CN107017311B - It is stacked for the sintered multilayer of integrated circuit and solar battery - Google Patents

It is stacked for the sintered multilayer of integrated circuit and solar battery Download PDF

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Publication number
CN107017311B
CN107017311B CN201611045541.1A CN201611045541A CN107017311B CN 107017311 B CN107017311 B CN 107017311B CN 201611045541 A CN201611045541 A CN 201611045541A CN 107017311 B CN107017311 B CN 107017311B
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layer
improvement
intercalation
sintered multilayer
metal particle
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CN107017311A (en
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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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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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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
    • H01L31/0256—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 characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
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    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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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
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    • 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
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    • 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
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    • 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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    • H01B1/14—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
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    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
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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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Abstract

Disclose the insertion slurry being used together with semiconductor device.Slurry includes noble metal, imbedded particle and organic carrier, and can be used for the material properties for improving metal particle layer.Specific formation has developed into direct silk-screen printing and sintering in dry metal particle layer and is stacked so that sintered multilayer is made.Sintered multilayer stacking is special to generate solderable surface, high mechanical strength and low contact resistance.In some embodiments, sintered multilayer stacking can be etched by dielectric layer, to be improved to the attachment of base.This slurry can be used for the efficiency for increasing silicon solar cell, especially polycrystalline and monocrystalline silicon back surface field (BSF) and passivation emitter and rear contact (PERC) photovoltaic cell.Other application includes integrated circuit, and widely, electronic device.

Description

It is stacked for the sintered multilayer of integrated circuit and solar battery
Cross reference to related applications
This application claims on the April 5th, 62/259,636,2016 of U.S. Provisional Patent Application filed on November 24th, 2015 U.S. Provisional Patent Application 62/371,236 filed in U.S. Provisional Patent Application on August 5th, 62/318,566,2016 of application With on November 16th, 2016 filed in U.S. Provisional Patent Application 62/423,020 priority, their full content passes through ginseng Examine merging herein.
The statement of governmental support
Based on the IIP-1430721 contract number that NSF is authorized, governmental support is had been obtained in the present invention.In the present invention, political affairs Mansion can have specific rights.
Technical field
The present invention relates to insertion slurries, and it includes noble metal, imbedded particle and organic carriers.
Insertion slurry (intercalation paste) can be used for the power conversion efficiency for improving solar battery.Base In silver insertion slurry be printed on aluminium layer, have after firing appropriate 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 battery based on silicon, makes With aluminum back surface field (BSF).Typically, the 85-92% of the silicon wafer of mono- and more-crystal silicon solar batteries of commercial production Back surface area covered by aluminum shot sublayer, which form back surface field and with silicon carry out Ohmic contact (ohmic contact). The rear silicon face of remaining 5-10% is covered by reference lamina after silver, is not generated field and is not carried out Ohmic contact with silicon wafer. Reference lamina is mainly used for soft soldering colored belt to be electrically connected solar battery afterwards.
When the silicon base layer (substrate) on the rear side of silver layer and solar battery directly contacts, instead of contact base When aluminum shot sublayer, estimate that the absolute standard of the transfer efficiency of solar battery reduces 0.1% to 0.2%.Therefore, height needs The entire rear portion of aluminum shot sublayer covering solar battery is used, and still is able to be connected to solar battery using colored belt Together.Past, researcher have attempted to the top that silver is directly printed on to 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.It is 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 execute most preferably, and entire solar battery efficiency reduces 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, be greater than 650 DEG C) with sinterable silicon nitrogen oxides, to carry out Ohmic contact with silicon base layer.Recently, researcher has used directly The ultrasonic wave soft soldering of tin alloy at the top of the aluminium, to generate solderable surface (solderable surface).This technology It has been realized in enough peel strengths (that is, 1-1.5N/mm), but needs additional equipment and use a large amount of tin, this increasing Expense is added.In addition, will increase at chip breach and reduction on friable material, such as aluminium and silicon wafer using ultrasonic wave soft soldering Manage yield.
With the demand for developing printable slurry, the material of (modify) lower metal particle layer can be improved during firing Expect attribute.For example, the noble metal (precious metal) comprising slurry, can be printed directly on aluminium and use standard too Positive energy Battery disposal condition is fired, and solar battery efficiency can be improved.These slurries can reduce the phase counterdiffusion of Ag/Al, thus Keep solderable to colored belt.Need slurry be it is screen printing and effect be plug-in type replace, will not bring additional It is important to pay and be integrated to immediately in existing production line.
Summary of the invention
It discloses sintered multilayer and stacks (fired multilayer stack).In an embodiment of the invention, Stacking has base, in the metal particle layer in substrate surface at least part, the improvement in substrate surface at least part Metal particle layer, and the improvement intercalation directly at least part of improvement metal particle layer.Improvement intercalation, which has, to be faced Solderable surface far from base.Improveing metal particle layer includes metallic identical with metal particle layer and at least one Material from improvement intercalation.Improve intercalation include noble metal and the material from lower group selection, include: 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, a combination thereof and its alloy, its oxide, its synthetic and its other combinations.In a kind of arrangement In, improvement intercalation includes noble metal and the material from lower group selection, includes: bismuth, boron, indium, lead, silicon, tellurium, tin, vanadium, zinc, group Conjunction and its alloy, its oxide, its synthetic and its other combinations.
In an embodiment of the invention, there are two phase (phase): noble metal phase for improvement intercalation tool (precious metal phase) and insertion phase (intercalation phase).Improvement intercalation greater than 50% can Soldering surfaces may include noble metal phase.Improvement metal particle layer may include metallic discussed above and carry out self-embedding phase At least one material.Be embedded in phase include including from the material of lower group selection: 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, a combination thereof and its alloy, its oxide, its synthetic and its other combinations.Noble metal phase includes from lower group selection At least one material, include: 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 improveing Sub- intercalation (intercalation sublayer) at least part of metal particle layer, and directly sub- intercalation extremely Noble metal sublayer (precious metal sublayer) in few a part.Your gold is the solderable surface for improveing intercalation include Belong to sublayer.Improveing metal particle layer may include metallic discussed above and at least one material from sub- intercalation.For The possibility material of sub- intercalation be described above to insertion phase it is identical.For noble metal sublayer possibility material and above Description is used for the identical of noble metal phase.
In yet another embodiment of the present invention, sintered multilayer, which stacks, has the improvement that metal particle layer is improved as it Aluminum shot sublayer.It has the improvement intercalation there are two sublayer: the 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.Improvement aluminum shot sublayer includes aluminum particulate and also may include at least one material from lower group selection, comprising: aluminum oxide, Bismuth and bismuth oxide.
In one arrangement, at least one dielectric layer is directly at least part of substrate surface.Dielectric layer include from At least one material of lower group selection includes: silicon, aluminium, germanium, gallium, hafnium and oxide, nitride, synthetic and combinations thereof.? In another kind arrangement, alumina medium layer is directly at least part of substrate surface and silicon nitride medium layer is directly aoxidizing On aluminium dielectric layer.
In one arrangement, solid (for example, eutectic (eutectic)) composite layer (compound layer) is directly in base In layer surface.Solid composite layer includes one or more metals from lower group selection, includes: aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, Titanium, and from one or more materials of lower group selection, include: silicon, oxygen, carbon, germanium, gallium, arsenic, nitrogen, indium and phosphorus.
Base's a part on adjacent base layer surface can include doped at least one material from lower group selection: aluminium, copper, Iron, nickel, molybdenum, tungsten, tantalum, titanium, steel and combinations thereof.
In an embodiment of the invention, a part that sintered multilayer stacks has variable thickness.Sintered multilayer heap The folded average peak that can have greater than 12 μm is to Gu Gaodu.
At least 70wt% (weight percent) for improveing the solderable surface of intercalation may include from the material of lower group selection, packet Contain: silver, gold, platinum, palladium, rhodium and alloy, synthetic and its other combinations.
Base may include at least one material from lower group selection, include: silicon, silica, silicon carbide, aluminium oxide, indigo plant Jewel, germanium, GaAs, gallium nitride and indium phosphide.Alternatively, base may include including from the material of lower group selection: aluminium, copper, Iron, nickel, titanium, steel, zinc and alloy, synthetic and its other combinations.Metal particle layer may include from the material of lower group selection, packet 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, include: 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 stacking can have 0 to the contact resistance between 5mOhm, as by What transmission route survey determined.
Directly there can also be colored belt at least part of the solderable surface of improvement intercalation.In one arrangement, Peel strength between colored belt and improvement intercalation is greater than 1N/mm.
In yet another embodiment of the present invention, sintered multilayer, which stacks, has base, in base's at least part Metal particle layer, the improvement metal particle layer in base's at least part, and directly improveing metal particle layer at least Improvement intercalation in a part.Improveing intercalation has two sublayers: directly at least part of improvement metal particle layer Sub- intercalation, and the noble metal sublayer directly at least part 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, which stacks, has silicon base layer, in base's at least part Aluminum shot sublayer, the improvement aluminum shot sublayer in base's at least part, and directly improvement aluminum shot sublayer on improvement insert Layer.Improveing intercalation has two sublayers: the rich bismuth sublayer directly in improvement aluminum shot sublayer, and directly in rich bismuth sublayer Rich silver layer.Improvement aluminum shot sublayer includes at least one material from lower group selection, includes: aluminium, aluminum oxide, bismuth and bismuth oxidation Object.
In an embodiment of the invention, solar battery has silicon base layer, directly in the front surface of silicon base layer At least one front medium layer at least part, multiple fine grid blocks lines in a part of the front surface of silicon base layer (fine grid line), at least one preceding layer (front that converge at least one electrical contact of multiple fine grid blocks lines Busbar layer), aluminum shot sublayer at least part of the rear surface of silicon base layer, and the rear surface in silicon base layer Rear reference lamina (rear tabbing layer) in a part.Reference lamina includes afterwards, in a part of the rear surface of silicon base layer On improvement aluminum shot sublayer, and directly improvement aluminum shot sublayer at least part on improvement intercalation.Improvement intercalation has In face of the solderable surface far from silicon base layer.Improvement 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 thickness between 1 μm to 50 μm 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 has p-type substrate or n-type substrate.Silicon base layer can be polycrystalline silicon wafer, have p-type substrate or n-type substrate.
In an embodiment of the invention, improvement intercalation includes two phases: noble metal phase and insertion 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 In above description.
In yet another embodiment of the present invention, improvement intercalation includes two sublayers: directly in improvement metal particle layer At least part on sub- intercalation, and the noble metal sublayer directly at least part 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 the rich silver layer directly in rich bismuth sublayer.Improveing aluminum shot sublayer further comprises from lower group selection At least one material includes: aluminum oxide, bismuth and bismuth oxide.In one arrangement, improvement aluminum shot sublayer further comprises bismuth And/or bismuth oxide, and bismuth and bismuth add the weight ratio (Bi:(Bi+Al) of aluminium) in improvement aluminum shot sublayer at least than in 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 part of the rear surface of silicon base layer.After be situated between Matter layer includes below one or more: silicon, aluminium, germanium, hafnium, gallium and oxide, nitride, synthetic and combinations thereof.Medium afterwards Layer may include silicon nitride.In another kind arrangement, dielectric layer is directly at least part of silicon base layer rear surface after aluminium oxide And after silicon nitride dielectric layer directly after aluminium 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 of adjacent silicon base layer rear surface further comprises rear surface field, and rear surface field Doped p type is to every cm3Have 1017To 1020Between atom (atoms).
In an embodiment of the invention, a part of rear reference lamina has variable thickness and can have greater than 12 μm Average peak to Gu Gaodu.
Directly there can be colored belt at least part of the solderable surface of improvement intercalation.Solderable surface can be Fu Yin's.Solderable surface may include at least silver of 75wt%.The colored belt of soft soldering to rich silver-colored solderable surface can have greatly In the peel strength of 1N/mm.
A part of improvement aluminum shot sublayer can have variable thickness.A part of improvement aluminum shot sublayer can have greater than 12 μm Average peak to Gu Gaodu.The contact resistance between reference lamina and aluminum shot sublayer can be 0 between 5mOhm, as power transmission line afterwards What drive test amount determined.
In yet another embodiment of the present invention, solar battery has silicon base layer, directly in the front surface of silicon base layer At least part at least one front medium layer, multiple fine grid blocks lines in a part of the front surface of silicon base layer, With at least one electrical contact of multiple fine grid blocks lines at least one before converge layer, at least one of rear surface of silicon base layer Aluminum shot sublayer on point, and the rear reference lamina in a part of the rear surface of silicon base layer.Reference lamina has solderable table afterwards Face.Reference lamina includes the improvement aluminum shot sublayer at least part of silicon base layer rear surface afterwards, directly in improvement aluminum shot sublayer At least part on rich bismuth sublayer, and the rich silver layer directly at least part of rich bismuth sublayer.Improve aluminum shot Sublayer includes aluminum particulate and at least one material from lower group selection, comprising: aluminum oxide, bismuth and bismuth oxide.
In yet another embodiment of the present invention, after solar cell module has 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 herein.Solar battery Also there is module the first battery to interconnect (first cell interconnect) comprising before the first silicon solar cell Converge the first colored belt of both rear reference laminas electrical contact of layer and the second silicon solar cell, rear piece (rear sheet), after Post package layer (rear encapsulant layer) in the rear surface of piece.The first part of post package layer and the first silicon sun Energy battery and the contact of the second silicon solar cell, and the second part 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 may include 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 includes 10wt% between 70wt% Noble metal, at least imbedded particle of 10wt% (intercalating particle) and organic carrier (organic vehicle).Imbedded particle includes aoxidizing from the one or more of lower group selection comprising low temperature substrates metallic, crystalline metal Object 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, include: 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 of noble metal can have the shape of for example spherical, sheet and/or 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.It is embedded in grain A part of son can have the shape of for example spherical, sheet and/or elongated shape.Imbedded particle can have unimodal size distribution or more The distribution of peak size.
Low temperature substrates metallic may include: bismuth, tin, tellurium, antimony, lead and alloy, conjunction At object and its other combinations.In one embodiment, low temperature substrates metallic includes bismuth and has 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 comprising from the material of lower group selection, include: 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 comprising from the material of lower group selection, includes: silica, oxidation Magnesium, boron oxide and any combination thereof.
Crystalline metal oxide particle may include oxygen and the metal from lower group selection, include: bismuth, tin, tellurium, antimony, lead, vanadium, Chromium, molybdenum, boron, manganese, cobalt and alloy, synthetic and its other combinations.
Glass melt grain include including from the material of lower group selection: 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, Alloy, its oxide, its synthetic and its other combinations.
Slurry can have 30wt% to the solids laden between 80wt%.Imbedded particle constitutes slurry at least 15wt%.In one arrangement, slurry include the Ag particle of 45wt%, 30wt% bismuth granule and 25wt% organic carrier. Another kind arrangement in, slurry include the Ag particle of 30wt%, 20wt% bismuth granule and 50wt% organic carrier.Slurry exists 25 DEG C at 4 seconds (sec)-1Shear velocity (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) coating wet metal particle layer, b at least part of substrate surface) the wet metallic of drying Layer, to form dry metal particle layer, c) at least part of dry metal particle layer wet intercalation is directly coated, it is more to be formed Layer heap is folded, d) multiple-level stack and e) combined firing multiple-level stack are dried, 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 packet Containing step: a) coating wet metal particle layer, b at least part of substrate surface) the wet metal particle layer of drying, to form drying Metal particle layer, c) fire dry metal particle layer, to form metal particle layer, d) metal particle layer at least part it is straight Connect and coat wet intercalation, to form multiple-level stack, e) it dries multiple-level stack and f) fires multiple-level stack, to form sintered multilayer It stacks.
In one arrangement, for combined firing method and two kinds of sequential grammar, wet intercalation has 10wt% to 70wt% Between noble metal, at least imbedded particle of 10wt% and organic carrier.Imbedded particle may include from the one of lower group selection Kind is a variety of, melts grain comprising low temperature substrates metallic, crystalline metal oxide particle and glass.Wet metal particle layer may include From the metallic of lower group selection, include: aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, steel and alloy, synthetic and its other groups It closes.
In one arrangement, for combined firing method and two kinds of sequential grammar, there is additional step before step a).It is attached Adding step includes that at least one dielectric layer is deposited at least part of substrate surface.In this arrangement, step a) packet Contain, directly coats wet metal particle layer at least part of dielectric layer.
For combined firing method and two kinds of sequential grammar, each coating step may include from the method for lower group selection, packet It includes: silk-screen printing, intaglio printing (gravure printing), jet deposition (spray deposition), slit coating, 3D Printing and ink jet printing.In one arrangement, step a) includes to carry out silk-screen printing by figuratum silk screen, to generate tool There is the wet metal particle layer of variable thickness.
For combined firing method and two kinds of sequential grammar, step b) and d) may include, lower than 500 DEG C at a temperature of it is dry It is dry between 1 second to 90 minutes, or at a temperature of between 150 DEG C to 300 DEG C it is 1 second to 60 minutes dry between.Step e) can It include to be heated rapidly in air between constant temperature 0.5 second to 60 minutes greater than 600 DEG C, or add rapidly in air Heat to more than constant temperature 0.5 to 3 second of 700 DEG C.
In one arrangement, for combined firing method and two kinds of sequential grammar, include in additional step f), it is more being sintered Soft soldering colored belt in the folded a part of layer heap.
Low temperature substrates metallic, crystalline metal oxide particle, glass melt grain and metal particle layer is being retouched in detail above It states.
In yet another embodiment of the present invention, the method for manufacturing solar battery includes step: silicon wafer a) is provided, B) at least part at the silicon wafer back side coats wet aluminum shot sublayer, c) wet aluminum shot sublayer is dried to form aluminum shot sublayer, d) At least part of aluminum shot sublayer directly coats wet intercalation, to form multiple-level stack, e) drying multiple-level stack, f) in silicon wafer Front surface coat a plurality of fine grid blocks line and at least one before converge layer, g) dry a plurality of fine grid blocks line and at least one before converge Fluid layer with formed 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 includes, after silicon wafer At least one dielectric layer is deposited in at least part on surface.At this in arrangement, step b) includes, at least the one of dielectric layer Directly coat wet aluminum shot sublayer in part.
Each coating step may include the method from lower group selection, comprising: silk-screen printing, intaglio printing, jet deposition, narrow Slot coating, 3D printing and ink jet printing.In one arrangement, step b) includes to carry out silk-screen printing by figuratum silk screen, To generate the wet aluminum shot sublayer with variable thickness.
For combined firing method and two kinds of sequential grammar, step e) and g) may include, lower than 500 DEG C at a temperature of it is dry It is dry between 1 second to 90 minutes, or at a temperature of between 150 DEG C to 300 DEG C it is 1 second to 60 minutes dry between.Step h) can It include to be heated rapidly in air between constant temperature 0.5 second to 60 minutes greater than 600 DEG C, or add rapidly in air Heat to more than constant temperature 0.5 to 3 second of 700 DEG C.
Low temperature substrates metal, crystalline metal oxide particle and glass melt grain in above-detailed.
Detailed description of the invention
When being read in conjunction with the figure to description below exemplary embodiment, those skilled in the art be will be readily appreciated that Aforementioned and other aspects.Attached drawing is not drawn to scale.Attached drawing is only signal and is not intended in detail or limits the present invention.
Attached drawing 1 is the schematic sectional view of the multiple-level stack according to embodiments of the present invention, before firing.
Attached drawing 2 is the schematic sectional view stacked according to embodiments of the present invention, sintered multilayer.
Attached drawing 3 is the schematic sectional view that sintered multilayer stacks, and wherein intercalation (intercalation layer), which has, divides From phase.
Attached drawing 4 is the schematic sectional view that sintered multilayer stacks, and wherein intercalation has the phase for being divided into two sublayers.
Attached drawing 5 is that a part that attached sintered multilayer shown in Fig. 2 stacks schematically is cut according to embodiments of the present invention Face figure.
Attached drawing 6 is according to embodiments of the present invention, the scanning electron microscope (SEM) of joint sintering (co-fired) multiple-level stack Sectional view.
Attached drawing 7 is that the scanning electron microscope (SEM) that there is the joint sintered multilayer of silver-bismuth frit layer (frit layer) to stack is cut Face figure.
Attached drawing 8 is scanning electron microscope (SEM) sectional view of the aluminum shot sublayer on silicon base layer (in SE2 mode).
Attached drawing 9 is scanning electron microscope (SEM) sectional view of the aluminum shot sublayer on attached silicon base layer shown in Fig. 8 (in InLens mould Formula).
Attached drawing 10 is section scanning electron microscope (SEM) of a part of the silicon solar cell stacked comprising joint sintered multilayer Scheme (in InLens mode).
Attached drawing 11 is the scanning of the part of the attached silicon solar cell shown in Fig. 10 stacked comprising joint sintered multilayer Electronic Speculum (SEM) sectional view (in SE2 mode).
Attached drawing 12 is 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.
Attached drawing 13 is the EDX spectrum on the surface according to embodiments of the present invention, comprising the rear reference lamina of aluminium-bismuth intercalation.
Attached drawing 14 shows the x- of the joint sintered multilayer film on the rear reference lamina for being stacked on silicon solar cell Ray scattering pattern.
Attached drawing 15 is according to embodiments of the present invention, includes the multi-layer thin membrane stack of dielectric layer (dielectric layer) The schematic sectional view being stacked in front of firing.
Attached drawing 16 is the schematic cross-sectional of the sintered multilayer stacks of thin films according to embodiments of the present invention, comprising dielectric layer Figure.
Attached drawing 17 is the plan view light micrograph for having occurred that curved joint sintered multilayer stacks of thin films.
Attached drawing 18 is to can be used for the silk screen design during the deposition of wet metal particle layer according to embodiments of the present invention (not proportional drafting).
Attached drawing 19 is that have the dry of the variable thickness for using silk-screen deposition shown in attached drawing 18 according to embodiments of the present invention The schematic section of dry metal particle layer.
Attached drawing 20 be according to embodiments of the present invention, have using silk-screen deposition shown in attached drawing 18 variable thickness and with That is the schematic section of joint sintering improvement metal particle layer.
Attached drawing 21 is the plan view light micrograph that joint sintered multilayer as shown in Fig. 20 stacks.
Attached drawing 22 is the cross-sectional SEM image of a part that there is the sintered multilayer of variable thickness to stack.
Attached drawing 23 is the cross-sectional SEM image with a part of the aluminum particulate film on the silicon base layer of flat thickness.
Attached drawing 24 is the surface topology scanning that there is the sintered multilayer of variable thickness to stack.
Attached drawing 25 is the surface topology scanning of sintered aluminium particle layer.
Attached drawing 26 is the schematic diagram of (or illuminated) side before showing silicon solar cell.
Attached drawing 27 is to show the schematic diagram of the rear side of silicon solar cell.
Attached drawing 28 is the schematic of the solar cell module according to embodiments of the present invention, including sintered multilayer stacking Sectional view.
Attached drawing 29 is to stack the solar-electricity with the colored belt of soft soldering including sintered multilayer according to embodiments of the present invention Scanning electron microscope (SEM) sectional view of the back side in pond.
Attached drawing 30 is the transmission route survey drawing of reference lamina after the silvery on traditional silicon.
Attached drawing 31 is that silver-bismuth intercalation transmission route survey in the aluminum shot sublayer for the rear reference lamina being used as on silicon is drawn Figure.
Specific embodiment
Preferred embodiment is had been illustrated in the background of sintering insertion slurry in metal particle layer.However, this field Technical staff will readily appreciate that material disclosed herein and method have the application under a variety of backgrounds, need herein and half Conductor or conductor material carry out excellent electric contact, especially good attachment, high-performance and low expense and are important.
The whole publications referred to herein are incorporated herein by the reference of all of which content, are used to exist such as it This purpose fully expounded.
The composition and purposes of insertion slurry is disclosed, insertion slurry includes noble metal and imbedded particle, can It is printed in metal particle layer, to change the attribute of metal particle layer after they are sintered to sintered multilayer stacking.? In an embodiment of the invention, insertion slurry can not pass through it for providing solderable surface in metal particle layer Itself soft soldering.Insertion slurry may be additionally used for the adhesion improved fire in multiple-level stack or change metal particle layer and go to a grassroots level Interaction.Insertion slurry can be widely applied 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
Scanning electron microscope (SEM) as used herein and x-ray energy dispersive spectrum (EDX) (collectively referenced as SEM/EDX) use Zeiss Gemini Ultra-55 parses field emission scanning electron microscope, equipped with Bruker6 | 60 detectors are held Row.Details about operating condition is described in each analysis.The cross-sectional SEM image that sintered multilayer stacks passes through ion milling (ion milling) and prepare.Thin epoxy resin layer is painted on the top of sintered multilayer stacking and drying at least 30 minutes.The sample Originally it is then passed to JEOL IB-03010CP ion milling machine, is operated 8 hours in 5kV and 120uA, to be removed from sample edge 80 microns.The sample of milling is stored in nitrogen casing before SEM/EDX.
Term " dry (drying) " describes a kind of heat treatment, or lower than 500 DEG C temperature or lower than 400 DEG C or Lower than 300 DEG C, period between for 1 seconds to 90 minutes or any range being contained therein.Slurry is typically via silk screen Printing or other deposition methods are applied to base, with generation " wet " layer.Wet layer can be dried to reduce or remove volatile organic matter Matter, such as solvent generate " drying " layer.
Term " fire (firing) " describe be higher than 500 DEG C, higher than 600 DEG C or the heating of the temperature higher than 700 DEG C, Period between for 1 seconds to 60 minutes or any range being contained therein.Term " sinter layer (dried layer) " description The drying layer that has been sintered.
Herein using term " multiple-level stack (multilayer stack) " to describe base, thereon with different materials Two or more layers." sintered multilayer stacks (fired multilayer stack) " is that its each layer has been dried and is sintered Multiple-level stack.There are many methods to fire this multiple-level stack.Term " joint sintering (co-firing) " is for describing to multilayer The only once sintered processing stacked.For example, one layer of aluminum particulate slurry is applied to first during silicon solar cell manufacture It base and is dried.Then, mark pulp layer is painted in a part of dry aluminum shot sublayer afterwards, is dried, is brought later Dry aluminum shot sublayer and dry rear reference lamina.During combined firing, two drying layers are burnt simultaneously in one step Knot.Term " sequence sintering (sequential firing) " is for describing the processing being repeatedly sintered to multiple-level stack.In sequence During processing, metallic slurry is painted in base, dries and then sintering.Insertion slurry is then coated in dry and sintered gold In a part for belonging to particle slurry (referred to as metal particle layer).Then, entire multiple-level stack is dried and is sintered for the second time.It should infuse It anticipates and arrives, description joint sintered multilayer stacks or the embodiments of the present invention of structure apply also for the multilayer being sequentially sintered Stacking or structure.
Term " insertion (intercalation) " as used herein is for describing the infiltration of porous material (penetration).In the context of embodiment described herein, 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, the imbedded particle material at least part of metallic is brought Coating (part or all of).Term " improvement metal particle layer (modified metal particle as used herein Layer) " for describing this sintering metal particle layer that the material from imbedded particle has permeated.
In relationship between description adjacent layer, preposition "upper" as used herein means that each layer may or may not be each other Direct physical contact.For example, one layer is said on base, which is positioned to direct neighbor base or indirectly above base Or it is adjacent thereto.Certain layer can have or can between certain layer and base indirectly above base or theory adjacent thereto With none or multiple extra plays.In relationship between description adjacent layer, this preposition used " directly on " meaning Each layer be in direct physical contact with each other.For example, saying on base between one layer, which is positioned to direct neighbor base.
When metal particle layer mainly includes metal A particle, " metal A particle layer " can be described as.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 particle, can be described as " changing Good metal A particle layer ".For example, can be described as improvement aluminum shot sublayer when improveing metal particle layer includes mainly aluminum particulate.
Term " solderable surface (solderable surface) " is known in the art." solderable surface " expression can By the surface of soft soldering to welding.Personnel with ordinary skill are familiar with the change of solderable surface.Generate solderable table The examples of materials in face includes but is not limited to tin, cadmium, gold, silver, palladium, rhodium, copper, zinc, lead, nickel, alloy, a combination thereof, its synthetic And its mixture.In one embodiment, when at least 70wt% on surface including, for example, silver, gold, platinum, palladium, rhodium and its is closed When gold, synthetic and other combined materials, surface is solderable.
Particle described herein can take on any of a number of shapes, size, specific surface area and oxygen content.Particle can be spherical, needle 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 indicates general spherical form, and may include spherical, granular, tubercle Shape, and sometimes irregular shape.Term " thin slice (flake) " indicates thin slice, and sometimes angular, fibrous and not Regular shape.Term " elongated (elongated) " indicate it is acicular and sometimes angular, dendritic, fibrous and Irregular shape, as ISO3252:1999 is defined.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 value limit It is set to a value, the particle of half quantity of one has straight higher than the value with the particle of diameter and half quantity lower than the value Diameter.Measurement particle diameter distribution is typically executed using laser diffraction particle size analyzer, such as Horiba LA-950.For example, Spherical particle disperse in a solvent, wherein they separate well and transmit the distribution of light and be directly linked from being minimal to maximum The size of diameter is distributed.Common approach is to indicate laser diffraction the result is that the D50 value being distributed for report based on volume.Particle size Statistical distribution also can be used 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, which is distributed in particle size distribution, has more than one peak (or vertex).Multimodal particle size distribution can increase powder Tap density (tap intensity) typically brings higher partial veil density (green film density).
In certain embodiments of the present invention, particle can have thin slice or elongated shape as defined above.Thin slice can have There are diameter between 1 μm to 100 μm or between 1 μm to 15 μm and 100nm to the thickness between 500nm.Elongated shape can have 200nm is to the diameter between 100nm and the length greater 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 measure.The ratio of particle disclosed herein and especially silver and bismuth granule Surface area is determined by following test method: being executed using TriStar 3000 (coming from Micromeritics instrument company) BET measurement, is operated based on physical absorption analytical technology.Sample prepares to include degasification, to remove the molecule absorbed.Nitrogen is analysis Gas and helium are used to determine the void volume of sample tube.Micromeritics provides sial (silica alumina), is used for As reference material, it is accompanied by preparation routine and test condition.Measurement starts from increasing the reference material of known quality to sample It manages and sample tube is installed on BET device manifold.Thermostabilization ingredient manifold, sample tube and for measuring saturation pressure (Po) it is special It is drained with pipe.When reaching enough vacuum degrees, manifold is filled with helium (non-absorbing gas) and sample port is opened, with determination 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 executed 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 that nitrogen be allowed to absorb on sample.Some After time, port shutdown reaches balance to allow to absorb.The amount of absorption is that the nitrogen quantity removed from manifold subtracts in sample tube Any residual nitrogen.Along absorption isotherm measurement point be used for calculate reference material with m2The specific area of/g meter；This journey Sequence is repeated by any interested sample, particle for example described herein.
Particle described herein has significant hot attribute: fusing point and/or softening point, the two both depend on the crystallization of material Degree.The fusing point of particle can by using by TA instrument manufacturing 2500 differential scanning calorimeter of DSC carry out differential scanning calorimetry and It is determined using the method described in ASTM E794-06 (2012).The fusing point of crystalline material also warm table and x can be used to penetrate Line diffraction determines.Since 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.
For manufacturing the material of sintered multilayer stacking
In an embodiment of the invention, base, metallic slurry and insertion slurry form sintered multilayer heap It is folded.Base can be solid, plane or rigid material.In one embodiment, base includes from least the one of lower group selection Material is planted, includes: silicon, silica, silicon carbide, aluminium oxide, sapphire, germanium, GaAs, gallium nitride and indium phosphide.This base Layer is commonly used in the deposition of layer, composition transistor, light emitting diode, integrated circuit and photovoltaic cell.Base, which can also be, to be led It is electricity and/or flexible.In another embodiment, base includes at least one material from lower group selection, includes: 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 setting, metallic slurry further includes inorganic bond (inorganic binder), such as frit (glass frit).? In a kind of arrangement, common, 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) sale.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 have 100nm to 100 μm between, 500nm D50 between to 50 μm, between 500nm to 200 μm or in any range for being contained therein.Metallic can have it is spherical, Elongated shape or slice-shaped shape, and can have the distribution of unimodal or multi-modal size.Frit can be contained in metallic slurry on a small quantity In (that is, be less than 5wt%).In one embodiment, metallic slurry include 70wt% to 80wt% aluminum particulate, be less than 2wt% frit and organic carrier.
In an embodiment of the invention, insertion 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 herein further includes organic carrier, although itself and be infrequently expressly stated.
It is embedded in paste composition
In an embodiment of the invention, as described in this, noble metal include from lower group selection at least A kind of material includes: 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 range for being contained therein.In multiple realities It applies in mode, noble metal has from about 0.4 to 7.0m2/ g or from about 1 to 5m2The range of/g is contained therein Specific surface area in any range.Noble metal can have the up to oxygen content of 2wt%；Oxygen can be mixed throughout uniform particle, or Oxygen can find there is the thickness of up to 500nm in oxidation shell.Noble metal can have spherical, elongated shape or slice-shaped Shape, and there is unimodal or multi-modal size to be distributed.Silver particles are commonly used in the Metal slurry in solar industry.In an allusion quotation In type embodiment, at least some noble metals are silver, with the D50 and 1 to 3m between 300nm to 2.5 μm2Between/g Specific surface area.
Term " imbedded particle " works as adjacent other metallics for describing deformable particle when heated When porous layer positions, porous metals particle layer can be at least partly sandwiched, and based on the influence of heating from other metallic phases Separation.In a variety of arrangements, imbedded particle has between 50nm to 50 μm, between 50nm to 10 μm, between 300nm to 5 μm or The D50 in any range 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 4m2The range of/g Or the specific surface area in any range being contained therein.According to an embodiment, imbedded particle is slice-shaped and has big About 1.0 to 3.0m2The specific surface area of/g.Imbedded particle can have spherical, elongated shape or slice-shaped shape, and can have it is unimodal or Multi-modal size distribution.
Here there are three groups of particles, be used as imbedded particle: low temperature substrates metallic (lotemperaturebase 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 does not become with 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) be describe exclusively or substantially include any base metal or metal alloy particle, with low-temperature melting point, That is, being lower than 450 DEG C of fusing point.In some arrangements, LTBM also includes the up to oxygen of 2wt%；Oxygen can be mixed throughout uniform particle, Or oxygen can be found in oxidation shell, have the thickness of up to 500nm, and coat or be partially coated with the particle.Some In arrangement, the fusing point of LTMB is lower, such as less than 350 DEG C or be lower 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 only includes bismuth and with the D50 and 1 to 2m between 1.5 to 4 μm2Specific surface area between/g.
In another embodiment, LTBM imbedded particle is the bismuth core particle surrounded by metal or metal oxide shell. In another embodiment, LTBM imbedded particle is bismuth core particle, is surrounded by monoshell, 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, is silica, magnesia, boron oxide or any combination thereof.Any of these shells can have Have from 0.5nm to 1 μm or thickness of the 0.5nm to 200nm range or comprising any range in the inner.
In another embodiment, imbedded particle is crystalline metal oxide particle.Metal oxide is that have at least The compound of one oxygen atom (oxidation state of anion is -2) and at least one metallic atom.Many metal oxides include more A metallic atom can all be identical or may include various metals.The metal of wide scope with oxygen atom ratio be 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 radiate 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 following metals the oxide of at least one: 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 The low temperature of the temperature of significant phase counterdiffusion can occur in lower than the structure between metallic or between different synthetics for fruit, They start fusing (that is, reaching 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 determine；As sample is heated on its fusing point, diffraction peak reduces and then disappears.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 during firing process and embedding Enter in adjacent porous metals particle layer, generates the metal particle layer of improvement.In an exemplary embodiment, imbedded particle is Crystal bismuth oxide, with the D50 and 1 to 5m between 50nm to 2 μm2Specific surface area between/g.In another embodiment, Crystalline metal oxide particle also includes a small amount of (that is, one or more additional elements less than 10wt%), can adjust 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 lower than 900 DEG C or is lower than 800 DEG C of softening point, this is useful, to effectively deform during firing.In an exemplary embodiment, it is embedded in grain Son is that silicic acid bismuth glass melts grain, with the D50 and 1 to 5m between 50nm to 2 μm2Specific surface area between/g.
Term " organic carrier " describes the mixture or solution of organic chemistry or compound, auxiliary dissolution, dispersion and/ Or the solid component in suspended nitride.For insertion slurry described herein, many different organic carrier mixtures can be used. This organic carrier may or may not include thixotropic agent (thixotrope), stabilizer, emulsifier, thickener, plasticizer, table Face activating agent and/or other common additives.
The ingredient 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 respectively alternately or big (block copolymer) of block.Polysaccharide is usually used polymeric binder, and includes but is not limited to, and alkylcellulose and alkyl spread out Biology such as methylcellulose, ethyl cellulose, propyl cellulose, butyl cellulose, ethylhydroxyethylcellulose, cellulose are derivative Object and its mixture.Other polymeric binders include but is not limited to polyester, polyethylene, polypropylene, and polycarbonate, gathers polyurethane Acrylate (including polymethacrylates and polymethyl methacrylate), polyethylene (including polyvinyl chloride, polyvinyl pyrrole Alkanone, polyvinyl butyral, 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 type, usually in machine process thermally, for example evaporate and removed from slurry.Always For, the solvent that can be used in slurry described herein includes but is not limited to, polarity, nonpolarity, proton, non-proton, fragrant Race, non-aromatic, chlorination and non-chlorinated solvent.The solvent that can be used in slurry described herein includes but is not limited to alcohol, and two First alcohol (including ethylene glycol), polyalcohol (including glycerol), mono- and polyethers are mono- and polyester, alcohol ether, alcohol ester, mono- and disubstituted Adipate ester, mono- 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 branch (including α-, β-, γ-and 4- are loose for saturation and unsaturated alkyl chain (including butane, pentane, hexane, octane number and decane), terpene Oleyl alcohol), 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates (also are known as texanolTM), 2- (2- ethoxyethoxy) 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 ingredient can be adjusted, with distribution or suspension, required carbon content and/or required stream needed for realizing pulp particle Become attribute, as the skilled person will appreciate.For example, addition thixotropic agent, such as can be passed throughCome Change slurry rheology.In another example, it can pass through and to change adhesive and thixotropic agent and consider to occur during annealing Peak value firing temperature, the carbon content fired profile (firing profile) and air-flow and increase or decrease 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 field It is well known, and can determine this ingredient by routine experiment has dosage, to maximize unit efficiency and reliability.In a reality It applies in mode, Metal slurry has at 25 DEG C and at 4 seconds-1Shear velocity under have 10,000 between 200,000cP Viscosity uses the Brookfield RVDV-II+Pro viscosity meter of controlled temperature.
It is embedded in formula of size
The Exemplary compositions range that slurry is embedded according to some embodiments of the present invention is shown in Table I.In multiple realities Apply in mode, insertion slurry have 30wt% between 80wt% solids laden, be embedded in slurry 10wt% to 70wt% it Between noble metal composition, insertion slurry at least 10wt%, 15wt%, 20wt%, 25wt%, 30wt% or 40wt% Imbedded particle composition, and the weight ratio of imbedded particle and noble metal is at least 1:5.In an exemplary embodiment, Noble metal content is 50wt%, and imbedded particle composition is at least 10wt% for being embedded in slurry.In multiple embodiments, Being embedded in the weight ratio of imbedded particle and noble metal in slurry is at least 1:5 or 2:5 or 3:5 or 1:1 or 5:2.
Table I
It is embedded in formula of size, with weight percent (wt%)
Slurry types Noble metal Imbedded particle Organic carrier
It is embedded in slurry (range I) 10-70 10-50 20-70
It is embedded in slurry (range II) 20-50 10-35 30-60
It is embedded in slurry A 50 12.5 37.5
It is embedded in slurry B 45 30 25
It is embedded in slurry C 45 30 25
It is embedded in slurry D 30 20 50
In an embodiment of the invention, for solar cell application, be embedded in slurry include 20 to 50wt% it Between noble metal (that is, in Table I be embedded in slurry range II) and 10 to the imbedded particle between 35wt%, may include LTBM, crystalline metal oxide, frit or combinations thereof.In one embodiment, imbedded particle is bismuth metal particle.Insertion Slurry A (Table I) may include 50wt% silver particles, 12.5wt% bismuth granule and 37.5wt% organic carrier, bring imbedded particle Compare with the 1:4 (weight) of noble metal.Insertion slurry C (Table I) may include 45wt% silver particles, 30wt% bismuth granule and 25wt% organic carrier, the 1:1.5 (weight) for bringing imbedded particle and noble metal compare.When insertion slurry includes silver and bismuth When particle, annotation Ag:Bi is used.
In another embodiment, imbedded particle is that glass melts grain.Being embedded in slurry B (Table I) may include 45wt% silver granuel Son, 30wt% melt grain and 25wt% organic carrier based on the glass of bismuth, bring the 1:1.5 of imbedded particle and noble metal (weight) ratio.In another embodiment, imbedded particle is the mixing that LTBM, crystalline metal oxide particle and glass melt grain Object.Insertion slurry D (Table I) may include 30wt% silver particles, 15wt% bismuth metal particle, 5wt% high lead content glass melt grain and 50wt% organic carrier.The required bulk resistor, contact with that can be adjusted, with realization for special metal layer of insertion slurry Resistance, thickness degree and/or peel strength.
In yet another embodiment of the present invention, formed insertion slurry method comprising steps of provide noble metal, Imbedded particle is provided, and mixes noble metal and imbedded particle in organic carrier.In one arrangement, embedding Enter particle and is added into organic carrier and the mixing in epicyclic mixer (for example, Thinky AR-100), subsequent noble metal (and additional organic carrier, if necessary) is added and mixes in epicyclic mixer.Being embedded in slurry may or may not It is then ground, for example, by using three-high mill (three roll mill) (for example, Exakt 50I).In a kind of arrangement In, insertion slurry includes 10 to the noble metal between 70wt% and greater than the imbedded particle of 10wt%.
Form the method that sintered multilayer stacks
In an embodiment of the invention, the multiple-level stack of sintering includes base, there is at least one clipped wire thereon Sublayer and at least one intercalation.In one embodiment, more using the combined firing process formation sintering comprising following step Layer heap is folded: in substrate surface coated with metal particle layer, dry metal particle layer is direct in a part of dry metal particle layer Coat intercalation, dry intercalation, and then combined firing multiple-level stack.In another embodiment, using including following step Sequence fire process and form sintered multilayer and stack: in substrate surface coated with metal particle layer, dry metal particle layer fires gold Belong to particle layer, intercalation is directly coated in a part of sintering metal particle layer, dry intercalation and then fires multiple-level stack.? In one embodiment, during firing, a part of intercalation is infiltrated into metal particle layer, thus metal particle layer is converted To improve metal particle layer.In some embodiments, each coating step includes the method from the following group independent choice, comprising: Silk-screen printing, intaglio printing, jet deposition, slit coating, 3D printing and ink jet printing.In one embodiment, clipped wire Sublayer is coated onto a part of base by screen-printed metal particle slurry, and intercalation passes through silk screen after by drying Printing insertion slurry is directly applied in a part of metal particle layer.In one embodiment, a part of substrate surface quilt The covering of at least one dielectric layer, and metal particle layer is painted in a part of dielectric layer.
Dry and sintering multiple-level stack form
Attached drawing 1 is to show the schematic of the multiple-level stack 100 before joint sintering according to embodiments of the present invention Sectional view.Dry metal particle layer 120 is directly in a part of base 110.Intercalation 130, by imbedded particle and noble metal grain Son composition, as described above, directly in a part of dry metal particle layer 120.In multiple embodiments of the invention, insert Layer 130 is between 0.25 μm to 50 μm, between 1 μm to 25 μm, between 1 μm to 10 μm or in any range for being contained therein Average thickness.In an embodiment of the invention, intercalation 130 includes noble metal, imbedded particle and optionally has Machine adhesive (it can be retained in after drying in intercalation 130).Before combined firing, noble metal and imbedded particle can It is distributed in intercalation 130 in heterogeneity.In one arrangement, noble metal and imbedded particle (and are being fired after drying It is before) and indeformable, keep their original size and shape.
In an embodiment of the invention, dry metal particle layer 120 is 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, it before combined firing, does 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 typically after drying (and before firing) and indeformable, keeps them Original size and shape.
During firing, adjacent (as shown in 1 lower section of the attached drawing) intercalation 130 of imbedded particle insertion from intercalation 130 is done In a part of 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 purpose disclosed in this.After firing, metal layer 120 is dried Remainder, non-conterminous intercalation and the intercalation metal material for having no or only trace penetrate into wherein, referred to as " metallic Layer ", to purpose disclosed in this.In one arrangement, during firing, the particle in dry metal particle layer 120 can be burnt Knot or fusing, so that metal particle layer has different forms and has smaller porosity than dry metal particle layer 120.Hereafter It will be discussed in more detail occurring the multilayer lamination structure of the change and sintering during firing.
Attached drawing 2 is according to embodiments of the present invention, and showing sintered multilayer stacking 200, (structure 100 of attached drawing 1 is at it After being sintered) schematic sectional view.It includes changing at least part of of adjacent base layer 210 that sintered multilayer, which stacks 200, Improvement (due to firing) intercalation 230 of good (due to firing) metal particle layer 222 and adjacent improvement metal particle layer 222.? At least part noble metal and imbedded particle during firing, 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 form and reduces the hole of improvement intercalation 230 Gap rate.The fusing of at least part imbedded particle and flowing are embedded in adjacent improvement metal particle layer 222, at least part Noble metal (its sinterable or fusing) is moved towards the solderable surface 230S of improvement intercalation 230.Improve metal particle layer 222 include metallic, from intercalation (before firing, it is shown in Figure 1 be 130) in imbedded particle material It is permeated wherein, the dry metal layer 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 fills in improvement metal particle layer 222 Metallic or its can be coated in the metallic that has been in contact with each other in improvement metal particle layer 222.
In some arrangements, there are also metal particle layer 220, almost without or the imbedded particle material of only trace seeped Thoroughly to wherein.In one arrangement, metal particle layer 220 do not contact directly with improvement intercalation 230, and do not include from embedding Enter the increase concentration of the element of particle.In some arrangements, metal particle layer 220 and improvement metal particle layer 222 are burnt in joint The mixture of base 210 is formd with base 210 or adulterated during (not shown) processed.Although attached drawing 2 indicates metallic Sharp boundary between layer 220 and improvement metal particle layer 222, it should be appreciated that boundary is not generally sharp.? In some arrangements, enter the lateral dispersion range of metal particle layer 220 during combined firing by improvement 230 material of intercalation Determine boundary.
In certain embodiments of the present invention, the material in the improvement intercalation 230 in attached drawing 2 is divided into comprising from embedding Enter the phase of the material of particle and the phase of the phase comprising noble metal.Attached drawing 3 is to show sintered multilayer to stack 390 (quite In the structure 200 of attached drawing 2) schematic sectional view, and wherein improvement intercalation 330 have separation phase.Sintered multilayer stacks 390 (only in multiple-level stack region 350) includes the multilayer between a part of base 300 and improvement (during firing) intercalation 330 (during firing) improvement metal particle layer 322 in stack region 350.Metal particle layer 320 comprising metallic 392 exists In the base 300 in adjacent multiple-level stack region 350.
Improveing intercalation 330 includes two phases: noble metal phase 335 and insertion phase 333, and has solderable surface 335S.The solderable surface of most of (at least more than 50%) is made of noble metal phase 335.In some arrangements, noble metal Phase 335 and insertion the phase 333 not fully PHASE SEPARATION during firing, so that there are also 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 intercalation 330 and improvement metal particle layer 322.Interface 322I can not It is size and shape and firing condition that are smooth and depending on metallic 392.In optional frit before firing It is already contained in the embodiment in dry metal particle layer (120 in attached drawing 1), improves metal particle layer 322 and gold Belonging to particle layer 320 also may include a small amount of frit (not shown), and form this layer is less than 3wt%.
In other embodiments, the material phase improved in attached drawing 2 in intercalation 230 is separated to form layered structure.It is attached Fig. 4 is to show sintered multilayer to stack the signal that 400 (structures 200 for being equivalent to attached drawing 2) include the intercalation with two sublayers Property sectional view.Sintered multilayer stack 400 (only in multiple-level stack region 450) include a part of base 410 and improvement ( During firing) improvement (during firing) metal particle layer 422 in multiple-level stack region 450 between intercalation 430.Include gold Belong to the metal particle layer 420 of particle 402 in the base 410 in adjacent multiple-level stack region 450.
Improveing intercalation 430 includes two sublayers: the sub- intercalation 433 directly in improvement metal particle layer 422, and directly Noble metal sublayer 435 on sub- 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 sub- intercalation 433) and change There is interface 422I between top metallic 402 in good metal particle layer 422.Optional frit before firing It is comprised in the embodiment in dry metal particle layer (120 in attached drawing 1), improves metal particle layer 422 and metal Particle layer 420 also may include a small amount of frit (not shown), and form this layer is less than 3wt%.
Cross-sectional SEM image for identification each layer and measure multiple-level stack in thickness degree.Each layer in multiple-level stack it is flat Equal thickness degree is obtained by an average of at least ten thickness measurements, passes through cross-sectional image, and every part is at least 10 μm separations.At this Invention multiple embodiments in, metal particle layer (such as 220 in attached 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 range that is contained therein.In base This metal particle layer be typically it is smooth, on 1x1mm area with average metal particle thickness degree 20% within Minimum and maximum thickness degree.In addition to section SEM, Olympus LEXT is can be used in thickness degree and variation on description area OLS4000 3D laser measurement microscope and/or profilograph (profilometer), such as 150 essence of Veeco Dektak Really measurement.
In an exemplary embodiment, metal particle layer (such as 220 in attached 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 instrument Pascal 140 (low Pressure) or Pascal 440 (high pressure), measured into the range between 2Mpa in 0.01kPa.Sintering metal particle layer can have 1% Between to 50, between 2% to 30%, between 3% to 20% or in which comprising any range in porosity.By aluminum particulate system It obtains and the sintering metal particle layer in application of solar energy can have the porosity between 10% to 18%.
The thickness of sub- intercalation and noble metal sublayer, such as it is respectively schematically shown as 433 and 435 in figure 4, it uses Section SEM/EDX is measured in practical multiple-level stack.Each sublayer is in the contrast differences in SEM due to being embedded between noble metal phase It is different and distinguish.EDX maps (mapping) interface location for identification, 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 what is be contained therein appoints Thickness in what range.In multiple embodiments, sub- intercalation has between 0.01 μm to 5 μm, between 0.25 μm to 5 μm, 0.5 μm to the thickness between 2 μm or in any range for being contained therein.
In an embodiment of the invention, improvement intercalation includes two phases: noble metal phase and insertion phase.This One structure is shown specifically in figure 4.Typically, insertion phase is not solderable, so, if solderable surface 230S is big Part includes noble metal phase, it is useful to ensure solderability.In a variety of arrangements, solderable surface includes to be greater than 50%, the noble metal phase greater than 60% or greater than 70%.In one arrangement, the solderable surface for improveing intercalation is largely wrapped Containing (a variety of) noble metal.Plan view EDX is for determining the concentration of the element on improvement intercalation surface.SEM/EDX uses public above The equipment opened executes, and in the acceleration voltage of 10kV, has 7mm sample operating distance and 500 times of amplifications.In multiple embodiments In, improve intercalation 230 solderable surface 230S 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, Imbedded particle and noble metal type and size all reflect the PHASE SEPARATION degree in improvement intercalation form.
It includes more that metal particle layer (being shown as 222 in attached drawing 2), which is improved, than metal particle layer (being shown as 220 in attached drawing 2) The imbedded particle material of high concentration.It is obtained from the metal particle layer in the section and practical multiple-level stack of improvement metal particle layer The comparison of EDX spectrum can be used to determine the material concentration from improvement intercalation for being embedded in improvement metal particle layer.Above The SEM/EDX equipment of description, operation has 7mm operating distance in 20kV, 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 (insertion metal with Total metal ratio) it is known as IM:M ratio.Baseline EDX analysis executes in the region of metal particle layer, is at least distally from improvement clipped wire 500 μm of sublayer to ensure reproducible measurement.2nd EDX spectrum is obtained from improvement metal particle layer, and comparative spectrum.? In the determination of IM:M ratio, the peak value (that is, the peak value from carbon, sulphur and oxygen is ignored) of metallic element is only considered.When analysis ratio When, noble metal and any metallic element from base are excluded, to prevent insecure result.In an embodiment In, when dry metal particle layer (being shown as 120 in attached drawing 1) includes aluminum particulate and intercalation 130 includes bismuth and silver particles, metal Particle layer (that is, after firing) includes the bismuth of approximation 1wt% and the aluminium greater than 98wt%, the Bi:(Al+Bi with 1:99) (IM:M) compare.Other insertion metal compositions are less than the improvement metal particle layer of 0.25wt%, and are not consider calculating IM:M ratio. In a number of other embodiments, IM:M ratio is 1:106, 1:1000,1:100,1:50,1:25 or 1:10.
But it should be noted that some rough surface of base, it is also coarse for will lead to their interface.Attached drawing 5 be according to According to embodiments of the present invention, a part of this base 510, improvement metal particle layer 522 and improvement intercalation 530 is shown Schematic sectional view.There is non-planar interfaces 501B between base 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 in IM:M ratio, it might be useful to limit this analysis to sample areas 522A, to avoid the falseness as caused by interface roughness As a result.
In exemplary embodiment, the IM:M improved in metal particle layer is (golden in separate improvement than in metal particle layer Belong at least 500 μm of particle layer of region) high 20%, it is high 50%, high 100%, high 200%, high by 500% or high 1000%. In an exemplary embodiment, the intercalation comprising bismuth granule improves metal particle layer (such as in sample in aluminum shot sublayer Analyzed in region, such as be shown as 522A in attached drawing 5) it include the bismuth of 4wt% and the aluminium of 96wt%, the Bi:(Al with 1:25 + Bi) (or IM:M) ratio.Improvement metal particle layer in Bi:(Al+Bi) compare it is high by 400% in metal particle layer.
When intercalation includes crystalline metal oxide and/or frit, it includes when more than one metal, it is embedded in metal component It is quantified by EDX and phase Calais determines IM:M ratio.For example, then this is than being defined as (Bi+ if frit includes bismuth and two kinds of lead Pb):(Bi+Pb+Al)。
In multiple embodiments, sintered multilayer stacking further includes by the metallic in dry metal particle layer and base Between during firing interaction formed solid mixed layer.Solid mixed layer may include but be not limited to, alloy, eutectic, Synthetic, mixture or combinations thereof.In one arrangement, metal particle layer and base are improved and forms solid at their interface Mix (more) region.It may include one or more alloys that solid, which mixes (more) region,.Solid mixing (more) region can be continuously It is (one layer) or semi-continuous.Depending on the synthetic of base and metal particle layer, other mixtures of (more) alloy 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, based on cooling, can bring solid aluminium-silicon (Al-Si) Eutectic Layer in 660 DEG C of eutectics formed above at silicon interface.? In one exemplary embodiment, solid mixture layer is formed in the solid Al-Si Eutectic Layer in silicon base layer a part.Solid The formation of Al-Si Eutectic Layer and form are well known in silicon solar cell.In another embodiment, base 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 provide more aluminium doping Object is known as back surface field to form height p-type doping region in silicon base layer.
Depending on atmospheric conditions, imbedded particle melts and is embedded in the improvement metallic in sintered multilayer stacking with them In layer, multiple phase can be undergone to change.Depending on the material in improvement metal particle layer and base, imbedded particle is embedding with them Enter to improve and yet forms mixed crystal 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 reduces between the metal layer in sintered multilayer stacking Contact resistance.In one embodiment, improvement intercalation and improvement metal particle layer include crystal, by bismuth and oxygen, silicon and At least one of silver and its alloy, synthetic and other combinations composition.
In one embodiment, noble metal phase includes at least one material from lower group selection, includes: gold, silver, Platinum, palladium, rhodium and its alloy, its synthetic and its other combinations.In one arrangement, noble metal phase substantially includes 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 It states as rich in this material.For example, if noble metal phase, layer of precious metal or noble metal sublayer largely include silver, it can quilt It is referred to as the region Fu Yin, rich silver layer or rich silver layer.
Being embedded in phase includes the element from imbedded particle, and also may include the element (for example, oxygen) from external environment On a small quantity from adjacent metal particle layer and during firing near integrator the noble metal of base element. It can be depended in the extensive arrangement of the element in insertion 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), insertion phase includes From at least one material of lower group selection, include: 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), insertion phase include from lower group selection to Lack a kind of material, includes: bismuth oxide, tin, tellurium, antimony, lead, vanadium chromium, molybdenum, boron, manganese, cobalt and its alloy, synthetic and other groups It closes.In another embodiment (when imbedded particle is only frit), insertion phase include 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 It closes.When a kind of main body in composition of these materials insertion region, insertion region is described as rich in this material.For example, such as It largely includes bismuth that fruit, which is embedded in region, intercalation or sub- intercalation, can be hereinafter referred to as rich bismuth region, rich bismuth layer or rich bismuth sublayer.
The example and application that sintered multilayer stacks
Most of metallic comprising aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum and titanium cannot use mild living after firing Property (mildly activated) (RMA) solder flux (fluxes) and solder and soft soldering based on tin.However, in solar battery and In other devices, soft soldering band is highly needed, to be in electrical contact with metal particle layer, such as aluminum shot sublayer.As disclosed herein, it invents Comprising noble metal, such as insertion slurry of silver and gold can be used in metal particle layer and be sintered in air, with generate can The surface of height soft soldering.This is compared with other trials, the solderability of metal particle layer is increased by adding noble metal, due to expensive Firing of the metal based on multiple-level stack and usually diffused into one another with metal particle layer (for example, aluminium), bring comprising considerably less The solderable surface of noble metal, thus good soft soldering.For example, being fired in aluminum shot sublayer commercially available comprising being less than Indicate slurry after the silvery of the frit of 10wt%, solderable surface will not be brought.These layers experienced during the firing step 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, thus, 1) stop noble metal Diffusion and provide solderable surface, 2) mechanical to reinforce metal particle layer and 3) each layer below assisted etch metal particle layer. In an embodiment of the invention, multiple-level stack is formed using insertion slurry comprising the noble metal and bismuth of silvery Imbedded particle made from metal or frit based on bismuth, and the adjacent metal particle layer comprising aluminum particulate.Sintered multilayer heap Folded formation is to pass through: silk-screen printing aluminum slurry (being commonly used in solar cell application) on exposed silicon wafer, dry at 250 DEG C Dry sample 30 seconds, silk-screen printing is embedded in slurry in a part in dry aluminum shot sublayer, sample 30 seconds dry at 250 DEG C, 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 it is greater than 10 DEG C/sec and ramps up and cooling velocity.Whole dryings and the firing step use Despatch CDF 7210 smelting furnaces execute, and are commonly used in silicon solar manufacture.
SEM/EDS analysis is used to determine the elemental composition of the multiple regions in the firing multiple-level stack in the section of polishing and grinds Study carefully insertion process.SEM/EDX is executed using previously described equipment using two kinds of different operation modes.SEM micrograph makes It is shot with Zeiss Gemini Ultra-55 analysis Flied emission SEM using the both of which of referred to as SE2 and Inlens.SE2 mould Formula operates the operating distance in 5-10kV and 5-7mm, uses the second electron detector of SE2 and 10 seconds scan cycle time.It is bright Degree and contrast change between 0 to 50% and between 0 to 60% respectively, in order to maximize between insertion region and Al particle Comparison.Inlens mode operates the operating distance in 1-3kV and 3-7mm, uses the second electron detector of InLens and 10 seconds The scan cycle time.In order to shoot BSF in Inlens mode, brightness is set as 0% and contrast is set as 40% or so.
In an embodiment of the invention, the insertion slurry of the imbedded particle including 10-15wt% stops noble metal Phase counterdiffusion between (that is, silver) and metallic (that is, aluminium).Being embedded in slurry A (showing in Table I) includes 12.5wt% bismuth granule And 50wt%Ag, bring the 1:4 weight ratio of imbedded particle and noble metal.Sintered multilayer stacks system as described above ?.The SEM that sintered multilayer stacks is executed in SE2 mode, using equipment described above, in the acceleration voltage of 5kV, 7mm Operating distance and 4000 times of magnifying powers.
Attached drawing 6 is the scanning electron microscope sectional view that joint sintered multilayer stacks.Intercalation 630 is improved directly in improvement metallic On layer 622.Improveing intercalation 630 includes rich bismuth sublayer 632 (insertion phase) comprising bismuth oxide, and rich silver layer 634 are (expensive Metal).Improveing metal particle layer 622 includes aluminum particulate 621 and insertion phase material 623, is spread from rich bismuth sublayer 632 Place.Rich bismuth sublayer 632 is directly on aluminum particulate 621, at least near interface zone 631.Rich bismuth sublayer 632 seems to prevent Silver is from intercalation 630 and aluminium is improved from the phase counterdiffusion for improveing metal particle layer 622 during combined firing process.Attached drawing 6 is above The example layered described in figure 4.Rich silver layer 634 provide can height soft soldering surface (far from improvement Metal particle layer 622).It is embedded in phase material 623 and not far infiltrating into improves in metal particle layer 622.Improve metallic Most of layer 622 includes aluminum particulate, is feebly sintered together and has the mechanical strength of difference after combined firing.Here There is no available enough bismuth to penetrate deep into improvement metal particle layer 622, and rich bismuth sublayer 632 can be to improvement clipped wire Sublayer 622 applies pressure, mechanically the multiple-level stack of weak joint sintering.The removing of the multiple-level stack of this joint sintering Intensity is lower than 0.4N/mm (Newton per millimeter), with the dominant failure mechanism between Al particle.Need the removing greater than 1N/mm The considered commercial viability of the existing solar industry standard of intensity.
Insertion slurry B (showing in Table I) uses frit as imbedded particle to realize solderable surface.It is embedded in slurry B (insertion) particle and 45wt%Ag are melted based on the glass of bismuth comprising 30wt%, bring the 1 of imbedded particle and noble metal: 1.5 weight ratio.Frit mainly includes bismuth and has 387 DEG C of glass transformation temperature and 419 DEG C of softening point.Sintered multilayer heap Folded SEM is executed in SE2 mode, using equipment described above, in the acceleration voltage of 5kV, the operating distance of 7mm and 4000 Times magnifying power.Attached drawing 7 is the scanning electron microscope sectional view that this joint sintered multilayer stacks according to embodiments of the present invention.Change Good aluminum shot sublayer 722 is the improvement metal particle layer comprising aluminum particulate 730.During combined firing, the frit based on bismuth is simultaneously Not with the complete PHASE SEPARATION of Ag particle, bringing tool, there are two the improvement intercalations 750 of phase: noble metal phase 721 and based on bismuth Insertion phase 740, be similar to attached drawing 3 above shown in.Improve the surface 750S on intercalation 750 includes your gold more than 50% Symbolic animal of the birth year position 721.Surface 750S can be used commonly used in solar cell industry solder flux (for example, Kester 952S, Kester 951 and Alpha NR205) soft soldering.The whole peel strength that sintered multilayer stacks is lower than 0.5N/mm, can be due to base Enter the hyposmosis of improvement aluminum shot sublayer 722 in the insertion phase 740 of bismuth.In general, the form of improvement intercalation can be by changing intercalation In imbedded particle ingredient and load and improve.
Slurry is embedded in stop the counterdiffusion of element phase and strengthen lower metal particle layer
Above example shows two kinds of formula of size, designs your technology (that is, silver) and metallic (that is, aluminium) stopped Between phase counterdiffusion, but their sinter layer lacks enough mechanical strengths when by soft soldering.Insertion slurry C (is shown in Table I Out) comprising 30wt% bismuth granule and 45wt% silver particles (that is, Ag:Bi is embedded in slurry), imbedded particle and noble metal grain are brought The 1:1.5 weight ratio of son.Increased imbedded particle content generates the insertion of higher concentration in improvement metal particle layer in slurry Material, and mechanically stronger sintered multilayer is brought to stack.Insertion slurry C is used as, in BSF, polycrystal, p-type solar battery Manufacture during, after business silvery indicate slurry plug-in type replacement.Insertion slurry C may be additionally referred to as silver (Ag-on- on aluminium Al), indicate or indicate insertion slurry after rear mark, floating.The sintered multilayer heap that one group of characterization tool is used in acquirement is stacked on, thus IM:M (insertion metal: metal) ratio, precious metal surface coverage area is evaluated, and determines in insertion region whether form crystal.
By illustrating the form of the sintered aluminium particle layer on the not silicon base layer of intercalation first, intercalation is in metal particle layer Influence by best illustrated.Attached drawing 8 is this scanning electron microscope of sintered aluminium particle layer 822 in SE2 mode on silicon base layer 810 (SEM) sectional view, along the region for the silicon solar cell for not including intercalation.About 20 μ m-thick of sintered aluminium particle layer 822 and packet 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 It is shown in attached drawing 9.In InLens mode, aluminum shot sublayer 922, aluminum particulate 921 and silicon base layer 910 are high-visible, in addition to this There are also back surface field regions 970 and solidified aluminum-silicon (Al-Si) Eutectic Layer 980.
After combined firing, influence of the intercalation in generation improvement metal particle layer can refer to attached drawing 10 and understand.It is attached Figure 10 is the InLens SEM surface chart for the identical silicon solar cell in image shown in attached drawing 8, but along comprising making The region stacked with insertion slurry C (being shown in Table I) joint sintered multilayer obtained.Joint sintered multilayer stacks 1000 comprising changing Good intercalation 1030, improvement aluminum shot sublayer 1022, the region back surface field (BSF) 1070 for solidifying Al-Si Eutectic Layer 1080, adulterated al With silicon base layer 1010.In an exemplary embodiment, BSF doped p type in silicon base layer to 1017To 1020Every cm3Between.
The SE2 Mode scans Electronic Speculum that the joint sintered multilayer of attached drawing 10 stacks is shown in Figure 11.Although InLens mould Formula clearly illustrates the region BSF, the bismuth (insertion phase) that SE2 mode is preference pattern to reflect in improvement aluminum shot sublayer.Connection It closes sintered multilayer and stacks 1100 comprising improveing 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.The region BSF and solidification Al- are not clearly visible in this image Si Eutectic Layer.Improveing aluminum shot sublayer 112 includes a large amount of bismuth insert material 1103, and aluminum particulate is surrounded during combined firing 1102 insertions.In some instances, the contrast between bismuth and silver will not be sufficiently strong clearly to identify sublayer and bismuth insertion aluminium Degree in particle layer.Mapping in the element of these example sectional views SEM/EDX can be used to obtain, to determine that joint is burnt completely Silver and bismuth position in multiple-level stack processed.
It improves since insertion metal (that is, bismuth) amount of insertion can be determined by comparing EDX spectrum in aluminum shot sublayer, from identical Improvement aluminum particulate layer region and aluminum particulate layer region in cross-section sample carry out.If interregional be spaced each other greater than 1 μm, this is It is the most useful.The mode that this compares is carried out to have been described above as IM:M or Bi:(Bi+Al) ratio.This analysis determine it is embedding Enter slurry and whether is used in the manufacture of solar battery be useful.Metalization layer in solar battery includes limited subgroup Metal, for example including aluminium, silver, bismuth, lead and zinc.In commercial solar cell, aluminum shot sublayer almost entirely includes aluminium.
In one example, the imbedded particle being embedded in slurry C only includes bismuth, and the metallic in metal particle layer is big Part is aluminium.Compare the ratio Bi:(Bi+Al that bismuth and bismuth in aluminum shot sublayer (that is, itself and insertion slurry do not interact) add aluminium) It is useful module determining whether insertion slurry is incorporated into solar battery with improvement aluminum shot sublayer.For this two The EDX spectrum of layer is measured approximation three minutes, using above equipment, under the acceleration voltage of 20kV and the operating distance of 7mm.With The EDX spectrum of sintered aluminium particle layer 822 in attached drawing 8 is collected from region 898.For the improvement aluminum shot sublayer in attached drawing 11 1122 EDX spectrum is collected from region 1199.Element is quantitative spectrally to be executed at these, uses Bruker Quantax 2.0 software of Esprit is used for automatic elemental recognition, background subtraction and peak fitting.EDX spectrum is shown in Figure 12.Aluminium and Bismuth metallic peak area is quantified and calculates the wt% for two layers from the EDX spectrum in attached drawing 12, and in following Table II Middle summary.There is no significant amount of any other metal that can identify in EDX spectrum.Aluminum shot sublayer EDX shown in attached drawing 12A The Bi:(Bi+Al of spectrum generation 1:244) wt% ratio, and improvement aluminum shot sublayer spectrum shown in attached drawing 12B generates the Bi of 1:4: (Bi+Al) wt% ratio, it is such as shown in table ii.Improve aluminum shot sublayer 1122 in Bi:(Bi+Al) wt% ratio about than not with Ag:Bi intercalation contact sintered aluminium particle layer 822 it is 62 times high.In multiple embodiments, sintered multilayer stack in Bi: (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% ratio
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
Concentration of element after plan view EDX can be used to determine in silicon solar cell on the surface of reference lamina.It is looking squarely In figure, EDX probe area surface to about 4 μm or smaller depth, so that this is useful technology, joint is stacked for identification Mutual diffusance in multiple-level stack: higher precious metal concentration means the phase counterdiffusion for having less here, and lower expensive Metal concentration means there are more phase counterdiffusion here.Attached drawing 13 is to insert according to embodiments of the present invention from comprising Ag:Bi The plan view EDX spectrum that the surface of the rear reference lamina of layer carries out.EDX spectrum is collected using SEM, operates the acceleration electricity in 10kV Pressure, 7mm operating distance 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 identifies 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 quantitatively uses 2.0 software of Bruker Quantax Esprit to execute automatically, 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 It is shown in the Table III of text.The overall silver covering on the surface of reference lamina is 96.3 weight percent (wt%) afterwards.
Table III
Indicate the elemental standards weight percent 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 sintering is in the dry metal particle layer based on aluminium Position.XRD can be used for, stacked in intercalation using the sintered multilayer of bismuth granule and using tradition based on silver-colored colored belt, have It is distinguished less than 10wt% frit as between the sintered multilayer stacking of inorganic bond.Using equipped with VANTEC-500 The Bruker ZXS D8Discover GADDS x-ray of area detector and the cobalt x-ray source for operating in 35kV and 40mA is spread out It penetrates instrument and executes XRD.The sintered multilayer shown on the rear colored belt of silicon solar cell in attached drawing 14 stacks XRD diagram case (pattern).Using cobalt K α wavelength in combination for measuring diffraction pattern in two 25 ° of frames of 25-80 ° of total window in 2 Θ.Often A frame measures 30 minutes under x-ray irradiation.Background subtraction is not carried out on two diffraction patterns of attached drawing 14.Pattern quilt Standardization is to meet peak-peak, and 0.01 background is increased to data, thus with log (intensity) drawing.
XRD diffraction pattern is shown, the sintering metal formed using Ag:Bi intercalation stack or solar battery in after Reference lamina has different pattern compared with one of no bismuth formation.XRD diagram case A is on the rear reference lamina of silicon solar cell Joint sintered multilayer stack.It includes improvement intercalation that joint sintered multilayer, which stacks, is formed using insertion slurry, it includes approximations The organic carrier of the silver of 45wt%, the Bi of 30wt% and 25wt% (such as above for the slurry C in Table I).Peak value 1410 identifies For silver and peak value 1420 is bismuth oxide (Bi2O3) crystal.Joint of the XRD diagram case B on the rear reference lamina of silicon solar cell Sintered multilayer stacks, and is formed using commercially available rear mark slurry, and it includes the frits for being less than 10wt%, as aluminum shot Intercalation in sublayer.Joint sintered multilayer stacking be it is dark, indicate significant silver-aluminium phase counterdiffusion.Peak value 1450 identifies 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 It arrives, is accompanied by bismuth oxide mixture, and do not have in pattern B, only observe silver as silver-aluminium alloy part herein.This It further demonstrates, bismuth prevents the mutual expanding in sintered multilayer stacking.In one embodiment, in silicon solar cell Rear reference lamina include bismuth and at least one other element crystal, such as silicon, silver, its oxide, its alloy, its synthetic or Its other combination.In another embodiment, rear reference lamina includes bismuth oxide crystal.In another embodiment, embedding Enter region experienced multiple phase transitions during firing.
Intercalation is etchable during firing to pass through dielectric layer
In the application of some devices, dielectric layer is deposited in substrate surface before deposition of metal, to be passivated base Surface and improvement electrical attributes.Dielectric layer can also prevent the substance phase counterdiffusion between base and adjacent metal particle (more) layer. In some cases, it can highly need to be etching through dielectric layer, so that the mixture between base and metal particle layer is formed, with Improve the electrical conduction between base and metal particle layer.Frit comprising bismuth and lead be it is known, in silicon solar cell Combined firing during be etching through a variety of dielectric layers (for example, silicon nitride).In an exemplary embodiment, it is embedded in slurry D (from Table I above) includes about 30wt% silver, (15wt% bismuth metal particle, 5wt% high lead contain 20wt% imbedded particle Measure frit) and 50wt% organic carrier.It is etching through dielectric layer if necessary, this insertion slurry is particularly useful.
Attached drawing 15 is shown according to embodiments of the present invention, before firing, including is coated at least one dielectric layer The schematic sectional view of the multiple-level stack 1500 of 1513 base 1510.Dry metal particle layer 1520 is the one of dielectric layer 1513 On part.Intercalation 1530, is made of imbedded particle and noble metal, as described above, directly in dry metal particle layer 1520 A part on.Before firing, noble metal and imbedded particle can be distributed in heterogeneity in intercalation 1530.Dielectric layer packet 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 silicon nitride layer of 75nm thickness.In another embodiment, have between dielectric layer 1513 and base 1510 Second dielectric layer (not shown).In one arrangement, second dielectric layer is the aluminium oxide of the 10nm thickness directly in base 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 Deposited metal particle slurry and dry immediately and formed on dielectric layer 1513.In one arrangement, dry metal particle layer 1520 It is 20 μ m-thicks and includes aluminum particulate.Intercalation 1530 includes imbedded particle, such as frit, and it includes lead or bismuths, are deposited on drying In metal particle layer 1520, at least part of dry metal particle layer 1520 is covered, and is subsequently dried.
Attached drawing 16 is to show sintered multilayer according to embodiments of the present invention and stack the 1600 (structures 1500 of attached drawing 15 After it has been sintered) schematic sectional view.A part of base 1610 is coated at least one dielectric layer 1613.Joining It closes during firing, at least some of improvement intercalation 1630 imbedded particle (it includes the frit described with reference to attached drawing 15) fusing And start to flow, it is embedded in improvement metal particle layer 1622.In one arrangement, the glass in improvement intercalation 1630 is molten 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), some metals from improvement metal particle layer 1622 to be allowed chemically and electrically to interact with base 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 can provide structural support.In one arrangement, it is such as described in more detail above with reference to attached drawing 2 , improve the phase that at least part noble metal and imbedded particle in intercalation 1630 form phase with one another separation.? In some arrangements, there are also metallic region 1620 (on dielectric layer 1613), almost without or only trace imbedded particle material Material infiltrates 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
Intercalation will lead to the pressure in following improvement metal particle layer during firing, will lead to bending or corrugation and Electric connection between the layer intensity and layer of difference therefore.For example, intercalation can have it is different from adjacent improvement metal particle layer Thermal expansion coefficient leads to the expansion or shrinkage that each layer is different 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 will lead to the clipped wire of improvement Sublayer and/or the bending of the intercalation of improvement or corrugation.Bending or corrugation can be described as big, the period the or non-week in thickness degree The deviation of phase.In general, which results in the layerings between layer.For example, before the intercalation in dry metal particle layer is sintered, packet The original depth of stacking containing intercalation and dry metal particle layer is throughout approximately uniform.After combined firing, include The thickness that the sintered multilayer of the metal particle layer of the intercalation and improvement of improvement stacks can be up to original depth in some regions Three times.
Attached drawing 17 is the plan view light micrograph for wherein having occurred that curved joint sintered multilayer and stacking.Change Good intercalation 1730 is visible.Improvement intercalation 1730 has been bent；Some peak regions 1712 indicate in figure 17.Adjacent gold Belong to particle layer 1720 not to be bent and keep smooth or near flat.Even if improvement intercalation 1730 has deformed, combine sintering The mechanical integrity of multiple-level stack keeps strong by the peel strength greater than 1N/mm.However, bending meeting so that it with choosing War is connect with being got well when improveing between intercalation 1730 and colored belt (not shown) when them by soft soldering together, firm Touching.The curved surface of improvement intercalation 1730 will lead to incomplete solder in the range of improvement intercalation 1730 and moisten, and can reduce Peel strength and solder bonds reliability.The bending in combined firing multiple-level stack is reduced or eliminated, usefully to ensure into Function soft soldering 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.By forming the pattern of a part of first layer and directly having figure in first layer immediately The second layer is printed on case part and generates variable thickness, to generate 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 are quantified before and after firing.In multiple embodiments, when in 1x1mm area It is middle measurement it have at least 20% be greater than or at least 20% be less than this layer average thickness thickness change when, one layer can be described For with variable thickness.
Attached 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 area 1810, and has area of the pattern 1820.There is figure Case region 1820 includes closing area 1821 and open area 1822.When silk screen is for during the printing of wet metal particle layer, Slurry flows open area 1822 and open mesh area 1810 and be closed area 1821 blocking, cause deposition wet metal Particle layer has variable thickness.In one embodiment, wet metal particle layer is dried immediately to form the dry gold of variable thickness Belong to particle layer, and is embedded in slurry and is deposited directly in the dry metal particle layer of variable thickness.
There are Multiple factors to will affect the variable thickness in dry metal particle layer, such as mesh count, linear diameter and shape, phase To the line angle degree, emulsion (emulsion) thickness and silk screen design of frame.Mesh size and linear diameter have been determined and can be printed Minimum pattern shape and opening.Flowing of the thickness change also by metallic slurry in dry metal particle layer is influenced, It has impact on layer slidings.Slurry can be configured with high viscosity and thixotropy, accurately to control the position that they are deposited in base. It is still possible that changing the size of the thickness change in metal particle layer by adjusting the emulsion thickness of silk screen.Silk screen can be set It is calculated as ensuring in substrate surface continuously drying metal particle layer that there is entirety or only variable layer thickness in a particular area. In an exemplary embodiment, metallic slurry uses 230 mesh screens of the emulsion thickness with 5 μm to print.? In a kind of arrangement, have area of the pattern 1820 have 100 μm by 3mm open area 1822 it is adjacent by 3mm closing area 1821 100 μm of series.There is no limit in terms of types of patterns, period (or lacking it) or size.Many patterns can bring variable thickness, And pattern can be adjusted for a variety of printing conditions and formula of size.
Attached drawing 19 is to be deposited in base 1910 according to embodiments of the present invention using silk screen 1800 shown in attached drawing 18 The schematic section of drying metal particle layer with variable thickness.Dry 1920 lateral area 1925 of metal particle layer is by passing through The 1810 deposited metal particle slurry of open mesh area of silk screen 1800 and immediately dry metallic slurry and formed.Region The dry metal particle layer 1922 of variable thickness in 1925 has area of the pattern 1820 to deposit and with variable by silk screen 1800 Thickness.In the dry metal particle layer 1922 of the variable thickness that is directly printed in region 1925 immediately of insertion slurry and dried with Form intercalation 1930.
Attached drawing 20 is to be deposited according to embodiments of the present invention using silk screen 1800 shown in attached drawing 18 (structure of attached drawing 19) The attached drawing 19 in base 2010 structure its by joint sintering after the drying metallic with variable thickness The schematic sectional view of layer.There is metal particle layer 2020 (from 1920 shape of drying metal particle layer of attached drawing 19 outside region 2025 At).As described above, combined firing causes the material from intercalation 1930 (attached drawing 19) to be embedded in the dry gold of following variable thickness Belong in particle layer 1922 (attached drawing 19), converts variable thickness metal particle layer 1922 as variable thickness and improve metal particle layer 2022 And conversion intercalation 1930 is improvement intercalation 2030.In one arrangement, improvement metal particle layer 2022 has figuratum thickness Degree variation, including but not limited to, period protuberance, ridge, edge and other feature shapes.It should be noted that the thickness of improvement intercalation 2030 Degree is usually unified, and the non-planar interfaces (due to its variable thickness) improveing intercalation and improveing between metal particle layer can The change in total thickness degree by measuring multiple-level stack is inferred.
Attached drawing 21 is the plan view light micrograph that joint sintered multilayer stacks, and wherein metallic slurry is using for example Screen printing shown in attached 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 improves intercalation 2121 to be formed on the top, in the metal of near flat The side every side Shang You of particle layer 2120.Metal particle layer 2120 has planar top surface.The surface of improvement intercalation 2121 is uneven Smooth, there is the pattern for 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 of the invention one In embodiment, a part that joint sintered multilayer stacks has variable thickness.
In order to compare peak value thickness and valley thickness and average layer thickness when useful linear module is to describe variable thickness.? In random layer, there can be some unintentionally thickness changes, but these variations are typically less than average layer thickness 20%.If one layer Thickness change and be less than the 20% of average layer thickness, then the layer is seen as being flat and (has non-uniform thickness).By carefully setting Meter is used for the silk screen of type metal particle slurry, it is possible to generate the layer with variable thickness, have in 1x1mm area Measurement, at least 20% be greater than or at least 20% be less than this layer average thickness thickness change.
Variable thickness in sintered multilayer stacking can be measured from the SEM image of the cross-section sample of polishing.Attached drawing 22 be according to Embodiments of the present invention, the sintered multilayer with variable thickness stack the cross-sectional SEM image of 2210 a part.Cross-section sample Prepared using the above method and is drawn.Sintered multilayer stacks 2210 and includes improvement intercalation 2211, improvement aluminum shot sublayer 2212 and silicon Base 2213.Two interfaces improved on every side of aluminum shot sublayer 2212 identify 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.Also show Solderable surface 2216 out.For comparing, attached drawing 23 shows silicon base layer 2322, has and does not have the flat of variable thickness Aluminum particulate film 2321.
The average thickness of improvement aluminum shot sublayer 2212 in attached drawing 22 is calculated by average thickness measured value.In attached drawing 22 Thickness between two interfaces 2217 and 2218 is passing through sample with regular intervals (for example, 10 microns) measurement.Also 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 entire sintered multilayer and stack.Therefore, 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 sample shown in attached drawing 22, improve aluminum shot sublayer 2212 with 11.3 μm average thickness, 18.4 μm Peak value thickness and 5.2 μm of valley thickness.Peak value thickness bigger than average thickness 64% and valley is smaller than average thickness by 54%.? In multiple embodiments, the layer with variable thickness has bigger than average layer thickness 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 smaller than average layer thickness at least 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 close Seemingly it is parallel to interface 2217.In an embodiment of the invention, the whole for improveing aluminum shot sublayer 2212 is surveyed 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 the comparison of thickness measure for two combination layers has been is only used for improvement aluminum particulate for comparing The thickness measure of layer 2212.For the combination layer in attached drawing 22, peak value thickness is bigger by 44% than 13.2 μm of average integral thickness, and Valley is smaller than average integral thickness by 43%.This alternative systematically can measure the thickness in sintering stacked multilayer in lower section and become Change.
For some applications, only a fraction sintered multilayer stacking is needed with variable thickness.For example, silicon solar cell Aluminum shot sublayer on back side is typically flat.Usefully (it is wrapped the rear reference lamina part on the back side of this battery Include improvement intercalation) in introduce variable thickness.Compare the thickness change and surrounding aluminum shot sublayer a part in rear reference lamina a part In thickness change whether can be used to determine the layer with variable thickness on the back side of solar battery.
Another useful metrics unit for determining the variable thickness in sintered multilayer stacks of thin films is 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 guarantee 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.Profilograph another example is Bruker or Veeco Dektak 150 or equivalents. Olympus LEXT OLS4000 3D measuring microscope can be used to execute for relevant scanning interferometer.Software appended by these methods The difference of average peak to paddy can be calculated automatically.
In an example embodiment, talysurf is used to determine that average peak to Gu Gaodu, is used in identical sample It is stacked in the sintered multilayer with variable thickness and for both aluminum shot sublayers with non-uniform thickness.Veeco Dektak 150 The surface in 1x1mm area is measured for using 12.5mm radius probe, to generate 3D topology surface map.Attached drawing 24 is tool The 3D surface topology map for thering is the sintered multilayer of variable thickness to stack, and attached drawing 25 is with non-uniform thickness (adjacent) aluminum particulate The 3D surface topology map of layer.Brightest area in attached drawing indicates local maximum and most dark areas indicates Local Minimum Value.Attached drawing 24 shows thickness change (from -20.2 μm to 15.9 μm), will be expected to include variable thickness improvement metal The sintered multilayer of particle layer stacks.Attached drawing 25 shows thickness change (from -4.9 μm to 5.5 μm), will be expected to have The aluminum shot sublayer of non-uniform thickness.Average peak to paddy height using program Veeco Vision v4.20 calculate, automatic identification and Average local maximum and minimum value, and then subtract difference.Average peak to sintered multilayer of the paddy height for attached drawing 24 stacks It is 35.54 μm and is 9.51 μm for the aluminium layer of attached drawing 25.In multiple embodiments, when average peak to paddy height is greater than 10 μ M, when being greater than 12 μm or being greater than 15 μm, layer has a variable thickness, and when average peak to paddy height 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 attached drawing 20 when one of showing by soft soldering to colored belt, and peel strength is that the removing that the sintered multilayer without variable thickness stacks is strong Twice of degree.In one arrangement, the improvement intercalation on surface that this variable thickness sintered multilayer stacks is by soft soldering to being based on The colored belt of tin, and they have greater than 1.5N/mm or greater than 2N/mm or greater than the peel strength of 3N/mm.Thickness change It can be optimized, to provide continuous metal particle layer and back surface field in the base 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 stacks.In an exemplary embodiment, when using insertion slurry to be etching through medium When layer, the thickness change in transformation and improvement metal particle layer includes being lower than the region of 20 μm, 10 μm, 5 μm or 2 μ m thicks.
Above-described variable thickness (more) layer, (more) group being used as in any sintered multilayer stacking described herein At.Variable thickness (more) layer, such as variable thickness is dry and improves metal particle layer, can be used in any silicon solar cell On, with the bending of reference lamina after reduction.
Slurry is embedded in as the plug-in type replacement in silicon solar cell
In one embodiment, the noble metal comprising 45wt%, the imbedded particle of 30wt% and 25wt%'s has The insertion slurry of airborne body (slurry C in Table I above) is used as plug-in type replacement (drop in replacement), with Form the rear reference lamina 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 processing flow to manufacture back surface field silicon solar cell, is referred to as " standard c-Si Solar battery ".Referring to " the monocrystalline silicon photovoltaic power generation road-map based on chip: the known skill of use of Goodrich et al. Art improves chance for further decreasing manufacturing expense ", solar energy materials and solar battery (2013), the 110-135 pages, Herein by reference to and merge.In one embodiment, for manufacturing the method for electrode of solar battery comprising steps of providing There is a part of front surface to be coated at least one dielectric layer, coat aluminum shot sublayer at the back side of silicon wafer for silicon wafer, do Dry aluminum shot sublayer coats insertion slurry (rear mark) layer, dry insertion pulp layer, in silicon wafer in a part of aluminum shot sublayer A plurality of fine grid blocks line and confluence layer before at least one, dry and combined firing silicon wafer are coated on dielectric layer in front surface. Such as silk-screen printing, intaglio printing, jet deposition, slit coating, 3D printing and/or inkjet printing method can be used for coating Multiple layers.As an example, Ekra or Baccini screen process press can be used for deposition of aluminum particle layer, insertion pulp layer and Front side grid lines and confluence layer.In another embodiment, solar battery has at least one dielectric layer, covers silicon wafer Rear surface at least part.For PERC (battery (passivated emitter rear cell) after passivation emitter) Framework, after two dielectric layers (that is, aluminium oxide and silicon nitride) are applied to silicon solar cell before the application of aluminum shot sublayer Side.Dry multilayer can be completed in band oven (belt furnace), and constant temperature between 150 DEG C to 300 DEG C 30 seconds is extremely 15 minutes.In one arrangement, 7210 band oven of Despatch CDF is used for dry and combined firing silicon solar cell, It is stacked comprising sintered multilayer described herein.In one arrangement, the completion of combined firing is using rapid heating technique and in sky It is heated in gas between constant temperature 0.5 to 3 second greater than 760 DEG C, is for the normal of aluminum back surface field silicon solar cell With temperature profile (temperature profile).The temperature profile of chip is usually using with the warm for being connected to exposed chip Galvanic coupleSystem calibration.
Attached drawing 26 is the schematic diagram of (or illuminated) side before showing silicon solar cell 2600.Silicon solar cell 26-- has silicon wafer 2610, has at least one dielectric layer (not shown), has fine grid blocks line 2620 and preceding remittance on top Streamline 2630.In one embodiment, the dielectric layer on silicon wafer frontside includes at least one material from lower group selection, packet Siliceous, nitrogen, oxygen, aluminium, gallium, germanium, hafnium, synthetic and combinations thereof.In another embodiment, the dielectric layer on silicon wafer frontside It is silicon nitride and is less than 200nm thickness.The silver metallized slurry in commercially available front side as known in the art may be used to form Fine grid blocks line 2620 and preceding bus bar 2630.It should be noted that front side silver layer is (that is, the fine net as made from silver metallized slurry Ruling 2620 and preceding bus bar 2630) it can be etching through dielectric layer during combined firing and directly contacted with silicon wafer 2610. In one embodiment, silicon wafer 2610 is monocrystalline and doping N-shaped or p-type.In another embodiment, silicon wafer 2610 be polycrystalline and doping N-shaped or p-type.In an exemplary embodiment, base is the polycrystalline p with N-shaped emitter Type silicon wafer.
Attached drawing 27 is to show the schematic diagram of the rear side of silicon solar cell 2700.Rear side be coated with aluminum shot sublayer 2730 and With rear reference lamina 2740, it is distributed on silicon wafer 2710.In one embodiment, the dielectric layer on rear side includes under At least one material of group selection includes: silicon, nitrogen, aluminium, oxygen, germanium, gallium, hafnium, synthetic and its group in silicon wafer front surface It closes.In another exemplary embodiment, the dielectric layer in silicon wafer front surface is silicon nitride and is less than 200nm thickness.One In a embodiment, no dielectric layer on the rear side of silicon wafer.Commercially available aluminum slurry as known in the art can be Fire before be printed on the silicon wafer back side total surface area at least 85% or at least 90% or at least 95% or at least 97%, entire Al covering can be described as.Aluminum shot sublayer (after combined firing) 2730 has flat between 20 to 30 μm Equal thickness.In multiple embodiments, aluminum shot sublayer 2730 has between 3 to 20%, between 10 to 18% or is contained therein Any range porosity.For traditional BSF (back surface field (back surface field)) solar battery framework, Reference lamina is directly applied to silicon wafer afterwards.However, in order to improve the power conversion efficiency of solar battery, 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 of dry aluminum shot sublayer to be formed Reference lamina 2740.Attached 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, rear reference lamina (or improvement is inserted Layer) 2740 with the thickness between 1 μm to 20 μm or between 2 μm to 10 μm or between 2.5 μm to 8 μm.
Above previously described variable thickness metal (aluminium) particle layer, can be used on the back side of silicon solar cell, With the bending of reference lamina after reduction and improve 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, a part for improveing aluminum shot sublayer has and can thicken 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, bring greater than 0.7N/mm, greater than 1.5N/mm, greater than 2N/mm or greater than the peel strength of 3N/mm.Thickness change can It is optimized, to provide continuous metal particle layer and back surface field in the base for silicon solar cell.In another reality It applies in mode, in rear mark layer region, a part of the combination layer (improvement aluminum shot sublayer and rear reference lamina) in that region With the thickness than the average combined thickness degree at least 20%, 30% or 40% greatly that are measured on 1x1mm area.In another reality It applies in mode, in rear mark layer region, a part of the combination layer (improvement aluminum shot sublayer and rear reference lamina) in that region With small at least 20%, 30% or 40% thickness of average combined thickness degree than being measured on 1x1mm area.
In an embodiment of the invention, the solar battery stacked including any sintered multilayer discussed herein can It is incorporated into solar energy module.Here there are many possible solar energy modules designs, which use this solar battery, Just as the skilled person will be aware of.The quantity of solar battery is not intended to be limited in module.Typically, 60 or 72 Each solar battery is merged into commercially available module, but likely merge it is more or fewer, this depend on answer With (that is, consumer electronics, house, business, communal facility, etc.).Module typically comprises by-pass diode (not shown), connects Wire box (not shown) and the braced frame (not shown) for being not directly contacted with solar battery.By-pass diode and terminal box can be with It is the considerations of battery interconnects component.
Attached drawing 28 is that the schematic cross-sectional of a part of solar cell module is shown according to embodiments of the present invention Figure.Solar cell module includes at least one silicon solar cell 2840.The front side 2840F connection 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 back plate 2860 thereon.Colored belt 2832, 2834 adjacent solar batteries connect power contacts to the front side of a battery (that is, the preceding busbar on front side by soft soldering (front busbar)) and adjacent solar battery back side (that is, rear colored belt on back side).It is a large amount of in solar energy module Solar battery can be used colored belt and be electrically coupled together as battery interconnection.
Typical battery interconnection includes that the metal of the metal flag band and connection colored belt in soft soldering to solar battery 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 comprising in the inner appoint The thickness of what range.The width of the colored belt of coated with solder can 0.1 between 10mm, 0.2 between 1.5mm or being contained in it Interior any range.The length of colored belt is determined by application, design and base's size.Solder coat can have 0.5 to 100 μm it Between, the thickness between 10 to 50 μm or in any range for being contained therein.Solder coat may 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 between 1 μm to 1000 μm, 50 to 500 Thickness between μm, between 75 to 200 μm or in any range for being contained therein.Metal flag band may include 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 range in the inner.In one embodiment, colored belt is copper strips, 200 μm Thick and 1mm wide and the tin that 20 μ m-thicks are coated on every side: lead (60:40wt%) solder coat.
Anter 2810 in attached drawing 28 provides some mechanical supports for module and is designed as in silicon solar cell 2840 The optical delivery attribute having had on the part of the solar spectral of absorption.Solar energy module is positioned to so that anter 2810 faces Light source, such as sunlight 2890.Anter 2810 is typically made by low iron content soda-lime glass (soda-lime glass).Before Encapsulated layer 2820 and post package layer 2850 protect silicon solar cell 2840 to pierce during operation far from electric power, chemically and physically Swash.Encapsulation is typically 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 (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.
Back plate 2860 is that silicon solar cell 2840 provides protection, and can be or can not be optically transparent from rear side 's.Solar energy module is positioned to so that back plate 2860 is far from face of light source, such as sunlight 2890.Back plate 2860 can be by three Multilayered structure made from layers of polymer film.DuPontTM Polyvinyl fluoride (polyvinyl fluoride) (PVF) is thin Film 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 can also It is used as rear piece, can assists providing the structural support to solar energy module.Braced frame (not shown) may be additionally used for improving Structural support；Braced frame is typically made by aluminium.
In an embodiment of the invention, the method for being used to form solar cell module is provided.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 includes any sintered multilayers described herein to stack).Then, independent battery by direct soft soldering it Be electrically connected in series to colored belt.Bring structure is known as " battery strings (cell string) ".In general, multiple battery strings cloth It sets on the preceding encapsulated layer for having been applied to anter.These multiple battery strings are connected to each other using bus bar with generation circuit.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 applied To the battery strings of connection 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.Frame 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 It is connected during battery interconnection process in inside modules.
In an embodiment of the invention, the method to form solar energy module is provided, comprising: a) provide at least one A solar battery, with front surface and rear surface；Wherein, rear surface includes that sintered multilayer stacks, b) in rear reference lamina and A part of soft soldering colored belt in a part of preceding confluence layer, to generate battery strings, c) optionally, soft soldering colored belt to bus bar To complete circuit, d) battery strings, e are arranged on the preceding encapsulated layer for having been applied to anter) apply post package layer to battery strings and Piece is to post package layer after connection, 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, whether with determination multiple-level stack as described above It is merged.Piece and post package are after dismounting to expose the rear surface of the mark of solar battery.Solar battery colored belt and Apply fast-curing epoxy resin in surrounding rear surface.From module removing battery and using golden after epoxy resin has been cured Hard rock is sawed to cut off colored belt/solar battery segment.Using previously described ion milling machine with section of polishing, and execute SEM/EDX determines whether structure is as described in embodiments of the present invention.Attached drawing 29 is the back of solar battery The cross-sectional SEM image of the polishing of (not illuminating) side.Sample comes from solar battery (it includes that novel sintered multilayer stacks), It has been incorporated into solar energy module and has then removed as described above.Image shows metal flag band 2932 and its solder applies Layer 2931, soft soldering to sintered multilayer stack 2902.The techonosphere that sintered multilayer stacks 2902 is high-visible.Just applied in solder 2931 lower section of layer is improvement intercalation 2945, improvement metal particle layer 2944 and silicon base layer 2941.The layer identified in attached drawing can make It is more easily identified with EDX.
Other PV battery architectures
Insertion slurry can be used for generating a variety of sintered multilayers stackings, be used as many different solar battery frameworks Front and back sides on metalization layer.As disclosed herein, it is embedded in slurry and sintered multilayer stacking can be used for solar-electricity Pond framework comprising but be not limited to, BSF silicon solar cell, passivation emitter and rear contact (passivated emitter And rear contact) (PERC) solar battery and two-sided fourchette back contact solar cell (bifacial and interdigitated back contact solar cell)。
PERC solar battery framework is based on BSF solar energy framework and improves, by using silicon base layer and back contacts it Between Dielectric (dielectric barrier) and reduce after contact surface recombination.In PERC battery, the back side of silicon wafer A part of (that is, not illuminating) is passivation at least one dielectric layer, to reduce current carrier compound.It is disclosed herein Novel sintered multilayer stacking can be used in PERC solar battery.In one embodiment, Jie on silicon wafer back side 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 back side includes the silicon nitride of the alumina layer of the 10nm thickness on silicon face and the 75nm thickness on alumina layer Layer.The usually used aluminum slurry (for example, monocrystal EFX-39, EFX-85) designed for PERC battery is impermeable by being situated between Matter layer.In order to make aluminum shot sublayer carry out chemical reaction and carry out Ohmic contact with silicon, the small part region of dielectric layer is in aluminum particulate It is removed before layer deposition by laser ablation.
(emitter is passivated back side local diffusion (passivated emitter with rear locally to PERL )) and PERT (passivation emitter, rear (passivated emitter, the rear totally of diffusion completely diffused It diffused is)) two kinds of PERC battery architectures, which further improves equipment performances.Both types are dependent on doping silicon substrate The rear portion of layer is compound to contact after further forbidding, and is used as the role for the back surface field being similar in BSF battery.In PERL In battery, the back side of silicon base layer surrounds the opening in the medium contacted with rear aluminium layer and adulterates.Doping usually by using Boron mixture or the aluminum shot sublayer aluminium contacted after composition are propagated dopant by dielectric openings and are realized, BSF is similar to Manufacture process.PERT battery is similar to PERL, but other than the silicon of the dielectric openings contacted after adjacent contact, with rear medium Whole silicon of layer contact are doped.
In one embodiment, be embedded in slurry, it includes the imbedded particle for not being etching through dielectric layer, be used as PERC, Rear reference lamina on PERL or PERT battery." non-etched (non-etching) " insertion slurry is for providing solderable silver surface With mechanical enhancer lower layer (improvement) aluminum shot sublayer.It includes silicon wafer that bring sintered multilayer, which stacks, is covered at least one Jie Matter layer, improvement aluminum shot sublayer and improvement intercalation；For PERL or PERT, silicon only adulterates or also extends through respectively Jie at dielectric openings Matter interface.The etching of dielectric layer can be further decreased using non-etched insertion slurry and reduces surface recombination.For example, traditionally using The busbar slurry of rear reference lamina in PERC battery is printed directly on dielectric layer and part is etching through dielectric layer, Surface recombination is increased during combined firing.
It is embedding according to an embodiment of the invention for using the battery (that is, PERC, PERL, PERT) of rear dielectric layer Entering slurry can be modified to be etching through the propagation of the silicon area of dielectric layer and assist medium opening doping." etching (etching) " for providing solderable silver surface, mechanical enhancer lower layer (changes for insertion slurry (for example, insertion slurry D in Table I) It is good) aluminum shot sublayer, and it is etching through dielectric layer, silicon face is exposed to aluminum particulate, aluminium is can lead to and is doped into exposed silicon.Band The sintered multilayer come is stacked comprising silicon wafer, improvement aluminum shot sublayer and improvement intercalation.Sintered multilayer stacking can further comprise silicon Surface nearby adulterate Al region (similar to the back surface field in BSF battery), and silicon wafer and improvement aluminum shot sublayer it Between interface solid silicon-aluminium Eutectic Layer.Using insertion slurry be etching through (more) dielectric layer have the advantages that it is a variety of.It is first First, it is in the cheap substitution for being proved to be expensive and insecure laser ablation step in the past.Second, combine when chip and burns When knot, laser ablation often removes the tens of to hundreds of microns of silicon substrate layer material, and can bring between silicon base layer and aluminum shot sublayer Big gap formation.Be sintered insertion slurry not will lead to the change of wafer surface before joint sintering, it is compared with when use When laser ablation, brings and preferably combine formation, the gap of reduction is formed and better reproducibility.
According to an embodiment of the invention, being embedded in slurry can be used for providing the solderable surface of battery structure, Depending on aluminum shot sublayer to carry out Ohmic contact with p-type silicon.The example of these constructions includes fourchette back contact solar cell, n Type BSF battery architecture and double-sided solar battery.In one embodiment, slurry C (coming from Table I) is embedded in be applied to finger On the Al layer for pitching back contact solar framework, such as Zebra battery.For N-shaped BSF framework, have been obtained for complete for Al 20% power conversion efficiency of the battery of portion's covering, insertion slurry can replace the traditional rear mark Ag slurry for directly contacting silicon, Thus reduce the V of solar batteryoc.In a variety of solar battery frameworks based on N-shaped chip, before insertion slurry can be used in On side (that is, illumination side).Insertion slurry may also be combined with the use of Al slurry, to reduce the expense of double-sided solar battery.It is existing Double-sided solar battery framework uses Ag slurry, it includes a small amount of aluminium the Al of 5wt% (for example, be less than), with p-type silicon layer into Row Ohmic contact.Existing two-sided framework uses the silver content of BSF framework almost twice, 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 it) can be printed on Al slurry in double-sided design, and provide mechanical stability and sinterable surface to reduce the use of Ag simultaneously Amount.
The material properties that sintered multilayer stacks and the influence to silicon solar cell.
Including for interested material properties in the sintered multilayer of solar battery and other electronic equipments stacking can be soft Weldering property, peel strength and contact resistance.
Solderability is, lower than 400 DEG C at a temperature of, pass through the fusing brazing metal 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 stacks can It is executed after being heated to 650 DEG C or more in air.Soft soldering include use flux, be fusing solder reflux before clean or Etch the chemical reagent on one or two surface.Be typically used in the solder flux of solar battery, 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 aluminium oxide (Al being formed in when being sintered in air on aluminum particulate2O3) 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 coated with 0.8 to 20mm wide and the metal tape of 100-300um thickness can be dipped into solder flux and drying.It Being placed into the temperature on improvement intercalation and between 200 DEG C to 400 DEG C uses soldering iron (solder iron) by soft soldering.Removing is strong Degree is to separate with soft soldering direction at 180 ° of angles, by the width of soft soldering band, the peeling rate to give, and is removed needed for soft soldering band Power.The soft soldering point (solder joint) formed during soft soldering process has at 1mm/sec is greater than 1N/mm (for example, 2mm Colored belt needs the peeling force greater than 2N to remove soft soldering band) mean peel strength.Solar battery is electrically connected by colored belt It connects, by the rear reference lamina of the preceding busbar of soft soldering to battery and 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.It is marked when using sintered multilayer to stack after When will layer, dominant failure mode can plan view SEM/EDX can be used to determine near the interface Al-Si.It is schematically real at one It applies in mode, when the layer soft soldering of (improvement intercalation) rich silver layer has the colored belt based on tin, peel strength is greater than 1N/mm.
Meier et al. describes how to determine each metal on complete solar battery using four-point probe electrical measurement Change the resistance of layer.Referring to " the determining the ingredient of series resistance from the measurement on the battery of completion " of Meier et al., IEEE (2006), page 2615, by reference to being incorporated herein.The bulk resistor (bulk resistance) of metalization layer directly about The bulk resistor of its material is made.In an embodiment of the invention, the bulk resistor of pure Ag is 1.5x10-8Ω-m；It is used in Pure Ag metalization layer on industrial solar battery, which has, is higher than pure Ag bulk resistor 1.5 again to 5 times of bulk resistor.Bulk resistor for Fine grid blocks line is important, and must upload transmission of electricity stream in the length of relatively long (that is, being greater 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 battery framework, the electric current from metal particle layer flows through improvement gold Belong to particle layer and enters improvement intercalation.Sintered multilayer is stacked, 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 in sintered multilayer stacking between these layers (transmission line measurement) (TLM) (reference: Meier et al., " copper back side convergent belt: crystalline silicon too Ag is eliminated in positive energy battery and module and covers full aluminium ", IEEE PVSC (2015), the 1-6 pages).TLM draw be electrode it Between resistance relative distance.TLM be used in particular for measure contact resistance, 1) metal particle layer and improvement metal particle layer between, And it 2) improves between 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 stacks is the half of the y-intercept value of the linear fit of resistance relative distance measurements.Busbar Between the measurement of resistance use 2410 digital sourcemeter of Keithley (Sourcemeter) that is arranged with four-point probe, ource electric current Between -0.5A to+0.5A and measure voltage.In multiple embodiments, sintered multilayer stack contact resistance 0 to 5mOhm, 0.25 to 3mOhm, 0.3 are between 1mOhm or in any range for being contained therein.The sheet resistance of metal particle layer is logical Line gradient is crossed multiplied by electrode length to determine.Contact resistance is with sheet resistance for numerically determining conveying length contact with therewith Resistance coefficient.Change in series resistance is determined by contact resistance coefficient divided by the area covering of 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 will affect the electrical power conversion of series resistance and solar battery afterwards Efficiency.This contact resistance can be measured by transmission route survey.It is overlapped with 300 μm traditional on the silicon of aluminum shot sublayer The transmission line of electricity of reference lamina is drawn shown in Figure 30 after silver.Improvement intercalation in aluminum shot sublayer, as the defeated of rear reference lamina Electric line is drawn, shown in Figure 31.Y-intercept value in attached drawing 31 is 1.11mOhm, the y-intercept compared in attached drawing 30 0.88 Value.Indicate that the contact resistance between (slotting) layer and aluminum shot sublayer is 0.56mOhm afterwards.For indicating the contact electricity of framework after tradition Resistance is 0.44mOhm.In multiple embodiments, the rear contact resistance indicated between (slotting) layer and aluminum shot sublayer is 0 to 5mOhm Between, 0.25 between 3mOhm or 0.3 between 1mOhm or in any range for being contained therein.The piece of aluminium layer Resistance is determined multiplied by electrode length by line gradient, and is about 9mOhm/ squares (square) in attached drawing 30 and 31.
Although TLM is the accurate preferred side for extracting sintered multilayer and stacking (that is, rear reference lamina and aluminum shot sublayer) contact resistance Method, it is possible to, the contact resistance in the complete sun on battery is determined using four-point probe method.The use of this method passes through, Reference lamina (R after measuring two firstAg-to-Ag) between resistance, and then on Al particle layer (in the 1mm of rear reference lamina) Traveling probe is to obtain RAl-to-Al.Contact resistance passes through RAl-to-AlSubtract RAg-to-AgIt is obtained again divided by 2.This measures that unlike TLM It is accurate, but when being averaged from the measured value of multiple solar batteries, it can be approximate among 0.50mOhm.
Resistance and sheet resistance are used to numerically determine conveying length and contact resistance coefficient therewith.In attached 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 number Estimate divided by the area covering of improvement intercalation.In attached drawing 31, the estimation change in series resistance is 0.023 Ω- cm2, it is equal to 0.020 Ω-cm of the calculating measured in attached drawing 30 for reference lamina after tradition2Series resistance change.String The change of connection resistance can be directly measured, by manufacturing the control BSF (back surface field) with full Al covering and without rear reference lamina Silicon solar cell and manufacture have the BSF silicon solar cell of full Al covering and Ag:Bi intercalation.The series resistance of battery can It is 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 battery 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, more traditional BSF Solar battery with comprising Ag:Bi insertion slurry BSF solar battery and directly measure, as described in this, when two fill When setting rear confluence surface area having the same.Traditional BSF silicon solar cell uses the rear mark slurry based on silver straight Printing is connect to surround on silicon and by aluminum shot sublayer to manufacture.Intercalation (for example, being manufactured using insertion slurry C) is used as having On the silicon solar cell for having the full surface Al covering.The V of two kinds of solar batteriesocPass through the electric current-under a kind of sunlight intensity Voltage tester measures.It is greater than 5cm for having2The solar battery of sign face product 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, being inserted when using After layer architecture replacement tradition when Mark Designing, short-circuit current density (short-circuit current density) (Jsc) and Fill 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, can by executed on complete or incomplete solar battery electroluminescent or photoluminescence measurement come Estimation.JscIncrease and can also have the battery of telescope structure to compare the battery of rear reference lamina directly on silicon to survey by testing Amount.Another benefit is the increase of fill factor, may depend on VocIncrease, contact resistance reduction and/or solar-electricity Compound dynamic change and positive change on rear side of pond.
It is to be understood that invention described herein can be executed by distinct device, material and device, and to setting A variety of modifications of both standby and operating process can be implemented, without departing from the range of the present invention itself.

Claims (23)

1. a kind of sintered multilayer stacks, comprising:
Base with substrate surface；
Metal particle layer in substrate surface at least part, metal particle layer include metallic；
Improvement metal particle layer in substrate surface at least part；And
Improvement intercalation directly at least part of improvement metal particle layer, improvement intercalation have solderable surface, improvement Intercalation includes two sublayers:
Sub- intercalation directly at least part of improvement metal particle layer；And
Noble metal sublayer directly at least part of sub- intercalation；
Wherein, solderable surface includes noble metal sublayer；
Wherein, improvement metal particle layer includes metallic and at least one material from sub- intercalation；And
Wherein, sub- intercalation includes including from the material of lower group selection: antimony, arsenic, barium, bismuth, boron, cadmium, calcium, cerium, caesium, chromium, cobalt, gallium, Germanium, hafnium, indium, iron, lanthanum, lead, lithium, magnesium, manganese, molybdenum, niobium, phosphorus, potassium, rhenium, selenium, silicon, sodium, strontium, sulphur, tellurium, tin, vanadium, zinc, zirconium, oxygen Compound, and combinations thereof.
2. sintered multilayer as described in claim 1 stacks, wherein improvement intercalation includes noble metal and the material from lower group selection Material includes: bismuth, boron, indium, lead, silicon, tellurium, tin, vanadium, zinc, oxide, and combinations thereof.
3. sintered multilayer as described in claim 1 stacks, in which:
Improvement metal particle layer includes aluminum particulate and is improvement aluminum shot sublayer；
Sub- intercalation includes the rich bismuth sublayer directly in the improvement aluminum shot sublayer；And
Noble metal sublayer includes the rich silver layer directly in rich bismuth sublayer；
Wherein, solderable surface includes rich silver layer；
Wherein, improvement metal particle layer further comprises at least one material from lower group selection, includes: aluminum oxide, bismuth, and Bismuth oxide.
4. sintered multilayer as described in claim 1 stacks, further comprise: at least one dielectric layer, directly in base's table In at least part in face, wherein dielectric layer includes including from the material of lower group selection: silicon, aluminium, germanium, hafnium, gallium, oxidation Object, its nitride, and combinations thereof.
5. sintered multilayer as described in claim 1 stacks, further comprise: first medium layer comprising directly in base's table Aluminium oxide and second dielectric layer in at least part in face comprising the silicon nitride directly on first medium layer.
6. sintered multilayer as described in claim 1 stacks, further comprise: directly improveing the solderable surface of intercalation extremely Colored belt in few a part.
7. sintered multilayer as described in claim 1 stacks, further comprise: the solid composite layer directly in substrate surface； Wherein, solid composite layer includes one or more metals from lower group selection, includes: aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, with And one or more materials from lower group selection, include: silicon, oxygen, carbon, germanium, gallium, arsenic, nitrogen, indium and phosphorus.
8. sintered multilayer as described in claim 1 stacks, wherein base's a part on adjacent base layer surface is doped with from the following group The material of selection includes: aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, steel and combinations thereof.
9. sintered multilayer as described in claim 1 stacks, wherein a part that sintered multilayer stacks has variable thickness.
10. sintered multilayer as described in claim 1 stacks, wherein a part that sintered multilayer stacks has greater than 12 μm Average peak is to Gu Gaodu.
11. sintered multilayer as described in claim 1 stacks, wherein base includes at least one material from lower group selection, packet Contain: silicon, silica, silicon carbide, aluminium oxide, sapphire, germanium, GaAs, gallium nitride and indium phosphide.
12. sintered multilayer as described in claim 1 stacks, wherein metal particle layer includes from the material of lower group selection, packet Contain: aluminium, copper, iron, nickel, molybdenum, tungsten, tantalum, titanium, steel, and combinations thereof.
13. sintered multilayer as described in claim 1 stacks, wherein noble metal includes including from the material of lower group selection: silver, Gold, platinum, palladium, rhodium, and combinations thereof.
14. sintered multilayer as described in claim 1 stacks, wherein base includes including from the material of lower group selection: aluminium, Copper, iron, nickel, titanium, steel, zinc, and combinations thereof.
15. sintered multilayer as described in claim 1 stacks, wherein metal particle layer has the thickness between 0.5 μm to 100 μm Degree.
16. sintered multilayer as described in claim 1 stacks, wherein metal particle layer has the porosity between 1 to 50%.
17. sintered multilayer as described in claim 1 stacks, wherein improvement intercalation has the thickness between 0.5 μm to 10 μm.
18. sintered multilayer as described in claim 1 stacks, wherein sintered multilayer is stacked with 0 to the contact between 5mOhm Resistance, as being determined by transmission route survey.
19. sintered multilayer as described in claim 1 stacks, further comprise: soft soldering to the colored belt for improveing intercalation, wherein There is peel strength, and the peel strength is greater than 1N/mm between colored belt and improvement intercalation.
20. sintered multilayer as described in claim 1 stacks, wherein a part for improveing metal particle layer has variable thickness.
21. a kind of sintered multilayer stacks, comprising:
Base；
Metal particle layer in base's at least part, metal particle layer include metallic；
Improvement metal particle layer in base's at least part；And
Improvement intercalation directly at least part of improvement metal particle layer, improvement intercalation have solderable surface；
Wherein, improvement intercalation includes two phases: noble metal phase and insertion phase；
Wherein, the solderable surface greater than 50% includes noble metal phase；
Wherein, improvement metal particle layer includes metallic and at least one material for carrying out self-embedding phase；And
Wherein, insertion phase include including from the material of lower group selection: antimony, arsenic, barium, bismuth, boron, cadmium, calcium, cerium, caesium, chromium, cobalt, Gallium, germanium, hafnium, indium, iron, lanthanum, lead, lithium, magnesium, manganese, molybdenum, niobium, phosphorus, potassium, rhenium, selenium, silicon, sodium, strontium, sulphur, tellurium, tin, vanadium, zinc, zirconium, Oxide, and combinations thereof.
22. sintered multilayer as claimed in claim 21 stacks, wherein improve at least 70wt% packet of the solderable surface of intercalation The material from lower group selection is included, includes: silver, gold, platinum, palladium, rhodium, and combinations thereof.
23. a kind of sintered multilayer stacks, comprising:
Silicon base layer；
Aluminum shot sublayer in silicon base layer at least part；
Improvement aluminum shot sublayer in silicon base layer at least part；And
Improvement intercalation directly in improvement aluminum shot sublayer；
Wherein, improvement intercalation includes two sublayers: the rich bismuth sublayer directly in improvement aluminum shot sublayer, and directly in rich bismuth Rich silver layer on layer；And
Wherein, improvement aluminum shot sublayer includes aluminum particulate and at least one material from lower group selection, comprising: aluminum oxide, bismuth With bismuth oxide.
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