TWI704625B - Semiconductor processing sheet and manufacturing method of semiconductor device - Google Patents

Abstract

A adhesive film 13 of the present invention is a curable film-like adhesive, wherein the adhesive film 13 of a single layer before curing with a thickness of 60 m, or a laminate of two or more layers of the adhesive film 13 before curing with a total thickness of 60 m has a breaking elongation of 60% or less as measured at a measurement temperature of 0℃, and wherein the adhesion to a semiconductor wafer before curing of the adhesive film 13 is 300mN / 25mm or more. A sheet 1 for semiconductor processing of the present invention is including an adhesive film 13 provided on a support sheet 10 having a substrate 11.

Description

Semiconductor processing sheet and semiconductor device manufacturing method

The present invention relates to a film adhesive, a semiconductor processing sheet, and a method of manufacturing a semiconductor device.

This application claims priority based on Japanese Patent Application No. 2016-069604 filed in Japan on March 30, 2016, and the content of this application is incorporated herein.

A dicing sheet is used when dicing a semiconductor wafer into a semiconductor wafer. The dicing sheet is composed of, for example, an adhesive layer on a substrate, and is used by attaching the adhesive layer to a semiconductor wafer. After dicing, it is hardened by irradiating energy rays such as ultraviolet rays to reduce the adhesive force of the aforementioned adhesive layer, thereby pulling the semiconductor chip away from the hardened adhesive layer for easy pickup.

On the other hand, for the semiconductor chip after pickup, for example, die bonding is performed on the circuit surface of the substrate by die bonding, and if necessary One or more other semiconductor chips are further laminated on the semiconductor chip, and after wire bonding, the whole is sealed by resin.

Using the semiconductor package obtained in this way, the target semiconductor device is finally manufactured. Therefore, it may be configured to pick up the semiconductor wafer in a state where the surface of the semiconductor wafer to be the target of die bonding is provided with a film-like adhesive.

In the case of using a film-like adhesive in this way, sometimes a dicing die bonding sheet is used. The dicing die bonding sheet is provided on the adhesive layer of the above-mentioned dicing sheet. The film-like adhesive. On the other hand, a plurality of semiconductor wafers singulated in advance may be placed on the film-like adhesive. In this case, a semiconductor processing sheet having the same structure as the dicing die bonding sheet is also used. In the case of using such a semiconductor processing sheet, for example, a plurality of previously singulated semiconductor wafers may be placed on the film adhesive in the semiconductor processing sheet, and the semiconductor processing sheet may be stretched at a low temperature ( expand), whereby the film adhesive is cut corresponding to the outer shape of the semiconductor wafer, and a semiconductor wafer with the cut film adhesive on the target surface is manufactured.

As a semiconductor processing sheet provided with such a film-like adhesive, there are disclosed: the shear adhesive force when the film-like adhesive (ie die bonding film) is adhered to a semiconductor wafer at 25°C, and the adhesion to a dicing sheet (I.e., cutting the film) when the shear adhesive force is set within a specific range for semiconductor processing sheets (refer to Patent Document 1); film-like adhesive before thermal curing (i.e., die bonding film) The elongation at break at 25°C and the ratio of the tensile storage elastic modulus at 0°C to the tensile storage elastic modulus at 25°C are respectively set within a specific range for semiconductor processing sheets (see Patent Document 2); When the thickness of the semiconductor wafer is A (μm), the thickness of the film-like adhesive (ie, the die bonding film) is B (μm), and the thickness of the substrate is C (μm), C/ A, C/B, and A/B are respectively set within a specific range of the semiconductor processing sheet (refer to Patent Document 3); the film-like adhesive (ie, the adhesive sheet) in the B-stage state breaks elongation at 25°C The thickness and elastic modulus, and the thickness of the dicing sheet (that is, the dicing tape) is set to A and the thickness of the film-like adhesive is set to B. Refer to Patent Document 4).

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2011-171588.

Patent Document 2: Japanese Patent Application Publication No. 2011-228399.

Patent Document 3: JP 2012-222002 A.

Patent Document 4: JP 2009-283925 A.

For semiconductor processing sheets provided with a film-like adhesive, in particular, from the viewpoint of improving the cutting characteristics of the film-like adhesive by stretching, further improvement in performance is desired.

Therefore, the object of the present invention is to provide a novel semiconductor processing sheet, which is provided with a film-like adhesive, and the film-like adhesive has good cutting characteristics based on stretching.

In order to solve the above-mentioned problems, the present invention provides a film-like adhesive, which is a curable film-like adhesive; a single layer of the aforementioned film-like adhesive before curing with a thickness of 60 μm, or two or more layers of the aforementioned film-like adhesive before curing The elongation at break of the laminate formed by laminating the adhesive so that the total thickness becomes 60 μm at 0° C. is 60% or less, and the adhesive force of the film-like adhesive to the semiconductor wafer before curing is 300 mN/25 mm or more.

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

As the semiconductor processing sheet of the present invention, it is preferable that 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.

In addition, the present invention provides a method of manufacturing a semiconductor device using the aforementioned film-like adhesive; the method of manufacturing the aforementioned semiconductor device includes the following steps: a step of forming a layered structure to form the following layered structure, the layered structure system being on a support sheet The film-shaped adhesive is provided, and a plurality of divided semiconductor wafers are provided on the surface of the film-shaped adhesive on the opposite side to the side on which the support sheet is provided; The film-like adhesive in the layered structure is cooled while extending in the direction along the surface of the film-like adhesive to cut the film-like adhesive; and the pull-off step is to cut the film-like adhesive with the cut The aforementioned semiconductor chip of the agent is pulled away from the aforementioned supporting sheet.

The manufacturing method of the semiconductor device of the present invention may further include the following step before the step of forming the layered structure: a step of forming a modified layer, irradiating the infrared region to a focal point set inside the semiconductor wafer The laser light is used to form a modified layer inside the semiconductor wafer; and the dividing step is to grind the surface of the semiconductor wafer on which the modified layer is formed on which the film-like adhesive is provided, and to grind the semiconductor The force during grinding is applied to the wafer to divide the semiconductor wafer at the portion of the modified layer to obtain a plurality of semiconductor wafers; the plurality of semiconductor wafers obtained in the above-mentioned dividing step are used in the above-mentioned layered structure forming step in.

According to the present invention, a novel sheet for semiconductor processing is provided, which is provided with a film-like adhesive, and the film-like adhesive has good cutting characteristics based on stretching.

1: Chips for semiconductor processing

8: Semiconductor wafer

8b: The back side of the semiconductor wafer

8': semiconductor wafer

8a': surface of semiconductor wafer

8b': The back side of the semiconductor wafer

10: Support film

11: Substrate

11a: The surface of the substrate

12: Adhesive layer

12a: The surface of the adhesive layer

13: Film adhesive

13a: Surface of film adhesive

13b: The back of the film adhesive

13': Film adhesive after cutting

61: Lifting part

62: Grinding machine

63: Back grinding belt

81': Modified layer of semiconductor wafer

101: Multilayer structure

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

2 is a cross-sectional view for schematically explaining one embodiment of a method of manufacturing a semiconductor device when the film-like adhesive or semiconductor processing sheet of the present invention is used.

FIG. 3 is a cross-sectional view for schematically explaining an embodiment of a method of forming a trench in a semiconductor wafer to obtain a semiconductor wafer.

4 is a cross-sectional view for schematically explaining an embodiment of a method of forming a modified layer on a semiconductor wafer to obtain a semiconductor wafer.

<Film Adhesive>

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

The film-like adhesive of the present invention has a breaking elongation of 60% or less. When forming a semiconductor processing sheet as described later, the sheet (ie, the film-like adhesive) is stretched at a low temperature. When spreading in the direction along the surface of the sheet, the film-like adhesive can be easily cut at the target site.

In addition, the film adhesive of the present invention has the aforementioned adhesive force of 300 mN/25 mm or more, and when it is stretched at a low temperature as described above, the film adhesive can be cut at the target site without abnormalities such as defects of the film adhesive. The reason is presumably because the film adhesive has sufficient adhesive force to the semiconductor wafer, so that when the film adhesive is stretched, the force during stretching tends to be concentrated in the area near the end of the semiconductor wafer in the film adhesive. On the other hand, when the aforementioned adhesive force is less than 300mN/25mm, the film-like adhesive becomes brittle at low temperatures. Therefore, in the stretched film-like adhesive, defects are generated in regions other than the vicinity of the end of the semiconductor wafer. As a result, the force during stretching is dispersed in the film-like adhesive, and therefore, the film-like adhesive is insufficiently cut at the target site. Furthermore, the film-like adhesive before curing shows the same adhesive force to the semiconductor wafer and the semiconductor wafer.

The aforementioned film adhesive has curability. The aforementioned film adhesive preferably has thermosetting properties, and preferably has pressure-sensitive adhesive properties. The film-like adhesive that has both thermosetting and pressure-sensitive adhesive properties can be attached by gently pressing on various adherends in an uncured state. In addition, the film-like adhesive can be applied to various adherends by heating it to soften it. The film-like adhesive finally becomes a cured product with high impact resistance through curing, and the cured product maintains sufficient adhesive properties even under severe high temperature and high humidity conditions.

The film adhesive may be composed of one layer (that is, a single layer), or may be composed of two or more layers. When the film adhesive is composed of multiple layers, These plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited within a range that does not impair the efficacy of the present invention.

Furthermore, in this specification, it is not limited to the case of the film-like adhesive. The term "a plurality of layers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different, and only a part of the layers may be the same" Furthermore, the so-called "multiple layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other".

The thickness of the aforementioned film 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 more than the aforementioned lower limit, higher adhesive force to the adherend (ie, semiconductor wafer) can be obtained. In addition, when the thickness of the film-like adhesive is equal to or less than the aforementioned upper limit, the film-like adhesive can be more easily cut by the stretching described later.

Here, the "thickness of the film adhesive" means the thickness of the entire film adhesive. For example, the thickness of the film adhesive composed of a plurality of layers means the total thickness of all layers constituting the film adhesive. In addition, as a measuring method of the thickness of a film-like adhesive agent, the following method etc. are mentioned, for example, the thickness is measured using a contact thickness meter at arbitrary 5 places, and the average of measured values is calculated.

The laminated system, which is the target for determining the elongation at break, is obtained by laminating two or more layers of the film-like adhesive before curing whose thickness is less than 60 μm so that the total thickness becomes 60 μm.

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

That is, the aforementioned film-like adhesive or laminate having a width of 6 mm, a length of 5 mm, and a thickness of 60 μm is used as a test piece, and the load applied to the test piece is changed from 1N to 18N at a rate of 1N/min. The elongation at break was determined by stretching and measuring the elongation of the test piece at break.

In addition, in this specification, the term "elongation at break X% (where X is a positive number)" means that the test piece (ie, film-like adhesive or laminate) is stretched in the above-mentioned measuring method and the test piece is placed in When the test piece is stretched to X% of the original length (that is, the unstretched length) in the tensile direction, the test piece breaks, that is, the entire length of the test piece in the tensile direction becomes the stretch When the previous length is [1+X/100] times, the test piece breaks.

The elongation at break (%) of the aforementioned film-like adhesive or laminate is 60% or less, preferably 57% or less, and more preferably 54% or less. When the elongation at break is equal to or lower than the upper limit, the film-like adhesive can be cut well by stretching.

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

The aforementioned elongation at break (%) can be appropriately adjusted, for example, by adjusting the type and amount of the components contained in the film adhesive.

For example, by adjusting the molecular weight and content of the polymer component (a) 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 can be easily adjusted.

However, these adjustment methods are just one example.

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

That is, a laminated sheet of a film-like adhesive and adhesive tape having a width of 25 mm and an arbitrary length was produced. The laminated sheet is provided with a film-like adhesive layered on the adhesive area of the adhesive tape. Then, the laminated sheet is attached to the semiconductor wafer by using a film adhesive heated to 40°C to 70°C to produce a laminate in which the adhesive tape, the film adhesive, and the semiconductor wafer are sequentially laminated. Immediately leave the laminated product at 15°C to 27°C for 30 minutes, and then perform the following so-called 180° peeling: The contact surface of the film-like adhesive and the semiconductor wafer is at an angle of 180°. In this way, the laminated sheet of the film-like adhesive and adhesive tape is peeled from the semiconductor wafer at a peeling speed of 300mm/min. The peeling force at this time was measured, and the measured value of the peeling force was taken as the adhesive force (N/25mm) of the film-like adhesive before curing to the semiconductor wafer. The length of the laminated sheet used for the measurement is not particularly limited as long as it is a range in which the peeling force can be measured stably, and it is preferably 100 mm to 300 mm.

The adhesive force of the film-like adhesive to the semiconductor wafer before curing is 300mN/25mm or more. For example, it can be any of 310mN/25mm or more, 340mN/25mm or more, 380mN/25mm or more, but it is not limited to these .

In addition, the upper limit of the aforementioned adhesive force is not particularly limited. For example, it can be selected from 10N/25mm, 800mN/25mm, 700mN/25mm, 600mN/25mm, 500mN/25mm, etc., but these are just examples.

The adhesive force of the film-like adhesive before curing to the semiconductor wafer can be appropriately adjusted by, for example, adjusting the types and amounts of components contained in the film-like adhesive.

For example, by adjusting the molecular weight of the polymer component (a) described later, the ratio of each monomer component constituting the polymer component (a), the softening point of the components constituting the epoxy-based thermosetting resin (b), and the film The content of each component contained in the adhesive agent can easily adjust the adhesive force of the film adhesive.

However, these adjustment methods are just one example.

The film adhesive of the present invention shows good cutting characteristics even at a relatively slow extension speed. For example, the film-like adhesive of the present invention is particularly preferred in the following situations: as described later, the extension speed is slowed down to 0.5 mm/sec to 100 mm/sec, etc. for use. In such a situation where the extension speed is slow, the semiconductor chip becomes less susceptible to damage when the film-like adhesive is cut, and more significant effects of the present invention can be obtained.

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

[Adhesive composition]

The film adhesive may be formed of an adhesive composition containing the constituent material of the film adhesive. For example, by coating the adhesive composition on the surface to be formed of the film-like adhesive, and drying the adhesive composition as necessary, the film-like adhesive can be formed on the target site. A more specific method of forming the film adhesive will be described in detail later together with the method of forming other layers. The content ratio of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the film adhesive. In addition, in this specification, the "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C, etc.

The adhesive composition can be applied by a known method. For example, the following methods can be used for coating machines: air knife coater, knife coater, bar coater, gravure coater, missing corner wheel Coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, meyer bar coater , Contact coating machine, etc.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains the solvent described later, it is preferable to perform heating and drying. In the case, for example, it is preferable to perform drying under the conditions of 70°C to 130°C and 10 seconds to 5 minutes.

As a preferable adhesive composition, the adhesive composition containing a polymer component (a) and epoxy-type 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 the polymerization reaction of a polymerizable compound, and is used to impart film-forming properties or flexibility to the film-like adhesive and to improve the adhesion to semiconductor wafers and other bonding objects (also That is, adhesive) polymer compound. In addition, the polymer component (a) is also a component that does not belong to the epoxy resin (b1) and the thermosetting agent (b2) described later.

The polymer component (a) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrary select.

As the polymer component (a), for example, acrylic resin, polyester, urethane resin, acrylic urethane resin, silicone resin, rubber resin, phenoxy resin, The thermosetting polyimide or the like is preferably an acrylic resin.

As the aforementioned acrylic resin in the polymer component (a), known acrylic polymers can be cited.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 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 adhesive or laminate and the adhesive force of the film adhesive are easily adjusted to the above range.

On the other hand, when the weight average molecular weight of the acrylic resin is greater than or equal to the aforementioned lower limit, the shape stability of the film adhesive (that is, the stability with time during storage) improves. In addition, since the weight average molecular weight of the acrylic resin is below the above upper limit, the film adhesive can easily follow the uneven surface of the adherend, and the generation of voids between the adherend and the film adhesive can be further suppressed Wait.

In addition, in this specification, the so-called "number average molecular weight" and "weight average molecular weight", unless otherwise specified, are polystyrene conversion values measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) .

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin is more than the aforementioned lower limit, the adhesive force between the film-like adhesive and the support sheet described later is suppressed, and the semiconductor wafer provided with the film-like adhesive can be more easily pulled off from the support sheet during pickup. In addition, when the Tg of the acrylic resin is equal to or lower than the aforementioned upper limit, the adhesive force between the film-like adhesive and the semiconductor wafer is improved. Furthermore, Ben said In the specification, the "glass transition temperature" is a DSC (Differential Scanning Calorimetry) curve of a sample measured with a differential scanning calorimeter, and is expressed by the inflection point temperature of the obtained DSC curve.

Examples of acrylic resins include (meth)acrylate copolymers having structural units derived from (meth)acrylate monomers. The aforementioned (meth)acrylates constituting the acrylic resin herein include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, ( Hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid N-nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as (meth) Lauryl acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate , Cetyl (meth)acrylate (also known as (meth)palmityl acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as ( Stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms; isobornyl (meth)acrylate, (meth) Cycloalkyl (meth)acrylates such as dicyclopentyl acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; (meth) (Meth) cycloalkenyl acrylate such as dicyclopentenyl acrylate; cycloalkenyl (meth) acrylate such as dicyclopentenoxy ethyl (meth)acrylate; (meth) propylene Diimines; (meth)acrylates containing glycidyl groups such as glycidyl (meth)acrylate; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-hydroxypropyl ester, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Hydroxyl-containing (meth)acrylate; (meth)acrylate N-methylaminoethyl (meth)acrylate and other substituted amino group-containing (meth)acrylates. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

In addition, in this 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)acrylic acid" The concept of "Acryl" and "Methacryl" includes both.

Regarding the acrylic resin, for example, in addition to the aforementioned (meth)acrylate, it may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide. One or more of the monomers are copolymerized.

The monomer constituting the acrylic resin may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

In addition to the above-mentioned hydroxyl groups, acrylic resins may also have the following functional groups that can be bonded to other compounds: vinyl groups, (meth)acrylic groups, amino groups, carboxyl groups, isocyanate groups, and the like. These functional groups represented by the hydroxyl group in the acrylic resin may be bonded to other compounds via the crosslinking agent (f) described later, or may be directly bonded to other compounds without the crosslinking agent (f). Acrylic resins are bonded to other compounds via the aforementioned functional groups, thereby tending to improve the reliability of packages obtained by using film adhesives.

In the present invention, as the polymer component (a), a thermoplastic resin other than the acrylic resin (hereinafter, abbreviated as "thermoplastic resin") may be used alone instead of the acrylic resin, or may be used in combination with the acrylic resin. By containing the aforementioned thermoplastic resin, it may be easier to pull the semiconductor wafer with the film-like adhesive from the supporting sheet during pickup, or the film-like adhesive may easily follow the uneven surface of the adherend, which can further suppress the 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 1,000 to 100,000, more preferably 3,000 to 80,000.

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

As said thermoplastic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

The aforementioned thermoplastic resin contained in the adhesive composition and the film-like adhesive may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

In the adhesive 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 adhesive), regardless of the polymer component ( Regardless of the type of a), it is preferably 20% by mass to 75% by mass, and more preferably 30% by mass to 65% by mass.

(Epoxy-based 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 one type or two or more types; in the case of two or more types, a combination of these two or more types And the ratio can be chosen arbitrarily.

‧Epoxy resin (b1)

As the epoxy resin (b1), well-known epoxy resins can be cited, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, ortho-cresol novolac epoxy Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. Compound.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by containing an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film adhesive is improved.

As an epoxy resin having an unsaturated hydrocarbon group, for example, a compound obtained by replacing a part of the epoxy group of a polyfunctional epoxy resin with a group having an unsaturated hydrocarbon group is mentioned. Such a compound is obtained, for example, by performing an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group. In addition, in this specification, the "derivative", unless otherwise specified, means a compound in which one or more groups of the original compound are substituted with groups other than the group (that is, a substituent). Here, the so-called "radical" not only refers to a group of atoms formed by bonding a plurality of atoms, but also includes one atom.

In addition, as an epoxy resin having an unsaturated hydrocarbon group, for example, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin or the like can be cited.

The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include: ethylene group (that is, vinyl group), 2-propenyl group (that is, allyl group), (methyl) The acrylic group, (meth)acrylamide group, etc. are preferably acrylic group.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but in terms of the curability of the film-like adhesive, and the strength and heat resistance of the film-like adhesive after curing, it is preferably 300 to 30,000, and more It is preferably 400 to 10,000, particularly preferably 500 to 3,000.

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

The epoxy resin (b1) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrary select.

‧Thermal hardener (b2)

The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1).

As a thermosetting agent (b2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned function The group includes, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acid group formed by anhydride, etc., preferably a phenolic hydroxyl group, an amino group, or an acid group formed by anhydride , More preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (b2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenol resins, biphenols, novolac type phenol resins, biphenyl type phenol resins, aralkyl type phenol resins, etc. .

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

The thermosetting agent (b2) may have an unsaturated hydrocarbon group.

As the thermosetting agent (b2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group; a compound having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin Compounds etc.

The aforementioned unsaturated hydrocarbon group in the thermosetting agent (b2) is the same as the unsaturated hydrocarbon group in the aforementioned epoxy resin having an unsaturated hydrocarbon group.

In the case of using a phenolic curing agent as the thermosetting agent (b2), the thermosetting agent (b2) is preferably a softening point or in terms of the ease of adjusting the aforementioned adhesive force of the film adhesive to within the above range The glass transition temperature is high.

The thermosetting agent (b2) includes resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin. The number average molecular weight of is preferably 300 to 30,000, more preferably 400 to 10,000, particularly preferably 500 to 3,000.

In the thermosetting agent (b2), the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, and for example, it is preferably 60 to 500.

The thermosetting agent (b2) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrary select.

In the adhesive composition and the film-like adhesive, the content of the thermosetting agent (b2) is relative to 100 parts by mass of the epoxy resin (b1), preferably 0.1 to 500 parts by mass, more preferably 1 part by mass To 200 parts by mass. When the aforementioned content of the thermosetting agent (b2) is greater than or equal to the aforementioned lower limit, the film-like adhesive is more easily cured. In addition, when the aforementioned content of the thermosetting agent (b2) is below the aforementioned upper limit, the moisture absorption rate of the film-like adhesive decreases, and the reliability of the package obtained by using the film-like adhesive is further improved.

In the adhesive composition and film adhesive, when the content of the polymer component (a) is set to 100 parts by mass, the content of the epoxy-based thermosetting resin (b) (that is, the epoxy resin (b1) and thermal The total content of the hardener (b2)) is preferably 5 parts by mass to 100 parts by mass, more preferably 7 parts by mass to 90 parts by mass, particularly preferably 9 parts by mass to 80 parts by mass, for example, may be 9 parts by mass to 70 parts by mass. Any one of parts by mass, 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, etc. With epoxy-based thermosetting resin The aforementioned content of (b) is in this range, and the aforementioned elongation at break of the film-like adhesive or laminate and the aforementioned adhesive force of the film-like adhesive are easily adjusted to the aforementioned range.

In the aforementioned film adhesive, in addition to the polymer component (a) and epoxy-based thermosetting resin (b), other components that do not belong to these may be further included as necessary to improve various physical properties of the film adhesive .

As other preferable components contained in the film-like adhesive, for example, curing accelerator (c), filler (d), coupling agent (e), crosslinking agent (f), energy ray curable resin (g), photopolymerization initiator (h), general additives (i), etc.

(Hardening accelerator (c))

The hardening accelerator (c) is a component used to adjust the hardening speed of the adhesive composition.

As a preferable hardening accelerator (c), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol can be cited; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (that is, imidazoles in which more than one hydrogen atom is replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (that is, 1 Phosphine in which more than one hydrogen atom is substituted by an organic group); tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate, triphenyl phosphine tetraphenyl borate, etc.

The hardening accelerator (c) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrary select.

When the curing accelerator (c) is used, when the content of the epoxy-based thermosetting resin (b) in the adhesive composition and the film-like adhesive is 100 parts by mass, the curing accelerator (c) is The content is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the hardening accelerator (c) is more than the aforementioned lower limit, more remarkable effects of using the hardening accelerator (c) can be obtained. In addition, since the content of the hardening accelerator (c) is below the aforementioned upper limit, for example, the high-polar hardening accelerator (c) is prevented from adhering to the adherend in the film-like adhesive under high temperature and high humidity conditions. The effect of segregation due to the movement of the interface side becomes higher, and the reliability of the package obtained by using the semiconductor processing sheet is further improved.

(Filling material (d))

When the film adhesive contains the filler (d), it becomes easy to adjust the thermal expansion coefficient of the film adhesive so that the thermal expansion coefficient is optimal for the object to be attached to the film adhesive, thereby using a film The reliability of the package obtained by the adhesive is further improved. In addition, when the film adhesive contains the filler (d), the moisture absorption rate of the cured film adhesive can be reduced, or the heat dissipation can be improved.

The filling material (d) may be any one of an organic filling material and an inorganic filling material, preferably an inorganic filling material.

As a preferable inorganic filler, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by sphericalization Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.

Among these, the inorganic filler material is preferably silica or alumina.

The filling material (d) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected .

When the filler (d) is used, 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 (d) in the film adhesive) The content of) is preferably 5 mass% to 80 mass%, more preferably 7 mass% to 60 mass%. When the content of the filler (d) is in this range, it is easier to adjust the thermal expansion coefficient.

(Coupling agent (e))

By containing the coupling agent (e), the film-like adhesive improves the adhesion and adhesion to the adherend. In addition, since the film-like adhesive contains the coupling agent (e), the cured product of the film-like adhesive improves water resistance without impairing heat resistance. high. The coupling agent (e) has a functional group that can react with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group possessed by the polymer component (a), epoxy-based thermosetting resin (b), etc., and more preferably a silane coupling agent.

As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxyoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyl triethoxysilane, imidazole silane, etc.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected .

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

With the aforementioned content of the coupling agent (e) above the aforementioned lower limit, the following more significant effects brought 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 Improve the adhesion between the adhesive and the adherend. In addition, when the aforementioned content of the coupling agent (e) is not more than the aforementioned upper limit, the generation of outgassing can be further suppressed.

(Crosslinker (f))

When using the above-mentioned acrylic resin and other polymer components having functional groups such as vinyl groups, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds, as the polymer component (a) In this case, the adhesive composition and the film-like adhesive may also contain a crosslinking agent (f), which is used to bond the aforementioned functional group to another compound for crosslinking. By using the crosslinking agent (f) for crosslinking, the initial adhesive force and cohesive force of the film-like adhesive can be adjusted.

As the crosslinking agent (f), for example, an organic polyisocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (ie, a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent Agents (ie, crosslinking agents with aziridinyl groups) and the like.

Examples of the aforementioned organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate bodies and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with polyol compounds Wait. The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, which contains ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. The reactant of a low-molecular-weight active hydrogen compound, as an example of the adduct, includes the xylylene diisocyanate adduct of trimethylolpropane and the like described later. In addition, the so-called "terminal isocyanate urethane prepolymer" is as described above.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate Isocyanate; Diphenylmethane-4,4'-Diisocyanate; Diphenylmethane-2,4'-Diisocyanate; 3-Methyldiphenylmethane Diisocyanate; Hexamethylene Diisocyanate; Isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; All or part of the hydroxyl groups of polyols such as trimethylolpropane are added to toluene diisocyanate, Hexamethylene bis A compound of any one or more of isocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

As the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridine methamide), trimethylolpropane-tri-β-nitrogen Propidinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinylmethamine) triethylene Based on melamine and so on.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component (a). 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 the reaction between the crosslinking agent (f) and the polymer component (a) Into the film adhesive.

The crosslinking agent (f) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrary select.

In the case of using the crosslinking agent (f), when the content of the polymer component (a) in the adhesive composition is 100 parts by mass, the content of the crosslinking agent (f) is preferably 0.01 to 20 parts by mass Parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, particularly preferably 0.3 parts by mass to 5 parts by mass. When the aforementioned content of the cross-linking agent (f) is above the aforementioned lower limit, more significant results can be obtained by using the cross-linking agent (f) The effect brought by. In addition, when the aforementioned content of the crosslinking agent (f) is below the aforementioned upper limit, excessive use of the crosslinking agent (f) can be suppressed.

(Energy ray curable resin (g))

By containing the energy-ray curable resin (g), the film-like adhesive can change its characteristics by irradiation with energy rays.

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

Examples of the aforementioned energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth)acryloyl group are preferred.

Examples of the acrylate-based compounds include: trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Base) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol two(meth)acrylate, 1,6-hexanediol two (Meth)acrylates and other (meth)acrylates containing chain aliphatic skeletons; (meth)acrylates such as dicyclopentyl di(meth)acrylates containing cyclic aliphatic skeletons; polyethylene glycol Polyalkylene glycol (meth)acrylate such as di(meth)acrylate; oligoester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modification (former Base) acrylate; the aforementioned polyalkylene Polyether (meth)acrylates other than glycol (meth)acrylates; itaconic acid oligomers, etc.

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

The energy ray curable resin (g) contained in the adhesive composition may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

In the case of using energy ray curable resin (g), the ratio of the content of the energy ray curable resin (g) to the total content of all components other than the solvent in the adhesive composition is preferably 1% by mass to 95% % By mass, more preferably 5% by mass to 90% by mass, particularly preferably 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 also be contained so that the energy ray curable resin (g) can be polymerized efficiently.

As the photopolymerization initiator (h) in the adhesive composition, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin Benzoin compounds such as dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1- Acetophenone compounds such as phenyl-propane-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzyl) Phosphine oxide compounds such as phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide; sulfur such as benzyl phenyl sulfide and tetramethyl thiuram monosulfide Ether compounds; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; Peroxide compounds; diketone compounds such as diacetyl; benzil; benzil; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy -2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; Quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone, etc.

In addition, as the photopolymerization initiator (h), for example, photosensitizers such as amines can also be cited.

The photopolymerization initiator (h) contained in the adhesive composition may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

In the case of using the photopolymerization initiator (h), when the content of the energy ray curable resin (g) in the adhesive composition is 100 parts by mass, the content of the photopolymerization initiator (h) is preferable It is 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.

(General additives (i))

The general-purpose additive (I) may be a well-known general-purpose additive, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred general-purpose additives (I) include, for example, plasticizers, antistatic agents, antioxidants, and coloring. Agents (ie dyes or pigments), getters, etc.

The general additives (i) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected .

The content of the adhesive 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, the polymer component (a) and the epoxy-based thermosetting resin (b) are used to improve the film-forming properties such as the surface condition of the film-like adhesive becomes better. And the total content of filler (d) (that is, the total content of polymer component (a), epoxy resin (b1), thermosetting agent (b2) and filler (d)) is set to 100 parts by mass, polymerization The content of the substance component (a) is preferably 30 parts by mass or more, more preferably 38 parts by mass or more. In addition, in terms of the above, the upper limit of the aforementioned 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 film adhesive, in terms of improving the reliability of the film adhesive, the polymer component (a), epoxy-based thermosetting resin (b), and filler The total content of (d) (that is, the total content of polymer component (a), epoxy resin (b1), thermal hardener (b2) and filler (d) When content) is set to 100 parts by mass, the content of the polymer component (a) is preferably 45 parts by mass or more. In addition, in terms of the above, the upper limit of the aforementioned content of the polymer component (a) is not particularly limited, but is preferably 65 parts by mass.

(Solvent)

The adhesive composition preferably further contains a solvent. The workability of the solvent-containing adhesive composition becomes better.

The aforementioned solvent is not particularly limited, and preferred solvents include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1- Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (that is, those with amide bonds Compound) and so on.

The solvent contained in the adhesive composition may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

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

[Method of manufacturing adhesive composition]

The adhesive composition is obtained by compounding the components used to form the adhesive composition.

The order of adding each component is not particularly limited, and it can also be added at the same time. Add more than 2 ingredients.

When a solvent is used, it can be used in the following way: mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; it can also be used in the following way: not using any other than the solvent The compounding ingredients are diluted in advance, and the solvent is mixed with these compounding ingredients.

The method of mixing each component at the time of compounding is not particularly limited, and can be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; and applying ultrasonic waves. Methods of mixing, etc.

Regarding the temperature and time when each component is added and mixed, it is not particularly limited as long as it does not degrade each compounded component and may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

◎Semiconductor processing wafers

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

The semiconductor processing sheet of the present invention is suitable for the following steps: a plurality of pre-divided semiconductor wafers are placed on the film adhesive in the semiconductor processing sheet, and the so-called stretching is performed at a low temperature, even if the film adhesive Together with the support sheet, it expands in a direction along the surface of the film-like adhesive, thereby cutting the film-like adhesive corresponding to the outer shape of the semiconductor wafer. Half of the film-like adhesive after cutting is provided on the surface (that is, the back surface) opposite to the surface on which the circuit is formed (hereinafter sometimes referred to as "circuit formation surface") Conductor wafers (sometimes referred to as "semiconductor wafers with film-like adhesive" in this specification) are used to manufacture semiconductor devices after being picked up.

By using the semiconductor processing sheet of the present invention, when the film-like adhesive is cut by stretching, the film-like adhesive can be cut at the target site, and the generation of the film-like adhesive at the cut site can be suppressed. Defects and other abnormalities, showing excellent cutting characteristics. Therefore, the semiconductor wafer with the film-like adhesive can be easily picked up without any abnormality in the process.

The above-mentioned film-like adhesive is suitably applied to the production of a semiconductor wafer with a film-like adhesive including a thin-thickness semiconductor wafer, for example, when the cutting system based on the stretching is used.

A plurality of divided semiconductor wafers can be produced, for example, by the following method: from the circuit forming surface (that is, the surface) on the opposite side to the attachment surface (that is, the back surface) of the film-like adhesive in the semiconductor wafer A groove is formed, and the back surface is ground until the groove is reached. In this way, the operation of cutting into the semiconductor wafer without dividing the semiconductor wafer and leaving the bottom of the trench is called half cutting. However, in the present invention, the so-called "half cut" does not only mean the operation of cutting the semiconductor wafer so that the depth of the trench becomes a specific value such as half of the thickness of the semiconductor wafer, but it means the operation of cutting the semiconductor wafer with the remaining trench as described above. The bottom of the groove cuts into all operations of the semiconductor wafer.

As a method of forming the aforementioned groove, for example, the following method can be cited: a method of forming a groove by cutting into a semiconductor wafer with a blade (that is, a blade Cutting); a method of forming grooves by cutting into a semiconductor wafer by using laser irradiation (ie laser cutting); a method of forming grooves by cutting into a semiconductor wafer by blowing water containing abrasives (ie, water Cutting) etc. However, as these, when manufacturing a semiconductor wafer by cutting off a part of the semiconductor wafer, corresponding to the cutting off of a part of the semiconductor wafer (that is, the formation of grooves in the semiconductor wafer), the semiconductor wafer Loss, the number of semiconductor wafers obtained from one semiconductor wafer decreases. In addition, the film adhesive after the final cutting is larger than the semiconductor wafer, so when cutting the film adhesive or picking up a semiconductor wafer with a film adhesive described later, the film adhesive after cutting may be wound On the side of a semiconductor wafer, etc.

On the other hand, a plurality of divided semiconductor wafers can also be produced by the following method: irradiate laser light in the infrared region to focus on a focal point set inside the semiconductor wafer to form a modified semiconductor wafer. After the quality layer, the back surface of the semiconductor wafer is ground, and the grinding force is further applied to the semiconductor wafer during the back surface grinding, thereby dividing the semiconductor wafer at the portion where the modified layer is formed. In this method, since there is no step of cutting off a part of the semiconductor wafer, it is possible to suppress the reduction in the number of semiconductor wafers produced as described above, and the film-like adhesive after cutting from being wound on the side surface of the semiconductor wafer. favorable.

<<Support film>>

As said support sheet, the support sheet which has a base material is mentioned. Such a support sheet may be composed of a substrate (that is, only a substrate), or may have a substrate And other layers other than the substrate. As the support sheet having the aforementioned other layer, for example, a support sheet having an adhesive layer on a base material can be cited.

In the semiconductor processing sheet 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 with an adhesive layer on the substrate, a film-like adhesive is provided on the adhesive layer and when the support sheet is composed of a substrate, the substrate is directly contacted Film adhesive.

The aforementioned support sheet may be composed of one layer (that is, a single layer), or may be composed of two or more layers. When the supporting sheet is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

As the support sheet, it is preferably a support sheet provided with an adhesive layer on the substrate, and more preferably a support sheet provided with an adhesive layer in direct contact with the substrate.

That is, as the semiconductor processing sheet of the present invention, an adhesive layer is preferably provided on the substrate and a film-like adhesive is provided on the adhesive layer, and it is more preferably in direct contact with the substrate A sheet for semiconductor processing provided with an adhesive layer and a film-like adhesive on the adhesive layer, particularly preferably with an adhesive layer in direct contact with the substrate and a film-like adhesive in direct contact with the adhesive layer Chips for semiconductor processing.

<Substrate>

The constituent material of the aforementioned substrate is preferably various resins. Specifically, for example, polyethylene (low density polyethylene (sometimes abbreviated as LDPE), linear low-density polyethylene (sometimes abbreviated as LLDPE), high Density polyethylene (sometimes referred to as HDPE), polypropylene, polybutene, polybutadiene, polymethylpentene, styrene-ethylene butene-styrene block copolymer, polyvinyl chloride, chlorine Ethylene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyacrylate urethane, polyimide, ethylene-vinyl acetate copolymer, Ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, polystyrene, polycarbonate, fluororesin, hydrogenated product, modified product, and crosslinked of any of these resins Materials or copolymers, etc.

The resin constituting the base material may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

The base material may be composed of one layer (that is, a single layer), or may be composed of two or more layers. When the substrate is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

The surface of the substrate composed of a single layer can also be peeled off by a known method.

The thickness of the substrate can be appropriately selected according to the purpose, and is preferably 50 μm to 300 μm, more preferably 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 layers constituting the base material. In addition, as a measuring method of the thickness of a base material, the following method etc. are mentioned, for example, the thickness is measured using a contact thickness meter at arbitrary 5 places, and the average of measured values is calculated.

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

In addition, the surface of the substrate may also be subjected to primer treatment.

In addition, the substrate may also have an antistatic coating to prevent the substrate from being attached to other sheets or the substrate to the layer of the suction table when the semiconductor processing sheets are stacked and stored.

<Adhesive layer>

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

The aforementioned adhesive layer may be a well-known adhesive layer.

Examples of the aforementioned adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ether, and polycarbonate. It is an acrylic resin.

Furthermore, in the present invention, the concept of "adhesive resin" includes both adhesive resins and adhesive resins. For example, not only resins with adhesive properties, but also adhesives and additives, etc. Resins that exhibit adhesiveness by combining components, or resins that exhibit adhesiveness by the presence of triggers such as heat or water.

The adhesive layer may be either energy ray hardenability or non-energy ray hardenability, and is preferably non-energy ray hardenability.

In the present invention, the term "energy rays" means electromagnetic waves or charged particle beams having energy quantum, and examples of the energy rays include ultraviolet rays, electron beams, and the like.

The ultraviolet rays can be irradiated by using, for example, 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 be irradiated with an electron beam generated by an electron beam accelerator or the like.

In the present invention, the "energy ray curability" refers to the property of curing by irradiation with energy rays, and the "non-energy ray curability" refers to the property of not curing even if energy rays are irradiated.

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

However, the preferred adhesive layer is not limited to this.

The adhesive layer to be used for obtaining the aforementioned storage elastic modulus may be a single-layer adhesive layer with a thickness of 200 μm, or two or more adhesive layers with a thickness of less than 200 μm may be laminated so that the total thickness becomes 200 μm And the laminated body obtained.

Furthermore, in this specification, the adhesive layer to be used for obtaining the storage elastic modulus may be either a single-layer adhesive layer or the aforementioned laminate, and may be simply described as an "adhesive layer".

In addition, in this specification, the above-mentioned "storage elastic modulus of the adhesive layer" and "storage elastic modulus of the laminate" respectively mean "the adhesive before curing" when the adhesive layer is curable unless otherwise specified. Storage elastic modulus of layer", "Storage elastic modulus of laminate before hardening of adhesive layer".

The storage elastic modulus of the aforementioned adhesive layer or laminate at 0°C is preferably 1000 MPa or less, and more preferably 996 MPa or less. Since the storage elastic modulus is not more than the upper limit, as described later, when the film-like adhesive is cut by stretching, it is possible to prevent the semiconductor chip with the film-like adhesive from swelling or scattering from the adhesive layer.

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

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

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

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

However, these adjustment methods are just one example.

The adhesive force of the aforementioned adhesive layer to the semiconductor wafer is preferably 200 mN/25mm or less, more preferably 196 mN/25mm or less. Since the aforementioned adhesive force is below the aforementioned upper limit value, as described later, even if the adhesive layer is not cured by irradiation of energy rays or the like, the semiconductor wafer with the film-like adhesive can be easily picked up.

The lower limit of the adhesive force of the aforementioned adhesive layer to the semiconductor wafer is not particularly limited. For example, it can be set to any of 10 mN/25 mm, 30 mN/25 mm, and 50 mN/25 mm, but these are just examples.

In addition, in this specification, the "adhesive force of the adhesive layer to the semiconductor wafer" means that the "adhesion of the adhesive layer to the semiconductor wafer before curing" is used when the adhesive layer is curable unless otherwise specified. Adhesion". In addition, unless otherwise specified, the measurement of the aforementioned adhesive force is the measurement of the adhesive force in the standard state specified in JIS Z0237 2008.

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

Even if the types of semiconductor wafers such as silicon wafers are different or the types are the same but the manufacturing batches are different, as long as the same adhesive layer is attached to the same part of the semiconductor wafer such as silicon wafers, the adhesion to the adhesive layer The unevenness is small. Therefore, the adhesive force of the adhesive layer can be specified with high accuracy by selecting the semiconductor wafer as the measurement target of the adhesive force. In the present invention, by selecting the adhesive layer whose adhesive force of the adhesive layer to the mirror surface of the semiconductor wafer is 200mN/25mm or less, the adhesive force of the adhesive layer to the film-like adhesive can be adjusted, so as to attach the film-like adhesive When the semiconductor wafer of the adhesive is pulled away from the adhesive layer and picked up, it is possible to suppress the occurrence of step abnormalities and easily pick up. For all film adhesives used in the aforementioned fields, the effect of the present invention will be exhibited.

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

For example, by adjusting the combination of monomers constituting the adhesive resin, the ratio of the aforementioned monomers, the blending amount of the crosslinking agent, the content of the filler, etc., the adhesive force of the adhesive layer can be easily adjusted.

However, these adjustment methods are just one example.

The adhesive layer may be composed of one layer (that is, a single layer), or may be composed of two or more layers. When the adhesive layer is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

The thickness of the adhesive layer can be appropriately selected according to the purpose, and is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 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 measuring method of the thickness of an adhesive layer, the following method etc. are mentioned, for example, the thickness is measured using a contact thickness meter at arbitrary 5 places, and the average of measured values is calculated.

The aforementioned adhesive layer may be formed of an adhesive composition containing an adhesive. For example, the adhesive composition is applied to the surface to be formed of the adhesive layer, and the adhesive composition is dried as necessary, thereby forming the adhesive layer on the target site. Regarding the more specific forming method of the adhesive layer, it is different from other layers The formation method will be described in detail later. The content ratio of the components that do not vaporize at room 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 it can be performed by the same method as the application of the adhesive composition described above.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains the solvent described later, it is preferable to heat and dry. In this case, for example, it is preferably at 70°C to 130°C for 10 seconds to Dry under 5 minutes.

[Adhesive composition]

The aforementioned adhesive composition is preferably non-energy ray curable.

As the non-energy-ray-curable adhesive composition, for example, it may contain the aforementioned acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, or poly A composition of adhesive resin (hereinafter referred to as "adhesive resin (i)") such as carbonate.

(Adhesive resin (i))

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

As the aforementioned acrylic resin in the adhesive resin (i), for example, an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate is mentioned.

The structural unit possessed by the aforementioned acrylic resin may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

Examples of the aforementioned alkyl (meth)acrylate include alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the aforementioned alkyl group is preferably linear or branched. shape.

As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (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 palmetyl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as (meth)acrylate (Base) stearyl acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.

In terms of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from the alkyl (meth)acrylate alkyl ester having a carbon number of 4 or more. In addition, in terms of further improving the adhesive force of the adhesive layer, the carbon number of the aforementioned alkyl group is preferably 4-12, more preferably 4-8. In addition, the alkyl (meth)acrylate whose alkyl group has 4 or more carbon atoms is preferably an alkyl acrylate.

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

As the aforementioned functional group-containing monomers, for example, the following monomers can be exemplified, which can be the starting point of crosslinking by reacting the aforementioned functional group with the crosslinking agent described later, or can be made by the aforementioned functional group and the unsaturated group-containing The unsaturated group in the compound reacts, and the 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 amino group, and an epoxy group.

That is, as a monomer containing a functional group, for example, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an amine group, a monomer containing an epoxy group, and the like can be cited.

Examples of the aforementioned hydroxyl-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl ester, (meth)acrylic acid 2-hydroxy Butyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; non-(meth)acrylic acids such as vinyl alcohol and allyl alcohol Saturated alcohols (that is, unsaturated alcohols without (meth)acrylic acid skeleton) and the like.

Examples of the aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid (that is, monocarboxylic acids having ethylenically unsaturated bonds); fumaric acid, Itaconic acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (that is, dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; methacrylic acid Carboxyalkyl (meth)acrylates such as 2-carboxyethyl and the like.

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

The functional group-containing monomer constituting the aforementioned acrylic polymer may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

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

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

The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylates and the like.

Examples of the aforementioned other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

The aforementioned other monomers constituting the aforementioned acrylic polymer may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

The adhesive resin (i) other than the aforementioned acrylic polymer, like the aforementioned acrylic polymer, preferably has a structural unit derived from a functional group-containing monomer.

The adhesive resin (i) contained in the adhesive composition may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

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

(Crosslinker (ii))

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

The crosslinking agent (ii) reacts with the aforementioned functional group, for example, to crosslink the adhesive resins (i).

Examples of the crosslinking agent (ii) include isocyanate-based crosslinking agents such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates (that is, having isocyanate groups). Crosslinking agent); Epoxy crosslinking agent such as ethylene glycol glycidyl ether (ie, crosslinking agent with glycidyl group); Six [1-(2-methyl)-aziridinyl] three An aziridine crosslinking agent such as phosphine triazine (that is, a crosslinking agent with an aziridin group); a metal chelate crosslinking agent such as aluminum chelate (that is, a crosslinking agent with a metal chelate structure) Agent); Isocyanurate-based crosslinking agent (that is, a crosslinking agent having an isocyanuric acid skeleton) and the like.

The crosslinking agent (ii) is preferably an isocyanate-based crosslinking agent in terms of enhancing the cohesive force of the adhesive and enhancing the adhesive force of the adhesive layer, and easy availability.

The crosslinking agent (ii) contained in the adhesive composition may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

When the adhesive composition contains the crosslinking agent (ii), when the content of the adhesive resin (i) in the adhesive composition is 100 parts by mass, the content of the crosslinking agent (ii) is preferably 5 Parts by mass to 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 aforementioned content of the cross-linking agent (ii) is above the aforementioned lower limit, more significant effects brought about by the use of the cross-linking agent (ii) can be obtained. In addition, when the aforementioned content of the crosslinking agent (ii) is below the aforementioned upper limit, it becomes easier to adjust the adhesive force of the adhesive layer to the film-like adhesive.

(Other additives)

To the extent that the effect of the present invention is not impaired, the adhesive composition may also contain other additives that do not belong to any of the above-mentioned components.

As the aforementioned other additives, for example, antistatic agents, antioxidants, softeners (that is, plasticizers), fillers (that is, fillers), rust inhibitors, colorants (that is, pigments or dyes), sensitization Well-known additives such as agents, adhesion imparting agents, reaction delay agents, crosslinking accelerators (ie, catalysts).

Furthermore, the so-called "reaction delay agent", for example, suppresses the off-target crosslinking reaction in the adhesive composition under storage due to the action of the catalyst mixed in the adhesive composition. Examples of the reaction delay agent include a reaction delay agent that forms a chelate complex by chelation to a catalyst, and more specifically, includes two or more carbonyl groups (-C(=O) per molecule). -) The reaction delay agent.

The other additives contained in the adhesive composition may be only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

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

(Solvent)

The adhesive composition may also contain a solvent. By containing a solvent, the adhesive composition has improved coating suitability to the surface to be coated.

The aforementioned solvent is preferably an organic solvent. Examples of the aforementioned organic solvent include: ketones such as methyl ethyl ketone and acetone; carboxylic acid esters such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

As the aforementioned solvent, for example, the solvent used in the production of the adhesive resin (i) can be directly used in the adhesive composition without removing the solvent used in the production of the adhesive resin (i), or it can be added and manufactured separately during 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 only one type or two or more types; in the case of two or more types, the combination and ratio of these two or more types can be arbitrarily selected.

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

[Method of manufacturing adhesive composition]

The adhesive composition is obtained by blending the components used to form the adhesive composition. For example, it can be manufactured by the same method as in the case of the above-mentioned adhesive composition, except for the aspect of the different blending components.

Fig. 1 is a cross-sectional view schematically showing an embodiment of the semiconductor processing sheet of the present invention. In addition, the figures used in the following description may be enlarged to show the main parts in order to facilitate the understanding of the features of the present invention, and are not limited to the fact that the dimensional ratios of the components are the same as the actual ones.

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

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

That is, in the sheet 1 for semiconductor processing, a support sheet 10 having an adhesive layer 12 provided on a substrate 11 is used, and a film-like adhesive 13 is provided in direct contact with the adhesive layer 12.

Furthermore, 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 within a range that does not impair the effects of the present invention. Part of the composition.

<<Method of manufacturing semiconductor processing sheet>>

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

For example, in the case of laminating an adhesive layer or a film-like adhesive on a substrate, apply the adhesive composition or the adhesive composition on the release film, and dry the adhesive composition or the adhesive composition as necessary, thereby An adhesive layer or a film-like adhesive is formed on the release film in advance, and the exposed surface of the formed adhesive layer or film-like adhesive that is opposite to the side in contact with the release film is the surface of the substrate Just fit it. In this case, the adhesive composition or the adhesive composition is preferably applied to the release treatment surface of the release film. After the build-up structure is formed, the release film can be removed as necessary.

For example, in the manufacture of a semiconductor processing sheet (ie, a support sheet) in which an adhesive layer is laminated on a substrate, and a film-like adhesive is laminated on the aforementioned adhesive layer. In the case of a semiconductor processing sheet of a laminate of a substrate and an adhesive layer, in the above method, an adhesive layer is preliminarily laminated on the substrate, and the adhesive composition is separately coated on the release film, and the adhesive composition is applied as necessary. The agent composition is dried to form a film-like adhesive 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 that has been laminated on the substrate, and the film-like adhesive is laminated On the adhesive layer to obtain a semiconductor processing sheet. In the case of forming a film-like adhesive on the release film, it is also preferable to apply the adhesive composition to the release treatment surface of the release film, and after forming the laminated structure, the release film may be removed as necessary.

In this way, since all layers other than the base material constituting the semiconductor processing sheet can be laminated on the release film beforehand and attached to the surface of the target layer, as long as the layer adopting this step is appropriately selected as necessary Manufacturing wafers for semiconductor processing.

Furthermore, the semiconductor processing sheet is usually stored in the following state: After setting all necessary layers such as a jig adhesive layer for fixing the semiconductor processing sheet to a jig such as a dicing ring frame, etc., it is placed on the semiconductor A release film was bonded to the surface of the outermost layer on the side opposite to the support sheet in the processing sheet.

<<Method of Manufacturing Semiconductor Device>>

The manufacturing method of the semiconductor device of the present invention uses the above-mentioned film-like adhesive of the present invention, and includes the following steps: a step of forming a layered structure to form the following layered structure, the layered structure system being provided on a support sheet The film-like adhesive is placed, and a plurality of divided semiconductor wafers are placed on the surface of the film-like adhesive on the opposite side to the side where the support sheet is placed; the cutting step is to place the aforementioned laminated structure The film-like adhesive is cooled while extending in a direction parallel to the surface of the film-like adhesive to cut the film-like adhesive; and the pulling-off step is to cut the semiconductor with the cut-off film-like adhesive The chip (in this specification, sometimes referred to as "semiconductor chip with film adhesive") is picked up (that is, pulled away) from the aforementioned support sheet.

The film-like adhesive provided on the support sheet is the sheet for semiconductor processing of the present invention. As described later, the method of manufacturing a semiconductor device of the present invention uses the film-like adhesive or the sheet for semiconductor processing of the present invention.

By using the film-like adhesive or semiconductor processing sheet of the present invention, in the aforementioned cutting step, when the film-like adhesive is cut by the extension of the film-like adhesive, there is no abnormality such as defects of the film-like adhesive. , And the film-like adhesive can be easily cut at the target site.

In addition, in the case of using a semiconductor processing sheet having the above-mentioned non-energy-ray-curable adhesive layer, in the aforementioned pull-off step, even if the adhesive layer is not cured by irradiating energy rays, a film-like adhesive can be applied The semiconductor chip of the adhesive is easily pulled away from the adhesive layer for pickup. In this case, the manufacturing steps of the semiconductor device can be simplified.

Hereinafter, the aforementioned manufacturing method will be described with reference to FIG. 2. Figure 2 is used to schematically illustrate the use of the film adhesive or semiconductor processing sheet of the present invention In this case, a cross-sectional view of an embodiment of a method of manufacturing a semiconductor device. Here, the manufacturing method in the case of using the film-like adhesive 13 or the semiconductor processing sheet 1 shown in FIG. 1 is demonstrated. In addition, after FIG. 2, for the same constituent elements as those shown in FIG. 1, the same symbols as in the case of FIG. 1 are attached, and detailed descriptions of the symbols are omitted. In addition, in FIG. 2, only the configuration related to the semiconductor processing sheet and the semiconductor wafer is shown in cross-section.

<Steps of forming multilayer structure>

The laminated structure 101 shown in (a) in FIG. 2 has an adhesive layer 12 on the substrate 11, a film adhesive 13 is provided on the surface 12a of the adhesive layer 12, and the film adhesive 13 and The surface 13a on the opposite side where the adhesive layer 12 is provided is formed by placing a plurality of divided semiconductor wafers 8 thereon.

Furthermore, in FIG. 2, the gap between the plurality of semiconductor wafers 8 (that is, derived from the aforementioned groove) is emphasized.

In the aforementioned step of forming the laminated structure, for example, after attaching one sheet of film-like adhesive 13 to the back surface 8b of a plurality of divided semiconductor wafers 8, the film-like adhesive 13 is opposite to the side with the semiconductor wafer 8 The side surface (that is, the back surface) 13b is attached to the adhesive layer 12 in the support sheet 10, thereby forming the laminated structure 101. In addition, using the semiconductor processing sheet 1 of the present invention, the surface 13a of the film-like adhesive 13 of the semiconductor processing sheet 1 opposite to the side with the adhesive layer 12 is attached to the divided surface 13a The back 8b of the plurality of semiconductor wafers 8 can also form the laminated structure 101 by this.

A plurality of divided semiconductor wafers 8 can be produced by the following method as described above: from the circuit forming surface (also known as the back side) of the semiconductor wafer on the opposite side to the attaching surface (that is, the back surface) of the film-like adhesive 13 That is, a groove is formed on the surface, and the back surface is ground until the groove is reached. In addition, the aforementioned grooves can be formed by methods such as blade cutting, laser cutting, and water cutting.

FIG. 3 is a cross-sectional view for schematically explaining an embodiment of a method of forming a trench in such a semiconductor wafer to obtain a semiconductor wafer.

In this method, as shown in FIG. 3(a), the semiconductor wafer 8'is cut from a surface of the semiconductor wafer 8'as a circuit formation surface by blade cutting, laser cutting, water cutting, etc. 8a' forms a trench 80'.

Then, as shown in FIG. 3(b), the surface (that is, the back surface) 8b' of the semiconductor wafer 8'on the opposite side to the aforementioned surface (that is, the circuit forming surface) 8a' is ground. The grinding of the aforementioned back surface 8b' can be performed by a known method, for example, using a grinder 62. The grinding of the back surface 8b' is preferably performed by attaching a back grinding 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 groove 80', whereby as shown in FIG. 3(c), a plurality of semiconductor wafers 8 are obtained from the semiconductor wafer 8'. The aforementioned back surface 8b' of the semiconductor wafer 8'becomes 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 foregoing manufacturing method of a semiconductor device, it is preferable to adopt a method of forming a modified layer inside the semiconductor wafer and dividing the semiconductor wafer at the portion where the modified layer is formed as described above, rather than cutting off. Part of these semiconductor wafer methods.

That is, in the manufacturing method of the semiconductor device of the present invention, it is preferable to further include the following step before the step of forming the layered structure: a step of forming a modified layer to focus on the focus set inside the semiconductor wafer The method irradiates laser light in the infrared region to form a modified layer inside the semiconductor wafer; and the dividing step is to grind the surface of the semiconductor wafer on which the modified layer is formed on which the film-like adhesive is placed , And applying grinding force to the semiconductor wafer, thereby dividing the semiconductor wafer at the portion of the modified layer, thereby obtaining a plurality of semiconductor wafers; using the plurality of semiconductor wafers obtained in the aforementioned dividing step for the aforementioned In the step of forming a laminated structure.

4 is a cross-sectional view for schematically illustrating an embodiment of a method for forming a modified layer on such a semiconductor wafer to obtain a semiconductor wafer.

<Procedure for forming modified layer>

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

In the reforming layer forming step, for example, it is preferable to irradiate laser light with a large aperture (NA) so as to minimize damage to the surface of the semiconductor wafer 8'or the area near the surface due to the laser light. The modified layer 81'.

<Segmentation Step>

Then, in the aforementioned dividing step, as shown in FIG. 4(b), the surface (ie, the back surface) 8b' of the semiconductor wafer 8'that is the opposite side to the aforementioned surface (ie, the circuit forming surface) 8a' Carry out grinding. The grinding at this time can be performed by the same method as the grinding of the back surface of the trench-formed 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 a back grinding tape 63 to the surface 8a' of the semiconductor wafer 8'.

Then, the aforementioned back surface 8b' of the semiconductor wafer 8'is ground, and the grinding force 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 Therefore, as shown in (c) of FIG. 4, a plurality of semiconductor wafers 8 are obtained from the semiconductor wafer 8'. In this case, as in the case described with reference to FIG. 3, the aforementioned back surface 8 b ′ of the semiconductor wafer 8 ′ becomes the back surface 8 b of the semiconductor wafer 8, that is, the surface on which the film-like adhesive 13 is provided.

In any of the above methods, when the back grinding tape 63 is used, the obtained plural semiconductor wafers 8 are maintained in a state of being arranged on the back grinding 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, a more significant effect when using the semiconductor processing wafer of the present invention can be obtained.

<cutting step>

In the cutting step in the above-mentioned method of manufacturing a semiconductor device, after the step of forming the layered structure, as shown in (b) of FIG. 2, while cooling the film-like adhesive 13 in the layered structure 101, While extending the film-shaped adhesive 13 in a direction parallel to the surface 13a of the film-shaped adhesive 13, the film-shaped adhesive 13 is cut. The film-like adhesive 13 only needs to extend together with the base material 11 and the adhesive layer 12 (that is, the support sheet 10). Here, the film-like adhesive after cutting is indicated by the symbol 13', but the film-like adhesive 13' after such cutting is sometimes simply referred to as "film-like adhesive 13". In addition, the extending direction of the film-like adhesive 13 is indicated by arrow I.

In the aforementioned cutting step, the cooling temperature of the film adhesive 13 is not particularly limited, but in terms of easier cutting of the film adhesive 13, it is preferably -15°C to 10°C.

In the aforementioned cutting step, the extension speed (that is, the extension 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, and more It is preferably 0.5 mm/sec to 60 mm/sec, and may be, for example, 1 mm/sec to 50 mm/sec. By the extension speed being within this range, more significant effects of the present invention can be obtained. Furthermore, since the stretching speed is below the aforementioned upper limit, the semiconductor wafer 8 is less likely to be damaged during the stretching of the film-like adhesive 13.

In the aforementioned cutting step, by using the film-like adhesive 13 (that is, the semiconductor processing sheet 1), the film-like adhesive 13 can be cut at the target site, and the occurrence of film-like adhesion at the cut site can be suppressed Defects and other abnormalities of agent 13'.

In the aforementioned cutting step, by using the adhesive layer whose storage elastic modulus at 0°C is 1000 MPa or less, when the film adhesive 13 is cut, it is possible to suppress the semiconductor wafer with the film adhesive 13' after cutting 8 (that is, a semiconductor chip with a film-like adhesive) bulges or scatters from the adhesive layer 12.

<Pull-away step>

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

In the aforementioned pulling-off step, the semiconductor chip 8 is pulled up by the pulling part 61 of the manufacturing apparatus of the semiconductor device, whereby the film-like adhesive 13' after cutting attached to the back surface 8b of the semiconductor chip 8 is self-adhesive Layer 12 peels off. The method of pulling up the semiconductor wafer 8 may be a well-known method, and for example, a method of pulling up by sucking the surface of the semiconductor wafer 8 by a vacuum collet, etc. may be mentioned. Here, arrow II indicates the pulling direction of the semiconductor wafer 8.

In the aforementioned pull-off step, by using the above-mentioned adhesive layer whose adhesion to the semiconductor wafer is 200mN/25mm or less, even if the adhesive layer is not hardened by irradiating energy rays, the film-like shape can be easily picked up Adhesive semiconductor chip.

In the aforementioned manufacturing method of the semiconductor device, the semiconductor chip 8 (ie, the semiconductor wafer with the film-like adhesive attached) that is pulled apart (ie picked up) together with the cut film-like adhesive 13' is used, and it can be used with the previous method The semiconductor device is manufactured by the same method, that is, the semiconductor device can be manufactured through the step of bonding the aforementioned semiconductor wafer to the circuit surface of the substrate through the film-like adhesive die. For example, the aforementioned semiconductor chip 8 is bonded to the circuit surface of the substrate with a film-like adhesive 13' die, and if necessary, one or more semiconductor chips are further laminated on the semiconductor chip 8, and after wire bonding is performed, the resin is used to bond The whole is sealed to form a semiconductor package (not shown). Then, it is sufficient to use the semiconductor package to manufacture the target semiconductor device.

The method of manufacturing a semiconductor device using the film-like adhesive or semiconductor processing sheet of the present invention is not limited to the above-mentioned method described with reference to FIG. 2, and may be modified in the above-mentioned method within the scope of not impairing the effect of the present invention. Delete or add part of the composition.

[Example]

Hereinafter, the present invention will be described in more detail through specific embodiments. However, the present invention is not limited at all by the examples shown below.

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

‧Polymer composition

(a)-1: Copolymerizing methyl acrylate (hereinafter referred to as "MA") (95 parts by mass) and 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (5 parts by mass) Acrylic resin (weight average molecular weight 800,000, glass transition temperature 9 ℃).

‧Epoxy resin

(b1)-1: Cresol novolac type epoxy resin ("CNA147" manufactured by Nippon Kayaku Co., Ltd.) with acryl group added, epoxy equivalent 518g/eq, number average molecular weight 2100, unsaturated group content and ring Oxygen equivalent).

‧Thermal hardener

(b2)-1: Aralkyl phenol resin ("Milex XLC-4L" manufactured by Mitsui Chemicals, with a number average molecular weight of 1100).

‧Filler

(d)-1: Spherical silicon dioxide ("YA050C-MJE" manufactured by Admatechs, with an average particle size of 50 nm, treated with methacrylic silane).

‧Coupling agent

(e)-1: Silane coupling agent, 3-glycidoxypropylmethyl diethoxysilane ("KBE-402" manufactured by Shin-Etsu Chemical Co., Ltd.).

‧Crosslinking agent

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

<Production of film adhesive and semiconductor processing sheet>

[Example 1]

(Manufacture of adhesive composition)

Make polymer component (a)-1, epoxy resin (b1)-1, thermosetting agent (b2)-1, filler (d)-1, coupling agent (e)-1, and crosslinking agent (f) )-1, these were dissolved or dispersed in methyl ethyl ketone so that the content (parts by mass) became the value shown in Table 1, and stirred at 23°C to obtain an adhesive composition.

(Manufacture of film adhesive)

On one side of a polyethylene terephthalate film (thickness 38μm), the peeling treatment surface of the peeling film that was peeled off by the silicone treatment was applied with the adhesive composition obtained above to 120 It was heated and dried at ℃ for 3 minutes to form a film-like adhesive with a thickness of 20 μm.

Then, the release-treated surface of the release film is separately attached to the exposed surface of the film-shaped adhesive, thereby obtaining a film-shaped adhesive laminate having the release film attached to both sides of the film-shaped adhesive.

(Manufacturing 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-ray-curable adhesive composition. In addition, all the blending parts shown here are solid content conversion values.

The aforementioned adhesive resin is an acrylic polymer (weight average molecular weight 860,000, glass transition) made by copolymerizing 2-ethylhexyl acrylate (80 parts by mass) and 2-hydroxyethyl acrylate (20 parts by mass) Temperature -61℃). In addition, the aforementioned crosslinking agent is a toluene diisocyanate trimer adduct of trimethylolpropane ("Coronate L" manufactured by Tosoh).

(Manufacture of Adhesive Sheet)

On one side of the polyethylene terephthalate film, a peeling film ("SP-PET381031" made by Lintec, thickness 38μm) that was peeled off by silicone treatment was applied to the aforementioned peeling treated surface. The obtained adhesive composition was heated and dried at 120° C. for 2 minutes, thereby forming an adhesive layer with a thickness of 10 μm.

Then, a low-density polyethylene (LDPE) film with a thickness of 110 μm, which is a base material, was attached to the exposed surface of the adhesive layer to obtain an adhesive sheet with a release film.

(Manufacture of wafers for semiconductor processing)

After storing the aforementioned film-like adhesive layered product at room temperature for 1 week immediately after production, one release film was removed to expose one surface of the film-like adhesive. In addition, the release film was removed from the adhesive sheet obtained above, and one surface of the adhesive layer was exposed. Then, the exposed surface of the film adhesive and the exposed surface of the adhesive layer are bonded to obtain a semiconductor processing sheet in which a substrate, an adhesive layer, a film adhesive, and a release film are sequentially laminated.

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

The components contained in the adhesive composition were as shown in Table 1 or Table 2. Except for this point, the same method as in Example 1 was used to produce a film-like adhesive and a semiconductor processing sheet.

Furthermore, the solid content concentration of the adhesive composition manufactured in the above-mentioned Examples and Comparative Examples is 18% by mass to 24% by mass.

<Evaluation of film adhesives and semiconductor processing sheets>

With respect to the film-like adhesive and semiconductor processing sheet obtained above, the following items were evaluated.

(Elongation at break of laminate)

A laminating machine is used to laminate multiple layers of the film-like adhesive obtained above to produce a laminated film-like adhesive with a total thickness of 60μm. The multilayer body. Furthermore, the laminate was cut to produce test pieces 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 device ("DMA Q800" manufactured by TA instruments) to obtain the breaking elongation (%) of the test piece. That is, the elongation at break (%) of the aforementioned laminate formed by laminating the film-like adhesive before curing. When the test piece is stretched, the load applied to the test piece is changed from 1N/min to 18N/min. The results are shown in Table 1 or Table 2.

(Adhesion of film adhesive to semiconductor wafer)

An adhesive tape made of a single-area layer of a strong adhesive layer (thickness 24 μm) made of polyethylene terephthalate film (thickness 50 μm) is prepared. One release film is removed from the film-like adhesive laminate obtained above, and one surface of the film-like adhesive is exposed. Then, on the exposed surface of the film-like adhesive, the adhesive layer of the aforementioned adhesive tape was bonded using a laminator to produce a laminated sheet. Furthermore, after cutting this laminated sheet into a size of 25 mm in width and 150 mm in length, the remaining release film was removed from the film-like adhesive to prepare a test piece.

Using a laminating machine, the test piece was bonded to the mirror surface of the silicon wafer via a film-like adhesive heated to 50°C, and left to stand at a temperature of 23°C for 30 minutes. Then, using a universal tensile testing machine ("Autograph" manufactured by Shimadzu Corporation), keeping the same temperature unchanged, perform the following so-called 180° peeling: the test piece (that is, the film-like adhesive) and the silicon wafer contact each other Face to face In this way, the angle is 180°. The test piece is peeled from the silicon wafer at a peeling speed of 300mm/min, and the peeling force at this time is measured. The measured value of the peeling force is set as the film-like adhesive pair before curing Adhesion of semiconductor wafer (mN/25mm). The results are shown in Table 1 or Table 2.

(Cutting characteristics of film adhesive (1))

Using a dicing device ("DFD6361" manufactured by Disco), the following half-cutting is performed on the mirror surface of an 8-inch silicon wafer (thickness 720μm): by drawing a square with a size of 10mm×10mm, the dicing blade The surface of the silicon wafer is cut to a depth of 80 μm to form a groove.

Then, using a tape laminating machine ("RAD-3510" manufactured by Lintec), at room temperature, the back polishing tape ("ADWILL E-3125KN" manufactured by Lintec) was attached via the adhesive layer of the back polishing tape The above-mentioned mirror surface of the silicon wafer with grooves formed.

Then, a polishing machine ("DFG8760" manufactured by Disco) was used to grind the surface of the silicon wafer opposite to the above-mentioned mirror surface on which the grooves were formed. At this time, grinding is carried out so that the thickness of the silicon wafer becomes 50 μm, and the silicon wafer is divided and singulated into silicon wafers. The obtained silicon wafers are fixed on the back polishing belt with a space of about 30 μm.

Then, using a tape laminator (“ADWILL RAD2500” manufactured by Lintec), the film heated to 60°C in the semiconductor processing sheet The adhesive agent attaches the semiconductor processing sheet obtained above to the grinding surface of the obtained silicon wafer to obtain a laminate.

Then, the obtained laminate was fixed by attaching the exposed surface of the adhesive layer in the laminate to a ring frame for dicing, and peeling the back polishing tape from the silicon wafer to obtain the following laminate structure The test piece is formed by arranging a plurality of semiconductor wafers singulated in advance on an uncut film-like adhesive in the semiconductor processing sheet in this laminated structure system.

Set the above-obtained test piece in the extension unit of the expansion machine ("ME-300B" manufactured by JCM). Under the environment of 0℃, the extension amount (that is, the extension amount) is 10mm, and the extension speed (that is, the extension Speed) Under the condition of 1mm/sec, stretch the wafer for semiconductor processing and try to cut the film-like adhesive along the outline of the silicon wafer.

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

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

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

C: The film-like adhesive cannot be cut at all target parts.

(Cutting characteristics of film adhesive (2))

Using a tape laminating machine for back grinding (“RAD-3510F/12” manufactured by Lintec), a 12-inch silicon wafer was laminated on one side of the back grinding tape (“E-3125KL” manufactured by Lintec).

Then, the following stealth dicing is performed: From the exposed side of the unlaminated backside grinding tape in the silicon wafer, the laser light in the infrared region is irradiated to focus on the focal point set inside the silicon wafer , To form a modified layer inside the silicon wafer. The invisible cutting uses "DFL7361" manufactured by Disco as a device to obtain a silicon wafer with a size of 8mm×10mm for adjustment.

Then, a grinder ("DGP8761" manufactured by Disco) was used to grind the exposed surface of the silicon wafer. At this time, grinding is carried out so that the thickness of the silicon wafer becomes 40 μm, and the silicon wafer is divided and singulated into silicon wafers. The obtained silicon wafer is fixed on a belt for back grinding.

Then, using a tape laminator ("DFM2800" manufactured by Disco), the semiconductor processing sheet obtained above was attached to the obtained semiconductor processing sheet with a film-like adhesive heated to 60°C in the semiconductor processing sheet The aforementioned grinding surface of the silicon wafer to obtain a laminate.

Then, the obtained laminate was attached to the dicing ring frame by the exposed surface of the adhesive layer in the laminate to fix, and the back grinding tape was peeled from the silicon wafer to obtain the following laminate structure A bulk test piece, the laminated structure system is formed by arranging a plurality of pre-singulated semiconductor wafers on an uncut film adhesive in a semiconductor processing sheet.

Set the above-obtained test piece in a widening machine ("DDS2300" manufactured by Disco), and under the conditions of 0°C, under the conditions of a table ejection height of 15mm and a table ejection speed of 1mm/sec, the semiconductor processing The sheet is stretched, trying to cut the film-like adhesive along the shape of the silicon wafer.

Then, the table is lowered to release the extension, and the extended test piece is set on another table different from the above-mentioned expander table. Then, without attaching the test piece to the stage, eject the test piece under the conditions of a stage ejection height of 8mm and a stage ejection speed of 1mm/sec. When the stage is fully raised, the test piece is adsorbed on the stage, and the semiconductor processing wafer Extend, try to widen the gap between adjacent silicon wafers (that is, the slit width). In addition, the stage is lowered without changing the state of the test piece adsorbed to the stage, and the width of the slit is maintained without changing, and the strain on the outer periphery of the test piece without the silicon wafer is eliminated by the shrinkage of the heating at 250°C . Through the above steps, try to obtain a test piece with a wider slit width.

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

(Reliability of film adhesive)

‧Silicon wafer manufacturing

Using a tape laminator ("Adwill RAD2700" manufactured by Lintec), heat the semiconductor processing wafer obtained above to 60°C and attach it to a dry polished 12-inch silicon wafer (thickness 75μm), and install the ring状Frame.

Then, a dicing device ("DFD6361" manufactured by Disco) was used to singulate the aforementioned silicon wafer into a silicon wafer with a size of 8mm×8mm. The cutting at this time is based on the blade speed of 50mm/sec, the blade speed of 40,000 rpm, and the Carry out under the condition of cutting water volume 1L/min. In addition, the amount of cutting into the substrate during cutting was set to 20 μm.

‧Semiconductor packaging manufacturing

As the substrate, the following substrate (“LN001E-001 PCB (Au) AUS308” manufactured by Chino Technology Co., Ltd.) was used. The substrate was used on the copper foil (thickness of the copper clad laminate (“OCL-HL830” manufactured by Mitsubishi Gas Chemical) 18μm) is formed with a circuit pattern, and solder resist ("PSR-4000 AUS308" manufactured by Sun Ink Co., Ltd.) on the circuit pattern. The silicon wafer on the wafer for semiconductor processing obtained above is peeled from the base material together with the film-like adhesive, and the silicon wafer is crimped on the aforementioned substrate under the conditions of 120°C, 250gf, and 0.5 seconds. The agent fixes the silicon wafer on the substrate to obtain a laminate.

Then, the obtained laminate was placed in an oven heated to 175°C for 4 hours or 2 hours, and a thermal history of virtual wire bonding was applied to the foregoing laminate.

Then, using a molding resin ("KE-G1250" manufactured by KYOCERA Chemical) and a sealing device ("G-CUBE MZ549-1" manufactured by Apic Yamada), the sealing thickness becomes 400μm at a sealing temperature of 175 Under the conditions of ℃, sealing pressure of 7 MPa, and sealing time of 2 minutes, the above-mentioned laminate after the thermal history was applied was sealed. Furthermore, the aforementioned molding resin was cured at 175°C for 5 hours.

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

Through the above steps, a semiconductor package is obtained.

‧Surface mounting of semiconductor packages and evaluation of package reliability (that is, the reliability of film adhesives)

Place the semiconductor package obtained above at a temperature of 85°C and a relative humidity of 60% for 168 hours. After absorbing moisture, use a reflow oven (“WL-15-20DNX” manufactured by Sagami Riko Co., Ltd.). Under the conditions of a temperature of 260°C and a heating time of 1 minute, IR (Infrared Radiation) reflow soldering was performed 3 times on the semiconductor package after moisture absorption.

Then, a scanning ultrasonic flaw detection device ("Hye-Focus" manufactured by Hitachi Construction Machinery Finetec) was used to confirm whether cracks occurred in the semiconductor package, and the package reliability (that is, the film-like adhesive reliability). The results are shown in Table 1 or Table 2.

A: In the case of using the aforementioned laminate with thermal history at 175°C for 4 hours, no cracks occurred in the semiconductor package after IR reflow.

B: In the case of using the aforementioned laminate with thermal history at 175°C for 2 hours, no cracks occurred in the semiconductor package after IR reflow, but when used at 175°C for 4 hours Given under conditions In the case of the aforementioned laminate of the thermal history, cracks occurred in the semiconductor package after IR reflow.

C: Either the case of using the aforementioned layered product with a thermal history at 175°C for 2 hours, and the case of using the aforementioned layered product with a thermal history given at 175°C for 4 hours In this case, the semiconductor packages after IR reflow soldering all had cracks.

(Film-forming properties of film adhesive)

When manufacturing the above-mentioned film-like adhesive, the film-forming properties of the film-like adhesive were also evaluated.

That is, for the surface of the obtained film-like adhesive, when the adhesive composition is applied to the peeling film, the appearance of the surface formed by the contact between the adhesive composition and the peeling film is visually observed according to the following The benchmark evaluates the film-forming properties of the film adhesive. The results are shown in Table 1 or Table 2.

A: No abnormality is confirmed on the surface, and the surface condition is good.

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

C: Agglomerates are generated on the surface, and the surface state is not uniform.

[Table 1]

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

Regarding the film-like adhesives of Examples 1 to 7, when evaluating the cutting characteristics (1), they can be cut by extending to the target part, and no defects of the film-like adhesive etc. were confirmed at the cut part. Abnormal, showing excellent cutting characteristics. In addition, regarding the film adhesives of Example 1, Example 3, and Example 6, when the cutting characteristics (2) were evaluated, they also showed excellent cutting characteristics (the films of Example 2, Example 4, and Example 5) The cutting characteristics (2) were not evaluated for the adhesive agent).

Furthermore, the reliability and film forming properties of the film adhesives of Examples 1 to 6 are good, and there is no problem with the basic properties as a film adhesive.

In contrast, 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 characteristics (1) were evaluated, it was not possible The film adhesive is cut into a target shape, and the film adhesive has poor cutting characteristics.

In addition, in Comparative Example 3, Comparative Example 4, and Comparative Example 7, the adhesive force of the film adhesive was 260 mN/25 mm or less. When the cutting characteristic (1) was evaluated, the film adhesive could not be cut at a part of the target site. In addition, even if it was cut at the target site, abnormalities such as defects in the film adhesive were confirmed at the cut site, and the film adhesive had poor cutting characteristics. In addition, regarding the film adhesives of Comparative Example 3, Comparative Example 4, and Comparative Example 7, when the cutting characteristics (2) were evaluated, the cutting characteristics were also poor (Comparative Example 1, Comparative Example 2, Comparative Example 5, and Comparative Example 6). The film-like adhesive has not been evaluated for cutting characteristics (2)).

In addition, in Comparative Example 5 and Comparative Example 6, neither the elongation at break of the laminate at 0°C nor the adhesive force of the film adhesive could be measured, and neither the cutting characteristics (1) nor the cutting characteristics (2) could be evaluated. .

Furthermore, the film adhesives of Comparative Example 3 and Comparative Example 4 are poor in reliability, and the film adhesives of Comparative Example 5 and Comparative Example 6 have poor film forming properties, and these have problems in terms of basic characteristics as a film adhesive.

In addition, here, the cutting characteristic (2) of some film adhesives was not evaluated, and it can be considered that the cutting characteristic (2) of these film adhesives and the cutting characteristic (1) are the same evaluation results. The reason is that if there is no abnormality in the semiconductor wafer used for evaluation, the method of manufacturing the semiconductor wafer (that is, the method of dividing the semiconductor wafer) will not affect the aforementioned evaluation step. It can be considered that Example 1, Example 3, and Example in which cutting characteristics (1) and cutting characteristics (2) are evaluated together 6. The evaluation results of Comparative Example 3, Comparative Example 4 and Comparative Example 7 prove the above-mentioned situation.

(Industrial availability)

The present invention can be preferably used to manufacture semiconductor devices, so it is extremely useful in industry.

1: Chips for semiconductor processing

10: Support film

11: Substrate

11a: The surface of the substrate

12: Adhesive layer

12a: The surface of the adhesive layer

13: Film adhesive

Claims (4)

A sheet for semiconductor processing, on a support sheet provided with an adhesive layer on a substrate, and provided with a film-like adhesive; a single layer of the aforementioned film-like adhesive before curing with a thickness of 60μm or two or more layers before curing The elongation at break of the laminate formed by layering the aforementioned film-like adhesive so that the total thickness becomes 60μm at 0°C is 60% or less; the adhesive force of the aforementioned film-like adhesive to the semiconductor wafer before curing is 300mN/ 25mm or more; the aforementioned adhesive layer is non-energy ray curable. In the semiconductor processing sheet described in claim 1, the film-like adhesive is provided in direct contact with the adhesive layer. A method of manufacturing a semiconductor device, using the semiconductor processing sheet as described in claim 1 or 2; the manufacturing method of the aforementioned semiconductor device includes the following steps: a step of forming a layered structure to form the following layered structure, the layered structure system A plurality of divided semiconductor wafers are placed on the surface of the film adhesive on the opposite side to the side where the support sheet is provided; the cutting step is to cool the film adhesive in the laminate structure Extend in the direction along the surface of the aforementioned film-like adhesive, and cut the film-like adhesive; and In the pulling-off step, the semiconductor wafer provided with the film-like adhesive after being cut is pulled away from the supporting sheet. The method of manufacturing a semiconductor device as recited in claim 3, wherein before the step of forming the layered structure, further comprising the following step: a step of forming a modified layer to focus on a focal point set in the semiconductor wafer The laser light in the infrared region forms a modified layer inside the semiconductor wafer; and the dividing step is to grind the surface of the semiconductor wafer on which the modified layer is formed on which the film-like adhesive is provided, and Applying the grinding force to the semiconductor wafer, thereby dividing the semiconductor wafer at the modified layer portion, thereby obtaining a plurality of semiconductor wafers; using the plurality of semiconductor wafers obtained in the aforementioned dividing step in the aforementioned laminated structure Body forming step.

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