CN102754534A - Electronic component, conductive paste, and method for manufacturing electronic component - Google Patents

Electronic component, conductive paste, and method for manufacturing electronic component Download PDF

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Publication number
CN102754534A
CN102754534A CN2010800632603A CN201080063260A CN102754534A CN 102754534 A CN102754534 A CN 102754534A CN 2010800632603 A CN2010800632603 A CN 2010800632603A CN 201080063260 A CN201080063260 A CN 201080063260A CN 102754534 A CN102754534 A CN 102754534A
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China
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particle
electronic unit
aluminium
electrode
conductive paste
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CN2010800632603A
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CN102754534B (en
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青柳拓也
内藤孝
山本浩贵
加藤隆彦
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Hitachi Ltd
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Hitachi Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10128—Display
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0315—Oxidising metal

Abstract

Disclosed is a conductive paste having a plurality of particles (4), which are dispersed in a phosphoric acid solution, and are composed of aluminum (Al) and/or an alloy containing aluminum. An electrode wiring line (2) is formed by applying and baking the conductive paste on a substrate (3). The electrode wiring line (2) has: the particles (4) composed of aluminum and/or the alloy containing aluminum; and an oxide (5) that fixes the particles (4) on the substrate (3). The oxide (5) contains phosphorus (P) and aluminum mixed therein. The particles (4) contains at least one kind of element selected from among a group composed of silver (Ag), copper (Cu), silicon (Si), magnesium (Mg), and calcium (Ca). The electrode wiring line (2) has 84.2-99.7 vol % of particles (4).

Description

The manufacturing approach of electronic unit, conductive paste and electronic unit
Technical field
The present invention relates to possess the electrode distribution electronic unit, be used for conductive paste and the manufacturing approach of this electronic unit of the formation of this electrode distribution.
Background technology
In electronic units such as solar cell device, plasma display panel (PDP), LCD (LCD), ceramic multilayer wiring substrate, be formed with the electrode distribution.This electrode distribution uses conductive paste to form.In conductive paste, use silver (Ag) or aluminium (Al) as metallic.The electrode distribution forms through conductive paste is burnt till with high temperature in air; But conductive paste also has glass particle except metallic; When the burning till of conductive paste, through the temperature more than the softening point that is heated to this glass particle, glass particle is softening to flow; It is fine and close that the electrode distribution becomes, and bonding securely with substrate.
Used in the conductive paste of metallic of aluminium, motion has glass particle to use the conductive paste (with reference to patent documentation 1 etc.) of phosphate-based glass frit.The motion conductive paste that has metallic with the metallic of aluminium and silver to mix to use (with reference to patent documentation 2 etc.) also as metallic.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2000-11927 communique
Patent documentation 2: TOHKEMY 2008-108716 communique
Summary of the invention
The problem that invention will solve
Aluminium generates stable oxide film on the surface, and therefore, the metallic of aluminium presents hard-to-sinter property.Therefore, can know for the conductive paste with the metallic that has used aluminium obtains sufficient electrical characteristic, as long as firing temperature is set at more than 660.4 ℃ of aluminium fusing point.Like patent documentation 1, firing temperature is reduced under 550 ℃～600 ℃ the situation, the manufacturing of electronic unit becomes easily, but thinks and can not obtain sufficient electrical characteristic, in the design of electronic unit, produces restriction sometimes.In patent documentation 2, the metallic of metallic through aluminum mixture in conductive paste and silver, the temperature when successfully making the sintering temperature of metallic be lower than metallic to be aluminium.In patent documentation 2, can reduce the temperature of burning till, also can access sufficient electrical characteristic, but think because metallic uses silver, therefore, be difficult to reduce cost.
Therefore, the objective of the invention is to, even the method for the electronic unit, conductive paste and this electronic unit of manufacturing that possess low firing temperature and also can obtain the electrode distribution of sufficient electrical characteristic is provided with low cost.
Be used to solve the means of problem
In order to realize said purpose, the present invention provides electronic unit, and it possesses the electrode distribution, and said electrode distribution has: by aluminium (Al) and/or contain a plurality of particles that the alloy of aluminium constitutes; And said particle is fixed on the oxide on the substrate, it is characterized in that,
Said oxide contains the phosphorus (P) and the aluminium of mixing.
In addition, the present invention provides conductive paste, it is characterized in that, has:
Phosphoric acid solution; And
A plurality of particles, said a plurality of particles are dispersed in the said phosphoric acid solution, are made up of aluminium (Al) and/or the alloy that contains aluminium.
In addition, the present invention provides the manufacturing approach of electronic unit, it is characterized in that, conductive paste is coated on the substrate, said conductive paste have be dispersed in the phosphoric acid solution by aluminium and/or contain a plurality of particles that the alloy of aluminium constitutes,
The said conductive paste that applies is burnt till, form the electrode distribution.
The invention effect
According to the present invention, even the method for the electronic unit, conductive paste and this electronic unit of manufacturing that possess low firing temperature and also can obtain the electrode distribution of sufficient electrical characteristic can be provided with low cost.
Description of drawings
Fig. 1 is the part of the profile of the electrode distribution that possesses of electronic unit that first embodiment of the invention relates to;
Fig. 2 is the part of the profile of the plasma display panel (electronic unit) that relates to of second embodiment of the invention;
Fig. 3 A is the ground plan of the solar cell device (electronic unit) that relates to of third embodiment of the invention;
Fig. 3 B be turn upside down presentation graphs 3A the A-A direction to pseudosection;
Fig. 4 is the profile of the ceramic multilayer wiring substrate (electronic unit) that relates to of four embodiment of the invention;
Fig. 5 is an example of the temperature-time table of ceramic multilayer wiring substrate (electronic unit) when burning till that relate to of four embodiment of the invention.
Embodiment
Below, suitably execution mode of the present invention is elaborated with reference to accompanying drawing.In addition, in each figure, to the identical symbol of common part mark and omit the explanation of repetition.In addition, the present invention is not limited to a plurality of each execution mode in this proposition, also can appropriate combination.
(first execution mode)
As shown in table 1, in the first embodiment, form 13 kinds of electrode distributions of total of an embodiment 1～12 and a comparative example, and various characteristics is estimated.When forming the electrode distribution, conductive paste also changes to create conditions in each embodiment 1～12 and comparative example to be made, and the firing condition of conductive paste (electrode distribution) also changes in each embodiment 1～12 and comparative example.In addition, in the creating conditions of conductive paste, change the mix proportion of aluminium (Al) particle that constitutes by 3 kinds of particle groups, and by phosphorus pentoxide (P 2O 5), water (H 2O) and ethanol (C 2H 5The weight ratio of the phosphoric acid solution that OH) constitutes.In addition, along with the variation of the weight ratio of phosphoric acid solution, the volume of aluminium also changes with respect to the ratio of the volume sum of aluminium and phosphorus pentoxide.In addition, as the characteristic of estimating, the electrode distribution is carried out the measurement of disbonded test, Water Resistance Test, resistivity.
Below, the formation of electrode distribution is elaborated.
[table 1]
(the 1. formation of electrode distribution)
(cooperation of 1-1. aluminum particulate)
At first, with the aluminium fusion, form spherical particle with water atomization.Utilize sieve from the part of this particle, to remove the particle more than the particle diameter 8 μ m, utilize sieve to remove the particle of particle diameter less than 0.5 μ m.Remaining particle is promptly utilized the particle after sieve is removed big particle and little particle, and further utilize sieve to be divided into: particle group A, its particle diameter have about volume fraction more than 95% in the scope of the above less than 1.5 μ m of 0.5 μ m; Particle group B, its particle diameter have about volume fraction more than 95% in the scope of the above less than 8 μ m of 1.5 μ m.
In addition, the part of the particle that will directly form with water atomization is handled with ball mill in organic solvent, forms tabular particle.In addition, in order to improve the thermal stability of this tabular particle, in reducing atmosphere, carry out the annealing in process of 700 ℃ of temperature.Utilize sieve from this tabular particle, to remove the particle more than the particle diameter 8 μ m, and utilize sieve to remove the particle of particle diameter less than 1.5 μ m again.The particle that remaining particle promptly utilizes sieve to remove behind big particle and the little particle has the tabular particle group of about volume fraction more than 95%, i.e. particle group C as particle diameter in the scope of the above less than 8 μ m of 1.5 μ m.
As shown in table 1, in embodiment 1～11 and comparative example, the mode that the particle that becomes 50 weight %, particle group B with the particle of particle group A becomes 50 weight % is used the particle of particle group A and particle group B.In embodiment 12, the mode that the particle that becomes 50 weight %, particle group C with the particle of particle group A becomes 50 weight % is used the particle of particle group A and particle group C.
(generation of 1-2. phosphoric acid solution)
Then, in each embodiment 1～12, generate phosphoric acid solution.Phosphoric acid solution mixes generation phosphorus pentoxide, water and ethanol with the weight ratio shown in the table 1.In addition, ethanol is for the evaporation of quickening phosphoric acid solution and drying, and after drying, is difficult to absorb water use.From embodiment 1 to embodiment 8, the weight ratio of phosphorus pentoxide increases successively, and the weight ratio of water reduces successively, and the weight ratio of phosphorus pentoxide and water sum is made as necessarily.In addition, the weight ratio of ethanol is made as necessarily.The weight ratio of the phosphorus pentoxide of embodiment 9～12, water and ethanol is the same with embodiment 3, is made as 10 weight %, 80 weight %, 10 weight %.In addition, also can use phosphoric acid (H 3PO 4) the replacement phosphorus pentoxide.Under this situation, the amount of regulating water with the impartial mode of the concentration of phosphorus atoms.In addition, in comparative example, do not use phosphoric acid solution, replace, having used plumbous (Pb) is glass.
(generation of 1-3. conductive paste)
In each embodiment 1～12,100 weight portions of the aluminum particulate that cooperates with 1-1 are added the phosphoric acid solution that mixes 30 weight portions that generate with 1-2.Through to 10 minutes ultrasonic wave of this mixture irradiation, aluminum particulate is scattered in the phosphoric acid solution, obtain conductive paste.
In comparative example, to 100 weight portions of the aluminum particulate that cooperates with 1-1, add the lead glass powder that mixes 10 weight portions, as the acetate of butyl carbitol of solvent, as the ethyl cellulose of adhesive.Through to 10 minutes ultrasonic wave of this mixture irradiation, making aluminum particulate, lead is that the powder and the adhesive of glass is scattered in the solvent, obtains conductive paste.
(burning till of 1-4. electrode distribution)
In each embodiment 1～12 and comparative example, with scraper at aluminium oxide (Al 2O 3) coating electrically conductive property slurry on the substrate.After coating, conductive paste was made it dry in 30 minutes with 150 ℃ of heating of temperature in air.Then, in air, be warmed up to the firing temperature of representing in the firing condition of table 1 with 5 ℃/minute programming rate, and keep burning till the firing time of representing in the firing condition of table 1 with this firing temperature with electric furnace, then, natural cooling.Burn till through this, accomplish the electrode distribution.(electrode distribution) thickness of filming after the burning till in embodiment 1～12 and the comparative example all is about 10 μ m.The firing temperature of the firing condition of embodiment 1～8, embodiment 12 and comparative example is all 700 ℃, firing time and was all 30 minutes.In embodiment 9～11, firing temperature is changed to 400 ℃, 500 ℃, 600 ℃, firing time was all 30 minutes.
(the 2. characteristic of electrode distribution)
(2-1. disbonded test)
In each embodiment 1～12 and comparative example, the electrode distribution of accomplishing through the disbonded test evaluation is to the adhesive strength of substrate.In disbonded test, peel after commercially available cellotape is attached to the electrode distribution.And, after peeling, the electrode distribution is observed evaluation.As metewand; Use following benchmark: the situation that most of aluminum particulate peels and the electrode distribution becomes the broken string state is made as " * "; The part of aluminum particulate is peeled and the part of electrode distribution is cut off and the situation that becomes the broken string state is made as " △ ", and the situation that aluminum particulate not being peeled (aluminum particulate on surface that comprises the electrode distribution than unfertile land attached to the degree on the cellotape) and electrode distribution does not become the broken string state is made as " zero ".As shown in table 1, the result of disbonded test, embodiment 1 and embodiment 9 are " * ", and embodiment 2 is " △ ", and embodiment 3～8, embodiment 10～12, comparative example are " zero ".
The result of disbonded test is compared between embodiment 1～8; Hence one can see that; Preferably count more than the 1 weight % with the weight ratio of phosphorus pentoxide; Count (embodiment 2～8: obtain the evaluation of " △ " at least) below the 89 weight % with the weight ratio of water, more preferably count more than the 10 weight %, count (embodiment 3～8: obtain the evaluation of " zero ") below the 80 weight % with the weight ratio of water with the weight ratio of phosphorus pentoxide.Like this, the result of disbonded test exists with ... the weight ratio of the phosphorus pentoxide in the phosphoric acid solution, thinks that this is because the weight ratio of this phosphorus pentoxide is relevant with respect to the ratio of the volume of the aluminium in the electrode distribution with phosphorus pentoxide.That is, this be because, think for fixing aluminum particulate on substrate, with respect to the volume of aluminium, need the phosphorus pentoxide of the volume more than the certain proportion.The volume of table 1 expression aluminium is with respect to the ratio of the volume sum of aluminium and phosphorus pentoxide; But with the ratio of this volume estimate disbonded test as a result the time; Can know preferably and count (embodiment 2～8: obtain the evaluation of " △ " at least) below the 99.7 volume %, more preferably (embodiment 3～8: obtain the evaluation of " zero ") below the 97.4 volume % with the ratio of this volume.
In addition; The result of disbonded test is compared between embodiment 3 and embodiment 9～11; Thus, if can know under the firing temperature of firing condition 400 ℃ (embodiment 9), then obtain the evaluation of " * "; If but 500 ℃ (embodiment 10), 600 ℃ (embodiment 11), 700 ℃ (embodiment 3) then obtain the evaluation of " zero ".Thus, think that the firing temperature of electrode distribution of the present invention can not adhere to below 400 ℃ on substrate, be easy to peel, but, in the time of for example more than 500 ℃, become densification and driving fit on substrate surpassing 400 ℃.
In addition, the result of disbonded test is compared in embodiment 3 and embodiment 12, thus, can know and use any particle group B (embodiment 3) and particle group C (embodiment 12), all obtain the evaluation of " zero ".Also can know in comparative example the evaluation that also obtains " zero ".
(2-2. Water Resistance Test)
In each embodiment 1～12 and comparative example, the electrode distribution of accomplishing is estimated with respect to the saprophagous character of water with Water Resistance Test.In Water Resistance Test, the electrode distribution was flooded 30 minutes in 70 ℃ warm water.After dipping, the electrode distribution is observed, estimated.As metewand, use following benchmark: after test, the situation that the electrode distribution is formed black is made as " * ", and the situation that the color of electrode distribution is changed a little is made as " △ ", and the almost unchanged situation of color is made as " zero ".As shown in table 1, the result of disbonded test is " * " in embodiment 1 and embodiment 9, is " △ " in embodiment 2, is " zero " in embodiment 3～8, embodiment 10～12 and comparative example.As shown in table 1, the result of Water Resistance Test is " * " in embodiment 9 and comparative example, is " △ " in embodiment 1, in embodiment 2～8 and embodiment 10～12, is " zero ".
The result of Water Resistance Test is compared between embodiment 1～8 and comparative example; Hence one can see that; The weight ratio of preferred phosphorus pentoxide is more than the 0.5 weight %; The weight ratio of water is (embodiment 1～8: obtain the evaluation of " △ " at least) below the 89.5 weight %, and more preferably the weight ratio of phosphorus pentoxide is more than the 1 weight %, and the weight ratio of water is (embodiment 2～8: obtain the evaluation of " zero ") below the 89 weight %.On the other hand, can know that comparative example becomes " * ".Compare with comparative example, can know electrode distribution one side's of embodiment 1～8 resistance to water excellence.In addition; When estimating with respect to the result of the comparison Water Resistance Test of the volume sum of aluminium and phosphorus pentoxide with the volume of aluminium; Can know; Be preferably below the 99.9 volume % (embodiment 1～8: obtain the evaluation of " △ " at least), more preferably (embodiment 2～8: obtain the evaluation of " zero ") below the 99.7 volume %.
In addition; The result of Water Resistance Test is compared between embodiment 3 and embodiment 9～11; Hence one can see that, if the firing temperature of firing condition is 400 ℃ (embodiment 9), then obtains the evaluation of " * "; If but 500 ℃ (embodiment 10), 600 ℃ (embodiment 11), 700 ℃ (embodiment 3) then obtain the evaluation of " zero ".Thus, if think the firing temperature of electrode distribution of the present invention below 400 ℃, then aluminum particulate can not be covered by the oxide of densification; Can not obtain higher resistance to water, but if surpass 400 ℃, for example more than 500 ℃; It is fine and close that the oxide of aluminium coating particle becomes, and obtains higher resistance to water.On the other hand, in comparative example,, can not obtain resistance to water, be evaluated as " * " even firing temperature is 700 ℃.Because in embodiment 3, embodiment 9～11 and comparative example, the formation method of the oxide of aluminium coating particle is different.
In addition, the result of Water Resistance Test is compared in embodiment 3 and embodiment 12, hence one can see that, uses any particle group B (embodiment 3) and particle group C (embodiment 12) all can obtain the evaluation of " zero ".
(2-3. determination of resistivity)
In each embodiment 1～12 and comparative example, measure the resistivity of the electrode distribution of accomplishing.In determination of resistivity, measure the resistance and the thickness of electrode distribution, calculate resistivity based on this resistance and thickness.The result of determination of resistivity is compared between embodiment 1～8 and comparative example, and hence one can see that, with the resistivity (5.6 * 10 than comparative example -5Ω cm) little by 5.0 * 10 -5Ω cm compares, and resistivity becomes lower in embodiment 1～7.In addition, through between embodiment 1～8, comparing, can know that resistivity obtains minimum value in embodiment 3, become 0.68 * 10 -5Ω cm.
In weight ratio, along with the increase (from embodiment 1 to embodiment 3) of phosphorus pentoxide from 0.5 weight % to 10 weight %, resistivity reduces, and in 10 weight % (embodiment 3), resistivity becomes minimum value (0.68 * 10 -5Ω cm), along with the increase from 10 weight % to 70 weight % (from embodiment 3 to embodiment 8), resistivity increases.In weight ratio, phosphorus pentoxide is the scope from 1 weight % to 15 weight % (embodiment 2～4), and resistivity becomes 1.0 * 10 -5Below the Ω cm.In weight ratio, phosphorus pentoxide the scope from 0.5 weight % to 65 weight % (embodiment 1～7), the resistivity resistivity (5.6 * 10 of comparative example that becomes than is lower than -5Ω cm) 5.0 * 10 -5Ω cm is little.
When estimating with respect to the result of the comparison determination of resistivity of the volume sum of aluminium and phosphorus pentoxide with the volume of aluminium; In volume ratio; Along with its minimizing (from embodiment 1 to embodiment 3) from 99.9 volume % to 97.4 volume %; Resistivity reduces, and resistivity becomes minimum value (0.68 * 10 at 97.4 volume % (embodiment 3) -5Ω cm), along with the minimizing from 97.4 volume % to 84.2 volume % (from embodiment 3 to embodiment 8), resistivity increases.In this volume ratio, the scope from 99.7 volume % to 96.1 volume % (embodiment 2～4), resistivity becomes 1.0 * 10 -5Below the Ω cm.In this volume ratio, the scope from 99.9 volume % to 85.1 volume % (embodiment 1～7), resistivity is the resistivity (5.6 * 10 than comparative example -5Ω cm) little less than 5.0 * 10 -5Ω cm.
The result of determination of resistivity is compared between embodiment 3, embodiment 9～11 and comparative example, and hence one can see that, with the resistivity (5.6 * 10 than comparative example -5Ω cm) little by 5.0 * 10 -5Ω cm compares, and resistivity is lower at embodiment 3, embodiment 10 and embodiment 11.In addition,, can know that resistivity obtains minimum value at embodiment 3, becomes 0.68 * 10 through between embodiment 3 and embodiment 9～11, comparing -5Ω cm.
In firing temperature, along with firing condition from 400 ℃ to 700 ℃ increase (from embodiment 9,10,11 to embodiment 3), resistivity reduces, resistivity becomes minimum value (0.68 * 10 700 ℃ (embodiment 3) -5Ω cm).In firing temperature, from 600 ℃ to 700 ℃ scope (embodiment 11 and embodiment 3), resistivity becomes 1.0 * 10 -5Below the Ω cm.In firing temperature, surpassing 400 ℃, for example in the scope more than 500 ℃ (embodiment 10, embodiment 11, embodiment 3), resistivity is the resistivity (5.6 * 10 than comparative example -5Ω cm) little less than 5.0 * 10 -5Ω cm.
In addition, the result of determination of resistivity is compared in embodiment 3 and embodiment 12, hence one can see that, compares with particle group B (spherical particle: embodiment 3), uses one of particle group C (tabular particle: embodiment 12) can further reduce resistivity.
(optimization that 2-4. creates conditions)
When the volume of aluminium being estimated with respect to the ratio of the volume sum of aluminium and phosphorus pentoxide by the result of disbonded test, Water Resistance Test and determination of resistivity; Can know; This volume ratio is (embodiment 2～8) in the above scope of 84.2 volume % below the 99.7 volume % time, obtains good tack (disbonded test result) and excellent water tolerance (Water Resistance Test result).In addition; When rewriting this volume ratio with the volume ratio of phosphorus pentoxide; The value that deducts the volume ratio of aluminium with 100 volume % becomes the volume ratio of phosphorus pentoxide; Therefore, in the time of in the scope more than 0.3 volume % below the 15.8 volume % (embodiment 2～8), obtain good tack (disbonded test result) and excellent water tolerance (Water Resistance Test result).
Also can know; This volume ratio in the scope more than the 85.1 volume % time (embodiment 2～7), obtains good tack (disbonded test result), excellent water tolerance (Water Resistance Test result) and good resistivity (determination of resistivity result) below 99.7 volume %.Can know that also this volume ratio is below 97.4 volume % in the scope more than the 96.1 volume % time (embodiment 3,4), obtaining better tack (disbonded test result), excellent water tolerance (Water Resistance Test result), resistivity is 1.0 * 10 -5Better resistivity (determination of resistivity result) below the Ω cm.
In addition; When firing temperature is estimated; Can know; This firing temperature is (embodiment 10,11,3) when the scope below 700 ℃ is interior more than 500 ℃, obtains good tack (disbonded test result), excellent water tolerance (Water Resistance Test result) and good resistivity (determination of resistivity result).Can know that also this firing temperature is more than 600 ℃ in the scope below 700 time (embodiment 11,3), obtaining good tack (disbonded test result), excellent water tolerance (Water Resistance Test result), resistivity is 1.0 * 10 -5Better resistivity (determination of resistivity result) below the Ω cm.
In addition; When the cooperation of the particle group B of aluminum particulate and particle group C is estimated; Can know; When using particle group C to replace particle group B when (embodiment 12), obtain good tack (disbonded test result), excellent water tolerance (Water Resistance Test result), than the better resistivity (determination of resistivity result) of situation of the particle group B that uses embodiment 3.
Fig. 1 representes the partial enlarged drawing of the profile of the electrode distribution 2 that the electronic unit 1 of first embodiment of the invention possesses.The electrode distribution 2 that electronic unit 1 has aluminum oxide substrate 3 and on aluminum oxide substrate 3, is adhesively fixed.Electrode distribution 2 has by aluminium (Al) and/or contains a plurality of particles 4 that the alloy of aluminium constitutes and make particle 4 be fixed in the oxide 5 on the substrate 3.
Fig. 1 is based on the figure that use sweep electron microscope-energy dispersion type x-ray analysis equipment (SEM-EDX) is observed the result of the electrode distribution of making among the for example embodiment 11 of table 12.Through sintering, a plurality of particles 4 be bonded to each other (necking down).In this necking down joint portion 6, do not observe the layer of the natural oxide of aluminium from the analysis result of energy dispersion type x-ray analysis equipment (EDX).
It is the phosphorous oxides of principal component that oxide 5 has with phosphorus and oxygen (O), and not consider the component ratio of oxygen, the containing ratio of phosphorus becomes more than the 50 atom %.In addition, in oxide 5, except phosphorus, also detect aluminium.Infer thus; Conductive paste is in burning till preceding or burning till, and the natural oxide film that covers the aluminium on particle 4 surfaces that are scattered in the phosphoric acid solution is dissolved by phosphoric acid solution, and aluminium is stripping in phosphoric acid solution; Through burning till, the phosphoric acid solution that contains this aluminium finally becomes the oxide 5 that contains phosphorus and aluminium.The natural oxide film of the aluminium that the surface coverage of the particle 4 of aluminium and aluminium alloy disappears when burning till, and thus, necking down joint portion 6 is easy to generate, and can reduce the resistivity of electrode distribution 2.
In addition, utilize the high-hydrophilic on particle 4 surfaces of aluminium that the interpolation etc. of ethanol causes and aluminium alloy, whole of particle 4 surfaces is moistening by phosphoric acid solution, and is covered by phosphoric acid solution.Therefore, when burning till, the whole surperficial oxide 5 of having removed the particle 4 of necking down joint portion 6 covers.In addition, through removing the natural oxide film of aluminium, oxide 5 directly joins with particle 4, and oxide 5 forms bilayer but not individual layer, and therefore, in the oxide 5, phosphorus (P) atom and the mixing of aluminium atom are contained in the integral body in the film.
In addition, with shown in the embodiment 11, also demonstrate excellent conductivity at the firing temperature of fusing point below 660.4 ℃ of aluminium like the embodiment 10 of table 1 even distinguish electrode distribution 2.At present, the sintering of aluminium is progress not, thinks that this oxide-film (natural oxide film) is reason, and needing the above firing temperature of fusing point is to be used to destroy this oxide film thereon.In the electrode distribution 2, in the phosphoric acid solution of acidity, the oxide-film on particle 4 surfaces of aluminium is corroded and removes.That is, in burning till, aluminium component is stripping in phosphoric acid solution, in phosphoric acid solution or in the phosphoric acid oxide 5, separates out as the oxidized compound of phosphorus and aluminium or aluminium oxide etc.Through removing oxide film thereon, promote the sintering of aluminium, even infer and utilize fusing point to carry out burning till of low temperature, also bring into play good electrical conductivity.
In addition, the surface of phosphoric acid solution coated particle 4, when burning till, the aluminium component of phosphoric acid and stripping reacts, and becomes the oxide 5 of compound (oxidized compound).In electrode distribution 2; Think that main cause that resistance to water improves is owing to dredge thin oxide-film from the whole surface removal of aluminum particulate 4, form the fine and close phosphorus and the compound of aluminium on the whole uniform surface ground of the particle 4 of aluminium, therefore; The surface that can not expose particle 4, the stability of chemical improves.But,, under the situation of for example burning till more than 500 ℃, obtain excellent water tolerance surpassing 400 ℃.
On the other hand, when using the electrode distribution of making in the comparative example shown in sweep electron microscope-energy dispersion type x-ray analysis equipment (SEM-EDX) observation table 12, plumbous (Pb) metal is separated out at particle 4 interface each other of aluminium, observes the segregation of glass ingredient.Think that this is that the Pb of the particle 4 through aluminium is the oxidation that glass causes, Pb is the result that the lead of glass is restored.Therefore, the Pb that uses at present is in the glass, and the remained on surface of aluminum particulate is dredged thin oxide film thereon, aluminum particulate surperficial oxidized, and therefore, the oxide film thereon that supposition can form again also for dredging thin oxide film thereon, can not be covered densely.
In particle 4, not only aluminum particulate 4, also can use the particle 4 that is made up of the alloy that contains aluminium.As the alloy that contains aluminium, contain at least a element in silver (Ag), copper (Cu), silicon (S i), magnesium (Mg), the calcium (Ca).For example, through adding silver, can improve the conductance of alloy (Al-Ag).In addition, through adding copper, can improve the intensity of alloy (Al-Cu).Through adding silicon, can improve the abrasion performance of alloy (Al-Si).Through adding magnesium or calcium, can improve intensity and the corrosion resistance of alloy (Al-Mg, Al-Ca).
Particle 4 is had a volume fraction of about 95% in the scope of the above less than 1.5 μ m of 0.5 μ m by particle diameter particle group A (the first particle group) 4A and particle diameter has about 95% volume fraction in the scope of the above less than 8 μ m of 1.5 μ m particle group B (the second particle group) 4B constitutes.The total weight of a plurality of particles 4 of the total weight of a plurality of particles 4 of particle group A (4A) and particle group B (4B) about equally.Thus, the particle of the particle group A (4B) that particle diameter is little 4 gets into the gap between the particle 4 of the big particle group B (4B) of particle diameters, can improve the density of particle 4, therefore, can form fine and close electrode distribution 2.
(second execution mode)
Fig. 2 representes the plasma display panel (PDP: the part of 11 (1) profile electronic unit) that second embodiment of the invention relates to.In second execution mode,, be that example is enumerated explanation with plasma display panel 11 as using electronic unit 1 of the present invention.At the show electrode 20 of plasma display panel 11 (1) and the electrode distribution 2 of address electrode 21 uses electronic unit 1 of the present invention.The front panel 12 (3) of plasma display panel 11 (1) and backplate 13 (3) have the configuration of subtend with gap of 100～150 μ m, and keep with next door 14 in the gap of front panel 12 (3) and backplate 13 (3).The circumference of front panel 12 (3) and backplate 13 (3) carries out hermetic seal with encapsulating material 15, in front the inner rare gas of filling of the display panel in plate 12 (3) and backplate 13 (3) gaps.
Be formed with show electrode 20 (2) on the plate 12 (3) in front.Front panel 12 (3) is suitable with the substrate 3 of first execution mode, and show electrode 20 (2) is suitable with the electrode distribution 2 of first execution mode.On show electrode 20 (2), be formed with dielectric layer 23, on dielectric layer 23, be formed with the protective layer 25 (for example, the vapor-deposited film of magnesia (MgO)) that is used to protect show electrode 20 (2) etc. from discharge.
Be formed with address electrode 21 (2) on the plate 13 (3) overleaf.Backplate 13 (3) is suitable with the substrate 3 of first execution mode, and address electrode 21 (2) is suitable with the electrode distribution 2 of first execution mode.The plane sees that address electrode 21 (2) forms with the mode with show electrode 20 (2) quadratures.On address electrode 21 (2), be formed with dielectric layer 24, on dielectric layer 24, be provided with the next door 14 that is used to constitute unit 16.Next door 14 is the tectosome of striated or grid (chest) shape.
In the gap between front panel 12 (3) and the backplate 13 (3), the short space of being divided by next door 14 becomes unit 16.16 are filled with fluorophor 17,18,19 in the unit.Corresponding 3 unit 16 of 3 primary colors of filling the unit 16 of the unit 16 of red-emitting phosphors 17, the unit 16 of filling green-emitting phosphor 18, filling blue emitting phophor 19 constitute a pixel.Each pixel can be sent versicolor light according to the signal that puts on show electrode 20 (2) and address electrode 21 (2).
Then, the manufacturing approach of article on plasma display panel 11 (1) describes.
(making of conductive paste)
At first, the particle group A that explains in the preparation table 1 is as the particle that is contained in the conductive paste.Particle is made as the metallic of aluminium.The particle of particle group A is that particle diameter has about volume fraction more than 95% in the scope of the above less than 1.5 μ m of 0.5 μ m.Do not use particle group B and particle group C, use particle group A in mix proportion 100 weight %.In addition, aspect phosphoric acid solution, prepare phosphoric acid solution with the embodiment 3 identical weight ratio of table 1.That is, prepare the phosphoric acid solution of weight ratio of ethanol of water, the 10 weight % of phosphorus pentoxide, the 80 weight % of 10 weight %.To before 100 weight portions of the powder prepared add this phosphoric acid solutions of 30 weight portions.To 10 minutes ultrasonic wave of these mixture irradiations, thus, particle is scattered in the phosphoric acid solution, accomplish conductive paste.
(making of plasma display panel)
Then, make plasma display panel.At first, through silk screen print method whole coating electrically conductive property slurry of plate 12 (3) and backplate 13 (3) in front, dry in 150 ℃ in atmosphere.Through the unnecessary position of coated film that photoetching process and etch are removed conductive paste, carry out the composition of show electrode 20 (2) and address electrode 21 (2).Then, the same with the firing condition of the embodiment 11 of table 1, in atmosphere, burnt till in 30 minutes with 600 ℃ of firing temperatures, firing time, accomplish show electrode 20 (2) and address electrode 21 (2).In this burnt till, firing atmosphere was acid atmosphere, but through burning till, the metallic of the particularly aluminium of show electrode 20 (2) and address electrode 21 (2) does not carry out chemical reaction and variable color etc.
Then, plate 12 (3) and backplate 13 (3) apply the dielectricity slurry that becomes dielectric layer 23,24 respectively in front, in atmosphere, burn till in 30 minutes with 600 ℃ of firing temperatures, firing time.In addition; In this burnt till, firing atmosphere became acid atmosphere, and dielectric layer 23 directly joins with show electrode 20 (2); Dielectric layer 24 directly joins with address electrode 21 (2); But burn till through this, dielectric layer 23 does not carry out chemical reaction with show electrode 20 (2), and dielectric layer 24 does not carry out chemical reaction with address electrode 21 (2).Dielectric layer 23 side vapor deposition protective layers 25 from front panel 12 (3).
The material forming that next door 14 will be contained pulverous glass component and filler at least is striated or clathrate, makes the tectosome of this shaping with 500～600 ℃ of sintering.This next door 14 of configuration constitutes unit 16 on dielectric layer 24.And, fill the fluorophor corresponding to each unit 16 and burn till with slurry and with 450～500 ℃ with three primary colors, thus, formation red-emitting phosphors 17, green-emitting phosphor 18 and blue emitting phophor 19 in unit 16.
Then, through dotting glue method or print process etc., arbitrary side's of plate 12 (3) or backplate 13 (3) circumference applies encapsulating material 15 in front.And, encapsulation front panel 12 (3) and backplate 13 (3).In front in the encapsulation of plate 12 (3) and backplate 13 (3), make the correct position of front panel 12 (3) and backplate 13 (3) aim at the ground subtend and dispose, and be heated to 420～500 ℃.When this heated, the gas in the deliverying unit 16 replaced, and enclosed rare gas.Fluorophor when in addition, encapsulating material 15 also can be with the formation of fluorophor 17～19 temporarily burns till with burning till of slurry simultaneously.Through temporarily burning till encapsulating material 15, can reduce and contain bubble in the encapsulating material 15.In addition, in Fig. 2, encapsulating material 15 directly joins with address electrode 21 (2), but for to outside extraction electrode, show electrode 20 (2) also directly joins with encapsulating material 15.Encapsulating material 15 heats when temporarily burning till and during glass packaging, and firing atmosphere adds at this pines for being acid atmosphere, but through this heating, encapsulating material 15 does not carry out chemical reaction with show electrode 20 (2) and address electrode 21 (2).More than, accomplish plasma display panel 11 (1).
(evaluation of plasma display panel)
(visual examination)
Carry out the visual examination on every side of show electrode 20 (2) and address electrode 21 (2).The interface portion of show electrode 20 (2) and front panel 12 (3), and the interface portion of show electrode 20 (2) and dielectric layer 23 do not see the generation and the variable color in space.In addition, the interface portion of address electrode 21 (2) and backplate 13 (3), and the interface portion of address electrode 21 (2) and dielectric layer 24 do not see the generation and the variable color in space.Can make plasma display panel 11 (1) with good state in appearance.
(lighting experiment)
Then, the plasma display panel of making 11 (1) light experiment.In order to light the unit 16 of (luminous) plasma display panel 11 (1); Between the show electrode 20 (2) of the unit that will light 16 and address electrode 21 (2), apply voltage; In unit 16, carry out the address discharge, rare gas is excited be plasmoid, make accumulation wall electric charge in the unit 16.Then, show electrode 20 (2) is applied certain voltage, thus, only cause to show discharge and produce ultraviolet ray 22 in the unit 16 of accumulation wall electric charge.And utilization should ultraviolet ray 22 make fluorophor 17～19 luminous, display image (information).
Before and after the demonstration of this image information, the resistivity of show electrode 20 (2) and address electrode 21 (2) can not increase.In addition, the address electrode 21 (2) that reaches adjacency at the show electrode 20 (2) of adjacency each other waits each other, and proof voltage can not reduce, but booster voltage, can lighting unit 16.In addition, can not produce the mobile phenomenon of the electrode distribution of silver thick film yet, particularly not find to hinder other point.The show electrode 20 (2) of the plasma display panel 11 (1) of second execution mode and address electrode 21 (2) do not use high price silver, therefore, can help the remarkable reduction of cost yet.
(the 3rd execution mode)
Fig. 3 A representes the ground plan (rear side) of the solar cell device (electronic unit) 31 (1) of third embodiment of the invention, the A-A direction of Fig. 3 B presentation graphs 3A to pseudosection, sensitive surface side (face side) is made as upside, rear side is made as downside.In the 3rd execution mode,, be that example is enumerated explanation with solar cell device 31 as using electronic unit 1 of the present invention.Among Fig. 3 A and Fig. 3 B, be that an example is represented with back contact type (back electrode type) crystal silicon solar energy battery element 31 (1).P type electrode 37 uses the electrode distribution 2 of electronic unit 1 of the present invention at the back side of solar cell device 31 (1).In addition, on the battery wafer 38 that the silicon substrate by the p type constitutes, be formed with back side p type electrode 37 (2).Element wafer 38 (3) is suitable with the substrate 3 of first execution mode, and back side p type electrode 37 (2) is suitable with the electrode distribution 2 of first execution mode.In the solar cell device 31 of back contact type (back electrode type), side is formed with back side p type electrode 37 (2) and back side n type electrode 36 overleaf.
Be formed with the through hole 39 that connects between surface and the two sides, the back side at element wafer 38 (1), be formed with n type semiconductor layer 33 at the sidewall of through hole 39 and the sensitive surface side (face side) of element wafer 38 (1).Be embedded in the through hole electrode 34 of silvery at through hole 39.With with through hole electrode 34 ways of connecting, the grid shape current collection that is formed with silvery in the sensitive surface side (face side) of element wafer 38 (1) is with gate electrode 32.
In the rear side of element wafer 38 (1), leave through hole 39 and be formed with high concentration dope layer 35 with through hole electrode 34 ground.High concentration dope layer 35 prevents the combination again of charge carrier.With with the mode of high concentration dope layer 35 location matches, be formed with the grid shape back side p type electrode 37 (2) of aluminum in the rear side of element wafer 38 (1).In addition, with the mode of through hole electrode 34 location matches, be formed with the grid shape back side n type electrode 36 of silvery in the rear side of element wafer 38 (1).
Then, the manufacturing approach to solar cell 31 (1) describes.
(making of conductive paste)
In the 3rd execution mode,, make to use the identical slurry of conductive paste of use among the embodiment 2 with table 1 as conductive paste.
(making of solar cell)
Prepare p type silicon substrate as element wafer 38 (3).Then, through laser drilling or corrosion etc., form through hole 39 at element wafer 38 (3).Then, diagram is omitted, but owing to improve light incident efficient, therefore, uses 1% caustic soda (NaOH: NaOH) with 10% isopropyl alcohol (CH 3CH (OH) CH 3) mixed liquor, the sensitive surface side (face side) of corrosion element wafer 38 (3) and the texture that forms.
Sensitive surface side (face side) at element wafer 38 (3) applies the liquid that contains phosphorus pentoxide, carries out handling in 30 minutes with 900 ℃, thus, makes phosphorus 38 (1) (P) diffusions from the phosphorus pentoxide to the element wafer, forms n type semiconductor layer 33 in the sensitive surface side.In addition, diagram is omitted, but also can on n type semiconductor layer 33, form silicon nitride film (Si in the same thickness ground 3N 4) antireflection film.This silicon nitride film can pass through with silane (SiH 4) and ammonia (NH 3) mist be that the plasma CVD method of raw material forms.
Then, to the commercially available silver paste of the through hole that forms before 39 inner fillings, in addition,, above-mentioned silver paste is printed as the grid shape, thus, forms through hole electrode 34 and current collection with gate electrode 32 in the sensitive surface side with print process.Through hole electrode 34 and the current collection that makes formation with gate electrode 32 with 150 ℃ of dryings 30 minutes.
In the rear side of the opposition side of sensitive surface, use silver paste, through silk screen printing, carry out the striated printing, form back side n type electrode 36.In addition, in the rear side of the opposition side of sensitive surface, use with embodiment 2 in the identical conductive paste of conductive paste that uses, through silk screen printing, carry out the striated printing, formation back side p type electrode 37 (2).The back side n type electrode 36 that makes formation and back side p type electrode 37 (2) were with 150 ℃ of dryings 30 minutes.
Through hole electrode 34, current collection with gate electrode 32, back side n type electrode 36 and back side p type electrode 37 (2), are kept 2 seconds burn till with 850 ℃, thus, accomplish back contact type solar cell device 31 (1).In addition, burn till through this, p type electrode 37 (2) is formed for the high concentration dope layer 35 that prevents that charge carrier from combining again to element wafer 38 (3) diffusions of p type electrode 37 (2) bottoms, the back side to aluminium simultaneously from the back side.
In addition, as relatively, use the identical conductive paste of conductive paste that uses in the comparative example with table 1, make the back contact type solar cell device 31 (1) of formation back side p type electrode 37 (2).
(evaluation of solar cell device)
Compare with the solar cell of making because of comparison, distinguish that the conversion efficiency of the back contact type solar cell 31 (1) of the 3rd execution mode becomes higher efficient.Think that this is owing to can reduce the resistance value of back side p type electrode 37 (2).More than, confirm that electrode distribution 2 of the present invention (with reference to Fig. 1) can be as the back side p type electrode 37 (2) of back contact type solar cell 31 (1).In addition, the manufacture method of the back side p type electrode 37 (2) of the solar cell of above-mentioned explanation is not limited to back contact type solar cell, also can be the corresponding method of manufacture method with the p type electrode of various solar cells.
(the 4th execution mode)
Fig. 4 representes the profile of the ceramic multilayer wiring substrate (electronic unit) 41 (1) of four embodiment of the invention.In the 4th execution mode, the example that electronic unit 1 of the present invention (with reference to Fig. 1) is applied to multi-layered wiring board describes.As 1 example of multi-layered wiring board, expression is by the multi-layered wiring board 41 (1) of 5 layers of low-temperature sintering ceramic (LTCC:Low Temperature Co-fired Ceramics) formation among Fig. 4.The through hole electrode 43 (2) of multi-layered wiring board 41 (1) and distribution 44 (2) use the electrode distribution 2 of electronic unit 1 of the present invention.Ceramic substrate 42 (3) separately above with below be formed with distribution 44 (2).Among Fig. 4, distribution 44 (2) is formed with 6 layers.The distribution 44 (2) of each layer is connected by through hole electrode 43 (2).Through hole electrode 43 (2) connects ceramic substrate 42 (3).At multi-layered wiring board 41 (1), dimensional topography becomes to have distribution 44 (2) and through hole electrode 43 (2).Ceramic substrate 42 (3) is suitable with the substrate 3 of first execution mode, and through hole electrode 43 (2) and distribution 44 (2) are suitable with the electrode distribution 2 of first execution mode.
Then, the manufacturing approach to multi-layered wiring board 41 (1) describes.
(making of conductive paste)
In the 4th execution mode,, make to use the identical slurry of conductive paste of use among the embodiment 2 with table 1 as conductive paste.
(making of multi-layered wiring board)
At first, prepare many raw cooks of stirred glass powder, ceramic powders and the mixing formation of adhesive.Raw cook through after state burn till the ceramic substrate 42 (3) that becomes each layer.Then, offer through hole in the position of the hope of raw cook.To offering the raw cook of through hole, will with the identical conductive paste of slurry that uses among the embodiment 2, be coated with into the Wiring pattern of hope with print process.At this moment, also filled conductive property slurry in through hole.The conductive paste that is applied as Wiring pattern through after state burn till and become through hole electrode 43 (2) and distribution 44 (2).As required, for example, with print process at the undermost raw cook back side that Fig. 4 representes, also coating electrically conductive property slurry and form Wiring pattern.Under the situation about applying to the raw cook back side, after making the conductive paste drying that is coated on the surface, carry out.
Range upon range of a plurality of raw cooks and the one that has formed the Wiring pattern of regulation burnt till.An example of the temperature-time table when Fig. 5 representes to burn till.As shown in Figure 5, be made as the atmosphere from the temperature-rise period of room temperature to 700 ℃, the process of 700 ℃～900 ℃ temperature range (comprise 60 minutes with retention time of 900 ℃) is made as in the blanket of nitrogen, is made as the atmosphere once more from 700 ℃ of temperature-fall periods to room temperature.In addition, heating rate and rate of temperature fall are made as 5 ℃/minute.In addition, the temperature-time table that burns till is not limited to Fig. 5.In addition, 700 ℃～900 ℃ temperature range is made as in the blanket of nitrogen, and this is in order to suppress the oxidation of the particle 4 in the conductive paste.
(evaluation of multi-layered wiring board)
Carry out distribution 44 (2) visual examination on every side.In the interface portion of distribution 44 (2) and ceramic substrate 42 (3), do not find the generation and the variable color in space.Can make multi-layered wiring board 41 (1) with good state in appearance.Measure the resistivity of distribution 44 (2) and through hole electrode 43 (2), obtain value like the design the same with the embodiment of table 12.The cross-section of the multi-layered wiring board of then, making 41 (1).Its result, the multi-layered wiring board 41 (1) of making is burnt till very densely.Therefore, think that resistivity also becomes the value like good design.Think this be since raw cook in 700 ℃ temperature-rise period, the removal of adhesive roughly finishes fully.The glass powder of also confirming raw cook can not carry out chemical reaction with through hole electrode 43 (2) and distribution 44 (2), can not produce the space at each other near interface yet.More than, affirmation can be used distribution 44 (2) and the through hole electrode 43 (2) of electrode distribution 2 of the present invention (with reference to Fig. 1) as multi-layered wiring board 41 (1).As distribution 44 (2) and through hole electrode 43 (2), need not use the electrode distribution of the silver thick film of high price, therefore, also can help the remarkable reduction of cost.
In execution mode; Electronic unit 1 is illustrated for the situation of plasma display panel 11, solar cell device 31 and ceramic installation base plate 41; But electronic unit 1 is not limited to these parts, can the expanding application scope to the electronic unit of the electrode distribution that can use aluminium.
Symbol description
1 electronic unit
2 electrode distributions
3 substrates
4 particles
4A particle group A (the first particle group)
4B particle group B (the second particle group)
5 oxides
6 necking down joint portions

Claims (13)

1. electronic unit, it possesses the electrode distribution, and said electrode distribution has: by aluminium (A l) and/or contain a plurality of particles that the alloy of aluminium constitutes and said particle is fixed on the oxide on the substrate, it is characterized in that,
Said oxide contains the phosphorus (P) and the aluminium of mixing.
2. electronic unit as claimed in claim 1 is characterized in that, said particle contains at least a element in silver (Ag), copper (Cu), silicon (S i), magnesium (Mg), the calcium (Ca).
3. according to claim 1 or claim 2 electronic unit is characterized in that, in the said electrode distribution, said particle is below the above 99.7 volume % of 84.2 volume %.
4. like each described electronic unit in the claim 1～3, it is characterized in that a plurality of said particles are made up of following particle group:
Particle diameter has the first particle group of about 95% volume fraction more than 0.5 μ m and in the scope of less than 1.5 μ m;
Particle diameter has the second particle group of about 95% volume fraction more than 1.5 μ m and in the scope of less than 8 μ m;
The weight of said first particle group and the said second particle group about equally.
5. like each described electronic unit in the claim 1～4, it is characterized in that said particle contains tabular particle.
6. like each described electronic unit in the claim 1～5, it is characterized in that said oxide is a principal component with phosphorus and oxygen (O), not consider the component ratio of said oxygen, the containing ratio of phosphorus is more than the 50 atom %.
7. like each described electronic unit in the claim 1～6, it is characterized in that a plurality of said particles pass through sinter bonded each other.
8. conductive paste is characterized in that, has:
Phosphoric acid solution; And
In said phosphoric acid solution, disperse, and by aluminium (Al) and/or contain a plurality of particles that the alloy of aluminium constitutes.
9. electronic unit is characterized in that, possess on substrate to apply the described conductive paste of claim 8, carry out sintering and the electrode distribution that forms,
Said electrode distribution has:
The a plurality of said particle that is bonded to each other through sintering; And
Form and said particle be adhered to the oxide of the phosphorus on the substrate by said phosphoric acid solution.
As claim 1～7, and 9 in each described electronic unit, it is characterized in that the resistivity less than 5 * 10 of said electrode distribution -5Ω cm.
11. as claim 1～7, and claim 9～10 in each described electronic unit, it is characterized in that the resistivity less than 1 * 10 of said electrode distribution -5Ω cm.
12. as claim 1～7, and claim 9～11 in each described electronic unit, it is characterized in that electronic unit is any of plasma display panel, solar cell device, ceramic installation base plate.
13. the manufacturing approach of electronic unit is characterized in that, coating electrically conductive property slurry on substrate, said conductive paste have by being dispersed in the aluminium in the phosphoric acid solution and/or containing a plurality of particles that the alloy of aluminium constitutes,
Said conductive paste to applying burns till, and forms the electrode distribution.
CN201080063260.3A 2010-02-26 2010-02-26 The manufacture method of electronic unit, conductive paste and electronic unit Expired - Fee Related CN102754534B (en)

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