WO2012029709A1 - Amorphous silicon nitride film and method for producing same - Google Patents

Amorphous silicon nitride film and method for producing same Download PDF

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WO2012029709A1
WO2012029709A1 PCT/JP2011/069433 JP2011069433W WO2012029709A1 WO 2012029709 A1 WO2012029709 A1 WO 2012029709A1 JP 2011069433 W JP2011069433 W JP 2011069433W WO 2012029709 A1 WO2012029709 A1 WO 2012029709A1
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film
silicon nitride
amorphous silicon
nitride film
sinx
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PCT/JP2011/069433
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French (fr)
Japanese (ja)
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智子 上野
鈴木　正康
小西　善之
東　和文
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株式会社島津製作所
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Priority to CN2011800409395A priority Critical patent/CN103119197A/en
Priority to JP2012531862A priority patent/JPWO2012029709A1/en
Priority to KR1020137004182A priority patent/KR20130057460A/en
Publication of WO2012029709A1 publication Critical patent/WO2012029709A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1868—Passivation
    • 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
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • 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
    • C23C16/44—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 method of coating
    • C23C16/50—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 method of coating using electric discharges
    • C23C16/511—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 method of coating using electric discharges using microwave discharges
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an amorphous silicon nitride film having a high water vapor barrier property and a method for producing the same.
  • organic electronics In recent years, the progress of organic electronics has been remarkable, and light emitting devices represented by organic EL, organic thin-film solar cells, organic thin-film transistors, etc. are showing wide spread.
  • organic electronics composed of these organic materials, in combination with plastic substrates are responding to needs that take advantage of the characteristics of organic materials such as light weight, impact resistance, and flexibility.
  • the plastic substrate has lower water vapor and gas barrier properties than the conventional glass substrate, and water and oxygen cause fatal deterioration particularly with respect to organic materials.
  • This barrier thin film needs to be formed at a low temperature due to the limitation of the heat-resistant temperature of the plastic substrate, but conventionally, a SiO 2 film is generally formed by a sputtering method (see, for example, Patent Document 1). However, at present, the barrier performance necessary for improving the reliability to the glass substrate level has not been obtained.
  • organic EL display elements are attracting attention as the next technology for liquid crystal display elements.
  • oxidation at the organic layer and the electrode interface in contact with the organic layer leads to serious deterioration in display performance. Therefore, a very high barrier property of 10-5 g / m2 / day level is required as the water vapor transmission rate.
  • the organic layer to be used has a low glass transition temperature of 100 ° C. or lower, a thin film that can be formed at a low temperature and has high barrier properties is desired.
  • the above barrier film needs to have high light transmittance.
  • a barrier film having high light transmittance is indispensable.
  • SiNx film An amorphous silicon nitride film (hereinafter referred to as SiNx film) used for a semiconductor passivation film or the like is generally formed by a plasma CVD method using a capacitively coupled parallel plate RF plasma or the like.
  • the temperature is usually about 350 ° C.
  • the reason why the temperature at the time of formation is high is that in the low-temperature formation SiNx film, the water vapor barrier property is lowered due to the oxidation of the film after the formation, so that the water vapor barrier property is maintained by increasing the formation temperature. .
  • a low-temperature formation SiNx film having a high barrier property has been developed, there is no single film having both a barrier property and a light transmittance, only a colored film having a low light transmittance.
  • Patent Documents 2 and 3 are cited as means for obtaining a high water vapor barrier property by laminating low-temperature-formed SiNx films having different compositions.
  • Patent Document 2 describes Si—N, Si—H, and N—H spectra measured at a low temperature of 200 ° C. or less by a Si / N element ratio in a film or Fourier transform infrared spectroscopy (FTIR method).
  • FTIR method Fourier transform infrared spectroscopy
  • Patent Document 3 films having different bond density ratios are laminated continuously or stepwise from the substrate side based on the correlation between the NH / Si—H bond density ratio calculated from the peak area of the FTIR spectrum and the stress. is doing. As a result, the stress of the laminated film is reduced and a high water vapor barrier property is obtained. As a guideline for the film quality, a guideline that the hydrogen content should be reduced is shown.
  • Patent Document 2 in order to obtain moisture resistance under high temperature and high humidity, a silicon nitride layer having a large Si / N ratio and high oxidation resistance is provided.
  • a large Si / N ratio means that the light transmittance is low.
  • a high barrier property and a high optical transparency are achieved by stacking with a film having a small Si / N ratio and being easily oxidized but having a high light transmittance. Since such a laminated structure complicates the manufacturing process, the manufacturing throughput and cost are deteriorated.
  • Patent Document 3 since it is a continuous or stepwise laminated structure, it is considered that not only the manufacturing process is complicated, but also film quality reproducibility is deteriorated.
  • Patent Document 3 shows a guideline for hydrogen content, but the hydrogen content is the sum of each hydrogen bond calculated from the peak area of the FTIR spectrum.
  • the bond density calculated from the peak area of the FTIR spectrum is not necessarily accurate as will be described later.
  • the amorphous silicon nitride film formed by conventional plasma CVD shows a vague direction that the hydrogen content needs to be lowered in order to improve the moisture resistance, but the film A clear correlation between composition and film structure and moisture resistance is not shown, and a silicon nitride film having both barrier properties and light transmission properties could not be stably formed at a low temperature.
  • the hydrogen concentration in the film has been measured by Fourier transform infrared spectroscopy (FTIR method). For example, in the Si-Nasymmetric stretching mode region around 830 cm ⁇ 1 which is a typical spectrum of SiN, (SiH2 ) Or (SiH2) n absorption due to the bending mode overlaps, so the hydrogen content cannot be defined only by the peak intensity ratio.
  • the hydrogen content calculated by the FTIR method is not sufficiently accurate, the measurement result can only show a vague direction for improving the moisture resistance of the amorphous silicon nitride film.
  • an amorphous silicon nitride film having moisture resistance that can withstand practical use has not yet been obtained under film forming conditions at a low temperature that can be used as a barrier film on the view site side of an organic EL element.
  • the inventor of the present invention has studied the hydrogen concentration in the amorphous silicon nitride film measured by the Rutherford backscattering (RBS) method and the Rutherford forward scattering (HFS) method, and the water vapor of the amorphous silicon nitride film.
  • An amorphous silicon nitride film having water vapor permeability that can withstand practical use is found by finding that there is a clear correlation in permeability and forming the hydrogen concentration in the film to be a predetermined value or less.
  • an amorphous silicon nitride film formed using a surface wave plasma CVD apparatus under a predetermined condition has a hydrogen concentration in the film that is not more than the predetermined value.
  • an amorphous silicon nitride film formed on a film formation object at a temperature of the film formation object of 200 ° C. or less, comprising Rutherford backscattering (RBS) And hydrogen concentration in the amorphous silicon nitride film measured by Rutherford forward scattering (HFS) method is 25 atm% or less.
  • a method for forming an amorphous silicon nitride film using a surface wave plasma CVD apparatus wherein SiH 4 gas and NH 3 gas are used as film forming gases.
  • the temperature of the film formation target is adjusted so that the amorphous silicon nitride film is formed at a temperature of 200 ° C. or less, and the distance between the dielectric window of the surface wave plasma CVD apparatus and the film formation target Is set to a predetermined value of 175 mm or more.
  • the N / (Si + N) ratio of the formed amorphous silicon nitride film is substantially 0. It is preferable to adjust the flow rate ratio of SiH 4 gas and NH 3 gas released from the film forming gas outlet as the film forming gas for forming the amorphous silicon nitride film so as to be .6.
  • the amorphous silicon nitride film formed by using the amorphous silicon nitride film forming method according to any one of the second to third aspects The hydrogen concentration in the film is 25 atm% or less.
  • the method for forming the amorphous silicon nitride film of the first aspect or the amorphous silicon nitride film of any one of the second to third aspects is used.
  • This is a semiconductor device provided with a passivation film made of an amorphous silicon nitride film.
  • a gas barrier thin film of an amorphous silicon nitride film (SiNx film) having high water vapor barrier properties and high light transmittance can be obtained under low temperature film formation conditions.
  • FIG. 1 is a schematic vertical sectional view of a plasma CVD apparatus used in the present invention.
  • the hydrogen concentration in the film is shown.
  • the hydrogen concentration in the film is measured by Rutherford forward scattering (HFS) method and Rutherford backscattering (RBS) method.
  • FIG. 2 shows the relationship between the ratio of the sum of the bond density of hydrogen bonds (NH and SiH) measured by the FTIR method and the SiN bond density, and the gap and the substrate temperature for the SiNx film measured in FIG.
  • the relationship between the water vapor permeability of the SiNx film formed by the SiNx film forming method of the present invention and the hydrogen concentration in the film is shown.
  • the water vapor permeability is measured by the Mocon method and the Ca corrosion method.
  • the relationship between the water vapor permeability of the SiNx film formed by the SiNx film forming method of the present invention and the N / (Si + N) ratio in the film is shown. Note that the measurement points (a) to (d) in the figure correspond to the measurement points (a) to (d) in FIG.
  • the relationship between the hydrogen concentration in the SiNx film formed by the SiNx film forming method of the present invention and the gap is shown.
  • the surface wave plasma CVD apparatus used for forming the barrier film of the present invention a known apparatus is used (for example, see Japanese Patent Application Laid-Open No. 2004-335127).
  • the microwave generated by the microwave generator (not shown) is conveyed by the microwave waveguide 1 and reaches the dielectric window 3 through the slot antenna 2. This microwave is introduced into the reaction chamber 4 through the dielectric window, and becomes a surface wave that propagates along the surface of the dielectric window 3.
  • Ar gas is discharged from the discharge gas outlet 5 into the reaction chamber 4, and the Ar gas is excited by a surface wave propagating along the surface of the dielectric window, so that plasma 6 is formed near the surface of the dielectric window. .
  • the plasma 6 contains excited Ar and radicals, which diffuse into the reaction chamber 4 from the surface wave plasma generated near the dielectric window.
  • a film forming gas blowing provided between the discharge gas blowing outlet 5 and a film formation target 9 (a sealing material such as a substrate or a plastic film, which is a semiconductor substrate in the example of FIG. 1).
  • a film-forming gas composed of SiH 4 and NH 3 is released from the port 7, and these film-forming gases are dissociated by excited argon and radicals, and SiN x is generated and deposited on the substrate 9 to form a SiN x film.
  • a substrate 9 as a film formation target is placed on a stage 8 and heated by a heater 10 incorporated in the stage 8 for each stage as necessary.
  • the reaction chamber 4 is evacuated by a vacuum pump (not shown) connected via the exhaust port 11.
  • the gas pressure in the reaction chamber is controlled by the supply amount of the discharge gas and the film forming gas and the exhaust of the vacuum pump.
  • the discharge gas outlet 5 and the film forming gas outlet 7 are connected to a gas supply device (not shown) provided outside the reaction chamber 4.
  • the distance between the stage 8 and the surface wave plasma generated in the vicinity of the dielectric window can be varied by adjusting the stage position in the height direction of the reaction chamber 4 using a lifting device (not shown).
  • SiNx amorphous silicon nitride
  • a surface wave plasma CVD apparatus is used to form a barrier film made of SiNx.
  • SiNx is generated by the reaction of silane (SiH4) gas and ammonia (NH3) gas, which are the materials, with excited Ar and radicals generated by surface wave plasma. It can be performed at a location away from the plasma. Therefore, a SiNx barrier film can be formed on a substrate at a low temperature by installing a substrate at a location distant from the surface wave plasma generation region and forming a SiNx barrier film on the substrate. it can.
  • the stage position is adjusted by using the above-described lifting device, and the temperature of the substrate placed on the stage is adjusted to 200 ° C. or lower to generate a SiNx barrier film. be able to.
  • the method for producing an amorphous silicon nitride film according to the present invention is mainly intended to produce SiNx having a specific hydrogen concentration in a film at a low temperature of 200 ° C. or lower.
  • An apparatus other than the surface wave plasma CVD apparatus may be used as long as it can generate SiNx having a specific hydrogen concentration in the film at a low temperature.
  • the substrate surface temperature is low, so that sufficient kinetic energy is not given to the surface during film formation, and the unstable film structure is easily oxidized after film formation. It is easy to become. Further, since the substrate temperature is low, many Si—H and N—H bonds remain in the film, and hydrogen in the film exists at several tens% or more.
  • a SiNx film generated by plasma CVD may contain hydrogen up to several tens of percent, and it is necessary to analyze the film composition and film structure including not only Si and N but also H.
  • the conductance of the exhaust port 11 was adjusted so that the gas pressure of these gases was 10 Pa.
  • the microwave power of the applied microwave is 700 W, and the power density of the microwave in this case is 1.59 W / cm 2.
  • the processing time was adjusted so that the film thickness to be formed was approximately 200 nm.
  • the SiNx film formed at the flow rate ratio (35 sccm: 250 sccm) of SiH 4 gas and NH 3 gas described above has the highest transmittance in visible light (transmittance of about 95%). Therefore, the flow rate of such a film forming gas is set (see Japanese Patent Application No. 2010-101056).
  • FIG. 2 shows the hydrogen concentration (atm%) in the SiNx film formed by SWP-CVD under the above conditions.
  • the hydrogen content is reduced from 40% to 25% by raising the substrate temperature from 100 ° C. to 230 ° C.
  • the decrease in the hydrogen concentration in the film is thought to be due to an increase in the rate of hydrogen desorption in the substrate surface reaction as the substrate temperature increases.
  • the hydrogen content in the SiNx film formed by SWP-CVD with a gap of 200 mm is almost constant regardless of the substrate temperature, and even when the substrate temperature is as low as about 120 ° C. (the leftmost of the three measurement points in the figure). It is as low as 20% or less.
  • the hydrogen content in the film is about 30%. From these, it can be seen that the hydrogen content when the film is formed by SWP-CVD with a gap of 200 mm is very low.
  • the hydrogen concentration in the film is about 30% even though the substrate temperature is as low as about 100 ° C.
  • membrane by this invention has measured the hydrogen concentration in the film
  • RBS Rutherford backscattering
  • HFS Rutherford forward scattering
  • FIG. 3 shows the bond density ratio calculated from the FTIR spectrum area of the same SiNx film as shown in FIG. 2 measured by the FTIR method.
  • the bond density ratio is obtained by dividing the sum of the bond density of N—H and Si—H, which is the sum of hydrogen bonds in the SiNx film, by the SiN bond density. This ratio is proportional to the hydrogen concentration, but is inaccurate as a method for measuring the hydrogen concentration in the film, and the measurement results of the Rutherford backscattering (RBS) method and Rutherford forward scattering (HFS) method used in the present invention. Often different measurement results are obtained.
  • RBS Rutherford backscattering
  • HFS Rutherford forward scattering
  • the measurement results by the Rudford backscattering (RBS) method and Rutherford forward scattering (HFS) method in FIG. 3 are greatly different in relative relationship with SiNx according to the present invention.
  • the hydrogen concentration in the film formed by the parallel plate type plasma CVD apparatus (substrate temperature 100 ° C.) is lower than that formed by the present invention (Gap 150 mm, substrate temperature 150 ° C.).
  • the relationship shown in FIG. 2 is reversed at the point corresponding to the bond density ratio of FIG.
  • FIG. 4 shows the relationship between the water vapor permeability of the SiNx film and the hydrogen concentration in the film
  • FIG. 5 shows the relation between the water vapor permeability and the N / (Si + N) ratio in the film.
  • the hydrogen concentration in the film and the N / (Si + N) ratio in the film were measured by the Rutherford backscattering (RBS) method and the Rutherford forward scattering (HFS) method, and the water vapor permeability was measured by the Mocon method and the Ca corrosion method.
  • 4A to 4D correspond to FIGS. 5A to 5D and show the measurement results of the SiNx films formed at the substrate temperature of about 100 ° C.
  • FIG. 4A to 4D correspond to FIGS. 5A to 5D and show the measurement results of the SiNx films formed at the substrate temperature of about 100 ° C.
  • FIG. 5 shows the measurement results of the SiNx films formed at the substrate temperature of about 100 ° C.
  • (a) to (c) are SiNx films formed on one side of a polyimide film having a thickness of 50 ⁇ m (single stacked layer), (a) and (b) are Gap 150 mm, and (c) is The film was formed with a gap of 200 mm.
  • the film thickness is 200 nm for (a) and 1 ⁇ m for (b) and (c).
  • a 1 ⁇ m SiNx film (double stacked layer) is formed on both sides of a polyimide film with a gap of 200 mm.
  • the polyimide film is a base material of the SiNx film when measured by the Mocon method and the Ca corrosion method, and the water vapor permeability is sufficiently high, that is, the presence or absence of the polyimide film affects the measurement result of the water vapor permeability. Absent.
  • the water vapor transmission rate decreases as the hydrogen concentration in the film decreases. That is, it turns out that water vapor
  • the N / (Si + N) ratio is approximately 0.6, which is a substantially constant value.
  • a SiNx film having a composition having a high water vapor barrier property with a water vapor permeability of 10 ⁇ 3 g / m 2 / day or less is obtained.
  • the N / (Si + N) ratio is about 0.6, and the film It can be seen that the intermediate hydrogen concentration is 25% or less.
  • the N / (Si + N) ratio is constant at about 0.6 because the ratio is determined by the flow rate ratio of SiH4 gas and NH3 gas.
  • this result also shows the stability of the film forming method of the present invention.
  • the SiNx film having high visible light transmittance is stably generated as described above.
  • (d) shows a 1 ⁇ m SiNx film formed on both sides of the polyimide film, and the thickness of the SiNx film is 2 ⁇ m on both sides.
  • the thickness of the entire SiNx film is the same as (b) and (c), but the water vapor permeability is 1 ⁇ 10-5 g / m2 / day, which is below the measurement limit by the Ca corrosion method. Yes.
  • the polyimide film on which the SiNx film is formed is warped due to a temperature rise during the film formation, or film stress is applied only to the formed one side. The polyimide film is deformed and the SiNx film is easily cracked.
  • the measured value of water vapor permeability may increase due to cracks, that is, the barrier property may deteriorate.
  • SiNx films are formed on both sides of the polyimide film, such warpage and cracks are unlikely to occur, so that the original water vapor permeability measurement result of the film can be obtained.
  • a plastic substrate or a glass substrate is used, and even if a SiNx film is formed on only one side, these substrates do not warp or deform.
  • the measured value of water vapor permeability in the case of (d) in which the SiNx film is formed on both surfaces of the polyimide film as described above is equivalent to that in the case where the SiNx film is formed on an actual plastic substrate or glass substrate. It is considered to be a characteristic.
  • FIG. 6 shows the relationship between the hydrogen concentration in the film and the gap more clearly.
  • the hydrogen concentration in the SiNx film formed by changing the gap from 150 mm to 250 mm at a substrate temperature of about 100 ° C. was measured.
  • the hydrogen concentration in the film is as low as 20% or less and is almost constant, although the substrate temperature is as low as about 100 ° C.
  • the hydrogen concentration in the film can be increased even if the substrate temperature is as low as about 100 ° C. if the gap is 175 mm or more. It is possible to stably form a SiNx film having a thickness of 20% or less.
  • an object of the present invention is to form a SiNx film having a low water vapor permeability, that is, a high water vapor barrier property, as stably as possible at a low temperature.
  • a SiNx film can be formed by using a SWP-CVD apparatus. By increasing the distance between the plasma generated in the SWP-CVD apparatus and the substrate, that is, Gap, the SiNx film having a reduced hydrogen concentration in the film at a low temperature of 100 ° C. or less is formed with a stable composition. can do.
  • the film can be formed at such a low temperature, an SiNx film having a high water vapor barrier property can be formed on the organic material without damaging the organic material, and a liquid crystal display element or an organic EL display can be formed.
  • the present invention can be widely applied to light emitting elements such as elements and circuits including these elements.
  • a SiNx film having a desired N / (Si + N) ratio can be formed by changing the flow ratio of SiH4 gas and NH3 gas used as a film forming gas.
  • the transmittance of visible light is best when the N / (Si + N) ratio is about 0.6 (the transmittance is about 95%).
  • the SiNx film in which the hydrogen concentration in the film is reduced can be formed with a stable composition at a temperature of 100 ° C. or lower.
  • the SiNx film forming method of the present invention can also be applied in a temperature environment exceeding 100 ° C. In the case where film formation can be performed at a higher temperature depending on the substrate 9 or material used for film formation, the temperature can be adjusted by adjusting the heater 10 incorporated in the stage 8.
  • the parameters (substrate temperature, gap, microwave power, film forming gas flow rate) in the film forming conditions of the film forming method of the present invention described above are the devices such as the substrate or organic material to be formed.
  • Various modifications can be made in accordance with the heat resistance of the base material and material. Therefore, the film forming method of the present invention is not limited to the above-described examples, and various embodiments are possible within the scope of the present invention.
  • the SiNx film having a high water vapor barrier property using the film forming method of the present invention can be used as a sealing film for various devices, and is particularly suitable for a device that needs to be formed at a low temperature of 200 ° C. or lower. Can be applied. Furthermore, a SiNx film having a high water vapor barrier property can be formed on a material that cannot withstand high temperatures such as organic EL. Such a low-temperature formation SiNx film having a high water vapor barrier property can be used for sealing various flexible devices. In particular, when the sealing film requires transparency, the SiNx film of the present invention is extremely useful.
  • the SiNx film according to the present invention as described above can be used as a passivation film or a sealing film of a semiconductor device including, for example, an organic electroluminescent element, an organic transistor, an organic solar battery, a liquid crystal display element, electronic paper, an LED, and the like.
  • a semiconductor device including, for example, an organic electroluminescent element, an organic transistor, an organic solar battery, a liquid crystal display element, electronic paper, an LED, and the like.

Abstract

The amorphous silicon nitride film of the present invention is formed on a film formation object using a surface-wave plasma CVD apparatus. The amorphous silicon nitride film is formed under conditions where the distance between the dielectric window of the surface-wave plasma CVD apparatus and the film formation object is 175 mm or more and the temperature of the film formation object is 200°C or lower. The hydrogen concentration in the amorphous silicon nitride film is 25 atm% or lower as measured by the Rutherford backscattering spectrometry (RBS) method and the hydrogen forward scattering spectrometry (HFS) method.

Description

非晶質窒化珪素膜およびその製造方法Amorphous silicon nitride film and manufacturing method thereof
　本発明は、高水蒸気バリア性を有する非晶質窒化珪素膜およびその製造方法に関する。 The present invention relates to an amorphous silicon nitride film having a high water vapor barrier property and a method for producing the same.
　近年有機エレクトロニクスの進展が目覚ましく、有機ＥＬに代表される発光素子、有機薄膜太陽電池や有機薄膜トランジスタなど幅広い広がりを見せている。特にこれら有機材料から構成される有機エレクトロニクスでは、プラスチック基板との組み合わせで、軽量、耐衝撃性、フレキシブルといった有機材料の特長を活かしたニーズに応えようとしている。ここでプラスチック基板は従来のガラス基板と比較して水蒸気およびガスバリア性が低く、特に有機材料に対して水や酸素は致命的な劣化の原因となる。プラスチック基板を用いたこれら有機エレクトロニクスにおいては、よりバリア性の高い膜との組み合わせでデバイスを構成する必要がある。 In recent years, the progress of organic electronics has been remarkable, and light emitting devices represented by organic EL, organic thin-film solar cells, organic thin-film transistors, etc. are showing wide spread. In particular, organic electronics composed of these organic materials, in combination with plastic substrates, are responding to needs that take advantage of the characteristics of organic materials such as light weight, impact resistance, and flexibility. Here, the plastic substrate has lower water vapor and gas barrier properties than the conventional glass substrate, and water and oxygen cause fatal deterioration particularly with respect to organic materials. In these organic electronics using a plastic substrate, it is necessary to configure a device in combination with a film having a higher barrier property.
　液晶表示素子においてもフレキシブル基板の要求が高まり、用いる基板としてガラスからより軽量で耐衝撃性の高いフレキシブルなプラスチック基板に置き換えようとする傾向がある。しかしながら、プラスチック基板では水や酸素等の透過率がガラス基板に比べて非常に高く、そのために液晶中に外部から不純物が混入して表示特性が劣化するという問題がある。この対策として、プラスチック基板の両面に水や酸素等を通しにくくするためのバリア薄膜を形成する検討が行われている。このバリア薄膜はプラスチック基板の耐熱温度の制約から、低温形成が必要であるが、従来はスパッタリング法によるＳｉＯ２膜を形成することが一般的である（例えば特許文献１参照）。しかしながら、現状ではガラス基板レベルにまで信頼性を向上させるために必要なバリア性能が得られていない。 Demand for flexible substrates in liquid crystal display elements also increases, and there is a tendency to replace glass with a flexible plastic substrate that is lighter and has higher impact resistance. However, a plastic substrate has a very high transmittance of water, oxygen, and the like compared to a glass substrate, and therefore, there is a problem that impurities are mixed into the liquid crystal from the outside and display characteristics deteriorate. As a countermeasure, studies have been made to form a barrier thin film that makes it difficult to pass water, oxygen, or the like on both surfaces of a plastic substrate. This barrier thin film needs to be formed at a low temperature due to the limitation of the heat-resistant temperature of the plastic substrate, but conventionally, a SiO 2 film is generally formed by a sputtering method (see, for example, Patent Document 1). However, at present, the barrier performance necessary for improving the reliability to the glass substrate level has not been obtained.
　また、液晶表示素子の次の技術として有機ＥＬ表示素子が注目されている。この有機ＥＬ表示素子では、有機層やそれに接する電極界面での酸化が、深刻な表示性能劣化につながるため、水蒸気透過率として、１０－５ｇ／ｍ２／ｄａｙレベルの非常に高いバリア性が要求される。また、用いる有機層はガラス転移温度が１００℃以下と低いため、低温で形成でき、かつ高いバリア性を有する薄膜が望まれている。 Also, organic EL display elements are attracting attention as the next technology for liquid crystal display elements. In this organic EL display element, oxidation at the organic layer and the electrode interface in contact with the organic layer leads to serious deterioration in display performance. Therefore, a very high barrier property of 10-5 g / m2 / day level is required as the water vapor transmission rate. The Further, since the organic layer to be used has a low glass transition temperature of 100 ° C. or lower, a thin film that can be formed at a low temperature and has high barrier properties is desired.
　更に、液晶表示素子や有機ＥＬ表示素子などの発光素子およびこれらを含む回路においては、上記のバリヤ膜は光透過性が高いことが必要である。例えば上記の有機ＥＬ表示素子で特にトップエミッション方式のものにおいて、プラスチック基板による封止を行う場合は、光透過性の高いバリヤ膜が不可欠となる。 Furthermore, in a light emitting element such as a liquid crystal display element or an organic EL display element and a circuit including these elements, the above barrier film needs to have high light transmittance. For example, in the case of the above-mentioned organic EL display element, particularly in a top emission type, when sealing with a plastic substrate, a barrier film having high light transmittance is indispensable.
　半導体用パッシベーション膜などに用いられている非晶質窒化ケイ素膜（以下、ＳｉＮｘ膜）は、一般的に容量結合型平行平板ＲＦプラズマなどを利用したプラズマＣＶＤ法により形成され、形成時の温度は通常３５０℃程度の高温である。形成時の温度が高温である理由は、低温形成ＳｉＮｘ膜では形成後に膜が酸化することにより水蒸気バリア性が低下するため、形成温度を高温とすることにより、水蒸気バリア性を維持するためである。近年、高バリア性を有する低温形成ＳｉＮｘ膜も開発されてはいるものの、光透過性の低い着色している膜のみで、単膜でバリア性と光透過性とを両立させたものはない。 An amorphous silicon nitride film (hereinafter referred to as SiNx film) used for a semiconductor passivation film or the like is generally formed by a plasma CVD method using a capacitively coupled parallel plate RF plasma or the like. The temperature is usually about 350 ° C. The reason why the temperature at the time of formation is high is that in the low-temperature formation SiNx film, the water vapor barrier property is lowered due to the oxidation of the film after the formation, so that the water vapor barrier property is maintained by increasing the formation temperature. . In recent years, although a low-temperature formation SiNx film having a high barrier property has been developed, there is no single film having both a barrier property and a light transmittance, only a colored film having a low light transmittance.
　先行技術として、組成の異なる低温形成ＳｉＮｘ膜を積層することにより、高水蒸気バリア性を得る手段として、特許文献２および３が挙げられる。
　特許文献２は、形成温度２００℃以下の低温において、膜中のＳｉ／Ｎ元素比やフーリエ変換赤外分光分析法で測定した（ＦＴＩＲ法）Ｓｉ－Ｎ、Ｓｉ－Ｈ、Ｎ－Ｈスペクトルのピーク強度比をある範囲に規定した膜を積層することにより、積層膜の耐酸化性を高め
、高水蒸気バリア性を得ると共に、高光学透過性を両立させるというものである。すなわち、基板温度２００℃以下で光透過性が８０％以上のバリア膜を、積層構造により実現している。
　特許文献３は、ＦＴＩＲスペクトルのピーク面積から算出したＮ－Ｈ／Ｓｉ－Ｈ結合密度比と応力の相関関係を基に、結合密度比の異なる膜を、基板側から連続的または段階的に積層している。これにより、積層膜の応力を低減し、高水蒸気バリア性を得るというものであり、膜質の指針として、水素含有量を少なくすべきという指針が示されている。 As prior art, Patent Documents 2 and 3 are cited as means for obtaining a high water vapor barrier property by laminating low-temperature-formed SiNx films having different compositions.
Patent Document 2 describes Si—N, Si—H, and N—H spectra measured at a low temperature of 200 ° C. or less by a Si / N element ratio in a film or Fourier transform infrared spectroscopy (FTIR method). By laminating films whose peak intensity ratio is defined within a certain range, the oxidation resistance of the laminated film is improved, high water vapor barrier properties are obtained, and high optical transparency is compatible. That is, a barrier film having a light transmittance of 80% or more at a substrate temperature of 200 ° C. or less is realized by a laminated structure.
In Patent Document 3, films having different bond density ratios are laminated continuously or stepwise from the substrate side based on the correlation between the NH / Si—H bond density ratio calculated from the peak area of the FTIR spectrum and the stress. is doing. As a result, the stress of the laminated film is reduced and a high water vapor barrier property is obtained. As a guideline for the film quality, a guideline that the hydrogen content should be reduced is shown.
特開平１１－２５６３３８号公報JP 11-256338 A 特開２００８－２１４６７７号公報JP 2008-214677 A 特開平６－２９１１１４号公報JP-A-6-291114
　特許文献２では、高温高湿下での耐湿性を得るために、Ｓｉ／Ｎ比の大きい耐酸化性の高い窒化シリコン層を設けている。しかしながら、Ｓｉ／Ｎ比が大きいということは、すなわち、光透過性が低いことを意味する。このため特許文献２では、Ｓｉ／Ｎ比が小さい、酸化されやすいが光透過性の高い膜と積層することで、高バリア性と高光学透過性を両立している。このような積層構造は製造工程を複雑にするため、製造のスループットやコストを悪化させることになる。
　特許文献３においても連続的または段階的な積層構造である為、製造工程の複雑化のみならず、膜質再現性の悪化に繋がると考えられる。 In Patent Document 2, in order to obtain moisture resistance under high temperature and high humidity, a silicon nitride layer having a large Si / N ratio and high oxidation resistance is provided. However, a large Si / N ratio means that the light transmittance is low. For this reason, in Patent Document 2, a high barrier property and a high optical transparency are achieved by stacking with a film having a small Si / N ratio and being easily oxidized but having a high light transmittance. Since such a laminated structure complicates the manufacturing process, the manufacturing throughput and cost are deteriorated.
Also in Patent Document 3, since it is a continuous or stepwise laminated structure, it is considered that not only the manufacturing process is complicated, but also film quality reproducibility is deteriorated.
　特許文献３では、水素含有量の指針が示されているが、水素含有量はＦＴＩＲスペクトルのピーク面積から算出した各水素結合の総和である。ＦＴＩＲスペクトルのピーク面積から算出された結合密度は、後述するように、必ずしも正確であるとは言いがたい。 Patent Document 3 shows a guideline for hydrogen content, but the hydrogen content is the sum of each hydrogen bond calculated from the peak area of the FTIR spectrum. The bond density calculated from the peak area of the FTIR spectrum is not necessarily accurate as will be described later.
　このように、従来のプラズマＣＶＤにより成膜される非晶質窒化珪素膜では、耐湿性を高めるために、水素含有率を低下させる必要があるという漠然とした方向性は示されているものの、膜組成及び膜構造と耐湿性との明確な相関については示されておらず、バリア性と光透過性を両立した窒化珪素膜を低温でかつ安定に成膜することができなかった。
　つまり、膜中水素濃度はフーリエ変換赤外分光分析法（ＦＴＩＲ法）で測定されてきたが、例えばＳｉＮの代表的なスペクトルである８３０ｃｍ－１付近のＳｉ－Ｎasymmetric　stretching mode領域には、（ＳｉＨ２）または（ＳｉＨ２）ｎのbending modeによる吸収が重なるため、ピーク強度比だけで水素含有率を規定することはできない。さらに、ＦＴＩＲスペクトルにピーク面積から水素含有量を算出する場合も、算出式の係数に膜の屈折率をパラメータとして入力する必要があり、膜の組成によって屈折率が変化しうるＳｉＮｘ膜において係数は一意に定まらず、算出した水素含有率は正確ではない。この様に、ＦＴＩＲ法によって算出された水素含有率では、その測定結果の正確性は充分でないため、非晶質窒化珪素膜の耐湿性を高めるための漠然とした方向性を示すことができるのみであり、実質的には様々な成膜条件を変更して最適な条件を模索するほか無い。殊に、有機ＥＬ素子のビュウサイト側のバリア膜として使用できるような低温での成膜条件において、実用に耐え得る耐湿性を備えた非晶質窒化珪素膜は未だ得られていない。 As described above, the amorphous silicon nitride film formed by conventional plasma CVD shows a vague direction that the hydrogen content needs to be lowered in order to improve the moisture resistance, but the film A clear correlation between composition and film structure and moisture resistance is not shown, and a silicon nitride film having both barrier properties and light transmission properties could not be stably formed at a low temperature.
In other words, the hydrogen concentration in the film has been measured by Fourier transform infrared spectroscopy (FTIR method). For example, in the Si-Nasymmetric stretching mode region around 830 cm−1 which is a typical spectrum of SiN, (SiH2 ) Or (SiH2) n absorption due to the bending mode overlaps, so the hydrogen content cannot be defined only by the peak intensity ratio. Furthermore, when calculating the hydrogen content from the peak area in the FTIR spectrum, it is necessary to input the refractive index of the film as a parameter in the coefficient of the calculation formula. In the SiNx film whose refractive index can change depending on the composition of the film, the coefficient is It is not uniquely determined and the calculated hydrogen content is not accurate. Thus, since the hydrogen content calculated by the FTIR method is not sufficiently accurate, the measurement result can only show a vague direction for improving the moisture resistance of the amorphous silicon nitride film. There are practically no choice but to search for optimum conditions by changing various film forming conditions. In particular, an amorphous silicon nitride film having moisture resistance that can withstand practical use has not yet been obtained under film forming conditions at a low temperature that can be used as a barrier film on the view site side of an organic EL element.
　本願発明の発明者は鋭意検討の結果、ラザフォード後方散乱（ＲＢＳ）法およびラザフォード前方散乱（ＨＦＳ）法で測定した非晶質窒化珪素膜の膜中水素濃度と、該非晶質窒化珪素膜の水蒸気透過度に明確な相関が存在することを見出し、この膜中水素濃度を所定
の値以下となるように成膜することによって、実用に耐え得る水蒸気透過度を具備する非晶質窒化珪素膜が得られることを見出した、更に、表面波プラズマＣＶＤ装置を所定の条件で使用して成膜した非晶質窒化珪素膜は、上記所定の値以下の膜中水素濃度となることを見出した。
　つまり、
（１）本発明の第１の態様によると、成膜対象物の温度が２００℃以下で成膜対象物上に成膜された非晶質窒化珪素膜であって、ラザフォード後方散乱（ＲＢＳ）法および、ラザフォード前方散乱（ＨＦＳ）法によって測定される非晶質窒化珪素膜の膜中水素濃度が２５ａｔｍ％以下である。
（２）本発明の第２の態様によると、表面波プラズマＣＶＤ装置を用いた非晶質窒化珪素膜の成膜方法であって、成膜ガスとしてＳｉＨ４ガスおよびＮＨ３ガスを使用し、成膜対象物の温度が２００℃以下で非晶質窒化珪素膜が成膜されるように成膜対象物の温度を調整するとともに、表面波プラズマＣＶＤ装置の誘電体窓と成膜対象物との距離を１７５ｍｍ以上の所定の値に設定して成膜する。
（３）本発明の第３の態様によると、第２の態様の非晶質窒化珪素膜の成膜方法において、成膜される非晶質窒化珪素膜のＮ／（Ｓｉ＋Ｎ）比が略０．６となるように、非晶質窒化珪素膜を成膜するための成膜ガスとして成膜ガス吹き出し口から放出するＳｉＨ４ガスおよびＮＨ３ガスの流量比を調整することが好ましい。
（４）本発明の第４の態様によると、第２乃至第３の態様のいずれか１つの態様の非晶質窒化珪素膜の成膜方法を用いて成膜された非晶質窒化珪素膜であって、膜中水素濃度が２５ａｔｍ％以下である。　
（５）本発明の第５の態様によると、第１の態様の非晶質窒化珪素膜、または第２乃至第３のいずれか１つの態様の非晶質窒化珪素膜の成膜方法を用いて成膜した非晶質窒化珪素膜からなるパッシベーション膜を備えた半導体デバイスである。 As a result of intensive studies, the inventor of the present invention has studied the hydrogen concentration in the amorphous silicon nitride film measured by the Rutherford backscattering (RBS) method and the Rutherford forward scattering (HFS) method, and the water vapor of the amorphous silicon nitride film. An amorphous silicon nitride film having water vapor permeability that can withstand practical use is found by finding that there is a clear correlation in permeability and forming the hydrogen concentration in the film to be a predetermined value or less. Further, it has been found that an amorphous silicon nitride film formed using a surface wave plasma CVD apparatus under a predetermined condition has a hydrogen concentration in the film that is not more than the predetermined value.
In other words,
(1) According to the first aspect of the present invention, an amorphous silicon nitride film formed on a film formation object at a temperature of the film formation object of 200 ° C. or less, comprising Rutherford backscattering (RBS) And hydrogen concentration in the amorphous silicon nitride film measured by Rutherford forward scattering (HFS) method is 25 atm% or less.
(2) According to the second aspect of the present invention, there is provided a method for forming an amorphous silicon nitride film using a surface wave plasma CVD apparatus, wherein SiH 4 gas and NH 3 gas are used as film forming gases. The temperature of the film formation target is adjusted so that the amorphous silicon nitride film is formed at a temperature of 200 ° C. or less, and the distance between the dielectric window of the surface wave plasma CVD apparatus and the film formation target Is set to a predetermined value of 175 mm or more.
(3) According to the third aspect of the present invention, in the method for forming an amorphous silicon nitride film according to the second aspect, the N / (Si + N) ratio of the formed amorphous silicon nitride film is substantially 0. It is preferable to adjust the flow rate ratio of SiH 4 gas and NH 3 gas released from the film forming gas outlet as the film forming gas for forming the amorphous silicon nitride film so as to be .6.
(4) According to the fourth aspect of the present invention, the amorphous silicon nitride film formed by using the amorphous silicon nitride film forming method according to any one of the second to third aspects The hydrogen concentration in the film is 25 atm% or less.
(5) According to the fifth aspect of the present invention, the method for forming the amorphous silicon nitride film of the first aspect or the amorphous silicon nitride film of any one of the second to third aspects is used. This is a semiconductor device provided with a passivation film made of an amorphous silicon nitride film.
　本発明により、高い水蒸気バリア性を備え、かつ、光透過性の高い非晶質窒化珪素膜（ＳｉＮｘ膜）のガスバリア性薄膜を、低温の成膜条件で得ることができる。 According to the present invention, a gas barrier thin film of an amorphous silicon nitride film (SiNx film) having high water vapor barrier properties and high light transmittance can be obtained under low temperature film formation conditions.
本発明で使用したプラズマＣＶＤ装置の概略の垂直断面図である。1 is a schematic vertical sectional view of a plasma CVD apparatus used in the present invention. 図１のプラズマＣＶＤを用いた本発明のＳｉＮｘ膜の成膜方法により、誘電体窓とステージ間の距離（Ｇａｐ）が１５０ｍｍおよび２００ｍｍの場合で、それぞれステージ温度を変えて成膜されたＳｉＮｘ膜の膜中水素濃度を示す。膜中水素濃度はラザフォード前方散乱（ＨＦＳ）法およびラザフォード後方散乱（ＲＢＳ）法で測定している。The SiNx film formed by changing the stage temperature when the distance (Gap) between the dielectric window and the stage is 150 mm and 200 mm by the SiNx film forming method of the present invention using plasma CVD in FIG. The hydrogen concentration in the film is shown. The hydrogen concentration in the film is measured by Rutherford forward scattering (HFS) method and Rutherford backscattering (RBS) method. 図２で測定したＳｉＮｘ膜に対し、ＦＴＩＲ法で測定した水素結合（ＮＨおよびＳｉＨ）の結合密度の和とＳｉＮ結合密度との比、とＧａｐおよび基板温度との関係を示す。FIG. 2 shows the relationship between the ratio of the sum of the bond density of hydrogen bonds (NH and SiH) measured by the FTIR method and the SiN bond density, and the gap and the substrate temperature for the SiNx film measured in FIG. 本発明のＳｉＮｘ膜の成膜方法により成膜されたＳｉＮｘ膜の水蒸気透過度と膜中水素濃度の関係を示す。水蒸気透過度はＭｏｃｏｎ法およびＣａ腐食法で測定している。The relationship between the water vapor permeability of the SiNx film formed by the SiNx film forming method of the present invention and the hydrogen concentration in the film is shown. The water vapor permeability is measured by the Mocon method and the Ca corrosion method. 本発明のＳｉＮｘ膜の成膜方法により成膜されたＳｉＮｘ膜の水蒸気透過度と膜中Ｎ／（Ｓｉ＋Ｎ）比との関係を示す。なお、図中（ａ）～（ｄ）の測定点は図３の（ａ）～（ｄ）の測定点に対応する。The relationship between the water vapor permeability of the SiNx film formed by the SiNx film forming method of the present invention and the N / (Si + N) ratio in the film is shown. Note that the measurement points (a) to (d) in the figure correspond to the measurement points (a) to (d) in FIG. 本発明のＳｉＮｘ膜の成膜方法により成膜されたＳｉＮｘ膜の膜中水素濃度とＧａｐの関係を示す。The relationship between the hydrogen concentration in the SiNx film formed by the SiNx film forming method of the present invention and the gap is shown.
＜装置の説明＞
　以下に本発明で使用する表面波プラズマ装置の概略を、図１を用いて簡単に説明する。
なお、本発明のバリヤ膜を成膜するために用いた表面波プラズマＣＶＤ装置は公知のものを用いている（例えば特開２００４－３３５１２７号公報参照）。
　本発明で用いた表面波プラズマＣＶＤ装置では、マイクロ波発生装置（非表示）で発生されたマイクロ波がマイクロ波導波管１によって搬送され、スロットアンテナ２を通して誘電体窓３に到達する。このマイクロ波は反応室４に誘電体窓を介して導入され、誘電体窓３の表面に沿って伝播する表面波となる。放電ガス吹き出し口５から反応室４内にＡｒガスが放出され、この誘電体窓の表面に沿って伝播する表面波によってＡｒガスが励起され、誘電体窓の表面付近にプラズマ６が形成される。このプラズマ６には励起されたＡｒやラジカルが含まれており、これらは誘電体窓付近に発生した表面波プラズマから反応室４内に拡散してゆく。 <Description of the device>
An outline of the surface wave plasma apparatus used in the present invention will be briefly described below with reference to FIG.
As the surface wave plasma CVD apparatus used for forming the barrier film of the present invention, a known apparatus is used (for example, see Japanese Patent Application Laid-Open No. 2004-335127).
In the surface wave plasma CVD apparatus used in the present invention, the microwave generated by the microwave generator (not shown) is conveyed by the microwave waveguide 1 and reaches the dielectric window 3 through the slot antenna 2. This microwave is introduced into the reaction chamber 4 through the dielectric window, and becomes a surface wave that propagates along the surface of the dielectric window 3. Ar gas is discharged from the discharge gas outlet 5 into the reaction chamber 4, and the Ar gas is excited by a surface wave propagating along the surface of the dielectric window, so that plasma 6 is formed near the surface of the dielectric window. . The plasma 6 contains excited Ar and radicals, which diffuse into the reaction chamber 4 from the surface wave plasma generated near the dielectric window.
　放電ガス吹き出し口５と成膜が行われる成膜対象物９（基板またはプラスチックフィルム等の封止材であり、図１の例では半導体基板である）との間に設けられた成膜ガス吹き出し口７から、ＳｉＨ４、ＮＨ３からなる成膜ガスが放出され、励起されたアルゴンやラジカルによってこれらの成膜ガスが解離され、ＳｉＮｘが生成されて基板９に堆積してＳｉＮｘ膜が形成される。成膜対象物である基板９は、ステージ８に戴置され、必要に応じステージごと、ステージ８に組み込まれたヒーター１０で加熱される。反応室４は、排気口１１を介して接続された真空ポンプ（非表示）により真空引きされる。プラズマ発生中は、放電ガスおよび成膜ガスの供給量と真空ポンプの排気により、反応室内のガス圧が制御される。なお、放電ガス吹き出し口５と成膜ガス吹き出し口７は反応室４の外部に設けられたガス供給装置（不図示）に接続されている。
　ステージ８と誘電体窓付近に生成される表面波プラズマとの距離は、反応室４の高さ方向のステージ位置を図示しない昇降装置を用いて調整することにより可変である。 A film forming gas blowing provided between the discharge gas blowing outlet 5 and a film formation target 9 (a sealing material such as a substrate or a plastic film, which is a semiconductor substrate in the example of FIG. 1). A film-forming gas composed of SiH 4 and NH 3 is released from the port 7, and these film-forming gases are dissociated by excited argon and radicals, and SiN x is generated and deposited on the substrate 9 to form a SiN x film. A substrate 9 as a film formation target is placed on a stage 8 and heated by a heater 10 incorporated in the stage 8 for each stage as necessary. The reaction chamber 4 is evacuated by a vacuum pump (not shown) connected via the exhaust port 11. During plasma generation, the gas pressure in the reaction chamber is controlled by the supply amount of the discharge gas and the film forming gas and the exhaust of the vacuum pump. The discharge gas outlet 5 and the film forming gas outlet 7 are connected to a gas supply device (not shown) provided outside the reaction chamber 4.
The distance between the stage 8 and the surface wave plasma generated in the vicinity of the dielectric window can be varied by adjusting the stage position in the height direction of the reaction chamber 4 using a lifting device (not shown).
＜バリヤ膜の形成＞
　ここで本発明による非晶質窒化珪素（ＳｉＮｘ）膜の形成方法について説明する。
　本発明ではＳｉＮｘからなるバリヤ膜の形成に、表面波プラズマＣＶＤ装置を用いている。表面波プラズマＣＶＤ装置ではＳｉＮｘが、この材料となるシラン（ＳｉＨ４）ガスおよびアンモニア（ＮＨ３）ガスと表面波プラズマで発生した励起Ａｒやラジカルとの反応によって生成するが、このＳｉＮｘの生成を表面波プラズマから離れた場所で行うことが可能である。従って、表面波プラズマ発生領域から離れた場所に基板を設置し、この基板上にＳｉＮｘからなるバリヤ膜が形成されるようにすることにより、基板上に低温でＳｉＮｘのバリヤ膜を生成することができる。
　本発明による非晶質窒化珪素膜では上記の昇降装置を用いてステージ位置を調整し、ステージに戴置する基板の温度が２００℃以下となるように調整して、ＳｉＮｘのバリヤ膜を生成することができる。 <Formation of barrier film>
Here, a method for forming an amorphous silicon nitride (SiNx) film according to the present invention will be described.
In the present invention, a surface wave plasma CVD apparatus is used to form a barrier film made of SiNx. In the surface wave plasma CVD apparatus, SiNx is generated by the reaction of silane (SiH4) gas and ammonia (NH3) gas, which are the materials, with excited Ar and radicals generated by surface wave plasma. It can be performed at a location away from the plasma. Therefore, a SiNx barrier film can be formed on a substrate at a low temperature by installing a substrate at a location distant from the surface wave plasma generation region and forming a SiNx barrier film on the substrate. it can.
In the amorphous silicon nitride film according to the present invention, the stage position is adjusted by using the above-described lifting device, and the temperature of the substrate placed on the stage is adjusted to 200 ° C. or lower to generate a SiNx barrier film. be able to.
　しかしながら、以下に記載するように、本発明による非晶質窒化珪素膜の製造方法では特定の膜中水素濃度のＳｉＮｘを２００℃以下の低温で生成することを主たる目的とするものであり、従って低温で特定の膜中水素濃度のＳｉＮｘを生成できるものであれば表面波プラズマＣＶＤ装置以外の装置であってよい。 However, as described below, the method for producing an amorphous silicon nitride film according to the present invention is mainly intended to produce SiNx having a specific hydrogen concentration in a film at a low temperature of 200 ° C. or lower. An apparatus other than the surface wave plasma CVD apparatus may be used as long as it can generate SiNx having a specific hydrogen concentration in the film at a low temperature.
　熱ＣＶＤでは通常数百℃以上の温度で成膜が行われ、これにより成膜された窒化珪素膜では膜中水素が非常に少ない。非晶質窒化珪素の成膜では、原料ガスの表面付近での反応によって膜構造が決まるため、基板表面温度が高いと、窒化珪素膜の前駆体（ＳｉＨ４およびＮＨ３から生成されたＳｉＨｘとＮＨｘ）が表面で安定した場所に移動するための十分なエネルギーが与えられ、緻密な膜となる。同時に基板表面温度が高いためＳｉ－Ｈ、Ｎ－Ｈ結合が切れやすく、膜中水素量が少ない膜となる。また、基板表面温度が高いと膜表面への付着係数が小さくなり、膜中への酸素の混入は少なくなる。 In thermal CVD, film formation is usually performed at a temperature of several hundred degrees Celsius or higher, and the silicon nitride film formed thereby has very little hydrogen in the film. In the film formation of amorphous silicon nitride, the film structure is determined by the reaction near the surface of the source gas. Therefore, when the substrate surface temperature is high, the precursor of the silicon nitride film (SiHx and NHx generated from SiH4 and NH3) Enough energy is given to move to a stable place on the surface, and a dense film is formed. At the same time, since the substrate surface temperature is high, Si—H and N—H bonds are easily broken, resulting in a film with a small amount of hydrogen in the film. Further, when the substrate surface temperature is high, the adhesion coefficient to the film surface becomes small, and the oxygen is less mixed into the film.
　これに対して２００℃以下の低温で成膜する場合では、基板表面温度が低いために、成膜中に表面で十分な移動エネルギーが与えられず、成膜後に酸化されやすい不安定な膜構造になり易い。また、基板温度が低いため、Ｓｉ－Ｈ、Ｎ－Ｈ結合が多く膜中に残り、膜中水素は数十％以上存在する。
　一般的には、プラズマＣＶＤ（ＰＥＣＶＤ）によって生成したＳｉＮｘ膜は水素を数十％程度まで含むことがあり、ＳｉやＮだけでなくＨも含めた膜組成および膜構造を分析する必要がある。 On the other hand, when the film is formed at a low temperature of 200 ° C. or lower, the substrate surface temperature is low, so that sufficient kinetic energy is not given to the surface during film formation, and the unstable film structure is easily oxidized after film formation. It is easy to become. Further, since the substrate temperature is low, many Si—H and N—H bonds remain in the film, and hydrogen in the film exists at several tens% or more.
In general, a SiNx film generated by plasma CVD (PECVD) may contain hydrogen up to several tens of percent, and it is necessary to analyze the film composition and film structure including not only Si and N but also H.
　以下に、上記の窒化ケイ素膜の形成方法を用いて、実際に成膜した窒化ケイ素膜の特性について説明する。
　上記の表面波プラズマＣＶＤ装置（ＳＷＰＣＶＤ装置）を用い、Ａｒガスを流量１７５ｓｃｃｍとして放電ガス放出口５から放出し、ＳｉＨ４ガスおよびＮＨ３ガスはそれぞれ３５ｓｃｃｍ、２５０ｓｃｃｍとして成膜ガス放出口７から反応室４に放出した。誘電体窓とステージ間の距離（以下この距離をＧａｐと呼ぶ）は１５０ｍｍから２５０ｍｍとした。基板温度が１００℃～３００℃となるようにヒーター１０を調整した。成膜中は、これらのガスによるガス圧が１０Ｐａとなるように排気口１１のコンダクタンスを調整した。印加されたマイクロ波のマイクロ波電力は７００Ｗとし、この場合のマイクロ波の電力密度は１．５９Ｗ／ｃｍ２である。成膜される膜厚がほぼ２００ｎｍとなるように処理時間を調整した。 The characteristics of a silicon nitride film actually formed using the above-described silicon nitride film forming method will be described below.
Using the above surface wave plasma CVD apparatus (SWPCVD apparatus), Ar gas is discharged from the discharge gas discharge port 5 at a flow rate of 175 sccm, and SiH4 gas and NH3 gas are respectively set to 35 sccm and 250 sccm from the film formation gas discharge port 7 to the reaction chamber 4. Released. The distance between the dielectric window and the stage (hereinafter, this distance is referred to as Gap) was set to 150 mm to 250 mm. The heater 10 was adjusted so that the substrate temperature was 100 ° C. to 300 ° C. During the film formation, the conductance of the exhaust port 11 was adjusted so that the gas pressure of these gases was 10 Pa. The microwave power of the applied microwave is 700 W, and the power density of the microwave in this case is 1.59 W / cm 2. The processing time was adjusted so that the film thickness to be formed was approximately 200 nm.
　なお、ここでは詳述しないが、上記に示すＳｉＨ４ガスおよびＮＨ３ガスの流量比（３５ｓｃｃｍ：２５０ｓｃｃｍ）で成膜されたＳｉＮｘ膜が、可視光での透過度が最も高くなる（透過度約９５％）ことが分かっているので、このような成膜ガスの流量としている（特願２０１０－１０１０５６号公報参照）。 Although not described in detail here, the SiNx film formed at the flow rate ratio (35 sccm: 250 sccm) of SiH 4 gas and NH 3 gas described above has the highest transmittance in visible light (transmittance of about 95%). Therefore, the flow rate of such a film forming gas is set (see Japanese Patent Application No. 2010-101056).
　このように成膜されたＳｉＮｘ膜の組成をラザフォード後方散乱（ＲＢＳ）法およびラザフォード前方散乱（ＨＦＳ）法で分析するとともに、Ｃａ腐食法により水蒸気透過度を測定した。
　図２に、上記の条件のＳＷＰ－ＣＶＤで成膜したＳｉＮｘ膜の膜中水素濃度（ａｔｍ％）を示す。併せて、比較のため一般的な成膜法である、容量結合型の平行平板型プラズマＣＶＤ装置（平行平板型ＰＥ－ＣＶＤ装置）を用いた一般的なＰＥ－ＣＶＤで成膜したＳｉＮｘ膜の水素含有量を示す。 The composition of the SiNx film thus formed was analyzed by the Rutherford backscattering (RBS) method and the Rutherford forward scattering (HFS) method, and the water vapor transmission rate was measured by the Ca corrosion method.
FIG. 2 shows the hydrogen concentration (atm%) in the SiNx film formed by SWP-CVD under the above conditions. In addition, a SiNx film formed by general PE-CVD using a capacitively coupled parallel plate type plasma CVD apparatus (parallel plate type PE-CVD apparatus), which is a general film formation method for comparison. Indicates the hydrogen content.
　ＳＷＰ－ＣＶＤによりＧａｐ１５０ｍｍでＳｉＮｘ膜を成膜する場合では、基板温度を１００℃から２３０℃に上げることにより、水素含有量は４０％から２５％に低下する。膜中水素濃度の低下は、基板温度の上昇と共に、基板表面反応における水素脱離の割合が増加するためと考えられる。 In the case of forming a SiNx film with a gap of 150 mm by SWP-CVD, the hydrogen content is reduced from 40% to 25% by raising the substrate temperature from 100 ° C. to 230 ° C. The decrease in the hydrogen concentration in the film is thought to be due to an increase in the rate of hydrogen desorption in the substrate surface reaction as the substrate temperature increases.
　一方、Ｇａｐ２００ｍｍでＳＷＰ－ＣＶＤにより成膜したＳｉＮｘ膜では、水素含有量は基板温度によらずほぼ一定で、基板温度が１２０℃程度の低温（図中下の３測定点の一番左側）でも２０％以下と低くなっている。同様にＧａｐ２００ｍｍでＰＥ－ＣＶＤにより成膜した場合（図中白抜き三角のデータ）の膜中水素含有量は約３０％となっている。これらよりＧａｐ２００ｍｍでＳＷＰ－ＣＶＤによって成膜した場合の水素含有量が非常に低いことがわかる。 On the other hand, in the SiNx film formed by SWP-CVD with a gap of 200 mm, the hydrogen content is almost constant regardless of the substrate temperature, and even when the substrate temperature is as low as about 120 ° C. (the leftmost of the three measurement points in the figure). It is as low as 20% or less. Similarly, when the film is formed by PE-CVD at a gap of 200 mm (data in the white triangle in the figure), the hydrogen content in the film is about 30%. From these, it can be seen that the hydrogen content when the film is formed by SWP-CVD with a gap of 200 mm is very low.
　これに対し、平行平板型ＰＥＣＶＤ装置を用いてＳｉＮｘ膜を成膜した場合は、基板温度が約１００℃と低いにも拘わらず、膜中水素濃度は約３０％となっている。 On the other hand, when the SiNx film is formed using the parallel plate type PECVD apparatus, the hydrogen concentration in the film is about 30% even though the substrate temperature is as low as about 100 ° C.
　なお、本発明によるＳｉＮｘ膜は、その膜中水素濃度を上記のようにラザフォード後方散乱（ＲＢＳ）法およびラザフォード前方散乱（ＨＦＳ）法で測定している。 In addition, the SiNx film | membrane by this invention has measured the hydrogen concentration in the film | membrane by the Rutherford backscattering (RBS) method and the Rutherford forward scattering (HFS) method as mentioned above.
　従来は膜中水素濃度はフーリエ変換赤外分光分析法（ＦＴＩＲ法）で測定されてきたが、先述の理由から、その測定結果の正確性は充分ではなかった。
　図３に、図２で示したものと同じＳｉＮｘ膜をＦＴＩＲ法で測定し、そのＦＴＩＲスペクトル面積から算出した結合密度比を示す。結合密度比は、ＳｉＮｘ膜中の水素結合の総和であるＮ－ＨとＳｉ－Ｈの結合密度の和をＳｉＮ結合密度で割っている。この比は水素濃度と比例の関係にあるが、膜中水素濃度の測定法としては不正確であり、本発明で用いたラザフォード後方散乱（ＲＢＳ）法およびラザフォード前方散乱（ＨＦＳ）法の測定結果と異なった測定結果が得られることがしばしばある。 Conventionally, the hydrogen concentration in the film has been measured by Fourier transform infrared spectroscopy (FTIR method), but for the reasons described above, the accuracy of the measurement results has not been sufficient.
FIG. 3 shows the bond density ratio calculated from the FTIR spectrum area of the same SiNx film as shown in FIG. 2 measured by the FTIR method. The bond density ratio is obtained by dividing the sum of the bond density of N—H and Si—H, which is the sum of hydrogen bonds in the SiNx film, by the SiN bond density. This ratio is proportional to the hydrogen concentration, but is inaccurate as a method for measuring the hydrogen concentration in the film, and the measurement results of the Rutherford backscattering (RBS) method and Rutherford forward scattering (HFS) method used in the present invention. Often different measurement results are obtained.
　本発明におけるＳｉＮｘ膜の評価においても、平行平板型プラズマＣＶＤ装置で成膜したＳｉＮｘ膜に対し、図２でのザフォード後方散乱（ＲＢＳ）法およびラザフォード前方散乱（ＨＦＳ）法での測定結果と、図３でのＦＴＩＲ法での測定結果（それぞれの図の白抜き三角）は、本発明によるＳｉＮｘとの相対的な関係が大きく異なっている。図２では平行平板型プラズマＣＶＤ装置で成膜したもの（基板温度１００℃）の膜中水素濃度は、本発明により成膜されたもの（Ｇａｐ１５０ｍｍ、基板温度１５０℃）より膜中水素濃度が低く測定されているが、図３の結合密度比ではこれに対応した点において、図２で示す関係が逆転している。 Also in the evaluation of the SiNx film in the present invention, with respect to the SiNx film formed by the parallel plate type plasma CVD apparatus, the measurement results by the Rudford backscattering (RBS) method and Rutherford forward scattering (HFS) method in FIG. The measurement results by the FTIR method in FIG. 3 (open triangles in the respective drawings) are greatly different in relative relationship with SiNx according to the present invention. In FIG. 2, the hydrogen concentration in the film formed by the parallel plate type plasma CVD apparatus (substrate temperature 100 ° C.) is lower than that formed by the present invention (Gap 150 mm, substrate temperature 150 ° C.). Although measured, the relationship shown in FIG. 2 is reversed at the point corresponding to the bond density ratio of FIG.
　上記で明らかなように、膜中水素濃度の測定を本発明のようにラザフォード後方散乱（ＲＢＳ）法およびラザフォード前方散乱（ＨＦＳ）法で行うことは極めて重要であり、これにより膜中水素濃度の制御を行うことが水蒸気バリア性の高いＳｉＮｘ膜を安定して成膜するために必要となる。 As apparent from the above, it is extremely important to measure the hydrogen concentration in the film by the Rutherford backscattering (RBS) method and the Rutherford forward scattering (HFS) method as in the present invention. Control is necessary to stably form a SiNx film having a high water vapor barrier property.
　図４には、ＳｉＮｘ膜の水蒸気透過度と膜中水素濃度の関係を示し、図５には、水蒸気透過度と膜中Ｎ／（Ｓｉ＋Ｎ）比の関係を示す。膜中水素濃度および膜中Ｎ／（Ｓｉ＋Ｎ）比はラザフォード後方散乱（ＲＢＳ）法およびラザフォード前方散乱（ＨＦＳ）法で測定し、水蒸気透過度はＭｏｃｏｎ法およびＣａ腐食法で測定している。
　図４の（ａ）～（ｄ）は図５の（ａ）～（ｄ）に対応し、基板温度約１００℃にて成膜されたＳｉＮｘ膜のそれぞれの測定結果を示している。図４、図５において（ａ）～（ｃ）はＳｉＮｘ膜を厚み５０μｍのポリイミドフィルムの片面に成膜したもの（single stacked layer）であり、（ａ）（ｂ）はＧａｐ１５０ｍｍ、（ｃ）はＧａｐ２００ｍｍで成膜が行われたものであ。膜厚は、（ａ）は２００ｎｍ、（ｂ）（ｃ）は１μｍである。（ｄ）はポリイミドフィルムの両面にそれぞれ１μｍのＳｉＮｘ膜を（double stacked layer）、Ｇａｐ２００ｍｍで成膜したものである。ここで、ポリイミドフィルムはＭｏｃｏｎ法およびＣａ腐食法で測定する際のＳｉＮｘ膜の基材であり、水蒸気透過度は十分に高い、すなわち、ポリイミドフィルムの有無は水蒸気透過度の測定結果に影響を及ぼさない。 FIG. 4 shows the relationship between the water vapor permeability of the SiNx film and the hydrogen concentration in the film, and FIG. 5 shows the relation between the water vapor permeability and the N / (Si + N) ratio in the film. The hydrogen concentration in the film and the N / (Si + N) ratio in the film were measured by the Rutherford backscattering (RBS) method and the Rutherford forward scattering (HFS) method, and the water vapor permeability was measured by the Mocon method and the Ca corrosion method.
4A to 4D correspond to FIGS. 5A to 5D and show the measurement results of the SiNx films formed at the substrate temperature of about 100 ° C. FIG. 4 and 5, (a) to (c) are SiNx films formed on one side of a polyimide film having a thickness of 50 μm (single stacked layer), (a) and (b) are Gap 150 mm, and (c) is The film was formed with a gap of 200 mm. The film thickness is 200 nm for (a) and 1 μm for (b) and (c). In (d), a 1 μm SiNx film (double stacked layer) is formed on both sides of a polyimide film with a gap of 200 mm. Here, the polyimide film is a base material of the SiNx film when measured by the Mocon method and the Ca corrosion method, and the water vapor permeability is sufficiently high, that is, the presence or absence of the polyimide film affects the measurement result of the water vapor permeability. Absent.
　図４（ａ）～（ｃ）から明らかなように、膜中水素濃度の低下に伴い、水蒸気透過度が低下する。すなわち、水蒸気バリア性が高くなっていることが分かる。
　一方、図５では、Ｎ／（Ｓｉ＋Ｎ）比は０．６程度とほぼ一定値を示している。以上より、水蒸気透過度が１０－３ｇ／ｍ２／ｄａｙ以下となる高水蒸気バリア性を有する組成のＳｉＮｘ膜が得られ、このＳｉＮｘ膜ではＮ／（Ｓｉ＋Ｎ）比が０．６程度で、かつ膜中水素濃度が２５％以下であることがわかる。
　なお、このＮ／（Ｓｉ＋Ｎ）比が０．６程度と一定しているのは、この比がＳｉＨ４ガスおよびＮＨ３ガスの流量比で定まるためであり、本発明の成膜方法では、上記のとおりＳｉＨ４ガスおよびＮＨ３ガスの流量比を固定しているためである。しかしながら、この結果は同時に本発明の成膜方法の安定性も示している。また、本発明の成膜方法では、上記のように可視光での透過度の高いＳｉＮｘ膜が安定して生成されることを示している。 As is clear from FIGS. 4A to 4C, the water vapor transmission rate decreases as the hydrogen concentration in the film decreases. That is, it turns out that water vapor | steam barrier property is high.
On the other hand, in FIG. 5, the N / (Si + N) ratio is approximately 0.6, which is a substantially constant value. As described above, a SiNx film having a composition having a high water vapor barrier property with a water vapor permeability of 10 −3 g / m 2 / day or less is obtained. In this SiNx film, the N / (Si + N) ratio is about 0.6, and the film It can be seen that the intermediate hydrogen concentration is 25% or less.
The N / (Si + N) ratio is constant at about 0.6 because the ratio is determined by the flow rate ratio of SiH4 gas and NH3 gas. In the film forming method of the present invention, as described above, This is because the flow rate ratio of SiH 4 gas and NH 3 gas is fixed. However, this result also shows the stability of the film forming method of the present invention. In addition, in the film forming method of the present invention, it is shown that the SiNx film having high visible light transmittance is stably generated as described above.
　図４および図５において、（ｄ）は１μｍのＳｉＮｘ膜をポリイミドフィルムの両側に成膜したものであり、ＳｉＮｘ膜の厚さは両側合わせて２μｍとなっている。全体のＳｉＮｘ膜の厚さは（ｂ）（ｃ）と同じであるが、水蒸気透過度は１×１０－５ｇ／ｍ２／ｄａｙとなっており、これはＣａ腐食法による測定限界以下となっている。
　ポリイミドフィルムの片面にＳｉＮｘ膜を成膜した場合は、成膜時の温度上昇により、ＳｉＮｘ膜を成膜したポリイミドフィルムに反りが生じたり、また、成膜した片面のみに膜応力がかかることによりポリイミドフィルムが変形し、ＳｉＮｘ膜に亀裂を生じやすい。つまり、膜自体が良好なバリアを性を有している場合でも、亀裂により水蒸気透過度の測定値が上昇、すなわち、バリア性が悪化する場合がある。これに対しポリイミドフィルムの両面にＳｉＮｘ膜を成膜した場合は、このような反りや亀裂が生じにくいため、膜本来の水蒸気透過度測定結果が得られる。
　実際のデバイスではプラスチック基板やガラス基板が用いられており、これらの基板はＳｉＮｘ膜を片面のみに成膜しても、反りや変形を生じない。したがって、上記のようなポリイミドフィルムの両面にＳｉＮｘ膜を成膜した（ｄ）の場合での水蒸気透過度の測定値は、実際のプラスチック基板やガラス基板にＳｉＮｘ膜を成膜した場合と同等の特性であると考えられる。 4 and 5, (d) shows a 1 μm SiNx film formed on both sides of the polyimide film, and the thickness of the SiNx film is 2 μm on both sides. The thickness of the entire SiNx film is the same as (b) and (c), but the water vapor permeability is 1 × 10-5 g / m2 / day, which is below the measurement limit by the Ca corrosion method. Yes.
When a SiNx film is formed on one side of a polyimide film, the polyimide film on which the SiNx film is formed is warped due to a temperature rise during the film formation, or film stress is applied only to the formed one side. The polyimide film is deformed and the SiNx film is easily cracked. That is, even when the film itself has a good barrier property, the measured value of water vapor permeability may increase due to cracks, that is, the barrier property may deteriorate. On the other hand, when SiNx films are formed on both sides of the polyimide film, such warpage and cracks are unlikely to occur, so that the original water vapor permeability measurement result of the film can be obtained.
In an actual device, a plastic substrate or a glass substrate is used, and even if a SiNx film is formed on only one side, these substrates do not warp or deform. Therefore, the measured value of water vapor permeability in the case of (d) in which the SiNx film is formed on both surfaces of the polyimide film as described above is equivalent to that in the case where the SiNx film is formed on an actual plastic substrate or glass substrate. It is considered to be a characteristic.
　上記の結果から膜中水素濃度が概ね２５ａｔｍ％以下となるように成膜された厚さ２μｍのＳｉＮｘ膜を用いことにより、当初に述べた実際に必要とされる１０－５ｇ／ｍ２／ｄａｙレベルの水蒸気透過度が達成されることがわかる。 Based on the above results, by using a 2 μm thick SiNx film formed so that the hydrogen concentration in the film is approximately 25 atm% or less, the 10-5 g / m 2 / day level actually required as described above is used. It can be seen that the water vapor permeability is achieved.
　図６は膜中水素濃度とＧａｐとの関係をさらに明瞭に示すものである。基板温度約１００℃にて、Ｇａｐを１５０ｍｍから２５０ｍｍまで変えて成膜したＳｉＮｘ膜の膜中水素濃度を測定したものである。 FIG. 6 shows the relationship between the hydrogen concentration in the film and the gap more clearly. The hydrogen concentration in the SiNx film formed by changing the gap from 150 mm to 250 mm at a substrate temperature of about 100 ° C. was measured.
　図６から明らかなように、Ｇａｐが１７５ｍｍ以上では、基板温度が約１００℃と低いにも拘わらず、いずれも膜中水素濃度が２０％以下と低く、また、ほぼ一定値となっている。
　図２の結果と合わせると明らかなように、ＳＷＰ－ＣＶＤ装置を用いてＳｉＮｘ膜を成膜する場合は、Ｇａｐを１７５ｍｍ以上とすれば、基板温度約１００℃と低い場合でも、膜中水素濃度が２０％以下のＳｉＮｘ膜を安定して成膜することが可能である。 As is apparent from FIG. 6, when the gap is 175 mm or more, the hydrogen concentration in the film is as low as 20% or less and is almost constant, although the substrate temperature is as low as about 100 ° C.
As is clear from the results shown in FIG. 2, when the SiNx film is formed using the SWP-CVD apparatus, the hydrogen concentration in the film can be increased even if the substrate temperature is as low as about 100 ° C. if the gap is 175 mm or more. It is possible to stably form a SiNx film having a thickness of 20% or less.
＜本発明による成膜方法の効果＞
　上記のように本発明は、水蒸気透過度の低い、すなわち水蒸気バリア性の高いＳｉＮｘ膜を、できる限り低温でかつ安定して成膜することが目的である。このようなＳｉＮｘ膜の成膜は、ＳＷＰ－ＣＶＤ装置を用いることで可能である。ＳＷＰ－ＣＶＤ装置で発生するプラズマと基板との距離、すなわち、Ｇａｐを大きくすることによって、基板温度１００℃以下の低温の状態で膜中水素濃度を低下させたＳｉＮｘ膜を安定した組成で成膜することができる。
　このような低温で成膜が可能であることにより、有機材料上においても、有機材料にダメージを与えることなく水蒸気バリア性の高いＳｉＮｘ膜を成膜することができ、液晶表示素子や有機ＥＬ表示素子などの発光素子およびこれらを含む回路に広く適用することが可能となる。 <Effect of the film forming method according to the present invention>
As described above, an object of the present invention is to form a SiNx film having a low water vapor permeability, that is, a high water vapor barrier property, as stably as possible at a low temperature. Such a SiNx film can be formed by using a SWP-CVD apparatus. By increasing the distance between the plasma generated in the SWP-CVD apparatus and the substrate, that is, Gap, the SiNx film having a reduced hydrogen concentration in the film at a low temperature of 100 ° C. or less is formed with a stable composition. can do.
Since the film can be formed at such a low temperature, an SiNx film having a high water vapor barrier property can be formed on the organic material without damaging the organic material, and a liquid crystal display element or an organic EL display can be formed. The present invention can be widely applied to light emitting elements such as elements and circuits including these elements.
　また本発明では、成膜ガスとして使用するＳｉＨ４ガスおよびＮＨ３ガスの流量比を変えることにより、所望のＮ／（Ｓｉ＋Ｎ）比を持つＳｉＮｘ膜を成膜することができる。上記のように、Ｎ／（Ｓｉ＋Ｎ）比が約０．６で可視光の透過度が最も良くなる（透過度約９５％）ことが分かっているので、特にこの条件で水蒸気バリア性の高いＳｉＮｘ膜を成膜することにより、液晶表示素子や有機ＥＬ表示素子などの発光素子およびこれらを含
む回路での使用に極めて適したＳｉＮｘ膜を成膜することができる。 Further, in the present invention, a SiNx film having a desired N / (Si + N) ratio can be formed by changing the flow ratio of SiH4 gas and NH3 gas used as a film forming gas. As described above, it is known that the transmittance of visible light is best when the N / (Si + N) ratio is about 0.6 (the transmittance is about 95%). By forming the film, it is possible to form a SiNx film that is extremely suitable for use in a light emitting element such as a liquid crystal display element or an organic EL display element and a circuit including these elements.
＜本発明による成膜方法の変形実施方法および適用例＞
　ＳＷＰ－ＣＶＤ装置を用いた本発明のＳｉＮｘ膜の成膜方法では、上記の通り、１００℃以下の温度で膜中水素濃度を低下させたＳｉＮｘ膜を安定した組成で成膜することができるが、本発明のＳｉＮｘ膜の成膜方法を１００℃を越えた温度環境においても適用することができる。成膜を行う基板９や材料の材質によって、より高い温度で成膜可能な場合には、ステージ８に組み込んだヒーター１０の調整により、温度調整が可能である。 <Modification Method and Application Example of Film Formation Method According to the Present Invention>
In the SiNx film forming method of the present invention using the SWP-CVD apparatus, as described above, the SiNx film in which the hydrogen concentration in the film is reduced can be formed with a stable composition at a temperature of 100 ° C. or lower. The SiNx film forming method of the present invention can also be applied in a temperature environment exceeding 100 ° C. In the case where film formation can be performed at a higher temperature depending on the substrate 9 or material used for film formation, the temperature can be adjusted by adjusting the heater 10 incorporated in the stage 8.
　以上で説明した本発明の成膜方法での成膜条件におけるパラメータ（基板温度、Ｇａｐ、マイクロ波電力、成膜ガス流量）は、成膜される基板あるいは有機材料などの、デバイスを構成している基材、材料の耐熱性に対応して、種々の変形実施が可能である。従って本発明の成膜方法は上記の実施例に限定されることなく、本発明の範囲で種々の実施形態が可能である。 The parameters (substrate temperature, gap, microwave power, film forming gas flow rate) in the film forming conditions of the film forming method of the present invention described above are the devices such as the substrate or organic material to be formed. Various modifications can be made in accordance with the heat resistance of the base material and material. Therefore, the film forming method of the present invention is not limited to the above-described examples, and various embodiments are possible within the scope of the present invention.
　本発明の成膜方法を用いた水蒸気バリア性の高いＳｉＮｘ膜は、種々のデバイスの封止膜に用いることができ、特に２００℃以下の低温で成膜される必要があるデバイスに対し好適に適用することができる。
　さらに、有機ＥＬ等の高温に耐えない材料に対して水蒸気バリア性の高いＳｉＮｘ膜を成膜できる。このような高水蒸気バリア性を有する低温形成ＳｉＮｘ膜は、さらに種々のフレキシブルなデバイスの封止に使用することが可能である。特に封止膜に透明性が要求される場合は本発明のＳｉＮｘ膜は極めて有用である。 The SiNx film having a high water vapor barrier property using the film forming method of the present invention can be used as a sealing film for various devices, and is particularly suitable for a device that needs to be formed at a low temperature of 200 ° C. or lower. Can be applied.
Furthermore, a SiNx film having a high water vapor barrier property can be formed on a material that cannot withstand high temperatures such as organic EL. Such a low-temperature formation SiNx film having a high water vapor barrier property can be used for sealing various flexible devices. In particular, when the sealing film requires transparency, the SiNx film of the present invention is extremely useful.
　上記のような本発明によるＳｉＮｘ膜は、たとえば有機電界発光素子、有機トランジスタ、有機太陽電池、液晶表示素子、電子ペーパー、ＬＥＤ等を含む半導体デバイスのパッシベーション膜あるいは封止膜として用いることができる。 The SiNx film according to the present invention as described above can be used as a passivation film or a sealing film of a semiconductor device including, for example, an organic electroluminescent element, an organic transistor, an organic solar battery, a liquid crystal display element, electronic paper, an LED, and the like.
　本発明は、上記で説明した実施の形態および変形実施例に限定されるものではない。本発明の技術的思想の範囲内で考えられるその他の態様も本発明の範囲内に含まれる。 The present invention is not limited to the embodiments and modified examples described above. Other embodiments conceivable within the scope of the technical idea of the present invention are also included in the scope of the present invention.
　次の優先権基礎出願の開示内容は引用文としてここに組み込まれる。
　日本国特許出願２０１０年第１９４９７３号（２０１０年８月３１日出願）。 The disclosure of the following priority application is hereby incorporated by reference.
Japanese Patent Application 2010 No. 194973 (filed on August 31, 2010).

Claims (5)

  1. 　成膜対象物の温度が２００℃以下で前記成膜対象物上に成膜された非晶質窒化珪素膜であって、ラザフォード後方散乱（ＲＢＳ）法および、ラザフォード前方散乱（ＨＦＳ）法によって測定される前記非晶質窒化珪素膜の膜中水素濃度が２５ａｔｍ％以下であることを特徴とする非晶質窒化珪素膜。 An amorphous silicon nitride film formed on the film formation object at a temperature of the film formation object of 200 ° C. or less, and measured by Rutherford backscattering (RBS) method and Rutherford forward scattering (HFS) method An amorphous silicon nitride film having a hydrogen concentration in the amorphous silicon nitride film of 25 atm% or less.
  2. 　表面波プラズマＣＶＤ装置を用いた非晶質窒化珪素膜の成膜方法であって、
    　成膜ガスとしてＳｉＨ４ガスおよびＮＨ３ガスを使用し、
    　前記成膜対象物の温度が２００℃以下で非晶質窒化珪素膜が成膜されるように成膜対象物の温度を調整するとともに、前記表面波プラズマＣＶＤ装置の誘電体窓と前記成膜対象物との距離を１７５ｍｍ以上の所定の値に設定して成膜することを特徴とする非晶質窒化珪素膜の成膜方法。     A method of forming an amorphous silicon nitride film using a surface wave plasma CVD apparatus,
    SiH4 gas and NH3 gas are used as the film forming gas,
    The temperature of the film formation target is adjusted so that an amorphous silicon nitride film is formed at a temperature of 200 ° C. or less, and the dielectric window of the surface wave plasma CVD apparatus and the film formation are adjusted. A method for forming an amorphous silicon nitride film, wherein the film is formed by setting a distance from an object to a predetermined value of 175 mm or more.
  3. 　請求項２に記載の非晶質窒化珪素膜の成膜方法において、
    　成膜される非晶質窒化珪素膜のＮ／（Ｓｉ＋Ｎ）比が略０．６となるように、前記非晶質窒化珪素膜を成膜するための成膜ガスとして前記成膜ガス吹き出し口から放出するＳｉＨ４ガスおよびＮＨ３ガスの流量比を調整することを特徴とする非晶質窒化珪素膜の成膜方法。     The method for forming an amorphous silicon nitride film according to claim 2,
    The film forming gas outlet is used as a film forming gas for forming the amorphous silicon nitride film so that the N / (Si + N) ratio of the amorphous silicon nitride film to be formed is approximately 0.6. A method for forming an amorphous silicon nitride film, comprising adjusting a flow rate ratio of SiH 4 gas and NH 3 gas released from the substrate.
  4. 　請求項２乃至３のいずれか１項に記載の非晶質窒化珪素膜の成膜方法を用いて成膜された非晶質窒化珪素膜であって、膜中水素濃度が２５ａｔｍ％以下であることを特徴とする非晶質窒化珪素膜。 An amorphous silicon nitride film formed by using the method for forming an amorphous silicon nitride film according to claim 2, wherein a hydrogen concentration in the film is 25 atm% or less. An amorphous silicon nitride film characterized by the above.
  5. 　請求項１に記載の非晶質窒化珪素膜、または請求項２乃至３のいずれか１項に記載の非晶質窒化珪素膜の成膜方法を用いて成膜した非晶質窒化珪素膜からなるパッシベーション膜を備えた半導体デバイス。 An amorphous silicon nitride film according to claim 1 or an amorphous silicon nitride film formed by using the method for forming an amorphous silicon nitride film according to any one of claims 2 to 3. A semiconductor device provided with a passivation film.
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