Laminate, laminate with member for electronic device, method for manufacturing electronic device

Abstract

The present invention provides: a laminated body with which a substrate having a member for an electronic device can be peeled off by laser peeling after the member for the electronic device is formed on the substrate by a method involving heating treatment (e.g., 200°C or higher) and which has a seed layer for performing a plating process on the substrate that has the member for the electronic device and that has been peeled off; a laminated body with a member for an electronic device; and a method for producing an electronic device. A laminated body according to the present invention has a supporting base material, an adhesive layer, a metal layer, and a substrate in this order, and the metal layer contains at least one metal selected from the group consisting of copper, titanium, palladium, gold, nickel, tungsten, and molybdenum.

Description

Technical Field

[0001] The present invention relates to a laminate, a laminate with an electronic device member, and a method for manufacturing an electronic device.

Background Art

[0002] The thinning and weight reduction of electronic devices such as solar cells (PV), liquid crystal panels (LCD), organic EL panels (OLED), and receiving sensor panels that sense electromagnetic waves, X-rays, ultraviolet rays, visible light, infrared rays, etc. are progressing. Along with this, the thinning of substrates such as glass substrates used in electronic devices is also progressing. If the strength of the substrate is insufficient due to thinning, the handleability of the substrate decreases, and problems may occur in a process of forming an electronic device member on the substrate (member forming process) and the like.

[0003] Recently, in order to address the above problems, a method has been proposed in which a glass laminate obtained by laminating a glass substrate and a reinforcing plate is prepared, an electronic device member such as a display device is formed on the glass substrate of the glass laminate, and then the reinforcing plate is separated from the glass substrate (see, for example, Patent Document 1). The reinforcing plate has a support base material and a silicone resin layer fixed on the support base material, and in the glass laminate, the silicone resin layer and the glass substrate are adhered so as to be peelable.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In Patent Document 1, when peeling the glass substrate on which the electronic device member is disposed from the reinforcing plate, mainly mechanical peeling is performed in which a physical force is applied to the glass substrate to peel it from the reinforcing plate. On the other hand, in recent years, with the increasing functionality and complexity of components for electronic devices, it has become necessary to handle components for electronic devices even more carefully. When mechanical peeling as described in Patent Document 1 is performed, there is a risk of adversely affecting components for electronic devices.

[0006] As a method different from the above-described mechanical peeling, there is laser peeling in which a laser is irradiated onto an object to be processed to cause peeling between two members. Laser peeling is preferable because it can suppress the application of physical force to components for electronic devices. Usually, heat treatment is often involved when forming components for electronic devices on a substrate. Therefore, it is desirable that after forming a component for an electronic device on a substrate by a method involving heat treatment, the substrate having the component for the electronic device can be peeled off from the obtained laminate by laser peeling. In addition, if it is possible to directly perform a plating process on the substrate having the peeled component for the electronic device, it is desirable because a new circuit can be efficiently formed on the substrate.

[0007] In view of the above circumstances, an object of the present invention is to provide a laminate in which, after forming a component for an electronic device on a substrate by a method involving heat treatment (for example, 200°C or higher), the substrate having the component for the electronic device can be peeled off by laser peeling, and the substrate having the peeled component for the electronic device has a seed layer for performing a plating process. Another object of the present invention is to provide a laminate with a component for an electronic device and a method for manufacturing an electronic device.

Means for Solving the Problems

[0008] As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the following configuration.

[0009] (1) A laminate having a support substrate, an adhesion layer, a metal layer, and a substrate in this order, wherein the metal layer contains at least one metal selected from the group consisting of copper, titanium, palladium, gold, nickel, tungsten, and molybdenum. (2) The laminate according to (1), wherein the metal layer contains at least one metal selected from the group consisting of copper, titanium, palladium, gold, and nickel. (3) The metal layer has a first metal layer and a second metal layer disposed on the first metal layer. The laminate according to (1) or (2), wherein the type of metal contained in the first metal layer is different from the type of metal contained in the second metal layer. (4) The first metal layer is disposed closer to the substrate side than the second metal layer. The laminate according to (3), wherein the first metal layer contains titanium. (5) The laminate according to (4), wherein the second metal layer contains copper. (6) The metal layer has a first through hole extending in the thickness direction. The substrate has a second through hole extending in the thickness direction. The laminate according to any one of (1) to (5), wherein the first through hole and the second through hole communicate with each other. (7) The laminate according to (6), further comprising a metal coating portion made of metal that covers at least a part of the inner wall surface of the second through hole. (8) The laminate according to any one of (1) to (7), wherein the adhesion layer is a silicone resin layer. (9) The laminate according to any one of (1) to (8), wherein the substrate is a glass substrate. (10) The laminate according to any one of (1) to (9), wherein the support substrate is a glass substrate. (11) A laminate with an electronic device member, comprising the laminate according to any one of (1) to (10) and an electronic device member disposed on the substrate in the laminate. The laminate with an electronic device member. (12) A member forming step of forming an electronic device member on the surface of the substrate of the laminate according to any one of (1) to (10) to obtain a laminate with an electronic device member, and a separation step of irradiating a laser from the support substrate side of the laminate with an electronic device member to peel off the support substrate and the adhesion layer from the laminate with an electronic device member to obtain an electronic device having the electronic device member, the substrate, and the metal layer. A method for manufacturing an electronic device. The manufacturing method of the electronic device includes a member forming step of forming an electronic device member on the surface of the substrate of the laminate according to any one of (1) to (10) to obtain a laminate with an electronic device member, and a separation step of irradiating a laser from the support substrate side of the laminate with an electronic device member to peel off the support substrate and the adhesion layer from the laminate with an electronic device member to obtain an electronic device having the electronic device member, the substrate, and the metal layer.

Advantages of the Invention

[0010] According to the present invention, in view of the above circumstances, after forming a member for an electronic device on a substrate by a method involving heat treatment, the substrate having the member for the electronic device can be peeled off by laser peeling, and a laminate having a seed layer for subjecting the peeled substrate having the member for the electronic device to a plating treatment can be provided. According to the present invention, a laminate with a member for an electronic device and a method for manufacturing an electronic device can be provided.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying Out the Invention

[0012] Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following embodiments are exemplary for explaining the present invention, and the present invention is not limited to the embodiments shown below. Various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention. A numerical range represented by “~” means a range including the numerical values described before and after “~” as the lower limit value and the upper limit value.

[0013] As a characteristic point of the laminate of the present invention, the use of a metal layer containing a predetermined metal can be mentioned. By adopting the above configuration, it has been found that a desired effect can be obtained. First, when the laminate of the present invention is irradiated with a laser, peeling occurs between the adhesion layer and the metal layer, and so-called laser peeling becomes possible. Further, the substrate having the peeled member for an electronic device has a metal layer, and this metal layer can be used as a seed layer during plating treatment.

[0014] <First Embodiment of the Laminate> FIG. 1 is a cross-sectional view schematically showing a first embodiment of the laminate of the present invention. The laminate 10A includes a support substrate 12, an adhesion layer 14, a metal layer 16A, and a substrate 18A in this order.

[0015] As will be described later, after a member for an electronic device is formed on the substrate 18A of the laminate 10A by a method involving heat treatment, when the laminate 10A having the member for an electronic device is irradiated with a laser, peeling occurs at the interface between the adhesion layer 14 and the metal layer 16A. The two-layer portion composed of the support substrate 12 and the adhesion layer 14 has a function of reinforcing the substrate 18A. Note that the two-layer portion composed of the support substrate 12 and the adhesion layer 14, which is manufactured in advance for the production of the laminate 10A, is also referred to as a support substrate with an adhesion layer 20.

[0016] As described above, in this laminate 10A, the support substrate with an adhesion layer 20 is separated. The separated support substrate with an adhesion layer 20 can be laminated with a laminate substrate having a new metal layer 16A and a substrate 18A and reused as a new laminate 10A.

[0017] Hereinafter, each layer constituting the laminate 10A will be described in detail, and then the manufacturing method of the laminate 10A will be described in detail.

[0018] (Support Substrate) The support substrate 12 is a member that supports and reinforces the substrate 18A. Examples of the support substrate 12 include a glass substrate, a plastic plate, and a metal plate (e.g., SUS plate). Among them, a glass substrate is preferred.

[0019] As the type of glass, alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high-silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferred. As the oxide-based glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide conversion is preferred. More specifically, as the glass substrate, a glass substrate made of alkali-free borosilicate glass (trade name "AN100" manufactured by AGC Inc.) can be mentioned. The manufacturing method of the glass substrate is usually obtained by melting glass raw materials and forming the molten glass into a plate shape. Such a forming method may be a general one, and examples include the float method, the fusion method, and the slot down draw method.

[0020] The shape (shape of the main surface) of the support substrate 12 is not particularly limited, but a rectangular shape or a circular shape is preferred.

[0021] The thickness of the support substrate 12 may be thicker or thinner than the substrate 18A. From the viewpoint of the handleability of the laminate 10A, the thickness of the support substrate 12 is preferably thicker than the substrate 18A.

[0022] The support substrate 12 is preferably not flexible. Therefore, the thickness of the support substrate 12 is preferably 0.3 mm or more, and more preferably 0.5 mm or more. On the other hand, the thickness of the support substrate 12 is preferably 2.0 mm or less, and more preferably 1.0 mm or less.

[0023] (Adhesion layer) The adhesion layer 14 is a layer that adheres to the metal layer 16A in order to prevent the displacement of the metal layer 16A and the substrate 18A until laser peeling is performed. As described later, peeling occurs between the adhesion layer 14 and the metal layer 16A by laser irradiation.

[0024] The adhesion layer 14 may be an organic layer or an inorganic layer. Examples of the material of the organic layer include acrylic resin, polyolefin resin, polyurethane resin, polyimide resin, silicone resin, polyimide silicone resin, and fluororesin. Also, the adhesion layer 14 can be formed by mixing several types of resins. Examples of the material of the inorganic layer include oxides, nitrides, oxynitrides, carbides, carbonitrides, silicides, and fluorides. Examples of the oxides (preferably metal oxides), nitrides (preferably metal nitrides), and oxynitrides (preferably metal oxynitrides) include oxides, nitrides, and oxynitrides of one or more elements selected from the group consisting of Si, Hf, Zr, Ta, Ti, Y, Nb, Na, Co, Al, Zn, Pb, Mg, Bi, La, Ce, Pr, Sm, Eu, Gd, Dy, Er, Sr, Sn, In, and Ba. Examples of the carbides (preferably metal carbides) and carbonitrides (preferably metal carbonitrides) include carbides, carbonitrides, and carbon oxides of one or more elements selected from the group consisting of Ti, W, Si, Zr, and Nb. Examples of the silicides (preferably metal silicides) include silicides of one or more elements selected from the group consisting of Mo, W, and Cr. Examples of the fluorides (preferably metal fluorides) include fluorides of one or more elements selected from the group consisting of Mg, Y, La, and Ba.

[0025] The adhesion layer 14 may be a plasma polymerized film. When the adhesion layer 14 is a plasma polymerized film, examples of the material for forming the plasma polymerized film include fluorocarbon monomers such as CF4, CHF3, C2H6, C3H6, C2H2, CH3F, C4H8, hydrocarbon monomers such as methane, ethane, propane, ethylene, propylene, acetylene, benzene, toluene, hydrogen, and SF6.

[0026] Among these, from the viewpoints of heat resistance and peelability, as the material of the adhesion layer 14, a silicone resin or a polyimide silicone resin is preferable, a silicone resin is more preferable, and a silicone resin formed from an addition reaction type silicone or a condensation reaction type silicone is even more preferable. That is, the adhesion layer 14 is preferably a silicone resin layer.

[0027] Hereinafter, an embodiment in which the adhesion layer 14 is a silicone resin layer will be described in detail. The silicone resin constituting the silicone resin layer is a resin containing a predetermined organosiloxy unit and is usually obtained by curing a curable silicone. The curable silicone is classified into an addition reaction type silicone, a condensation reaction type silicone, an ultraviolet curable type silicone, and an electron beam curable type silicone according to its curing mechanism, and any of them can be used. Among these, an addition reaction type silicone or a condensation reaction type silicone is preferable.

[0028] The adhesion layer 14 is preferably formed using a curable composition containing a curable silicone. In addition to the curable silicone, the curable composition may contain a solvent, a platinum catalyst (when an addition reaction type silicone is used as the curable silicone), a leveling agent, a metal compound, and the like. Examples of the metal element contained in the metal compound include a 3d transition metal, a 4d transition metal, a lanthanoid series metal, bismuth, aluminum, and tin. The content of the metal compound is not particularly limited and is appropriately adjusted.

[0029] The adhesion layer 14 is preferably bonded to the support substrate 12 with a strong bonding force. As a method for enhancing the adhesion between the two, for example, when the adhesion layer 14 is a silicone resin layer, the silicone resin layer is formed on the surface of the support substrate 12 (more specifically, a curable silicone (organopolysiloxane) capable of forming a predetermined silicone resin is cured on the support substrate 12), whereby the silicone resin in the silicone resin layer is adhered to the surface of the support substrate 12, and a high bonding force can be obtained. Further, a treatment for generating a strong bonding force between the surface of the support substrate 12 and the silicone resin layer (for example, a treatment using a coupling agent) can be performed to enhance the bonding force between the surface of the support substrate 12 and the silicone resin layer.

[0030] The thickness of the adhesion layer 14 is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. On the other hand, the thickness of the adhesion layer 14 is preferably more than 1 μm, and more preferably 4 μm or more. The above thickness is obtained by measuring the thickness of the adhesion layer 14 at any 5 or more positions with a contact type film thickness measuring device and calculating their arithmetic mean.

[0031] (Metal layer) The metal layer 16A is in contact with the adhesion layer 14 and is peeled off from above the adhesion layer 14 together with the substrate 18A after laser irradiation. The metal layer 16A then functions as a seed layer for the plating process.

[0032] The metal layer 16A contains at least one metal selected from the group consisting of copper, titanium, palladium, gold, nickel, tungsten, and molybdenum. Among them, from the viewpoint of good peelability during laser peeling, the metal layer 16A preferably contains at least one metal selected from the group consisting of copper, titanium, palladium, gold, and nickel. The metal layer 16A may contain only one kind of metal or may contain a plurality of kinds of metals.

[0033] The metal layer 16A may have a single-layer structure or a multi-layer structure. When the metal layer 16A has a single-layer structure, after peeling off the substrate having the metal layer 16A by laser lift-off, the metal layer 16A preferably contains at least one metal selected from the group consisting of titanium, palladium, gold, nickel, tungsten, and molybdenum in terms of better adhesion between the metal layer 16A and the substrate 18A.

[0034] When the metal layer 16A has a multilayer structure, the metal layer 16 may have a structure in which a plurality of layers each containing different types of metals are laminated. For example, when the metal layer 16A has a two-layer structure, the metal layer 16A has a first metal layer and a second metal layer disposed on the first metal layer, and the type of metal contained in the first metal layer is different from the type of metal contained in the second metal layer. Although the form in which the metal layer 16A has a two-layer structure has been described in detail above, the metal layer 16A may have a laminated structure of three or more layers.

[0035] When the metal layer 16A has a multilayer structure, after forming a member for an electronic device on the substrate 18A by a method involving heat treatment, the metal layer 16A has the first metal layer and the second metal layer disposed on the first metal layer, and the first metal layer is disposed closer to the substrate 18A side than the second metal layer, and the first metal layer preferably contains titanium in terms of better adhesion between the metal layer 16A and the substrate 18A. In addition, in this form, the second metal layer preferably contains copper.

[0036] The thickness of the metal layer 16A is not particularly limited, and is preferably 5 to 1000 nm, more preferably 10 to 500 nm in terms of better adhesion between the metal layer 16A and the substrate 18A after peeling off the substrate having the metal layer 16A by laser lift-off. When the metal layer 16A has a two-layer structure having a first metal layer and a second metal layer, and the first metal layer is disposed closer to the substrate 18A side than the second metal layer, the thickness of the first metal layer is preferably 5 to 300 nm, more preferably 10 to 200 nm, and the thickness of the second metal layer is preferably 5 to 600 nm, more preferably 10 to 400 nm.

[0037] (Substrate) The substrate 18A is a member for forming device members thereon. The type of the substrate 18A is not particularly limited, and examples thereof include a glass substrate, a plastic plate, and a metal plate (e.g., SUS plate). Among them, a glass substrate is preferable. Specific examples of the glass substrate include those described for the support substrate 12 above.

[0038] From the viewpoints of thinning and / or weight reduction, the thickness of the substrate 18A is preferably 0.5 mm or less, more preferably 0.4 mm or less, still more preferably 0.2 mm or less, and particularly preferably 0.10 mm or less. When the thickness is 0.5 mm or less, it is possible to impart good flexibility to the substrate 18A. When the thickness is 0.2 mm or less, it is possible to wind the substrate 18A into a roll shape. Also, from the viewpoint of easy handling of the substrate 18A, the thickness of the substrate 18A is preferably 0.03 mm or more.

[0039] Note that the substrate 18A may be composed of two or more layers. In this case, the materials for forming each layer may be the same or different.

[0040] <Manufacturing method of the laminate> The manufacturing method of the laminate 10A is not particularly limited, and known methods can be mentioned. Among them, from the viewpoint of more excellent productivity, a contact layer forming step of forming a contact layer 14 on the support substrate 12 to obtain a support substrate with a contact layer, a metal layer forming step of forming a metal layer 16A on the substrate 18A to obtain a substrate with a metal layer, and a laminating step of laminating the support substrate with a contact layer and the substrate with a metal layer so that the contact layer 14 and the metal layer 16A are in contact with each other to obtain the laminate 10A are preferably included. Hereinafter, the contact layer forming step, the metal layer forming step, and the laminating step will be described in detail.

[0041] (Contact layer forming step) The adhesion layer forming step is a step of forming an adhesion layer 14 on the support substrate 12 to obtain a support substrate with an adhesion layer. The method of forming the adhesion layer 14 is not particularly limited, and a known method can be adopted, which varies depending on the type of material constituting the adhesion layer 14. For example, when the adhesion layer 14 is an organic layer, as a method of producing the organic layer, for example, a method of applying a curable resin composition containing a curable resin on the support substrate 12 and curing the formed curable resin composition layer to form an adhesion layer 14 fixed on the support substrate 12 (coating method), or a method of fixing a film-like adhesion layer 14 on the surface of the support substrate 12 (attachment method) can be mentioned. Among them, the coating method is preferable in that the adhesion strength of the adhesion layer 14 to the support substrate 12 is more excellent. In the coating method, as a method of forming a curable resin composition layer on the surface of the support substrate 12, for example, a method of coating the curable resin composition on the surface of the support substrate 12 can be mentioned. As the coating method, for example, spray coating method, die coating method, spin coating method, dip coating method, roll coating method, bar coating method, screen printing method, gravure coating method can be mentioned. The curing method is not particularly limited, and the optimum curing conditions are selected depending on the resin used. Usually, heat treatment is adopted as the curing method.

[0042] In addition to the above, an organic layer may be produced by a known method. For example, the method of producing an adhesion layer containing a fluororesin is not particularly limited, and a method of producing an adhesion layer using a composition containing a fluororesin, or a method of producing an adhesion layer on the surface of an object by irradiating plasma using a fluorine-based gas can be mentioned.

[0043] Also, when the adhesion layer 14 is an inorganic layer, as a method of manufacturing the inorganic layer, a known method can be adopted. For example, a method of providing an inorganic layer composed of a predetermined component on the support substrate 12 by vapor deposition method, sputtering method, CVD method can be mentioned. As a method for producing an inorganic layer made of a carbide (carbon material), for example, there is a method in which a resin composition containing a resin component such as a phenol resin is applied onto a support substrate 12 and then sintered and carbonized. The manufacturing conditions for various methods are appropriately selected as optimal conditions according to the materials used.

[0044] (Metal layer formation step) The metal layer formation step is a step of forming a metal layer 16A on a substrate 18A to obtain a substrate with a metal layer. The method for forming the metal layer 16A is not particularly limited, and a known method can be adopted. For example, there is a method of providing a metal layer 16A composed of a predetermined component on the substrate 18A by vapor deposition, sputtering, or CVD method.

[0045] (Lamination step) The lamination step is a step of laminating the support substrate with an adhesion layer and the substrate with a metal layer so that the adhesion layer 14 of the support substrate with an adhesion layer obtained in the above adhesion layer formation step and the metal layer 16A of the substrate with a metal layer obtained in the above metal layer formation step are in contact with each other, to obtain a laminate 10A.

[0046] The method for laminating the support substrate with an adhesion layer and the substrate with a metal layer is not particularly limited, and a known method can be adopted. For example, there is a method of overlapping the support substrate with an adhesion layer and the substrate with a metal layer in an atmospheric pressure environment. Incidentally, if necessary, after overlapping the support substrate with an adhesion layer and the substrate with a metal layer, the support substrate with an adhesion layer and the substrate with a metal layer may be pressure-bonded using a roll or a press. Pressure-bonding with a roll or a press is preferable because bubbles mixed between the adhesion layer 14 and the metal layer 16 can be relatively easily removed.

[0047] Pressure-bonding by a vacuum lamination method or a vacuum press method is more preferable because it can suppress the mixing of bubbles and ensure good adhesion. By pressure-bonding under vacuum, even if minute bubbles remain, the bubbles do not grow due to heating, and there is also an advantage that it is less likely to lead to distortion defects. When laminating a support substrate with an adhesion layer and a substrate with a metal layer, it is preferable to thoroughly clean the surface of the adhesion layer 14 and the surface of the metal layer 16A and perform the lamination in an environment with a high degree of cleanliness.

[0048] In addition, after laminating the support substrate with the adhesion layer and the substrate with the metal layer, a pre-annealing treatment (heat treatment) may be performed as necessary. By performing this pre-annealing treatment, the adhesion between the support substrate with the adhesion layer and the substrate with the metal layer is improved.

[0049] <Second Embodiment of the Laminate> FIG. 2 is a cross-sectional view schematically showing a second embodiment of the laminate of the present invention. FIG. 3 is a top view of the laminate shown in FIG. 2. Note that FIG. 2 corresponds to a cross-sectional view taken along line A-A in FIG. 3. The laminate 10B includes a support substrate 12, an adhesion layer 14, a metal layer 16B, and a substrate 18B in this order. In the laminate 10B of the second embodiment, the metal layer 16B and the substrate 18B have the same configuration as the laminate 10A of the first embodiment described above, except that they each have a through hole. For the same components in the laminate 10B and the laminate 10A, the same reference numerals are given and the description thereof is omitted.

[0050] The metal layer 16B has a plurality of first through holes 22 extending along the thickness direction of the metal layer 16B. In addition, the substrate 18B has a plurality of second through holes 24 extending along the thickness direction of the substrate 18B. The first through holes 22 and the second through holes 24 communicate with each other. Note that the boundary between the first through holes 22 and the second through holes 24 is located at the interface in the thickness direction between the metal layer 16B and the substrate 18B. When the substrate in the laminate has a through hole as described above, conduction between electronic devices arranged on both sides of the substrate can be achieved by filling the through hole with a conductor (for example, metal). Note that, as described later, an example of a method for filling the through hole with a conductor is plating treatment.

[0051] The diameter of the opening of the first through hole 22 is not particularly limited, but from the viewpoint of facilitating filling of metal into the first through hole 22, 5 to 500 μm is preferable, and 10 to 200 μm is more preferable. When the shape of the opening of the first through hole is not circular, the major axis is taken as the above diameter. The diameter of the opening of the second through hole 24 is not particularly limited, but from the viewpoint of facilitating filling of metal into the second through hole 24, 10 to 500 μm is preferable, and 15 to 200 μm is more preferable. When the shape of the opening of the second through hole is not circular, the major axis is taken as the above diameter.

[0052] The number of the first through holes 22 and the second through holes 24 may be one or a plurality respectively. When a plurality of the first through holes 22 and the second through holes 24 are provided, an optimum distance in the in-plane direction between the through holes (for example, it may be 20 to 400 μm) is selected according to the application to be used.

[0053] In FIG. 2, the openings of the first through hole 22 and the second through hole 24 are of the same size, but the present invention is not limited to this form, and the sizes of the two may be different.

[0054] The manufacturing method of the laminate 10B shown in FIG. 2 is not particularly limited. After performing the above-described metal layer forming step, a through hole forming step of providing through holes penetrating the substrate and the metal layer respectively is performed, and then, using the substrate with a metal layer having the obtained through holes, the above-described lamination step is performed.

[0055] As a modification of the second embodiment, the form shown in FIG. 4 can be cited. The laminate 10C shown in FIG. 4 has a support substrate 12, an adhesion layer 14, a metal layer 16C, and a substrate 18C in this order, and the metal layer 16C and the substrate 18C each have a first through hole 22 and a second through hole 24. The laminate 10C further has a metal coating portion 26 made of metal that covers at least a part of the inner wall surface of the second through hole 24 of the substrate 18C. The metal coating portion 26 corresponds to a portion that covers at least a part of the inner wall surface of the second through hole 24 on the substrate 18C side from the interface in the thickness direction between the metal layer 16C and the substrate 18C.

[0056] Since the laminate 10C has the metal coating portion 26, the peelability between the adhesion layer 14 and the metal layer 16C is improved during laser lift-off. Although the details of the reason for the improvement of the peelability are unknown, when the metal layer 16C has the first through hole 22 and the substrate 18C has the second through hole 24, the adhesion layer 14 may reach the inner wall surface of the second through hole 24 of the substrate 18C through the first through hole 22. In particular, when the adhesion layer 14 is easily plastically deformed like a resin layer (for example, a silicone resin layer), such a phenomenon is likely to occur. When a part of the adhesion layer 14 reaches and contacts the inner wall surface of the second through hole 24 of the substrate 18C, it may affect the peelability of the substrate with the metal layer from the adhesion layer 14. On the other hand, when the metal coating portion 26 is provided, it is possible to prevent the adhesion layer 14 from directly contacting the inner wall surface of the second through hole 24 of the substrate 18C, and it is possible to suppress peeling failure of the substrate with the metal layer during laser lift-off.

[0057] In the laminate 10C shown in FIG. 4, the metal coating portion 26 and the metal layer 16C are integrated and continuous, but at least a part of the metal coating portion 26 may be separated from the metal layer 16C. In the laminate 10C shown in FIG. 4, the metal coating portion 26 is provided so as to cover the entire circumference of the inner wall surface on the metal layer 16C side of the second through hole 24 of the substrate 18C. However, the present invention is not limited to this form, and it may be provided on a part of the inner wall surface of the second through hole 24.

[0058] As shown in FIG. 4, the metal coating portion 26 is preferably provided so as to extend from the interface in the thickness direction between the metal layer 16C and the substrate 18C toward the substrate 18C side.

[0059] The type of metal constituting the metal coating portion 26 is not particularly limited, but at least one metal selected from the group consisting of copper, titanium, palladium, gold, nickel, tungsten, and molybdenum, which is the metal constituting the metal layer 16C, is preferable. The type of metal constituting the metal coating portion 26 may be the same as or different from the type of metal constituting the metal layer 16C, but from the viewpoint of productivity, it is preferably the same.

[0060] The method for manufacturing the laminate 10C shown in FIG. 4 is not particularly limited. For example, a metal layer - attached substrate composed of the metal layer 16C and the substrate 18C can be formed by depositing a metal on one surface of a substrate having a through - hole extending along the thickness direction by a vapor deposition method, a sputtering method, or a CVD method, and a method of performing the above - described lamination process using the obtained metal layer - attached substrate can be mentioned.

[0061] <Applications of the laminate> The laminate (the laminates of the first embodiment and the second embodiment described above) can be used for various applications. For example, applications for manufacturing electronic components such as a panel for a display device, PV, a thin - film secondary battery, a semiconductor wafer with a circuit formed on its surface, and a reception sensor panel can be mentioned. In these applications, the laminate may be exposed to high - temperature conditions (for example, 450°C or higher) for a certain period (for example, 20 minutes or more) in an air atmosphere. The panel for a display device includes an LCD, an OLED, an electronic paper, a plasma display panel, a field emission panel, a quantum dot LED panel, a micro - LED display panel, a MEMS shutter panel, and the like. The reception sensor panel includes an electromagnetic wave reception sensor panel, an X - ray light - receiving sensor panel, an ultraviolet light - receiving sensor panel, a visible light - receiving sensor panel, an infrared light - receiving sensor panel, and the like. The substrate used for the reception sensor panel may be reinforced by a reinforcing sheet such as resin.

[0062] <Method for manufacturing an electronic device> An electronic device including a member for an electronic device described later is manufactured using the laminate. A method for manufacturing an electronic device, for example, as shown in FIGS. 5 and 6, forms an electronic device member 28 on a substrate 18A of a laminate 10A (on the surface of the substrate 18A opposite to the metal layer 16A side) to obtain a laminate 30 with an electronic device member, and irradiates a laser from the support substrate 12 side of the laminate 30 with an electronic device member to separate the support substrate 12 and the adhesion layer 14 from the laminate 30 with an electronic device member, obtaining an electronic device 32 having the electronic device member 28, the substrate 18A, and the metal layer 16A. In the above description, as a representative example of the laminate, the laminate 10A described in the first embodiment is taken as an example. However, an electronic device can be manufactured by the same procedure using the laminate 10B and the laminate 10C described in the second embodiment.

[0063] Hereinafter, the step of forming the electronic device member 28 is referred to as the "member forming step", and the step of separating into the electronic device 32 and the support substrate 20 with an adhesion layer is referred to as the "separation step". The materials and procedures used in each step are described in detail below.

[0064] (Member Forming Step) The member forming step is a step of forming an electronic device member on the substrate 18A of the laminate 10A. More specifically, as shown in FIG. 5, an electronic device member 28 is formed on the substrate 18A (on the surface of the substrate 18A opposite to the metal layer 16A side) to obtain a laminate 30 with an electronic device member. First, the electronic device member 28 used in this step is described in detail, and then the procedure of the subsequent steps is described in detail.

[0065] (Electronic Device Member) The member 28 for an electronic device is a member that constitutes at least a part of the electronic device formed on the substrate 18A of the laminate 10A. More specifically, examples of the member 28 for an electronic device include members used for a panel for a display device, a solar cell, a thin-film secondary battery, or an electronic component such as a semiconductor wafer having a circuit formed on its surface, a receiving sensor panel, etc. (for example, a member for a display device such as a thin-film transistor, a member for a solar cell, a member for a thin-film secondary battery, a circuit for an electronic component, a member for a receiving sensor). For example, the member for a solar cell described in paragraph

[0192] of U.S. Patent Application Publication No. 2018 / 0178492, the member for a thin-film secondary battery described in paragraph

[0193] , and the circuit for an electronic component described in paragraph

[0194] can be mentioned.

[0066] (Procedure of the process) The manufacturing method of the laminate 30 with the member for an electronic device described above is not particularly limited, and the member 28 for an electronic device is formed on the substrate 18 of the laminate 10A by a conventionally known method according to the type of the constituent member of the member for an electronic device. The member 28 for an electronic device may not be all of the members finally formed on the substrate 18A (hereinafter referred to as "all members"), but may be a part of the all members (hereinafter referred to as "partial member"). The substrate with the partial member peeled off from the adhesion layer 14 can also be made into a substrate with all members (corresponding to an electronic device described later) in a subsequent process. Another member for an electronic device may be formed on the peeled surface of the substrate with all members peeled off from the adhesion layer 14. Further, the members 28 for an electronic device of two laminates 30 with the member for an electronic device are opposed to each other, and the two are bonded together to assemble a laminate with all members. Then, the two support substrates 20 with adhesion layers are peeled off from the laminate with all members to manufacture an electronic device.

[0067] For example, taking the case of manufacturing an OLED as an example, in order to form an organic EL structure on the surface of the substrate 18A of the laminate 10A on the side opposite to the metal layer 16A side, a transparent electrode is formed, and a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, etc. are vapor-deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and sealing is performed using a sealing plate. Various layer formations and processes such as these are carried out. Specific examples of these layer formations and processes include, for example, film formation processes, vapor deposition processes, adhesion processes of the sealing plate, and the like.

[0068] In addition, when using the laminate 10B and the laminate 10C, since through holes are provided in the substrates 18B and 18C, when forming a member for an electronic device, by performing a plating process, the through holes can be filled with a conductor (metal).

[0069] (Separation step) As shown in FIG. 6, the separation step is a step of irradiating a laser from the support substrate 12 side of the laminate 30 with an electronic device member, peeling the support substrate 12 and the adhesion layer 14 from the laminate 30 with an electronic device member, and obtaining an electronic device 32 including the electronic device member 28, the substrate 18A, and the metal layer 16A.

[0070] When the electronic device member 28 on the peeled substrate 18A is a part of the formation of all necessary constituent members, after separation, the remaining constituent members can also be formed on the substrate 18A.

[0071] When a laser is irradiated from the support substrate 12 side of the laminate 30 with an electronic device member, laser absorption occurs in the metal layer 16A, and peeling occurs between the adhesion layer 14 and the metal layer 16A. The detailed reason for the occurrence of peeling is unknown, but it is considered that when the metal layer 16A absorbs the laser, the temperature of the metal layer 16A locally rises, decomposition of the adhesion layer 14 adjacent to the metal layer 16A occurs, and peeling occurs between the two.

[0072] The irradiation conditions of the laser are not particularly limited, but the laser wavelength is preferably 193 to 10600 nm, and more preferably 300 to 1064 nm. The beam size (area) of the laser is preferably 10 to 500 mm 2 . The repetition frequency of the laser is preferably 10 to 10,000 Hz. The overlap rate of the laser is preferably 10 to 90%. The irradiation energy is preferably 10 to 300 mJ / cm 2 .

[0073] Since the obtained electronic device contains a metal layer, it is possible to further perform a plating process on the obtained electronic device.

Example

[0074] Hereinafter, the present invention will be specifically described by way of examples and the like, but the present invention is not limited by these examples. Hereinafter, Examples 1 to 17 are examples, and Examples 18 to 22 are comparative examples.

[0075] Hereinafter, as a support substrate, a glass plate (「AN100」, manufactured by AGC Inc.) having a size of 200×200 mm and a thickness of 0.5 mm was used. As substrates, a glass plate (「AN100」, manufactured by AGC Inc.) having a size of 200×200 mm and a thickness of 0.15 mm, and a substrate having through holes (hole diameter: 100 μm, hole pitch (distance between hole centers): 200 μm) formed in the central portion (180×180 mm) of a glass plate (「AN100」, manufactured by AGC Inc.) having a size of 200×200 mm and a thickness of 0.13 mm were used. The support substrate and the substrate were washed with an aqueous glass detergent (「PK-LCG213」, manufactured by Parker Corporation), and then washed with pure water.

[0076] <Evaluation> (Evaluation of the presence or absence of a metal-coated portion on the inner wall surface of the through hole of the substrate) In Examples 12 to 17, a cross section of the through-hole portion of the substrate having through holes on which a metal layer was formed was observed with a scanning electron microscope (SEM), and the presence or absence of a metal-coated portion on the inner wall surface of the through hole of the substrate was evaluated. When there was a metal coating part, it was evaluated as "present", and when there was no metal coating part, it was evaluated as "absent". When not evaluated, it was set as "-".

[0077] (Peeling evaluation) For the laminate after heat treatment, a peeling test was conducted using a laser device with a laser wavelength of 355 nm, a beam size of 40×0.4 mm, and a laser repetition frequency of 20 Hz. For the laminate, laser light was incident from the support substrate side, and the overlap rate (overlap ratio) of the irradiation shape of the laser light was 50 - 90%, and the irradiation energy density was 10 - 260 mJ / cm 2 was adjusted. After laser light irradiation, the state of peeling from the adhesion layer of the substrate with a metal layer including the metal layer and the substrate, with the interface between the adhesion layer and the metal layer as the peeling interface, was visually confirmed and evaluated according to the following criteria. In the following evaluation criteria, if it is Evaluation A or B, it can be judged to be within the practical allowable range. A: Peeling occurred over the entire surface between the adhesion layer and the metal layer. B: There were partially existing non-peeled portions between the adhesion layer and the metal layer. C: No peeling occurred between the adhesion layer and the metal layer.

[0078] (Seed layer function evaluation) On the surface of the metal layer of the substrate with a metal layer peeled off by performing the above (peeling evaluation), an attempt was made to form a copper or gold plating film by electrolytic plating or electroless plating. The state of the plating film formation was visually confirmed and evaluated according to the following criteria. In the following evaluation criteria, if it is Evaluation A or B, it can be judged to be within the practical allowable range. A: The plating film was formed over the entire surface of the metal layer. B: The plating film was partially formed on the metal layer. C: No plating film was formed on the metal layer at all.

[0079] (Adhesion evaluation of metal layer) An adhesive tape ("600-1-18DN", manufactured by 3M Japan Limited) was attached to the surface of the metal layer of the substrate with a metal layer that had been peeled off after performing the above (peeling evaluation). The tape was pulled perpendicular to the film surface, and the tape was peeled off. The state of the metal layer after peeling off the tape was visually confirmed and evaluated according to the following criteria. In the following evaluation criteria, if the evaluation is A or B, it can be determined that it is within the practical allowable range. A: No peeling of the metal layer was observed. B: Partial peeling was observed in the metal layer. C: Peeling was observed over the entire surface of the metal layer.

[0080] <Preparation of curable silicone 1 and curable composition 1> (Preparation of curable silicone 1) A curable silicone 1 was obtained by mixing an organohydrogensiloxane and an alkenyl group-containing siloxane. The composition of curable silicone 1 had a molar ratio of M units, D units, and T units of 9:59:32, a molar ratio of methyl groups and phenyl groups of organic groups of 44:56, a molar ratio of all alkenyl groups to hydrogen atoms bonded to all silicon atoms (hydrogen atom / alkenyl group) of 0.7, and an average number of OX groups of 0.1. The average number of OX groups was a numerical value representing the average number of OX groups (X is a hydrogen atom or a hydrocarbon group) bonded to one Si atom.

[0081] (Preparation of curable composition 1) To a solution obtained by mixing diethylene glycol diethyl ether ("Hysolb EDE", manufactured by Toho Chemical Industry Co., Ltd.) (84.9 g) and curable silicone 1 (200 g), Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (CAS No. 68478-92-2) was added so that the content of platinum element with respect to curable silicone 1 was 120 ppm to obtain mixture A. Methylphenyl-modified silicone ("AP 1000", manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) (0.500 g) was mixed into mixture A, and the resulting mixed solution was filtered using a filter with a pore size of 0.45 μm to obtain curable composition 1.

[0082] <Example 1> The prepared curable composition 1 was applied to a support substrate and heated at 140 °C for 5 minutes using a hot plate, and then at 250 °C for 30 minutes using an oven to form a silicone resin layer with a thickness of 10 μm, and a support substrate with a silicone resin layer was obtained. Next, a metal layer was formed on the surface of a separately prepared substrate using a sputtering apparatus. In Example 1, a Ti layer was formed as the first layer and a Cu layer was formed as the second layer to obtain a substrate with a metal layer. Thereafter, the support substrate with a silicone resin layer and the substrate with a metal layer were bonded together using a bonding apparatus so that the silicone resin layer and the metal layer were in contact with each other to obtain a laminate. The obtained laminate was heated at 300 °C for 30 minutes in a nitrogen atmosphere using an inert gas oven. Various evaluations described above were performed on the obtained laminate.

[0083] <Examples 2 to 22> As shown in the table described later, various evaluations were performed according to the same procedure as in Example 1 except that the type of the substrate used and the type of the metal film were changed. Regarding Examples 12 to 15, a substrate having through holes was used, and a metal layer was formed on the surface of the substrate using a sputtering apparatus. Regarding Examples 16 to 17, after obtaining a substrate with a metal layer according to the same procedure as in Example 1, through holes penetrating the substrate and the metal layer were provided, and then bonding with a support substrate with a silicone resin layer was performed.

[0084] In Tables 1 to 4, the notations in the "metal layer" column represent the metal species and thickness in the metal layer. For example, "Ti / 50 nm" represents a Ti layer with a thickness of 50 nm. In Tables 1 to 4, the "adhesion evaluation of the metal-coated part" column shows the results of the above-described (evaluation of the presence or absence of the metal-coated part on the inner wall surface of the through hole of the substrate).

[0085]

Table 1

[0086]

Table 2

[0087]

Table 3

[0088]

Table 4

[0089] As shown in Tables 1 to 4, the laminate of the present invention exhibited the desired effects. From the comparison between Example 5 and Examples 1 to 4, it was confirmed that when the metal layer has a multilayer structure, the adhesion of the metal layer is more excellent. From the comparison between Example 14 and Example 16, it was confirmed that when there is a metal-coated portion on the inner wall surface of the through hole, the peelability is more excellent.

[0090] <Manufacture of Organic EL Display Device (corresponding to electronic device)> Using the laminate substrates obtained in Examples 1 to 17, an organic EL display device was manufactured according to the following procedure. First, silicon nitride, silicon oxide, and amorphous silicon were sequentially deposited on the surface of the laminate substrate on the side opposite to the support substrate side by plasma CVD method. Next, low-concentration boron was implanted into the amorphous silicon layer by an ion doping apparatus, and heat treatment and dehydrogenation treatment were performed. Next, crystallization treatment of the amorphous silicon layer was performed by a laser annealing apparatus. Next, etching using photolithography and low-concentration phosphorus was implanted into the amorphous silicon layer from an ion doping apparatus to form N-type and P-type TFT areas. Next, after forming a gate insulating film by depositing a silicon oxide film by plasma CVD on the surface of the laminate on the side opposite to the support base material side of the substrate, molybdenum was deposited by sputtering, and a gate electrode was formed by etching using a photolithography method. Next, high-concentration boron and phosphorus were implanted into desired areas of the N-type and P-type, respectively, by a photolithography method and an ion doping apparatus to form a source area and a drain area. Next, an interlayer insulating film was formed by depositing silicon oxide by plasma CVD on the surface of the laminate on the side opposite to the support base material side of the substrate, and a TFT electrode was formed by depositing aluminum by sputtering and etching using a photolithography method. Next, after heat treatment and hydrogenation treatment in a hydrogen atmosphere, a passivation layer was formed by depositing silicon nitride by plasma CVD. Next, an ultraviolet curable resin was applied on the surface of the laminate on the side opposite to the support base material side of the substrate, and a planarization layer and contact holes were formed by a photolithography method. Next, indium tin oxide was deposited by sputtering, and a pixel electrode was formed by etching using a photolithography method. Subsequently, by vapor deposition, 4,4’,4”-tris(3-methylphenylphenylamino)triphenylamine as a hole injection layer, bis[(N-naphthyl)-N-phenyl]benzidine as a hole transport layer, a mixture of 8-hydroxyquinoline aluminum complex (Alq3) and 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl]naphthalene-1,5-dicarbonitrile (BSN-BCN) at 40% by volume as a light-emitting layer, and Alq3 as an electron transport layer were deposited in this order on the side opposite to the glass plate side of the polyimide resin layer. Next, aluminum was deposited by sputtering, and a counter electrode was formed by etching using a photolithography method. Next, another glass plate was bonded and sealed via an ultraviolet curable adhesive layer on the surface of the laminate on the side opposite to the support base material side of the substrate. By the above procedure, an organic EL structure was formed on the polyimide resin layer. A structure having an organic EL structure on a substrate (hereinafter referred to as Panel A) is a laminate with a member for an electronic device according to the present invention. Subsequently, with the sealing body side of Panel A vacuum-sucked onto the surface plate, a laser was irradiated from the support base material side to peel between the adhesion layer (silicone resin layer) and the metal layer. As a result, the support base material with the silicone resin layer could be peeled off.

[0091] Although the present invention has been described in detail with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2020-101638) filed on June 11, 2020, the content of which is incorporated herein by reference.

Explanation of Reference Numerals

[0092] 10A, 10B, 10C laminate 12 support base material 14 adhesion layer 16A, 16B, 16C metal layer 18A, 18B, 18C substrate 20 support base material with adhesion layer 22 first through hole 24 second through hole 26 metal coating part 28 member for electronic device 30 laminate with member for electronic device 32 electronic device

Claims

1. A laminate having a support substrate, an adhesion layer, a metal layer, and a substrate in this order, wherein the metal layer contains at least one metal selected from the group consisting of copper, titanium, palladium, gold, nickel, tungsten, and molybdenum, wherein the metal layer is in contact with the substrate, wherein the adhesion layer is an organic layer, and wherein the substrate is a glass substrate.

2. The laminate according to claim 1, wherein the metal layer contains at least one metal selected from the group consisting of copper, titanium, palladium, gold, and nickel.

3. The laminate according to claim 1 or 2, wherein the metal layer has a first metal layer and a second metal layer disposed on the first metal layer, and wherein the type of metal contained in the first metal layer is different from the type of metal contained in the second metal layer.

4. The laminate according to claim 3, wherein the first metal layer is disposed closer to the substrate side than the second metal layer, and wherein the first metal layer contains titanium.

5. The laminate according to claim 4, wherein the second metal layer contains copper.

6. The laminate according to any one of claims 1 to 5, wherein the metal layer has a first through hole extending in the thickness direction, wherein the substrate has a second through hole extending in the thickness direction, and wherein the first through hole and the second through hole communicate with each other.

7. The laminate according to claim 6, further comprising a metal coating portion made of metal that covers at least a part of the inner wall surface of the second through hole.

8. The laminate according to any one of claims 1 to 7, wherein the adhesion layer is a silicone resin layer.

9. The laminate according to any one of claims 1 to 8, wherein the support substrate is a glass substrate.

10. A laminate with an electronic device member, comprising the laminate according to any one of claims 1 to 9, and an electronic device member disposed on the substrate in the laminate.

11. A member forming step of forming an electronic device member on the surface of the substrate of the laminate according to any one of claims 1 to 9 to obtain a laminate with an electronic device member, and a separation step of irradiating the laminate with an electronic device member from the support substrate side with a laser to peel off the support substrate and the adhesion layer from the laminate with an electronic device member to obtain an electronic device having the electronic device member, the substrate, and the metal layer.

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