WO2012026464A1 - Matériau de film d'étanchéité, film d'étanchéité et son utilisation - Google Patents

Matériau de film d'étanchéité, film d'étanchéité et son utilisation Download PDF

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WO2012026464A1
WO2012026464A1 PCT/JP2011/068974 JP2011068974W WO2012026464A1 WO 2012026464 A1 WO2012026464 A1 WO 2012026464A1 JP 2011068974 W JP2011068974 W JP 2011068974W WO 2012026464 A1 WO2012026464 A1 WO 2012026464A1
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sealing film
compound
film
carbon atoms
hydrogen atom
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PCT/JP2011/068974
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English (en)
Japanese (ja)
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原　大治
真郷 清水
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東ソー株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides

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  • the present invention relates to a sealing film formed from an organic silicon nitride compound and its use.
  • the present invention relates to a sealing film formed by a plasma enhanced chemical vapor deposition method (PECVD method: Plasma Enhanced Chemical Vapor Deposition method).
  • PECVD method Plasma Enhanced Chemical Vapor Deposition method
  • FPD flat panel displays
  • a glass substrate is used as the base material of the display panel, but it is thinned, reduced in weight, improved in impact resistance, made flexible.
  • organic transistors on plastic substrates using organic semiconductors, LSIs, Si thin film solar cells, organic dye-sensitized solar cells, organic semiconductor solar cells, and the like.
  • a gas barrier plastic substrate provided with gas barrier performance against water vapor and oxygen gas is required.
  • transparent plastic films imparted with gas barrier properties are increasingly used in the future as packaging materials for foodstuffs, pharmaceuticals, electronic materials, electronic parts, etc., instead of opaque aluminum foil laminated films.
  • a physical film formation method and a chemical vapor deposition method hereinafter referred to as a CVD method.
  • Patent Document 1 As a proposal using a carbon nitride film, and a carbon nitride film is formed by PECVD using methane gas and nitrogen gas to form an adhesion layer between a glass substrate and a resin film. Further, Patent Document 2 discloses a film formation by PECVD of a carbon nitride film using an amine compound such as trimethylamine. In the semiconductor field, Patent Document 3 proposes to use a carbon nitride thin film formed using an unsaturated carbon compound such as ethylene or acetylene and nitrogen or ammonia as an interlayer insulating film or a gate insulating film of a thin film transistor.
  • an unsaturated carbon compound such as ethylene or acetylene and nitrogen or ammonia
  • Patent Document 4 proposes to use a carbon nitride film formed by a CVD method as a gate insulating film of a field effect transistor.
  • the raw material is a two-component system, and the composition of the resulting film is not constant.
  • the nitrogen content was not stable or the nitrogen content was low.
  • the film is not sufficiently dense so that the gas barrier performance against water vapor and oxygen is insufficient, or when used as an insulating film for semiconductors, the insulating properties are insufficient.
  • the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to use organic compounds that can be used as gas barriers and barrier films for semiconductors, etch stop films, hard mask films, etc., using compounds suitable for CVD devices as raw materials. It is an object to provide a gas barrier film and a semiconductor device using silicon nitride-containing films and using these films.
  • the present inventors use a specific organic silicon nitride compound as a raw material, and a method of forming a sealing film by a CVD method is a preferable method for forming dense films for gas barriers and semiconductor devices. As a result, the present invention has been completed. That is, the present invention has the following gist.
  • the organosilicon nitride compound is represented by the following general formula (1) (In the formula, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • N represents an integer of 1 to 10.
  • the sealing film according to [1] above which is a compound having a chain or cyclic structure represented by: [3]
  • the organosilicon nitride compound is represented by the following general formula (2) (Wherein R 2 and R 4 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and R 3 and R 5 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)
  • X represents an integer of 1 to 10.
  • the organosilicon nitride compound is represented by the following general formula (3): (Wherein R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and y represents an integer of 2 to 10)
  • a flat panel display device comprising the sealing film according to any one of [1] to [7] above.
  • a semiconductor device comprising the sealing film according to any one of [1] to [7] above.
  • the sealing film material according to [11] above, wherein the compound having a chain or cyclic structure represented by the general formula (1) is a chain compound represented by the general formula (2).
  • the sealing film material according to [11] above, wherein the compound having a chain or cyclic structure represented by the general formula (1) is a cyclic compound represented by the general formula (3).
  • a film obtained by a CVD method using an organic silicon nitride compound having a structure in which at least one hydrogen atom is directly bonded to a silicon atom and at least one hydrogen atom is directly bonded to a nitrogen atom is sealed. It can be used as a film, and a dense and high mechanical strength material can be provided as a gas barrier film or a gas barrier layer for a gas barrier substrate.
  • the organic silicon nitride compound having a structure in which at least one hydrogen atom that can be used as a raw material for the CVD method is directly connected to silicon and at least one hydrogen atom is directly connected to a nitrogen atom is not particularly limited.
  • a compound having a chain or cyclic structure represented by the general formula (1) is preferable.
  • R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • the hydrocarbon group may be either saturated or unsaturated, and may be linear or branched. Any structure of a ring shape may be used.
  • those in which R 1 are bonded to each other are also included in the scope of the present invention. When the number of carbon atoms exceeds 20, it may be difficult to procure the corresponding raw material such as organic halide, or even if it can be procured, the purity may be low.
  • R 1 is preferably a hydrogen atom or a saturated or unsaturated group having 1 to 10 carbon atoms from the viewpoint that the vapor pressure of the organic silicon nitride compound does not become too low when considering stable use in a CVD apparatus.
  • Hydrocarbon groups such as hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups, arylalkyl groups, alkylaryl groups, alkenyl groups, arylalkenyl groups, alkenylaryl groups, alkynyl groups, arylalkynyl groups, alkynyls
  • An aryl group can be mentioned.
  • R 1 may be the same or different.
  • R 1 examples include a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert.
  • -Alkyl groups such as amyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, 1-adamantyl, Aryl groups such as phenyl, diphenyl and naphthyl; arylalkyl groups such as benzyl and methylbenzyl; o-toluyl, m-toluyl, p-toluyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5 -Alkylaryl groups such as dimethylphenyl, 2,4,6-trimethylphenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, Vinyl, allyl, 1-propenyl, 1-butenyl, 1,3-buta
  • alkenyl group of Arylalkenyl groups such as 2-phenyl-1-ethenyl, alkenyl aryl groups such as o-styryl, m-styryl, p-styryl, Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 3-hexynyl, 5-hexynyl, etc.
  • alkynyl group of There may be mentioned at least one selected from the group consisting of arylalkynyl groups such as 2-phenyl-1-ethynyl and alkynylaryl groups such as 2-ethynyl-2-phenyl.
  • n represents an integer of 1 to 10.
  • n is an integer of 1 to 6 in that the vapor pressure of the organic silicon nitride compound does not become too low.
  • n is an integer of 1 to 4.
  • n is preferably 1 or 2.
  • Examples of the general formula (1) include a chain compound represented by the general formula (2).
  • R 2 and R 4 are each independently a saturated or unsaturated hydrocarbon group having a linear, branched or cyclic structure having 1 to 20 carbon atoms. it can.
  • R 3 and R 5 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is a saturated or unsaturated carbon having a linear, branched, or cyclic structure. Hydrogen groups can be used.
  • those in which R 2 and R 4 and R 3 and R 5 are bonded to each other are also included in the scope of the present invention.
  • R 2 to R 5 are preferably hydrocarbon groups having 1 to 10 carbon atoms in that the vapor pressure of the organic silicon nitride compound is not too low. More preferably, a saturated hydrocarbon group having 1 to 4 carbon atoms, specifically, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl.
  • R 2 to R 5 are preferably methyl, ethyl, or i-propyl.
  • R 2 and R 4 and R 3 and R 5 may be the same or different.
  • x represents an integer of 1 to 10.
  • x is an integer of 1 to 6 in that the vapor pressure of the organic silicon nitride compound does not become too low.
  • x is an integer of 1 to 4.
  • x is preferably 1 or 2.
  • Specific examples of the compound represented by the general formula (2) include 1-methyldisilazane, 1,1-dimethyldisilazane, 1,3-dimethyldisilazane, 1,1,3-trimethyldisilazane, 1,1,3,3-tetramethyldisilazane 1-methyltrisilazane, 3-methyltrisilazane, 1,3-dimethyltrisilazane, 1,5-dimethyltrisilazane, 1,1,3-trimethyltrisilazane, 1,3,5-trimethyltrisilazane, 1,1,3,5- Tetramethyltrisilazane, 1,1,5,5-tetramethyltrisilazane, 1,1,3,5,5-pentamethyltrisilazane, 1-methyltetrasilazane, 3-methyltetrasilazane, 1,1-dimethyl Tetrasilazane, 1,3-dimethyltetrasilazane, 1,5-dimethyltetrasila
  • 1-methylpentasilazane 3-methylpentasilazane, 5-methylpentasilazane, 1,1-dimethylpentasilazane, 1,3-dimethylpentasilazane, 1,5-dimethylpentasilazane, 1,7-dimethylpentasilazane 1,9-dimethyl pentasilazane, 1,1,3-trimethyl pentasilazane, 1,1,5-trimethyl pentasilazane, 1,1,7-trimethyl pentasilazane, 1,1,9-trimethyl pentasilazane, , 3,5-trimethylpentasilazane, 1,3,7-trimethylpentasilazane, 1,3,9-trimethylpentasilazane, 3,5,9-trimethylpentasilazane, 1,1,3,5-tetramethylpenta Silazane, 1,1,3,7-tetramethylpenta
  • 1,3-diphenyldisilazane 1,3-diphenyl-1,3-dimethyldisilazane, 1,1,3,3-tetraphenyldisilazane, 1,3,5-triphenyltrisilazane, 1,1 , 3,5,5-pentaphenyltrisilazane, 1,3,5,7-tetraphenyltetrasilazane, 1,1,3,5,7,7-hexaphenyltetrasilazane, 1,3,5,7, 9-pentaphenylpentasilazane, 1,1,3,5,7,9,9-heptaphenylpentasilazane, 1,3,5-tritoluyltrisilazane, 1,1,3,5,5-pentatoluyltrisilazane, 1,1,3,5,5-pentatoluyltri Silazane, 1,3,5,7-tetratoluyltetrasil
  • the compounds represented by the general formula (2) are preferably the above-mentioned disilazanes and trisilazanes from the viewpoint of high vapor pressure and reduction of the carbon content of the resulting thin film, more preferably 1,1- Dimethyldisilazane, 1,3-dimethyldisilazane, 1,1,3-trimethyldisilazane, 1,1,3,3-tetramethyldisilazane.
  • examples of the general formula (1) include the cyclic compounds represented by the general formula (3).
  • R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is saturated or unsaturated having a linear, branched or cyclic structure. These hydrocarbon groups can be used. Further, those in which R 6 are bonded to each other are also included in the scope of the present invention. When the number of carbon atoms exceeds 20, it may be difficult to procure the corresponding raw material such as organic halide, or even if it can be procured, the purity may be low.
  • R 6 is preferably a hydrocarbon group having 1 to 10 carbon atoms, and preferably having 1 to 4 carbon atoms in that the vapor pressure of the organic silicon nitride compound is not too low.
  • Saturated hydrocarbon groups are more preferred, specifically methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl.
  • R 6 is preferably methyl, ethyl, or i-propyl.
  • R 6 may be the same or different.
  • y represents an integer of 2 to 10.
  • y is an integer of 2 to 6 in that the vapor pressure of the organic silicon nitride compound does not become too low.
  • y is 3 or 4.
  • Specific examples of the compound represented by the general formula (3) include 1-methylcyclodisilazane, 1,3-dimethylcyclodisilazane, 1-methylcyclotrisilazane, 1,3-dimethylcyclotrisilazane, 1,3,5-trimethylcyclotrisilazane, 1-methylcyclotetrasilazane, 1,3-dimethylcyclotetrasilazane, 1,5-dimethylcyclotetrasilazane, 1,3,5-trimethylcyclotetrasilazane, 1,3,5,7-tetramethylcyclotetrasilazane, 1,3-dimethylcyclopenta Silazane, 1,5-dimethylcyclopenta Silazane, 1,5-dimethylcyclopenta Sila
  • 1,3-di-n-pentylcyclodisilazane 1,3,5-tri-n-pentylcyclotrisilazane, 1,3,5,7-tetran-pentylcyclotetrasilazane, 1,3,5,7 , 9-penta-n-pentylcyclopentasilazane, 1,3,5,7,9,11-hexa-n-pentylcyclohexalazane, 1,3-dicyclopentylcyclodisilazane, 1,3,5-tricyclopentylcyclo Trisilazane, 1,3,5,7-tetracyclopentylcyclotetrasilazane, 1,3,5,7,9-pentacyclopentylcyclopentasilazane, 1,3,5,7,9,11-hexacyclopentylcyclohexasilazane 1,3-di tert.
  • 1,3-di-n-hexylcyclodisilazane 1,3,5-tri-n-hexylcyclotrisilazane, 1,3,5,7-tetra-n-hexylcyclotetrasilazane, 1,3,5,7 , 9-penta-n-hexylcyclopentasilazane, 1,3,5,7,9,11-hexane-hexylcyclohexalazane, 1,3-dicyclohexylcyclodisilazane, 1,3,5-tricyclohexylcyclotri Silazane, 1,3,5,7-tetracyclohexylcyclotetrasilazane, 1,3,5,7,9-pentacyclohexylcyclopentasilazane, 1,3,5,7,9,11-hexacyclohexylcyclohexasilazane, 1,3-di-n-heptyl
  • the compounds represented by the general formula (3) are preferably the above cyclotrisilazanes and cyclotetrasilazanes from the viewpoint of high vapor pressure and reduction of the carbon content of the resulting thin film, and more preferably 1, 3,5-trimethylcyclotrisilazane and 1,3,5,7-tetramethylcyclopentasilazane.
  • the method for producing the organic silicon nitride compounds represented by the general formulas (1) to (3) is not particularly limited. For example, it is produced by reacting a hydrogen atom, a hydrocarbon group-substituted halogenated silane compound with ammonia gas. And a method of producing a halogenated silane compound by reacting with a metal amide can be used. At this time, the halogenated silane compound itself may be used as the reaction medium, but an inert solvent may be used as the reaction medium.
  • the reaction solvent that can be used is not particularly limited as long as it is used in the art, and examples thereof include n-pentane, i-pentane, n-hexane, cyclohexane, n-heptane, and n-decane.
  • Saturated hydrocarbons unsaturated hydrocarbons such as toluene, xylene, decene-1, diethyl ether, dipropyl ether, tert. -Ethers such as butyl methyl ether, dibutyl ether, cyclopentyl methyl ether, and tetrahydrofuran can be used.
  • reaction temperature during the production it is usually carried out in the range of ⁇ 100 to 200 ° C., preferably in the range of ⁇ 85 to 150 ° C., which is an industrially used temperature.
  • the pressure conditions for the reaction can be any of under pressure, normal pressure, and reduced pressure.
  • a purification means such as filtration using a glass filter, sintered porous body, etc., atmospheric pressure or vacuum distillation, or column separation using silica, alumina, polymer gel, etc. Can do. At this time, these means may be used in combination as necessary.
  • the method in the field of the organometallic compound synthesis is followed. That is, the dehydration and deoxygenation is performed in a nitrogen or argon atmosphere, and the solvent to be used and the column filler for purification are preferably subjected to a dehydration operation in advance. It is also preferable to remove impurities such as metal residues and particles (foreign matter such as dust).
  • the compound having a chain or cyclic structure represented by the general formulas (1) to (3) can be used as a sealing film material for a CVD method.
  • the organic silicon nitride compound is formed by a CVD method and can be used as a sealing film.
  • the sealing film contains silicon atoms, carbon atoms and nitrogen atoms, and the composition of the surface is 1.0 to 1.33, preferably 0.2, with respect to silicon 1.0 in terms of atomic ratio. Is 1.33 or less, the carbon content is 0 or more and 1.0 or less, preferably 0 or more and 0.5 or less, and absorption of 1200 to 1300 cm ⁇ 1 and 2800 to 3200 cm ⁇ 1 of the infrared absorption spectrum is observed. A membrane that is substantially below the detection limit can be obtained. At this time, the composition of the surface of the film can be measured by XPS or the like.
  • the absorption at 1200 to 1300 cm ⁇ 1 is derived from the Si-methyl bond, and the absorption at 2800 to 3200 cm ⁇ 1 indicates the presence of a hydrocarbon group at the bond terminal. Therefore, the fact that all of them are substantially below the detection limit means that all the hydrocarbon groups in the membrane are involved in crosslinking and do not exist so much that they are detected as binding ends. is there. In the present invention, the fact that the absorption in a specific region of the infrared absorption spectrum is substantially below the detection limit means that the absorption is not observed when the infrared absorption spectrum chart is visually observed. .
  • the water permeability is 1.0 ⁇ 10 ⁇ 2 g / m 2 ⁇ day or less, preferably 5.0 ⁇ 10 ⁇ 3 g / m 2 ⁇ day or less, and the water permeability is extremely low.
  • a sealing film can be obtained.
  • Examples of the CVD method used for film formation in the present invention include a PECVD method or a catalytic chemical vapor deposition method (Cat. CVD method).
  • the type of PECVD method and the apparatus to be used are not particularly limited, but the PECVD method may be used in the technical fields such as semiconductor manufacturing field, liquid crystal display manufacturing field, roll-to-roll polymer film surface processing field, and the like. Commonly used ones are used.
  • a PECVD apparatus an organic silicon nitride compound is vaporized by a vaporizer and introduced into a film forming chamber, applied to an electrode in the film forming chamber by a high frequency power source, plasma is generated, and A PECVD thin film can be formed on a silicon substrate or the like.
  • an inert gas such as helium, argon, krypton, neon, or xenon and an organic nitrogen-based gas such as ammonia, hydrazine, or nitrogen are used to improve the nitrogen content of carbon nitride. It is also within the scope of the present invention to be introduced with a silicon nitride compound.
  • the plasma generation method of the PECVD apparatus is not particularly limited, and inductively coupled plasma, capacitively coupled plasma, ECR plasma, or the like used in the art can be used.
  • the plasma generation source various types such as a parallel plate type and an antenna type can be used, and PECVD under any pressure conditions such as atmospheric pressure PECVD, reduced pressure PECVD, and pressurized PECVD can be used.
  • the PECVD conditions at this time are not particularly limited, but the power is preferably from 1.0 to 10,000 W, and more preferably from 1.0 to 2000 W.
  • a parallel plate capacitively coupled PECVD apparatus is shown in FIG. 1 as a PECVD apparatus.
  • the parallel plate capacitively coupled PECVD apparatus shown in FIG. 1 includes a showerhead upper electrode, a lower electrode capable of controlling the temperature of the substrate in the PECVD apparatus chamber, a vaporizer apparatus for supplying a raw material compound to the chamber by vaporization, a high frequency power supply, and a matching circuit.
  • the plasma generator comprises an exhaust system comprising a vacuum pump.
  • the PECVD apparatus 1 includes a PECVD chamber 2, an upper electrode 3 having a shower head for uniformly supplying a raw material compound into the chamber, and a temperature control apparatus 8 for installing a thin film forming substrate 5 such as a Si substrate.
  • the electrode 4 includes vaporizers 9 to 15 for vaporizing raw material compounds, a matching circuit 6 and an RF power source 7 as a plasma generation source, and an exhaust device 16 for exhausting unreacted substances and by-products in the chamber. Reference numerals 17 and 18 are grounds.
  • the matching circuit 6 and the RF power source 7 which are plasma generation sources are connected to the upper electrode 3 and generate plasma by discharge.
  • the standard of the RF power source 7 is not particularly limited, but the power used in this technical field is 1 to 2000 W, preferably 10 to 1000 W, the frequency is 50 kHz to 2.5 GHz, preferably 100 kHz to 100 MHz, particularly preferably 200 kHz to A 50 MHz RF power supply can be used.
  • the control of the substrate temperature is not particularly limited, but is in the range of ⁇ 90 to 1000 ° C., preferably 0 to 500 ° C.
  • the vaporizer is filled with a raw material compound 13 at room temperature and normal pressure, and is provided with a container 12 having a dip pipe and a pipe 15 for pressurization with the inert gas, and a liquid flow rate for controlling the flow rate of the raw material compound 13. It comprises a control device 10, a vaporizer 9 for vaporizing the raw material compound 13, a pipe 14 for supplying the inert gas into the PECVD chamber through the vaporizer, and a gas flow rate control device 11 for controlling the flow rate thereof. .
  • This vaporizer is connected by piping from the vaporizer 9 to the upper electrode 3 having a shower head.
  • the supply amount of the raw material compound into the chamber is not particularly limited, but is 0.1 to 10000 sccm, preferably 10 to 5000 sccm.
  • the supply amount of the inert gas is not particularly limited, but is 0.1 to 10,000 sccm, preferably 10 to 5000 sccm.
  • an inductively coupled remote PECVD apparatus is shown in FIG. 2 as a PECVD apparatus.
  • the inductively coupled remote PECVD apparatus shown in FIG. 2 is a plasma generator wound in a coil around the quartz at the top of the PECVD apparatus chamber, a temperature-controllable substrate installation part, and a vaporizer that vaporizes and feeds raw material compounds into the chamber. It comprises a plasma generator comprising a device, a high-frequency power source and a matching circuit, and an exhaust system having a vacuum pump.
  • the PECVD apparatus 19 includes a PECVD chamber 20, a coil 21 as a plasma generation unit, a quartz tube 22, a heater unit 23 for installing a thin film forming substrate 24 such as a Si substrate, a temperature control unit 27, and a material compound for vaporization. Vaporizing devices 28 to 35, a matching circuit 25 serving as a plasma generation source, an RF power source 26, and an exhaust device 36 for exhausting unreacted substances and by-products in the chamber.
  • Reference numeral 37 denotes a ground.
  • a coil around quartz which is a plasma generation unit, is connected to a matching circuit 25 and is discharged in an antenna current magnetic field by RF current in a quartz tube to generate plasma.
  • the standard of the RF power supply 26 is not particularly limited, but the power used in the technical field is 1 to 2000 W, preferably 10 to 1000 W, the frequency is 50 kHz to 2.5 GHz, preferably 100 kHz to 100 MHz, particularly preferably 200 kHz to A 50 MHz RF power supply can be used.
  • the control of the substrate temperature is not particularly limited, but is in the range of ⁇ 90 to 1000 ° C., preferably 0 to 500 ° C.
  • the vaporizer is filled with a raw material compound 33 that is liquid at normal temperature and pressure, a container 32 having a dip pipe and a pipe 35 that is pressurized with the inert gas, and a liquid flow rate that controls the flow rate of the raw material compound 33 that is liquid.
  • the supply amount of the raw material compound into the chamber is not particularly limited, but is 0.1 to 10000 sccm, preferably 10 to 5000 sccm.
  • the supply amount of the inert gas is not particularly limited, but is 0.1 to 10,000 sccm, preferably 10 to 5000 sccm.
  • the raw material compound is supplied into the chamber as a raw material compound gasified with an inert gas or as a gasified raw material compound using the PECVD apparatus exemplified above, and plasma is generated by discharge by an RF power source to control the temperature. A film is formed on the substrate.
  • the pressure in the chamber at this time is not particularly limited, but is 0.1 to 10,000 Pa, preferably 1 to 5000 Pa.
  • a microwave PECVD apparatus is shown at 38 in FIG.
  • the matching circuit 51 and the microwave transmitter 52 which are microwave generation sources, are connected to the quartz chamber, and generate plasma by irradiating the quartz chamber with microwaves.
  • the frequency of the microwave is not particularly limited, and a microwave having a frequency of 1 MHz to 50 GHz, preferably 0.5 to 10 GHz, particularly preferably 1 to 5 GHz used in this technical field can be used.
  • the microwave output can be 0.1 to 20000 W, preferably 1 to 10000 W.
  • the control of the substrate temperature is not particularly limited, but is in the range of ⁇ 90 to 1000 ° C., preferably 0 to 500 ° C.
  • the vaporizer is filled with a raw material compound 48 that is liquid at room temperature and normal pressure, and includes a container 47 that includes a dip pipe and a pipe 50 that is pressurized with the inert gas, and a liquid flow rate that controls the flow rate of the raw material compound 48 that is a liquid.
  • a shower head 46 for uniformly supplying the inert gas and the gasified raw material compound 48 into the chamber.
  • the supply amount of the raw material compound into the chamber is not particularly limited, but is 0.1 to 10000 sccm, preferably 10 to 5000 sccm.
  • the supply amount of the inert gas is not particularly limited, but is 0.1 to 10,000 sccm, preferably 10 to 5000 sccm.
  • the raw material compound is supplied into the chamber as a raw material compound gasified with an inert gas or as a gasified raw material compound using the PECVD apparatus exemplified above, and plasma is generated by microwave irradiation to control the temperature. A film is formed on the substrate.
  • the pressure in the chamber at this time is not particularly limited, but is 0.1 to 10,000 Pa, preferably 1 to 5000 Pa.
  • the sealing film obtained from the above organic silicon nitride compound can be heat-treated, ultraviolet irradiation treatment, or electron beam treatment to obtain a sealing film with improved densification or mechanical strength,
  • the film obtained by the above treatment is suitable as a gas barrier film.
  • the sealing film of the present invention can be used as a gas barrier layer and is useful as a gas barrier member.
  • the FPD device, semiconductor device, etc. which comprise the sealing film of this invention have the characteristic preferable as a device.
  • the physical properties of the obtained film were evaluated and measured as follows.
  • the thickness measurement was performed using a stylus type surface shape measuring instrument (Dektak 6M) manufactured by ULVAC.
  • the oxygen permeability was measured by a method based on the JIS K 7126-1 method, and the water permeability was measured by a method based on the JIS K 7129A method or the JIS K 7129 C method.
  • the total light transmittance was measured by a method based on JIS K 7361-1.
  • the linear expansion coefficient was determined by measuring a film sample in an unloaded state in an oven at 5 deg. / Min.
  • the film length was calculated by measuring the change in the film length with a CCD camera.
  • the surface roughness was measured by tapping mode AFM using a scanning probe microscope (NanoScope IIIa) manufactured by Veecoo.
  • the yellow index was measured by a method based on JIS Z-8722 using ZE2000 manufactured by Nippon Denshoku.
  • Example 1 (deposition of a sealing film using 1,1,3,3-tetramethyldisilazane by a parallel plate capacitive coupling type PECVD apparatus)
  • the film was formed on a polyethylene naphthalate film substrate using the parallel plate capacitively coupled PECVD apparatus shown in FIG.
  • the film forming conditions were: vaporized 1,1,3,3-tetramethyldisilazane flow rate 50 sccm, helium gas flow rate 50 sccm, chamber internal pressure 133 Pa, substrate temperature room temperature, RF power supply power 200 W, and RF power supply frequency 13.56 MHz.
  • the film was formed under the conditions of 5 minutes. The result was a film thickness of 3190 nm.
  • the oxygen permeability was 0.70 cc / m 2 ⁇ day
  • the water permeability was 0.12 g / m 2 ⁇ day.
  • the total light transmittance was 91.7%
  • the linear expansion coefficient was 12 ppm / deg.
  • the surface roughness was 0.5 nm.
  • the yellow index was 1.0.
  • Example 2 (deposition of a sealing film using 1,1,3,3-tetramethyldisilazane by a parallel plate capacitive coupling type PECVD apparatus) A sealing film was formed in the same manner as in Example 1 except that the helium gas flow rate was changed to 50 sccm and the helium gas flow rate was 50 sccm and oxygen was 50 sccm in Example 1. The result was a film thickness of 4360 nm. When the gas permeability was measured, the oxygen permeability was 0.35 cc / m 2 ⁇ day, and the water permeability was 0.01 g / m 2 ⁇ day. The total light transmittance was 91.8%, and the linear expansion coefficient was 11 ppm / deg. The surface roughness was 0.6 nm. The yellow index was 0.4.
  • Example 3 (deposition of a sealing film using 1,1,3,3-tetramethyldisilazane by a parallel plate capacitive coupling type PECVD apparatus)
  • a sealing film was formed in the same manner as in Example 1 except that the flow rate of helium gas was changed to 50 sccm, oxygen was 100 sccm, and the film formation time was 0.5 minutes. The result was a film thickness of 385 nm.
  • the oxygen permeability was 0.01 cc / m 2 ⁇ day
  • the water permeability was 0.0060 g / m 2 ⁇ day.
  • the total light transmittance was 92.0%, and the linear expansion coefficient was 11 ppm / deg.
  • the surface roughness was 0.4 nm.
  • the yellow index was 0.4.
  • Si 24 atom%
  • O 53 atom%
  • C 18 atom%
  • N 5 atom%.
  • infrared absorption spectrum analysis confirmed that the absorption at 1200 to 1300 cm ⁇ 1 and 2800 to 3200 cm ⁇ 1 was substantially below the detection limit.
  • Comparative Example 1 (deposition of carbon-containing silicon oxide sealing film using hexamethyldisilazane by parallel plate capacitive coupling type PECVD apparatus)
  • the film was formed on a polyethylene naphthalate film substrate using the parallel plate capacitively coupled PECVD apparatus shown in FIG.
  • the film formation conditions were as follows: vaporized hexamethyldisilazane flow rate 50 sccm, helium gas flow rate 50 sccm, chamber internal pressure 133 Pa, substrate temperature room temperature, RF power supply power 200 W, and RF power supply frequency 13.56 MHz. .
  • the result was a film thickness of 1370 nm.
  • the oxygen permeability was 2.73 cc / m 2 ⁇ day
  • the water permeability was 1.77 g / m 2 ⁇ day.
  • the total light transmittance was 83.5%
  • the linear expansion coefficient was 30 ppm / deg.
  • the surface roughness was 10 nm.
  • the yellow index was 11.5.
  • Comparative Example 2 (deposition of carbon-containing silicon oxide sealing film using tetramethoxysilane by parallel plate capacitive coupling type PECVD apparatus) The film was formed on a polyethylene naphthalate film substrate using the parallel plate capacitively coupled PECVD apparatus shown in FIG. Film formation was performed for 10 minutes under the conditions of vaporized tetramethoxysilane flow rate of 50 sccm, helium gas flow rate of 50 sccm, chamber internal pressure 133 Pa, substrate temperature room temperature, RF power supply power 200 W, and RF power supply frequency 13.56 MHz. The result was a film thickness of 136 nm.
  • the oxygen permeability was 1.75 cc / m 2 ⁇ day and the water permeability was 1.67 g / m 2 ⁇ day.
  • the total light transmittance was 86.4%, and the linear expansion coefficient was 32 ppm / deg.
  • the surface roughness was 26 nm.
  • the yellow index was 2.4.
  • Comparative Example 3 When the gas permeability, total light transmittance, and linear expansion coefficient of the polyethylene naphthalate film substrate used were measured, the oxygen permeability was 21.0 cc / m 2 ⁇ day, and the water permeability was 6.70 g / m 2 ⁇ day. Met. The total light transmittance was 86.9%, and the linear expansion coefficient was 35 ppm / deg. The surface roughness was 1.4 nm. The yellow index was 0.4.
  • Example 4 (deposition of a sealing film using 1,3,5,7-tetramethylcyclotetrasilazane by a parallel plate capacitively coupled PECVD apparatus)
  • the film was formed on a polyethylene naphthalate film substrate using the parallel plate capacitively coupled PECVD apparatus shown in FIG.
  • the film forming conditions were: vaporized 1,3,5,7-tetramethylcyclotetrasilazane flow rate 50 sccm, helium gas flow rate 50 sccm, chamber internal pressure 133 Pa, substrate temperature room temperature, RF power supply power 200 W, and RF power supply frequency 13.
  • the film was formed for 2 minutes under the condition of 56 MHz. The result was a film thickness of 575 nm.
  • the oxygen permeability was 0.02 cc / m 2 ⁇ day
  • the water permeability was 0.0048 g / m 2 ⁇ day.
  • the total light transmittance was 91.7%
  • the linear expansion coefficient was 11 ppm / deg.
  • the surface roughness was 0.5 nm.
  • the yellow index was 1.0.
  • Example 5 (deposition of a sealing film using 1,3,5,7-tetramethylcyclotetrasilazane by a parallel plate capacitive coupling type PECVD apparatus)
  • a sealing film was formed in the same manner as in Example 4 except that the flow rate of helium gas was changed to 50 sccm in Example 4 and the flow rate of helium gas was 50 sccm and oxygen was 50 sccm.
  • the result was a film thickness of 428 nm.
  • the oxygen permeability was 0.01 cc / m 2 ⁇ day
  • the water permeability was 0.0035 g / m 2 ⁇ day.
  • the total light transmittance was 91.9%, and the linear expansion coefficient was 10 ppm / deg.
  • the surface roughness was 0.4 nm.
  • the yellow index was 0.3.
  • Example 6 (deposition of a sealing film using 1,3,5,7-tetramethylcyclotetrasilazane by a parallel plate capacitive coupling type PECVD apparatus)
  • a sealing film was formed in the same manner as in Example 4 except that the flow rate of helium gas was changed to 50 sccm, oxygen was set to 100 sccm, and the film formation time was 0.5 minutes. The result was a film thickness of 428 nm.
  • the oxygen permeability was 0.01 cc / m 2 ⁇ day
  • the water permeability was 0.0026 g / m 2 ⁇ day.
  • the total light transmittance was 92.0%, and the linear expansion coefficient was 10 ppm / deg.
  • the surface roughness was 0.4 nm.
  • the yellow index was 0.3.
  • fraction obtained by distillation is 1,3,5,7-tetramethylcyclotetrasilazane indicates that gas chromatography, 13 C-NMR (nuclear magnetic resonance), 1 H-NMR, IR (infrared spectroscopy) ), GC-MS (gas chromatograph mass spectrometry) and the like.
  • the sealing film obtained by using the sealing film material of the present invention can be used as a densified gas barrier layer with improved mechanical strength, and can be used in devices such as FPD devices and semiconductor devices. Is possible.
  • the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2010-190725 filed on August 27, 2010 are cited here as disclosure of the specification of the present invention. Incorporated.

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Abstract

Cette invention concerne un film de silicium organique contenant des nitrures, qui peut être utilisé en tant que film de protection pour les barrières contre les gaz et les semi-conducteurs, en tant que film d'arrêt de gravure, en tant que film de masque dur et similaires. Ledit film est formé à partir d'un composé convenant comme matière première pour un appareil de dépôt chimique en phase vapeur. L'invention concerne en outre un film de protection contre les gaz et un dispositif à semi-conducteur utilisant chacun le film de silicium organique contenant des nitrures. Un film d'étanchéité est formé par dépôt chimique en phase vapeur, la matière première utilisée étant un composé de nitrure de silicium organique (par exemple un des composés représentés par les formules générales (1) à (3)). La structure dudit composé présente au moins un atome d'hydrogène directement lié à un atome de silicium et au moins un atome d'hydrogène directement lié à un atome d'azote. Le film d'étanchéité ainsi formé est utilisé pour former un élément de protection contre les gaz, un dispositif FPD, un dispositif à semi-conducteur et similaires.
PCT/JP2011/068974 2010-08-27 2011-08-23 Matériau de film d'étanchéité, film d'étanchéité et son utilisation WO2012026464A1 (fr)

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