WO2006129458A1 - Wafer with fixing agent and method for producing wafer with fixing agent - Google Patents

Wafer with fixing agent and method for producing wafer with fixing agent Download PDF

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Publication number
WO2006129458A1
WO2006129458A1 PCT/JP2006/309483 JP2006309483W WO2006129458A1 WO 2006129458 A1 WO2006129458 A1 WO 2006129458A1 JP 2006309483 W JP2006309483 W JP 2006309483W WO 2006129458 A1 WO2006129458 A1 WO 2006129458A1
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WO
WIPO (PCT)
Prior art keywords
wafer
fixing agent
acid
support
support wafer
Prior art date
Application number
PCT/JP2006/309483
Other languages
French (fr)
Japanese (ja)
Inventor
Katsuhiko Hieda
Original Assignee
Jsr Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corporation filed Critical Jsr Corporation
Priority to JP2007518886A priority Critical patent/JP4784604B2/en
Publication of WO2006129458A1 publication Critical patent/WO2006129458A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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
    • 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

Definitions

  • Wafer with fixing agent and method for producing wafer with fixing agent
  • the present invention relates to a wafer with a fixing agent and a method for producing a wafer with a fixing agent, and more specifically, when a supporting wafer and a wafer to be processed (wafer) are bonded and fixed with a fixing agent, the fixing agent is used. It is possible to prevent the support wafer from protruding between the wafers, to prevent contamination of the work environment, and also to prevent the liquid material from infiltrating between the support wafer and the wafer.
  • the present invention relates to a wafer with a fixing agent that can be used, and a method for manufacturing a wafer with a fixing agent that efficiently manufactures such a wafer with a fixing agent.
  • a large number of circuits such as ICs and LSIs are formed in a lattice shape on the surface of a substantially disc-shaped semiconductor wafer, and each region where the circuits are formed is formed into a predetermined cut line.
  • Individual semiconductor elements are manufactured by dicing along.
  • the thickness of the semiconductor element is reduced in order to improve the heat dissipation of the semiconductor element and to realize the miniaturization and low cost of the mobile device such as a mobile phone. It is desired to form it as thin as possible.
  • a grinding process is performed in which the back surface is ground to a predetermined thickness.
  • the semiconductor element needs to be firmly fixed to a support such as a surface plate of a grinding machine with a temporary adhesive, but the support body force needs to be peeled off after grinding.
  • wax has been widely used as a temporary fixing adhesive for such semiconductor wafers, and various waxes have been proposed.
  • wax containing polyglycerin having an HLB value of 7 to 13 as an active ingredient see, for example, Patent Document 1
  • rosin resin having an acid value of 100 or more rosin resin derivatives
  • rosin resin A wax containing one or more of a modified product, a styrene′acrylic copolymer is disclosed.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-224270
  • Patent Document 2 JP-A-9 157628
  • Patent Document 3 Pamphlet of International Publication No. 03Z095579
  • the present invention has been made in view of such problems of the prior art, and when the support wafer and the wafer to be processed (wafer) are bonded and fixed with a fixative, the fixative is supported by the support wafer. It is possible to prevent the wafer and the working environment from being contaminated, and to prevent the liquid material from penetrating between the support wafer and the wafer. It is an object of the present invention to provide a wafer with a fixing agent that can be used, and a method for manufacturing a wafer with a fixing agent that can efficiently manufacture such a wafer with a fixing agent.
  • a wafer with a fixing agent and a method for producing a wafer with a fixing agent of the present invention that solves the above-described problems are as follows.
  • a wafer with a fixing agent comprising a supporting wafer and a fixing agent disposed on the surface of the supporting wafer, wherein the fixing agent serves as an edge portion (supporting wafer edge portion) of the supporting wafer.
  • a wafer with a fixing agent further comprising a permeation preventive structure disposed at the removed portion and disposed at the support wafer edge portion.
  • the penetration preventing structure is formed of a ring-like penetration preventing member.
  • the wafer with a fixing agent according to [1] or [2].
  • a method for producing a wafer with a fixing agent wherein a fixing agent is applied to a surface of a supporting wafer to produce a wafer with a fixing agent, and soaks into an edge portion (supporting wafer edge portion) of the supporting wafer.
  • the manufacturing method of the wafer with a fixing agent which has the process of arrange
  • [5] A step of applying the fixing agent to the surface of the supporting wafer in a liquid state, and dissolving the fixing agent on the edge of the supporting wafer with a solvent capable of dissolving the fixing agent.
  • the step of applying the fixing agent to the surface of the supporting wafer includes placing the fixing agent on the surface of the supporting wafer, and heating and melting the fixing agent in the surface of the supporting wafer.
  • the step of disposing a permeation preventing structure on the support wafer edge portion is a step of disposing a ring-shaped permeation prevention member on the support wafer edge portion.
  • the manufacturing method of the wafer with a fixing agent in any one.
  • the penetration preventing structure is provided at the edge of the supporting wafer, when the workpiece wafer is bonded and fixed to the wafer with the fixing agent, the penetration preventing structure is used. It becomes possible to prevent the fixing agent from protruding between the supporting wafer and the wafer to be processed. In addition, it is possible to prevent the liquid material from permeating between the support wafer and the workpiece wafer.
  • the method for producing a wafer with a fixing agent of the present invention it is possible to dispose a permeation preventing structure at the edge of the supporting wafer and apply the fixing agent to the surface of the supporting wafer thinly and uniformly. As a result, it is possible to prevent the fixing agent from protruding between the support wafer and the wafer to be processed, and to prevent contamination of the wafer and the work environment. Further, a liquid substance is provided between the support wafer and the wafer to be processed. A wafer with a fixing agent capable of preventing the penetration of water is obtained.
  • FIG. 1 is a perspective view schematically showing an embodiment of a wafer with a fixing agent of the present invention
  • Fig. 1 (b) is an A- It is A 'sectional drawing.
  • FIG. 2 (a) is a perspective view schematically showing another embodiment of a wafer with a fixing agent of the present invention
  • FIG. 2 (b) is a cross-sectional view taken along line B-B ′ of FIG. 2 (a). It is sectional drawing.
  • FIG. 3 (a) is a plan view schematically showing another embodiment of a wafer with a fixing agent of the present invention
  • FIG. 3 (b) is a cross-sectional view along CC ′ in FIG. 3 (a). It is.
  • FIG. 4A is a perspective view schematically showing one step of one embodiment of a method for producing a wafer with a fixing agent of the present invention.
  • FIG. 4B is a sectional view taken along the line DD ′ in FIG. 4A.
  • FIG. 5A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention.
  • FIG. 5B is a cross-sectional view taken along the line EE ′ in FIG. 5A.
  • FIG. 6A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention.
  • FIG. 6B is a cross-sectional view taken along the line FF ′ in FIG. 6A.
  • FIG. 7A is a perspective view schematically showing one step of one embodiment of a method for producing a wafer with a fixing agent of the present invention.
  • FIG. 7B is a GG ′ sectional view in FIG. 7A.
  • FIG. 8A is a perspective view schematically showing one step of one embodiment of a method for producing a wafer with a fixing agent of the present invention.
  • FIG. 8B is a cross-sectional view taken along line H—H ′ in FIG. 8A.
  • FIG. 9A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
  • FIG. 9B is a cross-sectional view taken along line I I ′ in FIG. 9A.
  • FIG. 10A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
  • FIG. 10B is a cross-sectional view taken along the line JJ ′ in FIG. 10A.
  • FIG. 11A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
  • FIG. 11B is a KK ′ sectional view in FIG. 11A.
  • FIG. 12A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
  • FIG. 12B is an LL ′ cross-sectional view in FIG. 12A.
  • an embodiment of the wafer with a fixing agent of the present invention includes a supporting wafer 1 and a fixing agent 2 disposed on the surface of the supporting wafer 1.
  • 1 is a wafer 100 with a fixing agent provided with an infiltration prevention structure (infiltration prevention portion) 3 disposed on an edge portion (support wafer edge portion) 4 of the support wafer 1.
  • the fixing agent 2 is disposed in a portion excluding the support wafer edge portion 4, whereby the fixing agent 2 is disposed in a recess formed by the support wafer 1 and the penetration preventing portion 3. It has become.
  • FIG. 1 (a) is a perspective view schematically showing one embodiment of a wafer with a fixing agent of the present invention
  • FIG. 1 (a) is a perspective view schematically showing one embodiment of a wafer with a fixing agent of the present invention
  • FIG. 1 (b) is a cross-sectional view taken along line AA ′ of FIG. 1 (a).
  • FIG. 1 is a cross-sectional view of a wafer 100 with a fixing agent taken along a plane perpendicular to the support 1 through A—A ′.
  • the shape of the support wafer used in the present embodiment is not particularly limited, and is preferably a disc shape as shown in FIGS. 1 (a) and 1 (b). This is because the wafer to be processed is usually formed in a circular shape (disk shape), and accordingly, it is preferable to form the support wafer in a circular shape having substantially the same size. Accordingly, when the wafer to be processed has another shape, it is preferable to use the same shape.
  • the thickness of the support wafer is not particularly limited, but is preferably 300 ⁇ m to 725 ⁇ m in the case of a so-called 20 Omm wafer having a diameter of 200 mm. If the back surface of the support wafer (the surface on the side where the fixing agent or the like is not disposed) is used as the reference surface, the distance (thickness) between the back surface and the front surface is determined by the bonding accuracy with the wafer to be processed and the post-bonding Since this affects the handling accuracy in the process, it is preferable that the thickness accuracy has a flatness of ⁇ 5 m or less, preferably ⁇ 1 m or less, more preferably ⁇ 0.3 m or less in the surface.
  • the material of the support wafer is not particularly limited, but ceramics, metal compounds, glass materials, and the like are preferable.
  • ceramics include silicon carbide, nitrogen carbide, alumina, aluminum nitride, zircoaure, and titanium.
  • metal compound include austenide stainless materials such as SUS302B, SUS304, SUS309S, SUS310S, SUS316, SUS316Ti, SUS317, SUS321, SUS347, and SUSXM15J1.
  • the glass material include alkali-free glass and quartz.
  • Semiconductor wafers such as recon, GaAs, and GaN can also be used as support wafers.
  • the thickness of the fixing agent 2 disposed on the surface of the support wafer 1 shown in FIGS. 1 (a) and 1 (b) is preferably 1 ⁇ m to 1 mm. More preferably, it is ⁇ 100 ⁇ m. If it is thinner than 1 ⁇ m, the adhesive strength may not be sufficient when the wafer to be processed is fixed. If it is thicker than 1 mm, the fixative 2 may be used unnecessarily, resulting in increased costs.
  • the fixing agent used in the present embodiment is preferably a hot-melt adhesive.
  • the hot-melt adhesive is solid at room temperature, but can be adhered by heating and melting, adhering the adherend and cooling, and again hot-melting by heat.
  • the hot melt adhesive composition preferably contains a crystalline compound as a main component in order to impart cohesion to the composition.
  • the “main component” means a component contained in 70% by mass or more.
  • the melting temperature of the crystalline compound is preferably 50 to 300 ° C, more preferably 55 to 250 ° C.
  • the melting temperature refers to the peak temperature in the main melting peak curve measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the crystalline compound has a molecular weight of 1000 or less, preferably 150 to 800, more preferably 200 to 600. If the molecular weight of the crystalline compound exceeds the above range, the solubility of the crystalline compound in the solvent decreases, so the wafer to be processed and the wafer with the fixing agent are separated using a solvent, and then the solvent is used. When cleaning, peeling and cleaning with the solvent may be insufficient.
  • the crystalline compound does not damage the wiring and insulating film formed on the semiconductor wafer, does not cause contamination, and does not denature the fixing agent when melted.
  • it is preferably a neutral compound without an active functional group such as a carboxylic acid group or an amino group.
  • the total metal content of alkali metals, etc. (such as Na, K, Ca, Fe, Cu, Ni, Cr, Al, etc.) that diffuse into the medium and adversely affect the insulation properties is less than lOOppm. It is more preferable that the metal-free treatment is performed until it becomes 10 ppm or less.
  • a stable form such as a metal oxide, is not this limitation.
  • Examples of such crystalline compounds include -tro compounds such as 1, 3, 5 tri-trobenzene, 2, 3, 6 tri-trophenol, 2, 4, 5 tri-trotoluene, and the like.
  • -tro compounds such as 1, 3, 5 tri-trobenzene, 2, 3, 6 tri-trophenol, 2, 4, 5 tri-trotoluene, and the like.
  • an organic compound that does not contain N element and has only C, H, and O elements is preferable.
  • Specific examples include aromatic compounds, aliphatic compounds, and alicyclic compounds as exemplified below.
  • aromatic compounds include 9H xanthene, benzofuran 3 (2H) on, 1,5 diphenyl 2,4 pentagen 1 on, di 2 naphthyl ether, cis -1,8 terpine, 2, 3 dimethyl Naphthalene, 1, 2 naphthalene diol, G 1 naphthylmethane, biphenyl 2, 2, diol, di 1 naphthyl ether, bis (diphenylmethyl) ether, 9, 10 dihydroanthracene, 2, 3, 5, 6-tetramethyl-p Benzoquinone, 2,6 dimethylnaphthalene, syringaldehyde, vanillyl alcohol, 1,3 diphenylisobenzofuran, 2,3,1 dihydroxybenzophenone, isohydrobenzoin, 4,4 'dimethylbiphenyl, 1,3 naphthalenediol, 4 Phenanthrol, 3, 3-Diphenylphthalide, Pentamethylphenol
  • Examples of the aliphatic compound include ribitol, D-arabitol, furyl, ⁇ -carotene, / 3 striking tenten, cantharidin, pentaerythritol, trans, trans-1,4 diacetoxybutadiene, D Glucitol, D-mannitol, idose, decanal, ⁇ -strength, 2, 4, 6 trimethylphloroglucinol, galactitol, echirin, echlenine, trans-1,2-cyclobentandiol, manol, 1 heptadecanol, 1-octadecanol, 1-icosanol, dihydroxyacetone, ⁇ -terpineol, 1-hexacosanol, 1-hentriacontanol, stearone and the like.
  • Examples of the alicyclic compounds include coprostanol, timosterol, ergocalciferol, ⁇ -sitosterol, lanosterol, 11-deoxycorticosterone, cholesterol, and cholesterol, testosterone, enolegostero and cholesterol.
  • the crystalline compound may be used alone or in combination of two or more.
  • the crystalline compound is used so that the content in the fixing agent is 70% by mass or more, preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the melting temperature may not be sharp and the melt viscosity may be increased.
  • the fixing agent containing the crystalline compound as a main component as described above preferably has a melting temperature range of 1 to 30 ° C, more preferably 1 to 20 ° C. It is particularly preferable that the temperature is 10 ° C.
  • the melt viscosity at the melting temperature of the fixative is preferably 0.0001-0. LPa's, preferably 0.001-0.05 Pa's S, more preferably 0.001-0. OlPa's. It is particularly preferred that
  • the melting temperature range refers to the difference between the starting point temperature and the ending point temperature in the main melting peak curve measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the melting temperature range and the melt viscosity of the fixing agent strongly depend on the melting temperature range and the melt viscosity of the crystalline compound, it is necessary to use a crystalline compound with a narrow melting temperature range and a low melt viscosity. desirable.
  • the crystalline compound as the main component has a melting temperature of 50 to 300 ° C, a melting temperature range of 1 to 30 ° C, and a melt viscosity at the melting temperature of 0.0001 to 0.1 lPa's. are preferred.
  • Crystalline compounds examples include: (a) a method in which a crystalline compound is dissolved in a solvent, and the solvent is gradually distilled off for recrystallization to increase purity; and (b) a crystalline compound is dissolved in a solvent. And a method of reducing the metal content by removing the free metal by bringing the solution into contact with an ion exchange resin.
  • a nonionic surfactant is used as necessary to adjust the wettability and Z or adhesion to the support wafer and the workpiece wafer, or to adjust the melt viscosity of the fixing agent.
  • Surface tension modifiers such as agents can be added as long as the intended function is not impaired.
  • nonionic surfactant examples include a fluorine-based surfactant having a fluorinated alkyl group such as a perfluoroalkyl group, and a polyether alkyl-based surfactant having an oxyalkyl group. Can be mentioned.
  • fluorosurfactant examples include C F CONHC H and C F SO N.
  • polyether alkyl surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene alkyl ether.
  • examples include reoxyethylene sorbitan fatty acid ester and oxyethylene oxypropylene block polymer.
  • nonionic surfactants other than the above include polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyalkylene oxide block copolymers, and the like. Specifically, “CHEMISTAT 2500 "Sanyo Kasei Kogyo Co., Ltd.”, “SN-EX9228” (San Nopco Co., Ltd.), “Nonal 530” (Toho Chemical Co., Ltd.), etc.
  • the surface tension adjusting agent can be used in an amount of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the crystalline compound.
  • the amount used exceeds the above range, the hardness of the fixing agent at room temperature may be low, or the adhesiveness may be too high, making it difficult to process into a predetermined shape.
  • the amount used is lower than the above range, the effect of improving wettability and Z or adhesion may not appear.
  • the adhesive strength by the fixing agent is preferably 0.5 MPa or more at 25 ⁇ 2 ° C, more preferably IMPa or more, and particularly preferably 5 MPa or more. If the bonding strength is lower than the above range, the bonded surface may be partially peeled depending on the processing conditions after bonding, and the in-plane uniformity of processing may be impaired.
  • the adhesive strength at 25 ⁇ 2 ° C is A (MPa)
  • the melting temperature of the fixing agent Differential scanning calorific value
  • the peak temperature in the main melting peak curve measured with the analyzer (DSC) is 20 ° C lower and the bond strength at the temperature is B (MPa).
  • the liquid crystal compounds described in Patent Document 3 can also be used. Specifically, iso sodium butyrate, sodium oleate, potassium hexahydrobenzoate, sodium stearate, sodium myristate, sodium palmitate, sodium benzoate, ethyl-p-azoxybenzoate, 1-n —Dodecyl pyridi-um chloride, 1 n —Dodecyl pyridi-um bromide, l—n—Dodecyl pyridi-um Mudeodide, 2-n-tridecylpyridyl-um chloride, 3-n-dodecyloxymethyl pyridinium methylsulfonate, 3-n-dodecyloxymethylpyridium-p-methylphenol sulfonate, 4-cyano 4, one O-lipped Ruo carboxymethyl bi Hue - le, 4 Shiano - 4, one dodecyl O carboxymethyl bi
  • liquid crystal compounds may be used alone or in combination of two or more liquid crystal compounds.
  • these compounds having liquid crystallinity those having a melting point of 35 ° C or more are preferred, and those having a single or Z or a mixture of two or more are preferably those having a melting point of 35 ° C or more and 200 ° C or less. Those having a temperature of from ° C to 150 ° C are particularly preferred.
  • liquid crystal compound When the liquid crystal compound is used as a fixing agent, fine particles of metal oxides such as acid aluminum, acid zirconium, titanium oxide, and silicon oxide are used as necessary to adjust the viscosity. And can be used in appropriate mixture.
  • metal oxides such as acid aluminum, acid zirconium, titanium oxide, and silicon oxide are used as necessary to adjust the viscosity. And can be used in appropriate mixture.
  • the liquid crystal compound may contain an organic polymer, for example, poly (caseyl anhydride), poly [2, 6bis (hydroxymethyl) -4 methylphenol — co-4 hydroxy, as necessary, in order to adjust the viscosity.
  • organic polymer for example, poly (caseyl anhydride), poly [2, 6bis (hydroxymethyl) -4 methylphenol — co-4 hydroxy, as necessary, in order to adjust the viscosity.
  • the penetration preventing structure (penetration preventing portion) 3 is provided on the supporting wafer edge portion 4 on the supporting wafer edge portion. It is formed in a ring shape so as to surround the outer periphery of the fixing agent 2 disposed in the portion excluding 4.
  • the penetration preventing structure is formed in a ring shape so as to surround the outer periphery of the fixing agent, so that the fixing agent is disposed in the recess formed by the support wafer and the penetration preventing structure and fixed. It is possible to prevent the agent from protruding between the support wafer and the workpiece wafer. In addition, it is possible to prevent the liquid material from permeating between the support wafer and the workpiece wafer.
  • the soaking prevention part 3 is constituted by a ring-like soaking prevention member.
  • the thickness of the penetration preventing part 3 is preferably 80% to 200% of the thickness of the fixing agent 2, more preferably 95% to 150%, and even more preferably 95 to 105%. I like it. If it is thinner than 80%, the fixative 2 is likely to protrude and liquid substances can easily penetrate. If it is thicker than 200%, it may be difficult to fix the wafer to be covered.
  • the upper surface of the infiltration prevention unit 3 is approximately the same as that of the wafer to be processed. It is preferable that the upper surface of the permeation prevention part 3 and the Z or material are elastic member forces so that they deform along the workpiece wafer during bonding. ,.
  • the outer peripheral shape of the infiltration preventing portion 3 is circular. This is because the wafer to be processed is usually formed in a circular shape (disc shape), and it is preferable to form the supporting wafer 1 in a circular shape having almost the same size. Is also adapted to its size and shape. Further, the outer peripheral radius of the permeation preventing unit 3 is preferably 80 to 120% of the outer peripheral radius of the support wafer 1, and more preferably 90 to 100%.
  • the width of the permeation prevention part 3 (the difference between the radius of the outer periphery and the inner periphery of the ring shape) is 1 to 20% of the outer periphery radius of the permeation prevention part 3 2 to More preferably, it is 10%. If it is shorter than 1%, the ability to prevent the leakage of the fixing agent 2 may be reduced, and if it is longer than 20%, the amount of the fixing agent 2 that can be disposed is reduced, and the adhesive fixing effect may be reduced. .
  • the material of the penetration prevention member is a resin material containing fluoride, a metal whose surface is water-repellent treated with a fluorine-based material, etc., and Z Or a metal oxide material etc. are preferable.
  • the penetration preventing member (penetration preventing portion) is preferably attached to the supporting wafer 1 with the fixing agent 2 and is adhered to the supporting wafer 1 or directly attached to the supporting wafer 1.
  • FIGS. 3 (a) and 3 (b) a gap may be opened between the penetration preventing part 3 and the fixing agent 2.
  • the gap is preferably 20% or less with respect to the width W of the supporting wafer edge portion.
  • FIG. 3 (a) is a plan view of the wafer 102 with the fixing agent in which a gap is formed between the penetration preventing part 3 and the fixing agent 2 obtained by the method for manufacturing the wafer with the fixing agent of the present invention.
  • Fig. 3 (b) is a cross-sectional view of CC '.
  • a cover film is further provided in the embodiment of the wafer with a fixing agent of the present invention described above.
  • the wafer 101 with the fixing agent of the present embodiment is further provided on the surface of the fixing agent 2 and the permeation preventing portion 3 disposed on the surface of the support wafer 1.
  • a cover film 5 is provided.
  • FIG. 2 (a) is a perspective view schematically showing another embodiment of the wafer with a fixing agent of the present invention
  • FIG. 2 (b) is a cross-sectional view taken along the line BB ′ of FIG. 2 (a).
  • the size of the cover film is preferably large enough to cover the entire surface of the fixing agent, and more preferably large enough to cover the entire surface of the fixing agent and the entire top surface of the infiltration prevention portion.
  • the cover film is preferably a circular shape having a radius not exceeding 120% (maximum radius) of the outer peripheral radius of the support wafer, or a square having a length of one side twice the maximum radius.
  • the thickness of the cover film is 5 to: 10 to 50 ⁇ m, preferably LOO ⁇ m Is more preferable. If it is thinner than 5 ⁇ m, the strength of the cover film will be insufficient, and the force bar film may be easily damaged by external force, and the surface of the fixing agent may not be protected. If it is thicker than 100 m, the flexibility of the cover film will be insufficient. It may be difficult to remove when using it.
  • the cover film is preferably a heat-resistant and releasable film.
  • a polyimide film, a PTFE (polytetrafluoroethylene) film, a PFA (tetrafluoroethylene perfluoroalkyl butyl ether copolymer) film, and the like can be given.
  • a PET (polyethylene terephthalate) film that has been subjected to a release treatment can be used.
  • the cover film it is preferable that the cover film has been subjected to metal-free treatment or the like so as not to contaminate the wafer to be covered.
  • the method for producing a wafer with a fixing agent according to the present invention is a method for manufacturing a wafer with a fixing agent by applying a fixing agent to the surface of a supporting wafer to produce a wafer with a fixing agent, wherein the edge portion of the supporting wafer (supporting wafer edge portion) ) Is a method for manufacturing a wafer with a fixing agent, which has a step of providing a penetration preventing structure.
  • a structure for preventing penetration can be provided at the edge of the support wafer, and the fixing agent can be applied thinly and uniformly on the surface of the support wafer.
  • One embodiment of the method for producing a wafer with a fixing agent of the present invention includes a step of applying the fixing agent to the surface of the support wafer in a liquid state, and a supporting wafer edge with a solvent capable of dissolving the fixing agent.
  • FIGS. 4A, 4B, 5A, and 5B schematically show one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention
  • FIGS. 4A and 5A are perspective views
  • FIGS. 5B is a sectional view taken along the line DD ′ in FIG. 4A and a sectional view taken along the line EE ′ in FIG. 5A, respectively.
  • solid fixing agent 12 is placed on the surface of support wafer 11 at room temperature, and fixing agent 12 is heated and melted.
  • Figure 5B No. 11 has a step of applying a molten state fixing agent 12 to the surface of 11.
  • a liquid fixing agent may be directly spin-coated on the support wafer.
  • the support wafer 11 is rotated to apply the fixing agent 12.
  • the fixing agent 12 is heated and melted
  • the support wafer 11 is rotated to fix the fixing agent 12. 12 may be applied.
  • solid at room temperature means a solid state at a temperature of 25 ° C or lower.
  • the fixing agent 12 that is solid at room temperature is placed on the center (rotation center) portion of the surface of the support wafer 11, the fixing agent 12 is heated and melted, and the support wafer 11 is centered perpendicular to the surface. While rotating in the direction indicated by the rotation direction R about the axis, the fixing agent 12 is applied to the supporting wafer 11 by spin coating that expands the molten fixing agent 12 to the outer periphery by the centrifugal force caused by the rotation of the supporting wafer 11. Preferable to apply.
  • the rotation speed of the support wafer 11 is preferably 50 rpm to l, OOO rpm, more preferably lOOrp m to 300 rpm! /. It may be difficult to apply the fixative 2 evenly over the entire surface of the support wafer 11, and if it is faster than 1, OOOrpm, there will be too much fixative 12, which also eliminates the upper force of the support wafer 11. is there.
  • the rotational speed of the support wafer 11 is preferably further optimized in accordance with the melt viscosity of the fixing agent 12 and the like. Further, the rotation speed of the support wafer 11 may be changed with time. For example, rotate the fixing agent 12 to the desired thickness by rotating at low speed until the fixing agent 12 spreads over the entire surface of the support wafer 11, then rotating at high speed and optimizing each time. Can do. For example, it can be rotated at a low speed (about lOOrpm) at first, and then at a desired film thickness at about 700rpm.
  • the fixing agent when applying the fixing agent to the surface of the supporting wafer while rotating the supporting wafer, the fixing agent is placed at the center of the supporting wafer surface, heated and melted, and the supporting wafer is rotated at, for example, 100 rpm to 200 rpm. It is preferable that the fixing agent is spread over the entire surface of the supporting wafer, and then the temperature is raised, and in that state, the rotating speed of the supporting wafer is set to, for example, 500 rpm to 700 rpm, and the fixing agent is applied in a thin uniform film thickness. .
  • the shape of the fixing agent 12 before melting placed in the central portion of the support wafer 1 shown in FIGS. 4A and 4B is not particularly limited.
  • it may be a thick disk, or a polygonal plate, an elliptical plate, or any other irregular plate instead of a circular plate. Or a lump.
  • the size of the fixing agent 12 placed on the support wafer 11 is, for example, in the case of a diameter of 6 to 8 inch support wafer 11 is preferably about 1, 000 mm 3 from about 500 mm 3.
  • the diameter of the supporting wafer 11 is 8 to 12 inches (excluding 8 inches) or more, it is preferable to determine the size of the fixing agent 12 according to the size of the supporting wafer 11.
  • a plurality of fixing agents may be arranged in a dispersed manner. Furthermore, it is preferable to adjust the amount of the fixing agent so that it is uniformly distributed over the entire wafer surface.
  • the thickness of the fixing agent 12 applied to the surface of the support wafer 11 shown in FIGS. 5A and 5B is the same as the thickness of the fixing agent in the wafer with the fixing agent of the present invention.
  • the material of the fixing agent, the physical properties such as the melting temperature and the adhesive strength, the additive and the like are preferably the same as those of the fixing agent in the wafer with the fixing agent of the present invention.
  • the shape, thickness, material, and the like of the support wafer used in this embodiment are preferably the same as those of the support wafer in the wafer with a fixing agent of the present invention.
  • the method for manufacturing a wafer with a fixing agent further uses a solvent 22 that can dissolve the fixing agent 12, and the edge portion of the support wafer 11 (support wafer edge portion).
  • the step of dissolving and removing the fixing agent 12 applied to 14 is included.
  • the penetration preventing portion can be easily formed so as to surround the outer periphery of the fixing agent 12.
  • Fixing agent that prevents sticking out of the fixing agent and infiltration of the liquid substance by first applying the fixing agent to the entire surface of the supporting wafer 11 and then dissolving and removing the fixing agent 12 on the supporting wafer edge 14.
  • An attached support wafer can be manufactured efficiently.
  • FIG. 6A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention
  • FIG. 6B is a sectional view taken along line FF ′, which is supported by a solvent 22. A state after the fixing agent 12 applied to the wafer edge portion 14 is dissolved and removed is shown.
  • the solvent 22 was discharged from the tip of the solvent nozzle 21, and the fixing agent 12 was applied to the entire surface. It is supplied to the edge portion from the back surface portion of the support wafer.
  • the supply speed of the solvent 22, the opening diameter of the tip of the solvent nozzle 21, the angle applied to the back surface of the support wafer, and the number of rotations of the support wafer need to be optimized depending on the region where the fixing agent is removed.
  • the solvent 22 used in the present embodiment is not particularly limited as long as it can dissolve the fixing agent 12, and can be appropriately determined depending on the type of the fixing agent 12.
  • the fixing agent 12 is the above crystalline compound, isopropanol, butanol, hexanol, ethanol, methanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, phenol, t- Alcohols such as aminole alcohol and cyclohexanol; n —pentane, cyclopentane, n-hexane, cyclohexane, n —heptane, cycloheptane, n-octane, cyclooctane, n-decane, cyclodecane, Hydrocarbon solutions such as dicyclopentagen hydride, benzene, toluene, xylene, durene, indene, decalin, tetralin,
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc .
  • Ethyl ether ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, jet ethylene glycol jetyl ether, tetrahydrofuran , Ethers such as dioxane; ethyl acetate, butyl acetate, ethyl butyrate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl enoate acetate, ethylene glycol monoacetate, diethylene glycol monomethenoate etherate Acetate, diethylene glycolenomonoethylenoate acetate, propylene glycolenomethinoatenoacetate, prop Esters such as pyreneglycol-monoethylenoleetheno
  • isopropanol, ethanol, methanol, acetone, methyl ethyl ketone, and tetrahydrofuran are preferred.
  • the solvent 22 may be used alone or in combination of two or more. You may mix and use the above.
  • the method for manufacturing a wafer with a fixing agent further includes a permeation preventing member disposed on the support wafer edge portion 14 from which the fixing agent 12 has been cleaned and removed. It is preferable to install a permeation prevention part 13) and use a wafer with a fixing agent.
  • the permeation preventive part 13 is formed by a method of forming a preventive part directly adhered to the support wafer by applying a permeation preventive member (permeation preventive agent) such as fluoride-containing sallow on the edge of the support wafer from which the fixing agent has been removed.
  • the permeation preventing structure (stain prevention portion) 13 may be formed by discharging a permeation prevention agent from the tip of a nozzle (not shown) for applying the permeation prevention agent and spin-coating the support wafer edge portion 14.
  • a permeation prevention agent from the tip of a nozzle (not shown) for applying the permeation prevention agent and spin-coating the support wafer edge portion 14.
  • the soaking prevention part 13 it is possible to prevent the fixing agent 12 from protruding, and it is possible to prevent the etching solution from soaking when the wafer to be covered is etched.
  • FIG. 7A is a perspective view schematically showing one step of an embodiment of the method for manufacturing a wafer with a fixing agent of the present invention, and FIG. The state after the prevention member is arranged on the supporting wafer edge portion 14 and the infiltration prevention structure is arranged is shown.
  • the shape, material, and the like of the soaking prevention part are preferably the same as those of the soaking prevention part in the wafer with a fixing agent of the present invention.
  • the method for producing a wafer with a fixing agent of this embodiment preferably further includes a step of attaching a cover film 15 to the surface of the fixing agent 12 as shown in FIGS. 8A and 8B.
  • a cover film 15 to the surface of the fixing agent 12 as shown in FIGS. 8A and 8B.
  • contamination of the surface of the fixing agent and the permeation preventive part due to metal, dust or the like can be prevented.
  • FIG. 8A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention
  • FIG. 8A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention.
  • FIG. 5 is a cross-sectional view taken along the line H-H ′, showing a state after the cover film 15 is attached to the surface of the fixing agent 12.
  • the cover film 15 is obtained by attaching a large film material to the surface of the fixing agent 12, It may be cut into a predetermined size, or may be affixed to the surface of the fixing agent 12 after being formed into a predetermined size.
  • the cover film 15 preferably covers at least the entire surface of the fixing agent 12 and more preferably covers the entire surface of the infiltration preventing part 13.
  • the shape, material, and the like of the cover film 15 are preferably the same as those in the case of the cover film in the wafer with the fixing agent of the present invention.
  • Another embodiment of the method for manufacturing a wafer with a fixing agent according to the present invention is a method for manufacturing a wafer with a fixing agent by applying a fixing agent to the surface of a supporting wafer to manufacture a wafer with a fixing agent, and is provided at the edge of the supporting wafer.
  • the manufacturing method of the present embodiment first includes a step of disposing a permeation prevention structure (a permeation prevention unit 13) on the support wafer edge portion 14 of the support wafer 11.
  • FIG. 9A and FIG. 9B schematically show one process of another embodiment of the method for producing a wafer with a fixing agent of the present invention
  • FIG. 9A is a plan view
  • FIG. 9B is a cross-sectional view taken along line I ⁇ in FIG.
  • the same components as those in the drawings for explaining the embodiment of the method for producing a wafer with a fixing agent of the present invention are denoted by the same reference numerals. Yes.
  • the soaking prevention part 13 is preferably arranged by placing a ring-like soaking prevention member on the support wafer edge part 14. By providing the permeation preventing part 13 on the support wafer edge part 14, a recess 31 is formed by the support wafer 11 and the permeation prevention part 13.
  • the conditions of the support wafer and the permeation prevention unit in the present embodiment are preferably the same as the conditions of the support wafer and the permeation prevention unit in the wafer with a fixing agent of the present invention.
  • FIGS. 10A and 10B A step of disposing a fixing agent at a predetermined position of the support wafer;
  • the step of arranging the fixing agent 12 in the recess 31 formed by the support wafer 11 and the penetration preventing structure 13 is performed next.
  • the position of the fixing agent on the support wafer 11 is not particularly limited. Regarding the material, size, melting temperature, adhesive strength, and other physical properties, additives, etc. of the fixing agent 12 before being applied to the support wafer, in the case of one embodiment of the method for manufacturing a wafer with a fixing agent of the present invention described above It is preferable to be the same as in this case.
  • FIG. 10A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention
  • FIG. 10B is a JJ ′ sectional view thereof.
  • the method for producing a wafer with a fixing agent of this embodiment preferably has a step of arranging a cover film 15 on the surface of the fixing agent 12 as shown in FIGS. 11A and 11B.
  • a rectangular cover film 15 larger than the support wafer 11 is disposed on the surface of the fixing agent 12.
  • the size of the cover film 15 is thus large, and may be cut into a predetermined size later, or may be affixed to the fixing agent 12 after being cut into a predetermined size.
  • the thickness, material, etc. of the cover film 15 are preferably the same as those in the case of the cover film in the wafer with a fixing agent of the present invention.
  • FIG. 11A is a plan view schematically showing a process of another embodiment of the method for producing a wafer with a fixing agent of the present invention
  • FIG. 11B is a sectional view taken along the line KK ′.
  • the manufacturing method of the wafer with a fixing agent of the present embodiment next applies a force f from the top of the cover film 15 while pressing the cover film 15 and the fixing agent 12. It is preferable to have a step of heating the fixing agent 12 to a liquid state and applying the fixing agent 12 to the surface of the support wafer 11. This allows the fixative 12 to be evenly spread in the recess 31 (see FIGS. 11A and B).
  • the force f is applied uniformly to the entire fixing agent 12. Thereby, the fixing agent 12 can be spread with a uniform thickness.
  • the force f is not particularly limited, but is preferably 1 to: LOOOgZcm 2 .
  • the penetration preventing part 13 is fixed by spreading the fixing agent 12 over the entire depression 31 (see FIGS. 11A and 11B). It can be fixed to the supporting wafer edge portion 14 by the agent 12.
  • FIG. 12A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
  • FIG. 12B is an L L ′ cross-sectional view thereof.
  • FIG. 12A and FIG. 12B show one embodiment of the method for producing the wafer with a fixing agent of the present invention shown in FIG. 8A and FIG. 8B by cutting the portion of the cover film 15 that protrudes from the penetration preventing portion 13.
  • a wafer with a fixing agent similar to the wafer 104 with a fixing agent obtained in the embodiment is obtained.
  • a method for processing a wafer to be processed using the wafer with a fixing agent of the present invention will be described.
  • a wafer with a fixing agent shall be provided with a cover film.
  • the cover film of the wafer with the fixing agent of the present invention described above is peeled off, and the wafer to be processed (Ueno) is placed on the surface on which the fixing agent is disposed. Arrange them so that they face outward (the back side is exposed to the outside), heat and melt the fixing agent, and then cool it down to bond and fix the wafer to the wafer with the fixing agent.
  • the wafer is placed on the wafer with the fixing agent, and the whole is depressurized by sandwiching them between the heat presses, and the heater is fixed. It is preferable to raise the temperature to + 20 ° C. and press with pressure, then return to normal pressure in the pressed state, slowly cool the heater, solidify the fixing agent again, and complete the adhesion.
  • the depressurization is performed to remove bubbles between the support wafer and the fixing agent may volatilize if the degree of vacuum is too high at about 100 to 1 Torr.
  • the slow cooling may be within the range of the solidification temperature of the fixing agent ⁇ 10 ° C, and it is desirable to slowly cool at a rate of 5 ° C Zmin or less, preferably 2 ° C Zmin or less. If the cooling is fast, bubbles can be easily taken into the inside due to the heat shrinkage and crystallization of the fixing agent, which may deteriorate the adhesive strength.
  • the back surface of the wafer is polished or etched to thin the wafer to 100 ⁇ m to 300 ⁇ m.
  • the wafer bonded to the wafer with the fixing agent is set together with the wafer with the fixing agent, for example, in a back grinding apparatus, and rough grinding is performed until the wafer thickness reaches about 100 / zm. It is preferable. After that, the grinding distortion layer generated by grinding is removed, and the desired 10 m to: L 00 m thickness is covered. Especially about the rough grinding method at this time Any known method can be used.
  • the grinding strain can be removed by selecting a force such as felt wheel method, plasma etching method, CMP method and chemical etching method. In particular, when the chemical etching method is used, since the wafer with the fixing agent has a permeation preventing portion, the permeation of the etching solution can be effectively prevented.
  • the felt grindstone used in the felt grindstone method is produced, for example, by impregnating a felt material described in JP-A-2002-28311, JP-A-2002-283212, etc. with abrasive grains.
  • a grindstone can be used suitably.
  • RIE reactive ion etching
  • the CMP method is used for flatness even during device formation.
  • polishing the back surface it is switched to a simple slurry in which silicon fine particles are dispersed in water in order to eliminate contaminant ions as much as possible. Polishing can be performed.
  • the chemical etching method is carried out using about 40-50% KOH solution, HFZ nitric acid mixed solution, etc. as an etching solution, and it is implemented as an apparatus like “GL-210S” manufactured by SEZ. It is possible to be.
  • the wafer that can be processed with the wafer with a fixing agent of the present invention is not particularly limited, but is preferably a semiconductor wafer.
  • a semiconductor wafer suitable for the application and processing method can be used, and it is likely to have a large area or a variety of complicated structures on the surface.
  • the process (V) includes a semiconductor element formed in a region defined by a plurality of die cinder streets, and the die cinder streets are cut corresponding to the thickness of the semiconductor chip.
  • a semiconductor wafer having grooves formed by tip dicing can be used.
  • a hole having a predetermined depth is formed on the surface, the inner wall of the hole is covered with an insulating film, and the hole covered with the insulating film is formed into a conductive electrode material.
  • a semiconductor wafer in which is embedded can be used. Further, the semiconductor wafer may have a conductive electrode on the surface, for example, a solder bump, etc., formed on the surface.
  • the processed wafer and the wafer with the fixing agent are peeled off.
  • at least one of the wafer and the supporting wafer is heated to a temperature equal to or higher than the melting temperature of the used fixing agent, so that the fixing agent is melted and the wafer can be peeled off from the supporting wafer.
  • the penetration preventing part fixed to the support wafer with the fixing agent can also be removed.
  • the fixing agent remains on the surface of the wafer after peeling (the surface on the side fixed with the fixing agent), it can be removed by washing with a solvent capable of dissolving the fixing agent. . this As such a solvent, it is preferable to use the solvent used for dissolving the fixing agent on the support wafer edge portion in the method for producing a wafer with a fixing agent of the present invention.
  • Examples of the cleaning method include a method of immersing a wafer in a solvent, and a method of spraying a cleaning liquid onto the wafer.
  • the temperature of the solvent is not particularly limited, but is preferably 20 to 80 ° C, more preferably 30 to 50 ° C.
  • the support wafer after peeling is preferably washed with the above-mentioned solvent and reused.
  • the wafer with a fixing agent of the present invention can be used for polishing polishing of a wafer to be processed such as a semiconductor wafer, and the workpiece to be processed by the fixing agent used for bonding and fixing the support wafer and the processing wafer. Contamination of the wafer and the working environment can be prevented, and further, it is possible to prevent the liquid material from infiltrating between the supporting wafer and the wafer to be covered. Further, the method for producing a wafer with a fixing agent of the present invention can be used for efficiently producing a wafer with a fixing agent that can be used for polishing 1 polishing of a wafer to be processed such as a semiconductor wafer.

Abstract

A wafer (100) with a fixing agent, having a supporting wafer (1) and the fixing agent (2) arranged on the surface of the supporting wafer (1). The wafer (100) further has an infiltration preventive structure (3) arranged at an edge section of the supporting wafer (1). The fixing agent (2) is arranged in a recess formed by the supporting wafer (1) and the infiltration preventive structure (3). When the supporting wafer (1) and a wafer to be processed are bonded and fixed, the fixing agent (2) is prevented from projecting and contaminating the work environment, and further, a liquid substance can be prevented from infiltrating between the supporting wafer (1) and the wafer to be processed.

Description

明 細 書  Specification
固定剤付きウェハ及び固定剤付きウェハの製造方法  Wafer with fixing agent and method for producing wafer with fixing agent
技術分野  Technical field
[0001] 本発明は、固定剤付きウェハ及び固定剤付きウェハの製造方法に関し、更に詳し くは、支持ウェハと被加工ウェハ (ウェハ）とを固定剤により接着固定するときに、固 定剤が支持ウェハとウェハとの間からはみ出してくることを防止し、作業環境の汚染 を防止することが可能であり、更に、支持ウェハとウェハとの間に液状物質が染み込 むことを防止することが可能な固定剤付きウェハと、そのような固定剤付きウェハを効 率的に製造する固定剤付きウェハの製造方法に関する。  [0001] The present invention relates to a wafer with a fixing agent and a method for producing a wafer with a fixing agent, and more specifically, when a supporting wafer and a wafer to be processed (wafer) are bonded and fixed with a fixing agent, the fixing agent is used. It is possible to prevent the support wafer from protruding between the wafers, to prevent contamination of the work environment, and also to prevent the liquid material from infiltrating between the support wafer and the wafer. The present invention relates to a wafer with a fixing agent that can be used, and a method for manufacturing a wafer with a fixing agent that efficiently manufactures such a wafer with a fixing agent.
背景技術  Background art
[0002] 半導体デバイスの製造工程において、略円板形状である半導体ウェハの表面に I C、 LSIなどの回路を格子状に多数形成し、該回路が形成された各領域を所定の切 断ラインに沿ってダイシングすることにより、個々の半導体素子が製造されている。こ のようにして半導体素子を製造するに際し、半導体素子の放熱性を良好にするととも に、携帯電話などのモパイル機器の小型化および低コストィ匕を実現するために、半 導体素子の厚さをできるだけ薄く形成することが望まれている。そのため、半導体ゥ ェハを個々の素子に分割する前に、その裏面を研削して所定の厚さに加工する研削 工程が行われている。この研削工程においては、半導体素子は研削機の定盤などの 支持体に、仮止め接着剤にて堅固に固定されている必要があるが、研削終了後は支 持体力 剥離する必要がある。  [0002] In a semiconductor device manufacturing process, a large number of circuits such as ICs and LSIs are formed in a lattice shape on the surface of a substantially disc-shaped semiconductor wafer, and each region where the circuits are formed is formed into a predetermined cut line. Individual semiconductor elements are manufactured by dicing along. In manufacturing a semiconductor element in this way, the thickness of the semiconductor element is reduced in order to improve the heat dissipation of the semiconductor element and to realize the miniaturization and low cost of the mobile device such as a mobile phone. It is desired to form it as thin as possible. For this reason, before the semiconductor wafer is divided into individual elements, a grinding process is performed in which the back surface is ground to a predetermined thickness. In this grinding process, the semiconductor element needs to be firmly fixed to a support such as a surface plate of a grinding machine with a temporary adhesive, but the support body force needs to be peeled off after grinding.
[0003] 従来、このような半導体ウェハの仮止め接着剤としてワックスが広く用いられており、 種々のワックスが提案されている。たとえば、 HLB値が 7〜13のポリグリセリン類を有 効成分とするワックス (例えば、特許文献 1参照。）や、酸価が 100以上のロジン榭脂 、ロジン榭脂の誘導体、ロジン榭脂の変成物、スチレン 'アクリル共重合体の 1種また は 2種以上を含むワックス (例えば、特許文献 2参照。）が開示されている。  Conventionally, wax has been widely used as a temporary fixing adhesive for such semiconductor wafers, and various waxes have been proposed. For example, wax containing polyglycerin having an HLB value of 7 to 13 as an active ingredient (see, for example, Patent Document 1), rosin resin having an acid value of 100 or more, rosin resin derivatives, rosin resin A wax containing one or more of a modified product, a styrene′acrylic copolymer (for example, see Patent Document 2) is disclosed.
[0004] 上記従来のワックスは、ウェハの研削処理におけるプロセス温度では接着強度が 保てないこと、薄く研削された半導体ウェハ等の剥離性が悪いこと、更に加工処理後 の洗浄が難しいこと等の問題があった。 [0004] The above-mentioned conventional wax cannot maintain the adhesive strength at the process temperature in the grinding process of the wafer, has poor peelability on a thinly ground semiconductor wafer, etc., and further after processing There were problems such as difficult cleaning.
[0005] これに対し、液晶化合物やそれを含有する組成物を接着剤として使用して半導体 ウェハを固定することにより、上記問題を解決する方法が開示されている（例えば、特 許文献 3参照。）。  [0005] On the other hand, a method for solving the above problem by fixing a semiconductor wafer using a liquid crystal compound or a composition containing the same as an adhesive has been disclosed (for example, see Patent Document 3). .)
[0006] しかし、上記ワックスや液晶化合物を使用して半導体ウェハ (被加工ウェハ）を支持 体 (支持ウェハ等）に固定する場合には、半導体ウェハとその支持体との間に挟まれ たワックス又は液晶化合物がはみ出して外部に漏れ出し、半導体ウェハや作業環境 を汚染するという問題があった。また、支持ウェハに被加工ウェハを固定し、化学エツ チング方式等により被カ卩ェウェハを加工するときに、エッチング液等の液状物質が支 持ウェハと被加工ウェハとの間に染み込み、回路等が形成された被加工ウェハの表 面が腐食すると 、う問題があった。  However, when a semiconductor wafer (wafer to be processed) is fixed to a support (support wafer, etc.) using the wax or liquid crystal compound, the wax sandwiched between the semiconductor wafer and the support is used. Or, there was a problem that the liquid crystal compound overflowed and leaked outside, contaminating the semiconductor wafer and the work environment. Also, when a wafer to be processed is fixed to a support wafer and the wafer to be processed is processed by a chemical etching method or the like, a liquid substance such as an etchant penetrates between the supporting wafer and the wafer to be processed, and a circuit, etc. There was a problem when the surface of the wafer to be processed on which corrosion was formed corroded.
特許文献 1：特開平 7— 224270号公報  Patent Document 1: Japanese Patent Laid-Open No. 7-224270
特許文献 2：特開平 9 157628号公報  Patent Document 2: JP-A-9 157628
特許文献 3：国際公開第 03Z095579号パンフレット  Patent Document 3: Pamphlet of International Publication No. 03Z095579
発明の開示  Disclosure of the invention
[0007] 本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、支持 ウェハと被加工ウェハ (ウェハ)とを固定剤により接着固定するときに、固定剤が支持 ウェハとウェハとの間からはみ出してくることを防止し、ウェハや作業環境の汚染を防 止することが可能であり、更に、支持ウェハとウェハとの間に液状物質が染み込むこ とを防止することが可能な固定剤付きウエノ、、及びそのような固定剤付きウェハを効 率的に製造することが可能な固定剤付きウェハの製造方法を提供することを目的と する。  [0007] The present invention has been made in view of such problems of the prior art, and when the support wafer and the wafer to be processed (wafer) are bonded and fixed with a fixative, the fixative is supported by the support wafer. It is possible to prevent the wafer and the working environment from being contaminated, and to prevent the liquid material from penetrating between the support wafer and the wafer. It is an object of the present invention to provide a wafer with a fixing agent that can be used, and a method for manufacturing a wafer with a fixing agent that can efficiently manufacture such a wafer with a fixing agent.
[0008] 上記課題を解決する本発明の固定剤付きウェハ及び固定剤付きウェハの製造方 法は、以下に示す通りである。  [0008] A wafer with a fixing agent and a method for producing a wafer with a fixing agent of the present invention that solves the above-described problems are as follows.
[0009] [1] 支持ウェハと、前記支持ウェハの表面に配設される固定剤とを備える固定剤付 きウェハであって、前記固定剤が前記支持ウェハのエッジ部（支持ウェハエッジ部） を除いた部分に配設され、前記支持ウェハエッジ部に配設される染み込み防止構造 を更に備える固定剤付きウェハ。 [0010] [2] 前記固定剤の表面に配設されるカバーフィルムを更に備える [1]に記載の固定 剤付きウェハ。 [1] A wafer with a fixing agent comprising a supporting wafer and a fixing agent disposed on the surface of the supporting wafer, wherein the fixing agent serves as an edge portion (supporting wafer edge portion) of the supporting wafer. A wafer with a fixing agent, further comprising a permeation preventive structure disposed at the removed portion and disposed at the support wafer edge portion. [0010] [2] The wafer with a fixing agent according to [1], further comprising a cover film disposed on a surface of the fixing agent.
[0011] [3] 前記染み込み防止構造が、リング状の染み込み防止部材により形成されている  [3] The penetration preventing structure is formed of a ring-like penetration preventing member.
[1]又は [2]に記載の固定剤付きウェハ。  The wafer with a fixing agent according to [1] or [2].
[0012] [4] 固定剤を支持ウェハの表面に塗布して固定剤付きウェハを製造する固定剤付 きウェハの製造方法であって、前記支持ウェハのエッジ部（支持ウェハエッジ部）に、 染み込み防止構造を配設する工程を有する固定剤付きウェハの製造方法。  [0012] [4] A method for producing a wafer with a fixing agent, wherein a fixing agent is applied to a surface of a supporting wafer to produce a wafer with a fixing agent, and soaks into an edge portion (supporting wafer edge portion) of the supporting wafer. The manufacturing method of the wafer with a fixing agent which has the process of arrange | positioning a prevention structure.
[0013] [5] 前記固定剤を、液体の状態で、前記支持ウェハの表面に塗布する工程と、前 記固定剤を溶解することができる溶剤で前記支持ウェハエッジ部上の前記固定剤を 溶解除去する工程と、前記支持ウェハエッジ部に、染み込み防止構造を配設するェ 程とを有する [4]に記載の固定剤付きウェハの製造方法。 [5] A step of applying the fixing agent to the surface of the supporting wafer in a liquid state, and dissolving the fixing agent on the edge of the supporting wafer with a solvent capable of dissolving the fixing agent. The method for producing a wafer with a fixing agent according to [4], further comprising a step of removing and a step of disposing a permeation prevention structure at the edge of the supporting wafer.
[0014] [6] 前記支持ウェハエッジ部に、染み込み防止構造を配設した後に、更に、カバー フィルムを前記固定剤の表面に貼り付ける工程を有する [5]に記載の固定剤付きゥ ェハの製造方法。 [6] The wafer with the fixing agent according to [5], further comprising a step of attaching a cover film to a surface of the fixing agent after the penetration preventing structure is provided on the edge of the supporting wafer. Production method.
[0015] [7] 前記支持ウェハエッジ部に、染み込み防止構造を配設する工程と、前記固定 剤を、前記支持ウェハと前記染み込み防止構造とにより形成される窪みに配置し、前 記固定剤を液体状態として、前記支持ウェハの表面に塗布する工程とを有する [4] に記載の固定剤付きウェハの製造方法。  [7] A step of providing a penetration preventing structure at the edge of the supporting wafer, and the fixing agent is disposed in a recess formed by the supporting wafer and the penetration preventing structure, and the fixing agent is [4] The method for producing a wafer with a fixing agent according to [4], further comprising: applying a liquid state to the surface of the support wafer.
[0016] [8] 前記固定剤を液体状態とする前に、カバーフィルムを前記固定剤の表面に配 置し、前記カバーフィルムの上から押圧しながら前記固定剤を液体状態とし、前記固 定剤を前記支持ウェハの表面に塗布する [7]に記載の固定剤付きウェハの製造方 法。  [0016] [8] Before the fixing agent is in a liquid state, a cover film is placed on the surface of the fixing agent, and the fixing agent is in a liquid state while pressing from above the cover film, so that the fixing is performed. The method for producing a wafer with a fixing agent according to [7], wherein an agent is applied to the surface of the support wafer.
[0017] [9] 前記固定剤を、前記支持ウェハの表面に塗布する工程が、前記固定剤を前記 支持ウェハの表面に乗せ、前記固定剤を、加熱溶融した状態で、前記支持ウェハの 表面に塗布する工程である [4]〜 [8]の 、ずれかに記載の固定剤付きウェハの製造 方法。  [9] The step of applying the fixing agent to the surface of the supporting wafer includes placing the fixing agent on the surface of the supporting wafer, and heating and melting the fixing agent in the surface of the supporting wafer. The method for producing a wafer with a fixing agent according to any one of [4] to [8], which is a step of applying to a wafer.
[0018] [10] 前記支持ウェハエッジ部に染み込み防止構造を配設する工程が、前記支持 ウェハエッジ部に、リング状の染み込み防止部材を配設する工程である [4]〜 [9]の いずれかに記載の固定剤付きウェハの製造方法。 [0018] [10] The step of disposing a permeation preventing structure on the support wafer edge portion is a step of disposing a ring-shaped permeation prevention member on the support wafer edge portion. The manufacturing method of the wafer with a fixing agent in any one.
[0019] 本発明の固定剤付きウェハによれば、染み込み防止構造が、支持ウェハエッジ部 に配設されるため、固定剤付きウェハに被加工ウェハを接着固定するときに、染み込 み防止構造により、固定剤が支持ウェハと被加工ウェハとの間からはみ出すことを防 止することが可能となる。また、支持ウェハと被加工ウェハとの間に液状物質が染み 込むことを防止することが可能となる。  [0019] According to the wafer with the fixing agent of the present invention, since the penetration preventing structure is provided at the edge of the supporting wafer, when the workpiece wafer is bonded and fixed to the wafer with the fixing agent, the penetration preventing structure is used. It becomes possible to prevent the fixing agent from protruding between the supporting wafer and the wafer to be processed. In addition, it is possible to prevent the liquid material from permeating between the support wafer and the workpiece wafer.
[0020] 本発明の固定剤付きウェハの製造方法によれば、支持ウェハエッジ部に染み込み 防止構造を配設するとともに、固定剤を支持ウェハの表面に薄く均一に塗布すること ができる。それにより、支持ウェハと被カ卩ェウェハとの間から固定剤がはみ出すことを 防止し、ウェハや作業環境の汚染を防止することができ、更に、支持ウェハと被加工 ウェハとの間に液状物質が染み込むことを防止することが可能な固定剤付きウェハ が得られる。  [0020] According to the method for producing a wafer with a fixing agent of the present invention, it is possible to dispose a permeation preventing structure at the edge of the supporting wafer and apply the fixing agent to the surface of the supporting wafer thinly and uniformly. As a result, it is possible to prevent the fixing agent from protruding between the support wafer and the wafer to be processed, and to prevent contamination of the wafer and the work environment. Further, a liquid substance is provided between the support wafer and the wafer to be processed. A wafer with a fixing agent capable of preventing the penetration of water is obtained.
図面の簡単な説明  Brief Description of Drawings
[0021] [図 1]図 1 (a)は、本発明の固定剤付きウェハの一実施形態を模式的に示す斜視図 であり、図 1 (b)は、図 1 (a)の A— A'断面図である。  [0021] [Fig. 1] Fig. 1 (a) is a perspective view schematically showing an embodiment of a wafer with a fixing agent of the present invention, and Fig. 1 (b) is an A- It is A 'sectional drawing.
[図 2]図 2 (a)は、本発明の固定剤付きウェハの他の実施形態を模式的に示す斜視 図であり、図 2 (b)は、図 2 (a)の B— B'断面図である。  [FIG. 2] FIG. 2 (a) is a perspective view schematically showing another embodiment of a wafer with a fixing agent of the present invention, and FIG. 2 (b) is a cross-sectional view taken along line B-B ′ of FIG. 2 (a). It is sectional drawing.
[図 3]図 3 (a)は、本発明の固定剤付きウェハの他の実施形態を模式的に示す平面 図であり、図 3 (b)は図 3 (a)の C C'断面図である。  [FIG. 3] FIG. 3 (a) is a plan view schematically showing another embodiment of a wafer with a fixing agent of the present invention, and FIG. 3 (b) is a cross-sectional view along CC ′ in FIG. 3 (a). It is.
[図 4A]本発明の固定剤付きウェハの製造方法の一実施形態の一工程を模式的に示 す斜視図である。  FIG. 4A is a perspective view schematically showing one step of one embodiment of a method for producing a wafer with a fixing agent of the present invention.
[図 4B]図 4Aにおける D— D'断面図である。  FIG. 4B is a sectional view taken along the line DD ′ in FIG. 4A.
[図 5A]本発明の固定剤付きウェハの製造方法の一実施形態の一工程を模式的に示 す斜視図である。  FIG. 5A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention.
[図 5B]図 5Aにおける E— E'断面図である。  FIG. 5B is a cross-sectional view taken along the line EE ′ in FIG. 5A.
[図 6A]本発明の固定剤付きウェハの製造方法の一実施形態の一工程を模式的に示 す斜視図である。  FIG. 6A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention.
[図 6B]図 6Aにおける F— F'断面図である。 [図 7A]本発明の固定剤付きウェハの製造方法の一実施形態の一工程を模式的に示 す斜視図である。 FIG. 6B is a cross-sectional view taken along the line FF ′ in FIG. 6A. FIG. 7A is a perspective view schematically showing one step of one embodiment of a method for producing a wafer with a fixing agent of the present invention.
[図 7B]図 7Aにおける G— G'断面図である。  FIG. 7B is a GG ′ sectional view in FIG. 7A.
[図 8A]本発明の固定剤付きウェハの製造方法の一実施形態の一工程を模式的に示 す斜視図である。  FIG. 8A is a perspective view schematically showing one step of one embodiment of a method for producing a wafer with a fixing agent of the present invention.
[図 8B]図 8Aにおける H— H'断面図である。  FIG. 8B is a cross-sectional view taken along line H—H ′ in FIG. 8A.
[図 9A]本発明の固定剤付きウェハの製造方法の他の実施形態の一工程を模式的に 示す平面図である。  FIG. 9A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
[図 9B]図 9Aにおける I I'断面図である。  FIG. 9B is a cross-sectional view taken along line I I ′ in FIG. 9A.
[図 10A]本発明の固定剤付きウェハの製造方法の他の実施形態の一工程を模式的 に示す平面図である。  FIG. 10A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
[図 10B]図 10Aにおける J-J'断面図である。  FIG. 10B is a cross-sectional view taken along the line JJ ′ in FIG. 10A.
[図 11A]本発明の固定剤付きウェハの製造方法の他の実施形態の一工程を模式的 に示す平面図である。  FIG. 11A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
[図 11B]図 11Aにおける K K'断面図である。  FIG. 11B is a KK ′ sectional view in FIG. 11A.
[図 12A]本発明の固定剤付きウェハの製造方法の他の実施形態の一工程を模式的 に示す平面図である。  FIG. 12A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
[図 12B]図 12Aにおける L L'断面図である。  FIG. 12B is an LL ′ cross-sectional view in FIG. 12A.
符号の説明  Explanation of symbols
[0022] 1, 11 :支持ウェハ、 2, 12 :固定剤、 3, 13 :染み込み防止部 (染み込み防止構造）、 4, 14 :支持ウェハエッジ部、 5, 15 :カバーフィルム、 21 :溶剤ノズル、 22 :溶剤、 31 ：窪み、 f :力、 W:染み込み防止剤の幅、 R:回転方向、 100, 101, 102, 103, 104 ：固定剤付きウェハ。  [0022] 1, 11: Support wafer, 2, 12: Fixing agent, 3, 13: Infiltration prevention part (infiltration prevention structure), 4, 14: Support wafer edge part, 5, 15: Cover film, 21: Solvent nozzle, 22: solvent, 31: dent, f: force, W: width of penetration inhibitor, R: rotation direction, 100, 101, 102, 103, 104: wafer with fixing agent.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0023] 次に、本発明を実施するための最良の形態 (以下、「実施形態」という。）を図面を 参照しながら詳細に説明するが、本発明は以下の実施形態に限定されるものではな ぐ本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、適宜設計 の変更、改良等が加えられることが理解されるべきである。 [0024] (1)固定剤付きウェハ： Next, the best mode for carrying out the present invention (hereinafter referred to as “embodiment”) will be described in detail with reference to the drawings. However, the present invention is limited to the following embodiment. However, it should be understood that design changes and improvements can be made as appropriate based on the general knowledge of those skilled in the art without departing from the spirit of the present invention. [0024] (1) Wafer with fixing agent:
図 1 (a)、図 1 (b)に示すように、本発明の固定剤付きウェハの一の実施形態は、支 持ウェハ 1と、支持ウェハ 1の表面に配設される固定剤 2と、支持ウェハ 1のエッジ部 分 (支持ウェハエッジ部) 4に配設される染み込み防止構造 (染み込み防止部） 3とを 備える固定剤付きウェハ 100である。そして、固定剤 2は、支持ウェハエッジ部 4を除 いた部分に配設されており、これにより固定剤 2が、支持ウェハ 1と染み込み防止部 3 とにより形成される窪みに配設される構造となっている。ここで、図 1 (a)は、本発明の 固定剤付きウェハの一の実施形態を模式的に示す斜視図であり、図 1 (b)は、図 l (a )の A— A'断面図、すなわち A— A'を通り支持体 1に垂直な平面で固定剤付きゥェ ハ 100を切断した断面図である。  As shown in FIGS. 1 (a) and 1 (b), an embodiment of the wafer with a fixing agent of the present invention includes a supporting wafer 1 and a fixing agent 2 disposed on the surface of the supporting wafer 1. 1 is a wafer 100 with a fixing agent provided with an infiltration prevention structure (infiltration prevention portion) 3 disposed on an edge portion (support wafer edge portion) 4 of the support wafer 1. The fixing agent 2 is disposed in a portion excluding the support wafer edge portion 4, whereby the fixing agent 2 is disposed in a recess formed by the support wafer 1 and the penetration preventing portion 3. It has become. Here, FIG. 1 (a) is a perspective view schematically showing one embodiment of a wafer with a fixing agent of the present invention, and FIG. 1 (b) is a cross-sectional view taken along line AA ′ of FIG. 1 (a). FIG. 1 is a cross-sectional view of a wafer 100 with a fixing agent taken along a plane perpendicular to the support 1 through A—A ′.
[0025] (1 1)支持ウェハ；  [1 1] support wafer;
本実施形態において使用される支持ウェハの形状については、特に限定されるも のではなぐ図 1 (a)、図 1 (b)に示すように、円板状であることが好ましい。これは、通 常被加工ウェハが円形（円板状）に形成されることが多ぐそれに合わせて支持ゥェ ハをほぼ同じ大きさの円形に形成することが好ましいためである。従って、被加工ゥ ェハが他の形状である場合には、それと同じ形状とすることが好ましい。  The shape of the support wafer used in the present embodiment is not particularly limited, and is preferably a disc shape as shown in FIGS. 1 (a) and 1 (b). This is because the wafer to be processed is usually formed in a circular shape (disk shape), and accordingly, it is preferable to form the support wafer in a circular shape having substantially the same size. Accordingly, when the wafer to be processed has another shape, it is preferable to use the same shape.
[0026] 支持ウェハの厚さは、特に限定されるものではないが、直径 200mmのいわゆる 20 Ommウェハの場合は 300 μ m〜725 μ mであることが好ましい。支持ウェハの裏面（ 固定剤等が配設されな ヽ側の面)を基準面とすれば、その裏面と表面との距離 (厚み )は、被加工ウェハとの貼り合わせ精度および貼り合わせ後のプロセスでの取り扱い 精度に影響するため、この厚み精度が面内で ± 5 m以下、好ましくは ± 1 m以下 、さらに好ましくは ±0. 3 m以下の平坦性を有することが好ましい。  The thickness of the support wafer is not particularly limited, but is preferably 300 μm to 725 μm in the case of a so-called 20 Omm wafer having a diameter of 200 mm. If the back surface of the support wafer (the surface on the side where the fixing agent or the like is not disposed) is used as the reference surface, the distance (thickness) between the back surface and the front surface is determined by the bonding accuracy with the wafer to be processed and the post-bonding Since this affects the handling accuracy in the process, it is preferable that the thickness accuracy has a flatness of ± 5 m or less, preferably ± 1 m or less, more preferably ± 0.3 m or less in the surface.
[0027] 支持ウェハの材質は特に限定されるものではないが、セラミックス、金属化合物、ガ ラス素材等が好ましい。セラミックスとしては、例えば、炭化珪素、炭化窒素、アルミナ 、窒化アルミニウム、ジルコユア、チタ-ァ等が挙げられる。金属化合物としては、例 えば、 SUS302B, SUS304, SUS309S, SUS310S, SUS316, SUS316Ti、 S US317、 SUS321、 SUS347, SUSXM15J1等のオーステナイド系ステンレス素材 が挙げられる。ガラス素材としては、無アルカリガラス、石英等が挙げられる。また、シ リコン、 GaAs、 GaNなどの半導体ウェハも支持ウェハとして用いることができる。 [0027] The material of the support wafer is not particularly limited, but ceramics, metal compounds, glass materials, and the like are preferable. Examples of ceramics include silicon carbide, nitrogen carbide, alumina, aluminum nitride, zircoaure, and titanium. Examples of the metal compound include austenide stainless materials such as SUS302B, SUS304, SUS309S, SUS310S, SUS316, SUS316Ti, SUS317, SUS321, SUS347, and SUSXM15J1. Examples of the glass material include alkali-free glass and quartz. In addition, Semiconductor wafers such as recon, GaAs, and GaN can also be used as support wafers.
[0028] (1 2)固定剤； [0028] (1 2) fixative;
本実施形態において、図 1 (a)、図 1 (b)に示す支持ウェハ 1の表面に配設された 固定剤 2の厚さは 1 μ m〜 lmmであることが好ましぐ 5 μ m〜100 μ mであることが 更に好ましい。 1 μ mより薄いと、被加工ウェハを固定したときに、接着力が十分でな いことがある。 1mmより厚いと、固定剤 2を無駄に多く使用しコストアップになることが ある。  In this embodiment, the thickness of the fixing agent 2 disposed on the surface of the support wafer 1 shown in FIGS. 1 (a) and 1 (b) is preferably 1 μm to 1 mm. More preferably, it is ˜100 μm. If it is thinner than 1 μm, the adhesive strength may not be sufficient when the wafer to be processed is fixed. If it is thicker than 1 mm, the fixative 2 may be used unnecessarily, resulting in increased costs.
[0029] 本実施形態において使用する固定剤は、ホットメルト型接着剤であることが好ましい 。本実施形態において、ホットメルト型接着剤とは、常温では固体であるが、加熱溶 融して被着物を付着させ冷却することにより、被着物を接着することができ、再度カロ 熱溶融することで被着物を剥離することができる接着剤をいう。なお、接着面に楔の ようなものを挟み込んで剥離してもよ ヽ。上記ホットメルト型接着剤組成物としては、 組成物に凝集力を付与するために結晶性化合物を主成分として含有することが好ま しい。ここで、「主成分」とは 70質量％以上含有される成分をいう。そして、その結晶 性化合物の溶融温度は 50〜300°Cであることが好ましぐ 55〜250°Cであること力 S 更に好ましい。ここで、溶融温度とは、示差走査熱量分析装置 (DSC)で測定したメイ ンの溶融ピーク曲線におけるピーク温度をいう。結晶性化合物の溶融温度が上記範 囲にあることにより、接着時の耐熱温度を向上させることができる。  [0029] The fixing agent used in the present embodiment is preferably a hot-melt adhesive. In the present embodiment, the hot-melt adhesive is solid at room temperature, but can be adhered by heating and melting, adhering the adherend and cooling, and again hot-melting by heat. Refers to an adhesive that can peel off the adherend. It is also possible to put something like a wedge on the adhesive surface and peel it off. The hot melt adhesive composition preferably contains a crystalline compound as a main component in order to impart cohesion to the composition. Here, the “main component” means a component contained in 70% by mass or more. The melting temperature of the crystalline compound is preferably 50 to 300 ° C, more preferably 55 to 250 ° C. Here, the melting temperature refers to the peak temperature in the main melting peak curve measured by a differential scanning calorimeter (DSC). When the melting temperature of the crystalline compound is in the above range, the heat-resistant temperature at the time of adhesion can be improved.
[0030] 上記結晶性ィ匕合物は、分子量が 1000以下、好ましくは 150〜800、より好ましくは 200〜600である。結晶性ィ匕合物の分子量が上記範囲を超えると、結晶性化合物の 溶剤への溶解性が低くなるため、被加工ウェハと固定剤付きウェハとを溶剤を使用し て剥離し、その後溶剤で洗浄する場合に、その溶剤による剥離'洗浄が不十分となる ことがある。  [0030] The crystalline compound has a molecular weight of 1000 or less, preferably 150 to 800, more preferably 200 to 600. If the molecular weight of the crystalline compound exceeds the above range, the solubility of the crystalline compound in the solvent decreases, so the wafer to be processed and the wafer with the fixing agent are separated using a solvent, and then the solvent is used. When cleaning, peeling and cleaning with the solvent may be insufficient.
[0031] また、上記結晶性ィ匕合物は、半導体ウェハ上に形成される配線および絶縁膜に対 してダメージを与えず、汚染源ともならず、溶融時に固定剤が変性しないなどの観点 から、カルボン酸基ゃァミノ基などの活性な官能基を有しな 、中性ィ匕合物であること が好ましい。また、媒質中に拡散して絶縁性に悪影響を及ぼすアルカリ金属等 (例え ば、 Na、 K、 Ca、 Fe、 Cu、 Ni、 Cr、 Al等）の金属含有量の合計が lOOppm以下であ ることが好ましぐ lOppm以下となるまでメタルフリー化処理したものであることが更に 好ましい。なお、金属酸ィ匕物など安定な形態で含有するものはこの限りではない。 [0031] In addition, the crystalline compound does not damage the wiring and insulating film formed on the semiconductor wafer, does not cause contamination, and does not denature the fixing agent when melted. Further, it is preferably a neutral compound without an active functional group such as a carboxylic acid group or an amino group. In addition, the total metal content of alkali metals, etc. (such as Na, K, Ca, Fe, Cu, Ni, Cr, Al, etc.) that diffuse into the medium and adversely affect the insulation properties is less than lOOppm. It is more preferable that the metal-free treatment is performed until it becomes 10 ppm or less. In addition, what is contained with a stable form, such as a metal oxide, is not this limitation.
[0032] このような結晶性化合物としては、 1, 3, 5 トリ-トロベンゼン、 2, 3, 6 トリ-トロ フエノール、 2, 4, 5 トリ-トロトルエン等の-トロ化合物なども挙げることができるが 、取扱上の安全性が高ぐ溶融時の耐熱性に優れ、着色が少ないなどの観点から、 N元素を含まない C、 H、 Oの元素のみ力もなる有機化合物が好ましい。具体的には 、以下に例示するような芳香族化合物、脂肪族化合物および脂環式化合物などが挙 げられる。 [0032] Examples of such crystalline compounds include -tro compounds such as 1, 3, 5 tri-trobenzene, 2, 3, 6 tri-trophenol, 2, 4, 5 tri-trotoluene, and the like. However, from the viewpoints of high safety in handling, excellent heat resistance during melting, and low coloring, an organic compound that does not contain N element and has only C, H, and O elements is preferable. Specific examples include aromatic compounds, aliphatic compounds, and alicyclic compounds as exemplified below.
[0033] 芳香族化合物としては、例えば、 9H キサンテン、ベンゾフラン 3 (2H) オン、 1, 5 ジフエ二ルー 2, 4 ペンタジェン 1 オン、ジ 2 ナフチルエーテル、 cis —1, 8 テルピン、 2, 3 ジメチルナフタレン、 1, 2 ナフタレンジオール、ジー1 ナフチルメタン、ビフエ二ルー 2, 2，ージオール、ジ 1 ナフチルエーテル、ビス（ジ フエニルメチル）エーテル、 9, 10 ジヒドロアントラセン、 2, 3, 5, 6—テトラメチルー p べンゾキノン、 2, 6 ジメチルナフタレン、シリンガアルデヒド、バニリルアルコー ル、 1, 3 ジフエニルイソべンゾフラン、 2, 3， 一ジヒドロキシベンゾフエノン、イソヒドロ ベンゾイン、 4, 4' ジメチルビフエニル、 1, 3 ナフタレンジオール、 4 フエナント ロール、 3, 3—ジフエ-ルフタリド、ペンタメチルフエノール、へキサェチルベンゼン、 3, 4 ジヒドロキシベンゾフエノン、 2, 4 ジヒドロキシベンズアルデヒド、 p ヒドロキ シベンゾフエノン、 4, 5, 9, 10—テトラヒドロピレン、 2, 3, 4 トリヒドロキシベンゾフエ ノン、へマトキシリン、 2—イソプロピル一 5—メチルヒドロキノン、 1, 9 ジフエニル一 1 , 3, 6, 8 ノナテトラェン一 5—オン、 9 フエニルフルオレン、 1, 4, 5 ナフタレン トリオール、 1 アントロール、 1, 4ージフエ二ルー 1, 3 ブタジエン、ガルビノキシル 、ピレン、 9 フエ二ルアントラセン、トリフエニルメタノール、 1, 1， 一ビナフチル、 m— キシレン 2, 4, 6 トリオール、 4, 4'ーメチレンジフエノール、へキサメチルベンゼ ン、ジベンゾ一 18 クラウン一 6、ジフエノキノン、ビフエ-ルー 4—オール、 1H フエ ナレン、 10 ヒドロキシアントロン、フラボノール、ベンゾアントロン、 9H キサンテン —9—オン、テトラフエ二ルフラン、 2—メチルアントラキノン、 4 ヒドロキシ一 1—ナフ トアルデヒド、 1, 7 ナフタレンジオール、 2, 5 ジエトキシ p べンゾキノン、クル クミン、 2, 2'—ビナフチル、 1, 8 ジヒドロキシアントラキノン、 1, 4 ナフタレンジォ ール、 1ーヒドロキシアントラキノン、 3, 4ージヒドロキシアントロン、 p—テルフエニル、 4, 4'ージヒドロキシベンゾフエノン、アントラセン、 2, 4, 6 トリヒドロキシァセトフエノ ン、 [0033] Examples of aromatic compounds include 9H xanthene, benzofuran 3 (2H) on, 1,5 diphenyl 2,4 pentagen 1 on, di 2 naphthyl ether, cis -1,8 terpine, 2, 3 dimethyl Naphthalene, 1, 2 naphthalene diol, G 1 naphthylmethane, biphenyl 2, 2, diol, di 1 naphthyl ether, bis (diphenylmethyl) ether, 9, 10 dihydroanthracene, 2, 3, 5, 6-tetramethyl-p Benzoquinone, 2,6 dimethylnaphthalene, syringaldehyde, vanillyl alcohol, 1,3 diphenylisobenzofuran, 2,3,1 dihydroxybenzophenone, isohydrobenzoin, 4,4 'dimethylbiphenyl, 1,3 naphthalenediol, 4 Phenanthrol, 3, 3-Diphenylphthalide, Pentamethylphenol, Hexaethyl benzene 3, 4, dihydroxybenzophenone, 2,4 dihydroxybenzaldehyde, p-hydroxybenzophenone, 4, 5, 9, 10-tetrahydropyrene, 2, 3, 4 trihydroxybenzophenone, hematoxylin, 2-isopropyl-5- Methylhydroquinone, 1,9 diphenyl-1,3,6,8 Nonatetraen-1-one, 9 phenylfluorene, 1,4,5 naphthalene triol, 1 anthrol, 1,4-diphenyl1,3 butadiene, galvinoxyl , Pyrene, 9 phenylanthracene, triphenylmethanol, 1, 1, 1-binaphthyl, m-xylene 2, 4, 6 triol, 4, 4'-methylene diphenol, hexamethylbenzen, dibenzo-18 crown-1, 6, Diphenoquinone, biphenol-4-ol, 1H phenalene, 10 hydroxyanthrone, flavonol, ben Anthrone, 9H-xanthene-9-one, Tetorafue two furan, 2-methyl anthraquinone, 4-hydroxy-one 1-naphthoquinone collected by aldehydes, 1, 7-naphthalene diol, 2, 5-diethoxy p base Nzokinon, Kuru Cumin, 2,2'-binaphthyl, 1,8 dihydroxyanthraquinone, 1,4 naphthalene diol, 1-hydroxyanthraquinone, 3,4-dihydroxyanthrone, p-terphenyl, 4,4'-dihydroxybenzophenone, anthracene, 2, 4, 6 Trihydroxyacetophenone,
1, 8 アントラセンジオール、テトラフェニルエチレン、 1, 7 ジヒドロキシー9ーキ サンテノン、 2, 7 ジメチルアントラセン、ェピカテキン、ナリンゲ-ン、 2 アントロー ル、 1, 5 ナフタレンジオール、ベンジリデンフタリド、 2 フエ二ルナフタレン、 cis— デカヒドロ一 2 ナフトール（cisoid)、 (2R, 3R)— 2, 3 ビス（ジフエ-ルホスフイノ） ブタン、 trans— 1, 2 ジベンゾィルエチレン、 trans— 1, 4 ジフエ二ノレ一 2 ブテ ン一 1, 4 ジオン、ビス（2 ヒドロキシェチル）テレフタラート、フルオランテン、ビフエ -レン、イソバニリン、フルオレン、 9—アントロール、 p フエ-レンジァセタート、 tran s—スチルベン、ビフエ二ルー 3, 3，ージオール、 2, 5 ジヒドロキシベンゾフエノン、 ピノールヒドラート、ベンゾイン、ヒドロべンゾイン、 1, 2—ビス（ジフエ-ルホスフイノ） ェタン、 2, 4 ジヒドロキシベンゾフエノン、 1, 8 ナフタレンジオール、 1, 2 ナフト キノン、 2, 4'—ジヒドロキシベンゾフエノン、 5 ヒドロキシ 1, 4 ナフトキノン、 1 フエナントロール、アントロン、 9 フルォレノール、トリフエ-ルホスフィンォキシド、ベ ンゾ [a]アントラセン、 1, 2 アントラセンジオール、 2, 3 ナフタレンジオール、 2, 4 , 6 トリヒドロキシベンゾフエノン、ジー2 ナフチルケトン、 3, 3 '—ジヒドロキシベン ゾフエノン、アルブチン、 1, 2, 3, 5 ベンゼンテトラオール、ジフエ二ルキノメタン、 2 —フエナントロール、 2, 3, 4 トリヒドロキシァセトフエノン、カプサンチン、 1, 3, 5— トリフエニルベンゼン、 3, 4, 5—トリヒドロキシベンゾフエノン、ベンゾ [a]ピレン、トリフ ェ-ルメチルペルォキシド、へキセストロール、 1, 1, 2, 2—テトラフエ-ルー 1, 2— エタンジオール、 1, 8 ジヒドロキシー3—メチルアントラキノン、ショウノウキノン、 2, 2' , 5, 6，ーテトラヒドロキシベンゾフエノン、エスクリン、 3, 4'ージヒドロキシベンゾフ ェノン、 2, 4, 5 トリヒドロキシァセトフエノン、 9, 10 フエナントレンキノン、 1, 1, 2, 2—テトラフエ-ルェタン、ルチン、 （一）一ヘスペレチン、 2, 3 ' , 4, 4，， 6 ペンタヒ ドロキシベンゾフエノン、 7—ヒドロキシクマリン、 dl—ヘスペレチン、ニンヒドリン、トリプ チセン、フルォレシン、タリセン、ジェチルスチルベストロール、ジベンゾ [a, h]アント ラセン、ペンタセン、 1, 6 ジヒドロキシアントラキノン、 3, 4' , 5, 7—テトラヒドロキシ フラボン、 2, 6 アントラセンジオール、ゲニスティン等が挙げられる。 1,8 anthracenediol, tetraphenylethylene, 1,7 dihydroxy-9-chi santenone, 2,7 dimethylanthracene, epicatechin, naringen, 2 anthrool, 1,5 naphthalenediol, benzylidenephthalide, 2 phenyl Naphthalene, cis—decahydro-2-naphthol (cisoid), (2R, 3R) — 2,3 bis (diphenylphosphino) butane, trans—1, 2 dibenzoylethylene, trans—1,4 diphenol 2 Ten 1,4 dione, bis (2hydroxyethyl) terephthalate, fluoranthene, biphenol-ene, isovanillin, fluorene, 9-antrol, p-phenolic dicetate, tran s-stilbene, biphenyl 2, 3, diol , 2, 5 dihydroxybenzophenone, pinol hydrate, benzoin, hydrobenzoin, 1, 2-bis ( Diphenol-phosphino) ethane, 2,4 dihydroxybenzophenone, 1,8 naphthalenediol, 1,2 naphthoquinone, 2,4'-dihydroxybenzophenone, 5 hydroxy 1,4 naphthoquinone, 1 phenanthrol, anthrone, 9 Fluorenol, triphenylphosphine oxide, benzo [a] anthracene, 1,2 anthracenediol, 2,3 naphthalenediol, 2,4,6 trihydroxybenzophenone, di-2 naphthyl ketone, 3, 3 ' —Dihydroxy benzophenone, arbutin, 1, 2, 3, 5 benzenetetraol, diphenylquinomethane, 2 —phenanthrol, 2, 3, 4 trihydroxyacetophenone, capsanthin, 1, 3, 5— triphenylbenzene 3, 4, 5-trihydroxybenzophenone, benzo [a] pyrene, triphenylmethyl peroxide, Hexestrol, 1, 1, 2, 2—Tetraphenol- 1,2—ethanediol, 1,8 dihydroxy-3-methylanthraquinone, camphorquinone, 2, 2 ', 5, 6, -tetrahydroxybenzophenone , Esculin, 3,4'-dihydroxybenzophenone, 2, 4, 5 trihydroxyacetophenone, 9, 10 phenanthrenequinone, 1, 1, 2, 2—tetraphenyl-rutan, rutin, (1) Hesperetin, 2, 3 ', 4, 4 ,, 6 Pentahydroxybenzophenone, 7-hydroxycoumarin, dl-Hesperetin, Ninhydrin, Triptycene, Fluoresin, Talycene, Jethylstilbestrol, Dibenzo [a, h] Ant Examples include helix, pentacene, 1,6 dihydroxyanthraquinone, 3,4 ′, 5,7-tetrahydroxy flavone, 2,6 anthracenediol, and genistein.
[0035] 脂肪族化合物としては、例えば、リビトール、 D ァラビトール、フリル、 γ—カロテ ン、 /3一力口テン、カンタリジン、ペンタエリトリトーノレ、 trans, trans— 1, 4 ジァセト キシブタジエン、 D グルシトール、 D—マンニトール、イドース、デカナール、 α—力 口テン、 2, 4, 6 トリメチルフロログルシノール、ガラクチトール、ェキリン、ェキレニン 、 trans- 1, 2—シクロベンタンジオール、マノオール、 1 ヘプタデカノール、 1ーォ クタデカノール、 1 ィコサノール、ジヒドロキシアセトン、 γ テルピネオール、 1一へ キサコサノール、 1—ヘントリアコンタノール、ステアロン等が挙げられる。 [0035] Examples of the aliphatic compound include ribitol, D-arabitol, furyl, γ-carotene, / 3 striking tenten, cantharidin, pentaerythritol, trans, trans-1,4 diacetoxybutadiene, D Glucitol, D-mannitol, idose, decanal, α-strength, 2, 4, 6 trimethylphloroglucinol, galactitol, echirin, echlenine, trans-1,2-cyclobentandiol, manol, 1 heptadecanol, 1-octadecanol, 1-icosanol, dihydroxyacetone, γ-terpineol, 1-hexacosanol, 1-hentriacontanol, stearone and the like.
[0036] 脂環式化合物としては、例えば、コプロスタノール、チモステロール、ェルゴカルシ フエロール、 β—シトステロール、ラノステロール、 11—デォキシコルチコステロン、コ レスタノ一ノレ、コレステロ一ノレ、テストステロン、エノレゴステロ一ノレ、スチグマステロ一ノレ 、エストラジオール、コルチコステロン、ェピコレスタノール、アンドロステロン、 17 α— ヒドロキシ一 11—デォキシコルチコステロン、ギトキシゲニン、ェピコプロスタノール、 カルシフエロール、プロゲステロン、デヒドロェピアンドロステロン、 7—デヒドロコレステ ロール、ァグノステロール、 11—デヒドロコルチコステロン、プレドニソロン、ジギトキシ ゲニン、エストロン、 13—エストラジオール、コルチソン、 D フルクトース（0；开 、 D— リキソース（ α形）、 D リキソース（ j8形）、イソマルトース、 D タロース（ j8形）、 D— タロース（α形）、 D ァロース（j8形）、 D—マンノース（j8形）、 D—マンノース（α形） 、 D キシロース（α形）、 D ガラクトース（j8形）、 Lーフコース（α形）、 D ダルコ ース（0；开 、 2—デォキシ— D グルコース、マルトトリオース、 D— altro ヘプッロ ース、 Lーァラビノース（ビラノース α形）、 D ァラビノース、カフェストール、 Lーァラ ビノース（ビラノース 13形）、 D—ガラクトース（ α形）、リコペン、ァゥクビン、スクロース 、フリーデリン、 cis- 1, 3, 5 シクロへキサントリオール、 D—イノシトール、ルティン 、ジォスゲニン、チゴゲニン、ゼアキサンチン、 myo イノシトール、セロビオース、ジ べレリン A3、へマテイン、べッリン、 D フルクトース（j8形）、 D アルトロース（j8形） 、ジベンゾ一 24 クラウン一 8、メチル D—ダルコビラノシド（ j8形）、 D ジギタロー ス、サリノマイシン、メチル D ガラクトピラノシド（α形）、 a , α—トレハロース、ビ キシン（全 trans形）、パラチノース、 trans— 1 , 4—テルピン、 D—キノボース（α形） 、 D— glycero— D— galacto ヘプトース、 D フコース（ α开 、 D—グノレコース（ j8 开 、 D— manno ヘプッロース、 D— glycero— D— gluco ヘプトース、ソホロー ス、サルササポゲニン、 L ソルボース、 D— altro— 3—ヘプッロース、ツイスタン、 ( + )一ボルネオール、イノシトール、（一） イソボルネオール、 Lーァラビノース（フラ ノース形）、 L ガラクトース（ひ形）、 a—サントニン、メチル D ガラクトピラノシド（ j8形）、シクロペンタデカノン、 δ—バレロラタトン、 cis— 2—メチルシクロへキサノー ル、下記化学式（1)〜（8)で表される化合物等が挙げられる。 [0036] Examples of the alicyclic compounds include coprostanol, timosterol, ergocalciferol, β-sitosterol, lanosterol, 11-deoxycorticosterone, cholesterol, and cholesterol, testosterone, enolegostero and cholesterol. , Stigmasterol, estradiol, corticosterone, epicholestanol, androsterone, 17 α-hydroxy-11-deoxycorticosterone, gitoxigenin, epicoprostanol, calcipherol, progesterone, dehydroepiandrosterone 7-dehydrocholesterol, agnosterol, 11-dehydrocorticosterone, prednisolone, digitoxigenin, estrone, 13-estradiol, cortisone, D fructose (0; open, D- Kisosu (alpha form), D-lyxose (j8 form) isomaltose, D-talose (j8 form) D-talose (alpha form), D Arosu (j8 form) D-mannose (j8 form) D-mannose ( α form), D xylose (alpha form), D galactose (j8 form), L-fucose (alpha form), D dalcoose (0; open, 2—deoxy—D glucose, maltotriose, D—altro heplaro , L-arabinose (bilanose α form), D arabinose, cafe stall, L-arabinose (bilanose 13 form), D-galactose (alpha form), lycopene, alkvin, sucrose, freederin, cis-1, 3, 5 cyclohe Xanthriol, D—inositol, rutin, diosgenin, tigogenin, zeaxanthin, myo inositol, cellobiose, gibberellin A3, hematein, belli , D fructose (j8 form), D altrose (j8 form), dibenzo 1-24 crown 1-8, methyl D-darcobilanoside (j8 form), D digitalose, salinomycin, methyl D galactopyranoside (alpha form), a, α-trehalose, bi Xin (all trans form), palatinose, trans-1, 4, terpin, D-quinoboose (alpha form), D-glycero- D-galacto heptose, D fucose (alpha-opening, D-gnolecose (j8 opening, D-manno Heprose, D—glycero— D—gluco heptose, sophorose, salsasapogenin, L sorbose, D—altro— 3—heptulose, Twistan, (+) one borneol, inositol, (one) isoborneneol, Larabinose (furanose) Form), L galactose (diamond), a-santonin, methyl D galactopyranoside (j8 form), cyclopentadecanone, δ-valerolataton, cis-2-methylcyclohexanol, the following chemical formulas (1) to ( Examples thereof include compounds represented by 8).
[化 1] [Chemical 1]
Figure imgf000014_0001
上記化合物の中では、加工性の観点から、コレステロール、コプロスタノール、チモ ステローノレ、エノレゴカノレシフェローノレ、 βーシトステロ一ノレ、ラノステロ一ノレ、 11ーデ ォキシコノレチコステロン、コレスタノ一ノレ、テストステロン、エノレゴステロ一ノレ、スチグマ ステロール、エストラジオール、コルチコステロン、ェピコレスタノール、アンドロステロ ン、 17 α—ヒドロキシ一 11—デォキシコルチコステロン、ギトキシゲニン-ェピコプロ スタノール、カルシフエロール、プロゲステロン、デヒドロェピアンドロステロン、 7—デ ヒドロコレステロ一ノレ、ァグノステロ一ノレ、 11—デヒドロコノレチコステロン、プレドニソロ ン、ジギトキシゲニン、エストロン、 13 エストラジオール、コルチソンおよび上記化学 式（1)〜（8)で表される化合物などのステロイド骨格を有する化合物、 trans— 1, 2 ーシクロペンタンジオール、マノオール、 1 ヘプタデカノール、 1ーォクタデカノール 、 1—ィコサノール、 γ—テルピネオール、 1—へキサコサノール、 1—ヘントリアコンタ ノールなどの水酸基含有化合物およびこれらの誘導体が特に好ましい。ただし、エス テル誘導体は、融点が低ぐ熱分解したときに酸性となって接着面を浸食する可能性 があるなどの理由力も好ましくない。
Figure imgf000014_0001
Among the above compounds, from the viewpoint of processability, cholesterol, coprostanol, timosteronore, enolego canreciferonore, β-sitostero-nore, lanostero-nore, 11-deoxy-cono-reticosterone, cholestano-nore, testosterone , Enoregosterol, stigmasterol, estradiol, corticosterone, epicholestanol, androsterol, 17 α-hydroxy 1-deoxycorticosterone, gitoxigenin-epicopro Stanol, calcipherol, progesterone, dehydroepandrosterone, 7-dehydrocholesterol, gnostello, 11-dehydroconoleticosterone, prednisolone, digitoxigenin, estrone, 13 estradiol, cortisone and the above formula ( Compounds having a steroid skeleton such as compounds represented by 1) to (8), trans-1,2-cyclopentanediol, manol, 1 heptadecanol, 1-octadecanol, 1-icosanol, γ -terpineol Hydroxyl-containing compounds such as 1-hexacosanol and 1-hentriacontanol and derivatives thereof are particularly preferable. However, ester derivatives are not preferable because they may become acidic when thermally decomposed with a low melting point and may erode the adhesive surface.
[0039] 上記結晶性ィ匕合物は、単独で用いてもよぐ 2種類以上を混合して用いてもよい。  [0039] The crystalline compound may be used alone or in combination of two or more.
上記結晶性ィ匕合物は、固定剤中における含有量が 70質量％以上、好ましくは 80質 量％以上、特に好ましくは 90質量％以上となるように用いられる。含有量が上記範囲 よりも低いと、溶融温度がシャープにならず、また溶融粘度も高くなることがある。  The crystalline compound is used so that the content in the fixing agent is 70% by mass or more, preferably 80% by mass or more, and particularly preferably 90% by mass or more. When the content is lower than the above range, the melting temperature may not be sharp and the melt viscosity may be increased.
[0040] 上記のような結晶性化合物を主成分として含む固定剤は、溶融温度幅が 1〜30°C であることが好ましぐ 1〜20°Cであることが更に好ましぐ 1〜10°Cであることが特に 好ましい。固定剤の溶融温度における溶融粘度が 0. 0001-0. lPa' sであることが 好ましく、 0. 001〜0. 05Pa' sであること力 S更に好ましく、 0. 001〜0. OlPa' sであ ることが特に好ましい。ここで、溶融温度幅とは、示差走査熱量分析装置 (DSC)で 測定したメインの溶融ピーク曲線における始点の温度と終点の温度との差をいう。溶 融温度幅および溶融粘度が上記範囲にあることにより、剥離容易性が向上するため 、被加工ウェハを支持ウェハから剥離する際に加える外力を小さくすることができる。  [0040] The fixing agent containing the crystalline compound as a main component as described above preferably has a melting temperature range of 1 to 30 ° C, more preferably 1 to 20 ° C. It is particularly preferable that the temperature is 10 ° C. The melt viscosity at the melting temperature of the fixative is preferably 0.0001-0. LPa's, preferably 0.001-0.05 Pa's S, more preferably 0.001-0. OlPa's. It is particularly preferred that Here, the melting temperature range refers to the difference between the starting point temperature and the ending point temperature in the main melting peak curve measured by a differential scanning calorimeter (DSC). When the melting temperature range and the melt viscosity are in the above ranges, the ease of peeling is improved, so that the external force applied when the wafer to be processed is peeled from the support wafer can be reduced.
[0041] 固定剤の溶融温度幅および溶融粘度は、上記結晶性化合物の溶融温度幅および 溶融粘度に強く依存することから、溶融温度幅が狭ぐ溶融粘度が低い結晶性化合 物を用いることが望ましい。すなわち、主成分である結晶性ィ匕合物としては、溶融温 度が 50〜300°C、溶融温度幅が 1〜30°C、溶融温度における溶融粘度が 0. 0001 〜0. lPa' sのものが好ましい。  [0041] Since the melting temperature range and the melt viscosity of the fixing agent strongly depend on the melting temperature range and the melt viscosity of the crystalline compound, it is necessary to use a crystalline compound with a narrow melting temperature range and a low melt viscosity. desirable. In other words, the crystalline compound as the main component has a melting temperature of 50 to 300 ° C, a melting temperature range of 1 to 30 ° C, and a melt viscosity at the melting temperature of 0.0001 to 0.1 lPa's. Are preferred.
[0042] 結晶性ィ匕合物の溶融温度幅を狭くし、溶融粘度を低減し、さらに遊離金属イオン量 を低減するために、結晶性化合物の精製を行うことが好ましい。結晶性化合物の精 製方法としては、たとえば、（a)結晶性化合物を溶剤に溶解し、溶剤を徐々に留去し て再結晶化させることで純度を高める方法、および (b)結晶性ィ匕合物を溶剤に溶解 し、その溶液をイオン交換樹脂に接触させて遊離金属を除去することで金属含有量 を減らす方法などが挙げられる。 [0042] In order to narrow the melting temperature range of the crystalline compound, to reduce the melt viscosity, and to further reduce the amount of free metal ions, it is preferable to purify the crystalline compound. Crystalline compounds Examples of the production method include: (a) a method in which a crystalline compound is dissolved in a solvent, and the solvent is gradually distilled off for recrystallization to increase purity; and (b) a crystalline compound is dissolved in a solvent. And a method of reducing the metal content by removing the free metal by bringing the solution into contact with an ion exchange resin.
[0043] 固定剤には、支持ウェハ及び被加工ウェハへの濡れ性及び Z又は接着性を調整 するために、あるいは固定剤の溶融粘度を調整するために、必要に応じて非イオン 系界面活性剤などの表面張力調節剤を、 目的とする機能を損なわない範囲で添カロ することができる。 [0043] For the fixing agent, a nonionic surfactant is used as necessary to adjust the wettability and Z or adhesion to the support wafer and the workpiece wafer, or to adjust the melt viscosity of the fixing agent. Surface tension modifiers such as agents can be added as long as the intended function is not impaired.
[0044] 添加することのできる非イオン系界面活性剤としては、パーフルォロアルキル基な どのフッ化アルキル基を有するフッ素系界面活性剤や、ォキシアルキル基を有する ポリエーテルアルキル系界面活性剤などを挙げることができる。  [0044] Examples of the nonionic surfactant that can be added include a fluorine-based surfactant having a fluorinated alkyl group such as a perfluoroalkyl group, and a polyether alkyl-based surfactant having an oxyalkyl group. Can be mentioned.
[0045] 上記フッ素系界面活性剤としては、たとえば、 C F CONHC H 、 C F SO N  [0045] Examples of the fluorosurfactant include C F CONHC H and C F SO N.
9 19 12 25 8 17 2 9 19 12 25 8 17 2
H- (C H O) H、「エフトップ EF301」、「同 EF303」、「同 EF352」（新秋田化成（H- (C H O) H, “F-top EF301”, “EF303”, “EF352” (Shin Akita Chemical (
2 4 6 2 4 6
株)製）、「メガファック F171」、「同 F173」（大日本インキ (株)製）、「アサヒガード AG 710」（旭硝子（株）製）、「フロラード FC— 170C」、「同 FC430」、「同 FC431」（住友 スリーェム（株）製）、「サーフロン S— 382」、「同 SC101」、「同 SC102」、「同 SC103 」、「同 SC104」、「同 SC105」、「同 SC106」（旭硝子（株）製）、「： BM— 1000」、「同 1100」（B. M— Chemie社製）、「Schsego— Fluor」（Schwegmann社製）、「FS1 265」（東レダウコーユングシリコーン (株)製)などを挙げることができる。  Co., Ltd.), “MegaFuck F171”, “Same F173” (Dainippon Ink Co., Ltd.), “Asahi Guard AG 710” (Asahi Glass Co., Ltd.), “Florard FC—170C”, “Same FC430” , "FC431" (Sumitomo 3EM), "Surflon S-382", "SC101", "SC102", "SC103", "SC104", "SC105", "SC106" (Made by Asahi Glass Co., Ltd.), “: BM-1000”, “1100” (made by B. M-Chemie), “Schsego-Fluor” (made by Schwegmann), “FS1 265” (Toray Dow Cowing Silicone) (Manufactured by Co., Ltd.).
[0046] 上記ポリエーテルアルキル系界面活性剤としては、たとえば、ポリオキシエチレンァ ルキルエーテル、ポリオキシエチレンァリルエーテル、ポリオキシエチレンアルキルフ ェ-ルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポ リオキシエチレンソルビタン脂肪酸エステル、ォキシエチレンォキシプロピレンブロッ クポリマーなどを挙げることができ、具体的には「ェマルゲン 105」、「同 430」、「同 81 0」、 「同 920」、 「レオドール SP— 40S」、 「同 TW— L120」、 「エマノール 3199」、 「同 4110」、 「ェキセル P— 40S」、 「ブリッジ 30」、 「同 52」、 「同 72」、 「同 92」、 「ァラッセ ル 20」、 「ェマゾール 320」、 「ツイーン 20」、 「同 60」、 「マージ 45」（以上、 （株）花王 製）、「ノニボール 55」 (三洋化成 (株）製）、「SH— 28PA」、「同一 190」、「同— 193」 、 「SZ— 6032」、 「SF— 8428」（以上、東レダウコーユングシリコーン (株)製)等を挙 げることができる。 [0046] Examples of the polyether alkyl surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene alkyl ether. Examples include reoxyethylene sorbitan fatty acid ester and oxyethylene oxypropylene block polymer. Specifically, Emulgen 105, 430, 810, 920, Leodol SP -40S, TW-L120, Emanol 3199, 4110, Exel P-40S, Bridge 30, 52, 72, 92, Alasse "Le 20", "Emazol 320", "Tween 20", "Same 60", "Merge 45" (above, made by Kao Corporation), "Nonibo" Le 55 "(manufactured by Sanyo Chemical Co., Ltd.)," SH-28PA "," Same 190 "," Same-193 " , “SZ-6032”, “SF-8428” (made by Toray Dow Cowing Silicone Co., Ltd.), and the like.
[0047] 上記以外の非イオン系界面活性剤としては、たとえば、ポリオキシエチレン脂肪酸 エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリアルキレンオキサイドブ ロック共重合体などが挙げられ、具体的には「ケミスタツト 2500」（三洋化成工業 (株） 製）、「SN— EX9228」（サンノプコ (株)製）、「ノナール 530」（東邦化学工業 (株)製 )等を挙げることがでさる。  [0047] Examples of nonionic surfactants other than the above include polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyalkylene oxide block copolymers, and the like. Specifically, “CHEMISTAT 2500 "Sanyo Kasei Kogyo Co., Ltd.", "SN-EX9228" (San Nopco Co., Ltd.), "Nonal 530" (Toho Chemical Co., Ltd.), etc.
[0048] 上記表面張力調整剤は、上記結晶性化合物 100質量部に対して 0. 1〜50質量部 、好ましくは 1〜30質量部の量で用いることができる。使用量が上記範囲を超えると、 常温における固定剤の硬度が低くなつたり、粘着性が高すぎて所定形状への加工が 困難となることがある。一方、使用量が上記範囲よりも低いと濡れ性及び Z又は接着 性の改善効果が表れな 、ことがある。  [0048] The surface tension adjusting agent can be used in an amount of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the crystalline compound. When the amount used exceeds the above range, the hardness of the fixing agent at room temperature may be low, or the adhesiveness may be too high, making it difficult to process into a predetermined shape. On the other hand, if the amount used is lower than the above range, the effect of improving wettability and Z or adhesion may not appear.
[0049] 固定剤による接着強度は、 25± 2°Cにおいて 0. 5MPa以上であることが好ましぐ IMPa以上であることが更に好ましぐ 5MPa以上であることが特に好ましい。接着強 度が上記範囲よりも低いと接着後の加工条件によっては接着面が部分的に剥がれ 加工の面内均一性が損なわれる場合がある。  [0049] The adhesive strength by the fixing agent is preferably 0.5 MPa or more at 25 ± 2 ° C, more preferably IMPa or more, and particularly preferably 5 MPa or more. If the bonding strength is lower than the above range, the bonded surface may be partially peeled depending on the processing conditions after bonding, and the in-plane uniformity of processing may be impaired.
[0050] また、固定剤を用いて、被カ卩ェウェハと支持ウェハとを接着したときの、 25± 2°Cに おける接着強度を A (MPa)とし、固定剤の溶融温度 (示差走査熱量分析装置 (DSC )で測定したメインの溶融ピーク曲線におけるピーク温度を 、う。）より 20°C低 、温度 における接着強度を B (MPa)とした場合、該接着強度 Aおよび Bが下記関係式（1) を満たすことにより、接着強度の温度依存性が小さぐ溶融温度以下の広い範囲で 良好な接着状態を保持できる。  [0050] Further, when the fixing wafer is used to bond the wafer to be covered and the supporting wafer, the adhesive strength at 25 ± 2 ° C is A (MPa), and the melting temperature of the fixing agent (differential scanning calorific value) The peak temperature in the main melting peak curve measured with the analyzer (DSC) is 20 ° C lower and the bond strength at the temperature is B (MPa). By satisfying (1), a good adhesion state can be maintained in a wide range below the melting temperature where the temperature dependence of the adhesive strength is small.
[0051] 0<A-B< 0. 5 · · · (1)  [0051] 0 <A-B <0.5 (1)
[0052] また、固定剤としては、上記特許文献 3に記載の液晶化合物を使用することもでき る。すなわち、具体的には、 iso 酪酸ナトリウム、ォレイン酸ナトリウム、へキサヒドロ 安息香酸カリウム、ステアリン酸ナトリウム、ミリスチン酸ナトリウム、パルミチン酸ナトリ ゥム、安息香酸ナトリウム、ェチル—p ァゾキシベンゾエート、 1— n—ドデシルピリジ -ゥムクロライド、 1 n—ドデシルピリジ -ゥムブロマイド、 l—n—ドデシルピリジ-ゥ ムョードダイド、 2— n—トリデシルピリジ -ゥムクロライド、 3— n—ドデシルォキシメチ ルピリジ-ゥムメチルスルホネート、 3—n—ドデシルォキシメチルピリジ-ゥム—p—メ チルフエ-ルスルホネート、 4—シァノ 4，一ォクチルォキシビフエ-ル、 4—シァノ —4，一ドデシルォキシビフエ-ル、 4—シァノ 4，一オタタノィルォキシビフエ-ル、 p—ォクチルォキシ安息香酸ー4 シァノフエ-ルエステル、ヘプター 2, 4 ジェン 酸、オタター 2, 4 ジェン酸、ノナ 2, 4 ジェン酸、デカー 2, 4 ジェン酸、ゥン デカー 2, 4 ジェン酸、ノナー2 ェンー4 イン酸、パルミチック酸、ドコサン（ベへ ン）酸、 1, 10—デカンジカルボン酸（ドデカン二酸）、 1, 12—ドデカンジカルボン酸 、 1, 10—デカンジカルボン酸ジヒドラジド、 p—n—ブチル安息香酸、 p—n—ァミル 安息香酸、 ρ— n—へキシルォキシ安息香酸、 p— n—ォクチルォキシー m フルォ 口安息香酸、 ω— η—ブチルソルビン酸、 ρ，ーメトキシ—ρ ビフエ-ルカルボン酸、 Ρ ァゾキシァ-ノール、 ρ ァゾキシフエネトール、ァ-シリデン ρ ァミノフエ-ル アセテート、 ρ—メトキシベンジリデン—ρ ブチルァ-リン、 ρ—エトキシベンジリデン —ρ ブチルァニリン、 5 クロ口 6— η—プロピルォキシ—2 ナフトェ酸、 1—ベ ンゼンァゾーァニサルー 4 ナフチルァミン、 ρ—メトキシ—ρ'—ブチルァゾキシベン ゼン、ジへキシルォキシァゾベンゼン、 ρ へキシルカルボネート ρ' へプチルォ キシフエ-ル安息香酸、 ρ ァセトキシケィヒ酸、 ρ—メトキシ一 —ケィヒ酸、フエ-ル ペンタジェン酸、 ρ —へキシルォキシ m ブロモケィヒ酸、 p—メトキシー p ビ フエ-ルカルボン酸、 p，—エトキシ m，—クロ口— p ビフエ-ルカルボン酸、 p， - ブチルォキシ—m—ブロモー p ビフエ-ルカルボン酸、 p，—n—プロピルォキシ m，一-トロ— p ビフエ-ルカルボン酸、 [0052] As the fixing agent, the liquid crystal compounds described in Patent Document 3 can also be used. Specifically, iso sodium butyrate, sodium oleate, potassium hexahydrobenzoate, sodium stearate, sodium myristate, sodium palmitate, sodium benzoate, ethyl-p-azoxybenzoate, 1-n —Dodecyl pyridi-um chloride, 1 n —Dodecyl pyridi-um bromide, l—n—Dodecyl pyridi-um Mudeodide, 2-n-tridecylpyridyl-um chloride, 3-n-dodecyloxymethyl pyridinium methylsulfonate, 3-n-dodecyloxymethylpyridium-p-methylphenol sulfonate, 4-cyano 4, one O-lipped Ruo carboxymethyl bi Hue - le, 4 Shiano - 4, one dodecyl O carboxymethyl bi Hue - le, 4 Shiano 4, single OTA Tano I Ruo carboxymethyl bi Hue - le, p- Okuchiruokishi benzoic San 4 Cyanophyl ester, hepter 2, 4 Genic acid, Otata 2, 4 Genic acid, Nona 2, 4 Genic acid, Deca 2, 4 Genic acid, Undeca 2, 4 Genic acid, Noner 2 Gen 4 Inic acid, Palmitic acid , Docosane (benhenic) acid, 1,10-decanedicarboxylic acid (dodecanedioic acid), 1,12-dodecanedicarboxylic acid, 1,10-decanedicarboxylic acid dihydrazide, p-n-butylbenzoic acid, p-n —A Mil Benzoic acid, ρ- n-Hexyloxybenzoic acid, p- n-Octyloxy m Fluorobenzoic acid, ω- η-Butyl sorbic acid, ρ, -Methoxy-ρ biphenylcarboxylic acid, Ρ Azoxy-nol, ρ Azo Xylphenetol, silylidene ρ aminophenol acetate, ρ-methoxybenzylidene-ρ butylarlin, ρ-ethoxybenzylidene —ρ butylaniline, 5-chloro 6- η-propyloxy-2 naphthoic acid, 1-benzene Zonisalu 4 naphthylamine, ρ-methoxy-ρ'-butylazoxybenzene, dihexyloxyazobenzene, ρ-hexyl carbonate ρ 'heptyloxyphenyl benzoic acid, ρ-acetoxykehic acid, ρ —Methoxy mono —Caihynoic acid, Phenolpentaenoic acid, ρ —Hexyloxy m Bromokehiic acid, p-methoxy -P-biphenylcarboxylic acid, p, -ethoxy m, -clog opening- p-biphenylcarboxylic acid, p, -butyloxy-m-bromo-p-biphenylcarboxylic acid, p, -n-propyloxy m, 1-tro- p Biphenyl carboxylic acid,
7—メトキシ一 2 フルオレン酸、 6—メトキシ一 2 ナフチル酸、 6 エトキシ一 2— ナフチル酸、 6— n—プロピルォキシ—5 クロ口 2，—ナフチル酸、 6— n—プロピ ルォキシ— 5 ブロモ—2，—ナフチル酸、 6— n—ブチルォキシ—5 クロ口 2 ナ フチル酸、 6— n ブチルォキシ 5 ブロモー 2 ナフチル酸、 6— n—ブチルォキ シ— 5 ョード—2 ナフチル酸、 p，—n—へキシルォキシ—p ビフエ二ルカルボン 酸メチルエステル、 p， —へキシルォキシ—p ビフエ二ルカルボン酸ェチルエス テル、 p，—n—へキシルォキシ—p ビフエ-ルカルボン酸プロピルエステル、 p，— n —ドデシルォキシ—m，—クロロビフエ-ルカルボン酸プロピルエステル、 p， n—ド デシルォキシ— m'—-トロビフエ-ルカルボン酸プロピルエステル、 p, p，—ビフエ二 ルジカルボン酸ビフエ-ルエステル、 p, p，一テルフエ-ルジカルボン酸ジメチルエス テル、エチレングリコールビス（o—カルボエトキシ— p—ォキシフエ-ルエステル）、ビ ス（ρ—メトキシシンナミル）アセトン、ジァリリデンシクロペンタノン一ビス（p—メトキシ ベンザル）シクロペンタノン、ジァリリデンシクロへキサノン一ビス（p—メトキシベンザル )シクロへキサノン、ビス〔p— (ベンゾィルォキシ）ベンザル〕 - β—メチルシクロへキ サノン、 ρ, ρ，一ビス（ビフエ-ルカルビノール）ビフエ-ル、 1—クロ口 1 , 2—ビス（ρ —ァセトキシフエ-ル）エチレン、 ρ ァセトキシベンザルー ρ，一メトキシァ-リン、 ρ— メトキシベンザルー ρ '—シァノア-リン、 ρ—メトキシベンザルー ρ '—メトキシァ-リン、 ρ—メトキシシンナミルー ρ，ーメチルァニリン、 ρ 二トロシンナミルー ρ，一メチルァニリ ン、 ρ—メトキシフエ-ルペンタジェナルァ-リン、ベンザルー ρ ァミノ安息香酸 ρ— シァノベンザルー Ρ ァミノ安息香酸、ベンザルー ρ ァミノ（j8—メチル）ケィヒ酸、 p —メトキシベンザル p アミノー o—メチルケィヒ酸、 p—メトキシベンザル p アミ ノ o メチルヒドロケィヒ酸、 7-Methoxy-1-fluorenic acid, 6-Methoxy-2-naphthylic acid, 6-Ethoxy-2-naphthylic acid, 6-n-propyloxy-5 Chromium 2, -naphthylic acid, 6-n-propyloxy-5-bromo-2 , -Naphthylic acid, 6- n-Butyloxy-5 Chromium 2 Naphthylic acid, 6- n Butyloxy 5 Bromo-2 naphthylic acid, 6- n-Butyloxy-5 Jodo-2 Naphthylic acid, p, -n-Hexyloxy —P Biphenylcarboxylic acid methyl ester, p , —hexyloxy—p Biphenylcarboxylic acid ethyl ester, p, —n—hexyloxy—p Biphenylcarboxylic acid propyl ester, p, — n —Dodecyloxy-m, -chlorobiphenylcarboxylic acid propyl ester, p, n-dodecyloxy—m ′ —- trobiphenylcarboxylic acid propyl ester, p, p, —biphenyldicarboxylic acid biphenyl ester, p, p, one Dimethyl terphenyl dicarboxylate, ethylene glycol bis (o-carboethoxy-p-oxyphenyl ester), bis (ρ-methoxycinnamyl) acetone, diarylidenecyclopentanone monobis (p-methoxybenzal) ) Cyclopentanone, diarylidenecyclohexanone monobis (p-methoxybenzal) cyclohexanone, bis [p- (benzoyloxy) benzal] -β-methylcyclohexanone, ρ, ρ, monobis (bihue) -Lucalbinol) biphenyl, 1-black mouth 1, 2-bis (ρ-acetoxyphenyl) ethylene, ρ Toxibenzal ρ, Monomethoxy-line, ρ-Methoxybenzal ρ '-Cyanoa-line, ρ-Methoxybenzal ρ' -Methoxy-line, ρ-Methoxycinnamyl-ρ, -Methylaniline, ρ Nitrocinnamyl-ρ, Monomethylaniline, ρ-Methoxyphenol pentagenarine, benzal ρ Aminobenzoic acid ρ—Cyanobenzal Ρ Aminobenzoic acid, Benzal ρ Amino (j8-methyl) kehynoic acid, p-methoxybenzal p Amino-o-methylkehynoic acid, p-methoxy Benzal p amino o methylhydrokehynoic acid,
p エトキシベンザルー p ァミノ安息香酸ェチルエステル、 p エトキシベンザル — p アミノケィヒ酸ブチルエステル、 p -シァノベンザル p アミノケィヒ酸ェチル エステル、 ρ—メチルベンザルー ρ アミノケィヒ酸ァミルエステル、 p—メトキシベンザ ルー P アミノメチルケィヒ酸メチルエステル、 p—メトキシベンザルー p— a—メチル ケィヒ酸プロピルエステル、 ρ—エトキシベンザルー ρ—アミノー α—ェチルケィヒ酸ェ チルエステル、 ρ—メトキシシンナミルー ρ ァミノ安息香酸ェチルエステル、 ρ—メトキ シベンザルー ρ アミノビフエ-ル、ベンザルー ρ アミノー ρ，一ァセチルビフエ-ル 、ベンザルー ρ アミノー ρ，一ジメチルアミノビフエ-ル、ベンザルー ρ アミノー ρ， - ホルミルアミノビフエ-ル、 ρ メチルベンザルー ρ—アミノー ρ '—ァセチルアミノビフ ェニル、 ρ—メチルベンザルー ρ アミノー ρ，一ベンゾィルアミノビフエ-ル、シンナミ ルー Ρ アミノー P '—ァセチルビフエ-ル、 2— ρ—メトキシベンザルァミノフルオレン 、 2— ρ—メトキシベンザルァミノフエナンスレン、 2— ρ—メトキシベンザルァミノフルォ レン、 2— ρ—η—ブチルォキシベンザルァミノフルオレン、 ρ ノ-ルォキシベンザル フエ-ルヒドラジン、ビス（p—メトキシベンザル） - (ジメチル）ァジン、ビス（p フエ- ルベンザル）ァジン、 p—メトキシフエ二ルペンタジェナルフエニルヒドラジン、テレフタ ルービス一（p クロロア-リン）、テレフタル一ビス（p ァミノ安息香酸ェチルエステ ル）、ビス（p クロ口ベンザル） p フエ-レンジァミン、ビス（p—メチルベンザル） - p トルイレンジァミン、ジベンザルー p, p，一ジアミノビフエ-ル、ビス（O—ォキシベ ンザル） p, ρ，一ジアミノビフエ-ル、ジシンナミルー p, p，一ジアミノビフエ-ル、ビ ス（P—メトキシベンザル） p, p，一ジァミノジメチルビフエ-ル、ビス（p—メトキシベン ザル）一 2, 7 ジァミノフルオレン、ビス（p—メトキシベンザル）一 2, 7 ジァミノフル オレン、ビス（p—メトキシベンザル）一 1, 4 ジァミノナフタレン、ビス（p—メトキシ一 m—メチルベンザル） p, p，ージァミノテルフエ-ル、ジシンナミルー p, p，ージァミノ テルフエ-ル、ジベンザルー p, p，一ジァミノクォーターフエ-ル、 p—メトキシ一 p ' - 才キシァゾベンゼン、 p, p '—ジメトキシァゾベンゼン、 p, p '—ジー n—へキシノレ才キ シァゾベンゼン、 p-Ethoxybenzal p-aminobenzoic acid ethyl ester, p-ethoxybenzal — p-amino benzoic acid butyl ester, p-cyanobenzal p-amino cinnamate ethyl ester, ρ-methylbenzal ρ-amino cinnamate amyl ester, p-methoxybenzal lu P-aminomethyl key Acid methyl ester, p-methoxybenzal p- a-methyl cinnamate propyl ester, ρ-ethoxybenzal ρ-amino-α-ethyl cinnamate ethyl ester, ρ-methoxycinnamyl ρ aminobenzoic acid ethyl ester, ρ-methoxy benzal ρ Aminobiphenyl, Benzal ρ Amino ρ, Monoacetyl benzyl, Benzal ρ Amino ρ, One dimethylamino biphenyl, Benzal ρ Amino ρ,-Formylaminobiphenyl, ρ Methyl benzal ρ— Minnow ρ '—Acetylaminobiphenyl, ρ-Methylbenzal ρ Amino-ρ, Monobenzoylbiphenyl, Cinnamic Luo Ρ Amino-P' -Acetylbiphenyl, 2-ρ-methoxybenzalaminofluorene, 2-ρ-methoxybenzalaminophenanthrene, 2-ρ-methoxybenzalaminofluorene, 2-ρ-η-butyloxybenzalaminofluorene, ρ-noroxybenzal Phenylhydrazine, bis (p-methoxybenzal)-(dimethyl) azine, bis (pphenylbenzalazine), p-methoxyphenylpentaphenylhydrazine, terephthal bis (p-chloroa-line), terephthal Bis (p-aminobenzoyl ethyl ester), Bis (p black benzal) p Hue-rendiamine, Bis (p-methylbenzal)-p Toluylenediamine, Dibensalu p, p, Monodiaminobiphenyl, Bis (O— (Xoxybensal) p, ρ, monodiaminobiphenyl, dicinnamylo p, p, monodiaminobiphenyl, bis (P-methoxybenzal) p, p, monodiaminodimethylbiphenyl, bis (p-methoxybenzen) Colander) 1,7 diaminofluorene, bis (p-methoxybenzal) -1,2,7 diaminofluorene, bis (p-methoxybenzal) 1,4 Aminonaphthalene, bis (p-methoxy-m-methylbenzal) p, p, diaminoterphenyl, dicinnamyl p, p, diamino terphel, dibensalu p, p, monodaminoquarter , P-methoxy-one p'-age xiazobenzene, p, p'-dimethoxyazobenzene, p, p'-ji n-hexynole-age xiazobenzene,
p ァセトキシベンゼン—p ァゾ安息香酸ェチルエステル、ベンゾィルー p—ォキ シベンゼン p ァゾー α—メチルケィヒ酸ァミルエステル、 ρ, ρ，ーァゾ安息香酸モ ノエチルエステル、 1—ァセトキシナフタリン— 4— ρ ァセチルァゾベンゼン、ベンザ ル一 Ρ アミノアゾベンゼン、 ρ—メトキシベンザル一 ρ ァミノ一 ρ'—メチルァゾベン ゼン、 ρ—メトキシベンザルー ρ アミノー ρ'—ェトキシァゾベンゼン、シンナミルー ρ -アミノアゾベンゼン、 ρ メトキシベンザル 1 ァミノナフタリン一 4 ァゾベンゼン 、 ρ—メトキシベンザルー 1—ァミノナフタリン一 4— (ρ，一ァセチルァゾベンゼン）、 ρ —メチルベンザルー 1—ァミノナフタリン一 4— (ρ，一メトキシァゾベンゼン）、 ρ—メチ ルベンザルー 1—ァミノナフタリン一 4— (ρ，一ェトキシァゾベンゼン）、 ρ—メチルベン ザルー 1—ァミノナフタリン— 4— (ρ，—ァゾ安息香酸ェチルエステル）、 ρ シンナミ ルー 1—ァミノナフタリン— 4— (ρ，—ァゾ安息香酸ェチルエステル）、ビス（ρ—イソプ 口ピルベンザル）一 ρ, ρ，一ジアミノアゾベンンゼン、 （ρ エトキシベンゼン）一 ρ ァ ゾ（ρ—メトキシベンゾィル） ο—ォキシベンザルー（ρ，一エトキシ）ァ-リン、 ρ, ρ， - ァゾベンザルービス一ァ-リン、ベンザルー ρ アミノビフエ-ルァゾベンゼン、テレフ タル一ビス（ρ アミノアゾベンゼン）、 ρ, ρ，一ジァセトキシァゾキシベンゼン、 ρ, ρ， - ジメトキシァゾキシベンゼン（ァゾキシァニソーノレ）、 p—メトキシベンゼン p ァゾキ シ安息香酸メチルエステル、 p—メトキシベンゼン p ァゾキシ安息香酸フエ-ルェ ステル、 p, p，ーァゾキシ安息香酸ジメチルエステル、 p, p， 一ァゾキシチォ安息香酸 ジェチルエステル、 p, p， 一ァゾキシケィヒ酸ジヘプチルエステル、 p, p，ーァゾキシ o—メチルケィヒ酸ジォクチルエステル、 p, p，ーァゾキシ o—メチルー βーブロ ムケィヒ酸ジェチルエステル、 ρ, ρ，ーァゾキシー 13ーメチルケィヒ酸ジメチルエステ ル、ジ—ρ—メトキシベンゾィルジスルフイド、 p-acetoxybenzene—p-azobenzoic acid ethyl ester, benzoyl p-oxybenzene p-azol, α-methylkemic acid amyl ester, ρ, ρ, benzobenzoic acid monoethyl ester, 1-acetoxynaphthalene—4--rho Cetylazobenzene, benzal Ρ aminoazobenzene, ρ-methoxybenzal ρ amino ρ'-methylazobenzen, ρ-methoxybenzal ρ amino-ρ'-ethoxyazobenzene, cinnamyl ρ -aminoazobenzene, ρ methoxy Benzal 1 4-aminonaphthalene 1-azobenzene, ρ-Methoxybenzal 1-amino-naphthalene 4- (ρ, 1-acetylazobenzene), ρ-Methylbenzal 1-amino-naphthalene 1- (ρ, 1-methoxyazobenzene), ρ-methylbenzal 1-aminonaphthalene 4- (ρ, 1 Xyazobenzene), ρ-methylbenzalu 1-aminonaphthalene-4— (ρ, -azobenzoic acid ethyl ester), ρ cinnamulu 1-aminonaphthalene-4— (ρ, -azobenzoic acid ethyl ester), bis ( ρ-Isopropyl pyrbenzal) 1 ρ, ρ, 1 diaminoazobenzen, (ρ ethoxybenzene) 1 ρ azo (ρ-methoxybenzoyl) ο-oxybenzal (ρ, 1 ethoxy) aline, ρ, ρ ,-Azobenzalbisbis-line, benzalu ρ aminobiphenol azobenzene, terephthalic bis (ρ aminoazobenzene), ρ, ρ, monodiacetoxyzoxybenzene, ρ, ρ,- Dimethoxyazoxybenzene (Azoxyanisanol), p-methoxybenzene p-Azoxybenzoic acid methyl ester, p-methoxybenzene p-Azoxybenzoic acid ester, p, p, -Azoxybenzoic acid dimethyl ester, p , p, monoazoxythiobenzoic acid jetyl ester, p, p, monoazoxykehynoic acid diheptyl ester, p, p, -azoxy o-methylkehynoic acid dioctylester, p, p, -azoxy o-methyl-β-bromoketiic acid jetyl Ester, ρ, ρ, -Azoxy 13-Methylkehynoic acid dimethyl ester, Di-ρ-methoxybenzoyl disulfide,
[0056] 炭酸メチルコレステリルエステル、炭酸ェチルコレステリルエステル、安息香酸 Δ 5, 6 コレステン— 3 j8—01 エステル、 p—メトキシ安息香酸コレステリルエステル 、 p ァミノ安息香酸コレステリルエステル、 p—n—へプチル安息香酸 p，ーシァノフ ェ-ルエステル、 4—シァノ—4，—ペンチルジシクロへキシル、 4—ペンチルシクロへ キシル 1—カルボン酸 p シァノフエ-ルエステル、 1— (p シァノフエ-ル） 2 - (4 ペンチルシクロへキシル）ェタン、 p シァノー（4 へプチルー 2, 6 ジォキ サシクロへキシル）ベンゼン、 p シァノー（5 ペンチルー 2 ピリミジル）ベンゼン、 p シァノー〔4— (3—ペンテ-ル）シクロへキシル〕ベンゼン、 4— (p シァノフエ- ル） 4， 一へプチルビシクロへキシル、 p シァノー（4—ペンチルシクロへキシル）ベ ンゼン、 1— (p シァノフエ-ル） 2— (4，一プロピル一 4 ビシクロへキシル）エタ ン、 p— (4 プロビルシクロへキシル）安息香酸 2 シァノー 4 ペンチルフエ-ル エステル、 ρ— (4 プロビルシクロへキシル）安息香酸 2, 3 ジシァノー 4 ペン チルォキシフエ-ルエステル、 p— (3—ペンチルー 6—ピリダジ -ル）ペンチルォキシ ベンゼン、 p— (1—シァノ 4 プロビルシクロへキシル） p，一ペンチルビフエ-ル 、 2, 3 ジフルオロー 4 エトキシ— 4'— (4 ペンチルシクロへキシル）ビフエ-ル、 4 (3, 4ージフルオロフェ -ル）—4' ペンチルビシクロへキシル、 1 〔4 (3, 4 -ジフルオロフェ -ル）シクロへキシル〕 2— (4 ペンチルシクロへキシル）ェタン、 3, 4ージフルオロー 4'一（4 ペンチルシクロへキシル）ビフエ-ル、  [0056] Carbonic acid methyl cholesteryl ester, carbonic acid cholesteryl ester, benzoic acid Δ 5, 6 cholestene-3j8-01 ester, p-methoxybenzoic acid cholesteryl ester, p-aminobenzoic acid cholesteryl ester, p-n-heptylbenzoic acid Acid p, -Cyanophenol ester, 4-Cyano-4, -pentyldicyclohexyl, 4-pentylcyclohexyl 1-carboxylic acid p Cyanophenol ester, 1- (p Cyanophenol) 2-(4 Pentylcyclohexane Hexyl) ethane, p-cyanol (4 heptiloux 2, 6 dioxacyclohexyl) benzene, p-cyanol (5-pentyl-2-pyrimidyl) benzene, p-cyano [4- (3-pentayl) cyclohexyl] benzene, 4 — (P cyanophyl) 4, monoheptylbicyclohexyl, p cyano (4-pentylcyclohexyl) Zen, 1— (p cyanophyl) 2— (4,1 propyl 1 4 bicyclohexyl) ethane, p— (4 propylcyclohexyl) benzoic acid 2 cyanol 4 pentylphenol ester, ρ— (4 Propylcyclohexyl) benzoic acid 2,3 dicyanol 4-pentyloxyphenyl ester, p— (3-pentyl-6-pyridazil) pentyloxy benzene, p— (1-cyanol 4-propyl cyclohexyl) p, 1 pentylbiphenol , 2, 3 difluoro-4 ethoxy-4 ′ — (4 pentylcyclohexyl) biphenyl, 4 (3,4-difluorophenyl) —4 ′ pentylbicyclohexyl, 1 [4 (3, 4-difluoro (Phenyl) cyclohexyl] 2— (4 pentylcyclohexyl) ethane, 3,4-difluoro-4′-one (4-pentylcyclohexyl) biphenyl,
[0057] プロピオン酸コレステロール、安息香酸コレステロール、パルミチン酸コレステロ一 ル、塩化コレステロール、ギ酸コレステロール、酢酸コレステロール、ペラルゴン酸コ レステロール、 p アミノケィヒ酸コレステリルエステル、安息香酸— Δ 5, 6 ; 7, 8—コ レスタジェンー 3 j8— 01—エステル、 ρ— n—ォクチルォキシ安息香酸、 p— n オタ チルォキシー m クロル安息香酸、 p— n—ドデシルォキシ安息香酸、 5—クロロー 6 —n—ヘプチルォキシ— 2—ナフトェ酸、 p— n—ノ-ルォキシベンザルー p，—トルイ ジン、ミリスチン酸コレステロール、オクタン酸コレステロール、 p—n—ノ-ルォキシ m—フルォロ安息香酸、 5 ョードー 6—n—ノ-ルー 2 ナフトェ酸、 n—ノナン酸コ レステロール、 p， n—へキシルォキシ m，一-トロ一 ρ ビフエ-ルカルボン酸、 ρ n へキシノレォキシ m クロロケィヒ酸、 p アミロキシ p ビフエ二ノレ力ノレボン 酸、 ρ，—ブチルォキシ—m，—クロ口— p ビフエ-ルカルボン酸、 ρ， n—へキシル ォキシ—m'—二トロー p ビフエ二ルカルボン酸、 7—n—へプチルォキシー2 フル オレン酸、 6 n—ノ-ルォキシー5 ョードー 2 ナフチル酸、 6 n—ノ-ルォキシ 5 -トロー 2 ナフチル酸、 7— n ヘプチルォキシ 2 フルオレン酸プロピル エステル、 2 ァセチルー 7—n—へプチルォキシフルオレン、ジ—p, p，ーェチルー 3, 6—ビフエ二ルビリダジン、ジメチルー p, p，一ジォキシテルフエ-ル、 p, p'—ジァ ミノクォータフエ-ルキンキフエ-ル、 ρ— n—ノ-ルォキシベンザルー p'—ェチルァ 二リン、 [0057] Cholesterol propionate, cholesterol benzoate, cholesterol palmitate, cholesterol chloride, cholesterol formate, cholesterol acetate, cholesterol, pelargonic acid cholesterol, p-aminokehic acid cholesteryl ester, benzoic acid — Δ 5, 6; 7, 8 Restagene 3 j8— 01—ester, ρ— n—octyloxybenzoic acid, p— n octyloxyoxy m chlorobenzoic acid, p— n—dodecyloxybenzoic acid, 5-chloro-6 —n—heptyloxy-2-naphthoic acid, p— n—Noroxybenzalu p, —Toluidine, Myristic acid cholesterol, Octanoic acid cholesterol, p—n—Noroxy m—Fluorobenzoic acid, 5 Yodo 6—n—Nolulu 2 Naphthoic acid, n— Cholesterol nonanoate, p , n-hexyloxy m, 1-tro ρ biphenol carboxylic acid, ρ n hexenoreoxy m chlorochenoic acid, p amyloxy p biphenylenorenorenoic acid, ρ, —butyloxy-m, —chloro Mouth-p Biphenylcarboxylic acid, ρ, n-Hexyloxy-m'-Nitro-p Biphenylcarboxylic acid, 7-n-Heptyloxy-2 fluoro Renoic acid, 6 n—Noroxy-5 odor-2 naphthylic acid, 6 n—Noroxy-5-troh 2 naphthylic acid, 7—n Heptyloxy 2 fluoric acid propyl ester, 2 Acetyl 7-n-heptyloxyfluorene, Di-p, p, -ethylol 3,6-biphenylbilidazine, dimethyl-p, p, mono-dioxyterphenyl, p, p'-dia-minotaquater-quinkinfel, ρ-n-no-loxybenzal p'—
p— n—ノ-ルォキシベンザルー p，一プロピルァ-リン、 p へキシルォキシベンザ ルー p アミノケィヒ酸ェチルエステル、 p—メトキシベンザル p アミノケィヒ酸アミ ルエステル、 2— p—n—へキシルォキシベンザルァミノフエナンスレン、 p エトキシ ベンザルー p ァミノテルフエ-ル、ビス（p アミノォキシベンザル） p，一フエ-レン ジァミン、ビス（p—n—ブチルォキシベンザル） p, p，一ジアミノビフエ-ル、ビス（p プロポキシベンザル） 2, 7 ジァミノフルオレン、ビス（p ペンチルォキシベン ザル） 2, 7 ジァミノフルオレン、ジベンザルー p, p，一ジァミノテルフエ-ル、 p— メトキシベンゼン p ァゾケィヒ酸ェチルエステル、 p, p，ーァゾケィヒ酸ジメチルェ ステル、（ベンゾィル） p—ォキシ m—メトキシベンゼン p，一ァセチルァゾベン ゼン、（ベンゾィル） p—ォキシ o—メトキシベンゼン一 p'—ァセチルァゾベンゼン 、（ベンゾィル） p—ォキシ o エトキシベンゼン p，一ァセチルァゾベンゼン、 p , p' ジへキシル才キシァゾキシベンゼン、 p エトキシベンゼン p ァゾキシチ才 安息香酸ェチルエステル、 p エトキシベンゼン p ァゾキシ安息香酸 (p ェチル )フエ-ルエステル、ビス（p エトキシベンゼン p ァゾキシ安息香酸） m ジォ キシベンゼンエステル、 4— (p フルオロフェ -ル）—4'—ペンチルビシクロへキシ ル、 1— (3, 4—ジフルオロフェ -ル）—2—〔4— (4，—ペンチルビシクロへキシル）〕 ェタン、 4— (p トリフルォロメトキシフエニル） 4'—ペンチルビシクロへキシル、 4 一（p ジフルォロメトキシフエニル） 4 ' ペンチルビシクロへキシル、 4 トリフルォ ロメトキシー 4， - (4—ペンチルシクロへキシル）ビフエ-ル、 p トリフルォロメトキシフ ェニル p— (4 ペンチルシクロへキシル）フエ-ルアセチレン、 1つのベンゼン環の 1, 3, 5位にステロイドエステル基を有する化合物などのディスコチック液晶、芳香族 ポリエステル、ポリアミド、ポリイミドなどの液晶性を有する高分子液晶化合物等を用 いることがでさる。 p- n-N-oxybenzallu p, 1-propyloxylin, p-hexyloxybenzal lu p-aminokehylic acid ethyl ester, p-methoxybenzal p-aminokemic acid amyl ester, 2-p-n-hexyloxy Benzalaminophenanthrene, p ethoxy benzal p paminoterphenol, bis (p-aminoxybenzal) p, mono-phenol diamine, bis (p-n-butyloxybenzal) p, p, mono-diaminobiphenol- Bis (p-propoxybenzal) 2,7 diaminofluorene, bis (p-pentyloxybenzal) 2,7 diaminofluorene, dibenzal p, p, mono-diaminoterfell, p-methoxybenzene p azokehi Acid ethyl ester, p, p, dimethyl ester of azoke arsenate, (benzoyl) p-oxy m-methoxybenzene p, monoacetyl azoben Zen, (Benzoyl) p-oxy o-methoxybenzene p'-acetylazobenzene, (Benzoyl) p-oxy o Ethoxybenzene p, monoacetylazobenzene, p, p ' Zoxybenzene, p-Ethoxybenzene p-Azoxychi, Benzoic acid ethyl ester, p-Ethoxybenzene p-Azoxybenzoic acid (p-ethyl) ) Phenol ester, bis (p ethoxybenzene pazoxybenzoic acid) m dioxybenzene ester, 4- (p fluorophenyl) -4'-pentylbicyclohexyl, 1- (3,4-difluorophenol- ) —2— [4— (4, -pentylbicyclohexyl)] ethane, 4— (p trifluoromethoxyphenyl) 4′-pentylbicyclohexyl, 4 mono (p difluoromethoxyphenyl) 4 'pentylbicyclohexyl, 4 trifluoromethoxy 4,-(4-pentylcyclohexyl) biphenyl, p trifluoromethoxyphenyl p- (4 pentylcyclohexyl) phenylacetylene, 1 benzene ring Liquid crystal compounds such as discotic liquid crystals such as compounds having steroid ester groups at the 1, 3, and 5 positions, aromatic polyesters, polyamides, polyimides, etc. You can use things.
[0059] これら液晶性を有する化合物は、単独で用いてもよぐ 2種類以上の液晶性を有す る化合物を混合して用いてもよい。これら液晶性を有する化合物のうち、単独及び Z 又は 2種類以上の混合物の融点が 35°C以上のものが好ましぐ 35°C以上 200°C以 下のものが更に好ましぐ融点が 40°C以上 150°C以下のものが特に好ましい。  [0059] These liquid crystal compounds may be used alone or in combination of two or more liquid crystal compounds. Among these compounds having liquid crystallinity, those having a melting point of 35 ° C or more are preferred, and those having a single or Z or a mixture of two or more are preferably those having a melting point of 35 ° C or more and 200 ° C or less. Those having a temperature of from ° C to 150 ° C are particularly preferred.
[0060] 上記液晶化合物を固定剤として使用するときは、粘度を調整するために必要に応 じて酸ィ匕アルミニウム、酸ィ匕ジルコニウム、酸化チタン、酸化ケィ素などの金属酸化物 の微粒子などと適宜混合して使用することができる。  [0060] When the liquid crystal compound is used as a fixing agent, fine particles of metal oxides such as acid aluminum, acid zirconium, titanium oxide, and silicon oxide are used as necessary to adjust the viscosity. And can be used in appropriate mixture.
[0061] また、液晶化合物は、粘度を調整するために、必要に応じて有機ポリマー、例えば ポリ（無水ァゼライン酸）、ポリ〔2, 6 ビス（ヒドロキシメチル）ー4 メチルフエノール — co— 4 ヒドロキシ安息香酸〕、ポリ（ 1 , 4 ブタンジオール）ビス（4 -ァミノべンゾ エート）、ポリ（1—ブテン）、ポリ（1, 4 ブテンアジペート一 co— 1, 4 ブチレンスク シネート）の 1, 6 ジイソシァネートへキサン反応物、ポリ（1, 4ーブチレンアジペート )ジオール、ポリ（1, 4 ブチレンアジペート一 co ポリ力プロラタタム）、ポリ（1, 4 - ブチレンスクシネート）の 1, 6 ジイソシァネートへキサン反応物、ポリ〔ブチレンテレ フタレート一 co ポリ（アルキレングリコール）テレフタレート〕、ポリ力プロラタトンジォ ール、ポリカルボメチルシラン、ポリクロ口プレン、ポリ（クロ口トリフルォロエチレン —ビ-リデンフルオライド）、ポリ〔（o クレシルグリシジルエーテル） co ホルムァ ルデヒド〕、ポリ〔ジメチルシロキサン— co—メチル (ステアロイルォキシアルキル）シロ キサン〕、ポリエチレン、ポリ（エチレン一 CO アクリル酸）、ポリ（エチレン一 CO—アタリ ル酸）のナトリウムまたは亜鉛塩、ポリ（エチレンアジペート）のトリレン— 2, 4 ジイソ シァネート反応物、ポリ（エチレンァゼレート）、ポリ（エチレン— co— 1—ブテン）、ポリ (エチレン 1—ブテン co— 1—へキセン）、ポリ（エチレン co ブチノレアク リレートー co—カーボンモノォキシド）、ポリ（エチレン co ブチルアタリレート co 無水マレイン酸）、ポリ（エチレン co ブチレン）ジオール、ポリ（エチレン co— ェチルアタリレート）、ポリ（エチレン CO ェチルアタリレート CO—無水マレイン酸 )、ポリ（エチレン CO グリシジノレメタタリレート）、ポリ（エチレングリコーノレ）、ポリエ チレン graft 無水マレイン酸、ポリ（エチレン co—メタクリル酸）、ポリ（エチレン — co—メタクリル酸）のナトリウムまたはリチウムまたは亜鉛塩、ポリ（エチレン一 co—メ チルアタリレート）、ポリ（エチレン一 co—メチルアタリレート一 co アクリル酸）、ポリエ チレンモノアルコール、ポリ（エチレン co— 1—オタテン）、ポリエチレンォキシド、ポ リエチレン block ポリ（エチレングリコール）、ポリ（エチレンスクシネート）、ポリ（ェ チレン co—トリアルコキシビュルシラン）、ポリ（エチレン co—酢酸ビュル）、ポリ（ へキサフルォロプロピレンォキシドー co ジフルォロメチレンォキシド）モノアルキル アミド、ポリ（1, 6 へキサメチレンアジペート）、ポリ（へキサメチレンカーボネート）、 ポリ（3—ヒドロキシブタン酸）、ポリイソプレン、ポリラウリルラタタム一 block ポリテトラ ヒドロフラン、ポリ（ォキシメチレン）アセテート、ポリプロピレン、ポリ（1, 3 プロピレン アジペート）、ポリ（プロピレン一 co— 1—ブテン）、ポリ（プロピレン一 co エチレン）、 ポリ（1, 3 プロピレングルタレート）、ポリ（1, 3 プロピレンスクシネート）、ポリ（無水 セバシン酸）、ポリスチレン、ポリ（ビュルアルコール— co エチレン）、ポリ（ビ -リデ ンクロライド一 co—メチルアタリレート）、ポリ（ビユリデンク口ライド一 co—ビュルクロラ イド）、ポリ（ビ-リデンフルオライド）、ポリ（ビ-リデンフルオライド co へキサフル ォロプロピレン）、ポリ（ビュル N ォクタデシルカルバメート）、ポリ（ビュルトルエン -co - a—メチルスチレン）などを添カ卩して用いてもよい。これら有機ポリマーの添カロ 量は、本発明に用いる液晶性を有する化合物の融点に依存するが、液晶性を有する 化合物に対して 200質量％以下、好ましくは 150質量％以下で用いることができる。 (1 3)染み込み防止構造； 図 1 (a)、図 1 (b)に示すように、本実施の形態の固定剤付きウェハ 100において、 染み込み防止構造 (染み込み防止部） 3は、支持ウェハエッジ部 4上に、支持ウェハ エッジ部 4を除く部分に配設されている固定剤 2の外周を囲むようにリング状に形成さ れて 、る。このように染み込み防止構造が固定剤の外周を囲むようにリング状に形成 されることにより、固定剤が、支持ウェハと染み込み防止構造とにより形成される窪み に配設された状態になり、固定剤が支持ウェハと被加工ウェハとの間からはみ出すこ とを防止することが可能となる。また、支持ウェハと被加工ウェハとの間に液状物質が 染み込むことを防止することが可能となる。 [0061] In addition, the liquid crystal compound may contain an organic polymer, for example, poly (caseyl anhydride), poly [2, 6bis (hydroxymethyl) -4 methylphenol — co-4 hydroxy, as necessary, in order to adjust the viscosity. 1,6 of (benzoic acid), poly (1,4 butanediol) bis (4-aminobenzoate), poly (1-butene), poly (1,4 butene adipate-co-1,4 butylene succinate) 1,6 diisocyanate hexane reaction of diisocyanate hexane reactant, poly (1,4-butylene adipate) diol, poly (1,4 butylene adipate-co-poly-prolactam), poly (1,4-butylene succinate) , Poly [butylene terephthalate-co-poly (alkylene glycol) terephthalate], poly force prolatathondiol, polycarbomethylsilane, polychloro Puren, poly (black port triflate Ruo Russia ethylene - bi - isopropylidene fluoride), poly [(o-cresyl glycidyl ether) co Horumua aldehyde], poly [dimethylsiloxane - co- methyl (stearoyl Ruo carboxyalkyl) White Xanthine], polyethylene, poly (ethylene mono-CO acrylic acid), sodium or zinc salt of poly (ethylene mono-CO-atallylic acid), tolylene-2,4 diisocyanate reactant of poly (ethylene adipate), poly (ethylene Gellate), poly (ethylene-co-1-butene), poly (ethylene-1-butene co-1-hexene), poly (ethylene co-butanolate ligatoto-co-carbon monooxide), poly (ethylene co-butyl acrylate) co (maleic anhydride), poly (ethylene cobutylene) diol, poly (ethylene co-ethyl acrylate), poly (ethylene CO ethyl acrylate CO-maleic anhydride), poly (ethylene CO glycidinoremethacrylate) , Poly (ethylene glycolanol), polyethylene graft maleic anhydride, poly (ethylene c o-methacrylic acid), sodium or lithium or zinc salt of poly (ethylene-co-methacrylic acid), poly (ethylene mono-co-methyl acrylate), poly (ethylene mono-co-methyl acrylate / co-acrylic acid), Polyethylene monoalcohol, poly (ethylene co-1-octene), polyethylene oxide, polyethylene block poly (ethylene glycol), poly (ethylene succinate), poly (ethylene co-trialkoxybutyrsilane), poly ( Ethylene (co-butyl acetate), poly (hexafluoropropylene oxide co difluoromethylene oxide) monoalkyl amide, poly (1, 6 hexamethylene adipate), poly (hexamethylene carbonate), poly (3-hydroxybutanoic acid), polyisoprene, polylauryllatatam block polytetrahydrofuran, poly (oxymethylene) acetate, polypropylene, poly (1,3 propylene adipate), poly (propylene monoco-1-butene), poly (propylene monocoethylene), poly (1,3 propylene glutarate), Poly (1,3 propylene succinate), poly (sebacic anhydride), polystyrene, poly (bulcoalcohol-co-ethylene), poly (bi-lidene chloride- co -methyl acrylate), poly (vinylidene chloride) co —Burchloride), poly (bi-lidene fluoride), poly (bi-lidene fluoride co-hexafluoropropylene), poly (Bule N octadecyl carbamate), poly (Bultoluene-co-a-methylstyrene) Etc. may be used together. The amount of addition of these organic polymers depends on the melting point of the compound having liquid crystallinity used in the present invention, but can be used at 200% by mass or less, preferably 150% by mass or less with respect to the compound having liquid crystallinity. (1 3) Infiltration prevention structure; As shown in FIGS. 1 (a) and 1 (b), in the wafer 100 with the fixing agent of the present embodiment, the penetration preventing structure (penetration preventing portion) 3 is provided on the supporting wafer edge portion 4 on the supporting wafer edge portion. It is formed in a ring shape so as to surround the outer periphery of the fixing agent 2 disposed in the portion excluding 4. In this way, the penetration preventing structure is formed in a ring shape so as to surround the outer periphery of the fixing agent, so that the fixing agent is disposed in the recess formed by the support wafer and the penetration preventing structure and fixed. It is possible to prevent the agent from protruding between the support wafer and the workpiece wafer. In addition, it is possible to prevent the liquid material from permeating between the support wafer and the workpiece wafer.
[0063] 染み込み防止部 3は、リング状の染み込み防止部材により構成されていることが好 ましい。染み込み防止部 3の厚さは、固定剤 2の厚さの 80%〜200%であることが好 ましぐ 95%〜150%であることが更に好ましぐ 95〜105%であることが特に好まし い。 80%より薄いと、固定剤 2がはみ出したり、液状物質が染み込んできやすくなるこ と力 Sある。 200%より厚いと、被カ卩ェウェハを固定し難くなることがある。  [0063] It is preferable that the soaking prevention part 3 is constituted by a ring-like soaking prevention member. The thickness of the penetration preventing part 3 is preferably 80% to 200% of the thickness of the fixing agent 2, more preferably 95% to 150%, and even more preferably 95 to 105%. I like it. If it is thinner than 80%, the fixative 2 is likely to protrude and liquid substances can easily penetrate. If it is thicker than 200%, it may be difficult to fix the wafer to be covered.
[0064] 染み込み防止部 3は被加工ウェハを貼り合わせた際に被加工ウェハ表面と密着し て固定剤が漏れ出さない機能をさらに高めるため、染み込み防止部 3の上面が被カロ ェウェハと同程度の平坦度を有して変形しないか、もしくは、染み込み防止部 3の上 面および Zまたは材質が弾性を有する部材力 なり、貼り合わせの際に被加工ゥェ ハに沿って変形することが好ま 、。  [0064] In order to further enhance the function of the infiltration prevention unit 3 to adhere to the surface of the wafer to be processed when the wafers to be processed are bonded to each other and prevent the fixing agent from leaking out, the upper surface of the infiltration prevention unit 3 is approximately the same as that of the wafer to be processed. It is preferable that the upper surface of the permeation prevention part 3 and the Z or material are elastic member forces so that they deform along the workpiece wafer during bonding. ,.
[0065] 染み込み防止部 3の外周形状は円形であることが好ましい。これは、通常被加工ゥ ェハが円形（円板状）に形成されることが多ぐそれに合わせて支持ウェハ 1をほぼ同 じ大きさの円形に形成することが好ましいため、染み込み防止部 3も、その大きさ、形 状に合わせたものである。また、染み込み防止部 3の外周半径は、支持ウェハ 1の外 周半径の 80〜120%であることが好ましぐ 90〜100%であることが更に好ましい。 また、染み込み防止部 3の幅 (リング形状の外周の半径と内周の半径との差)が、染 み込み防止部 3の外周の半径の 1〜20%であることが好ましぐ 2〜10%であること が更に好ましい。 1%より短いと、固定剤 2の漏洩を防止する能力が低下することがあ り、 20%より長いと、配設できる固定剤 2の量が少なくなり、接着固定効果が低減する ことがある。 [0066] 染み込み防止部材 (染み込み防止部)の材質としては、耐薬品性、耐熱性の観点 から、フッ化物を含有する榭脂材料、表面をフッ素系材料などで表面撥水加工した 金属および Zまたは金属酸化物材料等が好ましい。 [0065] It is preferable that the outer peripheral shape of the infiltration preventing portion 3 is circular. This is because the wafer to be processed is usually formed in a circular shape (disc shape), and it is preferable to form the supporting wafer 1 in a circular shape having almost the same size. Is also adapted to its size and shape. Further, the outer peripheral radius of the permeation preventing unit 3 is preferably 80 to 120% of the outer peripheral radius of the support wafer 1, and more preferably 90 to 100%. In addition, it is preferable that the width of the permeation prevention part 3 (the difference between the radius of the outer periphery and the inner periphery of the ring shape) is 1 to 20% of the outer periphery radius of the permeation prevention part 3 2 to More preferably, it is 10%. If it is shorter than 1%, the ability to prevent the leakage of the fixing agent 2 may be reduced, and if it is longer than 20%, the amount of the fixing agent 2 that can be disposed is reduced, and the adhesive fixing effect may be reduced. . [0066] From the viewpoint of chemical resistance and heat resistance, the material of the penetration prevention member (penetration prevention part) is a resin material containing fluoride, a metal whose surface is water-repellent treated with a fluorine-based material, etc., and Z Or a metal oxide material etc. are preferable.
[0067] 染み込み防止部材 (染み込み防止部）は、固定剤 2により支持ウェハ 1に貼り付けら れて 、る力、もしくは支持体ウェハ 1に直接接着されて 、ることが好まし 、。  [0067] The penetration preventing member (penetration preventing portion) is preferably attached to the supporting wafer 1 with the fixing agent 2 and is adhered to the supporting wafer 1 or directly attached to the supporting wafer 1.
[0068] また、図 3 (a)、図 3 (b)に示すように、染み込み防止部 3と固定剤 2との間に隙間が 開いていてもよい。隙間が開いているときは、その隙間が支持ウェハエッジ部の幅 W に対して、 20%以下であることが好ましい。ここで、図 3 (a)は、本発明の固定剤付き ウェハの製造方法により得られた、染み込み防止部 3と固定剤 2との間に隙間が形成 された固定剤付きウェハ 102の平面図、図 3 (b)はその C C'断面図である。  Further, as shown in FIGS. 3 (a) and 3 (b), a gap may be opened between the penetration preventing part 3 and the fixing agent 2. When the gap is open, the gap is preferably 20% or less with respect to the width W of the supporting wafer edge portion. Here, FIG. 3 (a) is a plan view of the wafer 102 with the fixing agent in which a gap is formed between the penetration preventing part 3 and the fixing agent 2 obtained by the method for manufacturing the wafer with the fixing agent of the present invention. Fig. 3 (b) is a cross-sectional view of CC '.
[0069] (1 4)カバーフィルム；  [0069] (1 4) Cover film;
本発明の固定剤付きウェハの他の実施形態は、上述した本発明の固定剤付きゥェ ハの一の実施形態に、更に、カバーフィルムを備えたものである。図 2 (a)、図 2 (b)に 示すように、本実施形態の固定剤付きウェハ 101は、支持ウェハ 1の表面に配設され た固定剤 2及び染み込み防止部 3の表面に、更にカバーフィルム 5が配設されている 。カバーフィルム 5を固定剤 2及び染み込み防止部 3の表面に配設することにより、金 属、埃等による固定剤 2及び染み込み防止部 3の表面の汚染を防止することができる 。また、固定剤 2が支持ウエノ、から剥がれ、欠落することを防止することができ、ハンド リング性を向上させることが可能となる。本実施形態の、カバーフィルムを備えた固定 剤付きウェハを使用するときは、カバーフィルムを剥がして力も使用する。ここで、図 2 (a)は、本発明の固定剤付きウェハの他の実施形態を模式的に示す斜視図であり、 図 2 (b)は、図 2 (a)の B— B'断面図である。  In another embodiment of the wafer with a fixing agent of the present invention, a cover film is further provided in the embodiment of the wafer with a fixing agent of the present invention described above. As shown in FIGS. 2 (a) and 2 (b), the wafer 101 with the fixing agent of the present embodiment is further provided on the surface of the fixing agent 2 and the permeation preventing portion 3 disposed on the surface of the support wafer 1. A cover film 5 is provided. By disposing the cover film 5 on the surfaces of the fixing agent 2 and the permeation preventing portion 3, contamination of the surfaces of the fixing agent 2 and the permeation preventing portion 3 due to metal, dust or the like can be prevented. In addition, it is possible to prevent the fixing agent 2 from being peeled off and missing from the support wells, and to improve handling properties. When using a wafer with a fixing agent provided with a cover film of this embodiment, the cover film is peeled off and the force is also used. Here, FIG. 2 (a) is a perspective view schematically showing another embodiment of the wafer with a fixing agent of the present invention, and FIG. 2 (b) is a cross-sectional view taken along the line BB ′ of FIG. 2 (a). FIG.
[0070] カバーフィルムの大きさは、固定剤の表面全体を覆える大きさであることが好ましく 、固定剤の表面全体と染み込み防止部上面の全体とを覆える大きさであることが更 に好ましい。また、カバーフィルムは、支持ウェハの外周半径の 120% (最大半径）を 超えない半径の円形、又は、一辺の長さがその最大半径の 2倍の長さの正方形であ ることが好ましい。  [0070] The size of the cover film is preferably large enough to cover the entire surface of the fixing agent, and more preferably large enough to cover the entire surface of the fixing agent and the entire top surface of the infiltration prevention portion. preferable. Further, the cover film is preferably a circular shape having a radius not exceeding 120% (maximum radius) of the outer peripheral radius of the support wafer, or a square having a length of one side twice the maximum radius.
[0071] カバーフィルムの厚さは、 5〜： LOO μ mであることが好ましぐ 10〜50 μ mであること が更に好ましい。 5 μ mより薄いと、カバーフィルムとしての強度が不足し、外力で力 バーフィルムが損傷しやすく固定剤表面を保護できないことがあり、 100 mより厚い と、カバーフィルムの屈曲性が不足して使用する際にはがしにく 、ことがある。 [0071] The thickness of the cover film is 5 to: 10 to 50 μm, preferably LOO μm Is more preferable. If it is thinner than 5 μm, the strength of the cover film will be insufficient, and the force bar film may be easily damaged by external force, and the surface of the fixing agent may not be protected. If it is thicker than 100 m, the flexibility of the cover film will be insufficient. It may be difficult to remove when using it.
[0072] カバーフィルムとしては、耐熱性があり、離形性のフィルムであることが好まし 、。例 えば、ポリイミドフィルム、 PTFE (ポリテトラフルォロエチレン）フィルム、 PFA (テトラフ ルォロエチレン.パーフルォロアルキルビュルエーテル共重合体）フィルム等を挙げ ることができる。また、固定剤の溶融温度が低い場合は、離形処理を施した PET (ポリ エチレンテレフタレート）フィルム等も使用可能である。カバーフィルムとしては、いず れも、被カ卩ェウェハを汚染しないため、メタルフリー化処理等を施してあることが好ま しい。 [0072] The cover film is preferably a heat-resistant and releasable film. For example, a polyimide film, a PTFE (polytetrafluoroethylene) film, a PFA (tetrafluoroethylene perfluoroalkyl butyl ether copolymer) film, and the like can be given. In addition, when the melting temperature of the fixing agent is low, a PET (polyethylene terephthalate) film that has been subjected to a release treatment can be used. As the cover film, it is preferable that the cover film has been subjected to metal-free treatment or the like so as not to contaminate the wafer to be covered.
[0073] (2)固定剤付きウェハの製造方法：  [0073] (2) Manufacturing method of wafer with fixing agent:
本発明の固定剤付きウェハの製造方法は、固定剤を支持ウェハの表面に塗布して 固定剤付きウェハを製造する固定剤付きウェハの製造方法であって、支持ウェハの エッジ部 (支持ウェハエッジ部）に、染み込み防止構造を配設する工程を有する固定 剤付きウェハの製造方法である。これにより支持ウェハエッジ部に染み込み防止構 造を配設するとともに、固定剤を支持ウェハの表面に薄く均一に塗布することができ る。  The method for producing a wafer with a fixing agent according to the present invention is a method for manufacturing a wafer with a fixing agent by applying a fixing agent to the surface of a supporting wafer to produce a wafer with a fixing agent, wherein the edge portion of the supporting wafer (supporting wafer edge portion) ) Is a method for manufacturing a wafer with a fixing agent, which has a step of providing a penetration preventing structure. As a result, a structure for preventing penetration can be provided at the edge of the support wafer, and the fixing agent can be applied thinly and uniformly on the surface of the support wafer.
[0074] (2- 1)固定剤付きウェハの製造方法の一の実施形態；  [0074] (2-1) One embodiment of a method for producing a wafer with a fixing agent;
本発明の固定剤付きウェハの製造方法の一の実施形態は、固定剤を、液体の状 態で、支持ウェハの表面に塗布する工程と、固定剤を溶解することができる溶剤で支 持ウェハエッジ部上の固定剤を溶解除去する工程と、支持ウェハエッジ部に、染み 込み防止構造を配設する工程とを有する固定剤付きウェハの製造方法である。  One embodiment of the method for producing a wafer with a fixing agent of the present invention includes a step of applying the fixing agent to the surface of the support wafer in a liquid state, and a supporting wafer edge with a solvent capable of dissolving the fixing agent. This is a method for producing a wafer with a fixing agent, which comprises a step of dissolving and removing the fixing agent on the part and a step of disposing an infiltration preventing structure at the edge of the supporting wafer.
[0075] (2- 1 - 1)固定剤を支持ウェハに塗布する工程； [0075] (2-1-1) applying a fixing agent to the support wafer;
図 4A、図 4B及び図 5A、図 5Bは、本発明の固定剤付きウェハの製造方法の一実 施形態の一工程を模式的に示し、図 4A及び図 5Aは斜視図、図 4B及び図 5Bはそ れぞれ図 4Aの D— D'断面図及び図 5Aの E— E'断面図である。本実施形態の製 造方法は、まず、図 4A、図 4Bに示すように、室温で固体の固定剤 12を支持ウェハ 1 1の表面に乗せ、固定剤 12を加熱溶融した後、図 5A、図 5Bに示すように支持ゥェ ノ、 11の表面に溶融状態の固定剤 12を塗布する工程を有する。または、液体の固定 剤を支持ウェハに直接回転塗布しても良い。本実施形態では、固定剤 12を加熱溶 融した後に支持ウェハ 11を回転させて固定剤 12を塗布して 、るが、固定剤 12を加 熱溶融しながら支持ウェハ 11を回転させて固定剤 12を塗布するようにしてもよい。こ こで、「室温で固体」とは、 25°C以下の温度で固体状態であることをいう。 4A, 4B, 5A, and 5B schematically show one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention, and FIGS. 4A and 5A are perspective views, FIGS. 5B is a sectional view taken along the line DD ′ in FIG. 4A and a sectional view taken along the line EE ′ in FIG. 5A, respectively. In the manufacturing method of this embodiment, first, as shown in FIGS. 4A and 4B, solid fixing agent 12 is placed on the surface of support wafer 11 at room temperature, and fixing agent 12 is heated and melted. As shown in Figure 5B No. 11 has a step of applying a molten state fixing agent 12 to the surface of 11. Alternatively, a liquid fixing agent may be directly spin-coated on the support wafer. In the present embodiment, after the fixing agent 12 is heated and melted, the support wafer 11 is rotated to apply the fixing agent 12. However, while the fixing agent 12 is heated and melted, the support wafer 11 is rotated to fix the fixing agent 12. 12 may be applied. Here, “solid at room temperature” means a solid state at a temperature of 25 ° C or lower.
[0076] 本実施形態においては、室温で固体の固定剤 12を支持ウェハ 11の表面の中心（ 回転中心)部分に置き、固定剤 12を加熱溶融し、支持ウェハ 11をその表面に垂直 な中心軸を中心に回転方向 Rで示される方向に回転させながら、支持ウェハ 11の回 転による遠心力により溶融状態の固定剤 12を中心力も外周に広げるスピンコートに より固定剤 12を支持ウェハ 11に塗布することが好ま 、。  In this embodiment, the fixing agent 12 that is solid at room temperature is placed on the center (rotation center) portion of the surface of the support wafer 11, the fixing agent 12 is heated and melted, and the support wafer 11 is centered perpendicular to the surface. While rotating in the direction indicated by the rotation direction R about the axis, the fixing agent 12 is applied to the supporting wafer 11 by spin coating that expands the molten fixing agent 12 to the outer periphery by the centrifugal force caused by the rotation of the supporting wafer 11. Preferable to apply.
[0077] 支持ウェハ 11の回転速度は、 50rpm〜l, OOOrpmであることが好ましぐ lOOrp m〜300rpmであることが更に好まし!/、。 50rpmより遅!、と固定剤 2が支持ウェハ 11 の表面全体に均一に塗布され難いことがあり、 1, OOOrpmより早いと、支持ウェハ 11 上力も排除される固定剤 12が多くなり過ぎることがある。  [0077] The rotation speed of the support wafer 11 is preferably 50 rpm to l, OOO rpm, more preferably lOOrp m to 300 rpm! /. It may be difficult to apply the fixative 2 evenly over the entire surface of the support wafer 11, and if it is faster than 1, OOOrpm, there will be too much fixative 12, which also eliminates the upper force of the support wafer 11. is there.
[0078] 支持ウェハ 11の回転速度は、固定剤 12の溶融粘度等に合わせて更に最適化する ことが好ましい。また、支持ウェハ 11の回転速度は、時間により変化させてもよい。例 えば、固定剤 12が支持ウェハ 11の表面全体に広がるまでは低速で回転させ、その 後高速で回転させ、それぞれの時間を最適化することにより、固定剤 12を所望の厚 さにすることができる。例えば最初は低速（lOOrpm程度）で回転させ、次に 700rpm 程度で所望の膜厚にすることが出来る。また、例えば、支持ウェハを回転させながら 固定剤を支持ウェハの表面に塗布するときには、固定剤を支持ウェハ表面の中心部 分に置き、加熱溶融して支持ウェハを例えば 100rpm〜200rpmで回転させて、固 定剤を支持ウェハ表面全体に厚めに広げ、その後、昇温し、その状態で支持ウェハ 回転数を例えば 500rpm〜700rpmとして、固定剤を薄ぐ均一な膜厚で塗布するこ とが好ましい。  [0078] The rotational speed of the support wafer 11 is preferably further optimized in accordance with the melt viscosity of the fixing agent 12 and the like. Further, the rotation speed of the support wafer 11 may be changed with time. For example, rotate the fixing agent 12 to the desired thickness by rotating at low speed until the fixing agent 12 spreads over the entire surface of the support wafer 11, then rotating at high speed and optimizing each time. Can do. For example, it can be rotated at a low speed (about lOOrpm) at first, and then at a desired film thickness at about 700rpm. For example, when applying the fixing agent to the surface of the supporting wafer while rotating the supporting wafer, the fixing agent is placed at the center of the supporting wafer surface, heated and melted, and the supporting wafer is rotated at, for example, 100 rpm to 200 rpm. It is preferable that the fixing agent is spread over the entire surface of the supporting wafer, and then the temperature is raised, and in that state, the rotating speed of the supporting wafer is set to, for example, 500 rpm to 700 rpm, and the fixing agent is applied in a thin uniform film thickness. .
[0079] 本実施形態において、図 4A、図 4Bに示す支持ウェハ 1の中心部に置く溶融前の 固定剤 12の形状は特に限定されるものではない。例えば、図 4Aに示すように、厚め の円板状であってもよいし、円板ではなく多角形板、楕円板、その他不定形状の板 や塊であってもよい。 In the present embodiment, the shape of the fixing agent 12 before melting placed in the central portion of the support wafer 1 shown in FIGS. 4A and 4B is not particularly limited. For example, as shown in FIG. 4A, it may be a thick disk, or a polygonal plate, an elliptical plate, or any other irregular plate instead of a circular plate. Or a lump.
[0080] 支持ウェハ 11に置く固定剤 12の大きさは、例えば、支持ウェハ 11の直径が 6〜8 インチの場合には、 500mm3程度から 1, 000mm3程度であることが好ましい。支持 ウェハ 11の直径が 8〜12インチ（8インチを除く）又はそれ以上の場合には、その支 持ウェハ 11の大きさに合わせて固定剤 12の大きさを決定することが好ま 、。また、 複数の固定剤を分散して配置しても良ぐ更には、ウェハ全面に均一に分布するよう に固定剤の量を調整することが好ましい。 [0080] The size of the fixing agent 12 placed on the support wafer 11 is, for example, in the case of a diameter of 6 to 8 inch support wafer 11 is preferably about 1, 000 mm 3 from about 500 mm 3. When the diameter of the supporting wafer 11 is 8 to 12 inches (excluding 8 inches) or more, it is preferable to determine the size of the fixing agent 12 according to the size of the supporting wafer 11. In addition, a plurality of fixing agents may be arranged in a dispersed manner. Furthermore, it is preferable to adjust the amount of the fixing agent so that it is uniformly distributed over the entire wafer surface.
[0081] 本実施形態において、図 5A、図 5Bに示す支持ウェハ 11の表面に塗布された固 定剤 12の厚さは、上記本発明の固定剤付きウェハにおける、固定剤の厚さと同様で あることが好ましい。また、固定剤の材質、溶融温度、接着強度等の物性、添加剤等 についても、上記本発明の固定剤付きウェハにおける固定剤の場合と同様であるこ とが好ましい。  In this embodiment, the thickness of the fixing agent 12 applied to the surface of the support wafer 11 shown in FIGS. 5A and 5B is the same as the thickness of the fixing agent in the wafer with the fixing agent of the present invention. Preferably there is. Further, the material of the fixing agent, the physical properties such as the melting temperature and the adhesive strength, the additive and the like are preferably the same as those of the fixing agent in the wafer with the fixing agent of the present invention.
[0082] 本実施形態において使用される支持ウェハの形状、厚さ、材質等については、上 記本発明の固定剤付きウェハにおける、支持ウェハの場合と同様であることが好まし い。  [0082] The shape, thickness, material, and the like of the support wafer used in this embodiment are preferably the same as those of the support wafer in the wafer with a fixing agent of the present invention.
[0083] (2- 1 - 2)支持ウェハエッジ部上の固定剤を溶解除去する工程；  [0083] (2-1-2) Dissolving and removing the fixing agent on the supporting wafer edge portion;
本実施形態の固定剤付きウェハの製造方法は、更に、図 6A、図 6Bに示すように、 固定剤 12を溶解することができる溶剤 22で、支持ウェハ 11のエッジ部分 (支持ゥェ ハエッジ部） 14に塗布された固定剤 12を溶解除去する工程を有する。このように、支 持ウェハエッジ部 14上の固定剤 12を溶解除去することにより、染み込み防止部を、 固定剤 12の外周を囲むようにして、容易に形成することができるようになる。支持ゥェ ノ、 11の表面全体にまず固定剤を塗布し、その後、支持ウェハエッジ部 14上の固定 剤 12を溶解除去するという方法により、固定剤のはみ出し及び液状物質の染み込み を防止できる固定剤付き支持ウェハを効率的に製造することができる。ここで、図 6A は、本発明の固定剤付きウェハの製造方法の一実施形態の一工程を模式的に示す 斜視図、図 6Bは、その F— F'断面図であり、溶剤 22により支持ウェハエッジ部 14に 塗布された固定剤 12を溶解除去した後の状態を示している。  As shown in FIGS. 6A and 6B, the method for manufacturing a wafer with a fixing agent according to the present embodiment further uses a solvent 22 that can dissolve the fixing agent 12, and the edge portion of the support wafer 11 (support wafer edge portion). ) The step of dissolving and removing the fixing agent 12 applied to 14 is included. Thus, by dissolving and removing the fixing agent 12 on the supporting wafer edge portion 14, the penetration preventing portion can be easily formed so as to surround the outer periphery of the fixing agent 12. Fixing agent that prevents sticking out of the fixing agent and infiltration of the liquid substance by first applying the fixing agent to the entire surface of the supporting wafer 11 and then dissolving and removing the fixing agent 12 on the supporting wafer edge 14. An attached support wafer can be manufactured efficiently. Here, FIG. 6A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention, and FIG. 6B is a sectional view taken along line FF ′, which is supported by a solvent 22. A state after the fixing agent 12 applied to the wafer edge portion 14 is dissolved and removed is shown.
[0084] 溶剤 22は溶剤ノズル 21の先端より吐出され、固定剤 12が表面全体に塗布された 支持ウェハの裏面部よりエッジ部分に供給される。溶剤 22の供給速度、溶剤ノズル 2 1の先端の開口径、支持ウェハの裏面に当てる角度、支持ウェハの回転数は固定剤 を除去する領域によって最適化する必要がある。 [0084] The solvent 22 was discharged from the tip of the solvent nozzle 21, and the fixing agent 12 was applied to the entire surface. It is supplied to the edge portion from the back surface portion of the support wafer. The supply speed of the solvent 22, the opening diameter of the tip of the solvent nozzle 21, the angle applied to the back surface of the support wafer, and the number of rotations of the support wafer need to be optimized depending on the region where the fixing agent is removed.
[0085] 本実施形態において使用する溶剤 22は、固定剤 12を溶解できるものであれば特 に限定されるものではなぐ固定剤 12の種類によって適宜決定することができる。例 えば、固定剤 12が上記結晶性ィ匕合物である場合には、イソプロパノール、ブタノール 、へキサノーノレ、エタノーノレ、メタノーノレ、エチレングリコーノレ、ジエチレングリコーノレ、 プロピレングリコール、ジプロピレングリコール、フエノール、 t—アミノレアルコール、シ クロへキサノール等のアルコール類； n—ペンタン、シクロペンタン、 n—へキサン、シ クロへキサン、 n—ヘプタン、シクロヘプタン、 n—オクタン、シクロオクタン、 n—デカン 、シクロデカン、ジシクロペンタジェン水素化物、ベンゼン、トルエン、キシレン、デュ レン、インデン、デカリン、テトラリン、テトラヒドロナフタレン、デカヒドロナフタレン、スク ヮラン、ェチルベンゼン、 t ブチルベンゼン、トリメチルベンゼン等の炭化水素系溶 媒；アセトン、メチルェチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロへ キサノン等のケトン類；ェチルエーテル、エチレングリコールジメチルエーテル、ェチ レングリコールジェチルエーテル、ジエチレングリコールジメチルエーテル、ジェチレ ングリコールジェチルエーテル、テトラヒドロフラン、ジォキサン等のエーテル類；酢酸 ェチル、酢酸ブチル、酪酸ェチル、エチレングリコールモノメチルエーテルアセテート 、エチレングリコーノレモノェチノレエーテノレアセテート、エチレングリコーノレモノァセテ ート、ジエチレングリコーノレモノメチノレエーテノレアセテート、ジエチレングリコーノレモノ ェチノレエーテノレアセテート、プロピレングリコーノレモノメチノレエーテノレアセテート、プ ロピレングリコーノレモノェチノレエーテノレアセテート、ジプロピレングリコーノレモノメチノレ エーテルアセテート、ジプロピレングリコールモノェチルエーテルアセテート等のエス テル類；およびジメチルホルムアミド、ジメチルァセトアミド、 N—メチルピロリドン、へキ サメチルホスホミド、ジメチルスルホキシド、 y ブチロラタトン、クロ口ホルム、塩化メ チレン等の極性溶媒、フォトレジスト剥離液などを用いることができる。 [0085] The solvent 22 used in the present embodiment is not particularly limited as long as it can dissolve the fixing agent 12, and can be appropriately determined depending on the type of the fixing agent 12. For example, when the fixing agent 12 is the above crystalline compound, isopropanol, butanol, hexanol, ethanol, methanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, phenol, t- Alcohols such as aminole alcohol and cyclohexanol; n —pentane, cyclopentane, n-hexane, cyclohexane, n —heptane, cycloheptane, n-octane, cyclooctane, n-decane, cyclodecane, Hydrocarbon solutions such as dicyclopentagen hydride, benzene, toluene, xylene, durene, indene, decalin, tetralin, tetrahydronaphthalene, decahydronaphthalene, squalane, ethylbenzene, t-butylbenzene, trimethylbenzene, etc. Medium: Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc .; Ethyl ether, ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, jet ethylene glycol jetyl ether, tetrahydrofuran , Ethers such as dioxane; ethyl acetate, butyl acetate, ethyl butyrate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl enoate acetate, ethylene glycol monoacetate, diethylene glycol monomethenoate etherate Acetate, diethylene glycolenomonoethylenoate acetate, propylene glycolenomethinoatenoacetate, prop Esters such as pyreneglycol-monoethylenoleethenoleacetate, dipropyleneglycololemonomethinole ether acetate, dipropyleneglycol monoethyl ether acetate; and dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Polar solvents such as xamethyl phosphomide, dimethyl sulfoxide, y-butyrolataton, black mouth form, and methylene chloride, and a photoresist stripping solution can be used.
[0086] これらの中では、イソプロパノール、エタノール、メタノール、アセトン、メチルェチル ケトン、テトラヒドロフランが好ましい。また、上記溶剤 22は、単独で用いても、 2種以 上を混合して用いてもよい。 Of these, isopropanol, ethanol, methanol, acetone, methyl ethyl ketone, and tetrahydrofuran are preferred. In addition, the solvent 22 may be used alone or in combination of two or more. You may mix and use the above.
[0087] (2— 1 3)染み込み防止構造を配設する工程；  [2-1] (2) 3) Step of disposing an infiltration preventing structure;
本実施形態の固定剤付きウェハの製造方法は、更に、図 7A、図 7Bに示すように、 固定剤 12を洗浄除去した支持ウェハエッジ部 14に、染み込み防止部材を配置して 、染み込み防止構造 (染み込み防止部 13)を配設し、固定剤付きウェハとすることが 好まし 、。染み込み防止部 13は固定剤を除去した支持体ウェハエッジ部にフッ化物 含有榭脂など染み込み防止部材 (染み込み防止剤)を塗布することで支持体ウェハ に直接接着した防止部を形成する方法により形成される。染み込み防止剤を、染み 込み防止剤塗布用のノズル（図示せず)の先端より吐出し、支持ウェハエッジ部 14に スピンコートすることにより染み込み防止構造 (染み込み防止部） 13を形成してもよい 。染み込み防止部 13を配設することにより、固定剤 12のはみ出しを防止することが でき、さらに、被カ卩ェウェハをエッチングする時等においてエッチング液が染み込む ことを防止することが可能となる。ここで、図 7Aは、本発明の固定剤付きウェハの製 造方法の一実施形態の一工程を模式的に示す斜視図であり、図 7Bは、その G— G' 断面図であり、染み込み防止部材を支持ウェハエッジ部 14に配設して染み込み防 止構造を配設した後の状態を示して!/ヽる。  As shown in FIGS. 7A and 7B, the method for manufacturing a wafer with a fixing agent according to the present embodiment further includes a permeation preventing member disposed on the support wafer edge portion 14 from which the fixing agent 12 has been cleaned and removed. It is preferable to install a permeation prevention part 13) and use a wafer with a fixing agent. The permeation preventive part 13 is formed by a method of forming a preventive part directly adhered to the support wafer by applying a permeation preventive member (permeation preventive agent) such as fluoride-containing sallow on the edge of the support wafer from which the fixing agent has been removed. The The permeation preventing structure (stain prevention portion) 13 may be formed by discharging a permeation prevention agent from the tip of a nozzle (not shown) for applying the permeation prevention agent and spin-coating the support wafer edge portion 14. By disposing the soaking prevention part 13, it is possible to prevent the fixing agent 12 from protruding, and it is possible to prevent the etching solution from soaking when the wafer to be covered is etched. Here, FIG. 7A is a perspective view schematically showing one step of an embodiment of the method for manufacturing a wafer with a fixing agent of the present invention, and FIG. The state after the prevention member is arranged on the supporting wafer edge portion 14 and the infiltration prevention structure is arranged is shown.
[0088] 染み込み防止部の、形状、材質等は、上記本発明の固定剤付きウェハにおける、 染み込み防止部の場合と同様であることが好ましい。  [0088] The shape, material, and the like of the soaking prevention part are preferably the same as those of the soaking prevention part in the wafer with a fixing agent of the present invention.
[0089] (2- 1 4)カバーフィルムを貼り付ける工程；  [0089] (2-1 4) A process of applying a cover film;
本実施形態の固定剤付きウェハの製造方法は、更に、図 8A、図 8Bに示すように、 固定剤 12の表面にカバーフィルム 15を貼り付ける工程を有することが好ましい。これ により、金属、埃等による固定剤及び染み込み防止部の表面の汚染を防止すること ができる。また、固定剤が支持ウエノ、から剥がれ、欠落することを防止することができ 、ハンドリング性を向上させることが可能となる。ここで、図 8Aは、本発明の固定剤付 きウェハの製造方法の一実施形態の一工程を模式的に示す斜視図であり、図 8Bは The method for producing a wafer with a fixing agent of this embodiment preferably further includes a step of attaching a cover film 15 to the surface of the fixing agent 12 as shown in FIGS. 8A and 8B. Thereby, contamination of the surface of the fixing agent and the permeation preventive part due to metal, dust or the like can be prevented. In addition, it is possible to prevent the fixing agent from being peeled off and missing from the support well, and it is possible to improve handling properties. Here, FIG. 8A is a perspective view schematically showing one step of an embodiment of the method for producing a wafer with a fixing agent of the present invention, and FIG.
、その H— H'断面図であり、固定剤 12の表面にカバーフィルム 15を貼り付けた後の 状態を示している。 FIG. 5 is a cross-sectional view taken along the line H-H ′, showing a state after the cover film 15 is attached to the surface of the fixing agent 12.
[0090] カバーフィルム 15は、大きめのフィルム材料を固定剤 12の表面に貼り付けた後に、 所定の大きさに切断してもよいし、あら力じめ所定の大きさに形成したものを固定剤 1 2の表面に貼り付けてもよい。カバーフィルム 15は、少なくとも固定剤 12の全面を覆う ことが好ましぐ染み込み防止部 13の全面をも覆うことが更に好ましい。カバーフィル ム 15の、形状、材質等は、上記本発明の固定剤付きウェハにおける、カバーフィル ムの場合と同様であることが好ましい。 [0090] The cover film 15 is obtained by attaching a large film material to the surface of the fixing agent 12, It may be cut into a predetermined size, or may be affixed to the surface of the fixing agent 12 after being formed into a predetermined size. The cover film 15 preferably covers at least the entire surface of the fixing agent 12 and more preferably covers the entire surface of the infiltration preventing part 13. The shape, material, and the like of the cover film 15 are preferably the same as those in the case of the cover film in the wafer with the fixing agent of the present invention.
[0091] (2- 2)固定剤付きウェハの製造方法の他の実施形態； (2-2) Another embodiment of a method for producing a wafer with a fixing agent;
本発明の固定剤付きウェハの製造方法の他の実施形態は、固定剤を支持ウェハ の表面に塗布して固定剤付きウェハを製造する固定剤付きウェハの製造方法であつ て、支持ウェハエッジ部に、染み込み防止構造を配設する工程と、固定剤を、支持ゥ ェハと染み込み防止構造とにより形成される窪みに配置し、固定剤を液体状態として 、支持ウェハの表面に塗布する工程とを有する固定剤付きウェハの製造方法である  Another embodiment of the method for manufacturing a wafer with a fixing agent according to the present invention is a method for manufacturing a wafer with a fixing agent by applying a fixing agent to the surface of a supporting wafer to manufacture a wafer with a fixing agent, and is provided at the edge of the supporting wafer. A step of disposing the infiltration prevention structure, and a step of disposing the fixing agent in a recess formed by the support wafer and the infiltration prevention structure, and applying the fixing agent to the surface of the support wafer in a liquid state. It is a manufacturing method of a wafer with a fixing agent having
[0092] (2— 2— 1)支持ウェハエッジ部に染み込み防止構造を配設する工程； [0092] (2-2-1) A step of providing a permeation preventing structure at the edge of the supporting wafer;
本実施形態の製造方法は、まず、図 9A、図 9Bに示すように、支持ウェハ 11の支 持ウェハエッジ部 14に、染み込み防止構造 (染み込み防止部 13)を配設する工程を 有する。図 9A、図 9Bは、本発明の固定剤付きウェハの製造方法の他の実施形態の 一工程を模式的に示し、図 9Aは平面図、図 9Bは図 9Aの I Γ断面図である。また、 本実施形態を説明する図面において、上記本発明の固定剤付きウェハの製造方法 の一の実施形態を説明する図面における各構成要素と同一の構成要素については 、同一の符号を付している。  9A and 9B, the manufacturing method of the present embodiment first includes a step of disposing a permeation prevention structure (a permeation prevention unit 13) on the support wafer edge portion 14 of the support wafer 11. FIG. 9A and FIG. 9B schematically show one process of another embodiment of the method for producing a wafer with a fixing agent of the present invention, FIG. 9A is a plan view, and FIG. 9B is a cross-sectional view taken along line I Γ in FIG. In the drawings for explaining the present embodiment, the same components as those in the drawings for explaining the embodiment of the method for producing a wafer with a fixing agent of the present invention are denoted by the same reference numerals. Yes.
[0093] 染み込み防止部 13は、リング状の染み込み防止部材を支持ウェハエッジ部 14に 配置することにより配設することが好ましい。支持ウェハエッジ部 14に、染み込み防 止部 13を配設することにより、支持ウェハ 11と染み込み防止部 13とにより窪み 31が 形成される。  The soaking prevention part 13 is preferably arranged by placing a ring-like soaking prevention member on the support wafer edge part 14. By providing the permeation preventing part 13 on the support wafer edge part 14, a recess 31 is formed by the support wafer 11 and the permeation prevention part 13.
[0094] 本実施の形態における、支持ウェハ及び染み込み防止部の各条件は、上記本発 明の固定剤付きウェハにおける、支持ウェハ及び染み込み防止部の各条件と同様 であることが好ましい。  [0094] The conditions of the support wafer and the permeation prevention unit in the present embodiment are preferably the same as the conditions of the support wafer and the permeation prevention unit in the wafer with a fixing agent of the present invention.
[0095] (2- 2- 2)固定剤を支持ウェハの所定の位置に配置する工程； 本実施形態の固定剤付きウェハの製造方法は、次に、図 10A、図 10Bに示すよう に、固定剤 12を、支持ウェハ 11と染み込み防止構造 13とにより形成される窪み 31 に配置する工程を有する。固定剤の、支持ウェハ 11上の位置は特に限定されない 力 支持ウェハ 11の中央部に配置することが好ましい。支持ウェハに塗布する前の 固定剤 12の材質、大きさ、溶融温度'接着強度等の物性、添加剤等については、上 記本発明の固定剤付きウェハの製造方法の一の実施形態の場合の場合と同様であ ることが好ましい。図 10Aは、本発明の固定剤付きウェハの製造方法の他の実施形 態の一工程を模式的に示す平面図であり、図 10Bは、その J J'断面図である。 (2-2-2) A step of disposing a fixing agent at a predetermined position of the support wafer; In the method for manufacturing a wafer with a fixing agent according to the present embodiment, as shown in FIGS. 10A and 10B, the step of arranging the fixing agent 12 in the recess 31 formed by the support wafer 11 and the penetration preventing structure 13 is performed next. Have The position of the fixing agent on the support wafer 11 is not particularly limited. Regarding the material, size, melting temperature, adhesive strength, and other physical properties, additives, etc. of the fixing agent 12 before being applied to the support wafer, in the case of one embodiment of the method for manufacturing a wafer with a fixing agent of the present invention described above It is preferable to be the same as in this case. FIG. 10A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention, and FIG. 10B is a JJ ′ sectional view thereof.
[0096] (2- 2- 3)カバーフィルムを固定剤の表面に配置する工程； [0096] (2-2-3) A step of disposing a cover film on the surface of the fixing agent;
本実施形態の固定剤付きウェハの製造方法は、次に、図 11A、図 11Bに示すよう に、カバーフィルム 15を固定剤 12の表面に配置する工程を有することが好ましい。 本実施形態においては、図 11A、図 11Bに示すように、支持ウェハ 11より大きい四 角形のカバーフィルム 15を固定剤 12の表面に配設している。カバーフィルム 15の大 きさは、このように大き目とし、後で所定の大きさに切断してもよいし、所定の大きさに 切断したものを固定剤 12に貼り付けてもよい。カバーフィルム 15の厚さ、材質等は、 上記本発明の固定剤付きウェハにおける、カバーフィルムの場合と同様であることが 好ましい。図 11Aは、本発明の固定剤付きウェハの製造方法の他の実施形態の一 工程を模式的に示す平面図であり、図 11Bは、その K K'断面図である。  The method for producing a wafer with a fixing agent of this embodiment preferably has a step of arranging a cover film 15 on the surface of the fixing agent 12 as shown in FIGS. 11A and 11B. In this embodiment, as shown in FIGS. 11A and 11B, a rectangular cover film 15 larger than the support wafer 11 is disposed on the surface of the fixing agent 12. The size of the cover film 15 is thus large, and may be cut into a predetermined size later, or may be affixed to the fixing agent 12 after being cut into a predetermined size. The thickness, material, etc. of the cover film 15 are preferably the same as those in the case of the cover film in the wafer with a fixing agent of the present invention. FIG. 11A is a plan view schematically showing a process of another embodiment of the method for producing a wafer with a fixing agent of the present invention, and FIG. 11B is a sectional view taken along the line KK ′.
[0097] (2- 2-4)固定剤を支持ウェハに塗布する工程； [0097] (2-2-4) A step of applying a fixing agent to the support wafer;
本実施形態の固定剤付きウェハの製造方法は、次に、図 12A、図 12Bに示すよう に、カバーフィルム 15の上から力 fをカ卩えて、カバーフィルム 15及び固定剤 12を押 圧しながら固定剤 12を加熱して液体状態とし、固定剤 12を支持ウェハ 11の表面に 塗布する工程を有することが好ましい。これにより固定剤 12を窪み 31 (図 11A, B参 照）内に均一に広げることができる。カバーフィルム 15の上力も力 fをカ卩えて、カバー フィルム 15及び固定剤 12を押圧するときは、固定剤 12全体に均一に力 fが加わるこ とが好ましい。これにより、固定剤 12を均一な厚さで広げることができる。また、力 fと しては、特に限定されないが、 1〜： LOOOgZcm2であることが好ましい。また、固定剤 12を窪み 31 (図 11A, B参照）内全体に広げることで、染み込み防止部 13を、固定 剤 12により支持ウェハエッジ部 14に固定することができる。図 12Aは、本発明の固 定剤付きウェハの製造方法の他の実施形態の一工程を模式的に示す平面図でありAs shown in FIGS. 12A and 12B, the manufacturing method of the wafer with a fixing agent of the present embodiment next applies a force f from the top of the cover film 15 while pressing the cover film 15 and the fixing agent 12. It is preferable to have a step of heating the fixing agent 12 to a liquid state and applying the fixing agent 12 to the surface of the support wafer 11. This allows the fixative 12 to be evenly spread in the recess 31 (see FIGS. 11A and B). When pressing the cover film 15 and the fixing agent 12 with the upper force of the cover film 15 as well, it is preferable that the force f is applied uniformly to the entire fixing agent 12. Thereby, the fixing agent 12 can be spread with a uniform thickness. The force f is not particularly limited, but is preferably 1 to: LOOOgZcm 2 . In addition, the penetration preventing part 13 is fixed by spreading the fixing agent 12 over the entire depression 31 (see FIGS. 11A and 11B). It can be fixed to the supporting wafer edge portion 14 by the agent 12. FIG. 12A is a plan view schematically showing one step of another embodiment of the method for producing a wafer with a fixing agent of the present invention.
、図 12Bは、その L L'断面図である。 FIG. 12B is an L L ′ cross-sectional view thereof.
[0098] 図 12A、図 12Bに示す、カバーフィルム 15の染み込み防止部 13からはみ出た部 分を切断して、図 8A、図 8Bに示す本発明の固定剤付きウェハの製造方法の一の実 施形態で得られた固定剤付きウェハ 104と同様の固定剤付きウェハが得られる。  FIG. 12A and FIG. 12B show one embodiment of the method for producing the wafer with a fixing agent of the present invention shown in FIG. 8A and FIG. 8B by cutting the portion of the cover film 15 that protrudes from the penetration preventing portion 13. A wafer with a fixing agent similar to the wafer 104 with a fixing agent obtained in the embodiment is obtained.
[0099] (3)ウェハの加工：  [0099] (3) Wafer processing:
次に、本発明の固定剤付きウェハを使用した被加工ウェハの加工方法について説 明する。尚、固定剤付きウェハは、カバーフィルムを備えるものとする。  Next, a method for processing a wafer to be processed using the wafer with a fixing agent of the present invention will be described. In addition, a wafer with a fixing agent shall be provided with a cover film.
[0100] ウェハの加工方法は、まず、上述した本発明の固定剤付きウェハのカバーフィルム を剥がし、固定剤が配設されている側の面に、被加工ウェハ（ウエノ、）を、その裏面が 外側を向くように (裏面側が外側に露出するように)配置し、固定剤を加熱溶融させた 後、冷却して、ウェハと固定剤付きウェハとを接着固定する。  [0100] In the wafer processing method, first, the cover film of the wafer with the fixing agent of the present invention described above is peeled off, and the wafer to be processed (Ueno) is placed on the surface on which the fixing agent is disposed. Arrange them so that they face outward (the back side is exposed to the outside), heat and melt the fixing agent, and then cool it down to bond and fix the wafer to the wafer with the fixing agent.
[0101] 具体的には、固定剤付きウェハからカバーフィルムを剥がした後、固定剤付きゥェ ハにウェハを配置し、これらをヒートプレスの間に挟んで全体を減圧にし、ヒーターを 固定剤の融点 + 20°Cまで昇温して加圧プレスし、次に、プレスした状態で常圧に戻 し、ヒーターを徐冷し、固定剤を再度固化して接着を完了させることが好ましい。  [0101] Specifically, after removing the cover film from the wafer with the fixing agent, the wafer is placed on the wafer with the fixing agent, and the whole is depressurized by sandwiching them between the heat presses, and the heater is fixed. It is preferable to raise the temperature to + 20 ° C. and press with pressure, then return to normal pressure in the pressed state, slowly cool the heater, solidify the fixing agent again, and complete the adhesion.
[0102] 減圧は支持ウェハとウェハとの間の気泡除去のために行うものであり、 100〜lTor r程度でよぐ真空度を高くし過ぎると固定剤が揮発することがある。また、徐冷は固定 剤の固化温度 ± 10°C程度の範囲内であってもよぐ 5°CZmin以下、好ましくは 2°C Zmin以下の速度で徐冷することが望ましい。冷却が早いと固定剤の熱収縮や結晶 化の影響で内部に気泡を取り込みやすくなるため、接着強度が悪ィ匕することがある。  [0102] The depressurization is performed to remove bubbles between the support wafer and the fixing agent may volatilize if the degree of vacuum is too high at about 100 to 1 Torr. In addition, the slow cooling may be within the range of the solidification temperature of the fixing agent ± 10 ° C, and it is desirable to slowly cool at a rate of 5 ° C Zmin or less, preferably 2 ° C Zmin or less. If the cooling is fast, bubbles can be easily taken into the inside due to the heat shrinkage and crystallization of the fixing agent, which may deteriorate the adhesive strength.
[0103] 次に、ウェハと固定剤付きウェハとを接着固定した後に、ウェハ裏面を研磨又はェ ツチングして、ウェハを 100 μ m〜300 μ mに薄肉化する。  Next, after the wafer and the wafer with the fixing agent are bonded and fixed, the back surface of the wafer is polished or etched to thin the wafer to 100 μm to 300 μm.
[0104] 具体的には、まず、固定剤付きウェハに貼り合わされたウェハを固定剤付きウェハ ごと、例えばバックグラインド装置にセットし、ウェハの厚みが約 100 /z mに達する程 度まで荒研削することが好ましい。その後、研削で生じた研削歪み層の除去を行い、 所望の 10 m〜： L 00 m厚にまでカ卩ェする。この時の荒研削方法については特に 制限はなぐ公知の方法を用いることができる。研削歪みの除去方法については、フ エルト砥石方式、プラズマエッチング方式、 CMP方式および化学エッチング方式な ど力も選択して行うことができる。特に化学エッチング方式を用いた場合、固定剤付き ウェハが染み込み防止部を有するため、エッチング液が染み込むことを効果的に防 止することができる。 [0104] Specifically, first, the wafer bonded to the wafer with the fixing agent is set together with the wafer with the fixing agent, for example, in a back grinding apparatus, and rough grinding is performed until the wafer thickness reaches about 100 / zm. It is preferable. After that, the grinding distortion layer generated by grinding is removed, and the desired 10 m to: L 00 m thickness is covered. Especially about the rough grinding method at this time Any known method can be used. The grinding strain can be removed by selecting a force such as felt wheel method, plasma etching method, CMP method and chemical etching method. In particular, when the chemical etching method is used, since the wafer with the fixing agent has a permeation preventing portion, the permeation of the etching solution can be effectively prevented.
[0105] 上記フェルト砥石方式で用いられるフェルト砥石としては、たとえば、特開 2002— 2 83211号公報、特開 2002— 283212号公報などに記載されているフェルト素材に 砥粒を含浸させて作製した砥石を好適に用いることができる。  [0105] The felt grindstone used in the felt grindstone method is produced, for example, by impregnating a felt material described in JP-A-2002-28311, JP-A-2002-283212, etc. with abrasive grains. A grindstone can be used suitably.
[0106] 上記プラズマエッチング方式では、特開平 6— 338479号公報、再表 98/01695 0号公報、特開 2003— 100718号公報、特開 2003— 229418号公報などに示され ている装置を用い、 CF、 C F、 C F (ォクタフルォロシクロペンテン）などのエツチン  [0106] In the above plasma etching method, an apparatus described in Japanese Patent Laid-Open No. 6-338479, Japanese Patent Laid-Open No. 98/016950, Japanese Patent Laid-Open No. 2003-100718, Japanese Patent Laid-Open No. 2003-229418, or the like is used. , CF, CF, CF (octafluorocyclopentene), etc.
4 4 8 5 8  4 4 8 5 8
グガスを用いて行うことができる。プラズマエッチング方法としては、ウェハの温度制 御および異方エッチングが可能なリアクティブイオンエッチング (RIE)法力 加工速 度およびウェハへの温度付カ卩が少な 、点で好ま U、。  It can be performed using ggus. As a plasma etching method, the reactive ion etching (RIE) method capable of controlling the temperature of the wafer and anisotropic etching is preferred in terms of the processing speed and the temperature attached to the wafer.
[0107] CMP方式は、素子形成時にも平坦ィ匕のために用いられる方式で、裏面研磨の際 は、汚染イオンを極力排除するためシリコン微粒子を水分散させた単純なスラリーに 切り替えることで、研磨を行うことができる。 [0107] The CMP method is used for flatness even during device formation. When polishing the back surface, it is switched to a simple slurry in which silicon fine particles are dispersed in water in order to eliminate contaminant ions as much as possible. Polishing can be performed.
[0108] 化学エッチング方式は、約 40〜50%の KOH溶液、 HFZ硝酸混合溶液などをェ ツチング液として行われ、 SEZ社製「GL— 210S」の様に装置化されており、これを用 いることがでさる。 [0108] The chemical etching method is carried out using about 40-50% KOH solution, HFZ nitric acid mixed solution, etc. as an etching solution, and it is implemented as an apparatus like “GL-210S” manufactured by SEZ. It is possible to be.
[0109] 所望の厚みに研磨を終えたウェハを半導体チップにして実装するまでの加工処理 は、半導体チップの用途に応じて異なるが、本発明の固定剤付きウェハを使用する と、ウェハを支持ウェハに貼り合わせた状態でカ卩ェ処理できるため、これまで成し得 な力つたプロセスが可能となる。そのようなプロセスの一例を以下に示す。  [0109] The processing up to mounting a wafer that has been polished to a desired thickness as a semiconductor chip differs depending on the application of the semiconductor chip, but when the wafer with a fixing agent of the present invention is used, the wafer is supported. Since it can be processed in a state of being bonded to a wafer, a powerful process that could be achieved so far becomes possible. An example of such a process is shown below.
[0110] (i)研磨面（裏面）にレジストパターンを形成し、これをマスクとしてウェハをエツチン グすることにより、所望の構造体、たとえば、空洞、穴 (貫通孔含む)、突起、溝などを ウェハ裏面に形成する。  [0110] (i) By forming a resist pattern on the polished surface (back surface) and etching the wafer using this as a mask, the desired structure, for example, cavity, hole (including through-hole), protrusion, groove, etc. On the backside of the wafer.
[0111] (ii)研磨面に有機膜層を塗布し、焼成して成膜することにより、研磨面のイオン汚 染防止膜とする。 [0111] (ii) An organic film layer is applied to the polished surface, and baked to form a film. Use a dye-preventing film.
[0112] (iii)所望の硬度および接着力を有する固定剤を選択することにより、ダイシングテ ープに貼り替えることなくウェハをダイシングする。  [0112] (iii) The wafer is diced without being attached to the dicing tape by selecting a fixing agent having desired hardness and adhesive strength.
[0113] (iv)貫通ビアを検査電極に用い、薄肉化後にウェハレベルバーンインテストを行う [0113] (iv) Using a through via as an inspection electrode and performing a wafer level burn-in test after thinning
[0114] (V)先ダイシングによりダイシンダストリートに切削溝を形成したウェハを、上記加工 方法に従って切削溝が露出するまで薄肉化し、小片化された半導体チップを、固定 剤を溶融させると同時にピックアップし、該チップに付着残留した固定剤をアンダー フィル剤またはチップボンディング剤として活用してパッケージ基板に実装する。 [0114] (V) The wafer in which the cutting groove is formed in the die cinder street by the tip dicing is thinned until the cutting groove is exposed according to the above processing method, and the semiconductor chip which has been cut into pieces is picked up simultaneously with melting the fixing agent. Then, the fixing agent adhering and remaining on the chip is utilized as an underfill agent or a chip bonding agent, and mounted on the package substrate.
[0115] 本発明の固定剤付きウェハで加工することが可能なウェハは特に制限されないが 、半導体ウェハであることが好ましい。半導体ウェハとしては、用途や加工方法に応 じた半導体ウェハを用いることができ、大面積のものや、多様で複雑な構造を表面に 有するちのでちょい。  [0115] The wafer that can be processed with the wafer with a fixing agent of the present invention is not particularly limited, but is preferably a semiconductor wafer. As the semiconductor wafer, a semiconductor wafer suitable for the application and processing method can be used, and it is likely to have a large area or a variety of complicated structures on the surface.
[0116] たとえば、上記 (V)のプロセスには、複数のダイシンダストリートによって区画された 領域内に形成された半導体素子を有し、該ダイシンダストリートに、半導体チップの 厚さに相当する切削溝を先ダイシングにより形成した半導体ウェハを用いることがで きる。  [0116] For example, the process (V) includes a semiconductor element formed in a region defined by a plurality of die cinder streets, and the die cinder streets are cut corresponding to the thickness of the semiconductor chip. A semiconductor wafer having grooves formed by tip dicing can be used.
[0117] また、上記プロセス (iv)には、表面に所定の深さの孔が形成され、該孔の内壁が絶 縁膜で被覆され、該絶縁膜で被覆された孔に導電性電極材料が埋め込まれた半導 体ウェハを用いることができる。さらに、上記半導体ウェハは、導通用の突起電極、た とえばノヽンダバンプなどが表面に形成されて 、てもよ 、。  [0117] In the process (iv), a hole having a predetermined depth is formed on the surface, the inner wall of the hole is covered with an insulating film, and the hole covered with the insulating film is formed into a conductive electrode material. A semiconductor wafer in which is embedded can be used. Further, the semiconductor wafer may have a conductive electrode on the surface, for example, a solder bump, etc., formed on the surface.
[0118] 次に、加工したウェハと固定剤付きウェハとを剥離させる。この剥離工程に際しては 、ウェハおよび支持ウェハの少なくとも一方を、使用した固定剤の溶融温度以上に加 熱することにより、該固定剤が溶融され、ウェハを支持ウェハから剥離することができ る。このとき、固定剤で支持ウェハに固定されていた染み込み防止部も取り外すこと ができる。 [0118] Next, the processed wafer and the wafer with the fixing agent are peeled off. In this peeling step, at least one of the wafer and the supporting wafer is heated to a temperature equal to or higher than the melting temperature of the used fixing agent, so that the fixing agent is melted and the wafer can be peeled off from the supporting wafer. At this time, the penetration preventing part fixed to the support wafer with the fixing agent can also be removed.
[0119] 剥離後のウェハの表面（固定剤で固定されていた側の面）に固定剤が残存してい る場合は、固定剤を溶解することができる溶剤で洗浄して除去することができる。この ような溶剤としては、上記本発明の固定剤付きウェハの製造方法において、支持ゥェ ハエッジ部上の固定剤を溶解するために使用した溶剤を使用することが好ましい。 [0119] If the fixing agent remains on the surface of the wafer after peeling (the surface on the side fixed with the fixing agent), it can be removed by washing with a solvent capable of dissolving the fixing agent. . this As such a solvent, it is preferable to use the solvent used for dissolving the fixing agent on the support wafer edge portion in the method for producing a wafer with a fixing agent of the present invention.
[0120] 洗浄方法としては、ウェハを溶剤に浸漬する方法、ウェハに洗浄液をスプレーする 方法などが挙げられる。溶剤の温度は特に限定されないが、好ましくは 20〜80°C、 より好ましくは 30〜50°Cである。  [0120] Examples of the cleaning method include a method of immersing a wafer in a solvent, and a method of spraying a cleaning liquid onto the wafer. The temperature of the solvent is not particularly limited, but is preferably 20 to 80 ° C, more preferably 30 to 50 ° C.
[0121] 剥離後の支持ウェハは上記溶剤等により洗浄し、再利用することが好ましい。再利 用をするに際しては、上記剥離後のウェハ表面に残存する固定剤の洗浄に使用した 溶剤を使用して、上記方法により付着している固定剤を洗浄することが好ましい。そ して、洗浄、乾燥の後、再度、固定剤及び染み込み防止部を配設して、固定剤付き ウェハとして使用することが好まし 、。  [0121] The support wafer after peeling is preferably washed with the above-mentioned solvent and reused. When reusing, it is preferable to wash the fixing agent adhering by the above method using the solvent used for cleaning the fixing agent remaining on the wafer surface after peeling. Then, after cleaning and drying, it is preferable to arrange the fixing agent and the permeation prevention part again and use it as a wafer with the fixing agent.
産業上の利用可能性  Industrial applicability
[0122] 本発明の固定剤付きウェハは、半導体ウェハ等の被加工ウェハの研肖 研磨加工 に利用することができ、支持ウェハと被加工ウェハとの接着固定に使用する固定剤 による、被加工ウェハや作業環境の汚染を防止することが可能となり、更に、支持ゥ エノ、と被カ卩ェウェハとの間に液状物質が染み込むことを防止することが可能となる。 また、本発明の固定剤付きウェハの製造方法は、半導体ウェハ等の被加工ウェハの 研肖 1 研磨加工に使用できる固定剤付きウェハを効率的に製造するために利用する ことができる。 [0122] The wafer with a fixing agent of the present invention can be used for polishing polishing of a wafer to be processed such as a semiconductor wafer, and the workpiece to be processed by the fixing agent used for bonding and fixing the support wafer and the processing wafer. Contamination of the wafer and the working environment can be prevented, and further, it is possible to prevent the liquid material from infiltrating between the supporting wafer and the wafer to be covered. Further, the method for producing a wafer with a fixing agent of the present invention can be used for efficiently producing a wafer with a fixing agent that can be used for polishing 1 polishing of a wafer to be processed such as a semiconductor wafer.

Claims

請求の範囲 The scope of the claims
[1] 支持ウェハと、前記支持ウェハの表面に配設される固定剤とを備える固定剤付きゥ ェハであって、  [1] A wafer with a fixing agent comprising a supporting wafer and a fixing agent disposed on the surface of the supporting wafer,
前記固定剤が前記支持ウェハのエッジ部 (支持ウェハエッジ部）を除 、た部分に配 設され、前記支持ウェハエッジ部に配設される染み込み防止構造を更に備える固定 剤付きウェハ。  A wafer with a fixing agent, wherein the fixing agent is disposed on a portion excluding an edge portion (supporting wafer edge portion) of the support wafer, and further includes a penetration preventing structure disposed on the support wafer edge portion.
[2] 前記固定剤の表面に配設されるカバーフィルムを更に備える請求項 1に記載の固 定剤付きウェハ。  [2] The wafer with a fixing agent according to [1], further comprising a cover film disposed on a surface of the fixing agent.
[3] 前記染み込み防止構造が、リング状の染み込み防止部材により形成されている請 求項 1又は 2に記載の固定剤付きウェハ。  [3] The wafer with a fixing agent according to claim 1 or 2, wherein the penetration preventing structure is formed of a ring-like penetration preventing member.
[4] 固定剤を支持ウェハの表面に塗布して固定剤付きウェハを製造する固定剤付きゥ ェハの製造方法であって、 [4] A method of manufacturing a wafer with a fixing agent by applying a fixing agent to a surface of a support wafer to manufacture a wafer with a fixing agent,
前記支持ウェハのエッジ部（支持ウェハエッジ部）に、染み込み防止構造を配設す る工程を有する固定剤付きウェハの製造方法。  A method for producing a wafer with a fixing agent, comprising a step of disposing a permeation preventing structure on an edge portion (support wafer edge portion) of the support wafer.
[5] 前記固定剤を、液体の状態で、前記支持ウェハの表面に塗布する工程と、 [5] Applying the fixing agent to the surface of the support wafer in a liquid state;
前記固定剤を溶解することができる溶剤で前記支持ウェハエッジ部上の前記固定 剤を溶解除去する工程と、  Dissolving and removing the fixative on the support wafer edge with a solvent capable of dissolving the fixative;
前記支持ウェハエッジ部に、染み込み防止構造を配設する工程とを有する請求項 4に記載の固定剤付きウェハの製造方法。  5. The method for producing a wafer with a fixing agent according to claim 4, further comprising a step of disposing a permeation preventing structure at the edge of the supporting wafer.
[6] 前記支持ウェハエッジ部に、染み込み防止構造を配設した後に、更に、カバーフィ ルムを前記固定剤の表面に貼り付ける工程を有する請求項 5に記載の固定剤付きゥ ェハの製造方法。 6. The method for producing a wafer with a fixing agent according to claim 5, further comprising a step of attaching a cover film to the surface of the fixing agent after disposing an infiltration preventing structure on the supporting wafer edge portion.
[7] 前記支持ウェハエッジ部に、染み込み防止構造を配設する工程と、  [7] A step of disposing an infiltration structure on the support wafer edge portion;
前記固定剤を、前記支持ウェハと前記染み込み防止構造とにより形成される窪み に配置し、前記固定剤を液体状態として、前記支持ウェハの表面に塗布する工程と を有する請求項 4に記載の固定剤付きウェハの製造方法。  The fixing agent according to claim 4, further comprising: disposing the fixing agent in a recess formed by the support wafer and the penetration preventing structure, and applying the fixing agent to a surface of the support wafer in a liquid state. A method for manufacturing a wafer with an agent.
[8] 前記固定剤を液体状態とする前に、カバーフィルムを前記固定剤の表面に配置し[8] Before the fixing agent is in a liquid state, a cover film is placed on the surface of the fixing agent.
、前記カバーフィルムの上から押圧しながら前記固定剤を液体状態とし、前記固定剤 を前記支持ウェハの表面に塗布する請求項 7に記載の固定剤付きウェハの製造方 法。 The fixing agent is in a liquid state while pressing from above the cover film, and the fixing agent The method for producing a wafer with a fixing agent according to claim 7, wherein is applied to the surface of the support wafer.
[9] 前記固定剤を、前記支持ウェハの表面に塗布する工程が、  [9] The step of applying the fixing agent to the surface of the support wafer,
前記固定剤を前記支持ウェハの表面に乗せ、前記固定剤を、加熱溶融した状態で The fixing agent is placed on the surface of the support wafer, and the fixing agent is heated and melted.
、前記支持ウェハの表面に塗布する工程である請求項 4〜8のいずれかに記載の固 定剤付きウェハの製造方法。 The method for producing a wafer with a fixing agent according to any one of claims 4 to 8, which is a step of applying to the surface of the support wafer.
[10] 前記支持ウェハエッジ部に染み込み防止構造を配設する工程が、前記支持ウェハ エッジ部に、リング状の染み込み防止部材を配設する工程である請求項 4〜9の 、ず れかに記載の固定剤付きウェハの製造方法。 [10] The method according to any one of claims 4 to 9, wherein the step of disposing a permeation prevention structure at the support wafer edge portion is a step of disposing a ring-shaped permeation prevention member at the support wafer edge portion. Manufacturing method of wafer with fixing agent.
PCT/JP2006/309483 2005-05-30 2006-05-11 Wafer with fixing agent and method for producing wafer with fixing agent WO2006129458A1 (en)

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