TWI720004B - Substrate separating method - Google Patents

Abstract

The present invention prevents light from being irradiated to the circuit formed on the substrate, At the same time, the support can be quickly separated from the laminate.

Enclose in the substrate 1 on which the circuit is formed. At least a part of the separation layer 4 is laminated so that the entire circumference of the circuit formation area and the specific area that occupies more than 65% of the radial width of the non-circuit formation area and less than 100% of the area is interposed by the support plate 2 The laser light L is irradiated, and the support plate is separated by the laminated body 10.

Description

Support separation method

The present invention relates to a method for separating a support.

In recent years, electronic devices such as IC cards and portable phones have been required to be thinner, smaller, and lighter. In order to meet these requirements, the semiconductor chip to be mounted must also be a thin semiconductor chip. Therefore, the thickness (film thickness) of the wafer substrate used as the base of the semiconductor chip is 125~150μm in the current state, but it must be 25μm~50μm for the next-generation chip. Therefore, in order to obtain the above-mentioned thickness of the wafer substrate-based wafer substrate, a thinning step is necessary.

The strength of the wafer substrate is reduced due to the thinning of the wafer substrate. In order to prevent damage to the thinned wafer substrate, the wafer substrate is automatically transported in the state where the wafer substrate is bonded to the support plate during the manufacturing process, and the circuit is mounted on the wafer substrate. And other structures. Then, after the manufacturing process, the wafer substrate is separated from the support plate. Therefore, various methods of peeling the support from the wafer substrate have been used up to now.

Patent Document 1 describes a method for peeling off a member, which It includes at least a part of the outer edge of the first main surface, the step of disposing the light-to-heat conversion layer, and the step of disposing the light-to-heat conversion layer between the first main surface and the second main surface. The second main surface, the step of bonding to each other via the adhesive layer, the step of irradiating the light-to-heat conversion layer with laser light, and the outer peripheral portion of any one of the first member and the second member, face the first A step of applying force in the direction separating the other member from the second member and the second member, and at least partially peeling the first member from the second member.

[Prior technical literature] 〔Patent Literature〕

[Patent Document 1] JP 2015-122370 A (published on July 2, 2015)

Compared with the member peeling method described in Patent Document 1, if there is a new support body that can be irradiated with light on the separation layer (light-to-heat conversion layer), and at the same time, the support body can be smoothly separated from the laminated body. This method is useful because it is useful to avoid irradiating the circuit formed on the substrate with light, and the support can be quickly separated from the laminated body. Therefore, this support separation method is expected.

The present invention is made in view of the aforementioned problems, and the purpose is to provide a new support separation method, which can prevent The circuit is irradiated with light, and the support can be quickly separated from the laminated body at the same time.

In order to solve the above-mentioned problems, the support separation method of the present invention is to separate the substrate and the light-transmitting support via an adhesive layer and a separation layer that is degraded by absorption of light. The method for separating the support of the support is characterized in that the substrate has a circuit formation area where a circuit is formed, and a non-circuit formation area surrounding the entire circumference of the circuit formation area where the circuit is not formed, and the method includes A step of irradiating light, interposing the support body, facing the substrate to surround the entire circumference of the circuit forming area and occupying more than 65% but less than 100% of the width of the non-circuit forming area in the radial direction Light is applied to at least a part of the separation layer that is laminated in the specific region, and a separation step is performed in which force is applied to the laminated body that has been irradiated with the light, and the supporting body is separated from the laminated body.

If the present invention exhibits an effect, it is possible to provide a new support separation method, which can prevent the circuit formed on the substrate from being irradiated with light, and at the same time, the support can be quickly separated from the laminated body.

1‧‧‧Substrate

2‧‧‧Support plate (support body)

3‧‧‧Next layer

4‧‧‧Separation layer

4A‧‧‧area (separation layer)

4B‧‧‧area (separation layer)

4C‧‧‧area (separation layer)

4C-1‧‧‧Separated area (separation layer)

4C-2‧‧‧Separated area (separation layer)

5‧‧‧Cutting tape

6‧‧‧Cutting frame

10‧‧‧Laminated body

50‧‧‧Laser Irradiation Device

L‧‧‧Light

W1‧‧‧Width

W2‧‧‧Width

[Figure 1] Explains the support components related to one embodiment of the present invention A schematic diagram from the method.

[Figure 2] A diagram for explaining the outline of the region of light irradiated to the separation layer in the support separation method according to one embodiment of the present invention.

[FIG. 3] A diagram explaining the outline of the light irradiation stage included in the support separation method related to one embodiment and a modification of the present invention.

[Figure 4] A diagram showing the outline of a light irradiation pattern related to a support separation method according to an embodiment of the present invention.

<About the support separation method of the first embodiment>

Using FIGS. 1 to 4, the support separation method of one embodiment of the present invention (the first embodiment) will be described in more detail.

As shown in Figure 1(a), the support separation method of this embodiment is to separate the substrate 1 made of silicon and the support plate (support) 2 made of silicon through the adhesive layer 3, and The laminated body 10 formed by layering the separation layer 4 that has been degraded by absorbing the laser light L separates the support plate 2. In addition, the laminated body 10 has a circular shape in a plan view. In addition, the laminated body 10 has a dicing tape 5 attached to the substrate 1 side, and the dicing tape 5 is provided with a dicing frame 6.

As shown in Fig. 1(b), the support separation method of this embodiment includes a light irradiation step. The light irradiation step alternately repeats the light irradiation stage and the rotation stage, and the area 4C of the separation layer 4 The whole area is irradiated with laser light L (Figure 2(a)). Shang, in relation to this reality The method of separating the support body in the form of application is as long as the so-called rotating stage and the light irradiation stage are not performed at the same time, and either of them may be performed first.

In addition, as shown in Figure 1 (c) and (d), the support separation method of this embodiment includes applying force to the laminated body 10 that has been irradiated with laser light L, and separating the support plate 2 by the laminated body 10 Separation step.

[Light irradiation step]

The light irradiation step included in the support separation method of this 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 stage and the rotation stage are alternately repeated. The region 4C of the separation layer 4 laminated in a specific region that occupies more than 65% of the radial width of the non-circuit formation region and less than 100% is irradiated with light through the support plate 2.

As a result, the area where the laser light L is irradiated to the separation layer 4 can be reduced. Therefore, the time required to perform the light irradiation step can be shortened.

(Circuit formation area)

The circuit formation area means an area where a structure such as an integrated circuit is formed on the inner periphery of the substrate 1. Furthermore, in the circuit formation area, a structure such as an integrated circuit can be formed on both the surface exposed to the outside of the laminate 10 of the substrate 1 and the surface opposite to the adhesive layer 3 of the substrate 1 Or either party. The circuit formation area on the substrate 1 is in the laminated body 10 so as to be located within the dashed line A1 of the separation layer 4 with respect to The area 4A on the side is arranged in a manner (Figure 2(a)).

(Non-circuit formation area)

The term "non-circuit formation area" means that the substrate 1 surrounds the entire circumference of the circuit formation area and occupies an area outside the outer peripheral end of the circuit formation area and inside the substrate 1 outer peripheral end. The non-circuit forming area on the substrate 1 is in the laminate 10, and is arranged so as to be opposite to the area 4B located in the dashed line A1 and the dashed line A2 of the separation layer 4 (Figure 2(a)). Here, the outer peripheral end of the substrate 1 is arranged on the broken line A2 of the separation layer 4.

(Specific area)

The term "specified area" means an area that encompasses the entire circumference of the circuit formation area and occupies more than 65% but less than 100% of the radius of the non-circuit formation area. The area is composed of divided specific areas. In addition, in the support separation method related to this embodiment, the inner peripheral end of the specific area of the substrate 1 is separated from the outer peripheral end of the circuit formation area, and the outer peripheral end of the specific area is separated from the outer peripheral end of the substrate 1. . In the laminated body 10, the separation layer 4 is located in a specific area of the substrate 1, and is arranged so as to be opposite to the area 4C located on the broken line B1 and the broken line B2 (Figure 2(a)).

(Split a specific area)

The so-called dividing a specific area means setting the center point of the laminated body 10 As the center, a specific area of the substrate 1 is equally divided at a specific angle. The divided specific area on the substrate 1 is in the laminate 10 to correspond to the divided area 4C divided by the area 4C by the one-dot chain lines C1 to C3 of the separation layer 4 shown in (a) of Figure 2 -1 and 4C-2 exemplified the arrangement of the divided regions. However, the angle for equally dividing the specific area of the substrate 1 may be an angle that can be equally divided with the center point of the laminated body 10 as the center. For example, 20°, 30°, or 45° is ideal, and 20° is more desirable.

(Light irradiation stage)

In the light irradiation stage, the laminated body 10 is irradiated with light for each divided area of the separation layer 4 via the support plate 2. For example, the laser light L is irradiated to each divided area equally divided by 20° at a specific angle. As a result, the scanning range of the laser light L irradiated by the laser irradiation device 50 can be narrowed, and the shape irregularity of the irradiation pattern generated when the laser light L is scanned can be reduced. Therefore, it is possible to prevent the laser light L irradiated on the divided area 4C-1 of the separation layer 4 from being irradiated beyond the range of the divided area, and it is possible to appropriately prevent the circuit provided on the substrate 1 and the dicing tape 5 from being irradiated with light.

In addition, as shown in Fig. 3(a), in the light irradiation stage, the area occupied by the non-circuit formation area having the width W1 in the radial direction of the substrate 1 is 65% or more, but less than 100% of the area of the width W2 The separation layer 4 that divides a specific area is irradiated with laser light L. Furthermore, the width W1 is also the width in the radial direction of the region 4B of the separation layer 4 shown in (a) of FIG. 2. In addition, the width W2 is also the width in the radial direction of the divided region 4C-1 of the separation layer 4 shown in (a) of FIG. 2.

The width W1 of the non-circuit formation area is set appropriately according to the size of the substrate, so it is not limited, but if the diameter of the substrate used in this embodiment is about 300mm (12 inches), it is greater than 1.0mm, 3.0 A wide range of mm or less is ideal, and a wide range of greater than 1.3 mm and 2.0 mm or less is ideal.

In addition, the width W2 of the divided specific area (in other words, the width of the divided area 4C-1 in the separation layer 4) is 65% or more of the width W1 of the non-circuit formation area, and the width within the range of less than 100% is ideal. The smaller W1 is, the larger the ratio of width W1 to width W2 becomes, it is ideal. Thus, at least a part of the separation layer 4 can be altered in such a manner that the support plate 2 can be appropriately separated from the laminate 10 by performing a separation step later.

In the light irradiation stage, when the laser light L is irradiated to the separation layer 4 in the area 4C-1 through the support plate 2, the laser light L changes the quality of the separation layer 4, and at the same time, passes through the separation layer 4 and irradiates the substrate 1 to divide a specific area. Here, in the substrate 1, the divided specific area occupying the width W2 is separated by the circuit formation area of the substrate 1. Therefore, compared to the case where the inside of the divided specific area is set to be in contact with the circuit formation area, it is possible to smoothly prevent the laser light L from irradiating the circuit formed in the circuit formation area of the substrate 1. Therefore, the circuit can be prevented from being damaged by the laser light L. In addition, in the substrate 1, the divided specific area occupying the width W2 is separated by the outer peripheral end of the substrate 1. Therefore, compared to the case where the outer peripheral end of the divided specific area is set to overlap the outer peripheral end of the substrate 1, the laser light L can be smoothly prevented from irradiating the outer peripheral end of the substrate 1 to the outside. Therefore, it is possible to more appropriately prevent the dicing tape 5 located outside the outer peripheral end of the substrate 1 from being irradiated with the laser light L and the dicing tape 5 from being damaged.

In this specification, the term "deteriorated" of the separation layer means a state in which the separation layer can be destroyed by a slight external force, or a phenomenon in which the adhesive force of the layer in contact with the separation layer is low. 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 irradiated with light. In short, by absorbing light, the separation layer 4 becomes brittle. The so-called deterioration of the separation layer may refer to the decomposition of the material constituting the separation layer due to the energy of the absorbed light, the change in spatial arrangement, or the dissociation of functional groups. The deterioration of the separation layer 4 occurs as a result of light absorption.

Therefore, it is possible to easily separate the support plate and the substrate by changing the quality of the support plate only by raising the support plate and causing damage. More specifically, for example, one of the substrate and the support plate in the laminate is fixed to the mounting table by a support separation device or the like, and the other is held and lifted by an adsorption pad (holding portion) provided with adsorption means. High, separate the support plate and the substrate, or the chamfered part of the peripheral part of the support plate is grasped by a separation plate equipped with a clamp (claw portion), etc., and force is applied to separate the substrate and the support plate. In addition, for example, the support plate may be peeled from the substrate on the laminate by a support separation device provided with a peeling means for supplying a peeling liquid for peeling the adhesive. By the peeling means, the peeling liquid is supplied to at least a part of the peripheral end of the adhesive layer of the laminate, and the adhesive layer of the laminate is swelled, so that the adhesive layer has been swollen and the force is concentrated on the separation layer The way to the substrate Apply force with the support plate. Therefore, the substrate and the support plate can be appropriately separated.

Furthermore, external force is applied to the laminated body, that is, the external force is appropriately adjusted according to the size of the laminated body, and the material of the supporting plate (supporting body) such as glass and silicon, etc. There is no limitation but for example A laminated body with a diameter of about 300 mm has a force of about 0.1 to 5 kgf, for example. By applying an external force of about 0.1~5kgf, the substrate and the support plate can be properly separated.

_{In the support separation method according to this embodiment, a CO 2} laser (carbonic acid laser) is used as the laser light L that emits the light irradiated on the separation layer 4. As a result, it is possible to generate laser light L transmitted through the support plate 2 made of silicon.

The laser light irradiation conditions in the light irradiation stage are that the average output value of the laser light is 1.0W or more and 5.0W or less, preferably 3.0W or more and 4.0W or less. The repetition frequency of laser light is above 20kHz and below 60kHz is ideal, and above 30kHz and below 50kHz is ideal. It is ideal that the scanning speed of the laser light is above 100mm/s and below 10000mm/s. In this way, the laser irradiation conditions can be set to appropriate conditions for deteriorating the separation layer 4.

Here, the irradiation pattern of the laser light L is, for example, as shown in (a) to (f) in Fig. 4, and any one of linear, spiral, polygonal, dot, polygonal, or circular is ideal. In the light irradiation stage, between the dashed lines B1 and B2 at the boundary of the radial direction of the separation layer 4, the method occupies more than 50% of the area of the divided regions 4C-1 and 4C-2 as the beginning of the divided regions , Forming a pattern of light irradiation. Thus, you can make The separation layer 4 in the divided region 4C-1 is appropriately deteriorated and becomes brittle.

For example, as shown in Fig. 4(a), when a linear pattern is adopted, the direction of the linear pattern is not limited. In addition, if the pattern can be formed over 50% of the area of the divided region, the width of the line pattern and the number of lines are not limited. Still, among the patterns shown in (a) to (f) of Fig. 4, a straight line pattern is the most ideal at the point where the irradiation time of the laser light L to the divided area can be minimized .

In addition, as shown in Fig. 4(b), the irradiation pattern of the laser light L may also be a spiral pattern. The pattern of the line drawing the spiral is the same as the pattern of the line, and it can be continuously formed in the divided regions of the separation layer 4, which is ideal in terms of shortening the irradiation time of the laser light L. Furthermore, when irradiating the divided area 4C-1 of the separation layer 4, the spiral pattern is generated in a place where the laser light L is repeatedly irradiated. However, in the support separation method according to the present embodiment, the laser light L that has passed through the separation layer 4 is irradiated to the divided specific area of the substrate 1 and therefore is not irradiated to the circuit formed on the substrate 1 and the dicing tape 5. Therefore, in a place where the laser light L is repeatedly irradiated, even if the irradiation output of the laser light L is not adjusted in such a way that the irradiation output of the laser light L is excessively weakened, the integrated circuit formed on the substrate 1 and the dicing tape 5 can be prevented from being damaged.

In addition, as shown in FIG. 4(c), the irradiation pattern of the laser light L is a polygonal dot shape, for example, it may be a quadrangular dot shape. Here, the size of each point of the quadrangular dot shape can be formed on the inner circumference of the divided area 4C-1 to occupy more than 50% of the area of the divided area. It is not limited. Similarly, as shown in Fig. 4(d), the irradiation pattern of the laser light L can also be a dot shape. These polygonal and dot-like dot-shaped patterns can be inferior to linear shapes and shorten the time for irradiating the divided area, which is ideal for the point where the divided area can form the pattern densely.

In addition, as shown in Fig. 4(e), the irradiation pattern of the laser light L may also be a polygonal ring. In addition, as shown in Fig. 4(f), the irradiation pattern of the laser light L may also be a ring. By forming these polygonal ring and ring patterns, the separation layer 4 in the divided region 4C-1 can be appropriately changed in quality. Furthermore, in each ring pattern, the width of the ring pattern and the size of the pattern can also be adjusted appropriately.

(Spinning stage)

In the rotating stage, the laminated body 10 that irradiates the laser light L to the divided area is the light irradiation stage, and the center point of the laminated body 10 is used as the center, so that the plane of the laminated body 10 is rotated at a specific angle . In the support separation method according to this embodiment, the region 4C of the separation layer 4 is equally divided at a specific angle of 20°. Therefore, in the rotation stage, the laser light L is irradiated to the divided region 4C-1 of the separation layer 4 by the light irradiation stage, and the laminated body 10 is rotated at a specific angle of 20°. Thus, the laser irradiation device 50 is arranged on the divided region 4C-2 of the separation layer 4 of the laminated body 10.

After that, the separation layer 4 in the divided region 4C-2 is changed in quality by the light irradiation stage. Furthermore, the rotation stage and the light irradiation stage are alternately repeated, and the laser light L is irradiated to the entire area 4C of the separation layer 4.

Still, the cutting glue with the cutting frame 6 will be provided in the rotating stage The tape 5 is attached to the laminated body 10 on the side of the substrate 1, for example, it is fixed to a mounting table with a porous portion, a rotatable platform (not shown), etc., and it can be rotated at a specific angle.

(Separation step)

In the separation step, force is applied to the laminated body 10 that has been irradiated with the laser light L, and the supporting plate 2 is separated from the laminated body 10 (Fig. 1(c)). More specifically, for example, in a state where the substrate 1 side of the laminate 10 is fixed by a rotatable platform, it is adsorbed by a separation plate (holding part, not shown) provided with a suction pad such as a bellows pad. Keep the upper face of the support plate 2 while raising the separation plate. As a result, force is applied to the laminate 10, and the support plate 2 is separated by the laminate 10.

Furthermore, in the support separation method according to the present embodiment, the light irradiation step and the rotation stage are alternately performed in the light irradiation step to alter the quality of the separation layer 4 in the entire area 4C. In short, in the layered body 10, the entire periphery of the separation layer 4 is deteriorated. Therefore, after the light irradiation step, the direction of the laminated body 10 is not specified, and the laminated body 10 can be held on the peripheral edge portion of the supporting plate 2 of the laminated body 10 to perform the separation step. In addition, when a force is applied to the laminated body 10 in the separation step, the force is concentrated on the degraded separation layer 4 in the region 4C. Thus, first, the separation layer 4 in the region 4C is destroyed, and then, by the force concentrated on the separation layer 4 outside the region C, the separation layer 4 outside the region C is destroyed. Thereby, the support plate 2 can be appropriately separated from the laminated body 10.

Still, in the separation step, for example, via floating joints or universal For joints such as joints (not shown), the support plate 2 is separated from the laminated body 10 by raising the separating plate. Such a joint is rotatable, and is movable in an inclined manner with respect to the plane of the laminated body 10 fixed to the platform.

If a force is applied to the laminated body 10 via a floating joint or the like by a separating plate, when the force is concentrated on a part of the outer peripheral end of the laminated body 10, the floating joint is movable and is directed toward a part of the outer peripheral end. The adsorption pad is connected to the surface of the support plate 2, and the separation plate is inclined. Along with this, the support plate 2 on the way of separation from the laminated body 10 is inclined. As a result, it is possible to prevent excessive force from being applied to a part of the support plate 2 and the substrate 1 and to concentrate the force on the separation layer 4 laminated between the support plate 2 and the adhesive layer 3. Therefore, the support plate 2 and the substrate 1 can be prevented from being damaged due to excessive force, and the support plate 2 can be peeled off from the substrate 1 appropriately.

[Other steps]

After the separation step, as shown in Figure 1(d), the substrate 1 from which the support plate 2 is separated is in the state where the dicing tape 5 is attached, for example, the adhesive is removed by a peeling liquid containing an organic solvent. The step of washing the residue of layer 3 and separation layer 4. In addition, after the cleaning step, a dicing step of manufacturing a semiconductor wafer from the substrate 1 to which the dicing tape 5 has been attached is performed. Here, the dicing tape 5 to which the substrate 1 has been adhered has been prevented from being damaged by the laser light L irradiation. Therefore, according to the support separation method according to this embodiment, the dicing tape 5 can be adhered to the laminated body 10, and a series of steps from the substrate 1 to the semiconductor wafer manufacturing can be performed smoothly. Therefore, the substrate 1 that has been thinned in the step of forming the circuit on the substrate 1 can avoid cutting on the adhesive. It breaks when tape 5 is cut.

〔Laminated body 10〕

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

[Substrate 1]

In the support separation method according to this embodiment, as the substrate 1, a wafer substrate made of silicon is used. The substrate 1 is supported by the support plate 2 via the adhesive layer 3 and the separation layer 4, and can be used for thinning, mounting, and other processes. In addition, the circuit formation area on the substrate 1 is, for example, a structure where an integrated circuit or a metal bump is mounted.

Although the support separation method in this embodiment uses a silicon wafer substrate as a substrate, the substrate 1 is not limited to a silicon wafer substrate, and ceramic substrates, thin film substrates, flexible substrates, etc. can also be used. A substrate made of any of the materials.

〔Support plate 2〕

The support plate (support body) 2 is a support body that supports the substrate 1, and the substrate 1 is adhered via the adhesive layer 3. Therefore, when the support plate 2 is used in the process of thinning, conveying, and mounting of the substrate 1, it is sufficient to have the necessary strength in order to prevent damage or deformation of the substrate 1. In addition, what is necessary is just to transmit light for changing the quality of the separation layer 4.

For the supporting system, a supporting plate made of glass, silicon, or acrylic resin can be used. However, the support plate 2 made of silicon is used in the support separation method related to this embodiment. By laminating the support plate 2 made of silicon on the substrate 1, the difference in the thermal expansion coefficient between the substrate 1 and the support plate 2 can be reduced, so that the bending of the laminated body 10 due to heating can be reduced.

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

〔Layer 3〕

The next layer 3 is used for attaching the substrate 1 to the support plate 2 on which the separation layer 4 has been formed. In addition, the adhesive layer 3 is a layer formed by an adhesive used for attaching the substrate 1 and the support plate 2.

The thickness of the subsequent layer 3 may be appropriately set according to the types of the substrate 1 and the support plate 2 to be attached, the treatment applied to the substrate 1 after attachment, etc., but the range of 10 to 150 μm is ideal. The range of 15~100μm is ideal.

The adhering layer 3 can be formed by applying an adhesive by methods such as spin coating, dipping, roll blade method, spray coating, and slit coating. In addition, the adhesive layer 3 may be formed by, for example, instead of directly applying the adhesive to the substrate 1, a film (ie, a dry film) in which the adhesive is applied to both sides in advance, and then attached to the substrate 1.

As the adhesive for forming the adhesive layer 3, for example, acrylic, phenolic, naphthoquinone, hydrocarbon, polyimide, elastomer, Polyurethane is a wide variety of adhesives generally known in the field.

As the resin contained in the adhesive, that is, the resin contained in the adhesive layer 3 has adhesive properties. For example, hydrocarbon resins, acrylic-styrene resins, maleimide resins, and elastomers can be preferably used. Resin, polycarbonate-based resin, etc., or a combination of these. Hereinafter, the composition of the resin contained in the adhesive layer 3 of the embodiment of this embodiment will be described.

(Hydrocarbon resin)

The hydrocarbon resin system has a hydrocarbon skeleton and is a resin obtained by polymerizing a monomer composition. Examples of hydrocarbon resins include cycloolefin polymers (hereinafter referred to as "resin (A)", and at least one resin selected from the group consisting of terpene resins, rosin resins, and petroleum resins) ( Hereinafter, there are those referred to as "resin (B)") etc., but it is not limited to this.

The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin-based monomer. Specifically, a ring-opening (co)polymer containing a monomer component of a cycloolefin-based monomer, a resin obtained by addition (co)polymerizing a monomer component containing a cycloolefin-based monomer, etc. are mentioned.

Examples of the aforementioned cycloolefin-based monomers contained in the monomer component constituting the resin (A) include bicyclic products such as norbornene and norbornadiene, dicyclopentadiene, and hydroxydicyclopentadiene Such as tricyclic compounds, tetracyclic compounds such as tetracyclododecene, pentacyclic compounds such as cyclopentadiene trimers, heptacyclic compounds such as tetracyclopentadiene, or alkyl groups of such polycyclic compounds (Methyl, ethyl, propyl, butyl, etc.) substituents, alkenyl (vinyl, etc.) substituents, alkylene (ethylene, etc.) substituents, aryl (phenyl, tolyl, naphthyl, etc.) Etc.) Substitutes Wait. Among these, the norbornene-based monomer selected from the group consisting of norbornene, tetracyclododecene, or these alkyl substituents is particularly preferable.

The monomer component system that constitutes the resin (A) may also contain other monomers copolymerizable with the above-mentioned cycloolefin-based monomer, for example, it is desirable to contain an ethylenic monomer. Examples of the olefin monosystem include ethylene, propylene, 1-butene, isobutene, 1-hexene, and α-olefins. The olefin monosystem can be linear or branched.

In addition, as the monomer component constituting the resin (A), the case where a cycloolefin monomer is contained is preferable from the viewpoint of high heat resistance (low thermal decomposition and thermal weight reduction). The ratio of the cycloolefin monomer in the total monomer components constituting the resin (A) is preferably 5 mole% or more, more preferably 10 mole% or more, and more preferably 20 mole% or more. In addition, the ratio of cycloolefin monomers constituting the total monomer components of the resin (A) is not particularly limited, but from the viewpoints of solubility and stability in solution over time, 80 mole% or less is ideal, and 70 mole% or less is Ideal.

In addition, as a monomer component constituting the resin (A), a linear or branched ethylenic monomer may be contained. From the viewpoint of solubility and flexibility, the ratio of the alkene monomer constituting the total monomer component of the resin (A) is 10 to 90 mole%, 20 to 85 mole% is more preferable, and 30 to 80 mole% is more preferable.

Furthermore, the resin (A) is, for example, a resin formed by polymerizing a monomer component composed of a cycloolefin-based monomer and an alkene monomer. It is a resin without a polar group and is effective in suppressing gas generation at high temperatures. As ideal.

Regarding the polymerization method or polymerization conditions when polymerizing monomer components The system is not particularly limited, and can be appropriately set in accordance with a general method.

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

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

As such a cycloolefin copolymer system, APL 8008T, APL 8009T, APL 6013T (all manufactured by Mitsui Chemicals), etc. can be used.

In addition, as commercially available products that can be used as resin (A), for example, "TOPAS" manufactured by POLYPLASTICS, "APEL" manufactured by Mitsui Chemicals Co., Ltd., "ZEONOR" and "ZEONEX" manufactured by Zeon Co., Ltd., and JSR "ARTON" of the company system, etc.

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

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

The softening point of the resin (B) is not particularly limited, but 80 to 160°C is ideal. If the softening point of the resin (B) is 80 to 160°C, the laminate can be prevented from softening when exposed to a high-temperature environment, and adhesion failures will not occur.

The weight average molecular weight of the resin (B) is not particularly limited, but it is preferably 300 to 3,000. If the weight average molecular weight of the resin (B) is 300 or more, the heat resistance will be sufficient, and the exhaust gas will be reduced in a high-temperature environment. On the other hand, if the weight average molecular weight of the resin (B) is 3,000 or less, the dissolution rate of the adhesive layer to the hydrocarbon-based solvent is good. Therefore, the residue of the adhesive layer on the substrate after the support plate is separated can be quickly dissolved and removed. In addition, the weight average molecular weight of the resin (B) in this embodiment means a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

Still, as the resin, a mixture of resin (A) and resin (B) may also be used. By mixing, it becomes one with good heat resistance. For example, as the mixing ratio of resin (A) and resin (B) (A): (B)=80:20~55:45 (mass ratio), it is ideal because of its excellent heat resistance and flexibility in high temperature environments .

(Acrylic-styrene resin)

Examples of the acrylic-styrene resin system include resins polymerized by using styrene or styrene derivatives, and (meth)acrylate esters as monomers.

Examples of the (meth)acrylate series include alkyl (meth)acrylates composed of a chain structure, (meth)acrylates having an aliphatic ring, and (meth)acrylic acid having an aromatic ring. ester. The (meth)acrylic acid alkyl esters composed of a chain structure include acrylic long alkyl esters having an alkyl group with 15 to 20 carbons, and acrylic alkyls having an alkyl group with 1 to 14 carbons. Base ester and so on. Examples of the acrylic long alkyl ester series include n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, Alkyl esters of acrylic acid or methacrylic acid such as n-eicosyl. Furthermore, the alkyl group may be branched.

Examples of the acrylic alkyl esters having an alkyl group having 1 to 14 carbon atoms include generally known acrylic acid alkyl esters used in existing acrylic adhesives. For example, the alkyl group is composed of methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, tridecyl Acrylic acid or methacrylic acid alkyl ester.

Examples of (meth)acrylates having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl (Meth) acrylate, isobornyl (meth) acrylate, tricyclodecyl (meth) propylene Ester, tetracyclododecyl (meth)acrylate, and dicyclopentyl (meth)acrylate, but isobornyl methacrylate and dicyclopentyl (meth)acrylate are preferable.

The (meth)acrylate system having an aromatic ring is not particularly limited, but examples of the aromatic ring system include phenyl, benzyl, tolyl, stubyl, biphenyl, naphthyl, anthracenyl, and benzene. Oxymethyl, phenoxyethyl, etc. In addition, the aromatic ring system may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is desirable.

(Maleimide resin)

As the maleimide resin system, for example, as a monomer, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-iso Propyl maleimide, Nn-butyl maleimide, N-isobutyl maleimide, N-sec-butyl maleimide, N-tertiary butyl maleimide Imine, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide Amines, N-stearyl maleimines and other maleimines with alkyl groups, N-cyclopropyl maleimines, N-cyclobutyl maleimines, N-ring Maleic acid with aliphatic hydrocarbon groups such as pentyl maleimide, N-cyclohexyl maleimide, N-cycloheptyl maleimide, N-cyclooctyl maleimide, etc. Amine, N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, Np-methylphenylmaleimide, etc. Resins obtained by polymerization of aromatic maleimides such as aryl groups.

(Elastomer)

The elastic system preferably contains a styrene unit as a constituent unit of the main chain, and the "styrene unit" may have a substituent. Examples of the substituent system include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, alkoxyalkyl groups having 1 to 5 carbon atoms, acetoxy groups, and carboxyl groups. In addition, the content of the styrene unit is preferably within the range of 14% by weight or more and 50% by weight or less. Furthermore, it is desirable that the weight average molecular weight of the elastic system is within the range of 10,000 or more and 200,000 or less.

If the content of the styrene unit is within the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is within the range of 10,000 or more and 200,000 or less, it will easily dissolve in the hydrocarbon-based solvent described later. The adhesive layer can be removed easily and quickly. In addition, since the content of styrene units and the weight average molecular weight are within the above ranges, the wafer substrate is suitable for resist solvents (such as PGMEA, PGME, etc.), acids (hydrofluorocarbons, etc.) exposed to the resist lithography step. Acids, etc.) and alkalis (TMAH, etc.) exhibit excellent resistance.

Furthermore, the above-mentioned (meth)acrylate may be further mixed with the elastomer.

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

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

As an elastic system, for example, the content of styrene unit is within the range of 14% by weight or more and 50% by weight or less, the weight average molecular weight of the elastomer A variety of elastomers can be used within the range of 10,000 or more and 200,000 or less. For example, polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene Block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), and, these hydrogenated products, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene block Copolymer (SEEPS), styrene block is a reaction cross-linked styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (manufactured by Kuraray), Septon V9475 (manufactured by Kuraray)), styrene intercalation The stage is a reactive cross-linked styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by Kuraray) with reactive polystyrene hard blocks), polystyrene-poly(ethylene- Ethylene/propylene) block-polystyrene block copolymer (SEEPS-OH: modified by terminal hydroxyl group), etc., can use elastomers whose styrene unit content and weight average molecular weight are within the above-mentioned ranges.

In addition, hydrides are also ideal in elastomers. If it is a hydride, the heat stability is improved, and it is difficult to cause deterioration such as decomposition or polymerization. In addition, it is also desirable from the viewpoint of solubility to hydrocarbon solvents and resistance to resist solvents.

In addition, it is also preferable to use a block polymer of styrene at both ends of the elastomer. Blocking styrene with high heat stability at both ends shows higher heat resistance.

More specifically, a hydrogenated product of a block copolymer of styrene and conjugated diene, which is an elastic system, is more desirable. The heat stability is improved, and it is difficult to cause deterioration such as decomposition or polymerization. In addition, it exhibits higher heat resistance by blocking styrene with high heat stability at both ends. Furthermore, the viewpoints of solubility to hydrocarbon solvents and resistance to resist solvents are also desirable.

Commercial products used as elastomers included in the adhesive constituting the adhesive layer 3 include, for example, "Septon (trade name)" manufactured by Kuraray, "HYBRAR (trade name)" manufactured by Kuraray, and "HYBRAR (trade name)" manufactured by Asahi Kasei Co., Ltd. "Tuftec (trade name)", "DYNARON (trade name)" manufactured by JSR, etc.

The content of the elastomer contained in the adhesive constituting the adhesive layer 3 is, for example, 100 parts by weight of the entire adhesive composition, preferably within a range of 50 parts by weight or more and 99 parts by weight, and 60 parts by weight or more, The range of 99 parts by weight or less is preferable, and the range of 70 parts by weight or more and 95 parts by weight or less is most preferable. By setting it within these ranges, it is possible to appropriately bond the substrate and the support plate while maintaining heat resistance.

In addition, multiple types of elastomers may be mixed. In short, the adhesive constituting the adhesive layer 3 may contain plural kinds of elastomers. Then, at least one of the plural types of elastomers may contain a styrene unit as a structural unit of the main chain. In addition, if at least one of the plural types of elastomers is within the range of 14% by weight or more and 50% by weight or less of the styrene unit, or the weight average molecular weight is within the range of 10,000 or more and 200,000 or less, then This is the scope of the invention. In addition, in the construction When the adhesive forming the adhesive layer 3 contains a plurality of types of elastomers, as a result of mixing, the content of the styrene unit may be adjusted so that the content of the styrene unit falls within the above-mentioned range. For example, if the content of styrene unit is 30% by weight of Septon (trade name) manufactured by Kuraray, Septon 4033, and the content of styrene unit is 13% by weight of Septon (trade name) Septon 2063 in a weight ratio of 1 to 1. When mixed, the styrene content of the entire elastomer contained in the adhesive becomes 21 to 22% by weight, and therefore becomes 14% by weight or more. In addition, for example, if the styrene unit is 10% by weight and 60% by weight are mixed in a weight ratio of 1 to 1, the result is 35% by weight, which falls within the above-mentioned range. The present invention may also be in such a form. In addition, the plural types of elastic systems contained in the adhesive constituting the adhesive layer 3 all contain styrene units within the above-mentioned range, and the weight average molecular weight within the above-mentioned range is the most desirable.

Still, it is desirable to form the adhesive layer 3 using a resin other than a photocurable resin (for example, a UV curable resin). It is possible to prevent the use of resins other than the photocurable resin from generating residues around the microscopic unevenness of the substrate 1 after peeling or removing the adhesive layer 3. In particular, the adhesive system constituting the adhesive layer 3 is not dissolved in all solvents, but is preferably dissolved in a specific solvent. This is because the substrate 1 does not apply physical force, but can be removed by dissolving the adhesive layer 3 in a solvent. When the adhesive layer 3 is removed, the adhesive layer 3 can be easily removed without breaking or deforming the substrate 1 even if the strength of the substrate 1 is low.

(Polymer resin)

The adhesive used to form the adhesive layer 3 may also contain a polymer resin. By forming the adhesive layer 3 with a polymer-based resin, even if the laminate is processed at a high temperature, it is possible to dissolve the adhesive layer in a subsequent step and peel off the support plate from the substrate. If the adhesive layer 3 contains a polycarbonate resin, the laminated body can be suitably used even in a high-temperature process in which the laminated body is processed at a high temperature of 300° C. or higher by annealing or the like.

The polycarbonate-based resin has a structure composed of a structural unit represented by the following general formula (3) and at least one of the structural units represented by the following general formula (4).

(Here, 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 composed of phenylene, naphthylene and anthracenyl Selected from the group, X'is an alkylene group having a carbon number of 1 or more and 3 or less).

The polyether-based resin is provided with at least one of the polyether constitutional unit represented by the formula (3) and the polyether constitutional unit represented by the formula (4) to form a laminated body, which is attached After the substrate 1 and the support plate 2, even if the substrate 1 is processed under high temperature conditions, the adhesive layer 3 can be prevented from being insolubilized due to decomposition and polymerization. In addition, if the polymer resin system is a polymer resin composed of a polymer structural unit represented by the above formula (3), even if it is added Heat to a higher temperature is also stable. Therefore, it is possible to prevent residues caused by the adhesive layer from being generated on the substrate 1 after cleaning.

The weight average molecular weight (Mw) of the polymer resin is preferably within the range of 30,000 or more and 70,000 or less, and more preferably within the range of 30,000 or more and 50,000 or less. If the weight average molecular weight (Mw) of the polyimide-based resin is within the range of 30,000 or more, for example, an adhesive composition that can be used at a high temperature of 300° C. or more can be obtained. In addition, if the weight average molecular weight (Mw) of the polymer resin is within the range of 70,000 or less, it can be dissolved appropriately depending on the solvent. That is, an adhesive composition that can be appropriately removed depending on the solvent can be obtained.

(Diluent solvent)

As the dilution solvent system used when forming the adhesive layer 3, for example, a straight chain such as hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane, tridecane, etc. Hydrocarbons, branched hydrocarbons with carbon numbers 4 to 15, for example, cyclohexane, cycloheptane, cyclooctane, naphthalene, decalin, tetrahydronaphthalene and other cyclic hydrocarbons, p-menthane, o- Menthane, m-menthane, diphenyl menthane, 1,4-terpene diol, 1,8-terpene diol, campane, norbornane, pinane, thumberane, carane, phyllene, Geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene -1-ol, terpinen-4-ol, dihydroterpineyl acetate, 1,4-cineole, 1,8-cineole, camphenol, carvone, ionone, arborvitae Terpene solvents such as ketone, camphor, d-limonene, l-limonene, and dipentene; lactones such as γ-butyrolactone; acetone, methyl Ketones such as ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isoamyl ketone, 2-heptanone, etc.; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc. Multivalent alcohols; compounds with ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, and the aforementioned multivalent alcohols Or polyvalent alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., or monophenyl ether, such as the compound having an ether bond, such as the aforementioned ester bond compound Derivatives (among these are propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are ideal); cyclic ethers such as dioxane, or methyl lactate, Ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, butyl methoxyacetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate Esters such as esters; aromatic organic solvents such as anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, etc.

(Other ingredients)

The adhesive that constitutes the adhesive layer 3 is within a range that does not impair the essential characteristics, and may further include other substances that are miscible. For example, additional resins, plasticizers, adhesive auxiliary agents, stabilizers, colorants, thermal polymerization inhibitors, and surfactants, etc., which are used to improve the performance of the adhesive, can be used, as well as various commonly used additives.

[Separation layer 4]

Next, the so-called separation layer 4 is irradiated through the support plate 2 by absorbing A layer of material that is degraded by the light.

The thickness of the separation layer 4 is preferably within a range of 0.05 μm or more and 50 μm or less, and more preferably within a range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer 4 is included in the range of 0.05 μm or more and 50 μm or less, the separation layer 4 can be altered as desired by short-time light irradiation and low-energy light irradiation. In addition, the thickness of the separation layer 4 is considered from the viewpoint of productivity, and it is particularly desirable to include it in the range of 1 μm or less.

Furthermore, in the laminate 10, another layer may be formed between the separation layer 4 and the support plate 2. In this case, the other layers may be made of materials that transmit light. Thereby, it is possible to appropriately add a layer that does not hinder the incidence of light to the separation layer 4 and imparts desired properties to the laminated body 10. Depending on the type of material constituting the separation layer 4, the wavelength of light that can be used is different. Therefore, it is not necessary for the material constituting the other layer to transmit all light, and a material capable of transmitting light of a wavelength that can change the material constituting the separation layer 4 can be appropriately selected.

In addition, it is desirable that the separation layer 4 is formed of only a material having a structure that absorbs light, but within a range that does not impair the essential characteristics of the present invention, a material that does not have a structure that absorbs light may be added to form the separation layer 4 . In addition, it is desirable that the surface of the separation layer 4 on the side opposite to the adhesive layer 3 is flat (no unevenness is formed), so that the separation layer 4 can be easily formed, and it can also be applied uniformly during sticking. .

The material of the separation layer 4 may be appropriately selected according to the type of the substrate and the support plate 2 and the performance required for the laminate. In the support separation method of this embodiment, among the separation layers shown below, it is preferable to use separation that can be degraded by CO ₂ laser that can irradiate infrared rays passing through the support plate 2 made of silicon. Floor.

(Fluorocarbon)

The separation layer 4 may also be composed of fluorocarbon. Since the separation layer 4 is made of fluorocarbon, it absorbs light and changes its quality. As a result, it loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, raising the support plate 2 etc.), the separation layer 4 can be destroyed, and the support plate 2 and the substrate 1 can be easily separated. The fluorocarbon system constituting the separation layer 4 can be suitably formed into a film by a plasma CVD (chemical vapor deposition) method.

Fluorocarbon absorbs light with a wavelength within a specific range depending on the type. By irradiating the separation layer with light of a wavelength used in the fluorocarbon absorption range of the separation layer 4, the fluorocarbon can be appropriately modified. However, it is desirable that the light absorption rate in the separation layer 4 is 80% or more.

As the light system irradiated on the separation layer 4 according to the wavelength that can be absorbed by fluorocarbon, for example _{, solid lasers such as YAG lasers, ruby lasers, glass lasers, YVO 4} lasers, LD lasers, and fiber lasers are suitably used. , Liquid lasers such as pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers and other gas lasers, semiconductor lasers, free electron lasers and other lasers, or non- Laser light is fine. The wavelength at which the fluorocarbon can be modified is not limited here. For example, those in the range of 600 nm or less can be used.

(Polymer containing a light-absorbing structure in the repeating unit)

The separation layer 4 may contain a polymer in which a structure having light absorption is included in the repeating unit. The polymer is irradiated by light and deteriorated. The deterioration of the polymer is produced by absorbing the light irradiating the above-mentioned structure. As a result of the deterioration of the polymer, the separation layer 4 loses its strength or adhesion before being irradiated with light. Therefore, by applying a slight external force (for example, raising the support plate 2 etc.), the separation layer 4 can be destroyed, and the support plate 2 and the substrate 1 can be easily separated.

The above-mentioned structure having light absorption is a chemical structure that absorbs light and changes the polymer containing the structure as a repeating unit. This structure system contains, for example, a conjugated π-electron atomic group composed of a substituted or unsubstituted benzene ring, a condensed ring, or a heterocyclic ring. In more detail, the structure may be a cardo structure, or a diphenyl ketone structure, a diphenyl sulfene structure, a diphenyl sulfide structure (bisphenyl sulfide structure), or a diphenyl ketone structure present in the side chain of the above-mentioned polymer. Diphenyl structure or diphenylamine structure.

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

(In the formula, R is independently an alkyl, aryl, halogen, hydroxyl, ketone, sulfo, or N(R ⁴ )(R ⁵ ) (here, R ⁴ and R ⁵ are Each independent hydrogen atom or C1-C5 alkyl), Z is not present or -CO-, -SO ₂ -, -SO- or -NH-, n is an integer of 0 or 1 to 5).

In addition, the above-mentioned polymer contains, for example, a repeating unit represented by any one of (a) to (d), or represented by (e), or the structure of (f) is included in the main chain in the following formula: .

(In the formula, l is an integer of 1 or more, m is 0 or an integer of 1~2, X is any of the formulae shown in (a)~(e) above "Chemical 3", in (f) It is any one of the formulae shown in the above-mentioned "Chemical 3", or does not exist, Y ₁ and Y ₂ are each independently -CO- or SO _{2 -.} l is ideally an integer of 10 or less).

As an example of the benzene ring, condensed ring and heterocyclic ring represented by the above-mentioned "Chemical 3" The system can include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, acridine, substituted acridine, azobenzene, substituted azobenzene , Fluorescent amine, substituted fluorescent amine, Furuorimon, substituted Furuorimon, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene, substituted pyrene. When the exemplified substituent has more substituents, examples of the substituent system include alkyl groups, aryl groups, halogen atoms, alkoxy groups, nitro groups, aldehydes, cyano groups, amides, and dialkylamino groups. , Sulfonamide, imine, acid, carboxylic acid ester, sulfonic acid, sulfonic acid ester, alkyl amine group and aryl amine group selection.

Among the substituents shown in the above "Chemical 3", the fifth substituent having two phenyl groups, as an _{example of the case where Z is -SO 2} -is bis(2,4-dihydroxy Phenyl) clump, bis(3,4-dihydroxyphenyl) clump, bis(3,5-dihydroxyphenyl) clump, bis(3,6-dihydroxyphenyl) clump, bis(4-hydroxybenzene) Bis(3-hydroxyphenyl), bis(2-hydroxyphenyl), and bis(3,5-dimethyl-4-hydroxyphenyl), etc.

Among the substituents shown in the above "Chemical 3", the fifth substituent having two phenyl groups, as an example of the case where Z is -SO-, bis(2,3-dihydroxybenzene Group) sulphurous acid, bis(5-chloro-2,3-dihydroxyphenyl) sulphurite, bis(2,4-dihydroxyphenyl) sulphurite, bis(2,4-dihydroxy-6-methyl) Phenyl) sulfene, bis(5-chloro-2,4-dihydroxyphenyl) sulfene, bis(2,5-dihydroxyphenyl) sulfene, bis(3,4-dihydroxyphenyl) sulfide Sulphurite, bis(3,5-dihydroxyphenyl) sulphurite, bis(2,3,4-trihydroxyphenyl) sulphurite, bis(2,3,4-trihydroxy-6-methylphenyl) Supplementary, bis(5-chloro-2,3,4-trihydroxyphenyl) sulfene, bis(2,4,6-trihydroxyphenyl) sulfonite, bis(5-chloro-2,4,6 -Trihydroxyphenyl) 碸 etc.

Among the substituents shown in the above "Chemical 3", the fifth substituent having 2 phenyl groups, as an example of the case where Z is -C(=O)-, 2,4-di Hydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2',5,6'-tetrahydroxybenzophenone Methyl ketone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecylbenzophenone, 2,2' -Dihydroxy-4-methoxybenzophenone, 2,6-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxydiphenyl Methyl ketone, 4-amino-2'-hydroxybenzophenone, 4-dimethylamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone , 4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2',4'-dihydroxybenzophenone, and 4-di Methylamino-3',4'-dihydroxybenzophenone, etc.

In the case where the above-mentioned structure is present in the side chain of the above-mentioned polymer, the proportion of the repeating unit including the above-mentioned structure occupying the above-mentioned polymer is within the range of 0.001% or more and 10% or less of the light transmittance of the separation layer 4 . If the polymer is prepared so that the ratio is included in such a range, the separation layer 4 can sufficiently absorb light and can be surely and rapidly deteriorated. That is, the removal from the support plate 2 of the laminate 10 is easy, and the light irradiation time required for the removal can be shortened.

The above-mentioned structure can absorb light having a wavelength in a desired range through the selection of this type. For example, the wavelength of light that can be absorbed by the above-mentioned structure is preferably within a range of 100 nm or more and 2,000 nm or less. Within this range, the wavelength of light that can be absorbed by the above structure is a shorter wavelength The side is, for example, within the range of 100 nm or more and 500 nm or less. For example, it is desirable that the above-mentioned structure is such that by absorbing ultraviolet light having a wavelength in the range of approximately 300 nm or more and 370 nm or less, the polymer containing the structure can be modified.

Light systems that can be absorbed by the above structure are high-pressure mercury lamps (wavelength range: 254nm or more and 436nm or less), KrF excimer lasers (wavelength: 248nm), ArF excimer lasers (wavelength: 193nm), F2 excimer lasers (wavelength : 157nm), XeCl laser (wavelength: 308nm), XeF laser (wavelength: 351nm) or solid UV laser (wavelength: 355nm), g-line (wavelength: 436nm), h-line (wavelength: 405nm) or i-line (wavelength: 365nm), etc.

The above-mentioned separation layer 4 contains a polymer having the above-mentioned structure as a repeating unit, but the separation layer 4 is further and may contain components other than the above-mentioned polymer. Examples of the component system include fillers, plasticizers, and components that can improve the releasability of the support plate 2. These components can be appropriately selected from previously generally known substances or materials that do not hinder or promote the absorption of light and the deterioration of the polymer according to the above-mentioned structure.

(Inorganic)

The separation layer 4 may also be composed of an inorganic substance. Since the separation layer 4 is made of an inorganic substance, it absorbs light and changes its quality. As a result, it loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, raising the support plate 2 etc.), the separation layer 4 can be destroyed, and the support plate 2 and the substrate 1 can be easily separated.

The above-mentioned inorganic substance system should just be a structure which changes quality by absorption of light, For example, 1 or more types of inorganic substances selected from the group which consists of a metal, a metal compound, and carbon can be used suitably. The so-called metal compound refers to a compound containing a metal atom, and may be, for example, a metal oxide or a metal nitride. Examples of such inorganic substances are not limited to this, and examples include the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon Choose more than one inorganic substance. Moreover, the so-called carbon series may also contain the concept of allotropes of carbon, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, etc.

The above-mentioned inorganic substance absorbs light having a wavelength within a specific range according to the type. By irradiating the separation layer with light of a wavelength used in the absorption range of the inorganic substance of the separation layer 4, the above-mentioned inorganic substance can be appropriately changed in quality.

As the light irradiated on the separation layer 4 made of inorganic substances, according to the wavelength that the above-mentioned inorganic substances can absorb, for example, YAG lasers, ruby lasers, glass lasers, YVO ₄ lasers, LD lasers, and fiber lasers are suitably used. Solid lasers such as solid lasers, liquid lasers such as pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers and other gas lasers, semiconductor lasers, free electron lasers, etc. Laser light or non-laser light is fine.

The separation layer 4 made of an inorganic substance can be formed on the support plate 2 by commonly known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating, and the like. The thickness of the separation layer 4 made of inorganic substances is not particularly limited, if it is sufficient to absorb The film thickness of the light used may be sufficient, and it is preferable to set the film thickness within the range of 0.05 μm or more and 10 μm or less, for example. In addition, an adhesive may be applied to both sides or one side of an inorganic film (for example, a metal film) composed of an inorganic substance constituting the separation layer 4 in advance, and then attached to the support plate 2 and the substrate 1.

Furthermore, when a metal film is used as the separation layer 4, the conditions such as the film quality of the separation layer 4, the type of laser light source, and the laser output can cause reflection of the laser or charging to the film. Therefore, it is desirable to provide an anti-reflection film or an anti-static film on or above the separation layer 4, and to seek such countermeasures.

(Compounds with infrared absorbing structure)

The separation layer 4 may be formed of a compound having an infrared absorbing structure. The compound deteriorates 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, by applying a slight external force (for example, raising the support plate 2 etc.), the separation layer 4 can be destroyed, and the support plate 2 and the substrate 1 can be easily separated.

As an infrared-absorbing structure or a compound system containing an infrared-absorbing structure, for example, alkanes, alkenes (vinyl, trans, cis, vinylidene, tri-substituted, tetra-substituted, conjugated, accumulated Alkenes, cyclic), alkynes (monosubstituted, disubstituted), monocyclic aromatics (benzene, monosubstituted, disubstituted, trisubstituted), alcohols and phenols (OH radicals, intramolecular hydrogen bonds, intermolecular Hydrogen bond, saturated secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetals, ketals, aliphatic ethers, aromatic ethers, vinyl ethers, ethylene oxide cyclic ethers , Peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3-diketone enol, o-hydroxyaryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylic acid Acid anion), formate, acetate, conjugated ester, non-conjugated ester, aromatic ester, lactone (β-, γ-, δ-), aliphatic acid chloride, aromatic acid chloride, Acid anhydrides (conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, internal amine, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic) , Tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic Isonitrile, isocyanate, thiocyanate, aliphatic thiocyanate, aromatic thiocyanate, aliphatic nitro compound, aromatic nitro compound, nitramine, nitrosamine, nitrate, nitrite, nitros Group bonds (aliphatic, aromatic, monomer, dimer), sulfur compounds such as mercaptans, thiophenols, and sulfuric acid, thiocarbonyl, sulfenite, sulfonium, sulfonyl chloride, primary sulfonamide, secondary sulfonamide Amine, sulfate, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O, or halogen), PA ² bond (A ² is H, C, or O), or Ti-O bond.

As the structural formula system containing the above-mentioned carbon number-halogen bond, for example, -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF= CF ₂ , fluorinated aryl, and chlorinated aryl, etc.

Examples of the structure system containing the above-mentioned Si-A ¹ _{bonding include 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 etc. As a structural system containing Si-A ¹ bonding, it is particularly desirable to form a siloxane skeleton and a silsesquioxane skeleton.

Examples of the structure system containing the above-mentioned PA ² _{bonding include PH, PH 2} , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -PO (A ³ is aliphatic or aromatic), (A ⁴ O) ₃ -PO (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH, and O=P-OH, etc.

The above-mentioned structure can absorb infrared rays having a desired range of wavelengths by the selection of this type. Specifically, the above-mentioned structure is such that the wavelength of the infrared ray that can be absorbed is, for example, within the range of 1 μm or more and 20 μm or less, and it can be more appropriately absorbed within the range of 2 μm or more and 15 μm or less. Furthermore, in the case where the above-mentioned structure is Si-O bonding, Si-C bonding, and Ti-O bonding, it may be within a range of 9 μm or more and 11 μm or less. Moreover, the wavelength of infrared rays that can be absorbed by each structure can be easily understood by the industry. For example, as the absorption band in each structure, refer to the non-patent literature: SILVERSTEIN. BASSLER. Morrill's "Spectrum Identification Method of Organic Compounds (5th Edition)-Combination of MS, IR, NMR, and UV -" (published in 1992) pages 146 to 151.

As used in the formation of the separation layer 4, the compound having the infrared absorbing structural formula is among the compounds having the above-mentioned structure, such as those that can be dissolved in a solvent for coating and can be cured to form a solid layer, It is not particularly limited. However, in order to effectively change the quality of the compound in the separation layer 4, it is desirable to easily separate the support plate 2 from the substrate 1 because the absorption of infrared rays in the separation layer 4 is large, that is, when the separation layer 4 is irradiated with infrared rays. The transmittance is low. Specifically, it is ideal that the infrared transmittance of the separation layer 4 is less than 90%, and the infrared transmittance is less than 80%. Ideal.

As an example, as the compound system having a siloxane skeleton, for example, a resin of a copolymer of a repeating unit represented by the following chemical formula (5) and a repeating unit represented by the following chemical formula (6), or It is a resin of a copolymer of a repeating unit represented by the following chemical formula (5) and a repeating unit derived from an acrylic compound.

(In the chemical formula (6), R ⁶ is hydrogen, an alkyl group with a carbon number of 10 or less, or an alkoxy group with a carbon number of 10 or less).

Among them, as a compound having a siloxane skeleton, t-butyl styrene (TBST)-dimethyl styrene is a copolymer of the repeating unit represented by the above chemical formula (5) and the repeating unit represented by the following chemical formula (7) The base silicone copolymer is more ideal. The repeating unit represented by the above chemical formula (5) and the repeating unit represented by the following chemical formula (7) are contained in a ratio of 1:1, TBST-dimethylsiloxane copolymer For more ideal.

In addition, as the compound having a silsesquioxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (8) and a repeating unit represented by the following chemical formula (9) can be used.

(In the chemical formula (8), R ⁷ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in the chemical formula (9), R ⁸ is an alkyl group or phenyl group having 1 to 10 carbon atoms).

As a compound with a silsesquioxane skeleton, it can also be combined Appropriate use can be found in Japanese Patent Application Publication No. 2007-258663 (published on October 4, 2007), Japanese Patent Application Publication No. 2010-120901 (published on June 3, 2010), and Japanese Patent Application Publication No. 2009-263316 (2009). Published on November 12), and each silsesquioxane resin disclosed in Japanese Patent Application Laid-Open No. 2009-263596 (published on November 12, 2009).

Among them, as a compound having a silsesquioxane skeleton, a copolymer having a repeating unit represented by the following chemical formula (10) and a repeating unit represented by the following chemical formula (11) is preferable, and the following chemical formula (10) The repeating unit represented and the repeating unit represented by the following chemical formula (11) are more preferably a copolymer containing 7:3.

As the polymer system with a silsesquioxane skeleton, there can be random structure, ladder structure, cage structure, and any structure is acceptable.

In addition, the compound system containing Ti-O bonding includes, for example, (i) tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexyloxy) titanium, and titanium -i-propoxy octyl glycolate and other titanium alkoxides; (ii) di-i-propoxy‧bis(acetacetone)titanium, and propanedioxytitanium bis(ethylacetone) (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 and other titanium polymers; (iv) Tri-n-butoxy titanium monostearate, titanium stearate, di-i-propoxy Titanium diisostearate, and (2-n-butoxycarbonylbenzyloxy) tributoxy titanium, etc.; (v) bis-n-butoxy‧bis(tri Ethanolamine) titanium and other water-soluble titanium compounds.

Among them, the compound containing Ti-O bond is bis-n-butoxy‧bis(triethanolamine) titanium (Ti(OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N(C ₂ H ₄ OH) ₂ ] ₂ ) is ideal.

The above-mentioned separation layer 4 contains a compound having an infrared absorbing structure, but the separation layer 4 is further and may contain components other than the above-mentioned compounds. Examples of the component system include fillers, plasticizers, and components that can improve the releasability of the support plate 2. These components can be appropriately selected from previously generally known substances or materials that do not hinder or promote the absorption of infrared rays and the deterioration of the compound according to the above-mentioned structure.

(Infrared absorbing material)

The separation layer 4 may contain an infrared absorbing substance. Since the separation layer 4 is composed of an infrared absorbing material, it absorbs light to cause deterioration, and as a result, it loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, raising the support plate 2, etc.), By destroying the separation layer 4, the support plate 2 and the substrate 1 can be easily separated.

The infrared absorbing material may be a structure that changes its quality by absorbing infrared rays. For example, carbon black, iron particles, or aluminum particles can be suitably used. Infrared absorbing materials absorb light with a wavelength within a specific range depending on the type. By irradiating the separation layer 4 with light of a wavelength used in the range where the infrared absorbing material of the separation layer 4 absorbs, the infrared absorbing material can be appropriately changed in quality.

(Reactive polysilsesquioxane)

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

In this specification, the so-called 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 , By condensing the silanol group or functional groups that can form a silanol group, which can be polymerized with each other. In addition, if the reactive polysilsesquioxane system has a silanol group or a functional group capable of forming a silanol group, a silsesquioxane skeleton having a random structure, a cage structure, a ladder structure, etc. can be used.

In addition, it is desirable that the reactive polysilsesquioxane system has a structure represented by the following formula (12).

In the formula (12), R" is each independently selected from the group consisting of hydrogen and an alkyl group with a carbon number of 1 or more and 10 or less, and a group consisting of hydrogen and an alkyl group with a carbon number of 1 or more and 5 or less It is more desirable to select from the group. If R" is hydrogen or an alkyl group with a carbon number of 1 or more and 10 or less, the heating in the separation layer formation step can make the reactive polymerization represented by formula (12) multiply Semisiloxane is suitably condensed.

In formula (12), p is preferably an integer of 1 or more and 100 or less, and an integer of 1 or more and 50 or less is more preferable. The reactive polysilsesquioxane is formed by having the repeating unit shown in formula (12), and is formed by using other materials. The content of Si-O bond is higher, and it can be formed in infrared light (0.78μm or more, 1000 μm or less), preferably far-infrared rays (3 μm or more and 1000 μm or less), and more preferably a separation layer 4 having a high absorbance with a wavelength of 9 μm or more and 11 μm or less.

In addition, in the formula (12), R'is an organic group that is independent of each other and is the same or different from each other. Here, the R system is, for example, an aryl group, an alkyl group, an alkenyl group, etc., and these organic groups may have a substituent.

When R'is an aryl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, etc. can be mentioned, and a phenyl group is preferable. In addition, the aryl group may be bonded to the polysilsesquioxane skeleton through an alkylene group having 1 to 5 carbon atoms.

When R'is an alkyl group, examples of the alkyl group include linear, branched, or cyclic alkyl groups. In addition, when R is an alkyl group, the carbon number system is preferably 1 to 15, and 1 to 6 are more desirable. In addition, when R is a cyclic alkyl group, it may be an alkyl group having a monocyclic or di- to tetracyclic structure.

When R'is an alkenyl group, it is the same as in the case of an alkyl group. Examples include linear, branched, or cyclic alkenyl groups. The alkenyl group preferably has 2 to 15 carbon atoms, and 2 to 6 For more ideal. In addition, when R is a cyclic alkenyl group, it may be a monocyclic or di-tetracyclic alkenyl group. As an alkenyl group, a vinyl group, an allyl group, etc. are mentioned, for example.

In addition, examples of the substituent system that R'may have include a hydroxyl group, an alkoxy group, and the like. In the case where the substituent is an alkoxy group, linear, branched, or cyclic alkyl alkoxy groups can be mentioned. The carbon number of the alkoxy group is preferably 1-15, and the number of carbon atoms in the alkoxy group is preferably 1~10. ideal.

In addition, in one point of view, the siloxane content of the reactive polysilsesquioxane is preferably 70 mole% or more and 99 mole% or less, and more preferably 80 mole% or more and 99 mole% or less. If the silicone content of the reactive polysilsesquioxane is 70 mole% or more and 99 mole% or less, it can be formed by irradiating infrared rays (ideally far infrared rays, more preferably light with a wavelength of 9 μm or more and 11 μm or less). A properly deteriorated separation layer.

In addition, from one viewpoint, 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. Reactive poly sesqui The weight average molecular weight (Mw) of siloxane is above 500 and below 50,000, so it can be dissolved in a solvent and can be applied to a support plate.

Examples of commercially available products that can be used as reactive polysilsesquioxanes include SR-13, SR-21, SR-23, SR-33 manufactured by Konishi Chemical Industry Co., Ltd., and the like.

〔other〕

In the support separation method according to this embodiment, as another configuration, a dicing tape 5 provided with a dicing frame 6 can be used.

(Cutting tape 5)

A dicing tape 5 is attached to the side of the substrate 1 of the laminate 10. The dicing tape 5 is used for manufacturing a semiconductor wafer by dicing the substrate 1 after peeling off the support plate 2.

As the dicing tape 5, for example, the dicing tape 5 can be used for the structure of forming an adhesive layer of a base film. As the base film system, for example, resin films such as PVC (polyvinyl chloride), polyolefin, or polypropylene can be used. The outer diameter of the dicing tape 5 is greater than the outer diameter of the substrate 1. If it is adhered, a part of the dicing tape 5 will be exposed at the outer edge of the substrate 1.

(Cutting box 6)

A cutting frame 6 is installed on the outer periphery of the exposed surface of the dicing tape 5 to prevent bending of the dicing tape 5. Examples of the cutting frame 6 include cutting frames made of metals such as aluminum, and cutting frames made of alloys such as stainless steel (SUS). Frames, and cut frames made of resin.

<Related Support Separation Method for Modifications>

The support separation method according to the present invention is not limited to the above-mentioned embodiment. For example, in a method for separating a support body according to a modified example, as shown in Figure 3(b), the laminated body 10 encompasses the entire circumference of the circuit formation area and occupies a range of the width W'1 in the radial direction. Among the non-circuit formation areas, the specific area occupying the range of the width W′2 has a structure that is not separated from the circuit formation area on the substrate 1. Regarding the support separation method of this modification, for example, when the value of the width W'1 is less than 2mm, the width W'2 of the divided region of the separation layer 4 irradiated by the laser light L can be easily ensured to be about 1.3mm The key points above are effective.

Since the above-mentioned configuration can prevent the laser light L from being directly irradiated to the circuit formation area of the substrate 1, it is possible to prevent the integrated circuit formed on the substrate 1 from being damaged by the laser light L.

In addition, in another modification of the support separation method, as shown in Figure 3(c), the entire circumference of the circuit formation area is surrounded, and the range of the width W"2 in the radial direction of the specific area occupies the non-circuit The width of the formation area is less than 100%.

Because of the above configuration, the laser light L can also be prevented from irradiating the outer peripheral end of the substrate 1 further outside, and the laser light L can be prevented from irradiating the circuit formation area of the substrate 1. This modification example is effective when the width of the non-circuit formation area of the substrate 1 is about 1.3 mm, and it is effective at the point that the area where the laser light L is irradiated on the separation layer 4 can be secured.

<About the support separation method of the second embodiment>

The support separation method according to the present invention is not limited to the above-mentioned embodiment. For example, the support separation method of one embodiment (the second embodiment) further includes a detection step of detecting the direction of the laminated body 10 before the light irradiation step. In the separation step, according to the layer detected in the detection step In the direction of the integrated body 10, the separation plate (holding part, not shown) provided with an adsorption pad holding the support plate (support body) 2 in order to apply force to the laminated body 10 is arranged in the divided area 4C where the laser light L is irradiated -1~4C-6 above the way, the laminated body 10 is rotated. Here, when the separation plate holds the support plate 2, the peripheral portion of the support plate 2 is provided with four suction pads arranged at equal intervals.

With the above-mentioned configuration, even if the laser light L is not irradiated to the entire area 4C of the separation layer 4, the detection step is based on the direction of the specific layered body 10, and the layered body 10 is only in line with the separation plate. It is sufficient that the divided area of the position where the suction pad is arranged is subjected to the light irradiation stage. Therefore, the time for irradiating the laser light L to the separation layer 4 can be further shortened, and the support plate 2 can be separated from the laminated body 10 more quickly. In addition, regarding the support separation method related to this embodiment, only the differences from the support separation method related to the first embodiment will be described, and the description of the similarities will be omitted.

[Detection steps]

In the detection step, before the light irradiation step, by detecting the optical alignment device (not shown) provided in the notch portion (notch, not shown) of the support plate 2 (Illustration), the direction of the laminate 10 is specified using the notch as a reference. Therefore, the subsequent light irradiation step can be performed in such a way that it can be specified whether or not any divided region of the separation layer 4 has been irradiated with light.

In the detection step, for example, as shown in (b) of Figure 2, at the position of the one-dot chain line C1, the direction of the laminated body 10 before the light irradiation step is set so as to be arranged in the notch of the support plate 2. can.

[Light irradiation step]

As shown in Figure 2(b), the light irradiation step included in the support separation method of this embodiment is after the detection step. By repeating the light irradiation stage and the rotating stage, the single-point chain line The separation layer 4 of the divided regions 4C-1 to 4C-6 divided by C1 to C10 is deteriorated. By this, the separation layer 4 of the divided regions 4C-1 to 4C-6 arranged in a total of 4 locations is changed in a manner of being separated at equal intervals in the peripheral portion of the separation layer 4.

(Separation step)

In the separation step, first, according to the direction of the laminated body 10 detected in the detection step, the adsorption pads of the four separation plates holding the support plate 2 are arranged in the division areas 4C-1 to 4C- where the laser light L is irradiated. 6 above, the above-mentioned laminated body 10 is rotated. After that, the support plate 2 located above the divided areas 4C-1 to 4C-6 is held by each suction pad and raised. As a result, it is possible to concentrate the force applied from the separation plate in the separation layer 4 that has deteriorated in the divided regions 4C-1 to 4C-6. Therefore, after the separation layer 4 that has been deteriorated in the divided regions 4C-1 to 4C-6 is destroyed, it can be used in the area not irradiated with the laser light L. The separation layer 4 of the domain concentrates the force. Thereby, the support plate 2 can be appropriately separated from the laminated body 10.

<Related Support Separation Methods in Other Embodiments>

The support separation method according to the present invention is not limited to the above-mentioned embodiment (the first embodiment and the second embodiment). For example, in the support separation method in other embodiments, the materials of the support plate (support) and the separation layer can be appropriately selected in accordance with the required performance of the laminate. Therefore, the laser system that emits the light irradiated on the separation layer is not limited to CO ₂ lasers, but solid lasers such as YAG lasers, ruby lasers, glass lasers, YVO ₄ lasers, LD lasers, fiber lasers, etc. Lasers, liquid lasers such as pigment lasers, _{gas lasers such as CO 2} lasers, excimer lasers, Ar lasers, He-Ne lasers, semiconductor lasers, free electron lasers, etc., or It is non-laser light or the like, and it can be appropriately selected and used in accordance with the wavelength that can change the quality of the material constituting the separation layer 4.

In addition, in the support separation method of the present embodiment, the holding portion of the support plate 2 held on the laminated body 10 is provided with a plurality of clamps (claws, not shown) for holding the outer peripheral end of the support plate 2, for example. The separation plate shown) can also be used.

In addition, in the support separation method according to another embodiment, the light irradiation step is performed, and the number and arrangement of the divided regions to be irradiated with light are based on the number or arrangement of the adsorption pads of the holding portion, and the design can be appropriately changed.

The present invention is not limited to the above-mentioned embodiments, please The range shown in the terms can be changed in various ways, and embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

〔Industrial availability〕

The support separation method according to the present invention can be suitably used in the manufacturing steps of miniaturized semiconductor devices.

1‧‧‧Substrate

2‧‧‧Support plate (support body)

3‧‧‧Next layer

4‧‧‧Separation layer

5‧‧‧Cutting tape

6‧‧‧Cutting frame

10‧‧‧Laminated body

50‧‧‧Laser Irradiation Device

Claims (9)

A method for separating a support body, which is a laminated body obtained by laminating a substrate, a support body that transmits light, and a separation layer that is degraded by absorption of light through an adhesive layer, and separates the support of the support body The method for body separation is characterized in that the substrate has a circuit formation area where a circuit is formed, and a non-circuit formation area surrounding the entire circumference of the circuit formation area where the circuit is not formed; and the method has the following steps: interposing the support body , Laminated in such a way that it faces a specific area of the substrate that surrounds the entire circumference of the circuit formation area and occupies more than 65% of the radius of the non-circuit formation area, but less than 100% of the area A light irradiation step of irradiating at least a part of the separated layer with light, and a separation step of applying force to the laminated body irradiated with the light, and separating the support from the laminated body, and the light irradiation step includes a light irradiation The stage is at least one of the above-mentioned separation layers laminated so as to face the divided specific regions with the center of the plane of the above-mentioned laminated body as the center point and the above-mentioned specific regions are equally divided at a specific angle In one part, light is irradiated to each divided area of equal division, and a rotation stage, which uses the center of the plane of the laminated body as the center point to rotate the plane of the laminated body at the specific angle. The support separation method of claim 1, wherein the inner peripheral end of the specific area is separated from the outer peripheral end of the circuit formation area, In addition, the outer peripheral end portion of the specific region is separated from the outer peripheral end portion of the substrate. Such as the support separation method of claim 1 or 2, wherein the width in the radial direction of the non-circuit forming area is within the range of greater than 1.3 mm and 2.0 mm, and the width in the radial direction of the specific area is 1.3 Above mm but less than 2.0mm. The support separation method of claim 1, wherein, before the light irradiation step, a detection step of detecting the direction of the laminate body is further included, and in the separation step, based on the direction of the laminate body detected by the detection step In order to apply a force to the laminated body, the holding portion holding the support body rotates the laminated body so as to be arranged on the divided specific region of the irradiated light. The support separation method according to claim 4, wherein, before the separation step, the light irradiation stage and the rotation stage are alternately repeated, and they are laminated so as to face all the divided specific regions. The above-mentioned separation layer is irradiated with light. The support separation method according to claim 1, wherein light is irradiated to an area of 50% or more of the separation layer laminated so as to face the divided specific region. Such as the support separation method of claim 1, wherein the light irradiation pattern is any one of linear, dot, ring, polygonal dot, polygonal ring, or spiral. Such as the support separation method of claim 1, wherein the support system is composed of silicon, The above-mentioned optical carbonic acid laser. The support separation method of claim 1, wherein a dicing tape is attached to the substrate side of the laminate, and a part of the dicing tape is exposed at the outer edge of the substrate.

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