CN115746371A - Surface treatment method for polyimide and polyimide - Google Patents
Surface treatment method for polyimide and polyimide Download PDFInfo
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Abstract
The application relates to the technical field of material surface treatment, and discloses a surface treatment method of polyimide and the polyimide. The surface treatment method of the polyimide comprises the steps of carrying out chemical degreasing treatment on the polyimide by adopting a chemical degreasing solution, carrying out chemical roughening treatment by adopting a chemical roughening treatment solution to form a roughened layer, carrying out neutralization treatment on the roughened layer, cleaning the roughened layer by adopting deionized water until the roughened layer is neutral, carrying out plasma etching on the roughened layer to form an embedded layer, wherein the embedded layer comprises a plurality of embedded units distributed at intervals, and an embedded groove is formed between every two adjacent embedded units. Compared with the prior art, the chemical degreasing, chemical roughening and neutralization treatment are carried out on the surface of the polyimide material, the roughened layer is subjected to plasma etching, and a micro-nano embedded layer structure which is microscopically uneven and has chemical activity is obtained, so that the polyimide material and the surface metal layer are embedded with each other on the interface, and the binding force between the coating and the polyimide material is further improved.
Description
Technical Field
The application relates to the technical field of material surface treatment, in particular to a polyimide surface treatment method and polyimide.
Background
Polyimide (PI) materials are polymers with a molecular main chain containing an imide ring (CO-NH-CO) structure, the use temperature can reach-250 ℃ to +450 ℃, and the Polyimide (PI) materials have excellent mechanical properties, chemical stability, low dielectric constant and good radiation resistance, and can be widely applied to the fields of electronic appliances, aerospace, microelectronics and the like. Polyimide, a typical non-metallic material, has high volume resistance and surface resistance and high surface insulation, and therefore, when applied to products such as electronic circuits and radar antennas, surface metallization is required. Due to the fact that the polyimide material is smooth and compact in surface, high in chemical inertness and poor in hydrophilicity, active particles cannot be effectively attached when metal layers such as chemical plating and electroplating are deposited, and the problems that a plating layer is discontinuous and bonding strength between a deposited metal plating layer and a polyimide base material is poor easily occur.
Disclosure of Invention
In order to solve the technical problems that the adhesion of polyimide active particles is poor, a coating is discontinuous, and the binding force between the polyimide active particles and the coating is poor, the application mainly aims to provide a polyimide surface treatment method and polyimide, which can improve the adhesion of the active particles of a polyimide material, ensure the continuity of the coating, and have high binding force between the polyimide active particles and the coating.
In order to achieve the purpose of the invention, the following technical scheme is adopted in the application:
according to an aspect of the present application, there is provided a surface treatment method of polyimide, including the steps of:
chemical degreasing treatment is carried out on the polyimide by adopting a chemical degreasing solution;
carrying out chemical roughening treatment on the polyimide through a chemical roughening treatment solution to form a roughened layer;
neutralizing the coarsening layer, including cleaning the coarsening layer with deionized water until the coarsening layer is neutral;
and carrying out plasma etching on the rough layer to form a tabling layer, wherein the tabling layer comprises a plurality of tabling units distributed at intervals, and tabling grooves are arranged between every two adjacent tabling units.
According to an embodiment of the present application, the fitting unit is a protruding structure protruding toward one side of the plating layer, the fitting unit includes a main body and a plurality of extending portions distributed on the periphery side of the main body, a occupying space is provided between adjacent extending portions, and the occupying space is communicated with the fitting space.
According to an embodiment of the present application, the chemical degreasing solution comprises a sodium hydroxide solution, a sodium phosphate solution and a sodium carbonate solution, wherein the concentration of the sodium hydroxide solution is 5-10g/L, the concentration of the sodium phosphate is 30-40g/L, and the concentration of the sodium carbonate solution is 25-30g/L.
According to an embodiment of the present application, the chemical degreasing treatment is performed at a treatment temperature of 70-95 ℃ for 20s-3min.
According to an embodiment of the present application, the chemical roughening solution comprises a strong alkali solution, a potassium permanganate solution, a sodium carbonate solution, ammonia water, a sodium dodecyl benzene sulfonate solution, and hydrazine hydrate, wherein the concentration of the strong alkali solution is 300-500g/L, the concentration of the potassium permanganate solution is 30-50g/L, the concentration of the sodium carbonate solution is 10-20g/L, the concentration of the ammonia water is 5-10mL/L, the concentration of the sodium dodecyl benzene sulfonate solution is 2-5g/L, the concentration of the hydrazine hydrate is 10-20g/L, the temperature of the chemical roughening treatment is 50-60 ℃, and the time of the chemical roughening treatment is 5-15min.
According to an embodiment of the present application, wherein preparing the chemical roughening treatment solution comprises the steps of:
dissolving strong base in water, and stirring to obtain a strong base solution;
adding potassium permanganate and stirring;
adding sodium carbonate and ammonia water and stirring;
adding hydrazine hydrate and sodium dodecyl benzene sulfonate, and stirring to obtain the chemical roughening treatment solution.
According to an embodiment of the present application, the neutralization solution comprises phosphoric acid and oxalic acid, wherein the concentration of the phosphoric acid is 30-50mL/L, and the concentration of the oxalic acid is 5-10g/L.
According to one embodiment of the present application, wherein the neutralization treatment temperature is 20 to 30 ℃ and the neutralization treatment time is 1 to 2min.
According to an embodiment of the application, the plasma etching treatment comprises the step of etching the polyimide film by using etching gas under the action of an electric field, wherein the etching gas is nitrogen plasma or mixed gas of argon and hydrogen, the etching power is 300W-500W, the etching time is 5-20min, and the air inflow of the etching gas is 80-120sccm.
According to another aspect of the present application, there is provided a polyimide obtained by the above-mentioned surface treatment method of polyimide.
According to the technical scheme, the surface treatment method of the polyimide and the polyimide have the advantages and positive effects that:
the method is designed by a plating pretreatment method of chemically degreasing, chemically roughening and neutralizing the surface of the polyimide material, and plasma etching is carried out on the roughened layer, so that a micro-nano embedded layer structure which is microscopically uneven and has chemical activity is obtained, an attachment site is provided for metal particle deposition, an interface mutual embedding function of the polyimide material and a surface metal layer is formed, and the binding force between a plating layer and the polyimide material is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive labor.
Fig. 1 is a schematic flow chart of a surface treatment method of polyimide according to an embodiment of the present disclosure;
FIG. 2 shows a micro-morphology of the chemically roughened polyimide material after surface chemical roughening when the concentration of the chemical roughening solution is low (potassium hydroxide is lower than 300g/L, and potassium permanganate is lower than 30 g/L);
FIG. 3 is a micro-pore structure obtained by atomic force microscope test after surface chemical roughening of a polyimide material when the concentration of a chemical roughening solution is low (potassium hydroxide is lower than 300g/L, and potassium permanganate is lower than 30 g/L);
FIG. 4 is a photograph of a hydrophilicity test of the polyimide material after surface chemical roughening when the concentration of the chemical roughening solution is low (potassium hydroxide is less than 300g/L, and potassium permanganate is less than 30 g/L);
FIG. 5 shows the microstructure of the PI material of example 1 after surface chemical roughening;
FIG. 6 shows the micro-pore structure obtained from the atomic force microscope test after the surface of the PI material is chemically roughened in example 1;
FIG. 7 shows the result of the hydrophilicity test after the surface of the PI material is chemically roughened in example 1;
FIG. 8 shows the results of the IR test after the surface of the PI material was chemically roughened in example 1;
FIG. 9 shows a micro-topography of a polyimide prepared by a method for surface treatment of polyimide according to an embodiment of the present disclosure after plasma etching;
FIG. 10 shows another micro-topography of a polyimide prepared by a method of surface treatment of polyimide according to an embodiment of the present application after plasma etching;
fig. 11 shows a micro-topography and a cross-sectional topography of a polyimide material subjected to electroless copper plating after plasma etching on a surface of the polyimide material prepared by the surface treatment method for polyimide according to the embodiment of the present application;
FIG. 12 is a macroscopic photograph of the electroless copper plated layer after the plasma etching on the surface of the polyimide material prepared in example 1 according to the method for surface treatment of polyimide in the present application, after being subjected to a thermal shock test;
fig. 13 shows the micro-topography of the PI material after surface chemical roughening at a roughening temperature lower than 50 ℃ (e.g., normal temperature);
FIG. 14 shows the microstructure of the PI material of example 2 after surface chemical roughening;
FIG. 15 is a photograph showing the appearance of the PI material after surface chemical roughening at a roughening temperature higher than 60 ℃;
FIG. 16 shows a micro-topography of the surface of the polyimide material of example 2 after plasma etching, prepared by a method of surface treatment of polyimide according to the present application;
FIG. 17 shows another micro-topography of a surface of a polyimide material of example 2 after plasma etching, prepared by a method of surface treatment of polyimide according to an embodiment of the present application;
FIG. 18 is a graph showing the effect of plasma etch power on the bond strength of a surface coating of a polyimide material;
FIG. 19 is a micro-topography of the polyimide material of example 4 after plasma etching of the surface;
fig. 20 is a schematic surface structure diagram of a fitting layer formed after the polyimide plasma etching according to an embodiment of the present disclosure;
FIG. 21 is a schematic cross-sectional view of a tabling layer formed after plasma etching of polyimide according to an embodiment of the present disclosure;
fig. 22 is a schematic cross-sectional view of a polyimide material prepared by a method for surface treatment of polyimide according to an embodiment of the present disclosure, after being subjected to plating treatment.
Wherein:
100. a chimeric layer; 11. a fitting unit; 1. an extension portion; 2. a position occupying groove; 12. a fitting groove; 200. plating; 300. a substrate.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Polyimide (PI) materials are polymers with a molecular main chain containing an imide ring (CO-NH-CO) structure, the use temperature can reach-250 ℃ to +450 ℃, and the Polyimide (PI) materials have excellent mechanical properties, chemical stability, low dielectric constant and good radiation resistance, and can be widely applied to the fields of electronic appliances, aerospace, microelectronics and the like. Polyimide, a typical non-metallic material, has high volume resistance and surface resistance and high surface insulation, and therefore needs to be subjected to surface metallization when applied to products such as electronic circuits and radar antennas. Due to the fact that the polyimide material is smooth and compact in surface, high in chemical inertness and poor in hydrophilicity, active particles cannot be effectively attached when metal layers such as chemical plating and electroplating are deposited, and the problems that the plating layer 200 is discontinuous and the bonding strength between the deposited metal plating layer 200 and the polyimide base material 300 is poor easily occur.
Therefore, the surface of the polyimide material needs to be pretreated before plating, so as to improve the hydrophilicity and chemical activity of the surface of the material and improve the adhesion of the metal plating layer 200 on the surface of the polyimide material. The mechanical roughening method adopted at present can improve the hydrophilicity of the surface of the polyimide material, and the chemical roughening method by utilizing alkali liquor etching can improve the chemical activity of the surface of the polyimide material, but the effective combination between the material surface plating layer 200 after mechanical roughening and chemical roughening and the base material 300 is insufficient, and the requirement on the binding force of the plating layer 200 under the condition of wide temperature range cannot be met.
In order to realize the continuous and compact metal plating layer 200 and improve the binding force between the polyimide material and the metal layer, an interface mutual embedding structure is designed between the polyimide material and the metal plating layer 200, so that the binding strength between the polyimide material surface plating layer 200 and the polyimide material is effectively improved, and the application provides a surface treatment method of polyimide and polyimide.
According to an aspect of the present application, there is provided a surface treatment method of polyimide, including the steps of:
chemical degreasing treatment is carried out on polyimide by adopting a chemical degreasing solution;
chemically roughening the polyimide by using a chemical roughening solution to form a roughened layer;
neutralizing the coarsened layer, and cleaning the coarsened layer by using deionized water until the coarsened layer is neutral;
and performing plasma etching on the rough layer to form a fitting layer 100, wherein the fitting layer 100 comprises a plurality of fitting units 11 distributed at intervals, and a fitting groove 12 is formed between every two adjacent fitting units 11.
As an example, (1) chemical degreasing is performed on the surface of the polyimide material by using a chemical degreasing solution to remove oil stains on the surface of the polyimide material, which is beneficial to the subsequent roughening process.
(2) And (2) carrying out chemical roughening treatment on the surface of the polyimide material obtained in the step (1) to form a roughened layer, so that the surface tension of the polyimide material can be reduced, the hydrophilicity is improved, and good surface chemical activity is obtained. The surface activity of the material is improved, and chemical bonds with strong binding force and high stability are formed, so that active sites are provided for the adhesion of active particles and metal deposition, and the adhesion of the active particles and the metal particles on the surface of the polyimide material is improved.
In order to obtain good surface chemical activity, the roughening time needs to be controlled at the same time of chemical roughening treatment, so that on one hand, the defect that due to the fact that the roughening time is too short, roughening is not sufficient, active center sites deposited on the surface of the polyimide material are not uniform, and therefore the thickness of a plating layer 200 is not uniform when a metal plating layer 200 deposited on the surface of the subsequent polyimide material is likely to be deposited is avoided, and on the other hand, the problem that due to the fact that the roughening time is too long, the active center sites deposited on the surface of the subsequent polyimide material are too thick, and the bonding force between the plating layer 200 and the polyimide material is insufficient is avoided.
(3) And (3) neutralizing the product obtained in the step (2), and washing the product to be neutral by using deionized water.
(4) And (3) cleaning the product obtained in the step (3), and then performing plasma etching treatment to further form a micro embedding layer 100 with an anchoring embedding structure on the surface of the polyimide material, wherein the embedding units 11 are arranged at intervals, so that the interface mutual embedding effect between the plating layer 200 and the polyimide material during the subsequent metal layer deposition is facilitated, and the binding force between the plating layer 200 and the polyimide material is improved.
Through plasma etching treatment, the surface activity of the polyimide material is improved, a rivet-shaped embedding structure with uneven surfaces of the polyimide material is constructed, an anchoring point is provided for metal layer deposition, the interface mutual embedding effect between the subsequent plating layer 200 and the polyimide material is improved, and the binding force between the polyimide material and the plating layer 200 is improved.
The polyimide surface treatment method provided by the invention is simple, has strong operability, and is suitable for treating the surface structure of the polyimide to form a polyimide material meeting the requirement.
According to another aspect of the present application, there is provided a polyimide obtained by the above-mentioned surface treatment method of polyimide.
Referring to fig. 1 to 22, in the polyimide material of the present invention, an interface embedded design with a bonding force with a surface plating layer 200 is formed by an embedded layer 100, such that good hydrophilicity and surface activity of the surface of the polyimide material are achieved, good active sites and anchor points are provided for active particle adhesion and metal deposition, and the polyimide material can be directly used for chemical plating of a metal layer on the surface of the polyimide material, such that continuous and dense deposition of the metal layer is achieved, and the bonding strength between the metal plating layer 200 and the polyimide material is improved.
According to an embodiment of the present application, the engaging unit 11 is a protruding structure protruding toward one side of the plating layer 200, the engaging unit 11 includes a main body and a plurality of extending portions distributed on the periphery of the main body, a occupying space 2 is provided between adjacent extending portions, and the occupying space 2 is communicated with the engaging space 12.
Referring to fig. 20, 21 and 22, the fitting unit 11 is used to form a mutual fitting structure with the plating layer 200, and as an example, when the fitting unit 11 is a protruding structure protruding toward the plating layer 200 side, and includes an extending portion 1 on the periphery of the body, the contact area between the fitting layer 100 and the plating layer 200 is increased by the extending portion 1, the bonding strength is further increased by the occupying groove 2 and the plating layer 200 at the position of the fitting unit 11, and the occupying groove 2 communicates with the fitting groove 12, and further, the plating layer 200 can form a continuous film structure on the surface of the fitting layer 100, and the bonding force between the plating layer 200 and the fitting layer 100 is further increased.
According to an embodiment of the present application, the chemical degreasing solution comprises a sodium hydroxide solution, a sodium phosphate solution and a sodium carbonate solution, wherein the concentration of the sodium hydroxide solution is 5-10g/L, the concentration of the sodium phosphate solution is 30-40g/L, and the concentration of the sodium carbonate solution is 25-30g/L.
According to an embodiment of the present application, the treatment temperature of the chemical degreasing treatment is 70-95 ℃ and the time is 20s-3min.
According to an embodiment of the present application, the chemical roughening solution comprises a strong alkali solution, a potassium permanganate solution, a sodium carbonate solution, ammonia water, a sodium dodecyl benzene sulfonate solution, and hydrazine hydrate, wherein the concentration of the strong alkali solution is 300-500g/L, the concentration of the potassium permanganate solution is 30-50g/L, the concentration of the sodium carbonate solution is 10-20g/L, the concentration of the ammonia water is 5-10mL/L, the concentration of the sodium dodecyl benzene sulfonate solution is 2-5g/L, the concentration of the hydrazine hydrate is 10-20g/L, the temperature of the chemical roughening treatment is 50-60 ℃, and the time of the chemical roughening treatment is 5-15min.
According to an embodiment of the present application, wherein the preparing of the chemical roughening treatment solution comprises the steps of:
dissolving strong base in water, and stirring to obtain strong base solution;
adding potassium permanganate and stirring;
adding sodium carbonate and ammonia water and stirring;
adding hydrazine hydrate and sodium dodecyl benzene sulfonate, and stirring to obtain a chemical roughening treatment solution.
Further, the strong base in the chemical roughening treatment liquid is sodium hydroxide or potassium hydroxide, and the raw materials are stirred after being added every time, so that the raw materials are quickly dissolved.
According to an embodiment of the present application, the neutralization solution comprises phosphoric acid and oxalic acid, wherein the concentration of phosphoric acid is 30-50mL/L, and the concentration of oxalic acid is 5-10g/L.
According to one embodiment of the present application, wherein the neutralization treatment temperature is 20 to 30 ℃ and the neutralization treatment time is 1 to 2min.
According to an embodiment of the application, the plasma etching process includes etching the polyimide film by using an etching gas under the action of an electric field, wherein the etching gas is nitrogen plasma or a mixed gas of argon and hydrogen, the etching power is 300W-500W, the etching time is 5-20min, and the air inflow of the etching gas is 80-120sccm.
The plasma etching treatment steps are as follows: and (2) etching the polyimide material by adopting nitrogen plasma or argon and hydrogen mixed gas (the volume fraction ratio of argon to hydrogen is 8-9).
As an example:
example 1
A surface treatment method for improving the binding force of polyimide and a surface coating layer 200, and an interface mutual embedding design method for the binding force of a polyimide material and the surface coating layer, comprises the following steps:
referring to fig. 1, firstly, a substrate is provided as a polyimide material, and then chemical degreasing solution is used to chemically degrease the surface of the polyimide material, so as to remove oil stains on the surface of the polyimide material, thereby facilitating the subsequent roughening process.
The chemical degreasing treatment solution comprises the following components: 5g/L of sodium hydroxide, 30g/L of sodium phosphate and 25g/L of sodium carbonate. The chemical degreasing temperature is 70 ℃, and the chemical degreasing time is 20s.
And then, chemical roughening treatment is carried out on the surface of the polyimide material by adopting a chemical roughening solution, so that the surface tension of the polyimide material is reduced, the hydrophilicity is improved, and good surface chemical activity is obtained.
The chemical roughening liquid comprises the following components: 300g/L of potassium hydroxide, 30g/L of potassium permanganate, 10g/L of sodium carbonate, 5mL/L of ammonia water, 2g/L of sodium dodecyl benzene sulfonate and 10g/L of hydrazine hydrate. Firstly, dissolving potassium hydroxide in water to obtain a potassium hydroxide solution, then adding potassium permanganate, then adding sodium carbonate and ammonia water, finally adding hydrazine hydrate and sodium dodecyl benzene sulfonate, and stirring after adding the raw materials each time to quickly dissolve the raw materials. The chemical roughening treatment temperature is 50 ℃, and the chemical roughening treatment time is 5min.
The concentration of the chemical roughening solution is controlled, when the concentration of the chemical roughening solution is low, the surface of the PI material basically has no change, the surface chemical activity and the hydrophilicity are insufficient, and when the concentration of the chemical roughening solution is high, the roughening degree of the surface of the PI material is too serious, so that the PI material substrate is seriously damaged, and the physical performance of the substrate material is damaged. FIG. 2, FIG. 3 and FIG. 4 show that the concentration of the chemical roughening solution is low (potassium hydroxide is low)300g/L and potassium permanganate lower than 30 g/L), the microscopic morphology of the surface of the PI material after chemical roughening, the microscopic pore structure obtained by atomic force microscope test and the hydrophilicity test result. Fig. 5, 6 and 7 show the microstructure of the PI material after surface chemical roughening, the micro-pore structure obtained by atomic force microscope test, and the hydrophilicity test results in example 1, respectively. Compared with fig. 2 to 4, after the surface of the PI material is chemically roughened, the surface of the PI material microscopically presents a more obvious etching hole structure, and the hydrophilicity is enhanced. FIG. 8 is an infrared test result of the coarsened surface of the PI material, which shows that COO is grafted on the PI molecular chain after chemical coarsening - And the surface of the PI material is chemically activated by the isoactive functional groups.
Similarly, the coarsening time is controlled, so that the defect that the thickness of the plating layer 200 is not uniform when the metal plating layer 200 on the surface of the subsequent material is deposited due to the fact that coarsening is insufficient due to too short coarsening time is avoided, and the problem that the bonding force between the plating layer 200 and the polyimide material is insufficient due to the fact that the thickness of the plating layer 200 is not uniform when the metal plating layer 200 on the surface of the subsequent material is deposited due to too long coarsening time is avoided. And then neutralizing the surface of the polyimide material by using a neutralizing solution, and washing the polyimide material to be neutral by using deionized water. The neutralizing solution comprises the following components: 30mL/L of phosphoric acid and 5g/L of oxalic acid. The neutralization temperature is 20 deg.C, and the neutralization time is 1min. And the neutralization process is mainly used for neutralizing redundant etching liquid in the chemical roughening process.
Finally, the polyimide material is subjected to plasma etching treatment, so that a microscopic anchoring embedded structure is further formed on the surface of the polyimide material, the interface interaction between the metal layer and the base material 300 during the subsequent metal layer deposition is facilitated, and the binding force between the metal coating 200 and the polyimide material is improved.
The plasma etching treatment method comprises the following steps: and (3) etching the polyimide material by adopting nitrogen plasma under the action of an electric field, wherein the etching power is 300W, the etching time is 5min, and the air inflow of etching gas is 80sccm.
Fig. 20 and 21 show the microscopic morphology of the surface of the polyimide material after plasma etching, and it is understood that the fitting layer 100 is formed on the surface of the polyimide material, and the fitting layer 100 has a rivet-like structure with microscopically uneven surface.
Performing chemical copper plating treatment on the roughened and etched polyimide material, wherein the chemical copper plating solution comprises the following components: 6g/L of copper sulfate, 12mL/L of formaldehyde, 2g/L of potassium hydroxide, 28g/L of sodium potassium tartrate and 0.2mg/L of stabilizer.
The temperature of the solution is 33 ℃ when in electroless copper plating, and the electroless copper plating time is 100min.
Fig. 11 shows the micro-morphology and the cross-sectional morphology of the electroless copper plating layer after the surface of the polyimide material prepared in example 1 is etched by the plasma, and the plating layer 200 is uniform and dense. And (3) placing the plated part in a 220 ℃ oven, baking at high temperature for 10 minutes, then quickly taking out and placing in liquid nitrogen for 10 minutes, wherein after a cold-hot impact test, the metal layer on the surface of the polyimide material has no phenomena of bulging, cracking and the like, and the plating layer 200 has good bonding force.
FIG. 12 shows the macroscopic morphology of the surface chemical copper-plating layer of the polyimide material after the cold and hot shock test. The solder joint peel strength of the plating layer 200 was measured, and the bond strength test value was 2.94MPa.
Referring to fig. 22, after the plating layer 200 is treated, the plating layer 200 has metal atoms in the fitting groove 12 in the fitting layer 100, thereby improving the bonding force between the plating layer 200 and the polyimide surface.
Example 2
An interface mutual embedding design method for improving the binding force of a polyimide material and a surface plating layer 200 comprises the following steps:
firstly, providing a substrate as a polyimide material, and then chemically degreasing the surface of the polyimide material by adopting a chemical degreasing solution so as to remove oil stains on the surface of the polyimide material, thereby being beneficial to the subsequent roughening process.
The chemical degreasing treatment solution comprises the following components: 5g/L of sodium hydroxide, 30g/L of sodium phosphate and 25g/L of sodium carbonate. The chemical degreasing temperature is 70 ℃, and the chemical degreasing time is 20s.
And then, chemical roughening treatment is carried out on the surface of the polyimide material by adopting a chemical roughening solution, so that the surface tension of the polyimide material is reduced, the hydrophilicity is improved, and good surface chemical activity is obtained.
The chemical roughening liquid comprises the following components: 300g/L of potassium hydroxide, 30g/L of potassium permanganate, 10g/L of sodium carbonate, 5mL/L of ammonia water, 2g/L of sodium dodecyl benzene sulfonate and 10g/L of hydrazine hydrate. Firstly, dissolving potassium hydroxide in water to obtain a potassium hydroxide solution, then adding potassium permanganate, then adding sodium carbonate and ammonia water, finally adding hydrazine hydrate and sodium dodecyl benzene sulfonate, and stirring after adding the raw materials each time to quickly dissolve the raw materials. The chemical roughening treatment temperature is 60 ℃, and the chemical roughening treatment time is 5min.
The chemical roughening treatment temperature is controlled, on one hand, the defect that due to insufficient roughening temperature, roughening is insufficient, active center sites deposited on the surface of the polyimide material are uneven, and therefore the thickness of a plating layer 200 is uneven when a metal plating layer 200 on the surface of a subsequent material is deposited is possibly caused is avoided, and on the other hand, the defect that due to the fact that the roughening temperature is too high, damage to a PI (polyimide) matrix material is caused is avoided. Fig. 13 and 14 are the micro-morphologies after the roughening temperature is lower than 50 ℃ (e.g., normal temperature condition) and the surface chemical roughening of the PI material in example 2. Fig. 15 is a picture of the appearance of the PI material after the surface is roughened at a roughening temperature higher than 60 ℃, wherein small uniformly distributed saw teeth appear on the PI edge, which affects the use of actual products.
And then neutralizing the surface of the polyimide material by using a neutralizing solution, and cleaning the polyimide material to be neutral by using deionized water. The neutralizing solution comprises the following components: 30mL/L of phosphoric acid and 5g/L of oxalic acid. The neutralization temperature is 20 deg.C, and the neutralization time is 1min. The neutralization process is mainly used for neutralizing redundant etching liquid in the chemical roughening process.
Finally, the polyimide material is subjected to plasma etching treatment, so that a microscopic anchoring embedded structure is further formed on the surface of the polyimide material, the interface interaction between the metal layer and the base material 300 during the subsequent metal layer deposition is facilitated, and the binding force between the metal coating 200 and the polyimide material is improved.
The plasma etching treatment method comprises the following steps: and (3) etching the polyimide material by adopting nitrogen plasma under the action of an electric field, wherein the etching power is 300W, the etching time is 5min, and the air inflow of etching gas is 80sccm.
Carrying out chemical copper plating treatment on the roughened and etched polyimide material, wherein the chemical copper plating solution comprises the following components: 6g/L of copper sulfate, 12mL/L of formaldehyde, 2g/L of potassium hydroxide, 28g/L of potassium sodium tartrate and 0.2mg/L of stabilizer.
The solution temperature is 33 ℃ during the electroless copper plating, and the electroless copper plating time is 100min. The solder joint peel strength of the plating layer 200 was measured, and the bond strength test value was 3.21MPa.
Example 3
An interface mutual embedding design method for improving the binding force of a polyimide material and a surface plating layer 200 comprises the following steps:
firstly, providing a substrate as a polyimide material, and then chemically degreasing the surface of the polyimide material by adopting a chemical degreasing solution so as to remove oil stains on the surface of the polyimide material, thereby being beneficial to the subsequent roughening process.
The chemical degreasing treatment solution comprises the following components: 5g/L of sodium hydroxide, 30g/L of sodium phosphate and 25g/L of sodium carbonate. The chemical degreasing temperature is 70 ℃, and the chemical degreasing time is 20s.
And then, chemical roughening treatment is carried out on the surface of the polyimide material by adopting a chemical roughening solution, so that the surface tension of the polyimide material is reduced, the hydrophilicity is improved, and good surface chemical activity is obtained.
The chemical roughening liquid comprises the following components: 300g/L of potassium hydroxide, 30g/L of potassium permanganate, 10g/L of sodium carbonate, 5mL/L of ammonia water, 2g/L of sodium dodecyl benzene sulfonate and 10g/L of hydrazine hydrate. Firstly, dissolving potassium hydroxide in water to obtain a potassium hydroxide solution, then adding potassium permanganate, then adding sodium carbonate and ammonia water, finally adding hydrazine hydrate and sodium dodecyl benzene sulfonate, and stirring after adding the raw materials each time to quickly dissolve the raw materials. The chemical roughening treatment temperature is 50 ℃, and the chemical roughening treatment time is 5min.
And then neutralizing the surface of the polyimide material by using a neutralizing solution, and washing the polyimide material to be neutral by using deionized water. The neutralizing solution comprises the following components: phosphoric acid 30mL/L, oxalic acid 5g/L. The neutralization temperature is 20 deg.C, and the neutralization time is 1min. The neutralization process mainly neutralizes the redundant etching solution in the chemical roughening process.
Finally, the polyimide material is subjected to plasma etching treatment, so that a microscopic anchoring embedded structure is further formed on the surface of the polyimide material, the interface interaction between the metal layer and the base material 300 during the subsequent metal layer deposition is facilitated, and the binding force between the metal plating layer 200 and the polyimide material is improved.
The plasma etching treatment method comprises the following steps: and (3) etching the polyimide material by adopting nitrogen plasma under the action of an electric field, wherein the etching power is 500W, the etching time is 5min, and the air inflow of etching gas is 80sccm. The plasma etching treatment can further form an uneven rivet-shaped structure on the basis of the micro-nano structure on the surface of the polyimide material, so that the anchoring and embedding effect between the subsequent plating layer 200 and the polyimide material is improved. Fig. 16 and 17 show the microscopic morphology of the polyimide material surface after plasma etching, and the polyimide material surface is microscopically an uneven rivet-like structure.
Compared with the embodiment 1, the embodiment 3 adjusts the power of plasma etching, the micro-embedded network structure of the polyimide surface after the treatment of the embodiment 3 is more obvious, and the active points and the metal particles are anchored in the process of subsequent metal layer deposition.
Performing chemical copper plating treatment on the roughened and etched polyimide material, wherein the chemical copper plating solution comprises the following components: 6g/L of copper sulfate, 12mL/L of formaldehyde, 2g/L of potassium hydroxide, 28g/L of potassium sodium tartrate and 0.2mg/L of stabilizer.
The temperature of the solution is 33 ℃ when in electroless copper plating, and the electroless copper plating time is 100min. The solder joint peel strength of the plating layer 200 was measured, and the bond strength test value was 3.48MPa.
The effect of the plasma etching power on the bonding strength of the polyimide material surface plating layer 200 under the same conditions is shown in fig. 18. In the power range of 300 to 500W, the bonding strength of the plating layer 200 increases with the increase of the etching power, but when the etching power is increased to 600W, the bonding strength of the plating layer 200 decreases, whereas the bonding strength of the plating layer 200 is relatively low at the 200W treatment, so that the preferable range of the plasma etching power is set to 300 to 500W. Similarly, the influence of the amount of air taken or the etching time of the plasma etching on the bonding strength of the polyimide material surface plating layer 200 is similar to the etching power under the same other conditions. In the range of 80-120sccm and the etching time of 5-20min, the bonding strength of the plating layer 200 is increased with the increase of the air input and the increase of the etching time, so the preferable range of the air input of the plasma etching is set to be 80-120sccm, and the preferable range of the etching time is 5-20 min.
Example 4
An interface mutual embedding design method for improving the binding force of a polyimide material and a surface plating layer 200 comprises the following steps:
firstly, providing a substrate as a polyimide material, and then carrying out surface chemical degreasing on the polyimide material by adopting a chemical degreasing solution so as to remove oil stains on the surface of the polyimide material and facilitate the subsequent roughening process.
The chemical degreasing treatment solution comprises the following components: 5g/L of sodium hydroxide, 30g/L of sodium phosphate and 25g/L of sodium carbonate. The chemical degreasing temperature is 70 ℃, and the chemical degreasing time is 20s.
And then, chemical roughening treatment is carried out on the surface of the polyimide material by adopting a chemical roughening solution, so that the surface tension of the polyimide material is reduced, the hydrophilicity is improved, and good surface chemical activity is obtained.
The chemical roughening liquid comprises the following components: 300g/L of potassium hydroxide, 30g/L of potassium permanganate, 10g/L of sodium carbonate, 5mL/L of ammonia water, 2g/L of sodium dodecyl benzene sulfonate and 10g/L of hydrazine hydrate. Firstly, dissolving potassium hydroxide in water to obtain a potassium hydroxide solution, then adding potassium permanganate, then adding sodium carbonate and ammonia water, finally adding hydrazine hydrate and sodium dodecyl benzene sulfonate, and stirring after adding the raw materials each time to quickly dissolve the raw materials. The chemical roughening treatment temperature is 50 ℃, and the chemical roughening treatment time is 5min.
And then neutralizing the surface of the polyimide material by using a neutralizing solution, and cleaning the polyimide material to be neutral by using deionized water. The neutralizing solution comprises the following components: 30mL/L of phosphoric acid and 5g/L of oxalic acid. The neutralization temperature is 20 deg.C, and the neutralization time is 1min. The neutralization process is mainly used for neutralizing redundant etching liquid in the chemical roughening process.
Finally, the polyimide material is subjected to plasma etching treatment, so that a microscopic anchoring embedded structure is further formed on the surface of the polyimide material, the interface interaction between the metal layer and the base material 300 during the subsequent metal layer deposition is facilitated, and the binding force between the metal plating layer 200 and the polyimide material is improved.
The plasma etching treatment method comprises the following steps: and (2) etching the polyimide material by adopting argon and hydrogen mixed gas (the volume fraction ratio of argon to hydrogen is 9). The plasma etching treatment can further form an uneven rivet-shaped structure on the basis of the micro-nano structure on the surface of the polyimide material, so that the anchoring and embedding effect between the subsequent plating layer 200 and the polyimide material is improved. In example 4, the gas composition of plasma etching was adjusted and an etching gas such as hydrogen was added, as compared with example 1. FIG. 19 shows the micro-topography of the surface of the polyimide material after plasma etching. The hole network structure of the treated PEEK surface is more obvious, and the anchoring of active points and metal particles during the subsequent metal layer deposition is facilitated.
Performing chemical copper plating treatment on the roughened and etched polyimide material, wherein the chemical copper plating solution comprises the following components: 6g/L of copper sulfate, 12mL/L of formaldehyde, 2g/L of potassium hydroxide, 28g/L of potassium sodium tartrate and 0.2mg/L of stabilizer.
The solution temperature is 33 ℃ during the electroless copper plating, and the electroless copper plating time is 100min. The solder joint pull strength of the plating layer 200 was measured, and the bond strength test value was 3.55MPa.
It is noted that, in this document, relational terms such as "first" and "second," and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A surface treatment method of polyimide is characterized by comprising the following steps:
chemical degreasing treatment is carried out on the polyimide by adopting a chemical degreasing solution;
carrying out chemical roughening treatment by adopting a chemical roughening treatment solution to form a roughened layer;
neutralizing the coarsening layer, and cleaning the coarsening layer by using deionized water until the coarsening layer is neutral;
and carrying out plasma etching on the rough layer to form a tabling layer, wherein the tabling layer comprises a plurality of tabling units distributed at intervals, and tabling grooves are arranged between every two adjacent tabling units.
2. The surface treatment method of polyimide according to claim 1, wherein the fitting unit is a protruding structure protruding toward one side of the plating layer, the fitting unit includes a main body and a plurality of extending portions distributed on a peripheral side of the main body, a holding groove is provided between adjacent extending portions, and the holding groove communicates with the fitting groove.
3. The surface treatment method of polyimide according to claim 1, wherein the chemical degreasing solution comprises a sodium hydroxide solution, a sodium phosphate solution, and a sodium carbonate solution, and the concentration of the sodium hydroxide solution is 5 to 10g/L, the concentration of the sodium phosphate is 30 to 40g/L, and the concentration of the sodium carbonate solution is 25 to 30g/L.
4. The surface treatment method of polyimide according to claim 1, wherein the chemical degreasing treatment is carried out at a treatment temperature of 70 to 95 ℃ for 20s to 3min.
5. The surface treatment method of polyimide according to claim 1, wherein the chemical roughening solution comprises a strong alkali solution, a potassium permanganate solution, a sodium carbonate solution, ammonia water, a sodium dodecylbenzenesulfonate solution, and hydrazine hydrate, wherein the concentration of the strong alkali solution is 300 to 500g/L, the concentration of the potassium permanganate solution is 30 to 50g/L, the concentration of the sodium carbonate solution is 10 to 20g/L, the concentration of the ammonia water is 5 to 10mL/L, the concentration of the sodium dodecylbenzenesulfonate solution is 2 to 5g/L, the concentration of the hydrazine hydrate is 10 to 20g/L, the temperature of the chemical roughening treatment is 50 to 60 ℃, and the time of the chemical roughening treatment is 5 to 15min.
6. The surface treatment method of polyimide according to claim 4, wherein preparing the chemical roughening treatment solution comprises the steps of:
dissolving strong base in water, and stirring to obtain strong base solution;
adding potassium permanganate and stirring;
adding sodium carbonate and ammonia water and stirring;
adding hydrazine hydrate and sodium dodecyl benzene sulfonate, and stirring to obtain the chemical roughening solution.
7. The surface treatment method of polyimide according to claim 1, wherein the neutralization solution comprises phosphoric acid and oxalic acid, wherein the concentration of phosphoric acid is 30 to 50mL/L, and the concentration of oxalic acid is 5 to 10g/L.
8. The surface treatment method of a polyimide film according to claim 1, wherein the neutralization treatment temperature is 20 to 30 ℃ and the neutralization treatment time is 1 to 2min.
9. The surface treatment method of polyimide according to claim 1, wherein the plasma etching treatment comprises etching the polyimide by using an etching gas under the action of an electric field, wherein the etching gas is a mixed gas of nitrogen or argon and hydrogen, the etching power is 300W-500W, the etching time is 5-20min, and the gas inflow amount of the etching gas is 80-120sccm.
10. A polyimide obtained by the surface treatment method of a polyimide according to any one of claims 1 to 9.
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