CN117966096A - Polyimide/Cu composite film and preparation method and application thereof - Google Patents
Polyimide/Cu composite film and preparation method and application thereof Download PDFInfo
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- CN117966096A CN117966096A CN202410132198.2A CN202410132198A CN117966096A CN 117966096 A CN117966096 A CN 117966096A CN 202410132198 A CN202410132198 A CN 202410132198A CN 117966096 A CN117966096 A CN 117966096A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000004642 Polyimide Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 92
- 230000007704 transition Effects 0.000 claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 30
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910018575 Al—Ti Inorganic materials 0.000 claims description 6
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 60
- 238000004544 sputter deposition Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 230000007246 mechanism Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Physical Vapour Deposition (AREA)
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Abstract
The invention provides a polyimide/Cu composite film, a preparation method and application thereof, and belongs to the technical field of copper-clad plates and current collecting films. The invention sputters the transition layer and the Cu layer on one side or two sides of the polyimide film by magnetron sputtering, controls the specific types of the transition layer, adopts high-activity Al, ti, cr or alloys thereof, can form chemical bonds with functional groups in the polyimide film and can form metallurgical bonding with the Cu layer, thereby improving the bonding force between polyimide and Cu, and has simple preparation method, high efficiency and no environmental pollution. The results of the examples show that the peel strength of the composite film prepared by the invention is more than 18.34N/cm, which exceeds the requirements of the electronic industry.
Description
Technical Field
The invention relates to the technical field of copper-clad plates or current collecting films, in particular to a polyimide/Cu composite film and a preparation method and application thereof.
Background
In recent years, with the rapid development of 3C products, new energy automobiles and other industries, various electronic products propose a development path for lightening, thinning and multifunctionality, and higher density integration and higher bearing power of electronic circuits are required. The Flexible Copper-clad plate (Flexible Copper CLAD LAMINATE, FCCL) serving as the base material of the printed circuit board has the advantages of light weight, flexibility and the like, and is widely applied to the fields of mobile phones, flat plates, liquid crystal displays and the like at present. At the same time, the rapid development of secondary batteries requires a thinner current collecting Cu thin film (Cu foil) with higher conductivity. The copper-clad plate for the integrated circuit or the current collecting film for the secondary battery can be realized by using a polyimide/Cu film, and the key technical difficulty is how to improve the bonding force of a polyimide/Cu interface.
The copper-clad plate is provided with three layers of flexible copper-clad plates (3L-FCCL) and two layers of flexible copper-clad plates (2L-FCCL). Currently, 3L-FCCL is the main stream of products, and the middle layer of adhesive mainly comprises epoxy adhesive and acrylic cool adhesive. However, adhesives suffer from heat resistance, dimensional stability, and long term reliability, and efforts have been made to develop 2L-FCCL products without intermediate adhesives. At present, the production process of the two-layer flexible copper clad laminate mainly comprises three processes: coating, lamination, sputtering/electroplating. The coating method is relatively simple in process for manufacturing the 2L-FCCL, easy to implement, but the polyimide/Cu layer interface bonding force is poor, and the product dimensional stability is poor, more importantly, the coating method can only produce the single-sided 2L-FCCL, and the ultrathin FCCL is difficult to produce. The lamination method can produce single-sided or double-sided 2L-FCCL products, has relatively good adhesive force and dimensional stability, but the interfacial bonding force of polyimide/Cu layers is related to the thickness of Cu layers, is not suitable for producing ultrathin 2L-FCCL, and has poor bending performance and high production cost. The sputtering-electroplating method or sputtering method uses polyimide film as base, and firstly, a Cu film is deposited on the base by magnetron sputtering, then, the Cu film is deposited by electroplating method, so that the thickness of the Cu film is thickened. The sputtering method has the advantages of high surface smoothness and capability of forming a thin layer conductor, however, the peeling strength and the insulation reliability are slightly poor, the electroplating causes pollution to the environment, and the interfacial bonding force between polyimide and Cu film is small.
In analyzing published papers and patents at home and abroad, researchers have made many researches on how to improve the bonding force between polyimide/Cu films and increase the bonding strength, for example, chemical treatment, corona treatment, low-pressure plasma treatment of polyimide films. The method can improve the interfacial bonding force of the Cu/polyimide to a certain extent, but has higher cost, lower environmental pollution and lower production efficiency of products, and the interfacial bonding force of the polyimide/Cu is still more common. Therefore, how to manufacture a polyimide/Cu composite film having excellent interfacial bonding force at low cost and high efficiency is a problem to be solved in the art.
Disclosure of Invention
The invention aims to provide a polyimide/Cu composite film, and a preparation method and application thereof. The composite film prepared by the preparation method provided by the invention has excellent binding force, and the method is simple, low in cost and high in efficiency.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a polyimide/Cu composite film, which comprises the following steps:
(1) Performing magnetron sputtering transition layers on one side or two sides of the polyimide film to obtain a polyimide film coated with the single-side or two-side transition layers; the transition layer comprises an Al layer, a Ti layer, a Cr layer, an Al-Ti alloy layer, an Al-Cr alloy layer, a Ti-Cr alloy layer or an Al-Ti-Cr alloy layer;
(2) And (3) performing magnetron sputtering on the surface of the transition layer of the single-sided or double-sided transition layer coated polyimide film obtained in the step (1) to obtain the polyimide/Cu composite film.
Preferably, the thickness of the polyimide film in the step (1) is 1 to 200 μm.
Preferably, the thickness of the transition layer in the step (1) is 2-100 nm.
Preferably, the back vacuum degree of the magnetron sputtering in the step (1) is less than 1 multiplied by 10 -3 Pa, the Ar pressure of the magnetron sputtering is 0.1-2 Pa, and the magnetron sputtering rate is 10-100 nm/min.
Preferably, the thickness of the copper layer in the step (2) is 1 to 10 μm.
Preferably, the back vacuum degree of the magnetron sputtering in the step (2) is less than 1 multiplied by 10 -3 Pa, the Ar pressure of the magnetron sputtering is 0.1-2 Pa, and the magnetron sputtering rate is 50-2000 nm/min.
Preferably, in the step (2), a bias voltage is also applied during the magnetron sputtering.
Preferably, the bias voltage is 50 to 500V.
The invention provides the polyimide/Cu composite film prepared by the preparation method.
The invention also provides application of the polyimide/Cu composite film as a flexible copper-clad plate or a secondary battery current collecting film.
The invention provides a preparation method of a polyimide/Cu composite film, which comprises the following steps:
(1) Performing magnetron sputtering transition layers on one side or two sides of the polyimide film to obtain a polyimide film coated with the single-side or two-side transition layers; the transition layer comprises an Al layer, a Ti layer, a Cr layer, an Al-Ti alloy layer, an Al-Cr alloy layer, a Ti-Cr alloy layer or an Al-Ti-Cr alloy layer; (2) And (3) performing magnetron sputtering on the surface of the transition layer of the single-sided or double-sided transition layer coated polyimide film obtained in the step (1) to obtain the polyimide/Cu composite film. The invention sputters the transition layer and the Cu layer on one side or two sides of the polyimide film by magnetron sputtering, controls the specific types of the transition layer, adopts high-activity Al, ti, cr or alloys thereof, can form chemical bonds with functional groups in the polyimide film and can form metallurgical bonding with the Cu layer, thereby improving the bonding force between polyimide and Cu, and has simple preparation method, high efficiency and no environmental pollution. The results of the examples show that the peel strength of the composite film prepared by the invention is more than 18.34N/cm, which exceeds the requirements of the electronic industry.
Drawings
FIG. 1 is an XRD pattern of a composite film prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of the composite thin film prepared in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of a polyimide/Cu composite film, which comprises the following steps:
(1) Performing magnetron sputtering transition layers on one side or two sides of the polyimide film to obtain a polyimide film coated with the single-side or two-side transition layers;
(2) And (3) performing magnetron sputtering on the surface of the transition layer of the single-sided or double-sided transition layer coated polyimide film obtained in the step (1) to obtain the polyimide/Cu composite film.
The invention carries out magnetron sputtering transition layer on one side or two sides of the polyimide film to obtain the polyimide film coated by the single-side or two-side transition layer.
In the present invention, the thickness of the polyimide film is preferably 1 to 200. Mu.m. The length and the width of the polyimide film are not particularly limited, and the polyimide film can be selected according to the needs. The method can realize the preparation of the large-size composite film. When the length of the polyimide film is large, the invention preferably unwinds and winds simultaneously, so that continuous preparation of the large-size reel-to-reel composite film is realized, namely, one side of the magnetron sputtering chamber is the polyimide film unwinding, and the other side is the winding. In a preferred embodiment of the present invention, when the length of the polyimide film is large, the moving rate of the polyimide film is preferably 90 to 110mm/min.
In the present invention, the transition layer includes an Al layer, a Ti layer, a Cr layer, an Al-Ti alloy layer, an Al-Cr alloy layer, a Ti-Cr alloy layer, or an Al-Ti-Cr alloy layer. When the transition layer is an Al-Ti alloy layer, an Al-Cr alloy layer, a Ti-Cr alloy layer or an Al-Ti-Cr alloy layer, the content of each element in the alloy layer is not particularly limited, and any proportion can be used. The invention controls the type of the transition layer, adopts high-activity Al, ti, cr or alloy thereof as the transition layer, and can form chemical bonds with functional groups in the polyimide film and form metallurgical bonding with the Cu layer, thereby improving the bonding force between polyimide and Cu.
In the present invention, the thickness of the transition layer is preferably 2 to 100nm, more preferably 5 to 50nm, and still more preferably 10 to 30nm. The present invention limits the thickness of the transition layer within the above range, and can provide the composite film with excellent bonding force.
In the present invention, the target material of the magnetron sputtering is preferably a pure Al target, a pure Ti target, a pure Cr target, an Al-Ti alloy target, an Al-Cr alloy target, a Ti-Cr alloy target or an Al-Ti-Cr alloy target. The shape of the target material is not particularly limited, and a target material having a shape well known to those skilled in the art may be used. In the present invention, the target is preferably a planar target or a cylindrical rotary target.
In the invention, the target is preferably pre-sputtered before use; the pre-sputtering time is preferably 1 to 5 minutes.
In the invention, the back vacuum degree of the magnetron sputtering is preferably less than 1 multiplied by 10 -3 Pa; the Ar pressure of the magnetron sputtering is preferably 0.1 to 2Pa, more preferably 0.2 to 1.2Pa; the magnetron sputtering rate is preferably 10 to 100nm/min, more preferably 10 to 50nm/min, and still more preferably 10 to 20nm/min. The time of the magnetron sputtering is not particularly limited, and the thickness of the transition layer is ensured to be within the range. The invention limits each parameter of the magnetron sputtering in the above range, can make the transition layer more uniform, better combine with the polyimide film, further improve the bonding force of the composite film.
The present invention preferably controls the magnetron sputtering power to control the magnetron sputtering rate. The invention preferably comprises the steps of firstly fixing magnetron sputtering power to 200W, sputtering for 5min on a glass substrate, then increasing the power to 500W, stabilizing for 2min, sputtering for 5min on another glass substrate, increasing the power by 300W each time, respectively sputtering for 5min on different glass substrates until the power is increased to 10kW, taking out the glass substrates, measuring the thickness of a sputtered film by using a step meter, and obtaining the quantitative relation between the sputtering power and the sputtering rate.
After the polyimide film coated by the single-sided or double-sided transition layer is obtained, the invention carries out magnetron sputtering copper layer on the surface of the transition layer of the polyimide film coated by the single-sided or double-sided transition layer to obtain the polyimide/Cu composite film.
In the present invention, the thickness of the copper layer is preferably 1 to 10 μm.
In the invention, the target material of the magnetron sputtering is preferably a pure Cu target.
In the invention, the back vacuum degree of the magnetron sputtering is preferably less than 1 multiplied by 10 -3 Pa; the Ar pressure of the magnetron sputtering is preferably 0.1 to 2Pa, more preferably 0.2 to 1.2Pa; the magnetron sputtering rate is preferably 50 to 2000nm/min,100 to 1000nm/min, and more preferably 200 to 300nm/min. In the present invention, it is also preferable to apply a bias voltage at the time of the magnetron sputtering; the bias voltage is preferably 50 to 500V. In the invention, the bias voltage can realize control of the texture of the Cu layer (111), which is beneficial to improving the conductivity of the composite film. The time of the magnetron sputtering is not particularly limited, and the thickness of the copper layer is ensured to be within the range. The invention limits each parameter of the magnetron sputtering in the above range, can make the copper layer more uniform, and realizes metallurgical bonding with the transition layer, thereby further improving the bonding force of the composite film.
The invention can form chemical bond with functional group in polyimide film and metallurgical bond with Cu layer, to improve the bonding force between polyimide and Cu, and realize large-size composite film preparation with simple method, low cost, high efficiency and no environmental pollution.
The invention provides the polyimide/Cu composite film prepared by the preparation method.
The composite film prepared by the invention has excellent binding force, and the thickness can be adjusted according to the requirement.
The invention also provides application of the polyimide/Cu composite film as a flexible copper-clad plate or a secondary battery current collecting film.
The operation of the application is not particularly limited, and the application technical scheme well known to those skilled in the art can be adopted.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) And installing a pure Al target and a pure Cu target in the magnetron sputtering chamber, and installing a series of glass substrates on a continuous sample rack for testing the quantitative relation between magnetron sputtering power and sputtering rate. When the vacuum degree of the magnetron sputtering chamber reaches 3X 10 -4 Pa, high-purity Ar gas is filled, in the whole magnetron sputtering process, the flowing Ar gas pressure is 0.5Pa, an Al target is started to perform pre-sputtering for 3 minutes, the sputtering power is fixed at 200W, then an Al film is subjected to magnetron sputtering on a glass substrate, and the sputtering time is 5 minutes; continuously increasing the Al magnetron sputtering power to 500W, stabilizing for 2 minutes, continuously moving the next glass substrate, and performing magnetron sputtering for 5 minutes; in the same way, the magnetron sputtering power of the Al target is increased to 10kW. Taking out the glass substrate, measuring the thickness of the Al film by using a step instrument, and obtaining a series of quantitative relations between magnetron sputtering power and the magnetron sputtering rate of Al;
By the same method, a series of Cu films under different powers are subjected to magnetron sputtering, and a quantitative relation between the magnetron sputtering power of a Cu target and the magnetron sputtering rate of Cu is constructed.
(2) Loading a roll of polyimide film (with the thickness of 0.05 mm) into an unreeling device of a magnetron sputtering chamber, fixing the polyimide film on a reeling mechanism at the other side, vacuumizing the whole magnetron sputtering device, filling high-purity Ar gas when the vacuum degree reaches 3X 10 -4 Pa, starting an Al target to perform pre-sputtering for 3 minutes in the whole magnetron sputtering process, starting the unreeling and reeling mechanism to enable the polyimide film to run in the magnetron sputtering chamber, fixing the magnetron sputtering rate of an Al target to be 10nm/min, enabling the moving rate of the polyimide film to be 100mm/min, and performing magnetron sputtering on one side of the polyimide film to obtain the polyimide film coated by the Al transition layer with the thickness of 20 nm;
(3) And loading the polyimide film coated by the Al transition layer into an unreeling device of a magnetron sputtering chamber, fixing the polyimide film on a reeling mechanism at the other side, vacuumizing the whole magnetron sputtering device, filling high-purity Ar gas when the vacuum degree is 3×10 -4 Pa, starting a Cu target to perform pre-sputtering for 3 minutes in the whole magnetron sputtering process, starting the unreeling and reeling mechanism to enable the polyimide film to run in the magnetron sputtering chamber, wherein the magnetron sputtering rate of a fixed Cu target is 300nm/min, and the moving rate of the polyimide film is 100mm/min, so that the Cu layer with the thickness of 1.2 mu m is obtained.
The XRD pattern of the composite film prepared in example 1 is shown in FIG. 1. It can be seen from fig. 1 that the surface of the composite film is entirely composed of copper, and there is no diffraction peak of the transition layer metal Al, which means that the transition layer Al has an excellent ability to join the polyimide film and the Cu layer.
The internal resistivity of the composite film prepared in example 1 was measured by the four-probe resistance method, and as a result, it was 3.8. Mu. Ohm. Cm, which is lower than the square resistivity of Cu of the same thickness in the current market by 5 to 8. Mu. Ohm. Cm.
The peel strength value of the composite film prepared in example 1 was 18.34N/cm according to GB/T13557-2017 test, exceeding the electronic industry requirements.
Example 2
(1) And installing a pure Ti target and a pure Cu target in the magnetron sputtering chamber, and installing a series of glass substrates on a continuous sample rack for testing the quantitative relation between magnetron sputtering power and sputtering rate. When the vacuum degree of the magnetron sputtering chamber reaches 3X 10 -4 Pa, high-purity Ar gas is filled, in the whole magnetron sputtering process, the flowing Ar gas pressure is 0.8Pa, a Ti target is started to perform pre-sputtering for 3 minutes, the sputtering power is fixed at 200W, then a Ti film is subjected to magnetron sputtering on a glass substrate, and the sputtering time is 5 minutes; continuously increasing the Ti magnetron sputtering power to 500W, stabilizing for 2 minutes, continuously moving the next glass substrate, and performing magnetron sputtering for 5 minutes; in the same way, the magnetron sputtering power of the Ti target is increased to 10kW. Taking out the glass substrate, measuring the thickness of the Ti film by using a step instrument, and obtaining a series of quantitative relations between the magnetron sputtering power and the magnetron sputtering rate of Ti;
By the same method, a series of Cu films under different powers are subjected to magnetron sputtering, and a quantitative relation between the magnetron sputtering power of a Cu target and the magnetron sputtering rate of Cu is constructed.
(2) Loading a roll of polyimide film (with the thickness of 0.15 mm) into an unreeling device of a magnetron sputtering chamber, fixing the polyimide film on a reeling mechanism at the other side, vacuumizing the whole magnetron sputtering device, filling high-purity Ar gas when the vacuum degree reaches 3X 10 -4 Pa, starting a Ti target to perform pre-sputtering for 3 minutes when the flowing Ar gas pressure is 0.8Pa in the whole magnetron sputtering process, starting the unreeling and reeling mechanism to enable the polyimide film to run in the magnetron sputtering chamber, fixing the magnetron sputtering rate of a Ti target to be 15nm/min, enabling the moving rate of the polyimide film to be 100mm/min, and performing magnetron sputtering on one side of the polyimide film to obtain the polyimide film coated by the Ti transition layer with the thickness of 15 nm;
(3) And loading the polyimide film coated by the Ti transition layer into an unreeling device of a magnetron sputtering chamber, fixing the polyimide film on a reeling mechanism at the other side, vacuumizing the whole magnetron sputtering device, filling high-purity Ar gas when the vacuum degree is 3×10 -4 Pa, starting a Cu target to perform pre-sputtering for 3 minutes in the whole magnetron sputtering process, starting the unreeling and reeling mechanism to enable the polyimide film to run in the magnetron sputtering chamber, wherein the magnetron sputtering rate of a fixed Cu target is 200nm/min, and the moving rate of the polyimide film is 100mm/min, so that the Cu layer with the thickness of 1.5 mu m is obtained.
The XRD pattern of the composite film prepared in example 2 is shown in FIG. 2. It can be seen from fig. 2 that the surface of the composite film is entirely composed of copper, and there is no diffraction peak of the transition layer metal Ti, which means that the transition layer Ti has an excellent ability to join the polyimide film with the Cu layer.
The internal resistivity of the composite film prepared in example 2 was measured by the four-probe resistance method, and as a result, it was 3.2. Mu. Ω. Cm, which is lower than the square resistivity of Cu of the same thickness in the current market by 5 to 8. Mu. Ω. Cm.
The composite film prepared in accordance with GB/T13557-2017 test example 2 had a peel strength value of 19.67N/cm, exceeding the electronic industry requirements.
Comparative example 1
The transition layer in example 1 was replaced with Fe, and the other parameters were the same as in example 1.
The internal resistivity of the composite film prepared in comparative example 1 was measured by a four-probe resistance method, and found to be 4.2. Mu. Ω. Cm.
The peel strength value of the composite film prepared in accordance with comparative example 1 was 7.86N/cm as measured in accordance with GB/T13557-2017.
Comparative example 2
The transition layer in example 1 was replaced with Ni, and the other parameters were the same as in example 1.
The internal resistivity of the composite film prepared in comparative example 2 was measured by a four-probe resistance method, and found to be 4.4. Mu. Ω. Cm.
The peel strength value of the composite film prepared in accordance with comparative example 2 was 10.35N/cm as measured in accordance with GB/T13557-2017.
Comparative example 3
The transition layer in example 1 was replaced with Mg, and the other parameters were the same as in example 1.
The internal resistivity of the composite film prepared in comparative example 3 was measured by a four-probe resistance method, and found to be 4.2. Mu. Ω. Cm.
The peel strength value of the composite film prepared in comparative example 3 was 6.18N/cm according to GB/T13557-2017 test.
Comparative example 4
The transition layer in example 1 was omitted and the other parameters were the same as in example 1.
The internal resistivity of the composite film prepared in comparative example 4 was measured by a four-probe resistance method, and found to be 3.9. Mu. Ω. Cm.
The peel strength value of the composite film prepared in accordance with comparative example 4 was 2.58N/cm as measured in accordance with GB/T13557-2017.
In conclusion, the invention magnetron sputters the transition layer on the surface of the polyimide film, controls the types of the transition layer and improves the binding force of the composite film.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of a polyimide/Cu composite film comprises the following steps:
(1) Performing magnetron sputtering transition layers on one side or two sides of the polyimide film to obtain a polyimide film coated with the single-side or two-side transition layers; the transition layer comprises an Al layer, a Ti layer, a Cr layer, an Al-Ti alloy layer, an Al-Cr alloy layer, a Ti-Cr alloy layer or an Al-Ti-Cr alloy layer;
(2) And (3) performing magnetron sputtering on the surface of the transition layer of the single-sided or double-sided transition layer coated polyimide film obtained in the step (1) to obtain the polyimide/Cu composite film.
2. The method according to claim 1, wherein the polyimide film in the step (1) has a thickness of 1 to 200. Mu.m.
3. The method according to claim 1, wherein the thickness of the transition layer in the step (1) is 2 to 100nm.
4. The method according to claim 1, wherein the back vacuum degree of the magnetron sputtering in the step (1) is less than 1×10 -3 Pa, the Ar pressure of the magnetron sputtering is 0.1-2 Pa, and the magnetron sputtering rate is 10-100 nm/min.
5. The method according to claim 1, wherein the copper layer in the step (2) has a thickness of 1 to 10 μm.
6. The method according to claim 1, wherein the back vacuum degree of the magnetron sputtering in the step (2) is less than 1×10 -3 Pa, the Ar pressure of the magnetron sputtering is 0.1-2 Pa, and the magnetron sputtering rate is 50-2000 nm/min.
7. The method of claim 6, wherein the step (2) is performed by magnetron sputtering while applying a bias voltage.
8. The method of claim 7, wherein the bias voltage is 50-500V.
9. The polyimide/Cu composite film produced by the production method according to any one of claims 1 to 8.
10. The use of the polyimide/Cu composite film of claim 9 as a flexible copper-clad laminate or a secondary battery current collector.
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| CN202410132198.2A CN117966096A (en) | 2024-01-31 | 2024-01-31 | Polyimide/Cu composite film and preparation method and application thereof |
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