CN110785006A - A substrate with carrier and circuit board - Google Patents

Abstract

The invention relates to the technical field of materials, and discloses a substrate with a carrier and a circuit board, wherein the substrate with a carrier comprises a composite metal foil, an insulating adhesive layer and a base film layer, and the composite metal foil is arranged on the base through the insulating adhesive layer. On the film layer, the composite metal foil includes a carrier layer, a barrier layer, a release layer and a metal foil layer; the carrier layer, the barrier layer, the release layer and the metal foil layer are stacked in sequence; or, the carrier layer, the release layer, the barrier layer and the metal foil The layers are stacked in sequence; wherein, at a temperature of 20-400°C, the diffusion depth from the carrier layer to the metal foil layer is less than or equal to 3 μm, and the diffusion depth from the metal foil layer to the carrier layer is less than or equal to 3 μm, which is avoided by setting the barrier layer. The carrier layer and the metal foil layer are bonded by mutual diffusion at high temperature, so that the carrier layer and the metal foil layer can be easily peeled off, so that a relatively complete ultra-thin metal foil layer with fewer pinholes can be obtained, which is beneficial to the subsequent fine lines. preparation.

Description

A substrate with carrier and circuit board

technical field

The invention relates to the technical field of materials, in particular to a substrate with a carrier and a circuit board.

Background technique

With the high-density integration of electronic components, the wiring patterns of circuit boards are also becoming denser and denser (that is, forming fine circuit boards). Since thick metal foils are prone to breakage problems when making fine circuits, forming Thin metal foils are required for fine wiring boards. Currently, in order to obtain a substrate for forming a fine wiring board, the existing substrate is usually composed of a flexible insulating base film and a composite metal foil. When the substrate is prepared in the prior art, the side of the composite metal foil (including the carrier layer and the metal foil layer) with the metal foil layer is usually laminated with the flexible insulating base film first, so as to obtain the substrate with the carrier. When a substrate with a carrier is used, the carrier layer needs to be peeled off. However, since the composite metal foil and the flexible insulating base film need to be pressed under high temperature conditions, and the carrier layer and the metal foil layer are prone to mutual diffusion under high temperature conditions, the carrier layer and the metal foil layer are bonded, making the It is difficult to peel off the carrier layer and the metal foil layer, resulting in many pinholes in the metal foil layer, which is not conducive to the preparation of subsequent micro-circuits.

SUMMARY OF THE INVENTION

The purpose of the embodiments of the present invention is to provide a substrate with a carrier and a circuit board, which can avoid adhesion between the carrier layer and the metal foil layer of the composite metal foil in the existing substrate with a carrier due to mutual diffusion at high temperature, so that the carrier The layer is easily peeled off from the metal foil layer.

In order to solve the above technical problems, an embodiment of the present invention provides a substrate with a carrier, the substrate with a carrier includes a composite metal foil, an insulating adhesive layer and a base film layer, and the composite metal foil includes a carrier layer, a barrier layer, Release layer and metal foil layer;

The carrier layer, the barrier layer, the peeling layer and the metal foil layer are stacked in sequence; or,

The carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence;

The composite metal foil is arranged on the base film layer through the insulating adhesive layer, and the insulating adhesive layer is arranged on the side of the metal foil layer away from the carrier layer, and the base film layer is arranged on the side of the insulating adhesive layer away from the metal foil layer;

Wherein, at a temperature of 20-400° C., the diffusion depth from the carrier layer to the metal foil layer is less than or equal to 3 μm, and the diffusion depth from the metal foil layer to the carrier layer is less than or equal to 3 μm.

As a preferred solution, the diffusion depth from the carrier layer to the metal foil layer is less than or equal to 1 μm, and the diffusion depth from the metal foil layer to the carrier layer is less than or equal to 1 μm.

As a preferred solution, the carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence, and the peeling strength between the metal foil layer and the barrier layer is greater than that between the peeling layer and the metal foil layer. Peel strength between the barrier layers.

As a preferred solution, the barrier layer includes a high temperature resistant layer, and the high temperature resistant layer is an organic high temperature resistant layer; or, the high temperature resistant layer is made of any of tungsten, chromium, zirconium, titanium, nickel, molybdenum, cobalt and graphite. one or more materials.

As a preferred solution, the high temperature resistant layer is a single-layer alloy structure or a multi-layer structure composed of a single metal layer or a multi-layer structure composed of an alloy layer and a single metal layer.

As a preferred solution, the carrier layer, the barrier layer, the peeling layer and the metal foil layer are stacked in sequence, and the barrier layer further includes a metal bonding layer, and the metal bonding layer is arranged on the carrier. layer and the high temperature resistant layer.

As a preferred solution, the carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence, and the barrier layer further includes a metal bonding layer, and the metal bonding layer is provided on the resistant layer. between the high temperature layer and the metal foil layer.

As a preferred solution, the metal bonding layer is made of any one or more of copper, zinc, nickel, iron and manganese; or, the metal bonding layer is made of one of copper or zinc. and one of nickel, iron and manganese.

As a preferred solution, the peeling layer is made of any one or more materials selected from nickel, silicon, molybdenum, graphite, titanium and niobium; or, the peeling layer is made of an organic polymer material.

As a preferred solution, the thickness of the metal foil layer is less than or equal to 9 μm.

As a preferred solution, the metal foil layer is a copper foil or an aluminum foil; and/or, the carrier layer is a carrier copper or a carrier aluminum or an organic film.

As a preferred solution, the roughness Rz of the side of the carrier layer close to the metal foil layer is less than or equal to 5 μm; and/or the roughness Rz of the side of the metal foil layer away from the carrier layer is less than or equal to 3.0 μm.

As a preferred solution, a first anti-oxidation layer is provided on the side of the carrier layer close to the barrier layer; and/or, a second anti-oxidation layer is provided on the side of the metal foil layer away from the barrier layer .

As a preferred solution, the thickness of the insulating adhesive layer is 0.01-25 μm; and/or the thickness of the base film layer is 1-30 μm.

As a preferred solution, the insulating adhesive layer is made of thermoplastic resin or thermosetting resin, wherein the thermoplastic resin includes polystyrene, vinyl acetate, polyester, polyethylene, polyamide, and rubber. Or acrylate thermoplastic resin, the thermosetting resin includes phenolic, epoxy, urethane, melamine or alkyd thermosetting resin; and/or, the base film layer is made of polyimide, thermoplastic polymer Imide, modified epoxy resin, modified acrylic resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene, polyethylene naphthalate, polystyrene , polyvinyl chloride, polysulfone, polyphenylene sulfide, polyether ether ketone, polyphenylene ether, polytetrafluoroethylene, liquid crystal polymer, polyoxalide, one or more materials.

As a preferred solution, the number of the composite metal foil and the insulating adhesive layer is two, and one of the composite metal foil is provided on one side of the base film layer through one of the insulating adhesive layers. , the other composite metal foil is provided on the other side of the base film layer through the other insulating adhesive layer.

In order to solve the same technical problem, an embodiment of the present invention further provides a circuit board obtained by using the substrate with a carrier.

Embodiments of the present invention provide a substrate with a carrier and a circuit board, wherein the substrate with a carrier includes a composite metal foil, an insulating adhesive layer and a base film layer, and the composite metal foil includes a carrier layer, a barrier layer, a peeling layer and a metal foil layer, the carrier layer, the barrier layer, the peeling layer and the metal foil layer are stacked in sequence; or, the carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence; the composite metal foil is arranged on the base film layer through the insulating adhesive layer The insulating adhesive layer is arranged on the side of the metal foil layer away from the carrier layer, and the base film layer is arranged on the side of the insulating adhesive layer away from the metal foil layer. The diffusion depth of the foil layer is less than or equal to 3 μm, and the diffusion depth of the metal foil layer to the carrier layer is less than or equal to 3 μm, wherein the release layer is provided to facilitate the release of the carrier layer, and the barrier layer is provided to avoid the carrier layer and the metal foil layer. At high temperature, mutual diffusion causes bonding, so that the carrier layer and the metal foil layer can be easily peeled off, and then a relatively complete ultra-thin metal foil layer with fewer pinholes can be obtained, which is conducive to the preparation of subsequent micro circuits.

Description of drawings

FIG. 1 is a schematic structural diagram of a carrier layer, a barrier layer, a peeling layer and a metal foil layer in an embodiment of the single-sided substrate with a carrier provided by the present invention, which are stacked in sequence;

2 is a schematic structural diagram of an embodiment of a single-sided substrate with a carrier provided by the present invention comprising a metal adhesive layer and a high temperature resistant layer, and a carrier layer, a barrier layer, a release layer and a metal foil layer are stacked in sequence;

3 is a schematic structural diagram of a carrier layer, a peeling layer, a barrier layer and a metal foil layer arranged in sequence in an embodiment of the single-sided substrate with a carrier provided by the present invention;

4 is a schematic structural diagram of an embodiment of a single-sided substrate with a carrier provided by the present invention comprising a metal adhesive layer and a high temperature resistant layer, and a carrier layer, a peeling layer, a barrier layer and a metal foil layer are stacked in sequence;

FIG. 5 is a schematic view of peeling that the carrier layer, the barrier layer, the peeling layer and the metal foil layer are sequentially stacked in an embodiment of the single-sided substrate with a carrier provided by the present invention;

6 is a schematic view of the peeling of the carrier layer, the barrier layer, the peeling layer and the metal foil layer in sequence in another embodiment of the single-sided substrate with a carrier provided by the present invention;

7 is a schematic view of the peeling of the carrier layer, the peeling layer, the barrier layer and the metal foil layer in an embodiment of the single-sided substrate with a carrier provided by the present invention in sequence;

FIG. 8 is a schematic view of the peeling of the carrier layer, the peeling layer, the barrier layer and the metal foil layer in sequence in another embodiment of the single-sided substrate with a carrier provided by the present invention;

9 is a schematic structural diagram of a carrier layer, a barrier layer, a peeling layer and a metal foil layer in an embodiment of the double-sided substrate with a carrier provided by the present invention in sequence;

10 is a schematic structural diagram of an embodiment of a double-sided substrate with a carrier provided by the present invention comprising a metal adhesive layer and a high temperature resistant layer, and a carrier layer, a barrier layer, a peeling layer and a metal foil layer are stacked in sequence;

11 is a schematic structural diagram of a carrier layer, a peeling layer, a barrier layer and a metal foil layer arranged in sequence in an embodiment of the double-sided substrate with a carrier provided by the present invention;

12 is a schematic structural diagram of an embodiment of a double-sided substrate with a carrier provided by the present invention comprising a metal adhesive layer and a high temperature resistant layer, and a carrier layer, a peeling layer, a barrier layer and a metal foil layer are sequentially stacked;

13 is a schematic view of peeling that the carrier layer, the barrier layer, the peeling layer and the metal foil layer are sequentially stacked in an embodiment of the double-sided substrate with a carrier provided by the present invention;

FIG. 14 is a schematic view of peeling that the carrier layer, the barrier layer, the peeling layer and the metal foil layer are stacked in sequence in another embodiment of the double-sided substrate with a carrier provided by the present invention;

FIG. 15 is a schematic view of peeling that the carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence in an embodiment of the double-sided substrate with a carrier provided by the present invention;

16 is a schematic view of peeling that the carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence in another embodiment of the double-sided substrate with a carrier provided by the present invention;

17 is a schematic flowchart of an embodiment of a method for preparing a substrate with a carrier provided by the present invention;

18 is a schematic flowchart of an embodiment of the method for preparing a composite metal foil provided by the present invention;

FIG. 19 is a schematic flowchart of another embodiment of the method for preparing a composite metal foil provided by the present invention;

Among them, 1, carrier layer; 2, barrier layer; 21, high temperature resistant layer; 22, metal bonding layer; 3, peeling layer; 4, metal foil layer; 5, insulating bonding layer; 6, base film layer.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Referring to FIG. 1 , a substrate with a carrier according to a preferred embodiment of the present invention, the substrate with a carrier includes a composite metal foil, an insulating adhesive layer 5 and a base film layer 6 , and the composite metal foil includes a carrier layer 1 , barrier layer 2, peeling layer 3 and metal foil layer 4;

The carrier layer 1 , the barrier layer 2 , the peeling layer 3 and the metal foil layer 4 are stacked in sequence; or,

Referring to FIG. 3 , the carrier layer 1 , the peeling layer 3 , the barrier layer 2 and the metal foil layer 4 are stacked in sequence;

The composite metal foil is arranged on the base film layer 6 through the insulating adhesive layer 5, and the insulating adhesive layer 5 is arranged on the side of the metal foil layer 6 away from the carrier layer 1, The base film layer 6 is disposed on the side of the insulating adhesive layer 5 away from the metal foil layer 6;

Wherein, at a temperature of 20-400° C., the diffusion depth from the carrier layer 1 to the metal foil layer 4 is less than or equal to 3 μm, and the diffusion depth from the metal foil layer 4 to the carrier layer 1 is less than or equal to 3μm.

In the embodiment of the present invention, the substrate with carrier includes a composite metal foil, an insulating adhesive layer 5 and a base film layer 6, and the composite metal foil includes a carrier layer 1, a barrier layer 2, a peeling layer 3 and a metal foil layer 4. The carrier layer 1 , the barrier layer 2 , the peeling layer 3 and the metal foil layer 4 are stacked in sequence; alternatively, the carrier layer 1 , the peeling layer 3 , the barrier layer 2 and the metal foil layer 4 The foil layers 4 are stacked and arranged in sequence; the composite metal foil is arranged on the base film layer 6 through the insulating adhesive layer 5, and the insulating adhesive layer 5 is arranged on the side of the metal foil layer 4 away from the carrier layer 1, and the base film layer 6 is arranged on the side of the metal foil layer 4 away from the carrier layer 1. On the side of the insulating adhesive layer 5 away from the metal foil layer 4, at a temperature of 20-400° C., the diffusion depth of the carrier layer 1 to the metal foil layer 4 is less than or equal to 3 μm, and the metal foil layer 4. The diffusion depth in the direction of the carrier layer 1 is less than or equal to 3 μm, wherein the release layer 3 is arranged to facilitate the release of the carrier layer 1, and the barrier layer 2 is arranged to prevent the carrier layer 1 and the metal foil layer 4 from being caused by mutual diffusion at high temperature. Bonding, so that the carrier layer 1 and the metal foil layer 4 can be easily peeled off, so that a relatively complete ultra-thin metal foil layer 4 with fewer pinholes can be obtained, which is beneficial to the preparation of subsequent micro circuits.

Preferably, the diffusion depth from the carrier layer 1 to the metal foil layer 4 is less than or equal to 1 μm, and the diffusion depth from the metal foil layer 4 to the carrier layer 1 is less than or equal to 1 μm.

3 and 8, preferably, when the carrier layer 1, the peeling layer 3, the barrier layer 2 and the metal foil layer 4 are stacked in sequence, the metal foil layer 4 and the The peel strength between the barrier layers 2 is greater than the peel strength between the peel layer 3 and the barrier layer 2 . When the carrier layer 1 , the peeling layer 3 , the barrier layer 2 and the metal foil layer 4 are stacked in sequence, the peeling strength between the metal foil layer 4 and the barrier layer 2 is greater than that of all The peeling strength between the peeling layer 3 and the barrier layer 2 is determined, so that when the substrate with carrier is used, peeling occurs between the peeling layer 3 and the barrier layer 2, and the barrier layer 2 It still remains on the metal foil layer 4 , so that the barrier layer 2 can prevent oxidation of the metal foil layer 4 , so as to protect the metal foil layer 4 . Of course, the peel strength between the metal foil layer 4 and the barrier layer 2 may also be less than or equal to the peel strength between the peel layer 3 and the barrier layer 2, so that the composite metal foil is peeled off. At this time, the barrier layer 2 can be partially or completely left on the peeling layer 3, and simultaneously peeled off from the metal foil layer 4 along with the carrier layer 1 and the peeling layer 3, referring to FIG. 3 and FIG. 7, and no further description is given here.

As shown in FIG. 1 and FIG. 6 , when the carrier layer 1 , the barrier layer 2 , the peeling layer 3 and the metal foil layer 4 are stacked in sequence, the peeling layer 3 and the metal foil layer The peel strength between 4 is greater than or equal to the peel strength between the peeling layer 3 and the barrier layer 2 . Since the peeling strength between the peeling layer 3 and the metal foil layer 4 is greater than or equal to the peeling strength between the peeling layer 3 and the barrier layer 2, when peeling the composite metal foil, the The peeling layer 3 can be partially or completely left on the metal foil layer 4 , so as to prevent the metal foil layer 4 from being oxidized, thereby effectively protecting the metal foil layer 4 . Of course, the peeling strength between the peeling layer 3 and the metal foil layer 4 may also be smaller than the peeling strength between the peeling layer 3 and the barrier layer 2, so that when the composite metal foil is peeled off, The peeling layer 3 can be partially or completely left on the barrier layer 2 and peeled off the metal foil layer 4 along with the carrier layer 1 and the barrier layer 2 at the same time. Therefore, no further details are given here.

1 to 4 , the barrier layer 2 includes a high temperature resistant layer 21, and the high temperature resistant layer 21 is an organic high temperature resistant layer 21; Made of any one or more of nickel, molybdenum, cobalt and graphite. Preferably, the high temperature resistant layer 21 is a single-layer alloy structure, or a multi-layer structure composed of a single metal layer, or a multi-layer structure composed of an alloy layer and a single metal layer. Specifically, the single-layer alloy structure is a single-layer structure made of an alloy material, for example, a single-layer structure made of a tungsten-chromium alloy; the multi-layer structure composed of the single metal layer is composed of multiple single-layer structures The multi-layer structure, each single-layer structure is made of a metal, for example, a multi-layer structure composed of a tungsten metal layer and a chromium metal layer; the multi-layer structure composed of the alloy layer and the single-metal layer is a plurality of monolayers A multi-layer structure composed of structures, each single-layer structure is composed of a metal or alloy material, such as a multi-layer structure composed of a zirconium metal layer and a tungsten-chromium alloy layer.

优选地，所述阻隔层2的厚度优选为

1 and 2 , when the carrier layer 1 , the barrier layer 2 , the peeling layer 3 and the metal foil layer 4 are stacked in sequence, in order to prevent the barrier layer 2 from interacting with the carrier The layers 1 are peeled off and delaminated. In this embodiment, the barrier layer 2 further includes a metal adhesive layer 22 , and the metal adhesive layer 22 is provided between the carrier layer 1 and the high temperature resistant layer 21 . For example, the barrier layer 2 includes a metal A that can be bonded to the carrier layer 1 and/or a metal B that can bond to the high temperature resistant layer 21 , so as to prevent the carrier layer 1 and the barrier layer 2 from interacting with each other. peel off. For example, metal A is copper or zinc; and metal B is nickel, iron or manganese. It can be understood that the metal bonding layer 22 is made of any one or more of copper, zinc, nickel, iron and manganese; or, the metal bonding layer 22 is made of one of copper or zinc material and one of nickel, iron and manganese. The structure of the metal bonding layer 22 may include but is not limited to the following situations: (1) the metal bonding layer 22 is a single metal layer composed of metal A, wherein the metal A is copper or zinc; (2) The metal bonding layer 22 is a single metal layer composed of metal B, wherein the metal B is nickel, iron or manganese; (3) The metal bonding layer 22 is composed of metal A and metal B (4) The metal bonding layer 22 includes a multi-layer structure composed of an alloy layer and a single metal layer; wherein, the metal bonding layer The alloy layer of 22 is made of metal A and metal B, and the single metal layer of the metal bonding layer 22 is made of metal A or metal B; for example, the alloy layer made of copper-nickel alloy and the single metal layer of manganese. Metal layer; (5) The metal bonding layer 22 is a multi-layer structure composed of a single-layer structure of metal A and a single-layer structure of metal B, for example, a multi-layer structure composed of a copper metal layer and a nickel metal layer. When the metal bonding layer 22 is a multi-layer structure composed of a single-layer structure of metal A and a single-layer structure of metal B, the single-layer structure of metal A is provided on the carrier layer 1 and the metal B Between the single-layer structures, since the bonding force between the metal A and the carrier layer 1 is relatively strong, and the bonding force between the metal B and the high temperature resistant layer 21 is relatively strong, the bonding force between the metal A and the high temperature resistant layer 21 is relatively strong. The single-layer structure of B is disposed between the carrier layer 1 and the single-layer structure of the metal B, so that the barrier layer 2 is not easily separated from the carrier layer 1 . By disposing the metal adhesive layer 22 , the barrier layer 2 can be firmly connected with the carrier layer 1 , thereby preventing the separation between the barrier layer 2 and the carrier layer 1 . In addition, the thickness of the barrier layer 2 is greater than or equal to

Preferably, the thickness of the barrier layer 2 is preferably

In this embodiment, the thickness of the metal foil layer 4 is less than or equal to 9 μm. In order to meet the requirements of fine circuit fabrication of circuit boards, preferably, the thickness of the metal foil layer 4 can be 6 μm, 5 μm, 4 μm or 2 μm, etc., so as to obtain an ultra-thin metal foil layer 4 that is conducive to the formation of fine circuit boards. In addition, in order to be able to peel off the carrier layer 1 to obtain a very thin metal foil layer 4 (especially a metal foil layer with a thickness of 2 μm, 4 μm, etc.) with few pinholes and completeness, in this embodiment, a metal adhesive layer is provided 22, so that the use of the metal bonding layer 22 not only makes the barrier layer 2 and the carrier layer 1 have a strong peeling strength, but also effectively ensures that the metal foil layer 4 can be stably peeled off from the carrier layer 1, thereby obtaining a complete polar The thin metal foil layer 4, and the surface of the carrier layer 1 is also treated with the metal bonding layer 22, so that the entire surface of the carrier layer 1 is more uniform and dense, which is conducive to peeling off the carrier layer 1 to obtain pinholes. Fewer ultra-thin metal foil layers 4 are needed, which is beneficial to the fabrication of subsequent circuits. In addition, the metal foil layer 4 is a copper foil or an aluminum foil; the carrier layer 1 can be a carrier copper, a carrier aluminum or an organic film, etc. Since the carrier layer 1 mainly plays a bearing role, a certain thickness is required. When the layer 1 is a carrier copper or a carrier aluminum, the thickness of the carrier layer 1 is preferably 9-50 μm; when the carrier layer 1 is an organic thin film, the thickness of the carrier layer 1 is preferably 20-100 μm.

3 and 4, similarly, when the carrier layer 1, the peeling layer 3, the barrier layer 2 and the metal foil layer 4 are stacked in sequence, in order to peel off the composite metal foil At this time, the barrier layer 2 can stay on the metal foil layer 4, so as to prevent the metal foil layer 4 from being oxidized. The barrier layer 2 may also include a metal adhesive layer 22. between the high temperature resistant layer 21 and the metal foil layer 4 . For example, the barrier layer 2 includes a metal A that can be bonded to the metal foil layer 4 and/or a metal B that can be bonded to the high temperature resistant layer 21 , thereby preventing the metal foil layer 4 from interacting with the barrier layer. Peel between 2. For example, metal A is copper or zinc; and metal B is nickel, iron or manganese. It can be understood that the metal bonding layer 22 is made of any one or more of copper, zinc, nickel, iron and manganese; or, the metal bonding layer 22 is made of one of copper or zinc material and one of nickel, iron and manganese. The structure of the metal bonding layer 22 may include but is not limited to the following situations: (1) the metal bonding layer 22 is a single metal layer composed of metal A, wherein the metal A is copper or zinc; (2) The metal bonding layer 22 is a single metal layer composed of metal B, wherein the metal B is nickel, iron or manganese; (3) The metal bonding layer 22 is composed of metal A and metal B (4) The metal bonding layer 22 includes a multi-layer structure composed of an alloy layer and a single metal layer; wherein, the metal bonding layer The alloy layer of 22 is made of metal A and metal B, and the single metal layer of the metal bonding layer 22 is made of metal A or metal B; for example, the alloy layer made of copper-nickel alloy and the single metal layer of manganese. Metal layer; (5) The metal bonding layer 22 is a multi-layer structure composed of a single-layer structure of metal A and a single-layer structure of metal B, for example, a multi-layer structure composed of a copper metal layer and a nickel metal layer. When the metal bonding layer 22 is a multi-layer structure composed of a single-layer structure of metal A and a single-layer structure of metal B, the single-layer structure of metal A is provided on the metal foil layer 4 and the metal foil layer 4 Between the single-layer structures of B, since the adhesive force between the metal A and the metal foil layer 4 is relatively strong, and the adhesive force between the metal B and the high temperature resistant layer 21 is relatively strong, the The single-layer structure of metal A is disposed between the metal foil layer 4 and the single-layer structure of metal B, so that the barrier layer 2 is not easily separated from the metal foil layer 4 . By arranging the metal adhesive layer 22, the barrier layer 2 can be firmly connected with the metal foil layer 4, thereby preventing peeling between the barrier layer 2 and the carrier layer 1, so that the When the composite metal foil is peeled off, the barrier layer 2 can remain on the metal foil layer 4 , so as to prevent the metal foil layer 4 from being oxidized, thereby protecting the metal foil layer 4 . In addition, the thickness of the barrier layer 2 is greater than or equal to Preferably, the thickness of the barrier layer 2 is preferably

由于当所述剥离层3过厚时难以形成均匀的金属箔层4，从而容易导致金属箔层4上产生大量针孔(当金属箔层4上具有针孔时，在其蚀刻成线路后，将容易出现断路现象)；当所述剥离层3过薄时，容易导致其与金属箔层4之间难以剥离；因此通过将所述剥离层3的厚度优选为从而确保了能够形成均匀的金属箔层4，避免了在金属箔层4上产生大量针孔，同时使得所述剥离层3与所述金属箔层4之间易于剥离。In the embodiment of the present invention, the peeling layer 3 is made of any one or more materials selected from nickel, silicon, molybdenum, graphite, titanium and niobium; or, the peeling layer 3 is made of an organic polymer material . Wherein, the thickness of the peeling layer 3 is preferably

Since it is difficult to form a uniform metal foil layer 4 when the peeling layer 3 is too thick, it is easy to cause a large number of pinholes on the metal foil layer 4 (when the metal foil layer 4 has pinholes, after it is etched into lines, It will be easy to open circuit phenomenon); when the peeling layer 3 is too thin, it is easy to cause it to be difficult to peel off from the metal foil layer 4; therefore, the thickness of the peeling layer 3 is preferably Thus, it is ensured that a uniform metal foil layer 4 can be formed, a large number of pinholes are avoided on the metal foil layer 4 , and at the same time, the peeling layer 3 and the metal foil layer 4 are easily peeled off.

In the embodiment of the present invention, the roughness Rz of the side of the carrier layer 1 close to the metal foil layer 4 is less than or equal to 5 μm; and/or, the side of the metal foil layer 4 away from the carrier layer 1 has a roughness Rz. The roughness Rz is 3.0 μm or less. When the metal foil layer 4 is copper foil, the greater the roughness of the copper foil, the greater the bonding force between it and other materials, but when the roughness of the copper foil is too large, it will not be used in high-frequency signal transmission In the circuit board, the roughness Rz of the general copper foil is 0.5-3.0μm; when the copper foil is used in high frequency, the roughness of the copper foil is set to be less than 0.5μm, so as to ensure the copper foil and other materials. Under the premise of the adhesion between the copper foils, the copper foil can be applied to circuit boards for high frequency signal transmission.

In the embodiment of the present invention, it should be noted that the roughness Rz represents the maximum height of the contour: the distance between the contour peak line and the valley bottom line. Among them, the sampling length is the length of the reference line specified for evaluating the surface roughness. The sampling length should be based on the actual surface formation and texture characteristics of the part, and the length that can reflect the surface roughness characteristics should be selected. The sampling length should be measured according to the actual situation. The general orientation of the surface profile is carried out.

In this embodiment of the present invention, in order to prevent the carrier layer 1 from being oxidized, a first anti-oxidation layer is provided on the side of the carrier layer 1 close to the barrier layer 2 in this embodiment; 1. A first anti-oxidation layer is provided on the side close to the blocking layer 2 to prevent the carrier layer 1 from being oxidized, thereby protecting the carrier layer 1. In order to prevent the metal foil layer 4 from being oxidized, a second anti-oxidation layer is provided on the side of the metal foil layer 4 away from the barrier layer 2 . A second anti-oxidation layer is provided on the side to prevent the metal foil layer 4 from being oxidized, thereby protecting the metal foil layer 4 .

In the embodiment of the present invention, the thickness of the insulating adhesive layer 5 is preferably 0.01-25 μm, and the insulating adhesive layer 5 may be made of thermoplastic resin or thermosetting resin, wherein the thermoplastic resin includes polystyrene series , vinyl acetate, polyester, polyethylene, polyamide, rubber or acrylate thermoplastic resin, the thermosetting resin includes phenolic, epoxy, urethane, melamine or alkyd Thermosetting resin; the thickness of the base film layer 6 is preferably 1-30 μm, and the base film layer 6 can be made of polyimide, thermoplastic polyimide, modified epoxy resin, modified acrylic resin, polyparaphenylene ethylene dicarboxylate, polybutylene terephthalate, polyethylene, polyethylene naphthalate, polystyrene, polyvinyl chloride, polysulfone, polyphenylene sulfide, polyetheretherketone, It is made of one or more materials selected from polyphenylene ether, polytetrafluoroethylene, liquid crystal polymer and polyoxalide.

1 to 8 , when the substrate with a carrier is a single-sided substrate with a carrier, the number of the composite metal foil and the insulating adhesive layer 5 is one; with reference to FIGS. 5 to 8 As shown, when the substrate with a carrier is a double-sided substrate with a carrier, the number of the composite metal foil and the insulating adhesive layer 5 is both two, and one of the composite metal foils passes through one of them. The insulating adhesive layer 5 is provided on one side of the base film layer 6 , and the other composite metal foil is provided on the other side of the base film layer 6 through the other insulating adhesive layer 5 .

In the embodiment of the present invention, the insulating adhesive layer 5 and the base film layer 6 may be formed separately, or may be integrally formed. Specifically, when the insulating adhesive layer 5 and the base film layer 6 are formed separately, when preparing a single-sided substrate with a carrier or a double-sided substrate with a carrier, a layer may be first formed on the base film layer 6 Insulating adhesive layer 5, and then pressing the composite metal foil on the surface of the base film layer 6 on which the insulating adhesive layer 5 is formed, or on the side of the metal foil layer 4 in the composite metal foil that is far away from the carrier layer 1 A layer of insulating adhesive layer 5 is formed, and then the side of the composite metal foil on which the insulating adhesive layer 5 is formed is pressed onto the side of the base film layer 6 . It should be known that when the insulating adhesive layer 5 and the base film layer 6 are formed separately, the thickness of the insulating adhesive layer 5 is relatively thick, preferably 7-25 μm, for example, can be 8 μm, 10 μm, 12 μm etc., and when the metal foil layer 4 is a copper foil, the substrate with a carrier formed at this time is a glue-type three-layer flexible coating composed of a metal foil layer 4, an insulating adhesive layer 5 and a base film layer 6. Copper plate (referred to as "3L-FCCL").

When the insulating adhesive layer 5 and the base film layer 6 are integrally formed, the base film structure formed by the insulating adhesive layer 5 and the base film layer 6 as a whole constitutes the base film structure of the substrate with the carrier. A part of the base film structure makes the surface of the base film structure have a certain viscosity, so when preparing a single-sided substrate with a carrier or a double-sided substrate with a carrier, the composite copper foil and the base film structure are directly pressed against each other. can be combined. It should be known that when the insulating adhesive layer 5 and the base film layer 6 are integrally formed, the thickness of the insulating adhesive layer 5 is very thin, preferably 0.01-5 μm, for example, can be 0.01 μm, 0.1 μm, etc., And when the metal foil layer 4 is copper foil, the substrate with carrier formed at this time is equivalent to the glue-free two-layer flexible copper clad laminate (referred to as "2L-FCCL") composed of the metal foil layer 4 and the base film structure. .

In order to solve the same technical problem, an embodiment of the present invention also provides a circuit board, which is obtained by using the substrate with a carrier; wherein, the method for preparing the circuit board from the substrate with a carrier can adopt existing It should be known that when using the substrate with the carrier to make a circuit board, the carrier layer 1 needs to be peeled off first, and then the circuit board is prepared by using the prior art method for preparing a circuit board, for example, in When using the metal foil layer 4 as a copper foil substrate with a carrier to make a circuit board, the carrier layer 1 can be peeled off first to obtain a non-adhesive two-layer flexible copper clad laminate or a glue-type three-layer flexible copper clad laminate. The circuit board is prepared by using the method for preparing circuit boards in the prior art.

17 to 19 , in order to solve the same technical problem, an embodiment of the present invention further provides a method suitable for preparing the substrate with a carrier, including the following steps:

S1, prepare one or two composite metal foils;

S2, pressing one of the composite metal foils on one side of the base film layer 6 through the insulating adhesive layer 5, or pressing two of the composite metal foils on the base film layer through the insulating adhesive layer 5 respectively On both sides of 6, a substrate with a carrier is obtained;

Wherein, preparing the composite metal foil specifically includes the following steps:

S11, forming the carrier layer 1;

S12, forming a barrier layer 2 on one side of the carrier layer 1;

S13, forming a peeling layer 3 on the barrier layer 2;

S14, forming a metal foil layer 4 on the peeling layer 3 to obtain a composite metal foil;

or,

S21, forming the carrier layer 1;

S22, forming a peeling layer 3 on one side of the carrier layer 1;

S23, forming a barrier layer 2 on the peeling layer 3;

S24, forming a metal foil layer 4 on the barrier layer 2 to obtain a composite metal foil;

Wherein, at a temperature of 20-400° C., the diffusion depth from the carrier layer 1 to the metal foil layer 4 is less than or equal to 3 μm, and the diffusion depth from the metal foil layer 4 to the carrier layer 1 is less than or equal to 3μm.

Preferably, the diffusion depth from the carrier layer 1 to the metal foil layer 4 is less than or equal to 1 μm, and the diffusion depth from the metal foil layer 4 to the carrier layer 1 is less than or equal to 1 μm.

In a specific implementation, when preparing a single-sided substrate with a carrier, one of the composite metal foils is pressed on one side of the base film layer 6 through the insulating adhesive layer 5; when preparing a double-sided substrate with a carrier, The two composite metal foils are respectively laminated on both sides of the base film layer 6 through the insulating adhesive layer 5 . In addition, in order to realize the lamination of the composite metal foil on the side of the base film layer 6 through the insulating adhesive layer 5, the metal foil layer 4 in the composite metal foil can be formed on the side away from the carrier layer 1 first. Insulating adhesive layer 5, and then pressing the side of the composite metal foil formed with the insulating adhesive layer 5 on the base film layer 6, or forming the insulating adhesive layer 5 on the base film layer 6 first, and then compounding the composite metal foil. The metal foil is press-bonded on the surface of the base film layer 6 on which the insulating adhesive layer 5 is formed.

3 and 8, preferably, when the carrier layer 1, the peeling layer 3, the barrier layer 2 and the metal foil layer 4 are stacked in sequence, the metal foil layer 4 and the The peel strength between the barrier layers 2 is greater than the peel strength between the peel layer 3 and the barrier layer 2 . When the carrier layer 1 , the peeling layer 3 , the barrier layer 2 and the metal foil layer 4 are stacked in sequence, the peeling strength between the metal foil layer 4 and the barrier layer 2 is greater than that of all The peeling strength between the peeling layer 3 and the barrier layer 2 is determined, so that when the substrate with carrier is used, peeling occurs between the peeling layer 3 and the barrier layer 2, and the barrier layer 2 It still remains on the metal foil layer 4 , so that the barrier layer 2 can prevent oxidation of the metal foil layer 4 , so as to protect the metal foil layer 4 . Of course, the peel strength between the metal foil layer 4 and the barrier layer 2 may also be less than or equal to the peel strength between the peel layer 3 and the barrier layer 2, so that the composite metal foil is peeled off. At this time, the barrier layer 2 can be partially or completely left on the peeling layer 3, and simultaneously peeled off from the metal foil layer 4 along with the carrier layer 1 and the peeling layer 3, referring to FIG. 3 and FIG. 7, and no further description is given here.

In the embodiment of the present invention, the formation of the barrier layer 2 on one side of the carrier layer 1 is specifically:

S131, forming a metal bonding layer 22 on one side of the carrier layer 1;

S132 , forming a high temperature resistant layer 21 on the metal bonding layer 22 .

In the embodiment of the present invention, the formation of the barrier layer 2 on the peeling layer 3 is specifically:

S231, forming a high temperature resistant layer 21 on the peeling layer 3;

S232 , forming a metal bonding layer 22 on the high temperature resistant layer 21 .

In the embodiment of the present invention, the metal bonding layer 22 and the high temperature resistant layer 21 may be formed by sputtering, the current of the sputtering method is preferably 6-12A, and the voltage is preferably 300-500V. The metal bonding layer 22 may be made of any one or more of copper, zinc, nickel, iron and manganese; or, the metal bonding layer 22 may be made of one of copper or zinc and Made of one of nickel, iron and manganese. The high temperature resistant layer 21 may be an organic high temperature resistant layer 21; or, the high temperature resistant layer 21 may be made of any one or more materials selected from tungsten, chromium, zirconium, titanium, nickel, molybdenum, cobalt and graphite , the high temperature resistant layer 21 may be a single-layer alloy structure or a multi-layer structure composed of a single metal layer or a multi-layer structure composed of an alloy layer and a single metal layer.

In the embodiment of the present invention, the forming of the carrier layer 1 specifically includes the following steps:

S111, performing a first electroplating to generate a first metal layer;

S112, performing a second electroplating on the surface of the first metal layer to generate a second metal layer, and the first metal layer and the second metal layer constitute a carrier layer;

In this embodiment of the present invention, after the carrier layer 1 is formed, the following steps are further included:

S113, roughening the carrier layer 1 to obtain a roughened carrier layer 1;

S114, forming a first anti-oxidation layer on the roughened carrier layer 1;

Wherein, the carrier layer 1 may be carrier copper or carrier aluminum. When the carrier layer 1 is carrier copper, both the first metal layer and the second metal layer are copper metal layers. When 1 is the carrier aluminum, both the first metal layer and the second metal layer are aluminum metal layers. The plating solution used for the first electroplating may include a copper sulfate solution, wherein the copper content of the plating solution used for the first electroplating is: 15-25g/L, and the pH value is 6-9; Electroplating may include copper sulfate solution, wherein the copper content of the plating solution used for the second electroplating is 70-80 g/L, the acid content is 90-100 g/L, and the plating solution used for the second electroplating also has a copper content of 70-80 g/L. Including additives, the additives include brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene glycol, the mass fraction of the brightening agent sodium sulfonate is preferably 0.1-2g/L, the leveling agent The mass fraction of thiourea is preferably 0.01-1 g/L, and the mass fraction of the wetting agent polyethylene glycol is preferably 0.1-5 g/L. The carrier layer 1 can be roughened by means of acid electroplating, wherein the plating solution for acid copper plating can include copper sulfate solution, wherein the copper content of the plating solution used for acid copper plating is 10 -15g/L, acid content 90-100g/L, molybdenum content 600-800PPM. Wherein, the formation of the first anti-oxidation layer can be in the form of zinc-nickel alloy; in addition, after the first anti-oxidation layer is formed on the roughened carrier layer 1, the first anti-oxidation layer can also be subjected to plasma treatment Cleaning (plasma), wherein the voltage during plasma cleaning is preferably 1500-2500V, and the current is preferably 0.1-1.5A.

In the embodiment of the present invention, in order to further prevent the bonding between the carrier layer 1 and the metal foil layer 4, after the formation of the carrier layer 1 in this embodiment, the following further includes:

S115 , annealing the carrier layer 1 under heat treatment conditions; wherein, the heat treatment conditions are: the heat treatment temperature is 200-300° C., and the heating time is 30-300 minutes. Preferably, the heating time is 1 hour. By annealing the carrier layer 1 under the heat treatment conditions, the crystal growth of the carrier layer 1 in the heating process is suppressed, the diffusion of the carrier layer 1 in the heating process is delayed, and the carrier layer 1 and the metal foil layer 4 are further prevented. bonding occurs between.

In the embodiment of the present invention, the peeling layer 3 may be made of any one or more materials selected from nickel, silicon, molybdenum, graphite, titanium and niobium. In addition, the formation of the peeling layer 3 on the barrier layer 2 or the forming of the peeling layer 3 on one side of the carrier layer 1 may specifically adopt the method of sputtering, wherein the peeling layer is formed by the method of sputtering The sputtering conditions of 3 may include: the current is preferably 6-12A, and the voltage is preferably 300-500V.

Since the roughness of the barrier layer 2 and the peeling layer 3 is easily affected by the current during electroplating, the surface roughness of the barrier layer 2 and the peeling layer 3 is very uneven, so As a result, the surface roughness of the metal foil layer 4 in the subsequent formation is not uniform, which is not conducive to the formation of excellent peeling stability and the number of pinholes, and is also not conducive to the fabrication of subsequent circuits. Based on this, in the embodiment of the present invention, the metal bonding layer 22, the high temperature resistant layer 21 and the peeling layer 3 are preferably sputtered, the current of the sputtering method is preferably 6-12A, and the voltage is preferably Use 300-500V. The metal bonding layer 22 and the high temperature resistant layer 21 formed by sputtering constitute the barrier layer 2 to ensure a uniform and dense barrier layer 2, and a uniform and dense peeling layer 3 is formed by sputtering, thereby having It is beneficial to improve the peeling stability of the composite metal foil and can effectively reduce the number of pinholes; in addition, the metal foil layer 4 is preferably formed by electroplating, and before the metal foil layer 4 is formed, uniformity is formed by sputtering The dense barrier layer 2 and the peeling layer 3 are conducive to the uniform electroplating of the metal foil layer 4, so that the surface roughness of the formed metal foil layer 4 is relatively uniform, which is further conducive to the production of subsequent circuits, and is conducive to the production of Thinner said metal foil layer 4.

In the embodiment of the present invention, the forming of the metal foil layer 4 on the peeling layer 3 is specifically:

S141, sputtering a third metal layer on the peeling layer 3;

S142, electroplating a fourth metal layer on the sputtered third metal layer, where the third metal layer and the fourth metal layer constitute the metal foil layer; or,

The forming of the metal foil layer 4 on the barrier layer 2 is as follows:

S241, sputtering a third metal layer on the barrier layer 2;

S242, electroplating a fourth metal layer on the sputtered third metal layer, where the third metal layer and the fourth metal layer constitute the metal foil layer.

The metal foil layer 4 may be copper foil or aluminum foil. When the metal foil layer 4 is copper foil, the third metal layer and the fourth metal layer are both copper metal layers; When 4 is aluminum foil, both the third metal layer and the fourth metal layer are aluminum metal layers. Since the peeling layer 3 has peeling properties, if the electroplating method is simply used, it is easy to cause unevenness of the electroplated metal layer. In order to obtain the metal foil layer 4 with a uniform surface, in this embodiment, the third metal layer is first sputtered, and then the fourth metal layer is electroplated. metal layer, thereby avoiding pinholes in the metal foil layer 4 and obtaining a metal foil layer 4 with a uniform surface. The sputtering conditions for sputtering the third metal layer on the peeling layer 3 or sputtering the third metal layer on the barrier layer 2 are as follows: the current is preferably 6-12A, the voltage is preferably 300-500V, and the vacuum The thickness is preferably 0.1-0.5Pa, the sputtering speed is preferably 4-10m/min, and the winding and unwinding tension is preferably 60-150N.

In the embodiment of the present invention, the electroplating of the fourth metal layer on the sputtered third metal layer specifically includes the following steps:

S31, carry out the third electroplating to generate the fifth metal;

S32, performing fourth electroplating on the surface of the fifth metal layer to generate a sixth metal layer, where the fifth metal layer and the sixth metal layer constitute the fourth metal layer;

Wherein, the plating solution used for the third electroplating may include copper sulfate solution, wherein the copper content of the plating solution used for the third electroplating is: 15-25g/L, and the pH value is 6-9; The plating solution for the fourth electroplating may include a copper sulfate solution, wherein the plating solution for the fourth electroplating has a copper content of 70-80 g/L and an acid content of 90-100 g/L, and the plating solution used for the fourth electroplating has a copper content of 70-80 g/L and an acid content of 90-100 g/L. The liquid includes additives, the additives include brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene glycol, the mass fraction of the brightening agent sodium sulfonate is preferably 0.1-2g/L, the leveling agent The mass fraction of the agent thiourea is preferably 0.01-1 g/L, and the mass fraction of the wetting agent polyethylene glycol is preferably 0.1-5 g/L. The metal foil layer 4 can be copper foil or aluminum foil. When the metal foil layer 4 is copper foil, the fifth metal layer and the sixth metal layer are both copper metal layers; When 4 is an aluminum foil, both the fifth metal layer and the sixth metal layer are aluminum metal layers. In the embodiment of the present invention, in order to avoid the warpage of the composite metal foil, in this embodiment, the plating solutions for preparing the carrier layer 1 and the metal foil layer 4 (including the plating solution for the first electroplating, the plating solution for the first The plating solution for the second electroplating, the plating solution for the third electroplating, and the plating solution for the fourth electroplating) are set to be the same, so that the stress action and the tensile force action of the carrier layer 1 and the metal foil layer 4 are the same, Therefore, the bending degrees of the carrier layer 1 and the metal foil layer 4 are the same, thereby avoiding the warpage of the composite metal foil.

In the embodiment of the present invention, the preparation method of the substrate with a carrier further comprises the steps of:

S41 , roughening the side of the metal foil layer 4 away from the carrier layer 1 .

S42 , forming a second anti-oxidation layer on the roughened side of the metal foil layer 4 away from the carrier layer 1 .

Wherein, the roughening treatment of the surface of the metal foil layer 4 away from the carrier layer 1 can be performed by acid electroplating, wherein the copper content of the acid copper plating solution is 10-15g/L, The acid content is 90-100g/L, and the molybdenum content is 600-800PPM; wherein, the second anti-oxidation layer can be formed in the form of a zinc-nickel alloy; in addition, after the second anti-oxidation layer is formed, the Plasma cleaning (plasma) is performed on the second anti-oxidation layer, wherein the voltage during plasma cleaning is preferably 1500-2500V, and the current is preferably 0.1-1.5A.

The following examples are provided below to illustrate the preparation method of the composite metal foil, as follows:

Example 1

S51, forming the carrier layer 1; specifically, firstly performing first electroplating to generate a first metal layer; then, performing a second electroplating on the surface of the first metal layer to generate a second metal layer, the first metal layer and the The second metal layer constitutes a carrier layer; then, the carrier layer 1 is roughened, and a first anti-oxidation layer is formed on the roughened carrier layer 1 . The carrier layer 1 is annealed under heat treatment conditions; wherein, the heat treatment conditions are: the heat treatment temperature is 250° C. and the heating time is 1 hour. Wherein, the carrier layer 1 is carrier copper, the plating solution used for the first electroplating includes copper sulfate solution, and the copper content of the plating solution used for the first electroplating is: 20g/L, and the pH value is 7; For the second electroplating, a copper sulfate solution may be included, wherein the copper content of the plating solution for the second electroplating is 75 g/L, the acid content is 95 g/L, and the plating solution for the second electroplating also has a copper content of 75 g/L. Including additives, the additives include brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene glycol, the mass fraction of the brightening agent sodium sulfonate is 0.8g/L, the leveling agent thiourea The mass fraction of the wetting agent is 0.5g/L, and the mass fraction of the wetting agent polyethylene glycol is 3g/L. In addition, the carrier layer 1 is roughened by means of acid electroplating, wherein the plating solution used for acid copper plating includes copper sulfate solution, wherein the copper content of the plating solution used for acid copper plating is 13 g/ L, the acid content is 95g/L, and the molybdenum content is 700PPM. Wherein, forming the first anti-oxidation layer adopts the form of zinc-nickel alloy.

S52, forming a barrier layer 2 on one side of the carrier layer 1 by sputtering; specifically, firstly forming a metal bonding layer 22 on one side of the carrier layer 1 by sputtering, and then forming a metal bonding layer 22 on the side of the carrier layer 1 by sputtering A high temperature resistant layer 21 is formed on the metal adhesive layer 22 . Wherein, the metal bonding layer 22 is a structure composed of a copper metal layer and a nickel metal layer, and the copper metal layer is connected to the carrier layer 1, and the nickel metal layer is connected to the high temperature resistant layer 21; the high temperature resistant layer 21 is a single-layer alloy structure made of tungsten-titanium alloy;

S53, forming a peeling layer 3 on the barrier layer 2 by sputtering; wherein, the peeling layer 3 is a graphite layer;

S54, forming a metal foil layer 4 on the peeling layer 3; specifically, firstly, sputtering a third metal layer on the peeling layer 3, and then electroplating a fourth metal layer on the sputtered third metal layer, The third metal layer and the fourth metal layer constitute the metal foil layer. Wherein, the metal foil layer 4 is copper foil, the third metal layer and the fourth metal layer are both copper metal layers, and the sputtering conditions for sputtering the third metal layer on the peeling layer 3 are: The current is preferably 9A, the voltage is preferably 400V, the vacuum degree is preferably 0.3Pa, the sputtering speed is preferably 7m/min, and the winding and unwinding tension is preferably 100N; in this example, the carrier layer 1 and the metal foil will be prepared. The plating solutions of the layer 4 (including the plating solution for the first plating, the plating solution for the second plating, the plating solution for the third plating, and the plating solution for the fourth plating) were set to be the same.

S55, roughening the side of the metal foil layer 4 away from the carrier layer 1, and using acid electroplating to form a first Two anti-oxidation layers; wherein, the copper content of the acid copper plating solution is 13g/L, the acid content is 95g/L, and the molybdenum content is 600-800PPM; in addition, the second anti-oxidation layer is formed by zinc-nickel plating Alloy form.

Example 2

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of tungsten-nickel alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 3

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of tungsten-molybdenum alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 4

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of a chromium-nickel alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 5

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of zirconium-titanium alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 6

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of titanium-nickel alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 7

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of titanium-molybdenum alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 8

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of titanium-cobalt alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 9

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of nickel-molybdenum alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 10

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a single-layer alloy structure made of molybdenum-cobalt alloy. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 11

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a structure made of a tungsten metal layer and a graphite layer, the tungsten metal layer is connected to the metal bonding layer 22 , and the graphite layer is connected to the peeling layer 3 connections. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 12

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a structure made of a chromium metal layer and a graphite layer, the chromium metal layer is connected to the metal bonding layer 22 , and the graphite layer is connected to the peeling layer 3 connections. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 13

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a structure made of a nickel metal layer and a graphite layer, and the nickel metal layer is connected to the metal bonding layer 22, and the graphite layer is connected to the peeling layer 3 connections. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 14

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is made of a tungsten-nickel alloy and a chromium metal layer, and the tungsten-nickel alloy is connected to the metal bonding layer 22, and the chromium metal layer is connected to the metal bonding layer 22. The peeling layer 3 is connected. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 15

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is a structure made of a nickel-molybdenum alloy and a chromium metal layer, and the nickel-molybdenum alloy is connected to the metal bonding layer 22, and the chromium metal layer is connected to the metal bonding layer 22. The peeling layer 3 is connected. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 16

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is made of a molybdenum-cobalt alloy and a chromium metal layer, and the molybdenum-cobalt alloy is connected to the metal bonding layer 22, and the chromium metal layer is connected to the metal bonding layer 22. The peeling layer 3 is connected. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Example 17

The difference between this embodiment and Embodiment 1 is that the high temperature resistant layer 21 is made of a titanium-nickel alloy and a chromium metal layer, and the titanium-nickel alloy is connected to the metal bonding layer 22, and the chromium metal layer is connected to the metal bonding layer 22. The peeling layer 3 is connected. Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Comparative Example 1

The difference between this embodiment and Embodiment 1 is that after the carrier layer 1 is formed, the barrier layer 2 is not formed, but a peeling layer 3 is directly formed on the carrier layer 1 . Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Comparative Example 2

The difference between this embodiment and Embodiment 1 is that after the metal bonding layer 22 is formed, the high temperature resistant layer 21 is not formed, but the peeling layer 3 is directly formed on the metal bonding layer 22 . Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Comparative Example 3

The difference between this embodiment and Embodiment 1 is that after the carrier layer 1 is formed, the metal bonding layer 22 is not formed, but a high temperature resistant layer 21 is directly formed on the carrier layer 1 . Other processes and steps in this embodiment are the same as those in Embodiment 1, and are not repeated here.

Table 1 shows that the composite metal foils prepared in Examples 1-17 were directly tested for multiple times at normal temperature (such as 16-27°C, taking 25°C as an example), or at different temperatures (200°C and 340°C). ) and the base film layer 6 are pressed together, and the test results of multiple tests are carried out under normal temperature conditions. The measured diffusion depth from the carrier layer 1 to the metal foil layer 4 and the metal foil layer 4 Diffusion depth in the direction of the carrier layer 1 .

Table 1

Since the carrier layer 1 and the metal foil layer 4 will undergo a certain degree of mutual diffusion under high temperature conditions, resulting in a certain degree of bonding between the carrier layer 1 and the metal foil layer 4, it can be seen from Table 1 that It can be seen that the diffusion depth from the carrier layer 1 to the metal foil layer 4 and the diffusion depth from the metal foil layer 4 to the carrier layer 1 increases with increasing temperature. In the composite metal foils prepared in Examples 1-17, the diffusion depth from the carrier layer 1 to the metal foil layer 4 and the direction of the metal foil layer 4 to the carrier layer 1 were observed at normal temperature or high temperature. The diffusion depths are all less than 3 μm. Therefore, when the substrate with carrier is used, the carrier layer 1 and the metal foil layer 4 are prevented from interdiffusion caused by bonding at high temperature, so that the carrier layer 1 and the metal foil layer 4 can be easily peeled off. However, the interdiffusion of the composite metal foils prepared in Comparative Examples 1 and 2 is relatively serious under high temperature conditions, so that the carrier layer 1 and the metal foil layer 4 are bonded to a large extent, which leads to the use of all In the case of the substrate with carrier, it is inconvenient to peel off the carrier layer 1, the barrier layer 2 and the peeling layer 3 from the metal foil layer 4 at the same time; in addition, because the composite metal foil prepared in Comparative Example 3 has For the high temperature resistant layer 21, under high temperature conditions, the diffusion depth from the carrier layer 1 to the metal foil layer 4 and the diffusion depth from the metal foil layer 4 to the carrier layer 1 are both less than 3 μm, but , since the composite metal foil prepared in Comparative Example 3 does not have the metal bonding layer 22, its diffusion is more serious than that of the composite metal foils prepared in Examples 1-17.

To sum up, the embodiment of the present invention provides a substrate with a carrier and a preparation method thereof, wherein the substrate with a carrier includes a composite metal foil, an insulating adhesive layer 5 and a base film layer 6, and the insulating adhesive layer 5 is provided on the composite metal foil. Between the metal foil and the base film layer 6, the composite metal foil includes a carrier layer 1, a barrier layer 2, a peeling layer 3 and a metal foil layer 4, through the carrier layer 1, the barrier layer 2, the peeling layer 3 and the The metal foil layers 4 are stacked in sequence; alternatively, the carrier layer 1 , the peeling layer 3 , the barrier layer 2 and the metal foil layer 4 are stacked in sequence; the composite metal foil is provided by the insulating adhesive layer 5 . On the base film layer 6, and the insulating adhesive layer 5 is arranged on the side of the metal foil layer 4 away from the carrier layer 1, the base film layer 6 is arranged on the side of the insulating adhesive layer 5 away from the metal foil layer 4, At a temperature of 20-400°C, the diffusion depth from the carrier layer 1 to the metal foil layer 4 is less than or equal to 3 μm, and the diffusion depth from the metal foil layer 4 to the carrier layer 1 is less than or equal to 3 μm, wherein , by setting the peeling layer 3 to facilitate the peeling of the carrier layer 1, and by setting the barrier layer 2 to prevent the carrier layer 1 and the metal foil layer 4 from interdiffusion and bonding at high temperature, so that the carrier layer 1 and the metal foil layer 4 are easy to peel off, and then A relatively complete ultra-thin metal foil layer 4 with fewer pinholes can be obtained, which is beneficial to the preparation of subsequent fine circuits.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the technical principle of the present invention, several improvements and replacements can be made. These improvements and replacements It should also be regarded as the protection scope of the present invention.

Claims (17)

1. A substrate with a carrier, characterized in that the substrate with a carrier comprises a composite metal foil, an insulating adhesive layer and a base film layer, and the composite metal foil comprises a carrier layer, a barrier layer, a peeling layer and a metal foil Floor; The carrier layer, the barrier layer, the peeling layer and the metal foil layer are stacked in sequence; or, The carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence; The composite metal foil is arranged on the base film layer through the insulating adhesive layer, and the insulating adhesive layer is arranged on the side of the metal foil layer away from the carrier layer, and the base film layer is arranged on the side of the insulating adhesive layer away from the metal foil layer; Wherein, at a temperature of 20-400° C., the diffusion depth from the carrier layer to the metal foil layer is less than or equal to 3 μm, and the diffusion depth from the metal foil layer to the carrier layer is less than or equal to 3 μm. 2 . The substrate with carrier according to claim 1 , wherein the diffusion depth of the carrier layer to the metal foil layer is less than or equal to 1 μm, and the diffusion of the metal foil layer to the carrier layer direction is 1 μm or less. 3 . The depth is less than or equal to 1 μm. 3 . The substrate with carrier according to claim 1 , wherein the carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence, and the metal foil layer and the The peel strength between the barrier layers is greater than the peel strength between the peel layer and the barrier layer. 4. The substrate with carrier according to claim 1, wherein the barrier layer comprises a high temperature resistant layer, and the high temperature resistant layer is an organic high temperature resistant layer; or, the high temperature resistant layer is made of tungsten, chromium, Made of any one or more of zirconium, titanium, nickel, molybdenum, cobalt and graphite. 5 . The substrate with carrier according to claim 4 , wherein the high temperature resistant layer is a single-layer alloy structure, a multi-layer structure composed of a single metal layer, or a multi-layer structure composed of an alloy layer and a single metal layer. 6 . 6 . The substrate with carrier according to claim 4 , wherein the carrier layer, the barrier layer, the peeling layer and the metal foil layer are stacked in sequence, and the barrier layer further comprises a metal adhesive layer. 7 . A junction layer, the metal bonding layer is arranged between the carrier layer and the high temperature resistant layer. 7 . The substrate with carrier according to claim 4 , wherein the carrier layer, the peeling layer, the barrier layer and the metal foil layer are stacked in sequence, and the barrier layer further comprises a metal adhesive layer. 8 . A junction layer, the metal bonding layer is arranged between the high temperature resistant layer and the metal foil layer. 8. The substrate with carrier according to claim 6 or 7, wherein the metal adhesive layer is made of any one or more of copper, zinc, nickel, iron and manganese; or, The metallic bonding layer is made of one of copper or zinc and one of nickel, iron and manganese. 9 . The substrate with carrier according to claim 1 , wherein the peeling layer is made of any one or more materials selected from nickel, silicon, molybdenum, graphite, titanium and niobium. 10 . ; or, the peeling layer is made of an organic polymer material. 10 . The substrate with carrier according to claim 1 , wherein the thickness of the metal foil layer is less than or equal to 9 μm. 11 . 11. The substrate with carrier according to any one of claims 1 to 7, wherein the metal foil layer is copper foil or aluminum foil; and/or the carrier layer is copper carrier or aluminum carrier or organic film. 12. The substrate with carrier according to any one of claims 1-7, wherein the roughness Rz of the side of the carrier layer close to the metal foil layer is less than or equal to 5 μm; and/or, the The roughness Rz of the side of the metal foil layer away from the carrier layer is less than or equal to 3.0 μm. 13. The substrate with a carrier according to any one of claims 1 to 7, wherein a first anti-oxidation layer is provided on the side of the carrier layer close to the barrier layer; and/or, the A second anti-oxidation layer is provided on the side of the metal foil layer away from the barrier layer. 14 . The substrate with carrier according to claim 1 , wherein the insulating adhesive layer has a thickness of 0.01-25 μm; and/or the base film layer has a thickness of 1-25 μm. 15 . 30μm. 15. The substrate with carrier according to any one of claims 1-7, wherein the insulating adhesive layer is made of thermoplastic resin or thermosetting resin, wherein the thermoplastic resin comprises polystyrene, Vinyl acetate, polyester, polyethylene, polyamide, rubber, or acrylate thermoplastic resins, including phenolic, epoxy, urethane, melamine, or alkyd thermosets resin; and/or, the base film layer is made of polyimide, thermoplastic polyimide, modified epoxy resin, modified acrylic resin, polyethylene terephthalate, polybutylene terephthalate Diol ester, polyethylene, polyethylene naphthalate, polystyrene, polyvinyl chloride, polysulfone, polyphenylene sulfide, polyether ether ketone, polyphenylene ether, polytetrafluoroethylene, liquid crystal polymer, Made of one or more of the polyoxalides. 16. The substrate with carrier according to any one of claims 1-7, wherein the number of the composite metal foil and the insulating adhesive layer is two, and one of the composite metal foil passes through One of the insulating adhesive layers is provided on one side of the base film layer, and the other composite metal foil is provided on the other side of the base film layer through the other insulating adhesive layer. 17. A circuit board, characterized in that, the circuit board is obtained by using the substrate with a carrier according to any one of claims 1-16.

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