Copper-clad plate with plated-through hole, circuit board with plated-through hole, and manufacturing methods therefor

Abstract

The present invention relates to a copper-clad plate with plated-through holes, a circuit board with plated-through holes, and manufacturing methods therefor. Specifically, a method for manufacturing a copper-clad plate with plated-through holes comprises the following steps: drilling an insulating substrate; performing a pre-treatment on the substrate with holes; simultaneously treating the surface and hole walls of the substrate by means of a combination of a plurality of physical vapor deposition methods, so as to form conductive seed layers on the surface and hole walls of the substrate, thereby obtaining a metallized substrate with plated-through holes; and performing electroplating thickening on the metallized substrate, so as to obtain a copper-clad plate with plated-through holes.

Description

Copper-clad plate with metallized holes, circuit board and manufacturing method thereof Technical Field

[0001] The invention relates to a copper-clad plate with metallized holes, a circuit board and a manufacturing method thereof. Background Art

[0002] In the production process of copper-clad laminates or circuit boards, insulating materials are usually used as substrates. Metal materials are composited on one or both sides of the substrate to produce copper-clad laminates, which are then etched to produce circuit boards. As examples of insulating substrates, rigid substrates (also called hard boards) can be used, such as one or more of organic polymer rigid boards, ceramic boards (such as silica boards), and glass boards. Organic polymer rigid boards can include one or more of LCP, PTFE, CTFE, FEP, PPE, synthetic rubber boards, and glass fiber cloth / ceramic filler reinforced boards. Glass fiber cloth / ceramic filler reinforced boards are boards with organic polymer materials such as epoxy resin, modified epoxy resin, PTFE, PPO, CE, BT, etc. as base materials and glass fiber cloth / ceramic filler as reinforcement 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.

[0003] 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, so as to facilitate the design of multi-layer circuit patterns.

[0004] In the prior art, one method for laminating metal materials onto substrates is to laminate ultrathin copper foil onto the substrate to produce a copper-clad laminate. However, the difficulty in producing and laminating ultrathin copper foil during lamination, as well as limitations in etching precision, make it difficult to create fine circuits. Furthermore, lamination itself cannot form a conductive layer on the via hole walls; this can only be achieved in subsequent processes. Therefore, the continuity and thickness consistency between the conductive layer on the substrate surface and the conductive layer on the via hole walls cannot be guaranteed.

[0005] In the prior art, another method for cladding metal materials on substrates is to use techniques such as conductive inks, nanoimprinting, and conventional magnetron sputtering to uniformly clad the metal materials to produce copper-clad laminates, or to directly pattern the metal materials to produce circuit boards. However, circuit boards produced using these technologies have a fatal flaw: the bonding between the conductive circuit and the substrate is poor, failing to meet the requirements of subsequent processes. In particular, when metallizing the holes using these technologies, the bonding between the electroplated copper layer and the hole walls is poor, and the copper layer easily detaches from the hole walls. Moreover, the uneven current density distribution within the hole region causes the copper deposition rate on the hole surface to be greater than the deposition rate on the hole walls. As a result, holes or cracks are easily formed in the conductor layer on the hole walls during the deposition process. Furthermore, the conductor layer on the hole walls is prone to delamination or blistering when subjected to thermal shock, resulting in a high resistance change rate. Furthermore, the thickness of the conductor layer on the hole surface is greater than the thickness of the conductor layer on the hole walls. Furthermore, these technologies suffer from low processing efficiency.

[0006] There is a continuous demand in the art for a method for manufacturing copper clad laminates and circuit boards, which has strong bonding strength between the conductor layer on the surface of the substrate and the conductor layer on the hole wall, a smooth and flat interface, uniform thickness, and can be processed efficiently.

[0007] Summary of the Invention

[0008] The purpose of the present invention is to overcome the defects existing in the above-mentioned prior art field. It provides a copper-clad laminate 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 carried out efficiently.

[0009] Technical Solution 1. A method for manufacturing a copper-clad laminate with metallized holes, comprising the following steps:

[0010] Step S1: drilling a hole in an insulating substrate;

[0011] Step S2: pre-treating the porous substrate;

[0012] Step S3: treating the surface of the substrate and the hole walls simultaneously by a combination of multiple physical vapor deposition methods to form a conductive seed layer on the surface of the substrate and the hole walls, thereby obtaining a metallized substrate with metallized holes;

[0013] Step S4: performing electroplating to thicken the metallized substrate, thereby obtaining a copper-clad plate with metallized holes.

[0014] Technical Solution 2. The method according to Technical Solution 1 is characterized in that, after step S4, it also includes step S5: using the copper-clad laminate with metallized holes to make a circuit board.

[0015] Technical Solution 3. The method according to Technical Solution 2 is characterized in that, in step S5, the circuit board is manufactured using a semi-additive method.

[0016] Technical Solution 4. The method according to Technical Solution 1 is characterized in that the substrate is a polyimide film.

[0017] Technical Solution 5. The method according to Technical Solution 1 is characterized in that in the step S1, mechanical drilling or laser drilling is used to drill the substrate.

[0018] Technical Solution 6. The method according to Technical Solution 5 is characterized in that the drilled hole is a blind hole or a through hole with a pore diameter of 20-500μm.

[0019] Technical Solution 7. The method according to Technical Solution 5 is characterized in that the drilled hole is a blind hole or a through hole with a pore diameter of 20-200 μm.

[0020] Technical Solution 8. The method according to any one of Technical Solutions 5-7 is characterized in that the depth of the drilled hole is 5-200 μm.

[0021] Technical Solution 9. The method according to Technical Solution 1 is characterized in that the pretreatment in step S2 includes one or more of plasma cleaning treatment, dehydration treatment, and alkaline solution surface treatment.

[0022] Technical Solution 10. The method according to Technical Solution 1 is characterized in that the multiple physical vapor depositions in step S3 include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

[0023] Technical Solution 11. The method according to Technical Solution 1 is characterized in that the combination of multiple physical vapor deposition in step S3 includes high-power pulsed magnetron sputtering.

[0024] Technical Solution 12. The method according to Technical Solution 1 is characterized in that the processing in step S3 using a combination of multiple physical vapor deposition methods includes:

[0025] First, ion implantation is performed, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0026] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0027] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition, and finally conventional magnetron sputtering;

[0028] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by conventional magnetron sputtering;

[0029] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition;

[0030] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering;

[0031] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by ion implantation.

[0032] Technical Solution 13. The method according to Technical Solution 10 or 12 is characterized in that during ion implantation, the energy of the implanted ions is 3-20 keV.

[0033] Technical Solution 14. The method according to Technical Solution 10 or 12 is characterized in that during the ion implantation, the implantation dose is 1.0×10 14 -5.0×10 16 ions / cm 2 .

[0034] Technical Solution 15. The method according to Technical Solution 10 or 12 is characterized in that during plasma deposition, the energy of the deposited ions is 30-100 eV.

[0035] Technical Solution 16. The method according to any one of Technical Solutions 10-12 is characterized in that 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%.

[0036] Technical Solution 17. The method according to any one of Technical Solutions 10-12 is characterized in that during high-power pulsed magnetron sputtering, the acceleration bias is 0-100 kV.

[0037] Technical Solution 18. The method according to any one of Technical Solutions 10-12 is characterized in that during high-power pulsed magnetron sputtering, the acceleration bias is 0-50KV.

[0038] Technical Solution 19. The method according to any one of Technical Solutions 10-12, characterized in that during high-power pulsed magnetron sputtering, the target surface power density is 1-100 W / cm 2 .

[0039] Technical Solution 20. The method according to any one of Technical Solutions 10-12, characterized in that during high-power pulsed magnetron sputtering, the target surface power density is 3-20 W / cm 2 .

[0040] Technical Solution 21. The method according to any one of Technical Solutions 10-12 is characterized in that during high-power pulsed magnetron sputtering, the pulse width is 80-3000 μs.

[0041] Technical Solution 22. The method according to any one of Technical Solutions 10-12 is characterized in that during high-power pulsed magnetron sputtering, the frequency is 200-5000 Hz.

[0042] Technical Solution 23. The method according to any one of Technical Solutions 10-12 is characterized in that during high-power pulsed magnetron sputtering, the peak current is 50-2000A.

[0043] Technical Solution 24. The method according to any one of Technical Solutions 10-12 is characterized in that during high-power pulsed magnetron sputtering, the movement speed of the substrate in the equipment is 0.5-15 m / s.

[0044] Technical Solution 25. The method according to Technical Solution 10 or 12 is characterized in that the conventional magnetron sputtering is DC magnetron sputtering, and during DC magnetron sputtering, the voltage is 100V-2000V and the current is 1-100A.

[0045] Technical Solution 26. The method according to Technical Solution 1, 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 diameter of 20-200 μm;

[0046] The processing in step S3 by combining multiple physical vapor deposition methods includes:

[0047] First, high-power pulsed magnetron sputtering is performed to form the nickel layer, followed by plasma deposition to deposit the nickel layer, and finally conventional magnetron sputtering is performed to sputter the copper layer.

[0048] Technical Solution 27. The method 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 nickel layer with a thickness of 6-200nm is formed on the surface of the substrate and the pore wall.

[0049] Technical Solution 28. The method according to Technical Solution 27 is characterized in that the pulse width is 80-180μs, the frequency is 340-400Hz, and the peak current is 90-230A.

[0050] Technical Solution 29. The method according to Technical Solution 26 is characterized in that during plasma deposition, nickel is used as the target material, the arc current is 40-100A, the extraction current is 7-15A, and the nickel layer is deposited.

[0051] Technical Solution 30. The method according to Technical Solution 29 is characterized in that the lead-out current is 9-11A.

[0052] Technical Solution 31. The method according to Technical Solution 26 is characterized in that the conventional magnetron sputtering is DC magnetron sputtering, and during the DC magnetron sputtering, copper is used as the target material, the voltage is 300-2000V, the current is 4-100A, and the power is 1.2-200KW to produce a sputtered copper layer.

[0053] Technical Solution 32. The method according to Technical Solution 31 is characterized in that the voltage is 310-330V, the current is 4-5A, and the power is 1.3-1.6KW.

[0054] Technical Solution 33. The method according to Technical Solution 26 is characterized in that the total thickness of the plasma-deposited nickel layer and the conventional magnetron sputtered copper layer is 50-2000 nm.

[0055] Technical Solution 34. The method according to Technical Solution 26 is characterized in that 0.5-25 μm of copper is electroplated on the conventional magnetron sputtered copper layer to obtain a copper-clad board with metallized holes.

[0056] Technical Solution 35. The method according to Technical Solution 1, 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 diameter of 20-200 μm;

[0057] The processing in step S3 by combining multiple physical vapor deposition methods includes:

[0058] High-power pulsed magnetron sputtering is first performed to form the nickel layer, followed by plasma deposition to deposit the copper layer, and finally conventional magnetron sputtering is performed to sputter the copper layer.

[0059] Technical Solution 36. The method according to Technical Solution 35 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 nickel layer with a thickness of 6-200nm is formed on the surface of the substrate and the pore wall.

[0060] Technical Solution 37. The method according to Technical Solution 36 is characterized in that the pulse width is 90-110μs, the frequency is 410-430Hz, and the peak current is 90-110A.

[0061] Technical Solution 38. The method according to Technical Solution 35 is characterized in that during plasma deposition, copper is used as the target material, the arc current is 40-100A, the extraction current is 7-15A, and the copper layer is deposited.

[0062] Technical Solution 39. The method according to Technical Solution 38 is characterized in that the lead-out current is 9-11A.

[0063] Technical Solution 40. The method according to Technical Solution 35 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 of 50-2000nm thick is sputtered.

[0064] Technical Solution 41. The method according to Technical Solution 40 is characterized in that the voltage is 370-390V, the current is 9-11A, and the power is 3.4-4.2KW.

[0065] Technical Solution 42. The method according to Technical Solution 35 is characterized in that 0.5-25 μm of copper is electroplated on the conventional magnetron sputtered copper layer to obtain a copper-clad board with metallized holes.

[0066] Technical Solution 43. The method according to Technical Solution 1, 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 diameter of 20-200 μm;

[0067] The processing in step S3 by combining multiple physical vapor deposition methods includes:

[0068] High-power pulsed magnetron sputtering is first performed to form the nickel layer, followed by conventional magnetron sputtering to sputter the copper layer.

[0069] Technical Solution 44. The method according to Technical Solution 43 is characterized in that during high-power pulsed magnetron sputtering, nickel is used as a target material, the pulse width is 80-3000 μs, the frequency is 200-5000 Hz, the peak current is 70-2000 A, there are one or more sputtering sources, and the power of each sputtering source is 1.5-50 kW, and a nickel layer 6-200 nm thick is formed on the surface of the substrate and the pore wall.

[0070] Technical Solution 45. The method according to Technical Solution 44 is characterized in that the pulse width is 80-120μs, the frequency is 400-420Hz, the current is 110-300A, and the power is 1.0-6.0KW.

[0071] Technical Solution 46. The method according to Technical Solution 43 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 of 50-2000nm thick is sputtered.

[0072] Technical Solution 47. The method according to Technical Solution 46 is characterized in that the voltage is 340-350V, the current is 5.0-6.0A, and the power is 1.7-2.1KW.

[0073] Technical Solution 48. The method according to Technical Solution 43 is characterized in that 0.5-25 μm of copper is electroplated on the conventional magnetron sputtered copper layer to obtain a copper-clad board with metallized holes.

[0074] Technical Solution 49. The method according to Technical Solution 1 is characterized in that the standard deviation of the thickness of the conductive seed crystal layer is 5%-20%; after step S4, 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.

[0075] Technical Solution 50. A method for manufacturing a circuit board with metallized holes, comprising the following steps:

[0076] Step S1: drilling a hole in an insulating substrate;

[0077] Step S2: pre-treating the porous substrate;

[0078] Step S3: treating the surface of the substrate and the hole walls simultaneously by a combination of multiple physical vapor deposition methods to form a conductive seed layer on the surface of the substrate and the hole walls, thereby obtaining a metallized substrate with metallized holes; and

[0079] Step S4: adding patterned metal on the metallized substrate with the metallized holes to fabricate circuits on the conductive seed crystal layer of the metallized substrate with the metallized holes, thereby producing a single-layer circuit board.

[0080] Technical Solution 51. The method according to Technical Solution 50 is characterized in that in step S4, patterned metal is added to both surfaces of the metallized substrate with metallized holes to produce a double-sided circuit board.

[0081] Technical Solution 52. The method according to Technical Solution 51 is characterized in that the double-sided circuit board is used as the substrate, the upper and lower surfaces of the double-sided circuit board are covered with semi-cured sheets, and steps S1 to S4 are repeated once or multiple times on the double-sided circuit board covered with the semi-cured sheets, thereby preparing a multi-layer circuit board.

[0082] Technical Solution 53. The method according to Technical Solution 50 is characterized in that the substrate is a polyimide film.

[0083] Technical Solution 54. The method according to Technical Solution 50 is characterized in that in the step S1, mechanical drilling or laser drilling is used to drill the substrate.

[0084] Technical Solution 55. The method according to Technical Solution 54 is characterized in that the drilled hole is a blind hole or a through hole with a pore diameter of 20-500μm.

[0085] Technical Solution 56. The method according to Technical Solution 54 is characterized in that the drilled hole is a blind hole or a through hole with a pore diameter of 20-200μm.

[0086] Technical Solution 57. The method according to any one of Technical Solutions 54-56 is characterized in that the depth of the drilled hole is 5-200 μm.

[0087] Technical Solution 58. The method according to Technical Solution 50 is characterized in that the pretreatment in step S2 includes one or more of plasma cleaning treatment, dehydration treatment, and alkaline solution surface treatment.

[0088] Technical Solution 59. The method according to Technical Solution 50 is characterized in that the multiple physical vapor depositions in step S3 include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

[0089] Technical Solution 60. The method according to Technical Solution 50 is characterized in that the combination of multiple physical vapor deposition in step S3 includes high-power pulsed magnetron sputtering.

[0090] Technical Solution 61. The method according to Technical Solution 50 is characterized in that the processing in step S3 using a combination of multiple physical vapor deposition methods includes:

[0091] First, ion implantation is performed, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0092] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0093] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition, and finally conventional magnetron sputtering;

[0094] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by conventional magnetron sputtering;

[0095] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition;

[0096] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering;

[0097] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by ion implantation.

[0098] Technical Solution 62. The method according to Technical Solution 59 or 61 is characterized in that during ion implantation, the energy of the implanted ions is 3-20 keV.

[0099] Technical Solution 63. The method according to Technical Solution 59 or 61 is characterized in that during the ion implantation, the implantation dose is 1.0×10 14 -5.0×10 16 ions / cm 2 .

[0100] Technical Solution 64. The method according to Technical Solution 59 or 61 is characterized in that during plasma deposition, the energy of the deposited ions is 30-100 eV.

[0101] Technical Solution 65. A method according to any one of Technical Solutions 59-61, characterized in that 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%.

[0102] Technical Solution 66. A method according to any one of Technical Solutions 59-61, characterized in that during high-power pulsed magnetron sputtering, the acceleration bias is 0-100 kV.

[0103] Technical Solution 67. A method according to any one of Technical Solutions 59-61, characterized in that during high-power pulsed magnetron sputtering, the acceleration bias is 0-50KV.

[0104] Technical Solution 68. The method according to any one of Technical Solutions 59-61 is characterized in that during high-power pulsed magnetron sputtering, the target surface power density is 1-100 W / cm 2 .

[0105] Technical Solution 69. The method according to any one of Technical Solutions 59-61 is characterized in that during high-power pulsed magnetron sputtering, the target surface power density is 3-20 W / cm 2 .

[0106] Technical Solution 70. A method according to any one of Technical Solutions 59-61, characterized in that during high-power pulsed magnetron sputtering, the pulse width is 80-3000 μs.

[0107] Technical Solution 71. A method according to any one of Technical Solutions 59-61, characterized in that during high-power pulsed magnetron sputtering, the frequency is 200-5000 Hz.

[0108] Technical Solution 72. A method according to any one of Technical Solutions 59-61, characterized in that during high-power pulsed magnetron sputtering, the peak current is 50-2000A.

[0109] Technical Solution 73. The method according to Technical Solution 59 or 61 is characterized in that the conventional magnetron sputtering is DC magnetron sputtering, and during the DC magnetron sputtering, the voltage is 100V-2000V and the current is 1-100A.

[0110] Technical Solution 74. The method according to Technical Solution 50 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 diameter of 20-200 μm;

[0111] The processing in step S3 by combining multiple physical vapor deposition methods includes:

[0112] First, high-power pulsed magnetron sputtering is performed to form the nickel layer, followed by plasma deposition to deposit the nickel layer, and finally conventional magnetron sputtering is performed to sputter the copper layer.

[0113] Technical Solution 75. The method according to Technical Solution 74 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 nickel layer with a thickness of 6-200nm is formed on the surface of the substrate and the pore wall.

[0114] Technical Solution 76. The method according to claim 75 is characterized in that the pulse width is 90-110 μs, the frequency is 340-360 Hz, and the peak current is 110-130 A.

[0115] Technical Solution 77. The method according to Technical Solution 74 is characterized in that during plasma deposition, nickel is used as the target material, the arc current is 40-100A, the extraction current is 7-15A, and the nickel layer is deposited.

[0116] Technical Solution 78. The method according to Technical Solution 77 is characterized in that the lead-out current is 9-11A.

[0117] Technical Solution 79. The method according to Technical Solution 73 is characterized in that the conventional magnetron sputtering is DC magnetron sputtering, and during the DC magnetron sputtering, copper is used as the target material, the voltage is 300-2000V, the current is 4-100A, and the power is 1.2-200KW.

[0118] Technical Solution 80. The method according to Technical Solution 79 is characterized in that the voltage is 310-330V, the current is 4-5A, and the power is 1.25-1.65KW.

[0119] Technical Solution 81. The method according to Technical Solution 74 is characterized in that the total thickness of the plasma-deposited nickel layer and the conventional magnetron sputtered copper layer is 50-2000 nm.

[0120] Technical Solution 82. The method according to Technical Solution 74 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.

[0121] Technical Solution 83. The method according to Technical Solution 50, 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 diameter of 20-200 μm;

[0122] The processing in step S3 by combining multiple physical vapor deposition methods includes:

[0123] High-power pulsed magnetron sputtering is first performed to form the nickel layer, followed by plasma deposition to deposit the copper layer, and finally conventional magnetron sputtering is performed to sputter the copper layer.

[0124] Technical Solution 84. The method according to Technical Solution 83 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 nickel layer with a thickness of 6-200nm is formed on the surface of the substrate and the pore wall.

[0125] Technical Solution 85. The method according to Technical Solution 84 is characterized in that the pulse width is 90-110μs, the frequency is 410-430Hz, and the peak current is 100-110A.

[0126] Technical Solution 86. The method according to Technical Solution 83 is characterized in that during plasma deposition, copper is used as the target material, the arc current is 40-100A, the extraction current is 7-15A, and the copper layer is deposited.

[0127] Technical Solution 87. The method according to Technical Solution 86 is characterized in that the lead-out current is 9-11A.

[0128] Technical Solution 88. The method according to Technical Solution 83 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 of 50-2000nm thick is sputtered.

[0129] Technical Solution 89. The method according to Technical Solution 88 is characterized in that the voltage is 370-390V, the current is 9-11A, and the power is 3.4-4.3KW.

[0130] Technical Solution 90. The method according to Technical Solution 83 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.

[0131] Technical Solution 91. The method according to Technical Solution 50, 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 diameter of 20-200 μm;

[0132] The processing in step S3 by combining multiple physical vapor deposition methods includes:

[0133] High-power pulsed magnetron sputtering is first performed to form the nickel layer, followed by conventional magnetron sputtering to sputter the copper layer.

[0134] Technical Solution 92. The method according to Technical Solution 91 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 nickel layer with a thickness of 6-200nm is formed on the surface of the substrate and the pore wall.

[0135] Technical Solution 93. The method according to Technical Solution 92 is characterized in that the pulse width is 100-110μs, the frequency is 400-410Hz, the current is 110-130A, and the power is 2.0-4.5KW.

[0136] Technical Solution 94. The method according to Technical Solution 91 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.

[0137] Technical Solution 95. The method according to Technical Solution 94 is characterized in that during the DC magnetron sputtering, copper is used as the target material, the voltage is 300-340V, the current is 3-6A, and the power is 0.9-2KW.

[0138] Technical Solution 96. The method according to Technical Solution 91 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.

[0139] Technical Solution 97. The method according to Technical Solution 50 is characterized in that the standard deviation of the thickness of the conductive seed crystal layer is 5%-20%, and after step S4, 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.

[0140] Technical Solution 98. A copper-clad laminate with metallized holes, comprising:

[0141] Insulating substrate with holes;

[0142] 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;

[0143] The electroplating thickening layer is formed by electroplating thickening the conductive seed crystal layer.

[0144] Technical Solution 99. The copper-clad laminate according to Technical Solution 98 is characterized in that the substrate is a polyimide film.

[0145] Technical Solution 100. The copper-clad laminate according to Technical Solution 98 is characterized in that the holes are formed by mechanical drilling or laser drilling.

[0146] Technical Solution 101. The copper-clad laminate according to Technical Solution 100 is characterized in that the hole is a blind hole or a through hole with a pore diameter of 20-500 μm.

[0147] Technical Solution 102. The copper-clad laminate according to Technical Solution 100 is characterized in that the hole is a blind hole or a through hole with a pore diameter of 20-200 μm.

[0148] Technical Solution 103. A copper-clad laminate according to any one of Technical Solutions 100-102, characterized in that the depth of the blind hole is 5-200 μm.

[0149] Technical Solution 104. The copper-clad laminate according to Technical Solution 98 is characterized in that the multiple physical vapor deposition methods include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

[0150] Technical Solution 105. The copper-clad laminate according to Technical Solution 98 is characterized in that the combination of multiple physical vapor depositions includes high-power pulsed magnetron sputtering.

[0151] Technical Solution 106. The copper-clad laminate according to Technical Solution 98, wherein the processing by a combination of multiple physical vapor deposition methods comprises:

[0152] First, ion implantation is performed, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0153] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0154] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition, and finally conventional magnetron sputtering;

[0155] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by conventional magnetron sputtering;

[0156] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition;

[0157] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering;

[0158] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by ion implantation.

[0159] Technical Solution 107. The copper-clad laminate according to Technical Solution 98 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.

[0160] Technical Solution 108. The copper-clad laminate according to Technical Solution 98, wherein the substrate is a polyimide film with a thickness of 5-200 μm, and the drilled holes are through holes with a pore diameter of 20-200 μm;

[0161] Processing in a combination of various physical vapor deposition methods includes:

[0162] High-power pulsed magnetron sputtering is first performed to form the nickel layer, followed by conventional magnetron sputtering to sputter the copper layer.

[0163] Technical Solution 109. The copper-clad laminate according to Technical Solution 108 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 nickel layer with a thickness of 6-200nm is formed on the surface of the substrate and the pore wall.

[0164] Technical Solution 110. The copper-clad laminate according to Technical Solution 108 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 300-2000 V, the current is 4-100 A, the power is 1.2-200 kW, and a copper layer with a thickness of 100-500 nm is sputtered.

[0165] Technical Solution 111. The copper-clad laminate according to Technical Solution 108 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.

[0166] Technical Solution 112. A circuit board with metallized holes, comprising:

[0167] Insulating substrate with holes;

[0168] 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;

[0169] A circuit is formed by adding patterned metal on the conductive seed layer.

[0170] Technical Solution 113. The circuit board according to Technical Solution 112 is characterized in that the substrate is a polyimide film.

[0171] Technical Solution 114. The circuit board according to Technical Solution 112 is characterized in that the holes are formed by mechanical drilling or laser drilling.

[0172] Technical Solution 115. The circuit board according to Technical Solution 114 is characterized in that the hole is a blind hole or a through hole with a pore diameter of 20-500μm.

[0173] Technical Solution 116. The circuit board according to Technical Solution 114 is characterized in that the hole is a blind hole or a through hole with a pore diameter of 20-200μm.

[0174] Technical Solution 117. A circuit board according to any one of Technical Solutions 114-116, characterized in that the depth of the blind hole is 5-200 μm.

[0175] Technical Solution 118. The circuit board according to Technical Solution 112 is characterized in that the multiple physical vapor deposition methods include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

[0176] Technical Solution 119. The circuit board according to Technical Solution 112 is characterized in that the combination of multiple physical vapor deposition methods includes high-power pulsed magnetron sputtering.

[0177] Technical Solution 120. The circuit board according to Technical Solution 112 is characterized in that the processing by a combination of multiple physical vapor deposition methods includes:

[0178] First, ion implantation is performed, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0179] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0180] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition, and finally conventional magnetron sputtering;

[0181] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by conventional magnetron sputtering;

[0182] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition;

[0183] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering;

[0184] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by ion implantation.

[0185] Technical Solution 121. The circuit board according to Technical Solution 112 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.

[0186] Technical Solution 122. The circuit board according to Technical Solution 112 is characterized in that the circuit board is a single-layer circuit board or a multi-layer circuit board.

[0187] Technical Solution 123. The circuit board according to Technical Solution 112, 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 diameter of 20-200 μm;

[0188] Processing in a combination of various physical vapor deposition methods includes:

[0189] High-power pulsed magnetron sputtering is first performed to form the nickel layer, followed by conventional magnetron sputtering to sputter the copper layer.

[0190] Technical Solution 124. The circuit board according to Technical Solution 123 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 nickel layer with a thickness of 6-200nm is formed on the surface of the substrate and the hole wall.

[0191] Technical Solution 125. The circuit board according to Technical Solution 123 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.

[0192] Technical Solution 126. The circuit board according to Technical Solution 123 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.

[0193] According to the above technical solution, copper-clad laminates 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 deposition methods according to the present invention, especially the combination of multiple physical vapor deposition methods 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 strength (up to 1.0N / mm) and a smooth and flat interface with uniform thickness (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). There will be no holes or cracks. The conductor layer on the hole wall will not delaminate or bubble 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 production line speed is as high as 1.5-3m / s. Compared with ion implantation plasma deposition technology, the film speed of the production line is increased by 3-10 times. Thus, the defects that are easy to exist in the conductor layer on the surface of the substrate and the conductor layer on the hole wall in the prior art are avoided.

[0194] 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

[0195] These and other features, aspects, and advantages of the present invention will be more readily understood by those skilled in the art after reading the following detailed description with reference to the accompanying drawings. For the sake of clarity, the drawings are not necessarily drawn to scale, and some parts may be exaggerated to show details. In all figures, the same reference numerals represent the same or similar parts, wherein:

[0196] 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 invention;

[0197] 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 invention;

[0198] FIG3 is a flow chart of a method for manufacturing a circuit board with metallized holes according to an exemplary embodiment of the present invention;

[0199] 4a-c are photographs of copper clad laminates with metallized holes produced using a combination of multiple physical vapor deposition processes according to the present invention;

[0200] 5a-b are photographs of a copper clad laminate with metallized holes produced using another combination of multiple physical vapor deposition methods according to the present invention;

[0201] 6a-c are photographs of copper-clad laminates with metallized holes produced using yet another combination of multiple physical vapor deposition methods according to the present invention;

[0202] FIG7 is a photograph of a copper clad plate with metallized holes made according to an embodiment of the present invention;

[0203] FIG8 is a photograph of a copper-clad laminate with metallized holes made according to another embodiment of the present invention;

[0204] 9a-b are photos of a circuit board with metallized holes made using another embodiment of the present invention. DETAILED DESCRIPTION

[0205] The embodiments of the present invention are described in detail below 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 not intended to limit the scope of protection of the present invention.

[0206] Figure 1 is a flow chart of a method for manufacturing a copper-clad laminate with plated holes according to an exemplary embodiment of the present invention. As shown in Figure 1, 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 walls simultaneously using a combination of multiple physical vapor deposition methods to form a conductive seed layer on the surface of the substrate and the hole walls, thereby obtaining a metallized substrate with plated holes (step S3); and electroplating and thickening the metallized substrate to obtain a copper-clad laminate with plated holes (step S4).

[0207] The method further includes fabricating a circuit board using the copper-clad laminate with metallized holes (step S5), as shown in FIG2 . In step S5, the circuit board is fabricated using a semi-additive process, which involves fabricating a copper layer on a patterned photoresist layer and then stripping the photoresist layer.

[0208] Thus, a copper-clad laminate with metallized holes is produced, comprising: an insulating substrate with holes; a conductive seed layer formed on the substrate surface and the hole walls by simultaneously treating the substrate surface and the hole walls with a combination of multiple physical vapor deposition methods; and an electroplating thickening layer formed by electroplating the conductive seed layer. Furthermore, the copper-clad laminate with metallized holes can be used to manufacture circuit boards.

[0209] Figure 3 is a flow chart of a method for manufacturing a circuit board with plated holes according to an exemplary embodiment of the present invention. As shown in Figure 3, the method includes the following steps: drilling holes in an insulating substrate (step S1); pre-treating the substrate with holes (step S2); simultaneously treating the substrate surface and the hole walls using a combination of multiple physical vapor deposition methods to form a conductive seed layer on the substrate surface and the hole walls, thereby obtaining a metallized substrate with plated holes (step S3); adding patterned metal to the metallized substrate with plated holes, thereby forming circuits on the conductive seed layer of the metallized substrate with plated holes, thereby producing a single-layer circuit board (step S4). In step S4, patterned metal is added to both surfaces of the metallized substrate with plated holes, thereby producing a double-sided circuit board. Using the double-sided circuit board as the substrate, prepreg is covered on the upper and lower surfaces of the double-sided circuit board, and steps S1 to S4 are repeated one or more times on the double-sided circuit board covered with prepreg, thereby producing a multi-layer circuit board.

[0210] Thus, a circuit board with metallized holes is produced, comprising: an insulating substrate with holes; a conductive seed layer formed on the substrate surface and the hole walls by simultaneously treating the substrate surface and the hole walls using a combination of multiple physical vapor deposition methods; and circuits formed by adding patterned metal to the conductive seed layer. The circuit board can be a single-layer circuit board or a multi-layer circuit board.

[0211] Specifically, the substrate is a polyimide film. If the pore diameter is large, mechanical drilling can be used. When the pore diameter 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 a pore diameter 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; among which 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 filled holes and blind buried holes (especially small holes), which has advantages for filling holes in flexible circuit boards. For example, for a hole with a depth of 30 μm, when the copper layer thickness on the plated hole wall is 15 μm and the copper layer thickness on the surface of the substrate is also 15 μm, the hole can be filled.

[0212] 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 a carbonized layer formed during drilling.

[0213] 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.

[0214] More specifically, processing in a combination of multiple physical vapor deposition methods includes:

[0215] First, ion implantation is performed, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0216] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering, and finally conventional magnetron sputtering;

[0217] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition, and finally conventional magnetron sputtering;

[0218] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by conventional magnetron sputtering;

[0219] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by plasma deposition;

[0220] Alternatively, plasma deposition is performed first, followed by high-power pulsed magnetron sputtering;

[0221] Alternatively, high-power pulsed magnetron sputtering is performed first, followed by ion implantation.

[0222] 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, the conductive material in the target material is ionized by the action of an electric arc to generate ions, and then the ions are accelerated under a high voltage electric field to obtain very high energy. The high-energy conductive material ions then directly collide with 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 magnetic 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 ; The injection depth is 5-50nm.

[0223] Plasma deposition is similar to the ion implantation described above, except that a lower voltage is applied, resulting in lower energy for the conductive material ions. Specifically, a conductive material is used as a target. In a vacuum environment, an arc is applied to ionize the conductive material in the target to generate ions. These ions are then accelerated under an electric field to gain a certain energy. The accelerated conductive material ions fly toward 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 50-1000 eV, preferably 30-100 eV.

[0224] Conventional magnetron sputtering can be achieved by using a conductive material as a target. In a DC magnetron sputtering device under a vacuum environment, a positive voltage is applied to the target using a power supply, generating ion bombardment. A magnetic field is simultaneously applied to the target surface to guide the ions, causing the atoms or molecules generated by ion bombardment to deposit on the surface of the substrate and the pore walls. Specifically, conventional magnetron sputtering primarily 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.

[0225] High-power pulsed magnetron sputtering uses a high-power pulse power supply (therefore, it is different from conventional magnetron sputtering), so the presence of pulses increases the pulse width, frequency, duty cycle, peak voltage, peak current and other parameters, making it more flexible and controllable. In particular, high-power pulsed magnetron sputtering can achieve high plasma density and high metal ionization rate, thereby optimizing 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 / cm 2 , preferably 3-20W / cm 2 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 substrate moving speed in the device is 0.5-15m / s. The present invention includes the beneficial effects of high-power pulsed magnetron sputtering in the combination of multiple physical vapor deposition methods: the target surface power density of high-power pulsed magnetron sputtering can reach 10-80W / cm 2 , thereby achieving nickel ionization rates >30% and copper ionization rates >50% in the generated metal plasma. More specifically, the present invention utilizes 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. Furthermore, through ion energy control technology, it achieves the one-step continuous production of high-bonding-strength, high-density metal films on the surface of the substrate.

[0226] By using the combination of multiple physical vapor deposition methods of the present invention, a uniform conductive seed layer is formed on both the substrate surface and the hole walls. This eliminates the need for special processing of the hole portion, resulting in a uniform conductive seed layer with strong adhesion to the substrate. Specifically, the standard deviation of the conductive seed layer thickness is 5%-20%. Furthermore, the ratio of the thickness of the conductive layer on the hole wall of the metallized hole to the thickness of the conductive layer on the substrate surface is greater than or equal to 1:1.

[0227] Several examples of combinations of various physical vapor deposition methods according to the present invention are illustrated below to enhance understanding of the present invention.

[0228] (Combination 1)

[0229] 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.

[0230] 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 walls.

[0231] Then, plasma deposition is performed, using nickel as a target material, selecting an arc current of 40-100A, an extraction current of 10A, a vacuum degree of 0.022-0.024Pa, an argon flow rate of 5-12sccm, and depositing a nickel layer.

[0232] Finally, a copper layer was deposited by DC magnetron sputtering using copper as a target at a voltage of 320 V and a current of 4.5 A. The total thickness of the plasma-deposited nickel layer and the DC magnetron sputtered copper layer was greater than 100 nm.

[0233] 12 μm of copper was electroplated on the DC magnetron sputtered copper layer to obtain a copper clad laminate with metallized holes.

[0234] The results of the above processing are shown in Figures 4a-c. Figure 4a is a FIB-TEM image of a nickel layer deposited by high-power pulsed magnetron sputtering, showing a thickness of 20-30 nm. Figure 4b is a FIB-TEM-EDX image of elemental line scan qualitative and quantitative analysis. Figure 4c is an optical microscope image of a section of a copper-clad laminate with a plated hole, showing that the copper layer thickness on both the substrate surface and the hole wall is approximately 12 μm, with a thickness ratio of 1:1, and the hole diameter is 100 μm. Furthermore, the bonding strength of the copper layer on the substrate surface is 1.0 N / mm @ 12 μm copper thickness. The copper layer on the hole wall shows no delamination or blistering under thermal shock, and the resistance change rate is less than 5%.

[0235] (Combination 2)

[0236] 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.

[0237] 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 walls.

[0238] Then, plasma deposition is performed, using copper as the target material, selecting an arc current of 40-100 A, an extraction current of 7-15 A (preferably 10 A), a vacuum degree of 0.022-0.024 Pa, an argon flow rate of 5-12 sccm, and depositing a copper layer 8-60 nm thick.

[0239] Finally, direct current magnetron sputtering is performed, using copper as a target material, selecting a voltage of 380 V and a current of 10 A, and sputtering a copper layer with a thickness of >100 nm, thereby obtaining a conductive seed crystal layer.

[0240] The results of the above processing are shown in Figures 5a-b. Figure 5a is a FIB-TEM image of a nickel layer sputtered by high-power pulsed magnetron sputtering. Carbon, oxygen, and a small amount of copper were detected at spectrum 10. Nickel, copper, and carbon derived from surface adsorption were detected at spectra 6, 7, and 8. Copper was detected at spectrum 9. Figure 5b is a FIB-TEM-EDX image obtained by qualitative and quantitative elemental line scanning.

[0241] (Combination 3)

[0242] 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 through-hole diameters of 20 μm and 50 μm.

[0243] 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 was 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.

[0244] Then, DC magnetron sputtering was performed, using copper as a target material, selecting a voltage of 345 V, a current of 5.2 A, a power of 0.8 KW, and a vacuum degree of 0.38 Pa, to sputter a copper layer with a thickness of >100 nm.

[0245] Copper is electroplated on the DC magnetron sputtered copper layer to a thickness of 2 μm, thereby obtaining a copper clad laminate with metallized holes.

[0246] The results of the above processing are shown in Figures 6a-c. Figure 6a is a FIB-TEM photograph of a nickel layer deposited by high-power pulsed magnetron sputtering, showing a thickness of 6 nm. Figure 6b is a FIB-TEM-EDX photograph of an electroplated copper layer, showing a thickness of 1.9 μm. Figure 6c is an optical microscope photograph of a section of a copper-clad laminate with a plated hole, showing that the copper layer thickness on both the substrate surface and the hole wall is approximately 2 μm, with a thickness ratio of 1:1. The hole diameter is 40 μm. Furthermore, the bonding strength of the copper layer on the substrate surface is 0.8 N / mm, and the copper layer on the hole wall exhibits no delamination or blistering under thermal shock, with a resistance change rate of less than 5%.

[0247] Several embodiments of a copper-clad laminate with metallized holes, a circuit board, and a manufacturing method thereof for implementing the present invention are illustrated below to enhance understanding of the present invention.

[0248] (Example 1)

[0249] 1.1 A 25 μm thick polyimide film was selected as a substrate. Through holes were laser drilled in the polyimide film. The apertures of the through holes were 20 μm, 40 μm, and 50 μm, respectively.

[0250] 1.2 Pre-treatment. Specifically, the substrate (rolled polyimide film) was placed into the ion implantation equipment through a continuous feeding mechanism and vacuumed to 5.0×10 -3 Pa, the substrate is irradiated with ion beams (Plasma treatment). In a vacuum environment, the upper and lower surfaces of the polyimide film are irradiated with argon ion beams at the same time, with an argon flow rate of 20-50 sccm, an ion energy of 300-500 eV, and an irradiation dose of 1.0-5.0x10 12 ions / cm 2 The irradiation time is 2-10 seconds. At this time, the temperature is controlled to rise to no more than 75 degrees to perform dehydration treatment, and the water vapor in the ion beam chamber is extracted using an exhaust device. Ion beam irradiation has the effect of both surface cleaning and dehydration.

[0251] 1.3 The conductive seed layer is produced by a combination of plasma deposition + high power pulsed magnetron sputtering + DC magnetron sputtering.

[0252] First, in a vacuum device, the chamber is evacuated to 0.022-0.024 Pa, and plasma deposition is performed using nickel as the target. A magnetically filtered vacuum cathode arc source is used to simultaneously plasma deposit nickel on the polyimide membrane surface 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.

[0253] 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 nickel ionization rate was greater than 30%, and a 5nm thick nickel layer was sputtered. The sheet resistance after sputtering was 5-120 ohms.

[0254] Finally, using copper as a target, DC magnetron sputtering is performed 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.

[0255] 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 on the hole walls was thickened to 12 μm on a copper electroplating production line.

[0256] The copper-clad laminate with plated holes produced in Example 1 has the following structure: a double-sided copper-clad laminate with plated through holes, a polyimide film with a thickness of 25 μm, and through-hole diameters of 20 μm, 40 μm, and 50 μm, respectively. The polyimide film surface and the plated hole walls, from inner to outer layers, consist of: 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 plated holes and the copper layer on the hole walls is smooth and uniform in thickness.

[0257] The resulting copper-clad laminate has a bonding strength of 1.0 N / mm on the surface of the substrate, no delamination or blistering of the copper layer on the hole walls under thermal shock, and a resistance change rate of less than 5%. Furthermore, the interface between the copper layer on the surface of the substrate and the copper layer on the hole walls of the copper-clad laminate with metallized holes is smooth and uniform in thickness.

[0258] (Example 2)

[0259] 2.1 A 38 μm thick polyimide film was selected as the substrate. Through holes and blind holes were laser drilled in the polyimide film. The diameter of the through holes was 40 μm, and the diameter of the blind holes was 20 μm.

[0260] 2.2 Pre-treatment: Place the substrate (rolled polyimide film) into the ion implantation equipment through a continuous feeding mechanism and evacuate to 1.2×10 -2Pa, the substrate is irradiated with an ion beam. In a vacuum environment, the upper and lower surfaces of the polyimide film are simultaneously irradiated with an argon and oxygen mixture at a flow rate of 100 seem. The temperature is then raised to over 75°C for dehydration, while a vacuum system is used to remove water vapor from the ion beam chamber. Ion beam irradiation simultaneously cleans and dehydrates the surface.

[0261] 2.3 The conductive seed layer is produced by a combination of high power pulsed magnetron sputtering + plasma deposition + DC magnetron sputtering.

[0262] First, in the vacuum equipment, evacuate to 0.2 Pa, use nickel as the target material, turn on the high-power pulsed magnetron sputtering power supply, 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, and the target surface power density is 5-15W / cm 2 , high-power pulsed magnetron sputtering was performed, the nickel ionization rate was greater than 30%, and a nickel layer with a sputtering thickness of 28nm was formed.

[0263] Then, the chamber was evacuated to 0.020-0.022 Pa, 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 5-12 sccm, the deposition ion energy was 75 eV, the arc current was 100 A, the extraction current was 10 A, and a nickel layer with a thickness of 60 nm was deposited. The square resistance after deposition was 5-120 ohms.

[0264] Finally, using copper as a target, 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 sheet resistance after sputtering was 0.1-50 ohms, preferably 2-30 ohms.

[0265] 2.4 Electroplating thickening to produce double-sided flexible copper-clad laminates with metallized holes. Specifically, the copper film on both the upper and lower surfaces of the substrate and on the hole walls is thickened to 5μm on the copper electroplating line. As an optional embodiment, through-holes and / or blind vias can be electroplated to fill or buried vias.

[0266] 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 with a 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 walls of the metallized holes are, from the inner layer to the outer layer, the following: a nickel layer with a thickness of 30 nm by high-power pulsed magnetron sputtering; a plasma-deposited nickel layer with a thickness of 60 nm; a copper layer with a thickness of 100 nm by DC magnetron sputtering; and an electroplated copper layer with a thickness of 5 μm. The interface between the copper layer on the surface of the substrate and the copper layer on the hole walls of the product is smooth and uniform in thickness. As an optional embodiment, the hole structure can be a metallized through hole and blind hole structure, or a filled hole and blind buried hole structure. 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 walls does not delaminate or blister under thermal shock, and the resistance change rate is less than 5%.

[0267] (Example 3)

[0268] 3.1 A 25 μm thick polyimide film was selected as the substrate. Laser drilling of through holes was performed on the polyimide film, with a hole diameter of 100 μm.

[0269] 3.2 Pre-treatment: Place the substrate (rolled polyimide film) into the ion implantation equipment through the continuous feeding mechanism and evacuate to 5.0×10 -2 Pa, the substrate is irradiated with an ion beam. In a vacuum environment, both the upper and lower surfaces of the polyimide film are simultaneously irradiated with an argon ion beam at a flow rate of 10 sccm. The temperature is then raised to over 75°C for dehydration, while a vacuum system is used to remove water vapor from the ion beam chamber. Ion beam irradiation simultaneously cleans and dehydrates the surface.

[0270] 3.3 The conductive seed layer is produced by a combination of high power pulsed magnetron sputtering + DC magnetron sputtering.

[0271] First, in a vacuum device, evacuate to 0.1-0.3 Pa, use nickel as the target material, turn on the high-power pulsed magnetron sputtering power supply, the voltage is 750 V, the current is 90 A, there are one or more sputtering sources, the power of each sputtering source is 2 kW, the pulse width is 100 μs, the frequency is 450 Hz, the peak current is 130 A, and the target surface power density is 15-20 W / cm 2 , high-power pulsed magnetron sputtering is performed, the nickel ionization rate is greater than 30%, the nickel layer with a sputtering thickness of 20nm, and the square resistance after nickel deposition is 40-80 ohms.

[0272] 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 thickness of 80 nm was sputtered. The sheet resistance after sputtering was 0.1-50 ohms, preferably 0.5-30 ohms.

[0273] 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 on the hole walls is thickened to 5 μm on a copper electroplating production line.

[0274] The copper-clad laminate with plated holes produced in Example 3 has the following structure: a double-sided copper-clad laminate with plated through holes, a polyimide film with a thickness of 25 μm, and a through-hole diameter of 100 μm. The polyimide film surface and the plated hole walls are composed, from inner to outer layers, of a 20 nm thick nickel layer deposited by high-power pulsed magnetron sputtering, an 80 nm thick copper layer deposited by DC magnetron sputtering, and a 5 μm thick electroplated copper layer. The interface between the copper layer on the surface of the substrate and the copper layer on the hole walls of the copper-clad laminate with plated holes is smooth and uniform in thickness. The copper layer on the surface of the substrate of the copper-clad laminate with plated holes exhibited a bonding strength of 0.9 N / mm. The copper layer on the hole walls showed no delamination or blistering under thermal shock (immersed in hot oil at 260°C for 10 seconds, three times; see IPC-TM-650 Test Method Manual 2.6.8 and 2.1.1 for testing procedures). The resistance change rate was less than 4% (the acceptable acceptance requirement is no more than 10%). Specifically, a photograph of the copper-clad laminate with plated holes after thermal shock is shown in Figure 7.

[0275] (Example 4)

[0276] 4.1 A 20 μm thick polyimide film was selected as the substrate. The polyimide film was laser drilled with a 30 μm diameter hole and mechanically drilled with a 150 μm diameter hole.

[0277] 4.2 Pre-treatment: Place the substrate (rolled polyimide film) into the ion implantation equipment through the continuous feeding mechanism and evacuate to 9.0×10 -2Pa, the substrate is subjected to ion beam irradiation treatment. In a vacuum environment, the upper and lower surfaces of the polyimide film are simultaneously irradiated with argon ion beams 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 the surface and dehydrates it. As another embodiment, the pre-treatment can also be cleaned by chemical cleaning. 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 then an alkaline solution) 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.

[0278] 4.3 The conductive seed layer is produced by a combination of high power pulsed magnetron sputtering + DC magnetron sputtering.

[0279] First, in the vacuum equipment, evacuate to 0.018 Pa, use nickel as the target material, turn on the high-power pulsed magnetron sputtering power supply, the voltage is 600 V, the current is 110 A, there are one or more sputtering sources, the power of each sputtering source is 2.5 kW, the pulse width is 100 μs, the frequency is 370 Hz, the peak current is 110 A, and the target surface power density is 15-20 W / cm 2 , high-power pulsed magnetron sputtering is performed, the nickel ionization rate is greater than 30%, the nickel layer with a sputtering thickness of 18nm, and the sheet resistance after sputtering is 50-80 ohms.

[0280] 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.

[0281] 4.4 Electroplating Thickening to Prepare Double-Sided Flexible Copper Clad Laminates with Metallized Holes Specifically, the copper film on both the upper and lower surfaces of the substrate and on the hole walls was thickened to 9 μm on a copper electroplating production line.

[0282] The structure of the copper-clad laminate with plated holes produced in Example 4 is as follows: a double-sided copper-clad laminate with plated through holes, a polyimide film with a thickness of 20 μm, and through-hole diameters of 30 μm and 150 μm. The surface of the polyimide film and the hole walls of the plated holes are, from inner to outer layers, composed of: a nickel layer formed by high-power pulsed magnetron sputtering with a thickness of 18 nm; a copper layer formed by DC magnetron sputtering with a thickness of 120 nm; and an electroplated copper layer with a thickness of 9 μm. The interface between the copper layer on the surface of the substrate of the copper-clad laminate with plated holes and the copper layer on the hole walls is smooth and uniform in thickness. The bonding strength of the copper layer on the surface of the substrate of the copper-clad laminate with plated holes is 0.8 N / mm @ 9 μm copper thickness. The copper layer on the hole walls shows no delamination or blistering under thermal shock, and the resistance change rate is less than 4% (the acceptable requirement is no more than 10%). Specifically, a photograph of the copper-clad laminate with plated holes after thermal shock is shown in Figure 8.

[0283] (Example 5)

[0284] 5.1 A 50 μm thick polyimide film is selected as a substrate. Laser drill holes in the polyimide film, with a diameter of 30 μm.

[0285] 5.2 Pre-treatment: Place the substrate (rolled polyimide film) into the ion implantation equipment through the continuous feeding mechanism and evacuate to 7.0×10 -2 Pa, the substrate is irradiated with an ion beam. In a vacuum environment, both the upper and lower surfaces of the polyimide film are simultaneously irradiated with an argon ion beam at a flow rate of 10 sccm. The temperature is then raised to over 75°C for dehydration, while a vacuum system is used to remove water vapor from the ion beam chamber. Ion beam irradiation simultaneously cleans and dehydrates the surface.

[0286] 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.

[0287] First, in the vacuum equipment, evacuate to 0.18 Pa, use nickel as the target material, turn on the high-power pulse magnetron sputtering power supply, 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, and the target surface power density is 15-20W / cm 2 With an accelerating bias of 30V, high-power pulsed magnetron sputtering was performed, achieving a nickel ionization rate of >30% and a nickel layer with a thickness of 22nm. Selecting an accelerating bias can increase the energy of deposited metal particles, facilitating the metallization of the inner walls of deep holes with higher aspect ratios.

[0288] Then, using copper as the target material, continue to turn on the high-power pulsed magnetron sputtering power supply, and use continuous high-power pulsed magnetron sputtering technology to sputter the copper film. The power density of the sputtering target surface is 100W / cm 2 The accelerating bias is 40V, and the accelerating bias adopts a DC voltage. The ionization rate of copper is greater than 50%. The sputtering thickness of the copper layer is 0.1 μm, and the square resistance after sputtering is 2-10 ohms.

[0289] 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.

[0290] 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 on the hole walls was thickened to 2 μm on a copper electroplating production line.

[0291] 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 with a thickness of 50 μm, and a through-hole diameter of 30 μm. The surface of the polyimide film and the hole walls of the metallized holes are, from the inner layer to the outer layer, the following: a nickel layer formed by high-power pulsed magnetron sputtering with a thickness of 22 nm; a copper layer formed by high-power pulsed magnetron sputtering with a thickness of 0.1 μm; a copper layer formed by DC magnetron sputtering with a thickness of 0.3 μm; and an electroplated copper layer with a thickness of 1.7 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 walls is smooth and uniform in 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 walls does not delaminate or blister under thermal shock, with a resistance change rate of less than 4%.

[0292] (Example 6)

[0293] 6.1 Select 20 μm thick ABF as the substrate. Laser drill blind holes in the ABF with a hole diameter of 20 μm.

[0294] 6.2 Pre-treatment. Specifically, the substrate is placed into the ion implantation equipment through the continuous feeding mechanism and vacuumed to 7.0×10 -2 Pa, 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. The temperature is then raised to over 75°C for dehydration, while a vacuum system is used to remove water vapor from the ion beam chamber. Ion beam irradiation simultaneously cleans and dehydrates the surface.

[0295] 6.3 The conductive seed layer was fabricated by a combination of high power pulsed magnetron sputtering + plasma deposition (nickel) + plasma deposition (copper).

[0296] First, in the vacuum equipment, the vacuum is evacuated to 0.18 Pa. With nickel as the target material, the high-power pulsed magnetron sputtering power supply is turned on with a voltage of 750 V, a current of 300 A, a pulse width of 100 μs, a frequency of 580 Hz, one or more sputtering sources, and a power of 3.2 kW for each sputtering source. The target surface power density is 27 W / cm 2 With an accelerating bias of 50V, high-power pulsed magnetron sputtering was performed, achieving a nickel ionization rate of >30% and a nickel layer with a thickness of 50nm. The use of an accelerating bias can increase the energy of the deposited metal particles, facilitating the metallization of the inner walls of deep holes with higher aspect ratios.

[0297] Then, using nickel as the target material, plasma deposition was performed using a magnetically filtered vacuum cathode arc source. The argon flow rate was 5-12 sccm, the deposition ion energy was 100 eV, the arc current was 100 A, the extraction current was 7 A, and a nickel layer with a thickness of 100 nm was deposited. The square resistance after deposition was 20-45 ohms.

[0298] Finally, plasma deposition is continued using copper as a target to deposit a copper layer with a thickness of 250 nm. The sheet resistance after deposition is 0.5-3 ohms.

[0299] 6.4 Electroplating thickening to produce a double-sided copper-clad laminate with metallized holes. Specifically, the copper film on both the upper and lower surfaces of the substrate and on the hole walls is thickened to 25 μm on the copper electroplating line. The blind holes are then filled with electroplating. The surface of the substrate where the blind holes were originally located is covered with a copper layer, resulting in a smooth and flat surface, identical to the surface elsewhere on the substrate.

[0300] 6.5 Expose, develop, and etch the prepared double-sided copper clad laminate to make a circuit board, and add insulating material as raw material to laminate and make a multi-layer circuit board.

[0301] The structure of the circuit board with plated through holes produced in Example 6 is as follows: a double-sided circuit board with plated through holes, an ABF substrate with a thickness of 20 μm, and blind vias with a diameter of 20 μm. The substrate surface and the plated through hole walls are, from inner to outer layers, composed of: a 50 nm thick nickel layer deposited by high-power pulsed magnetron sputtering; a 100 nm thick plasma-deposited nickel layer; a 250 nm thick plasma-deposited copper layer; and a 25 μm thick electroplated copper layer.

[0302] Specifically, optical micrographs of sections of blind buried vias formed after blind via filling are shown in Figures 9a-b, demonstrating a blind via filling structure formed by electroplating. The surface at the blind via location is also covered with a copper layer, identical to the surface appearance of the rest of the substrate, with a smooth and flat interface. The copper layer on the substrate surface of this circuit board with plated vias exhibits a bonding strength of 0.7 N / mm, and the copper layer on the hole walls exhibits no delamination or cracking under thermal shock, with a resistance change rate of less than 3%.

[0303] The foregoing description merely mentions preferred embodiments of the present invention. However, the present invention is not limited to the specific embodiments described herein. It will be readily apparent to those skilled in the art that various obvious modifications, adjustments, and substitutions may be made to these embodiments to adapt them to specific circumstances without departing from the gist of the present invention. In fact, the scope of protection of the present invention is defined by the claims and may include other examples that may be envisioned 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

1. A method for manufacturing a copper-clad laminate with metallized holes, comprising the following steps: Step S1: drilling holes in an insulating substrate; Step S2: pre-treating the porous substrate; Step S3: 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 crystal layer on the surface of the substrate and the hole wall, thereby obtaining a metallized substrate with metallized holes; Step S4: electroplating and thickening the metallized substrate to obtain a copper-clad laminate with metallized holes.

2. The method according to claim 1, characterized in that After step S4, the method further includes step S5: using the copper-clad laminate with metallized holes to manufacture a circuit board.

3. The method according to claim 2, characterized in that In the step S5, the circuit board is manufactured using a semi-additive method.

4. The method according to claim 1, characterized in that: The substrate is a polyimide film.

5. The method according to claim 1, characterized in that: In the step S1 , mechanical drilling or laser drilling is used to drill holes in the substrate.

6. The method according to claim 5, characterized in that The drilled holes are blind holes or through holes with a hole diameter of 20-500μm.

7. The method according to claim 5, characterized in that The drilled holes are blind holes or through holes with a hole diameter of 20-200 μm.

8. The method according to any one of claims 5 to 7, characterized in that: The hole depth of the drilled holes is 5-200 μm.

9. The method according to claim 1, characterized in that: The pre-treatment in step S2 includes one or more of plasma cleaning, dehydration, and alkaline solution surface treatment.

10. The method according to claim 1, characterized in that The various physical vapor deposition methods in step S3 include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

11. The method according to claim 1, characterized in that: The combination of multiple physical vapor deposition methods in step S3 includes high-power pulsed magnetron sputtering.

12. The method according to claim 1, characterized in that The processing in step S3 by combining 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.

13. The method according to claim 10 or 12, characterized in that: During ion implantation, the energy of the implanted ions is 3-20 keV.

14. The method according to claim 10 or 12, characterized in that: During ion implantation, the implantation dose is 1.0×10 14 -5.0×10 16 ions / cm 2 .

15. The method according to claim 10 or 12, characterized in that: During plasma deposition, the energy of the deposited ions is 30-100 eV.

16. The method according to any one of claims 10 to 12, characterized in that: During high power pulsed magnetron sputtering, the ionization rate of nickel is >30% and the ionization rate of copper is >50%.

17. The method according to any one of claims 10 to 12, characterized in that: During high power pulsed magnetron sputtering, the accelerating bias was 0-100 kV.

18. The method according to any one of claims 10 to 12, characterized in that: During high power pulsed magnetron sputtering, the accelerating bias voltage was 0-50 KV.

19. The method according to any one of claims 10 to 12, characterized in that: During high power pulsed magnetron sputtering, the target power density is 1-100W / cm 2 .

20. The method according to any one of claims 10 to 12, characterized in that During high power pulsed magnetron sputtering, the target power density is 3-20W / cm 2 .

21. The method according to any one of claims 10 to 12, characterized in that: During high-power pulsed magnetron sputtering, the pulse width is 80-3000 μs.

22. The method according to any one of claims 10 to 12, characterized in that During high power pulsed magnetron sputtering, the frequency is 200-5000 Hz.

23. The method according to any one of claims 10 to 12, characterized in that During high power pulsed magnetron sputtering, the peak current is 50-2000A.

24. The method according to any one of claims 10 to 12, characterized in that During high-power pulsed magnetron sputtering, the substrate moves through the device at a speed of 0.5-15 m / s.

25. The method according to claim 10 or 12, characterized in that The conventional magnetron sputtering is DC magnetron sputtering. During the DC magnetron sputtering, the voltage is 100V-2000V and the current is 1-100A.

26. The method according to claim 1, 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; The processing in step S3 by a combination of multiple physical vapor deposition methods includes: First, high-power pulsed magnetron sputtering is performed to form the nickel layer, followed by plasma deposition to deposit the nickel layer, and finally conventional magnetron sputtering is performed to sputter the copper layer.

27. The method according to claim 26, 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 pore wall.

28. The method according to claim 27, characterized in that The pulse width is 80-180 μs, the frequency is 340-400 Hz, and the peak current is 90-230A.

29. The method according to claim 26, characterized in that During plasma deposition, nickel was used as the target, the arc current was 40-100A, and the extraction current was 7-15A to deposit the nickel layer.

30. The method according to claim 29, characterized in that The extraction current is 9-11A.

31. The method according to claim 26, characterized in that The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, copper is used as a target material, the voltage is 300-2000V, the current is 4-100A, and the power is 1.2-200KW to produce a sputtered copper layer.

32. The method according to claim 31, characterized in that The voltage is 310-330V, the current is 4-5A, and the power is 1.3-1.6KW.

33. The method according to claim 26, characterized in that The total thickness of the plasma deposited nickel layer and the conventional magnetron sputtered copper layer is between 50 and 2000 nm.

34. The method according to claim 26, characterized in that Electroplating copper with a thickness of 0.5-25 μm is performed on the conventional magnetron sputtered copper layer to obtain a copper-clad laminate with metallized holes.

35. The method according to claim 1, 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; The processing in step S3 by a combination of multiple physical vapor deposition methods includes: First, high-power pulsed magnetron sputtering is performed to form the nickel layer, followed by plasma deposition to deposit the copper layer, and finally conventional magnetron sputtering is performed to sputter the copper layer.

36. The method according to claim 35, 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 pore wall.

37. The method according to claim 36, characterized in that The pulse width is 90-110 μs, the frequency is 410-430 Hz, and the peak current is 90-110A.

38. The method according to claim 35, characterized in that During plasma deposition, copper was used as the target, the arc current was 40-100A, and the extraction current was 7-15A to deposit the copper layer.

39. The method according to claim 38, characterized in that The extraction current is 9-11A.

40. The method according to claim 35, characterized in that The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, copper is used as a 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 50-2000nm is sputtered.

41. The method according to claim 40, characterized in that The voltage is 370-390V, the current is 9-11A, and the power is 3.4-4.2KW.

42. The method according to claim 35, characterized in that Electroplating copper with a thickness of 0.5-25 μm is performed on the conventional magnetron sputtered copper layer to obtain a copper-clad laminate with metallized holes.

43. The method according to claim 1, 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; The processing in step S3 by a combination of multiple 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.

44. [Corrected 12.09.2024 in accordance with Rule 26] A method according to claim 43, 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 pore wall.

45. The method according to claim 44, characterized in that The pulse width is 80-120 μs, the frequency is 400-420 Hz, the current is 110-300 A, and the power is 1.0-6.0 KW.

46. ​​The method according to claim 43, characterized in that The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, copper is used as a 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 50-2000nm is sputtered.

47. The method according to claim 46, characterized in that The voltage is 340-350V, the current is 5.0-6.0A, and the power is 1.7-2.1KW.

48. The method according to claim 43, characterized in that Electroplating copper with a thickness of 0.5-25 μm is performed on the conventional magnetron sputtered copper layer to obtain a copper-clad laminate with metallized holes.

49. The method according to claim 1, characterized in that The standard deviation of the thickness of the conductive seed crystal layer is 5%-20%; after step S4, 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.

50. A method for manufacturing a circuit board with metallized holes, comprising the following steps: Step S1: drilling holes in an insulating substrate; Step S2: pre-treating the porous substrate; Step S3: treating the surface of the substrate and the hole wall by a combination of multiple physical vapor deposition methods at the same time to form a conductive seed crystal layer on the surface of the substrate and the hole wall, thereby obtaining a metallized substrate with metallized holes; and Step S4: adding patterned metal on the metallized substrate with the metallized holes to make circuits on the conductive seed crystal layer of the metallized substrate with the metallized holes, thereby making a single-layer circuit board.

51. The method according to claim 50, characterized in that In step S4, patterned metal is added to both surfaces of the metallized substrate with metallized holes, thereby manufacturing a double-sided circuit board.

52. The method according to claim 51, characterized in that The double-sided circuit board is used as a substrate, the upper and lower surfaces of the double-sided circuit board are covered with prepregs, and steps S1 to S4 are repeated once or multiple times on the double-sided circuit board covered with prepregs, thereby preparing a multi-layer circuit board.

53. The method according to claim 50, characterized in that The substrate is a polyimide film.

54. The method according to claim 50, characterized in that In the step S1 , mechanical drilling or laser drilling is used to drill holes in the substrate.

55. The method according to claim 54, characterized in that The drilled holes are blind holes or through holes with a hole diameter of 20-500μm.

56. The method according to claim 54, characterized in that The drilled holes are blind holes or through holes with a hole diameter of 20-200 μm.

57. The method according to any one of claims 54 to 56, characterized in that The hole depth of the drilled holes is 5-200 μm.

58. The method according to claim 50, characterized in that The pre-treatment in step S2 includes one or more of plasma cleaning, dehydration, and alkaline solution surface treatment.

59. The method according to claim 50, characterized in that The various physical vapor deposition methods in step S3 include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

60. The method according to claim 50, characterized in that The combination of multiple physical vapor deposition methods in step S3 includes high-power pulsed magnetron sputtering.

61. The method according to claim 50, characterized in that The processing in step S3 by combining 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.

62. The method according to claim 59 or 61, characterized in that During ion implantation, the energy of the implanted ions is 3-20 keV.

63. The method according to claim 59 or 61, characterized in that During ion implantation, the implantation dose is 1.0×10 14 -5.0×10 16 ions / cm 2 .

64. The method according to claim 59 or 61, characterized in that During plasma deposition, the energy of the deposited ions is 30-100 eV.

65. The method according to any one of claims 59 to 61, characterized in that During high power pulsed magnetron sputtering, the ionization rate of nickel is >30% and the ionization rate of copper is >50%.

66. The method according to any one of claims 59 to 61, characterized in that During high power pulsed magnetron sputtering, the accelerating bias was 0-100 kV.

67. The method according to any one of claims 59 to 61, characterized in that During high power pulsed magnetron sputtering, the accelerating bias voltage was 0-50 KV.

68. The method according to any one of claims 59 to 61, characterized in that During high power pulsed magnetron sputtering, the target power density is 1-100W / cm 2 .

69. The method according to any one of claims 59 to 61, characterized in that During high power pulsed magnetron sputtering, the target power density is 3-20W / cm 2 .

70. The method according to any one of claims 59 to 61, characterized in that During high-power pulsed magnetron sputtering, the pulse width is 80-3000 μs.

71. The method according to any one of claims 59 to 61, characterized in that During high power pulsed magnetron sputtering, the frequency is 200-5000 Hz.

72. The method according to any one of claims 59 to 61, characterized in that During high power pulsed magnetron sputtering, the peak current is 50-2000A.

73. The method according to claim 59 or 61, characterized in that The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, the voltage is 100V-2000V and the current is 1-100A.

74. The method of claim 50, wherein: 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; The processing in step S3 by a combination of multiple physical vapor deposition methods includes: First, high-power pulsed magnetron sputtering is performed to form the nickel layer, followed by plasma deposition to deposit the nickel layer, and finally conventional magnetron sputtering is performed to sputter the copper layer.

75. The method according to claim 74, 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 pore wall.

76. The method according to claim 75, characterized in that The pulse width is 90-110 μs, the frequency is 340-360 Hz, and the peak current is 110-130A.

77. The method of claim 74, wherein: During plasma deposition, nickel was used as the target, the arc current was 40-100A, and the extraction current was 7-15A to deposit the nickel layer.

78. The method according to claim 77, characterized in that The extraction current is 9-11A.

79. The method according to claim 73, characterized in that The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, copper is used as a target material, the voltage is 300-2000V, the current is 4-100A, and the power is 1.2-200KW.

80. The method according to claim 79, characterized in that The voltage is 310-330V, the current is 4-5A, and the power is 1.25-1.65KW.

81. The method of claim 74, wherein: The total thickness of the plasma deposited nickel layer and the conventional magnetron sputtered copper layer is between 50 and 2000 nm.

82. The method of claim 74, wherein: 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.

83. The method according to claim 50, 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; The processing in step S3 by a combination of multiple physical vapor deposition methods includes: First, high-power pulsed magnetron sputtering is performed to form the nickel layer, followed by plasma deposition to deposit the copper layer, and finally conventional magnetron sputtering is performed to sputter the copper layer.

84. The method according to claim 83, 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 pore wall.

85. The method according to claim 84, characterized in that The pulse width is 90-110 μs, the frequency is 410-430 Hz, and the peak current is 100-110A.

86. The method according to claim 83, characterized in that During plasma deposition, copper was used as the target, the arc current was 40-100A, and the extraction current was 7-15A to deposit the copper layer.

87. The method according to claim 86, characterized in that The extraction current is 9-11A.

88. The method according to claim 83, characterized in that The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, copper is used as a 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 50-2000nm is sputtered.

89. The method according to claim 88, characterized in that The voltage is 370-390V, the current is 9-11A, and the power is 3.4-4.3KW.

90. The method of claim 83, wherein: 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.

91. The method according to claim 50, 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; The processing in step S3 by a combination of multiple 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.

92. The method according to claim 91, 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 pore wall.

93. The method according to claim 92, characterized in that The pulse width is 100-110 μs, the frequency is 400-410 Hz, the current is 110-130 A, and the power is 2.0-4.5 KW.

94. The method according to claim 91, characterized in that The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, copper is used as a 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.

95. The method according to claim 94, characterized in that During the DC magnetron sputtering, copper is used as a target material, the voltage is 300-340V, the current is 3-6A, and the power is 0.9-2KW.

96. The method according to claim 91, 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.

97. The method according to claim 50, characterized in that The standard deviation of the thickness of the conductive seed crystal layer is 5%-20%. After step S4, 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.

98. 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.

99. The copper clad laminate according to claim 98, characterized in that The substrate is a polyimide film.

100. The copper clad laminate according to claim 98, characterized in that The holes are formed by mechanical drilling or laser drilling.

101. The copper clad laminate according to claim 100, characterized in that: The hole is a blind hole or a through hole with a pore diameter of 20-500 μm.

102. The copper clad laminate according to claim 100, characterized in that: The holes are blind holes or through holes with a hole diameter of 20-200 μm.

103. The copper clad laminate according to any one of claims 100-102, characterized in that: The blind hole has a hole depth of 5-200 μm.

104. The copper clad laminate according to claim 98, characterized in that The various physical vapor deposition methods include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

105. The copper clad laminate according to claim 98, characterized in that The combination of various physical vapor deposition methods includes high power pulsed magnetron sputtering.

106. The copper clad laminate according to claim 98, characterized in that Processing in a combination of various 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.

107. The copper clad laminate according to claim 98, 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.

108. The copper clad laminate according to claim 98, 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.

109. The copper clad laminate according to claim 108, 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 pore wall.

110. The copper clad laminate according to claim 108, characterized in that: The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, copper is used as a 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.

111. The copper clad laminate according to claim 108, characterized in that: Electroplating copper with a thickness of 1-25 μm is performed on the conventional magnetron sputtered copper layer to obtain a copper-clad laminate with metallized holes.

112. 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.

113. The circuit board according to claim 112, characterized in that The substrate is a polyimide film.

114. The circuit board according to claim 112, characterized in that The holes are formed by mechanical drilling or laser drilling.

115. The circuit board according to claim 114, characterized in that The hole is a blind hole or a through hole with a pore diameter of 20-500 μm.

116. The circuit board according to claim 114, characterized in that The holes are blind holes or through holes with a hole diameter of 20-200 μm.

117. The circuit board according to any one of claims 114-116, characterized in that: The blind hole has a hole depth of 5-200 μm.

118. The circuit board according to claim 112, characterized in that The various physical vapor deposition methods include: ion implantation, plasma deposition, high-power pulsed magnetron sputtering, and conventional magnetron sputtering.

119. The circuit board according to claim 112, characterized in that The combination of various physical vapor deposition methods includes high power pulsed magnetron sputtering.

120. The circuit board according to claim 112, characterized in that Processing in a combination of various 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.

121. The circuit board according to claim 112, 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.

122. The circuit board according to claim 112, characterized in that: The circuit board is a single-layer circuit board or a multi-layer circuit board.

123. The circuit board according to claim 112, 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.

124. The circuit board according to claim 123, 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 pore wall.

125. The circuit board according to claim 123, characterized in that The conventional magnetron sputtering is direct current magnetron sputtering. During the direct current magnetron sputtering, copper is used as a 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.

126. The circuit board according to claim 123, 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.

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