WO2019201145A1 - Easy-to-peel carrier foil, preparation method therefor, and application thereof - Google Patents
Easy-to-peel carrier foil, preparation method therefor, and application thereof Download PDFInfo
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- WO2019201145A1 WO2019201145A1 PCT/CN2019/082220 CN2019082220W WO2019201145A1 WO 2019201145 A1 WO2019201145 A1 WO 2019201145A1 CN 2019082220 W CN2019082220 W CN 2019082220W WO 2019201145 A1 WO2019201145 A1 WO 2019201145A1
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- carrier foil
- foil
- easily peelable
- graphite
- roughened
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1152—Replicating the surface structure of a sacrificial layer, e.g. for roughening
Definitions
- the invention belongs to the technical field of semiconductors, and in particular relates to an easily peelable carrier foil and a preparation method and application thereof.
- PCB printed circuit board
- electrolytic copper foil As the main raw material of printed circuit board (PCB), the development of electrolytic copper foil has been following the development of PCB technology, and more than 95% is used in the manufacture of printed circuit board substrates.
- PCBs are constantly improving with the rapid development of electronic products.
- electronic products are developing in the direction of low cost, high reliability, high stability and high functionality. Therefore, the performance and variety of electrolytic copper foils are updated and higher.
- Copper foil has developed a new trend, and its thickness has been thinner and thinner. With the recent generalization, miniaturization and densification of electronic devices, the width and spacing of printed circuit boards have become thinner and thinner.
- the requirements for electrolytic copper foil are also increasing. At present, copper foil is getting thinner and thinner, and its preparation is more difficult, and it is easy to crack and wrinkle during transportation.
- a peelable type carrier-coated electrolytic ultra-thin copper foil has been widely used for lamination with a substrate by hot press processing, and then the ultra-thin copper foil layer is peeled off from the carrier foil to be used as a copper-clad laminate, in which case the carrier is used.
- the peeling is unstable at the joint interface between the foil and the ultra-thin copper foil, and some of the carrier ultra-thin copper foil is peeled off during processing, and some may not be completely peeled off or partially peeled off after hot press processing.
- the peeling layer used at home and abroad mainly includes an organic layer as a peeling layer and an inorganic layer as a peeling layer.
- the organic compound which is used in the organic release layer is carboxybenzotriazole (CBTA), a nitrogen-containing compound, a sulfur-containing compound, a carboxylic acid, etc., and one or two or more of them may be used.
- the organic release layer can be formed very easily by dipping or coating an aqueous solution containing the selected organic compound.
- the organic peeling layer is difficult to peel at high temperature, so that the peeling strength of the carrier foil is not stable enough;
- the inorganic peeling layer is a metal base layer or an alloy layer, and the most commonly used metal base layer is a chromium base layer, and the alloy layer generally has a Ni-Mo alloy, Ni- Co alloy, Cr-Co alloy, Mo-Co alloy, and the like.
- the temperature of the chromium base layer exceeds 450 ° C, the peel strength is unstable, and the metal chromium as the separator is itself toxic, harmful to the environment and the human body, and generally not used.
- a defect of the inorganic release layer is that the release layer formed of the metal base layer or the alloy layer is affected by the adhesion amount of the metal when the carrier is peeled off, and in actual operation, the adhesion amount of these metals is not easily controlled, and at a high temperature
- the carrier foil layer, the release layer and the ultra-thin copper foil layer cause mutual diffusion, resulting in a phenomenon in which the carrier foil layer and the ultra-thin copper foil layer are partially peeled off or not peeled at all.
- the present invention provides an easy-peeling carrier foil and a preparation method and application thereof, which can effectively solve the problem that the existing peeling layer is easy to make the peeling strength of the carrier foil unstable under high temperature, and the carrier foil layer and the ultra-thin copper are produced. A technical defect in which the foil layer is partially peeled off or not peeled at all.
- the present invention provides an easily peelable carrier foil comprising: a roughened carrier foil and a graphite-based material adhered to the roughened surface of the roughened carrier foil.
- the roughening treatment specifically comprises forming a convex structure on the surface of the carrier foil by a chemical method or a plasma etching method.
- the graphite-based material is specifically graphite or graphene.
- attaching the graphite-based material to the surface of the roughened carrier foil comprises specifically attaching the graphite-based material to the roughened carrier by chemical vapor deposition or magnetron sputtering. The rough side of the foil.
- the carrier foil is in particular a metal foil or an organic film.
- the metal foil is one or more of copper, copper alloy, aluminum, aluminum alloy or stainless steel.
- the organic film is PET, PI or PEN.
- the invention also provides the application described.
- the invention also provides a preparation method of an easily peelable carrier foil, comprising the following steps:
- Step 1 roughening the surface of the carrier foil to obtain a roughened carrier foil
- Step 2 adhering to the graphite-based material on the rough surface of the roughened carrier foil by chemical vapor deposition or magnetron sputtering to obtain an easily peelable carrier foil.
- the use of the easily peelable carrier foil provided by the present invention or the easy-peeling carrier foil prepared by the method for preparing the easily peelable carrier foil is used for preparing an ultra-thin copper foil.
- the application comprises the following steps:
- Step 1 preparing an easily peelable carrier foil
- Step 2 plating a copper foil on the surface of the graphite-based material of the easily peelable carrier foil;
- Step 3 The easily peelable carrier foil is peeled off from the ultra-thin copper foil by a physical method.
- the physical method of the step 3 is that the easily peelable carrier foil is peeled off from the ultra-thin copper foil by hot pressing.
- the invention provides an easily peelable carrier foil, and the roughened carrier foil has a specific function of rough forming a convex structure, and the contact structure of the convex structure and the graphite material is larger, and the graphite material and the carrier foil can be ensured.
- the bonding force is greater than the bonding strength between the graphite material and the ultra-thin copper foil. Since the bonding force between the graphite material and the carrier foil is not large, the graphite material of the carrier foil and the ultra-thin copper foil layer are not peeled off during transportation. After hot pressing, it can be completely peeled off without impurities.
- the graphite-based material is a material having small thermal expansion property and a certain adhesion, and its chemical property is stable and moderately bonded to an ultra-thin copper foil, and can effectively serve as a peeling layer.
- the graphite-based material used in this patent has a certain adhesion at normal temperature as a peeling layer, so that the ultra-thin copper foil does not fall off; the thermal expansion property at a high temperature is small, and the carrier foil layer, the peeling layer and the super layer are not generated.
- the problem of interdiffusion of metals between the thin copper foil layers does not cause partial peeling or partial peeling of the carrier foil layer and the ultra-thin copper foil layer.
- the chemical properties of graphite materials are stable and do not form compounds with ultra-thin copper foil, so that it does not cause difficult peeling; in addition, due to the small thermal expansion of graphite, it is not easy to produce warpage and deformation during heating processing;
- the yield of ultra-thin copper foil reduces the production cost; moreover, graphite is a common material, rich in resources and cheap, which is beneficial to reduce the manufacturing cost of ultra-thin copper foil.
- FIG. 1 is a schematic structural view of a roughened carrier foil in a specific embodiment of the present invention.
- FIG. 2 is a schematic structural view of an easily peelable carrier foil in a specific embodiment of the present invention.
- FIG. 3 is a schematic structural view of an easily peelable carrier foil and an ultra-thin copper foil in a specific embodiment of the present invention
- the reference numerals the convex structure 1, the roughened carrier foil 2, the graphite material 3, the copper foil 4, and the side A of the graphite-based material.
- the invention provides an easy-peeling carrier foil and a preparation method and application thereof, which are used for solving the problem that the existing peeling layer is easy to make the peeling strength of the carrier foil unstable at a high temperature, and the carrier foil layer and the ultra-thin copper foil layer are partially peeled off. Or technical defects that cannot be stripped at all.
- the present invention provides an easily peelable carrier foil comprising: a roughened carrier foil 2 and a graphite-based material 3 attached to the roughened roughened carrier foil 2 surface.
- the roughening treatment specifically includes forming the convex structure 1 on the surface of the carrier foil by a chemical method or/and a plasma etching method.
- the chemical method is specifically a photochemical etching method.
- the photochemical etching method removes the protective film to be etched by exposure, and after developing, contacts the chemical solution during etching to achieve dissolution and corrosion, and forms an effect of unevenness or hollowing.
- the plasma etching is specifically: using a glow discharge of a specific gas (or a mixed gas) having a gas pressure of 10 to 1000 Pa, to generate a molecular or molecular group capable of undergoing an ionic chemical reaction with the film, and the generated reaction product is volatilized. Sexual. It is evacuated in a low pressure vacuum chamber to effect etching. By selecting and controlling the composition of the discharge gas, better etch selectivity and higher etch rate can be obtained.
- the graphite-based material 3 specifically includes graphite or graphene.
- the adhesion of the graphite-based material 3 to the surface of the roughened carrier foil 2 specifically includes attaching the graphite-based material 3 to the rough surface of the roughened carrier foil 2 by a CVD method or a magnetron sputtering method.
- the carrier foil specifically comprises a metal foil or an organic film.
- the metal foil comprises one or more of copper, copper alloy, aluminum, aluminum alloy or stainless steel.
- the organic film includes PET, PI or PEN.
- the carrier foil 2 has a thickness of 18 to 35 ⁇ m.
- the invention also discloses a preparation method of an easily peelable carrier foil, comprising the following steps:
- Step 1 roughening the surface of the carrier foil to obtain a roughened carrier foil 2;
- Step 2 The graphite material 3 is adhered to the rough surface of the roughened carrier foil 2 by a chemical vapor deposition method or a magnetron sputtering method to obtain an easily peelable carrier foil.
- the above application includes the following steps:
- Step 1 roughening the surface of the carrier foil to obtain a roughened carrier foil 2;
- Step 2 attaching the rough surface of the roughened carrier foil 2 to the graphite-based material 3 to obtain an easily peelable carrier foil;
- Step 3 electroplating the copper foil 4 on the surface A of the graphite-based material of the easily peelable carrier foil;
- Step 4 The easily peelable carrier foil is peeled off from the ultra-thin copper foil by hot pressing.
- the surface of the surface A of the graphite-based material 3 of the step 3 is smooth and flat.
- the thickness of the copper foil 4 of the step 3 is 1 to 9 ⁇ m.
- the raw materials of the following examples are all commercially available or self-made
- the PET film is a high temperature resistant polyester film
- the PI film is a polyimide film
- the PEN film is a polyethylene naphthalate film
- the CVD method is a chemical vapor phase. Deposit.
- a specific embodiment of the present invention provides a method for preparing an easily peelable carrier foil and an application thereof, and Embodiment 1 includes the following steps:
- Step 1 Take a carrier copper foil with a thickness of 20 microns
- Step 2 forming a raised structure on the carrier copper foil by photochemical etching
- Step 3 The surface of the convex structure of the carrier copper foil is plated with graphite by CVD, and the surface of the graphite (on the side of the convex structure away from the carrier copper foil) is smooth and flat;
- Step 4 preparing an ultra-thin copper foil having a thickness of 2 ⁇ m by chemical plating on a smooth and flat graphite surface;
- Step 5 hot pressing on the carrier copper foil by hot pressing, and completely peeling the carrier copper foil from the ultra-thin copper foil.
- the graphite surface (on the side of the convex structure away from the carrier copper foil) is the A side of FIG.
- a specific embodiment of the present invention provides a method for preparing an easily peelable carrier foil and an application thereof, and Embodiment 2 includes the following steps:
- Step 1 Take a carrier aluminum foil with a thickness of 25 microns
- Step 2 forming a raised structure on the carrier aluminum foil by photochemical etching
- Step 3 The surface of the convex structure of the carrier aluminum foil is plated with graphite by CVD, and the surface of the graphite (on the side of the convex structure away from the carrier aluminum foil) is smooth and flat;
- Step 4 preparing an ultra-thin copper foil having a thickness of 3 ⁇ m by chemical plating on a smooth and flat graphite surface;
- Step 5 hot pressing on the carrier aluminum foil by hot pressing, and completely peeling the carrier aluminum foil from the ultra-thin copper foil.
- a specific embodiment of the present invention provides a method for preparing an easily peelable carrier foil and an application thereof, and Embodiment 3 includes the following steps:
- Step 1 Take an organic film with a thickness of 30 microns
- Step 2 forming a raised structure on the organic film by plasma etching
- Step 3 The surface of the convex structure of the organic film is plated with graphite by magnetron sputtering, and the surface of the graphite (on the side of the convex structure away from the organic film) is smooth and flat;
- Step 4 preparing an ultra-thin copper foil having a thickness of 4 ⁇ m by chemical plating on a smooth and flat graphite surface;
- Step 5 The organic film is completely peeled off from the ultra-thin copper foil by hot pressing on the organic film.
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Abstract
The present invention relates to the technical field of semiconductors, and in particular to an easy-to-peel carrier foil and preparation method therefor, and an application of the easy-to-peel carrier foil in the preparation of an ultrathin copper foil. The easy-to-peel carrier foil comprises a roughened carrier foil (2) and a graphite material (3), the graphite material (3) being adhered onto the surface of the roughened carrier foil (2). The present invention overcomes the technical defect that a carrier foil layer is partially peeled off from an ultrathin copper foil layer or cannot be peeled off from the ultrathin copper foil layer at all due to that an existing peelable layer easily causes unstable peeling strength of the carrier foil at a high temperature.
Description
本发明属于半导体技术领域，尤其涉及一种易剥离载体箔及其制备方法和应用。The invention belongs to the technical field of semiconductors, and in particular relates to an easily peelable carrier foil and a preparation method and application thereof.
近年来，我国电解铜箔业发展迅速，作为印刷电路板(PCB)的主要原材料，电解铜箔的发展一直追随着PCB技术的发展，95％以上用于印制电路板基材的制造，而PCB则随着电子产品的日新月异不断提高，目前电子产品正向低成本、高可靠、高稳定、高功能化方向发展，由此对电解铜箔的性能、品种提出了更新更高的要求，电解铜箔出现了全新的发展趋势，其厚度向薄、超薄方向发展，随着近来电子设备的普遍化、小型化和致密化，印刷线路板的布线图案宽度和间距变得越来越薄，对电解铜箔的要求也越来越高。目前，铜箔越来越薄，则它的制备就更加困难，而且在运输过程中很容易破裂和起皱。In recent years, China's electrolytic copper foil industry has developed rapidly. As the main raw material of printed circuit board (PCB), the development of electrolytic copper foil has been following the development of PCB technology, and more than 95% is used in the manufacture of printed circuit board substrates. PCBs are constantly improving with the rapid development of electronic products. At present, electronic products are developing in the direction of low cost, high reliability, high stability and high functionality. Therefore, the performance and variety of electrolytic copper foils are updated and higher. Copper foil has developed a new trend, and its thickness has been thinner and thinner. With the recent generalization, miniaturization and densification of electronic devices, the width and spacing of printed circuit boards have become thinner and thinner. The requirements for electrolytic copper foil are also increasing. At present, copper foil is getting thinner and thinner, and its preparation is more difficult, and it is easy to crack and wrinkle during transportation.
传统加工工艺对超薄铜箔的生产大多采用具有一定厚度的载体箔作阴极，在其上电沉积铜，在其上电镀超薄铜箔，然后将镀上的超薄铜箔连同阴极的载体箔一同经热压、固化压制在绝缘材料板上，再将用作阴极的载体箔用化学或机械方法剥离除去，载体箔的材料一般为不锈钢，金属铝和金属铜。Conventional processing technology for the production of ultra-thin copper foil mostly uses a carrier foil with a certain thickness as a cathode, on which copper is electrodeposited, an ultra-thin copper foil is plated thereon, and then the ultra-thin copper foil plated together with the carrier of the cathode The foil is pressed together on the insulating material plate by hot pressing and curing, and the carrier foil used as the cathode is peeled off by chemical or mechanical means. The material of the carrier foil is generally stainless steel, metallic aluminum and metallic copper.
一直以来，可剥离型带载体的电解超薄铜箔广泛用来与基材通过热压加工进行层叠，然后将超薄铜箔层与载体箔剥离，作为敷铜层压板使用，这时在载体箔与超薄铜箔的接合界面处存在着剥离不稳定的情况，有的载体超薄铜箔在加工时就剥离，有的在热压加工后还不能完全剥离，或者部分剥离。Conventionally, a peelable type carrier-coated electrolytic ultra-thin copper foil has been widely used for lamination with a substrate by hot press processing, and then the ultra-thin copper foil layer is peeled off from the carrier foil to be used as a copper-clad laminate, in which case the carrier is used. There is a case where the peeling is unstable at the joint interface between the foil and the ultra-thin copper foil, and some of the carrier ultra-thin copper foil is peeled off during processing, and some may not be completely peeled off or partially peeled off after hot press processing.
为了解决这些问题，需要在载体箔和超薄铜箔之间形成一个剥离层，使得载体箔和超薄铜箔之间具有合适的剥离强度，解决载体箔和超薄铜箔之间难剥离的难题。目前，国内外所使用的剥离层主要有：有机层作为剥离层，无机层作为剥离层。有机剥离层使用较多的有机化合物是羧基苯并***(CBTA)、含氮化合物、含硫化合物和羧酸等，可以使用它们中的一种或两种以上的物质。有机剥离层可以通过浸渍或涂覆含有所选的有机化合物的水 溶液非常容易地形成。但是，有机剥离层在高温下剥离困难，使得载体箔的剥离强度不够稳定；无机剥离层为金属基层或合金层，最常用的金属基层是铬基层，合金层一般有Ni-Mo合金、Ni-Co合金、Cr-Co合金、Mo-Co合金等。但是，铬基层在温度超过450℃时剥离强度就不稳定，而且，作为隔离层的金属铬本身有毒，对环境和人体有害，一般不采用。无机剥离层的缺陷在于，由金属基层或合金层形成的剥离层，剥离载体时的剥离强度受到这些金属附着量的影响，而在实际操作中，这些金属附着量不容易控制，而且在高温下，载体箔层、剥离层与超薄铜箔层之间引起相互扩散，产生载体箔层与超薄铜箔层部分剥离或完全不能剥离的现象。In order to solve these problems, it is necessary to form a peeling layer between the carrier foil and the ultra-thin copper foil so as to have a suitable peeling strength between the carrier foil and the ultra-thin copper foil, and to solve the problem that the carrier foil and the ultra-thin copper foil are difficult to peel off. problem. At present, the peeling layer used at home and abroad mainly includes an organic layer as a peeling layer and an inorganic layer as a peeling layer. The organic compound which is used in the organic release layer is carboxybenzotriazole (CBTA), a nitrogen-containing compound, a sulfur-containing compound, a carboxylic acid, etc., and one or two or more of them may be used. The organic release layer can be formed very easily by dipping or coating an aqueous solution containing the selected organic compound. However, the organic peeling layer is difficult to peel at high temperature, so that the peeling strength of the carrier foil is not stable enough; the inorganic peeling layer is a metal base layer or an alloy layer, and the most commonly used metal base layer is a chromium base layer, and the alloy layer generally has a Ni-Mo alloy, Ni- Co alloy, Cr-Co alloy, Mo-Co alloy, and the like. However, when the temperature of the chromium base layer exceeds 450 ° C, the peel strength is unstable, and the metal chromium as the separator is itself toxic, harmful to the environment and the human body, and generally not used. A defect of the inorganic release layer is that the release layer formed of the metal base layer or the alloy layer is affected by the adhesion amount of the metal when the carrier is peeled off, and in actual operation, the adhesion amount of these metals is not easily controlled, and at a high temperature The carrier foil layer, the release layer and the ultra-thin copper foil layer cause mutual diffusion, resulting in a phenomenon in which the carrier foil layer and the ultra-thin copper foil layer are partially peeled off or not peeled at all.
发明内容Summary of the invention
有鉴于此，本发明提供了一种易剥离载体箔及其制备方法和应用，能有效解决现有的剥离层在高温下容易使得载体箔的剥离强度不稳定，产生载体箔层与超薄铜箔层部分剥离或完全不能剥离的技术缺陷。In view of the above, the present invention provides an easy-peeling carrier foil and a preparation method and application thereof, which can effectively solve the problem that the existing peeling layer is easy to make the peeling strength of the carrier foil unstable under high temperature, and the carrier foil layer and the ultra-thin copper are produced. A technical defect in which the foil layer is partially peeled off or not peeled at all.
本发明提供了一种易剥离载体箔，包括：经粗糙化处理的载体箔和石墨类材料，所述石墨类材料附着在所述经粗糙化处理的载体箔的粗糙面。The present invention provides an easily peelable carrier foil comprising: a roughened carrier foil and a graphite-based material adhered to the roughened surface of the roughened carrier foil.
作为优选，所述粗糙化处理具体包括通过化学方法或等离子刻蚀方法在载体箔的表面形成凸起结构。Preferably, the roughening treatment specifically comprises forming a convex structure on the surface of the carrier foil by a chemical method or a plasma etching method.
作为优选，所述石墨类材料具体为石墨或石墨烯。Preferably, the graphite-based material is specifically graphite or graphene.
作为优选，所述石墨类材料附着在所述经粗糙化处理的载体箔的表面具体包括通过化学气相沉积法或磁控溅射法将所述石墨类材料附着在所述经粗糙化处理的载体箔的粗糙面。Preferably, attaching the graphite-based material to the surface of the roughened carrier foil comprises specifically attaching the graphite-based material to the roughened carrier by chemical vapor deposition or magnetron sputtering. The rough side of the foil.
作为优选，所述载体箔具体为金属箔或有机薄膜。Preferably, the carrier foil is in particular a metal foil or an organic film.
作为优选，所述金属箔为铜、铜合金、铝、铝合金或不锈钢中的一种或多种。Preferably, the metal foil is one or more of copper, copper alloy, aluminum, aluminum alloy or stainless steel.
作为优选，所述有机薄膜为PET、PI或PEN。Preferably, the organic film is PET, PI or PEN.
本发明还提供了所述中的应用。The invention also provides the application described.
本发明还提供了一种易剥离载体箔的制备方法，包括以下步骤：The invention also provides a preparation method of an easily peelable carrier foil, comprising the following steps:
步骤一：将载体箔的表面进行粗糙化处理，得到经粗糙化处理的载体箔；Step 1: roughening the surface of the carrier foil to obtain a roughened carrier foil;
步骤二：通过化学气相沉积法或磁控溅射法在经粗糙化处理的载体箔的 粗糙面附着在所述石墨类材料，得到易剥离载体箔。Step 2: adhering to the graphite-based material on the rough surface of the roughened carrier foil by chemical vapor deposition or magnetron sputtering to obtain an easily peelable carrier foil.
本发明提供的所述的易剥离载体箔或所述的易剥离载体箔的制备方法制得的易剥离载体箔在制备超薄铜箔中的应用。The use of the easily peelable carrier foil provided by the present invention or the easy-peeling carrier foil prepared by the method for preparing the easily peelable carrier foil is used for preparing an ultra-thin copper foil.
作为优选，所述应用，包括以下步骤：Preferably, the application comprises the following steps:
步骤1：制备易剥离载体箔；Step 1: preparing an easily peelable carrier foil;
步骤2：在所述易剥离载体箔的石墨类材料的表面电镀铜箔；Step 2: plating a copper foil on the surface of the graphite-based material of the easily peelable carrier foil;
步骤3：通过物理方法将所述易剥离载体箔从所述超薄铜箔上剥离。Step 3: The easily peelable carrier foil is peeled off from the ultra-thin copper foil by a physical method.
具体的，所述步骤3的物理方法为通过热压加工使得所述易剥离载体箔与所述超薄铜箔进行剥离。Specifically, the physical method of the step 3 is that the easily peelable carrier foil is peeled off from the ultra-thin copper foil by hot pressing.
本发明提供的一种易剥离载体箔，经粗糙化处理的载体箔具体作用是粗糙形成凸起结构，该凸起结构与石墨类材料的接触面积更大，能保证石墨类材料与载体箔的结合力大于石墨类材料与超薄铜箔的结合力，由于石墨类材料与载体箔的结合力不大，能够保证运输过程中载体箔的石墨类材料和超薄铜箔层不剥离，而在热压加工后可完全剥离且无杂质残留；利用石墨类材料代替有机剥离层，能解决有机剥离层会有杂质残留在超薄铜箔层上且高温下剥离困难；而金属合金做剥离层时，载体箔层、剥离层与超薄铜箔层之间具有相互扩散的作用，引起载体箔层与超薄铜箔层部分剥离或完全不能剥离。同时，石墨类材料是一种热膨胀性小，具有一定的粘附力的材料，其化学性能稳定且与超薄铜箔的结合力适中，可以有效的充当剥离层。本专利所采用的石墨类材料作为剥离层，在常温下具有一定的粘附力，使得超薄铜箔不会发生脱落；在高温下热膨胀性小，不会产生载体箔层、剥离层与超薄铜箔层之间的金属间相互扩散的问题，不会发生载体箔层与超薄铜箔层部分剥离或完全不能剥离的现象。石墨类材料的化学性能稳定不会与超薄铜箔生成化合物，从而不会造成难剥离的问题；此外，由于石墨的热膨胀性小，在加热加工的过程中不易产生翘曲变型；也同时提高超薄铜箔的成品率，降低生产成本；而且，石墨作为一种常见的材料，资源丰富，价格便宜，有利于减低超薄铜箔的制作成本。The invention provides an easily peelable carrier foil, and the roughened carrier foil has a specific function of rough forming a convex structure, and the contact structure of the convex structure and the graphite material is larger, and the graphite material and the carrier foil can be ensured. The bonding force is greater than the bonding strength between the graphite material and the ultra-thin copper foil. Since the bonding force between the graphite material and the carrier foil is not large, the graphite material of the carrier foil and the ultra-thin copper foil layer are not peeled off during transportation. After hot pressing, it can be completely peeled off without impurities. By using graphite material instead of organic peeling layer, it can solve the problem that impurities in the organic peeling layer remain on the ultra-thin copper foil layer and it is difficult to peel at high temperature. When the metal alloy is used as the peeling layer The carrier foil layer, the release layer and the ultra-thin copper foil layer have an interdiffusion effect, causing the carrier foil layer and the ultra-thin copper foil layer to be partially peeled off or not peeled at all. At the same time, the graphite-based material is a material having small thermal expansion property and a certain adhesion, and its chemical property is stable and moderately bonded to an ultra-thin copper foil, and can effectively serve as a peeling layer. The graphite-based material used in this patent has a certain adhesion at normal temperature as a peeling layer, so that the ultra-thin copper foil does not fall off; the thermal expansion property at a high temperature is small, and the carrier foil layer, the peeling layer and the super layer are not generated. The problem of interdiffusion of metals between the thin copper foil layers does not cause partial peeling or partial peeling of the carrier foil layer and the ultra-thin copper foil layer. The chemical properties of graphite materials are stable and do not form compounds with ultra-thin copper foil, so that it does not cause difficult peeling; in addition, due to the small thermal expansion of graphite, it is not easy to produce warpage and deformation during heating processing; The yield of ultra-thin copper foil reduces the production cost; moreover, graphite is a common material, rich in resources and cheap, which is beneficial to reduce the manufacturing cost of ultra-thin copper foil.
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实 施例或现有技术描述中所需要使用的附图作简单地介绍。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings to be used in the embodiments or the prior art description will be briefly described below.
图1示本发明具体实施方式中的经粗糙化处理的载体箔的结构示意图；1 is a schematic structural view of a roughened carrier foil in a specific embodiment of the present invention;
图2示本发明具体实施方式中的易剥离载体箔的结构示意图；2 is a schematic structural view of an easily peelable carrier foil in a specific embodiment of the present invention;
图3示本发明具体实施方式中的易剥离载体箔与超薄铜箔的结构示意图；3 is a schematic structural view of an easily peelable carrier foil and an ultra-thin copper foil in a specific embodiment of the present invention;
其中，附图标记，凸起结构1，经粗糙化处理的载体箔2，石墨类材料3，铜箔4，石墨类材料的一侧A。Here, the reference numerals, the convex structure 1, the roughened carrier foil 2, the graphite material 3, the copper foil 4, and the side A of the graphite-based material.
本发明提供了一种易剥离载体箔及其制备方法和应用，用于解决现有的剥离层在高温下容易使得载体箔的剥离强度不稳定，产生载体箔层与超薄铜箔层部分剥离或完全不能剥离的技术缺陷。The invention provides an easy-peeling carrier foil and a preparation method and application thereof, which are used for solving the problem that the existing peeling layer is easy to make the peeling strength of the carrier foil unstable at a high temperature, and the carrier foil layer and the ultra-thin copper foil layer are partially peeled off. Or technical defects that cannot be stripped at all.
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are clearly and completely described below. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
请参阅图1至3，本发明提供了一种易剥离载体箔，包括：经粗糙化处理的载体箔2和石墨类材料3，石墨类材料3附着在经粗糙化处理的载体箔2的粗糙面。Referring to Figures 1 to 3, the present invention provides an easily peelable carrier foil comprising: a roughened carrier foil 2 and a graphite-based material 3 attached to the roughened roughened carrier foil 2 surface.
其中，粗糙化处理具体包括通过化学方法或/和等离子刻蚀方法在载体箔的表面形成凸起结构1。Wherein, the roughening treatment specifically includes forming the convex structure 1 on the surface of the carrier foil by a chemical method or/and a plasma etching method.
具体的，化学方法具体为光化学刻蚀法。光化学刻蚀法为通过曝光制版、显影后，将要蚀刻区域的保护膜去除，在蚀刻时接触化学溶液，达到溶解腐蚀的作用，形成凹凸或者镂空成型的效果。Specifically, the chemical method is specifically a photochemical etching method. The photochemical etching method removes the protective film to be etched by exposure, and after developing, contacts the chemical solution during etching to achieve dissolution and corrosion, and forms an effect of unevenness or hollowing.
具体的，等离子刻蚀具体为：利用气压为10～1000帕的特定气体(或混合气体)的辉光放电，产生能与薄膜发生离子化学反应的分子或分子基团，生成的反应产物是挥发性的。它在低气压的真空室中被抽走，从而实现刻蚀。通过选择和控制放电气体的成分，可以得到较好的刻蚀选择性和较高的刻蚀速率。Specifically, the plasma etching is specifically: using a glow discharge of a specific gas (or a mixed gas) having a gas pressure of 10 to 1000 Pa, to generate a molecular or molecular group capable of undergoing an ionic chemical reaction with the film, and the generated reaction product is volatilized. Sexual. It is evacuated in a low pressure vacuum chamber to effect etching. By selecting and controlling the composition of the discharge gas, better etch selectivity and higher etch rate can be obtained.
其中，石墨类材料3具体包括石墨或石墨烯。Among them, the graphite-based material 3 specifically includes graphite or graphene.
其中，石墨类材料3附着在经粗糙化处理的载体箔2的表面具体包括通 过CVD法或磁控溅射法将石墨类材料3附着在经粗糙化处理的载体箔2的粗糙面。Among them, the adhesion of the graphite-based material 3 to the surface of the roughened carrier foil 2 specifically includes attaching the graphite-based material 3 to the rough surface of the roughened carrier foil 2 by a CVD method or a magnetron sputtering method.
其中，载体箔具体包括金属箔或有机薄膜。Wherein, the carrier foil specifically comprises a metal foil or an organic film.
其中，金属箔包括铜、铜合金、铝、铝合金或不锈钢中的一种或多种。Wherein, the metal foil comprises one or more of copper, copper alloy, aluminum, aluminum alloy or stainless steel.
其中，有机薄膜包括PET、PI或PEN。Among them, the organic film includes PET, PI or PEN.
优选的，载体箔2的厚度为18～35μm。Preferably, the carrier foil 2 has a thickness of 18 to 35 μm.
本发明还公开了一种易剥离载体箔的制备方法，包括以下步骤：The invention also discloses a preparation method of an easily peelable carrier foil, comprising the following steps:
步骤一：将载体箔的表面进行粗糙化处理，得到经粗糙化处理的载体箔2；Step 1: roughening the surface of the carrier foil to obtain a roughened carrier foil 2;
步骤二：通过化学气相沉积法或磁控溅射法在经粗糙化处理的载体箔2的粗糙面附着在石墨类材料3，得到易剥离载体箔。Step 2: The graphite material 3 is adhered to the rough surface of the roughened carrier foil 2 by a chemical vapor deposition method or a magnetron sputtering method to obtain an easily peelable carrier foil.
本发明公开的易剥离载体箔或上述易剥离载体箔的制备方法制得的易剥离载体箔在制备超薄铜箔中的应用。The use of the easily peelable carrier foil prepared by the method for preparing the exfoliable carrier foil or the above-mentioned easy-peeling carrier foil disclosed in the present invention for preparing an ultra-thin copper foil.
具体的，上述应用，包括以下步骤：Specifically, the above application includes the following steps:
步骤1：载体箔的表面进行粗糙化处理，得到经粗糙化处理的载体箔2；Step 1: roughening the surface of the carrier foil to obtain a roughened carrier foil 2;
步骤2：在经粗糙化处理的载体箔2的粗糙面附着在石墨类材料3，得到易剥离载体箔；Step 2: attaching the rough surface of the roughened carrier foil 2 to the graphite-based material 3 to obtain an easily peelable carrier foil;
步骤3：在易剥离载体箔的石墨类材料的表面A电镀铜箔4；Step 3: electroplating the copper foil 4 on the surface A of the graphite-based material of the easily peelable carrier foil;
步骤4：通过热压加工将所述易剥离载体箔从所述超薄铜箔上剥离。Step 4: The easily peelable carrier foil is peeled off from the ultra-thin copper foil by hot pressing.
具体的，步骤3的石墨类材料3的表面A的表面光滑平整。Specifically, the surface of the surface A of the graphite-based material 3 of the step 3 is smooth and flat.
具体的，步骤3的铜箔4的厚度为1-9μm。Specifically, the thickness of the copper foil 4 of the step 3 is 1 to 9 μm.
其中，以下实施例的原料均为市售或自制，PET膜为耐高温聚酯薄膜，PI膜为聚酰亚胺薄膜，PEN膜为聚萘二甲酸乙二醇酯膜，CVD法为化学气相淀积。Among them, the raw materials of the following examples are all commercially available or self-made, the PET film is a high temperature resistant polyester film, the PI film is a polyimide film, the PEN film is a polyethylene naphthalate film, and the CVD method is a chemical vapor phase. Deposit.
实施例1Example 1
本发明的具体实施方式提供一种易剥离载体箔的制备方法及其应用，实施例1包括以下步骤：A specific embodiment of the present invention provides a method for preparing an easily peelable carrier foil and an application thereof, and Embodiment 1 includes the following steps:
步骤1：取一块厚度为20微米的载体铜箔；Step 1: Take a carrier copper foil with a thickness of 20 microns;
步骤2：对载体铜箔通过光化学蚀刻形成一层凸起结构；Step 2: forming a raised structure on the carrier copper foil by photochemical etching;
步骤3：对载体铜箔的凸起结构表面通过CVD法电镀石墨，石墨表面(远 离载体铜箔的凸起结构一侧)为光滑平整；Step 3: The surface of the convex structure of the carrier copper foil is plated with graphite by CVD, and the surface of the graphite (on the side of the convex structure away from the carrier copper foil) is smooth and flat;
步骤4：在光滑平整的石墨表面通过化学电镀的方法制备厚度为2微米的超薄铜箔；Step 4: preparing an ultra-thin copper foil having a thickness of 2 μm by chemical plating on a smooth and flat graphite surface;
步骤5：通过热压加工的方式热压在载体铜箔上，将载体铜箔与超薄铜箔完全剥离。Step 5: hot pressing on the carrier copper foil by hot pressing, and completely peeling the carrier copper foil from the ultra-thin copper foil.
具体的，石墨表面(远离载体铜箔的凸起结构一侧)为图3的A侧。Specifically, the graphite surface (on the side of the convex structure away from the carrier copper foil) is the A side of FIG.
实施例2Example 2
本发明的具体实施方式提供一种易剥离载体箔的制备方法及其应用，实施例2包括以下步骤：A specific embodiment of the present invention provides a method for preparing an easily peelable carrier foil and an application thereof, and Embodiment 2 includes the following steps:
步骤1：取一块厚度为25微米的载体铝箔；Step 1: Take a carrier aluminum foil with a thickness of 25 microns;
步骤2：对载体铝箔通过光化学蚀刻形成一层凸起结构；Step 2: forming a raised structure on the carrier aluminum foil by photochemical etching;
步骤3：对载体铝箔的凸起结构表面通过CVD法镀石墨，石墨表面(远离载体铝箔的凸起结构一侧)为光滑平整；Step 3: The surface of the convex structure of the carrier aluminum foil is plated with graphite by CVD, and the surface of the graphite (on the side of the convex structure away from the carrier aluminum foil) is smooth and flat;
步骤4：在光滑平整的石墨表面通过化学电镀的方法制备厚度为3微米的超薄铜箔；Step 4: preparing an ultra-thin copper foil having a thickness of 3 μm by chemical plating on a smooth and flat graphite surface;
步骤5：通过热压加工的方式热压在载体铝箔上，将载体铝箔与超薄铜箔完全剥离。Step 5: hot pressing on the carrier aluminum foil by hot pressing, and completely peeling the carrier aluminum foil from the ultra-thin copper foil.
实施例3Example 3
本发明的具体实施方式提供一种易剥离载体箔的制备方法及其应用，实施例3包括以下步骤：A specific embodiment of the present invention provides a method for preparing an easily peelable carrier foil and an application thereof, and Embodiment 3 includes the following steps:
步骤1：取一块厚度为30微米的有机薄膜；Step 1: Take an organic film with a thickness of 30 microns;
步骤2：对有机薄膜通过等离子刻蚀方法形成一层凸起结构；Step 2: forming a raised structure on the organic film by plasma etching;
步骤3：对有机薄膜的凸起结构表面通过磁控溅射法镀石墨，石墨表面(远离有机薄膜的凸起结构一侧)光滑平整；Step 3: The surface of the convex structure of the organic film is plated with graphite by magnetron sputtering, and the surface of the graphite (on the side of the convex structure away from the organic film) is smooth and flat;
步骤4：在光滑平整的石墨表面通过化学电镀的方法制备厚度为4微米的超薄铜箔；Step 4: preparing an ultra-thin copper foil having a thickness of 4 μm by chemical plating on a smooth and flat graphite surface;
步骤5：通过热压加工的方式热压在有机薄膜上，将有机薄膜与超薄铜箔完全剥离。Step 5: The organic film is completely peeled off from the ultra-thin copper foil by hot pressing on the organic film.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普 通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the present invention. It should be considered as the scope of protection of the present invention.
Claims (10)
- 一种易剥离载体箔，其特征在于，包括：经粗糙化处理的载体箔和石墨类材料，所述石墨类材料附着在所述经粗糙化处理的载体箔的粗糙面。An easily peelable carrier foil comprising: a roughened carrier foil and a graphite-based material attached to a roughened surface of the roughened carrier foil.
- 根据权利要求1所述的易剥离载体箔，其特征在于，所述粗糙化处理具体包括通过化学方法或等离子刻蚀方法在载体箔的表面形成凸起结构。The easily peelable carrier foil according to claim 1, wherein the roughening treatment specifically comprises forming a convex structure on a surface of the carrier foil by a chemical method or a plasma etching method.
- 根据权利要求1所述的易剥离载体箔，其特征在于，所述石墨类材料具体包括石墨或石墨烯。The easily peelable carrier foil according to claim 1, wherein the graphite-based material specifically comprises graphite or graphene.
- 根据权利要求1所述的易剥离载体箔，其特征在于，所述石墨类材料附着在所述经粗糙化处理的载体箔的表面具体包括通过化学气相沉积法或磁控溅射法将所述石墨类材料附着在所述经粗糙化处理的载体箔的粗糙面。The easily peelable carrier foil according to claim 1, wherein the graphite-based material is attached to the surface of the roughened carrier foil, specifically comprising the method by chemical vapor deposition or magnetron sputtering A graphite-based material is attached to the rough surface of the roughened carrier foil.
- 根据权利要求1所述的易剥离载体箔，其特征在于，所述载体箔包括金属箔或有机薄膜。The easily peelable carrier foil according to claim 1, wherein the carrier foil comprises a metal foil or an organic film.
- 根据权利要求5所述的易剥离载体箔，其特征在于，所述金属箔包括铜、铜合金、铝、铝合金或不锈钢中的一种或多种。The easily peelable carrier foil according to claim 5, wherein the metal foil comprises one or more of copper, copper alloy, aluminum, aluminum alloy or stainless steel.
- 根据权利要求5所述的易剥离载体箔，其特征在于，所述有机薄膜包括PET、PI或PEN。The easily peelable carrier foil according to claim 5, wherein the organic film comprises PET, PI or PEN.
- 一种易剥离载体箔的制备方法，其特征在于，包括以下步骤：A method for preparing an easily peelable carrier foil, comprising the steps of:步骤一：将载体箔的表面进行粗糙化处理，得到经粗糙化处理的载体箔；Step 1: roughening the surface of the carrier foil to obtain a roughened carrier foil;步骤二：通过化学气相沉积法或磁控溅射法在经粗糙化处理的载体箔的粗糙面附着所述石墨类材料，得到易剥离载体箔。Step 2: attaching the graphite-based material to the rough surface of the roughened carrier foil by chemical vapor deposition or magnetron sputtering to obtain an easily peelable carrier foil.
- 权利要求1至7任意一项所述的易剥离载体箔或权利要求8所述的易剥离载体箔的制备方法制得的易剥离载体箔在制备超薄铜箔中的应用。Use of the easily peelable carrier foil according to any one of claims 1 to 7 or the easily peelable carrier foil prepared by the method for producing an easily peelable carrier foil according to claim 8 for the preparation of an ultra-thin copper foil.
- 根据权利要求9所述的应用，其特征在于，包括以下步骤：The application according to claim 9, comprising the steps of:步骤1：制备易剥离载体箔；Step 1: preparing an easily peelable carrier foil;步骤2：在所述易剥离载体箔的石墨类材料的表面电镀超薄铜箔；Step 2: plating an ultra-thin copper foil on the surface of the graphite-based material of the easily peelable carrier foil;步骤3：通过物理方法将所述易剥离载体箔从所述超薄铜箔上剥离。Step 3: The easily peelable carrier foil is peeled off from the ultra-thin copper foil by a physical method.
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|---|---|---|---|---|
| CN108541144A (en) * | 2018-04-17 | 2018-09-14 | 广东工业大学 | A kind of easily peelable carrier foils and its preparation method and application |
| CN108948399A (en) * | 2018-09-29 | 2018-12-07 | 江苏墨泰新材料有限公司 | polymer-graphite composite membrane and its preparation method and application |
| CN110798986A (en) * | 2018-12-10 | 2020-02-14 | 广州方邦电子股份有限公司 | Metal foil with carrier |
| CN115058711B (en) * | 2022-06-17 | 2022-12-27 | 山东大学 | Preparation method of easily-stripped ultrathin carrier copper foil |
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| JP2007307767A (en) * | 2006-05-17 | 2007-11-29 | Mitsui Mining & Smelting Co Ltd | Copper foil with carrier foil, its manufacturing method, surface-treated copper foil with carrier foil and copper clad laminated sheet using it |
| CN103430642A (en) * | 2011-03-30 | 2013-12-04 | 三井金属矿业株式会社 | Multilayer printed wiring board manufacturing method, and multilayer printed wiring board obtained by said manufacturing method |
| CN108541144A (en) * | 2018-04-17 | 2018-09-14 | 广东工业大学 | A kind of easily peelable carrier foils and its preparation method and application |
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| JPH0818401B2 (en) * | 1989-05-17 | 1996-02-28 | 福田金属箔粉工業株式会社 | Composite foil and its manufacturing method |
| JP2001068804A (en) * | 1999-08-31 | 2001-03-16 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil with carrier foil and its manufacture, and copper plated laminate provided therewith |
| DE102015112649B4 (en) * | 2015-07-31 | 2021-02-04 | Infineon Technologies Ag | METHOD OF FORMING A SEMICONDUCTOR COMPONENT AND A SEMICONDUCTOR COMPONENT |
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- 2018-04-17 CN CN201810346597.3A patent/CN108541144A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007307767A (en) * | 2006-05-17 | 2007-11-29 | Mitsui Mining & Smelting Co Ltd | Copper foil with carrier foil, its manufacturing method, surface-treated copper foil with carrier foil and copper clad laminated sheet using it |
| CN103430642A (en) * | 2011-03-30 | 2013-12-04 | 三井金属矿业株式会社 | Multilayer printed wiring board manufacturing method, and multilayer printed wiring board obtained by said manufacturing method |
| CN108541144A (en) * | 2018-04-17 | 2018-09-14 | 广东工业大学 | A kind of easily peelable carrier foils and its preparation method and application |
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