CN114163259A - Method for metallizing ceramic surfaces and metallized ceramics - Google Patents
Method for metallizing ceramic surfaces and metallized ceramics Download PDFInfo
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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 by adopting laser beams, and writing a circuit pattern area on the ceramic substrate; immersing the irradiated ceramic substrate in a 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; etching to expose the ceramic substrate in the non-circuit pattern region. 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 lighting effect is higher and higher, the photoelectric conversion efficiency of the high-power LED chip can only reach 70-80%, which means that about 20% -30% of electric energy is converted into heat energy, in order to meet the requirement of technology upgrade, at present, in order to improve the photoelectric conversion efficiency, reduce the conversion of electric energy into heat energy, and improve the heat conduction efficiency, the ceramic substrate is adopted as a functional module on a large scale, and at present, the DBC process and the DPC process are mostly adopted in the market.
The DBC process is a technology for metallizing the surface of a ceramic substrate by directly coating copper. The technology is mainly used for packaging and widely applying power electronic modules, semiconductor refrigeration, LED devices and the like. However, the copper clad copper foil in the process has a large thickness, a high-precision etching circuit is difficult to obtain by post-process etching, and oxygen elements remained on an interface after sintering are difficult to control, so that air holes are formed between the copper foil and a ceramic substrate, and finally the performance of a power device is unstable.
The DPC technology is a technology for metalizing the surface of the ceramic substrate in a vacuum magnetron sputtering mode, a Ti layer 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, the Ti is required to be etched after the pattern transfer is completed, and the technology 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 the method, the invention provides a method for metallizing the surface of the ceramic. Can form thicker copper layer on ceramic substrate surface, and can form high accuracy circuit pattern, and the cohesion of copper layer and base plate is good.
The technical scheme is as follows:
a method of metallizing a ceramic surface comprising the steps of:
irradiating a ceramic substrate by adopting laser beams, and writing a circuit pattern area on the ceramic substrate;
immersing the irradiated ceramic substrate in a 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;
etching to expose the ceramic substrate in the non-circuit pattern region.
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 mi n)-1)-350V/(mm*mi n-1)。
In one embodiment, the copper plating solution comprises a solvent and the following components in concentration:
Cu2+0.8g*L-1-1g*L-10.3g of reducing agent-1-0.5g*L-1Complexing agent 4.5g-1-5g*L-14g of stabilizer L-1-5g*L-12.5g of sodium hydroxide-1-3*L-1。
In one embodiment, the seed copper layer has a thickness of 800nm to 1200nm, and the copper foil has a thickness of 0.5mm to 1.0 mm.
In one embodiment, the solder is selected from one of a Ni-based amorphous solder, a Cu-based amorphous solder, and a Ti-based amorphous solder.
In one embodiment, the brazing filler metal is CuNi12Ti35。
In one embodiment, the process parameters of the brazing copper foil include: the brazing temperature is 1115K-1200K, the time is 20min-30min, and the vacuum degree is 290-300 Pa.
In one embodiment, the method further comprises the steps of film pasting, exposure and development before etching, and further comprises the step of film stripping after etching.
In one embodiment, the ceramic substrate is an aluminum nitride ceramic substrate.
In one embodiment, after the non-circuit pattern region exposes the ceramic substrate, a step of depositing gold or silver is further included.
The invention also provides a metallized ceramic prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a seed copper layer is plated on a circuit pattern area of the ceramic substrate by a laser direct writing technology and chemical plating, then the seed copper layer is thickened by a brazing process, and then a high-precision ceramic circuit board can be obtained by etching, so that the surface metallization of the ceramic substrate is realized. According to the method, a thick copper layer can be formed on the surface of the ceramic substrate, the copper layer has high thermal conductivity, a high-precision circuit pattern can be formed on the basis of the thick copper layer, and the bonding force between the copper layer and the substrate is good (the bonding force between the seed copper layer and the ceramic substrate is good, and the bonding force between the seed copper layer and the copper foil is also good). In addition, sintering is avoided, oxygen element residue is avoided, the problem that the performance of the power device is unstable due to air holes between the copper foil and the ceramic substrate is solved, the preparation method is more advanced, and the preparation cost is more economic.
Drawings
FIG. 1 is a process flow diagram of the present invention;
fig. 2 is a schematic diagram of the peel strength test.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying 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 "secured 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 in the description of the invention herein 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" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
In the present invention, "one or more" means any one, any two or more of the listed items. Wherein, the 'several' means any two or more than any two.
In the present invention, the terms "combination thereof", "any combination thereof", and the like include all suitable combinations of any two or more of the listed items.
In the present invention, the term "suitable" used in "suitable combination", "suitable method", "any suitable method", and the like is based on the technical solution of the present invention that can be implemented, the technical problem of the present invention can be solved, and the intended technical effect of the present invention can be achieved.
In the present invention, "preferred" is only an embodiment or an example for better description, and it should be understood that the scope of the present invention is not limited thereto.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical range is defined to include both end points of the numerical range unless otherwise specified.
In the present invention, the percentage content refers to both mass percentage for solid-liquid mixing and solid-solid phase mixing and volume percentage for liquid-liquid phase mixing, unless otherwise specified.
In the present invention, the percentage concentrations are referred to as final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.
In the present invention, the temperature parameter is not particularly limited, and the treatment is allowed to be performed at a constant temperature or within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The traditional ceramic surface metallization method is DBC process and DPC process.
The DBC process is a technology for metallizing the surface of a ceramic substrate by directly coating copper. The technology is mainly used for packaging and widely applying power electronic modules, semiconductor refrigeration, LED devices and the like. However, the copper clad copper foil in the process has a large thickness, a high-precision etching circuit is difficult to obtain by post-process etching, and oxygen elements remained on an interface after sintering are difficult to control, so that air holes are formed between the copper foil and a ceramic substrate, and finally the performance of a power device is unstable.
The DPC technology is a technology for metalizing the surface of the ceramic substrate in a vacuum magnetron sputtering mode, a Ti layer 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, the Ti is required to be etched after the pattern transfer is completed, and the technology is complex. In addition, the manufacturing equipment of the vacuum film technology is expensive, and the production efficiency is low.
The invention provides a method for metalizing the surface of the ceramic, which is different from the traditional method.
As shown in fig. 1, a method for metallizing a ceramic surface according to an embodiment of the present invention comprises the following steps:
s1, irradiating the ceramic substrate by using laser beams, and writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in a copper plating solution for electroless copper plating, and growing a seed copper layer on the circuit pattern area;
s3, brazing a copper foil on the seed copper layer by using brazing filler metal;
s4, etching to expose the ceramic substrate 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. The irradiation area is a circuit pattern area, covalent bonds between metal atoms and non-metal atoms on the irradiated area on the ceramic substrate are broken by the energy of laser beams, free metal atoms are exposed and distributed in the irradiated area, and the free metal atoms can serve as a catalyst in the subsequent chemical copper plating process, so that copper can be plated in the circuit pattern area, and a seed copper layer grows; and the surface of the ceramic substrate in the non-laser beam irradiation area is not changed, and copper plating is not generated.
In addition, the laser beam irradiates the ceramic substrate, so that free metal atoms which can be used as a catalyst in electroless copper plating later are generated, the surface of the ceramic substrate can be roughened, and 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 mi n)-1)-350V/(mm*mi n-1). The ceramic substrate is irradiated by 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 combining a laser direct writing technique and electroless copper plating. Electroless copper plating is a plating method in which metal ions in a plating solution are reduced to metal by means of a suitable reducing agent without application of an electric current and deposited on the surface of a part. In the electroless copper plating process of the embodiment, due to the early laser irradiation, a 'catalytic' center of metal atoms is formed in the circuit pattern area, and the decomposition of the copper-containing compound in the plating solution is induced, 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', and the patterning of the ceramic circuit board is realized. Secondly, the chemical plating process does not need external current, and copper salt and reducing agent in the chemical plating solution are used for carrying out oxidation-reduction reaction on the surface of the ceramic matrix with catalytic activity to generate copper deposition, so that the aim of forming a seed copper layer is fulfilled.
Optionally, the copper plating solution comprises a solvent and the following components in concentrations:
Cu2+0.8g*L-1-1g*L-10.3g of reducing agent-1-0.5g*L-1Complexing agent 4.5g-1-5g*L-14g of stabilizer L-1-5g*L-12.5g of sodium hydroxide-1-3*L-1。
Further, Cu2+Cu which may be copper sulfate2+Or Cu of copper chloride2+。
Further, the reducing agent is formaldehyde.
Further, the stabilizer is EDTA2NA
Further, the complexing agent is potassium sodium tartrate.
The seed copper layer formed on the ceramic substrate by the method can reduce the patterned combination stress of the circuit board and reduce the stress problem caused by high heat of the ceramic circuit board.
In this embodiment, the seed copper layer has a thickness of 800nm to 1200nm, so that a good bonding force between the ceramic substrate and the copper layer can be maintained.
In this example, the copper layer on the ceramic substrate was thickened by the AMB technique.
The AMB technology is an active metal brazing copper-clad technology, and high-temperature metallurgical bonding of a ceramic substrate and oxygen-free copper is realized by means of active brazing filler metal.
Specifically, a brazing material and a copper foil are firstly laid on the seed copper layer, and then brazing is carried out.
The selection of the brazing filler metal is very important, and the brazing quality and the mechanical property can be directly influenced. Therefore, factors such as wettability, spreadability, diffusion between the brazing material and the base material, and uniformity of the composition of the brazing material are sufficiently considered in selecting the brazing material.
It is verified that the metal solder (such as silver-based solder, gold-based solder, copper-based solder, etc.) has poor wettability with the seed copper layer and is expensive. This example uses an amorphous solder (made from an amorphous alloy).
Optionally, the solder is selected from one of N i-based amorphous solder, Cu-based amorphous solder, and Ti-based amorphous solder.
Further optionally, the brazing filler metal is selected from the group consisting of CuNi12Ti35。
The brazing filler metal has a unique structure and uniform components, has good wettability with the 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 1.0 mm. The 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 time is 20min-30min, and the vacuum degree is 290-300 Pa.
During brazing, the brazing filler metal wets the matrix and forms a brazing layer such as solid solution through physical and chemical action with the matrix, so that the welding materials are tightly combined. In this embodiment, the solder wets the seed copper layer and forms a solder layer between the seed copper layer and the copper foil, so that the seed copper layer and the copper foil are tightly bonded.
It is understood that the amorphous solder of the present embodiment is a liquid, which inevitably extends to a non-wiring pattern region in addition to being laid on the seed copper layer. Meanwhile, in order to make the circuit pattern more precise and avoid the connection of the circuit after the processing of each process, the present embodiment also etches the impurity in the non-circuit pattern region to expose the ceramic substrate in the region.
The impurities include, but are not limited to, copper on the non-wiring pattern area, a solder layer, a solder, a copper foil, etc.
It can be understood that the etching process further comprises the steps of film pasting, exposure and development before etching, and the etching process further comprises the step of film stripping after etching.
Specifically, the method comprises the following steps:
film pasting: and sticking a dry film on the whole surface of the ceramic substrate with the circuit copper layer.
Exposure: an ultraviolet radiation line pattern region.
And (3) developing: the part of the dry film which is not irradiated by ultraviolet rays is dissolved away by using sodium carbonate, and the irradiated part is remained.
Etching: according to a certain proportion of solution, the impurities exposed by dissolving the dry film are dissolved by acid copper chloride etching solution.
Film stripping: dissolving the protective dry film on the circuit according to a certain proportion of liquid medicine under the specific temperature and speed environment.
In this embodiment, the etching solution is a mixture of hydrofluoric acid and hydrogen peroxide, and the stripping solution is a strong alkaline 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 region, a step of depositing gold or silver is further included. The ceramic substrate is exposed in the non-circuit pattern area, the ceramic substrate is provided with a complete circuit layer, and gold or silver can be deposited on the circuit layer through chemical plating to form a final required circuit pattern.
According to the invention, a seed copper layer is plated on a circuit pattern area of the ceramic substrate by a laser direct writing technology and chemical plating, then the seed copper layer is thickened by a brazing process, and then a high-precision ceramic circuit board can be obtained by etching, so that the surface metallization of the ceramic substrate is realized. According to the method, a thick copper layer can be formed on the surface of the ceramic substrate, the copper layer has high thermal conductivity, a high-precision circuit pattern can be formed on the basis of the thick copper layer, and the bonding force between the copper layer and the substrate is good (the bonding force between the seed copper layer and the ceramic substrate is good, and the bonding force between the seed copper layer and the copper foil is also good). In addition, sintering is avoided, oxygen element residue is avoided, the problem that the performance of the power device is unstable due to air holes between the copper foil and the ceramic substrate is solved, the preparation method is more advanced, and the preparation cost is more economic.
The invention also provides the metallized ceramic prepared by the preparation method. The ceramic substrate of the metallized ceramic has good bonding force with a copper layer, precise circuit, thicker copper layer and good heat conductivity.
The metallized ceramic provided by the invention can be used in an LED ceramic bracket.
The following examples and comparative examples are further illustrated by reference to the following examples and comparative examples, wherein the starting materials used in the following examples and comparative examples are commercially available without specific reference, the equipment used therein is commercially available without specific reference, and the processes involved therein are routinely selected by those skilled in the art without specific reference.
Example 1
The embodiment provides a method for metallizing a ceramic surface and a metallized ceramic, which comprises the following steps:
s1, irradiating the ceramic substrate by using laser beams, wherein the parameters of the laser beams are as follows: laser pulse width 2.4t/ms, laser frequency 4.5f/Hz, laser scanning speed 330V/(mm mi n)-1) Writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in a 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 components with the concentration: copper sulfate 0.8g-10.5g of formaldehyde-15g of potassium sodium tartrate-1、EDTA2NA 5g*L-12.5g of sodium hydroxide-1。
S3, spreading liquid brazing filler metal CuNi on the seed copper layer12Ti35Then, a copper foil of 0.8mm in thickness was laid, and 30mi n was brazed at a temperature of 1115K under a vacuum of 300Pa to form a brazing layer between the seed copper layer and the copper foil.
S4, pasting a dry film on the ceramic substrate with the circuit copper layer, radiating the circuit pattern area with ultraviolet rays, dissolving the part of the dry film which is not radiated by the ultraviolet rays with sodium carbonate, dissolving the impurities exposed by the dissolved dry film with acid copper chloride etching solution, exposing the ceramic substrate in the non-circuit pattern area, and dissolving the dry film on the circuit pattern to obtain the ceramic with the complete circuit layer.
Example 2
This example provides a method for metallizing a ceramic surface and a metallized ceramic, which is different from the process parameters of example 1 in the following steps:
s1, irradiating the ceramic substrate by using laser beams, wherein the parameters of the laser beams are as follows: laser pulse width 2.3t/ms, laser frequency 5f/Hz, laser scanning speed 320V/(mm mi n)-1) Writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in a 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 components with the concentration: copper chloride 1g L-10.4g of formaldehyde-15g of potassium sodium tartrate-1、EDTA2NA 5g*L-13g of sodium hydroxide-1。
S3, spreading liquid brazing filler metal CuNi on the seed copper layer12Ti35Then, a copper foil of 0.5mm thickness was laid, and 20mi n was brazed at a temperature of 1200K under a vacuum of 290Pa to form a brazing layer between the seed copper layer and the copper foil.
S4, pasting a dry film on the ceramic substrate with the circuit copper layer, radiating the circuit pattern area with ultraviolet rays, dissolving the part of the dry film which is not radiated by the ultraviolet rays with sodium carbonate, dissolving the impurities exposed by the dissolved dry film with acid copper chloride etching solution, exposing the ceramic substrate in the non-circuit pattern area, and dissolving the dry film on the circuit pattern to obtain the ceramic with the complete circuit layer.
Example 3
This example provides a method for metallizing a ceramic surface and a metallized ceramic, which is different from the process parameters of example 1 in the following steps:
s1, irradiating the ceramic substrate by using laser beams, wherein the parameters of the laser beams are as follows: laser pulse width 2.4t/ms, laser frequency 4.5f/Hz, laser scanning speed 330V/(mm mi n)-1) Writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in a copper plating solution for electroless copper platingGrowing a seed copper layer with the thickness of 1200nm on the circuit pattern area; wherein, the copper plating solution comprises water and the following components with the concentration: copper sulfate 0.8g-10.5g of formaldehyde-15g of potassium sodium tartrate-1、EDTA2NA 5g*L-12.5g of sodium hydroxide-1。
S3, spreading liquid brazing filler metal CuNi on the seed copper layer12Ti35Then, a copper foil of 1.0mm in thickness was laid, and 30mi n was brazed under a vacuum of 300Pa and a temperature of 1115K to form a brazing layer between the seed copper layer and the copper foil.
S4, pasting a dry film on the ceramic substrate with the circuit copper layer, radiating the circuit pattern area with ultraviolet rays, dissolving the part of the dry film which is not radiated by the ultraviolet rays with sodium carbonate, dissolving the impurities exposed by the dissolved dry film with acid copper chloride etching solution, exposing the ceramic substrate in the 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, and is different from example 1 mainly in that a copper layer having the same thickness as that of example 1 is formed by a laser direct writing technique and an electroless plating technique.
The method comprises the following steps:
s1, irradiating the ceramic substrate by using laser beams, wherein the parameters of the laser beams are as follows: laser pulse width 2.4t/ms, laser frequency 4.5f/Hz, laser scanning speed 330V/(mm mi n)-1) Writing a circuit pattern area on the ceramic substrate;
s2, immersing the irradiated ceramic substrate in a 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 components with the concentration: copper sulfate 0.8g-10.5g of formaldehyde-15g of potassium sodium tartrate-1、EDTA2NA 5g*L-12.5g of sodium hydroxide-1。
Comparative example 2
This comparative example provides a method of metallizing a ceramic surface and a metallized ceramic, the main difference from example 1 is that a copper layer of the same thickness as in example 1 is formed by a brazing technique. The method comprises the following steps:
s1, spreading liquid brazing filler metal CuNi on the ceramic substrate12Ti35Then, a copper foil of 0.8mm in thickness was laid, and 30mi n was brazed at a temperature of 1115K under a vacuum of 300Pa to form a brazing layer between the seed copper layer and the copper foil.
S2, pasting a dry film on the ceramic substrate with the circuit copper layer, radiating the circuit pattern area with ultraviolet rays, dissolving the part of the dry film which is not radiated by the ultraviolet rays with sodium carbonate, dissolving the impurities exposed by the dissolved dry film with acid copper chloride etching solution, exposing the ceramic substrate in the 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 thermal shock test.
The procedure is as follows, and the results are shown in tables 1 and 2:
1) peel Strength test
Testing an instrument: a tensile tester STX 500; an oven (needs to be kept at 125 +/-2) DEG C; 3M adhesive tape; measuring tool
Testing materials: preparing a test sample, preparing 10 copper foil strips, wherein the width (3mm +/-0.2 mm) of the copper foil strips is 75mm, the length of the copper foil strips is 1 strip on the front side and the back side respectively, and 2 strips form a group; in total, 5 groups were prepared, corresponding to examples 1 to 3 and comparative examples 1 to 2, respectively.
The test 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, the other end of the copper foil strip was fixed to a tensile tester, clamped with a clamp and secured perpendicular to the substrate plane as shown in fig. 2.
b. The tensile tester is zeroed.
c. The tester is started to apply a pulling force at a speed of 50mm/mi n, and the peel length is not less than 30mm.
d. The minimum pull force at which it peeled off was recorded.
TABLE 1
2) Cold and heat shock test
Testing an instrument: the cold-hot impact test box HM-1400P (-40 ℃ - +150 ℃);
testing materials: examples 1-3 and comparative examples 1-2, for a total of 5 sheets of metallized ceramic.
The test method comprises the following steps: 5 pieces of metallized ceramics are used as sample pieces, the test temperature is 150 ℃ per liter to 45 ℃ according to the measurement of GB/T2423.22-2012, the circulation is carried out for 500 times, the high temperature and the low temperature of each circulation are respectively kept for 0.5H, and the conversion time is 15S.
And (4) judging the result: more than 300 times, the copper foil does not fall off.
TABLE 2
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only express preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method of metallizing a ceramic surface, comprising: the method comprises the following steps:
irradiating a ceramic substrate by adopting laser beams, and writing a circuit pattern area on the ceramic substrate;
immersing the irradiated ceramic substrate in a 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;
etching to expose the ceramic substrate in the non-circuit pattern region.
2. The method of claim 1, wherein 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 min)-1)-350V/(mm*min-1)。
3. The method of claim 1, wherein the copper plating solution comprises a solvent and the following concentrations of components:
Cu2+0.8g*L-1-1g*L-10.3g of reducing agent-1-0.5g*L-1Complexing agent 4.5g-1-5g*L-14g of stabilizer L-1-5g*L-12.5g of sodium hydroxide-1-3*L-1。
4. The method of claim 1, wherein the seed copper layer has a thickness of 800nm to 1200nm and the copper foil has a thickness of 0.5mm to 1.0 mm.
5. The method of claim 1, wherein the solder is selected from one of a Ni-based amorphous solder, a Cu-based amorphous solder, and a Ti-based amorphous solder.
6. The method of claim 1, wherein the process parameters of the braze copper foil include: the brazing temperature is 1115K-1200K, the time is 20min-30min, and the vacuum degree is 290-300 Pa.
7. The method of any one of claims 1 to 6, further comprising the steps of film pasting, exposure and development before the etching, and film stripping after the etching.
8. The method of any one of claims 1 to 6, wherein the ceramic substrate is an aluminum nitride ceramic substrate.
9. The method of any one of claims 1 to 6, further comprising the step of gold or silver deposition after the non-circuit pattern region is exposed out of the ceramic substrate.
10. A metallized ceramic prepared by the method of any one of claims 1 to 9.
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