KR20210075965A - Method of manufacturing a semiconductor device - Google Patents

Abstract

To provide a method of manufacturing a semiconductor device capable of achieving both thinning of the semiconductor wafer and suppression of warpage of the semiconductor wafer while protecting the bump neck of the semiconductor wafer having bumps with a protective film formed from the curable resin layer made it a task. And it was set as the manufacturing method of the semiconductor device which includes the following processes (A)-(E) in this order. (A) The step of forming a curable resin layer on the bump formation surface of the semiconductor wafer having bumps (B) The step of curing the curable resin layer to form a protective film (C) The above steps of the semiconductor wafer having the bumps Step (D) of affixing back grind tape on the protective film formation surface (D) A step of grinding the surface opposite to the bump formation surface of the semiconductor wafer having the bumps while the back grind tape is affixed (E) ) The process of peeling the said back grind tape from the semiconductor wafer provided with the said bump after the said grinding|grinding

Description

Method of manufacturing a semiconductor device

The present invention relates to a method for manufacturing a semiconductor device.

DESCRIPTION OF RELATED ART In recent years, manufacture of the semiconductor device using the mounting method called a so-called face-down method is performed. In the face-down method, a semiconductor chip having bumps on the circuit surface (hereinafter simply referred to as "chip") and a board for mounting the chip are laminated so that the circuit surface of the chip and the substrate are opposed to each other, whereby the chip is formed. It is mounted on the said board|substrate.

In addition, the said chip|tip is normally obtained by separating the semiconductor wafer which has bumps on the circuit surface into pieces.

In the following description, the semiconductor wafer is also simply referred to as a "wafer". In addition, a semiconductor wafer provided with bumps on a circuit surface is also called "a wafer with bumps." In addition, the circuit surface of the wafer with bumps is also called "bump formation surface".

By the way, on a wafer with bumps, a protective film may be formed for the purpose of protecting the bonding part (henceforth a "bump neck") between a bump and a wafer.

For example, in patent document 1, the bump formation surface of the wafer with a bump making the laminated body in which the support base material, the adhesive layer, and the thermosetting resin layer were laminated|stacked in this order, and the thermosetting resin layer as a bonding surface, After pressure-bonding and bonding together, the protective film is formed by heating and hardening the said thermosetting resin layer.

Japanese Patent Laid-Open No. 2015-092594

In recent years, with the increase in the performance of electronic devices and the expansion of the Internet of Things (IoT) market, it is required to mount chips at high density.

One of the countermeasures to such a demand is to reduce the thickness of the chip. As one of the methods for thinning the chip, a method of thinning the wafer with bumps by grinding the back surface of the wafer with bumps is mentioned. In Patent Document 1, in a state in which the laminate is affixed to the bump-formed surface of the wafer with bumps, the back surface of the wafer with bumps is ground, and the supporting base material and the pressure-sensitive adhesive layer of the laminate are separated from the thermosetting resin layer. After peeling, heating and curing the thermosetting resin layer is described.

In addition, in this specification, "the back surface of the wafer with bumps" means the surface opposite to the bump formation surface of the wafer with bumps.

However, in recent years, the wafer used in a semiconductor manufacturing process has been enlarged from a viewpoint of improving batch processing efficiency. Further, from the viewpoint of thinning the chip, the wafer tends to be thinned. Therefore, like the technique described in Patent Document 1, if the step of heating and curing the thermosetting resin layer is performed after grinding the back surface of the bumped wafer, the bumped wafer is accompanied by shrinkage of the thermosetting resin layer. is prone to warping. When a warpage occurs in a wafer with bumps, it is easy to store a wafer with bumps in a wafer carrier, a wafer cassette, a wafer boat, etc., and it becomes a factor of damage to a wafer with a bump. Further, in the conveyance of the bumped wafer, furthermore, in the conveyance of the chip after the bumped wafer is divided into pieces to form a chip, a problem tends to occur at the time of adsorption of the wafer or the chip, A conveyance defect becomes easy to occur.

Further, the above problem is not limited to the case of forming the protective film by heating and curing the thermosetting resin layer, but may occur in the case of forming the protective film from the overall curable resin layer that can shrink during curing.

The present invention has been made in view of such a problem, and while protecting the bump neck of a semiconductor wafer having bumps with a protective film formed from a curable resin layer, both thinning of the semiconductor wafer and suppression of warpage of the semiconductor wafer are achieved. An object of the present invention is to provide a method of manufacturing a semiconductor device that can be

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solvable by the manufacturing method of the semiconductor device which includes the following processes (A)-(E) in this order, as a result of earnest examination.

That is, the present invention relates to the following [1] to [7].

[1] A method for manufacturing a semiconductor device comprising the following steps (A) to (E) in this order.

(A) Process of forming a curable resin layer in the bump formation surface of the semiconductor wafer provided with bumps

(B) The step of curing the curable resin layer to form a protective film

(C) A step of affixing a back grind tape to the surface on which the protective film of the semiconductor wafer having the bumps is formed

(D) The process of grinding the surface opposite to the said bump formation surface of the semiconductor wafer provided with the said bump in the state in which the said back grind tape was stuck.

(E) The process of peeling the said back grind tape from the semiconductor wafer provided with the said bump after the said grinding|grinding

[2] The method for manufacturing a semiconductor device according to the above [1], wherein the step (A) includes the following steps (A1) and (A2) in this order.

(A1) A step of attaching a laminate for forming a protective film having a laminated structure in which a support sheet and the curable resin layer are laminated on the bump formation surface of the semiconductor wafer having the bump, with the curable resin layer as the sticking surface

(A2) The process of peeling the said support sheet from the said laminated body for protective film formation, and forming the said curable resin layer in the said bump formation surface of the said bump-provided semiconductor wafer.

[3] The method for manufacturing a semiconductor device according to [1] or [2], wherein the curable resin layer is a thermosetting resin layer.

[4] The method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the thickness of the semiconductor wafer used in the step (A) is 300 µm or more.

[5] Before step (A), between step (A) and step (B), between step (B) and step (C), and between step (C) and step (D) The method for manufacturing a semiconductor device according to any one of [1] to [4], wherein a division starting point for dividing the semiconductor wafer having the bumps into pieces is formed.

[6] In any of the steps (B) and (C) and after the step (E), the protective film covering the top of the bump or the protective film adhering to a part of the top of the bump is removed, , The method for manufacturing a semiconductor device according to any one of [1] to [5], wherein an exposure treatment for exposing the top portion of the bump is performed.

[7] The method for manufacturing a semiconductor device according to [6], wherein the exposure treatment is a plasma etching treatment.

According to the method for manufacturing a semiconductor device of the present invention, while protecting the bump neck of a semiconductor wafer having bumps with a protective film formed from a curable resin layer, achieving both thinning of the semiconductor wafer and suppression of warpage of the semiconductor wafer thing becomes possible

1 is a schematic cross-sectional view showing an example of a wafer with bumps.
2 is a schematic diagram showing steps (A) to (E) of the method for manufacturing a semiconductor device of the present invention.
Fig. 3 is a schematic diagram showing steps (A1) and (A2) of a method for manufacturing a semiconductor device according to an embodiment of the present invention.
Fig. 4 is a schematic diagram showing an example of a mode in which division starting points are formed and separated into pieces in a method for manufacturing a semiconductor device according to one embodiment of the present invention.
Fig. 5 is a schematic diagram showing another example of an aspect in which a division origin is formed and divided into pieces in a method for manufacturing a semiconductor device according to an aspect of the present invention.

[Method for manufacturing semiconductor device of the present invention]

The method for manufacturing a semiconductor device of the present invention includes the following steps (A) to (E) in this order.

(A) Process of forming a curable resin layer in the bump formation surface of the semiconductor wafer provided with bumps

(B) The step of curing the curable resin layer to form a protective film

(C) A step of affixing a backgrind tape to the surface on which the protective film is formed of the semiconductor wafer.

(D) The process of grinding the surface opposite to the bump formation surface of the said semiconductor wafer in the state which the said back grind tape was affixed

(E) The process of peeling the said back grind tape from the said semiconductor wafer after the said grinding

Hereinafter, the semiconductor wafer having bumps used in the method for manufacturing a semiconductor device of the present invention will be described in detail, and then, the manufacturing method of the semiconductor device of the present invention will be described in detail for each process.

In addition, in this specification, a "protective film" may be changed to a "protective layer".

<Semiconductor Wafer with Bump>

An example of the semiconductor wafer provided with the bump used in the manufacturing method of the semiconductor device of this invention is shown in FIG. The semiconductor wafer 10 provided with bumps is equipped with the bumps 12 in the circuit surface 11a of the semiconductor wafer 11. FIG. A plurality of bumps 12 are usually provided.

In addition, similarly to the definition of said abbreviation, also in the following description, a "semiconductor wafer provided with bumps" is also called a "wafer with bumps." A "semiconductor wafer" is also called a "wafer". A "circuit surface" is also called a "bump formation surface."

The shape of the bump 12 is not specifically limited, Any shape may be sufficient as long as it can contact and fix to the electrode etc. on the board|substrate for chip mounting. For example, in FIG. 1 , the bumps 12 are spherical, but the bumps 12 may be ellipsoids. The spheroid may be, for example, a spheroid extending in a vertical direction with respect to the bump formation surface 11a of the wafer 11, or may be a spheroid extending in a horizontal direction with respect to the bump formation surface 11a of the wafer 11 It may be a spheroid.

The height of the bump 12 is not specifically limited, For example, 30 micrometers - 300 micrometers, Preferably they are 60 micrometers - 250 micrometers, More preferably, they are 80 micrometers - 200 micrometers.

In addition, when paying attention to one bump, "height of the bump 12" means the height in the site|part which exists in the highest position from the bump formation surface 11a.

The wafer 11 is a semiconductor wafer in which circuits, such as wiring, a capacitor, a diode, and a transistor, were formed in the surface, for example. The material of the said wafer is not specifically limited, For example, a silicon wafer, a silicon carbide wafer, a compound semiconductor wafer, a sapphire wafer, etc. are mentioned.

The size of the wafer 11 is usually 8 inches (200 mm in diameter) or more, and preferably 12 inches (300 mm in diameter) or more from the viewpoint of increasing batch processing efficiency. In addition, the shape of a wafer is not limited to a circle, For example, square shapes, such as a square and a rectangle, may be sufficient. In the case of a square wafer, it is preferable that the length of the longest side of the size (diameter) of the wafer 11 is more than the said size (diameter) from a viewpoint of improving batch processing efficiency.

The thickness of the wafer 11 is, from the viewpoint of suppressing the curvature of the wafer 11 accompanying curing the curable resin layer in the step (B), for example, 300 µm or more, preferably 400 µm or more, More preferably, it is 500 micrometers or more, More preferably, it is 600 micrometers or more. Moreover, it is preferable that the thinning process by back surface grinding is not given to the wafer 11.

The ratio [wafer size (diameter)/wafer thickness] of the size (diameter: unit mm) to the thickness (unit µm) of the wafer 11 is preferably 1000 or less, more preferably 700 or less, still more preferably 500 Hereinafter, more preferably, it is 400 or less, More preferably, it is 300 or less. Moreover, the ratio [wafer size (diameter)/wafer thickness] of the size (diameter: unit mm) and thickness (unit micrometer) of the wafer 11 is 100 or more normally, Preferably it is 200 or more.

<Step (A)>

In the step (A), as shown in FIG. 2A , the curable resin layer 20 is formed on the bump formation surface 11a of the wafer 10 with bumps. The formation method of the curable resin layer 20 is not specifically limited, For example, after apply|coating the curable resin composition mentioned later to the bump formation surface 11a of the wafer 10 with a bump, the method of drying and the like.

Here, in one aspect of this invention, formation of the curable resin layer 20 is preferably performed using the laminated body for protective film formation which has a laminated structure which laminated|stacked the support sheet and the curable resin layer.

Specifically, it is preferable that the step (A) includes the following steps (A1) and (A2) in this order.

(A1) A step of affixing a laminate for forming a protective film having a laminated structure in which a support sheet and a curable resin layer are laminated on the bump formation surface of the semiconductor wafer having the bump, with the curable resin layer as the affixing surface

(A2) The process of peeling the said support sheet from the said laminated body for protective film formation, and forming the said curable resin layer in the said bump formation surface of the said bump-provided semiconductor wafer.

Hereinafter, the steps (A1) and (A2) will be described in detail.

(Process (A1))

In the step (A1), the support sheet constituting the laminate for forming a protective film is not particularly limited as long as it is a sheet-like member capable of supporting the curable resin layer. For example, a support base material may be sufficient as a support sheet, the peeling film by which the peeling process was given to one surface of a support base material may be sufficient, and the laminated body which has a support base material and an adhesive layer may be sufficient as it.

When a support sheet is a peeling film, curable resin layer is formed in the peeling process surface of a support base material.

In addition, when a support sheet is a laminated body of a support base material and an adhesive layer, curable resin layer is bonded together with the adhesive layer of the said support sheet.

Here, in one aspect of the present invention, as shown in Fig. 3(A1), the support sheet 30a includes the first support substrate 31, the first buffer layer 32, and the first pressure-sensitive adhesive layer 33. It is preferable to have a laminated structure laminated in this order. And the laminated body 30 for protective film formation has the laminated structure in which the 1st support base material 31, the 1st buffer layer 32, the 1st adhesive layer 33, and the curable resin layer 20 were laminated|stacked in this order. It is preferable to have

When the laminate 30 for forming a protective film is pressed against the bump formation surface 11a of the wafer 10 with bumps with the curable resin layer 20 as the bonding surface, the curability of the laminate 30 for forming a protective film The resin layer 20 , the first pressure-sensitive adhesive layer 33 , and the first buffer layer 32 are pressed by the bumps 12 . Therefore, in the initial stage of crimping, the curable resin layer 20 , the first pressure-sensitive adhesive layer 33 , and the first buffer layer 32 are deformed into a concave shape following the shape of the bump 12 . And when the pressure from the bump 12 is continued, the top of the bump 12 will finally penetrate the curable resin layer 20 and contact|connect the support sheet 30a. At this time, the pressure applied to the bumps 12 is dispersed by the first pressure-sensitive adhesive layer 33 and the first buffer layer 32 of the support sheet 30a, and damage to the bumps 12 is suppressed.

However, the bump 12 does not necessarily need to protrude toward the support sheet 30a side, and the state embedded in the inside of the curable resin layer 20 may be sufficient. Even in such a state, the top part of the bump 12 can be exposed from the protective film 40 by the exposure process etc. mentioned later.

Here, in the support sheet constituting the laminate for forming a protective film used in the step (A1), good embedding property with respect to bumps and the ease of peeling of the support sheet from the laminate for forming a protective film in the step (A2) are excellent. is required

In one aspect of the present invention, the first buffer layer 32 included in the support sheet 30a preferably has a thickness of 100 to 500 µm, and preferably 150 to 500 µm, from the viewpoint of easily ensuring good embedding properties with respect to bumps. It is more preferable that it is 450 micrometers, and it is still more preferable that it is 200-400 micrometers.

From the same viewpoint, the first pressure-sensitive adhesive layer 33 of the support sheet 30a has a thickness of preferably 5 to 50 µm, more preferably 5 to 30 µm, still more preferably 5 to 15 µm. .

Moreover, in one aspect of this invention, the 1st buffer layer 32 which the support sheet 30a has is a viewpoint of making it easy to ensure the ease of peeling of the support sheet from the laminated body for protective film formation in a process (A2). The shear storage modulus G' (23°C) at room temperature (23°C) is preferably 200 MPa or less, more preferably 180 MPa or less, and still more preferably 150 MPa or less. Moreover, the shear storage modulus G' (23 degreeC) of the 1st buffer layer 32 is 80 normally from a viewpoint of fully ensuring the retainability at normal temperature of the curable resin layer 20 by the 1st support base material 31. more than MPa.

In addition, in this specification, the shear storage modulus G' (23 degreeC) in normal temperature (23 degreeC) is diameter 8mm x thickness 3mm formed from the same composition as the composition which forms the 1st buffer layer 32. A test sample was prepared and using a viscoelasticity measuring device (manufactured by Anton Paar, device name “MCR300”), test start temperature: -20°C, test end temperature: 150°C, temperature increase rate: 3°C/min, frequency: It is a value measured by the torsional shearing method on the conditions of 1 Hz.

Moreover, the support sheet which comprises the laminated body for protective film formation used in a process (A1) has favorable embedding property with respect to a bump as mentioned above, and the support sheet from the laminated body for protective film formation in a process (A2). On the other hand, the fixing performance of the adherend to the temperature increase during back grinding (that is, the retention of the adhesive force of the pressure-sensitive adhesive layer against the temperature increase during back grinding), such as that required for the back grind tape, is required. doesn't happen In addition, the design of the buffer layer in consideration of dimple suppression at the time of grinding the back surface is not required. Therefore, in one aspect of this invention, the 1st buffer layer 32 which the support sheet 30a has has favorable embedding property with respect to a bump, and peeling of the support sheet from the laminated body for protective film formation in a process (A2). Since it can be formed in consideration of easiness, it has the advantage of being able to improve the degree of freedom in design of the first buffer layer 32 as compared with a general back grind tape.

(Process (A2))

At a process (A2), a support sheet is peeled from the laminated body for protective film formation, and curable resin layer is formed in the bump formation surface of the wafer with a bump. For example, as shown in Fig. 3(A2), a support sheet having a laminated structure in which the first support substrate 31, the first buffer layer 32, and the first pressure-sensitive adhesive layer 33 are laminated in this order ( 30a) is peeled from the curable resin layer 20, and isolate|separates from the laminated body 30 for protective film formation. Thereby, the curable resin layer 20 is formed in the bump formation surface 11a of the wafer 10 with a bump. The surface opposite to the bump formation surface 11a side of the curable resin layer 20 is in an exposed state.

Further, in one aspect of the present invention, as described above, the shear storage modulus G' (23°C) of the first buffer layer 32 of the support sheet 30a at room temperature (23°C) is 200 MPa or less. By carrying out, the support sheet 30a can be easily peeled at normal temperature from the laminated body 30 for protective film formation. However, the method of peeling the support sheet 30a from the laminated body 30 for protective film formation is not limited to this method. For example, when the first pressure-sensitive adhesive layer 33 is a pressure-sensitive adhesive layer formed from an energy-beam curing pressure-sensitive adhesive, a heat-foaming pressure-sensitive adhesive, or a water-swelling pressure-sensitive adhesive, it is subjected to energy-beam curing, thermal foaming, or water swelling. You may peel the support sheet 30a from the laminated body 30 for protective film formation by this.

The bump-attached wafer 10 in which the curable resin layer 20 was formed on the bump formation surface 11a by the said process (A) is provided in the next process (B).

<Step (B)>

In a process (B), the curable resin layer formed in the bump formation surface of the wafer with a bump is hardened, and a protective film is formed. For example, as shown in Fig. 2(B) , by curing the curable resin layer 20 to form a protective film 40, the bump formation surface 11a and the bump neck of the wafer 10 with bumps are protected. do.

The protective film formed by hardening|curing curable resin layer becomes firmer than curable resin layer at normal temperature. Therefore, the bump neck is favorably protected by forming a protective film.

Depending on the kind of curable component contained in the curable resin layer, hardening of a curable resin layer can be performed by either thermosetting and hardening by irradiation of an energy ray.

In addition, in this specification, an "energy beam" means having an energy proton in an electromagnetic wave or a charged particle beam, and an ultraviolet-ray, an electron beam, etc. are mentioned as an example, Preferably it is an ultraviolet-ray.

As the conditions in the case of thermosetting, the curing temperature is preferably 90°C to 200°C, and the curing time is preferably 1 hour to 3 hours.

Conditions in the case of curing by energy ray irradiation are appropriately set according to the type of energy ray to be used. For example, when using ultraviolet rays, the illuminance is preferably 170 mw/cm 2 to 250 mw/cm 2 and the amount of light is preferably 600 mJ/cm 2 to 1500 mJ/cm 2 .

In addition, the detail of the curable resin layer for forming a protective film is mentioned later.

Here, in one aspect of the present invention, in the process of curing the curable resin layer to form a protective film, the curable resin layer flows by heating during thermosetting, from the viewpoint of improving the flatness of the protective film, the curable resin layer is , it is preferable that it is a thermosetting resin layer. In addition, when the curable resin layer is a thermosetting resin layer, in the step (A), even when the curable resin layer is formed in a state where the bump does not penetrate completely from the curable resin layer and is embedded therein, the heating during thermosetting By allowing the curable resin to flow through the surface, the top of the bump can be exposed from the protective film 40 . Also from such a viewpoint, it is preferable that curable resin layer is a thermosetting resin layer.

The wafer used in the step (B) and constituting the bumped wafer has a large diameter from the viewpoint of improving batch processing efficiency, and has a sufficient thickness as described above. In one aspect of the present invention, the thickness of the semiconductor wafer is 300 µm or more. Therefore, the curvature of the wafer accompanying shrinkage|contraction by hardening of curable resin layer is suppressed. Therefore, in the subsequent process, the bad effect which arises by the curvature of a wafer is suppressed.

Specifically, the storage failure of the wafer with bumps in a wafer carrier, a wafer cassette, a wafer boat, etc. is suppressed, and the damage|damage of a wafer with a bump is suppressed. Further, it is possible to suppress the transfer failure of the wafer with bumps, and furthermore, the transfer failure of the chip after the bumped wafer is divided into pieces to form a chip. Moreover, since the curvature of a wafer is suppressed, the back surface grinding in a process (D) can also be performed with high precision.

The bump-attached wafer 10 in which the curable resin layer 20 is hardened by the said process (B) and the protective film 40 was formed on the bump formation surface 11a is provided in the next process (C).

Further, in the method for manufacturing a semiconductor device of the present invention, when the curable resin layer is a thermosetting resin layer, the support sheet or back grind tape constituting the laminate for forming a protective film is subjected to heat treatment for curing the thermosetting resin layer. No exposure to heat. Therefore, since heat resistance to heat when curing the thermosetting resin layer is not required for the support sheet or the back grind tape, there is an advantage in that the design freedom of the support sheet or the back grind tape is greatly improved.

<Step (C)>

At a process (C), a back grind tape is affixed on the surface of a protective film.

The back grind tape used in a process (C) is not specifically limited, A general back grind tape used at the time of back grinding of the bumped wafer with a protective film can be used.

Here, in one aspect of the present invention, the back grind tape is, for example, like the back grind tape 50 shown in FIG. 2(C), the second support substrate 51, the second buffer layer 52, and it is preferable to have a laminated structure in which the second pressure-sensitive adhesive layer 53 is laminated in this order.

When the back grind tape 50 is pressed against the surface of the protective film 40 formed on the bumped wafer 10 with the second pressure-sensitive adhesive layer 53 as a bonding surface, the second pressure-sensitive adhesive layer of the back grind tape 50 is applied. The pressure-sensitive adhesive layer 53 and the second buffer layer 52 are pressed by the bumps 12 . Therefore, the 2nd adhesive layer 53 and the 2nd buffer layer 52 deform|transform into the concave shape which followed the shape of the bump 12, and the bump 12 is embedded and protected.

Thereby, the bumped wafer 10 in which the protective film 40 was formed is fixed to the back grind tape 50, and back surface grinding can be performed favorably.

Here, the back grind tape affixed to the surface of the protective film in the step (C) is required to have good embedding properties with respect to the bumps and the fixing performance for fixing the bumped wafer on which the protective film is formed at the time of back grinding.

In one aspect of the present invention, the second buffer layer 52 included in the back grind tape 50 preferably has a thickness of 50 to 450 µm from the viewpoint of easily ensuring good embedding properties with respect to bumps, and 100 It is more preferable that it is -400 micrometers, and it is still more preferable that it is 150-350 micrometers.

It is preferable that thickness is 5-50 micrometers, as for the 2nd adhesive layer 53 which the back grind tape 50 has from the same viewpoint, It is more preferable that it is 5-30 micrometers, It is still more preferable that it is 5-15 micrometers Do.

Further, in one aspect of the present invention, the second buffer layer 52 included in the back grind tape 50 preferably has a peak value of tan δ of 1.2 or more, more preferably 1.3 or more, and still more preferably 1.4 or more. Moreover, the peak value of tan-delta is 5.0 or less normally, Preferably it is 4.0 or less.

When the peak value of tanδ of the second buffer layer 52 is in the above range, even when the flexibility of the protective film 40 is increased due to heat generated during back grinding, the movement of the wafer 10 with bumps can be suppressed. have. If the bumped wafer 10 moves during back grinding, irregularities are likely to occur on the ground surface, and when a recess (dimple) is generated at a site corresponding to the bump formation site, a crack is taken from the concave portion as a starting point. There is a risk that this may occur. When the peak value of tan δ of the second buffer layer 52 is within the above range, the occurrence of dimples is suppressed, and thus the occurrence of cracks starting from the dimples is suppressed.

In addition, in this specification, the peak value of tanδ produces a test sample of diameter 8mm x thickness 3mm formed from the same composition as the composition which forms the 2nd buffer layer 52, and a viscoelasticity measuring apparatus (Anton Paar company) Manufactured, using the device name "MCR300"), test start temperature: -20 ° C, test end temperature: 150 ° C, temperature increase rate: 3 ° C / min, frequency: 1 Hz, measured by the torsional shear method is the value

Here, in one aspect of the present invention, the sticking direction of the back grind tape 50 to the bumped wafer 10 on which the protective film 40 is formed, and the bumped wafer in the step (A1) ( It is preferable to make different the sticking directions of the laminated body 30 for protective film formation with respect to 10). Specifically, to the bumped wafer 10 on which the protective film 40 was formed with respect to the sticking direction of the laminated body 30 for forming a protective film to the bumped wafer 10 in the step (A1). It is preferable to shift the sticking direction of the back grind tape 50 to 30° to 90°, more preferably to shift it by 45° to 90°, even more preferably to shift it by 60° to 90°, and to shift it by 90° more preferably.

In this way, the sticking direction of the back grind tape 50 to the bumped wafer 10 on which the protective film 40 was formed is for forming a protective film on the bumped wafer 10 in the step (A1). By changing the sticking direction of the stacked body 30, the bumped wafer 10 generated by the force applied when the protective film forming layered body 30 is pressed against the bumped wafer 10 is minute. The warpage can be canceled by the force applied when the back grind tape 50 is pressed against the bumped wafer 10 , and the warpage of the bumped wafer 10 can be further suppressed.

<Step (D)>

In a process (D), the surface opposite to the bump formation surface of the wafer with a bump is ground with the back grind tape affixed. In other words, the back surface of the bumped wafer 10 is ground to thin the wafer 11 .

The back surface grinding of the bumped wafer 10 is performed, for example, by fixing the front surface side of the bumped wafer 10 to which the dicing tape is affixed on a stationary table such as a chuck table, and the wafer 11 This is carried out by grinding the back surface 11b of the

In the present invention, the thickness of the bumped wafer 10 after grinding can be 250 µm or less. As described above, in the present invention, even when the thickness of the wafer 11 is made thin, the curvature of the wafer 11 is suppressed. For this reason, the storage failure of the bumped wafer 10 with respect to a wafer carrier, a wafer cassette, a wafer boat, etc. is suppressed, and the damage|damage of the bumped wafer 10 is suppressed. Further, it is possible to suppress the transfer failure of the wafer 10 with bumps, and furthermore, the transfer failure of the chip after the bumped wafer is divided into pieces to form chips.

<Step (E)>

In a process (E), the said back grind tape is peeled from the said semiconductor wafer after the said grinding.

Although the back grind tape 50 may peel at room temperature, in one aspect of this invention, the back grind tape 50 is heated to increase the fluidity|liquidity of the 2nd adhesive layer 53 which the back grind tape 50 has. The adhesive force may be reduced by this, and you may make it peel the back grind tape 50. However, the peeling method of the back grind tape 50 is not limited to these methods. For example, when the second pressure-sensitive adhesive layer 53 is a pressure-sensitive adhesive layer formed from an energy ray-curable pressure-sensitive adhesive, a heat-foaming pressure-sensitive adhesive, or a water-swelling pressure-sensitive adhesive, it is subjected to energy ray curing, thermal foaming, or water swelling. You may peel the back grind tape 50 by this.

<Formation of the division origin>

In one aspect of the present invention, before the step (A), between the step (A) and the step (B), between the step (B) and the step (C), and between the step (C) and the step ( In any of D), it is preferable to have the process of forming the division|segmentation origin for segmenting the semiconductor wafer with a bump into pieces.

As a method of forming the division|segmentation origin for segmenting the semiconductor wafer with a bump into pieces, the line dicing method, the stealth dicing (trademark) method, etc. are mentioned, for example.

Further, the manufacturing method of a semiconductor device according to one aspect of the present invention may be applied to a semiconductor wafer with bumps in which the division origin for segmentation has been completed, and in this case, the step of forming the division origin is You may omit it.

(Sun dicing method)

In the sun dicing method, for example, as shown in FIG. 4 , a groove 61 is formed in the bump formation surface 11a of the bumped wafer 10 along a line to be divided, and the bumped wafer is formed. By grinding the back surface 11b of (10), the bumped wafer 10 is thinned until at least reaching the groove 61, and the bumped wafer 10 is separated into a separate body (CP). ) to reorganize it.

In the sun dicing method, the dividing starting point for dividing the bumped wafer 10 into pieces is the groove 61 .

Here, in one aspect of the present invention, the formation of the grooves 61 is performed after the step (B), that is, after the protective film 40 is formed on the bump formation surface 11a of the wafer 10 to which the bumps are attached. It is preferable to carry out In this case, it is preferable to form the groove|channel 61 toward the inside of the wafer 11 of the wafer 10 with a bump from the surface of the protective film 40, as shown in FIG. Thereby, the bumped wafer 10 with the protective film 40 formed thereon can be easily divided into pieces with the protective film attached thereto.

Further, after forming a groove 61 from the bump formation surface 11a of the wafer 10 with bumps toward the inside of the wafer 11, the bump formation surface 11a of the wafer 10 with bumps Even when the protective film 40 is formed on the surface, it is possible to separate the bumped wafer 10 on which the protective film 40 is formed in a state with the protective film 40 attached thereto. That is, the bumped wafer 10 is thinned until at least reaching the groove 61 by grinding the back surface 11b of the bumped wafer 10, and then applying an external force such as a pressing force. By doing so, using the groove 61 as a division starting point, the protective film 40 is also cut together with the bumped wafer 10, and the bumped wafer 10 on which the protective film 40 is formed is converted into a protective film. (40) It can be divided into pieces in the state of being attached.

(Stealth dicing method)

The stealth dicing method is a method in which a modified region is formed inside a wafer of a bumped wafer with laser light, and the bumped wafer is divided into pieces using the modified region as a division starting point.

Specifically, as shown in FIG. 5 , the modified region 71 by multiphoton absorption is applied to the wafer 11 of the bumped wafer 10 by irradiating a laser beam with a condensing point inside the wafer. ) is formed as a division starting point. Then, with this modified region 71 , a cutting origin region is formed within a predetermined distance from the laser light incident surface along the division scheduled line of the bumped wafer 10 . Then, the bumped wafer 10 is ground and thinned on the back side, and then cut with a machining pressure such as a grinding wheel, and then divided into individual chips to separate the wafer 10 into pieces.

When the modified region 71 is formed before the step (A), the laser light incident surface may be the bump formation surface or the back surface of the wafer with bumps, but circuits formed on the bump formation surface of the wafer with bumps From a viewpoint of suppressing the influence on the like, it is preferable that the laser light incident surface is the back surface of the wafer with bumps.

In addition, after the process (A), the protective film 40 is formed on the bump formation surface 11a of the wafer 10 with a bump. Moreover, the back grind tape 50 etc. are affixed on the surface of the protective film 40 in some cases. Accordingly, even when the modified region 71 is formed after the step (A), it is preferable that the laser light incident surface is the back surface of the wafer with bumps.

<Exposure treatment>

In one aspect of the present invention, between the step (B) and the step (C) and after the step (E), the protective film covering the top of the bump or a part of the top of the bump is attached It is preferable to remove the protective film and perform an exposure treatment for exposing the top of the bump.

As an exposure process for exposing the top of a bump, etching processes, such as a wet etching process and a dry etching process, are mentioned, for example.

Here, as a dry etching process, a plasma etching process etc. are mentioned, for example. Although the plasma etching treatment is sometimes performed under high-temperature conditions, in any of the steps (B) and (C) and in the above-mentioned step (E), when the plasma etching treatment is performed under high-temperature conditions, the curable water Since the base layer has already been cured and a protective film has been formed, curing shrinkage of the curable resin layer does not occur due to the high temperature conditions of the plasma etching process, and therefore, warpage of the wafer accompanying curing shrinkage of the curable resin layer does not occur.

In addition, in the case where the top of the bump is not exposed on the surface of the protective film, the exposure treatment may be performed for the purpose of retreating the protective film until the top of the bump is exposed.

Next, about the laminated body for protective film formation and the back grind tape used in the manufacturing method of the semiconductor device of this invention, the detail of each member which comprises these is demonstrated.

[Curable resin layer]

In the manufacturing method of the semiconductor device of one aspect|mode of this invention, the laminated body for protective film formation is used. The said laminated body for protective film formation has a curable resin layer.

The thermosetting resin layer in which hardening reaction advances by heat processing may be sufficient as curable resin layer, and the energy-beam curable resin layer in which hardening reaction advances by energy-beam irradiation may be sufficient as it.

A thermosetting resin layer and an energy-beam curable resin layer are not specifically limited, A well-known thermosetting resin layer and an energy-beam curable resin layer can be employ|adopted suitably.

Here, as described above, in one aspect of the present invention, the curable resin layer is preferably a thermosetting resin layer from the viewpoint of improving the flatness of the protective film by making the curable resin layer flow by heat treatment at the time of curing. Do.

Hereinafter, the thermosetting resin layer used in one aspect of the present invention will be described in detail.

<Thermosetting resin layer>

The thermosetting resin layer used in one aspect of the present invention is, for example, a composition for forming a thermosetting resin layer containing a polymer component (XA) and a thermosetting component (XB) (hereinafter simply referred to as “composition for forming a resin layer”). (X)").

(Polymer component (XA))

A polymer component (XA) is a polymer compound for providing film-forming property, flexibility, etc. to a thermosetting resin layer, It is a component which can be regarded as being formed by polymerization reaction of a polymeric compound. In addition, in this specification, a polycondensation reaction is also included in polymerization reaction.

One type may be sufficient as the polymer component (XA) which the composition (X) for resin layer formation and a thermosetting resin layer contain, and 2 or more types may be sufficient as it. In the case of two or more types, their combination and ratio can be arbitrarily selected.

Examples of the polymer component (XA) include polyvinyl acetal, acrylic resin, polyester, urethane-based resin, acrylic urethane resin, silicone-based resin, polyolefin-based resin (eg, rubber-based resin), phenoxy resin, thermoplastic Polyimide etc. are mentioned. In addition, it is easy to adjust the shear viscosity at 90°C to 200°C, which is the temperature range of the thermosetting process, and the thermosetting resin layer is attached to the bump-forming surface of the wafer with bumps, and thermosetting. When it is made, the effect of suppressing repelling of the surface of a semiconductor wafer becomes high, and since it is easy to suppress the protective film formation defect by repelling, polyvinyl acetal and an acrylic resin are preferable among these.

Hereinafter, polyvinyl acetal and acrylic resin preferable as a polymer component (XA) are mentioned and demonstrated as an example.

In addition, in this specification, the meaning of "the adjustment of the shear viscosity in 90 degreeC - 200 degreeC is easy" is the thermosetting resin layer before hardening in 90 degreeC - 200 degreeC (preferably 90 degreeC - 130 degreeC). The lowest shear viscosity when the temperature is raised at 10 ° C / min, preferably 500 Pa s or more, more preferably 1,000 Pa s or more, more preferably 2,000 Pa s or more · It means that it can be adjusted more than s. By adjusting the minimum shear viscosity in 90 degreeC - 200 degreeC (preferably 90 degreeC - 130 degreeC) in the said range, it is easy to suppress the protective film formation defect by repelling.

In addition, in this specification, the minimum shear viscosity in 90 degreeC - 200 degreeC (preferably 90 degreeC - 130 degreeC) of curable resin layer is measured by the method as described in an Example.

(polyvinyl acetal)

It does not specifically limit as polyvinyl acetal used as a polymer component (XA), For example, well-known polyvinyl acetal can be used.

Here, among polyvinyl acetal, polyvinyl formal, polyvinyl butyral, etc. are mentioned, for example, Polyvinyl butyral is more preferable.

As polyvinyl butyral, those having structural units represented by the following formulas (i-1), (i-2), and (i-3) are heated to 90°C to 200°C, which is a temperature range in the process of thermosetting. When it is easy to adjust the shear viscosity, and when the thermosetting resin layer is affixed to the bump-formed surface of the wafer with bumps and subjected to thermosetting, the effect of suppressing the repelling of the surface of the semiconductor wafer is higher preferred from

[Formula 1]

In said formulas (i-1), (i-2), and (i-3), p, q, and r are the content rates (mol%) of each structural unit.

The weight average molecular weight (Mw) of polyvinyl acetal is preferably 5,000 to 200,000, more preferably 8,000 to 100,000, still more preferably 9,000 to 80,000, and particularly preferably 10,000 to 50,000. When the weight average molecular weight of polyvinyl acetal is within such a range, adjustment of the shear viscosity at 90°C to 200°C becomes easier, and the thermosetting resin layer is affixed to the bump formation surface of the bumped wafer, and heat When hardened, the effect which suppresses the repelling of the surface of a semiconductor wafer becomes higher. Moreover, the effect of suppressing the residual|survival of the thermosetting resin layer in the upper part of a bump (top part of a bump and its vicinity area|region) becomes higher.

In this specification, the weight average molecular weight of a polymer (resin) can be measured as a standard polystyrene conversion value by gel permeation chromatography (GPC) which uses tetrahydrofuran (THF) as a solvent.

As for the content rate p (butyralization degree) of the structural unit of the butyral group represented by said formula (i-1), 40-90 mol% is preferable on the basis of all the structural units of a polymer component (XA), and 50-85 mol % is more preferable, and 60-76 mol% is especially preferable.

The content ratio q of the structural unit having an acetyl group represented by the formula (i-2) is preferably 0.1 to 9 mol%, more preferably 0.5 to 8 mol%, based on all the structural units of the polymer component (XA), , 1 to 7 mol% is particularly preferable.

The content ratio r of the structural unit having a hydroxyl group represented by the formula (i-3) is preferably 10 to 60 mol%, more preferably 10 to 50 mol%, based on all the structural units of the polymer component (XA), , 20-40 mol% is especially preferable.

It is preferable that it is 40-80 degreeC, and, as for the glass transition temperature (Tg) of polyvinyl acetal, it is more preferable that it is 50-70 degreeC. When the Tg of the polyvinyl acetal is within such a range, the effect of suppressing the residual of the thermosetting resin layer in the upper portion of the bump when the thermosetting resin layer is attached to the bump-forming surface of the wafer with bumps is higher. Moreover, the hardness of the protective film formed by thermosetting a thermosetting resin layer can be made sufficient.

In addition, in this specification, the glass transition temperature (Tg) of a polymer (resin) is a value measured by the method as described in the Example mentioned later.

You may adjust the content rate of the said 3 types of structural units which comprises polyvinyl butyral arbitrarily according to desired physical properties.

In addition, although polyvinyl butyral may have structural units other than the said 3 types of structural units, Content of the said 3 types of structural units is based on the total amount of polyvinyl butyral, Preferably it is 80-100 mol. %, more preferably 90-100 mol%, still more preferably 100 mol%.

(Acrylic resin)

It does not specifically limit as said acrylic resin in a polymer component (XA), For example, a well-known acrylic polymer can be used.

It is preferable that it is 10,000-2,000,000, and, as for the weight average molecular weight (Mw) of acrylic resin, it is more preferable that it is 100,000-1,500,000. When the weight average molecular weight of the acrylic resin is within this range, adjustment of the shear viscosity at 90 ° C. to 200 ° C. becomes easier, and the thermosetting resin layer is affixed to the bump formation surface of the bumped wafer and thermosetted. At this time, the effect which suppresses the repelling of the surface of a semiconductor wafer becomes higher. Moreover, it is excellent in shape stability, and a thermosetting resin layer becomes easy to follow to the uneven|corrugated surface of a to-be-adhered body, and generation|occurrence|production of a void etc. between a to-be-adhered body and a thermosetting resin layer is suppressed more.

It is preferable that it is -50-70 degreeC, and, as for the glass transition temperature (Tg) of acrylic resin, it is more preferable that it is -30-50 degreeC. When Tg of acrylic resin is more than the said lower limit, the adhesive force of a thermosetting resin layer and a support sheet is suppressed, and the peelability of a support sheet improves. Moreover, when Tg of an acrylic resin is below the said upper limit, the adhesive force with the to-be-adhered body of a thermosetting resin layer improves.

As acrylic resin, For example, 1 type(s) or the polymer of 2 or more types (meth)acrylic acid ester; In addition to (meth)acrylic acid ester, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N- methylolacrylamide, etc., copolymers formed by copolymerization of one or two or more monomers selected can be mentioned. have.

In addition, in this specification, let "(meth)acrylic acid" be a concept including both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid. For example, "(meth)acrylate" is a concept including both "acrylate" and "methacrylate", and "(meth)acryloyl group" "" is a concept including both "acryloyl group" and "methacryloyl group."

As the (meth)acrylic acid ester constituting the acrylic resin, for example, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth)acrylic acid isopropyl, (meth)acrylic acid n -Butyl, (meth) acrylate isobutyl, (meth) acrylic acid sec-butyl, (meth) acrylic acid tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylic acid 2- Ethylhexyl, (meth) acrylate isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate undecyl, (meth) Dodecyl acrylate ((meth) acrylate lauryl), (meth) acrylic acid tridecyl, (meth) acrylate tetradecyl ((meth) acrylate myristyl), (meth) acrylate pentadecyl, (meth) acrylate hexadecyl ((meth) acrylate The alkyl group constituting the alkyl ester, such as palmityl acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl (meth)acrylate) has a chain structure having 1 to 18 carbon atoms (meth) ) Acrylic acid alkyl ester;

(meth)acrylic acid cycloalkyl esters, such as (meth)acrylic-acid isobornyl and (meth)acrylic-acid dicyclopentanyl;

(meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate;

(meth)acrylic acid cycloalkenyl esters, such as (meth)acrylic acid dicyclopentenyl ester;

(meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester;

(meth)acrylic acid imide;

Glycidyl group-containing (meth)acrylic acid esters, such as (meth)acrylic-acid glycidyl; (meth) acrylic acid hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) ) Hydroxyl group-containing (meth)acrylic acid esters, such as 3-hydroxybutyl acrylic acid and 4-hydroxybutyl (meth)acrylic acid;

Substituted amino group-containing (meth)acrylic acid esters, such as (meth)acrylic-acid N-methylaminoethyl, etc. are mentioned. 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.

The number of monomers constituting the acrylic resin may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

Acrylic resin may have a functional group which can couple|bond with other compounds, such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group. The said functional group of acrylic resin may couple|bond with another compound via the crosslinking agent (XF) mentioned later, and may couple|bond with another compound directly without via a crosslinking agent (XF). When the acrylic resin is bonded to another compound by the above functional group, the reliability of a package having a protective film formed using the laminate for forming a protective film tends to be improved.

In one aspect of the present invention, for example, as the polymer component (XA), a thermoplastic resin other than polyvinyl acetal and an acrylic resin (hereinafter, it may be simply abbreviated as “thermoplastic resin”) is polyvinyl. It may be used independently, without using acetal and an acrylic resin, and may be used together with polyvinyl acetal or an acrylic resin. By using the thermoplastic resin, the releasability of the thermosetting resin layer from the support sheet is improved, or the thermosetting resin layer tends to follow the concave-convex surface of the adherend, so that there is a void between the adherend and the thermosetting resin layer. may be more suppressed.

It is preferable that it is 1,000-100,000, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that it is 3,000-80,000.

It is preferable that it is -30-150 degreeC, and, as for the glass transition temperature (Tg) of the said thermoplastic resin, it is more preferable that it is -20-120 degreeC.

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

The number of the said thermoplastic resins which the composition (X) for resin layer formation and the thermosetting resin layer contain may be one, or two or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

In the composition (X) for forming a resin layer, the ratio of the content of the polymer component (XA) to the total content of all components other than the solvent (that is, the content of the polymer component (XA) in the thermosetting resin layer) is the polymer component Regardless of the kind of (XA), it is preferably 5-85 mass%, more preferably 5-80 mass%, for example, 5-70 mass%, 5-60 mass%, 5-50 mass% %, 5-40 mass %, and any of 5-30 mass % may be sufficient. However, these contents in the composition (X) for resin layer formation are an example.

Here, a polymer component (XA) may correspond also to a thermosetting component (XB). In one aspect of the present invention, when the composition (X) for forming a resin layer contains a component corresponding to both of such a polymer component (XA) and a thermosetting component (XB), the composition (X) for forming a resin layer ) is considered to contain the polymer component (XA) and the thermosetting component (XB).

(thermosetting component (XB))

A thermosetting component (XB) is a component for hardening a thermosetting resin layer by heat processing, and forming a hard protective film.

The number of the composition (X) for resin layer formation and the thermosetting component (XB) which the thermosetting resin layer contains may be 1 type, and 2 or more types may be sufficient as them, When 2 or more types, those combinations and ratio can be selected arbitrarily. .

Examples of the thermosetting component (XB) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters and silicone resins, and among these, epoxy thermosetting resins are preferable.

(epoxy thermosetting resin)

An epoxy-type thermosetting resin consists of an epoxy resin (XB1) and a thermosetting agent (XB2).

One type may be sufficient as the epoxy type thermosetting resin which the composition for resin layer formation and the thermosetting resin layer contain, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and ratio can be selected arbitrarily.

It does not specifically limit as an epoxy resin (XB1), For example, a well-known epoxy resin can be used. For example, polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated substance, orthocresol novolak epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type Bifunctional or more than bifunctional epoxy compounds, such as an epoxy resin, a bisphenol F type|mold epoxy resin, and a phenylene skeleton type|mold epoxy resin, are mentioned.

As the epoxy resin (XB1), an epoxy resin having an unsaturated hydrocarbon group may be used. The epoxy resin which has an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than the epoxy resin which does not have an unsaturated hydrocarbon group. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the package which has a protective film formed using the laminated body for protective film formation improves.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by conversion into the group which has an unsaturated hydrocarbon group in part of the epoxy group of a polyfunctional epoxy resin is mentioned, for example. Such a compound is obtained, for example by making an epoxy group addition-react (meth)acrylic acid or its derivative(s).

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple|bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.

The unsaturated hydrocarbon group is an unsaturated group having polymerizability, and specific examples thereof include an ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, and (meth)acrylamide group. and an acryloyl group is preferable.

It is preferable that it is 15,000 or less, as for the weight average molecular weight of an epoxy resin (XB1), It is more preferable that it is 10,000 or less, It is especially preferable that it is 5,000 or less. When the weight average molecular weight of the epoxy resin (XB1) is below the upper limit, adjustment of the shear viscosity at 90 ° C. to 200 ° C. becomes easier, and the thermosetting resin layer is affixed to the bump formation surface of the wafer with bumps, When thermosetting is carried out, the effect which suppresses the repelling of the surface of a semiconductor wafer becomes higher. Moreover, the effect which suppresses the residual|survival of a protective film residue in the top part of a bump becomes higher.

The lower limit of the weight average molecular weight of an epoxy resin (XB1) is not specifically limited. However, it is preferable that it is 300 or more, and, as for the weight average molecular weight of an epoxy resin (XB1), it is more preferable that it is 500 or more from the point which sclerosis|hardenability of a thermosetting resin layer, and the intensity|strength and heat resistance of a protective film improve more.

The weight average molecular weight of an epoxy resin (XB1) can be suitably adjusted so that it may become in the range set by combining the preferable lower limit and upper limit mentioned above arbitrarily.

For example, in one aspect of the present invention, the weight average molecular weight of the epoxy resin (XB1) is preferably 300 to 15,000, more preferably 300 to 10,000, particularly preferably 300 to 3,000. Further, in one embodiment, the weight average molecular weight of the epoxy resin (XB1) is preferably 500 to 15,000, more preferably 500 to 10,000, particularly preferably 500 to 3,000. However, these are examples of the preferable weight average molecular weight of an epoxy resin (XB1).

It is preferable that it is 100-1,000 g/eq, and, as for the epoxy equivalent of an epoxy resin (XB1), it is more preferable that it is 130-800 g/eq.

In addition, in this specification, "epoxy equivalent" means the number of grams (g/eq) of the epoxy compound containing 1 gram equivalent of an epoxy group, It is a value measured based on JISK7236:2009.

As for the epoxy resin (XB1), it is preferable that it is liquid at room temperature (in this specification, it may simply call "liquid epoxy resin (XB1)"). When an epoxy that is liquid at room temperature is used, it is easy to adjust the shear viscosity. Moreover, the thermosetting resin layer becomes easy to follow to the uneven|corrugated surface of a to-be-adhered body, and generation|occurrence|production of a void etc. between a to-be-adhered body and a thermosetting resin layer is suppressed more. In addition, "liquid at room temperature" as used herein means "liquid at 25 degreeC", and it is the same also in the following description.

An epoxy resin (XB1) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combination and a ratio can be selected arbitrarily.

It is preferable that the ratio of the epoxy resin (XB1) liquid at room temperature among the epoxy resin (XB1) contained in the composition (X) for resin layer formation and the thermosetting resin layer is 40 mass % or more, It is 50 mass % or more More preferably, it is especially preferable that it is 55 mass % or more, For example, any of 60 mass % or more, 70 mass % or more, 80 mass % or more, and 90 mass % or more may be sufficient. When the thermosetting resin film before curing is heated at 10°C/min because the ratio is equal to or greater than the lower limit, the minimum value of the shear viscosity at 90°C to 200°C can be easily adjusted to 500 Pa·s or more, and heat When a curable resin layer is affixed to the bump formation surface of a wafer with a bump and it is made to thermoset, the effect which suppresses the repelling of the surface of a semiconductor wafer becomes higher. Moreover, the effect which suppresses the residual|survival of a protective film residue in the top part of a bump becomes higher.

The upper limit of the said ratio is not specifically limited, The said ratio should just be 100 mass % or less.

The thermosetting agent (XB2) functions as a curing agent for the epoxy resin (XB1).

As a thermosetting agent (XB2), the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is anhydrideized, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrideized is preferable, and phenol It is more preferable that they are a sexual hydroxyl group or an amino group.

Among the thermosetting agents (XB2), examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, a biphenol, a novolak phenol resin, a dicyclopentadiene phenol resin, an aralkyl phenol resin, and the like. can be heard

Among the thermosetting agents (XB2), examples of the amine-based curing agent having an amino group include dicyandiamide.

The thermosetting agent (XB2) may have an unsaturated hydrocarbon group.

As the thermosetting agent (XB2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin and the like.

The said unsaturated hydrocarbon group in a thermosetting agent (XB2) is the same thing as the unsaturated hydrocarbon group in the epoxy resin which has the above-mentioned unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermal curing agent (XB2), the thermal curing agent (XB2) preferably has a high softening point or glass transition temperature from the viewpoint of improving the releasability of the thermal curing resin layer from the supporting sheet.

Among the thermosetting agents (XB2), for example, the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene-type phenol resin, and an aralkyl-type phenol resin is 300 to 30,000. It is preferable, it is more preferable that it is 400-10,000, It is especially preferable that it is 500-3,000.

Although the molecular weight of non-resin components, such as a biphenol and dicyandiamide, is not specifically limited among thermosetting agents (XB2), For example, it is preferable that it is 60-500.

A thermosetting agent (XB2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combination and a ratio can be selected arbitrarily.

Composition (X) for resin film formation and thermosetting resin layer WHEREIN: It is preferable that content of thermosetting agent (XB2) is 0.1-500 mass parts with respect to content of 100 mass parts of epoxy resin (XB1), 1-200 It is more preferable that it is a mass part, For example, any of 1-150 mass parts, 1-100 mass parts, 1-75 mass parts, 1-50 mass parts, and 1-30 mass parts may be sufficient. When the said content of a thermosetting agent (XB2) is more than the said lower limit, hardening of a thermosetting resin layer advances more easily. Moreover, when the said content of the thermosetting agent (XB2) is below the said upper limit, the moisture absorption of a thermosetting resin layer is reduced, and the reliability of the package which has a protective film formed using the laminated body for protective film formation improves more.

In the composition (X) for forming a resin film and the thermosetting resin layer, the content of the thermosetting component (XB) (eg, the total content of the epoxy resin (XB1) and the thermosetting agent (XB2)) is the polymer component (XA) ) It is preferable that it is 50-1,000 mass parts with respect to content of 100 mass parts, It is more preferable that it is 60-950 mass parts, It is especially preferable that it is 70-900 mass parts. When the said content of a thermosetting component (XB) is such a range, the adhesive force of a thermosetting resin layer and a support sheet is suppressed, and the peelability of a support sheet improves.

(curing accelerator (XC))

The composition (X) for resin layer formation and the thermosetting resin layer may contain the hardening accelerator (XC). A hardening accelerator (XC) is a component for adjusting the cure rate of a thermosetting resin layer.

As a preferable hardening accelerator (XC), For example, tertiary amines, such as triethylenediamine, benzyl dimethylamine, a triethanolamine, dimethylamino ethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 imidazoles such as -hydroxymethylimidazole (imidazole in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine (phosphine in which at least one hydrogen atom is substituted with an organic group); Tetraphenyl boron salts, such as tetraphenylphosphonium tetraphenyl borate and a triphenylphosphine tetraphenyl borate, etc. are mentioned.

The number of the composition (X) for resin layer formation and the hardening accelerator (XC) which the thermosetting resin layer contains may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

When using a curing accelerator (XC), in the composition (X) for forming a resin layer and a thermosetting resin layer, the content of the curing accelerator (XC) is 0.01 to 100 parts by mass of the content of the thermosetting component (XB). It is preferable that it is -10 mass parts, and it is more preferable that it is 0.1-5 mass parts. When the said content of a hardening accelerator (XC) is more than the said lower limit, the effect by using a hardening accelerator (XC) is acquired more notably. In addition, when the content of the curing accelerator (XC) is below the upper limit, for example, the high polar curing accelerator (XC) moves to the adhesive interface side with the adherend in the thermosetting resin layer under high temperature and high humidity conditions. The effect of suppressing segregation becomes high, and the reliability of the package which has a protective film formed using the laminated body for protective film formation improves more.

(Filling (XD))

The composition (X) for resin layer formation and the thermosetting resin layer may contain the filler (XD). When a thermosetting resin layer contains a filler (XD), adjustment of a thermal expansion coefficient becomes easy for the protective film obtained by hardening|curing a thermosetting resin layer. And the reliability of the package which has a protective film formed using the laminated body for protective film formation improves more by optimizing this thermal expansion coefficient with respect to the object to be formed of a protective film. Moreover, when a thermosetting resin layer contains a filler (XD), the moisture absorption of a protective film can be reduced, or heat dissipation can also be improved.

Although any of an organic filler and an inorganic filler may be sufficient as a filler (XD), it is preferable that it is an inorganic filler.

As a preferable inorganic filler, For example, powders, such as a silica, alumina, a talc, a calcium carbonate, a titanium white, bengala, a silicon carbide, and boron nitride; beads obtained by spheroidizing these inorganic fillers; Surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; Glass fiber etc. are mentioned.

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

One type may be sufficient as the filler (XD) which the composition (X) for resin layer formation and a thermosetting resin layer contain, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

It is preferable that it is 1 micrometer or less, as for the average particle diameter of a filler (XD), it is more preferable that it is 0.5 micrometer or less, It is especially preferable that it is 0.1 micrometer or less. When the average particle diameter of the filler (XD) is equal to or less than the upper limit, adjustment of the shear viscosity at 90°C to 200°C becomes easier, the thermosetting resin layer is affixed to the bump formation surface of the wafer with bumps, and heat When hardened, the effect which suppresses the repelling of the surface of a semiconductor wafer becomes higher. Moreover, the effect which suppresses the residual|survival of a protective film residue in the top part of a bump becomes higher.

In addition, "average particle diameter" in the present specification refers to a particular value of the particle diameter (D ₅₀₎ of from, unless noted, 50% of the integrated value in the particle size distribution curve obtained by the laser diffraction scattering method.

The lower limit of the average particle diameter of a filler (XD) is not specifically limited. For example, it is preferable that the average particle diameter of a filler (XD) is 0.01 micrometer or more at the point from which acquisition of a filler (XD) is easier.

When the filler (XD) is used, in the composition (X) for forming a resin layer, the ratio of the content of the filler (XD) to the total content of all components other than the solvent (hereinafter also referred to as “active ingredient”) (i.e. It is preferable that it is 3-60 mass %, and, as for content of filler (XD) of a thermosetting resin layer), it is more preferable that it is 3-55 mass %. When the content of the filler (XD) is within such a range, adjustment of the shear viscosity at 90°C to 200°C becomes easier, the thermosetting resin layer is affixed to the bump formation surface of the wafer with bumps, and thermosetting When made, the repelling of the surface of a semiconductor wafer can be suppressed. Moreover, while the effect which suppresses the residual|survival of a protective film residue becomes higher in the head part of a bump, adjustment of the said thermal expansion coefficient becomes easier.

(Coupling agent (XE))

The composition (X) for resin layer formation and the thermosetting resin layer may contain the coupling agent (XE). By using what has a functional group which can react with an inorganic compound or an organic compound as a coupling agent (XE), the adhesiveness and adhesiveness with respect to the to-be-adhered body of a thermosetting resin layer can be improved. Moreover, water resistance improves the protective film obtained by hardening|curing a thermosetting resin layer by using a coupling agent (XE), without impairing heat resistance.

It is preferable that it is a compound which has a functional group which can react with the functional group which a polymer component (XA), a thermosetting component (XB), etc. have, and, as for a coupling agent (XE), it is more preferable that it is a silane coupling agent.

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- Glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyl Triethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned.

One type may be sufficient as the coupling agent (XE) which the composition (X) for resin layer formation and a thermosetting resin layer contain, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

When using a coupling agent (XE), the composition (X) for resin layer formation and a thermosetting resin layer WHEREIN: Content of a coupling agent (XE) is the total content of a polymer component (XA) and a thermosetting component (XB) It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts, It is more preferable that it is 0.05-10 mass parts, It is especially preferable that it is 0.1-5 mass parts. When the content of the coupling agent (XE) is equal to or greater than the lower limit, the improvement of the dispersibility of the filler (XD) with respect to the resin, the improvement of the adhesiveness of the thermosetting resin layer with the adherend, etc., by using the coupling agent (XE) The effect is obtained more conspicuously. Moreover, generation|occurrence|production of an outgas is suppressed more because the said content of a coupling agent (XE) is below the said upper limit.

(crosslinking agent (XF))

As the polymer component (XA), when using a polymer component (XA) having a functional group such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxy group, and isocyanate group capable of bonding with other compounds, such as the above-mentioned acrylic resin, the resin layer The composition for formation (X) and the thermosetting resin layer may contain the crosslinking agent (XF). The crosslinking agent (XF) is a component for crosslinking by bonding the functional group in the polymer component (XA) to another compound, and by crosslinking in this way, the initial adhesive force and cohesive force of the thermosetting resin layer can be adjusted.

Examples of the crosslinking agent (XF) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate crosslinking agent (crosslinking agent having a metal chelate structure), and an aziridine crosslinking agent (crosslinking agent having an aziridinyl group).

As said organic polyhydric isocyanate compound, For example, an aromatic polyhydric isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyhydric isocyanate compound (Hereinafter, these compounds are collectively abbreviated as "aromatic polyvalent isocyanate compound etc."); a trimer, an isocyanurate body, and an adduct body, such as the said aromatic polyhydric isocyanate compound; The terminal isocyanate urethane-free polymer etc. which are obtained by making the said aromatic polyhydric isocyanate compound etc. react with a polyol compound are mentioned. The "adduct body" is an aromatic polyhydric isocyanate compound, an aliphatic polyvalent isocyanate compound, or an alicyclic polyvalent isocyanate compound, and a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. means reactants. As an example of the said adduct body, the xylylene diisocyanate adduct etc. which are mentioned later of trimethylol propane are mentioned.

As said organic polyhydric isocyanate compound, More specifically, For example, 2, 4- tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; compound which added any 1 type(s) or 2 or more types of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate to all or some hydroxyl groups of polyols, such as a trimethylol propane; Lysine diisocyanate etc. are mentioned.

Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate. , tetramethylolmethane-tri-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine, and the like.

When using an organic polyvalent isocyanate compound as a crosslinking agent (XF), as a polymer component (XA), it is preferable to use a hydroxyl-containing polymer. When the crosslinking agent (XF) has an isocyanate group and the polymer component (XA) has a hydroxyl group, the crosslinking structure can be easily introduced into the thermosetting resin layer by reaction of the crosslinking agent (XF) with the polymer component (XA).

The number of crosslinking agents (XF) which the composition (X) for resin layer formation and the thermosetting resin layer contain may be one, and two or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

When a crosslinking agent (XF) is used, in the composition (X) for forming a resin layer, the content of the crosslinking agent (XF) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (XA), It is more preferable that it is 0.1-10 mass parts, and it is especially preferable that it is 0.5-5 mass parts. When the said content of a crosslinking agent (XF) is more than the said lower limit, the effect by using a crosslinking agent (XF) is acquired more notably. Moreover, excessive use of a crosslinking agent (XF) is suppressed because the said content of a crosslinking agent (XF) is below the said upper limit.

(other ingredients)

The composition (X) for resin layer formation and a thermosetting resin layer are within the range which does not impair the effect of this invention, WHEREIN: The polymer component (XA) mentioned above, a thermosetting component (XB), a hardening accelerator (XC), a filler You may contain other components other than (XD), a coupling agent (XE), and a crosslinking agent (XF).

As said other component, an energy-beam curable resin, a photoinitiator, a coloring agent, a general-purpose additive, etc. are mentioned, for example. The general-purpose additive is known, can be arbitrarily selected according to the purpose, and is not particularly limited, but preferably, for example, a plasticizer, an antistatic agent, an antioxidant, a colorant (dye, pigment), a gettering agent, etc. can be heard

The composition (X) for resin layer formation and the said other component which a thermosetting resin layer contains may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

Content of the composition (X) for resin layer formation and said other component of a thermosetting resin layer is not specifically limited, What is necessary is just to select suitably according to the objective.

The composition (X) for resin layer formation and the thermosetting resin layer contain a polymer component (XA) and a thermosetting component (XB), and contain polyvinyl acetal as a polymer component (XA), and also an epoxy resin (XB1) It is preferable to contain a liquid thing at room temperature as this, and it is more preferable to contain a hardening accelerator (XC) and a filler (XD) other than these components further. And it is preferable that filler (XD) in this case has the above-mentioned average particle diameter. By using such a composition (X) for resin layer formation and a thermosetting resin layer, adjustment of the shear viscosity in 90 degreeC - 200 degreeC becomes further easy, and the bump formation surface of a wafer with a bump is a thermosetting resin layer. When it affixes on the surface which has and makes it thermoset, the repelling of the surface of a semiconductor wafer can be suppressed. Moreover, the effect which suppresses the residual|survival of a protective film residue in the top part of a bump becomes higher.

(menstruum)

It is preferable that the composition (X) for resin layer formation further contains a solvent. The handleability of the composition (X) for resin layer formation containing a solvent becomes favorable.

Although the said solvent is not specifically limited, As a preferable thing, For example, Hydrocarbons, such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; Ester, such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

The number of solvents which the composition (X) for resin layer formation contains may be one, and two or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

It is preferable that the solvent which the composition (X) for resin layer formation contains is methyl ethyl ketone etc. at the point which can mix more uniformly the containing component in the composition (X) for resin layer formation.

Content of the solvent of the composition (X) for resin layer formation is not specifically limited, For example, what is necessary is just to select suitably according to the kind of components other than a solvent.

[materials]

The 1st support base material used for the support sheet which the laminated body for protective film formation used in the manufacturing method of the semiconductor device of one aspect of this invention has is a sheet form or a film form, As its constituent material, for example, various and resin.

Moreover, the 2nd support base material used for the back grind tape used in the manufacturing method of the semiconductor device of one aspect of this invention is also sheet form or film form, As its constituent material, various resins are used, for example. can be heard

As said resin, For example, polyethylene, such as a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), and a high density polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer (copolymer obtained using ethylene as a monomer) ; Vinyl chloride-type resin (resin obtained using vinyl chloride as a monomer), such as polyvinyl chloride and a vinyl chloride copolymer; polystyrene; polycycloolefin; Polyester, such as a polyethylene terephthalate, a polyethylene naphthalate, a polybutylene terephthalate, a polyethylene isophthalate, a polyethylene-2, 6- naphthalene dicarboxylate, and wholly aromatic polyester in which all structural units have an aromatic cyclic group; Copolymer of 2 or more types of said polyester; poly(meth)acrylic acid ester; Polyurethane ; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; Polyether ketone etc. are mentioned.

Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than that, are also mentioned, for example. In the polymer alloy of the polyester and the resin other than that, it is preferable that the amount of the resin other than the polyester is relatively small.

Moreover, as said resin, for example, 1 type(s) or 2 or more types of the said resin illustrated so far crosslinked crosslinked resin; Modified resins, such as an ionomer using 1 type, or 2 or more types of the said resin illustrated so far, are also mentioned.

One type may be sufficient as resin which comprises a 1st support base material and a 2nd support base material, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

One layer (single layer) may be sufficient as a 1st support base material and a 2nd support base material, and two or more layers may be sufficient as multiple layers, In the case of multiple layers, these multiple layers may mutually be same or different, and a combination of these multiple layers. is not particularly limited.

In addition, in this specification, not only in the case of a 1st support base material and a 2nd support base material, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers are different. and only some layers may be the same", and "a plurality of layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other."

It is preferable that the thickness of a 1st support base material and a 2nd support base material is 5-1000 micrometers, It is more preferable that it is 10-500 micrometers, It is still more preferable that it is 15-300 micrometers, It is especially preferable that it is 20-150 micrometers. Do.

Here, the "thickness of a 1st support base material" and "thickness of a 2nd support base material" mean the thickness of the whole 1st support base material and the thickness of the whole 2nd support base material, For example, the 1st which consists of multiple layers The thickness of the supporting substrate means the total thickness of all the layers constituting the first supporting substrate. Similarly, the thickness of the 2nd support base material which consists of multiple layers means the thickness of the sum total of all the layers which comprise a 2nd support base material.

Here, from the viewpoint of further improving the precision of back grinding, the second supporting substrate used for the back grind tape preferably has a high precision in thickness, that is, a thickness variation is suppressed regardless of the site. Among the constituent materials described above, examples of the material usable for constituting the second supporting base material having such a high precision in thickness include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. and the like.

In addition, the second supporting substrate used for the back grind tape preferably has a Young's modulus of 600 MPa or more, and preferably 800 MPa or more, from the viewpoint of improving the supporting performance of the bumped wafer and further improving the precision of the back surface grinding. It is more preferable, and it is still more preferable that it is 1,000 Mpa or more. In addition, from the viewpoint of relieving the stress acting on an adherend, such as a wafer with bumps or a piece thereof, when peeling the back grind tape, the Young's modulus of the second supporting substrate is preferably 30,000 MPa or less, and 20,000 MPa It is more preferable that it is less than, and it is still more preferable that it is 10,000 MPa or less.

On the other hand, about the 1st support base material used for the support sheet which the laminated body for protective film formation has, since it is not necessary to consider the precision improvement of back grinding, the peelability of the support sheet from a curable resin layer is considered and the 1st support base material You can set the Young's modulus of From this viewpoint, the Young's modulus of the first supporting substrate is preferably 10,000 MPa or less, more preferably 5,000 MPa or less, still more preferably less than 1,000 MPa, and still more preferably less than 600 MPa. Moreover, the Young's modulus of a 1st support base material is 100 MPa or more normally, Preferably it is 200 MPa or more.

The Young's modulus of the substrate is a value measured in accordance with JISK-7127 (1999).

The first supporting substrate and the second supporting substrate may contain, in addition to the main constituent materials such as the resin, known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers). .

The 1st support base material and the 2nd support base material may be transparent, may be opaque, may be colored according to the objective, and another layer may be vapor-deposited.

When the thermosetting resin film is energy ray-curable, it is preferable that the first supporting substrate and the second supporting substrate transmit energy rays.

A 1st support base material and a 2nd support base material can be manufactured by a well-known method. For example, the 1st support base material and 2nd support base material containing resin can be manufactured by shape|molding the resin composition containing the said resin.

[Buffer layer]

The first buffer layer used in the support sheet of the laminate for forming a protective film used in the method for manufacturing a semiconductor device of one embodiment of the present invention is not particularly limited as long as it is a buffer layer generally used for back grind tape, but From the viewpoint of making it easy to ensure good embedding properties and easy peeling of the support sheet from the laminate for forming a protective film in the step (A2), as described above, the first buffer layer is stored in shear at room temperature (23°C). It is preferable that elastic modulus G' (23 degreeC) is 200 MPa or less, It is more preferable that it is 180 MPa or less, It is more preferable that it is 150 MPa or less. In addition, the shear storage modulus G' (23 degreeC) of a 1st buffer layer is 80 Mpa or more normally from a viewpoint of fully ensuring the maintainability at normal temperature of the curable resin layer by a 1st support base material.

In addition, the second buffer layer used for the back grind tape used in the method for manufacturing a semiconductor device according to one embodiment of the present invention is not particularly limited as long as it is a buffer layer generally used for the back grind tape. , from the viewpoint of easily securing good fixing performance of fixing the wafer with bumps during back grinding, as described above, the peak value of tanδ of the second buffer layer is preferably 1.2 or more, more preferably 1.3 or more, and 1.4 More preferably. Moreover, the peak value of tan-delta is 5.0 or less normally, Preferably it is 4.0 or less.

In addition, the thickness of a 1st buffer layer and a 2nd buffer layer is as above-mentioned.

Here, in the method for manufacturing a semiconductor device according to one embodiment of the present invention, the protective film-forming laminate and the back grind tape are used separately, and when the back grind tape is used, the bump neck of the wafer with bumps is protected by the protective film has been Therefore, the bump filling performance of the back grind tape may be lower than the bump filling performance of the laminated body for protective film formation. Therefore, the thickness of a 2nd buffer layer can be made thinner than the thickness of a 1st buffer layer. Specifically, the ratio of the thickness of the second buffer layer to the thickness of the first buffer layer [(thickness of the second buffer layer)/thickness of the first buffer layer] is preferably 0.9 or less, more preferably 0.8 or less, still more preferably It is usually less than 0.7. Moreover, it is 0.5 or more normally.

Here, in one aspect of the present invention, the first buffer layer and the second buffer layer are urethane (meth) acrylate and a thiol group-containing compound from the viewpoint of making it easy to adjust the shear storage modulus (23° C.) and tan δ to the above ranges. It is preferably formed from a resin composition comprising a.

Hereinafter, details of each component contained in the resin composition for forming the 1st buffer layer and the 2nd buffer layer (henceforth "resin composition for buffer layer formation") are demonstrated.

<Urethane (meth)acrylate>

Urethane (meth)acrylate is a compound which has at least a (meth)acryloyl group and a urethane bond, and has the property of superposing|polymerizing by energy-beam irradiation.

The number of (meth)acryloyl groups in the urethane (meth)acrylate may be monofunctional, bifunctional, or trifunctional or more, but the shear storage modulus G' (23 ° C.) and tan δ are adjusted to the above ranges to form a buffer layer From a viewpoint, it is preferable to include a monofunctional urethane (meth)acrylate.

When the monofunctional urethane (meth)acrylate is included in the film forming composition, the monofunctional urethane (meth)acrylate does not participate in the formation of the three-dimensional network structure in the polymerization structure, so that the three-dimensional network structure is not easily formed. In particular, it becomes easy to form a buffer layer in which the shear storage modulus G' (23°C) and tan δ were adjusted to the above ranges.

As a urethane (meth)acrylate used in the resin composition for forming a buffer layer, for example, a (meth)acrylate having a hydroxyl group is added to a terminal isocyanate urethane-free polymer obtained by reacting a polyol compound and a polyvalent isocyanate compound. can be obtained by reacting.

In addition, urethane (meth)acrylate may be used 1 type or in combination of 2 or more type.

(polyol compound)

The polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups.

Specific examples of the polyol compound include alkylenediol, polyether-type polyol, polyester-type polyol, and polycarbonate-type polyol.

Among these, polyether-type polyols are preferable.

Moreover, as a polyol compound, although any of a bifunctional diol, a trifunctional triol, and a tetrafunctional or more than polyol may be sufficient, a bifunctional diol is preferable from a viewpoint of easiness of availability, versatility, reactivity, etc., and polyether A type diol is more preferable.

As for polyether type diol, the compound represented by following formula (1) is preferable.

[Formula 2]

In said formula (1), although R is a divalent hydrocarbon group, an alkylene group is preferable and a C1-C6 alkylene group is more preferable. Among the C1-C6 alkylene group, an ethylene group, a propylene group, and a tetramethylene group are preferable, and a propylene group and a tetramethylene group are more preferable.

Moreover, n is the number of repeating units of an alkylene oxide, Preferably it is 10-250, More preferably, it is 25-205, More preferably, it is 40-185. If n is the said range, it is easy to adjust the urethane bond density|concentration of the urethane (meth)acrylate obtained, and to adjust tan-delta of a buffer layer to the said range.

Among the compounds represented by the formula (1), polyethylene glycol, polypropylene glycol and polytetramethylene glycol are preferable, and polypropylene glycol and polytetramethylene glycol are more preferable.

A terminal isocyanate urethane-free polymer into which an ether linkage moiety [-(-R-O-)n-] is introduced is produced by reaction of a polyether-type diol and a polyvalent isocyanate compound. By using such polyether type diol, urethane (meth)acrylate contains the structural unit derived from polyether type diol.

As a polybasic acid component used for manufacture of a polyester-type polyol, the compound generally known as a polybasic acid component of polyester can be used.

Specific examples of the polybasic acid component include dibasic acids such as adipic acid, maleic acid, succinic acid, oxalic acid, fumaric acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, and suberic acid; Dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid, aromatic polybasic acids such as polybasic acids such as trimellitic acid and pyromellitic acid, anhydrides and derivatives thereof, dimer acids, and hydrogen Addition dimer acid etc. are mentioned.

Among these, an aromatic polybasic acid is preferable from a viewpoint of forming the coating film which has moderate hardness.

You may use various well-known catalysts for the esterification reaction for manufacturing a polyester-type polyol as needed.

Examples of the catalyst include tin compounds such as dibutyl tin oxide and stannous octylic acid, and alkoxy titanium such as tetrabutyl titanate and tetrapropyl titanate.

It does not specifically limit as a polycarbonate type polyol, For example, the reaction product of the glycols mentioned above and alkylene carbonate, etc. are mentioned.

As a number average molecular weight computed from the hydroxyl value of a polyol compound, Preferably it is 1,000-10,000, More preferably, it is 2,000-9,000, More preferably, it is 3,000-7,000. When the number average molecular weight is 1,000 or more, it is preferable to avoid a situation in which control of the shear storage modulus of the buffer layer becomes difficult due to the generation of an excessive amount of urethane bonds. On the other hand, since it can prevent that the buffer layer obtained as the said number average molecular weight is 10,000 or less from softening excessively, it is preferable.

In addition, the number average molecular weight computed from the hydroxyl value of a polyol compound is the value computed from [number of polyol functional groups] x 56.11 x 1,000/[hydroxyl value (unit: mgKOH/g)].

(polyvalent isocyanate compound)

As a polyhydric isocyanate compound, For example, Aliphatic polyisocyanate, such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethyl hexamethylene diisocyanate; Alicyclic type such as isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and ω,ω'-diisocyanate dimethylcyclohexane diisocyanates; and aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, and naphthalene-1,5-diisocyanate. have.

Among these, from a viewpoint of a handleability, isophorone diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are preferable.

((meth)acrylate having a hydroxyl group)

It will not specifically limit, if it is a compound which has a hydroxyl group and a (meth)acryloyl group in at least 1 molecule as (meth)acrylate which has a hydroxyl group.

As (meth)acrylate which has a specific hydroxyl group, For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, hydroxyalkyl (meth)acrylates such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate; Hydroxyl group-containing (meth)acrylamide, such as N-methylol (meth)acrylamide; The reaction product obtained by making (meth)acrylic acid react with the diglycidyl ester of vinyl alcohol, vinyl phenol, and bisphenol A, etc. are mentioned.

Among these, hydroxyalkyl (meth)acrylate is preferable and 2-hydroxyethyl (meth)acrylate is more preferable.

As the conditions for reacting the terminal isocyanate urethane-free polymer and the (meth)acrylate having a hydroxyl group, in the presence of a solvent and a catalyst added as needed, the conditions for reacting at 60 to 100°C for 1 to 4 hours are preferable. .

The urethane (meth)acrylate for the resin composition for forming a buffer layer obtained in this way may be any of an oligomer, a high molecular weight substance, or a mixture thereof, but a urethane (meth)acrylate oligomer is preferable.

The weight average molecular weight of this urethane (meth)acrylate becomes like this. Preferably it is 1,000-100,000, More preferably, it is 3,000-80,000, More preferably, it is 5,000-65,000. When the weight average molecular weight is 1,000 or more, in the polymer of urethane (meth) acrylate and a polymerizable monomer to be described later, due to the intermolecular force between structures derived from urethane (meth) acrylate, appropriate hardness is imparted to the buffer layer. It is preferable because

The blending amount of the urethane (meth)acrylate in the resin composition for forming a buffer layer is preferably 20 to 70 mass%, more preferably 25 to 60 mass%, still more preferably 30 to 50 mass%, still more preferably It is 33-47 mass %. When the compounding quantity of urethane (meth)acrylate exists in such a range, it will become easier to adjust the shear storage modulus (23 degreeC) and tan-delta of a buffer layer to the said range.

<A compound containing a thiol group>

The thiol group-containing compound is not particularly limited as long as it is a compound having at least one thiol group in the molecule, but a polyfunctional thiol group-containing compound is preferable from the viewpoint of facilitating formation of a buffer layer in which tan δ is adjusted to the above range, A tetrafunctional thiol group containing compound is more preferable.

Specific examples of the thiol group-containing compound include nonyl mercaptan, 1-dodecanthiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, triazinedithiol, and triazinetrithiol. , 1,2,3-propanetrithiol, tetraethylene glycol-bis(3-mercaptopropionate), trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate) propionate), pentaerythritol tetrakisthioglucolate, dipentaerythritol hexakis (3-mercaptopropionate), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3, 5-triazine-2,4,6-(1H,3H,5H)-trione etc. are mentioned.

In addition, you may use these thiol group containing compounds 1 type or in combination of 2 or more type.

The molecular weight of the thiol group-containing compound is preferably 200 to 3,000, more preferably 300 to 2,000. Compatibility with urethane (meth)acrylate becomes favorable as the said molecular weight is the said range, and film forming property can be made favorable.

To [ the compounding quantity of a thiol group containing compound / a total of 100 mass parts of a urethane (meth)acrylate and the polymerizable monomer mentioned later ], Preferably it is 1.0-4.9 mass parts, More preferably, it is 1.5-4.8 mass parts.

If the said compounding quantity is 1.0 mass part or more, it will become easy to form the buffer layer whose tan-delta was adjusted to the said range. On the other hand, leaching of the buffer layer when the said compounding quantity is 4.9 mass parts or less when it winds up in roll shape can be suppressed.

(Polymerizable Monomer)

It is preferable that a polymerizable monomer is further included in the resin composition for buffer layers used by this invention from a viewpoint of improving film forming property.

The polymerizable monomer is a polymerizable compound other than the above urethane (meth) acrylate, and is a compound that can be polymerized with other components by irradiation with energy rays, excluding the resin component, having at least one (meth) acryloyl group compounds are preferred.

In addition, in this specification, a "resin component" refers to an oligomer or a high molecular weight body having a repeating structure in the structure, and refers to a compound having a weight average molecular weight of 1,000 or more.

Examples of the polymerizable monomer include (meth)acrylate having an alkyl group having 1 to 30 carbon atoms, (meth)acrylate having a functional group such as a hydroxyl group, an amide group, an amino group and an epoxy group, and an alicyclic structure (meth) ) acrylate, (meth)acrylate having an aromatic structure, (meth)acrylate having a heterocyclic structure, styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpi Vinyl compounds, such as rollidone and N-vinyl caprolactam, etc. are mentioned.

As (meth)acrylate which has a C1-C30 alkyl group, For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate , n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl ( Meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylic a rate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. are mentioned.

As (meth)acrylate which has a functional group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2- hydroxyl group-containing (meth)acrylates such as hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-butyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methylolpropane (meth)acrylamide, N-methyl amide group-containing compounds such as oxymethyl (meth)acrylamide and N-butoxymethyl (meth)acrylamide; amino group-containing (meth)acrylates such as primary amino group-containing (meth)acrylate, secondary amino group-containing (meth)acrylate, and tertiary amino group-containing (meth)acrylate; Epoxy group-containing (meth)acrylates, such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and allyl glycidyl ether, etc. are mentioned.

As (meth)acrylate which has an alicyclic structure, for example, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, cyclohexyl (meth)acrylate, adamantane (meth)acrylate, etc. are mentioned.

As (meth)acrylate having an aromatic structure, for example, phenylhydroxypropyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. can be heard

As (meth)acrylate which has a heterocyclic structure, tetrahydrofurfuryl (meth)acrylate, morpholine (meth)acrylate, etc. are mentioned, for example.

Among these, from the viewpoint of compatibility with the urethane (meth)acrylate, it is preferable to have a relatively bulky group, more specifically (meth)acrylate having an alicyclic structure, (meth) having an aromatic structure The (meth)acrylate which has an acrylate and a heterocyclic structure is preferable, and the (meth)acrylate which has an alicyclic structure is more preferable. In addition, from the viewpoint of obtaining a resin composition for forming a buffer layer that is easy to form a buffer layer having tan δ adjusted to the above range, as a polymerizable monomer, (meth) acrylate having a functional group and (meth) acrylate having an alicyclic structure are included. It is preferable to do it, and it is more preferable to include hydroxypropyl (meth)acrylate and isobornyl (meth)acrylate.

The compounding quantity of the (meth)acrylate which has an alicyclic structure in the resin composition for buffer layer formation becomes like this from the said viewpoint, Preferably it is 32-53 mass %, More preferably, it is 35-51 mass %, More preferably, 37-48 mass %. It is mass %, More preferably, it is 40-47 mass %.

Moreover, the compounding quantity of the (meth)acrylate which has an alicyclic structure with respect to the total amount of the polymerizable monomer contained in the resin composition for buffer layer formation is from the said viewpoint, Preferably it is 52-87 mass %, More preferably, It is 55-85 mass %, More preferably, it is 60-80 mass %, More preferably, it is 65-77 mass %. If the compounding quantity of the (meth)acrylate which has an alicyclic structure is such a range, it will become easier to adjust the shear storage modulus (23 degreeC) of a buffer layer to the above-mentioned range.

Moreover, the compounding quantity of the polymerizable monomer in the resin composition for buffer layer formation becomes like this. Preferably it is 30-80 mass %, More preferably, 40-75 mass %, More preferably, 50-70 mass %, More preferably, 53 -67 mass %. When the blending amount of the polymerizable monomer is in such a range, the buffer layer tends to become flexible because the mobility of the portion formed by polymerization of the polymerizable monomer in the buffer layer is high, forming a buffer layer with tan δ adjusted to the above range. , it becomes easier to form a buffer layer whose shear storage modulus is adjusted to the above range.

In addition, from the same viewpoint, the mass ratio [urethane (meth)acrylate/polymerizable monomer] of the urethane (meth)acrylate and the polymerizable monomer in the resin composition for forming a buffer layer is preferably 20/80 to 60/40, more Preferably it is 30/70 - 50/50, More preferably, it is 35/65 - 45/55.

(energy ray polymerization initiator)

When forming a buffer layer by hardening the coating film which consists of a resin composition for buffer layer formation using an ultraviolet-ray etc. as an energy beam, it is preferable that the resin composition for buffer layer formation further contains an energy-beam polymerization initiator. Since an energy-beam polymerization initiator is also generally called "a photoinitiator", in this specification, hereafter, it is also simply called a "photoinitiator."

As a photoinitiator, For example, Photoinitiators, such as a benzoin compound, an acetophenone compound, an acyl phosphinoxide compound, a titanocene compound, a thioxanthone compound, a peroxide compound, Photosensitizers, such as an amine and a quinone etc. are mentioned, More specifically, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzoin, benzoin methyl ether , benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like.

You may use these photoinitiators 1 type or in combination of 2 or more type.

To [ the compounding quantity of a photoinitiator / a total of 100 mass parts of a urethane (meth)acrylate and a polymerizable monomer / ], Preferably it is 0.05-15 mass parts, More preferably, it is 0.1-10 mass parts, More preferably, it is 0.3- 5 parts by mass.

(Other additives)

The resin composition for buffer layer formation is a range which does not impair the effect of this invention. WHEREIN: You may make it contain another additive.

As another additive, a crosslinking agent, antioxidant, a softener (plasticizer), a filler, a rust preventive agent, a pigment, dye etc. are mentioned, for example.

When mix|blending these additives, the compounding quantity of another additive becomes like this with respect to a total of 100 mass parts of a urethane (meth)acrylate and a thiol group containing compound, Preferably it is 0.01-6 mass parts, More preferably, it is 0.1-3 mass parts. is wealth

Moreover, in the range which does not impair the effect of this invention in the resin composition for buffer layer formation, although you may contain resin components other than urethane (meth)acrylate, it is preferable to contain only urethane (meth)acrylate as a resin component. Do.

Content of the resin component other than urethane (meth)acrylate contained in the resin composition for buffer layer formation becomes like this. Preferably it is 5 mass % or less, More preferably, it is 1 mass % or less, More preferably, it is 0.1 mass % or less, and further Preferably it is 0 mass %.

In addition, in the case where it becomes easier to form a buffer layer with tan δ adjusted to the above range, or to form a buffer layer with a shear storage modulus adjusted to the above range, the buffer layer is formed from the above-mentioned resin composition for forming a buffer layer. , a cured product of a curable composition containing a non-reactive urethane polymer or oligomer and a polymerizable monomer, or an ethylene-α-olefin copolymer may be used. The non-reactive urethane polymer or oligomer may use a well-known thing, and as a polymerizable monomer, the thing similar to what was mentioned above can be used. Such a curable composition may contain the above-mentioned energy-beam polymerization initiator.

The ethylene-α-olefin copolymer is obtained by polymerizing ethylene and an α-olefin monomer. Examples of the α-olefin monomer include propylene, 1-butene, 2-methyl-1-butene, 2-methyl-1-pentene, 1-hexene, 2,2-dimethyl-1-butene, and 2-methyl-1-hexene. , 4-methyl-1-pentene, 1-heptene, 3-methyl-1-hexene, 2,2-dimethyl-1-pentene, 3,3-dimethyl-1-pentene, 2,3-dimethyl-1-pentene , 3-ethyl-1-pentene, 2,2,3-trimethyl-1-butene, 1-octene, 2,2,4-trimethyl-1-octene, and the like. These α-olefin monomers can be used alone or in combination of two or more.

In addition, other polymerizable monomers can also be used for the ethylene-alpha-olefin copolymer other than the said monomer. As another polymerizable monomer, For example, vinyl compounds, such as vinyl acetate, styrene, acrylonitrile, methacrylonitrile, vinyl ketone; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, methyl methacrylate, ethyl methacrylate, and methacrylic acid-n-propyl; Unsaturated carboxylic acid amides, such as acrylamide and methacrylamide, etc. are mentioned. These polymerizable monomers can be used 1 type or in combination of 2 or more type.

[Adhesive layer]

The 1st adhesive layer used for the support sheet which the laminated body for protective film formation has used in the manufacturing method of the semiconductor device of one aspect|mode of this invention has a curable resin layer in a support sheet shape until the said process (A2) is performed. can be maintained, and in the step (A2), the support sheet can be peeled and separated from the curable resin layer while maintaining the state in which the curable resin layer is affixed to the bumped wafer, and is not particularly limited.

In addition, the 2nd adhesive layer used for the back grind tape used in the manufacturing method of the semiconductor device of one aspect of this invention is not specifically limited as long as it can fix and protect the bumped wafer with a protective film formed. .

The adhesive which forms a 1st adhesive layer and a 2nd adhesive layer is not specifically limited, The various adhesives conventionally used for the back grind tape can be used. Specifically, adhesives such as rubber, acrylic, silicone, and polyvinyl ether are used. Moreover, you may use the adhesive of an energy ray hardening type, a heat foaming type, and a water swelling type.

In addition, the thickness of a 1st adhesive layer and a 2nd adhesive layer is as mentioned above.

In addition, a peeling film may be further bonded together, and the adhesive layer may be protected by the peeling film. A release film is not specifically limited, What carried out the peeling process with a release agent for sheets, such as a film and paper, can be used.

[Method for producing a laminate for forming a protective film]

It does not restrict|limit especially as a manufacturing method of the laminated body for protective film formation used in one aspect|mode of this invention, It can manufacture by a well-known method.

Specifically, for example, a support sheet is produced by forming a 1st buffer layer on a 1st support base material, and forming a 1st adhesive layer after that. And the laminated body for protective film formation can be manufactured by apply|coating the composition (X) for resin film formation on a release material, forming a curable resin layer, and bonding together the 1st adhesive layer and curable resin layer of a support sheet.

As a method of forming the first buffer layer on the first support substrate, a resin composition for forming a buffer layer is applied to one surface of the first support substrate to form a coating film, and then a curing treatment is performed to obtain the first buffer layer. After forming a coating film by applying the resin composition for forming a buffer layer to the release treatment surface of the forming method or the release material, a semi-cured treatment is performed to form a semi-cured layer on the release material, and the semi-cured layer and the first support After bonding a base material and removing a peeling material, the method of completely hardening a semi-hardened layer, and forming a 1st buffer layer, etc. are mentioned.

As a method of forming the first pressure-sensitive adhesive layer on the first buffer layer, a method of applying a pressure-sensitive adhesive composition for forming the first pressure-sensitive adhesive layer on the first buffer layer, or a method of applying the pressure-sensitive adhesive composition to the peeling treatment surface of a release material and peeling it The method of forming a 1st adhesive layer on a material and bonding a 1st adhesive layer with a 1st buffer layer is mentioned.

As a method of apply|coating the resin composition for buffer layer formation, an adhesive composition, or the composition (X) for resin film formation on a 1st support base material or a release material, For example, the spin coating method, the spray coating method, the bar coat method, knife coat method, roll coat method, blade coat method, die coat method, gravure coat method, etc. are mentioned.

In addition, when the resin composition for buffer layer formation, an adhesive composition, or the composition (X) for resin film formation is in the form of a solution containing an organic solvent, after apply|coating this, at the temperature of 80-150 degreeC for 30 second - 5 minutes It is preferable to perform a drying process by heating. In addition, the said heat processing performed with respect to the composition (X) for resin film formation is not contained in the hardening process of the curable resin layer in the manufacturing method of the semiconductor device of this invention.

As a hardening process after apply|coating the resin composition for buffer layer formation and forming a coating film, the method of irradiating energy rays, such as an ultraviolet-ray, to the formed coating film, and polymerization hardening is preferable. In addition, a hardening process may be made to harden completely at once, and may be divided into multiple times and may be hardened.

As an energy beam, an ultraviolet-ray, an electron beam, etc. are mentioned, for example, An ultraviolet-ray is preferable.

In addition, the irradiation amount of an energy beam is changed suitably according to the kind of energy beam. For example, when using an ultraviolet-ray, the illuminance of the ultraviolet-ray to irradiate becomes like this. Preferably it is 50-500 mW/cm<2>, More preferably, it is 100-340 mW/cm<2>, The irradiation amount of an ultraviolet-ray becomes like this. Preferably it is 100-2,500. It is mJ/cm<2>, More preferably, it is 150-2,000 mJ/cm<2>.

[Manufacturing method of back grind tape]

The manufacturing method of the back grind tape used in one aspect of this invention is not specifically limited, It can manufacture by a well-known method.

Specifically, for example, by the method similar to the manufacturing method of the support sheet which comprises the laminated body for protective film formation, a 2nd buffer layer is formed on a 2nd support base material, After that, the method of forming a 2nd adhesive layer can be heard

Example

The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples.

[Method of measuring various physical properties]

The physical property values in the following examples and comparative examples are values measured by the following methods.

<Weight Average Molecular Weight>

It measured under the following conditions using the gel permeation chromatography apparatus (The Tosoh Corporation make, product name "HLC-8020"), and the value measured by standard polystyrene conversion was used.

(Measuring conditions)

· Column: "TSK guard column HXL-L" "TSK gel G2500HXL" "TSK gel G2000HXL" "TSK gel G1000HXL" (all manufactured by Tosoh Corporation) sequentially connected

· Column temperature: 40℃

· Developing solvent: tetrahydrofuran

· Flow rate: 1.0 ㎖/min

<Measurement of the thickness of each layer>

It was measured using the static pressure thickness measuring machine manufactured by Techlock Corporation (model number: "PG-02J", standard standard: conforming to JIS K6783, Z1702, Z1709).

<Glass transition temperature>

The glass transition temperature (Tg) of the polymer component (XA), which will be described later, is measured using a differential scanning calorimeter (PYRIS Diamond DSC) manufactured by Perkin Elmer Corporation in a temperature profile of -70°C to 150°C at an elevating temperature rate of 10°C/min. was measured, and the inflection point was confirmed and obtained.

<Epoxy equivalent>

It measured based on JISK7236:2009.

<Average particle size>

The particles to be measured are dispersed in water by ultrasonic waves, and the particle size distribution of the particles is measured on a volume basis with a dynamic light scattering method particle size distribution analyzer (manufactured by Horiba Corporation, LB-550), and the median diameter ( D ₅₀ ) was taken as the average particle diameter.

[Preparation of the composition (X) for forming a resin layer]

The composition (X) for resin layer formation used for manufacture of the laminated body for protective film formation used by the following Example and the comparative example was prepared with the following method.

<The component used for preparation of the composition (X) for resin layer formation>

The component used for preparation of the composition (X) for resin layer formation is shown below.

(Polymer component (XA))

Polyvinyl butyral (Sekisui Chemical Industry Co., Ltd., S-Rec (registered trademark) B BL having structural units represented by the following formulas (i-1), (i-2), and (i-3) -10, a weight average molecular weight of 25,000, a glass transition temperature of 59 degreeC, in the following formula, p is 68-74 mol%, q is 1-3 mol%, and r is about 28 mol%) was used.

[Formula 3]

(epoxy resin (XB1))

The following two types of epoxy resins were used.

Epoxy resin (XB1-1): liquid bisphenol A epoxy resin (manufactured by DIC Corporation, EPICLON (registered trademark) EXA-4850-1000, epoxy equivalent 404 to 412 g/eq)

Epoxy resin (XB1-2): dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, EPICLON (registered trademark) HP-7200, epoxy equivalent 254 to 264 g/eq)

(thermal curing agent (XB2))

A novolac-type phenol resin (manufactured by Showa Denko Co., Ltd., Shonol (registered trademark) BRG-556) was used.

(curing accelerator (XC))

2-phenyl-4,5-dihydroxymethylimidazole (the Shikoku Chemical Industry Co., Ltd. make, Qazole (trademark) 2PHZ) was used.

(Filling (XD))

Spherical silica modified with an epoxy group (manufactured by Admatex Co., Ltd., Admanano (registered trademark) YA050C-MKK, average particle diameter of 0.05 µm) was used.

<Preparation of the composition (X) for resin layer formation>

A polymer component (XA), an epoxy resin (XB1-1), an epoxy resin (XB1-2), a thermal curing agent (XB2), a curing accelerator (XC), and a filler (XD) are mixed with the composition (X) for forming a resin layer. Based on the total amount (100 mass%), the composition (X) for forming a resin layer having an active ingredient (solid content) concentration of 55 mass% by dissolving or dispersing in methyl ethyl ketone so as to have the following content and stirring at 23 ° C. prepared.

- Polymer component (XA): 9.9 mass %

· Epoxy resin (XB1-1): 37.9 mass%

· Epoxy resin (XB1-2): 24.7 mass%

· Thermal curing agent (XB2): 18.3 mass%

· Curing accelerator (XC): 0.2 mass%

· Filler (XD): 9.0 mass%

[Production of a laminate for forming a protective film]

The laminated body for protective film formation used by the following Example and the comparative example was manufactured by the following method.

First, the composition (X) for forming a resin layer on the release treatment surface of the release material made of polyethylene terephthalate (manufactured by Lintec Co., Ltd., SP-PET381031, thickness 38 µm) having a release surface treated with a release treatment with silicone. was applied and dried by heating at 120°C for 2 minutes to prepare a laminate in which a thermosetting resin layer and a release material were laminated.

Next, as a support sheet, a first base material (thickness: 100 µm), a first buffer layer (thickness: 400 µm), and a first pressure-sensitive adhesive layer (thickness: 10 µm) are laminated in this order. Using Lintec Co., Ltd. make, E-8510HR), the 1st adhesive layer of this affixing tape, and the thermosetting resin layer of the laminated body of a thermosetting resin layer and a release material are bonded together, a support sheet, a thermosetting resin layer, and peeling A laminate for forming a protective film in which ashes were laminated in this order was prepared.

[Evaluation of lowest shear viscosity of thermosetting resin layer]

The release material was peeled from the laminate in which the thermosetting resin layer and the release material were laminated|stacked, and a 500-micrometer-thick thermosetting resin layer was formed by laminating|stacking a plurality of thermosetting resin layers. From this, a cylindrical evaluation sample having a diameter of 25 mm and a thickness of 500 µm was prepared, and this sample was installed in a shear viscosity measuring device. At this time, the sample was mounted on the mounting point of the measuring device, and the sample was fixed to the mounting point and installed by pressing the measuring jig from the upper surface of the sample.

The shear viscosity from room temperature (23°C) to 150°C was measured under the measurement conditions of frequency: 1 Hz and temperature increase rate: 10°C/min, and the minimum value of the shear viscosity at 90°C to 130°C was obtained. .

[Example 1]

(Example 1)

The bump formation surface of the semiconductor wafer by removing the release material from the laminate for forming a protective film, and pressing the exposed surface (exposed surface) of the thermosetting resin layer to the bump formation surface of the wafer with 8 inch φ bumps. The laminated body for protective film formation was affixed to this. At this time, sticking of the laminated body for protective film formation uses a sticking apparatus (a roller-type laminator, Lintech Co., Ltd. product "RAD-3510F/12"), and table temperature 90 degreeC, sticking speed 2 mm/sec, and sticking pressure 0.5 It implemented under the conditions of MPa, heating a thermosetting resin layer. As a wafer with 8-inch φ bumps, the height of the bumps is 210 μm, the width of the bumps is 250 μm, and the distance between adjacent bumps is 400 μm, a 0.4 mm pich BGA semiconductor wafer (WLPTEG M2 manufactured by Walts, wafer thickness of 700 µm) was used.

By the above, the laminated structure comprised by sticking the laminated body for protective film formation on the bump formation surface of a semiconductor wafer was obtained.

Next, after UV irradiation and peeling of the supporting sheet of the laminate for forming a protective film (manufactured by Lintec Corporation, RAD-2700), the bumped wafer to which the thermosetting resin layer was affixed was heated in a pressurized oven (RAD manufactured by Lintec Corporation). -9100), temperature: 130°C, time: 2 h, and furnace pressure: 0.5 MPa under heating conditions to thermoset the thermosetting resin layer to form a protective film.

Then, after affixing E-8510HR, manufactured by Lintec Co., Ltd., as a back grind tape on the protective film formation surface, back grinding is performed to make the wafer thickness 200 µm, the back grind tape is peeled off, and the warpage of the wafer is visually observed. Confirmed.

As a result, the warpage of the wafer was hardly seen.

In addition, as a result of scanning the bump surface with a digital microscope after the formation of the protective film, it became clear that points such as pinholes in which the bump formation surface of the wafer was exposed were not detected and that no repelling occurred. In addition, the minimum shear viscosity of the thermosetting resin layer was 2,700 Pa.s.

10 ; semiconductor wafer with bumps
11 ; semiconductor wafer
11a; bump forming surface
11b; back side
12 ; bump
20 ; curable resin layer
30 ; laminate for forming a protective film
30a; support sheet
40 ; shield
50 ; back grind tape
61 ; Split Origin (Home)
71; Split origin (reformed region)

Claims (7)

A method for manufacturing a semiconductor device comprising the following steps (A) to (E) in this order.
(A) Process of forming a curable resin layer in the bump formation surface of the semiconductor wafer provided with bumps
(B) The step of curing the curable resin layer to form a protective film
(C) A step of affixing a back grind tape to the surface on which the protective film of the semiconductor wafer having the bumps is formed
(D) The process of grinding the surface opposite to the said bump formation surface of the semiconductor wafer provided with the said bump in the state which the said back grind tape was stuck.
(E) The process of peeling the said back grind tape from the semiconductor wafer provided with the said bump after the said grinding|grinding The method of claim 1,
The method for manufacturing a semiconductor device, wherein the step (A) includes the following steps (A1) and (A2) in this order.
(A1) A step of affixing a laminate for forming a protective film having a laminate structure in which a support sheet and a curable resin layer are laminated on the bump formation surface of the semiconductor wafer having the bump, with the curable resin layer as the affixing surface
(A2) The process of peeling the said support sheet from the said laminated body for protective film formation, and forming the said curable resin layer in the said bump formation surface of the semiconductor wafer provided with the said bump. 3. The method according to claim 1 or 2,
The manufacturing method of the semiconductor device whose said curable resin layer is a thermosetting resin layer. 4. The method according to any one of claims 1 to 3,
The thickness of the said semiconductor wafer used in the said process (A) is 300 micrometers or more, The manufacturing method of a semiconductor device. 5. The method according to any one of claims 1 to 4,
Before the step (A), between the step (A) and the step (B), between the step (B) and the step (C), and between the step (C) and the step (D) , A method for manufacturing a semiconductor device that forms a dividing starting point for dividing a semiconductor wafer having the bumps into pieces. 6. The method according to any one of claims 1 to 5,
Between the step (B) and the step (C) and after the step (E), the protective film covering the top of the bump or the protective film adhering to a part of the top of the bump is removed, and the bump is The manufacturing method of the semiconductor device which performs the exposure process which exposes the top part of. 7. The method of claim 6,
The said exposure process is a plasma etching process, The manufacturing method of the semiconductor device.

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