KR20170048149A - Substrate separating method - Google Patents

Abstract

A support is quickly separated from a laminate while preventing light from being irradiated onto a circuit formed on the substrate.
(Solution) In a substrate 1 on which a circuit is formed, a predetermined area surrounding the entire circumference of the circuit formation region and occupying an area of 65% or more and less than 100% of the width in the radial direction of the non- Laser light L is irradiated to at least a part of the separation layer 4 laminated to the support plate 2 via the support plate 2 to separate the support plate from the laminate 10. [

Description

{SUBSTRATE SEPARATING METHOD}

The present invention relates to a support separation method.

BACKGROUND ART [0002] In recent years, electronic equipment such as IC cards and cellular phones have been required to be made thinner, smaller, and lighter. In order to satisfy these requirements, a thin semiconductor chip must be used for the mounted semiconductor chip. For this reason, it is said that the thickness (film thickness) of the wafer substrate as a base of the semiconductor chip should be 125 μm to 150 μm in the current situation, but should be 25 μm to 50 μm in the next generation chip. Therefore, in order to obtain a wafer substrate having the above-described film thickness, a step of thinning the wafer substrate is indispensable.

In order to prevent breakage of the thinned wafer substrate, the wafer substrate is automatically transferred to the wafer substrate in a state in which the support plate is stuck to the wafer substrate, Circuits and other structures are mounted. Then, after the manufacturing process, the wafer substrate is separated from the support plate. So far, various methods for peeling the support from the wafer substrate have been used.

Patent Document 1 discloses a method for manufacturing a light emitting device, comprising the steps of: arranging a photo-thermal conversion layer on at least a part of an outer edge of a first main surface; and a step of arranging a photo- A step of irradiating a laser beam to the photo-thermal conversion layer, and a step of irradiating laser light onto the outer circumferential portion of either one of the first member and the second member so that the other of the first member and the second member And a step of applying a force in a direction away from the member to at least partly peel the first member from the second member.

Japanese Laid-Open Patent Publication No. 2015-122370 (published on July 2, 2015)

In addition to the member peeling method described in Patent Document 1, there is a new method of separating the support from the laminate, while reducing the area irradiated with light to the separation layer (photo-thermal conversion layer) It is possible to quickly separate the support from the laminate while avoiding the irradiation of light to the circuit having the support. Therefore, the support separation method is desired.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a novel method for separating a support member from a laminate body while preventing light from being irradiated onto a circuit formed on the substrate It is on.

In order to solve the above problems, a supporting body separating method according to the present invention is a method for separating a supporting body from a laminate composed of a substrate, a support for transmitting light, and an adhesive layer and a separating layer deformed by absorbing light, Wherein the substrate has a circuit formation region in which a circuit is formed and a non-circuit formation region that surrounds the entire periphery of the circuit formation region and in which the circuit is not formed, wherein in the substrate, And at least a part of the separation layer which surrounds the entire circumference of the circuit formation region and is stacked so as to face a predetermined region occupying an area of 65% or more and less than 100% of the width in the radial direction of the non- A light irradiation step of irradiating light through a support, and a step of applying a force to the laminate to which the light is irradiated, Emitter and is characterized in that it comprises a separation step of separating the support.

According to the present invention, it is possible to provide a novel method for separating a support member from a laminate body while preventing light from being irradiated on a circuit formed on the substrate.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view for explaining an outline of a support separating method according to an embodiment of the present invention. FIG.
Fig. 2 is a view for explaining the outline of a region for irradiating light in the separation layer in the support separation method according to one embodiment of the present invention. Fig.
Fig. 3 is a view for explaining the outline of a light irradiation step which is included in a support separation method according to one embodiment and a modification of the present invention. Fig.
4 is a view for explaining an outline of an irradiation pattern of light in a support separation method according to an embodiment of the present invention.

 ≪ Support member separation method according to the first embodiment >

1 to 4, a support separating method according to an embodiment (first embodiment) of the present invention will be described in more detail.

As shown in Fig. 1A, a support separation method according to the present embodiment is a method of separating a substrate 1 made of silicon and a support plate (support) 2 made of silicon from an adhesive layer 3, The support plate 2 is separated from the laminate 10, which is formed by laminating a separating layer 4 which is deformed by absorbing the liquid L as shown in Fig. The laminate 10 has a circular shape when viewed from the top. The dicing tape 5 is stuck to the side of the substrate 1 and the dicing tape 5 is provided with a dicing frame 6. The dicing tape 5 has a dicing die-

As shown in Fig. 1 (b), the supporting body separating method according to the present embodiment includes a light irradiation step, and the light irradiation step is performed by alternately repeating the light irradiation step and the pivoting step The laser light L is irradiated to the entire region 4C of the layer 4 (Fig. 2 (a)). In the supporting body separating method according to the present embodiment, the turning step and the light irradiation step need not be performed simultaneously, and any of them may be performed first.

1 (c) and 1 (d), the supporting body separation method according to the present embodiment is a method in which a force is applied to the laminate 10 irradiated with the laser light L, And separating the plate (2).

[Light irradiation step]

The light irradiation step included in the support member separation method according to the present embodiment will be described in more detail. As shown in Fig. 1 (b) and Fig. 2 (a), in the light irradiation step, the light irradiation step and the pivoting step are alternately repeated to surround the entire circumference of the circuit formation region of the substrate 1, The support plate 2 is provided in the region 4C of the separation layer 4 stacked so as to face a predetermined region occupying 65% or more and less than 100% of the width in the radial direction of the circuit formation region Light is irradiated.

This makes it possible to reduce the area irradiated with the laser light (L) to the separation layer (4). Therefore, the time required for carrying out the light irradiation step can be shortened.

(Circuit forming region)

The circuit formation region means an area where a structure such as an integrated circuit is formed in the inner periphery of the substrate 1, for example. In the circuit formation region, the structure such as an integrated circuit is formed on the side of the substrate 1 that is exposed to the outside of the laminate 10 and the side of the substrate 1 opposite to the adhesive layer 3 Or both of them. The circuit formation region of the substrate 1 is arranged so as to face the region 4A located inwardly of the dotted line A1 in the separation layer 4 in the layered body 10 (a)).

(Non-circuit forming region)

The non-circuit forming region means a region surrounding the entire circumference of the circuit forming region of the substrate 1, outside the outer peripheral end of the circuit forming region, and occupying the inner side than the outer peripheral end of the substrate 1. The non-circuit forming region of the substrate 1 is arranged so as to face the region 4B located between the dotted line A1 and the dotted line A2 in the separation layer 4 in the laminated body 10 (Fig. 2 (a)). Here, the outer circumferential end of the substrate 1 is arranged on a dotted line A2 in the separation layer 4.

(Predetermined area)

The predetermined region is an area surrounding the whole circumference of the circuit formation area and occupying an area of 65% or more and less than 100% of the width in the radial direction of the non-circuit formation area, and means a region formed by the predetermined divided area. In the supporting body separating method according to the present embodiment, the inner circumferential end of the predetermined region of the substrate 1 is separated from the outer circumferential end of the circuit forming region, and the outer circumferential end of the predetermined region is the outer circumferential end of the substrate 1 . In the laminate 10, the predetermined region of the substrate 1 is disposed so as to face the region 4C located between the broken line B1 and the broken line B2 in the separation layer 4 2 (a)).

(Divided predetermined area)

The divided predetermined region means a region in which a predetermined region of the substrate 1 is equally divided at a predetermined angle with the center of the layered body 10 as a center. The divided predetermined regions of the substrate 1 are divided from the region 4C by the one-dot chain lines C1 to C3 in the separation layer 4 shown in Fig. 2 (a) Are arranged so as to correspond to the divided regions exemplified by the divided regions 4C-1 and 4C-2. The angle at which the predetermined area of the substrate 1 is evenly divided may be an angle which can be equally divided centered on the center point of the laminate 10 and may be, for example, 20 °, 30 °, or 45 ° More preferably 20 [deg.].

(Light irradiation step)

In the light irradiation step, light is irradiated to each divided region of the separation layer 4 via the support plate 2 in the layered product 10. For example, the laser light L is irradiated for each of the divided regions which are equally divided at a predetermined angle of 20 DEG. Thereby, the scanning range of the laser light L emitted from the laser irradiation device 50 can be narrowed, and the deformation of the shape of the irradiation pattern generated when the laser light L is scanned can be reduced. It is therefore possible to prevent the laser light L irradiated on the divided region 4C-1 of the separation layer 4 from being irradiated out of the divided region and to prevent the circuit formed on the substrate 1 and the dicing tape 5 can be preferably prevented from being irradiated with light.

3 (a), in the light irradiation step, a width W2 of not less than 65% and less than 100% of the non-circuit forming area having the width W1 in the radial direction of the substrate 1, The laser beam L is irradiated to the separation layer 4 opposed to the divided predetermined area occupying the area of the separation layer 4. The width W1 is also the width in the radial direction of the region 4B in the separation layer 4 shown in Fig. 2 (a). The width W2 is also the width in the radial direction of the divided region 4C-1 in the separation layer 4 shown in Fig. 2 (a).

The width W1 of the non-circuit forming area is appropriately set according to the size of the substrate. For example, if the substrate used in this embodiment has a diameter of about 300 mm (12 inches) More preferably greater than 1.0 mm and less than 3.0 mm, more preferably greater than 1.3 mm and less than 2.0 mm.

The width W2 of the divided predetermined region (in other words, the width of the divided region 4C-1 in the separation layer 4) is 65% or more and 100% or less of the width W1 of the non- , And it is preferable that the smaller the width W1, the larger the ratio of the width W2 to the width W1. Thereby, at least a part of the separation layer 4 can be altered so that the support plate 2 can be preferably separated from the laminate 10 by carrying out a separation process thereafter.

In the light irradiation step, when the laser light L is irradiated to the separation layer 4 in the region 4C-1 via the support plate 2, the laser light L is irradiated onto the separation layer 4 4 is transmitted through the separating layer 4 and is irradiated onto a predetermined divided region of the substrate 1. [ Here, in the substrate 1, the divided predetermined area occupying the width W2 is separated from the circuit formation area of the substrate 1. [ Therefore, it is possible to smoothly prevent the laser light L from being irradiated onto the circuit formed in the circuit formation area of the substrate 1, as compared with the case where the inside of the divided predetermined area is set to contact the circuit formation area. Therefore, it is possible to prevent the circuit from being damaged by the laser light L. In the substrate 1, the divided predetermined area occupying the width W2 is separated from the outer peripheral end of the substrate 1. [ Therefore, it is possible to smoothly prevent the laser light L from being irradiated outside the outer peripheral end of the substrate 1, as compared with the case where the outer peripheral end of the divided predetermined region is set to overlap the outer peripheral end of the substrate 1 . Therefore, it is possible to more preferably prevent the dicing tape 5 from being damaged by irradiating the dicing tape 5 located outside the outer peripheral end of the substrate 1 with the laser light L.

In the present specification, the "deteriorated" of the separation layer means a phenomenon in which the separation layer receives a slight external force and can be broken, or a state in which the adhesive force between the separation layer and the layer in contact with the separation layer is reduced . As a result of the deterioration of the separation layer caused by the absorption of light, the separation layer loses its strength or adhesion before being subjected to light irradiation. In short, by absorbing light, the separation layer 4 becomes fragile. The alteration of the separation layer may be such that the material constituting the separation layer causes decomposition by energy of the absorbed light, change of solid configuration, dissociation of functional groups, and the like. Deterioration of the separation layer 4 occurs as a result of absorption of light.

Therefore, for example, it is possible to easily detach the support plate from the substrate by altering the support plate to be destroyed only by lifting the support plate. More specifically, for example, one of the substrate and the support plate in the laminate is fixed to a mounting table by a support separating device or the like, and a suction pad (holding portion) provided with suction means The supporting plate and the substrate are separated or the chamfered portion of the end portion of the periphery of the support plate is held by a separating plate provided with a clamp or the like To separate the substrate and the support plate. In addition, for example, the support plate may be peeled off from the substrate in the laminate by the support separating apparatus provided with the peeling means for supplying the peeling liquid for peeling the adhesive. The peeling liquid is supplied to at least a part of the peripheral edge portion of the adhesive layer in the laminate by the peeling means and the adhesive layer in the laminate is swelled so that the force is concentrated on the separating layer at the time when the adhesive layer is swollen, Force can be applied to the substrate and the support plate. Therefore, the substrate and the support plate can be preferably separated.

The external force applied to the laminate, that is, the external force may be properly adjusted by the size of the laminate, the material of the support plate (support) such as glass and silicon, and the like. For example, about 0.1 to 5 kgf. By applying an external force of about 0.1 to 5 kgf, the substrate and the support plate can be preferably separated.

In the support material separation method according to the present embodiment, a CO ₂ laser (carbonic acid laser) is used as the laser light L for emitting light to the separation layer 4. This is because the laser beam L transmitted through the support plate 2 made of silicon can be generated.

The laser light irradiation condition in the light irradiation step preferably has an average output value of 1.0 W or more and 5.0 W or less, more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of the laser light is preferably 20 kHz or more and 60 kHz or less, more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10000 mm / s or less. Thereby, laser irradiation conditions can be set under appropriate conditions for deteriorating the separation layer 4. [

Here, as shown in Figs. 4 (a) to 4 (f), the irradiation pattern of the laser light L may be a line shape, a spiral shape, a polygonal dot shape, a circular dot shape, Is preferable. In the light irradiation step, an area of 50% or more of the area of the divided areas including the divided areas 4C-1 and 4C-2 is set between the broken lines B1 and B2 of the separating layer 4 in the radial direction An irradiation pattern of light is formed. As a result, the separation layer 4 in the divided region 4C-1 can be preferably deteriorated, making it vulnerable.

For example, as shown in Fig. 4 (a), when adopting a linear line-shaped pattern, the direction of the line-shaped pattern is not limited. If the pattern can be formed at 50% or more of the area of the divided area, the thickness of the line-shaped pattern and the number of lines are not limited. Among the respective patterns shown in Figs. 4 (a) to 4 (f), a linear line-shaped pattern is most preferable in that the irradiation time of the laser light L to the divided area can be shortened most.

As shown in Fig. 4 (b), the irradiation pattern of the laser light L may be a helical pattern. The line-shaped pattern for drawing the helix can be continuously formed in the divided region of the separation layer 4 like the line-shaped pattern, and the irradiation time of the laser light L can be shortened desirable. In addition, when irradiating the divided region 4C-1 of the separation layer 4, a spiral pattern generates a spot where the laser light L is irradiated in a redundant manner. However, in the support member separation method according to the present embodiment, since the laser light L transmitted through the separation layer 4 is irradiated on the predetermined divided area of the substrate 1, The dicing tape 5 is not irradiated. Therefore, the integrated circuit formed on the substrate 1 and the dicing tape 5 can be formed at a position where the irradiation output of the laser light L is excessively weakened at the point where the laser light L is irradiated repeatedly It is possible to prevent damage.

As shown in Fig. 4 (c), the irradiation pattern of the laser light L may be a polygonal dot shape, for example, a rectangular dot shape. Here, the size of each dot of the rectangular dot shape is not limited as long as the pattern can be formed so as to occupy an area of 50% or more of the area of the divided area in the inner peripheral portion of the divided area 4C-1. Similarly, as shown in Fig. 4 (d), the irradiation pattern of the laser light L may be in the form of a dot. The dot-like pattern such as the polygonal dot shape and the original dot shape is preferable in that it is possible to shorten the irradiation time to the divided area subsequent to the line shape, and to form a precise pattern in the divided area.

4 (e), the irradiation pattern of the laser light L may be a polygonal ring shape. 4 (f), the irradiation pattern of the laser light L may be ring-shaped. By forming these multiple ring-shaped and ring-shaped patterns, the separation layer 4 in the division region 4C-1 can be preferably altered. Also, in each ring-shaped pattern, the thickness of the ring-shaped pattern and the size of the pattern can be appropriately adjusted.

(Conversion step)

The turning step is a step in which the layered product 10 irradiated with the laser light L in the divided region is irradiated with the laser light so that the plane of the layered product 10 is set at a predetermined As shown in Fig. In the support member separation method according to the present embodiment, the region 4C in the separation layer 4 is equally divided into 20 degrees which is a predetermined angle. Therefore, in the rotating step, the layered product 10 irradiating the laser light L to the divided region 4C-1 of the separation layer 4 is rotated at a predetermined angle of 20 DEG by the light irradiation step. Thus, the laser irradiation device 50 is arranged on the divided region 4C-2 of the separation layer 4 in the laminate 10. [

Thereafter, the separation layer 4 in the divided region 4C-2 is altered by the light irradiation step. Further, the rotating step and the light irradiation step are alternately repeated to irradiate the entire region 4C of the separation layer 4 with laser light L.

The dicing tape 5 with the dicing frame 6 is stuck to the substrate 1 side and the laminated body 10 is provided with a porous portion, (Not shown) or the like, and may be rotated at a predetermined angle.

[Separation Process]

In the separation step, a force is applied to the laminate 10 irradiated with the laser light L to separate the support plate 2 from the laminate 10 (Fig. 1 (c)). More specifically, for example, in a state in which the substrate 1 side of the laminate 10 is fixed by a rotatable stage, a separation plate (holding portion, not shown) provided with a suction pad such as a bellows pad Thereby lifting the separating plate while holding the upper surface portion of the support plate 2 by suction. Thereby, a force is applied to the laminate (10) to separate the support plate (2) from the laminate (10).

In the supporting member separation method according to the present embodiment, in the light irradiation step, the light irradiation step and the pivoting step are carried out alternately to deteriorate the separation layer 4 in the entire region 4C. That is, in the layered product 10, the entire periphery of the separation layer 4 is altered. Therefore, after the light irradiation step, the peripheral edge portion of the support plate 2 in the laminate 10 can be held without specifying the direction of the laminate 10, and the separation step can be performed. In addition, in the separation step, when a force is applied to the laminate 10, the force concentrates on the detached separation layer 4 in the region 4C. Thereby, the separation layer 4 in the region 4C is first broken and the force is concentrated on the separation layer 4 other than the region C so that the separation layer 4 other than the region C ) Is destroyed. Thereby, the support plate 2 can be preferably separated from the laminate 10.

In the separation step, the support plate 2 is separated from the laminate 10 by lifting the separation plate, for example, through a joint (not shown) such as a floating joint or a universal joint. Such a joint is movable to be tiltable with respect to the plane of the laminate 10 which is rotatable and fixed to the stage.

When a force is applied to the laminate 10 from the separation plate via a floating joint or the like, when the force concentrates on a part of the outer peripheral end of the laminate 10, the floating joint is activated, The separation plate is inclined such that the adsorption pad faces the surface contacting the support plate 2. Along with this, the support plate 2 on the way of being separated from the laminate 10 tilts. As a result, excessive force can be prevented from being exerted on the support plate 2 and a part of the substrate 1, and force can be applied to the separation layer 4 stacked between the support plate 2 and the adhesive layer 3 Can concentrate. Therefore, it is possible to peel off the support plate 2 from the substrate 1 preferably while preventing the support plate 2 and the substrate 1 from being damaged by excessive force.

[Other processes]

After the separation process is performed, the substrate 1 on which the support plate 2 shown in Fig. 1 (d) is separated is peeled off, for example, in a state where the dicing tape 5 is attached, A cleaning step of removing residues of the adhesive layer 3 and the separation layer 4 is performed by a liquid or the like. After the cleaning process, a dicing process for manufacturing a semiconductor chip is performed from the substrate 1 to which the dicing tape 5 is pasted. Here, the dicing tape 5 attached to the substrate 1 is prevented from being damaged by irradiation with the laser light L. Therefore, according to the supporting body separating method according to the present embodiment, a series of processes from the substrate 1 to a semiconductor chip can be smoothly performed in a state where the dicing tape 5 is attached to the laminate 10 . Therefore, in the step of forming the circuit on the substrate 1, the thinned substrate 1 can be prevented from being damaged when the dicing tape 5 is attached.

[Layered product (10)]

The laminate 10 used in the support member separation method according to the present embodiment will be described in more detail. The laminate 10 is formed by laminating a substrate 1, an adhesive layer 3, a separation layer 4, and a support plate 2 in this order.

[Substrate (1)]

In the support member separation method according to the present embodiment, a wafer substrate made of silicon is used as the substrate 1. The substrate 1 can be provided in processes such as thinning and mounting while being supported on the support plate 2 via the adhesive layer 3 and the separation layer 4. [ In addition, in the circuit formation region of the substrate 1, for example, a structure such as an integrated circuit or a metal bump is mounted.

In the support member separation method according to the present embodiment, a silicon wafer substrate is used as the substrate. However, the substrate 1 is not limited to a silicon wafer substrate but may be any substrate such as a ceramics substrate, a thin film substrate, A substrate made of a material may be used.

[Support plate (2)]

The support plate (support) 2 is a support for supporting the substrate 1 and is attached to the substrate 1 with the adhesive layer 3 interposed therebetween. Therefore, the support plate 2 may have a strength required for preventing breakage or deformation of the substrate 1 during the process of thinning, transportation, and mounting of the substrate 1. It is also possible to transmit light for altering the separation layer 4.

A support plate made of glass, silicon, or acrylic resin can be used as the support, but in the support separation method according to this embodiment, the support plate 2 made of silicon is used. The difference in thermal expansion coefficient between the substrate 1 and the support plate 2 can be reduced by stacking the support plate 2 made of silicon on the substrate 1 to reduce the warpage of the laminate 10 by heating It is because.

The support plate 2 is provided with a cutout (notch, not shown) for specifying the direction of the support plate 2.

[Adhesive Layer (3)]

The adhesive layer 3 is used to adhere the substrate 1 and the support plate 2 on which the separation layer 4 is formed. The adhesive layer 3 is a layer formed by an adhesive used for bonding the substrate 1 and the support plate 2.

The thickness of the adhesive layer 3 may be suitably set according to the type of the substrate 1 and the support plate 2 to be adhered and the treatment to be performed on the substrate 1 after the application, And more preferably in the range of 15 to 100 占 퐉.

The adhesive layer 3 can be formed by applying an adhesive by a method such as spin coating, dipping, roller blade, spray coating, slit coating, or the like. The adhesive layer 3 is formed by pasting a film (so-called dry film) on which an adhesive is applied on both surfaces in advance, to the substrate 1, instead of applying the adhesive directly to the substrate 1 .

As the adhesive for forming the adhesive layer 3, various adhesives known in the art such as acrylic, novolac, naphthoquinone, hydrocarbon, polyimide, elastomer and polysulfone can be used .

The resin contained in the adhesive, that is, the resin contained in the adhesive layer 3, may be any resin having adhesiveness, and examples thereof include a hydrocarbon resin, an acryl-styrene resin, a maleimide resin, an elastomer resin, A phthalic resin, and the like, or a combination thereof may be more preferably used. Hereinafter, the composition of the resin contained in the adhesive layer 3 in the present embodiment will be described.

(Hydrocarbon resin)

The hydrocarbon resin is a resin having a hydrocarbon skeleton and polymerizing the monomer composition. (Hereinafter sometimes referred to as " resin (A) ") and at least one resin selected from the group consisting of terpene resin, rosin resin and petroleum resin (B) "), but the present invention is not limited to this.

The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin-based monomer. Specific examples thereof include a ring-opening (co) polymer of a monomer component containing a cycloolefin-based monomer, and a resin obtained by addition (co) polymerization of a monomer component containing a cycloolefin-based monomer.

Examples of the cycloolefin-based monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, dicyclopentadiene, hydroxydicyclopentadiene and the like (Methyl, ethyl, propyl, butyl (meth) acrylate of a cyclic compound such as a cyclic compound such as a cyclic compound such as cyclopentadiene or cyclopentadiene or a cyclic compound such as a cyclic compound such as a cyclic compound Etc.), alkenyl (vinyl, etc.) substituents, alkylidene (ethylidene etc.) substituents, aryl (phenyl, tolyl, naphthyl, etc.) substituents and the like. Of these, norbornene monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl substituents thereof are particularly preferable.

The monomer component constituting the resin (A) may contain other monomer copolymerizable with the cycloolefin-based monomer described above, and preferably contains, for example, an alkene monomer. Examples of the alkene monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene, and -olefin. The alkene monomer may be linear or branched.

In addition, it is preferable that a monomer component constituting the resin (A) contains a cycloolefin monomer in view of high heat resistance (low thermal decomposition and thermogravimetric reduction). The proportion of the cycloolefin monomer to the whole monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more. The ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is not particularly limited, but from the viewpoints of solubility and stability over time in the solution, it is preferably 80 mol% or less, more preferably 70 mol% Is more preferable.

The monomer component constituting the resin (A) may contain linear or branched alkene monomers. The proportion of the alkene monomer to the whole monomer component constituting the resin (A) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, still more preferably from 30 to 80 mol%, from the viewpoints of solubility and flexibility, Is more preferable.

The resin (A) is, for example, a resin having no polar group, such as a resin obtained by polymerizing a monomer component comprising a cycloolefin-based monomer and an alkene monomer. In suppressing the generation of gas under high temperature desirable.

The polymerization method, polymerization conditions, and the like at the time of polymerizing the monomer component are not particularly limited and may be suitably set according to a conventional method.

For example, a cycloolefin copolymer which is a copolymer of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2) can be used as the resin (A) of the adhesive component.

[Chemical Formula 1]

(In the general formula (2), n is 0 or an integer of 1 to 3)

As such cycloolefin copolymers, APL 8008T, APL 8009T, and APL 6013T (both manufactured by Mitsui Chemicals, Inc.) can be used.

Examples of commercially available products that can be used as the resin (A) include "TOPAS" manufactured by Polyplastics Co., Ltd., "APEL" manufactured by Mitsui Chemicals, Inc., "ZEONOR" and "ZEONEX" manufactured by Nippon Zeon Co., &Quot; ARTON " manufactured by Kokusan Co., Ltd., and the like.

The glass transition temperature (Tg) of the resin (A) is preferably 60 占 폚 or higher, and particularly preferably 70 占 폚 or higher. When the glass transition temperature of the resin (A) is 60 DEG C or more, softening of the adhesive layer (3) can be further suppressed when the laminate is exposed to a high temperature environment.

The resin (B) is at least one resin selected from the group consisting of a terpene resin, a rosin resin and a petroleum resin. Specifically, examples of the terpene resin include a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, a hydrogenated terpene phenol resin, and the like. Examples of the rosin-based resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of the petroleum resin include an aliphatic or aromatic petroleum resin, a hydrogenated petroleum resin, a modified petroleum resin, an alicyclic petroleum resin, a coumarone-indene petroleum resin, and the like. Of these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferable.

The softening point of the resin (B) is not particularly limited, but is preferably 80 to 160 ° C. When the softening point of the resin (B) is 80 to 160 占 폚, the laminate can be prevented from being softened when exposed to a high temperature environment, and adhesion failure is not caused.

The weight average molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance becomes sufficient, and the amount of degassing is reduced in a high temperature environment. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the dissolution rate of the adhesive layer to the hydrocarbon solvent becomes good. Therefore, the residue of the adhesive layer on the substrate after separating the support plate can be quickly dissolved and removed. The weight average molecular weight of the resin (B) in the present embodiment means the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

As the resin, a mixture of the resin (A) and the resin (B) may be used. By mixing, the heat resistance becomes good. For example, the mixing ratio of the resin (A) and the resin (B) is preferably from 80:20 to 55:45 (mass ratio) of (A) :( B) Which is preferable.

(Acrylic-styrenic resin)

Examples of the acryl-styrene type resin include resins obtained by polymerizing a derivative of styrene or styrene with (meth) acrylic acid ester as a monomer.

(Meth) acrylic esters include, for example, (meth) acrylic acid alkyl esters having a chain structure, (meth) acrylic esters having aliphatic rings, and (meth) acrylic esters having aromatic rings. Examples of the (meth) acrylic acid alkyl ester having a chain structure include an acrylic long-chain alkyl ester having an alkyl group having a carbon number of 15 to 20 and an acrylic alkyl ester having an alkyl group having a carbon number of 1 to 14. Examples of the acrylic long chain alkyl ester include acrylic acid or methacrylic acid in which the alkyl group is n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, Of alkyl esters. The alkyl group may be branched.

Examples of acrylic alkyl esters having an alkyl group of 1 to 14 carbon atoms include known acrylic alkyl esters used in conventional acrylic adhesives. For example, when the alkyl group is an acrylic acid or methacrylic acid group such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, And alkyl esters of acrylic acid.

Examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) (Meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like can be given, but isobornyl methacrylate, Cyclopentanyl (meth) acrylate is more preferable.

The (meth) acrylic ester having an aromatic ring is not particularly limited, and examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, , A phenoxyethyl group, and the like. The aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.

(Maleimide resin)

Examples of the maleimide-based resin include monomers such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N- N-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-heptylmaleimide, N-heptylmaleimide, N-heptylmaleimide, N-tert-butylmaleimide, Maleimide having an alkyl group such as stearyl maleimide, N-cyclopropyl maleimide, N-cyclobutyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-cycloheptyl maleimide, N- Maleimide having an aliphatic hydrocarbon group such as cyclooctylmaleimide, aromatic maleimide having an aryl group such as N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide and Np-methylphenylmaleimide, etc. Can be .

(Elastomer)

The elastomer preferably contains a styrene unit as a constitutional unit of the main chain, and the " styrene unit " may have a substituent. Examples of the substituent include an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxyalkyl group of 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group. It is more preferable that the content of the styrene unit is within a range of 14 wt% or more and 50 wt% or less. The elastomer preferably has a weight average molecular weight of 10,000 or more and 200,000 or less.

When the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, it is easily dissolved in the hydrocarbon solvent described later Also, the adhesive layer can be quickly removed. When the content of the styrene unit and the weight average molecular weight fall within the above ranges, resist solvents (for example, PGMEA, PGME, etc.) exposed when the wafer substrate is provided to the resist lithography process, acids (hydrofluoric acid, etc.) TMAH and the like).

The above-mentioned (meth) acrylic acid ester may be further mixed in the elastomer.

The content of the styrene unit is more preferably 17% by weight or more, and still more preferably 40% by weight or less.

A more preferable range of the weight average molecular weight is 20,000 or more, and a more preferable range is 150,000 or less.

As the elastomer, various elastomers can be used so long as the styrene unit content is in the range of 14 wt% or more and 50 wt% or less and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000. Styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymers (Styrene-isoprene-styrene block copolymer) (hereinafter referred to as " styrene-ethylene-styrene block copolymer " SEPE), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene block copolymer styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461, manufactured by Kuraray Co., Ltd., Septon V9475 Styrene block copolymer having a reactive styrene block (Septon V9827 (manufactured by Kuraray Co., Ltd.) having a reactive polystyrene-based hard block), styrene-ethylene-butylene- (Ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group-modified), and the elastomer having a styrene unit content and a weight average molecular weight within the above- have.

Among the elastomers, hydrous materials are more preferable. If it is a water-soluble material, stability against heat is improved, and deterioration such as decomposition or polymerization does not occur. It is more preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a resist solvent.

Further, among the elastomers, styrene block polymers at both ends are more preferable. This is because styrene having high heat stability is blocked at both ends to exhibit higher heat resistance.

More specifically, it is more preferable that the elastomer is a hydrogenated product of a block copolymer of styrene and a conjugated diene. The stability to heat is improved, and deterioration such as decomposition or polymerization does not occur well. Further, styrene having high thermal stability is blocked at both ends to exhibit higher heat resistance. From the viewpoints of solubility in a hydrocarbon solvent and resistance to a resist solvent.

Examples of commercially available products that can be used as the elastomer contained in the adhesive constituting the adhesive layer 3 include "Septon (trade name)" manufactured by Kuraray Co., Ltd., "Hiabra (trade name)" manufactured by Kuraray Co., Ltd., (Trade name) manufactured by JSR Corporation, and DYNARON (trade name) manufactured by JSR Corporation.

The content of the elastomer contained in the adhesive constituting the adhesive layer 3 is preferably from 50 parts by weight to 99 parts by weight, more preferably from 60 parts by weight or more, for example, 100 parts by weight as the total amount of the adhesive composition , 99 parts by weight or less, and most preferably 70 parts by weight or more and 95 parts by weight or less. By making these ranges fall within this range, the substrate and the support plate can be preferably bonded together while maintaining the heat resistance.

The elastomer may be mixed with a plurality of kinds. In short, the adhesive constituting the adhesive layer 3 may contain a plurality of kinds of elastomers. At least one of the plural kinds of elastomers may contain a styrene unit as a constitutional unit of the main chain. When at least one of the plural kinds of elastomers has a styrene unit content of 14 wt% or more and 50 wt% or less, or a weight average molecular weight of 10,000 or more and 200,000 or less, to be. When a plurality of kinds of elastomers are contained in the adhesive constituting the adhesive layer 3, the content of the styrene units may be adjusted so as to be in the above range as a result of mixing. For example, when Septon 4033 (trade name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon 2063 (trade name) having a styrene unit content of 13% by weight are mixed at a weight ratio of 1: 1, The content of styrene relative to the total amount of the elastomer contained in the adhesive is 21 to 22% by weight, and therefore 14% by weight or more. For example, when the styrene unit is 10 wt% and 60 wt% is mixed in a weight ratio of 1: 1, it becomes 35 wt%, which is in the above range. The present invention may be of such a form. It is most preferable that the plurality of kinds of elastomers contained in the adhesive constituting the adhesive layer 3 contain styrene units within the above-mentioned range, and the weight average molecular weight within the above range is the most preferable.

Further, it is preferable to form the adhesive layer 3 using a resin other than the photocurable resin (for example, UV curable resin). By using a resin other than the photocurable resin, it is possible to prevent residues from being formed around the minute unevenness of the substrate 1 after the peeling or removal of the adhesive layer 3. In particular, as the adhesive constituting the adhesive layer 3, it is preferable that the adhesive is not dissolved in all the solvents but dissolved in a specific solvent. This is because the adhesive layer 3 can be removed by dissolving the adhesive layer 3 in a solvent without applying a physical force to the substrate 1. The adhesive layer 3 can be easily removed without damaging or deforming the substrate 1 even on the substrate 1 whose strength has been reduced at the time of removing the adhesive layer 3. [

(Polysulfone resin)

The adhesive for forming the adhesive layer 3 may contain a polysulfone resin. By forming the adhesive layer 3 with a polysulfone resin, it is possible to produce a laminate capable of peeling the support plate from the substrate by dissolving the adhesive layer in subsequent steps even if the laminate is treated at a high temperature. When the adhesive layer 3 contains a polysulfone resin, the laminate can be preferably used also in a high-temperature process for treating the laminate at a high temperature of 300 DEG C or higher, for example, by annealing or the like.

The polysulfone resin has a structure composed of at least one constituent unit of a constituent unit represented by the following general formula (3) and a constituent unit represented by the following general formula (4).

(2)

(Wherein R ¹ , R ² and R ³ in the general formula (3) and R ¹ and R ² in the general formula (4) are each independently selected from the group consisting of a phenylene group, a naphthylene group and an anthrylene group And X 'is an alkylene group having a carbon number of 1 or more and 3 or less)

The polysulfone resin includes at least one of the polysulfone constituent unit represented by the formula (3) and the polyether sulfone constituent unit represented by the formula (4), whereby the substrate 1 and the support plate 2 are bonded to each other It is possible to form a laminate capable of preventing insolubilization of the adhesive layer 3 by decomposition, polymerization or the like even if the substrate 1 is treated under a high temperature condition. The polysulfone resin is stable even when heated to a higher temperature as long as it is a polysulfone resin composed of the polysulfone constituent unit represented by the above formula (3). Therefore, residues caused by the adhesive layer on the cleaned substrate 1 can be prevented.

The weight average molecular weight (Mw) of the polysulfone resin is preferably 30,000 or more and 70,000 or less, more preferably 30,000 or more and 50,000 or less. When the weight average molecular weight (Mw) of the polysulfone resin is within a range of 30,000 or more, an adhesive composition which can be used at a high temperature of, for example, 300 DEG C or more can be obtained. When the weight average molecular weight (Mw) of the polysulfone resin is within a range of 70,000 or less, it can be preferably dissolved by a solvent. In short, an adhesive composition which can be preferably removed by a solvent can be obtained.

(Diluting solvent)

Examples of the diluting agent for use in forming the adhesive layer 3 include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane and tridecane, Cyclic hydrocarbon such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; and cyclic hydrocarbons such as p-menthane, o-menthane, m- Phenylenemethane, 1,4-terpine, 1,8-terpine, borane, norbornane, pyrazine, bullzan, karan, longpolene, geraniol, nerol, linalool, citral, But are not limited to, menthol, isomenthol, neomenthol,? -Terpineol,? -Terpineol,? -Terpineol, terpinene-1-ol, terpinene- Terpene solvents such as cineol, 1,8-cineol, borneol, carbone, yonon, toluene, campa, d-limonene, l-limonene and dipentene; lactones such as? -butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; A compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; a monomethyl ether, monoethyl ether, Monoalkyl ethers such as monopropyl ether and monobutyl ether, and compounds having an ether bond such as monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); Cyclic ethers such as dioxane and esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate Ryu; Aromatic organic solvents such as anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether and the like.

(Other components)

The adhesive constituting the adhesive layer 3 may further contain another miscible substance in a range that does not impair the essential properties. For example, various additives commonly used such as an additive resin for improving the performance of the adhesive, a plasticizer, an adhesion promoter, a stabilizer, a colorant, a thermal polymerization inhibitor and a surfactant may be further used.

[Separation layer (4)]

Next, the separation layer 4 is a layer formed of a material which changes by absorbing light irradiated via the support plate 2. [

The thickness of the separation layer 4 is more preferably in the range of 0.05 탆 or more and 50 탆 or less, and more preferably in the range of 0.3 탆 or more and 1 탆 or less. If the thickness of the separation layer 4 is in the range of 0.05 탆 or more and 50 탆 or less, desired deterioration can be caused in the separation layer 4 by irradiation with light for a short time and irradiation with low energy light. It is particularly preferable that the thickness of the separation layer 4 is in the range of 1 占 퐉 or less from the viewpoint of productivity.

Further, another layer may be additionally formed between the separation layer 4 and the support plate 2 in the layered product 10. In this case, the other layer may be made of a material that transmits light. Thus, it is possible to appropriately add a layer which gives desirable properties to the laminate 10 without interfering with the incidence of light into the separation layer 4. Depending on the kind of the material constituting the separation layer 4, the wavelength of the usable light is different. Therefore, the material constituting the other layer is not necessarily required to transmit all the light, but can be appropriately selected from a material capable of transmitting light having a wavelength capable of deteriorating the material constituting the separation layer 4.

Although it is preferable that the separation layer 4 is formed only of a material having a structure that absorbs light, it is preferable to use a material that does not have a structure that absorbs light in the range that does not impair the essential characteristics of the present invention The separation layer 4 may be formed. It is preferable that the separation layer 4 has a flat surface (not provided with unevenness) on the side opposite to the adhesive layer 3, whereby the separation layer 4 can be easily formed, It is possible to evenly apply the adhesive sheet to the adhesive sheet.

The separation layer 4 may be appropriately selected depending on the kind of the substrate and the support plate 2, and the performance required for the laminate. In the support member separation method according to the present embodiment, the separation layer denatured by the CO ₂ laser capable of transmitting infrared rays capable of transmitting the support plate 2 made of silicon among the separation layers shown below is more preferably Can be used.

(Fluorocarbon)

The separating layer 4 may be made of fluorocarbon. The separation layer 4 is constituted by fluorocarbons, so that the separation layer 4 is deteriorated by absorbing light, and as a result, the separation layer 4 loses its strength or adhesiveness before it is irradiated with light. Therefore, the separating layer 4 is broken by applying a slight external force (for example, lifting the support plate 2), so that the support plate 2 and the substrate 1 can be easily separated from each other . The fluorocarbon constituting the separation layer 4 can be preferably formed by a plasma CVD (chemical vapor deposition) method.

Fluorocarbon absorbs light having a wavelength in a specific range depending on its kind. By irradiating the separation layer with light having a wavelength in the range that the fluorocarbon used in the separation layer 4 absorbs, the fluorocarbon can be preferably altered. It is preferable that the light absorption rate in the separation layer 4 is 80% or more.

As the light to be irradiated to the separation layer 4, a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, or the like may be used depending on the wavelength at which the fluorocarbon can be absorbed. A gas laser such as a liquid laser such as a laser, a CO ₂ laser, an excimer laser, an Ar laser, or a He-Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be suitably used. The wavelength at which the fluorocarbon can be altered is not limited to this. For example, a wavelength in the range of 600 nm or less can be used.

(A polymer containing a structure having light absorptivity in the repeating unit)

The separation layer 4 may contain a polymer containing a structure having light absorption properties in the repeating unit. The polymer is altered by light irradiation. The deterioration of the polymer occurs when the structure absorbs the irradiated light. The separation layer 4 loses strength or adhesiveness before irradiation with light as a result of alteration of the polymer. Therefore, the separating layer 4 is broken by applying a slight external force (for example, lifting the support plate 2), so that the support plate 2 and the substrate 1 can be easily separated from each other .

The above structure having light absorption property is a chemical structure which absorbs light and changes a polymer containing the structure as a repeating unit. The structure thereof is, for example, an atomic group containing a conjugated pi-electron system comprising a substituted or unsubstituted benzene ring, a condensed ring or a heterocyclic ring. More specifically, the structure may be a carbodiimide structure or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (biphenyl sulfone structure), a diphenyl structure or a diphenylamine structure in a side chain of the polymer Structure.

When the structure is present in the side chain of the polymer, its structure can be represented by the following formula.

(3)

(Wherein, R is each independently an alkyl group, an aryl group, a halogen, a hydroxyl group, a ketone group, a sulfoxide group, a sulfone group or an ^{N (R 4) (R 5} ) , and (wherein, R ⁴ and R ⁵ are each independently is a hydrogen atom or an alkyl group having a carbon number of 1-5), Z is absent, or -CO-, -SO ₂ -, and -SO- or -NH-, n is an integer of 0 or 1 to 5)

The polymer may contain, for example, a repeating unit represented by any one of the following formulas (a) to (d), or may be represented by (e) It is contained in the main chain.

[Chemical Formula 4]

(1) wherein l is an integer of 1 or more, m is 0 or an integer of 1 to 2, X is any one of the formulas shown in the above formula (3) in (a) to (e) And Y ₁ and Y ₂ are each independently -CO- or SO ₂ -, and l is preferably an integer of 10 or less.

Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above-mentioned "Formula 3" include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, , Substituted acridine, azobenzene, substituted azobenzene, fluoride, substituted fluoride, fluorimone, substituted fluorimone, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenan Threne, substituted phenanthrene, pyrene and substituted pyrene. When the exemplified substituent further has a substituent, the substituent can be, for example, an alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amide, dialkylamino, sulfonamide, imide, Acid, carboxylic acid ester, sulfonic acid, sulfonic acid ester, alkylamino and arylamino.

Among the substituents represented by the above-mentioned "Formula 3 ", examples of the case where Z is -SO ₂ - as the fifth substituent having two phenyl groups include bis (2,4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (Hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone.

Among the substituents represented by the above-mentioned "Formula 3 ", examples of the case where Z is -SO- as the fifth substituent having two phenyl groups include bis (2,3-dihydroxyphenyl) sulfoxide, bis Dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxyphenyl) sulfoxide, bis (2,5-dihydroxyphenyl) sulfoxide, bis (3,4-dihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxy- Bis (2,4,6-trihydroxyphenyl) sulfoxide, bis (2,4,6-trihydroxyphenyl) sulfoxide, bis .

Among the substituents represented by the above-mentioned "Formula 3 ", examples of the case where Z is -C (= O) - as a fifth substituent having two phenyl groups include 2,4- Tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 5,6'-tetrahydroxybenzophenone, 2-hydroxy-4- 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-di Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-dimethylamino- Hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2 ', 4'-dihydro Hydroxybenzophenone, and 4-dimethylamino-3 ', 4'-dihydroxybenzophenone.

When the structure is present in the side chain of the polymer, the proportion of the repeating unit containing the structure in the polymer is in the range of not less than 0.001% and not more than 10% of the light transmittance of the separation layer 4 . If the polymer is prepared so that the ratio falls within such a range, the separating layer 4 absorbs light sufficiently and can be surely and quickly deteriorated. That is, it is easy to remove the support plate 2 from the laminate 10, and it is possible to shorten the irradiation time of the light necessary for the removal.

The structure can absorb light having a wavelength in a desired range according to the selection of the kind. For example, the wavelength of the absorbable light of the above structure is more preferably in the range of 100 nm or more and 2,000 nm or less. Within this range, the wavelength of the light absorbable by the above structure is on the shorter wavelength side, for example, in the range of 100 nm or more and 500 nm or less. For example, the structure may deform the polymer containing the structure, preferably by absorbing ultraviolet light having a wavelength within a range of about 300 nm to 370 nm inclusive.

(Wavelength: 254 nm or more, 436 nm or less), KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F2 excimer laser (Wavelength: 157 nm), XeCl laser (wavelength: 308 nm), XeF laser (wavelength: 351 nm), or solid UV laser (wavelength: 355 nm) Line (wavelength: 405 nm) or an i-line (wavelength: 365 nm).

Although the above-described separation layer 4 contains a polymer containing the above structure as a repeating unit, the separation layer 4 may further contain components other than the polymer. Examples of the components include fillers, plasticizers, and components capable of improving the releasability of the support plate 2 and the like. These components are appropriately selected from conventionally known materials or materials that do not interfere with or accelerate the absorption of light by the above structure and the deterioration of the polymer.

(Mineral)

The separation layer 4 may be made of an inorganic material. The separating layer 4 is constituted by an inorganic substance, so that it is deformed by absorbing light, and as a result, the separating layer 4 loses strength or adhesiveness before light irradiation. Therefore, the separating layer 4 is broken by applying a slight external force (for example, lifting the support plate 2), so that the support plate 2 and the substrate 1 can be easily separated from each other .

The inorganic material may be modified so as to absorb light. For example, one or more inorganic materials selected from the group consisting of metals, metal compounds and carbon may be preferably used. The metal compound refers to a compound containing a metal atom, and may be, for example, a metal oxide or a metal nitride. In this example of such minerals it includes, but are not limited to this, but gold is selected from copper, iron, nickel, aluminum, titanium, chromium, SiO _2, SiN, Si ₃ N _4, the group consisting of TiN, and carbon And at least one kind of inorganic substance. Also, carbon is a concept that can include carbon isotopes, and can be, for example, diamond, fullerene, diamond like carbon, carbon nanotubes, and the like.

The inorganic material absorbs light having a wavelength in a specific range depending on the kind thereof. By irradiating the separation layer with light having a wavelength in the range that the inorganic material used in the separation layer 4 absorbs, the inorganic material can be preferably altered.

As the light to be irradiated to the separation layer 4 made of an inorganic material, a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, , A liquid laser such as a dye laser, a gas laser such as a CO ₂ laser, an excimer laser, an Ar laser or a He-Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam.

The separation layer 4 made of an inorganic material can be formed on the support plate 2 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating or the like. The thickness of the separating layer 4 made of an inorganic material is not particularly limited and may be any thickness that can sufficiently absorb the light to be used. For example, it is preferable that the thickness of the separating layer 4 is in the range of 0.05 mu m or more and 10 mu m or less desirable. An adhesive may be applied to both surfaces or one side of an inorganic film (for example, a metal film) made of an inorganic material constituting the separation layer 4 in advance, and the support plate 2 and the substrate 1 may be pasted.

Further, when a metal film is used as the separation layer 4, reflection of the laser or electrification of the film may occur depending on conditions such as the film quality of the separation layer 4, the type of the laser light source, the laser output, and the like . Therefore, it is preferable to form an antireflection film or an antistatic film on the upper or lower part of the separation layer 4, or to take measures against them.

(A compound having an infrared absorbing structure)

The separation layer 4 may be formed by a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. As a result of the deterioration of the compound, the separation layer 4 loses its strength or adhesiveness before being irradiated with infrared rays. Therefore, the separating layer 4 is broken by applying a slight external force (for example, lifting the support plate 2), so that the support plate 2 and the substrate 1 can be easily separated from each other .

Examples of the compound containing a structure having an infrared absorbing property or a structure having an infrared absorbing property include an alkane, an alkene (vinyl, a trans, a cis, a vinylidene, a trisubstituted, a tetrasubstituted, a conjugated, Alcohol, and phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds, saturated secondary alcohols, saturated aliphatic alcohols), monocyclic aromatic (benzene, monosubstituted, Unsaturated secondary, and tertiary unsaturated), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ring ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3 (Dicarboxylic acid anhydrides), formic acid esters, acetic acid esters, conjugated esters, non-conjugated esters, aromatic esters, carboxylic acid esters, Lactones (? -,? -,? -), (Aliphatic, aromatic, aliphatic, aromatic, aliphatic, aromatic, or aromatic), an aliphatic acid chloride, an aromatic acid chloride, an acid anhydride (conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, Aromatic amines, aliphatic amines, aliphatic amines, aliphatic amines, aliphatic amines, aromatic amines, aromatic amines, aliphatic amines, aliphatic amines, aliphatic amines, An aliphatic nitro compound, an aromatic nitro compound, a nitroamine, a nitrosoamine, a nitrate ester, a nitrite ester, a nitroso bond, a nitrile bond, a nitrile bond, an isocyanate bond, a nitrile bond, an isocyanate bond, a thiocyanate bond, an aliphatic isothiocyanate bond, an aromatic isothiocyanate bond, (Aliphatic, aromatic, monomeric, dimeric), mercaptans and sulfur compounds such as thiophenol and thiol acid, thiocarbonyl groups, sulfoxide, sulfone, sulfonyl chloride, primary sulfonamides, secondary Sulfonamides, sulfate esters, the carbon-halogen bond, a bond Si-A ¹ (A ¹ is H, C, O, or halogen), PA ² bond (A ² is H, C, or O), or be a Ti-O bond have.

The structure containing the carbon-halogen bond includes, for example, -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH═CF ₂ , -CF═CF _{2 2} , fluoroaryl, and aryl chloride.

A structure containing the combination Si-A ¹ _{is, SiH, SiH 2, SiH 3} , Si-CH 3, Si-CH 2 -, Si-C 6 H 5, SiO- aliphatic, Si-OCH _3, Si- OCH ₂ CH ₃ , Si-OC ₆ H ₅ , Si-O-Si, Si-OH, SiF, SiF ₂ and SiF ₃ . The structure containing a Si-A ¹ bond preferably forms a siloxane skeleton and a silsesquioxane skeleton.

A structure containing the PA ² is _{coupled, PH, PH 2, P-} CH 3, P-CH 2 -, PC 6 H 5, A 3 3 -PO (A 3 is an aliphatic or aromatic), (A ⁴ O ) ₃ -PO (A ⁴ is alkyl), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH and O═P-OH.

The above structure can absorb infrared rays having a desired wavelength range according to the selection of the type. Specifically, the wavelength of infrared rays capable of absorbing the above structure is, for example, in the range of 1 占 퐉 or more and 20 占 퐉 or less and more preferably in a range of 2 占 퐉 to 15 占 퐉. When the structure is Si-O bond, Si-C bond and Ti-O bond, it may be within the range of 9 탆 or more and 11 탆 or less. In addition, the wavelength of infrared rays that each structure can absorb is easily understood by those skilled in the art. For example, as an absorption band in each structure, a method of determining the absorption spectrum of an organic compound (fifth edition) -SM, IR, NMR, and UV together (1992), Non-Patent Document: SILVERSTEIN BASSLER MORRILL Published on pages 146 to 151 can be referred to.

As the compound having the infrared absorbing structure used in the formation of the separation layer 4, among the compounds having the above-described structure, a compound which can be dissolved in a solvent for application and solidified to form a high- It is not particularly limited as long as it can be formed. However, in order to effectively deteriorate the compound in the separation layer 4 and facilitate separation of the support plate 2 and the substrate 1, it is preferable that the absorption of infrared rays in the separation layer 4 is large, that is, , It is preferable that the infrared ray transmittance when the infrared ray is irradiated to the separation layer 4 is low. Specifically, the transmittance of infrared rays in the separation layer 4 is preferably lower than 90%, and it is more preferable that the transmittance of infrared rays is lower than 80%.

For example, the compound having a siloxane skeleton may be a resin that is a copolymer of a repeating unit represented by the following general formula (5) and a repeating unit represented by the following general formula (6) ) And a repeating unit derived from an acrylic compound can be used.

[Chemical Formula 5]

(In the general formula (6), R ⁶ is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms)

Among them, the compound having a siloxane skeleton is preferably a t-butylstyrene (TBST) -dimethylsiloxane copolymer which is a copolymer of a repeating unit represented by the formula (5) and a repeating unit represented by the following formula (7) , And a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the general formula (5) and a repeating unit represented by the following general formula (7) at a ratio of 1: 1.

[Chemical Formula 6]

As the compound having a silsesquioxane skeleton, for example, a resin which is a copolymer of a repeating unit represented by the following general formula (8) and a repeating unit represented by the following general formula (9) can be used.

(7)

(In the general formula (8), R ⁷ is hydrogen or an alkyl group having a carbon number of 1 or more and 10 or less, and in the general formula (9), R ⁸ is an alkyl group having a carbon number of 1 or more and 10 or less,

Examples of compounds having a silsesquioxane skeleton include compounds disclosed in JP-A-2007-258663 (published on October 4, 2007), JP-A-2010-120901 (published on June 3, 2010) Each silsesquioxane resin disclosed in Japanese Patent Laid-Open Publication No. 2009-263316 (published on November 12, 2009) and Japanese Patent Laid-Open Publication No. 2009-263596 (published on November 12, 2009) Can be used.

Among them, a compound having a silsesquioxane skeleton is more preferably a copolymer of a repeating unit represented by the following general formula (10) and a repeating unit represented by the following general formula (11) And a repeating unit represented by the following general formula (11) in a ratio of 7: 3 is more preferable.

[Chemical Formula 8]

The polymer having a silsesquioxane skeleton may have a random structure, a ladder structure, and a basket structure, but any structure may be used.

Examples of the compound containing a Ti-O bond include (i) tetra-i-propoxytitan, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) alkoxytitaniums such as -i-propoxy octylene glycolate; (ii) titanium chelates such as di-i-propoxy bis (acetylacetonato) titanium and propanedioxy titanium bis (ethylacetoacetate); _{(iii) iC 3 H 7 O} - [- Ti (OiC 3 H 7) 2 -O-] n -iC 3 H 7, and _{nC 4 H 9 O - [-} Ti (OnC 4 H 9) 2 -O- ] _n- nC ₄ H ₉ ; (iv) an acyl group such as tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate, and (2-n-butoxycarbonylbenzoyloxy) Lattice titanium; (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium and the like.

Among these, a compound containing a Ti-O bond, di -n- butoxy-bis (triethanolamine Oh Minato) titanium _{(Ti (OC 4 H 9)} 2 [OC 2 H 4 N (C 2 H 4 OH) ₂ ] ₂ ) is preferable.

Although the above-described separation layer 4 contains a compound having an infrared absorbing structure, the separation layer 4 may further contain components other than the above compounds. Examples of the components include fillers, plasticizers, and components capable of improving the releasability of the support plate 2 and the like. These components are appropriately selected from conventionally known materials or materials that do not interfere with or accelerate the absorption of infrared rays by the above structure and the deterioration of the compound.

(Infrared absorbing material)

The separation layer 4 may contain an infrared absorbing material. The separating layer 4 is constituted by containing an infrared absorbing material, so that the separating layer 4 is deformed by absorbing light, and as a result, the separating layer 4 loses its strength or adhesiveness before being irradiated with light. Therefore, the separating layer 4 is broken by applying a slight external force (for example, lifting the support plate 2), so that the support plate 2 and the substrate 1 can be easily separated from each other .

The infrared absorbing material can be any structure that is altered by absorbing infrared rays. For example, carbon black, iron particles, or aluminum particles can be preferably used. The infrared absorbing material absorbs light having a wavelength in a specific range depending on its type. The infrared absorbing material can be preferably altered by irradiating the separation layer 4 with light having a wavelength in the range that the infrared absorbing material used in the separation layer 4 absorbs.

(Reactive polysilsesquioxane)

The separating layer 4 can be formed by polymerizing reactive polysilsesquioxane, whereby the separating layer 4 has high chemical resistance and high heat resistance.

In the present specification, the reactive polysilsesquioxane is a polysilsesquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis, and the silanol group or Can be polymerized with each other by condensing a functional group capable of forming a silanol group. When the reactive polysilsesquioxane is provided with a silanol group or a functional group capable of forming a silanol group, those having a silsesquioxane skeleton such as a random structure, a basket structure and a ladder structure can be employed have.

It is more preferable that the reactive polysilsesquioxane has a structure represented by the following formula (12).

[Chemical Formula 9]

In the formula (12), R "is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 10 carbon atoms and more preferably selected from the group consisting of hydrogen and alkyl groups having 1 to 5 carbon atoms. When R "is hydrogen or an alkyl group having a carbon number of 1 or more and 10 or less, the reactive polysilsesquioxane represented by the formula (12) can be preferably condensed by heating in the separation layer formation step.

In the formula (12), p is preferably an integer of 1 or more and 100 or less, more preferably 1 or more and 50 or less. The reactive polysilsesquioxane has a repeating unit represented by the formula (12), so that the content of Si-O bonds is higher than that formed by using other materials, and the infrared rays (0.78 탆 or more and 1000 탆 or less) It is possible to form the separation layer 4 having high absorbance at far infrared rays (3 탆 or more and 1000 탆 or less), more preferably at wavelengths of 9 탆 or more and 11 탆 or less.

In the formula (12), R 'are each independently an identical or different organic group. Here, R is, for example, an aryl group, an alkyl group, an alkenyl group and the like, and these organic groups may have a substituent.

When R 'is an aryl group, examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group, and more preferably a phenyl group. The aryl group may be bonded to the polysilsesquioxane skeleton via an alkylene group having 1 to 5 carbon atoms.

When R 'is an alkyl group, examples of the alkyl group include a linear, branched, or cyclic alkyl group. When R is an alkyl group, the number of carbon atoms is preferably 1 to 15, more preferably 1 to 6. When R is a cyclic alkyl group, it may be a monocyclic or an alkyl group having 2 to 4 ring structures.

When R 'is an alkenyl group, examples of the alkyl group include a linear, branched, or cyclic alkenyl group. The alkenyl group preferably has 2 to 15 carbon atoms, 6 is more preferable. When R is a cyclic alkenyl group, it may be a monocyclic or an alkenyl group having 2 to 4 ring structures. Examples of the alkenyl group include a vinyl group, an allyl group and the like.

Examples of the substituent that R 'may have include a hydroxyl group and an alkoxy group. When the substituent is an alkoxy group, there may be mentioned a linear, branched, or cyclic alkylalkoxy group, and the number of carbon atoms in the alkoxy group is preferably 1 to 15, more preferably 1 to 10.

In one aspect, the siloxane content of the reactive polysilsesquioxane is preferably 70 mol% or more and 99 mol% or less, and more preferably 80 mol% or more and 99 mol% or less. When the siloxane content of the reactive polysilsesquioxane is 70 mol% or more and 99 mol% or less, it is preferably modified by irradiating with infrared rays (preferably far-infrared rays, more preferably light having a wavelength of 9 탆 or more and 11 탆 or less) A separation layer can be formed.

In one aspect, the weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 or more and 50,000 or less, and more preferably 1,000 or more and 10,000 or less. When the weight average molecular weight (Mw) of the reactive polysilsesquioxane is 500 or more and 50,000 or less, the reactive polysilsesquioxane can be preferably dissolved in a solvent and can be preferably applied onto a support plate.

Examples of commercially available products usable as the reactive polysilsesquioxane include SR-13, SR-21, SR-23 and SR-33 manufactured by Konishi Chemical Industry Co., Ltd.

[Other]

In the supporting body separating method according to the present embodiment, the dicing tape 5 provided with the dicing frame 6 is used as the other constitution.

(Dicing tape 5)

On the side of the substrate 1 of the layered product 10, a dicing tape 5 is bonded. The dicing tape 5 is used for manufacturing a semiconductor chip by dicing the substrate 1 after the support plate 2 is peeled off.

As the dicing tape 5, for example, a dicing tape 5 having a structure in which an adhesive layer is formed on the base film can be used. As the base film, for example, a resin film such as PVC (polyvinyl chloride), polyolefin, or polypropylene can be used. The outer diameter of the dicing tape 5 is larger than the outer diameter of the substrate 1 and when the dicing tape 5 and the dicing tape 5 are stacked together, a portion of the dicing tape 5 is exposed to the outer edge portion of the substrate 1.

(Dicing frame 6)

A dicing frame 6 for preventing warping of the dicing tape 5 is mounted on the outer periphery of the exposed surface of the dicing tape 5. As the dicing frame 6, for example, a dicing frame made of metal such as aluminum, an alloyed dicing frame made of stainless steel (SUS) or the like, and a dicing frame made of resin can be given.

≪ Support Separation Method Related to Modification Examples >

The support separation method according to the present invention is not limited to the above embodiment. For example, as shown in Fig. 3 (b), in the support separating method according to one modification, in the laminate 10, the width W 'in the radial direction is set so as to surround the entire circumference of the circuit formation region, 1), the predetermined area occupying the range of the width W'2 is not spaced apart from the circuit formation area of the substrate 1. In this case, The supporting body separation method according to the present modification example is a method for separating the support body from the divided region 4 in the separation layer 4 to which the laser light L is irradiated in the case where the value of the width W'1 is smaller than 2 mm It is effective in that the width W'2 can be easily secured at about 1.3 mm or more.

It is possible to prevent the laser light L from directly irradiating the circuit formation region of the substrate 1 with the above arrangement so that the integrated circuit formed on the substrate 1 is irradiated with the laser light L It is possible to prevent the user from receiving the damage.

3 (c), the range of the width (W "2) in the radial direction of the predetermined region surrounding the entire circumference of the circuit formation region is, for example, Occupies less than 100% of the width of the non-circuit forming area.

The laser light L can be prevented from being irradiated to the outside of the outer peripheral end portion of the substrate 1 and the laser light L is irradiated to the circuit formation region of the substrate 1 . This modified example is a case where the region for irradiating the laser light L in the separation layer 4 is secured in the case where the width of the non-circuit formation region in the substrate 1 is about 1.3 mm, for example It is effective in that it can do.

≪ Support member separation method according to the second embodiment >

The support separation method according to the present invention is not limited to the above embodiment. For example, in the support separation method related to the embodiment (the second embodiment), the detection step of detecting the direction of the layered body 10 before the light irradiation step is further included, and in the separation step, (Holding portion, not shown) provided with a suction pad for holding a support plate (support) 2 for applying a force to the stacked body 10 based on the direction of the stacked body 10 And the laminated body 10 is rotated so as to be placed on the divided regions 4C-1 to 4C-6 irradiated with the laser light L. Here, the separation plate has four adsorption pads arranged at regular intervals in the peripheral edge portion of the support plate 2 when the support plate 2 is held.

According to the above configuration, even if the laser light L is not irradiated to the whole area 4C of the separation layer 4, the laminate ( 10), it is sufficient to perform the light irradiation step only in the divided region corresponding to the position where the adsorption pad of the separation plate is disposed. Therefore, the time for irradiating the separation layer 4 with the laser light L can be further shortened, and the support plate 2 can be separated from the laminate 10 more quickly. The supporting body separating method according to the present embodiment will be described with respect to only the difference from the supporting body separating method according to the first embodiment, and description of the same point will be omitted.

[Detection process]

In the detection step, the optical alignment apparatus (not shown) that detects the notch (notch, not shown) formed on the support plate 2 before the light irradiation step is performed is used as a reference, The direction of the body 10 is specified. Thus, it is possible to specify in which of the divided regions in the separation layer 4 the light is irradiated in the subsequent light irradiation step.

In the detection step, for example, the direction of the laminate 10 before the light irradiation step is set so that the cutout portion in the support plate 2 is arranged at the position of the one-dot chain line C1 shown in Fig. 2 (b) .

[Light irradiation step]

As shown in Fig. 2 (b), in the light irradiation step included in the support member separation method according to the present embodiment, by repeating the light irradiation step and the pivoting step after the detection step, And detaches the separation layer 4 in the divided areas 4C-1 to 4C-6. As a result, the separation layer 4 of the divided regions 4C-1 to 4C-6, which are divided into four positions in total, are deteriorated at equal intervals in the peripheral edge portion of the separation layer 4.

[Separation Process]

In the separation step, first, the four adsorption pads in the separation plate for holding the support plate 2 are divided into a plurality of sub-areas (hereinafter referred to as " sub-areas ") irradiated with the laser light L based on the direction of the layered body 10 detected in the detection step (4C-1 to 4C-6). Thereafter, the support plates 2 positioned on the divided areas 4C-1 to 4C-6 are held and lifted by the respective adsorption pads. This makes it possible to concentrate the force applied from the separation plate to the detached separation layer 4 in the divided areas 4C-1 to 4C-6. Therefore, after the deteriorated separation layer 4 in the divided areas 4C-1 to 4C-6 is destroyed, the force (force) is applied to the separation layer 4 in the area not irradiated with the laser light L . Thereby, the support plate 2 can be preferably separated from the laminate 10.

[Method for separating support body according to another embodiment]

The support separation method according to the present invention is not limited to the above-described embodiments (the first embodiment and the second embodiment). For example, in the support separation method according to another embodiment, the material of the support plate (support) and the separation layer can be appropriately selected in accordance with the performance required for the laminate. Therefore, the laser for emitting the light to be irradiated to the separation layer is not limited to the CO ₂ laser, and may be a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser or a fiber laser, A laser such as a gas laser such as a laser, a CO ₂ laser, an excimer laser, an Ar laser or a He-Ne laser, a laser beam such as a semiconductor laser or a free electron laser, And may be appropriately selected depending on the wavelength that can be used.

In the supporting member separating method according to still another embodiment of the present invention, the holding portion for holding the support plate 2 in the laminate 10 is, for example, a plurality of holding portions for holding the outer peripheral end portion of the support plate 2 Or a separating plate provided with a clamp (claw portion, not shown).

In the supporting member separating method according to still another embodiment, the number and arrangement of the divided regions to be irradiated with light in the light irradiation step may be appropriately changed depending on the number and arrangement of the adsorption pads of the holding portion.

It is to be understood that the present invention is not limited to the embodiments described above and that various changes and modifications can be made to the technical scope of the present invention without departing from the scope of the present invention. .

Industrial availability

The support separating method according to the present invention can be suitably used in the manufacturing process of the miniaturized semiconductor device.

1 substrate
2 Support plate (support)
3 adhesive layer
4 separating layer
4A region (separation layer)
4B region (separation layer)
4C region (separation layer)
4C-1, 4C-2, ... The partition (separation layer)
5 Dicing Tape
10 laminate
L light

Claims (10)

A supporting body separating method for separating a supporting body from a laminate comprising a substrate and a supporting body that transmits light through an adhesive layer and a separating layer which is deformed by absorbing light,
Wherein the substrate has a circuit formation region in which a circuit is formed and a non-circuit formation region in which the circuit is not formed and which surrounds the entire periphery of the circuit formation region,
Wherein the substrate is provided with a separation layer which surrounds the entire circumference of the circuit formation region and is stacked so as to face a predetermined region occupying an area of 65% or more and less than 100% of the width in the radial direction of the non- A light irradiation step of irradiating light at least partly through the support,
And separating the support from the laminate by applying a force to the laminate to which the light is irradiated. The method according to claim 1,
Wherein an inner circumferential end of the predetermined region and an outer circumferential end of the circuit forming region are spaced apart from each other and an outer circumferential end of the predetermined region and an outer circumferential end of the substrate are spaced apart. 3. The method according to claim 1 or 2,
Wherein the width in the radial direction of the non-circuit forming region is larger than 1.3 mm and smaller than 2.0 mm and the width in the radial direction of the predetermined region is smaller than 1.3 mm and smaller than 2.0 mm Support separation method. 4. The method according to any one of claims 1 to 3,
Wherein the light irradiation step is a step of irradiating light to at least a part of the separation layer which is laminated so as to face a predetermined divided area which equally divides the predetermined area at a predetermined angle with the center of the plane of the laminate as a center point An irradiation step,
And a rotating step of rotating the plane of the laminate at the predetermined angle with the center of the plane of the laminate as a center point. 5. The method of claim 4,
Further comprising a detecting step of detecting a direction of the laminate before the light irradiation step,
A holding portion for holding the supporting body for applying a force to the laminated body based on the direction of the laminated body detected in the detecting step is disposed on the divided predetermined region irradiated with the light, Thereby rotating the laminate. The method according to claim 4 or 5,
Wherein the light irradiation step and the rotation step are alternately repeated to irradiate light to the separation layer laminated so as to face all the divided predetermined areas before the separation step. 7. The method according to any one of claims 4 to 6,
Wherein light is irradiated to an area of 50% or more of the separation layer laminated so as to face the divided predetermined area. 8. The method according to any one of claims 1 to 7,
Wherein the irradiation pattern of the light is any of a line shape, a circular dot shape, a ring shape, a polygonal dot shape, a polygonal ring shape, or a spiral shape. 9. The method according to any one of claims 1 to 8,
Wherein the support is made of silicon,
Wherein the light is a carbonic acid laser. 10. The method according to any one of claims 1 to 9,
Wherein a dicing tape is pasted on a substrate side of the laminate, and a part of the dicing tape is exposed on an outer edge portion of the substrate.

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