WO2003034488A1 - Substrate and method for producing the same - Google Patents
Substrate and method for producing the same Download PDFInfo
- Publication number
- WO2003034488A1 WO2003034488A1 PCT/JP2002/010414 JP0210414W WO03034488A1 WO 2003034488 A1 WO2003034488 A1 WO 2003034488A1 JP 0210414 W JP0210414 W JP 0210414W WO 03034488 A1 WO03034488 A1 WO 03034488A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- conductive layer
- via hole
- ceramic
- conductive
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/15—Ceramic or glass substrates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49827—Via connections through the substrates, e.g. pins going through the substrate, coaxial cables
-
- 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
- H05K1/02—Details
- H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
- H05K1/0203—Cooling of mounted components
- H05K1/0204—Cooling of mounted components using means for thermal conduction connection in the thickness direction of the substrate
- H05K1/0206—Cooling of mounted components using means for thermal conduction connection in the thickness direction of the substrate by printed thermal vias
-
- 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
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
- H05K1/111—Pads for surface mounting, e.g. lay-out
- H05K1/112—Pads for surface mounting, e.g. lay-out directly combined with via connections
- H05K1/114—Pad being close to via, but not surrounding the via
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- 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
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0302—Properties and characteristics in general
- H05K2201/0317—Thin film conductor layer; Thin film passive component
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0347—Overplating, e.g. for reinforcing conductors or bumps; Plating over filled vias
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
- H05K2201/10621—Components characterised by their electrical contacts
- H05K2201/10674—Flip chip
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/16—Inspection; Monitoring; Aligning
- H05K2203/167—Using mechanical means for positioning, alignment or registration, e.g. using rod-in-hole alignment
-
- 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
- H05K3/0008—Apparatus or processes for manufacturing printed circuits for aligning or positioning of tools relative to the circuit board
-
- 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
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0082—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the exposure method of radiation-sensitive masks
-
- 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
- H05K3/06—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 the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/245—Reinforcing conductive patterns made by printing techniques or by other techniques for applying conductive pastes, inks or powders; Reinforcing other conductive patterns by such techniques
- H05K3/246—Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
-
- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
- H05K3/4053—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques
- H05K3/4061—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques for via connections in inorganic insulating substrates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
- Y10T29/49155—Manufacturing circuit on or in base
- Y10T29/49156—Manufacturing circuit on or in base with selective destruction of conductive paths
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
- Y10T29/49155—Manufacturing circuit on or in base
- Y10T29/49165—Manufacturing circuit on or in base by forming conductive walled aperture in base
Definitions
- the present invention relates to a ceramic substrate having via holes that can be suitably used as a submount, and a method for manufacturing the same.
- Conventional technology
- a submount is an insulating substrate located between a semiconductor laser element and a heat sink (a block made of metal such as copper), and has the ability to efficiently transfer the heat generated by the semiconductor laser element to the heat sink side. is there.
- circuit patterns are provided on the upper and lower surfaces of a ceramic substrate, and these upper and lower circuit patterns are electrically connected by conductive via holes penetrating between the upper and lower surfaces. What is connected.
- An element such as a semiconductor laser is bonded on one side and a heat sink is bonded on the other side by soldering or the like.
- a through-hole is formed in a plate-like molded body (green sheet) containing ceramic powder, and a paste containing a conductive material is filled therein.
- this method is called cofire method
- polishing the surface metallizing the entire surface of the ceramic substrate to form a conductive layer, and then applying the lithography method to the circuit
- a method of forming a pattern has been adopted.
- a photoresist is applied on a conductive layer covering the entire surface of the substrate, and an exposure process using a circuit pattern mask, a development rinsing process, and, if necessary, an etching process after a post bake process
- the circuit pattern is formed by removing the unnecessary conductive layer and removing the resist. Note that, depending on the implementation, On the surface on which the element is mounted, the circuit pattern may be composed of a conductive layer covering the entire surface in some cases, but even in this case, the circuit pattern is present on the portion where the element is actually mounted and on the base.
- a via hole filled with a conductive material a metal is often used as the conductive material, so such a via hole is hereinafter also simply referred to as a metal via hole). Is provided for the purpose of electrical connection of the circuit patterns formed on both sides of the ceramic substrate.
- the surface of the metal via holes by (more particularly a surface exposed portion of the electrically conductive material filled in the via holes) dividing lines to form a circuit pattern so as to cover the entire surface and its surroundings in the circuit pattern.
- the circuit pattern mask photomask
- the contact between the metal via hole and the circuit pattern on the surface of the ceramic substrate is made.
- the contact area is reduced, which causes defective products such as increased electrical resistance and poor connection. Therefore, it is necessary to accurately align the mask. Even when the latter circuit pattern is formed of a conductive layer covering the entire surface, positioning of the mask for forming the solder film is important.
- the present invention relates to a “double-sided circuit board having a metal via hole” which can be suitably used as a submount for mounting a semiconductor element, wherein the electrical connection between the metal via hole and the circuit pattern is good, and the element is bonded. It is an object to provide a substrate that can be easily positioned, and a method for efficiently manufacturing such a substrate. Means for solving the problem
- the present inventors have conducted intensive research to solve the above technical problems. That is, in general, when a conductive layer is formed on a substrate, it is considered that the substrate surface is preferably smooth from the viewpoint of adhesion between the substrate and the conductive layer. If the conductive layer is formed by artificially projecting the conductive layer, the position of the metal via hole may be easily confirmed even after the conductive layer is formed.
- the authors conducted intensive studies on the conditions for forming the protruding portions that can be distinguished as described above, while also ensuring the reliability when mounting directly on a metal via hole. As a result, it was found that when the surface roughness of the ceramic substrate was set to a specific value or less and the metal via hole was protruded from the substrate surface at a specific height, the expected effect was obtained. Complete I came to.
- a conductive layer covering the entire surface of the exposed portion of the conductive material filled in the via hole is formed on the surface of the ceramic substrate having the via hole filled with the conductive material therein.
- the conductive material filled in the via hole present in the substrate protrudes from the surface at a height of 0.3 to 5.
- the substrate of the present invention (hereinafter also referred to as the product substrate of the present invention) can be suitably used as a submount.
- the product substrate of the present invention is characterized in that not only the reliability of die attachment when mounting elements is high, but also a highly reliable substrate is easily and efficiently obtained by using a lithography method. Further, among the product substrates of the present invention, those having a conductive layer covering the entire surface of the ceramic substrate on which the elements are mounted can easily confirm the position of the metal via hole existing in the underlayer. A solder film pattern for element bonding can be formed on the conductive layer by arbitrarily controlling the relative positional relationship with the metal via hole.
- a second aspect of the present invention is a ceramic substrate having a via hole filled with a conductive substance therein, wherein the ceramic portion on at least one surface of the ceramic substrate has a surface roughness of Ra 0.
- the conductive material filled in the via hole present on at least one surface of the ceramic portion having a surface roughness of R a ⁇ 0.8 ⁇ m is 0.8 Aim.
- the substrate of the present invention (hereinafter also referred to as the “raw material substrate of the present invention”) is used as a raw material substrate for producing the product substrate of the present invention which can be suitably used as the above submount. Can be suitably used.
- the raw material substrate has a feature that even if a conductive layer is formed on the surface, the position of the metal via hole can be easily confirmed visually.
- the conductive material filled in the via hole of the raw material substrate of the present invention protrudes at a height of 0.3 to 5.3 ⁇ from the surface of the ceramic portion of the substrate.
- a part of the conductive layer is removed by lithography to form a conductive layer covering the entire surface of the exposed portion of the protruding conductive material.
- the conductive material filled in the via hole of the raw material substrate according to the present invention is 0.3 to 5.0 from the surface of the ceramic portion of the substrate. protruding at a height of m After forming a conductive layer covering the entire surface on at least one surface, the position of a via hole existing under the conductive layer is confirmed based on the position of a convex portion of the conductive layer derived from the via hole.
- FIG. 1 is a perspective view and a vertical sectional view of a typical embodiment of the product substrate of the present invention.
- the substrate of the present invention (the raw material substrate of the present invention and the product substrate of the present invention) has a ceramic portion having a surface roughness of R on a surface serving as an element mounting surface of a ceramic substrate having metal via holes. a ⁇ 0.8 ⁇ or less, and further has a common feature that the conductive material filled in the via hole protrudes from the surface of the surface at a height of 0.3 to 5. . ⁇ .
- the protrusion height is less than 0.3 ⁇ , it is difficult to visually check the position of the metal via hole when the entire surface of the substrate is covered with the conductive layer. If the protrusion height exceeds 5.0 ⁇ m, a large step is formed between the conductive layer on the metal via hole and the peripheral conductive layer when the entire surface of the substrate is covered with the conductive layer. In particular, the adhesiveness in the vicinity of the step is deteriorated, and there is a possibility that a poor electrical conduction may occur when a circuit pattern is formed. When the surface roughness of the ceramic portion is Ra> 0.8 / im, the reliability in mounting an element such as a semiconductor laser is reduced. From the viewpoint of the above effects, it is particularly preferable that the protrusion height is from 0.3 to 1.8 ⁇ , and the surface roughness is Ra ⁇ 0.05 m.
- the substrate of the present invention having such characteristics is provided with a conductive layer covering the entire surface of the exposed portion of the conductive material filled in the via hole protruding from the surface of the ceramic substrate (the present invention).
- a product substrate) itself can be suitably used as a submount, and a substrate having no conductive layer on its surface (a raw material substrate of the present invention) can be suitably used as a raw material substrate for manufacturing the product substrate of the present invention. .
- FIG. 1 shows an alternative to the product substrate of the present invention in which a solder film pattern for mounting an element is formed.
- the substrate has a ceramic surface having an element mounting surface 101 with a surface roughness of R a ⁇ 0.8 ⁇ m and a via hole (metallic via hole) 200 filled with a conductive substance therein.
- the entire surface of the via-hole protruding portion of the substrate 100 and the surface of the ceramic substrate in the vicinity thereof are covered with the conductive layer 300, and the solder film pattern 400 for mounting elements is mounted on the conductive layer. Have been. Note that, in the perspective view of FIG.
- the end face of the metal via hole 200 is described as being exposed, but this indicates the position of the metal via hole, and as shown in the sectional view, Is covered with a conductive layer 300.
- a conductive layer may be formed on the surface 102 opposite to the device mounting surface.
- the projecting height h of the via hole 200 from the surfaces 101 and 102 is 03 to 5. . ⁇ .
- the product substrate shown in FIG. 1 excluding the conductive layer 300 and the element mounting solder film pattern 400 is the raw material substrate of the present invention.
- the material of the ceramic substrate used in the raw material substrate and the product substrate of the present invention known materials can be used without particular limitation. Specifically, aluminum nitride, beryllium oxide, silicon carbide, alumina, mullite, boron nitride, glass borosilicate, and the like are used. Among them, aluminum nitride has high thermal conductivity, so when it is used as a submount, for example, it efficiently dissipates the heat generated from the semiconductor laser element to the heat sink, has a low dielectric constant, and has a low thermal conductivity. Since the coefficient is equivalent to the material of the semiconductor laser element such as Si, it can be used particularly preferably. When used as a submount for mounting a semiconductor laser element, the ceramic substrate preferably has a higher thermal conductivity, more preferably 170 W / mK or more, particularly preferably 20 O WZmK or more. Used for
- the ceramic substrate used in the raw material substrate and the product substrate of the present invention has a via hole filled therein with a conductive substance.
- a conductive substance a known substance is used without any particular limitation. Generally, tungsten, molybdenum, copper, silver, gold, nickel, palladium and the like can be suitably used.
- the conductive material used in the production of the substrate described in the above “Is the heat-resistant substance used ? : can be used appropriately.
- the size, shape and number of via holes can be arbitrarily determined. The via hole does not need to penetrate the ceramic substrate, and if a conductive layer is formed inside the ceramic substrate, the via hole has a depth that reaches the conductive layer.
- the conductive material does not necessarily need to be filled so as to completely fill the via hole, and may be filled so as to cover the inner surface. It is preferable to have a via hole filled with a conductive material so as to completely fill a hole (through hole) penetrating the upper and lower surfaces of the ceramic substrate because the hole is easily formed.
- a via hole is usually formed by filling a paste containing a conductive substance into the inside of the through-hole.
- the diameter of the through-hole is 0.03 to 0. It is preferably 0.5 mm, more preferably 0.05 to 0.4 mm, and the ratio of its length to diameter (length / diameter) is preferably 40 or less.
- the electrical resistance of the via hole filled with the conductive material is not particularly limited, but should be 0.5 ⁇ or less, more preferably 0.1 ⁇ or less, in order to sufficiently exhibit the performance of the semiconductor laser device. Is preferred.
- the conductive layer formed so as to cover the entire surface of the exposed portion of the conductive material filled in the via hole on the surface on which the element is mounted is not particularly limited as long as it is a conductive film.
- a thin metal film or a thick film made of a metal powder and an inorganic binder or an organic binder is used.
- a metal thin film is most preferably used because of its high electric conductivity.
- any known metal can be used without limitation. It is preferably used. These metals may be used alone, or two or more These may be used in combination.
- the conductive layer may be a single layer, or may be used by laminating two or more layers in combination.
- the above-mentioned metal has good adhesion to the ceramic substrate, and thus can be suitably used for the first layer directly in contact with the ceramic substrate.
- Known metals can also be used for the metal of the second layer laminated on the first layer, but when the circuit pattern of the two-layer laminated film is used and the second layer is the uppermost layer, platinum, nickel, At least one of palladium, copper, silver and gold is preferably used because of its good electrical conductivity.
- a film is further laminated on the second layer and used as a circuit pattern of three or more layers, diffusion of elements between the first layer and the third layer is prevented, and the circuit pattern and the ceramic material are used.
- Platinum, nickel, palladium, tungsten, tungsten titanium, and molybdenum, which have a high diffusion-preventing ability, are more preferably used in order to secure a stable adhesion strength to the substrate.
- Known metals can be used for the third layer, for example, platinum, nickel, and platinum.
- At least one of radium, copper, silver, and gold is preferably used because of its good electrical conductivity.
- platinum, palladium, silver and gold are particularly preferably used because of their excellent corrosion resistance.
- solder film such as solder may be laminated and puttering.
- the method for producing the raw material substrate of the present invention is not particularly limited, except that the surface roughness of the ceramic substrate and the protrusion height of the metal via hole are controlled to be within the above ranges, and a conventionally known method can be employed.
- the raw material substrate of the present invention is a so-called cofire, in which a paste containing a conductive substance is directly filled into a through hole of a green sheet having a through hole, and firing of the ceramic powder and firing of the conductive substance are simultaneously performed. Method.
- it can also be obtained by a so-called post-fire method in which a through hole is formed in a sintered body using a laser or the like, and then a paste containing a conductive substance is filled and refired.
- the obtained raw material substrate can be suitably manufactured by polishing the surface of the substrate.
- a known technique can be used for the method of polishing without limitation, and a method such as lapping, polishing, barrel polishing, sand blasting, or polishing with a grinder is usually used.
- the method of setting the surface roughness of the ceramic substrate to R a ⁇ 0.8 ⁇ and the height of the metal via hole to 0.3 to 5.0 m is not particularly limited. i) After firing the green sheet with the through hole, fill the through hole with a paste containing a conductive material in a slightly excessive amount and fire again, and then make the surface of the substrate have surface roughness and protrusion of metal via holes. A method of controlling polishing conditions so that the height is within the above range; (ii) drilling a hole in the surface of the fired substrate using a laser or the like; 0. After polishing, the through hole is filled with a paste containing a slightly excessive amount of conductive material and refired.
- a ceramic substrate including a via hole fired as described above has abrasive particles (abrasives) because the conductive substance filled in the via hole is harder than a ceramic base plate made of a material such as ceramic.
- abrasive particles abrasives
- the soft ceramic substrate is more polished, and the hard metal via holes are projected.
- R a ⁇ 0.8 / m preferably R a ⁇ 0.05 zm, which is generally considered to have high reliability in mounting the semiconductor laser element, a small If the polishing using the cannonball is continued, the protruding height of the metal via hole becomes too large.
- the present inventors Based on the finding that the above tendency becomes smaller when large abrasive grains are used, and larger when small abrasive grains are used, the surface roughness of the ceramic substrate is reduced and the amount of protrusion of the metal via hole is reduced.
- first use large abrasive grains perform polishing, reduce the surface roughness of the ceramic substrate to a certain extent while suppressing the amount of protrusion of metal via holes, and then reduce
- By reducing the surface roughness of the ceramic substrate while maintaining the amount of protrusion of the metal via hole by polishing using abrasive grains we succeeded in obtaining a raw material substrate satisfying the above conditions. Things.
- Such polishing is 2 stage limited regardless number or more stages, it is also possible to carry out by selectively using abrasive grains of several grain size c
- the polishing conditions for each stage of the ceramic substrate and the conductive material used Since it differs depending on the material, vial diameter, etc., it cannot be specified unconditionally, but polishing is performed by changing the size of the cannonball and the polishing time for each system, these conditions, the amount of protrusion of the metal via hole and the ceramic It can be easily determined by examining the relationship with the surface roughness of the substrate.
- the position of the via hole can be easily visually checked from the surface of the thin-film conductive layer.
- It can be suitably used as an intermediate material when manufacturing a product substrate. That is, (1) After covering the entire surface of the surface of the raw material substrate of the present invention on which the element is mounted, that is, the surface on the side where the metal via holes protrude at a height of 0.3 to 5.0 Aim with a conductive layer. At least a part of the conductive layer is removed by using a lithography method to form a conductive layer that covers at least the entire surface of the exposed portion of the protruding metal via hole.
- the photomask Aligning the photomask based on the position of the convex portion of the conductive layer derived from the via hole existing under the conductive layer, or (2) adjusting the position of the raw material substrate of the present invention.
- the position of the via hole existing under the conductive layer After covering the entire surface of the surface on which the element is mounted, that is, the surface on which the metal via hole protrudes at a height of 0.3 to 5.0 / zm, with a conductive layer, the position of the via hole existing under the conductive layer To the via hole
- the product substrate of the present invention can be suitably manufactured by forming a solder film pattern for element bonding on the conductive layer by checking based on the position of the protruding portion of the conductive layer derived therefrom.
- the lithography method used in the above method (1) is one of the typical pattern formation methods.
- This is a method in which a circuit pattern is formed by baking an arbitrary circuit pattern using optical transfer technology and etching the underlying conductive layer using this resist pattern as a mask. It consists of a process of applying (pasting) a resist on top, (2) an exposure process of printing a pattern using a photomask on the resist, (3) a development and rinsing process, (4) an etching process, and (4) a resist removal process.
- the alignment of the photomask in the exposure step is performed based on the position of the convex portion of the conductive layer derived from the metal via hole projecting from the raw material substrate, so that the photomask can be misaligned.
- the rate of occurrence of defective products due to this can be reduced.
- the conductive layer formed by the above manufacturing method so as to cover the entire surface of the side where the metal via hole of the raw material substrate protrudes at a height of 0.3 to 5.0 ⁇ m is formed on the exposed surface of the metal via hole.
- the product substrate of the present invention having a circuit pattern of a desired shape can be obtained by leaving a part to cover the entire surface and removing a part of the part by etching. Therefore, the circuit pattern composed of the remaining conductive layer basically has the same structure as the conductive layer described in the product substrate of the present invention, but is selected later on the conductive layer remaining after etching.
- a metallized layer can also be formed on the fly.
- the conductive layer that finally becomes the circuit pattern has a multilayer structure
- at least the lowermost layer may be formed and etched.
- known film forming methods such as a physical vapor deposition method, a chemical vapor deposition method, a thermal spray method, an electroless plating method, a melting plating method, an anodic oxidation method, and a coating method can be used without limitation.
- the lithography method employed in the present invention is a conventional lithography method except that the alignment of the photoresist is performed based on the position of the projection of the conductive layer derived from the metal via hole projecting from the raw material substrate of the present invention.
- the various materials and chemicals such as a resist, a photomask, and a resist stripping agent, those used in a general lithography method can be used without limitation, and the use conditions are not particularly limited.
- the formation of the solder film pattern in the method (2) is performed by forming a mask made of a metal plate or the like having a portion corresponding to the solder film pattern on the conductive layer of the substrate by projecting a metal via hole. It can be performed by positioning and mounting based on the position of the projection of the conductive layer to be formed, forming a solder film by a vapor deposition method, a sputtering method, or the like, and then removing the mask.
- a solder film layer can be selectively formed only in a portion where there is no metal via hole immediately below the conductive layer. Note that, as shown in FIG. 1, even when a circuit pattern having a desired shape is formed by the method (1), similarly, only a portion where a metal via hole does not exist directly below the conductive layer is selectively formed. It is of course possible to form a solder film layer.
- Example 1
- the residual carbon ratio of the degreased test sample of the degreased test sample was 1950 ppm.
- the degreased body is placed in a container made of aluminum nitride, heated in a nitrogen atmosphere at 1615 ° C for 4 hours, and further baked at 1870 ° C for 9 hours to obtain a ⁇ 200 / zm diameter.
- An aluminum nitride substrate having a length of 48 mm, a width of 48 mm, and a thickness of 0.48 mm having a tungsten via hole was obtained.
- the warpage of the substrate was 35 Aim.
- the thermal conductivity of a test sample with a substrate thickness of 0.48 mm, degreased and fired was 210 W / mK when measured by the laser flash method.
- the surface of the aluminum nitride substrate having the tungsten via hole was polished for 30 minutes with 360 ⁇ m gun granules, and then polished for 1 hour and 20 minutes with 120 ⁇ m abrasive particles to reduce the surface roughness of the aluminum nitride substrate plane.
- the alignment of the metal mask could be easily performed because the position of the tungsten via hole could be confirmed as the position of the projection of the conductive layer.
- the substrate on which the conductive layer and the solder film layer were formed was cut into a 1.3 mm square to obtain a chip shape. For everything that was cut When the positional relationship between the solder film pattern and the via hole was examined, no via hole was found under the solder film pattern.
- a nail head with nickel plating was soldered vertically to a portion of the conductive layer located immediately above the tungsten via hole.
- a raw substrate was obtained in which tungsten via holes protruded from the surface of the aluminum nitride substrate at a height of 0.1 m.
- a conductive layer and a solder film pattern were formed on the surface of the raw material substrate.
- the alignment of the metal mask was performed with reference to one corner of the substrate because the position of the via hole could not be visually confirmed from above the conductive layer and the solder film layer.
- Example 2 the substrate on which the conductive layer and the solder film layer were formed was cut in the same manner as in Example 1, and the position relationship between the solder film pattern and the tungsten via holes was examined for all cut substrates. There were 419 defective chips with tungsten via holes under the film pattern. Further, the adhesion strength of the conductive layer was measured to be 10.5 kgZm m 2 , and the peeling mode was solder breakdown. In addition, the via hole When the air resistance was measured, it was 0.025 ⁇ (measured average value of 10 chips). Comparative Example 2
- a source substrate was obtained in which the tungsten via hole protruded from the substrate surface at a height of 6.5 im.
- a conductive layer and a solder film pattern were formed on the substrate surface in the same manner as in Example 1.
- the alignment of the metal mask could be easily performed because the position of the via hole could be confirmed as the position of the protrusion of the metallized layer, and the positional relationship between the solder film pattern and the via hole was examined. There was no via hole below.
- the adhesion strength of the conductive layer was measured to be as low as 2.1 kg / mm 2, and the peeling mode was destruction of the interface between the substrate and the conductive layer of the thin film.
- the electrical resistance of the via hole was measured, it was as high as 0.55 ⁇ (measured average value of 10 chips), and partial conduction failure occurred.
- the protrusion height of the via hole filled with the conductive material is limited to a certain height from the plane of the ceramic substrate, so that the position of the via hole can be visually confirmed even after metallization, and the circuit pattern Positioning of the mask for formation can be facilitated.
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Semiconductor Lasers (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Die Bonding (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60236526T DE60236526D1 (ja) | 2001-10-10 | 2002-10-07 | |
US10/450,182 US20040016570A1 (en) | 2001-10-10 | 2002-10-07 | Substrate and method of manufacturing the same |
EP02779905A EP1435658B1 (en) | 2001-10-10 | 2002-10-07 | Substrates and method for producing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001312516A JP4030285B2 (ja) | 2001-10-10 | 2001-10-10 | 基板及びその製造方法 |
JP2001-312516 | 2001-10-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003034488A1 true WO2003034488A1 (en) | 2003-04-24 |
Family
ID=19131163
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2002/010414 WO2003034488A1 (en) | 2001-10-10 | 2002-10-07 | Substrate and method for producing the same |
Country Status (6)
Country | Link |
---|---|
US (1) | US20040016570A1 (ja) |
EP (1) | EP1435658B1 (ja) |
JP (1) | JP4030285B2 (ja) |
CN (1) | CN1329978C (ja) |
DE (1) | DE60236526D1 (ja) |
WO (1) | WO2003034488A1 (ja) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005311205A (ja) * | 2004-04-23 | 2005-11-04 | Nec Corp | 半導体装置 |
JP2006013367A (ja) * | 2004-06-29 | 2006-01-12 | Sanyo Electric Co Ltd | 回路装置およびその製造方法 |
EP1946268A4 (en) * | 2005-09-12 | 2012-08-01 | Kritikal Securescan Pvt Ltd | METHOD AND SYSTEM FOR AUTOMATIC AND INTERACTIVE INSPECTION OF VEHICLES BASED ON A NETWORK |
US7877866B1 (en) | 2005-10-26 | 2011-02-01 | Second Sight Medical Products, Inc. | Flexible circuit electrode array and method of manufacturing the same |
JP2007250996A (ja) * | 2006-03-17 | 2007-09-27 | Kyocera Corp | 配線基板、並びにその配線基板を備えた電子装置およびプローブカード |
KR100754407B1 (ko) | 2006-06-08 | 2007-08-31 | 삼성전자주식회사 | 서브마운트 및 이를 구비하는 멀티 빔 레이저 다이오드모듈 |
FI20070904A0 (fi) * | 2007-06-07 | 2007-11-26 | Focoil Oy | Menetelmä piirilevyjen valmistuksessa |
JP5305787B2 (ja) * | 2008-08-27 | 2013-10-02 | セイコーインスツル株式会社 | 電子部品パッケージの製造方法 |
JP5349007B2 (ja) * | 2008-10-29 | 2013-11-20 | 京セラ株式会社 | 配線基板およびその製造方法 |
DE102009003178A1 (de) * | 2009-05-18 | 2010-11-25 | Endress + Hauser Gmbh + Co. Kg | Keramisches Bauteil mit mindestens einer elektrischen Durchführung, Verfahren zu dessen Herstellung und Drucksensor mit einem solchen Bauteil |
JP5461913B2 (ja) * | 2009-07-31 | 2014-04-02 | 日本特殊陶業株式会社 | 多層セラミック基板の製造方法 |
DE102009054909A1 (de) * | 2009-12-17 | 2011-06-22 | Endress + Hauser GmbH + Co. KG, 79689 | Keramisches Produkt und Verfahren zu dessen Herstellung |
KR101089936B1 (ko) * | 2010-01-13 | 2011-12-05 | 삼성전기주식회사 | 다층 세라믹 회로 기판 및 제조방법 |
CN103534802A (zh) * | 2011-06-01 | 2014-01-22 | E.I.内穆尔杜邦公司 | 用于高频应用的低温共烧陶瓷结构及其制造方法 |
DE102012101057A1 (de) * | 2011-12-27 | 2013-06-27 | Curamik Electronics Gmbh | Verfahren zur Herstellung von DCB-Substraten |
JP5831984B2 (ja) * | 2012-02-08 | 2015-12-16 | 日本特殊陶業株式会社 | 配線基板の製造方法 |
TW201422352A (zh) * | 2012-12-13 | 2014-06-16 | Viking Tech Corp | 基板製法 |
KR20150103653A (ko) * | 2013-01-07 | 2015-09-11 | 가부시끼가이샤 아라이도 마테리아루 | 세라믹 배선 기판, 반도체 장치, 및 세라믹 배선 기판의 제조 방법 |
CN103337580A (zh) * | 2013-06-19 | 2013-10-02 | 苏州信亚科技有限公司 | 一种带陶瓷散热基板的led灯 |
JP6867102B2 (ja) * | 2014-10-22 | 2021-04-28 | Jx金属株式会社 | 銅放熱材、キャリア付銅箔、コネクタ、端子、積層体、シールド材、プリント配線板、金属加工部材、電子機器、及び、プリント配線板の製造方法 |
CN106921923A (zh) * | 2015-12-24 | 2017-07-04 | 北京卓锐微技术有限公司 | Mems麦克风 |
JP6833818B2 (ja) * | 2016-03-29 | 2021-02-24 | 株式会社東芝 | セラミック回路基板およびそれを用いた半導体装置 |
JP6904094B2 (ja) * | 2016-06-23 | 2021-07-14 | 三菱マテリアル株式会社 | 絶縁回路基板の製造方法 |
CN112312688A (zh) * | 2019-07-23 | 2021-02-02 | Oppo广东移动通信有限公司 | 壳体、壳体的制造方法和电子设备 |
TW202119877A (zh) * | 2019-11-05 | 2021-05-16 | 南韓商普因特工程有限公司 | 多層配線基板及包括其的探針卡 |
CN115500011B (zh) * | 2022-11-03 | 2023-02-03 | 四川富乐华半导体科技有限公司 | 一种用于dpc陶瓷基板加工的定位方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1117297A (ja) * | 1997-06-25 | 1999-01-22 | Kyocera Corp | 配線基板 |
EP0987748A2 (en) * | 1998-09-18 | 2000-03-22 | Nec Corporation | Multilayered circuit board for semiconductor chip module, and method of manufacturing the same |
JP2001044323A (ja) * | 1999-07-30 | 2001-02-16 | Kyocera Corp | 電子部品実装用回路基板 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62142396A (ja) * | 1985-12-17 | 1987-06-25 | アルプス電気株式会社 | 薄膜回路基板 |
US4963701A (en) * | 1988-01-25 | 1990-10-16 | Kabushiki Kaisha Toshiba | Circuit board |
US5117069A (en) * | 1988-03-28 | 1992-05-26 | Prime Computer, Inc. | Circuit board fabrication |
JPH02267989A (ja) * | 1989-04-07 | 1990-11-01 | Ngk Insulators Ltd | セラミック回路基板およびその製造方法 |
JP2633366B2 (ja) * | 1989-11-24 | 1997-07-23 | 株式会社日立製作所 | 計算機モジュール用リードレスチップキャリア |
JPH04202074A (ja) * | 1990-11-30 | 1992-07-22 | Toshiba Corp | 薄膜用セラミックス基板 |
JPH05145230A (ja) * | 1991-11-22 | 1993-06-11 | Fujitsu Ltd | ガラスセラミツク基板の配線パターン形成方法 |
EP0560072A3 (en) * | 1992-03-13 | 1993-10-06 | Nitto Denko Corporation | Anisotropic electrically conductive adhesive film and connection structure using the same |
US5435480A (en) * | 1993-12-23 | 1995-07-25 | International Business Machines Corporation | Method for filling plated through holes |
US5581876A (en) * | 1995-01-27 | 1996-12-10 | David Sarnoff Research Center, Inc. | Method of adhering green tape to a metal support substrate with a bonding glass |
US5599744A (en) * | 1995-02-06 | 1997-02-04 | Grumman Aerospace Corporation | Method of forming a microcircuit via interconnect |
JPH08316271A (ja) * | 1995-05-12 | 1996-11-29 | Nitto Denko Corp | フィルムキャリアおよびこれを用いた半導体装置 |
JP3165779B2 (ja) * | 1995-07-18 | 2001-05-14 | 株式会社トクヤマ | サブマウント |
JP3166611B2 (ja) * | 1996-04-19 | 2001-05-14 | 富士ゼロックス株式会社 | プリント配線板及びその製造方法 |
US5787580A (en) * | 1996-11-19 | 1998-08-04 | Lg Information & Communications, Ltd. | Method for making radio-frequency module by ball grid array package |
JP3173410B2 (ja) * | 1997-03-14 | 2001-06-04 | 松下電器産業株式会社 | パッケージ基板およびその製造方法 |
JP3889856B2 (ja) * | 1997-06-30 | 2007-03-07 | 松下電器産業株式会社 | 突起電極付きプリント配線基板の製造方法 |
JP3344956B2 (ja) * | 1998-01-08 | 2002-11-18 | 日本特殊陶業株式会社 | 積層セラミック基板の製造方法 |
US6854985B1 (en) * | 1998-12-16 | 2005-02-15 | Paricon Technologies Corporation | Elastomeric interconnection device and methods for making same |
JP2000299560A (ja) * | 1999-04-15 | 2000-10-24 | Matsushita Electric Ind Co Ltd | セラミック回路板の製造方法 |
US6465084B1 (en) * | 2001-04-12 | 2002-10-15 | International Business Machines Corporation | Method and structure for producing Z-axis interconnection assembly of printed wiring board elements |
-
2001
- 2001-10-10 JP JP2001312516A patent/JP4030285B2/ja not_active Expired - Fee Related
-
2002
- 2002-10-07 WO PCT/JP2002/010414 patent/WO2003034488A1/ja active Application Filing
- 2002-10-07 EP EP02779905A patent/EP1435658B1/en not_active Expired - Fee Related
- 2002-10-07 DE DE60236526T patent/DE60236526D1/de not_active Expired - Lifetime
- 2002-10-07 CN CNB028031555A patent/CN1329978C/zh not_active Expired - Fee Related
- 2002-10-07 US US10/450,182 patent/US20040016570A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1117297A (ja) * | 1997-06-25 | 1999-01-22 | Kyocera Corp | 配線基板 |
EP0987748A2 (en) * | 1998-09-18 | 2000-03-22 | Nec Corporation | Multilayered circuit board for semiconductor chip module, and method of manufacturing the same |
JP2001044323A (ja) * | 1999-07-30 | 2001-02-16 | Kyocera Corp | 電子部品実装用回路基板 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1435658A4 * |
Also Published As
Publication number | Publication date |
---|---|
CN1329978C (zh) | 2007-08-01 |
US20040016570A1 (en) | 2004-01-29 |
CN1476632A (zh) | 2004-02-18 |
EP1435658A4 (en) | 2006-10-25 |
DE60236526D1 (ja) | 2010-07-08 |
EP1435658A1 (en) | 2004-07-07 |
JP4030285B2 (ja) | 2008-01-09 |
EP1435658B1 (en) | 2010-05-26 |
JP2003124397A (ja) | 2003-04-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2003034488A1 (en) | Substrate and method for producing the same | |
US7580240B2 (en) | Via array capacitor, wiring board incorporating a via array capacitor, and method of manufacturing the same | |
TWI357140B (en) | Substrate having a built-in semiconductor element | |
JP5093840B2 (ja) | 発光素子実装用多層配線基板とその製造方法 | |
US8139368B2 (en) | Component-containing module | |
JP2002359446A (ja) | 配線基板およびその製造方法 | |
JP2003198069A (ja) | 回路基板及びその製造方法 | |
US10157753B2 (en) | Wiring board, electronic device, and electronic module | |
JP2002198660A (ja) | 回路基板及びその製造方法 | |
JP2008258214A (ja) | 発光素子実装用多層配線基板とその製造方法 | |
JP5535451B2 (ja) | セラミック配線基板およびその製造方法 | |
US11395405B2 (en) | Wiring substrate and electronic device | |
JP4454105B2 (ja) | 多層配線基板の製造方法 | |
JP3199637B2 (ja) | 多層配線基板の製造方法 | |
JP2008159969A (ja) | 回路基板、電子装置および回路基板の製造方法 | |
JPH09293968A (ja) | 多層配線基板およびその製造方法 | |
JP4817835B2 (ja) | 配線基板 | |
JP2006066658A (ja) | 回路基板の製造方法 | |
JP2003008216A (ja) | セラミック多層基板の製造方法 | |
JP2001015895A (ja) | 配線基板およびその製造方法 | |
KR102360856B1 (ko) | 세라믹 기판 및 이를 포함하는 엘이디 패키지 | |
JP2001210746A (ja) | 半導体素子搭載用基板 | |
JP2002231860A (ja) | 電子部品装置 | |
JP4422452B2 (ja) | 配線基板 | |
JP2002124590A (ja) | セラミック回路基板及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CN |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FR GB GR IE IT LU MC NL PT SE SK TR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 028031555 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10450182 Country of ref document: US |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2002779905 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2002779905 Country of ref document: EP |