TW201743385A - Film-like adhesive, sheet for semiconductor processing, and method of manufacturing semiconductor device - Google Patents

Abstract

The film-like adhesive 13 of the present invention is a curable film-like adhesive; the film-like adhesive 13 of a single layer before curing having a thickness of 60 μm or the film-like adhesive 13 of two or more layers before curing becomes a total thickness The laminate having a thickness of 60 μm has an elongation at break at 0° C. of 60% or less, and the adhesion of the film-like adhesive 13 before curing to the semiconductor wafer is 300 mN/25 mm or more. The sheet for semiconductor processing 1 of the present invention is provided with a film-like adhesive 13 on a support sheet 10 having a substrate 11.

Description

Film-like adhesive, sheet for semiconductor processing, and method of manufacturing semiconductor device

The present invention relates to a film-like adhesive, a sheet for semiconductor processing, and a method of producing a semiconductor device.

The priority of Japanese Patent Application No. 2016-069604, filed on Jan. 30,,,,,,,,,,,,

A dicing sheet is used when dicing a semiconductor wafer into a semiconductor wafer by dicing. The dicing sheet is formed, for example, by providing an adhesive layer on a substrate, and is used by attaching the above-mentioned adhesive layer to a semiconductor wafer. After the dicing, the adhesive layer is cured by, for example, irradiation with an energy ray such as ultraviolet rays, whereby the adhesive force of the adhesive layer is lowered, whereby the semiconductor wafer is pulled away from the cured adhesive layer, and is easily picked up.

On the other hand, for the semiconductor wafer after the pickup, for example, die bonding is performed on the circuit surface of the substrate by a film-like adhesive, and if necessary Further, one or more other semiconductor wafers are laminated on the semiconductor wafer, and after wire bonding, the entire body is sealed by a resin.

The semiconductor device obtained in this manner is used to finally manufacture a target semiconductor device. Therefore, the semiconductor wafer may be picked up in a state in which a film-like adhesive is provided on the surface of the semiconductor wafer to be a target for die bonding.

In the case where a film-like adhesive is used as such, a dicing die bonding sheet is sometimes used, and the dicing die bonding sheet is provided with an uncut material on the adhesive layer in the above-mentioned dicing sheet. Membrane adhesive. On the other hand, a plurality of semiconductor wafers which are singulated in advance may be provided on the film-like adhesive. In this case, a sheet for semiconductor processing having the same configuration as that of the dicing die-bonding sheet is also used. In the case of using such a sheet for semiconductor processing, for example, a plurality of semiconductor wafers which are singulated in advance are provided on the film-like adhesive in the sheet for semiconductor processing, and the sheet for semiconductor processing is stretched at a low temperature ( In this manner, the film-like adhesive is cut in accordance with the outer shape of the semiconductor wafer, and the semiconductor wafer having the film-like adhesive after the cutting is prepared on the surface to be coated.

As a film for semiconductor processing including such a film-like adhesive, a film-like adhesive (that is, a die-bonding film) is attached to a semiconductor wafer at 25 ° C, and a cutting adhesive force is applied, and then a dicing sheet is attached. The shearing force at the time of cutting the film (that is, the dicing film) is set to a sheet for semiconductor processing in a specific range (see Patent Document 1); a film-like adhesive before thermosetting (that is, a grain bonding film) The ratio of the elongation at break at 25 ° C, the ratio of the tensile storage elastic modulus at 0 ° C to the tensile storage elastic modulus at 25 ° C, is set to a sheet for semiconductor processing within a specific range (see Patent Document 2); The thickness of the semiconductor wafer is A (μm), the thickness of the film-like adhesive (that is, the die-bonding film) is B (μm), and when the thickness of the substrate is C (μm), C/ A, C/B, and A/B are sheets for semiconductor processing set in a specific range (see Patent Document 3); and elongation at break at 25 ° C in a film-like adhesive (that is, a sheet) in a B-stage state. The semiconductor processing sheet set such that the thickness of the dicing sheet (that is, the dicing tape) is A and the thickness of the film-like adhesive is B is set to be within a specific range ( Refer to Patent Document 4).

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2011-171588.

Patent Document 2: Japanese Laid-Open Patent Publication No. 2011-228399.

Patent Document 3: Japanese Laid-Open Patent Publication No. 2012-222002.

Patent Document 4: Japanese Laid-Open Patent Publication No. 2009-283925.

In the sheet for semiconductor processing having a film-like adhesive, in particular, from the viewpoint of improving the cutting property of the film-based adhesive based on the elongation, the desired performance is further improved.

Accordingly, an object of the present invention is to provide a novel sheet for semiconductor processing which comprises a film-like adhesive and which has excellent cutting properties based on elongation.

In order to solve the above problems, the present invention provides a film-like adhesive which is a curable film-like adhesive; a film-like adhesive having a thickness of 60 μm before curing, or two or more layers before curing; The laminate having a thickness of 60 μm in total has an elongation at break at 0° C. of 60% or less, and the adhesion of the film-form adhesive to the semiconductor wafer before curing is 300 mN/25 mm or more.

Further, the present invention provides a sheet for semiconductor processing, in which the film-like adhesive is provided on a support sheet.

In the sheet for semiconductor processing of the present invention, it is preferable that the support sheet has an adhesive layer provided on the substrate, and the film-like adhesive is provided in direct contact with the adhesive layer.

Further, the present invention provides a method of manufacturing a semiconductor device using the film-like adhesive; the method for manufacturing a semiconductor device comprising the steps of forming a laminated structure to form a laminated structure on a support sheet The film-like adhesive is provided, and a plurality of divided semiconductor wafers are provided on a surface of the film-like adhesive opposite to the side on which the support sheet is provided; the cutting step is performed before The film-like adhesive in the laminated structure extends in the direction along the surface of the film-like adhesive while cooling, and cuts the film-like adhesive; and the pulling-off step, and the film-like shape after cutting is provided The aforementioned semiconductor wafer of the agent is pulled away from the aforementioned support sheet.

In the method of manufacturing a semiconductor device of the present invention, before the step of forming the stacked structure, the method further includes the step of forming a modified layer to irradiate the infrared region in such a manner as to focus on a focus set inside the semiconductor wafer. a laser beam forming a reforming layer inside the semiconductor wafer; and a dividing step of grinding a surface of the semiconductor wafer on which the modified layer is formed to provide the film-like adhesive, and the semiconductor Applying a force during grinding to the wafer, thereby dividing the semiconductor wafer at a portion of the modified layer to obtain a plurality of semiconductor wafers; and using the plurality of semiconductor wafers obtained in the dividing step in the laminated structure forming step in.

According to the present invention, there is provided a novel sheet for semiconductor processing comprising a film-like adhesive, and the film-like adhesive has good cutting properties based on elongation.

1‧‧‧Slices for semiconductor processing

8‧‧‧Semiconductor wafer

8b‧‧‧Back of semiconductor wafer

8'‧‧‧Semiconductor wafer

8a'‧‧‧ Surface of semiconductor wafer

8b'‧‧‧ Back of semiconductor wafer

10‧‧‧Support tablets

11‧‧‧Substrate

11a‧‧‧ Surface of the substrate

12‧‧‧Adhesive layer

12a‧‧‧ Surface of the adhesive layer

13‧‧‧membranous adhesive

13a‧‧‧ Surface of film-like adhesive

13b‧‧‧Back of the film-like adhesive

13'‧‧‧Filmed adhesive after cutting

61‧‧‧Tira

62‧‧‧ Grinder

63‧‧‧Back grinding belt

81'‧‧‧Modified layer of semiconductor wafer

101‧‧‧Layered structure

Fig. 1 is a cross-sectional view showing an embodiment of a semiconductor processing sheet of the present invention in a schematic manner.

2 is a cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device in a case where a film-like adhesive or a sheet for semiconductor processing of the present invention is used.

3 is a cross-sectional view showing an embodiment of a method of forming a semiconductor wafer by forming a trench in a semiconductor wafer.

4 is a cross-sectional view showing an embodiment of a method of forming a semiconductor wafer by forming a modified layer on a semiconductor wafer in a schematic manner.

<film-like adhesive>

The film-like adhesive of the present invention is a curable film-like adhesive; the film-like adhesive agent of a single layer before curing having a thickness of 60 μm or the film-like adhesive of two or more layers before curing is 60 μm in total. In the laminated body, the elongation at break at 0 ° C is 60% or less, and the adhesion of the film-like adhesive before curing to the semiconductor wafer is 300 mN / 25 mm or more.

In the film-like adhesive of the present invention, when the elongation at break is 60% or less, when a sheet for semiconductor processing is formed as will be described later, even when the sheet is stretched at a low temperature, the sheet (that is, a film-like adhesive) is used. When expanding in the direction along the surface of the sheet, the film-like adhesive can be easily cut at the target portion.

In addition, when the film-like adhesive of the present invention has a bonding strength of 300 mN/25 mm or more and is extended at a low temperature as described above, it can be cut at a target portion without an abnormality such as a defect of the film-like adhesive. It is presumed that the film-like adhesive has a sufficient adhesion to the semiconductor wafer, and when the film-like adhesive is extended, the force at the time of stretching is likely to concentrate on the region near the end of the semiconductor wafer in the film-like adhesive. On the other hand, when the adhesive force is less than 300 mN/25 mm, the film-like adhesive becomes brittle at a low temperature, and therefore, in the stretched film-like adhesive, defects occur in a region other than the vicinity of the end portion of the semiconductor wafer. As a result, the force at the time of stretching is dispersed in the film-like adhesive, and thus the film-like adhesive is insufficiently cut at the target portion. Further, the film-like adhesive before curing exhibits an equivalent adhesion to the semiconductor wafer and the semiconductor wafer.

The film-like adhesive has curability. The film-like adhesive is preferably thermosetting, and preferably has pressure-sensitive adhesiveness. The film-like adhesive which has both thermosetting property and pressure-sensitive adhesive property can be attached by gently pressing it to various adherends in an uncured state. Further, it may be attached to various adherends by heating the film-like adhesive to soften it. The film-like adhesive is finally cured into a cured product having high impact resistance by curing, and the cured product can maintain sufficient adhesive properties under severe high temperature and high humidity conditions.

The film-like adhesive may be composed of one layer (that is, a single layer), or may be composed of a plurality of layers of two or more layers. In the case where the film-like adhesive is composed of a plurality of layers, The plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited insofar as the effects of the present invention are not impaired.

In addition, in the present specification, the present invention is not limited to the case of a film-like adhesive. The phrase "the plural layers may be the same or different from each other" means that "all layers may be the same, or all layers may be different, and only a part of the layers may be the same". Further, the phrase "the plural layers are different from each other" means that "at least one of the constituent materials and the thickness of each layer is different from each other".

The thickness of the film-like adhesive is not particularly limited, but is preferably 1 μm to 50 μm, more preferably 3 μm to 40 μm. When the thickness of the film-like adhesive is at least the above lower limit value, a higher adhesion force to the adherend (that is, a semiconductor wafer) can be obtained. In addition, by the thickness of the film-like adhesive being less than or equal to the above upper limit, the film-like adhesive can be more easily cut by the extension described later.

Here, the "thickness of the film-like adhesive" means the thickness of the entire film-like adhesive. For example, the thickness of the film-like adhesive composed of a plurality of layers means the total thickness of all the layers constituting the film-like adhesive. In addition, as a method of measuring the thickness of the film-like adhesive, for example, the following method can be used, and the thickness is measured using a contact thickness meter at any five locations, and the average of the measured values is calculated.

The above-mentioned laminated system for obtaining the above-mentioned rupture elongation is obtained by laminating two or more layers of a film-like adhesive agent before curing having a thickness of less than 60 μm in a total thickness of 60 μm.

The elongation at break (%) of the film-like adhesive or laminate at 0 ° C can be measured by the following method.

In other words, the film-like adhesive or laminate having a width of 6 mm, a length of 5 mm, and a thickness of 60 μm was used as a test piece, and the load applied to the test piece was changed from 1 N to 18 N at a rate of 1 N/min. The elongation was measured, and the elongation at break of the test piece was measured, whereby the elongation at break was determined.

In the present specification, "the elongation at break is X% (where X is a positive number)" means a tensile test piece (that is, a film-like adhesive or a laminate) in the above measurement method and the test piece is When the test piece is stretched in the stretching direction to a length of X% of the original length (that is, the length at the time of unstretching), the test piece is broken, that is, the entire length of the test piece in the stretching direction is stretched. When the front length is [1+X/100] times, the test piece is broken.

The film-like adhesive or laminate has an elongation at break (%) of 60% or less, preferably 57% or less, more preferably 54% or less. When the breaking elongation is equal to or less than the above upper limit value, the film-like adhesive can be favorably cut by stretching.

In addition, the lower limit of the elongation at break (%) of the film-like adhesive or the laminate is not particularly limited, and is preferably, for example, 5%. When the breaking elongation is equal to or higher than the lower limit value, the workability of the film-like adhesive is improved, and the effect of suppressing the scattering of the film-like adhesive at the time of stretching is increased.

The breaking elongation (%) can be appropriately adjusted by, for example, adjusting the kind and amount of the component contained in the film-like adhesive.

For example, by adjusting the molecular weight and content of the polymer component (a) to be described later, the structure of the components constituting the epoxy-based thermosetting resin (b), the softening point and content, and the content of the filler (c), etc. The aforementioned elongation at break is easily adjusted.

However, these adjustment methods are only one example.

The adhesion of the film-like adhesive before curing to the semiconductor wafer (N/25 mm) can be measured by the following method.

That is, a laminated sheet of a film-like adhesive and an adhesive tape having a width of 25 mm and an arbitrary length was produced. The laminated sheet is provided with a film-like adhesive on the adhesive area layer of the adhesive tape. Then, the laminated sheet was attached to the semiconductor wafer by heating to a film-like adhesive of 40 ° C to 70 ° C to form a laminate in which an adhesive tape, a film-like adhesive, and a semiconductor wafer were sequentially laminated. Immediately after the production of the laminate in the environment of 15 ° C to 27 ° C for 30 minutes, the following 180° peeling is performed: the surfaces in which the film-like adhesive and the semiconductor wafer are in contact with each other are 180° from each other. In this manner, the laminated sheets of the film-like adhesive and the adhesive tape were peeled off from the semiconductor wafer at a peeling speed of 300 mm/min. The peeling force at this time was measured, and the measured value of the peeling force was set as the adhesive force (N/25 mm) of the film-form adhesive agent for the semiconductor wafer before hardening. The length of the laminated sheet used for the measurement is not particularly limited as long as it can stably measure the peeling force, and is preferably 100 mm to 300 mm.

The adhesion of the film-form adhesive to the semiconductor wafer before curing is 300 mN/25 mm or more, and may be, for example, 310 mN/25 mm or more, 340 mN/25 mm or more, 380 mN/25 mm or more, but is not limited thereto. .

In addition, the upper limit of the above-mentioned adhesive force is not particularly limited, and may be selected from, for example, 10N/25mm, 800mN/25mm, 700mN/25mm, 600mN/25mm, 500mN/25mm, etc., but these are examples.

The adhesion of the film-like adhesive agent before the curing to the semiconductor wafer can be appropriately adjusted by, for example, adjusting the kind and amount of the component contained in the film-like adhesive.

For example, the molecular weight of the polymer component (a) to be described later, the ratio of each monomer component constituting the polymer component (a), the softening point of the component constituting the epoxy thermosetting resin (b), and the film are adjusted. The adhesive strength of the film-like adhesive can be easily adjusted by the content of each component contained in the adhesive.

However, these adjustment methods are only one example.

The film-like adhesive of the present invention exhibits good cutting characteristics even at a relatively slow elongation speed. For example, the film-like adhesive of the present invention is particularly preferably used in the following manner: as will be described later, the stretching speed is reduced to 0.5 mm/sec to 100 mm/sec or the like. In the case where the stretching speed is so slow, the semiconductor wafer becomes less susceptible to damage when the film-like adhesive is cut, and the effect of the present invention is more remarkable.

As a preferable film-like adhesive agent, the film-form adhesive agent containing the polymer component (a) and the epoxy-type thermosetting resin (b) is mentioned, for example.

[Binder composition]

The film-like adhesive may be formed of an adhesive composition containing a constituent material of the film-like adhesive. For example, the adhesive composition is applied to the surface to be formed of the film-like adhesive, and if necessary, the adhesive composition is dried, whereby a film-like adhesive can be formed at the target portion. A more specific method of forming the film-like adhesive will be described in detail later together with the formation method of the other layers. The content ratio of the components which are not vaporized at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the film-like adhesive. In the present specification, the term "normal temperature" means a temperature which is not particularly cold or particularly hot, that is, a normal temperature, and examples thereof include a temperature of 15 ° C to 25 ° C.

The adhesive composition may be applied by a known method, and examples thereof include the following various coaters: air knife coater, knife coater, bar coater, gravure coater, and corner washer Coater, roll coater, roll coater, curtain coater, die coater, knife coater, screen coater, meyer bar coater , contact coater, etc.

The drying conditions of the composition of the second embodiment are not particularly limited, and when the composition of the adhesive contains a solvent to be described later, it is preferably heated and dried. In the case, for example, drying is preferably carried out at 70 ° C to 130 ° C for 10 seconds to 5 minutes.

As a preferable adhesive composition, the adhesive composition containing the polymer component (a) and the epoxy thermosetting resin (b) is mentioned, for example. Hereinafter, each component will be described.

(polymer component (a))

The polymer component (a) can be regarded as a component formed by a polymerization reaction of a polymerizable compound, and is used to impart film forming property or flexibility to a film-like adhesive, and to improve adhesion to a semiconductor wafer or the like. That is, the polymer compound of the attached). Further, the polymer component (a) is also a component which does not belong to the epoxy resin (b1) and the heat curing agent (b2) which will be described later.

The polymer component (a) to be contained in the adhesive composition and the film-like adhesive agent may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrary. select.

Examples of the polymer component (a) include an acrylic resin, a polyester, a urethane resin, an urethane acrylate resin, a polyoxyn resin, a rubber resin, and a phenoxy resin. The thermosetting polyimine or the like is preferably an acrylic resin.

A well-known acrylic polymer is mentioned as said acrylic resin in the polymer component (a).

The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is within such a range, the elongation at break of the film-like adhesive or the laminate and the adhesion of the film-like adhesive are easily adjusted to the above range.

On the other hand, when the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability of the film-like adhesive (that is, the stability over time during storage) is improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the above-described upper limit, the film-like adhesive can easily follow the uneven surface of the adherend, and it is possible to further suppress the occurrence of voids between the adherend and the film-like adhesive. Wait.

In the present specification, the "number average molecular weight" and the "weight average molecular weight" are polystyrene-converted values measured by a gel permeation chromatography (GPC) method unless otherwise specified. .

The glass transition temperature (Tg) of the acrylic resin is preferably from -60 ° C to 70 ° C, more preferably from -30 ° C to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit value, the adhesion between the film-like adhesive and the support sheet described later is suppressed, and it is easier to pull the semiconductor wafer having the film-like adhesive from the support sheet at the time of pick-up. In addition, when the Tg of the acrylic resin is at most the above upper limit value, the adhesion between the film-like adhesive and the semiconductor wafer is improved. Furthermore, this is said In the specification, the "glass transition temperature" is a DSC (Differential Scanning Calorimetry) curve of a sample measured by a differential scanning calorimeter, and is expressed by the inflection point temperature of the obtained DSC curve.

Examples of the acrylic resin include a (meth) acrylate copolymer having a structural unit derived from a (meth) acrylate monomer. Examples of the (meth) acrylate constituting the acrylic resin herein include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, ( Methyl)hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid N-decyl ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as (methyl)) Lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also known as myristyl (meth) acrylate), pentadecyl (meth) acrylate , cetyl (meth) acrylate (also known as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as ( Methyl)stearyl acrylate The alkyl group of the alkyl ester is an alkyl (meth)acrylate having a chain structure of 1 to 18; isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. (methyl a cycloalkyl acrylate; an arylalkyl (meth) acrylate such as benzyl (meth) acrylate; (methyl) (cyclo)alkyl (meth) acrylate such as dicyclopentenyl acrylate; cycloalkenyloxyalkyl (meth) acrylate such as dicyclopentenyloxyethyl (meth)acrylate; (meth) propylene a glycidyl group-containing (meth) acrylate such as glycidyl (meth)acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylate 2-hydroxypropyl ester, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. A hydroxyl group-containing (meth) acrylate; a (meth) acrylate containing a substituted amine group such as N-methylaminoethyl (meth) acrylate. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of an amine group are substituted with a group other than a hydrogen atom.

Further, in the present specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The terms similar to (meth)acrylic acid are also the same. For example, the concept of "(meth) acrylate" includes both "acrylate" and "methacrylate", "(meth) propylene sulfhydryl" The concept includes both "acryloyl" and "methacryl".

The acrylic resin may be selected, for example, from (meth)acrylic acid ester, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol acrylamide. One or two or more kinds of monomers are copolymerized.

The number of the monomers constituting the acrylic resin may be one or two or more. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected.

In addition to the above-mentioned hydroxyl group, the acrylic resin may have the following functional groups which may be bonded to other compounds: a vinyl group, a (meth)acrylinyl group, an amine group, a carboxyl group, an isocyanate group or the like. These functional groups represented by a hydroxyl group in the acrylic resin may be bonded to other compounds via a crosslinking agent (f) to be described later, or may be directly bonded to other compounds without via the crosslinking agent (f). Since the acrylic resin is bonded to another compound by the above functional group, the reliability of the package obtained by using the film-like adhesive tends to be improved.

In the present invention, a thermoplastic resin other than the acrylic resin (hereinafter sometimes referred to simply as "thermoplastic resin") may be used alone as the polymer component (a), and may be used in combination with the acrylic resin. By including the thermoplastic resin, it is possible to more easily pull the semiconductor wafer having the film-like adhesive from the support sheet at the time of pick-up, or the film-like adhesive can easily follow the uneven surface of the adherend, and can be further suppressed. A void or the like is generated between the adherend and the film-like adhesive.

The weight average molecular weight of the aforementioned thermoplastic resin is preferably from 1,000 to 100,000, more preferably from 3,000 to 80,000.

The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably from -30 ° C to 150 ° C, more preferably from -20 ° C to 120 ° C.

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

The thermoplastic resin may be used alone or in combination of two or more kinds, and two or more kinds of combinations and ratios may be arbitrarily selected.

In the subsequent composition, the ratio of the content of the polymer component (a) to the total content of all components other than the solvent (that is, the content of the polymer component (a) in the film-like adhesive), regardless of the polymer component ( The type of a) is preferably from 20% by mass to 75% by mass, more preferably from 30% by mass to 65% by mass.

(epoxy thermosetting resin (b))

The epoxy-based thermosetting resin (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2).

The epoxy-based thermosetting resin (b) contained in the adhesive composition and the film-like adhesive may be used alone or in combination of two or more kinds; in the case of two or more types, two or more of these combinations may be used. And the ratio can be arbitrarily chosen.

. Epoxy resin (b1)

Examples of the epoxy resin (b1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolac epoxy. Two or more epoxy resins such as resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenyl skeleton type epoxy resin Compound.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained by using the film-like adhesive is improved by containing an epoxy resin having an unsaturated hydrocarbon group.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of the epoxy group of the polyfunctional epoxy resin is replaced with a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction with an epoxy group. In the present specification, the term "derivative" means a compound in which one or more groups of the original compound are substituted with a group other than the group (that is, a substituent) unless otherwise specified. Here, the "base" is not only an atomic group in which a plurality of atoms are bonded, but also includes one atom.

In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include a secondary ethyl group (ie, a vinyl group), a 2-propenyl group (ie, an allyl group), and a (meth) group. The acrylonitrile group, the (meth) acrylamide group, and the like are preferably an acrylonitrile group.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, and is preferably from 300 to 30,000 in terms of the curability of the film-like adhesive and the strength and heat resistance of the film-like adhesive after curing. Good for 400 to 10,000, especially for 500 to 3000.

The epoxy equivalent of the epoxy resin (b1) is preferably from 100 g/eq to 1000 g/eq, more preferably from 150 g/eq to 800 g/eq.

The epoxy resin (b1) contained in the adhesive composition and the film-like adhesive may be used alone or in combination of two or more kinds. In the case of two or more types, the combination and ratio of the two or more types may be arbitrary. select.

. Thermal hardener (b2)

The heat hardener (b2) functions as a hardener for the epoxy resin (b1).

The thermosetting agent (b2) is, for example, a compound having two or more functional groups reactive with an epoxy group in one molecule. As the aforementioned functional Examples of the group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and a group in which an acid group is anhydride-formed. Preferably, the phenolic hydroxyl group, the amine group, or the acid group is formed by anhydride. More preferably, it is a phenolic hydroxyl group or an amine group.

In the thermosetting agent (b2), examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, a biphenol, a novolak type phenol resin, a biphenyl type phenol resin, and an aralkyl type phenol resin. .

In the thermosetting agent (b2), examples of the amine-based curing agent having an amine group include dicyandiamide ("DICY").

The heat hardener (b2) may also have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (b2) having an unsaturated hydrocarbon group include a compound in which a part of a hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group; and an unsaturated hydrocarbon group is directly bonded to an aromatic ring of the phenol resin. a compound such as a base.

The aforementioned unsaturated hydrocarbon group in the heat hardener (b2) is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermal curing agent (b2), it is easy to adjust the aforementioned adhesive force of the film-like adhesive to the above range, and the thermal curing agent (b2) is preferably a softening point or The glass transfer temperature is high.

In the thermosetting agent (b2), for example, a resin component such as a polyfunctional phenol resin, a novolak type phenol resin, a dicyclopentadiene type phenol resin, or an aralkyl type phenol resin. The number average molecular weight is preferably from 300 to 30,000, more preferably from 400 to 10,000, still more preferably from 500 to 3,000.

In the thermal curing agent (b2), the molecular weight of the non-resin component such as biphenol or dicyandiamide is not particularly limited, and is preferably, for example, 60 to 500.

The thermal curing agent (b2) contained in the adhesive composition and the film-like adhesive may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrary. select.

In the subsequent composition and the film-like adhesive, the content of the thermosetting agent (b2) is preferably 0.1 parts by mass to 500 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the epoxy resin (b1). Up to 200 parts by mass. When the content of the thermal curing agent (b2) is at least the above lower limit value, the film-like adhesive agent is more easily cured. In addition, when the content of the thermal curing agent (b2) is at most the above upper limit value, the moisture absorption rate of the film-like adhesive is lowered, and the reliability of the package obtained by using the film-like adhesive is further improved.

In the adhesive composition and the film-like adhesive, when the content of the polymer component (a) is 100 parts by mass, the content of the epoxy-based thermosetting resin (b) (that is, the epoxy resin (b1) and heat The total content of the hardener (b2) is preferably from 5 parts by mass to 100 parts by mass, more preferably from 7 parts by mass to 90 parts by mass, even more preferably from 9 parts by mass to 80 parts by mass, for example, from 9 parts by mass to 70 parts by mass. The mass part, 9 parts by mass to 60 parts by mass, 9 parts by mass to 50 parts by mass, and 9 parts by mass to 40 parts by mass or the like. Epoxy-based thermosetting resin The content of the above-mentioned (b) is in such a range, and it is easy to adjust the breaking elongation of the film-like adhesive or the laminated body and the above-mentioned adhesive force of the film-like adhesive to the above range.

In addition to the polymer component (a) and the epoxy-based thermosetting resin (b), the film-like adhesive may further contain various components other than these, as needed, to improve various physical properties of the film-like adhesive. .

Examples of preferred other components contained in the film-like adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), and an energy ray-curable resin. (g), photopolymerization initiator (h), general additive (i), and the like.

(hardening accelerator (c))

The hardening accelerator (c) is a component for adjusting the hardening speed of the adhesive composition.

Examples of preferred curing accelerators (c) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- An imidazole such as hydroxymethylimidazole (that is, an imidazole in which one or more hydrogen atoms are substituted by a group other than a hydrogen atom); an organic phosphine such as tributylphosphine, diphenylphosphine or triphenylphosphine (ie, 1) a phosphine in which one or more hydrogen atoms are substituted by an organic group; a tetraphenylborate such as tetraphenylphosphonium tetraphenylborate or triphenylphosphine tetraphenylborate; and the like.

The curing accelerator (c) contained in the adhesive composition and the film-like adhesive may be used alone or in combination of two or more kinds. In the case of two or more kinds, the combination and ratio of the two or more types may be arbitrary. select.

In the case of using the curing accelerator (c), when the content of the epoxy-based thermosetting resin (b) is 100 parts by mass in the adhesive composition and the film-like adhesive, the curing accelerator (c) The content is preferably from 0.01 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 5 parts by mass. When the content of the curing accelerator (c) is at least the above lower limit value, a more remarkable effect by the use of the curing accelerator (c) can be obtained. In addition, when the content of the curing accelerator (c) is at most the above upper limit value, for example, the high-polarity curing accelerator (c) is prevented from adhering to the adherend in a film-like adhesive under high-temperature and high-humidity conditions. The effect of segregation on the interface side is increased, and the reliability of the package obtained by using the semiconductor processing sheet is further improved.

(filling material (d))

When the film-like adhesive contains the filler (d), it is easy to adjust the thermal expansion coefficient of the film-like adhesive, and the thermal expansion coefficient is most suitable for the attachment of the film-like adhesive, whereby the film is used. The reliability of the package obtained by the subsequent agent is further improved. Further, since the film-like adhesive contains the filler (d), the moisture absorption rate of the film-like adhesive after curing can be lowered, or heat dissipation can be improved.

The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.

Examples of preferred inorganic fillers include powders of cerium oxide, aluminum oxide, talc, calcium carbonate, titanium white, iron oxide, tantalum carbide, and boron nitride; and these inorganic filler materials are spheroidized. Beads; surface modification of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, and the like.

Among these, the inorganic filler is preferably cerium oxide or aluminum oxide.

The filler (d) contained in the adhesive composition and the film-like adhesive may be used alone or in combination of two or more kinds. In the case of two or more types, the combination and ratio of the two or more types may be arbitrarily selected. .

In the case of using the filler (d), the ratio of the content of the filler (d) to the total content of all components other than the solvent in the adhesive composition (that is, the filler in the film-like adhesive (d) The content is preferably from 5% by mass to 80% by mass, more preferably from 7% by mass to 60% by mass. By the content of the filler (d) being such a range, it is easier to adjust the above thermal expansion coefficient.

(coupler (e))

The film-like adhesive improves the adhesion to the adherend and the adhesion by containing the coupling agent (e). Further, since the film-like adhesive contains the coupling agent (e), the cured product of the film-like adhesive is resistant to water resistance without loss of heat resistance. high. The coupling agent (e) has a functional group reactive with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group reactive with a functional group of the polymer component (a) or the epoxy thermosetting resin (b), and more preferably a decane coupling agent.

Preferred examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyl group. Triethoxy decane, 3-glycidoxymethyl diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethyl Oxydecane, 3-aminopropyltrimethoxydecane, 3-(2-aminoethylamino)propyltrimethoxydecane, 3-(2-aminoethylamino)propylmethyl Diethoxydecane, 3-(phenylamino)propyltrimethoxydecane, 3-anilinopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropyltrimethyl Oxydecane, 3-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfide, methyltrimethoxydecane, methyltriethoxydecane, ethylene Trimethoxy decane, vinyl triethoxy decane, imidazolium, and the like.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected. .

When the coupling agent (e) is used, when the total content of the polymer component (a) and the epoxy thermosetting resin (b) is 100 parts by mass in the adhesive composition and the film-like adhesive, The content of the coupling agent (e) is preferably from 0.03 parts by mass to 20 parts by mass, more preferably from 0.05 part by mass to 10 parts by mass, still more preferably from 0.1 part by mass to 5 parts by mass.

When the content of the coupling agent (e) is at least the above lower limit value, more remarkable effects by the use of the coupling agent (e) can be obtained: the dispersibility of the filler (d) in the resin is improved, and the film is improved. The adhesion between the adhesive and the adherend is improved. Further, when the content of the coupling agent (e) is at most the above upper limit value, generation of outgas can be further suppressed.

(crosslinking agent (f))

As the polymer component (a), a polymer component having a functional group such as a vinyl group, a (meth) acryl fluorenyl group, an amine group, a hydroxyl group, a carboxyl group or an isocyanate group which can be bonded to another compound such as the above acrylic resin is used. In the case where the adhesive composition and the film-like adhesive agent may further contain a crosslinking agent (f), the crosslinking agent (f) is used to bond the aforementioned functional group to another compound to carry out crosslinking. The initial adhesion and cohesive force of the film-like adhesive can be adjusted by crosslinking using the crosslinking agent (f).

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (that is, a crosslinking agent having a metal chelate structure), and an aziridine crosslinking. Agent (that is, a crosslinking agent having an aziridine group) or the like.

Examples of the organic polyvalent isocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compounds"); a trimer, an isocyanurate body, and an adduct of the aromatic polyvalent isocyanate compound, and a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyisocyanate compound or the like with a polyol compound. Wait. The term "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and is contained in ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. The reactant of the compound of the low molecular weight active hydrogen, as an example of the adduct, may be a benzodimethyl diisocyanate adduct of trimethylolpropane as described later. Further, the "terminal isocyanate urethane prepolymer" is as described above.

As the above-mentioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-benzenedimethyl diisocyanate; 1,4-dimethylbenzene Isocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; addition of toluene diisocyanate to all or a part of hydroxyl groups of polyhydric alcohols such as trimethylolpropane Hexamethylene di A compound obtained by using one or two or more kinds of isocyanate and benzodimethyl diisocyanate; an isocyanuric acid diisocyanate or the like.

The organic polyimine compound may, for example, be N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide) or trimethylolpropane-tri-beta-nitrogen. Propidyl propionate, tetramethylolmethane-tri-β-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarbamamine) Based on melamine and the like.

In the case where an organic polyvalent isocyanate compound is used as the crosslinking agent (f), as the polymer component (a), a hydroxyl group-containing polymer is preferably used. When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the crosslinking structure can be easily introduced by reacting the crosslinking agent (f) with the polymer component (a). To the film-like adhesive.

The crosslinking agent (f) contained in the adhesive composition and the film-like adhesive may be used alone or in combination of two or more kinds. When two or more kinds are used, the combination and ratio of the two or more types may be arbitrary. select.

In the case of using the crosslinking agent (f), when the content of the polymer component (a) is 100 parts by mass in the adhesive composition, the content of the crosslinking agent (f) is preferably from 0.01 part by mass to 20 parts by mass. The parts by mass are more preferably from 0.1 part by mass to 10 parts by mass, particularly preferably from 0.3 part by mass to 5 parts by mass. When the content of the crosslinking agent (f) is at least the above lower limit value, a more remarkable use of the crosslinking agent (f) can be obtained. The effect brought about. In addition, when the content of the crosslinking agent (f) is at most the above upper limit value, excessive use of the crosslinking agent (f) can be suppressed.

(energy curing resin (g))

The film-like adhesive can change the characteristics by irradiating the energy ray by containing the energy ray-curable resin (g).

The energy ray-curable resin (g) is obtained by polymerizing (hardening) an energy ray-curable compound.

The energy ray-curable compound may, for example, be a compound having at least one polymerizable double bond in the molecule, and is preferably an acrylate-based compound having a (meth) acrylonitrile group.

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(a). Acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth) acrylate containing a chain aliphatic skeleton such as (meth) acrylate; (meth) acrylate containing a cyclic aliphatic skeleton such as dicyclopentanyl (meth) acrylate; polyethylene glycol Poly(alkyl) diol (meth) acrylate such as di(meth) acrylate; oligoester (meth) acrylate; (meth) acrylate urethane oligomer; epoxy modified (A) Acrylate; the aforementioned polyalkylene A polyether (meth) acrylate other than a diol (meth) acrylate; an itaconic acid oligomer or the like.

The weight average molecular weight of the energy ray-curable resin (g) is preferably from 100 to 30,000, more preferably from 300 to 10,000.

The energy ray-curable resin (g) to be used in the composition of the second embodiment may be used alone or in combination of two or more kinds. In the case of two or more types, the combination and ratio of the two or more types may be arbitrarily selected.

In the case of using the energy ray-curable resin (g), the ratio of the content of the energy ray-curable resin (g) to the total content of all the components other than the solvent in the adhesive composition is preferably from 1% by mass to 95%. The mass% is more preferably from 5% by mass to 90% by mass, particularly preferably from 10% by mass to 85% by mass.

(Photopolymerization initiator (h))

When the adhesive composition contains the energy ray-curable resin (g), the photopolymerization initiator (h) may be contained so that the energy ray-curable resin (g) can be efficiently polymerized.

As the photopolymerization initiator (h) in the composition of the adhesive, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin Benzoin compounds such as dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1- Acetophenone compound such as phenyl-propan-1-one or 2,2-dimethoxy-1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzene) Sulfhydryl phosphine compounds such as phenylphosphine oxide, phenylphosphine oxide, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide; benzyl phenyl sulfide, tetramethyl thiuram monosulfide, etc. An ether compound; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; a titanocene compound such as ferrocene; a thioxanthone compound such as thioxanthone; Peroxide compound; diketone compound such as diethyl hydrazine; benzoin; diphenyl oxime; benzophenone; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; -2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; an anthracene compound such as 1-chloroindole or 2-chloroindole.

Further, examples of the photopolymerization initiator (h) include a photosensitizer such as an amine.

The photopolymerization initiator (h) contained in the composition of the second embodiment may be used alone or in combination of two or more kinds. In the case of two or more types, the combination and ratio of the two or more types may be arbitrarily selected.

When the photopolymerization initiator (h) is used, when the content of the energy ray-curable resin (g) is 100 parts by mass, the content of the photopolymerization initiator (h) is preferably It is from 0.1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass, particularly preferably from 2 parts by mass to 5 parts by mass.

(General additive (i))

The general-purpose additive (I) is a general-purpose additive, and can be arbitrarily selected according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives (I) include a plasticizer, an antistatic agent, an antioxidant, and a coloring. Agent (ie dye or pigment), getter, etc.

The general-purpose additive (i) contained in the adhesive composition and the film-like adhesive may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected. .

The content of the subsequent composition and the film-like adhesive is not particularly limited, and may be appropriately selected according to the purpose.

In the adhesive composition and the film-like adhesive agent, the polymer component (a) and the epoxy-based thermosetting resin (b) are improved in terms of improving the film formation property such as the surface state of the film-like adhesive. And when the total content of the filler (d) (that is, the total content of the polymer component (a), the epoxy resin (b1), the thermosetting agent (b2), and the filler (d)) is 100 parts by mass, polymerization The content of the component (a) is preferably 30 parts by mass or more, more preferably 38 parts by mass or more. Further, in the above aspect, the upper limit of the content of the polymer component (a) is not particularly limited, but is preferably 65 parts by mass.

On the other hand, in the adhesive composition and the film-like adhesive, the polymer component (a), the epoxy-based thermosetting resin (b), and the filler are improved in terms of improving the reliability of the film-like adhesive. Total content of (d) (ie total of polymer component (a), epoxy resin (b1), thermal hardener (b2) and filler (d) When the content is 100 parts by mass, the content of the polymer component (a) is preferably 45 parts by mass or more. Further, in the above aspect, the upper limit of the content of the polymer component (a) is not particularly limited, but is preferably 65 parts by mass.

(solvent)

The subsequent composition preferably further contains a solvent. The workability of the solvent-containing adhesive composition became good.

The solvent is not particularly limited, and examples of preferred solvents include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1- An alcohol such as butanol; an ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; or a guanamine such as dimethylformamide or N-methylpyrrolidone (i.e., having a guanamine bond) Compound) and the like.

The solvent contained in the composition of the second embodiment may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected.

The solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like in terms of more uniformly mixing the components contained in the adhesive composition.

[Method for Producing Adhesive Composition]

The composition of the subsequent agent is obtained by formulating the components constituting the composition of the adhesive.

The order in which the ingredients are added is not particularly limited, and may be added at the same time. Add two or more ingredients.

In the case of using a solvent, it may be used by mixing a solvent with any of the formulation components other than the solvent to preliminarily dilute the formulation component; or by using any of the following solvents: The formulated ingredients are pre-diluted and the solvent is mixed with these formulated ingredients.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by stirring a stirring blade or a stirring blade, a method of mixing using a mixer, and applying ultrasonic waves. The method of mixing, etc.

The temperature and time when the components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and may be appropriately adjusted, and the temperature is preferably from 15 ° C to 30 ° C.

◎Semiconductor processing film

The film for semiconductor processing of the present invention is provided with the above-mentioned film-like adhesive of the present invention on a support sheet.

The sheet for semiconductor processing of the present invention is suitably used in the step of providing a plurality of semiconductor wafers which have been divided in advance on the film-like adhesive in the sheet for semiconductor processing, and performing so-called stretching at a low temperature, even a film-like adhesive Together with the support sheet, it spreads in the direction along the surface of the film-like adhesive, whereby the film-like adhesive is cut in accordance with the outer shape of the semiconductor wafer. The surface opposite to the surface on which the circuit is formed (hereinafter sometimes referred to simply as "circuit forming surface") (that is, the back surface) is provided with half of the film-like adhesive after cutting. A conductor wafer (in this specification, sometimes referred to as "a semiconductor wafer with a film-like adhesive") is used for manufacturing a semiconductor device after picking up.

By using the sheet for semiconductor processing of the present invention, when the film-like adhesive is cut by the stretching, the film-like adhesive can be cut at the target portion, and the film-like adhesive can be suppressed from being formed at the cut portion. An abnormality such as a defect indicates excellent cutting characteristics. Therefore, the semiconductor wafer with the film-like adhesive can be easily picked up without the step abnormality.

The above-mentioned film-like adhesive is preferably applied to, for example, a semiconductor wafer having a film-like adhesive having a thin semiconductor wafer, based on the extended cutting system.

The divided plurality of semiconductor wafers can be produced, for example, by a circuit forming surface (ie, a surface) opposite to the bonding surface (ie, the back surface) of the film-like adhesive in the semiconductor wafer. A groove is formed and the aforementioned back surface is ground until it reaches the groove. As such, the operation of cutting into the semiconductor wafer in such a manner that the semiconductor wafer is not divided and the bottom of the trench remains is referred to as half-cut. However, in the present invention, the term "half-cut" does not mean merely the operation of cutting into the semiconductor wafer so that the depth of the trench becomes a specific value such as half the thickness of the semiconductor wafer, but means that the groove is left as described above. The bottom of the slot cuts through all operations of the semiconductor wafer.

As a method of forming the above-described trench, for example, a method of forming a trench by cutting a semiconductor wafer using a blade (that is, a blade) a method of forming a trench by laser irradiation into a semiconductor wafer (ie, laser cutting); a method of forming a trench by using a water containing an abrasive to cut into a semiconductor wafer (ie, water) Cutting) and so on. However, as in the case of manufacturing a semiconductor wafer by cutting a part of the semiconductor wafer, a part of the semiconductor wafer is removed (that is, a trench is formed in the semiconductor wafer), and a semiconductor wafer is produced. Loss, the number of semiconductor wafers obtained from one semiconductor wafer is reduced. In addition, since the film-like adhesive after the final cutting is larger than the semiconductor wafer, the film-like adhesive may be wound after being cut at the time of cutting the film-like adhesive or when picking up the semiconductor wafer with the film-like adhesive described later. On the side of the semiconductor wafer, etc.

On the other hand, the divided plurality of semiconductor wafers can also be fabricated by irradiating the laser light in the infrared region to focus on the focus set inside the semiconductor wafer, and forming a modified inside the semiconductor wafer. After the quality layer, the back surface of the semiconductor wafer is ground, and a force during grinding is applied to the semiconductor wafer in the back grinding to divide the semiconductor wafer at a portion where the modified layer is formed. In this method, since there is no step of cutting a part of the semiconductor wafer, the number of semiconductor wafers to be produced is reduced, and the film-like adhesive after cutting is wound onto the side surface of the semiconductor wafer or the like. advantageous.

<<Support film>>

As the support sheet, a support sheet having a substrate can be cited. Such a support sheet may be composed of, for example, a substrate (ie, having only a substrate), or may have a substrate. And other layers than the substrate. Examples of the support sheet having the other layer described above include a support sheet having an adhesive layer on a substrate.

In the sheet for semiconductor processing of the present invention, the film-like adhesive is provided on the support sheet. Therefore, for example, when the support sheet is a support sheet having an adhesive layer on the substrate, a film-like adhesive is provided on the adhesive layer, and when the support sheet is composed of the substrate, the substrate is directly in contact with the substrate. Film-like adhesive.

The support sheet may be composed of one layer (that is, a single layer), or may be composed of a plurality of layers of two or more layers. In the case where the support sheet is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

As the support sheet, a support sheet provided with an adhesive layer on the substrate is preferable, and it is more preferable to directly contact the support sheet provided with the adhesive layer on the substrate.

In other words, the sheet for semiconductor processing of the present invention is preferably a sheet for semiconductor processing in which an adhesive layer is provided on a substrate and a film-like adhesive is provided on the adhesive layer, and it is more preferable to directly contact the substrate. a sheet for semiconductor processing provided with an adhesive layer and provided with a film-like adhesive on the adhesive layer, and it is particularly preferable to provide an adhesive layer in direct contact with the substrate and to provide a film-like adhesive in direct contact with the adhesive layer. A sheet for semiconductor processing.

<Substrate>

The constituent material of the substrate is preferably various resins, and specific examples thereof include polyethylene (low density polyethylene (sometimes abbreviated as LDPE), linear low density polyethylene (sometimes abbreviated as LLDPE), and high. Density polyethylene (sometimes referred to as HDPE, etc.), polypropylene, polybutene, polybutadiene, polymethylpentene, styrene-ethylene butene-styrene block copolymer, polyvinyl chloride, chlorine Ethylene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyacrylic acid urethane, polyimide, ethylene-vinyl acetate copolymer, Ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, polystyrene, polycarbonate, fluororesin, hydride, modification, cross-linking of any of these resins Or a copolymer or the like.

The resin constituting the substrate may be one type or two or more types. When two or more types are used, the combination and ratio of the two types or more may be arbitrarily selected.

The substrate may be composed of one layer (that is, a single layer), or may be composed of a plurality of layers of two or more layers. In the case where the substrate is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The surface of the substrate composed of a single layer can also be subjected to a release treatment by a known method.

The thickness of the substrate may be appropriately selected depending on the purpose, and is preferably from 50 μm to 300 μm, more preferably from 70 μm to 150 μm.

Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. In addition, as a method of measuring the thickness of the base material, for example, the following method may be used: the thickness is measured using a contact thickness gauge at any five locations, and the average of the measured values is calculated.

The surface of the substrate may be subjected to the following treatment to improve adhesion to other layers such as an adhesive layer to be described later on the substrate: embossing by sandblasting, solvent treatment, or the like; or corona discharge Treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc.

Alternatively, the surface of the substrate may be subjected to a primer treatment.

Further, the substrate may have an antistatic coating layer, and when the semiconductor processing sheet is stacked and stored, the substrate may be adhered to another layer or the substrate to the layer of the adsorption stage.

<Adhesive layer>

The adhesive layer is in the form of a sheet or a film and contains an adhesive.

The aforementioned adhesive layer may be a known adhesive layer.

Examples of the pressure-sensitive adhesive include an adhesive resin such as an acrylic resin, an urethane resin, a rubber resin, a polyoxyn resin, an epoxy resin, a polyvinyl ether or a polycarbonate. It is an acrylic resin.

Further, in the present invention, the term "adhesive resin" includes both an adhesive resin and a resin having adhesive properties, for example, a resin which is not only adhesive to the resin itself, but also includes other additives and the like. A resin which exhibits adhesiveness in combination with a component, or a resin which exhibits adhesiveness by the presence of a trigger agent such as heat or water.

The adhesive layer may be either an energy ray hardening property or a non-energy ray hardening property, and is preferably non-energy ray curability.

In the present invention, the "energy line" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples of the energy line include ultraviolet rays, electron beams, and the like.

The ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a fusion H-type lamp, a xenon lamp, or a light emitting diode as an ultraviolet source. The electron beam can illuminate an electron beam generated by an electron beam accelerator or the like.

In the present invention, the term "energy ray hardenability" means a property of being hardened by irradiation with an energy ray, and "non-energy ray curability" means a property that does not harden even when irradiated with an energy ray.

As a preferred adhesive layer in the present invention, for example, an adhesive layer having a thickness of 200 μm has a storage elastic modulus at 0 ° C of 1000 MPa or less, and the adhesion of the adhesive layer to a mirror surface of a semiconductor wafer is 200 mN/25 mm. The following adhesive layer.

However, a preferred adhesive layer is not limited thereto.

The adhesive layer for obtaining the storage elastic modulus may be a single-layer adhesive layer having a thickness of 200 μm, or may be formed by laminating two or more adhesive layers having a thickness of less than 200 μm to a total thickness of 200 μm. And get the layered body.

Further, in the present specification, the adhesive layer for determining the storage elastic modulus may be either a single-layer adhesive layer or the above-mentioned laminated body, and may be simply referred to as an "adhesive layer".

In the present specification, the "storage elastic modulus of the adhesive layer" and the "storage elastic modulus of the laminated body" are respectively referred to as "adhesive before curing" when the adhesive layer is curable unless otherwise specified. The storage elastic modulus of the layer" and the storage elastic modulus of the laminate before the adhesive layer is cured.

The storage elastic modulus of the pressure-sensitive adhesive layer or laminate at 0 ° C is preferably 1000 MPa or less, more preferably 996 MPa or less. When the storage elastic modulus is equal to or less than the above upper limit value, as will be described later, when the film-like adhesive is cut based on the stretching, the semiconductor wafer of the film-like adhesive can be prevented from being swelled or scattered from the adhesive layer.

The lower limit of the storage elastic modulus of the pressure-sensitive adhesive layer or the laminate at 0 ° C is not particularly limited, and may be, for example, any of 100 MPa, 300 MPa, and 500 MPa, but these are examples.

The storage elastic modulus (MPa) was obtained by the following method: under the conditions of a temperature increase rate of 10 ° C/min and a frequency of 11 Hz, the aforementioned measurement target was used. The adhesive layer or the laminate is heated, for example, from -50 ° C to 50 ° C to a temperature within a specific temperature range, and the storage elastic modulus (MPa) at this time is measured.

The storage elastic modulus can be appropriately adjusted by, for example, adjusting the type and amount of the component contained in the adhesive layer.

For example, the storage elastic modulus of the adhesive layer and the storage elastic modulus of the laminate can be easily adjusted by adjusting the ratio of the monomer constituting the adhesive resin, the blending amount of the crosslinking agent, the content of the filler, and the like.

However, these adjustment methods are only one example.

The adhesion of the adhesive layer to the semiconductor wafer is preferably 200 mN/25 mm or less, more preferably 196 mN/25 mm or less. When the adhesive force is equal to or less than the above upper limit, the semiconductor wafer with the film-like adhesive can be easily picked up without curing the adhesive layer by irradiation of an energy ray or the like as will be described later.

The lower limit of the adhesion of the adhesive layer to the semiconductor wafer is not particularly limited, and may be, for example, any of 10 mN/25 mm, 30 mN/25 mm, and 50 mN/25 mm, but these are examples.

In the present specification, the term "adhesion of the adhesive layer to the semiconductor wafer" means that the adhesive layer before curing is applied to the semiconductor wafer unless otherwise specified. Adhesion." In addition, unless otherwise indicated, the measurement of the adhesive force is the measurement of the adhesive force in the standard state prescribed by JIS Z02372008.

In the present invention, the adhesion (mN/25 mm) can be measured by the following method. That is, the support sheet obtained by providing an adhesive layer on a substrate having a width of 25 mm and an arbitrary length was produced. Then, the support sheet is attached to the semiconductor wafer by an adhesive layer at normal temperature. Then, while maintaining the temperature, the following so-called 180° peeling is performed: the support sheet is peeled at a peeling speed of 300 mm/min from the semiconductor wafer so that the surfaces where the adhesive layer and the semiconductor wafer contact each other are at an angle of 180° to each other. Stripped. The peeling force at this time was measured, and the measured value of the peeling force was made into the said adhesive force (mN / 25 mm). The length of the support sheet used for the measurement is not particularly limited as long as it is a range in which the peeling force can be stably measured.

Even if the types of semiconductor wafers such as germanium wafers are different or the types are the same, but the manufacturing lot is different, the adhesion to the adhesive layer is applied when the same adhesive layer is attached to the same portion of the semiconductor wafer such as the germanium wafer. The unevenness is small. Therefore, the adhesive force of the adhesive layer can be specified with high precision by selecting a semiconductor wafer as the measurement target of the adhesive force. In the present invention, by selecting an adhesive layer of the adhesive layer to the mirror surface of the semiconductor wafer of 200 mN/25 mm or less, the adhesion of the adhesive layer to the film-like adhesive can be adjusted to follow the film shape. When the semiconductor wafer of the agent is pulled out from the adhesive layer and picked up, it is possible to suppress the abnormality of the production step and easily pick up. The efficacy of the present invention is exhibited for all of the film-like adhesives used in the aforementioned fields.

The adhesion of the adhesive layer to the semiconductor wafer can be appropriately adjusted by, for example, adjusting the type and amount of the component contained in the adhesive layer.

For example, the adhesion of the adhesive layer can be easily adjusted by adjusting the combination of the monomers constituting the adhesive resin, the ratio of the above monomers, the amount of the crosslinking agent, the content of the filler, and the like.

However, these adjustment methods are only one example.

The adhesive layer may be composed of one layer (that is, a single layer), or may be composed of a plurality of layers of two or more layers. In the case where the adhesive layer is composed of a plurality of layers, the plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the adhesive layer can be appropriately selected depending on the purpose, and is preferably from 1 μm to 100 μm, more preferably from 1 μm to 60 μm, still more preferably from 1 μm to 30 μm.

Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer. In addition, as a method of measuring the thickness of the pressure-sensitive adhesive layer, for example, the following method may be used: the thickness is measured using a contact thickness meter at any five locations, and the average of the measured values is calculated.

The aforementioned adhesive layer may be formed of an adhesive composition containing an adhesive. For example, an adhesive composition is applied to the surface to be formed of the adhesive layer, and the adhesive composition is dried as needed, whereby an adhesive layer can be formed at the target portion. More specific methods of forming the adhesive layer, with other layers The formation method will be described in detail later. The content ratio of the components which are not vaporized at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer.

The adhesive composition may be applied by a known method, and may be carried out by the same method as the application of the above-mentioned adhesive composition.

The drying condition of the adhesive composition is not particularly limited. When the adhesive composition contains a solvent to be described later, it is preferably heated and dried. In this case, for example, it is preferably at 70 ° C to 130 ° C for 10 seconds. Drying was carried out under 5 minutes.

[Adhesive composition]

The above adhesive composition is preferably non-energy line hardenability.

Examples of the non-energy-curable adhesive composition include the acrylic resin, the urethane resin, the rubber resin, the polyoxyn resin, the epoxy resin, the polyvinyl ether, or the poly A composition of an adhesive resin such as carbonate (hereinafter referred to as "adhesive resin (i)").

(adhesive resin (i))

The adhesive resin (i) is preferably the acrylic resin.

The acrylic resin in the adhesive resin (i) may, for example, be an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

The number of the structural units of the acrylic resin may be one or two or more. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected.

The alkyl (meth)acrylate may, for example, be an alkyl (meth)acrylate having a carbon number of 1 to 20 constituting an alkyl group of an alkyl ester, and the alkyl group is preferably a linear or branched chain. shape.

Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (A) Ethyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Anthracene ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as (meth)acrylic acid) Lauryl ester), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, Cetyl (meth) acrylate (also known as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as (A) (poly) stearyl acrylate), (meth) acrylate Nine alkyl ester, (meth) acrylate, eicosyl acrylate.

The acrylic polymer is preferably a structural unit having an alkyl (meth)acrylate having a carbon number of 4 or more derived from the alkyl group, in terms of improving the adhesion of the adhesive layer. Further, the alkyl group preferably has a carbon number of 4 to 12, more preferably 4 to 8, in terms of further improving the adhesion of the adhesive layer. Further, the alkyl (meth)acrylate having a carbon number of 4 or more in the alkyl group is preferably an alkyl acrylate.

The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the alkyl (meth)acrylate.

Examples of the functional group-containing monomer include a monomer which can be reacted with a crosslinking agent described later to form a starting point of crosslinking, or a functional group and an unsaturated group-containing group. The unsaturated group in the compound reacts, and an unsaturated group is introduced into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group.

That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl ester, 2-hydroxyl (meth)acrylate Non-(meth)acrylic acid such as butyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; non-(meth)acrylic acid such as vinyl alcohol or allyl alcohol Saturated alcohol (that is, an unsaturated alcohol having no (meth) acrylonitrile skeleton) and the like.

Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid such as (meth)acrylic acid or crotonic acid (that is, a monocarboxylic acid having an ethylenically unsaturated bond); fumaric acid, An ethylenically unsaturated dicarboxylic acid such as itaconic acid, maleic acid or citraconic acid (that is, a dicarboxylic acid having an ethylenically unsaturated bond); an anhydride of the above ethylenically unsaturated dicarboxylic acid; methacrylic acid A carboxyalkyl (meth)acrylate such as 2-carboxyethyl ester.

The functional group-containing monomer is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, more preferably a hydroxyl group-containing monomer.

The number of the functional group-containing monomers constituting the acrylic polymer may be one or two or more. When two or more kinds are used, the combination and ratio of the two or more types may be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably from 1% by mass to 35% by mass, more preferably from 3% by mass to 32% by mass, based on the total amount of the structural unit. More preferably, it is 5 mass% to 30 mass%.

In addition to the structural unit derived from the alkyl (meth)acrylate and the structural unit derived from the functional group-containing monomer, the acrylic polymer may further have a structural unit derived from another monomer.

The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth)acrylate or the like.

Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

The other monomers constituting the acrylic polymer may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected.

Similarly to the acrylic polymer, the adhesive resin (i) other than the acrylic polymer preferably has a structural unit derived from a monomer having a functional group.

The adhesive resin (i) contained in the adhesive composition may be one type or two or more types. When two or more types are used, the combination and ratio of these two types may be arbitrarily selected.

In the adhesive composition, the ratio of the content of the adhesive resin (i) to the total content of the components other than the solvent (that is, the content of the adhesive resin (i) in the adhesive layer) is preferably from 45% by mass to 90%. % by mass, more preferably 55% by mass It is 87% by mass, and particularly preferably 65% by mass to 84% by mass. When the aforementioned ratio of the content of the adhesive resin (i) is in such a range, the adhesiveness of the adhesive layer becomes more favorable.

(crosslinking agent (ii))

The adhesive composition preferably contains a crosslinking agent (ii).

The crosslinking agent (ii) reacts with the aforementioned functional groups to crosslink the adhesive resin (i) with each other.

Examples of the crosslinking agent (ii) include isocyanate crosslinking agents such as toluene diisocyanate, hexamethylene diisocyanate, benzodimethyl diisocyanate, and an adduct of these diisocyanates (that is, having an isocyanate group). Crosslinking agent); epoxy crosslinking agent such as ethylene glycol glycidyl ether (that is, a crosslinking agent having a glycidyl group); hexa[1-(2-methyl)-aziridine group] Aziridine-based cross-linking agent such as phosphine triazine (that is, a cross-linking agent having an aziridine group); a metal chelate-based cross-linking agent such as an aluminum chelate compound (that is, a cross-linking having a metal chelate structure) An isocyanurate-based crosslinking agent (that is, a crosslinking agent having an isocyanuric acid skeleton) or the like.

The crosslinking agent (ii) is preferably an isocyanate crosslinking agent in terms of improving the cohesive force of the adhesive, improving the adhesion of the adhesive layer, and facilitating the acquisition.

The crosslinking agent (ii) contained in the adhesive composition may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected.

In the case where the adhesive composition contains the crosslinking agent (ii), the content of the crosslinking agent (ii) is preferably 5 when the content of the adhesive resin (i) is 100 parts by mass. The mass fraction is 50 parts by mass, more preferably 10 parts by mass to 45 parts by mass, particularly preferably 15 parts by mass to 40 parts by mass. When the content of the crosslinking agent (ii) is at least the above lower limit value, more remarkable effects by the use of the crosslinking agent (ii) can be obtained. Further, when the content of the crosslinking agent (ii) is at most the above upper limit value, it is easier to adjust the adhesion of the adhesive layer to the film-like adhesive.

(other additives)

The adhesive composition may also contain other additives not belonging to any of the above components within the scope of the effects of the present invention.

Examples of the other additives include antistatic agents, antioxidants, softeners (i.e., plasticizers), fillers (i.e., fillers), rust inhibitors, colorants (i.e., pigments or dyes), and sensitization. A known additive such as a agent, an adhesion-imparting agent, a reaction retarder, and a crosslinking accelerator (that is, a catalyst).

In addition, the "reaction retarder" suppresses the cross-linking reaction outside the target in the adhesive composition during storage by, for example, the action of the catalyst mixed in the adhesive composition. Examples of the reaction retardation agent include a reaction retardation agent which forms a chelate complex by chelation with a catalyst, and more specifically, it has two or more carbonyl groups (-C(=O) in one molecule. -) Reaction retarder.

The other additives contained in the adhesive composition may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected.

The content of the other additives in the adhesive composition is not particularly limited, and may be appropriately selected depending on the type of the other additives.

(solvent)

The adhesive composition may also contain a solvent. The adhesive composition has an applicability to the coating target surface by containing a solvent.

The solvent is preferably an organic solvent, and examples of the organic solvent include a ketone such as methyl ethyl ketone or acetone; a carboxylic acid ester such as ethyl acetate; an ether such as tetrahydrofuran or dioxane; and cyclohexane. An aliphatic hydrocarbon such as n-hexane; an aromatic hydrocarbon such as toluene or xylene; an alcohol such as 1-propanol or 2-propanol; or the like.

The solvent can be directly used for the adhesive composition without removing the solvent used in the production of the adhesive resin (i) from the adhesive resin (i), and can be separately added and manufactured in the production of the adhesive composition. The solvent used in the adhesive resin (i) is the same or a different type of solvent.

The solvent contained in the adhesive composition may be one type or two or more types. When two or more types are used, the combination and ratio of the two or more types may be arbitrarily selected.

The content of the solvent in the adhesive composition is not particularly limited, and may be appropriately adjusted.

[Method of Manufacturing Adhesive Composition]

The adhesive composition is obtained by blending the components constituting the adhesive composition, and for example, it can be produced by the same method as the above-described adhesive composition except for the difference in the formulation components.

Fig. 1 is a cross-sectional view showing an embodiment of a semiconductor processing sheet of the present invention in a schematic manner. In the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, a part which is a main part may be enlarged and displayed in a convenient manner, and the size ratio of each component is not limited to the actual one.

The semiconductor processing sheet 1 shown here is obtained by providing an adhesive layer 12 on a substrate 11, and a film-like adhesive 13 on the adhesive layer 12.

In the sheet 1 for semiconductor processing, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the film-like adhesive 13 is laminated on one surface of the adhesive layer 12, that is, laminated on the adhesive layer 12 and provided with a base. The side of the material 11 is the surface 12a on the opposite side. The film-like adhesive 13 is the above-mentioned film-like adhesive of the present invention.

In other words, in the sheet for semiconductor processing 1, the support sheet 10 on which the adhesive layer 12 is provided on the substrate 11 is used, and the film-like adhesive 13 is directly provided in contact with the adhesive layer 12.

In addition, the semiconductor processing sheet of the present invention is not limited to the semiconductor processing sheet shown in FIG. 1, and the semiconductor processing sheet shown in FIG. 1 may be changed, deleted or added without departing from the effects of the present invention. Part of the composition.

<<Manufacturing method of sheet for semiconductor processing>>

The sheet for semiconductor processing can be produced by sequentially laminating the above layers in a corresponding positional relationship. The formation method of each layer is as described above.

For example, when an adhesive layer or a film-like adhesive is laminated on a substrate, an adhesive composition or an adhesive composition is applied onto the release film, and the adhesive composition or the adhesive composition is dried as needed. Adhesive layer or film-like adhesive is preliminarily formed on the release film to expose the surface of the formed adhesive layer or film-like adhesive on the opposite side to the side in contact with the release film, and the surface of the substrate Fit it. At this time, the adhesive composition or the adhesive composition is preferably applied to the release-treated surface of the release film. After forming the laminate structure, the release film may be removed as needed.

For example, a semiconductor processing sheet (that is, a support sheet) obtained by laminating an adhesive layer on a substrate and laminating a film-like adhesive on the adhesive layer In the case of the semiconductor processing sheet which is a laminate of the substrate and the adhesive layer, in the above method, an adhesive layer is previously laminated on the substrate, and an adhesive composition is applied to the release film separately, and if necessary, After the agent composition is dried, a film-like adhesive is formed on the release film in advance, and the exposed surface of the film-like adhesive is bonded to the exposed surface of the adhesive layer deposited on the substrate to laminate the film-like adhesive. On the adhesive layer, a sheet for semiconductor processing was obtained. In the case where a film-like adhesive is formed on the release film, it is also preferred to apply the adhesive composition to the release-treated surface of the release film to form a laminated structure, and then remove the release film as necessary.

In this way, since the layers other than the substrate constituting the semiconductor processing sheet can be laminated on the release film and bonded to the surface of the target layer, it is possible to appropriately select the layer using such a step as needed. A sheet for semiconductor processing is produced.

In addition, the semiconductor processing sheet is usually stored in a state in which the semiconductor processing sheet is fixed to a necessary layer such as an adhesive layer for a jig for a jig for cutting, etc., and then the semiconductor is used. The surface of the processing sheet is bonded to the surface of the outermost layer on the opposite side of the support sheet.

<<Manufacturing method of semiconductor device>>

In the method for producing a semiconductor device of the present invention, the film-like adhesive of the present invention described above is used, and the step of forming a laminated structure is carried out to form a laminated structure having a laminated structure on a support sheet. The film-like adhesive is provided, and a plurality of divided semiconductor wafers are provided on a surface of the film-like adhesive opposite to the side on which the support sheet is provided; and a cutting step is performed in the laminated structure The film-like adhesive is extended in a direction parallel to the surface of the film-like adhesive while cooling, and the film-like adhesive is cut; and the pulling-off step is performed to form the semiconductor having the film-like adhesive after cutting The wafer (in the present specification, sometimes referred to simply as "a semiconductor wafer with a film-like adhesive") is picked up from the support sheet (that is, pulled away).

In the above-described support sheet, the film-like adhesive is provided in the above-described semiconductor processing sheet of the present invention. As will be described later, the film-forming adhesive or the semiconductor processing sheet of the present invention is used in the method for producing a semiconductor device of the present invention.

When the film-like adhesive or the film for semiconductor processing of the present invention is used, when the film-like adhesive is cut by the extension of the film-like adhesive in the cutting step, the film-like adhesive may be omitted. The film-like adhesive is easily cut at the target site.

Further, in the case of using a sheet for semiconductor processing having the above-described non-energy-curable adhesive layer, in the step of pulling apart, even if the adhesive layer is not cured by irradiation of an energy ray, the film may be attached. The semiconductor wafer of the agent is easily pulled away from the adhesive layer for picking. In this case, the manufacturing steps of the semiconductor device can be simplified.

Hereinafter, the above manufacturing method will be described with reference to Fig. 2 . Figure 2 is a schematic view for explaining the use of the film-like adhesive or semiconductor processing sheet of the present invention. A cross-sectional view of an embodiment of a method of manufacturing a semiconductor device in the case of the semiconductor device. Here, a description will be given of a manufacturing method in the case where the film-like adhesive 13 or the semiconductor processing sheet 1 shown in Fig. 1 is used. It is to be noted that the same components as those in FIG. 1 are denoted by the same reference numerals as those in FIG. 1 and the detailed description of the symbols will be omitted. In addition, in FIG. 2, the structure related to the semiconductor processing sheet and the semiconductor wafer is shown only in the sectional view.

<Laminated structure forming step>

The laminated structure 101 shown in Fig. 2(a) is provided with an adhesive layer 12 on the substrate 11, and a film-like adhesive 13 is provided on the surface 12a of the adhesive layer 12, and is formed in the film-like adhesive 13. The surface 13a on the side opposite to the side on which the adhesive layer 12 is provided is provided with a plurality of divided semiconductor wafers 8.

Further, in FIG. 2, the gap portion between the plurality of semiconductor wafers 8 (i.e., originating from the above-described trench) is emphasized.

In the step of forming the laminated structure, for example, after attaching one film-like adhesive 13 to the back surface 8b of the plurality of divided semiconductor wafers 8, the film-like adhesive 13 is opposite to the side having the semiconductor wafer 8. The side surface (i.e., the back surface) 13b is attached to the adhesive layer 12 in the support sheet 10, whereby the laminated structure body 101 can be formed. In addition, the surface 13a of the film-like adhesive 13 of the semiconductor processing sheet 1 on the side opposite to the side having the adhesive layer 12 is attached to the divided sheet 13 of the semiconductor processing sheet 1 of the present invention. The back surface 8b of the plurality of semiconductor wafers 8 can also form the laminated structure 101.

The plurality of divided semiconductor wafers 8 can be fabricated as described above from the circuit forming surface on the opposite side of the bonding surface (ie, the back surface) of the film-like adhesive 13 in the semiconductor wafer (also That is, the surface is formed with a groove, and the aforementioned back surface is ground until it reaches the groove. Also, the aforementioned grooves may be formed by a method such as blade cutting, laser cutting, water cutting, or the like.

3 is a cross-sectional view showing an embodiment of a method of forming a semiconductor wafer by forming a trench in such a semiconductor wafer.

In the method, as shown in (a) of FIG. 3, on the semiconductor wafer 8', a surface of the semiconductor wafer 8' as a circuit forming surface is formed by blade cutting, laser cutting, water cutting, or the like. 8a' forms a groove 80'.

Then, as shown in FIG. 3(b), the surface (ie, the back surface) 8b' on the opposite side to the surface (that is, the circuit forming surface) 8a' of the semiconductor wafer 8' is ground. The grinding of the back surface 8b' can be carried out by a known method, for example, using a grinder 62. The grinding of the back surface 8b' is preferably performed by attaching the back surface polishing tape 63 to the surface 8a' of the semiconductor wafer 8' as shown here.

Then, the back surface 8b' is ground until it reaches the trench 80', whereby a plurality of semiconductor wafers 8 are obtained from the semiconductor wafer 8' as shown in (c) of FIG. The back surface 8b' of the semiconductor wafer 8' is the back surface 8b of the semiconductor wafer 8, that is, the surface on which the film-like adhesive 13 is provided.

However, in the above-described manufacturing method of the semiconductor device, it is preferable to form a modified layer inside the semiconductor wafer and to divide the semiconductor wafer at a portion where the modified layer is formed, instead of being cut as described above. A method of a portion of these semiconductor wafers.

That is, in the method of fabricating the semiconductor device of the present invention, preferably, before the step of forming the stacked structure, the method further includes the step of forming a modified layer to focus on a focus set inside the semiconductor wafer. a method of irradiating a laser beam in an infrared region to form a modified layer inside the semiconductor wafer; and a dividing step of grinding a surface of the semiconductor wafer on which the modified layer is formed to provide the film-like adhesive And applying a force during grinding to the semiconductor wafer, thereby dividing the semiconductor wafer at a portion of the modified layer to obtain a plurality of semiconductor wafers; and using the plurality of semiconductor wafers obtained in the dividing step in the foregoing The laminated structure is formed in the step.

4 is a cross-sectional view showing an embodiment of a method of obtaining a semiconductor wafer by forming a modified layer on such a semiconductor wafer.

<Modification layer formation step>

In the method, in the reforming layer forming step, as shown in (a) of FIG. 4, the laser light in the infrared region is irradiated to focus on the focus set inside the semiconductor wafer 8' on the semiconductor wafer. The modified layer 81' is formed inside the 8'.

In the reforming layer forming step, for example, it is preferable to irradiate laser light having a large opening degree (NA) so that the surface of the semiconductor wafer 8' or the vicinity of the surface is damaged by the irradiation of the laser light to a minimum. Modification layer 81'.

<Segmentation step>

Then, in the dividing step, as shown in FIG. 4(b), the surface (ie, the back surface) 8b' on the opposite side to the surface (that is, the circuit forming surface) 8a' of the semiconductor wafer 8' is formed. Perform grinding. The grinding at this time can be carried out in the same manner as the grinding of the back surface of the grooved semiconductor wafer described with reference to Fig. 3 above. For example, the grinding of the back surface 8b' at this time is preferably performed by attaching the back surface polishing tape 63 to the surface 8a' of the semiconductor wafer 8'.

Then, the back surface 8b' of the semiconductor wafer 8' is ground, and the force at the time of grinding is further applied to the semiconductor wafer 8' under grinding, thereby dividing the semiconductor wafer 8 at the portion where the modified layer 81' is formed. Thus, as shown in (c) of FIG. 4, a plurality of semiconductor wafers 8 are obtained from the semiconductor wafer 8'. In this case as well, the back surface 8b' of the semiconductor wafer 8' is the back surface 8b of the semiconductor wafer 8, that is, the surface on which the film-like adhesive 13 is provided, as in the case of the description with reference to FIG.

In any of the above methods, when the back surface polishing tape 63 is used, the plurality of semiconductor wafers 8 obtained are kept in a state of being aligned on the back surface polishing tape 63.

The thickness of the semiconductor wafer 8 is not particularly limited, but is preferably 5 μm to 60 μm, more preferably 10 μm to 55 μm. In the case of using such a thin semiconductor wafer, it is possible to obtain a more remarkable effect when using the sheet for semiconductor processing of the present invention.

<cutting step>

In the cutting step in the method of manufacturing a semiconductor device described above, after the laminated structure forming step, the film-like adhesive 13 in the laminated structure 101 is cooled as shown in FIG. 2(b). The film-like adhesive 13 is cut while extending the film-like adhesive 13 in a direction parallel to the surface 13a of the film-like adhesive 13. The film-like adhesive 13 may be extended together with the substrate 11 and the adhesive layer 12 (that is, the support sheet 10). Here, the film-like adhesive agent after cutting is denoted by reference numeral 13', but the film-like adhesive 13' after the cutting may be simply referred to as "film-like adhesive 13". Further, the direction in which the film-like adhesive 13 is extended is indicated by an arrow I.

In the cutting step, the cooling temperature of the film-like adhesive 13 is not particularly limited, and in view of the fact that the film-like adhesive 13 is more easily cut, it is preferably -15 ° C to 10 ° C.

In the cutting step, the stretching speed (that is, the expansion speed) of the film-like adhesive 13 is not particularly limited as long as it does not impair the efficacy of the present invention, and is preferably 0.5 mm/sec to 100 mm/sec. It is preferably from 0.5 mm/sec to 60 mm/sec, and may be, for example, from 1 mm/sec to 50 mm/sec. By extending the speed to such a range, more remarkable effects of the present invention can be obtained. Further, when the stretching speed is equal to or less than the above upper limit value, the semiconductor wafer 8 is less likely to be damaged when the film-like adhesive 13 is extended.

In the cutting step, by using the film-like adhesive 13 (that is, the sheet for semiconductor processing 1), the film-like adhesive 13 can be cut at the target portion, and the film can be prevented from being formed in the cut portion. The defect of the agent 13' is abnormal.

In the cutting step, by using the above-mentioned adhesive layer having a storage elastic modulus at 0 ° C of 1000 MPa or less, when the film-like adhesive 13 is cut, the semiconductor wafer having the film-like adhesive 13' after cutting can be suppressed. 8 (i.e., a semiconductor wafer with a film-like adhesive) is swelled or scattered from the adhesive layer 12.

<Pull off step>

In the pulling-off step, after the cutting step, as shown in FIG. 2(c), the semiconductor wafer 8 including the film-like adhesive 13' after cutting is self-supporting sheet 10 (that is, the adhesive layer 12). ) Pull away and pick it up.

In the pulling-off step, the semiconductor wafer 8 is pulled up by the pulling portion 61 of the manufacturing apparatus of the semiconductor device, whereby the film-like adhesive 13' adhered to the back surface 8b of the semiconductor wafer 8 is self-adhesive Layer 12 is peeled off. The method of pulling up the semiconductor wafer 8 may be a known method, and examples thereof include a method of pulling up the surface of the semiconductor wafer 8 by a vacuum collet, and the like. Here, the pulling direction of the semiconductor wafer 8 is indicated by an arrow II.

In the above-described detachment step, by using the above-described adhesive layer having an adhesion to the semiconductor wafer of 200 mN/25 mm or less, the adhesive layer can be easily picked up without being cured by irradiation of an energy ray or the like. A semiconductor wafer of the following agent.

In the foregoing manufacturing method of the semiconductor device, the semiconductor wafer 8 (that is, the semiconductor wafer with the film-like adhesive) which is pulled apart (that is, picked up) together with the film-like adhesive 13' after the cutting is used, and can be utilized and previously used. The semiconductor device can be manufactured by the same method, and the semiconductor device can be manufactured by the step of bonding the semiconductor wafer to the circuit surface of the substrate by a film-like adhesive die. For example, the semiconductor wafer 8 is die-bonded to the circuit surface of the substrate by the film-like adhesive 13', and if necessary, a semiconductor wafer is further laminated on the semiconductor wafer 8 to be bonded, and then the resin is used. The whole is sealed, thereby making a semiconductor package (not shown). Then, the target semiconductor device can be fabricated using the semiconductor package.

The method for producing a semiconductor device using the film-like adhesive or the semiconductor processing sheet of the present invention is not limited to the above-described method described with reference to FIG. 2, and may be modified in the above method within the range in which the effects of the present invention are not impaired. Delete or add a part of the composition.

[Examples]

Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited by the examples shown below.

The components used in the production of the adhesive composition are shown below.

. Polymer composition

(a)-1: copolymerization of methyl acrylate (hereinafter abbreviated as "MA") (95 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (5 parts by mass) An acrylic resin (weight average molecular weight 800,000, glass transition temperature 9 ° C).

. Epoxy resin

(b1)-1: a cresol novolak type epoxy resin (acrylic acid varnish type "CNA147" manufactured by Nippon Kayaku Co., Ltd., an epoxy equivalent of 518 g/eq, a number average molecular weight of 2,100, an unsaturated group content and a ring Oxygen equivalent).

. Thermal hardener

(b2)-1: aralkylphenol resin ("Milex XLC-4L" manufactured by Mitsui Chemicals Co., Ltd., number average molecular weight: 1100).

. Filler

(d)-1: Spherical cerium oxide ("YA050C-MJE" manufactured by Admatechs Co., Ltd., average particle diameter: 50 nm, methacrylonitrile-decane treated product).

. Coupler

(e)-1: a decane coupling agent, 3-glycidoxypropylmethyldiethoxydecane ("KBE-402" manufactured by Shin-Etsu Chemical Co., Ltd.).

. Crosslinker

(f)-1: Toluene diisocyanate-based crosslinking agent ("BHS8515" manufactured by Toyo Ink Manufacturing Co., Ltd.).

<Manufacture of film-like adhesive and sheet for semiconductor processing>

[Example 1]

(Manufacture of adhesive composition)

Polymer component (a)-1, epoxy resin (b1)-1, thermosetting agent (b2)-1, filler (d)-1, coupling agent (e)-1, and crosslinking agent (f) In the above, the content (parts by mass) was dissolved or dispersed in methyl ethyl ketone so as to have a value shown in Table 1, and the mixture was stirred at 23 ° C to obtain an adhesive composition.

(Manufacture of film-like adhesive)

The above-mentioned peeling-treated surface of the release film which was subjected to the release treatment by polyfluorination treatment on the single side of a polyethylene terephthalate film (thickness: 38 μm), and the above-mentioned obtained adhesive composition was applied thereto. The film was dried by heating at ° C for 3 minutes to form a film-like adhesive having a thickness of 20 μm.

Then, the release-treated surface of the release film was attached to the exposed surface of the film-like adhesive to obtain a film-like adhesive laminate in which the release film was adhered to both surfaces of the film-like adhesive.

(Manufacture of adhesive composition)

To the adhesive resin (100 parts by mass), a crosslinking agent (30.16 parts by mass) was added, and the mixture was stirred at 23 ° C to obtain a non-energy-curable adhesive composition. In addition, all the compounding parts shown here are the solid content conversion value.

The adhesive resin is an acrylic polymer obtained by copolymerizing 2-ethylhexyl acrylate (80 parts by mass) and 2-hydroxyethyl acrylate (20 parts by mass) (weight average molecular weight 86,000, glass transfer) Temperature -61 ° C). Further, the crosslinking agent is a toluene diisocyanate trimer adduct of trimethylolpropane ("Coronate L" manufactured by Tosoh Corporation).

(Manufacture of adhesive sheets)

The peeling treatment surface of the release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness: 38 μm) which was subjected to a release treatment on the single side of the film made of polyethylene terephthalate, was coated with the above-mentioned peeling treatment surface. The obtained adhesive composition was dried by heating at 120 ° C for 2 minutes, thereby forming an adhesive layer having a thickness of 10 μm.

Then, a film of a low-density polyethylene (LDPE) having a thickness of 110 μm as a base material was bonded to the exposed surface of the pressure-sensitive adhesive layer to obtain an adhesive sheet having a release film.

(Manufacture of sheets for semiconductor processing)

After the film-like adhesive laminate was stored at room temperature for one week from the time of production, one of the release films was removed to expose one surface of the film-like adhesive. Further, the release film was removed from the above-obtained adhesive sheet to expose one surface of the adhesive layer. Then, the exposed surface of the film-like adhesive is bonded to the exposed surface of the adhesive layer, whereby a semiconductor processing sheet in which a substrate, an adhesive layer, a film-like adhesive, and a release film are sequentially laminated is obtained.

[Example 2 to Example 7, Comparative Example 1 to Comparative Example 7]

A film-like adhesive and a sheet for semiconductor processing were produced in the same manner as in Example 1 except that the components of the adhesive composition were as shown in Table 1 or Table 2.

Further, the concentration of the solid content of the adhesive composition produced in the above examples and comparative examples was from 18% by mass to 24% by mass.

<Evaluation of film-like adhesives and sheets for semiconductor processing>

The following items were evaluated for the film-like adhesive obtained above and the sheet for semiconductor processing.

(Elongation at break of laminate)

The film-like adhesive obtained above was bonded to a plurality of layers by a laminator to prepare a laminate film-like adhesive having a total thickness of 60 μm. The layered body. Further, the laminate was cut to prepare a test piece having a width of 6 mm, a length of 5 mm, and a thickness of 60 μm.

Then, the temperature of the obtained test piece was set to 0 ° C, and the test piece was stretched using a dynamic viscoelasticity measuring apparatus ("DMA Q800" manufactured by TA Instruments Co., Ltd.) to obtain the elongation at break (%) of the test piece. That is, the elongation at break (%) of the laminate obtained by laminating the film-like adhesive before curing. When the test piece was stretched, the load applied to the test piece was changed from 1 N/min to 18 N/min. The results are shown in Table 1 or Table 2.

(adhesion of film-like adhesive to semiconductor wafer)

An adhesive tape (having a thickness of 24 μm) of a polyethylene terephthalate film (thickness: 50 μm) was prepared as an adhesive layer (having a thickness of 24 μm). One of the film-like adhesive laminates obtained from the above-mentioned film-like adhesive laminate was removed to expose one surface of the film-like adhesive. Then, the adhesive layer of the above-mentioned adhesive tape was bonded to the exposed surface of the film-like adhesive using a bonding machine, thereby producing a laminated sheet. Further, after the laminated sheet was cut into a width of 25 mm and a length of 150 mm, the remaining release film was removed from the film-like adhesive to prepare a test piece.

The test piece was bonded to the mirror surface of the tantalum wafer via a film-like adhesive heated to 50 ° C using a laminator, and allowed to stand at a temperature of 23 ° C for 30 minutes. Then, using the universal tensile tester ("Autograph" manufactured by Shimadzu Corporation), the same temperature was maintained, and the following 180° peeling was performed: the test piece (that is, the film-like adhesive) and the tantalum wafer were in contact with each other. Face to face In this manner, the test piece was peeled off from the tantalum wafer at a peeling speed of 300 mm/min, and the peeling force at this time was measured. The measured value of the peeling force was set as a film-like adhesive pair before curing. The adhesion of the semiconductor wafer (mN / 25mm). The results are shown in Table 1 or Table 2.

(Cutting characteristics of film-like adhesive (1))

Using a cutting device ("DSD6361" manufactured by Disco Corporation), the mirror surface of a wafer of 8 厚度 (thickness: 720 μm) was subjected to the following half-cut: in the form of a square of 10 mm × 10 mm, by cutting the blade The surface of the germanium wafer was cut out to a depth of 80 μm to form a groove.

Then, using a tape laminating machine ("RAD-3510" manufactured by Lintec Co., Ltd.), the back grinding belt ("ADWILL E-3125KN" manufactured by Lintec Co., Ltd.) was attached to the adhesive layer of the back grinding belt at room temperature. The mirror surface of the trenched wafer is formed as described above.

Then, using a grinder ("DFG8760" manufactured by Disco Corporation), the surface of the tantalum wafer opposite to the mirror surface on which the groove was formed was ground. At this time, the thickness of the germanium wafer was 50 μm, and the germanium wafer was divided and singulated into a germanium wafer. The obtained tantalum wafers were vacated at intervals of about 30 μm from each other and fixed to the back grinding belt.

Then, using a tape bonding machine ("ADWILL RAD2500" manufactured by Lintec Co., Ltd.), a film heated to 60 ° C in a sheet for semiconductor processing The semiconductor processing sheet obtained above was attached to the above-mentioned grinding surface of the obtained ruthenium wafer to obtain a laminate.

Then, the obtained laminate is attached to the dicing ring frame by the exposed surface of the adhesive layer in the laminate, and the back surface polishing tape is peeled off from the enamel wafer, thereby obtaining the following laminated structure. In the test piece, the laminated structure system is formed by arranging a plurality of semiconductor wafers which are singulated in advance in an uncut film-like adhesive in a sheet for semiconductor processing.

The above-obtained test piece is set in the extension unit of the expander ("ME-300B" manufactured by JCM Corporation), and the extension amount (that is, the expansion amount) is 10 mm and the extension speed (that is, the expansion) in an environment of 0 °C. At a speed of 1 mm/sec, the sheet for semiconductor processing was stretched, and an attempt was made to cut the film-like adhesive along the outer shape of the tantalum wafer.

Then, using a digital microscope ("VH-Z100" manufactured by Keyence Corporation), a film-like adhesive was observed, and the cutting property (1) of the film-like adhesive was evaluated based on the following criteria. The results are shown in Table 1 or Table 2.

A: The film-like adhesive can be cut at all target sites.

B: The film-like adhesive could not be cut at a part of the target.

C: The film-like adhesive could not be cut at all the target sites.

(Cutting characteristics of film-like adhesive (2))

The back grinding tape ("E-3125KL" manufactured by Lintec Co., Ltd.) was laminated on one side of a 12-inch silicon wafer using a tape bonding machine for back grinding ("RAD-3510F/12" manufactured by Lintec Co., Ltd.).

Then, the following stealth dicing is performed: the exposed side of the unlaminated back grinding belt in the self-twisting wafer, and the laser light irradiated in the infrared region in a manner of focusing on the focus set inside the germanium wafer A modified layer is formed inside the wafer. The invisible cutting was performed by using "DFL7361" manufactured by Disco as a device to obtain a wafer of 8 mm × 10 mm in size.

Then, the exposed surface of the silicon wafer was ground using a grinder ("DGP8761" manufactured by Disco Corporation). At this time, the thickness of the germanium wafer was 40 μm, and the germanium wafer was divided and the wafer was singulated into a germanium wafer. The obtained crucible wafer was fixed to the back grinding belt.

Then, the film for semiconductor processing obtained as described above was attached to the film-form adhesive which was heated to 60 ° C in the sheet for semiconductor processing by using a tape bonding machine ("DFM2800" manufactured by Disco). Thereafter, the ground surface of the wafer is obtained to obtain a laminate.

Then, the obtained laminate is adhered to the dicing ring frame by the exposed surface of the adhesive layer in the laminate, and the back grinding tape is peeled off from the enamel wafer, thereby obtaining the following laminated structure. In the test piece of the body, the laminated structure system is formed by arranging a plurality of semiconductor wafers which are singulated in advance on an uncut film-like adhesive in a sheet for semiconductor processing.

The test piece obtained above was set up in a tenter ("DDS2300" manufactured by Disco Co., Ltd.), and the semiconductor processing was carried out under the condition of a ceiling height of 15 mm and a table ejection speed of 1 mm/sec in an environment of 0 ° C. The sheet was stretched and an attempt was made to cut the film-like adhesive along the outer shape of the tantalum wafer.

Then, the stage is lowered and released, and the extended test piece is set on the other stage different from the above-mentioned expansion machine. Then, the test piece was not adsorbed to the stage, and the test piece was ejected under the conditions of a table top height of 8 mm and a table ejection speed of 1 mm/sec, and the test piece was adsorbed to the stage at the stage where the stage was completely raised, and the semiconductor processing piece was subjected to Extend, try to widen the spacing between adjacent wafers (ie, the kerf width). Further, the state in which the test piece is adsorbed to the stage is kept constant, the stage is lowered, the slit width is maintained without change, and the strain in the outer periphery of the test piece which is not provided in the test piece is eliminated by shrinkage by heating at 250 ° C. . Through the above steps, an attempt was made to obtain a test piece that widened the width of the slit.

Then, a film-like adhesive was observed using a digital microscope ("VH-Z100" manufactured by Keyence Corporation), and the film-like adhesive was evaluated based on the same criteria as in the case of the cutting property (1) of the film-like adhesive described above. Cutting characteristics (2). The results are shown in Table 1 or Table 2.

(reliability of film adhesive)

.矽 wafer manufacturing

The above-mentioned semiconductor processing sheet was heated to 60 ° C using a tape bonding machine ("Adwill RAD 2700" manufactured by Lintec Co., Ltd.), and attached to a dry-polished 12-inch wafer (thickness: 75 μm), and a ring was attached. Box.

Then, the tantalum wafer was singulated into a ruthenium wafer of a size of 8 mm × 8 mm using a dicing apparatus ("DDF6361" manufactured by Disco Corporation). The cutting at this time is at a blade speed of 50 mm/sec, a blade rotation speed of 40,000 rpm, and cutting. The water cut amount was 1 L/min. Further, the amount of cut into the substrate at the time of cutting was set to 20 μm.

. Semiconductor package manufacturing

As the substrate, the following substrate ("LN001E-001 PCB (Au) AUS308" manufactured by Chikaku Tech Co., Ltd.) was used, and the substrate was a copper foil (thickness of a copper-clad laminate) ("OCL-HL830" manufactured by Mitsubishi Gas Chemical Co., Ltd.). 18 μm) was formed with a circuit pattern and a solder resist ("PSR-4000 AUS308" manufactured by Sun Ink Co., Ltd.) on the circuit pattern. The tantalum wafer on the sheet for semiconductor processing obtained above was peeled off from the substrate together with the film-like adhesive, and the tantalum wafer was pressure-bonded to the substrate at 120 ° C, 250 gf, 0.5 second, followed by film formation. The agent fixes the germanium wafer on the substrate to obtain a laminate.

Then, the obtained laminate was allowed to stand in an oven heated to 175 ° C for 4 hours or 2 hours to impart a thermal history of the imaginary wire bonding to the laminate.

Then, a molding resin ("KE-G1250" manufactured by KYOCERA Chemical Co., Ltd.) was used, and a sealing device ("G-CUBE MZ549-1" manufactured by Apic Yamada Co., Ltd.) was used, and the sealing thickness was 400 μm at a sealing temperature of 175. The layered material after the heat history was sealed under the conditions of ° C, a sealing pressure of 7 MPa, and a sealing time of 2 minutes. Further, the aforementioned molding resin was cured at 175 ° C for 5 hours.

Then, the sealed substrate is bonded to a dicing tape ("Adwill D-510T" manufactured by Lintec), and a cutting device (manufactured by Disco Co., Ltd.) is used. "DFD6361"), the sealed substrate is singulated into a size of 15 mm × 15 mm. The cutting at this time was performed under the conditions of a blade speed of 50 mm/sec, a blade rotation speed of 40,000 rpm, and a cutting water volume of 1 L/min.

Through the above steps, a semiconductor package is obtained.

. Evaluation of surface mount and package reliability of semiconductor packages (ie reliability of film-like adhesives)

The semiconductor package obtained above was allowed to stand at a temperature of 85 ° C and a relative humidity of 60% for 168 hours to absorb moisture, and then a reflow furnace ("WL-15-20DNX type" manufactured by Sagami Polytec Co., Ltd.) was used. The infrared-irradiated semiconductor package was subjected to three times of IR (Infrared Radiation) reflow soldering under the conditions of a temperature of 260 ° C and a heating time of 1 minute.

Then, using a scanning ultrasonic flaw detector ("Hye-Focus" manufactured by Hitachi Construction Machinery Finetec Co., Ltd.), it was confirmed whether or not cracks occurred in the semiconductor package, and the package reliability was evaluated based on the following criteria (that is, the film-like adhesive was used). reliability). The results are shown in Table 1 or Table 2.

A: When the laminate having a thermal history was applied at 175 ° C for 4 hours, the semiconductor package after IR reflow was not cracked at all.

B: When the laminate having a thermal history was applied at 175 ° C for 2 hours, the semiconductor package after IR reflow was not cracked at all, but was used at 175 ° C for 4 hours. Given under conditions In the case of the above-mentioned laminate in the thermal history, cracks occur in the semiconductor package after IR reflow.

C: a case where the laminate having a thermal history is applied at 175 ° C for 2 hours, and a case where the laminate is given a thermal history at 175 ° C for 4 hours In the case, cracks are generated in the semiconductor package after IR reflow.

(film-forming property of film-like adhesive)

When the film-like adhesive was produced, the film-forming property of the film-like adhesive was evaluated at the same time.

In other words, when the adhesive composition is applied to the release film on the surface of the obtained film-like adhesive, the appearance of the surface formed by the contact of the adhesive composition with the release film is visually observed, according to the following. The film formation properties of the film-like adhesive were evaluated by reference. The results are shown in Table 1 or Table 2.

A: No abnormality was observed on the surface, and the surface condition was good.

B: Streaks or ridges are formed on the surface, but the disorder of the surface state is mild.

C: Aggregates are formed on the surface, and the surface state is not uniform.

[Table 1]

From the above results, it is clear that in the examples 1 to 7, the elongation at break of the laminate at 0 ° C is 52% or less, and the adhesion of the film-like adhesive is 300 mN / 25 mm or more.

In the film-like adhesives of the first to seventh embodiments, when the cutting property (1) is evaluated, it can be cut by the portion extending to the target, and the defect of the film-like adhesive is not confirmed at the cut portion. Abnormal, showing excellent cutting characteristics. Further, in the film-like adhesives of Examples 1, 3, and 6, when the cutting property (2) was evaluated, excellent cutting properties were also exhibited (films of Example 2, Example 4, and Example 5). The cutting property was not evaluated for the cutting property (2).

Further, the film-like adhesives of Examples 1 to 6 were excellent in reliability and film-forming property, and had no problem as a basic property of the film-like adhesive.

On the other hand, in Comparative Example 1 and Comparative Example 2, the elongation at break of the laminate at 0 ° C was 61% or more, and when the cutting property (1) was evaluated, it was impossible. The film-like adhesive is cut into a target shape, and the film-shaped adhesive has poor cutting properties.

In addition, in Comparative Example 3, Comparative Example 4, and Comparative Example 7, the adhesion of the film-like adhesive was 260 mN/25 mm or less, and when the cutting property (1) was evaluated, the film-like adhesive could not be cut at a part of the target portion. In addition, even if the target portion was cut, an abnormality such as a defect of the film-like adhesive was observed at the cut portion, and the cutting property of the film-like adhesive was inferior. Further, in the film-like adhesives of Comparative Example 3, Comparative Example 4, and Comparative Example 7, when the cutting property (2) was evaluated, the cutting properties were also inferior (Comparative Example 1, Comparative Example 2, Comparative Example 5, and Comparative Example 6). The film-like adhesive was not evaluated for the cutting property (2).

Further, in Comparative Example 5 and Comparative Example 6, the elongation at break at 0 ° C and the adhesion of the film-like adhesive were not measured, and neither the cutting property (1) nor the cutting property (2) could be evaluated. .

Further, the film-like adhesives of Comparative Example 3 and Comparative Example 4 were inferior in reliability, and the film-like adhesives of Comparative Examples 5 and Comparative Example 6 were inferior in film formability, and these had problems in terms of basic properties as a film-like adhesive.

Here, in the case where a part of the film-like adhesive does not evaluate the cutting property (2), it is considered that the cutting property (2) and the cutting property (1) of these film-like adhesives are the same evaluation results. The reason is that if the semiconductor wafer used for evaluation has no abnormality, the method of manufacturing the semiconductor wafer (that is, the method of dividing the semiconductor wafer) does not affect the evaluation step described above. Example 1, Example 3, and Example in which the cutting characteristics (1) and the cutting characteristics (2) were evaluated together 6. The evaluation results of Comparative Example 3, Comparative Example 4, and Comparative Example 7 demonstrate the above.

(industry availability)

The present invention can be preferably used for manufacturing a semiconductor device, and thus is extremely useful industrially.

1‧‧‧Slices for semiconductor processing

10‧‧‧Support tablets

11‧‧‧Substrate

11a‧‧‧ Surface of the substrate

12‧‧‧Adhesive layer

12a‧‧‧ Surface of the adhesive layer

13‧‧‧membranous adhesive

Claims (5)

A film-like adhesive agent is a curable film-like adhesive; the film-like adhesive agent of a single layer before curing having a thickness of 60 μm or the film-like adhesive agent of two or more layers before curing is 60 μm in total. The laminate obtained by laminating the laminate has an elongation at break at 0 ° C of 60% or less, and the adhesion of the film-like adhesive before curing to the semiconductor wafer is 300 mN / 25 mm or more. A sheet for semiconductor processing is provided with a film-like adhesive as described in claim 1 on a support sheet. The sheet for semiconductor processing according to claim 2, wherein the support sheet is provided with an adhesive layer on a substrate, and the film-like adhesive is provided in direct contact with the adhesive layer. A method of manufacturing a semiconductor device using the film-like adhesive according to claim 1, wherein the method for manufacturing a semiconductor device includes the step of forming a laminated structure to form a laminated structure in which the laminated structure is supported The film-like adhesive is provided on the sheet, and a plurality of divided semiconductor wafers are provided on a surface of the film-like adhesive opposite to the side on which the support sheet is provided; and the cutting step is performed on the laminated structure The film-like adhesive agent in the film is extended in the direction along the surface of the film-like adhesive while cooling, and the film-like adhesive is cut; In the pulling-off step, the semiconductor wafer including the film-like adhesive after the cutting is pulled away from the support sheet. The method of manufacturing a semiconductor device according to claim 4, further comprising the step of: forming a modified layer forming step of focusing on a focus set inside the semiconductor wafer before the step of forming the laminated structure; a laser beam in the infrared region forms a reforming layer inside the semiconductor wafer; and a dividing step of grinding a surface of the semiconductor wafer on which the modified layer is formed to provide the film-like adhesive, and Applying a force during grinding to the semiconductor wafer, thereby dividing the semiconductor wafer at a portion of the modified layer to obtain a plurality of semiconductor wafers; and using the plurality of semiconductor wafers obtained in the dividing step in the laminated structure In the body formation step.