CN114163259B - Method for metallizing ceramic surface and metallized ceramic - Google Patents
Method for metallizing ceramic surface and metallized ceramic Download PDFInfo
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- CN114163259B CN114163259B CN202111527789.2A CN202111527789A CN114163259B CN 114163259 B CN114163259 B CN 114163259B CN 202111527789 A CN202111527789 A CN 202111527789A CN 114163259 B CN114163259 B CN 114163259B
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Abstract
The invention relates to the technical field of electronic product manufacturing, in particular to a method for metallizing a ceramic surface and metallized ceramic, which comprises the following steps: irradiating a ceramic substrate with a laser beam, and writing a circuit pattern area on the ceramic substrate; immersing the irradiated ceramic substrate in copper plating solution for electroless copper plating, and growing a seed copper layer on the circuit pattern area; sequentially placing brazing filler metal and copper foil on the seed copper layer for brazing; and etching to expose the ceramic substrate in the non-circuit pattern area. The method can form a thicker copper layer on the surface of the ceramic substrate, can form a high-precision circuit pattern, and has good bonding force between the copper layer and the substrate.
Description
Technical Field
The invention relates to the technical field of electronic product manufacturing, in particular to a method for metallizing a ceramic surface and metallized ceramic.
Background
In recent years, the LED technology is continuously upgraded, the LED light efficiency is higher and higher, the photoelectric conversion efficiency of a high-power LED chip can only reach 70-80%, which means that about 20% -30% of electric energy is converted into heat energy, so as to meet the technical upgrading requirement, the conversion from electric energy to heat energy is reduced, the heat conduction efficiency is improved, a ceramic substrate is adopted in a large scale as a functional module, and the DBC technology and the DPC technology are adopted in most of the market at present.
The DBC process is a technique for directly metallizing the surface of a ceramic substrate by copper coating. The technology is mainly used for packaging power electronic modules, semiconductor refrigeration, LED devices and the like and has wide application. However, the copper foil coated with copper by the process has larger thickness, the high-precision etched circuit is difficult to obtain by post-process etching, and because oxygen elements remained at the interface after sintering are difficult to control, air holes are formed between the copper foil and the ceramic substrate, and finally, the performance of the power device is unstable.
The DPC process is a technology for metallizing the surface of a ceramic substrate by a vacuum magnetron sputtering mode, a layer of Ti is required to be deposited as a transition layer before a Cu layer is deposited so as to enhance the bonding force between the Cu layer and the ceramic substrate, and the Ti is required to be etched after pattern transfer is completed, so that the process is complex. In addition, the manufacturing equipment of the vacuum film technology is expensive, and the production efficiency is low.
Disclosure of Invention
Based on this, the present invention provides a method of metallizing a ceramic surface. The copper layer can be formed thicker on the surface of the ceramic substrate, the high-precision circuit pattern can be formed, and the bonding force between the copper layer and the substrate is good.
The technical proposal is as follows:
a method of metallizing a ceramic surface comprising the steps of:
irradiating a ceramic substrate with a laser beam, and writing a circuit pattern area on the ceramic substrate;
immersing the irradiated ceramic substrate in copper plating solution for electroless copper plating, and growing a seed copper layer on the circuit pattern area;
brazing copper foil on the seed copper layer by using brazing filler metal;
and etching to expose the ceramic substrate in the non-circuit pattern area.
In one embodiment, the parameters of the laser beam include: laser pulse width 2.3t/ms-2.5t/ms, laser frequency 4.5f/Hz-5f/Hz, laser scanning speed 320V/(mm. Times.mi) -1 )-350V/(mm*mi n -1 )。
In one embodiment, the copper plating solution includes a solvent and the following concentration components:
Cu 2+ 0.8g*L -1 -1g*L -1 0.3g of reducing agent L -1 -0.5g*L -1 Complexing agent 4.5g L -1 -5g*L -1 Stabilizer 4g L -1 -5g*L -1 Sodium hydroxide 2.5g L -1 -3*L -1 。
In one embodiment, the thickness of the seed copper layer is 800nm-1200nm, and the thickness of the copper foil is 0.5mm-1.0mm.
In one embodiment, the braze is selected from one of a Ni-based amorphous braze, a Cu-based amorphous braze, and a Ti-based amorphous braze.
In one embodiment, the solder is CuNi 12 Ti 35 。
In one embodiment, the process parameters of the braze foil include: the brazing temperature is 1115K-1200K, the brazing time is 20min-30min, and the vacuum degree is 290-300Pa.
In one embodiment, the method further comprises the steps of film pasting, exposure and development before etching, and the step of film stripping after etching.
In one embodiment, the ceramic substrate is an aluminum nitride ceramic substrate.
In one embodiment, after exposing the ceramic substrate in the non-circuit pattern area, the method further comprises a step of depositing gold or silver.
The invention also provides metallized ceramic which is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly plates a seed copper layer on a circuit pattern area of a ceramic substrate by a laser direct writing technology and chemical plating, then thickens the seed copper layer by a brazing process, and finally obtains a high-precision ceramic circuit board by etching, thereby realizing the surface metallization of the ceramic substrate. The method of the invention can form a thicker copper layer on the surface of the ceramic substrate, has high heat conductivity, can form a high-precision circuit pattern on the basis of the thicker copper layer, and can ensure that the copper layer has good bonding force with the substrate (the bonding force between the seed copper layer and the ceramic substrate is good, and meanwhile, the bonding force between the seed copper layer and the copper foil is also good). In addition, sintering is avoided, oxygen element residues are avoided, the problem of unstable performance of the power device caused by air holes between the copper foil and the ceramic substrate is avoided, the preparation method is advanced, and the preparation cost is economical.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic diagram of peel strength test.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "fixed to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or," and/or, "and/or" includes any one of two or more of the listed items and also includes any and all combinations of the listed items, including any two or more of the listed items, any or all of the listed items.
In the present invention, "one or more" means any one, any two or more of the listed items. Wherein "several" means any two or more.
In the present invention, the use of "a combination thereof", "any combination thereof", and the like includes all suitable combinations of any two or more of the listed items.
In the present invention, "suitable" in "suitable combination manner", "suitable manner", "any suitable manner", etc. are used in order to implement the technical solution of the present invention, solve the technical problem of the present invention, and achieve the technical effects expected by the present invention.
In the present invention, "preferred" is merely to describe embodiments or examples that are more effective, and it should be understood that they are not intended to limit the scope of the present invention.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical range is referred to, and both ends of the numerical range are included unless otherwise specified.
In the present invention, the content of the components is referred to as mass percent for solid-liquid mixing and solid-solid mixing, and volume percent for liquid-liquid mixing unless otherwise specified.
In the present invention, the term "percent concentration" refers to the final concentration unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
In the present invention, the temperature parameter is not particularly limited, and it is allowed to perform the constant temperature treatment or the treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
Traditional methods of ceramic surface metallization are the DBC process and the DPC process.
The DBC process is a technique for directly metallizing the surface of a ceramic substrate by copper coating. The technology is mainly used for packaging power electronic modules, semiconductor refrigeration, LED devices and the like and has wide application. However, the copper foil coated with copper by the process has larger thickness, the high-precision etched circuit is difficult to obtain by post-process etching, and because oxygen elements remained at the interface after sintering are difficult to control, air holes are formed between the copper foil and the ceramic substrate, and finally, the performance of the power device is unstable.
The DPC process is a technology for metallizing the surface of a ceramic substrate by a vacuum magnetron sputtering mode, a layer of Ti is required to be deposited as a transition layer before a Cu layer is deposited so as to enhance the bonding force between the Cu layer and the ceramic substrate, and the Ti is required to be etched after pattern transfer is completed, so that the process is complex. In addition, the manufacturing equipment of the vacuum film technology is expensive, and the production efficiency is low.
Unlike conventional methods, the present invention provides a method for metallizing ceramic surfaces.
As shown in fig. 1, a method for metallizing a ceramic surface according to one embodiment of the invention comprises the steps of:
s1, irradiating a ceramic substrate by using a laser beam, and writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in copper plating solution for electroless copper plating, and growing a seed copper layer on the circuit pattern area;
s3, brazing copper foil on the seed copper layer by using brazing filler metal;
and S4, etching, wherein the ceramic substrate is exposed in the non-circuit pattern area.
Specifically, the ceramic substrate of the present embodiment may be an aluminum nitride ceramic substrate.
Based on the laser direct writing technology, in this embodiment, a laser beam is used to irradiate a ceramic substrate, and a circuit pattern area is written on the ceramic substrate. It can be understood that the irradiation area is a circuit pattern area, covalent bonds between metal atoms and non-metal atoms on the irradiated area of the ceramic substrate are broken by obtaining energy of a laser beam, and free metal atoms are exposed and distributed in the irradiated area, and in the subsequent electroless copper plating process, the free metal atoms can serve as catalysts, so that copper plating can be realized in the circuit pattern area through the laser beam irradiation area, and a seed copper layer is grown; the surface of the ceramic substrate in the area not irradiated by the laser beam is not changed, and copper plating is not performed.
In addition, the laser beam irradiates the ceramic substrate, and besides generating free metal atoms which can be used as catalysts in electroless copper plating, the surface of the ceramic substrate can be roughened, so that the bonding force between the copper layer and the surface of the ceramic substrate is enhanced.
Optionally, the parameters of the laser beam include: laser pulse width 2.3t/ms-2.5t/ms, laser frequency 4.5f/Hz-5f/Hz, laser scanning speed 320V/(mm. Times.mi) -1 )-350V/(mm*mi n -1 ). The ceramic substrate is irradiated with a numerical control laser beam with variable intensity, so that a precise circuit pattern area can be written.
In this example, a seed copper layer was grown on a ceramic substrate by a combination of laser direct writing and electroless copper plating. Electroless copper plating is a plating process that reduces metal ions in a plating bath to metal with the aid of a suitable reducing agent and deposits the metal onto the surface of a part without the application of an electrical current. In the electroless copper plating process of this embodiment, the "catalytic" centers of metal atoms are formed in the circuit pattern area due to the preliminary laser irradiation, and the copper-containing compound in the plating solution is induced to decompose, so that copper is deposited on the surface of the ceramic substrate in the circuit pattern area, and copper particles on the surface of the ceramic substrate are "implanted", thereby realizing the patterning of the ceramic circuit board. Secondly, the electroless plating process does not need external current, and copper salt and reducing agent in the electroless plating solution are utilized to carry out oxidation-reduction reaction on the surface of the ceramic matrix with catalytic activity to generate copper deposition, so that the purpose of forming a seed copper layer is achieved.
Optionally, the copper plating solution includes a solvent and the following concentration components:
Cu 2+ 0.8g*L -1 -1g*L -1 0.3g of reducing agent L -1 -0.5g*L -1 Complexing agent 4.5g L -1 -5g*L -1 Stabilizer 4g L -1 -5g*L -1 Sodium hydroxide 2.5g L -1 -3*L -1 。
Further, cu 2+ Cu which may be copper sulfate 2+ Or Cu of copper chloride 2+ 。
Further, the reducing agent is formaldehyde.
Further, the stabilizer is EDTA2NA
Further, the complexing agent is sodium potassium tartrate.
The seed copper layer formed on the ceramic substrate by the method can reduce the patterned bonding stress of the circuit board and reduce the stress problem caused by high heat of the ceramic circuit board.
In this embodiment, the thickness of the seed copper layer is 800nm-1200nm, and at this time, a good bonding force between the ceramic substrate and the copper layer can be maintained.
In this embodiment, the copper layer on the ceramic substrate is thickened by AMB technology.
The AMB technology is an active metal brazing copper-clad technology, and the high-temperature metallurgical bonding of the ceramic substrate and the oxygen-free copper is realized by means of active brazing filler metal.
Specifically, a brazing filler metal and a copper foil are laid on the seed copper layer, and then brazing is performed.
The selection of the brazing filler metal is very important, and the brazing quality and mechanical properties can be directly influenced. Therefore, factors such as wettability, spreadability, diffusion between the brazing filler metal and the base material, and uniformity of the brazing filler metal components are sufficiently considered in selecting the brazing filler metal.
It has been verified that metallic solders (e.g., silver-based solders, gold-based solders, copper-based solders, etc.) are poor in wettability with seed copper layers and are expensive. This example uses amorphous solder (made from amorphous alloy).
Alternatively, the brazing filler metal is selected from one of N i-based amorphous brazing filler metal, cu-based amorphous brazing filler metal, and Ti-based amorphous brazing filler metal.
Further alternatively, the braze is selected from the group consisting of CuNi 12 Ti 35 。
The brazing filler metal has a unique structure, uniform components and good wettability with a seed copper layer, and the prepared brazing filler metal layer has the advantages of high joint strength, good corrosion resistance, high bonding strength with the seed copper layer, small stress and the like.
In this example, the thickness of the copper foil is 0.5mm to 1.0mm. Copper thickness is further increased on the seed copper layer by means of brazing.
Optionally, the brazing process parameters include: the brazing temperature is 1115K-1200K, the brazing time is 20min-30min, and the vacuum degree is 290-300Pa.
During brazing, brazing filler metal wets the matrix and performs physical and chemical actions with the matrix to form a brazing layer such as a solid solution so as to realize the tight combination of welding materials. In this embodiment, the solder wets the seed copper layer and forms a braze layer between the seed copper layer and the copper foil, causing the seed copper layer to bond tightly with the copper foil.
It will be appreciated that the amorphous solder of this embodiment is a liquid that, in addition to being laid on the seed copper layer, inevitably extends to the non-line pattern areas. Meanwhile, in order to make the circuit pattern finer and avoid the connection condition of the circuit after each process treatment, the embodiment also etches the impurity in the non-circuit pattern area to expose the ceramic substrate in the area.
Impurities include, but are not limited to, copper on non-wiring pattern areas, braze layers, solder, copper foil, and the like.
It is understood that the steps of film pasting, exposure and development are further included before etching, and the step of film stripping is further included after etching.
Specifically:
sticking film: and (3) sticking a dry film on the whole surface of the ceramic substrate with the circuit copper layer.
Exposure: an ultraviolet radiation pattern region.
Developing: the portion of the dry film which has not been irradiated with ultraviolet light is dissolved away by sodium carbonate, and the irradiated portion remains.
Etching: according to a certain proportion of the solution, the impurities which are exposed by dissolving the dry film are dissolved by using an acidic copper chloride etching solution.
And (3) film removal: and dissolving the protective dry film on the circuit according to the liquid medicine with a certain proportion under the specific temperature and speed environment.
In this example, the etching solution is a hydrofluoric acid-hydrogen peroxide mixture, the film stripping liquid medicine is a strong alkali solution, and the specific temperature is 25 ℃ and the speed is 2.5 m/min.
In this embodiment, after the ceramic substrate is exposed in the non-circuit pattern area, the method further includes a step of depositing gold or silver. The ceramic substrate is exposed in the non-circuit pattern area, and has a complete circuit layer, and gold or silver can be deposited on the circuit layer through electroless plating to form the final required circuit pattern.
The invention firstly plates a seed copper layer on a circuit pattern area of a ceramic substrate by a laser direct writing technology and chemical plating, then thickens the seed copper layer by a brazing process, and finally obtains a high-precision ceramic circuit board by etching, thereby realizing the surface metallization of the ceramic substrate. The method of the invention can form a thicker copper layer on the surface of the ceramic substrate, has high heat conductivity, can form a high-precision circuit pattern on the basis of the thicker copper layer, and can ensure that the copper layer has good bonding force with the substrate (the bonding force between the seed copper layer and the ceramic substrate is good, and meanwhile, the bonding force between the seed copper layer and the copper foil is also good). In addition, sintering is avoided, oxygen element residues are avoided, the problem of unstable performance of the power device caused by air holes between the copper foil and the ceramic substrate is avoided, the preparation method is advanced, and the preparation cost is economical.
The invention also provides metallized ceramic prepared by the preparation method. The ceramic substrate of the metallized ceramic has good binding force with the copper layer, precise circuit, thicker copper layer and good thermal conductivity.
The metallized ceramic can be used in an LED ceramic bracket.
The following examples and comparative examples are further illustrated by the fact that the materials used, unless otherwise indicated, are commercially available and that the equipment used, unless otherwise indicated, are commercially available and that the processes involved, unless otherwise indicated, are routine selections by those skilled in the art.
Example 1
The embodiment provides a method for metallizing a ceramic surface and metallized ceramic, comprising the following steps:
s1, irradiating a ceramic substrate by using a laser beam, wherein parameters of the laser beam are as follows: laser pulse width 2.4t/ms, laser frequency 4.5f/Hz, laser scanning speed 330V/(mm. Times.mi) -1 ) Writing on the ceramic substrateA line pattern area;
s2, immersing the irradiated ceramic substrate in copper plating solution for electroless copper plating, and growing a seed copper layer with the thickness of 1000nm on the circuit pattern area; wherein, the copper plating solution comprises water and the following concentration components: copper sulphate 0.8g x L -1 0.5g of formaldehyde -1 5g of potassium sodium tartrate -1 、EDTA2NA 5g*L -1 Sodium hydroxide 2.5g L -1 。
S3, paving liquid solder CuNi on the seed copper layer 12 Ti 35 Then, a copper foil of 0.8mm thickness was laid, and 30mi n was brazed at a vacuum of 300Pa and a temperature of 1115K to form a brazing layer between the seed copper layer and the copper foil.
S4, sticking a dry film on the ceramic substrate with the circuit copper layer comprehensively, radiating a circuit pattern area by ultraviolet rays, dissolving the part of the dry film which is not radiated by the ultraviolet rays by sodium carbonate, dissolving impurities exposed by the dissolved dry film by using an acid copper chloride etching solution, exposing the ceramic substrate in a non-circuit pattern area, and dissolving the dry film on the circuit pattern to obtain the ceramic with the complete circuit layer.
Example 2
The present example provides a method for metallizing a ceramic surface and a metallized ceramic, which, unlike the process parameters of example 1, comprises the following steps:
s1, irradiating a ceramic substrate by using a laser beam, wherein parameters of the laser beam are as follows: laser pulse width 2.3t/ms, laser frequency 5f/Hz, laser scanning speed 320V/(mm. Times.mi) -1 ) Writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in copper plating solution for electroless copper plating, and growing a seed copper layer with the thickness of 1100nm on the circuit pattern area; wherein, the copper plating solution comprises water and the following concentration components: copper chloride 1g x L -1 Formaldehyde 0.4g x L -1 5g of potassium sodium tartrate -1 、EDTA2NA 5g*L -1 Sodium hydroxide 3g x L -1 。
S3, paving liquid solder CuNi on the seed copper layer 12 Ti 35 Then lay down 0.5mm thickCopper foil having a degree of vacuum of 290Pa and a temperature of 1200K was brazed at 20min to form a brazing layer between the seed copper layer and the copper foil.
S4, sticking a dry film on the ceramic substrate with the circuit copper layer comprehensively, radiating a circuit pattern area by ultraviolet rays, dissolving the part of the dry film which is not radiated by the ultraviolet rays by sodium carbonate, dissolving impurities exposed by the dissolved dry film by using an acid copper chloride etching solution, exposing the ceramic substrate in a non-circuit pattern area, and dissolving the dry film on the circuit pattern to obtain the ceramic with the complete circuit layer.
Example 3
The present example provides a method for metallizing a ceramic surface and a metallized ceramic, which, unlike the process parameters of example 1, comprises the following steps:
s1, irradiating a ceramic substrate by using a laser beam, wherein parameters of the laser beam are as follows: laser pulse width 2.4t/ms, laser frequency 4.5f/Hz, laser scanning speed 330V/(mm. Times.mi) -1 ) Writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in copper plating solution for electroless copper plating, and growing a seed copper layer with the thickness of 1200nm on a circuit pattern area; wherein, the copper plating solution comprises water and the following concentration components: copper sulphate 0.8g x L -1 0.5g of formaldehyde -1 5g of potassium sodium tartrate -1 、EDTA2NA 5g*L -1 Sodium hydroxide 2.5g L -1 。
S3, paving liquid solder CuNi on the seed copper layer 12 Ti 35 Then, a copper foil of 1.0mm thickness was laid, and 30mi n was brazed at a vacuum of 300Pa and a temperature of 1115K to form a brazing layer between the seed copper layer and the copper foil.
S4, sticking a dry film on the ceramic substrate with the circuit copper layer comprehensively, radiating a circuit pattern area by ultraviolet rays, dissolving the part of the dry film which is not radiated by the ultraviolet rays by sodium carbonate, dissolving impurities exposed by the dissolved dry film by using an acid copper chloride etching solution, exposing the ceramic substrate in a non-circuit pattern area, and dissolving the dry film on the circuit pattern to obtain the ceramic with the complete circuit layer.
Comparative example 1
This comparative example provides a method of metallizing a ceramic surface and a metallized ceramic, which are mainly different from example 1 in that a copper layer of the same thickness as example 1 is formed by a laser direct writing technique and an electroless plating technique.
The method comprises the following steps:
s1, irradiating a ceramic substrate by using a laser beam, wherein parameters of the laser beam are as follows: laser pulse width 2.4t/ms, laser frequency 4.5f/Hz, laser scanning speed 330V/(mm. Times.mi) -1 ) Writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in copper plating solution for electroless copper plating, and growing a seed copper layer with the thickness of 1000nm on the circuit pattern area; wherein, the copper plating solution comprises water and the following concentration components: copper sulphate 0.8g x L -1 0.5g of formaldehyde -1 5g of potassium sodium tartrate -1 、EDTA2NA 5g*L -1 Sodium hydroxide 2.5g L -1 。
Comparative example 2
This comparative example provides a method of metallizing a ceramic surface and a metallized ceramic, which differs from example 1 primarily in that a copper layer of the same thickness as example 1 is formed by a brazing technique. The method comprises the following steps:
s1, paving liquid solder CuNi on a ceramic substrate 12 Ti 35 Then, a copper foil of 0.8mm thickness was laid, and 30mi n was brazed at a vacuum of 300Pa and a temperature of 1115K to form a brazing layer between the seed copper layer and the copper foil.
S2, sticking a dry film on the ceramic substrate with the circuit copper layer comprehensively, radiating a circuit pattern area by ultraviolet rays, dissolving the part of the dry film which is not radiated by the ultraviolet rays by sodium carbonate, dissolving impurities exposed by the dissolved dry film by using an acid copper chloride etching solution, exposing the ceramic substrate in a non-circuit pattern area, and dissolving the dry film on the circuit pattern to obtain the ceramic with the complete circuit layer.
The metallized ceramics of the above examples and comparative examples were subjected to a peel strength test and a cold heat shock test.
The procedure is as follows, the results are shown in tables 1 and 2:
1) Peel strength test
Test instrument: tensile tester STX500; an oven (125+ -2 deg.C is required); 3M adhesive tape; measuring tool
Test material: preparing a test sample, namely preparing 10 copper foil strips, wherein the width (3 mm plus or minus 0.2 mm) of each copper foil strip is 75mm, and the front side and the back side of each copper foil strip are respectively 1 strip and 2 strips are in a group; a total of 5 groups were prepared, corresponding to examples 1-3 and comparative examples 1-2, respectively.
The testing method comprises the following steps: a. one end of the copper foil strip was adhered to the outer copper foil of the metallized ceramic leaving the other end approximately 10mm for peeling, and the other end of the copper foil strip was fixed to a tensile tester, clamped with a clamp, and secured to remain perpendicular to the plane of the substrate, as shown in fig. 2.
b. And (4) zeroing the tensile force tester.
c. The tester is started, pulling force is applied at the speed of 50 mm/min, and the stripping length is not less than 30mm.
d. The minimum pull force to peel was recorded.
TABLE 1
2) Cold and hot impact test
Test instrument: HM-1400P (-40 ℃ to +150 ℃) of the cold and hot impact test box;
test material: examples 1-3 and comparative examples 1-2, a total of 5 sheets of metallized ceramic.
The testing method comprises the following steps: 5 pieces of metallized ceramic are used as sample pieces, the test temperature is 150 ℃/-45 ℃ according to the requirements of GB/T2423.22-2012, the test is circulated for 500 times, each cycle is kept at high and low temperatures for 0.5H, and the conversion time is 15S.
Determination result: and the copper foil is not fallen off more than 300 times.
TABLE 2
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples only represent preferred embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method of metallizing a ceramic surface, characterized by: the method comprises the following steps:
irradiating a ceramic substrate with a laser beam, and writing a circuit pattern area on the ceramic substrate;
immersing the irradiated ceramic substrate in copper plating solution for electroless copper plating, and growing a seed copper layer with the thickness of 800-1200 nm on a circuit pattern area;
brazing copper foil with the thickness of 0.5mm-1.0mm on the seed copper layer by using brazing filler metal;
and etching to expose the ceramic substrate in the non-circuit pattern area.
2. The method of claim 1, wherein the parameters of the laser beam include: laser pulse width is 2.3t/ms-2.5t/ms, laser frequency is 4.5f/Hz-5f/Hz, laser scanning speed is 320V/(mm. Times.min) -1 )-350V/(mm*min -1 )。
3. The method of metallizing a ceramic surface according to claim 1, wherein the copper plating solution comprises a solvent and the following concentration components:
Cu 2+ 0.8g*L -1 -1g*L -1 0.3g of reducing agent L -1 -0.5g*L -1 Complexing agent 4.5g L -1 -5g*L -1 Stabilizer 4g L -1 -5g*L -1 Sodium hydroxide 2.5g L -1 -3*L -1 。
4. The method of claim 1, wherein the seed copper layer has a thickness of 1000nm to 1200nm.
5. The method of metallizing a ceramic surface according to claim 1, wherein said braze is selected from one of a Ni-based amorphous braze, a Cu-based amorphous braze, and a Ti-based amorphous braze.
6. The method of metallizing a ceramic surface according to claim 1, wherein the process parameters of the braze foil include: the brazing temperature is 1115K-1200K, the brazing time is 20min-30min, and the vacuum degree is 290 Pa-300 Pa.
7. The method of claim 1-6, wherein the method further comprises the steps of film pasting, exposure and development before etching, and the step of film stripping after etching.
8. The method of metallizing a ceramic surface according to any one of claims 1-6, wherein said ceramic substrate is an aluminum nitride ceramic substrate.
9. The method of claim 1-6, further comprising the step of depositing gold or silver after exposing the ceramic substrate in the non-circuit pattern area.
10. A metallized ceramic prepared by the method of any one of claims 1-9.
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