CN102754534B - The manufacture method of electronic unit, conductive paste and electronic unit - Google Patents
The manufacture method of electronic unit, conductive paste and electronic unit Download PDFInfo
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- CN102754534B CN102754534B CN201080063260.3A CN201080063260A CN102754534B CN 102754534 B CN102754534 B CN 102754534B CN 201080063260 A CN201080063260 A CN 201080063260A CN 102754534 B CN102754534 B CN 102754534B
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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
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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
- 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
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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
- 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
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- Engineering & Computer Science (AREA)
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Abstract
The invention provides conductive paste, it has and to be dispersed in phosphoric acid solution and by aluminium (Al) and/or multiple particles (4) of forming containing the alloy of aluminium.This conductive paste is coated in substrate (3) go up and burn till, forms electrode wiring (2).This electrode wiring (2) has by aluminium and/or the multiple particles (4) formed containing the alloy of aluminium and the oxide (5) be fixed on by this particle (4) on substrate (3), the phosphorus (P) of oxide (5) containing mixing and aluminium.Particle (4) is containing at least one element in silver (Ag), copper (Cu), silicon (Si), magnesium (Mg), calcium (Ca).In electrode wiring (2), particle (4) is 84.2 more than volume % 99.7 volume below %.
Description
Technical field
The present invention relates to possess electrode wiring electronic unit, for the conductive paste of the formation of this electrode wiring and the manufacture method of this electronic unit.
Background technology
Electrode wiring is formed in the electronic units such as solar cell device, plasma display panel (PDP), liquid crystal display (LCD), ceramic multilayer wiring substrate.This electrode wiring uses conductive paste to be formed.In conductive paste, use silver (Ag) or aluminium (Al) as metallic.Electrode wiring is formed by being burnt till with high temperature in atmosphere by conductive paste, but conductive paste also has glass particle except metallic, when the burning till of conductive paste, by the temperature more than softening point that is heated to this glass particle, the softening flowing of glass particle, electrode wiring becomes fine and close, and bonding securely with substrate.
Employ in the conductive paste of the metallic of aluminium, motion has glass particle to use the conductive paste (with reference to patent documentation 1 etc.) of phosphate-based glass frit.Also motion has the conductive paste (with reference to the patent documentation 2 etc.) metallic of aluminium and the mixing of silver-colored metallic used as metallic.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-11927 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-108716 publication
Summary of the invention
The problem that invention will solve
Aluminium is at the stable oxide-film of Surface Creation, and therefore, the metallic of aluminium presents hard-to-sinter.Therefore, known in order to obtain sufficient electrical characteristic with the conductive paste of the metallic employing aluminium, as long as firing temperature to be set as more than 660.4 DEG C of aluminium fusing point.As patent documentation 1, when firing temperature being reduced to 550 DEG C ~ 600 DEG C, the manufacture of electronic unit becomes easy, but thinks and can not obtain sufficient electrical characteristic, sometimes in the design of electronic unit, produces restriction.In patent documentation 2, by the metallic of aluminum mixture in conductive paste and the metallic of silver, temperature when successfully making the sintering temperature of metallic be aluminium lower than metallic.In patent documentation 2, the temperature of burning till can be reduced, also can obtain sufficient electrical characteristic, but think because metallic uses silver, therefore, be difficult to reduce costs.
Therefore, the object of the invention is to, possess even provide with low cost the method that low firing temperature also can obtain the electronic unit of the electrode wiring of sufficient electrical characteristic, conductive paste and this electronic unit of manufacture.
For solving the means of problem
In order to realize described object, the invention provides electronic unit, it possesses electrode wiring, and described electrode wiring has: by aluminium (Al) and/or multiple particles of forming containing the alloy of aluminium; And the oxide described particle is fixed on substrate, it is characterized in that,
Described oxide contains phosphorus (P) and the aluminium of mixing.
In addition, the invention provides conductive paste, it is characterized in that, have:
Phosphoric acid solution; And
Multiple particle, described multiple particle dispersion, in described phosphoric acid solution, is formed by aluminium (Al) and/or containing the alloy of aluminium.
In addition, the invention provides the manufacture method of electronic unit, it is characterized in that, conductive paste is coated on substrate, described conductive paste have be dispersed in phosphoric acid solution by aluminium and/or multiple particles of forming containing the alloy of aluminium,
The described conductive paste of coating is burnt till, forms electrode wiring.
Invention effect
According to the present invention, possess even can provide with low cost the method that low firing temperature also can obtain the electronic unit of the electrode wiring of sufficient electrical characteristic, conductive paste and this electronic unit of manufacture.
Accompanying drawing explanation
Fig. 1 is a part for the profile of the electrode wiring that electronic unit that first embodiment of the invention relates to possesses;
Fig. 2 is a part for the profile of the plasma display panel (electronic unit) that second embodiment of the invention relates to;
Fig. 3 A is the ground plan of the solar cell device (electronic unit) that third embodiment of the invention relates to;
Fig. 3 B be turn upside down the A-A direction that represents Fig. 3 A to pseudosection;
Fig. 4 is the profile of the ceramic multilayer wiring substrate (electronic unit) that four embodiment of the invention relates to;
Fig. 5 is an example of ceramic multilayer wiring substrate (electronic unit) that four embodiment of the invention relates to temperature-time table when burning till.
Embodiment
Below, suitably with reference to accompanying drawing, embodiments of the present invention are described in detail.In addition, in the various figures, also the repetitive description thereof will be omitted to mark identical symbol to common part.In addition, the present invention is not limited to the multiple each execution mode proposed at this, also can be appropriately combined.
(the first execution mode)
As shown in table 1, in the first embodiment, form total 13 kinds of electrode wirings of embodiment 1 ~ 12 and a comparative example, and various characteristic is evaluated.When forming electrode wiring, conductive paste also changes manufacturing condition manufacture in each embodiment 1 ~ 12 and comparative example, and the firing condition of conductive paste (electrode wiring) also changes in each embodiment 1 ~ 12 and comparative example.In addition, in the manufacturing condition of conductive paste, change aluminium (Al) particle be made up of 3 kinds of particle groups mix proportion and by phosphorus pentoxide (P
2o
5), water (H
2and ethanol (C O)
2h
5the weight ratio of the phosphoric acid solution OH) formed.In addition, along with the change of the weight ratio of phosphoric acid solution, the volume of aluminium also changes relative to the ratio of the volume sum of aluminium and phosphorus pentoxide.In addition, as the characteristic evaluated, electrode wiring is carried out to the measurement of disbonded test, Water Resistance Test, resistivity.
Below, the formation of electrode wiring is described in detail.
[table 1]
(1. the formation of electrode wiring)
(cooperation of 1-1. aluminum particulate)
First, by aluminium melting, with the glomerate particle of water atomization shape.Utilize sieve from a part for this particle, remove the particle of particle diameter more than 8 μm, utilize sieve to remove the particle of particle diameter less than 0.5 μm.Namely the particle after being utilized by remaining particle sieve to remove large particle and little particle, utilizes sieve to be divided into: particle group A further, its particle diameter more than 0.5 μm less than the volume fraction in the scope of 1.5 μm with about more than 95%; Particle group B, its particle diameter more than 1.5 μm less than the volume fraction in the scope of 8 μm with about more than 95%.
In addition, by the part of particle directly formed with water atomization, process with ball mill in organic solvent, form the particle of tabular.In addition, in order to improve the thermal stability of the particle of this tabular, in reducing atmosphere, carry out the annealing in process of temperature 700 DEG C.Utilize sieve from the particle of this tabular, remove the particle of particle diameter more than 8 μm, and the particle of particle diameter less than 1.5 μm removed by recycling sieve.Particle after namely remaining particle utilizes sieve to remove large particle and little particle as particle diameter more than 1.5 μm less than the particle group of tabular of volume fraction in the scope of 8 μm with about more than 95%, i.e. particle group C.
As shown in table 1, in embodiment 1 ~ 11 and comparative example, become 50 % by weight with the particle of particle group A, mode that the particle of particle group B becomes 50 % by weight is with the use of the particle of particle group A and particle group B.In embodiment 12, become 50 % by weight with the particle of particle group A, mode that the particle of particle group C becomes 50 % by weight is with the use of the particle of particle group A and particle group C.
(generation of 1-2. phosphoric acid solution)
Then, in each embodiment 1 ~ 12, phosphoric acid solution is generated.Phosphoric acid solution generates phosphorus pentoxide, water and ethanol with the weight ratio mixing shown in table 1.In addition, ethanol is evaporation in order to accelerate phosphoric acid solution and drying, and be difficult to after the drying absorb water and use.From embodiment 1 to embodiment 8, the weight ratio of phosphorus pentoxide increases successively, and the weight ratio of water reduces successively, the weight ratio of phosphorus pentoxide and water sum is set to necessarily.In addition, the weight ratio of ethanol is set to necessarily.The weight ratio of the phosphorus pentoxide of embodiment 9 ~ 12, water and ethanol in the same manner as in Example 3, is set to 10 % by weight, 80 % by weight, 10 % by weight.In addition, also phosphoric acid (H can be used
3pO
4) replace phosphorus pentoxide.In this situation, regulate the amount of water in the mode of the concentration equalization of phosphorus atoms.In addition, in a comparative example, do not use phosphoric acid solution, replace, employing lead (Pb) is glass.
(generation of 1-3. conductive paste)
In each embodiment 1 ~ 12,100 weight portions of the aluminum particulate coordinated with 1-1 are added to the phosphoric acid solution of 30 weight portions that mixing generates with 1-2.By irradiating the ultrasonic wave of 10 minutes to this mixture, make aluminum particulate be scattered in phosphoric acid solution, obtain conductive paste.
In a comparative example, to 100 weight portions of the aluminum particulate coordinated with 1-1, add lead glass powder, the acetate of butyl carbitol as solvent, the ethyl cellulose as adhesive of mixing 10 weight portion.By irradiating the ultrasonic wave of 10 minutes to this mixture, make the powder of aluminum particulate, lead system glass and adhesive be scattered in solvent, obtain conductive paste.
(burning till of 1-4. electrode wiring)
In each embodiment 1 ~ 12 and comparative example, with scraper at aluminium oxide (Al
2o
3) coating electrically conductive slurry on substrate.After coating, conductive paste is made it dry for 30 minutes with temperature 150 DEG C heating in atmosphere.Then, be warmed up to the firing temperature represented in the firing condition of table 1 in atmosphere with the programming rate of 5 DEG C/min with electric furnace, and keep burning till the firing time represented in the firing condition of table 1 with this firing temperature, then, naturally cool.Burnt till by this, complete electrode wiring.Film (electrode wiring) thickness after burning till in embodiment 1 ~ 12 and comparative example is all about 10 μm.The firing temperature of the firing condition of embodiment 1 ~ 8, embodiment 12 and comparative example is all 700 DEG C, firing time is all 30 minutes.In embodiment 9 ~ 11, firing temperature is changed to 400 DEG C, 500 DEG C, 600 DEG C, firing time is all 30 minutes.
(2. the characteristic of electrode wiring)
(2-1. disbonded test)
In each embodiment 1 ~ 12 and comparative example, the electrode wiring completed by disbonded test evaluation is to the adhesive strength of substrate.In disbonded test, peel after commercially available cellotape is attached to electrode wiring.And, after peeling, observation evaluation is carried out to electrode wiring.As metewand, use following benchmark: to be peeled by most of aluminum particulate and the situation that electrode wiring becomes broken string state is set to "×", a part for aluminum particulate to be peeled and the situation that a part for electrode wiring is cut off and become broken string state is set to " △ ", aluminum particulate is not peeled (aluminum particulate comprising the surface of electrode wiring is attached to the degree on cellotape compared with unfertile land) and the situation that electrode wiring does not become broken string state is set to "○".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 "○".
The result of disbonded test is compared between embodiment 1 ~ 8, it can thus be appreciated that, be preferably more than 1 % by weight with the mass ratio range of phosphorus pentoxide, be less than 89 % by weight (embodiments 2 ~ 8: the evaluation at least obtaining " △ ") with the mass ratio range of water, more preferably being more than 10 % by weight with the mass ratio range of phosphorus pentoxide, is less than 80 % by weight (embodiments 3 ~ 8: the evaluation obtaining "○") with the mass ratio range of water.Like this, the result of disbonded test depends on the weight ratio of the phosphorus pentoxide in phosphoric acid solution, thiss is presumably because that the weight ratio of this phosphorus pentoxide is relevant relative to the ratio of the volume of the aluminium in electrode wiring to phosphorus pentoxide.That is, this is because, thinking to fix aluminum particulate on substrate, relative to the volume of aluminium, needing the phosphorus pentoxide of the volume of more than certain proportion.Table 1 represents the ratio of the volume of aluminium relative to the volume sum of aluminium and phosphorus pentoxide, but when evaluating the result of disbonded test with the ratio of this volume, knownly preferably count 99.7 below volume % (embodiment 2 ~ 8: the evaluation at least obtaining " △ ") with the ratio of this volume, be more preferably 97.4 below volume % (embodiment 3 ~ 8: the evaluation obtaining "○").
In addition, the result of disbonded test is compared between embodiment 3 and embodiment 9 ~ 11, thus, known under the firing temperature of firing condition 400 DEG C if (embodiment 9), then obtain the evaluation of "×", but 500 DEG C if (embodiment 10), 600 DEG C (embodiment 11), 700 DEG C (embodiment 3), then obtain the evaluation of "○".Thus, think that the firing temperature of electrode wiring of the present invention can not adhere to below 400 DEG C on substrate, be easy to peel, but more than 400 DEG C, such as more than 500 DEG C time, become fine and close and be sealed on substrate.
In addition, the result of disbonded test compared in embodiment 3 and embodiment 12, thus, known use Arbitrary Particles group B (embodiment 3) and particle group C (embodiment 12), all obtain the evaluation of "○".The also known evaluation also obtaining "○" in a comparative example.
(2-2. Water Resistance Test)
In each embodiment 1 ~ 12 and comparative example, with Water Resistance Test, the saprophagous character of the electrode wiring completed relative to water is evaluated.In Water Resistance Test, electrode wiring is flooded 30 minutes in the warm water of 70 DEG C.After immersion, electrode wiring observed, evaluate.As metewand, use following benchmark: after experiment, situation electrode wiring being formed black is set to "×", the situation that the color of electrode wiring changes a little is set to " △ ", by color almost unchanged situation be set to "○".As shown in table 1, the result of disbonded test is "×" in embodiment 1 and embodiment 9, is " △ " in example 2, is "○" 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 " △ ", is "○" in embodiment 2 ~ 8 and embodiment 10 ~ 12.
The result of Water Resistance Test is compared between embodiment 1 ~ 8 and comparative example, it can thus be appreciated that, the weight ratio of preferred phosphorus pentoxide is more than 0.5 % by weight, the weight ratio of water is less than 89.5 % by weight (embodiments 1 ~ 8: the evaluation at least obtaining " △ "), more preferably the weight ratio of phosphorus pentoxide is more than 1 % by weight, and the weight ratio of water is less than 89 % by weight (embodiments 2 ~ 8: the evaluation obtaining "○").On the other hand, known comparative example becomes "×".Compared with comparative example, the excellent water resistance of electrode wiring one side of known embodiment 1 ~ 8.In addition, when evaluating relative to the result of the comparison Water Resistance Test of the volume sum of aluminium and phosphorus pentoxide with the volume of aluminium, known, be preferably 99.9 below volume % (embodiment 1 ~ 8: the evaluation at least obtaining " △ "), be more preferably 99.7 below volume % (embodiment 2 ~ 8: the evaluation obtaining "○").
In addition, the result of Water Resistance Test is compared between embodiment 3 and embodiment 9 ~ 11, it can thus be appreciated that, if the firing temperature of firing condition is 400 DEG C (embodiments 9), then obtain the evaluation of "×", but 500 DEG C if (embodiment 10), 600 DEG C (embodiment 11), 700 DEG C (embodiment 3), then obtain the evaluation of "○".Thus, if think the firing temperature less than 400 DEG C of electrode wiring of the present invention, then aluminum particulate can not be covered by the oxide of densification, higher resistance to water can not be obtained, if but more than 400 DEG C, such as more than 500 DEG C, the oxide of aluminium coating particle becomes fine and close, obtains higher resistance to water.On the other hand, in a comparative example, even if firing temperature is 700 DEG C, can not resistance to water be obtained, be evaluated as "×".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, it can thus be appreciated that, use Arbitrary Particles group B (embodiment 3) and particle group C (embodiment 12) all can obtain the evaluation of "○".
(2-3. determination of resistivity)
In each embodiment 1 ~ 12 and comparative example, the resistivity of the electrode wiring measured.In determination of resistivity, measure resistance and the thickness of electrode wiring, calculate resistivity based on this resistance and thickness.The result of determination of resistivity is compared between embodiment 1 ~ 8 and comparative example, it can thus be appreciated 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, by comparing between embodiment 1 ~ 8, known resistivity obtains minimum value in embodiment 3, becomes 0.68 × 10
-5Ω cm.
With mass ratio range, along with the increase (from embodiment 1 to embodiment 3) of phosphorus pentoxide from 0.5 % by weight to 10 % by weight, resistivity reduces, and in 10 % by weight (embodiments 3), resistivity becomes minimum value (0.68 × 10
-5Ω cm), along with from 10 % by weight to 70 % by weight increase (from embodiment 3 to embodiment 8), resistivity increase.With mass ratio range, phosphorus pentoxide is from the scope (embodiment 2 ~ 4) of 1 % by weight to 15 % by weight, and resistivity becomes 1.0 × 10
-5below Ω cm.With mass ratio range, phosphorus pentoxide is from the scope (embodiment 1 ~ 7) of 0.5 % by weight to 65 % by weight, and resistivity becomes than the resistivity (5.6 × 10 lower than comparative example
-5Ω cm) 5.0 × 10
-5Ω cm is little.
When evaluating relative to the result of the comparison determination of resistivity of the volume sum of aluminium and phosphorus pentoxide with the volume of aluminium, with volume basis, 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 embodiment 3 to embodiment 8) from 97.4 volume % to 84.2 volume %, resistivity increases.With this volume basis, in the scope (embodiment 2 ~ 4) from 99.7 volume % to 96.1 volume %, resistivity becomes 1.0 × 10
-5below Ω cm.With this volume basis, in the scope (embodiment 1 ~ 7) from 99.9 volume % to 85.1 volume %, resistivity is the resistivity (5.6 × 10 than comparative example
-5Ω cm) little of 5.0 × 10
-5Ω cm.
By the result of determination of resistivity in embodiment 3, compare between embodiment 9 ~ 11 and comparative example, it can thus be appreciated that, with the resistivity (5.6 × 10 than comparative example
-5Ω cm) little by 5.0 × 10
-5Ω cm compares, and resistivity is lower in embodiment 3, embodiment 10 and embodiment 11.In addition, by comparing between embodiment 3 and embodiment 9 ~ 11, known, resistivity obtains minimum value in embodiment 3, becomes 0.68 × 10
-5Ω cm.
In firing temperature, along with firing condition is from the increase (from embodiment 9,10,11 to embodiment 3) of 400 DEG C to 700 DEG C, resistivity reduces, and resistivity becomes minimum value (0.68 × 10 700 DEG C (embodiments 3)
-5Ω cm).In firing temperature, from the scope (embodiment 11 and embodiment 3) of 600 DEG C to 700 DEG C, resistivity becomes 1.0 × 10
-5below Ω cm.In firing temperature, more than 400 DEG C, such as, in the scope (embodiment 10, embodiment 11, embodiment 3) of more than 500 DEG C, resistivity is the resistivity (5.6 × 10 than comparative example
-5Ω cm) little of 5.0 × 10
-5Ω cm.
In addition, the result of determination of resistivity is compared in embodiment 3 and embodiment 12, it can thus be appreciated that, compared with particle group B (spherical particle: embodiment 3), use one of particle group C (platy particles: embodiment 12) can reduce resistivity further.
(optimization of 2-4. manufacturing condition)
When the volume of aluminium being evaluated relative 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, known, when this volume ratio is in the scope of 99.7 below volume % 84.2 volume more than % (embodiment 2 ~ 8), obtain good tack (disbonded test result) and good resistance to water (Water Resistance Test result).In addition, when rewriting this volume ratio by the volume ratio of phosphorus pentoxide, the volume ratio of phosphorus pentoxide is become by the value that 100 volume % deduct the volume ratio of aluminium, therefore, time in the scope of 0.3 more than volume % 15.8 volume below % (embodiment 2 ~ 8), obtain good tack (disbonded test result) and good resistance to water (Water Resistance Test result).
Also known, when this volume ratio is in the scope of 99.7 below volume % 85.1 volume more than % (embodiment 2 ~ 7), obtain good tack (disbonded test result), good resistance to water (Water Resistance Test result) and good resistivity (determination of resistivity result).Also known, when this volume ratio is in the scope of 97.4 below volume % 96.1 volume more than % (embodiment 3,4), obtain better tack (disbonded test result), good resistance to water (Water Resistance Test result), resistivity is 1.0 × 10
-5the better resistivity (determination of resistivity result) of below Ω cm.
In addition, when firing temperature is evaluated, known, when this firing temperature is in the scope of more than 500 DEG C less than 700 DEG C (embodiment 10,11,3), obtain good tack (disbonded test result), good resistance to water (Water Resistance Test result) and good resistivity (determination of resistivity result).Also known, when this firing temperature is in the scope of more than 600 DEG C less than 700 (embodiment 11,3), obtain good tack (disbonded test result), good resistance to water (Water Resistance Test result), resistivity is 1.0 × 10
-5the better resistivity (determination of resistivity result) of below Ω cm.
In addition, when the particle group B of aluminum particulate and the cooperation of particle group C are evaluated, known, during use particle group C replacement particle group B time (embodiment 12), obtain good tack (disbonded test result), good resistance to water (Water Resistance Test result), the resistivity (determination of resistivity result) better than the situation of the particle group B using embodiment 3.
Fig. 1 represents the partial enlarged drawing of the profile of the electrode wiring 2 that the electronic unit 1 of first embodiment of the invention possesses.The electrode wiring 2 that electronic unit 1 has aluminum oxide substrate 3 and is adhesively fixed on aluminum oxide substrate 3.Electrode wiring 2 have by aluminium (Al) and/or multiple particles 4 of forming containing the alloy of aluminium with make particle 4 and be fixed on oxide 5 on substrate 3.
Fig. 1 is the figure based on using sweep electron microscope-energy dispersion-type X-ray analytical equipment (SEM-EDX) to observe the result of the electrode wiring 2 made in the such as embodiment 11 of table 1.By sintering, multiple particle 4 is 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 analytical equipment (EDX).
The phosphorous oxides that it is principal component that oxide 5 has with phosphorus and oxygen (O), not consider the component ratio of oxygen, the containing ratio of phosphorus becomes 50 more than atom %.In addition, in oxide 5, except phosphorus, also aluminium is detected.Infer thus and arrive, conductive paste is before burning till or in burning till, and the natural oxide film covering the aluminium on particle 4 surface be scattered in phosphoric acid solution is dissolved by phosphoric acid solution, and aluminium is stripping in phosphoric acid solution, by burning till, the phosphoric acid solution containing this aluminium finally becomes the oxide 5 containing phosphorus and aluminium.The natural oxide film of the aluminium that the surface coverage of the particle 4 of aluminum and its alloy disappears when burning till, and thus, necking down joint portion 6 can be made easily to produce, can reduce the resistivity of electrode wiring 2.
In addition, the high-hydrophilic on particle 4 surface of the aluminum and its alloy utilizing the interpolation etc. of ethanol to cause, whole of particle 4 surface moistening by phosphoric acid solution, and covered by phosphoric acid solution.Therefore, when burning till, the whole surperficial oxide 5 eliminating the particle 4 of necking down joint portion 6 covers.In addition, by removing the natural oxide film of aluminium, oxide 5 directly connects with particle 4, and oxide 5 forms bilayer but not individual layer, and therefore, in oxide 5, phosphorus (P) atom and the mixing of aluminium atom are contained in the entirety in film.
In addition, as shown in the embodiment 10 of table 1 and embodiment 11, even if distinguish that electrode wiring 2 also presents excellent conductivity at the firing temperature of the fusing point less than 660.4 DEG C of aluminium.At present, the sintering of aluminium is not in progress, and thinks that this oxide-film (natural oxide film) is reason, needs the firing temperature of more than fusing point to be for destroying this oxide film thereon.In electrode wiring 2, in the phosphoric acid solution of acidity, the oxide-film on particle 4 surface 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 phosphoric acid oxide 5, as the precipitation such as oxidized compound or aluminium oxide of phosphorus and aluminium.By removing oxide film thereon, promoting the sintering of aluminium, even if infer to utilizing fusing point to carry out burning till of low temperature, also playing good conductivity.
In addition, the surface of phosphoric acid solution coated particle 4, when burning till, the aluminium component reaction of phosphoric acid and stripping, becomes the oxide 5 of compound (oxidized compound).In electrode wiring 2, think that the main cause that resistance to water improves is because the whole surface removal from aluminum particulate 4 dredges thin oxide-film, the particle 4 of aluminium whole uniform surface form fine and close phosphorus and the compound of aluminium, therefore, can not expose the surface of particle 4, stability chemically improves.Such as, but more than 400 DEG C, more than 500 DEG C when carrying out burning till, obtain good resistance to water.
On the other hand, when using sweep electron microscope-energy dispersion-type X-ray analytical equipment (SEM-EDX) to observe the electrode wiring 2 made in the comparative example shown in table 1, plumbous (Pb) metal is separated out at particle 4 interface each other of aluminium, observes the segregation of glass ingredient.Think that this is the oxidation caused by the Pb system glass of the particle 4 of aluminium, the result that the lead of Pb system glass is restored.Therefore, in the Pb system glass used at present, the remained on surface of aluminum particulate dredges thin oxide film thereon, and the surface of aluminum particulate is oxidized, therefore, infers that the oxide film thereon that can again be formed is also for dredging thin oxide film thereon, can not be coated to densely.
In particle 4, not only aluminum particulate 4, also can use the particle 4 be made up of the alloy containing aluminium.As the alloy containing aluminium, containing at least one element in silver (Ag), copper (Cu), silicon (Si), magnesium (Mg), calcium (Ca).Such as, by adding silver, the conductance of alloy (Al-Ag) can be improved.In addition, by adding copper, the intensity of alloy (Al-Cu) can be improved.By adding silicon, the abrasion performance of alloy (Al-Si) can be improved.By adding magnesium or calcium, intensity and the corrosion resistance of alloy (Al-Mg, Al-Ca) can be improved.
Particle 4 is made up of less than particle group B (the second particle group) 4B of the volume fraction in the scope of 8 μm with about 95% more than 1.5 μm less than particle group A (the first particle group) 4A of volume fraction and particle diameter in the scope of 1.5 μm with about 95% more than 0.5 μm particle diameter.The total weight of the total weight of multiple particles 4 of particle group A (4A) and multiple particles 4 of particle group B (4B) is roughly equal.Thus, the particle 4 of the particle group A (4B) that particle diameter is little enters the gap between the particle 4 of the large particle group B (4B) of particle diameter, can improve the density of particle 4, therefore, it is possible to form fine and close electrode wiring 2.
(the second execution mode)
Fig. 2 represents a part for the profile of the plasma display panel (PDP: electronic unit) 11 (1) that second embodiment of the invention relates to.In this second embodiment, as electronic unit 1 of the present invention can be applied, carry out enumerating explanation for plasma display panel 11.The electrode wiring 2 of electronic unit 1 of the present invention is used at the show electrode 20 of plasma display panel 11 (1) and address electrode 21.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 μm, and the gap of front panel 12 (3) and backplate 13 (3) maintains with next door 14.The circumference encapsulating material 15 of front panel 12 (3) and backplate 13 (3) carries out hermetic seal, fills rare gas in the display panel inside in front panel 12 (3) and backplate 13 (3) gap.
Front panel 12 (3) is formed show electrode 20 (2).Front panel 12 (3) is suitable with the substrate 3 of the first execution mode, and show electrode 20 (2) is suitable with the electrode wiring 2 of the first execution mode.Show electrode 20 (2) is formed with dielectric layer 23, dielectric layer 23 is formed the protective layer 25 (such as, the vapor-deposited film of magnesium oxide (MgO)) from discharging for the protection of show electrode 20 (2) etc.
Overleaf plate 13 (3) is formed with address electrode 21 (2).Backplate 13 (3) is suitable with the substrate 3 of the first execution mode, and address electrode 21 (2) is suitable with the electrode wiring 2 of the first execution mode.Plane is seen, address electrode 21 (2) is formed in the mode orthogonal with show electrode 20 (2).Address electrode 21 (2) is formed with dielectric layer 24, dielectric layer 24 is provided with the next door 14 for Component units 16.Next door 14 is the tectosome of striated or grid (chest) shape.
In gap between front panel 12 (3) and backplate 13 (3), become unit 16 by the short space that next door 14 divides.Fluorophor 17,18,19 is filled with at unit 16.3 unit 16 of fill the unit 16 of red-emitting phosphors 17, fill the unit 16 of green-emitting phosphor 18, filling 3 primary colors of the unit 16 of blue emitting phophor 19 corresponding form a pixel.Each pixel can send the light of shades of colour according to the signal putting on show electrode 20 (2) and address electrode 21 (2).
Then, the manufacture method of article on plasma display panel 11 (1) is described.
(making of conductive paste)
First, the particle group A preparing to illustrate in table 1 is as particle contained in conductive paste.Particle is set to the metallic of aluminium.The particle of particle group A be particle diameter more than 0.5 μm less than the volume fraction in the scope of 1.5 μm with about more than 95%.Do not use particle group B and particle group C, use in the particle group A of mix proportion 100 % by weight.In addition, in phosphoric acid solution, prepare the phosphoric acid solution with the embodiment 3 identical weight ratio of table 1.That is, the phosphoric acid solution of weight ratio of the phosphorus pentoxide of 10 % by weight, the water of 80 % by weight, the ethanol of 10 % by weight is prepared.100 weight portions of the powder prepared before are added to this phosphoric acid solution of 30 weight portions.These mixtures are irradiated to the ultrasonic wave of 10 minutes, thus, make particle dispersion in phosphoric acid solution, complete conductive paste.
(making of plasma display panel)
Then, plasma display panel is made.First, by whole the coating electrically conductive slurry of silk screen print method at front panel 12 (3) and backplate 13 (3), dry in 150 DEG C in an atmosphere.Lithographically remove the position that the coated film of conductive paste is unnecessary with etch, 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 an atmosphere, within 30 minutes, burn till with firing temperature 600 DEG C, firing time, complete show electrode 20 (2) and address electrode 21 (2).In this burns till, firing atmosphere is acid atmosphere, but by 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, apply at front panel 12 (3) and backplate 13 (3) the dielectricity slurry becoming dielectric layer 23,24 respectively, in an atmosphere, within 30 minutes, burn till with firing temperature 600 DEG C, firing time.In addition, in this burns till, firing atmosphere becomes acid atmosphere, dielectric layer 23 directly connects with show electrode 20 (2), dielectric layer 24 directly connects with address electrode 21 (2), but burnt till by this, dielectric layer 23 and show electrode 20 (2) do not carry out chemical reaction, and dielectric layer 24 and address electrode 21 (2) do not carry out chemical reaction.From the dielectric layer 23 side evaporation protective layer 25 of front panel 12 (3).
Material forming at least containing pulverous glass component and filler is striated or clathrate by next door 14, makes the tectosome of this shaping with 500 ~ 600 DEG C of sintering.Dielectric layer 24 configures this next door 14, Component units 16.And, fill the fluorophor slurry corresponding with three primary colors to each unit 16 and burn till with 450 ~ 500 DEG C, thus, in unit 16, forming red-emitting phosphors 17, green-emitting phosphor 18 and blue emitting phophor 19.
Then, by dotting glue method or print process etc., encapsulating material 15 is applied at the circumference of either party of front panel 12 (3) or backplate 13 (3).And, encapsulation front panel 12 (3) and backplate 13 (3).In the encapsulation of front panel 12 (3) and backplate 13 (3), make the correct position of front panel 12 (3) and backplate 13 (3) alignedly subtend and configuring, and be heated to 420 ~ 500 DEG C.When this heating, the gas in deliverying unit 16, replaces, and encloses rare gas.In addition, encapsulating material 15 also can formation with fluorophor 17 ~ 19 time burning till of fluorophor slurry temporarily burn till simultaneously.By temporarily burning till encapsulating material 15, contained bubble in encapsulating material 15 can be reduced.In addition, in fig. 2, encapsulating material 15 and address electrode 21 (2) directly connect, but in order to externally extraction electrode, show electrode 20 (2) also directly connects with encapsulating material 15.Encapsulating material 15 when temporarily burning till and glass packaging time heat, firing atmosphere adds hanker for acid atmosphere at this, but by this heating, encapsulating material 15 does not carry out chemical reaction with show electrode 20 (2) and address electrode 21 (2).Above, plasma display panel 11 (1) is completed.
(evaluation of plasma display panel)
(visual examination)
Carry out surrounding's visual examination of show electrode 20 (2) and address electrode 21 (2).Generation and the variable color in space is not seen in show electrode 20 (2) and the interface portion of front panel 12 (3) and the interface portion of show electrode 20 (2) and dielectric layer 23.In addition, generation and the variable color in space is not seen in address electrode 21 (2) and the interface portion of backplate 13 (3) and the interface portion of address electrode 21 (2) and dielectric layer 24.Plasma display panel 11 (1) can be made with state good in appearance.
(lighting experiment)
Then, the plasma display panel 11 (1) carrying out making light experiment.In order to light the unit 16 of (luminescence) plasma display panel 11 (1), voltage is applied between the show electrode 20 (2) and address electrode 21 (2) of the unit 16 that will light, address electric discharge is carried out in unit 16, rare gas is excited as plasmoid, makes accumulation Wall charge in unit 16.Then, certain voltage is applied to show electrode 20 (2), thus, only cause display discharge and produce ultraviolet 22 at the unit 16 of accumulation Wall charge.And, utilize this ultraviolet 22 to make fluorophor 17 ~ 19 luminous, display image (information).
Before and after the display of this image information, the resistivity of show electrode 20 (2) and address electrode 21 (2) can not increase.In addition, adjacent show electrode 20 (2) each other and adjacent address electrode 21 (2) each other etc., proof voltage can not reduce, can booster voltage, can lighting unit 16.In addition, also can not produce the mobile phenomenon of the electrode wiring of silver thick film, particularly not find the point hindering other.The show electrode 20 (2) of the plasma display panel 11 (1) of the second execution mode and address electrode 21 (2) do not use high price silver, therefore, can contribute to the remarkable reduction of cost yet.
(the 3rd execution mode)
Fig. 3 A represents the ground plan (rear side) of the solar cell device (electronic unit) 31 (1) of third embodiment of the invention, Fig. 3 B represent the A-A direction of Fig. 3 A to pseudosection, sensitive surface side (face side) is set to upside, rear side is set to downside.In the third embodiment, as electronic unit 1 of the present invention can be applied, carry out enumerating explanation for solar cell device 31.In Fig. 3 A and Fig. 3 B, be that an example represents with back contact type (back electrode type) crystal silicon solar energy battery element 31 (1).The electrode wiring 2 of electronic unit 1 of the present invention is used at the back side p-type electrode 37 of solar cell device 31 (1).In addition, the battery wafer 38 be made up of the silicon substrate of p-type is formed with back side p-type electrode 37 (2).Element wafer 38 (3) is suitable with the substrate 3 of the first execution mode, and back side p-type electrode 37 (2) is suitable with the electrode wiring 2 of the 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 between through surface and 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).The through hole electrode 34 of silvery is embedded at through hole 39.In the mode be connected with through hole electrode 34, be formed with the grid shape current collection gate electrode 32 of silvery in the sensitive surface side (face side) of element wafer 38 (1).
In the rear side of element wafer 38 (1), leave through hole 39 and through hole electrode 34 ground is formed with high concentration dope layer 35.High concentration dope layer 35 prevents combining again of charge carrier.In the mode with 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, in the mode with 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 manufacture method of solar cell 31 (1) is described.
(making of conductive paste)
In the third embodiment, as conductive paste, make and use the slurry identical with the conductive paste used in the embodiment 2 of table 1.
(making of solar cell)
Prepare p-type silicon substrate as element wafer 38 (3).Then, by laser drilling or corrosion etc., through hole 39 is formed at element wafer 38 (3).Then, diagram is omitted, but owing to improving the incident efficiency of light, therefore, uses 1% caustic soda (NaOH: NaOH) and 10% isopropyl alcohol (CH
3cH (OH) CH
3) mixed liquor, the sensitive surface side (face side) of corrosion element wafer 38 (3) and form texture.
At the liquid of the sensitive surface side (face side) of element wafer 38 (3) coating containing phosphorus pentoxide, process in 30 minutes is carried out with 900 DEG C, thus, make phosphorus 38 (1) (P) diffusion from phosphorus pentoxide to element wafer, form n-type semiconductor layer 33 in sensitive surface side.In addition, diagram is omitted, but also in n-type semiconductor layer 33, can form silicon nitride film (Si the same thickness
3n
4) antireflection film.This silicon nitride film can pass through with silane (SiH
4) and ammonia (NH
3) mist be raw material plasma CVD method formed.
Then, filling commercially available silver paste by print process to through hole 39 inside formed before, in addition, in sensitive surface side, is grid shape by above-mentioned silver paste printing, thus, forms through hole electrode 34 and current collection gate electrode 32.Make the through hole electrode 34 of formation and current collection gate electrode 32 with 150 DEG C of dryings 30 minutes.
In the rear side of the opposition side of sensitive surface, use silver paste, by silk screen printing, carry out striated printing, form back side n-type electrode 36.In addition, in the rear side of the opposition side of sensitive surface, use the conductive paste identical with the conductive paste used in embodiment 2, by silk screen printing, carry out striated printing, form back side p-type electrode 37 (2).Make the back side n-type electrode 36 of formation and back side p-type electrode 37 (2) with 150 DEG C of dryings 30 minutes.
To through hole electrode 34, current collection gate electrode 32, back side n-type electrode 36 and back side p-type electrode 37 (2), carry out burning till of maintenance 2 seconds with 850 DEG C, thus, complete back contact type solar cell device 31 (1).In addition, burnt till by this, aluminium from back side p-type electrode 37 (2) rearwardly p-type electrode 37 (2) bottom element wafer 38 (3) spread, form the high concentration dope layer 35 for preventing charge carrier from combining again simultaneously.
In addition, as a comparison, use the conductive paste identical with the conductive paste used in the comparative example of table 1, the back contact type solar cell device 31 (1) forming back side p-type electrode 37 (2) is made.
(evaluation of solar cell device)
Compared with the solar cell made because comparing, distinguish that the conversion efficiency of the back contact type solar cell 31 (1) of the 3rd execution mode becomes higher efficiency.This is presumably because the resistance value that can reduce back side p-type electrode 37 (2).Above, confirm that electrode wiring 2 (with reference to Fig. 1) of the present invention can be used 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 method corresponding with the manufacture method of the p-type electrode of various solar cell.
(the 4th execution mode)
Fig. 4 represents 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 (with reference to Fig. 1) of the present invention is applied to multi-layered wiring board is described.As 1 of multi-layered wiring board example in Fig. 4, represent the multi-layered wiring board 41 (1) be made up of 5 layers of low-temperature sintering ceramic (LTCC:LowTemperatureCo-firedCeramics).The through hole electrode 43 (2) of multi-layered wiring board 41 (1) and distribution 44 (2) use the electrode wiring 2 of electronic unit 1 of the present invention.On ceramic substrate 42 (3) is respective and below be formed with distribution 44 (2).In 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).The through ceramic substrate 42 (3) of through hole electrode 43 (2).At multi-layered wiring board 41 (1), be dimensionally formed with distribution 44 (2) and through hole electrode 43 (2).Ceramic substrate 42 (3) is suitable with the substrate 3 of the first execution mode, and through hole electrode 43 (2) is suitable with the electrode wiring 2 of the first execution mode with distribution 44 (2).
Then, the manufacture method of multi-layered wiring board 41 (1) is described.
(making of conductive paste)
In the 4th execution mode, as conductive paste, make and use the slurry identical with the conductive paste used in the embodiment 2 of table 1.
(making of multi-layered wiring board)
First, multiple raw cooks of stirred glass powder, ceramic powders and the mixing formation of adhesive are prepared.Raw cook burns till by described later the ceramic substrate 42 (3) becoming each layer.Then, through hole is offered in the position of the hope of raw cook.To the raw cook offering through hole, by the conductive paste identical with the slurry used in embodiment 2, be coated into the Wiring pattern of hope by print process.Now, also filled conductive slurry in through hole.The conductive paste being applied as Wiring pattern becomes through hole electrode 43 (2) and distribution 44 (2) by described later burning till.As required, such as, the undermost raw cook back side represented at Fig. 4 by print process, also coating electrically conductive slurry and form Wiring pattern.When carrying out applying to the raw cook back side, carry out after making to be coated on surperficial conductive paste drying.
The stacked multiple raw cooks defining the Wiring pattern of regulation also integrally burn till.Fig. 5 represents an example of temperature-time table when burning till.As shown in Figure 5, temperature-rise period from room temperature to 700 DEG C is set to air, the process of the temperature range of 700 DEG C ~ 900 DEG C (comprise 60 minutes with the retention time of 900 DEG C) is set in blanket of nitrogen, is again set to air from 700 DEG C to the temperature-fall period of room temperature.In addition, heating rate and rate of temperature fall are set to 5 DEG C/min.In addition, the temperature-time table burnt till is not limited to Fig. 5.In addition, the temperature range of 700 DEG C ~ 900 DEG C is set in blanket of nitrogen, and this is the oxidation in order to suppress the particle 4 in conductive paste.
(evaluation of multi-layered wiring board)
Carry out distribution 44 (2) visual examination around.In the interface portion of distribution 44 (2) and ceramic substrate 42 (3), do not find generation and the variable color in space.Multi-layered wiring board 41 (1) can be made with state good in appearance.Measure the resistivity of distribution 44 (2) and through hole electrode 43 (2), obtain the value of design as the same in the embodiment 2 with table 1.Then, the cross-section of the multi-layered wiring board 41 (1) made is carried out.Its result, the multi-layered wiring board 41 (1) of making is burnt till very densely.Therefore, think that resistivity also becomes the value as good design.This is presumably because that raw cook is in the temperature-rise period of 700 DEG C, the removal of adhesive terminates roughly completely.Also confirm that the glass powder of raw cook can not carry out chemical reaction with through hole electrode 43 (2) and distribution 44 (2), also can not produce space near interface each other.Above, confirmation can apply electrode wiring of the present invention 2 (with reference to Fig. 1) as the distribution 44 (2) of multi-layered wiring board 41 (1) and through hole electrode 43 (2).As distribution 44 (2) and through hole electrode 43 (2), do not need the electrode wiring of the silver thick film using high price, therefore, can contribute to the remarkable reduction of cost yet.
In embodiments, to electronic unit 1 be plasma display panel 11, the situation of solar cell device 31 and ceramic installation base plate 41 is illustrated, but electronic unit 1 is not limited to these parts, range of application can be expanded to the electronic unit of the electrode wiring can applying aluminium.
Symbol description
1 electronic unit
2 electrode wirings
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 (28)
1. electronic unit, it possesses electrode wiring, and described electrode wiring has: by aluminium (Al) and/or the multiple particle formed containing the alloy of aluminium and the oxide be fixed on while being directly coated to by described particle on substrate, it is characterized in that,
Described oxide contains phosphorus (P) and the aluminium of mixing;
Multiple described particle is made up of following particle group:
There is in the scope of particle diameter more than 0.5 μm and less than 1.5 μm the first particle group of the volume fraction of 95%; With
There is in the scope of particle diameter more than 1.5 μm and less than 8 μm the second particle group of the volume fraction of 95%;
The weight of described first particle group and described second particle group is roughly equal.
2. electronic unit as claimed in claim 1, it is characterized in that, described particle contains at least one element in silver (Ag), copper (Cu), silicon (Si), magnesium (Mg), calcium (Ca).
3. electronic unit as claimed in claim 1, it is characterized in that, in described electrode wiring, described particle is 84.2 more than volume % 99.7 volume below %.
4. electronic unit as claimed in claim 2, it is characterized in that, in described electrode wiring, described particle is 84.2 more than volume % 99.7 volume below %.
5. the electronic unit according to any one of Claims 1 to 4, is characterized in that, described particle contains platy particles.
6. the electronic unit according to any one of Claims 1 to 4, is characterized in that, described oxide is with phosphorus and oxygen (O) for principal component, and not consider the component ratio of described oxygen, the containing ratio of phosphorus is 50 more than atom %.
7. electronic unit as claimed in claim 5, is characterized in that, described oxide is with phosphorus and oxygen (O) for principal component, and not consider the component ratio of described oxygen, the containing ratio of phosphorus is 50 more than atom %.
8. the electronic unit according to any one of Claims 1 to 4, is characterized in that, multiple described particle is each other by sinter bonded.
9. electronic unit as claimed in claim 5, it is characterized in that, multiple described particle is each other by sinter bonded.
10. electronic unit as claimed in claim 6, it is characterized in that, multiple described particle is each other by sinter bonded.
11. electronic units as claimed in claim 7, it is characterized in that, multiple described particle is each other by sinter bonded.
12. conductive pastes, is characterized in that, have:
Phosphoric acid solution; And
Disperse in described phosphoric acid solution, and the multiple particles be made up of at least one element of argentiferous, copper, silicon, magnesium, calcium and the alloy of aluminium;
Multiple described particle is made up of following particle group:
There is in the scope of particle diameter more than 0.5 μm and less than 1.5 μm the first particle group of the volume fraction of 95%; With
There is in the scope of particle diameter more than 1.5 μm and less than 8 μm the second particle group of the volume fraction of 95%;
The weight of described first particle group and described second particle group is roughly equal.
13. electronic units, is characterized in that, possess on substrate, to apply conductive paste according to claim 12, carry out the electrode wiring that sinters,
Described electrode wiring has:
The multiple described particle be bonded to each other by sintering; And
Formed by described phosphoric acid solution and be adhered to the oxide of the phosphorus on substrate while being directly coated to by described particle.
14. electronic units according to any one of Claims 1 to 4, claim 7, claim 9 ~ 11 and claim 13, it is characterized in that, the resistivity of described electrode wiring is less than 5 × 10
-5Ω cm.
15. electronic units as claimed in claim 5, it is characterized in that, the resistivity of described electrode wiring is less than 5 × 10
-5Ω cm.
16. electronic units as claimed in claim 6, it is characterized in that, the resistivity of described electrode wiring is less than 5 × 10
-5Ω cm.
17. electronic units as claimed in claim 8, it is characterized in that, the resistivity of described electrode wiring is less than 5 × 10
-5Ω cm.
18. electronic units according to any one of Claims 1 to 4, claim 7, claim 9 ~ 11 and claim 13, it is characterized in that, the resistivity of described electrode wiring is less than 1 × 10
-5Ω cm.
19. electronic units as claimed in claim 5, it is characterized in that, the resistivity of described electrode wiring is less than 1 × 10
-5Ω cm.
20. electronic units as claimed in claim 6, it is characterized in that, the resistivity of described electrode wiring is less than 1 × 10
-5Ω cm.
21. electronic units as claimed in claim 8, it is characterized in that, the resistivity of described electrode wiring is less than 1 × 10
-5Ω cm.
22. electronic units according to any one of Claims 1 to 4, claim 7, claim 9 ~ 11, claim 13, claim 15 ~ 17 and claim 19 ~ 21, it is characterized in that, electronic unit be plasma display panel, solar cell device, ceramic installation base plate any one.
23. electronic units as claimed in claim 5, is characterized in that, electronic unit be plasma display panel, solar cell device, ceramic installation base plate any one.
24. electronic units as claimed in claim 6, is characterized in that, electronic unit be plasma display panel, solar cell device, ceramic installation base plate any one.
25. electronic units as claimed in claim 8, is characterized in that, electronic unit be plasma display panel, solar cell device, ceramic installation base plate any one.
26. electronic units as claimed in claim 14, is characterized in that, electronic unit be plasma display panel, solar cell device, ceramic installation base plate any one.
27. electronic units as claimed in claim 18, is characterized in that, electronic unit be plasma display panel, solar cell device, ceramic installation base plate any one.
The manufacture method of 28. electronic units, is characterized in that, coating electrically conductive slurry on substrate, and described conductive paste has the multiple particles be made up of at least one element of the argentiferous be dispersed in phosphoric acid solution, copper, silicon, magnesium, calcium and the alloy of aluminium,
The described conductive paste of coating is burnt till, forms electrode wiring;
Multiple described particle is made up of following particle group:
There is in the scope of particle diameter more than 0.5 μm and less than 1.5 μm the first particle group of the volume fraction of 95%; With
There is in the scope of particle diameter more than 1.5 μm and less than 8 μm the second particle group of the volume fraction of 95%;
The weight of described first particle group and described second particle group is roughly equal.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2010/053077 WO2011104859A1 (en) | 2010-02-26 | 2010-02-26 | Electronic component, conductive paste, and method for manufacturing electronic component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102754534A CN102754534A (en) | 2012-10-24 |
| CN102754534B true CN102754534B (en) | 2016-04-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080063260.3A Expired - Fee Related CN102754534B (en) | 2010-02-26 | 2010-02-26 | The manufacture method of electronic unit, conductive paste and electronic unit |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5480360B2 (en) |
| CN (1) | CN102754534B (en) |
| TW (1) | TWI407457B (en) |
| WO (1) | WO2011104859A1 (en) |
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| JP5646936B2 (en) * | 2010-09-29 | 2014-12-24 | 東洋アルミニウム株式会社 | Conductive aluminum filler, conductive paste composition containing the same, and conductive film formed using the conductive paste composition |
| CN103117130B (en) * | 2012-12-07 | 2016-08-31 | 蚌埠市智峰科技有限公司 | A kind of preparation method of the solar cell conductive mixed slurry containing plastic of poly vinyl acetate |
| CN103212763A (en) * | 2013-04-11 | 2013-07-24 | 中国电子科技集团公司第十四研究所 | LTCC (Low Temperature Co-fired Ceramic) device assembly welding method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2550630B2 (en) * | 1987-12-23 | 1996-11-06 | 株式会社村田製作所 | Copper paste for conductive film formation |
| JP3328004B2 (en) * | 1993-06-18 | 2002-09-24 | 富士通株式会社 | Flash fixing toner and electrophotographic apparatus |
| JP3656410B2 (en) * | 1998-06-18 | 2005-06-08 | 双葉電子工業株式会社 | Electrode structure and manufacturing method of fluorescent display tube with three-dimensional grid |
| JP4180734B2 (en) * | 1999-05-18 | 2008-11-12 | 太陽インキ製造株式会社 | PHOTOSENSITIVE PASTE COMPOSITION AND PANEL FORMED BY USING THE SAME PATTERN |
| JP3452034B2 (en) * | 2000-07-05 | 2003-09-29 | 株式会社村田製作所 | Conductive paste and multilayer ceramic electronic components |
| JP3523633B2 (en) * | 2001-11-13 | 2004-04-26 | Ｔｄｋ株式会社 | Ceramic capacitors |
| JP2008108716A (en) * | 2006-09-27 | 2008-05-08 | Kyoto Elex Kk | Conductive paste composition for low-temperature firing |
| JP2009087557A (en) * | 2007-09-27 | 2009-04-23 | Futaba Corp | Fluorescent display tube and conductive material paste for fluorescent display tube |
| JP2011034894A (en) * | 2009-08-05 | 2011-02-17 | Hitachi Chem Co Ltd | Cu-Al ALLOY POWDER, ALLOY PASTE USING IT, AND ELECTRONIC PARTS |
-
2010
- 2010-02-26 JP JP2012501588A patent/JP5480360B2/en not_active Expired - Fee Related
- 2010-02-26 WO PCT/JP2010/053077 patent/WO2011104859A1/en active Application Filing
- 2010-02-26 CN CN201080063260.3A patent/CN102754534B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011104859A1 (en) | 2013-06-17 |
| TWI407457B (en) | 2013-09-01 |
| WO2011104859A1 (en) | 2011-09-01 |
| JP5480360B2 (en) | 2014-04-23 |
| TW201212044A (en) | 2012-03-16 |
| CN102754534A (en) | 2012-10-24 |
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