Method for manufacturing semiconductor device, thermosetting resin composition, and die cutting and bonding integrated film

Abstract

The invention relates to a method for manufacturing a semiconductor device, a thermosetting resin composition, and a die cutting and bonding integrated film. A method for manufacturing a semiconductor device according to one aspect of the present invention comprises: a step for preparing a die-bonding integrated film provided with an adhesive layer formed from a thermosetting resin composition having a melt viscosity at 120 DEG C of 3100 Pa * s or more, a pressure-sensitive adhesive layer, and a base film; a step for bonding the semiconductor wafer to a surface on the adhesive layer side of the die-bonding integrated film; a step for dicing the semiconductor wafer; a step for obtaining a semiconductor element with an adhesive by expanding the base film; picking up the semiconductor element with the adhesive from the pressure-sensitive adhesive layer; a step in which the semiconductor element is laminated on another semiconductor element via the adhesive; and a step for thermally curing the adhesive.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 201980045678.2, filed on July 10, 2019, with a priority date of July 11, 2018, entitled "Method for manufacturing a semiconductor device, thermosetting resin composition and integrated crystal-cut and crystal-bonded film". Technical Field

[0002] This invention relates to a method for manufacturing a semiconductor device, a thermosetting resin composition, and a die-cutting and die-bonding integrated film. Background Technology

[0003] Semiconductor devices are manufactured through the following processes. First, a semiconductor wafer is fixed in place using a pressure-sensitive adhesive sheet, in which the semiconductor wafer is monolithically formed into a semiconductor chip. Subsequently, expansion, pick-up, die bonding, reflow, and die bonding processes are performed.

[0004] One of the key characteristics required for semiconductor devices is connection reliability. To improve connection reliability, development is underway of film-type adhesives for die bonding that take into account properties such as heat resistance, moisture resistance, and reflow resistance. For example, Patent Document 1 discloses an adhesive sheet containing a resin and fillers, wherein the resin comprises a high molecular weight component and a thermosetting component primarily composed of epoxy resin.

[0005] Previous technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2016-190964 Summary of the Invention

[0006] The technical problem to be solved by the invention The inventors are developing a thermosetting adhesive for use in the manufacturing process of semiconductor devices (e.g., three-dimensional NAND memory) that achieve high capacity by stacking semiconductor elements into multiple segments. Three-dimensional NAND wafers contain complex circuit layers and relatively thin semiconductor layers (e.g., about 15 μm to 25 μm), thus presenting a problem where the semiconductor elements obtained by monolithically stacking them are prone to warping.

[0007] Figure 5 (a) is a schematic cross-sectional view of a structure in the manufacturing process of a semiconductor device. Figure 5(a) The structure 30 shown includes: a substrate 10 and four semiconductor elements S1, S2, S3, and S4 stacked on the substrate 10. In order to connect with electrodes (not shown) formed on the surface of the substrate 10, the four semiconductor elements S1, S2, S3, and S4 are stacked at offset positions in the lateral direction (orthogonal to the stacking direction) (see reference). Figure 1 Semiconductor element S1 is glued to substrate 10 by an adhesive, and adhesive is also present between the three semiconductor elements S2, S3 and S4.

[0008] According to the research of the inventors, when semiconductor element S1, semiconductor element S2, semiconductor element S3, and semiconductor element S4 each have a complex circuit layer (upper surface side) and a relatively thin semiconductor layer (lower surface side), such as Figure 5 As shown in (b), delamination easily occurs between the semiconductor element S1 in the first segment and the semiconductor element S2 in the second segment. The inventors speculate as follows regarding the reason for this.

[0009] • As described above, due to the complex circuit layers and thin semiconductor layers, semiconductor elements S1, S2, S3, and S4 have a tendency to warp (warping stress).

[0010] • A protrusion H is formed by stacking multiple semiconductor elements in a laterally staggered manner.

[0011] • It has been confirmed that no peeling will occur during the stage of installing the second semiconductor element S2. Therefore, by installing the third semiconductor element S3 and the fourth semiconductor element S4, the upward force (warping stress in the direction of peeling from the first semiconductor element S1) in the overhang of the second semiconductor element S2 increases.

[0012] The present invention addresses the aforementioned problems by providing a method for manufacturing a semiconductor device, wherein the semiconductor device is a semiconductor device in which multiple semiconductor elements are stacked, and it is difficult to generate delamination between adjacent semiconductor elements. Furthermore, the present invention also provides a thermosetting resin composition and a die-cutting and die-bonding integrated film suitable for use in this manufacturing method.

[0013] means for solving technical problems One aspect of the present invention provides a method for manufacturing a semiconductor device (e.g., a three-dimensional NAND flash memory) in which multiple semiconductor elements are stacked. The manufacturing method includes: a step of preparing a die-cutting and die-bonding integrated film, the die-cutting and die-bonding integrated film sequentially comprising an adhesive layer, a pressure-sensitive adhesive layer, and a substrate film, the adhesive layer being formed of a thermosetting resin composition having a melt viscosity of 3100 Pa·s or higher at 120°C; a step of bonding the adhesive layer side of the die-cutting and die-bonding integrated film to a semiconductor wafer; a step of dicing the semiconductor wafer; a step of obtaining a semiconductor element with adhesive by monolithizing the semiconductor wafer and the adhesive layer by expanding the substrate film; a step of picking up the semiconductor element with adhesive from the pressure-sensitive adhesive layer; a step of stacking the semiconductor element with adhesive on other semiconductor elements via the adhesive of the semiconductor element with adhesive; and a step of thermally curing the film-like adhesive.

[0014] As a thermosetting resin composition, by using a composition with a melt viscosity of 3100 Pa·s or higher at 120°C, interfacial bonding force capable of withstanding the warping stress can be achieved even if the semiconductor element to be bonded has strong warping stress. Therefore, even when multiple semiconductor elements are stacked, delamination between adjacent semiconductor elements can be sufficiently suppressed.

[0015] For example, in order to obtain semiconductor devices by monolithically integrating thinner semiconductor wafers, from the viewpoint of high yield, it is preferable to expand the semiconductor wafer under cooling conditions (e.g., -15°C to 0°C) after stealth dicing or blade dicing.

[0016] One aspect of the present invention provides a thermosetting resin composition for use in the manufacturing process of a semiconductor device, wherein the thermosetting resin composition has a melt viscosity of 3100 Pa·s or higher at 120°C. This thermosetting resin composition is suitable for use in the aforementioned semiconductor device manufacturing method.

[0017] The thermosetting resin composition contains a thermosetting resin, a high molecular weight component (e.g., acrylic resin) with a molecular weight of 100,000 to 1,000,000, and fillers. Based on the total mass of the thermosetting resin composition, the content of the high molecular weight component is preferably 15% to 50% by mass, and the content of the filler is preferably 25% to 45% by mass. By setting the contents of the high molecular weight component and the filler within the above ranges, it is possible to more efficiently and stably fabricate adhesive-coated semiconductor devices by expanding and picking them up under cooling conditions after stealth dicing or blade dicing of semiconductor wafers.

[0018] This invention provides a die-cutting and die-bonding integrated film comprising: a pressure-sensitive adhesive layer; and an adhesive layer formed from the aforementioned thermosetting resin composition. This integrated film is suitable for use in the aforementioned semiconductor device manufacturing method. From the viewpoint of cost and adhesive strength, the thickness of the adhesive layer is, for example, 3 μm to 40 μm.

[0019] Invention Effects According to the present invention, a method for manufacturing a semiconductor device is provided, wherein the semiconductor device is a semiconductor device in which multiple semiconductor elements are stacked, and peeling between adjacent semiconductor elements is not easily generated. Furthermore, according to the present invention, a thermosetting resin composition and a die-cutting and die-bonding integrated film suitable for the above-described manufacturing method are also provided. Attached Figure Description

[0020] Figure 1 This is a cross-sectional view schematically representing an example of a semiconductor device.

[0021] Figure 2 This is a cross-sectional view schematically illustrating an example of an adhesive-coated semiconductor element comprising a film adhesive and a semiconductor element.

[0022] Figure 3 (a) ~ Figure 3 (f) is a cross-sectional view schematically illustrating the process of manufacturing a semiconductor device with adhesive.

[0023] Figure 4 It is a schematic representation of manufacturing. Figure 1 A cross-sectional view of the process of the semiconductor device shown.

[0024] Figure 5 (a) is a schematic representation of manufacturing. Figure 1 A cross-sectional view of the process of the semiconductor device shown. Figure 5 (b) is a cross-sectional view showing the structure in which a stripping occurs between the semiconductor element in the first segment and the semiconductor element in the second segment.

[0025] Figure 6 It is a schematic representation of manufacturing. Figure 1 A cross-sectional view of the process of the semiconductor device shown.

[0026] Figure 7 This is a cross-sectional view schematically representing another example of a semiconductor device. Detailed Implementation

[0027] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, identical or equivalent parts will be labeled with the same symbols, and repeated descriptions will be omitted. Furthermore, unless otherwise specified, positional relationships such as up, down, left, and right refer to the positional relationships shown in the drawings. Moreover, the scale of the drawings is not limited to the scales shown. Additionally, in this specification, "(meth)acrylic acid" refers to "acrylic acid" and its corresponding "methacrylic acid".

[0028] Semiconductor Devices Figure 1 This is a schematic cross-sectional view of the semiconductor device according to this embodiment. The semiconductor device 100 shown in this figure includes: a substrate 10; four semiconductor elements S1, S2, S3, and S4 stacked on the surface of the substrate 10; wires W1, W2, W3, and W4 electrically connecting electrodes (not shown) on the surface of the substrate 10 to the four semiconductor elements S1, S2, S3, and S4; and a sealing layer 50 sealing these.

[0029] The substrate 10 may be an organic substrate, or a metal substrate such as a lead frame. Regarding the substrate 10, from the viewpoint of suppressing warping of the semiconductor device 100, the thickness of the substrate 10 may be, for example, 90 μm to 180 μm, or 90 μm to 140 μm.

[0030] Four semiconductor elements S1, S2, S3, and S4 are bonded together via a film adhesive 3P (reference). Figure 2 The semiconductor elements S1, S2, S3, and S4 are stacked in layers as a solidified mixture. When viewed from above, the shapes of the semiconductor elements S1, S2, S3, and S4 are, for example, rectangular (square or elongated). The length of one side of each semiconductor element S1, S2, S3, and S4 is, for example, less than 5 mm, but can also be 2 mm to 4 mm or 1 mm to 4 mm. The thickness of each semiconductor element S1, S2, S3, and S4 is, for example, 10 μm to 170 μm, but can also be 10 μm to 30 μm. Furthermore, the length of one side of each of the four semiconductor elements S1, S2, S3, and S4 can be the same or different, and the same applies to their thicknesses.

[0031] <Semiconductor components with adhesive> Figure 2 This is a cross-sectional view schematically illustrating an example of a semiconductor element with adhesive. Figure 2 The semiconductor device 20 shown with adhesive includes a film adhesive 3P and a semiconductor device S1. For example... Figure 2As shown, the film adhesive 3P and the semiconductor element S1 are essentially the same size. The same applies to the film adhesive 3P and semiconductor elements S2, S3, and S4. As explained below, the semiconductor element 20 with adhesive is manufactured through a dicing process and a pick-and-place process.

[0032] refer to Figure 3 (a) ~ Figure 3 (f), for Figure 2 An example of a method for fabricating the semiconductor element 20 with adhesive (a laminate of film adhesive 3P and semiconductor element S1) will be described. First, a die-cut and die-bonded integrated film 8 (hereinafter referred to as "film 8") is prepared and placed in a prescribed apparatus (not shown). Film 8 sequentially comprises a substrate film 1, a pressure-sensitive adhesive layer 2, and an adhesive layer 3A. The substrate film 1 is, for example, a polyethylene terephthalate film (PET film). The semiconductor wafer W is, for example, a thin semiconductor wafer with a thickness of 10 μm to 100 μm. The semiconductor wafer W can be monocrystalline silicon, polycrystalline silicon, various ceramics, gallium arsenide, or other compound semiconductors.

[0033] As described later, adhesive layer 3A is formed from a thermosetting resin composition. From the viewpoint of cost and adhesive strength of the cured product, the thickness of adhesive layer 3A is, for example, 3 μm to 40 μm, or 3 μm to 30 μm or 3 μm to 25 μm.

[0034] like Figure 3 (a) and Figure 3 As shown in (b), the film 8 is attached such that the adhesive layer 3A contacts one side of the semiconductor wafer W. This process is preferably performed at a temperature of 50°C to 100°C, more preferably at a temperature of 60°C to 80°C. If the temperature is above 50°C, good adhesion between the semiconductor wafer W and the adhesive layer 3A can be obtained, and if the temperature is below 100°C, excessive flow of the adhesive layer 3A can be suppressed in this process.

[0035] like Figure 3 As shown in (c), a modified region R (stealth dicing) is formed on the semiconductor wafer W by irradiating it with a laser along a predetermined dicing line. Alternatively, a cut can be formed on the semiconductor wafer by cutting with a blade instead of stealth dicing. Alternatively, the semiconductor wafer W can be thinned by grinding before laser irradiation or blade cutting.

[0036] like Figure 3 As shown in (d), the semiconductor wafer W is segmented in the modified region R by expanding the substrate film 1 under ambient temperature or cooling conditions. This monolithizes the semiconductor wafer W into multiple semiconductor elements S1, and monolithizes the adhesive layer 3A into a film-like adhesive 3P. Figure 3As shown in (e), when the pressure-sensitive adhesive layer 2 is, for example, a UV-curable type, in a state where the adhesive-coated semiconductor elements 20 are separated from each other by expansion, the pressure-sensitive adhesive layer 2 is cured by irradiating it with ultraviolet light, thereby reducing the bond force between the pressure-sensitive adhesive layer 2 and the adhesive layer 3A. After ultraviolet irradiation, the adhesive-coated semiconductor elements 20 are peeled off from the pressure-sensitive adhesive layer 2 by using a needle 42 to lift them, and the adhesive-coated semiconductor elements 20 are attracted and picked up by a suction chuck 44 (see reference). Figure 3 (f)). Obtained in this manner Figure 2 The semiconductor element 20 with adhesive shown.

[0037] From the viewpoint of obtaining a film-like adhesive 3P of a specified shape and size by properly dividing the adhesive layer 3A, the expansion of the substrate film 1 is preferably carried out under cooling conditions. Such temperature conditions may be, for example, -15°C to 0°C.

[0038] <Methods for Manufacturing Semiconductor Devices> refer to Figures 4-6 The manufacturing method of the semiconductor device 100 will be described. First, as follows... Figure 4 As shown, a first semiconductor element S1 is pressed onto the surface of the substrate 10. That is, the semiconductor element S1 is pressed onto a predetermined position on the substrate 10 via a film adhesive 3P of the semiconductor element 20 with adhesive. This pressing process is preferably performed, for example, at 80°C to 180°C and 0.01 MPa to 0.50 MPa for 0.5 to 3.0 seconds. Next, the film adhesive 3P is cured by heating. This curing process is preferably performed, for example, at 60°C to 175°C and 0.01 MPa to 1.0 MPa for 5 minutes or more. Thus, the film adhesive 3P is cured to become cured material 3. From the viewpoint of reducing voids, the curing process of the film adhesive 3P can also be performed under pressure.

[0039] Similar to the mounting of semiconductor element S1 relative to substrate 10, a second semiconductor element S2 is mounted on the surface of semiconductor element S1. Furthermore, by mounting a third semiconductor element S3 and a fourth semiconductor element S4, a semiconductor device is fabricated. Figure 5 (a) shows the structure 30. After semiconductor elements S1, S2, S3, and S4 are electrically connected to the substrate 10 using wires W1, W2, W3, and W4 (see reference). Figure 5 The semiconductor components and wires are sealed by the sealing layer 50, thereby forming a semiconductor device. Figure 1 The semiconductor device 100 shown.

[0040] <Thermosetting Resin Composition> The thermosetting resin composition constituting the film adhesive 3P will be described. Furthermore, the film adhesive 3P is a film adhesive obtained by monolithically forming the adhesive layer 3A, and both are formed from the same thermosetting resin composition. This thermosetting resin composition can, for example, pass through a semi-cured state (stage B) and then, through a subsequent curing process, become a fully cured product (stage C).

[0041] The thermosetting resin composition has a melt viscosity of 3100 Pa·s or higher at 120°C. By using the thermosetting resin composition, even if the semiconductor element to be bonded has strong warpage stress, an interfacial adhesive force capable of withstanding said warpage stress can be achieved. Therefore, even when multiple semiconductor elements are stacked, delamination between adjacent semiconductor elements can be sufficiently suppressed. The melt viscosity of the thermosetting resin composition at 120°C can be 3100 Pa·s to 40000 Pa·s, or 5000 Pa·s to 35000 Pa·s. The lower limit of this melt viscosity can be 13000 Pa·s or 14000 Pa·s. Furthermore, the melt viscosity refers to the measured value under the following conditions: using ARES (manufactured by TA Instruments), while applying a 5% strain to the thermosetting resin composition formed into a film, the temperature is increased at a rate of 5°C / min, and the measurement is performed simultaneously.

[0042] Regarding the thermosetting resin composition (before curing), for example, the storage modulus at 35°C is 70 MPa or higher. By using this thermosetting resin composition, even if the semiconductor element to be bonded has strong warpage stress, cohesion capable of withstanding said warpage stress can be achieved. Therefore, even when multiple semiconductor elements are stacked, delamination between adjacent semiconductor elements can be sufficiently suppressed. The storage modulus of the thermosetting resin composition at 35°C can be 70 MPa to 1000 MPa, or 80 MPa to 900 MPa. Furthermore, the storage modulus refers to a value obtained by measurement based on the following apparatus and conditions.

[0043] • Dynamic viscoelasticity measuring device: Rheogel E-4000 (manufactured by UBM Corporation) • Test subject: Thermosetting resin composition formed into a film • Heating rate: 3℃ / minute • Frequency: 10Hz Thermosetting resin compositions preferably contain the following components.

[0044] (a) Thermosetting resin (hereinafter sometimes simply referred to as "(a) component") (b) High molecular weight components (hereinafter sometimes referred to as "(b) components") (c) Filler (hereinafter sometimes simply referred to as "(c) component") In this embodiment, when (a) the thermosetting resin includes epoxy resin (hereinafter, sometimes simply referred to as "component (a1)"), (a) the thermosetting resin preferably includes phenolic resin (hereinafter, sometimes simply referred to as "component (a2)") which can serve as a curing agent for epoxy resin. Furthermore, when (b) the high molecular weight component has functional groups (such as glycidyl groups) that can be thermosetting with phenolic resin, epoxy resin may not be used separately as the thermosetting resin (a).

[0045] Thermosetting resin compositions may also contain the following components.

[0046] (d) Coupling agent (hereinafter sometimes simply referred to as "(d) component") (e) Curing accelerator (hereinafter sometimes simply referred to as "(e) component") Based on the total mass of the thermosetting resin composition, the content of component (a) is, for example, 30% by mass or less, or 5% by mass to 30% by mass. Based on the total mass of the thermosetting resin composition, the content of component (b) is, for example, 15% by mass to 66% by mass, or 15% by mass to 50% by mass. Based on the total mass of the thermosetting resin composition, the content of component (c) is, for example, 25% by mass to 50% by mass, or 25% by mass to 45% by mass. By setting the contents of components (b) and (c) within the above ranges, it is possible to more efficiently and stably manufacture adhesive-bonded semiconductor devices by expanding and picking them up under cooling conditions after stealth dicing or blade dicing of semiconductor wafers.

[0047] Specifically, when the content of component (b) is 66% by mass or less, excellent splitting properties tend to be obtained when expansion is carried out under cooling conditions (see reference). Figure 3 (d) Furthermore, with component (b) having a content of 15% by mass or more and component (c) having a content of 50% by mass or less, the bulk intensity under cooling conditions is sufficiently high, making it easy to expand and cut into the specified shapes and sizes. Additionally, to set the melt viscosity of the thermosetting resin composition at 120°C within the aforementioned range, the amounts of (a) the thermosetting resin, (b) the high molecular weight component, and (c) the filler can be appropriately adjusted.

[0048] From the viewpoint of connection reliability, the storage modulus of the cured thermosetting resin composition (C stage) at 150°C is preferably 10 MPa or more, more preferably 25 MPa or more, and may also be 50 MPa or more or 100 MPa or more. Furthermore, the upper limit of the storage modulus is, for example, 600 MPa, and may also be 500 MPa. The storage modulus of the cured thermosetting resin composition at 150°C can be measured using a dynamic viscoelastic apparatus as a sample formed by curing the thermosetting resin composition at 175°C.

[0049] The following describes the components contained in the thermosetting resin composition.

[0050] • (a) Thermosetting resins (a1) Any component containing an epoxy group within its molecule can be used without particular restriction. Examples of components (a1) include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic varnish type epoxy resin, cresol varnish type epoxy resin, bisphenol A varnish type epoxy resin, bisphenol F varnish type epoxy resin, epoxy resin containing a dicyclopentadiene skeleton, stilbene type epoxy resin, epoxy resin containing a triazine skeleton, epoxy resin containing a fluorene skeleton, pyrophenol methane type epoxy resin, biphenyl type epoxy resin, xylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, polyfunctional phenols, anthracene, and other polycyclic aromatic diglycidyl ether compounds. These can be used alone or in combination of two or more. Of these, from the viewpoint of heat resistance, component (a1) may be cresol varnish-type epoxy resin, bisphenol F type epoxy resin or bisphenol A type epoxy resin.

[0051] The epoxy equivalent of component (a1) can be 90 g / eq to 300 g / eq, 110 g / eq to 290 g / eq, or 130 g / eq to 280 g / eq. If the epoxy equivalent of component (a1) is in this range, it tends to maintain the overall strength of the film adhesive while ensuring its flowability.

[0052] Relative to the total mass of components (a), (b), and (c) 100 parts by mass, the content of component (a1) can be less than 50 parts by mass, 5 to 50 parts by mass, 10 to 40 parts by mass, or 20 to 30 parts by mass. If the content of component (a1) is more than 5 parts by mass, the film adhesive tends to have better embedding properties. If the content of component (a1) is less than 50 parts by mass, it tends to further inhibit the occurrence of exudation.

[0053] (a2) Any component containing a phenolic hydroxyl group within its molecule can be used without particular restriction. Examples of components (a2) include: phenolic varnish-type phenolic resins obtained by condensing or co-condensing phenolic compounds such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc., and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthol, etc., with aldehyde compounds such as formaldehyde under an acidic catalyst; phenolic aralkyl resins and naphthol aralkyl resins synthesized from allylated bisphenol A, allylated bisphenol F, allylated naphthalene glycol, phenolic varnish, phenol, and / or naphthols with dimethoxy-p-xylene or bis(methoxymethyl)biphenyl. These can be used alone or in combination of two or more. Among these, from the viewpoint of hygroscopicity and heat resistance, component (a2) may be phenolic alkyl resin, naphthol alkyl resin or phenolic varnish type phenolic resin.

[0054] The hydroxyl equivalent of component (a2) can be 80 g / eq to 250 g / eq, 90 g / eq to 200 g / eq, or 100 g / eq to 180 g / eq. If the hydroxyl equivalent of component (a2) is in this range, it tends to maintain the fluidity of the film adhesive while maintaining higher adhesive strength.

[0055] (a2) The softening point of the component may be 50℃~140℃, 55℃~120℃, or 60℃~100℃.

[0056] Relative to the total mass of components (a), (b), and (c) 100 parts by mass, the content of component (a2) can be 5 to 50 parts by mass, 10 to 40 parts by mass, or 20 to 30 parts by mass. If the content of component (a2) is 5 parts by mass or more, better curing properties tend to be obtained. If the content of component (a2) is less than 50 parts by mass, better embedding properties of the film adhesive tend to be obtained.

[0057] From the perspective of curability, the ratio of the epoxy equivalent of component (a1) to the hydroxyl equivalent of component (a2) (epoxy equivalent of component (a1) / hydroxyl equivalent of component (a2)) can be 0.30 / 0.70 to 0.70 / 0.30, 0.35 / 0.65 to 0.65 / 0.35, 0.40 / 0.60 to 0.60 / 0.40, or 0.45 / 0.55 to 0.55 / 0.45. If this equivalent ratio is 0.30 / 0.70 or higher, more sufficient curability is obtained. If this equivalent ratio is 0.70 / 0.30 or lower, excessive viscosity can be prevented, and more sufficient flowability can be obtained.

[0058] • (b) High molecular weight components (b) The preferred component is one with a glass transition temperature (Tg) of 50°C or lower. Examples of components (b) include: acrylic resin, polyester resin, polyamide resin, polyimide resin, silicone resin, butadiene resin, acrylonitrile resin, and their modifiers.

[0059] From a flowability perspective, component (b) may contain acrylic resin. Here, acrylic resin refers to a polymer containing structural units derived from (meth)acrylates. Preferably, the acrylic resin is a polymer containing structural units derived from (meth)acrylates having crosslinking functional groups such as epoxy groups, alcoholic or phenolic hydroxyl groups, or carboxyl groups. Furthermore, the acrylic resin may also be an acrylic rubber, such as a copolymer of (meth)acrylate and acrylonitrile.

[0060] The glass transition temperature (Tg) of acrylic resin can be -50°C to 50°C or -30°C to 30°C. If the Tg of the acrylic resin is above -50°C, it tends to prevent the adhesive composition from becoming too flexible. Therefore, the film adhesive is easily cut during wafer dicing, preventing burrs. If the Tg of the acrylic resin is below 50°C, it tends to suppress the decrease in the flexibility of the adhesive composition. Therefore, when the film adhesive is attached to the wafer, it tends to easily embed the voids sufficiently. Furthermore, it can prevent chipping during dicing caused by a decrease in wafer adhesion. Here, the glass transition temperature (Tg) refers to the value measured using DSC (Differential Scanning Calorimetry) (e.g., Rigaku Corporation's "Thermo Plus 2").

[0061] The weight-average molecular weight (Mw) of acrylic resins is, for example, 100,000 to 3,000,000, and can be 100,000 to 1,000,000, 100,000 to 800,000, or 300,000 to 2,000,000. If the Mw of the acrylic resin is within this range, film-forming properties, film strength, flexibility, viscosity, etc., can be appropriately controlled, and excellent reflux properties can be achieved, improving embeddability. Here, Mw refers to the value determined by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

[0062] Commercially available acrylic resins include, for example: SG-70L, SG-708-6, WS-023 EK30, SG-P3, SG-280 EK23, HTR-860P-3CSP, and HTR-860P-3CSP-3DB (all manufactured by Nagase ChemteX Corporation).

[0063] Relative to the total mass of components (a), (b), and (c) 100 parts by mass, the content of component (b) can be 5 to 70 parts by mass, 10 to 50 parts by mass, or 15 to 30 parts by mass. If the content of component (b) is 5 parts by mass or more, the flowability control during molding and the operability at high temperatures can be further improved. If the content of component (b) is 70 parts by mass or less, the embeddability can be further improved.

[0064] •(c) packing Component (c) may include, for example, inorganic fillers such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, and silicon dioxide. These may be used alone or in combination of two or more. Of these, from the viewpoint of resin compatibility, component (c) may be silicon dioxide.

[0065] From the perspective of improving adhesiveness, the average particle size of component (c) can be 0.005 μm to 1 μm or 0.05 μm to 0.5 μm. Here, the average particle size refers to the value obtained by conversion based on the BET specific surface area.

[0066] Relative to the total mass of components (a), (b), and (c) 100 parts by mass, the content of component (c) can be 5 to 50 parts by mass, 15 to 45 parts by mass, or 25 to 40 parts by mass. If the content of component (c) is 5 parts by mass or more, the fluidity of the film adhesive tends to be further improved. If the content of component (c) is less than 50 parts by mass, the cutting properties of the film adhesive tend to be better.

[0067] • (d) Coupling agents (d) The component may be a silane coupling agent. Examples of silane coupling agents include: γ-ureopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

[0068] The content of component (d) can be 0.01 to 5 parts by mass relative to the total mass of components (a), (b) and (c) of 100 parts by mass.

[0069] • (e) Curing accelerator (e) There are no particular limitations on the ingredients; commonly used ingredients may be used. Examples of ingredients (e) include: imidazoles and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, etc. These may be used alone or in combination of two or more. Among these, from a reactivity point of view, imidazoles and their derivatives may be used.

[0070] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. These can be used alone or in combination of two or more.

[0071] The content of component (e) may be 0.01 to 1 part by mass relative to the total mass of components (a), (b) and (c) of 100 parts by mass.

[0072] <Integrated Crystal-Cutting and Crystal-Bonding Film and its Manufacturing Method> right Figure 3 (a) The integrated crystal-cut and crystal-bonded film 8 and its manufacturing method are described. The manufacturing method of film 8 includes: a step of applying a varnish containing a solvent-based adhesive composition to a substrate film (not shown) for the adhesive layer; and a step of forming the adhesive layer 3A by heating and drying the applied varnish at 50°C to 150°C.

[0073] Varnishes of adhesive compositions can be prepared, for example, by mixing or kneading components (a) to (c), and, if necessary, components (d) and (e) in a solvent. Mixing or kneading can be carried out using conventional mixers, pounders, three-rod roll mills, ball mills, or other dispersants, in appropriate combinations.

[0074] The solvent used to make the varnish can be any conventionally known solvent, as long as it can uniformly dissolve, mix, or disperse the above-mentioned components. Examples of such solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, and xylene. Methyl ethyl ketone and cyclohexanone are preferred for their fast drying speed and low cost.

[0075] There are no particular limitations on the substrate film used as an adhesive layer. Examples include: polyester film, polypropylene film (OPP film, etc.), polyethylene terephthalate film, polyimide film, polyetherimide film, polyether naphthalene ester film, methylpentene film, etc.

[0076] As a method for applying varnish to a substrate film, known methods can be used, such as: blade coating, roller coating, spray coating, gravure coating, bar coating, curtain coating, etc. There are no particular restrictions on the heating and drying conditions, as long as the solvent used is sufficiently evaporated; for example, heating at 50°C to 150°C for 1 to 30 minutes can be performed. Heating and drying can be carried out in stages within the temperature range of 50°C to 150°C. By evaporating the solvent contained in the varnish through heating and drying, a laminated film of the substrate film and the adhesive layer 20A can be obtained.

[0077] By bonding the laminated film obtained in the above manner with a cut film (a laminate of substrate film 1 and pressure-sensitive adhesive layer 2), film 8 can be obtained. Examples of substrate film 1 include: polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polyimide film, and other plastic films. Furthermore, substrate film 1 can undergo surface treatments such as primer coating, UV treatment, corona discharge treatment, polishing treatment, and etching treatment as needed. Pressure-sensitive adhesive layer 2 can be UV-curable or pressure-sensitive. Film 8 may also include a protective film (not shown) covering pressure-sensitive adhesive layer 2.

[0078] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments. For example, in the above embodiments, a package in which four semiconductor elements are stacked is illustrated, but the number of semiconductor elements stacked is not limited to this. Furthermore, in the above embodiments, a method in which multiple semiconductor elements are stacked in a staggered manner in a direction orthogonal to the stacking direction of the semiconductor elements is illustrated, but it is also possible to stack multiple semiconductor elements as described above. Figure 7 As shown, semiconductor devices are stacked in non-isolated positions.

[0079] Example The present invention will be described in more detail below with examples. However, the present invention is not limited to the following examples.

[0080] (Examples 1 to 12 and Comparative Examples 1 to 5) Varnishes containing the components shown in Tables 1 to 4 (a total of 17 types) were prepared as follows: Cyclohexanone was added to a composition containing epoxy resin and phenolic resin as thermosetting resins, and fillers, and the mixture was stirred. Acrylic rubber, as a high molecular weight component, was added and stirred, followed by the addition of a coupling agent and a curing accelerator, and stirring continued until all components were fully homogenized, thereby obtaining the varnish.

[0081] The components listed in Tables 1 to 4 are as follows.

[0082] (Epoxy resin) •YDCN-700-10: Cresol phenolic resin for clear varnish, manufactured by NIPPON STEEL Chemical & Material Co., Ltd., with an epoxy equivalent of 210 and a softening point of 75℃~85℃. •EXA-830CRP (trade name): Bisphenol F type epoxy resin, manufactured by DIC Corporation, epoxy equivalent 162, liquid at room temperature. •YDF-8170C: Bisphenol F type epoxy resin, manufactured by NIPPON STEEL Chemical & Material Co., Ltd., with an epoxy equivalent of 159, and is liquid at room temperature. (Phenolic resin) • Mirex XLC-LL (“Mirex” is a registered trademark): Manufactured by Mitsui Chemicals, Inc., with a hydroxyl equivalent of 175 and a softening point of 77°C. • Phenolite LF-4871 (“Phenolite” is a registered trademark): Manufactured by DIC Corporation, with a hydroxyl equivalent of 118 and a softening point of 130°C. (High molecular weight components) •HTR-860P: Manufactured by Nagase ChemteX Corporation, acrylic rubber, weight-average molecular weight of 800,000, Tg of -7℃ (filler) •SC-2050-HLG: Manufactured by Admatechs, silica filler dispersion with an average particle size of 0.50 μm and a maximum particle size of less than 1.0 μm. •Aerosil R972 (“Aerosil” is a registered trademark): Manufactured by NIPPON AEROSIL CO., LTD., silica particles with an average particle size of 0.016 μm and a maximum particle size of less than 1.0 μm. (Coupled agent) • A-189: γ-Mercaptopropyltrimethoxysilane, manufactured by Momentive Performance Materials Inc. • A-1160: γ-Ureapropyltriethoxysilane, manufactured by Momentive Performance Materials Inc. (Curing accelerator) • Curezol 2PZ-CN (“Curezol” is a registered trademark): 1-Cyanoethyl-2-phenylimidazolium, manufactured by SHIKOKUCHEMICALS CORPORATION. The varnish was filtered through a 500-mesh filter and then defoamed under vacuum. The defoamed varnish was then applied to a polyethylene terephthalate (PET) film (38 μm thick) that had undergone mold release treatment. The applied varnish was then dried in two stages at 90°C for 5 minutes, followed by 140°C for 5 minutes. This resulted in an adhesive film (7 μm thick) with a film-like adhesive in stage B on the PET film used as the substrate.

[0083] (Determination of melt viscosity of film adhesives) The melt viscosity of the film adhesive at 120°C was determined by the following method: Multiple layers of film adhesive with a thickness of 7 μm were stacked to a thickness of approximately 300 μm, and then punched into 10 mm × 10 mm dimensions to obtain a test sample. A circular aluminum plate clamp with a diameter of 8 mm was mounted on a dynamic viscoelastic apparatus ARES (manufactured by TA Instruments), and the sample was then mounted there. Subsequently, while applying a strain of 5% at 35°C, the temperature was increased to 130°C at a heating rate of 5°C / min, and the melt viscosity at 120°C was recorded. The results are shown in Tables 1 to 4.

[0084] (Determination of storage modulus of film adhesives) The storage modulus of the film adhesive at 35°C was determined using a dynamic viscoelasticity measuring apparatus (Rheogel E-4000) manufactured by UBM Corporation. Specifically, a sample for testing was obtained by stacking multiple layers of film adhesive with a thickness of 7 μm to achieve a thickness of approximately 170 μm, and setting the sample dimensions to 4 mm wide × 33 mm long. The sample was mounted on the dynamic viscoelasticity measuring apparatus (product name: Rheogel E-4000, manufactured by UBM Corporation) and a tensile load was applied. The storage modulus at 35°C was measured at a frequency of 10 Hz and a heating rate of 3°C / min. The results are shown in Tables 1 to 4.

[0085] [Evaluation of the segmentation properties of film adhesives] A crystalline-cutter integrated film was fabricated by bonding the various film-like adhesives (120 μm thick) involved in the examples and comparative examples to a pressure-sensitive adhesive film for cutting (manufactured by Maxell, Ltd.).

[0086] As described below, the slicing properties of the film adhesive were evaluated by performing an expansion process under low-temperature conditions after forming a modified region by irradiating a semiconductor wafer with a laser. Specifically, a semiconductor wafer (silicon wafer, 50 μm thick, 12 inches in outer diameter) was prepared. A die-cutting and die-bonding integrated film was bonded to the semiconductor wafer to ensure the film adhesive adhered tightly to one side of the semiconductor wafer. Stealth cutting was performed on the laminate containing the semiconductor wafer (semiconductor wafer / film adhesive / pressure-sensitive adhesive layer / substrate layer) using a laser cutting apparatus (manufactured by TOKYO SEIMITSU CO., LTD., MAHOHDICING MACHINE). The conditions are described below.

[0087] • Laser source: Semiconductor laser-excited Nd(YAG laser) Wavelength: 1064nm Laser spot cross-sectional area: 3.14 × 10 -8 cm 2 Oscillation mode: Q-switching pulse Repetition frequency: 100kHz Pulse width: 30ns Output: 20μJ / pulse Laser quality: TEM00 Polarization characteristics: linear polarization • Concentrating lens magnification: 50x •NA: 0.55 • Transmittance to laser wavelength: 60% • Stage speed for placing semiconductor wafers: 100 mm / s A laminate (semiconductor wafer / adhesive layer / pressure-sensitive adhesive layer / substrate layer) containing the modified region is fixed to an expansion device. Next, the dicing film (pressure-sensitive adhesive layer / substrate layer) is expanded under the following conditions, thereby separating the film-like adhesive and the semiconductor wafer. Thus, a semiconductor device with adhesive is obtained.

[0088] Device: DDS2300 (Fully Automatic Die Separator) manufactured by Disco Corporation Cold expansion conditions: Temperature: -15℃, Height: 9mm, Cooling time: 60 seconds Speed: 300mm / second, Waiting time: 0 seconds For the pressure-sensitive adhesive layer after the expansion process, from the substrate layer side, with an illuminance of 70mW / cm 2Ultraviolet light was applied for 3 seconds. The pick-up performance of the adhesive-coated semiconductor device was evaluated using a flexible diebonder DB-730 (trade name) manufactured by Renesas Eastern Japan Semiconductor. The pick-up chuck was a RUBBER TIP 13-087E-33 (trade name, size: 5mm × 5mm) manufactured by Micromechanics Co., Ltd. The top pins were EJECTOR NEEDLE SEN2-83-05 (trade name, diameter: 0.7mm, front end shape: 350μm diameter semicircle) manufactured by Micromechanics Co., Ltd. Five top pins were arranged with a pin center spacing of 4.2mm. The pick-up conditions are as follows.

[0089] • Pin lifting speed: 10mm / second • Lifting height: 200μm After the stealth dicing process, the presence of any undivided semiconductor components with adhesive was visually inspected, and the evaluation was performed according to the following criteria. The results are shown in Tables 1 to 4.

[0090] A: Undivided semiconductor components with adhesive.

[0091] B: There is more than one undivided semiconductor element with adhesive.

[0092] [The presence or absence of peeling after four layers] Samples (semiconductor devices with adhesive) that were appropriately divided using a film adhesive were prepared for the examples or comparative examples, and were compared with... Figure 5 (a) shows a structure with the same structure. After stacking the fourth semiconductor element, visual inspection was conducted to determine whether delamination had occurred between the first and second segments, and the results were evaluated according to the following criteria. The results are shown in Tables 1 to 4.

[0093] A: No peeling occurred in any of the samples.

[0094] B: More than one sample has been delaminated.

[0095] [Evaluation of reflow resistance] In the samples prepared to evaluate the presence or absence of peeling, samples that did not exhibit peeling were used, and reflow resistance was evaluated using the following method. Specifically, a semiconductor device was laminated into four segments using a molding sealant (manufactured by Showa Denko Materials Co., Ltd., trade name "CEL-9750ZHF10"), thereby obtaining the evaluation package. Furthermore, the resin sealing conditions were set to 175°C / 6.7 MPa / 90 seconds, and the curing conditions were set to 175°C for 5 hours.

[0096] Twenty of the above-described packages were prepared and subjected to moisture absorption under conditions specified by JEDEC (Level 3, 30°C, 60% RH, 192 hours). The moisture-absorbed packages were then subjected to three cycles in an IR reflow oven (260°C, maximum temperature 265°C). Evaluation was performed according to the following criteria. The results are shown in Tables 1 to 4.

[0097] A: None of the 20 packages showed signs of damage, thickness variation, or delamination at the interface between the film adhesive and the semiconductor element.

[0098] B: At least one of the 20 packages showed signs of damage, thickness variation, or delamination at the interface between the film adhesive and the semiconductor element.

[0099] [Table 1]

[0100] [Table 2]

[0101] [Table 3]

[0102] [Table 4]

[0103] Industrial availability According to the present invention, a method for manufacturing a semiconductor device is provided, wherein the semiconductor device is a semiconductor device in which multiple semiconductor elements are stacked, and peeling between adjacent semiconductor elements is not easily generated. Furthermore, according to the present invention, a thermosetting resin composition and a die-cutting and die-bonding integrated film suitable for the above-described manufacturing method are also provided.

[0104] Symbol Explanation 1-Substrate film, 2-Pressure-sensitive adhesive layer, 3-Curated film adhesive, 3A-Adhesive layer, 3P-Film adhesive, 8-Cut and bonded integrated film, 20-Semiconductor component with adhesive, 100-Semiconductor device, W-Semiconductor wafer.

Claims

1. A method for manufacturing a semiconductor device, comprising: The process of preparing a crystal-cut and crystal-bonded integrated film, wherein the crystal-cut and crystal-bonded integrated film sequentially comprises an adhesive layer, a pressure-sensitive adhesive layer and a substrate film, wherein the adhesive layer is formed of a thermosetting resin composition with a melt viscosity of 3100 Pa·s or higher at 120°C. The process of bonding the adhesive layer side of the integrated die-cutting and die-bonding film to a semiconductor wafer; The process of cutting the semiconductor wafer; The process of obtaining a semiconductor device with adhesive by monolithically forming the semiconductor wafer and the adhesive layer by expanding the substrate film; The process of picking up the adhesive-coated semiconductor element from the pressure-sensitive adhesive layer; The process of laminating the adhesive-bearing semiconductor element onto other semiconductor elements via the adhesive of the adhesive-bearing semiconductor element; and The process of heat curing the adhesive, The thermosetting resin composition contains a thermosetting resin, a high molecular weight component with a molecular weight of 100,000 to 1,000,000, and fillers. The thermosetting resin composition contains epoxy resin, and the content of the epoxy resin is 5 to 20 parts by weight relative to 100 parts by weight of the total mass of the thermosetting resin, the high molecular weight component, and the filler. Based on the total mass of the thermosetting resin composition, the content of the high molecular weight component is 30% to 66% by mass. Multiple semiconductor components are stacked in a staggered manner in the lateral direction.

2. The method for manufacturing a semiconductor device according to claim 1, wherein, The storage modulus of the thermosetting resin composition at 35°C is 80 MPa ~ 450 MPa.

3. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein, The thermosetting resin composition has a melt viscosity of 13000 Pa·s or higher at 120°C.

4. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein, The content of the high molecular weight component is 30 to 60 parts by mass relative to the total mass of the thermosetting resin, the high molecular weight component, and the filler (100 parts by mass).

5. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein, Based on the total mass of the thermosetting resin composition, the filler content is 25% to 45% by mass.

6. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein, The semiconductor wafer is monolithized by one of stealth dicing and blade dicing, and the substrate film is expanded under cooling conditions.

7. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the method is a method for manufacturing a three-dimensional NAND type memory.

8. A thermosetting resin composition used in a semiconductor device manufacturing process, The thermosetting resin composition has a melt viscosity of 3100 Pa·s or higher at 120°C. The thermosetting resin composition contains a thermosetting resin, a high molecular weight component with a molecular weight of 100,000 to 1,000,000, and fillers. The thermosetting resin composition contains epoxy resin, and the content of the epoxy resin is 5 to 20 parts by weight relative to 100 parts by weight of the total mass of the thermosetting resin, the high molecular weight component, and the filler. Based on the total mass of the thermosetting resin composition, the content of the high molecular weight component is 30% to 66% by mass.

9. The thermosetting resin composition according to claim 8, wherein the storage modulus at 35°C is 80 MPa to 450 MPa.

10. The thermosetting resin composition according to claim 8 or 9, wherein the melt viscosity at 120°C is 13000 Pa·s or higher.

11. The thermosetting resin composition according to claim 8 or 9, wherein, The content of the high molecular weight component is 30 to 60 parts by mass relative to the total mass of the thermosetting resin, the high molecular weight component, and the filler (100 parts by mass).

12. The thermosetting resin composition according to claim 8 or 9, wherein, Based on the total mass of the thermosetting resin composition, the filler content is 25% to 45% by mass.

13. The thermosetting resin composition according to claim 8 or 9, used in the manufacturing process of a three-dimensional NAND type memory.

14. The thermosetting resin composition according to claim 8 or 9, used in a method for manufacturing a semiconductor device according to any one of claims 1 to 7.

15. A crystal-cutting and crystal-adhesive integrated film, comprising: Pressure-sensitive adhesive layer; and An adhesive layer formed from the thermosetting resin composition according to any one of claims 8 to 14.

16. The integrated crystal-cutting and crystal-adhesive film according to claim 15, wherein, The thickness of the adhesive layer is 3μm to 40μm.

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