JP2021019061A - Printed wiring board and manufacturing method thereof - Google Patents
Printed wiring board and manufacturing method thereof Download PDFInfo
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本発明は、ＳＡＰ法を用いて製造したプリント配線板およびその製造方法に関する。 The present invention relates to a printed wiring board manufactured by using the SAP method and a method for manufacturing the printed wiring board.
ＳＡＰ法を用いたプリント配線板の製造において、熱硬化性樹脂と無機フィラーとの混合物からなる層間絶縁層にレーザー（ＣＯ２、ＵＶ−ＹＡＧ、エキシマなど）でビア形成した後、層間絶縁層の表面およびビアの側面ならびに底面にビア形成で発生した残渣を、ＣＦ４を用いたプラズマにより除去するデスミア・粗化プロセスが行われている（特許文献１）。 In the production of printed wiring boards using the SAP method, vias are formed on the interlayer insulating layer made of a mixture of thermosetting resin and inorganic filler with a laser (CO 2 , UV-YAG, excimer, etc.), and then the interlayer insulating layer is formed. A desmear / roughening process is performed on the surface, the side surface of the via, and the bottom surface to remove the residue generated by the formation of vias by plasma using CF 4 (Patent Document 1).
図３（ａ）〜（ｄ）は、従来のＣＦ４プラズマを用いたデスミア・粗化プロセスの問題を説明するための図である。従来のＣＦ４プラズマを用いたデスミア・粗化プロセスは小径ビア形成に有利である。しかし、ビア形成後、熱硬化性樹脂５２と無機フィラー５３との混合物からなる層間絶縁層５１（図３（ａ））に、ＣＦ４プラズマを用いたデスミア・粗化プロセスを行うと、熱硬化性樹脂５２に比べて無機フィラー５３のエッチングレートが低いため、無機フィラー５３が多く突出した表面（図３（ｂ））となる。この層間絶縁層５１の表面に例えば配線層５４を形成すると（図３（ｃ））、熱硬化性樹脂５２と配線層５４との接触部分が少ないため、配線層５４のピール強度が低くなり、層間絶縁層５１から配線層５４が脱落し易くなる（図３（ｄ））。 Figure 3 (a) ~ (d) are diagrams for explaining a conventional CF 4 plasma problems desmear-roughening process using. The desmear-roughening process using a conventional CF 4 plasma is advantageous to small-sized via formation. However, after the vias are formed, the interlayer insulating layer 51 (FIG. 3 (a)) made of a mixture of the thermosetting resin 52 and the inorganic filler 53 is thermally cured by performing a desmear / roughening process using CF 4 plasma. Since the etching rate of the inorganic filler 53 is lower than that of the sex resin 52, the surface has a large amount of the inorganic filler 53 (FIG. 3B). When the wiring layer 54 is formed on the surface of the interlayer insulating layer 51 (FIG. 3C), the peel strength of the wiring layer 54 is lowered because the contact portion between the thermosetting resin 52 and the wiring layer 54 is small. The wiring layer 54 is likely to fall off from the interlayer insulating layer 51 (FIG. 3 (d)).
本発明に係るプリント配線板は、層間絶縁層として熱硬化性樹脂と無機フィラーとの混合物を用いたプリント配線板において、前記層間絶縁層の表面および前記層間絶縁層に設けたビアの側面ならびに底面が、無機フィラーの突出がなく凹部を有する粗面であることを特徴とする。 The printed wiring board according to the present invention is a printed wiring board using a mixture of a thermosetting resin and an inorganic filler as an interlayer insulating layer, and the surface of the interlayer insulating layer and the side surface and the bottom surface of vias provided on the interlayer insulating layer. However, it is characterized in that it is a rough surface having recesses without protrusion of the inorganic filler.
また、本発明に係るプリント配線板の製造方法は、少なくとも、熱硬化性樹脂と無機フィラーとの混合物からなる層間絶縁層にビアを形成するビア形成工程、その後のデスミア・粗化工程、クリーニング工程を含むＳＡＰ法によるプリント配線板の製造方法において、前記デスミア・粗化工程は、フルオロカーボン系ガスを含む反応性イオンエッチング（ＲＩＥ）により、前記層間絶縁層内の前記熱硬化性樹脂より前記無機フィラーを優先的にエッチングする条件で行うことを特徴とする。 Further, the method for manufacturing a printed wiring board according to the present invention is at least a via forming step of forming vias in an interlayer insulating layer made of a mixture of a thermosetting resin and an inorganic filler, a desmear / roughening step, and a cleaning step thereafter. In the method for manufacturing a printed wiring board by the SAP method including the above, the desmear / roughening step is performed by reactive ion etching (RIE) containing a fluorocarbon-based gas to obtain the inorganic filler from the thermosetting resin in the interlayer insulating layer. It is characterized in that it is carried out under the condition of preferentially etching.
本発明の実施形態によれば、熱硬化性樹脂と無機フィラーとの混合物からなる層間絶縁層を用いた場合でも、層間絶縁層の表面およびビアの側面ならびに底面を、無機フィラーの突出がなく凹部を有する粗面とすることで、層間絶縁層の表面に設けたシード層および配線層の脱落を防止できるとともに、層間絶縁層に設けたビアの側面および底面に設けたシード層およびビアめっき層の脱落を防止することができる。その結果、配線層のファインパターン（５μｍ以下）を達成することができる。 According to the embodiment of the present invention, even when an interlayer insulating layer made of a mixture of a thermosetting resin and an inorganic filler is used, the surface of the interlayer insulating layer and the side surface and the bottom surface of the via are recessed without protrusion of the inorganic filler. The seed layer and the wiring layer provided on the surface of the interlayer insulating layer can be prevented from falling off, and the seed layer and the via plating layer provided on the side surface and the bottom surface of the via provided in the interlayer insulating layer can be prevented from falling off. It can be prevented from falling off. As a result, a fine pattern (5 μm or less) of the wiring layer can be achieved.
また、本発明の実施形態によれば、熱硬化性樹脂と無機フィラーとの混合物からなる層間絶縁層へのビア形成後、ビアにより発生する層間絶縁層の表面およびビアの側面ならびに底面の熱硬化性樹脂の残渣を除去するデスミア・粗化工程を、フルオロカーボン系ガスを含む反応イオンエッチング（ＲＩＥ）により行うことで、小径ビア形成に有利となる。 Further, according to the embodiment of the present invention, after forming vias on the interlayer insulating layer composed of a mixture of a thermosetting resin and an inorganic filler, the surface of the interlayer insulating layer generated by the vias and the side surfaces and bottom surfaces of the vias are thermally cured. By performing the desmear / roughening step of removing the residue of the sex resin by reactive ion etching (RIE) containing a fluorocarbon-based gas, it is advantageous for forming small-diameter vias.
さらに、好適例として、ＲＩＥのプロセスガスとして、ＣＨＦ３またはＣＨＦ３およびＯ２からなり、流量比Ｏ２／（ＣＨＦ３＋Ｏ２）が０〜５％であるガスを用いた場合は、層間絶縁層の表面およびビアの側面ならびに底面を、安価に、無機フィラーの突出がなく凹部を有する粗面とすることができる。 Further, as a preferred example, when a gas composed of CHF 3 or CHF 3 and O 2 and having a flow rate ratio O 2 / (CHF 3 + O 2 ) of 0 to 5% is used as the RIE process gas, interlayer insulation is used. The surface of the layer and the sides and bottom of the via can be inexpensively roughened with recesses without protrusion of the inorganic filler.
図１（ａ）〜（ｇ）は、それぞれ、本発明が対象とするＳＡＰ（セミアディティブ法）の一例の工程を説明するための図である。まず、図１（ａ）に示すように、基板１上に、熱硬化性樹脂と無機フィラーとの混合物からなる層間絶縁層２を形成する。次に、図１（ｂ）に示すように、層間絶縁層２にレーザービア加工を施してビア３を形成するとともに、ビア３を形成した層間絶縁層２に対しデスミア・粗化工程を実施する。次に、図１（ｃ）に示すように、デスミア・粗化工程後クリーニング工程を経た、ビア３を有する層間絶縁層２の表面に、無電解銅めっきを施し、シード層４を形成する。次に、図１（ｄ）に示すように、非回路部分にめっきレジスト５を形成し、図１（ｅ）に示すように、ビア３（および層間絶縁層２の表面の回路部分にも）めっき層６を形成する。その後、図１（ｆ）に示すように、めっきレジスト５を剥離し、図１（ｇ）に示すように、シード層４をエッチングして除去する。 1 (a) to 1 (g) are diagrams for explaining an example process of SAP (semi-additive method), which is the subject of the present invention, respectively. First, as shown in FIG. 1A, an interlayer insulating layer 2 made of a mixture of a thermosetting resin and an inorganic filler is formed on the substrate 1. Next, as shown in FIG. 1 (b), the interlayer insulating layer 2 is subjected to laser via processing to form the via 3, and the interlayer insulating layer 2 on which the via 3 is formed is subjected to a desmear / roughening step. .. Next, as shown in FIG. 1C, electroless copper plating is applied to the surface of the interlayer insulating layer 2 having the via 3 which has undergone the desmear / roughening step and then the cleaning step to form the seed layer 4. Next, as shown in FIG. 1 (d), a plating resist 5 is formed in the non-circuit portion, and as shown in FIG. 1 (e), the via 3 (and the circuit portion on the surface of the interlayer insulating layer 2) is also formed. The plating layer 6 is formed. Then, as shown in FIG. 1 (f), the plating resist 5 is peeled off, and as shown in FIG. 1 (g), the seed layer 4 is etched and removed.
本発明のプリント配線板およびその製造方法の特徴は、図１（ａ）〜（ｇ）に示すＳＡＰの各工程のうち、熱硬化性樹脂と無機フィラーとの混合物からなる層間絶縁層２を、デスミア・粗化工程を実施する工程の改良にある。 The feature of the printed wiring board of the present invention and the manufacturing method thereof is that the interlayer insulating layer 2 made of a mixture of a thermosetting resin and an inorganic filler in each process of SAP shown in FIGS. 1 (a) to 1 (g) is provided. It is in the improvement of the process of carrying out the desmear / roughening process.
すなわち、本発明のプリント配線板は、層間絶縁層２として熱硬化性樹脂と無機フィラーとの混合物を用いたプリント配線板において、層間絶縁層２の表面および層間絶縁層２に設けたビア３の側面ならびに底面が、無機フィラーの突出がなく凹部を有する粗面であることを特徴としている。また、本発明のプリント配線板の製造方法は、少なくとも、熱硬化性樹脂と無機フィラーとの混合物からなる層間絶縁層２にビア３を形成するビア形成工程、その後のデスミア・粗化工程、クリーニング工程を含むＳＡＰ法によるプリント配線板の製造方法において、デスミア・粗化工程は、フルオロカーボン系ガスを含む反応性イオンエッチング（ＲＩＥ）により、層間絶縁層２内の熱硬化性樹脂より無機フィラーを優先的にエッチングする条件で行うことを特徴とする。 That is, the printed wiring board of the present invention is a printed wiring board using a mixture of a thermosetting resin and an inorganic filler as the interlayer insulating layer 2, and the via 3 provided on the surface of the interlayer insulating layer 2 and the interlayer insulating layer 2. The side surface and the bottom surface are rough surfaces having recesses without protrusion of the inorganic filler. Further, the method for manufacturing a printed wiring board of the present invention is at least a via forming step of forming a via 3 in an interlayer insulating layer 2 made of a mixture of a thermosetting resin and an inorganic filler, a subsequent desmear / roughening step, and cleaning. In the method for manufacturing a printed wiring board by the SAP method including the process, in the desmear / roughening process, the inorganic filler is prioritized over the thermosetting resin in the interlayer insulating layer 2 by reactive ion etching (RIE) containing a fluorocarbon gas. It is characterized in that it is carried out under the condition of etching.
図２（ａ）〜（ｄ）は、それぞれ、本発明のプリント配線板の製造方法の一例の各工程を説明するための図である。図２（ａ）〜（ｄ）に示した例においては、層間絶縁層２の平らな表面を示しているが、本発明の対象となる表面とは、層間絶縁層２の表面の回路を形成する部分のみならず、層間絶縁層２に設けたビア３の側面および底面も対象となる。 2 (a) to 2 (d) are diagrams for explaining each step of an example of the method for manufacturing a printed wiring board of the present invention, respectively. In the examples shown in FIGS. 2 (a) to 2 (d), the flat surface of the interlayer insulating layer 2 is shown, but the surface to be the subject of the present invention forms a circuit on the surface of the interlayer insulating layer 2. Not only the portion to be provided, but also the side surface and the bottom surface of the via 3 provided in the interlayer insulating layer 2.
まず、図２（ａ）に示すように、基板（図示せず）の上に、熱硬化性樹脂１１と無機フィラー１２との混合物からなる層間絶縁層２を形成し、レーザービア加工により必要な個所にビア３を形成する。ここで、層間絶縁層２の表面２ａは、層間絶縁層２の表面および層間絶縁層２に設けたビア３の側面ならびに底面のいずれかを示している。また、熱硬化性樹脂１１および無機フィラー１２としては、従来から知られているものを使用することができる。 First, as shown in FIG. 2A, an interlayer insulating layer 2 made of a mixture of a thermosetting resin 11 and an inorganic filler 12 is formed on a substrate (not shown), which is required by laser via processing. Via 3 is formed at the location. Here, the surface 2a of the interlayer insulating layer 2 indicates either the surface of the interlayer insulating layer 2 or the side surface or the bottom surface of the via 3 provided on the interlayer insulating layer 2. Further, as the thermosetting resin 11 and the inorganic filler 12, conventionally known ones can be used.
次に、ビア３形成時のレーザー加工により、層間絶縁層２の表面およびビア３の側面ならびに底面に残る残渣を除去して粗面とするための、デスミア・粗化工程を行い、図２（ｂ）に示すような層間絶縁層２の表面２ａを得る。この際、デスミア・粗化工程は、フルオロカーボン系ガスを含む反応性イオンエッチング（ＲＩＥ）により、層間絶縁層２内の熱硬化性樹脂１１より無機フィラー１２を優先的にエッチングする条件で行う。その結果、図２（ｂ）に示すように、層間絶縁層２の表面２ａを、熱硬化性樹脂１１の表面１１ａと熱硬化性樹脂１１の表面１１ａに対し凹形状に窪んだ無機フィラー１２の凹部１２ａとから構成し、無機フィラー１２の熱硬化性樹脂１１の表面１１ａからの突出を少なくしている。 Next, a desmear / roughening step was performed to remove residues remaining on the surface of the interlayer insulating layer 2 and the side surfaces and the bottom surface of the via 3 by laser processing at the time of forming the via 3 to make a rough surface. The surface 2a of the interlayer insulating layer 2 as shown in b) is obtained. At this time, the desmear / roughening step is performed under the condition that the inorganic filler 12 is preferentially etched over the thermosetting resin 11 in the interlayer insulating layer 2 by reactive ion etching (RIE) containing a fluorocarbon gas. As a result, as shown in FIG. 2B, the surface 2a of the interlayer insulating layer 2 is formed by the inorganic filler 12 having a concave shape with respect to the surface 11a of the thermosetting resin 11 and the surface 11a of the thermosetting resin 11. It is composed of recesses 12a to reduce the protrusion of the inorganic filler 12 from the surface 11a of the thermosetting resin 11.
ここで、ＲＩＥのプロセスガスが、ＣＨＦ３またはＣＨＦ３およびＯ２からなり、流量比Ｏ２／（ＣＨＦ３＋Ｏ２）が０〜５％であること、および、ＲＩＥのプロセスガスの圧力が１０Ｐａ以下であること、が好ましい態様となる。なお、デスミア・粗化工程を行うことにより、上記熱硬化性樹脂の表面１１ａおよび無機フィラー１２の凹部１２ａ上に、フッ化物被膜１３が形成される。 Here, the process gas of RIE is composed of CHF 3 or CHF 3 and O 2 , the flow rate ratio O 2 / (CHF 3 + O 2 ) is 0 to 5%, and the pressure of the process gas of RIE is 10 Pa. The following is a preferred embodiment. By performing the desmear / roughening step, the fluoride film 13 is formed on the surface 11a of the thermosetting resin and the recess 12a of the inorganic filler 12.
このフッ化物被膜１３を除去するために、クリーニング工程を行い、図２（ｃ）に示すように、表面のフッ化物被膜１３を除去した熱硬化性樹脂１１の表面１１ａおよび無機フィラー１２の凹部１２ａを得ている。クリーニング工程は、スパッタリングにより行われることが好ましい。また、クリーニング工程のエッチング量は、ＲＩＥ時に層間絶縁層２の表面に形成されるフッ化物被膜１３の除去に十分な量であり、無機フィラーの露出が少ない状態が保たれるように設定されるこることが好ましい。さらに、クリーニング工程のエッチング量は、１ｎｍ〜（無機フィラー１２の平均粒径×２）の範囲であることが好ましい。いずれも、その後のシード層の形成に好ましい層間絶縁層２ａの表面を得ることができる。 In order to remove the fluoride coating 13, a cleaning step was performed, and as shown in FIG. 2C, the surface 11a of the thermosetting resin 11 from which the fluoride coating 13 on the surface was removed and the recess 12a of the inorganic filler 12 were removed. Is getting. The cleaning step is preferably performed by sputtering. Further, the etching amount in the cleaning step is an amount sufficient for removing the fluoride film 13 formed on the surface of the interlayer insulating layer 2 at the time of RIE, and is set so that the state where the inorganic filler is less exposed is maintained. It is preferable to do this. Further, the etching amount in the cleaning step is preferably in the range of 1 nm to (average particle size of the inorganic filler 12 × 2). In either case, the surface of the interlayer insulating layer 2a, which is preferable for the subsequent formation of the seed layer, can be obtained.
次に、図２（ｄ）に示すように、層間絶縁層２の表面２ａに無電解銅めっきによりシード層４を形成する。この際、層間絶縁層２の表面２ａとシード層４とは、シード層４と熱硬化性樹脂１１の表面１１ａとの接触面積が大きくなるとともに、シード層４が無機フィラー１２の凹形状の窪んだ凹部１２ａの内部に入り込む状態となる。そのため、層間絶縁層２とシード層４とが強固に密着し、シード層４のピール強度が高くなり、シード層４が層間絶縁層２から脱落することはなくなる。 Next, as shown in FIG. 2D, a seed layer 4 is formed on the surface 2a of the interlayer insulating layer 2 by electroless copper plating. At this time, the surface 2a of the interlayer insulating layer 2 and the seed layer 4 have a large contact area between the seed layer 4 and the surface 11a of the thermosetting resin 11, and the seed layer 4 has a concave recess of the inorganic filler 12. It is in a state of entering the inside of the recess 12a. Therefore, the interlayer insulating layer 2 and the seed layer 4 are firmly adhered to each other, the peel strength of the seed layer 4 is increased, and the seed layer 4 does not fall off from the interlayer insulating layer 2.
（実施例）
以下の条件で、熱硬化性樹脂と無機フィラーとの混合物からなる層間絶縁層の表面に、デスミア・粗化工程およびクリーニング工程を実施した後、銅からなるシード層を形成した。そして、シード層に対し高速加速寿命試験（ＨＡＳＴ）を実施し、ＨＡＳＴ後のシード層のピール強度を測定した。また、デスミア・粗化工程実施後の表面形状をＳＥＭで撮影した。
(Example)
Under the following conditions, a seed layer made of copper was formed on the surface of the interlayer insulating layer made of a mixture of a thermosetting resin and an inorganic filler after performing a desmear / roughening step and a cleaning step. Then, a high-speed accelerated life test (HAST) was carried out on the seed layer, and the peel strength of the seed layer after HAST was measured. In addition, the surface shape after the desmear / roughening process was photographed by SEM.
条件は以下の通りである。
・層間絶縁材：
ＡＢＦ（シリカフィラー４０％入り、平均粒径１００ｎｍ）、
・ドライデスミア・粗化工程：
ＣＣＰ方式ＲＩＥ装置、Ｏ２＋ＣＨＦ３流量１００−５００ｓｃｃｍ、
Ｏ２／（Ｏ２＋ＣＨＦ３）０％−１０％、プロセスガス圧１−１０Ｐａ、
ＲＦ出力１００−５００Ｗ、処理時間１−２０分
・クリーニング処理：
Ａｒ逆スパッタ、５００−１００Ｗ、０．５−５分、
・シード層形成：
スパッタＣｕ／Ｔｉ合計１００−３００ｎｍ厚み、
・シード層後銅めっき：
３５μｍ厚み、
・ＨＡＳＴ：
１３０℃／８５％ＲＨ／１００ｈｒ。
結果を以下の表１に示す。
The conditions are as follows.
・ Interlayer insulation material:
ABF (40% silica filler, average particle size 100 nm),
・ Dry desmear ・ Roughening process:
CCP RIE apparatus, O 2 + CHF 3 flow rate 100-500 sccm,
O 2 / (O 2 + CHF 3 ) 0% -10%, process gas pressure 1-10 Pa,
RF output 100-500W, processing time 1-20 minutes ・ Cleaning processing:
Ar reverse sputtering, 500-100W, 0.5-5 minutes,
・ Seed layer formation:
Sputtered Cu / Ti total 100-300 nm thickness,
・ Copper plating after seed layer:
35 μm thickness,
・ HAST:
130 ° C / 85% RH / 100hr.
The results are shown in Table 1 below.
表１の結果から、デスミア・粗化工程後の層間絶縁層表面のＳＥＭ写真とＨＡＳＴ後ピール強度とから、層間絶縁層の表面（層間絶縁層の表面および層間絶縁層に設けたビアの側面ならびに底面）が、無機フィラーの突出がなく凹部を有する粗面である場合に、高いＨＡＳＴ後ピール強度を得ることができることがわかった。 From the results in Table 1, from the SEM photograph of the surface of the interlayer insulating layer after the desmear / roughening step and the peel strength after HAST, the surface of the interlayer insulating layer (the surface of the interlayer insulating layer and the side surface of the via provided on the interlayer insulating layer and the side surface of the via It was found that a high peel strength after HAST can be obtained when the bottom surface) is a rough surface having recesses without protrusion of the inorganic filler.
また、デスミア・粗化工程のＲＩＥにおけるＯ２／（Ｏ２＋ＣＨＦ３）比とＳＥＭ写真（ＨＡＳＴ後ピール強度）とから、デスミア・粗化工程のＲＩＥにおけるプロセスガスが、ＣＨＦ３またはＣＨＦ３およびＯ２からなり、流量比Ｏ２／（ＣＨＦ３＋Ｏ２）が０〜５％であると、上記無機フィラーの突出がなく凹部を有する粗面を得ることができることがわかった。 Further, from the O 2 / (O 2 + CHF 3 ) ratio in the RIE of the desmear / roughening process and the SEM photograph (peel strength after HAST), the process gas in the RIE of the desmear / roughening process is CHF 3 or CHF 3 It was found that when it was composed of O 2 and the flow rate ratio O 2 / (CHF 3 + O 2 ) was 0 to 5%, a rough surface having recesses could be obtained without the above-mentioned inorganic filler protruding.
１ 基板
２ 層間絶縁層
２ａ 表面
３ ビア
４ シード層
５ めっきレジスト
１１ 熱硬化性樹脂
１１ａ 表面
１２ 無機フィラー
１２ａ 凹部
１３ フッ化物被膜
1 Substrate 2 Interlayer insulation layer 2a Surface 3 Via 4 Seed layer 5 Plating resist 11 Thermosetting resin 11a Surface 12 Inorganic filler 12a Recess 13 Fluoride coating
Claims (7)
前記デスミア・粗化工程は、フルオロカーボン系ガスを含む反応性イオンエッチング（ＲＩＥ）により、前記層間絶縁層内の前記熱硬化性樹脂より前記無機フィラーを優先的にエッチングする条件で行うことを特徴とするプリント配線板の製造方法。 At least in the method for manufacturing a printed wiring board by the SAP method, which includes a via forming step of forming vias in an interlayer insulating layer composed of a mixture of a thermosetting resin and an inorganic filler, a subsequent desmear / roughening step, and a cleaning step.
The desmear / roughening step is characterized in that the inorganic filler is preferentially etched over the thermosetting resin in the interlayer insulating layer by reactive ion etching (RIE) containing a fluorocarbon-based gas. Manufacturing method of printed wiring board.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114284504A (en) * | 2021-12-22 | 2022-04-05 | 上海恩捷新材料科技有限公司 | Composite current collector, preparation method thereof, pole piece thereof and battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114284504A (en) * | 2021-12-22 | 2022-04-05 | 上海恩捷新材料科技有限公司 | Composite current collector, preparation method thereof, pole piece thereof and battery |
| CN114284504B (en) * | 2021-12-22 | 2023-11-28 | 上海恩捷新材料科技有限公司 | Composite current collector, preparation method thereof, pole piece and battery |
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