CN107851551B - Substrate processing method and semiconductor device - Google Patents
Substrate processing method and semiconductor device Download PDFInfo
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- CN107851551B CN107851551B CN201680041470.XA CN201680041470A CN107851551B CN 107851551 B CN107851551 B CN 107851551B CN 201680041470 A CN201680041470 A CN 201680041470A CN 107851551 B CN107851551 B CN 107851551B
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- temporary fixing
- substrate
- layer
- support
- fixing material
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- 238000003672 processing method Methods 0.000 title description 3
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- 239000000203 mixture Substances 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 65
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- 238000012545 processing Methods 0.000 claims abstract description 21
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
- H01L21/7806—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices involving the separation of the active layers from a substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a method for treating a substrate, a composition for temporary fixation, and a semiconductor device. The method for treating a substrate of the present invention comprises, in order: a step of forming a laminate having a support, a temporary fixing material, and a base material, wherein the temporary fixing material is a temporary fixing material having a temporary fixing material layer (I) which is in contact with a support-side surface of the base material and is formed of a composition containing at least one polymer selected from a polybenzoxazole precursor and a polybenzoxazole, and a temporary fixing material layer (II) which is formed on the support-side surface of the layer (I) and contains a light absorbing agent; a step of processing the base material and/or moving the laminate; a step of irradiating the layer (II) with light; a step of separating the substrate from the support; and a step of removing the layer (I) from the substrate.
Description
Technical Field
The invention relates to a method for treating a substrate, a composition for temporary fixation, and a semiconductor device.
Background
Proposed are: a method of performing steps such as back grinding and photolithography (photolithography) on a base material such as a semiconductor wafer while the base material is bonded to a support such as a glass substrate via a temporary fixing member. The temporary fixing material is required to be: the substrate can be temporarily fixed to the support during the processing, and the substrate can be easily separated from the support after the processing.
Proposed are: in the separation treatment, the temporary fixing material in the laminate including the support, the temporary fixing material and the substrate is irradiated with radiant energy such as ultraviolet light and infrared light to reduce the adhesion force of the temporary fixing material and separate the substrate from the support.
For example, patent document 1 discloses a laminate in which a transparent support and a semiconductor wafer are temporarily fixed to each other by a temporary fixing member including a peeling layer and an adhesive layer, and proposes a method of peeling a substrate from the support by irradiating the peeling layer with a laser beam while scanning the peeling layer from the transparent support side, thereby reducing the adhesive force of the peeling layer.
Documents of the prior art
Patent document
Patent document 1: U.S. patent publication No. 2014/0106473
Disclosure of Invention
Problems to be solved by the invention
In the conventional method of peeling a substrate from a support, since the peeling layer is irradiated with a laser beam from the transparent support side, heat locally reaching about 1000 ℃ may be generated in the peeling layer by the laser beam irradiation. The generated heat is also conducted to the adhesive layer, thereby causing deterioration of the adhesive layer. The deterioration of the adhesive layer causes the following problems: the adhesive layer on the peeled substrate cannot be easily removed by a peeling treatment or a cleaning treatment using a solvent.
The present invention has an object to provide a method for processing and moving a substrate in a state where the substrate is temporarily fixed to a support via a temporary fixing member, in which an adhesive layer remaining on the substrate after the substrate is separated from the support can be easily removed by, for example, peeling and/or solvent cleaning.
Means for solving the problems
The present inventors have made diligent studies in order to solve the problems. As a result, the present inventors have found that the above problems can be solved by a method for treating a substrate having the following constitution, and have completed the present invention.
That is, the present invention relates to, for example, the following [1] to [8 ].
[1] A method of treating a substrate comprising, in order: (1) a step of forming a laminate having a support, a temporary fixing material, and a base material, wherein the temporary fixing material has a temporary fixing material layer (I) which is in contact with a support-side surface of the base material and is formed from a composition containing at least one polymer selected from a polybenzoxazole precursor and a polybenzoxazole, and a temporary fixing material layer (II) which is formed on the support-side surface of the temporary fixing material layer (I) and contains a light absorbing agent; (2) a step of processing the base material and/or moving the laminate; (3) irradiating the temporary fixing material layer (II) with light; (4) a step of separating the substrate from the support; and (5) a step of removing the temporary securing material layer (I) from the base material.
[2] The method for treating a substrate according to [1], wherein the composition contains a polybenzoxazole precursor.
[3] The method for treating a substrate according to [1] or [2], wherein the temporary holding material layer (II) further contains a thermally decomposable resin.
[4] The method for treating a base material according to any one of [1] to [3], wherein in the step (3), the light irradiated to the temporary fixing material layer (II) is ultraviolet light.
[5] The method for treating a substrate according to [4], wherein the ultraviolet ray has a wavelength of 300nm to 400 nm.
[6] The method of treating a substrate according to any one of [1] to [5], wherein in the step (5), the temporary fixing material layer (I) is removed from the substrate by a treatment of peeling the temporary fixing material layer (I) from the substrate and/or a treatment of washing the temporary fixing material layer (I) with a solvent.
[7] A semiconductor device obtained by the method for treating a substrate according to any one of [1] to [6 ].
[8] A composition for temporary fixation, which contains at least one polymer selected from the group consisting of polybenzoxazole precursors and polybenzoxazoles.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a method for processing and moving a base material in a state where the base material is temporarily fixed to a support via a temporary fixing member, wherein an adhesive layer remaining on the base material after the base material is separated from the support can be easily removed by, for example, peeling and/or solvent cleaning.
Drawings
Fig. 1 is a sectional view of an embodiment of a laminate in the present invention.
Description of the symbols
1: laminated body
10: support body
20: temporary fixing material
21: temporary holding material layer (I)
22: temporary fixing material layer (II)
30: base material
Detailed Description
Hereinafter, a laminate formed in the present invention and a temporary fixing composition which is a raw material composition constituting a temporary fixing material of the laminate will be described, and then a method for treating a substrate and a semiconductor device obtained by the method for treating a substrate will be described.
In the present invention, the temporary fixing material is used for temporarily fixing the base material to the support so that the base material does not move away from the support when the base material is processed and/or moved.
1. Laminated body
In the laminate formed in the present invention, the base material to be processed or moved is temporarily fixed to the support via the temporary fixing member. In one embodiment, the temporary fixing member is sandwiched between the base member and the support member.
The temporary fixing material has a temporary fixing material layer (I) that is in contact with the support-side surface of the base material, and a temporary fixing material layer (II) that is formed on the support-side surface of the layer (I). The layer (I) is formed from a temporary fixing composition containing at least one polymer selected from polybenzoxazole precursors and polybenzoxazoles. The layer (II) contains a light absorbing agent, and preferably further contains a thermally decomposable resin.
In the case of using a temporary fixing composition containing a polybenzoxazole precursor, it is considered that the polybenzoxazole precursor is changed into polybenzoxazole having excellent heat resistance by heating the temporary fixing material layer (I) in contact with the substrate at the time of forming the layer (I), the time of forming a laminate or the time of processing the substrate. Therefore, deterioration of the temporary fixing material layer (I) due to heat locally generated by light irradiation to the temporary fixing material layer (II) can be suppressed. Therefore, it is estimated that the layer (I) remaining on the substrate after the separation treatment of the substrate can be removed by a simple method such as peeling or solvent cleaning.
In the present invention, the temporary fixing material has a layer (I) and a layer (II) formed in direct contact with the layer (I) or with another layer interposed therebetween. Thus, the temporary fixing material having two or more layers can protect the circuit surface of the substrate, the adhesion between the substrate and the support, the separability of the substrate from the support, and the heat resistance during processing and light irradiation treatment in a well-balanced manner.
An example of the laminate is shown in fig. 1. The laminate 1 includes a support 10, a temporary fixing member 20 formed on the support 10, and a base 30 temporarily fixed to the support 10 by the temporary fixing member 20. The temporary fixing material 20 includes a temporary fixing material layer (I)21 that is in contact with the base material 30, and a temporary fixing material layer (II)22 that is formed on the temporary fixing material layer (I)21 and is in contact with the support 10.
In the laminate, the temporary fixing material may have any other layer in addition to the layer (I) and the layer (II). For example, an intermediate layer may be provided between the layer (I) and the layer (II), and another layer may be provided between the layer (II) and the support. Particularly preferred is a temporary fixing material composed of two layers of the layer (I) and the layer (II).
The total thickness of the temporary fixing material can be arbitrarily selected depending on the size of the temporary fixing surface of the substrate, the heat resistance required for the processing treatment and the light irradiation treatment, and the degree of adhesion between the substrate and the support. The total thickness of the temporary fixing material is usually 0.2 μm or more and 1mm or less, preferably 2 μm or more and 0.5mm or less, and more preferably 2 μm or more and 0.3mm or less. The thickness of each of the layers (I) and (II) is usually 0.1 to 500. mu.m, preferably 1 to 250. mu.m, and more preferably 1 to 150. mu.m. If the thickness of the temporary fixing member is within the above range, the temporary fixing member has a sufficient holding force to temporarily fix the base material, and the base material does not fall off from the temporary fixing surface during the processing or the transfer processing.
The temporary fixing material can be suitably used as a temporary fixing material for a base material in various processing treatments required in the context of modern economic activities, for example, in microfabrication treatment of surfaces of various materials, various surface mounting, transportation of semiconductor wafers or semiconductor devices, and the like.
[ temporary holding Material layer (I) ]
The temporary fixing material layer (I) may be formed of a temporary fixing composition (I) containing at least one polymer selected from a polybenzoxazole precursor and polybenzoxazole. The temporary fixing composition (I) may contain a solvent.
The composition (I) for temporary fixation is preferably a composition containing a polybenzoxazole precursor in order to form a temporary fixing material layer (I) that is uniform in plane.
From the viewpoint of heat resistance of the layer (I), the 5% weight reduction temperature of the temporary fixing material layer (I) is preferably 350 ℃ or more, and more preferably 400 ℃ or more. The 5% weight loss temperature of the layer (I) can be measured by Thermogravimetric Analysis (TGA) under nitrogen atmosphere at a temperature rise rate of 10 ℃/min.
< polybenzoxazole precursor and polybenzoxazole >
When heat is applied, the polybenzoxazole precursor reacts in a molecule and rapidly changes to polybenzoxazole having heat resistance. Therefore, it is considered that when the layer having the polybenzoxazole precursor is heated to a high temperature, the polybenzoxazole precursor is changed into polybenzoxazole, and thus heat resistance is improved.
Examples of the polybenzoxazole precursor include polymers having a structural unit represented by formula (1). The polybenzoxazole precursor may be a polymer having one kind of structural unit, or a polymer having two or more kinds of structural units.
[ solution 1]
In the formula (1), X is a direct bond or a divalent organic group, Y is a tetravalent aromatic group, N and OH bonded to Y are paired, and each pair of N and OH is bonded to adjacent carbon atoms on the same aromatic ring.
Examples of the divalent organic group in X include: optionally halogenated arylene having 6 to 20 carbon atoms, formula (g 1): -Ar1-R1-Ar1A divalent group represented by the formula (I), an alkanediyl group having 1 to 10 carbon atoms, a cycloalkanediyl group having 3 to 20 carbon atoms, and a divalent silicon-containing group.
In the formula (g1), Ar1Each independently a C6-20 arylene group which may be halogenated, R1Is a direct bond or a divalent radical. Examples of divalent groups include: oxygen atom, sulfur atom, sulfonyl group, carbonyl group, optionally halogenated alkanediyl having 1 to 10 carbon atoms.
Examples of the arylene group having 6 to 20 carbon atoms which may be halogenated include: phenylene, methylphenylene, tert-butylphenylene, fluorophenylene, chlorophenylene, bromophenylene, naphthylene. Examples of the alkanediyl group having 1 to 10 carbon atoms include: methylene, ethane-1, 2-diyl. Examples of the C1-10 alkanediyl group which may be halogenated include: methylene, dimethylmethylene, bis (trifluoromethyl) methylene. Examples of the cycloalkanediyl group having 3 to 20 carbon atoms include: cyclobutyldiyl, cyclopentyldiyl, cycloadipyl. Examples of the divalent silicon-containing group include tetraphenylsilane-4, 4' -diyl group.
Examples of the tetravalent aromatic group in Y include: tetravalent derived from aromatic hydrocarbons such as benzene, naphthalene, anthracene ringsGroup, formula (g 2): ar > Ar2-R2-Ar2< tetravalent radical indicated.
In the formula (g2), Ar2Each independently is a trivalent radical derived from an aromatic hydrocarbon such as a benzene ring, a naphthalene ring, an anthracene ring, or the like, R2Is a direct bond or a divalent radical. Examples of divalent groups include: oxygen atom, sulfur atom, sulfonyl group, carbonyl group, optionally halogenated alkanediyl having 1 to 10 carbon atoms.
As formation of Y or Ar2Examples of the aromatic hydrocarbon of (b) include: aromatic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene, and anthracene. Examples of the C1-10 alkanediyl group which may be halogenated include: methylene, dimethylmethylene, bis (trifluoromethyl) methylene.
The polybenzoxazole precursor can be obtained, for example, by using one or both of a dicarboxylic acid and a derivative thereof and a dihydroxydiamine as raw materials.
Examples of the dicarboxylic acid include: aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 2-bis (4-carboxyphenyl) hexafluoropropane, 4 ' -biphenyldicarboxylic acid, 4 ' -dicarboxydiphenyl ether, 4 ' -dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2-bis (p-carboxyphenyl) propane, 5-t-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, and 2, 6-naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as 1, 2-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, and succinic acid. One kind of the dicarboxylic acid may be used alone, or two or more kinds thereof may be used in combination. Among these, aromatic dicarboxylic acids are preferable in terms of obtaining a polybenzoxazole precursor having good heat resistance.
Examples of the derivatives of the dicarboxylic acid include: dicarboxylic acid halides, and active esters of dicarboxylic acids and hydroxybenzotriazoles. The dicarboxylic acid derivatives may be used singly or in combination of two or more.
Examples of the dihydroxydiamine include: 3, 3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, aromatic diamines such as bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 4, 6-diaminoresorcinol and 4, 5-diaminoresorcinol. The dihydroxydiamine may be used singly or in combination of two or more. By using an aromatic diamine, a polybenzoxazole precursor having good heat resistance can be obtained.
In the polybenzoxazole precursor, the content of the structural unit represented by formula (1) is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. The content can be determined, for example, by Nuclear Magnetic Resonance hydrogen spectroscopy (Proton Nuclear Magnetic Resonance reaction,1h NMR) was performed.
The polybenzoxazole can be obtained by subjecting a polybenzoxazole precursor to a ring-closing reaction by heating, for example, a polymer in which at least a part of the structural unit represented by formula (1) is converted into the structural unit represented by formula (2) in the precursor. The polybenzoxazole precursor may be a polymer having one kind of structural unit, or a polymer having two or more kinds of structural units.
[ solution 2]
In the formula (2), X and Y are the same as those in the formula (1). The N and O bound to Y are paired and each pair of N and O is bound to an adjacent carbon atom on the same aromatic ring to form a benzoxazole ring.
The polystyrene-equivalent weight average molecular weight (Mw) of the polybenzoxazole precursor and polybenzoxazole by Gel Permeation Chromatography (GPC) is preferably 1,000 to 1,000,000, and more preferably 10,000 to 100,000. The polymer having Mw within the above range is easy to handle when the temporary fixing material layer (I) is formed using the composition (I), and the temporary fixing material layer (I) obtained from the composition (I) has sufficient strength.
The total content of the polybenzoxazole precursor and the polybenzoxazole in 100% by mass of the solid content of the temporary fixing composition (I) is usually 50% by mass or more, preferably 70% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass. The term "solid" as used herein means all components other than the solvent. When the total content is within the above range, the temporary fixing material layer (I) is preferable in terms of adhesiveness, releasability and heat resistance.
< other ingredients >
The temporary fixing composition (I) may optionally contain one or more selected from the group consisting of an adhesion imparting resin such as a petroleum resin or a terpene-based resin, an antioxidant, a polymerization inhibitor, an adhesion promoter, a surfactant, crosslinked polystyrene particles, and metal oxide particles such as alumina, zirconia, titania, and silica.
[ temporary holding Material layer (II) ]
The temporary fixing material layer (II) can be formed of, for example, a temporary fixing composition (II) containing a light absorbing agent. The composition (II) preferably further contains a thermally decomposable resin. The composition (II) may also contain a solvent.
< light absorbing agent >
Examples of the light absorber include: organic light absorbers such as benzotriazole-based light absorbers, hydroxyphenyl triazine-based light absorbers, benzophenone-based light absorbers, salicylic acid-based light absorbers, radiation-sensitive radical polymerization initiators, and light-sensitive acid generators; resins having condensed polycyclic aromatic rings such as phenol novolak and naphthol novolak; black pigments (e.g., carbon black) such as c.i. pigment black 7, c.i. pigment black 31, c.i. pigment black 32, and c.i. pigment black 35; non-black pigments such as c.i. pigment blue (c.i. pigment blue)15:3, c.i. pigment blue 15:4, c.i. pigment blue 15:6, c.i. pigment green (c.i. pigment green)7, c.i. pigment green 36, c.i. pigment green 58, c.i. pigment yellow (c.i. pigment yellow)139, c.i. pigment red (c.i. pigment red) 242, c.i. pigment red 245, and c.i. pigment red 254; c.i. vat blue (c.i. blue)4, c.i. acid blue (c.i. blue)40, c.i. direct green (c.i. direct green)28, c.i. direct green 59, c.i. acid yellow (c.i. acid yellow)11, c.i. direct yellow (c.i. direct yellow) 12, c.i. active yellow (c.i. reactive yellow)2, c.i. acid red (c.i. acid red)37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red (c.i. direct red)28 and c.i. direct red 83.
Further, among the resins having condensed polycyclic aromatic rings, there are also resins that function as a thermally decomposable resin described later. The content of the resin can be calculated as a content corresponding to the light absorbing agent or a content corresponding to the heat decomposable resin.
Among these, a black pigment is preferable in terms of improving the separability of the substrate. In the present invention, as the black pigment, besides the carbon black monomer, a carbon black dispersion such as MHI carbon black #201, MHI carbon black #209, MHI carbon black #220, MHI carbon black #273 (manufactured by yugo pigment (stock)), or the like can be used.
The light absorber may be used alone or in combination of two or more.
The content of the light absorber in 100% by mass of the solid content of the temporary fixing composition (II) is usually 1% by mass to 60% by mass, preferably 10% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass. The term "solid" as used herein means all components other than the solvent. When the content of the light absorbing agent is in the above range, the separability of the base material is further improved, and the base material can be prevented from being deteriorated by light irradiation.
< thermally decomposable resin >
The composition (II) for temporary fixation preferably further contains a heat-decomposable resin. The thermally decomposable resin is thought to be decomposed or modified by light irradiation, thereby further improving the separability of the base material.
In the present specification, the term "thermally decomposable resin" means a resin having a 5% weight loss temperature of 300 ℃ or less. The 5% weight reduction temperature of the thermally decomposable resin is preferably 250 to 150 ℃. The 5% weight loss temperature of the resin can be measured by thermogravimetric analysis (TGA) under nitrogen at a temperature ramp rate of 10 ℃/min.
Examples of the thermally decomposable resin include: cycloolefin polymers, acrylic resins, terpene resins, petroleum resins, novolak resins, and elastomers. Of these, preferred are cycloolefin polymers, terpene resins, petroleum resins, and elastomers.
Examples of the cycloolefin-based polymer include: an addition copolymer of a cyclic olefin compound and a non-cyclic olefin compound, a ring-opening metathesis polymer of one or more cyclic olefin compounds, and a polymer obtained by hydrogenating the ring-opening metathesis polymer.
Examples of the cycloolefin-based compound include: norbornene-based olefins, tetracyclododecene-based olefins, dicyclopentadiene-based olefins, and derivatives thereof. Examples of the derivative include substituted derivatives having one or two or more kinds selected from the group consisting of an alkyl group, an alkylene group, an aralkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an acetyl group, a cyano group, an amide group, an imide group, a silane group, an aromatic ring, an ether bond, and an ester bond.
The acyclic olefin compound includes 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.
The weight average molecular weight (Mw) of the cycloolefin polymer in terms of polystyrene by GPC 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, aromatic modified hydrogenated terpene resins.
Examples of the petroleum resin include: a C5-based petroleum resin, a C9-based petroleum resin, a C5-based/C9-based mixed petroleum resin, a cyclopentadiene-based resin, a polymer of a vinyl-substituted aromatic compound, a copolymer of an olefin and a vinyl-substituted aromatic compound, a copolymer of a cyclopentadiene-based compound and a vinyl-substituted aromatic compound, a hydride of these, and a mixture of two or more kinds selected from these.
Examples of the elastomer include conjugated diene polymer rubbers such as liquid butadiene rubber, liquid isoprene rubber, liquid styrene butadiene rubber, and liquid styrene isoprene rubber which are liquid at room temperature (25 ℃). The elastomer has a number average molecular weight (Mn) of usually 1,000 to 100,000 in terms of polystyrene by GPC.
The thermally decomposable resin may be used alone or in combination of two or more.
The layer containing at least one selected from the group consisting of cycloolefin polymers, terpene resins, petroleum resins, and elastomers has high resistance to chemical liquids used in the photoimprinting process, for example, organic solvents having high polarity or aqueous chemical liquids. Therefore, when the substrate is processed and/or moved, the temporary fixing material layer (II) is prevented from being deteriorated by the chemical liquid, and the substrate is prevented from moving away from the support.
The content of the thermally decomposable resin in 100% by mass of the solid content of the composition (II) for temporary fixation is usually 10% by mass to 95% by mass, preferably 30% by mass to 90% by mass, and more preferably 50% by mass to 80% by mass. The term "solid" as used herein means all components other than the solvent. When the content of the resin is within the above range, the temperature at the time of temporarily fixing the base material to the support is preferably lowered, or the base material is preferably not displaced from the support when the base material is processed and moved.
< other ingredients >
The temporary fixing composition (II) may optionally contain one or more selected from antioxidants, polymerization inhibitors, adhesion promoters, surfactants, crosslinked polystyrene particles, and metal oxide particles such as alumina, zirconia, titania, and silica.
< production of composition for temporary fixation (I) and composition for temporary fixation (II) >
The temporary fixing composition (I) and the temporary fixing composition (II) can be produced by mixing the respective components using a known apparatus used for processing the resin composition, for example, a twin-screw extruder, a single-screw extruder, a continuous kneader, a roll mixer, a pressure kneader, and an internal mixer (Banbury mixer), if necessary. In addition, filtration may be suitably performed in order to remove impurities.
In the production of the temporary fixing composition (I) and the temporary fixing composition (II), a solvent may be used in order to set the viscosity of the compositions in a range suitable for application.
Examples of the solvent used in the composition (I) for temporary fixation include: sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; amide solvents such as 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 3-hexyloxy-N, N-dimethylpropionamide, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, and N, N-diethylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-pentyl-2-pyrrolidone, N- (methoxypropyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; ketone solvents such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; phosphoramide solvents such as hexamethylphosphoramide; and lactone solvents such as gamma-butyrolactone.
Examples of the solvent used in the composition (II) for temporary fixation include: xylene, limonene, mesitylene, dipentene, pinene, bicyclohexene (Bicyclo [2.2.0 ]]hex-1(4)-ene，C6H8) Hydrocarbon solvents such as cyclododecene, 1-tert-butyl-3, 5-dimethylbenzene, butylcyclohexane, cyclooctane, cycloheptane, cyclohexane, and methylcyclohexane; alcohol/ether solvents such as anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether (diglyme); ester/lactone solvents such as ethylene carbonate, ethyl acetate, butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene carbonate, and γ -butyrolactone; ketone solvents such as cyclopentanone, cyclohexanone, methyl isobutyl ketone, and 2-heptanone; amide/lactam solvents such as N-methyl-2-pyrrolidone.
One solvent may be used alone, or two or more solvents may be used in combination.
Since the temporary fixing composition (I) and the temporary fixing composition (II) contain a solvent, the viscosity of these temporary fixing compositions can be easily adjusted, and thus the temporary fixing material can be easily formed on the substrate or the support. For example, the solvent may be used in a range in which the solid content concentration of the temporary fixing composition (I) and the temporary fixing composition (II) is usually 5 to 70% by mass, and more preferably 15 to 50% by mass. The "solid content concentration" herein means the total concentration of all components except the solvent.
<2 > method for treating substrate >
The method for treating a substrate of the present invention comprises: (1) a step of forming the laminate; (2) a step of processing the base material and/or moving the laminate; (3) irradiating the temporary fixing material layer (II) with light; (4) a step of separating the substrate from the support; and (5) a step of removing the temporary securing material layer (I) from the base material.
Hereinafter, the steps are also referred to as step (1) to step (5).
<2-1. step (1) >
In the step (1), for example, (1-1) the substrate can be temporarily fixed to the support by forming the temporary fixing material on the surface of the support and/or the substrate and bonding the substrate to the support via the temporary fixing material. In addition, (1-2) the temporary fixing material is formed on the surface of the support, and a base material such as a resin coating film is formed on the temporary fixing material, whereby the base material can be temporarily fixed to the support. The substrate may also be surface treated if desired.
Examples of the method for forming the temporary fixing material include: (α) a method of forming each layer of the temporary fixing material directly on the support and/or the base material; (β) a method of forming a film of a film such as a polyethylene terephthalate film subjected to a release treatment with a temporary fixing composition in a predetermined thickness, and then transferring each layer to a support and/or a substrate by a lamination method. The (α) method is preferable in terms of uniformity of film thickness.
Examples of the coating method of the temporary fixing composition (I) and the temporary fixing composition (II) for forming each layer of the temporary fixing material include a spin coating method and an ink jet method. As the spin coating method, for example, a method of spin coating the composition under conditions of a spin speed of 300 to 3,500rpm, preferably 500 to 1,500rpm, an acceleration of 500 to 15,000 rpm/sec, and a spin time of 30 to 300 seconds is cited.
After the temporary fixing composition (I) is applied to form a coating film, the temporary fixing layer (I) is formed by, for example, heating to evaporate the solvent. The heating conditions may be appropriately determined depending on the boiling point of the solvent, and for example, the heating temperature is usually 100 to 350 ℃ and the heating time is usually 1 to 60 minutes.
After the temporary fixing composition (II) is applied to form a coating film, the temporary fixing material layer (II) is formed by, for example, heating to evaporate the solvent. The heating conditions may be appropriately determined depending on the boiling point of the solvent, and for example, the heating temperature is usually 100 to 300 ℃ and the heating time is usually 1 to 60 minutes.
The heating of the coating film may be performed in multiple stages as necessary.
In the method (α), examples of the method for bonding the substrate to the support include: method 1, forming a layer (I) on a substrate surface and a layer (II) on a support surface, and bonding these in such a manner that the layers (I) and (II) are in contact; method 2, sequentially forming a layer (I) and a layer (II) on the surface of the substrate and attaching a support body on the layer (II); method 3, layer (II) and layer (I) are formed in this order on the support surface and the substrate is bonded to layer (I). The temperature at this time can be appropriately selected depending on the components contained in the temporary fixing composition (I) and the temporary fixing composition (II), the coating method, and the like. Among these, the above method 1 is preferable from the viewpoint of avoiding mixing of the layer (I) and the layer (II) in the formation of each layer.
The pressure bonding condition between the substrate and the support may be, for example, performed by applying a pressure of 0.01MPa to 100MPa in the lamination direction of each layer at a temperature of preferably room temperature or higher and 400 ℃ or lower, more preferably 150 ℃ to 400 ℃ for 1 minute to 20 minutes. After the pressure bonding, the heating treatment may be further performed at a temperature of 150 to 300 ℃ for 10 minutes to 3 hours. In this way, the base material is firmly held on the support via the temporary fixing member.
In the temporary fixing material layer (I), the total content of the polybenzoxazole precursor and the polybenzoxazole is usually 50% by mass or more, preferably 70% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass. When the content is within the above range, the temporary fixing material layer (I) is preferably adhesive to the temporary fixing material layer (I), releasable from the temporary fixing material layer, and heat resistant.
The content of the light absorber in the temporary fixing material layer (II) is usually 1 to 60 mass%, preferably 10 to 50 mass%, and more preferably 20 to 40 mass%. When the content of the light absorbing agent is in the above range, it is preferable from the viewpoint of the peelability of the substrate. The content of the thermally decomposable resin in the temporary fixing material layer (II) is usually 10 to 95% by mass, preferably 30 to 90% by mass, and more preferably 50 to 80% by mass.
Examples of the substrate as the object to be processed (moved) include: semiconductor wafer, glass substrate, resin substrate, metal foil, polishing pad, and resin coating film. Bumps, wirings, insulating films, and the like may be formed on the semiconductor wafer. Examples of the resin coating film include a layer containing an organic component as a main component; specific examples thereof include: a photosensitive resin layer formed of a photosensitive material, an insulating resin layer formed of an insulating material, a photosensitive insulating resin layer formed of a photosensitive insulating resin material, and the like.
When the temporary fixing material layer (II) is modified by the irradiation of light from the support side in step (3), the support is preferably a substrate transparent to the light used for the light irradiation, and examples thereof include a glass substrate and a quartz substrate.
When the layer (I) is formed on the substrate, the surface of the substrate (for example, a circuit surface) may be subjected to a surface treatment in advance in order to make the in-plane spread of the temporary fixing material uniform. As a method of surface treatment, for example, a method of coating a surface treatment agent on a substrate surface in advance is cited. Examples of the surface treatment agent include coupling agents such as silane coupling agents.
<2-2. step (2) >
The step (2) is a step of processing the base material temporarily fixed to the support and/or moving the resulting laminate. The moving step is a step of moving a substrate such as a semiconductor wafer from a certain apparatus to another apparatus together with a support. Examples of the processing treatment of the substrate temporarily fixed to the support include: cutting, back grinding, etc. to form a thin film on the substrate, and photoetching. The photoetching process includes, for example, one or more processes selected from the group consisting of formation of a resist pattern, etching, formation of a sputtered film, plating, and reflow plating. The etching and the formation of the sputtered film are performed at a temperature of, for example, about 25 to 300 ℃, and the plating and the reflow plating are performed at a temperature of, for example, about 225 to 300 ℃. The processing of the base material is not particularly limited as long as it is performed at a temperature at which the holding force of the temporary fixing material does not disappear.
<2-3. step (3) >
After the processing of the base material or the movement of the laminate, the temporary fixing material layer (II) of the temporary fixing material is irradiated with light, for example, from the support side. When the light irradiation is performed, the light absorbing agent as a component contained in the temporary fixing material layer (II) absorbs the light, and the adhesion of the temporary fixing material layer (II) is reduced. Therefore, after the light irradiation of the temporary fixing material layer (II), the substrate can be easily separated from the support without particularly requiring a heat treatment of the temporary fixing material.
The light irradiation is preferably performed by using ultraviolet rays, and for example, ultraviolet rays having a wavelength of 10nm to 400nm, particularly preferably ultraviolet rays having a wavelength of 300nm to 400nm, can be used. Examples of the light source for irradiating light include: low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, laser.
Among these, laser light is preferable. The entire surface of the temporary fixing material layer (II) is preferably irradiated with the laser beam while scanning the laser beam from the support side, and the laser beam is more preferably irradiated with the laser beam while focusing the laser beam on the temporary fixing material layer (II). The scanning method is not particularly limited, and examples thereof include: a method of irradiating the entire surface of the temporary holding material layer (II) with laser light in a linear manner in the X-axis direction and sequentially moving the irradiation unit in the Y-axis direction in the XY plane; or a method of irradiating the entire surface by irradiating the laser beam in a circumferential pattern at an angle and moving the irradiation portion from the central portion to the peripheral portion to the outside in this order or moving the irradiation portion from the peripheral portion to the central portion to the inside in this order.
Examples of the laser include a solid-state laser (e.g., a fully solid-state laser using a photoexcited semiconductor laser, a Yttrium Aluminum Garnet (YAG) laser), a liquid laser (e.g., a dye laser), and a gas laser (e.g., an excimer laser). Of these, all-solid-state laser (wavelength: 355nm), YAG laser (wavelength: 355nm), and excimer laser, which are optically excited semiconductor lasers, are preferably used.
Examples of excimer lasers include: f2Excimer laser (wavelength: 157nm), ArF excimer laser (wavelength: 193nm), KrF excimer laser (wavelength: 248nm), XeCl excimer laser (wavelength: 308nm), XeF excimer laser (wavelength: 351 nm).
The conditions of light irradiation vary depending on the type of light source, and when a YAG laser or an all-solid-state laser using a photo-excited semiconductor laser, the total dose is usually 1mW to 100W, and the integrated dose is usually 1.4 × 10-7mJ/cm2～1.4×107mJ/cm2。
<2-4. step (4) >
After the processing or moving treatment of the substrate, a force is applied to the substrate or the support, whereby the substrate or the like is peeled from the support, and the substrate and the support are separated from each other. Examples thereof include: a method of separating a substrate or a support by applying a force to the substrate or the support in a direction parallel to the substrate surface; a method of separating one of the substrate and the support from the other by fixing the substrate or the support and lifting the other at a predetermined angle from a direction parallel to the substrate surface.
The former method includes the following methods: the substrate is separated from the support by applying a force to the support that counters the force applied to the support or the fixed support while sliding the substrate in a horizontal direction relative to the surface of the support.
In the latter method, it is preferable that the substrate is separated from the support by applying a force in a direction substantially perpendicular to the surface of the substrate. The phrase "a force is applied in a direction substantially perpendicular to the substrate surface" means that a force is applied in a direction perpendicular to the substrate surface, that is, in a range of usually 0 ° to 60 °, preferably 0 ° to 45 °, more preferably 0 ° to 30 °, further preferably 0 ° to 5 °, particularly preferably 0 °. The separation method may be performed, for example, by a method (hook-and-pull method) in which the peripheral edge of the substrate or the support is lifted (a part or all of the peripheral edge is peeled off from the temporary fixing member) and a force is applied in a direction substantially perpendicular to the substrate surface, and the substrate or the support is sequentially peeled off from the peripheral edge toward the center.
The separation can be carried out at a temperature of usually 5 to 100 ℃, preferably 10 to 45 ℃, and more preferably 15 to 30 ℃. The temperature here refers to the temperature of the support. In addition, in order to prevent the base material from being damaged during the separation, a reinforcing tape, for example, a commercially available dicing tape may be attached to the surface of the base material opposite to the temporary fixing surface of the support.
In the present invention, as described above, the temporary fixing material has the layer (I) and the layer (II), and the substrate is protected by the layer (I), and mainly the separation occurs in the layer (II), so that in the case where the substrate has the bump, the bump can be prevented from being broken at the time of the separation step.
<2-5. step (5) >
The step (5) is a step of removing the temporary securing material layer (I) from the base material. When the temporary fixing material layer (I) is formed of the temporary fixing composition (I) containing a polybenzoxazole precursor, it is considered that the precursor changes to polybenzoxazole having excellent heat resistance by heat applied in, for example, steps (1) to (2). Therefore, deterioration of the temporary fixing material layer (I) due to heat locally generated by light irradiation to the temporary fixing material layer (II) can be suppressed. Therefore, the layer (I) remaining on the substrate after the separation treatment of the substrate can be removed by a simple method such as peeling and solvent cleaning.
As the peeling treatment, for example, a method of peeling the temporary fixing material layer (I) from the base material in a direction substantially perpendicular to the base material surface, specifically, a method of applying a force in a direction substantially perpendicular to the base material surface and sequentially peeling the temporary fixing material layer (I) from the peripheral edge of the base material toward the center (hook-and-pull method) can be cited. The meaning of the substantially vertical direction is as explained in the column of step (4).
Examples of the cleaning treatment using a solvent include a method of immersing the base material in a solvent, a method of spraying a solvent onto the base material, and a method of applying ultrasonic waves while immersing the base material in a solvent. The temperature of the solvent is not particularly limited, but is preferably 10 to 80 ℃ and more preferably 20 to 50 ℃. Examples of the solvent include those described in the section of production of the temporary fixing composition (I) and the temporary fixing composition (II).
Among these, the peeling treatment is preferable in terms of preventing the breakage of the bump.
As described above, the substrate can be separated from the support.
3. Semiconductor device with a plurality of semiconductor chips
The semiconductor device of the present invention can be manufactured by processing a substrate by the substrate processing method of the present invention. After the semiconductor device (e.g., semiconductor element) obtained by separating the processed base material from the support, the temporary fixing material is easily removed in the step (5), and therefore, in the semiconductor device, the contamination (e.g., stain and focal spot) of the temporary fixing material is reduced as much as possible.
[ examples ]
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description of examples and the like, "parts" are used in the meaning of "parts by mass" unless otherwise mentioned.
The average molecular weights (Mw, Mn) of the polymer and the resin were measured by using a GPC column (2G 2000HXL, 1G 3000HXL, 1G 4000HXL) manufactured by Tosoh (Strand Co.) and polystyrene conversion using a measuring apparatus "HLC-8220-GPC" (manufactured by Tosoh (Strand Co.)).
1. Production of composition for temporary fixation
Production example 1 production of composition (I-1) for temporary fixation
50 parts of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 270 parts of N-methyl-2-pyrrolidone were charged into a 0.3L flask and dissolved by stirring. Then, a solution prepared by dissolving 50 parts of 4, 4' -oxybis (benzoyl chloride) in 230 parts of N-methyl-2-pyrrolidone was added dropwise over 30 minutes while maintaining the temperature at 0 to 10 ℃, and the mixture was stirred for 60 minutes. The stirred solution was put into pure water, and a precipitate was recovered, washed 3 times with pure water, and then vacuum-dried to obtain a polybenzoxazole precursor (a 1). The weight average molecular weight of the precursor (A1) was 48,600. The precursor (a1) was dissolved in gamma-butyrolactone/N-methyl-2-pyrrolidone (mass ratio) 8/2 to prepare a composition (I-1) for temporary fixation so that the solid content concentration became 30 mass%.
Production example 2 production of composition (I-2) for temporary fixation
50 parts of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 400 parts of N-methyl-2-pyrrolidone were charged into a 0.3L flask and dissolved by stirring. Then, 50 parts of succinyl dichloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 10 ℃, and then the mixture was stirred for 60 minutes. The stirred solution was put into pure water, and a precipitate was recovered, washed 3 times with pure water, and then vacuum-dried to obtain a polybenzoxazole precursor (a 2). The weight average molecular weight of the precursor (A2) was 58,500. The precursor (a2) was dissolved in gamma-butyrolactone/N-methyl-2-pyrrolidone (mass ratio) 8/2 to prepare a composition (I-2) for temporary fixation, the solid content concentration of which was 30 mass%.
Production example 3 production of composition (I-3) for temporary fixation
50 parts of 2, 2-bis (3-amino-4-hydroxyphenyl) isopropylidene and 270 parts of N-methyl-2-pyrrolidone were added to a flask having a capacity of 0.3L and dissolved by stirring. Then, a solution prepared by dissolving 50 parts of 4, 4' -oxybis (benzoyl chloride) in 230 parts of N-methyl-2-pyrrolidone was added dropwise over 30 minutes while maintaining the temperature at 0 to 10 ℃, and the mixture was stirred for 60 minutes. The stirred solution was put into pure water, and a precipitate was recovered, washed 3 times with pure water, and then vacuum-dried to obtain a polybenzoxazole precursor (a 3). The weight average molecular weight of the precursor (A3) was 26,300. The precursor (a3) was dissolved in gamma-butyrolactone/N-methyl-2-pyrrolidone (mass ratio) 8/2 to prepare a composition (I-3) for temporary fixation, the solid content concentration of which was 30 mass%.
Production example 4 production of composition (I-4) for temporary fixation
50 parts of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 50 parts of 1, 4-cyclohexanedicarboxylic acid (cis-form or trans-form mixture) and 500 parts of polyphosphoric acid were added to a flask having a capacity of 0.3L and dissolved by stirring. Then, the temperature was raised to 200 ℃ under a nitrogen atmosphere, and stirring was continued for 30 minutes. The stirred solution was put into pure water, and a precipitate was recovered, washed 3 times with pure water, and then vacuum-dried to obtain a polybenzoxazole precursor (a 4). The weight-average molecular weight of the precursor (A4) was 41,000. The precursor (A4) was dissolved in cyclohexanone to prepare a solution having a solid content concentration of 30 mass%, thereby producing a temporary fixing composition (I-4).
Production example 5 production of composition for temporary fixation (I-5)
70 parts of p-tert-butoxystyrene and 10 parts of styrene were dissolved in 150 parts of propylene glycol monomethyl ether, and polymerization was carried out for 10 hours using 4 parts of azobisisobutyronitrile while maintaining the reaction temperature at 70 ℃ under a nitrogen atmosphere. Then, sulfuric acid was added to the solution after polymerization, and the reaction was carried out for 10 hours while maintaining the reaction temperature at 90 ℃ to deprotect the p-tert-butoxystyrene structural unit and convert it into a p-hydroxystyrene structural unit. To the shifted solution was added ethyl acetate, and the ethyl acetate was removed by 5 water washes to obtain a p-hydroxystyrene/styrene copolymer (a 5). The weight average molecular weight (Mw) of the copolymer (A5) was 10,000. Further, the copolymer (a5) was a polymer having 80 mol% of p-hydroxystyrene units and 20 mol% of styrene units according to NMR. The copolymer (A5) was dissolved in ethyl lactate to prepare a solution having a solid content concentration of 30% by mass, thereby producing a composition (I-5) for temporary fixation.
Production example 6 production of composition for temporary fixation (I-6)
5.0 g of 2, 2' -azobisisobutyronitrile as a polymerization initiator and 150g of propylene glycol monomethyl ether acetate as a polymerization solvent were put into a flask purged with nitrogen and stirred. 11g of methacrylic acid, 15g of p-isopropenylphenol, and tricyclo [5.2.1.0 ] were put into the stirred solution2，6]Decyl methacrylate 15g, isobornyl acrylate 39g, and phenoxy polyethylene glycol acrylate 20g, and the temperature was raised to 80 ℃ while starting stirring. Thereafter, the mixture was heated at 80 ℃ for 6 hours. The heated solution was added dropwise to a large amount of cyclohexane and solidified. The coagulum was washed with water, redissolved in tetrahydrofuran of the same weight as the coagulum, and the resulting solution was added dropwise to a large amount of cyclohexane and allowed to coagulate again. After the total of the above redissolution and coagulation operations was carried out 3 times, the obtained coagulated product was vacuum-dried at 40 ℃ for 48 hours to obtain a copolymer (A6). The weight average molecular weight (Mw) of the copolymer (A6) was 10,000. The copolymer (A6) was dissolved in propylene glycol monomethyl ether acetate to prepare a solution having a solid content concentration of 30% by mass, thereby producing a composition (I-6) for temporary fixation.
Production example 7 production of composition for temporary fixation (II-1)
80 parts of a cycloolefin polymer (trade name "Arton RX 4500", manufactured by JSR (Strand)), 20 parts of a hydrogenated terpene resin (trade name "Kurilong (CLEON) P150", manufactured by Yasuhara Chemical) (Strand)), 20 parts of a liquid styrene butadiene rubber (trade name "L-SBR-820", manufactured by Colorary (Strand)), 3 parts of a hindered phenol antioxidant (trade name "Yinous (IRGANOX) 1010", manufactured by BASF corporation), 125 parts of a carbon black dispersion (trade name "MHI carbon black # 209", manufactured by Yuguo pigment (Strand having a solid content of 35 mass%), and 367 parts of mesitylene were mixed to manufacture a temporary fixing composition (II-1).
2. Evaluation of
Examples 1 to 4 and comparative examples 1 to 4
The temporary fixing compositions (I-1) to (I-6) were spin-coated on a 4-inch silicon wafer (substrate 1), and then heated under the film formation conditions described in table 1 using a hot plate, to obtain a substrate 1 having a uniform temporary fixing material layer (I) with a thickness of 10 μm. The temporary fixing composition (II-1) was spin-coated on a 4-inch glass wafer (substrate 2), and then heated at 160 ℃ for 5 minutes and further at 230 ℃ for 10 minutes using a hot plate, thereby producing a substrate 2 having a uniform temporary fixing material layer (II) with a thickness of 3 μm.
After the substrate 1 and the substrate 2 were cut into a length of 1cm and a width of 1cm, respectively, the temporary holding material layer (I) and the temporary holding material layer (II) were bonded to each other in contact with each other, and a pressure of 15MPa was applied for 5 minutes at a pressure bonding temperature shown in table 1 using a die bonding apparatus, thereby obtaining a laminate in which the substrate 1 and the substrate 2 were laminated via the temporary holding material layers.
An all-solid-state high-output laser device (trade name "Gilles (genetics) CX 355 STM Compact", manufactured by Coherent Japan) was used to output 100mW and integrated light quantity was 2.08X 10-4mJ/cm2The laminate thus obtained was irradiated with an Ultraviolet (UV) laser (wavelength 355nm) from the substrate 2 side. The substrate 2 was removed from the test laminate after the light irradiation. Next, whether or not the temporary fixing material layer (I) on the substrate 1 can be peeled off, and whether or not the temporary fixing material layer (I) can be washed with a solvent used in the preparation of each temporary fixing material composition for forming the temporary fixing material layer (I) is evaluated. The evaluation results are shown in table 1.
In the peeling treatment of the layer (I), the layer (I) was peeled off by applying a force (23 ℃ c. at a speed of 500 μm/sec) in the direction of the axis (z axis) perpendicular to the surface of the substrate 1 by using a universal bond strength tester (trade name "Dage 4000", manufactured by Dage corporation) in a hook-pull manner.
In the cleaning treatment of the layer (I), the laminate from which the substrate 2 was removed was immersed in the same solvent as used for the preparation of each of the temporary fixing compositions (I-1) to (I-6) for forming the temporary fixing material layer (I) at 23 ℃ for 20 minutes. For example, in the case of example 1, the laminate from which the substrate 2 was removed was immersed in 8/2 (mass ratio) γ -butyrolactone/N-methyl-2-pyrrolidone, and in the case of comparative example 1, the laminate from which the substrate 2 was removed was immersed in ethyl lactate.
[ Table 1]
Claims (6)
1. A method of treating a substrate comprising, in order:
(1) a step of forming a laminate having a support, a temporary fixing material, and a base material,
the temporary fixing material is a layer I of the temporary fixing material which is in contact with the surface of the support body side of the base material and is formed by a composition containing at least one polymer selected from a polybenzoxazole precursor and polybenzoxazole, and
a temporary fixing material layer II formed on the support-side surface of the temporary fixing material layer I and containing one or more selected from the group consisting of an organic light absorber, a resin having a condensed polycyclic aromatic ring, a black pigment, a non-black pigment, and a dye, and one or more thermally decomposable resins selected from the group consisting of a cycloolefin polymer, a terpene resin, a petroleum resin, and an elastomer,
the thermal decomposition resin is a resin with 5% weight reduction temperature below 300 ℃;
(2) a step of processing the base material and/or moving the laminate;
(3) irradiating the temporary fixing material layer II with light;
(4) a step of separating the substrate from the support; and
(5) a step of removing the temporary securing material layer I from the base material.
2. The method of treating a substrate according to claim 1, wherein the composition comprises a polybenzoxazole precursor.
3. The method for treating a substrate according to claim 1 or 2, wherein in the step (3), the light irradiated to the temporary fixing material layer II is ultraviolet light.
4. The method for treating a substrate according to claim 3, wherein the ultraviolet ray is an ultraviolet ray having a wavelength of 300nm to 400 nm.
5. The method for treating a substrate according to claim 1 or 2, wherein in the step (5), the temporary securing material layer I is removed from the substrate by a process of peeling the temporary securing material layer I from the substrate and/or a process of washing the temporary securing material layer I with a solvent.
6. A semiconductor device obtained by the method for treating a substrate according to any one of claims 1 to 5.
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| PCT/JP2016/071548 WO2017033639A1 (en) | 2015-08-21 | 2016-07-22 | Method for processing substrate, composition for temporary fixing, and semiconductor device |
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| CN115551962A (en) * | 2020-05-21 | 2022-12-30 | 电化株式会社 | Composition comprising a fatty acid ester and a fatty acid ester |
| WO2023243488A1 (en) * | 2022-06-13 | 2023-12-21 | 日東電工株式会社 | Adhesive sheet for provisional fixation of electronic component |
| WO2023243487A1 (en) * | 2022-06-13 | 2023-12-21 | 日東電工株式会社 | Adhesive sheet for provisional fixation of electronic component |
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| CN1885500A (en) * | 2005-06-24 | 2006-12-27 | 精工爱普生株式会社 | Manufacturing method for a semiconductor device |
| CN101030526A (en) * | 2006-03-03 | 2007-09-05 | 株式会社半导体能源研究所 | Method of manufacyuring semiconductor device |
| CN102625952A (en) * | 2009-09-16 | 2012-08-01 | 住友电木株式会社 | Film for forming spacer, method for manufacturing semiconductor wafer bonded body, semiconductor wafer bonded body, and semiconductor device |
| WO2015030030A1 (en) * | 2013-08-30 | 2015-03-05 | 富士フイルム株式会社 | Laminate and application therefor |
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| WO2017033639A1 (en) | 2017-03-02 |
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