JPH04210481A - Composition for forming palladium or palladium alloy thin film and its manufacture - Google Patents

Abstract

PURPOSE:To form a dense thin film fine line in which the number of films to be laminated can remarkably be increased by specifying the components of a conductive composition and their ratios. CONSTITUTION:The composition for forming a palladium or palladium alloy thin film in this invention is as follows. Namely, it is a one contg., simple grain dispersed ultrafine powder of palladium or a palladium alloy having 30 to 1000Angstrom average grain size by 5 to 70wt.% as metal, simple grain dispersed ultrafine powder of rhodium or iridium having 30 to 1000Angstrom average grain size by 0.005 to 1.0wt.% as metal, arbitrarily contg. simple grain dispersed ultrafine powder of gold having 30 to 1000Angstrom average grain size by 2.5 to 35wt.% as metal and furthermore 0.5 to 10wt.% of one or more kinds among lead, boron, silicon, bismuth, vanadium, Ti and Ba having the same grain size.

Description

[Detailed description of the invention]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a formulation for forming palladium or palladium alloy thin films and a method for producing the same. [00021 The composition of the present invention can be used in particular for manufacturing multilayer ceramic capacitors, low-temperature fired multilayer ceramic substrates, glass substrates, glazed substrates, alumina substrates, etc. used in consumer or industrial electronics equipment to produce conductive circuits and multilayer circuits. can do. [0003]

[Prior Art and Its Problems] Multilayer capacitors and multilayer ceramic substrates are generally produced by molding a ceramic composition in which ceramic powder is uniformly dispersed in a vehicle, and placing conductive metal powder on an unfired sheet. An electrode or circuit layer is formed by screen printing a conductive metal powder-containing formulation (hereinafter also simply referred to as a conductive formulation) consisting of a vehicle, and after drying, the desired number of sheets are stacked, and finally the electrode or by stacking and compressing unprinted sheets of circuitry, or by alternately screen-printing said ceramic and conductive formulations, drying and laminating, and alternating ceramic layers with electrode or circuit layers. It was not possible to form a laminate with the same material. The unfired laminate thus obtained is cut into a predetermined size, then fired at a sufficient temperature, and external electrodes, circuits, semiconductor chips, etc. are mounted on the integrated laminate to form a multilayer capacitor. They had completed multilayer ceramic substrates, etc. [0004] This conductive formulation has previously been commonly adapted from conductive formulations for thick film hybrid ICs. There are currently many types of conductive formulations for thick film hybrid ICs on the market, but some use metal powder particles as large as several μm, which is the raw material for the conductive formulations. Although the primary particles were fine, they caused secondary aggregation and the size of the agglomerated particles increased to several μm. Therefore, in order to produce a uniform and dense fired film, the dry film thickness had to be about ten micrometers. For this reason, when sheets with circuits formed on them are laminated and compressed, the sheets themselves are greatly distorted because the parts on which no circuits are formed are brought into close contact with each other. Therefore, it became difficult to uniformly press the sheets, and the laminate was prone to delamination. In addition, there is a tendency to increase the number of laminated layers as miniaturization and performance increases, but if conductive formulations for thick-film hybrid ICs are repurposed, the dry film thickness must be significantly reduced due to problems with the uniformity of the fired film. This made it difficult to increase the number of laminated sheets with the same total film thickness. [0005]

[Object of the Invention] Therefore, the object of the present invention is to provide a conductive composition that is dense and can be formed into a thin film, which can reduce delamination and cracking by forming thin film fine lines, and greatly increase the number of laminated sheets. The purpose is to provide a method for manufacturing the same. [0006]

[Means for Solving the Problems] According to the present invention, the above object is to provide a single-particle dispersed ultrafine powder of palladium or palladium alloy having an average particle size of 30 to 1000 Å, which is dispersed in an organic solvent in the form of single particles. A metal-organic compound of rhodium and/or iridium containing 5% to 70% by weight as a metal and/or having an average particle size of 30 to 1000 dispersed in an organic solvent as a single particle.
1 (contains 0.005 to 1.0% by weight of a single-particle dispersed ultrafine powder of rhodium and/or iridium as a metal, optionally containing a gold metal-organic compound and/or a single-particle dispersed ultrafine powder in an organic solvent in the state of a single particle of gold). Contains 2.5% to 35% by weight of metal, single-particle dispersed ultrafine powder of gold having an average particle diameter of 30 to 1000A, and optionally dispersed in an organic solvent as a single particle. The average particle size was 30
to 10,000,000,000,000,000,000,000,000,000,000,000,000,000,000 Contains 0.5% to 10% by weight of particle-dispersed ultrafine powder as metal,
Furthermore, lead, boron, silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron, zirconium,
One or more selected from the group consisting of titanium and barium
This is achieved by a formulation for forming palladium or palladium alloy thin films, which is characterized by containing 0.51% to 10% by weight of one or more metal-organic compounds as metal. [0007] The above object is also achieved by adding rhodium and/or rhodium to a single-particle dispersed ultrafine powder of palladium or palladium alloy having an average particle size of 30 to 1000 Å, which is dispersed in an organic solvent in the form of single particles. Or a metal-organic compound of iridium and/or a single particle dispersed in an organic solvent with an average particle size of 30 to 1000 Å.
Single-particle dispersed ultrafine powder of rhodium and/or iridium, optionally a metal organic compound of gold, and/or a single-particle dispersed ultrafine powder in an organic solvent with an average particle size of 3.
Single-particle dispersion ultrafine powder of gold having a size of 0 to 1000 Å, optionally lead, boron, silicon, bismuth, vanadium, zinc with an average particle size of 30 to 1000 Å dispersed in an organic solvent in a single particle state. , nickel, chromium, tin, iron,
One or more single-particle dispersed ultrafine powders selected from the group consisting of zirconium, titanium, barium, and their oxides, and optionally lead, boron, silicon, bismuth, vanadium, zinc, nickel, chromium, and tin. This is achieved by a method for producing a palladium or palladium alloy thin film-forming formulation, which comprises blending one or more metal-organic compounds selected from the group consisting of iron, zirconium, titanium, and barium. [00081] Hereinafter, the palladium or palladium alloy thin film forming composition of the present invention and the method for producing the same will be explained in detail. [00091 The palladium or palladium alloy thin film forming formulation of the present invention comprises palladium or palladium alloy monomers having an average particle size of 30 to 1000 Å, preferably 30 to 50 OA, dispersed in an organic solvent in the form of single particles. 5% to 70% by weight of particle-dispersed ultrafine powder as metal
The content is preferably from 15% to 45% by weight. [00101 The reason why the content of single-particle dispersed ultrafine powder of palladium and/or palladium alloy was changed from 5% by weight to 70% by weight is because it is difficult to create a uniform fired thin film if it is less than 5% by weight. This is because if it exceeds 70% by weight, the conductive formulation will have too high a viscosity and the printing properties will deteriorate. [00111 With single-particle dispersed ultrafine powders having an average particle diameter of 1000 Å or more, it tends to be difficult to suppress the granulation of palladium or palladium alloy thin films with rhodium or iridium. [00121 The palladium or palladium alloy thin film forming formulation of the present invention further comprises a metal-organic compound of rhodium and/or iridium and/or a compound having an average particle size of 30 to 10
0.005 to 1.0% heavy air as a metal using single-particle dispersed ultrafine powder of rhodium and/or iridium with a diameter of 0.00 Å
, preferably 0.01% to 0.5% by weight. [0013] If the rhodium and/or iridium content is 0.005% by weight or less, it is difficult to suppress agglomeration of the fired film, and if the rhodium and/or iridium content is 1.0% by weight or more, the film This is because not only the effect of formation is not sharp, but also the resistance value increases greatly. [00141 The palladium or palladium alloy thin film forming composition of the present invention comprises a metal organic compound of gold and/or a single gold particle having an average particle size of 30 to 1000 Å dispersed in an organic solvent in the form of a single particle. 2.5% to 35% by weight of the dispersed ultrafine powder as metal, preferably 1
It may be contained in an amount of 0% to 20% by weight. [0015] 2.5% by weight to 3S% by weight of the gold metal organic compound and/or the above-mentioned gold single particle dispersed ultrafine powder
The reason why it is included is to better form a palladium or palladium alloy thin film. In order to maintain the properties of palladium, the gold content is 50% relative to palladium metal.
% or less is preferable. [00161 The metal-organic compounds that are formulation components of the formulations of the present invention are organic acid salts of metals, such as resinates, carboxylates, and metal complexes that are soluble in organic solvents. [0017] The palladium or palladium alloy thin film-forming formulation of the present invention also contains lead, boron, silicon, bismuth, vanadium having an average particle size of 30 to 1000 Å dispersed in an organic solvent in the form of single particles. , zinc, nickel, chromium, tin, iron, zirconium, titanium, barium, and their oxides.
The content may be from 10% by weight, preferably from 1% to 5% by weight. [00181 The palladium or palladium alloy H pus-forming formulation of the present invention further comprises lead, boron, silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron,
One or more metal-organic compounds selected from the group consisting of zirconium, titanium, and barium as a metal.
．． 5% to 10% by weight, preferably 1% to 5% by weight
It may contain % by weight. [00191 The above single particle dispersed ultrafine powder and/or L
The metal-organic compound was added because the single-particle dispersed ultrafine powder of palladium and/or palladium alloy in the conductive formulation is extremely fine, so that the sintered film of the single-particle dispersed ultrafine powder and the ceramic substrate are closely bonded. In order to achieve this, the particles of conventional glass frits and metal oxides are too large, which may actually destroy the formation of a dense sintered film, and it is necessary to add a small amount compared to single-particle dispersed ultrafine powder of palladium or palladium alloy. Therefore, large particles can only be bonded partially and the adhesion force is low, so the purpose is to improve this situation. The palladium or palladium alloy thin film-forming formulation of the present invention may be made of rosin, asphalt, alkyd resin, epoxy resin, acrylic resin, polyvinyl butyral resin in order to increase the viscosity of the formulation or to make the formulation into a paste. , cellulose resin, etc. may be contained as appropriate. [002ON] Furthermore, the formulation of the present invention may optionally contain waxes such as paraffin wax and microwax,
It may contain a plasticizer such as dioctyl phthalate, a surfactant such as sorbitan monostearate, an organic solvent, etc. as appropriate. [0021] This formulation can be used for brush painting, screen printing, stamping, letterpress printing, etc. depending on the R combination balance of the resin and organic solvent. [00221 The single-particle dispersed ultrafine powder used in the present invention can be produced by a method in which an organic solvent is adsorbed on the surface of the metal or oxide ultrafine powder produced by an evaporation method in a gas, and the single-particle dispersed state is taken out. can. [0023] For example, after the metal is heated and evaporated in an atmosphere of an inert gas such as helium at a pressure of 10 Torr or less, it is condensed in the inert gas to generate particles, and the particles are collected by riding on the gas flow. While the particles are being transported to the chamber, organic solvents such as terpineol, anethole, borneol, limonene, turpentine oil, rosemary oil, butylcarpitol, toluene, hexane, benzyl acetate, and terpenyl acetate are introduced to coat the surface of the particles. It can be manufactured by a method in which particles are coated with water to prevent adhesion and agglomeration of particles, and then the particles are attached and collected on a cooling surface. It is also possible to further stabilize the dispersion of the particles by adding an additive to the single-particle dispersed ultrafine particles recovered together with the organic solvent. [0024] Furthermore, the single-particle dispersed ultrafine powder of palladium or palladium alloy used in the present invention includes those obtained by oxidizing the surface of the single-particle dispersed ultrafine powder. [0025] The palladium or palladium alloy thin film forming formulation of the present invention is a single-particle dispersed ultrafine powder of palladium or palladium alloy having an average particle size of 30 to 1000 Å, which is dispersed in an organic solvent in the form of single particles. metal-organic compounds of rhodium and/or iridium and/or rhodium and/or having an average particle size of 30 to 10008 dispersed in an organic solvent in the form of single particles.
or a single-particle dispersed ultrafine powder of iridium, optionally a metal-organic compound of gold, and/or a single-particle dispersed ultrafine gold particle having an average particle size of 30 to 1000, dispersed in an organic solvent in the form of a single particle. Lead, boron, silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron, zirconium, titanium, barium with an average particle size of 30 to 1000 Å dispersed in an organic solvent in the form of powder or single particles. and one or more types of single particle dispersed ultrafine powder selected from the group consisting of oxides thereof and optionally lead,
Produced by a method including a step of blending one or more metal organic compounds selected from the group consisting of boron, silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron, zirconium, titanium, and barium. be able to. [0026] In the production of the formulation of the present invention, rosin, asphalt, alkyd resin, epoxy resin, acrylic resin, polyvinyl butyral resin,
Cellulose resin etc. can be blended. [0027] In the production of the formulation of the present invention, waxes such as paraffin wax and microwax, plasticizers such as dioctyl phthalate, surfactants such as sorbitan monostearate, organic solvents, etc. may be added as necessary. They may be blended as appropriate. [0028] The blend obtained in the above step may be used as it is as a blend of the present invention, but if necessary, the blend may be shaken, stirred, coarsely kneaded, or mixed by a known method, for example. The formulations of the present invention can also be obtained by processing by heating or other methods. [0029] The formulation of the present invention for screen printing, stamping, letterpress printing, etc. can be prepared by, for example, mixing the above-mentioned single-particle dispersed ultrafine powder with a resin and an organic solvent in a mortar or the like for a small amount, or by universal mixing and stirring for a large amount. It can be produced by thoroughly kneading the mixture using a mill or a mixer such as a Raikai machine, and then thoroughly kneading it using a three-roll mill. [00301] The formulation of the present invention for brush application can also be obtained by, for example, reducing the amount of resin etc. added to the above printing formulation to reduce the viscosity and shaking or stirring. [00311 The palladium or palladium alloy thin film forming formulation of the present invention has the following characteristics compared to commonly used thick film vibe knot IC formulations:
The palladium or palladium alloy thin film forming formulation of the present invention has a raw material metal powder having a particle size of 30A to 1000Å, which is extremely fine compared to conventional thick film hybrid IC formulations, and each individual particle is in the form of particles. Since it is made of dispersed ultrafine particles, thin layer printing and 50 μm fine lines can be easily printed. [0032] ■ The palladium or palladium alloy thin film forming formulation of the present invention can be used to form conventional thick film hybrid ICs.
The particle size of the raw metal powder is 308 to 10 compared to the formulation for
Ultrafine particles of 00A, each of which is dispersed in the form of a single particle, are made by dispersing rhodium and/or iridium metal organic compounds and/or ultrafine powder in an organic solvent in the form of single particles. Since it contains ultrafine powder dispersed in single particles of rhodium and/or iridium, it is possible to form a coating that prevents the generation of sintered agglomerates of the ultrafine powder. [0033]■ The palladium or palladium alloy thin film forming formulation of the present invention can be used to form conventional thick film hybrid ICs.
The particle size of the raw metal powder is 30A to 10A compared to the formulation for
Because it contains ultrafine particles as small as 00A, each of which is dispersed in the form of a single particle, it has strong reactivity and can be fired at lower temperatures. [00341■ The palladium or palladium alloy thin film forming formulation of the present invention can be used to form conventional thick film hybrid ICs.
The particle size of the raw metal powder is 30 to 100 compared to the formulation for
0A, each particle is dispersed in the state of a single particle, and the glass component to increase adhesion to the substrate and the raw material powder for chemical bonding are mixed into ultrafine powder into single particles. Since it is a single-particle dispersed ultrafine powder dispersed in an organic solvent, a single-particle dispersed ultrafine powder oxide and/or a metal organic compound is mixed in the state, so even a thin layer can be dense and have good adhesion to the substrate. It is possible to obtain a film with [0035] ■ The palladium or palladium alloy thin film forming formulation of the present invention can be used to form conventional thick film hybrid ICs.
The particle size of the raw metal powder is 30A to 10A compared to the formulation for
00A, which is very fine and each particle is dispersed in the state of a single particle, so even if the printed film thickness is thin, it can form a uniform film, making it easier to stack layers, which causes delamination. tendency can be reduced. [0036]

[Examples and Comparative Examples] The present invention will be explained in detail below using Examples and Comparative Examples. [0037]

Example 1 illustrates the preparation of a palladium film forming formulation according to the present invention for forming a palladium film and the formation of a palladium film using the formulation. [0038] The following formulation ingredients (a), (b), (
c), (d) and (e) (a) A dispersion containing 60% by weight of Pd in which ultrafine palladium powder with an average particle size of 50 A is dispersed in terpineol (hereinafter referred to as an ultrafine powder dispersion containing single particles of palladium) (b) A solution containing 5% by weight of Ph, which is obtained by dissolving rhodium octoate in a solvent prepared by mixing rosemary oil and benzyl acetate at a weight ratio of 6:4 (hereinafter abbreviated as rhodium salt solution). ) (C) A solution in which 20% by weight of rosin is dissolved in a solvent containing anethole and limonene mixed at a weight ratio of 7:3 (hereinafter abbreviated as rosin solution) (d) Ethyl cellulose (manufactured by Percules N-1)
,0(e) Prepare butyl calpitol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), and prepare these preparation ingredients (a), (b), (C),
Mix (d) and (e) with the following weight ratios: weight ratio (a)
) Palladium single particle dispersion ultrafine powder dispersion 80.
0(b) Rhodium salt solution
5.0(c) Rosin solution
5.0(d) Ethylcellulose
3.0(e) Butylcarpitol
Mix at 7.0 and add the blended ingredients (
Blends of a), (b), (e), (d) and (e) were obtained. [0039] After thoroughly kneading 50 g of the above platform in an agate mortar, the mixture was kneaded in a three-roll mill to obtain a palladium thin film-forming formulation. [00403 The formulation was used to deposit 50 μm on a glass substrate.
Screen print a pattern of wide slits and heat at 125℃
After drying for 15 minutes at 550℃, the temperature was raised at a rate of 20℃/min in a tunnel furnace, held at 550℃ for 10 minutes, and then heated to 20℃.
The temperature was lowered at a rate of 1/min, and a conductive circuit was manufactured. [00411 The thickness of the fine line of the obtained conductive circuit is 1.0 μm, and the specific resistance is 25 × 10−6Ω・
It was cm. [0042]

Example 2 illustrates the preparation of a palladium-gold alloy thin film forming formulation according to the present invention for forming a palladium-gold alloy thin film and the formation of a palladium-gold alloy thin film using the formulation. [0043] Preparation components (a) and (b) described in Example 1
), (c), (d), (e) and the following preparation ingredients (f) (f) A dispersion containing 60% by weight of Au, in which a single particle of all ultrafine powder with an average particle size of 100 is dispersed in terpineol (
Hereinafter, it will be abbreviated as a total single particle dispersed ultrafine powder dispersion. ) are prepared, and these preparation ingredients (a) to (f) are prepared as follows:
Palladium single particle dispersion ultrafine powder dispersion 70.0
(b) Rhodium salt solution
5.0(c) Rosin solution
5,0(d) ethylcellulose
3.0(e) Butylcarpitol
7.0 (f) Total single particle dispersion ultrafine powder dispersion 10.0 to mix the preparation components (a), (b), (C), (d), (e) and (f) I got something. [0044] After thoroughly kneading 50 g of the above platform in an agate mortar, the mixture was kneaded with three rolls to obtain a palladium-gold alloy film-forming formulation. [00451 Using this, a pattern of 50 μm wide slits was screen printed on a green sheet of glass-ceramics for low-temperature firing, and after being thoroughly dried, 30 layers were laminated and pressure molded to form a 200 μm wide slit pattern in an electric furnace. After increasing the temperature at a rate of ℃/hour and holding it at 1000℃ for 2 hours,
The temperature decreases at a rate of 0°C/hour, forming a laminated conductive circuit (laminated circuit).
was manufactured. [00461 No cracking or delamination was observed in the obtained laminated circuit. [00471

[Example 3] Production of a formulation for forming a palladium-gold alloy film to obtain a glossy palladium-colored thin film by applying the formulation to a glass glaze substrate by a brush coating method and baking it, and the formulation The following is an example of a palladium-gold alloy thin film using . [0048] Preparation components (a) and (b) described in Example 1
), and (C), formulation component (f) as described in Example 2.
and the following formulation components (g), (h), (i) and (j) (g) Cr5 weight in which chromium octoate is dissolved in a solvent prepared by mixing rosemary oil and benzyl acetate in a weight ratio of 6:4. % solution (hereinafter abbreviated as chromium salt solution) (h) Bi 5% solution by weight (hereinafter referred to as bismuth (abbreviated as salt solution) (i) P in which lead octoate is dissolved in a solvent containing rosemary oil and benzyl acetate in a weight ratio of 6:4.
b5% by weight solution (hereinafter abbreviated as lead salt solution) (j)
A solution (hereinafter abbreviated as Giltonite solution) in which 10% Giltonite (manufactured by Ziegler Chemical & Minerals) was dissolved in a solvent containing anethole and limonene in a weight ratio of 3:7 was prepared. Preparation ingredients (a), (b), (C
), (f), (g), (h), (i) and (j
) to the following weight ratio preparation components Weight ratio (a
) Palladium single particle dispersion ultrafine powder dispersion 6o,
0(b) Rhodium salt solution
5.0(c) Rosin solution
11.0(f) Total single particle dispersion ultrafine powder dispersion
12.0 (g) Chromium salt solution
2.0(h) bismuth salt solution
2.0(i) Lead salt solution
2.0 (j) Giltonite solution Mix at 6.0 and prepare ingredients (a), (b), (C), (f), (
Blends of g), (h), (i) and (j) were obtained. [00491 100 g of the above formulation was placed in a 500 ml bottle and shaken for 1 hour in a shaker to obtain a palladium-gold alloy thin film forming formulation. [00501 This formulation was applied to a glass glaze substrate by brush painting and baked at 750° C. for 10 minutes to obtain a glossy palladium-gold alloy thin film with a thickness of 0.671 m. [00511] Example 4 illustrates the production of a palladium alloy thin film forming formulation according to the present invention for forming a palladium alloy thin film and the formation of a palladium alloy thin film using the formulation. [00521 The following formulation ingredients (k), (1), (m), (
n), (o), (p), (q) and (r) (k) Pd-Ag (70/30
) 65% by weight dispersion (hereinafter abbreviated as palladium-silver single particle dispersion ultrafine powder dispersion) (1) Ni in which ultrafine nickel powder with an average particle size of 50 A is dispersed in single particles in terpenyl acetate, Dispersion liquid containing 40% by weight (hereinafter abbreviated as nickel single particle dispersion ultrafine powder dispersion) (m) Containing 40% by weight Pb, which is a single particle dispersion of ultrafine lead powder with an average particle size of 50 A in terpineol. Dispersion liquid (hereinafter abbreviated as lead single particle dispersed ultrafine powder dispersion liquid) (n)
A dispersion containing 25% by weight of Ti0z, which is a single particle dispersion of ultrafine titanium oxide powder with an average particle size of 200 in butyl cellosolve (hereinafter abbreviated as titanium oxide single particle dispersed ultrafine powder dispersion) ( 0) Zr, 20% by weight solution in which zirconium octoate is dissolved in a solvent prepared by mixing rosemary oil and benzyl acetate at a weight ratio of 6:4 (hereinafter abbreviated as zirconium salt solution) (p) Rosemary Ir, 20% by weight solution (hereinafter abbreviated as iridium salt solution) in which iridium octoate is dissolved in a solvent mixed with oil and benzyl acetate at a weight ratio of 6:4 (q) Polyvinyl butyral resin (Building Chemical Co., Ltd.) (manufactured by) (r)
Prepare toluene and prepare these ingredients (k), (1), (m
), (n), (o), (p), (q) and (r
) to the following weight ratio preparation components Weight ratio (
k) Palladium-silver single particle dispersion ultrafine powder dispersion
70.1 (1) Nickel single particle dispersed ultrafine powder dispersion liquid
1.0 (m) Lead single particle dispersed ultrafine powder dispersion 1.0 (n) Titanium oxide single particle dispersed ultrafine powder dispersion 1.0 (o) Zirconium salt solution 2.0 (
p) Iridium salt solution
3.0(q) Polyvinyl butyral resin
3.0(r) toluene
19.0 to obtain a blend of formulation components (k) to (r). [0053] After thoroughly kneading 30 g of the above compound in an agate mortar, the mixture was kneaded in a three-roll mill to obtain a palladium alloy thin film-forming formulation. Using this, a 50 μm wide slit pattern was screen printed on a capacitor green sheet, dried at 150°C for 15 minutes, heated in an electric furnace at a rate of 200°C/hour, and held at 1100°C for 2 hours. After that, the temperature was lowered at a rate of 200° C./hour to produce a laminated circuit. [0054] No cracking or delamination was observed in the obtained laminated circuit. [0055] Comparative Example 1 This example illustrates the production of a palladium film-forming formulation and the formation of a palladium film using the formulation according to conventional techniques for forming palladium membranes. [0056] Preparation components (C) and (d) described in Example 1
), (e) and the following preparation ingredients (s) (S) palladium powder (the average particle size of the primary particles is 1.ttm and the secondary particles are 1.ttm).
Aggregation of up to 0 grains is observed) is mixed with the following volume ratio adjustment ingredients.
Weight ratio (s) Palladium powder (average particle size 1 (t, m) 6
0.0(c) Rosin solution
15.0(d) Ethylcellulose
3.0 (e) butylcarpitol 22.0 blended,
A blend of formulation components (s), (c), (d) and (e) was obtained. [0057] 50 g of the above platform was thoroughly kneaded in an agate mortar and then kneaded in a three-roll mill to obtain a palladium film-forming formulation. [0058] A pattern of 50 μm wide slits similar to those in Example 1 was screen printed on an alumina substrate using the formulation, dried at 125°C for 15 minutes, and then heated at 20°C/min in a tunnel furnace. Although the temperature was raised at a rate of 550°C and maintained at 550°C for 10 minutes, the temperature was lowered at a rate of 20°C/min, but a good fine line could not be obtained. Further, the slit width that allowed formation of a good line was 300 μm, and the thickness of the line was 5 μm. [0059]

Comparative Example 2 This example illustrates the production of a palladium film-forming formulation in which rhodium is added to the palladium film-forming formulation according to a conventional technique for forming a palladium membrane, and the formation of a palladium membrane using the formulation. [00601 Preparation ingredients (b) and (c) described in Example 1
), (d) and (e) and the following formulation ingredients (S) (S) Palladium powder (average particle size 17Lm) in the following weight ratio formulation ingredients (
s) Palladium powder (average particle size 1 μm)
60.0(b) Rhodium salt solution
5.0(c) Rosin solution
10.0(d) Ethylcellulose 3.0(e)
Butyl calpitol 2
2.0, the preparation ingredients (s), (b), (c
), (d) and (e) were obtained. [00611 50 g of the above mixture was thoroughly kneaded in an agate mortar and then kneaded in a three-roll mill to obtain a palladium film-forming composition. [0062] Example 1 on an alumina substrate using the formulation
A similar 50 μm wide slit pattern was screen printed, dried at 125°C for 15 minutes, heated at a rate of 20°C/min in a tunnel furnace, held at 550°C for 10 minutes, and then dried at 20°C. Although the temperature was lowered at a rate of 1/min, a good fine line could not be obtained. Further, the slit width that allowed formation of a good line was 300 μm, and the thickness of the line was 57 zm. [0063]

Comparative Example 3 illustrates the production of a palladium film-forming formulation and the formation of a palladium film using the formulation according to conventional techniques for forming palladium membranes. [0064] Preparation components (C) and (d) described in Example 1
), (e) and the following preparation ingredients (1) (1) palladium powder (the average particle size of the primary particles was 0.1 μm, and spongy aggregation of up to several microns was observed in the secondary particles). Weight ratio adjustment component Weight ratio (
1) Palladium powder (average particle size 0.1μm with agglomeration)
50.0(c) Rosin solution
15.0(d) Ethylcellulose
3.0 (e) Butylcarpitol 32.0 to formulate ingredients (1), (c), (d) and (e)
A formulation of was obtained. [0065] After 50 g of the above-mentioned platform was made coarse and sticky in an agate mortar, it was kneaded in a three-roll mill to obtain a palladium film-forming composition. [0066] Using this, a 50 μm wide slit pattern was screen printed on a titanium oxide dielectric ceramic green sheet, 30 layers were laminated, pressure molded, and the product was heated in an electric furnace at a rate of 200° C./hour. Raise the temperature to 1100
After being held at ℃ for 2 hours, the temperature was lowered at a rate of 200 ℃/hour, but a good fine line could not be obtained. Further, the slit width that allowed formation of a good line was 200 u[II, and the thickness of the line was 3 μm. [0067]

[Comparative Example 4] In order to form a palladium film, Example 1
In the production method described in , the production of a palladium film-forming formulation from which the rhodium salt solution has been removed and the formation of a palladium film using this formulation will be exemplified. [0068] Preparation components (a) and (c) described in Example 1
), (d) and (e) Preparation ingredients Weight ratio (
a) Palladium single particle dispersion ultrafine powder dispersion
80.0(c) Rosin solution
5.0(d) Ethylcellulose
3.0 (e) Butylcarpitol 12.0 to obtain a blend of formulation components (a), (c), (d) and (e). [0069] After thoroughly kneading 50 g of the above platform in an agate mortar, the mixture was kneaded in a three-roll mill to obtain a palladium film-forming formulation. [00701 The formulation was used to deposit 50 μm on a glass substrate.
Screen print a pattern of wide slits and heat at 125℃
After drying for 15 minutes at 550℃, the temperature was raised at a rate of 20℃/min in a tunnel furnace, held at 550℃ for 10 minutes, and then heated to 20℃.
The temperature was lowered at a rate of /min to form a fine line, but
The conductivity of the fine line was poor. [00711 Examples 1.2 and 4 and Comparative Examples 1-
Table 1 shows the results of testing the fine line formability, thickness, and conductivity of the conductive circuit obtained in Example 4. [0072] Also, Examples 2 and 4 and Comparative Example 1
Table 1 also shows the results of testing the crack occurrence rate and delamination occurrence rate for the laminated circuits obtained in steps 4 to 4. [0073]

Effects of the Invention By using the formulation for forming a palladium or palladium alloy thin film obtained by the present invention, a thin and dense palladium or palladium alloy film can be formed on a substrate such as a glass substrate or a ceramic substrate. The thickness of the film formed with the knee is reduced by a factor of 3 to 5 compared to the thickness of the film obtained with conductive formulations for thick film hybrid ICs. [0074] Furthermore, by using the formulation for forming palladium or palladium alloy thin films obtained by the present invention, a conductive circuit having thin and dense fine lines of palladium or palladium alloy on a substrate such as a glass substrate or a ceramic substrate can be manufactured. can do. [0075] Furthermore, by using the formulation for forming palladium or palladium alloy thin films obtained by the present invention, it is possible to produce a laminated circuit in which the above-mentioned conductive circuits are laminated and the occurrence of cracks and delamination is reduced. [0076]

Claims (8)

[Claims] Claim 1: Contains 5% to 70% by weight of metal as a single particle dispersed ultrafine powder of palladium or palladium alloy with an average particle size of 30 to 1000 Å, which is dispersed in an organic solvent in the form of a single particle. and a metal-organic compound of rhodium and/or iridium and/or a single-particle dispersed ultrafine powder of rhodium and/or iridium having an average particle size of 30 to 1000 Å dispersed in an organic solvent as a single particle as a metal. 0.005-1.0
A formulation for forming a thin film of palladium or palladium alloy, characterized by containing % by weight of palladium or palladium alloy. [Claim 2] A metal organic compound of gold and/or a single particle dispersed in an organic solvent with an average particle size of 30
2. The composition for forming a palladium or palladium alloy thin film according to claim 1, which contains 2.5% to 35% by weight of the metal as a single particle dispersed ultrafine powder of gold having a diameter of 1000 Å. 3. Lead, boron, and the average particle size of 30 to 1000 Å dispersed in an organic solvent in the form of single particles;
One or more single-particle dispersed ultrafine powders selected from the group consisting of silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron, zirconium, titanium, barium, and their oxides are used as metals. The palladium or palladium alloy thin film forming formulation according to claim 1 or 2, characterized in that it contains 5% to 10% by weight. 4. One or more metal-organic compounds selected from the group consisting of lead, boron, silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron, zirconium, titanium, and barium as the metal. The palladium or palladium alloy thin film forming formulation according to claim 1, 2 or 3, characterized in that it contains 0.5% to 10% by weight. 5. A metal-organic compound of rhodium and/or iridium and/or a metal-organic compound of rhodium and/or iridium is added to a single-particle dispersed ultrafine powder of palladium or palladium alloy having an average particle size of 30 to 1000 Å, which is dispersed in an organic solvent as a single particle. Claim 1, characterized in that a single-particle dispersed ultrafine powder of rhodium and/or iridium having an average particle diameter of 30 to 1000 Å is blended in an organic solvent in a single-particle state. A method for producing a formulation for forming a palladium or palladium alloy thin film as described. 6. A metal-organic compound of rhodium and/or iridium and/or a metal-organic compound of rhodium and/or iridium is added to a single-particle dispersed ultrafine powder of palladium or palladium alloy having an average particle size of 30 to 1000 Å, which is dispersed in an organic solvent as a single particle. or ultrafine rhodium and/or iridium particles with an average particle size of 30 to 1000 Å dispersed in an organic solvent in the form of single particles, and metal-organic compounds of gold and/or in the form of single particles. A formulation for forming a thin film of palladium or palladium alloy according to claim 2, which contains ultrafine gold particles dispersed in an organic solvent and having an average particle diameter of 30 to 1000 Å. manufacturing method. 7. A metal organic compound of rhodium and/or iridium and/or a metal organic compound of rhodium and/or iridium is added to a single-particle dispersed ultrafine powder of palladium or palladium alloy having an average particle size of 30 to 1000 Å, which is dispersed in an organic solvent in the form of a single particle. or a single-particle dispersed ultrafine powder of rhodium and/or iridium with an average particle size of 30 to 1000 Å dispersed in an organic solvent in the form of a single particle, optionally a metal organic compound of gold and/or in the form of a single particle; Single-particle dispersion ultrafine powder of gold with an average particle size of 30 to 1000 Å when dispersed as is in an organic solvent, and lead with an average particle size of 30 to 1000 Å dispersed as a single particle in an organic solvent. ,
Contains one or more single-particle dispersed ultrafine powders selected from the group consisting of boron, silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron, zirconium, titanium, barium, and their oxides. A method for producing a formulation for forming a palladium or palladium alloy thin film according to claim 3. 8. A metal organic compound of rhodium and/or iridium and/or a metal organic compound of rhodium and/or iridium is added to a single-particle dispersed ultrafine powder of palladium or palladium alloy having an average particle size of 30 to 1000 Å, which is dispersed in an organic solvent in the state of a single particle. or a single-particle dispersed ultrafine powder of rhodium and/or iridium with an average particle size of 30 to 1000 Å dispersed in an organic solvent in the form of a single particle, optionally a metal organic compound of gold and/or in the form of a single particle; Single-particle dispersion ultrafine powder of gold with an average particle size of 30 to 1000 Å when dispersed as is in an organic solvent, optionally dispersed as a single particle in an organic solvent with an average particle size of 30 to 1000 Å Some lead,
One or more single particle dispersed ultrafine powder selected from the group consisting of boron, silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron, zirconium, titanium, barium and oxides thereof, and lead. , boron,
Claim No. 1, characterized in that one or more metal-organic compounds selected from the group consisting of silicon, bismuth, vanadium, zinc, nickel, chromium, tin, iron, zirconium, titanium, and barium are blended. 5. A method for producing a palladium or palladium alloy thin film-forming formulation according to item 4.