KR101700636B1 - Composition for removing an adhesive and method for porducing thin wafer using the same - Google Patents

Composition for removing an adhesive and method for porducing thin wafer using the same Download PDF

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KR101700636B1
KR101700636B1 KR1020150054203A KR20150054203A KR101700636B1 KR 101700636 B1 KR101700636 B1 KR 101700636B1 KR 1020150054203 A KR1020150054203 A KR 1020150054203A KR 20150054203 A KR20150054203 A KR 20150054203A KR 101700636 B1 KR101700636 B1 KR 101700636B1
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wafer
acid
adhesive
weight
layer
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KR20160123707A (en
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이진규
이민규
한정현
심재원
유현규
정래형
김현탁
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재원산업 주식회사
(주) 이엠테크
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5027—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/76—Making of isolation regions between components
    • H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
    • H01L21/7624—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology
    • H01L21/76251—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques
    • H01L21/76259—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques with separation/delamination along a porous layer

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  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

The present invention relates to a composition for removing adhesives and a method of manufacturing a thin wafer using the same. More particularly, the present invention relates to a method of manufacturing a thin wafer by using a protective layer formed of a non-silicone thermoplastic resin sequentially laminated on a wafer and a thermoplastic siloxane resin polymer Wherein the organic solvent is less than 95% by weight of the organic solvent, and the additive is more than 5% by weight and less than 40% by weight based on the total weight of the organic solvent and the additive, Wherein the additive is at least one selected from the group consisting of acetic acid, toluenesulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, oxalic acid, butylic acid, sulfuric acid, hydrofluoric acid and nitric acid, and a thin wafer And a method for producing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a composition for removing an adhesive, and a method for manufacturing a thin wafer using the same. BACKGROUND ART [0002]

The present invention relates to a composition for removing an adhesive and a method of manufacturing a thin wafer using the same. More particularly, the present invention relates to a method for removing a protective layer formed of a non-silicone thermoplastic resin and an adhesive layer formed of a thermoplastic siloxane resin polymer simultaneously And a method for producing a thin wafer using the same.

The semiconductor device manufacturing process includes a step of forming a fine circuit pattern on one surface of a semiconductor wafer having a predetermined thickness, a step of grinding the back surface of the wafer to reduce the thickness of the wafer, a step of cutting the wafer A step of packaging each die chip with a semiconductor device is carried out after making the die chip.

In the process of polishing the back surface of the wafer, a fine circuit formed on the wafer is protected. In order to fix the wafer or the like, a support such as silicon or glass is generally attached to the circuit surface of the wafer using an adhesive polymer, The backside of the wafer is prevented from being damaged during grinding. Then, the support and the adhesive polymer are peeled and removed from the circuit surface of the wafer, respectively.

On the other hand, the method of reducing the minimum wiring width to increase the degree of integration of semiconductor devices has gradually reached a physical limit. In addition to a method of increasing the degree of integration of the semiconductor device itself, a method of stacking chips using wire bonding, Recently, development of a three-dimensional semiconductor mounting technology using a through silicon vias (hereinafter referred to as TSV) is actively under way.

The three-dimensional mounting technology is a semiconductor fabrication technique in which one semiconductor chip is made thinner and the semiconductor chip is connected by TSV and accumulated in multiple layers. In order to realize this, a step of thinning the back surface of the substrate on which the semiconductor circuit is formed by grinding and forming electrodes including TSV on the back surface is required. In the back side grinding step of the silicon substrate, a separate support is attached to the circuit forming side opposite to the grinding side via an adhesive layer formed using an adhesive, thereby preventing wafer breakage during grinding, The wafer can withstand sufficiently in the process of forming electrodes, metal wiring, and the like. At this time, the adhesive layer needs to bond the wafer and the support to each other without gaps, requires sufficient durability to withstand the subsequent process, and finally, it is necessary that the support can be easily peeled off from the thin wafer. According to this need, it is preferable that the adhesive layer is formed of a plurality of layer structures made of materials having different properties from each other than a single layer, and a non-silicone thermoplastic resin and a thermoplastic siloxane resin polymer are used as materials constituting the adhesive layer .

The support and the adhesive layer need to be peeled from the wafer after the grinding process. At this time, a part of the adhesive layer may remain on the surface of the wafer without peeling off. The remaining adhesive layer has a two-layer structure of a non-silicone thermoplastic resin layer and a thermoplastic siloxane resin polymer layer, and therefore, it is difficult to completely remove both layers at the same time with a conventional remover.

Korean Patent Laid-Open Publication No. 10-2014-0070359 discloses a process for removing a bonding layer, wherein a double layer of a non-silicon thermoplastic resin layer and a thermoplastic siloxane resin polymer layer is not dissolved and removed at the same time, The silicone thermoplastic resin layer is dissolved to remove the thermoplastic siloxane resin polymer layer in a lift-off fashion. In the case of removing the double layer of the non-silicone thermoplastic resin layer and the thermoplastic siloxane resin polymer layer using the remover described in this prior art, the residue of the adhesive layer which is not sufficiently dissolved remains on the surface of the wafer, Equipment contamination, pipe clogging, and the like, and furthermore, a small amount remains in the bumps of the wafer, thereby deteriorating the performance of the completed package.

Accordingly, it is possible to remove the adhesive layer of the double-layer structure of the non-silicon thermoplastic resin layer and the thermoplastic siloxane resin polymer layer remaining on the wafer after peeling off the support adhered to the wafer, There is a need to develop a composition for removal and a removal process.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method of manufacturing a semiconductor device, which comprises a step of bonding a protective layer formed of a non-silicon thermoplastic resin and an adhesive layer of a double- The present invention is intended to provide a composition for removing adhesives and a method of manufacturing a thin wafer using the same, which can effectively prevent the wafer from being damaged, defective, equipment contaminated, and clogged with pipes and improving the performance of the finished package.

According to an aspect of the present invention, there is provided a composition for removing an adhesive, which comprises a protective layer formed of a non-silicone thermoplastic resin sequentially laminated on a wafer and an adhesive layer formed of a thermoplastic siloxane resin polymer Wherein the organic solvent is added in an amount of 60 wt% or more to less than 95 wt%, preferably 70-90 wt%, and the additive is added in an amount of 5 wt% or more to 40 wt% or less, preferably 10 wt% or less, -30% by weight.

Preferably, the additive may be at least one selected from the group consisting of acetic acid, toluenesulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, oxalic acid, butyl acid, sulfuric acid, hydrofluoric acid and nitric acid, more preferably toluenesulfonic acid or dodecylbenzenesulfonic acid Silylbenzenesulfonic acid. When dodecylbenzenesulfonic acid is used as an additive, it is more than 5 wt% to 40 wt%, preferably 20-30 wt%, based on the total weight of the composition, and when toluenesulfonic acid is used, it is more than 5 wt% By weight is 20-30% by weight.

Preferably, the organic solvent is selected from the group consisting of pentane, hexane, heptane, hexene, octane, nonane, decane, decene, undecane, dodecane, tetradecane, cyclohexane, methylcyclohexane, Benzene, toluene, ethylbenzene, propylbenzene, 1,4-dimethylbenzene, 1-methyl-4-ethylbenzene, 1-methyl-4-isopropylcyclohexane, decalin, limonene, Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N, N-dimethylacetoacetamide, N, N-dimethylacrylamide, N, N-diethylpropionamide, N, N-dimethyl methacrylamide, N, Amide, N, N- Acetylpiperazine, 1-acetylpyrrolidine, and 1-methyl-2-pyrrolidone, such as N, N-dimethylacetamide, N, Pyrrolidone, and 2-pyrrolidone. More preferably, the organic solvent may be 1-methyl-4-isopropylcyclohexane and / or decalin. Even when an organic solvent containing two or more compounds is used, the mixture is preferably used in an amount of 60 wt% or more to less than 95 wt%, preferably 70-90 wt%.

Preferably, the composition for removing adhesives of the present invention comprises at least one organic solvent selected from the group consisting of 1-methyl-4-isopropylcyclohexane and decalin; And at least one additive selected from the group consisting of toluene sulfonic acid and dodecylbenzene sulfonic acid, wherein the organic solvent is 70-90 wt% and the additive is 10-30 wt% based on the total weight of the composition.

Preferably, the composition for removing adhesives comprises 70-90% by weight of p-menthane and 10-30% by weight of dodecylbenzenesulfonic acid, or comprises 70-80% by weight of p-menthane and 20-30% Toluenesulfonic acid, 70-90 wt% decalin and 10-30 wt% dodecylbenzenesulfonic acid, 70-80 wt% decalin and 20-30 wt% toluenesulfonic acid, or p- An organic solvent composed of 40% by weight of menthane and 40% by weight of decalin, and 20% by weight of toluene sulfonic acid or 20% by weight of dodecylbenzene sulfonic acid.

The composition for removing an adhesive may be used in a debonding step of removing an adhesive on the wafer on which a circuit is formed by a silicon penetration electrode method.

The protective layer may be formed of a thermoplastic non-silicone resin represented by the following formula (1).

≪ Formula 1 >

Figure 112015037434427-pat00001

In the above formula (1), R 13 to R 16 are each independently hydrogen or a substituted or unsubstituted C 1 -C 10 monovalent hydrocarbon group, and l is 5000 to 10000.

The adhesive layer may be formed of a thermoplastic siloxane resin polymer represented by the following formula (2).

(2)

Figure 112015037434427-pat00002

In Formula 2, R 11 and R 12 are each independently a substituted or unsubstituted C 1 -C 10 monovalent hydrocarbon group, and n is 5000 to 10000.

The present invention also provides a method for manufacturing a semiconductor device, comprising the steps of: bonding a support to a circuit formation surface of a wafer having a circuit formation surface on a surface thereof and a circuit formation surface on a back surface thereof with an adhesive layer, A protective layer formed of a silicone thermoplastic resin, an adhesive layer formed of a thermoplastic siloxane resin polymer, and a support layer formed of a thermosetting siloxane modified polymer; Grinding or polishing a circuit non-formation surface of the wafer bonded to the support; Forming a non-circuit forming surface of the wafer; Peeling the processed wafer from the support, wherein the support and the support layer are peeled off, and the protective layer and the adhesive layer sequentially remain on the wafer; And a step of simultaneously dissolving and removing the protective layer and the adhesive layer on the wafer using the composition for removing an adhesive of the present invention.

According to an embodiment of the present invention, there is provided a composition for removing an adhesive and a method for manufacturing a thin wafer using the same, wherein a double layer comprising a protective layer formed of a non-silicone thermoplastic resin and an adhesive layer formed of a thermoplastic siloxane resin polymer, The structure's adhesive layer can be effectively removed to prevent breakage, defects, equipment contamination and pipe clogging of the wafer and improve the performance of the finished package.

Fig. 1 is a cross-sectional view showing an example of a wafer-processed body with a support provided thereon with an adhesive layer interposed therebetween, according to an embodiment of the present invention.
2 is a cross-sectional view showing an adhesive layer remaining on a wafer and a wafer after peeling off a support in a wafer-processed body according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference symbols as possible even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, the terms first, second, A, B, (a), (b), and the like can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

In describing the components of the present invention, it is to be understood that when an element such as a layer, film, region, plate, or the like is referred to as being "on" or "on" another element, It is to be understood that the present invention may include the case where there are other components in between. On the contrary, when an element is referred to as being "directly on " another element, it should be understood that it does not have another element in the middle.

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

As used herein, the term "alkyl" or "alkyl group" refers to an alkyl group having from 1 to 30 carbon atoms unless otherwise specified and includes straight chain alkyl groups, branched chain alkyl groups, cycloalkyl (alicyclic) Alkyl " means a radical of a saturated aliphatic group, including alkyl, cycloalkyl-substituted alkyl groups.

The term "alkenyl group" or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 30 carbon atoms and include straight chain or branched chain groups, It is not.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 30 carbon atoms, but is not limited thereto.

The term "alkoxyl group "," alkoxy group ", or "alkyloxy group" as used in the present invention means an alkyl radical attached with an oxygen radical and has 1 to 30 carbon atoms, It is not.

In addition, a no explicit description, the terms used in this invention in the "unsubstituted or substituted", "substituted" is an alkyl group of deuterium, a halogen, an amino group, a nitrile group, a nitro group, C 1 -C 20, C 1 -C 20 alkoxy group, C 1 -C 20 alkyl amine group, C 1 -C 20 alkyl thiophene group, C 6 -C 20 aryl thiophene group, C 2 -C 20 alkenyl, C 2 -C of 20 alkynyl, C 3 -C 20 cycloalkyl group, C 6 -C 20 aryl group, of a C 6 -C 20 aryl group substituted with a heavy hydrogen, C 8 -C 20 aryl alkenyl group, a silane group, a boron And a C 2 -C 20 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, with the proviso that at least one substituent And is not limited to these substituents.

The composition for removing adhesives according to one embodiment of the present invention is used to remove the double layered adhesive layer of the non-silicone thermoplastic resin layer and the thermoplastic siloxane resin polymer layer in the debonding process during the TSV process.

A typical TSV process uses a laser drilling method or a chemical etching method to punch a hole in a wafer and then to fill the hole using a plating method. As a problem of wafer alignment and byproduct treatment, chemical etching is preferred over laser drilling, and DRIE (Deep Reactive Ion Etching) is a typical chemical etching method.

DRIE uses a plasma to drill holes perpendicular to silicon wafers and fill holes with metal, the most common being copper. First, a seed layer of three layers is formed inside the hole for copper plating. The seed layer is formed on the inner wall of the hole in the following order: a dielectric layer for insulation between copper and silicon; an adhesion / diffusion preventing layer for preventing lethal copper from diffusing into silicon; and a copper seed layer for copper plating.

After such basic processes, the back surface of the wafer on which the semiconductor circuit is formed is thinned by grinding, and a step of forming electrodes including TSV on the back surface is performed. In the back grinding process of the wafer, a separate support is attached via an adhesive layer formed on the circuit formation surface opposite to the grinding surface using an adhesive, thereby preventing wafer breakage during grinding.

After the wafer grinding process, a process of debonding the attached support is carried out in order to prevent wafer breakage.

Hereinafter, with reference to FIG. 1, a wafer-processed body having a support provided thereon with an adhesive layer interposed therebetween in order to prevent wafer breakage in the grinding process will be described, and with reference to FIG. 2, a debonding step for peeling the support on a wafer I will explain.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a wafer processed body with a support interposed therebetween on a wafer according to an embodiment of the present invention.

1, the wafer-processed body includes a wafer 10 having a circuit-formed surface and a back surface to be processed, a support 30 for supporting the wafer 10 when the wafer 10 is processed, And an adhesive layer 20 sandwiched between the wafer 10 and the support 30.

As the support 30, a silicon carrier is typically used, and it supports the wafer in a process of forming a back electrode, a metal wiring, or the like on the grinding surface of the wafer while sufficiently supporting the wafer.

An adhesive layer 20 is formed on the wafer 10 to adhere the support 30 to the wafer 10 in order from the side of the wafer 10 through the protective layer 21, the adhesive layer 22, A support layer 23, and the like, and may preferably be formed in these three-layer structures. Further, illustratively, the protective layer 21 may be formed of a non-silicone thermoplastic resin, the adhesive layer 22 may be formed of a thermoplastic siloxane resin polymer, and the support layer 23 may be formed of a thermosetting siloxane- have.

The protective layer 21 is formed on the side opposite to the circuit forming surface of the wafer, and may be formed of a thermoplastic non-silicone resin represented by the following formula (1).

≪ Formula 1 >

Figure 112015037434427-pat00003

In the above formula (1), R 13 to R 16 may be, independently of each other, hydrogen or a substituted or unsubstituted C 1 -C 10 monovalent hydrocarbon group. For example, R 13 to R 16 may be a C 1 -C 10 alkyl group, a C 2 -C 10 alkenylene group, or a C 2 -C 10 alkynyl group, and these may be substituted with one or more substituents. Also, l is 5000 to 10000.

On the protective layer 21, an adhesive layer 22 may be formed. The adhesive layer 22 may be formed of a thermoplastic siloxane resin, which is a compound represented by the following formula (2) to facilitate peeling from the support layer 23.

(2)

Figure 112015037434427-pat00004

In Formula 2, R 11 and R 12 independently represent a substituted or unsubstituted C 1 -C 10 monovalent hydrocarbon group such as a C 1 -C 10 alkyl group, a C 2 -C 10 alkenylene group, or C 2 or the like may alkynyl group of -C 10, which may be substituted with one or more substituents. In the above formula (2), n is 5000 to 10000.

A support layer 23 may be formed on the adhesive layer 22. The support layer 23 may be formed of a thermosetting organopolysiloxane, for example, a compound represented by the following formula (3).

(3)

Figure 112015037434427-pat00005

In the formula (3), R 1 to R 4 may be the same or different and are each independently a substituted or unsubstituted C 1 -C 8 monovalent hydrocarbon group such as a C 1 -C 10 alkyl group, a C 2 -C 10 Or an alkynyl group of C 2 -C 10 , and the like, which may be substituted with one or more substituents. A is 0 or a positive integer, m is an integer of 1 to 100, B is a positive integer, and X is a divalent organic group represented by one of the following Chemical Formulas 4 and 5: a weight average molecular weight of 3,000 to 500,000 to be.

&Lt; Formula 4 > < EMI ID =

Figure 112015037434427-pat00006
Figure 112015037434427-pat00007

In the general formulas (4) and (5), R 5 to R 8 may be the same or different from each other, and are independently a C 1 -C 4 alkyl group or an alkoxy group, k and h are each an integer of 0 to 2, Z And V is

Figure 112015037434427-pat00008
, And N and p are each 0 or 1.

The adhesive layer 20 described above is interposed to bond the wafer 10 and the support body 30 and the support body 30 and the adhesive layer 20 need to be separated from the wafer 10 after the grinding process. This peeling step is referred to as a debonding step. The support layer 23 immediately adjacent to the support 30 in the adhesive layer 20 and the support 30 can be easily peeled off from the wafer by a peeling process or a debonding process.

Therefore, after the peeling process, the protective layer 21 and some of the adhesive layers 20 'such as the adhesive layer 22 remain on the wafer 10 without peeling off, as shown in FIG. 2 is a cross-sectional view showing an adhesive layer remaining on a wafer and a wafer after peeling off a support in a wafer processing body according to an embodiment of the present invention.

2, the adhesive layer 20 'remaining on the surface of the wafer 10 such as the protective layer 21 and the adhesive layer 22 is formed of a protective layer 21 formed of a non-silicon thermoplastic resin and a thermoplastic The adhesive layer 22 formed of a siloxane resin polymer is different in properties from each other, and since it is difficult to completely remove both layers simultaneously with a conventional removing agent, the residue of the adhesive layer 20 ' Remains on the surface.

In this case, if the residue of the adhesive layer 20 'is not cleanly removed, the wafer may be damaged, defective, equipment contaminated and piping clogged in a subsequent process, and furthermore, a small amount of residue may remain in the bump of the wafer, A problem arises.

The composition for removing an adhesive according to an embodiment of the present invention comprises a protective layer formed of a non-silicone thermoplastic resin remaining on a wafer after peeling off a support adhered to the wafer, and a double layer structure of an adhesive layer formed of a thermoplastic siloxane resin polymer The adhesive layer can be simultaneously removed efficiently.

The composition for removing an adhesive according to an embodiment of the present invention includes an organic solvent and an additive. Hereinafter, the components for removing the adhesive according to an embodiment of the present invention will be described in more detail.

The organic solvent may be at least one selected from the group consisting of a chain type or cyclic hydrocarbon compound having 5 to 15 carbon atoms, an acetate compound, an amide compound, and the like. That is, one type of organic solvent may be used, or two or more kinds of organic solvents may be mixed and used.

Specifically, the hydrocarbon compound may be selected from the group consisting of pentane, hexane, heptane, hexene, octane, nonane, decane, decene, undecane, dodecane, tetradecane, cyclohexane, methylcyclohexane, 1,4 dimethylcyclohexane, Methyl-4-ethylbenzene, 1-methyl-4-isopropylcyclohexane, decalin, benzene, toluene, ethylbenzene, propylbenzene, , Evacuation, pinen, and the like.

The acetate compounds may be methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and the like.

The amide compound may be selected from the group consisting of N, N-dimethylacetamide, N, N-dimethylpropionamide, N, N-diethylacetamide, N, N-dimethylacrylamide, -Dimethyl methacrylamide, N, N-dimethylacetoacetamide, N, N-dimethyldecanamide, N, N-diethylacrylamide, N, N-diethylacetoacetamide, , 1-acetylpiperazine, 1-acetylpyrrolidine, 1-methyl-2-pyrrolidone, and the like.

Preferably, the organic solvent may be 1-methyl-4-isopropylcyclohexane (p-Menthane), decalin, and the like.

The organic solvent is preferably 60-90 wt%, more preferably 70-90 wt%, based on the total weight of the composition. If the amount of the organic solvent is less than 60 wt%, the solubility of the thermoplastic non-silicon layer in the protective layer 21 may be lowered. If the amount of the organic solvent is more than 90 wt%, the thermoplastic siloxane layer The solubility may be lowered.

As the above-mentioned additive, an organic acid or an inorganic acid may be used, and one kind of additives may be used, or two or more kinds of additives may be mixed and used. As the organic acid, acetic acid, toluenesulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, oxalic acid, and butyric acid can be used. As the inorganic acid, sulfuric acid, hydrofluoric acid, nitric acid and the like can be used. Preferably, the additive may be toluenesulfonic acid and dodecylbenzenesulfonic acid and the like.

Further, in addition to the above-described additive components, surfactants commonly used in this field may be further added.

The additive may be 10-40 wt%, preferably 10-30 wt%, based on the total weight of the composition. When the additive is contained in an amount less than 10% by weight, the solubility of the thermoplastic siloxane layer in the adhesive layer 22 may be lowered, and in the case of more than 40% by weight, the solubility in the protective layer 21 in the thermoplastic non- There may be a problem of falling.

The composition for removing an adhesive according to one aspect of the present invention can be specifically used in a debonding process for removing an adhesive on the wafer on which a circuit is formed by a silicon penetration electrode method.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples, so that those skilled in the art can sufficiently convey the spirit of the present invention.

1. Preparation of compositions for removing adhesives

The components shown in Tables 1 and 2 were mixed at the composition ratios to prepare the compositions for removing adhesives of Examples 1 to 22 and Comparative Examples 1 to 6. However, the content of each component is% by weight.

2. Adhesive Removal power  Test

The wafer sample coated with the adhesive was cut into a size of 2 X 2 cm 2 and immersed in the compositions of Examples 1 to 22 and Comparative Examples 1 to 10 for 5 minutes. At the time of immersion, the temperature of the composition was adjusted to 25 캜, and the stirrer was rotated at a speed of 350 rpm and stirred. The immersed wafer samples were taken out and cleaned with isopropyl alcohol (IPA) and dried. Viscosity and SEM of the removal rate of the adhesive in the removal rate and the removed form were observed with the naked eye and SEM, and the results are shown in Tables 1 and 2 .

p-M Decalin TsOH DBSA Adhesive removal power Fine residue Removal rate Removal type Example 1 90 10 △ Dissolution handful Example 2 90 10 ◎ Dissolution none Example 3 90 10 △ Dissolution handful Example 4 90 10 ◎ Dissolution none Example 5 85 15 ○ Dissolution handful Example 6 85 15 ◎ Dissolution none Example 7 85 15 ○ Dissolution thimbleful Example 8 85 15 ◎ Dissolution none Example 9 80 20 ◎ Dissolution none Example 10 80 20 ◎ Dissolution none Example 11 80 20 ◎ Dissolution none Example 12 80 20 ◎ Dissolution none Example 13 40 40 20 ◎ Dissolution none Example 14 40 40 20 ◎ Dissolution none Example 15 70 30 ◎ Dissolution none Example 16 70 30 ◎ Dissolution none Example 17 70 30 ◎ Dissolution none Example 18 70 30 ◎ Dissolution none Example 19 60 40 ○ Dissolution thimbleful Example 20 60 40 ○ Dissolution thimbleful Example 21 60 40 ○ Dissolution thimbleful Example 22 60 40 ○ Dissolution thimbleful Removal speed: ◎ - Very fast, ○ - Fast, △ - Normal, X- Not removed

IN IDD p-M Decalin TsOH DBSA Adhesive removal power Fine residue Removal rate Removal type Comparative Example 1 100 △ Lift-off much Comparative Example 2 100 △ Lift-off much Comparative Example 3 95 5 △ Dissolution much Comparative Example 4 95 5 △ Dissolution handful Comparative Example 5 95 5 △ Dissolution much Comparative Example 6 95 5 △ Dissolution handful Comparative Example 7 50 50 △ Dissolution handful Comparative Example 8 50 50 △ Dissolution handful Comparative Example 9 50 50 △ Dissolution handful Comparative Example 10 50 50 △ Dissolution handful Removal speed: ◎ - Very fast, ○ - Fast, △ - Normal, X- Not removed

Abbreviations used in the above Tables 1 and 2 are as follows.

p-M: p-Menthane

IN: Isononane

IDD: Isododecane

TsOH: Toluenesulfonic acid

DBSA: Dodecylbenzenesulfonic acid

Examples 1 to 22, in which the adhesive was removed using the composition for removing adhesives according to an embodiment of the present invention, are shown in Table 1, and the removal rate of the adhesive is usually very fast, Is dissolved and removed. In addition, the fine residue in the examples is relatively good such as not remaining at all or remaining in a very small amount or a small amount even if it is present.

Particularly, in the case of Examples 2, 4, 6 and 8 to 18, since the adhesive is removed in a dissolved form, its removal rate is very fast and no fine residue is present at all, The effect of removing the fine residue is maximized. Thus, if the composition for removing adhesives comprises 70-90% by weight of an organic solvent comprising at least one of p-menthane and decalin and 10-30% by weight of an additive of either toluenesulfanic acid or dodecylbenzenesulfonic acid, It can be seen that it is maximized. Preferably, the composition for removing the adhesive comprises 70-90% by weight of p-menthane and 10-30% by weight of dodecylbenzenesulfonic acid, or 70-80% by weight of p-menthane and 20-30% Or 70-90% by weight of decalin and 10-30% by weight of dodecylbenzenesulfonic acid, 70-80% by weight of decalin and 20-30% by weight of toluenesulfonic acid, or p An organic solvent composed of 40% by weight of menthane and 40% by weight of decalin, and 20% by weight of toluene sulfonic acid or 20% by weight of dodecylbenzene sulfonic acid.

On the other hand, with reference to the comparative examples in Table 2, all of the compositions for removing an adhesive having the same compositions as those of Comparative Examples 1 to 10 had a normal removal rate, and Comparative Examples 1 and 2 had a lift- , And Comparative Examples 3 to 10 are shown to be dissolved and removed. In addition, it can be seen that the fine residue remains in a large amount or in a small amount and is unsuitable as a composition for removing an adhesive. That is, a composition comprising 95% by weight of p-menthane or decalin and 5% by weight of toluenesulfonic acid or dodecylbenzenesulfonic acid, 50% by weight of p-menthane or decalin and 50% by weight of toluenesulfonic acid or dodecylbenzenesulfonic acid Is not excellent in terms of the removal rate of the adhesive, and a small amount or a large amount of fine residue remains, and thus it is difficult to expect excellent quality.

In order to improve the production yield and quality in the semiconductor manufacturing process and the like, it is necessary to consider both the removal rate, the removal form, and the amount of the fine residue. In the lift-off form as in Comparative Example 1 and Comparative Example 2, the thermoplastic siloxane layer The adhesive layer 21 is separated from the wafer in the form of a film, thereby causing equipment defects such as clogging of the drain pipe, equipment contamination, etc., and a small amount of the thermoplastic siloxane layer in the process of separating the adhesive layer 21 from the wafer Of the siloxane material remains on the bump surface, causing a problem on the wafer that reduces the efficiency of the wafer. Therefore, in order to minimize the occurrence of a problem on the wafer during the debonding process, the adhesive layer 20 'is removed in the form of a melt rather than removed in the form of a lift-off, and the amount of fine residue after removal of the adhesive is small Advantageously, the faster the removal rate, the better the production yield.

Considering this point, it can be seen that the production of thin semiconductor wafers according to the present invention is advantageous in terms of quality and yield.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

10: wafer 20, 20 ': adhesive layer
21: protective layer 22:
23: support layer 30: support

Claims (7)

A composition for removal of an adhesive for simultaneously removing a protective layer formed of a non-silicone thermoplastic resin sequentially laminated on a wafer and an adhesive layer formed of a thermoplastic siloxane resin polymer at the wafer debonding step,
By weight of an additive of 10-30% by weight of toluenesulfonic acid or dodecylbenzenesulfonic acid and 70-90% by weight of decalin. delete delete delete delete The method according to claim 1,
Wherein the protective layer is formed of a thermoplastic non-silicone resin represented by the following Chemical Formula 1, and the adhesive layer is a thermoplastic siloxane resin polymer represented by Chemical Formula 2:
&Lt; Formula 1 >
Figure 112016090525990-pat00013

(2)
Figure 112016090525990-pat00014

In the above formula (1), R 13 to R 16 are each independently hydrogen or a substituted or unsubstituted C 1 -C 10 monovalent hydrocarbon group, l is 5000 to 10000,
In Formula 2, R 11 and R 12 are each independently a substituted or unsubstituted C 1 -C 10 monovalent hydrocarbon group, and n is 5000 to 10000. delete
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