US20200404784A1 - Micro-roughened electrodeposited copper foil and copper clad laminate - Google Patents

Micro-roughened electrodeposited copper foil and copper clad laminate Download PDF

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Publication number
US20200404784A1
US20200404784A1 US16/899,630 US202016899630A US2020404784A1 US 20200404784 A1 US20200404784 A1 US 20200404784A1 US 202016899630 A US202016899630 A US 202016899630A US 2020404784 A1 US2020404784 A1 US 2020404784A1
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Prior art keywords
copper
micro
nodule
clad laminate
roughened electrodeposited
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Abandoned
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US16/899,630
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English (en)
Inventor
Yun-Hsing SUNG
Shih-Shen Lee
Hung-Wei Hsu
Chun-Yu Kao
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Co Tech Development Corp
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Co Tech Development Corp
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Priority to US16/899,630 priority Critical patent/US20200404784A1/en
Assigned to CO-TECH DEVELOPMENT CORP. reassignment CO-TECH DEVELOPMENT CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HSU, HUNG-WEI, KAO, CHUN-YU, LEE, SHIH-SHEN, SUNG, YUN-HSING
Publication of US20200404784A1 publication Critical patent/US20200404784A1/en
Priority to US17/355,515 priority patent/US12120816B2/en
Priority to US18/760,054 priority patent/US12557213B2/en
Abandoned legal-status Critical Current

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    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B15/12—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 paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2255/06—Coating on the layer surface on metal 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
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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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H05K1/0242—Structural details of individual signal conductors, e.g. related to the skin effect
    • 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
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0248—Needles or elongated particles; Elongated cluster of chemically bonded particles
    • 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
    • H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer or layered thin film adhesion layer
    • 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

Definitions

  • the present invention relates to a copper foil, especially an electrodeposited copper foil and a copper clad laminate comprising the electrodeposited copper foil.
  • the existing technology may inhibit or reduce the insertion loss of the electronic products in high-frequency transmission as much as possible by a compensating method based on the circuit technology, or by the selection of suitable conducting materials and/or dielectric materials, and try to minimize the loss generated by the electronic products in high-frequency transmission.
  • the selection of suitable conducting materials and/or dielectric materials may reduce the insertion loss of the electronic products in high-frequency transmission, but it also weakens the peel strength between the copper foil and the resin substrate of the copper clad laminate (CCL), which results in the peel-off of the copper foil and the resin substrate of the copper clad laminates in the follow-up processing or application preparation processes, and even affects the defect-free rate of the follow-up products.
  • CCL copper clad laminate
  • one purpose of the present invention is to inhibit or reduce the insertion loss of the electronic products in high-frequency transmission under the premise that the desired peel strength between the copper foil and the resin substrate is maintained.
  • the present invention provides a micro-roughened electrodeposited copper foil, comprising: a micro-rough surface, having multiple copper nodule-free areas and multiple copper nodule-arranged areas, in which part of the copper nodule-free areas are dispersed among the copper nodule-arranged areas; multiple copper nodules, being formed on the micro-rough surface and located in the copper nodule-arranged areas, in which the copper nodules are not located in the copper nodule-free areas, and the copper nodules in each copper nodule-arranged area are arranged and formed along a direction on the micro-rough surface; wherein, in the micro-rough surface of 120 square micrometers ( ⁇ m 2 ), the number of the copper nodule-free areas is 5 or higher, each copper nodule-free area has a size of 62500 square nanometers (nm 2 ) or higher, each copper nodule-arranged area has a length of 300 nanometers (nm) to 2500 nm, the copper no
  • the present invention not only gives the desired peel strength between the micro-roughened electrodeposited copper foil and the resin substrate, but also inhibits or reduces the insertion loss of the copper clad laminate in high-frequency transmission, thereby promoting the high-frequency signal transmission efficiency of the electronic products comprising the micro-roughened electrodeposited copper foil.
  • the term “the micro-rough surface of 120 ⁇ m 2 ” refers to the size of a specific area on the micro-rough surface of the micro-roughened electrodeposited copper foil, not to the real size of the micro-rough surface.
  • the micro-rough surface of the micro-roughened electrodeposited copper foil is observed by a scanning electron microscope (SEM) with a magnification of 10,000 ⁇ , and the image shown in each SEM image corresponds to an area of 12.7 micrometers (m) ⁇ 9.46 ⁇ m, which is approximately 120 ⁇ m 2 .
  • the structural feature described as “in the micro-rough surface of 120 ⁇ m 2 , the number of the copper nodule-free areas is 5 or higher, and each copper nodule-free area has a size of 62500 nm 2 or higher” in the disclosure refers to the number of the copper nodule-free areas with the specific size in the specific range of the micro-rough surface.
  • the size of the multiple copper nodule-free areas is 62500 nm 2 or higher, but the sizes of the multiple copper nodule-free areas are not limited to be the same. In other words, the copper nodule-free areas can have optionally the same or different sizes. For example, part of the copper nodule-free areas may have a size equal to 62500 nm 2 , and another part of the copper nodule-free areas may have a size of larger than 62500 nm 2 . In an embodiment, the size of the copper nodule-free areas may be 250 nm ⁇ 250 nm, but not limited thereto.
  • the number of the copper nodule-free areas having a size of 62500 nm 2 or higher can be 5 or more (inclusive).
  • the number of the copper nodule-free areas having a size of 62500 nm 2 or higher can be 5 to 100 or more, 10 to 100 or more, even more.
  • each copper nodule-free area can be 250 nm ⁇ 250 nm or higher; namely, each copper nodule-free area can be an approximate square area. In another embodiment, the size of each copper nodule-free area can be 500 nm ⁇ 250 nm or higher; namely, each copper nodule-free area can be an approximate rectangular area. In the micro-rough surface of 120 ⁇ m 2 , the number of the copper nodule-free areas having a size of 500 nm ⁇ 250 nm or higher can be 10 to 50. In another embodiment, the size of part of the copper nodule-free areas can be 250 nm ⁇ 250 nm or higher, and the size of another part of the copper nodule-free areas can be 500 nm ⁇ 250 nm or higher.
  • the copper nodules in each copper nodule-arranged area are arranged and formed along a direction on the micro-rough surface.
  • the copper nodules in each copper nodule-arranged area can be optionally arranged side-by-side and formed along the direction on the micro-rough surface.
  • the copper nodules in each copper nodule-arranged area when the copper nodules in each copper nodule-arranged area are side-by-side arranged and formed along the direction on the micro-rough surface, the copper nodules are arranged closely adjacent to each other and formed along the direction on the micro-rough surface; and in another embodiment, when the copper nodules in each copper nodule-arranged area are not arranged side-by-side but formed along the direction on the micro-rough surface, the copper nodules are arranged spaced apart and formed along the direction on the micro-rough surface.
  • the copper nodules in part of the copper nodule-arranged areas are side-by-side arranged and formed along the direction on the micro-rough surface, and the copper nodules in another part of the copper nodule-arranged areas are not side-by-side arranged but formed along the direction on the micro-rough surface.
  • part of the copper nodules in a copper nodule-arranged area are side-by-side arranged and formed along the direction on the micro-rough surface, and another part of the copper nodules in the copper nodule-arranged area are not side-by-side arranged but formed along the direction on the micro-rough surface.
  • the length of a copper nodule-arranged area is the sum of the width values of multiple copper nodules having different or different sizes in this area.
  • the length of each copper nodule-arranged area can be 300 nm to 2500 nm, or 500 nm to 2500 nm.
  • the mean width of the copper nodules in each copper nodule-arranged area can be 10 nm to 100 nm, 100 nm to 150 nm, or 150 nm to 280 nm.
  • the copper nodules in each copper nodule-arranged area have a mean width of 10 nm to 200 nm. More preferably, the copper nodules in each copper nodule-arranged area have a mean width of 50 nm to 200 nm.
  • the number of the copper nodules in each copper nodule-arranged area can be 3 to 6, or 7 to 15, or 16 to 50. Preferably, the number of the copper nodules in each copper nodule-arranged area is 3 to 10.
  • the roughness (Rz, within JIS94) of the micro-roughened electrodeposited copper foil can be 3.0 ⁇ m or lower, 2.0 ⁇ m or lower, 1.5 ⁇ m or lower, 1.2 ⁇ m or lower, 1.0 ⁇ m or lower, 0.7 ⁇ m or lower, or 0.5 ⁇ m or lower.
  • the Rz of the micro-roughened electrodeposited copper foil can be 1.2 ⁇ m to 2.0 ⁇ m.
  • the Rz of the micro-roughened electrodeposited copper foil can be 1.4 ⁇ m to 2.5 ⁇ m.
  • the Rz of the micro-roughened electrodeposited copper foil can be 1.0 ⁇ m to 1.5 ⁇ m.
  • the thickness of the micro-roughened electrodeposited copper foil can be 5 ⁇ m to 210 ⁇ m, but not limited thereto.
  • the present invention provides a micro-roughened electrodeposited copper foil comprising a micro-rough surface, wherein the micro-rough surface has an Rlr value of 1.05 to 1.60.
  • the present invention provides a micro-roughened electrodeposited copper foil comprising a micro-rough surface, wherein the micro-rough surface has an Sdr value of 0.01 to 0.08.
  • the present invention not only gives the desired peel strength between the micro-roughened electrodeposited copper foil and resin substrate, but also inhibits or reduces the insertion loss of the copper clad laminate in high-frequency transmission, thereby promoting the high-frequency signal transmission efficiency of the electronic products comprising the micro-roughened electrodeposited copper foil.
  • the micro-roughened electrodeposited copper foil of the present invention also has the above-mentioned surface profile: the micro-rough surface of the micro-roughened electrodeposited copper foil also has multiple copper nodule-free areas and multiple copper nodule-arranged areas; part of the copper nodule-free areas are dispersed among the copper nodule-arranged areas; multiple copper nodules are formed on the micro-rough surface and located in the copper nodule-arranged areas, not located in the copper nodule-free areas; and the copper nodules in each copper nodule-arranged area are arranged and formed along a direction on the micro-rough surface; and, in the micro-rough surface of 120 ⁇ m 2 , the number of the copper nodule-free areas is 5 or higher, each copper nodule-free area has a size of 62500 nm 2 or higher, each copper nodule-arranged area has a length of 300 nm to 2500 nm,
  • the micro-rough surface has an Rlr value of 1.10 to 1.30. More preferably, the micro-rough surface has an Rlr value of 1.10 to 1.28.
  • Rlr refers to an expanded length ratio, i.e., the length ratio of the surface profile of an object per unit length. A higher Rlr value indicates that the surface profile is more uneven, and the surface is completely flat when the Rlr value is equal to 1.
  • the micro-rough surface has an Sdr value of 0.01 to 0.08. More preferably, the micro-rough surface has an Sdr value of 0.010 to 0.023.
  • Sdr refers to an expanded interfacial area ratio, i.e., the increment ratio of the projected area of an object per unit area.
  • the surface is completely flat when the Sdr value is equal to 0.
  • the present invention also provides a copper clad laminate comprising the above-mentioned micro-roughened electrodeposited copper foil and a substrate, wherein the substrate and the micro-roughened electrodeposited copper foil are laminated.
  • the micro-roughened electrodeposited copper foil of the present invention when used, since the micro-rough surface of the micro-roughened electrodeposited copper foil has specific surface profile and/or characteristics, the peel strength between the micro-roughened electrodeposited copper foil and the resin substrate in the copper clad laminate meets the industry standard, and the insertion loss of the copper clad laminate in high-frequency transmission can be inhibited or reduced as much as possible, thereby promoting the high frequency signal transmission efficiency of the high-frequency high-speed electronic products comprising the copper clad laminate.
  • the copper clad laminate comprising the micro-roughened electrodeposited copper foil of the present invention can be applied to the fifth generation mobile networks (5G) to achieve the goal of high-frequency high-speed transmission.
  • 5G fifth generation mobile networks
  • the peel strength between the micro-roughened electrodeposited copper foil and the substrate in the copper clad laminate can be 2.5 pounds per inch (lb/in) or higher, which meets the industry standard. Furthermore, the peel strength between the micro-roughened electrodeposited copper foil and the substrate in the copper clad laminate can be 3.0 lb/in to 5.5 lb/in.
  • the insertion loss at 4 GHz of the copper clad laminate can be ⁇ 0.26 dB/in to ⁇ 0.32 dB/in; more preferably, the insertion loss at 4 GHz of the copper clad laminate can be ⁇ 0.27 dB/in to ⁇ 0.32 dB/in. Even more preferably, the insertion loss at 4 GHz of the copper clad laminate can be ⁇ 0.27 dB/in to ⁇ 0.30 dB/in.
  • the insertion loss at 8 GHz of the copper clad laminate can be ⁇ 0.41 to ⁇ 0.51 dB/in; more preferably, the insertion loss at 8 GHz of the copper clad laminate can be ⁇ 0.43 dB/in to ⁇ 0.51 dB/in. Even more preferably, the insertion loss at 8 GHz of the copper clad laminate can be ⁇ 0.43 to ⁇ 0.48 dB/in.
  • the insertion loss at 12.89 GHz of the copper clad laminate can be ⁇ 0.57 to ⁇ 0.73 dB/in; more preferably, the insertion loss at 12.89 GHz of the copper clad laminate can be ⁇ 0.61 dB/in to ⁇ 0.73 dB/in. Even more preferably, the insertion loss at 12.89 GHz of the copper clad laminate can be ⁇ 0.61 dB/in to ⁇ 0.67 dB/in.
  • the insertion loss at 16 GHz of the copper clad laminate can be ⁇ 0.67 to ⁇ 0.83 dB/in; more preferably, the insertion loss at 16 GHz of the copper clad laminate can be ⁇ 0.71 dB/in to ⁇ 0.83 dB/in. Even more preferably, the insertion loss at 16 GHz of the copper clad laminate can be ⁇ 0.71 dB/in to ⁇ 0.79 dB/in.
  • the substrate can have a low dielectric constant and/or a low dissipation factor (Df).
  • the substrate can be a resin substrate (i.e., prepreg, which is semi-cured), which is obtained by impregnating a base body in a synthetic resin and curing the resin-impregnated base body.
  • the base body may be a phenolic cotton paper, a cotton paper, a resin fiber fabric, a resin fiber non-woven fabric, a glass board, a glass woven fabric, or a glass non-woven fabric, but not limited thereto;
  • the synthetic resin may be an epoxy resin, a polyester resin, a polyimide resin, a cyanate ester resin, a bismaleimide triazine resin, polyphenylene ether resin, or phenol resin, but not limited thereto; and the synthetic resin may form a mono-layer or a multiple-layer structure on the base body.
  • the product numbers of the commercial resin substrates may be TU933 + , TU863 + , EM890, EM891(K), EM891, IT958G, IT968, IT988G, IT150DA, S7040G, S7439G, Synamic 6GX, Synamic 8G, MEGTRON 4, MEGTRON 6 or MEGTRON 7, but not limited thereto.
  • FIG. 1A is a scanning electron microscope (SEM) image of the micro-roughened electrodeposited copper foil of Example 1, with a magnification of 5,000 ⁇ .
  • FIG. 1B and FIG. 1C are marked SEM images for illustrating the structural features of the micro-roughened electrodeposited copper foil of Example 1, in which FIG. 1B is a SEM image with a magnification of 10,000 ⁇ , and the copper nodule-arranged areas are marked thereon; and FIG. 1C is a SEM image with a magnification of 10,000 ⁇ , and the multiple copper nodule-free areas are marked thereon.
  • FIG. 2A is a SEM image of the micro-roughened electrodeposited copper foil of Example 2, with a magnification of 5,000 ⁇ .
  • FIG. 2B and FIG. 2C are marked SEM images for illustrating the structural features of the micro-roughened electrodeposited copper foil of Example 2, in which FIG. 2B is a SEM image with a magnification of 10,000 ⁇ , and the copper nodule-arranged areas are marked thereon; and FIG. 2C is a SEM image with a magnification of 10,000 ⁇ , and the multiple copper nodule-free areas are marked thereon.
  • FIG. 3A is a SEM image of the micro-roughened electrodeposited copper foil of Example 3, with a magnification of 5,000 ⁇ .
  • FIG. 3B and FIG. 3C are marked SEM images for illustrating the structural features of the micro-roughened electrodeposited copper foil of Example 3, in which FIG. 3B is a SEM image with a magnification of 10,000 ⁇ , and the copper nodule-arranged areas are marked thereon; and FIG. 3C is a SEM image with a magnification of 10,000 ⁇ , and the multiple copper nodule-free areas are marked thereon.
  • FIG. 4 is a SEM image of the commercial copper foil of the Comparative Example, with a magnification of 10,000 ⁇ .
  • FIG. 5 is a schematic diagram of the 8-layer laminate of Delta L for the insertion loss test.
  • a copper electrolyte comprising copper ions (Cu 2+ ) of about 65 grams per liter (g/L) to 100 g/L, sulfuric acid (H 2 SO 4 ) of about 85 g/L to 105 g/L, chloride ions (Cl ⁇ ) of 1.0 ppm to 30 ppm was prepared, and the resulting copper electrolyte was introduced into a raw foil electrolysis equipment with a rotating cathode roll and an insoluble anode, and a current having a current density of 30 amperes per square decimeter (A/dm 2 ) to 60 A/dm 2 was applied to the cathode roll and an insoluble anode to produce a very low profile (VLP) raw foil at a liquid temperature of 50° C. to 58° C., and the VLP raw foil was continuously wound on a guiding roll.
  • Cu 2+ copper ions
  • H 2 SO 4 sulfuric acid
  • Cl ⁇ chloride ions
  • the VLP raw foil was sent at a production speed of 10 meters per minute (m/min) by guiding rolls into the 11 connecting tanks shown in Table 1, and sequentially subjected to the following treatments: one roughening treatment, two curing treatments, two roughening treatments, two curing treatments, one nickel (Ni) electroplating treatment, one zinc (Zn) electroplating treatment, one chromium (Cr) electroplating treatment, and one silanization treatment, to obtain a micro-roughened electrodeposited copper foil having a thickness of about 35 ⁇ m.
  • each of the 11 tanks corresponded to a surface treatment listed in Table 1.
  • the parameters of the preparation processes of the previous 10 tanks, including the main metal ion and its concentration in the electroplating solution, the chloride ion concentration and trace metal concentration in the electroplating solution, the acid and its concentration in the electroplating solution, the liquid temperature and pH value of the electroplating solution, and the treatment time were shown in Table 1.
  • the silane coupling agent used for the silanization treatment was (3-glycidoxypropyl) trimethoxysilane coupling agent with a concentration of 5 g/L to 7 g/L, and the parameters of silanization including the trace metal concentration, the liquid temperature and pH value of the treatment solution, and the treatment time for the silanization treatment tank were also shown in Table 1.
  • the trace metal present in the electroplating solution might be in the form of Ni +2 , Pd +2 , Ag + , or W +6 .
  • the trace metal In the first (1 st ) to seventh (7 th ), ninth (9 th ), and tenth (10 th ) tanks, the trace metal might be Ni +2 , Pd +2 , Ag + , or W +6 ; in the eighth (8 th ) tank, the trace metal might be Pd +2 , Ag + , or W +6 ; and in the ninth (9 th ) tank, the trace metal might be Pd +2 , Ag + , or W +6 .
  • the main difference in the surface treatments between the micro-roughened electrodeposited copper foils of Examples 1 to 3 was the current density of each surface treatment, and this parameter of the preparation processes was shown in Table 2.
  • the deviation of the current density for each surface treatment was controlled within ⁇ 10%.
  • Comparative Example was the very low profile copper foil produced by the Furukawa Electric Co., Ltd., with a production number of FT1-UP, which was a commercial copper foil having a weight of 1 ounce (oz) and a thickness of about 35 ⁇ m.
  • micro-roughened electrodeposited copper foils of Examples 1, 2 and 3 were observed with a magnification of 5,000 ⁇ , and the SEM images taken were shown in FIGS. 1A, 2A and 3A , respectively.
  • the commercial copper foil of the Comparative Example was observed with a magnification of 10,000 ⁇ , and the SEM image taken were shown in FIG. 4 .
  • the surface profile of the micro-roughened electrodeposited copper foil of the present invention was similar to the structure of gum and teeth, which was different from the evenly dispersed copper nodules in the commercial copper foil shown in FIG. 4 .
  • FIGS. 1B and 1C which were originated from the same SEM image with a magnification of 10,000 ⁇ , were used, in which the structural features of the copper nodule-arranged areas were marked in FIG. 1B , and the structural features of the copper nodule-free areas were marked in FIG. 1C .
  • FIGS. 2B and 2C originated from the same SEM image with a magnification of 10,000 ⁇
  • FIGS. 3B and 3C originated from the same SEM image with a magnification of 10,000 ⁇ were used for the surface profile analysis.
  • the micro-roughened electrodeposited copper foils of Examples 1 to 3 had a micro-rough surface and multiple copper nodules, in which the micro-rough surface had multiple copper nodule-arranged areas and multiple copper nodule-free areas, part of the copper nodule-free areas were dispersed among the copper nodule-arranged areas, the copper nodule-free areas were arranged adjacent to the copper nodule-arranged areas, the copper nodules were formed on the micro-rough surface and located in the copper nodule-arranged areas, the copper nodules were not located in the copper nodule-free areas (i.e., each copper nodule-free area substantively had no copper nodule), the copper nodules in each copper nodule-arranged area were arranged and formed along a direction on the micro-rough surface, and the direction of the arranged copper nodules was approximately
  • the areas adjacent to the copper nodule-arranged areas were pointed and marked with full lines in FIGS. 1B, 2B and 3B , in which multiple copper nodules were formed on the micro-rough surface in each copper nodule-arranged area, and the multiple copper nodules in each copper nodule-arranged area were arranged continuously side-by-side and formed on the micro-rough surface.
  • the copper nodule-arranged areas were designated as the number (No.) 01 to 10.
  • the No. 1B-01 in FIG. 1B corresponded to the measurement result of No. 01 of Example 1 shown in Table 3
  • the No. 1B-02 in FIG. 1B corresponded to the measurement result of No.
  • Example 1 Ten copper nodule-arranged areas (Nos. 01 to 10) in the micro-roughened electrodeposited copper foils of Examples 1, 2 to 3 were randomly selected and measured in accordance with FIGS. 1B, 2B and 3B , respectively.
  • the length of each copper nodule-arranged area, the number of the copper nodules in each copper nodule-arranged area, the mean width of the copper nodules of each copper nodule-arranged area were measured, and the results were listed in Table 3.
  • the individual length of the above-mentioned 10 copper nodule-arranged areas were measured and averaged to obtain the mean length of the multiple copper nodule-arranged areas of Example 1.
  • the individual number of the copper nodules of the above-mentioned 10 copper nodule-arranged areas were measured and averaged to obtain the mean number of the multiple copper nodules of Example 1.
  • the mean widths of the copper nodules of the above-mentioned 10 copper nodule-arranged areas were measured and averaged to obtain the mean of the mean widths of the multiple copper nodules of Example 1. The calculation results were also listed in Table 3.
  • the copper nodule-free areas having a size of 250 nm ⁇ 250 nm (62,500 nm 2 ) were marked by squares, and the copper nodule-free areas having a size of 500 nm ⁇ 250 nm (125,000 nm 2 ) were marked by rectangles in FIGS. 1C, 2C and 3C , in which each copper nodule-free area substantively had no copper nodule.
  • the numbers of copper nodule-free areas in different sizes were listed in Table 4, in which the number of copper nodule-free areas of 250 nm ⁇ 250 nm is the sum of the number of squares and 2 ⁇ the number of rectangles marked in the figures.
  • the micro-roughened electrodeposited copper foils of Examples 1, 2 and 3 and the commercial copper foil of the Comparative Example were used as the specimens, and Sdr values of randomly selected five points on each specimen were measured by the ISO 25178-2012 method using a contact-free scanning laser microscope (purchased from Keyence Corporation, with the controller of VK-X150K and a measurement head of VK-X160K) with a magnification of objective lens of 50 ⁇ (X50), an L-filter ( ⁇ c) of 0.2 mm, and an S-filter ( ⁇ s) of 2 ⁇ m, and the resulting values were averaged to obtain the mean Sdr.
  • the micro-roughened electrodeposited copper foils of Examples 1, 2 and 3 and the commercial copper foil of the Comparative Example were used as the specimens and Rlr values of randomly selected five points of each specimen were measured by the contact-free scanning laser microscope (purchased from Keyence Corporation, with the controller of VK-X150K, a measurement head of VK-X160K) with a magnification of objective lens of 50 ⁇ (X50), an L-filter ( ⁇ c) of 0, and an S-filter ( ⁇ s) of 0, and the resulting values were averaged to obtain the mean Rlr.
  • any of the micro-roughened electrodeposited copper foils of Examples 1, 2, 3 and the commercial copper foil of the Comparative Example, and the prepreg purchased from Elite Material Co. Ltd., with a product No. of EM890) were used to prepare an 8-layer laminate of Delta L as shown in FIG. 5 .
  • the laminates were prepared and their insertion loss was tested according to the Delta L methodology provided by INTEL.
  • the test coupon preparation and the testing method met the standards of the Delta L methodology.
  • the copper clad laminates of Examples 1C, 2C, 3C and the Comparative Example C were used as the test coupons for testing the insertion loss.
  • Example 3 when the micro-roughened electrodeposited copper foil of Example 3 was applied to the copper clad laminate, it could further inhibit the signal loss of the copper clad laminate at a high frequency, and promote the effect and quality of the follow-up products using the copper clad laminate.
  • the copper clad laminate comprising any of the micro-roughened electrodeposited copper foils of Examples 1 to 3 could comprehensively inhibit or reduce the insertion loss of the copper clad laminate at a high frequency (4 GHz, 8 GHz, 12.89 GHz, and 16 GHz) under the premise that the desired peel strength between the copper foil and the resin substrate is maintained, thereby promoting the high-frequency transmission efficiency.
  • the present invention could give the desired peel strength, and promote the effect and quality of the follow-up products comprising the copper clad laminate.
  • the present invention can comprehensively inhibit or reduce the insertion loss of the copper clad laminate in high-frequency transmission resulted from the copper foil under the premise that the desired peel strength between the copper foil and the resin substrate is maintained by controlling the surface profile and surface characteristics of the micro-roughened electrodeposited copper foil, thereby promoting the efficiency of high-frequency signal transmission of the electronic products.

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