Ultrathin copper foil with carrier and method for producing same

Abstract

The invention discloses an ultrathin copper foil with a carrier and a manufacturing method thereof. The ultra-thin copper foil with the carrier comprises a carrier copper foil, a release layer and an ultra-thin copper foil layer. The release layer is formed on one side surface of the carrier copper foil. The release layer is composed of a copper-containing organic compound, and the chemical structure of the copper-containing organic compound has at least a copper-nitrogen bond (Cu-N bond). The ultrathin copper foil layer is formed on the surface of one side, far away from the carrier copper foil, of the release layer. And the carrier copper foil can be separated from the ultrathin copper foil layer through the release layer. Therefore, the carrier copper foil and the ultra-thin copper foil layer in the ultra-thin copper foil with the carrier have a better release effect, and the technical problem that the tearing force is difficult to control due to the fact that the distribution and the content of the release layer are not uniform in the prior art can be solved.

Description

Technical Field

[0001] The invention relates to a copper foil, in particular to an ultra-thin copper foil with a carrier and a manufacturing method thereof. Background Art

[0002] In the prior art, the fine lines of a printed circuit board (PCB) are made by using an ultra-thin copper foil product. The structure of the ultra-thin copper foil product is a laminated structure of an ultra-thin copper foil, a release layer, and a carrier copper foil.

[0003] After the existing ultra-thin copper foil products are hot-pressed with Prepreg (semi-cured bonding sheet), the distribution and size of the tearing force between the ultra-thin copper foil and the carrier copper foil are related to the distribution and content of the release layer.

[0004] The release layer in existing ultra-thin copper foil products is formed of a single or multiple alloy metals, and the metal components include Ni, Co, Mo, W, or a combination thereof. However, the release layer deposited on the carrier copper foil by electroplating may be difficult to control the tearing force due to uneven thickness distribution and content.

[0005] Therefore, the inventors believe that the above defects can be improved, and have devoted themselves to research and applied scientific principles, and finally proposed the present invention which has a reasonable design and effectively improves the above defects. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide an ultra-thin copper foil with a carrier and a manufacturing method thereof in view of the deficiencies of the prior art.

[0007] In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a method for manufacturing an ultra-thin copper foil with a carrier, which comprises: providing a carrier copper foil; forming a release layer on one side surface of the carrier copper foil; wherein the release layer is composed of a copper-containing organic compound, and the chemical structure of the copper-containing organic compound has at least a copper-nitrogen bond (Cu-N bond); and forming an ultra-thin copper foil layer (ultra-thin copper foil) on one side surface of the release layer away from the carrier copper foil.

[0008] Wherein, the carrier copper foil can be separated from the ultra-thin copper foil layer through the release layer.

[0009] Preferably, the release layer is analyzed by Fourier transform infrared spectroscopy (FTIR) at 1020 cm -1 ~1025cm -1 and 1098cm -1 ~1103cm -1 There are infrared characteristic absorption peaks at the positions of .

[0010] Preferably, the copper-containing organic compound forming the release layer is an organic copper complex.

[0011] Preferably, the release layer is formed by electroplating the carrier copper foil with an electroplating solution; wherein the electroplating solution comprises the following components (1) to (3): (1) a nitrogen-containing heterocyclic compound; (2) a copper-containing metal salt; and (3) a buffer; wherein, in the electroplating solution, the concentration of the nitrogen-containing heterocyclic compound is between 0.05 g / L and 40 g / L, the concentration of the copper-containing metal salt is between 5 g / L and 100 g / L, and the concentration of the buffer is between 10 g / L and 600 g / L.

[0012] Preferably, in the electroplating solution, the mass ratio of the nitrogen-containing heterocyclic compound: the copper-containing metal salt: the buffer is between 1:5-40:100-600.

[0013] Preferably, the nitrogen-containing heterocyclic compound is a bicyclic nitrogen-containing heterocyclic compound; wherein the copper-containing metal salt is selected from at least one of the material group consisting of: copper pyrophosphate, copper sulfate, copper carbonate, copper acetate, copper nitrate, copper oxide, cuprous cyanide, sodium copper cyanide and potassium copper cyanide; wherein the buffer is selected from at least one of the material group consisting of: potassium pyrophosphate, boric acid, sulfuric acid, ammonium sulfate, citric acid, ammonium citrate, sodium citrate, sodium acetate, sodium carbonate, potassium tartrate, and sodium gluconate.

[0014] Preferably, the carrier copper foil is electroplated in the electroplating solution for a predetermined time, the predetermined time being between 1 and 20 seconds, the electroplating conditions being that the current density is between 0.1 and 5 ASD, and the temperature of the electroplating solution is between 30 and 60°C.

[0015] Preferably, the chemical structure of the copper-containing organic compound further has a carbon-hydrogen bond (CH bond), a carbon-nitrogen bond (CN bond), and a nitrogen-hydrogen bond (NH bond).

[0016] Preferably, the nitrogen content of the release layer measured by X-ray photoelectron spectroscopy (XPS) is between 0.1 mass % and 25 mass %.

[0017] Preferably, the element ratio of the release layer obtained by analyzing the X-ray photoelectron spectrometer is that the N1s peak area value accounts for 15-25 atomic%, the O1s peak area value accounts for 25-35 atomic%, the C1s peak area value accounts for 30-40 atomic%, and the Cu2p peak area value accounts for 5-18 atomic%; wherein the ratio of the Cu2p peak area value to the N1s peak area value is 0.3-0.9.

[0018] In order to solve the above technical problems, another technical solution adopted by the present invention is to provide an ultra-thin copper foil with a carrier, which includes: a carrier copper foil; a release layer formed on one side surface of the carrier copper foil, the release layer is composed of a copper-containing organic compound, and the chemical structure of the copper-containing organic compound has at least a copper-nitrogen bond (Cu-N bond); and an ultra-thin copper foil layer (ultra-thin copper foil) formed on the side surface of the release layer away from the carrier copper foil; wherein the carrier copper foil can be separated from the ultra-thin copper foil layer through the release layer.

[0019] Preferably, the release layer is analyzed by Fourier transform infrared spectroscopy (FTIR) at 1020-1025 cm -1 and 1098~1103cm -1 and the positions thereof respectively have characteristic infrared absorption peaks; and the copper-containing organic compound forming the release layer is an organic copper complex.

[0020] Preferably, the thickness of the carrier copper foil is between 10 micrometers and 50 micrometers, the thickness of the release layer is between 20 nanometers and 300 nanometers, and the thickness of the ultra-thin copper foil layer is between 1 micrometer and 5 micrometers.

[0021] Preferably, the release layer is formed by electroplating the carrier copper foil with an electroplating solution, and the electroplating solution comprises: (1) a nitrogen-containing heterocyclic compound, (2) a copper-containing metal salt, and (3) a buffer.

[0022] Preferably, the surface roughness of the side surface of the ultra-thin copper foil layer away from the release layer is greater than the surface roughness of the surface of the ultra-thin copper foil layer in contact with the release layer.

[0023] Preferably, the peeling strength of the carrier copper foil from the ultra-thin copper foil layer through the release layer is between 1 and 20 gf / cm according to JIS Z 0237-2009 test.

[0024] Preferably, the release layer can obtain characteristic absorption peaks of carbon-hydrogen bond (CH bond), carbon-nitrogen bond (CN bond), and nitrogen-hydrogen bond (NH bond) through Fourier transform infrared spectroscopy analysis.

[0025] Preferably, the nitrogen content of the release layer measured by an X-ray photoelectron spectrometer (XPS) is between 0.1 mass % and 25 mass %; wherein, the element ratio of the release layer analyzed by the X-ray photoelectron spectrometer is 15-25 atomic % for N1s peak area value, 25-35 atomic % for O1s peak area value, 30-40 atomic % for C1s peak area value, and 5-18 atomic % for Cu2p peak area value; wherein, the ratio of the Cu2p peak area value to the N1s peak area value is 0.3-0.9.

[0026] Preferably, the N1s peak area value accounts for 20.63 atomic %, the O1s peak area value accounts for 29.78 atomic %, the C1s peak area value accounts for 36.77 atomic %, and the Cu2p peak area value accounts for 12.82 atomic %; wherein the ratio of the Cu2p peak area value to the N1s peak area value is 0.6214.

[0027] Preferably, X-ray photoelectron spectroscopy (XPS) and focused ion beam analysis (FIB) of the release layer have a curve graph of Cu2p peak.

[0028] The beneficial effect of the present invention lies in that the ultra-thin copper foil with a carrier and the manufacturing method thereof provided by the present invention can achieve better release effect between the carrier copper foil and the ultra-thin copper foil layer in the ultra-thin copper foil with a carrier through the technical scheme of "carrier copper foil; release layer, formed on one side surface of the carrier copper foil, the release layer is composed of a copper-containing organic compound, and the chemical structure of the copper-containing organic compound has at least a copper-nitrogen bond (Cu-N bond); and an ultra-thin copper foil layer is formed on the side surface of the release layer away from the carrier copper foil", and can solve the technical problem in the prior art that the release layer may be difficult to control the tearing force due to uneven distribution and content.

[0029] To further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only for reference and description and are not intended to limit the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Schematic diagram of step S110 of the method for manufacturing ultra-thin copper foil with carrier according to an embodiment of the present invention.

[0031] Figure 2 Schematic diagram of step S120 of the method for manufacturing ultra-thin copper foil with carrier according to an embodiment of the present invention.

[0032] Figure 3Schematic diagram of step S130 of the method for manufacturing ultra-thin copper foil with carrier according to an embodiment of the present invention.

[0033] Figure 4 Schematic diagram of step S210 of the method for manufacturing a printed circuit board substrate according to an embodiment of the present invention.

[0034] Figure 5 Schematic diagram of step S220 of the method for manufacturing a printed circuit board substrate according to an embodiment of the present invention.

[0035] Figure 6 Schematic diagram of step S230 of the method for manufacturing a printed circuit board substrate according to an embodiment of the present invention.

[0036] Figure 7 It is a schematic diagram of an ultra-thin copper foil layer formed on a dielectric layer material according to an embodiment of the present invention.

[0037] Figure 8 It is a schematic diagram of immersing a carrier copper foil into an electroplating solution for electroplating according to an embodiment of the present invention.

[0038] Fig. 9 It is a schematic diagram of a carrier copper foil in an embodiment of the present invention that is a continuous and rollable sheet.

[0039] Fig.10 It shows the effect of the release layer formed by different organic compound concentrations in the electroplating solution on the peeling strength between the carrier copper foil and the ultra-thin copper foil layer.

[0040] Fig.11 The characteristic absorption spectrum of the release layer of the ultra-thin copper foil with carrier according to the embodiment of the present invention is obtained by Fourier transform infrared spectroscopy (FTIR) testing and analysis.

[0041] Fig.12 Graphs showing the Cu2p peak from X-ray photoelectron spectroscopy (XPS) and focused ion beam analysis (FIB) are shown. DETAILED DESCRIPTION

[0042] The following is an explanation of the embodiments disclosed in the present invention through specific embodiments. Those skilled in the art can understand the advantages and effects of the present invention from the contents disclosed in this specification.

[0043] The present invention can be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed based on different viewpoints and applications without deviating from the concept of the present invention. In addition, the drawings of the present invention are only simple schematic illustrations and are not depicted according to actual sizes. It is stated in advance. The following implementation methods will further explain the relevant technical content of the present invention in detail, but the disclosed content is not intended to limit the scope of protection of the present invention.

[0044] It should be understood that, although the terms "first", "second", "third", etc. may be used herein to describe various components or signals, these components or signals should not be limited by these terms. These terms are mainly used to distinguish one component from another component, or one signal from another signal. In addition, the term "or" used herein may include any one or more combinations of the associated listed items depending on the actual situation.

[0045] [Method for manufacturing ultra-thin copper foil with carrier]

[0046] See also Figures 1 to 3 As shown, an embodiment of the present invention provides a method for manufacturing an ultra-thin copper foil with a carrier, comprising step S110, step S120, and step S130. It should be noted that the order of the steps described in this embodiment and the actual operation method can be adjusted according to needs and are not limited to the description of this embodiment. It is worth mentioning that the copper foil material formed by the method for manufacturing an ultra-thin copper foil with a carrier described in this embodiment is particularly suitable for use in the production of substrates for printed circuit boards, but the present invention is not limited thereto.

[0047] like Figure 1 As shown, the step S110 includes: providing a carrier copper foil 1. The carrier copper foil 1 may be, for example, an electrolytic copper foil or a rolled copper foil. In one embodiment of the present invention, the carrier copper foil 1 is an electrolytic copper foil, but the present invention is not limited thereto.

[0048] In addition, in terms of thickness range, the thickness of the carrier copper foil 1 may be, for example, between 10 micrometers and 50 micrometers, preferably between 15 micrometers and 40 micrometers, and particularly preferably between 18 micrometers and 35 micrometers.

[0049] In this embodiment, the step S110 further includes: washing the carrier copper foil 1 with water to remove impurities or chemical residues on the surface of the carrier copper foil 1 , but the present invention is not limited thereto.

[0050] like Figure 2As shown, the step S120 includes: forming a release layer 2 on one side surface of the carrier copper foil 1. The release layer 2 is composed of a copper-containing organic compound (or copper-based polymer), and the chemical structure of the copper-containing organic compound at least has a copper-nitrogen bond (Cu-N bond). It is worth mentioning that the copper-nitrogen bond (Cu-N bond) in the chemical structure of the copper-containing organic compound can be obtained, for example, by Fourier-transform infrared spectroscopy (FTIR) test analysis.

[0051] For example, see Fig.11 As shown, the release layer 2 composed of the copper-containing organic compound is at 1020-1025 cm -1 and 1098~1103cm -1 There are infrared characteristic absorption peaks at the positions of , which represent that the chemical structure of the copper-containing organic compound contains at least a copper-nitrogen bond.

[0052] In one embodiment of the present invention, the copper-containing organic compound is an organic copper complex, but the present invention is not limited thereto.

[0053] In addition, in terms of thickness range, the thickness of the release layer 2 may be, for example, between 20 nanometers and 300 nanometers, preferably between 35 nanometers and 200 nanometers, and particularly preferably between 50 nanometers and 100 nanometers.

[0054] Specifically, the release layer 2 is formed by electroplating the carrier copper foil 1 with an electroplating solution L (see also Figure 8 and Fig. 9 shown).

[0055] That is to say, the release layer 2 is formed by electroplating the electroplating solution L.

[0056] In this embodiment, the electroplating solution L comprises the following components (1) to (3):

[0057] (1) Nitrogen-containing heterocyclic compounds;

[0058] (2) Copper-containing metal salts;

[0059] (3) Buffer.

[0060] Wherein, (1) the nitrogen-containing heterocyclic compound is an organic compound, preferably a bicyclic nitrogen-containing heterocyclic compound, and particularly preferably benzotriazole, but the present invention is not limited thereto. For example, the bicyclic nitrogen-containing heterocyclic compound may also be indoline or 1,4-diazabicyclic.

[0061] Among them, the chemical formula of benzotriazole is C6H5N3, and its chemical structure is as follows.

[0062]

[0063] The concentration of the nitrogen-containing heterocyclic compound in the electroplating solution L is between 0.05 g / L and 40 g / L, preferably between 0.1 g / L and 20 g / L, and particularly preferably between 0.1 g / L and 10 g / L.

[0064] It is worth mentioning that the nitrogen-containing heterocyclic compound is the organic material source of the copper-containing organic compound constituting the release layer 2 .

[0065] Furthermore, (2) the copper-containing metal salt is an inorganic compound, which is the source of the copper element in the release layer 2 (or the source of the copper ions in the electroplating solution L), and the copper-containing metal salt can form an organic copper complex with (1) the nitrogen-containing heterocyclic compound, thereby forming the release layer 2 on the carrier copper foil 1.

[0066] In some embodiments of the present invention, the copper-containing metal salt can be, for example, at least one selected from the following material group: copper pyrophosphate, copper sulfate, copper carbonate, copper acetate, copper nitrate, copper oxide, cuprous cyanide, sodium copper cyanide, and potassium copper cyanide. In a preferred embodiment of the present invention, the copper-containing metal salt is copper pyrophosphate, the chemical formula is Cu2P2O7, and the chemical structure is as follows.

[0067] The chemical structure below represents copper pyrophosphate in a dissociated state in water.

[0068]

[0069] The concentration of the copper-containing metal salt (such as copper pyrophosphate) in the electroplating solution L is between 5 g / L and 100 g / L, preferably between 5 g / L and 50 g / L, and particularly preferably between 10 g / L and 30 g / L.

[0070] Furthermore, (3) the buffering agent can allow the copper-containing metal salt to be better dispersed or dissolved in the electroplating solution L, and the buffering agent can be used to adjust the pH value of the electroplating solution L, but the present invention is not limited thereto.

[0071] In some embodiments of the present invention, the buffer may be at least one selected from the following group of materials: potassium pyrophosphate, boric acid, sulfuric acid, ammonium sulfate, citric acid, ammonium citrate, sodium citrate, sodium acetate, sodium carbonate, potassium tartrate, and sodium gluconate.

[0072] In a preferred embodiment, the buffer is potassium pyrophosphate, which has the chemical formula K4P2O7 and the chemical structure as follows.

[0073] The chemical structure below represents potassium pyrophosphate in a dissociated state in water.

[0074]

[0075] The concentration of the buffer (eg, potassium pyrophosphate) in the electroplating solution L is between 10 g / L and 600 g / L, preferably between 100 g / L and 500 g / L, and particularly preferably between 200 g / L and 500 g / L.

[0076] In some embodiments of the present invention, in the electroplating solution L, the mass ratio of all organic compounds (such as nitrogen-containing heterocyclic compounds): copper-containing metal salts (such as copper pyrophosphate): buffer (such as potassium pyrophosphate) can be, for example, 1:5-40:100-600, preferably 1:10-30:100-500, and particularly preferably 1:15-25:200-500, but the present invention is not limited thereto. However, the present invention is not limited to the concentration ranges listed in the above embodiments.

[0077] In this embodiment, the liquid component of the antioxidant liquid 2 is water, which may be, for example, deionized water (DI), reverse osmosis water (RO), or ultrapure water (MQ), preferably deionized water, but the present invention is not limited thereto.

[0078] like Figure 8 As shown, the electroplating method of this embodiment is to immerse the carrier copper foil 1 in the electroplating solution L for electroplating to form a release layer 2 on at least one side surface of the carrier copper foil 1. The electroplating solution L can be pre-configured in a liquid storage tank T, for example.

[0079] Specifically, the carrier copper foil 1 is electroplated in the electroplating solution L for a predetermined time to form the anti-release layer 2 on at least one side surface of the carrier copper foil 1 .

[0080] In some embodiments of the present invention, the predetermined time is between 1 second and 20 seconds, preferably between 1 second and 15 seconds, and particularly preferably between 3 seconds and 15 seconds.

[0081] For example, the predetermined time may be 3 seconds, 5 seconds, 7 seconds, 9 seconds, 11 seconds, 13 seconds, or 15 seconds.

[0082] In addition, the electroplating condition of the carrier copper foil 1 in the electroplating solution L is that the current density is between 0.1 and 5 ASD (i.e., A / dm2, amperes per square decimeter), and preferably between 0.2 and 2 ASD. For example, the current density can be 0.2 ASD, 0.6 ASD, 1.0 ASD, 1.5 ASD, or 2 ASD.

[0083] Furthermore, the liquid temperature of the electroplating solution L is between 30° C. and 60° C., preferably between 40° C. and 60° C. For example, the liquid temperature of the electroplating solution L is 40° C., 45° C., 50° C., 55° C., or 60° C.

[0084] It is worth mentioning that in this embodiment, the carrier copper foil 1 is described by taking a single copper foil immersed in the electroplating solution L as an example, but the present invention is not limited thereto.

[0085] like Fig. 9In another embodiment of the present invention, the carrier copper foil 1 is a continuous and rollable sheet. The carrier copper foil 1 can be guided into the electroplating solution L by a plurality of guide rollers R disposed in and around the liquid storage tank T. Furthermore, the carrier copper foil 1 can be configured by adjusting the rolling speed of the plurality of guide rollers R so that the carrier copper foil 1 can stay in the electroplating solution L and be electroplated for the predetermined time. Further, at least one pair of electrodes E is disposed in the liquid storage tank T so that the carrier copper foil 1 immersed in the electroplating solution L can be electroplated by energizing the electrodes E, thereby forming the release layer, but the present invention is not limited to the above manner.

[0086] The step S120 further includes: taking out the carrier copper foil 1 with the release layer 2 , and blowing and drying the carrier copper foil 1 to remove excess liquid components (such as water) in the release layer 2 .

[0087] According to the above configuration, the release layer 2 can be formed by electroplating the carrier copper foil 1 with an electroplating solution L. In other words, the release layer 2 is formed by the electroplating solution L.

[0088] like Figure 3 As shown, the step S130 includes: forming an ultra-thin copper foil layer 3 (ultra-thin copper foil) on a surface of the release layer 2 which is away from the carrier copper foil 1 .

[0089] In one embodiment of the present invention, the ultra-thin copper foil layer 3 can be formed by depositing copper metal on the release layer 2 through a wet electrolysis / electroplating process, but the present invention is not limited thereto.

[0090] In addition, in terms of thickness range, the thickness of the ultra-thin copper foil layer 3 may be, for example, between 1 micrometer and 5 micrometers, preferably between 1.5 micrometers and 4 micrometers, and particularly preferably between 1.5 micrometers and 3 micrometers.

[0091] It is worth mentioning that Figure 3 As shown, the surface of the side of the ultra-thin copper foil layer 3 away from the release layer 2 is a rough surface with uneven surfaces. In other words, the surface roughness (e.g., Ra) of the side surface of the ultra-thin copper foil layer 3 away from the release layer 2 is greater than the surface roughness of the surface where the ultra-thin copper foil layer 3 contacts the release layer 2, but the present invention is not limited thereto.

[0092] According to the above configuration, the laminated body composed of the carrier copper foil 1, the release layer 2, and the ultra-thin copper foil layer 3 is defined as the ultra-thin copper foil with carrier E (or copper foil laminated structure E) described in the embodiment of the present invention.

[0093] In some embodiments of the present invention, the carrier copper foil 1 can be separated from the ultra-thin copper foil layer 3 through the release layer 2. The peel strength of the carrier copper foil 1 separated from the ultra-thin copper foil layer 3 through the release layer 2 can be, for example, between 1 and 20 gf / cm, and preferably between 5 and 10 gf / cm.

[0094] The peel strength may be, for example, a value measured according to the JIS Z 0237-2009 test method, but the present invention is not limited thereto.

[0095] According to the above configuration, the carrier copper foil 1 can have better release force with the ultra-thin copper foil layer 3 through the design of the special release layer 2, thereby solving the technical problem in the prior art that the material thickness of the release layer material deposited on the carrier copper foil is uneven, making it difficult to control the tearing force.

[0096] It is worth mentioning that in the above embodiment, the laminate composed of the carrier copper foil 1, the release layer 2, and the ultra-thin copper foil layer 3 is subjected to a peel strength test after being heat treated at 180-220° C. for 70-110 minutes to obtain the above test results.

[0097] Further, if Fig.10 As shown, Fig.10 The figure shows the effect of the release layer formed by different organic compound concentrations (abbreviated as organic concentration, but expressed as g / L) in the electroplating solution on the tearing force (peel strength) between the carrier copper foil and the ultra-thin copper foil layer.

[0098] Among them, in a specific embodiment of the present invention (such as Fig.10 In Experimental Example 1), the concentration of the organic compound in the plating solution L forming the release layer is 1g / L (including benzotriazole), and the concentration of copper pyrophosphate (copper ion source) is 20g / L, and the concentration of potassium pyrophosphate is 390g / L. The current density of the electroplating is 0.2-2ASD (such as 1ASD), the electroplating time is 3-15 seconds (such as 9 seconds), and the electroplating temperature is 40-60°C (such as 50°C). The obtained carrier ultra-thin copper foil E and the dielectric layer material PP (such as Prepreg) are heat treated at 200°C for 90 minutes to obtain a hard board material, and the peel strength between the carrier copper foil and the ultra-thin copper foil is about 5gf / cm.

[0099] The concentration ratio (g / L) of the organic compound and the copper pyrophosphate (copper ion source) of the other experimental groups is fixed. For example, in Experiment 2, 0.95 g / L of the organic compound is matched with 19 g / L of the copper pyrophosphate (copper ion source), that is, the weight ratio of the organic compound to the copper pyrophosphate (copper ion source) is 1:20. Fig.10It can be seen from the experimental table that by adjusting the concentration of the organic compound in the electroplating solution L, the peel strength between the carrier copper foil and the ultra-thin copper foil can be adjusted within a desired range to achieve a better tearing force.

[0100] It is worth mentioning that, as mentioned above, according to the test results of the above-mentioned embodiment 1, the release layer 2 is composed of a copper-containing organic compound, and the chemical structure has at least a copper-nitrogen bond (Cu-N bond). Fig.11 The release layer 2 can also obtain characteristic absorption peaks of carbon-hydrogen bond (CH bond), carbon-nitrogen bond (CN bond), and nitrogen-hydrogen bond (NH bond) through FTIR analysis.

[0101] Furthermore, the nitrogen content of the release layer 2 measured by X-ray photoelectron spectroscopy (XPS) is between 0.1 mass % and 25 mass %, and preferably between 1 mass % and 20 mass %. For example, the nitrogen content of the release layer 2 may be 5 mass %, 10 mass %, 15 mass %, or 20 mass %.

[0102] From another perspective, the element ratio (atomic %) of the release layer 2 obtained by X-ray photoelectron spectrometer (XPS) analysis is that the N1s peak area value (associated with nitrogen element) accounts for 15-25 atomic %, the O1s peak area value (associated with oxygen element) accounts for 25-35 atomic %, the C1s peak area value (associated with carbon element) accounts for 30-40 atomic %, and the Cu2p peak area value (associated with copper element) accounts for 5-18 atomic %. Further, the ratio of the Cu2p peak area value to the N1s peak area value is 0.3-0.9, and preferably 0.5-0.7, but the present invention is not limited thereto.

[0103] In a specific embodiment of the present invention, the release layer 2 has an N1s peak area value of 20.63 atom %, an O1s peak area value of 29.78 atom %, a C1s peak area value of 36.77 atom %, and a Cu2p peak area value of 12.82 atom % as analyzed by XPS.

[0104] The table below shows the element ratio (atomic %) test results obtained by XPS analysis.

[0105] name N1s O1s C1s Cu2P atom% 20.63 29.78 36.77 12.82

[0106] Furthermore, the ratio of the Cu2p peak area value to the N1s peak area value is 0.6214 (ie, the ratio obtained by dividing 12.82 by 20.63).

[0107] In addition, by Fig.12 It can be known that Fig.12 The graph showing the Cu2p peak from X-ray photoelectron spectroscopy (XPS) and focused ion beam analysis (FIB) indicates that the release layer 2 of the embodiment of the present invention does contain copper.

[0108] From the above qualitative analysis, it can be known that the above-mentioned benzotriazole (nitrogen-containing organic compound) is indeed included in the organic copper complex forming the release layer 2 .

[0109] It should be noted that the nitrogen element in the release layer 2 is derived from the nitrogen-containing heterocyclic compound in the electroplating solution L.

[0110] It is worth mentioning that X-ray photoelectron spectroscopy (XPS) is a quantitative spectroscopy technique used to determine the elemental composition, empirical formula, and chemical and electronic states of the elements contained in the material. This technique uses X-rays to irradiate the material to be analyzed, and simultaneously measures the kinetic energy and number of electrons escaping from the range of 1nm to 10nm below the surface of the material, thereby obtaining an X-ray photoelectron spectrum.

[0111] [Ultra-thin copper foil with carrier]

[0112] The above is a technical description of the method for manufacturing the ultra-thin copper foil with carrier according to an embodiment of the present invention. Figure 3 As shown, an embodiment of the present invention also provides an ultra-thin copper foil E with a carrier (or copper foil laminated structure E), which includes: a carrier copper foil 1, a release layer 2 formed on the carrier copper foil 1, and an ultra-thin copper foil layer 3 formed on the release layer 2 and away from the carrier copper foil 1.

[0113] In one embodiment of the present invention, the carrier copper foil 1 is an electrolytic copper foil and has a thickness between 10 μm and 50 μm, preferably between 15 μm and 40 μm, and particularly preferably between 18 μm and 35 μm, but the present invention is not limited thereto.

[0114] The release layer 2 is composed of a copper-containing organic compound (or copper-based polymer), and the chemical structure of the copper-containing organic compound at least has a copper-nitrogen bond (Cu—N bond).

[0115] It is worth mentioning that the Cu-N bond in the chemical structure of the copper-containing organic compound can be known, for example, by Fourier transform infrared spectroscopy analysis. For example, see Fig.11 As shown, the release layer 2 composed of the copper-containing organic compound is at 1020-1025 cm -1 and 1098~1103cm -1The positions of the copper-containing organic compound and the copper-containing organic compound have infrared characteristic absorption peaks, respectively, indicating that the chemical structure of the copper-containing organic compound has at least a copper-nitrogen bond. In addition, the copper-containing organic compound is an organic copper complex, but the present invention is not limited thereto.

[0116] The thickness of the release layer 2 may be, for example, between 20 nanometers and 300 nanometers, preferably between 35 nanometers and 200 nanometers, and particularly preferably between 50 nanometers and 100 nanometers.

[0117] The release layer 2 is formed by electroplating the carrier copper foil 1 with an electroplating solution L. The electroplating solution L comprises: (1) a nitrogen-containing heterocyclic compound, (2) a copper-containing metal salt (such as copper pyrophosphate), and (3) a buffer (such as potassium pyrophosphate). The characteristics of each component in the electroplating solution L have been described above, so they are not repeated here. It is worth mentioning that the nitrogen-containing heterocyclic compound is the source of the organic component of the copper-containing organic compound constituting the release layer 2.

[0118] In addition, the copper-containing metal salts (such as copper pyrophosphate) are the source of copper elements constituting the release layer 2 .

[0119] Furthermore, the ultra-thin copper foil layer 3 can be formed, for example, by depositing copper metal on the release layer 2 through a wet electrolysis / electroplating process. The ultra-thin copper foil layer 3 has a thickness between 1 μm and 5 μm, preferably between 1.5 μm and 4 μm, and particularly preferably between 1.5 μm and 3 μm.

[0120] In addition, in the present embodiment, the surface of the ultra-thin copper foil layer 3 away from the release layer 2 is a rough surface with uneven surfaces, but the present invention is not limited thereto.

[0121] The carrier copper foil 1 can be torn off from the ultra-thin copper foil layer 3 through the release layer 2. The peel strength of the carrier copper foil 1 to be torn off from the ultra-thin copper foil layer 3 through the release layer 2 can be, for example, between 1 and 20 gf / cm, and preferably between 5 and 10 gf / cm. The peel strength can be, for example, a value measured according to the JIS Z0237-2009 test method, but the present invention is not limited thereto.

[0122] According to the above configuration, the carrier copper foil 1 can have better release force with the ultra-thin copper foil layer 3 through the design of the special release layer 2 .

[0123] [Manufacturing method of printed circuit board substrate]

[0124] See also Figures 4 to 7 As shown, the embodiment of the present invention also provides a method for manufacturing a printed circuit board substrate, which includes step S210, step S220, and step S230.

[0125] like Figure 4 As shown, the step S210 includes: attaching the ultra-thin copper foil with carrier E of the above embodiment to the dielectric layer material PP (such as Prepreg sheet) through its ultra-thin copper foil layer 3 .

[0126] like Figure 5 As shown, the step S220 includes: performing a hot pressing operation H on the ultra-thin copper foil E with a carrier and the dielectric layer material PP. Accordingly, the concavo-convex microstructure of the rough surface of the ultra-thin copper foil layer 3 can be more closely combined with the dielectric layer material PP to enhance the bonding between the ultra-thin copper foil layer 3 and the dielectric layer material PP.

[0127] like Figure 6 As shown, the step S230 includes: separating the carrier copper foil 1 from the ultra-thin copper foil layer 3 through the release layer 2 thereon, so that the ultra-thin copper foil layer 3 remains on the dielectric layer material PP. Figure 7 As shown, it is a schematic diagram showing that an ultra-thin copper foil layer 3 is formed on the dielectric layer material PP.

[0128] The above is a method for manufacturing a printed circuit board substrate according to one embodiment of the present invention. However, the application of the ultra-thin copper foil E with a carrier is not limited to the above method.

[0129] [Beneficial Effects of Embodiments]

[0130] The beneficial effect of the present invention lies in that the ultra-thin copper foil with a carrier and the manufacturing method thereof provided by the present invention can achieve better release effect between the carrier copper foil and the ultra-thin copper foil layer in the ultra-thin copper foil with a carrier through the technical scheme of "carrier copper foil; release layer, formed on one side surface of the carrier copper foil, the release layer is composed of a copper-containing organic compound, and the chemical structure of the copper-containing organic compound has at least a copper-nitrogen bond (Cu-N bond); and an ultra-thin copper foil layer is formed on the side surface of the release layer away from the carrier copper foil", and can solve the technical problem in the prior art that the release layer may be difficult to control the tearing force due to uneven distribution and content.

[0131] The contents disclosed above are only preferred feasible embodiments of the present invention, and are not intended to limit the scope of the present invention. Therefore, all equivalent technical changes made using the contents of the present invention description and drawings are included in the scope of the present invention.

Claims

1. A method for manufacturing an ultra-thin copper foil with a carrier, characterized in that: The method for manufacturing the ultra-thin copper foil with a carrier comprises: Providing carrier copper foil; forming a release layer on one surface of the carrier copper foil; wherein the release layer is composed of a copper-containing organic compound, and the chemical structure of the copper-containing organic compound has at least a copper-nitrogen bond; and forming an ultra-thin copper foil layer on a surface of the release layer on a side away from the carrier copper foil; Wherein, the carrier copper foil can be separated from the ultra-thin copper foil layer through the release layer.

2. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 1, characterized in that: The release layer was analyzed by Fourier transform infrared spectroscopy at 1020 cm -1 ~1025cm -1 and 1098cm -1 ~1103cm -1 There are infrared characteristic absorption peaks at the positions of .

3. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 1, characterized in that: The copper-containing organic compound forming the release layer is an organic copper complex.

4. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 1, characterized in that: The release layer is formed by electroplating the carrier copper foil with an electroplating solution; wherein the electroplating solution comprises the following components (1) to (3): (1) Nitrogen-containing heterocyclic compounds; (2) Metal salts containing copper; and (3) Buffer; Wherein, in the electroplating solution, the concentration of the nitrogen-containing heterocyclic compound is between 0.05 g / L and 40 g / L, the concentration of the copper-containing metal salt is between 5 g / L and 100 g / L, and the concentration of the buffer is between 10 g / L and 600 g / L.

5. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 4, characterized in that: In the electroplating solution, the mass ratio of the nitrogen-containing heterocyclic compound: the copper-containing metal salt: the buffer is between 1:5-40:100-600.

6. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 4, characterized in that: The nitrogen-containing heterocyclic compound is a bicyclic nitrogen-containing heterocyclic compound; wherein the copper-containing metal salt is selected from at least one of the material group consisting of: copper pyrophosphate, copper sulfate, copper carbonate, copper acetate, copper nitrate, copper oxide, cuprous cyanide, sodium copper cyanide and potassium copper cyanide; wherein the buffer is selected from at least one of the material group consisting of: potassium pyrophosphate, boric acid, sulfuric acid, ammonium sulfate, citric acid, ammonium citrate, sodium citrate, sodium acetate, sodium carbonate, potassium tartrate, and sodium gluconate.

7. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 4, characterized in that: The carrier copper foil is electroplated in the electroplating solution for a predetermined time, the predetermined time being between 1 and 20 seconds, the electroplating conditions being that the current density is between 0.1 and 5 ASD, and the temperature of the electroplating solution is between 30 and 60°C.

8. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 1, characterized in that: The chemical structure of the copper-containing organic compound further has carbon-hydrogen bonds, carbon-nitrogen bonds, and nitrogen-hydrogen bonds.

9. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 1, characterized in that: The nitrogen content of the release layer measured by an X-ray photoelectron spectrometer is between 0.1 mass % and 25 mass %.

10. The method for manufacturing an ultra-thin copper foil with a carrier according to claim 9, characterized in that: The element ratio of the release layer obtained by analyzing the X-ray photoelectron spectrometer is: N1s peak area value accounts for 15-25 atomic%, O1s peak area value accounts for 25-35 atomic%, C1s peak area value accounts for 30-40 atomic%, and Cu2p peak area value accounts for 5-18 atomic%; wherein, the ratio of the Cu2p peak area value to the N1s peak area value is 0.3-0.

9.

11. An ultra-thin copper foil with a carrier, characterized in that: The ultra-thin copper foil with carrier comprises: Carrier copper foil; A release layer is formed on one side surface of the carrier copper foil, wherein the release layer is composed of a copper-containing organic compound, and the chemical structure of the copper-containing organic compound has at least a copper-nitrogen bond; and An ultra-thin copper foil layer is formed on a surface of the release layer on a side away from the carrier copper foil; Wherein, the carrier copper foil can be separated from the ultra-thin copper foil layer through the release layer.

12. The ultra-thin copper foil with carrier according to claim 11, characterized in that: The release layer was analyzed by Fourier transform infrared spectroscopy at 1020-1025 cm -1 and 1098~1103cm -1 and the positions thereof respectively have characteristic infrared absorption peaks; and the copper-containing organic compound forming the release layer is an organic copper complex.

13. The ultra-thin copper foil with carrier according to claim 11, characterized in that: The thickness of the carrier copper foil is between 10 micrometers and 50 micrometers, the thickness of the release layer is between 20 nanometers and 300 nanometers, and the thickness of the ultra-thin copper foil layer is between 1 micrometer and 5 micrometers.

14. The ultra-thin copper foil with carrier according to claim 11, characterized in that: The release layer is formed by electroplating the carrier copper foil with an electroplating solution, and the electroplating solution comprises: (1) a nitrogen-containing heterocyclic compound, (2) a copper-containing metal salt, and (3) a buffer.

15. The ultra-thin copper foil with carrier according to claim 11, characterized in that: The surface roughness of the side surface of the ultra-thin copper foil layer away from the release layer is greater than the surface roughness of the surface of the ultra-thin copper foil layer in contact with the release layer.

16. The ultra-thin copper foil with carrier according to claim 11, characterized in that: The peel strength of the carrier copper foil being torn off from the ultra-thin copper foil layer through the release layer is between 1 and 20 gf / cm according to JIS Z 0237-2009.

17. The ultra-thin copper foil with carrier according to claim 11, characterized in that: The release layer can obtain characteristic absorption peaks of carbon-hydrogen bonds, carbon-nitrogen bonds, and nitrogen-hydrogen bonds through Fourier transform infrared spectroscopy analysis.

18. The ultra-thin copper foil with carrier according to claim 11, characterized in that: The nitrogen content of the release layer measured by an X-ray photoelectron spectrometer is between 0.1 mass % and 25 mass %; wherein, the element ratio of the release layer analyzed by the X-ray photoelectron spectrometer is 15-25 atomic % for N1s peak area value, 25-35 atomic % for O1s peak area value, 30-40 atomic % for C1s peak area value, and 5-18 atomic % for Cu2p peak area value; wherein, the ratio of the Cu2p peak area value to the N1s peak area value is 0.3-0.

9.

19. The ultra-thin copper foil with carrier according to claim 18, characterized in that: The N1s peak area value accounts for 20.63 atomic %, the O1s peak area value accounts for 29.78 atomic %, the C1s peak area value accounts for 36.77 atomic %, and the Cu2p peak area value accounts for 12.82 atomic %; The ratio of the Cu2p peak area value to the N1s peak area value is 0.6214.

20. The ultra-thin copper foil with carrier according to claim 17, characterized in that: X-ray photoelectron spectroscopy and focused ion beam analysis of the release layer have a curve graph of Cu2p peak.

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