microns.
• These narrow interdigitated stripes each have a width in the range of approximately 7 to 15 microns, depending upon their number. There are a plurality of them located between each of the-rear contact members 25, for example, in the range from ten to twenty such interdigitated stripes. Eighteen of them are shown in FIG. 1.
• the first back surface reflector (BSR) mirror layer 56 of tin is plated or applied by metal organic chemical vapor deposition (MOCVD) preferably at least 50 Anstro s thick. On this layer 56 is then applied by plating or MOCVD a chromium layer 58 forming a seond back surface reflector (BSR) having a thickness in the range from 0.5 to 2 microns.
• MOCVD metal organic chemical vapor deposition
• Each such double BSR 56, 58 may, if desired, also be used as charge carrier collection means by electrically connecting the double BSR to the rear contact members 25.
• Strike barriers 59 are then deposited by MOCVD in the rear contact regions. Each such barrier is approximately 100 Angstroms thick and approximately 6 microns wide.
• These strike barriers 59 are formed of titanium nitride and cobalt nitride, at least 90% titan- ium nitride by weight and in the range of 1% to 10% cobalt nitride by weight of the total composition of the strike barrier. They prevent migration of silver atoms from the contact member 25 into the silicon alloy 51. They reduce the contact resistance and assure good electroplating adhesion of the silver contact layers 33 to be formed. The resist still covers the entire rear 22 of the cell 20 except at the strike barriers 59.
• a thin insulating layer 34 less than 15 Angstroms thick of silicon dioxide is formed by chemical vapor deposition.
• This thin insulating layer 34 electrically insulates the front contact members 27 to be formed from the semi-conductive window and one-way mirror layer 36 described above.
• This thin layer 34 acts as a tunneling layer for allow- ing the electrical current carriers to reach the front collection grid contact members 27.
• a resist is applied over the layer 34 except in the regions where the front contact members 27 are to be located. Strike barriers 59 are then chemical vapor deposited similar to those on the rear of the cell for the same purposes.
• OMPI Silver is then plated onto the strike barriers 59 to a depth of approximately 2 microns.
• This plated silver forms the front contact members 27, which are approximately 6 microns wide, being spaced apart approxi ⁇ mately 151 microns on centers and having a chevron pattern as seen in FIGS. 2, 3 and 4.
• This plated silver also forms the layers 33 as shown in FIGS. 4, 5, 7 and 8.
• the silver layer 33 approximately 2 microns thick is also seen in FIG. 1 as the front layer of the rear contacts 25. resist is applied over the front contacts
• a copper layer 35 (FIGS. 1, 4, 5, 7 and 8) approximately 10 microns thick is then plated over the silver layer 33 for forming the intermediate, main and side rail buses 28, 29 and 26, respectively, and rear contact members 25 (FIG. 1).
• solder 37 is applied by a wave solder application technique to form the solder layer 37 of the main buses 29 and of the side rail buses 26 (FIGS. 5 and 7).
• This solder layer 37 has a thickness of approxi ⁇ mately 20 microns.
• the molten solder bath is vibrationally agitated for forming standing waves on the surface of the molten solder.
• the copper layers 35 to be plated with solder are positioned above the solder bath, so that these copper layers touch the crests of the standing waves, without immersion of the remainder of the cell 20 into the solder bath.
• the resist is then removed from the front and rear of the cell, and the lowest (rear) layer 32 of the anti-reflection-coating (ARC) assembly 39 is applied.
• This ARC assembly 39 is a three-layer coating, and it is applied over the contact members 27, as seen in FIGS. 1, 4, 5 and 6.
• This ARC assembly 39 also is applied over the intermediate buses 28, over the main buses 29, and over the side rail buses 26, as seen in FIGS. 4, 5, 7 and 8.
• the lowest anti-reflection-coating layer 32 comprises a mixture of cobalt nitride and titanium nitride which is formed by chemical vapor deposition.
• This layer 32 is less than 100 Angstroms thick, and it cooperates with the transparent mirror-like "window" layer 36 described above for advantageously acting as an internal mirror.
• This internal miror advantageously causes radiation in the visible range of the electro ⁇ magnetic spectrum ("light rays") to be reflected back and forth within the cell between the rear and front of the cell for traversing the light rays multiple times back and forth through the cell for improving the likelihood of photovoltaic interaction between the photons of light and the active photovoltaic regions of this cell.
• the middle ARC layer 31 serves to bond the other two ARC layers 30 and 32 together and advantageous ⁇ ly acts as a secondary, protective glass-like layer for protecting the photovoltaic cell from degradation due to attack from oxidizing agents or pollutants in the atmosphere.
• This middle ARC layer 31 is a semi-vitreous glass which advantageously serves also as an encapsulant anti-oxidation protective layer.
• this layer 31 also protects the interior by acting partially as a heat-conducting layer which diminishes and disperses any tendency toward localized heating resulting from non-uniform illumination.
• this middle layer 31 serves as a semi-vitreous bonding medium for bonding together these three ARC layers 30, 31 and 32 to form the assembly 39.
• the middle anti-reflection layer 31 is a light- transparent, semi-vitreous glass composition containing silicon dioxide (Si ⁇ 2), alumina (AI2O3), boron trioxide (B2O3), sodium oxide (Na2 ⁇ ) and phosphor ⁇ ous pentoxide (P2O5). It has a thickness in the range from 50 to 400 Angstroms, the presently preferred thickness being approximately 150 Angstroms.
• This semi-vitreous glass composition layer 31 contains said ingredients in the following ranges of weight percent of the total composition:
• the ratio of Si ⁇ 2 to AI2O3 in the composi- tion is in the range of 4.8 to 1 to 16.4 to 1.
• composition of this middle anti-reflection layer 31 which advantageously serves the various functions decsribed above is: Weight Percent of Ingredient Total Composition Si ⁇ 2 73
• the ratio of Si ⁇ 2 to AI2O3 is 10.4 to 1.
• composition of this middle anti-reflection layer 31 which advantageously serves the various functions described above is:
• the layer 31 is bonded to the front surface of said layer 32 by heating the layer 31 to a tempera ⁇ ture of from about 750° C. to a temperature of less than about 850° C.
• the front light-transparent ARC layer 30 is mainly comprised of silicon dioxide (Si ⁇ 2) having a thickness in the range from 200 to 650 Angstroms, the presently preferred thickness being approximately 450 Angstroms. It constitutes the top ARC layer, is formed by chemical vapor deposition, and is at the very front of the solar cell 20.
• the intermediate bus bars 28 (FIGS. 4 and 7) have a width of approximately 15 microns and a thickness of approximately 12 microns, including a silver layer 33 which is 2 microns thick and a copper layer 35 which is 10 microns thick.
• the main bus bars 29 (FIGS. 4 and 5) have a width of approximately 48 microns and a thickness of approximately 32 microns, comprising a silver layer 33 (FIG. 5) which is approximately 2 microns thick, a copper layer 35 which is approximately 10 microns thick and a solder layer 37 which is approximately 20 microns thick.
• the side rail buses 26 (FIG. 8) have a width of approximately 96 microns and a thickness of approxi ⁇ mately 32 microns, the same as the main buses 29, as seen in FIGS. 5 and 8.
• the side rail buses 26 have respective silver, copper and solder layers 33, 35, and 37 which are of the same thicknesses as these three respective layers of the main bus 29 (FIG. 5).
• the region 42 has a resistivity in the range of 0.01 to 0.5 ohm centimeters and preferably has a resistivity of 0.05 ohm centimeters.
• the region 50 has a resistivity in the range of 0.15 to 1.0 ohm centi ⁇ meters and preferably has a resistivity in this range and less than 0.5 ohm centimeters.
• the regions 49 and 51 are each shown in an n+- ⁇ -p+ type configuration, but the cell 20 would also be operable with these regions each in p+-n-n+ type configuration. This latter configuration is obtained by interchanging the locations of the phosphorous-containing dopant and boron-containing dopant in FIG. 11.
• the laminate 100 (FIG. 10) after rinsing and after passing the guide roller 158, is edge trimmed by laser beams to a width of 10 centimeters.
• FIGURE 8 shows the edge region of the edge-trimmed laminate substrate.
• the front contact members 27 in the chevron pattern are spaced 151 microns on centers and as shown in FIG. 4, extend at an angle of 60° to the intermediate buses 28.
• the rear contact members 25 (FIG. 1) have a width of approximately 6 microns and a thickness of approximately 12 microns, comprising the layer of silver 33 which is approximately 2 microns thick and the layer of copper 35 which is approximately 10 microns thick.
• the rear contact members 25 are in a chevron pattern and are also spaced 151 microns on centers. Electrical connection with the rear contact members 25 is made by placing their copper layers 35 against a conductive mount (not shown).
• the intermediate bus bars 28 are spaced 0.5 centimeters on centers.
• the main bus bars 29 are spaced 1.0 centimeters on centers, and they connect at their respective ends with both of the side rail buses 26. These side rail buses 26 extend along opposite edges of the cell 20 which is trimmed to a width of 10 centi ⁇ meters, as described above, and thus these side rail buses 26 are spaced apart slightly less than 10 centi ⁇ meters.
• the cell 20 is a continuous ribbon and can be cut to any desired length for forming an individual photovoltaic cell for a particular application. Electrical connection with the front 21 of the cell 20 is made by a plurality of conductive clamps (not shown) which clamp onto the side rail buses 26 at spaced points along the length of these side rail buses in regions where the ARC layer assembly 39 (FIG. 8) has been removed from these side rail buses.
• the ceramic metallic glass semi-conductor alloy compositions of the front region 49 and rear region 51 of the cell 20 enable the respective spectral sensi ⁇ tivities, i.e. the respective band gaps, of these two regions to be individually tailored to the desired frequency ranges of the incident light rays for optimiz ⁇ ing the collection efficiency of the cell 20.
• the preferred band gap for the front cell region 49 is in the range from 1.35 to 1.65 electron volts
• the prefer- red band gap for the rear cell region 51 is in the range from 0.9 to 1.35 electron volts with these two cell regions operating in series electrically as shown in FIG. 1.
• the metalization on the front 21 of the cell provided by the contact members 27 and the intermediate and main buses 28, 29 and the side rail buses 26 enable this cell 20 to be operated at a solar radiation concen ⁇ tration intensity up to 250 suns.
• the metalization on the front 21 including contact members 27, intermediate bus bars 28 and main bus bars 29 is a three-level metalization.
• the shadowing caused by this metalization is less than 5%.
• the active, unshadowed area of this cell is advantageously more than 95%.
• the compositions of this layer 31 may include a flux for lowering its melting temperature.
• Said flux is in an amount less than 20% by weight of the total composition and includes a fluxing compound selected from the group consisting of tin dioxide, antimony dioxide and antimony trioxide.
• the balance of said total composition of layer 31 is trace elements in an amount less than 2% by weight of the total.
• the ceramic metallic glass semi-conductive silicon alloy ribbons 49, 51 and the laminate 100 are preferably heated to be at a level of approximately 20° C. to 60° C. below their semi-liquidus condition.
• Said alloy advantageously melts in the range of approximately 800° C. to 1,150° C.
• the preferred temperature of the silicon alloy in said chambers is in the range from 740° C. to 1,130° c.

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• 1984
  • 1984-10-16 EP EP84903907A patent/EP0197034A1/de not_active Withdrawn
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