CN221768383U - Copper-clad plate with metallized holes and circuit board - Google Patents

Abstract

The utility model relates to a copper-clad plate with metallized holes and a circuit board. Specifically, a copper-clad plate with metallized holes comprises: an insulating substrate with holes; a conductive seed layer formed on the surface and the hole wall of the substrate by simultaneously treating the surface of the substrate and the hole wall in a combination of a plurality of physical vapor depositions; and electroplating a thickening layer formed by electroplating and thickening the conductive seed layer.

Description

Copper clad boards and circuit boards with metallized holes

Technical Field

The utility model relates to a copper-clad plate and a circuit board with metallized holes.

Background Art

In the process of making copper-clad laminates or circuit boards, insulating materials are usually used as substrates, and metal materials are composited on one or both sides of the substrate to make copper-clad laminates and etched to make circuit boards. As an example of an insulating substrate, a rigid substrate (also called a hard board) can be used, such as one or more of an organic polymer rigid board, a ceramic board (such as a silicon dioxide board), a glass board, etc. The organic polymer rigid board can include one or more of LCP, PTFE, CTFE, FEP, PPE, synthetic rubber board, and glass fiber cloth/ceramic filler reinforced board, wherein the glass fiber cloth/ceramic filler reinforced board is a board with organic polymer materials such as epoxy resin, modified epoxy resin, PTFE, PPO, CE, BT, etc. as the base material and glass fiber cloth/ceramic filler as the reinforcing phase. In addition, the insulating substrate can also use a flexible board (also called a soft board), such as an organic polymer film, which includes one or more of PI (i.e., polyimide), PTO, PC, PSU, PES, PPS, PS, PE, PP, PEI, PTFE, PEEK, PA, PET, PEN, LCP or PPA.

In addition, in the circuit board industry, metallized vias are widely used to connect the circuit patterns or electronic components on the surface and back of the circuit board, or to electrically connect the conductor layers between the layers of the circuit boards in a double-layer or multi-layer circuit board to facilitate the design of multi-layer circuit patterns.

In the prior art, one method of compounding metal materials on a substrate is to press an ultra-thin copper foil onto the substrate to produce a copper-clad laminate. However, since ultra-thin copper foil is difficult to produce and laminate in the pressing method, and due to the limitation of etching accuracy, it is difficult to produce fine circuits. Moreover, the pressing method itself cannot realize the conductor layer on the hole wall of the via hole, but can only produce the conductor layer on the hole wall of the via hole in the subsequent process, so the continuity and thickness consistency between the conductor layer on the surface of the substrate and the conductor layer on the hole wall of the via hole cannot be guaranteed.

In the prior art, another method of compounding metal materials on a substrate is to use conductive ink, nanoimprinting, conventional magnetron sputtering and other technologies to uniformly compound metal materials to obtain copper-clad laminates, or directly composite metal materials graphically to obtain circuit boards. However, the circuit boards produced by these technologies have fatal defects: the bonding force between the conductive circuit and the substrate is poor, and the requirements of the back-end process cannot be met. In particular, when these technologies metallize the holes, the bonding force between the electroplated copper layer and the hole wall is poor, and the copper layer is easily detached from the hole wall. Moreover, in the hole area, the uneven distribution of current density will cause the deposition rate of copper on the hole surface to be greater than the deposition rate of the hole wall. Therefore, it is easy to form holes or cracks in the conductor layer on the hole wall during the deposition process, and the conductor layer on the hole wall is easy to delaminate or bubble when subjected to thermal shock and has a high resistance change rate, which will also cause the thickness of the conductor layer on the hole surface to be greater than the thickness of the conductor layer on the hole wall. In addition, these technologies have low processing efficiency.

There is a continuous demand in the art for a method for manufacturing copper clad laminates and circuit boards, which have strong bonding strength between the conductor layer on the surface of the substrate and the conductor layer on the hole wall, are flat and smooth at the junction, have uniform thickness, and can be processed efficiently.

Utility Model Content

The purpose of the utility model is to overcome the defects existing in the above-mentioned prior art field, and provide a copper-clad plate with metallized holes, a circuit board and a manufacturing method thereof, thereby achieving the technical effect that the conductor layer on the surface of the substrate and the conductor layer on the hole wall have strong bonding force, the junction is flat and smooth, the thickness is uniform, and the process can be efficiently performed.

Technical Solution 1. A copper-clad laminate with metallized holes, comprising:

Insulating substrate with holes;

A conductive seed layer is formed on the surface of the substrate and the pore walls by simultaneously treating the surface of the substrate and the pore walls in a combination of multiple physical vapor deposition methods;

The electroplating thickening layer is formed by electroplating thickening the conductive seed crystal layer.

Technical Solution 2. The copper-clad laminate according to Technical Solution 1 is characterized in that the substrate is a polyimide film.

Technical Solution 3. The copper clad laminate according to Technical Solution 1 is characterized in that the holes are formed by mechanical drilling or laser drilling.

Technical Solution 4. The copper-clad laminate according to Technical Solution 3 is characterized in that the hole is a blind hole or a through hole with a hole diameter of 20-500 μm.

Technical Solution 5. The copper-clad laminate according to Technical Solution 3 is characterized in that the hole is a blind hole or a through hole with a hole diameter of 20-200 μm.

Technical Solution 6. A copper-clad laminate according to any one of Technical Solutions 3-5, characterized in that the depth of the blind hole is 5-200 μm.

Technical Solution 7. The copper-clad laminate according to Technical Solution 1 is characterized in that the multiple physical vapor deposition methods include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

Technical Solution 8. The copper-clad laminate according to Technical Solution 1 is characterized in that the combination of multiple physical vapor depositions includes high-power pulsed magnetron sputtering.

Technical Solution 9. The copper-clad laminate according to Technical Solution 1 is characterized in that the treatment in a combination of multiple physical vapor deposition methods includes:

First, ion implantation is performed, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition, and finally conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition;

Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering;

Alternatively, high power pulsed magnetron sputtering is performed first, followed by ion implantation.

Technical Solution 10. The copper-clad laminate according to Technical Solution 1 is characterized in that the standard deviation of the thickness of the conductive seed crystal layer is 5%-20%; the ratio of the thickness of the conductor layer on the hole wall to the thickness of the conductor layer on the surface of the substrate is greater than or equal to 1:1.

Technical Solution 11. The copper-clad laminate according to Technical Solution 1 is characterized in that the substrate is a polyimide film with a thickness of 5-200 μm, and the drilled hole is a through hole with a pore size of 20-200 μm;

Processing in a combination of various physical vapor deposition methods includes:

High power pulsed magnetron sputtering is first performed to form the nickel layer, followed by conventional magnetron sputtering to sputter the copper layer.

Technical Solution 12. The copper-clad laminate according to Technical Solution 11 is characterized in that, during high-power pulsed magnetron sputtering, nickel is used as the target material, the pulse width is 80-3000μs, the frequency is 200-5000Hz, the peak current is 70-2000A, there are one or more sputtering sources, the power of each sputtering source is 1.5-50KW, and a 6-200nm thick nickel layer is formed on the surface of the substrate and the pore wall.

Technical Solution 13. The copper-clad laminate according to Technical Solution 11 is characterized in that the conventional magnetron sputtering is DC magnetron sputtering. During the DC magnetron sputtering, copper is used as the target material, the voltage is 300-2000V, the current is 4-100A, the power is 1.2-200KW, and a copper layer with a thickness of 100-500nm is sputtered.

Technical Solution 14. The copper-clad laminate according to Technical Solution 11 is characterized in that 1-25 μm of copper is electroplated on the conventional magnetron sputtered copper layer to obtain a copper-clad laminate with metallized holes.

Technical Solution 15. A circuit board with metallized holes, comprising:

Insulating substrate with holes;

A conductive seed layer is formed on the surface of the substrate and the pore walls by simultaneously treating the surface of the substrate and the pore walls in a combination of multiple physical vapor deposition methods;

A circuit is formed by adding patterned metal on the conductive seed layer.

Technical Solution 16. The circuit board according to Technical Solution 15 is characterized in that the substrate is a polyimide film.

Technical Solution 17. The circuit board according to Technical Solution 15 is characterized in that the holes are formed by mechanical drilling or laser drilling.

Technical Solution 18. The circuit board according to Technical Solution 17 is characterized in that the hole is a blind hole or a through hole with a hole diameter of 20-500μm.

Technical Solution 19. The circuit board according to Technical Solution 17 is characterized in that the hole is a blind hole or a through hole with a hole diameter of 20-200μm.

Technical Solution 20. A circuit board according to any one of Technical Solutions 17-19, characterized in that the depth of the blind hole is 5-200 μm.

Technical Solution 21. The circuit board according to Technical Solution 15 is characterized in that the multiple physical vapor deposition methods include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

Technical Solution 22. The circuit board according to Technical Solution 15 is characterized in that the combination of multiple physical vapor deposition methods includes high-power pulsed magnetron sputtering.

Technical Solution 23. The circuit board according to Technical Solution 15 is characterized in that the processing in a combination of multiple physical vapor deposition methods includes:

First, ion implantation is performed, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition, and finally conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition;

Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering;

Alternatively, high power pulsed magnetron sputtering is performed first, followed by ion implantation.

Technical Solution 24. The circuit board according to Technical Solution 15 is characterized in that the standard deviation of the thickness of the conductive seed crystal layer is 5%-20%, and the ratio of the thickness of the conductor layer on the hole wall to the thickness of the conductor layer on the surface of the substrate is greater than or equal to 1:1.

Technical Solution 25. The circuit board according to Technical Solution 15 is characterized in that the circuit board is a single-layer circuit board or a multi-layer circuit board.

Technical Solution 26. The circuit board according to Technical Solution 15 is characterized in that the substrate is a polyimide film with a thickness of 5-200 μm, and the drilled holes are through holes with a pore size of 20-200 μm;

Processing in a combination of various physical vapor deposition methods includes:

High power pulsed magnetron sputtering is first performed to form the nickel layer, followed by conventional magnetron sputtering to sputter the copper layer.

Technical Solution 27. The circuit board according to Technical Solution 26 is characterized in that during high-power pulsed magnetron sputtering, nickel is used as the target material, the pulse width is 80-3000μs, the frequency is 200-5000Hz, the peak current is 70-2000A, there are one or more sputtering sources, and the power of each sputtering source is 1.5-50KW, and a 6-200nm thick nickel layer is formed on the surface of the substrate and the hole wall.

Technical Solution 28. The circuit board according to Technical Solution 26 is characterized in that the conventional magnetron sputtering is DC magnetron sputtering. During the DC magnetron sputtering, copper is used as the target material, the voltage is 300-2000V, the current is 4-100A, the power is 1.2-200KW, and a copper layer with a thickness of 100-500nm is sputtered.

Technical Solution 29. The circuit board according to Technical Solution 26 is characterized in that a 0.5-25 μm thick patterned copper layer is added to the conventional magnetron sputtered copper layer to obtain a circuit board with metallized holes.

According to the above technical scheme, copper-clad boards with metallized holes, single-sided or double-sided circuit boards, and arbitrary layer interconnect (HDI) circuit boards can be formed. Due to the combination of multiple physical vapor depositions according to the utility model, especially the combination of multiple physical vapor depositions including high-power pulsed magnetron sputtering, the conductor layer on the surface of the substrate and the conductor layer on the hole wall have strong bonding force (up to 1.0N/mm), and the junction is flat and smooth, and the thickness is uniform (the ratio of the thickness of the conductor layer on the hole wall to the thickness of the conductor layer on the surface of the substrate can reach or even exceed 1:1), and there will be no holes or cracks. The conductor layer on the hole wall has no delamination and blistering under thermal shock and has a low resistance change rate (<5%). At the same time, the processing efficiency is high and the processing speed is fast. The line speed of the production line is as high as 1.5-3m/s. Compared with the ion implantation plasma deposition technology, the film speed of the production line is increased by 3-10 times. Thereby, the defects that the conductor layer on the surface of the substrate and the conductor layer on the hole wall in the prior art are easily present are avoided.

The power of high-power pulsed magnetron sputtering and conventional magnetron sputtering, including the power of DC magnetron sputtering, mentioned in this application refer to the power of a single sputtering source, rather than the power of multiple sources superimposed.

BRIEF DESCRIPTION OF THE DRAWINGS

After reading the following detailed description with reference to the accompanying drawings, those skilled in the art will more easily understand these and other features, aspects and advantages of the present invention. For the sake of clarity, the drawings are not necessarily drawn to scale, but some parts thereof may be exaggerated to show details. In all drawings, the same reference numerals represent the same or similar parts, wherein:

FIG1 is a flow chart of a method for manufacturing a copper clad laminate with metallized holes according to an exemplary embodiment of the present utility model;

FIG2 is a flow chart of a method for manufacturing a copper-clad laminate with metallized holes and then manufacturing a circuit board according to an exemplary embodiment of the present utility model;

FIG3 is a flow chart of a method for manufacturing a circuit board with metallized holes according to an exemplary embodiment of the present utility model;

4a-c are photos of copper-clad laminates with metallized holes made using a combination of multiple physical vapor deposition methods according to the present invention;

5a-b are photos of a copper-clad laminate with metallized holes made by another combination of multiple physical vapor deposition processes according to the present invention;

6a-c are photos of a copper-clad laminate with metallized holes made by using yet another combination of multiple physical vapor deposition processes according to the present invention;

FIG7 is a photograph of a copper-clad laminate with metallized holes made using an embodiment of the present invention;

FIG8 is a photograph of a copper-clad laminate with metallized holes made using another embodiment of the present invention;

9a-b are photos of a circuit board with metallized holes made using yet another embodiment of the present invention.

DETAILED DESCRIPTION

The following describes the embodiments of the present invention in detail with reference to the accompanying drawings. It should be understood by those skilled in the art that these descriptions merely list exemplary embodiments of the present invention and are by no means intended to limit the protection scope of the present invention.

Fig. 1 is a flow chart of a method for manufacturing a copper-clad laminate with metallized holes according to an exemplary embodiment of the utility model. As shown in Fig. 1, the method comprises the following steps: drilling holes in an insulating substrate (step S1); pre-treating the substrate with holes (step S2); treating the surface of the substrate and the hole wall simultaneously in a combination of multiple physical vapor deposition methods to form a conductive seed layer on the surface of the substrate and the hole wall, thereby obtaining a metallized substrate with metallized holes (step S3); and electroplating and thickening the metallized substrate to obtain a copper-clad laminate with metallized holes (step S4).

The method further includes making a circuit board using a copper-clad laminate with metallized holes (step S5), as shown in Figure 2. In step S5, the circuit board is made using a semi-additive process, which is a processing method in which a copper layer is formed on a patterned photoresist layer and then the photoresist layer is peeled off.

Thus, a copper-clad laminate with metallized holes is obtained, which includes: an insulating substrate with holes; a conductive seed crystal layer formed on the surface of the substrate and the hole wall by treating the surface of the substrate and the hole wall simultaneously in a combination of multiple physical vapor deposition methods; and an electroplating thickening layer formed by electroplating and thickening the conductive seed crystal layer. Furthermore, the copper-clad laminate with metallized holes can be used to make circuit boards.

FIG3 is a flow chart of a method for manufacturing a circuit board with metallized holes according to an exemplary embodiment of the utility model. As shown in FIG3 , the method includes the following steps: drilling holes in an insulating substrate (step S1); pre-treating the substrate with holes (step S2); treating the surface of the substrate and the hole wall simultaneously in a combination of multiple physical vapor deposition methods to form a conductive seed layer on the surface of the substrate and the hole wall, thereby obtaining a metallized substrate with metallized holes (step S3); adding patterned metal to the metallized substrate with metallized holes, thereby making a circuit on the conductive seed layer of the metallized substrate with metallized holes, thereby obtaining a single-layer circuit board (step S4). In step S4, patterned metal is added to both surfaces of the metallized substrate with metallized holes, thereby obtaining a double-sided circuit board. Using the double-sided circuit board as the substrate, the upper and lower surfaces of the double-sided circuit board are covered with a prepreg, and steps S1 to S4 are repeated once or multiple times for the double-sided circuit board covered with the prepreg, thereby obtaining a multi-layer circuit board.

Thus, a circuit board with metallized holes is prepared, which includes: an insulating substrate with holes; a conductive seed crystal layer, which is formed on the surface of the substrate and the hole wall by treating the surface of the substrate and the hole wall simultaneously in a combination of multiple physical vapor deposition methods; and a circuit, which is formed by adding patterned metal on the conductive seed crystal layer. The circuit board is a single-layer circuit board or a multi-layer circuit board.

Specifically, the substrate is a polyimide film. If the aperture is large, mechanical drilling can be used. When the aperture is small (for example, less than 100 μm), laser drilling can be used. More specifically, the drilled hole is a blind hole or a through hole with an aperture of 20-500 μm, preferably 20-200 μm. In addition, depending on the thickness of the film, the depth of the drilled hole is 5-200 μm; wherein the film thickness is mainly 25 μm, 12.5 μm, 20 μm, 38 μm and 50 μm. Subsequent electroplating may electroplate the through hole and blind hole into a filled hole and a blind buried hole (especially a small aperture), which is advantageous for the filling of the flexible circuit board. For example, for a hole with a depth of 30 μm, when the thickness of the copper layer on the electroplated hole wall is 15 μm and the thickness of the copper layer on the surface of the substrate is also 15 μm, the hole can be filled.

The pre-treatment of the porous substrate after drilling includes one or more of plasma cleaning, dehydration, and alkaline solution surface treatment to remove dirt or the perforated carbonized layer.

Specifically, the various physical vapor deposition methods include: ion implantation, plasma deposition, high power pulsed magnetron sputtering (HiPIMS), and conventional magnetron sputtering. In particular, the combination of various physical vapor deposition methods includes high power pulsed magnetron sputtering.

More specifically, processing in a combination of multiple physical vapor deposition methods includes:

First, ion implantation is performed, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition, and finally conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by conventional magnetron sputtering;

Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition;

Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering;

Alternatively, high power pulsed magnetron sputtering is performed first, followed by ion implantation.

Ion implantation can be achieved by the following method: using a conductive material as a target material, in an ion implantation device under a vacuum environment, ionizing the conductive material in the target material by arc action to generate ions, and then accelerating the ions under a high voltage electric field to obtain very high energy. The high-energy conductive material ions then directly impact the surface of the substrate and the pore walls of the pores at a very high speed, and are implanted to a certain depth below the surface of the substrate and the pore walls. Specifically, the ion source used for ion implantation is a magnetically filtered vacuum cathode arc (i.e., FCVA) source. During ion implantation, depending on the type of polyimide film, the energy of the implanted ions is 5-1000 keV, preferably 3-20 keV; the implantation dose is 1.0×10 ¹⁴ -5.0×10 ¹⁶ ions/cm ² ; and the implantation depth is 5-50 nm.

Plasma deposition is similar to the ion implantation described above, except that a lower voltage is applied to make the conductive material ions have lower energy. That is, a conductive material is used as a target material, and in a vacuum environment, the conductive material in the target material is ionized by an arc to generate ions, and then the ions are accelerated under an electric field to obtain a certain amount of energy. The accelerated conductive material ions fly to the surface and pore walls of the substrate and deposit. Specifically, the ion source used for plasma deposition is a magnetically filtered vacuum cathode arc source. During plasma deposition, the energy of the deposited ions is 50-1000eV, preferably 30-100eV.

Conventional magnetron sputtering can be achieved by the following method: using a conductive material as a target material, in a DC magnetron sputtering device under a vacuum environment, using a power supply to apply a positive voltage to the target material to generate ion bombardment, and at the same time applying a magnetic field to the surface of the target material for guidance, so that the atoms or molecules generated when the ions bombard the surface of the target material are deposited on the surface and pore walls of the substrate. Specifically, conventional magnetron sputtering mainly includes DC magnetron sputtering. More specifically, when the power supply used is a DC power supply, conventional magnetron sputtering is DC magnetron sputtering. Specifically, during DC magnetron sputtering, the voltage is 100V-2000V and the current is 1-100A.

High-power pulsed magnetron sputtering uses a high-power pulsed power supply (therefore, it is different from conventional magnetron sputtering), so that the presence of pulses increases the parameters such as pulse width, frequency, duty cycle, peak voltage, peak current, etc., and is therefore more flexible and controllable. In particular, high-power pulsed magnetron sputtering can achieve high plasma density and high metal ionization rate, thereby optimizing the film quality. Specifically, during high-power pulsed magnetron sputtering, the ionization rate of nickel is greater than 30%, and the ionization rate of copper is greater than 50%; the acceleration bias is 0-100kV, preferably 0-50V; the target surface power density is 1-100W/ ^cm2 , preferably 3-20W/ ^cm2 ; the pulse width is 80-3000μs, preferably 100μs; the frequency is 200-5000Hz, preferably 300-450Hz; the peak current is 50-2000A, preferably 100A; the moving speed of the substrate in the equipment is 0.5-15m/s. The utility model includes the beneficial effects of high-power pulsed magnetron sputtering in the combination of multiple physical vapor depositions: the target surface power density of high-power pulsed magnetron sputtering can reach 10-80W/ ^cm2 , so that in the generated metal plasma, the ionization rate of nickel can be >30%, and the ionization rate of copper can be >50%. More specifically, the utility model adopts high-power pulsed magnetron sputtering or continuous high-power pulsed magnetron sputtering, relying on its high-intensity glow discharge, to achieve high-efficiency, high-ionization rate vacuum sputtering, and through ion energy control technology, it realizes the one-step continuous completion of high-bonding strength and high-density metal film preparation on the surface of the substrate.

After using the combination of multiple physical vapor deposition methods of the utility model, the same conductive seed crystal layer is formed on the surface of the substrate and the hole wall. In this way, there is no need to perform special separate treatment on the hole part, and the resulting conductive seed crystal layer has a uniform texture and a strong bonding force with the substrate. Specifically, the standard deviation of the thickness of the conductive seed crystal layer is 5%-20%. Moreover, the ratio of the thickness of the conductor layer on the hole wall of the metallized hole to the thickness of the conductor layer on the surface of the substrate is greater than or equal to 1:1.

Several combinations of various physical vapor deposition methods according to the present invention are exemplified below to enhance understanding of the present invention.

(Combination 1)

This combination is high-power pulsed magnetron sputtering + plasma deposition + DC magnetron sputtering. Specifically, the substrate used is a Dupont 100EN-C type polyimide film with a thickness of 25 μm and a through-hole diameter of 100 μm.

First, high-power pulsed magnetron sputtering is performed, with nickel as the target material, a pulse width of 100 μs, a frequency of 350 Hz, a peak current of 120 A, one or more sputtering sources, and a power of 1.5-4 kW for each sputtering source, to form a 20-30 nm thick nickel layer on the surface of the substrate and the pore wall.

Then, plasma deposition is performed, with nickel as the target material, arc current of 40-100A, extraction current of 10A, vacuum degree of 0.022-0.024Pa, argon flow rate of 5-12sccm, and a nickel layer is deposited.

Finally, direct current magnetron sputtering was performed, using copper as a target material, selecting a voltage of 320 V and a current of 4.5 A to sputter a copper layer. The total thickness of the plasma deposited nickel layer and the direct current magnetron sputtered copper layer was greater than 100 nm.

12 μm of copper is electroplated on the DC magnetron sputtered copper layer to obtain a copper clad laminate with metallized holes.

The results of the above processing are shown in Figures 4a-c. Figure 4a is a FIB-TEM photo of the nickel layer sputtered by high-power pulsed magnetron sputtering, showing that the thickness of the nickel layer sputtered by high-power pulsed magnetron sputtering is 20-30nm; Figure 4b is a FIB-TEM-EDX photo of the element line scanning qualitative and quantitative analysis; Figure 4c is a slice optical microscope photo of the copper clad board with metallized holes, showing that the thickness of the copper layer on the surface of the substrate and the hole wall is about 12μm, the thickness ratio is 1:1, and the hole diameter is 100μm. In addition, the bonding force of the copper layer on the surface of the substrate is 1.0N/mm@12μm copper thickness, and the copper layer on the hole wall has no delamination or blistering under thermal shock, and the resistance change rate is <5%.

(Combination 2)

This combination is high-power pulsed magnetron sputtering + plasma deposition + DC magnetron sputtering. Specifically, the substrate used is a polyimide film with a thickness of 38 μm and a through-hole diameter of 20 μm.

First, high-power pulsed magnetron sputtering is performed, with nickel as the target material, a pulse width of 100 μs, a frequency of 420 Hz, a peak current of 100 A, one or more sputtering sources, and a power of 1.5-4 kW for each sputtering source, to form a 0-15 nm thick nickel layer on the surface of the substrate and the pore wall.

Then, plasma deposition is performed, with copper as the target material, arc current of 40-100A, extraction current of 7-15A (preferably 10A), vacuum degree of 0.022-0.024Pa, argon flow rate of 5-12sccm, and a copper layer of 8-60nm thickness is deposited.

Finally, direct current magnetron sputtering was performed, with copper as the target material, a voltage of 380 V and a current of 10 A were selected, and a copper layer with a thickness of >100 nm was sputtered, thereby obtaining a conductive seed crystal layer.

The results of the above processing are shown in Figure 5a-b. Figure 5a is a FIB-TEM photo of the nickel layer sputtered by high-power pulsed magnetron sputtering. Carbon, oxygen and a small amount of copper were detected at spectrum 10, nickel and copper elements and carbon elements derived from surface adsorption were detected at spectrum 6, spectrum 7, and spectrum 8, and copper element was detected at spectrum 9; Figure 5b is a FIB-TEM-EDX photo of element line scanning qualitative and quantitative analysis.

(Combination 3)

The combination of this example is high-power pulsed magnetron sputtering + DC magnetron sputtering. Specifically, the substrate used is a polyimide film with a thickness of 12.5 μm and a through-hole diameter of 20 μm and 50 μm.

First, high-power pulsed magnetron sputtering was performed with nickel as the target material. The current was 90A, the voltage was 750V, the vacuum was 0.14Pa, the pulse width was 100μs, the frequency was 400Hz, the peak current was 120A, and there were one or more sputtering sources. The power of each sputtering source was 1.5-4KW, and a 6nm thick nickel layer was formed on the surface of the substrate and the pore wall.

Then, direct current magnetron sputtering was performed, with copper as the target material, a voltage of 345 V, a current of 5.2 A, a power of 0.8 KW, a vacuum degree of 0.38 Pa, and a copper layer with a thickness of >100 nm was sputtered.

2 μm of copper is electroplated on the DC magnetron sputtered copper layer to obtain a copper clad laminate with metallized holes.

The results of the above processing are shown in Figures 6a-c. Figure 6a is a FIB-TEM photo of the nickel layer sputtered by high-power pulsed magnetron sputtering, showing that the thickness of the nickel layer sputtered by high-power pulsed magnetron sputtering is 6nm; Figure 6b is a FIB-TEM-EDX photo of the electroplated copper layer, showing that the thickness of the electroplated copper layer is 1.9μm; Figure 6c is a slice optical microscope photo of the copper-clad board with metallized holes, showing that the thickness of the copper layer on the surface of the substrate and the hole wall is about 2μm, the thickness ratio is 1:1, and the hole diameter is 40μm. In addition, the bonding force of the copper layer on the surface of the substrate is 0.8N/mm, and the copper layer on the hole wall has no delamination or blistering under thermal shock, and the resistance change rate is <5%.

Several embodiments of a copper-clad laminate with metallized holes, a circuit board, and a manufacturing method thereof for implementing the utility model will be illustrated below to enhance understanding of the utility model.

(Example 1)

1.1 A 25 μm thick polyimide film is selected as a substrate. Through holes are drilled by laser in the polyimide film, and the apertures of the through holes are 20 μm, 40 μm, and 50 μm, respectively.

1.2 Pre-treatment. Specifically, the substrate (rolled polyimide film) is placed in the ion implantation equipment through a continuous feeding mechanism, and the vacuum is evacuated to 5.0×10 ^-3 Pa, and the substrate is subjected to ion beam irradiation treatment (Plasma treatment). In a vacuum environment, the upper and lower surfaces of the polyimide film are irradiated with an argon ion beam at the same time, with an argon flow rate of 20-50sccm, an ion energy of 300-500eV, an irradiation amount of 1.0-5.0x10 ¹² ions/cm ² , and an irradiation time of 2-10 seconds. At this time, the temperature is controlled to rise to no more than 75 degrees for dehydration treatment, and the water vapor in the ion beam chamber is extracted using a vacuum device. Ion beam irradiation simultaneously cleans and dehydrates the surface.

1.3 The conductive seed layer is produced by a combination of plasma deposition + high power pulsed magnetron sputtering + DC magnetron sputtering.

First, in a vacuum device, the chamber is evacuated to 0.022-0.024 Pa, and plasma deposition is performed using nickel as a target. A magnetically filtered vacuum cathode arc source is used to simultaneously perform plasma deposition of nickel on the surface of the polyimide membrane and the pore wall. The deposition ion energy is 75 eV, the arc current is 100 A, the extraction current is 10 A, and the deposited nickel thickness is 8 nm.

Then, nickel was used as the target material, and a high-power pulsed magnetron sputtering power supply was turned on. The voltage was 720V, the current was 95A, the pulse width was 100μs, the frequency was 350Hz, the peak current was 110A, and there were one or more sputtering sources. The power of each sputtering source was 1.5KW. High-power pulsed magnetron sputtering was performed. The ionization rate of nickel was >30%, and a 5nm thick nickel layer was sputtered. The sheet resistance after sputtering was 5-120 ohms.

Finally, copper is used as a target material to perform DC magnetron sputtering at a voltage of 435 V and a current of 5.2 A to sputter a 120 nm thick copper layer. The sheet resistance after sputtering is 0.1-50 ohms, preferably 0.5-30 ohms.

1.4 Electroplating thickening to prepare a double-sided flexible copper-clad laminate with metallized holes. Specifically, the copper film on both the upper and lower surfaces of the substrate and the hole wall is thickened to 12 μm on the electroplating copper production line.

The structure of the copper-clad laminate with metallized holes obtained in Example 1 is as follows: a double-sided copper-clad laminate with metallized through holes, the polyimide film thickness is 25 μm, and the through hole diameters are 20 μm, 40 μm, and 50 μm, respectively. The surface of the polyimide film and the hole wall of the metallized hole are, from the inner layer to the outer layer, the following: a plasma-deposited nickel layer with a thickness of 8 nm; a high-power pulsed magnetron sputtered nickel layer with a thickness of 5 nm; a DC magnetron sputtered copper layer with a thickness of 120 nm; and an electroplated copper layer with a thickness of 12 μm. The interface between the copper layer on the surface of the substrate of the copper-clad laminate with metallized holes and the copper layer on the hole wall is smooth and uniform in thickness.

The bonding force of the copper layer on the surface of the substrate of the copper-clad laminate finally obtained is 1.0 N/mm, the copper layer on the hole wall has no delamination and blistering under thermal shock, and the resistance change rate is less than 5%. Moreover, the junction between the copper layer on the surface of the substrate of the copper-clad laminate with metallized holes and the copper layer on the hole wall is flat and smooth, and has uniform thickness.

(Example 2)

2.1 A 38 μm thick polyimide film is selected as the substrate. Through holes and blind holes are laser drilled in the polyimide film, with the diameter of the through hole being 40 μm and the diameter of the blind hole being 20 μm.

2.2 Pre-treatment: Place the substrate (rolled polyimide film) into the ion implantation equipment through the continuous feeding mechanism, evacuate to 1.2×10 ^-2 Pa, and irradiate the substrate with ion beam. In a vacuum environment, ion beams are irradiated on both the upper and lower surfaces of the polyimide film with a mixed gas of argon and oxygen at a flow rate of 100 sccm. At this time, the temperature is controlled to rise to more than 75 degrees for dehydration treatment, and the water vapor in the ion beam chamber is extracted using a vacuum device. Ion beam irradiation simultaneously cleans and dehydrates the surface.

2.3 The conductive seed layer is produced by a combination of high power pulsed magnetron sputtering + plasma deposition + DC magnetron sputtering.

First, in a vacuum device, the vacuum is evacuated to 0.2Pa, nickel is used as a target material, a high-power pulse magnetron sputtering power supply is turned on, the voltage is 680V, the current is 300A, the pulse width is 100μs, the frequency is 320Hz, the peak current is 240A, there are one or more sputtering sources, the power of each sputtering source is 4KW, the target surface power density is 5-15W/ ^cm2 , high-power pulse magnetron sputtering is performed, the nickel ionization rate is>30%, and the sputtering thickness is 28nm of the nickel layer.

Then, the chamber was evacuated to 0.020-0.022Pa, and nickel was used as the target material. A magnetically filtered vacuum cathode arc source was used to simultaneously perform plasma deposition on the polyimide membrane surface and the pore wall. The argon flow rate was 5-12sccm, the deposition ion energy was 75eV, the arc current was 100A, the extraction current was 10A, and a nickel layer with a thickness of 60nm was deposited. The square resistance after deposition was 5-120 ohms.

Finally, using copper as the target material, DC magnetron sputtering was started with a voltage of 380 V and a current of 10 A to sputter a copper layer with a thickness of 100 nm. The square resistance after sputtering was 0.1-50 ohms, preferably 2-30 ohms.

2.4 Electroplating thickening to prepare a double-sided flexible copper-clad laminate with metallized holes. Specifically, the copper film on both the upper and lower surfaces of the substrate and the hole wall is thickened to 5 μm on the copper electroplating production line. As an optional embodiment, the through holes and/or blind holes can be electroplated into filled holes and blind buried holes.

The structure of the copper-clad laminate with metallized holes obtained in Example 2 is as follows: a double-sided copper-clad laminate with metallized through holes, a polyimide film thickness of 38 μm, a through hole diameter of 40 μm, and a blind hole diameter of 20 μm. The surface of the polyimide film and the hole wall of the metallized hole are, from the inner layer to the outer layer, in order: a nickel layer of high-power pulsed magnetron sputtering with a thickness of 30 nm; a plasma deposited nickel layer with a thickness of 60 nm; a DC magnetron sputtering copper layer with a thickness of 100 nm; and an electroplated copper layer with a thickness of 5 μm. The junction between the copper layer on the surface of the substrate of the product and the copper layer on the hole wall is smooth and uniform in thickness. As an optional embodiment, the hole structure can be a metallized through hole and a blind hole structure, or a filled hole and a blind buried hole structure. The bonding force of the copper layer on the surface of the substrate of the copper-clad laminate with metallized holes is 0.9 N/mm, and the copper layer on the hole wall has no delamination or blistering under thermal shock, and the resistance change rate is <5%.

(Example 3)

3.1 A 25 μm thick polyimide film is selected as a substrate. A through hole is laser drilled in the polyimide film, and the diameter of the through hole is 100 μm.

3.2 Pre-treatment: Place the substrate (rolled polyimide film) into the ion implantation equipment through the continuous feeding mechanism, evacuate to 5.0×10 ^-2 Pa, and irradiate the substrate with ion beam. In a vacuum environment, argon ion beams are irradiated on both the upper and lower surfaces of the polyimide film at a flow rate of 10 sccm. At this time, the temperature is controlled to rise to more than 75 degrees for dehydration treatment, and the water vapor in the ion beam chamber is extracted using a vacuum device. Ion beam irradiation simultaneously cleans and dehydrates the surface.

3.3 The conductive seed layer is produced by a combination of high power pulsed magnetron sputtering + DC magnetron sputtering.

First, in a vacuum device, evacuate to 0.1-0.3Pa, use nickel as a target material, turn on a high-power pulse magnetron sputtering power supply, the voltage is 750V, the current is 90A, there are one or more sputtering sources, the power of each sputtering source is 2KW, the pulse width is 100μs, the frequency is 450Hz, the peak current is 130A, the target surface power density is 15-20W/ ^cm2 , and high-power pulse magnetron sputtering is performed. The ionization rate of nickel is greater than 30%, the sputtering thickness is 20nm of the nickel layer, and the sheet resistance after nickel deposition is 40-80 ohms.

Then, using copper as the target material, DC magnetron sputtering was started with a voltage of 345 V, a current of 5.2 A, a power of 3.0 KW, a vacuum degree of 0.35 Pa, and a copper layer with a sputtering thickness of 80 nm. The square resistance after sputtering was 0.1-50 ohms, preferably 0.5-30 ohms.

3.4 Electroplating thickening to prepare a double-sided flexible copper-clad laminate with metallized holes. Specifically, the copper film on both the upper and lower surfaces of the substrate and the hole wall is thickened to 5 μm on the electroplating copper production line.

The structure of the copper-clad laminate with metallized holes obtained in Example 3 is as follows: a double-sided copper-clad laminate with metallized through holes, a polyimide film thickness of 25 μm, and a through hole diameter of 100 μm. The surface of the polyimide film and the hole wall of the metallized hole are, from the inner layer to the outer layer, a nickel layer of high-power pulsed magnetron sputtering with a thickness of 20 nm; a copper layer of DC magnetron sputtering with a thickness of 80 nm; and an electroplated copper layer with a thickness of 5 μm. The interface between the copper layer on the surface of the substrate of the copper-clad laminate with metallized holes and the copper layer on the hole wall is flat and smooth, and has uniform thickness. The copper layer on the surface of the substrate of the copper-clad laminate with metallized holes has a bonding force of 0.9 N/mm, and the copper layer on the hole wall has no delamination or blistering under thermal shock (in hot oil at 260°C for 10 seconds, and shocks 3 times; the detection process refers to IPC-TM-650 test method manual 2.6.8 and 2.1.1), and the resistance change rate is less than 4% (the qualified requirement is no more than 10%). Specifically, the photo of the copper-clad laminate with metallized holes after thermal shock is shown in Figure 7.

(Example 4)

4.1 A 20 μm thick polyimide film was selected as a substrate. The polyimide film was laser drilled with a hole diameter of 30 μm and mechanically drilled with a hole diameter of 150 μm.

4.2 Pre-treatment: Place the substrate (rolled polyimide film) into the ion implantation equipment through a continuous feeding mechanism, evacuate to 9.0×10 ^-2 Pa, and perform ion beam irradiation on the substrate. In a vacuum environment, argon ion beams are simultaneously irradiated on the upper and lower surfaces of the polyimide film at a flow rate of 10 sccm. At this time, the temperature is controlled to rise to more than 75 degrees for dehydration treatment, and the water vapor in the ion beam chamber is extracted using a vacuum device. Ion beam irradiation simultaneously cleans and dehydrates the surface. As another embodiment, chemical cleaning can also be used for pre-treatment. Since laser drilling will have a carbonized layer and mechanical drilling will have high-temperature molten slag, the principle of chemical cleaning is that a weak alkaline solution (or an acidic solution first and an alkaline solution later) reacts chemically with the resin to remove the carbonized layer or slag, and at the same time, a micro-roughened surface can be formed to remove dirt generated by mechanical drilling and carbon deposits generated during laser drilling.

4.3 The conductive seed layer is produced by a combination of high power pulsed magnetron sputtering + DC magnetron sputtering.

First, in a vacuum device, the vacuum is evacuated to 0.018Pa, nickel is used as a target material, a high-power pulse magnetron sputtering power supply is turned on, the voltage is 600V, the current is 110A, there are one or more sputtering sources, the power of each sputtering source is 2.5KW, the pulse width is 100μs, the frequency is 370Hz, the peak current is 110A, the target surface power density is 15-20W/ ^cm2 , and high-power pulse magnetron sputtering is performed, the nickel ionization rate is greater than 30%, the sputtering thickness is 18nm, and the sheet resistance after sputtering is 50-80 ohms.

Then, using copper as the target material, DC magnetron sputtering was started with a voltage of 343 V, a current of 5.4 A, a power of 1.8 KW, a vacuum degree of 0.38 Pa, and a copper layer with a sputtering thickness of 120 nm. The square resistance after sputtering was 0.1-1 ohm, preferably 0.5-1 ohm.

4.4 Electroplating thickening to prepare a double-sided flexible copper-clad laminate with metallized holes. Specifically, the copper film on both the upper and lower surfaces of the substrate and the hole wall is thickened to 9 μm on the electroplating copper production line.

The structure of the copper-clad laminate with metallized holes obtained in Example 4 is as follows: a double-sided copper-clad laminate with metallized through holes, a polyimide film thickness of 20 μm, and through hole diameters of 30 μm and 150 μm. The surface of the polyimide film and the hole wall of the metallized hole are, from the inner layer to the outer layer, in order: a nickel layer of high-power pulsed magnetron sputtering, with a thickness of 18 nm; a copper layer of DC magnetron sputtering, with a thickness of 120 nm; and an electroplated copper layer, with a thickness of 9 μm. The junction between the copper layer on the surface of the substrate of the copper-clad laminate with metallized holes and the copper layer on the hole wall is smooth and uniform in thickness. The bonding force of the copper layer on the surface of the substrate of the copper-clad laminate with metallized holes is 0.8 N/mm@9 μm copper thickness, and the copper layer on the hole wall has no delamination or blistering under thermal shock, and the resistance change rate is <4% (the qualified requirement is not more than 10%). Specifically, a photo of the copper-clad laminate with metallized holes after thermal shock is shown in Figure 8.

(Example 5)

5.1 A 50 μm thick polyimide film is selected as a substrate. Laser drilling is performed on the polyimide film, and the aperture of the through hole is 30 μm.

5.2 Pre-treatment: Place the substrate (rolled polyimide film) into the ion implantation equipment through the continuous feeding mechanism, evacuate to 7.0×10 ^-2 Pa, and irradiate the substrate with ion beam. In a vacuum environment, ion beams are irradiated with argon on both the upper and lower surfaces of the polyimide film at a flow rate of 10 sccm. At this time, the temperature is controlled to rise to more than 75 degrees for dehydration treatment, and the water vapor in the ion beam chamber is extracted using a vacuum device. Ion beam irradiation simultaneously cleans and dehydrates the surface.

5.3 The conductive seed layer is produced by a combination of high power pulsed magnetron sputtering (nickel) + high power pulsed magnetron sputtering (copper) + DC magnetron sputtering.

First, in a vacuum device, the vacuum is evacuated to 0.18Pa, nickel is used as a target material, a high-power pulse magnetron sputtering power supply is turned on, the voltage is 750V, the current is 90A, the pulse width is 100μs, the frequency is 480Hz, there are one or more sputtering sources, the power of each sputtering source is 2.2KW, the target surface power density is 15-20W/ ^cm2 , the acceleration bias is 30V, and high-power pulse magnetron sputtering is performed, the nickel ionization rate is greater than 30%, and the sputtering thickness is 22nm of the nickel layer. Among them, the selection of the acceleration bias can increase the energy of the deposited metal particles, which is conducive to the metallization of the inner wall of the deep hole with a higher aspect ratio.

Then, with copper as the target material, the high-power pulsed magnetron sputtering power supply is continuously turned on, and the copper film is sputtered using continuous high-power pulsed magnetron sputtering technology. The power density of the sputtering target surface is 100W/ ^cm2 , the acceleration bias is 40V, and the acceleration bias uses a DC voltage. The ionization rate of copper is greater than 50%, and the sputtering thickness is 0.1μm. The square resistance after sputtering is 2-10 ohms.

Finally, DC magnetron sputtering was turned on with a voltage of 345 V, a current of 5.2 A, a power of 0.8 KW, a vacuum degree of 0.38 Pa, and the thickness of the sputtered copper layer was reduced to 0.3 μm.

5.4 Electroplating thickening to prepare a double-sided flexible copper-clad laminate with metallized holes. Specifically, the copper film on both the upper and lower surfaces of the substrate and the hole wall is thickened to 2 μm on the electroplating copper production line.

The structure of the copper-clad laminate with metallized holes obtained in Example 5 is as follows: a double-sided copper-clad laminate with metallized through holes, a polyimide film thickness of 50 μm, and a through hole diameter of 30 μm. The surface of the polyimide film and the hole wall of the metallized hole are, from the inner layer to the outer layer, in order: a nickel layer sputtered by high-power pulse magnetron sputtering, with a thickness of 22 nm; a copper layer sputtered by high-power pulse magnetron sputtering, with a thickness of 0.1 μm; a copper layer sputtered by DC magnetron sputtering, to a thickness of 0.3 μm; and an electroplated copper layer with a thickness of 1.7 μm. The junction between the copper layer on the surface of the substrate of the copper-clad laminate with metallized holes and the copper layer on the hole wall is flat and smooth, with uniform thickness. The copper layer on the surface of the substrate of the copper-clad laminate with metallized holes has a bonding force of 0.8 N/mm, and the copper layer on the hole wall has no delamination or blistering under thermal shock, and the resistance change rate is less than 4%.

(Example 6)

6.1 Select 20 μm thick ABF as the substrate. Laser drill blind holes in the ABF with a hole diameter of 20 μm.

6.2 Perform pretreatment. Specifically, the substrate is placed in the ion implantation equipment through a continuous discharge mechanism, vacuumed to 7.0×10 ^-2 Pa, and the substrate is irradiated with an ion beam. In a vacuum environment, the upper and lower surfaces of the substrate are simultaneously irradiated with an argon ion beam at a flow rate of 10 sccm. At this time, the temperature is controlled to rise to more than 75 degrees for dehydration treatment, and the water vapor in the ion beam chamber is extracted using an exhaust device. Ion beam irradiation simultaneously cleans and dehydrates the surface.

6.3 The conductive seed layer is produced by a combination of high power pulsed magnetron sputtering + plasma deposition (nickel) + plasma deposition (copper).

First, in a vacuum device, evacuate to 0.18Pa, use nickel as the target material, turn on the high-power pulse magnetron sputtering power supply, the voltage is 750V, the current is 300A, the pulse width is 100μs, the frequency is 580Hz, there are one or more sputtering sources, the power of each sputtering source is 3.2KW, the target surface power density is 27W/ ^cm2 , the acceleration bias is 50V, and high-power pulse magnetron sputtering is performed, the nickel ionization rate is greater than 30%, and the sputtering thickness is 50nm. Among them, the selection of the acceleration bias can increase the energy of the deposited metal particles, which is conducive to the metallization of the inner wall of the deep hole with a higher aspect ratio.

Then, using nickel as the target material, a magnetically filtered vacuum cathode arc source was used for plasma deposition. The argon flow rate was 5-12sccm, the deposition ion energy was 100eV, the arc current was 100A, the extraction current was 7A, and a nickel layer with a thickness of 100nm was deposited. The square resistance after deposition was 20-45 ohms.

Finally, plasma deposition was continued with copper as the target material to deposit a copper layer with a thickness of 250 nm. The square resistance after deposition was 0.5-3 ohms.

6.4 Electroplating thickening to prepare double-sided copper-clad laminates with metallized holes. Specifically, the copper film on both the upper and lower surfaces of the substrate and the hole wall is thickened to 25μm on the electroplating copper production line. The blind holes are then electroplated to fill the holes. The surface of the original blind hole position of the substrate is also covered with the same appearance as the surface of other positions of the substrate, all covered with a copper layer, and the surface is smooth and flat.

6.5 The prepared double-sided copper clad laminate is exposed, developed and etched to make a circuit board, and insulating materials are added as raw materials to laminate and make a multi-layer circuit board.

The structure of the circuit board with metallized holes obtained in Example 6 is as follows: a double-sided circuit board with metallized through holes, the ABF substrate is 20 μm thick, and the blind hole diameter is 20 μm. The surface of the substrate and the hole wall of the metallized hole are, from the inner layer to the outer layer, the nickel layer of high-power pulsed magnetron sputtering, with a thickness of 50 nm; the plasma deposited nickel layer, with a thickness of 100 nm; the plasma deposited copper layer, with a thickness of 250 nm; and the electroplated copper layer, with a thickness of 25 μm.

Specifically, the optical microscope photos of the blind buried vias formed after the blind vias are shown in Figures 9a-b, which have a blind via filling structure formed by electroplating. The surface of the blind via position is also covered with the same appearance as the surface of other positions of the substrate, all covered with a copper layer, and the interface is smooth and flat. The bonding force of the copper layer on the surface of the substrate of the circuit board with metallized holes is 0.7N/mm, and the copper layer on the hole wall has no delamination or cracking under thermal shock, and the resistance change rate is less than 3%.

The above description only mentions the preferred embodiments of the utility model. However, the utility model is not limited to the specific embodiments described herein. It will be easy for those skilled in the art to realize that various obvious modifications, adjustments and replacements can be made to these embodiments without departing from the gist of the utility model to make them suitable for specific situations. In fact, the scope of protection of the utility model is defined by the claims and may include other examples that can be anticipated by those skilled in the art. If such other examples have structural elements that are indistinguishable from the literal language of the claims, or if they include equivalent structural elements that are not significantly different from the literal language of the claims, then they will fall within the scope of protection of the claims.

Claims (29)

1. Copper-clad plate with metallized holes, its characterized in that, copper-clad plate includes:

An insulating substrate with holes;

A conductive seed layer formed on the surface of the substrate and the hole wall by simultaneously treating the surface of the substrate and the hole wall in a combination of a plurality of physical vapor depositions;

And an electroplated thickening layer formed by electroplating thickening the conductive seed layer.

2. The copper-clad laminate according to claim 1, wherein the base material is a polyimide film.

3. The copper-clad plate according to claim 1, wherein the hole is formed by mechanical drilling or laser drilling.

4. A copper clad laminate according to claim 3, wherein the holes are blind holes or through holes having a pore size of 20-500 μm.

5. A copper clad laminate according to claim 3, wherein the holes are blind holes or through holes having a pore size of 20-200 μm.

6. The copper-clad plate according to any one of claims 4 to 5, wherein the blind hole has a hole depth of 5 to 200 μm.

7. The copper-clad plate of claim 1, wherein the plurality of physical vapor depositions comprises: ion implantation, plasma deposition, high power pulsed magnetron sputtering, conventional magnetron sputtering.

8. The copper-clad plate of claim 1, wherein the combination of the plurality of physical vapor depositions comprises high power pulsed magnetron sputtering.

9. The copper-clad plate according to claim 1, wherein the processing in a combination of a plurality of physical vapor depositions comprises:

Firstly, ion implantation is carried out, then high-power pulse magnetron sputtering is carried out, and finally conventional magnetron sputtering is carried out;

Or firstly performing plasma deposition, then performing high-power pulse magnetron sputtering, and finally performing conventional magnetron sputtering;

Or firstly performing high-power pulse magnetron sputtering, then performing plasma deposition, and finally performing conventional magnetron sputtering;

or firstly performing high-power pulse magnetron sputtering, and then performing conventional magnetron sputtering;

Or firstly performing high-power pulse magnetron sputtering, and then performing plasma deposition;

Or firstly performing plasma deposition, and then performing high-power pulse magnetron sputtering;

Or high-power pulse magnetron sputtering is firstly carried out, and then ion implantation is carried out.

10. The copper-clad plate according to claim 1, wherein the standard deviation of the thickness of the conductive seed layer is 5% -20%; the ratio of the thickness of the conductor layer on the hole wall to the thickness of the conductor layer on the surface of the substrate is greater than or equal to 1:1.

11. The copper-clad plate according to claim 1, wherein the base material is a polyimide film having a thickness of 5-200 μm, and the drilled holes are through holes having a hole diameter of 20-200 μm;

Processing in a combination of physical vapor deposition includes:

First high power pulse magnetron sputtering is performed to form a nickel layer, followed by conventional magnetron sputtering to sputter a copper layer.

12. The copper-clad plate according to claim 11, wherein during high power pulse magnetron sputtering, nickel is used as a target material, the pulse width is 80-3000 μs, the frequency is 200-5000Hz, the peak current is 70-2000A, one or more sputtering sources are used, the power of each sputtering source is 1.5-50KW, and a nickel layer with the thickness of 6-200nm is formed on the surface of the substrate and the hole wall.

13. The copper-clad plate according to claim 11, wherein the conventional magnetron sputtering is direct current magnetron sputtering, copper is used as a target during the direct current magnetron sputtering, the voltage is 300-2000V, the current is 4-100A, the power is 1.2-200KW, and a copper layer with a thickness of 100-500nm is sputtered.

14. The copper-clad plate according to claim 11, wherein copper is electroplated on a copper layer of conventional magnetron sputtering by 1-25 μm to obtain the copper-clad plate with metallized holes.

15. A circuit board with metallized holes, the circuit board comprising:

An insulating substrate with holes;

A conductive seed layer formed on the surface of the substrate and the hole wall by simultaneously treating the surface of the substrate and the hole wall in a combination of a plurality of physical vapor depositions;

A line formed by adding a patterned metal on the conductive seed layer.

16. The circuit board of claim 15, wherein the substrate is a polyimide film.

17. The circuit board of claim 15, wherein the holes are formed using mechanical drilling or laser drilling.

18. The circuit board of claim 17, wherein the holes are blind holes or through holes having a pore size of 20-500 μm.

19. The circuit board of claim 17, wherein the holes are blind holes or through holes having a pore size of 20-200 μm.

20. The circuit board of any one of claims 18-19, wherein the blind holes have a hole depth of 5-200 μιη.

21. The circuit board of claim 15, wherein the plurality of physical vapor depositions comprises: ion implantation, plasma deposition, high power pulsed magnetron sputtering, conventional magnetron sputtering.

22. The circuit board of claim 15, wherein the combination of physical vapor depositions comprises high power pulsed magnetron sputtering.

23. The circuit board of claim 15, wherein processing in a combination of physical vapor deposition comprises:

Firstly, ion implantation is carried out, then high-power pulse magnetron sputtering is carried out, and finally conventional magnetron sputtering is carried out;

Or firstly performing plasma deposition, then performing high-power pulse magnetron sputtering, and finally performing conventional magnetron sputtering;

Or firstly performing high-power pulse magnetron sputtering, then performing plasma deposition, and finally performing conventional magnetron sputtering;

or firstly performing high-power pulse magnetron sputtering, and then performing conventional magnetron sputtering;

Or firstly performing high-power pulse magnetron sputtering, and then performing plasma deposition;

Or firstly performing plasma deposition, and then performing high-power pulse magnetron sputtering;

Or high-power pulse magnetron sputtering is firstly carried out, and then ion implantation is carried out.

24. The circuit board of claim 15, wherein the standard deviation of the thickness of the conductive seed layer is 5% -20%, and the ratio of the thickness of the conductor layer on the hole wall to the thickness of the conductor layer on the surface of the substrate is greater than or equal to 1:1.

25. The circuit board of claim 15, wherein the circuit board is a single-layer circuit board or a multi-layer circuit board.

26. The wiring board according to claim 15, wherein the base material is a polyimide film having a thickness of 5 to 200 μm, and the drilled holes are through holes having a hole diameter of 20 to 200 μm;

Processing in a combination of physical vapor deposition includes:

First high power pulse magnetron sputtering is performed to form a nickel layer, followed by conventional magnetron sputtering to sputter a copper layer.

27. The circuit board of claim 26, wherein during high power pulsed magnetron sputtering, nickel is used as a target, the pulse width is 80-3000 μs, the frequency is 200-5000Hz, the peak current is 70-2000A, the number of sputtering sources is one or more, the power of each sputtering source is 1.5-50KW, and a nickel layer with a thickness of 6-200nm is formed on the surface of the substrate and the hole wall.

28. The circuit board of claim 26, wherein the conventional magnetron sputtering is direct current magnetron sputtering, during which copper is used as a target, the voltage is 300-2000V, the current is 4-100A, the power is 1.2-200KW, and a copper layer 100-500nm thick is sputtered.

29. The circuit board of claim 26, wherein a patterned copper layer of 0.5-25 μm thickness is added to a conventional magnetron sputtered copper layer to provide the circuit board with metallized holes.