DE3134918A1 - "Electrode on heat-resistant, insulating substrate and method for manufacturing it" - Google Patents

Abstract

Electrode on a heat-resistant, insulating substrate, which can be manufactured cheaply and has stable properties. To this end, a paste containing from 0.05 to 40% by weight of a metal material which contains from 0.5 to 100% by weight of a silver component, the remainder being an organic excipient, is applied to the substrate, a heat treatment is carried out at temperatures of from 250 to 900 DEG C, so that a metal particle layer having a thickness of from 0.05 to 2 micrometres (microns) is formed on the substrate, after which an electrode consisting of nickel or copper is applied in a thickness of from 0.1 to 20 micrometers by electroless metallisation.

Description

Electrode on heat-resistant insulating

Substrate and Method of Making Same The invention relates to Electrodes for heat-resistant insulating substrates that are inexpensive to manufacture and has stable properties, and an improved method for their manufacture.

The use of a metal glaze electrode made from essentially expensive Metals such as Ag, Ag-Pd, Ag-Pt, Ag-Ni as an electrode on heat-resistant and insulating Substrates is known.

If you use such silver electrodes, however, where there is a potential difference Standing over adjacent electrodes in high humidity can cause short circuits as well a silver migration may occur. Furthermore, the electrode needs to be soldered on.

As a result of the high rise in silver prices, the conventional silver electrodes have become too expensive.

Therefore, one has to pay more attention to the rising metal prices on the production of electrodes using galvanic or electroless metallization processes related. Such electrodes are generally generated without current. To do this, dives to sensitize the substrate in a tin (II) chloride solution, then for activation in a palladium chloride solution and finally metallized without current.

However, the electrolessly applied conventional electrode does not adhere tight enough to the substrate and their properties deteriorate over time. Furthermore, this electrode is also disadvantageous in terms of its manufacture. That Process is the manufacture of electrodes on dielectric, piezoelectric and adapted to semiconducting substrates and the like; there are coverings on the formed over the entire surface of the substrate. The electrode is then hit along the circumferential contour and forms it surface to surface.

The dielectric strength results from the thickness of the electrode and the insulation can quickly become through stress concentrations at the edges of the Electrode can be destroyed.

The use of very thin substrates was therefore not possible.

To solve these manufacturing problems, methods have been proposed which contain a partial metallization.

For example, a metal film was applied to part of the surface formed of a ceramic substrate carrying a resist material so that only the required area parts have been activated. The metal layer became electroless everywhere formed where the resist layer was removed.

Furthermore, etching, vapor deposition and sputtering processes were used in part Metallization applied. However, these procedures are not entirely satisfactory, because the electrodes formed after them do not adhere firmly enough to the substrate and showed insufficient properties. From the manufacturing point of view and They are therefore reluctant to use because of the effort involved.

It is thus an object of the present invention to provide an excellent one and a stable electrode on a heat-resistant insulating substrate and a specify new and improved process that is easy to manufacture and can be used with little effort.

The present invention therefore provides an electrode on a substrate, those made of a silver-containing metal layer produced by a heat treatment as well as an electrolessly applied metallization layer, firmly on the Substrate adheres, has good properties and is excellent for manufacturing suitable.

The present invention shall hereinafter be considered with reference to the accompanying Drawing will be described in detail.

Fig. 1 is a section through the electrode of the present invention on a heat-resistant insulating substrate, with 1 being the heat-resistant insulating Substrate, 2 the metal layer with a silver component and 3 the electroless metallization layer describe; Fig. Shows the pattern of the electrode on an alumina substrate, where 1 is the alumina substrate, 2 is the electrode for measuring adhesive strength and 3 denotes the electrode for determining the silver migration; Fig. 3 shows a section and a top view of the electrode on a dielectric Ceramic substrate, where 1 is the dielectric ceramic substrate, 2 is the metal layer with the silver component and 3 denote the electroless metallization layer.

According to the present invention, an electrode is provided as follows made of a heat-resistant and insulating substrate: one brings on that Substrate a paste with 0.05 to 40 wt .-% of a metal material containing 0.5 to Contains 100 wt .-% of a silver component, then heated to 250 to 9000C, so that a metal layer forms on the substrate, and ultimately brings about de-energized an electrode made of nickel or copper in a thickness of 0.1 to 20; im on the Electroless metal layer.

The method proposed here is used as the silver component in the metal material of the paste a silver powder and / or a silver compound such as for example silver nitrate, silver carbonate, silver chloride, which under heat treatment forms a metallic silver layer.

The silver component is good for the purpose of the present invention suitable because it forms metallic silver easily, is hardly oxidized and is cheap.

The metallic components - with the exception of the silver - are made made of simple metals and alloys - for example, copper, aluminum, Zinc, tin, tungsten, molybdenum, iron, cobalt, chromium and especially nickel as Base metal particularly suitable.

The powder of the silver and the base metal should have a diameter of less than 2 m. If more than 2 iim, the adhesion of the electrode will suffer, the electrical properties as well as the printing properties of the paste.

The silver and base metal are in proportions from 0.5 to 100 Weight percent silver and 0 to 99.5 weight percent base metal; preferably one chooses 5 to 80% by weight of the silver component and 95 to 20% by weight of the base metal.

If there is too little silver component compared to the C-round metal, the forming metal layer oxidizes too easily during the heat treatment and the electrolessly applied metal layer becomes uneven; you get a bad one Adhesion, as well as inadequate electrical properties; Even with too much silver it sticks the electrode bad.

By adding 0.01 to 5 wt% palladium component to the mentioned Metal component gives an excellent activation for electroless metallization, also a uniform electrode, better adhesive strength and better Electrical Properties.

The proportion of the metal material in the paste is 0.05 to 40% by weight. If the proportion is too small, the uniformity of the deposit will suffer when the device is not powered Plating and the adhesive strength of the electrode; sticks if there is too much metal material the resulting electrode is also poor, showing poor electrical properties and becomes too expensive. The proportion is preferably in the range from 5 to 30 Cew.-t.

According to the present invention, the further addition of 0.5 to 5% by weight of glass powder or low-melting oxide like for example Bi2O3, B203 PbO to paste improve the adhesive strength of the electrode, while B2O3 also prevents the oxidation of the active metal for electroless plating. Therefore, a glass powder containing B2O3 is desired.

The proportion of these surcharges is not effective enough below 0.5 wt .-%; at more than 5 pw - the adhesive strength and the electrical properties the electrode is affected.

Since conventional melt type silver paste is a main component of the When the powder is silver, the printing accuracy of the paste is good. However, the bigger the Resin content in the paste, the worse we print accuracy, since it is the paste can run out.

On the other hand, since the paste according to the present invention is less Contains parts of the metal components, it runs out easily. If you give her 1 to 30 Sew.-t carbon powder or inorganic powder such as SiO2, MgO, CaO and clay from 2 Micrometer, leakage of the paste can be effectively prevented, and the Paste does not affect the other properties.

The minimum of the amount to be added is that which was explained above Effect results; the maximum is where there is even deposition at the electroless metallization, the adhesive strength and the electrical properties begin to deteriorate.

According to the present invention, the substrate is heated to temperatures between 250 and 9000C after applying the paste in the desired areas to the heat resistant insulating Substrate printed or sprayed on and then dried.

The purpose of the heat treatment is on one surface of the substrate to form a stable layer of metal particles. Is the treatment temperature lower than the specified limit value, it is difficult because of the resin residues achieve a uniform layer of metal particles; the then trained Electrode has poor adhesive strength and poor electrical properties. If the temperature is above the limit, no uniform layer is formed Metal particles as the metal melts or oxidizes, so that the adhesive strength and the electrical properties also suffer. For the reasons mentioned lies the optimal temperature between 350 and 600 "C.

Is the metal particle layer formed on the substrate by the heat treatment Evenly between 0.05 and 2 micrometers thick, it can function as an activation layer exercise well for electroless plating.

In contrast, the conventional fused silver electrode is used as a thick film of about 5 to 20 micrometers - and works itself as an electrode. the thin metal film according to the present invention can neither itself as an electrode still work, it can be soldered before the electroless metallization layer is applied to it has been. Therefore, the metal layer differs significantly from the conventional ones Melt-type silver electrodes.

If the metal layer is thinner than the specified limit, the The metallization layer turns out unevenly and the electrode shows poor results Properties.

If the metal layer is too thick, no clear electrode outlines can be seen for electroless plating achieve; furthermore you don't get just one poor adhesive strength and poor electrical properties, but also at the endurance test, in which a voltage under high humidity is applied to the electrode lies, a silver hike.

Furthermore, a metal particle layer is of a thickness as that of the conventional one Silver electrode undesirable for reasons of cost. So the metal layer is best between 0.2 and 1 micrometer thick. Then, in the case of the heat treatment, it can be smaller Ceramic capacitors achieve a good accuracy of the metal layer by one in a mass of inorganic material such as alumina from 0.1 to 10 millimeters Diameter heated.

According to the present invention is an electroless plating with copper and nickel for reasons of electrical properties and solderability and suitability for mass production is preferred.

The electroless plating bath mainly contains one water-soluble copper compound, a copper (II) complexing agent, an alkali compound and formaldehyde as a reducing agent. An electroless nickel plating bath generally includes Nickel sulfate and phosphite as reducing agents; a boron compound as a reducing agent in the bathroom is preferred for reasons of soldering properties.

According to the present invention, the thickness is that of the electroless applied Metallization 0.1 to 20 micrometers. Of the lower limit is on the effectiveness as an electrode, the upper limit due to the electrical properties and determines the cost; the optimum range of thicknesses is between 1 and 10 Micrometer. If the metal layer formed during the heat treatment is pre-treated electroless plating with a solution containing at least one ion of the group Containing Pd, Pt, Os, Ir and Ru, it is used for the electroless plating reaction activated and you get a uniform electrode. If you continue to treat the Metal layer in a solution containing an organic acid, ammonium solution, nitric acid, Contains sulfuric acid individually or as a mixture, before using the solution, for example Substitution-treated of the Pd ion, better dimensional accuracy can be obtained of the electrolessly applied electrode.

For the present invention, it must be heat-resistant and insulating Substrate be heat resistant at temperatures above 2500C; preferably used one ceramic substrate.

By roughening the substrate surface with chemical resp.

mechanical means can improve the adhesive strength of the electrode and improve their electrical properties.

Fig. 1 shows in section the structure of an electrode on the heat-resistant insulating substrate as obtained according to the present invention. In the In Fig. 1, 1 is the heat-resistant insulating substrate, 2 is the metal layer with a silver component and 3 the electrolessly applied metallization layer.

The electrodes produced according to the present invention on a heat-resistant insulating substrates are suitable as coverings for cable runs, Capacitors, piezoelectric components, etc.

Example 1 As a heat-resistant and insulating substrate, a 50 x 50 mm aluminum oxide substrate with a thickness of 1 mm used, which is in a Mixed solution of fluoric acid and nitric acid had been etched.

The paste that was printed on the substrate was rated 0.05 to 40% by weight of the metal material, the 0 to 100% by weight of the silver component and 100 to 0 wt .-% base metal, the remainder an organic carrier.

Silver powder with an average was used as the silver component 1 micron diameter and / or silver nitrate.

A metal powder such as Ni, Cu, Al, Zn, Sn, W, Mo, Fe, Co, Cr with an average diameter of less than 2 microns.

The organic carrier was a resin such as ethyl cellulose, Acet cellulose, butyl rubber, polyvinyl butyral, phenol and a solvent such as Carbitol, Terpineol, Cellosolve, or Alcohol.

The C-laser powder components used as additives were as follows: Glass powder A made from PbO, B203, Al203, Na2O; Glass powder B made from B203, Nu203, CaO, ZnO; Glass powder C made of Na2O, P203, CaO, ZnO, B2O3.

This paste was applied to the alumina in the pattern shown in FIG printed, then dried at 100 to 1200C and then by heat treatment at 200 to 9000C on an electric stove, the metal particle layer was formed.

The substrate was then immersed in a palladium ion solution of 0.01% dipped, then a copper and nickel layer 0.1 to 20 microns thick formed by electroless plating on the substrate.

One component of the electroless copper plating bath was treated with copper sulfate, EDTA as a complexing agent, formaldehyde as a reducing agent, sodium hydroxide as a pE regulator and additives, then electroless copper plating in the bath at a bath temperature carried out from 70 to 750C. Part of the electroless nickel plating bath was with Nickel sulfate, sodium citrate as a complexing agent, sodium phosphite as a reducing agent and then electrolessly nickel-plated at a bath temperature of 88 to 920C.

To measure the adhesive strength of the electrodes on the substrate in each case one electrode with a diameter of 5 mm (see Fig. 2-2) is provided and a 0.5mm thick wire soldered to it.

In the silver migration test, a voltage of 10V was found between two Electrodes placed in the form shown in Fig. 2-3. The test was carried out at a Temperature of 600C and a relative humidity of 95% for the duration of 1,000 hours

Silver migration was observed after the test.

As an example of conventional electroless electrodes the substrate by immersion in a tin (II) ion solution and a palladium ion solution immersed and covered with a resist material an electrode with a diameter of 5 mm applied to the substrate by electroless nickel plating.

As an example of a conventional melt type silver electrode a silver paste on the substrate in the Fig.

2-2, 2-3 pattern shown, dried at 1200C for ten minutes and then heat treated at 8600C for 10 minutes.

The results of this example are summarized in Table I.

The table shows an estimate of the state of the de-energized Metal order with the character "o" for "good", t. for "still good" and "x" for "schletht" was used for the samples marked with "Ag compound only" in the "Comments" only silver powder as Ag component.

A circle around the sample number indicates a comparative example.

Example 2 A ceramic substrate (dielectric) with a diameter of 4 to 10 mm and 0.15 to 1 mm thickness of BaTiO3 BaZrO2 and CaTiO3 was in a mixed solution Etched from fluoric and nitric acid and then served as a heat-resistant insulating Substrate.

The same paste as in Example 1 was prepared and used in in Fig. 3 is printed using a cover so that a uniform margin of 0.5 to 1 mm remained on each side of the substrate.

The subsequent treatment and measurement of the adhesive strength was like in example 1.

The dielectric properties were given before and after the endurance test (1,000 hours at 850C, relative humidity 85 t) at a temperature of 200C measured with a frequency of 20 kHz on a capacitance bridge.

The results are summarized in Table II. -The table II contains an estimate of the state of the electrolessly applied metallization with the same symbols as in Table I; denotes a circle around a sample number also a reference example.

As can be seen from the previous description and the data in the tables results, according to the present invention on the heat-resistant insulating Substrate formed electrode has better properties and is cheaper to create than a conventional silver fusible electrode; she is towards this after her Properties preferred and more suitable for industrial mass production than the electroless nickel electrode applied by the conventional method.

The electrode on the heat-resistant insulating substrate and the Manufacturing processes according to the invention are therefore of great value to industry.

TABLE I Sample Composition Metal Additions Tempe Avg. Thickness d. Condition Accurate - Adhesion - Silver - Comments No. of the metal component i.d. paste thickness d. currentless d.current n.d. Festig- wanderatur d.

nente i.d. Heat metal sh. upset upset current cure paste treated after heat Metallic Metallic Metallic after soldering 60 ° C, 95% Ag-Ant. Reason- treatment treatment ization ization Electrode 5 # 10V metal # # Wire 0.5 # 1000 Hours.

% By weight% by weight% by weight ° C μm μm μm Kp 1 100 0 10-450 0.5 3 (Ni) 0 ~ # + 70 ~ + 100 0.6 no 2 80 20 (Ni) 10 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 2.6 no 3 60 40 (Ni) 10 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 3.3 No 4 40 60 (Ni) 10 - 450 0.5 3 (Ni) 0 + 40 ~ + 60 3.6 No 5 20 80 (Ni) 10 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 3.8 No 6 10 90 (Ni) 10 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 3.2 No 7 5 95 (Ni) 10 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 2.7 no 8 0.5 99.5 (Ni) 10 - 450 0.5 3 (Ni) 0 ~ # + 20 ~ + 40 1.0 no 9 0 100 (Ni) 10 - 450 0.5 3 (Ni) # ~ x + 10 ~ + 30 0.2 No 10 20 80 (Ni) 0.02 - 450 0.02 - x - - -11 20 80 (Ni) 0.05 - 450 0.05 3 (Ni) # + 120 ~ + 200 0.4 No 12 20 80 (Ni) 0.5 - 450 0.1 3 (Ni) 0 ~ # + 100 ~ + 200 0.5 No 13 20 80 (Ni) 1 - 450 0.1 3 (Ni) 0 ~ # + 100 ~ + 200 0.9 no 14 20 80 (Ni) 5 - 450 0.2 3 (Ni) 0 + 80 ~ + 160 2.7 no 15 20 80 (Ni) 20 - 450 0.7 3 (Ni) 0 + 40 ~ + 60 3.6 No 16 20 80 (Ni) 30 - 450 1.0 3 (Ni) 0 + 20 ~ + 50 3.3 No 17 20 80 (Ni) 30 - 450 1.5 3 (Ni) 0 + 80 ~ + 150 1.5 No 18 20 80 (Ni) 40 - 450 2 3 (Ni) 0 + 100 ~ + 200 1.1 No 19 20 80 (Ni) 60 - 450 4 3 (Ni) 0 + 180 ~ + 300 0.3 No 20 100 0 (Ni) 0.05 - 450 0.05 3 (Ni) # + 150 ~ + 250 0.6 No only Ag connection TABEL I - continued sample composition metal surcharges tempe- avg. thickness d. Condition Accurate- Hold- Silver- Comments No. of the metal component in the paste rature thickness d. de-energized d.current .n.d. stigkeit walled duck i.d. the metal sh. upset upset currentless after soldering paste heat- after Metallic metallic metallic Electrode 5 # 60 ° C, 95% # # Ag-Ant. Basic treatment ization ization Wire 0.5 # 10 V metal lung 1000h.

Wt .-% wt .-% wt .-% wt .-% ° C µm µm µm Kp 21 100 0 1 - 450 0.1 3 (Ni) 0 ~ # + 150 ~ + 250 0.9 No only Ag-Verb.

22 100 0 1 20 (carbon) 450 0.1 3 (Ni) 0 ~ # + 20 ~ + 30 1.0 no only Ag-conn.

Ag-VerbiW.% 23 100 0 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 70 2.7 No Ag powder 14% by weight 24 20 80 (Cu) 15 - 450 0.5 3 (Ni) 0 + 100 ~ + 200 3.4 No 25 20 80 (Al) 15 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 3.2 No 26 20 80 (Zn) 15 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 3.0 No 27 20 80 (Sn) 15 - 450 0.5 3 (Ni) 0 + 60 ~ + 80 3.4 No 28 20 80 (W) 15 - 450 0.5 3 (Ni) 0 + 50 ~ + 70 3.0 No 29 20 80 (Mo) 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 70 3.0 No 30 20 80 (Fe) 15 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 3.2 No 31 20 80 (Co) 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 70 3.6 No 32 20 80 (Cr) 15 - 450 0.5 3 (Ni) 0 + 60 ~ + 80 3.1 No 33 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 3.7 No Pd powder 0.01 % By weight 34 20 79.9 (Ni) 15 - 450 0.5 3 (Ni) 0 + 20 ~ + 50 3.8 No Pd powder 0.1% by weight 35 20 79.8 (Ni) 15 - 450 0.5 3 (Ni) 0 + 20 ~ + 40 3.9 No Pd powder 0.2% by weight 36 20 79.5 (Ni) 15 - 450 0.5 3 (Ni) 0 + 20 ~ + 40 4.0 No Pd powder 0.5% by weight 37 20 75 (Ni) 15 - 450 0.5 3 (Ni) 0 + 30 ~ + 60 3.5 No Pd powder 5% by weight 38 20 80 (Ni) 15 - 180 0.5 - x - -39 20 80 (Ni) 15 - 250 0.5 3 (Ni) # + 50 ~ + 80 0.3 No 40 20 80 (Ni) 15 - 300 0.5 3 (Ni) 0 ~ # + 50 ~ + 70 0.8 No. TABLE I - Continued sample composition metal surcharges tempe- avg. Thickness d. State Accurate- Adhesive- Silver- Remarks No. of the metal component in the paste rature Thickness d. currentless d. current ability n.d. stigkeit walled duck i.d. the metal sh. upset upset electroless after soldering paste heat after heat metallic metallic metallic Electrode 5 # # # Ag-Ant. Basic treatment ization ization wire 0.5 # 60 ° C, 95% metal development 10 V wt% wt% wt% wt% ° C µm µm µm Kp 1000 Hours.

41 20 80 (Ni) 15 - 350 0.5 3 (Ni) 0 + 60 ~ + 80 3.3 No 42 20 80 (Ni) 15 - 400 0.5 3 (Ni) 0 + 50 ~ + 80 3.7 No 43 20 80 (Ni) 15 - 600 0.5 3 (Ni) 0 + 60 ~ + 90 3.4 No 44 20 80 (Ni) 15 - 800 0.5 3 (Ni) 0 + 40 ~ + 60 1.8 No 45 20 80 (Ni) 15 - 900 0.5 3 (Ni) # + 40 ~ + 60 0.5 No 46 20 80 (Ni) 15 - 1050 - x - - -47 20 80 (Ni) 15 - 450 0.5 0.02 (Ni) x - - -48 20 80 (Ni) 15 - 450 0.5 0.1 (Ni) # + 30 ~ + 50 0.3 No 49 20 80 (Ni) 15 - 450 0.5 0.5 (Ni) 0 +, 40 ~ + 60 2.8 No 50 20 80 (Ni) 15 - 450 0.5 1 (Ni) 0 + 40 ~ + 70 3.5 No 51 20 80 (Ni) 15 - 450 0.5 5 (Ni) 0 + 60 ~ + 80 3.8 No 52 20 80 (Ni) 15 - 450 0.5 10 (Ni) 0+ 60 ~ + 90 3.8 No 53 20 80 (Ni) 15 - 450 0.5 20 (Ni) 0+ 70 ~ + 120 3.4 No 54 20 80 (Ni) 15 0.1 (B2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 60 3.6 No 55 20 80 (Ni) 15 0.5 (B2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 60 4.1 No 56 20 80 (Ni) 15 5 (B2O3) 450 0.5 3 (Ni) 0 + 30 ~ + 60 3.9 No 57 20 80 (Ni) 15 10 (B2O3) 450 0.5 3 (Ni) 0 + 30 ~ + 50 3.5 No 58 20 80 (Ni) 15 1 (Bi2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 60 3.7 No 59 20 80 (Ni) 15 1 (Sb2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 70 3.7 no 60 20 80 (Ni) 15 1 (PbO) 450 0.5 3 (Ni) 0 + 40 ~ + 70 3.8 no 61 20 80 (Ni) 15 1 glass powder 550 0.5 3 (Ni) 0 + 40 ~ + 60 4.1 no glass powder A 62 20 80 (Ni) 15 1 glass powder 500 0.5 3 (Ni) 0 + 40 ~ + 60 4.1 no glass powder B 63 20 80 (Ni) 15 1 glass powder 500 0.5 3 (Ni) 0 + 40 ~ + 70 4.2 no glass powder C 64 20 80 (Ni) 15 1 carbon 450 0.5 3 (Ni) 0 + 30 ~ + 50 3.8 no carbon powder 65 20 80 (Ni) 15 10 carbon 450 0.5 3 (Ni) 0 + 10 ~ + 20 3.7 no carbon powder 66 20 80 (Ni) 15 30 carbon 450 0.5 3 (Ni) 0 0 ~ + 10 3.2 no carbon powder 67 20 80 (Ni) 15 50 carbon 450 0.5 3 (Ni) # + 10 ~ + 20 0.9 no carbon powder 68 20 80 (Ni) 15 10 (SiO2) 450 0.5 3 (Ni) 0 + 10 ~ + 30 3.6 No SiO2 powder 69 20 80 (Ni) 15 10 (MgO) 450 0.5 3 (Ni) 0 + 20 ~ + 30 3.6 No MgO powder 70 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 60 0.6 no without etching d. Substrate TABLE I - Continuation Sample Composition Metal Additions Tempe Avg. Thickness d. Condition true to size Adhesive Silver Remarks No. of the metal component in the paste rature Thickness of the currentless d.current n.d. sitgkeit wandente i.d. the metal sh. upset upset currentless after soldering paste heat resisting heat metal metal metal metal electrode 5 # 60 ° C, 95% # # hand treat. ization ization wire 0.5 # 10 V Ag-Ant. Basic 1000 hours

metal wt .-% wt .-% wt .-% wt .-% ° C µm µm µm Kp 71 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 3.6 No H2SO4 treatment 72 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 3.7 No HNO3 treatment 73 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 80 ~ + 150 2.0 No metal powder 4µ 74 20 80 (Ni) 15 - 450 0.5 3 (Cu) 0 + 50 ~ + 90 3.2 No de-energized without current 75 Ni-electrode applied without current (conventional) 3 (Ni) 0 - 0.5 No 76 conventional sliver melting electrode 5 (Ag) - - 3.0 Yes 77 conventional sliver melting electrode 10 (Ag) - - 3.3 Yes 78 conventional sliver melting electrode 20 (Ag) - - 3.3 Yes TABLE II sample composition metal add. Tempe- Diameter- Thickness Condition Dimensional Accurate- Adhesive- Dielectric Remarks No. of Metal components i.d. rature beautiful. d. d. ability n.d. strength properties i.d. Paste d. Heat thickness current current current ability n.d. (1 KHz, 20 ° C) paste mebe- d.Melos metallization soldering before the after the Ag content basic handlg.tall- up endurance test endurance test layer metal n.d. br. br. tan # 85 ° C, 85% rd.F.

Heat- Metal- Metal- x10-4 1000 hrs.

Wt .-% wt .-% wt .-% wt .-% ° C µm µm µm Kp # # x10-4 1 100 0 10 - 450 0.5 3 (Ni) 0 ~ # + 60 ~ + 90 1.0 19000 130 17600 168 2 80 20 (Ni) 10 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 3.4 20 200 120 18 400 162 3 60 40 (Ni) 10 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 4.2 20 900 110 19050 140 4 40 60 (Ni) 10 - 450 0.5 3 (Ni) 0 + 40 ~ + 70 4.5 21 200 105 19500 132 5 20 80 (Ni) 10 - 450 0.5 3 (Ni) 0 + 30 ~ + 60 4.6 21700 102 20 100 127 6 10 90 (Ni) 10 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 4.0 21000 109 19200 138 7 5 95 (Ni) 10 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 3.4 20700 111 18800 136 8 0.5 99.5 (Ni) 10 - 450 0.5 3 (Ni) 0 ~ # + 20 ~ + 40 1.7 18700 135 17 500 156 9 0 100 (Ni) 10 - 450 0.5 3 (Ni) # ~ x + 10 ~ + 30 0.4 16200 186 13800 420 10 20 80 (Ni) 0.02 - 450 0.02 - x - - - - - -11 20 80 (Ni) 0.05 - 450 0.05 3 (Ni) # + 150 ~ + 250 0.6 16800 150 14800 220 12 20 80 (Ni) 0.5 - 450 0.1 3 (Ni) 0 ~ # + 150 ~ + 250 0.8 18600 132 17200 172 13 20 80 (Ni) 1 - 450 0.1 3 (Ni) 0 ~ # + 120 ~ + 200 1.5 19300 127 17900 165 14 20 80 (Ni) 5 - 450 0.2 3 (Ni) 0 + 120 ~ + 180 3.5 21000 108 19300 137 15 20 80 (Ni) 20 - 450 0.7 3 (Ni) 0 + 50 ~ + 70 4.5 21500 103 20000 127 16 20 80 (Ni) 30 - 450 1.0 3 (Ni) 0 + 20 ~ + 40 4.1 21300 1006 19600 130 17 20 80 (Ni) 30 - 450 1.5 3 (Ni) 0 + 80 ~ + 150 2.2 20 100 120 18300 162 18 20 80 (Ni) 40 - 450 2 3 (Ni) 0 - 70 ~ + 130 1.5 19500 125 17700 166 19 20 80 (Ni) 60 - 450 4 3 (Ni) + 180 ~ + 300 0.7 17 200 145 15 300 210 20 100 0 0.05 - 450 0.05 3 (Ni) # + 180 ~ + 300 1.0 17600 140 15200 200 only Ag-conn.

21 100 0 1 - 450 0.1 3 (Ni) 0 ~ # + 150 ~ + 300 1.4 19200 125 17800 165 only Ag-Verbdg.

22 100 0 1 20 carbon 450 0.15 3 (Ni) 0 ~ # + 10 ~ + 20 1.6 19400 122 18 100 160 only Ag connection.

fabric 23 100 0 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 70 3.5 19800 125 1800 165 Ag-Verbg. 1% by weight 24 20 80 (Cu) 15 - 450 0.5 3 (Ni) 0 + 100 ~ + 200 4.1 20 900 112 19500 139 Ag powder 14 "25 20 80 (Al) 15 - 450 0.5 3 (Ni) 0 + 50 ~ + 70 3.9 20700 112 19400 140 26 20 80 (Zn) 15 - 450 0.5 3 (Ni) 0 + 60 ~ + 80 3.8 20700 114 19300 140 27 20 80 (Sn) 15 - 450 0.5 3 (Ni) 0 + 60 ~ + 80 4.2 21300 106 19400 134 28 20 80 (W) 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 70 3.6 20000 122 18 100 161 TABEL II - continuation sample composition metal add. Tempe- Thickness Condition Dimensionally Accurate- Adhesive- Dielectric Comments No. of the metal component i.d. rature nice d. d. ability n.d. solid-property nente i.d. Paste d.Wär- Thick Strom-Strom- current ability n.d. (1 KHz, 20 ° C) paste mebe- d.Mellos metallisir- soldering before that after the Ag-Ant. Basic handlg. tall-up-up endurance test endurance test metal layer br. br. tan # 85 ° C, 85% rd.h.

n.d.Wär-Metal-Metal- # x10-4 1000 hours

mebehdg.lisier.lisier. tan # # wt% wt% wt% wt% ° C µm µm µm Kp x10-4 29 20 80 (Mo) 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 60 3.7 20 100 118 18 300 158 30 20 80 (Fe) 15 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 3.9 20 500 113 19 300 140 31 20 80 (Co) 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 70 4.4 21200 105 19200 133 32 20 80 (Cr) 15 - 450 0.5 3 (Ni) 0 + 50 ~ + 80 3.7 20 100 120 18 100 157 33 20 80 (Ni) 15 - 180 0.5 - x - - - - - -34 20 80 (Ni) 15 - 250 0.5 3 (Ni) # + 60 ~ + 80 0.6 16800 160 14600 230 35 20 80 (Ni) 15 - 300 0.5 3 (Ni) 0 ~ # + 60 ~ + 80 1.6 18800 137 17600 157 36 20 80 (Ni) 15 - 350 0.5 3 (Ni) 0 + 60 ~ + 80 4.2 20700 112 19000 140 37 20 80 (Ni) 15 - 400 0.5 3 (Ni) 0 + 50 ~ + 70 4.6 21600 103 20 100 129 38 20 80 (Ni) 15 - 600 0.5 3 (Ni) 0 + 60 ~ + 90 4.0 21200 108 19300 136 39 20 80 (Ni) 15 - 800 0.5 3 (Ni) 0 + 50 ~ + 70 2.4 19900 119 18100 163 40 20 80 (Ni) 15 - 900 0.5 3 (Ni) # + 40 ~ + 60 1.0 17300 142 15800 180 41 20 80 (Ni) 15 - 1050 0.5 - x - - - - - -42 20 80 (Ni) 15 - 450 0.5 0.02 (Ni) x - - - - - -43 20 80 (Ni) 15 - 450 0.5 0.1 (Ni) # + 30 ~ + 60 0.6 16900 160 14 800 235 44 20 80 (Ni) 15 - 450 0.5 1 (Ni) 0 + 30 ~ + 60 3.5 21 100 110 19 400 138 45 20 80 (Ni) 15 - 450 0.5 5 (Ni) 0 + 30 ~ + 60 4.2 21400 107 19600 130 46 20 80 (Ni) 15 - 450 0.5 10 (Ni) 0 + 50 ~ + 70 4.7 21500 103 20000 128 47 20 80 (Ni) 15 - 450 0.5 20 (Ni) 0 + 60 ~ + 80 4.8 21200 108 19500 133 48 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 80 ~ + 120 4.2 21200 112 19300 140 49 20 80 (Ni) 15 0.1 (B2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 60 4.4 21400 104 19300 130 50 20 80 (Ni) 15 0.5 (B2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 60 5.0 21800 102 19200 130 51 20 80 (Ni) 15 5 (B2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 60 4.8 21 900 102 19 100 135 52 20 80 (Ni) 15 10 (B2O3) 450 0.5 3 (Ni) 0 + 30 ~ + 50 4.4 21000 110 17900 148 53 20 80 (Ni) 15 1 (Bi2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 60 4.7 21200 105 19200 130 54 20 80 (Ni) 15 1 (Sb2O3) 450 0.5 3 (Ni) 0 + 40 ~ + 70 4.8 21100 107 19000 132 55 20 80 (Ni) 15 1 (PbO) 450 0.5 3 (Ni) 0 + 40 ~ + 70 4.9 2100 106 19 100 131 56 20 80 (Ni) 15 1 glass 550 0.5 3 (Ni) 0 + 40 ~ + 60 5.2 21 800 105 19500 125 glass powder A powder TABLE II - continued sample composition Metal surcharge Tempe- Through Thick Condition Dimensionally Accurate- Half- Dielectric Remarks No. d. Metal components i.d. rature beautiful. d. d. ability n.d. solid-property nente i.d. Paste d.Wär- Thickness strom-strom- stroml. ability n.d. (1KHz, 20 ° C) paste mebe- d.Melos metallization soldering before after the Ag-Ant. Basic hand tall- open endurance test endurance test metal lg. cut br. br. tan # 85 ° C, 85% approx.

n.d.Wär-Metal-Metal- # x10-4 1000 hours

mebehdg. lisier. lisier. tan. # # wt% wt% wt% wt% ° C µm µm µm Kp x10-4 57 20 80 (Ni) 15 1 glass 500 0.5 3 (Ni) 0 + 40 ~ + 60 5.0 21 600 103 19400 127 glass powder B powder 58 20 80 (Ni) 15 1 glass 500 0.5 3 (Ni) 0 + 40 ~ + 60 5.1 21500 102 19400 125 glass powder C powder 59 20 80 (Ni) 15 1 carbon 450 0.5 3 (Ni) 0 + 30 ~ + 60 4.7 21400 104 20 100 129 Carbon powder 60 20 80 (Ni) 15 10 carbon-450 0.5 3 (Ni) 0 + 0 ~ + 20 4.6 21500 105 20 200 130 carbon powder 61 20 80 (Ni) 15 30 carbon-450 0.5 3 (Ni) 0 + 10 ~ - 10 4.0 21000 110 19200 137 carbon powder 62 20 80 (Ni) 15 50 carbon-450 0.5 3 (Ni) # + 10 ~ + 20 1.5 18 100 140 16 200 159 carbon powder 63 20 80 (Ni) 15 10 (SiO2) 450 0.5 3 (Ni) 0 + 10 ~ + 30 4.5 21300 108 19500 132 SiO2 powder 64 20 80 (Ni) 15 10 (MgO) 450 0.5 3 (Ni) 0 + 15 ~ + 30 4.4 21200 109 19500 130 MgO powder 65 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 40 ~ + 60 1.3 19500 135 17700 160 without etching d.

Substrate 66 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 30 ~ + 50 4.5 21 500 102 20 200 127 H2SO4 treatment

67 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 30 ~ + 60 4.6 21 600 102 20 100 129 HNO3 treatment 68 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 80 ~ + 150 2.8 20 300 118 18500 157 metal powder 4µ 69 20 80 (Ni) 15 - 450 0.5 3 (Ni) 0 + 50 ~ + 100 4.2 21000 110 19200 130 de-energized 70 conventional. currentless applied Ni electrode 3 (Ni) 0 - 0.7 17000 170 14200 250 71 conventional silver melting electrode 5 (Ag) - - 3.8 20600 115 18600 161 72 conventional silver fusible electrode 10 (Ag) - - 4.1 20800 114 18600 161 73 conventional silver fusible electrode 20 (Ag) - - 4.2 21000 114 18700 160 Blank page

Claims (28)

A method for producing an electrode on a heat-resistant insulating substrate by making a paste of 0.05 to 40 wt. t a metal material containing 0.5 to 100 C-ew.-t of a silver component, Remainder an organic carrier, applied to the substrate, at a temperature of Heat treated 250 to 9000C, leaving a 0.05 to 2 micrometer thick layer of metal particles and then an electrode made of nickel or on the metal particle layer Forms copper in a thickness of 0.1 to 20 micrometers by electroless plating. 2. The method according to claim 1, characterized in that it is the heat-resistant insulating substrate is a ceramic substrate. 3. The method according to claim 1, characterized in that the The substrate is roughened by chemical and / or mechanical treatment. 4. The method according to claim 1, characterized in that the metal material 0.5 to 100% by weight of a silver component and 99.5 to 0% by weight of a base metal component contains, which is at least one metal from the group nickel, copper, Aluminum, zinc, tin, tungsten, molybdenum, iron, cobalt and chromium are involved. 5. The method according to claim 4, characterized in that the base metal component Nickel is. 6. The method according to claim 4, characterized in that the metal material Contains 0.01 to 5% by weight of palladium. 7. The method according to claim 4, characterized in that it is the silver component is silver powder with a diameter of less than 2 micrometers and / or a silver compound which reduces to silver on heat treatment and that the base metal component is a powder of metal and / or alloy is less than 2 micrometers in diameter. 8. The method according to claim 4, characterized in that the silver component 5 to 80% by weight and the base metal component makes up 95 to 20% by weight. 9.'Verfahren according to claim 1, characterized in that the metal material 5 to 30 wt. t is present in the paste. 10. The method according to claim 1, characterized in that the paste furthermore contains 0.5 to 5% by weight of glass powder or low-melting oxide. 11. The method according to claim 10, characterized in that the clasp powder Contains B203 and that the oxide is B2O3. 12. The method according to claim 1, characterized in that the paste furthermore contains 1 to 30% by weight of carbon powder or inorganic powder. 13. The method according to claim 1, characterized in that at Heat treated from 350 to 600 ° C. 14. The method according to claim 1, characterized in that the at the metal particle layer resulting from the heat treatment has an average thickness from 0.2 to 1 micrometer. 15. The method according to claim 2, characterized in that the by Electroless plating electrode is 1 to 10 microns thick. 16. The method according to claim 1, characterized in that the heat-treated substrate before electroless plating with a Pt, Os-, Ir- or Ru-Ion treated. 17. The method according to claim 1, characterized in that the heat-treated substrate in a solution with at least one organic acid, treated with an ammonium solution, nitric acid and sulfuric acid. 18. Electrode on a heat-resistant insulating substrate, consisting from a 0.05 to 2 micrometer thick metal layer made of a silver component and a 0.1 to 20 micrometer thick layer of nickel or copper passing through electroless plating was applied. 19.Electrode according to claim 18, characterized in that the heat-resistant insulating substrate is a ceramic substrate. 20. Electrode according to claim 18, characterized in that the substrate has been roughened by chemical and / or mechanical treatment. 21. Electrode according to claim 18, characterized in that the metal layer 0.5 to 100% by weight of silver component and 99.5 to 0% by weight of a base metal component which consists of at least one element from the group consisting of nickel, copper, aluminum, Zinc, tin, tungsten, molybdenum, iron, cobalt, chromium. 22. Electrode according to claim 21, characterized in that the base metal component Nickel is. 23. Electrode according to claim 21, characterized in that the metal layer Contains 0.01 to 5 wt .-% palladium component. 24. Electrode according to claim 21, characterized in that the silver component 5 to 80 wt .-% and the base metal component make up 95 to 20 wt .-%. 25. Electrode according to claim 18, characterized in that the metal layer Contains glass or low-melting oxide. 26. Electrode according to claim 25, characterized in that the glass component Contains B203 and the low melting point oxide is B203. 27. Electrode according to claim 18, characterized in that the metal layer is 0.2 to 1 micrometer thick on average. 28. Electrode according to claim 18, characterized in that the through electroless plating applied layer is 1 to 10 micrometers thick.