WO2019220711A1

WO2019220711A1 - Cleaning agent, cleaning agent production method, and target object processing method

Info

Publication number: WO2019220711A1
Application number: PCT/JP2019/004969
Authority: WO
Inventors: 洋平大石
Original assignee: Jsr株式会社
Priority date: 2018-05-16
Filing date: 2019-02-13
Publication date: 2019-11-21
Also published as: JP2021127351A; TW202003825A

Abstract

The present invention addresses the problem of providing a cleaning agent capable of adequately eliminating residue in semiconductor production processes such as in the elimination of a temporary fixing material residue. The cleaning agent contains 3 to 10% by mass of tetramethylammonium hydroxide (A), 20 to 60% by mass of water (B), dimethylsulfoxide (C), and a compound (D) represented by formula (1). (In formula (1), R1 represents an alkanediyl group having 1 to 3 carbons; n represents an integer from 1 to 3; when n is 2 or greater, the plurality of R1 may be identical or different from one another; and R2 represents an alkyl group having 1 to 6 carbons.)

Description

Cleaning agent, manufacturing method of cleaning agent, and processing method of object

The present invention relates to a cleaning agent, a manufacturing method of the cleaning agent, and a processing method of an object.

A method has been proposed in which an object such as a semiconductor wafer is bonded to a support such as a glass substrate via a temporary fixing material, and processing such as back grinding and photofabrication is performed on the object. . The temporary fixing material needs to be able to temporarily fix the object on the support during the processing, and to easily separate the support and the object after the processing.

In the separation process, by irradiating the temporary fixing material in the laminate having the support, the temporary fixing material, and the object with light energy such as ultraviolet rays and infrared rays, the adhesive force of the temporary fixing material is reduced, Subsequently, a method of separating the support and the object has been proposed (see Patent Documents 1 and 2).

International Publication No. 2017/056662 US Published Patent No. 2014/0106473

When the object is separated from the support, there is usually a residue of temporarily fixing material on the object, and thus the object is cleaned with a cleaning agent in order to remove the residue. However, even if this cleaning is performed, the temporary fixing material residue may not be removed well.

The present invention provides a cleaning agent capable of satisfactorily removing a residue in a semiconductor manufacturing process such as removal of a residue of a temporary fixing material, and also provides a method for manufacturing the cleaning agent, and temporary fixing. In a method of processing and moving an object in a state where the object to be treated is temporarily fixed on the support using a material, and subsequently separating the support from the object, the residue of the temporarily fixed material on the object It is an object of the present invention to provide a method for processing an object with a small amount.

The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by a cleaning agent having the following configuration, and have completed the present invention. That is, the present invention relates to, for example, the following [1] to [5].

[1] Contains 3 to 10% by mass of tetramethylammonium hydroxide (A), 20 to 60% by mass of water (B), dimethyl sulfoxide (C), and compound (D) represented by the following formula (1) A cleaning agent characterized by.

(In the formula (1), R ¹ represents an alkanediyl group having 1 to 3 carbon atoms; n represents an integer of 1 to 3; and when n is 2 or more, the plurality of R ¹ are the same. And R ² represents an alkyl group having 1 to 6 carbon atoms.)

[2] The cleaning agent according to [1], wherein the content ratio of the dimethyl sulfoxide (C) contained in the cleaning agent is 10 to 40% by mass.

[3] The cleaning agent according to [1] or [2], wherein the content ratio of the compound (D) represented by the formula (1) contained in the cleaning agent is 10 to 40% by mass.

[4] A step of preparing an aqueous solution by mixing 3 to 10 parts by mass of tetramethylammonium hydroxide (A) and 20 to 60 parts by mass of water (B), the aqueous solution and the compound (D) represented by the formula (1) A method for producing a cleaning agent, comprising: a step of mixing to form a mixed solution; and a step of mixing the mixed solution and dimethyl sulfoxide (C).

[5] (1) A step of forming a laminated body having a support, a temporary fixing material, and a processing object, wherein the object is held on the temporary fixing material;
(2) processing the object and / or moving the laminate;
(3) a step of separating the object from the support; and (4) a step of washing the object with the cleaning agent according to any one of [1] to [3];
A method for processing an object, comprising:

ADVANTAGE OF THE INVENTION According to this invention, in the semiconductor manufacturing processes, such as removal of the residue of temporary fixing material, the cleaning agent which can remove a residue favorably, the manufacturing method of the cleaning agent which can manufacture a cleaning agent favorably, and temporary In a method of processing and moving an object in a state where the object to be processed is temporarily fixed on the support using a fixing material, and subsequently separating the support and the object, the temporary fixing material on the object A method for treating an object with little residue can be provided.

FIG. 1 is a diagram showing an embodiment relating to processing of an object according to the present invention.

Each component exemplified in this specification, for example, each component in the cleaning agent may be used alone or in combination of two or more unless otherwise specified.

<1> Cleaning Agent The cleaning agent of the present invention comprises 3 to 10% by mass of tetramethylammonium hydroxide (A), 20 to 60% by mass of water (B), dimethyl sulfoxide (C), and the following formula (1) It contains the compound (D) shown in the above.

In addition, other components can be contained as necessary within a range not losing the performance of the cleaning agent of the present invention.

In the separation treatment, it is estimated that the residue of the temporary fixing material after irradiation with light energy such as ultraviolet rays and infrared rays is a high carbon content film.
A high carbon content film is generally soluble in water but contains a lot of oil, so it has the property of inhibiting it, that is, a thick hydrophilic film (hydroxyl group, carboxyl group, etc.) on the surface layer of the high carbon content film. It is necessary to design a cleaning agent in which the hydrophobic film in the inner layer of the high carbon-containing film is dissolved and peeled off with an aprotic solvent.

The cleaning agent of the present invention contains basic tetramethylammonium hydroxide (A) for acting on the acidic groups of the hydrophilic film, and decomposes the hydrophilic film with tetramethylammonium hydroxide (A). And in order to melt | dissolve tetramethylammonium hydroxide (A), water (B) is needed. On the other hand, in order to dissolve the hydrophobic membrane, an aprotic organic solvent mixed with tetramethylammonium hydroxide (A) and water (B) is required. In the present invention, dimethyl sulfoxide (C) is used as the aprotic organic solvent. However, in order to decompose the thick hydrophilic film, a large amount of tetramethylammonium hydroxide (A) and accompanying it are contained in the cleaning agent. Since a large amount of water (B) is contained, tetramethylammonium hydroxide (A) and water (B) and dimethyl sulfoxide (C) cannot be mixed uniformly, and as a result, the cleaning power of the cleaning agent is reduced. It became clear.

In the cleaning agent of the present invention, the compound (D) of a protic solvent is used as a component miscible with tetramethylammonium hydroxide (A) and water (B) or dimethyl sulfoxide (C). It is presumed that the components were mixed uniformly and thus became a cleaning agent having good detergency.
Compound (D) is presumed to have a co-solvent effect with dimethyl sulfoxide (C), and by containing compound (D) in the cleaning agent, it becomes a cleaning agent having good detergency. Estimated.

<1-1> Tetramethylammonium hydroxide (A)
Tetramethylammonium hydroxide (A) is a component that acts on the hydrophilic film in the surface layer of the residue of the temporary fixing material and decomposes.

The content of tetramethylammonium hydroxide (A) contained in the cleaning agent is 3 to 10% by mass, preferably 3.5 to 7% by mass, more preferably 4 to 6% by mass.
If it is in the said range, the residue of a temporary fixing material can be removed favorably, without having a bad influence on the part (for example, copper film) weak to the base contained in a process target board | substrate.

<1-2> Water (B)
Water (B) is a component used for dissolving tetramethylammonium hydroxide (A).

The content of water (B) contained in the cleaning agent is 20 to 60% by mass, preferably 30 to 55% by mass, more preferably 40 to 50% by mass.
If it is within the above range, water (B) can be mixed well with other components contained in the cleaning agent, so that a transparent cleaning agent can be obtained without becoming cloudy. The residue of the material can be removed well.

<1-3> Dimethyl sulfoxide (C)
Dimethyl sulfoxide (C) is an aprotic component and is a component that acts and dissolves in the hydrophobic membrane in the inner layer of the residue of the temporary fixing material.

Dimethyl sulfoxide (C) is a component that is difficult to mix with tetramethylammonium hydroxide (A) and water (B), while it is considered to have a cosolvent effect with compound (D). Therefore, the content ratio of dimethyl sulfoxide (C) contained in the cleaning agent depends on the total content ratio of tetramethylammonium hydroxide (A) and water (B) contained in the cleaning agent, and the content ratio of compound (D). adjust.

The content ratio of dimethyl sulfoxide (C) contained in the cleaning agent is usually 10 to 40% by mass, preferably 15 to 35% by mass, and more preferably 20 to 35% by mass.
Within the above range, dimethyl sulfoxide (C) can be mixed well with other components contained in the cleaning agent, so that a transparent cleaning agent can be obtained without becoming cloudy. The fixing material residue can be removed satisfactorily.

<1-4> Compound (D)
Compound (D) is a protic component that is miscible with water (B) and is a component that functions as a co-solvent for dimethyl sulfoxide (C).

Compound (D) is a compound represented by the following formula (1).

(In the formula (1), R ¹ represents an alkanediyl group having 1 to 3 carbon atoms; n represents an integer of 1 to 3; and when n is 2 or more, the plurality of R ¹ are the same. R ² represents an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.)

Examples of the compound (D) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylbutyl ether, and the like. Alkyl ethers; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether; propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Propylene glycol monoalkyl ethers such as dimonobutyl ether and propylene glycol monomethyl ether; and dipropylene glycol monoalkyl ethers such as dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether And the like.
Among these, dipropylene glycol monoalkyl ethers are preferable because they are excellent in the cosolvent effect with dimethyl sulfoxide (C) and the residue of the temporary fixing material can be removed well.

The content ratio of the compound (D) contained in the cleaning agent is usually 10 to 40% by mass, preferably 15 to 35% by mass, more preferably 15 to 30% by mass.
Within the above range, compound (D) can be mixed well with other components contained in the cleaning agent, so that a transparent cleaning agent can be obtained without becoming cloudy, and as a result, temporarily fixed. The residue of the material can be removed well.

<1-5> Other Components The cleaning agent of the present invention can contain other components as needed within a range not losing the effect of the cleaning agent of the present invention. Examples of the other components include bases (excluding tetramethylammonium hydroxide (A)), aprotic organic solvents (excluding dimethyl sulfoxide (C)), protic organic solvents (excluding compound (D)) ), Corrosion inhibitors and surfactants.

The base is used for decomposing the hydrophilic film on the surface of the high carbon-containing film in the same manner as tetramethylammonium hydroxide (A).
Examples of the base include quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetraphenylammonium hydroxide; alkanolamines such as trimethanolamine; potassium hydroxide, potassium hydrogencarbonate And inorganic bases such as sodium carbonate; amines such as triethylamine and diethylamine.

The surfactant is used to improve the wettability of the cleaning agent to the residue of the temporary fixing material.
Examples of the surfactant include nonionic surfactants such as polyoxyalkylene phenyl ether, polyoxyalkylene methyl phenyl ether, polyoxyalkylene octyl phenyl ether, polyoxyalkylene nonyl phenyl ether; sodium dodecylbenzenesulfonate, and the like. And anionic surfactants such as alkylaryl sulfonates.
The content of the surfactant contained in the cleaning agent is usually 0.01 to 1% by mass.

<1-6> Use form of cleaning agent The cleaning agent of the present invention can be divided into combined products. For example, in order to reduce the weight of the cleaning agent during transportation, the amount of water (B) contained in the cleaning agent is limited to the amount capable of dissolving tetramethylammonium hydroxide (A), and the reduced amount of water (B) is used. It can be a combined product that is mixed immediately before.

Since the cleaning agent of the present invention contains dimethyl sulfoxide (C) which can be oxidized, it is preferable to store the cleaning agent of the present invention by enclosing an inert gas such as nitrogen.

The content ratio of impurities including metal (including metal ions) contained in the cleaning agent of the present invention does not adversely affect the substrate to be processed, particularly when the substrate to be processed is a precise substrate such as a semiconductor element. Therefore, it is preferably as small as possible and is usually 1 wtppm or less.

The viscosity of the cleaning agent of the present invention at 23 ° C. according to JIS Z8803 (2011) is usually 0.4 to 50 mPa · s, preferably 0.8 to 10 mPa · s.
The vapor pressure according to JIS K2258-1 (2009) of the cleaning agent of the present invention is usually 100 hPa or less, preferably 40 hPa or less. If it is in the said range, it will become the cleaning agent excellent in the point of the washing | cleaning property at high temperature.
If it is in the said range, since a cleaning agent can be made to contact the residue of a temporary fixing material uniformly, the residue of a temporary fixing material can be removed favorably.

<2> Manufacturing method of cleaning agent The cleaning agent of the present invention can be mixed with tetramethylammonium hydroxide (A), water (B), dimethyl sulfoxide (C) and compound (D) uniformly. Although they may be mixed in any order, the method for producing the cleaning agent of the present invention described below is preferred.
In addition, although the usage-amount (mass part) of each component is described below, these are the quantity when the cleaning agent finally obtained is 100 mass parts.

The method for producing a cleaning agent of the present invention comprises a step of preparing an aqueous solution by mixing 3 to 10 parts by mass of tetramethylammonium hydroxide (A) and 20 to 60 parts by mass of water (B) (hereinafter referred to as “step (I)”). A step of mixing the aqueous solution and the compound (D) to form a mixed solution (hereinafter also referred to as “step (II)”), and a step of mixing the mixed solution and dimethyl sulfoxide (C) (hereinafter, referred to as “step (II)”). (Also referred to as “step (III)”).

Since tetramethylammonium hydroxide (A) and water (B) and dimethyl sulfoxide (C) contained in the detergent are difficult to mix, tetramethylammonium hydroxide (A) and water (B) and dimethyl sulfoxide When (C) is directly mixed, there is a possibility that it will not mix uniformly due to the addition shock.
Therefore, before the tetramethylammonium hydroxide (A) and water (B) are combined with the dimethyl sulfoxide (C), the compound (D) which is a co-solvent of the dimethyl sulfoxide (C) is first mixed.
Further, since dimethyl sulfoxide (C) may be oxidized by oxygen in the air, the time of contact with air is made as short as possible.

The manufacturing method of the cleaning agent of the present invention is based on the above-mentioned possibility. That is, in the step (I), tetramethylammonium hydroxide (A) and water (B) are mixed and tetrahydroxide hydroxide is mixed. By preparing an aqueous solution of methylammonium (A), then mixing the compound (D) in the step (II) and finally mixing the dimethyl sulfoxide (C) in the step (III). Without any possibility, the cleaning agent according to the invention can be produced.

<2-1> Step (I)
In the step (I), an aqueous solution is prepared by mixing 3 to 10 parts by mass of tetramethylammonium hydroxide (A) and 20 to 60 parts by mass of water (B) in a vessel equipped with a stirring blade.
Here, since tetramethylammonium hydroxide (A) is usually sold in the form of an aqueous solution, finally, 3 to 10 parts by mass of tetramethylammonium hydroxide (A) and 20 to 60 water (B) are finally obtained. It is carried out by mixing tetramethylammonium hydroxide (A) and water (B) with a stirring blade so as to be part by mass.

The liquid temperature during mixing is usually 5 to 50 ° C., preferably 15 to 35 ° C. under 1 atm. In mixing, in order to reduce the amount of dissolved oxygen contained in the aqueous solution, it is preferable to mix while bubbling an inert gas such as nitrogen.

<2-2> Step (II)
In step (II), the aqueous solution and compound (D) are mixed to form a mixed solution.
The mixing is performed by adding the compound (D) to the container while stirring the aqueous solution. The liquid temperature during mixing is usually 5 to 50 ° C., preferably 15 to 35 ° C. under 1 atm. Further, as in the step (I), in order to reduce the amount of dissolved oxygen contained in the mixed solution, it is preferable to mix while bubbling an inert gas such as nitrogen.
The amount of compound (D) to be used is usually 10 to 40 parts by mass.

In addition, when the other components are included in the cleaning agent, the other components are usually mixed before and after the step (II).

<2-3> Step (III)
In step (III), the mixed solution and dimethyl sulfoxide (C) are mixed.
In mixing, the dimethyl sulfoxide (C) is put into the container while stirring the aqueous solution.
The amount of dimethyl sulfoxide (C) used is usually 10 to 40 parts by mass.

Tetramethylammonium hydroxide (A) and water (B) are not miscible with dimethyl sulfoxide (C). Therefore, when adding dimethyl sulfoxide (C), the total amount of dimethyl sulfoxide (C) is small. It is preferable to divide and input.

The liquid temperature during mixing is usually 5 to 50 ° C., preferably 15 to 35 ° C. under 1 atm. Further, as in the step (I), in order to reduce the amount of dissolved oxygen contained in the mixed solution, it is preferable to mix while bubbling an inert gas such as nitrogen.

After step (III), the mixed solution can be aged, and usually a detergent having excellent storage stability by aging at 5 to 50 ° C. for 12 hours or longer, preferably 15 to 35 ° C. for 24 hours or longer. Can be manufactured.
Since the cleaning agent of the present invention contains tetramethylammonium hydroxide (A) and dimethyl sulfoxide (C), the hydroxide anion of tetramethylammonium hydroxide (A) and polarized dimethyl sulfoxide (C) May form an ion-bonded compound (AC).

It is presumed that a detergent having excellent storage stability can be produced by performing the aging.

As described above, the cleaning agent of the present invention does not contain one or both of tetramethylammonium hydroxide (A) and dimethyl sulfoxide (C), and even when compound (AC) is contained. It is a cleaning agent of the invention.

Further, after the step (III), filtration such as a capsule filter can be performed in order to remove impurities.

<3> Method for processing an object In the present invention, the temporarily fixing material means that an object is temporarily fixed on a support so that the object does not move due to being shifted from the support when the object to be processed is processed and / or moved. It is the material used to do. The object to be processed means an object to be subjected to a processing process or a movement process in a process (2) described later (for example, a stage in the process (1) or (2) described later), and the process has been received. It may mean a later object (for example, a stage in steps (3) and (4) described later). Hereinafter, the processing object is also simply referred to as “object”.

The method for treating an object of the present invention includes a step of forming a laminate having a support, a temporary fixing material, and an object to be treated (hereinafter also referred to as “step (1)”), wherein the object is the temporary A step of processing the object and / or moving the laminate (hereinafter also referred to as “step (2)”); a step of separating the object from the support; (Hereinafter also referred to as “step (3)”), and a step of cleaning the object with the cleaning agent of the present invention (hereinafter also referred to as “step (4)”). An embodiment is shown in FIG.

<3-1> Step (1)
In the step (1), as shown in FIG. 1 (1), for example, the temporary fixing material 30 is formed on the surface of the support 10 and / or the object 20, and the object is interposed via the temporary fixing material 30. The object 20 is temporarily fixed on the support 10 by laminating 20 and the support 10 to form the laminate 40. Further, the temporary fixing material 30 is formed on the surface of the support 10, and an object such as a resin coating film or a wiring layer is formed on the temporary fixing material 30, whereby the target 20 is placed on the support 10. It may be temporarily fixed. The object can be surface-treated as necessary.

The temporary fixing material may be a temporary fixing material consisting of one layer or a temporary fixing material consisting of two or more layers, and as a method of forming the temporary fixing material, for example, the temporary fixing material has A method of directly forming each layer on a support and / or an object, after forming a film with a fixed thickness on a film subjected to a release treatment using a temporary fixing composition, And / or a method of transferring to an object by a laminating method. From the viewpoint of film thickness uniformity, the direct forming method is preferable.

When forming the temporarily fixed material on the object, the surface of the object (for example, the circuit surface) can be pretreated in order to make the spread of the temporarily fixed material in the surface uniform. Examples of the surface treatment method include a method in which a surface treatment agent is applied to the surface of an object in advance. Examples of the surface treatment agent include a coupling agent such as a silane coupling agent.

Examples of the method for applying the temporary fixing composition include a spin coating method and an ink jet method. After the temporary fixing composition is applied and a coating film is formed, each layer of the temporary fixing material is formed by heating as necessary to volatilize the solvent. The heating conditions are appropriately determined according to the type of the temporary fixing composition. For example, the heating temperature is usually 100 to 350 ° C., and the heating time is usually 1 to 60 minutes.

The temporary fixing of the object and the support via the temporary fixing material is performed by, for example, preferably laminating each layer with a pressure of 0.01 to 100 MPa for 1 to 20 minutes at 5 to 400 ° C., more preferably 150 to 400 ° C. By adding in the direction. Further, if necessary, heat treatment is performed at 150 to 300 ° C. for 10 minutes to 3 hours. In this way, the object is firmly fixed on the support via the temporary fixing material.

Examples of the temporary fixing composition and the temporary fixing material include known temporary fixing compositions and temporary fixing materials. For example, Japanese Patent Application Laid-Open No. 2013-235919, International Publication No. 2015/077983, Japan Temporary fixing of the type in which the object is separated from the support by mechanical force such as published patent 2013-179135, published US 2012/291919, and published US 2011/065257 Composition and temporary fixing material; and Japanese Patent Publication No. 2012-052031, International Publication No. 2017/056662, U.S. Publication No. 2007/077685, Japanese Publication No. 2012-106486, and Japan Temporary fixing material is altered by light irradiation as described in Japanese Patent Publication No. 2016-215394. The object of the temporary fixing composition of the type separating from the support and the temporary fixing material (light-irradiating temporary fixing material) and the like by causing.
Among these, preferably a light irradiation type temporary fixing material, more preferably light is a light irradiation type temporary fixing material by laser light, and the reason is that in step (4), a higher carbon residue is washed. This is because the effect of the cleaning agent of the present invention can be utilized more.

Examples of the object to be processed (moved) include a semiconductor wafer, a semiconductor chip, a glass substrate, a resin substrate, a metal substrate, a metal foil, a polishing pad, a resin coating, and a wiring layer. At least one selected from bumps, wirings, through holes, through hole vias, insulating films, and various elements can be formed on the semiconductor wafer and the semiconductor chip. Various elements can be formed or mounted on the substrate. Examples of the resin coating include a layer containing an organic component as a main component; specifically, a photosensitive resin layer formed from a photosensitive material, an insulating resin layer formed from an insulating material, A photosensitive insulating resin layer formed from a photosensitive insulating resin material can be used.

The support may be any material as long as it does not cause damage or alteration when the object to be processed is processed and / or moved, such as a silicon wafer substrate, a sapphire substrate, or a glass substrate. And quartz substrate and transparent resin substrate. In particular, in the step (3), when using a temporarily fixing material that separates the object from the support by altering the temporarily fixed material by light irradiation, the support is irradiated with light from the support side to temporarily fix the material. Therefore, it is preferable to use a substrate having a high transmittance with respect to light used in light irradiation, and examples thereof include a glass substrate, a quartz substrate, and a transparent resin substrate.

<3-2> Step (2)
In the step (2), as shown in FIG. 1 (2), the object 20 temporarily fixed on the support 10 is processed to obtain the processed object 21, and / or the obtained laminate 41 is obtained. It is a process of moving. The moving process is a process of moving an object such as a semiconductor wafer together with a support from one apparatus to another apparatus. Examples of processing of the object temporarily fixed on the support include dicing of the object, thinning of the object (backside grinding, etc.), photofabrication, stacking of semiconductor wafers or chips, mounting of various elements, Resin sealing is mentioned. The photofabrication includes, for example, one or more processes selected from resist pattern formation, etching processing, sputtered film formation, plating process, and plating reflow process.

<3-3> Step (3)
After the processing of the object or the movement of the laminate, in step (3), the processed object 21 is separated from the support 10 as shown in FIG. Examples of the method for separating the object and the support include, for example, a method in which a force is applied to the object or the support in a direction parallel to the support surface or the object surface to separate the two; one of the object or the support Is fixed, and the other is lifted at a certain angle from the parallel direction with respect to the support surface or the object surface to separate the two.

In the former method, the object is slid horizontally with respect to the surface of the support, and at the same time, the support is fixed, or a force that antagonizes the force applied to the object is applied to the support. And a method of separating the support and the object.

In the latter method, it is preferable to separate the support and the object by applying a force in a direction substantially perpendicular to the support surface or the object surface. “Applying a force in a direction substantially perpendicular to the support surface or the object surface” means that the z axis, which is an axis perpendicular to the support surface or the object surface, is usually 0 ° to 60 °. It means to apply a force in the range, preferably in the range 0 ° to 45 °, particularly preferably 0 °, ie perpendicular to the support surface or the object surface. As the separation method, for example, a method in which the peripheral edge of the object or the support is lifted and peeled in order from the peripheral edge toward the center while applying a force in a direction substantially perpendicular to the support surface or the object surface (hook-pull method). Can be done.

The separation can be performed usually at 5 to 100 ° C., preferably 10 to 45 ° C., more preferably 15 to 30 ° C. Moreover, when separating, in order to prevent damage to the object, a reinforcing tape, for example, a commercially available dicing tape, can be applied to the surface of the object opposite to the temporary fixing surface with the support.

In the step (3), the temporary fixing material is irradiated with light to decompose or alter the temporary fixing material, thereby reducing the strength and adhesive force of the temporary fixing material, and then separating the object from the support. It is preferable to do. In one embodiment, the temporary fixing material is irradiated with light from the support side. By light irradiation, the components contained in the temporary fixing material absorb light, and the strength and adhesive strength of the temporary fixing material are reduced. Therefore, if it is after the light irradiation with respect to a temporarily fixed material, a support body can be easily isolate | separated from a target object, without specifically requiring the heat processing of a temporarily fixed material.

For the light irradiation, ultraviolet rays are preferably used. For example, ultraviolet rays having a wavelength of 10 to 400 nm are employed, and ultraviolet rays having a wavelength of 250 to 400 nm are particularly preferred. Examples of the light source of irradiation light include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a laser. Among these, a laser is preferable. It is preferable to irradiate the entire surface of the temporarily fixed material while scanning the laser from the support side, and it is more preferable to irradiate the laser to the temporarily fixed material with a focus.

Examples of the laser include a solid laser (eg, all solid laser using a photoexcited semiconductor laser, YAG laser), a liquid laser (eg, dye laser), and a gas laser (eg, excimer laser). Among these, YAG laser (wavelength: 355 nm) and excimer laser (wavelength: 200 to 310 nm) are preferable.

The light irradiation conditions vary depending on the type of light source and the like, but in the case of an all-solid-state laser using a light-excited semiconductor laser and a YAG laser, it is usually 1 mW to 100 W, and the integrated light quantity is usually 1.4 × 10 ⁻⁷ to 1. 4 × 10 ⁷ mJ / cm ² .

Subsequently, by applying a force to the object or the support, the object is separated from the support by separating the object from the support. Note that separation is preferably performed after the light irradiation, but the separation can be performed while performing the light irradiation.

<3-4> Step (4)
Step (4) is a step of cleaning with the cleaning agent 50 of the present invention. After separating the support and the object, the temporary fixing material usually remains on the object. The temporary fixing material remaining on the object after the separation step, that is, the residue 31 of the temporary fixing material can be favorably removed by using the cleaning agent of the present invention as described above.

Examples of the cleaning method include a method of immersing an object in the cleaning agent of the present invention and a method of spraying the cleaning agent of the present invention on the object as shown in FIG. Ultrasound may be applied. The temperature of the cleaning agent for cleaning the object is not particularly limited, but is usually 10 to 80 ° C., preferably 15 to 55 ° C., more preferably 20 to 40 ° C., and further preferably 25 to 40 ° C. The washing time, for example, the immersion time is usually 2 to 20 minutes, preferably 5 to 15 minutes.

In one embodiment, the dissolved oxygen content of the cleaning agent of the present invention is preferably small from the viewpoint of preventing the above-described processing object from deteriorating. For this reason, it is preferable to perform the said washing | cleaning using the cleaning agent of this invention bubble-treated with inert gas, such as nitrogen. For example, in the method of immersing an object in the cleaning agent of the present invention, it is preferable that the cleaning is performed while the cleaning agent is subjected to the bubbling treatment.

In step (4), the object to be treated can be cleaned using another cleaning agent after being cleaned using the cleaning agent of the present invention. In one embodiment, cleaning with the cleaning agent of the present invention, cleaning with water, cleaning with an acid cleaning agent, and cleaning with water are sequentially performed.

Examples of the acid in the acid detergent include inorganic acids such as sulfuric acid; organic acids such as acetic acid, oxalic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid. The acid content in the acid detergent is usually more than 0% by mass and 10% by mass or less, preferably 0.001 to 8% by mass, more preferably 0.01 to 1% by mass. Such an embodiment is preferable because cleaning can be performed while suppressing corrosion of the metal.

Examples of the solvent in the acid cleaning agent include the solvents exemplified in the cleaning agent of the present invention, and water is preferable. That is, an acid aqueous solution is preferable as the acid cleaning agent. Examples of the cleaning method using the acid cleaning agent include a method of immersing the object in the acid cleaning agent and a method of spraying the acid cleaning agent on the object, and ultrasonic waves may be applied during the immersion. The temperature of the acid detergent is not particularly limited, but is usually 10 to 80 ° C., preferably 15 to 55 ° C. The washing time, for example, the immersion time is usually 0.02 to 15 minutes, preferably 0.5 to 10 minutes.

Examples of other cleaning agents include various solvents exemplified in the cleaning agent of the present invention, and water is preferable. The cleaning method and conditions using other cleaning agents are the same as the cleaning method and conditions using acid cleaners.

After performing the above washing | cleaning, it can dry and can obtain a process target object.
As described above, it is possible to obtain an object to be processed that is free of residue of the temporarily fixing material.

<4> Uses of the cleaning agent The cleaning agent of the present invention can satisfactorily remove residues having both hydrophilic and hydrophobic properties such as a high carbon-containing film. Residues that are difficult to remove can be satisfactorily removed, such as residues of photoresist after etching and plating of the substrate to be processed and residues of temporary fixing materials.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of Examples and the like, “part” means “part by mass” unless otherwise specified.

[Production Example 1] Production of temporary fixing composition A reactor equipped with a condenser, a thermometer and a stirrer was charged with 100 parts of phenol, 100 parts of propylene glycol monomethyl ether acetate, and 50 parts of paraformaldehyde (in terms of formaldehyde). 2 parts of oxalic acid was added and heated at 120 ° C. for 5 hours while dehydrating.
Water was added to the reaction solution and stirred. After collecting the precipitate, it was washed with water and dried at 50 ° C. for 17 hours to obtain a phenol / formaldehyde condensate (Mw = 1,550).
100 parts of the condensate was uniformly dissolved with 550 parts of a mixed solvent of cyclohexanone / methoxypropyl acetate = 60/40 (mass%) to produce a temporary fixing composition.

[Example 1A]
In a container equipped with a stirring blade, 35 parts of water and a 25 mass% tetramethylammonium hydroxide aqueous solution were added and stirred at 25 ° C. While stirring, 22 parts of propylene glycol monomethyl ether as compound (D) was placed in a container, and then 27 parts of dimethyl sulfoxide was added in small portions. After stirring at 25 ° C. for 1 hour, the mixture was aged at 25 ° C. for 12 hours to produce a uniform and transparent cleaning agent of Example 1A.
The content ratio of the components contained in the cleaning agent of Example 1A was tetramethylammonium hydroxide / water / dimethylsulfoxide / propylene glycol monomethyl ether = 4/47/27/22 (mass%).

[Examples 2A to 10A and Comparative Examples 1A to 11A]
In the same procedure as in Example 1A, the cleaning agents of Examples 2A to 10A and Comparative Examples 1A to 11A containing the respective components and the content ratios shown in Table 1 were produced. The unit of numerical values in Table 1 is mass%.

Details of each component in Table 1 are as follows.
TMAH: Tetramethylammonium hydroxide TEAH: Tetraethylammonium hydroxide DIW: Water DMSO: Dimethyl sulfoxide PGME: Propylene glycol monomethyl ether dEGBE: Diethylene glycol monobutyl ether dPGBE: Dipropylene glycol monomethyl ether PG: Propylene glycol PGMEA: Propylene glycol monomethyl ether acetate PGdME : Propylene glycol dimethyl ether

<Processing of the object>
[Example 1B]

A 4-inch silicon wafer was spin-coated with the composition for temporary fixing of Production Example 1, heated at 180 ° C. for 1 minute using a hot plate, and further heated at 300 ° C. for 2 minutes to form a uniform layer having a thickness of 10 μm ( A substrate 1 having I) was obtained.
After the substrate 1 was cut into a square of 1 cm in length and 1 cm in width, it was bonded to a glass substrate (a square of 1 cm in length and 1 cm in width; a support) through the layer (I), and 250 ° C. using a die bonder device. Then, a pressure of 0.2 MPa was applied for 2 minutes to produce a laminate.

A glass substrate with an output of 100 mW and an integrated light amount of 2.08 × 10 ⁻⁴ mJ / cm ² is applied to the laminate using an all-solid-state high-power laser device (trade name “Genesis CX355 STM Compact”, manufactured by Coherent Japan Co., Ltd.). UV laser (wavelength 355 nm) was irradiated from the side. Using a universal bond tester (trade name “Daily 4000”, manufactured by Daisy) for the test laminate after light irradiation, in the direction of the axis (z axis) perpendicular to the glass substrate surface by the hook-pull method. A glass substrate was separated from the silicon wafer by applying a force (speed of 500 μm / second, 23 ° C.). A residue substrate having a residue of layer (I) on a silicon wafer was obtained.

The cleaning agent of Example 1A was put in a container, and the residue substrate was immersed at 25 ° C. for 5 minutes while stirring at 250 rpm with a stirrer chip. Next, the surface of the silicon wafer was washed away by spraying with pure water for 2 minutes and then dried.
The presence or absence of the residue after drying was observed with an optical microscope, and the removal area ratio of the residue on the surface of the wafer was measured. The result of the removal area ratio of the residue with an optical microscope was evaluated according to the following criteria. The evaluation results are shown in Table 2.
AA: The residue is peeled off by 80% or more.
BB: The residue is peeled off by 40% or more and less than 80%.
CC: The residue is peeled off less than 40% or not peeled off.

[Examples 2B to 10B and Comparative Examples 1B to 11B]
In Example 1B, the treatment of the object was performed in the same procedure as Example 1B, except that the cleaning agents of Examples 1A to 10A and Comparative Examples 1A to 11A were used instead of the cleaning agent of Example 1A, respectively. And the removal area ratio of the residue was measured and evaluated according to the same criteria as in Example 1B. The evaluation results are shown in Table 2.

10: Support 20: Object 21: Processed object 30: Temporary fixing material 31: Residue of temporary fixing material 40: Laminated body 41: Laminated body 50 after processing: Cleaning agent

Claims

Containing 3 to 10% by mass of tetramethylammonium hydroxide (A), 20 to 60% by mass of water (B), dimethyl sulfoxide (C), and compound (D) represented by the following formula (1) Characteristic cleaning agent.

(In the formula (1), R 1 represents an alkanediyl group having 1 to 3 carbon atoms; n represents an integer of 1 to 3; and when n is 2 or more, the plurality of R 1 are the same. And R 2 represents an alkyl group having 1 to 6 carbon atoms.)
The cleaning agent according to claim 1, wherein the content ratio of the dimethyl sulfoxide (C) contained in the cleaning agent is 10 to 40% by mass.
The cleaning agent according to claim 1 or 2, wherein the content of the compound (D) represented by the formula (1) contained in the cleaning agent is 10 to 40% by mass.
Step of preparing an aqueous solution by mixing 3 to 10 parts by mass of tetramethylammonium hydroxide (A) and 20 to 60 parts by mass of water (B), mixing and mixing the aqueous solution and the compound (D) represented by the following formula (1) The manufacturing method of the cleaning agent characterized by having the process of forming a liquid, and the process of mixing the said liquid mixture and dimethylsulfoxide (C).

(In the formula (1), R 1 represents an alkanediyl group having 1 to 3 carbon atoms; n represents an integer of 1 to 3; and when n is 2 or more, the plurality of R 1 are the same. And R 2 represents an alkyl group having 1 to 6 carbon atoms.)
(1) A step of forming a laminate having a support, a temporarily fixing material, and a processing object, wherein the object is held on the temporarily fixing material;
(2) processing the object and / or moving the laminate;
(3) a step of separating the object from the support; and (4) a step of washing the object with the cleaning agent according to any one of claims 1 to 3;
A method for processing an object, comprising: