TWI535815B - Temporal fixative and method of processing a base material - Google Patents

Description

Temporary fixative and substrate processing method

The present invention relates to a method for processing a temporary fixing agent and a substrate, and more particularly to a temporary fixing agent used for temporarily fixing the substrate to a supporting substrate during processing of the substrate, and a substrate using the temporary fixing agent. processing methods.

The present application claims priority based on Japanese Patent Application No. 2010-278687 and Japanese Patent Application No. 2010-278678, the entire disclosure of which is hereby incorporated by reference.

When a semiconductor wafer is subjected to processing such as polishing or etching, it is necessary to temporarily fix the semiconductor wafer on a substrate for supporting a semiconductor wafer, and various methods have been proposed. For example, there are a number of methods for fixing a semiconductor wafer to a film for fixing a PET film as a substrate with an adhesive layer.

In this method, if the grinding precision (about 1 μm) of the general back grinding machine used for the combined grinding and the thickness correction (about 5 μm) of the general back grinding (BG) tape for fixing the semiconductor wafer exceeds the requirement, Thickness accuracy results in a non-uniform thickness of the ground wafer.

Further, in the case of processing a semiconductor wafer used in a through silicon via (Through Silicon Via), a through hole or a film is formed in a state in which a BG tape is attached, but at this time, even if the temperature is low, it may reach about 150 ° C, which may cause The adhesion of the BG tape is improved. Further, the adhesive layer of the BG tape is eroded by the chemical solution for forming the plating of the film, and peeling occurs.

Further, a semiconductor wafer which is weakly represented by a compound semiconductor may be damaged by mechanical grinding, and therefore thinned by etching. During the etching, There is no particular problem in the amount of etching for the purpose of removing stress. However, when the number of etching is several μm, the BG tape may be deteriorated by the etching solution.

On the other hand, in recent years, a method of fixing a semiconductor wafer to a support substrate having a smooth surface with a fixing material interposed therebetween has been gradually adopted.

For example, when etching is performed for the purpose of removing stress, it is required to be heated to a high temperature, but the PET film cannot withstand such a high temperature. In such a case, a method of using a supporting substrate should be applied.

It has been proposed to use a fixing material which is softened at a high temperature and can be easily detached from a semiconductor wafer, and is used as a fixing material for fixing a substrate (semiconductor wafer) to a supporting substrate (for example, refer to Patent Document 1), or may be due to a specific chemical solution. A fixing material to be dissolved (for example, refer to Patent Document 2).

However, among the above, the former needs to be a fixing material having a melting temperature which does not soften when processing a semiconductor wafer, and as a result, when the semiconductor wafer is detached, it is necessary to expose the semiconductor wafer to a higher temperature than when it is processed. Therefore, the processed semiconductor wafer may deteriorate and deteriorate.

Further, when semiconductor wafer processing is performed using the former fixing material, it is required to be firmly fixed to the supporting substrate when the semiconductor wafer is processed, and can be easily detached from the supporting substrate when the semiconductor wafer is detached. However, the current state of the art for processing semiconductor wafers using such fixed materials has not been found.

Furthermore, the latter requires processing of the support substrate in such a manner that the fixed material is uniformly contacted with the chemical solution. Therefore, it is impossible to provide sufficient strength to the support substrate, and the semiconductor wafer and the support substrate may be damaged during semiconductor wafer processing.

Moreover, the problem is not limited to the processing of semiconductor wafers, Various substrates which are processed in a state of being fixed to a supporting substrate may also occur.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2010-531385

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-191550

SUMMARY OF THE INVENTION An object of the present invention is to provide a temporary fixing agent which can reduce damage to a substrate and at the same time can perform high-precision processing, and can easily perform detachment of the substrate from the supporting substrate at a low heating temperature after processing; A method of processing a substrate using the temporary fixative is provided.

Another object of the present invention is to provide a method for processing a substrate, which is capable of temporarily fixing a substrate to a support substrate when the substrate is temporarily fixed to a support substrate and subjected to substrate processing. When the substrate is detached from the support substrate after the processing, the substrate can be easily detached from the support substrate.

The above object can be achieved by the following inventions (1) to (20).

(1) A temporary fixing agent for temporarily fixing the base material to a support substrate when processing a substrate, and after heating the active energy ray after processing the substrate, The substrate is detached from the support substrate;

The method has the following characteristics: after irradiating the active energy ray, the melt viscosity at 180 ° C is 0.01 to 100 Pa. s.

(2) The temporary fixing agent according to (1), wherein the irradiation of the active energy ray is performed by irradiating light having a wavelength of 365 mm at 2000 mJ/cm ² .

(3) The temporary fixing agent according to (1) or (2), wherein the melting viscosity at 180 ° C is 100 to 10000 Pa before the irradiation of the active energy ray. s.

(4) The temporary fixing agent according to any one of (1) to (3), wherein the melt viscosity at 180 ° C before the irradiation of the active energy ray is defined as A [Pa. s], and the melting viscosity at 180 ° C after irradiation of the aforementioned active energy ray is determined as B [Pa. When s], the relationship of A/B is 10~10000.

(5) The temporary fixing agent according to any one of (1) to (4), wherein the temporary fixing agent is in a molten state by heating after the irradiation of the active energy ray, and thereby the substrate is made Detachment from the aforementioned support substrate.

(6) The temporary fixing agent according to any one of (1) to (5) wherein, after the irradiation of the active energy ray, the 50% weight loss temperature is 260 ° C or higher.

(7) The temporary fixing agent according to any one of (1) to (6), which is composed of a resin composition comprising the following components: a resin component having a reduced melt viscosity due to heating in the presence of an acid or a base; An acid or base active agent is produced by irradiation of the aforementioned active energy ray.

(8) The temporary fixing agent of (7), wherein the resin component is a polycarbonate resin.

(9) The temporary fixing agent of (8), wherein the polycarbonate-based resin is composed of at least two annular bodies in the carbonate constituent unit.

(10) A method of processing a substrate, comprising the steps of: forming a film comprising the temporary fixing agent according to any one of (1) to (9) on the substrate and the support At least one of the substrates; In the second step, the substrate and the support substrate are bonded together via the film; in the third step, the surface of the substrate opposite to the support substrate is processed; and the fourth step is After the film is irradiated with the active energy ray, the film is heated to be in a molten state, whereby the substrate is detached from the support substrate, and in the fifth step, the film remaining on the substrate is washed.

(11) The method for processing a substrate according to (10), wherein the support substrate is translucent.

(12) A method for processing a substrate, comprising the steps of: a first step of thermally decomposing by heating to form a temporary fixing agent composed of a resin composition containing a molten or vaporized resin component; At least one of the material and the support substrate is dried to form a film; in the second step, the substrate is bonded to the support substrate via the film; and in the third step, the substrate is bonded to the substrate The support substrate is processed on the opposite side; in the fourth step, the film is irradiated with an active energy ray; and in the fifth step, the film is heated to thermally decompose the resin component, whereby the substrate is supplied from the support group. In the fourth step, when the irradiation amount of the active energy ray is set to E [J/cm ² ], the average thickness of the film is set to M [cm], and in the fifth step, the film is heated. When the temperature is set to T [° C.] and the time for heating the film is set to t [minute], the relationship is set to satisfy the relationship of the following formula 1 to the following formula 3.

Log(T ² .t)≦-10 ^-4 . (E ² /M)+5.7.........Form 1

Log(T ² .t)≧-10 ^-4 . (E ² /M)+3.8.........Form 2

3.3×10 ^-5 ≦E ² /M≦8.0×10 ⁵ .........3

(13) The method for processing a substrate according to (12), wherein the irradiation amount E of the active energy ray is 0.001 to 20 J/cm ² .

(14) The method of processing a substrate according to (12) or (13), wherein the thickness M of the film is 5 × 10 ^-4 to 3 × 10 ^-2 cm.

(15) The method for processing a substrate according to any one of (12) to (14) wherein the temperature T of the film is heated to 60 to 400 °C.

(16) The method for processing a substrate according to any one of (12) to (15) wherein the time t for heating the film is 1.67 × 10 ^-3 to 60 minutes.

The method for processing a substrate according to any one of the preceding claims, wherein the resin component is thermally decomposed in the fifth step by irradiating the film with an active energy ray in the fourth step. The temperature is lowered.

(18) The method for processing a substrate according to (17), wherein the resin component is reduced in temperature at which the thermal decomposition is carried out in the presence of an acid or a base, and the resin composition further includes irradiation of the active energy ray. An acid or base active agent.

(19) The method for processing a substrate according to (18), wherein the active agent contains 0.01 to 50% by weight based on the resin component in the resin composition.

(20) The method for processing a substrate according to any one of the preceding claims, wherein, in the first step, the support substrate is selectively supplied to the support substrate and the support substrate. The aforementioned film is formed by temporarily fixing the agent.

According to the temporary fixing agent of the first embodiment of the present invention, the melting temperature is lowered by heating the active energy ray after the processing of the substrate. Therefore, the substrate can be fixed on the support substrate during the processing of the substrate, and the substrate can be detached from the support substrate at a low heating temperature when the substrate is detached, so that damage to the substrate can be reduced and at the same time High-precision processing, and can be used to easily remove the substrate from the support substrate at a low heating temperature after processing.

Further, according to the method for processing a substrate according to the second embodiment of the present invention, the substrate can be processed in a state in which the substrate is firmly fixed to the support substrate by a film formed by using a temporary fixing agent. Further, it is possible to appropriately set the irradiation amount of the active energy ray to be irradiated to the film after the substrate processing, and the heating condition when the substrate is detached from the supporting substrate, thereby facilitating the detachment of the substrate from the supporting substrate. effect.

[Formation of the Invention]

Hereinafter, a method of processing a temporary fixing agent and a substrate of the present invention will be described in detail based on a preferred embodiment shown in the accompanying drawings.

[First Embodiment]

First, the temporary fixing agent of the first embodiment of the present invention will be described.

<temporary fixative>

In the temporary fixing agent according to the first embodiment of the present invention, the base material is temporarily fixed to a support substrate in order to process the substrate, and after the substrate is processed, the active energy ray is irradiated and heated. The substrate is detached from the support substrate, and the user has a melting viscosity of 0.01 to 100 Pa at 180 ° C after the irradiation of the active energy ray. s.

As described above, in the temporary fixing agent of the present embodiment, the melt viscosity at 180 ° C after the irradiation of the active energy ray is lowered to the above range. So, temporary fixatives when Heating in a temperature range of about 130 to 200 ° C becomes a molten state, and becomes a melt viscosity which can easily remove the substrate from the supporting substrate. Thereby, the step of releasing (peeling) the support substrate from the substrate after the substrate processing can be easily performed without causing damage such as cracks to the substrate after the processing.

The temporary fixing agent of the present embodiment is composed of a resin composition containing the following components: a resin component having a reduced melt viscosity by heating in the presence of an acid or a base; and an acid generated by irradiation of the active energy ray or Alkali active agent.

Hereinafter, each component constituting the resin composition will be described in order.

(resin component)

The resin component has a function of fixing the substrate to the support substrate when temporarily fixed, and is reduced in melting viscosity due to heating after irradiation with active energy rays. Therefore, there is a function of facilitating the detachment of the substrate from the support substrate by heating after irradiation with the active energy ray.

The resin component is not particularly limited as long as it has a reduced melt viscosity by heating in the presence of an acid or a base, and examples thereof include a polycarbonate resin, a polyester resin, a polyamide resin, and a polyimine. The resin, the polyether resin, the polyurethane resin, and the (meth) acrylate resin may be used alone or in combination of two or more. Among these, a polycarbonate resin, a vinyl resin, and a (meth)acrylic resin are preferable, and a polycarbonate resin is preferable. These are preferred as the resin component because they are more significantly reduced in melt viscosity due to heating in the presence of an acid or a base.

The vinyl resin is not particularly limited, and examples thereof include a polymer of a styrene derivative such as polystyrene or poly-α-methylstyrene, poly(ethyl vinyl ether), and poly(butyl vinyl ether). And a polyvinyl ether or a derivative thereof, such as a polyvinyl acetal, may be used alone or in combination of two or more. Among these, poly-α-methylstyrene is preferred. This resin component is particularly preferable from the viewpoint of excellent workability.

Further, the (meth)acrylic resin is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate. A copolymer selected from various (meth)acrylic monomers such as (meth)acrylic acid or 2-hydroxyethyl (meth)acrylate. Among these, polymethyl methacrylate or polyethyl methacrylate is preferred. This resin component is particularly preferable from the viewpoint of excellent workability.

Further, the polycarbonate resin is not particularly limited, and examples thereof include a linear chemical structure such as a polypropylene carbonate containing a carbonate constituent unit, a polyvinyl carbonate, a polybutylene carbonate, or a carbonate. The structural unit is composed of a cyclic chemical structure. Among these, it is preferred that the carbonate structural unit contains a cyclic chemical structure. This resin component is particularly preferable from the viewpoint of excellent workability.

Hereinafter, the polycarbonate resin in which the carbonate structural unit contains the cyclic chemical structure will be described in detail.

The polycarbonate resin may have any structure as long as it has a cyclic chemical structure (hereinafter sometimes referred to as a "ring"), but it is preferably one having at least two annular bodies. In the polycarbonate resin, by appropriately selecting the number and type of the cyclic body, heating is carried out in the presence of an acid or a base generated from the active agent by irradiation with an active energy ray, and the melt viscosity can be easily set to As in the aforementioned range

Further, the number of the annular bodies is preferably 2 to 5, more preferably 2 or 3, and still more preferably 2. By including such a number of annular bodies in the carbonate constituent unit, the temporary fixing agent can be bonded to the support substrate with excellent adhesion before the active energy ray irradiation.

Further, a plurality of annular bodies may have a polycyclic ring structure formed by connecting their respective apexes to each other, but it is preferred that each of the annular bodies has a side condensed to form each other. Condensed polycyclic structure. Thereby, the planarity of the carbonate structural unit is improved, so that the difference in the melt viscosity at 180 ° C before and after the irradiation of the active energy ray can be set larger.

Furthermore, most of the annular bodies may each be a 5-membered ring or a 6-membered ring. Thereby, the planarity of the carbonate constituent unit can be more maintained, so that the difference in melt viscosity at 180 ° C before and after the irradiation of the active energy ray can be set larger, and at the same time, the solubility to the solvent described later can be made more stable.

Most of such cyclic bodies are preferably alicyclic compounds. When each of the cyclic bodies is an alicyclic compound, the above effects can be exhibited more remarkably.

In the polycarbonate (resin component), a preferred structure of the carbonate constituent unit is, for example, the following chemical formula (1).

Further, a polycarbonate having a carbonate structural unit represented by the above chemical formula (1) can be obtained by a polycondensation reaction of decalindiol with a carbonic acid diester such as diphenyl carbonate.

Further, in the carbonate constituent unit represented by the above chemical formula (1), the hydroxyl group of decalindiol is bonded to the difference between the decahydronaphthalene (that is, the two cyclic bodies constituting the condensed polycyclic structure). Preferably, the carbon atom and the carbon atom bonded to the hydroxyl group are preferably the shortest inserted with three or more atoms.

Thereby, the linearity of the polycarbonate can be maintained, and as a result, the difference in the melt viscosity at 180 ° C before and after the irradiation of the active energy ray can be more surely set to be large. Further, the solubility of the solvent described later can be made more stable.

Such a carbonate constituent unit is, for example, represented by the following chemical formulae (1A) and (1B).

Further, most of the cyclic bodies may be heteroalicyclic compounds in addition to the alicyclic compounds. When each of the cyclic bodies is a heteroalicyclic compound, the above effects can be more significantly exhibited.

In this case, in the polycarbonate (resin component), the carbonate constituent unit is, for example, a preferred structure represented by the following chemical formula (2).

Further, the polycarbonate having the carbonate structural unit represented by the above chemical formula (2) can be an ether diol represented by the following chemical formula (2a) and a carbonic acid diester such as diphenyl carbonate. Obtained by the polycondensation reaction.

Further, in the carbonate structural unit represented by the above chemical formula (2), the hydroxyl group of the cyclic ether diol represented by the above chemical formula (2a) is bonded to each other to form the cyclic ether (that is, to form a condensed polycyclic ring system). It is preferable that the carbon atoms of the two cyclic structures of the structure are different from each other, and it is preferable to insert three or more atoms between the carbon atoms of the hydroxyl groups. Thereby, the linearity of the polycarbonate can be maintained, and as a result, the difference in the melt viscosity at 180 ° C before and after the irradiation of the active energy ray can be more surely set to be large. Further, the solubility of the solvent described later can be made more stable.

Such a carbonate constituent unit is, for example, a 1,4:3,6-dihydro-D-sorbitol (isosorbide) type represented by the following chemical formula (2A), or represented by the following chemical formula (2B) 1,4:3,6-di-dehydrated-D-mannitol (isomannide) type.

The weight average molecular weight (Mw) of the resin component varies depending on the kind of the resin component, etc., but is preferably from 1,000 to 1,000,000, more preferably from 5,000 to 800,000. By setting the weight average molecular weight to the above lower limit or more, the sacrificial layer forming step described later can provide an effect of improving the moisture permeability of the support substrate by the temporary fixing agent, and further, film formation can be obtained. The effect of sexual improvement.

Further, the resin component is preferably blended in a proportion of about 10 to 100% by weight based on the total amount of the resin composition (temporary fixing agent), and more preferably blended in a ratio of 30 to 100% by weight. When the content of the resin component is at least the above lower limit value, the adhesion of the temporary fixing agent to the substrate or the support substrate can be surely reduced after the detachment step described later. Therefore, the temporary fixing agent remaining on the substrate can be easily removed in the washing step.

(active agent)

The active agent is an active material such as an acid or a base which is applied by irradiation of an active energy ray, and has a function of reducing the melt viscosity of the resin component by heating in the presence of the active material.

The active agent is not particularly limited, and examples thereof include a photoacid generator which generates an acid due to irradiation with an active energy ray, or a photobase generator which generates an alkali due to irradiation with an active energy ray.

The photoacid generator is not particularly limited, and is, for example, ruthenium (pentafluorophenyl)borate-4-methylphenyl[4-(1-methylethyl)phenyl]fluorene (DPI-TPFPB), ginseng (4) -T-butylphenyl)indole-(pentafluorophenyl)borate (TTBPS-TPFPB), ginseng (4-t-butylphenyl)phosphonium hexafluorophosphate (TTBPS-HFP), triphenyl Trifluoromethanesulfonate (TPS-Tf), bis(4-t-butylphenyl)phosphonium triflate (DTBPI-Tf), three (TAZ-101), triphenylsulfonium hexafluoroantimonate (TPS-103), triphenylsulfonium bis(perfluoromethanesulfonyl) quinone imine (TPS-N1), di-(for the third Phenyl hydrazine, bis(perfluoromethanesulfonyl) quinone imine (DTBPI-N1), triphenylsulfonium, ginseng (perfluoromethanesulfonyl) methide (TPS-C1), di-( For the tributyl phenyl) hydrazine (perfluoromethanesulfonyl) methide (DTBPI-C1), one or a combination of two or more of them may be used. Among these, yttrium (pentafluorophenyl)borate-4-methylphenyl[4-(1-methylethyl)phenyl] is especially used from the viewpoint of efficiently reducing the melt viscosity of the resin component.錪 (DPI-TPFPB) is preferred.

Further, the photobase generator is not particularly limited, and examples thereof include 5-benzyl-1,5-diazabicyclo (4.3.0) decane and 1-(2-nitrobenzylideneamine carbhydryl)imidazole. For example, one type or a combination of two or more types may be used. Among these, in particular, 5-benzyl-1,5-diazabicyclo(4.3.0) decane and derivatives thereof are preferably used from the viewpoint of efficiently reducing the melt viscosity of the resin component.

The active agent is preferably from about 0.01 to 50% by weight, more preferably from about 0.1 to 30% by weight, based on the total amount of the resin composition (temporary fixative). Within this range, the melt viscosity of the resin component can be stably lowered to the intended range.

An active substance such as an acid or a base can be produced by adding such an active agent and irradiating an active energy ray. It is presumed that when the resin composition is heated in the presence of the active material, a structure in which the melt viscosity is lowered in the main chain of the resin component is formed.

(sensitizer)

Further, the temporary fixing agent may contain, in addition to the active agent, a sensitizer which is a component which exhibits a function of exhibiting or increasing the reactivity of the active agent. The sensitizer can broaden the range of wavelengths at which the active agent can be activated. The most suitable sensitizer is a compound that has a maximum absorption coefficient near the source of use and can efficiently transfer absorbed energy to the photoacid generator. In particular, when the light source is a long wavelength (ultraviolet to visible light region) such as g line (435 nm) and i line (365 nm), the sensitizer is effective for activating the photoacid generator.

The sensitizer is not particularly limited, but when it contains a photoacid initiator, for example, 2-isopropyl-9H-thioxanthene-9-one, 4-iso Propyl-9H-thioxan-9-one, 1-chloro-4-propoxythioxanthene-9-one, thiophene Or a combination of these, etc.

Such a sensitizer can be added in a range that does not directly affect the photothermal reaction of the resin. The content of the sensitizer is preferably 100 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the total of the active agents such as the photoacid generator.

(Antioxidants)

Further, the resin composition (temporary fixing agent) may also contain an antioxidant.

This antioxidant has a function of preventing generation of an acid in a resin composition (temporary fixing agent) or preventing natural oxidation.

The antioxidant is not particularly limited. For example, Ciba Fine Chemicals Co., Ltd., "Ciba IRGANOX (registered trademark) 1076" and "Ciba IRGAFOS (registered trademark) 168" are preferred.

Further, as the other antioxidant, for example, "Ciba Irganox 129", "Ciba Irganox 1330", "Ciba Irganox 1010", "Ciba Cyanox (registered trademark) 1790", "Ciba Irganox 3114, Ciba Irganox 3125", or the like can be used.

The content of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the above resin component.

(additive)

Further, the resin composition (temporary fixing agent) may contain an acid scavenger, an acrylic, an anthrone, a fluorine-based, a vinyl-based coating agent, a decane coupling agent, a diluent, or the like, as needed.

The decane coupling agent is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyl group. Triethoxy decane, p-styryl trimethoxy decane, 3-methyl propylene methoxypropyl methyl dimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-methyl Propylene oxime propyl methyl diethoxy decane, 3-methyl propylene oxypropyl triethoxy decane, 3-propenyl propyl propyl trimethoxy decane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3- Aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, 3 -巯基 Propylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxypropyl)tetrasulfide, 3-isocyanatepropyltriethoxydecane, etc., one of which can be used. Use two or more types in combination.

The resin composition (temporary fixing agent) can improve the adhesion between the substrate and the supporting substrate by including a decane coupling agent.

Further, the diluent is not particularly limited, and examples thereof include a cyclic ether compound such as epoxycyclohexane or α-pinene oxide, and [methylenebis(4,1-phenyleneoxymethylene)]dioxyethylene B. One type or a combination of two or more types may be used, for example, a cyclic aliphatic vinyl ether compound such as an aromatic cyclic ether such as an alkane or a 1,4-cyclohexanedimethanol divinyl ether.

The resin composition (temporary fixing agent) can improve the fluidity of the temporary fixing agent by including a diluent, and can improve the moisture permeability of the temporary fixing agent to the supporting substrate in the sacrificial layer forming step described later.

(solvent)

Further, the resin composition (temporary fixing agent) may contain a solvent.

The solvent is not particularly limited, for example: Hydrocarbons such as decahydronaphthalene, mineral spirits, anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, diethylene glycol ether, etc. Ethyl ester, ethyl acetate, n-butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propyl carbonate, γ - esters such as butyrolactone/endoester, cyclopentanone, cyclohexanone, methyl isobutyl ketone, 2-heptanone, etc., N-methyl-2-pyrrolidone The guanamine or the decylamine may be used alone or in combination of two or more. Thereby, the temporary fixing agent can easily adjust the viscosity of the temporary fixing agent by including a solvent, and it becomes easy to form a sacrificial layer (film) composed of a temporary fixing agent on the supporting substrate.

The content of the solvent is not particularly limited, and is a total of a resin composition (temporary fixative). The amount is preferably 5 to 98% by weight, more preferably 10 to 95% by weight.

In the present embodiment, the various constituent materials contained in the resin composition, particularly the combination of the resin component and the active agent, and the contents thereof are set so that the temporary fixing agent has a melt viscosity at 180 ° C after irradiation with active energy rays. Become 0.01~100Pa. s.

If such a temporary fixing agent (resin composition) is heated at a temperature of about 130 to 200 ° C, the temporary fixing agent can be made molten, and the substrate can be easily removed from the supporting substrate. The degree of melting of the degree of detachment. As a result, the substrate can be detached (peeled) from the support substrate after the substrate is processed, and can be easily carried out without causing damage such as cracks to the substrate after the processing.

Moreover, the temporary fixing agent has a melt viscosity of 0.01 to 100 Pa at 180 ° C after irradiation with active energy rays. s can be, but especially about 0.1~50Pa. s is preferred. Thereby, the aforementioned effects can be more significantly exhibited.

Further, the melt viscosity at 180 ° C before the irradiation of the active energy ray is not particularly limited and is about 100 to 10,000 Pa. s is better, about 100~1000Pa. s is better. Thereby, even if the temporary fixing agent is heated to about 180 ° C at the time of processing of the substrate, the temporary fixing agent has sufficient strength for fixing the substrate to the supporting substrate, and can surely prevent the substrate from being supported by the processing of the substrate. The substrate is detached.

Furthermore, the melt viscosity at 180 ° C before the irradiation of the active energy ray is defined as A [Pa. s], and the melt viscosity at 180 ° C after irradiation with active energy ray is set to B [Pa. When s], A/B satisfies the relationship of 100~10000, and the relationship of 200~1000 is better. By satisfying the relationship of A/B, the substrate can be reliably fixed to the support substrate by the temporary fixing agent during the processing of the substrate, and when the substrate is detached from the support substrate, the processed substrate can be easily Detach from the support substrate.

Further, in order to prevent the temporary fixing agent from diffusing into the gas atmosphere when heating the substrate from the support substrate, that is, the temporary atmosphere is prevented from being contaminated by the gas atmosphere caused by the temporary fixing agent, the temporary fixing agent is preferably heated. It does not vaporize in a gas atmosphere, but is preferably between the substrate and the support substrate.

Therefore, after the active agent is irradiated with the active energy ray, the 50% weight loss temperature of the temporary fixing agent is preferably 260 ° C or higher, more preferably 300 ° C or higher. Thereby, it is possible to more reliably suppress or prevent the temporary fixing agent from diffusing into the gas atmosphere during the aforementioned heating.

Further, the melt viscosity of the temporary fixing agent can be measured by a rheometer method.

Specifically, first, a solution of a temporary fixing agent is applied onto a ruthenium substrate, and dried on a hot plate at 120 ° C for 300 seconds, and the light from the ultrahigh pressure mercury lamp as an active energy ray is irradiated at a wavelength of 365 nm. After 2000 mJ/cm ² , the film-like test piece obtained by peeling off from the substrate was set by a rheometer (Haake RS150 type, manufactured by Thermo Fischer Scientific Co., Ltd.) at intervals of 30 μm, and the temperature increase rate was 10 ° C / minute at 30 to 300. The temperature was raised at °C, and shear stress was applied at a time of 1 Hz. The displacement at this time was measured, and the melt viscosity of the temporary fixing agent was obtained.

Further, in the present specification, the 50% weight loss temperature means a temperature at which the weight of the resin component is lost by 50% due to heating. At this temperature, the range of the heating temperature at which the resin component starts to decompose to the end can be measured, in other words, the temperature at which the resin component starts to decompose and the end temperature at which the decomposition of the resin component is completed (completed) are measured by dynamic thermogravimetric analysis (TGA). And based on the results of the results.

Specifically, first, a resin component dissolved in N-methyl-2-pyrrolidone (NMP) is applied onto a ruthenium substrate by spin coating, and then soft baked at a temperature of about 110 ° C for 10 minutes on a hot plate. This causes the solvent to evaporate. Next, a film (sample) composed of a resin component formed on the substrate was elevated from 30 ° C to 500 ° C at a rate of 5 ° C / min in a nitrogen atmosphere, and analyzed by dynamic TGA. The temperature at which the 50% weight loss of the temporary fixing agent (resin composition) measured by the dynamic TGA was determined was taken as the 50% weight loss temperature (T _d50 ).

Further, when the active energy ray is irradiated to the temporary fixing agent, the optimum condition is changed depending on, for example, the thickness of the temporary fixing agent used, and the like, and is not particularly limited. It is preferably irradiated at a wavelength of 365 nm at 1 to 2000 mJ/cm ² . Light. By setting this condition, a sufficient amount of an active substance such as an acid or a base can be generated from the active agent, and by heating in the presence of the active material, the melt viscosity of the resin component can be more reliably reduced. Therefore, the conditions of the active energy ray for the temporary fixative should be suitably used.

<Method of Manufacturing Semiconductor Device>

Next, an example in which the temporary fixing agent according to the first embodiment of the present invention is applied to the manufacture of a semiconductor device will be described.

In the method of manufacturing a semiconductor device, an example of an embodiment of a method for processing a substrate according to the first embodiment of the present invention is applied to the processing of a semiconductor wafer.

The processing of the semiconductor wafer (substrate) has the following steps: in the first step, forming a sacrificial layer (film) composed of the temporary fixing agent of the embodiment on at least one of the substrate and the supporting substrate; In the second step, the support substrate and the semiconductor wafer are bonded together via the sacrificial layer; in the third step, the surface of the semiconductor wafer opposite to the support substrate is processed; and in the fourth step, the sacrificial layer is irradiated. After the active energy ray, the sacrificial layer is heated to be in a molten state, thereby disengaging the semiconductor wafer from the supporting substrate; and in the fifth step, the sacrificial layer remaining in the semiconductor wafer is washed.

Fig. 1 is a longitudinal cross-sectional view showing a processing procedure for processing a semiconductor wafer by using a temporary fixing agent according to a first embodiment of the present invention. In the following description, in FIG. 1, the upper side is described as "upper" and the lower side is described as "lower".

The steps are described in the following order.

(sacrificial layer forming step)

First, the support substrate 1 is prepared, and the support substrate (or substrate) 1 is used. The temporary fixing agent of the embodiment forms the sacrificial layer 2 (refer to Fig. 1 (a)).

The sacrificial layer 2 can be easily formed by supplying the temporary fixing agent of the present embodiment to the support substrate 1 and then drying it.

Further, the method of supplying the temporary fixing agent of the present embodiment to the support substrate 1 is not particularly limited, and for example, a spin coating method, a spray coating method, a printing method, a film transfer method, a slit coating method, or a scanning coating can be used. Various coating methods such as the law. Among these, spin coating is preferred. According to the spin coating method, a more uniform and flat sacrificial layer 2 can be easily formed.

Further, the support substrate 1 is not particularly limited as long as it has a strength capable of supporting the semiconductor wafer 3, and is preferably a light-transmitting one. Thereby, even if the semiconductor wafer 3 does not have translucency, the active energy ray can be penetrated from the support substrate 1 side and the sacrificial layer 2 can be surely irradiated with the active energy ray in the active energy ray irradiation step.

The light-transmitting support substrate 1 is, for example, a glass material such as quartz glass or soda glass, or polyethylene terephthalate, polyethylene naphthalate, polypropylene, or cycloolefin. A substrate made of a main material such as a polymer material such as a polymer, a polyamide or a polycarbonate.

(Fitting step)

Next, a semiconductor wafer (substrate) 3 is placed on the surface of the support substrate 1 on which the sacrificial layer 2 is placed, and the functional surface 31 is placed on the sacrificial layer 2 side. Thereby, the semiconductor wafer 3 is bonded to the support substrate 1 via the sacrificial layer 2 (see FIG. 1(b)).

This bonding can be easily performed, for example, using a vacuum press, a wafer bonder or the like.

(processing steps)

Next, the semiconductor wafer 3 is fixed to the support substrate 1 via the sacrificial layer 2 The functional surface 31 is processed on the opposite side (back surface).

The processing of the semiconductor wafer 3 is not particularly limited. For example, the back surface of the semiconductor wafer 3 shown in FIG. 1(c) is polished, the through hole is formed in the semiconductor wafer 3, and the semiconductor wafer 3 for releasing stress is performed. The back surface is etched, lithographically coated, and coated on the back side of the semiconductor wafer 3, vapor deposited, or the like.

Further, in the processing of the semiconductor wafer in the present embodiment, the sacrificial layer 2 having excellent uniformity of film thickness and smooth surface is formed by using the temporary fixing agent of the present embodiment in the sacrificial layer forming step. Therefore, the effect of processing the semiconductor wafer 3 with excellent precision can be exhibited.

Further, in this processing step, the sacrificial layer 2 is heated and undergoes a temperature history in response to the kind of processing as described above. At this time, active energy ray irradiation is not performed on the sacrificial layer 2, and the sacrificial layer 2 is maintained at a high melt viscosity. Therefore, since the back surface can be processed without peeling or the like between the semiconductor wafer 3 and the support substrate 1, the above-described processing can be performed with excellent dimensional accuracy.

Further, as described above, in the present embodiment, the melt viscosity at 180 ° C before the irradiation of the active energy ray is preferably from 100 to 10,000 Pa. s. As described above, when the melt viscosity at 180 ° C is within the above range, the above effects can be exhibited more remarkably.

(Active energy ray irradiation/heating step)

Next, as shown in FIG. 1(d), the sacrificial layer 2 is irradiated with an active energy ray.

Thereby, energy can be imparted to the active agent contained in the temporary fixing agent (resin composition), and as a result, the active agent such as an acid or a base can be produced as the active agent.

Further, the active energy ray is not particularly limited, and for example, light having a wavelength of about 200 to 800 nm is preferable, and light having a wavelength of about 300 to 500 nm is more preferable.

Further, the amount of the active energy ray to be irradiated is not particularly limited, and is preferably from about 1 to 2,000 mJ/cm ^{2 , more} preferably from about 10 to 1,000 mJ/cm ² .

By setting the conditions for irradiating the active energy ray as described above, it is possible to obtain from the active agent that the melt viscosity at 180 ° C after the irradiation of the active energy ray is 0.01 to 100 Pa. s sufficient amount of active substance required.

Next, as shown in FIG. 1(e), the sacrificial layer 2 is heated to bring the sacrificial layer 2 into a molten state.

Thereby, the semiconductor wafer 3 can be surely detached from the support substrate 1 in the detachment step described later.

Here, in the present embodiment, before the heating of the sacrificial layer 2, the sacrificial layer 2 is irradiated with an active energy ray to generate an acid or a base, and the melt viscosity of the resin component is lowered by the action of the acid or the alkali. That is, the melting viscosity of the sacrificial layer 2 after irradiation with the active energy ray at 180 ° C is 0.01 to 100 Pa. s.

Therefore, the heating temperature for causing the sacrificial layer 2 to be in a molten state can be set to be low. Specifically, in order to make the melt viscosity at 180 ° C after the irradiation of the active energy ray within the above range, the heating temperature may be set to about 130 to 200 ° C. Therefore, it is possible to surely suppress or prevent deterioration and deterioration of the semiconductor wafer 3 due to the heating, and it is possible to shorten the time required for the sacrificial layer 2 to be in a molten state.

(out of step)

Next, the semiconductor wafer 3 is detached from the support substrate 1.

At this time, the sacrificial layer 2 is in a molten state by the above-described active energy ray irradiation/heating step, so that the semiconductor wafer 3 can be easily detached from the support substrate 1.

Here, in the present specification, the detachment means that the semiconductor wafer 3 is supported from the support substrate 1 The peeling operation, for example, the operation of, for example, detaching the semiconductor wafer 3 in a direction perpendicular to the surface of the support substrate 1, or sliding the semiconductor wafer 3 horizontally with respect to the surface of the support substrate 1. As a method of separating, or as shown in FIG. 1(f), the semiconductor wafer 3 is floated and detached from the one end side of the semiconductor wafer 3, and the like.

At this time, the sacrificial layer 2 can be removed from between the semiconductor wafer 3 and the support substrate 1 by the above-described heating step, so that the semiconductor wafer 3 can be easily detached from the support substrate 1.

(washing step)

Next, the sacrificial layer 2 remaining on the functional surface 31 of the semiconductor wafer 3 is washed.

That is, the residue of the sacrificial layer 2 remaining on the functional surface 31 is removed.

The method for removing the residue is not particularly limited, and examples thereof include a plasma treatment, a chemical liquid immersion treatment, a polishing treatment, and a heat treatment.

Further, in the present embodiment, the sacrificial layer 2 is formed on the support substrate 1 in the sacrificial layer forming step. However, the sacrificial layer 2 may be formed on both the support substrate 1 and the semiconductor wafer 3 in this case. The formation of the sacrificial layer 2 on the support substrate 1 and the formation of the sacrificial layer 2 on the semiconductor wafer 3 can be omitted.

Although the temporary fixing agent and the processing method of the base material according to the first embodiment of the present invention have been described above based on the embodiments shown in the drawings, the present invention is not limited thereto.

For example, each constituent material contained in the temporary fixing agent may be replaced by any one that can exhibit the same function, or may be added to any constituent.

Further, the method for processing the substrate of the present invention may be added to any step as needed.

[Second Embodiment]

First, before describing the method of processing the substrate according to the second embodiment of the present invention, the temporary fixing agent used in the present invention will be described.

<temporary fixative>

The temporary fixing agent according to the second embodiment of the present invention is used for temporarily fixing the base material to a support base material for processing a base material, and heating the active energy ray after the processing of the base material. The substrate is used to be detached from the support substrate, and is composed of a resin composition containing a resin component thermally decomposed by heating after irradiation with the active energy ray.

By using the temporary fixing agent, the substrate can be processed in a state in which the substrate is temporarily fixed to the supporting substrate by a film formed using a temporary fixing agent, and further, the film is melted by heating after irradiation with active energy rays. Or gasification to detach the substrate from the support substrate.

Hereinafter, each component constituting the resin composition containing the resin component will be described in order.

The resin component has a function of fixing the substrate to the support substrate when temporarily fixed (during processing of the substrate), and since heating is performed after the active energy ray irradiation, the temperature of thermal decomposition is higher than when the active energy ray is not irradiated. Since it is low, it has a function of easily detaching a substrate from a support substrate by heating after irradiation with an active energy ray.

The resin component is not particularly limited as long as it is reduced in molecular weight in the presence of an acid or a base, and is, for example, a polycarbonate resin, a polyester resin, a polyamide resin, or a polyether. The resin, the polyurethane resin, the (meth) acrylate resin, and the like may be used alone or in combination of two or more. Among these, a polycarbonate resin, a vinyl resin, and a (meth)acrylic resin are preferable, and a polycarbonate resin is preferable. These are due to their low molecular weight in the presence of acid or base The temperature will be significantly lower, so it should be used as a resin component.

The vinyl-based resin is not particularly limited, and examples thereof include polymers of styrene derivatives such as polystyrene and poly-α-methylstyrene, such as poly(ethyl vinyl ether) and poly(butyl vinyl). One type or a combination of two or more types may be used, for example, a polyvinyl ether such as an ether or a methyl acetal or a derivative thereof. Among these, poly-α-methylstyrene is preferred. This resin component is particularly preferable from the viewpoint of excellent workability.

Further, the (meth)acrylic resin is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate. A copolymer selected from various (meth)acrylic monomers such as (meth)acrylic acid or 2-hydroxyethyl (meth)acrylate. Among these, polymethyl methacrylate or polyethyl methacrylate is preferred. This resin component is particularly preferable from the viewpoint of excellent workability.

The polycarbonate resin is not particularly limited, and examples thereof include a polypropylene carbonate resin, a polyvinyl carbonate resin, a 1,2-polybutylene carbonate resin, a 1,3-polybutylene carbonate resin, and 1,4- Polybutylene carbonate resin, cis-2,3-polybutylene carbonate resin, trans-2,3-polybutylene carbonate resin, α,β-polyisobutylene carbonate resin, α,γ-poly Isobutylene carbonate resin, cis-1,2-polycyclobutene carbonate resin, trans-1,2-polycyclobutene carbonate resin, cis-1,3-polycyclobutene carbonate resin, Trans-1,3-polycyclobutene carbonate resin, polyhexene carbonate resin, polycyclopropene carbonate resin, polycyclohexene carbonate resin, 1,3-polycyclohexane carbonate resin, poly (Methylcyclohexene carbonate) resin, poly(vinylcyclohexene carbonate) resin, polydihydronaphthalene carbonate resin, polyhexahydrostyrene carbonate resin, polycyclohexane propylene carbonate resin, poly Styrene carbonate resin, poly(3-phenylpropene carbonate) resin, poly(3-trimethylmethoxy propylene carbonate) resin, poly(3-methacryloxy propylene carbonate) resin, Polyfluoropropylene Acid ester resin, polynorthene carbonate resin, polynordecane carbonate resin, exo-polynorthene carbonate resin, endo-polynorthene carbonate resin, trans-poly The decylene carbonate resin and the cis-poly decene carbonate resin may be used alone or in combination of two or more.

Further, as the polycarbonate resin, for example, a polypropylene carbonate/polycyclohexene carbonate copolymer, a 1,3-polycyclohexane carbonate/polypentene carbonate copolymer, a poly[( Oxycarbonyloxy-1,1,4,4-tetramethylbutane)-alt-(oxycarbonyloxy-5-norpredene-2-intro-3-endo-dimethane)] resin, Poly[(oxycarbonyloxy-1,4-dimethylbutane)-alt-(oxycarbonyloxy-5-nordecene-2-intro-3-endo-dimethane)] resin, poly [(oxycarbonyloxy-1,1,4,4-tetramethylbutane)-alt-(oxycarbonyloxy-p-xylene)] resin, and poly[(oxycarbonyloxy-1) , 4-dimethylbutane)-alt-(oxycarbonyloxy-p-xylene)] resin, 1,3-polycyclohexane carbonate resin/exo-polynorthene carbonate resin, 1, a copolymer of 3-polycyclohexane carbonate resin/inward-polynorthene carbonate resin.

Further, in addition to the above, a polycarbonate resin having at least two annular bodies in a carbonate constituent unit may be used.

The number of the cyclic bodies may be two or more in the carbonate constituent unit, preferably 2 to 5, more preferably 2 or 3, and still more preferably 2. By including such a ring body in the carbonate constituent unit, the adhesion between the support substrate and the substrate can be excellent. Further, the polycarbonate resin is thermally decomposed by the heating of the temporary fixing agent to lower the molecular weight, thereby becoming a melter.

Further, many of the annular bodies may have a polycyclic ring structure in which their respective vertices are connected to each other, but it is preferable to have a condensed polycyclic ring structure in which one of them is connected to each other. Thereby, the heat resistance as a temporary fixing agent and the thermal decomposition time at the time of melting can be shortened.

Furthermore, most of the annular bodies are preferably a 5-membered ring or a 6-membered ring. Thereby, the planarity of the carbonate constituent unit can be maintained, so that the solubility in the solvent can be made more stable.

Most of such cyclic bodies are preferably alicyclic compounds. When each of the cyclic bodies is an alicyclic compound, the above effects can be exhibited more remarkably.

In consideration of such factors, a particularly preferable structure of the carbonate constituent unit in the polycarbonate resin is represented by the following chemical formula (1X).

Further, the polycarbonate-based resin having a carbonate structural unit represented by the above chemical formula (1X) can be obtained by a polycondensation reaction of decalindiol and a carbonic acid diester such as diphenyl carbonate.

Further, in the carbonate constituent unit represented by the above chemical formula (1X), the decahydronaphthalenediol has a carbon atom to which a hydroxyl group is bonded, and preferably each constitutes decahydronaphthalene (that is, a condensed polycyclic structure is formed). The other two carbon atoms are bonded to each other, and three or more atoms are interposed between the carbon atoms to which the hydroxyl groups are bonded. Thereby, the decomposability of the polycarbonate resin can be controlled, and as a result, the heat resistance as a temporary fixing agent and the thermal decomposition time at the time of melting can be shortened. Furthermore, the solubility in the solvent can be made more stable.

Such a carbonate constituent unit is represented, for example, by the following chemical formulae (1A) and (1B).

Further, most of the cyclic bodies may be heteroalicyclic compounds in addition to the alicyclic compound. When each of the cyclic bodies is a heteroalicyclic compound, the above effects can be exhibited more remarkably.

In this case, among the polycarbonate resins, a preferable structure of the carbonate constituent unit is represented by the following chemical formula (2X), for example.

In addition, the polycarbonate resin having the carbonate structural unit represented by the above chemical formula (2X) can be obtained by a polycondensation reaction of an ether diol represented by the following chemical formula (2a) with a carbonic acid diester such as diphenyl carbonate. .

Further, in the carbonate constituent unit represented by the above chemical formula (2X), the above chemistry The cyclic ether diol represented by the formula (2a) has a carbon atom bonded to a hydroxyl group, and preferably each of the other cyclic ethers (that is, two cyclic forms forming a condensed polycyclic structure) The carbon atoms are bonded and three or more atoms are interposed between the carbon atoms. Thereby, the heat resistance as a temporary fixing agent and the thermal decomposition time at the time of melting can be shortened. Furthermore, the solubility in a solvent can be made more stable.

Such a carbonate constituent unit is, for example, a 1,4:3,6-dihydro-D-sorbitol (isosorbide) type represented by the following chemical formula (2A), or represented by the following chemical formula (2B) 1,4:3,6-di-dehydrated-D-mannitol (isomannide) type.

The weight average molecular weight (Mw) of the polycarbonate resin is preferably from 1,000 to 1,000,000, more preferably from 5,000 to 800,000. When the weight average molecular weight is at least the above lower limit, the effect of improving the moisture permeability of the supporting substrate can be obtained, and the film forming property improving effect can be obtained. Further, by being at most the above upper limit value, more remarkable effects on solubility in various solvents and melting and oxidation due to heating of the temporary fixing agent can be obtained.

Further, the polymerization method of the polycarbonate resin is not particularly limited, and for example, a known polymerization method such as a phosgene method (solvent method) or a transesterification method (melting method) can be used.

Further, the resin component is preferably blended at a ratio of 10% by weight to 100% by weight based on the total amount of the resin composition (the total amount other than the solvent when the solvent is contained). More preferably, it is preferably blended at a ratio of 50% by weight or more, particularly preferably 80% by weight to 100% by weight. By 10 wt% or more, particularly preferably 80 wt% or more, can have an effect of reducing the residue after thermal decomposition of the temporary fixing agent. Further, by increasing the amount of the resin component in the resin composition, the effect of thermally decomposing the temporary fixing agent in a short period of time can be obtained.

Further, as the above resin component, the thermal decomposition temperature in the presence of an acid or a base is lowered. Further, among the polycarbonate resins, in particular, polypropylene carbonate, 1,4-polybutene carbonate, 1,3-polycyclohexane carbonate/polypentene carbonate copolymer are considered to be the heat. The decrease in the temperature of decomposition is more pronounced.

Further, by including, in addition to the resin component, a composition of an active agent which generates an acid or a base due to irradiation of an active energy ray with respect to the temporary fixing agent, the resin component can be caused by irradiation of the active energy ray to the temporary fixing agent. The thermal decomposition temperature is lowered.

Therefore, by including the resin component in the temporary fixing agent (resin composition) and the active agent which generates an acid or a base by irradiating the active energy ray to the temporary fixing agent, the thermal decomposition temperature of the resin component is lowered by the irradiation of the active energy ray. . As a result, by heating the temporary fixing agent after the irradiation of the active energy ray, the effect of easily detaching the substrate from the supporting substrate even at a lower temperature can be obtained.

(active agent)

The active agent, as described above, is capable of producing an active substance such as an acid or a base by energy applied by irradiation with an active energy ray, and has a thermal decomposition temperature of the aforementioned resin component due to the action of the active material. The function of the person.

The active agent is not particularly limited, and examples thereof include a photoacid generator which generates an acid due to irradiation with an active energy ray, or a photobase generator which generates an alkali due to irradiation with an active energy ray.

The photoacid generator is not particularly limited, and is, for example, ruthenium (pentafluorophenyl)borate-4-methylphenyl[4-(1-methylethyl)phenyl]fluorene (DPI-TPFPB), ginseng (4) -T-butylphenyl)indole-(pentafluorophenyl)borate (TTBPS-TPFPB), ginseng (4-t-butylphenyl)phosphonium hexafluorophosphate (TTBPS-HFP), triphenyl Trifluoromethanesulfonate (TPS-Tf), bis(4-t-butylphenyl)phosphonium triflate (DTBPI-Tf), three (TAZ-101), triphenylsulfonium hexafluoroantimonate (TPS-103), triphenylsulfonium bis(perfluoromethanesulfonyl) quinone imine (TPS-N1), di-(for the third Phenyl hydrazine, bis(perfluoromethanesulfonyl) quinone imine (DTBPI-N1), triphenylsulfonium, ginseng (perfluoromethanesulfonyl) methide (TPS-C1), di-( For the tributyl phenyl) hydrazine (perfluoromethanesulfonyl) methide (DTBPI-C1), one or a combination of two or more of them may be used. Among these, yttrium (pentafluorophenyl)borate-4-methylphenyl[4-(1-methylethyl)phenyl] is especially used from the viewpoint of efficiently reducing the melt viscosity of the resin component.錪 (DPI-TPFPB) is preferred.

Further, the photobase generator is not particularly limited, and examples thereof include 5-benzyl-1,5-diazabicyclo (4.3.0) decane and 1-(2-nitrobenzylideneamine carbhydryl)imidazole. For example, one type or a combination of two or more types may be used. Among these, in particular, 5-benzyl-1,5-diazabicyclo(4.3.0) decane and derivatives thereof are preferably used from the viewpoint of efficiently reducing the melt viscosity of the resin component.

The active agent is preferably from about 0.01 to 50% by weight, more preferably from about 0.1 to 30% by weight, based on the resin component. By this range, a sufficient amount of active material for lowering the thermal decomposition temperature of the resin component can be generated from the active agent. Therefore, by the irradiation of the active energy ray, the thermal decomposition temperature of the resin component can be more reliably lowered. As a result, the substrate can be easily detached from the support substrate by heating after irradiation with the active energy ray.

Since the active energy ray is irradiated by the active energy ray, an active substance such as an acid or a base is generated, and due to the action of the active material, a structure in which the thermal decomposition temperature is lowered in the main chain of the resin component is formed. As a result, it is estimated that the thermal decomposition temperature of the resin component is lowered.

Here, a polypropylene carbonate resin which is a polycarbonate resin is used for the resin component, and when the photoacid generator is used as the active agent, the thermal decomposition temperature is lowered. As shown in the following formula (1Z), first, H ⁺ from the photoacid generator first protonates the carbonyl oxygen of the polypropylene carbonate resin, and shifts to a polar transition state, resulting in an unstable tautomeric intermediate [A] And [B]. Next, the intermediate [A] is fragmented into a thermal cut of acetone and CO ₂ , and thus the thermal decomposition temperature is lowered. Further, the intermediate [B] forms a propyl carbonate, and the propyl carbonate is fragmented into CO ₂ and propylene oxide to form a heat-closed structure. Therefore, the thermal decomposition temperature is lowered.

(sensitizer)

Further, the temporary fixing agent may contain, in addition to the above-mentioned active agent, a sensitizer which is a component which has a function of exhibiting an active energy ray of a specific wavelength or increasing reactivity.

The sensitizer is not particularly limited, for example, bismuth, phenanthrene, Benzopyrene, (fluoranthene), rubrene, rubidium, Xanthone, indanthrene, thioxanthene-9-ketone, 2-isopropyl-9H-thioxanthene-9-one, 4-isopropyl-9H- Thioxanthene-9-ketone, 1-chloro-4-propoxythioxanthone, and mixtures thereof.

The content of the sensitizer is preferably 100 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the total of the active agent such as the photoacid generator and the photoradical initiator.

As the above resin composition, other components as shown below may also be contained.

(Antioxidants)

That is, the resin composition (temporary fixative) may also contain an antioxidant.

The antioxidant can be used in the same manner as the antioxidant in the first embodiment, and thus the description thereof is omitted here.

(additive)

Further, the resin composition (temporary fixing agent) may contain an acid scavenger, an acrylic, an anthrone, a fluorine-based, a vinyl-based coating agent, a decane coupling agent, a diluent, or the like, as needed. These additives can be used in the same manner as the additives in the first embodiment, and thus the description thereof will be omitted.

(solvent)

Further, the resin composition (temporary fixing agent) may contain a solvent.

The resin composition can easily adjust the viscosity of the resin composition by including a solvent.

The solvent is not particularly limited, for example: Hydrocarbons such as decahydronaphthalene and mineral spirit, aromatic hydrocarbons such as toluene, xylene, and trimethylbenzene, anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, and diethylene glycol mono Alcohol/ether, such as diethyl ether and diglyme, ethyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, propyl carbonate, γ-butyrolactone and other esters / lactones, cyclopentanone, cyclohexanone, methyl isobutyl ketone, 2-heptanone and other ketones, N- The guanamine/indoleamine such as N-methyl-2-pyrrolidone may be used alone or in combination of two or more. Thereby, the viscosity of the temporary fixing agent can be easily adjusted, and it is easy to form a sacrificial layer (film) composed of a temporary fixing agent on the supporting substrate.

The content of the solvent is not particularly limited, and is preferably from 5 to 98% by weight, more preferably from 10 to 95% by weight, based on the total amount of the resin composition (temporary fixing agent).

<Method of Manufacturing Semiconductor Device>

The temporary fixing agent as described above can be applied, for example, to a method of manufacturing a semiconductor device.

That is, in the processing of the semiconductor wafer in the method of manufacturing a semiconductor device, a method of processing the substrate of the present embodiment using a temporary fixing agent can be applied.

Hereinafter, an example of the second embodiment of the method for processing a substrate of the present invention will be described.

The processing of the semiconductor wafer (substrate) includes the following steps: in the first step, the temporary fixing agent is supplied to at least one of the semiconductor wafer and the supporting substrate, and then dried to form a sacrificial layer (film); a step of bonding the semiconductor wafer to the support substrate via the sacrificial layer; a third step of processing the surface of the semiconductor wafer opposite to the support substrate; and a fourth step of irradiating the sacrificial layer with active energy Radiation; In the fifth step, the sacrificial layer is heated to thermally decompose the resin component, thereby detaching the semiconductor wafer from the support substrate.

In the semiconductor wafer processing method of the above configuration, in the present embodiment, the irradiation amount of the active energy ray in the fourth step is set to E [J/cm ² ], and the average thickness of the sacrificial layer is set to M [cm]. When the temperature of the heating sacrificial layer in the fifth step is set to T [° C.] and the time for heating the sacrificial layer is t [minute], the relationship is set to satisfy the relationship of the following formula 1 to the following formula 3.

Log(T ² .t)≦-10 ^-4 . (E ² /M)+5.7.........Form 1

Log(T ² .t)≧-10 ^-4 . (E ² /M)+3.8.........Form 2

3.3×10 ^-5 ≦E ² /M≦8.0×10 ⁵ .........3

1 is a longitudinal cross-sectional view for explaining a processing procedure of semiconductor wafer processing applied to a method of processing a substrate according to a second embodiment of the present invention, and FIG. 2 is an exposure amount of an active energy ray, an average thickness of a film, and The relationship between the temperature of the heated film and the time to heat the film. In the following description, in FIG. 1, the upper side is described as "upper" and the lower side is described as "lower".

The following steps are described in detail for each of the steps. In the following, an example in which a sacrificial layer is selectively formed on a support substrate among a semiconductor wafer and a support substrate will be described.

(sacrificial layer forming step)

First, the support substrate 1 is prepared, and as shown in FIG. 1(a), the sacrificial layer 2 is formed on the support substrate (or substrate) 1 using the temporary fixing agent (first step).

The sacrificial layer 2 can be easily formed by heating and drying the temporary fixing agent to the support substrate 1.

Here, the Tama (Thermomechanical Analysis) softening point of the film-formed sacrificial layer 2 is not particularly limited, and is preferably less than 200 ° C, more preferably about 50 to 180 ° C. Thereby, in the next step (bonding step), at least the surface can be melted by heating.

In addition, the TMA softening point is measured by a thermomechanical measuring device (TMA), and the temperature of the object to be measured is raised at a fixed temperature increase rate in a state where a fixed load is applied, and the phase of the object to be measured is observed. In the present specification, the temperature at which the phase of the sacrificial layer 2 starts to change is defined as the TMA softening point. Specifically, the TMA softening point can be measured by using, for example, a thermomechanical measuring device ("Q400EM" manufactured by TA Instruments Co., Ltd.). The temperature range is set at 25~250°C, so that when the heating rate is 5°C/min, for 1mm When a quartz glass needle was applied with a load of 10 g, the temperature at which the phase began to change was measured.

Further, the method of supplying the temporary fixing agent to the support substrate 1 is not particularly limited, and various coatings such as a spin coating method, a spray coating method, a printing method, a film transfer method, a slit coating method, and a scanning coating method can be used. Bufa. Among these, spin coating is particularly preferred. According to the spin coating method, a more uniform and flat sacrificial layer 2 can be easily formed.

When the spin coating method is used, the temporary fixing agent uses a viscosity (25 ° C) of 500 to 100,000 mPa. s is better, use about 1,000~50,000mPa. s is better.

Further, the viscosity (25 ° C) can be measured as a value at a cone temperature of 25 ° C for 3 minutes using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., viscosity meter TVE-22 type).

Further, the rotation speed of the support substrate 1 to which the temporary fixing agent is supplied is preferably set to about 300 to 4,000 rpm, more preferably about 500 to 3,500 rpm.

When the spin coating method is used, the sacrificial layer 2 can be formed into a film by satisfying the conditions, and the obtained sacrificial layer 2 can have an average thickness of about 50 to 100 μm. Further, the sacrificial layer 2 having the thickness can be formed into a film having a substantially uniform thickness.

Furthermore, when the viscosity of the temporary fixative (25 ° C) is set to A [mPa. s] and the support substrate 1 has a rotational speed of B [rpm], A/B is preferably 0.13 to 330, and more preferably 0.5 to 100. Thereby, a film of the sacrificial layer 2 having an average thickness of 5 × 10 ^-4 to 3 × 10 ^-2 cm can be formed with a particularly uniform and flat thickness.

Further, the support base material 1 is not particularly limited as long as it has strength to support the base material 3, and is preferably light transmissive. Thereby, when the temporary fixative is made active When the thermal ray is lowered by the irradiation of the energy ray, the active energy ray can be penetrated from the support substrate 1 side, and the sacrificial layer 2 is surely irradiated with the active energy ray.

The light-transmitting support substrate 1 is, for example, a glass material such as quartz glass or soda glass, or polyethylene terephthalate, polyethylene naphthalate, polypropylene, or a cycloolefin polymer. A substrate made of a main material such as a resin material such as polyamide or polycarbonate.

(Fitting step)

Next, as shown in FIG. 1(b), a semiconductor wafer (substrate) 3 is placed on the surface of the support substrate 1 on which the sacrificial layer 2 is placed, and the functional surface 31 is placed on the sacrificial layer 2 side. Perform thermocompression bonding. Thereby, the semiconductor wafer 3 is bonded to the support substrate 1 via the sacrificial layer 2 (second step).

That is, the semiconductor wafer 3 and the support substrate 1 are bonded to each other on the side of the support substrate 1 with the functional surface 31 interposed therebetween via the sacrificial layer 2.

The bonding by this thermocompression bonding can be easily performed using a device such as a vacuum press or a wafer bonder.

Here, in the state in which the sacrificial layer 2 is inserted, the pressure when the semiconductor wafer 3 and the support substrate 1 are pressed in the direction in which they are close to each other is not particularly limited, and is preferably about 0.01 to 3 MPa, more preferably about 0.012 to 2.5 MPa. , about 0.05~2MPa is the best.

Further, the temperature at which the sacrificial layer 2 is heated at this time is not particularly limited, and is preferably about 100 to 300 ° C, more preferably about 120 to 250 ° C.

Further, the time of pressurization and heating is not particularly limited, and is preferably from about 0.1 to 10 minutes, more preferably from about 0.5 to 10 minutes.

By thermally pressing the sacrificial layer 2 to the functional surface 31 under this condition, the sacrificial layer 2 comes into contact with the functional surface 31 in a state where at least the surface is melted. Here, since the functional surface 31 of the semiconductor wafer 3 is formed with wirings or bumps made of a conductive material, the functional surface 31 forms an uneven surface. In this way, although the functional surface 31 is composed of the uneven surface, at least the sacrificial layer 2 is in a molten state. Thereby, when the sacrificial layer 2 contacts the functional surface 31, the sacrificial layer 2 is buried in the functional surface 31 following the concavo-convex shape, so that the sacrificial layer 2 can be maintained between the semiconductor wafer 3 and the support substrate 1 via the sacrificial layer 2 The semiconductor wafer 3 is bonded to the support substrate 1 in a state of being spaced.

Further, when the TMA softening point of the sacrificial layer 2 is within the range described in the sacrificial layer forming step, the sacrificial layer 2 can be thermocompression bonded to the functional surface 31 under the above-described pressing conditions and temperature conditions, thereby being more excellent. The bonding of the semiconductor wafer 3 and the support substrate 1 via the sacrificial layer 2 is performed with precision.

Further, the unevenness of the functional surface 31 is usually less than 50 μm even if a large volume such as a bump is formed. Therefore, according to the present embodiment, in the sacrificial layer forming step, the sacrificial layer 2 having an average film thickness of about 5 × 10 ^-4 to 3 × 10 ^-2 cm is formed, and the sacrificial layer 2 can be buried in the concave-convex surface. Functional surface 31. Thereby, the semiconductor wafer 3 and the support substrate 1 can be kept at a fixed distance from each other via the sacrificial layer 2.

(processing steps)

Next, the surface (back surface) on the opposite side to the functional surface 31 of the semiconductor wafer 3 fixed to the support substrate 1 via the sacrificial layer 2 is processed (third step).

The processing of the semiconductor wafer 3 is not particularly limited. For example, the back surface of the semiconductor wafer 3 shown in FIG. 1(c) is ground and polished. Further, a through hole is formed in the semiconductor wafer 3 for release. The back surface of the semiconductor wafer 3 is etched, lithographically, and coated on the back surface of the semiconductor wafer 3 by a stress, vapor deposition, or the like.

Here, in the present embodiment, the sacrificial layer forming step and the bonding are as described above. As described in the step, the sacrificial layer 2 is formed with a uniform film thickness, and the sacrificial layer 2 is bonded to the functional surface 31 composed of the uneven surface to follow the uneven shape. Thereby, the semiconductor wafer 3 is bonded to the support substrate 1 via the sacrificial layer 2 while maintaining a fixed interval between the semiconductor wafer 3 and the support substrate 1. Therefore, for example, when the semiconductor wafer 3 is bonded to the support substrate 1 via a sacrificial layer having a non-uniform film thickness, when the surface opposite to the functional surface 31 is ground and polished, there is a sacrifice of the sacrificial layer 2 The thickness of the semiconductor wafer 3 is not uniform due to the uneven film thickness. However, as described above, the distance between the semiconductor wafer 3 and the support substrate 1 is maintained at a constant interval, and the thickness is not surely prevented. Qi Yi.

(Active energy ray irradiation step)

Next, as shown in FIG. 1(d), the sacrificial layer 2 is irradiated with an active energy ray (fourth step).

Thereby, the sacrificial layer (resin composition) 2 contains a resin component which lowers the thermal decomposition temperature due to the presence of an acid or a base, and an active agent which generates an acid or a base due to irradiation of an active energy ray with a temporary fixing agent. When an active agent is contained in the temporary fixing agent (resin composition), an active substance such as an acid or a base is generated from the active agent. As a result, the thermal decomposition temperature of the resin component is lowered by the action of the active material.

Therefore, the active energy ray is irradiated to the sacrificial layer 2 before the heating of the sacrificial layer 2 in the next step (disengagement step), and the heating temperature at the time of heating the sacrificial layer 2 or the heating time can be reduced. Therefore, the heating can be carried out under milder conditions.

Further, in the present embodiment, the conditions for irradiating the active energy ray are set to an appropriate range, but this point will be described in detail later.

(out of step)

Next, as shown in FIG. 1(e), the resin component is heated by heating the sacrificial layer 2 After decomposing and lowering the molecular weight, the sacrificial layer 2 is melted or vaporized, and then the semiconductor wafer 3 is detached from the support substrate 1 (the fifth step).

Here, in the present specification, the detachment refers to an operation of peeling off the semiconductor wafer 3 from the support substrate 1, and the sacrificial layer 2 is not in a molten state or vaporized. For example, the operation is performed, for example, to make the semiconductor wafer 3 a method of detaching the surface of the support substrate 1 in a perpendicular direction or a method of sliding the semiconductor wafer 3 in a horizontal direction with respect to the surface of the support substrate 1, or as shown in FIG. 1(f) A method in which the semiconductor wafer 3 is floated from the support substrate 1 from one end side of the semiconductor wafer 3, and the like.

Further, when the sacrificial layer 2 is vaporized by the above-described heating step, since the sacrificial layer 2 has been removed from between the semiconductor wafer 3 and the support substrate 1, the semiconductor crystal can be more easily performed from the support substrate 1. Circle 3 is detached.

In the present embodiment, the temperature at which the sacrificial layer 2 is heated is appropriately set in accordance with the irradiation amount of the active energy ray described in the above-described step (active energy ray irradiation step), but this point will be described in detail later.

(washing step)

Next, in the detaching step, when the sacrificial layer 2 is heated to heat the sacrificial layer 2, or a part of the vaporized sacrificial layer 2 remains, the remaining functional surface 31 of the semiconductor wafer 3 remains as needed. Sacrifice layer 2.

That is, the residue of the sacrificial layer 2 remaining on the functional surface 31 is removed.

The method for removing the residue is not particularly limited, and examples thereof include a plasma treatment, a chemical liquid immersion treatment, a polishing treatment, and a heat treatment.

Further, in the present embodiment, the sacrificial layer 2 is formed on the support substrate 1 in the sacrificial layer forming step. However, the sacrificial layer 2 may be formed on both the support substrate 1 and the semiconductor wafer 3 in this case. The formation of the sacrificial layer 2 on the support substrate 1 can be omitted and the selectivity A sacrificial layer 2 is formed on the semiconductor wafer 3.

As described above, the semiconductor wafer 3 is processed on the back surface of the semiconductor wafer 3. However, in the present embodiment, in order to easily separate the semiconductor wafer 3 from the support substrate 1 under mild conditions, the active energy ray is required. The irradiation conditions for irradiating the sacrificial layer 2 with the active energy ray in the irradiation step are set within an appropriate range.

The inventors of the present invention paid attention to this point and worked hard to find out that the irradiation amount of the active energy ray in the active energy ray irradiation step was set to E [J/cm ² ], and the average thickness of the sacrificial layer 2 was set to M [cm]. When the temperature of the heating sacrificial layer 2 is set to T [° C.] and the time for heating the sacrificial layer 2 is set to t [minute], the relationship between the following formula 1 and the following formula 3 is satisfied by setting. The semiconductor wafer 3 can be easily detached from the support substrate 1.

Log(T ² .t)≦-10 ^-4 . (E ² /M)+5.7.........Form 1

Log(T ² .t)≧-10 ^-4 . (E ² /M)+3.8.........Form 2

3.3×10 ^-5 ≦E ² /M≦8.0×10 ⁵ .........3

By satisfying this relationship, an active material can be generated from an appropriate amount of the active agent contained in the sacrificial layer 2 to which the active energy ray is irradiated, and the temperature at which the resin component is thermally decomposed can be surely lowered by the action of the active material. In addition, by heating the resin component having such a thermal decomposition temperature under appropriate heating conditions (temperature and time) and melting or vaporizing the resin component, the semiconductor wafer 3 can be easily deteriorated and deteriorated without causing deterioration. The semiconductor wafer 3 is detached from the support substrate 1.

Here, by satisfying the relationship of the above formulas 1 to 3, the semiconductor wafer 3 can be easily separated from the support substrate 1, and the result of the investigation by the inventors of the present invention can be obtained.

That is, the relationship between the irradiation amount E of the active energy ray, the average thickness M of the sacrificial layer 2, the temperature T of the heating sacrificial layer 2, and the time t at which the sacrificial layer 2 is heated is examined. As a result, learn about T ² . The relationship between t and E ² /M determines whether or not the semiconductor wafer 3 can be separated from the boundary of the support substrate 1. Moreover, the inventor of the present invention further explored the result: when log(T ² .t) is the Y coordinate and E ² /M is the X coordinate, the relationship between the functions is obviously one time, so the semiconductor is obtained by the least square method. Whether or not the wafer 3 can be separated from the boundary of the support substrate 1 yields the relationship of the following formula 4. That is, the following formula 4 is such that when the position marked with ■ in FIG. 2 is reached, the semiconductor wafer 3 cannot be separated from the support substrate 1, and when it becomes the position of the mark in FIG. 2, the semiconductor wafer 3 can be detached from the support. The boundary of the substrate 1.

Log(T ² .t)=-10 ^-4 . (E ² /M)+3.8.........Form 4

Therefore, if the irradiation amount E of the active energy ray, the average thickness M of the sacrificial layer 2, the temperature T of heating the sacrificial layer 2, and the time t at which the sacrificial layer 2 is heated are set in the manner of satisfying the formula 2, the semiconductor wafer 3 can be made. When the support base material 1 is separated, the value of the Y coordinate, that is, the log (T ² .t) becomes too large, the heating conditions become too strict, and the semiconductor wafer 3 deteriorates and deteriorates. Therefore, for further discussion of the boundary that can avoid this point, it is understood that Equation 5 below is the boundary. According to this, it has been found that deterioration of the semiconductor wafer 3 and deterioration can be surely prevented or suppressed by satisfying Expression 1.

Log(T ² .t)=-10 ^-4 . (E ² /M)+5.7.........Form 5

Further, for the X coordinate (E ² /M), that is, the appropriate range of the irradiation amount E of the active energy ray and the average thickness M of the sacrificial layer 2, it is understood that the sacrificial layer 2 can be obtained by satisfying the formula 3. A sufficient amount of active material is generated, and the sacrificial layer 2 functions as a fixing agent for bonding the semiconductor wafer 3 and the support substrate 1 in the processing step.

Therefore, the inventors of the present invention have found that by satisfying the above formula (1) to the above formula (3), that is, setting the irradiation amount E of the active energy ray, the average thickness M of the sacrificial layer 2, and the temperature of heating the sacrificial layer 2, respectively. T and heating the sacrificial layer 2 for the time t to make the semiconductor wafer 3 easily detach from the support substrate 1 in the region of the oblique line in Fig. 2, completes the present invention.

In addition, the irradiation amount E of the active energy ray may be set to satisfy the above formula (1) to the above formula (3), but is preferably about 0.001 to 20 J/cm ^{2 and more} preferably about 0.1 to 10 J/cm ² . Thereby, a more appropriate amount of the active material can be generated in the sacrificial layer 2.

Further, the thickness M of the sacrificial layer 2 is preferably about 5 × 10 ^-4 to 3 × 10 ^-2 cm, more preferably about 1 × 10 ^-3 to 1 × 10 ^-2 cm. Thereby, the sacrificial layer 2 can ideally function as a fixing agent for bonding the semiconductor wafer 3 and the supporting substrate 1 in the processing step, and at the same time, can more reliably make the semiconductor wafer via the sacrificial layer 2 The spacing distance between the 3 and the support substrate 1 is maintained at a fixed size.

Furthermore, the conditions for heating the sacrificial layer 2, that is, the heating temperature T and the heating time t, are each about 60 to 400 ° C and about 1.67 × 10 ^-3 to 60 minutes, preferably about 100 to 300 ° C and about 1.0 ×. 10 ^-2 ~ 10 minutes is better. By setting the heating conditions of the sacrificial layer 2 within this range, it is possible to more reliably suppress or prevent deterioration and deterioration of the semiconductor wafer 3.

Further, in the present embodiment, the sacrificial layer 2 is selectively formed on the support substrate 1. However, the present invention is not limited thereto, and may be selectively formed on the semiconductor wafer 3 or on the support substrate 1 and the semiconductor wafer 3. Formed. However, according to the present embodiment, by selectively forming the support substrate 1, the time and trouble for forming the sacrificial layer 2 can be simplified, and the surface of the sacrificial layer 2 on which the support substrate 1 is formed can be formed by a flat surface. Therefore, it is also possible to obtain an effect of surely providing the sacrificial layer 2 with a uniform film thickness.

In the present embodiment, the case where the semiconductor wafer 3 is used as the substrate is described as an example. However, the present invention is not limited to this, and a wiring board, a circuit board, or the like may be used.

Although the method of processing the substrate according to the second embodiment of the present invention has been described above based on the embodiment of the drawings, the present invention is not limited thereto.

For example, each constituent material contained in the temporary fixing agent used in the method for processing a substrate of the present invention may be replaced with any of the same functions, or may be added in any configuration.

Moreover, the method of processing the substrate of the present invention may be added as needed.

[Examples]

Next, a specific embodiment corresponding to the first embodiment of the present invention will be described.

1. Preparation of temporary fixative

First, temporary fixing agents of Examples 1A to 2A and Comparative Example A shown below were prepared.

[Example 1A] <Synthesis of Polycarbonate>

Isosorbide 102.01 g (0.698 mol), diphenyl carbonate 149.33 g (0.698 mol), and cesium carbonate 0.0023 g (6.98 x 10 ^-6 mol) were weighed separately, and then placed in a reaction vessel.

In the first step of the reaction, the reaction vessel was immersed in a heating bath heated to 120 ° C under a nitrogen atmosphere and stirred to dissolve the raw material, and stirring was continued for 2 hours.

Next, in the second step of the reaction, the inside of the reaction vessel was depressurized to 10 kPa, and stirring was continued at 120 ° C for 1 hour.

Next, in the third step of the reaction, the inside of the reaction vessel was depressurized to 0.5 kPa or less, and stirring was continued at 120 ° C for 1.5 hours.

Next, in the fourth step of the reaction, the pressure in the reaction vessel was reduced to 0.5 kPa or less, and it took about 30 minutes to maintain the temperature of the heating vessel at a temperature of 180 ° C, and the mixture was continuously stirred at 180 ° C for 1.5 hours.

Further, the phenol produced in the second to fourth steps of the above reaction was distilled off to the outside of the reaction vessel.

Further, after the pressure in the reaction vessel was returned to normal pressure, 1200 mL of γ-butyrolactone was added to dissolve the product.

Next, a solution in which the product was dissolved was added dropwise while stirring a solution of 12.0 L of a mixed solution of isopropyl alcohol/water = 9/1 (v/v).

Next, the precipitate which precipitated was recovered by suction filtration, and the recovered precipitate was washed with 4.0 L of a mixed solution of isopropyl alcohol/water = 9/1 (v/v), and recovered by suction filtration.

The recovered precipitate was dried in a vacuum dryer at 80 ° C for 18 hours, whereby 123.15 g of a powder of the isosorbide-type polycarbonate represented by the above chemical formula (2B) was obtained.

<Preparation of temporary fixative>

100 g of the isosorbide-type polycarbonate obtained, 5 g of an actinic acid photoacid generator (manufactured by Bruestar Silicones, model "Rhodorsil Photoinitiator 2074"), and a thioxanthone compound as a sensitizer (Lambson Corporation) 1.3 g of the model "SPEEDCURE CPTX" was dissolved in 193.4 g of N-methyl-2-pyrrolidone to prepare a temporary fixing agent having a resin component concentration of 33.3% by weight.

[Example 2A] <Synthesis of Polycarbonate>

Isosorbide 51.01g (0.349 moles), 1,4-cyclohexanedimethanol 50.30g (0.349 moles), diphenyl carbonate 149.33g (0.698 moles), and cesium carbonate 0.0023g (6.98×) were weighed separately. 10 ^-6 moles, after which they are placed in the reaction vessel.

In the first step of the reaction, the reaction vessel was immersed in a heating bath heated to 120 ° C under a nitrogen atmosphere and stirred to dissolve the raw material, and stirring was continued for 2 hours.

Next, in the second step of the reaction, the inside of the reaction vessel was depressurized to 10 kPa, and stirring was continued at 120 ° C for 1 hour.

Next, in the third step of the reaction, the inside of the reaction vessel was depressurized to 0.5 kPa or less, and stirring was continued at 120 ° C for 1.5 hours.

Next, in the fourth step of the reaction, the pressure in the reaction vessel was reduced to 0.5 kPa or less, and the state was maintained. The temperature of the heating vessel was raised to 180 ° C in about 30 minutes, and the mixture was continuously stirred at 180 ° C for 1.5 hours.

Further, the phenol produced in the second to fourth steps of the above reaction was distilled off to the outside of the reaction vessel.

Further, after the pressure in the reaction vessel was returned to normal pressure, 1200 mL of γ-butyrolactone was added to dissolve the product.

Next, a solution in which the product was dissolved was added dropwise while stirring a solution of 12.0 L of a mixed solution of isopropyl alcohol/water = 9/1 (v/v).

Next, the precipitate which precipitated was recovered by suction filtration, and the recovered precipitate was washed with 4.0 L of a mixed solution of isopropyl alcohol/water = 9/1 (v/v), and recovered by suction filtration.

The recovered precipitate was dried in a vacuum dryer at 80 ° C for 18 hours, whereby 108.72 g of the polycarbonate of the above formula (2C) was obtained.

<Preparation of temporary fixative>

100 g of the obtained polycarbonate, a bismuth photoacid generator as an active agent (manufactured by Bruestar Silicones, model "Rhodorsil Photoinitiator" 2078") 5g, a thioxanthone-based compound ("SPEEDCURE CPTX", manufactured by Lambson Co., Ltd.), which is a sensitizer, was dissolved in N-methyl-2-pyrrolidone (193.4 g) to prepare a resin component concentration of 33.3% by weight. Temporary fixative.

[Comparative Example A] <Synthesis of 5-N-decyl-decene-addition polymer>

Ethyl acetate (430 g), cyclohexane (890 g), 5-decylpentene (223 g, 0.95 mol) were introduced into a sufficiently dried reaction vessel, and dry nitrogen gas was passed through the system at 40 ° C. In minutes, remove dissolved oxygen. A solution of 1.33 g of bis(toluene)bis(perfluorophenyl)nickel (0.275 m mole) dissolved in 12 g of ethyl acetate was added to the reaction system, and the above system was heated from 20 ° C to 35 ° C for 15 minutes. The reaction system was stirred for 3 hours while maintaining this temperature.

After cooling the reaction system to room temperature, 26 g of glacial acetic acid was dissolved in about 1500 g of pure water to which 49 g of 30% hydrogen peroxide water was added, and this was added to the reaction system, and the reaction was stirred at 50 ° C for 5 hours. After that, the stirring was stopped and the separated aqueous layer was removed. The remaining organic layer was washed by adding - stirring to remove 220 g of methanol and 220 g of isopropanol. Further, 510 g of cyclohexane and 290 g of ethyl acetate were added to the reaction system, and the mixture was uniformly dissolved. Then, 156 g of methanol and 167 g of isopropyl alcohol were mixed, and the mixture was washed by adding ~ stirring to remove the washing. Times.

Add 180 mL of cyclohexane to the organic layer after washing to dissolve the reaction system evenly, and then add 670g. And, the cyclohexane is evaporated and removed under reduced pressure by a rotary evaporator, thereby taking 35% The 5-nonylnordecene addition polymer was obtained in the form of a solution, yield: 543 g. This solution was used as a temporary fixative.

2. Evaluation 2-1. Determination of melt viscosity before exposure

The temporary fixing agents of the above-prepared Examples 1A to 2A and Comparative Example A were coated on a ruthenium wafer under the conditions of a film having a thickness of 50 μm, and were exposed to 120 ° C in the atmosphere. Soft bake for 5 minutes.

Next, the temporary fixing agent was applied again on the crucible wafer under the same conditions, and soft baked in the air at 120 ° C for 5 minutes, followed by hard baking in the atmosphere at 220 ° C for 5 minutes.

Then, the film of the temporary fixing agent was cut out into a 30×30 mm slit by a cutter, and immersed in a 2% hydrofluoric acid solution, thereby peeling off the temporary fixing agent from the crucible wafer, and preparing a measurement sample having a thickness of 100 μm (temporary fixing agent) Floor). The prepared measurement sample was washed with pure water and dried at 60 ° C / 10 hr.

Using the obtained measurement sample, a viscoelasticity measuring device (manufactured by HAAKE Co., Ltd., Rheo stress RS150) was used, and the temperature was raised at a frequency of 1 Hz from 25 ° C at a rate of 10 ° C / minute, and the melt viscosity was measured at a fixed shear rate. The melt viscosity of the gas atmosphere at 180 ° C was taken as the measured value. The results are shown in Table 1.

2-2. Determination of melt viscosity after exposure

A temporary fixing agent layer was formed on the crucible wafer in the same manner as in the above 2-1, and the temporary fixing agent was peeled off from the crucible wafer, and then the i-line was irradiated with an ultrahigh pressure mercury lamp to be 2000 mJ/cm ² (i-line conversion). Then, using a viscoelasticity measuring device (manufactured by HAAKE Co., Ltd., Rheo stress RS150), the temperature was raised from 25 ° C at a rate of 10 ° C / min at a frequency of 1 Hz, and the melt viscosity was measured at a fixed shear rate, and the gas atmosphere was at 180 ° C. The melt viscosity is taken as the measured value. The results are shown in Table 1 below.

2-3. Detachment of the substrate from the support substrate

The temporary fixing agents prepared in the above Examples 1A and 2A and Comparative Example A were each applied to the glass by a spin coating method, and soft baked in the air at 120 ° C for 5 minutes. Next, the temporary fixing agent prepared in Examples 1A, 2A and Comparative Example A was applied to the glass under the same conditions again, and soft baked in the air at 120 ° C for 5 minutes, and then in the atmosphere. Hard baking was carried out under the conditions of 220 ° C × 5 minutes to obtain a temporary fixing agent layer having a thickness of 50 μm. Thereafter, a semiconductor wafer was placed on the temporary fixing agent layer, and the semiconductor wafer and the glass were placed at 240 ° C (Example 1A, Comparative Example A) or 220 ° C (Example 2A), 10 kN, 5 minutes via a temporary fixing agent. The conditions are fixed.

Next, the semiconductor wafer was polished, and then the laminate of the semiconductor wafer and the glass was heated in the air at 230 ° C for 10 minutes. After that, the semiconductor wafer and the glass laminate were irradiated with an i-line from a glass side at a condition of 2000 mJ/cm ² (i-line conversion), and then sandwiched between hot and cold plates at 180° C., and vacuum-adsorbed. The semiconductor wafer was slid at a speed of 2.0 mm/sec to detach from the glass. Thereafter, the semiconductor wafer and the glass were immersed in γ-butyrolactone in a shaking state for 5 minutes to remove the residue of the temporary fixing agent on the semiconductor wafer and the glass.

As a result, in the first embodiment and the second embodiment, the semiconductor wafer can be detached without damaging the semiconductor wafer, and the residue of the temporary fixing agent can be removed by immersing in γ-butyrolactone. However, in Comparative Example A, the semiconductor wafer could not be detached under these conditions.

Next, a specific embodiment corresponding to the second embodiment of the present invention will be described.

[Example 1B] <Synthesis of Polycarbonate>

Isosorbide 102.01 g (0.698 mol), diphenyl carbonate 149.33 g (0.698 mol), and cesium carbonate 0.0023 g (6.98 x 10 ^-6 mol) were weighed separately, and then placed in a reaction vessel.

In the first step of the reaction, the reaction vessel was immersed in a heating bath heated to 120 ° C under a nitrogen atmosphere and stirred to dissolve the raw material, and stirring was continued for 2 hours.

Next, in the second step of the reaction, the inside of the reaction vessel was depressurized to 10 kPa, and stirring was continued at 120 ° C for 1 hour.

Next, in the third step of the reaction, the inside of the reaction vessel was depressurized to 0.5 kPa or less, and stirring was continued at 120 ° C for 1.5 hours.

Next, in the fourth step of the reaction, the pressure in the reaction vessel was reduced to 0.5 kPa or less, and the state was maintained. The temperature of the heating vessel was raised to 180 ° C in about 30 minutes, and the mixture was continuously stirred at 180 ° C for 1.5 hours.

Further, the phenol produced in the second to fourth steps of the above reaction was distilled off to the outside of the reaction vessel.

Further, after the pressure in the reaction vessel was returned to normal pressure, 1200 mL of γ-butyrolactone was added to dissolve the product.

Next, a solution in which the product was dissolved was added dropwise while stirring a solution of 12.0 L of a mixed solution of isopropyl alcohol/water = 9/1 (v/v).

Next, the precipitate which precipitated was recovered by suction filtration, and the recovered precipitate was washed with 4.0 L of a mixed solution of isopropyl alcohol/water = 9/1 (v/v), and recovered by suction filtration.

The recovered precipitate was dried in a vacuum dryer at 80 ° C for 18 hours, whereby 123.15 g of a powder of the isosorbide-type polycarbonate represented by the above chemical formula (2A) was obtained.

<Preparation of temporary fixative>

100.0 g of the isosorbide-type polycarbonate obtained and 2.0 g of GSID26-1 (manufactured by BASF JAPAN Co., Ltd.) as an active agent (photoacid generator) were dissolved in γ-butyrolactone 198.0 g to prepare a resin component concentration of 33% by weight. % temporary fixative.

<Wab Bonding Sample Preparation>

The temporary fixing agent prepared above was applied by spin coating to 200 mm The glass wafer was soft baked in the air at 120 ° C for 5 minutes and at 220 ° C for 5 minutes to obtain a temporary fixing agent layer (film) having a thickness of 50 μm. Thereafter, a bare crucible wafer of 8 inches was placed on the temporary fixing agent layer, and the semiconductor wafer and the glass were fixed by a temporary fixing agent using a substrate bonder (model SB-8e, manufactured by SUSS Microtec Co., Ltd.) (gas atmosphere) : 10 ^-2 mbar, temperature: 220 ° C, load: 10 kN, time: 5 minutes).

<Wab Peel Test>

The laminate of the glass wafer and the tantalum wafer using the temporary fixing agent prepared above was irradiated with an i-line from a glass side at a condition of 200 mJ/cm ² (i-line conversion), and a hot plate of 240 ° C was applied up and down. After clamping and vacuum adsorption, it takes 1 minute to slide the semiconductor wafer to detach the semiconductor wafer from the glass. Further, the residue on the wafer and the glass can be removed by immersing the γ-butyrolactone in a state of shaking for 5 minutes.

[Example 2B] <Wab Peel Test>

The laminate of the glass wafer and the tantalum wafer obtained in Example 1B was irradiated with an i-line from a glass side at a condition of 200 mJ/cm ² (i-line conversion), and sandwiched between hot plates of 230 ° C on the upper and lower sides, and After vacuum adsorption, it takes 9 minutes to slide the crucible wafer, thereby separating the glass. Further, the residue on the semiconductor wafer and the glass can be removed by immersing the γ-butyrolactone in a state of shaking for 5 minutes.

[Example 3B] <Synthesis of Polycarbonate>

1,3-cyclohexanediol 30.43g (0.262 moles), inward (endo), inward (endo)-2,3-norbornane dimethanol 23.02g (0.147 moles), diphenyl carbonate 84.63 g (0.395 mol), lithium carbonate 0.0163 g (0.0021 mol) was placed in the reaction vessel. In the first step of the reaction, the reaction vessel is immersed and heated under a nitrogen atmosphere. The heating bath was stirred at 120 ° C to dissolve the raw materials and stirring was continued for 2 hours. In the second step of the reaction, the inside of the reaction vessel was depressurized to 10 kPa, and stirring was continued at 120 ° C for 1 hour. In the third step of the reaction, the inside of the reaction vessel was depressurized to 0.5 kPa or less, and stirring was continued at 120 ° C for 1.5 hours. In the fourth step of the reaction, the pressure in the reaction vessel was reduced to 0.5 kPa or less, and the state was maintained. The temperature of the heating vessel was raised to 180 ° C in about 30 minutes, and stirring was continued at 180 ° C for 1 hour. The phenol produced in the second to fourth steps of the reaction is distilled off to the outside of the reaction vessel.

After the pressure in the reaction vessel was returned to normal pressure, 600 ml of tetrahydrofuran was added to dissolve the product. The solution in which the product was dissolved was added dropwise while stirring a mixed solution of isopropyl alcohol/water = 9/1 (v/v) in 6.0 L. The precipitate precipitated was recovered by suction filtration, and the recovered precipitate was isopropanol/water = 9/1 (v/v). After the mixed solution was washed with 3.0 L, it was recovered by suction filtration.

The recovered precipitate was dried in a vacuum dryer at 60 ° C for 18 hours to obtain 49.27 g of a polycarbonate powder.

<Preparation of temporary fixing materials>

100.0 g of the obtained resin and 2.0 g of GSID26-1 (manufactured by BASF JAPAN Co., Ltd.) as an active agent (photoacid generator) were dissolved in 198.0 g of γ-butyrolactone to prepare a temporary fixing agent having a resin component concentration of 33% by weight.

<Wab Bonding Sample Preparation>

The temporary fixing agent prepared above was spin-coated on 200 mm by spin coating The glass wafer was soft baked in the air at 120 ° C for 5 minutes and at 220 ° C for 5 minutes to obtain a temporary fixing agent layer having a thickness of 15 μm. Then, a bare boring wafer of 8 Å was placed on the temporary fixing agent layer, and the semiconductor wafer and the glass substrate fixing device (Model SB-8e, manufactured by SUSS Microtec Co., Ltd.) were fixed via a temporary fixing agent (gas atmosphere: 10) ^-2 mbar, temperature: 220 ° C, load: 10 kN, time: 5 minutes).

<Wab Peel Test>

The laminate of the glass wafer and the tantalum wafer using the temporary fixing agent prepared above was irradiated with i-line from the glass side at a temperature of 1140 mJ/cm ² (i-line conversion), and a hot plate of 130 ° C was applied up and down. After clamping and vacuum adsorption, it takes 6.5 minutes to slide the semiconductor wafer to detach the germanium wafer from the glass. Further, the residue on the wafer and the glass can be removed by immersing the γ-butyrolactone in a state of shaking for 5 minutes.

[Example 4B] <Preparation of temporary fixing materials>

100.0 g of a polypropylene carbonate QPAC40 (manufactured by EMPOWER MATERIALS Co., Ltd.), Rhodorsil Photoinitiator 2074 (Rhoodorsil Photoinitiator 2074, manufactured by Rhodia JAPAN Co., Ltd.) of an active agent (photoacid generator), 5 g of a sensitizer, and 1-chloro-4-prop. 1.5 g of oxythioxanthone (SPEEDCURE CPTX (trade name) manufactured by Lambson Co., Ltd.) was dissolved in 340.0 g of γ-butyrolactone to prepare a temporary fixing agent having a resin component concentration of 22% by weight.

<Wab Bonding Sample Preparation>

The temporary fixing agent prepared above was spin-coated on 200 mm by spin coating The glass wafer was soft baked in the air at 120 ° C for 5 minutes and at 220 ° C for 5 minutes to obtain a temporary fixing agent layer having a thickness of 50 μm. Then, a bare boring wafer of 8 Å was placed on the temporary fixing agent layer, and the semiconductor wafer and the glass substrate fixing device (Model SB-8e, manufactured by SUSS Microtec Co., Ltd.) were fixed via a temporary fixing agent (gas atmosphere: 10) ^-2 mbar, temperature: 160 ° C, load: 10 kN, time: 5 minutes).

<Wab Peel Test>

The laminate of the glass wafer and the tantalum wafer using the temporary fixing agent prepared above was irradiated with an i-line from a glass side at a condition of 1000 mJ/cm ² (i-line conversion), and a hot plate of 140 ° C was applied up and down. After clamping and vacuum adsorption, it takes 1 minute to slide the semiconductor wafer to detach the wafer from the glass. Further, the residue on the wafer and the glass can be removed by immersing the γ-butyrolactone in a state of shaking for 5 minutes.

[Comparative Example 1B] <Wab Bonding Sample Preparation>

The temporary fixing agent prepared in Example 4B was spin-coated on 200 mm by spin coating. The glass wafer was soft baked in the air at 120 ° C for 5 minutes and at 220 ° C for 5 minutes to obtain a temporary fixing agent layer having a thickness of 15 μm. Then, a bare boring wafer of 8 Å was placed on the temporary fixing agent layer, and the semiconductor wafer and the glass substrate fixing device (Model SB-8e, manufactured by SUSS Microtec Co., Ltd.) were fixed via a temporary fixing agent (gas atmosphere: 10) ^-2 mbar, temperature: 160 ° C, load: 10 kN, time: 5 minutes).

<Wab Peel Test>

The laminate of the glass wafer and the tantalum wafer using the temporary fixing agent prepared above was irradiated with an i-line from the glass side at a temperature of 1140 mJ/cm ² (i-line conversion), and a hot plate of 100 ° C was applied up and down. After clamping and vacuum adsorption, it took 20 seconds to slide the semiconductor wafer, but the load during sliding was overloaded and could not be detached from the glass.

[induction]

The evaluation results of Examples 1B to 4B and Comparative Example 1B are shown in Table 2 below.

As shown in Table 2, in each of the examples, the relationship between the irradiation amount E of the active energy ray, the average thickness M of the temporary fixing agent layer, the temperature T of the heating temporary fixing agent layer, and the time t of heating the temporary fixing agent layer satisfies the above formula 1 The relationship of Equation 3 enables the semiconductor wafer to be easily detached from the glass wafer.

On the other hand, in Comparative Example 1B, since the above parameters did not satisfy the relationship of Formulas 1 to 3 above, the semiconductor wafer could not be detached from the glass wafer.

[Industrial use]

According to the temporary fixing agent of the first embodiment of the present invention, the melting temperature is lowered by heating the active energy ray after processing the substrate. Therefore, the substrate can be fixed to the support substrate during processing of the substrate, and the substrate can be detached from the support substrate at a low heating temperature when the substrate is detached, so that damage to the substrate can be reduced while high precision is achieved. The processing can exert the effect that the substrate can be easily separated from the supporting substrate after processing at a low heating temperature.

Further, according to the method for processing a substrate according to the second embodiment of the present invention, the substrate can be processed in a state in which the substrate is firmly fixed to the support substrate via a film formed using a temporary fixing agent. Further, by appropriately setting the irradiation amount of the active energy ray irradiated to the film after processing of the substrate and the heating condition when the substrate is detached from the support substrate, the substrate can be easily detached from the support substrate. Effect.

Therefore, the present invention can be suitably applied to a temporary fixing agent used for temporarily fixing the substrate to a supporting substrate when processing a substrate, and a method of processing a substrate using the temporary fixing agent.

1‧‧‧Support substrate

2‧‧‧ sacrificial layer (film)

3‧‧‧Semiconductor wafer (substrate)

31‧‧‧ functional surface

1(a) to 1(f) are longitudinal cross-sectional views for explaining a processing step of processing a semiconductor wafer using the temporary fixing agent of the present invention.

Figure 2 is a graph showing the relationship between the amount of irradiation of the active energy ray, the average thickness of the film, the temperature of the heated film, and the time of heating the film.

1‧‧‧Support substrate

2‧‧‧ sacrificial layer (film)

3‧‧‧Semiconductor wafer (substrate)

31‧‧‧ functional surface

Claims (19)

A temporary fixing agent for temporarily fixing the substrate to a supporting substrate for processing a substrate, and after processing the substrate, heating the substrate by irradiation of an active energy ray to remove the substrate from the supporting substrate The material is used for detachment; characterized in that: after the active energy ray is irradiated, the melt viscosity at 180 ° C is 0.01 to 100 Pa ‧ s; and is composed of a resin composition containing the following components: melting in the presence of an acid or a base due to heating a resin component having a reduced viscosity; and an active agent which generates an acid or a base due to the irradiation of the active energy ray. The temporary fixing agent of the first aspect of the invention, wherein the irradiation of the active energy ray is performed by irradiating light having a wavelength of 365 nm at 2000 mJ/cm ² . The temporary fixing agent according to claim 1 or 2, wherein the melt viscosity at 180 ° C is 100 to 10000 Pa s before the irradiation of the active energy ray. The temporary fixing agent according to claim 1 or 2, wherein the melt viscosity at 180 ° C before the irradiation of the active energy ray is set to A [Pa ‧ s], and the active energy ray is irradiated and melted at 180 ° C When the viscosity is set to B [Pa ‧ s], the relationship of A/B is 10 to 10000 is satisfied. The temporary fixing agent according to claim 1 or 2, wherein the temporary fixing agent is brought into a molten state by heating after the irradiation of the active energy ray, thereby detaching the substrate from the supporting substrate. The temporary fixing agent according to claim 1 or 2, wherein the 50% weight loss temperature is 260 ° C or higher after the irradiation of the active energy ray. The temporary fixing agent of claim 6, wherein the resin component is a polycarbonate resin. The temporary fixing agent of the seventh aspect of the invention, wherein the polycarbonate resin is composed of at least two annular bodies in the carbonate constituent unit. A method for processing a substrate, comprising the steps of: forming a film comprising a temporary fixing agent according to any one of claims 1 to 8 in the substrate and the supporting substrate At least one of them; In the second step, the substrate is bonded to the support substrate via the film; in the third step, the surface of the substrate opposite to the support substrate is processed; and the fourth step is After irradiating the active energy ray, the film is heated to be in a molten state to thereby detach the substrate from the support substrate, and in the fifth step, the film remaining on the substrate is washed. The method for processing a substrate according to claim 9, wherein the support substrate is translucent. A method for processing a substrate, comprising the steps of: a first step of temporarily fixing a resin composition comprising a resin component which is melted or vaporized by thermal decomposition by heating, for a substrate and a support base At least one of the materials is supplied to be dried to form a film; in the second step, the substrate is bonded to the support substrate via the film; and in the third step, the substrate is bonded to the support substrate Processing the surface on the opposite side; in the fourth step, irradiating the film with an active energy ray; and in the fifth step, heating the film to thermally decompose the resin component, thereby detaching the substrate from the support substrate; In the fourth step, when the irradiation amount of the active energy ray is set to E [J/cm ² ], the average thickness of the film is set to M [cm], and in the fifth step, the temperature of heating the film is set to T[°C], when the time for heating the film is t [minute], the settings are such that the relationship of the following formula 1 to the following formula 3 is satisfied: log (T ² ‧ t) ≦ -10 ^-4 ‧ (E ² / M)+5.7‧‧‧Form 1 log(T ² ‧t)≧-10 ^-4 ‧(E ² /M)+3.8‧‧‧Formula 2 3.3×10 ^-5 ≦E ² /M≦8.0× 10 ⁵ ‧‧‧Form 3. The method for processing a substrate according to claim 11, wherein the irradiation amount E of the active energy ray is 0.001 to 20 J/cm ² . The method for processing a substrate according to claim 11 or 12, wherein the film has a thickness M of 5 × 10 ^-4 to 3 × 10 ^-2 cm. The method for processing a substrate according to claim 11 or 12, wherein the temperature T of the film is heated to 60 to 400 °C. The method for processing a substrate according to claim 11 or 12, wherein the time t for heating the film is 1.67 × 10 ^-3 to 60 minutes. The method for processing a substrate according to claim 11 or 12, wherein the film is irradiated with an active energy ray in the fourth step, so that the temperature at which the resin component is thermally decomposed in the fifth step is lowered. The method for processing a substrate according to claim 16, wherein the temperature of the thermal decomposition of the resin component in the presence of an acid or a base is lowered, and the resin composition further comprises irradiation of the active energy ray. An active agent that produces an acid or a base. The method for processing a substrate according to claim 17, wherein the active agent is contained in the resin composition in an amount of 0.01 to 50% by weight based on the resin component. The method for processing a substrate according to claim 11 or 12, wherein in the first step, the temporary fixing agent is selectively supplied to the substrate and the supporting substrate in the supporting substrate to form the film. .