CN112673071B - Method for producing non-conductive film and semiconductor laminate - Google Patents
Method for producing non-conductive film and semiconductor laminate Download PDFInfo
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- CN112673071B CN112673071B CN202080004772.6A CN202080004772A CN112673071B CN 112673071 B CN112673071 B CN 112673071B CN 202080004772 A CN202080004772 A CN 202080004772A CN 112673071 B CN112673071 B CN 112673071B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
The present disclosure relates to a non-conductive film and a method of manufacturing a semiconductor laminate using the non-conductive film, the non-conductive film comprising: an adhesive layer comprising a low molecular weight epoxy resin; and an adhesive layer comprising a predetermined composition.
Description
Technical Field
Cross Reference to Related Applications
This application claims the benefit of korean patent application No. 10-2019-0070250, filed at 13.6.2019 and korean patent application No. 10-2020-0071597, filed at 12.6.2020 and incorporated herein by reference in its entirety.
The present disclosure relates to a non-conductive film and a method for manufacturing a semiconductor laminate.
Background
Recently, as the trend toward miniaturization, high functionality, and capacity increase of electronic devices is expanding, and the demand for densification and high integration of semiconductor packages is rapidly increasing, the size of semiconductor chips is becoming larger. In terms of improving the integration, stack packaging methods for laminating chips in multiple stages are increasing.
Further, recently, a semiconductor using Through Silicon Vias (TSVs) has been developed, and signal transmission Via bump bonding is performed. Thermal compression bonding techniques are mainly applied for bump bonding. At this time, in the thermocompression bonding technique, the thermosetting property of the adhesive affects package manufacturing workability and package reliability.
A Non-Conductive Paste (NCP) in the form of a Paste has been developed as an adhesive for filling between TSV layers, but there is a problem in that the pitch of the bumps becomes narrower and filling becomes difficult. To overcome this problem, a Non-Conductive Film (NCF) implemented in the form of a Film has been developed.
In thermocompression bonding for bump bonding, the adhesive must be rapidly cured at high temperature, and curing is suppressed at room temperature, and storage stability should be good. Among these adhesives, catalysts play an important role in controlling the degree of curing, and heat latent catalysts for this purpose are being developed.
In addition, in order for the adhesive film to absorb the bump electrode height difference well, the adhesive film must contain a low molecular weight epoxy resin. However, the low molecular weight epoxy resin of the adhesive film migrates toward the adhesive film, which causes a problem of a change in physical properties of the adhesive film, and thus development of a protective film for overcoming the problem is required.
Disclosure of Invention
Technical problem
An object of the present disclosure is to provide a non-conductive film having excellent storage stability at room temperature and having high product stability and reliability.
Another object of the present disclosure is to provide a method for manufacturing a semiconductor laminate using the above non-conductive film.
Technical scheme
Provided herein are non-conductive films comprising: an adhesive layer comprising a low molecular weight epoxy resin; and an adhesive layer, wherein the adhesive layer comprises: a (meth) acrylate resin containing 1 to 10% by weight of a repeating unit derived from a hydroxyl-containing acrylate monomer or oligomer; and a crosslinking agent containing an isocyanate-based compound.
Also provided herein is a method for manufacturing a semiconductor laminate, the method comprising laminating the above-described non-conductive film on a substrate having a conductive bump or a semiconductor chip having a through electrode.
Hereinafter, a non-conductive film and a method for manufacturing a semiconductor laminate according to a specific embodiment of the present disclosure will be described in more detail.
The terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the disclosure. The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
It will be understood that the terms "comprises," "comprising," and "having," as used herein, are intended to specify the presence of stated features, amounts, steps, components, or combinations thereof, but it will be understood that it does not preclude the presence or addition of one or more other features, amounts, steps, components, or combinations thereof.
Since various modifications can be made to the disclosure and various forms of the disclosure can exist, specific examples are shown and will be described in detail below. It should be understood, however, that there is no intention to limit the disclosure to the specific forms disclosed herein, and the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and technical scope of the disclosure.
As used herein, (meth) acrylate is meant to include both acrylates and (meth) acrylates.
According to one embodiment of the present disclosure, there may be provided: an adhesive layer comprising a low molecular weight epoxy resin; and an adhesive layer, wherein the adhesive layer comprises: a (meth) acrylate resin containing 1 to 10% by weight of a repeating unit derived from a hydroxyl-containing acrylate monomer or oligomer; and a crosslinking agent containing an isocyanate-based compound.
The present inventors have found through experiments that, when an adhesive layer comprising a (meth) acrylate resin containing 1 to 10% by weight of repeating units derived from a hydroxyl-containing acrylate monomer or oligomer, and a crosslinking agent containing an isocyanate-based compound is formed on an adhesive layer comprising a low molecular weight epoxy resin, this suppresses the migration of the low molecular weight epoxy resin in the adhesive layer to the adhesive layer, and thus a non-conductive film may have excellent storage stability at room temperature, and may achieve high product stability and reliability without changing physical properties or shape, thereby completing the present disclosure.
More specifically, when the (meth) acrylate resin includes 1 to 10 wt%, or 1.5 to 8 wt%, or 2 to 6 wt%, or 2 to 5 wt% of the repeating units derived from the hydroxyl group-containing acrylate monomer or oligomer, it prevents the low molecular weight epoxy resin in the adhesive layer from migrating to the adhesive layer, and thus may ensure a certain level or higher of the degree of crosslinking of the adhesive layer while maximizing the storage stability of the non-conductive film, thereby achieving an appropriate level of peel strength.
Meanwhile, when the content of the repeating unit derived from the hydroxyl group-containing acrylate monomer or oligomer in the (meth) acrylate resin is less than 1% by weight, a degree of crosslinking of the adhesive layer to a certain degree or more cannot be obtained, and thus peeling between the adhesive layer and the adhesive layer after the process may become difficult. When the content is more than 10% by weight, there is a problem that the low molecular weight epoxy resin in the adhesive layer migrates to the adhesive layer and the storage stability of the non-conductive film deteriorates.
At this time, the hydroxyl group-containing acrylate monomer may be a monomer derived from a primary alcohol, for example, it may be one or more selected from the group consisting of: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, and 2-hydroxypropanediol (meth) acrylate.
Meanwhile, the (meth) acrylate resin may include: a (meth) acrylate-based repeating unit having an alkyl group having 2 to 12 carbon atoms or a (meth) acrylate-based repeating unit containing a crosslinkable functional group, and a repeating unit derived from a hydroxyl-containing acrylate monomer or oligomer.
At this time, the (meth) acrylate resin may include 1 to 10% by weight, or 1.5 to 8% by weight, or 2 to 6% by weight, or 2 to 5% by weight of the repeating units derived from the hydroxyl-containing acrylate monomer or oligomer as described above, and may further include 90 to 99% by weight, or 92 to 98.5% by weight, or 94 to 98% by weight, or 95 to 98% by weight of the (meth) acrylate-based repeating units having an alkyl group having 2 to 12 carbon atoms or the (meth) acrylate-based repeating units including a crosslinkable functional group.
When the (meth) acrylate resin is used in the above content range, the finally formed nonconductive film prevents the low molecular weight epoxy resin in the adhesive layer from migrating to the adhesive layer, and the degree of crosslinking of the adhesive layer at a certain level or higher can be ensured while maximizing the storage stability of the nonconductive film, thereby achieving an appropriate level of peel strength.
The (meth) acrylate-based repeating unit having an alkyl group having 2 to 12 carbon atoms may be a repeating unit derived from one or more monomers or oligomers selected from the group consisting of: pentyl (meth) acrylate, n-butyl (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, or decyl (meth) acrylate.
Specific examples of the (meth) acrylate-based repeating unit including a crosslinkable functional group include a (meth) acrylate-based repeating unit including a carboxyl group, a nitrogen-containing functional group, and the like, and the (meth) acrylate-based repeating unit including a crosslinkable functional group may be derived from a (meth) acrylate-based monomer including a crosslinkable functional group.
At this time, examples of the (meth) acrylate-based monomer including a carboxyl group include (meth) acrylic acid and the like, and examples of the (meth) acrylate-based monomer including a nitrogen-containing functional group include (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam and the like, but are not limited thereto.
The weight average molecular weight of the (meth) acrylate resin may be 100000 to 1500000, preferably 200000 to 1000000. When the weight average molecular weight of the (meth) acrylate resin is less than 100000, coating properties or cohesion may be reduced, a residue remains on an adherend upon peeling, or a fracture phenomenon of the adhesive may occur. Further, when the weight average molecular weight of the (meth) acrylate resin exceeds 1500000, the viscosity is high, and thus an excessive amount of a diluting solvent must be added and the coating characteristics may be deteriorated.
The weight average molecular weight means a weight average molecular weight measured according to polystyrene by a GPC method.
In addition, the (meth) acrylate-based resin may further contain a low molecular weight compound containing a carbon-carbon double bond, etc. of vinyl acetate, styrene, or acrylonitrile, from the viewpoint of improving other functions such as compatibility.
Meanwhile, the adhesive layer may include a crosslinking agent containing an isocyanate-based compound, and the crosslinking agent containing the isocyanate-based compound may be included in the adhesive layer in an amount of 1 to 10 wt%, or 3 to 9 wt%, or 3 to 8 wt%, or 3 to 7 wt%, with respect to the (meth) acrylate resin.
The crosslinking agent containing the isocyanate-based compound is used for improving the cohesive force of the adhesive in the adhesive layer and for controlling the peel strength. At this time, when the crosslinking agent containing the isocyanate-based compound is contained in the adhesive layer in the above range, an appropriate level of peel strength can be secured, which is preferable.
When the content of the crosslinking agent containing the isocyanate-based compound is less than 1% by weight with respect to the (meth) acrylate resin, the cohesive force of the adhesive layer may be insufficient, and thus a residue may remain, or peeling between the protective film and the non-conductive film (NCF) may become difficult. When the content is more than 10% by weight, the peel strength between the protective film and the non-conductive film (NCF) becomes too low, so that the protective film may be peeled off from the non-conductive film (NCF) during processing.
The isocyanate-based compound is not particularly limited as long as it has two or more isocyanate groups in its molecule, and for example, it may include at least one selected from the group consisting of: toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and naphthalene diisocyanate, as well as the above reactants with any polyol (e.g., trimethylolpropane).
Meanwhile, the adhesive layer may contain a heat-curable adhesive. In the case of a heat-curable adhesive, the cohesive force is reduced by the application of temperature.
In addition, the adhesive layer may further contain a polyfunctional (meth) acrylate compound.
The multifunctional (meth) acrylate compound has a weight average molecular weight of 100 to 100000, and may include one or more selected from the group consisting of a multifunctional urethane (meth) acrylate and a multifunctional (meth) acrylate monomer or oligomer.
The weight average molecular weight means a weight average molecular weight measured by GPC method in terms of polystyrene.
The adhesive layer may further include at least one crosslinking agent selected from the group consisting of aziridine compounds, epoxy compounds, and metal chelate compounds.
The adhesive layer may further comprise at least one tackifier selected from the group consisting of rosin resins, terpene resins, phenol resins, styrene resins, aliphatic petroleum resins, aromatic petroleum resins, and aliphatic aromatic copolymerized petroleum resins.
The method of coating and drying the adhesive composition forming the adhesive layer is not particularly limited, and for example, the following methods may be used: coating a composition comprising each of the above components as is; or the composition is diluted with a suitable organic solvent, coated by a known apparatus such as a comma coater, a gravure coater, a die coater or a reverse coater, and then the solvent is dried at a temperature of 60 to 200 c for 10 seconds to 30 minutes. Further, in the above process, an aging step for promoting a sufficient crosslinking reaction of the adhesive may be additionally performed.
Meanwhile, the thickness of the adhesive layer is not particularly limited, but may be 5 μm to 50 μm, or 7 μm to 40 μm, or 10 μm to 30 μm.
When the adhesive layer satisfies the thickness range, peeling is easy without adhesive adhesion and residue on the surface of the non-conductive film (NCF). However, when the thickness of the adhesive layer is outside the above range, it is difficult to obtain a uniform adhesive layer, and the physical properties of the film may not be uniform.
When the thickness of the adhesive layer is less than 5 μm, there is a problem that the thickness of the layer is too thin, which causes a problem that uniform coating is difficult and cohesion is reduced. On the contrary, when the thickness is more than 50 μm, there may be a problem that cohesion becomes high due to an excessive thickness, or a residue remains on the surface of the non-conductive film (NCF) when removing the adhesive layer.
Meanwhile, the non-conductive film according to an embodiment of the present disclosure may include an adhesive layer containing a low molecular weight epoxy resin.
At this time, the low molecular weight epoxy resin is a resin having one or more epoxy groups in a molecule while having a molecular weight of less than 500 g/mol.
More specifically, the low molecular weight epoxy resin may have a weight average molecular weight of 150g/mol to 450g/mol, or 250g/mol to 400g/mol.
The non-conductive film may be distinguished from other types of films for semiconductor processes that include an epoxy resin having a relatively high molecular weight, which includes a low molecular weight epoxy resin having a weight average molecular weight as described above.
In particular, since the adhesive layer of the non-conductive film includes a low molecular weight epoxy resin, conductive bumps formed on a substrate or a semiconductor chip, which are applied to a semiconductor manufacturing process using Through Silicon Vias (TSVs), can be more easily embedded.
More specifically, the adhesive layer including the low molecular weight epoxy resin may have a melt viscosity of 100Pa · s to 10000Pa · s as measured by applying a shear rate of 10Hz and a temperature rise rate of 10 ℃/minute. Since the adhesive layer has such a melt viscosity, the embedding of the conductive bump formed on the substrate or the semiconductor chip at a high temperature can be more smoothly performed, and the generation of voids can be prevented, thereby improving the manufacturing workability and the reliability of the final product.
If the molecular weight of the low molecular weight epoxy resin is 500g/mol or more, there is a problem in that: the film becomes too brittle and breaks during the cutting of the film or during the cutting process, and does not fill the entire area around the bumps, voids may occur, and reliability is reduced.
The low molecular weight epoxy resin as described above forms a crosslinked hard structure through a curing process, and thus may exhibit excellent adhesion, heat resistance, and mechanical strength. In one example, as the epoxy resin, an epoxy resin having an average epoxy equivalent of 180 to 1000 may be used. When the epoxy equivalent of the epoxy resin is less than 180, the crosslinking density becomes too high, and the adhesive layer as a whole exhibits hard characteristics. When the epoxy equivalent is more than 1000, there is a fear that heat resistance is lowered.
Specifically, the epoxy resin may be one or more selected from the group consisting of: bisphenol-based epoxy resins, biphenyl-based epoxy resins, naphthalene-based epoxy resins, fluorene-based epoxy resins, glycidylamine-type epoxy resins, trishydroxyphenylmethane epoxy resins, tetraphenylmethane-based epoxy resins, dicyclopentadiene-type epoxy resins, and dicyclopentadiene-modified phenol-type epoxy resins.
Here, the bisphenol-based epoxy resin may include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol AF type epoxy resin, and the like.
Meanwhile, according to an embodiment of the present disclosure, the adhesive layer may further include a thermoplastic resin, a thermosetting resin, a curing agent, an inorganic filler, and a catalyst.
As the thermoplastic resin, thermosetting resin, curing agent, inorganic filler and catalyst contained in the adhesive layer, conventional components known for adhesive layer compositions in the field of non-conductive films may be used.
The type of the thermoplastic resin is not particularly limited, and for example, it may include at least one polymer resin selected from the group consisting of: polyimides, polyetherimides, polyesterimides, polyamides, polyethersulfones, polyetherketones, polyolefins, polyvinylchloride, phenoxy resins, reactive butadiene acrylonitrile copolymer rubbers, and (meth) acrylate resins.
Further, examples of the thermosetting resin are not particularly limited, and for example, an epoxy resin can be preferably used as the thermosetting resin.
As the curing agent, a compound known to be used as a curing agent for thermosetting resins can be used. More specifically, the curing agent may include at least one compound selected from the group consisting of an amine-based curing agent and an anhydride-based curing agent.
As the curing agent, a novolac-based phenol resin can be preferably applied.
Novolac-based phenol resins have a chemical structure in which the ring is located between reactive functional groups. Due to these structural characteristics, the novolac-based phenol resin may further reduce hygroscopicity of the adhesive layer composition, and may further improve stability during high-temperature IR reflow, which may be used to prevent a peeling phenomenon or reflow cracking of the adhesive layer.
Specific examples of the novolac-based phenol resin include one or more selected from the group consisting of: novolac phenolic resins, neophenol (Xylok) novolac phenolic resins, cresol novolac phenolic resins, biphenol novolac phenolic resins, bisphenol a novolac phenolic resins, and bisphenol F novolac phenolic resins.
Meanwhile, as the inorganic filler, one or more inorganic particles selected from the group consisting of: alumina, silica, barium sulfate, magnesium hydroxide, magnesium carbonate, magnesium silicate, magnesium oxide, calcium silicate, calcium carbonate, calcium oxide, aluminum hydroxide, aluminum nitride, and aluminum borate.
In addition, a catalyst is used to accelerate the action of the curing agent or the curing of the adhesive layer composition, and a catalyst known for the adhesive layer composition may be used without particular limitation. For example, as the catalyst, one or more selected from the group consisting of a phosphorus-based compound, a boron-based compound, and a phosphorus-boron-based compound and an imidazole-based compound may be used.
Meanwhile, the thickness of the adhesive layer is not particularly limited, but may be appropriately adjusted within a range of 5 μm to 40 μm, or 8 μm to 30 μm.
When the thickness of the adhesive layer is less than 5 μm, there may be a problem of reliability degradation because it does not fill the entire area around the bump. In contrast, when the thickness is more than 40 μm, there may be a problem that the connection between the bump and the pad is difficult or the semiconductor package becomes thick.
Meanwhile, the peel strength of the adhesive layer on the adhesive layer may be 10g/25mm to 60g/25mm, or 15g/25mm to 55g/25mm, or 20g/25mm to 50g/25mm as measured at a peel angle of 180 degrees and a peel rate of 300 mm/min.
When the peel strength of the adhesive layer on the adhesive layer exceeds 60g/25mm, there may be a problem that peeling is difficult when the protective film is peeled from the non-conductive film (NCF) after processing. In contrast, when the peel strength of the adhesive layer on the adhesive layer is less than 10g/25mm, there may be a problem that the protective film is not well adhered to the non-conductive film (NCF) to be separated during processing.
The non-conductive film may further include a release film formed on one surface of the adhesive layer to be opposite to the adhesive layer.
Specific examples of the release film are not particularly limited, and polyester films such as PET and polyolefin films such as PE and PP can be used.
The release film may be removed after laminating the non-conductive film on the substrate having the conductive bump or the semiconductor chip including the through electrode.
Meanwhile, according to another embodiment of the present disclosure, there may be provided a method for manufacturing a semiconductor laminated body, including laminating the non-conductive film of the above embodiment on a substrate having a conductive bump or a semiconductor chip having a through electrode.
Specifically, the nonconductive film of the embodiment is attached on the surface of the bump wafer by vacuum lamination, separated into individual chips by a dicing process, and the bump chips to which the individual nonconductive films are attached are subjected to thermocompression bonding using a thermocompression bonding machine.
Subsequently, depending on the application, additional compression bonding processes and molding processes, as well as individualized steps of molding the wafer, may additionally be applied.
Advantageous effects
According to the present disclosure, it is possible to provide a non-conductive film having excellent storage stability at room temperature and having high product stability and reliability, and a method of manufacturing a semiconductor laminate using the same.
Detailed Description
Specific embodiments of the present disclosure are described in more detail with reference to the following examples. However, these examples are provided for illustrative purposes only and should not be construed as limiting the scope of the present disclosure.
Preparation example 1: preparation of (meth) acrylate resins
Preparation examples 1 to 1
97.5g of 2-ethylhexyl acrylate (2-EHA), 2.5g of 4-hydroxybutyl acrylate (4-HBA), 0.1g of benzoyl peroxide as a polymerization initiator and 170g of Methyl Ethyl Ketone (MEK) were used to prepare 270g of a (meth) acrylate resin.
Preparation examples 1 to 2
97g of 2-ethylhexyl acrylate (2-EHA), 3g of 2-hydroxyethyl acrylate (2-HEA), 0.1g of benzoyl peroxide and 170g of Methyl Ethyl Ketone (MEK) were used to prepare 270g of a (meth) acrylate resin.
Preparation examples 1 to 3
93g of 2-ethylhexyl acrylate (2-EHA), 1g of 2-hydroxyethyl acrylate (2-HEA), 6g of 4-hydroxybutyl acrylate (4-HBA), 0.1g of benzoyl peroxide as a polymerization initiator and 170g of Methyl Ethyl Ketone (MEK) were used to prepare 270g of a (meth) acrylate resin.
Preparation examples 1 to 4
99g of 2-ethylhexyl acrylate (2-EHA), 1g of 2-hydroxypropyl acrylate (2-HPA), 0.1g of benzoyl peroxide as a polymerization initiator, and 170g of Methyl Ethyl Ketone (MEK) were used to prepare 270g of a (meth) acrylate resin.
Preparation example 2: preparation of the adhesive layer
50g of bisphenol F type epoxy resin (KDS-8170, kukdo Chemical, molecular weight: 340 g/mol) as a low molecular weight epoxy resin, 40g of bisphenol aldehyde varnish epoxy resin (NC-3000H, nippon Kayaku, epoxy equivalent: 288g/eq, softening point: 70), 70g of phenol resin KPH-F3075 (Kolon Chemical, hydroxyl equivalent: 175g/eq, softening point 75), 40g of thermoplastic acrylate resin KG-3015 (Negami Chemical), 0.5g of 2-phenyl-4-methyl-5-dimethyloimidazole (2PMH4Z, shikoku Kasei) as a catalyst, and 70g of filler SC1050 (spherical silica, average particle diameter: 0.3 μm) were dissolved in methyl ethyl ketone to obtain an adhesive layer composition (solid content concentration: 35% by weight).
The prepared adhesive layer composition was coated on a polyethylene terephthalate film (38 μm thick), and then dried at 110 ℃ for 5 minutes to obtain an adhesive layer of 20 μm thickness.
The above adhesive layers were laminated and laminated until they reached 320 μm, and then measured by applying a shear rate of 10Hz and a temperature rise rate of 10 ℃/min using Anton Parr MCR302, and the minimum value of the measurement was determined by the melt viscosity.
Example 1: preparation of non-conductive films
(1) Preparation of the adhesive layer composition
100g of the (meth) acrylate resin prepared in preparation example 1-1, 2.5g of MHG-80B (Asahi Kasei) as a crosslinking agent (the content of the crosslinking agent is 5% by weight compared with the solid content of the (meth) acrylate resin), and 1.1mg of DBTDL were mixed to prepare an adhesive layer composition.
(2) Preparation of non-conductive films
The adhesive layer composition was coated on a release PET and allowed to stand in an oven at a temperature of 110 ℃ for 3 minutes to form an adhesive layer having a thickness of 20 μm, which was then attached to the upper portion of the adhesive layer prepared in preparation example 2 to manufacture a non-conductive film including the adhesive layer and the adhesive layer.
Example 2 and comparative examples 1 to 6
A non-conductive film was manufactured in the same manner as in example 1 except that an adhesive layer composition was prepared by combining the components used in table 1 below.
[ Table 1]
* A crosslinking agent: MHG-80B (Asahi Kasei)
[ test examples ]
The physical properties of the non-conductive films prepared in examples and comparative examples were evaluated by the following methods, and the results are shown in table 2 below.
(1)Measurement of peel Strength
In order to measure the peel strength between the adhesive layer and the adhesive layer, the non-conductive films prepared in examples 1 to 2 and comparative examples 1 to 5 were left at room temperature for 1 hour, and then a sample having a width of 25mm was prepared to measure the peel strength at room temperature. The peel strength was measured using a texture analyzer at a peel angle of 180 degrees and a peel rate of 300 mm/min.
For each sample, the peel strength was measured three or more times, and an average value was obtained.
(2) Comparison of storage stability-measurement of calorific value Change Rate
For the adhesive layer prepared in preparation example 2, the initial calorific value of the adhesive layer in terms of the area at the curing temperature was measured using a differential thermal analyzer (DSC).
Then, the adhesive layer composition was applied to the upper portion of the adhesive layer to prepare the non-conductive films of examples 1 to 2 and comparative examples 1 to 5 including the adhesive layer and the adhesive layer, and then the prepared non-conductive films were left at 60 ℃ for 24 hours.
Then, the nonconductive film was separated into an adhesive layer and an adhesive layer, and then the calorific value of the adhesive layer was measured using a differential thermal analyzer (DSC).
The rate of change was calculated using the following equation 1.
[ formula 1]
Change rate (%) = [ (peak area of initial adhesive layer-peak area after standing at 60 ℃ for 24 hours)/peak area of initial adhesive layer ] × 100
(3) Evaluation of voids
By Scanning Acoustic Tomography (SAT), if the area occupied by the voids between bump chips is 1% or less, it is evaluated as acceptable (O), and if it is greater than 1%, it is evaluated as unacceptable (X).
[ Table 2]
| Peel strength (g/25 mm) | Rate of change in Heat value (%) | Evaluation of voids | |
| Example 1 | 35 | 11 | O |
| Example 2 | 28 | 14 | O |
| Comparative example 1 | 12 | 26 | X |
| Comparative example 2 | 20 | 21 | X |
| Comparative example 3 | 150 | 8 | O |
| Comparative example 4 | 23 | 17 | X |
| Comparative example 5 | 68 | 9 | O |
As shown in table 2, it was confirmed that in the non-conductive films provided in examples 1 and 2, the peel strength of the adhesive layer on the adhesive layer satisfied the range of 10g/25mm to 60g/25mm, the separation problem of the adhesive layer on the adhesive layer was reduced when this process was performed, and the pick-up (pick-up) success rate was increased when the adhesive layer and the adhesive layer were peeled.
Further, it was confirmed that the non-conductive films provided in examples 1 and 2 had a low rate of change when stored at room temperature and thus had excellent storage stability at room temperature, and the adhesive film absorbed the bump electrode height difference so that voids did not actually occur during bonding of the bump chips.
Claims (13)
1. A non-conductive film, comprising: an adhesive layer comprising a low molecular weight epoxy resin; and an adhesive layer, wherein the adhesive layer,
wherein the adhesive layer comprises: a (meth) acrylate resin containing from 2 to 6% by weight of repeating units derived from a hydroxyl-containing acrylate monomer or oligomer; and a crosslinking agent containing an isocyanate-based compound,
wherein the crosslinking agent containing an isocyanate-based compound is contained in the adhesive layer in an amount of 3 to 9% by weight relative to the (meth) acrylate resin.
2. The non-conductive film of claim 1,
wherein the non-conductive film is used in a semiconductor manufacturing process using through silicon vias.
3. The non-conductive film of claim 1,
wherein the low molecular weight epoxy resin has a weight average molecular weight of 150g/mol to 450g/mol.
4. The non-conductive film of claim 1,
wherein the (meth) acrylate resin comprises: a (meth) acrylate-based repeating unit having an alkyl group having 2 to 12 carbon atoms or a (meth) acrylate-based repeating unit containing a crosslinkable functional group, and a repeating unit derived from the hydroxyl-containing acrylate monomer or oligomer.
5. The non-conductive film of claim 4,
wherein the (meth) acrylate resin comprises 1 to 10 weight percent of the repeating units derived from the hydroxyl-containing acrylate monomer or oligomer; and 90 to 99% by weight of a (meth) acrylate-based repeating unit having an alkyl group having 2 to 12 carbon atoms or a (meth) acrylate-based repeating unit containing a crosslinkable functional group.
6. The non-conductive film of claim 1,
wherein the hydroxyl-containing acrylate monomer comprises one or more selected from the group consisting of: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, and 2-hydroxypropanediol (meth) acrylate.
7. The non-conductive film of claim 1,
wherein the isocyanate-based compound comprises at least one selected from the group consisting of: toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, and naphthalene diisocyanate.
8. The non-conductive film of claim 1,
wherein the adhesive layer has a thickness of 5 to 50 μm.
9. The non-conductive film of claim 1,
wherein the adhesive layer has a thickness of 5 to 40 μm.
10. The non-conductive film of claim 1,
wherein the peel strength of the adhesive layer on the adhesive layer is 10g/25mm to 60g/25mm as measured at a peel angle of 180 degrees and a peel rate of 300 mm/min.
11. The non-conductive film of claim 1,
wherein the adhesive layer has a melt viscosity of 100Pa s to 10000Pa s as measured by applying a shear rate of 10Hz and a temperature rise rate of 10 ℃/min.
12. The nonconductive film as set forth in claim 1, further comprising a release film formed on one surface of the adhesive layer to be opposed to the adhesive layer.
13. A method for manufacturing a semiconductor laminated body, comprising laminating the nonconductive film according to claim 1 on a substrate having a conductive bump or a semiconductor chip having a through electrode.
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| KR10-2019-0070250 | 2019-06-13 | ||
| PCT/KR2020/007665 WO2020251307A1 (en) | 2019-06-13 | 2020-06-12 | Non-conductive film and preparation method for semiconductor laminate |
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| Publication number | Publication date |
|---|---|
| KR20200143289A (en) | 2020-12-23 |
| CN112673071A (en) | 2021-04-16 |
| KR102405907B1 (en) | 2022-06-07 |
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