WO2016099562A1 - Pâte de métallisation solaire composite à base de nanoparticules d'argent - Google Patents

Pâte de métallisation solaire composite à base de nanoparticules d'argent Download PDF

Info

Publication number
WO2016099562A1
WO2016099562A1 PCT/US2014/071608 US2014071608W WO2016099562A1 WO 2016099562 A1 WO2016099562 A1 WO 2016099562A1 US 2014071608 W US2014071608 W US 2014071608W WO 2016099562 A1 WO2016099562 A1 WO 2016099562A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
metallization
paste
nondeformable
inorganic material
Prior art date
Application number
PCT/US2014/071608
Other languages
English (en)
Inventor
Brian Hardin
Stephen CONNOR
James Randy GROVES
Craig PETERS
Jose PORTILLA
Original Assignee
Plant Pv, Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Plant Pv, Inc filed Critical Plant Pv, Inc
Priority to PCT/US2014/071608 priority Critical patent/WO2016099562A1/fr
Publication of WO2016099562A1 publication Critical patent/WO2016099562A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • Embodiments of the present disclosure relate to conductive metallization pastes and inks for use with silicon based solar cells and other semiconductor devices.
  • Embodiments of the present disclosure relate to conductive metallization pastes and inks for use with silicon based solar cells and other semiconductor devices.
  • FIG. 1 is a schematic drawing that shows an example of silver-based metallization paste 100.
  • the paste 100 has silver particles 110, glass frit 120, and an organic binder 130 mixed with solvent.
  • Examples of pure silver, rear tabbing pastes made by DuPontTM (Solamet® PV52A) and by Heraeus (SOL230H) contain 45-66% conductive particles by weight and are designed to reduce silver loading and have a resulting thickness between 3 and 10 ⁇ after screen printing, drying, and co-firing.
  • the silver particles are a mixture of silver flakes that are 1 to 3 ⁇ in diameter and silver spheres with a distribution of sizes ranging in diameter from 100 nm to 5 ⁇ .
  • Examples of pure silver, front metallization pastes made by DuPontTM (Solamet® (PV17x) and Heraeus (SOL9235H) contain more than 90 wt% conductive particles.
  • Such front metallization pastes contain spherical silver particles that range in size between 300 nm and 5 ⁇ . Such pastes are formulated to print lines that have a high aspect ratio, compact densely to improve bulk conductivity, and make ohmic contact to the emitter layer of a silicon solar cell.
  • Silver based metallization pastes are inherently expensive because of the amount of Ag required and the commodity price of Ag, which is close to $625/kg in 2014. Silver based metallization pastes are the second largest materials cost for Si PV modules, and it is estimated that the PV industry currently uses more than 5% of all annual silver production. Continued, large increases in PV cell production will use more and more silver, which may become prohibitively expensive and unsustainable in the long-term.
  • Silver nanoparticles may offer the advantages of higher compaction and lower roughness, which enables the use of thinner printed films.
  • Silver nanoparticles are known to deform and sinter at relatively low temperatures (e.g., less than 300°C), and micron-sized silver particles are known to deform in the presence of glass frits (e.g. PbO and B1 2 O 3 ) at higher temperatures.
  • One method to make silver film electrodes is to print silver particles and heat them to form a dense sintered network.
  • the size of the silver particles, the composition of the frits, the firing temperatures, and ramp up and cool down rates are all important factors that affect the internal stress of the resulting films and their ability to adhere to a substrate (e.g., silicon) that has a different coefficient of thermal expansion.
  • Silver nanoparticles have been printed to form thin films (i.e., less than 1 ⁇ ) and annealed at relatively low temperatures (i.e., less than 600°C).
  • thin films i.e., less than 1 ⁇
  • annealed at relatively low temperatures i.e., less than 600°C.
  • thick films made from pastes where nanoparticles form the majority of particles by weight have high internal stresses and often crack and delaminate when the films become thicker than 500 nm, which render them useless for solar cell electrodes (see J.R. Greer, "Mechanical characterization of solution-derived nanoparticle silver ink thin films," J. App. Phys. 101, 103529 (2007)).
  • Figure 2A is a schematic cross-section illustration of such a silver nanoparticle metallization layer 210 on a substrate 220 before firing.
  • Figure 2B is a schematic cross- section illustration of such a silver nanoparticle metallization layer 215 on a substrate 220 after firing.
  • silver nanoparticle pastes can be printed as a layer 210 onto a substrate 220, the layer 210 cracks and curls up after firing, as shown in layer 215 in Figure 2B, losing contact to the substrate 220 at the edges.
  • Such profiles cannot be used in solar cells or any other semiconductor devices that are fired to temperatures greater than 700°C, as they have reduced contact area and are prone to even further peeling.
  • Figure 1 is a schematic drawing of a silver metallization paste (prior art).
  • Figure 2A is a schematic cross-section illustration of a silver nanoparticle metallization layer on a substrate before firing.
  • Figure 2B is a schematic cross-section illustration of a silver nanoparticle
  • Figure 3 A is a schematic illustration that shows a silver particle that has a spherical shape.
  • Figure 3B is a schematic illustration that shows a silver particle that has a flake shape.
  • Figure 4 is a schematic plan- view illustration of a core-shell particle, according to an embodiment of the invention.
  • Figure 5 is a SEM image of a film that resulted from firing a paste that contained silver microparticles and nondeformable inorganic material particle.
  • Figure 6 is a SEM image of a film that resulted from firing a paste that contained silver nanoparticles and nondeformable inorganic material particle, according to an embodiment of the invention.
  • Figure 7 is a schematic drawing that shows the rear side of a silicon solar cell.
  • Figure 8 is a schematic drawing that shows the front (or illuminated) side of a silicon solar cell.
  • Figure 9 is a schematic cross-section drawing that shows an embodiment of metallization layer on the front face of a solar cell.
  • Figure 10 is a schematic cross-section drawing that shows another embodiment of metallization layers on the front face of a solar cell.
  • a metallization paste that can be used to make electrodes contains a plurality of silver particles that make up between 10 wt% and 50 wt% of the paste. More than 50 wt% of the silver particles are nanoparticles that have a D50 diameter between 10 nm and 1000 nm. The nanoparticles are configured to deform upon firing at temperatures greater than 500°C. Less than 50 wt% of the silver particles are microparticles with at least one dimension greater than 1000 nm.
  • the paste also contains a plurality of nondeformable inorganic material particles that make up more than 10 wt% of the paste and glass frit.
  • silver nanoparticle pastes due to their notably high silver nanoparticle component versus conventional thick film metallization pastes.
  • the metallization paste has a viscosity between 10,000 and 200,000 cP at 25 °C and at a sheer rate of 4 sec "1 . In one arrangement, the metallization paste has a solids loading between 30 wt% and 70 wt%.
  • the nondeformable inorganic material particles may be made of a metal such as nickel (Ni), cobalt (Co), aluminum (Al), boron (B), or alloys thereof.
  • the nondeformable inorganic material particles may be made of a material such as aluminum (Al), tin (Sn), zinc (Zn), lead (Pb), antimony (Sb), nickel (Ni), boron (B), phosphorus (P), magnesium (Mg), molybdenum (Mo), manganese (Mn), tungsten (W), or alloys, composites, or other combinations thereof.
  • the nondeformable inorganic material particles may be made of copper (Cu).
  • the nondeformable inorganic material particles may be made of an oxide that includes at least one element such as silicon (Si), boron (B), nickel (Ni), cobalt (Co), aluminum (Al), molybdenum (Mo), manganese (Mn), tungsten (W), chromium (Cr), tin (Sn), zinc (Zn), lead (Pb), or antimony (Sb).
  • the nondeformable inorganic material particles may be core-shell particles that have an outer shell made of a nondeformable inorganic material such as any of those described herein.
  • the silver nanoparticles have a D50 that is between 10 nm and 500 nm, between 10 nm and 300 nm, between 10 nm and 200 nm, or between 10 nm and 100 nm. In some arrangements, the silver nanoparticles have a D50 range between 100 nm and 800 nm, between 150 nm and 500 nm, or between 150 nm and 300 nm.
  • the nondeformable inorganic material particles have a D50 range between 200 nm and 1000 nm, between 500 nm and 1000 nm, or between 750 nm and 1000 nm.
  • the nondeformable inorganic material particles have a D50 range between 200 nm and 2500 nm, between 500 nm and 2000 nm, or between 750 nm and 1500 nm.
  • the metallization paste comprises 40 wt% silver nanoparticles, 11 wt% silver microparticles, 21 wt % nondeformable inorganic material particles, 3 wt% glass frit, and 25 wt% organic vehicle.
  • the metallization paste comprises 33 wt% silver nanoparticles, 9.5 wt% silver microparticles, 17.5 wt % nondeformable inorganic material particles, 2 wt% glass frit, and 38 wt% organic vehicle.
  • the metallization paste comprises 33 wt% silver nanoparticles, 0 wt% silver microparticles, 27 wt % nondeformable inorganic material particles, 1 wt% glass frit, and 39 wt% organic vehicle.
  • the metallization paste comprises 21 wt% silver nanoparticles, 4 wt% silver microparticles, 25 wt % nondeformable inorganic material particles, 3 wt% glass frit, and 47 wt% organic vehicle.
  • the metallization paste comprises 12 wt% silver nanoparticles, 3 wt% silver microparticles, 35 wt % nondeformable inorganic material particles, 4 wt% glass frit, and 46 wt% organic vehicle.
  • the metallization paste comprises 40 wt% silver nanoparticles, 8 wt% silver microparticles, 37 wt % nondeformable inorganic material particles, 5 wt% glass frit, and 10 wt% organic vehicle.
  • a method for using a metallization paste involves applying or printing (e.g., screen printing or inkjet printing) the metallization paste onto at least a portion of a surface of a substrate.
  • the metallization paste contains a plurality of silver particles that make up between 10 wt% and 50 wt% of the paste. More than 50 wt% of the silver particles are nanoparticles that have a D50 between 10 nm and 1000 nm. The nanoparticles are configured to deform upon firing at temperatures greater than 500°C. Less than 50 wt% of the silver particles are microparticles with at least one dimension greater than 1000 nm.
  • the paste also contains a plurality of nondeformable inorganic material particles that make up more than 10 wt% of the paste and glass frit.
  • the silver particles, the nondeformable inorganic material particles, and the glass frit are all mixed together in an organic vehicle to form the paste. More specific paste formulations, as described above, may also be used in this method.
  • the substrate is heated to between 100°C and 250°C for between 10 and 900 seconds to dry the metallization paste. Then the substrate is fired to a peak firing temperature between 650°C and 900°C to form a metallization film.
  • the substrate may be a silicon solar cell.
  • the metallization paste may be applied to form fine grid lines on the front surface of the silicon solar cell.
  • the metallization paste may be applied to form front busbars on the front surface of the silicon solar cell.
  • the metallization paste may be applied to form floating busbars on the front surface of the silicon solar cell.
  • the metallization paste may be applied to form rear tabbing structures on the back surface of the silicon solar cell.
  • the metallization film has a porosity less than 40%.
  • the metallization film may have a density greater than 6 g/cm 3 .
  • the metallization film may have a resistivity between 3.0 x 10 "8 and 1.5 x 10 "7 ohm-cm 2 .
  • the metallization film may have a thickness between 3 and 10 microns.
  • the metallization film has a peel strength between 1 and 3 N/mm when soldered using a flux and tabbing ribbon.
  • the metallization film may alternately have a peel strength greater than 1 N/mm, greater than 1.5 N/mm, or greater than 2 N/mm when soldered using a flux and tabbing ribbon.
  • a solar cell has a silicon substrate that has a plurality of fine grid lines on its front surface. There is at least one front busbar layer on the front surface of the silicon substrate, and the front busbar layers are in electrical contact with the plurality of fine grid lines. There are an aluminum layer and at least one rear tabbing layer on the back surface of the silicon substrate. At least one of the plurality of fine grid lines, the front busbar layer, or the rear tabbing layer has a condensed particle morphology that consists of nondeformable inorganic material particles dispersed in a silver matrix, such that the weight ratio of silver to nondeformable inorganic material particles is about 5: 1.
  • the nondeformable inorganic material particles comprise aluminum (Al), tin (Sn), zinc (Zn), lead (Pb), antimony (Sb), nickel (Ni), boron (B), phosphorus (P), magnesium (Mg), molybdenum (Mo), manganese (Mn), tungsten (W), and alloys, composites, or other combinations thereof.
  • the rear tabbing layer has the condensed particle morphology described above, it has a peel strength of more than 1 N/mm when soldered to tin coated copper tabbing ribbons using tin based solders and fluxes.
  • the rear tabbing layer may have a a thickness between 3 and 10 ⁇ .
  • the rear tabbing layer may have a conductivity that is 2 to 10 times less than the conductivity of bulk silver.
  • the front busbar layer has the condensed particle morphology described above, it has a peel strength of more than 1 N/mm when soldered to tin coated copper tabbing ribbons using tin based solders and fluxes.
  • the front busbar layer may have a thickness between 3 ⁇ and 50 ⁇ .
  • the front busbar layer may have a conductivity that is 2 to 10 times less than the conductivity of bulk silver.
  • the the front busbar layers may be parallel to one another. The distance between the front busbar layers may be less than 4 cm.
  • the front surface of the silicon substrate has an anti-reflective coating, and the front busbar layers do not penetrate through the anti-reflective coating and do not make electrical contact to the silicon substrate.
  • the front surface of the silicon substrate has a silicon emitter layer, and the front busbar layer makes electrical contact to the silicon emitter layer.
  • the fine grid lines may have the condensed particle morphology described above.
  • the fine grid lines may have a thickness between 20 ⁇ and 50 ⁇ .
  • the solar fine grid lines may have a conductivity that is 1.5 to 7 times less than the conductivity of bulk silver.
  • the front surface of the silicon substrate has a silicon emitter layer, and the fine grid lines make electrical contact to the silicon emitter layer with a contact resistance less than 100 mohm-cm 2 .
  • nanoparticle is used herein to mean particles with a D50 that is greater than 1 nm and less than 1000 nm.
  • D50 is a common metric that is used to define the median diameter of particles; the D50 value is defined as the value where half of the particle population has a diameter below and half the particle population has a diameter above the value.
  • D10 is the value where 10% of the volume of the population is below the value and D90 is where 90% of the volume of the population is below the value.
  • Measuring particles smaller than one micron is typically performed with a laser particle size analyzer such as the Horiba LA-300.
  • spherical particles are dispersed in a solvent in which they are well separated and the scattering of transmitted light is directly correlated to the size distribution from smallest to largest dimensions.
  • the most common approach to express laser diffraction results is to report the D10, D50, and D90 values, which are based on volume distributions.
  • more specific ranges are given for the dimensions of nanoparticles.
  • Various shapes of nanoparticles are included within the definition, and their dimensions are specified herein.
  • nondeformable inorganic material particle (NIMP) is used herein to mean any particle that, when used in a paste with glass frits, experiences little or no change at glass flowing temperatures (approximately 500°C-800°C).
  • solids loading is used herein to mean the amount or proportion of solids in a metallization paste.
  • the solids include silver particles, nondeformable inorganic material particles (NIMPs), and frit.
  • the D10 and D90 values also give an indication of the polydispersity of the nanoparticles measured. While low polydipersity is important for tight packing of systems with two different particle sizes, it is less important for nanoparticle systems, where the D50 of the nondeformable inorganic material particles may be as much as four times greater than the D50 of the silver nanoparticles.
  • porosity used herein to mean the percentage of a film's volume that is empty space as compared to the total film volume.
  • the porosity can be measured by comparing the weighted density average for the given solids loading (e.g., silver, NIMP, and frit composition) versus the measured density, which can be obtained by dividing the fired film weight by the film volume (i.e., the fired film thickness, as measured by scanning electron microscopy or atomic force microscopy, times the print area).
  • pastes containing silver nanoparticles, silver microparticles, and NIMPs will be referred to as silver nanoparticle pastes.
  • Metallization pastes are used to form three different layers on the solar cell: rear tabbing, fine grid lines, and front busbars. These layers have different materials properties that fall into four primary categories:
  • Solderability is the ability to form a strong physical bond between two metal surfaces by the flow of a molten metal solder between them at temperatures below 400°C. All soldering on a solar cell is performed after heating in air to over 750°C for approximately one second, and the term, "high-temperature solderability,” is used herein to mean the ability to be soldered after heating to over 750C in air. High-temperature solderability has a stricter standard than solderability and precludes the use of metals which form thick layers of oxide on heating to 750C. High-temperature solderability involves the use of flux, which is any chemical agent that cleans or etches one or both of the surfaces prior to ref ow of the molten solder. This becomes even more difficult because many metal oxides are resistant to commonly used fluxes after oxidation above 750C.
  • peel strength is greater than lN/mm (Newton per millimeter).
  • the peel strength is defined as the force required to peel a soldered ribbon, at a 180° angle from the soldering direction, divided by the width of the soldered ribbon. It is common for the peel strength to be between 1.5 and 3 N/mm on contacts to the tabbing ribbons in commercially available solar cells. Peel strength is a metric of solder joint strength for solar cells.
  • the conductivity of a solar cell is determined by directly measuring the resistance of individual layers on the solar cell.
  • Meier et al. describes how to use a four-point probe electrical measurement to determine the resistivity of each metallization layer (Reference: Meier et al. "Determining components of series resistance from measurements on a finished cell", IEEE (2006) ppl315). Because Ag based metallization layers are relatively compact (i.e., have low porosity) the bulk resistivity of the metallization layer is often considered a more useful metric than the actual resistivity of the metallization layers themselves. However, for some types of metallization pastes, the films do not completely compact.
  • the bulk resistivity may not provide an accurate comparison between different types of metallization pastes with the same printed thickness, and it is best to measure the resistance of individual layers in the method described by Meier et al. for an accurate comparison.
  • Ohmic contact resistivity is a measure of the contact resistivity between the fired metal film and the silicon surface. The contact resistivity can be measured by TLM (transfer length method) and is in the range of 1 to 100 ⁇ -cm 2
  • the purpose of the fine grid lines is to collect current from the front side of the solar cell and transport it to the busbars.
  • highly conductive materials e.g., silver
  • the silver paste Upon firing the front side, the silver paste is designed to condense with a minimum amount of voids and to achieve a bulk resistivity that is 1.2-1.5 times the bulk resistivity of pure silver (1.5E-8 ohm-m).
  • the front side silver paste is also designed to print with a high aspect ratio to form fine grid lines that are 20-60 ⁇ wide and 20-50 ⁇ high. Reducing the width of the grid lines can improve the light absorption of the PV cell by exposing more silicon to sunlight. Increasing the height of the fine grid lines can further reduce the series resistance. Fine grid lines also form ohmic contacts with silicon; it is useful if the ohmic contacts have a resistance less than about 100 ⁇ -cm 2 . It should be noted that the fine grid lines are not physically connected to the tabbing ribbon, so solderability and peel strength are not important metrics for fine grid lines.
  • busbars make ohmic contact to both the fine grid lines and the tabbing ribbon. It is important that the front busbar layer is high-temperature solderable and adheres well to the front side of the solar cell.
  • the front busbars transfers current from the fine grid lines to the copper tabbing ribbon to connect multiple solar cells in a module. Importantly, current transport occurs vertically through the thickness of a continuously tabbed busbar layer, which is 10-20 ⁇ thick, and not laterally as in the case of the fine grid lines. Therefore, though it may be non-obvious, busbars can have a bulk conductivity that is less than 100 times that of silver without impacting solar cell performance significantly. It is useful if the front busbar layer has a peel strength greater than lN/mm after it is soldered to the tabbing ribbon.
  • the busbar and fine grid lines are printed at the same time using the same front side metallization paste. After both layers are dried, they are fired at the same conditions as described above, at which time they partially decompose the silicon nitride (anti-reflective) layer and make electrical contact to the underlying silicon.
  • the busbars make ohmic contact to the silicon with a contact resistance less than 100 ⁇ - cm 2 .
  • a floating busbar is a busbar that does not make significant direct electrical contact to the silicon but only to the fine electrical grid lines on the front side of the silicon solar cell. This means that the contact resistivity between the fired floating metal busbar and the silicon surface exceeds 0.1 ⁇ -cm 2 .
  • metal pastes that do not fully penetrate through the anti-reflective coating after firing are formulated.
  • Such a stack may not be resilient against temperature fluctuations during regular use of the solar cell, which could lead to copper oxidation and copper diffusion into the silicon. Copper diffusion is especially problematic because it can cause local shunting through the emitter region.
  • One other problem with this approach is that as nickel reacts with silicon a nickel silicide may form.
  • the emitter region of the solar cell is thin (e.g., 50-500 nm), and there is a risk that the nickel silicide may consume the entire emitter layer and shunt the solar cell.
  • the purpose of the rear tabbing layer is to make ohmic contact to an Al layer on the back side of the silicon.
  • the Al layer collects current from the rear side of the solar cell. It is useful if the rear tabbing layer is high-temperature solderable and adheres well to the silicon.
  • the rear tabbing layer is soldered to the copper tabbing ribbon in order to transport current from the rear side of the solar cell to the tabbing ribbon. Importantly, current transport occurs vertically through the thickness of the rear tabbing layer, which is 3-10 ⁇ thick, and not laterally as in the case of the fine grid lines, as discussed above.
  • rear tabbing layers can have a bulk conductivity that is less than 100 times that of silver without impacting solar cell performance significantly.
  • the rear tabbing layer does not make ohmic contact to the rear side of the solar cell. It is useful if the rear tabbing layer has a peel strength greater than IN/mm after it is soldered to the tabbing ribbon.
  • An alternative paste for use in solar cell metallization layers has been developed.
  • the alternative paste has both silver nanoparticles and nondeformable inorganic material particles.
  • the formulations described herein can be used to form metallization layers that have good characteristics and are highly robust for film thicknesses greater than 500 nm.
  • Such metallization layers can be fired at temperatures of 750°C and greater, have good solderability and peel strength, make low resistance ohmic contacts to silicon and are highly conductive.
  • the addition of silver nanoparticles to alternative metallization pastes provides better particle compaction during firing.
  • State-of-the-art silver rear tabbing metallization pastes contain a mixture of micron-sized spherical and flake silver particles with a small amount of silver nanoparticles (e.g., less than 20% of the total silver weight).
  • Such pastes print films that have a relatively low density upon drying, but compact by as much 40-50%) during firing to form dense, strong films.
  • silver metallization films that merely increasing the proportion of nano- versus micro- silver particles does not improve the overall peel strengths of the resulting films.
  • increasing the silver nanoparticle content in such films can result in reduced film quality and lower peel strengths.
  • Ag/nondeformable particle systems typically compact by less than 20% upon firing.
  • Such films can have densities that are less than the densities of pure Ag films, resulting in concomitant lower peel strengths.
  • deformable, micron- sized Ag particles of various shapes are mixed with non-deformable, non-Ag, micron-sized particles in metallization pastes, the films that result are porous, do not compact well and may become even more porous after firing.
  • Such films often have significantly lower peel strengths when soldered to tabbing ribbons than do state-of-the-art silver pastes.
  • a rear tabbing and front busbar silver nanoparticles metallization paste includes the following components:
  • a front side or fine grid line silver nanoparticles metallization paste includes the following components:
  • the silver nanoparticles have a D50 between about 10 nm and 1000 nm.
  • the silver nanoparticles may have a D50 that is less than 1000 nm, or less than 500 nm, or less than 300 nm, or less than 200 nm, or less than 100 nm, or any range therein.
  • the silver nanoparticles have a D50 that is between 100 nm and 800 nm, or between 150 nm and 500 nm, or between 150 nm and 300 nm, or any range therein.
  • silver nanoparticle powders are spheres with a D50 of 100 nm, a D10 of 50 nm, and a D90 of 300 nm.
  • silver nanoparticle powders are spheres with a D50 of 200 nm, a D10 of 100 nm, and a D90 of 500 nm.
  • silver nanoparticle powders are spheres with a D50 of 250 nm, a D10 of 100 nm, and a D90 of 350 nm.
  • the polydispersity (i.e., D10 and D90) of nanoparticle powders can vary significantly depending on the synthesis technique and the supplier. There are several D10 and D90 levels that can result in acceptable compact films.
  • FIG. 3 A An example of a spherical silver particle 310 is shown in Figure 3 A. Such a particle has only one dimension, a diameter, indicated by 315.
  • the sphere 310 is shown to illustrate a shape that is equiaxed - one whose largest dimension and smallest dimension are the same. It is unlikely that silver particles would take on such a perfect shape 310, but shapes that are approximately equiaxed are possible within the embodiments of the invention.
  • silver nanoparticles have a D50 diameter 315 between 10 nm and 1000 nm.
  • silver microparticles have at least one dimension greater than 1000 nm. It should be noted that it is not necessary for the nanoparticles to have a spherical shape. In some instances, non-spherical particles, which have higher surface areas and may have depressed melting temperatures may be more desirable.
  • flake particle 320 An example of a flake particle 320 is shown in Figure 3B.
  • the flake 320 has a smallest dimension given by its thickness 322 and a largest dimension indicated by 324. Again, it is unlikely that silver particles would take on such a perfectly planar shape, but approximations to this are possible within the embodiments of the invention.
  • flake particles have largest dimensions 324 that are greater than 1000 nm and can be described as microparticles.
  • Silver particles deform when fired at temperatures greater than 700°C. Deformation is a result of the interaction of the silver particles with heavy metal-containing glass frits at firing temperatures above the glass transition temperature of the glass frit. At such temperatures, the flowing glass enables rapid diffusion, sintering, and reorganization of the silver particles in a manner that resembles melting. The morphology of films made with pastes that include such particles has reduced void space after firing due to settling and coalescence of silver as the glass flows.
  • a third particle component in the paste is a nondeformable inorganic material particle (NIMP).
  • nondeformable particles are not highly soluble in glass frit and experience little or no change at glass flowing temperatures, which are between about 500°C and 800°C.
  • the nondeformable particles contain a homogeneous material that has a melting point higher than 800°C and that is chemically inert to the glass.
  • the nondeformable particles have a composite core-shell morphology, with an inert shell surrounding a melting or glass-interacting material, such that the overall particle acts as a nondeformable material at glass-flowing temperatures.
  • nondeformable inorganic material particles include pure or coated particles of aluminum (Al), tin (Sn), zinc (Zn), lead (Pb), antimony (Sb), nickel (Ni), boron (B), phosphorus (P), magnesium (Mg), molybdenum (Mo), manganese (Mn), tungsten (W), and alloys, composites, or other combinations thereof.
  • the nondeformable inorganic material particles may be made of copper (Cu).
  • nondeformable inorganic materials also include compounds of oxygen with at least one element such as silicon (Si), boron (B), nickel (Ni), cobalt (Co), aluminum (Al), molybdenum (Mo), manganese (Mn), tungsten (W), chromium (Cr), tin (Sn), zinc (Zn), lead (Pb), or antimony (Sb).
  • Si silicon
  • B boron
  • Ni nickel
  • Co cobalt
  • Al aluminum
  • Mo molybdenum
  • Mn manganese
  • W tungsten
  • Cr chromium
  • Sn zinc
  • Pb lead
  • antimony Sb
  • nondeformable inorganic material particles contain no Ag. It is especially useful if care is taken to ensure that there is chemical compatibility between the NIMPs and the glass frits in the pastes.
  • FIG. 4 is a schematic drawing of a core-shell or coated nondeformable inorganic material particle 400, according to an embodiment of the invention.
  • a core particle 410 that is surrounded by a first shell 420.
  • the outer surface 425 of the shell 420 is also indicated.
  • the core particle 410 may be made of any of the metals or alloys listed above.
  • the first shell 420 may be made of any nondeformable inorganic material listed above.
  • One route to improve flow of silver nanoparticles around nondeformable inorganic material particles is to coat the nondeformable inorganic material particles with silver.
  • the silver coating can be non-conformal such as with silver nanoparticle decoration or conformal such as with a thin silver shell formed, for example, by a reduction reaction.
  • Nanoparticle decoration is a technique known to one skilled in the art by which small silver nanoparticles, with diameters between 1 and 50nm, can be attached in a single or multiple layers onto other larger particles.
  • Coating nondeformable inorganic material particles with silver also introduces ligands similar to those on commercially available silver nanoparticles onto the surfaces of the nondeformable inorganic material particles, thus ensuring similar levels of dispersion in the organic vehicle.
  • nondeformable inorganic nickel particles are coated first with a shell of nickel boron and then with a conformal shell of silver using industrial standard practices.
  • the nondeformable inorganic material particles include a mixture of possible particles, such as particles of different metals and alloys or particles of both metals and alloys and particles of oxygen compounds.
  • the nondeformable inorganic material particles have a D50 between about 200 nm and 2500 nm.
  • the nondeformable inorganic material particles may have a D50 that is less than 2500 nm, or less than 2000 nm, or less than 1500 nm, or less than 1000 nm, or less than 500 nm, or any range therein.
  • the nondeformable inorganic material particles have a D50 that is between 500 nm and 2000 nm, or between 750 nm and 1500 nm, or any range therein.
  • nondeformable inorganic material particles are spheres with a D50 of 500 nm, a D 10 of 200 nm, and a D90 of 1000 nm.
  • nondeformable inorganic material particle powders are spheres with a D50 of 1000 nm, a D10 of 600 nm, and a D90 of 2000 nm.
  • nondeformable inorganic material particle powders are spheres with a D50 of 2500 nm, a D10 of 1200 nm, and a D90 of 4000 nm.
  • the polydispersity (i.e., D10 and D90) of nanoparticle powders can vary significantly depending on the synthesis technique and the supplier. There are several D10 and D90 levels that can result in acceptable compact films.
  • the silver nanoparticles, silver microparticles, and nondeformable inorganic material particles are all mixed together with a glass frit and an organic vehicle (that also contains a binder) to form a paste.
  • the paste is suitable for screen printing.
  • the paste is suitable for inkjet printing.
  • the total solid component of the paste, including all particles is between 30 wt% and 90 wt%, or between 30 wt% and 75 wt%, or between 40 wt% and 60 wt%, or any range therein.
  • the paste has a viscosity between 10,000 and 200,000 cP as measured by a viscometer at 25 °C and at a shear rate of 4 sec "1 for screen printable paste or between 1 and 10,000 cP for inkjet printable pastes, or any range therein.
  • films resulting from the firing of silver nanoparticle metallization pastes are called Ag/NIMP composite layers or films.
  • films made from firing the metallization pastes disclosed herein have porosities less than 40%, less than 30%, less than 20%>, or less than 10%>.
  • films made from the metallization pastes disclosed herein have densities greater than 6 g/cm 3 , greater than 7 g/cm 3 , greater than 8 g/cm 3 , or greater than 9 g/cm 3 , or any range therein.
  • the metallization film has a resistivity between 3.0 x 10 "8 and 1.5 x 10 "7 ohm -cm 2 , or any range therein.
  • the remaining non-silver portions of the metallization pastes are made up of organic vehicle and glass frit.
  • Commercially available glass frit e.g. , Ceradyne product #V2027) and other additives can be used in front side metallization pastes to penetrate through anti-reflective coatings, improve silver sintering, and make ohmic contact to doped silicon.
  • Glass frit may be a mixture of the oxides of bismuth, zinc, tellurium, sodium, lithium, lead, and silicon, with the final ratios and compositions varied to achieve a melting point between 500°C and 800°C.
  • the doping density of the emitter region in the silicon and the additives in the metallization pastes can be adjusted relative to one another to optimize electrical contact.
  • the organic vehicle is a mixture of organic solvents and binders.
  • Organic vehicle can be adjusted depending on the exact paste deposition conditions.
  • the viscosity of metallization pastes can be tuned by adjusting the amounts of organic binders and solvents in organic vehicle and by including thixotropic additives, organic binders, and solvents.
  • various pastes can be made to apply coatings that can range in fired thickness between about 3 and 10 ⁇ or between 3 and 15 ⁇ (e.g., for rear tabbing and front busbar layers) and between about 20 and 50 ⁇ (e.g., for front side or fine grid lines). It should be noted that it is possible to make much thicker films by printing again and again over previously- printed lines.
  • Common coating solvents include terpineol and the family of glycol ethers (diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and texanol).
  • Common organic binders include ethyl cellulose, carboxymethyl cellulose, poly(vinyl alcohol), poly(vinyl butyral), and poly(vinyl pyrrolidinone).
  • a first metallization paste was made from a silver/nondeformable inorganic material particle paste where silver content in the paste contained a majority (by weight) of micron-sized particles (i.e., silver flake and lum sized spheres).
  • the paste was applied to a silicon wafer and fired in a rapid thermal annealer to a peak firing temperature of 800°C.
  • Figure 5 is a SEM image of the resulting film. As can be seen in Figure 5, the film is relatively porous.
  • the micron sized Ag particles 510 do not completely surround the nondeformable inorganic particles 520.
  • a second metallization paste was made from a nanosilver/nondeformable inorganic material particle paste where silver content in the paste contained a majority (by weight) of nanoparticles, according to an embodiment of the invention.
  • the paste was applied to a silicon wafer and fired in a rapid thermal annealer to a peak firing temperature of 800°C.
  • Figure 6 is a SEM image of the resulting film. As can be seen in Figure 6, the film is densely packed with low apparent porosity. It is difficult to distinguish individual nondeformable inorganic material particles as the silver particles have covered them extensively.
  • the silver matrix connects in many points around the NIMPs, with small nodes and high connectivity.
  • FIG. 7 is a schematic drawing that shows the rear side of a silicon solar cell 700.
  • the rear side is coated with an aluminum rear contact 730 and has rear side tabbing layers 740 distributed over the silicon wafer 710.
  • Metallization layers on solar cells are fabricated by first printing the front side silver paste followed by the silver rear tabbing paste and then the aluminum paste. Each paste is dried individually at between lOOC and 250C for between 10 and 900 seconds and then co-fired at a peak temperature between 650 and 900C for approximately one second.
  • silicon solar cells are connected to one another by soldering tin solder coated copper tabbing ribbons to the front busbars and rear tabbing layers.
  • Solder fluxes that are commercially designated as either RMA (e.g. Kester® 186) or R (e.g. Kester® 952) are deposited on the front busbars and rear tabbing layers.
  • a tinned copper ribbon which is between 1.3 and 3 mm wide and 100-300 um thick is then placed on the solar cell and contacted to the front busbars and the rear tabbing layers with a solder iron at a temperature between 200°C and 400°C.
  • the solder joints formed during this process have a mean peel strength that is greater than 1 N/mm (e.g. a 2 mm tabbing ribbon would require a peel force of greater than 2N to dislodge the tabbing ribbon).
  • Silver nanoparticle metallization pastes disclosed herein can be used as drop in replacements for commercial Ag based pastes to form the rear tabbing layer.
  • a commercially available front side metallization paste is screen printed onto the front side of a solar cell and dried at 100-250°C to form the fine grid line and busbar layers on the front surface of the wafer.
  • a silver nanoparticle metallization rear tabbing paste such as any of those described in Table I, is then screen printed onto the back side of a solar cell and dried at 100-250C°C to form the rear tabbing layer 720.
  • a rear aluminum paste is subsequently printed and dried and the entire wafer is co-fired to 650-900C°C for approximately one second in air.
  • Ag/NIMP pastes used for the rear tabbing layer of a solar cell can have a bulk resistivity that is several times higher than pure Ag pastes but have identical power conversion efficiencies.
  • Table II shows the key photovoltaic properties averaged over 10 solar cells for mono crystalline solar cells made with pure Ag pastes and those made with pure Ag pastes on the front side and Ag/NIMP paste used for the rear tabbing layer. Properties include open-circuit voltage (V oc ), short circuit current (I sc ), short circuit current density (J sc ), fill factor (FF), efficiency (Eff), idealty factor (n-factor), series resistance (RSERIES), and shunt resistance (RSHUNT).
  • the Ag/NIMP paste contained over 25% wt Ag nanoparticles and over 20 wt% NIMP, which were core shell particles with a Ni core and a Ni:B shell.
  • the Ag/NIMP has nearly identical electrical properties and standard deviations for all key PV cell metrics including power conversion efficiency, open-circuit voltage, and short circuit current.
  • FIG. 8 is a schematic drawing that shows the front (or illuminated) side of a silicon solar cell, according to an embodiment of the invention.
  • a commercially available front side metallization paste is screen printed and dried at 100-250°C to form the fine grid line 810.
  • a silver nanoparticle front busbar paste is then screen printed and dried at 100-250°C to form the front busbar layers 820.
  • the rear tabbing paste and rear aluminum paste are subsequently printed and dried, as described above, and the entire wafer is co-fired to 650-900°C for approximately one second in air.
  • screen printed front busbar coatings range in thickness between about 3 and 15 ⁇ after co-firing.
  • the front busbar layer has a bulk conductivity that is 2 to 10 times less conductive than bulk silver, which has a bulk resistivity of about 1.5E-8 ohms-m.
  • the resulting morphology of the front busbar layer is a condensed particle morphology, which is defined as a sintered and compacted silver matrix that contains dispersed NIMP, elements from the glass frit and/or reaction products from the glass frit and silicon.
  • Sintered and compacted silver films are defined as having tightly packed spherical or distorted spherical silver regions with less porosity than randomly packed hard spheres, and the contact areas between regions of silver are higher than in the case of tightly packed hard spheres.
  • the morphology of some embodiments can also be described as a sintered and compacted silver matrix with dispersed NIMP.
  • the resulting front busbar layer can have a weight ratio of silver to nondeformable inorganic material particles
  • the fine grid lines and/or the rear tabbing layer can also have a weight ratio of silver to nondeformable inorganic material particles (Ag:NIMP) of 1 : 9, or 1 : 1 , or 5 : 1.
  • Figure 9 is a schematic cross-section drawing that shows metallizations on the front side of a solar cell, according to an embodiment of the invention.
  • Figure 9 shows solar cell 900 that is coated with an anti-reflective coating 910 on its front side.
  • a silver paste is applied to the anti-reflective coating 910 to form fine grid lines 920 that fire through the antireflective coating.
  • Such grid lines may have a thickness between about ⁇ and 50 ⁇ .
  • the fine grid layers 920 are seen in transverse cross section and run into and out of the page.
  • a silver nanoparticle front busbar paste is then screen printed and dried at 100-250°C to form second fine grid line layers 930 over the fine grid line layers 920 and additionally form front busbar layer (not shown).
  • the stacked fine grid layers have a Ag film 920 on the surface of the anti-reflective coating and a NIMP/Ag composite film 930 available for contacting a tabbing ribbon.
  • the moderately conductive NIMP/Ag composite layer 930 on the silver fine grid line 920 can further reduce the overall series resistance of the fine grid lines, as current travels in parallel between the layers.
  • a stacked fine grid layer that has a 20 ⁇ thick Ag layer with a bulk resistance that is that of pure Ag and a 20 ⁇ thick
  • FIG. 10 is a schematic cross-sectional drawing that shows metallizations layer and wafer on the front side of a solar cell 1000, according to another embodiment of the invention, in which the order of deposition is reversed.
  • a silver nanoparticle front busbar paste is screen printed onto the solar cell 1000 and then dried at 100-250°C to form front busbar layers (not shown) and to form a first fine grid line layer 1030 for a stacked fine grid line structure.
  • a silver paste is applied over the fine grid line layer 1030 to form a second layer 1020.
  • the resulting stacked fine grid line layer has a Ag/NIMP composite film on the surface of the solar cell 1000 and a silver film available for contacting a tabbing ribbon.
  • the moderately conductive Ag/NIMP composite layer 1030 reduces the overall series resistance of the fine grid lines as current travels in parallel between the layers.
  • Silver nanoparticle pastes can be used in other, more complex, Si PV architectures, such as emitter wrap through and selective emitter cell architectures. Other examples include architectures where only fine grid lines are printed with no busbars and those that use fine wire network technologies to connect cells in a module.
  • the metallization pastes described above may also be used in metal wrap through as well as passivated emitter rear contact (PERC) solar cells.
  • the silver nanoparticle paste, described herein, can be used as a drop in replacement for Ag based pastes anywhere that Ag pastes are used currently.
  • Fine grid lines on solar cells are responsible for making good electrical contact to the silicon emitter layer and transporting current from the emitter over a distance of centimeters to the busbar of the solar cell.
  • Two important materials properties affect fine grid line design on solar cells: the bulk resistivity and the contact resistance between the fine grid line and the emitter layer.
  • the fine grid lines are highly conductive (e.g. within a factor of two of bulk Ag, which is the most conductive element) then the grid lines can be made thinner to reduce shading losses.
  • Frits and other additives can be used in metallization pastes to fire through the anti-reflective coating and make ohmic contact to doped silicon.
  • the additives in the metallization pastes determine the minimum required doping density of the emitter to make good electrical contact.
  • the doping density of the emitter also affects the optimal grid spacing on a silicon solar cell.
  • the total series resistance of the solar cell may be dominated by series resistance of individual fine grid lines.
  • the series resistance from the fine grid lines represents 73% of the total series resistance (D.L. Meier
  • Fine grid layers have been made up of pure Ag particles and have a bulk conductivity that is 1.1 to 2 times less conductive than bulk silver, which has a bulk resistivity of about 1.5E-8 ohms-m.
  • the series resistance of fine grid lines is proportional to the spacing between busbars (a), the bulk resistivity (p f ), fine grid line thickness (t), and fine grid line width (w) as shown in equation (1). It should be noted that increasing the number of busbars by a factor of two reduces the fine grid line series resistance by a factor of four.
  • Table III below highlights the effect of the number of busbars versus the series resistance of the fine grid lines. For a large number of busbars (e.g., >4) the series resistance drops significantly. When a six inch solar cell has four or more busbars, the spacing between the busbars is less than 4 cm or less than 2 cm.
  • busbars By adding additional busbars to a solar cell, the current per tabbing ribbon can be reduced, thus reducing the overall power loss in the module.
  • the busbar density on the solar cell By increasing the busbar density on the solar cell, the average distance that current must travel along the fine grid lines can be drastically reduced, which can lower the overall series resistance of the cell. This also allows for using metallization layers for fine grid lines that are less conductive than silver. If fine grid lines with a slightly higher bulk resistivity than silver are used, it may be possible to offset those losses by adding a higher density of busbars. Table III
  • a silver nanoparticle paste is screen printed and dried at
  • the resulting morphology of the fine grid line layer is a condensed particle morphology that comprises a silver phase that can contain elements from the glass frit and a phase resulting from the NIMP. These phases can be measured using x-ray diffraction and the individual elemental compositions can be seen using energy dispersive x-ray
  • the resulting fine grid line layers can have a weight ratio of silver to NIMP (Ag:NIMP) of 1 :9, or 1 : 1 , or 4: 1 depending on the desired conductivity and peel strength.
  • Ag:NIMP silver to NIMP
  • screen printed coatings range in thickness between about
  • the resulting fine grid line layers have a conductivity that is 1.5 to 7 times lower than the bulk resistivity of pure silver.
  • the ratio of silver particles to NIMP can vary from 1 :9 by weight (i.e., 10 wt% Ag particles to 90 wt% core-shell NIMP ), to 4: 1 by weight (i.e. 80 wt% Ag particles versus 20 wt% NIMP) depending on the desired conductivity for various applications.
  • the fraction of NIMP is between about 80wt% and 20wt%, between about 70wt% 30wt%, or between about 60wt% and 40wt%.
  • the weight ratio of silver particles to NIMP is between about 1 :9 and 4: 1, about 1 :5 and 4: 1, between about 3 :7 and 7:3, between about 2:3 and 3:2, or about 1 :1.
  • these pastes form a condensed particle network on the substrate, that is, their volumes are reduced by one or more processes during firing, such as, evaporation of carrier, sintering, etc.
  • film thicknesses are between about 4 and 50 ⁇ with a bulk resistivity that is 1.5 to 10 times higher than that of pure Ag using a four point Van der Pauw measurement on insulating substrates.
  • the bulk resistivity is dependent upon the NIMP:Ag weight ratio and the choice of glass frits.
  • the films have a bulk resistivity that is 1.5 to 7 times greater than the bulk resistivity of silver, which is 1.5E-8 ohms-m.
  • the films have a bulk resistivity between about 2 E-8 and 10 E-8 ohms-m.
  • the same paste composition is printed for both front side layers simultaneously and would technically be considered a front side paste.
  • NIMP and Ag based pastes that can be deposited onto silicon solar cells.
  • One example is to use silver nanoparticle pastes to form both front busbar and rear tabbing electrodes while the fine grid lines are made with Ag pastes.
  • Many different architectures can be fabricated using the three types of silver nanoparticle metallization pastes described above.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne des pâtes de métallisation destinées à être utilisées avec des dispositifs à semi-conducteur. Les pâtes contiennent des nanoparticules d'argent, des microparticules d'argent, et des particules de matériau inorganique non déformables. Des formulations spécifiques ont été développées afin d'obtenir des lignes imprimées présentant de faibles porosités et des résistances au pelage élevées.
PCT/US2014/071608 2014-12-19 2014-12-19 Pâte de métallisation solaire composite à base de nanoparticules d'argent WO2016099562A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2014/071608 WO2016099562A1 (fr) 2014-12-19 2014-12-19 Pâte de métallisation solaire composite à base de nanoparticules d'argent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2014/071608 WO2016099562A1 (fr) 2014-12-19 2014-12-19 Pâte de métallisation solaire composite à base de nanoparticules d'argent

Publications (1)

Publication Number Publication Date
WO2016099562A1 true WO2016099562A1 (fr) 2016-06-23

Family

ID=56127192

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/071608 WO2016099562A1 (fr) 2014-12-19 2014-12-19 Pâte de métallisation solaire composite à base de nanoparticules d'argent

Country Status (1)

Country Link
WO (1) WO2016099562A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017035102A1 (fr) * 2015-08-26 2017-03-02 Plant Pv, Inc Pâtes de métallisation sans contact d'argent-bismuth pour cellules solaires au silicium
US9698283B2 (en) 2013-06-20 2017-07-04 PLANT PV, Inc. Core-shell nickel alloy composite particle metallization layers for silicon solar cells
US9741878B2 (en) 2015-11-24 2017-08-22 PLANT PV, Inc. Solar cells and modules with fired multilayer stacks
US10550291B2 (en) 2015-08-25 2020-02-04 Hitachi Chemical Co., Ltd. Core-shell, oxidation-resistant, electrically conducting particles for low temperature conductive applications
CN114846093A (zh) * 2019-12-11 2022-08-02 吉尼斯油墨公司 基于银纳米粒子的油墨

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090211626A1 (en) * 2008-02-26 2009-08-27 Hideki Akimoto Conductive paste and grid electrode for silicon solar cells
WO2013036510A1 (fr) * 2011-09-09 2013-03-14 Ferro Corporation Contacts de cellule solaire à pastille d'argent
US20130098431A1 (en) * 2011-10-25 2013-04-25 Heraeus Precious Metals North America Conshohocken Llc Electroconductive Paste Composition Containing Metal Nanoparticles
US20140026953A1 (en) * 2011-01-18 2014-01-30 Heraeus Precious Metals North America Conshohocken Llc Electroconductive Paste Compositions and Solar Cell Electrodes and Contacts Made Therefrom

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090211626A1 (en) * 2008-02-26 2009-08-27 Hideki Akimoto Conductive paste and grid electrode for silicon solar cells
US20140026953A1 (en) * 2011-01-18 2014-01-30 Heraeus Precious Metals North America Conshohocken Llc Electroconductive Paste Compositions and Solar Cell Electrodes and Contacts Made Therefrom
WO2013036510A1 (fr) * 2011-09-09 2013-03-14 Ferro Corporation Contacts de cellule solaire à pastille d'argent
US20130098431A1 (en) * 2011-10-25 2013-04-25 Heraeus Precious Metals North America Conshohocken Llc Electroconductive Paste Composition Containing Metal Nanoparticles

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9698283B2 (en) 2013-06-20 2017-07-04 PLANT PV, Inc. Core-shell nickel alloy composite particle metallization layers for silicon solar cells
US10550291B2 (en) 2015-08-25 2020-02-04 Hitachi Chemical Co., Ltd. Core-shell, oxidation-resistant, electrically conducting particles for low temperature conductive applications
WO2017035102A1 (fr) * 2015-08-26 2017-03-02 Plant Pv, Inc Pâtes de métallisation sans contact d'argent-bismuth pour cellules solaires au silicium
US10418497B2 (en) 2015-08-26 2019-09-17 Hitachi Chemical Co., Ltd. Silver-bismuth non-contact metallization pastes for silicon solar cells
US9741878B2 (en) 2015-11-24 2017-08-22 PLANT PV, Inc. Solar cells and modules with fired multilayer stacks
US10000645B2 (en) 2015-11-24 2018-06-19 PLANT PV, Inc. Methods of forming solar cells with fired multilayer film stacks
US10233338B2 (en) 2015-11-24 2019-03-19 PLANT PV, Inc. Fired multilayer stacks for use in integrated circuits and solar cells
US10696851B2 (en) 2015-11-24 2020-06-30 Hitachi Chemical Co., Ltd. Print-on pastes for modifying material properties of metal particle layers
CN114846093A (zh) * 2019-12-11 2022-08-02 吉尼斯油墨公司 基于银纳米粒子的油墨

Similar Documents

Publication Publication Date Title
US20150243812A1 (en) Silver nanoparticle based composite solar metallization paste
US9698283B2 (en) Core-shell nickel alloy composite particle metallization layers for silicon solar cells
US9331216B2 (en) Core-shell nickel alloy composite particle metallization layers for silicon solar cells
EP2625722B1 (fr) Métallisation par pâte de cuivre pour cellules solaires au silicium
JP2018535557A (ja) 集積回路に使用するための焼成多層スタック及び太陽電池
WO2016099562A1 (fr) Pâte de métallisation solaire composite à base de nanoparticules d'argent
EP2137739A1 (fr) Formulations de conducteur à couche épaisse comprenant de l'argent et du nickel ou des alliages d'argent et de nickel et cellules solaires préparées à partir de celles-ci
JP5957546B2 (ja) 導電性組成物
JPWO2008078374A1 (ja) 太陽電池用導電性ペースト
WO2011140205A1 (fr) Pâtes pour film épais et piles solaires fabriquées à partir de celles-ci
WO2010124161A1 (fr) Pâtes métalliques et utilisation de celles-ci dans la fabrication d'électrodes positives sur des surfaces de silicium de type p
CN102369168A (zh) 用于光伏电池导体中的玻璃组合物
CN102348656A (zh) 用于光伏电池导体中的玻璃组合物
CA2729870A1 (fr) Composition contenant du metal, procede de fabrication de structures de contact electrique sur des composants electroniques ainsi que composant electronique
TWI447186B (zh) 用於太陽能電池上部電極之漿料組成物與包括其之太陽能電池
US20120119163A1 (en) Solderable polymer thick film silver electrode composition for use in thin-film photovoltaic cells and other applications
US20200098938A1 (en) Silver-bismuth non-contact metallization pastes for silicon solar cells
KR101633192B1 (ko) 태양전지의 전면 전극 및 이의 제조 방법
TWI660516B (zh) 機械性變形的金屬粒子
WO2015115567A1 (fr) Pile solaire, module de pile solaire, composant muni d'une électrode, dispositif à semi-conducteur et composant électronique
CN115611521A (zh) 一种玻璃粉以及含该玻璃粉铜浆在ZnO压敏陶瓷基体上的应用
EP4107788B1 (fr) Cellule solaire et procédé de fabrication associé
TW201623638A (zh) 基於銀奈米粒子之複合太陽能金屬化漿料
WO2016029397A1 (fr) Pâtes conductrices contenant du cuivre et électrodes fabriquées à partir de ces pâtes
WO2016029398A1 (fr) Cellules solaires pourvues d'électrodes en cuivre

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14908631

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14908631

Country of ref document: EP

Kind code of ref document: A1