TW202218076A - Method for producing multilayer body, multilayer body and method for producing semiconductor package - Google Patents

Abstract

The present invention relates to a method for producing a multilayer body, said method comprising: a step for forming a multilayer body precursor which comprises two glass substrates and a thermosetting resin layer that is arranged between the two glass substrates; and a step for obtaining a multilayer body with a warp, said multilayer body comprising the two glass substrates and a resin layer that is arranged between the two glass substrates, by forming the resin layer by thermally curing the thermosetting resin layer, while maintaining the multilayer body precursor in a deformed state.

Description

Manufacturing method of laminated body, laminated body, and manufacturing method of semiconductor package

The present invention relates to a method for manufacturing a laminate, a method for manufacturing the laminate, and a semiconductor package.

A semiconductor device including an integrated circuit or the like is electrically connected to a redistribution layer (RDL) by bonding wires, solder balls, or the like, and is mounted, and further sealed with resin to form a semiconductor package. The semiconductor package is produced, for example, by the following method. First, after the rewiring layer is formed on the glass substrate, the semiconductor device and the rewiring layer are electrically connected by bonding wires, solder balls, or the like. Thereafter, the semiconductor device is sealed with resin. Next, a semiconductor package is obtained by peeling off the rewiring layer on which the resin-sealed semiconductor device is mounted from the glass substrate. Considering the deformation of the substrate due to heat in the manufacturing process of the semiconductor package, the glass substrate having warpage described in Patent Document 1 is used as the glass substrate for manufacturing the semiconductor package. Patent Document 1 describes a glass substrate having a warpage of 2 to 300 μm and an inclination angle due to the warpage of 0.0004 to 0.12°. prior art literature Patent Literature

Patent Document 1: Japanese Patent No. 6601493

[Problems to be Solved by Invention]

The glass substrate of the above-mentioned Patent Document 1 is warped through a forming process and a slow cooling process. Although the warpage and the inclination angle due to warpage can be adjusted by adjusting the slow cooling temperature of the slow cooling process, the adjustment of the warpage amount and the like is not easy. Therefore, an object of the present invention is to provide a method for producing a laminate that can easily produce a laminate that has warpage and maintains warp even after being exposed to high temperature, and further, an object of the present invention is to provide a laminate having warpage. A warped laminate, and a manufacturing method of a semiconductor package are provided. [Technical means to solve problems]

As a result of earnest research, the present inventors found that the above-mentioned object can be achieved by the following constitution. An aspect of the present invention provides a method for producing a layered product, which includes the steps of forming a precursor layered product having two glass substrates and thermosetting properties disposed between the two glass substrates resin layer; and obtaining a laminated body, thermosetting the thermosetting resin layer in a state in which the precursor laminated body is deformed to form a resin layer to obtain a laminated body, the laminated body having two glass substrates and arranged in 2 The resin layer between the glass substrates has warpage. Preferably, the difference between the average thermal expansion coefficients of the two glass substrates is 1.5 ppm/°C or less. Preferably, after the step of forming the precursor layered body, there is further a step of chamfering, grinding, and polishing the glass substrate of the precursor layered body. Preferably, the temperature of the thermosetting resin layer at the time of thermosetting is 400° C. or lower. Preferably, the thermosetting of the thermosetting resin layer is performed at a temperature 20° C. or more higher than the thermosetting initiation temperature of the thermosetting resin layer.

An aspect of this invention provides the laminated body which has a 1st glass substrate, a resin layer, and a 2nd glass substrate in this order, and the laminated body has a warpage. Preferably, the first glass substrate, the resin layer, and the second glass substrate are bent so that the outer surface of the first glass substrate protrudes, and the electronic device is arranged on the bent first glass substrate. Preferably, the difference between the average thermal expansion coefficients of the first glass substrate and the second glass substrate is 1.5 ppm/°C or less. Preferably, the total thickness of the laminate is 0.3 to 3.0 mm. Preferably, the warpage amount of the laminate is more than 0 μm and 500 μm or less. Preferably, the amount of warpage of the laminate after being heated at 250° C. for 3 hours exceeds 0 μm and is 500 μm or less. Aspects of the present invention provide a method of manufacturing a semiconductor package, the manufacturing method including the steps of: preparing a laminate having a first glass substrate, a resin layer, and a second glass substrate in this order and having warpage; A rewiring layer is formed on the outer surface of the first glass substrate; the semiconductor device is electrically connected to the rewiring layer; the semiconductor device is sealed with a resin; and the rewiring layer on which the resin-sealed semiconductor device is mounted is peeled off from the first glass substrate . [Inventive effect]

According to the present invention, it is possible to easily manufacture a laminate having warpage and maintaining warpage even after exposure to high temperature. Furthermore, a laminated body having warpage can be provided. Further, a semiconductor package can be manufactured.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. However, the following embodiments are exemplary embodiments for explaining the present invention, and the present invention is not limited to the embodiments shown below. Furthermore, various changes and substitutions may be added to the following embodiments without departing from the scope of the present invention. The numerical range indicated by "~" means the range including the numerical values before and after the "~" as the lower limit value and the upper limit value.

In the method for producing a laminate of the present invention, a precursor laminate having two glass substrates and a thermosetting resin layer disposed between the two glass substrates is formed, and the precursor laminate is deformed. In this state, thermosetting of the thermosetting resin layer was performed to form a resin layer between two glass substrates. Thereby, the laminated body in which the resin layer was arrange|positioned between two glass substrates, and the laminated body which has a curvature was obtained. Since the resin layer is formed in a state in which the precursor layered body is deformed, a layered body having warpage can be formed at a temperature such that the thermosetting resin is hardened. Therefore, the laminated body can be easily produced without raising the temperature. Furthermore, the laminate system with warpage thermally hardens the resin layer and thus maintains warpage even after exposure to high temperature. Moreover, as for the laminated body, the selection range of glass substrates is wide regardless of what kind of glass substrates it is. Hereinafter, the manufacturing method of a laminated body is demonstrated.

<Manufacturing method of laminated body> [An example of a method for manufacturing a laminate] FIGS. 1( a ) to ( d ) are schematic cross-sectional views showing a method for producing a layered body according to an embodiment of the present invention in order of steps, and FIG. 2 is a schematic cross-sectional view showing an example of the layered body according to the embodiment of the present invention. The manufactured laminate 30 (see FIG. 2 ) has warpage, a resin layer is disposed between two glass substrates, and includes the first glass substrate 14 (see FIG. 1( b )) and the second glass substrate 10 (see FIG. 1( b )) Figure 1(b)). Both the first glass substrate 14 (see FIG. 1( b )) and the second glass substrate 10 (see FIG. 1( b )) are discs. First, as shown in FIG. 1( a ), the thermosetting resin layer 12 is formed on one surface (surface 10 a ) of the second glass substrate 10 . In FIG. 1( a ), the thermosetting resin layer 12 is in an uncured state. Next, as shown in FIG.1(b), the 1st glass substrate 14 is arrange|positioned on the surface 12a of the opposite side to the surface on which the 2nd glass substrate 10 of the thermosetting resin layer 12 is arrange|positioned. Thereby, the precursor laminated body 16 which has two glass substrates and the thermosetting resin layer 12 arrange|positioned between the two glass substrates is formed. Next, as shown in FIG. 1( c ), the peripheral edge 16 c of the precursor layered body 16 is chamfered. Furthermore, the surface 14a of the outer side of the 1st glass substrate 14 and the surface 10b of the 2nd glass substrate 10 are ground and polished. Thereby, the thickness and TTV (Total Thickness Variation) of the precursor layered body 16 are adjusted. Furthermore, it is preferable to perform chamfering, grinding, and grinding, but it is not necessary to perform chamfering, grinding, and grinding. It is desirable to perform at least chamfering, grinding, and grinding.

Next, as shown in FIG. 1( d ), the precursor layered body 16 is mounted on the mold 20 at room temperature (25° C.). The mold 20 has an upper mold 22 and a lower mold 24 . The upper mold 22 and the lower mold 24 are made of carbon, for example. The upper die 22 has a concave portion 22a having a concave shape. The lower die 24 has a convex portion 24a having a convex shape. In the mold 20, the concave portion 22a of the upper mold 22 and the convex portion 24a of the lower mold 24 are arranged to face each other. The shape of the inner wall of the mold 20 is formed by the space between the concave portion 22a and the convex portion 24a. The outer surface 14a of the first glass substrate 14 is deformed in a convex manner by the concave portion 22a of the upper mold 22, and the surface 10b of the second glass substrate 10 is concave by the convex portion 24a of the lower mold 24. deformed. The 1st glass substrate 14 is arrange|positioned on the upper mold|type 22 so that the surface 14a side may face the upper mold|type 22, and the 2nd glass substrate 10 may be arrange|positioned on the lower mold|type 24 so that the surface 10b side may face the lower mold|type 24. By tightening the upper mold 22 and the lower mold 24 with the bolts 26 and the nuts 27, the first glass substrate 14 is deformed according to the shape of the concave portion 22a of the upper mold 22, and the second glass substrate 10 is made to conform to the shape of the lower mold 24. The shape of the convex portion 24a is deformed. Thereby, the 1st glass substrate 14 deforms so that the surface 14a of the outer side of the 1st glass substrate 14 may protrude. Next, the precursor layered body 16 is heated, and the thermosetting resin layer 12 is thermally cured to form the resin layer 13 (see FIG. 2 ). The heating of the precursor layered body 16 is carried out, for example, in a nitrogen atmosphere at a rate of 10°C/min from a temperature of 25°C to 250°C, then maintained at 250°C for 30 minutes, and thereafter, at a rate of -10°C/min. 250°C cooled to 150°C.

After the mold 20 is cooled, the nut 27 is removed from the bolt 26 and the precursor layered body 16 is taken out from the mold 20 . Thereby, as shown in FIG. 2, the laminated body 30 which has the 1st glass substrate 14, the resin layer 13, and the 2nd glass substrate 10 in this order and has a curvature is obtained. The laminated body 30 maintains the warpage even after being exposed to high temperature. The laminated body 30 shown in FIG. 2 has a circular outer shape. Furthermore, in the above description, the first glass substrate 14 and the second glass substrate 10 are respectively set as circular plates, but the shapes of the first glass substrate 14 and the second glass substrate 10 are not particularly limited, and may be rectangular, for example. . Moreover, since the laminated body 30 is formed by laminating the first glass substrate 14 and the second glass substrate 10 and deforming them equally, the first glass substrate 14 and the second glass substrate 10 are preferably similar in shape. In addition, when manufacturing the layered body 30, instead of using the glass substrate of the circular plate, for example, the precursor layered body may be formed using the rectangular first glass substrate 14 and the second glass substrate 10, and then the precursor layered body may be cut. It is rounded, chamfered, ground, and ground to form a precursor layered body with a round shape.

<Laminated body> The laminated body 30 shown in FIG. 2 has a circular shape as described above. For example, when the laminated body 30 is disposed on the plane B by contacting the surface 10b of the second glass substrate 10 on the plane B, the first glass substrate 14, the resin layer 13, and the second glass substrate 10 are formed by the first glass substrate 14. The outer surface 14a is curved in a convex manner. As described above, when the surface 10b of the second glass substrate 10 is placed on the plane B in contact with the plane B, the outer diameter of the first glass substrate 14 becomes the diameter D of the laminate 30 in a state where the first glass substrate 14 is warped. The diameter D is not particularly limited, and can be set to a size approximately the same as the diameter of the semiconductor wafer, for example, 8 inches or 12 inches. 3 is a schematic cross-sectional view showing an example of a use example of the laminate according to the embodiment of the present invention. In addition, in FIG. 3, the same code|symbol is attached|subjected to the same structure as the laminated body 30 shown in FIG. 2, and the detailed description is abbreviate|omitted. In the laminated body 30, the 1st glass substrate 14, the resin layer 13, and the 2nd glass substrate 10 are curved so that the outer surface 14a of the 1st glass substrate 14 may protrude as mentioned above. In addition, the surface 14a of the outer side of the 1st glass substrate 14 means the surface on the opposite side to the surface on which the resin layer 13 of the 1st glass substrate 14 is arrange|positioned.

In addition, when the operation of the conveyance process and the peeling of the rewiring layer 42 are considered, the total thickness h ( FIG. 2 ) of the laminate 30 is preferably 0.3 to 3.0 mm, more preferably 0.5 to 2.0 mm. The total thickness h of the laminated body 30 can be measured using a spectroscopic laser displacement meter. Moreover, the warpage amount of the laminated body 30 is preferably more than 0 μm and 500 μm or less, and more preferably 50 to 300 μm. When the warpage amount of the laminated body 30 exceeds 0 μm, the warpage correction effect in the packaging process of the electronic device is sufficient. When the warpage amount of the laminated body 30 is 500 μm or less, it is easy to hold (hold) the substrate in the packaging process of the electronic device. The warpage amount of the laminate 30 after being heated at 250° C. for 3 hours is preferably more than 0 μm and 500 μm or less, more preferably 50 to 300 μm. If the warpage amount of the laminated body 30 after heating at 250° C. for 3 hours exceeds 0 μm and is 500 μm or less, the laminated body 30 maintains the warpage even after being exposed to high temperature, and can be repeatedly used for manufacturing semiconductor packages. In addition, after heating at 250 degreeC for 3 hours, after heating at 250 degreeC for 3 hours in nitrogen atmosphere, it means that the laminated body has reached the state of room temperature (25 degreeC).

(Semiconductor package and its manufacturing method) As shown in FIG. 3 , a semiconductor package 40 is provided on the surface 14 a of the curved first glass substrate 14 . The semiconductor package 40 has, for example, an electronic device 44 mounted on the rewiring layer 42 . The electronic device 44 is arranged on the curved first glass substrate 14 . The surface on the opposite side of the first glass substrate 14 and the surface on which the resin layer 13 is arranged, that is, the surface 14a on the outer side of the first glass substrate 14 is a surface on which the electronic device 44 is formed. The rewiring layer 42 and the electronic device 44 are electrically connected by bonding wires, solder balls, or the like. Electronic device 44 is sealed by resin 46 . The rewiring layer 42 is formed on the surface 14 a of the first glass substrate 14 . The semiconductor package 40 is taken out by peeling off the rewiring layer 42 from the surface 14a of the first glass substrate 14 . The electronic device 44 is a semiconductor device having an integrated circuit or the like, and specifically, is, for example, a MEMS (Micro Electro Mechanical Systems), an ASIC (Application Specific Integrated Circuit), or the like. The resin 46 is a sealing resin for sealing the electronic device 44, and a resin used in a semiconductor package can be appropriately used. For example, as the resin 46, a well-known thermosetting resin such as epoxy resin is used to mix silica fine particles.

(Amount of warpage of laminated body) FIGS. 4( a ) and ( b ) are schematic cross-sectional views illustrating a method of measuring the amount of warpage of the laminate according to the embodiment of the present invention. As shown in FIG.4(a), the laminated body 30 was arrange|positioned so that the surface 10b of the 2nd glass substrate 10 may face the surface 50a of the precision stage 50, and the warpage amount of the laminated body 30 was measured. The laser displacement meter 52 was used for the measurement of the warpage amount. The laser beam L is irradiated from the laser displacement meter 52 to the outer surface 14a of the first glass substrate 14, and the height from the surface 50a of the precision stage 50 to the surface 14a of the first glass substrate 14 irradiated with the laser beam L is measured. For example, the laser beam L is irradiated at intervals of 3 mm in a direction parallel to the surface 50a of the precision stage 50, and the height at each irradiation position is measured. Thereby, the in-plane maximum height hc of the 1st glass substrate 14 and the height hi of an edge part are obtained. The value (hc−hi) obtained by subtracting the height hi of the end portion of the first glass substrate 14 from the maximum height hc in the plane of the first glass substrate 14 in the thickness direction of the laminate 30 was calculated as the warpage amount. As shown in FIG. 4( a ), when the laminate 30 has a convex shape, that is, the end of the surface 10 b of the second glass substrate 10 is in contact with the surface 50 a of the precision stage 50 , and the center is not in contact with the precision stage In the state of the surface 50a of 50, the warpage amount of the laminated body 30 is positive. On the other hand, as shown in FIG. 4B , when the laminate 30 has a concave shape, that is, the end of the surface 10b of the second glass substrate 10 is not in contact with the surface 50a of the precision stage 50, and the center is in contact with the precision stage 50. In the state of the surface 50a of the platform 50, the warpage amount of the laminated body is the difference between the minimum height hm in the plane and the height hi of the end. In this case, the warpage amount is negative.

[Manufacturing method of laminated substrate] As described above, the method for manufacturing a laminated substrate includes at least the following steps: forming a precursor layered body (precursor layered body forming step) having two glass substrates and a thermal curing process disposed between the two glass substrates and forming a resin layer by thermosetting the thermosetting resin layer in a state in which the precursor laminate is deformed (molding step). Hereinafter, each of the above-mentioned steps will be described.

(Precursor Laminated Body Forming Step) <The thermosetting resin layer forming step> In the thermosetting resin layer forming step, for example, a thermosetting silicone layer is formed on the surface 10a of the second glass substrate 10 as a thermosetting resin layer. The formation method of the thermosetting resin layer (thermosetting silicone layer) is not particularly limited, and for example, a spray coating method, a die nozzle coating method, a spin coating method, a dip coating method, a roll coating method, and a bar coating method are used. Coating method, screen printing method, and gravure coating method.

<Lamination process> The lamination process is a process of laminating the first glass substrate 14 on the surface 12 a of the thermosetting resin layer 12 . As a specific example of the method of laminating the first glass substrate 14 on the surface 12a of the thermosetting resin layer 12, the method of laminating the first glass substrate 14 on the surface 12a of the thermosetting resin layer 12 in a normal pressure environment can be mentioned . If necessary, after stacking the first glass substrate 14 on the surface 12a of the thermosetting resin layer 12, the first glass substrate 14 may be press-bonded to the thermosetting resin layer using a roll or a press. It is preferable that the air bubbles mixed between the thermosetting resin layer 12 and the first glass substrate 14 can be relatively easily removed by pressure-bonding with a roll or a press. When crimping is performed by a vacuum lamination method or a vacuum pressing method, it is possible to suppress the mixing of air bubbles and to achieve good adhesion, which is preferable. By performing pressure-bonding under vacuum, there is also an advantage that, even when minute air bubbles remain, the air bubbles are less likely to grow by the heat treatment. When laminating the first glass substrate 14 on the surface 12a of the thermosetting resin layer 12, it is preferable to thoroughly clean the surface of the first glass substrate 14 in contact with the thermosetting resin layer, and perform lamination in an environment with high cleanliness . In addition, in the precursor layered body forming step, after the thermosetting resin layer 12 is formed on the surface of the first glass substrate 14 in the thermosetting resin layer forming step, the second glass substrate may be formed in the lamination step. 10 is laminated on the surface of the thermosetting resin layer 12 .

<Chamfering process> The chamfering step is a step of chamfering the peripheral edge 16 c of the precursor layered body 16 . The chamfering method is not particularly limited, and a known method such as a method using a chamfering machine for glass substrates can be used. After chamfering, the front and back surfaces of the precursor layered body 16 may be ground using a grinder or the like, and the front and back surfaces of the precursor layered body 16 may be ground by a grinder. By performing chamfering or the like, when the precursor layered body 16 is installed in the mold, it is possible to prevent the precursor layered body 16 from damaging the mold. In addition, by grinding and polishing the front and back surfaces of the precursor layered body 16 , the thickness and TTV (Total Thickness Variation) of the precursor layered body 16 can be adjusted.

(forming process) The molding step is a step of forming the resin layer 13 by thermally curing the thermosetting resin layer 12 in a state in which the precursor layered body 16 is deformed. As described above, the precursor laminate 16 is mounted on the mold 20 (see FIG. 1( d )), the first glass substrate 14 is deformed according to the shape of the concave portion 22 a of the upper mold 22 , and the second glass substrate 10 is The shape of the convex part 24a of the mold 24 is deformed. In this state, the precursor layered body 16 is heated to thermally harden the thermosetting resin layer 12 to form the resin layer 13 (see FIG. 2 ). When the thermosetting resin layer 12 is made of thermosetting silicone, the thermosetting silicone is cured by heat treatment to form a silicone resin layer as the resin layer 13 . For example, condensation reaction type silicone and addition reaction type silicone are used as thermosetting silicone. The silicone resin layer will be described below. Regarding the conditions of thermal curing, for example, the temperature conditions of thermal curing are preferably 50 to 400°C, more preferably 100 to 300°C. The heating time is preferably 10 to 300 minutes, more preferably 20 to 120 minutes. The temperature of the thermosetting resin layer at the time of thermosetting is preferably 400°C or lower, more preferably 300°C or lower. Thereby, the temperature at the time of molding can be suppressed from being high. In addition, the thermosetting of the thermosetting resin layer is performed at a temperature higher than the thermosetting initiation temperature of the thermosetting resin layer, preferably 20°C or higher, more preferably 50°C or higher. By thermosetting the thermosetting resin layer at the above temperature, the thermosetting resin layer can be surely thermosetted, and a resin layer can be obtained. The thermosetting initiation temperature of the thermosetting resin layer is preferably 40°C or higher and 300°C or lower, more preferably 80°C or higher and 200°C or lower. When the thermosetting initiation temperature of the thermosetting resin layer is too low, the thermosetting resin layer is hardened before the molding process, and there is a possibility that a laminate having a desired amount of warpage cannot be obtained after the molding process. On the other hand, when the thermosetting initiation temperature of the thermosetting resin layer is too high, the temperature at the time of molding may become high. Furthermore, regarding the definition of the initiation temperature of thermosetting, differential scanning calorimetry (DSC) was performed on the thermosetting resin under the condition of a heating rate of 10°C/min, and the reference line of the DSC curve and the tangent at the inverse inflection point of the peak were measured. The intersection point is set as the thermal hardening start temperature.

Hereinafter, the layered body will be described. <1st glass substrate, 2nd glass substrate> The glass constituting the first glass substrate and the second glass substrate is not particularly limited. As the type of glass, alkali-free borosilicate glass, borosilicate glass, soda lime glass, high-oxide silica glass, and other oxide-based glasses mainly composed of silica are preferred. The oxide-based glass is preferably a glass whose content of silicon oxide obtained by oxide conversion is 40 to 90% by mass. As an example of a glass plate, the glass plate (trade name "AN100" by AGC Co., Ltd. product) containing alkali-free borosilicate glass is mentioned more specifically. In addition, the trade names "FL900" and "FL960" manufactured by AGC Co., Ltd. can also be used. As an example of the manufacturing method of a glass plate, the method which melts a glass raw material and shape|molds a molten glass into a plate shape is mentioned normally. Such a molding method may be a common method, for example, a float method, a melting method, and a downdraft method can be mentioned.

As described above, the glass constituting the first glass substrate and the second glass substrate is not particularly limited, but the difference between the average thermal expansion coefficients of the first glass substrate and the second glass substrate is preferably 1.5 ppm/°C or less, and the average thermal expansion coefficient is The lower limit of the difference is 0 ppm/°C. In addition, when a 1st glass substrate and a 2nd glass substrate are the same glass substrate, the difference of an average thermal expansion coefficient is made into 0 ppm/degreeC. By making the difference of the average thermal expansion coefficient small, generation|occurrence|production of a crack in a glass substrate by heating in a shaping|molding process or a device manufacturing process can be suppressed. On the other hand, when the difference of the average thermal expansion coefficients is too large and is 3 ppm/°C or more, cracks may occur in the first glass substrate or the second glass substrate due to heating in the molding process or the device manufacturing process. The average thermal expansion coefficients of the first glass substrate and the second glass substrate are measured using a differential thermal dilatometer (TMA) in accordance with the method specified in JIS (Japanese Industrial Standards) R3102 (1995) at a temperature of 30 to 220°C The average coefficient of thermal expansion below. In addition, the thickness of the first glass substrate and the thickness of the second glass substrate are preferably 0.1 to 1.8 mm, respectively, from the viewpoint of cracks or the like caused by heating in the production process and forming process of the laminate, or the device production process. , more preferably 0.15~1.0 mm. In addition, the preferable range of the thickness of the said 1st glass substrate and the thickness of a 2nd glass substrate shows the preferable range of both the thickness before a laminated body is produced, and the thickness of a laminated body. The thicknesses of the first glass substrate and the second glass substrate can be measured using a spectroscopic laser displacement meter.

<Resin layer> The resin layer 13 is a layer for laminating the first glass substrate 14 and the second glass substrate 10 and maintaining the deformed state of the first glass substrate 14 and the second glass substrate 10 . The thermosetting resin layer 12 is cured in a state in which the first glass substrate and the second glass substrate are deformed, and the resin layer 13 is obtained. Thereby, the resin layer 13 maintains the deformed state of the first glass substrate 14 and the second glass substrate 10 . The thickness of the resin layer 13 is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less. On the other hand, the thickness of the resin layer 13 is preferably more than 1 μm, more preferably 4 μm or more. The thickness described above is obtained by measuring the thickness of the resin layer 13 at an arbitrary position of 5 points or more with a contact-type film thickness measuring apparatus, and calculating the arithmetic mean value thereof.

<Silicone resin layer> If the thermosetting resin layer 12 is made of thermosetting silicone, the resin layer 13 is a silicone resin layer. The silicone resin layer is an example of the layer constituting the resin layer 13 . The silicone resin layer is a layer mainly containing silicone resin. The structure of the silicone resin is not particularly limited. The silicone resin is usually obtained by curing (cross-linking and curing) a curable silicone that can become a silicone resin by curing treatment. Specific examples of the curable silicone include condensation reaction type silicone and addition reaction type silicone. The weight average molecular weight of the curable silicone is preferably 5,000 to 60,000, more preferably 5,000 to 30,000.

The silicone resin layer is formed by applying a curable composition containing curable silicone to become a silicone resin to form a thermosetting resin layer, and is formed by heat treatment. The curable composition may contain, in addition to the curable silicone, a solvent, a platinum catalyst (in the case of using an addition reaction type silicone as the curable silicone), a leveling agent, a metal compound, and the like. Specific examples of the metal element contained in the metal compound include 3d transition metals, 4d transition metals, lanthanoid metals, bismuth, aluminum, and tin. The content of the metal compound can be appropriately adjusted. Examples of the resin layer 13 include acrylic resins, phenolic resins, naphthoquinone-based resins, hydrocarbon-based resins, polyimide-based resins, elastomers, and the like. The resin layer 13 may be composed of, for example, a hydrocarbon-based resin, an acrylic-styrene-based resin, a maleimide-based resin, an elastomer, or the like, or a resin in which they are combined. Example

Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited to these Examples. The following Examples 1 to 17 are examples, and Examples 18 and 19 are comparative examples. Examples 1 to 18 were all used as laminates having a circular shape. Example 19 is a single glass substrate with a circular shape.

＜Assessment＞ "Heat Test" The circular layered body was placed in an inert gas oven, and heated at 250° C. for 3 hours under a nitrogen atmosphere. After confirming that the circular layered product taken out of the oven had reached room temperature (25° C.), the amount of warpage was measured. The method for measuring the warpage amount will be described below.

<Preparation of curable silicone and curable composition> "Preparation of Curable Silicone" Curable silicones are obtained by mixing organohydrosiloxanes with alkenyl-containing siloxanes. The composition of curable silicone is that the molar ratio of M unit, D unit and T unit is 9:59:32, the molar ratio of methyl group and phenyl group of organic group is 44:56, and the total alkenyl group is bonded to The molar ratio of hydrogen atoms to total silicon atoms (hydrogen atoms/alkenyl group) was 0.7, and the average OX group number was 0.1. The average number of OX groups represents the number of OX groups (X is a hydrogen atom or a hydrocarbon group) bonded to one Si atom on average.

"Preparation of Curable Composition 1" In a solution of diethylene glycol diethyl ether ("HYSORB EDE", manufactured by Toho Chemical Industry Co., Ltd.) (1986 g) and curable silicone (2997 g), the ratio of platinum element to curable silicone Mixture A was obtained by adding platinum(0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane (CAS No. 68478-92-2) in such a way that the ketone content was 120 ppm . To the mixture A was mixed methylbenzene-modified silicone ("AP 1000", manufactured by Asahi Kasei Wacker Silicones Co., Ltd.) (4.5 g), and the obtained mixture was filtered using a filter with a pore size of 0.45 μm, whereby A curable composition is obtained.

Hereinafter, Examples 1 to 19 will be described. <Examples 1 to 17> "Preparing the Glass Substrate" The glass substrates described in Table 1 were prepared as the first glass substrate and the second glass substrate. The size of the first glass substrate was set to 450 mm×450 mm, and the size of the second glass substrate was set to 500 mm×500 mm. The glass substrate was washed with a water-based glass cleaner ("PK-LCG213", manufactured by Parker Co., Ltd.), and then washed with pure water.

"Methods for Determination of Physical Properties of Glass Substrates" (average thermal expansion coefficient) According to the method specified in JIS R3102 (1995), use a differential thermal expansion meter (TMA) to measure the average thermal expansion coefficient at 30~220℃. (thickness) The thickness of the glass substrate was measured by a spectroscopic laser displacement meter (manufactured by KEYENCE Co., Ltd.).

"Production of Precursor Laminates" The prepared curable composition was applied to the second glass substrate using a die coater, and heated at 120° C. for 3 minutes using a hot plate, thereby forming a silicone resin layer with a thickness of 10 μm. Then, the layer of the silicone resin on the second glass substrate was bonded to the first glass substrate using a bonding apparatus to produce a precursor layered body. After forming scribe lines on both surfaces of the precursor laminate using a glass cutter, stress was applied to the end of the precursor laminate to cut it to obtain a circular precursor laminate with a diameter of 300 mm. Next, the edge of the circular precursor layered body was chamfered with a glass grindstone. After that, grinding and polishing are performed on one or both surfaces of the circular precursor layered body to obtain a desired thickness.

"Formed Laminate" The molding method will be described with reference to Fig. 1(d). The circular precursor layered body is mounted on a carbon mold (die 20 (refer to FIG. 1(d)) at room temperature, and the circular precursor layered body is deformed into carbon by tightening the bolts and nuts of the carbon mold. The shape of the inner wall of the mold (the shape of the concave portion 22a and the shape of the convex portion 24a (refer to FIG. 1(d)). Then, the circular precursor layered body installed in the carbon mold is placed in an inert gas oven, and placed in a nitrogen atmosphere Heating at 10°C/min from 25°C to 250°C, kept at 250°C for 30 minutes, and cooled from 250°C to 150°C at -10°C/min. After cooling to 150°C At the same time, the atmosphere was introduced into the inert gas oven, and the circular precursor layered body installed in the carbon mold was taken out from the oven. After confirming that the precursor layered body had become room temperature (25°C), it was removed from the carbon mold The circular precursor layered body was taken out to obtain a circular layered body, and the total thickness of the layered body and the amount of warpage of the circular layered body were measured.

<Example 18> A silicon nitride film 19 (SiN film) was formed on one side of the first glass substrate 14 (see FIG. 5 ) cleaned in the same procedure as in Example 1 using a sputtering apparatus to obtain a laminate having a circular shape. The thickness of the silicon nitride film 19 (refer to FIG. 5 ) was set to 200 nm. After the silicon nitride film 19 is formed, the total thickness of the laminate and the amount of warpage of the laminate are measured. Then, the same heat resistance test as in Example 1 was performed, and the warpage amount after the heat resistance test was measured. <Example 19> When the first glass substrate is produced, in the step of forming the molten glass into a plate shape and slowly cooling it, the temperature of the center portion of the glass ribbon in the width direction of the glass ribbon perpendicular to the advancing direction of the glass ribbon and the end portion of the glass ribbon are adjusted. At the temperature, a first glass substrate 60 having warpage was produced (see FIG. 6 ). After confirming that the first glass substrate 60 (see FIG. 6 ) was cooled to room temperature, the amount of warpage was measured. Then, the same heat resistance test as in Example 1 was performed, and the warpage amount after the heat resistance test was measured. In addition, in Example 19, the plate thickness of the 1st glass substrate 60 (refer FIG. 6) was made into the total thickness shown in the following Table 1.

<Measurement of warpage amount> A method of measuring the amount of warpage of the laminate will be described with reference to FIGS. 4( a ) and ( b ). Figures 4(a) and (b) schematically show the warpage of the laminate. On the surface 50a of the precision stage 50, the laminated body 30 is arrange|positioned so that the 1st glass substrate 14 may become an upper side, and the 2nd glass substrate 10 may become a lower side. The height in the thickness direction of the outer surface 14a of the first glass substrate 14 was measured at intervals of 3 mm along the direction parallel to the surface 50a of the precision stage 50 by the non-contact laser displacement meter 52 . The value obtained by subtracting the height of the edge part of the 1st glass substrate 14 from the maximum height in the plane of the 1st glass substrate 14 in the thickness direction of the laminated body 30 was calculated as the warpage amount. As shown in FIG. 4( a ), when the laminated body 30 has a convex shape, the amount of warpage of the laminated body 30 is positive, and as shown in FIG. 4( b ), when the laminated body 30 has a concave shape The amount of warpage of the laminated body 30 is set to be negative.

In Example 18, as shown in FIG. 5, on the surface 50a of the precision stage 50, the non-film-forming surface of the silicon nitride film 19 is placed on the upper side and the film-forming surface side is the lower side. 19. The first glass substrate 14. The height in the thickness direction of the non-film-forming surface side was measured by the laser displacement meter 52, and the value obtained by subtracting the height of the edge part from the maximum height in the plane of a board|substrate was computed as the warpage amount. In Example 19, as shown in FIG. 6 , the first glass substrate 60 is placed on the surface 50 a of the precision stage 50 in the same manner as the laminate, and the maximum value from the surface of the first glass substrate 60 is calculated by the laser displacement meter 52 . The value obtained by subtracting the height of the end from the height was used as the warpage amount. In addition, in FIG.5 and FIG.6, the same code|symbol is attached|subjected to the same structure as the structure shown to FIG.4(a) and (b), and the detailed description is abbreviate|omitted. In addition, the total thickness of the laminated body was measured with a spectroscopic laser displacement meter (manufactured by Keyence Corporation).

[Table 1] Table 1 1st glass substrate 2nd glass substrate Total thickness [mm] Difference between the average thermal expansion coefficients of the first glass substrate and the second glass substrate [ppm/°C] Warpage [μm] Average thermal expansion coefficient [ppm/℃] Thickness [mm] Average thermal expansion coefficient [ppm/℃] Thickness [mm] Before heat resistance test After heat resistance test example 1 3.3 0.5 3.3 0.5 1.0 0.0 199 198 Example 2 3.7 0.5 3.7 0.5 1.0 0.0 198 200 Example 3 3.7 0.3 3.7 0.7 1.0 0.0 195 196 Example 4 3.7 0.2 3.7 0.5 0.7 0.0 212 205 Example 5 4.8 0.5 4.8 0.5 1.0 0.0 195 190 Example 6 5.8 0.5 5.8 0.5 1.0 0.0 200 200 Example 7 6.8 0.5 6.8 0.5 1.0 0.0 199 198 Example 8 8.2 0.5 8.2 0.5 1.0 0.0 201 210 Example 9 8.7 0.5 8.7 0.5 1.0 0.0 219 220 Example 10 8.7 0.3 8.7 0.7 1.0 0.0 210 202 Example 11 8.7 0.2 8.7 0.5 0.7 0.0 200 201 Example 12 9.6 0.5 9.6 0.5 1.0 0.0 217 216 Example 13 10.5 0.5 10.5 0.5 1.0 0.0 220 209 Example 14 12.1 0.5 12.1 0.5 1.0 0.0 212 215 Example 15 3.7 0.5 4.8 0.5 1.0 1.1 192 182 Example 16 8.7 0.5 9.6 0.5 1.0 0.9 210 200 Example 17 8.2 0.5 8.7 0.5 1.0 0.5 203 197 Example 18 3.7 0.7 - - 0.7 0.0 192 40 Example 19 3.7 0.7 - - 0.7 0.0 210 210

<Summary of evaluation results> As shown in Table 1 above, in Examples 1 to 17 satisfying the specific requirements, the change in the amount of warpage before and after the heat resistance test was small, and the heat resistance was excellent. In Example 18, although a warped glass substrate can be produced from a silicon nitride film (SiN film), the stress of the SiN film is relaxed due to the heating in the heat resistance test, and the amount of warpage becomes small. Thus, in Example 18, warpage in the semiconductor process could not be suppressed. In Example 19, there was no change in the amount of warpage before and after the heat resistance test, and there was no problem. However, since molding was performed at a high temperature, it was difficult to produce a glass substrate having warpage with high molding accuracy. It is disadvantageous in terms of production efficiency such as production volume per unit time, and production cost.

The present invention has been described in detail with reference to the specific embodiment, but it is understood by those skilled in the art that various changes and corrections can be added without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2020-134018 filed on August 6, 2020, the contents of which are incorporated herein by reference.

10: Second glass substrate 10a, 10b, 12a, 14a, 50a: Surface 12: Thermosetting resin layer 13: Resin layer 14: The first glass substrate 16: Precursor Laminate 16c: Perimeter 19: Silicon nitride film 20: Mold 22: Upper die 22a: Recess 24: Lower die 24a: convex part 26: Bolts 27: Nut 30: Laminate 40: Semiconductor packaging 42: Rewiring layer 44: Electronics 46: Resin 50: Precision Platform 52: Laser Displacement Meter 60: 1st glass substrate B: Flat D: diameter L: laser light h: total thickness hc: maximum height within the plane hi: the height of the end hm: the minimum height within the plane

FIGS. 1( a ) to ( d ) are schematic cross-sectional views showing a method for producing a layered body according to an embodiment of the present invention in order of steps. FIG. 2 is a schematic cross-sectional view showing an example of the laminate according to the embodiment of the present invention. 3 is a schematic cross-sectional view showing an example of a use example of the laminate according to the embodiment of the present invention. FIGS. 4( a ) and ( b ) are schematic cross-sectional views illustrating a method of measuring the amount of warpage of the laminate according to the embodiment of the present invention. FIG. 5 is a schematic diagram illustrating a method of measuring the amount of warpage in Example 18. FIG. FIG. 6 is a schematic diagram illustrating a method of measuring the amount of warpage in Example 19. FIG.

10: Second glass substrate

10a: Surface

10b: Surface

12: Thermosetting resin layer

12a: Surface

14: The first glass substrate

14a: Surface

16: Precursor Laminate

16c: Perimeter

20: Mold

22: Upper die

22a: Recess

24: Lower die

24a: convex part

26: Bolts

27: Nut

Claims (12)

A method of manufacturing a layered product, comprising the following steps: forming a precursor laminate having two glass substrates and a thermosetting resin layer disposed between the two glass substrates; and A laminate is obtained, and the thermosetting resin layer is thermally cured in a state in which the precursor laminate is deformed to form a resin layer, thereby obtaining a laminate comprising the above-mentioned two glass substrates and the two The resin layer between the glass substrates has warpage. The method for producing a laminate according to claim 1, wherein the difference between the average thermal expansion coefficients of the two glass substrates is 1.5 ppm/°C or less. The method for producing a laminate according to claim 1 or 2, further comprising the step of chamfering, grinding, and grinding the glass substrate of the precursor laminate after the step of forming the precursor laminate. one. The manufacturing method of the laminated body of any one of Claims 1-3 whose temperature of the said thermosetting resin layer at the time of said thermosetting is 400 degrees C or less. The method for producing a laminate according to any one of claims 1 to 3, wherein the thermosetting of the thermosetting resin layer is performed at a temperature 20° C. or more higher than the thermosetting initiation temperature of the thermosetting resin layer . A laminate having a first glass substrate, a resin layer, and a second glass substrate in this order, and The above-mentioned laminated body has warpage. The laminate according to claim 6, wherein the first glass substrate, the resin layer, and the second glass substrate are bent so that the outer surface of the first glass substrate is convex, and on the bent first glass substrate Configure the electronics. The layered product according to claim 6 or 7, wherein the difference between the average thermal expansion coefficients of the first glass substrate and the second glass substrate is 1.5 ppm/°C or less. The laminate according to any one of claims 6 to 8, wherein the total thickness of the laminate is 0.3 to 3.0 mm. The laminated body according to any one of claims 6 to 9, wherein the amount of warpage of the laminated body exceeds 0 μm and is 500 μm or less. The laminate according to any one of claims 6 to 10, wherein the amount of warpage of the laminate after being heated at 250° C. for 3 hours exceeds 0 μm and is 500 μm or less. A method of manufacturing a semiconductor package, comprising the following steps: preparing a laminate having a first glass substrate, a resin layer, and a second glass substrate in this order and having warpage; forming a rewiring layer on the outer surface of the first glass substrate; electrically connecting the semiconductor device with the redistribution layer; sealing the above-mentioned semiconductor device with resin; and The said rewiring layer mounted with the said semiconductor device sealed with the said resin is peeled from the said 1st glass substrate.

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