Method for cleaning semiconductor chip and method for manufacturing semiconductor device

Abstract

Provided is a method for cleaning a semiconductor chip, comprising: (a) a step for cleaning a plurality of semiconductor chips disposed in a region on the surface of an adhesive film and in a region within a dicing ring attached to the surface with a chemical solution; and (b) a step for picking up the cleaned semiconductor chip from the surface. The adhesive film includes a substrate film and an adhesive layer formed on a surface of the substrate film. The adhesive layer contains an adhesive composition containing a predetermined resin (A) and a photopolymerization initiator (B). The chemical solution is one chemical solution selected from the group consisting of a solvent system, an acid system and an alkali system.

Description

Technical Field

[0001] This invention relates to a method for cleaning a semiconductor chip and a method for manufacturing a semiconductor device. Background Technology

[0002] Conventionally, semiconductor devices are manufactured through the following processes: attaching a semiconductor wafer to a dicing bonding pad, and then monolithically converting the semiconductor wafer into a semiconductor chip (dicing process). Following this, processes such as picking up the semiconductor chip and bonding the semiconductor chip to a substrate (e.g., a substrate) are performed. With the increasing versatility of various components, stacked MCPs (Multi-Chip Packages) that achieve high capacity through multi-level stacking of semiconductor components are becoming increasingly popular. To achieve even higher levels of three-dimensional integration, hybrid bonding methods for connecting dissimilar components have also been developed. Patent Document 1 discloses bonding multiple semiconductor chips onto a substrate using hybrid bonding.

[0003] Previous technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2001-197431 Summary of the Invention

[0006] The technical problem to be solved by the invention

[0007] However, based on research conducted by the inventors and others from various perspectives toward the practical application of highly sophisticated three-dimensional integrated technologies, such as hybrid bonding, it has been found that it is useful to clean semiconductor chips more thoroughly than before before bonding them to the substrate. In the manufacturing process of semiconductor devices, foreign matter such as shavings is sometimes generated during processes such as thinning and dicing semiconductor wafers, and semiconductor chips with such foreign matter attached are then used in the next process. For example, hybrid bonding often involves bonding dissimilar components to each other on surfaces; if foreign matter remains between the two surfaces, even minute amounts of this foreign matter can reduce the connection reliability of the semiconductor device.

[0008] This invention provides a method for cleaning semiconductor chips that can effectively and efficiently remove foreign matter adhering to the semiconductor chip during the manufacturing process of a semiconductor device. Furthermore, this invention provides a method for manufacturing a semiconductor device using a semiconductor chip cleaned by this method.

[0009] means for solving technical problems

[0010] One aspect of the present invention relates to a method for cleaning semiconductor chips. The method includes: (a) cleaning a plurality of semiconductor chips disposed on a surface of an adhesive film and attached to a region within a dicing ring on the surface using a chemical solution; and (b) picking up the cleaned semiconductor chips from the surface. The adhesive film comprises a substrate film and an adhesive layer formed on the surface of the substrate film. The adhesive layer contains an adhesive composition comprising a resin (A) represented by formula (1-1) and a photopolymerization initiator (B). The chemical solution is selected from the group consisting of solvents, acids, and bases.

[0011]

[0012] In formula (1-1), k, l, m, and n represent the molar composition ratio when k + l + m + n = 100, k is greater than 0 and less than 92, l is 0 to 50, m is greater than 0 and less than 90, the sum of k, l, and m is 65 to 95, and n is 5 to 35. 1 R 2 R 3 and R 4 R is a hydrogen atom or a methyl group. 5 It is an alkyl group having 1 to 16 carbon atoms, R 6 R is an alicyclic hydrocarbon group with 3 to 30 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms. 7 It can be a hydrogen atom or -(CH2). j -COOH (where j is 1 or 2), R 8 The basis represented by equation (1-2) or equation (1-3).

[0013]

[0014] In equations (1-2) and (1-3), p and q are integers from 0 to 2. When p is 0, s is 0; when p is 1 or 2, s is 1. 9 (For hydrogen atoms or methyl groups).

[0015] Conventionally, on the surface of an adhesive film (also known as a "dicing tape") with dicing rings attached, even when water is used to clean the semiconductor chip, chemical solutions are not used to clean the semiconductor chip. That is, for example, when the semiconductor chip is bonded to a substrate via bumps formed on the semiconductor chip, water-based cleaning does not present a problem. In contrast, according to the present invention, by cleaning the semiconductor chip on the adhesive film with a chemical solution, foreign matter adhering to the semiconductor chip through various prior processes can be highly removed. By using highly cleaned semiconductor chips, excellent connectivity reliability of semiconductor devices manufactured using advanced three-dimensional integration technology can be achieved.

[0016] Furthermore, based on the research of the inventors, it was discovered that the specified resin contained in the above-mentioned adhesive composition is resistant to the chemical solution and its adhesion is not easily reduced. Therefore, according to the present invention, during the cleaning process of the semiconductor chip in the chemical solution, it is possible to prevent the semiconductor chip from detaching from the surface of the adhesive film.

[0017] The aforementioned cleaning method is useful in that it can be effectively implemented in semiconductor manufacturing processes. Specifically, in the manufacturing process of semiconductor devices, transferring semiconductor chips to a device for high-level cleaning and then returning the cleaned chips to the mounting equipment is inefficient. In contrast, according to the present invention, high-level cleaning based on the cleaning solution is performed on the surface of the adhesive film with a dicing ring attached, thus allowing the cleaned semiconductor chips to be picked up and directly supplied to the next process.

[0018] One aspect of the present invention relates to a method for manufacturing a semiconductor device. The method includes a step of bonding a semiconductor chip, having undergone a process of performing the aforementioned semiconductor chip cleaning method, to a substrate. According to this method, a highly cleaned semiconductor chip is used, thus enabling the manufacture of a semiconductor device with excellent interconnect reliability.

[0019] Invention Effects

[0020] According to the present invention, a method for cleaning a semiconductor chip is provided that can effectively and efficiently remove foreign matter adhering to the semiconductor chip during the manufacturing process of a semiconductor device. Furthermore, according to the present invention, a method for manufacturing a semiconductor device using a semiconductor chip cleaned by this method is provided. Attached Figure Description

[0021] Figure 1 This is a schematic cross-sectional view showing the state in which the cleaning method of the present invention is ready to be implemented.

[0022] Figure 2 It is a schematic cross-sectional view showing what a semiconductor chip looks like after it has been picked up and cleaned.

[0023] Figure 3 In the diagram, (a), (b), and (c) are schematic cross-sectional views illustrating the process of manufacturing a semiconductor device by the method of the first embodiment.

[0024] Figure 4 In the diagram, (a), (b), and (c) are schematic cross-sectional views illustrating the process of manufacturing a semiconductor device by the method of the first embodiment.

[0025] Figure 5 It is a cross-sectional view schematically showing how the spacing between two adjacent semiconductor chips is increased by applying tension to the adhesive film.

[0026] Figure 6 It is a schematic cross-sectional view showing a semiconductor chip bonded to a substrate.

[0027] Figure 7 It is a schematic cross-sectional view showing a state in which multiple semiconductor chips are stacked on a substrate.

[0028] Figure 8 This is a cross-sectional view schematically illustrating an example of a semiconductor device having a structure with multiple semiconductor chips stacked on top of each other.

[0029] Figure 9 In the diagram, (a) and (b) are schematic cross-sectional views illustrating the process of manufacturing a semiconductor device by the method of the second embodiment.

[0030] Figure 10 In the diagram, (a) and (b) are schematic cross-sectional views illustrating the process of manufacturing a semiconductor device by the method of the second embodiment.

[0031] Figure 11 In the diagram, (a) and (b) are schematic cross-sectional views illustrating the process of manufacturing a semiconductor device by the method of the third embodiment.

[0032] Figure 12 In the diagram, (a) and (b) are schematic cross-sectional views illustrating the process of manufacturing a semiconductor device by the method of the third embodiment.

[0033] Figure 13 In the diagram, (a) and (b) are schematic cross-sectional views illustrating the process of manufacturing a semiconductor device by the method of the fourth embodiment.

[0034] Figure 14 In the diagram, (a), (b), and (c) are schematic cross-sectional views illustrating the process of manufacturing a semiconductor device by the method of the fifth embodiment. Detailed Implementation

[0035] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including processes, etc.) are not essential unless specifically indicated otherwise. In the following description, the same or equivalent parts are labeled with the same symbols, and repeated descriptions are omitted. Furthermore, unless otherwise stated, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. The sizes of the constituent elements in each drawing are conceptual, and the scale of the drawings is not limited to the scale shown in the drawings.

[0036] The numerical values ​​and their ranges in this specification are not limited to this invention. In this specification, the numerical range indicated by "~" represents the range encompassed by the numerical values ​​recorded before and after "~" as the minimum and maximum values, respectively. Within the numerical ranges described in stages in this specification, the upper or lower limit value recorded in one numerical range can be replaced by the upper or lower limit value of other numerical ranges described in stages.

[0037] <Semiconductor Chip Cleaning Methods>

[0038] refer to Figure 1 , Figure 2 The method for cleaning the semiconductor chip in this embodiment will be described. Figure 1 This is a cross-sectional view schematically showing the state in which the cleaning method of this embodiment is ready to be implemented. Figure 1 The multiple semiconductor chips C shown are the objects to be cleaned. Figure 2 This is a schematic cross-sectional view showing the appearance of the semiconductor chip C after cleaning. The semiconductor chip C is obtained by... Figure 3 (a) The workpiece Pw shown is obtained through a monolithic process and has a circuit layer C1 and a die C2. The circuit layer C1 is formed by monolithicizing the circuit layer Lc, and the die C2 is formed by monolithicizing the semiconductor wafer W (see reference). Figure 4 (c)).

[0039] The cleaning method of this embodiment includes the following steps.

[0040] (a) A process of cleaning a plurality of semiconductor chips C in a region R within a cutting ring DR attached to a surface 5f of an adhesive film 5 with a cleaning solution.

[0041] (b) The process of picking up the cleaned semiconductor chip C from the surface.

[0042] like Figure 1 As shown, multiple semiconductor chips C are arranged in a region R surrounded by a dicing ring DR. The specific method for cleaning the semiconductor chips C is not particularly limited, but for example, it can be done by spraying a cleaning solution from a nozzle toward the semiconductor chips C. The cleaning solution is, for example, a solution selected from the group consisting of solvents, acids, and bases.

[0043] Solvent-based solutions, such as those containing NMP (N-methyl-2-pyrrolidone), MEK (methyl ethyl ketone), PGMEA (propylene glycol monomethyl ether acetate), DMSO (dimethyl sulfoxide), or cyclopentanone, can remove foreign matter such as cutting chips, grinding chips, machining chips, and debris from the C-height of semiconductor chips.

[0044] Acidic solutions, such as those containing sulfuric acid, citric acid, or fluorine, can remove foreign matter such as cutting chips, grinding chips, machining chips, and debris from the C-axis of semiconductor chips.

[0045] Alkaline solutions, such as those containing potassium hydroxide, sodium hydroxide, ammonium hydroxide, sodium bicarbonate, hydroxylamine, TMAH (tetramethylammonium hydroxide), or ammonia, can remove foreign matter such as cutting chips, grinding chips, machining chips, and debris from the C-axis of semiconductor chips.

[0046] The adhesive film 5 comprises a substrate film 1 and an adhesive layer 2 formed on the surface of the substrate film 1. Examples of substrate films 1 include polytetrafluoroethylene (PTFE) films, polyethylene terephthalate (PET) films, polyethylene films, polypropylene films, polymethylpentene (PMM) films, and polyimide films. Among these, films resistant to the cleaning solutions used in the semiconductor chip C can be used. Surface treatments such as primer coating, UV treatment, corona discharge treatment, polishing, and etching can be performed as needed.

[0047] Adhesive layer 2 comprises an adhesive composition including a resin (A) represented by formula (1-1) and a photopolymerization initiator (B). This adhesive composition is resistant to the cleaning solutions used in the cleaning of the semiconductor chip C. Adhesive layer 2 is formed by the following steps: applying a coating solution containing the adhesive composition to the surface of the substrate film 1; or using a coating solution containing the adhesive composition to form a film of the adhesive composition and adhering it tightly to the surface of the substrate film 1. Adhesive layer 2 has the property of reducing adhesion by irradiation with activation energy (e.g., ultraviolet light (UV)).

[0048] Resin (A) is the compound (resin) represented by formula (1-1).

[0049]

[0050] In equation (1-1), k, l, m, and n represent the molar composition ratios when k + l + m + n = 100. k is greater than 0 and less than 92, l is 0–50, m is greater than 0 and less than 90, the sum of k, l, and m is 65–95, and n is 5–35. R 1 R 2 R 3 and R 4 R is a hydrogen atom or a methyl group. 5 It is an alkyl group having 1 to 16 carbon atoms, R 6 R is an alicyclic hydrocarbon group with 3 to 30 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms. 7 It can be a hydrogen atom or -(CH2). j -COOH (where j is 1 or 2), R 8 It is the basis represented by equation (1-2) or equation (1-3).

[0051] If the total of k, l, and m is 65 or more, it becomes an adhesive composition that can obtain sufficient adhesion to the substrate before activation energy irradiation. The total of k, l, and m is preferably 70 to 94, more preferably 80 to 90.

[0052] In formula (1-1), the structural unit within parentheses of k (hereinafter referred to as "structural unit k") is an essential structural unit. Structural unit k contributes to the adhesion of the adhesive composition before activation energy irradiation. The number of structural units in structural unit k is greater than 0 and less than 92, preferably 45 to 90, and more preferably 60 to 88.

[0053] In equation (1-1), the structural unit within the parentheses of l (hereinafter referred to as "structural unit l") is not necessarily a necessary structural unit. In other words, the number of structural units in structural unit l can be 0.

[0054] Structural unit 1 contributes to the heat resistance of the bonding composition. The number of structural units in structural unit 1 is 0 to 50, preferably 4 to 40, and more preferably 5 to 30.

[0055] In formula (1-1), the structural unit enclosed in parentheses of m (hereinafter referred to as "structural unit m") is an essential structural unit. Structural unit m contributes to the adhesion and heat resistance of the adhesive composition before activation energy irradiation. Furthermore, when the adhesive composition contains a crosslinking agent having a functional group that reacts with a carboxyl group, structural unit m reacts with the crosslinking agent to improve the cohesive strength of the adhesive composition. The number of structural units m is greater than 0 and less than 90, preferably 1 to 15, and more preferably 1 to 5.

[0056] In formula (1-1), the structural unit enclosed in parentheses for n (hereinafter referred to as "structural unit n") is an essential structural unit. Structural unit n contributes to the heat resistance of the adhesive composition. The number of structural units n is 5 to 35, preferably 10 to 33, and more preferably 10 to 20. If the number of structural units n is 35 or less, the adhesive composition is cured by the formation of a three-dimensional cross-linked structure from the unsaturated bonds in the resin (A) through irradiation activation energy, and the adhesion strength decreases within an appropriate range. Furthermore, if n is 5 or more, an improvement in heat resistance due to the structure derived from the alicyclic compound can be obtained.

[0057] Through the synergistic effect of the functions contributed by these structural units, the balance between the adhesion force of the adhesive composition containing resin (A) before and after activation energy irradiation becomes even better. As a result, an adhesive composition is obtained that achieves sufficient adhesion to the substrate before activation energy irradiation and exhibits superior peelability due to reduced adhesion force after activation energy irradiation. Moreover, even after the adhesive composition is at a high temperature before activation energy irradiation and then returns to room temperature, the adhesion force does not become excessively high, excellent peelability is obtained after activation energy irradiation, and it is difficult to leave residue on the substrate after peeling.

[0058] In structural unit k, R 1 Preferably, it contains hydrogen atoms (-H) or methyl groups (-CH3), with hydrogen atoms (-H). R 5 It is an alkyl group having 1 to 16 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 2, 4 or 8 carbon atoms.

[0059] The structural unit k can be R 1 and R 5 Different complex structural units. When structural unit k contains a complex number of structural units, the molar composition ratio of structural unit k represents the sum of the molar composition ratios of the complex structural units. For example, when structural unit k contains R... 1 and / or R 5 When there are different structural units A and B, and the molar composition ratio of structural unit A is 2 mol% and the molar composition ratio of structural unit B is 3 mol%, the molar composition ratio of the number of structural units k is the total molar composition ratio of structural unit A and structural unit B, which becomes "5".

[0060] In structural unit l, R 2 Preferably, it contains hydrogen atoms (-H) or methyl groups (-CH3), with hydrogen atoms (-H). R 6 It is an alicyclic hydrocarbon group with 3 to 30 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms, preferably an alicyclic hydrocarbon group with 6 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 10 carbon atoms.

[0061] Structural unit l can be R 2 and R 6 Different complex structural units. When structural unit l contains a complex number of structural units, the molar composition ratio of structural unit l represents the sum of the molar composition ratios of the complex structural units.

[0062] In structural unit m, R 3 It is a hydrogen atom (-H) or a methyl group (-CH3), preferably a hydrogen atom (-H). R 7 It can be a hydrogen atom (-H) or -(CH2). j-COOH (where j is 1 or 2), preferably a hydrogen atom (-H).

[0063] The structural unit m can be R 3 and R 7 Different complex structural units. In this case, the molar composition ratio of structural unit m represents the sum of the molar composition ratios of the complex structural units.

[0064] In structural unit n, R 4 It is a hydrogen atom (-H) or a methyl group (-CH3), preferably a hydrogen atom (-H). R 8 The base represented by formula (1-2) or formula (1-3). The base represented by formula (1-2) or formula (1-3) contains a structure derived from alicyclic compounds and has the function of improving the heat resistance of the bonding composition.

[0065]

[0066] In equations (1-2) and (1-3), p and q are integers from 0 to 2. When p is 0, s is 0; when p is 1 or 2, s is 1, and R... 9 It can be a hydrogen atom or a methyl group.

[0067] The structural unit n can be R 4 and R 8 Different complex structural units. In this case, the molar composition ratio of structural unit n represents the sum of the molar composition ratios of the complex structural units.

[0068] The resin (A) represented by formula (1-1) can be any one of a random copolymer, block copolymer, or alternating copolymer formed by structural unit k, structural unit l, structural unit m, and structural unit n. The resin (A) represented by formula (1-1) may not contain structural unit l, or it may be any one of a random copolymer, block copolymer, or alternating copolymer formed by structural unit k, structural unit m, and structural unit n.

[0069] The weight-average molecular weight (Mw) of resin (A) is preferably between 200,000 and 1,000,000, more preferably between 300,000 and 800,000. If the weight-average molecular weight of resin (A) is 200,000 or more, the adhesive layer is less likely to remain on the substrate after peeling off the adhesive layer containing the adhesive composition. If the weight-average molecular weight of resin (A) is 1,000,000 or less, the viscosity of resin (A) will not become too high and the workability will be good. The weight-average molecular weight of resin (A) refers to a value determined by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene, and can be determined, for example, by the following apparatus and under the following conditions.

[0070] The determination was performed using gel permeation chromatography (Shodex GPC-101, manufactured by Resonac Holdings Corporation) at room temperature (25°C), and the result was calculated using polystyrene conversion.

[0071] Tubes: Resonac Holdings Corporation, Shodex (registered trademark) LF-804

[0072] Column temperature: 40℃

[0073] Sample: 0.2% by mass tetrahydrofuran solution of resin (A)

[0074] Flow rate: 1 ml / min

[0075] Solution: Tetrahydrofuran

[0076] Detector: RI detector

[0077] The glass transition temperature (Tg) of resin (A) is preferably -80 to 0°C, more preferably -60 to -10°C, and even more preferably -50 to -10°C. If the glass transition temperature of resin (A) is within the range of -80°C to 0°C, the adhesion of the adhesive composition before activation energy irradiation becomes good. The Tg of resin (A) refers to the value determined by the method described below. First, a 10 mg sample is taken from resin (A). Next, using a differential scanning calorimeter (DSC), the temperature of the sample is changed from -100°C to 200°C at a heating rate of 10°C / min, and differential scanning calorimetry is performed. The observed endothermic onset temperature based on glass transition is set as Tg. Furthermore, if two Tg values ​​are observed, the simple average of the two Tg values ​​is set as Tg.

[0078] The acid value of resin (A) is preferably greater than 0 and 20 mg KOH / g, more preferably 3 to 10 mg KOH / g. If the acid value of resin (A) is in the range of greater than 0 and 20 mg KOH / g, there is no contamination (residue) of the adherend after heating, resulting in good adhesion. Furthermore, when the bonding composition includes a crosslinking agent, if the acid value of resin (A) is within the above range, the resin (A) reacts with the crosslinking agent, resulting in good cohesion of the bonding composition. The acid value of resin (A) refers to the value measured according to JIS K0070:1992.

[0079] Resin (A) can be manufactured, for example, by the method shown below. First, a raw material monomer comprising a carboxyl-containing olefinic unsaturated monomer (a) and an olefinic unsaturated monomer (d) is polymerized to produce a carboxyl-containing resin (b). Here, the olefinic unsaturated monomer (d) may be a monomer that, after polymerization, contains both a monomer that imparts structural unit k and a monomer that imparts structural unit l. Next, resin (A) can be manufactured by an addition reaction between the carboxyl-containing resin (b) and an olefinic unsaturated compound (c) containing a specific alicyclic epoxy group.

[0080] The carboxyl-containing olefinic unsaturated monomer (a) is a monomer that acquires structural unit m through polymerization. The carboxyl-containing olefinic unsaturated monomer (a) has one carboxyl group.

[0081] Examples of carboxyl-containing olefinic unsaturated monomers (a) include (meth)acrylic acid, β-carboxyethyl (meth)acrylic acid, and carboxypentyl (meth)acrylic acid. Among these, (meth)acrylic acid and / or β-carboxyethyl (meth)acrylic acid are preferred as carboxyl-containing olefinic unsaturated monomers (a) from a reactivity perspective.

[0082] In this specification, (meth)acrylic acid means "acrylic acid" or "methacrylic acid". (meth)acrylate means "acrylate" or "methacrylate". Other similar expressions are the same.

[0083] The carboxyl-containing resin (b) is made by copolymerizing raw material monomers containing at least a carboxyl-containing olefinic unsaturated monomer (a) and an olefinic unsaturated monomer (d) capable of copolymerizing with the carboxyl-containing olefinic unsaturated monomer (a).

[0084] The carboxyl-containing resin (b) is the main skeleton component of the resin (A) represented by formula (1-1). Structural unit k, structural unit l, and structural unit m are all structural units derived from the carboxyl-containing resin (b).

[0085] As an olefinic unsaturated monomer (d), one or more monomers that impart structural unit k through polymerization are used. As an olefinic unsaturated monomer (d), one or more monomers that impart structural unit l through polymerization may be used together with the monomer that imparts structural unit k through polymerization.

[0086] The olefinic unsaturated monomer (d) that imparts structural unit k through polymerization is an alkyl methacrylate with 1 to 16 carbon atoms. From the viewpoint of adjusting the peel strength of the adhesive composition, it is preferable to include an alkyl methacrylate with 2 to 16 carbon atoms, and more preferably an alkyl methacrylate with 4 to 12 carbon atoms. Specifically, examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecanyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate, lauryl methacrylate, etc. Among these, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, or isooctyl methacrylate are preferred.

[0087] Examples of olefinic unsaturated monomers (d) that impart structural unit l through polymerization include (meth)acrylates containing cyclic alkyl groups with 3 to 30 carbon atoms and (meth)acrylates containing aromatic groups with 6 to 20 carbon atoms.

[0088] Examples of (meth)acrylates containing cyclic alkyl groups with 3 to 30 carbon atoms, used as olefinic unsaturated monomers (d) that impart structural unit l through polymerization, include cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyl oxyethyl (meth)acrylate, and tricyclodecane dihydroxymethyl (di(meth)acrylate). Among these, isobornyl (meth)acrylate is particularly preferred. If the raw material monomer of the carboxyl-containing resin (b) contains a cyclic (meth)acrylate alkyl ester, the heat resistance of the bonding composition containing the resin (A) manufactured using the carboxyl-containing resin (b) becomes good.

[0089] Examples of (meth)acrylates containing aromatic groups with 6 to 20 carbon atoms, used as olefinic unsaturated monomers (d) that impart structural unit l through polymerization, include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, phenoxypropyl (meth)acrylate, and phenoxy polyethylene glycol (meth)acrylate. Among these, benzyl (meth)acrylate is particularly preferred. By using a carboxyl-containing resin (b) containing an aromatic (meth)acrylate as a raw material monomer, the bonding composition comprising a resin (A) manufactured using a carboxyl-containing resin (b) exhibits good heat resistance.

[0090] In the raw material monomers of the carboxyl-containing resin (b), in addition to the carboxyl-containing olefinic unsaturated monomer (a) and olefinic unsaturated monomer (d), there may also be monomers other than olefinic unsaturated monomer (d) that can copolymerize with the carboxyl-containing olefinic unsaturated monomer (a).

[0091] Examples of olefinic unsaturated monomers that can copolymerize with carboxyl-containing olefinic unsaturated monomers (a), other than olefinic unsaturated monomers (d), include (meth)acrylate alkoxyalkyl esters, (meth)acrylate alkoxy (poly)alkylene glycol esters, hydroxyl-containing (meth)acrylates, (meth)acrylate fluorinated alkyl esters, (meth)acrylate dialkylaminoalkyl esters, (meth)acrylamide, etc.

[0092] Examples of alkoxyalkyl esters of (meth)acrylate include ethoxyethyl ester of (meth)acrylate, methoxyethyl ester of (meth)acrylate, butoxyethyl ester of (meth)acrylate, 2-methoxyethoxyethyl ester of (meth)acrylate, and 2-ethoxyethoxyethyl ester of (meth)acrylate.

[0093] Examples of alkoxy (poly)alkylene glycol (meth)acrylates include, for example, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, and methoxydipropylene glycol (meth)acrylate.

[0094] Examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,3-butanediol (meth)acrylate, 1,4-butanediol (meth)acrylate, 1,6-hexanediol (meth)acrylate, and 3-methylpentanediol (meth)acrylate.

[0095] Examples of fluorinated alkyl esters of (meth)acrylate include, for example, octafluoropentyl (meth)acrylate.

[0096] Examples of dialkylaminoalkyl esters of (meth)acrylate include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate.

[0097] Examples of (meth)acrylamides include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropylacrylamide, N-hexyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, (meth)acryloylmorpholine, diacetone acrylamide, etc.

[0098] Specific examples of monomers other than those described above that can copolymerize with carboxyl-containing vinyl unsaturated monomers (a), besides olefinic unsaturated monomers (d), include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, allyl ether, vinyltoluene, N-vinylpyridine, N-vinylpyrrolidone, dialkyl isocitrate, dialkyl transbutenedioic acid, allyl alcohol, hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, triethylene glycol monovinyl ether, diethylene glycol monovinyl ether, methyl vinyl ketone, trimethylallyl ammonium chloride, dimethylallyl vinyl ketone, etc.

[0099] There are no particular limitations on the method for manufacturing carboxyl-containing resin (b). For example, it can be obtained by copolymerizing a raw material monomer containing a carboxyl-containing olefinic unsaturated monomer (a) and an olefinic unsaturated monomer (d) that become components of the carboxyl-containing resin (b) using a known polymerization method.

[0100] Specifically, as polymerization methods, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and alternating copolymerization can be used. Among these polymerization methods, considering the addition reaction between the carboxyl-containing resin (b) obtained after polymerization and the olefinic unsaturated compound (c) containing alicyclic epoxy groups, solution polymerization is preferred from the perspective of ease of reaction.

[0101] When manufacturing carboxyl-containing resins (b) by solution polymerization, free radical polymerization initiators and / or solvents may be used as needed.

[0102] As a free radical polymerization initiator, it is not particularly limited and can be appropriately selected from known substances. Examples of free radical polymerization initiators include azo-based polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentanitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carboxylonitrile), 2,2'-azobis(2,4,4-trimethylpentane), and dimethyl-2,2'-azobis(2-methylpropionate); and peroxide-based polymerization initiators such as benzoyl peroxide, tert-butyl hydrogenated peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, diisopropylphenyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(tert-butylperoxy)cyclododecane, etc. These free radical polymerization initiators can be used alone or in combination of two or more.

[0103] The amount of free radical polymerization initiator used is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the raw material monomers of the carboxyl-containing resin (b), more preferably 0.02 to 4 parts by mass, and even more preferably 0.03 to 3 parts by mass.

[0104] As the polymerization solvent used in the manufacture of carboxyl-containing resin (b), a variety of general solvents can be used. Examples of solvents include esters such as ethyl acetate, n-propyl acetate, and n-butyl acetate; aromatic hydrocarbons such as toluene, xylene, and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycols such as ethylene glycol, propylene glycol, and dipropylene glycol; glycol ethers such as methyl acetate, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; and glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate. These solvents can be used alone or in combination of two or more.

[0105] When manufacturing the carboxyl-containing resin (b), the content of the carboxyl-containing olefinic unsaturated monomer (a) in the raw material monomer, which includes the carboxyl-containing olefinic unsaturated monomer (a), the olefinic unsaturated monomer (d), and other monomers as needed, is preferably set to 5-40% by mass, more preferably 7-30% by mass, and even more preferably 10-25% by mass. By setting the content of the carboxyl-containing olefinic unsaturated monomer (a) in the raw material monomer within the above range, the adhesion of the adhesive layer obtained from the adhesive composition containing the resin (A) manufactured by the addition reaction of the carboxyl-containing resin (b) with an olefinic unsaturated compound (c) containing an alicyclic epoxy group becomes good before activation energy irradiation.

[0106] The olefinic unsaturated compound (c) containing an alicyclic epoxy group is a compound having an olefinic unsaturated group containing an alicyclic epoxy group and being endowed with a group represented by formula (1-2) or formula (1-3). Here, an alicyclic epoxy group refers to an epoxy group formed by bonding one oxygen atom to two adjacent carbon atoms on the ring of an alicyclic hydrocarbon compound.

[0107] The olefinic unsaturated compound (c) containing an alicyclic epoxy group is used to attach a group represented by formula (1-2') or formula (1-3') as part of the structure of the structural unit n of the resin (A) represented by formula (1-1). The group represented by formula (1-2') or formula (1-3') in the structural unit n of formula (1-1) is a group derived from the olefinic unsaturated compound (c) containing an alicyclic epoxy group.

[0108]

[0109] In equations (1-2') and (1-3'), q is an integer from 0 to 2. 9 It can be a hydrogen atom or a methyl group.

[0110] As an olefinic unsaturated compound (c) containing an alicyclic epoxy group, for example, compounds represented by formula (1) or formula (2) can be listed.

[0111]

[0112] In equation (1), R 9 It is a hydrogen atom or a methyl group. q is an integer from 0 to 2. In formula (1), R 9 It can be a hydrogen atom or a methyl group. q is an integer from 0 to 2.

[0113] In equation (1), R 9 It is a hydrogen atom (-H) or a methyl group (-CH3). q is an integer from 0 to 2, preferably q is 1.

[0114] In equation (2), R 9 It is a hydrogen atom (-H) or a methyl group (-CH3). q is an integer from 0 to 2, preferably q is 1.

[0115] As the olefinic unsaturated compound (c) containing an alicyclic epoxy group, the compound represented by formula (1) is preferred, and methyl 3,4-epoxycyclohexyl methacrylate is more preferred. The olefinic unsaturated compound (c) containing an alicyclic epoxy group can be used alone or in combination of two or more.

[0116] Resin (A) can be manufactured by adding the alicyclic epoxy group of an olefinic unsaturated monomer (c) containing an alicyclic epoxy group to the carboxyl group of a carboxyl-containing resin (b).

[0117] Resin (A) is preferably manufactured by adding a carboxyl group to an alicyclic epoxy-based olefinic unsaturated compound (c) for every 1 mol of carboxyl group in a carboxyl-containing resin (b). The amount of the alicyclic epoxy-based olefinic unsaturated compound (c) is preferably 0.2 to 0.99 mol, more preferably 0.3 to 0.95 mol, and even more preferably 0.6 to 0.95 mol. The adhesive composition comprising resin (A) obtained by using carboxyl-containing resin (b) and alicyclic epoxy-based olefinic unsaturated compound (c) in the above proportions exhibits sufficient adhesion to the substrate before activation energy irradiation and reduces adhesion after activation energy irradiation, resulting in superior peelability. Furthermore, even after being at a high temperature before activation energy irradiation and then returning to room temperature, the adhesive composition does not easily increase adhesion, exhibits excellent peelability after activation energy irradiation, and more effectively prevents residual adhesive on the substrate after peeling.

[0118] The addition reaction temperature during the manufacture of resin (A) is preferably 80–130°C, more preferably 90–120°C. If the addition reaction temperature is 80°C or higher, a sufficient reaction rate can be obtained. If the addition reaction temperature is 130°C or lower, it is possible to prevent the double bond from crosslinking through heat-based free radical polymerization and forming a gel.

[0119] In the addition reaction during the manufacture of resin (A), a known catalyst can be used as needed. Examples of catalysts include tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, 1,8-diazabicyclo[5,4,0]undecene-7-ene, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,4-diazabicyclo[2,2,2]octane, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide, alkyl ureas such as tetramethylurea, alkyl guanidines such as tetramethylguanidine, triphenylphosphine, dimethylphenylphosphine, tricyclohexylphosphine, tributylphosphine, tri(4-methylphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, tri(2,6-dimethoxyphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, and tri(2,4,6-trimethoxyphenyl)phosphine compounds. Of these, from a reactivity perspective, phosphine compounds are preferred as catalysts.

[0120] The amount of catalyst used in the addition reaction is preferably 0.01 to 30 parts by mass relative to a total of 100 parts by mass of the carboxyl-containing resin (b) and the olefinic unsaturated monomer (c) containing an alicyclic epoxy group, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass.

[0121] In addition, during addition reactions, a gas with polymerization-inhibiting effects can be introduced into the reaction system or a polymerization inhibitor can be added. By introducing a gas with polymerization-inhibiting effects into the reaction system or adding a polymerization inhibitor, gelation during the addition reaction can be prevented.

[0122] As gases that have a polymerization-inhibiting effect, examples include gases containing oxygen at levels not included in the explosive range of substances within the system, such as air.

[0123] As polymerization inhibitors, well-known substances can be used without particular restrictions, such as 4-methoxyphenol, hydroquinone, methylhydroquinone, 2,6-di-tert-butylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), phenothiazine, etc. Only one of these polymerization inhibitors can be used, or two or more can be used in combination.

[0124] The amount of polymerization inhibitor used is preferably 0.005 to 5 parts by mass relative to 100 parts by mass of the carboxyl-containing resin (b) and the olefinic unsaturated monomer (c) containing an alicyclic epoxy group, more preferably 0.03 to 3 parts by mass, and most preferably 0.05 to 1.5 parts by mass. If the amount of polymerization inhibitor is too small, the polymerization inhibition effect may be insufficient. On the other hand, if the amount of polymerization inhibitor is too large, the exposure sensitivity of the resin (A) may be reduced.

[0125] Furthermore, if a gas with polymerization inhibition effect and a polymerization inhibitor are used together, the amount of polymerization inhibitor used can be reduced or the polymerization inhibition effect can be improved, which is therefore preferred.

[0126] Based on the total amount of the adhesive composition (the total amount of solid components of the adhesive composition excluding the solvent), the content of resin (A) can be 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 98% by mass or more.

[0127] Examples of photopolymerization initiators (B) include benzophenone, phenylethylene glycol, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropylacetophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michallanto, benzoin methyl ether, and benzoin isobutyl ether. Benzoin-n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, methyl benzoyl carboxylate, 2,2-diethoxyacetophenone, 4-N,N'-dimethylacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one and other carbonyl-based photopolymerization initiators.

[0128] As photopolymerization initiators (B), examples include sulfide-based photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide; quinone-based photopolymerization initiators such as benzoquinone and anthraquinone; sulfonyl chloride-based photopolymerization initiators; and thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.

[0129] Among these photopolymerization initiators (B), from the viewpoint of solubility of the bonding composition, 1-hydroxycyclohexylphenyl ketone and / or 2,4,6-trimethylbenzoyldiphenyl phosphine oxide are preferred. Photopolymerization initiators (B) can be used alone or in combination of two or more.

[0130] The photopolymerization initiator (B) is preferably 0.1 to 5.0 parts by weight relative to 100 parts by weight of resin (A), more preferably 0.5 to 2.0 parts by weight. If the content of the photopolymerization initiator (B) is 0.1 parts by weight or more relative to 100 parts by weight of resin (A), the adhesive composition is cured at a sufficiently fast curing speed by irradiation activation energy, and the adhesion of the adhesive composition after activation energy irradiation becomes sufficiently small, which is therefore preferable. If the content of the photopolymerization initiator (B) is 5.0 parts by weight or less, the adhesive layer is less likely to remain on the substrate after peeling off the adhesive layer containing the adhesive composition.

[0131] In addition to the resin (A) and photopolymerization initiator (B), the composition may also contain a crosslinking agent (C). By including the crosslinking agent (C), a better bonding composition is achieved, resulting in a better balance between the adhesion before and after activation energy irradiation.

[0132] As a crosslinking agent (C), there are no particular limitations, but compounds having two or more hydroxyl groups of structural unit n or hydroxyl groups of structural unit n and carboxyl groups of structural unit m are preferably reactive functional groups.

[0133] Examples of crosslinking agents (C) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4-diisocyanate, isoflavone diisocyanate, 1,3-bis(N,N'-diepoxypropylaminomethyl)cyclohexane, 1,3-bis(isocyanoxymethyl)cyclohexane, isocyanurate of hexamethylene diisocyanate, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, toluene diisocyanate adduct of trimethylolpropane, xylene diisocyanate adduct of trimethylolpropane, triphenylmethane triisocyanate, methylene bis(4-phenylmethane) triisocyanate, and other isocyanate compounds.

[0134] Bisphenol A-epoxychlorohydrin type epoxy resin, N,N'-[1,3-phenylenebis(methylene)]bis[bis(ethylene oxide-2-ylmethyl)amine], ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether and other epoxy compounds;

[0135] Tetramethylolpropane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, N,N'-diphenylmethane-4,4'-bis(1-azacyclopropane carboxyformamide), N,N'-hexamethylene-1,6-bis(1-azacyclopropane carboxyformamide), and other azacyclopropane compounds;

[0136] Melamine compounds such as hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentoxymethyl melamine, and hexahexoxymethyl melamine.

[0137] Among these, epoxy compounds and / or isocyanate compounds are preferably used as crosslinking agents (C) to ensure good reactivity with resin (A). Crosslinking agent (C) can be used alone or in combination of two or more.

[0138] The crosslinking agent (C) is preferably 0.05 to 10 parts by weight relative to 100 parts by weight of resin (A), more preferably 0.1 to 5 parts by weight, and even more preferably 0.1 to 1.0 parts by weight. If the content of the crosslinking agent (C) is 0.05 parts by weight or more relative to 100 parts by weight of resin (A), a three-dimensional crosslinked structure is sufficiently formed in the adhesive composition. As a result, the adhesion of the adhesive composition after activation energy irradiation is sufficiently reduced, which is therefore preferred. If the content of the crosslinking agent (C) is 10 parts by weight or less relative to 100 parts by weight of resin (A), the adhesion of the adhesive composition before activation energy irradiation becomes good.

[0139] The composition may then contain other components besides the resin (A), photopolymerization initiator (B), and crosslinking agent (C), as needed. Examples of other components include bonding agents, various additives, etc.

[0140] As an adhesive, conventionally known substances can be used without particular limitation. Examples of adhesives include terpene resins, phenolic resins, rosin resins, aliphatic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, alicyclic petroleum resins, xylene resins, epoxy resins, polyamide resins, ketone resins, and elastic resins. These adhesives can be used alone or in combination of two or more.

[0141] When the bonding composition contains a bonding agent, its content is preferably 30 parts by weight or less, more preferably 5 to 20 parts by weight, relative to 100 parts by weight of resin (A).

[0142] As additives, examples include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, benzotriazole light stabilizers, phosphate esters and other flame retardants, surfactants and other antistatic agents, etc.

[0143] The composition can then be used as a solvent-containing coating liquid (followed by a varnish) to coat the adhesive composition.

[0144] As solvents, organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, n-propyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol, and isopropanol can be used. These solvents can be used alone or in combination of two or more.

[0145] The composition can then be manufactured by conventionally known methods. For example, it can be manufactured by mixing resin (A) and photopolymerization initiator (B) with crosslinking agent (C), subsequent additives, and various additives in a solvent and stirring, using conventionally known methods.

[0146] Adhesive layer 2 can be manufactured, for example, by the following method. First, the above-described adhesive composition is dissolved or dispersed in a solvent to prepare a coating solution (adhesive varnish). Next, the coating solution (adhesive varnish) is applied to a substrate film and heated and dried to form an adhesive layer. Alternatively, as another method of manufacturing the adhesive layer, the coating solution (adhesive varnish) is applied to a release film and heated and dried to form an adhesive layer. Then, for example, a release film having the adhesive layer can be placed on a substrate film with the adhesive layer side facing the substrate, and the adhesive layer can be transferred onto the substrate.

[0147] As a method for applying a coating liquid (followed by a varnish) to a substrate film (or release film), known methods can be used. Specifically, methods that use conventional coating machines, such as gravure roller coating machines, reverse roller coating machines, contact roller coating machines, dip roller coating machines, bar coating machines, doctor blade coating machines, spray coating machines, comma coating machines, direct coating machines, etc., can be listed.

[0148] The thickness of layer 2 can be 1–100 μm, 2–80 μm, or 5–50 μm.

[0149] like Figure 2 As shown, the semiconductor chip C is peeled off from the adhesive layer 2 by pushing it upward with the upward jig 42, and then picked up by the suction clamp 44. If the adhesion of the adhesive layer 2 is reduced due to irradiation with activation energy, the adhesive layer 2 is irradiated with activation energy lines before picking it up. The irradiation dose is, for example, 10–1000 mJ / cm². 2 It can be 100–700 mJ / cm2 Or 200~500mJ / cm 2 .

[0150] According to the cleaning method of this embodiment, by cleaning the semiconductor chip C on the bonding film 5 with a chemical solution, foreign matter adhering to the semiconductor chip C can be removed more effectively than water-based cleaning. Furthermore, according to the cleaning method of this embodiment, during the cleaning process in the chemical solution containing the semiconductor chip, the semiconductor chip can be prevented from detaching from the surface of the bonding film. By using a highly cleaned semiconductor chip C, a semiconductor device with excellent connection reliability can be manufactured. This cleaning method is also useful in that it can be effectively implemented in semiconductor manufacturing processes. That is, according to this cleaning method, the high-level cleaning based on the chemical solution is performed on the surface 5f of the bonding film 5 with the dicing ring DR attached to the bonding film 5, so the cleaned semiconductor chip C can be picked up and directly supplied to the next process. Alternatively, the semiconductor chip C can also be cleaned with pure water before and / or after chemical-based cleaning.

[0151] <Methods for Manufacturing Semiconductor Devices>

[0152] [First Implementation Method]

[0153] A method for manufacturing a semiconductor device, including the steps of performing the cleaning method described above, will be specifically described. The method for manufacturing a semiconductor device according to the first embodiment includes the following steps.

[0154] (1a) A process for forming a photoresist Rp over a workpiece Pw having a semiconductor wafer W having a first surface f1 and a second surface f2 and a circuit layer Lc formed on the first surface f1, in a manner that covers the circuit layer Lc (see reference). Figure 3 (a)).

[0155] (2a) A process of forming a trench G1 on the photoresist Rp that reaches the circuit layer Lc by exposing and developing the photoresist Rp (see reference) Figure 3 (b)).

[0156] (3a) The process of forming trench G2 by plasma cutting the circuit layer Lc via trench G1 and half-cutting the semiconductor wafer W (see reference) Figure 3 (c)).

[0157] (4a) The process of stripping photoresist Rp from circuit layer Lc (refer to) Figure 4 (a)).

[0158] (5a) The back-side polishing tape T is attached in a manner that covers the circuit layer Lc. BG Process (reference) Figure 4 (b)).

[0159] (6a) Grinding the back surface of the semiconductor wafer W by grinding from the second surface f2 side to grind the tape T. BG The process of obtaining multiple semiconductor chips C on the surface (refer to) Figure 4 (c)).

[0160] (7a) Grinding belt T from the back side BG The process of transferring multiple semiconductor chips C onto the surface 5f of the bonding film 5, and attaching a dicing ring DR onto the surface 5f in a manner that surrounds the multiple semiconductor chips C (see reference). Figure 1 ).

[0161] (8a) The process of implementing the cleaning method for semiconductor chip C.

[0162] (9a) The process of bonding the cleaned semiconductor chip C to the substrate (refer to) Figure 6 ).

[0163] Figure 3 (a) The workpiece Pw shown has a semiconductor wafer W and a circuit layer Lc. The thickness of the semiconductor wafer W is, for example, 5 to 775 μm, or 50 to 300 μm. The diameter of the semiconductor wafer W is, for example, 50 to 300 mm, or 150 to 300 mm. The circuit layer Lc is formed with various electronic circuits (e.g., integrated circuits and power supply circuits) depending on the application of the semiconductor device. The thickness of the circuit layer Lc is, for example, 0.01 to 50 μm, or 0.1 to 10 μm. The photoresist Rp is made of a photosensitive insulating material, and trenches G1 can be formed on the photoresist Rp by a photolithography process. Figure 3 (b)).

[0164] Figure 3(c) shows a trench G2 that penetrates the circuit layer Lc and extends from the first surface f1 into the interior of the semiconductor wafer W. The trench G2 does not reach the second surface f2. The trench G2 is formed by plasma cutting. One known plasma cutting process is the Bosch process. In the Bosch process, a passivation process using C4F8 plasma and an etching process using SF6 plasma are performed alternately to etch the silicon constituting the semiconductor wafer W. Specifically, in the passivation process, a perfluorocarbon polymer film (hereinafter simply referred to as the "polymer film") is isotropically formed on the entire inner surface of the trench G1. Subsequently, in the etching process, a bias voltage is applied to the semiconductor wafer W, and the polymer film at the bottom of the trench G1 is removed by ion-based etching. On the other hand, the polymer film on the sidewalls of the trench G1 is not removed and constitutes the sidewalls of the trench G1. Only the silicon exposed at the bottom of the trench G1 after the polymer film has been removed is etched by fluorine radicals. These processes are repeated to form the trench G2. The sides of the trench G2 thus formed are covered with a polymer film. If the polymer film is peeled off in subsequent processes, it may become a foreign object that reduces the reliability of the semiconductor device. The circuit layer Lc is divided by the trench G2, thereby forming multiple circuit layers C1.

[0165] After the process described in (6a), the thickness of the die C2 (the thickness of the portion from which the circuit layer C1 is removed from the semiconductor chip C) is, for example, 5 to 775 μm, or it can be 50 to 300 μm. The shavings generated in the process described in (6a) can also become foreign matter that reduces the reliability of the semiconductor device.

[0166] After the process described in (7a) and before performing the cleaning method for the semiconductor chip C, the spacing between two adjacent semiconductor chips C can be increased by applying tension to the bonding film 5. That is, as... Figure 5 As shown, tension is applied to the adhesive film 5 by pushing the inner side of the cutting ring DR upward from the substrate film 1 side of the adhesive film 5 using the ring Ra. Therefore, in the process described above (8a), the solution can be easily supplied to the side of the semiconductor chip C, and the polymer film attached to the side can be thoroughly removed with the solution. For removing the polymer film, HFE (hydrofluoroether) based or HAD (hydroxylamine) based solutions are preferably used as the solution. On the other hand, for removing shavings, the above-mentioned solvent-based, acid-based, or alkali-based solutions are preferably used as the solution.

[0167] Figure 6 This is a schematic cross-sectional view showing the state of the cleaned semiconductor chip C bonded to the substrate 10 (the adherend). In the bonding of the semiconductor chip C to the substrate 10, for example, a die bonding film (not shown) is used. Figure 7As shown, in the case of stacked semiconductor chips C, the object (attached body) to which the second and subsequent semiconductor chips C are attached is the next semiconductor chip C. The process involves connecting the substrate 10 and the multiple semiconductor chips C with wires w, and sealing the multiple semiconductor chips C with resin material 20, to fabricate... Figure 8 The semiconductor device 30 shown.

[0168] [Second Implementation]

[0169] The semiconductor device manufacturing method of the second embodiment includes the following steps.

[0170] (1b) The process of placing the workpiece Pw on the region R within the cutting ring DR on the surface 5f of the adhesive film 5 (refer to) Figure 9 (a)).

[0171] (2b) The process of forming photoresist Rp by covering the circuit layer Lc (refer to) Figure 9 (b)).

[0172] (3b) The process of forming a trench G3 on the photoresist reaching the circuit layer Lc by exposing and developing the photoresist Rp (see reference). Figure 10 (a)).

[0173] (4b) A process of obtaining multiple semiconductor chips C on the surface 5f of the bonding film 5 by plasma cutting through the trench portion G3 to cut the circuit layer Lc and the semiconductor wafer W (refer to) Figure 10 (b)).

[0174] (5b) Procedure for implementing the cleaning method for semiconductor chip C (refer to) Figure 1 , Figure 2 ).

[0175] (6b) The process of bonding the cleaned semiconductor chip C to the substrate (refer to) Figure 6 ).

[0176] Regarding this embodiment, the differences from the first embodiment will be mainly described. In this embodiment, the processes (2b) to (5b) described above are performed on the surface of the adhesive film 5 to which the cutting ring DR is attached. After the process (4b) described above, as Figure 10 As shown in (b), photoresist Rp remains on the upper surface of the semiconductor chip C. Regarding the photoresist Rp, it can be removed using a resist remover before performing the process described in (5b), or it can be removed using a chemical solution during the process described in (5b). For removing the photoresist Rp, a solvent-based chemical solution (especially NMP) is preferred. Furthermore, Figure 10(b) The trench G4 shown penetrates the circuit layer Lc and the semiconductor wafer W to reach the surface 5f of the bonding film 5. The trench G4 can be formed by plasma cutting in the same way as the trench G2 described above. The removal of the polymer film caused by plasma cutting can be carried out using HFE-based or HDA-based solutions in the same way as in the first embodiment.

[0177] [Third Implementation Method]

[0178] The semiconductor device manufacturing method of the third embodiment includes the following steps.

[0179] (1c) The process of placing the workpiece Pw on the area R within the cutting ring DR on the surface 5f of the adhesive film 5 (refer to) Figure 11 (a)).

[0180] (2c) The process of forming a protective film Mp by covering the circuit layer Lc (refer to) Figure 11 (b)).

[0181] (3c) The process of forming a trench G5 reaching the first surface f1 of the semiconductor wafer W by cutting the protective film Mp and the circuit layer Lc with a laser (see reference). Figure 12 (a)).

[0182] (4c) A process of cutting a semiconductor wafer W via a trench G5 using plasma cutting to obtain multiple semiconductor chips C on the surface 5f of the bonding film 5 (see reference). Figure 12 (b)).

[0183] (5c) Procedure for implementing the cleaning method for semiconductor chip C (refer to) Figure 1 , Figure 2 ).

[0184] (6c) The process of bonding the cleaned semiconductor chip C to the substrate (refer to) Figure 6 ).

[0185] Regarding this embodiment, the main differences from the first and second embodiments will be described. In this embodiment, a protective film Mp is formed in the process (2c) described above. The protective film Mp is used to prevent damage to the circuit layer Lc. The protective film Mp is, for example, made of a water-soluble resin, and can be formed by applying a coating containing the resin to the surface of the workpiece Pw. After the process (4c) described above, the protective film Mp remains on the upper surface of the semiconductor chip C (see reference). Figure 12 (b) The protective film Mp is removed with pure water in the process described in (5c) above. Additionally, Figure 12(b) The trench G6 shown penetrates the semiconductor wafer W and reaches the surface 5f of the bonding film 5. The trench G6 can be formed by plasma cutting in the same way as the trench G2 described above. The removal of the polymer film caused by plasma cutting can be carried out using an HFE-based or HDA-based solution in the same way as in the first embodiment.

[0186] In this embodiment, the trench G6 can be formed by blade cutting instead of plasma cutting. For example, when the circuit layer Lc contains a Low-k film, from the viewpoint of suppressing the peeling of the Low-k film with low mechanical strength, the trench G5 is formed by cutting the circuit layer Lc with a laser. On the other hand, the subsequent process of cutting the semiconductor wafer W (the process of forming the trench G6) can be carried out by blade cutting. In addition, the Low-k film is a film made of a material with a low dielectric constant, and is mainly used as an insulating material between metal wirings that electrically connect different electronic components within the chip in the interconnect layer. By using the Low-k film, the parasitic capacitance between wirings can be reduced, thereby improving the signal transmission speed and suppressing crosstalk between wirings. In addition, the process of forming trenches on the circuit layer Lc by laser is called laser grooving.

[0187] [Fourth Implementation Method]

[0188] The method for manufacturing a semiconductor device according to the fourth embodiment includes the following steps.

[0189] (1d) The process of placing the workpiece Pw on the region R within the cutting ring DR on the surface 5f of the adhesive film 5 (refer to) Figure 13 (a)).

[0190] (2d) A process of obtaining multiple semiconductor chips C on the surface 5f of the bonding film 5 by cutting the workpiece Pw with a blade (see reference). Figure 13 (b)).

[0191] (3d) Procedure for implementing the cleaning method for semiconductor chip C (refer to) Figure 1 , Figure 2 ).

[0192] (4d) The process of bonding the cleaned semiconductor chip C to the substrate (refer to) Figure 6 ).

[0193] Regarding this embodiment, the differences from the first, second, and third embodiments will be mainly described. In this embodiment, in the process (2d) described above, the workpiece Pw is monolithically divided into multiple semiconductor chips C by blade cutting. The trench G7 formed by blade cutting penetrates the circuit layer Lc and the semiconductor wafer W, reaching the surface 5f of the bonding film 5. The shavings generated in the process (2d) described above can become foreign matter that reduces the reliability of the semiconductor device. Regarding the removal of shavings generated in blade cutting, the solvent-based, acid-based, or alkaline-based solution described above is preferably used as the cleaning solution. According to this embodiment, there is no need for a process to form a photoresist or protective film, and there is also no need for a process to remove these.

[0194] [Fifth Implementation Method]

[0195] The method for manufacturing a semiconductor device according to the fifth embodiment includes the following steps.

[0196] (1e) The process of placing the workpiece Pw on the area R within the cutting ring DR on the surface 5f of the adhesive film 5 (refer to) Figure 14 (a)).

[0197] (2e) The process of forming a trench G8 reaching the first surface f1 of the semiconductor wafer W by cutting the circuit layer Lc with a laser (see reference). Figure 14 (b)).

[0198] (3e) The process of obtaining multiple semiconductor chips C on the surface 5f of the bonding film 5 by cutting semiconductor wafer W through the trench G8 with a blade (see reference) Figure 14 (c)).

[0199] (4e) Procedures for implementing the semiconductor chip cleaning method (refer to) Figure 1 , Figure 2 ).

[0200] (5e) The process of bonding the cleaned semiconductor chip C to the substrate (see reference) Figure 6 ).

[0201] Regarding this embodiment, the main differences from the fourth embodiment will be described. In this embodiment, in the process described above (2e), the circuit layer Lc is cut using a laser. Since the cutting of the circuit layer Lc uses a laser, even if the circuit layer Lc contains a Low-k film, the stripping of the Low-k film can be suppressed. Next, the semiconductor wafer W is cut using a blade cutter. Figure 14(c) The trench G9 shown penetrates the semiconductor wafer W and reaches the surface 5f of the bonding film 5. The grinding debris generated in processes (2e) and (3e) above can become foreign matter that reduces the reliability of the semiconductor device. According to this embodiment, the grinding debris generated in these processes can be removed in the subsequent process (4e) above. As the solution, the solvent-based, acid-based, or alkaline-based solution described above is preferably used.

[0202] 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 second, third, fourth, and fifth embodiments described above, it can be illustrated that the semiconductor wafer W can be used directly without back-side polishing, but the semiconductor wafer W can be back-side polished before being placed on the region R of the bonding film 5. That is, in the embodiments specified above, before placing the workpiece Pw on the region R of the bonding film 5, the semiconductor wafer W can be polished from the second surface f2 side while the workpiece Pw is attached with a back-side polishing tape covering the circuit layer Lc. In this case, the circuit layer Lc can include a Low-k film.

[0203] Symbol Explanation

[0204] 1-Substrate film, 2-Adhesive layer, 5-Adhesive film, 5f-Surface of adhesive film, 10-Substrate (attached body), 20-Resin material, 30-Semiconductor device, 42-Push-up fixture, 44-Suction clamp, C-Semiconductor chip, C1-(Monolithic) circuit layer, C2-Die, DR-Cut ring, f1-First surface, f2-Second surface, G1, G2, G3, G4, G5, G6, G7, G8, G9-Trench, Lc-Circuit layer, Mp-Protective film, Pw-Workpiece, R-Region, Rp-Photoresist, T BG - Backside grinding tape, W- Semiconductor wafer, w- Conductor wire.

Claims

1. A cleaning method of semiconductor chips, comprising the steps of: (a) cleaning a plurality of semiconductor chips disposed on a region of a surface of an adhesive film and a region within a dicing ring attached to the surface with a chemical liquid; and (b) picking up the cleaned semiconductor chips from the surface, the adhesive film comprising a base film and an adhesive layer formed on a surface of the base film, the adhesive layer containing an adhesive composition comprising a resin (A) represented by the following formula (1-1) and a photopolymerization initiator (B), the resin (A) being represented by the following formula (1-1), the chemical liquid being one selected from the group consisting of a solvent-based, an acid-based, and a base-based chemical liquid.

2. A manufacturing method of a semiconductor device, comprising the step of carrying out the cleaning method of semiconductor chips according to claim 1, wherein the manufacturing method of a semiconductor device comprises the steps of: forming a resist on a workpiece having a semiconductor wafer having a first surface and a second surface and a circuit layer formed on the first surface so as to cover the circuit layer; forming a groove portion reaching the circuit layer on the resist by exposing and developing the resist; cutting the circuit layer through the groove portion and half-cutting the semiconductor wafer by plasma dicing; peeling the resist from the circuit layer; attaching a backside polishing tape so as to cover the circuit layer; obtaining a plurality of semiconductor chips on a surface of the backside polishing tape by polishing the semiconductor wafer from the second surface side; transferring the plurality of semiconductor chips from the surface of the backside polishing tape to a surface of the adhesive film, and attaching a dicing ring on the surface of the adhesive film so as to surround the plurality of semiconductor chips on the surface; carrying out the cleaning method of semiconductor chips according to claim 1; and bonding the cleaned semiconductor chips to an adherend.

3. A manufacturing method of a semiconductor device, comprising the step of carrying out the cleaning method of semiconductor chips according to claim 1, wherein the manufacturing method of a semiconductor device comprises the steps of: disposing a workpiece having a semiconductor wafer having a first surface and a second surface and a circuit layer formed on the first surface on a region of a surface of an adhesive film and a region within a dicing ring attached to the surface; forming a resist so as to cover the circuit layer; forming a groove portion reaching the circuit layer on the resist by exposing and developing the resist; obtaining a plurality of semiconductor chips on a surface of the adhesive film by cutting the circuit layer and the semiconductor wafer through the groove portion by plasma dicing; carrying out the cleaning method of semiconductor chips according to claim 1; and bonding the cleaned semiconductor chips to an adherend.

4. A manufacturing method of a semiconductor device, comprising the step of carrying out the cleaning method of semiconductor chips according to claim 1, wherein the manufacturing method of a semiconductor device comprises the steps of: ​ ​ In equation (1-1), k, l, m, and n represent the molar composition ratios when k + l + m + n = 100, k is greater than 0 and less than 92, l is 0 to 50, m is greater than 0 and less than 90, the sum of k, l, and m is 65 to 95, and n is 5 to 35. 1 R 2 R 3 and R 4 R is a hydrogen atom or a methyl group. 5 It is an alkyl group having 1 to 16 carbon atoms, R 6 R is an alicyclic hydrocarbon group with 3 to 30 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms. 7 It can be a hydrogen atom or -(CH2). j -COOH (where j is 1 or 2), R 8 For a basis represented by either equation (1-2) or equation (1-3), In formula (1-2) and formula (1-3), p and q are integers from 0 to 2, s is 0 when p is 0, s is 1 when p is 1 or 2, R 9 is a hydrogen atom or a methyl group. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ A workpiece including a semiconductor wafer having a first surface and a second surface and a circuit layer formed on the first surface is arranged in a region on a surface of the adhesive film and in a region inside a dicing ring attached to the surface; A protective film is formed so as to cover the circuit layer; A groove portion reaching the first surface is formed by laser cutting the protective film and the circuit layer; A plurality of semiconductor chips are obtained on the surface of the adhesive film by cutting the semiconductor wafer through the groove portion by plasma cutting; The cleaning method for the semiconductor chip according to claim 1 is implemented; and The semiconductor chips after cleaning are bonded to a bonded body.

5. The method for manufacturing a semiconductor device according to claim 4, wherein the step of implementing the cleaning method includes a step of removing the protective film.

6. A method for manufacturing a semiconductor device, including a step of implementing the cleaning method for the semiconductor chip according to claim 1, wherein the method for manufacturing a semiconductor device includes the following steps: A workpiece including a semiconductor wafer having a first surface and a second surface and a circuit layer formed on the first surface is arranged in a region on a surface of the adhesive film and in a region inside a dicing ring attached to the surface; A plurality of semiconductor chips are obtained on the surface of the adhesive film by cutting the workpiece by blade dicing; The cleaning method for the semiconductor chip according to claim 1 is implemented; and The semiconductor chips after cleaning are bonded to a bonded body.

7. A method for manufacturing a semiconductor device, including a step of implementing the cleaning method for the semiconductor chip according to claim 1, wherein the method for manufacturing a semiconductor device includes the following steps: A workpiece including a semiconductor wafer having a first surface and a second surface and a circuit layer formed on the first surface is arranged in a region on a surface of the adhesive film and in a region inside a dicing ring attached to the surface; A plurality of single-chip circuit layers are obtained by forming groove portions on the circuit layer by laser, thereby dividing the circuit layer; A plurality of semiconductor chips are obtained on the surface of the adhesive film by cutting the semiconductor wafer through the groove portions by blade dicing; The cleaning method for the semiconductor chip according to claim 1 is implemented; and The semiconductor chips after cleaning are bonded to a bonded body.

8. A method for manufacturing a semiconductor device, including a step of implementing the cleaning method for the semiconductor chip according to claim 1, wherein the method for manufacturing a semiconductor device includes the following steps: A workpiece including a semiconductor wafer having a first surface and a second surface and a circuit layer formed on the first surface is arranged in a region on a surface of the adhesive film and in a region inside a dicing ring attached to the surface; A protective film is formed so as to cover the circuit layer; A groove portion reaching the first surface is formed by laser cutting the protective film and the circuit layer; A plurality of semiconductor chips are obtained on the surface of the adhesive film by cutting the semiconductor wafer through the groove portion by blade dicing; The cleaning method for the semiconductor chip according to claim 1 is implemented; and The semiconductor chips after cleaning are bonded to a bonded body.

9. The method for manufacturing a semiconductor device according to claim 8, wherein the process of carrying out the cleaning method includes a process of removing the protective film.

10. The method for manufacturing a semiconductor device according to any one of claims 7 to 9, wherein the circuit layer formed on the first surface of the semiconductor wafer includes a Low-k film.

11. The method for manufacturing a semiconductor device according to any one of claims 3 to 9, further comprising a process of, grinding the semiconductor wafer from the second surface side in a state where the workpiece is attached with a back grinding tape in a manner of covering the circuit layer, before the region on the surface of the adhesive film is provided with the workpiece.

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