EP2760611A1 - Starting material for a sintered bond and method for producing the sintered bond - Google Patents
Starting material for a sintered bond and method for producing the sintered bondInfo
- Publication number
- EP2760611A1 EP2760611A1 EP12766629.5A EP12766629A EP2760611A1 EP 2760611 A1 EP2760611 A1 EP 2760611A1 EP 12766629 A EP12766629 A EP 12766629A EP 2760611 A1 EP2760611 A1 EP 2760611A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- starting material
- sintered
- flux
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
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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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
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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
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3013—Au as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
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- H—ELECTRICITY
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- H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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- 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
- C22C1/0425—Copper-based alloys
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- 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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
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- H01L2224/29344—Gold [Au] as principal constituent
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Definitions
- the invention relates to a sintered compound, a starting material thereof and a method for the production thereof, furthermore an electronic circuit containing the sintered connection, according to the preamble of the independent
- Power electronics are used in many areas of technology. Especially in electrical or electronic devices in which large currents flow, the use of power electronics is unavoidable. The currents required in the power electronics lead to a self-heating of the electrical or electronic components contained.
- the components of the power electronics can be used in places that are constantly exposed to an elevated temperature. Examples include control devices in the automotive sector, which are arranged directly in the engine compartment or in the gear compartment. In this case, the control unit is also exposed to a constant temperature change, whereby the electrical and / or electronic components contained are subjected to high thermal loads. In general, temperature changes in a range up to a temperature of 200 degrees Celsius are common. However, more and more operating temperatures are increasingly required. As a result, overall increased demands are placed on the reliability and reliability of electrical or electronic devices with power electronics.
- solder joints are known, for example, lead-free solder joints of tin-silver or tin-silver-copper.
- lead-containing soldered joints can be used.
- lead-containing solder joints are severely limited by legal regulations for reasons of environmental protection in terms of their permissible technical applications.
- lead-free brazing alloys are available for use at elevated or high temperatures, in particular above 200 degrees Celsius.
- Lead-free brazing alloys generally have a higher melting point than 200 ° C. The problem with this is that with the use of brazing material to form a bonding layer only a few electrical or electronic components come as joining partners in question, which can withstand the high temperatures during melting of the brazing alloys.
- sintered connections which can be processed at low temperatures and yet are suitable for operation at elevated temperatures.
- the patent application DE 102007046901 AI shows such sintered connections.
- a paste-like starting material comprising readily decomposable silver compounds and silver flakes or nanosilver is used.
- copper may be contained in the starting material, for example.
- Solvents are added to form the paste.
- the silver compounds decompose to form the elemental silver and form together with the silver flakes and the nanosilver, the sintered compound.
- the sintered compound is used to contact two elements. When using the described starting material, the contacting can already take place with low contact pressures of the contacting partners.
- DE 60221433 T2 discloses a sintered compound which is produced from a paste containing particles of a silver compound. In addition to the particles from the silver compound, a reducing agent in dissolved form is also included. At a temperature treatment of the sintering paste below 200 ° C, the silver compound is reduced to the elemental silver to form the
- Metals numerous nano- or micro-sized metallic particles, coatings gen, solvents, additives, reducing agents, crystallization inhibitors, wetting agents and others.
- the invention is based on the object to provide a starting material of a sintered compound, with which a sintered compound can be produced in a simple manner, which generally has good adhesion in particular on copper surfaces and on precious metal surfaces.
- the starting material according to the invention of a sintered compound comprises sinterable particles of at least one metal or at least one metal compound and at least one flux in the function of a reducing agent. Characteristic of the invention is that the flux is at the same time the solvent of the starting material.
- the solvent which is usually provided in a starting material of a sintered compound, replaced by the use of the flux - in particular completely. It should preferably be provided no solvent in addition to the flux in the material.
- the flux contained in the starting material is advantageously capable of reducing (ie, deoxidizing) the surface of a joining partner on which the starting material is applied on sintering, preventing re-oxide formation on the surface before and during the sintering process, and To reduce inclusions of foreign substances.
- the function of the flux differs fundamentally from that of the commonly used solvent, which is by definition inert to the dissolved or dispersed constituents.
- an oxide-free surface of the joining partner is ensured by means of the flux provided in the starting material, so that the sintered connection to be formed adheres to it can.
- the flux is also able to act as a reducing agent with respect to the particles contained in the starting material.
- particles containing a metal compound, in particular an oxide compound are reduced to the elemental metal. In this way, it is ensured that the particles contained in the starting material, in particular at their contact surfaces to each other, have particularly good conditions for sintering.
- rosin rosin-based resin systems or systems based on carboxylic acids
- carboxylic acids having 2-50 carbon atoms and with up to two aromatic rings, such as benzoic acid, citric acid, adipic acid, cinnamic acid and benzylic acid
- Fatty acids for example saturated fatty acids, such as oleic acid, myristic acid, palmitic acid, margaric acid, stearic acid or arachic acid
- dicarboxylic acids for example malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid
- amino acids for example glutamic acid, hydroxycarboxylic acids, for example Lactic acid, naphthols, enols, phenols, amines, such as 6-100 carbon amines, which may preferably be tertiary, alcohols, such as glycol or glycerin.
- the flux is non-volatile at storage temperature, such as room temperature.
- the flux is selected such that a reduction process described above is still below the sintering temperature of the particles contained in the starting material.
- the volume ratio of particles used to flux used in the starting material according to the invention for example, 1: 1. However, it can also be varied, for example, to adjust the viscosity and the sintering properties in a wide range.
- the proportion by weight of the flux based on the total weight of the starting material may for example be between 5% by weight and 40% by weight.
- the proportion of the flux is preferably in the range of 5-20% by weight, more preferably in the range of 7-18% by weight and particularly preferably in the range of 9-16% by weight, based on the weight of the starting material.
- a particularly high thermal and / or electrical conductivity of the sintered compounds produced from the starting material according to the invention then results.
- due to the reduction process only small amounts of gaseous by-products accumulate.
- the sinterable particles are particularly high thermal and / or electrical conductivity of the sintered compounds produced from the starting material according to the invention.
- Suitable metal particles are flakes or powders with particle sizes in the nanometer or micrometer range.
- the sinterable particles may be selected, for example, based on silver, copper or aluminum and mixtures thereof which are readily soluble in one another, such as Cu / Ag, Au / Ag, Cu / Au, Ag / Au, Ag / Pd, and Pd / Pt.
- metal compounds, in particular oxide compounds, of the aforementioned materials are also conceivable.
- the sinterable particles can be coated with an organic material, with an organic metal compound and / or with a metal oxide or with a mixture thereof.
- the coating of the sinterable particles as organic material can be a primary or secondary alcohol, an amine, an organic acid and / or a fatty acid, in particular isostearic acid, stearic acid, oleic acid, lauric acid, myristic acid, palmitic acid, octanoic acid , Decanoic acid or a mixture thereof.
- the reducing effect of the flux can be positively influenced with regard to the surface of the sinterable particles made available in situ.
- a silver carbonate, a silver lactate, a silver stearate or a sodium carbonate is present as the organic metal compound and / or silver oxide or copper oxide as the noble metal oxide, in particular as a coating on the particles.
- these are
- the sintered compound formed in this way from the starting material has a particularly high thermal and / or electrical conductivity.
- the sinterable particles are preferably spherical and / or platelet-shaped.
- a mixture of such particle geometries optionally together with spherical particles allows a high density of the sintered compound formed from the starting material.
- the flux is an organic acid, in particular an aromatic carboxylic acid such as, for example, benzoic acid, formic acid, acetic acid, malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid; Glutamic acid, citric acid, adipic acid, cinnamic acid or lactic acid.
- aromatic carboxylic acid such as, for example, benzoic acid, formic acid, acetic acid, malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid
- Glutamic acid citric acid, adipic acid, cinnamic acid or lactic acid.
- the starting material is preferably provided as a paste.
- the viscosity of the paste is significantly adjustable by the admixed flux or a flux mixture.
- the invention further relates to a sintered compound prepared from a starting material as described above, wherein the sintered compound has an electrical conductivity between 30 MS / m and 45 MS / m, in particular between 36 MS / m and 44 MS / m.
- a sintered compound made of a raw material as described above may have a thermal conductivity between 200 W / mK and 300 W / mK.
- the thermal conductivity of the sintered connection can be between 220 W / mK and 275 W / mK.
- the sintered compound may be a silver sintered compound.
- the silver sintered compound is formed from a starting material containing particles of silver and / or silver compounds and formic acid as a flux.
- formic acid is present in Partially excellent chemical reactivity to oxides and is easy to evaporate residue.
- a silver sintered bonding layer is particularly preferred because silver particles are readily sinterable and processable with excellent electrical and thermal conductivity properties and mechanical properties of the sintered layer.
- the invention further relates to an electronic circuit with a sintered connection as described above, wherein the electronic circuit is the sintered connection as an electrical, thermal and / or mechanical connection of an electronic component to, in particular, a copper component or a component with copper surface.
- a sintered compound which is made from the starting material according to the invention, can achieve a very good adhesion.
- the flux which in particular keeps the copper surface oxide-free during the joining operation, is provided sufficiently and the contacting of the surface to be joined is not disturbed by additionally present solvent, which develops additional volumes of vapor during the joining process.
- the invention further relates to a method for forming a thermally and / or electrically conductive sintered compound.
- a starting material of the type described which is brought between, for example, two joining partners.
- Preferred joining partners are electrical and / or electronic components with contact points, which are brought into direct physical contact with the starting material.
- the starting material can be applied in the form of a printing paste, for example by means of screen or stencil printing on the contact points.
- the order is possible through injection or dispensing.
- the sintered compound by a temperature treatment of the
- the temperature treatment can be in one Step by step or in several steps. Typically, the temperatures in this step in the range of 150 ° C to about 350 ° C, in particular, the components to be joined and their materials represent an upward limiting factor, since a deterioration of the electronic components by the temperature treatment is to be avoided ,
- Bonding partners with contact points made of a noble metal for example gold, silver or an alloy of gold or silver, are preferably provided. More preferably, contact points are provided with a copper surface.
- the flux can then cause a reduction in particular of possible oxides on the surface of the joining partner and / or on the surface of the sinterable particles, which results in improved results of the resulting assembly.
- the flux can dissolve a possibly present coating of the sinterable particles in order to activate them for the subsequent sintering step. This can be done, for example, by the flux catalyzing a combustion reaction of the coating, bringing the coating into the liquid phase and thereby allowing it to evaporate more easily or bonding to the coating to form an inert material.
- the component to be joined can first be immersed in a bath of pure flux at least with the surface to be joined, and then the starting material is provided on the joining surface.
- Fig. 1 shows schematically the starting material according to the present invention in the form of a paste
- Fig. 2 shows schematically an electronic circuit according to the present invention.
- FIG. 1 schematically shows a starting material 100 of a sintered compound 12 according to the present invention in paste form, which comprises sinterable particles 102 of at least one metal or at least one metal compound and at least one flux 103.
- the flux 103 is at the same time the solvent of the starting material 100, which can advantageously be used in particular on copper surfaces.
- the sinterable particles 102 may in particular contain silver, gold, platinum, palladium and / or copper and have an optional coating 105 which is formed from an organic material, with an organic metal compound and / or with a metal oxide or a mixture thereof.
- the optional coating 105 of the sinterable particles 102 may contain as organic material a primary or secondary alcohol, an amine, an organic acid and / or a fatty acid, in particular isostearic acid, stearic acid, oleic acid, lauric acid or a mixture thereof.
- the coating 105 may contain silver carbonate, silver lactate, silver stearate or sodium carbonate, and as the metal oxide, the optional coating 105 of the sinterable particles 102 may include, in particular, silver oxide or copper oxide.
- the flux 103 is preferably an organic acid, in particular an aromatic carboxylic acid, such as benzoic acid, formic acid, acetic acid, citric acid, adipic acid, cinnamic acid, a dicarboxylic acid, such as malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid; an amino acid such as glutamic acid, a hydroxycarboxylic acid acid, such as lactic acid, or a naphthol, enol or phenol, and preferably liquid or liquefiable at drying or sintering temperatures.
- aromatic carboxylic acid such as benzoic acid, formic acid, acetic acid, citric acid, adipic acid, cinnamic acid, a dicarboxylic acid, such as malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid
- an amino acid such as glutamic acid, a hydroxycarboxylic
- FIG. 2 schematically shows an electronic circuit with a sintered connection 112 made of the starting material of the present invention, the electronic circuit comprising the sintered connection 112 as electrical, thermal and / or mechanical connection of an electronic component 110 to, in particular, a copper component or a component with a copper surface 1 11 includes.
- the starting material for the sintered compound 1 12 is in the form of a printing paste or an ink-jet ink or as a molded part and was applied with a printing or adhesive or with a lamination process on the components to be joined 11 1 and 1 10 or contacted with these. Subsequently, the sintered compound 1 12 is formed by temperature and / or pressurization of the starting material.
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Abstract
The invention relates to a sintered bond, a starting material for the same and a method for the production thereof, but also to an electronic circuit containing the sintered bond, wherein the starting material comprises sinterable particles (102) of at least one metal or at least one metal compound and at least one flux (103). According to the invention, the flux (103) is a reducing agent and at the same time the solvent of the starting material (100).
Description
Beschreibung description
Titel title
Ausgangswerkstoff einer Sinterverbindung und Verfahren zur Herstellung derStarting material of a sintered compound and method for producing the
Sinterverbindung sintered connection
Die Erfindung betrifft eine Sinterverbindung, einen Ausgangswerkstoff derselben und ein Verfahren zu deren Herstellung, weiterhin eine die Sinterverbindung ent- haltende elektronische Schaltung, gemäß dem Oberbegriff der unabhängigenThe invention relates to a sintered compound, a starting material thereof and a method for the production thereof, furthermore an electronic circuit containing the sintered connection, according to the preamble of the independent
Ansprüche. Claims.
Stand der Technik State of the art
Leistungselektronik wird in vielen Bereichen der Technik eingesetzt. Gerade in elektrischen oder elektronischen Geräten, in welchen große Ströme fließen, ist der Einsatz von Leistungselektronik unumgänglich. Die in der Leistungselektronik notwendigen Stromstärken führen zu einer Eigenerwärmung der enthaltenen elektrischen oder elektronischen Komponenten. Zusätzlich können die Komponenten der Leistungselektronik an Orten eingesetzt sein, die ständig einer erhöhten Temperatur ausgesetzt sind. Als Beispiele sind Steuergeräte im Automobilbereich zu nennen, die unmittelbar im Motorraum oder im Getrieberaum angeordnet sind. Dabei ist das Steuergerät außerdem einem ständigen Temperaturwechsel ausgesetzt, wodurch die enthaltenen elektrischen und/oder elektronischen Komponenten thermisch stark belastet werden. Im Allgemeinen sind Temperaturwechsel in einem Bereich bis zu einer Temperatur von 200 Grad Celsius üblich. Es werden jedoch zunehmend auch darüber hinaus gehende Einsatztemperaturen gefordert. Dadurch werden insgesamt erhöhte Anforderungen an die Zuverlässigkeit und die Funktionssicherheit von elektrischen oder elektronischen Geräten mit Leistungselektronik gestellt. Power electronics are used in many areas of technology. Especially in electrical or electronic devices in which large currents flow, the use of power electronics is unavoidable. The currents required in the power electronics lead to a self-heating of the electrical or electronic components contained. In addition, the components of the power electronics can be used in places that are constantly exposed to an elevated temperature. Examples include control devices in the automotive sector, which are arranged directly in the engine compartment or in the gear compartment. In this case, the control unit is also exposed to a constant temperature change, whereby the electrical and / or electronic components contained are subjected to high thermal loads. In general, temperature changes in a range up to a temperature of 200 degrees Celsius are common. However, more and more operating temperatures are increasingly required. As a result, overall increased demands are placed on the reliability and reliability of electrical or electronic devices with power electronics.
Üblicherweise erfolgt eine Anbindung von elektrischen oder elektronischen Komponenten - beispielsweise auf ein Trägersubstrat - durch eine Verbindungsschicht. Als eine derartige Verbindungsschicht sind Lotverbindungen bekannt, beispielsweise bleifreie Lotverbindungen aus Zinn-Silber oder Zinn-Silber-Kupfer.Usually, a connection of electrical or electronic components - for example, to a carrier substrate - by a connecting layer. As such a bonding layer solder joints are known, for example, lead-free solder joints of tin-silver or tin-silver-copper.
Bei höheren Einsatztemperaturen sind bleihaltige Lotverbindungen einsetzbar.
Bleihaltige Lotverbindungen sind jedoch durch gesetzliche Bestimmungen aus Gründen des Umweltschutzes hinsichtlich ihrer zulässigen technischen Anwendungen stark beschränkt. Alternativ bieten sich für den Einsatz bei erhöhten bzw. hohen Temperaturen, insbesondere über 200 Grad Celsius, bleifreie Hartlote an. Bleifreie Hartlote weisen in der Regel einen höheren Schmelzpunkt als 200°C auf. Problematisch daran ist, dass bei der Verwendung von Hartlot zur Ausbildung einer Verbindungsschicht nur wenige elektrische oder elektronische Komponenten als Fügepartner in Frage kommen, die den hohen Temperaturen beim Schmelzen der Hartlote standhalten können. At higher operating temperatures, lead-containing soldered joints can be used. However, lead-containing solder joints are severely limited by legal regulations for reasons of environmental protection in terms of their permissible technical applications. Alternatively, lead-free brazing alloys are available for use at elevated or high temperatures, in particular above 200 degrees Celsius. Lead-free brazing alloys generally have a higher melting point than 200 ° C. The problem with this is that with the use of brazing material to form a bonding layer only a few electrical or electronic components come as joining partners in question, which can withstand the high temperatures during melting of the brazing alloys.
Eingesetzt werden auch Sinterverbindungen, die bereits bei niedrigen Temperaturen verarbeitet werden können und die dennoch für einen Betrieb bei erhöhten Temperaturen geeignet sind. So zeigt die Patentanmeldung DE 102007046901 AI derartige Sinterverbindungen. Zur Herstellung einer Sinterverbindung wird ein pastenförmiger Ausgangswerkstoff umfassend leicht zersetzbare Silberverbindungen sowie Silberflocken oder Nanosilber verwendet. Weiterhin kann im Ausgangswerkstoff beispielsweise Kupfer enthalten sein. Zur Ausbildung der Pastenform werden Lösungsmittel beigemischt. Bei einer Temperaturbehandlung des Ausgangswerkstoffs unter 300°C zersetzen sich die Silberverbindungen unter Ausbildung des elementaren Silbers und bilden zusammen mit den Silberflocken und dem Nanosilber die Sinterverbindung aus. Die Sinterverbindung wird eingesetzt zum Kontaktieren zweier Elemente. Die Kontaktierung kann bei einer Verwendung des beschriebenen Ausgangswerkstoffes bereits mit niedrigen Anpressdrücken der Kontaktierungspartner erfolgen. Also used are sintered connections, which can be processed at low temperatures and yet are suitable for operation at elevated temperatures. Thus, the patent application DE 102007046901 AI shows such sintered connections. To produce a sintered compound, a paste-like starting material comprising readily decomposable silver compounds and silver flakes or nanosilver is used. Furthermore, copper may be contained in the starting material, for example. Solvents are added to form the paste. At a temperature treatment of the starting material below 300 ° C, the silver compounds decompose to form the elemental silver and form together with the silver flakes and the nanosilver, the sintered compound. The sintered compound is used to contact two elements. When using the described starting material, the contacting can already take place with low contact pressures of the contacting partners.
Die DE 60221433 T2 offenbart eine Sinterverbindung, die aus einer Paste hergestellt wird, welche Partikel aus einer Silberverbindung enthält. Neben den Partikeln aus der Silberverbindung ist auch ein Reduktionsmittel in gelöster Form enthalten. Bei einer Temperaturbehandlung der Sinterpaste unterhalb von 200°C wird die Silberverbindung zum elementaren Silber reduziert unter Bildung derDE 60221433 T2 discloses a sintered compound which is produced from a paste containing particles of a silver compound. In addition to the particles from the silver compound, a reducing agent in dissolved form is also included. At a temperature treatment of the sintering paste below 200 ° C, the silver compound is reduced to the elemental silver to form the
Sinterverbindung. Sintered connection.
Die US 6,951 ,666 zeigt die Herstellung unterschiedlicher Sinterverbindungen. Dabei werden allgemeine Kombinationsmöglichkeiten verschiedener Ausgangs- elemente beschrieben. Als Ausgangselemente sind unter Anderem molekulareUS Pat. No. 6,951,666 shows the preparation of different sintered compounds. Here, general combinations of different starting elements are described. As starting elements are, inter alia, molecular
Metalle, zahlreiche metallische Partikel in Nano- oder Mikrogröße, Beschichtun-
gen, Lösungsmittel, Additive, reduzierende Mittel, Kristallisationshemmer, Benetzungsmittel und weitere genannt. Metals, numerous nano- or micro-sized metallic particles, coatings gen, solvents, additives, reducing agents, crystallization inhibitors, wetting agents and others.
Offenbarung der Erfindung Disclosure of the invention
Der Erfindung liegt die Aufgabe zu Grunde, einen Ausgangswerkstoff einer Sinterverbindung bereitzustellen, mit welchem in einfacher Weise eine Sinterverbindung hergestellt werden kann, welche insbesondere auf Kupferoberflächen und auf Edelmetalloberflächen allgemein eine gute Haftung aufweist. The invention is based on the object to provide a starting material of a sintered compound, with which a sintered compound can be produced in a simple manner, which generally has good adhesion in particular on copper surfaces and on precious metal surfaces.
Diese Aufgabe wird durch eine Sinterverbindung, einen Ausgangswerkstoff derselben und ein Verfahren zu deren Herstellung, weiterhin durch eine die Sinterverbindung enthaltende elektronische Schaltung mit den kennzeichnenden Merkmalen der unabhängigen Ansprüche gelöst. This object is achieved by a sintered compound, a starting material thereof and a process for their preparation, further by an electronic circuit containing the sintered compound having the characterizing features of the independent claims.
Der erfindungsgemäße Ausgangswerkstoff einer Sinterverbindung umfasst sinterbare Partikel aus mindestens einem Metall oder mindestens einer Metallverbindung und mindestens ein Flussmittel in der Funktion eines Reduktionsmittels. Kennzeichnend für die Erfindung ist, dass das Flussmittel zugleich das Lösungsmittel des Ausgangswerkstoffs ist. The starting material according to the invention of a sintered compound comprises sinterable particles of at least one metal or at least one metal compound and at least one flux in the function of a reducing agent. Characteristic of the invention is that the flux is at the same time the solvent of the starting material.
Mit anderen Worten wird das Lösungsmittel, welches üblicherweise in einem Ausgangswerkstoff einer Sinterverbindung vorgesehen ist, durch die Verwendung des Flussmittels - insbesondere vollständig - ersetzt. Es soll bevorzugt kein Lösungsmittel zusätzlich zum Flussmittel im Werkstoff vorgesehen sein. In other words, the solvent, which is usually provided in a starting material of a sintered compound, replaced by the use of the flux - in particular completely. It should preferably be provided no solvent in addition to the flux in the material.
Das in dem Ausgangswerkstoff enthaltene Flussmittel ist in vorteilhafter Weise in der Lage, die Oberfläche eines Fügepartners, auf welcher der Ausgangswerkstoff aufgetragen ist, beim Sintern zu reduzieren (d. h. zu entoxidieren), die erneute Oxidbildung vor und während des Sintervorgangs auf der Oberfläche zu verhindern und Einschlüsse von Fremdstoffen zu verringern. Hierin unterscheidet sich die Funktion des Flussmittels grundlegend von der des üblich eingesetzten Lösungsmittels, welches definitionsgemäß inert ist gegenüber den gelösten oder dispergierten Bestandteilen. In vorteilhafter Weise ist mittels dem im Ausgangs- werkstoff vorgesehene Flussmittel eine oxidfreie Oberfläche des Fügepartners sichergestellt, so dass die auszubildende Sinterverbindung an dieser anhaften
kann. Ferner ist das Flussmittel in der Lage auch gegenüber den im Ausgangswerkstoff enthaltenen Partikeln als Reduktionsmittel zu wirken. Bevorzugt werden Partikel, enthaltend eine Metallverbindung, insbesondere eine Oxidverbindung, zum elementaren Metall reduziert. Auf diese Weise ist sichergestellt, dass die im Ausgangswerkstoff enthaltenen Partikel, insbesondere an ihren Kontaktflächen zueinander, besonders gute Voraussetzungen zum Versintern aufweisen. The flux contained in the starting material is advantageously capable of reducing (ie, deoxidizing) the surface of a joining partner on which the starting material is applied on sintering, preventing re-oxide formation on the surface before and during the sintering process, and To reduce inclusions of foreign substances. Here, the function of the flux differs fundamentally from that of the commonly used solvent, which is by definition inert to the dissolved or dispersed constituents. Advantageously, an oxide-free surface of the joining partner is ensured by means of the flux provided in the starting material, so that the sintered connection to be formed adheres to it can. Furthermore, the flux is also able to act as a reducing agent with respect to the particles contained in the starting material. Preferably, particles containing a metal compound, in particular an oxide compound, are reduced to the elemental metal. In this way, it is ensured that the particles contained in the starting material, in particular at their contact surfaces to each other, have particularly good conditions for sintering.
Durch die in den abhängigen Ansprüchen aufgeführten Maßnahmen sind vorteilhafte Weiterbildungen und Verbesserungen des im unabhängigen Anspruch angegebenen Ausgangswerkstoffs möglich. The measures listed in the dependent claims advantageous refinements and improvements of the independent claim specified starting material are possible.
Als Flussmittel können beispielsweise Kolophonium, auf Kolophonium basierende Harzsysteme oder Systeme auf der Basis von Carbonsäuren eingesetzt werden, wie zum Beispiel Carbonsäuren mit 2-50 C-Atomen und mit bis zu zwei aromatischen Ringen, wie Benzoesäure, Zitronensäure, Adipinsäure, Zimtsäure und Benzylsäure, Fettsäuren, wie zum Beispiel gesättigte Fettsäuren, wie Ölsäure, Myristinsäure, Palmitinsäure, Margarinsäure, Stearinsäure oder Arachinsäure, Dicarbonsäuren, wie zum Beispiel Malonsäure, Maleinsäure, Octan-, Nonan-, Dodecansäure, Aminsäuren wie zum Beispiel Glutaminsäure, Hydroxycarbon- säuren wie zum Beispiel Milchsäure, Naphtholen, Enolen, Phenolen, Aminen, wie zum Beispiel Amine mit 6-100 C-Atomen, die vorzugsweise tertiär sein können, Alkohole, wie zum Beispiel Gylkol oder Glycerin. As a flux, for example rosin, rosin-based resin systems or systems based on carboxylic acids can be used, such as carboxylic acids having 2-50 carbon atoms and with up to two aromatic rings, such as benzoic acid, citric acid, adipic acid, cinnamic acid and benzylic acid, Fatty acids, for example saturated fatty acids, such as oleic acid, myristic acid, palmitic acid, margaric acid, stearic acid or arachic acid, dicarboxylic acids, for example malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid, amino acids, for example glutamic acid, hydroxycarboxylic acids, for example Lactic acid, naphthols, enols, phenols, amines, such as 6-100 carbon amines, which may preferably be tertiary, alcohols, such as glycol or glycerin.
Vorzugsweise ist das Flussmittel bei Lagerungstemperatur, wie beispielsweise Raumtemperatur, nicht flüchtig. Bevorzugt ist das Flussmittel derart ausgewählt, dass ein oben beschriebener Reduktionsvorgang noch unterhalb der Sintertemperatur der im Ausgangswerkstoff enthaltenen Partikel einsetzt. Preferably, the flux is non-volatile at storage temperature, such as room temperature. Preferably, the flux is selected such that a reduction process described above is still below the sintering temperature of the particles contained in the starting material.
Das Volumenverhältnis von eingesetzten Partikel zu verwendetem Flussmittel beträgt in dem erfindungsgemäßen Ausgangswerkstoff beispielsweise 1 : 1. Es kann aber auch beispielsweise zur Anpassung der Viskosität und der Sintereigenschaften in weitem Rahmen variiert werden. The volume ratio of particles used to flux used in the starting material according to the invention, for example, 1: 1. However, it can also be varied, for example, to adjust the viscosity and the sintering properties in a wide range.
Der Gewichtsanteil des Flussmittels bezogen auf das Gesamtgewicht des Ausgangswerkstoffs kann beispielsweise zwischen 5 Gew.-% und 40 Gew.-% liegen.
Der Anteil des Flussmittels liegt vorzugsweise im Bereich von 5-20 Gew.-%, mehr bevorzugt im Bereich von 7-18 Gew.-% und insbesondere bevorzugt im Bereich von 9-16 Gew.-%, bezogen auf das Gewicht des Ausgangswerkstoffs. In günstiger Weise ergibt sich dann eine besonders hohe thermische und/oder elektrische Leitfähigkeit der aus dem erfindungsgemäßen Ausgangswerkstoff hergestellten Sinterverbindungen. Zusätzlich fallen infolge des Reduktionsprozesses nur geringe Mengen an gasförmigen Nebenprodukten an. In einer vorteilhaften Ausgestaltung der Erfindung können die sinterbaren PartikelThe proportion by weight of the flux based on the total weight of the starting material may for example be between 5% by weight and 40% by weight. The proportion of the flux is preferably in the range of 5-20% by weight, more preferably in the range of 7-18% by weight and particularly preferably in the range of 9-16% by weight, based on the weight of the starting material. Conveniently, a particularly high thermal and / or electrical conductivity of the sintered compounds produced from the starting material according to the invention then results. In addition, due to the reduction process, only small amounts of gaseous by-products accumulate. In an advantageous embodiment of the invention, the sinterable particles
Silber, Gold, Platin, Palladium und/oder Kupfer enthalten oder daraus gebildet sein. Als Metallpartikel eignen sich Flakes oder Pulver mit Partikelgrößen im na- no- oder mikrometer-Bereich. Insbesondere können die sinterbaren Partikel beispielsweise auf Basis von Silber, Kupfer oder Aluminium und ineinander gut lösli- che Mischungen davon wie Cu/Ag, Au/Ag, Cu/Au, Ag/Au, Ag/Pd, und Pd/Pt ausgewählt sein. Ebenso denkbar sind Metallverbindungen, insbesondere Oxidverbindungen, der zuvor genannten Werkstoffe. Silver, gold, platinum, palladium and / or copper contained or formed from it. Suitable metal particles are flakes or powders with particle sizes in the nanometer or micrometer range. In particular, the sinterable particles may be selected, for example, based on silver, copper or aluminum and mixtures thereof which are readily soluble in one another, such as Cu / Ag, Au / Ag, Cu / Au, Ag / Au, Ag / Pd, and Pd / Pt. Also conceivable are metal compounds, in particular oxide compounds, of the aforementioned materials.
In einer weiteren vorteilhaften Ausgestaltung der Erfindung können die sinterba- ren Partikel beschichtet sein mit einem organischen Material, mit einer organischen Metallverbindung und/oder mit einem Metalloxid oder mit einer Mischung daraus. In a further advantageous embodiment of the invention, the sinterable particles can be coated with an organic material, with an organic metal compound and / or with a metal oxide or with a mixture thereof.
In einer weiteren vorteilhaften Ausgestaltung der Erfindung kann die Beschich- tung der sinterbaren Partikel als organisches Material einen primären oder sekundären Alkohol, ein Amin, eine organische Säure und/oder eine Fettsäure, insbesondere Isostearinsäure, Stearinsäure, Ölsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Octansäure, Decansäure oder eine Mischung daraus, enthalten. Je nach Wahl der organischen Beschichtung der sinterbaren Partikel kann die reduzierende Wirkung des Flussmittels hinsichtlich der in situ zur Verfügung gestellten Oberfläche der sinterbaren Partikel positiv beeinflusst werden. In a further advantageous embodiment of the invention, the coating of the sinterable particles as organic material can be a primary or secondary alcohol, an amine, an organic acid and / or a fatty acid, in particular isostearic acid, stearic acid, oleic acid, lauric acid, myristic acid, palmitic acid, octanoic acid , Decanoic acid or a mixture thereof. Depending on the choice of the organic coating of the sinterable particles, the reducing effect of the flux can be positively influenced with regard to the surface of the sinterable particles made available in situ.
In einer weiteren vorteilhaften Form der Erfindung ist ein Silbercarbonat, ein Sil- berlactat, ein Silberstearat oder ein Natriumcarbonat als organische Metallver- bindung und/oder Silberoxid oder Kupferoxid als Edelmetalloxid enthalten, insbesondere als Beschichtung auf den Partikeln. Grundsätzlich werden bei diese wei-
teren vorteilhaften Formen des Ausgangswerkstoffs die organischen Metallverbindungen bzw. das bevorzugte Edelmetalloxid bei einer Temperaturbehandlung des Ausgangswerkstoffes mittels des Flussmittels zu dem elementar zugrunde liegenden Metall bzw. Edelmetall, z.B. Silber, reduziert. Dadurch weist die auf diese Weise aus dem Ausgangswerkstoff gebildete Sinterverbindung eine besonders hohe thermische und/oder elektrische Leitfähigkeit auf. In a further advantageous embodiment of the invention, a silver carbonate, a silver lactate, a silver stearate or a sodium carbonate is present as the organic metal compound and / or silver oxide or copper oxide as the noble metal oxide, in particular as a coating on the particles. Basically, these are In other advantageous forms of the starting material, the organic metal compounds or the preferred noble metal oxide at a temperature treatment of the starting material by means of the flux to the elemental underlying metal or noble metal, for example silver, reduced. As a result, the sintered compound formed in this way from the starting material has a particularly high thermal and / or electrical conductivity.
Des Weiteren sind die sinterbaren Partikel bevorzugt sphärisch und/oder plätt- chenförmig ausgebildet. Eine Mischung derartiger Partikelgeometrien gegebenenfalls zusammen mit kugelförmigen Partikeln ermöglicht eine hohe Dichte der aus dem Ausgangswerkstoff gebildeten Sinterverbindung. Furthermore, the sinterable particles are preferably spherical and / or platelet-shaped. A mixture of such particle geometries optionally together with spherical particles allows a high density of the sintered compound formed from the starting material.
In einer bevorzugten weiteren Ausgestaltung der Erfindung ist das Flussmittel eine organische Säure, insbesondere eine aromatische Carbonsäure wie zum Beispiel Benzeosäure, Ameisensäure, Essigsäure, Malonsäure, Maleinsäure, Octan- , Nonan-, Dodecansäure; Glutaminsäure, Zitronensäure, Adipinsäure, Zimtsäure oder Milchsäure. In a preferred further embodiment of the invention, the flux is an organic acid, in particular an aromatic carboxylic acid such as, for example, benzoic acid, formic acid, acetic acid, malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid; Glutamic acid, citric acid, adipic acid, cinnamic acid or lactic acid.
Der Ausgangswerkstoff wird vorzugsweise als Paste bereitgestellt. Die Viskosität der Paste ist dabei maßgeblich durch das beigemischte Flussmittel oder ein Flussmittelgemisch einstellbar. The starting material is preferably provided as a paste. The viscosity of the paste is significantly adjustable by the admixed flux or a flux mixture.
Die Erfindung betrifft weiterhin eine Sinterverbindung hergestellt aus einem Ausgangswerkstoff wie vorstehend beschrieben, wobei die Sinterverbindung eine elektrische Leitfähigkeit zwischen 30 MS/m und 45 MS/m, insbesondere zwischen 36 MS/m und 44 MS/m, aufweist. The invention further relates to a sintered compound prepared from a starting material as described above, wherein the sintered compound has an electrical conductivity between 30 MS / m and 45 MS / m, in particular between 36 MS / m and 44 MS / m.
Eine Sinterverbindung hergestellt aus einem Ausgangswerkstoff wie vorstehend beschrieben kann eine thermische Leitfähigkeit zwischen 200 W/mK und 300 W/mK aufweisen. Insbesondere kann die thermische Leitfähigkeit der Sinterverbindung zwischen 220 W/mK und 275 W/mK betragen. A sintered compound made of a raw material as described above may have a thermal conductivity between 200 W / mK and 300 W / mK. In particular, the thermal conductivity of the sintered connection can be between 220 W / mK and 275 W / mK.
In einer Ausgestaltung der Sinterverbindung kann die Sinterverbindung eine Silbersinterverbindung sein. Bevorzugt ist die Silbersinterverbindung aus einem Ausgangswerkstoff enthaltend Partikel aus Silber und/oder Silberverbindungen und Ameisensäure als Flussmittel ausgebildet. Dabei weist Ameisensäure in vor-
teilhafter Weise eine hervorragende chemische Reaktivität gegenüber Oxiden auf und ist leicht rückstandsfrei zu verdampfen. Gleichzeitig ist eine Silbersinterver- bindungsschicht besonders bevorzugt, weil Silberpartikel gut sinterbar und verarbeitbar sind bei exzellenten Eigenschaften im Hinblick auf elektrische und ther- mische Leitfähigkeit sowie hinsichtlich der mechanischen Eigenschaften der gesinterten Schicht. In one embodiment of the sintered compound, the sintered compound may be a silver sintered compound. Preferably, the silver sintered compound is formed from a starting material containing particles of silver and / or silver compounds and formic acid as a flux. Here, formic acid is present in Partially excellent chemical reactivity to oxides and is easy to evaporate residue. At the same time, a silver sintered bonding layer is particularly preferred because silver particles are readily sinterable and processable with excellent electrical and thermal conductivity properties and mechanical properties of the sintered layer.
Die Erfindung betrifft weiterhin auch eine elektronische Schaltung mit einer Sinterverbindung wie vorstehend beschrieben, wobei die elektronische Schaltung die Sinterverbindung als elektrische, thermische und/oder mechanische Verbindung einer elektronischen Komponente zu insbesondere einer Kupferkomponente oder einer Komponente mit Kupferoberfläche darstellt. The invention further relates to an electronic circuit with a sintered connection as described above, wherein the electronic circuit is the sintered connection as an electrical, thermal and / or mechanical connection of an electronic component to, in particular, a copper component or a component with copper surface.
Insbesondere im Zusammenwirken mit Kupferoberflächen kann eine Sinterver- bindung, welche aus dem erfindungsgemäßen Ausgangswerkstoff hergestellt ist, eine sehr gute Haftung erzielen. Das Flussmittel, das insbesondere die Kupferoberfläche während des Fügevorgangs oxidfrei hält, wird in ausreichendem Maße zur Verfügung gestellt und die Kontaktierung der zu fügenden Oberfläche wird nicht durch zusätzlich anwesendes Lösungsmittel, welches während des Füge- Vorgangs zusätzliche Volumina Dampf entwickelt, gestört. In particular, in cooperation with copper surfaces, a sintered compound, which is made from the starting material according to the invention, can achieve a very good adhesion. The flux, which in particular keeps the copper surface oxide-free during the joining operation, is provided sufficiently and the contacting of the surface to be joined is not disturbed by additionally present solvent, which develops additional volumes of vapor during the joining process.
Eine elektronische Schaltung kann auf diese Weise mit einer reduzierten Gefahr von Fehlstellen in der Anbindung der elektronischen Komponenten hergestellt werden. Die Erfindung betrifft weiterhin auch ein Verfahren zur Ausbildung einer thermisch und/oder elektrisch leitenden Sinterverbindung. Ausgegangen wird hierbei von einem Ausgangswerkstoff der vorbeschriebenen Art, der zwischen beispielsweise zwei Fügepartner gebracht wird. Bevorzugte Fügepartner sind elektrische und/oder elektronische Komponenten mit Kontaktstellen, die in unmittelba- ren physischen Kontakt mit dem Ausgangswerkstoff gebracht werden. Hierbei kann der Ausgangswerkstoff in Form einer Druckpaste beispielsweise mittels Sieb- oder Schablonendruck auf die Kontaktstellen aufgetragen werden. Ebenso ist der Auftrag durch Injekt- oder Dispensverfahren möglich. Anschließend wird die Sinterverbindung durch eine Temperaturbehandlung des An electronic circuit can be manufactured in this way with a reduced risk of defects in the connection of the electronic components. The invention further relates to a method for forming a thermally and / or electrically conductive sintered compound. This is based on a starting material of the type described, which is brought between, for example, two joining partners. Preferred joining partners are electrical and / or electronic components with contact points, which are brought into direct physical contact with the starting material. Here, the starting material can be applied in the form of a printing paste, for example by means of screen or stencil printing on the contact points. Likewise, the order is possible through injection or dispensing. Subsequently, the sintered compound by a temperature treatment of the
Ausgangswerkstoffes ausgebildet. Die Temperaturbehandlung kann in einem
Schritt oder in mehreren Schritten stufenweise erfolgen. Typischerweise liegen die Temperaturen in diesem Schritt im Bereich von 150°C bis ca. 350°C, wobei insbesondere die zu fügenden Bauteile und deren Materialien einen nach oben limitierenden Faktor darstellen, da eine Beeinträchtigung der elektronischen Bau- teile durch die Temperaturbehandlung zu vermeiden ist. Starting material formed. The temperature treatment can be in one Step by step or in several steps. Typically, the temperatures in this step in the range of 150 ° C to about 350 ° C, in particular, the components to be joined and their materials represent an upward limiting factor, since a deterioration of the electronic components by the temperature treatment is to be avoided ,
Bevorzugt sind Fügepartner mit Kontaktstellen aus einem Edelmetall vorgesehen, beispielsweise aus Gold, Silber oder einer Legierung aus Gold oder Silber. Weiter bevorzugt sind Kontaktstellen mit einer Kupferoberfläche vorgesehen. Bonding partners with contact points made of a noble metal, for example gold, silver or an alloy of gold or silver, are preferably provided. More preferably, contact points are provided with a copper surface.
Bei der Temperaturbehandlung zur Ausbildung der Sinterverbindung oder auch in einer vor gelagerten Temperaturbehandlung mit einer insbesondere geringeren Temperatur als die Sintertemperatur kann das Flussmittel dann eine Reduktion insbesondere von möglichen Oxiden auf der Oberfläche des Fügepartners und/oder auf der Oberfläche der sinterbaren Partikel bewirken, welches zu verbesserten Ergebnissen der resultierenden Baugruppe führt. Alternativ kann das Flussmittel auch in diesem Fall eine möglicherweise vorhandene Beschichtung der sinterbaren Partikel auflösen, um diese für den nachfolgenden Sinterschritt zu aktivieren. Dies kann zum Beispiel dadurch geschehen, dass das Flussmittel eine Verbrennungsreaktion der Beschichtung katalysiert, die Beschichtung in die flüssige Phase bringt und dadurch leichter verdampfen lässt oder mit der Beschichtung unter Bildung eines inerten Materials bindet. During the temperature treatment for the formation of the sintered compound or also in a pre-stored temperature treatment with a particular lower temperature than the sintering temperature, the flux can then cause a reduction in particular of possible oxides on the surface of the joining partner and / or on the surface of the sinterable particles, which results in improved results of the resulting assembly. Alternatively, in this case too, the flux can dissolve a possibly present coating of the sinterable particles in order to activate them for the subsequent sintering step. This can be done, for example, by the flux catalyzing a combustion reaction of the coating, bringing the coating into the liquid phase and thereby allowing it to evaporate more easily or bonding to the coating to form an inert material.
Auf diese Weise kann im Fügebereich vorteilhafterweise vor der Ausbildung einer Sinterschicht ein Flussmittel zur Verfügung gestellt werden, ohne dass es mit einem aufwendigen Auftragungsverfahren auf die Oberfläche aufgebracht wird. In this way, in the joining region, advantageously before the formation of a sintered layer, a flux can be made available without being applied to the surface with a complicated application process.
In einer weiteren Ausgestaltung des Verfahrens kann das zu fügende Bauteil zunächst zumindest mit der zu fügenden Fläche in ein Bad aus reinem Flussmittel eingetaucht werden und danach wird der Ausgangswerkstoff auf der Fügefläche bereitgestellt. In a further embodiment of the method, the component to be joined can first be immersed in a bath of pure flux at least with the surface to be joined, and then the starting material is provided on the joining surface.
Hierdurch ist es vorteilhaft möglich, eine zusätzliche Menge des Flussmittels unmittelbar auf der zu fügenden Oberfläche bereit zu stellen. Insbesondere für sol- che Fügeverfahren, in denen das Flussmittel auch die Aufgabe übernimmt, eineAs a result, it is advantageously possible to provide an additional quantity of the flux directly on the surface to be joined. In particular for such joining methods, in which the flux also takes over the task, a
Beschichtung der sinterbaren Partikel aufzulösen, ist dies bevorzugt.
Kurze Beschreibung der Zeichnungen To dissolve coating of the sinterable particles, this is preferred. Brief description of the drawings
Weitere Vorteile, Merkmale und Einzelheiten der Erfindung ergeben sich aus der nachfolgenden Beschreibung bevorzugter Ausführungsbeispiele sowie anhand der Zeichnungen. Diese zeigen in: Further advantages, features and details of the invention will become apparent from the following description of preferred embodiments and from the drawings. These show in:
Fig. 1 schematisch den Ausgangswerkstoff gemäß der vorliegenden Erfindung in Form einer Paste, und Fig. 1 shows schematically the starting material according to the present invention in the form of a paste, and
Fig. 2 schematisch eine elektronische Schaltung gemäß der vorliegenden Erfindung. Fig. 2 shows schematically an electronic circuit according to the present invention.
In den Figuren sind gleiche Bauteile und Bauteile mit der gleichen Funktion mit den gleichen Bezugszeichen gekennzeichnet. In the figures, the same components and components with the same function with the same reference numerals.
In Figur 1 wird schematisch ein Ausgangswerkstoff 100 einer Sinterverbindung 1 12 gemäß der vorliegenden Erfindung in Pastenform gezeigt, welcher sinterbare Partikel 102 aus mindestens einem Metall oder mindestens einer Metallverbindung und mindestens ein Flussmittel 103 umfasst. Das Flussmittel 103 ist zugleich das Lösungsmittel des Ausgangswerkstoffs 100, welcher insbesondere auf Kupferoberflächen vorteilhaft einsetzbar ist. Die sinterbaren Partikel 102 können insbesondere Silber, Gold, Platin, Palladium und/oder Kupfer enthalten und weisen eine optionale Beschichtung 105 auf, welche aus einem organischen Material, mit einer organischen Metallverbindung und/oder mit einem Metalloxid oder aus einer Mischung daraus gebildet ist. Die optionale Beschichtung 105 der sinterbaren Partikel 102 kann als organisches Material einen primären oder sekundären Alkohol, ein Amin, eine organische Säure und/oder eine Fettsäure, insbesondere Isostearinsäure, Stearinsäure, Ölsäure, Laurinsäure oder eine Mischung daraus, enthalten. Als organische Metallverbindung kann die Beschichtung 105 Silbercarbonat, Silberlactat, Silberstearat oder Natriumcarbonat enthalten und als Metalloxid kann die optionale Beschichtung 105 der sinterbaren Partikel 102 insbesondere Silberoxid oder Kupferoxid enthalten. Das Flussmittel 103 ist vorzugsweise eine organische Säure, insbesondere eine aromatische Carbonsäure wie Benzoesäure, Ameisensäure, Essigsäure, Zitronensäure, Adipinsäure, Zimtsäure eine Dicarbonsäure wie Malonsäure, Maleinsäure, Octan-, No- nan-, Dodecansäure; eine Aminsäure wie Glutaminsäure, eine Hydroxycarbon-
säure wie Milchsäure, oder ein Naphthol, Enol, oder Phenol, und bevorzugt flüssig oder verflüssigbar bei Trocknungs- oder Sintertemperaturen. FIG. 1 schematically shows a starting material 100 of a sintered compound 12 according to the present invention in paste form, which comprises sinterable particles 102 of at least one metal or at least one metal compound and at least one flux 103. The flux 103 is at the same time the solvent of the starting material 100, which can advantageously be used in particular on copper surfaces. The sinterable particles 102 may in particular contain silver, gold, platinum, palladium and / or copper and have an optional coating 105 which is formed from an organic material, with an organic metal compound and / or with a metal oxide or a mixture thereof. The optional coating 105 of the sinterable particles 102 may contain as organic material a primary or secondary alcohol, an amine, an organic acid and / or a fatty acid, in particular isostearic acid, stearic acid, oleic acid, lauric acid or a mixture thereof. As the organic metal compound, the coating 105 may contain silver carbonate, silver lactate, silver stearate or sodium carbonate, and as the metal oxide, the optional coating 105 of the sinterable particles 102 may include, in particular, silver oxide or copper oxide. The flux 103 is preferably an organic acid, in particular an aromatic carboxylic acid, such as benzoic acid, formic acid, acetic acid, citric acid, adipic acid, cinnamic acid, a dicarboxylic acid, such as malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid; an amino acid such as glutamic acid, a hydroxycarboxylic acid acid, such as lactic acid, or a naphthol, enol or phenol, and preferably liquid or liquefiable at drying or sintering temperatures.
In Figur 2 wird schematisch eine elektronische Schaltung mit einer Sinterverbindung 112 aus dem Ausgangswerkstoff der vorliegenden Erfindung gezeigt, wobei die elektronische Schaltung die Sinterverbindung 112 als elektrische, thermische und/oder mechanische Verbindung einer elektronischen Komponente 1 10 zu insbesondere einer Kupferkomponente oder einer Komponente mit Kupferoberfläche 1 11 umfasst. Der Ausgangswerkstoff für die Sinterverbindung 1 12 ist in Form einer Druckpaste oder einer Ink-Jet-Tinte oder als Formteil ausgebildet und wurde mit einem Druck- oder Klebe- beziehungsweise mit einem Laminierverfah- ren auf die zu fügenden Komponenten 11 1 und 1 10 aufgebracht beziehungsweise mit diesen in Kontakt gebracht. Anschließend wird die Sinterverbindung 1 12 durch Temperatur- und/oder Druckbeaufschlagung aus dem Ausgangswerkstoff ausgebildet.
FIG. 2 schematically shows an electronic circuit with a sintered connection 112 made of the starting material of the present invention, the electronic circuit comprising the sintered connection 112 as electrical, thermal and / or mechanical connection of an electronic component 110 to, in particular, a copper component or a component with a copper surface 1 11 includes. The starting material for the sintered compound 1 12 is in the form of a printing paste or an ink-jet ink or as a molded part and was applied with a printing or adhesive or with a lamination process on the components to be joined 11 1 and 1 10 or contacted with these. Subsequently, the sintered compound 1 12 is formed by temperature and / or pressurization of the starting material.
Claims
1. Ausgangswerkstoff einer Sinterverbindung (101), insbesondere auf Kupferoberflächen, umfassend sinterbare Partikel (102) aus mindestens einem Metall oder mindestens einer Metallverbindung und mindestens ein Flussmittel (103), dadurch gekennzeichnet, dass das Flussmittel ein Reduktionsmittel und (103) zugleich das Lösungsmittel des Ausgangswerkstoffs (100) ist. 1. Starting material of a sintered connection (101), in particular on copper surfaces, comprising sinterable particles (102) of at least one metal or at least one metal compound and at least one flux (103), characterized in that the flux is a reducing agent and (103) at the same time the solvent of the starting material (100).
2. Ausgangswerkstoff nach Anspruch 1 , dadurch gekennzeichnet, dass die sinterbaren Partikel (102) Silber, Gold, Platin, Palladium und/oder Kupfer enthalten. 2. Starting material according to claim 1, characterized in that the sinterable particles (102) silver, gold, platinum, palladium and / or copper.
3. Ausgangswerkstoff nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die sinterbaren Partikel (102) beschichtet sind mit einem organischen Material, mit einer organischen Metallverbindung und/oder mit einem Metalloxid oder mit einer Mischung daraus. 3. Starting material according to one of claims 1 or 2, characterized in that the sinterable particles (102) are coated with an organic material, with an organic metal compound and / or with a metal oxide or with a mixture thereof.
4. Ausgangswerkstoff nach Anspruch 3, dadurch gekennzeichnet, dass die Be- schichtung (105) der sinterbaren Partikel (102) als organisches Material einen primären oder sekundären Alkohol, ein Amin, eine organische Säure und/oder eine Fettsäure, insbesondere Isostearinsäure, Stearinsäure, Ölsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Octansäure, Decansäure oder eine Mischung daraus, enthält. 4. Starting material according to claim 3, characterized in that the coating (105) of the sinterable particles (102) as organic material is a primary or secondary alcohol, an amine, an organic acid and / or a fatty acid, in particular isostearic acid, stearic acid, Oleic acid, lauric acid, myristic acid, palmitic acid, octanoic acid, decanoic acid or a mixture thereof.
5. Ausgangswerkstoff nach einem der Ansprüche 3 bis 4, dadurch gekennzeichnet, dass die Beschichtung (105) der sinterbaren Partikel (102) als organische Metallverbindung Silbercarbonat, Silberlactat, Silberstearat oder Natriumcarbonat enthält. 5. Starting material according to one of claims 3 to 4, characterized in that the coating (105) of the sinterable particles (102) contains as an organic metal compound silver carbonate, silver lactate, silver stearate or sodium carbonate.
6. Ausgangswerkstoff nach einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, dass die Beschichtung (105) der sinterbaren Partikel (102) als Metalloxid Silberoxid oder Kupferoxid enthält. 6. Starting material according to one of claims 3 to 5, characterized in that the coating (105) of the sinterable particles (102) contains as the metal oxide silver oxide or copper oxide.
7. Ausgangswerkstoff nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Flussmittel (103) eine organische Säure, insbesondere Benzeosäure, Ameisensäure, Essigsäure, Malonsäure, Maleinsäure, Octan-, Nonan-, Dodecansäure; Glutaminsäure, Zitronensäure, Adipinsäure, Zimtsäure oder Milchsäure, ist. 7. Starting material according to one of claims 1 to 6, characterized in that the flux (103) is an organic acid, in particular benzoic acid, formic acid, acetic acid, malonic acid, maleic acid, octanoic, nonanoic, dodecanoic acid; Glutamic acid, citric acid, adipic acid, cinnamic acid or lactic acid.
8. Sinterverbindung (1 12) hergestellt aus einem Ausgangswerkstoff nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Sinterverbindung eine elektrische Leitfähigkeit zwischen 30 MS/m und 45 MS/m, insbesondere zwischen 36 MS/m und 44 MS/m, aufweist. 8. sintered compound (1 12) prepared from a starting material according to any one of the preceding claims, characterized in that the sintered compound has an electrical conductivity between 30 MS / m and 45 MS / m, in particular between 36 MS / m and 44 MS / m ,
9. Sinterverbindung (112) hergestellt aus einem Ausgangswerkstoff nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Sinterverbindung eine thermische Leitfähigkeit zwischen 200 W/mK und 300 W/mK, insbesondere zwischen 220 W/mK und 275 W/mK, aufweist. 9. sintered compound (112) prepared from a starting material according to any one of the preceding claims, characterized in that the sintered compound has a thermal conductivity between 200 W / mK and 300 W / mK, in particular between 220 W / mK and 275 W / mK.
10. Sinterverbindung (1 12) nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass die Sinterverbindung (112) eine Silbersinterverbindung ist. 10. sintered connection (1 12) according to claim 8 or 9, characterized in that the sintered compound (112) is a silver sintered compound.
1 1. Elektronische Schaltung mit einer Sinterverbindung nach einem der Ansprüche 8, 9 oder 10, wobei die elektronische Schaltung die Sinterverbindung (1 12) als elektrische, thermische und/oder mechanische Verbindung einer elektronischen Komponente (1 10) zu insbesondere einer Kupferkomponente oder einer Komponente mit Kupferoberfläche (111) darstellt. 1 1. Electronic circuit with a sintered connection according to one of claims 8, 9 or 10, wherein the electronic circuit, the sintered connection (1 12) as an electrical, thermal and / or mechanical connection of an electronic component (1 10) in particular a copper component or a Component with copper surface (111) represents.
12. Verfahren zur Ausbildung einer Sinterverbindung (112), insbesondere auf einer Kupferoberfläche (111), wobei ein Ausgangswerkstoff der Sinterverbindung nach einem der Ansprüche 1 bis 7 vorgesehen wird, umfassend folgende Schritte: 12. A method for forming a sintered connection (112), in particular on a copper surface (111), wherein a starting material of the sintered connection is provided according to one of claims 1 to 7, comprising the following steps:
Bereitstellen des Ausgangswerkstoffs, Providing the starting material,
- Ausbilden der Sinterverbindung durch eine Temperaturbehandlung des Ausgangswerkstoffs, wobei die Temperatur oberhalb der Schmelztemperatur des Flussmittels und unterhalb der Schmelztemperatur der Partikel liegt. - Forming the sintered compound by a temperature treatment of the starting material, wherein the temperature is above the melting temperature of the flux and below the melting temperature of the particles.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass mittels des im Ausgangswerkstoff enthaltenen Flussmittels (103) auf der Oberfläche eines Fügepartners (1 11), auf welcher der Ausgangswerkstoff aufgetragen wird, und/oder auf den Kontaktflächen der im Ausgangswerkstoff enthaltenen Partikel (102) beim Sintern ein Reduktionsvorgang noch unterhalb der Sintertemperatur der im Ausgangswerkstoff enthaltenen Partikel (102) einsetzt. 13. The method according to claim 12, characterized in that by means of the flux contained in the starting material (103) on the surface of a joining partner (1 11) on which the starting material is applied, and / or on the contact surfaces of the particles contained in the starting material (102 ) during sintering, a reduction process still below the sintering temperature of the particles contained in the starting material (102) begins.
14. Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, dass das zu fügende Bauteil (110) zunächst zumindest mit der zu fügenden Fläche in ein Bad aus reinem Flussmittel (103) eingetaucht wird und danach der Ausgangswerkstoff auf der Fügefläche bereitgestellt wird. 14. The method according to claim 12 or 13, characterized in that the component to be joined (110) is first immersed at least with the surface to be joined in a bath of pure flux (103) and then the starting material is provided on the joint surface.
15. Verfahren nach einem der Ansprüche 12, oder 13, dadurch gekennzeichnet, dass der Ausgangswerkstoff in Form einer Druckpaste ausgebildet ist. 15. The method according to any one of claims 12, or 13, characterized in that the starting material is in the form of a printing paste.
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DE102011083893A DE102011083893A1 (en) | 2011-09-30 | 2011-09-30 | Starting material of a sintered compound and method for producing the sintered compound |
PCT/EP2012/068644 WO2013045360A1 (en) | 2011-09-30 | 2012-09-21 | Starting material for a sintered bond and method for producing the sintered bond |
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WO2010020400A2 (en) * | 2008-08-22 | 2010-02-25 | W. C. Heraeus Gmbh | Material comprised of metal and lactic acid condensate and electronic component |
DE102009040078A1 (en) * | 2009-09-04 | 2011-03-10 | W.C. Heraeus Gmbh | Metal paste with CO precursors |
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US20030148024A1 (en) * | 2001-10-05 | 2003-08-07 | Kodas Toivo T. | Low viscosity precursor compositons and methods for the depositon of conductive electronic features |
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JP5006081B2 (en) * | 2007-03-28 | 2012-08-22 | 株式会社日立製作所 | Semiconductor device, manufacturing method thereof, composite metal body and manufacturing method thereof |
DE102007046901A1 (en) | 2007-09-28 | 2009-04-09 | W.C. Heraeus Gmbh | Production of electrically conductive or heat-conductive component for producing metallic contact between two elements e.g. cooling bodies or solar cells, comprises forming elemental silver from silver compound between contact areas |
DE102009040076A1 (en) * | 2009-09-04 | 2011-03-10 | W.C. Heraeus Gmbh | Metal paste with oxidizing agent |
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2011
- 2011-09-30 DE DE102011083893A patent/DE102011083893A1/en not_active Withdrawn
-
2012
- 2012-09-21 WO PCT/EP2012/068644 patent/WO2013045360A1/en active Application Filing
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WO2005079353A2 (en) * | 2004-02-18 | 2005-09-01 | Virginia Tech Intellectual Properties, Inc. | Nanoscale metal paste for interconnect and method of use |
WO2010020400A2 (en) * | 2008-08-22 | 2010-02-25 | W. C. Heraeus Gmbh | Material comprised of metal and lactic acid condensate and electronic component |
DE102009040078A1 (en) * | 2009-09-04 | 2011-03-10 | W.C. Heraeus Gmbh | Metal paste with CO precursors |
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WO2013045360A1 (en) | 2013-04-04 |
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