WO2008082128A1 - Norbornene-based silsesquioxane copolymers, norbornene-based silane derivative used for preparation of the same and method of preparing low dielectric insulating film comprising the same - Google Patents

Norbornene-based silsesquioxane copolymers, norbornene-based silane derivative used for preparation of the same and method of preparing low dielectric insulating film comprising the same Download PDF

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WO2008082128A1
WO2008082128A1 PCT/KR2007/006794 KR2007006794W WO2008082128A1 WO 2008082128 A1 WO2008082128 A1 WO 2008082128A1 KR 2007006794 W KR2007006794 W KR 2007006794W WO 2008082128 A1 WO2008082128 A1 WO 2008082128A1
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norbornene
solvent
insulating film
chemical
polysilsesquioxane
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PCT/KR2007/006794
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French (fr)
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Joo-Hyeon Park
Bu-Geun Ryu
Jin-Youp Kim
Soo-Suk Song
Jae-Ho Choi
Seung-Hun Lee
Jin-A Kim
Jung-Sik Choi
Doe Kim
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Samyang Corporation
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/02137—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material comprising alkyl silsesquioxane, e.g. MSQ
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to norbornene-based polysilsesquioxane copolymers, norbornene-based silane derivatives used for preparation of the same and a method of preparing an insulating film of a semiconductor device comprising the same, in particular, to norbornene-based polysilsesquioxane copolymers used effectively as a material for an insulating film of a semiconductor device and norbornene-based silane derivatives used for preparation of the same.
  • SiO silicon oxide film
  • a low hygroscopic rate a low hygroscopic rate
  • thermal stability e.g.
  • 3,615,272 discloses a method for preparing completely condensed hydrogensilsesquioxane, in which trichlorosilane, trimethoxysilane or triacetoxysilane is condensed in a medium of a solvent mixture consisted of a sulfuric acid, a fuming sulfuric acid and a hydrocarbon and is washed by a mixture of a sulfuric acid and water.
  • trichlorosilane, trimethoxysilane or triacetoxysilane is condensed in a medium of a solvent mixture consisted of a sulfuric acid, a fuming sulfuric acid and a hydrocarbon and is washed by a mixture of a sulfuric acid and water.
  • 5,010,159 discloses a method for preparing hydrogensilsesquioxane, in which hydri- dosilanes are hydrolyzed in a medium containing an arylsulfonic acid hydrate produced by mixing an aromatic solvent with a sulfuric acid thereby to form silsesquioxane and the silsesquioxane is contacted with a neutralizing agent.
  • U.S. Patent Nos. 3,615,272, 4,399,266, 4,756,977 and 4,999,397 disclose a polyalkylsilsesquioxane insulating film having a dielectric constant of about 2.5 to about 3.1, prepared by a spin coating method.
  • an insulating film may be made of a polymer prepared using tetraalkoxysilane having a low organic carbon content and a Q structure, but the insulating film has a high hygroscopic rate, thereby increasing a dielectric constant, and thus the polymer has limitations in use as a material for an insulating film.
  • an organic nanopore forming material such as hyperbranched polyester [C. Nguyen, C. J. Hawker, R. D. Miller and J. L. Hedrick, Macromoleucles, 33, 4281 (2000)] or ethylene-propylene-ethylene tri-block copolymer (pluonicsTM) [S. Yang, P. A. Mirau, E.K. Lin, HJ. Lee and D.W. Gidley, Chem.
  • Mater., 13, 2762 (2001)] is mixed with polysilsesquioxane to form an organic-inorganic nanohybrid thin film and the organic- inorganic nanohybrid thin film is heated to high temperature, thereby obtaining a nonaporous thin film.
  • a norbornene-based silane monomer is addition-polymerized to form a polynorbornene polymer and the polynorbornene polymer is mixed with a polymethylsilsesquioxane polymer [A.M. Padovani, L.R. Riester, L. Rhodes, S. A. Bidstrup and P.A. Kohl, J. Electrochem. Soc, 149, F171, (2002)].
  • the nanopore forming material may conglomerate due to a phase separation between the nanopore forming material and polysilsesquioxane, and consequently a pore size is increased, thereby reducing the mechanical strength of the insulating film. Disclosure of Invention Technical Problem
  • the present invention provides a norbornene-based silane derivative represented by any of the following Chemical Figures 1 to 6:
  • L , L and L are linkers for linking Si atom with norbornene, each is independently selected from the group consisting of an alkyl group of C ⁇ C and structures represented by any of the following Chemical Figures 7 to 10, and A , A and A each is independently a functional group selected from the group consisting of a hydroxy group, a methoxy group, an ethoxy group, a propoxy group and a chloride group;
  • the present invention also provides norbornene-based polysilsesquioxane copolymers prepared by hydrolyzing and condensation-polymerizing at least one kind of monomer selected from the norbornene-based silane derivatives represented by the above Chemical Figures 1 to 6, and at least one kind of monomer selected from polysilsesquioxane precursors represented by the following Chemical Figures 11 and 12 in an organic solvent in the presence of an acid or base catalyst and water:
  • R is hydrogen, methyl or an ethyl group
  • x is an integer of 0 to 4
  • R a is an alkyl group of C 1 ⁇ C6
  • B is an alkoxy group of C 1 ⁇ C3 or an chloride group.
  • the present invention provides a method of preparing an insulating film comprising: preparing norbornene-based polysilsesquioxane copolymers by hydrolyzing and condensation-polymerizing at least one kind of monomer selected from the norbornene-based silane derivatives represented by the above Chemical Figures 1 to 6, and at least one kind of monomer selected from the polysilsesquioxane precursors represented by the above Chemical Figures 11 and 12 in an organic solvent in the presence of an acid or base catalyst and water; preparing a coating solution by dissolving the norbornene-based polysilsesquioxane copolymers in an organic solvent; and applying the coating solution on a silicon wafer to form a thin film and curing the thin film.
  • FIG. 1 is a reaction formula for preparing a polysilsesquioxane copolymer
  • copolymer 4 of an example 2 from a norbornene-based silane derivative according to an example (example 1-3) of the present invention and methyltrimethoxysilane.
  • FIG. 2 is a graph showing Si-NMR spectrum of a copolymer 4 of an example 2 of the present invention.
  • FIG. 3 is a TGA (thermogravimetric analysis) graph of a copolymer 13 of the example 2 of the present invention.
  • Polysilsesquioxane copolymers have excellent properties including an excellent heat resistance and a low hygroscopic rate, and thus have a good reputation as a material for an interlayer insulating film of a semiconductor device, however their low dielectric characteristic falls short of the required extent, and therefore, to use the polysilsesquioxane copolymers as a material for an insulating film, it is required to reinforce their low dielectric characteristic.
  • the inventors of the present invention polymerized a kind of cyclic olefin, i.e. modified norbornene-based silane derivatives with polysilsesquioxane precursors to develop norbornene-based polysilsesquioxane copolymers with inherently excellent properties and improved low dielectric characteristic.
  • a copolymer of a norbornene-based silane derivative and a polysilsesquioxane precursor of the present invention provides a low dielectric constant due to norbornene of a ring structure serving as a molecular cage. And, because norbornene has ring strain, norbornene is susceptible to decomposition by stimulation of an external energy such as heat of 45O 0 C or more or ultraviolet (UV) ray, and thus the present invention forms a nanopore in an insulating film comprising the norbornene-based polysilsesquioxane copolymers, thereby providing improved low dielectric characteristic.
  • an external energy such as heat of 45O 0 C or more or ultraviolet (UV) ray
  • the norbornene-based polysilsesquioxane copolymers of the present invention are prepared by hydrolyzing and condensation-polymerizing at least one kind of monomer selected from the norbornene-based silane derivatives represented by the above Chemical Figures 1 to 6 and at least one kind of monomer selected from the polysilsesquioxane precursors represented by the above Chemical Figures 11 and 12 in an organic solvent in the presence of an acid or base catalyst and water.
  • a mixing molar ratio of a monomer selected from the norbornene-based silane derivatives to a monomer selected from the polysilsesquioxane precursors is preferably 1:99 to 99:1, more preferably 20:80 to 90:10.
  • compounds represented by the above Chemical Figure 11 may be methyltrimethoxysilane (MTMS), triethoxysilane (TES), bistrimethoxysilylethane (BTMSE), trichlorosilane (TCS), trimethoxysilane (TMS), methyltriethoxysilane (MTES), ethyltrichlorosilane (ETCS), ethyltrimethoxysilane (ETMS), ethyltri- ethoxysilane (ETES), propyltrichlorosilane (PTCS), propyltriethoxysilane (PTES), hexyltrichlorosilane (HTCS), hexyltrimethoxysilane (HTMS), hexyltriethoxysilane (HTES), octyltrichlorosilane (OTCS), octyltrimethoxysilane (OTMS) or octtyltrich
  • compounds represented by the above Chemical Figure 12 may be bistrimethoxysilylmethane (BTMSM), bistrimethoxysilylpropane (BTMSP), bistrimethoxysilylhexane (PTMSH), hexamethoxydisiloxane (HMDS), hexachloro- disiloxane (HCDS) or hexsaethoxydisiloxane (HEDS).
  • BTMSM bistrimethoxysilylmethane
  • BTMSP bistrimethoxysilylpropane
  • PTMSH bistrimethoxysilylhexane
  • HMDS hexamethoxydisiloxane
  • HCDS hexachloro- disiloxane
  • HEDS hexsaethoxydisiloxane
  • the acid or base catalyst used in preparing the norbornene-based polysilsesquioxane copolymers may be hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, benzene sulfonic acid, p-toluene sulfonic acid, formic acid, oxalic acid, potassium hydroxide, sodium hydroxide, triethylamine, sodium bicarbonate or pyridine.
  • the catalyst may be used with its molar ratio to the monomers of 1:0.000001 to 1:10.
  • the water added in the hydrolysis and condensation-polymerization reactions may be used with its molar ratio to the monomers of 1:0 to 1:1,000.
  • the organic solvent used in preparing the norbornene-based polysilsesquioxane copolymers may be at least one solvent selected from the group consisting of an aliphatic hydrocarbon solvent such as hexane or heptane; an aromatic hydrocarbon solvent such as anisol, mesitylene or xylene; a ketone-based solvent such as methyl isobutyl ketone, l-methyl-2-pyrrolidinone, cyclohexanone or acetone; an ether-based solvent such as tetrahydrofuran or isopropyl ether; an acetate-based solvent such as ethyl acetate, butyl acetate or propylene glycol methyl ether acetate; an alcohol-based solvent such as isopropyl alcohol or butyl alcohol; an amide-based solvent such as dimethylacetamide or dimethylformamide; and a silicon-based solvent, or mixtures thereof.
  • an aliphatic hydrocarbon solvent such as
  • temperature is adjusted to 0 to 200 0 C, preferably 50 to 11O 0 C and a reaction time is adjusted to 0.1 to 100 hours, preferably 5 to 48 hours.
  • the above-mentioned norbornene-based polysilsesquioxane copolymers have a weight average molecular weight of 500 to 300,000, and Si-OR content is 5% or more in the total terminals of the prepared copolymers.
  • the above-mentioned norbornene-based polysilsesquioxane copolymers of the present invention have an excellent mechanical properties and a low dielectric characteristic, and thus can be effectively used as a material for an insulating film of a semiconductor device.
  • a method of preparing an insulating film comprising the norbornene-based polysilsesquioxane copolymers of the present invention is described.
  • the detailed description and specific examples, while indicating preferred embodiments of the invention are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
  • the insulating film comprising the norbornene-based polysilsesquioxane copolymers may be formed by dissolving the norbornene-based polysilsesquioxane copolymers in an organic solvent to prepare a coating solution, applying the coating solution on a silicon wafer and thermally curing the coating solution.
  • the organic solvent used in preparing the coating solution may be at least one solvent selected from the group consisting of an aliphatic hydrocarbon solvent such as hexane or heptane; an aromatic hydrocarbon solvent such as anisol, mesitylene or xylene; a ketone-based solvent such as methyl isobutyl ketone, l-methyl-2-pyrrolidinone, cyclohexanone or acetone; an ether-based solvent such as tetrahydrofuran or isopropyl ether; an acetate-based solvent such as ethyl acetate, butyl acetate or propylene glycol methyl ether acetate; an alcohol-based solvent such as isopropyl alcohol or butyl alcohol; an amide-based solvent such as dimethylacetamide or dimethylformamide; and a silicon-based solvent, or mixtures thereof.
  • an aliphatic hydrocarbon solvent such as hexane or heptane
  • an aromatic hydrocarbon solvent
  • the solvent should be contained with a sufficient amount to the concentration required to apply the norbornene-based polysilsesquioxane copolymers on a substrate, and preferably the content of the solvent in the coating composition is 20 to 99.9 weight%, more preferably 70 to 95 weight%. In the case that the content of the solvent is less than 20 weight%, it is not preferable because the copolymers may not be completely dissolved in the solvent, and in the case that the content of the solvent is more than 99.9 weight%, it is not preferable because the insulating film may be formed as thin as 1000 A or less.
  • the solids content of the coating solution is adjusted to 5 to 80 weight% based on the total weight of the coating solution.
  • a method for coating the coating solution on the silicon wafer is not limited to a specific method, however typically the prepared copolymer solution is directly dropped onto a pre- surface treated silicon wafer while being filtered by a filter (for example: 0.2D filter) and a desired thickness of insulating film may be prepared by changing the rotation number (rpm) of a spin coater for a predetermined time.
  • the rotation number of the spin coater is preferably 500 to 10,000 rpm, more preferably 1,000 to 5,000 rpm.
  • the rotation time of the spin coater is preferably 10 to 150 seconds, more preferably 20 to 50 seconds.
  • the coating solution is thermally cured, and thermal curing is performed at temperature of 150 to 300 0 C for 1 to 150 minutes, preferably at temperature of 200 to 300 0 C.
  • the thin film free of cracks means a thin film having no crack visible with naked eyes when observed by an optical microscope of 1000 magnifications
  • the insoluble thin film means a thin film insoluble essentially to a film-forming solvent or a solvent useful in applying a resin after coating and curing the norbornene -based polysilsesquioxane copolymers.
  • the curing process is performed under a nitrogen atmosphere, however the present invention is not limited in this regard.
  • the insulating film prepared by the above-mentioned method exhibits a low dielectric constant because norbornene molecules of a ring structure serve as a molecular cage.
  • An insulating film having a nanopore may be prepared from the insulating film prepared by the above-mentioned process through a thermal decomposition of norbornene molecules by heating or a decomposition of norbornene molecules by UV irradiation, and the insulating film having a nanopore has a still lower dielectric constant.
  • the nanopore formed by decomposition of norbornene molecules may have 1 to 10 D size.
  • the heating temperature is preferably 250 to 600 0 C, more preferably 300 to 55O 0 C, and most preferably 350 to 45O 0 C.
  • the heating time is preferably at least 30 minutes to 10 hours, more preferably 2 to 5 hours.
  • the heating process is performed under a nitrogen atmosphere, however the present invention is not limited in this regard.
  • the nanopore forming process by ultraviolet ray irradiation may be performed by after thermal curing of the insulating film, irradiating ultraviolet ray on the insulating film using a ultraviolet lamp having multi-wavelength of 250 D to 450 D at room temperature to 300 0 C for 1 minute to 3 hours, and through this process, the norbornene molecules are decomposed to form a nanopore.
  • the thermal curing process followed by the ultraviolet ray irradiation process is performed at temperature of 150 to 300 0 C for 1 to 15 minutes.
  • the thermal curing process may be omitted. That is, the polysilsesquioxane copolymer coating solution is coated on the silicon wafer to form a thin film, and ultraviolet ray irradiation is performed on the thin film without a thermal curing process to form a nanopore while curing the thin film, thereby preparing an insulating film. And, in the case that the nanopore forming process is performed by ultraviolet ray irradiation, ultraviolet irradiation is first performed and then thermal curing is performed later, thereby preparing an insulating film.
  • the polysilsesquioxane copolymer coating solution is coated on the silicon wafer to form a thin film, ultraviolet ray irradiation is performed on the thin film and then thermal curing is performed on the thin film to prepare an insulating film.
  • the insulating films prepared by the above-mentioned methods have a low dielectric constant, and thus can be effectively used to a semiconductor device.
  • Example 1-21 Synthesis of derivative (U) [178] Derivative (U) [179] [180] 97 h 0 D of THF, 1.536 mol (190.74 g) of norbomenemethanol, 0.015 mol (4.95 g) of tetrabutylammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 75 0 C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 75 0 C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
  • TBAB tetrabutylammoniumbromide
  • Example 2 Synthesis of polvsilsesquioxane copolymers
  • At least one kind of monomer selected from the norbornene-based silane derivatives prepared according to the above-mentioned examples 1-1 to 1-27 and at least one kind of monomer selected from polysilsesquioxane precursors, i.e. methyltrimethoxysilane (MTMS), triethoxysilane (TES) and bistrimethoxysilylethane (BTMSE) were put into a flask, tetrahydrofuran was added 15 times as much as the total amount of the added monomers to dilute the monomers and the internal temperature of the flask was decreased to 1O 0 C.
  • MTMS methyltrimethoxysilane
  • TES triethoxysilane
  • BTMSE bistrimethoxysilylethane
  • Heating up to 45O 0 C or ultraviolet ray irradiation at room temperature was performed to cure the copolymer thin film, an aluminum electrode was vacuum-deposited on the thin film, and an electrical characteristic of the thin film was measured.
  • the aluminum electrode deposition was made on conditions of diameter of 5 D, pressure of id torr or less, and evaporation speed of 0.5 nm/sec or less thereby to obtain an electrode having uniform thickness of 100 D or so.
  • the norbornene-based silane derivatives of the present invention have high reactivity and the norbornene-based polysilsesquioxane copolymers of the present invention, prepared using the same, have excellent mechanical properties, thermal stability and crack resistance and a low dielectric constant, and thus can be effectively used as a material for a semiconductor interlayer insulating film with a low dielectric constant.

Abstract

The present invention relates to norbornene-based polysilsesquioxane copolymers, norbornene-based silane derivatives used for preparation of the same and a method of preparing an insulating film of a semiconductor device. The norbornene-based polysilsesquioxane copolymers of the present invention are prepared by hydrolyzing and condensation-polymerizing a kind of cyclic olefin, i.e. a predetermined norbornene-based silane derivative and a predetermined polysilsesquioxane precursor used as monomers in an organic solvent in the presence of an acid or base catalyst and water. The norbornene-based silane derivatives of the present invention have high reactivity and the norbornene-based polysilsesquioxane copolymers of the present invention prepared using the same, have excellent mechanical properties, thermal stability and crack resistance and a low dielectric constant, and thus can be effectively used as a material for an interlayer insulating film of a semiconductor device with a low dielectric constant.

Description

Description
NORBONENE-BASED SILSESQUIOXANE COPOLYMERS,
NORBORNENE-BASED SILANE DERIVATIVE USED FOR
PREPARATION OF THE SAME AND METHOD OF
PREPARING LOW DIELECTRIC INSULATING FILM
COMPRISING THE SAME
Technical Field
[1] The present invention relates to norbornene-based polysilsesquioxane copolymers, norbornene-based silane derivatives used for preparation of the same and a method of preparing an insulating film of a semiconductor device comprising the same, in particular, to norbornene-based polysilsesquioxane copolymers used effectively as a material for an insulating film of a semiconductor device and norbornene-based silane derivatives used for preparation of the same. Background Art
[2] In a recent semiconductor industry, as density of a semiconductor device increases, a signal delay problem becomes severer that is caused by increase in RC delay indicated as resistance of a wiring material and a charge capacity of an insulating film. In order to solve the problem, attempts have been taken to reduce resistance of metal wirings by using copper with better conductivity as a metal wiring material instead of aluminum, and at the same time, to develop an insulating film having a low dielectric constant for reinforcing an insulating property between the metal wirings. Conventionally, in particular, a silicon oxide film (SiO ) having a dielectric constant of about 4.0 has been mainly used as an insulating film, however it is now essential to use an insulating film having a low dielectric constant because of increase in wiring density and consequently a signal delay problem.
[3] Polysilsesquioxane is a typical material having a low dielectric constant, and among the polysilsesquioxane, polyhydrogensilsesquioxane (R=hydrogen group) and polymethyl/ethylsilsesquioxane(R=methyl group/ethyl group) having a molecular formula of (RSiO3/2)n have properties including a low dielectric constant (k=2.7~3.0), a low hygroscopic rate and a high thermal stability, and thus they are noticed as next- generation dielectric materials. Specifically, U.S. Patent No. 3,615,272 discloses a method for preparing completely condensed hydrogensilsesquioxane, in which trichlorosilane, trimethoxysilane or triacetoxysilane is condensed in a medium of a solvent mixture consisted of a sulfuric acid, a fuming sulfuric acid and a hydrocarbon and is washed by a mixture of a sulfuric acid and water. And, U.S. Patent No. 5,010,159 discloses a method for preparing hydrogensilsesquioxane, in which hydri- dosilanes are hydrolyzed in a medium containing an arylsulfonic acid hydrate produced by mixing an aromatic solvent with a sulfuric acid thereby to form silsesquioxane and the silsesquioxane is contacted with a neutralizing agent. Meanwhile, U.S. Patent Nos. 3,615,272, 4,399,266, 4,756,977 and 4,999,397 disclose a polyalkylsilsesquioxane insulating film having a dielectric constant of about 2.5 to about 3.1, prepared by a spin coating method.
[4] However, insulating films prepared using polysilsesquioxane according to the above-mentioned patents do not provide a sufficiently low dielectric constant or have a relatively low mechanical property (elastic modulus; 3-4 GPa), and thus disadvan- tageously have less applicability to semiconductor processing. In order to solve the disadvantages, an insulating film may be made of a polymer prepared using tetraalkoxysilane having a low organic carbon content and a Q structure, but the insulating film has a high hygroscopic rate, thereby increasing a dielectric constant, and thus the polymer has limitations in use as a material for an insulating film.
[5] Meanwhile, with development of the above-mentioned materials, studies have been made to develop an ultralow dielectric substance having a lower dielectric constant, ultimately a dielectric constant of 2.0 or less by uniformly generating a nanopore having lowest dielectric constant (dielectric constant=l) in a dielectric material.
[6] As a typical example of the currently developed ultralow dielectric substance, an organic nanopore forming material such as hyperbranched polyester [C. Nguyen, C. J. Hawker, R. D. Miller and J. L. Hedrick, Macromoleucles, 33, 4281 (2000)] or ethylene-propylene-ethylene tri-block copolymer (pluonics™) [S. Yang, P. A. Mirau, E.K. Lin, HJ. Lee and D.W. Gidley, Chem. Mater., 13, 2762 (2001)] is mixed with polysilsesquioxane to form an organic-inorganic nanohybrid thin film and the organic- inorganic nanohybrid thin film is heated to high temperature, thereby obtaining a nonaporous thin film. And, there is a study of forming a nanopore in which a norbornene-based silane monomer is addition-polymerized to form a polynorbornene polymer and the polynorbornene polymer is mixed with a polymethylsilsesquioxane polymer [A.M. Padovani, L.R. Riester, L. Rhodes, S. A. Bidstrup and P.A. Kohl, J. Electrochem. Soc, 149, F171, (2002)].
[7] However, in preparing an insulating film by the above-mentioned methods in the case that the content of the nanopore forming material is 20 to 30%, the nanopore forming material may conglomerate due to a phase separation between the nanopore forming material and polysilsesquioxane, and consequently a pore size is increased, thereby reducing the mechanical strength of the insulating film. Disclosure of Invention Technical Problem
[8] It is an object of the present invention to provide norbornene-based polysilsesquioxane copolymers having excellent heat resistance and low dielectric characteristic as a material for an insulating film of a semiconductor device.
[9] And, it is another object of the present invention to provide norbornene-based silane derivatives used effectively in preparing the norbornene-based polysilsesquioxane copolymers having the above-mentioned properties.
[10] Also, it is still another object of the present invention to provide an insulating film of a semiconductor device comprising the norbornene-based polysilsesquioxane copolymers.
[H] Further, it is yet another object of the present invention to provide a method of preparing an insulating film of a semiconductor device having excellent mechanical properties, thermal stability and crack resistance and a method for preparing an insulating film having a nanopore. Technical Solution
[12] In order to achieve the above-mentioned objects, the present invention provides a norbornene-based silane derivative represented by any of the following Chemical Figures 1 to 6:
[13] ChemistryFigure 1
Figure imgf000004_0001
[14] ChemistryFigure 2
Figure imgf000004_0002
[15] ChemistryFigure 3
Figure imgf000005_0001
3
[16] ChemistryFigure 4
(A2
Figure imgf000005_0002
[17] ChemistryFigure 5
(A3
Figure imgf000005_0003
[18] ChemistryFigure 6
Figure imgf000005_0004
3
[19] wherein L , L and L are linkers for linking Si atom with norbornene, each is independently selected from the group consisting of an alkyl group of C ~C and structures represented by any of the following Chemical Figures 7 to 10, and A , A and A each is independently a functional group selected from the group consisting of a hydroxy group, a methoxy group, an ethoxy group, a propoxy group and a chloride group;
[20] ChemistryFigure 7
Figure imgf000006_0001
[21] ChemistryFigure 8
Figure imgf000006_0002
[22] ChemistryFigure 9
Figure imgf000006_0003
[23] ChemistryFigure 10
Figure imgf000006_0004
[24] wherein y is an integer of 0 to 2, z is an integer of 0 to 3, and q is an integer of 0 to
2.
[25] The present invention also provides norbornene-based polysilsesquioxane copolymers prepared by hydrolyzing and condensation-polymerizing at least one kind of monomer selected from the norbornene-based silane derivatives represented by the above Chemical Figures 1 to 6, and at least one kind of monomer selected from polysilsesquioxane precursors represented by the following Chemical Figures 11 and 12 in an organic solvent in the presence of an acid or base catalyst and water:
[26] ChemistryFigure 11
Figure imgf000006_0005
[27] ChemistryFigure 12
(B)SiR3Si (B)3
[28] wherein R is hydrogen, methyl or an ethyl group, x is an integer of 0 to 4, R a is an alkyl group of C 1 ~C6 , and B is an alkoxy group of C 1 ~C3 or an chloride group.
[29] In order to achieve the above-mentioned objects, the present invention provides a method of preparing an insulating film comprising: preparing norbornene-based polysilsesquioxane copolymers by hydrolyzing and condensation-polymerizing at least one kind of monomer selected from the norbornene-based silane derivatives represented by the above Chemical Figures 1 to 6, and at least one kind of monomer selected from the polysilsesquioxane precursors represented by the above Chemical Figures 11 and 12 in an organic solvent in the presence of an acid or base catalyst and water; preparing a coating solution by dissolving the norbornene-based polysilsesquioxane copolymers in an organic solvent; and applying the coating solution on a silicon wafer to form a thin film and curing the thin film. Brief Description of the Drawings
[30] FIG. 1 is a reaction formula for preparing a polysilsesquioxane copolymer
(copolymer 4 of an example 2) from a norbornene-based silane derivative according to an example (example 1-3) of the present invention and methyltrimethoxysilane.
[31] FIG. 2 is a graph showing Si-NMR spectrum of a copolymer 4 of an example 2 of the present invention.
[32] FIG. 3 is a TGA (thermogravimetric analysis) graph of a copolymer 13 of the example 2 of the present invention. Mode for the Invention
[33] Hereinafter, the present invention is described in detail.
[34] Polysilsesquioxane copolymers have excellent properties including an excellent heat resistance and a low hygroscopic rate, and thus have a good reputation as a material for an interlayer insulating film of a semiconductor device, however their low dielectric characteristic falls short of the required extent, and therefore, to use the polysilsesquioxane copolymers as a material for an insulating film, it is required to reinforce their low dielectric characteristic.
[35] The inventors of the present invention polymerized a kind of cyclic olefin, i.e. modified norbornene-based silane derivatives with polysilsesquioxane precursors to develop norbornene-based polysilsesquioxane copolymers with inherently excellent properties and improved low dielectric characteristic.
[36] A copolymer of a norbornene-based silane derivative and a polysilsesquioxane precursor of the present invention provides a low dielectric constant due to norbornene of a ring structure serving as a molecular cage. And, because norbornene has ring strain, norbornene is susceptible to decomposition by stimulation of an external energy such as heat of 45O0C or more or ultraviolet (UV) ray, and thus the present invention forms a nanopore in an insulating film comprising the norbornene-based polysilsesquioxane copolymers, thereby providing improved low dielectric characteristic. [37] The norbornene-based polysilsesquioxane copolymers of the present invention are prepared by hydrolyzing and condensation-polymerizing at least one kind of monomer selected from the norbornene-based silane derivatives represented by the above Chemical Figures 1 to 6 and at least one kind of monomer selected from the polysilsesquioxane precursors represented by the above Chemical Figures 11 and 12 in an organic solvent in the presence of an acid or base catalyst and water.
[38] In preparing the norbornene-based polysilsesquioxane copolymers, in which norbornenes are chemically joined, a mixing molar ratio of a monomer selected from the norbornene-based silane derivatives to a monomer selected from the polysilsesquioxane precursors is preferably 1:99 to 99:1, more preferably 20:80 to 90:10.
[39] For example, compounds represented by the above Chemical Figure 11 may be methyltrimethoxysilane (MTMS), triethoxysilane (TES), bistrimethoxysilylethane (BTMSE), trichlorosilane (TCS), trimethoxysilane (TMS), methyltriethoxysilane (MTES), ethyltrichlorosilane (ETCS), ethyltrimethoxysilane (ETMS), ethyltri- ethoxysilane (ETES), propyltrichlorosilane (PTCS), propyltriethoxysilane (PTES), hexyltrichlorosilane (HTCS), hexyltrimethoxysilane (HTMS), hexyltriethoxysilane (HTES), octyltrichlorosilane (OTCS), octyltrimethoxysilane (OTMS) or octyltrieth oxysilane (OTES).
[40] For example, compounds represented by the above Chemical Figure 12 may be bistrimethoxysilylmethane (BTMSM), bistrimethoxysilylpropane (BTMSP), bistrimethoxysilylhexane (PTMSH), hexamethoxydisiloxane (HMDS), hexachloro- disiloxane (HCDS) or hexsaethoxydisiloxane (HEDS).
[41] The acid or base catalyst used in preparing the norbornene-based polysilsesquioxane copolymers may be hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, benzene sulfonic acid, p-toluene sulfonic acid, formic acid, oxalic acid, potassium hydroxide, sodium hydroxide, triethylamine, sodium bicarbonate or pyridine. Preferably, the catalyst may be used with its molar ratio to the monomers of 1:0.000001 to 1:10.
[42] Preferably, the water added in the hydrolysis and condensation-polymerization reactions may be used with its molar ratio to the monomers of 1:0 to 1:1,000.
[43] The organic solvent used in preparing the norbornene-based polysilsesquioxane copolymers may be at least one solvent selected from the group consisting of an aliphatic hydrocarbon solvent such as hexane or heptane; an aromatic hydrocarbon solvent such as anisol, mesitylene or xylene; a ketone-based solvent such as methyl isobutyl ketone, l-methyl-2-pyrrolidinone, cyclohexanone or acetone; an ether-based solvent such as tetrahydrofuran or isopropyl ether; an acetate-based solvent such as ethyl acetate, butyl acetate or propylene glycol methyl ether acetate; an alcohol-based solvent such as isopropyl alcohol or butyl alcohol; an amide-based solvent such as dimethylacetamide or dimethylformamide; and a silicon-based solvent, or mixtures thereof.
[44] In the condensation-polymerization reaction, temperature is adjusted to 0 to 2000C, preferably 50 to 11O0C and a reaction time is adjusted to 0.1 to 100 hours, preferably 5 to 48 hours.
[45] Preferably, the above-mentioned norbornene-based polysilsesquioxane copolymers have a weight average molecular weight of 500 to 300,000, and Si-OR content is 5% or more in the total terminals of the prepared copolymers.
[46] The above-mentioned norbornene-based polysilsesquioxane copolymers of the present invention have an excellent mechanical properties and a low dielectric characteristic, and thus can be effectively used as a material for an insulating film of a semiconductor device. Hereinafter, a method of preparing an insulating film comprising the norbornene-based polysilsesquioxane copolymers of the present invention is described. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
[47] The insulating film comprising the norbornene-based polysilsesquioxane copolymers may be formed by dissolving the norbornene-based polysilsesquioxane copolymers in an organic solvent to prepare a coating solution, applying the coating solution on a silicon wafer and thermally curing the coating solution.
[48] The organic solvent used in preparing the coating solution may be at least one solvent selected from the group consisting of an aliphatic hydrocarbon solvent such as hexane or heptane; an aromatic hydrocarbon solvent such as anisol, mesitylene or xylene; a ketone-based solvent such as methyl isobutyl ketone, l-methyl-2-pyrrolidinone, cyclohexanone or acetone; an ether-based solvent such as tetrahydrofuran or isopropyl ether; an acetate-based solvent such as ethyl acetate, butyl acetate or propylene glycol methyl ether acetate; an alcohol-based solvent such as isopropyl alcohol or butyl alcohol; an amide-based solvent such as dimethylacetamide or dimethylformamide; and a silicon-based solvent, or mixtures thereof.
[49] The solvent should be contained with a sufficient amount to the concentration required to apply the norbornene-based polysilsesquioxane copolymers on a substrate, and preferably the content of the solvent in the coating composition is 20 to 99.9 weight%, more preferably 70 to 95 weight%. In the case that the content of the solvent is less than 20 weight%, it is not preferable because the copolymers may not be completely dissolved in the solvent, and in the case that the content of the solvent is more than 99.9 weight%, it is not preferable because the insulating film may be formed as thin as 1000 A or less.
[50] Preferably, the solids content of the coating solution is adjusted to 5 to 80 weight% based on the total weight of the coating solution.
[51] A method for coating the coating solution on the silicon wafer is not limited to a specific method, however typically the prepared copolymer solution is directly dropped onto a pre- surface treated silicon wafer while being filtered by a filter (for example: 0.2D filter) and a desired thickness of insulating film may be prepared by changing the rotation number (rpm) of a spin coater for a predetermined time. The rotation number of the spin coater is preferably 500 to 10,000 rpm, more preferably 1,000 to 5,000 rpm. And, the rotation time of the spin coater is preferably 10 to 150 seconds, more preferably 20 to 50 seconds.
[52] After the coating solution is applied on the silicon wafer, the coating solution is thermally cured, and thermal curing is performed at temperature of 150 to 3000C for 1 to 150 minutes, preferably at temperature of 200 to 3000C. As a result, an insoluble thin film free of cracks can be formed. The thin film free of cracks means a thin film having no crack visible with naked eyes when observed by an optical microscope of 1000 magnifications, and the insoluble thin film means a thin film insoluble essentially to a film-forming solvent or a solvent useful in applying a resin after coating and curing the norbornene -based polysilsesquioxane copolymers. Preferably, the curing process is performed under a nitrogen atmosphere, however the present invention is not limited in this regard.
[53] The insulating film prepared by the above-mentioned method exhibits a low dielectric constant because norbornene molecules of a ring structure serve as a molecular cage.
[54] An insulating film having a nanopore may be prepared from the insulating film prepared by the above-mentioned process through a thermal decomposition of norbornene molecules by heating or a decomposition of norbornene molecules by UV irradiation, and the insulating film having a nanopore has a still lower dielectric constant. The nanopore formed by decomposition of norbornene molecules may have 1 to 10 D size.
[55] In the nanopore forming process by thermal decomposition, the heating temperature is preferably 250 to 6000C, more preferably 300 to 55O0C, and most preferably 350 to 45O0C. The heating time is preferably at least 30 minutes to 10 hours, more preferably 2 to 5 hours. Preferably, the heating process is performed under a nitrogen atmosphere, however the present invention is not limited in this regard.
[56] The nanopore forming process by ultraviolet ray irradiation may be performed by after thermal curing of the insulating film, irradiating ultraviolet ray on the insulating film using a ultraviolet lamp having multi-wavelength of 250 D to 450 D at room temperature to 3000C for 1 minute to 3 hours, and through this process, the norbornene molecules are decomposed to form a nanopore. Preferably, the thermal curing process followed by the ultraviolet ray irradiation process is performed at temperature of 150 to 3000C for 1 to 15 minutes.
[57] In the case that the nanopore forming process is performed by ultraviolet ray irradiation, the thermal curing process may be omitted. That is, the polysilsesquioxane copolymer coating solution is coated on the silicon wafer to form a thin film, and ultraviolet ray irradiation is performed on the thin film without a thermal curing process to form a nanopore while curing the thin film, thereby preparing an insulating film. And, in the case that the nanopore forming process is performed by ultraviolet ray irradiation, ultraviolet irradiation is first performed and then thermal curing is performed later, thereby preparing an insulating film. That is, the polysilsesquioxane copolymer coating solution is coated on the silicon wafer to form a thin film, ultraviolet ray irradiation is performed on the thin film and then thermal curing is performed on the thin film to prepare an insulating film.
[58] The insulating films prepared by the above-mentioned methods have a low dielectric constant, and thus can be effectively used to a semiconductor device.
[59] Hereinafter, configuration and function of the present invention are described in detail through examples, however, the following examples are given by way of illustration only and various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
[60] Example 1: Synthesis of norbornene-based silane derivatives
[61] 1) Example 1-1: Synthesis of derivative (A)
[62] Derivative (A)
[63]
Figure imgf000011_0001
[64] 100 D of tetrahydrofuran (THF), 500 mmol (47.1 g) of norbornene and 0.1 mmol
(0.04 g) of H 2 PtCl 6 diluted in iso-propanol were put into a flask, temperature was increased to 8O0C, 600 mmol (73.3 g) of trimethoxysilane was added slowly through 2 hours. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (A) ( H-NMR (CDCl ): 1.0 ~ 3.0 (m, HH, norbornyl), 3.55 (s, 9H, OCH3)).
[65] Example 1-2: Synthesis of derivative (B) [66] Derivative (B) [67]
Figure imgf000012_0001
[68] 100 D of tetrahydrofuran (THF), 500 mmol (46.1 g) of norbornadiene and 0.1 mmol (0.04 g) of H 2 PtCl 6 diluted in iso-propanol were put into a flask, temperature was increased to 8O0C, 1.2 mol (146.64 g) of trimethoxysilane was added slowly through 2 hours. Then, reaction was performed at 8O0C for 24 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (B) (1H-NMR (CDCl ): 1.0 ~ 3.0 (m, 1OH, norbornyl), 3.57 (s, 18H, OCH )).
[69] Example 1-3: Synthesis of derivative (C) [70] Derivative (C) [71]
Figure imgf000012_0002
[72] 500 mmol (60.1 g) of 5-vinyl-2-norbornene and 0.1 mmol (0.04 g) of H 2 PtCl 6 diluted in iso-propanol were put into a flask, temperature was increased to 8O0C, 600 mmol (73.3 g) of trimethoxysilane was added slowly through 2 hours. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (C) ( H-NMR (CDCl ): 0.44 ~ 0.52 (m, 2H, CH ), 1.0 ~ 3.0 (m, 9H, norbornyl, CH ), 5.8-6.1 (m, 2H, CH=, norbornyl), 3.57 (s, 9H, OCH )).
[73] Example 1-4: Synthesis of derivative (D) [74] Derivative (D) [75]
Figure imgf000013_0001
[76] 500 mmol (60.1 g) of 5-vinyl-2-norbornene and 0.1 mmol (0.04 g) of H 2 PtCl 6 diluted in iso-propanol were put into a flask, temperature was increased to 8O0C, 1.2 mol (73.3 g) of trimethoxysilane was added slowly through 2 hours. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (D) ( H-NMR (CDCl3): 0.47 ~ 0.54 (m, 2H, CH^, 1.0 ~ 3.0 (m, 12H, norbornyl, CH2), 3.58 (s, 18H, OCH3)).
[77] Example 1-5: Synthesis of derivative (E) [78] Derivative (E) [79]
Figure imgf000013_0002
[80] A predertermined amount of NaH was put into a solution of 45 mmol (5.05 g) of norborneol dissolved in THF (40 D) at -2O0C, 50 mmol (6.9 g) of 4-chlorostyrene was added drop-wise, temperature was increased slowly and reaction was performed under reflux conditions. Cooling was performed to room temperature, excess NaH was removed using methanol, and a solvent was removed under reduced pressure. The obtained crude oil was dissolved in CH Cl , an organic layer was extracted and separated using saturated NaHCO 3 and a solvent was removed under reduced pressure again to prepare a liquid compound of the following Formula.
[81]
Figure imgf000014_0001
[82] 10 mmol (2.1 g) of this compound and 0.05 mmol (0.02 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 10 mmol (1.22 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (E) ( H-NMR (CDCl ): 0.87 ~ 0.91 (m, 2H, CH2), 1.0 ~ 3.0 (m, 13H, norbornyl, OT), 3.55 (s, 9H, OCH3), 6.8 ~ 7.0 (m, 4H, phenyl)).
[83] Example 1-6: Synthesis of derivative (F) [84] Derivative (F) [85]
Figure imgf000014_0002
[86] A predertermined amount of NaH was put into a solution of 45 mmol (4.96 g) of 5-norbornene-2-ol dissolved in THF (40 D) at -2O0C, 50 mmol (6.9 g) of 4-chlorostyrene was added drop-wise, temperature was increased slowly and reaction was performed under reflux conditions. Cooling was performed to room temperature, excess NaH was removed using methanol, and a solvent was removed under reduced pressure. The obtained crude oil was dissolved in CH Cl , an organic layer was extracted and separated using saturated NaHCO and a solvent was removed under reduced pressure again to prepare a liquid compound of the following Formula.
[87]
Figure imgf000015_0001
[88] 10 mmol (2.1 g) of this compound and 0.05 mmol (0.02 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 10 mmol (1.22 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (F) ( H-NMR (CDCl ): 0.87 ~ 0.91 (m, 2H, CH2), 1.0 ~ 3.0 (m, 9H, CH^norbornyl), 3.55 (s, 9H, OCH3), 6.0 ~ 6.2 (m, 2H, CH=, norbornyl), 6.8 ~ 7.0 (m, 4H, phenyl)).
[89] Example 1-7: Synthesis of derivative (G) [90] Derivative (G) [91]
Figure imgf000015_0002
[92] A predertermined amount of NaH was put into a solution of 45 mmol (4.96 g) of 5-norbornene-2-ol dissolved in THF (40 D) at -2O0C, 50 mmol (6.9 g) of 4-chlorostyrene was added drop-wise, temperature was increased slowly and reaction was performed under reflux conditions. Cooling was performed to room temperature, excess NaH was removed using methanol, and a solvent was removed under reduced pressure. The obtained crude oil was dissolved in CH Cl , an organic layer was extracted and separated using saturated NaHCO and a solvent was removed under reduced pressure again to prepare a liquid compound of the following Formula.
[93]
Figure imgf000016_0001
[94] 10 mmol (2.1 g) of this compound and 0.05 mmol (0.02 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 20 mmol (2.44 g) of trimethoxysilane was added slowly through 1 hour. Then, reaction was performed at 8O0C for 24 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (G) ( H-NMR (CDCl ): 0.87 ~ 0.91 (m, 2H, CH ), 1.0 ~ 3.0 (m, 12H, norbornyl, CH ), 3.58 (s, 18H, OCH ), 6.8 ~ 7.0 (m, 4H, phenyl)).
[95] Example 1-8: Synthesis of derivative (H) [96] Derivative (H) [97]
Figure imgf000016_0002
[98] A predertermined amount of NaH was put into a solution of 45 mmol (5.59 g) of 5-norbornene-2-methanol dissolved in THF (40 D) at -2O0C, 50 mmol (6.9 g) of 4-chlorostyrene was added drop-wise, temperature was increased slowly and reaction was performed under reflux conditions. Cooling was performed to room temperature, excess NaH was removed using methanol, and a solvent was removed under reduced pressure. The obtained crude oil was dissolved in CH Cl , an organic layer was extracted and separated using saturated NaHCO and a solvent was removed under reduced pressure again to prepare a liquid compound of the following Formula.
[99]
Figure imgf000017_0001
[100] 10 mmol (2.2 g) of this compound and 0.05 mmol (0.02 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 10 mmol (1.22 g) of trimethoxysilane was added slowly through 1 hour. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (H) ( H-NMR (CDCl ): 0.87 ~ 0.91 (m, 2H, CH2), 1.0 ~ 3.0 (m, 9H, norbornyl, OT), 3.58 (s, 9H, OCH3), 3.7 ~ 3.8 (m, 2H, CH2, norbornylmethyl), 5.7 ~ 6.0 (m, 2H, CH=, norbornyl), 6.8 ~ 7.0 (m, 4H, phenyl)).
[101] Example 1-9: Synthesis of derivative (D [102] Derivative (I) [103]
Figure imgf000017_0002
[104] A predertermined amount of NaH was put into a solution of 45 mmol (5.59 g) of 5-norbornene-2-methanol dissolved in THF (40 D) at -2O0C, 50 mmol (6.9 g) of 4-chlorostyrene was added drop-wise, temperature was increased slowly and reaction was performed under reflux conditions. Cooling was performed to room temperature, excess NaH was removed using methanol, and a solvent was removed under reduced pressure. The obtained crude oil was dissolved in CH Cl , an organic layer was extracted and separated using saturated NaHCO 3 and a solvent was removed under reduced pressure again to prepare a liquid compound of the following Formula.
[105]
Figure imgf000018_0001
[106] 10 mmol (2.2 g) of this compound and 0.05 mmol (0.02 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 20 mmol (2.44 g) of trimethoxysilane was added slowly through 1 hour. Then, reaction was performed at 8O0C for 24 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (I) ( H-NMR (CDCl ): 0.87 ~ 0.91 (m, 2H, CH ), 1.0 ~ 3.0 (m, 12H, norbornyl, CH ), 3.58 (s, 18H, OCH ), 3.7 ~ 3.8 (m, 2H, CH2, norbornylmethyl), 6.8 ~ 7.0 (m, 4H, phenyl)).
[107] Example 1-10: Synthesis of derivative (J) [108] Derivative (J) [109]
Figure imgf000018_0002
[HO] A predertermined amount of NaH was put into a solution of 45 mmol (5.68 g) of 2-norbornanemethanol dissolved in THF (40 D) at -2O0C, 50 mmol (6.9 g) of 4-chlorostyrene was added drop-wise, temperature was increased slowly and reaction was performed under reflux conditions. Cooling was performed to room temperature, excess NaH was removed using methanol, and a solvent was removed under reduced pressure. The obtained crude oil was dissolved in CH Cl , an organic layer was extracted and separated using saturated NaHCO and a solvent was removed under reduced pressure again to prepare a liquid compound of the following Formula.
[I l l]
Figure imgf000019_0001
[112] 10 mmol (2.2 g) of this compound and 0.05 mmol (0.02 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 10 mmol (1.22 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and thickening was performed to prepare a derivative (J) ( H-NMR (CDCl ): 0.87 ~ 0.91 (m, 2H, CH2), 1.0 ~ 3.0 (m, 13H, norbornyl, OT), 3.57 (s, 9H, OCH3), 3.7 ~ 3.8 (m, 2H, CH2, norbornylmethyl), 6.8 ~ 7.0 (m, 4H, phenyl)).
[113] Example 1-11: Synthesis of derivative (K) [114] Derivative (K) [115]
Figure imgf000019_0002
[116] 150 mmol (21 g) of 5-norbornene-2-carboxylic acid, 450 mmol (26.4 g) of allyl alcohol and 300 D of toluene were put into a reactor equipped with a Dean-stark trap, temperature of the reactor was increased slowly to 1150C, 0.1 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed to room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[117]
Figure imgf000020_0001
[118] 100 mmol (20 g) of this compound and 0.1 mmol (0.04 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 100 mmol (12.2 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (K) (1H-NMR (CDCl ): 0.47 ~ 0.54 (m, 2H, CH ), 1.0 ~ 3.0 (m, 9H, norbornyl), 3.57 (s, 9H, OCH3), 3.9 ~ 4.2 (m, 2H, norbornylester), 5.9 ~ 6.1 (m, 2H, CH=, norbornyl)).
[119] Example 1-12: Synthesis of derivative (L) [120] Derivative (L) [121]
Figure imgf000020_0002
[122] 150 mmol (21 g) of 5-norbornene-2-carboxylic acid, 450 mmol (26.4 g) of allyl alcohol and 300 D of toluene were put into a reactor equipped with a Dean-stark trap, temperature of the reactor was increased slowly to 1150C, 0.1 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed to room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[123]
Figure imgf000021_0001
[124] 100 mmol (20 g) of this compound and 0.1 mmol (0.04 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 200 mmol (24.4 g) of trimethoxysilane was added slowly through 1 hour. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (L) ( 1H-NMR (CDCl ): 0.47 ~ 0.54 (m, 2H, CH ), 1.0 ~ 3.0 (m, 1OH, norbornyl), 3.57 (s, 18H, OCH3), 3.9 ~ 4.2 (m, 2H, norbornylester)).
[125] Example 1-13: Synthesis of derivative (M) [126] Derivative (M) [127]
Figure imgf000021_0002
[128] 120 mmol (20 g) of 5-norbornene-exo-2,3-dicarboxylic anhydride, 600 mmol (35.4 g) of allyl alcohol and 300 D of toluene were put into a reactor equipped with a Dean- stark trap, temperature of the reactor was increased slowly to 1150C, 0.15 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed to room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[129]
Figure imgf000022_0001
[130] 100 mmol (16.58 g) of this compound and 0.1 mmol (0.04 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 200 mmol (24.4 g) of trimethoxysilane was added slowly through 1 hour. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (M) (1H-NMR (CDCl ): 0.47 ~ 0.58 (m, 4H, CH ), 1.0 ~ 3.0 (m, 8H, norbornyl), 3.55 (s, 18H, OCH3), 3.9 ~ 4.2 (m, 4H, norbornylester), 6.0-6.2 (m, 2H, CH=, norbornyl)).
[131] Example 1-14: Synthesis of derivative (N) [132] Derivative (N) [133]
Figure imgf000022_0002
[134] 120 mmol (20 g) of 5-norbornene-exo-2,3-dicarboxylic anhydride, 600 mmol (35.4 g) of allyl alcohol and 300 D of toluene were put into a reactor equipped with a Dean- stark trap, temperature of the reactor was increased slowly to 1150C, 0.15 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed at room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[135]
Figure imgf000023_0001
[136] 100 mmol (16.58 g) of this compound and 0.1 mmol (0.04 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 300 mmol (36.6 g) of trimethoxysilane was added slowly through 1 hour and 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (N) (1H-NMR (CDCl ): 0.47 ~ 0.54 (m, 2H, CH ), 1.0 ~ 3.0 (m, 9H, norbornyl), 3.55 ~ 3.57 (m, 18H, OCH3), 3.9 ~ 4.2 (m, 2H, nor- bornylester)).
[137] Example 1-15: Synthesis of derivative (O) [138] Derivative (O) [139]
Figure imgf000023_0002
[140] 120 mmol (15.6 g) of 2-norbornanemethanol, 180 mmol (13.1 g) of acrylic acid and 300 D of toluene were put into a reactor equipped with a Dean-stark trap, temperature of the reactor was increased slowly to 1150C, 0.10 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed to room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[141]
Figure imgf000024_0001
[142] 100 mmol (16.8 g) of this compound and 0.1 mmol (0.04 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 100 mmol (12.2 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (O) (1H-NMR (CDCl ): 0.91 ~ 0.97 (m, 2H, CH ), 1.0 ~ 2.0 (m, HH, norbornyl), 3.55 (s, 9H, OCH3), 3.8 ~ 4.0 (m, 2H, norbornylmethyl)).
[143] Example 1-16: Synthesis of derivative (P) [144] Derivative (P) [145]
Figure imgf000024_0002
[146] 120 mmol (15.3 g) of 2-norbornenemethanol, 180 mmol (13.1 g) of acrylic acid and 300 D of toluene were put into a reactor equipped with a Dean-stark trap, temperature of the reactor was increased slowly to 1150C, 0.10 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed to room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[147]
Figure imgf000025_0001
[148] 100 mmol (16.8 g) of this compound and 0.1 mmol (0.04 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 100 mmol (12.2 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (P) (1H-NMR (CDCl ): 0.91 ~ 0.97 (m, 2H, CH ), 1.0 ~ 2.3 (m, 9H, norbornyl), 3.55 (s, 9H, OCH3), 3.8 ~ 4.0 (m, 2H, norbornylmethyl, 5.9 ~ 6.1 (m, 2H, CH=, norbornyl)).
[149] Example 1-17: Synthesis of derivative (Q) [150] Derivative (Q) [151]
Figure imgf000025_0002
[152] 120 mmol (15.3 g) of 2-norbornenemethanol, 180 mmol (13.1 g) of acrylic acid and 300 D of toluene were put into a reactor equipped with a Dean-stark trap, temperature of the reactor was increased slowly to 1150C, 0.10 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed to room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[153]
Figure imgf000026_0001
[154] 100 mmol (16.8 g) of this compound and 0.1 mmol (0.04 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 200 mmol (24.4 g) of trimethoxysilane was added slowly through 1 hour. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (Q) (1H-NMR (CDCl ): 0.91 ~ 0.97 (m, 2H, CH ), 1.0 ~ 2.3 (m, 1OH, norbornyl), 3.55 (s, 18H, OCH3), 3.8 ~ 4.2 (m, 2H, norbornylmethyl)).
[155] Example 1-18: Synthesis of derivative (R) [156] Derivative (R) [157]
Figure imgf000026_0002
[158] 180 mmol (7.2 g) of LAH (Lithium Aluminum hydride) dissolved in 100 D of THF was added through 1 hour into 120 mmol (20 g) of 5-norbornene-exo-2,3-dicarboxylic anhydride dissolved in 100 D of THF at O0C, and reaction was performed for 15 hours under reflux conditions. Cooling was performed to O0C, and 100 D of diethyl ether and water were added to finish the reaction. The obtained organic layer was extracted and separated,and an organic solvent, THF was removed under reduced pressure to prepare a liquid compound of the following Formula.
[159]
Figure imgf000026_0003
[160] 100 mmol (15.4 g) of this compound and 150 mmol (10.9 g) of acrylic acid and 200 D of toluene were put into a reactor, temperature of the reactor was slowly increased to 1150C, 0.10 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed to room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[161]
Figure imgf000027_0001
[162] 90 mmol (23.8 g) of this compound and 0.1 mmol (0.04 g) of H PtCl diluted in iso-
2 6 propanol were put into a flask, temperature was increased to 8O0C, 180 mmol (22 g) of trimethoxysilane was added slowly through 1 hour. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (R) ( 1H-NMR (CDCl ): 0.91 ~ 0.97 (m, 4H, CH ), 1.0 ~ 2.3 (m, 9H, norbornyl), 3.55 (s, 18H, OCH ), 3.8 ~ 4.0 (m, 4H, norbornylmethyl, 5.9 ~ 6.1 (m, 2H, CH=, norbornyl)).
[163] Example 1-19: Synthesis of derivative (S) [164] Derivative (S) [165]
Figure imgf000027_0002
[166] 180 mmol (7.2 g) of LAH (Lithium Aluminum hydride) dissolved in 100 D of THF was added through 1 hour into 120 mmol (20 g) of 5-norbornene-exo-2,3-dicarboxylic anhydride dissolved in 100 D of THF at O0C, and reaction was performed for 15 hours under reflux conditions. Cooling was performed to O0C, and 100 D of diethyl ether and water were added to finish the reaction. The obtained organic layer was extracted and separated, and an organic solvent, THF was removed under reduced pressure to prepare a liquid compound of the following Formula.
[167]
Figure imgf000028_0001
[168] 100 mmol (15.4 g) of this compound and 150 mmol (10.9 g) of acrylic acid and 200 D of toluene were put into a reactor, temperature of the reactor was slowly increased to 1150C, 0.10 g of sulfuric acid was added and reaction was performed for 10 hours under reflux conditions. Cooling was performed to room temperature, neutralization was performed using NaHCO , and washing was made using diluted water five times to remove the remaining acid and base components. The obtained organic layer was extracted and separated, and an organic solvent, toluene was removed under reduced pressure to prepare a liquid compound of the following Formula.
[169]
Figure imgf000028_0002
[170] 90 mmol (23.8 g) of this compound and 0.1 mmol (0.04 g) of H 2 PtCl 6 diluted in iso- propanol were put into a flask, temperature was increased to 8O0C, 270 mmol (33 g) of trimethoxysilane was added slowly through 1 hour and 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (S) (1H-NMR (CDCl ): 0.91 ~ 0.97 (m, 4H, CH ), 1.0 ~ 2.3 (m, 9H, norbornyl), 3.55 (s, 18H, OCH ), 3.8 ~ 4.0 (m, 4H, CH , norbornylmethyl)).
[171] Example 1-20: Synthesis of derivative (T) [172] Derivative (T) [173]
Figure imgf000029_0001
[174] 970 D of THF, 1.536 mol (190.74 g) of norbomenemethanol, 0.015 mol (4.95 g) of tetrabutylammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 750C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 750C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
[175]
[176] 0r.416 mol (68.32 g) of this compound and 0.002 mol (0.853 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 0.5 mol (61 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (T) (1H-NMR (CDCl3): 0.5 ~ 0.7 (m, 2H, CH2), 1.0 ~ 2.5 (m, 9H, norbornyl, CH2), 3.0 ~ 3.45 (m, 4H, OCH3), 3.45 ~ 3.8 (m, 9H, OCH3), 6.0 ~ 6.2 (m, 2H, CH=, norbornyl).
[177] Example 1-21: Synthesis of derivative (U) [178] Derivative (U) [179] [180] 97 h0 D of THF, 1.536 mol (190.74 g) of norbomenemethanol, 0.015 mol (4.95 g) of tetrabutylammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 750C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 750C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
[181]
[182] 0r.416 mol (68.32 g) of this compound and 0.004 mol (1.706 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 1.0 mol (122 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (U) (1H-NMR (CDCl3): 0.5 ~ 2.8 (m, 14H, norbornyl, CH^, 3.0-3.45 (m, 4H, OCH2), 3.45 ~ 3.8 (m, 18H, OCH3).
[183] Example 1-22: Synthesis of derivative (Y) [184] Derivative (V) [185]
Figure imgf000030_0001
[186] 970 D of THF, 0.768 mol (118.43 g) of norbomenedimethanol, 0.015 mol (4.95 g) of tetrabutylammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 750C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 750C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
[187]
Figure imgf000031_0001
[188] 0.208 mol (48.74 g) of this compound and 0.002 mol (0.853 g) of H 2 PtCl 6 diluted in iso-propanol were put into a flask, temperature was increased to 8O0C, 0.5 mol (61 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (V) (1H-NMR (CDCl ): 0.5 ~ 0.7 (m, 4H, CH ), 1.0 ~ 2.5 (m, 1OH, norbornyl, CH2), 3.0-3.45 (m, 8H, OOy, 3.45 ~ 3.8 (m, 18H, OCH3), 6.0 ~ 6.2 (m, 2H, CH=, norbornyl).
[189] Example 1-23: Synthesis of derivative (W) [190] Derivative (W) [191]
Figure imgf000031_0002
[192] 970 D of THF, 0.768 mol (118.43 g) of norbomenedimethanol, 0.015 mol (4.95 g) of tetrabutylammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 750C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 750C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
[193]
[194] 0.208 mol (48.74 g) of this compound and 0.003 mol (1.28 g) of H 2 PtCl 6 diluted in iso-propanol were put into a flask, temperature was increased to 8O0C, 0.72 mol (91.5 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (W) (1H-NMR (CDCl3): 0.5 ~ 2.8 (m, 17H, norbornyl, CH2), 3.0-3.45 (m, 8H, OCH ), 3.45 ~ 3.8 (m, 27H, OCH ).
[195] Example 1-24: Synthesis of derivative (X) [196] Derivative (X) [197]
Figure imgf000032_0002
[198] 970 D of THF, 1.536 mol (193.82 g) of norbornanemethanol, 0.015 mol (4.95 g) of tetrabutylammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 750C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 750C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
[199]
Figure imgf000033_0001
[200] 0.416 mol (69.16 g) of this compound and 0.002 mol (0.853 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 0.5 mol (61 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (X) (1H-NMR (CDCl ): 0.5 ~ 0.7 (m, 2H, CH ), 0.8 ~ 2.5 (m, 13H, norbornyl, CH2), 3.0-3.45 (m, 4H, OCH ), 3.45 ~ 3.8 (m, 9H, OCH3).
[201] Example 1-25: Synthesis of derivative (Y) [202] Derivative (Y) [203]
Figure imgf000033_0002
[204] 970 D of THF, 1.536 mol (172.29 g) of norborneol, 0.015 mol (4.95 g) of tetrabuty- lammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 750C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 750C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
[205]
Figure imgf000033_0003
[206] 0.416 mol (63.33 g) of this compound and 0.002 mol (0.853 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 0.5 mol (61 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (Y) (1H-NMR (CDCl ): 0.5 ~ 0.7 (m, 2H, CH ), 0.8 ~ 2.5 (m, 12H, norbornyl, CH ), 3.0-3.45 (m, 2H, OCH ), 3.45 ~ 3.8 (m, 1OH, OCH , CH).
[207] Example 1-26: Synthesis of derivative (Z) [208] Derivative (Z) [209]
Figure imgf000034_0001
[210] 970 D of THF, 1.536 mol (169.21 g) of norbornenol, 0.015 mol (4.95 g) of tetrabuty- lammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 750C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 750C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
[211]
Figure imgf000034_0002
[212] 0.416 mol (62.49 g) of this compound and 0.002 mol (0.853 g) of H PtCl diluted in
2 6 iso-propanol were put into a flask, temperature was increased to 8O0C, 0.5 mol (61 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (Z) (1H-NMR (CDCl ): 0.5 ~ 0.7 (m, 2H, CH ), 1.0 ~ 2.5 (m, 8H, norbornyl, CH ), 3.0-3.45 (m, 2H, OCH ), 3.45 ~ 3.9 (m, 1OH, OCH , CH), 6.0 ~ 6.2 (m, 2H, CH=, norbornyl). [213] Example 1-27: Synthesis of derivative (AA)
[214] Derivative (AA)
[215]
Figure imgf000035_0001
[216] 970 D of THF, 1.536 mol (169.21 g) of norbornenol, 0.015 mol (4.95 g) of tetrabuty- lammoniumbromide (TBAB), 97 D of water and 4.61 mol (258.52 g) of potassium hydroxide were put into a reactor, temperature of the reactor was increased to 750C, and 3.07 mol (371.61 g) of allyl bromide was added slowly through 30 minutes. Then, reaction was performed at 750C for 13 hours, a product was extracted into an ether layer using diethyl ether and water, and evaporation was performed under reduced pressure to prepare a liquid compound of the following Formula.
[217]
Figure imgf000035_0002
[218] 0.416 mol (62.49 g) of this compound and 0.004 mol (1.706 g) of H 2 PtCl 6 diluted in iso-propanol were put into a flask, temperature was increased to 8O0C, 1.0 mol (122 g) of trimethoxysilane was added slowly through 30 minutes. Then, reaction was performed at 8O0C for 18 hours, a volatile solvent was removed under reduced pressure of about 0.1 torr and distillation was performed under reduced pressure to prepare a derivative (AA) (1H-NMR (CDCl ): 0.5 ~ 2.8 (m, 13H, norbornyl, CH ), 3.0-3.45 (m, 2H, OCH2), 3.45 ~ 3.8 (m, 19H, OCH3, CH).
[219] Example 2: Synthesis of polvsilsesquioxane copolymers [220] At least one kind of monomer selected from the norbornene-based silane derivatives prepared according to the above-mentioned examples 1-1 to 1-27 and at least one kind of monomer selected from polysilsesquioxane precursors, i.e. methyltrimethoxysilane (MTMS), triethoxysilane (TES) and bistrimethoxysilylethane (BTMSE) were put into a flask, tetrahydrofuran was added 15 times as much as the total amount of the added monomers to dilute the monomers and the internal temperature of the flask was decreased to 1O0C. Predetermined amounts of hydrochloric acid (HCl) and water were added at 1O0C, and temperature of a reactor was slowly increased to 7O0C. Then, reaction was performed at 7O0C for 20 hours. After the reaction solution was placed to a separatory funnel, diethyl ether and tetrahydrofuan were added with the same amount as that of the tetrahydrofuran put initially, washing was made three times using water of about 1/10 times as much as the total solvent, and a volatile material was removed under reduced pressure to obtain a white powder type copolymer. A small amount of acetone was added to the copolymer obtained by the above-mentioned method until a completely clear solution is produced. This solution was filtered using a filter having a pore size of 0.2 D to remove fine powder and other impurities and obtain a clear solution, and water was added to the clear solution slowly. The generated white powder and solution (mixed with acetone and water) were separated from each other, and the white powder was dried at 0 to 2O0C under reduced pressure of 0.1 torr for 10 hours to obtain a polysilsesquioxane copolymer composition. The amounts of the monomer used in synthesizing the precursor, the acid catalyst, water and the obtained copolymer each is shown in the following Table 1, Table 2 and Table 3. FIG. 1 shows a reaction formula by which a polysilsesquioxane copolymer (copolymer 4 of Table 1) is prepared from a norbornene-based silane derivative according to an example (example 1-3) of the present invention and methyltrimethoxysilane, and IG Si-NMR spectrum of the obtained copolymer 4. And, IGthermal decomposition behavior of a copolymer 13. Table 1
Figure imgf000036_0001
Figure imgf000037_0001
[222] [223] Table 2
Figure imgf000037_0002
[224] [225] Table 3
Figure imgf000037_0003
Figure imgf000038_0001
[226] [227] Electrical characteristic analysis test of thin film [228] The norbornene -based polysilsesquioxane copolymer prepared according to the example 2 was dissolved in MIBK (methyl isobutyl ketone) or PM Acetate solvent to prepare a solution in which the content of the norbornene -based polysilsesquioxane copolymer is 20 wt%, the solution was spin-coated at 3,000 rpm for 30 seconds to form a thin film. The thickness of the thin film is about 300 to 400 D when measured using Ellipsometer. Heating up to 45O0C or ultraviolet ray irradiation at room temperature was performed to cure the copolymer thin film, an aluminum electrode was vacuum-deposited on the thin film, and an electrical characteristic of the thin film was measured. The aluminum electrode deposition was made on conditions of diameter of 5 D, pressure of id torr or less, and evaporation speed of 0.5 nm/sec or less thereby to obtain an electrode having uniform thickness of 100 D or so.
[229] The electrical characteristic of the copolymer was measured such that a dielectric constant was calculated from a maximum capacitance value of a C-V (Capacitance- Voltage) curve in an MIS (Metal-Insulator-Semiconductor) structure, and a dielectric constant value of each copolymer is shown in Table 4, Table 5 and Table 6.
[230] [231] Table 4
Figure imgf000038_0002
Figure imgf000039_0001
[232] [233] Table 5
Figure imgf000039_0002
[234] [235] Table 6
Figure imgf000039_0003
[236] [237] According to the above-mentioned result, it is found that the copolymer containing the norbornene-based silane derivative of the present invention has lower dielectric constant than the conventional polymethylsilsesquioxane polymer having a dielectric constant of 2.75. Industrial Applicability
[238] The norbornene-based silane derivatives of the present invention have high reactivity and the norbornene-based polysilsesquioxane copolymers of the present invention, prepared using the same, have excellent mechanical properties, thermal stability and crack resistance and a low dielectric constant, and thus can be effectively used as a material for a semiconductor interlayer insulating film with a low dielectric constant.

Claims

Claims
[1] A norbornene -based silane derivative, represented by any of the following Chemical Figures 1 to 6: [Chemical Figure 1]
Figure imgf000041_0001
[Chemical Figure 2]
Figure imgf000041_0002
[Chemical Figure 3]
Figure imgf000041_0003
[Chemical Figure 4]
(A2J
Figure imgf000041_0004
[Chemical Figure 5] (
Figure imgf000042_0001
[Chemical Figure 6]
Figure imgf000042_0002
3 wherein L , L and L are linkers for linking Si atom with norbornene, each is independently selected from the group consisting of an alkyl group of C ~C and structures represented by any of the following Chemical Figures 7 to 10, and A , A and A each is independently a functional group selected from the group consisting of a hydroxy group, a methoxy group, an ethoxy group, a propoxy group and a chloride group;
[Chemical Figure 7]
Figure imgf000042_0003
[Chemical Figure 8]
Figure imgf000042_0004
[Chemical Figure 9]
Figure imgf000043_0001
[Chemical Figure 10]
Figure imgf000043_0002
wherein y is an integer of 0 to 2, z is an integer of 0 to 3, and q an integer of 0 to 2.
[2] Norbornene-based polysilsesquioxane copolymers, prepared by hydrolyzing and condensation-polymerizing at least one kind of monomer selected from the norbornene-based silane derivatives represented by the above Chemical Figures 1 to 6, as defined in the claim 1, and at least one kind of monomer selected from polysilsesquioxane precursors represented by the following Chemical Figures 11 and 12 in an organic solvent in the presence of an acid or base catalyst and water:
[Chemical Figure 11]
Figure imgf000043_0003
[Chemical Figure 12]
Figure imgf000043_0004
wherein R is hydrogen, methyl or an ethyl group, x is an integer of 0 to 4, R a is an alkyl group of C 1 ~C6 , and B is an alkoxy group of C 1 ~C3 or an chloride group.
[3] The norbornene-based polysilsesquioxane copolymers according to claim 2, wherein a mixing molar ratio of the norbornene-based silane derivative to the polysilsesquioxane precursor is 1:99 to 99:1.
[4] The norbornene-based polysilsesquioxane copolymers according to claim 2, wherein the polysilsesquioxane copolymer has a weight average molecular weight of 500 to 300,000.
[5] The norbornene-based polysilsesquioxane copolymers according to claim 2, wherein the organic solvent is at least one solvent selected from the group consisting of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a ketone-based solvent, an ether-based solvent, an acetate-based solvent, an alcohol-based solvent, amide -based solvent and a silicon-based solvent, or mixtures thereof. [6] An insulating film of a semiconductor device, comprising the norbornene-based polysilsesquioxane copolymers defined in any one of the claims 2 to 5. [7] The insulating film of a semiconductor device according to claim 6, wherein the insulating film has a pore of 1 to 1OD size. [8] A method of preparing an insulating film of a semiconductor device comprising: preparing norbornene-based polysilsesquioxane copolymers by hydrolyzing and condensation-polymerizing at least one kind of monomer selected from the norbornene-based silane derivatives represented by the above Chemical Figures
1 to 6, as defined in the claim 1, and at least one kind of monomer selected from polysilsesquioxane precursors represented by the above Chemical Figures 11 and
12 in an organic solvent in the presence of an acid or base catalyst and water; preparing a coating solution by dissolving the norbornene-based polysilsesquioxane copolymers in an organic solvent; and applying the coating solution on a silicon wafer to form a thin film and curing the thin film. [9] The method of preparing an insulating film of a semiconductor device according to claim 8, wherein the curing step is performed by applying heat or irradiating ultraviolet ray, or by applying heat after irradiating ultraviolet ray. [10] The method of preparing an insulating film of a semiconductor device according to claim 9, further comprising: after the curing step performed by applying heat, decomposing a norbornene molecule to form a pore. [11] The method of preparing an insulating film of a semiconductor device according to claim 10, wherein the pore forming step is performed by applying heat to decompose the norbornene molecule or by irradiating ultraviolet ray to decompose the norbornene molecule. [12] The method of preparing an insulating film of a semiconductor device according to claim 9 or 11, wherein the ultraviolet ray irradiating step is performed by irradiating ultraviolet ray using a ultraviolet lamp having multi- wavelength of 250D to 450D at room temperature to 3000C for 1 minute to 3 hours. [13] The method of preparing an insulating film of a semiconductor device according to claim 8, wherein the coating solution has 5 to 80 weight% of solids content based on the total weight thereof.
[14] The method of preparing an insulating film of a semiconductor device according to claim 8, wherein the organic solvent used in preparing the coating solution is at least one solvent selected from the group consisting of an aliphatic hydrocarbon solvent such as hexane or heptane; an aromatic hydrocarbon solvent such as anisol, mesitylene or xylene; a ketone-based solvent such as methyl isobutyl ketone, l-methyl-2-pyrrolidinone, cyclohexanone or acetone; an ether-based solvent such as tetrahydrofuran, isopropyl ether or propylene glycolpropyl ether; an acetate-based solvent such as ethyl acetate, butyl acetate or propylene glycol methyl ether acetate; an alcohol-based solvent such as isopropyl alcohol or butyl alcohol; an amide -based solvent such as dimethylacetamide or dimethyl- formamide; and a silicon-based solvent, or mixtures thereof.
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