CN1368904A - Method of forming thin metal layer on insulating substrate - Google Patents

Method of forming thin metal layer on insulating substrate Download PDF

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Publication number
CN1368904A
CN1368904A CN00811496A CN00811496A CN1368904A CN 1368904 A CN1368904 A CN 1368904A CN 00811496 A CN00811496 A CN 00811496A CN 00811496 A CN00811496 A CN 00811496A CN 1368904 A CN1368904 A CN 1368904A
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China
Prior art keywords
substrate
metal
deposit
conductive layer
coating
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Pending
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CN00811496A
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Chinese (zh)
Inventor
理查德·W·卡彭特
小爱德华·J·里尔登
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SIPOREI CORP
Rohm and Haas Electronic Materials LLC
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SIPOREI CORP
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Publication of CN1368904A publication Critical patent/CN1368904A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/453—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45519—Inert gas curtains
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45561—Gas plumbing upstream of the reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/20—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0092—Metallizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/02—Noble metals
    • B32B2311/06—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/22—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2363/00—Epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H05K1/167—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed resistors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Vapour Deposition (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Insulated Metal Substrates For Printed Circuits (AREA)

Abstract

The invention is directed to the formation of a very thin, uniform metal layer (306) on a resin substrate (307) such as a copper layer on an epoxy-based substrate. Such copper/resin laminates (306, 307) are useful, for example, as blanks for forming printed circuitry.

Description

On insulated substrate, form the method for thin metal layer
The present invention relates on resin substrate, form extremely thin even metal level, for example on the epoxy radicals substrate, form copper coating.For example this copper/resin lamination can be used as the blank that forms printed circuit.
Background of invention
Two kinds of universal methods that form printed circuit board (PCB) are " printing etching " method and " graphic plating " method.
In " printing etching " method, under Gao Re and the high pressure copper foil layer is being laminated on the two sides of glass fibre/epoxy prepreg (uncured), to form the printed circuit board (PCB) blank, this blank all has copper coating on the two sides of hard insulating barrier.Copper the most normally thickness is 1 ounce of copper of 1.2mils (30 microns).On blank, make through hole and blind hole.Plant in the through hole palladium is arranged.Electroplate the entire circuit plate with copper then, so that provide electrical connection by through hole.The thickness that this copper is electroplated reaches 1.2mils usually, makes the total copper thickness that is positioned on the circuit board two sides reach 2.4mils (60 microns).On the two sides of circuit board, apply photoresist, and make its exposure, development.For example utilize the copper chloride etching copper, peel off resist layer then.
In " graphic plating " method, form circuit board by " printing and etching " method.Drill through hole obstructed and that connect.Apply photoresist, and, develop then its exposure.The through hole kind has palladium.Copper is deposited on the circuit trace of exposure and passes through hole.To be electroplated onto the copper circuit track and the through hole of exposure as the metal of resist layer then, these resist layer metals are tin, tin/lead or gold for example.Peel off resist layer.Etching circuit board never is subjected to those zones of plated resist metal coating to remove copper then.In addition, the gross thickness of circuit trace (not including the plated metal resist layer) is about 1.2mils (30 microns) usually.
Printing etching and graphic plating method all are used to make live width down to the wide fine rule printed circuit board (PCB) of 2mils (50 microns).The advantage of printing lithographic method is that it can produce the high control of line preferably.The graphic plating method can a little easily be made little live width circuit.These two kinds of methods all will have benefited from the circuit board blank by the inventive method manufacturing.
Because printed circuit becomes more complicated, and because therefore the miniaturization requirement that improves constantly always exists the requirement of making the thinner printed circuit of resolution.To a restriction of printed circuit resolution copper coating (one or more layers) thickness of the printed circuit board (PCB) blank that is etched; The metal level that is etched is thin more, and the resolution that may reach is high approximately.In the copper etching process, copper not only dissolves towards glass fibre/epoxy insulation base material downwards, and also is that so lateral etching has reduced the resolution of etching track gradually in the horizontal.
Suppose the size that provides above, the etching energy in the printing lithographic method penetrates the copper coating of 2.4mils (60 microns); Etching energy in the graphic plating method penetrates the copper coating of 1.2mil (30 microns).The present invention attempts fully to reduce these thickness, and thinner printed circuit resolution is provided thus.
The present invention relates to provide a kind of circuit board blank, this blank has continuous, non-porous extremely thin copper layer on glass fibre/epoxy plate, and promptly its thickness is greatly between 0.5 to 3 micron.Copper layer thickness on the printed circuit board (PCB) blank only needs the sufficient formation through hole metapedes that can carry to get final product with the electric current of effectively electroplating.Be this purpose, find to resemble copper foot thin 0.5 micron the electric current that provides effective electroplating operations required can be provided.Compare with the copper electro-deposition additional thickness that the thick paper tinsel layer of traditional 1.2mil or 1.2mil are thick, the copper coating thickness of 0.5 to 3 micrometer range can be ignored.
In the printing lithographic method, begin to electroplate the annex copper of 1.2mil from the negligible blank coating of thickness, the copper that is etched is thick to be 1.2-1.3mils, rather than 2.4mils.
Adopt size discussed above, in graphic plating method, the paper tinsel of an etching circuit board blank initial protion.0.5 the paper tinsel layer between 3 microns by etching rapidly, can reduce mainly the circuit trace undercutting that the copper by electro-deposition constitutes thus substantially.
Therefore, when the initial copper coating of circuit board blank was extremely thin, printing lithographic method or graphic plating method were useful.
Chemical vapor deposition (CVD) is known for the deposit coating, and it can realized with the gas reaction material that produces solid deposits or coating on this surface near the substrate surface or in reaction on the substrate surface by providing.Described the new development of CVD method in No. the 5652021st, United States Patent (USP), it is called as combustion chemistry vapor deposition or CCVD, and is by reference that the document is incorporated at this.Reactant in this method is by dissolving or be suspended in the liquid and carry, and it can be a fuel, utilize as the oxidizing gas of jet fuel with its from the nozzle ejection to the reaction zone in.The mixture that ejects both can be lighted generation flame, perhaps was directed in the flame, simultaneously substrate was remained near the flame end.These reactants both can gasify before arriving flame and also can gasify in flame, produced deposition film thus on substrate.This patent has also been described a large amount of existing CVD methods, comprises the method that some carry gaseous states or gasification reactant, and some spray or the method for atomized soln and some are for carrying the method that can react pressed powder for utilizing.This patent has also been described the many paint-on techniques that can select, and these technology comprise: spray the Pintsch process technology, wherein solution is injected into and is subjected on the hot substrate, forms coating in this solution pyrolysis; And a kind of like this technology, wherein solid cladding material fusion or gasification in flame, plasma or other heater, and by spilling or be agglomerated to and form coating on the substrate.
The technology instruction that No. the 5652021st, United States Patent (USP) can be used for making the shallow layer of zero-valent metal, if be particularly suitable for metal sludge proof situation, platinum can be used as the example that is easy to by CCVD method metals deposited.More active metal, copper for example, it can utilize the method for this patent to carry out deposit in the reduction part of flame.Yet, because therefore the oxidisability of flame is difficult to control.
In the sequence number of on August 2nd, 1996 application is 08/691853 U.S. Patent application, the CCVD further improvements in methods have been described, by reference that it is incorporated at this.This application has been described a kind of CCVD method, wherein the coating precursor reactant is arranged in the liquid feed streamed mixture or solution, for liquid feed stream solution, it is forced near critical pressure before by nozzle or joint valve, and is heated to the supercritical temperature near it.When fluid left nozzle enter the zone (at this precursor can deposit be coating both, also can revert back to trickle powder) that coating precursor reacts on substrate, the nearly critical condition of liquid caused feed streams to obtain extraordinary atomizing or gasification.
Described a kind of improvement of CCVD method in No. the 09/067975th, the U.S. Patent application, this method can promote various zeroth orders, the deposit of active metal relatively, and the instruction of this application is incorporated with it by reference at this.Device and technology in No. the 09/067975th, the U.S. Patent application relate at this so-called " vapor deposition of controlled atmosphere combustion chemistry " or CACCVD.This method helps the deposit such as the zero-valent state active metal of copper, nickel.
In U.S. Patent application the 09/069427th, 09/069679 and 09/198285, found insulation and the resistance material example made by CCVD and/or CACCVD, this by reference with them the instruction of each incorporated.
CCVD and/the CACCVD technology is used in extremely thin, uniform, the continuous metal coating of deposit on the substrate.Produced thickness already and be 0.1 micron continuous metal film.0.1 the metallic film of micron thickness can be used among the present invention; Yet, if the electro-deposition that carries out the circuit operation with suitable speed need make the metals deposited coating layer thickness be at least about 0.5 micron usually.If CCVD and/or CACCVD technology can be used in the metal level (one or more layers) that forms the circuit board blank, just can obtain higher resolution.
Can be able to will approach metal coating by CCVD and/or CACCVD with imagining and directly be deposited on the insulating materials that has solidified, these insulating materials have for example been filled the epoxy resin board of glass fibre.Yet,, can not get CCVD and CACCVD device these coatings being coated to the resin plate field at present for circuit board manufacturer.In addition, CCVD and CACCVD method need point-device control, can not guarantee the quality and the uniformity of this field deposit at present.Therefore, preferably there are experience coating personnel to handle these methods by the present technique field.The present invention relates to thin metal layer is transferred to material and method on the insulating materials that forms printed circuit board (PCB).
Overall advantage of the present invention is to make blank for the printed circuit board (PCB) with extremely thin metal coating, and promptly metal coating thickness is about 0.1 to 3 micron, preferably is about 0.5 to 2 micron.
Summary of the invention
According to the present invention, conducting metal is deposited on the transfer base substrate of flat-satin, the thickness of this metal illuvium reaches 0.1 to 3 micron approximately, preferably approximately between 0.5 to 2 micron.Metal is generally copper, but also can be other conducting metal, for example nickel, platinum, silver, gold, tin, zinc etc.Metal also can be the alloy of two or more zero-valent metals that are deposited, the metal level of the another kind of element that perhaps mixed (or multiple element).The zero-valent metal that is deposited and the cohesive force of transfer base substrate must be enough to make deposited metal and transfer base substrate to keep bond state in transportation, processing procedure, and wherein said processing procedure generally includes the expansion of metal/substrate lamination.Yet the cohesive force between metals deposited coating and the transfer base substrate must be enough low, with convenient metal stacking to metal have big cohesive force such as on the material of prepreg the time, transfer base substrate can be peeled off, and can not cause damage to film.In this, aluminium foil is particularly preferred substrate, and reasoning is that to be formed in the cohesive force of aluminium and the deposited metal on surface formation very weak.Polymer thin films such as polyimides also is suitable as transfer base substrate, as long as film can hold out against deposition conditions, temperature particularly, and as long as the cohesive force between divert film and the metals deposited layer is enough low, so that back deposited metal and film can be separated from.After metal level is deposited on the substrate, the side facing of metal level is laminated on the uncured or partly solidified insulating resin, for example filled the epoxy resin of glass fibre.(can be with two such structural laminated to the opposite flank of uncured or local solidification resin bed, to form the two sides blank.) the heating resin bed, until the resin bed cure hard, and bonding with metals deposited layer (one or more layers) securely.At this moment, peel off the deposit substrate, stay thin, continuously and evenly and with the resin bonded metal level that has solidified, and be formed for making the blank of high-resolution printed circuit board (PCB).
Transfer method of the present invention also can be used for forming the thin layer passive device, particularly forms capacitor and resistor.
Brief description of drawings
Fig. 1 is the partial cutaway schematic by the device of controlled atmosphere combustion chemistry vapor deposition (CACCVD) applying coating;
Fig. 2 is the part section close-up perspective view of a part of dispense tip of using in Fig. 1 device;
Fig. 3 is the cutaway view of deposit substrate, on this substrate deposit metal coating;
Fig. 4 is the cutaway view that is layered in the two-layer Fig. 3 structure on the non-conductive resin;
Fig. 5 is the cutaway view that the deposit substrate is removed in expression;
Fig. 6 A-E represents by form the process of thin film resistor according to transfer method of the present invention;
Fig. 7 A-E represents by form the process of thin film capacitor according to transfer method of the present invention.
Some detailed description of preferred embodiment
For some special applications, printed circuit board (PCB) can be made of the noble metal such as silver, gold or platinum.In order to form these metal levels, be the traditional C CVD technology of utilizing instruction in No. the 5652021st, the U.S. Patent application of for example quoting and the U.S. Patent application of quoting No. 08/691853 in the above in the above easily.Yet the most frequently used copper, nickel, tin or other oxidizable metal not too commonly used also can be used as the selection of making printed circuit board (PCB).Preferably utilize as No. the 09/067975th, above-cited U.S. Patent application in these metals of CACCVD deposit of describing.
U.S. Patent application provides the apparatus and method that are used for chemical vapor deposition No. 09/067975, wherein carefully control and be isolated into the feed that forms coating and carry, and make the gas that goes out from the controlled atmosphere zone migration pass through barrier zones, at this barrier zones gas to flow out from described controlled atmosphere zone, by set up the atmosphere in the controlled atmosphere zone with upper type greater than 50 inches of per minutes, the average speed that is preferably more than 100 inches of per minutes.The controlled atmosphere zone has comprised reaction zone and deposit district, and coating precursor reacts at reaction zone, and in the deposit district, the product of coating precursor is the deposit coating on substrate.Gas passes flowing fast of barrier zones and has got rid of the gas in the ambient air basically toward the migration of deposit district, and in this deposit district, the gas in the ambient air can react with coating, the material that derives coating or substrate.
Can realize careful control by carry the coating precursor that fixed proportion is arranged in liquid medium to the material that forms coating.It is atomized when liquid medium is transported to reaction zone, is gasified at this liquid medium, and coating precursor reacts and forms the coating precursor reacted.What can select is that coating precursor (one or more) can be carried in the gas mode, also can carry in pure coating precursor mode or in the mixture mode in the carrier gas.The coating precursor that has reacted can be made up of part, whole and/or few reacted constituent, and they are mobile to substrate.The coating precursor that has reacted contacts with substrate surface in the deposit district, and on substrate surface the deposit coating.Can mobile inert gas heavy curtain be set around the reaction zone, so that protect reaction coating material/ion beam in this zone not to be subjected to the material that installs or the pollution of ambient air composition on every side.
The reaction needed of the gasification of liquid medium and coating gas input energy in the reaction zone.According to the respond of coating material and substrate, can utilize the various energy that required energy is provided, for example burning, resistance heated, induction heating, heating using microwave, RF heating, hot surface heating, LASER HEATING and/or mixed with long-range heated gas.
(CACCVD) technology provides the energy input of fair speed, and it can carry out high-speed coating deposit.Under some preferable case, fluid media (medium) and/or the secondary air that is used for the atomizing fluids medium can be fuel, and they are also as the energy.Particularly importantly CACCVD under atmospheric pressure or near atmospheric pressure can form high-quality attachment film deposit, avoids the needs to complicated vacuum or similar isolated cover thus.Owing to these reasons, in many cases, can be in the original place that substrate is set or " on the spot " apply the film coating of CACCVD.
Combustion chemistry vapor deposition (CCVD) is not suitable for these coatings applications, and wherein, coating and/or substrate need oxygen-free environment.For such application, be fit to adopt the embodiment of CACCVD method, this method adopts the energy that do not burn, and these energy are as infrared or LASER Light Source, for example hot gas, heat pipe, radiant energy, microwave and energization photon.In using, these it is highly important that all liquids and gases that are provided to reaction and deposit district are oxygen-free all.Coating precursor can the supply of solution form or is provided with the form of suspension in the liquid.Liquefied ammonia and propane are suitable for deposition of nitride and carbide respectively.Can be under atmospheric pressure or be higher than that to utilize these incombustible energy in the controlled atmosphere chemistry gas-phase precipitation system that forms deposit under the atmospheric pressure conditions are CACCVD particularly advantageous characteristics.Utilizing the energy that do not burn in the CVD system is another distinctive favourable characteristics of CACCVD, and it discharges by nozzle or similar joint valve under nearly critical-temperature and pressure condition fast by making the liquid coating precursor, and this provides the atomizing that strengthens.
Can be because the CACCVD method and apparatus provides relative to the controlled atmosphere zone that substrate moves, so it can make coating on than the big substrate in controlled atmosphere zone, this coating is bigger than the coating that obtains by traditional vacuum chamber deposition technology thus.
The further advantage of CACCVD system is that it need not to provide just energy coated substrate of additional-energy to substrate.Therefore, this system can not tolerate the great majority substrate of the high temperature that gives of systems formerly coated with preceding.For example, nickel coating can be arranged on the polyimides lamination substrate, and can not cause base plate deformation.In the past, the atmospheric pressure deposition technology is owing to the strong affinity of nickel to oxygen, therefore can not realize the chemical vapor deposition of metallic nickel, and to such as the application of vacuum of polyimides lamination substrate owing to can cause the getter action of water and organic material, therefore it also has problems, and its size is tended to instability when this substrate is subjected to heat and vacuum action.
Controlled atmosphere combustion chemistry vapor deposition (CACCVD) device as describing in No. the 09/067975th, the above-cited U.S. Patent application has been described in Fig. 1 and 2.In the formation district 14 that comprises stirring or holding tank 16, coating precursor 10 is mixed with liquid medium 12.Precursor 10 forms fluids stream with liquid medium 12, is the pressurization of fluid stream with pump 18, and with filter 20 filtrations, is transported to range of atomization 24 by pipeline 22 then, and fluid flows thus Continuous Flow and crosses reaction zone 26, deposit district 28 and barrier zones 30.Reaction zone 26 and deposit district 28 are included in the controlled atmosphere zone.
When flowing to into range of atomization 24, fluid is atomized.Atomizing can be finished by the recognized technology of the streaming flow stream that is used to atomize.In represented device, when fluid stream is discharged, flow direct neighbor on every side or with fluid by directly high speed atomization gas stream being discharged to fluid stream from pipeline 22, can cause atomizing.Atomization air flow is provided by gas cylinder or gas high-pressure air source.In the embodiment shown, utilize high pressure hydrogen (H 2) not only as atomization gas but also act as a fuel.Atomization gas is carried by hydrogen cylinder 32, and it enters pipeline 38 through control valve 34 and flowmeter 36.Pipeline 38 extends to the range of atomization with one heart with pipeline 22; at this two pipelines end hydrogen atomization gas is at a high speed contacted with the fluid stream that flows; the fine grained fluid that fluid stream is atomized into suspend in ambient gas/steam; this fluid flows into reaction zone 26; form reacted coating precursor in this liquid medium evaporation with the coating gas reaction; reaction comprises the ion that coating precursor is resolved into their composition, and this can produce the fluid stream of ion particles or plasma.Fluid stream is led with substrate 40 and is contacted then, thus in deposit district 28 on substrate deposit coating.
When liquid medium/coating precursor stream is discharged from pipeline 22, can be by directly coming atomizing fluids stream to their jet atomization gas.What can select is when liquid stream flows out from pipeline 22, can finish atomizing by go into ultrasonic or similar energy to the liquid conductance.The sequence number of quoting in the above is to have described further preferred atomization technique in No. 08/691853 the patent application, it comprises, in 50 ℃ under the pressure that is higher than its liquidus curve or critical pressure with in its critical-temperature, liquid medium/coating precursor is flowed to joint valve (restriction), for example by having the hollow needle of limited outlet or nozzle, liquid medium/coating precursor enters low-pressure area thus.The quick release of pressure of energized fluid medium/coating precursor produces its meticulous atomizing and gasification.
The gasification of liquid medium and the reaction needed of coating precursor are incited somebody to action very before they leave reaction zone, and macro-energy is input in the fluid stream.The energy input when passing through pipeline 22 and/or enter atomizing and reaction zone, energy takes place.Can finish energy input by various known heating techniques, for example fuel combustion of these technology, resistance heated, microwave or RF heating, induction heating, radiation heating, with fluid stream with the long-range liquid that is heated or gas mixes, for example utilize the photon of laser instrument to heat, carry out heat exchange etc. by hot surface.In described preferred embodiment, during through reaction zone, finish energy input with oxidant with the burning that fluid stream directly contacts by fuel at fluid stream.More intactly described this newer technology in No. the 5652021st, the United States Patent (USP) of quoting in the above, it is called as combustion chemistry vapor deposition (CCVD).In described embodiment, fuel, hydrogen is transported to pipeline 44 from hydrogen cylinder 32 by control valve, flowmeter 42.Oxidant-oxygen is transported to pipeline 52 from oxygen cylinder 46 by control valve 48 and flowmeter 50.Pipeline 52 extends around pipeline 44, and it is concentric with pipeline 44, and pipeline 44 extends around pipeline 22 and 38, and concentric with pipeline 22 and 38.In a single day hydrogen and oxygen discharge from their pipelines separately, produce combustion product with regard to burning, and this product is mixed with liquid medium that atomizes and coating precursor in conversion zone 26, thereby heats and caused the gasification of liquid medium and the reaction of coating precursor.
At least at the slumpability gas screen that is provided with around the reaction zone start-up portion with reacting gas and be arranged in the material that near the device the reaction zone exists and keep apart.To be transported to pipeline 60 from inert gas gas cylinder 54 by control valve 56 and flowmeter 58 such as the inert gas of argon.Pipeline 60 is along pipeline 52 extensions and concentric with pipeline 52.Pipeline 60 extends to beyond the end of other gas piping 22,38,44 and 52, and it extends near substrate, and it defines deposit district 28 with substrate 40 thus, and in this deposit district 28, coating 62 is deposited on the substrate with the shape of cross section of pipeline 60 usually.When inert gas flow was crossed oxygen pipeline 52 terminal, it formed the mobile screen that extends at first around reaction zone, be used to protect reacted constituent wherein not contact with pipeline 60.When inert gas when pipeline 60 advances, inert gas is mixed with the gas/plasma from reaction zone, becomes the part of the fluid stream that enters deposit district 28.
Need incendiary source initially to light hydrogen and oxygen.The Artificial Control igniting or the igniter of separating are enough for many application, yet utilize these devices to need the interim inert gas flow that reduces, up to having formed stable flame front.In some applications, total gas flow rate may be too big, so that can not form independently flame front.So can continuous or semicontinuous igniter of lighting fuel gas in the time of must being provided at fuel gas and entering reaction zone.Pilot flame or spark generator are the representative point burning things which may cause a fire disaster that can adopt.
At depositing region 28, coating precursor deposit coating 62 on substrate 40 of having reacted.The remainder of fluid stream flows through barrier zones 30 from depositing region, and around being discharged to or in the ambient air.Barrier zones 30 is used to protect controlled atmosphere district not to be subjected to the pollution of ambient atmosphere composition.The controlled atmosphere district comprises reaction zone, deposit district and additional space arbitrarily, and by additional space, fluid stream is by 28 backs, deposit district with obtained to lead the way before by barrier zones 30.When fluid flow is crossed barrier zones 30 is this regional property feature at a high speed.Speed reaches at least 50 inches of per minutes when requiring fluid flow to cross barrier zones, has eliminated the controlled atmosphere district basically by ambient atmosphere composition contamination of heavy in most of coating coating procedure.In major part to polluting in the higher coating procedure of sensitivity, for example in the process of making nitride or carbide coating, by requiring fluid stream to reach the speed of 100 inches of per minutes at least, can eliminate the controlled atmosphere district basically by the ambient atmosphere contamination of heavy.
In the device of Fig. 1, at pipeline 60 ends adjacent, a flange 64 and 60 terminal linking to each other of pipeline are arranged with deposit district 28, this flange is from the terminal outwards vertical extension of pipeline 60.Barrier zones 30 is limited by the gap that exists between flange 64 and the substrate 40.Construct flange shape to such an extent that matching surface 66 can be provided, this surface can be launched near substrate surface, provides less gap for the gas discharging that is discharged to from the deposit district the ambient atmosphere thus.The gap that forms between the matching surface 64 of flange and the substrate is enough little, is the required speed of passage between at least a portion flange and the substrate in the barrier zones so that exhaust is reached.For this reason, matching surface 64 shapes of flange 62 are configured to surperficial substantially parallel with substrate 40.In illustrated embodiment, when the surface of substrate 40 was essentially the plane, the matching surface of substrate also was smooth basically.
Contiguous pipeline 60 terminal edge effect, for example high temperature and the residual reaction compositions that take place can expand to the deposit district zone beyond the pipeline 60 terminal dead ahead substrate regions.Flange 64 enough distances that should stretch out from the junction of itself and pipeline 60; to stop the ambient atmos back-mixing that causes owing to (Venturi) effect in the possible texts and pictures to enter the deposit district; and because forenamed edge effect causes deposit district when expansion, the whole zone that can guarantee protection deposit district is not subjected to the influence of the ambient atmos backflow that high speed exhaust " wind " regional between inswept flange and the substrate causes.The flange that extends has guaranteed to comprise that whole controlled atmospheres district in whole expansion deposit district is not contaminated.The diameter of flange should be at least the twice of pipeline 60 internal diameters, preferably, should be 5 times of pipeline 60 internal diameters at least.The internal diameter of pipeline 60 is usually in 10 to 30 millimeters scope, preferably between 12 and 20 millimeters.
In operating process, flange 64 is arranged essentially parallel to the surface of substrate 40, and the distance of it and substrate surface is 1 centimetre or still less.Preferably, the apparent surface of flange and substrate separates 2 to 5 millimeters.On flange, escapement can be set, for example fix or the adjustable pin (not shown) for three, in order to keep suitable distance between accessory flange and the substrate.
Device shown in Fig. 1 is for being particularly advantageous to very big substrate applying coating, perhaps for the inconvenient situation advantageous particularly that will handle in the certain controlled environment such as vacuum chamber or clean room.Shown in the favourable reason of coating technology be: (a) can apply the substrate bigger, and (b) because can under atmospheric pressure and in more convenient " on the spot " place, finish coating than controlled atmosphere district. Concentric tube group 22,38,44,52 and 60 has formed dispense tip 68, and these concentric tubes can provide with less flexible pipe, and they will be small enough to and can carry.Energy is imposed on coating precursor to the heat that is produced by resistance by fuel combustion or by supply and less portable dispense tip matches.By making dispense tip repeatedly cross substrate with scan mode or similar preassigned pattern, or by make for progression provide uniform coating to be provided with the dispense tip array cross substrate, or, can apply very big substrate by scanning dispense tip array.Except realizing the thin film coated to and the workpiece that can not apply too big with cause, this technology can also be coated with the major part of preceding those substrates that need could apply under vacuum condition.Apply by major part, can reach and make economy, particularly when relating to the large-scale production of substrate these substrates.
Device shown in Fig. 1 and 2 also is particularly suitable for producing the coating to oxidation-sensitive, for example most of metal coating.For these coatings are provided, by pipeline 44 transfer the fuels of contiguous atomising liquid media and coating precursor, simultaneously by pipeline 52 delivery of oxidizing agent.Atomization gas of carrying by pipeline 38 and/or the liquid medium of carrying by pipeline 22 can be the materials with fuel value, they can be can with the material of coating precursor reaction, or inert substance.When the coating that produces or coating precursor are oxygen sensitive material, when guaranteeing to be restricted to the oxidant total amount of being supplied less than completing combustion when the reaction zone supplied fuel required amount, realize that stoichiometry less than oxidant keeps reacting and the deposit district in reducing atmosphere.Usually, fuel limitation is excessive, so that any flame zone that restriction produces when residue hot gas mixes with aerial oxygen at last.For example in producing most of oxide coating process, when the coating that is produced and precursor material be oxytolerant or can be because when oxygen occurring and being enhanced, reacting and the deposit district can provide oxidation or neutral atmosphere by stoichiometry or excessive oxidant are provided.In addition, because oxytolerant reagent or goods can pass through interior pipe 44 delivery of oxidizing agent, simultaneously by outer tube 52 transfer the fuels.
The essential foot of carrying by pipeline 60 of inert gas can shield the pipeline inner surface and contact with the reacting gas that produces in the reaction zone, and when other gas of being added with from the discharge of deposit district, inert gas must can provide gas velocity required in the barrier zones enough.
The combustion system of in Fig. 1 and 2, describing, also can realize the energy input by mechanical device.For example, by liquid medium/coating precursor and preheating fluid mixing energy are realized the energy input, these pre-heated flow styles such as temperature surpass 200 ℃ inert gas.Should be understood that, be not to need all pipelines 22,38,44,52 and 60 when realizing the energy input by the method beyond the burning.When the energy input is provided by a kind of non-combustion technology, generally can dispense the cover in pipeline 44 and 52, or two covers dispense all.
Can change the porosity or the density of deposit coating by the distance between change flame and the substrate surface deposit district.Shorten this apart from the increase that can realize coating density, and increase this apart from providing the hole more coating.Shown in the CACCVD technology in, reaction zone usually with the flame coexistence that produces by fuel combustion.Certainly, flame zone and substrate are essential to keep distance enough far away, so that substrate can not be subjected to the damage of the higher temperature that produces near substrate surface very much because of flame zone.When the substrate temperature susceptibility because of a kind of baseplate material and another kind of baseplate material not simultaneously, at least cold 600 ℃ usually of the temperature in the substrate surface deposit district than the highest flame temperature.
When utilizing some non-combustion methods that energy when input is provided, the maximum temperature that occurs in the reaction zone is lower than those temperature that exist during combustion fuel in the reaction zone basically.In some cases, be in the reaction zone or under the situation of the preheating fluid that is mixing with fluid stream before arriving this reaction zone for example, need not to consider that by the distance between change reaction zone and the substrate surface superheated substrate can regulate coating performance in main energy input.In some cases, make reaction zone directly with substrate adjacent become ideal situation apart from what cause than dense coating owing to shortening to greatest extent between reaction zone and the substrate.Therefore, term reaction zone and deposit district can be used for the functional areas of definition device, rather than will define the zone of mutual repulsion, and in some applications promptly, the reaction of coating precursor can occur on the substrate surface in the deposit district.
Fluid stream leave input energy that reaction zone forward direction fluid stream carries out do not need usually to resemble need in other paint-on technique provide energy by heated substrates to the deposit district.In this deposition system, substrate is used as the heat-sink shell of the gas that exists in the cooling deposit district usually, rather than is used to heat this gas.Therefore, the suffered temperature of substrate is lower than substrate basically and need transmitting suffered temperature in the system of energy to the deposit district by substrate.Therefore, the CACCVD painting method can be used for applying the responsive baseplate material of various temperature, and these materials can not utilize and comprise by substrate and applying to the technology that the deposit district transmits heat in the past.In addition, the controlled atmosphere district of extending on the substrate portion that is under the high temperature protects same degree with its protective finish material with substrate, can be used to apply the substrate to the pollutant sensitivity thus, for example to the substrate of oxidation-sensitive.
Fluid media (medium) can be a flammable liquid organic solvent or such as the gas of alkane, alkene or ethanol, or it also can be oxidant or exothermic material, for example nitrogen oxide (N 2O), or it can comprise not flammable or nonflammable material, for example water, carbon dioxide or ammoniacal liquor.
The precursor material that is used for the depositing metal coating can be the organic or inorganic compound, and they can react, comprise cracking or ion reaction, formation can be on substrate the product of deposit coating.Because the heat release of emitting in the reaction zone can reduce other required energy input, the precursor material that therefore heat release cracking or precursor exothermic reaction can take place is specially suitable.Coating precursor can be transported to reaction zone with liquid, gas or part as the solid form of finely-divided.When carrying, it can be mingled with in the carrier gas in the gas mode.Carrier gas can be an inertia, perhaps also can be used as fuel.
When the precursor of metal coating is when providing with liquid form, preferably, make the coating precursor material that exists with fine particulate form in the liquid medium up to 50%.Yet preferably, the coating precursor material can be dissolved in the liquid medium fully.The concentration of coating precursor in liquid medium is usually less than 0.1M, preferably between 0.0005M and 0.05M, with coating precursor be transported to coating precursor material concentration required in those paint-on techniques of coating procedure with gaseous state or vapor state compare, this concentration is rarer relatively.In addition, the metal coating precursor material does not need to resemble in other paint-on technique and need have higher vapor pressure with the precursor material of gaseous state or the conveying of steam attitude.Can use vapour pressure under 300 ℃, to be lower than the precursor of 10 holders.Therefore, can use the precursor material of relative wide region in present technique, many these precursor materials are more cheap than the volatile material that other paint-on technique needs basically.
The precursor of wide region can be used as gas, steam or solution.Preferred use can produce the most cheap precursor of ideal form.Various metals of deposit or nonmetallic appropriate precursors are enumerated following (and not meaning that restriction): Pt acetylacetonate platinum [Pt (CH 3COCHCOCH 3) 2] (in toluene and methanol),
Platinum-(HFAC 2),
Biphenyl-[(Pt (COD) is at toluene-third for (1, the 5-cyclo-octadiene) platinum (II)
In the alkane)
Platinum nitrate (in ammonium hydroxide aqueous solution) Mg magnesium naphthenate, 2 ethyl hexanoic acid magnesium [Ma (OOCCH (C 2H 5) C 4H 9) 2], magnesium naphthenate,
Mg-TMHD, Mg-acac, magnesium nitrate, 2,4-glutaric acid MgSi tetraethoxysilane [Si (OC 2H 5) 4], tetramethylsilane, disilicic acid, silicic acid, P triethyl phosphate [(C 2H 5O) 3PO 4], tricresyl phosphite ethyl ester, tricresyl phosphite phenylester La 2 ethyl hexanoic acid lanthanum [La (OOCCH (C 2H 5) C 4H 9) 3], lanthanum nitrate [La (NO 3) 3],
La-acac, different third lanthana
Three (2,2,6,6-tetramethyl-3,5-heptadione root closes (hepanedionato)
Lanthanum [La (C 11H 19O 2) 3] Cr chromic nitrate [Cr (NO 3) 3], 2 ethyl hexanoic acid chromium [Cr (OOCCH (C 2H 5) C 4H 9) 3],
Chromium sulfate, chromium carbonyl, acetylacetonate chromium (III) Ni nickel nitrate [Ni (NO 3) 2] (in moisture ammonium hydroxide), acetylacetonate nickel,
2 ethyl hexanoic acid nickel, naphthols nickel, dicarbapentaborane nickel Al aluminum nitrate [Al (NO 3) 3], acetylacetonate aluminium [Al (CH 3COCHCOCH 3) 3],
Triethyl aluminum, aluminium-sec-butylate,
The I-aluminium propoxide, 2 ethyl hexanoic acid aluminium Pb 2 ethyl hexanoic acid lead [Pb (OOCCH (C 2H 5) C 4H 9) 2], lead naphthenate, Pb-TMHD,
Plumbi nitras Zr 2 ethyl hexanoic acid zirconium [Zr (OOCCH (C 2H 5) C 4H 9) 4], positive fourth oxygen zirconium,
Zirconium (HFAC 2), zirconium acetylacetonate, zirconium-n-propylate, zirconium nitrate Ba 2 ethyl hexanoic acid barium [Ba (OOCCH (C 2H 5) C 4H 9) 2], barium nitrate, acetylacetonate barium,
Ba-TMHDNb ethyoxyl niobium, four (2,2,6,6-tetraethyl-3,5-heptadione root closes
(hepanedionato)) niobium Ti I-titanium propanolate (IV) [Ti (OCH (CH 3) 2) 4], acetylacetonate titanium (IV),
Two-I-propoxyl group-two-acetylacetonate titanium,
Titanium n-butoxide, 2 ethyl hexanoic acid titanium, two (acetylacetone,2,4-pentanedione) titanium oxide Y 2 ethyl hexanoic acid yttrium [Y (OOCCH (C 2H 5) C 4H 9) 3], yttrium nitrate, I-propoxyl group yttrium,
Aphthenic acids yttrium Sr strontium nitrate [Sr (NO 3) 2], 2 ethyl hexanoic acid strontium, Sr (TMHD) Co cobalt naphthenate, carbonyl cobalt, cobalt nitrate Au chlorination triethyl phosphine gold (I), chlorinated triphenyl base phosphine gold (I) B trimethylborate, B-trimethoxyboroxine K ethyoxyl potassium, tert-butoxy potassium, 2,2,6,6-tetramethyl heptane-3,5-two ketonizes-potassium Na 2,2,6,6-tetramethyl heptane-3,5-two ketonizes-sodium, sodium ethoxide, tert-butoxy sodium Li 2,2,6,6-tetramethyl heptane-3,5-two ketonizes-lithium, the ethyoxyl lithium, tert-butoxy lithium Cu Cu (2 ethyl hexanoic acid) 2, copper nitrate, acetylacetonate copper Pd palladium nitrate (in the aqueous solution of ammonium hydroxide) (NH 4) 2Pd (NO 2) 2, the acetylacetonate palladium,
Six ammonium palladic chloride Ir H 2IrCl 6(in 50% ethanol water), acetylacetonate iridium, carbonyl iridium Ag silver nitrate (in water) silver nitrate, fluoroacetic acid silver, silver acetate, cyclohexane butyric acid silver,
2 ethyl hexanoic acid silver Cd cadmium nitrate (in water), cadmium 2-ethylhexoate Nb 2 ethyl hexanoic acid niobium Mo (NH 4) 6Mo7O 24, Mo (CO) 6, two (acetylacetone,2,4-pentanedione) molybdenum dioxide Fe Fe (NO 3) 39H 2O, acetylacetonate iron Sn SnCl 22H 2O, 2 ethyl hexanoic acid tin, tin-tetra-n-butyl tin, tetramethyl tin In In (NO 3) 3XH 2O, acetylacetonate indium Bi bismuth nitrate, 2 ethyl hexanoic acid bismuth Ru acetylacetonate ruthenium Zn 2 ethyl hexanoic acid zinc, zinc nitrate, zinc acetate W six carbonylation tungsten, tungsten hexafluoride, wolframic acid Ce 2 ethyl hexanoic acid cerium
Although top listed many metals and nonmetally be not suitable for forming conductive layer, conceivable is that some element can be to carry out codeposition than small scale and major metal, to influence electricity, machinery or adhesion property.The precursor that can mix two or more metals comes deposited alloys.
According to the present invention, as shown in Figure 3, deposit thin on transfer base substrate 112, conduction, non-porous continuously and even metal coating 110 shift lamination 114 to form.To the major requirement of transfer base substrate 112 is that the bonding force of it and metal level 110 is enough low, with convenient metal bond to a kind of resin and the bonding force of this resin and this metal than with the bonding force of transfer base substrate 112 when big, substrate 112 can be stripped from.The bonding force of substrate 112 and metal level is preferably between about 1/2lb/in 2With about 2lb/in 2Between.The preferable substrate 112 that is used for cement copper coating 110 according to the present invention is aluminium foils.The bonding force that records copper coating 110 and aluminum foil substrate 112 is 1 to 1.2lb/in 2In addition, substrate must have enough temperature stabilities and tolerate coated conditions, particularly temperature.Transfer base substrate 112 is generally film or paillon foil, and in order to transport and to store, they can curl with the metal level that is deposited, but transfer base substrate 112 must have enough rigidity, so that can support this metal level before metal level adheres on the resin.Typical aluminum foil thickness as transfer base substrate 112 is approximately 50 microns.
Can on transfer base substrate 112, metal level 110 be deposited to the thickness of any needs by CCVD or CACCVD, however according to metal level of the present invention to be deposited to about 0.1 and about 3 microns between, preferably between about 0.5 to 2 micron.Usually be 0.1 to 500 milligram/minute speed metallizing layer with every dispense tip, preferably the speed with 0.5 to the 2.0 milligram/every dispense tip of per minute applies.
In CACCVD, substrate temperature remains on below 600 ℃ usually, preferably remains on below 400 ℃, and when needs were avoided ill-effect to substrate or other parts, substrate will remain on below 200 ℃.When applying the more responsive substrate of temperature, it is that preferably wherein said energy input source is heated fluid, radiation or microwave energy for example that the present invention adopts the embodiment of non-burning capacity input source.By the inertia cooling fluid that will be preferably gas import on the surface away from the deposit district, for example be exposed on the opposing substrates surface, surface, deposit district, just can cooling base.This creative method also is particularly suitable for applying when being heated can produce the substrate of adverse reaction with the composition in the atmosphere, for example is subject to the substrate of oxidation affects.Controlled atmosphere around low temperature that substrate is suffered and the deposit district all helps to reduce substantially the adverse reaction that produces between substrate and the Atmospheric components.
Though, preferably under environment or atmospheric pressure, implement CACCVD usually basically and apply operation, control combustion flame temperature or other parameter also of great use by the control combustion pressure sometimes.Can under the low like that pressure of 10 holders, keep combustion flame.Usually, when particularly using the energy beyond the combustion flame, can realize maximum cost and Production Gain by operation under environment and elevated pressures.
Shown in Figure 4 is two transfer laminations 114, is to form two sides circuit board blank structure, and they are bonded on the uncured or partly solidified dielectric resin material 116.Insulating materials can be selected from various materials, for example epoxy resin commonly used, FR epoxy resin, prepreg (mylar), polyimides, cyanate ester or the liquid crystals polymer that obtains by means of the conventional composite process.In common lamination process, under heat and pressure condition, shift lamination 114 and keep in touch with insulating materials, solidify fully up to dielectric resin material, between metal level 110 and dielectric resin material 116, form strong bond thus.Necessary is that the bonding force that forms between dielectric resin material 116 and the metal level 110 will be provided with greater than the bonding force between metal level 110 and the deposit substrate 112.Bonding force between transfer base substrate 112 and the metal level is usually about 1/2lb/in 2With 2lb/in 2Between, usually approximately less than 1.5lb/in 2, preferably, the bonding force between metal level 110 and the resin material 116 is approximately greater than 5lb/in 2, preferably approximately greater than 9lb/in 2In related fields, the bonding force between resin material 116 and the metal level 110 should be at least about 3lb/in 2, preferred at least than the high approximately 6lb/in of the bonding force between metal level 110 and the transfer base substrate 112 2As shown in Figure 5, this can make transfer base substrate 112 strip down from metal level 110.
Bonding force between metal level 110 and the resin material 116 not only depends on the composition of two kinds of materials, and depends on the surface smoothness or the roughness of metal level (with transfer base substrate 112 facing surfaces).In the process by CCVD or the deposit of CACCVD method, deposited metal has from smooth to very coarse surface the metal level after the deposit; So, can easily reach the ideal surfaced roughness that it and resin material 116 have good bonding power by changing deposition parameters.These deposition parameters that can change comprise temperature, carrier fluid, precursor compound, precursor concentration, flow velocity etc.Because can the various widely materials of deposit, therefore must rule of thumb determine for the specified conditions that reach the ideal surfaced roughness by CCVD and CACCVD; Yet, in those of ordinary skills' skill, change deposition parameters and determine when that it is very easy arriving desired roughness.With respect to other method that form to shift lamination, those technology of describing in No. the 3969199th, 4431710,4357395,5322975 and 5418002, the United States Patent (USP) for example, the transfer lamination of making the controlled surface roughness is an advantage of the present invention.
The operation of handling metal level for the formation printed circuit board (PCB) is a traditional approach, for example by above-mentioned " graphic plating " or printing etching " method.
What Fig. 6 A-E represented is the method that forms thin film resistor by transfer method of the present invention.On the support 201 of for example aluminium, as described in No. the 09/198954th, the U.S. Patent application of quoting in the above, by CCVD or CACCVD layer of conductive material 202, copper for example, and by CCVD deposit resistance elements 203, for example the mixed platinum of silicon provides the structure of Fig. 6 A thus.The resistance material layer thickness is usually approximately between 0.1 to 0.75 micron, preferably between about 0.1 to 0.2 micron.
As described in No. the 09/198954th, the U.S. Patent application of quoting in the above, the platinum of the silicon that mixed is porous, and it can form figure by the ablation lithographic technique.On the platinum of the silicon that mixed, apply photoresist, photoresist is exposed to the radiation that forms figure, and makes its development.The platinum of silicon of will having mixed then is exposed to the etching agent of copper.Etching agent penetrates the platinum layer of the silicon that mixed, and the interface between the platinum layer 203 of the decomposition copper coating 202 and the silicon that mixed.Before significantly decomposing, stop etching at copper coating 203.This has produced the resistance material paster, Fig. 6 B.Although only show such paster, can produce a plurality of resistance material pasters.
Shown in Fig. 6 C, resistance material paster 204 is embedded in the uncured insulating materials, in for example glass fibre/epoxy " prepreg " 205, and prepreg solidifies then.Prepreg after the curing is that the lamination in the operation of back provides support.Can see that in Fig. 6 C aluminium foil support 201 strips down from copper coating 202.
Then, on copper coating 202, apply photoresist figure 206 (Fig. 6 D), and the electrical connector 207 of electro-coppering in the above.Peel off resist (Fig. 6 E).Then, for example utilize iron chloride, only stay electrical connector 207 in the opposite end of resistance material paster 204 by being etched away copper coating 202 fast.Usually, this structure is embedded in the extra play (not shown) of prepreg.
Can utilize the capacitor shown in the similar approach shop drawings 7A-E.Shown in Fig. 7 A is aluminum support 301, on this support successively deposit copper coating 302, silicon layer and another copper coating 304.The thickness of insulation (silicon) layer is usually between about 0.1 to about 0.75 micron, preferably between about 0.1 to 0.25 micron.On copper coating 304, form the photoresist figure 305 of forming figure, Fig. 7 B, electro-coppering capacitor plate 306 on that part of copper coating 304 of uncoated photoresist figure 305 (showing two), peel off photoresist 305, produce the structure of Fig. 7 C, by being etched away copper coating 304 fast, shown in Fig. 7 D, stayed discontinuous capacitor plate 306, they contact with insulating barrier 303.Capacitor plate 306 is embedded in the prepreg 307, when prepreg solidifies, just can peel off Copper Foil 301 strippings.Copper coating 302 is also repeated period treatment to coating 304, on another side of insulating barrier 303, formed capacitor plate 306 thus.This side also is embedded in the prepreg 307.
By particular examples the present invention is described in more detail now.Nickel coating on example 1 polyimide substrate
In device shown in Figure 1 on polyimide substrate deposit the nickel film.Be that the molten silicon capillary (22) of 75um is carried with the flow velocity of 0.25sccm (cc/min of standard) 0.0688M Ni (NO is arranged by internal diameter 3) 21.20M NH 4OH solution.Carry hydrogen with the speed of 1.20lpm (standard liter/min) and by pipeline (44) with the speed of 756sccm by atomizing pipeline (38).By pipeline (52) with 1.40lpm speed delivery of oxygen.Carry argon by pipeline (68) with the speed of 28.1lpm, the internal diameter of described pipeline (68) is 5/8 inch.Reduce argon gas stream so that carry out manual ignition, afterwards the argon gas flow velocity is returned into the initial value of setting.In case light, do not need to ignite gas or other incendiary source are kept igniting.Approximately the gas temperature of 1mm position is 600 ℃ above deposit point.With the velocity scanning substrate of 20 inch per minute clocks, crossing twice " 4 * 4 " area with 0.0625 inch step pitch in the position of distance nozzle flange (64) 2mm, once is horizontal sweep, is vertical sweep afterwards.Required total time of scanning motion is 16 minutes.So deposit average thickness be approximately 0.1 micron nickel.Copper coating on the example 2-aluminium foil
Utilize the anhydrous ethyl ethereal solution cement copper of two (2-ethyl acetic acid) copper (II) of 0.035M.Speed with 1.00sccm is ejected into solution in the pipe, and this pipe also is supplied with the preheating gas of 40lpm, and this gas is 500 ℃ 10%H 2The mist of/Ar.The injection of discharging by the mouth of pipe about 5cm that grows up.Substrate is vertical with air-flow, from the about 2mm of the mouth of pipe.By this method on 50 microns aluminium foil deposit 1.5 microns metallic copper coating.Platinum coating on the example 3-polyimide substrate
In device shown in Figure 1 on polyimides deposit platinum film.Carry 5.3mM (NH by capillary (22) with the speed of 0.25sccm 3) 2Pt (NO 2) 21.20M NH 4OH solution.Carry argon by pipeline (18) with the speed of 1.60lpm.Carry hydrogen by pipeline (44) with the speed of 1.6lpm.By the speed delivery of oxygen of pipeline (52) with 800sccm.Carry argon by pipeline (68) with the speed of 28.1lpm.About 1mm place gas temperature is 400 ℃ above deposit point.In the position of distance nozzle flange (64) 2mm the regional interscan substrate of " 6 * 6 " three times, the twiceth, horizontal sweep is a vertical sweep afterwards.Produced the platinum coating of 3 micron thickness thus.Nickel coating on the example 4-polyimide substrate
In the device of Fig. 1 on polyimide substrate deposit the nickel film.Stainless steel nozzle needle by 22ga is carried with 0.25 sccm speed from the pressurizing vessel of 300cc 2.00g Ni (NO 3) 26H 2The 25.0gH of O 2O and 180gNH 3 (t)Solution, wherein said stainless steel nozzle needle top is inserted with the molten silicon capillary that internal diameter is 20um.Hydrogen passes through pipeline (38) and (44) with the flow velocity of 1.20lpm and 756sccm respectively.By the speed delivery of oxygen of pipeline (52) with 1.20lpm.Carry argon by pipeline (68) with the speed of 28.1lpm.Approximately the temperature at 2mm place is 600 ℃ on deposit point.At the about position scanning substrate twice of 2mm of distance nozzle flange (64), be 16 minutes sweep time, then deposit average thickness be 0.1 micron nickel coating.

Claims (21)

1. method of making the printed circuit board (PCB) blank, described circuit board blank have the insulating materials substrate and are positioned at metal level at least one side of described substrate, and between 0.1 and 3 micron, this method comprises metal layer thickness approximately:
Transfer base substrate is provided, and it can show will being deposited on the low bonding force of metal level on the substrate,
The deposited metal on described transfer base substrate by combustion chemistry vapor deposition or controlled atmosphere combustion chemistry vapour deposition, described metal layer thickness approximately between 0.1 and 3 micron,
The insulating materials substrate is provided, the described metal level that is deposited is adhered on the described insulating materials substrate forms bondingly, its bonding force is than the bonding force height between described deposit substrate and the described metal level, and
Remove described transfer base substrate from described metal level.
2. method according to claim 1, the metal level that wherein is deposited adhere on two sides of described insulating materials substrate.
3. method according to claim 1, the described metal level of deposit wherein, make its with described substrate facing surfaces on have the surface roughness of institute's deposit, this roughness can strengthen the bonding force of it and described insulating materials substrate enough.
4. method according to claim 1, the bonding force that forms between the rough surface of wherein said deposited metal and the described insulating materials substrate is at least about 5lbs/in 2
5. method according to claim 1, wherein said depositing metal is a copper.
6. method according to claim 1, wherein said depositing metal is a nickel.
7. method according to claim 1, wherein said depositing metal is a platinum.
8. method according to claim 1, wherein said depositing metal are to select from the group of being made up of silver, gold, tin and zinc.
9. method according to claim 1, wherein said transfer base substrate is an aluminium foil.
10. method according to claim 1, wherein said deposit substrate is a Kapton.
11. method according to claim 1, the bonding force between wherein said deposited metal and the described transfer base substrate is approximately 1.5lbs/in 2Or it is lower.
12. method according to claim 1, the bonding force that forms between wherein said deposited metal and the described insulating materials substrate is at least about 5lbs/in 2
13. method according to claim 1, the bonding force that forms between wherein said deposited metal and the described insulating materials substrate is at least about 3lbs/in 2, it is greater than the bonding force between described transfer base substrate and the described deposited metal.
14. transfer lamination that is used for providing thin film metal layer to insulated substrate, described transfer lamination comprises pliable and tough transfer base substrate and the thickness metal level between 0.1 to 3 micron approximately, metal level bonds on the described pliable and tough transfer base substrate releasedly, and deposition surface roughness that described metal level has on the side relative with described insulated substrate foot can promote afterwards the bonding force with insulated substrate.
15. transfer lamination according to claim 14, wherein said metal level is a copper.
16. transfer lamination according to claim 14, wherein said transfer base substrate is an aluminium foil.
17. transfer lamination according to claim 14, the bonding force between wherein said transfer base substrate and the described metal level are approximately between 1/2 to 2lbs/in 2Between.
18. a transfer lamination that is used for providing thin metal layer, described transfer lamination to insulated substrate comprise pliable and tough transfer base substrate, thickness approximately between between 0.1 to 3 micron and can and the bonding releasedly metal level of described pliable and tough transfer base substrate and thickness approximately between 0.1 to 0.75 micron and will with the insulation material layer of described metal bonding layer.
19. a transfer lamination that is used for providing thin metal layer, described transfer lamination to insulated substrate comprise pliable and tough transfer base substrate, thickness approximately between between 0.1 to 3 micron and can and the bonding releasedly metal level of transfer base substrate and thickness approximately between 0.1 to 0.75 micron and with the resistance elements of described metal bonding layer.
20. a method of making thin film resistor, this method comprises:
In the following manner at deposit conductive layer on the support substrate: a little less than the bonding force of described conductive layer and described substrate is wanted enough, so that described support substrate can strip down from described conductive layer,
Deposit resistance elements on described conductive layer,
Be described resistance elements constructing graphic, so that a resistance elements paster is provided at least,
Described resistance material paster is imbedded in the insulating materials of supporting lamination,
Peel off down described support substrate from described conductive layer, and
On the relative position on the described resistance material paster,, remove that part of described conductive layer on the described resistance material paster, so that between described electrical contact, limit Electricity conductive plaster by described resistance material paster by described conductive layer structure electrical contact.
21. a method of making thin film capacitor, this method comprises:
In the following manner at first conductive layer of deposit on the support substrate: a little less than the bonding force of described first conductive layer and described substrate is wanted enough, so that described support substrate can strip down from described conductive layer,
Deposit resistance elements on described conductive layer,
Deposit second conductive layer on described insulation material layer,
Form at least one capacitor plate by described second conductive layer,
To imbed in the insulating materials of supporting lamination by the described capacitor plate that described second conductive layer forms,
Peel off down described support substrate from described first conductive layer, and
Make at least one capacitor plate by described first conductive layer.
CN00811496A 1999-07-09 2000-07-07 Method of forming thin metal layer on insulating substrate Pending CN1368904A (en)

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CN103855037A (en) * 2012-11-28 2014-06-11 同和金属技术有限公司 Electronic part mounting substrate and method for producing same
CN105531805A (en) * 2013-09-09 2016-04-27 同和金属技术有限公司 Electronic-component-equipped substrate and method for producing same
CN111115563A (en) * 2019-12-23 2020-05-08 湖南大学 Method for stripping functional material by full-dry method

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CN101795856A (en) * 2007-09-06 2010-08-04 美商绩优图科技股份有限公司 Porous washcoat-bonded fiber substrate
CN103855037A (en) * 2012-11-28 2014-06-11 同和金属技术有限公司 Electronic part mounting substrate and method for producing same
CN105531805A (en) * 2013-09-09 2016-04-27 同和金属技术有限公司 Electronic-component-equipped substrate and method for producing same
CN105531805B (en) * 2013-09-09 2018-06-22 同和金属技术有限公司 Electronic device mounted board and its manufacturing method
CN111115563A (en) * 2019-12-23 2020-05-08 湖南大学 Method for stripping functional material by full-dry method

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