Copper foil composite structure and method of manufacturing the same

Abstract

PURPOSE: To provide a copper foil composite structure with an excellent performance of peel strength, and a production method thereof.SOLUTION: A production method of a copper foil composite structure includes: providing a carrier; forming a copper-nitrogen composite layer on the carrier by performing a co-plating process using a copper plating solution and a nitrogen-containing compound; and forming a copper foil layer on the copper-nitrogen composite layer. The copper foil composite structure is also provided.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a copper foil composite structure and a method for making the same. [Background technology]

[0002] Current copper foil structures typically use release layers, but the stability of the release layer affects the peel strength during subsequent manufacturing processes. For example, the inorganic layer in the current release layer is prone to sagging during the manufacturing process, resulting in uneven distribution of the release layer and uneven peel strength. Furthermore, the organic layer increases its peel strength at high temperatures, making it difficult to separate the carrier from the copper foil. Summary of the Invention [Problem to be solved by the invention]

[0003] The inorganic layer in the current release layer is prone to sagging during the manufacturing process, which causes problems such as uneven distribution of the release layer and uneven peel strength. [Means for solving the problem]

[0004] The present invention provides a copper foil composite structure having excellent performance in peel strength and a method for manufacturing the same.

[0005] The method for producing a copper foil composite structure of the present invention includes providing a carrier, performing a co-plating process using a copper plating solution and a nitrogen-containing compound to form a copper-nitrogen composite layer on the carrier, and forming a copper foil layer on the copper-nitrogen composite layer.

[0006] In one embodiment of the present invention, the concentration range of copper ions in the above-mentioned copper plating solution is between 10 g / L and 60 g / L.

[0007] In one embodiment of the present invention, the copper plating solution described above contains copper pyrophosphate or copper sulfate.

[0008] In one embodiment of the present invention, the concentration range of the nitrogen-containing compound is between 1 ppm and 100 ppm.

[0009] In one embodiment of the present invention, the nitrogen-containing compound includes 5-mercapto-1-phenyltetrazole, triaminotriazole, benzotriazole, 5-aminotetrazole, 5-tolyltriazole, 3,5-diamino-1,2,4-triazole, 5-chlorobenzotriazole, carboxybenzotriazole, or a combination thereof.

[0010] In one embodiment of the present invention, the current density of the above-mentioned co-plating step is between 1.5 ASD and 4.5 ASD, the co-plating temperature is between 40°C and 55°C, and / or the co-plating time is between 10 seconds and 30 seconds.

[0011] The copper foil composite structure of the present invention includes a carrier, a copper foil layer, and a copper-nitrogen composite layer, the copper-nitrogen composite layer being located between the carrier and the copper foil layer.

[0012] In one embodiment of the present invention, the thickness of the above-mentioned copper-nitrogen composite layer is between 50 nm and 200 nm, and the thickness of the copper foil layer is between 1 μm and 5 μm.

[0013] In one embodiment of the present invention, the two opposing surfaces of the above-mentioned copper-nitrogen composite layer are in direct contact with the carrier and the copper foil layer, respectively.

[0014] In one embodiment of the present invention, the above-mentioned copper foil composite structure further includes a roughening layer, an anti-oxidation layer, an anti-corrosion layer, and a silicide layer stacked in order on the copper foil layer. [Effects of the Invention]

[0015] As described above, the present invention forms a highly stable copper-nitrogen composite layer on the surface of the carrier through a co-plating process, which forms part of the copper foil composite structure, thereby effectively preventing mutual bonding between the carrier and copper atoms in the copper foil layer during subsequent processes (e.g., heat treatment, etc.), thereby achieving excellent peel strength performance.

[0016] In order to make the above features and advantages of the present invention more clearly comprehensible, the following embodiments are provided and described in detail in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a partial flow diagram of a method for manufacturing a copper foil composite structure according to one embodiment of the present invention. [Figure 2] 1 is a partially layered schematic diagram of a copper foil composite structure according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0018] In the following detailed description, for purposes of explanation and not limitation, exemplary embodiments disclosing specific details are set forth to provide a thorough understanding of various principles of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced in other embodiments that deviate from the specific details disclosed herein. Also, descriptions of well-known devices, methods, and materials may be omitted so as not to obscure the description of various principles of the present invention.

[0019] The present invention will be described more fully hereinafter with reference to the drawings of the present embodiments, however, this invention may be embodied in many different ways and should not be limited to only the embodiments set forth herein.

[0020] Unless otherwise defined, all technical terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0021] The term "between" as used herein to define a range of values ​​is intended to encompass the range equal to and between the recited endpoints. For example, if a size range is between a first number and a second number, that means it can encompass the first number, the second number, and any value between the first and second numbers.

[0022] Figure 1 is a partial flow diagram of a method for manufacturing a copper foil composite structure according to one embodiment of the present invention. Figure 2 is a partial layering diagram of a copper foil composite structure according to one embodiment of the present invention.

[0023] 1 and 2, the method for manufacturing a copper foil composite structure 100 of this embodiment includes at least the following steps: First, as shown in step S1, a carrier 110 is provided. Next, as shown in step S2, a co-plating process is performed using a copper plating solution and a nitrogen-containing compound to form a copper-nitrogen composite layer 120 on the carrier 110. Then, as shown in step S3, a copper foil layer 130 is formed on the copper-nitrogen composite layer 120. In this way, the present invention forms a highly stable copper-nitrogen composite layer 120 on the surface of the carrier 110 through the co-plating process, thereby forming part of the copper foil composite structure 100. This effectively prevents copper atoms in the carrier 110 and the copper foil layer 130 from bonding to each other during subsequent processes (e.g., heat treatment, etc.), thereby achieving excellent peel strength.

[0024] In some embodiments, the copper-nitrogen composite layer 120 provides a release interface, allowing the structure to be easily separated from the carrier 110 after the copper foil layer 130 is pressed onto it, while the copper-nitrogen composite layer 120 can also protect the base. Therefore, the copper foil composite structure 100 of the present invention can omit the use of conventional release layers (inorganic and organic layers) and base layers, thereby avoiding problems such as uneven distribution and peel strength caused by sagging. At the same time, the easy processability of the co-plating process can simplify the manufacturing process and reduce manufacturing costs (current release layers are composed of relatively expensive metal components).

[0025] Furthermore, the performance of the product can be further improved by adjusting the parameters of the co-plating process, for example, by the following design:

[0026] In some embodiments, the copper ion concentration in the copper plating solution ranges from 10 grams per liter (g / L) to 60 g / L (e.g., 10 g / L, 20 g / L, 30 g / L, 40 g / L, 50 g / L, 60 g / L, or any suitable value between 10 g / L and 60 g / L), but the present invention is not limited thereto. Here, the copper ion concentration is calculated by converting grams of copper ions based on the copper content in the compound. For example, the copper plating solution contains copper sulfate pentahydrate with a copper content of 25.43%. That is, 100 g of copper sulfate pentahydrate contains 25.43 g of copper ions.

[0027] In some embodiments, the copper plating solution includes copper pyrophosphate or copper sulfate, although the invention is not limited thereto.

[0028] In some embodiments, the concentration of the nitrogen-containing compound ranges from 1 ppm to 100 ppm (e.g., 1 ppm, 10 ppm, 30 ppm, 50 ppm, 70 ppm, 100 ppm, or any suitable value between 1 ppm and 100 ppm), but the present invention is not limited thereto. Here, in calculating the concentration of the nitrogen-containing compound, 1 ppm represents 1 milligram (mg) of the nitrogen-containing compound added to 1 liter (L) of copper plating solution.

[0029] In some embodiments, the nitrogen-containing compound includes, but is not limited to, 5-mercapto-1-phenyltetrazole (5-mercapto-1-phenyl-1H-tetrazole, 5-PTZ), triaminotriazole (3-AT), benzotriazole (BTA), 5-aminotetrazole (5-ATZ), 5-tolyltriazole (TTA), 3,5-diamino-1,2,4-triazole, 5-chlorobenzotriazole (5-CLBTA), carboxybenzotriazole (CBTA), or a combination thereof.

[0030] In some embodiments, the current density of the co-plating step is between 1.5 ASD and 4.5 ASD (e.g., 1.5 ASD, 2.5 ASD, 3.5 ASD, 4.5 ASD, or any suitable value between 1.5 ASD and 4.5 ASD), although the present invention is not limited thereto.

[0031] In some embodiments, the co-plating temperature is between 40°C and 55°C (e.g., 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, or any suitable value between 40°C and 50°C), although the invention is not limited thereto.

[0032] In some embodiments, the co-plating time is between 10 seconds and 30 seconds (e.g., 10 seconds, 20 seconds, 25 seconds, 30 seconds, or any suitable value between 10 seconds and 30 seconds), although the present invention is not limited thereto.

[0033] In some embodiments, a high-temperature pressing process is employed in the manufacturing process of the copper foil composite structure 100, and the copper nitride composite layer 120 of the present invention can maintain excellent stability during the process. That is, temperatures (room temperature (e.g., 25°C) or high temperatures (e.g., temperatures higher than 350°C)) do not significantly adversely affect the copper nitride composite layer 120 of the present invention, but the present invention is not limited thereto.

[0034] In some embodiments, products often require fine wiring and high-frequency signal transmission, which requires the copper foil layer 130 to be designed with low roughness (e.g., Rz of 0.8 μm or less) and / or thin (e.g., between 1 μm and 5 μm). However, these designs are prone to creases and tears during transportation due to limitations in mechanical properties. The present invention can reduce the likelihood of these problems occurring by using a stacking design of the carrier 110, the copper-nitrogen composite layer 120, and the thin copper foil layer 130, but the present invention is not limited thereto.

[0035] In some embodiments, the co-plating and pressing processes can bring the two opposing surfaces of the copper-nitrogen composite layer 120 into direct contact with the carrier 110 and the copper foil layer 130, respectively, thereby further reducing the probability of the above-mentioned situation occurring, but the present invention is not limited thereto.

[0036] In some embodiments, copper foil or aluminum foil having a thickness of 18 μm or more is used as the carrier 110 to further reduce creases and tears during production and transportation, and to provide sufficient mechanical strength in the subsequent pressing process (e.g., bonding the thinned copper foil layer 130 and the prepreg). Here, the carrier 110 can be peeled off by an appropriate method after the pressing process, but the present invention is not limited thereto.

[0037] In some embodiments, the thickness of the copper-nitrogen composite layer 120 is between 50 nm and 200 nm (e.g., 50 nm, 100 nm, 150 nm, 200 nm, or any suitable number between 50 nm and 200 nm), which can provide excellent protection while reducing the possibility of adversely affecting the electroplating thickness of the copper foil layer 130, but the present invention is not limited thereto.

[0038] In some embodiments, an acid cleaning step is performed before step S1. The acid cleaning step is, for example, a step of cleaning the carrier 110 with sulfuric acid (e.g., with a concentration of 10%) to remove oxides on the surface, but the present invention is not limited thereto.

[0039] In some embodiments, after step S3, the copper foil composite structure may further include a roughening layer, an anti-oxidation layer, an anti-corrosion layer, and / or a silicide layer (not shown) sequentially formed on the copper foil layer.

[0040] In some embodiments, the roughened layer is electroplated using a copper plating solution, the copper concentration of the plating solution is between 5 g / L and 15 g / L, the sulfuric acid concentration is between 60 g / L and 90 g / L, a pulse current is used as the energy supply, and the thickness range is between 0.5 μm and 1.5 μm, but the present invention is not limited thereto.

[0041] In some embodiments, the antioxidant layer is formed from an electrolyte containing nickel ions and zinc ions, the zinc ion concentration is between 0 g / L and 8 g / L, the nickel ion concentration is between 0.5 g / L and 2 g / L, and the thickness range is between 5 nm and 10 nm, although the present invention is not limited thereto.

[0042] In some embodiments, the anti-corrosion layer is a chromic acid impregnated layer, the concentration of potassium dichromate is between 0.8 g / L and 1.5 g / L, and the thickness range is between 5 nm and 10 nm, but the present invention is not limited thereto.

[0043] In some embodiments, the silicide layer is sprayed or impregnated with silane, and the selected silane is an amino-based silane (3-aminopropyltrimethoxysilane), with a concentration between 1 g / L and 1.5 g / L and a thickness range between 5 nm and 10 nm, but the invention is not limited thereto.

[0044] It should be noted that the above-mentioned numerical ranges, specific types, and related details are not intended to limit the present invention, and related conditions can be adjusted according to actual design requirements. Any co-plating process using a copper plating solution and a nitrogen-containing compound to form a copper-nitrogen composite layer 120 on the carrier 110 falls within the scope of the present invention. In addition, the actual operating means, such as the co-plating process and the acid washing process, may be any appropriate content known to those skilled in the art, and therefore will not be described in detail herein.

[0045] The effects of the present invention will be described in detail below with reference to examples and comparative examples, but the scope of the present invention is not limited to the scope of the examples.

[0046] The copper foil composite structures produced in each of the examples and comparative examples were evaluated based on the following methods.

[0047] Peel strength: At room temperature: The roughened layer is attached to a glass plate with the test width of 1.27 cm, and the peel strength between the carrier and the copper foil layer is measured using a tensile tester. Peel strength at 200°C: The copper foil layer and prepreg are thermocompressed at 200°C. The peel strength between the carrier and the copper foil layer is measured using a tensile tester with a test width of 2.50 cm. Peel strength at 390°C: The ultra-thin copper foil is baked at 390°C for 5 minutes, and then attached to a glass plate with the roughened layer facing down. The test width is 1.27 cm, and the peel strength between the carrier and the copper foil layer is measured using a tensile tester.

[0048] Examples 1 to 3 and Comparative Example 1 are produced by the following methods.

[0049] Example 1

[0050] In Example 1, the copper foil composite structure was composed of a carrier (18 μm thick, copper foil), a copper-nitrogen composite layer (108 nm thick), a copper foil layer (3 μm thick), a roughening layer (copper nodule particles), an oxidation prevention layer (6 nm thick, nickel-zinc alloy), an anti-corrosion layer (5 nm thick, chromium-containing protective layer), and a silicide layer (5 nm thick, aminosiloxane). The conditions for the co-plating process to form the copper-nitrogen composite layer were as follows: the copper ion concentration in the copper plating solution was 20 g / L, the copper plating solution was a copper sulfate plating solution, the nitrogen-containing compound concentration was 25 ppm, the nitrogen-containing compound was 5-ATZ, the current density was 2 ASD, the co-plating temperature was 45°C, and the co-plating time was 15 seconds.

[0051] <Example 2>

[0052] In Example 2, the copper foil composite structure was composed of a carrier (18 μm thick, copper foil), a copper-nitrogen composite layer (144 nm thick), a copper foil layer (3 μm thick), a roughening layer (copper nodule particles), an oxidation prevention layer (5 nm thick, zinc metal layer), an anti-corrosion layer (5 nm thick, chromium layer), and a silicide layer (5 nm thick, aminosiloxane). The conditions for the co-plating process to form the copper-nitrogen composite layer were as follows: the copper ion concentration in the copper plating solution was 10 g / L, the copper plating solution was a copper pyrophosphate plating solution, the nitrogen-containing compound concentration was 15 ppm, the nitrogen-containing compound was 3-AT, the current density was 2 ASD, the co-plating temperature was 45°C, and the co-plating time was 20 seconds.

[0053] Example 3

[0054] In Example 3, the copper foil composite structure was composed of a carrier (18 μm thick, copper foil), a copper-nitrogen composite layer (180 nm thick), a copper foil layer (3 μm thick), a roughening layer (copper nodule particles), an oxidation prevention layer (5 nm thick, nickel-zinc metal layer), an anti-corrosion layer (5 nm thick, chromium layer), and a silicide layer (5 nm thick, aminosiloxane). The conditions for the co-plating process to form the copper-nitrogen composite layer were as follows: the copper ion concentration in the copper plating solution was 40 g / L, the copper plating solution was a copper pyrophosphate plating solution, the nitrogen-containing compound concentration was 10 ppm, the nitrogen-containing compound was CBTA, the current density was 2.5 ASD, the co-plating temperature was 45°C, and the co-plating time was 25 seconds.

[0055] <Comparative Example 1>

[0056] Comparative Example 1 is similar to Example 1, except that the copper-nitrogen composite layer was replaced with a known release layer and base layer (commercially available model number NPUE).

[0057] As can be seen from the results in Table 1, the peel strengths of Examples 1 to 3 having the copper-nitrogen composite layer of the present invention are lower than the peel strength of Comparative Example 1. For example, in Example 1, the peel strength can be reduced by about two times at room temperature and by about three times at high temperatures, so the copper foil composite structure of the present invention certainly has excellent performance in terms of peel strength.

[0058] [Table 1]

[0059] As described above, the present invention forms a highly stable copper-nitrogen composite layer on the surface of the carrier through a co-plating process, which forms part of the copper foil composite structure, thereby effectively preventing mutual bonding between the carrier and copper atoms in the copper foil layer during subsequent processes (e.g., heat treatment, etc.), thereby achieving excellent peel strength performance.

[0060] Although the present invention has been disclosed by the above embodiments, these are not intended to limit the present invention, and a person skilled in the art can make some changes and modifications without departing from the spirit and scope of the present invention, and therefore the protection scope of the present invention is to be defined by the appended claims. [Industrial Applicability]

[0061] The copper foil composite structure and its manufacturing method can be applied in the field of copper foil composite structures. [Explanation of symbols]

[0062] 100 Copper foil composite structure 110 Career 120 Copper-nitrogen composite layer 130 Copper foil layer S1, S2, S3 steps

Claims

1. Providing a career and Co-plating the carrier with a copper plating solution and a nitrogen-containing compound to form a copper-nitrogen composite layer on the carrier; forming a copper foil layer on the copper-nitrogen composite layer; Including, The concentration range of the nitrogen-containing compound is between 1 ppm and 100 ppm; The method for producing a copper foil composite structure, wherein the nitrogen-containing compound comprises 5-mercapto-1-phenyltetrazole, triaminotriazole, benzotriazole, 5-aminotetrazole, 5-tolyltriazole, 3,5-diamino-1,2,4-triazole, 5-chlorobenzotriazole, carboxybenzotriazole, or a combination thereof.

2. 2. The method for manufacturing a copper foil composite structure according to claim 1, wherein the concentration of copper ions in the copper plating solution is in the range of 10 g / L to 60 g / L.

3. The method for manufacturing a copper foil composite structure according to claim 1 , wherein the copper plating solution contains copper pyrophosphate or copper sulfate.

4. 2. The method for manufacturing a copper foil composite structure according to claim 1, wherein the current density of the co-plating step is between 1.5 ASD and 4.5 ASD, the co-plating temperature is between 40°C and 55°C, and / or the co-plating time is between 10 seconds and 30 seconds.

5. Career and a copper foil layer; a copper-nitrogen composite layer located between the carrier and the copper foil layer, the copper-nitrogen composite layer having a thickness of between 50 nm and 200 nm; A copper foil composite structure including a roughening layer, an anti-oxidation layer, an anti-corrosion layer, and a silicide layer stacked in this order on the copper foil layer.

6. A copper foil composite structure as described in claim 5, wherein the thickness of the copper foil layer is between 1 μm and 5 μm.

7. 6. The copper foil composite structure of claim 5, wherein two opposing surfaces of said copper-nitrogen composite layer are in direct contact with said carrier and said copper foil layer, respectively.

Images