CN115413119A - Surface-treated copper foil and copper foil substrate - Google Patents
Surface-treated copper foil and copper foil substrate Download PDFInfo
- Publication number
- CN115413119A CN115413119A CN202110764339.9A CN202110764339A CN115413119A CN 115413119 A CN115413119 A CN 115413119A CN 202110764339 A CN202110764339 A CN 202110764339A CN 115413119 A CN115413119 A CN 115413119A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- treated
- layer
- crystal plane
- treated copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
A surface-treated copper foil comprising a treated surface, wherein the root-mean-square height of the treated surface is 0.20 to 1.50 μm, and the aspect ratio of the surface properties of the treated surface is 0.65 or less. When the surface-treated copper foil is heated in an environment of 200 ℃ for 1 hour, the ratio of the integrated intensity of the diffraction peak of the (111) crystal face of the treated face to the sum of the integrated intensities of the diffraction peaks of the (111) crystal face, the (200) crystal face and the (220) crystal face is at least 60%.
Description
Technical Field
The present invention relates to a copper foil, and more particularly to a surface-treated copper foil and a copper foil substrate thereof.
Background
With the trend of electronic products towards being light and thin and transmitting high frequency signals, the demand for copper foil and copper foil substrate is increasing. Generally, the copper conductive traces of the copper foil substrate are carried by the insulating carrier, and the electrical signals can be transmitted to a predetermined area along a predetermined path by the layout design of the conductive traces. In addition, for the copper foil substrate used for transmitting high frequency electric signals (for example, higher than 10 GHz), the conductive traces of the copper foil substrate must be further optimized to reduce signal transmission loss (signal transmission loss) caused by skin effect. The skin effect means that as the frequency of the electrical signal increases, the transmission path of the current is more concentrated on the surface of the conductive wire, for example, the surface of the conductive wire close to the carrier. In order to reduce the signal transmission loss caused by the skin effect, it is a conventional practice to planarize the surface of the conductive wire in the copper foil substrate adjacent to the carrier as much as possible. In addition, in order to maintain the adhesion between the surface of the conductive wire and the carrier board, a reverse treated copper foil (RTF) may be used to fabricate the conductive wire. The reverse treated copper foil is a copper foil whose roll surface (dry side) is subjected to a roughening treatment process.
Even though the above method can reduce the signal transmission loss generated by the copper foil substrate, when the surface of the conductive wire is too flat, the adhesion between the conductive wire and the carrier is still reduced, so that the conductive wire in the copper foil substrate is easily peeled off from the surface of the carrier, and the electrical signal cannot be transmitted to the predetermined area along the predetermined path.
Therefore, there is still a need to provide a surface-treated copper foil and a copper foil substrate to solve the disadvantages and shortcomings of the prior art.
Disclosure of Invention
In view of the above, the present invention provides an improved surface-treated copper foil and a copper foil substrate, which solve the disadvantages of the prior art.
According to an embodiment of the present invention, there is provided a surface-treated copper foil including a treated surface, wherein a root-mean-square height of the treated surface is 0.20 to 1.50 μm, and a surface aspect ratio of the treated surface is 0.65 or less. When the surface-treated copper foil is heated in an environment of 200 ℃ for 1 hour, the ratio of the integrated intensity of the diffraction peak of the (111) crystal face of the treated face to the sum of the integrated intensities of the diffraction peaks of the (111) crystal face, the (200) crystal face and the (220) crystal face is at least 60%.
According to another embodiment of the present invention, a copper clad laminate is provided, which includes a carrier and a surface-treated copper foil disposed on at least one surface of the carrier. The surface treatment layer is arranged between the main copper foil and the carrier plate, the surface treatment layer comprises a treatment surface facing the carrier plate, the root-mean-square height of the treatment surface is 0.20-1.50 mu m, the surface property length-width ratio of the treatment surface is less than 0.65, and the ratio of the diffraction peak integral intensity of the (111) crystal face of the treatment surface to the sum of the diffraction peak integral intensities of the (111) crystal face, the (200) crystal face and the (220) crystal face is at least 60%.
According to the above embodiment, when the root mean square height of the treated surface of the surface-treated copper foil is 0.20 to 1.50 μm, the aspect ratio of the surface property of the treated surface is 0.65 or less, and when the surface-treated copper foil is heated at 200 ℃ for 1 hour, the ratio of the integrated intensity of the diffraction peak of the (111) crystal plane of the treated surface to the sum of the integrated intensities of the diffraction peaks of the (111) crystal plane, the (200) crystal plane, and the (220) crystal plane is at least 60%, when the surface-treated copper foil is subsequently bonded to the carrier plate, the adhesion and reliability between the treated surface and the carrier plate can be maintained, and the degree of signal transmission loss can be kept low, thereby satisfying the needs of the industry for the surface-treated copper foil and the copper foil substrate.
Drawings
Fig. 1 is a schematic cross-sectional view of a surface-treated copper foil according to an embodiment of the present invention.
Fig. 2 is a schematic diagram of a stripline (stripline) according to an embodiment of the present invention.
The reference numerals are explained below:
100: surface treatment of copper foil; 100A: processing the dough; 110: a main body copper foil; 110A: a first side; 110B: a second face; 112a: a first surface treatment layer; 112b: a second surface treatment layer; 114: a coarsening layer; 116a: a first passivation layer; 116b: a second passivation layer; 118a: a first antirust layer; 118b: second antirust layer 120: a coupling layer; 300: a strip line; 302: a wire; 304: a dielectric body; 306-1: a ground electrode; 306-2: a ground electrode; h: thickness; t: thickness; w: width.
Detailed Description
Hereinafter, embodiments of the surface-treated copper foil and the copper foil substrate are described in detail so that those skilled in the art can implement the present invention. Reference is made to the accompanying drawings, which form a part hereof. Although the embodiments of the present invention are disclosed below, the present invention is not limited thereto, and those skilled in the art can make modifications without departing from the spirit and scope of the present invention. The methods used in the examples and experimental examples were conventional unless otherwise specified.
The meaning of the terms "in 8230, above" and "above 8230"; etc. in the present invention should be interpreted in the broadest way so that the terms "in 8230, above" and "above 8230, etc. refer not only to being directly on something but also to being on something with an intermediate feature or layer in between, and" on 8230, above "or" above 8230, etc. refer not only to being on or above something, but also to being on or above something without an intermediate feature or layer in between (i.e. directly on something).
In addition, unless indicated to the contrary, the numerical parameters set forth in the following specification and claims are approximations that may vary depending upon the desired properties or requirements, or at least the numerical values set forth in the specific figures disclosed and the typical carry-over approach is used to interpret each numerical parameter. Ranges can be expressed herein as from one end to the other or between two ends. All ranges in this disclosure are inclusive of the endpoints unless specifically stated otherwise.
It is understood that features of the various embodiments described below may be interchanged, recombined, or mixed with one another to form additional embodiments without departing from the spirit of the invention.
The surface-treated copper foil described herein includes a treated surface that can face and be attached to a carrier when the surface-treated copper foil is subsequently laminated to the carrier.
The surface treated copper foil may include a bulk copper foil and an optional surface treatment layer. The bulk copper foil may be formed by an electrodeposition (or electrolytic, electrodeposition, electroplating) process, which may have two oppositely disposed roll surfaces (dry side) and a deposited side (deposited side). Optionally, a surface treatment layer can be disposed on at least one of the roll side and the deposition side of the bulk copper foil. The surface treatment layer may be a single layer structure or a multi-layer stacked structure. For example, the surface treatment layer may be a multi-layer stack including a plurality of sub-layers, and each surface treatment layer may be disposed on the roll surface and the deposition surface of the bulk copper foil, respectively, but is not limited thereto. The sub-layer in each surface treatment layer may be selected from the group consisting of a roughening layer, a passivation layer, a rust preventive layer, and a coupling layer, but is not limited thereto.
In the surface-treated copper foil according to the embodiment of the present invention, the root mean square height (Sq) of the treated surface may be 0.20 to 1.50 μm, and the surface aspect ratio (Str) of the treated surface may be 0.65 or less. Further, when the surface-treated copper foil is heated in an environment of 200 ℃ for 1 hour, the ratio of the integrated intensity of the diffraction peak of the (111) crystal plane of the treated plane to the sum of the integrated intensities of the diffraction peaks of the three of the (111) crystal plane, the (200) crystal plane and the (220) crystal plane may be at least 60%. Since the treated surface of the surface-treated copper foil is bonded to the carrier in the subsequent process, the peel strength between the surface-treated copper foil and the carrier can be improved and the surface-treated copper foil can pass the reliability test of the solder bath compared with the conventional surface-treated copper foil by controlling the root mean square height (Sq) and the surface property aspect ratio (Str) of the treated surface of the surface-treated copper foil within the above numerical range. In addition, when the ratio of the integrated intensity of the diffraction peak of each crystal plane is further controlled to the above range, a lower transmission loss of the high frequency signal can be further achieved.
The root mean square height (Sq) refers to the root mean square height of each point of a surface in a specific range, which corresponds to the standard deviation of the height. Since the rms height is the rms of the calculated height, it is more sensitive to changes in height. According to an embodiment of the present invention, the root mean square height (Sq) of the treated surface of the surface-treated copper foil is 0.20 μm to 1.50 μm, for example, 0.20 μm, 0.50 μm, 0.60 μm, 0.80 μm, 1.10 μm, 1.50 μm, or any value thereof. Preferably 0.21 μm to 1.44 μm, more preferably 0.60 μm to 1.25 μm.
The "surface aspect ratio (Str)" refers to an index for measuring the uniformity of a surface texture (surface texture) of a surface in each direction, i.e., the degree of isotropy (or "isotropy") and anisotropy (or "anisotropy") of the surface. The surface aspect ratio (Str) falls between 0 and 1, and when the surface aspect ratio (Str) is 0 or approaches 0, the surface texture of the surface is significantly anisotropic, and a highly regular surface topography is represented. For example, when the surface aspect ratio (Str) is 0, adjacent peaks and valleys may each appear as stripes and be arranged parallel to each other. In contrast, when the surface aspect ratio (Str) is 1 or approaches 1, the surface texture representing the surface is strongly isotropic, exhibiting a highly random surface topography. For example, when the surface texture aspect ratio (Str) is 1, the peaks and valleys appear to be randomly arranged. According to an embodiment of the present invention, the surface aspect ratio (Str) of the treated surface of the surface-treated copper foil is 0.65 or less, for example, 0.05, 0.15, 0.25, 0.35, 0.45, 0.55, 0.65, or any value thereof. Preferably 0.10 to 0.65, more preferably 0.60 or less.
The integrated intensities of the diffraction peaks of the copper (111) plane, the copper (200) plane, and the copper (220) plane are measured by low grazing angle X-ray diffraction (the grazing angle may be 0.5 ° to 1.0 °) on the treated surface of the surface-treated copper foil, and are used to characterize the percentage of each plane in the surface region of the surface-treated copper foil (for example, a region having a depth of 0 μm to 1 μm from the treated surface). Therefore, by low-grazing-angle X-ray diffraction, the crystal plane characteristics of the surface region of the copper foil can be exhibited, not for exhibiting the crystal plane characteristics of the inner region of the copper foil. In addition, since the copper (111) crystal plane is less likely to degrade the electric signal when transmitting the high-frequency electric signal, the degree of loss of the high-frequency electric signal can be reduced when the occupation ratio of the copper (111) crystal plane is increased. On the other hand, since the ratio of crystal planes of the bulk copper foil of the surface-treated copper foil may vary depending on the temperature and duration of the subsequent heat treatment process (e.g., thermocompression bonding process), the present invention simulates the crystal plane characteristics of the surface-treated copper foil after the thermocompression bonding process by heating the surface-treated copper foil in an environment of 200 ℃ for 1 hour. According to an embodiment of the present invention, after heating the surface-treated copper foil in an environment of 200 ℃ for 1 hour, the ratio of the integrated intensity of the diffraction peak of the (111) crystal plane of the treated surface to the sum of the integrated intensities of the diffraction peaks of the (111) crystal plane, the (200) crystal plane and the (220) crystal plane is at least 60%, preferably 60% to 90%, or the ratio of the integrated intensity of the diffraction peak of the (220) crystal plane of the treated surface to the sum of the integrated intensities of the diffraction peaks of the (111) crystal plane, the (200) crystal plane and the (220) crystal plane of the treated surface may be further less than 16.50%.
Fig. 1 shows an example of the structure of the surface-treated copper foil. Fig. 1 is a schematic cross-sectional view of a surface-treated copper foil according to an embodiment of the present invention. As shown in fig. 1, the surface-treated copper foil 100 includes at least a treated surface 100A, and the surface-treated copper foil 100 includes at least a bulk copper foil 110.
The bulk copper foil 110 may be, for example, an electrolytic copper foil or a rolled copper foil, and the thickness thereof is usually greater than or equal to 6 μm, for example, between 7 and 250 μm, or between 9 and 210 μm, but not limited thereto. In the case where the bulk copper foil 110 is an electrolytic copper foil, the electrolytic copper foil may be formed by an electrodeposition (or electrolytic, electrolytic deposition, electroplating) process. The bulk copper foil 110 has two oppositely disposed first and second sides 110A and 110B. According to an embodiment of the present invention, when the bulk copper foil 110 is an electrolytic copper foil, a roll surface (dry side) of the electrolytic copper foil may correspond to the first surface 110A of the bulk copper foil 110, and a deposition surface (deposited side) of the electrolytic copper foil may correspond to the second surface 110B of the bulk copper foil 110, but is not limited thereto. According to an embodiment of the present invention, when the bulk copper foil 110 is an electrodeposited copper foil and the first side 110A of the bulk copper foil 110 is a roll surface of the electrodeposited copper foil, in forming the electrodeposited copper foil by performing electrodeposition, the roll surface of the electrodeposited copper foil may be affected by the number of grains or the number of grains (grain size number) of a cathode roll of a foil maker, so that the roll surface of the electrodeposited copper foil may exhibit a specific surface topography, such as grinding marks, and the spatial distribution of the grinding marks may exhibit an isotropic (anisotropic) or anisotropic (anisotropic), preferably an anisotropic arrangement.
According to an embodiment of the present invention, the first side 110A and the second side 110B of the bulk copper foil 110 may be respectively provided with other layers, for example, a surface treatment layer, such as a first surface treatment layer 112a, may be provided on the first side 110A, and/or another surface treatment layer, such as a second surface treatment layer 112B, may be provided on the second side 110B. The outer side of the first surface treatment layer 112a can be regarded as a treatment surface 100A of the surface-treated copper foil 100, and the treatment surface 100A contacts the carrier through a subsequent process of pressing the surface-treated copper foil 100 to the carrier. According to other embodiments of the present invention, the first side 110A and the second side 110B of the bulk copper foil 110 may be further provided with other single-layer or multi-layer structures, or the surface treatment layers of the first side 110A and the second side 110B may be replaced with other single-layer or multi-layer structures, or the first side 110A and the second side 110B are not provided with any layer, but not limited thereto. Therefore, in these embodiments, the treated surface 100A of the surface-treated copper foil 100 may not correspond to the outer side surface of the first surface-treated layer 112a, but may correspond to the outer side surface of other single-layer or multi-layer structures, or may correspond to the first surface 110A and the second surface 110B of the bulk copper foil 110, but is not limited thereto.
The first surface treatment layer 112a and the second surface treatment layer 112b may each be a single layer or a stacked layer including a plurality of sublayers. For the case where the first surface treatment layer 112a is a stacked layer, each sub-layer may be selected from the group consisting of the roughening layer 114, the first passivation layer 116a, the first rust preventive layer 118a, and the coupling layer 120; and for the case where the second surface treatment layer 112b is a multi-layer stacked structure including a plurality of sub-layers, each sub-layer may be selected from a group consisting of the second passivation layer 116b and the second rust preventive layer 118 b. The compositions of the first passivation layer 116a and the second passivation layer 116b may be the same as or different from each other, and the compositions of the first rust preventive layer 118a and the second rust preventive layer 118b may be the same as or different from each other.
The roughened layer 114 includes roughened particles (nodule). The roughening particles may be used to enhance the surface roughness of the bulk copper foil 110, and may be copper roughening particles or copper alloy roughening particles. In order to prevent the roughening particles from peeling off from the bulk copper foil 110, the roughening layer 114 may further include a covering layer disposed on the roughening particles to cover the roughening particles. According to an embodiment of the present invention, in the case that the roughening particles in the roughening layer 114 are formed on the first surface 110A of the bulk copper foil 110 by electrodeposition, the distribution of the roughening particles may be influenced by the surface topography of the bulk copper foil 110 thereunder, such that the roughening particle arrangement exhibits an isotropic or anisotropic arrangement. For example, when the surface topography of the first surface 110A of the bulk copper foil 110 exhibits anisotropic alignment, the roughening particles correspondingly disposed on the surface may also exhibit anisotropic alignment. According to an embodiment of the present invention, since the sum of the thicknesses of the first passivation layer 116a, the first anti-rust layer 118a and the coupling layer 120 in the first surface treatment layer 112a is much smaller than the thickness of the roughening layer 114, the surface topography of the treated surface 100A of the copper foil 100, such as root mean square height (Sq) and surface aspect ratio (Str), is mainly affected by the roughening layer 114. In addition, the surface roughness of the treated surface 100A of the surface-treated copper foil 100 can be adjusted by adjusting the number and size of the roughening particles in the roughening layer 114. For example, the type and arrangement of the roughening particles and the covering layer formed by electrolytic deposition can be adjusted by adjusting the type, concentration and/or current density of the additive in the electrolyte, but not limited thereto.
The passivation layers, such as the first passivation layer 116a and the second passivation layer 116b, may be the same or different in composition, such as a metal layer or a metal alloy layer. Wherein the metal layer may be selected from, but not limited to, nickel, zinc, chromium, cobalt, molybdenum, iron, tin, and vanadium, such as: a nickel layer, a nickel-zinc alloy layer, a zinc-tin alloy layer or a chromium layer. In addition, the metal layer and the metal alloy layer may be a single layer or a multi-layer structure, such as single layers containing zinc and nickel stacked on each other. When the multilayer structure is used, the stacking order of the layers can be adjusted according to the need, and is not limited, for example, a zinc-containing layer is stacked on a nickel-containing layer, or a nickel-containing layer is stacked on a zinc-containing layer. According to an embodiment of the present invention, the first passivation layer 116a is a double-layer structure of a zinc-containing layer and a nickel-containing layer stacked on each other, and the second passivation layer 116b is a single-layer structure of a zinc-containing layer.
The foregoing rust preventive layers, such as the first rust preventive layer 118a and the second rust preventive layer 118b, are coating layers applied to the metal, which can be used for preventing the metal from being deteriorated by corrosion, oxidation, or the like. The rust-preventive layer contains a metal or an organic compound, but is not limited thereto. When the rust inhibiting layer comprises a metal, the metal can be chromium or a chromium alloy, and the chromium alloy can further comprise one selected from the group consisting of nickel, zinc, cobalt, molybdenum, vanadium, and combinations thereof. When the rust preventive layer contains an organic compound, non-limiting examples of organic molecules that can be used to form the organic rust preventive layer include porphyrin groups consisting of porphyrins, porphyrin macrocycles, enlarged porphyrins, contracted porphyrins, linear porphyrin polymers, porphyrin sandwich coordination complexes, porphyrin arrays, 5,10,15,20-tetrakis (4-aminophenyl) -porphyrin-zinc (II), and combinations thereof, benzotriazole, triazine trithiol, and combinations thereof. According to an embodiment of the present invention, both the first antirust layer 118a and the second antirust layer 118b use chromium.
The coupling layer 120 may be made of silane, and may be used to improve adhesion between the surface-treated copper foil 100 and other materials (e.g., substrate film). The coupling layer 120 may be selected from, but is not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 1- [3- (trimethoxysilyl) propyl ] urea, (3-chloropropyl) trimethoxysilane, dimethyldichlorosilane, 3- (trimethoxysilyl) propyl methacrylate, ethyltriacetoxysilane, isobutyltriethoxysilane, N-octyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane), trimethylchlorosilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, ethylene-trimethoxysilane, alkoxysilanes having 1 to 20 carbon atoms, vinylalkoxysilanes having 1 to 20 carbon atoms, (meth) acylsilanes, and combinations thereof, but is not limited thereto.
The surface-treated copper foil 100 may be further processed to form a Copper Clad Laminate (CCL). The copper foil substrate at least comprises a carrier plate and a surface treatment copper foil. The surface treatment copper foil is arranged on at least one surface of the carrier plate and comprises a treatment surface. Wherein, the processing surface of the surface treatment copper foil can face and directly contact the carrier plate.
The carrier plate may be a bakelite plate, a polymer plate, or a glass fiber plate, but is not limited thereto. Examples of the polymer component of the polymer sheet include: epoxy resin, phenol resin, polyester resin, polyimide resin, acryl, formaldehyde resin, bismaleimide triazine resin, cyanate ester resin (cyanate ester resin), fluoropolymer, polyethersulfone, cellulose thermoplastic, polycarbonate, polyolefin, polypropylene, polysulfide, polyurethane, polyimide resin, liquid Crystal Polymer (LCP), polyoxy xylene (PPO). The glass fiber plate may be a prepreg (preprg) formed by impregnating the glass fiber nonwoven fabric with the polymer (e.g., epoxy resin).
The copper foil substrate can be further processed into a printed circuit board, and the steps of the method can include patterning the electrolytic copper foil to form a conductive wire, and blackening the conductive wire. The blackening process is a chemical bath treatment process and may include at least one pretreatment (e.g., microetching or cleaning the surface of the conductive wire).
Hereinafter, the surface-treated copper foil and the method of manufacturing the copper foil substrate will be further exemplarily described. The preparation method comprises the following steps:
(1) Step A
Step a is performed to provide a bulk copper foil, such as an electrolytic copper foil. Electrolytic copper foil, or "bare copper foil", can be formed by electrodeposition (electrodeposition) using a foil-forming machine. Specifically, the foil maker may include at least a roller as a cathode, a pair of insoluble metallic anode plates, and an electrolyte inlet pipe (inlet). Wherein, the roller is a rotatable metal roller, and the surface of the roller is a mirror polished surface. The metal anode plate can be separately and fixedly arranged on the lower half part of the roller so as to surround the lower half part of the roller. The feeding pipe can be fixedly arranged right below the roller and is positioned between the two metal anode plates.
During the electrolytic deposition process, the electrolyte feeding pipe can continuously supply the electrolyte to a position between the roller and the metal anode plate. Copper can be electrodeposited on the roll by applying a current or voltage between the roll and a metallic anode sheet to form a bulk copper foil. In addition, by continuously rotating the roller and peeling the electrolytic copper foil from one side of the roller, a continuous body copper foil can be manufactured. Wherein the surface of the bulk copper foil facing the roll can be referred to as the roll side and the surface of the bulk copper foil facing away from the roll can be referred to as the deposition side. In addition, during the electrodeposition process, since the surface of the cathode roll is slightly oxidized, an uneven surface is generated, thereby reducing the flatness of the roll surface of the bulk copper foil. Therefore, a polishing roll (polish buff) may be further disposed adjacent to the cathode roll so that a contact surface is provided between the cathode roll and the polishing roll. By rotating the cathode roller and the polishing roller in opposite directions, the oxide layer on the surface of the cathode roller can be removed by the polishing roller, and the surface flatness of the cathode roller is maintained.
The manufacturing parameter ranges of the bulk copper foil are exemplified as follows:
electrolyte composition and electrolysis condition of raw foil
Copper sulfate (CuSO) 4 ·5H 2 O)：320g/L
Sulfuric acid: 95g/L
Chloride (from hydrochloric acid, RCI Labscan ltd.): 30mg/L (ppm)
Liquid temperature: 50 deg.C
Current density: 70A/dm 2
Thickness of green foil: 35 μm
1.2 cathode roller
The material quality is as follows: titanium (IV)
Surface grain size number (grain size number): 6. 7, 7.5, 9
Polishing roller (1.3)
Model (Nippon Tokushu Kento co., ltd): #500, #1000, #1500, #2000
(2) Step B
In step B, a surface cleaning process is performed on the bulk copper foil to ensure that the surface of the copper foil does not contain contaminants (e.g., oil stains and oxides), and the manufacturing parameters are as follows:
composition and cleaning conditions of cleaning liquid
Copper sulfate: 200g/L
Sulfuric acid: 100g/L
Liquid temperature: 25 deg.C
Dipping time: 5 seconds
(3) Step C
In step C, a roughened layer is formed on the roll surface of the main copper foil. For example, the roughening particles can be formed on the roll surface of the bulk copper foil by electrodeposition. In order to prevent the coarsened particles from falling, a coating layer may be further formed on the coarsened particles. The manufacturing parameter ranges of the roughened layer (including the roughened particles and the cover layer) are exemplified as follows:
< 3.1 parameters for making coarsened particles >
Copper sulfate (CuSO) 4 ·5H 2 O)：150g/L
Sulfuric acid: 100g/L
Titanium sulfate (Ti (SO) 4 ) 2 )：150～750mg/L(ppm)
Sodium tungstate (Na) 2 WO 4 )：50～450mg/L(ppm)
Liquid temperature: 25 deg.C
Current density: 40A/dm 2
Time: 10 seconds
Parameter for making covering layer
Copper sulfate (CuSO) 4 ·5H 2 O)：220g/L
Sulfuric acid: 100g/L
Liquid temperature: 40 deg.C
Current density: 15A/dm 2
Time: 10 seconds
(4) Step D
In step D, passivation layers are formed on the sides of the bulk copper foil, for example, by an electrodeposition process, so as to form passivation layers with a double-layer stacked structure (for example, but not limited to, a nickel-containing layer/a zinc-containing layer) on the sides of the bulk copper foil where the roughening layers are disposed, and passivation layers with a single-layer structure (for example, but not limited to, a zinc-containing layer) on the sides of the bulk copper foil where the roughening layers are not disposed. The manufacturing parameter ranges are exemplified as follows:
electrolyte composition containing nickel layer and electrolysis condition
Nickel sulfate (NiSO) 4 ·7H 2 O)：180g/L
Boric acid (H) 3 BO 3 )：30g/L
Sodium hypophosphite (NaH) 2 PO 2 )：3.6g/L
Liquid temperature: 20 deg.C
Current density: 0.2A/dm 2
Time: 10 seconds
< 4.2 composition of electrolyte containing zinc layer and electrolytic conditions >
Zinc sulfate (ZnSO) 4 ·7H 2 O)：9g/L
Ammonium vanadate ((NH) 4 ) 3 VO 4 )：0.3g/L
Liquid temperature: 20 deg.C
Current density: 0.2A/dm 2
Time: 10 seconds
(5) Step E
In the step E, a rust preventive layer, for example, a chromium-containing layer is formed on the passivation layer on each side of the main copper foil, and the production parameter ranges thereof are exemplified as follows:
electrolyte composition and electrolysis condition of 5.1 chromium-containing layer
Chromium trioxide (CrO) 3 )：5g/L
Liquid temperature: 30 deg.C
Current density: 5A/dm 2
Time: 10 seconds
(6) Step F
And F, forming a coupling layer on one side of the main copper foil provided with the coarsening layer, the passivation layer and the anti-rust layer. For example, after the above-mentioned electrodeposition process is completed, the copper foil is washed with water, but the surface of the copper foil is not dried. And then spraying an aqueous solution containing the silane coupling agent onto the anti-rust layer on the side of the copper foil provided with the roughened layer, so that the silane coupling agent is adsorbed on the surface of the anti-rust layer. Thereafter, the copper foil may be placed in an oven for drying. The manufacturing parameter ranges are exemplified as follows:
parameter of silane coupling agent (6.1)
Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyl trimethoxysilane, KBM-403)
Silane coupling agent concentration of aqueous solution: 0.25wt. -%)
Spraying time: 10 seconds
(7) Step G
In step G, the surface-treated copper foil (including the main copper foil and the surface-treated layers disposed on the respective sides of the main copper foil) formed in the above steps is pressed onto the carrier to form a copper foil substrate. According to an embodiment of the present invention, the copper foil substrate can be formed by hot-pressing the surface-treated copper foil 100 shown in fig. 1 to a carrier.
In order to enable those skilled in the art to practice the present invention, embodiments of the present invention will be described in further detail below to specifically illustrate the surface-treated copper foil and the copper foil substrate of the present invention. It should be noted that the following examples are merely illustrative and should not be construed as limiting the present invention. That is, the materials used in the respective embodiments, the amounts and ratios of the materials, the process flows, and the like can be appropriately changed without departing from the scope of the present invention.
Examples 1 to 16
Examples 1 to 16 are surface-treated copper foils, and the production process thereof includes steps a to F in the above-described production method. The manufacturing parameters of examples 1 to 16, which differ from the above-described manufacturing method, are shown in table 1. In the surface-treated copper foils of examples 1 to 16, a nickel-containing layer, a zinc-containing layer, a chromium-containing layer, and a coupling layer were sequentially formed on the roughened layer, and a zinc-containing layer and a chromium-containing layer were sequentially formed on the side of the main copper foil not provided with the roughened layer, as shown in fig. 1. The thickness of the surface-treated copper foil was 35 μm.
TABLE 1
The results of various tests on the surface-treated copper foils and the corresponding copper foil substrates of the above-described examples 1 to 16 are further described below, for example: root mean square height (Sq), < aspect ratio of surface features (Str), < proportion of crystal plane >, < peel strength >, < reliability >, and < signal transmission loss >. The results of the respective tests are shown in Table 2.
Root mean square height (Sq) and surface aspect ratio (Str)
According to standard ISO 25178-2:2012, the root mean square height (Sdq) and surface aspect ratio (Str) of the treated surface of the surface-treated copper foil were measured by surface texture analysis using a laser microscope (LEXT OLS5000-SAF, olympus). The specific measurement conditions were as follows:
wavelength of light source: 405nm
Magnification of objective lens: 100 times objective lens (MPLAPON-100x LEXT, olympus)
Optical zooming: 1.0 times of
Observation area: 129 μm × 129 μm
Resolution ratio: 1024 pixels × 1024 pixels
Conditions are as follows: automatic tilt elimination function (Auto tilt elimination) of laser microscope
A filter lens: no filter (unfiltered)
Air temperature: 24 + -3 deg.C
Relative humidity: 63 +/-3 percent
Proportion of crystalline surface
The oven temperature was set to 200 ℃. And (3) when the temperature of the oven is 200 ℃, putting the surface-treated copper foil in the oven to carry out heat treatment on the surface-treated copper foil. After the heat treatment for 1 hour, the surface-treated copper foil was taken out of the oven and placed in a room temperature environment. Then, a low grazing angle X-ray diffraction analysis (GIXRD) is performed on the processed surface (i.e., the side where the roughening layer, the passivation layer, the rust-preventive layer, and the coupling layer are disposed) of the surface-treated copper foil to determine the integral intensity of the diffraction peak of the crystal face of the surface-treated copper foil adjacent to the processed surface, such as the roll surface of the bulk copper foil and the integral intensity of the diffraction peak of the copper (111) crystal face, the copper (200) crystal face, and the copper (220) crystal face within a certain depth from the roll surface. The specific measurement conditions were as follows:
the measuring instrument is as follows: x-ray diffraction Analyzer (D8 ADVANCE Eco, bruker Co.)
Grazing angle: 0.8 degree.
Peeling Strength
6 sheets of commercially available resin sheets (S7439G, shengyi Technology co.) each having a thickness of 0.09mm were stacked together to form a resin sheet stacked layer, and the treated side of the surface-treated copper foil (size: 125mm × 25 mm) of any of the above examples was disposed toward the resin sheet stacked layer, followed by pressing both to form a copper foil substrate. The pressing conditions were as follows:
temperature: 200 deg.C
Pressure: 400psi
And (3) laminating time: 120 minutes
Thereafter, the surface-treated copper foil was peeled off from the copper foil substrate at an angle of 90 ° using a universal tester in accordance with JIS C6471. The stripping conditions were as follows:
stripping the instrument: shimadzu AG-I universal tensile machine
Peeling angle: 90 deg. C
Evaluation criteria: the peel strength is required to be higher than 4lb/in
Reliability
6 commercially available resin sheets (S7439G, syTech corp.) each having a thickness of 0.076mm were stacked together to form a resin sheet stack layer, and the treated surface of the surface-treated copper foil of any of the above embodiments was disposed facing the resin sheet stack layer, followed by pressing both to form a copper foil substrate. The pressing conditions were as follows: temperature 200 ℃, pressure 400psi, and press time 120 minutes.
Then, a Pressure Cooker Test (PCT) was performed, conditions in the oven were set to 121 ℃, 2atm, and 100% rh, and the copper foil substrate was placed in the oven for 30 minutes, and then taken out and cooled to room temperature. Then, a solder bath test (solder bath test) was performed, and the copper foil substrate subjected to the pressure cooker test was immersed in a molten solder bath at a temperature of 288 ℃ for 10 seconds.
The solder bath test may be repeated for the same sample, and after each solder bath test is completed, the copper foil substrate may be observed for the presence of any abnormal phenomenon such as blistering (blistering), cracking (crack), or delamination (delaminations), and if any of the above abnormal phenomena occurs, the copper foil substrate may be determined to fail the solder bath test. The results of the measurements are set forth in Table 2. The evaluation criteria were as follows:
a: after more than 50 times of solder bath tests, the copper foil substrate still has no abnormal phenomenon
B: after 10-50 times of solder bath test, the copper foil substrate generates abnormal phenomena
C: after less than 10 times of solder bath tests, the copper foil substrate generates abnormal phenomena
Loss of signal transmission
The surface-treated copper foil of any of the above examples was fabricated into a strip line (strip line) as shown in fig. 2, for example, and its corresponding signal transmission loss was measured. In the method for manufacturing the strip line 300, the surface-treated copper foil according to any of the above-described embodiments is first laminated on a 152.4 μm resin (S7439G, shengyi Technology co.), the surface-treated copper foil is then formed into the lead line 302, and the two other sheets of resin (S7439G, shengyi Technology co.) are used to cover both surfaces of the lead line 302, respectively, so that the lead line 302 is disposed in the dielectric body 304 (S7439G, shengyi Technology co.). The ribbon wire 300 may also include two ground electrodes 306-1 and 306-2, respectively disposed on opposite sides of the dielectric body 304. Ground electrode 306-1 and ground electrode 306-2 may be electrically connected to each other through conductive vias such that ground electrode 306-1 and ground electrode 306-2 have an equipotential. The specifications of the components in the ribbon wire 300 are as follows:
length of the wire 302: 100mm
Wire width w:120 μm
Thickness t of the wire: 35 μm
Dielectric characteristics of the dielectric body 304: dk =3.74, df =0.006 (measured as a 10GHz signal according to IPC-TM 650no.2.5.5.5)
Characteristic impedance: 50 omega
The state is as follows: without covering film
When measuring the signal transmission loss, according to the standard Cisco S3 method, an electrical signal is input from one end of the wire 302 by using a signal analyzer under the condition that the ground electrodes 306-1 and 306-2 are both at the ground potential, and the output value of the other end of the wire 302 is measured to judge the signal transmission loss generated by the strip line 300. The specific measurement conditions were as follows:
a signal analyzer: PNA N5227B (Keysight Technologies)
Frequency of the electric signal: 10MHz to 20GHz
Scanning points: 2000 o' clock
The correction method comprises the following steps: E-Cal (Cal kit: N4692D)
The degree of signal transmission loss of the corresponding strip line was evaluated in the case where the frequency of the electric signal was 10 GHz. Wherein, when the absolute value of the signal transmission loss is smaller, the loss degree of the representative signal in transmission is smaller. The evaluation criteria are as follows:
a (for signal transfer to perform best): the absolute value of the signal transmission loss is less than 0.80dB/in
B (representing good signal transfer): the absolute value of the signal transmission loss is between 0.80dB/in and 0.85dB/in
C (representing worst signal transfer performance): the absolute value of the signal transmission loss is more than 0.85dB/in
TABLE 2
According to table 2, in examples 1 to 9, when the root mean square height (Sq) of the treated surface of the surface-treated copper foil was 0.20 to 1.50 μm, the surface aspect ratio (Str) of the treated surface was 0.65 or less (for example, 0.10 to 0.65), and the ratio of the integrated intensity of the diffraction peak of the copper (111) crystal plane of the treated surface to the sum of the integrated intensities of the diffraction peaks of the three crystal planes of the copper (111), the copper (200) and the copper (220) after the surface-treated copper foil was subjected to the heat treatment was at least 60% (for example, 60% to 90%), the peel strength was higher than 4.06lb/in, the reliability was all the a-grade or the B-grade, and the signal transmission loss was all the a-grade or the B-grade. In contrast, for examples 10-16, when any one of the root mean square height (Sq), the surface aspect ratio (Str), or the ratio of the diffraction peak integrated intensities does not fall within the above range, even though the peel strength of a particular example (e.g., examples 10-13, 15) is still higher than 4.06lb/in, at least one of the corresponding reliability or signal transmission loss thereof falls within the C-class.
In examples 1 to 9, when the ratio of the integrated intensity of the diffraction peak of the copper (220) crystal plane of the treated surface to the total of the integrated intensities of the diffraction peaks of the three of the copper (111) crystal plane, the copper (200) crystal plane and the copper (220) crystal plane was less than 16.50% after the surface-treated copper foil was subjected to the heat treatment, the peel strength was higher than 4.06lb/in, the reliability was all class a or class B, and the signal transmission loss was all class a or class B.
According to the embodiments of the invention, by controlling the surface topography of the processing surface of the surface-treated copper foil and controlling the proportion of each crystal face of the main copper foil adjacent to the roller surface, for the corresponding copper foil substrate and the printed circuit board, not only the adhesion and reliability between the surface-treated copper foil and the carrier plate can be improved, but also the signal transmission loss generated when high-frequency electric signals are transmitted in the printed circuit board can be simultaneously reduced.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and all equivalent changes and modifications made by the claims of the present invention should be covered by the scope of the present invention.
Claims (11)
1. A surface-treated copper foil, comprising a treated surface, wherein the treated surface has a root-mean-square height of 0.20 to 1.50 [ mu ] m and a surface aspect ratio of 0.65 or less, and wherein the ratio of the integrated intensity of a diffraction peak for a (111) crystal plane to the sum of the integrated intensities of diffraction peaks for three (111), (200) and (220) crystal planes of the treated surface is at least 60% when the surface-treated copper foil is heated in an environment at 200 ℃ for 1 hour.
2. The surface-treated copper foil according to claim 1, wherein the treated surface has a surface aspect ratio of 0.10 to 0.65.
3. The surface-treated copper foil according to claim 1, wherein the ratio of the integrated intensity of diffraction peaks for (111) crystal plane and the sum of the integrated intensities of diffraction peaks for (111), (200) and (220) crystal planes is 60 to 90%.
4. The surface-treated copper foil according to claim 1, wherein the integrated intensities of diffraction peaks for (111) crystal plane, (200) crystal plane and (220) crystal plane of the treated surface are obtained by low-grazing-angle X-ray diffraction method, and the grazing angle of the low-grazing-angle X-ray diffraction method is 0.5 ° to 1.0 °.
5. The surface-treated copper foil according to claim 1, wherein the ratio of the integrated intensity of a diffraction peak for a (220) crystal plane of the treated surface to the sum of the integrated intensities of diffraction peaks for three of a (111) crystal plane, a (200) crystal plane and a (220) crystal plane is less than 16.50% and the absolute value of signal transmission loss of the surface-treated copper foil is less than or equal to 0.85dB/in, when the surface-treated copper foil is heated in an environment of 200 ℃ for 1 hour.
6. The surface-treated copper foil according to any one of claims 1 to 5, further comprising:
a main body copper foil; and
and the surface treatment layer is arranged on at least one surface of the main copper foil, wherein the outermost side of the surface treatment layer is the treatment surface.
7. The surface treated copper foil of claim 6, wherein the bulk copper foil is an electrodeposited copper foil and the surface treatment layer comprises a sublayer, the sublayer being a roughened layer.
8. The surface treated copper foil of claim 7, wherein said surface treatment layer further comprises at least one additional sublayer selected from the group consisting of a passivation layer and a coupling layer.
9. The surface treated copper foil of claim 8, wherein the passivation layer comprises at least one metal selected from the group consisting of nickel, zinc, chromium, cobalt, molybdenum, iron, tin, and vanadium.
10. A copper foil substrate, comprising:
a carrier plate; and
a surface-treated copper foil disposed on at least one surface of the carrier, wherein the surface-treated copper foil comprises:
a main body copper foil; and
a surface treatment layer disposed between the bulk copper foil and the carrier, wherein the surface treatment layer includes a treatment surface facing the carrier, the treatment surface has a root mean square height (Sq) of 0.20 to 1.50 μm, and a surface aspect ratio (Str) of 0.65 or less, wherein a ratio of a diffraction peak integral intensity of a (111) crystal plane to a sum of diffraction peak integral intensities of three (111), (200) and (220) crystal planes of the treatment surface is at least 60%.
11. The copper foil substrate of claim 10, wherein the treated side of the surface treatment layer directly contacts the carrier sheet.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110764339.9A CN115413119B (en) | 2021-07-06 | 2021-07-06 | Surface-treated copper foil and copper foil substrate |
| US17/485,482 US11540389B1 (en) | 2021-07-06 | 2021-09-26 | Surface-treated copper foil and copper clad laminate |
| JP2021158614A JP7174822B1 (en) | 2021-07-06 | 2021-09-29 | Surface treated copper foil and copper clad laminate |
| KR1020210133024A KR102482422B1 (en) | 2021-07-06 | 2021-10-07 | Surface-treated copper foil and copper clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110764339.9A CN115413119B (en) | 2021-07-06 | 2021-07-06 | Surface-treated copper foil and copper foil substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115413119A true CN115413119A (en) | 2022-11-29 |
| CN115413119B CN115413119B (en) | 2023-03-24 |
Family
ID=84156716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110764339.9A Active CN115413119B (en) | 2021-07-06 | 2021-07-06 | Surface-treated copper foil and copper foil substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115413119B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016003378A (en) * | 2014-06-18 | 2016-01-12 | 株式会社Ｓｈカッパープロダクツ | Surface-treated copper foil, production method thereof and laminate |
| CN107018623A (en) * | 2015-11-10 | 2017-08-04 | Ｊｘ金属株式会社 | Electrolytic copper foil and its manufacture method, copper-cover laminated plate, printing distributing board and its manufacture method and the manufacture method of e-machine |
| CN111519215A (en) * | 2019-02-01 | 2020-08-11 | 长春石油化学股份有限公司 | Electrolytic copper foil with low transmission loss for printed circuit board |
-
2021
- 2021-07-06 CN CN202110764339.9A patent/CN115413119B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016003378A (en) * | 2014-06-18 | 2016-01-12 | 株式会社Ｓｈカッパープロダクツ | Surface-treated copper foil, production method thereof and laminate |
| CN107018623A (en) * | 2015-11-10 | 2017-08-04 | Ｊｘ金属株式会社 | Electrolytic copper foil and its manufacture method, copper-cover laminated plate, printing distributing board and its manufacture method and the manufacture method of e-machine |
| CN111519215A (en) * | 2019-02-01 | 2020-08-11 | 长春石油化学股份有限公司 | Electrolytic copper foil with low transmission loss for printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115413119B (en) | 2023-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111936670B (en) | Surface-treated copper foil and copper foil substrate | |
| CN115413119B (en) | Surface-treated copper foil and copper foil substrate | |
| KR102482422B1 (en) | Surface-treated copper foil and copper clad laminate | |
| TWI809441B (en) | Surface-treated copper foil and copper clad laminate | |
| KR102563704B1 (en) | Surface-treated copper foil and copper clad laminate | |
| CN115589667B (en) | Surface-treated copper foil and copper foil substrate | |
| TWI761251B (en) | Surface-treated copper foil and copper clad laminate | |
| TWI756155B (en) | Surface-treated copper foil and copper clad laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |