Advanced electrodeposited copper foil having island-shaped microstructures and copper clad laminate using the same
11408087 · 2022-08-09
Assignee
Inventors
- Yun-Hsing Sung (Taoyuan, TW)
- Shih-Shen Lee (New Taipei, TW)
- Hung-Wei Hsu (Yun Lin, TW)
- Chun-Yu Kao (Yunlin County, TW)
Cpc classification
C25D5/605
CHEMISTRY; METALLURGY
Y10T428/12431
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C25D5/625
CHEMISTRY; METALLURGY
H05K1/09
ELECTRICITY
C25D5/16
CHEMISTRY; METALLURGY
International classification
B32B15/00
PERFORMING OPERATIONS; TRANSPORTING
C25D5/16
CHEMISTRY; METALLURGY
Abstract
An advanced electrodeposited copper foil having island-shaped microstructures and a copper clad laminate using the same are provided. The advanced electrodeposited copper foil includes a micro-roughened surface. The micro-roughened surface has a plurality of copper crystals, a plurality of copper whiskers and a plurality of copper crystal groups which are in a non-uniform distribution and form into island-shaped patterns.
Claims
1. An advanced electrodeposited copper foil having island-shaped microstructures, characterized by including a micro-roughened surface, wherein the micro-roughened surface has a plurality of copper crystals that are in a non-uniform distribution; wherein different quantities of the copper crystals are stacked together to form respective copper whiskers, and different quantities of the copper whiskers are grouped together to form respective copper crystal groups; wherein as observed by a scanning electron microscope operated with a +35 degrees tilt and under 10000× magnification, the micro-roughened surface has at least ten first smooth areas each having a length of 250 nm and a width of 250 nm, at least one second smooth area having a length of 500 nm and a width of 500 nm, and at least one island-shaped microstructure having a length of 1500 nm.
2. The advanced electrodeposited copper foil according to claim 1, wherein no copper crystals are present in each of the first and second smooth areas.
3. The advanced electrodeposited copper foil according to claim 1, wherein as observed by the scanning electron microscope operated with a +35 degrees tilt and under 10000× magnification, the at least one island-shaped microstructure has at least three of the copper crystals and/or copper whiskers.
4. The advanced electrodeposited copper foil according to claim 1, wherein each of the copper whiskers has a topmost copper crystal.
5. The advanced electrodeposited copper foil according to claim 4, wherein the topmost copper crystals are each in the shape of a conoid, a rod or a sphere.
6. The advanced electrodeposited copper foil according to claim 1, wherein the micro-roughened surface further has at least two stripe-shaped copper-free areas each having a length of 1000 nm.
7. The advanced electrodeposited copper foil according to claim 1, wherein the micro-roughened surface has a surface roughness (Rz JIS B 0601-1994) less than 2.1 μm.
8. The advanced electrodeposited copper foil according to claim 1, wherein the micro-roughened surface further includes a plurality of peaks and a plurality of grooves between the peaks, and the copper crystals, the copper whiskers and the copper crystal groups are correspondingly formed on the peaks.
9. The advanced electrodeposited copper foil according to claim 8, wherein each of the grooves has a U-shaped or V-shaped cross-sectional profile.
10. A copper clad laminate, comprising: a substrate; and an advanced electrodeposited copper foil disposed on the substrate and having a micro-roughened surface that is bonded to a surface of the substrate, wherein the micro-roughened surface has a plurality of copper crystals that are in a non-uniform distribution; wherein different quantities of the copper crystals are stacked together to form respective copper whiskers, and different quantities of the copper whiskers are grouped together to form respective copper crystal groups; wherein as observed by a scanning electron microscope operated with a +35 degrees tilt and under 10000× magnification, the micro-roughened surface has at least ten first smooth areas each having a length of 250 nm and a width of 250 nm, at least one second smooth area having a length of 500 nm and a width of 500 nm, and at least one island-shaped microstructure having a length of 1500 nm.
11. The copper clad laminate according to claim 10, wherein no copper crystals are present in each of the first and second smooth areas.
12. The copper clad laminate according to claim 10, wherein as observed by the scanning electron microscope operated with a +35 degrees tilt and under 10000× magnification, the at least one island-shaped microstructure has at least three of the copper crystals and/or the copper whiskers.
13. The copper clad laminate according to claim 10, wherein each of the copper whiskers has a topmost copper crystal.
14. The copper clad laminate according to claim 13, wherein the topmost copper crystals are each in the shape of a conoid, a rod or a sphere.
15. The copper clad laminate according to claim 10, wherein the micro-roughened surface further has at least two stripe-shaped copper-free areas each having a length of 1000 nm.
16. The copper clad laminate according to claim 10, wherein the micro-roughened surface has a surface roughness (Rz JIS B 0601-1994) less than 2.1 μm.
17. The copper clad laminate according to claim 10, wherein the micro-roughened surface further includes a plurality of peaks and a plurality of grooves between the peaks, and the copper crystals, the copper whiskers and the copper crystal groups are correspondingly formed on the peaks.
18. The copper clad laminate according to claim 17, wherein each of the grooves has a U-shaped or V-shaped cross-sectional profile.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The present disclosure will become more fully understood from the following detailed description and accompanying drawings.
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DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS
(11) The present disclosure is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. Like numbers in the drawings indicate like components throughout the views. As used in the description herein and throughout the claims that follow, unless the context clearly dictates otherwise, the meaning of “a”, “an”, and “the” includes plural reference, and the meaning of “in” includes “in” and “on”. Titles or subtitles can be used herein for the convenience of a reader, which shall have no influence on the scope of the present disclosure.
(12) The terms used herein generally have their ordinary meanings in the art. In the case of conflict, the present document, including any definitions given herein, will prevail. The same thing can be expressed in more than one way. Alternative language and synonyms can be used for any term(s) discussed herein, and no special significance is to be placed upon whether a term is elaborated or discussed herein. A recital of one or more synonyms does not exclude the use of other synonyms. The use of examples anywhere in this specification including examples of any terms is illustrative only, and in no way limits the scope and meaning of the present disclosure or of any exemplified term. Likewise, the present disclosure is not limited to various embodiments given herein. Numbering terms such as “first”, “second” or “third” can be used to describe various components, signals or the like, which are for distinguishing one component/signal from another one only, and are not intended to, nor should be construed to impose any substantive limitations on the components, signals or the like.
(13) Referring to
(14) In order to reduce insertion loss, the substrate 1 can be formed from a material having a low dissipation factor (Df). The Df of the substrate 1 can be less than or equal to 0.015 at 10 GHz, preferably less than or equal to 0.010, and more preferably less than or equal to 0.005.
(15) More specifically, the substrate 1 is formed from a resin-based composite material (i.e., a prepreg), which is obtained by the steps of impregnating a base material with a synthetic resin and then curing the impregnated base material. Specific examples of the base material include a phenolic cotton paper, a cotton paper, a fabric made of resin fibers, a non-woven fabric made of resin fibers, a glass board, a glass woven fabric and a glass non-woven fabric. Specific examples of the synthetic resin include an epoxy resin, a polyester resin, a polyimide resin, a cyanate ester resin, a bismaleimide triazine resin, a polyphenylene ether resin and a phenol resin. The synthetic resin can be formed into a single-layered or multi-layered structure. The resin-based composite material can be a mid loss, low loss, very low loss or ultra low loss material, which are well-known to people skilled in this art and are specifically exemplified by the products of EM890, EM890(K), EM891(K), EM528, EM526, IT170GRA1, IT958G, IT968G, IT150DA, S7040G, S7439G, S6GX, TU863+, TU883 (A,Sp), MEGTRON 4, MEGTRON 6, MEGTRON 7 and MEGTRON 8. However, these examples are not meant to limit the scope of the present disclosure.
(16) Referring to
(17) In certain embodiments, the average height of the copper whiskers W can be less than 3 μm, preferably less than 1.8 μm, and more preferably less than 1.0 μm. Furthermore, the average height of the copper crystal groups G can be less than 3.5 μm, preferably less than 1.8 μm, and more preferably less than 1.0 μm. In certain embodiments, each of the copper whiskers W can include up to twenty-five copper crystals 21, preferably up to twelve copper crystals 21, more preferably up to ten copper crystals 21, and most preferably up to eight copper crystals 21. In certain embodiments, the average outer diameter of the copper crystals 21 can be less than 0.5 μm, more preferably between 0.05 μm and 0.5 μm, and most preferably between 0.1 μm and 0.4 μm.
(18) It is worth mentioning that, it is different from the conventional electrodeposited copper foil that, the copper crystals are non-uniformly distributed on the copper foil surface, only a part of which are grouped together. That is, the advanced electrodeposited copper foil 2 of the present disclosure has a surface with an apparent uneven profile, in which not only are the copper crystals 21 non-uniformly distributed, but also the copper whiskers W are respectively formed by different quantities of the copper crystals 21, and the copper crystal groups G are respectively formed by different quantities of the copper whiskers W. Therefore, the advanced electrodeposited copper foil 2 of the present disclosure can increase signal integrity and suppress insertion loss, as well as maintaining good peel strength, to adapt high frequency and high speed signal transmission. In addition, the micro-roughened surface 20 has a surface roughness (Rz JIS B 0601-1994) less than 2.1 μm, which can facilitate a reduction in line width and line spacing.
(19) Reference is again made to
Manufacturing Example
(20) Reference is again made to
(21) As shown in
(22) In practice, the copper-containing plating solutions each contain copper ions, an acid and at least one metal additive. The source of copper ions can be copper sulfate, copper nitrate or a combination thereof. Specific examples of the acid include sulfuric acid, nitric acid or a combination thereof. Specific examples of the at least one metal additive include cobalt, iron, zinc, or a combination thereof. According to requirements, the copper-containing plating solutions can each contain at least one conventional additive such as gelatin, an organic nitride, hydroxyethyl cellulose (HEC), polyethylene glycol (PEG), sodium 3-mercaptopropane sulphonate (MPS), bis-(sodium sulfopropyl)-disulfide (SPS), and a thiourea group-containing compound. However, the above-recited examples are merely exemplary and are not intended to limit the scope of the present disclosure.
(23) It is worth mentioning that, the micro-roughening treatment of copper electrodeposition can be used to produce not only a reverse-treated copper foil, but also a high temperature elongation (HTE) copper foil or a very low profile (VLP) copper foil.
Performance Verification of Copper Foil
(24) An advanced electrodeposited copper foil having island-shaped microstructures of Example 1 (herein after referred to as “copper foil having island-shaped microstructures” or “ULVLP copper foil”) is obtained by the above-mentioned micro-roughening treatment of copper electrodeposition. Processing conditions of each treatment stage are shown in Table 1, and surface profiles of the ULVLP copper foil are shown in
(25) TABLE-US-00001 TABLE 1 First Second Third trace trace trace First Second Third Fourth Fifth Sixth Seventh metal metal metal Silane plating plating plating plating plating plating plating plating plating plating treat- stage stage stage stage stage stage stage stage stage stage ment Conditions Metal ions Cu.sup.+2 Cu.sup.+2 Cu.sup.+2 Cu.sup.+2 Cu.sup.+2 Cu.sup.+2 Cu.sup.+2 Ni.sup.+2 Zn.sup.+2 Cr.sup.+6 N/A of plating Metal 5.0-10 66-80 66-80 5.0-10 5.0-10 66-80 66-80 17-20 2-4 1-3 N/A solution concentration (g/L) Chlorine <3 <3 <3 <3 <3 <3 <3 <3 <3 <3 <3 concentration (Ppm) Acid Sulfuric Sulfuric Sulfuric Sulfuric Sulfuric Sulfuric Sulfuric Phosphoric Boric Phosphoric N/A concentration acid acid acid acid acid acid acid acid acid acid (g/L) 90-100 60-75 60-75 90-100 90-100 60-75 60-75 3-6 10-25 0.1-2.0 Trace metal 180-220 30-40 30-40 180-220 180-220 30-40 30-40 100-200 100-200 100-200 N/A concentration (Ni, Pd, Ag, W . . . ) (ppm or mg/L) Time (Sec) 1.69 2.06 2.06 1.69 1.69 2.06 2.06 2.25 2.06 2.25 3 Temperature 30 45 45 30 30 45 45 28 30 40 40 (° C.)(±5° C.) pH <1.5 <1.5 <1.5 <1.5 <1.5 <1.5 <1.5 3-4 4-5 3-4 5-7 Example 1 Current density 0.01 13.37 13.37 21.24 21.24 4.01 0.01 1.1 0.6 0.6 N/A (A/dm.sup.2)(±10%) Example 2 Current density 0.01 15.00 15.00 16.00 16.00 4.01 0.01 1.1 0.6 0.6 N/A (A/dm.sup.2)(±10%)
(26) It can be observed from
(27) It is worth mentioning that, the above-mentioned structural features are all observed from an image showing a copper foil surface profile, which is obtained by a scanning electron microscope (S-3400N, manufactured by Hitachi, Ltd.) operated with a +35 degrees tilt and under a suitable magnification (if the magnification is not specified, it means 10000x). The corresponding area size of the image is about 12.7 μm×9.46 μm, which is close to 120 μm2. The terms “first smooth area 20a” and “second smooth area 20b” mean areas where there are no copper crystals, as observed from a SEM image. The term “island-shaped microstructure 20c” means a structure having a contour shape close to an island or a peninsula and formed with smooth areas therearound, as observed from a SEM image. The term “stripe-shaped copper-free area 20d” means an area where there are no copper crystals, which has a width to length ratio less than ⅓ (for example, 1/10, 1/100 or 1/1000), and may have a linear or non-linear shape and an uniform or non-uniform width.
(28) The ULVLP copper foils of Example 1 are used to manufacture respective copper clad laminates together with different types of prepregs, which are tested for insertion loss value. The results are shown in Table 2.
(29) TABLE-US-00002 TABLE 2 Delta-L test PCIe-PCB material and loss target method (with reference to the target set by Intel) (Intel) Insertion loss Insertion loss Insertion loss Insertion loss Prepreg Electrical at 4 GHz at 8 GHz at 12.89 GHz at 16 GHz Type Df property item (dB/in) (dB/in) (dB/in) (dB/in) Mid loss 0.015- Stripline −0.65 −1.16 −1.74 −2.30 >0.010 Low loss 0.010- Stripline −0.50 −0.85 −1.25 −1.49 >0.005 Ultra low loss 0.005-0.0005 Stripline −0.35 −0.58 −0.83 −0.96
Test Example 11
(30) Each of ULVLP copper foils of Examples 1 and 2, an electrodeposited copper foil according to Taiwan Patent Application No. 107133827 (product name: RG311, herein after referred to as “RG311 copper foil”) and an electrodeposited copper foil produced by the C company (product name: RTF-3, herein after referred to as “RTF-3 copper foil”) is laminated with a mid loss prepreg (product name: IT170GRA1) produced by the I company, so as to form a single-layered copper clad laminate after being cured, respectively. The RG311 copper foil has a surface roughness (Rz JIS B 0601-1994) that is less than 2.3 μm. The surface profile of the RTF-3 copper foil is shown in
(31) TABLE-US-00003 TABLE 3 Increase compared Dk @ 10 Df @ 10 to Comparative Df GHz GHz Copper foil Copper SL Loss (dB/in) Example 1 Material level RC 50% RC 50% level model 8 GHz 16 GHz 8 GHz 16 GHz IT-170GRA1 Mid 3.90 0.0100 Comparative RTF-3 −0.9395 −1.7694 0.00% 0.00% Loss Example 1 Comparative RG311 −0.8321 −1.4986 11.43% 15.30% Example 2 Example 1 ULVLP −0.7839 −1.4022 16.56% 20.75% Example 2 ULVLP −0.7418 −1.3380 21.04% 24.38%
(32) It can be seen from the test results shown in Table 3 that, at a frequency of 8 GHz, the insertion loss of the ULVLP copper foil is about 16% to 21% less than that of the RTF-3 copper foil and is about 5% to 10% less than that of the RG311 copper foil. At a frequency of 16 GHz, the insertion loss of the ULVLP copper foil is about 20% to 24% less than that of the RTF-3 copper foil and is about 6% to 10% less than that of the RG311 copper foil. Therefore, compared to the RTF-3 and RG311 copper foils, the ULVLP copper foil has better signal integrity.
Test Example 2
(33) Each of ULVLP copper foils of Examples 1 and 2, an electrodeposited copper foil according to Taiwan Patent Application No. 107133827 (product name: RG311, herein after referred to as “RG311 copper foil”) and an electrodeposited copper foil produced by the C company (product name: RTF-3, herein after referred to as “RTF-3 copper foil”) is laminated with a mid loss prepreg (product name: IT985G) produced by the I company, so as to form a single-layered copper clad laminate after being cured, respectively. The RG311 has a surface roughness (Rz JIS B 0601-1994) that is less than 2.3 μm. The surface profile of the RTF-3 copper foil is shown in
(34) TABLE-US-00004 TABLE 4 Increase compared to Dk @ 10 Df @ 10 Comparative Df GHz GHz Copper foil Copper SL Loss (dB/in) Example 1 Material level RC 50% RC 50% level model 8 GHz 16 GHz 8 GHz 16 GHz IT- Low 3.70 0.0070 Comparative RTF-3 −0.7906 −1.4491 0.00% 0.00% 958G Loss Example 1 Comparative RG311 −0.6996 −1.2415 11.51% 14.33% Example 2 Example 1 ULVLP −0.6657 −1.1838 15.80% 18.31% Example 2 ULVLP −0.6283 −1.1063 20.53% 23.66%
(35) It can be seen from the test results shown in Table 4 that, at a frequency of 8 GHz, the insertion loss of the ULVLP copper foil is about 15.80% to 20.53% less than that of the RTF-3 copper foil and is about 3% to 9% less than that of the RG311 copper foil. At a frequency of 16 GHz, the insertion loss of the ULVLP copper foil is about 18% to 23% less than that of the RTF-3 copper foil and is about 4.6% to 10.8% less than that of the RG311 copper foil. Therefore, compared to the RTF-3 and RG311 copper foils, the ULVLP copper foil has better signal integrity.
Test Example 3
(36) Each of ULVLP copper foils of Examples 1 and 2, an electrodeposited copper foil according to Taiwan Patent Application No. 107133827 (product name: RG311, herein after referred to as “RG311 copper foil”) and an electrodeposited copper foil produced by the M company (product name: HS1-M2-VSP, herein after referred to as “HS1-M2-VSP copper foil”) are is laminated with an ultra low loss prepreg (product name: IT968) produced by the I company, so as to form a single-layered copper clad laminate after being cured, respectively. The RG311 has a surface roughness (Rz JIS B 0601-1994) that is less than 2.3 μm. The peel strengths of the single-layered copper clad laminates all meet the practical requirements of. The single-layered copper clad laminates are tested for signal integrity by the Delta-L test method provided by the Intel Corporation, and test conditions include a core thickness of 3 mils core (1 oz), 10 mils PP and 4.5 mils trace width. The results are shown in Table 5.
(37) TABLE-US-00005 TABLE 5 Increase compared to Dk @ 10 Df @ 10 Comparative Df GHz GHz Copper foil Copper SL Loss (dB/in) Example 1 Material level RC 50% RC 50% level model 8 GHz 16 GHz 8 GHz 16 GHz IT-968 Ultra 3.66 0.0050 Comparative HS1-M2-VSP −0.6013 −1.0403 0.00% 0.00% Low Example 1 Comparative RG311 −0.5489 −0.9208 8.71% 11.49% Example 2 Example 1 ULVLP −0.5209 −0.8667 13.37% 16.69% Example 2 ULVLP −0.4927 −0.8202 18.06% 21.06%
(38) It can be seen from the test results shown in Table 5 that, at a frequency of 8 GHz, the insertion loss of the ULVLP copper foil is about 16.04% to 19.73% less than that of the HS1-M2-VSP copper foil and is about 5% to 10% less than that of the RG311 copper foil. At a frequency of 16 GHz, the insertion loss of the ULVLP copper foil is about 16% to 21% less than that of the HS1-M2-VSP copper foil and is about 5% to 10% less than that of the RG311 copper foil. Therefore, compared to the HS1-M2-VSP and RG311 copper foils, the ULVLP copper foil has better signal integrity.
(39) One of the effects of the present disclosure is that, the advanced electrodeposited copper foil can, without lowering peel strength, reduce insertion loss to increase signal integrity so as to adapt high frequency and high speed signal transmission, thereby meeting the requirements of 5G applications, by the technical features of “the micro-roughened surface has at least ten first smooth areas each having a length of 250 nm and a width of 250 nm, at least one second smooth area having a length of 500 nm and a width of 500 nm, and at least one island-shaped microstructure having a length of 1500 nm which has at least three of the copper crystals and/or copper whiskers.” It should be noted that, the advanced electrodeposited copper foil is not limited to a reverse-treated electrodeposited copper foil, and can be applied to a copper foil having a surface roughness (Rz JIS B 0601-1994) less than 2.1 μm.
(40) It is worth mentioning that, the present disclosure substantially uses a technical solution that is discarded due to a technical prejudice in the art, which allows a copper foil surface to have a certain degree of unevenness. The technical solution can directly achieve the beneficial technical effect of further optimizing electrical properties on the premise of maintaining good peel strength.
(41) The foregoing description of the exemplary embodiments of the disclosure has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the disclosure to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching.
(42) The embodiments were chosen and described in order to explain the principles of the disclosure and their practical application so as to enable others skilled in the art to utilize the disclosure and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the present disclosure pertains without departing from its spirit and scope.