CN107039539A - The method for forming the solar cell with sintered multilayer stacks of thin films - Google Patents

The method for forming the solar cell with sintered multilayer stacks of thin films Download PDF

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Publication number
CN107039539A
CN107039539A CN201611044889.9A CN201611044889A CN107039539A CN 107039539 A CN107039539 A CN 107039539A CN 201611044889 A CN201611044889 A CN 201611044889A CN 107039539 A CN107039539 A CN 107039539A
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layer
particle layer
metal particle
intercalation
metal
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Inventor
布莱恩·E·哈丁
艾瑞克·索尔
迪埃·苏赛诺
杰西·J·欣李奇
黄钰淳
林于唐
史蒂芬·T·康纳
丹尼尔·J·赫尔布什
克雷格·H·彼得斯
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Resonac Corp
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Plante Photovoltaic Ltd
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Priority to CN202010089230.5A priority Critical patent/CN111276553A/en
Publication of CN107039539A publication Critical patent/CN107039539A/en
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    • H01L31/0248—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 characterised by their semiconductor bodies
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    • H01L31/0264—Inorganic materials
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    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components 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
    • H01L27/142—Energy conversion devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals
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    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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    • H01L31/02—Details
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    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
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    • H02S40/44—Means to utilise heat energy, e.g. hybrid systems producing warm water and electricity at the same time
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    • H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
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    • H10N30/053—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes by integrally sintering piezoelectric or electrostrictive bodies and electrodes
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Abstract

Describe the method to form sintered multilayer stacking.This method includes step：A) wet metal particle layer is coated at least a portion of substrate surface, b) wet metal particle layer is dried, metal particle layer is dried to be formed, c) wet intercalation is directly coated at least a portion for drying metal particle layer, to form multiple-level stack, d) multiple-level stack, and e) combined firing multiple-level stack are dried, to form sintered multilayer stacking.Intercalation may include that low temperature substrates metallic, crystalline metal oxide particle and glass melt the one or more of grain.Wet metal particle layer may include：Aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, steel or its combination.

Description

The method for forming the solar cell with sintered multilayer stacks of thin films
The cross reference of related application
This application claims U.S. Provisional Patent Application 62/259,636, on April 5th, 2016 filed in 24 days November in 2015 The U.S. Provisional Patent Application 62/318,566 of application, U.S. Provisional Patent Application 62/371 filed in August in 2016 5 days, U.S. Provisional Patent Application 62/423 filed in 16,236 and 2016 on November, 020 priority, their full content leads to Cross with reference to merging herein.
The statement of governmental support
The IIP-1430721 contracts number authorized based on NSF, the present invention has been obtained for governmental support.In the present invention, political affairs Mansion can have specific rights.
Technical field
The present invention relates to embedded slurry, it includes noble metal, imbedded particle and organic carrier.
Embedded slurry (intercalation paste) can be used for the power conversion efficiency for improving solar cell.Base In silver insertion slurry be printed on aluminium lamination, its after firing have appropriateness peel strength (peel strength) and with That is soft soldering is to colored belt (tabbing ribbon).This slurry is particularly well adapted for use in the solar cell based on silicon, and it makes With aluminum back surface field (BSF).Typically, the 85-92% of the silicon wafer of the list of commercial production-and many-crystal silicon solar batteries Back surface area covered by aluminum shot sublayer, which form back surface field and with silicon carry out Ohmic contact (ohmic contact). Remaining 5-10% rear silicon face reference lamina after silver is covered, and it does not produce field and does not carry out Ohmic contact with silicon wafer. Reference lamina is mainly used in soft soldering colored belt to electrically connect solar cell afterwards.
When the silicon base layer (substrate) on rear side of the silver layer with solar cell is directly contacted, instead of contacting basic unit During aluminum shot sublayer, estimate that the absolute standard of the conversion efficiency of solar cell reduces 0.1% to 0.2%.Therefore, height is needed Use aluminum shot sublayer to cover the whole rear portion of solar cell, and remain able to be connected to solar cell using colored belt Together.Past, researcher has attempted to silver being directly printed on the top of aluminum shot sublayer, but in the aerial burning of high temperature During system, aluminium and silver layer phase counterdiffusion (interdiffusion), and cause layer surface to become to aoxidize and lose solderability.Some Researcher has attempted to change atmospheric conditions to reduce oxidation；However, the silver paste of front side is in oxidation atmosphere, such as dry air In perform most preferably, and whole solar battery efficiency is reduced after the processing in inert atmosphere.Other researchers are The peak value firing temperature of reduction chip is attempted to reduce phase counterdiffusion, but the silver paste of front side needs peak value firing temperature (that is, more than 650 DEG C) with sinterable silicon nitrogen oxides, to carry out Ohmic contact with silicon base layer.Recently, researcher is using direct The ultrasonic wave soft soldering of tin alloy at the top of the aluminium, to produce solderable surface (solderable surface).This technology Enough peel strengths (that is, 1-1.5N/mm) are had been realized in, but needs extra equipment and uses substantial amounts of tin, this increasing Expense is added.In addition, can be increased at chip breach and reduction using ultrasonic wave soft soldering on friable material, such as aluminium and silicon wafer Manage yield.
Demand with the printable slurry of development, it can improve the material of (modify) lower metal particle layer during firing Expect attribute.For example, the noble metal (precious metal) comprising slurry, it can be printed directly on aluminium and use standard too Positive energy Battery disposal condition is fired, and can improve solar battery efficiency.These slurries can reduce Ag/Al phase counterdiffusion, so that Solderable is kept to colored belt.Need slurry be it is screen printing and act as plug-in type replacing, it will not bring extra It is important to pay and be integrated to immediately in existing production line.
The content of the invention
Disclose sintered multilayer and stack (fired multilayer stack).In an embodiment of the invention, Stacking has basic unit, the metal particle layer in substrate surface at least a portion, the improvement in substrate surface at least a portion Metal particle layer, and the improvement intercalation directly at least a portion of improvement metal particle layer.Improvement intercalation, which has, to be faced Solderable surface away from basic unit.Improveing metal particle layer includes and metal particle layer identical metallic and at least one Material from improvement intercalation.Improve intercalation and include noble metal and the material from lower group selection, comprising：Antimony, arsenic, barium, bismuth, boron, Cadmium, calcium, cerium, caesium, chromium, cobalt, gallium, germanium, indium, iron, lanthanum, hafnium, lead, lithium, magnesium, manganese, molybdenum, niobium, phosphorus, potassium, rhenium, selenium, silicon, sodium, strontium, Sulphur, tellurium, tin, vanadium, zinc, zirconium, it is combined, and its alloy, its oxide, its synthetic, and its other combinations.In one kind arrangement In, improvement intercalation includes noble metal and the material from lower group selection, comprising：Bismuth, boron, indium, lead, silicon, tellurium, tin, vanadium, zinc, its group Close and its alloy, its oxide, its synthetic, and its other combinations.
In an embodiment of the invention, improvement intercalation has two phases (phase)：Noble metal phase (precious metal phase) and embedded phase (intercalation phase).Improvement intercalation more than 50% can Soldering surfaces can include noble metal phase.Improvement metal particle layer may include metallic discussed above and carry out self-embedding phase At least one material.Embedded phase includes the material from lower group selection, comprising：Antimony, arsenic, barium, bismuth, boron, cadmium, calcium, cerium, caesium, Chromium, cobalt, gallium, germanium, indium, iron, lanthanum, hafnium, lead, lithium, magnesium, manganese, molybdenum, niobium, phosphorus, potassium, rhenium, selenium, silicon, sodium, strontium, sulphur, tellurium, tin, vanadium, Zinc, zirconium, it is combined, and its alloy, its oxide, its synthetic, and its other combinations.Noble metal phase is included from lower group selection At least one material, comprising：Au Ag Pt Pd, rhodium, and alloy, synthetic, and its other combinations.
In yet another embodiment of the present invention, improvement intercalation has two sublayers (sublayer)：Directly in improvement Sub- intercalation (intercalation sublayer) at least a portion of metal particle layer, and directly in sub- intercalation extremely Noble metal sublayer (precious metal sublayer) in a few part.Your gold is the solderable surface for improveing intercalation include Belong to sublayer.Improvement metal particle layer may include metallic discussed above and at least one material from sub- intercalation.For The possibility material of sub- intercalation is embedded in the identical of phase with being described above to.For noble metal sublayer possibility material with above What is described is used for the identical of noble metal phase.
In yet another embodiment of the present invention, sintered multilayer is stacked with the improvement that metal particle layer is improved as it Aluminum shot sublayer.It has the improvement intercalation of two sublayers：Rich bismuth (bismuth-rich) directly in improvement aluminum shot sublayer Sublayer；And Fu Yin (silver-rich) sublayer directly in rich bismuth sublayer.The solderable surface for improveing intercalation includes rich silver Sublayer.Aluminum shot sublayer is improved comprising aluminum particulate and at least one material from lower group selection can be also included, including：Aluminum oxide, Bismuth and bismuth oxide.
In one arrangement, at least one dielectric layer is directly at least a portion of substrate surface.Dielectric layer include from At least one material of lower group selection, comprising：Silicon, aluminium, germanium, gallium, hafnium, and oxide, nitride, synthetic and combinations thereof. In another arrangement, alumina medium layer is directly at least a portion of substrate surface and silicon nitride medium layer is directly in oxidation On aluminium dielectric layer.
In one arrangement, solid (for example, eutectic (eutectic)) composite bed (compound layer) is directly in base In layer surface.Solid composite bed includes one or more metals from lower group selection, comprising：Aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, Titanium, and from one or more materials of lower group selection, comprising：Silicon, oxygen, carbon, germanium, gallium, arsenic, nitrogen, indium and phosphorus.
Basic unit's part on adjacent base layer surface can doped with least one material from lower group selection, comprising：Aluminium, copper, Iron, nickel, molybdenum, tungsten, tantalum, titanium, steel and combinations thereof.
In an embodiment of the invention, the part that sintered multilayer is stacked has variable thickness.Sintered multilayer heap The average peak for being more than 12 μm can be had to paddy height by folding.
Improveing at least 70wt% (percentage by weight) of the solderable surface of intercalation may include the material from lower group selection, wrap Contain：Silver, gold, platinum, palladium, rhodium, and alloy, synthetic and its other combinations.
Basic unit may include at least one material from lower group selection, comprising：Silicon, silica, carborundum, aluminum oxide, indigo plant Jewel, germanium, GaAs, gallium nitride and indium phosphide.Alternatively, basic unit may include the material from lower group selection, comprising：Aluminium, copper, Iron, nickel, titanium, steel, zinc, and alloy, synthetic and its other combinations.Metal particle layer may include the material from lower group selection, bag Contain：Aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, steel and alloy, synthetic and its other combinations.Noble metal may include from lower group selection Material, comprising：Silver, gold, platinum, palladium, rhodium, and alloy, synthetic, and its other combinations.
Metal particle layer can have the porosity between the thickness and/or 1 to 50% between 0.5 μm to 100 μm.Improvement is inserted Layer can have the thickness between 0.5 μm to 10 μm.Sintered multilayer, which is stacked, can have 0 to the contact resistance between 5mOhm, as by What transmission route survey was determined.
Directly there can also be colored belt at least a portion of the solderable surface of improvement intercalation.In one arrangement, Peel strength between colored belt and improvement intercalation is more than 1N/mm.
In yet another embodiment of the present invention, sintered multilayer is stacked with basic unit, in basic unit's at least a portion Metal particle layer, the improvement metal particle layer in basic unit's at least a portion, and directly in improvement metal particle layer at least Improvement intercalation in a part.Improveing intercalation has two sublayers：Directly at least a portion of improvement metal particle layer Sub- intercalation, and the noble metal sublayer directly at least a portion of sub- intercalation.Improveing metal particle layer includes metallic With at least one material from sub- intercalation.Possibility material for sub- intercalation has been described above.
In yet another embodiment of the present invention, sintered multilayer is stacked with silicon base layer, in basic unit's at least a portion Aluminum shot sublayer, the improvement aluminum shot sublayer in basic unit's at least a portion, and directly improvement aluminum shot sublayer on improvement insert Layer.Improveing intercalation has two sublayers：Rich bismuth sublayer directly in improvement aluminum shot sublayer, and directly in rich bismuth sublayer Rich silver layer.Improveing aluminum shot sublayer includes at least one material from lower group selection, comprising：Aluminium, aluminum oxide, bismuth and bismuth oxidation Thing.
In an embodiment of the invention, solar cell has silicon base layer, directly on the preceding surface of silicon base layer At least one front medium layer at least a portion, multiple fine grid blockses lines in the part on the preceding surface of silicon base layer Conflux layer (front before at least one of at least one electrical contact of (fine grid line) and multiple fine grid blockses lines Busbar layer), the aluminum shot sublayer at least a portion on the rear surface of silicon base layer, and on the rear surface of silicon base layer Rear reference lamina (rear tabbing layer) in a part.Reference lamina includes afterwards, the part on the rear surface of silicon base layer On improvement aluminum shot sublayer, and directly improvement aluminum shot sublayer at least a portion on improvement intercalation.Improvement intercalation has In face of the solderable surface away from silicon base layer.Improveing aluminum shot sublayer includes aluminum particulate and at least one material from improvement intercalation Material.Possibility material for improveing intercalation has been described above.Aluminum shot sublayer can have 1 μm to 50 μm between thickness and/ Or the porosity between 3 to 20%.Reference lamina can have the thickness between 1 μm to 50 μm afterwards.Silicon base layer can be monocrystalline silicon wafer Piece, with p-type substrate or n-type substrate.Silicon base layer can be polycrystalline silicon wafer, with p-type substrate or n-type substrate.
In an embodiment of the invention, improvement intercalation includes two phases：Noble metal phase and embedded phase.Greatly Solderable surface in 50% can be made by noble metal phase.Improvement aluminum shot sublayer includes aluminum particulate and carrys out self-embedding phase extremely A kind of few material.Possibility material for being embedded in phase has been described above.Possibility material for noble metal phase is Described above.
In yet another embodiment of the present invention, improvement intercalation includes two sublayers：Directly in improvement metal particle layer At least a portion on sub- intercalation, and directly noble metal sublayer at least a portion of sub- intercalation.Solderable surface Include noble metal sublayer.Improveing aluminum shot sublayer includes aluminum particulate and at least one material from sub- intercalation.For sub- intercalation Possible material has been described above.Possibility material for noble metal sublayer has been described above.
In yet another embodiment of the present invention, improvement intercalation includes two sublayers：Directly in improvement aluminum shot sublayer Rich bismuth sublayer, and directly in rich bismuth sublayer rich silver layer.Improvement aluminum shot sublayer further comprises from lower group selection At least one material is included：Aluminum oxide, bismuth and bismuth oxide.In one arrangement, improvement aluminum shot sublayer further comprises bismuth And/or bismuth oxide, and bismuth adds the weight ratio (Bi of aluminium with bismuth:(Bi+Al)) at least than in aluminum shot sublayer in improvement aluminum shot sublayer It is middle high by 20%.Rich bismuth sublayer can have the thickness between 0.01 μm to 5 μm or between 0.25 μm to 5 μm.
In one arrangement, at least one rear dielectric layer is directly at least a portion on the rear surface of silicon base layer.After be situated between Matter layer includes following one or more：Silicon, aluminium, germanium, hafnium, gallium, and oxide, nitride, synthetic and combinations thereof.Medium afterwards Layer can include silicon nitride.In another arrangement, dielectric layer is directly after silicon base layer at least a portion on surface after aluminum oxide And after silicon nitride dielectric layer directly after aluminum oxide on dielectric layer.In one arrangement, solid aluminium-silicon Eutectic Layer is directly in silicon substrate On layer.In one arrangement, a part of silicon base layer on surface further comprises back surface field, and back surface field after adjacent silicon base layer Doped p type is to every cm3Have 1017To 1020Between atom (atoms).
In an embodiment of the invention, a part for rear reference lamina, which has variable thickness and can had, is more than 12 μm Average peak to paddy height.
Directly there can be colored belt at least a portion of the solderable surface of improvement intercalation.Solderable surface can be Fu Yin's.Solderable surface can include at least 75wt% silver.Soft soldering to the colored belt of the solderable surface of rich silver can have big In 1N/mm peel strength.
A part for improvement aluminum shot sublayer can have variable thickness.Improveing a part for aluminum shot sublayer can have more than 12 μm Average peak to paddy height.The contact resistance between reference lamina and aluminum shot sublayer can be 0 between 5mOhm, as power transmission line afterwards What drive test amount was determined.
In yet another embodiment of the present invention, solar cell has silicon base layer, directly on the preceding surface of silicon base layer At least a portion at least one front medium layer, multiple fine grid blockses lines in the part on the preceding surface of silicon base layer, With multiple fine grid blockses lines at least one electrical contact at least one before conflux layer, at least one on the rear surface of silicon base layer Aluminum shot sublayer on point, and the rear reference lamina in the part on the rear surface of silicon base layer.Reference lamina has solderable table afterwards Face.Reference lamina includes afterwards, the improvement aluminum shot sublayer after silicon base layer at least a portion on surface, directly in improvement aluminum shot sublayer At least a portion on rich bismuth sublayer, and directly at least a portion of rich bismuth sublayer rich silver layer.Improve aluminum shot Sublayer includes aluminum particulate and at least one material from lower group selection, including：Aluminum oxide, bismuth and bismuth oxide.
In yet another embodiment of the present invention, solar module has after anter (front sheet), anter Preceding encapsulated layer (front encapsulant layer) on surface, and the first silicon solar cell on preceding encapsulated layer and Second silicon solar cell.Each silicon solar cell can be any silicon solar cell described here.Solar cell Module also have the first battery interconnection (first cell interconnect), it include with before the first silicon solar cell The first colored belt that both rear reference laminas of layer and the second silicon solar cell that confluxes make electrical contact with, rear piece (rear sheet), after Post package layer (rear encapsulant layer) on the rear surface of piece.The Part I and the first silicon sun of post package layer Energy battery and the second silicon solar cell are contacted, and the Part II of post package layer is contacted with preceding encapsulated layer.
The interconnection of first battery may also include the terminal box (junction box) contacted with rear piece.Terminal box can be comprising at least One by-pass diode (bypass diode).There can also be at least one convergent belt for being connected to the first colored belt.
In an embodiment of the invention, slurry (paste) is disclosed.Slurry is comprising 10wt% between 70wt% Noble metal, at least 10wt% imbedded particle (intercalating particle) and organic carrier (organic vehicle).Imbedded particle includes the one or more from lower group selection, is aoxidized comprising low temperature substrates metallic, crystalline metal Thing particle and glass melt grain (glass frit particle).The weight ratio of imbedded particle and noble metal at least can be 1：5.
Noble metal may include at least one material from lower group selection, comprising：Au Ag Pt Pd, rhodium, and alloy, Synthetic, and its other combinations.Noble metal can have the D50 and 0.4 to 7.0m between 100nm to 50 μm2Between/g Specific surface area.A part for noble metal can have for example spherical, sheet and/or the shape of elongated shape.Noble metal can It is distributed with unimodal size distribution or multi-modal size.In one embodiment, noble metal is silver and has 300nm extremely D50 and 1.0 to 3.0m between 2.5 μm2Specific surface area between/g.
Imbedded particle can have the D50 and 0.1 to 6.0m between 100nm to 50 μm2Specific surface area between/g.Embedded grain A part for son can have for example spherical, sheet and/or the shape of elongated shape.Imbedded particle can have unimodal size distribution or many Peak Size Distribution.
Low temperature substrates metallic may include the material from lower group selection, comprising：Bismuth, tin, tellurium, antimony, lead, and alloy, conjunction Into thing, and its other combinations.In one embodiment, low temperature substrates metallic is comprising bismuth and between 1.5 to 4.0 μm D50 and 1.0 to 2.0m2Specific surface area between/g.
In an embodiment of the invention, at least some low temperature substrates metallics have by monoshell (singleshell) the bismuth core particle surrounded, it includes the material from lower group selection, comprising：Silver, nickel, nickel-boron, tin, tellurium, Antimony, lead, molybdenum, titanium, and alloy, synthetic, and its other combinations.In this another embodiment, at least some low temperature bases Bottom metallic has the bismuth core particle surrounded by monoshell, and it includes the material from lower group selection, comprising：Silica, oxidation Magnesium, boron oxide and its any combination.
Crystalline metal oxide particle may include oxygen and the metal from lower group selection, comprising：Bismuth, tin, tellurium, antimony, lead, vanadium, Chromium, molybdenum, boron, manganese, cobalt, and alloy, synthetic, and its other combinations.
Glass, which melts grain, includes the material from lower group selection, comprising：Antimony, arsenic, barium, bismuth, boron, cadmium, calcium, cerium, caesium, chromium, cobalt, Fluorine, gallium, germanium, indium, hafnium, iodine, iron, lanthanum, lead, lithium, magnesium, manganese, molybdenum, niobium, potassium, rhenium, selenium, silicon, sodium, strontium, tellurium, tin, vanadium, zinc, zirconium, its Alloy, its oxide, its synthetic, and its other combinations.
Slurry can have 30wt% to the solids laden between 80wt%.Imbedded particle can constitute slurry at least 15wt%.In one arrangement, slurry includes 45wt% Ag particles, 30wt% bismuth granule and 25wt% organic carrier. In another arrangement, slurry includes 30wt% Ag particles, 20wt% bismuth granule and 50wt% organic carrier.Slurry exists 25 DEG C at 4 seconds (sec)-1Shear rate (sheer rate) under can have 10,000 to the viscosity between 200,000cP.
In an embodiment of the invention, the combined firing (co-firing) to form sintered multilayer stacking is described Method.This method includes step：A) wet metal particle layer is coated at least a portion of substrate surface, b) dries wet metallic Layer, to form dry metal particle layer, c) directly coats wet intercalation at least a portion for drying metal particle layer, many to be formed Layer is stacked, and d) dries multiple-level stack, and e) combined firing multiple-level stack, to form sintered multilayer stacking.
In yet another embodiment of the present invention, the sequential grammar to form sintered multilayer stacking is described.This method bag Containing step：A) wet metal particle layer is coated at least a portion of substrate surface, wet metal particle layer b) is dried, to form drying Metal particle layer, c) fires and dries metal particle layer, d) straight at least a portion of metal particle layer to form metal particle layer Connect and coat wet intercalation, to form multiple-level stack, e) dry multiple-level stack, and f) fire multiple-level stack, to form sintered multilayer Stack.
In one arrangement, for two kinds of combined firing method and sequential grammar, wet intercalation has 10wt% to 70wt% Between noble metal, at least 10wt% imbedded particle and organic carrier.Imbedded particle may include one from lower group selection Plant or a variety of, include low temperature substrates metallic, crystalline metal oxide particle and glass and melt grain.Wet metal particle layer may include From the metallic of lower group selection, comprising：Aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, steel and alloy, synthetic and its other groups Close.
In one arrangement, for two kinds of combined firing method and sequential grammar, there is additional step before step a).It is attached Plus step is included, at least one dielectric layer is deposited at least a portion of substrate surface.In this arrangement, step a) bags Contain, wet metal particle layer is directly coated at least a portion of dielectric layer.
For two kinds of combined firing method and sequential grammar, each coating step can include the method from lower group selection, bag Include：Silk-screen printing, intaglio printing (gravure printing), jet deposition (spray deposition), slit coating, 3D Printing and ink jet printing.In one arrangement, step a) is included, and silk-screen printing is carried out by figuratum silk screen, to produce tool There is the wet metal particle layer of variable thickness.
It for two kinds of combined firing method and sequential grammar, step b) and can d) include, be done at a temperature of less than 500 DEG C It is dry between 1 second to 90 minutes, or between drying 1 second to 60 minutes at a temperature of between 150 DEG C to 300 DEG C.Step e) can Comprising the constant temperature for being heated rapidly to be more than 600 DEG C in atmosphere adds rapidly between 0.5 second to 60 minutes, or in atmosphere Constant temperature of the heat extremely more than 700 DEG C 0.5 to 3 second.
In one arrangement, for two kinds of combined firing method and sequential grammar, included in additional step f), it is many sintering Soft soldering colored belt in the part that layer is stacked.
Low temperature substrates metallic, crystalline metal oxide particle, glass melt grain and metal particle layer is being retouched in detail above State.
In yet another embodiment of the present invention, the method for manufacture solar cell includes step：A) silicon wafer is provided, B) at least a portion at the silicon wafer back side coats wet aluminum shot sublayer, c) dries wet aluminum shot sublayer to form aluminum shot sublayer, d) exists At least a portion of aluminum shot sublayer directly coats wet intercalation, to form multiple-level stack, multiple-level stack e) is dried, f) in silicon wafer A plurality of fine grid blockses line and the layer that confluxes before at least one are coated in preceding surface, g) dry a plurality of fine grid blockses line and remittance before at least one Fluid layer to form structure, and h) the combined firing structure to form silicon solar cell.
Wet intercalation has been described above.
In one arrangement, there is additional step between step a) and step b).Additional step is included, after silicon wafer At least one dielectric layer is deposited at least a portion on surface.At this so that in arrangement, step b) is included, at least the one of dielectric layer Directly coat wet aluminum shot sublayer in part.
Each coating step can include the method from lower group selection, including：It is silk-screen printing, intaglio printing, jet deposition, narrow Groove coating, 3D printing and ink jet printing.In one arrangement, step b) is included, and silk-screen printing is carried out by figuratum silk screen, To produce the wet aluminum shot sublayer with variable thickness.
It for two kinds of combined firing method and sequential grammar, step e) and can g) include, be done at a temperature of less than 500 DEG C It is dry between 1 second to 90 minutes, or between drying 1 second to 60 minutes at a temperature of between 150 DEG C to 300 DEG C.Step h) can Comprising the constant temperature for being heated rapidly to be more than 600 DEG C in atmosphere adds rapidly between 0.5 second to 60 minutes, or in atmosphere Constant temperature of the heat extremely more than 700 DEG C 0.5 to 3 second.
Low temperature substrates metal, crystalline metal oxide particle and glass melt grain in above-detailed.
Brief description of the drawings
When being read in conjunction with the figure to description below exemplary embodiment, those skilled in the art will be readily appreciated that Foregoing and other side.Accompanying drawing is not drawn to scale.Accompanying drawing is only signal and is not intended in detail or limits the present invention.
Accompanying drawing 1 is the schematic sectional view of the multiple-level stack before firing according to embodiments of the present invention.
Accompanying drawing 2 is the schematic sectional view stacked according to embodiments of the present invention, sintered multilayer.
Accompanying drawing 3 is the schematic sectional view that sintered multilayer is stacked, and wherein intercalation (intercalation layer), which has, divides From phase.
Accompanying drawing 4 is the schematic sectional view that sintered multilayer is stacked, and wherein intercalation has the phase for being divided into two sublayers.
Accompanying drawing 5 is that the schematic of a part stacked according to embodiments of the present invention, the sintered multilayer shown in accompanying drawing 2 cuts Face figure.
Accompanying drawing 6 is according to embodiments of the present invention, the ESEM (SEM) of joint sintering (co-fired) multiple-level stack Sectional view.
Accompanying drawing 7 is that the ESEM (SEM) that the joint sintered multilayer with silver-bismuth frit layer (frit layer) is stacked is cut Face figure.
Accompanying drawing 8 is ESEM (SEM) sectional view of the aluminum shot sublayer on silicon base layer (in SE2 patterns).
Accompanying drawing 9 is ESEM (SEM) sectional view of the aluminum shot sublayer on the silicon base layer shown in accompanying drawing 8 (in InLens moulds Formula).
Accompanying drawing 10 is ESEM (SEM) section of a part for the silicon solar cell stacked comprising joint sintered multilayer Figure is (in InLens patterns).
Accompanying drawing 11 is the scanning of the part of the silicon solar cell stacked comprising joint sintered multilayer shown in accompanying drawing 10 Electronic Speculum (SEM) sectional view (in SE2 patterns).
Accompanying drawing 12 shown according to embodiments of the present invention, from aluminum shot sublayer and from the energy color of improvement aluminum shot sublayer Dissipate x- ray (EDX) spectrum.
Accompanying drawing 13 is the EDX spectrum on the surface of the rear reference lamina comprising aluminium-bismuth intercalation according to embodiments of the present invention.
Accompanying drawing 14 shows the x- from the joint sintered multilayer film being stacked on the rear reference lamina of silicon solar cell Ray scattering pattern.
Accompanying drawing 15 is the multi-layer thin membrane stack that dielectric layer (dielectric layer) is included according to embodiments of the present invention It is stacked in the schematic sectional view before firing.
Accompanying drawing 16 is the schematic cross-sectional of the sintered multilayer stacks of thin films comprising dielectric layer according to embodiments of the present invention Figure.
Accompanying drawing 17 is the plan view light micrograph for the joint sintered multilayer stacks of thin films for having occurred that bending.
Accompanying drawing 18 is, according to embodiments of the present invention, to can be used for the silk screen design during the deposition of wet metal particle layer (not proportional to draw).
Accompanying drawing 19 is according to embodiments of the present invention, with the dry of the variable thickness using silk-screen deposition shown in accompanying drawing 18 The schematic section of dry metal particle layer.
Accompanying drawing 20 be according to embodiments of the present invention, with the variable thickness using silk-screen deposition shown in accompanying drawing 18 and with I.e. joint sintering improves the schematic section of metal particle layer.
Accompanying drawing 21 is the plan view light micrograph that joint sintered multilayer as shown in Figure 20 is stacked.
Accompanying drawing 22 is the cross-sectional SEM image for the part that the sintered multilayer with variable thickness is stacked.
Accompanying drawing 23 is the cross-sectional SEM image of a part for the aluminum particulate film on the silicon base layer with flat thickness.
Accompanying drawing 24 is the surface topology scanning that the sintered multilayer with variable thickness is stacked.
Accompanying drawing 25 is the surface topology scanning of sintered aluminium particle layer.
Accompanying drawing 26 shows before silicon solar cell the schematic diagram of (or illuminated) side.
Accompanying drawing 27 is the schematic diagram for the rear side for showing silicon solar cell.
Accompanying drawing 28 is that according to embodiments of the present invention, including the solar module that stacks of sintered multilayer is schematic Sectional view.
Accompanying drawing 29 is to stack the solar-electricity with the colored belt of soft soldering according to embodiments of the present invention, including sintered multilayer ESEM (SEM) sectional view of the dorsal part in pond.
Accompanying drawing 30 is the transmission route survey drawing of reference lamina after the silvery on traditional silicon.
Accompanying drawing 31 is that the transmission route survey of silver-bismuth intercalation in the aluminum shot sublayer for the rear reference lamina being used as on silicon is painted Figure.
Embodiment
Preferred embodiment is had been illustrated with the background that embedded slurry is sintered in metal particle layer.However, this area Technical staff will readily appreciate that material disclosed herein and method have the application under a variety of backgrounds, need herein and half It is important that conductor or conductor material, which carry out excellent electric contact, particularly good attachment, high-performance and low expense,.
The whole publications referred to herein are herein incorporated by the reference of all of which content, for having existed such as it This purpose elaborated completely.
The composition and purposes of embedded slurry are disclosed that, embedded slurry includes noble metal and imbedded particle, and it can It is printed in metal particle layer, to be sintered at them after sintered multilayer stacking, changes the attribute of metal particle layer. In an embodiment of the invention, embedded slurry is used to provide solderable surface in metal particle layer, and it can not be by it Itself soft soldering.Embedded slurry may be additionally used for improving the tack fired in multiple-level stack or change metal particle layer with going to a grassroots level Interaction.Embedded slurry can be extensively using to much applying, including transistor (transistor), light emitting diode And integrated circuit；However, example disclosed below will focus primarily on photovoltaic cell (photovoltaic cell).
Definition and method
ESEM (SEM) as used herein and x-ray energy dispersive spectrum (EDX) (collectively referenced as SEM/EDX) are used Zeiss Gemini Ultra-55 parse field emission scanning electron microscope, equipped with Bruker6 | 60 detectors are held OK.Details on operating condition is described in each analysis.The cross-sectional SEM image that sintered multilayer is stacked passes through ion milling (ion milling) and prepare.Thin epoxy resin layer is painted on the top of sintered multilayer stacking and dried at least 30 minutes.The sample Originally JEOL IB-03010CP ion milling machines are then passed to, are operated 8 hours in 5kV and 120uA, to be removed from sample edge 80 microns.The sample of milling is stored in before SEM/EDX in nitrogen casing.
Term " dry (drying) " describes a kind of heat treatment, or less than 500 DEG C temperature or less than 400 DEG C or Less than 300 DEG C, any scope for continuing the period between 1 second to 90 minutes or being contained therein.Slurry is typically via silk screen Printing or other deposition process are applied to basic unit, to produce " wet " layer.Wet layer can be dried to reduce or remove volatile organic matter Matter, such as solvent, produce " drying " layer.
Term " firing (firing) " describes the heating in the temperature higher than 500 DEG C, higher than 600 DEG C or higher than 700 DEG C, Any scope for continuing the period between 1 second to 60 minutes or being contained therein.Term " sinter layer (dried layer) " is described The drying layer that has been sintered.
Herein using term " multiple-level stack (multilayer stack) " to describe basic unit, thereon with different materials Two layers or multilayer." sintered multilayer stacks (fired multilayer stack) " is that its each layer is dried and sintered Multiple-level stack.There are a variety of methods to fire this multiple-level stack.Term " joint sintering (co-firing) " is used to describe to multilayer The only once sintered processing stacked.For example, during silicon solar cell is manufactured, one layer of aluminum particulate slurry is applied to first Basic unit and dried.Then, rear mark pulp layer is painted in a part for dry aluminum shot sublayer, is dried, is brought afterwards Dry aluminum shot sublayer and the rear reference lamina dried.During combined firing, two drying layers are burnt simultaneously in one step Knot.Term " order sintering (sequential firing) " is used to describe the processing to the multiple sintering of multiple-level stack.In order During processing, metallic slurry is painted in basic unit, dried and then sinters.Embedded slurry, which is then coated in, to be dried and sintered gold In the part for belonging to particle slurry (being referred to as metal particle layer).Then, whole multiple-level stack is dried and sintered for the second time.It should note Anticipate and arrive, description joint sintered multilayer is stacked or the embodiments of the present invention of structure apply also for the multilayer sequentially sintered Stack or structure.
Term " embedded (intercalation) " as used herein is used for the infiltration for describing porous material (penetration).In the context of embodiment described here, term " insertion " is described from intercalation The material of imbedded particle (intercalating particle) in (intercalation layer) is during firing process Adjacent porous dry metal particle layer is penetrated into, it brings the imbedded particle material at least a portion of metallic Coating (part or all of).Term " improvement metal particle layer (modified metal particle as used herein Layer) " it is used to describe this sintering metal particle layer that the material from imbedded particle has permeated.
In relation between description adjacent layer, preposition as used herein " on " mean that each layer may or may not be each other Direct physical contact.For example, one layer is said on basic unit, the layer is positioned to direct neighbor basic unit or is connected on above basic unit Or it is adjacent thereto.It is connected on above basic unit or theory adjacent thereto, can has between certain layer and basic unit or can between certain layer With neither one or multiple extra plays.In relation between description adjacent layer, this preposition used " directly on " meaning Each layer to be in direct physical contact with each other.For example, being said between one layer on basic unit, the layer is positioned to direct neighbor basic unit.
When metal particle layer mainly includes metal A particles, it can be described as " metal A particle layers ".For example, working as metal particle layer When mainly including aluminum particulate, aluminum shot sublayer can be described as.When improvement metal particle layer mainly includes metal A particles, it can be described as " changing Good metal A particle layers ".For example, when improvement metal particle layer mainly includes aluminum particulate, can be described as improveing aluminum shot sublayer.
Term " solderable surface (solderable surface) " is known in the art." solderable surface " is represented can By the surface of soft soldering to welding.Personnel with ordinary skill are familiar with the change of solderable surface.Produce solderable table The examples of materials in face includes but is not limited to, tin, cadmium, gold, silver, palladium, rhodium, copper, zinc, lead, nickel, its alloy, its combination, its synthetic And its mixture.In one embodiment, when at least 70wt% on surface includes such as silver, gold, platinum, palladium, rhodium and its conjunction When gold, synthetic and the material of other combinations, surface is solderable.
Particle described here can take on any of a number of shapes, size, specific surface area and oxygen content.Particle can be spherical, pin Shape, horn shape, dendroid, threadiness, sheet, particle, irregular and nodositas, as ISO 3252 is defined.It is understood that It is that term " spherical (spherical) " as used herein represents general spherical form, and may include spherical, granular, tubercle Shape, and sometimes irregular shape.Term " thin slice (flake) " represents thin slice, and sometimes angular, fibrous and not Regular shape.Term " elongated (elongated) " represents needle-like, and it is sometimes angular, dendritic, fibrous and Irregular shape, such as ISO3252:1999 definition.Shape of particle, form, size and Size Distribution generally depend on synthesis skill Art.One group of particle may include the combination of the particle of different shape and size.
Spherical or elongated particle is typically described by their D50, specific surface area and particle size distribution.D50 values are limited It is set to a value, the particle of the quantity of one half has the diameter for being less than the value and the particle of half quantity is with straight higher than the value Footpath.Measurement particle diameter distribution is typically performed using laser diffraction particle size analyzer, such as Horiba LA-950.For example, Spherical particle is scattered in a solvent, and they separate and transmit the distribution direct correlation of light from being minimal to maximum well wherein The Size Distribution of diameter.Common approach is to represent that laser diffraction result is to report the D50 values based on volume distributed median.Particle size Statistical distribution it is also possible to use laser diffraction particle size analyzer measurement.Commonly, for noble metal, can have it is unimodal or Multimodal particle size distribution.In Unimodal Distribution, particle size is monodispersed, and D50 is at the center of single distribution.Multimodal grain Sub- Size Distribution has more than one peak (or summit) in particle size distribution.Multimodal particle size distribution can increase powder Tap density (tap intensity), it typically brings higher partial veil density (green film density).
In certain embodiments of the present invention, particle can have thin slice as defined above or elongated shape.Thin slice can have There are diameter and 100nm between 1 μm to 100 μm or between 1 μm to 15 μm to the thickness between 500nm.Elongated shape can have 200nm is to the diameter between 100nm and the length more than 1 μm.In yet another embodiment of the present invention, do not have to shape of particle It is restricted；Any shape of particle can be used, as long as its maximum gauge is not more than 50 μm, 5 μm or 1 μm.
Brunauer-Emmett-Teller can be used in the specific surface area (specific surface area) of particle (BET) method, according to DIN ISO 9277,2003-05 measurement.The ratio of particle disclosed herein and particularly silver and bismuth granule Surface area, is determined by following method of testing：Performed using TriStar 3000 (coming from Micromeritics instrument companies) BET is measured, and it is operated based on physical absorption analytical technology.Sample prepares to include degasification, to remove the molecule of absorption.Nitrogen is analysis The void volume of gas and helium for determining sample tube.Micromeritics provides sial (silica alumina), is used for As reference material, with preparation routine and test condition.Measurement starts from increasing the reference material of known quality to sample Manage and sample tube is installed on BET device manifolds.Thermally-stabilised dispensing manifold, sample tube and for measuring saturation pressure (Po) it is special It is drained with pipe.When reaching enough vacuum, manifold is opened filled with helium (non-absorbing gas) and sample port, to determine The warm free space of sample at room temperature.Sample tube with reference material is immersed in liquid nitrogen and is cooled near 77K, and And free space analysis is performed again.Use PoThe saturation pressure of pipe measurement absorption, therewith on nitrogen dispensing to atmospheric pressure In manifold.The pressure and temperature of nitrogen is recorded, and then sample port is opened, so as to allow nitrogen to absorb on sample.At some After time, port shutdown, so as to allow to be absorbed to up to balance.The amount of absorption is during the nitrogen quantity removed from manifold subtracts sample tube Any residual nitrogen.Along absorption isotherm measurement point be used for calculate reference material with m2The specific area of/g meters；This journey Sequence is repeated by any sample interested, particle for example described here.
Particle described here has significant hot attribute：Fusing point and/or softening point, the two both depends on the crystallization of material Degree.The fusing point of particle can by using by TA instrument manufacturings DSC2500 differential scanning calorimeters carry out differential scanning calorimetry and Determined using the method described in ASTM E794-06 (2012).The fusing point of crystalline material it is also possible to use warm table and x is penetrated Line diffraction is determined.Because crystalline material is heated on its fusing point, diffraction peak starts to disappear.Softening point is amorphous or glass Glass plasmid starts the temperature of softening.Dilatometer (dilatometer) can be used to determine for the softening point of glass particle.Softening point is also It can be obtained by the fiber extension method described in ASTM C338-57.
Material for manufacturing sintered multilayer stacking
In an embodiment of the invention, basic unit, metallic slurry and embedded slurry form sintered multilayer heap It is folded.Basic unit can be solid, plane or rigid material.In one embodiment, basic unit is included from least the one of lower group selection Material is planted, comprising：Silicon, silica, carborundum, aluminum oxide, sapphire, germanium, GaAs, gallium nitride and indium phosphide.This base Layer is generally used for the deposition of layer, and it constitutes transistor, light emitting diode, integrated circuit and photovoltaic cell.Basic unit, which can also be, to be led Electricity and/or flexible.In another embodiment, basic unit includes at least one material from lower group selection, comprising：Aluminium, Copper, iron, nickel, titanium, steel, zinc, and alloy, synthetic and its other combinations.
In an embodiment of the invention, metallic slurry includes metallic and organic carrier.In a kind of cloth In putting, metallic slurry also includes inorganic bond (inorganic binder), such as frit (glass frit). In one kind arrangement, conventional, commercially available metallic slurry is used.Include the aluminium being generally used on silicon solar cell Metal paste, by Ruxing Technology (such as RX8252H1), Monocrystal (such as EFX-39) and GigaSolar Materials (such as M7) are sold.Metallic may include aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium or its conjunction At least one of gold, synthetic or other combinations.In a variety of arrangements, metallic there is 100nm to 100 μm between, 500nm D50 between to 50 μm, between 500nm to 200 μm or in any scope for being contained therein.Metallic can have it is spherical, Elongated shape or slice-shaped shape, and can have unimodal or multi-modal size to be distributed.Frit can be contained in metallic slurry on a small quantity In (that is, less than 5wt%).In one embodiment, metallic slurry include 70wt% to 80wt% aluminum particulates, be less than 2wt% frits and organic carrier.
In an embodiment of the invention, embedded slurry includes noble metal, imbedded particle and organic carrier.Art Language " solids laden (solids loading) " can be used in combination with slurry, to describe noble metal and imbedded particle solid in slurry Amount and ratio.Slurry described here also include organic carrier, although itself and be infrequently expressly stated.
Embedded paste composition
In an embodiment of the invention, as described in this, noble metal is included from lower group selection at least A kind of material, comprising：Au Ag Pt Pd and rhodium, and its alloy, synthetic or other combinations.In one embodiment, your gold Belonging to particle includes 10wt% to the slurry between 70wt%.In multiple embodiments, noble metal has about 100nm extremely D50 between 50 μm, between 300nm to 10 μm, between 300nm to 5 μm or in any scope for being contained therein.In multiple realities Apply in mode, noble metal has from about 0.4 to 7.0m2/ g or from about 1 to 5m2/ g scope is contained therein Specific surface area in any scope.Noble metal can have up to 2wt% oxygen content；Oxygen can be mixed throughout uniform particle, or Oxygen can find that it has up to 500nm thickness in oxidation shell.Noble metal can have spherical, elongated shape or slice-shaped Shape, and be distributed with unimodal or multi-modal size.Silver particles are generally used for the Metal slurry in solar industry.In an allusion quotation In type embodiment, at least some noble metals are silver, with the D50 between 300nm to 2.5 μm and 1 to 3m2Between/g Specific surface area.
Term " imbedded particle " is used to describe deformable particle when heated, also, when adjacent other metallics When porous layer is positioned, porous metals particle layer can be at least partly sandwiched, and the influence based on heating is from other metallic phases Separation.In a variety of arrangements, imbedded particle there is 50nm to 50 μm between, between 50nm to 10 μm, between 300nm to 5 μm or D50 in any scope being contained therein.In one embodiment, imbedded particle has the D50 between 300nm to 3 μm. In multiple embodiments, imbedded particle has from about 0.1 to 6m2/ g, about 0.5 to 3m2/ g or 0.5 to 4m2/ g scope Or the specific surface area in any scope being contained therein.According to an embodiment, imbedded particle is slice-shaped and had big About 1.0 to 3.0m2/ g specific surface area.Imbedded particle can have spherical, elongated shape or slice-shaped shape, and can have it is unimodal or Multi-modal size is distributed.
Here there are three groups of particles, it is used as imbedded particle：Low temperature substrates metallic (lo temperaturebase Metal particle) (LTBM), crystalline metal oxide particle (crystalline metal oxide particle) and Glass melts grain (glass frit particle).In some arrangements, imbedded particle only include low temperature substrates metallic or Crystalline metal oxide particle or glass melt grain.In other arrangements, imbedded particle is two or more grains from these groups The mixing of son.It is required that the element of imbedded particle has low soluble and not turned into the element in adjacent metal particle layer Alloy.
In one embodiment, imbedded particle is low temperature substrates metallic.Term " low temperature substrates grain as used herein Son " (LTBM) is to describe exclusively or substantially to include the particle of any base metal or metal alloy, and it has low-temperature melting point, That is, the fusing point less than 450 DEG C.In some arrangements, LTBM is also comprising up to 2wt% oxygen；Oxygen can be mixed throughout uniform particle, Or oxygen can find that it has up to 500nm thickness, and coats or be partially coated with the particle in oxidation shell.At some In arrangement, LTMB fusing point is lower, such as less than 350 DEG C or less than 300 DEG C.In an embodiment of the invention, LTBM Exclusively or substantially it is made by bismuth, tin, tellurium, antimony, lead or its alloy, synthetic or other combinations.In an embodiment In, imbedded particle is only comprising bismuth and with the D50 and 1 to 2m between 1.5 to 4 μm2Specific surface area between/g.
In another embodiment, LTBM imbedded particles are the bismuth core particles surrounded by metal or metal oxide shell. In another embodiment, LTBM imbedded particles are bismuth core particles, are surrounded by monoshell, and it is by silver, nickel, nickel alloy such as nickel Boron, tin, tellurium, antimony, lead, molybdenum, titanium, its synthetic and/or other combinations are made.In another embodiment, LTBM is embedded in grain Son is bismuth core particle, is surrounded by monoshell, and it is silica, magnesia, boron oxide or its any combinations.These any shells can have Have from 0.5nm to 1 μm or 0.5nm to 200nm scopes or includes the thickness of any scope in the inner.
In another embodiment, imbedded particle is crystalline metal oxide particle.Metal oxide is that have at least One oxygen atom (oxidation state of anion is -2) and the compound of at least one metallic atom.Many metal oxides are comprising more Individual metallic atom, it can all be identical or may include various metals.The metal of wide scope be with oxygen atom ratio it is possible, just As the skilled person will appreciate.When metal oxide forms orderly periodic structure, they are crystal.This crystalline substance Body metal oxide dispersive x-ray can be radiated in the peak pattern of the varying strength characteristic of their crystal structure.At one In embodiment, crystalline metal oxide particle only by or substantially include the oxide of at least one of following metals：Bismuth, Tin, tellurium, antimony, lead, vanadium, chromium, molybdenum, boron, manganese, cobalt, and its alloy, synthetic or other combinations.
For the structure for being disclosed and being described in more detail below, as crystalline metal oxide particle is heated, such as In less than the structure between metallic or between different synthetics the low temperature of the temperature of significant phase counterdiffusion can occur for fruit, They start fusing and (that is, reach their fusing point (TM)), this is useful.Heat can be used in the fusing point of crystalline material in mixed layer Rank and x-ray diffraction are determined；As sample is heated on its fusing point, diffraction peak reduces and then disappeared.At some In exemplary embodiment, boron (III) oxide (B2O3, TM=450 DEG C), vanadium (V) oxide (V2O5, TM=690 DEG C), tellurium (IV) Oxide (TeO2, TM=733 DEG C) and bismuth (III) oxide (Bi2O3, TM=817 DEG C) it can be deformed and embedding during firing process Enter in adjacent porous metals particle layer, produce the metal particle layer of improvement.In an exemplary embodiment, imbedded particle is Crystal bismuth oxide, with the D50 between 50nm to 2 μm and 1 to 5m2Specific surface area between/g.In another embodiment, Crystalline metal oxide particle also includes one or more additional elements of a small amount of (that is, less than 10wt%), its adjustable particle Fusing point.This additional elements may include but be not limited to：Silicon, germanium, lithium, sodium, potassium, magnesium, calcium, strontium, caesium, barium, zirconium, hafnium, vanadium, niobium, Chromium, molybdenum, manganese, iron, cobalt, rhenium, zinc, cadmium, gallium, indium, carbon, nitrogen, phosphorus, arsenic, antimony, sulphur, selenium, fluorine, chlorine, bromine, iodine, lanthanum and cerium.
In another embodiment, imbedded particle is that glass melts grain.In one embodiment, glass melt grain only by or Substantially comprise at least one combination of oxygen and following elements：Silicon, boron, germanium, lithium, sodium, potassium, magnesium, calcium, strontium, caesium, barium, zirconium, Hafnium, vanadium, niobium, chromium, molybdenum, manganese, iron, cobalt, rhenium, zinc, cadmium, gallium, indium, tin, lead, carbon, nitrogen, phosphorus, arsenic, antimony, bismuth, sulphur, selenium, tellurium, fluorine, Chlorine, bromine, iodine, lanthanum, cerium, oxygen, and its alloy, compound and other combinations.If glass, which melts grain, to be had less than 900 DEG C or is less than 800 DEG C of softening point, this is useful, so as to effectively be deformed during firing.In an exemplary embodiment, embedded grain Son is that silicic acid bismuth glass melts grain, with the D50 between 50nm to 2 μm and 1 to 5m2Specific surface area between/g.
Term " organic carrier " describes organic chemistry or the mixture or solution of compound, it aids in dissolving, it is scattered and/ Or the solid constituent in suspended nitride.For embedded slurry described here, many different organic carrier mixtures can be used. This organic carrier may or may not include thixotropic agent (thixotrope), stabilizer, emulsifying agent, thickener, plasticizer, table Face activating agent and/or other common additives.
The composition of organic carrier is well known to those skilled in the art.The main composition of organic carrier includes one kind Or a variety of adhesives and one or more solvents.Adhesive can be polymerization or monomer organic principle or " resin ", or both Mixture.Polymeric binder can have different kinds of molecules weight and a variety of polydispersity indexs.Polymeric binder may include two kinds not With the combination of monomeric unit, it is known as copolymer (copolymer), wherein, monomeric unit can be respective alternately or big (block copolymer) of block.Polysaccharide is usually used polymeric binder, and is included but is not limited to, and alkylcellulose and alkyl spread out Biological such as methylcellulose, ethyl cellulose, propyl cellulose, butyl cellulose, ethylhydroxyethylcellulose, cellulose derive Thing and its mixture.Other polymeric binders include but is not limited to, polyester, polyethylene, polypropylene, makrolon, polyurethane, poly- Acrylate (including polymethacrylates and polymethyl methacrylate), polyethylene (including polyvinyl chloride, polyvinyl pyrrole Alkanone, polyvinyl butyral resin, polyvinyl acetate), polyamide, polyglycols (including polyethylene glycol), phenolic resin, poly- terpene Alkene, its derivative and combinations thereof.Organic carrier adhesive may include 1 to the adhesive between 30wt%.
Solvent is organic species, and it thermally, for example evaporates and the removing from slurry generally in machine process.Always For, include but is not limited to available for the solvent in slurry described here, polarity, nonpolar, proton, non-proton, fragrance Race, non-aromatic, chlorination, and non-chlorinated solvent.Include but is not limited to available for the solvent in slurry described here, alcohol, two First alcohol (including ethylene glycol), polyalcohol (including glycerine), single-and polyethers, single-and polyester, alcohol ether, alcohol ester, list-and disubstituted Adipate ester, single-and poly- acetic acid esters, ether acetic acid ester, Ethylene glycol acetate, glycol ether (including ethylene glycol monobutyl ether, diethyl two Alcohol monobutyl ether, triethylene glycol butyl ether), ethyl cellosolve acetate (including ethylene glycol monomethyl ether acetate), linear or side chain Saturation and unsaturated alkyl chain (including butane, pentane, hexane, octane number and decane), terpene (including α-, β-, γ-and 4- pines Oleyl alcohol), 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates (also are known as texanolTM), 2- (2- ethoxyethoxies) second Alcohol (also is known as carbitolTM), derivative, combination and its mixture.
In one arrangement, organic carrier includes the solvent between 70-100wt%.Adhesive, solvent and any additive Ratio and composition can be adjusted, to realize distribution or suspension needed for pulp particle, required carbon content and/or required stream Become attribute, as the skilled person will appreciate.For example, can be by adding thixotropic agent, such asCome Change slurry rheology., can be by changing adhesive and thixotropic agent and considering will occur during annealing in another example Peak value firing temperature, fire profile (firing profile) and air-flow and the carbon content for increasing or decreasing organic carrier.May be used also Including additive slightly.This additive includes but is not limited to, thixotropic agent and surfactant.This additive is this area It is well known, and can determine this composition by normal experiment have consumption, to maximize unit efficiency and reliability.In a reality Apply in mode, Metal slurry has at 25 DEG C and at 4 seconds-1Shear rate under have 10,000 between 200,000cP Viscosity, the controlled Brookfield RVDV-II+Pro viscosity meters of temperature in use.
Embedded formula of size
Shown in Table I according to some embodiments of the present invention, the Exemplary compositions scope of embedded slurry.In multiple realities Apply in mode, embedded slurry have 30wt% to the solids laden between 80wt%, embedded slurry 10wt% to 70wt% it Between noble metal composition, at least 10wt%, 15wt%, 20wt%, 25wt%, 30wt% or 40wt% of embedded slurry Imbedded particle is constituted, and the weight ratio at least 1 of imbedded particle and noble metal:5.In an illustrative embodiments, Noble metal content is 50wt%, and imbedded particle composition is at least 10wt% of embedded slurry.In multiple embodiments, The weight ratio of imbedded particle and noble metal is at least 1 in embedded slurry:5 or 2:5 or 3:5 or 1:1 or 5:2.
Table I
Embedded formula of size, with percentage by weight (wt%)
Slurry types Noble metal Imbedded particle Organic carrier
Embedded slurry (scope I) 10-70 10-50 20-70
Embedded slurry (scope II) 20-50 10-35 30-60
Embedded slurry A 50 12.5 37.5
Embedded slurry B 45 30 25
Embedded slurry C 45 30 25
Embedded slurry D 30 20 50
In an embodiment of the invention, for solar cell application, embedded slurry comprising 20 to 50wt% it Between noble metal (that is, in Table I embedded slurry scope II) and 10 to the imbedded particle between 35wt%, it may include LTBM, crystalline metal oxide, frit or its combination.In one embodiment, imbedded particle is bismuth metal particle.It is embedded Slurry A (Table I) can bring imbedded particle comprising 50wt% silver particles, 12.5wt% bismuth granules and 37.5wt% organic carriers With the 1 of noble metal:4 (weight) compare.Embedded slurry C (Table I) can comprising 45wt% silver particles, 30wt% bismuth granules and 25wt% organic carriers, bring the 1 of imbedded particle and noble metal:1.5 (weight) compare.When embedded slurry includes silver and bismuth During particle, annotation Ag is used：Bi.
In another embodiment, imbedded particle is that glass melts grain.Embedded slurry B (Table I) can include 45wt% silver granuels Son, glass of the 30wt% based on bismuth melt grain and 25wt% organic carriers, bring the 1 of imbedded particle and noble metal:1.5 (weight) compares.In another embodiment, imbedded particle is the mixing that LTBM, crystalline metal oxide particle and glass melt grain Thing.Embedded slurry D (Table I) can be melted comprising 30wt% silver particles, 15wt% bismuth metals particle, the high lead content glass of 5wt% grain and 50wt% organic carriers.Matching somebody with somebody for embedded slurry can be adjusted, to realize for the bulk resistor needed for special metal layer, contact Resistance, thickness degree and/or peel strength.
In yet another embodiment of the present invention, forming the method for embedded slurry includes step：Offer noble metal, Imbedded particle is provided, and mixed noble metal and imbedded particle in organic carrier.In one arrangement, it is embedding Enter particle to be added into organic carrier and mix in epicyclic mixer (for example, Thinky AR-100), subsequent noble metal (and additional organic carrier, if desired) is added and mixed in epicyclic mixer.Embedded slurry may or may not Then it is ground, for example, by using three-high mill (three roll mill) (for example, Exakt 50I).In one kind arrangement In, embedded slurry includes 10 to the noble metal between 70wt% and the imbedded particle more than 10wt%.
Form the method that sintered multilayer is stacked
In an embodiment of the invention, the multiple-level stack of sintering includes basic unit, there is at least one clipped wire thereon Sublayer and at least one intercalation.In one embodiment, it is many using the combined firing process formation sintering comprising following step Layer is stacked：In substrate surface coated with metal particle layer, metal particle layer is dried, in the part for drying metal particle layer directly Intercalation is coated, intercalation, and then combined firing multiple-level stack is dried.In another embodiment, using including following step Order fire process formation sintered multilayer stack：In substrate surface coated with metal particle layer, metal particle layer is dried, gold is fired Belong to particle layer, intercalation is directly coated in a part for sintering metal particle layer, dry intercalation and then fire multiple-level stack. In one embodiment, during firing, a part for intercalation is infiltrated into metal particle layer, thus metal particle layer is changed For improvement metal particle layer.In some embodiments, each coating step includes the method independently selected from the following group, including： Silk-screen printing, intaglio printing, jet deposition, slit coating, 3D printing and ink jet printing.In one embodiment, clipped wire Sublayer is coated onto in a part for basic unit by screen-printed metal particle slurry, and intercalation is after by drying, passes through silk screen The embedded slurry of printing is directly applied in a part for metal particle layer.In one embodiment, a part of substrate surface quilt At least one dielectric layer is covered, and metal particle layer is painted in a part for dielectric layer.
Dry and sintering multiple-level stack form
Accompanying drawing 1 is, according to embodiments of the present invention, to show and combining the schematic of the multiple-level stack 100 before sintering Sectional view.Metal particle layer 120 is dried directly in a part for basic unit 110.Intercalation 130, by imbedded particle and noble metal grain Son composition, as described above, directly in the part for drying metal particle layer 120.In multiple embodiments of the present invention, insert Layer 130 has between 0.25 μm to 50 μm, between 1 μm to 25 μm, between 1 μm to 10 μm or in any scope for being contained therein Average thickness.In an embodiment of the invention, intercalation 130 includes noble metal, imbedded particle and optionally had Machine adhesive (it can be retained in intercalation 130 after drying).Before combined firing, noble metal and imbedded particle can It is distributed in heterogeneity in intercalation 130.In one arrangement, noble metal and imbedded particle after drying (and fire It is before) and indeformable, keep their original size and shape.
In an embodiment of the invention, dry metal particle layer 120 be porous, and including aluminium, copper, iron, nickel, At least one of molybdenum, tungsten, tantalum, titanium and its alloy, synthetic or other combinations.In one arrangement, before combined firing, do Dry metal particle layer 120 includes metallic, and may or may not include organic bond, and may or may not include Nonmetal particle, such as frit.Metallic is (and before firing) and indeformable typically after drying, keeps them Original size and shape.
During firing, the imbedded particle from intercalation 130 is embedded in the dry of adjacent (such as accompanying drawing 1 is shown below) intercalation 130 In a part for dry metal particle layer 120.Adjacent intercalation 130 and imbedded particle infiltration are to dry metal particle layer therein 120 parts are referred to as " improvement metal particle layer ", to this disclosed purpose.After firing, metal level 120 is dried Remainder, its non-conterminous intercalation and has no or only the intercalation metal material of trace and penetrates into wherein, is referred to as " metallic Layer ", to this disclosed purpose.In one arrangement, during firing, the particle dried in metal particle layer 120 can burn Knot melts so that metal particle layer has different forms and has smaller porosity than dry metal particle layer 120.Hereafter It will be discussed in occurring the multilayer lamination structure of the change and sintering during firing.
Accompanying drawing 2 is, according to embodiments of the present invention, to show that (structure 100 of accompanying drawing 1 is at it for sintered multilayer stacking 200 After being sintered) schematic sectional view.Sintered multilayer stacks 200 and changed including at least one of of adjacent base layer 210 Good (due to firing) metal particle layer 222, and adjacent improvement (due to firing) intercalation 230 for improveing metal particle layer 222. During firing, at least a portion noble metal and imbedded particle in intercalation (shown in Figure 1 before firing is 130) Form the phase of phase with one another separation.Noble metal is sinterable or melts, and changes the hole of form and reduction improvement intercalation 230 Gap rate.At least a portion imbedded particle melts and flowing or embedded adjacent improvement metal particle layer 222, with least a portion Noble metal (its sinterable or fusing) is moved towards improveing the solderable surface 230S of intercalation 230.Improve metal particle layer 222 include metallic, its from intercalation (before firing, it is shown in Figure 1 be 130) in imbedded particle material Through permeating wherein, the dry metal level of change (before firing, shown in Figure 1 is the material properties of a part 120), with Form improvement metal particle layer 222.Material from imbedded particle can loosely connect what is filled in improvement metal particle layer 222 Metallic, or it can be coated in the metallic that has been in contact with each other in improvement metal particle layer 222.
In some arrangements, also metallic region 220, has almost had no or only the imbedded particle material of trace Infiltrate into wherein.In one arrangement, metal particle layer 220, its not with improvement intercalation 230 directly contact, and do not include come from The increase concentration of the element of imbedded particle.In some arrangements, metal particle layer 220 and improvement metal particle layer 222 are in joint The mixture with basic unit 210 or basic unit 210 of adulterating is formd during firing (not shown).Although accompanying drawing 2 indicates clipped wire Sharp border between sublayer region 220 and improvement metal particle layer 222, it should be appreciated that border is not typically cutting edge of a knife or a sword Profit.In some arrangements, being dissipated by improveing the material of intercalation 230 during combined firing into the side of metal particle layer 220 Cloth scope and determine border.
In certain embodiments of the present invention, the material in the improvement intercalation 230 in accompanying drawing 2 is divided into including from embedding Enter the phase of the phase of the material of particle and the phase comprising noble metal.Accompanying drawing 3 is to show that sintered multilayer stacks 390 (quite In the structure 200 of accompanying drawing 2) schematic sectional view, and wherein intercalation 330 have separation phase.Sintered multilayer stacks 390 (only In region 350) it is included in the improvement in the region 350 between a part for basic unit 300 and improvement (during firing) intercalation 330 (during firing) metal particle layer 322.Metal particle layer 320 comprising metallic 392 is in adjacent multiple-level stack region 350 Basic unit 300 on.
Improve intercalation 330 and include two phases：Noble metal phase 335 and embedded phase 333, and with solderable surface 335S.The solderable surface of most of (at least above 50%) is made up of noble metal phase 335.In some arrangements, noble metal Phase 335 and embedded the phase 333 not fully PHASE SEPARATION during firing so that also have some embedding in solderable surface 335S Applying aspect 333.Improvement metal particle layer 322 includes metallic 392 and a part of material for carrying out self-embedding phase 333.Changing There is interface 322I between adjacent metal particle 392 in good embedded region 330 and improvement metal particle layer 322.Interface 322I can Be not it is smooth and depending on metallic 392 size and dimension and firing condition.Fired in optional frit It is already contained in before in the embodiment in dry metal particle layer (120 in accompanying drawing 1), improves metal particle layer 322 With metal particle layer 320 can also include a small amount of frit (not shown), its constitute this layer be less than 3wt%..
In other embodiments, the material phase improved in accompanying drawing 2 in intercalation 230 separates to form hierarchy.It is attached Fig. 4 is to show that sintered multilayer stacks 400 (equivalent to the structures 200 of accompanying drawing 2) and includes the signal of the intercalation with two sublayers Property sectional view.Sintered multilayer stack 400 (only in region 450) be included in basic unit 410 a part and improvement (fire the phase Between) improvement (during firing) metal particle layer 422 in region 450 between intercalation 430.Include the gold of metallic 402 Belong to particle layer 420 in the basic unit 410 in adjacent multiple-level stack region 450.
Improve intercalation 430 and include two sublayers：Sub- intercalation 433 directly in improvement metal particle layer 422, and directly Noble metal sublayer 435 on improvement intercalation 433.Noble metal sublayer 435 has solderable surface 435S.Improve metal particle layer 422 include metallic 402 and some materials 403 from sub- intercalation 433.In improvement intercalation 430 (or improvement intercalation 433) and There is interface 422I between top metallic 402 in improvement metal particle layer 422.In optional frit before firing It is already contained in the embodiment in dry metal particle layer (120 in accompanying drawing 1), improvement metal particle layer 422 and gold Belong to particle layer 420 can also include a small amount of frit (not shown), its constitute this layer be less than 3wt%.
Cross-sectional SEM image is used to recognize the thickness degree in each layer and measurement multiple-level stack.Each layer in multiple-level stack it is flat Equal thickness degree is obtained by average at least ten thickness measurements, and through cross-sectional image, every part is at least 10 μm separations.At this Invention multiple embodiments in, metal particle layer (such as 220 in accompanying drawing 2) have 0.5 μm to 100 μm between, 1 μm to 50 Between μm, between 2 μm to 40 μm, between 20 μm to 30 μm or the average thickness of any scope that is contained therein.In basic unit This metal particle layer is typically smooth, is had on 1x1mm areas within the 20% of average metal particle thickness degree Minimum and maximum thickness degree.Except section SEM, Olympus LEXT can be used in thickness degree and change on description area OLS4000 3D laser measurements microscopes and/or profilograph (profilometer), the essences of such as Veeco Dektak 150 Really measurement.
In an exemplary embodiment, metal particle layer (such as 220 in accompanying drawing 2) be made by sinterable aluminum particulate and With 25 μm of average thickness.The porosity of metal particle layer can be used mercury porosimeter, such as CE instruments Pascal 140 (low Pressure) or Pascal 440 (high pressure), measured into the scope between 2Mpa in 0.01kPa.Sintering metal particle layer can have 1% Porosity in any range included between to 50, between 2% to 30%, between 3% to 20% or wherein.By aluminum particulate system Obtain and there can be the porosity between 10% to 18% for the sintering metal particle layer in application of solar energy.
The thickness of sub- intercalation and noble metal sublayer, for example, be respectively schematically shown as 433 and 435, use in figure 4 Section SEM/EDX is measured in actual multiple-level stack.Each sublayer is in SEM due to the contrast differences between embedded and noble metal phase It is different and distinguish.EDX mappings (mapping) are used to recognize interface location, and shown in Figure 4 is 432I.In multiple embodiments In, noble metal sublayer has between 0.5 μm to 10 μm, between 0.5 μm to 5 μm, between 1 μm to 4 μm or appointing of being contained therein Thickness in what scope.In multiple embodiments, sub- intercalation there are 0.01 μm to 5 μm between, between 0.25 μm to 5 μm, 0.5 μm to the thickness between 2 μm or in any scope for being contained therein.
In an embodiment of the invention, improvement intercalation includes two phases：Noble metal phase and embedded phase.This One structure is shown specifically in figure 4.Typically, embedded phase is not solderable, so, if solderable surface 230S is big Part includes noble metal phase, and it is useful to ensure solderability.In a variety of arrangements, solderable surface, which is included, to be more than 50%th, the noble metal phase more than 60% or more than 70%.In one arrangement, the solderable surface of improvement intercalation is largely wrapped Containing (a variety of) noble metal.Plan view EDX is used for the concentration for determining the element on improvement intercalation surface.SEM/EDX uses public above The equipment opened is performed, and in 10kV accelerating potential, is amplified with 7mm samples operating distance and 500 times.In multiple embodiments In, improve the outer surface 230S of intercalation 230 at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt% or at least 98wt% includes the one or more of Au Ag Pt Pd, rhodium and its alloy, synthetic and other combinations.Firing condition, insertion Particle and noble metal type and size all reflect the PHASE SEPARATION degree in improvement intercalation form.
Metal particle layer (being shown as 222 in accompanying drawing 2) is improved than metal particle layer (being shown as 220 in accompanying drawing 2) comprising more The imbedded particle material of high concentration.Obtained from the metal particle layer in the section and actual multiple-level stack of improvement metal particle layer The comparison of EDX spectrum, can be used for the material concentration from improvement intercalation for determining to be embedded in improvement metal particle layer.Above The SEM/EDX equipment of description, operation is in 20kV, with 7mm operating distances, for measuring the section sample in improvement metal particle layer In this, the ratio of metal (for example, bismuth) and total metal (for example, bismuth adds aluminium) from imbedded particle.Weight ratio (embedded metal with Total metal ratio) it is referred to as IM:M ratios.Baseline EDX analyses are performed in the region of metal particle layer, and it is at least distally from improvement clipped wire 500 μm of sublayer is to ensure reproducible measurement.2nd EDX spectrum are obtained from improvement metal particle layer, and comparative spectrum. IM:M than determination in, only consider metallic element peak value (that is, the peak value from carbon, sulphur and oxygen is ignored).When analysis ratio When, noble metal and any metallic element from basic unit are excluded, so as to prevent insecure result.In an embodiment In, when dry metal particle layer (being shown as 120 in accompanying drawing 1) includes aluminum particulate and intercalation 130 includes bismuth and silver particles, metal Bismuth of the particle layer (i.e., after firing) comprising approximate 1wt% and the aluminium more than 98wt%, with 1：99 Bi:(Al+Bi) (IM:M) compare.Other embedded improvement metal particle layers of the metal composition less than 0.25wt%, and calculating IM:M ratios are not consider. In a number of other embodiments, IM:M ratios are 1:106、1:1000、1:100、1:50、1:25 or 1:10.
But it should be noted that some rough surface of basic unit, it is also coarse that it, which can cause with their interface,.Accompanying drawing 5 be according to According to embodiments of the present invention, show this basic unit 510, improvement metal particle layer 522 and improve a part for intercalation 530 Schematic sectional view.There is non-planar interfaces 501B between basic unit 510 and improvement metal particle layer 522.In improvement metallic There is non-planar interfaces 522B between layer 520 and improvement intercalation 530.Line 502 indicates sublayer 510 and enters improvement metal particle layer 522 most deep intrusion.Line 504 indicates the most deep intrusion that improvement intercalation 530 enters improvement metal particle layer 522.Line 502 and line The region of improvement metal particle layer 522 between 504 is referred to alternatively as sample areas 522A.In improvement metal particle layer 522 really Determine IM:In M ratios, it might be useful to limit this analysis to sample areas 522A, so as to avoid due to false caused by interface roughness As a result.
In exemplary embodiment, the IM in improvement metal particle layer:M is (golden in remote improvement than in metal particle layer Belong at least 500 μm of particle layer region in) it is high by 20%, high by 50%, high by 100%, high by 200%, high by 500% or high 1000%. In an exemplary embodiment, the intercalation comprising bismuth granule is in aluminum shot sublayer, and improvement metal particle layer is (such as in sample Analyzed in region, be such as shown as 522A in accompanying drawing 5) 4wt% bismuth and 96wt% aluminium are included, with 1:25 Bi:(Al + Bi) (or IM:M) compare.Improve the Bi in metal particle layer:(Al+Bi) compare high by 400% in metal particle layer.
When intercalation comprising crystalline metal oxide and/or frit, its include more than one metal when, embedded metal ingredient Quantified by EDX and phase Calais determines IM:M ratios.For example, if frit includes two kinds of bismuth and lead, then this is than being defined as (Bi+ Pb):(Bi+Pb+Al)。
In multiple embodiments, sintered multilayer, which is stacked, also to be included by drying the metallic in metal particle layer and basic unit Between during firing interaction formed solid mixed layer.Solid mixed layer may include but be not limited to, alloy, eutectic, Synthetic, mixture or its combination.In one arrangement, improvement metal particle layer and basic unit form solid at their interface Mix (many) regions.Solid mixing (many) regions can include one or more alloys.Solid mixing (many) regions can be continuous It is (one layer) or semi-continuous.Depending on basic unit and the synthetic of metal particle layer, other mixtures of (many) alloys or formation It may include the one or more of aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, silicon, oxygen, carbon, germanium, gallium, arsenic, indium and phosphorus.For example, aluminium and Silicon can be in 660 DEG C of eutectics formed above, and it is based on cooling, and solid aluminium-silicon (Al-Si) Eutectic Layer is brought at silicon interface. In one exemplary embodiment, solid mixture layer is formed in the solid Al-Si Eutectic Layers in a silicon base layer part.Solid The formation of Al-Si Eutectic Layers and form are well known in silicon solar cell.In another embodiment, basic unit doped with At least one of aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium and its alloy, synthetic and other combinations.In one example, aluminium is P-type dopant in silicon, and during firing, the aluminium in the aluminum shot sublayer from adjacent base layer adulterates there is provided more aluminium Thing in silicon base layer to form height p-type doped region, and it is known as back surface field.
Depending on atmospheric conditions, imbedded particle is with the improvement metallic in their fusings and embedded sintered multilayer stacking In layer, multiple phase change can be undergone.Depending on the material in improvement metal particle layer and basic unit, imbedded particle is embedding with them Enter to improve and mixed crystal is yet forms both in metal particle layer.This mixed crystal can improve the gold in improvement metal particle layer Belong to the cohesive force between particle, prevent the phase counterdiffusion of element-specific, and/or reduction sintered multilayer stack in metal level between Contact resistance.In one embodiment, improvement intercalation and improvement metal particle layer include crystal, by bismuth and oxygen, silicon and At least one composition of silver and its alloy, synthetic and other combinations.
In one embodiment, noble metal phase includes at least one material from lower group selection, comprising：Gold, silver, Platinum, palladium, rhodium, and its alloy, its synthetic and its other combinations.In one arrangement, noble metal phase is substantially comprising one kind Or these a variety of materials.When a kind of main body (majority) of composition noble metal phase of these materials, noble metal phase is retouched State as rich in this material.For example, if noble metal phase, layer of precious metal or noble metal sublayer are largely comprising silver, it can quilt It is referred to as Fu Yin regions, rich silver layer or rich silver layer.
Embedded phase includes the element from imbedded particle, and can also include the element (for example, oxygen) from external environment The element of the noble metal of basic unit near incorporated from adjacent metal particle layer and during firing on a small quantity. It can be depended in the extensive arrangement of the element in embedded phase, low temperature substrates metal, crystalline metal oxide and/or frit are It is no to be used as imbedded particle.In one embodiment (when imbedded particle is only low temperature substrates metal), embedded phase is included From at least one material of lower group selection, comprising：Bismuth, boron, tin, tellurium, antimony, lead, oxygen, and its alloy, synthetic and other combinations. In another embodiment (when imbedded particle is only crystalline metal oxide), embedded phase include from lower group selection to A kind of few material, comprising：Bismuth oxide, tin, tellurium, antimony, lead, vanadium chromium, molybdenum, boron, manganese, cobalt and its alloy, synthetic and other groups Close.In another embodiment (when imbedded particle is only frit), embedded phase includes oxygen and following elements at least One：Silicon, boron, germanium, lithium, sodium, potassium, magnesium, calcium, strontium, caesium, barium, zirconium, hafnium, vanadium, niobium, chromium, molybdenum, manganese, iron, cobalt, rhenium, zinc, cadmium, gallium, Indium, tin, lead, carbon, nitrogen, phosphorus, arsenic, antimony, bismuth, sulphur, selenium, tellurium, fluorine, chlorine, bromine, iodine, lanthanum, cerium, and its alloy, compound and other groups Close.When a kind of composition of these materials is embedded in the main body in region, embedded region is described as rich in this material.For example, such as The embedded region of fruit, intercalation or sub- intercalation largely include bismuth, and it can be hereinafter referred to as rich bismuth region, rich bismuth layer or rich bismuth sublayer.
Example and application that sintered multilayer is stacked
Most of metallic comprising aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum and titanium can not use gentle work after firing Property (mildly activated) (RMA) solder flux (fluxes) and the solder based on tin and soft soldering.However, in solar cell and In other devices, highly desirable soft soldering band, to be made electrical contact with metal particle layer, such as aluminum shot sublayer.As disclosed herein, invent Comprising noble metal, for example silver and gold insertion slurry can be used in metal particle layer and sinter in atmosphere, with produce can The surface of height soft soldering.This attempts to contrast with other, the solderability of metal particle layer is added by adding noble metal, due to expensive Metal is generally diffused into one another based on the firing of multiple-level stack with metal particle layer (for example, aluminium), is brought comprising considerably less The solderable surface of noble metal, so that soft soldering well.It is less than for example, firing commercially available including in aluminum shot sublayer Indicate slurry after the silvery of 10wt% frit, solderable surface will not be brought.These layers experienced during step is fired Significant silver-aluminium phase counterdiffusion, and bring the silver-colored aluminium surface of not solderable.
As disclosed herein, intercalation can be used for the material properties for improveing metal particle layer, so that, 1) stop noble metal Diffusion and offer solderable surface, 2) machinery reinforcement metal particle layer, and 3) each layer below assisted etch metal particle layer. In an embodiment of the invention, using embedded slurry formation multiple-level stack, it includes the noble metal and bismuth of silvery Metal or based on imbedded particle made from the frit of bismuth, and the adjacent metal particle layer comprising aluminum particulate.Sintered multilayer heap Folded is formed by：Silk-screen printing aluminum slurry (being generally used for solar cell application) on exposed silicon wafer, it is dry at 250 DEG C Silk-screen printing insertion slurry in dry sample 30 seconds, the part on aluminum shot sublayer is dried, in 250 DEG C of dry samples 30 seconds, with And combined firing sample, use spike igniting profile (the spike fire with the peak temperature between 700 DEG C to 820 DEG C Profile) and more than 10 DEG C/sec ramp up and cooling velocity.All dry and fire step and use Despatch CDF 7210 smelting furnaces are performed, and are commonly used in silicon solar manufacture.
SEM/EDS analyzes the elemental composition in multiple regions in the firing multiple-level stack in the section for determining polishing and ground Study carefully embedded process.SEM/EDX is performed using previously described equipment using two kinds of different operation modes.SEM micrograph makes Flied emission SEM is analyzed with Zeiss Gemini Ultra-55 to shoot using referred to as SE2 and Inlens both of which.SE2 moulds Formula operates the operating distance in 5-10kV and 5-7mm, uses the electron detectors of SE2 second and the scan cycle time of 10 seconds.It is bright Degree and contrast change between 0 to 50% and between 0 to 60% respectively, in order to maximize between embedded region and Al particles Contrast.Inlens patterns operate the operating distance in 1-3kV and 3-7mm, use the electron detectors of InLens second and 10 seconds The scan cycle time.In order to shoot BSF in Inlens patterns, brightness is set to 0% and contrast is set to 40% or so.
In an embodiment of the invention, including 10-15wt% imbedded particle insertion slurry stop noble metal The phase counterdiffusion of (that is, silver-colored) between metallic (that is, aluminium).Embedded slurry A (being shown in Table I) includes 12.5wt% bismuth granules And 50wt%Ag, bring the 1 of imbedded particle and noble metal:4 weight ratios.Sintered multilayer stacks system as described above .The SEM that sintered multilayer is stacked is performed in SE2 patterns, using equipment described above, the accelerating potential, 7mm in 5kV Operating distance and 4000 times of magnifying powers.
Accompanying drawing 6 is the ESEM sectional view that joint sintered multilayer is stacked.Intercalation 630 is improved directly in improvement metallic On layer 622.Improveing intercalation 630 includes rich bismuth (embedded phase) sublayer 632, and it includes bismuth oxide, and rich silver-colored (noble metal) son Layer 634.Improve metal particle layer 622 and include aluminum particulate 621 and embedded phase material 623, it spreads from rich bismuth sublayer 632 Place.Embedded region 632 is directly on aluminum particulate 621, at least near interface zone 631.Sub- intercalation 632 seems to prevent in connection Silver is from intercalation 630 and aluminium is improved from the phase counterdiffusion for improveing metal particle layer 622 during closing firing process.Accompanying drawing 6 is to exist above One example of the hierarchy described in accompanying drawing 4.Noble metal sublayer 634 provide can height soft soldering surface (away from improvement Metal particle layer 622).It is embedded in phase material 623 and not far infiltrating into is improved in metal particle layer 622.Improve metallic Layer 622 is most of to include aluminum particulate, and it is feebly sintered together after combined firing and with the mechanical strength of difference.Here Penetrated deep into without bismuth available enough into metal particle layer 622, and sub- intercalation 632 can be to improvement metal particle layer 622 apply pressure, its multiple-level stack that mechanically weak joint is sintered.The peel strength of the multiple-level stack of this joint sintering Less than 0.4N/mm (Newton per millimeter), with the dominant failure mechanism between Al particles.Need the peel strength more than 1N/mm Existing solar industry standard be considered commercial viability.
Slurry B (showing in Table I) is embedded in using frit as imbedded particle to realize solderable surface.Embedded slurry B Comprising 30wt%, the glass based on bismuth melts (insertion) particle and 45wt%Ag, brings the 1 of imbedded particle and noble metal: 1.5 weight ratios.Frit is mainly comprising bismuth and with 387 DEG C of glass transformation temperature and 419 DEG C of softening point.Sintered multilayer heap Folded SEM is performed in SE2 patterns, uses equipment described above, the operating distance and 4000 of accelerating potential, 7mm in 5kV Times magnifying power.Accompanying drawing 7 is the ESEM sectional view that this joint sintered multilayer is stacked according to embodiments of the present invention.Change Good metal particle layer 722 includes aluminum particulate 730.During combined firing, the frit based on bismuth not with the complete phase of Ag particles Position separation, brings the improvement intercalation 750 with two phases：Noble metal phase 721 and the insertion phase 740 based on bismuth, class It is similar to above shown in accompanying drawing 3.The surface 750S improved on intercalation 750 includes the noble metal phase 721 more than 50%.Surface The solder flux being generally used in solar cell industry can be used (for example, Kester 952S, Kester 951 and Alpha in 750S NR205) soft soldering.The overall peel strength that sintered multilayer is stacked is less than 0.5N/mm, and it can change because bismuth insertion phase 740 enters The hyposmosis of good aluminum shot sublayer 722.Generally, the form of improvement intercalation can be by changing imbedded particle composition and loading in intercalation And improve.
Embedded slurry stops the counterdiffusion of element phase and reinforcing lower metal particle layer
Above example shows two kinds of formula of size, designs that your technology (that is, silver-colored) and metallic (that is, aluminium) stopped Between phase counterdiffusion, but their sinter layer lacks enough mechanical strengths when by soft soldering.Embedded slurry C (is shown in Table I Go out) comprising 30wt% bismuth granules and 45wt% silver particles (that is, Ag：Bi is embedded in slurry), bring imbedded particle and noble metal grain The 1 of son:1.5 weight ratios.Increased imbedded particle content produces the insertion of higher concentration in improvement metal particle layer in slurry Material, and bring mechanically stronger sintered multilayer to stack.Embedded slurry C is used as, in BSF, polycrystal, p-type solar cell Manufacture during, after business silvery indicate slurry plug-in type change.Embedded slurry C may be additionally referred to as silver (Ag-on- on aluminium Al), mark or the embedded slurry of mark after rear mark, floating.The sintered multilayer heap that one group of characterization tool is used in acquirement is stacked on, so that Evaluate IM:M (embedded metals：Metal) ratio, precious metal surface coverage, and determine whether form crystal in embedded region.
By illustrating the form of the sintered aluminium particle layer on the silicon base layer without intercalation first, intercalation is in metal particle layer Influence by best illustrated.Accompanying drawing 8 is this ESEM of sintered aluminium particle layer 822 in SE2 patterns on silicon base layer 810 (SEM) sectional view, along the region of the silicon solar cell not comprising intercalation.The μ m-thick of sintered aluminium particle layer 822 about 20 and bag Containing aluminum particulate 821 and a small amount of inorganic bonds (that is, frit) 840.The InLens Mode scans Electronic Speculum of identical aluminum shot sublayer exists Shown in accompanying drawing 9.In InLens patterns, aluminum shot sublayer 922, aluminum particulate 921 and silicon base layer 910 are high-visible, in addition Also back surface field region 970 and solidified aluminum-silicon (Al-Si) Eutectic Layer 980.
After combined firing, influence of the intercalation on improvement metal particle layer is produced refers to accompanying drawing 10 and understood.It is attached Figure 10 is the InLens SEM surface charts for the identical silicon solar cell in image shown in accompanying drawing 8, but along comprising making The region stacked with the obtained joint sintered multilayer of embedded slurry C (being shown in Table I).Joint sintered multilayer, which stacks 1000 and included, to be changed Good intercalation 1030, improvement aluminum shot sublayer 1022, solidification Al-Si Eutectic Layers 1080, back surface field (BSF) region 1070 of adulterated al With silicon base layer 1010.In an exemplary embodiment, BSF doped p types in silicon base layer to 1017To 1020Per cm3Between.
The SE2 Mode scans Electronic Speculum that the joint sintered multilayer of accompanying drawing 10 is stacked is shown in Figure 11.Although InLens moulds Formula clearly illustrates BSF regions, and SE2 patterns are preference patterns to reflect the bismuth in improvement aluminum shot sublayer (embedded phase).Connection Close sintered multilayer stacking 1100 and include improvement intercalation 1130, improvement aluminum shot sublayer 1122 and silicon base layer 1110.Also it can be seen that improvement Silver layer 1134 and bismuth intercalation 1132 in intercalation 1130.BSF regions and solidification Al- are not clearly visible in this image Si Eutectic Layers.Improve aluminum shot sublayer 112 and include substantial amounts of bismuth insert material 1103, it surrounds aluminum particulate during combined firing 1102 insertions.In some instances, the contrast between bismuth and silver will not it is sufficiently strong with clearly recognize sublayer and bismuth insertion aluminium Degree in particle layer.SEM/EDX can be used to obtain in the element mapping of these example sectional views, so as to determine that joint is burnt completely Silver and bismuth position in multiple-level stack processed.
Because embedded insertion metal (that is, bismuth) amount can be determined by comparing EDX spectrum in improvement aluminum shot sublayer, from identical Improvement aluminum shot sublayer region and aluminum shot sublayer region in cross-section sample are carried out.If interregional be spaced more than 1 μm, this is Most useful.This mode compared is carried out to have been described above as IM:M or Bi:(Bi+Al) compare.This analysis is it is determined that embedding Whether enter slurry is used in the manufacture of solar cell be useful.Metal layer in solar cell includes limited subgroup Metal, such as including aluminium, silver, bismuth, lead and zinc.In commercial solar cell, aluminum shot sublayer almost entirely includes aluminium.
In one example, the metallic that the imbedded particle in embedded slurry C is only included in bismuth, and metal particle layer is big Part is aluminium.Compare the ratio Bi that bismuth and bismuth in aluminum shot sublayer (that is, it does not interact with embedded slurry) add aluminium:(Bi+Al) With improvement aluminum shot sublayer, it is determined that it is useful module that whether embedded slurry, which is incorporated into solar cell,.For this two The EDX spectrum of layer are measured approximate three minutes, using the said equipment, under 20kV accelerating potential and 7mm operating distance.With The EDX spectrum of sintered aluminium particle layer 822 in accompanying drawing 8 are collected from region 898.For the improvement aluminum shot sublayer in accompanying drawing 11 1122 EDX spectrum are collected from region 1199.Element is quantitative spectrally to be performed at these, uses Bruker Quantax The softwares of Esprit 2.0 are used for automatic elemental recognition, background subtraction and peak fitting.EDX spectrum are shown in Figure 12.Aluminium and Bismuth metallic peak area is quantified and calculates the wt% for two layers from the EDX spectrum in accompanying drawing 12, and in following Table II It is middle to summarize.There is no significant amount of any other metal to be recognized in EDX spectrum.The aluminum shot sublayer EDX shown in accompanying drawing 12A Spectrum produces 1:244 Bi:(Bi+Al) the improvement aluminum shot sublayer spectrum shown in wt% ratios, and accompanying drawing 12B produces 1:4 Bi: (Bi+Al) wt% ratios, as shown in table ii.Improve the Bi in aluminum shot sublayer 1122:(Bi+Al) wt% ratios about than not with Ag：Bi intercalations contact sintered aluminium particle layer 822 it is high 62 times.In multiple embodiments, the Bi in sintered multilayer stacking: (Bi+Al) than be in improvement aluminum shot sublayer at least 20% or at least 50% or high at least 2x in sintered aluminium particle layer or At least 5x or at least 10x or at least 50x.
Table II：
Aluminium bismuth EDX is quantified and result Bi:(Bi+Al) wt% ratios
Al Bi Bi:(Bi+Al) compare
Aluminum shot sublayer 40.290 0.166 1:244
Improve aluminum shot sublayer 43.641 14.974 1:3.91
Plan view EDX can be used for the concentration of element on the surface of reference lamina after determining in silicon solar cell.Looking squarely In figure, the depth on EDX probe areas surface to about 4 μm or smaller so that this is useful technology, for recognizing that joint is stacked Mutual diffusance in multiple-level stack：Higher precious metal concentration means there is less phase counterdiffusion here, and lower expensive Metal concentration means there are more phase counterdiffusion here.Accompanying drawing 13 is according to embodiments of the present invention, from including Ag：Bi is inserted The plan view EDX spectrum that the surface of the rear reference lamina of layer is carried out.EDX spectrum are collected using SEM, the acceleration electricity in 10kV is operated Pressure, 7mm operating distances and 500 times of magnifying powers.The relatively small leak of main peak and 0.3keV between 3.5 and 4keV is all identified as Silver.Remaining small leak is recognized as follows in spectrum：Carbon is 0.3keV (curling up has small silver-colored peak value)；Oxygen is in 0.52keV；Aluminium exists 1.48keV；And bismuth is in 2.4keV.Element is quantitatively performed automatically using the softwares of Bruker Quantax Esprit 2.0, to subtract Background, recognition element peak value, and the then peak strength of suitable x-ray energy.The normalized weight percentages of every kind of element are under Shown in the Table III of text.The overall silver covering on the surface of reference lamina is 96.3 percentage by weights (wt%) afterwards.
Table III
Indicate the elemental standards percentage by weight of layer surface afterwards
Element Standard wt%
Carbon 0.784
Silver 96.342
Silicon 0.002
Aluminium 0.153
Bismuth 1.912
Oxygen 0.807
Intercalation comprising silver and bismuth can form multiple monocrystalline phases when being sintered in the dry metal particle layer based on aluminium Position.XRD can be used for, in intercalation using bismuth granule sintered multilayer stack and using tradition based on silver colored belt, have Made a distinction less than 10wt% frits as between the sintered multilayer stacking of inorganic bond.Using equipped with VANTEC-500 The Bruker ZXS D8Discover GADDS x-rays of area detector and the cobalt x-ray source for operating in 35kV and 40mA are spread out Penetrate instrument and perform XRD.Show that the sintered multilayer on the rear colored belt of silicon solar cell stacks XRD case in accompanying drawing 14 (pattern).It is used in 2 Θ measure diffraction pattern in two 25 ° of frameworks of 25-80 ° of total window in combination using cobalt K α wavelength.Often Individual framework is measured 30 minutes under x-ray irradiation.Background subtraction is not carried out on two diffraction patterns of accompanying drawing 14.Pattern quilt Standardization is to meet peak-peak, and 0.01 background is increased to data, so as to be drawn with log (intensity).
XRD diffraction patterns are shown, use Ag：After in the sintering metal stacking or solar cell of the formation of Bi intercalations Reference lamina, has different pattern compared with one of no bismuth formation.On rear reference laminas of the XRD case A from silicon solar cell Joint sintered multilayer stack.Joint sintered multilayer, which is stacked, to be included improveing intercalation, is formed using embedded slurry, it is comprising approximate The organic carrier of 45wt% silver, 30wt% Bi and 25wt% (such as above for the slurry C in Table I).Peak value 1410 is recognized For silver and peak value 1420 is bismuth oxide (Bi2O3) crystal.Joint on rear reference laminas of the XRD case B from silicon solar cell Sintered multilayer is stacked, and is formed using commercially available rear mark slurry, and it includes the frit less than 10wt%, as aluminum shot Intercalation in sublayer.It is dark that joint sintered multilayer, which is stacked, indicates significant silver-aluminium phase counterdiffusion.Peak value 1450 is recognized For silicon-aluminium eutectic phase.Peak value 1460 is identified as silver-aluminium alloy phase (i.e. Ag2Al).Silver-colored peak value 1410 is observed in pattern A Arrive, do not have with bismuth oxide mixture, and in pattern B, only observe silver as the portion of silver-aluminium alloy 1450 herein Point.This further demonstrates bismuth prevents the mutual expanding in sintered multilayer stacking.In one embodiment, silicon solar Crystal of the rear reference lamina comprising bismuth and at least one other element in battery, such as silicon, silver, its oxide, its alloy, its conjunction Into thing or its other combination.In another embodiment, rear reference lamina includes bismuth oxide crystal.In another embodiment In, embedded region experienced multiple phase transitions during firing.
Intercalation etchable process dielectric layer during firing
In the application of some devices, dielectric layer is deposited in substrate surface before deposition of metal, so as to be passivated basic unit Surface and improvement electrical attributes.Dielectric layer can also prevent the material phase counterdiffusion between basic unit and adjacent metal particle (many) layers. In some cases, highly desirable dielectric layer can be etching through, so that the mixture formed between basic unit and metal particle layer, with Improve the electrical conduction between basic unit and metal particle layer.Frit comprising bismuth and lead is known, with silicon solar cell Combined firing during be etching through medium layer (for example, silicon nitride).In an exemplary embodiment, embedded slurry D (from Table I above) is comprising about 30wt% silver, (15wt% bismuth metals particle, 5wt% are high, and lead contains 20wt% imbedded particles Measure frit) and 50wt% organic carriers.Dielectric layer is etching through if desired, and this insertion slurry is particularly useful.
Accompanying drawing 15 is shown according to embodiments of the present invention, before firing, including is coated with least one dielectric layer The schematic sectional view of the multiple-level stack 1500 of 1513 basic unit 1510.Metal particle layer 1520 is dried the one of dielectric layer 1513 On part.Intercalation 1530, is made up of imbedded particle and noble metal, as described above, directly drying metal particle layer 1520 A part on.Before firing, noble metal and imbedded particle can be distributed in intercalation 1530 in heterogeneity.Dielectric layer bag Include at least one of silicon, aluminium, germanium, gallium, hafnium, and its oxide, its nitride, its synthetic and combinations thereof.In one arrangement, Dielectric layer 1513 is the thick silicon nitride layers of 75nm.In another embodiment, have between dielectric layer 1513 and basic unit 1510 Second dielectric layer (not shown).In one arrangement, second dielectric layer is the aluminum oxide of the 10nm thickness directly in basic unit 1510 Layer, and dielectric layer 1513 is the silicon nitride layer of the 75nm thickness directly on alumina layer.Dry metal particle layer 1520 by On dielectric layer 1513 deposited metal particle slurry and immediately dry and formed.In one arrangement, metal particle layer 1520 is dried It is 20 μ m-thicks and comprising aluminum particulate.Intercalation 1530 include imbedded particle, such as frit, its include lead or bismuth, be deposited on drying In metal particle layer 1520, at least a portion of metal particle layer 1520 is dried in covering, and is subsequently dried.
Accompanying drawing 16 is, according to embodiments of the present invention, to show that sintered multilayer stacks the 1600 (structures 1500 of accompanying drawing 15 After it has been sintered) schematic sectional view.A part of basic unit 1610 is coated with least one dielectric layer 1614.In connection Close during firing, at least some imbedded particles (it includes the frit of the description of refer to the attached drawing 15) fusing in improvement intercalation 1630 And start flowing, it is embedded in improvement metal particle layer 1622.In one arrangement, the glass in improvement intercalation 1630 melts The infiltration of grain is extremely and by improveing the metallic in metal particle layer 1622 and being etched into dielectric layer 1613 (before firing It is 1513), it is allowed to which some metals from improvement metal particle layer 1622 interact chemically and electrically with basic unit 1610, Form one or more new blends 1614.Other imbedded particles (for example, bismuth granule is sub) from improvement intercalation 1630 can also be embedding Enter to improve in metal particle layer 1622 and structural support can be provided.In one arrangement, such as refer to the attached drawing 2 is described in more detail above , at least a portion noble metal and imbedded particle in improvement intercalation 1630 form the phase of phase with one another separation. In some arrangements, also metallic region 1620 (on dielectric layer 1613), the imbedded particle material of trace is almost had no or only Material is infiltrated into wherein.In an exemplary embodiment, imbedded particle is that bismuth granule and glass melt grain, and metallic is aluminium.
The thickness for introducing metal particle layer changes to reduce bending
Pressure of the intercalation in it can cause following improvement metal particle layer during firing, its can cause to bend or wrinkle and Electric connection between poor layer intensity therefore and layer.For example, intercalation can have it is different from adjacent improvement metal particle layer Thermal coefficient of expansion, causes the different expansion or shrinkage of each layer during firing.Another in adjacent improvement metal particle layer Pressure source can be the insertion of the imbedded particle material of the fusing between metallic.These pressure can cause the clipped wire of improvement Sublayer and/or the bending of the intercalation of improvement wrinkle.Bending or corrugation can be described as big, the cycle the or non-week in thickness degree The deviation of phase.Generally, which results in the layering between layer.For example, before the intercalation on metal particle layer is dried is sintered, bag Original depth containing intercalation and the stacking for drying metal particle layer is throughout approximately uniform.After combined firing, comprising The thickness that the intercalation of improvement and the sintered multilayer of the metal particle layer of improvement are stacked can be up to original depth in some regions Three times.
Accompanying drawing 17 is wherein to have occurred that the plan view light micrograph that the joint sintered multilayer of bending is stacked.Change Good intercalation 1730 is visible.Improvement intercalation 1730 has been bent；Some peak regions 1712 are indicated in figure 17.Adjacent gold Category particle layer 1720 does not bend and keeps smooth or near flat.Even if intercalation 1730 has been deformed, combine the multilayer of sintering The mechanical integrity of stacking keeps strong by the peel strength more than 1N/mm.However, bending can cause it to have challenge, With improve between intercalation 1730 and colored belt (not shown) when they by soft soldering together when enter contact act charitably, firm. The curved surface of improvement intercalation 1730 can cause incomplete solder moistening in the scope of intercalation 1730, and it can reduce peel strength With solder bonds reliability.The bending in combined firing multiple-level stack is usefully reduced or eliminates, with the ground soft soldering that assures success To colored belt.
Variable thickness can be combined into sintered multilayer stacking, to significantly reduce the bending and/or corrugation of each layer.When one or When multiple layers have variable thickness, uneven interface can be brought between these layers.One instruction of variable thickness is sintered multilayer Non-planar interfaces between stacks of thin films.There is figure by the pattern of the part for forming first layer and immediately directly in first layer The second layer is printed on case part and produces variable thickness, so as to produce the non-planar interfaces between two layers.In one arrangement, have The layer of variable thickness is as using the result for having pattern silk screen and printing.After firing, the thickness of each layer can be lowered, But firing does not cause the layer with variable thickness to become the layer with non-uniform thickness.Variable thickness in one layer, which can be used, to be cut Face SEM and surface topology technology are measured and quantitative before and after firing.In multiple embodiments, when in 1x1mm areas It is middle measurement it have at least 20% be more than or at least 20% be less than this layer average thickness thickness change when, one layer can be described For with variable thickness.
Accompanying drawing 18 is according to embodiments of the present invention, to realize drying during can be used for the deposition of metallic slurry The silk screen of the variable thickness of metal particle layer.Silk screen 1800 has open mesh 1810, and some have area of the pattern 1820.There is figure Case region 1820 includes closing area 1821 and open area 1822.When during silk screen being used for the printing of wet metal particle layer, Slurry flows opening 1822 and open mesh 1810 and it is closed area 1821 and stops, it causes the wet metal particle layer tool of deposition There is variable thickness.In one embodiment, wet metal particle layer is dried immediately dries metal particle layer to form variable thickness, And embedded slurry is deposited directly to variable thickness and dried in metal particle layer.
There are Multiple factors to influence to dry the variable thickness in metal particle layer, such as mesh count, linear diameter and shape, phase Line angle degree, emulsion (emulsion) thickness and silk screen design to framework.Mesh size and linear diameter determine what can be printed Minimum pattern shape and opening.The thickness change dried in metal particle layer is also influenceed by the flowing of metallic slurry, It has impact on layer slip.Slurry can be configured with high viscosity and thixotropy, accurately to control them to be deposited on the position in basic unit. It is still possible that the emulsion thickness by adjusting silk screen, changes the size of the thickness change in metal particle layer.Silk screen can be set It is calculated as ensuring in substrate surface continuously drying metal particle layer, with variable layer thickness overall or only in a particular area. In an exemplary embodiment, metallic slurry uses 230 mesh screens with 5 μm of emulsion thickness to print. In one kind arrangement, pattern 1820 has by 100 μm of adjacent 100 μm that area 1821 is closed by 3mm of 3mm aperture areas 1822 Series.Do not limited in terms of types of patterns, cycle (or lacking it) or size.Many patterns can bring variable thickness, and scheme Case can be adjusted for a variety of printing conditions and formula of size.
Accompanying drawing 19 is, according to embodiments of the present invention, to be deposited on using silk screen 1800 shown in accompanying drawing 18 in basic unit 1910 The schematic section of drying metal particle layer with variable thickness.The exterior lateral area 1925 of metal particle layer 1920 is dried by passing through The deposited metal particle slurry of open mesh area 1810 of silk screen 1800 and immediately dry metallic slurry and formed.Region Variable thickness drying metal particle layer 1922 in 1925 is deposited and had by the hidden region 1820 of silk screen 1800 can be thickening Degree.The variable thickness that embedded slurry is directly printed in region 1925 immediately is dried in metal particle layer 1922 and dried with shape Into intercalation 1930.
Accompanying drawing 20 is that according to embodiments of the present invention, the structure of accompanying drawing 19 is at it by the signal after joint sintering Property sectional view.As described above, combined firing causes the material from intercalation 1930 (accompanying drawing 19) to be embedded in following variable thickness Dry in metal particle layer 1922 (accompanying drawing 19), change variable thickness metal particle layer 1922 and improve metallic into variable thickness Layer 2022 and conversion intercalation 1930 are improvement intercalation 2030.In one arrangement, improvement metal particle layer 2022 has figure The thickness change of case, includes but is not limited to, cycle protuberance, ridge, edge and other feature shapes.It should be noted that improvement intercalation 1930 thickness is typically unified, and improves the non-planar interfaces between intercalation and improvement metal particle layer (because it can Varying-thickness) can be by measuring multiple-level stack total thickness degree in change and infer.
Accompanying drawing 21 is the plan view light micrograph that joint sintered multilayer is stacked, and wherein metallic slurry is using for example Screen printing shown in accompanying drawing 18 is brushed with variable thickness (in some regions).Intercalation is directly printed on the variable of metal particle layer On thickness area, and multiple-level stack joint sintering to form improvement intercalation 2121 on the top, in the metal of near flat Every side Shang You sides of particle layer 2120.Metal particle layer 2120 has planar top surface.The surface of improvement intercalation 2121 is uneven Smooth, the pattern with the thickness change being reflected in following improvement metal particle layer.Improve the surface of intercalation 2121 not Display bending or corrugated symbol, as high-visible in improvement intercalation 1730 in figure 17.At one of the present invention In embodiment, the part that joint sintered multilayer is stacked has variable thickness.
Useful linear module is to describe during variable thickness to compare peak value thickness and valley thickness and average thickness. In random layer, there can be some unintentionally thickness changes, but these changes are typically less than averagely thickness 20%.If one layer Thickness change and be less than the 20% of average thickness, then this layer is regarded as flat (having non-uniform thickness).By carefully setting Count the silk screen for type metal particle slurry, it is possible to produce the layer with variable thickness, it has in 1x1mm areas Measurement, at least 20% be more than or at least 20% be less than this layer average thickness thickness change.
Variable thickness during sintered multilayer is stacked can be measured from the SEM image of the cross-section sample of polishing.Accompanying drawing 22 be according to Embodiments of the present invention, the sintered multilayer with variable thickness stacks the cross-sectional SEM image of 2210 part.Cross-section sample Prepared using the above method and drawn.Sintered multilayer stacks 2210 and includes improvement intercalation 2211, improvement aluminum shot sublayer 2212 and silicon Basic unit 2213.Two interfaces on every side of improvement aluminum shot sublayer 2212 are recognized in the picture：Silicon base layer 2213 and improvement aluminum shot Interface 2217 between interface 2218 between sublayer 2212, and improvement aluminum shot sublayer 2212 and improvement intercalation 2211.Interface 2216 be solderable surface.For comparing, accompanying drawing 23 shows silicon base layer 2322, and it has and does not have the flat of variable thickness Aluminum particulate film 2321.
The average thickness of improvement aluminum shot sublayer 2212 in accompanying drawing 22 is calculated by average thickness measured value.In accompanying drawing 22 Thickness between two interfaces 2217 and 2218 is measured through sample with regular intervals (for example, 10 microns).Also in part most Thickness is measured at big value and local minimum.Software, such as ImageJ 1.50a, can be used for obtaining average thickness and minimum And maximum gauge.The peak and valley seen in single transversal sample can not represent whole sintered multilayer and stack.Therefore, it is useful It is to carry out this measurement on multiple transversal samples, so that it is guaranteed that measurement and many peak and valleys.These methods are art technologies What personnel knew.
For the sample shown in accompanying drawing 22, improvement aluminum shot sublayer 2212 have 11.3 μm average thickness, 18.4 μm Peak value thickness and 5.2 μm of valley thickness.Peak value thickness ratio average thickness big 64% and valley is smaller than average thickness by 54%. In multiple embodiments, the layer with variable thickness is with than average thickness greatly at least 20%, at least 30%, at least 40% or extremely Few 50% peak value thickness.In multiple embodiments, the layer with variable thickness have as low as fewer than average thickness 20%, extremely Few 30%, at least 40% or at least 50% valley thickness.
When improvement interlayer 2211 is continuous and thickness is approximate consistent, the solderable surface 2216 for improveing interlayer 2211 is near Like parallel to interface 2217.In an embodiment of the invention, the described whole surveys for being used to improve aluminum shot sublayer 2212 Amount can be carried out for improveing the improvement interlayer 2211 between aluminum shot sublayer 2212 and solderable surface 2216 and interface 2217 Combination thickness.The approximation that comparison for the thickness measure of two combination layers has been, is only used for improveing aluminum particulate for comparing The thickness measure of layer 2212.For the combination layer in accompanying drawing 22, the average integral thickness of 13.2 μm of peak value thickness ratio is big by 44%, and Valley is smaller than average integral thickness by 43%.The thickness that this alternative can be measured systematically in sintering stacked multilayer in lower section becomes Change.
For some applications, only a fraction sintered multilayer, which is stacked, to be needed with variable thickness.For example, silicon solar cell Aluminum shot sublayer on dorsal part is typically flat.(it is wrapped rear mark layer segment usefully on the dorsal part of this battery Include improvement intercalation) middle introducing variable thickness.Compare the thickness change and a surrounding aluminum shot sublayer part in a rear reference lamina part In thickness change can be used for determine with variable thickness layer whether with the dorsal part of solar cell.
Another useful metrics unit for determining the variable thickness in sintered multilayer stacks of thin films be average paddy to peak heights, It is the average and local minimum of local maximum it is average between difference.In cross-sectional SEM image, do not ensure local maxima Value and local minimum in the picture, so surface topology measure, for example, talysurf, relevant scanning interferometer and Zoom microscope is more useful.One example of profilograph is Bruker or Veeco Dektak150 or equivalent.Phase Olympus LEXT OLS4000 3D measuring microscopes can be used to perform for dry scanning interferometer.Software appended by these methods can The automatic average peak that calculates is to the difference of paddy.
In an example embodiment, talysurf is used to determine that average peak, to paddy height, is used in identical sample Stacked in the sintered multilayer with variable thickness and for both aluminum shot sublayers with non-uniform thickness.Veeco Dektak 150 For measuring the surface in 1x1mm areas using 12.5mm radiuses probe, to produce the topological surface maps of 3D.Accompanying drawing 24 is tool The 3D surface topology maps that the sintered multilayer for having variable thickness is stacked, and accompanying drawing 25 is with non-uniform thickness (adjacent) aluminum particulate The 3D surface topology maps of layer.Brightest area in accompanying drawing indicates local maximum and most dark areas indicates Local Minimum Value.Accompanying drawing 24 shows thickness change (from -20.2 μm to 15.9 μm), and it will be expected to include variable thickness improvement metal The sintered multilayer of particle layer is stacked.Accompanying drawing 25 shows thickness change (from -4.9 μm to 5.5 μm), and it will be expected to have The aluminum shot sublayer of non-uniform thickness.Average peak to paddy is highly calculated using program Veeco Vision v4.20, its automatic identification and Average local maximum and minimum value, and then subtract difference.Average peak to sintered multilayer of the paddy height for accompanying drawing 24 is stacked It it is 35.54 μm and the aluminium lamination for accompanying drawing 25 is 9.51 μm.In multiple embodiments, when average peak to paddy is highly more than 10 μ M, more than 12 μm or more than 15 μm when, layer has a variable thickness, and when average peak to paddy highly less than 10 μm, it is less than 12 μm or small When 15 μm, layer has non-uniform thickness.
In an embodiment of the invention, when the variable thickness multiple-level stack of joint sintering improves intercalation, such as accompanying drawing 20 when one of showing by soft soldering to colored belt, and its peel strength is that the stripping that the sintered multilayer without variable thickness is stacked is strong Twice of degree.In one arrangement, the improvement intercalation on surface that this variable thickness sintered multilayer is stacked is by soft soldering to being based on The colored belt of tin, and they are with more than 1.5N/mm or the peel strength more than 2N/mm or more than 3N/mm.Thickness change It can be optimized, to provide continuous metal particle layer and back surface field in the basic unit for silicon solar cell.Thickness change It can be optimized so that the contact resistance of the variable thickness multiple-level stack of this joint sintering is equal to or less than the connection of near flat Close the contact resistance that sintered multilayer is stacked.In an exemplary embodiment, when using embedded slurry to be etching through medium During layer, the thickness change in transformation and improvement metal particle layer includes being less than the region of 20 μm, 10 μm, 5 μm or 2 μ m thicks.
Above-described variable thickness (many) layer, is used as (many) groups during any sintered multilayer described here is stacked Into.Variable thickness (many) layers, such as variable thickness are dried and improvement metal particle layer, can be used in any silicon solar cell On, with the bending of reference lamina after reduction.
Embedded slurry is changed as the plug-in type in silicon solar cell
In one embodiment, the noble metal comprising 45wt%, 30wt% imbedded particle and 25wt%'s has The insertion slurry of airborne body (slurry C in Table I above) is used as plug-in type and changes (drop in replacement), with The rear reference lamina formed in silicon solar cell.The manufacture that p-n junction closes silicon solar cell is well known in the art. Goodrich et al. provides complete work flow to manufacture back surface field silicon solar cell, and it is referred to as " standard c-Si Solar cell ".Referring to Goodrich et al. " the monocrystalline silicon photovoltaic generation road-map based on chip：Use known skill Art, which improves chance, to be used to further reduce manufacturing expense ", solar energy materials and solar cell (2013), the 110-135 pages, its Herein by reference to and merge.In one embodiment, step is included for manufacturing the method for electrode of solar battery：There is provided Silicon wafer, is coated at least one dielectric layer with a part of preceding surface, aluminum shot sublayer is coated at the back side of silicon wafer, does Dry aluminum shot sublayer, embedded slurry (rear mark) layer is coated in a part for aluminum shot sublayer, embedded pulp layer is dried, in silicon wafer A plurality of fine grid blockses line and the layer that confluxes before at least one are coated on dielectric layer on preceding surface, is dried and combined firing silicon wafer. The method of such as silk-screen printing, intaglio printing, jet deposition, slit coating, 3D printing and/or inkjet printing can be used for coating Multiple layers.As an example, Ekra or Baccini screen processes press can be used for deposition of aluminum particle layer, embedded pulp layer and Front side grid lines and the layer that confluxes.In another embodiment, solar cell has at least one dielectric layer, covers silicon wafer Rear surface at least a portion.For PERC (battery (passivated emitter rear cell) after passivation emitter) Framework, after two dielectric layers (that is, aluminum oxide and silicon nitride) are applied to silicon solar cell before the application of aluminum shot sublayer Side.Drying multilayer can complete in the band oven (belt furnace), and constant temperature between 150 DEG C to 300 DEG C 30 seconds is extremely 15 minutes.In one arrangement, the band ovens of Despatch CDF 7210 are used to dry and combined firing silicon solar cell, its Stacked comprising sintered multilayer described here.In one arrangement, the completion of combined firing is using rapid heating technique and in sky The constant temperature more than 760 DEG C is heated in gas between 0.5 to 3 second, it is for the normal of aluminum back surface field silicon solar cell With temperature profile (temperature profile).The heat that the temperature profile of chip is connected to exposed chip usually using having Galvanic coupleSystem calibration.
Accompanying drawing 26 shows before silicon solar cell 2600 schematic diagram of (or illuminated) side.Silicon solar cell 26-- has silicon wafer 2610, with least one dielectric layer (not shown), has fine grid blockses line 2620 and front side on its top Bus bar 2630.In one embodiment, the dielectric layer on silicon wafer frontside includes at least one material from lower group selection, Include silicon, nitrogen, oxygen, aluminium, gallium, germanium, hafnium, synthetic and combinations thereof.In another embodiment, the medium on silicon wafer frontside Layer is silicon nitride and thick less than 200nm.The silver metallized slurry in commercially available front side as known in the art can be used for shape Into fine grid blockses line 2620 and preceding bus bar 2630.It should be noted that front side silver layer is (that is, fine as made from silver metallized slurry Grid lines 2620 and preceding bus bar 2630) dielectric layer can be etching through during combined firing and is directly connect with silicon wafer 2610 Touch.In one embodiment, silicon wafer 2610 is monocrystalline and doping n-type or p-type.In another embodiment, silicon wafer Piece 2610 is polycrystalline and doping n-type or p-type.In an exemplary embodiment, basic unit is the polycrystalline with n-type emitter stage P-type silicon chip.
Accompanying drawing 27 is the schematic diagram for the rear side for showing silicon solar cell 2700.Rear side be coated with aluminum shot sublayer 2730 and With rear side reference lamina 2740, it is distributed on silicon wafer 2710.In one embodiment, the dielectric layer on rear side include from At least one material of lower group selection, comprising：Silicon, nitrogen, aluminium, oxygen, germanium, gallium, hafnium, synthetic on the preceding surface of silicon wafer and its Combination.In another exemplary embodiment, the dielectric layer on the preceding surface of silicon wafer is silicon nitride and thick less than 200nm. In one embodiment, there is no dielectric layer on the rear side of silicon wafer.Commercially available aluminum slurry as known in the art can Be printed on before firing the total surface area at the silicon wafer back side at least 85% or at least 90% or at least 95% or at least 97%, it can be described as whole Al coverings.Aluminum shot sublayer (after combined firing) 2730 has flat between 20 to 30 μm Equal thickness.In multiple embodiments, aluminum shot sublayer 2730 have 3 to 20% between, between 10 to 18% or be contained therein Any scope porosity.For traditional BSF (back surface field (back surface field)) solar cell framework, Reference lamina is directly applied to silicon wafer afterwards.However, the power conversion efficiency in order to improve solar cell, it might be useful to indicate by after Layer is imprinted in aluminum shot sublayer.In one embodiment, after intercalation is coated directly in a part for dry aluminum shot sublayer with formation Reference lamina 2740.Accompanying drawing 27 shows a kind of possible pattern for rear reference lamina 2740.Intercalation and following aluminum shot sublayer quilt Finally joint sintering is stacked with forming sintered multilayer as described herein.In multiple embodiments, improvement intercalation (or rear mark Layer) 2740 have 1 μm to 20 μm between or 2 μm to 10 μm between or 2.5 μm to 8 μm between thickness.
Above previously described variable thickness metal (aluminium) particle layer, can be used on the dorsal part of silicon solar cell, With the bending of reference lamina after reduction and improvement attachment and power contacts.In an embodiment of the invention, rear reference lamina A part has variable thickness.In yet another embodiment of the present invention, improvement aluminum shot sublayer a part have can be thickening Degree.In one arrangement, the rear reference lamina on the surface of this variable thickness improvement aluminum shot sublayer is by soft soldering to the mark based on tin Will band, brings the peel strength more than 0.7N/mm, more than 1.5N/mm, more than 2N/mm or more than 3N/mm.Thickness change can It is optimized, to provide continuous metal particle layer and back surface field in the basic unit for silicon solar cell.In another reality Apply in mode, in rear reference lamina region, a part for the combination layer (improvement aluminum shot sublayer and rear reference lamina) in that region Thickness with the average combined thickness degree big at least 20%, 30% or 40% than being measured on 1x1mm areas.In another reality Apply in mode, in rear reference lamina region, a part for the combination layer (improvement aluminum shot sublayer and rear reference lamina) in that region With the average combined thickness degree than being measured on 1x1mm areas it is small by least 20%, 30% or 40% thickness.
In an embodiment of the invention, including the solar cell that stacks of any sintered multilayer discussed herein can It is incorporated into solar energy module.Here there are many possible solar energy module designs, which use this solar cell, It is just as the skilled person will be aware of.The quantity of solar cell is not intended to be limited in module.Typically, 60 or 72 Each solar cell is merged into commercially available module, but likely merges more or less, and this is depended on should With (that is, consumer electronics, house, business, communal facility, etc.).Module typically comprises by-pass diode (not shown), connect Line box (not shown) and the support frame (not shown) for being not directly contacted with solar cell.By-pass diode and terminal box can be with It is the consideration part of battery interconnection.
Accompanying drawing 28 is the schematic cross-sectional for the part that solar module is shown according to embodiments of the present invention Figure.Solar module includes at least one silicon solar cell 2840.The front side 2840F connections of silicon solar cell 2840 To the first colored belt 2832 (it enters and leaves the page), there are preceding encapsulated layer 2820 and anter 2810 thereon.Silicon solar cell 2840 rear side 2840B is connected to the second colored belt 2834, there is post package layer 2850 and rear piece 2860 thereon.Colored belt 2832, 2834 adjacent solar batteries connect power contacts to front side (that is, the preceding busbar on front side of a battery by soft soldering (front busbar)) and adjacent solar battery dorsal part (that is, the rear colored belt on dorsal part).It is substantial amounts of in solar energy module Solar cell can be used colored belt and be electrically coupled together as battery interconnection.
Typical battery interconnection includes metal flag band of the soft soldering to solar cell and the metal of connection colored belt is total Tape (metal bus ribbon).In an embodiment of the invention, colored belt is the metal tape with solder coat. The colored belt of this coated with solder can have 20 to 1000 μm, 100 to 500 μm, 50 to 300 μ ms or include in the inner appoint The thickness of what scope.The width of the colored belt of coated with solder can be 0.1 between 10mm, 0.2 between 1.5mm or being contained in it Interior any scope.The length of colored belt is determined by application, design and basic unit's size.Solder coat can have 0.5 to 100 μm it Between, the thickness between 10 to 50 μm or in any scope for being contained therein.Solder coat can include tin, and lead is silver-colored, bismuth, copper, Zinc, antimony, manganese, indium or its alloy, synthetic or other combinations.Metal flag band can have 1 μm to 1000 μm between, 50 to 500 Thickness between μm, between 75 to 200 μm or in any scope for being contained therein.Metal flag band can comprising copper, aluminium, silver, Gold, carbon, tungsten, zinc, iron, tin or its alloy, synthetic or other combinations.The width of metal flag band can 0.1 to 10mm it Between, 0.2 between 1.5mm or including any scope in the inner.In one embodiment, colored belt is copper strips, its 200 μm Thick and 1mm is wide and the tin of 20 μ m-thicks is scribbled on every side：Lead (60:40wt%) solder coat.
Anter 2810 in accompanying drawing 28 provides some mechanical supports for module and is designed as inhaling in solar cell 2840 The optical delivery attribute having had on the part of the solar spectral of receipts.Solar energy module is positioned to so that anter 2810 is in face of shining Bright source, such as sunlight 2860.Anter 2810 is typically made by low iron content soda-lime glass (soda-lime glass).Preceding envelope Dress layer 2820 and post package layer 2850 protect solar cell to be stimulated during operation away from electric power, chemically and physically.Encapsulate allusion quotation Type in the form of polymeric sheet.The examples of materials that can be used as encapsulation includes but is not limited to, ethane-acetic acid ethyenyl ester (ethylene Vinyl acetate) (EVA), polyethylene -co- methacrylic acid (poly-ethylene-co-methacrylic acid) (ionomer), polyvinyl butyral resin (polyvinyl butyral) (PVB), thermoplastic polyurethane (thermoplastic Urethane) (TPU), polyalphaolefin (poly- α-olefin), dimethyl silicone polymer (poly-dimethylsiloxan) (PDMS), other polysiloxanes (polysiloxanes) (i.e. silicon (silicone)) and combinations thereof.
Piece 2860 is that solar cell 2840 provides protection from rear side afterwards, and can be or can not be optically transparent 's.Solar energy module is positioned to so that rear piece 2860 is away from face of light source, such as sunlight 2860.Piece 2860 can be by three afterwards Sandwich construction made from layers of polymer film.DuPontTM Polyvinyl fluoride (polyvinyl fluoride) (PVF) film It is typically used in rear piece.Fluoropolymer (fluoropolymer) and polyethylene terephthalate (fluoropolymers And polyethylene terephthalate) (PET) can also be used in rear piece.Sheet glass may also used as rear piece, and it can Auxiliary provides the structural support to solar energy module.Support frame (not shown) may be additionally used for improved structure support；Carriage Frame is typically made by aluminium.
There is provided the method for forming solar module in an embodiment of the invention.Weld tabs is artificial Ground is applied to by using Automatic Logos or wire drawing machine (automated tabbing or stringing machine) Independent solar battery (it is stacked comprising any sintered multilayer described here).Then, independent battery by direct soft soldering it Be electrically connected in series to colored belt.The structure brought is referred to as " battery strings (cell string) ".Generally, multiple battery strings cloth Put and having been applied on the preceding encapsulated layer of anter.These multiple battery strings are connected to each other with generation circuit using bus bar.Always Tape is more wider than for the colored belt in battery strings.When the circuit between all batteries string is completed, post package material is employed To connection battery strings the back side and rear piece be placed on post package material.The component is sealed using vacuum lamination process immediately And heating (typically lower than 200 DEG C) is with polymeric encapsulation material.Framework is typically cemented at around anter to provide structural support. Finally, terminal box is connected to battery interconnection and is connected to solar energy module.By-pass diode can be in terminal box or can be Connected during battery interconnection process in inside modules.
In an embodiment of the invention there is provided the method for forming solar energy module, including：A) at least one is provided Individual solar cell, it has preceding surface and rear surface；Wherein, rear surface includes sintered multilayer and stacked, b) in rear reference lamina and Before conflux layer a part on soft soldering colored belt a part, to produce battery strings, c) alternatively, soft soldering colored belt to bus bar To complete circuit, d) arrange battery strings on the preceding encapsulated layer for having been applied to anter, e) apply post package layer to battery strings and After connection piece to post package layer, to form modular assembly, f) laminated module component；G) electrical connection and physical engagement terminal box.
Solar energy module likely is decomposed using following step, to determine multiple-level stack as described above whether It is merged.Piece and post package are to expose the rear surface of the mark of solar cell after dismounting.Solar cell colored belt and Apply fast-curing epoxy resin on surface after surrounding.Slave module removing battery and use gold after epoxy resin has been cured Hard rock is sawed to cut off the fragment of colored belt/solar cell.Using previously described ion milling machine with section of polishing, and perform Whether SEM/EDX determines the structure as described in embodiments of the present invention.Accompanying drawing 29 is the back of the body of solar cell The cross-sectional SEM image of the polishing of (not illuminating) side.Sample comes from solar cell (its sintered multilayer for including novelty is stacked), its It has been incorporated into solar energy module and has then removed as described above.Image shows that metal flag band 2932 and its solder are applied Layer 2931, its soft soldering to sintered multilayer stacks 2902.The techonosphere that sintered multilayer stacks 2902 is high-visible.Just applied in solder The lower section of layer 2931 is improvement intercalation 2945, improvement metal particle layer 2944 and silicon base layer 2941.The layer recognized in accompanying drawing can make More easily recognized with EDX.
Other PV battery architectures
Embedded slurry can be used for producing a variety of sintered multilayers stackings, and it is used as many different solar cell frameworks Front side and dorsal part on metal layer.As disclosed herein, embedded slurry and sintered multilayer, which are stacked, can be used for solar-electricity Pond framework, it includes but is not limited to, BSF silicon solar cells, passivation emitter and rear contact (passivated emitter And rear contact) (PERC) solar cell, and two-sided fourchette back contact solar cell (bifacial and interdigitated back contact solar cell)。
PERC solar cells framework is improved based on BSF solar energy frameworks, by using silicon base layer and back contacts it Between Dielectric (dielectric barrier) and reduce after contact surface recombination.In PERC batteries, the dorsal part of silicon wafer The part of (that is, not illuminating) is passivation at least one dielectric layer, is combined with reducing current carrier.It is disclosed herein Novel sintered multilayer, which is stacked, can be used in PERC solar cells.In one embodiment, Jie on silicon wafer dorsal part Matter layer includes at least one of silicon, nitrogen, aluminium, oxygen, germanium, hafnium, gallium, synthetic and combinations thereof.In another embodiment, silicon wafer Dielectric layer on piece dorsal part includes the silicon nitride of the 75nm thickness on the alumina layer and alumina layer of the 10nm thickness on silicon face Layer.The usually used aluminum slurry (for example, monocrystal EFX-39, EFX-85) designed for PERC batteries is impermeable by being situated between Matter layer.In order that aluminum shot sublayer is chemically reacted and carries out Ohmic contact with silicon, the small part region of dielectric layer is in aluminum particulate Removed before layer deposition by laser ablation.
PERL (emitter stage passivation back side local diffusion (passivated emitter with rear locally )) and PERT (passivation emitter, rear (passivated emitter, the rear totally of diffusion completely diffused Diffused it is)) two kinds of PERC battery architectures, which further improves equipment performance.Both types are dependent on doping silicon substrate The rear portion of layer is compound with what is contacted after further forbidding, and it is used as the role for the back surface field being similar in BSF batteries.In PERL In battery, the dorsal part of silicon base layer surrounds the opening in the medium contacted with rear aluminium lamination and adulterated.Doping generally by using Boron mixture or the aluminum shot sublayer aluminium contacted after composition, propagate dopant by dielectric openings and realize, similar to BSF Manufacture process.PERT batteries are similar to PERL, but in addition to the silicon of the dielectric openings contacted after adjacent contact, with rear medium Whole silicon of layer contact are doped.
In one embodiment, embedded slurry, it includes the imbedded particle for not being etching through dielectric layer, as PERC, Rear reference lamina on PERL or PERT batteries." non-etched (non-etching) " embedded slurry is used to provide solderable silver surface With mechanical enhancer lower floor (improvement) aluminum shot sublayer.The sintered multilayer brought, which is stacked, includes silicon wafer, and it is situated between covered with least one Matter layer, improvement aluminum shot sublayer and improvement intercalation；For PERL or PERT, silicon adulterates or also extended through respectively Jie only at dielectric openings Matter interface.Etching and the reduction surface recombination of dielectric layer can further be reduced by being embedded in slurry using non-etched.For example, traditionally using The busbar slurry of rear reference lamina in PERC batteries is printed directly on dielectric layer and part is etching through dielectric layer, its Surface recombination is added during combined firing.
It is embedding according to an embodiment of the invention for the battery (that is, PERC, PERL, PERT) using rear dielectric layer The propagation doping for the silicon area for entering slurry and being modified be etching through at dielectric layer and assist medium opening." etching (etching) " embedded slurry (for example, insertion slurry D in Table I) is used to provide solderable silver surface, and mechanical enhancer lower floor (changes It is good) aluminum shot sublayer, and dielectric layer is etching through, silicon face is exposed to aluminum particulate, it can cause aluminium to be doped into exposed silicon.Band The sintered multilayer come is stacked comprising silicon wafer, improvement aluminum shot sublayer and improvement intercalation.Sintered multilayer, which is stacked, can further comprise silicon Near surface doping Al region (be similar to back surface field in BSF batteries), and silicon wafer and improvement aluminum shot sublayer it Between interface solid silicon-aluminium Eutectic Layer.There are a variety of advantages to be etching through (many) dielectric layers using embedded slurry.It is first First, it is to being proved to be the cheap replacement of expensive and insecure laser ablation step in the past.Second, combine when chip and burn During knot, laser ablation often removes tens of to hundreds of microns of silicon substrate layer material, and can bring between silicon base layer and aluminum shot sublayer Big space formation.The embedded slurry of sintering will not cause the change of wafer surface before joint sintering, and it is compared with when using During laser ablation, bring preferably combine to form, the space of reduction is formed and more preferable reproducibility.
According to an embodiment of the invention, embedded slurry can be used for the solderable surface for providing battery structure, its Depending on aluminum shot sublayer with p-type silicon carry out Ohmic contact.The example of these constructions includes fourchette back contact solar cell, n Type BSF battery architectures and double-sided solar battery.In one embodiment, embedded slurry C (coming from Table I) is applied to finger On fork back contact solar framework, the Al layers of such as Zebra batteries.For n-type BSF frameworks, it has been obtained for complete for Al 20% power conversion efficiency of the battery of portion's covering, embedded slurry can replace directly contacting traditional rear mark Ag slurries of silicon, Thus reduce the V of solar celloc.In a variety of solar cell frameworks based on n-type chip, before embedded slurry can be used in On side (that is, illumination side).Embedded slurry may also be combined with Al slurries and use, to reduce the expense of double-sided solar battery.It is existing Double-sided solar battery framework uses Ag slurries, and it includes a small amount of aluminium (for example, Al less than 5wt%), to enter with p-type silicon layer Row Ohmic contact.Existing two-sided framework is using the silver amount of BSF framework almost twices, and this forbids in expense.Usefully Fine aluminium slurry is used in two-sided framework, but Al is not solderable.Insertion slurry comprising silver is (for example, the slurry in Table I C) can be printed on Al slurries in double-sided design, and provide mechanical stability and sinterable surface reduces Ag use simultaneously Amount.
The material properties that sintered multilayer is stacked and the influence to silicon solar cell.
Sintered multilayer for solar cell and other electronic equipments material properties interested in stacking include can be soft Weldering property, peel strength and contact resistance.
Solderability is, at a temperature of less than 400 DEG C, passes through the fusing metal solder between two metal surfaces Flowing, forms the ability of strong physical bond between the two metal layers.The soft soldering on improvement intercalation that sintered multilayer is stacked can Performed after being heated to more than 650 DEG C in atmosphere.Soft soldering including the use of flux, its be before fusing solder backflow cleaning or Etch the chemical reagent on one or two surface.Be typically used in the solder flux of solar cell, be denoted as RMA (for example,186) or R (952), it is deposited on colored belt and in 70 DEG C of dryings.These flux are much worked as in etching Metal oxide, such as aluminum oxide (Al on aluminum particulate are formed when sintering in atmosphere2O3) when be not effective.
Peel strength be the measurement of solder joint strength and for integrated circuit, light emitting diode and application of solar energy can By the instruction of property.Solder flux and drying can be dipped into by being coated with 0.8 to 20mm wide and the thick metal tapes of 100-300um solder.It It is placed into the temperature on improvement intercalation and between 200 DEG C to 400 DEG C and uses soldering iron (solder iron) by soft soldering.Peel off strong Degree is, is separated with soft soldering direction into 180 ° of angles, by the width of soft soldering band, the peeling rate to give, needed for peeling off soft soldering band Power.The soft soldering point (solder joint) formed during soft soldering process has under 1mm/sec is more than 1N/mm (for example, 2mm Colored belt needs the peeling force more than 2N to remove soft soldering band) mean peel strength.Solar cell is electrically connected by colored belt Connect, it is by the preceding busbar of soft soldering to battery and the rear reference lamina of adjacent cell.Typically for commercially it is available too The contact of colored belt in positive energy battery, peel strength is 1.5 between 4N/mm.Marked after using sintered multilayer to stack conduct During will layer, dominant failure mode can be in Al-Si near interfaces, and plan view SEM/EDX can be used to determine for it.It is schematically real at one Apply in mode, when the layer soft soldering of (improvement intercalation) rich silver layer has the colored belt based on tin, peel strength is more than 1N/mm.
Meier et al. describes how to determine each metal on complete solar cell using four-point probe electrical measurement Change the resistance of layer.Referring to Meier et al. " composition that series resistance is determined from the measurement on the battery of completion ", IEEE (2006), page 2615, it is by reference to being incorporated herein.The bulk resistor (bulk resistance) of metal layer directly about The bulk resistor of its material is made.In an embodiment of the invention, pure Ag bulk resistor is 1.5x10-8Ω-m；It is used in Pure Ag metal layers on industrial solar cell have higher than pure Ag bulk resistors 1.5 again to 5 times of bulk resistor.Bulk resistor for Fine grid blockses line is important, and it must upload transmission of electricity stream in the length of relatively long (that is, more than 1cm).When battery it is flagged When in module, the resistance of preceding busbar and rear reference lamina is less important.
In most of integrated circuit, LED and solar cell framework, the electric current from metal particle layer flows through improvement gold Belong to particle layer and enter improvement intercalation.Stacked for sintered multilayer, the contact resistance between these three layers is played the part of in device performance Drill key player.Transmission route survey can be used in the measurement of contact resistance during sintered multilayer is stacked between these layers (transmission line measurement) (TLM) (reference：Meier et al., " copper dorsal part convergent belt：In crystalline silicon too Ag is eliminated in positive energy battery and module and full aluminium is covered ", IEEE PVSC (2015), the 1-6 pages).TLM draw for electrode it Between resistance relative distance.TLM is used in particular for measuring contact resistance, 1) between metal particle layer and improvement metal particle layer, And 2) between improvement metal particle layer and improvement intercalation.Sintered multilayer stack contact resistance be above-mentioned contact resistance 1) and 2) it With.The contact resistance that sintered multilayer is stacked is the half of the y-intercept value of the linear fit of resistance relative distance measurements.Busbar Between the measurement of resistance use the digital sourcemeters of Keithley 2410 (Sourcemeter) that are set with four-point probe, ource electric current In -0.5A between+0.5A and measurement voltage.In multiple embodiments, sintered multilayer stack contact resistance 0 to 5mOhm, 0.25 to 3mOhm, 0.3 are between 1mOhm or in any scope for being contained therein.The sheet resistance of metal particle layer leads to Line gradient is crossed to be multiplied by electrode length to determine.Contact resistance is used to numerically determine conveying length contact with therewith with sheet resistance Resistance coefficient.Change in series resistance covers to determine by the area of contact resistance coefficient divided by improvement intercalation. In multiple embodiments, the change in series resistance is less than 0.200 Ω-cm2, less than 0.100 Ω-cm2, less than 0.050 Ω- cm2, less than 0.010 Ω-cm2Or less than 0.001 Ω-cm2。
The contact resistance between reference lamina and aluminum shot sublayer can influence series resistance and the electrical power conversion of solar cell afterwards Efficiency.This contact resistance can be measured by transmission route survey.It is traditional on silicon with 300 μm of overlapping aluminum shot sublayers The transmission line of electricity of reference lamina is drawn shown in Figure 30 after silver.Intercalation is improved in aluminum shot sublayer, as the defeated of rear reference lamina Electric line is drawn, shown in Figure 31.Y-intercept value in accompanying drawing 31 is 1.11mOhm, the y-intercept compared in accompanying drawing 30 0.88 Value.The contact resistance between mark (slotting) layer and aluminum shot sublayer is 0.56mOhm afterwards.Contact electricity for indicating framework after tradition Resistance is 0.44mOhm.In multiple embodiments, the contact resistance between rear mark (slotting) layer and aluminum shot sublayer is 0 to 5mOhm Between, 0.25 between 3mOhm or 0.3 between 1mOhm or in any scope for being contained therein.The piece of aluminium lamination Resistance is multiplied by electrode length to determine by line gradient, and is about 9mOhm/ squares (square) in accompanying drawing 30 and 31.
Although TLM is the accurate preferred side for extracting sintered multilayer stacking (that is, rear reference lamina and aluminum shot sublayer) contact resistance Method, it is possible to, determine the contact resistance in the complete sun on battery using four-point probe method.The use of this method passes through, Reference lamina (R after two is measured firstAg-to-Ag) between resistance, and then on Al particle layers (in the 1mm of rear reference lamina) Traveling probe is to obtain RAl-to-Al.Contact resistance passes through RAl-to-AlSubtract RAg-to-AgAgain divided by 2 obtain.This measures that unlike TLM It is accurate, but when the measured value averagely from multiple solar cells, it can be approximately among 0.50mOhm.
Resistance and sheet resistance are used for numerically determination conveying length and contact resistance coefficient therewith.In accompanying drawing 31, connection The conveying length for closing sintered multilayer stacking is 5mm and contact resistance is 2.2m Ω.Change in series resistance passes through this numeral Divided by the area of improvement intercalation covers to estimate.In accompanying drawing 31, estimation in series resistance change be 0.023 Ω- cm2, it, which is equal to the calculating measured in accompanying drawing 30, is used for 0.020 Ω-cm of reference lamina after tradition2Series resistance change.String The change of connection resistance can be directly measured, by manufacturing the control BSF (back surface field) covered with full Al and without rear reference lamina Silicon solar cell and manufacture have full Al coverings and Ag：The BSF silicon solar cells of Bi intercalations.The series resistance of battery can Obtained by the current -voltage curve under a variety of luminous intensities, and the difference of series resistance can be attributed to rear reference lamina and burning Tie increased contact resistance between aluminum shot sublayer.In multiple embodiments, the change of the series resistance in solar cell is small In 0.200 Ω-cm2, less than 0.100 Ω-cm2, less than 0.050 Ω-cm2, less than 0.010 Ω-cm2Or less than 0.001 Ω-cm2。
It is using a benefit of intercalation on silicon solar cell, by forming continuous back surface field on silicon Bring open electric circuit voltage (open-circuit voltage) (Voc) improvement.VocGain can pass through, relatively more traditional BSF Solar cell is with including Ag：Bi insertion slurry BSF solar cells and direct measurement, as described in this, when two dress Put with conflux after identical surface area when.Traditional BSF silicon solar cells use the rear mark slurry based on silver straight Connect printing on silicon and manufactured by aluminum shot sublayer is surrounded.Intercalation (for example, being manufactured using embedded slurry C) is used as tool On the silicon solar cell for having full Al surfaces covering.The V of two kinds of solar cellsocBy the electric current under a kind of sunlight intensity- Voltage tester is measured.For with more than 5cm2The solar cell that sign face is accumulated afterwards, when using intercalation, compared with tradition Silicon framework on rear reference lamina, VocAt least 0.5mV, at least 1mV, at least 2mV or at least 4mV can be increased.Finally, when using slotting When layer architecture replaces Mark Designing after tradition, short-circuit current density (short-circuit current density) (Jsc) and Fill factor, curve factor (fill factor) is also modified.Silver does not carry out Ohmic contact with p-type silicon.Silicon reference lamina directly drops on p-type silicon Low current acquisition, its can by performed on complete or incomplete solar cell electroluminescent or photoluminescence measurement come Estimation.JscIncrease can also contrast the battery of directly rear reference lamina on silicon by testing the battery with telescope structure and survey Amount.Another benefit is the increase of fill factor, curve factor, and it may depend on VocIncrease, the reduction of contact resistance and/or solar-electricity Compound dynamic change on rear side of pond and positive change.
It is to be understood that invention described herein can be performed by distinct device, material and device, and pair set A variety of modifications of standby and both operating process can be implemented, without departing from the scope of itself of the invention.

Claims (37)

1. a kind of form the method that sintered multilayer is stacked, the method comprising the steps of：
A) wet metal particle layer is coated at least a portion of substrate surface；
B) wet metal particle layer is dried, to form dry metal particle layer；
C) wet intercalation is directly coated at least a portion for drying metal particle layer, to form multiple-level stack；
Wherein, wet intercalation includes：
Include 10wt% to the noble metal between 70wt%；
At least 10wt% imbedded particles；And
Organic carrier；
Wherein, imbedded particle includes the one or more from lower group selection, is aoxidized comprising low temperature substrates metallic, crystalline metal Thing particle and glass melt grain；
D) multiple-level stack is dried；And
E) combined firing multiple-level stack, to form sintered multilayer stacking.
2. the method for claim 1, wherein wet metal particle layer includes metallic, it is included from lower group selection Material, comprising：Aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, steel, and its alloy, synthetic and other combinations.
3. the method as described in claim 1, further comprises：Before step a), at least a portion of substrate surface The step of depositing at least one dielectric layer, and wherein, at least a portion that step a) is included in dielectric layer directly coats wet metal Particle layer.
4. the method for claim 1, wherein each coating step includes the method independently selected from the following group, including：Silk Wire mark brush, intaglio printing, jet deposition, slit coating, 3D printing and ink jet printing.
5. the method for claim 1, wherein step a) includes, silk-screen printing is carried out by figuratum silk screen, to produce The raw wet metal particle layer with variable thickness.
6. the method for claim 1, wherein step b) and dry 1 second to 90 at a temperature of d) being included in less than 500 DEG C Minute.
7. the method for claim 1, wherein step b) and d) be included at a temperature of between 150 DEG C to 300 DEG C dry 1 second to 60 minutes.
8. the method for claim 1, wherein step e) includes being heated rapidly to the temperature more than 600 DEG C in atmosphere, Continue 0.5 second to 60 minutes.
9. the method for claim 1, wherein step e) includes being heated rapidly to the temperature more than 700 DEG C in atmosphere, Continue 0.5 to 3 second.
10. the method as described in claim 1, further comprises：Step f), the soft soldering mark in the part that sintered multilayer is stacked Will band.
11. the method for claim 1, wherein low temperature substrates metallic includes the material from lower group selection, comprising： Bismuth, tin, tellurium, antimony, lead, and alloy, synthetic, and its other combinations.
12. the method for claim 1, wherein crystalline metal oxide particle includes oxygen and the gold from lower group selection Category,：Bismuth, tin, tellurium, antimony, lead, vanadium, chromium, molybdenum, boron, manganese, cobalt, and alloy, synthetic, and its other combinations.
13. the method for claim 1, wherein glass, which melts grain, includes the material from lower group selection, comprising：Antimony, arsenic, barium, Bismuth, boron, cadmium, calcium, cerium, caesium, chromium, cobalt, fluorine, gallium, germanium, indium, hafnium, iodine, iron, lanthanum, lead, lithium, magnesium, manganese, molybdenum, niobium, potassium, rhenium, selenium, Silicon, sodium, strontium, tellurium, tin, vanadium, zinc, zirconium, its alloy, its oxide, its synthetic, and its other combinations.
14. forming the method that sintered multilayer is stacked, the method comprising the steps of：
A) wet metal particle layer is coated at least a portion of substrate surface；
B) wet metal particle layer is dried, to form dry metal particle layer；
C) dry wet metal particle layer is fired, to form metal particle layer；
D) wet intercalation is directly coated at least a portion of metal particle layer, to form multiple-level stack；
Wherein, wet intercalation includes：
10wt% is to the noble metal between 70wt%；
At least 10wt% imbedded particles；And
Organic carrier；
Wherein, imbedded particle includes the one or more from lower group selection, is aoxidized comprising low temperature substrates metallic, crystalline metal Thing particle and glass melt grain；
E) multiple-level stack is dried；And
F) multiple-level stack is fired, to form sintered multilayer stacking.
15. method as claimed in claim 14, wherein, metal particle layer includes metallic, and it is included from lower group selection Material, comprising：Aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, steel, and its alloy, synthetic and other combinations.
16. method as claimed in claim 14, further comprises：Before step a), at least a portion of substrate surface The step of upper at least one dielectric layer of deposition, and wherein, at least a portion that step a) is included in dielectric layer directly coats wet gold Belong to particle layer.
17. method as claimed in claim 14, wherein, each coating step includes the method from lower group selection, including：Silk screen Printing, intaglio printing, jet deposition, slit coating, 3D printing and ink jet printing.
18. method as claimed in claim 14, wherein, step a) includes, and silk-screen printing is carried out by figuratum silk screen, with Produce the wet metal particle layer with variable thickness.
19. method as claimed in claim 14, wherein, step b) and 1 second is dried extremely at a temperature of e) being included in less than 500 DEG C 90 minutes.
20. method as claimed in claim 14, wherein, step b) and e) being included at a temperature of between 150 DEG C to 300 DEG C is done Dry 1 second to 60 minutes.
21. method as claimed in claim 14, wherein, step c) and f) include being heated rapidly to the temperature more than 600 DEG C, hold It is continuous 0.5 second to 60 minutes.
22. method as claimed in claim 14, wherein, step c) and f) include being heated rapidly to be more than 700 DEG C in atmosphere Temperature, continue 0.5 to 3 second.
23. the method as described in claim 1, further comprises：Step g), the soft soldering mark in the part that sintered multilayer is stacked Will band.
24. method as claimed in claim 14, wherein, low temperature substrates metallic includes the material from lower group selection, comprising： Bismuth, tin, tellurium, antimony, lead, and alloy, synthetic, and its other combinations.
25. method as claimed in claim 14, wherein, crystalline metal oxide particle includes oxygen and the gold from lower group selection Category,：Bismuth, tin, tellurium, antimony, lead, vanadium, chromium, molybdenum, boron, manganese, cobalt, and alloy, synthetic, and its other combinations.
26. method as claimed in claim 14, wherein, glass, which melts grain, includes the material from lower group selection, comprising：Antimony, arsenic, Barium, bismuth, boron, cadmium, calcium, cerium, caesium, chromium, cobalt, fluorine, gallium, germanium, indium, hafnium, iodine, iron, lanthanum, lead, lithium, magnesium, manganese, molybdenum, niobium, potassium, rhenium, Selenium, silicon, sodium, strontium, tellurium, tin, vanadium, zinc, zirconium, its alloy, its oxide, its synthetic, and its other combinations.
27. a kind of method for manufacturing solar cell, the method comprising the steps of：
A) silicon wafer is provided, it has preceding surface and rear surface；
B) at least a portion on surface coats wet aluminum shot sublayer after silicon wafer；
C) wet aluminum shot sublayer is dried, to form aluminum shot sublayer；
D) wet intercalation is directly coated at least a portion of aluminum shot sublayer, to form multiple-level stack；
Wherein, wet intercalation includes：
10wt% is to the noble metal between 70wt%；
At least 10wt% imbedded particles；And
Organic carrier；
Wherein, imbedded particle includes the one or more from lower group selection, is aoxidized comprising low temperature substrates metallic, crystalline metal Thing particle and glass melt grain；
E) multiple-level stack is dried；
F) a plurality of fine grid blockses line and the layer that confluxes before at least one are applied on the preceding surface of silicon wafer；
G) a plurality of fine grid blockses line and the layer that confluxes before at least one are dried, to form a structure；And
H) the combined firing structure is to form silicon solar cell.
28. method as claimed in claim 27, further comprises：Between step a) and step b), in the rear table of silicon wafer The step of at least one dielectric layer is deposited at least a portion in face, and wherein, step b), which is included on dielectric layer, directly to be coated Wet aluminum shot sublayer.
29. method as claimed in claim 27, wherein, each coating step includes the method from lower group selection, including：Silk screen Printing, intaglio printing, jet deposition, slit coating, 3D printing and ink jet printing.
30. method as claimed in claim 27, wherein, step b) includes, and silk-screen printing is carried out by figuratum silk screen, with Produce the wet metal particle layer with variable thickness.
31. method as claimed in claim 27, wherein, step e) and 1 second is dried extremely at a temperature of g) being included in less than 500 DEG C 90 minutes.
32. method as claimed in claim 27, wherein, step e) and g) being included at a temperature of between 150 DEG C to 300 DEG C is done Dry 1 second to 60 minutes.
33. method as claimed in claim 27, wherein, combined firing includes being heated rapidly in atmosphere more than 600 DEG C Temperature, continues 0.5 second to 60 minutes.
34. method as claimed in claim 27, wherein, combined firing includes being heated rapidly in atmosphere more than 700 DEG C Temperature, continues 0.5 to 3 second.
35. method as claimed in claim 27, wherein, low temperature substrates metallic includes the material from lower group selection, comprising： Bismuth, tin, tellurium, antimony, lead, and alloy, synthetic, and its other combinations.
36. method as claimed in claim 27, wherein, crystalline metal oxide particle includes oxygen and the gold from lower group selection Category,：Bismuth, tin, tellurium, antimony, lead, vanadium, chromium, molybdenum, boron, manganese, cobalt, and alloy, synthetic, and its other combinations.
37. method as claimed in claim 27, wherein, glass, which melts grain, includes the material from lower group selection, comprising：Antimony, arsenic, Barium, bismuth, boron, cadmium, calcium, cerium, caesium, chromium, cobalt, fluorine, gallium, germanium, indium, hafnium, iodine, iron, lanthanum, lead, lithium, magnesium, manganese, molybdenum, niobium, potassium, rhenium, Selenium, silicon, sodium, strontium, tellurium, tin, vanadium, zinc, zirconium, its alloy, its oxide, its synthetic, and its other combinations.
CN201611044889.9A 2015-11-24 2016-11-24 The method for forming the solar cell with sintered multilayer stacks of thin films Pending CN107039539A (en)

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