TW403793B - A method to deposit metal layer - Google Patents

Abstract

Polyimide substrates with copper layer are well known for applications in the electronic industry, they are produced by decomposition of metal-organic compound utilizing a glow discharge method, followed by a current free metallization process of the developed metallic film. In case that oxygen was not added during the decomposition of the first metal layer, layers containing carbon will be generated, which have smaller conductivity and smaller catalytic activity. If alkaline metallization solutions were used merely, a most firmly stuck metal layer will be deposit on the surface of the polyimide at the very beginning, but the stickiness of the metal layer to polyimide will reduce considerably after the metal was contact with a watery alkaline solution. If it is processed in an oxygen atmosphere, a palladium layer, which must be reduced later, will be generated. This kind of layers reveals only little or even no stickiness, as they are exposed to chemical or electrochemical processing solutions. Oxygen and carbon lacking layer will be generated by applying combination of oxygen containing compounds and inert gas in the glow discharge process for metal deposition. Nevertheless, the reducing of the stickiness after the metallized substrate was contact with a watery alkaline solution can be avoided by utilizing acid or neutral current free metallization solutions to generate the second metal layer. These methods developed first time the production of a high-density circuit carrier on a non-metallized polyimide foil.

Description

A 4 of 793_s' _ V. Description of the invention (1. ^ The present invention relates to a method for bonding a metal layer on the surface of a polyimide board, and a method for manufacturing a circuit carrier, and the method is applied to manufacture the same In the electronics industry, polyimide boards are used to manufacture circuit boards, hybrid circuits, semiconductor pedestals (wafer pedestals, multi-chip modules) and other base materials. Compared to In terms of traditional materials, such as epoxy resin, this material has many benefits. For example, its heat resistance is relatively high, so when this material encounters a thermal load, its expansion in length is greater than that of traditional materials. In addition, the base of the polyimide board has a better insulation resistance value. When it is used as the base material of the semiconductor base, the raw material of the polyimide can be placed on an appropriate base , And it is turned into a laminate by the spin-coating method, and then converted into polyimide. The laminate constructed in this way can be etched to the smallest drill in a simple and continuous production manner Holes. These drills It is used for the connection of many metallized layers. When manufacturing polyimide laminates, such as circuit boards, mostly polyimide films covered with copper films are used. The wires are mostly etched. The program is made on copper plating. In this regard, process technologies (such as Handbueh der

Leiteiplattentechnik, Hrsg. G. Herrmann, Volume 2, Eugen G

Leuze, Saulgau, 1991). Although this type of technology is basically suitable for making circuit boards, the width of the finest wires made by this technology is about 75-100 μm. This paper size applies Chinese National Standard (CNS) Α4 specification (210X297). -5- Please read the notes on the back before filling out this page.) Order 'Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives, Printing, Central Standards Bureau, Ministry of Economics Printed A7 by Bei Gong Consumer Cooperative Co., Ltd. "Q3793__ V. Description of the invention (2.) The steel film is adhered to the surface of the polyimide board with glue through the traditional method. However, this layer of adhesive will become soft after heat treatment, such as when soldering circuit boards, and it does not have sufficient toughness in the chemical tank provided for drilling metallization of polyimide laminates. In order to eliminate this layer of glue, a technique known to professionals such as "casting" was developed to make glue-free polyimide laminates. Among them, the liquid polyamide solution is poured onto a copper film before being dehydrated and cyclized to form a polyimide board. In this way, when the polyimide is formed on the copper film, a strong polymer / metal bond is formed. This method also has a disadvantage, that is, it is only suitable for very thick copper films, such as 17 μm thick. In addition, this material is particularly expensive, such as the product Espanex® manufactured by Nippon Steel Chemical co. Ltd, Tokyo. However, polyimide laminates with a thin copper film can still be manufactured. However, the manufacturing of such laminates is particularly expensive, so the material price is also considerable. There is also a problem when processing such a laminated board covered with a thin layer of copper film, because the copper film is very sensitive to mechanical effects. With the technology of "casting", this type of film cannot be used at all, because such laminated boards are discarded in large quantities during manufacturing. As long as a laminated board with a copper film on its surface is not used as a raw material, the finest wire can be produced in any case. In this case, the wire is formed directly on its surface by a metal plating method. Until now, neither sputter plating or metal evaporation, or chemical-free, non-adhesive polyimide substrates have been used in electrical paper standards (CNS) A4 specifications. (21GX297mm) ---- -6- (Please read the precautions on the back before filling this page)

1. Printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs, 1T. ___ ^ 03793_B7 V. Description of the invention (3 ·) The manufacture of road boards. If you want to make a metal layer with sufficient adhesion on a polyimide board, you first need to add a thin layer of chrome, and then coat it with copper. This is the case, for example, with Sheldahl's pre-drilled mesh-like material. However, chromium is difficult to corrode, so an additional corrosion procedure is required, and it is best to avoid the use of chromium plating as much as possible. From a technical point of view, what we are most looking forward to here is the use of uncoated polyimide boards to make circuit carriers. However, in practice, this technique has not been successful for the following reasons: Compared with other polymers, polyimide has the disadvantage of a large amount of water, especially when the metal plating method is used. Facts have proved that if the copper plating is plated on the polyimide plate with no current or electrolytic method, when b is heat treated, such as during welding, it adheres to the surface of the polyimide plate. Sex will decrease significantly or disappear completely. In order to prevent bubble-like peeling during heat treatment, it is generally recommended that the polyimide film coated with a coating be annealed after plating. However, if a polyimide film with copper plating on the whole or both sides is subjected to heat treatment, an annealing process alone is not enough to prevent the generation of bubbles. In this case, the internal water vapor generated by the chemical metallization process will not escape during the annealing process, so that when the water is heat treated, it is exploded from the polyimide plate like an explosion. Run out and tear the copper film on its surface. For these reasons, another method was developed to firmly metallize the base of the polyimide board. Because the metal layer it is coated with requires sufficient adhesion on the substrate during or after heat treatment, the vacuum process is introduced into metallization. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 gong) (Please read the precautions on the back before filling out this page) Order printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 40379. ^ V. Description of the invention (4 ·) Here, the method of using a glow discharge to crack a volatile metal compound to plate a metal layer is a method worth considering. In DE 35 10 982 A1, a method for producing conductive structures on non-conductors has been published, for example on polyfluorene imine films. b is to let the metal organic compound crack in the glow discharge area, and the surface of the non-conductor is coated with a metal thin film. This layer of metal film that has been plated is mainly used as the germ layer of active catalyst in the subsequent surface currentless metallization process. DE 38 06 587 A1 describes a process for producing metal structures by using a method in which a metal organic compound is cracked in a glow discharge region on a polyimide plate. Other methods of using glow discharge and metal organic compounds for metallization are described in DE 37 16 235 Al, DE 37 44 062 A1, and DE 38 28 211 C2. In order to use the glow discharge method to produce a metal layer that is as pure as possible, that is, a metal layer with a low content of carbon and oxygen impurities, it is recommended to heat the substrate as high as possible during metal plating. Its carbon-containing impurities are organic components derived from volatile metal organic compounds most commonly used in metallization. The effect of the substrate temperature on the carbon content in the metal plating layer by the glow discharge method is shown in, for example, "Thin palladium films prepared by metal-organic plasma-enhanced chemical vapour" by E. Feurer and H. Suhr. deposition ", Thin Solid Films, 152 (1988), 81, 84. According to the article, its carbon content is based on the increase in substrate temperature, and the paper size uses the Chinese National Standard (CNS) M specifications (210X297 mm) (please read the note on the back before filling out this page) Order 403793 V. Description of invention (5 ·) Decreasing. It can also be seen from this document that the palladium metal layer at room temperature contains less than 30 weight percent carbon. If the metal compound is not sufficiently cracked during the glow discharge, or the complex compounds that are only partially cracked are not completely desorbed from the surface of the substrate, so that the carbon content of the metal layer is too high, then The conductivity of the plated metal layer is quite small, and on its surface, its catalytic activity for initiating non-current metal deposition is not large enough, so it is easy to form a layer contaminated by oxides by the non-current method. Metal layer, or can not form a plating layer at all. Printed by the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) In the application of Sudo, heating the substrate is not welcome. So try to use other methods to reduce the carbon content in its metal layer. As mentioned in the aforementioned document by E. Feurer and H. Suhr, it has been suggested that the metal layer to be plated should be reprocessed with an oxygen plasma. According to the experiments made by these authors, another workaround is to replace argon, which is generally used as a carrier gas, with oxygen during metal plating. In this case, palladium oxide will be plated out instead of palladium. It can be placed in a hydrogen plasma ‘with a subsequent treatment’ to allow it to be reduced to palladium again. However, this approach is quite complicated and expensive. In addition, when oxygen is flowing through the storage tank of its compound, its metal organic compound is already cracking, so only a small part of it can reach the glow discharge region. The method for producing a metal plating layer by glow discharge can also produce a strongly adhered metal layer on the surface of a polyimide plate. All that is required is to use a non-current or electrolytic metallization bath on this metal layer, and then plate other metals. But it is obvious that if the required annealing size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 403793 A7 _______B7 5. After the description of the invention (6.), or after confirming its adhesion When or before the property test, the base plated with plating is brought into contact with an alkaline aqueous solution, the metal layer plated on the surface of the polyimide plate will not have sufficient adhesion. The so-called aqueous test solution, for example, is the developer or stripper used in the photoresist during the structuring process, so as to build the wire structure on the entire metal plating layer. This reduction in adhesion caused by contact with an alkaline aqueous solution cannot be recovered by a subsequent annealing process. From this point of view, the basic problem of the present invention is to avoid the shortcomings of the existing technology 'and find a method so that it can use a currentless method to plate a layer of pure metal on the surface of the polyimide board in order to The finest wire structure is produced, and the adhesion of the metal plating on its surface will not be damaged after the unavoidable procedure after contacting this key with an alkaline aqueous solution. And find a way to make the polyimide board, when used to make a circuit carrier, also be able to produce the finest and firmly adhered wire structure on the surface of the polyimide board. This problem is solved by applying the first and the first scope of the patent application (printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). And some excellent application forms are listed in the scope of the second patent application. This metal layer with strong adhesion on the polyimide board substrate can be manufactured by the basic method of the following steps: a- In a mixed gas environment, this gas contains an inert gas and oxygen or an oxygen-containing compound, A method of decomposing volatile metal compounds on the surface of polyimide board with a glow discharge to coat a paper with the size of China National Standard (CNS) A4 (210X297 mm) -10- Central Bureau of Standards, Ministry of Economic Affairs Employee Consumption Cooperative Seal 51 403793 at ------ B7 V. Description of Invention (7.) ----- The first metal layer with very low carbon and oxygen content, b- on top of the first metal layer From an acidic or neutral neutral gold coating, the second metal layer is mixed with a non-Wei method.佃: The first metal layer plated by the glow discharge method has a unique characteristic: After adjusting its deposition parameters appropriately, it can = make it smooth and bright. . ## — After the surface of the bond layer is rubbed, a part of the metal film will be easily removed. This-part of the coating has a relatively small adhesion to its base material. Using a high-magnification electron microscope (grating-type electron microscope, transmission electron microscope), it can be seen that the metal layer deposited has a relatively dense spherical particle stacking structure. Obviously, they have only a small bond with each other. If the first metal layer is plated in a gaseous environment containing oxygen compounds, and the second metal is plated with an acidic or neutral no-current metallizing solution, the first metal layer is loose. In part, it can be strengthened. In this way, an adhesive bond can be formed between the metal layer and the surface of the polyfluorene subplate, and it will not be damaged even in contact with the alkaline aqueous solution. In addition, compared to known methods, polyimide plates metalized in this manner will also absorb much less water when subjected to a chemical deposition process. Therefore, less hydroxyl ions remain in the material after treatment. Especially when the substrate is under thermal load, it may weaken its bonding bond through hydrolysis. When the finest wires are to be manufactured, the adhesion of the wires to the surface of the laminated board is particularly required. The reason is that the wire is only applicable to a particularly small paper size. The Chinese National Standard (CNS) A4 specification (210X297 mm) is applicable. -11-(Please read the precautions on the back before filling this page)

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.I I- I Printed by the Central Bureau of Quasi-Ministry of Economic Affairs, Shellfish Consumer Cooperative, 403793 V. Description of the invention (8. = Covered area, produced on the surface of the laminated board-, :: In this case, different Under the operating conditions, its = must = particularly high. Silk uses rotten solution of gastrointestinal gas phase, = side to Lai Qi Lin _ core, it is very easy to make the surface of the laminated board under the wire-an inclined surface. Therefore, for a wider wire, the inclined separation formed in this way has a greater effect on the weight of a thin wire than the wide wire. On the whole, it is oxygen or an oxygen-containing gas. After the first-layer metal layer is formed in the photovoltaic method in China, a metal layer having a high catalytic activity can be obtained, so that a very pure metal layer can be clocked on it by using a non-current method. The oxygen compound is preferably oxygen (〇 2). In addition to oxygen, nitrogen oxides (Ν 2〇 / Ν〇χ) can also be used, they'll form at least intermediate oxygen atoms and nitrogen when glow discharge Inert gas comes. Except for volatile metals In addition to compounds and oxygen-containing compounds, these 5 oxidizing mixed rhenium components are also some miscellaneous, such as nitrogen or rare gases. However, based on price considerations, the inert gas is usually argon β in the When metal is plated, the oxidizing ability of the oxygen-containing compounds in the mixed gas will clean a cleaned and activated surface of the substrate at the time of bonding metal. Here, it is usually during glow discharge, It is cleaned by the organic fragments of the formed metal organic compound, so the adhesion of the metal layer is improved. If a mixed gas containing an additional inert carrier gas is used, it can even be used completely

(Please read the precautions on the back before filling out this page) »——— ——— The size of the paper used in the edition is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -12- Employee Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs Printed A7 403793 B7 Description of the invention (9.) Prevent the formation of metal oxide layers' because their conductivity and catalytic activity when electroless metal plating is not high enough. In addition, it can prevent metal organic compounds from entering the glow discharge The zone was previously decomposed. This is because the carrier gas used for its compounds is not pure oxygen, but a mixed gas containing an inert gas. It will flow through most of the liquid metal compounds. A particularly suitable The partial pressure ratio of oxygen-containing compound to inert gas in the mixed gas used to build a metal layer completely free of carbon and oxygen is between 2.1 and 1: 8, and it is best adjusted to 丨: 3 and 1 : 4. Assuming that the ligand in the metal organic compound will be completely oxidized by oxygen to carbon dioxide and water ', then when its partial pressure is adjusted between 1: 3 and 1: 4, one can be determined Calculated value based on theoretical oxygen consumption (quantitative chemistry). For example, 'Steam bond at π-allyl-π-cyclopentadienyl-Ibar- (π), 45 ° C, ratio When adjusted to 1: 3, about 15% to 75% of the stoichiometric oxygen will be consumed 'to completely oxidize the ligands in the compound. The oxygen content in the gas mixture is amazing Both are quite high, but it can still produce a metal layer with few oxygen elements. This is due to the oxidation of the ligands mentioned above and the oxygen element they consume during the reaction. It is used to carry out In the reaction chamber for the decomposition of metal compounds, the total pressure of the mixed gas is preferably between 1 Pa and 50 Pa. Volatile metal compounds use some compounds known in the art, such as palladium, copper, gold, or Platinum compounds, or their mixtures. Similarly, other metal compounds can still be used, as long as the metal layer formed by it is used in the subsequent currentless metallization process. (CNS > A4 size (210X297 mm -13- (Please read the notes on the back before filling in this page) Order printed by the Central Consumers Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives 403793 Α7 Β7 V. Description of the invention (1〇 ·) It can have catalyst activity. It is particularly suitable The compounds are: dimethyl-cyclo ^ dienyl-platinum, dimethyl-gold_ethenyl acetate ', especially π-propylidene · π · hexamethylenedienyl_palladium_ (ΙΙ) The deposition conditions in the documents mentioned at the beginning can be appropriately transferred to the metal plating method of the present invention. Palladium is particularly excellent because it can be easily removed by using the corrosion method. And With a no-current method, it is not a problem when it is coated with another metal layer on the steel recording groove. In addition to palladium, if a non-catalytically active metal is used to plate the first metal layer, the substrate must be immersed in an active solution such as chlorine before being electrolessly metalized. Palladium solution. Because of the production of a thin layer of palladium metal, a metal layer with catalytic activity can be formed for the next process of non-current metal deposition, that is, no other steps for activating this metal layer, such as the application containing A solution of precious metals. By using the method of the present invention, a metal layer with scarce carbon and oxygen content can be produced by a glow discharge method in one process step. Other processing procedures, such as glow discharge in a reducing gas environment such as hydrogen, are no longer needed. It is mainly used for plating a thickness of 0.01 μηι to 0.1 μΙη thick. When manufacturing a relatively thin coating, its chemical solution must strengthen its chemical corrosive force on the surface of the polyimide board in the next processing procedure, but this also prevents it from achieving a sufficient adhesion. There is no benefit to plating on thick metal layers. In addition to its long processing time and high price, " problems can also arise when making particularly fine wire structures. In addition, a particularly thick surface metal layer is difficult to be engraved. This paper size applies to the Chinese national standard (CNS > Μ size (2 丨 〇X297mm) -14- (Please read the precautions on the back before filling in this page) Order printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperatives Crack 403793 at _ B7 V. Description of the invention (11.) When using the glow discharge method to make metal coatings, if a sufficient conductivity can be achieved to enable direct metallization by electrolytic method in the next step, you can also use Other metal compounds are used to plate its first metal layer, such as the i-mesh compound. In the currentless metallization method, the optimal pH value of the metallization tank is between 2 and 8, and the main value is between 2 and 8. To 7. The main coatings are nickel, copper, copper, thin, or alloy plating baths of these metals. The nickel / boron alloy coating is particularly suitable as its second metal layer, because it comes from the entire metal layer It is easier to etch when making metal structures. In another excellent embodiment, there is a thin palladium metal layer or a nickel / phosphorus alloy layer and a layer of phosphorus with a phosphorus content of 3 to 5 weight percent. Galvanized , As its second metal layer. 'When manufacturing circuit carriers with very small and highly dense conductor structures, they must be on non-conductive substrates with polyimide surfaces and mostly made of laminated boards. Make the smallest holes. Therefore, it is best to use a method with the following basic process steps: a- Add at least a metal layer on the surface of the substrate. A temporary etching mask such as a plating, If the evaporation method is used, b- using the optical army technology, the metal layer is structured in the following process steps: ° ba-a metal mask is coated on the metal layer, preferably a liquid normal phase Photoresist, this paper size applies to Chinese national rubbing (CNS > A4 size (210X 297 cm)) -15- (Please read the precautions on the back before filling this page) Order 403793 at ------- B7_ V. Description of the Invention (l2.) Bb- Expose and develop the photomask. Among them, the drilling position on the photomask that is intended as the base will be removed, and be-etched in the metal layer. C -Etching holes in its substrate, and d · A metal layer which is removed in the process before step c) 'or between the phantom and the process steps d), the light will again cover layer is removed from the substrate. When a thin aluminum metal layer is used as the plasma etching mask, the etching holes on the metal layer can be performed simultaneously with the development process of the photoresist. After using this thinly coated liquid photoresist, the stripping process of this layer of photoresist and the plasma etching process can be performed at the same time, and the process is simplified again. Then, the surface of the substrate will be constructed with wires in accordance with the planned process below. The width and spacing of the wires are basically below 100 μm, and a metal surface is built on the wall of its hole: e-Using a mixed gas with oxidizing capacity, the gas contains oxygen-containing compounds and even inert gas, its surface and tube wall have been treated in advance by glow discharge method, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs n · N ^ i ^^ 1 ^^ 1 nm ml I 1_1 HI. ^ 1 ^, vs (please read the notes on the back before filling this page) f- In a mixed gas environment, the gas contains inert gas and The oxygen-containing compound is bonded to the first metal layer by a method of glow discharge cracking the volatile metal compound. A second metal layer is then plated from an acidic or neutral metallization bath using a currentless metal layer plating method. As the case may be, you can use the no-current method and / or electrolytic method to apply a metal layer. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -16- --_ 403793_ B7 ——— I 丨 · II —-丨 V. Description of the invention (13.) g- Use photomask technology to structure each metal layer, and the most important is to use a normal phase photoresist layer. The following are some typical application forms of the present invention: There are many different materials' can be used as the base of polyimide board: In addition to polyimide film, it can also be used with other carrier materials Laminated on a laminated board such as FR4 material (epoxy / glass fiber) and steel membrane. In addition, both flat polyimide boards and spin-on coatings can be metalized according to the method of the present invention. Here, it is also reasonable to use a material made of melted and / or hardened polyimide under the polyimide plate. In addition, the polyimide boards used can also have different chemical structures. For example, KAPTON H, Warnzeichen der Firma DuPont de Nemours, Inc., Wilmington, Del., USA is a polymer product concentrated from pyromellitic dianhydride (PMDA) and diaminophenyl ether (DDE). "In contrast, upiLEX, the trade name of UBE Industries, Tokyo, Japan, is a concentrated product consisting of 3,4 3, 4, _biphenyl-tetracarbonic anhydride (BPDA), and DDE (UPILEX-R) Or p-phenylenediamine (PPD) (UPILEX-S). Before using the glow discharge method to deposit the first metal layer, it is sometimes necessary to fabricate a drilled hole on its polyimide substrate by punching, drilling, or preferably by etching '. In order to make an etching mask (drilling mask) to facilitate the drilling of holes on the surface of the polyimide plate, the metal layer introduced is only temporarily introduced onto the surface. In other words, E is removed again before the wires on the polyimide plate are formed. And it cannot be used as a guide wire for the formation of this paper. It is applicable to the Chinese National Standard (CNS) M specification (2lQx297). (Please read the precautions on the back before filling this page.) 1Τ- Staff of the Central Standards Bureau of the Ministry of Economic Affairs Consumption cooperative printing -17- 403793 at ------- B7 _ V. Description of the invention (14 ·) ~ —'— ---- 2 Basic metal layer. It can also be plated—a layer of metal suitable for making wires. Because the etching mask will be removed from the perforated substrate, and a new metal layer will be plated on to make the engraved mask. Therefore, when the iron hole is paid, the mask and the mask The damage caused by the connection between the base wire surfaces will not adversely affect the firmness of the wire produced later. A drilled mask formed on the surface of the substrate for the purpose of making a chain hole 'is manufactured photochemically using a mask. The photomask made with the better choice of positive photoresist basically has a higher optical resolution, and therefore can produce finer structures. For example, compared with dry film (the thickness of the photoresist layer is 30-50μηι), it can produce a relatively thin coating (5-1-10μm thick) when using photoresist paint, so it is exposed to light during exposure. The light in the coating will have a relatively small diffraction effect ^ Because the coating thickness of the photoresist paint is small, its adhesion on the base is also better. In addition, if a positive photoresist is used, we can use a positive image to expose the photoresist layer, so that the exposure error will not cause much impact. It is also possible to use a photoresist which is electroplated. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative II 11--I-1 1 ^ 1 I 1. III — ^ ϋ nn 1 ^ 1 (Please read the precautions on the back before filling this page) Holes on the substrate It will be made using a dry etching method. The glow discharge method is particularly suitable. For this purpose, the substrate will be placed in a suitable device together with a drilling mask above it, with a gas such as oxygen, and preferably with oxygen and carbon tetrafluoride (CF4) The resulting mixed gas is processed. After the processing parameters are optimized, such as the composition and pressure of the gas, the power of the glow discharge, the processing temperature and time, etc., a sufficiently steep and this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -18- 403793 a? _______B7 V. Description of the invention (15 ·) There is no hole wall on the cutting surface caused by excessive corrosion under the mask. This makes it possible to make very small drills on very thick substrates ^. When the borehole is formed, its metal etching surface will also be removed. The substrate with the drilled holes is then cleaned, for example with an aqueous solution containing a wetting agent. * 'Then the surface to be plated will be treated in advance by glow discharge method. For example, its surface needs to be etched, cleaned and / or activated with an active chemical group. This refers to the reaction of gases and chemical groups on the surface of polyimide plates. For pretreatment I *, the substrate is placed in a conventional plasma reactor, such as a parallel plate reactor. This reactor consists of a tubular or tunnel-shaped reactor. The glow discharge used as a pre-treatment can be generated by a direct current or an alternating current (high frequency in the range of kHz or MHz). The surface is preferably etched with oxygen-containing compounds, such as nitrogen oxides (N20 / NOX), oxygen / argon or a mixed gas of oxygen / nitrogen. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs.-N. Nn u H ^^ 1 I 1 ^ 1 n I---^^ 1 ϋ · ^^ 1 (Please read the notes on the back before filling (This page) The first metal layer, which is catalytically active and has the ability of the medium to adhere to it, will be treated by glow discharge cracking of volatile metal compounds. on the surface. There is an inert carrier gas, which will be directed towards this point and guided through a storage tank containing metal organic compounds. In this inert gas, it generally contains oxygen (02) or nitrogen oxide (N2O / N0x) in addition to oxygen-containing compounds. If its carrier gas is in accordance with the Chinese National Standard (CNS) A4 specification (210 > C297 mm) at this paper scale -19- Printed by the Sheller Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 403793 at B7 V. Description of the invention (l6 ·) When the metal compound vapors passing through the storage tank are not mixed with the oxygen-containing compounds, they will be respectively introduced into the plasma reactor, and will continue to flow into the glow discharge area in this way. In addition, its oxidizing carrier gas will also be split into two streams. One of them will flow through its preparation tank, while the other will be directed into the plasma reactor. It is also a feasible method to introduce metal organic compounds directly into the plasma reactor without the need to carry gas. The mixed gas with oxidizing power is directly introduced into the plasma reactor. The carbon and oxygen content of the metal layer plated by the glow discharge method can be measured using, for example, ESCA (Electronic Spectrometer for Chemistry). In response to this point, the metal layer that it is plated on will be placed in an ultra-high vacuum chamber and then irradiated with X-rays (Al-Ka or Mg-Ka lines). The atomic layer on the metal layer is excited by this high-energy ray and is released, causing electrons to run out of its material. Its energy can be measured, so that the composition of its metal layer can be quantitatively analyzed for its elements. In the case of a bond metal layer, the handle is particularly excellent. Because it will form a catalytically active metal layer for the next non-current metal plating layer, so that the activation process of this metal layer, such as activation by precious metal solution, is no longer necessary. The conditions required for metallization are basically the same as those for the pre-treatment of glow discharge. The pressure in the processing chamber is usually 1 Pa to 50 Pa. Most of the time, 'on the substrate there will be a temperature close to room temperature or slightly higher than it' and it can be adjusted by the electric power of the glow discharge. It is also beneficial to heat its base. Stay in Conformity · Treatment Standards (CNS) M Threat (2 丨 OX297) -------- Policy— V ... (Please read the note ^^ on the back before filling this page) < 11 -20- 403793 B77 V. Description of the invention (17.) On this base metal layer, the current-free metallization process can be used in an acidic or neutral plating bath to eliminate the need for nickel. / Shed alloy, or nickel / phosphorus alloy, etc. Here, metal-like gold and cobalt, or alloys thereof, and alloys of pure nickel and cobalt are also considered metals. On a completely superimposed metal structure, it is better to plate a layer of palladium in a non-current manner, because in the currently known weakly acidic chemical reduction copper tank, its metal quality is not sufficient to meet all technical aspects. Claim. If the wire is manufactured by a method other than the superposition technique, such as when the semi-superposition method is used to plate palladium as the second metal layer, it must be noted that the palladium metal layer can only be plated to a limited thickness. This can be avoided because 'the surface is more difficult to etch compared to the nickel / boron alloy layer', so only when the etchant can penetrate through the small holes and penetrate to the bottom of its plating layer, and put it from below When the palladium metal is peeled off, it can be simply removed from the surface. For the method of the present invention, the following aqueous electroless metallization plating baths are generally used: 1. A non-current nickel bath with hypophosphite as the reducing agent to produce a chain / phosphorus coating:

In ^^^ 1 —mil HI n I. nn m ^^^ 1 ^^^ 1 n, lseJ ..--(Please read the notes on the back before filling this page) Filled with nickel sulfate (NiS04.5H2〇) 25-30 g / liter sodium hypophosphite 30 g / liter citric acid 2 g / liter acetic acid 5 g / liter amine acetic acid 10 g / liter acetate in lead 2 mg / liter paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) -21-403793 at _ B7__ V. Description of the invention (is.) Acid test value 6.2

Temperature 80-84 ° C In nickel / phosphorus coatings, it contains approximately 4 weight percent phosphorus. In addition to nickel salts, cobalt salts can also be used to coat cobalt / phosphorus alloy layers, or a mixture of nickel salts and cobalt salts can be used to deposit nickel / cobalt / phosphorus coatings. 2. Dimethylamine boron is used as a reducing agent for non-current nickel baths to produce nickel / boron coatings: 2a. Nickel sulfate (NiS04.5H20) 25 g / L dimethylamine boron 4 g / L succinic acid Sodium 25 g / L sodium sulfate 15 g / L pH 5.0

Temperature 60 ° C 2b. Nickel sulfate (NiS04.5H20) 40 g / l dimethylamine boron 1-6 g / l sodium citrate 20 g / l lactic acid (85 weight percent) 10 g / l acid test value 7.0 economic Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the precautions on the back before filling this page) Temperature 40. C2c_ Nickel sulfate (NiS04.5H20) 50 g / l dimethylamine boron 2.5 g / l sodium citrate 25 g / l lactic acid (85% by weight) 25 g / l thiodiacetic acid 1.5 mg / l This paper size applies to China National Standard (CNS) M specification (210X297 mm) -22- 403793 A7 B7 V. Description of the invention (19 ·) pH value 6-7 Temperature 40 ° C We can also use plating bath containing nickel chloride or nickel acetate To replace nickel sulfate. Diethylamine boron is also very suitable to replace dimethylamine boron as a reducing agent. 3. Use formic acid or its derivative as the reducing agent for the palladium tank without current: printed by the Central Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 3a. Palladium acetate sodium ethylenediamine formate succinate pH ) Temperature 3b. Palladium dichloride 2-ethylaminoaminoethylamine methanoic acid ethyl ester potassium dihydrogen phosphate pH value (adjusted with formic acid) Temperature 3c. Palladium acetate 1,2-bis (3-amine Propylamine)-sodium ethane formate succinate pH value (adjusted with formic acid) temperature

0.05 mol / liter 0.1 mol / liter 0.2 mol / liter 0.15 mol / liter 5.5 67 ° C 0.5 mol / liter 0.6 mol / liter 0.3 mol / liter 0.2 mol / liter 6.0 70 ° C 0.05 mol Ear / liter 0.1 mole / liter 0.3 mole / liter 0.1 mole / liter 5.9 59 ° C 4. Hypoquinic acid is used as reducing agent for copper tank without current: This paper is applicable to China Standard (CNS) A4 (210X297 mm) -23-^^^^ 1 ^^^^ 1 ^^^^ 1 ^^^^ 1 m ^ in ^^^^ 1 nn n ^ i · ^^ i · — nil— nn-** (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs as 3793 V. Description of the invention (2〇 ·) Copper chloride (CuCl2 2Η2〇) 0.06 mol / L N- (hydroxyalkyl) -ethylenediamine triacetic acid trisodium salt 0.074 mol / L sodium dihydrogen perphosphate (NaH2P02.H2〇) 0.34 Molar / L pH 6

Temperature 65 ° C 4b. Copper sulfate (CuS04 · 5h2〇) 0.04 moles / litre N · (hydroxyalkyl) _ethylenediamine triacetic acid trisodium salt 0.05 moles / litre sodium dihydrogen phosphate ( (NaH2P02. Η2〇) 0.34 mol / L acid 絵 · value $ temperature 68. (: In addition to the plating baths mentioned here, other plating bath types, or other types of plating baths can also be used to plate other metals, as long as they are acidic or neutral. In other words, the acid-base value is below 8 'and mainly between 2 and 7. The currentless metallization bath should have a temperature as low as possible and / or a deposition as high as possible Speed, so that it can further improve the adhesion of its metal plating layer. On its second metal layer, you can also use a non-current or electrolytic method to plate other metal layers by a metallization tank. If Its second metal layer is already thick enough to make it non-permeable. 'The metal layer above it can also use an alkaline metallization tank. The paper size applies Chinese National Standard (CNS) Α4 Specifications (210X297mm) -24- (Please read the notes on the back before filling in this page) Order 403793 A7 _ B7 V. Invention description (21.) ~-to make. And this can basically be used all The metal used to bond It can use general electroless and electrolytic plating tanks. For example, the metallization can be carried out by the current-spreading method or the electrolytic method. The substrate will be in contact with the water-based treatment tank. However, we can also send it to a so-called horizontal processing device. Among them, its processing liquid is sent to the substrate by waves. The invention is described in the following embodiments:

In all the examples, the following conditions were followed: reactor type ... Parallel plate type reactor, high-frequency voltage was applied to the substrate electrode plate, frequency: 13.56MΗζ, substrate temperature: 35 ° C Example 1 ( Coating on Kapton Η-film): 1. Use Glow Discharge to pre-treat: Plant 1 body. Oxygen pressure: 25 Ρά, Airflow: 100 standard cubic centimeters / minute, Power density: 0.8 W / cm2. Processing time : 90 seconds, 2. Palladium plating by glow discharge method: Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Metal organic compounds: π- dilute propyl-π · Cyclopentadienyl-palladium- (II), gas: Ar / 02 or mixed at 3: 1 (volume ratio), pressure: 10Pa, airflow: 25 standard cubic centimeters / minute, power density · 0.5 W / square Centimeter evaporation temperature: 45. (: This paper size applies to the Chinese National Standard (CNS) A4 specification (21〇'〆297mm) -25- A7 B7 Wu 7 Yi Wei ^ ¾.) ~~ u will have Chronic milligrams (Δ1.4 millimoles) of gold financial compounds will evaporate and be directed to the reaction It will go inside the reactor. And it will have a total of 60 standard = cm of oxygen will be consumed in the argon / oxygen mixture. And = in his test, 240 standard cubic cm of oxygen will be consumed. ^ In both cases, 'we can get domain layers that are completely free of carbon. Assume that the ligands of the metal organic compounds are oxidized to oxygen by the oxygen element ^, and in water', in this case, we need to Move fresh cubic centimeters of gas. To make the wire, there are different processes to choose from: Example 2 (ascending technology): 1 · On a perforated κΑΡΤΝ Ε-film, cover with a layer of liquid photoresist The agent was exposed, developed in a Na2co3 solution with a concentration of 100% by weight, and 2. processed by the glow discharge method in advance: gas: oxygen pressure: 25Pa, air flow: 100 standard cubic centimeters / minute, Power density: 0.8 W / cm² Processing time: 90 seconds, 3. Palladium plating by glow discharge method: Metal organic compound: π-allyl-π-cyclofluoradienyl-palladium- (II), Gas: Ar / 02 or N2 / 02, respectively mixed with 3: 1 ' Pressure: 10Pa, Airflow: 25 standard cubic centimeters / minute, this paper is suitable for China National Standards (CNS) Α4 · (210X297 mm) -26- (Please read the precautions on the back before filling this page)

, I1T Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 403793 V. Description of the invention (23.) Power density: 0.5 W / cm² Evaporation temperature: 45. (:, Processing time: 10-15 minutes, 4. if necessary, in a plating bath with sacrificial acid as a reducing agent, electroless plating of palladium: temperature: 70. (:, pH value: 6.0, processing time: 5-8 minutes, 5. Remove the light army with acetone, 6. Like the method in step 4 of the process, use a non-current method to bond Iε to the desired bond thickness to make the wire. The advantage of the method is that in the place where the wire is not formed, it will only be covered by the metal used to make the drilling mask ', and it will still be removed afterwards. The metal used to make the wire is not It will be plated on these locations through the method of glow discharge cracking organic compounds of volatile metals. Therefore, at these locations, metal contamination will not be formed on the substrate surface, and the insulation resistance between the wires becomes special. The base metal layer on the mask area must be selected very thin, such as about 0 1 μπ1, so that it can be easily removed with the mask placed under it, in other words, there is no one Where there will be polymers The film remains on the surface of the substrate. When removing the polymer film, a general chemical solution is used. Example 3 (completely superimposed technology): This paper size applies the Chinese National Standard (CNS) A4 specification (210X297) Public address) -27- (Please read the precautions on the back before filling out this page) Order the printed oxygen of the Shellfish Consumer Cooperative of the Central Government of the Ministry of Economic Affairs _ 403793 A7 ----------- £ 7 ______ V. Description of the invention (24 ·) 1. Glow discharge method is used to pre-treat a piece of drilled UPILEX S, film: gas: oxygen pressure: 25Pa, air flow: 100 standard cubic centimeters / minute, power density: 0.8W / square Cm processing time: 90 seconds, 2. plating by glow discharge method | bar: metal organic compound: π_ 晞 propyl_π_cyclopentadienyl-palladium- (η), gas: Αγ / 〇2 or Ν2 / 〇2, respectively, 'mixed at 3: 1, pressure: 10Pa, delay. 25 standard cubic centimeters / minute, power density: 0.5 W / cm2 evaporation temperature: 45. (:, processing time: 10-15 Minutes, 3. Cover the film with a dry photoresist film, expose it, and Concentration of Na2C03 solution to develop, 4 · In a currentless manner, from a plating tank with formic acid as a reducing agent, 'palladium is completely superimposed between the channels of the photoresist: Temperature: 70. (:, acid Alkali value: 6.0, processing time: depending on the thickness of the desired coating, 5. Remove the photomask with acetone, 6. Use diluted hno3 / hci solution to separate and corrode. This paper size applies to China Standard (CNS) A4 (210X297mm) -28- -In ms mmf nmmmmf km n I in I kptu—-aJ r .- / {Please read the note on the back 闲 ιρ before filling this page) Central Ministry of Economic Affairs Standard Bureau employee consumer cooperative seal «. A7 --- 411379¾_b7 V. ^ If the base metal layer has a sufficiently large conductivity, it can be electroplated between the channels of its photoresist Its second metal layer. Example 4 (subtraction technology / planar coating): 1 · Pre-processed with glow discharge method—pre-existing drilled holes · Thin film: Gas: Oxygen pressure: 25Pa, Air flow: 100 standard cubic centimeters / minute, Power density: 0.8 W / cm² Processing time: 90 seconds, 2, plating by glow discharge method: Metal organic compound: π-allyl-π-cyclopentadienyl · palladium (Π), Gas: Αγ / 02 Or N2 / 〇2, respectively mixed at 3: 1, pressure: 10Pa, air flow: 25 standard cubic centimeters / minute, power density: 0.5W / cm2 evaporation temperature: 45. (:, Processing time: 10-15 minutes, 3. Nickel / boron is electrolessly plated from a weakly acidic nickel / boron plating bath using dimethylamine boron as a reducing agent: Temperature: 40. ( :, Processing time: 2 minutes, 4. Copper plating by electrolytic method in a copper sulfate plating tank: This paper size is applicable to China National Standard (CNS) A4 (210X297) and -29- (Please read first Note on the back, please fill in this page again.) Order the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperation, Du printed 403793 V. Description of Invention (26.)

Cupracid BL (Fa. Atotech Deutschland GmbH, Berlin, DE) Current density: 2 amps / square inch, Plating thickness: 25 μm, 5 · Cover the film with a dry photoresist film, expose it, and use 1% concentration Na2C03 solution to develop, 6 · Etch away the copper and nickel / boron plating: Etchant: CuCh / HCl, add 120 g / L copper to saturation, 1.5 weight percent HC1, add NaCl to saturation, 40 〇C, 7. Etch its palladium metal layer: Etching solution: 1 part concentrated nitric acid, 3 parts concentrated hydrochloric acid, 4 parts of water, room temperature, processing time: 15 seconds, 8. acetone to dry the photoresist film Remove. Example 5 (Semi-stack technology 'Pattern plating method using nickel / boron or copper plating as the second metal layer): 1. A glow-discharge method is used to pre-treat a piece of drilled polyethylene gas : Oxygen pressure: 25Pa, airflow: 100 standard cubic centimeters / minute, power density: 0.8 watts / square centimeter, processing time: 90 seconds, this paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -30- I HH I — ^ 1.-.-—II — ^ 1. ^ Ϋ I. Shiyi ^^ 1-------1-1 (Please read the notes on the back before filling this page) Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 403793 tl 丨 B7 Five 'Invention Description (27.) 2. Palladium plating by glow discharge method: Metal organic compound: π-allyl-π-cyclopentadienyl-palladium_ (Π), gas: Αγ / 〇2 or N2 / 〇2, respectively mixed at 3: 1, pressure: lOPa, air flow: 25 standard cubic centimeters / minute, power density: 0.5 W / cm2, evaporation temperature: 45 ° C, processing time: 10-15 minutes, 3. a keyway with dimethylamine rot as a reducing agent, no current method Plated with nickel / boron: Temperature: 40. (:, Processing time: 2 minutes, change: from a weakly acidic or neutral non-current copper tank, using hypophosphite as a reducing agent to copper, 4 · dry film to cover the film, and Expose and develop with a Na2C03 solution with a percentage concentration. 5- Use electrolytic copper plating to plate its wire structure (plating thickness: 25μηι) 6. Plate a metal photoresist layer (such as tin), 7. Etch away the copper and nickel / boron plating: Etchant. CuCb / HC Add 120g / L of copper to saturation, ^ $ weight percent of HC1, add NaCl to saturation, 40oC, 8. Palladium The metal layer is corroded: ΐThe paper is recognized as applicable to the Chinese National Standard f CNS) Α4 · (2 丨 Gx297 public envy) ---- --------- Installation— (Please read the precautions on the back before filling in this Page) Order-31 403793 V. Description of the invention (28.) Etching solution: 1 part concentrated nitric acid, 3 parts concentrated hydrochloric acid, 4 parts water, room temperature, processing time: 15 seconds, 9. Use acetone to dry the photoresist The film is removed. In the previous example, 'If the oxidizing mixed gas in process step 2' is replaced only by an inert gas, such as pure nitrogen or pure argon, but not oxygen ', when it is plated by glow discharge method At that time, a carbon-containing metal layer will form, but its amount is still small, depending on the metal organic compound used. In addition, the coating on this side will also have a relatively small catalyst activity, and its adhesion to the surface of the substrate is not sufficient to counteract the process steps of verification. In Examples 2 to 5, a metal layer having good adhesion was obtained without exception. After being heat-treated, such as a welding process, or when it is treated with an alkaline aqueous solution, such as a developing solution or a stripping solution for a photoresist film, or after it is processed, it can still maintain it at Adhesion on the surface of polyimide boards. Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ mv i ^ nm 1 ^ 19 Ai ^ —9 ^ mt 1 nn ϋ ^ — m Βϋκ In— 4, " (Please read the notes on the back before filling in this Page) The adhesion of the metal layer contained on the surface of the substrate can be improved by heat treatment (such as annealing at 120 ° C for one hour) after the metal layer is electrolessly or electrolytically plated. In contrast, as in Example 5 (semi-superimposed technology / pattern plating method), if it uses a non-current alkaline copper plating bath instead of an acidic non-current copper plating bath, it goes through its plating process and 150 After the annealing treatment of c, it can still get a good copper plating layer on the polyimide plate. If this piece of polyimide film with steel wire structure is dipped into this paper size, use China National Standard (CNS) A4 (210X297 mm) • 32- 403793 A7 _ B7 V. Description of the invention (29. )-If it is a Lai Yingye towel, its riding performance will be reduced to a very small value (for example, from 1.2N / mm to 0.4N / mm in the peel test). In the previous embodiment, we can also use other inert gases, such as neon, instead of argon, and they will have the same experimental results. A polydonimide film composed of a film and having a wire formed thereon according to the method of the present invention can be bonded to each other and stacked by a suitable method. A two-sided or four-layer circuit can also be glued or stacked on any rigid base, such as a ceramic or FR4 flat board (for example, a circuit board can also be used), or a silicon base. We can also use two, four or more multilayer circuits made by the method of the present invention to use an uncoated polyimide intermediate layer to bond them together, and then depending on the situation, this semi-finished product can be Mechanical drilling and traditional wet chemical methods to connect them with each other. The wires on each layer of the wire plane will pass through the walls of this hole, which have been chemically metalized, in a conventional manner after their stacks have been drilled through and are energized to each other. U-IH 11-jm · —mn-...... ......... j- — ^ ϋ 1 0 (Please read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Beigong Consumer Cooperative Co., Ltd. printed this paper wave scale free use of China's impoverished family car (CNS) size 8 (210X297 mm) -33-

Claims (1)

403793 Patent application scope Examination application patent application scope Zheng Zheng | 1.-A method for making a metal plating layer, the side of which is to coat a polyimide plate with a metal layer with sufficient adhesion to resist alkaline aqueous solution, especially As the manufacturing of the finest wire structure, it basically has the following process steps: a- in a mixed gas environment containing an inert gas and an oxygen-containing compound, 'a glow discharge is used to crack the volatile metal compounds of this metal Method 'is to coat the surface of the polyimide board with a first metal layer containing little carbon and oxygen, so that it can be made active when the second metal layer is subsequently formed by the galvanic method. , And its inert gas includes groups including inert gas and nitrogen, and oxygen-containing compounds include groups including oxygen and nitrogen dioxide, and in this mixed gas, part of the pressure of the inert gas and The partial pressure to partial pressure ratio of the oxygen compound is selected in such a way that it forms a layer that is active against the second metal layer that is subsequently formed Metal layer, printed by Shelley Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs, b- Above the first metal layer, the second metal is electrolessly plated from an acidic or neutralized metallization plating tank Floor. 2. The method according to item 1 of the scope of the patent application, characterized in that in the mixed gas, the partial pressure ratio of its oxygen-containing compound to its inert gas is a value between 2: 1 and 1: 8 , And the best is to adjust between ^ and 丨: bucket. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -34- 403793 Patent application scope Examination application patent application scope Zheng Zheng | 1.-A method for making a metal plating layer, the side of which is to coat a polyimide plate with a metal layer with sufficient adhesion to resist alkaline aqueous solution, especially As the manufacturing of the finest wire structure, it basically has the following process steps: a- in a mixed gas environment containing an inert gas and an oxygen-containing compound, 'a glow discharge is used to crack the volatile metal compounds of this metal Method 'is to coat the surface of the polyimide board with a first metal layer containing little carbon and oxygen, so that it can be made active when the second metal layer is subsequently formed by the galvanic method. , And its inert gas includes groups including inert gas and nitrogen, and oxygen-containing compounds include groups including oxygen and nitrogen dioxide, and in this mixed gas, part of the pressure of the inert gas and The partial pressure to partial pressure ratio of the oxygen compound is selected in such a way that it forms a layer that is active against the second metal layer that is subsequently formed Metal layer, printed by Shelley Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs, b- Above the first metal layer, the second metal is electrolessly plated from an acidic or neutralized metallization plating tank Floor. 2. The method according to item 1 of the scope of the patent application, characterized in that in the mixed gas, the partial pressure ratio of its oxygen-containing compound to its inert gas is a value between 2: 1 and 1: 8 , And the best is to adjust between ^ and 丨: bucket. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -34- A8B8C8D8 403793 VI. Application scope of patent 3. According to the method described in item 1 of the scope of patent application, it is characterized by its mixed gas The value of miscellaneous force is best adjusted between iPa and 50pa. 4. The method according to item 1 of the scope of patent application, wherein the volatile metal compound is a metal compound. 5. The method according to item 1 of the scope of patent application, characterized in that its first metal layer will be plated to a thickness of 0.01 to 0.1 m. 6. The method according to item 1 of the patent application park, characterized in that, in the electroless plating method, the pH value of the metallization tank should be adjusted between 2 and 8, and mainly between 2 and 7. between. 7. The method according to item 1 of the scope of patent application, characterized in that, in the currentless metallization method, nickel, copper, cobalt, palladium or an alloy plating bath of these metals is used. 8. The method according to item 1 of the scope of patent application, characterized in that the second metal layer is electrolessly plated with a nickel / boron alloy layer or a nickel / dish alloy layer, and its _ content Between 3 and 5 weight percent, or a palladium metal layer. 9. A method for manufacturing a circuit carrier, comprising a non-conductive substrate having a polyimide surface, a conductor having a width and a pitch of substantially 100 // m or less, and a diameter substantially of 100. Drilling holes below / Zm can be manufactured using the following process steps:-adding a metal layer on at least one substrate surface,-using photomask technology to structure its metal layer,-using true 2 etching Technology, drill holes in the base, remove the metal widely, and the paper size applies the Chinese National Standard (CNS) A4 (210 X 297 public love) -35 -mllllllll ·! ^ — — — — — — ^ »— — — — 1—. B, V < Please read the notes on the back before filling out this page > Printed by Employee Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 403793 A8B8C8D8 6. Application scope Mixed gas with oxidizing capacity, the gas contains oxygen-containing compounds, the compounds containing oxygen and nitrogen groups, the surface and the wall of the pores are treated in advance by the glow discharge method,- A method of plating a metal layer a-In a mixed gas environment containing an inert gas and an oxygen-containing compound, the method of glow discharge cracking volatile metal compounds of this metal is used to 'plating the surface of the polyimide board' The previous layer of the first metal layer with low carbon and oxygen content, so that when the second metal layer is formed by the currentless method, it can be made active ', and its inert gas contains an inert gas and nitrogen in the The internal group 'and the oxygen-containing compound includes the group including oxygen and nitrogen dioxide' and in this mixture, the partial pressure ratio of the partial pressure of the inert gas to the partial pressure of the oxygen-containing compound is selected , It is to make it form a metal layer which is active to the second metal layer formed subsequently, b- on top of the first metal layer, from an acidic or neutralized metallization bath, The second metal layer is electrolessly plated, and-using photomask technology, the metal layers are structured. < Please read the note on the back before filling out this page > ----—! | Order --- I ----- Xiang-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives This paper is applicable to China Standard (CNS) A4 specification (21G X 297 mm) -36-