CN1527656A - Magnetically controlled sputtering process of making printed circuit board - Google Patents
Magnetically controlled sputtering process of making printed circuit board Download PDFInfo
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- CN1527656A CN1527656A CNA031468918A CN03146891A CN1527656A CN 1527656 A CN1527656 A CN 1527656A CN A031468918 A CNA031468918 A CN A031468918A CN 03146891 A CN03146891 A CN 03146891A CN 1527656 A CN1527656 A CN 1527656A
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Abstract
The present invention provides one kind of magnetically controlled sputtering process of making printed circuit board. The process includes the following steps: drilling holes on the single layer base material; magnetically controlled sputtering the bottom dielectric and metal layer on the drilled single layer base material; magnetically controlled sputtering conducting copper layer on the single layer base material; drilling holes on multilayer board; magnetically controlled sputtering bottom dielectric and metal layer on the drilled multilayer board; magnetically controlled sputtering conducting copper layer on the drilled multilayer board; and repeating the foregoing steps until reaching the required layer number of the printed circuit board. The present invention combines unique hole forming method and sputtering method and has raised copper-plating and hole-metallizing efficiency, raised reliability and high fine circuit making capacity.
Description
Technical field
The present invention relates to be used to make the method for printed substrate, specifically, relate to a kind of process of utilizing magnetically controlled sputter method to make printed substrate.
Background technology
Along with microminiaturization, high speed and the digitlization of electronic product, the PCB product also must develop to the direction of ultrathin type, high density, miniaturization.High density is meant components and parts useful load and the wiring density that improves on the printed substrate unit are, and the measure of taking is wiring board fine rule, aperture and multilayer.Conductor width and spacing trend are less than 0.1mm (as the live width line-spacing of 3mil), the via aperture is less than φ 0.2mm, multi-layer sheet can use in a large number more than 10 layers, and a large amount of blind holes and buried via hole occur, and hole metallization and etching are two committed steps in the printed substrate manufacturing process.But there are following three shortcomings in traditional process: 1) production high accuracy multi-layer sheet difficulty height.Conductor width and spacing are more little, require copper thickness also thin more, copper thickness is thin more, time in etching solution is also short more, be difficult for side etching phenomenon takes place, traditional copper thickness mostly is more than the 12 μ m, and the demand for development copper thickness of modern technologies is accomplished below the 9 μ m, traditional calendering copper method is because the restriction of process conditions is difficult to make the following Copper Foil of 9 μ m, and price is also expensive.Traditional hole metallization realizes by chemical plating and Direct Electroplating method that mainly the increase chemical plating and the Direct Electroplating method difficulty that cause printed substrate of small-bore strengthen, and on the one hand, chemical degree copper liquid exchanges bad in the hole, produces the phenomenon that the hole is thick, the hole is broken; On the other hand, the electrolytic copper plating solution dispersibility does not reach and requires and inhomogeneous, the dog bone phenomenon of generation through-hole plating, and the reliability of plated-through hole reduces.2) high pollution.Traditional processing technology all is that the chemical reaction mode is carried out, and especially the chemical plating hole needs a large amount of organic substance carcinogens such as () formaldehyde as reducing agent, in addition, also to need inorganic heavy metallic salt (pb2+ etc.) and cyanide (CN-), fluoride etc.This class is polluted and is difficult to basically, be forced each PCB factory all will drop into many funds and be used for sewage disposal along with the attention of people to environmental protection by biodegradation and recovery at present, and this has brought certain influence for the running of fund.3) production process complexity, inefficiency.Must be through multiple tracks chemical reaction process or electroplating process, complex process, operation is long.In order to overcome the above problems, there has been the people that physical gas phase deposition technology is applied in the PCB industry, use the method for magnetron sputtering to make printed substrate, " make the process of printed substrate " (the applying date: 2000.7.26 as application for a patent for invention, publication number: disclose a kind of magnetron sputtering process of making printed circuit board of utilizing CN1335743A), on the base material of circuit negative-appearing image, plate face and through-hole wall can both can be plated the layer of metal film equably, solved above problem preferably, but there is following defective simultaneously in this process: 1) for the multi-layer sheet more than two layers, it is unreliable that the conducting in interlayer hole connects.Insulating material between the multi-layer sheet is the meeting partial liquefaction when carrying out the high temperature lamination, causes the effect forfeiture in hole after flowing.The effect in hole is by behind the hole metallization two-layer or multi-layer sheet being connected conducting, and the hole is divided into through hole, blind hole and buried via hole.The manufacture method of the described intermediate insulating layer of its technology is: by designing requirement, making the multi-layer sheet interlayer connects with copper dish position exposed, all the other places are adhered to by photosensitive material, after degreasing is cleaned, film in two face plating designing requirement cleans striping then, stays metallized hole, and periphery has the insulating barrier of certain width Copper Foil, and this circle is made the usefulness that layer is connected with the through hole conduction of layer.The method of its boring and lamination is: bored the hole by design earlier on base material, behind magnetron sputtering two double sided boards and intermediate insulation plate have been folded according to the aligned in position that sets in advance, carried out the high temperature lamination at last and promptly obtain four layers of wiring board.Because the intermediate insulation plate can be liquefied as fluid in the high temperature lamination process, space in the middle of the two-layer wiring board is filled up, because fluid can flow to the space of any direction, the surface that also can be full of iknsulating liquid and hole in the hole in event hole also can be insulated liquid on every side and cover, insulating barrier also can attenuation, causes interlayer to come conducting by the hole.2) magnetron sputtering is very remarkable for the making effect of preparation film, such as thickness is conductive layer below the 1 μ m, but because the efficient of magnetron sputtering is lower than the efficient of electro-coppering, for copper thickness is wiring board more than the 3 μ m, meet the requirements of thickness, the sputtering time that needs is long, and efficient is low-cost to rise.
Summary of the invention
Main purpose of the present invention provides a kind of method of utilizing magnetron sputtering method to make wiring board, solves the conduction problem that is connected that existing magnetron sputtering method is made circuit board technique middle level and interlayer hole, makes it to be applicable to large-scale production.An of the present invention purpose is to improve the efficient of copper facing and hole metallization.
For achieving the above object, a kind of magnetron sputtering process of making printed circuit board of utilizing that the present invention proposes is characterized in that may further comprise the steps: 1) single layer of substrate material boring: via is produced according to the designing requirement of wiring board in single layer of substrate material cleaning back; 2) single layer of substrate material after will holing is through clean, and the inwall magnetic control sputtering plating in one side surface or both side surface and hole is used to improve the bottom metal clad layer of Copper Foil and substrate affinity; 3) magnetic control sputtering plating conductive copper layer on the dielectric layer metal of the inwall in this single layer of substrate material one side surface or both side surface hole; 4) multi-layer sheet boring: will make the inner core multi-layer sheet through the high temperature pressing again through two or more single layer of substrate material plate therebetween of above-mentioned processing with insulating barrier, and clean, and on described multi-layer sheet, drill through via or blind hole according to the designing requirement of wiring board; 5) the inner core multi-layer sheet after will holing is through clean, and the inwall magnetic control sputtering plating in one side surface or both side surface and hole is used to improve the bottom metal clad layer of Copper Foil and substrate affinity; 6) magnetic control sputtering plating conductive copper layer on the dielectric layer metal of the inwall in this inner core multi-layer sheet one side surface or both side surface and hole.
As required, after step 6), can also may further comprise the steps: 7) through step 4), 5), 6) inner core multi-layer sheet after handling is as multilayer base plate, it with through step 1), 2), 3) single layer of substrate material after handling is referred to as backing material plate; Two or more backing material plate therebetween with insulating barrier, are made the inner core multi-layer sheet through the high temperature pressing again, clean, on described multi-layer sheet, drill through via or blind hole according to the designing requirement of wiring board; 8) the inner core multi-layer sheet after will holing is through clean, is used to improve the bottom metal clad layer of Copper Foil and substrate affinity at one side surface or both side surface magnetic control sputtering plating; 9) magnetic control sputtering plating conductive copper layer on the dielectric layer metal of this inner core multi-layer sheet one side surface or both side surface; Repeating step 7)-9), until the requirement that reaches the wiring board number of plies.
The present invention also increases following steps in order to improve copper facing efficient after step 3) or step 6): a) the designing requirement electrolysis plating according to copper thickness adds thick copper layer on conductive copper layer; B) adding sputter or plating top dielectric metal level on the thick copper layer.
Institute's plating bottom metal clad layer and top dielectric metal level are the metal level of 1 to 4 layer of different materials, for example combine the 1-4 layer in order by chromium, molybdenum, silver, zinc, gold, nickel, copper or its alloy.
Wherein can adopt lift-off technology to make line pattern, it comprise be positioned at step 1), 4) afterwards following steps: A) apply or attach the last layer photosensitive material and be placed on the mask aligner again and expose at the substrate surface that has cleaned, develop, clean the circuit negative-appearing image that substrate surface obtains having photosensitive material layer, then oven dry; Also comprise and be arranged in step 3), 6) afterwards step B): there is the base material of conductive layer to immerse the chemical cleaning solvent surperficial sputter and heats to 60 ℃-90 ℃, with ultrasonic waves for cleaning, fast will be with the coatings removing of photosensitive material.
The invention has the beneficial effects as follows:
Compare with existing magnetron sputtering process of making printed circuit board, improved the pore-forming mode.The present invention adopts the repeatedly mode of boring when making multi-layer sheet, each boring is to carry out through being operated on the plate behind the lamination, and the hole is divided into through hole and blind hole (buried via hole is the via of internal layer).For example being operated plate is four laminates, then be in the both sides of making the double sided board in line pattern and hole, boring again behind stack insulating material and the lamination, therefore can guarantee the connectedness of hole through after the copper facing to interlayer, and need not on the insulated substrate of centre, to hole separately and the plating hole, also need not the contraposition in hole.
In addition, the method that adopts magnetron sputtering and electro-coppering to combine can improve the efficient of copper facing and hole metallization and can control copper-plated thickness flexibly according to designing requirement again.Traditional calendering copper is made the method for copper-clad plate and can't the copper layer be accomplished below the 9 μ m according to the requirement of new technology, and adopting magnetron sputtering method copper facing to be subjected to the restriction of sputtering rate purely, production efficiency can reduce greatly when being used to produce thickness greater than the Copper Foil more than the 2 μ m.The present invention adopts magnetron sputtering method copper facing in the early stage of electro-coppering, guaranteed the good metallization in hole, small-bore, inhomogeneous and the hole dog bone phenomenon of through-hole plating of having avoided employing chemical plating and galvanoplastic to cause, later stage is adopted galvanoplastic copper facing, be beneficial to and accelerate copper-plated efficient, improve production efficiency of products.Owing to do not re-use electroless copper, reduced the pollution of harmful substance, reduced cost, help environmental protection.
Because conductive layer can be done thinlyyer, reduces side etching phenomenon effectively, thereby can make circuit meticulousr.Thinner copper layer needs etching solution still less, etch quantity also still less, side etching quantity is also more controlled, has guaranteed the quality of fine-line.
Feature of the present invention and advantage will be elaborated in conjunction with the accompanying drawings by embodiment.
Description of drawings
Fig. 1 represents the structural representation of individual layer wiring board of the present invention.
Fig. 2 represents magnetron sputtering copper facing flow chart of the present invention.
Fig. 3 represents the flow chart of a kind of embodiment of the present invention.
Fig. 4 represents the flow chart of another embodiment of the present invention.
Embodiment
The structure chart of individual layer wiring board of the present invention as shown in Figure 1 is base material 100, dielectric layer 101, conductive copper layer 102 from bottom to up successively, add thick copper layer 103 and protective layer 104.Base material 100 can adopt by epoxy resin fiberglass cloth, polyimides, polyester, pottery, the base material that metal or glass make, dielectric layer 101 forms 1-4 layer metal by magnetron sputtering, thickness is 5-500nm, the reason of sputter multilayer dielectricity layer metal is: the coefficient of expansion of base material and conductive copper layer differs bigger, if directly copper facing on base material, affinity is not strong, peel strength does not reach requirement, so it is excessive to carry out coefficient of expansion ladder between base material and conductive copper layer, the metal clad of selecting for use also is the big again coefficient of expansion of the little coefficient of expansion of elder generation, last excessively reduced the poor of thermal coefficient of expansion between coating and the metallic matrix, reduced the shrinkage of coating when variations in temperature and the stress of coating inside to copper.Suppress the coating be full of cracks, peeled off, improved the cohesive force and the impact resistance of coating.The thickness of conductive copper layer 102 is 0.1-5 μ m, and the thickness that adds thick copper layer 103 is 1-18 μ m.
Specific embodiment one: make multilayer printed circuit board, adopt the electric plating of whole board technology, it makes flow process as shown in Figure 2:
1) boring: will be operated plate cleaning back and drill through the hole on the plate being operated according to the designing requirement of wiring board.
2) be operated plate through clean after will holing, at this inwall that is operated a side surface of plate or both side surface and hole sputter chromium successively, nickel and monel, be used to improve the affinity of Copper Foil and substrate, the thickness of sputter time according to coating is made as 0.1-5min, the sputter electric current is unsuitable too small, in order to avoid efficient is low excessively, be made as 0.1-5A, sputter gas pressure＜1atm, gas are Ar gas, the distance of target and base material should not be too far away, in order to avoid the insufficient strength of sputter is made as 5-25cm, the sputter gas flow is 8 * 10
-3To 3 * 10
-3Torr;
3) sputter conductive copper layer 0.1-5 μ m on the dielectric layer metal of a side surface that is operated plate or both side surface and hole inwall, the thickness of sputter time according to coating is made as 0.1-30min, the sputter electric current is 0.1-5A, sputter gas pressure＜1atm, gas is Ar gas, the distance of target and base material is 5-25cm, and the sputter gas flow is 8 * 10
-3To 3 * 10
-3Torr; Vacuum system must be at base vacuum 2 * 10
-6Torr just can start working, the empty vacuum system of leaking of good base vacuum and nothing has crucial effect to the uniformity of the assurance coat of metal and the stability of product, and the molecule mean free path that the sputtering pressure of process gas and vacuum system are determined has relation, with target-substrate distance sizable relation is arranged again usually;
4) electric plating of whole board.Designing requirement plating according to copper thickness on conductive copper layer adds thick copper layer, and electroplating current is 0.5-1A, and electroplating time is made as 0.5-2hr according to the thickness of coating.
5) line pattern is made.Paste light-sensitive surface, behind exposure imaging, form line pattern.
6) make protective layer: its manufacture method is to electroplate one or more metals wherein such as adding on the thick copper layer magnetron sputtering or electrodeposited chromium, nickel, gold, zinc, tin at the skin that needs protection; If internal layer is then at the metal clad of its surperficial sputter increase with the insulating substrate affinity, the chromium of sputter 0.005-0.5 μ m in particular, this has very much progress for affinity, moisture resistance, chemical resistance and the thermal endurance aspect improved between conductive layer and insulating substrate.
7) circuit etching: place the chemical solution corrosion to clean out circuit base material;
8) lamination: will be operated the substrate alignment and fold, and behind high pressure-temperature, press together;
9) multi-layer sheet boring: will make the inner core multi-layer sheet through the high temperature pressing again through two or more single layer of substrate material plate therebetween of above-mentioned processing with insulating barrier, and clean, and on described multi-layer sheet, drill through via or blind hole according to the designing requirement of wiring board;
10) the inner core multi-layer sheet after will holing is through clean, and the inwall magnetic control sputtering plating in one side surface or both side surface and hole is used to improve the bottom metal clad layer of Copper Foil and substrate affinity, technology and technological requirement same 2);
11) magnetic control sputtering plating conductive copper layer on the dielectric layer metal of the inwall in this inner core multi-layer sheet one side surface or both side surface and hole, technology and technological requirement are with 3);
Repeating step 4), 5), 6), 7), 8) technological process.
Repeat above-mentioned steps 9 again), 10), 11), until the requirement that reaches the wiring board number of plies.
12) surface lines figure and protective layer are made.
Present embodiment increases protective layer on the outermost layer circuit, prevent that effective copper layer from being scratched, scratching, and the more important thing is to prevent that the copper layer is oxidized.
What deserves to be explained is, less as the thickness of required conductive copper layer, can not re-plating thickening copper after sputter copper.
" backing material plate " of indication of the present invention both can refer to alleged single layer of substrate material plate usually, also can refer to be called multilayer base plate through the inner core multi-layer sheet after the above-mentioned processing.
Specific embodiment two: make the printed on both sides wiring board, use the graphic plating technology, it makes flow process as shown in Figure 2:
1) boring: will be operated plate cleaning back and drill through the hole on the plate being operated according to the designing requirement of wiring board.
2) single layer of substrate material after will holing is through clean, and the inwall magnetic control sputtering plating in one side surface or both side surface and hole is used to improve the bottom metal clad layer of Copper Foil and substrate affinity, and technology and technological requirement are with embodiment one;
3) magnetic control sputtering plating conductive copper layer on the dielectric layer metal of this single layer of substrate material one side surface or both side surface and hole inwall, technology and technological requirement are with embodiment one;
4) line pattern is made.Paste light-sensitive surface, behind exposure imaging, form line pattern.Wherein the thickness of light-sensitive surface should be greater than the thickness of thickening copper electroplating layer.This step belongs to " lift-off " technology commonly used in the ITO technology with following step 7).
5) graphic plating.Designing requirement figure electrolysis plating according to copper thickness on conductive copper layer adds thick copper layer, and electroplating current is 0.5-1A, and electroplating time is made as 0.5-2hr according to the thickness of coating.
6) make protective layer: its manufacture method is to electroplate at the skin that needs protection to add one or more metals wherein such as magnetic control sputtering plating chromium, nickel, gold, zinc, tin on the thick copper layer; If internal layer is then at the metal clad of its surperficial sputter increase with the insulating substrate affinity, the chromium of sputter 0.005-0.5 μ m in particular, this has very much progress for affinity, moisture resistance, chemical resistance and the thermal endurance aspect improved between conductive layer and insulating substrate.
7) clean and circuit etching: be used for it is removed with protective layer of photosensitive material down and clean out circuit with corroding at chemical solution with the copper layer of photosensitive material it on, this protective layer can be used as resist layer, makes etching only work to the copper layer of logicalnot circuit part;
8) high temperature lamination: be used for being operated substrate alignment and folding, behind high pressure-temperature, press together with two-layer at least;
Repeating step 1 again) to 8) can be made into multi-layer sheet.Be particularly useful for being manufactured with the high density interconnect multilayer circuit board of a large amount of buried via holes and blind hole.
9) carry out the outer-layer circuit graphic making at last.
Present embodiment can solve the etch issues of fine-line better, and conductive layer and base material tack are good, and its peel strength can reach 1.0kgf/cm.
Specific embodiment three: make multilayer printed circuit board, lift-off technology is used in the circuit moulding, and it makes flow process as shown in Figure 4:
1) boring: will be operated backing material plate cleaning back and hole being operated on the plate according to the designing requirement of wiring board;
2) clean base material.
3) make the circuit negative-appearing image: apply or stick one deck photosensitive material at substrate surface base material is placed on exposure on the mask aligner, development, clean the circuit negative-appearing image that substrate surface obtains photosensitive material layer, then oven dry;
4) sputter dielectric layer: be operated plate through clean after will holing, at this inwall that is operated a side surface of plate or both side surface and hole adhesion layer of jet-plating metallization chromium, nickel and three kinds of metals of monel successively, technology and technological requirement are with embodiment one;
5) sputter copper: at this single layer of substrate material or one side surface of the multi-layer sheet behind lamination or both side surface sputter conductive copper layer 0.1-5 μ m, technology and technological requirement are with embodiment one;
6) sputter top dielectric metallic chromium layer, thickness is 5-100nm, process conditions are the same;
7) ultrasonic waves for cleaning: have the base material of conductive layer to immerse in the NaOH cleaning solvent surperficial sputter and heat,, will remove with the coatings of photosensitive material fast with ultrasonic waves for cleaning to 60 ℃-90 ℃;
8) high temperature lamination: will be two-layer at least be operated the plate alignment and fold, therebetween with insulation board after high pressure-temperature press together;
Repeating step 1 again) to 8) up to the requirement that reaches the wiring board number of plies.
9) carry out the outer-layer circuit graphic making at last.
Present embodiment can solve the etch issues of fine-line better, and conductive layer and base material tack are good, and its peel strength also can reach 1.0kgf/cm.
Claims (11)
1. one kind is utilized the magnetron sputtering process of making printed circuit board, it is characterized in that may further comprise the steps:
1) single layer of substrate material boring: via is produced according to the designing requirement of wiring board in single layer of substrate material cleaning back;
2) single layer of substrate material after will holing is through clean, and the inwall magnetic control sputtering plating in one side surface or both side surface and hole is used to improve the bottom metal clad layer of Copper Foil and substrate affinity;
3) magnetic control sputtering plating conductive copper layer on the dielectric layer metal of this single layer of substrate material one side surface or both side surface and hole inwall;
4) multi-layer sheet boring: will make the inner core multi-layer sheet through the high temperature pressing again through two or more single layer of substrate material plate therebetween of above-mentioned processing with insulating barrier, and clean, and on described multi-layer sheet, drill through via or blind hole according to the designing requirement of wiring board;
5) the inner core multi-layer sheet after will holing is through clean, and the inwall magnetic control sputtering plating in one side surface or both side surface and hole is used to improve the bottom metal clad layer of Copper Foil and substrate affinity;
6) magnetic control sputtering plating conductive copper layer on the dielectric layer metal of this inner core multi-layer sheet one side surface or both side surface and hole inwall.
2. process of making printed circuit board as claimed in claim 1 is characterized in that: further comprising the steps of after step 6):
7) through step 4), 5), 6) inner core multi-layer sheet after handling is as multilayer base plate, it and single layer of substrate material are referred to as backing material plate; Two or more backing material plate therebetween with insulating barrier, are made the inner core multi-layer sheet through the high temperature pressing again, clean, on described multi-layer sheet, drill through via or blind hole according to the designing requirement of wiring board;
8) the inner core multi-layer sheet after will holing is through clean, is used to improve the bottom metal clad layer of Copper Foil and substrate affinity at one side surface or both side surface magnetic control sputtering plating;
9) magnetic control sputtering plating conductive copper layer on the dielectric layer metal of this inner core multi-layer sheet one side surface or both side surface;
Repeating step 7)-9), until the requirement that reaches the wiring board number of plies.
3. process of making printed circuit board as claimed in claim 1 is characterized in that: also increase following steps after step 3) or step 6): a) the designing requirement electrolysis plating according to copper thickness adds thick copper layer on conductive copper layer; B) adding sputter or plating top dielectric metal level on the thick copper layer.
4. process of making printed circuit board as claimed in claim 1 is characterized in that: described single layer of substrate material is to be made by epoxy resin fiberglass cloth, polyimides, polyester, pottery, metal or glass.
5. as claim 1,3 described process of making printed circuit board, it is characterized in that: institute's plating bottom metal clad layer and top dielectric metal level are the metal level of 1 to 4 layer of different materials.
6. process of making printed circuit board as claimed in claim 5 is characterized in that: described bottom and top dielectric metal level combine the 1-4 layer in order by chromium, molybdenum, silver, zinc, gold, nickel, copper or its alloy.
7. process of making printed circuit board as claimed in claim 1, it is characterized in that: the described clean of step 1) is meant carries out FAR INFRARED HEATING to 40-200 ℃ to hole-drilled single layer of substrate material or the inwall through lamination and hole-drilled inner core multi-layer sheet surface and hole, handle with plasma bombardment again, make its surperficial oxygen ionization.
8. process of making printed circuit board as claimed in claim 1, it is characterized in that: described sputtering process condition is: the time is 0.1-30min, and the sputter electric current is 0.1-5A, sputter gas pressure＜1atm, gas is Ar gas, and the distance of target and base material is 5-25cm.
9. process of making printed circuit board as claimed in claim 2 is characterized in that: the process conditions of described electrolysis plating thickening copper are: electroplating current is 0.5-1A, and electroplating time is 0.5-2hr.
10. process of making printed circuit board as claimed in claim 3 is characterized in that: also comprise step before step a) or the step b): c) manufacture line pattern.
11. process of making printed circuit board as claimed in claim 1, it is characterized in that adopting lift-off technology to make line. the road figure, it comprise be positioned at step 1), 4) afterwards following steps: A) apply or attach the last layer photosensitive material and be placed on the mask aligner again and expose at the substrate surface that has cleaned, develop, clean the circuit negative-appearing image that substrate surface obtains having photosensitive material layer, then oven dry; Also comprise and be arranged in step 3), 6) afterwards step B): there is the base material of conductive layer to immerse the chemical cleaning solvent surperficial sputter and heats to 60 ℃-90 ℃, with ultrasonic waves for cleaning, fast will be with the coatings removing of photosensitive material.
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| CNA031468918A CN1527656A (en) | 2003-09-19 | 2003-09-19 | Magnetically controlled sputtering process of making printed circuit board |
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| CNA031468918A CN1527656A (en) | 2003-09-19 | 2003-09-19 | Magnetically controlled sputtering process of making printed circuit board |
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| CN116334556A (en) * | 2023-03-14 | 2023-06-27 | 中国科学院兰州化学物理研究所 | Preparation method of polymer composite copper foil copper seed layer |
-
2003
- 2003-09-19 CN CNA031468918A patent/CN1527656A/en active Pending
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