TW202245030A - Method for treating workpiece - Google Patents

Abstract

The present invention provides a method for treating workpiece, in which a workpiece such as wafer is treated in the state of a laminate that is obtained by fixing the workpiece to a support via a temporarily fixing material, and the method is capable of stably peeling the workpiece off the laminate by a relatively simple process such as mechanical peeling. This object can be solved by a method for treating workpiece that includes the following steps: step (1) of laminating a support (A), a temporarily fixing material (B), and a workpiece (C) situated on a surface of the temporarily fixing material (B) opposite to the side of the support (A); step (2) of applying at least one treatment selected from heat treatment, mechanical treatment, wet processing, and laser processing; and step (3) of separating the workpiece (C) from the laminate (D) having the treated workpiece (C); the ratio of "the 10 DEG peeling strength P1 between the support (A)/adhesive layer (B)" to "the 10 DEG peeling strength P2 between the adhesive layer (B)/workpiece (C)" (P2/P1) measured when each angle formed by the peeled layers is maintained at 10DEG is 1.1 or more.

Description

Workpiece handling method

The present invention relates to a processing method for workpieces such as wafers, which processes workpieces in a state where workpieces such as wafers are fixed to a support through a temporary fixing material, and more specifically relates to a processing method. By introducing a support body to improve the workability of the workpiece, it can be used in various processing processes, and at the same time, it can stably separate the workpiece by relatively simple processes such as mechanical peeling.

In the semiconductor manufacturing process, because of the thinness and breakage of the workpiece, sometimes it is necessary or preferable to temporarily fix the workpiece during processing. For example, wafers on which functional layers for semiconductor elements are formed are widely thinned due to the high accumulation of semiconductor elements, but here, if the thinness is reduced to the limit, only adhesive tape cannot support the wafer. The temporary fixing material temporarily fixes it on a hard carrier (support body) for processing after thinning. Such a semiconductor manufacturing process using a support is called a wafer support system.

As a method of peeling the support after the treatment, a method of using gas generated from the temporary fixing material (for example, refer to Patent Document 1), a method of peeling off using a laser, and melting the resin of the temporary fixing material to make the carrier slide off have been proposed. The peeling method, the method of pulling up one end of the carrier to peel it off (mechanical peeling), etc.

The mechanical exfoliation method has a cost advantage due to the simplicity of the device. However, the mechanical stripping method is In principle, at least a peeling force must be applied to the workpiece/temporary fixing material interface and the temporary fixing material/support interface, so it may not be easy to perform peeling stably at the expected interface. If peeling occurs at an unexpected interface (for example, the workpiece/temporary fixing material interface), problems such as damage to the support body or electronic parts will occur when the support body is peeled off.

On the other hand, in order to avoid peeling from the unexpected interface during mechanical peeling, the adhesive force of the unexpected interface can also be increased, but if the adhesive force is increased too much, for example, it will become difficult to peel the temporary fixing material from the workpiece.

[Prior Art Literature]

[Patent Document]

[Patent Document 1] International Publication No. 2014/024861 A1 Handbook

In view of the above-mentioned technical background, the purpose of the present invention is to provide a processing method for workpieces such as wafers, which is processed in a state where the workpiece is fixed to a laminated body of a support through a temporary fixing material, and can be mechanically peeled off. The process stably separates workpieces such as wafers from laminates.

As a result of in-depth studies by the inventors of the present invention, it was found that in a workpiece processing method in which a workpiece such as a wafer is fixed to a laminated body of a support through a temporary fixing material, the support/temporary measured under specific conditions Peel strength between fixing materials and temporary fixing materials When the peeling strength between workpieces satisfies specific conditions, workpieces such as wafers can be stably separated from the laminated body by relatively simple processes such as mechanical peeling, and the present invention has been completed

That is, the present invention relates to the following content:

[1]

A method for processing workpieces, comprising the following steps:

Step (1), laminating the support body (A), the temporary fixing material (B), and the workpiece (C) located on the side of the temporary fixing material (B) opposite to the side of the support body (A);

Step (2), subjecting the workpiece (C) to at least one treatment selected from heat treatment, mechanical processing, wet treatment and laser processing; and

Step (3), separating the workpiece (C) from the laminate (D) having the processed workpiece (C); wherein,

The "10° peel strength P ₁ between the support body (A)/temporary fixing material (B)" and "temporary fixing material (B)/temporary fixing material (B)/ The ratio P ₂ /P ₁ of the 10° peel strength P ₂ ″ between the workpieces (C) is 1.1 or more.

The following [2] to [13] are all preferred forms or implementation forms of the present invention.

[2]

The method for treating workpieces according to [1], wherein the peel strength P ₁ is 10N/25mm or less.

[3]

The method for processing workpieces as described in [1] or [2], wherein the temporary fixing material (B) is bonded between the adhesive material layer connected to the support (A) and the adhesive layer connected to the workpiece (C) The material layers have different compositions.

[4]

The processing method of the workpiece as described in any one of [1] to [3] is to separate the support body (A) from the temporary fixing material (B), and then remove the temporary fixing material ( B), whereby separation of the workpiece (C) from the laminate (D) is achieved.

[5]

The method for treating workpieces according to [4], wherein the method of separating the temporary fixing material (B) and the support (A) is mechanical peeling.

[6]

The workpiece processing method according to any one of [1] to [5], wherein the temporary fixing material (B) contains a hardening type adhesive material component.

[7]

The method for treating a workpiece according to any one of [1] to [5], wherein the temporary fixing material (B) contains a release agent.

[8]

The method for treating workpieces according to any one of [1] to [7], wherein the temporary fixing material (B) is a double-sided layered material bonded to the base film (B ₀ ).

[9]

The wafer processing method according to any one of [1] to [8], wherein the thickness of the workpiece (C) processed in step (2) is not less than 1 μm and not more than 200 μm.

[10]

The method for processing a workpiece according to any one of [1] to [8], wherein the thickness of the workpiece (C) is at least temporarily 1 μm to 200 μm.

[11]

A method of manufacturing an electronic device, comprising the step of implementing the workpiece processing method according to any one of [1] to [10].

[12]

The method of manufacturing an electronic device according to [11], wherein the electronic device has a structure in which semiconductor wafers are laminated.

[13]

A laminated body, which is a laminated body (D) formed by laminating a support body (A), a temporary fixing material (B), and a workpiece (C) located on the side of the temporary fixing material (B) opposite to the support body (A) side. ),in,

The "10° peel strength P ₁ between the support body (A)/temporary fixing material (B)" and the "temporary fixing material (B)/temporary fixing material (B)/ The ratio P ₂ /P ₁ of the 10° peel strength P ₂ ″ between the workpieces (C) is 1.1 or more.

According to the workpiece processing method of the present invention, the workability of thin or fragile workpieces such as workpieces is improved, wafers and other workpieces can be stably processed in various processing processes, and peeling at unexpected interfaces can be effectively suppressed. , and the processed wafers and other workpieces can be stably separated and taken out by a relatively simple and low-cost process such as mechanical peeling, so without damaging electronic components such as functional layers formed on wafers and other workpieces, Implementing a large number and/or multiple steps on workpieces such as wafers with high productivity and yield rate is very helpful to improve the productivity of electronic components such as electronic devices.

11: Support (A)

12: Temporary fixing material (B)

13: Workpiece (C)

14: Cutting Tape

15: ring frame

16: remover

17: Adhesive tape

18: Adhesive material layer (B ₂ ) on the workpiece (C) side

19: Substrate film (B ₀ )

20: Adhesive material layer (B ₁ ) on the support (A) side

21: Polyimide film

FIG. 1 is a schematic diagram illustrating mechanical peeling in one embodiment of the present invention.

Figure 2 is a schematic diagram illustrating the separation of the support (A) from the laminate (D) in one embodiment of the present invention, (a) shows a better separation pattern, (b) to (c) show poor separation type.

Figure 3 is a schematic diagram illustrating the specific 10° peel strength measurement method in the present invention, (a) shows the adhesive material layer (B) used on the side where the substrate film (B ₀ ) is laminated and the support (A) is connected ₁ ) When the ₁₀ ° peel strength P ₁ measurement sample is measured, (b) shows the adhesive material layer (B ₂ ) In the case of measuring the resulting ₁₀ ° peel strength P2 measurement sample, (c) shows that a polyimide film is laminated on a temporary fixing material (B) that does not have a base film (B ₀ ) In the case of measuring the 10°peel strength P ₁ of the measurement sample, (d) shows the measurement of the polyimide film laminated on the temporary fixing material (B) without the base film (B ₀ ) The case where a sample is used and the measurement of the 10° peel strength P ₂ is performed.

FIG. 4 is a schematic diagram showing a method for evaluating the removability of a temporary fixing material (B) from a workpiece (C) in an embodiment of the present invention.

Fig. 5 is a schematic view showing a laminate (D) in one embodiment of the present invention.

Fig. 6 is a schematic view showing a laminate (D) in another embodiment of the present invention.

The processing method of the workpiece of the present invention has:

Step (1), laminating the support body (A), the temporary fixing material (B) and the workpiece (C) located on the side of the temporary fixing material (B) opposite to the side of the support body (A);

Step (2), subjecting the workpiece (C) to at least one treatment selected from heat treatment, mechanical processing, wet treatment and laser processing; and

Step (3), separating the workpiece (C) from the laminate (D) having the processed workpiece (C);

The "10° peeling strength P ₁ between the support body (A)/temporary fixing material (B)" and the "temporary fixing material (B) The ratio P ₂ /P ₁ of the 10° peel strength P ₂ ″ between the workpieces (C) is 1.1 or more.

That is, in the processing method of this invention, when processing a workpiece|work (C), the temporary fixing material (B) which is a support body (A) and a temporary fixing material is used.

[Support (A)]

The support (A) preferably has sufficient strength and rigidity and is excellent in heat resistance and chemical resistance. By using such a support (A), even when the workpiece (C) is thinned, the workpiece (C) can be stably handled, and the workpiece (C) can be subjected to stress without bending or the like. High volume and/or multiple processes. For example, various processes required for manufacturing an electronic device having a structure in which semiconductor wafers are laminated such as TSV connections can be applied to the workpiece (C) on which the electronic circuit is formed.

Examples of materials suitable for the support (A) include silicon, sapphire, crystal, metals (such as aluminum, copper, steel), various glasses, and ceramics. The support body (A) may be composed of a single material, may be composed of multiple materials, and may include other materials deposited on the base material. For example, the silicon wafer may also have evaporated layers such as silicon nitride.

In order to adjust the 10° peel strength P ₁ with the temporary fixing material (B), surface treatment such as providing a silicone layer may be performed.

Depending on the temperature of the process performed on the laminate (D), the support (A) can also be made of plastic. For example, plastics such as polyimide, acrylic, polyolefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), nylon, and urethane can be preferably used. The formed sheet serves as support (A). From the point of view of having a certain degree of heat resistance, the Tejia series uses polymer imide.

In order to obtain uniform thickness of the workpiece (C) after grinding, etc., it is preferable that the thickness of the support (A) is uniform. For example, in order to make the silicon wafer as the workpiece (C) thinner than 50 μm and to make the uniformity less than ±10%, the thickness unevenness of the support (A) should be suppressed to less than ±2 μm.

The thickness of the support (A) is not particularly limited, but is preferably at least 300 μm, particularly preferably at least 500 μm, from the viewpoint of effectively preventing bending of the workpiece (C). From the viewpoint of suppressing the total weight during handling and reducing the stress required for mechanical peeling, etc., it is preferably 1500 μm or less, particularly preferably 1000 μm or less.

[temporary fixing materials (B)]

The temporary fixing material (B) is used to fix the workpiece (C) on the support body (A).

The temporary fixing material (B) is preferably one that can be easily peeled off from the support body (A) and the workpiece (C). Therefore, the temporary fixing material (B) preferably has sufficient adhesive force to fix the workpiece (C) to the support body (A), but has sufficiently low adhesive force to be peelable.

The temporary fixing material (B) is preferably an adhesive material, and the adhesive material used in such an embodiment can be, for example, rubber-based, acrylic-based, epoxy-based, urethane-based, allyl-based series, polysiloxane series, fluorine series, polyimide series adhesive materials, etc. Among them, acrylic or polysiloxane adhesive materials are preferred in terms of heat resistance and easy adjustment of adhesive force and adhesive force.

The above-mentioned adhesive material can be a hardening adhesive material or a non-hardening adhesive material, but it is hardened before heat treatment so that holes are not easily generated in the heat treatment in the manufacturing step, and the high temperature during the heat treatment is suppressed so that the adhesion is accelerated and not easy. It can be easily peeled off due to residual glue, so it is better to be a hardened adhesive material.

Examples of the above-mentioned hardening adhesive materials include light hardening materials that are crosslinked and hardened by exposure to light. Vulcanization-type adhesive materials, and thermosetting adhesive materials that are cross-linked and hardened by heating.

The above-mentioned light-curing adhesive material or thermosetting adhesive material can include, for example: acrylic, epoxy resin, urethane acrylate, epoxy acrylate, polysiloxane acrylate or polyester acrylate, etc. Photocurable adhesive materials and thermally curable adhesive materials that contain photopolymerization initiators, thermal polymerization initiators, and photopolymerization initiators as hardening components.

Among the above, the acrylic adhesive adhesive polymer can be obtained, for example, by pre-synthesizing a (meth)acrylic polymer having a functional group in the molecule (hereinafter referred to as a (meth)acrylic polymer containing a functional group). Polymer) is reacted with a compound having a functional group reactive with the above-mentioned functional group and a radically polymerizable unsaturated bond in the molecule (hereinafter referred to as an unsaturated compound containing a functional group).

The above-mentioned functional group-containing (meth)acrylic polymers use alkyl acrylates and/or alkyl methacrylates with alkyl carbon numbers generally ranging from 2 to 18 as the main monomers, and make them It is obtained by copolymerization with monomers containing functional groups and other monomers for modification that can be copolymerized with these monomers as required. The weight average molecular weight of the functional group-containing (meth)acrylic polymer is usually about 200,000 to 2 million.

The above-mentioned functional group-containing monomers include, for example, carboxyl-containing monomers such as acrylic acid and methacrylic acid, hydroxyl-containing monomers such as hydroxyethyl acrylate and hydroxyethyl methacrylate, glycidyl acrylate, methacrylic acid, etc. Monomers containing epoxy groups such as glycidyl ester, monomers containing isocyanate groups such as ethyl isocyanate acrylate and ethyl isocyanate methacrylate, monomers containing amino groups such as aminoethyl acrylate and aminoethyl methacrylate Monomer etc.

Examples of other monomers for modification that can be copolymerized include various monomers used in general (meth)acrylic polymers such as vinyl acetate, acrylonitrile, and styrene.

As the functional group-containing unsaturated compound reacting with the above-mentioned functional group-containing (meth)acrylic polymer, it can be used in accordance with the functional group of the above-mentioned functional group-containing (meth)acrylic polymer. of the same monomer. For example, when the functional group of the above-mentioned functional group-containing (meth)acrylic polymer is a carboxyl group, an epoxy group-containing monomer or an isocyanate group-containing monomer can be used. When the functional group is a hydroxyl group, an isocyanate group-containing monomer can be used. When the functional group is an epoxy group, a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide can be used. When the functional group is an amine group, an epoxy group-containing monomer can be used.

The said photoinitiator is mentioned, for example: What activates by irradiating the light of the wavelength of 250-800 nm. Examples of such photopolymerization initiators include acetophenone derivative compounds such as methoxyacetophenone, benzoin ether-based compounds such as benzoin propyl ether and benzoin isobutyl ether, benzyl dimethyl Ketals, ketal derivatives such as acetophenone diethyl ketal, phosphine oxide derivatives, bis(η5-cyclopentadienyl) titanocene derivatives, benzophenone, Michelerone (Michler's ketone), chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy A photoradical polymerization initiator such as methylphenylpropane. These photoinitiators may be used alone or in combination of two or more.

Examples of the above-mentioned thermal polymerization initiators include those that decompose into and generate active radicals that undergo polymerization and hardening due to heat. Specific examples include: tertiary butylperoxy-2-ethyl hexanoate, bis(4-methylbenzoyl) peroxide, benzoyl peroxide, 1,1-bis(tertiary hexyl) peroxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(4,4-bis-(tert-butylperoxy)cyclohexyl) Propane, tert-hexylperoxy isopropyl monocarboxylate, tert-butylperoxy acetate, 2,2-bis-(tert-butylperoxy)butane, 4,4-bis-( tertiary butyl peroxy) n-butyl pentanoate, di-tertiary peroxide Hexyl ester, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, bis(2-tert-butylperoxyisopropyl) Benzene, tert-butylcumene peroxide, di-tert-butyl 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, diisohydroperoxide Propylene, etc.

Among these thermal polymerization initiators, commercially available ones are not particularly limited, for example, PERBUTYL O, NYPER BMT, NYPER BW, PERHEXA HC, PERHEXA C, PERTETRA A, PERHEXYL I, PERBUTYL A, PERHEXA 22, PERHEXA V, PERHEXYL D, PERCUMYL D, PERHEXA 25B, PERBUTYL P, PERBUTYL C, PERHEXYNE 25B, PERCUMYL P (all manufactured by NOF), Perkadox 12XL25 (manufactured by Kayaku Nouryon), etc. These thermal polymerization initiators may be used alone or in combination of two or more.

The oligomer or monomer used as a curing component generally has a molecular weight of 10,000 or less and the number of radically polymerizable unsaturated bonds in the molecule is 1 to 40. From the viewpoint of three-dimensional network formation, the number of radically polymerizable unsaturated bonds is preferably 2 or more.

Examples of the oligomer or monomer of the hardening component include trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, neopentylthritol triacrylate, neopentylthritol tetraacrylate, diperythritol monohydroxypentaacrylate, diperythritol hexaacrylate, or the same methacrylates as above, and the like. Others include: 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available low polyester acrylate, urethane acrylate , the same methacrylates as above, and the like. These polyfunctional oligomers or monomers may be used alone or in combination of two or more.

The temporary fixing material (B) may also contain various thermal crosslinking agents such as acrylic polymers without unsaturated double bonds, isocyanate compounds, melamine compounds, and epoxides according to expectations, Conventional additives such as release agents, plasticizers, resins, surfactants, waxes, and microparticle fillers.

In the temporary fixing material (B), it is preferable to use a release agent from the viewpoint of adjusting the peeling strength with the (A) support and/or (C) workpiece.

The release agent is not particularly limited as long as it can exhibit a general release effect. Examples thereof include hydrocarbon-based compounds, polysiloxane-based compounds, fluorine-based compounds, polyethylene-based waxes, carnauba wax, behenic acid, and stearic acid known as release agents for plastic materials. Among them, polysiloxane-based and fluorine-based compounds are preferred, and polysiloxane-based and fluorine-based compounds having functional groups capable of cross-linking with hardening adhesives are more preferred.

In particular, polysiloxane, because of its excellent heat resistance, can prevent the adhesive material from scorching even after being treated with heating above 200°C. Because polysilicon oxide has a functional group that can cross-link with the above-mentioned hardening adhesive, it will chemically react with the above-mentioned hardening adhesive by irradiation or heating and then be incorporated into the above-mentioned hardening adhesive. The object will not adhere to the adhered object and cause pollution. In addition, the effect of preventing adhesive residue on the semiconductor wafer can also be exerted by mixing polysilicon oxide.

Moreover, a plasticizer etc. are mentioned as another mold release agent. Generally, the plasticizer is not particularly limited as long as it can reduce the adhesive force of the adhesive material to the adhered object. Examples thereof include plasticizers such as trimellitate, pyromellitate, phthalate, and adipate.

The addition amount of the release agent is not particularly limited, and the addition amount can be appropriately determined to obtain the release effect. On the other hand, in order to avoid obviously impairing the adhesive function of the temporary fixing material (B), the amount added is controlled to avoid excess. For example, with respect to 100 parts by mass of the temporary fixing material (B) as a whole, an addition amount of about 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 1 part by mass) is used as a standard, and depending on It is appropriate to adjust the peeling force.

Also, if a plasticizer is added, it is usually 5 to 50 parts by mass (preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass) as a standard, and it is advisable to adjust it according to the peeling force .

In this aspect, these release agents may be used alone or in combination.

The thickness of the temporary fixing material (B) is not particularly limited, but the lower limit is preferably 5 μm, and the upper limit is 250 μm. The lower limit of the thickness of the temporary fixing material (B) is more preferably 10 μm, and the upper limit is 200 μm. If the thickness of the temporary fixing material (B) is within this range, it can absorb the unevenness of the workpiece (C) and temporarily fix it to the support body (A) with sufficient strength. When the temporary fixing material (B) is peeled off, it is easy to remove The peeling force is adjusted in an appropriate range.

The temporary fixing material (B) may be a single layer or a multilayer laminate.

In the case of a multi-layer laminate, it is preferable to use a layer (adhesive material layer) having adhesive properties between the workpiece (C) side and the support body (A) side. At this time, the adhesive material layer (B ₁ ) on one side can be formed to have an appropriate peel strength with the support (A), and the adhesive material layer (B ₂ ) on the other side can be formed to be in contact with the workpiece (C) A form with an appropriate peel strength between them. At this time, the adhesive material layer (B 1 ) in contact with the support (A) and the adhesive material layer (B ₂ ) in contact with the workpiece (C ₎ preferably have different compositions. In this case, the interface between the adhesive material layer (B ₁ ) and the adhesive material layer (B ₂ ) may have a layered structure in the general sense in which the composition changes discontinuously, or may have a so-called continuous change in composition. Slanted composition composition.

The adhesive material layer (B 1 ) in contact with the support (A) and the adhesive material layer (B ₂ ) in contact with the workpiece (C ₎ can be laminated directly, but preferably through the substrate film (B ₀ ) The so-called double-sided adhesive tape that is laminated on both sides. In this aspect, the adhesive material layer (B ₁ ) can be designed from the viewpoint of optimizing the peel strength between it and the support (A), and the adhesive material layer (B ₂ ) can be designed from the viewpoint of making it bond with the workpiece (C) can be designed from the viewpoint of optimizing the peel strength, and the base film (B ₀ ) can be designed from the viewpoint of the mechanical strength and handleability of the entire temporary fixing material (B) and the entire laminate (D). , so it is particularly advantageous from the viewpoint of optimizing the performance of the temporary fixing material (B).

An example of a laminate (D) using a temporary fixing material (B) composed of an adhesive material layer (B ₁ ), a base film (B ₀ ), and an adhesive material layer (B ₂ ) is shown in FIG. 5 . In the figure, 11 denotes the support (A), 20 denotes the adhesive layer (B ₁ ) on the side of the support (A), 19 denotes the substrate film (B ₀ ), and 18 denotes the adhesive material on the side of the workpiece (C). Layer (B ₂ ), 13 represents the workpiece (C).

The material of the substrate film (B ₀ ) is not particularly limited, preferably a plastic film, such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polynaphthalene Films, sheets, sheets with a network structure, etc. of ethylene diformate (PEN), nylon, urethane, polyether ether ketone (PEEK), liquid crystal polymer (LCP), polyimide, etc. Perforated sheets, etc.

[Workpiece (C)]

The workpiece (C) processed by the method of the present invention is not particularly limited, as long as it can be processed in the step (2) of the present invention, it can be used. Among them, due to the reasons of thinness and breakage, it needs to be handled carefully, so it is suitable to use the method of the present invention in the treatment of workpieces that require temporary fixation (temporary fixation). The thinness and fragility of the workpiece here are often produced in steps (1) and/or (2) described later. For example, the method of the present invention is suitably used for workpiece processing in which the thickness is temporarily thinned in the middle of processing to hinder handling. In the case of temporary thinning, there are the cases of starting processing from a thin object at the beginning, the case of thinning the object with a predetermined thickness during the process, and the case of further processing the thinned object. The thickness of the temporarily thinned workpiece (C) is usually 1 to 200 μm.

For example, a semiconductor wafer on which the functional layer has been processed is temporarily fixed on the carrier so that the functional layer becomes the carrier side, and the surface (rear surface) opposite to the functional layer is thinned, and ion implantation is performed on the rear surface. annealing, electrode formation, and separation from the support, in this case the steps A semiconductor wafer corresponds to a workpiece (C).

For example, when a flexible film is temporarily fixed on a carrier, a so-called circuit formation or mounting of an electronic device is performed on the flexible film, and then it is separated from the carrier, in this case, the flexibility in the step The film corresponds to the workpiece (C).

Alternatively, this method can also be suitably used on a temporary fixing material (B) formed by temporarily fixing a device group such as a chip that is not necessarily thin on the support body (A) and sealing them all to form a molded wafer (mold). wafer), seal the panel, and then separate from the support. In such a usage method, what corresponds to the workpiece (C) is a device group such as a wafer, a sealed wafer, a panel, etc., and since these are easily damaged, they are temporarily fixed.

The workpiece (C) processed in the present invention is as described above, and also includes those whose state changes during the process.

As mentioned above, the workpiece (C) processed by the present invention is not particularly limited. As a more specific example, in semiconductor wafers, copper foil with resin, prepreg, thin multilayer circuit board, flexible Permanent circuit substrates, film substrates formed with organic electroluminescence (organic EL) or LEDs, thin display components, lens arrays, or semiconductor wafers. For example, compound semiconductor wafers such as silicon wafers, SiC, AlSb, AlAs, AlN, AlP, BN, BP, BAs, GaSb, GaAs, GaN, GaP, InSb, InAs, InN, or InP, crystal wafers, Sapphire, glass, encapsulated wafers or angular encapsulated panels, etc.

Silicon wafers or compound semiconductor wafers may also be doped.

Alternatively, lamination, coating, sputtering, vapor deposition, etching, chemical vapor growth (CVD), physical vapor growth, etc. (PVD), resist coating/patterning, reflow, plasma treatment, die bonding, wire bonding, resin encapsulation, etc. are combined and repeated several times, thereby forming a workpiece (C). Artifacts for this case The thickness of (C) is not particularly limited, but is usually 1 μm to 2000 μm. Examples of the workpiece (C) to be formed on the temporary fixing material (B) include a thin multilayer circuit board, a component built-in board, a rewiring layer, and a film formed by forming an organic electroluminescent body (organic EL) or an LED. Substrate, Mold Array Package, Mold Wafer, Mold Panel, etc.

Electrical/electronic functional layers can also be formed on the wafer workpiece (C) or in the workpiece (C). Examples of suitable functional layers include electronic circuits, capacitors, transistors, resistors, electrodes, optical elements, MEMS, etc., and microelements other than these may also be used.

The surface of these functional layers may also have a structure formed of one of the following materials, typically electrodes. Examples of materials for functional layers include silicon, polysilicon, silicon dioxide, (oxygen) silicon nitride, metals (such as copper, aluminum, gold, tungsten, and tantalum), low-k dielectrics, and polymer dielectrics. And various metal nitrides and metal silicides. On the surface of the workpiece (C) on which the device is formed, there may also be protruding structures such as solder bumps, metal strips, and pillars.

[step 1)]

The workpiece processing method of the present invention comprises: laminating the above-mentioned support body (A), the temporary fixing material (B), and the workpiece (C) located on the side of the temporary fixing material (B) opposite to the support body (A) side. step 1).

An example of the state after step (1) is shown in FIG. 6 . In the figure, 11 denotes a support body (A), 12 denotes a temporary fixing member (B), and 13 denotes a workpiece (C).

Fixing the workpiece (C) to the support plate (A) through the temporary fixing material (B) makes it easy to handle the workpiece (C) in the subsequent step (2), and prevents bending and damage.

The order of laminating the support (A), temporary fixing material (B) and workpiece (C) is not particularly limited, and these layers can be laminated together or sequentially. As mentioned above, it is also possible to include The workpiece (C) is formed on the temporary fixing material (B).

When supplying the temporary fixing material (B) in the form of a liquid hardening adhesive material or the like, the liquid hardening adhesive material or the like can be applied to any one of the workpiece (C), the support (A) or the like by spin coating or the like. In both, the laminate is produced after the temporary fixing material (B) or the precursor of the temporary fixing material (B) is formed.

When supplying the temporary fixing material (B) or the precursor of the temporary fixing material (B) in the form of a solid film, the adhesion strength to the support is usually set lower than that of the workpiece side, so from the viewpoint of preventing peeling during handling See, it is preferable to attach the film on the workpiece (C) before laminating the support (A).

Also, in the case where the film is attached at normal pressure and the laminate is formed only under reduced pressure, from the viewpoint of good absorption of the unevenness of workpieces such as wafers, it is preferable to temporarily apply the film in the form of a film. After the fixing material is attached to the support body (A), it is attached to the workpiece (C).

When the temporary fixing material (B) or the precursor of the temporary fixing material (B) contains a curable adhesive material component, the adhesive material can also be hardened in step (1) to form the temporary fixing material (B). Material hardening refers to irradiating or heating the curable adhesive material components to cross-link and harden the curable adhesive material components.

The hardening type adhesive material component that is cross-linked and hardened by light or heat has a dramatic improvement in chemical resistance, even if the workpiece (C) is not in contact with the temporary fixing material (B) in step (2). Applying chemical liquid treatment to the surface can also suppress the dissolution of the adhesive material in the chemical liquid. In addition, the modulus of elasticity of the cured adhesive material component after cross-linking and hardening increases, so even at high temperatures, it is difficult to cause adhesion and aggravation, and it is easier to peel off.

In this way, in this embodiment, no matter whether the workpiece (C) is subjected to heat treatment, machining treatment and/or wet treatment in step (2), sufficient adhesive force can be maintained when the workpiece (C) is processed, and After the workpiece (C) processing step is completed, the workpiece (C) can be removed in step (3) without damaging the workpiece (C) or leaving no glue It is peeled off from the temporary fixing material (B).

For example, as the above-mentioned light-curing adhesive material components that are crosslinked and hardened by irradiation, polymers containing unsaturated double bonds such as vinyl groups in side chains are used, and those that are activated by wavelengths from 250 to 800 nm are used. When bonding materials with photopolymerization initiators, it is preferable to irradiate such a photocurable adhesive material component with an illumination intensity of 5mW or more, more preferably with an illumination intensity of 10mW or more, and even more preferably with an illumination intensity of 20mW or more. Illumination irradiation, the best is to irradiate with an illumination intensity of 50mW or more. In addition, it is preferable to irradiate with a cumulative illuminance of 300mJ or more, more preferably 500mJ to 10000mJ, more preferably 500mJ to 7500mJ, and most preferably 1000mJ to 5000mJ. The cumulative illuminance is irradiated.

Also, for example, as the temporary fixing material (B) or the precursor of the temporary fixing material (B) is cross-linked and hardened by the above-mentioned heat-curing adhesive material component, it is used to contain unsaturated adhesives such as vinyl groups in side chains. When adhesive materials are made of polymers with double bonds and thermal polymerization initiators that are activated by heating at about 50 to 200°C, the above heat can be activated by heating at a temperature of about 50 to 200°C for 10 to 60 minutes. Hardening type adhesive material components are cross-linked and hardened.

As mentioned above, in the case of hardening the precursor of the temporary fixing material (B) to form the temporary fixing material (B), it may be laminated with the support (A) or the workpiece (C) after hardening, or may be laminated after the laminate. After hardening, it can also be laminated in a semi-hardened state and then finally hardened.

[step (2)]

In the workpiece processing method of the present invention, further comprising: the step (2) of applying at least one treatment selected from heat treatment, mechanical processing, wet processing, and laser processing to the workpiece (C) after step (1). .

The above-mentioned step (2) also includes TSV processing, processing required for forming a structure in which semiconductor wafers subjected to TSV processing are laminated.

The above-mentioned heat treatment (including treatment accompanied by heat generation, the same below) includes, for example, sputtering, vapor deposition, etching, chemical vapor deposition (CVD), physical vapor deposition (PVD), photoresist coating/patterning, resin Heated lamination of composition films, thermosetting of resin compositions, heat drying of resin compositions, baking of resin compositions, heat reflow, resin sealing, plasma treatment, die bonding, wire bonding, flip chip bonding, surface Activation direct conjugation, etc., but not limited thereto.

In the workpiece processing method of the present invention, in the above-mentioned steps, it can be properly handled even in the temperature range of 100°C, especially 150°C or higher.

The aforementioned mechanical processing is typically wafer grinding, grinding, drilling, and cutting, but is not limited thereto and includes singulation and the like.

When grinding or polishing the workpiece (C) on which the electrodes are formed, the surface (back surface) on which the electrodes are not formed is ground or polished. The thickness of the workpiece (C) after grinding/grinding on the back side varies depending on the electronic device used for the electronic device. Usually, it is set to 1 μm to 200 μm, preferably 5 μm to 100 μm, more preferably 5 μm to 50 μm the following. The obtained electronic device can be thinned by this, and the electronic equipment using the electronic device can be miniaturized.

In this embodiment, when the workpiece (C) is ground/grinded, the workpiece (C) can be ground with better machining accuracy by laminating the temporary fixing material (B) and the rigid support (A). , and after this grinding, etc., the workpiece (C) can be subjected to further processing steps without causing damage to the workpiece (C), or it can be easily removed from the support (A) and temporarily fixed material (B) separated.

The above-mentioned wet treatment includes coating treatments such as spin coating, inkjet, and screen printing, grinding treatments such as CMP, and treatments using acids, alkalis, or organic solvents. For example, plating treatments such as electroplating and electroless plating, etc. Wet etching treatment by hydrofluoric acid, tetramethylammonium hydroxide aqueous solution (TMAH), etc., photoresist stripping process by N-methyl-2-pyrrolidone, monoethanolamine, DMSO, etc., by Washing processes performed by concentrated sulfuric acid, ammonia water, hydrogen peroxide water, etc., but not limited thereto.

Examples of the aforementioned laser treatment include, but are not limited to, annealing, perforation processing, circuit formation treatment by direct drawing, and pre-separation treatment from a support.

In the workpiece processing method of the present invention, before step (3) described later, a dicing tape may also be pasted on the processed surface of the workpiece such as the wafer after the above-mentioned processing. By attaching the dicing tape in advance, the support body (A) and the temporary fixing material (B) can be peeled off in step (3) and can be diced quickly.

In the present invention, the support body (A) is separated from the temporary fixing material (B) in the step (3), but the treatment before peeling may be performed in the step (2) in advance.

Specifically, methods such as laser treatment, swelling and dissolution of the temporary fixing material (B) with a solvent may also be appropriately used before mechanical peeling, but from the viewpoints of simplification of the device and excellent cost, it is preferable to use No such processing takes place.

In this specification, the laminated body which has the workpiece|work (C) which passed through the process (2) is also called laminated body (D).

[step (3)]

In the processing method of the workpiece|work of this invention, it further has the step (3) of separating the said processed workpiece (C) from a laminated body (D).

The workpiece (C) is separated from the laminate (D), preferably by the following method: the support (A) is separated from The laminate (D) is separated, and then the temporary fixing material (B) remaining on the workpiece (C) is removed. In this embodiment, when the temporary fixing material (B) remaining on the workpiece (C) is removed, the generally rigid support (A) has been separated from the laminate (D), so it is not necessary to fix the workpiece (C) The workpiece (C) can be separated from the temporary fixing material (B) by applying excessive stress, so the risk of damaging the functional layer formed on the workpiece (C) can be reduced.

The method of separating the support (A) from the temporary fixing material (B) is not particularly limited, but mechanical peeling is preferably used.

The separation between the support (A)/temporary fixing material (B) and the separation between the temporary fixing material (B)/workpiece (C) can be performed by both mechanical peeling, or one of them can be performed by mechanical peeling. Methods.

In the processing method of the workpiece of the present invention, by making the above-mentioned peeling strength ratio P ₂ /P ₁ more than 1.1, the peeling between the support body (A)/temporary fixing material (B) is relatively easy, so mechanical peeling etc. can be compared. The support (A) is peeled from the laminate (D) stably and covers the entire surface of the laminate (D) in a simple process. At this time, since peeling at the unexpected interface, that is, the temporary fixing material (B)/workpiece (C), is effectively suppressed, the risk of damaging the functional layer formed on the workpiece (C) can be reduced.

In the laminate (D) composed of the support (A)/temporary fixing material (B)/work (C) separated in step (3), the angles formed by the respective peeled layers are kept at "10° peel strength P ₁ between support body (A)/temporary fixing material (B)" and "10° peel strength P ₂ between temporary fixing material (B)/workpiece (C)" measured at 10° " _The ratio P2/P1 is _1.1 or more. In addition, the 10° peel strength P 1 between the support body (A)/temporary fixing material (B) and the 10° peel strength P ₂ between the temporary fixing material (B)/workpiece (C ₎ are obtained through the following steps (2) The measured value after the same course. For example, in the case of applying a heat history of 150 to 200° C. in the step (2), it is a value after applying the heat history.

According to the processing method of the workpiece of the present invention, by setting the above-mentioned peeling strength ratio P ₂ /P ₁ to 1.1 or more, a relatively simple process such as mechanical peeling can be used to stabilize and cover the support (A) from the temporary fixing material (B). The entire surface of the laminate (D) is peeled off.

At this time, since peeling at the unexpected interface, that is, the temporary fixing material (B)/workpiece (C), is effectively suppressed, the risk of damaging the functional layer formed on the workpiece (C) can be reduced.

Also, because it also effectively suppresses the phenomenon that part of the temporary fixing material (B) remains on the support body (A) or part of the temporary fixing material (B) on the workpiece (C) is defective, so it also reduces the impact on the workpiece (C) or The support (A) exerts a risk of such breakage due to uneven stress.

The 10°peel strength P ₁ between the support (A)/temporary fixing material (B) and the 10°peeling strength P ₂ between the temporary fixing material (B)/workpiece (C) are the peeled layers ( The force (N /mm).

That is, the 10° peel strength P1 between the support body (A)/temporary fixing material (B) and the ₁₀ ° peel strength P2 between the temporary fixing material (B)/workpiece (C ₎ can be obtained by the following Method decision: in the state shown in Figure 3 or based on this state, carry out between 11 support body (A)/12 temporary fixing material (B) or 12 temporary fixing material (B)/13 workpiece (C) For the peeling between, measure the force required for peeling and divide it by the width of the peeling part; more specifically, it can be measured as follows.

The support (A) or workpiece (C) is usually rigid or brittle, and in the state of the laminate (D) formed by laminating the support (A)/temporary fixing material (B)/workpiece (C) Under the circumstances, the angle formed by the peeled layers is usually difficult to maintain at 10°, so when measuring the 10° peel strength P1 between the support ( _A )/temporary fixing material (B), it can be used without the workpiece ( C) 10 ° peel strength P ₁ measurement sample (Figure 3 (a), (c)), and when measuring the 10 ° peel strength P ₂ between the temporary fixing material (B) / workpiece (C), The measurement can be performed using a sample for measuring the 10° peel strength P ₂ that does not have the support (A) ( FIG. 3( b ), (d) ).

In the former case, when the temporary fixing material (B) has the base film (B ₀ ), the 10° peel strength P ₁ is constituted by the support (A) and the temporary fixing material (B) having the base film (B ₀ ). The measurement is carried out with a sample for measurement (Figure 3(a)), and when the temporary fixing material (B) does not have a base film but only an adhesive material layer, polyimide film or the like is used as the adhesive material layer. The substrate constituted a sample for measuring the 10° peel strength P ₁ and was measured ( FIG. 3( c )).

In the latter case, when the temporary fixing material (B) has the base film (B ₀ ), the 10° peel strength P ₂ is constituted by the temporary fixing material (B) having the base film (B ₀ ) and the workpiece (C). The measurement is carried out with a sample for measurement (Figure 3(b)), and when the temporary fixing material (B) does not have a base film but only an adhesive material layer, a polyimide film or the like is used as the adhesive material layer. The substrate constituted a sample for measuring the 10° peel strength P ₂ and was measured ( FIG. 3( d )).

The peel strength ratio P ₂ /P ₁ is preferably at least 1.1, particularly preferably at least 1.3.

The above-mentioned peel strength ratio P ₂ /P ₁ does not particularly have an upper limit, but from the viewpoint of properly peeling the workpiece (C) from the temporary fixing material (B), it is desirable that the temporary fixing material (B)/workpiece (C) The peeling strength P2 is not too large, and from the viewpoint of stably performing the treatment in step ( ₂ ), especially the mechanical processing, it is desirable to have a 10° peeling between the support (A)/temporary fixing material (B) The strength P ₁ is not too small, so the above-mentioned peel strength ratio P ₂ /P ₁ is preferably 30 or less, more preferably 15 or less, particularly preferably 7 or less.

In step (3), under the condition that no excessive stress is applied to the workpiece (C), the support (A) is stabilized from the temporary fixing material (B) and covers the laminate (D) by a relatively simple process such as mechanical peeling. ) from the viewpoint of peeling the entire surface, the 10° peel strength P ₁ between the support (A)/temporary fixing material (B) is preferably 10N/25mm or less.

The 10° peel strength P ₁ between the support (A)/temporary fixing material (B) is more preferably 8 N/25 mm or less, particularly preferably 7 N/25 mm or less.

From the standpoint of stably performing the treatment in step (2), especially the machining treatment, the 10° peel strength P1 between the support ( _A )/temporary fixing material (B) is preferably 1N/25mm or more, More preferably, it is 2N/25mm or more.

In step (3), the temporary fixing material (B) is separated from the workpiece (C), preferably by separating the support (A) from the laminate (D), and then removing the temporary fixing remaining on the workpiece (C) From this point of view, the 10° peel strength P ₂ between the temporary fixing material (B)/workpiece (C) is preferably 30N/25mm or less, more preferably 20N/25mm or less.

From the standpoint of stably performing the treatment in step ( ₂ ), especially the mechanical processing, the 10° peel strength P between the temporary fixing material (B)/work (C) is preferably 2N/25mm or more, more preferably Preferably it is more than 3N/25mm.

The means for adjusting the 10° peel strength P ₁ , the 10° peel strength P ₂ , and the peel strength ratio P ₂ /P ₁ are not particularly limited, and can be appropriately increased or decreased by means conventionally used in this technical field, for example. More specifically, it can be appropriately increased or decreased by the composition and manufacturing process of each layer, the manufacturing process of the laminate (D), for example, by increasing the adhesive agent or adhesive used in the temporary fixing material (B). The amount of adhesive material components can increase the 10° peel strength P ₁ or 10° peel strength P ₂ , and by adding a release agent to the temporary fixing material (B), the 10° peel strength P ₁ or 10° peel strength can be reduced Intensity _P2 .

The mechanical peeling method in this embodiment is also not particularly limited, and a commercially available device or the like can be used for peeling as appropriate. For example, it is preferable to perform peeling by the method shown in FIG. 1 .

In this method, the 13 workpiece (C) side of the laminate (D) is fixed on the chuck seat (not shown in the figure) through the dicing tape, and then the 11 supporting body (A) is held by the holding mechanism (not shown in the figure). .

Make 16 the remover (remover) slide into the interface of 11 support body (A) and 12 temporary fixing material (B), apply upward force on the end of 11 support body (A), between 11 support body (A) and 12 A peeling interface as a peeling origin is formed between the temporary fixing materials (B) ( FIG. 1( b )).

While applying pressure by the holding mechanism to bend the 11 support (A), the peeling interface is expanded to allow the peeling to proceed ( FIG. 1( c )).

When the peeling interface spreads to form a peeling interface on the entire surface between the 11 support (A) and the 12 temporary fixing material (B), the 11 support (A) is peeled from the 12 temporary fixing material (B).

Examples of such commercially available devices include XBC Gen from SUSS, EVG805 from EVG, TWH-SR series from TAZMO Co., Ltd., and the like.

At this time, according to the present invention, because the interface between the 12 temporary fixing materials (B) and the 13 workpieces (C) that are not expected to be peeled off at this stage can be effectively suppressed from peeling off, the 12 temporary fixing materials (B) can effectively protect the 13 workpieces ( The functional layers etc. formed on C) can reduce the risk of damage to these functional layers etc. (FIG. 2(a)).

In the prior art, before the separation between the 11 support (A) and the 12 temporary fixing material (B), sometimes the interface between the 12 temporary fixing material (B) and 13 workpiece (C) which is not expected to be peeled off at this stage Peeling occurred (Fig. 2(b)). As a result, 13 electronic circuits etc. formed on the workpiece (C) may be damaged during peeling or in subsequent processes that still need to be protected by 12 the temporary fixing material (B).

Also, in the prior art, there are 12 temporary fixing materials (B) partially remaining on the 11 support body (A) or 12 temporary fixing material (B) parts on the 13 workpiece (C) are partially defective and cannot completely peel off the support body ( The case of A) (Fig. 2(c)). As a result, uneven stress may also be applied to 13 the workpiece (C) or 11 the support (A) to cause such breakage.

In order to remove the temporary fixing material (B) remaining on the workpiece (C), it may also be dissolved with a solvent.

The present invention can solve these prior technical problems, prevent peeling and uneven peeling at unexpected interfaces, or at least greatly reduce the frequency of such occurrences, so as not to damage the functions formed on workpieces such as wafers layers, enabling a large number and/or variety of steps to be performed on workpieces with high productivity and yield.

The final product can be produced by further subjecting the workpiece such as the wafer processed by the workpiece processing method of the present invention to subsequent steps. When a functional layer is formed on the workpiece, the final product can be manufactured by further steps such as dicing, bonding, encapsulation, and sealing, which are generally used to manufacture electronic devices such as semiconductor elements.

[Example]

The present invention will be specifically described below. In addition, the present invention is not limited by the following examples in any sense.

Evaluation of physical properties and characteristics in Examples/Comparative Examples was performed by the following methods.

(1) Mechanical peelability

After applying the predetermined heat history shown in Table 1 to the manufactured laminate (D), set the 13 workpiece (C) side down at room temperature, and fix it on the 14 dicing tape attached to the 15 ring frame On, cut the tape with a vacuum chuck fixed 14 (Fig. 1(a)). Intentionally peel off at the interface between 11 support (A) and 12 temporary fixing material (B), as shown in Figure 1, slide 16 remover into the interface between 11 support (A) and 12 temporary fixing material (B) 11. The end of the support (A) typically applies an upward force within about 120N, thereby forming a peeling interface as a peeling starting point between the 11 support (A) and the temporary fixing material (B) (Fig. 1(b)).

Next, pressure is applied to the formed peeling interface to expand the peeling interface, whereby the 11 support (A) is peeled ( FIG. 1( c )). Peelability was evaluated by the following criteria.

◯: Delamination can be intentionally covering the entire interface of the support (A)/temporary fixing material (B), and the workpiece (C) is not damaged.

×: Unexpected peeling occurred at the temporary fixing material (B)/work (C) interface.

(2) Removability of temporary fixing material (B) from workpiece (C)

For the 13 workpiece (C)/12 temporary fixing material (B) laminate fixed on the 14 dicing tape attached to the 15 ring frame after the above mechanical peelability evaluation, on the entire surface of the 12 temporary fixing material (B) Attach 17 adhesive tapes. Fix 14 cutting tapes with a vacuum chuck, and peel off 12 temporary fixing materials (B) at a peeling angle of 90° and a peeling speed of 5 mm/s. Peelability was evaluated by the following criteria.

◯: The temporary fixing material (B) was completely peeled off from the workpiece (C), and the workpiece (C) was not damaged.

×: The temporary fixing material (B) cannot be peeled off from the workpiece (C).

(3) 10°peel strength P ₁ (Peel strength between support body/temporary fixing material)

(3-1) When the base film (B ₀ ) is used as the temporary fixing material

The adhesive material layer (B ₁ ) on the side that is in contact with the 20 support (A) is laminated on the 19 base film (B ₀ ) to prepare a sample for P ₁ measurement.

(3-2) When the temporary fixing material does not use the base film (B ₀ )

Prepare 21 polyimide films (double-sided plasma treatment, thickness 38 μm, DU PONT-manufactured by Toray Co., Ltd., trade name: Kapton (registered trademark) 150EN-A), and laminate the same layer as 12 temporary fixing materials on it. _The materials used to make P1 measurement samples.

(3-3) Measurement

Cut the P ₁ measurement sample made in the above (3-1) or (3-2) into 2.5cm×5cm, and roll it back and forth once with a 2kg roller to glue 20 of the P ₁ measurement sample The material layer (B ₁ ) or the same material side as the 12 temporary fixing material is attached to the attached surface side of the 11 support body (A) cut into 3cmx6cm. Next, the prepared support (A)/P ₁ measurement sample laminate was heated at 140° C. for 30 minutes, using the pretreatment in step (1) in each example and comparative example as a preset condition. Then use step (2) as the preset condition to apply the predetermined heat history shown in Table 1, and then place it at 22.5±1°C and relative humidity of 50±10% for 1 week. After cooling the sample for measurement, at this temperature, The peel strength P ₁ was measured at a tensile speed of 300 mm/min and a peel angle of 10° using VPA-S (manufactured by Kyowa Interface Science Co., Ltd.) under humidity conditions ( FIG. 3( a ) or ( c )).

(4) 10°peel strength P ₂ (peel strength between temporary fixing material/workpiece)

(4-1) When the base film (B ₀ ) is used as the temporary fixing material

On the 19 base film (B ₀ ), the adhesive material layer (B ₂ ) on the side that is in contact with the 18 workpiece (C) is laminated to prepare a P ₂ measurement sample.

(4-2) When the temporary fixing material does not use the base film (B ₀ )

Prepare 21 polyimide films (double-sided plasma treatment, thickness 38 μm, DU PONT-manufactured by Toray Co., Ltd., trade name: Kapton (registered trademark) 150EN-A), and laminate the same layer as 12 temporary fixing materials on it. materials to make samples for _P2 measurement.

(4-3) Measurement

Cut the P2 measurement sample made in (4-1) or ( _4-2 ) above into 2.5cmx5cm, and roll it back and forth once with a _2kg roller, so that the 18th adhesive layer of the P2 measurement sample (B ₂ ) or the surface of the same material side as 12 temporary fixing materials is attached to the attached surface side of the workpiece (C) cut into 3cmx6cm. Next, using the pretreatment in step (1) in each example and comparative example as a preset condition, the manufactured workpiece (C)/P ₂ measurement sample laminate was heated at 140° C. for 30 minutes. Then use step (2) as the preset condition, apply the predetermined heat history shown in Table 1, and place it at 22.5±1°C and relative humidity of 50±10% for 1 week, and cool the sample for measurement, then test it at this temperature, Using VPA-S (manufactured by Kyowa Interface Science Co., Ltd.) under humidity conditions, the peel strength P ₂ was measured at a tensile speed of 300 mm/min and a peel angle of 10 degrees ( FIG. 3( b ) or ( d )).

Details of materials and materials used in Examples/Comparative Examples are as follows.

[Support (A), and workpiece (C)]

The following glasses or Si were used for either the support (A) or the workpiece (C).

． Glass

Borosilicate heat-resistant glass made of borosilicate heat-resistant glass with an outer diameter of 300 or 200mm x thickness 700μm is used as a support substrate for silicon back grinding.

． Si

A Si mirror wafer with an outer diameter of 300 or 200 mm x a thickness of 750 μm is used.

[Resin for forming temporary fixing material (B)]

． (Meth)acrylic resin solution N:

In a solvent composed of 65 parts by mass of toluene and 50 parts by mass of ethyl acetate, 49 parts by mass of ethyl acrylate, 20 parts by mass of 2-ethylhexyl acrylate, 21 parts by mass of methyl acrylate, and 10 parts by mass of glycidyl acrylate and 0.5 parts by mass of a benzoyl peroxide-based polymerization initiator as a polymerization initiator were reacted for 10 hours. After the reaction was completed, the resulting solution was cooled, and 25 parts by mass of xylene, 5 parts by mass of acrylic acid and 0.5 parts by mass of tetradecyldimethylbenzyl ammonium chloride were added to the cooled solution, while blowing air into It was made to react at 85 degreeC for 32 hours, and the (meth)acrylic-type resin solution N was obtained.

． Silicone modified (meth)acrylic resin solution NS

To 270 parts by mass of the above-mentioned (meth)acrylic resin solution N, add 0.3 parts by mass of carboxy-modified organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22- 3710), reacted at 60° C. for 7 days to obtain polysiloxane-modified (meth)acrylic resin solution NS.

． (Meth)acrylic resin solution L

A (meth)acrylic adhesive (manufactured by Mitsui Chemicals Co., Ltd., Bind Seramu SA591) was used.

． (Meth)acrylic resin latex H

Using 0.5 parts by mass of ammonium persulfate as a polymerization initiator, 63 parts by mass of 2-ethylhexyl acrylate, 21 parts by mass of n-butyl acrylate, and 9 parts by mass of methyl methacrylate were prepared in deionized water at 70°C. Parts, 3 parts by mass of 2-hydroxyethyl methacrylate, 2 parts by mass of methacrylic acid, 1 part by mass of acrylamide, polytetramethylene glycol diacrylate (manufactured by NOF Co., Ltd., trade name; ADT-250) 1 part by mass, and 2 parts by mass of an aqueous solution of polyoxyethylene nonylpropenylphenyl ether ammonium sulfate (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., product name: Aqualon HS-1025) were emulsion-polymerized. After completion of the polymerization, the pH was adjusted to 7.0 using ammonia water to obtain a (meth)acrylic resin latex H having a solid content of 56.5% by mass.

． (Meth)acrylic resin latex B

Using 0.5 parts by mass of 4,4'-azobis-4-cyanovaleric acid (manufactured by Otsuka Chemical Co., Ltd., trade name: ACVA) as a polymerization initiator, acrylic acid was normalized at 70°C in deionized water. 74 parts by mass of butyl ester, 14 parts by mass of methyl methacrylate, 9 parts by mass of 2-hydroxyethyl methacrylate, 2 parts by mass of methacrylic acid, 1 part by mass of acrylamide, and 3 parts by mass of HS-1025 Perform emulsion polymerization. After completion of the polymerization, the pH was adjusted to 7.0 using ammonia water to obtain a (meth)acrylic resin latex B having a solid content of 42.5% by mass.

． (Meth)acrylic resin latex A

Using 0.65 parts by mass of ACVA as a polymerization initiator, in deionized water, 63 parts by mass of 2-ethylhexyl acrylate, 18 parts by mass of n-butyl acrylate, 12 parts by mass of methyl methacrylate, Emulsion polymerization was carried out with 3 parts by mass of 2-hydroxyethyl methacrylate, 2 parts by mass of methacrylic acid, 1 part by mass of acrylamide, ADT-250: 1 part by mass, and Aqualon HS-1025: 2 parts by mass. After completion of the polymerization, the pH was adjusted to 7.0 using ammonia water to obtain a (meth)acrylic resin latex A having a solid content of 42.5% by mass.

． (Meth)acrylic resin latex S

Using 0.5 parts by mass of ACVA as a polymerization initiator, 47 parts by mass of n-butyl acrylate, 22 parts by mass of methyl methacrylate, and 9 parts by mass of 2-hydroxyethyl methacrylate in deionized water at 70°C , 15 parts by mass of methacrylic acid, 8 parts by mass of acrylamide, and Aqualon HS-1025: 0.2 parts by mass were emulsified and polymerized to obtain a (meth)acrylic resin latex S with a solid content of 40 mass%.

[Substrate Film B ₀ ]

． PEN film

A polyethylene naphthalate film (double-sided corona treatment, thickness: 50 μm, manufactured by Toyobo Film Solutions Co., Ltd., Teonex Q83) was used.

． PET film

A biaxially stretched polyethylene terephthalate film (double-sided corona treatment, thickness 38 μm, manufactured by Toray Co., Ltd., Lumirror S10) was used.

(Example 1)

With respect to 250 parts by mass of (meth)acrylic resin solution L, 2.84 parts by mass of HDI isocyanurate (manufactured by Tosoh Co., Ltd., trade name: Coronate HX), 50 parts by mass of diperythritol penta /hexaacrylate (manufactured by Toa Gosei Co., Ltd., trade name: ARONIXM-402), 2.0 parts by mass of polysiloxane diacrylate (manufactured by DAICEL-ALLNEX Co., Ltd., trade name: Ebecryl 350) and 2 parts by mass of Perkadox 12XL25 manufactured by Kayaku Nouryon Co., Ltd. was used as the adhesive material layer (B ₁ ) on the support (A) side to obtain a coating solution for the adhesive material layer (B ₁ ) on the support (A) side. This coating solution was applied to the substrate B ₀ (PEN film), and dried at 100° C. for 10 minutes to form an adhesive resin layer with a thickness of 25 μm. Next, attach the polyethylene terephthalate film (separator) that has been treated with polysiloxane release type, thereby obtaining the adhesive material layer (B ₁ )/base on the support (A) side with the separator. A laminate of materials (B ₀ ).

42.6 parts by mass of (meth)acrylic resin latex H, 57.4 parts by mass of (meth)acrylic resin latex B, 0.4 parts by mass of dimethylethanolamine, 3.4 parts by mass of epoxy compounds (Nagase ChemteX Co., Ltd. Co., Ltd., product name: Ex-1610), 13 parts by weight of butyl carbinol and 20 parts by weight of pure water were mixed separately to prepare an adhesive coating solution, which was used as the adhesive material layer (B ₂ ). This coating solution was applied to a silicone release-treated polyethylene terephthalate film (separator) and dried at 120° C. for 3 minutes to form an adhesive resin layer with a thickness of 13 μm. Then stick it on the base material (B ₀ ) side of the above-mentioned adhesive material layer (B ₁ )/substrate (B ₀ ) laminate to make the adhesive material layer (B ₁ )/substrate ( B ₀ )/adhesive material layer (B ₂ ) three-layer precursor of temporary fixing material (B) before heat treatment. The separators used on both sides of the three-layer structure were peeled off, and the support (A) and workpiece (C) described in Table 1 were laminated with a vacuum laminator, heated at 140°C for 30 minutes, and the support ( Laminate (D) composed of A)/temporary fixing material (B)/work (C). Table 1 shows the results of evaluating the mechanical peelability and removability of the laminate (D).

In addition, the laminated body of adhesive material layer (B ₁ )/substrate (B ₀ ) and the laminated body of adhesive material layer (B ₂ )/substrate (B ₀ ) were prepared respectively (the coating conditions are the same), and measured by the above method 10°peel strength P ₁ and P ₂ . The measurement results are shown in Table 1.

(Example 2)

With respect to 270 parts by mass of the (meth)acrylic resin solution N, 0.5 parts by mass of HDI isocyanurate (manufactured by Tosoh Co., Ltd., trade name: CoronateHX), 12 parts by mass of diperythritol penta/ Hexaacrylate (manufactured by Toagosei Co., Ltd., trade name: ARONIXM-400), 1.5 parts by mass of polysiloxane diacrylate (manufactured by DAICEL-ALLNEX Co., Ltd., trade name: Ebecryl 350), and 2 parts by mass of Kayaku Perkadox 12XL25 manufactured by Nouryon Co., Ltd. was used as the adhesive material layer (B ₁ ) on the support (A) side to obtain a coating solution for the adhesive material layer (B ₁ ) on the support (A) side. This coating solution was applied to a silicone release-treated polyethylene terephthalate film (separator), and dried at 100° C. for 10 minutes to form an adhesive resin layer with a thickness of 100 μm. Then, the base material B ₀ (PET film) was laminated to obtain a laminate of the adhesive material layer (B ₁ )/substrate (B ₀ ) on the side of the support (A) with separator.

Next, apply the coating solution for the adhesive material layer (B ₂ ) on the workpiece (C) side in Example 1 to the polyethylene terephthalate film (separator) treated with silicone release, Dry it at 120°C for 3 minutes to form an adhesive resin layer with a thickness of 6 μm, and attach it to the substrate (B ₀ ) side of the above-mentioned adhesive layer (B ₁ )/substrate (B ₀ ) laminate, In this way, the precursor of the temporary fixing material (B) before heat treatment, which consists of three layers of adhesive material layer (B ₁ )/substrate (B ₀ )/adhesive material layer (B ₂ ) with a separator, is produced.

The separators used on both sides of the three-layer structure were peeled off, and the support (A) and workpiece (C) described in Table 1 were laminated with a vacuum laminator, heated at 140°C for 30 minutes, and the support ( Laminate (D) composed of A)/temporary fixing material (B)/work (C). Table 1 shows the results of evaluating the mechanical peelability and removability of the laminate (D).

In addition, the laminated body of adhesive material layer (B ₁ )/substrate (B ₀ ) and the laminated body of adhesive material layer (B ₂ )/substrate (B ₀ ) were prepared respectively (the coating conditions are the same), and measured by the above method 10°peel strength P ₁ and P ₂ . The measurement results are shown in Table 1.

(Example 3)

1.0 parts by mass of HDI isocyanurate (manufactured by Tosoh Co., Ltd., trade name: CoronateHX) and 2 parts by mass of Kayaku Nouryon stock were added to 269 parts by mass of polysiloxane-modified (meth)acrylic resin solution NS Co., Ltd. made Perkadox 12XL25 to obtain an adhesive material coating liquid for a temporary fixing material (B). This coating solution was applied to a polyethylene terephthalate film (separator) treated with silicone release, and then dried at 100° C. for 10 minutes to form an adhesive resin layer with a thickness of 100 μm. Then paste the polyethylene terephthalate film (separator) that has been treated with polysiloxane release type, so as to make the temporary fixing material (B) precursor (with separator on both sides) before heat treatment. The separators on both sides are peeled off, and the support plate (A) and the workpiece (C) described in Table 1 are laminated with a vacuum laminator, and heated at 140°C for 30 minutes to make a sequence of support (A)/temporary fixing material ( Laminate (D) composed of B)/workpiece (C). Table 1 shows the results of evaluating the mechanical peelability and removability of the laminate (D).

Also, the 10° peel strengths P ₁ and P ₂ were measured by the above method (when the base film (B ₀ ) was not used as the temporary fixing material). The measurement results are shown in Table 1.

(Example 4)

The coating solution for the adhesive material layer (B ₁ ) on the side of the support (A) in Example 1 was coated on the polyethylene terephthalate film (separator) treated with polysiloxane release type, and the It was dried at 100° C. for 10 minutes to form an adhesive resin layer with a thickness of 31 μm. Then, the base material B ₀ (PET film) was laminated to obtain a laminate of the adhesive material layer (B ₁ )/substrate (B ₀ ) on the support (A) side with partitions.

Next, 100 parts by mass of (meth)acrylic resin latex A, 0.7 parts by mass of (meth)acrylic resin latex S, 0.3 parts by mass of dimethylethanolamine, 5 parts by mass of epoxy compounds (Nagase Manufactured by ChemteX Co., Ltd., trade name: Ex-614), 9 parts by weight of butyl carbinol and 12 parts by weight of pure water were mixed separately to prepare an adhesive coating solution, which was used as the adhesive material layer on the side of the workpiece (C) ( B2 ₎ . This coating solution was applied to a silicone release-treated polyethylene terephthalate film (separator), and dried at 120° C. for 3 minutes to form an adhesive resin layer with a thickness of 20 μm. Next, stick it on the base material (B ₀ ) side of the above-mentioned adhesive material layer (B ₁ )/substrate (B ₀ ) laminate, thereby producing an adhesive material layer (B ₁ )/base material with a partition. Temporary fixing material (B) precursor before heat treatment consisting of three layers of material (B ₀ )/adhesive material layer (B ₂ ). The separators used on both sides of the three-layer structure were peeled off, and the support (A) and workpiece (C) described in Table 1 were laminated with a vacuum laminator, heated at 140°C for 30 minutes, and the support ( Laminate (D) composed of A)/temporary fixing material (B)/work (C). Table 1 shows the results of evaluating the mechanical peelability and removability of the laminate (D).

In addition, the laminate of adhesive material layer (B ₁ )/substrate (B ₀ ) and the laminate of adhesive material layer (B ₂ )/substrate (B ₀ ) were prepared respectively (the coating conditions are the same), and measured by the above method 10°peel strength P ₁ and P ₂ . The measurement results are shown in Table 1.

(comparative example 1)

With respect to 269 parts by mass of silicone modified (meth)acrylic resin solution N, 0.1 part by mass of HDI isocyanurate (manufactured by Tosoh Co., Ltd., trade name: Coronate HX), 6 parts by weight of new Pentaerythritol tri/tetraacrylate (manufactured by Toagosei Co., Ltd., trade name: M-450) and 2 parts by mass of Perkadox 12XL25 manufactured by Kayaku Nouryon Co., Ltd., thereby obtaining a temporary fixing material (B) Coating with an adhesive material liquid. This coating solution was applied to a silicone release-treated polyethylene terephthalate film (separator), and then dried at 100° C. for 10 minutes to form an adhesive resin layer with a thickness of 50 μm. Then, the bonding is treated with silicone release A polyethylene terephthalate film (separator) was used to prepare a temporary fixation material (B) precursor (double-sided separator) before heat treatment. The separators on both sides are peeled off, and the support plate (A) and the workpiece (C) described in Table 1 are laminated with a vacuum laminator, and heated at 140°C for 30 minutes, thereby making a sequential support (A)/temporary fixation Laminate (D) composed of material (B)/workpiece (C). Table 1 shows the results of evaluating the mechanical peelability and removability of the laminate (D).

Also, the 10° peel strengths P ₁ and P ₂ were measured by the above method (when the base film (B ₀ ) was not used as the temporary fixing material). The measurement results are shown in Table 1.

[Table 1]

[industrial availability]

The workpiece processing method of the present invention can implement a large number of and/or multiple steps on wafers and other workpieces with high productivity and yield without damaging electronic components such as functional layers formed on wafers and other workpieces Therefore, it is very helpful to improve the productivity of electronic devices. It has a great potential in various fields such as the electronic parts industry including the semiconductor process industry, the electrical and electronic industry using electronic parts, the transportation equipment industry, the information communication industry, and the precision equipment industry. High availability.

11: Support (A)

12: Temporary fixing material (B)

13: Workpiece (C)

Claims (13)

A method for processing workpieces, comprising the following steps: Step (1), laminating the support body (A), the temporary fixing material (B) and the workpiece (C) located on the side of the temporary fixing material (B) opposite to the side of the support body (A); Step (2), subjecting the workpiece (C) to at least one treatment selected from heat treatment, mechanical processing, wet treatment and laser processing; and Step (3), separating the workpiece (C) from the laminate (D) having the processed workpiece (C); wherein, The "10° peeling strength P ₁ between the support body (A)/temporary fixing material (B)" and the "temporary fixing material (B) The ratio P ₂ /P ₁ of the 10° peel strength P ₂ ″ between the workpieces (C) is 1.1 or more. The method for processing workpieces according to claim ₁ , wherein the peel strength P1 is 10N/25mm or less. The method for processing workpieces as described in claim 1 or 2, wherein the temporary fixing material (B) is an adhesive material layer connected to the support (A) and an adhesive material layer connected to the workpiece (C) have different compositions. The processing method of the workpiece as described in any one of claims 1 to 3 is to separate the support (A) from the temporary fixing material (B), and then remove the temporary fixing material (B) remaining on the workpiece (C) , thereby achieving separation of the workpiece (C) from the laminate (D). The method for processing workpieces according to claim 4, wherein the separation method of the temporary fixing material (B) and the support body (A) is mechanical peeling. The method for processing a workpiece according to any one of Claims 1 to 5, wherein the temporary fixing material (B) contains a hardening type adhesive material component. The method of processing a workpiece according to any one of claims 1 to 5, wherein the temporary fixing material (B) contains a release agent. The method for processing workpieces according to any one of Claims 1 to 7, wherein the temporary fixing material (B) is formed by bonding the double-sided layers of the base film (B ₀ ). The method for processing a workpiece according to any one of claims 1 to 8, wherein the thickness of the processed workpiece (C) in step (2) is not less than 1 μm and not more than 200 μm. The method for processing a workpiece according to any one of claims 1 to 8, wherein the thickness of the workpiece (C) is at least temporarily 1 μm to 200 μm. A method of manufacturing an electronic device, which has the step of implementing the workpiece processing method according to any one of Claims 1 to 10. The method of manufacturing an electronic device according to claim 11, wherein the electronic device has a structure formed by stacking semiconductor wafers. A laminated body, which is a laminated body (D) formed by laminating a support body (A), a temporary fixing material (B), and a workpiece (C) located on the side of the temporary fixing material (B) opposite to the support body (A) side. ),in, The "10° peeling strength P ₁ between the support body (A)/temporary fixing material (B)" and "temporary fixing material (B)/temporary fixing material (B)/ The ratio P ₂ /P ₁ of the 10° peel strength P ₂ ″ between the workpieces (C) is 1.1 or more.

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