US20140041912A1 - Method for manufacturing multilayer ceramic substrate and composite sheet - Google Patents
Method for manufacturing multilayer ceramic substrate and composite sheet Download PDFInfo
- Publication number
- US20140041912A1 US20140041912A1 US14/054,862 US201314054862A US2014041912A1 US 20140041912 A1 US20140041912 A1 US 20140041912A1 US 201314054862 A US201314054862 A US 201314054862A US 2014041912 A1 US2014041912 A1 US 2014041912A1
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- United States
- Prior art keywords
- ceramic green
- layer
- ceramic
- shrinkage
- green layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000000919 ceramic Substances 0.000 title claims abstract description 279
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000758 substrate Substances 0.000 title abstract description 63
- 238000004519 manufacturing process Methods 0.000 title description 18
- 239000004020 conductor Substances 0.000 claims abstract description 82
- 229910010293 ceramic material Inorganic materials 0.000 claims description 48
- 239000011230 binding agent Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 26
- 239000010410 layer Substances 0.000 description 248
- 239000002904 solvent Substances 0.000 description 37
- 239000003086 colorant Substances 0.000 description 18
- 238000010304 firing Methods 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
- 239000002002 slurry Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000009966 trimming Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000007606 doctor blade method Methods 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007729 constrained sintering Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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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
- H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
- H05K1/167—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed resistors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
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- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4614—Manufacturing multilayer circuits by laminating two or more circuit boards the electrical connections between the circuit boards being made during lamination
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- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
- H05K3/4629—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating inorganic sheets comprising printed circuits, e.g. green ceramic sheets
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/62—Forming laminates or joined articles comprising holes, channels or other types of openings
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/68—Forming laminates or joining articles wherein at least one substrate contains at least two different parts of macro-size, e.g. one ceramic substrate layer containing an embedded conductor or electrode
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
- C04B2237/702—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the constraining layers
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
- C04B2237/704—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/82—Two substrates not completely covering each other, e.g. two plates in a staggered position
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
- H01L2924/097—Glass-ceramics, e.g. devitrified glass
- H01L2924/09701—Low temperature co-fired ceramic [LTCC]
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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
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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
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
- H05K2203/013—Inkjet printing, e.g. for printing insulating material or resist
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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
- H05K2203/30—Details of processes not otherwise provided for in H05K2203/01 - H05K2203/17
- H05K2203/308—Sacrificial means, e.g. for temporarily filling a space for making a via or a cavity or for making rigid-flexible PCBs
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
Definitions
- the present invention relates to methods for manufacturing a multilayer ceramic substrate and to composite sheets.
- the present invention relates to a method for manufacturing a multilayer ceramic substrate in which a resistor pattern and/or conductor pattern is formed on the external surface of the multilayer ceramic substrate by an ink jet method, and to a composite sheet advantageously used in the manufacture of the multilayer ceramic substrate.
- a so-called constrained sintering process is a method for manufacturing a multilayer ceramic substrate relating to the present invention.
- a multilayer composite is prepared.
- the multilayer composite includes a plurality of ceramic green layers containing a low-temperature co-fired ceramic material and a shrinkage-retardant layer containing a sintering-resistant ceramic powder substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material.
- the shrinkage-retardant layer is disposed on at least one main surface of an unfired multilayer ceramic substrate including the plurality of ceramic green layers.
- the multilayer composite is subsequently fired under the condition for sintering the low-temperature co-fired ceramic material.
- a multilayer ceramic substrate is completed through sintering the ceramic green layers.
- the shrinkage-retardant layer is not shrunk by firing because the sintering-resistant ceramic powder contained in the shrinkage-retardant layer is not substantially sintered. Accordingly, the shrinkage-retardant layer restrains the ceramic green layers, so that the ceramic green layers shrink substantially only in the thickness direction, but are prevented from shrinking in the main surface direction. Consequently, the resulting multilayer ceramic substrate becomes difficult to deform non-uniformly, and the geometrical and dimensional precision of the multilayer ceramic substrate can be increased.
- the resistor pattern and/or conductor pattern may be formed after removing the shrinkage-retardant layer.
- a glass overcoat layer is additionally formed as a protective layer. The overcoat layer protects the resistor pattern from the influence of plating and ensures the reliability of the resistor pattern.
- firing steps are respectively performed. This means that the multilayer ceramic substrate undergoes repetition of firing steps, and the resulting multilayer ceramic substrate is brought into an excessively sintered state. Consequently, the mechanical strength and the electrical characteristics of the ceramic layers of the multilayer ceramic substrate may be varied, and the adhesion between the ceramic portion and the conductor portion may be reduced.
- the ceramic green layers and an unfired resistor pattern and overcoat layer are fired at one time in a state where the unfired resistor pattern and overcoat layer disposed on the outermost ceramic green layer of the multilayer composite are covered with a shrinkage-retardant layer.
- the ceramic green layer can avoid undergoing a plurality of firing steps.
- a process is proposed in which a resistor pattern and a conductor pattern are formed on the external surface of a ceramic substrate, such as the multilayer ceramic substrate, by an ink jet method.
- the ink jet method can not only efficiently conduct the steps of forming the resistor pattern and the conductor pattern, but also immediately cope with the alteration of the pattern.
- the resistor ink and conductor ink used for the ink jet method contain a solvent and have low viscosity. Such an ink is liable to spread out undesirably when it is applied onto a normal ceramic green layer.
- the resistor pattern and the conductor pattern cannot have high line fineness.
- the solvent in the resistor ink or the conductor ink may dissolve the binder contained in the ceramic green layer, thereby roughing the surfaces of the resistor pattern and the conductor pattern.
- preferred embodiments of the present invention provide a method for manufacturing a multilayer ceramic substrate through which the above problems can be solved.
- Additional preferred embodiments of the present invention provide a composite sheet that can be advantageously used in the method for manufacturing a multilayer ceramic substrate, and that includes a resistor pattern and/or conductor pattern.
- a method for manufacturing a multilayer ceramic substrate includes the steps of: preparing a first and a second low-temperature co-fired ceramic material, and a sintering-resistant ceramic powder that is substantially not sintered under a condition for sintering the first and the second low-temperature co-fired ceramic material; forming a composite sheet including a first ceramic green layer containing the first low-temperature co-fired ceramic material and a shrinkage-retardant layer containing a sintering-resistant ceramic powder; forming a resistor pattern and/or conductor pattern on the first ceramic green layer of the composite sheet by an ink jet method using a resistor ink and/or conductor ink; stacking a plurality of second ceramic green layers containing the second low-temperature co-fired ceramic material with the composite sheet having the resistor pattern and/or conductor pattern such that the shrinkage-retardant layer of the composite sheet defines an outermost layer, thus forming a multilayer composite including an unfire
- the resistor ink and/or conductor ink includes a solvent, and preferably, the first ceramic green layer can absorb the solvent to a greater extent than the second ceramic green layer.
- the first ceramic green layer has a voidage of about 30% or more, for example.
- the first ceramic green layer includes a binder, and preferably, the binder has a solubility of about 14 g or less, for example, in the resistor ink and/or conductor ink. There is no problem in practice as long as the solubility is about 14 g or less. More preferably, the solubility is about 4 g or less, and still more preferably about 2 g or less, for example.
- the first low-temperature co-fired ceramic material and the second low-temperature co-fired ceramic material are the same.
- the first low-temperature co-fired ceramic material is a glass-based low-temperature co-fired ceramic material.
- the first ceramic green layer has a different color from the shrinkage-retardant layer.
- the pattern-including composite sheet is obtained in the course of the above-described manufacturing method, and includes: a ceramic green layer containing a low-temperature co-fired ceramic material; a shrinkage-retardant layer disposed on the ceramic green layer and containing a sintering-resistant ceramic powder that is substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material; and a resistor pattern and/or conductor pattern formed on the ceramic green layer by an ink jet method using a resistor ink and/or conductor ink.
- the ceramic green layer preferably has a voidage of about 30% or more, for example, and the binder contained in the ceramic green layer preferably has a solubility of about 14 g or less, for example, in the resistor ink and/or conductor ink.
- a further preferred embodiment of the present invention is directed to a composite sheet advantageously used in the above method for manufacturing the multilayer ceramic substrate, and on which a resistor pattern and/or conductor pattern is to be formed.
- This composite sheet is obtained in the course of the above manufacturing method, and includes: a ceramic green layer containing a low-temperature co-fired ceramic material; and a shrinkage-retardant layer disposed on the ceramic green layer and containing a sintering-resistant ceramic powder that is substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material.
- the ceramic green layer has a higher voidage than the shrinkage-retardant layer.
- the composite sheet including the first ceramic green layer and the shrinkage-retardant layer is formed before forming the multilayer composite, which is a main portion of the multilayer ceramic substrate, including a plurality of second ceramic green layers.
- a resistor pattern and/or conductor pattern is formed on the composite sheet when it is in this state. Consequently, a large amount of the solvent contained in the resistor ink and/or conductor ink can be absorbed in the first ceramic green layer, and then in the shrinkage-retardant layer.
- the first ceramic green layer can more easily have a composition capable of rapidly absorbing the solvent than the second ceramic green layer.
- the resistor pattern and/or conductor pattern formed by an ink jet method can be prevented from undesirably spreading out, and the resistor pattern and/or conductor pattern can exhibit high line fineness.
- Any binder that is difficult to dissolve in the resistor ink and the conductor ink can be used as the binder contained in the first ceramic green layer substantially without limitation, and accordingly, it can be prevented that unevenness is formed at the surface of the resistor pattern and/or conductor pattern formed on the first ceramic green layer.
- the first ceramic green layer of the resulting multilayer ceramic substrate can serve as an overcoat layer protecting the resistor pattern and/or conductor pattern.
- the multilayer ceramic substrate including the resistor pattern and/or conductor pattern and the overcoat layer can be produced by firing only once. Thus, it can be prevented that the ceramic layers of the multilayer ceramic substrate are brought into an excessively sintered state, the characteristics of the ceramic layers are undesirably varied, and that the adhesion between the ceramic portion and the conductor portion is reduced.
- the first ceramic green layer having the above functions is handled in a state of composite sheet lined with the shrinkage-retardant layer. Therefore, the shrinkage-retardant layer can also absorb the solvent.
- the solvent content is high, a larger amount of the solvent can be absorbed more rapidly than in the case where only the first ceramic green layer absorbs the solvent. Consequently, the solvent remaining in the first ceramic green layer can be reduced. This contributes to achieving superior line fineness of the resistor pattern and/or conductor pattern, and contributes to forming a favorable surface.
- the solvent absorbed in the shrinkage-retardant layer is removed together with the shrinkage-retardant layer.
- the solvent remaining in the multilayer ceramic substrate can be reduced, and the influence of the solvent on the characteristics of the multilayer ceramic substrate can be reduced even more.
- the first ceramic green layer is generally thin and weak, the handling of the first ceramic green layer is not easy. By forming such a first ceramic green layer on the shrinkage-retardant layer, the first ceramic green layer can be handled easily. If the first ceramic green layer has a high voidage, in particular, the first ceramic green layer becomes brittle. It is effective that such a first ceramic green layer is reinforced by the shrinkage-retardant layer.
- the first ceramic green layer when the first ceramic green layer can absorb the solvent in the resistor ink and/or conductor ink to a greater extent than the second ceramic green layer, the above-described effects can be produced more reliably.
- the composition of the second ceramic green layer can be selected without particular limitation, and thus the flexibility of design can be enhanced. Since the second ceramic green layers defining the main portion of the multilayer ceramic substrate have a composition satisfying preferred characteristics for the multilayer ceramic substrate, the multilayer ceramic substrate can exhibit superior characteristics.
- the first ceramic green layer has a voidage of about 30% or more, for example, or the solubility of the binder contained in the first ceramic greens layer is about 14 g or less, for example, in the resistor ink and/or conductor ink, the line fineness of and the smoothness at the surface of the resistor pattern and/or conductor pattern can be enhanced reliably.
- the first low-temperature co-fired ceramic material and the second low-temperature co-fired ceramic material are the same as each other, the first ceramic green layer and the second ceramic green layers are shrunk substantially in the same manner when being fired. Accordingly, it is not easy to produce heterogeneous phases or sintering failure resulting from interdiffusion caused by the use of different materials. Consequently, the resulting multilayer ceramic substrate can exhibit stable characteristics and enhanced reliability.
- the first ceramic green layer has a different color from the shrinkage-retardant layer, a defect at a thin point of the ceramic green layer can easily be detected according to the difference in color, in a state of composite sheet.
- the ceramic green layer has a higher voidage than the shrinkage-retardant layer. Accordingly, the solvent of the ink in the ceramic green layer can be sucked to the shrinkage-retardant layer by capillary action. Thus, the solvent is not allowed to remain in the ceramic green layer.
- FIG. 1 is a representation of sectional views of representative steps of a method for manufacturing a multilayer ceramic substrate according to a first preferred embodiment of the present invention.
- FIG. 2 is a representation of sectional views of representative steps of a method for manufacturing a multilayer ceramic substrate according to a second preferred embodiment of the present invention.
- FIG. 1 illustrates a first preferred embodiment of the present invention.
- FIG. 1 shows sectional views of representative steps performed for manufacturing a multilayer ceramic substrate 1 shown in ( 5 ).
- the multilayer ceramic substrate 1 has a multilayer structure including a first ceramic layer 2 serving as an overcoat layer and a plurality of second ceramic layers 3 .
- a resistor pattern 4 and a conductor pattern 5 are formed at one surface in the stacking direction of the stack of the plurality of second ceramic layers 3 , and are covered with the first ceramic layer 2 .
- An external conductor pattern 6 is formed on the other surface in the stacking direction of the stack of the second ceramic layers 3 , and internal conductor patterns 7 are formed along the interfaces between the second ceramic layers 3 .
- via-conductors 8 are formed so as to pass through the second ceramic layers 3 in the thickness direction.
- a first and a second low-temperature co-fired ceramic material are prepared.
- the first low-temperature co-fired ceramic material and the second low-temperature co-fired ceramic material may be different from each other, the same material is preferably used in the present preferred embodiment.
- the low-temperature co-fired ceramic material refers to a ceramic material that can be sintered at about 1,050° C. or less, for example, and can be fired with a material having a low specific resistance, such as silver or copper.
- Examples of the low-temperature co-fired ceramic material include glass composite-based low-temperature co-fired ceramic materials prepared by mixing a borosilicate glass, such as SiO 2 —B 2 O 3 —CaO—Al 2 O 3 glass or SiO 2 —B 2 O 3 —CaO—Al 2 O 3 —R 20 glass (R: alkali metal), to a ceramic powder, such as alumina, zirconia, magnesia or forsterite; glass-based low-temperature co-fired ceramic materials containing ZnO—MgO—Al 2 O 3 —SiO 2 glass or borosilicate glass; and non-glass low-temperature co-fired ceramic materials containing BaO—Al 2 O 3 —SiO 2 ceramic powder or Al 2 O 3 —CaO—SiO 2 —MgO—B 2 O 3 ceramic powder, for example.
- a borosilicate glass such as SiO 2 —B 2 O 3 —Ca
- a sintering-resistant ceramic powder is prepared which is substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material, that is, at the sintering temperature of the low-temperature co-fired ceramic material.
- Alumina, zirconia, magnesia, forsterite or the like can be advantageously used as the sintering-resistant ceramic powder.
- FIG. 1 ( 1 A) a composite sheet 11 including a first ceramic green layer 2 a and a shrinkage-retardant layer 10 is formed.
- the first ceramic green layer 2 a is intended as the first ceramic layer 2 shown in FIG. 1 ( 5 ).
- a ceramic green sheet intended as the shrinkage-retardant layer 10 is formed.
- a ceramic slurry is prepared by mixing a solvent, an organic binder, a dispersant, a plasticizer and other additives to the sintering-resistant ceramic powder described above.
- the ceramic green sheet for the shrinkage-retardant layer can be formed by forming a sheet of the ceramic slurry on a carrier film (not shown), such as a PET film, by a doctor blade method.
- a ceramic slurry is prepared by adding an appropriate amount of each of solvent, organic binder, dispersant, plasticizer and so forth to the low-temperature co-fired ceramic material powder described above and mixing together.
- the first ceramic green layer 2 a is formed by forming a sheet of the ceramic slurry on the ceramic green sheet for the shrinkage-retardant layer by a doctor blade method or other suitable process.
- the first ceramic green layer 2 a may be prepared in a form of green sheet, and the green sheet may be stacked on the ceramic green sheet for the shrinkage-retardant layer and pressed to join together.
- the first ceramic green layer 2 a may also be formed on the ceramic green sheet for the shrinkage-retardant layer by, for example, screen printing.
- the first ceramic green layer 2 a contains the same low-temperature co-fired ceramic material as the second ceramic green layers 3 a described below, the first ceramic green layer 2 a and the second ceramic green layers 3 a are shrunk substantially in the same manner as each other when being fired. In addition, it becomes difficult to produce heterogeneous phases or sintering failure resulting from interdiffusion caused by the use of different materials. Consequently, the resulting multilayer ceramic substrate 1 can exhibit stable characteristics and enhanced reliability.
- the first low-temperature co-fired ceramic material is a glass based low-temperature co-fired ceramic material not containing a ceramic powder, it facilitates laser trimming and can increase the trimming speed.
- the low-temperature co-fired ceramic material contained in the second ceramic green layers 3 a may be the same as the glass-based low-temperature co-fired ceramic material of the first ceramic green layer 2 a , or may be glass composite-based low-temperature co-fired ceramic material or non-glass low-temperature co-fired ceramic material.
- a resistor pattern 4 is formed on the first ceramic green layer 2 a of the resulting composite sheet 11 by an ink jet method using a resistor ink, as shown in FIG. 1 ( 2 A).
- a conductor pattern 4 is formed on the first ceramic green layer 2 a of the resulting composite sheet 11 by an ink jet method using a conductor ink, as shown in FIG. 1 ( 3 A).
- the resistor pattern 4 can be formed uniformly, so that the variation in resistance can be reduced.
- the reliability in joining the resistor pattern 4 and the conductor pattern 5 can be enhanced.
- the solvent in the resistor ink of the resistor pattern 4 and the solvent in the conductor ink of the conductor pattern 5 are immediately absorbed into the first ceramic green layer 2 a , and the residual solvents, not absorbed in the first ceramic green layer 2 a , is then absorbed into the shrinkage-retardant layer 10 .
- the resistor pattern 4 and the conductor pattern 5 are prevented from undesirably spreading out, and their surfaces become smooth.
- the first ceramic green layer 2 a absorb the solvent to a greater extent than the below-described second ceramic green layer 3 a .
- the first ceramic green layer 2 a preferably has a voidage of about 30% or more, for example.
- the upper limit of the voidage is about 60%, for example.
- the binder content is reduced. If the binder content is excessively low, however, the inorganic components of the ink can penetrate the first ceramic green layer 2 a to cause a short circuit or a defect in characteristics.
- a first ceramic green layer having a voidage of about 60% or less, for example, can prevent these problems.
- the solubilities of the binder contained in the first ceramic green layer 2 a in the resistor ink and the conductor ink are 14 g or less.
- the solubility mentioned herein refers to the weight (unit: g) of solute dissolved in 100 g of solvent.
- the solubility of the binder also depends on the solvent of the ink.
- a butyral binder polyvinyl butyral resin having a butyralization degree of about 60 mol % or more and having about 30 mol % or more of hydroxy group can be used to obtain a solubility of about 14 g or less, particularly of about 2 g or less, for example.
- the solubilities of the binders contained in the shrinkage-retardant layer 10 and the second ceramic green layer 3 a are each higher than the maximum solubility of about 14 g of the binder contained in the first ceramic green layer 2 a.
- the solubility of the binder of the shrinkage-retardant layer 10 When the solubility of the binder of the shrinkage-retardant layer 10 is higher, the solvent of the ink penetrating the shrinkage-retardant layer 10 is mixed with the binder to reduce the flowability, and consequently the ink is prevented from flowing back to the first ceramic green layer 2 a .
- the solubility of the binder in the second ceramic green layer 3 a is higher, the solvents slightly remaining in the resistor pattern 4 and the conductor pattern 5 formed on the first ceramic green layer 2 a are mixed with the binder of the second ceramic green layer 3 a when stacking sheets, and consequently the adhesion between the resistor pattern 4 and conductor pattern 5 and the second ceramic green layer 3 a is increased.
- the solubilities of the shrinkage-retardant layer 10 and second ceramic green layers 3 a having larger thicknesses than the first ceramic green layer 2 a be higher than about 14 g, for example.
- a binder having a low solubility may easily be changed into a higher molecular weight compound or may increase the intermolecular force, and accordingly debinding becomes difficult.
- the first ceramic green layer 2 a has a thickness in the range of about 5 ⁇ m to about 50 ⁇ m, for example, before firing.
- a first ceramic green layer having a thickness of about 5 ⁇ m or more, for example, can sufficiently absorb the solvent of the ink.
- a first ceramic green layer 2 a having a thickness of about 50 ⁇ m, for example, or less can ensure superior printability, and if the laser trimming of the resistor pattern 4 is required, it can be performed in a short time with high precision. If the resistor pattern is not formed, or if the resistor pattern does not require laser trimming, disadvantages in increasing the thickness of the first ceramic green layer 2 a are few, and accordingly it is not a problem even if the thickness may be more than about 50 ⁇ m. More preferably, the first ceramic green layer 2 a has a thickness of about 5 ⁇ m to about 35 ⁇ m, for example.
- the shrinkage-retardant layer 10 has a thickness of about 50 ⁇ m to about 300 ⁇ m, for example, before firing.
- a shrinkage-retardant layer 10 having a thickness of about 50 ⁇ m or more, for example, can further absorb the solvent of the ink absorbed by the first ceramic green layer 2 a and can sufficiently prevent the shrinkage.
- the shrinkage-retardant layer 10 has a voidage in the range of about 10% to about 50%, for example.
- the shrinkage-retardant layer 10 preferably has a voidage of about 10% or more, for example. It is however preferable that the upper limit of the voidage be about 50%, for example, from the viewpoint of sufficiently preventing the shrinkage.
- the voidage of the shrinkage-retardant layer 10 is preferably lower than that of the first ceramic green layer 2 a .
- the solvent of the ink in the first ceramic green layer 2 a can be sucked to the shrinkage-retardant layer 10 by capillary action.
- the solvent cannot be allowed to remain in the first ceramic green layer 2 a.
- ceramic green sheets are prepared for the second ceramic green layers 3 a .
- the second ceramic green layers 3 a are intended as the second ceramic layers 3 shown in FIG. 1 ( 5 ).
- a ceramic slurry is prepared by adding an appropriate amount of each of solvent, organic binder, dispersant, plasticizer and so forth to the above described low-temperature co-fired ceramic material powder and mixing together.
- the ceramic green sheet for the second ceramic green layer 3 a is formed by forming a sheet of the ceramic slurry by a doctor blade method or other suitable process.
- through-holes 12 in which via-conductors 8 are to be provided are formed in the ceramic green sheets for the second ceramic green layers 3 a , as shown in FIG. 1 ( 1 B).
- the through-holes 12 are filled with an electroconductive paste to form via-conductors 8 , as shown in FIG. 1 ( 2 B).
- an electroconductive paste is printed on each ceramic green sheet for the second ceramic green layers 3 a by, for example, screen printing, thus forming an internal conductor pattern 7 , as shown in FIG. 1 ( 3 B).
- the external conductor pattern 6 is also formed in the same manner, but not shown in FIG. 1 ( 3 B).
- the electroconductive paste forming the via-conductor 8 , the internal conductor patterns 7 and the external conductor pattern 6 contains a conductive component essentially composed of preferably a low-melting-point metal, such as silver, copper or gold.
- the multilayer composite includes an unfired multilayer ceramic substrate 1 a and at least one shrinkage-retardant layer 10 disposed on a main surface of the multilayer ceramic substrate 1 a , and, in the present preferred embodiment, other shrinkage-retardant layers 10 is provided on the main surface opposite to the main surface on which the shrinkage-retardant layer 10 of the composite sheet 11 is disposed.
- the second ceramic green layers 3 a are preferably prepared in a form of ceramic green sheets, as described above, the sheets are not necessarily ceramic green sheets capable of being solely handled, and may be layers that are formed by application of a ceramic slurry and act as the second ceramic green layers 3 a as they are.
- the composite sheet 11 and the second ceramic green layers 3 a shown in FIG. 1 ( 4 ) are illustrated in such a manner that the composite sheet 11 shown in FIGS. 1 ( 1 A) to 1 ( 3 A) and the second ceramic green sheets 3 a shown in FIGS. 1 ( 1 B) to 1 ( 3 B) are turned upside down.
- the unfired multilayer composite 13 shown in FIG. 1 ( 4 ) is fired under a condition for sintering the low-temperature co-fired ceramic material, for example, at a temperature of about 800° C. to about 1000° C.
- the shrinkage-retardant layer 10 does not substantially shrink in this firing step, and restrains the unfired multilayer ceramic substrate 1 a so as not to shrink in the main surface direction.
- the shrinkage of the first and second ceramic green layers 2 a and 3 a of the unfired multilayer ceramic substrate 1 a is retarded in the main surface direction respectively, and while the low-temperature co-fired ceramic material contained in the unfired multilayer ceramic substrate is sintered and shrinks substantially only in the thickness direction, the first and second ceramic layers 2 and 3 are formed in the sintered multilayer ceramic substrate 1 .
- the resistor pattern 4 , the conductor pattern 5 , the external conductor pattern 6 , the internal conductor pattern 7 and the via-conductor 8 are sintered through the above firing step.
- the shrinkage-retardant layer 10 is removed by, for example, ultrasonic cleaning. Since the shrinkage-retardant layer 10 is not sintered in the firing step and is in a porous state, it can be removed easily.
- the first ceramic green layer 2 a and the shrinkage-retardant layer 10 are different in color to the extent that their colors are distinguished. Consequently, defects (including pin holes) caused at thin points in the first ceramic green layer 2 a of the composite sheet 11 can be easily detected according to the difference in color.
- the first ceramic green layer 2 a is as thin as about 5 ⁇ m to about 50 ⁇ m, particularly about 5 ⁇ m to about 35 ⁇ m, for example, as described above, it is difficult to form the first ceramic green layer uniformly without defects. For example, if the first ceramic green layer 2 a and the shrinkage-retardant layer 10 are given different colors by, for example, coloring either the first ceramic green layer 2 a or the shrinkage-retardant layer 10 , defects caused by reducing the thickness of the first ceramic green layer 2 a can easily be detected.
- the first ceramic green layer 2 a turns to the first ceramic layer 2 finally in the resulting multilayer ceramic substrate 1 obtained by firing, and the first ceramic layer 2 serves as an overcoat layer protecting the resistor pattern 4 being the surface layer of the multilayer ceramic substrate 1 from the influence of plating and ensuring the reliability of the resistor pattern 4 . If a defect is produced at a thin point in the overcoat layer, the overcoat layer cannot exhibit sufficient resistance to plating or ensure the reliability of the resistor pattern 4 .
- compositions form a white first ceramic green layer 2 a and shrinkage-retardant layer 10 . Even if a thin point is produced in the first ceramic green layer 2 a , therefore, it is difficult to find the thin point. On the other hand, if the first ceramic green layer 2 a and the shrinkage-retardant layer 10 have different colors, the color of the underlying shrinkage-retardant layer 10 can be easily observed at the region corresponding to the thin point of the first ceramic green layer 2 a . By coloring the first ceramic green layer 2 a or the shrinkage-retardant layer 10 , a distinct contrast occurs between the colors at the thin point and its surroundings, and thus the thin point can easily be detected.
- the difference in color between the first ceramic green layer 2 a and the shrinkage-retardant layer 10 makes clear the boundary between the first ceramic green layer 2 a and the shrinkage-retardant layer 10 when a section of the composite is observed in the stacking direction. Consequently, the thickness of the first ceramic green layer 2 a serving as an overcoat layer can easily be measured. This means that the thickness can be easily fed back and thus easily be controlled.
- an inorganic coloring agent may be added, or an organic coloring agent may be added.
- a commercially available inorganic pigment can be used as the inorganic coloring agent. Examples of such an inorganic coloring agent include oxide powders, such as of chromium, cobalt, copper, nickel, iron and titanium, for example.
- the organic coloring agent may be a commercially available organic pigment, such as azo or quinacridone pigment (or dye), for example.
- the inorganic coloring agent remains even after firing, the organic coloring agent disappears with the binder component by firing. Accordingly, the use of an inorganic coloring agent is advantageous in distinguishing between the first ceramic layer 2 and the shrinkage-retardant layer 10 in the multilayer ceramic substrate 1 after firing. In the use of an organic coloring agent, on the other hand, the difference in color is substantially not left between the first ceramic layer 2 and the shrinkage-retardant layer 10 in the multilayer ceramic substrate 1 after firing.
- an inorganic coloring agent be used, and is preferable that the inorganic coloring agent be added to the first ceramic green layer 2 a .
- the inorganic coloring agent may negatively affect the sintering properties or the like of the first ceramic green layer 2 a and other layers of the unfired multilayer composite 13 .
- its content is preferably 3 parts by weight or less relative to 100 parts by weight of the low-temperature co-fired ceramic material in the first ceramic green layer 2 a , for example.
- an organic coloring agent it is preferable, but not particularly limited to, that its content be 0.1 to 1.5 parts by weight relative to 100 parts by weight of the low-temperature co-fired ceramic material in the first ceramic green layer 2 a , for example.
- FIG. 2 is a representation illustrating a second preferred embodiment of the present invention, corresponding to FIG. 1 .
- the elements in FIG. 2 corresponding to the elements shown in FIG. 1 are designated by the same reference numerals, and the same descriptions will be omitted.
- the conductor pattern 5 preferably is first formed on the first ceramic green layer 2 a of the composite sheet 11 by an ink jet method, and subsequently the resistor pattern 4 is formed by an ink jet method, as shown in FIGS. 2 ( 2 A) and 2 ( 3 A).
- the other structure is the same as in the above-described first preferred embodiment.
- the composite sheet 11 having the resistor pattern 4 and the conductor pattern 5 is disposed only on one main surface of the multilayer composite 13 , the composite sheet 11 may be disposed on both main surfaces.
- the first ceramic layer 2 serving as an overcoat layer is formed so as to cover the entire main surface of the multilayer ceramic substrate 1 in the above preferred embodiments, it may be formed so as to expose part of, for example, the conductor pattern 5 .
- the first ceramic green layer 2 a may be formed so as to have an opening for partially exposing the conductor pattern 5 , or the opening may be formed by irradiating the first ceramic layer 2 with laser light after firing the first ceramic green layer 2 a formed over the entire main surface.
- resistor pattern 4 and the conductor pattern 5 are provided in the above preferred embodiments, the present invention can be applied to the case where either of them is provided.
- shrinkage-retardant layer 10 is disposed along both main surfaces of the unfired multilayer ceramic substrate 1 a , it may be disposed along only one of the main surfaces.
- a ceramic slurry was prepared by mixing 7 parts by weight of butyral resin, 2 parts by weight of phthalate-abased plasticizer, 20 parts by weight of ethanol, and 33 parts by weight of toluene to 100 parts by weight of Al 2 O 3 powder.
- the ceramic green sheet for the shrinkage-retardant layer 10 was formed by forming a sheet of the ceramic slurry to a thickness of 200 ⁇ m.
- a ceramic slurry was prepared by mixing a binder resin having a solubility in the ink solvent shown in Table 1 to a low-temperature co-fired ceramic material containing 55% by weight of SiO 2 —CaO—Al 2 O 3 —B 2 O 3 glass powder and 45% by weight of Al 2 O 3 powder, and then further mixing the resin mixture, toluene and ethanol in such proportions as the first ceramic green layer 2 a would have a voidage shown in Table 1.
- the first ceramic green layer 2 a was formed by forming a sheet of the ceramic slurry to a thickness of 30 ⁇ m on the ceramic green sheet for the shrinkage-retardant layer 10 .
- a resistor ink used for forming the resistor pattern 4 by an ink jet method was prepared by mixing 20% by weight of ruthenium dioxide powder and 80% by weight of glass powder, and further adding and mixing predetermined amounts each of ethyl cellulose-based resin and butyl Carbitol acetate as vehicle components to the mixture.
- a conductor ink used for forming the conductor pattern 5 by an ink jet method was prepared by mixing a predetermined amount of each of ethyl cellulose-based resin and butyl Carbitol acetate as vehicle components to silver powder.
- a ceramic slurry was prepared by adding acrylic resin, toluene and ethanol to a low-temperature co-fired ceramic material containing 55% by weight of SiO 2 —CaO—Al 2 O 3 —B 2 O 3 glass powder and 45% by weight of Al 2 O 3 powder.
- Ceramic green sheets for the second ceramic green layers 3 a were formed by forming sheets of the ceramic slurry to a thickness of 200 ⁇ m.
- An electroconductive paste for forming the external conductor pattern 6 , the internal conductor pattern 7 and the via-conductor 8 was prepared by adding a predetermined amount of each of ethyl cellulose-based resin and terpineol as vehicle components to a mixture containing silver powder and Al 2 O 3 powder in a weight ratio of 100:1.
- Samples 11 and 12 are comparative examples, which were formed such that the resistor pattern 4 and the conductor pattern 5 were formed on a single sheet defined by only the first ceramic green layer 2 a without using the shrinkage-retardant layer 10 .
- Sample 10 is an example of the present invention, the solubility of the binder contained in the first ceramic green layer 2 a was outside the preferred range and over 14 g.
- the resistor pattern 4 and the conductor pattern 5 at the surface of each resulting multilayer ceramic substrate of the examples were evaluated by observing the surface state and the line fineness through a microscope. The evaluation results are shown in Table 1.
- the line fineness in Table 1 is expressed by an index of the average width of actually printed lines with respect to the intended width defined as 100. When the line fineness is 115 or less, it is determined to be good; when it is more than 115 and 135 or less, it is determined to be nearly good; and when it is more than 135, the conductor pattern undesirably spreads out to cause a short circuit, or the resistor pattern undesirably spreads out to deviate the resistance from the intended value extensively.
- Samples 1 to 10 shown in Table 1 are within the scope of the present invention. Samples 1 to 10, particularly Samples 1 to 4, satisfy both the preferred condition that the binder solubility is about 2 g or less and the preferred condition that voidage is about 30% or more, and result in favorable surface states and line fineness.
- Samples 5, 7, 8 and 9 exhibited binder solubilities of more than about 2 g, but the solubilities were still as low as about 14 g or less. Accordingly, they have no problem in practice though the surface states were “Fair”. Samples 6, 7 and 9 of the Samples 6, 7, 8 and 9 exhibited voidages of less than 30%; hence, their line fineness was inferior to that of Sample 8 having a voidage of about 30% or more.
- Sample 10 exhibited a binder solubility of more than 14 g. Accordingly, the surface state was determined to be bad, but the line fineness was good because of the voidage of about 30% or more.
- Samples 11 and 12 of comparative examples do not have the shrinkage-retardant layer 10 . Accordingly, only the first ceramic green layer 2 a having a thickness of about 30 ⁇ m absorbs the ink solvent, but cannot absorb it sufficiently. Consequently, the surface state was determined to be bad and the line fineness was inferior even though the binder solubility and the voidage are within the preferred ranges.
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Abstract
A high-quality resistor pattern and conductor pattern is formed on an external surface of a multilayer ceramic substrate by an ink jet method. A composite sheet including a first ceramic green layer and a shrinkage-retardant layer is formed, and a resistor pattern and a conductor pattern are formed on the first ceramic green layer of the composite sheet by an ink jet method. Subsequently, a plurality of second ceramic green layers are stacked with the composite sheet such that the shrinkage-retardant layer of the composite sheet defines an outermost layer, thus forming a multilayer composite including an unfired multilayer ceramic substrate and the shrinkage-retardant layer. Then, the multilayer composite is fired, and the shrinkage-retardant layer is removed to obtain a sintered multilayer ceramic substrate.
Description
- 1. Field of the Invention
- The present invention relates to methods for manufacturing a multilayer ceramic substrate and to composite sheets. In particular, the present invention relates to a method for manufacturing a multilayer ceramic substrate in which a resistor pattern and/or conductor pattern is formed on the external surface of the multilayer ceramic substrate by an ink jet method, and to a composite sheet advantageously used in the manufacture of the multilayer ceramic substrate.
- 2. Description of the Related Art
- A so-called constrained sintering process is a method for manufacturing a multilayer ceramic substrate relating to the present invention. For manufacturing a multilayer ceramic substrate by a constrained sintering process, a multilayer composite is prepared. The multilayer composite includes a plurality of ceramic green layers containing a low-temperature co-fired ceramic material and a shrinkage-retardant layer containing a sintering-resistant ceramic powder substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material. The shrinkage-retardant layer is disposed on at least one main surface of an unfired multilayer ceramic substrate including the plurality of ceramic green layers.
- The multilayer composite is subsequently fired under the condition for sintering the low-temperature co-fired ceramic material. Thus, a multilayer ceramic substrate is completed through sintering the ceramic green layers. The shrinkage-retardant layer is not shrunk by firing because the sintering-resistant ceramic powder contained in the shrinkage-retardant layer is not substantially sintered. Accordingly, the shrinkage-retardant layer restrains the ceramic green layers, so that the ceramic green layers shrink substantially only in the thickness direction, but are prevented from shrinking in the main surface direction. Consequently, the resulting multilayer ceramic substrate becomes difficult to deform non-uniformly, and the geometrical and dimensional precision of the multilayer ceramic substrate can be increased.
- Subsequently, the shrinkage-retardant layer is removed, and thus a desired multilayer ceramic substrate is obtained.
- If a resistor pattern and/or conductor pattern is provided on the external surface of the multilayer ceramic substrate, the resistor pattern and/or conductor pattern may be formed after removing the shrinkage-retardant layer. If the resistor pattern is provided, in general, a glass overcoat layer is additionally formed as a protective layer. The overcoat layer protects the resistor pattern from the influence of plating and ensures the reliability of the resistor pattern. For forming the resistor pattern and/or conductor pattern and the overcoat layer, firing steps are respectively performed. This means that the multilayer ceramic substrate undergoes repetition of firing steps, and the resulting multilayer ceramic substrate is brought into an excessively sintered state. Consequently, the mechanical strength and the electrical characteristics of the ceramic layers of the multilayer ceramic substrate may be varied, and the adhesion between the ceramic portion and the conductor portion may be reduced.
- Accordingly, a process can be proposed in which the ceramic green layers and an unfired resistor pattern and overcoat layer are fired at one time in a state where the unfired resistor pattern and overcoat layer disposed on the outermost ceramic green layer of the multilayer composite are covered with a shrinkage-retardant layer. Thus, the ceramic green layer can avoid undergoing a plurality of firing steps.
- In this process, however, when the shrinkage-retardant layer is removed, the shrinkage-retardant layer and the resistor pattern may be disadvantageously removed together, because the adhesion of the resistor pattern to the multilayer ceramic substrate is relatively low. Japanese Unexamined Patent Application Publication No. 2005-39164 proposes that the glass component contained in the overcoat layer is improved in softening point and composition to overcome the above disadvantage.
- As another approach, a process is proposed in which a resistor pattern and a conductor pattern are formed on the external surface of a ceramic substrate, such as the multilayer ceramic substrate, by an ink jet method. The ink jet method can not only efficiently conduct the steps of forming the resistor pattern and the conductor pattern, but also immediately cope with the alteration of the pattern.
- Unfortunately, the resistor ink and conductor ink used for the ink jet method contain a solvent and have low viscosity. Such an ink is liable to spread out undesirably when it is applied onto a normal ceramic green layer.
- Accordingly, the resistor pattern and the conductor pattern cannot have high line fineness.
- In addition, the solvent in the resistor ink or the conductor ink may dissolve the binder contained in the ceramic green layer, thereby roughing the surfaces of the resistor pattern and the conductor pattern.
- In view of the above, preferred embodiments of the present invention provide a method for manufacturing a multilayer ceramic substrate through which the above problems can be solved.
- Additional preferred embodiments of the present invention provide a composite sheet that can be advantageously used in the method for manufacturing a multilayer ceramic substrate, and that includes a resistor pattern and/or conductor pattern.
- Further preferred embodiments of the present invention provide a composite sheet which can be advantageously used in the method for manufacturing a multilayer ceramic substrate, and onto which a resistor pattern and/or conductor pattern is to be formed.
- A method for manufacturing a multilayer ceramic substrate according to a preferred embodiment of the present invention includes the steps of: preparing a first and a second low-temperature co-fired ceramic material, and a sintering-resistant ceramic powder that is substantially not sintered under a condition for sintering the first and the second low-temperature co-fired ceramic material; forming a composite sheet including a first ceramic green layer containing the first low-temperature co-fired ceramic material and a shrinkage-retardant layer containing a sintering-resistant ceramic powder; forming a resistor pattern and/or conductor pattern on the first ceramic green layer of the composite sheet by an ink jet method using a resistor ink and/or conductor ink; stacking a plurality of second ceramic green layers containing the second low-temperature co-fired ceramic material with the composite sheet having the resistor pattern and/or conductor pattern such that the shrinkage-retardant layer of the composite sheet defines an outermost layer, thus forming a multilayer composite including an unfired multilayer ceramic substrate and the shrinkage-retardant layer disposed at least one main surface of the unfired multilayer ceramic substrate; firing the multilayer composite under the condition for sintering the first and the second low-temperature co-fired ceramic material, thereby producing a sintered multilayer ceramic substrate; and then removing the shrinkage-retardant layer to obtain the multilayer ceramic substrate.
- The resistor ink and/or conductor ink includes a solvent, and preferably, the first ceramic green layer can absorb the solvent to a greater extent than the second ceramic green layer.
- Preferably, the first ceramic green layer has a voidage of about 30% or more, for example.
- The first ceramic green layer includes a binder, and preferably, the binder has a solubility of about 14 g or less, for example, in the resistor ink and/or conductor ink. There is no problem in practice as long as the solubility is about 14 g or less. More preferably, the solubility is about 4 g or less, and still more preferably about 2 g or less, for example.
- Preferably, the first low-temperature co-fired ceramic material and the second low-temperature co-fired ceramic material are the same.
- Preferably, the first low-temperature co-fired ceramic material is a glass-based low-temperature co-fired ceramic material.
- Preferably, the first ceramic green layer has a different color from the shrinkage-retardant layer.
- Another preferred embodiment of the present invention is directed to a pattern-including composite sheet advantageously used in the method for manufacturing the multilayer ceramic substrate. The pattern-including composite sheet is obtained in the course of the above-described manufacturing method, and includes: a ceramic green layer containing a low-temperature co-fired ceramic material; a shrinkage-retardant layer disposed on the ceramic green layer and containing a sintering-resistant ceramic powder that is substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material; and a resistor pattern and/or conductor pattern formed on the ceramic green layer by an ink jet method using a resistor ink and/or conductor ink.
- In the pattern-including composite sheet as well, the ceramic green layer preferably has a voidage of about 30% or more, for example, and the binder contained in the ceramic green layer preferably has a solubility of about 14 g or less, for example, in the resistor ink and/or conductor ink.
- A further preferred embodiment of the present invention is directed to a composite sheet advantageously used in the above method for manufacturing the multilayer ceramic substrate, and on which a resistor pattern and/or conductor pattern is to be formed. This composite sheet is obtained in the course of the above manufacturing method, and includes: a ceramic green layer containing a low-temperature co-fired ceramic material; and a shrinkage-retardant layer disposed on the ceramic green layer and containing a sintering-resistant ceramic powder that is substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material. The ceramic green layer has a higher voidage than the shrinkage-retardant layer.
- In various preferred embodiments of the present invention, the composite sheet including the first ceramic green layer and the shrinkage-retardant layer is formed before forming the multilayer composite, which is a main portion of the multilayer ceramic substrate, including a plurality of second ceramic green layers. A resistor pattern and/or conductor pattern is formed on the composite sheet when it is in this state. Consequently, a large amount of the solvent contained in the resistor ink and/or conductor ink can be absorbed in the first ceramic green layer, and then in the shrinkage-retardant layer. Also, the first ceramic green layer can more easily have a composition capable of rapidly absorbing the solvent than the second ceramic green layer.
- Thus, the resistor pattern and/or conductor pattern formed by an ink jet method can be prevented from undesirably spreading out, and the resistor pattern and/or conductor pattern can exhibit high line fineness. Any binder that is difficult to dissolve in the resistor ink and the conductor ink can be used as the binder contained in the first ceramic green layer substantially without limitation, and accordingly, it can be prevented that unevenness is formed at the surface of the resistor pattern and/or conductor pattern formed on the first ceramic green layer.
- The first ceramic green layer of the resulting multilayer ceramic substrate can serve as an overcoat layer protecting the resistor pattern and/or conductor pattern. The multilayer ceramic substrate including the resistor pattern and/or conductor pattern and the overcoat layer can be produced by firing only once. Thus, it can be prevented that the ceramic layers of the multilayer ceramic substrate are brought into an excessively sintered state, the characteristics of the ceramic layers are undesirably varied, and that the adhesion between the ceramic portion and the conductor portion is reduced.
- The first ceramic green layer having the above functions is handled in a state of composite sheet lined with the shrinkage-retardant layer. Therefore, the shrinkage-retardant layer can also absorb the solvent. When the solvent content is high, a larger amount of the solvent can be absorbed more rapidly than in the case where only the first ceramic green layer absorbs the solvent. Consequently, the solvent remaining in the first ceramic green layer can be reduced. This contributes to achieving superior line fineness of the resistor pattern and/or conductor pattern, and contributes to forming a favorable surface. In particular, the solvent absorbed in the shrinkage-retardant layer is removed together with the shrinkage-retardant layer. Thus, the solvent remaining in the multilayer ceramic substrate can be reduced, and the influence of the solvent on the characteristics of the multilayer ceramic substrate can be reduced even more.
- Since the first ceramic green layer is generally thin and weak, the handling of the first ceramic green layer is not easy. By forming such a first ceramic green layer on the shrinkage-retardant layer, the first ceramic green layer can be handled easily. If the first ceramic green layer has a high voidage, in particular, the first ceramic green layer becomes brittle. It is effective that such a first ceramic green layer is reinforced by the shrinkage-retardant layer.
- In various preferred embodiments of the present invention, when the first ceramic green layer can absorb the solvent in the resistor ink and/or conductor ink to a greater extent than the second ceramic green layer, the above-described effects can be produced more reliably. By using a composition capable of sufficiently absorbing the solvent for only the first ceramic green layer, the composition of the second ceramic green layer can be selected without particular limitation, and thus the flexibility of design can be enhanced. Since the second ceramic green layers defining the main portion of the multilayer ceramic substrate have a composition satisfying preferred characteristics for the multilayer ceramic substrate, the multilayer ceramic substrate can exhibit superior characteristics.
- If the first ceramic green layer has a voidage of about 30% or more, for example, or the solubility of the binder contained in the first ceramic greens layer is about 14 g or less, for example, in the resistor ink and/or conductor ink, the line fineness of and the smoothness at the surface of the resistor pattern and/or conductor pattern can be enhanced reliably.
- If the first low-temperature co-fired ceramic material and the second low-temperature co-fired ceramic material are the same as each other, the first ceramic green layer and the second ceramic green layers are shrunk substantially in the same manner when being fired. Accordingly, it is not easy to produce heterogeneous phases or sintering failure resulting from interdiffusion caused by the use of different materials. Consequently, the resulting multilayer ceramic substrate can exhibit stable characteristics and enhanced reliability.
- If the first ceramic green layer has a different color from the shrinkage-retardant layer, a defect at a thin point of the ceramic green layer can easily be detected according to the difference in color, in a state of composite sheet.
- In the composite sheet of a preferred embodiment of the present invention, the ceramic green layer has a higher voidage than the shrinkage-retardant layer. Accordingly, the solvent of the ink in the ceramic green layer can be sucked to the shrinkage-retardant layer by capillary action. Thus, the solvent is not allowed to remain in the ceramic green layer.
- Other features, elements, steps, characteristics and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the present invention with reference to the attached drawings.
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FIG. 1 is a representation of sectional views of representative steps of a method for manufacturing a multilayer ceramic substrate according to a first preferred embodiment of the present invention. -
FIG. 2 is a representation of sectional views of representative steps of a method for manufacturing a multilayer ceramic substrate according to a second preferred embodiment of the present invention. -
FIG. 1 illustrates a first preferred embodiment of the present invention.FIG. 1 shows sectional views of representative steps performed for manufacturing a multilayerceramic substrate 1 shown in (5). - Referring to
FIG. 1 (5), the multilayerceramic substrate 1 has a multilayer structure including a firstceramic layer 2 serving as an overcoat layer and a plurality of secondceramic layers 3. - A
resistor pattern 4 and aconductor pattern 5 are formed at one surface in the stacking direction of the stack of the plurality of secondceramic layers 3, and are covered with the firstceramic layer 2. Anexternal conductor pattern 6 is formed on the other surface in the stacking direction of the stack of the secondceramic layers 3, andinternal conductor patterns 7 are formed along the interfaces between the secondceramic layers 3. Furthermore, via-conductors 8 are formed so as to pass through the secondceramic layers 3 in the thickness direction. - For manufacturing such a multilayer
ceramic substrate 1, the following process is performed. - First, a first and a second low-temperature co-fired ceramic material are prepared. Although the first low-temperature co-fired ceramic material and the second low-temperature co-fired ceramic material may be different from each other, the same material is preferably used in the present preferred embodiment. The low-temperature co-fired ceramic material refers to a ceramic material that can be sintered at about 1,050° C. or less, for example, and can be fired with a material having a low specific resistance, such as silver or copper.
- Examples of the low-temperature co-fired ceramic material include glass composite-based low-temperature co-fired ceramic materials prepared by mixing a borosilicate glass, such as SiO2—B2O3—CaO—Al2O3 glass or SiO2—B2O3—CaO—Al2O3—R20 glass (R: alkali metal), to a ceramic powder, such as alumina, zirconia, magnesia or forsterite; glass-based low-temperature co-fired ceramic materials containing ZnO—MgO—Al2O3—SiO2 glass or borosilicate glass; and non-glass low-temperature co-fired ceramic materials containing BaO—Al2O3—SiO2 ceramic powder or Al2O3—CaO—SiO2—MgO—B2O3 ceramic powder, for example.
- In addition, a sintering-resistant ceramic powder is prepared which is substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material, that is, at the sintering temperature of the low-temperature co-fired ceramic material. Alumina, zirconia, magnesia, forsterite or the like can be advantageously used as the sintering-resistant ceramic powder.
- Turning now to
FIG. 1 (1A), acomposite sheet 11 including a first ceramicgreen layer 2 a and a shrinkage-retardant layer 10 is formed. The first ceramicgreen layer 2 a is intended as the firstceramic layer 2 shown inFIG. 1 (5). - For forming the
composite sheet 11, first, a ceramic green sheet intended as the shrinkage-retardant layer 10 is formed. A ceramic slurry is prepared by mixing a solvent, an organic binder, a dispersant, a plasticizer and other additives to the sintering-resistant ceramic powder described above. The ceramic green sheet for the shrinkage-retardant layer can be formed by forming a sheet of the ceramic slurry on a carrier film (not shown), such as a PET film, by a doctor blade method. - A ceramic slurry is prepared by adding an appropriate amount of each of solvent, organic binder, dispersant, plasticizer and so forth to the low-temperature co-fired ceramic material powder described above and mixing together. The first ceramic
green layer 2 a is formed by forming a sheet of the ceramic slurry on the ceramic green sheet for the shrinkage-retardant layer by a doctor blade method or other suitable process. - Alternatively, the first ceramic
green layer 2 a may be prepared in a form of green sheet, and the green sheet may be stacked on the ceramic green sheet for the shrinkage-retardant layer and pressed to join together. The first ceramicgreen layer 2 a may also be formed on the ceramic green sheet for the shrinkage-retardant layer by, for example, screen printing. - If the first ceramic
green layer 2 a contains the same low-temperature co-fired ceramic material as the second ceramicgreen layers 3 a described below, the first ceramicgreen layer 2 a and the second ceramicgreen layers 3 a are shrunk substantially in the same manner as each other when being fired. In addition, it becomes difficult to produce heterogeneous phases or sintering failure resulting from interdiffusion caused by the use of different materials. Consequently, the resulting multilayerceramic substrate 1 can exhibit stable characteristics and enhanced reliability. - When the first low-temperature co-fired ceramic material is a glass based low-temperature co-fired ceramic material not containing a ceramic powder, it facilitates laser trimming and can increase the trimming speed. In this instance, the low-temperature co-fired ceramic material contained in the second ceramic
green layers 3 a may be the same as the glass-based low-temperature co-fired ceramic material of the first ceramicgreen layer 2 a, or may be glass composite-based low-temperature co-fired ceramic material or non-glass low-temperature co-fired ceramic material. - Subsequently, a
resistor pattern 4 is formed on the first ceramicgreen layer 2 a of the resultingcomposite sheet 11 by an ink jet method using a resistor ink, as shown inFIG. 1 (2A). - Then, a
conductor pattern 4 is formed on the first ceramicgreen layer 2 a of the resultingcomposite sheet 11 by an ink jet method using a conductor ink, as shown inFIG. 1 (3A). By forming theresistor pattern 4 before theconductor pattern 5, as in the present preferred embodiment, theresistor pattern 4 can be formed uniformly, so that the variation in resistance can be reduced. In addition, the reliability in joining theresistor pattern 4 and theconductor pattern 5 can be enhanced. - In the states shown in
FIGS. 1 (2A) and 1 (3A), the solvent in the resistor ink of theresistor pattern 4 and the solvent in the conductor ink of theconductor pattern 5 are immediately absorbed into the first ceramicgreen layer 2 a, and the residual solvents, not absorbed in the first ceramicgreen layer 2 a, is then absorbed into the shrinkage-retardant layer 10. Thus, theresistor pattern 4 and theconductor pattern 5 are prevented from undesirably spreading out, and their surfaces become smooth. - In order to ensure this effect, it is preferable that the first ceramic
green layer 2 a absorb the solvent to a greater extent than the below-described second ceramicgreen layer 3 a. In order to ensure the above effect more, the first ceramicgreen layer 2 a preferably has a voidage of about 30% or more, for example. Preferably, the upper limit of the voidage is about 60%, for example. In order to increase the voidage, the binder content is reduced. If the binder content is excessively low, however, the inorganic components of the ink can penetrate the first ceramicgreen layer 2 a to cause a short circuit or a defect in characteristics. A first ceramic green layer having a voidage of about 60% or less, for example, can prevent these problems. - In order to further ensure the above effect, preferably, the solubilities of the binder contained in the first ceramic
green layer 2 a in the resistor ink and the conductor ink are 14 g or less. The solubility mentioned herein refers to the weight (unit: g) of solute dissolved in 100 g of solvent. The solubility of the binder also depends on the solvent of the ink. For example, if BCA (butyl Carbitol acetate) is used as the ink solvent, a butyral binder (polyvinyl butyral resin) having a butyralization degree of about 60 mol % or more and having about 30 mol % or more of hydroxy group can be used to obtain a solubility of about 14 g or less, particularly of about 2 g or less, for example. - The solubilities of the binders contained in the shrinkage-
retardant layer 10 and the second ceramicgreen layer 3 a are each higher than the maximum solubility of about 14 g of the binder contained in the first ceramicgreen layer 2 a. - When the solubility of the binder of the shrinkage-
retardant layer 10 is higher, the solvent of the ink penetrating the shrinkage-retardant layer 10 is mixed with the binder to reduce the flowability, and consequently the ink is prevented from flowing back to the first ceramicgreen layer 2 a. In addition, when the solubility of the binder in the second ceramicgreen layer 3 a is higher, the solvents slightly remaining in theresistor pattern 4 and theconductor pattern 5 formed on the first ceramicgreen layer 2 a are mixed with the binder of the second ceramicgreen layer 3 a when stacking sheets, and consequently the adhesion between theresistor pattern 4 andconductor pattern 5 and the second ceramicgreen layer 3 a is increased. - From the viewpoint of enhancing the debinding properties, it is preferable that the solubilities of the shrinkage-
retardant layer 10 and second ceramicgreen layers 3 a having larger thicknesses than the first ceramicgreen layer 2 a be higher than about 14 g, for example. A binder having a low solubility may easily be changed into a higher molecular weight compound or may increase the intermolecular force, and accordingly debinding becomes difficult. - Preferably, the first ceramic
green layer 2 a has a thickness in the range of about 5 μm to about 50 μm, for example, before firing. A first ceramic green layer having a thickness of about 5 μm or more, for example, can sufficiently absorb the solvent of the ink. A first ceramicgreen layer 2 a having a thickness of about 50 μm, for example, or less can ensure superior printability, and if the laser trimming of theresistor pattern 4 is required, it can be performed in a short time with high precision. If the resistor pattern is not formed, or if the resistor pattern does not require laser trimming, disadvantages in increasing the thickness of the first ceramicgreen layer 2 a are few, and accordingly it is not a problem even if the thickness may be more than about 50 μm. More preferably, the first ceramicgreen layer 2 a has a thickness of about 5 μm to about 35 μm, for example. - Preferably, the shrinkage-
retardant layer 10 has a thickness of about 50 μm to about 300 μm, for example, before firing. A shrinkage-retardant layer 10 having a thickness of about 50 μm or more, for example, can further absorb the solvent of the ink absorbed by the first ceramicgreen layer 2 a and can sufficiently prevent the shrinkage. Also, a shrinkage-retardant layer having a thickness of about 300 μm or less, for example, is easy to form and has superior debinding properties. If the solvent content in the ink is low, the thickness of the shrinkage-retardant layer may be less than about 50 μm, for example. - Preferably, the shrinkage-
retardant layer 10 has a voidage in the range of about 10% to about 50%, for example. From the viewpoint of helping the first ceramicgreen layer 2 a absorb the solvent of the ink, the shrinkage-retardant layer 10 preferably has a voidage of about 10% or more, for example. It is however preferable that the upper limit of the voidage be about 50%, for example, from the viewpoint of sufficiently preventing the shrinkage. - The voidage of the shrinkage-
retardant layer 10 is preferably lower than that of the first ceramicgreen layer 2 a. In this instance, the solvent of the ink in the first ceramicgreen layer 2 a can be sucked to the shrinkage-retardant layer 10 by capillary action. Thus, the solvent cannot be allowed to remain in the first ceramicgreen layer 2 a. - Turning now to
FIG. 1 (1B), ceramic green sheets are prepared for the second ceramicgreen layers 3 a. The second ceramicgreen layers 3 a are intended as the secondceramic layers 3 shown inFIG. 1 (5). A ceramic slurry is prepared by adding an appropriate amount of each of solvent, organic binder, dispersant, plasticizer and so forth to the above described low-temperature co-fired ceramic material powder and mixing together. The ceramic green sheet for the second ceramicgreen layer 3 a is formed by forming a sheet of the ceramic slurry by a doctor blade method or other suitable process. - Then, through-
holes 12 in which via-conductors 8 are to be provided are formed in the ceramic green sheets for the second ceramicgreen layers 3 a, as shown inFIG. 1 (1B). - The through-
holes 12 are filled with an electroconductive paste to form via-conductors 8, as shown inFIG. 1 (2B). - Then, an electroconductive paste is printed on each ceramic green sheet for the second ceramic
green layers 3 a by, for example, screen printing, thus forming aninternal conductor pattern 7, as shown inFIG. 1 (3B). Theexternal conductor pattern 6 is also formed in the same manner, but not shown inFIG. 1 (3B). - The electroconductive paste forming the via-
conductor 8, theinternal conductor patterns 7 and theexternal conductor pattern 6 contains a conductive component essentially composed of preferably a low-melting-point metal, such as silver, copper or gold. - Turning now to
FIG. 1 (4), the ceramic green sheets for the second ceramicgreen layers 3 a are stacked with thecomposite sheet 11 having theresistor pattern 4 and theconductor pattern 5 such that the shrinkage-retardant layer 10 of thecomposite sheet 11 defines the outermost layer, and thus amultilayer composite 13 is completed. The multilayer composite includes an unfired multilayerceramic substrate 1 a and at least one shrinkage-retardant layer 10 disposed on a main surface of the multilayerceramic substrate 1 a, and, in the present preferred embodiment, other shrinkage-retardant layers 10 is provided on the main surface opposite to the main surface on which the shrinkage-retardant layer 10 of thecomposite sheet 11 is disposed. - Although the second ceramic
green layers 3 a are preferably prepared in a form of ceramic green sheets, as described above, the sheets are not necessarily ceramic green sheets capable of being solely handled, and may be layers that are formed by application of a ceramic slurry and act as the second ceramicgreen layers 3 a as they are. - The
composite sheet 11 and the second ceramicgreen layers 3 a shown inFIG. 1 (4) are illustrated in such a manner that thecomposite sheet 11 shown inFIGS. 1 (1A) to 1 (3A) and the second ceramicgreen sheets 3 a shown inFIGS. 1 (1B) to 1 (3B) are turned upside down. - Subsequently, the
unfired multilayer composite 13 shown inFIG. 1 (4) is fired under a condition for sintering the low-temperature co-fired ceramic material, for example, at a temperature of about 800° C. to about 1000° C. The shrinkage-retardant layer 10 does not substantially shrink in this firing step, and restrains the unfired multilayerceramic substrate 1 a so as not to shrink in the main surface direction. While the shrinkage of the first and second ceramicgreen layers ceramic substrate 1 a is retarded in the main surface direction respectively, and while the low-temperature co-fired ceramic material contained in the unfired multilayer ceramic substrate is sintered and shrinks substantially only in the thickness direction, the first and secondceramic layers ceramic substrate 1. - The
resistor pattern 4, theconductor pattern 5, theexternal conductor pattern 6, theinternal conductor pattern 7 and the via-conductor 8 are sintered through the above firing step. - Subsequently, the shrinkage-
retardant layer 10 is removed by, for example, ultrasonic cleaning. Since the shrinkage-retardant layer 10 is not sintered in the firing step and is in a porous state, it can be removed easily. - Thus, the multilayer
ceramic substrate 1 as shown inFIG. 1 (5) is completed. - Preferably, the first ceramic
green layer 2 a and the shrinkage-retardant layer 10 are different in color to the extent that their colors are distinguished. Consequently, defects (including pin holes) caused at thin points in the first ceramicgreen layer 2 a of thecomposite sheet 11 can be easily detected according to the difference in color. - Since the first ceramic
green layer 2 a is as thin as about 5 μm to about 50 μm, particularly about 5 μm to about 35 μm, for example, as described above, it is difficult to form the first ceramic green layer uniformly without defects. For example, if the first ceramicgreen layer 2 a and the shrinkage-retardant layer 10 are given different colors by, for example, coloring either the first ceramicgreen layer 2 a or the shrinkage-retardant layer 10, defects caused by reducing the thickness of the first ceramicgreen layer 2 a can easily be detected. - More specifically, the first ceramic
green layer 2 a turns to the firstceramic layer 2 finally in the resulting multilayerceramic substrate 1 obtained by firing, and the firstceramic layer 2 serves as an overcoat layer protecting theresistor pattern 4 being the surface layer of the multilayerceramic substrate 1 from the influence of plating and ensuring the reliability of theresistor pattern 4. If a defect is produced at a thin point in the overcoat layer, the overcoat layer cannot exhibit sufficient resistance to plating or ensure the reliability of theresistor pattern 4. - The above-described compositions form a white first ceramic
green layer 2 a and shrinkage-retardant layer 10. Even if a thin point is produced in the first ceramicgreen layer 2 a, therefore, it is difficult to find the thin point. On the other hand, if the first ceramicgreen layer 2 a and the shrinkage-retardant layer 10 have different colors, the color of the underlying shrinkage-retardant layer 10 can be easily observed at the region corresponding to the thin point of the first ceramicgreen layer 2 a. By coloring the first ceramicgreen layer 2 a or the shrinkage-retardant layer 10, a distinct contrast occurs between the colors at the thin point and its surroundings, and thus the thin point can easily be detected. - The difference in color between the first ceramic
green layer 2 a and the shrinkage-retardant layer 10 makes clear the boundary between the first ceramicgreen layer 2 a and the shrinkage-retardant layer 10 when a section of the composite is observed in the stacking direction. Consequently, the thickness of the first ceramicgreen layer 2 a serving as an overcoat layer can easily be measured. This means that the thickness can be easily fed back and thus easily be controlled. - In order to vary the color, an inorganic coloring agent may be added, or an organic coloring agent may be added. A commercially available inorganic pigment can be used as the inorganic coloring agent. Examples of such an inorganic coloring agent include oxide powders, such as of chromium, cobalt, copper, nickel, iron and titanium, for example. The organic coloring agent may be a commercially available organic pigment, such as azo or quinacridone pigment (or dye), for example.
- While the inorganic coloring agent remains even after firing, the organic coloring agent disappears with the binder component by firing. Accordingly, the use of an inorganic coloring agent is advantageous in distinguishing between the first
ceramic layer 2 and the shrinkage-retardant layer 10 in the multilayerceramic substrate 1 after firing. In the use of an organic coloring agent, on the other hand, the difference in color is substantially not left between the firstceramic layer 2 and the shrinkage-retardant layer 10 in the multilayerceramic substrate 1 after firing. - Accordingly, it is particularly preferable that an inorganic coloring agent be used, and is preferable that the inorganic coloring agent be added to the first ceramic
green layer 2 a. However, the inorganic coloring agent may negatively affect the sintering properties or the like of the first ceramicgreen layer 2 a and other layers of theunfired multilayer composite 13. For the use of an inorganic coloring agent, its content is preferably 3 parts by weight or less relative to 100 parts by weight of the low-temperature co-fired ceramic material in the first ceramicgreen layer 2 a, for example. If an organic coloring agent is used, it is preferable, but not particularly limited to, that its content be 0.1 to 1.5 parts by weight relative to 100 parts by weight of the low-temperature co-fired ceramic material in the first ceramicgreen layer 2 a, for example. -
FIG. 2 is a representation illustrating a second preferred embodiment of the present invention, corresponding toFIG. 1 . The elements inFIG. 2 corresponding to the elements shown inFIG. 1 are designated by the same reference numerals, and the same descriptions will be omitted. - In the second preferred embodiment, the
conductor pattern 5 preferably is first formed on the first ceramicgreen layer 2 a of thecomposite sheet 11 by an ink jet method, and subsequently theresistor pattern 4 is formed by an ink jet method, as shown inFIGS. 2 (2A) and 2 (3A). The other structure is the same as in the above-described first preferred embodiment. - While the present invention has been described with reference to exemplary preferred embodiments, it is to be understood that various modifications may be made without departing from the scope of the invention.
- Although in the preferred embodiments shown in the drawings, the
composite sheet 11 having theresistor pattern 4 and theconductor pattern 5 is disposed only on one main surface of themultilayer composite 13, thecomposite sheet 11 may be disposed on both main surfaces. - Although the first
ceramic layer 2 serving as an overcoat layer is formed so as to cover the entire main surface of the multilayerceramic substrate 1 in the above preferred embodiments, it may be formed so as to expose part of, for example, theconductor pattern 5. For forming the firstceramic layer 2 so as to expose part of theconductor pattern 5, the first ceramicgreen layer 2 a may be formed so as to have an opening for partially exposing theconductor pattern 5, or the opening may be formed by irradiating the firstceramic layer 2 with laser light after firing the first ceramicgreen layer 2 a formed over the entire main surface. - While both the
resistor pattern 4 and theconductor pattern 5 are provided in the above preferred embodiments, the present invention can be applied to the case where either of them is provided. - While the shrinkage-
retardant layer 10 is disposed along both main surfaces of the unfired multilayerceramic substrate 1 a, it may be disposed along only one of the main surfaces. - To confirm that the present invention is effective, the following experimental examples were conducted. In the experimental examples, a multilayer
ceramic substrate 1 was produced according to the process shown inFIG. 1 . - A ceramic slurry was prepared by mixing 7 parts by weight of butyral resin, 2 parts by weight of phthalate-abased plasticizer, 20 parts by weight of ethanol, and 33 parts by weight of toluene to 100 parts by weight of Al2O3 powder. The ceramic green sheet for the shrinkage-
retardant layer 10 was formed by forming a sheet of the ceramic slurry to a thickness of 200 μm. - A ceramic slurry was prepared by mixing a binder resin having a solubility in the ink solvent shown in Table 1 to a low-temperature co-fired ceramic material containing 55% by weight of SiO2—CaO—Al2O3—B2O3 glass powder and 45% by weight of Al2O3 powder, and then further mixing the resin mixture, toluene and ethanol in such proportions as the first ceramic
green layer 2 a would have a voidage shown in Table 1. The first ceramicgreen layer 2 a was formed by forming a sheet of the ceramic slurry to a thickness of 30 μm on the ceramic green sheet for the shrinkage-retardant layer 10. - A resistor ink used for forming the
resistor pattern 4 by an ink jet method was prepared by mixing 20% by weight of ruthenium dioxide powder and 80% by weight of glass powder, and further adding and mixing predetermined amounts each of ethyl cellulose-based resin and butyl Carbitol acetate as vehicle components to the mixture. - A conductor ink used for forming the
conductor pattern 5 by an ink jet method was prepared by mixing a predetermined amount of each of ethyl cellulose-based resin and butyl Carbitol acetate as vehicle components to silver powder. - A ceramic slurry was prepared by adding acrylic resin, toluene and ethanol to a low-temperature co-fired ceramic material containing 55% by weight of SiO2—CaO—Al2O3—B2O3 glass powder and 45% by weight of Al2O3 powder. Ceramic green sheets for the second ceramic
green layers 3 a were formed by forming sheets of the ceramic slurry to a thickness of 200 μm. - An electroconductive paste for forming the
external conductor pattern 6, theinternal conductor pattern 7 and the via-conductor 8 was prepared by adding a predetermined amount of each of ethyl cellulose-based resin and terpineol as vehicle components to a mixture containing silver powder and Al2O3 powder in a weight ratio of 100:1. - In Table 1,
Samples resistor pattern 4 and theconductor pattern 5 were formed on a single sheet defined by only the first ceramicgreen layer 2 a without using the shrinkage-retardant layer 10. AlthoughSample 10 is an example of the present invention, the solubility of the binder contained in the first ceramicgreen layer 2 a was outside the preferred range and over 14 g. - The
resistor pattern 4 and theconductor pattern 5 at the surface of each resulting multilayer ceramic substrate of the examples were evaluated by observing the surface state and the line fineness through a microscope. The evaluation results are shown in Table 1. -
TABLE 1 Binder Voidage Surface Line Sample No. solubility (g) (%) state fineness 1 0.16 44 Good 108 2 0.71 44 Good 108 3 2 44 Good 110 4 0.71 30 Good 111 5 3.77 42 Fair 113 6 0.16 25 Good 128 7 3.77 25 Fair 131 8 8.80 42 Fair 114 9 13.51 25 Fair 133 10 15.42 40 Bad 115 11 (Comparative 0.16 44 Bad 137 Example) 12 ( Comparative 2 30 Bad 140 Example) - In the column of the surface state in Table 1, “Good” represents that the resistor pattern and the conductor pattern had superior surfaces without unevenness; “Fair” represents that the surfaces of the patterns were slightly uneven to such an extent as not to affect the electric characteristics; and “Bad” represents that a pinhole or a crack occurred in the surface.
- The line fineness in Table 1 is expressed by an index of the average width of actually printed lines with respect to the intended width defined as 100. When the line fineness is 115 or less, it is determined to be good; when it is more than 115 and 135 or less, it is determined to be nearly good; and when it is more than 135, the conductor pattern undesirably spreads out to cause a short circuit, or the resistor pattern undesirably spreads out to deviate the resistance from the intended value extensively.
-
Samples 1 to 10 shown in Table 1 are within the scope of the present invention.Samples 1 to 10, particularlySamples 1 to 4, satisfy both the preferred condition that the binder solubility is about 2 g or less and the preferred condition that voidage is about 30% or more, and result in favorable surface states and line fineness. -
Samples Samples Samples Sample 8 having a voidage of about 30% or more. -
Sample 10 exhibited a binder solubility of more than 14 g. Accordingly, the surface state was determined to be bad, but the line fineness was good because of the voidage of about 30% or more. -
Samples retardant layer 10. Accordingly, only the first ceramicgreen layer 2 a having a thickness of about 30 μm absorbs the ink solvent, but cannot absorb it sufficiently. Consequently, the surface state was determined to be bad and the line fineness was inferior even though the binder solubility and the voidage are within the preferred ranges. - Although the results are not shown in Table 1, the
resistor pattern 4 and theconductor pattern 5 formed only on a second ceramicgreen layer 3 a or only on the shrinkage-retardant layer 10 were evaluated. The solubilities of both binders ere 14 g or more and the voidages were lower than about 30%. Thus the results were not good. - While preferred embodiments of the present invention have been described above, it is to be understood that variations and modifications will be apparent to those skilled in the art without departing the scope and spirit of the present invention. The scope of the present invention, therefore, is to be determined solely by the following claims.
Claims (5)
1. A pattern-including composite sheet comprising:
a ceramic green layer including a low-temperature co-fired ceramic material;
a shrinkage-retardant layer disposed on the ceramic green layer and containing a sintering-resistant ceramic powder that is substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material; and
a resistor pattern and/or conductor pattern formed on the ceramic green layer by an ink jet method using a resistor ink and/or a conductor ink.
2. The pattern-including composite sheet according to claim 1 , wherein the ceramic green layer has a voidage of about 30% or more.
3. The pattern-including composite sheet according to claim 1 , wherein the ceramic green layer contains a binder, and the binder has a solubility of about 14 g or less in the resistor ink and/or the conductor ink.
4. The pattern-including composite sheet according to claim 1, wherein the ceramic green layer has a different color than that of the shrinkage-retardant layer.
5. A composite sheet comprising:
a ceramic green layer containing a low-temperature co-fired ceramic material; and
a shrinkage-retardant layer disposed on the ceramic green layer and containing a sintering-resistant ceramic powder that is substantially not sintered under a condition for sintering the low-temperature co-fired ceramic material; wherein
the ceramic green layer has a higher voidage than the shrinkage-retardant layer.
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US14/054,862 US20140041912A1 (en) | 2008-03-28 | 2013-10-16 | Method for manufacturing multilayer ceramic substrate and composite sheet |
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PCT/JP2009/052847 WO2009119199A1 (en) | 2008-03-28 | 2009-02-19 | Method for producing multilayer ceramic substrate and composite sheet |
US12/621,642 US8585842B2 (en) | 2008-03-28 | 2009-11-19 | Method for manufacturing multilayer ceramic substrate and composite sheet |
US14/054,862 US20140041912A1 (en) | 2008-03-28 | 2013-10-16 | Method for manufacturing multilayer ceramic substrate and composite sheet |
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US14/054,862 Abandoned US20140041912A1 (en) | 2008-03-28 | 2013-10-16 | Method for manufacturing multilayer ceramic substrate and composite sheet |
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EP (1) | EP2131637B1 (en) |
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CN115119394A (en) * | 2016-01-13 | 2022-09-27 | 株式会社村田制作所 | Laminate and electronic component |
US10347553B2 (en) * | 2016-02-01 | 2019-07-09 | Mitsubishi Electric Corporation | Ceramic substrate and method for manufacturing the same |
WO2018016386A1 (en) * | 2016-07-21 | 2018-01-25 | Tdk株式会社 | Method for manufacturing stacked-type electronic component |
CN106550548B (en) * | 2016-10-31 | 2019-03-15 | 中国科学院理化技术研究所 | Laser printing forming method of flexible circuit |
CN114133217A (en) * | 2021-12-06 | 2022-03-04 | 中国振华集团云科电子有限公司 | Preparation method of LTCC ceramic heater for electronic cigarette |
US20230380077A1 (en) * | 2022-05-20 | 2023-11-23 | Kyocera International, Inc. | Multi-layer ceramic package having a multilayer ceramic base and at least one inkjet printed layer |
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JP4702481B2 (en) | 2011-06-15 |
US8585842B2 (en) | 2013-11-19 |
EP2131637A1 (en) | 2009-12-09 |
JPWO2009119199A1 (en) | 2011-07-21 |
US20100059252A1 (en) | 2010-03-11 |
EP2131637B1 (en) | 2012-10-31 |
EP2131637A4 (en) | 2010-08-25 |
CN101683011A (en) | 2010-03-24 |
CN101683011B (en) | 2013-01-09 |
WO2009119199A1 (en) | 2009-10-01 |
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