JP2012156330A - Laminated sheet and method for manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet which is capable of sufficiently securing connection reliability between a semiconductor chip and a circuit board, and to provide a method for manufacturing a semiconductor device using the same.SOLUTION: The laminated sheet comprises a base film and two or more resin layers laminated on the base film. Out of the two or more resin layers, a first resin layer closest to the base film has a faster rate of dissolution in an alkali developer or an organic solvent than a second resin layer farthest from the base film. At least the second resin layer has adhesiveness.

Description

  The present invention relates to a laminated sheet and a method for manufacturing a semiconductor device using the same.

  In recent years, with the progress of miniaturization and high functionality of electronic devices, semiconductor devices are required to be miniaturized, thinned, and improved in electrical characteristics (corresponding to high-frequency transmission, etc.). Along with this, the transition from the conventional method of mounting a semiconductor chip on a substrate by wire bonding to the flip chip connection method in which conductive bump electrodes called bumps are formed on the semiconductor chip and directly connected to the substrate electrode has begun. Yes.

  As bumps formed on a semiconductor chip, bumps made of solder or gold are used, but in order to cope with recent fine connection, bumps having a structure in which solder is formed at the tip of copper bumps are used. It has come to be used.

  In addition, for high reliability, connection by metal bonding is required, and not only C4 connection using solder bumps or solder bonding by a bump having a structure in which solder is formed at the tip of a copper bump, but also gold bumps. Even in the case of using, a connection method in which solder is formed on the substrate electrode side and gold-solder bonding is adopted.

  Furthermore, in the flip-chip connection method, thermal stress derived from the difference in thermal expansion coefficient between the semiconductor chip and the substrate may concentrate on the connection part and destroy the connection part. In order to increase, it is necessary to seal and fill the gap between the semiconductor chip and the substrate with resin. In general, resin sealing filling employs a system in which a semiconductor chip and a substrate are connected using solder or the like, and then a liquid sealing resin is injected into the gap by utilizing a capillary phenomenon.

  When connecting the chip and the substrate, a flux composed of rosin, organic acid, or the like is generally used to reduce and remove the oxide film on the solder surface to facilitate metal bonding. Here, if the residue of the flux remains, it may cause the generation of bubbles called voids when the liquid sealing resin is injected, or corrosion of the wiring may occur due to the acid component, resulting in a decrease in connection reliability. The step of washing was essential. However, as the connection pitch is narrowed, the gap between the semiconductor chip and the substrate is narrowed, which may make it difficult to clean the flux residue. Furthermore, there is a problem that it takes a long time to inject the liquid sealing resin into the narrow gap between the semiconductor chip and the substrate and the productivity is lowered.

  In order to solve the problem of such a liquid sealing resin, after supplying the sealing resin to the substrate using a sealing resin having the property of reducing and removing the oxide film on the solder surface (flux activity), the semiconductor At the same time as the connection between the chip and the substrate, the gap between the semiconductor chip and the substrate is sealed and filled with resin, and the connection method and the pre-supply method called a pre-supply method that can eliminate the cleaning of the flux residue Has been proposed (see Patent Document 1).

  The following are disclosed as resin compositions having flux activity. For example, a liquid epoxy resin composition (see Patent Document 2) having both flux performance and good pot life characteristics, a liquid resin composition containing a different first curing agent having a flux activity and a second curing agent ( Patent Document 3) or a resin composition containing an inorganic filler together with an epoxy resin and a curing agent (see Patent Document 4). On the other hand, a method of forming a resin composition into a film has been proposed in order to improve the handleability during semiconductor production. In this case, after laminating the film on the semiconductor wafer, the film is diced together with the semiconductor wafer, and the semiconductor chip with the resin layer is mounted on the circuit board.

JP 2007-107006 A JP 2007-284471 A JP 2007-326941 A JP 2009-203292 A

  However, in the first supply method, since the resin for paste filling or film sealing filling is supplied to the semiconductor chip or the substrate immediately before connecting the semiconductor chip and the circuit board, the circuit surface of the semiconductor wafer is exposed. Dicing is often performed as is. For this reason, there is a problem that the circuit is damaged due to chips generated during dicing, the connection reliability between the semiconductor chip and the circuit board is deteriorated, and the yield of semiconductor manufacturing is lowered. On the other hand, in the film system, a resin layer is laminated on the circuit surface of a semiconductor wafer and then dicing is performed, but chips and resin debris generated during dicing adhere to the resin layer. For this reason, the semiconductor chip and the circuit board are peeled off or migration occurs, leading to a decrease in reliability. In particular, when dicing a thin semiconductor wafer, since the resin layer and the semiconductor wafer are simultaneously cut using laser dicing, there is a possibility that the surface of the resin layer may be contaminated with resin waste scattered during cutting with a laser.

  In addition, in any of the above-described supply systems, the resin layer completely covers the protruding electrode of the semiconductor chip when connecting the semiconductor chip and the circuit board. For this reason, unless the resin, which is an insulator, is mechanically removed before connection, or the bonded portion is not pressure-bonded at the time of connection, the reliability of the connection portion is reduced due to the biting of the resin.

  The present invention has been made to solve the above-described problems, and improves the above-described problems, and a laminated sheet that can sufficiently secure the connection reliability between a semiconductor chip and a circuit board, and a semiconductor device using the same An object is to provide a manufacturing method.

  In order to achieve the above object, the present invention is a laminated sheet comprising a base film and two or more resin layers laminated on the base film, wherein the two or more resin layers are formed. Among them, the first resin layer closest to the base film has a higher dissolution rate in an alkali developer or an organic solvent than the second resin layer farthest from the base film, and at least the second resin layer has adhesiveness. Provided is a laminated sheet which is a layer having the same.

  When a semiconductor device is manufactured using the above laminated sheet, dicing can be performed with the laminated sheet attached to the semiconductor wafer, so that dicing is possible while protecting the circuit surface of the semiconductor wafer. In addition, since the first resin layer has a faster dissolution rate in an alkali developer or an organic solvent than the second resin layer, the first resin layer is alkali after dicing in a state where the laminated sheet is attached to the semiconductor wafer from the second resin layer side. By performing development using a developer or an organic solvent, only a part of the resin layer can be removed, such as removing only the first resin layer while leaving the second resin layer. For this reason, chips and resin waste generated during dicing of the semiconductor wafer can be easily removed. Furthermore, by removing a part of the resin layer as described above, it is possible to suppress the deterioration of connection reliability due to the biting of the resin in the connection portion when the semiconductor chip and the circuit board are connected. Therefore, according to the laminated sheet, the connection reliability between the semiconductor chip and the circuit board can be sufficiently secured when used for manufacturing a semiconductor device.

  Moreover, it is preferable that the fluidity of the second resin layer is higher than that of the first resin layer. Since the second resin layer attached to the semiconductor wafer has higher fluidity than the first resin layer, the second resin layer easily fills the gap between the protruding electrodes during the manufacture of the semiconductor device. Connection reliability with is improved. In addition, since the fluidity of the first resin layer is lower than that of the second resin layer, the laminated sheet can easily maintain the film shape, and the laminated sheet can be easily handled in the attaching process of the laminated sheet.

  The present invention also provides a dicing step of dicing the semiconductor wafer with the semiconductor wafer or substrate attached to the second resin layer side of the laminated sheet, and one of the two or more resin layers in the laminated sheet after the dicing step. And a development step of removing the portion by development using an alkali developer or an organic solvent.

  In such a manufacturing method, dicing can be performed with the laminated sheet attached to the semiconductor wafer, so that dicing is possible while protecting the circuit surface of the semiconductor wafer. In addition, since the first resin layer has a faster dissolution rate with respect to an alkaline developer or an organic solvent than the second resin layer to be attached to the semiconductor wafer, the first resin layer is left by the above development step. Only a part of the resin layer can be removed. For this reason, chips and resin waste generated during dicing of the semiconductor wafer can be easily removed. Furthermore, by removing a part of the resin layer as described above, it is possible to suppress the deterioration of connection reliability due to the biting of the resin in the connection portion when the semiconductor chip and the circuit board are connected. Therefore, according to the manufacturing method, a semiconductor device in which the connection reliability between the semiconductor chip and the circuit board is sufficiently secured can be manufactured.

  Further, in the manufacture of the semiconductor device of the present invention, the protruding electrode is formed on the semiconductor wafer, and the thickness of the remaining resin layer excluding the thickness of the resin layer to be removed by the phenomenon process is equal to or less than the height of the protruding electrode. It is preferable that In this case, the protruding electrode can be exposed from the resin layer after the development process. Therefore, when the semiconductor chip and the circuit board are electrically connected, there is no biting of the resin, and the connection reliability between the two can be ensured without pressing the bonding portion with high pressure.

  ADVANTAGE OF THE INVENTION According to this invention, the lamination sheet which can fully ensure the connection reliability of a semiconductor chip and a circuit board, and the manufacturing method of a semiconductor device using the same can be provided.

It is a schematic cross section which shows one Embodiment of the lamination sheet which concerns on this invention. It is a figure which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is a figure which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is a figure which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is a schematic cross section for demonstrating the thickness of the resin layer of the lamination sheet in the manufacturing method of the semiconductor device which concerns on this invention. It is a figure which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is a figure which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is the SEM image which image | photographed the resin layer surface before and behind image development in an Example.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

(Laminated sheet)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of a laminated sheet 10 according to the present invention. As shown in FIG. 1, the laminated sheet 10 has a configuration in which a resin layer 2 is laminated on a base film 1, and the resin layer 2 is a first resin layer 2 a closest to the base film 1. And the second resin layer 2b farthest from the base film 1 is laminated. As will be described later, the laminated sheet 10 is assumed to be attached to a semiconductor wafer provided with protruding electrodes when a semiconductor device is manufactured. At this time, the laminated sheet 10 is attached so that the surface F1 on the second resin layer 2b side of the laminated sheet 10 is in contact with the circuit surface on which the protruding electrode of the semiconductor wafer is located. For this reason, the 2nd resin layer 2b is a layer which has adhesiveness. In the present specification, the description of “resin layer 2” simply refers to a layer including the first resin layer 2a and the second resin layer 2b.

  The first resin layer 2a has a faster dissolution rate in an alkali developer or an organic solvent than the second resin layer 2b. Although the dissolution rate of the 1st resin layer 2a and the 2nd resin layer 2b is not specifically limited, It is preferable that the dissolution rate of the 1st resin layer 2a is 2 times or more of the dissolution rate of the 2nd resin layer 2b. 4 times or more is more preferable. When a semiconductor device is manufactured using the laminated sheet 10 whose dissolution rate is the above condition, the first resin layer 2a can be removed in a short time in the development process. For this reason, it becomes possible to remove chips and resin scraps more efficiently.

  The dissolution rate indicates the rate of dissolution in the alkali developer or organic solvent used, and is measured, for example, as follows. Prepare a single-layer resin layer of 10 mm × 10 mm × 0.05 mm (length × width × thickness), and place this single-layer resin layer in a sample bottle filled with an alkali developer or an organic solvent so that the whole sinks, Measure the time to complete dissolution. In the present specification, the measurement time is referred to as “dissolution rate”, and the shorter the measurement time, the faster the dissolution rate. That is, when the dissolution rate of the first resin layer 2a is 2 times or more than the dissolution rate of the second resin layer 2b and 4 times or more, the measurement time is 1/2 times or less, and 1/4 Means less than double.

  In the laminated sheet 10, the second resin layer 2b preferably has higher fluidity than the first resin layer 2a. Further, from the viewpoint of facilitating filling of the gaps between the protruding electrodes, the flow value indicating the fluidity of each layer is more preferably 1.1 times or more that the second resin layer 2b is 1st resin layer 2a. More preferably, it is 5 times or more, and most preferably 2 times or more.

  The flow value is defined as follows. Each single-layer resin layer film is cut out at 10 mm × 10 mm × 0.05 mm (length × width × thickness) and sandwiched between 20 mm × 20 mm × 0.14 mm (length × width × thickness) glass chips and temperature T The pressure and time of 5 kg / 10 s are applied at (laminate temperature), the distance that flows out of the most flowing part of each side is measured, and the average value is calculated. In this specification, this average distance is called a “flow value”, and a larger value means a higher flow value.

  The thickness of each layer of the first resin layer 2a and the second resin layer 2b is not particularly limited, but from the viewpoint of handleability, each layer is usually preferably 5 μm to 200 μm, such as a circuit board on which a semiconductor chip is mounted. From the viewpoint of ensuring embedding properties, 20 μm to 150 μm is more preferable.

  The first resin layer 2a and the second resin layer 2b can be formed using a resin composition. Hereinafter, the resin composition for forming the first resin layer 2a and the second resin layer 2b will be described. The resin composition contains at least (A) a thermoplastic resin soluble in an organic solvent or an alkaline aqueous solution. (A) Although there is no restriction | limiting in particular as a thermoplastic resin, For example, a polyester resin, a polyether resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a polyetherimide resin, a polyurethane resin, a polyurethaneimide resin, a polyurethaneamideimide resin , Siloxane polyimide resin, polyesterimide resin, copolymers thereof, precursors thereof (polyamic acid, etc.), polybenzoxazole resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyester resin, Examples include polyether resins, polycarbonate resins, polyether ketone resins, (meth) acrylic copolymers having a weight average molecular weight of 10,000 to 1,000,000, novolac resins, phenol resins, and the like. . These can be used alone or in combination of two or more. In addition, the main chain and / or side chain of these resins may be provided with a glycol group such as ethylene glycol or propylene glycol, a carboxyl group, and / or a hydroxyl group.

  In addition, in order to adjust solubility and fluidity and improve connection reliability, these resins may be appropriately selected from (B) thermosetting resin, (C) photocurable resin, (D) photoinitiator, (E) A flux agent (F) filler or the like may be added as appropriate.

  (B) Although there is no restriction | limiting in particular as a thermosetting resin, In this embodiment, a thermosetting component is a component comprised from the reactive compound which can raise | generate a crosslinking reaction with a heat | fever. Examples of such compounds include epoxy resins, cyanate resins, bismaleimide resins, phenol resins, urea resins, melamine resins, alkyd resins, acrylic resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, resorcinol formaldehyde resins, From xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, cyclopentadiene Examples thereof include a thermosetting resin synthesized and a thermosetting resin by trimerization of aromatic dicyanamide. Among them, an epoxy resin, a cyanate resin, or a bismaleimide resin is preferable because an excellent adhesive force can be given at a high temperature, and an epoxy resin is particularly preferable from the viewpoint of workability and productivity. These thermosetting resins can be used alone or in combination of two or more.

  As said epoxy resin, what contains at least 2 or more epoxy group in a molecule | numerator is more preferable, and the glycidyl ether type epoxy resin of phenol is especially preferable from the point of sclerosis | hardenability and hardened | cured material property. Examples of such resins include bisphenol A type (or AD type, S type, and F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide adduct. Bisphenol A type glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolac resin glycidyl ether, naphthalene resin glycidyl ether, trifunctional (or tetrafunctional) glycidyl ether, dicyclo Examples include glycidyl ether of pentadienephenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, glycidylamine of naphthalene resin, etc. It is. These can be used individually by 1 type or in combination of 2 or more types. In addition, for these epoxy resins, it is possible to use high-purity products in which alkali metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine are reduced to 300 ppm or less as impurity ions. This is preferable for preventing migration and corrosion of metal conductor circuits.

  (B) When using a thermosetting resin, in order to cure this, additives, such as a hardening | curing agent, a hardening accelerator, a catalyst, can be suitably added to a resin composition. When a catalyst is added, a cocatalyst can be used as necessary.

  Moreover, when using an epoxy resin as (B) thermosetting resin, it is preferable that a thermosetting component contains the hardening | curing agent and / or hardening accelerator of an epoxy resin. Examples of the curing agent and / or curing accelerator include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides. Dicyandiamide, organic acid dihydrazide, boron trifluoride amine complex, imidazoles, tertiary amines, phenolic compounds having at least two phenolic hydroxyl groups in the molecule, and the like.

  (C) As a photocurable resin, the compound which has an ethylenically unsaturated group is mentioned. Examples of the ethylenically unsaturated group include vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, and (meth) acryl group. From the viewpoint of reactivity, ) Acrylic groups are preferred.

  When such (meth) acrylic groups are used, (C1) monofunctional (meth) acrylate and (C2) polyfunctional (meth) acrylate are used in combination from the viewpoint of pattern formability and low-temperature thermocompression bonding. Is preferred.

  The monofunctional (meth) acrylate reduces void generation during thermocompression bonding and can suppress outgassing during heating, so the 5% mass reduction temperature is 100 ° C. or higher, and an imide group or It is preferable to use one containing an aromatic ring.

  (C) The total content of the photocurable resin is preferably 0 to 300 parts by mass, more preferably 10 to 250 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin. When this content exceeds 300 parts by mass, the fluidity at the time of heat melting decreases due to polymerization, and the adhesiveness at the time of thermocompression bonding tends to decrease.

  (D) As a photoinitiator, the photoradical initiator which produces | generates a free radical by irradiation, the photobase generator which generate | occur | produces a base by irradiation, the photoacid generator etc. which generate | occur | produce an acid by irradiation are mentioned. (D) As a photoinitiator, in order to improve a sensitivity, what has an absorption band in 300-500 nm is preferable, and it is more preferable that the molecular extinction coefficient with respect to the light of wavelength 365nm is 1000 ml / g * cm or more. Moreover, it is preferable to use the (D) photoinitiator whose 5% mass reduction | decrease temperature is 150 degreeC or more at the point of an outgas reduction and high temperature adhesive improvement. As for the molecular extinction coefficient, a 0.001% by mass acetonitrile solution of the sample is prepared, and the absorbance of this solution is measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, “U-3310” (trade name)). Is required.

  (D) Specific examples of the photoinitiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4- Methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Aromatic ketones such as hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone , Benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether Benzoin ethers such as tereline, benzoins such as methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 , 5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxy) 2,4,5-triarylimidazole dimer such as phenyl) -4,5-diphenylimidazole dimer, 9- Phenylacridine, acridine derivatives such as 1,7-bis (9,9′-acridinyl) heptane, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4 , 6, -Trimethylbenzoyl) -phenylphosphine oxide, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Moreover, it is preferable to add (E) flux agent suitably to a resin composition. In this case, when the semiconductor chip and the circuit board are connected using solder or the like, the oxide film on the solder surface can be reduced and removed, so that the connection is facilitated.

  (E) It is desirable to use at least one compound selected from alcohols, phenols and carboxylic acids as the fluxing agent.

  The alcohol is not particularly limited as long as it is a compound having at least two alcoholic hydroxyl groups in the molecule. For example, 1,3-dioxane-5,5-dimethanol, 1,5-pentanediol, 2,5-furandiethanol, diethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, 1,2,3-hexanetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, 3- Methylpentane-1,3,5-triol, glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, ribitol, sorbitol, 2,4-diethyl-1,5-pentanediol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, 1,3-butylene glycol, 2-ethyl-1,3-hexanediol, N-butyldiethanolamine, N-ethyldiethanolamine, diethanolamine, triethanolamine, N, N-bis (2-hydroxyethyl) Isopropanolamine, bis (2-hydroxymethyl) iminotris (hydroxymethyl) methane, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, 1,1 ′, 1 ″, 1 ′ ″ − (Ethylenedinitrilo) tetrakis (2-propanol) and the like can be used. These compounds may be used alone or in combination of two or more.

  The phenols are not particularly limited as long as they are compounds having at least two phenolic hydroxyl groups. For example, catechol, resorcinol, hydroquinone, biphenol, dihydroxynaphthalene, hydroxyhydroquinone, pyrogallol, methylidene biphenol (bisphenol F). Isopropylidenebiphenol (bisphenol A), ethylidenebiphenol (bisphenol AD), 1,1,1-tris (4-hydroxyphenyl) ethane, trihydroxybenzophenone, trihydroxyacetophenone, poly-p-vinylphenol, and the like. Furthermore, as the compound having at least two phenolic hydroxyl groups, at least one compound selected from compounds having at least one phenolic hydroxyl group in the molecule, and a halomethyl group, an alkoxymethyl group, or a hydroxylmethyl group It is also possible to use a polycondensate with at least one compound selected from the group consisting of an aromatic compound having two atoms in the molecule, divinylbenzene and aldehydes.

  Examples of the compound having at least one phenolic hydroxyl group in the molecule include phenol, alkylphenol, naphthol, cresol, catechol, resorcinol, hydroquinone, biphenol, dihydroxynaphthalene, hydroxyhydroquinone, pyrogallol, methylidene biphenol (bisphenol F), Examples thereof include isopropylidene biphenol (bisphenol A), ethylidene biphenol (bisphenol AD), 1,1,1-tris (4-hydroxyphenyl) ethane, trihydroxybenzophenone, trihydroxyacetophenone, and poly p-vinylphenol.

  Examples of the aromatic compound having two halomethyl groups, alkoxymethyl groups or hydroxylmethyl groups in the molecule include 1,2-bis (chloromethyl) benzene, 1,3-bis (chloromethyl) benzene, 1 , 4-bis (chloromethyl) benzene, 1,2-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,2-bis (hydroxy) And methyl) benzene, 1,3-bis (hydroxymethyl) benzene, 1,4-bis (hydroxymethyl) benzene, bis (chloromethyl) biphenyl, and bis (methoxymethyl) biphenyl. Examples of aldehydes include formaldehyde (formalin as an aqueous solution thereof), paraformaldehyde, trioxane, hexamethylenetetramine and the like.

  Examples of the polycondensate include a phenol novolac resin that is a polycondensate of phenol and formaldehyde, a cresol novolac resin that is a polycondensate of cresol and formaldehyde, a naphthol novolac resin that is a polycondensate of naphthols and formaldehyde, Phenol aralkyl resin, which is a polycondensation product of phenol and 1,4-bis (methoxymethyl) benzene, polycondensation product of bisphenol A and formaldehyde, polycondensation product of phenol and divinylbenzene, polycondensation of cresol, naphthol and formaldehyde These may be those obtained by modifying these polycondensates with rubber, or by introducing an aminotriazine skeleton or dicyclopentadiene skeleton into the molecular skeleton. The properties of these compounds may be either solid or liquid at room temperature, but in order to uniformly reduce and remove the oxide film on the metal surface and not hinder the wettability of the solder, it is necessary to use a liquid one. Desirably, for example, allylated phenol novolak resin, diallyl bisphenol A, diallyl bisphenol F, diallyl biphenol and the like can be mentioned as liquids obtained by allylating these compounds having a phenolic hydroxyl group. These compounds may be used alone or in combination of two or more.

  The carboxylic acids may be either aliphatic carboxylic acids or aromatic carboxylic acids, and are preferably solid at 25 ° C. Examples of the aliphatic carboxylic acid include malonic acid, methylmalonic acid, dimethylmalonic acid, ethylmalonic acid, allylmalonic acid, 2,2′-thiodiacetic acid, 3,3′-thiodipropionic acid, 2,2′- (Ethylenedithio) diacetic acid, 3,3′-dithiodipropionic acid, 2-ethyl-2-hydroxybutyric acid, dithiodiglycolic acid, diglycolic acid, acetylenedicarboxylic acid, maleic acid, malic acid, 2-isopropylmalic acid , Tartaric acid, itaconic acid, 1,3-acetone dicarboxylic acid, tricarbaric acid, muconic acid, β-hydromuconic acid, succinic acid, methyl succinic acid, dimethyl succinic acid, glutaric acid, α-ketoglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 2,2-bis (hydroxy Methyl) propionic acid, citric acid, adipic acid, 3-tert-butyladipic acid, pimelic acid, phenyloxalic acid, phenylacetic acid, nitrophenylacetic acid, phenoxyacetic acid, nitrophenoxyacetic acid, phenylthioacetic acid, hydroxyphenylacetic acid, dihydroxyphenylacetic acid , Mandelic acid, hydroxymandelic acid, dihydroxymandelic acid, 1,2,3,4-butanetetracarboxylic acid, suberic acid, 4,4′-dithiodibutyric acid, cinnamic acid, nitrocinnamic acid, hydroxycinnamic acid, Dihydroxycinnamic acid, coumaric acid, phenylpyruvic acid, hydroxyphenylpyruvic acid, caffeic acid, homophthalic acid, tolylacetic acid, phenoxypropionic acid, hydroxyphenylpropionic acid, benzyloxyacetic acid, phenyllactic acid, tropic acid, 3- (phenylsulfo) Nyl) propionic acid, 3,3-tetramethylene glutaric acid, 5-oxoazeleic acid, azelaic acid, phenylsuccinic acid, 1,2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid , Benzylmalonic acid, sebacic acid, dodecanedioic acid, undecanedioic acid, diphenylacetic acid, benzylic acid, dicyclohexylacetic acid, tetradecanedioic acid, 2,2-diphenylpropionic acid, 3,3-diphenylpropionic acid, 4,4-bis (4-Hydroxyphenyl) valeric acid, pimaric acid, parastrinic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, agatic acid and the like.

  Examples of the aromatic carboxylic acid include benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5- Dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 3,4,5-trihydroxy Benzoic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2- [bis (4-hydroxyphenyl) methyl] benzoic acid, 1- Naphthoic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6- Droxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 2,3-naphthalenedicarboxylic acid, 2, Examples include 6-naphthalenedicarboxylic acid, 2-phenoxybenzoic acid, biphenyl-4-carboxylic acid, biphenyl-2-carboxylic acid, and 2-benzoylbenzoic acid. Among these, from the viewpoint of storage stability and availability, succinic acid, malic acid, itaconic acid, 2,2-bis (hydroxymethyl) propionic acid, adipic acid, 3,3′-thiodipropionic acid, 3 , 3′-dithiodipropionic acid, 1,2,3,4-butanetetracarboxylic acid, suberic acid, sebacic acid, phenylsuccinic acid, dodecanedioic acid, diphenylacetic acid, benzylic acid, 4,4-bis (4- Hydroxyphenyl) valeric acid, abietic acid, 2,5-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2- [Bis (4-hydroxyphenyl) methyl] benzoic acid or the like is preferably used. These compounds may be used alone or in combination of two or more.

  The blending amount of these (E) fluxing agents is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin. More preferably, it is 1-10 mass parts. If the blending amount is less than 0.1, the effect of removing the oxide film on the solder surface may not be sufficiently exhibited and connection failure may occur. On the other hand, when it exceeds 15 mass parts, (E) flux agent may cause a void.

  Furthermore, the resin composition may contain (F) filler for viscosity adjustment and physical property control of the cured product. The filler may be either an organic filler or an inorganic filler. In particular, when used as a resin composition for semiconductor sealing filling, it is desirable to include an inorganic filler in order to achieve low thermal expansion.

  Examples of the inorganic filler include glass, silicon dioxide (silica), aluminum oxide (alumina), titanium oxide (titania), magnesium oxide (magnesia), carbon black, mica, and barium sulfate. You may use these individually or in mixture of 2 or more types. In addition, a composite oxide containing two or more types of metal oxides (not just a mixture of two or more types of metal oxides, but the metal oxides are chemically bonded to each other and cannot be separated) For example, a composite oxide composed of silicon dioxide and titanium oxide, silicon dioxide and aluminum oxide, boron oxide and aluminum oxide, silicon dioxide, aluminum oxide and magnesium oxide, and the like can be given.

  (F) The shape of the filler is not particularly limited to a crushed shape, a needle shape, a flake shape, and a spherical shape, but a spherical shape is preferably used from the viewpoint of dispersibility and viscosity control. Further, the filler may have any average particle size smaller than the gap between the semiconductor chip and the substrate when flip-chip connection is performed, but from the viewpoint of packing density and viscosity control, the average particle size is 10 μm or less. Those having a thickness of 5 μm or less are more preferable, those having a thickness of 3 μm or less are particularly preferable. Furthermore, in order to adjust the viscosity and the physical properties of the cured product, two or more types having different particle sizes may be used in combination.

  The blending amount of (F) filler is desirably 300 parts by mass or less, and more desirably 200 parts by mass or less with respect to 100 parts by mass of (A) thermoplastic resin. When the blending amount is more than 300 parts by mass, the melt viscosity of the resin composition becomes high and the fluidity is lowered, so that connection failure may occur.

  The resin composition may further contain additives such as a silane coupling agent, a titanium coupling agent, an antioxidant, a leveling agent, and an ion trapping agent. These may be used alone or in combination of two or more. What is necessary is just to adjust about a compounding quantity so that the effect of each additive may express.

  The resin composition can be produced by stirring and mixing each of the above-described components using a planetary mixer, a rake machine, a bead mill, or the like. Moreover, when mix | blending (F) filler, it is preferable to knead | mix using 3 rolls and to disperse | distribute (F) filler in a resin composition.

  Furthermore, when it is made into a film at room temperature, an organic solvent such as toluene, ethyl acetate, methyl ethyl ketone, cyclohexanone, N-methylpyrrolidone is further added to the resin composition, and a varnish is prepared by mixing using a planetary mixer or bead mill. Then, using a knife coater or roll coater, the varnish was applied onto a film substrate such as a polyethylene terephthalate resin that had been subjected to a release treatment, and then the organic solvent was removed by drying to form a film-like resin layer. Can be manufactured.

  The dissolution rate and fluidity of the first resin layer 2a and the second resin layer 2b in the alkali developer or the organic agent can be adjusted by changing the components of the resin composition forming each layer and the content thereof. In order to make the dissolution rate of the first resin layer 2a higher than the dissolution rate of the second resin layer 2b, (A) the concentration of the carboxyl group imparted to the main chain and / or side chain of the thermoplastic resin is increased. (A) The average molecular weight of the thermoplastic resin may be lowered. In order to make the dissolution rate of the second resin layer 2b slower than the dissolution rate of the first resin layer 2a, (C) a photocurable resin is added to the second resin layer 2b, and the laminated sheet 10 is added to the semiconductor wafer 3. The second resin layer 2b may be photocured by exposing after laminating. Furthermore, in order to give the adhesiveness to the second resin layer 2b, it is necessary to contain (B) a thermosetting resin in the resin composition of the second resin layer 2b. In order to further improve the reliability, it is preferable to contain (F) a filler in addition to (B) the thermosetting resin.

  The first resin layer 2a is a layer from which part or all of the first resin layer 2a is removed by development, and may or may not have adhesiveness. When giving adhesiveness to the 1st resin layer 2a, the component similar to the 2nd resin layer 2b mentioned above is contained. On the other hand, when the first resin layer 2a is not provided with adhesiveness, the first resin layer 2a may be composed only of (A) a thermoplastic resin or (A) a thermoplastic resin and (F) a filler.

  As a method of manufacturing the laminated sheet 10, a method of sequentially applying the first resin layer 2 a and the second resin layer 2 b on the base film 1, or a method of manufacturing the first resin layer 2 a and the second resin layer 2 b. A method of producing a film by pasting together each of them is mentioned.

  When applying the 1st resin layer 2a and the 2nd resin layer 2b sequentially, it can carry out by simultaneous coating (multilayer coating) or sequential coating. For example, (i) a method of laminating the first resin layer 2a on the base film 1 and then laminating the second resin layer 2b; (ii) a first resin layer 2a and a second layer on the base film 1; The method of laminating | stacking the two resin layer 2b simultaneously is mentioned, From the viewpoint of workability | operativity, the method of (ii) is preferable. In addition, the said coating can be performed by well-known methods, such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, for example.

  The method of laminating the first resin layer 2a and the second resin layer 2b in a film form is performed in the following procedure. First, the resin composition of the 1st resin layer 2a and the 2nd resin layer 2b is melt | dissolved or disperse | distributed to a solvent to make a varnish, and this is apply | coated on the another base film 1, respectively, Then, a solvent is removed by heating. Next, the base film to which each resin composition is applied is heat-pressed while being stacked in a state where the first resin layer 2a and the second resin layer 2b are in contact with each other to form a layered film. Then, the laminated sheet 10 can be obtained by peeling the base film 1 on the second resin layer 2b side of the layered film.

  Examples of the material of the base film 1 include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, polytetrafluoroethylene, release paper, copper foil, and aluminum foil such as aluminum foil. These may be used alone or in combination of two or more. The base film 1 may be subjected to mat treatment, corona treatment, and mold release treatment.

  The laminated sheet 10 is preferably stored by being wound around, for example, a cylindrical core. Moreover, when the laminated sheet 10 is wound around the core, it is preferable to wind the base film 1 so that it is on the outermost side. An end face separator is preferably installed on the end face of the roll-shaped photosensitive film from the viewpoint of end face protection, and a moisture proof end face separator is preferably installed from the viewpoint of edge fusion resistance.

(Method for manufacturing semiconductor device)
Next, a method for manufacturing a semiconductor device using the laminated sheet 10 will be described.

2 to 4 and FIGS. 6 and 7 are views showing a preferred embodiment of a method of manufacturing a semiconductor device according to the present invention. FIG. 5 is a schematic cross-sectional view for explaining the thickness of the resin layer 2 of the laminated sheet 10 in the method for manufacturing a semiconductor device according to the present invention. The manufacturing method according to this embodiment mainly includes the following steps.
Step 1 (FIGS. 2 and 3): After laminating the laminated sheet 10 on the circuit surface S1 of the semiconductor wafer 3, the base film 1 is peeled off to obtain a laminated body 30.
Process 2 (FIG. 4): After sticking the adhesive tape 4 on the back surface S2 side of the semiconductor wafer 3, the semiconductor wafer 3 is cut into a plurality of semiconductor chips 12 by dicing.
Step 3 (FIG. 5): A part of the resin layer 2 is removed by development using an alkali developer or an organic solvent.
Step 4 (FIGS. 6 and 7): The semiconductor chip 12 is picked up and pressure-bonded (mounted) to the support member 15 for mounting the semiconductor element. Hereinafter, each process will be described with reference to the drawings.

(A) Step 1 (FIGS. 2 and 3)
As shown in FIG. 2, after the semiconductor wafer 3 is disposed on the laminator R with the circuit pattern side (circuit surface) S <b> 1 facing upward, the circuit surface S <b> 1 of the semiconductor wafer 3 and the second resin of the laminated sheet 10 are disposed. The laminated sheet 10 is attached to the semiconductor wafer 3 so that the surface F1 on the layer 2b side is in contact with it. Then, the laminated body 30 by which the resin layer 2 / semiconductor wafer 3 was laminated | stacked is obtained by peeling the base film 1 (refer FIG. 3). A protruding electrode (not shown) is provided on the circuit surface S <b> 1 of the semiconductor wafer 3.

  Here, as the protruding electrode, a solder bump, a gold bump formed by plating, vapor deposition or metal wire, a copper bump, a nickel bump, or a bump having a structure in which a solder or tin layer is formed on the tip of a copper pillar, etc. Is mentioned. Further, a conductive resin bump formed of a resin or a resin core bump having a resin as a core and a metal deposited on the surface thereof may be used. The protruding circuit electrode does not need to be composed of a single metal, and may contain a plurality of metal components such as gold, silver, copper, nickel, indium, palladium, tin, and bismuth. May be laminated.

  For example, in the case of using a vacuum laminator, the lamination conditions in step 1 are determined in the range of the pressure / temperature in the chamber from 100 Pa to 1000 Pa / 20 ° C. to 100 ° C. In the case of pressure lamination, the temperature is 100 ° C. and the linear pressure is 4 kgf / cm. The feed rate is preferably 0.5 m / min. When laminating the semiconductor wafer 3 and the resin layer 2 under the above-described conditions, the embedding property of the semiconductor wafer 3 in the concave portion of the circuit surface S1 is improved, and the generation of voids can be suppressed.

(B) Step 2 (FIG. 4)
First, a peelable adhesive tape 4 such as a dicing tape is attached to the back surface S2 side of the semiconductor wafer 3. The adhesive tape 4 can be attached by a method of laminating an adhesive tape previously formed into a film shape. Next, as shown in FIG. 4, the semiconductor wafer 3 is cut along with the resin layer 2 along the dicing line D. By this dicing, the semiconductor wafer 3 is cut into a plurality of semiconductor chips 12 in which the resin layer 2 is provided on each circuit surface S1. Dicing is performed using a dicing blade 6 in a state where the whole is fixed to a frame (wafer ring) 5 with an adhesive tape (dicing tape) 4.

(C) Step 3 (FIG. 5)
After dicing, a part of the resin layer 2 is removed by development using an alkali developer or an organic solvent. Here, the thickness of the resin layer 2 will be described. FIG. 5 is a schematic cross-sectional view for explaining the thickness of the resin layer 2. FIG. 5A is a schematic cross-sectional view showing a state before a part of the resin layer 2 is removed by development after the resin layer 2 is attached to the circuit surface S1 of the semiconductor wafer 3 (before development). ) Is a schematic cross-sectional view of a state after a part of the resin layer 2 is removed by development (after development).

  When a semiconductor device is manufactured using the laminated sheet 10, the semiconductor wafer 3 provided with the protruding electrodes 13 is used as the semiconductor wafer 3. For example, as shown in FIG. 5, a semiconductor wafer 3 having a protruding electrode 13 on the surface of the terminal 8 on the circuit pattern 7 on the circuit surface S <b> 1 can be used. The protruding electrode 13 includes a pillar electrode 9 directly connected to the terminal 8 and a solder ball 11 provided at the tip of the pillar electrode 9. When the laminated sheet 10 is affixed to the circuit surface S1 of the semiconductor wafer 3 at the time of manufacturing the semiconductor, as shown in FIG. 5A, when the height of the protruding electrode 13 of the semiconductor wafer 3 is H, before the development. The thickness A of the resin layer 2 is preferably not less than the height H of the protruding electrode 13. In this case, since the protruding electrode 13 is covered with the resin layer 2 when the semiconductor wafer 3 is diced, it is possible to avoid the protruding electrode 13 from being damaged by chips generated during dicing. Further, as shown in FIG. 5B, the thickness B of the resin layer 20 after development is preferably equal to or less than the height H of the protruding electrode 13. In this case, since the protruding electrode 13 can be exposed from the resin layer 20 after development, there is no resin bite when the semiconductor chip 12 and the circuit board are electrically connected, and the bonded portion is crimped with high pressure. Even without this, connection reliability between the two can be ensured.

  The first resin layer 2a having a high dissolution rate is usually removed by development, and the second resin layer 2b remains. A part of the first resin layer 2a may remain or a part of the second resin layer 2b may be removed. Even in this case, since a part of the resin layer 2 is removed, it is possible to suppress the deterioration of connection reliability due to the resin biting in the connection portion when the semiconductor chip 12 and the substrate are connected. Therefore, a semiconductor device in which the connection reliability between the semiconductor chip 12 and the circuit board is sufficiently secured can be manufactured.

(D) Step 4 (FIGS. 6 and 7)
After the development, the cut semiconductor chip 12 is picked up together with the resin layer 20 by the die bonding apparatus 50 (FIG. 6), the semiconductor chip 12 is turned upside down, and then the semiconductor device substrate (on the heating platen 14) ( The semiconductor device 60 is obtained by pressure bonding (mounting) to the semiconductor element mounting support member 15 (FIG. 7). The pressure bonding is preferably performed while heating.

  The semiconductor chip 12 is bonded to the substrate 15 or another semiconductor chip by pressure bonding. The shear adhesive strength at 260 ° C. between the semiconductor chip 12 and the substrate 15 or another semiconductor chip is preferably 0.2 MPa or more, and more preferably 0.5 MPa or more. If the shear bond strength is less than 0.2 MPa, peeling tends to occur due to a thermal history such as a reflow process.

  The shear bond strength here can be measured using a shear bond strength tester “Dage-4000” (trade name). More specifically, for example, it is measured by the following method. First, after exposing the entire surface of the semiconductor wafer 3 on which a resin layer serving as an adhesive layer is formed, a 3 × 3 mm square semiconductor chip is cut out. The cut-out semiconductor chip with an adhesive layer is placed on a 5 × 5 mm square semiconductor chip prepared in advance, and is pressure-bonded at 120 ° C. for 2 seconds while being pressurized with 100 gf. Thereafter, the sample is heated in an oven at 120 ° C. for 1 hour and then at 180 ° C. for 3 hours to obtain a sample in which the semiconductor chips are bonded to each other. About the obtained sample, the shear adhesive force in 260 degreeC is measured using the shear adhesive strength tester "Dage-4000" (brand name).

  In the above, it demonstrated in detail based on embodiment of this invention. However, the present invention is not limited to the above embodiment. The present invention can be modified in various ways as described below without departing from the scope of the invention.

  For example, although the resin layer 2 of the laminated sheet 10 of the present embodiment is configured by two layers of the first resin layer 2a and the second resin layer 2b, the configuration of the resin layer 2 is not limited to two layers. The resin layer 2 may be composed of three or more layers. However, it is preferable that the resin layer 2 is two layers from the point which can simplify the manufacturing process of the lamination sheet 10 most.

  When the resin layer 2 is composed of three or more layers, it is preferable that the second resin layer 2b farthest from the base film 1 in the resin layer 2 has the slowest dissolution rate in an alkali developer or an organic solvent. When a semiconductor device is manufactured using such a laminated sheet 10, when the laminated sheet 10 is attached to the semiconductor wafer 3 from the second resin layer 2b side, an alkali developer or an organic solvent is added to the second resin layer 2b in the development process. It becomes difficult to penetrate. In this case, since the second resin layer 2b adhered to the semiconductor wafer 3 remains reliably after development, the semiconductor chip can be directly connected to the circuit board after the semiconductor wafer 3 is diced.

  Moreover, in the manufacturing method of the semiconductor device of this embodiment, it is possible to change suitably the order of each process of adhesion | attachment of the adhesive tape 4, dicing, and image development. Moreover, you may perform an exposure process before or after dicing of the semiconductor wafer 3 for the objective of making the melt | dissolution rate of the 2nd resin layer 2b still slower than the 1st resin layer 2a. The exposure step is performed by irradiating the resin layer 2 with actinic rays. At the time of exposure, a negative mask or a positive mask may be used. Further, a polishing step for the semiconductor wafer 3 may be added as appropriate.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, the scope of the present invention is not limited by these.

(Synthesis of polyimide resin PI-1)
In a flask equipped with a stirrer, a thermometer, a nitrogen displacement device (nitrogen inflow pipe), and a reflux condenser with a moisture receiver, MBAA (trade name, manufactured by Wakayama Seika Co., Ltd., 5,5′- 5.99 g (0.02 mol) of methylene-bis (anthranic acid), molecular weight 286.3), 12.99 g of D-400 (trade name, manufactured by BASF, polyether diamine, molecular weight: 452.4) (0.03 mol), 2.48 g of BY16-871EG (trade name, manufactured by Toray Dow Corning, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) -disiloxane) (0.01 mol) and 1,4-butanediol bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry, trade name: B-12, molecular weight: 204.31) 8.17 g (0.04 mol) When charged with N- methyl-2-pyrrolidone (NMP) 110g as a solvent, was stirred to a diamine is dissolved in a solvent.

  While cooling the flask in an ice bath, 27.9 g (0.09 mol) of ODPA (4,4-oxydiphthalic dianhydride) and 3.84 g (0.02 mol) of TAA (trimellitic anhydride) A small amount was added to the solution in the flask. After completion of the addition, the solution was heated to 180 ° C. while blowing nitrogen gas and kept for 5 hours. Next, the obtained varnish was reprecipitated in methanol, and the recovered polyimide was allowed to stand at room temperature for one day, and then dried at 60 ° C. for 8 hours using a vacuum dryer to obtain polyimide resin PI-1. . When GPC measurement of PI-1 was performed, it was Mw = 21,000 in terms of polystyrene. Moreover, Tg of PI-1 was 55 degreeC.

(Adjustment of varnish)
Based on the composition shown in Table 1, a varnish for forming the first resin layer and the second resin layer by dissolving and mixing each material in a toluene-ethyl acetate solvent so that the solid content concentration is 50% by mass. Each was produced.

Details of each component in the table are as follows.
(A) component: PI-1
PKCP-80 (ε-caprolactone-modified phenoxy resin (product name), manufactured by Inchem Corporation)
(B) component: EP1032H60 (Trisphenol methane type polyfunctional epoxy resin (product name of Japan Epoxy Resin Co., Ltd.))
YH307 (3,4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1,2-dicarboxylic anhydride 1-isopropyl-4-methylbicyclo- [2.2.2] octo- Mixture of 5-ene-2,3-dicarboxylic anhydride (product name of Japan Epoxy Resin Co., Ltd.))
Flux agent: Adipic acid (manufactured by Sigma-Aldrich, product name, melting point 152 ° C.)
Curing accelerator: PX-4PB (tetra (n-butyl) phosphonium tetraphenylborate (manufactured by Nippon Chemical Industry Co., Ltd., product name))
Filler: R972 (Nippon Aerosil, hydrophobic fumed silica (average particle size: about 16 nm))
SE2050 (spherical silica (manufactured by Admatex, product name))

(Production of film)
The prepared first resin layer varnish was applied on a separator film (PET film) using a knife coater and then dried in an oven at 70 ° C. for 10 minutes to produce a first resin layer film having a thickness of 25 μm. did. Similarly, after applying the prepared varnish of the second resin layer on a separator film (PET film) using a knife coater, the varnish of the second resin layer having a thickness of 30 μm is dried in an oven at 70 ° C. for 10 minutes. A film was prepared.

(Production of laminated sheet)
The film of the obtained first and second resin layers was laminated with a laminator in a state where the first resin layer and the second resin layer were in contact with each other (temperature 60 ° C., linear pressure 4 kgf / cm). , Feed rate 0.5 m / min). Then, the laminated sheet provided with the 1st resin layer and the 2nd resin layer in this order on the PET film by peeling the PET film by the side of the 2nd resin layer was obtained.

(Measurement of resin layer dissolution rate)
After the film of the single resin layer of the 1st resin layer and the 2nd resin layer was created, respectively, it cut out to 10 mm x 10 mm x 0.05 mm (length x width x thickness), and each cut out film was made into alkali developer ( The sample bottle containing tetramethylammonium hydroxide (TMAH) (2.38%) was placed so as to sink completely, and while rotating with a mix rotor, the time until complete dissolution was measured. Although the first resin layer was completely dissolved in 3 minutes, the film remained in the second resin layer even after 30 minutes had passed. From the above, it was found that the dissolution rate of the first resin layer was 10 times or more the dissolution rate of the second resin layer.

(Measurement of flow value of resin layer)
A single resin layer film of the first resin layer and the second resin layer is cut out at 10 mm × 10 mm × 0.05 mm (length × width × thickness), and 20 mm × 20 mm × 0.14 mm (length × width × thickness). The glass chip was sandwiched between the glass chips, and the pressure and time of 5 kg / 10 s were applied at a temperature of 80 ° C. (laminating temperature), the distance of the most flowing out part of each side was measured, and the average value was calculated. As a result, the first resin layer flowed 5 μm, and the second resin layer flowed 100 μm. From the above, it was found that the flow value of the second resin layer was 20 times the flow value of the first resin layer.

(Lamination on chip)
As a semiconductor chip on which a bump having a structure having a lead-free solder layer (Sn-3.5 Ag: melting point 221 ° C.) is formed at the tip of the copper pillar electrode, JTEG PHASE11_80 (size 7.3 mm × 7.3 mm, manufactured by Hitachi ULSI Systems) A bump pitch of 80 μm, a number of bumps of 328, a thickness of 0.55 mm, and a trade name) were prepared. Subsequently, the laminated sheet obtained above is roll-pressed (temperature 60 ° C., linear pressure 4 kgf / cm, feed rate 0.5 m / min), and the circuit surface having the second resin layer of the laminated sheet and the bumps of the semiconductor chip Were laminated so that At this time, it was confirmed that the bump was covered with the resin layer and was not exposed.

(developing)
Subsequently, the obtained semiconductor chip was immersed in a 2.38% aqueous TMAH solution in a bat, and after 3 minutes, immersed in a bat filled with pure water for 5 minutes. Then, the semiconductor chip was taken out and the surface was washed with a washing bottle. FIG. 8 is an SEM image obtained by photographing the surface of the second resin layer before and after development. FIG. 8A shows an SEM image before development, and FIG. 8B shows an SEM image after development. As shown in FIG. 8, it was confirmed that the surface of the bump that was not exposed before development was exposed from the resin layer after development.

(Chip and substrate connection)
A glass epoxy substrate having a copper wiring pattern having a rust-preventive film formed thereon by preflux treatment as a substrate was prepared. The substrate is sucked and fixed on a stage set to 40 ° C of a flip chip bonder FCB3 (manufactured by Panasonic Factory Solutions), aligned with the semiconductor chip, and then temporarily fixed at a load of 25 N and a head temperature of 100 ° C. Pressure bonding was performed for 2 seconds (attainment temperature 90 ° C.), and the semiconductor chip was temporarily fixed on the substrate. Next, as a first step, the head temperature of the flip chip bonder was set to 210 ° C., and pressure bonding was performed with a load of 25 N for 10 seconds (attainment temperature 180 ° C.). Further, as a second step, the head temperature of the flip chip bonder was set to 290 ° C., and pressure bonding was performed for 10 seconds with a load of 25 N (attainment temperature 250 ° C.).

(Continuity test)
For the semiconductor device in which the semiconductor chip and the substrate are connected, the 328 bump daisy chain connection was confirmed, and the continuity test was accepted.

  DESCRIPTION OF SYMBOLS 1 ... Base film, 2 ... Resin layer, 2a ... 1st resin layer, 2b ... 2nd resin layer, 3 ... Semiconductor wafer, 10 ... Laminated sheet, 13 ... Projection electrode, 60 ... Semiconductor device.

Claims (4)

A laminated sheet comprising a base film and two or more resin layers laminated on the base film,
Of the two or more resin layers, the first resin layer closest to the base film has a higher dissolution rate in an alkali developer or an organic solvent than the second resin layer farthest from the base film,
A laminated sheet in which at least the second resin layer is a layer having adhesiveness.   The laminated sheet according to claim 1, wherein the second resin layer has higher fluidity than the first resin layer. A dicing step of dicing the semiconductor wafer in a state where the semiconductor wafer is attached to the second resin layer side of the laminated sheet according to claim 1 or 2,
After the dicing step, a developing step of removing a part of the two or more resin layers in the laminated sheet by development using the alkaline developer or the organic solvent;
A method for manufacturing a semiconductor device, comprising:   The protruding electrode is formed in the said semiconductor wafer, The thickness of the remaining resin layers except the thickness of the resin layer removed by the said phenomenon process is below the height of the said protruding electrode. Semiconductor device manufacturing method.