WO2010147102A1 - 半導体ウェハの仮固定剤及びそれを用いた半導体装置の製造方法 - Google Patents
半導体ウェハの仮固定剤及びそれを用いた半導体装置の製造方法 Download PDFInfo
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- WO2010147102A1 WO2010147102A1 PCT/JP2010/060080 JP2010060080W WO2010147102A1 WO 2010147102 A1 WO2010147102 A1 WO 2010147102A1 JP 2010060080 W JP2010060080 W JP 2010060080W WO 2010147102 A1 WO2010147102 A1 WO 2010147102A1
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- semiconductor wafer
- fixing agent
- temporary fixing
- resin
- resin component
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
- H01L2221/68386—Separation by peeling
Definitions
- the present invention relates to a semiconductor wafer temporary fixing agent for temporarily fixing a semiconductor wafer when the semiconductor wafer is processed, and a semiconductor device manufacturing method using the same.
- a via hole or film is formed with a BG tape attached, and the temperature at that time reaches about 150 ° C., and the BG tape is formed. Will increase the adhesive strength. Further, the adhesive layer of the BG tape is eroded by the plating chemicals for film formation, and peeling may occur.
- fragile wafers typified by compound semiconductors may be damaged by mechanical grinding, so they are thinned by etching.
- this etching there is no particular problem as long as the etching amount is for the purpose of removing stress.
- the BG tape may be deteriorated by the etching chemical.
- a method of fixing to a supporting substrate having a smooth surface via a fixing material is adopted.
- a method using a supporting substrate Is preferably applied.
- the fixing material to the supporting base material As the fixing material to the supporting base material, a fixing material that is softened at a high temperature to facilitate the removal of the wafer and a fixing material that is dissolved by a specific chemical solution have been proposed.
- such materials are poor in handling, and it is necessary to wash the fixing material remaining inside the semiconductor wafer or the apparatus with a chemical solution or the like after detachment.
- the thinned wafer may not be able to withstand and may be damaged, but this possibility is expected to increase as the semiconductor wafer becomes thinner.
- Patent Documents 1 and 2 disclose polymers relating to the manufacture of semiconductor devices.
- An object of the present invention is to reduce damage to a semiconductor wafer, enable high-precision processing, and easily remove a semiconductor wafer after processing.
- An object of the present invention is to provide a method for manufacturing a semiconductor device that can be reduced, processed with high accuracy, and can shorten the time required for thermal decomposition.
- a semiconductor wafer is temporarily fixed to a support base material for processing the semiconductor wafer, and the semiconductor wafer is temporarily fixed to be used for detachment from the support base material by heating after processing.
- An agent is provided.
- the temporary fixing agent for the semiconductor wafer contains a resin component whose weight reduction temperature decreases by 50% after irradiation with active energy rays.
- the difference in 50% weight loss temperature before and after irradiation with the active energy ray is 20 to 100 ° C.
- a step of providing a temporary fixing agent for a semiconductor wafer containing a resin component whose weight reduction temperature decreases by 50% after irradiation with active energy rays on a supporting substrate, and the supporting base A step of placing a semiconductor wafer on a surface provided with a thin film on a material and bonding the semiconductor wafer to the thin film; a step of processing the semiconductor wafer; and a step of irradiating the thin film with active energy rays And a step of heating the thin film to detach the semiconductor wafer from the support substrate.
- the temporary fixing agent for a semiconductor wafer according to the present invention has the effect of reducing damage to the semiconductor wafer, enabling high-precision processing, and easy removal of the semiconductor wafer after processing.
- the semiconductor device manufacturing method using the temporary fixing agent for the semiconductor wafer has the effects of reducing damage to the semiconductor wafer, enabling highly accurate processing, and reducing the time required for thermal decomposition. .
- the 50% weight loss temperature before and after exposure means a temperature at which 50% weight is lost.
- 5% weight loss temperature and 95% weight loss temperature mean temperatures at which 5% and 95% weight are lost, respectively.
- the active energy ray means an electron beam containing ultraviolet rays, visible rays, infrared rays or the like.
- the type of the active energy ray does not require a special device and is simple, and therefore, the active energy ray is preferably ultraviolet or visible light.
- the temporary fixing agent for a semiconductor wafer according to the present embodiment is used for temporarily fixing a semiconductor wafer to a supporting base material in order to process the semiconductor wafer, and for removing the semiconductor wafer from the supporting base material by heating after processing.
- the temporary fixing agent to be used is a semiconductor wafer temporary fixing agent containing a resin component whose temperature decreases by 50% in weight after irradiation with active energy rays.
- the semiconductor wafer temporary fixing agent having the above-described structure includes a resin component whose weight reduction temperature is reduced by 50% by irradiation with active energy rays, the thermal decomposition temperature of the temporary fixing agent is reduced by irradiation with active energy rays.
- the semiconductor wafer can be easily detached after processing, and the temporary fixing agent hardly remains on the semiconductor wafer.
- the surface can be formed as a thin film on a support substrate having a smooth surface and sufficient accuracy, there is an effect that the accuracy of processing such as polishing is high.
- the resin component has a 50% weight loss temperature difference of 20 to 100 ° C. before and after irradiation with active energy rays. According to this, the effect that the semiconductor wafer can be easily detached after the processing of the semiconductor wafer and the temporary fixing agent hardly remains on the semiconductor wafer can be further improved. Moreover, since the thermal decomposition temperature of the temporary fixing agent can be lowered by irradiating the active energy ray after processing the semiconductor wafer, the effect of preventing damage due to the thermal history of the processed semiconductor wafer can be further improved. .
- the difference between the 95% weight reduction temperature and the 5% weight reduction temperature after irradiation with the active energy ray is as follows: 1 ° C ⁇ (95% weight loss temperature) ⁇ (5% weight loss temperature) ⁇ 200 ° C. It is preferable that According to this, the temperature range required for the thermal decomposition of the temporary fixing agent is narrow, the time required for the thermal decomposition can be shortened, and the effect of suppressing damage to the semiconductor wafer can be further improved. Further, it is possible to further improve the effect that the semiconductor wafer after processing is easily detached and the temporary fixing agent hardly remains on the semiconductor wafer.
- the temperature range which can be used stably can be ensured widely, it becomes possible to use for a various process process, temporarily fixing to a support base material.
- the surface can be formed as a thin film on a support substrate having a smooth surface and sufficient accuracy, the effect of high processing accuracy such as polishing can be further improved.
- the difference between the 95% weight reduction temperature and the 5% weight reduction temperature after irradiation with the active energy ray is: 80 ° C ⁇ (95% weight loss temperature) ⁇ (5% weight loss temperature) ⁇ 150 ° C. It is more preferable that According to this, the time required for thermal decomposition can be shortened, and the effect that a wide temperature range that can be stably used can be secured can be further improved.
- the temporary fixing agent includes an active agent that generates active species by applying energy by irradiation of the active energy ray, and the decomposition temperature of the resin component is lowered in the presence of the active species.
- resin component will not be specifically limited if a thermal decomposition temperature falls by irradiation of an active energy ray in presence of an activator.
- the main chain of the resin component is preferably thermally cut in the presence of the active species. This is because the thermal decomposition temperature of the temporary fixing agent can be effectively lowered, so that damage due to the thermal history of the semiconductor wafer can be effectively prevented, and the main chain of the resin component is thermally cut, resulting in a low molecular component. This is because the temporary fixing agent hardly remains on the semiconductor wafer.
- the resin component promotes the thermal ring closure reaction of the resin component in the presence of the active species. This is because the resin component is more easily thermally decomposed due to thermal ring closure of the resin component.
- the resin component preferably has an aliphatic quaternary carbon atom in the main chain. This is because the stability of the intermediate derived from the resin component when the resin component is thermally decomposed can be improved.
- the resin component has a hetero atom in the main chain. This is because the bonding electrons easily move, so that the thermal decomposition of the main chain and the thermal ring closure reaction are promoted, and the thermal decomposition of the resin component easily occurs. Moreover, it is preferable that the said resin component has the tertiary carbon atom adjacent to the hetero atom of the principal chain. This is because the stability of the intermediate derived from the resin component when the resin component is thermally decomposed, and further, the bond electrons are easily moved, and the thermal decomposition of the main chain and the thermal ring closure reaction are promoted.
- the hetero atom means an atom other than hydrogen and carbon.
- the resin component preferably has 5 to 7 repeating atoms in the main chain. This is because when the number of repeating atoms is 5 to 7, a cyclic structure (5 to 7-membered ring) is easily formed, and the resin component is easily decomposed thermally.
- the resin component preferably has an X—C ( ⁇ O) —Y structure in the main chain.
- X and Y are each an oxygen atom, a nitrogen atom, or a sulfur atom. This is because the bonding electrons easily move, so that the thermal decomposition of the main chain and the thermal ring closure reaction are promoted, and the thermal decomposition of the resin component easily occurs.
- the resin component has a primary or secondary carbon atom in the main chain, and a functional group is bonded to a side chain of the carbon atom. This is because the thermal decomposition of the main chain is promoted by the functional group.
- the functional group is preferably any one of a carbonyl group, a thiocarbonyl group, a formal group, and an acetal group. This is because thermal decomposition of the main chain is more effectively promoted.
- the resin component is any one of a polycarbonate resin, a polyester resin, a polyamide resin, a polyimide resin, a polyether resin, a polyurethane resin, and a (meth) acrylate resin. This is because the thermal decomposition temperature can be effectively lowered in the presence of an activator.
- the temporary fixing agent more preferably includes a photosensitive polycarbonate resin, vinyl resin, and (meth) acrylic resin.
- the photosensitive polycarbonate resin means a combination of the following polycarbonate resin and the activator.
- the polycarbonate resin is not particularly limited, and examples thereof include polypropylene carbonate, polyethylene carbonate, 1,2-polybutylene carbonate, 1,3-polybutylene carbonate, 1,4-polybutylene carbonate, cis-2,3- Polybutylene carbonate, trans-2,3-polybutylene carbonate, ⁇ , ⁇ -polyisobutylene carbonate, ⁇ , ⁇ -polyisobutylene carbonate, cis-1,2-polycyclobutylene carbonate, trans-1,2-polycyclobutylene Carbonate, cis-1,3-polycyclobutylene carbonate, trans-1,3-polycyclobutylene carbonate, polyhexene carbonate, polycyclopropene carbonate, polycyclohexene carbonate Poly (methylcyclohexene carbonate), poly (vinylcyclohexene carbonate), polydihydronaphthalene carbonate, polyhexahydrostyrene carbonate
- the vinyl resin is not particularly limited, and examples thereof include polymers of styrene derivatives such as polystyrene and poly- ⁇ -methylstyrene, polyvinyl ethers such as poly (ethyl vinyl ether), poly (butyl vinyl ether), and polyvinyl formal,
- guide_body and the combination of these 2 or more types can be mentioned.
- poly- ⁇ -methylstyrene is particularly preferable because the thermal decomposition temperature can be effectively lowered by irradiation with active energy rays and the workability is excellent.
- the weight average molecular weight (Mw) of the resin component is preferably 1,000 to 1,000,000, and particularly preferably 5,000 to 800,000.
- Mw weight average molecular weight
- the resin component is preferably blended at a ratio of 10% to 100% of the total amount of the temporary fixing agent. More preferably, it is blended at a ratio of 30% to 100%. This is because the temporary fixing agent can be prevented from remaining on the semiconductor wafer or the support after the desorption step described later by setting the content of the resin component to the lower limit value or more.
- the temporary fixing agent includes an active agent that generates active species by applying energy by irradiation of the active energy ray, and the decomposition temperature of the resin component is lowered in the presence of the active species.
- the photoacid generator is not particularly limited, but tetrakis (pentafluorophenyl) borate-4-methylphenyl [4- (1-methylethyl) phenyl] iodonium (DPI-TPFPB), tris (4-t-butyl) Phenyl) sulfonium tetrakis- (pentafluorophenyl) borate (TTBPS-TPFPB), tris (4-t-butylphenyl) sulfonium hexafluorophosphate (TTBPS-HFP), triphenylsulfonium triflate (TPS-Tf), bis (4 -Tert-butylphenyl) iodonium triflate (DTBPI-Tf), triazine (TAZ-101), triphenylsulfonium triflate (TPS-Tf), bis (4 -Tert-butylphenyl) iodonium triflate (
- tetrakis (pentafluorophenyl) borate-4-methylphenyl [4- (1-methylethyl) phenyl] iodonium (DPI) is particularly preferable because the thermal decomposition temperature of the resin component can be efficiently lowered.
- DPI tetrakis (pentafluorophenyl) borate-4-methylphenyl [4- (1-methylethyl) phenyl] iodonium
- the photobase generator is not particularly limited, and examples thereof include 5-benzyl-1,5-diazabicyclo (4.3.0) nonane and 1- (2-nitrobenzoylcarbamoyl) imidazole. Among these, 5-benzyl-1,5-diazabicyclo (4.3.0) nonane and derivatives thereof are preferable because the thermal decomposition temperature of the resin component can be efficiently lowered.
- the activator is preferably blended at a ratio of 0.01% to 50% of the total amount of the temporary fixing agent. More preferably, it is blended at a ratio of 0.1% to 30%.
- the photosensitive polycarbonate resin propylene carbonate, 1,4-polybutylene carbonate, or neopentyl carbonate is particularly preferable, and tetrakis (pentafluorophenyl) borate-4-methylphenyl [ 4- (1-methylethyl) phenyl] iodonium (DPI-TPFPB).
- the resin component is 30% to 100% of the total amount of the temporary fixing agent
- the active agent is 0.1% to 30% of the total amount of the temporary fixing agent
- the weight average molecular weight (Mw) of the temporary fixing agent is It is preferably 5,000 to 800,000.
- the polycarbonate resin forms a structure that facilitates thermal cleavage of the main chain of the polycarbonate resin in the presence of the activator, or forms a thermal ring closure structure in which the polycarbonate resin itself is easily pyrolyzed. Therefore, it is considered that the thermal decomposition temperature can be lowered.
- reaction formula (1) shows the mechanism of thermal cleavage of the main chain of the polypropylene carbonate resin and formation of a thermal ring closure structure.
- H + derived from the activator protonates the carbonyl oxygen of the polypropylene carbonate resin, and further shifts the polar transition state to produce unstable tautomeric intermediates [A] and [B].
- an intermediate [A] is fragmented as acetone and CO 2.
- intermediate [B] produces propylene carbonate, which is fragmented as CO 2 and propylene oxide.
- the temporary fixing agent may contain a solvent.
- Solvents are not particularly limited, but hydrocarbons such as mesitylene, decalin and mineral spirits, alcohols / ethers such as anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether and diglyme.
- Esters / lactones such as ethylene carbonate, ethyl acetate, N-butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene carbonate, ⁇ -butyrolactone, cyclopenta Non-, cyclohexanone, methyl isobutyl ketone, ketones such as 2-heptanone, and amide / lactams such as N-methyl-2-pyrrolidinone
- the temporary fixing agent contains a solvent, it becomes easy to adjust the viscosity of the temporary fixing agent, and it becomes easy to form a thin film of the temporary fixing agent on the semiconductor wafer or the support base.
- the content of the solvent is not particularly limited, but is preferably 5 to 98% by weight, and particularly preferably 10 to 95% by weight.
- the temporary fixing agent may contain a photo radical initiator.
- the radical photoinitiator is not particularly limited, and the temporary fixing agent contains a radical photoinitiator to form a temporary fixing agent at a desired position through an exposure / development process. Can do.
- the photo radical initiator is not particularly limited as long as it is decomposed into two or more compounds by irradiation with actinic radiation, and one or more of the compounds has a free radical.
- Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819 manufactured by Ciba Specialty Chemicals)
- 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- 1 (Ciba Specialty Chemicals Irgacure 369)
- 2,2-dimethoxy-1,2-diphenylethane-1-one (Ciba Specialty Chemicals Irgacure 651)
- 2-Methyl-1 [4- (Mechanicals) (Luthio) -phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals), benzoin ethyl
- the content of the photo radical initiator is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resin component.
- the temporary fixing agent may contain a sensitizer that is a component having a function of developing or increasing the reactivity of the photoradical initiator together with the photoradical initiator.
- the sensitizer is not particularly limited.
- the content of such a sensitizer is preferably 100 parts by weight or less, and 20 parts by weight or less with respect to 100 parts by weight of the total amount of the activator such as the photoacid generator and the photo radical initiator described above. More preferably.
- the temporary fixing agent may contain an antioxidant.
- the antioxidant has a function of preventing generation of undesirable acids and natural oxidation of the resin composition.
- the antioxidant is not particularly limited.
- Ciba IRGANOX registered trademark 1076
- Ciba IRGAFOS registered trademark 168 available from Ciba Fine Chemicals of Tarrytown, New York are preferably used. It is done.
- Ciba Irganox 129 Ciba Irganox 1330, Ciba Irganox 1010, Ciba Cyanox (registered trademark) 1790, Ciba Irganox 3114, Ciba I31, Ciga I31, etc.
- Ciba Irganox 129 Ciba Irganox 1330
- Ciba Irganox 1010 Ciba Cyanox (registered trademark) 1790
- Ciba Irganox 3114 Ciba I31, Ciga I31, etc.
- the content of the antioxidant is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin component.
- the temporary fixing agent may contain an acid scavenger, an acrylic, silicone, fluorine, vinyl or other leveling agent, an additive such as a silane coupling agent or a diluent, if necessary.
- the silane coupling agent is not particularly limited.
- the diluent is not particularly limited, and examples thereof include cycloether compounds such as cyclohexene oxide and ⁇ -pinene oxide, and aromatic cycloethers such as [methylenebis (4,1-phenyleneoxymethylene)] bisoxirane. And cycloaliphatic vinyl ether compounds such as 1,4-cyclohexanedimethanol divinyl ether.
- cycloether compounds such as cyclohexene oxide and ⁇ -pinene oxide
- aromatic cycloethers such as [methylenebis (4,1-phenyleneoxymethylene)] bisoxirane.
- cycloaliphatic vinyl ether compounds such as 1,4-cyclohexanedimethanol divinyl ether.
- the method for manufacturing a semiconductor device according to the present embodiment includes processing of a semiconductor wafer, and a temporary fixing agent for a semiconductor wafer containing a resin component whose temperature decreases by 50% in weight after irradiation with an active energy ray on a support substrate.
- a method of manufacturing a semiconductor device comprising: irradiating the thin film with active energy rays; and heating the thin film to detach the semiconductor wafer from the support base.
- the semiconductor device manufacturing method having the above-described structure includes a resin component whose weight loss temperature is reduced by 50% by irradiation with active energy rays, the thermal decomposition temperature of the temporary fixing agent can be lowered by irradiation with active energy rays. It can be easily detached after the processing of the semiconductor wafer, and the fixing agent hardly remains on the semiconductor wafer. Therefore, damage to the semiconductor wafer can be reduced and the time required for thermal decomposition can be shortened.
- the surface can be formed as a thin film on a support substrate having a smooth surface and sufficient accuracy, there is an effect that the accuracy of processing such as polishing is high.
- the temporary fixing agent is applied as a temporary fixing agent for a semiconductor wafer. That is, the temporary fixing agent used in the method for manufacturing a semiconductor device according to this embodiment has the characteristics of the temporary fixing agent. Below, each process of the manufacturing method of the said semiconductor device is demonstrated.
- a process of providing a thin film of a temporary fixing agent on the support substrate or the semiconductor wafer is performed.
- the thin film of the temporary fixing agent may be provided on either the supporting base material or the semiconductor wafer.
- a method for providing the temporary fixing agent in a thin film for example, a known method such as a spin coating method, a spray method, a printing method, a film transfer method, a slit coating method, or a scan coating method can be used. There is an advantage that no significant capital investment is required.
- a spin coating method is preferable, and a uniform and flat thin film can be formed, which is preferable.
- the support substrate or semiconductor wafer is placed on the surface of the support substrate or semiconductor wafer on which the thin film is provided, and the support substrate or semiconductor wafer is bonded to the thin film.
- an apparatus such as a vacuum press or a wafer bonder can be used.
- the processing of the semiconductor wafer includes polishing the back surface of the semiconductor wafer, forming a via hole, etching for stress release, lithography, coating, vapor deposition, and the like.
- the surface can be formed as a thin film on a support base having a smooth surface and sufficient accuracy, there is an effect that the processing accuracy is high.
- Active energy ray irradiation process Next, a process of irradiating active energy rays to the thin-film temporary fixing agent is performed.
- active species are generated from the active agent in the temporary fixing agent by irradiating the temporary fixing agent with active energy rays. And the thermal decomposition temperature of a resin component falls by this active species. In addition, you may perform this irradiation process before a process process.
- the thin film-like temporary fixing agent is heated and removed. Since the thermal decomposition temperature is lowered by the irradiation step, the thin temporary fixing agent can be removed at a temperature lower than the heating temperature in the conventional heating step. Therefore, damage to the semiconductor wafer can be reduced and the time required for thermal decomposition can be shortened.
- the desorption means an operation of peeling the semiconductor wafer from the support base material.
- this operation may be performed by a method of detaching in a direction perpendicular to the surface of the support substrate, a method of detaching by sliding in a horizontal direction with respect to the surface of the support substrate, or a semiconductor wafer floating from one side of the semiconductor wafer.
- the temporary fixing material remaining on the semiconductor wafer or the support base may be removed as necessary.
- the method for removing the remaining temporary fixing material is not particularly limited, and examples thereof include plasma treatment, chemical immersion treatment, polishing treatment, and heat treatment.
- the temporary fixing agent has a low molecular weight and can be detached without stress, so that the semiconductor wafer is hardly damaged.
- the temporary fixing agent temporary component having a low molecular weight is evaporated during heating, and the temporary fixing agent hardly remains on the semiconductor wafer. Therefore, it is possible to simplify post-cleaning and other post-processes and to improve handling.
- Example 1 In Example 1, a temporary fixative was prepared using the following compounds.
- reaction vessel was depressurized by about 30 kPa, and the temperature was 90 to 100 ° C. for 1 hour and 120 ° C. for 1 hour. Thereafter, the mixture was further stirred at 150 ° C. for 1 hour and 180 ° C. for 2 hours under a vacuum of 0.1 kPa.
- the weight average molecular weight of the synthesized 1,4-polybutylene carbonate was measured by GPC and found to be 35,000.
- Rhodosil Photophotoinitiator 2074 Rhodia Japan Co., Ltd., Rhodosil Photoinitiator 2074
- 1-chloro-4-propoxythioxanthone manufactured by Lambson, UK
- Neopentyl glycol (194.2 g, 1.864 mol) and diethyl carbonate (308.2 g, 2.610 mol) are added to a three-necked flask equipped with a stirrer, a raw material charging port, and a nitrogen gas introduction port. Heat at 0 ° C. to dissolve the mixture. Then, after adding a 20% sodium ethoxide ethanol solution (80 ml, 0.186 mol), the mixture was stirred at 120 ° C. for 2 hours under a nitrogen atmosphere. Thereafter, the inside of the reaction vessel was decompressed by about 30 kPa and stirred at 120 ° C. for 1 hour. Thereafter, the mixture was further stirred at 120 ° C. for 3 hours under a vacuum of 0.1 kPa.
- Example 3 In Example 3, a temporary fixative was prepared using the following compounds. ⁇ Synthesis of poly (1,3-cyclohexylene carbonate)> 8.13 g (0.070 mol) of 1,3-cyclohexanediol, 15.00 g (0.070 mol) of diphenyl carbonate, and 0.0028 g (0.0035 mol) of lithium carbonate were placed in a reaction vessel. As the first step of the reaction, the reaction vessel was immersed in a heating tank heated to 120 ° C. under a nitrogen atmosphere, stirred, the raw materials were dissolved, and stirring was continued for 2 hours.
- the pressure inside the reaction vessel was reduced to 10 kPa, and stirring was continued at 120 ° C. for 1 hour.
- the pressure inside the reaction vessel was reduced to 0.5 kPa or less, and stirring was continued at 120 ° C. for 1 hour.
- the temperature of the heating tank was raised to 180 ° C. over about 30 minutes while reducing the pressure inside the reaction vessel to 0.5 kPa or less, and then stirred at 180 ° C. for 1.5 hours.
- the phenol produced in the second to fourth steps of the reaction was distilled out of the reaction vessel.
- the temporary fixing agent after exposure the temporary fixing agent obtained in Examples was applied to an 8-inch transparent glass using a spin coater (rotation speed: 1,200 rpm, time: 30 seconds), and then 120 ° C. Pre-bake for 5 minutes, then use a mask aligner (model number: MA-8, manufactured by SUSS Microtec) to form a thin film made of a temporary fixing agent using a broadband light source (G line + H line + i line). It was prepared by exposure (exposure amount: 500 mj / cm 2 in terms of i-line).
- a semiconductor device was manufactured using the temporary fixing agent according to the above example.
- the temporary fixing agent obtained in the examples was applied to 8-inch transparent glass (rotation speed: 1,200 rpm, time: 30 seconds), and then on a hot plate at 120 ° C. for 5 minutes.
- Pre-baking was performed under the conditions described above to form a thin film made of a temporary fixing agent having a thickness of 5 ⁇ m.
- Example 1 a sample in which an 8-inch silicon wafer was temporarily fixed on an 8-inch transparent glass was put into an oven, subjected to a predetermined temperature and time treatment, and the temporary fixing agent was thermally decomposed.
- the temporary fixing agent of Example 1 was thermally decomposed at 200 ° C. for 30 minutes.
- the temporary fixing agent of Example 2 was thermally decomposed at 250 ° C. for 30 minutes.
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Abstract
Description
この方法では、研削に用いられる一般的なバックグラインドマシンの研削精度(約1μm)とウェハを固定するための一般的なBG(バックグラインド)テープの厚み精度(約5μm)とを合わせると、要求される厚み精度を超えてしまい、研削されたウェハの厚みにバラツキが生じる虞がある。
しかし、このような材料はハンドリングが悪く、脱離後に、半導体ウェハや装置の内部に残留した固定材料を薬液等で洗浄する必要がある。
また、支持基材から半導体ウェハを脱離させる際に、薄化したウェハが耐えられなくなり破損する虞があるが、半導体ウェハの薄型化が進むにつれてこの可能性が高まることが予想される。
また、半導体ウェハへのダメージを低減させ、精度の高い加工が可能であり、かつ熱分解に要する時間を短縮できる半導体装置の製造方法が望まれていた。
また、本発明の一態様では、前記活性エネルギー線の照射前後の50%重量減少温度の差が20~100℃である。
本発明において、露光前後の50%重量減少温度とは、50%の重量が失われる温度を意味する。
また、5%重量減少温度及び95%重量減少温度とは、それぞれ5%及び95%の重量が失われる温度を意味する。
前記活性エネルギー線の種類としては、特別な装置を必要とせず、簡便であるため、前記活性エネルギー線が紫外または可視光であることが好ましい。
本実施形態に係る半導体ウェハの仮固定剤は、半導体ウェハを加工するために半導体ウェハを支持基材に仮固定し、加工後に加熱することにより半導体ウェハを支持基材から脱離するために使用される仮固定剤において、活性エネルギー線の照射後に、50%重量減少温度が低下する樹脂成分を含む半導体ウェハの仮固定剤である。
また、表面が平滑で十分な精度を有する支持基材上に薄膜として形成できるため、研磨等の加工の精度が高いという効果を奏する。
これによれば、半導体ウェハ加工後の半導体ウェハの脱離が容易で、かつ半導体ウェハに仮固定剤が残留し難いという効果を一層向上させることができる。
また、半導体ウェハ加工後に活性エネルギー線を照射することにより仮固定剤の熱分解温度を下げることができるため、加工後の半導体ウェハの熱履歴による損傷を防止するという効果を一層向上させることができる。
1℃≦(95%重量減少温度)-(5%重量減少温度)≦200℃
であることが好ましい。
これによれば、仮固定剤の熱分解に要する温度範囲が狭く、熱分解に要する時間を短縮でき、半導体ウェハへのダメージを抑制するという効果を一層向上させることができる。
また、加工後の半導体ウェハの脱離が容易で、かつ半導体ウェハに仮固定剤が残留し難いという効果を一層向上させることができる。
また、安定に使用可能な温度領域が広く確保できるため、支持基材に仮固定をしたまま、種々の加工工程に供することが可能となる。
また、表面が平滑で十分な精度を有する支持基材上に薄膜として形成できるため、研磨等の加工の精度が高いという効果を一層向上させることができる。
80℃≦(95%重量減少温度)-(5%重量減少温度)≦150℃
であることがより好ましい。
これによれば、熱分解に要する時間を短縮でき、安定に使用可能な温度領域が広く確保できるという効果を一層向上させることができる。
樹脂成分は、活性剤存在下で、活性エネルギー線の照射により、熱分解温度が低下するものであれば、特に限定されない。
また、前記樹脂成分が、主鎖のヘテロ原子に隣接した3級の炭素原子を有することが好ましい。これは、樹脂成分を熱分解させる際の樹脂成分由来の中間体の安定性、さらには、結合電子を移動しやすくし、主鎖の熱分解および熱閉環反応が促進するという理由からである。
ここで、ヘテロ原子とは、水素及び炭素以外の原子を意味する。
また、前記官能基が、カルボニル基、チオカルボニル基、ホルマール基、アセタール基のいずれかであることが好ましい。これは、より効果的に主鎖の熱分解が促進されるという理由からである。
感光性のポリカーボネート系樹脂としては、以下のポリカーボネート系樹脂と前記活性剤との組み合わせを意味する。
これらの中でも、特に、活性剤存在下で、より効果的に熱分解温度を下げることができるという理由から、ポリプロピレンカーボネート、ポリシクロヘキシレンカーボネート、ポリブチレンカーボネートが好ましい。
これらの中でも、特に、活性エネルギー線の照射により効果的に熱分解温度を低下させることができ、また、作業性に優れるという理由から、ポリ―α―メチルスチレンが好ましい。
これらの中でも、特に、活性エネルギー線の照射により効果的に熱分解温度を低下させることができ、また、作業性に優れるという理由から、ポリメタクリル酸メチル、ポリメタクリル酸エチルが好ましい。
前記活性剤としては、特に限定されないが、例えば光酸発生剤、光塩基発生剤等が挙げられる。前記光酸発生剤としては、特に限定されないが、テトラキス(ペンタフルオロフェニル)ボレート-4-メチルフェニル[4-(1-メチルエチル)フェニル]ヨードニウム(DPI-TPFPB)、トリス(4-t-ブチルフェニル)スルホニウムテトラキス-(ペンタフルオロフェニル)ボレート(TTBPS-TPFPB)、トリス(4-t-ブチルフェニル)スルホニウムヘキサフルオロホスフェート(TTBPS-HFP)、トリフェニルスルホニウムトリフレート(TPS-Tf)、ビス(4-tert-ブチルフェニル)ヨードニウムトリフレート(DTBPI-Tf)、トリアジン(TAZ-101)、トリフェニルスルホニウムヘキサフルオロアンチモネート(TPS-103)、トリフェニルスルホニウムビス(パーフルオロメタンスルホニル)イミド(TPS-N1)、ジ-(p-t-ブチル)フェニルヨードニウム、ビス(パーフルオロメタンスルホニル)イミド(DTBPI-N1)、トリフェニルスルホニウム、トリス(パーフルオロメタンスルホニル)メチド(TPS-C1)、ジ-(p-t-ブチルフェニル)ヨードニウムトリス(パーフルオロメタンスルホニル)メチド(DTBPI-C1)、及びこれらの2種以上の組合せを挙げることができる。
これらの中でも特に、前記樹脂成分の熱分解温度を効率的に下げることができるという理由から、テトラキス(ペンタフルオロフェニル)ボレート-4-メチルフェニル[4-(1-メチルエチル)フェニル]ヨードニウム(DPI-TPFPB)が好ましい。
これらの中でも特に、前記樹脂成分の熱分解温度を効率的に下げることができるという理由から、5-ベンジルー1,5-ジアザビシクロ(4.3.0)ノナン及びこの誘導体が好ましい。
上記下限値以上とすることで、前記樹脂成分の熱分解温度を安定的に下げることが可能となり、上記上限値以下とすることで仮固定剤が半導体ウェハまたは支持基板に残渣として残留することを効果的に防止することが可能となる。
この場合、樹脂成分は、仮固定剤の全量の30%~100%、活性剤は、仮固定剤の全量の0.1%~30%であり、仮固定剤の重量平均分子量(Mw)は5,000~800,000であることが好ましい。これは、半導体ウェハまたは支持体に対する濡れ性、仮固定剤の成膜性、仮固定剤を構成する各種成分との相溶性や各種溶剤に対する溶解性、さらには、加熱工程における仮固定剤の熱分解性を確保するという理由からである。
先ず、前記活性剤由来のH+が、ポリプロピレンカーボネート樹脂のカルボニル酸素をプロトン化し、さらに極性遷移状態を転移させ不安定な互変異性中間体[A]及び[B]を生じる。
次に、主鎖の熱切断の場合には、中間体[A]は、アセトン及びCO2として断片化する。
熱閉環構造の形成(a又はb)の場合には、中間体[B]は炭酸プロピレンを生成し、炭酸プロピレンはCO2及びプロピレンオキシドとして断片化される。
前記仮固定剤がシランカップリング剤を含むことにより、半導体ウェハまたは支持基材との密着性を向上することが可能となる。
前記仮固定剤が希釈剤を含むことにより、仮固定剤の流動性を向上することができ、薄膜形成工程において、仮固定剤の半導体ウェハまたは支持基材に対する濡れ性を向上することが可能となる。
次に、本発明の半導体装置の製造方法の一実施形態を説明する。
本実施形態に係る半導体装置の製造方法は、半導体ウェハの加工を含み、支持基材上に、活性エネルギー線の照射後に、50%重量減少温度が低下する樹脂成分を含む半導体ウェハの仮固定剤を薄膜状に設ける工程と、前記支持基材上の薄膜が設けられた面上に半導体ウェハを載置し、該半導体ウェハを前記薄膜に貼り合わせる工程と、前記半導体ウェハを加工する工程と、前記薄膜に活性エネルギー線を照射する工程と、前記薄膜を加熱して前記半導体ウェハを前記支持基材から脱離する工程と、を含む半導体装置の製造方法である。
また、表面が平滑で十分な精度を有する支持基材上に薄膜として形成できるため、研磨等の加工の精度が高いという効果を奏する。
以下に、前記半導体装置の製造方法の各工程を説明する。
先ず、半導体ウェハを所定の支持基材上に固定するために、仮固定剤の薄膜を支持基材または半導体ウェハに設ける工程を経る。仮固定剤の薄膜は、支持基材および半導体ウェハのどちらに設けてもよい。
仮固定剤を薄膜状に設ける方法としては、例えば、スピンコート法、スプレー法、印刷法、フィルム転写法、スリットコート法、スキャン塗布法等の公知の方法を用いておこなうことができるため、新たな設備投資が必要ないという利点がある。
なお、仮固定剤を薄膜状に設ける方法としては、スピンコート法が好ましく、均一で平坦な薄膜を形成することができるので好ましい。
次に、支持基材または半導体ウェハ上の薄膜が設けられた面上に前記支持基材または半導体ウェハを載置し、該前記支持基材または半導体ウェハを前記薄膜に貼り合わせる工程を経る。貼り合わせには、真空プレス機、ウェハーボンダー等の装置を用いることができる。
次に、仮固定剤によって支持基材上に固定された半導体ウェハを加工する工程を経る。
半導体ウェハの加工は、半導体ウェハの裏面の研磨、Viaホールの形成、ストレスリリースのためのエッチング、リソグラフィー、コート、蒸着等である。
本実施形態に係る半導体装置の製造方法では、表面が平滑で十分な精度を有する支持基材上に薄膜として形成できるため、加工の精度が高いという効果を奏する。
(活性エネルギー線照射工程)
次に、薄膜状の仮固定剤に活性エネルギー線を照射する工程を経る。
この照射工程では、仮固定剤に活性エネルギー線を照射することにより、仮固定剤中の活性剤より活性種が発生する。そして、該活性種によって樹脂成分の熱分解温度が低下する。
なお、この照射工程は、加工工程の前に行ってもよい。
次に、薄膜状の仮固定剤を加熱して除去する工程を経る。
薄膜状の仮固定剤は、前記照射工程により、熱分解温度が低下しているため、従来の加熱工程での加熱温度よりも低い温度で除去することができる。そのため、半導体ウェハへのダメージを低減させ、かつ熱分解に要する時間を短縮できる。
次に、半導体ウェハを支持基材から脱離する工程を経る。
ここで、脱離とは、半導体ウェハを支持基材から剥離する操作を意味する。例えば、この操作は、支持基材の表面に対して垂直方向に脱離する方法や、支持基材の表面に対して水平方向にスライドさせて脱離する方法や半導体ウェハ片側から半導体ウェハを浮かして脱離する方法がある。
脱離工程後、必要に応じて、半導体ウェハまたは支持基材に残留した仮固定材を除去してもよい。残留した仮固定材の除去方法としては、特に限定されるものではないが、プラズマ処理、薬液浸漬処理、研磨処理、加熱処理などが挙げられる。
また、低分子化した仮固定剤仮の成分は、加熱の際に蒸散し、半導体ウェハに仮固定剤が残留し難いという効果を奏する。そのため、洗浄等の後工程を簡素化でき、ハンドリングが向上するといった利点もある。
(実施例1)
実施例1では、以下の化合物を用いて仮固定剤を作製した。
攪拌機、原料仕込み口、及び窒素ガス導入口を備えた三口フラスコに1,4-ブタンジオール(168g、1.864mol)と炭酸ジエチル(264.2g、2.236mol)を加え、窒素雰囲気下で90~100℃で加熱し、混合物を溶解した。次いで、20%ナトリウムエトキシドエタノール溶液(80ml、0.186mol)を加えた後、窒素雰囲気下、90~100℃で1時間攪拌した。その後、反応容器内を30kPa程度減圧し、90~100℃で1時間、120℃で1時間した。その後、更に、0.1kPaの真空下、150℃で1時間、180℃で2時間攪拌した。
合成した1,4-ポリブチレンカーボネートをGPCにより重量平均分子量を測定したところ、35,000であった。
得られた1,4-ポリブチレンカーボネート100g、活性剤としてRhodosil PhotoPhotoinitiator2074(FABA)(ローディアジャパン(株)社製 Rhodorsil Phoinitiator2074)5g、増感剤として1-クロロ-4‐プロポキシチオキサントン(英Lambson社製 SPEEDCURE CPTX(商品名))1.5gをアニソール(溶剤)958.5gに溶解し、樹脂濃度10%の仮固定剤を作製した。
実施例2では、以下の化合物を用いて仮固定剤を作製した。
攪拌機、原料仕込み口、及び窒素ガス導入口を備えた三口フラスコにネオペンチルグリコール(194.2g、1.864mol)と炭酸ジエチル(308.2g、2.610mol)を加え、窒素雰囲気下で、120℃で加熱し、混合物を溶解した。
次いで、20%ナトリウムエトキシドエタノール溶液(80ml、0.186mol)を加えた後、窒素雰囲気下、120℃で2時間攪拌した。その後、反応容器内を30kPa程度減圧し、120℃で1時間攪拌した。その後、更に、0.1kPaの真空下、120℃で3時間攪拌した。
合成したポリネオペンチルカーボネートをGPCにより重量平均分子量を測定したところ12,000であった。
得られたポリネオペンチルカーボネート100g、活性剤としてRhodosil PhotoPhotoinitiator2074(FABA)(ローディアジャパン(株)社製 Rhodorsil Phoinitiator2074)5g、増感剤として1-クロロ-4‐プロポキシチオキサントン(英Lambson社製 SPEEDCURE CPTX(商品名))1.5gをアニソール(溶剤)958.5gに溶解し、樹脂濃度10%の仮固定剤を作製した。
実施例3では、以下の化合物を用いて仮固定剤を作成した。
<ポリ(1,3-シクロへキシレンカーボネート)の合成>
1,3-シクロヘキサンジオール8.13g(0.070モル)、炭酸ジフェニル15.00g(0.070モル)、炭酸リチウム0.0028g(0.0035モル)を反応容器に入れた。反応の第1工程として、窒素雰囲気下で、120℃に加熱した加熱槽に反応容器を浸し、攪拌し、原料を溶解させ、2時間攪拌を続けた。反応の第2工程として、反応容器内を10kPaに減圧し、120℃で1時間攪拌を続けた。反応の第3工程として、反応容器内を0.5kPa以下に減圧し、120℃で1時間攪拌を続けた。反応の第4工程として、反応容器内を0.5kPa以下に減圧したまま、約30分かけて加熱槽の温度を180℃に昇温した後、180℃で1.5時間攪拌を続けた。反応の第2~4工程で生じたフェノールは反応容器外へ留去した。
合成したポリ(1,3-シクロへキシレンカーボネート)をGPCにより重量平均分子量を測定したところ、23,100、分子量分布は1.49であった。
得られたポリ(1,3-シクロへキシレンカーボネート)100g、活性剤としてRhodosil Photoinitiator2074(ローディアジャパン(株)社製)5g、増感剤として1-クロロ-4‐プロポキシチオキサントン(英Lambson社製 SPEEDCURE CPTX(商品名))1.5gをアニソール(溶剤)958.5gに溶解し、樹脂濃度10%の仮固定剤を作製した。
まず、スピンコータを用いて、実施例で得られた仮固定剤を8インチ透明ガラスに塗布し(回転数:1,200rpm、時間:30秒)、次いで、ホットプレート上で、120℃、5分の条件でプリベークを行い、厚さ5μmの仮固定剤からなる薄膜を形成した。
次に、マスクアライナー(型番:MA-8、ズース・マイクロテック社製)を用い、ブロードバンド光源(G線+H線+i線)により仮固定剤からなる薄膜を露光した(露光量:i線換算で500mj/cm2)。
実施例1の仮固定剤は、200℃、30分で熱分解を行った。また、実施例2の仮固定剤は、250℃、30分で熱分解を行った。
Claims (23)
- 半導体ウェハを加工するために半導体ウェハを支持基材に仮固定し、加工後に加熱することにより半導体ウェハを支持基材から脱離するために使用される仮固定剤において、
活性エネルギー線の照射後に、50%重量減少温度が低下する樹脂成分を含む半導体ウェハの仮固定剤。 - 前記活性エネルギー線の照射前後の50%重量減少温度の差が20~100℃である請求項1に記載の半導体ウェハの仮固定剤。
- 前記樹脂成分について、前記活性エネルギー線の照射後の95%重量減少温度と5%重量減少温度との差が、
1℃≦(95%重量減少温度)-(5%重量減少温度)≦200℃
である請求項1又は2に記載の半導体ウェハの仮固定剤。 - 前記樹脂成分について、前記活性エネルギー線の照射後の95%重量減少温度と5%重量減少温度との差が、
80℃≦(95%重量減少温度)-(5%重量減少温度)≦150℃
である請求項1又は2に記載の半導体ウェハの仮固定剤。 - 前記活性エネルギー線の照射によってエネルギーを加えることにより活性種を発生する活性剤を含み、該活性種の存在下で前記樹脂成分の分解温度が低下する請求項1ないし4のいずれかに記載の半導体ウェハの仮固定剤。
- 前記活性種の存在下で、前記樹脂成分の主鎖が熱切断する請求項1ないし5のいずれかに記載の半導体ウェハの仮固定剤。
- 前記活性種の存在下で、前記樹脂成分の熱閉環反応が促進される請求項1ないし6のいずれかに記載の半導体ウェハの仮固定剤。
- 前記樹脂成分が、主鎖に脂肪族4級の炭素原子を有する請求項1ないし7のいずれかに記載の半導体ウェハの仮固定剤。
- 前記樹脂成分が、主鎖にヘテロ原子を有する請求項1ないし7のいずれかに記載の半導体ウェハの仮固定剤。
- 前記樹脂成分が、主鎖のヘテロ原子に隣接した3級の炭素原子を有する請求項9に記載の半導体ウェハの仮固定剤。
- 前記樹脂成分が、主鎖の繰返し原子数が5~7である請求項1ないし10のいずれかに記載の半導体ウェハの仮固定剤。
- 前記樹脂成分が、主鎖にX-C(=O)-Y構造を有する請求項1ないし11のいずれかに記載の半導体ウェハの仮固定剤。
(ここで、XおよびYは、それぞれ、酸素原子、窒素原子、硫黄原子のいずれかである。) - 前記樹脂成分が、主鎖に1級あるいは2級の炭素原子を有し、該炭素原子の側鎖に官能基が結合する請求項1ないし12のいずれかに記載の半導体ウェハの仮固定剤。
- 前記官能基が、カルボニル、チオカルボニル、ホルマール、アセタールのいずれかである請求項13に記載の半導体ウェハの仮固定剤。
- 前記樹脂成分が、ポリカーボネート系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリエーテル系樹脂、ポリウレタン系樹脂、(メタ)アクリレート系樹脂のいずれかである請求項1ないし14のいずれかに記載の半導体ウェハの仮固定剤。
- 前記ポリカーボネート系樹脂が、ポリプロピレンカーボネート、ポリシクロヘキシレンカーボネート、ポリブチレンカーボネートのいずれかである請求項15に記載の半導体ウェハの仮固定剤。
- 前記活性種が酸または塩基である請求項1ないし16のいずれかに記載の半導体ウェハの仮固定剤。
- 前記活性エネルギー線が紫外または可視光である請求項1ないし17のいずれかに記載の半導体ウェハの仮固定剤。
- 前記半導体ウェハの仮固定剤が感光性のポリカーボネート系樹脂を含む請求項1ないし18のいずれかに記載の半導体ウェハの仮固定剤。
- 支持基材上に、活性エネルギー線の照射後に、50%重量減少温度が下がる樹脂成分を含む半導体ウェハの仮固定剤の薄膜を支持基材または半導体ウェハに設ける工程と、
前記支持基材または半導体ウェハ上の薄膜が設けられた面上に前記支持基材または半導体ウェハを載置し、該支持基材または半導体ウェハを前記薄膜に貼り合わせる工程と、
前記半導体ウェハを加工する工程と、
前記薄膜を加熱して前記半導体ウェハを前記支持基材から脱離する工程と、を含む半導体装置の製造方法。 - 前記半導体ウェハの仮固定剤が、前記活性エネルギー線の照射によってエネルギーを加えることにより活性種を発生する活性剤を含み、該活性種の存在下で前記樹脂成分の分解温度が低下する請求項20に記載の半導体装置の製造方法。
- 前記樹脂成分が、ポリカーボネート系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリエーテル系樹脂、ポリウレタン系樹脂、(メタ)アクリレート系樹脂のいずれかである請求項20又は21に記載の半導体装置の製造方法。
- 前記ポリカーボネート系樹脂が、ポリプロピレンカーボネート、ポリシクロヘキシレンカーボネート、ポリブチレンカーボネートのいずれかである請求項22に記載の半導体装置の製造方法。
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US13/126,999 US9399725B2 (en) | 2009-06-15 | 2010-06-15 | Temporary bonding adhesive for a semiconductor wafer and method for manufacturing a semiconductor device using the same |
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JP2010546973A JP5707941B2 (ja) | 2009-06-15 | 2010-06-15 | 半導体ウェハの仮固定剤及びそれを用いた半導体装置の製造方法 |
CN201080003313.2A CN102224215B (zh) | 2009-06-15 | 2010-06-15 | 用于半导体晶片的暂时粘合剂以及使用所述粘合剂制造半导体设备的方法 |
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TW201044109A (en) | 2010-12-16 |
JP5707941B2 (ja) | 2015-04-30 |
US9399725B2 (en) | 2016-07-26 |
EP2351804A1 (en) | 2011-08-03 |
TWI546360B (zh) | 2016-08-21 |
CN102224215A (zh) | 2011-10-19 |
KR101693055B1 (ko) | 2017-01-04 |
EP2351804A4 (en) | 2012-08-08 |
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