CN113213893A - 3D printing ceramic surface copper plating process based on laser activation - Google Patents
3D printing ceramic surface copper plating process based on laser activation Download PDFInfo
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Abstract
本发明公开了一种基于激光活化的3D打印陶瓷表面镀铜工艺，属于特种材料技术领域，本发明借助增材制造的优势制备异型氧化铝基体，然后通过激光预处理来“激活”陶瓷基体表面，最后结合化学镀铜工艺，常温下实现三维形状的陶瓷基体表面定向可控的金属化，获得精确度高，复现性好的致密堆积的铜层，得到的镀层具有令人满意的粗糙度、优秀的结合力与稳定性以及良好的可焊性，四探针电阻仪测得铜层的电阻率约为3.1mΩ·cm，金属线路的极限线宽约为33.2μm；可以被广泛应用于电子与射频电路行业，如大功率发光二极管（LED）、集成电路、滤波器等。
The invention discloses a 3D printing ceramic surface copper plating process based on laser activation, which belongs to the technical field of special materials. The invention uses the advantages of additive manufacturing to prepare a special-shaped alumina matrix, and then "activates" the surface of the ceramic matrix through laser pretreatment. , Finally, combined with the electroless copper plating process, the metallization of the three-dimensional shape of the surface of the ceramic substrate can be controlled at room temperature, and the densely packed copper layer with high accuracy and good reproducibility can be obtained, and the obtained coating has satisfactory roughness. , Excellent bonding force and stability and good solderability, the resistivity of the copper layer measured by the four-probe resistance meter is about 3.1mΩ·cm, and the limit line width of the metal circuit is about 33.2μm; it can be widely used in Electronics and RF circuit industries, such as high-power light-emitting diodes (LEDs), integrated circuits, filters, etc.
Description
Technical Field
The invention belongs to the technical field of special materials, and particularly relates to a 3D printing ceramic surface copper plating process based on laser activation.
Background
With the rapid development of microelectronic technology, the complexity and density of components in electronic devices and electronic apparatuses are increasing, and therefore higher requirements are put forward on the heat dissipation and insulation of circuit substrates of the components, especially for power integrated circuit components powered by large current or large voltage. Further, with the advent of the 5G era, new demands for miniaturization of devices, particularly millimeter wave antennas, filters, and the like in 5G devices, have been made by the devices. Compared with the traditional resin-based printed circuit board, the surface metallized ceramic has good thermal conductivity, high resistance and mechanical strength, can effectively reduce thermal stress and thermal strain in a high-power electrical appliance, improves dielectric constant and the like by adjusting powder proportion, and is widely applied to the electronic and radio frequency circuit industry, such as high-power Light Emitting Diodes (LEDs), integrated circuits, filters and the like.
Miniaturization of the device may require that the original planar layout be changed to a spatial three-dimensional layout, which requires a three-dimensional curved substrate. The conventional ceramic forming processes such as roll film forming, tape casting, etc. are advantageous for manufacturing ceramic having a regular shape such as a sheet, but are difficult to manufacture a ceramic substrate having a complicated structure. Nowadays, realization of ceramic devices having a complex structure through 3D printing has become a research focus, such as ceramic filters, ceramic-based antennas, etc., which are widely used in 5G mobile communication, satellite communication, and radar systems.
The chemical plating technique is widely used in the manufacture of integrated circuits and board-mounted antennas due to its advantages of low cost, high productivity, low processing temperature, etc. However, alumina ceramics do not have catalytic activity per se and therefore require activation. The traditional palladium active method has the defects of difficult waste liquid treatment, large pollution, high cost and unsuitability for large-scale use, so the process of taking nickel and copper as active catalysts is greatly developed. However, the process using the activated catalyst has a large dependence on the formulation of the activator and is not suitable for large-scale application. The combination of laser pre-activation and electroless copper plating is an effective method for making metal lines on ceramic surfaces.
Disclosure of Invention
The invention provides a 3D printing ceramic surface copper plating process based on laser activation, which is characterized in that a special-shaped alumina matrix is prepared by means of the advantages of additive manufacturing, then the surface of the ceramic matrix is activated by laser pretreatment, finally, the oriented controllable metallization of the surface of the ceramic matrix in a three-dimensional shape is realized at normal temperature by combining a chemical copper plating process, and a densely-piled copper layer with high accuracy and good reproducibility is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
A3D printing ceramic surface copper plating process based on laser activation comprises the following steps: firstly, carrying out three-dimensional grid modeling on a material to be processed and leading in a photocuring 3D printer; secondly, curing the photosensitive slurry layer by utilizing ultraviolet light to form a ceramic framework blank; thirdly, cleaning, drying, degreasing and sintering the formed ceramic framework blank; fourthly, drawing a required pattern, adjusting the focal length of laser, and selectively irradiating the ceramic substrate; fifthly, putting the ceramic substrate with the preset pattern after the laser treatment into an electroless copper plating solution, and heating in a water bath to keep the temperature at 43.8 ℃ to obtain the surface copper-plated ceramic body.
The steps specifically include the following steps:
and 7, degreasing and sintering: degreasing and sintering the ceramic blank obtained in the step 6 after secondary curing, and cooling the ceramic blank to room temperature along with a furnace to obtain a ceramic matrix;
In the above steps, the particle size of the oxide ceramic powder in step 2 is 50 nm-300 um, the oxide ceramic is at least one of alumina, titania or zirconia, and the specific proportion is in accordance with the performance proportion of the finally required ceramic;
in the step 3, the mass ratio of the ceramic powder to the photosensitive resin is 2.5: 1-3.5: 1, adding the dispersant in an amount of 2-53% of the total mass of the slurry;
the use parameters of the 3D printer in the step 4 are as follows: the light intensity is 8000-10000 uw/cm2, the exposure time is 8-12 s, the number of bottom reinforcing layers is 3-5, the bottom reinforcing light intensity is 3-5 times, and the thickness of the photocuring printing layer is 0.05-0.08 mm;
the degreasing and sintering process in the step 7 comprises the following steps: degreasing at 0-900 deg.C, and maintaining at 120 deg.C, 240 deg.C, 300 deg.C, 420 deg.C, 500 deg.C, and 900 deg.C for two hours; the sintering stage is 900-1600 ℃, the temperature is respectively maintained at 1100 ℃, 1300 ℃ and 1500 ℃ for two hours, and the temperature rise speed is controlled to be 0.5-3 ℃/min;
the chemical copper plating solution in the step 9 comprises anhydrous copper sulfate, formaldehyde, a complexing agent, a stabilizer and an accelerator, wherein the complexing agent is glycolic acid or triethanolamine; the stabilizer is dimercapto benzothiazole or alum pentoxide; the accelerator is propyl nitrile or phenanthroline; the copper plating time is not less than 80 min.
Has the advantages that: the invention provides a 3D printing ceramic surface copper plating process based on laser activation, and compared with the prior art, the process has the following advantages:
(1) according to the invention, through the good combination of three-dimensional modeling and 3D printing, the component content and the internal structure of the composite material can be directly designed and manufactured, and a composite material processing mode is innovated;
(2) based on the photocuring 3D printing technology, the combined printing of diversified lattice units can be realized, the design channel is widened, the structural design can be optimized in a targeted manner aiming at different application scenes, and the diversification function of the composite material is realized;
(3) the copper plating processing method of the invention provides possibility for the use of the ceramic substrate in miniaturized integrated circuits, antennas, filters and other radio frequency devices with simple, low-cost and effective method;
(4) the method realizes the oriented controllable metallization of the surface of the ceramic matrix with the three-dimensional shape at normal temperature, obtains the copper layer which is densely accumulated and has high precision and good reproducibility, and the obtained plating layer has better roughness, excellent bonding force and stability and good weldability, the resistivity of the copper layer measured by a four-probe resistance instrument is about 3.1m omega cm, and the limit line width of a metal line is about 33.2 mu m; the method can be widely applied to the electronic and radio frequency circuit industries, such as high-power Light Emitting Diodes (LEDs), integrated circuits, filters and the like.
Drawings
FIG. 1 is a flow chart of a 3D printing ceramic surface copper plating process based on laser activation in an embodiment of the invention;
FIG. 2 is a graph of the effect of copper plating using the process in an embodiment of the present invention;
FIG. 3 is a diagram of a DLP photocuring printer in an embodiment of the invention;
FIG. 4 is a pictorial view of a fiber optic pulsed laser;
FIG. 5 is a schematic diagram of a Bluetooth antenna manufactured by a 3D printing ceramic surface copper plating process based on laser activation in an embodiment of the invention;
FIG. 6 is a schematic diagram of a special-shaped quadrifilar helical antenna manufactured by a 3D printing ceramic surface copper plating process based on laser activation in the embodiment of the invention;
FIG. 7 shows the surface roughness of the copper plating layer obtained by the method in example 2 of the present invention;
FIG. 8 shows the resistivity and the thickness of the copper plating layer obtained by this method in example 2 of the present invention.
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
example 1
As shown in fig. 1, a process for manufacturing a bluetooth antenna based on a 3D printing ceramic surface copper plating process activated by laser comprises the following steps:
and 7, degreasing and sintering: degreasing and sintering the ceramic blank obtained in the step 6 after secondary curing, wherein the degreasing stage is carried out at 0-900 ℃, and the temperature is respectively kept at 120 ℃, 240 ℃, 300 ℃, 420 ℃, 500 ℃ and 900 ℃ for two hours; the sintering stage is 900-1600 ℃, the temperature is respectively kept at 1100 ℃, 1300 ℃ and 1500 ℃ for two hours, the temperature rise speed is controlled to be 0.5-3 ℃/min, and then the ceramic matrix is obtained after the ceramic matrix is cooled to the room temperature along with the furnace;
The electroless copper plating solution in the step 9 comprises anhydrous copper sulfate, formaldehyde, a complexing agent, a stabilizer and an accelerator; the complexing agent is glycolic acid or triethanolamine; the stabilizer is dimercapto benzothiazole or alum pentoxide; the accelerator is propyl nitrile or phenanthroline.
Example 2
As shown in fig. 1, a process for manufacturing a special-shaped quadrifilar helix antenna by a 3D printing ceramic surface copper plating process based on laser activation comprises the following steps:
and 7, degreasing and sintering: degreasing and sintering the ceramic blank obtained in the step 6 after secondary curing, wherein the degreasing stage is carried out at 0-900 ℃, and the temperature is respectively kept at 120 ℃, 240 ℃, 300 ℃, 420 ℃, 500 ℃ and 900 ℃ for two hours; the sintering stage is 900-1600 ℃, the temperature is respectively kept at 1100 ℃, 1300 ℃ and 1500 ℃ for two hours, the temperature rise speed is controlled to be 0.5-3 ℃/min, and then the ceramic matrix is obtained after the ceramic matrix is cooled to the room temperature along with the furnace;
The electroless copper plating solution in the step 9 comprises anhydrous copper sulfate, formaldehyde, a complexing agent, a stabilizer and an accelerator; the complexing agent is glycolic acid or triethanolamine; the stabilizer is dimercapto benzothiazole or alum pentoxide; the accelerator is propyl nitrile or phenanthroline.
The plated layer after copper plating as shown in FIG. 2 was tested
The surface roughness test is carried out by using a non-contact type roughness meter, the test result is shown in figure 7, the test result shows that the roughness change is small, and the surface quality is good.
The resistivity and the coating thickness are tested by using the four-probe resistance instrument probe and the contact type three-dimensional contourgraph, the test result is shown in fig. 8, the resistivity of the coating is lower and lower along with the increase of the chemical plating reaction time, namely, the conductivity is gradually improved and finally tends to be balanced, and the coating thickness also becomes thicker along with the increase of the time to reach the thickness required by the electronic field.
The above description is only for the preferred embodiment of the present invention and should not be used to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A3D printing ceramic surface copper plating process based on laser activation is characterized by comprising the following steps: firstly, carrying out three-dimensional grid modeling on a material to be processed and leading in a photocuring 3D printer; secondly, curing the photosensitive slurry layer by utilizing ultraviolet light to form a ceramic framework blank; thirdly, cleaning, drying, degreasing and sintering the formed ceramic framework blank; fourthly, drawing a required pattern, adjusting the focal length of laser, and selectively irradiating the ceramic substrate; fifthly, putting the ceramic substrate with the preset pattern after the laser treatment into an electroless copper plating solution, and heating in a water bath to keep the temperature at 43.8 ℃ to obtain the surface copper-plated ceramic body.
2. The laser activation based 3D printed ceramic surface copper plating process according to claim 1, characterized in that the process comprises in particular the steps of:
step 1, modeling: according to different application backgrounds, a required ceramic three-dimensional structure diagram is designed by modeling software and stored as an STL format file;
step 2, ball milling and mixing: mixing oxide ceramic powder and performing ball milling;
step 3, preparing slurry: adding the mixed ceramic powder obtained in the step 2 into photosensitive resin and a dispersing agent, and putting the mixture into a vacuum dispersion machine for uniformly mixing;
step 4, forming of a blank: leading the model file obtained in the step 1 into a photocuring 3D printer, and printing the slurry obtained in the step 3 into a ceramic blank by a photocuring forming method;
step 5, green body treatment: adding the ceramic blank obtained in the step (4) into absolute ethyl alcohol, ultrasonically cleaning to remove surface bonding slurry, and drying;
step 6, surface secondary curing: putting the dried blank obtained in the step 5 into an ultraviolet curing furnace for secondary curing treatment, wherein the curing time is 5 minutes;
and 7, degreasing and sintering: degreasing and sintering the ceramic blank obtained in the step 6 after secondary curing, and cooling the ceramic blank to room temperature along with a furnace to obtain a ceramic matrix;
step 8, laser activation: drawing a required pattern on a laser control display, adjusting the laser focal length according to the laser wavelength, and selectively irradiating the ceramic substrate obtained in the step 7 according to the designed pattern;
step 9, electroless copper plating: placing the ceramic substrate with the preset pattern after the laser treatment into an electroless copper plating solution, keeping the temperature at 43.8 ℃, and determining the copper plating time according to the required thickness of a copper plating layer;
step 10, anti-oxidation treatment: and after the chemical copper plating is finished, immersing the finished product into an antioxidant for carrying out anti-oxidation treatment to obtain a surface copper plated ceramic body.
3. The laser activation based 3D printing ceramic surface copper plating process according to claim 2, wherein the oxide ceramic powder in the step 2 has a particle size of 50 nm-300 um.
4. The laser activation based 3D printed ceramic surface copper plating process according to claim 2 or 3, characterized in that the oxide based ceramic in step 2 is at least one of alumina, titania or zirconia.
5. The laser activation based 3D printed ceramic surface copper plating process according to claim 2, wherein the mass ratio of the ceramic powder to the photosensitive resin in the step 3 is 2.5: 1-3.5: 1, the addition amount of the dispersing agent is 2-53% of the total mass of the slurry.
6. The laser activation based 3D printed ceramic surface copper plating process according to claim 2, characterized in that the 3D printer usage parameters in step 4 are: the light intensity is 8000-10000 uw/cm2The exposure time is 8-12 s, the number of bottom reinforcing layers is 3-5, the bottom reinforcing light intensity is 3-5 times, and the thickness of the photocuring printing layer is 0.05-0.08 mm.
7. The laser activation based 3D printing ceramic surface copper plating process according to claim 2, wherein the degreasing sintering process in the step 7 is as follows: degreasing at 0-900 deg.C, and maintaining at 120 deg.C, 240 deg.C, 300 deg.C, 420 deg.C, 500 deg.C, and 900 deg.C for two hours; and 900-1600 ℃ is a sintering stage, the temperature is respectively kept at 1100 ℃, 1300 ℃ and 1500 ℃ for two hours, and the temperature rise speed is controlled to be 0.5-3 ℃/min.
8. The laser activation based 3D printed ceramic surface copper plating process according to claim 2, characterized in that the electroless copper plating solution in step 9 comprises anhydrous copper sulfate, formaldehyde, complexing agents, stabilizers, accelerators.
9. The laser activation based 3D printed ceramic surface copper plating process according to claim 8, wherein the complexing agent is glycolic acid or triethanolamine; the stabilizer is dimercapto benzothiazole or alum pentoxide; the accelerator is propyl nitrile or phenanthroline.
10. The laser activation based 3D printed ceramic surface copper plating process according to claim 2, characterized in that the copper plating time in step 9 is not less than 80 min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110472611.6A CN113213893A (en) | 2021-04-29 | 2021-04-29 | 3D printing ceramic surface copper plating process based on laser activation |
| PCT/CN2021/093206 WO2022227118A1 (en) | 2021-04-29 | 2021-05-12 | Laser activation-based copper plating process for 3d-printed ceramic surface |
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| CN202110472611.6A CN113213893A (en) | 2021-04-29 | 2021-04-29 | 3D printing ceramic surface copper plating process based on laser activation |
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| CN202110472611.6A Pending CN113213893A (en) | 2021-04-29 | 2021-04-29 | 3D printing ceramic surface copper plating process based on laser activation |
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| WO (1) | WO2022227118A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163259A (en) * | 2021-12-14 | 2022-03-11 | 东莞智昊光电科技有限公司 | Method for metallizing ceramic surfaces and metallized ceramics |
| CN114770695A (en) * | 2022-04-12 | 2022-07-22 | 山东大学 | Method for photocuring 3D printing ceramic |
| CN114956793A (en) * | 2022-06-01 | 2022-08-30 | 东南大学 | Ceramic slurry for 3D printing ceramic electronic circuit, preparation technology thereof and mixed additive manufacturing method |
| CN115178881A (en) * | 2022-08-01 | 2022-10-14 | 成都科宁达材料有限公司 | Surface treatment method of alumina ceramic and alumina ceramic/metal heterogeneous brazing method |
| CN117843353A (en) * | 2023-12-29 | 2024-04-09 | 太仓市金鹿电镀有限公司 | Environment-friendly copper plating process for alumina ceramic substrate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI478641B (en) * | 2014-01-20 | 2015-03-21 | Rhema Technology & Trading Company Ltd | Ceramic circuit board of laser plate copper and manufacturing method thereof |
| CN109774132A (en) * | 2019-03-04 | 2019-05-21 | 东南大学 | A manufacturing method of circuit board based on photocuring 3D printing technology |
| CN109912303A (en) * | 2019-04-24 | 2019-06-21 | 南京航空航天大学 | A kind of calcium phosphate/zirconia gradient porous scaffold and preparation method and application |
| CN110272273A (en) * | 2019-07-22 | 2019-09-24 | 上海应用技术大学 | The controlled pore hydroxyl apatite bioceramic bracket and preparation method of 3D printing |
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2021
- 2021-04-29 CN CN202110472611.6A patent/CN113213893A/en active Pending
- 2021-05-12 WO PCT/CN2021/093206 patent/WO2022227118A1/en active Application Filing
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163259A (en) * | 2021-12-14 | 2022-03-11 | 东莞智昊光电科技有限公司 | Method for metallizing ceramic surfaces and metallized ceramics |
| CN114770695A (en) * | 2022-04-12 | 2022-07-22 | 山东大学 | Method for photocuring 3D printing ceramic |
| CN114956793A (en) * | 2022-06-01 | 2022-08-30 | 东南大学 | Ceramic slurry for 3D printing ceramic electronic circuit, preparation technology thereof and mixed additive manufacturing method |
| CN115178881A (en) * | 2022-08-01 | 2022-10-14 | 成都科宁达材料有限公司 | Surface treatment method of alumina ceramic and alumina ceramic/metal heterogeneous brazing method |
| CN117843353A (en) * | 2023-12-29 | 2024-04-09 | 太仓市金鹿电镀有限公司 | Environment-friendly copper plating process for alumina ceramic substrate |
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| WO2022227118A1 (en) | 2022-11-03 |
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