CN112624786B - Method for manufacturing composite substrate - Google Patents

Method for manufacturing composite substrate Download PDF

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CN112624786B
CN112624786B CN201910906376.1A CN201910906376A CN112624786B CN 112624786 B CN112624786 B CN 112624786B CN 201910906376 A CN201910906376 A CN 201910906376A CN 112624786 B CN112624786 B CN 112624786B
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copper foil
oxide film
copper
ceramic substrate
film layer
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CN112624786A (en
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曾继立
李茂昌
萧明阳
叶自立
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GIA TZOONG ENTERPRISE Co Ltd
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GIA TZOONG ENTERPRISE Co Ltd
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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
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/021—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles in a direct manner, e.g. direct copper bonding [DCB]
    • 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
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/343—Alumina or aluminates
    • 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
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C04B2237/366—Aluminium nitride
    • 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
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C04B2237/368—Silicon nitride
    • 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
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/407—Copper
    • 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
    • C04B2237/54—Oxidising the surface before joining

Abstract

The invention discloses a manufacturing method of a composite substrate. The method for manufacturing the composite substrate by bonding the copper foil and the ceramic substrate through eutectic reaction comprises the steps of cleaning the surface of the copper foil to remove oil stains or dirt on the surface; then treating the surface of the copper foil by using a liquid medicine with the pH value of less than 3, etching and roughening the surface of the copper foil by using the liquid medicine, and forming a copper oxide film layer of an organic metal compound with a macadam-shaped microstructure on the surface of the copper foil; and then the copper foil is heated to the eutectic temperature, so that the copper foil and the copper oxide film on the surface of the copper foil generate eutectic reaction, and the copper foil and the ceramic substrate are bonded.

Description

Method for manufacturing composite substrate
Technical Field
The invention relates to a method for manufacturing a composite substrate, in particular to a method for manufacturing a composite substrate by bonding a copper foil and a ceramic substrate through eutectic reaction.
Background
The method of forming a composite substrate by Copper foil and ceramic is Direct Copper Bonding (DCB, Direct Copper Bonding or DBC, Direct Bonding bonder), and earlier, a dry process was used, in which the Copper foil was placed in a vacuum furnace to form Copper oxide on the lower surface of the Copper foil in an oxygen atmosphere, and then the Copper foil with the Copper oxide layer was bonded to the surface of a ceramic substrate with an oxide surface layer
Figure BDA0002213391200000011
And performing eutectic sintering in a vacuum furnace at the temperature, wherein the copper foil is directly bonded to the surface of the ceramic substrate, copper oxide is formed on both sides of the copper foil, and the eutectic bonding of one side of the copper foil and the ceramic substrate is not facilitated. Furthermore, there are also related manufacturers that use alkaline solution to grow black fluff composed of copper oxide and cuprous oxide on the surface of copper foil, so that the copper foil can form a copper oxide layer on one side, but the following disadvantages exist:
1. because the copper oxide film layer is directly grown from the surface of the copper foil, the roughness of the surface of the copper foil is insufficient, and the surface of the copper foil needs to be roughened before the copper oxide film layer is manufactured, so that the binding force during eutectic reaction is increased, and the manufacturing process is complicated.
2. The black fluff of the copper oxide film layer grows at a low speed and is easy to break and fall off, the bonding force during eutectic reaction is greatly reduced except for the increase of the preparation time, and the copper foil is placed in the air, so that the copper oxide film layer continuously grows to cause the difficulty in controlling the thickness of the copper oxide film layer.
3. The waste water produced by the alkaline liquid medicine is not environment-friendly, and the treatment cost of the waste water is high.
4. Many fine gaps are formed in the copper oxide film layer, and during eutectic sintering, gas in the gaps cannot be discharged due to poor flow capacity of a eutectic liquid phase, so that many air gaps are mixed between the copper foil and the ceramic after the composite substrate is manufactured, and besides the heat conduction capacity is reduced, the bonding strength is also reduced.
Therefore, how to solve the problems and deficiencies of the prior art mentioned above is a problem that the related art needs to be researched and developed.
Disclosure of Invention
The invention mainly aims to treat the surface of a copper foil by using a liquid medicine with the pH value of less than 3, roughens the surface of the copper foil and generates a copper oxide film layer of an organic metal compound with a stone-like microstructure, improves the binding force between the copper foil and a ceramic substrate, is easy to control the thickness of the copper oxide film layer, can reduce the cost and increase the production speed.
The secondary objective of the present invention is to form a gas escape space in the copper oxide film layer formed on the surface of the copper foil by using the shielding region disposed on the surface of the copper foil, so that when the single surface of the copper foil is bonded with the ceramic substrate in an eutectic manner, the flow capacity of the eutectic liquid phase is increased, the number of air gaps between the copper foil and the ceramic substrate during the manufacturing of the composite substrate is reduced, and the heat conduction capacity and the bonding strength of the composite substrate are greatly improved.
In order to achieve the above purpose, the manufacturing method of the composite substrate of the invention is implemented by cleaning the surface of the copper foil to remove oil stains or dirt on the surface; then treating the surface of the copper foil by using liquid medicine with the pH value of less than 3, etching and roughening the surface of the copper foil by using the liquid medicine, and forming a copper oxide film layer of organic metal compound with a stone-like microstructure on the surface of the copper foil; and then the copper foil is heated to the eutectic temperature, so that the copper foil and the copper oxide film on the surface of the copper foil generate eutectic reaction, and the copper foil and the ceramic substrate are bonded.
In the method for manufacturing the composite substrate, the chemical liquid at least contains 2 to 20 weight percent of hydrogen peroxide, 2 to 20 weight percent of sulfuric acid and 0.5 to 5 weight percent of accelerator of a nitrogen-containing heterocyclic compound, and the accelerator is used for enhancing the bonding force of the copper oxide film layer.
In the method for manufacturing a composite substrate, the accelerator contains alkyl, phenyl, amino, or hydroxyl.
In the manufacturing method of the composite substrate, the ceramic substrate is an aluminum nitride ceramic substrate, an aluminum oxide ceramic substrate or a silicon nitride ceramic substrate.
In the method for manufacturing the composite substrate, after the surface of the copper foil is cleaned, a shielding area is disposed on the surface of the copper foil, and then the surface of the copper foil is treated with a chemical solution having a PH less than 3, so that the copper oxide film layer is not formed in the shielding area, and a gas escape space is formed in the copper oxide film layer.
In the manufacturing method of the composite substrate, the shielding regions on the surface of the copper foil are a plurality of regions.
Drawings
FIG. 1 is a flow chart of a first embodiment of the present invention;
FIG. 2 is a schematic flow chart of a first embodiment of the present invention;
FIG. 3 is a schematic view of a copper foil having a shaded area on its surface according to a second embodiment of the present invention;
FIG. 4 is a schematic view of a copper foil having a copper oxide film formed thereon according to a second embodiment of the present invention;
FIG. 5 is a cross-sectional view of a copper foil having a copper oxide film formed thereon according to a second embodiment of the present invention;
FIG. 6 is a partial cross-sectional view of a copper oxide film formed on a copper foil surface according to a second embodiment of the present invention;
fig. 7 is a schematic view illustrating eutectic bonding between a copper foil and a ceramic substrate according to a second embodiment of the present invention.
Description of the symbols:
10. composite substrate
1. Copper foil
2. Ceramic substrate
3. Copper oxide film layer
4. Shaded area
5. Air escape space
Detailed Description
Referring to fig. 1 and 2, it can be clearly seen that the method for manufacturing a composite substrate 10 according to the first embodiment of the present invention is implemented according to the following steps:
(A) a copper foil 1 and a ceramic substrate 2 are prepared, and the ceramic substrate 1 may be an aluminum nitride ceramic substrate, an aluminum oxide ceramic substrate or a silicon nitride ceramic substrate.
(B) The copper foil 1 is cleaned to remove stains or dirt on the surface of the copper foil 1.
(C) Treating the surface of the copper foil by using a liquid medicine with the pH value of less than 3, wherein the liquid medicine contains 2-20% by weight of hydrogen peroxide, 2-20% by weight of sulfuric acid and 0.5-5% by weight of an accelerator of a nitrogen-containing heterocyclic compound, and the accelerator contains alkyl, phenyl, amino or hydroxyl; the chemical solution and the surface of the copper foil 1 simultaneously generate two reactions, namely an etching reaction and a film forming reaction, wherein the etching reaction generates etching (etching) on the surface of the copper foil 1 to roughen the surface of the copper foil 1, the film forming reaction forms a copper oxide film layer 3 of an organic metal compound with a rubble microstructure and a compact structure on the surface of the copper foil 1, the surface of the copper foil 1 is roughened, so that the copper oxide film layer 3 and the surface of the copper foil 1 generate good binding force, and the binding force of the copper oxide film layer 3 is enhanced by the action of an accelerator.
(D) The copper oxide film layer 3 of the copper foil 1 is attached to the surface of the ceramic substrate 2, the copper foil 1 is heated to the eutectic temperature, so that the copper foil 1 and the copper oxide film layer 3 on the surface of the copper foil produce eutectic reaction, and the copper foil 1 and the ceramic substrate 2 are bonded to form the composite substrate 10.
Referring to fig. 3 to 7, a difference between the second embodiment of the present invention and the first embodiment is that after the surface of the copper foil 1 is cleaned, a plurality of shielding regions 4 are formed on the surface of the copper foil 1, the surface of the copper foil 1 is treated with a chemical solution having a pH less than 3, the shielding regions 4 on the surface of the copper foil 1 are removed after the chemical solution is treated, so that the copper oxide film 3 forms a copper oxide film 3 on the surface of the copper foil 1 not shielded by the shielding regions 4, and an air-escaping space 5 is formed in the copper oxide film 3, thereby increasing the flow capacity of the eutectic liquid phase of the copper oxide film 3 when the copper foil 3 of the copper foil 1 is attached to the surface of the ceramic substrate 2 and the copper foil 1 is heated to the eutectic temperature, reducing the generation of air gaps, and reducing the number of air gaps between the copper foil 1 and the ceramic substrate 2 when the composite substrate 10 is manufactured, the heat conduction capability and the bonding strength of the composite substrate are greatly improved. Furthermore, in the embodiment, the shielding regions 4 are disposed in a plurality of circular configurations, but the invention is not limited thereto, and the shape and number of the shielding regions 4 can be adjusted according to the thickness of the copper oxide film layer 3, the copper foil area …, and other factors.

Claims (5)

1. A method for manufacturing a composite substrate includes the following steps:
cleaning the surface of the copper foil to remove oil stains or dirt on the surface; after cleaning, arranging a shielding area on the surface of the copper foil;
treating the surface of the copper foil by using a liquid medicine with the pH value of less than 3, etching and roughening the surface of the copper foil by using the liquid medicine, and forming a copper oxide film layer of an organic metal compound with a macadam-shaped microstructure on the surface of the copper foil, wherein the copper oxide film layer cannot be formed in a shielding area, so that an air escape space is formed in the copper oxide film layer;
and (3) attaching the copper oxide film layer of the copper foil to the surface of the ceramic substrate, heating the copper foil to an eutectic temperature, so that the copper foil and the copper oxide film layer on the surface of the copper foil generate an eutectic reaction, and further bonding the copper foil and the ceramic substrate.
2. The method of claim 1, wherein the chemical solution comprises at least 2-20 wt% of hydrogen peroxide, 2-20 wt% of sulfuric acid, and 0.5-5 wt% of an accelerator of a nitrogen-containing heterocyclic compound, wherein the accelerator is used to enhance the bonding strength of the copper oxide film.
3. The method as claimed in claim 2, wherein the accelerator comprises alkyl, phenyl, amino or hydroxyl.
4. The method of claim 1, wherein the ceramic substrate is an aluminum nitride ceramic substrate, an aluminum oxide ceramic substrate, or a silicon nitride ceramic substrate.
5. The method as claimed in claim 1, wherein the shielding regions are disposed in plural numbers.
CN201910906376.1A 2019-09-24 2019-09-24 Method for manufacturing composite substrate Active CN112624786B (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5800859A (en) * 1994-12-12 1998-09-01 Price; Andrew David Copper coating of printed circuit boards
US5869130A (en) * 1997-06-12 1999-02-09 Mac Dermid, Incorporated Process for improving the adhesion of polymeric materials to metal surfaces
US6162503A (en) * 1997-06-12 2000-12-19 Macdermid, Incorporated Process for improving the adhesion of polymeric materials to metal surfaces
CN101351090A (en) * 2007-07-20 2009-01-21 广东省石油化工研究院 Ultra-roughening treating agent for cuprum surface
CN102159027A (en) * 2011-01-17 2011-08-17 开平依利安达电子第三有限公司 Method for manufacturing high frequency microwave printed circuit boards with Rogers ceramic wafer laminated copper foils
CN104072186A (en) * 2013-03-27 2014-10-01 比亚迪股份有限公司 A preparing method of a ceramic copper-clad plate
CN105050324A (en) * 2015-07-01 2015-11-11 广东光华科技股份有限公司 Copper surface roughening treatment solution and treatment method thereof
CN109608221A (en) * 2018-11-30 2019-04-12 合肥市闵葵电力工程有限公司 A kind of preparation method of aluminium nitride ceramic copper-clad substrate
CN110029336A (en) * 2019-05-24 2019-07-19 电子科技大学 A kind of multilayer printed circuit board manufacture copper surface treatment liquid and processing method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5800859A (en) * 1994-12-12 1998-09-01 Price; Andrew David Copper coating of printed circuit boards
US5869130A (en) * 1997-06-12 1999-02-09 Mac Dermid, Incorporated Process for improving the adhesion of polymeric materials to metal surfaces
US6162503A (en) * 1997-06-12 2000-12-19 Macdermid, Incorporated Process for improving the adhesion of polymeric materials to metal surfaces
CN101351090A (en) * 2007-07-20 2009-01-21 广东省石油化工研究院 Ultra-roughening treating agent for cuprum surface
CN102159027A (en) * 2011-01-17 2011-08-17 开平依利安达电子第三有限公司 Method for manufacturing high frequency microwave printed circuit boards with Rogers ceramic wafer laminated copper foils
CN104072186A (en) * 2013-03-27 2014-10-01 比亚迪股份有限公司 A preparing method of a ceramic copper-clad plate
CN105050324A (en) * 2015-07-01 2015-11-11 广东光华科技股份有限公司 Copper surface roughening treatment solution and treatment method thereof
CN109608221A (en) * 2018-11-30 2019-04-12 合肥市闵葵电力工程有限公司 A kind of preparation method of aluminium nitride ceramic copper-clad substrate
CN110029336A (en) * 2019-05-24 2019-07-19 电子科技大学 A kind of multilayer printed circuit board manufacture copper surface treatment liquid and processing method

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