CN115819120A - Pretreatment method of ceramic substrate and method for coating ceramic substrate - Google Patents
Pretreatment method of ceramic substrate and method for coating ceramic substrate Download PDFInfo
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Abstract
The invention belongs to the technical field of vacuum coating sputtering, and particularly relates to a pretreatment method of a ceramic substrate and a method for coating the ceramic substrate. The method comprises the steps of firstly, placing a ceramic substrate in an alkaline cleaning solution for ultrasonic cleaning to remove organic pollutants, protective film layers and the like on the surface of the ceramic and in the hole, wherein the ultrasonic cleaning can remove laser slag remained in the ceramic hole of the through hole after laser drilling, and then further remove residual grease, organic pollutants and the alkaline cleaning solution on the surface of the ceramic through calcination; and finally, etching and cleaning fine dust on the surface of the ceramic by an argon dry method and activating molecules on the surface of the ceramic, so as to improve the binding force between the ceramic substrate and the metal film layer.
Description
Technical Field
The invention belongs to the technical field of vacuum coating sputtering, and particularly relates to a pretreatment method of a ceramic substrate and a method for coating the ceramic substrate.
Background
There are various coating methods, including low-cost solution coating such as chemical reaction, sol-gel, electroplating, etc., and vacuum evaporation coating, sputtering coating, ion coating, and chemical vapor deposition which rely on expensive equipment. Sputtering is widely used in the production of thin films due to its advantages such as reliability, repeatability and uniformity.
The support for the film in sputter coating is typically a ceramic substrate. The existing ceramic substrate for manufacturing a film circuit, particularly a polished substrate, has smooth surface and small roughness, so that the bonding force between a metal film layer and the ceramic substrate is poor. In addition, after the existing through-hole ceramics such as aluminum oxide and aluminum nitride are drilled by laser, more laser slag is often left in the through-hole, and after the metal film is covered, the ceramics in the through-hole cannot be tightly combined with the metal film layer, so that air gaps exist, a high-temperature bubbling phenomenon is caused, and the quality of a coating film is influenced.
Disclosure of Invention
In view of the above, the present invention provides a method for pretreating a ceramic substrate and a method for coating a ceramic substrate, in which laser slag on the surface and inside the pores of the ceramic substrate is removed by pretreating the ceramic substrate before sputter coating, thereby preventing the occurrence of high-temperature bubbling after coating, and the bonding force between the ceramic and the metal film is improved by activating the surface of the ceramic substrate.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a pretreatment method of a ceramic substrate, which comprises the following steps:
carrying out ultrasonic cleaning on the ceramic substrate in an alkaline cleaning solution to obtain a clean ceramic substrate;
calcining the clean ceramic substrate in a nitrogen protection atmosphere to obtain a calcined ceramic substrate;
and performing argon dry etching on the calcined ceramic substrate.
Preferably, the alkaline cleaning solution comprises the following components in percentage by mass: 5 to 15 percent of polyethylene glycol, 10 to 20 percent of glycerol, 20 to 30 percent of sodium hydroxide and 45 to 55 percent of pure water.
Preferably, the frequency of the ultrasonic cleaning is 120-300 kHz, the power is 150-300W, and the time is 30-60 min.
Preferably, the calcining comprises:
heating to a first temperature for first heat preservation, wherein the first temperature is 25-30 ℃, and the first heat preservation time is 100-120 min;
raising the temperature from the first temperature to a second temperature for second heat preservation, wherein the second temperature is 450-500 ℃, and the second heat preservation time is 80-100 min;
raising the temperature from the second temperature to a third temperature for third heat preservation, wherein the third temperature is 1000-1100 ℃, and the third heat preservation time is 100-150 min;
raising the temperature from the third temperature to a fourth temperature, and carrying out fourth heat preservation, wherein the fourth temperature is 750-800 ℃, and the fourth heat preservation time is 120-150 min;
cooling from the fourth temperature to a fifth temperature, and performing fifth heat preservation, wherein the fifth temperature is 450-500 ℃, and the fifth heat preservation time is 120-170 min;
and reducing the temperature from the fifth temperature to a sixth temperature for sixth heat preservation, wherein the sixth temperature is 100-120 ℃, and the sixth heat preservation time is 120-150 min.
Preferably, the pressure of the calcination is 1.01 to 1.50X 10 5 Pa。
Preferably, the power of the argon dry etching is 250-300W, and the time is 3-5 min.
Preferably, the flow rate of argon in the argon dry etching is 60-80 mL/min.
Preferably, the purity of the nitrogen in the nitrogen protection atmosphere is not lower than 99.99%.
Preferably, after the ultrasonic cleaning in the alkaline cleaning solution, the method further comprises: and (3) carrying out ultrasonic cleaning and drying on the ceramic substrate obtained by ultrasonic cleaning in the alkaline cleaning solution in water in sequence.
The invention also provides a method for coating the ceramic substrate, which comprises the following steps: the ceramic substrate obtained by the pretreatment method in the technical scheme is subjected to sputtering of a seed layer and an electrogilding layer in sequence to obtain a plated film layer; the seed layer comprises tantalum nitride, titanium tungsten, nickel and gold which are sputtered in sequence, or titanium tungsten and gold which are sputtered in sequence.
The invention provides a pretreatment method of a ceramic substrate, which comprises the following steps: carrying out ultrasonic cleaning on the ceramic substrate in an alkaline cleaning solution to obtain a clean ceramic substrate; calcining the clean ceramic substrate in a nitrogen protection atmosphere to obtain a calcined ceramic substrate; and carrying out argon dry etching on the calcined ceramic substrate. The method comprises the steps of firstly placing a ceramic substrate in an alkaline cleaning solution for ultrasonic cleaning to remove organic pollutants, protective film layers and the like on the surface of the ceramic and in the hole, wherein the ultrasonic cleaning can enhance the cleaning effect of the alkaline cleaning solution to remove, laser slag remained in the through hole ceramic hole after laser drilling is further removed by calcining, the residual grease, organic pollutants and alkaline cleaning solution on the surface of the ceramic, the loose structure of the through hole ceramic after laser drilling can be densified by calcining, nitrogen introduced in the calcining process can be used as a protective gas in the calcining process to protect the nitrogen ceramic from reacting with oxygen at high temperature, and can also be used as an airflow gas to take away the slag in the through hole ceramic hole, so that the ceramic in the hole is tightly combined with the metal film layer, no air gap exists, and the phenomenon of high-temperature bubbling is avoided; and finally, cleaning fine dust on the surface of the ceramic substrate by argon dry etching and activating molecules on the surface of the ceramic, so as to improve the binding force between the ceramic substrate and the metal film layer.
Drawings
FIG. 1 is a graph showing the results of a bonding test of a plating film of a ceramic substrate obtained in example 1 of the present invention and a plating film of a ceramic substrate not subjected to a pretreatment in comparative example 1;
FIG. 2 is a graph showing the results of a 3M tape adhesion test of the plating films of the ceramic substrate obtained in example 1 of the present invention and the ceramic substrate of comparative example 1 without pretreatment;
FIG. 3 is a graph showing the results of a high-temperature test of the plating films of the ceramic substrate obtained in example 1 of the present invention and the ceramic substrate of comparative example 1 without pretreatment.
Detailed Description
The invention provides a pretreatment method of a ceramic substrate, which comprises the following steps:
carrying out ultrasonic cleaning on the ceramic substrate in an alkaline cleaning solution to obtain a clean ceramic substrate;
calcining the clean ceramic substrate in a nitrogen protection atmosphere to obtain a calcined ceramic substrate;
and performing argon dry etching on the calcined ceramic substrate.
Unless otherwise specified, the present invention does not require any particular source of the raw materials used, and commercially available products known to those skilled in the art may be used.
The ceramic substrate is subjected to ultrasonic cleaning in an alkaline cleaning solution to obtain the clean ceramic substrate.
In the present invention, the ceramic substrate preferably comprises a through-hole ceramic and/or a blind-hole ceramic; the thickness of the ceramic substrate is preferably 0.1-2 mm, more preferably 0.1-1.5 mm, and in the embodiment of the invention, the thickness of the ceramic is specifically 0.127mm, 0.254mm, 0.381mm, 0.508mm, 1.0mm or 1.5mm; the through-hole diameter of the through-hole ceramic is preferably 0.05 to 1mm, and more preferably 0.08 to 0.9mm. In the embodiment of the invention, the through hole diameter of the through hole ceramic is specifically 0.08mm, 0.15mm, 0.23mm, 0.3mm, 0.6mm or 0.9mm; the material of the ceramic substrate comprises aluminum oxide and/or aluminum nitride.
In the invention, the alkaline cleaning solution preferably comprises the following components in percentage by mass: 5 to 15 percent of polyethylene glycol, 10 to 20 percent of glycerol, 20 to 30 percent of sodium hydroxide and 45 to 55 percent of pure water.
The polyethylene glycol in the alkaline cleaning solution has the functions of providing dispersibility and adhesiveness, so that dust and residues in the through hole are easier to clean and fall off; the glycerol has the function of providing intersolubility of all effective components in the cleaning solution; the sodium hydroxide is used for removing grease on the surface of the ceramic substrate; pure water functions as a solvent.
In the present invention, the mass percentage of the polyethylene glycol in the alkaline cleaning solution is more preferably 8 to 12%, the mass percentage of the glycerin is more preferably 13 to 17%, the mass percentage of the sodium hydroxide is more preferably 23 to 27%, and the mass percentage of the pure water is more preferably 48 to 52%.
In the present invention, the molecular weight of the polyethylene glycol is preferably 200 to 600, more preferably 300 to 500.
In the embodiment of the invention, the alkaline cleaning agent specifically comprises the following components in percentage by mass: 10% of polyethylene glycol, 15% of glycerol, 25% of sodium hydroxide and 50% of pure water.
The invention adopts alkaline cleaning solution to clean organic pollutants, protective film layers and the like on the surface of the ceramic and in the hole, but can not clean the laser residues left on the surface of the ceramic and in the hole after melting and condensation.
In the present invention, the frequency of the ultrasonic cleaning is preferably 120 to 300kHz, more preferably 150 to 300kHz, the power is preferably 150 to 300W, more preferably 200 to 300W, and the time is preferably 30 to 60min, more preferably 40 to 60min.
The invention adopts ultrasonic to enhance the cleaning effect of the alkaline cleaning solution and remove loose and easily-fallen excess on the surface and in the hole of the ceramic, such as laser slag remained in the hole of the ceramic after laser drilling.
After the ultrasonic cleaning is performed in the alkaline cleaning solution, the method preferably further comprises the following steps: and sequentially carrying out ultrasonic cleaning and drying on the ceramic substrate obtained by ultrasonic cleaning in the alkaline cleaning solution in water. In the present invention, the frequency of the ultrasonic cleaning in water is preferably 120 to 300kHz, more preferably 280 to 300kHz, the power is preferably 150 to 300W, more preferably 200 to 300W, the time is preferably 30 to 60min, more preferably 40 to 60min, and the number of times is preferably 3. In the present invention, the drying is preferably performed by blowing with nitrogen gas.
The invention adopts pure water ultrasonic cleaning to clean the alkaline cleaning solution remained on the surface and in the hole of the ceramic.
After the clean ceramic substrate is obtained, the clean ceramic substrate is calcined in a nitrogen protection atmosphere to obtain a calcined ceramic substrate.
In the present invention, the calcination comprises:
raising the temperature to a first temperature for first heat preservation, wherein the first temperature is preferably 25-30 ℃, more preferably 30 ℃, and the first heat preservation time is preferably 100-120 min, more preferably 110-120 min;
raising the temperature from the first temperature to a second temperature for second heat preservation, wherein the second temperature is preferably 450-500 ℃, more preferably 500 ℃, and the second heat preservation time is preferably 80-100 min, more preferably 80-90 min;
raising the temperature from the second temperature to a third temperature for third heat preservation, wherein the third temperature is preferably 1000-1100 ℃, more preferably 1100 ℃, and the time for the third heat preservation is preferably 100-150 min, more preferably 100-120 min;
raising the temperature from the third temperature to a fourth temperature for fourth heat preservation, wherein the fourth temperature is preferably 750-800 ℃, more preferably 800 ℃, and the fourth heat preservation time is preferably 120-150 min, more preferably 120-130 min;
cooling from the fourth temperature to a fifth temperature, and performing fifth heat preservation, wherein the fifth temperature is preferably 450-500 ℃, and more preferably 500 ℃, and the time of the fifth heat preservation is preferably 120-170 min, and more preferably 120-150 min;
and reducing the temperature from the fifth temperature to a sixth temperature for sixth heat preservation, wherein the sixth temperature is preferably 100-120 ℃, more preferably 110-120 ℃, and the time for the sixth heat preservation is preferably 120-150 min, more preferably 120-130 min.
In the invention, the purity of the nitrogen in the nitrogen protection atmosphere is preferably not lower than 99.99%; the pressure of the calcination is preferably 1.01 to 1.50X 10 5 Pa, more preferably 1.1 to 1.2X 10 5 Pa; the equipment used for the calcination is preferably a quartz tube type atmosphere furnace.
The invention removes grease, organic pollutants and residual alkaline cleaning solution on the surface of the ceramic substrate by calcination, and the calcination can also make the loose ceramic structure compact after laser drilling. According to the invention, nitrogen is introduced in the calcining process, firstly, the nitrogen is used as a protective gas in the calcining process to protect the nitrogen ceramic from reacting with oxygen at high temperature, secondly, the nitrogen is used as an airflow gas to take away slag remained in the ceramic hole after laser drilling, so that loose slag does not exist in the ceramic hole, and after the metal film is covered, the ceramic and the metal film layer on the surface in the hole are tightly combined, and no air gap exists, so that the high-temperature bubbling phenomenon is avoided.
After the calcined ceramic is obtained, the calcined ceramic is subjected to argon dry etching to obtain the pretreated ceramic.
In the invention, the power of the argon dry etching is preferably 250-300W, more preferably 300W, the vacuum degree is preferably 0.5-1 Pa, more preferably 0.5Pa; the time is preferably 3 to 5min, more preferably 3min; the flow rate of argon in the argon dry etching is preferably 60-80 mL/min, and more preferably 80mL/min.
According to the invention, the calcined ceramic is preferably preheated before argon dry etching is carried out; the preheating temperature is preferably 150 to 200 ℃, more preferably 200 ℃, and the time is preferably 3 to 5min, more preferably 5min.
The invention activates the cooled ceramic by preheating the calcined ceramic before argon dry etching.
In the invention, the argon dry etching is preferably to wipe the carrier plate clean by absolute ethyl alcohol along the X \ Y axis direction, place the calcined ceramic on the carrier plate, enter a sputtering chamber, preheat and then carry out argon dry etching.
In the invention, the argon dry etching has the functions of cleaning fine dust on the surface of the ceramic substrate and activating molecules on the surface of the ceramic, thereby improving the binding force between the ceramic substrate and the metal film layer.
The invention also provides a method for coating the ceramic substrate, which comprises the following steps: and (3) sequentially sputtering the seed layer and electroplating the gold layer on the ceramic substrate obtained by the pretreatment method in the technical scheme to obtain the coating layer.
In the invention, the seed layer comprises tantalum nitride, titanium tungsten, nickel and gold which are sputtered in sequence, or titanium tungsten and gold which are sputtered in sequence, preferably titanium tungsten, nickel and gold which are sputtered in sequence; the sputtering power of each sublayer is preferably 1500-1800W independently, more preferably 1800W independently, the time is preferably 20-30 min independently, more preferably 30min independently, the pressure is preferably 0.5-1 Pa independently, more preferably 0.5-0.8 Pa independently, the temperature is preferably 150-200 ℃, more preferably 150-180 ℃; the total thickness of the various sublayers is preferably 0.3-0.5 μm, more preferably 0.5 μm; the thickness of the tantalum nitride seed layer is preferably 0.03-0.07 μm, and more preferably 0.05 μm; the thickness of the titanium tungsten seed layer is preferably 0.1-0.2 μm, and more preferably 0.15 μm; the thickness of the nickel seed layer is preferably 0.1-0.2, and more preferably 0.15 μm; the thickness of the gold seed layer is preferably 0.1 to 0.2 μm, and more preferably 0.2 μm.
In the present invention, the thickness of the gold plating layer is preferably 1 to 2 μm, more preferably 2 μm; the voltage of the electroplating is preferably 1-4V, more preferably 2V, the current is preferably 0.1-0.2A, more preferably 0.2A, and the current efficiency is preferably 80-100%, more preferably 90%; the electroplating solution is preferably a gold potassium citrate solution; the time of the electroplating is preferably 15-25 min, more preferably 20min, and the pH value of the electroplating solution is preferably 5-8, more preferably 6; the cathode used for electroplating is preferably a titanium mesh, and the anode used for electroplating is preferably a platinum titanium mesh; the area ratio of the cathode to the anode is preferably (0.5-1.5) to (1-2), more preferably 1; the temperature of the plating solution is preferably 50 to 70 ℃, more preferably 60 ℃.
The technical solutions in the present invention will be clearly and completely described below with reference to the embodiments of the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Using 0.127mm thick ceramic and 0.080mm through hole diameter ceramic, the quantity of which is enough to be distributed on the sputtering carrier plate, soaking a rack loaded with substrates into alkaline cleaning solution (comprising 10% of polyethylene glycol, 15% of glycerol, 25% of sodium hydroxide and 50% of pure water) to enable the cleaning solution to completely soak the substrates, carrying out ultrasonic treatment at the frequency of 300kHz and the power of 300W for 30min, soaking the substrates in the pure water for continuous ultrasonic treatment for 30min, repeating the ultrasonic treatment of the pure water for 3 times, gradually blowing the liquid on the substrates by nitrogen, then placing the ceramic substrates into a quartz tube type atmosphere furnace, introducing nitrogen with the purity of not less than 99.99% into the furnace tube, and enabling the gas pressure in the furnace tube to reach 1.01 multiplied by 10 5 After Pa, calcination was carried out, the temperature profile of calcination being set: the first temperature is 30 ℃, the heat preservation time is 100min, the second temperature is 500 ℃, the heat preservation time is 80min, the third temperature is 1100 ℃, the heat preservation time is 120min, the fourth temperature is 800 ℃, the heat preservation time is 100min, the fifth temperature is 500 ℃, the heat preservation time is 120min, the sixth temperature is 120 ℃, and the heat preservation time is 120min; and after heating is stopped, taking out the ceramic substrate, wiping the support plate clean by absolute ethyl alcohol along the X \ Y axis direction, placing the ceramic substrate on the support plate, entering a sputtering chamber with the vacuum degree of 0.5Pa, heating at 200 ℃ for 5min, and performing argon dry etching at 300W by using argon with the flow rate of 80mL/min for 3min to obtain the pretreated ceramic.
Example 2
Using ceramic with the thickness of 0.254mm and the diameter of a through hole of 0.15mm and blind hole ceramic with enough quantity of sputtering carrier plates, soaking a hanging rack loaded with a substrate into alkaline cleaning liquid (comprising 10 percent of polyethylene glycol, 15 percent of glycerol, 25 percent of sodium hydroxide and 50 percent of pure water) to ensure that the cleaning liquid completely soaks the substrate, carrying out ultrasonic treatment at the frequency of 300kHz and the power of 300W for 30min, soaking the substrate in the pure water for continuous ultrasonic treatment for 30min, repeating the ultrasonic treatment of the pure water for 3 times, using nitrogen to gradually blow and dry the liquid on the substrate, placing the ceramic substrate in a quartz tube type atmosphere furnace, introducing nitrogen with the purity of not less than 99.99 percent into a furnace tube, and ensuring that the pressure of the gas in the furnace tube reaches the pressure of the gasTo 1.01X 10 5 After Pa, calcination was carried out, the temperature profile of calcination being set: the first temperature is 30 ℃, the heat preservation time is 100min, the second temperature is 500 ℃, the heat preservation time is 80min, the third temperature is 1100 ℃, the heat preservation time is 120min, the fourth temperature is 800 ℃, the heat preservation time is 100min, the fifth temperature is 500 ℃, the heat preservation time is 120min, the sixth temperature is 120 ℃, and the heat preservation time is 120min; and after heating is stopped, taking out the ceramic substrate, wiping the support plate clean by absolute ethyl alcohol along the X \ Y axis direction, placing the ceramic substrate on the support plate, entering a sputtering chamber with the vacuum degree of 0.5Pa, heating at 200 ℃ for 5min, and performing argon dry etching at 300W by using argon with the flow rate of 80mL/min for 3min to obtain the pretreated ceramic.
Example 3
Using 0.381mm thick ceramic and 0.23mm through hole diameter ceramic, the quantity is enough to be covered with sputtering carrier plate, soaking the rack with substrate in alkaline cleaning solution (including 10% of polyethylene glycol, 15% of glycerin, 25% of sodium hydroxide and 50% of pure water) to make the cleaning solution completely soak the substrate, making ultrasonic treatment at 300kHz and 300W for 30min, soaking in pure water and continuing ultrasonic treatment for 30min, repeating ultrasonic treatment for 3 times, using nitrogen to gradually blow-dry the liquid on the substrate, placing the ceramic substrate in quartz tube type atmosphere furnace, introducing nitrogen whose purity is not less than 99.99% into the furnace tube, and making the gas pressure in the furnace tube reach 1.01 x 10 5 After Pa, calcination was carried out, the temperature profile of calcination being set: the first temperature is 30 ℃, the heat preservation time is 100min, the second temperature is 500 ℃, the heat preservation time is 80min, the third temperature is 1100 ℃, the heat preservation time is 120min, the fourth temperature is 800 ℃, the heat preservation time is 100min, the fifth temperature is 500 ℃, the heat preservation time is 120min, the sixth temperature is 120 ℃, and the heat preservation time is 120min; and after heating is stopped, taking out the ceramic substrate, wiping the support plate clean by absolute ethyl alcohol along the X \ Y axis direction, placing the ceramic substrate on the support plate, entering a sputtering chamber with the vacuum degree of 0.5Pa, heating at 200 ℃ for 5min, and performing argon dry etching at 300W by using argon with the flow rate of 80mL/min for 3min to obtain the pretreated ceramic.
Example 4
Using 0.508mm thick ceramic and 0.3mm diameter through hole ceramic, the quantity is enough to be covered with sputtering carrier plate, soaking the rack with substrate into alkaline cleaning solution (including 10% of polyethylene glycol, 15% of glycerin, 25% of sodium hydroxide and 50% of pure water) to make the cleaning solution completely soak the substrate, after making ultrasonic treatment with frequency of 300kHz and power of 300W for 30min, soaking in pure water and making ultrasonic treatment for 30min, after repeating ultrasonic treatment for 3 times with pure water, using nitrogen to gradually blow-dry the liquid on the substrate, placing the ceramic substrate in quartz tube type atmosphere furnace, introducing nitrogen whose purity is not less than 99.99% into the furnace tube, and making the gas pressure in the furnace tube reach 1.01 x 10 5 After Pa, calcination was carried out, the temperature profile of calcination being set: the first temperature is 30 ℃, the heat preservation time is 100min, the second temperature is 500 ℃, the heat preservation time is 80min, the third temperature is 1100 ℃, the heat preservation time is 120min, the fourth temperature is 800 ℃, the heat preservation time is 100min, the fifth temperature is 500 ℃, the heat preservation time is 120min, the sixth temperature is 120 ℃, and the heat preservation time is 120min; and after heating is stopped, taking out the ceramic substrate, wiping the support plate clean by absolute ethyl alcohol along the X \ Y axis direction, placing the ceramic substrate on the support plate, entering a sputtering chamber with the vacuum degree of 0.5Pa, heating at 200 ℃ for 5min, and performing argon dry etching at 300W by using argon with the flow rate of 80mL/min for 3min to obtain the pretreated ceramic.
Example 5
Using ceramics with the thickness of 1.0mm and the diameter of a through hole of 0.6mm and blind hole ceramics with enough quantity to be fully distributed with a sputtering carrier plate, soaking a hanging rack for loading a substrate into alkaline cleaning solution (comprising 10 percent of polyethylene glycol, 15 percent of glycerol, 25 percent of sodium hydroxide and 50 percent of pure water) to ensure that the cleaning solution completely soaks the substrate, carrying out ultrasonic treatment at the frequency of 300kHz and the power of 300W for 30min, soaking the substrate in the pure water for ultrasonic treatment for 30min, repeating the ultrasonic treatment of the pure water for 3 times, using nitrogen to gradually blow and completely blow and dry the liquid on the substrate, placing the ceramic substrate in a quartz tube type atmosphere furnace, introducing nitrogen with the purity of not less than 99.99 percent into a furnace tube, and ensuring that the gas pressure in the furnace tube reaches 1.01 multiplied by 10 5 After Pa, calcination was carried out, the temperature profile of calcination being set: the first temperature is 30 deg.C, the holding time is 100min, the second temperature is 500 deg.C, and the holding time is 80min, the third temperature is 1100 ℃, the heat preservation time is 120min, the fourth temperature is 800 ℃, the heat preservation time is 100min, the fifth temperature is 500 ℃, the heat preservation time is 120min, the sixth temperature is 120 ℃, and the heat preservation time is 120min; and after heating is stopped, taking out the ceramic substrate, wiping the support plate clean by absolute ethyl alcohol along the X \ Y axis direction, placing the ceramic substrate on the support plate, entering a sputtering chamber with the vacuum degree of 0.5Pa, heating at 200 ℃ for 5min, and performing argon dry etching at 300W by using argon with the flow rate of 80mL/min for 3min to obtain the pretreated ceramic.
Example 6
Using ceramics with the thickness of 1.5mm and the diameter of a through hole of 0.9mm and blind hole ceramics with enough quantity to be fully distributed with a sputtering carrier plate, soaking a hanging rack for loading a substrate into alkaline cleaning solution (comprising 10 percent of polyethylene glycol, 15 percent of glycerol, 25 percent of sodium hydroxide and 50 percent of pure water) to ensure that the cleaning solution completely soaks the substrate, carrying out ultrasonic treatment at the frequency of 300kHz and the power of 300W for 30min, soaking the substrate in the pure water for ultrasonic treatment for 30min, repeating the ultrasonic treatment of the pure water for 3 times, using nitrogen to gradually blow and completely blow and dry the liquid on the substrate, placing the ceramic substrate in a quartz tube type atmosphere furnace, introducing nitrogen with the purity of not less than 99.99 percent into a furnace tube, and ensuring that the gas pressure in the furnace tube reaches 1.01 multiplied by 10 5 After Pa, calcination was carried out, the temperature profile of calcination being set: the first temperature is 30 ℃, the heat preservation time is 100min, the second temperature is 500 ℃, the heat preservation time is 80min, the third temperature is 1100 ℃, the heat preservation time is 120min, the fourth temperature is 800 ℃, the heat preservation time is 100min, the fifth temperature is 500 ℃, the heat preservation time is 120min, the sixth temperature is 120 ℃, and the heat preservation time is 120min; and after heating is stopped, taking out the ceramic substrate, wiping the support plate clean by absolute ethyl alcohol along the X \ Y axis direction, placing the ceramic substrate on the support plate, entering a sputtering chamber with the vacuum degree of 0.5Pa, heating at 200 ℃ for 5min, and performing argon dry etching at 300W by using argon with the flow rate of 80mL/min for 3min to obtain the pretreated ceramic.
Comparative example 1
The ceramic with the thickness of 0.127mm and the diameter of a through hole of 0.080mm and the ceramic without the through hole are not pretreated.
Comparative example 2
The ceramic with the thickness of 0.254mm and the diameter of the through hole of 0.15mm and the ceramic without through hole are not pretreated.
Comparative example 3
The ceramic with the thickness of 0.381mm and the diameter of a through hole of 0.23mm and the ceramic without passing through the through hole are not pretreated.
Comparative example 4
The ceramic with the thickness of 0.508mm and the diameter of a through hole of 0.3mm and the ceramic without passing through the hole are not pretreated.
Comparative example 5
Ceramic with thickness of 1.0mm and through hole diameter of 0.6mm and non-through hole ceramic without pretreatment.
Comparative example 6
The ceramic with the thickness of 1.5mm and the diameter of a through hole of 0.9mm and the ceramic without passing through the hole are not pretreated.
Performance testing
(1) The pretreated ceramic obtained in example 1 and the ceramic substrate not pretreated in comparative example 1 were subjected to double-sided sputtering of seed layer, titanium tungsten, nickel, gold were sputtered in this order at a sputtering power of 1800w for 30min under a pressure of 0.5Pa, and the total thickness of the seed layer was 0.5 μm (wherein the thickness of the titanium tungsten layer was 0.15 μm, the thickness of the nickel layer was 0.15 μm, and the thickness of the gold layer was 0.2m, and then the gold layer was electroplated at a thickness of 2 μm, a plating voltage of 2V, a current of 0.2A, and a current efficiency of 90%, the plating solution was a gold potassium citrate solution, a plating time of 20min, and the plating solution had a pH of 6, the cathode used for plating was a titanium mesh, the anode was a platinum titanium mesh, an area ratio of the cathode to the anode was 1.5, the temperature of the plating solution was 60 ℃, then a gold wire having a diameter of 50 μm was used, and under the effect of a wedge bonder, that 5 gold wire groups were punched, and the tensile force test results were obtained in the following examples 1 and in comparative example 1, and in which the results are shown in the following table 1 are recorded as the following, and in the following drawings, wherein, and in the comparative example 1.
TABLE 1 gold wire tension of plating films obtained in example 1 and comparative example 1
As can be seen from Table 1, in the data of comparative example 1, peeling occurred in the solder point to which the gold wire was bonded when the tensile force values were 36gf, 22gf, and 30gf, respectively, as shown in FIG. 1; in contrast, in example 1, no peeling occurred in 10 tensile test values having a tensile value of 22 to 38 gf.
As can be seen from fig. 1, the film bonding force in example 1 was significantly better than that in comparative example 1 after the tensile test even though the tensile values were not very different.
As can be seen from FIG. 2, the plating tweezers obtained by magnetron sputtering using the pretreated ceramic obtained in example 1 as a substrate only scraped fine marks, and adhered with 3M adhesive tape without peeling, indicating pass; the bonding between the coating film obtained by using the ceramic which is not pretreated in comparative example 1 as the substrate by magnetron sputtering and the ceramic is not firm, the coating film can be scraped and lifted by tweezers, and the coating film can also be adhered and lifted by a 3M adhesive tape.
(2) The pretreated ceramic obtained in example 1 and the ceramic not pretreated in comparative example 1 were used as substrates, and the plating films obtained by magnetron sputtering were heated at 310 ℃ for 5min for heating inspection, and the swelling of the porous ceramic film layer was observed under a microscope, as shown in FIG. 3, wherein A is comparative example 1 and B is example 1.
As can be seen from FIG. 3, the ceramic obtained in example 1 as a pretreatment was used as a substrate to obtain a coating film without blistering, whereas the ceramic obtained in comparative example 1 without pretreatment was used as a substrate to obtain a coating film with blistering.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A method for pretreating a ceramic substrate, comprising the steps of:
carrying out ultrasonic cleaning on the ceramic substrate in an alkaline cleaning solution to obtain a clean ceramic substrate;
calcining the clean ceramic substrate in a nitrogen protection atmosphere to obtain a calcined ceramic substrate;
and performing argon dry etching on the calcined ceramic substrate.
2. The pretreatment method according to claim 1, wherein the alkaline cleaning solution comprises the following components in percentage by mass: 5 to 15 percent of polyethylene glycol, 10 to 20 percent of glycerol, 20 to 30 percent of sodium hydroxide and 45 to 55 percent of pure water.
3. The pretreatment method according to claim 1 or 2, wherein the ultrasonic cleaning is performed at a frequency of 120 to 300kHz at a power of 150 to 300W for 30 to 60min.
4. The pretreatment method according to claim 1, wherein the calcining includes:
heating to a first temperature for first heat preservation, wherein the first temperature is 25-30 ℃, and the first heat preservation time is 100-120 min;
raising the temperature from the first temperature to a second temperature for second heat preservation, wherein the second temperature is 450-500 ℃, and the second heat preservation time is 80-100 min;
raising the temperature from the second temperature to a third temperature for third heat preservation, wherein the third temperature is 1000-1100 ℃, and the third heat preservation time is 100-150 min;
raising the temperature from the third temperature to a fourth temperature, and carrying out fourth heat preservation, wherein the fourth temperature is 750-800 ℃, and the fourth heat preservation time is 120-150 min;
cooling from the fourth temperature to a fifth temperature, and performing fifth heat preservation, wherein the fifth temperature is 450-500 ℃, and the fifth heat preservation time is 120-170 min;
and reducing the temperature from the fifth temperature to a sixth temperature for sixth heat preservation, wherein the sixth temperature is 100-120 ℃, and the sixth heat preservation time is 120-150 min.
5. The pretreatment method according to claim 1 or 4, wherein the pressure of the calcination is 1.01 to 1.50X 10 5 Pa。
6. The pretreatment method according to claim 1, wherein the power of the argon dry etching is 250 to 300W, and the time is 3 to 5min.
7. The pretreatment method according to claim 1 or 6, wherein a flow rate of argon in the argon dry etching is 60 to 80mL/min.
8. The pretreatment method according to claim 1, wherein a purity of nitrogen in the nitrogen atmosphere is not less than 99.99%.
9. The pretreatment method according to claim 1, further comprising, after the ultrasonic cleaning in the alkaline cleaning solution: and (3) carrying out ultrasonic cleaning and drying on the ceramic substrate obtained by ultrasonic cleaning in the alkaline cleaning solution in water in sequence.
10. A method of coating a ceramic substrate, comprising the steps of: sequentially sputtering a seed layer and a gold electroplating layer on the ceramic substrate obtained by the pretreatment method of any one of claims 1 to 9 to obtain a coating layer; the seed layer comprises tantalum nitride, titanium tungsten, nickel and gold which are sputtered in sequence, or titanium tungsten and gold which are sputtered in sequence.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1347461A (en) * | 1970-05-01 | 1974-02-27 | Northrop Corp | Electron multiplier dynode plate and method making same |
| CN109092792A (en) * | 2018-09-25 | 2018-12-28 | 福建毫米电子有限公司 | A kind of ceramic substrate surface processing method |
| CN111952267A (en) * | 2020-09-16 | 2020-11-17 | 大连达利凯普科技股份公司 | Manufacturing process for improving bonding strength of single-layer capacitor |
| CN112779494A (en) * | 2020-12-04 | 2021-05-11 | 核工业西南物理研究院 | Surface metallization process of dielectric ceramic filter |
| CN115354278A (en) * | 2022-08-24 | 2022-11-18 | 广州天极电子科技股份有限公司 | Preparation method of thin film resistor in thin film resistance-capacitance network |
-
2022
- 2022-12-05 CN CN202211547230.0A patent/CN115819120A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1347461A (en) * | 1970-05-01 | 1974-02-27 | Northrop Corp | Electron multiplier dynode plate and method making same |
| CN109092792A (en) * | 2018-09-25 | 2018-12-28 | 福建毫米电子有限公司 | A kind of ceramic substrate surface processing method |
| CN111952267A (en) * | 2020-09-16 | 2020-11-17 | 大连达利凯普科技股份公司 | Manufacturing process for improving bonding strength of single-layer capacitor |
| CN112779494A (en) * | 2020-12-04 | 2021-05-11 | 核工业西南物理研究院 | Surface metallization process of dielectric ceramic filter |
| CN115354278A (en) * | 2022-08-24 | 2022-11-18 | 广州天极电子科技股份有限公司 | Preparation method of thin film resistor in thin film resistance-capacitance network |
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