Advanced electrodeposited copper foil and copper clad laminate using the same
11332839 · 2022-05-17
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
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
H05K1/09
ELECTRICITY
C25D5/16
CHEMISTRY; METALLURGY
International classification
B21C37/00
PERFORMING OPERATIONS; TRANSPORTING
C25D5/16
CHEMISTRY; METALLURGY
Abstract
An advanced electrodeposited copper foil and a copper clad laminate using the same are provided. The advanced electrodeposited copper foil has an uneven micro-roughened surface. As observed by a scanning electron microscope operated with a +35 degree tilt and under 1,000× magnification, the uneven micro-roughened surface has a plurality of production direction stripes formed by copper crystals.
Claims
1. An advanced electrodeposited copper foil having an uneven micro-roughened surface, characterized in that the micro-roughened surface has a plurality of production direction stripes and a plurality of fine strips which are formed by copper crystals, as observed by a scanning electron microscope operated with a +35 degree tilt and under 1,000× magnification, and at least five of the fine strips each have a minimum included angle that is greater than 20 degrees relative to the production direction stripes.
2. The advanced electrodeposited copper foil according to claim 1, wherein as observed by the scanning electron microscope operated with a +35 degree tilt and under 10,000× magnification, the fine strips each have a length and a width which satisfy the following relationship:
50 nm≤width≤1000 nm; and
1.0 μm≤length≤10 μm.
3. The advanced electrodeposited copper foil according to claim 1, wherein as observed by the scanning electron microscope operated with a +35 degree tilt and under 10,000× 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 and at least one second smooth area having a length of 500 nm and a width of 500 nm, and no copper crystals are present in each of the first and second smooth areas.
4. The advanced electrodeposited copper foil according to claim 1, 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 the scanning electron microscope operated with a +35 degree tilt and under 10,000× magnification, the copper crystals, the copper whiskers or the copper crystal groups have a median maximum diameter less than 550 nm.
5. The advanced electrodeposited copper foil according to claim 4, wherein each of the copper whiskers has a topmost copper crystal that is 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 has a surface roughness (Rz JIS B 0601-1994) less than 2.3 μm.
7. A copper clad laminate, comprising: a substrate; and an advanced electrodeposited copper foil disposed on the substrate and having an uneven micro-roughened surface that is bonded to a surface of the substrate, wherein the micro-roughened surface has a plurality of production direction stripes and a plurality of fine strips which are formed by copper crystals, as observed by a scanning electron microscope operated with a +35 degree tilt and under 1,000× magnification, and at least five of the fine strips each have a minimum included angle that is greater than 20 degrees relative to the production direction stripes.
8. The copper clad laminate according to claim 7, wherein as observed by the scanning electron microscope operated with a +35 degree tilt and under 10,000× magnification, the fine strips each have a length and a width which satisfy the following relationship:
50 nm≤width≤1000 nm; and
1.0 μm≤length≤10 μm.
9. The copper clad laminate according to claim 7, wherein as observed by the scanning electron microscope operated with a +35 degree tilt and under 10,000× 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 and at least one second smooth area having a length of 500 nm and a width of 500 nm, and no copper crystals are present in each of the first and second smooth areas.
10. The copper clad laminate according to claim 7, 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 the scanning electron microscope operated with a +35 degree tilt and under 10,000× magnification, the copper crystals, the copper whiskers or the copper crystal groups have a median maximum diameter less than 550 nm.
11. The copper clad laminate according to claim 10, wherein each of the copper whiskers has a topmost copper crystal that is in the shape of a conoid, a rod or a sphere.
12. The copper clad laminate according to claim 7, wherein the micro-roughened surface has a surface roughness (Rz JIS B 0601-1994) less than 2.3 μm.
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) 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.
(14) Referring to
(15) 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.
(16) 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 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.
(17) Referring to
(18) Referring to
(19) The reference line RL is defined as follows: acquiring images of the micro-roughened surface 20 as shown in
(20) The inclination angles of the fine strips 20b are measured by the following method: using the image analysis software (ImageJ software from the National Institutes of Health, http://rsb.info.nih.gov) to draw another horizontal line HL on the image under 3,000× magnification, and then draw a number of the reference lines RL that are parallel to each other based on the another horizontal line HL; and acquiring the minimum included angles β1, β2, β3, β4, β5, β6, β7, β8, β9 of the fine strips 20b respectively relative to the reference lines RL. As shown in
(21) Referring to
(22) It is worth mentioning that, different from the conventional electrodeposited copper foil, the micro-roughened surface 20 of the advanced electrodeposited copper foil 2 has a plurality of production direction stripes 20a and a plurality of fine strips 20b which are formed by copper crystals 21, in which at least five of the fine strips 20b each have a minimum included angle β1, β2, β3, β4, β5, β6, β7, β8, β9 greater than 20 degrees. Furthermore, on the micro-roughened surface 20, there are at least ten first smooth areas 20c each having a length of 250 nm and a width of 250 nm and at least one second smooth area 20d having a length of 500 nm and a width of 500 nm. Therefore, the advanced electrodeposited copper foil 2 of the present disclosure can increase signal integrity and suppress insertion loss on the premise of maintaining good peel strength, so as to be adaptable to 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 2.3 μm, which can facilitate a reduction in line width and line spacing.
(23) Reference is again made to
Manufacturing Example
(24) Referring again to
(25) As shown in
(26) In practice, the copper-containing plating solutions each contain copper ions, an acid and at least one metal additive. The source of the 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 a gelatin, an organic nitride, a hydroxyethyl cellulose (HEC), a polyethylene glycol (PEG), a sodium 3-mercaptopropane sulphonate (MPS), a 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.
(27) The power supplied to the micro-roughening treatment of copper electrodeposition may be in a constant current form, a constant voltage form, a pulse wave form or a saw wave form, but it is not limited thereto. The conditions of the micro-roughening treatment of copper electrodeposition are as shown in Table 1.
(28) It is worth mentioning that, the above-mentioned 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
(29) An advanced electrodeposited copper foil is obtained by a micro-roughening treatment of copper electrodeposition with seven stages, and the processing conditions for each stage are shown in Table 1. A scanning electron microscope (SEM) (S-3400N, manufactured by Hitachi, Ltd.) is operated at a +35 degree tilt to obtain images (i.e.,
(30) 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 (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 (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%)
(31) It can be observed from
(32) Different types of prepregs are used with the advanced electrodeposited copper foils of the present disclosure to produce respective copper clad laminates, which are tested for insertion loss value. The results are shown in Table 2.
(33) TABLE-US-00002 TABLE 2 Delta-L PCIe-PCB material and loss target test 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- Stripline −0.35 −0.58 −0.83 −0.96 >0.001
Test Example 11
(34) Each of advanced electrodeposited copper foils of Examples 3-1 and 3-2 that are produced by the conditions of Example 1 as shown in Table 1, an electrodeposited copper foil according to Taiwan Patent Application No. 107133827 (product name: RG311, herein after referred to as “RG311”) and an electrodeposited copper foil produced by the C company (product name: RTF-3, herein after referred to as “RTF-3”) 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 has a surface roughness (Rz JIS B 0601-1994) that is less than 2.3 μm. The RTF-3 has a plurality of copper crystals that are apparently present in a uniform distribution on a copper foil surface thereof, as observed from an image obtained by a scanning electron microscope (S-3400N, manufactured by Hitachi, Ltd.) with a +35 degree tilt and under 10,000× magnification (as shown in
(35) TABLE-US-00003 TABLE 3 Increase compared Dk @ 10 Df @ 10 to Comparative Df GHz GHz Copper Copper SL Loss (dB/in) Example 1 Material level RC 50% RC 50% foil 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 Advanced −0.7739 −1.3922 17.63% 21.32% electrodeposited copper foil Example 2 Advanced −0.7318 −1.3180 22.10% 25.51% electrodeposited copper foil
(36) It can be seen from the test results shown in Table 3 that, at a frequency of 8 GHz, the insertion loss of the advanced electrodeposited copper foil is 17.63% to 22.1% less than that of the RTF-3 and is 6.2% to 10.67% less than that of the RG311. At a frequency of 16 GHz, the insertion loss of the advanced electrodeposited copper foil is 21.32% to 25.51% less than that of the RTF-3 and is 6.01% to 10.21% less than that of the RG311. Therefore, compared to the RTF-3 and the RG311, the advanced electrodeposited copper foil has better signal integrity.
Test Example 2
(37) Each of advanced electrodeposited copper foils of Examples 4-1 and 4-2 that are produced by the conditions of Example 1 as shown in Table 1, an electrodeposited copper foil according to Taiwan Patent Application No. 107133827 (product name: RG311, herein after referred to as “RG311”) and an electrodeposited copper foil produced by the C company (product name: RTF-3, herein after referred to as “RTF-3”) 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 RTF-3 has a plurality of copper crystals that are apparently present in a non-uniform distribution on a copper foil surface thereof, as observed from an image obtained by a scanning electron microscope (S-3400N, manufactured by Hitachi, Ltd.) with a +35 degree tilt and under 10,000× magnification (as shown in
(38) TABLE-US-00004 TABLE 4 Increase compared Dk @ 10 Df @ 10 to Comparative Df GHz GHz Copper Copper SL Loss (dB/in) Example 1 Material level RC 50% RC 50% foil 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 11.52% 14.33% Example 2 Example 1 Advanced −0.6457 −1.1438 18.33% 21.07% electrodeposited copper foil Example 2 Advanced −0.6083 −1.0863 23.06% 25.04% electrodeposited copper foil
(39) It can be seen from the test results shown in Table 4 that, at a frequency of 8 GHz, the insertion loss of the advanced electrodeposited copper foil is 18.33% to 23.06% less than that of the RTF-3 and is about 18.33% less than that of the RG311. At a frequency of 16 GHz, the insertion loss of the advanced electrodeposited copper foil is about 21.07% less than that of the RTF-3. Therefore, compared to the RTF-3 and the RG311, the advanced electrodeposited copper foil has better signal integrity.
Test Example 3
(40) Each of advanced electrodeposited copper foils of Examples 5-1 and 5-2 that are produced by the conditions of Example 1 as shown in Table 1, an electrodeposited copper foil according to Taiwan Patent Application No. 107133827 (product name: RG311, herein after referred to as “RG311”) and an electrodeposited copper foil produced by the M company (product name: HS1-M2-VSP, herein after referred to as “HS1-M2-VSP”, as shown in
(41) TABLE-US-00005 TABLE 5 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-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 8.73% 11.49% Example 2 Example 1 Advanced −0.5049 −0.8467 16.04% 18.62% electrodeposited copper foil Example 2 Advanced −0.4827 −0.8002 19.73% 23.09% electrodeposited copper foil
(42) It can be seen from the test results shown in Table 5 that, at a frequency of 8 GHz, the insertion loss of the advanced electrodeposited copper foil is 16.04% to 19.73% less than that of the HS1-M2-VSP and is 7.31% to 11.00% less than that of the RG311. At a frequency of 16 GHz, the insertion loss of the advanced electrodeposited copper foil is 18.62% to 23.09% less than that of the HS1-M2-VSP and is 7.12% to 11.59% less than that of the RG311. Therefore, compared to the HS1-M2-VSP and the RG311, the advanced electrodeposited copper foil has better signal integrity.
(43) One of the beneficial effects of the present disclosure is that, the advanced electrodeposited copper foil and the copper clad laminate can increase signal integrity and suppress insertion loss, while maintaining good peel strength, to be adaptable to high frequency and high speed signal transmission so as to meet the requirements of 5G applications, by virtue of “the micro-roughened surface has a plurality of production direction stripes and a plurality of fine strips which are formed by copper crystals, and at least five of the fine strips each have a minimum included angle greater than 20 degrees relative to the production direction stripes.” 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 2.3 μm.
(44) More specifically, different from the conventional electrodeposited copper foil, the advanced electrodeposited copper foil has a plurality of copper crystals that are present in a non-uniform distribution on a micro-roughened surface thereof, and the copper crystals are stacked or arranged into different types of copper whiskers and copper crystal groups. Furthermore, the copper whiskers and the copper crystal groups have no special directionality, as observed from a scanning electron microscope image of the micro-roughened surface taken with a +35 degree tilt and under 10,000× magnification. The copper crystals form into a stripe pattern, in which at least five of the fine strips each have a minimum included angle greater than 20 degrees, as observed from a scanning electron microscope image of the micro-roughened surface taken with a +35 degree tilt and under 1,000× magnification. As proved by the tests, the advanced electrodeposited copper foil of the present disclosure has better signal integrity.
(45) 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.
(46) 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.