WO2017056662A1 - Method for processing work, composition for temporary fixation, semiconductor device, and process for producing same - Google Patents

Abstract

[Problem] To provide a method which comprises processing and transferring a work to be processed while keeping the work temporarily fixed to a support, with a temporary fixer interposed therebetween, and succesively separating the support from the work by a light-irradiation separation method, the method being capable of preventing the work from suffering photodeterioration. [Solution] A method for processing a work to be processed which comprises: the step of forming a laminate comprising a support, a temporary fixer comprising a layer (I) comprising a polymer (A) having a structural unit (A1), and the work; the step of processing the work and/or transferring the laminate; the step of irradiating the layer (I) with light from the support side; and the step of separating the support from the work. [In formula (A1), Ar is a fused aromatic ring; R¹ is a hydrogen atom or a C_1-20 hydrocarbon group; R² is a halogen atom or a C_1-20 hydrocarbon group; R³ is a hydrogen atom or an organic group; a is an integer of 1 or larger; and b is an integer of 0 or larger.]

Description

Method for processing object, composition for temporary fixing, semiconductor device and method for manufacturing the same

The present invention relates to an object processing method, a temporary fixing composition, a semiconductor device, and a manufacturing method thereof.

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. Yes. This 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, the adhesive force of the temporary fixing material is reduced by irradiating the temporary fixing material in the laminate having the support, the temporary fixing material, and the object with radiant energy such as ultraviolet rays and infrared rays. Subsequently, a method for separating the support and the object has been proposed (see Patent Documents 1 to 3). Hereinafter, a method of separating the support and the object after the temporary fixing material is irradiated with light to reduce its adhesive force or while performing light irradiation is also referred to as “light irradiation separation method”.

Patent Documents 1 to 3 disclose temporary fixing materials used in the light irradiation separation method. Here, the temporary fixing material of Patent Document 1 has a bonding layer and a release layer, and the temporary fixing material of Patent Document 2 includes an adhesive layer and a separation layer containing a polymer having a light absorption property. And the temporary fixing material of Patent Document 3 includes an adhesive layer, a light blocking layer, and a photothermal conversion layer.

US Published Patent No. 2014/0106473 JP 2012-106486 A JP 2011-077667 A

Since the object to be processed may be deteriorated by light used in the light irradiation separation method, the light is prevented from reaching the object by absorbing the light in the separation layer. It is necessary to prevent deterioration. However, the separation layer deteriorates due to heat during processing, and as a result, the separation layer cannot sufficiently absorb the light, and there is a problem that the light reaches the object.

An object of the present invention is to process and move an object in a state in which the object to be processed is temporarily fixed on a support via a temporary fixing material, and then separate the support and the object by a light irradiation separation method. It is an object of the present invention to provide a method that can prevent light degradation of the object.

The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by a processing method for an object having the following configuration, and the present invention has been completed.
That is, the present invention relates to, for example, the following [1] to [16].

[1] (1) A step of forming a laminate having a support, a temporary fixing material, and an object to be treated, wherein the temporary fixing material is a polymer (A) having a structural unit represented by the following formula (A1) And (2) a step of processing the object and / or moving the laminated body; and a layer (I) containing: the object is held on the temporary fixing material; (3) A method for treating an object, comprising: irradiating the layer (I) with light from the support side; and (4) a step of separating the support and the object.

[In the formula (A1), Ar represents a condensed polycyclic aromatic ring; —OR ¹ represents a group bonded to the condensed polycyclic aromatic ring, and R ¹ represents a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms. And a plurality of —OR ^{1 s} may be the same or different from each other; R ² is a group bonded to the condensed polycyclic aromatic ring, and is a halogen atom or having 1 to 20 carbon atoms. A hydrocarbon group, and when there are a plurality of R ^{2 s} , they may be the same or different from each other; R ³ is a hydrogen atom or an organic group, and R ³ may be the same or different from each other; Is an integer of 1 or more, and b is an integer of 0 or more. ]
[2] The method for treating an object according to [1], wherein the temporary fixing material further includes an adhesive layer (II).
[3] The method for processing an object according to [2], wherein the laminate includes the elements in the order of the support, the layer (I), the adhesive layer (II), and the processing object.
[4] The method for processing an object according to any one of [1] to [3], wherein, in the step (1), a processing object having at least a wiring layer is formed on the temporary fixing material.
[5] The object processing method according to [4], wherein the processing in the step (2) includes disposing at least one selected from a semiconductor wafer and a semiconductor chip on the wiring layer.
[6] The method for processing an object according to any one of [1] to [5], wherein the light in the step (3) is ultraviolet light.
[7] The method for treating an object according to [6], wherein the ultraviolet rays are ultraviolet rays having a wavelength of 300 to 400 nm.
[8] The method for treating an object according to any one of [1] to [7], wherein the layer (I) has a thickness of 0.1 to 500 μm.
[9] The method for treating an object according to any one of [1] to [8], wherein the condensed polycyclic aromatic ring in the formula (A1) is a naphthalene ring.
[10] The method for treating an object according to any one of [1] to [9], wherein R ¹ in the formula (A1) is a hydrogen atom or an alkynyl group.
[11] A composition for temporary fixing containing a polymer (A) having a structural unit represented by the following formula (A2).

[In the formula (A2), Ar represents a condensed polycyclic aromatic ring; —OR ¹ represents a group bonded to the condensed polycyclic aromatic ring; R ¹ represents a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms; And a plurality of —OR ^{1 s} may be the same or different from each other; R ² is a group bonded to the condensed polycyclic aromatic ring, and is a halogen atom or having 1 to 20 carbon atoms. A hydrocarbon group, and when there are a plurality of R ^{2 s} , they may be the same or different from each other; R ³ is a hydrogen atom or an organic group, and R ³ may be the same or different from each other; Is an integer of 2 or more, and b is an integer of 0 or more. ]
[12] The composition for temporary fixing according to [11], further containing a solvent.
[13] Temporary fixing according to [11] or [12], wherein the content of the polymer (A) contained in 100% by mass of the solid content of the composition for temporary fixing is 50% by mass or more. Composition.
[14] A semiconductor device manufacturing method for manufacturing a semiconductor device by processing an object by the processing method according to any one of [1] to [10].
[15] (1) A step of forming a laminate having a support, a temporary fixing material, and a wiring layer, wherein the temporary fixing material comprises a polymer (A) having a structural unit represented by the formula (A1). The wiring layer is formed on the temporary fixing material; and (2) at least one selected from a semiconductor wafer and a semiconductor chip is disposed on the wiring layer. (3) A step of irradiating the layer (I) with light from the support side; and (4) a step of separating the support and the wiring layer.
[16] A semiconductor device obtained by the manufacturing method according to [14] or [15].

According to the present invention, the object is processed and moved in a state where the object to be processed is temporarily fixed on the support through the temporarily fixing material, and then the support and the object are separated by the light irradiation separation method. In this method, it is possible to provide a method capable of preventing light degradation of the object.

FIG. 1 is a cross-sectional view of an embodiment according to a laminate formed in the present invention.

Hereinafter, the laminated body formed in the present invention will be described including a temporary fixing composition that is a raw material composition of the temporary fixing material constituting the laminated body, and then an object processing method, a semiconductor device, and a production thereof A method will be described.

In the present invention, the temporary fixing material refers to a material used for temporarily fixing an object on a support so that the object does not move due to being shifted from the support when the processing object is processed and / or moved. It is. 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”.

1. Laminate In the laminate formed according to the present invention, a processing object to be processed or moved is temporarily fixed on a support via a temporary fixing material. In one embodiment, the temporary fixing material is sandwiched between an object and a support.

The temporary fixing material has a layer (I) (hereinafter, also referred to as “separation layer (I)”) containing a polymer (A) described later. In one embodiment, the temporary fixing material is further bonded to the separation layer (I). And an agent layer (II). The laminate preferably has a separation layer (I) between the support and the adhesive layer (II). That is, the laminate preferably includes the layers in the order of the support, the separation layer (I), the adhesive layer (II), and the object.

The separation layer (I) contains the polymer (A). When the separation layer (I) is irradiated with light described later, the polymer (A) absorbs the light, and the polymer (A) is decomposed or altered. Due to this decomposition or alteration, the strength or adhesive strength of the separation layer (I) decreases before and after the light irradiation. By applying an external force to the laminate, cohesive failure occurs in the separation layer (I), or interfacial failure occurs between the separation layer (I) and the layer in contact with the layer. Therefore, the support and the object can be easily separated by applying an external force to the laminated body after the light irradiation treatment.

The temporary fixing material may have an adhesive layer (II) formed in direct contact with the layer (I) or sandwiching another layer in addition to the separation layer (I). In this way, the temporary fixing material having two or more layers is, for example, protection of the circuit surface of the object, adhesion / separation between the support and the object, light shielding used during light irradiation treatment, Moreover, it can have functions such as heat resistance during processing and light irradiation in a well-balanced manner.

An example of the laminate is shown in FIG. The laminate 1 includes a support 10, a temporarily fixed material 20 formed on the support 10, and an object 30 temporarily fixed to the support 10 by the temporarily fixed material 20. The temporary fixing material 20 includes an adhesive layer (II) 21 in contact with the object 30 and a separation layer (I) 22 formed on the layer (II) 21 and in contact with the support 10. In this example, the temporary fixing material having the adhesive layer (II) is shown, but a temporary fixing material not having the layer (II) may be used.

The temporary fixing material may have any other layer in addition to the layer (I) and the layer (II). In the case of a laminate having the above-mentioned elements in the order of the support, the separation layer (I), the adhesive layer (II) and the object, for example, an intermediate layer is provided between the layer (I) and the layer (II). In addition, another layer may be provided between the layer (I) and the support or between the layer (II) and the object. In particular, a two-layer temporary fixing material composed of the layer (I) and the layer (II) is preferable.

The total thickness of the temporary fixing material depends on the size of the temporary fixing surface of the object, the heat resistance and light shielding properties required in processing and light irradiation treatment, and the degree of adhesion between the object and the support. Can be selected arbitrarily. The total thickness of the temporary fixing material is usually 0.2 to 1000 μm, preferably 0.2 to 500 μm, more preferably 1 to 300 μm. The thickness of each of the layers (I) and (II) is usually independently 0.1 to 500 μm, preferably 0.1 to 250 μm, more preferably 0.5 to 150 μm. When these thicknesses are within the above ranges, the temporarily fixing material has sufficient holding force for temporarily fixing the object, and the object does not fall off from the temporarily fixing surface during the processing or moving process. .

The temporary fixing material is used in various processing processes required in the context of modern economic activities, such as miniaturization processing of various material surfaces, various surface mounting, transportation of semiconductor wafers and semiconductor chips, etc. It is suitably used as a temporary fixing material.

[Separation layer (I)]
The separation layer (I) contains a polymer (A) described below. The separation layer (I) can be formed from, for example, a temporary fixing composition containing the polymer (A). The composition for temporary fixing may contain a solvent.

Semiconductor wafers and semiconductor chips, which are examples of objects to be processed, are generally weak to light and may deteriorate when irradiated with light. The separation layer (I) needs to block the light so that the light used in the light irradiation separation method does not reach the object. Moreover, it is preferable that the separation layer (I) can block the light even after a processing process performed with the object temporarily fixed on the support, for example, a high-temperature process such as a plating process.

The separation layer (I) containing the polymer (A) has a low light transmittance for the light used in the light irradiation treatment. That is, the separation layer (I) has a light transmittance at the wavelength of light used in the light irradiation treatment, for example, a light transmittance at a wavelength of 355 nm, preferably 10% T or less, more preferably 5% T or less, and even more preferably. Is 1% T or less.

The separation layer (I) containing the polymer (A) can maintain a low light transmittance with respect to light used in the light irradiation treatment, even after being subjected to a high temperature treatment of about 300 ° C., for example. . That is, after the separation layer (I) is heat-treated at a temperature of 300 ° C. for 10 minutes in a nitrogen stream, the light transmittance at the wavelength of light used in the light irradiation treatment is preferably, for example, the light transmittance at a wavelength of 355 nm. Is 10% T or less, more preferably 5% T or less, and still more preferably 1% T or less.

Therefore, the separation layer (I) can prevent the light used in the light irradiation process from reaching the object to be processed, and can prevent the deterioration of the object. The separation layer (I) is a layer in which the polymer (A) absorbs the light and decomposes or deteriorates, so that the support and the object are separated from each other, and also blocks light used in the light irradiation treatment. It is also a layer to do.

The light transmittance of the separation layer (I) can be measured as follows. A laminate comprising a transparent substrate and the separation layer (I) is formed. About the said laminated body, using a spectrophotometer, the base line correction | amendment is carried out about the said board | substrate as needed, the light transmittance (% T) of the said laminated body is measured, and the light transmittance (%) of a separated layer (I) T).

<Polymer (A)>
The polymer (A) has a structural unit represented by the formula (A1) (hereinafter also referred to as “structural unit (A1)”).

In the formula (A1), details of each symbol are as follows.

Ar is a condensed polycyclic aromatic ring, preferably a condensed polycyclic aromatic hydrocarbon ring. The number of rings constituting the condensed polycyclic aromatic ring (eg, the number of benzene nuclei) is preferably 2 to 5, more preferably 2 to 3, and still more preferably 2. Examples of the condensed polycyclic aromatic ring include a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, a triphenylene ring, and a perylene ring, and the separation layer (I) is heated by heat during processing. A naphthalene ring is preferable because the light transmittance hardly increases.

—OR ¹ is a group bonded to the condensed polycyclic aromatic ring. R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, An alkyl group having 1 to 20 carbon atoms such as nonyl group and decyl group; a cycloalkyl group having 3 to 20 carbon atoms such as cyclopentyl group and cyclohexyl group; an aryl group having 6 to 18 carbon atoms such as phenyl group and naphthyl group; propargyl And an alkynyl group having 2 to 20 carbon atoms such as a group. R ¹ is preferably a hydrogen atom or an alkynyl group, more preferably a hydrogen atom or propargyl, in terms of adhesion to other layers and difficulty in increasing the light transmittance of the separation layer (I) due to heat during processing. It is a group. When a plurality of —OR ¹ are present, they may be the same as or different from each other.

R ² is a group bonded to the condensed polycyclic aromatic ring. R ² is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ² are present, they may be the same as or different from each other.
R ³ is a hydrogen atom or an organic group. R ³ may be the same as or different from each other.

a is an integer of 1 or more. The Ar—OR ¹ moiety in the structural unit (A1) is considered to form a quinone structure with high light-shielding properties when subjected to high-temperature heat treatment, for example, when a is an integer of 2 or more. From the viewpoint of quinone structure formation, a is preferably an integer of 2 or more, more preferably an integer of 2 to 4, and further preferably 2. b is an integer of 0 or more, preferably an integer of 0 to 4, more preferably an integer of 0 to 2. For example, when Ar is a naphthalene ring, a is an integer of 1 to 6, b is an integer of 0 to 4, and 1 ≦ a + b ≦ 6.

Examples of the halogen atom for R ² include fluorine, chlorine, and iodine.
Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, C1-C20 alkyl groups such as octyl, nonyl and decyl groups; C3-C20 cycloalkyl groups such as cyclopentyl and cyclohexyl groups; C6-C18 aryls such as phenyl and naphthyl groups Groups.

Examples of the organic group for R ³ include an alkyl group, a cycloalkyl group, an aryl group, a furyl group, and a thienyl group. In R ³ , examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group. Examples of the cycloalkyl group include carbon numbers such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include an aryl group having 6 to 18 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and a pyrenyl group.

In the organic group, at least one hydrogen atom contained in the alkyl group, cycloalkyl group and aryl group is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl having 6 to 18 carbon atoms. It may be substituted with at least one group selected from a group, an alkoxy group having 1 to 20 carbon atoms, a hydroxy group, a nitro group and a halogen atom. For example, aryl group substituted alkyl group, aryl group substituted cycloalkyl group, alkyl group substituted aryl group, cycloalkyl group substituted aryl group, aryl group substituted aryl group, alkoxy group substituted aryl group, hydroxy group substituted aryl group, nitro group substituted aryl Group, and a halogen atom-substituted aryl group.

In the structural unit (A1), the “group bonded to the condensed polycyclic aromatic ring” may be bonded to any of a plurality of rings (eg, benzene nucleus). Further, (1) when the -OR ¹ there are a plurality in the same structural units (A1), -OR ¹ may be bonded to the same ring in the condensed polycyclic aromatic ring, different rings may be bonded to; (2) when R ² there are a plurality in the same structural units (A1), even if R ² is bonded to the same ring in the fused polycyclic aromatic ring It may be bonded to different rings.

—C (R ³ ) ₂ — is a divalent group bonded to a condensed polycyclic aromatic ring. -C (R ³ ) ₂ -Ar (OR ¹ ) _a (R ² ) _b -C (R ³ ) _2- , -C (R ³ ) _2- is the same ring included in the condensed polycyclic aromatic ring May be bonded to each other or may be bonded to different rings. Specifically, when Ar is a naphthalene ring, two —C (R ³ ) ₂ — may be bonded to the same benzene nucleus contained in the naphthalene ring (for example, 1 below), and different benzenes It may be bonded to the nucleus (for example, the following 2).

As the bonding site of —C (R ³ ) ₂ — in the structural unit (A1), when Ar is a naphthalene ring, for example, 1, 2 position, 1, 3 position, 1, 4 position, 1, 5 position, 1st, 6th, 1st, 7th, 1st, 8th, 2nd, 3rd, 2,4th, 2,5th, 2,6th, 2,7th, 2,8th, 3,4th, Examples include 3,5, 3,6, 3,7, 3,8, 4,5, 4,6, 4,7, 4,8.

The structural unit (A1) is preferably a structural unit represented by the formula (A2) (hereinafter also referred to as “structural unit (A2)”). In this case, the sensitivity of the separation layer (I) to light irradiation is high, and the light shielding properties of the separation layer (I) tend to be excellent.

In the formula (A2), Ar, R ¹ to R ³ and b have the same meanings as the same symbols in the formula (A1), and a1 is an integer of 2 or more, more preferably an integer of 2 to 4. More preferably, 2.

Content of a structural unit (A1) is normally 80 mass% or more in a polymer (A) 100 mass%, Preferably it is 90 mass% or more, More preferably, it is 99 mass% or more. When the content is in the above range, the separation layer (I) having high sensitivity to light irradiation and excellent light shielding properties tends to be obtained. The content can be measured by ¹³ C NMR.

The weight average molecular weight (Mw) in terms of polystyrene measured by the gel permeation chromatography (GPC) method of the polymer (A) is usually 500 to 30,000, preferably 1,000 to 15,000, The preferred range is 1,300 to 10,000. When Mw is in the above range, the layer (I) excellent in film thickness uniformity can be formed. Details of the method for measuring Mw are described in the Examples.

A polymer (A) may be used individually by 1 type, and may use 2 or more types together.
The content of the polymer (A) is usually 15% by mass or more, preferably 20 to 100% by mass, and more preferably 25 to 100% by mass in 100% by mass of the solid content contained in the temporary fixing composition. . In one embodiment, the content of the polymer (A) is, for example, 40% by mass or more, 50 to 100% by mass, or 60 to 100% by mass in 100% by mass of the solid content contained in the temporary fixing composition. . Solid content means all components other than a solvent. When the content of the polymer (A) is in the above range, it is preferable from the viewpoint of the adhesion, separation, shading, and heat resistance of the separation layer (I).

The polymer (A) in which R ¹ is a hydrogen atom is preferably a novolak resin of a condensed polycyclic aromatic compound having —OH bonded to a condensed polycyclic aromatic ring and an aldehyde compound. In the polymer (A) in which R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, —OH of the novolak resin is converted to a halide represented by R ¹ X (R ¹ is a carbon group having 1 to 20 carbon atoms). It is preferably a substituted novolak resin obtained by a substitution reaction with a hydrocarbon group, wherein X represents a halogen atom such as a chlorine atom or a bromine atom.

The novolak resin can be obtained, for example, by addition condensation of the condensed polycyclic aromatic compound and the aldehyde compound in the presence of an acidic catalyst. As the reaction conditions, the condensed polycyclic aromatic compound and the aldehyde compound are usually reacted at 40 to 200 ° C. for about 0.5 to 10 hours in a solvent.
As said condensed polycyclic aromatic compound, the compound shown to a formula (a1) is mentioned, for example.

In the formula (a1), Ar ′ is a condensed polycyclic aromatic ring corresponding to Ar in the formula (A1), —OH and R ² are groups bonded to the condensed polycyclic aromatic ring, and R ² , A and b are synonymous with the same symbols in formula (A1).

Examples of the condensed polycyclic aromatic compound include a naphthalene derivative in which Ar ′ is a naphthalene ring in the formula (a1), specifically, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2, Dihydroxynaphthalene such as 4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, 3-methyl-2,6-dihydroxynaphthalene; α- And monohydroxynaphthalene such as naphthol and β-naphthol.

A condensed polycyclic aromatic compound may be used individually by 1 type, and may use 2 or more types together.
Examples of the aldehyde compound include a compound represented by the formula (a2), a compound represented by the formula (a3), and a compound represented by the formula (a4).

In the formulas (a2) to (a4), R ³¹ and R ³² have the same meaning as R ³ in the formula (A1). In the formula (a3), n1 is an integer of 2 or more, for example, an integer of 2 to 12 In the formula (a4), n2 is an integer of 2 or more, for example, an integer of 2 to 12.

Examples of the aldehyde compound include compounds of R ³¹ = R ³² = hydrogen such as formaldehyde, paraformaldehyde, and trioxane; compounds of R ³¹ = hydrogen and R ³² = alkyl group such as acetaldehyde and propionaldehyde; benzaldehyde, naphtho aldehyde, anthracene carboxaldehyde, fluorene-carboxaldehyde, such as pyrene carboxaldehyde, compound of R ³¹ = hydrogen and R ³² = aryl group; phenylacetaldehyde, naphthyl acetaldehyde, etc. phenylpropionaldehyde, R ³¹ = hydrogen and R ³² = aryl A compound of a group-substituted alkyl group; a compound of R ³¹ = hydrogen and R ³² = an alkyl group-substituted aryl group, such as methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde; Compounds of R ³¹ = hydrogen and R ³² = cycloalkyl group-substituted aryl groups such as tilbenzaldehyde and cyclohexylbenzaldehyde; Compounds of R ³¹ = hydrogen and R ³² = aryl group-substituted aryl groups such as phenylbenzaldehyde; Methoxybenzaldehyde, methoxy Compounds of R ³¹ = hydrogen and R ³² = alkoxy group substituted aryl groups such as naphthaldehyde and dimethoxynaphthaldehyde; Compounds of R ³¹ = hydrogen and R ³² = hydroxy group substituted aryl groups such as hydroxybenzaldehyde and hydroxynaphthaldehyde; such nitrobenzaldehyde, compound of R ³¹ = hydrogen and R ³² = nitro substituted aryl group; such as chlorobenzaldehyde, R ³¹ = hydrogen and compounds of R ³² = halogen atom-substituted aryl group; furfuraldehyde, thiophene aldehyde De, and the like.

Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, camphorsulfonic acid, tosylic acid, and trifluoromethanesulfonic acid. The amount of the acidic catalyst used is usually 0.01 to 10 mol per 1 mol of the condensed polycyclic aromatic compound.

In the addition condensation, the amount of the aldehyde compound used is usually 1 mol or more per 1 mol of the condensed polycyclic aromatic compound. When the aldehyde compound is a compound represented by the formula (a3) or a compound represented by the formula (a4), the amount used is an amount in terms of a compound represented by the formula (a2).

The substituted novolak resin can be obtained by reacting the novolak resin and the halide in the presence of a basic catalyst as described in a general method (for example, JP-T-2003-533502). it can.

Examples of the halide include methyl chloride, ethyl chloride, ethyl bromide, cyclopentyl chloride, cyclopentyl bromide, phenyl chloride, phenyl bromide, propargyl chloride, and propargyl bromide.
Examples of the basic catalyst include amines, metal hydroxides, metal carbonates, and metal alkoxides.

<Other light absorbers>
The temporary fixing composition, and thus the separation layer (I), may contain other light absorbers in addition to the polymer (A). The other absorbent has, for example, one or both of the following functions (a) and (b): (a) absorbs light used in the light irradiation treatment in step (3), and separates the layer. In (I), decomposition / degeneration of constituent components is generated. (B) Absorbs measurement light (usually light having a wavelength of 600 to 900 nm) used for detecting the separation layer (I) and aligning each element when arranging and laminating each element in the laminate. .
Examples of other light absorbers include benzotriazole-based light absorbers, hydroxyphenyltriazine-based light absorbers, benzophenone-based light absorbers, salicylic acid-based light absorbers, radiation-sensitive radical polymerization initiators, and light-sensitive acids. Organic light absorbers such as generators; reaction products of phenolic compounds and aldehyde compounds; I. Pigment black 7, C.I. I. Pigment black 31, C.I. I. Pigment black 32, and C.I. I. Black pigments such as CI Pigment Black 35; I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 139, C.I. I. Pigment red 242, C.I. I. Pigment red 245, and C.I. I. Non-black pigments such as CI Pigment Red 254, C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Acid Yellow 11, C.I. I. Direct Yellow 12, C.I. I. Reactive Yellow 2, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, and C.I. I. And dyes such as Direct Red 83.

Another light absorber may be used individually by 1 type, and may use 2 or more types together.
The content of the other light absorber is not particularly limited as long as the polymer (A) absorbs and decomposes or changes the light used in the light irradiation treatment in the separation layer (I), but the polymer (A) 100 mass. Preferably it is 20 mass parts or less with respect to a part.
In one embodiment, the content of the other light absorber is usually 20 to 400 parts by mass, preferably 50 to 300 parts by mass with respect to 100 parts by mass of the polymer (A). For example, by using the other light absorbent that absorbs the measurement light in such a range, the elements in the laminate can be aligned well.

<Other ingredients>
The composition for temporary fixing is, if necessary, a tackifier resin such as petroleum resin and terpene resin, antioxidant, polymerization inhibitor, adhesion aid, surfactant, polystyrene crosslinked particles, crosslinking agent and aluminum oxide, You may contain 1 type, or 2 or more types chosen from metal oxide particles, such as a zirconium oxide, a titanium oxide, and a silicon oxide.

[Adhesive layer (II)]
The adhesive layer (II) can be formed using a known adhesive for temporarily fixing an object. When the adhesive layer (II) is a laminate having the respective layers in the order of the support, the separation layer (I), the adhesive layer (II) and the object, the object is temporarily fixed on the support, and Cover and protect the surface of the object.

Examples of the adhesive include thermoplastic resin-based, elastomer-based, and thermosetting resin-based adhesives, and two or more mixed systems selected from these may be used. The adhesive may be any of a solvent type, an emulsion type, and a hot melt type.

<Thermoplastic resin>
Examples of thermoplastic resins include cycloolefin polymers, terpene resins, petroleum resins, novolak resins, (meth) acrylic resins, polyolefins, polyvinyl chloride, ethylene-vinyl acetate copolymers, phenoxy resins, thermoplastic polyimides. Resin, and thermoplastic polybenzoxazole resin. Of these, cycloolefin polymers are preferred.

Examples of the cycloolefin polymer include an addition copolymer of a cyclic olefin compound and an acyclic olefin compound, a ring-opening metathesis polymer of one or more cyclic olefin compounds, and the ring-opening metathesis polymer. A polymer obtained by hydrogenating the polymer may be mentioned.

Examples of cyclic olefin compounds include norbornene olefins, tetracyclododecene olefins, dicyclopentadiene olefins, and derivatives thereof. Examples of the derivatives include alkyl groups, alkylidene groups, aralkyl groups, cycloalkyl groups, hydroxy groups, alkoxy groups, acetyl groups, cyano groups, amide groups, imide groups, silyl groups, aromatic rings, ether bonds, and ester bonds. The substituted derivative which has 1 type, or 2 or more types chosen from is mentioned.

Examples of the acyclic olefin compound include linear or branched olefins having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably ethylene, propylene and butene, and particularly preferably ethylene. It is.

The weight average molecular weight (Mw) in terms of polystyrene by the GPC method of the cycloolefin polymer is usually 10,000 to 100,000, preferably 30,000 to 100,000.

Examples of the terpene resin include terpene resins, hydrogenated terpene resins, terpene phenol resins, hydrogenated terpene phenol resins, aromatic modified terpene resins, and aromatic modified hydrogenated terpene resins. The weight average molecular weight (Mw) in terms of polystyrene measured by the GPC method of the terpene resin is usually 50,000 or less, preferably 500 to 10,000.

Examples of petroleum resins include C5 petroleum resins, C9 petroleum resins, C5 / C9 mixed petroleum resins, cyclopentadiene resins, polymers of vinyl-substituted aromatic compounds, and copolymers of olefins and vinyl-substituted aromatic compounds. Examples thereof include a polymer, a copolymer of a cyclopentadiene compound and a vinyl-substituted aromatic compound, a hydrogenated product thereof, and a mixture of two or more selected from these. The weight average molecular weight (Mw) in terms of polystyrene measured by the GPC method of the petroleum resin is usually 20,000 or less, preferably 100 to 20,000.

The novolac resin can be obtained, for example, by addition condensation of a phenol compound and an aldehyde compound in the presence of an acidic catalyst such as oxalic acid. Preferable specific examples of the novolak resin include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, and a phenol-naphthol / formaldehyde condensed novolak resin. The weight average molecular weight (Mw) in terms of polystyrene measured by the GPC method of the novolak resin is usually 2,000 or more, preferably 2,000 to 20,000.

A thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.
The adhesive layer (II) preferably contains a cycloolefin polymer from the viewpoint of heat resistance. The adhesive layer (II) preferably contains at least one component selected from a cycloolefin polymer, a terpene resin and a petroleum resin. Such a layer has high resistance to chemicals used in photofabrication, for example, highly polar organic solvents or aqueous chemicals. For this reason, when processing and / or moving the object, it is possible to prevent a trouble that the adhesive layer (II) deteriorates due to the chemical solution and the object moves out of the support.

<Elastomer>
Examples of the elastomer include acrylic rubber, nitrile rubber, urethane rubber, and styrene butadiene rubber. These may be used alone or in combination of two or more.

<Thermosetting resin>
Examples of thermosetting resins include epoxy resins, resol resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, urethane resins, silicone resins, (meth) acryloyl group-containing resins, thermosetting polyimide resins, A thermosetting polybenzoxazole resin is mentioned. These may be used alone or in combination of two or more.

<Other ingredients>
The adhesive is selected from antioxidants, polymerization inhibitors, adhesion assistants, surfactants, polystyrene cross-linked particles, and metal oxide particles such as aluminum oxide, zirconium oxide, titanium oxide, and silicon oxide as necessary. You may contain 1 type, or 2 or more types.

<Manufacture of temporary fixing composition and adhesive>
The temporary fixing composition and the adhesive are known devices used for processing the resin composition as necessary, for example, a twin screw extruder, a single screw extruder, a continuous kneader, a roll kneader, a pressure kneader, a Banbury mixer. Can be produced by mixing each component. In addition, for the purpose of removing impurities, filtration can be appropriately performed.

In the production of the temporary fixing composition and the adhesive, a solvent may be used in order to set these viscosities in a range suitable for coating. Examples of the solvent include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethyl Amide solvents such as propanamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide; phosphoramide solvents such as hexamethylphosphoramide; N-methyl-2 -Pyrrolidone, N-vinyl-2-pyrrolidone, N-pentyl-2-pyrrolidone, N- (methoxypropyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, etc. Pyrrolidone solvents: 2-heptanone, 3-heptanone, 4 Ketone solvents such as heptanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; alcohol / ether solvents such as anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, diglyme; ethyl acetate, butyl acetate, isobutyl acetate , Ethyl lactate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, methoxypropyl acetate, ethylene carbonate, propylene carbonate, γ-butyrolactone, and other ester / lactone solvents; xylene, limonene, mesitylene, dipentene , Pinene, bicyclohexyl, cyclododecene, 1-tert-butyl-3,5-dimethylbenzene Zen, butyl cyclohexane, cyclooctane, cycloheptane, cyclohexane, hydrocarbon solvents such as methyl cyclohexane.

A solvent may be used individually by 1 type and may use 2 or more types together.
When the composition for temporary fixing and the adhesive contain a solvent, it becomes easy to adjust the viscosity, and therefore, it becomes easy to form a temporary fixing material on the object or the support. For example, the solvent can be used in such a range that the solid content concentrations of the temporary fixing composition and the adhesive are each independently usually 5 to 70% by mass, more preferably 15 to 50% by mass. Here, the “solid content concentration” is the total concentration of all components other than the solvent.

2. The processing method of the target object of this invention (1) The process of forming the said laminated body, (2) The process of processing the said target object, and / or moving the said laminated body, ( 3) a step of irradiating the separation layer (I) with light from the support side; and (4) a step of separating the support and the object.
Hereinafter, each of the above steps is also referred to as step (1) to step (4).

<2-1. Step (1)>
In the step (1), for example, (1-1) the temporary fixing material is formed on the surface of the support and / or the object, and the object and the support are bonded to each other through the temporary fixing material. The object can be temporarily fixed on the support. Further, (1-2) forming the temporary fixing material on the surface of the support, and forming an object such as a resin coating film or a wiring layer on the temporary fixing material, whereby the object is placed on the support. It can be temporarily fixed. The object may be surface-treated as necessary.

Examples of the method for forming the temporary fixing material include (α) a method of directly forming each layer of the temporary fixing material on the support and / or the object, and (β) polyethylene subjected to a release treatment. Examples thereof include a method of forming a film with a constant film thickness on a film such as a terephthalate film using a temporary fixing composition or an adhesive, and then transferring each layer to a support and / or an object by a laminating method. From the viewpoint of film thickness uniformity, the method (α) is preferred.

Examples of the method for applying the temporary fixing composition and the adhesive that form each layer of the temporary fixing material include a spin coating method and an ink jet method. In the spin coating method, for example, the composition is formed under the conditions that the rotation speed is 300 to 3,500 rpm, preferably 500 to 1,500 rpm, the acceleration is 500 to 15,000 rpm / second, and the rotation time is 30 to 300 seconds. The method of spin-coating is mentioned.

After applying the temporary fixing composition to form a coating film, the separation layer (I) is formed by, for example, heating to evaporate the solvent. The heating conditions are appropriately determined according to the boiling point of the solvent. For example, the heating temperature is usually 100 to 350 ° C., and the heating time is usually 1 to 60 minutes.

After the adhesive is applied to form a coating film, the adhesive layer (II) is formed by, for example, heating to evaporate the solvent. As described above, the temporary fixing material may not have the adhesive layer (II). The heating conditions are appropriately determined according to the boiling point of the solvent. For example, the heating temperature is usually 100 to 300 ° C., and the heating time is usually 1 to 60 minutes.
The coating film may be heated in multiple stages as necessary.

In the above method (α), as a method for bonding the object and the support, in the case of a laminate having the respective elements in the order of the support, the separation layer (I), the adhesive layer (II) and the object The following methods can be mentioned. For example, a method 1 in which the layer (II) is formed on the surface of the object, the layer (I) is formed on the surface of the support, and the layers (I) and (II) are bonded to each other; Method 2 in which layer (II) and layer (I) are sequentially formed on the surface, and a support is bonded to layer (I); layer (I) and layer (II) are sequentially formed on the support surface, (II) The method 3 which bonds a target object on is mentioned. The temperature at this time is appropriately selected according to the temporary fixing composition, the components contained in the adhesive, the coating method, and the like. Among these, the method 1 is preferable from the viewpoint of avoiding mixing of the layers (I) and (II) during the formation of each layer.

The pressure-bonding condition between the object and the support is, for example, preferably from room temperature to 400 ° C., more preferably from 150 to 400 ° C. for 1 to 20 minutes, and a pressure of 0.01 to 100 MPa is applied in the stacking direction of each layer. It may be performed by. After the pressure bonding, heat treatment may be further performed at 150 to 300 ° C. for 10 minutes to 3 hours. In this way, the object is firmly held on the support via the temporary fixing material.

In the separation layer (I), the content of the polymer (A) is usually 15% by mass or more, preferably 20 to 100% by mass, more preferably 25 to 100% by mass. In one embodiment, the content of the polymer (A) in the separation layer (I) is, for example, 40% by mass or more, 50-100% by mass, or 60-100% by mass. When the content of the polymer (A) is in the above range, it is preferable from the viewpoint of the adhesion, separation, shading, and heat resistance of the separation layer (I).

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. The semiconductor wafer and the semiconductor chip may be formed with at least one selected from bumps, wirings, through holes, through hole vias, insulating films, and various elements. Various elements may 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.

As the support, a substrate transparent to the light used in the light irradiation is preferable because the separation layer (I) is altered by light irradiation from the support side in the step (3). For example, a glass substrate, a quartz substrate And a transparent resin substrate.

Hereinafter, a processing object having at least a wiring layer will be described. In this process, a temporarily fixing material is formed on a support, and an object to be processed having at least a wiring layer is first formed on the temporarily fixing material, for example, as a layer independent of a semiconductor wafer or chip, and will be described later. In step (2), a semiconductor wafer or a semiconductor chip in which a plurality of semiconductor elements are formed on a wafer substrate is disposed on the wiring layer. The wiring layer functions as a rewiring layer of the semiconductor wafer or chip by being electrically connected to the semiconductor wafer or chip. The present invention can also be applied to an RDL (Redistribution Layer) -First structure in such FO-WLP (Fan-Out Wafer Level Package) technology.

The wiring layer has, for example, an insulating portion, a wiring portion, and a connecting conductor portion that can be connected to an electrode of a semiconductor wafer or a chip. A semiconductor wafer or chip is disposed on the wiring layer, and the connecting conductor portion of the wiring layer and the electrode of the semiconductor wafer or chip are electrically connected by a joining member such as solder, anisotropic conductive paste, anisotropic conductive film, etc. Connect to. When a gap is generated between the semiconductor wafer or chip and the wiring layer, an underfill material may be filled.

The internal structure in the wiring layer is not particularly limited. Examples of the material for the wiring part and the connecting conductor part include copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, ruthenium, and two or more of these. The alloy which becomes is mentioned. Examples of the material for the insulating portion include known synthetic resins such as polyimide resin, acrylic resin, polyether nitrile resin, polyether sulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. . The thickness of the wiring layer is usually 1 to 1,000 μm.

Subsequently, for example, the semiconductor wafer or chip is resin-sealed in the step (2), and the temporary fixing material and the wiring layer are separated in the step (4), whereby the semiconductor wafer or chip and the wiring layer (that is, the rewiring layer). ) Can be obtained.

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. As said surface treating agent, coupling agents, such as a silane coupling agent, are mentioned, for example.

Note that the placement of the object on the temporary fixing material, or the placement of the semiconductor wafer or chip on the wiring layer in the wiring layer forming process described above is based on the positional information of each element obtained using the measurement light. It may be performed after performing.

Measured light is preferably light having a wavelength of 600 to 900 nm from the viewpoint of suppressing deterioration of the object to be processed, and the measured light particularly preferably includes light having a wavelength of 633 nm, 670 nm, or 830 nm. As the measurement light source, for example, a visible semiconductor laser or a light emitting diode is preferably used.

Alignment is performed as follows, for example. As the separation layer (I), a layer containing another light absorbent that absorbs measurement light is used. Here, when the measurement light is irradiated and the separation layer (I) absorbs the measurement light, a decrease in intensity of the measurement light is observed, and position information of the separation layer (I) is obtained from the decrease in intensity. The installation position of the optical sensor used for measurement light irradiation / observation is not particularly limited. From the obtained position information, the temporary fixing material and the object are aligned, or the wiring layer and the semiconductor wafer or chip are aligned.

Examples of the light source of the light emitting unit include a visible semiconductor laser and a light emitting diode, and examples of the light receiving unit include a photosensor such as a photodiode and a phototransistor; and an image sensor such as a CCD image sensor and a CMOS image sensor. . Examples of the means for moving each component include a robot arm.

<2-2. Step (2)>
Step (2) is a step of processing the object temporarily fixed on the support and / or moving the obtained laminate. 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 thinning of the object such as dicing and back grinding, photofabrication, stacking of semiconductor chips, mounting of various elements, and resin sealing. . 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. The etching process and the formation of the sputtered film are performed, for example, in a temperature range of about 25 to 300 ° C., and the plating process and the plating reflow process are performed, for example, in a temperature range of about 225 to 300 ° C. The processing of the object is not particularly limited as long as it is performed at a temperature at which the holding force of the temporarily fixed material is not lost.

For example, in the RDL-First described above, a processing object having at least a wiring layer is formed on the temporary fixing material in the step (1), and a semiconductor wafer and a semiconductor chip are selected on the wiring layer in the step (2). At least one kind is arranged, and then the wiring layer and the semiconductor wafer or chip are electrically connected. Subsequently, resin sealing of the semiconductor wafer or chip is performed as necessary.

<2-3. Step (3)>
After the processing of the object or the movement of the laminate, the separation layer (I) of the temporary fixing material is irradiated with light from the support side. By light irradiation, the polymer (A) which is a component contained in the separation layer (I) absorbs light, and the strength and adhesive strength of the separation layer (I) are reduced. Therefore, if it is after the light irradiation with respect to separation layer (I), a support body and a target object can be easily isolate | separated, especially without requiring the heat processing of a temporary fixing 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 300 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.

Of these, laser is preferable. It is preferable to irradiate the entire surface of the separation layer (I) while scanning with a laser from the support side, and it is more preferable to irradiate the laser onto the separation layer (I) with a focus. The scanning method is not particularly limited. For example, in the XY plane of the separation layer (I), a laser is linearly irradiated in the X-axis direction, and the irradiation unit is sequentially moved in the Y-axis direction to irradiate the entire surface. And a method of irradiating the entire surface by irradiating the laser angularly and moving the irradiation part sequentially from the central part to the outer periphery or from the peripheral part to the inner part.

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, an all-solid-state laser (wavelength: 355 nm), YAG laser (wavelength: 355 nm), and excimer laser using a photoexcited semiconductor laser are preferable.

Examples of the excimer laser include F ₂ excimer laser (wavelength: 157 nm), ArF excimer laser (193 nm), KrF excimer laser (248 nm), XeCl excimer laser (308 nm), and XeF excimer laser (351 nm). It is done.
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 .

<2-4. Step (4)>
In the step (4), by applying force to the object or the support, the object is separated from the support, for example, to separate them. Note that the separation in the step (4) is preferably performed after the light irradiation in the step (3), but the separation in the step (4) may be performed while performing the light irradiation in the step (3).

As a separation method, for example, a method of applying force to the object or the support in a direction parallel to the object surface to separate them; fixing one of the object or the support and the other to the object surface On the other hand, there is a method of separating the two by lifting at a certain angle from the parallel direction.

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 apply a force in a direction substantially perpendicular to the object surface to separate the support and the object. “Applying a force in a direction substantially perpendicular to the object surface” means usually in the range of 0 ° to 60 °, preferably 0 ° with respect to the z-axis that is an axis perpendicular to the object surface. Applying a force in the range of ~ 45 °, more preferably in the range of 0 ° to 30 °, even more preferably in the range of 0 ° to 5 °, particularly preferably 0 °, ie perpendicular to the object plane. Means. As a separation method, for example, a method (hook pull method) in which the periphery of the object or the support is lifted and peeled in order from the periphery toward the center while applying a force in a direction substantially perpendicular to the object surface. Can do.

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

In the present invention, as described above, the temporary fixing material has the separation layer (I), and separation of the object and the support mainly occurs in the separation layer (I). When the object has bumps, the bumps can be prevented from being damaged during the separation process.

In addition, after separating the support and the object, the temporary fixing material may remain on the object. The temporarily fixed material remaining on the object after the separation step can be removed by a peeling treatment, and can be removed by washing with a solvent.

For the peeling of the temporary fixing material, it is preferable to use an adhesive tape that can form an adhesive force between the object and the temporary fixing material higher than that of the temporary fixing material. The temporary fixing material can be removed by laminating the adhesive tape on the temporary fixing material and peeling the adhesive tape together with the temporary fixing material.

Examples of the cleaning method include a method of immersing the object in a solvent, a method of spraying the solvent on the object, and a method of applying ultrasonic waves while immersing the object in the solvent. The temperature of the solvent is not particularly limited, but is preferably 20 to 80 ° C, more preferably 20 to 50 ° C. Examples of the solvent that can be used for cleaning include the solvents described in the columns of the temporary fixing composition and the adhesive production.
As described above, the support and the object can be separated. Further processing may be performed on the separated object. For example, in the above-described RDL-First, bump formation on a wiring layer, cutting out into individual packages by dicing, or the like may be performed.

3. Semiconductor device and manufacturing method thereof The semiconductor device of the present invention can be manufactured by processing the target object by the processing method of the target object of the present invention. The temporary fixing material can be easily removed by peeling treatment or solvent treatment after separating a semiconductor device (eg, semiconductor element) obtained by processing an object from a support. For this reason, in the semiconductor device of the present invention, deterioration due to light irradiation at the time of separation is small, and contamination such as spots and scorching due to the temporary fixing material is reduced.

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” is used to mean “part by mass” unless otherwise specified.

The average molecular weight (Mw, Mn) of the polymer and the resin was measured using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, and in terms of polystyrene, the measuring device “HLC-8220- It is measured using “GPC” (manufactured by Tosoh Corporation).

1. Production of temporary fixing composition and adhesive [Synthesis Example 1] Polymer (A1) synthesis reactor, reactor equipped with a thermometer and a stirrer, 100 parts of 2,6-dihydroxynaphthalene, propylene glycol monomethyl ether acetate 100 parts and 50 parts of paraformaldehyde (in terms of formaldehyde) were charged, 2 parts of oxalic acid was added, and the mixture was heated at 120 ° C. for 5 hours while dehydrating.

Water was added to the reaction solution and stirred. The precipitate was collected, washed with water, and dried at 50 ° C. for 17 hours to obtain 2,6-dihydroxynaphthalene / formaldehyde condensate (polymer (A1)). Mw of the polymer (A1) was 1,550.

[Synthesis Example 2] 10 parts of the polymer (A1), 13 parts of propargyl bromide, 10 parts of triethylamine, and 40 parts of tetrahydrofuran are charged into a separable flask equipped with a synthesis thermometer for the polymer (A2) and stirred. The reaction was carried out at 50 ° C. for 12 hours. After completion of the reaction, the reaction solution was cooled to 30 ° C. or lower by water cooling. After cooling, the reaction solution was poured into a large amount of n-heptane. Thereafter, the precipitated solid was separated by a decantation method and washed with a large amount of n-heptane. Subsequently, the solid was dissolved in methyl isobutyl ketone and washed with 1% by mass of oxalic acid and pure water to remove the remaining triethylamine. Thereafter, the organic layer was dried at 50 ° C. for 17 hours to obtain a polymer (A2). Mw of the polymer (A2) was 5,300, and the introduction rate of the propargyl group was 95 mol% when the hydroxyl group of the polymer (A1) was 100 mol% as measured by ¹³ C NMR.

[Examples 1A to 9A, Comparative Examples 1A to 4A]
Production of Temporary Fixing Compositions (I-1) to (I-13) The components shown in Table 1 were mixed in the blending amounts shown in Table 1, and the temporary fixing compositions (I-1) to (I-13) were mixed. ) Was manufactured. Details of each component in Table 1 are as described later.

Polymer A1: the polymer (A1)
A2: the polymer (A2)
A3: Cresol novolak resin (Mw = 6,500) comprising m-cresol / p-cresol = 60/40 (molar ratio)
A4: Polyamic acid (trade name “UPIA-AT”, manufactured by Ube Industries, Ltd.)
A5: cycloolefin polymer (trade name “ARTON RX4500”, manufactured by JSR Corporation)
Light absorber B1: 4,4'-bis (diethylamino) benzophenone B2: 2- [2-hydroxy-3- (4,5,6,7-tetrahydro-1,3-dioxo-1H-isoindole-2- Ylmethyl) -5-methylphenyl] -2H-benzotriazole B3: Solvent Blue 70
B4: Blue pigment dispersion (methoxypropyl acetate dispersion containing pigment number B15: 6 at a pigment concentration of 55% by mass)
B5: Green pigment dispersion (methoxypropyl acetate dispersion containing pigment number G58 at a pigment concentration of 55% by mass)
Solvent C1: Cyclohexanone C2: Methoxypropyl acetate C3: N-methyl-2-pyrrolidone C4: Mesitylene and others D1: Fluorosurfactant ("Futgent FTX-218", manufactured by Neos Co., Ltd.)
D2: Crosslinking agent (4- (1- {4- [1,1-bis (4-hydroxyphenyl) ethyl] phenyl} -1-methylethyl) phenol and formaldehyde reaction product)

[Production Example 1] Production of adhesive (II-1) 80 parts of cycloolefin polymer (trade name “ARTON RX4500”, manufactured by JSR Corporation) and 20 parts of hydrogenated terpene resin (trade name “CLEARON”) P150 ", manufactured by Yasuhara Chemical Co., Ltd.), 20 parts of liquid styrene butadiene rubber (trade name" L-SBR-820 ", manufactured by Kuraray Co., Ltd.), and 3 parts of hindered phenolic antioxidant (trade name) “IRGANOX1010” (manufactured by BASF) and 367 parts of mesitylene were mixed to produce an adhesive (II-1).

2. Measurement of transmittance A 6-inch glass wafer was spin-coated with the temporary fixing composition (I-1). Thereafter, in Example 1A, the sample was heated at 180 ° C. for 1 minute using a hot plate and then further heated at 300 ° C. for 2 minutes. The mixture was heated for 5 minutes to obtain a uniform layer (I-1) having a thickness of 0.5 μm. Also in other examples and comparative examples, a uniform layer (thickness of 0.5 μm) was formed by spin coating the temporary fixing compositions (I-2) to (I-13) and heating under a two-step heating condition. I-2) to (I-13) were obtained. Table 2 shows the two-step heating conditions. For the obtained layers (I-1) to (I-13), transmittance (initial transmittance) at a wavelength of 355 nm and a wavelength of 670 nm was measured using an ultraviolet-visible-near infrared spectrophotometer (JASCO, V-7000). It was measured.

The glass wafer having the layers (I-1) to (I-13) was heated in an oven at 300 ° C. for 10 minutes under a nitrogen stream. For the heated layers (I-1) to (I-13), transmittance at a wavelength of 355 nm and a wavelength of 670 nm using a UV-visible near-infrared spectrophotometer (JASCO, V-7000) (transmittance after heating) Was measured. The results are shown in Table 2.

3. Production of laminated body and evaluation thereof [Examples 1B to 9B]
A 4-inch glass wafer (substrate 1) was spin-coated with the temporary fixing compositions (I-1) to (I-9), and then heated under the film formation conditions shown in Table 3 using a hot plate, A substrate 1 having uniform separation layers (I-1) to (I-9) having a thickness of 10 μm was obtained. Also, a 4 inch silicon wafer (substrate 2) was spin-coated with adhesive (II-1), then heated at 160 ° C. for 5 minutes using a hot plate, and further heated at 230 ° C. for 10 minutes to obtain a thickness. A substrate 2 having a uniform adhesive layer (II-1) of 3 μm was produced.

After the substrate 1 and the substrate 2 were cut into a length of 1 cm and a width of 1 cm, respectively, the substrates were bonded so that the separation layer (I) and the adhesive layer (II) were in contact with each other, and a die bonder device was used and the pressure was 15 MPa Pressure was applied for 5 minutes, and the laminated body by which the board | substrate 1 and the board | substrate 2 were laminated | stacked through the temporary fixing material was obtained.

To the obtained test laminate, an output of 100 mW and an integrated light amount of 2.08 × 10 ⁻⁴ mJ / all solid high power laser device (trade name “Genesis CX355 STM Compact”, manufactured by Coherent Japan Co., Ltd.) A UV laser (wavelength 355 nm) was irradiated from the substrate 1 side at cm ² . Using a universal bond tester (trade name “Daily 4000”, manufactured by Daisy) for the test laminate after irradiation with light, in the direction of the axis (z axis) perpendicular to the surface of the substrate 1 by the hook-pull method. A force (speed of 500 μm / second, 23 ° C.) was applied, and peeling was performed at the interface between the layer (I) and the layer (II). The case where the peel strength at the time of peeling was 40 N / m ² or less was considered to be satisfactorily peeled. The evaluation results are shown in Table 3.

DESCRIPTION OF SYMBOLS 1 ... Laminated body 10 ... Support body 20 ... Temporary fixing material 21 ... Adhesive layer (II)
22... Separation layer (I)
30 ... Object

Claims (16)

1. (1) The process of forming the laminated body which has a support body, a temporary fixing material, and a process target object, Here, the said temporary fixing material contains the polymer (A) which has a structural unit shown to following formula (A1). Has a layer (I), and the object is held on the temporary fixing material;
   (2) processing the object and / or moving the laminate;
   (3) a step of irradiating the layer (I) with light from the support side; and (4) a step of separating the support and the object;
   A method for processing an object.
   

   

   [In the formula (A1),
   Ar is a fused polycyclic aromatic ring;
   —OR ¹ is a group bonded to the condensed polycyclic aromatic ring, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of —OR ¹ are present, they may be the same as each other May be different;
   R ² is a group bonded to the condensed polycyclic aromatic ring, and is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ² are present, they may be the same or different from each other. ;
   R ³ is a hydrogen atom or an organic group, and R ³ may be the same or different from each other;
   a is an integer of 1 or more, and b is an integer of 0 or more. ]
2. The method for processing an object according to claim 1, wherein the temporary fixing material further has an adhesive layer (II).
3. The method for processing an object according to claim 2, wherein the laminate includes the respective elements in the order of the support, the layer (I), the adhesive layer (II), and the processing object.
4. The method for processing an object according to any one of claims 1 to 3, wherein in the step (1), a processing object having at least a wiring layer is formed on the temporarily fixing material.
5. The processing method of the object according to claim 4, wherein the processing in the step (2) includes disposing at least one selected from a semiconductor wafer and a semiconductor chip on the wiring layer.
6. The method for processing an object according to any one of claims 1 to 5, wherein the light in the step (3) is ultraviolet light.
7. The method for treating an object according to claim 6, wherein the ultraviolet rays are ultraviolet rays having a wavelength of 300 to 400 nm.
8. The method for processing an object according to any one of claims 1 to 7, wherein the layer (I) has a thickness of 0.1 to 500 µm.
9. The method for treating an object according to any one of claims 1 to 8, wherein the condensed polycyclic aromatic ring in the formula (A1) is a naphthalene ring.
10. The method for treating an object according to any one of claims 1 to 9, wherein R ¹ in the formula (A1) is a hydrogen atom or an alkynyl group.
11. The composition for temporary fixing containing the polymer (A) which has a structural unit shown to following formula (A2).
    

    

    [In the formula (A2),
    Ar is a fused polycyclic aromatic ring;
    —OR ¹ is a group bonded to the condensed polycyclic aromatic ring, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of —OR ¹ are present, they may be the same as each other May be different;
    R ² is a group bonded to the condensed polycyclic aromatic ring, and is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ² are present, they may be the same or different from each other. ;
    R ³ is a hydrogen atom or an organic group, and R ³ may be the same or different from each other;
    a1 is an integer of 2 or more, and b is an integer of 0 or more. ]
12. Furthermore, the composition for temporary fixing of Claim 11 containing a solvent.
13. The composition for temporary fixing according to claim 11 or 12, wherein a content ratio of the polymer (A) contained in 100% by mass of the solid content of the temporary fixing composition is 50% by mass or more.
14. A method for manufacturing a semiconductor device, wherein a semiconductor device is manufactured by processing an object by the processing method according to any one of claims 1 to 10.
15. (1) A step of forming a laminate having a support, a temporary fixing material, and a wiring layer, wherein the temporary fixing material is a layer containing a polymer (A) having a structural unit represented by the following formula (A1) (I) and the wiring layer is formed on the temporary fixing material;
    (2) Arranging at least one selected from a semiconductor wafer and a semiconductor chip on the wiring layer;
    (3) a step of irradiating the layer (I) with light from the support side; and (4) a step of separating the support and the wiring layer;
    A method for manufacturing a semiconductor device, comprising:
    

    

    [In the formula (A1),
    Ar is a fused polycyclic aromatic ring;
    —OR ¹ is a group bonded to the condensed polycyclic aromatic ring, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of —OR ¹ are present, they may be the same as each other May be different;
    R ² is a group bonded to the condensed polycyclic aromatic ring, and is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ² are present, they may be the same or different from each other. ;
    R ³ is a hydrogen atom or an organic group, and R ³ may be the same or different from each other;
    a is an integer of 1 or more, and b is an integer of 0 or more. ]
16. A semiconductor device obtained by the manufacturing method according to claim 14 or 15.

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