WO2015119001A1 - Film d'oxynitrure de silicium, procédé de production associé et transistor - Google Patents

Film d'oxynitrure de silicium, procédé de production associé et transistor Download PDF

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WO2015119001A1
WO2015119001A1 PCT/JP2015/052244 JP2015052244W WO2015119001A1 WO 2015119001 A1 WO2015119001 A1 WO 2015119001A1 JP 2015052244 W JP2015052244 W JP 2015052244W WO 2015119001 A1 WO2015119001 A1 WO 2015119001A1
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film
silicon oxynitride
oxynitride film
transistor
coating
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PCT/JP2015/052244
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English (en)
Japanese (ja)
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梅田　賢一
田中　淳
鈴木　真之
下田　達也
井上　聡
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富士フイルム株式会社
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Priority to KR1020167014499A priority Critical patent/KR20160078490A/ko
Publication of WO2015119001A1 publication Critical patent/WO2015119001A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • H01L21/02222—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
    • 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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/0214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
    • 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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • 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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
    • H01L21/02348—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to UV light
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

Definitions

  • the present invention relates to a silicon oxynitride film, and in particular, silicon obtained by FT-IR measurement in which the ratio of the absorption intensity derived from the Si—N bond and the absorption intensity derived from the Si—O bond is within a predetermined range.
  • the present invention relates to an oxynitride film.
  • the present invention also relates to a method for producing the silicon oxynitride film and a transistor including the silicon oxynitride film.
  • Silicon-based ceramic thin films such as silicon oxynitride are used for various applications in terms of their excellent heat resistance, wear resistance, corrosion resistance, and the like.
  • a vapor phase growth method is known as a method for producing a silicon oxynitride film.
  • this method has room for improvement because of high process costs and relatively low productivity. Therefore, Patent Document 1 discloses a method for producing a silicon oxynitride film by a coating method.
  • an object of the present invention is to provide a silicon oxynitride film that has excellent insulating characteristics and can be suitably used as a gate insulating film of a transistor, and a manufacturing method thereof.
  • Another object of the present invention is to provide a transistor including a silicon oxynitride film.
  • the present inventors have found that the ratio between the absorption intensity derived from the Si—N bond and the absorption intensity derived from the Si—O bond obtained by FT-IR measurement is within a predetermined range. It has been found that a desired effect can be obtained by using a silicon oxynitride film, and the present invention has been completed. That is, the said subject is solved by the following means.
  • a silicon oxynitride film produced using a silazane compound In the absorption spectrum obtained by FT-IR measurement, the ratio of the absorption intensity (I Si-N ) derived from the Si—N bond to the absorption intensity (I Si—O ) derived from the Si—O bond (I Si-N / A silicon oxynitride film having I Si-O ) of 1.00 or more.
  • the silicon oxynitride film according to (1) or (2) which includes a silicon oxide film on at least one surface.
  • XPS X-ray Photoelectron Spectroscopy
  • a transistor comprising a gate insulating film made of the silicon oxynitride film according to any one of (1) to (8).
  • a silicon oxynitride film that has excellent insulating characteristics and can be suitably used as a gate insulating film of a transistor, and a method for manufacturing the same.
  • a transistor including a silicon oxynitride film can also be provided.
  • FIG. 1 is a schematic cross-sectional view of one embodiment of a transistor of the present invention. It is a figure which shows the composition distribution in the film thickness direction of the SiON film obtained in Example 1.
  • FIG. It is a figure which shows the composition distribution in the film thickness direction of the SiON film obtained in Example 2.
  • FIG. It is sectional drawing of a SiON film
  • the feature of the present invention compared with the prior art is that the absorption intensity derived from the Si—N bond (I Si—N ) and the absorption intensity derived from the Si—O bond in the absorption spectrum obtained by FT-IR measurement.
  • the ratio (I Si-N / I Si-O ) with (I Si-O ) is adjusted within a predetermined range. In other words, it has been found that the desired effect can be obtained by increasing the proportion of Si—N bonds contained in the silicon oxynitride film.
  • this silicon oxynitride film is subjected to ultraviolet irradiation and / or heat treatment without removing the solvent (that is, without providing a drying step) after forming the coating film. Can be manufactured. By performing this treatment, the Si—N bond ratio can be increased while suppressing the oxidation of the silicon oxynitride film.
  • Patent Document 1 described above since the process of removing the solvent is performed after the coating film is formed, a silicon oxynitride film having a desired ratio (I Si—N / I Si—O ) is obtained. I can't.
  • the method for producing a silicon oxynitride film includes an application step of forming a coating film containing a predetermined component, and irradiating the coating film with ultraviolet rays without removing the solvent and / or heat treatment. A conversion step to be applied.
  • the material used in each process and its procedure are explained in full detail.
  • a coating process is a process of apply
  • a coating film that is subjected to ultraviolet irradiation and / or heat treatment in the conversion step described later is obtained.
  • the material (silazane compound, a solvent, etc.) used at this process is explained in full detail first, and the procedure of the post process is explained in full detail.
  • silazane compound is a compound having a silicon-nitrogen bond (—SiN—) in its structure, and is a starting material when forming a SiON film.
  • the silazane compound may be a low molecular compound or a high molecular compound (a polymer having a predetermined repeating unit).
  • low molecular weight silazane compounds include hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, and the like. It is done.
  • the type of the high molecular weight silazane compound (polysilazane, polysilazane compound) is not particularly limited.
  • it has a main skeleton composed of units represented by the following general formula (1) described in JP-A-8-112879.
  • a compound is preferred.
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group. .
  • the polysilazane is preferably perhydropolysilazane (hereinafter, also referred to as “PHPS”) in which all of R 1 , R 2 , and R 3 are hydrogen atoms in that the insulating properties of the SiON film are more excellent.
  • PHPS perhydropolysilazane
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and can be a liquid or solid substance (depending on the molecular weight).
  • Perhydropolysilazane may be a commercially available product. Examples of commercially available products include AQUAMICA NN120, NN120-20, NN110, NAX120, NAX120-20, NAX110, NL120A, NL120-20, NL110A, NL150A, NP110, NP140 (AZ Electronic Materials Co., Ltd.).
  • polysilazane examples include silicon alkoxide addition polysilazane obtained by reacting polysilazane represented by the above general formula with silicon alkoxide (for example, JP-A-5-238827), glycidol addition obtained by reacting glycidol.
  • Polysilazane for example, JP-A-6-122852
  • alcohol-added polysilazane for example, JP-A-6-240208
  • metal carboxylate obtained by reacting a metal carboxylate
  • Polysilazane for example, JP-A-6-299118
  • acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex
  • metal fine particles are added.
  • Obtained metal fine particle Polysilazane e.g., JP-A-7-196986 JP
  • the molecular weight of polysilazane is not particularly limited, but for example, those having an average molecular weight in terms of polystyrene in the range of 1,000 to 20,000 are preferred, and those having a molecular weight in the range of 1,000 to 10,000 are more preferred. These polysilazanes can be used in combination of two or more.
  • the composition for coating film formation contains a solvent.
  • the solvent is not particularly limited as long as it can dissolve the silazane compound to be used, but specific examples of preferable solvents include the following.
  • aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, etc.
  • ethers such as dipropyl ether, dibutyl ether, diethyl ether, methyl tertiary butyl ether (hereinafter referred to as MTBE), anisole and the like, and (e) ketones such as methyl isobutyl ketone (hereinafter referred to as MIBK).
  • MIBK methyl isobutyl ketone
  • (b) saturated hydrocarbon compounds, (c) alicyclic hydrocarbon compounds, (d) ethers, and (e) ketones are preferred.
  • the mass ratio between the silazane compound and the solvent in the coating film forming composition is not particularly limited, and an optimal mass ratio is appropriately selected according to the thickness of the coating film. From the viewpoint of excellent coating properties, 0.01 to 0.50 is preferable, and 0.05 to 0.20 is more preferable.
  • the above-mentioned coating film forming composition can contain other additive components as required.
  • examples of such components include viscosity modifiers and crosslinking accelerators.
  • the structure of the substrate may be a single layer structure or a laminated structure.
  • the material of the substrate is not particularly limited, and for example, glass, inorganic materials such as YSZ (yttrium stabilized zirconium), resin materials, composite materials thereof, and the like can be used. Among these, a resin substrate or a composite material thereof is preferable from the viewpoint of light weight and flexibility.
  • Composite plastic material substrate, glass flakes, glass fiber, glass beads etc. and synthetic resin composite plastic material substrate, composite plastic material substrate of clay mineral or mica derivative crystal structure and synthetic resin, thin glass and above A laminated plastic material substrate having at least one bonding interface with a single organic material, a composite material substrate having barrier performance having at least one bonding interface by alternately laminating inorganic layers and organic layers, A stainless steel substrate or a metal multilayer substrate in which stainless and dissimilar metals are laminated, aluminum Beam substrate or oxidation treatment on the surface (e.g.
  • the resin substrate is preferably excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, workability, low air permeability, low moisture absorption, and the like.
  • the resin substrate may include a gas barrier layer for preventing permeation of moisture and oxygen, an undercoat layer for improving the flatness of the resin substrate and adhesion with the lower electrode, and the like.
  • the thickness of the substrate in the present invention is not particularly limited, but is preferably 50 to 1000 ⁇ m, more preferably 50 to 500 ⁇ m. When the thickness of the substrate is 50 ⁇ m or more, the flatness of the substrate itself is further improved. Further, when the thickness of the substrate is 500 ⁇ m or less, the flexibility of the substrate itself is further improved, and the use as a substrate for a flexible device becomes easier.
  • a conventionally known method can be used as a method of applying the coating film forming composition to the substrate surface.
  • a conventionally known method can be used.
  • an inkjet method, a slit coating method, a screen printing method, a dip coating method, a spin coating method, a spray method, a transfer method, and the like can be given.
  • the thickness of the coated film after application is preferably thin so that it can be efficiently cured (converted) during ultraviolet irradiation and / or heat treatment described below. For this reason, the thickness of the coating film is preferably 1.0 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
  • the coating film is formed on both sides of the substrate in order to suppress warpage of the substrate due to volume shrinkage that occurs when the coating film forming composition is converted into a SiON film.
  • a composition may be applied.
  • the conversion step irradiates the coating film with ultraviolet rays and / or heats the coating film in a non-oxidizing atmosphere without removing the solvent contained in the coating film obtained in the coating step (heating) Process).
  • the conversion including at least one treatment selected from the group consisting of the ultraviolet irradiation treatment and the heat treatment
  • the above-described treatment is carried out on the coating film obtained in the coating step without performing a drying treatment for removing the solvent.
  • “irradiating the coating film without removing the solvent” means irradiating the coating film in which the solvent-derived components remain (or heating the coating film).
  • a silazane compound is a material whose oxidation is accelerated by heat treatment in the presence of oxygen and moisture. Therefore, when the drying process is performed, the generation of Si—O bonds proceeds, and a SiON film having a desired ratio (I Si—N / I Si—O ) cannot be obtained.
  • the procedure of this step will be described in detail.
  • the coating film is irradiated with ultraviolet rays and / or subjected to heat treatment without removing the solvent contained in the coating film obtained in the coating step. carry out. That is, after the coating step, the coating film is subjected to ultraviolet irradiation treatment and / or heat treatment without providing a drying step for removing excess solvent in the coating film. By carrying out this step, the degree of Si—O bond formation in the coating film can be suppressed, and as a result, a SiON film having a desired ratio (I Si—N / I Si—O ) can be obtained. it can.
  • the process of performing a drying process on the temperature conditions of 50 to 150 degreeC is intended. In this invention, the ultraviolet irradiation or heat processing mentioned later is implemented, without implementing a drying process.
  • the atmosphere for ultraviolet irradiation and / or heat treatment is a non-oxidizing atmosphere.
  • the non-oxidizing atmosphere is intended to be at a low oxygen concentration that does not allow the oxidation reaction to proceed, and an atmosphere in which the oxygen concentration is 0.1% or less by volume is preferable. More specifically, a reduced pressure state with the above oxygen concentration (0.1% or less); an inert atmosphere such as nitrogen, argon, helium, or neon; a reducing atmosphere such as vacuum, carbon dioxide, hydrogen, ammonia, or the like.
  • at least one selected from the group consisting of nitrogen, argon, helium and carbon dioxide is preferable.
  • the conditions for ultraviolet irradiation are appropriately selected according to the thickness, composition, hardness, and the like of the SiON film to be formed, but are generally selected within the following range.
  • the wavelength of the ultraviolet rays to be irradiated is not particularly limited, but is preferably 450 nm or less, and more preferably 150 to 300 nm.
  • the ultraviolet irradiation time is not particularly limited, it is preferably 3 minutes or longer, and more preferably 20 minutes or longer.
  • the upper limit is not particularly limited, but is preferably 60 minutes or less from the viewpoint of productivity.
  • the necessary irradiation energy is an amount that the silazane compound contained in the coating film is sufficiently converted to silicon oxynitride, and is not particularly limited, but is preferably 0.5 J / cm 2 or more, and 1.0 J / cm. More preferably, it is 2 or more.
  • the upper limit is not particularly limited, but is preferably 1000 J / cm 2 or less from the viewpoint of productivity and economy.
  • Various kinds of such ultraviolet light sources are known, and arbitrary ones can be used.
  • Examples thereof include a xenon discharge tube, a mercury discharge tube, an excimer lamp, and an ultraviolet LED.
  • a silazane compound when applied on both sides, it is preferable to irradiate ultraviolet rays simultaneously from both sides in order to suppress warping of the flexible substrate.
  • the conditions for the heat treatment are not particularly limited, and optimal conditions are appropriately selected according to the type of silazane compound to be used.
  • the temperature condition is non-oxidation because the insulating properties of the resulting SiON film are more excellent.
  • 100 to 500 ° C. in a neutral atmosphere more preferably more than 150 ° C. and 400 ° C. or less.
  • the heating time is preferably 10 minutes or more, and more preferably 20 minutes or more in that the insulating properties of the resulting SiON film are more excellent.
  • the upper limit is not particularly limited, but is preferably 60 minutes or less from the viewpoint of productivity.
  • the said ultraviolet irradiation you may implement together with heat processing as needed.
  • the conditions for the heat treatment 150 ° C. or lower is preferable, and 100 ° C. or lower is more preferable.
  • the oxidizing atmosphere examples include at least one of oxygen, oxygen ions, ozone, oxygen plasma, oxygen radicals, water, hydroxide ions, and hydroxyl radicals. Of these, ozone, oxygen plasma, or oxygen radicals are preferable from the viewpoint of easy oxidation, and ozone is more preferable.
  • the ozone concentration in the ozone atmosphere is preferably 500 ppm or more. Note that in this specification, “ozone treatment” intends to perform an oxidation treatment in an ozone atmosphere (in addition, the case where a heat treatment is performed in an ozone atmosphere is also included in the “ozone treatment”). ).
  • a method of oxidation treatment a method of performing heat treatment and / or light irradiation treatment in an oxidizing atmosphere on the film obtained in the conversion step, ozone, oxygen plasma, oxygen radical, etc.
  • Examples thereof include a method for performing an oxidation treatment in an oxidizing atmosphere.
  • the method of performing heat processing in an ozone atmosphere is preferable at the point which the oxidation of the surface of the film
  • the conditions for the heat treatment are not particularly limited, but are preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and preferably 250 ° C. or lower, in that oxidation proceeds efficiently and decomposition of the film is suppressed. 200 degrees C or less is more preferable.
  • the coating process and the conversion process (especially the ultraviolet irradiation process) described above are an SiON film forming apparatus that includes the above-described coating process and the coating apparatus that performs the conversion process and the ultraviolet irradiation apparatus that performs the conversion process in-line. It is preferable to implement. Moreover, when performing the said oxidation process, it is preferable to implement by the SiON film formation apparatus which equips with the surface oxidation apparatus which implements an oxidation process further in-line.
  • in-line is intended to be a process of continuously passing the apparatus using a conveyor belt.
  • the silicon oxynitride film is a film mainly containing atoms such as oxygen, silicon, and nitrogen. This film may contain other atoms (hydrogen, carbon, etc.) as long as the effects of the invention are not impaired.
  • the silicon oxynitride film has an absorption intensity (I Si-N ) derived from an Si—N bond and an absorption intensity derived from an Si—O bond (I Si—O ) in an absorption spectrum obtained by FT-IR measurement.
  • the ratio (I Si—N / I Si—O ) is 1.00 or more, and is preferably 1.39 or more, more preferably 1.79 or more, from the viewpoint that the insulating properties of the SiON film are more excellent.
  • the upper limit is not particularly limited, but is usually 5.00 or less in many cases.
  • the ratio (I Si-N / I Si-O ) is less than 1.00, the insulating characteristics are inferior, and the TFT (thin film transistor) characteristics of the thin film transistor including this film are also inferior.
  • the maximum value of the absorption intensity derived from the Si—N bond within the range of 800 to 860 cm ⁇ 1 determined by the FT-IR ATR method is defined as “the absorption intensity derived from the Si—N bond (I Si-N )”.
  • the maximum value of the absorption intensity derived from the Si—O bond within the range of 1000 to 1060 cm ⁇ 1 is defined as “absorption intensity derived from the Si—O bond (I Si—O )”.
  • the FT-IR measurement is performed as follows. Specifically, using a Fourier transform infrared spectrophotometer manufactured by Thermo Fisher, the sample (film) is irradiated with infrared light and the amount of transmitted light is measured (transmission method). Measurement is carried out at any three locations of the SiON film, and the ratio (I Si-N / I Si-O ) obtained at each measurement location is arithmetically averaged.
  • the thickness of the SiON film is not particularly limited, but is preferably 70 nm or more and more preferably 90 nm or more in terms of excellent insulating characteristics.
  • the upper limit is not particularly limited, but is often 500 nm or less from the viewpoint of easy adjustment of the thickness of the coating film obtained in the coating step.
  • membrane is preferable at 200 nm or less at the point by which the curvature of the laminated body of the obtained SiON film
  • the SiON film may contain hydrogen, and the content ratio may contain 15 atomic% or more of hydrogen.
  • the upper limit is not particularly limited, but is often 30 atomic% or less.
  • the SiON film may contain carbon, and the content ratio thereof may contain 1 atomic% or less of carbon.
  • the lower limit is not particularly limited, but is often 0.001 atomic% or more.
  • These hydrogen and carbon may be derived from a solvent or a silazane compound raw material.
  • the surface of the SiON film may be partially oxidized, and the oxygen content on the surface of the SiON film measured by XPS (X-ray Photoelectron Spectroscopy) analysis is preferably 60 atomic% or more. More preferably, it is 64 atomic% or more. If it is in the said range, the joining characteristic of the interface with an oxide semiconductor layer will be more excellent.
  • the upper limit is not particularly limited, but is often 66.67 atomic% or less.
  • XPS measurement is performed using a Shimadzu Kratos AXIS-ULTRA DLD.
  • At least one surface of the SiON film includes a silicon oxide film. That is, it is preferable that the surface layer region (region from the surface to a predetermined depth position) extending from at least one surface of the SiON film in the depth direction is formed of silicon oxide (in other words, the surface layer region of the SiON film). It is preferable that N atom is not contained and Si atom and O atom are contained). If it is the said aspect, the joining characteristic of the interface with an oxide semiconductor layer is more excellent.
  • the thickness of the silicon oxide film is not particularly limited, but is preferably 25 nm or less, and more preferably 15 nm or less.
  • the lower limit is not particularly limited, but is often 5 nm or more. That is, it is preferably formed of silicon oxide from at least one surface of the SiON film to a position of 25 nm or less in the depth direction.
  • an SiON film in which the above-described oxidation process has been applied to the surface is preferable because the insulating characteristics of the obtained film are excellent and the bonding characteristics at the interface with the oxide semiconductor layer are more excellent.
  • the oxidation process is performed, many Si—O bonds exist on the surface of the SiON film subjected to the oxidation process. More specifically, the peak value of O1s binding energy when the surface subjected to the oxidation step is analyzed by XPS (X-ray Photoelectron Spectroscopy) is preferably larger than 532.0 eV.
  • the SiON film of the present invention can be suitably used for various applications. Examples thereof include a gate insulating film, an interlayer insulating film, a gas barrier film, and an optical thin film of a transistor.
  • FIG. 1 is a schematic cross-sectional view of one embodiment of a thin film transistor.
  • a thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 disposed on the gate electrode 20, and an oxide semiconductor disposed on the gate insulating film 30.
  • the layer 40 includes at least a source electrode 50 and a drain electrode 60 disposed on the oxide semiconductor layer 40.
  • the gate insulating film 30 is formed of the above-described SiON film.
  • the thin film transistor 100 is a bottom-gate thin film transistor.
  • the SiON film of the present invention may be applied to the gate insulating film of the top gate type thin film transistor.
  • the gate insulating film 30 is disposed adjacent to the oxide semiconductor layer 40. When the SiON film of the present invention is used, the interface characteristics with the oxide semiconductor layer 40 are further improved, and the performance as a thin film transistor is further improved.
  • FIG. 1 details an aspect of an oxide thin film transistor using an oxide semiconductor layer.
  • the SiON film of the present invention can be used as a gate insulating film of an organic thin film transistor using an organic semiconductor layer containing an organic semiconductor material. It can be used suitably.
  • the substrate, gate electrode, gate insulating film, oxide semiconductor layer, source electrode, and drain electrode will be described in detail.
  • the substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode and the like which will be described later.
  • substrate is not restrict
  • the gate electrode material e.g., gold (Au), silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, such as sodium metal; InO 2, of SnO 2, ITO, etc.
  • Examples include conductive oxides; conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polydiacetylene; semiconductors such as silicon, germanium, and gallium arsenide; carbon materials such as fullerene, carbon nanotube, and graphite.
  • the thickness of the gate electrode is not particularly limited, but is preferably 10 nm to 1000 nm, and more preferably 50 nm to 500 nm.
  • a method for forming the gate electrode is not particularly limited, and examples thereof include a method of vacuum depositing or sputtering an electrode material on a substrate, a method of applying or printing an electrode forming composition, and the like.
  • examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, letterpress printing; and a mask vapor deposition method.
  • the gate insulating film is formed from the SiON film.
  • the thickness of the gate insulating film is not particularly limited, but is preferably 70 to 1000 nm.
  • FIG. 1 shows a mode in which the gate insulating film is a SiON film, the present invention is not limited to this mode.
  • a laminated insulating film in which a SiON film and another gate insulating film are stacked may be used. .
  • the portion in contact with the oxide semiconductor layer is preferably the SiON film of the present invention.
  • the other gate insulating film include a polymer insulating film containing a polymer as an insulating material.
  • polyethylene polyethylene
  • PP polypropylene
  • PTFE polytetrafluoroethylene
  • PVC polyvinyl chloride
  • PVA polyvinyl alcohol
  • PVP polyvinyl phenol
  • PVP polyvinyl pyrrolidone
  • PS polystyrene
  • PMMA polymethyl methacrylate
  • PAN polyacrylonitrile
  • PC polycarbonate
  • PET poly (ethylene terephthalate)
  • PPS polyphenylene sulfide
  • PI polyimide
  • BCB benzocyclobutene
  • CyPe polycyclopentene
  • PI polysilsesquioxane
  • the oxide semiconductor layer functions as an active layer (channel).
  • one or more of indium (In), gallium (Ga), tin (Sn), and zinc (Zn) are used. It consists of an oxide of a mixture. Examples of such an oxide include indium gallium zinc oxide (IGZO, InGaZnO).
  • indium gallium zinc oxide In—Al—Zn—O, In—Sn—Zn—O, In—Zn—O, In—Sn—O, Zn—O, Sn—O, etc. May be used.
  • the thickness of the oxide semiconductor layer is not particularly limited, but is preferably 5 to 300 nm.
  • a method for forming the oxide semiconductor layer is not particularly limited, and a known method can be employed. For example, spin coating, ink jet, dispenser, screen printing, letterpress printing or intaglio printing can be used. Further, a vapor phase method such as a sputtering method or a vapor deposition method may be employed.
  • ⁇ Source electrode, drain electrode> Specific examples of the material of the source electrode and the drain electrode are the same as those of the gate electrode described above.
  • the method for forming the source electrode and the drain electrode is not particularly limited. For example, a method of vacuum-depositing or sputtering an electrode material on a substrate on which a gate electrode and a gate insulating film are formed, or applying or forming an electrode-forming composition Examples include a printing method. A specific example of the patterning method is the same as that of the gate electrode described above.
  • the channel length of the source electrode and the drain electrode is not particularly limited, but is preferably 0.01 to 1000 ⁇ m.
  • the channel width of the source electrode and the drain electrode is not particularly limited, but is preferably 0.01 to 5000 ⁇ m.
  • Example 1> Manufacture of SiON film
  • NN120-20 manufactured by AZ Electronics Material
  • Solution X was diluted 4-fold with AZ-Thinner to prepare Solution X.
  • the solution X was apply
  • the film thickness of the polysilazane coating film was 150 nm.
  • a non-doped silicon substrate was used to perform FT-IR measurement for bonding state evaluation, and a P-type silicon substrate was used to perform electrical measurement evaluation (insulation characteristic evaluation, TFT characteristic evaluation). .
  • the obtained polysilazane coating film was irradiated with ultraviolet rays for 30 minutes without using a drying treatment, using a SAMCO-UV300H (ultraviolet light source: low-pressure mercury lamp (185 nm and 254 nm)) with a distance of 1 cm from the light source.
  • An SiON film (film thickness: 90 nm) was obtained.
  • the irradiation energy was 100 J / cm 2 .
  • the ultraviolet irradiation atmosphere was performed in a nitrogen (N 2 ) atmosphere. As described later, various evaluations were performed on the obtained SiON film.
  • IGZO Formation of oxide semiconductor layer (TFT fabrication)
  • TFT fabrication Formation of oxide semiconductor layer (TFT fabrication)
  • IGZO film thickness 20 nm
  • the film forming conditions were DC: 200 W, Ar: 97 sccm, O 2 : 4.6 sccm.
  • the obtained IGZO film was patterned by a general photolithography process. Specifically, a resist pattern was formed using a TSMR8900LB positive resist, wet-etched with ITO06N, and then resist stripped with acetone.
  • a resist pattern was formed using a lift-off process. Using a positive / negative reversal resist (AZ5214E), a lift-off pattern is formed on the oxide semiconductor layer, and Al electrodes (thickness: 100 nm) corresponding to the source and drain electrodes are formed by sputtering (DC: 300 W, Ar: 58.5 sccm). Then, the resist was stripped with acetone ultrasonic waves to obtain a thin film transistor having a channel length of 20 ⁇ m and a channel width of 100 ⁇ m. The obtained thin film transistor was post-annealed at 200 ° C. for 30 minutes.
  • composition evaluation When the composition analysis was performed on the above-mentioned SiON film by RBS / HFS / NRA (Rutherford backscattering analysis / hydrogen forward scattering analysis / nuclear reaction analysis), the composition ratio of each element was as shown in Table 1 below. . Further, the composition distribution in the film thickness direction of the obtained SiON film is as shown in FIG. 2, and it is confirmed that the surface is formed of a SiO 2 layer (silicon oxide film) and the inside is SiON. It was.
  • the XPS measurement was performed on the above-described SiON film, and the peak value of the O1s binding energy on the SiON film surface was measured and found to be 532.0 eV. Further, the oxygen content on the surface of the SiON film was 63 atomic%.
  • the thin film transistors manufactured in Example 1 and Example 2 and Comparative Examples 1 to 3 described later all showed good On characteristics ( ⁇ > 10 cm 2 /V.s), but the off-state when Vg ⁇ 5 V Differences occurred in terms of current values and the presence or absence of hysteresis (including hump characteristics). Therefore, off characteristic evaluation and hysteresis evaluation were evaluated according to the following criteria.
  • the amount of Vth shift after stress application was evaluated according to the following criteria.
  • Stress reliability evaluation “A”: ⁇ Vth ⁇ 1V “B”: 1V ⁇ ⁇ Vth ⁇ 5V “C”: ⁇ Vth ⁇ 5 V
  • Example 2 A SiON film and a thin film transistor were prepared according to the same procedure as in Example 1 except that after the ultraviolet irradiation, a heat treatment at 200 ° C. was further performed in an ozone atmosphere for 30 minutes.
  • composition evaluation When the composition analysis was performed on the above-described SiON film by RBS / HFS / NRA (Rutherford backscattering analysis / hydrogen forward scattering analysis / nuclear reaction analysis), the composition ratio of each element was as shown in Table 2 below. . Further, the composition distribution in the film thickness direction of the obtained SiON film is as shown in FIG. 3, and it was confirmed that the surface was formed of a SiO 2 layer and the inside was SiON.
  • Example 1 According to the same procedure as in Example 1, except that the substrate having the polysilazane coating film on the surface was dried at 70 ° C. for 30 minutes before the ultraviolet irradiation after the formation of the polysilazane coating film. A SiON film and a thin film transistor were produced. This mode corresponds to the mode in the example column of Patent Document 1. Using the obtained SiON film or thin film transistor, the above (FT-IR measurement), (insulation characteristic evaluation), and (TFT characteristic evaluation) were performed. The results are summarized in Table 3.
  • Example 3 A SiON film and a thin film transistor were produced according to the same procedure as in Example 1, except that the ultraviolet irradiation under a nitrogen atmosphere was changed to a heat treatment (500 ° C., 2 hours) under an oxygen atmosphere. Using the obtained SiON film or thin film transistor, the above (FT-IR measurement), (insulation characteristic evaluation), and (TFT characteristic evaluation) were performed. The results are summarized in Table 3.
  • the ratio of the obtained SiON film (I Si-N / I Si- O ) is 1.39
  • the ratio of the obtained SiON film (I Si—N / I Si—O ) is 2.14
  • the ratio of SiON film obtained (I Si—N / I Si—O ) was 2.38.
  • FIG. 4 shows a cross-sectional TEM image of the SiON film obtained when the coating conditions are changed so that the thickness of the SiON film is 150 nm.
  • the coating conditions were set to 150 nm, it was confirmed that the surface SiO 2 layer was 25 nm.
  • Example 2 when a PEN substrate (100 nm) was used as a substrate and an SiON film and a thin film transistor were produced according to the same procedure as in Example 1, the same insulating characteristics and TFT characteristics as in Example 1 were obtained.
  • the thickness of the SiON film when the thickness was changed, when the thickness was less than 150 nm, the occurrence of warpage of the laminate of the substrate and the SiON film was further suppressed.
  • substrate 20 gate electrode 30: gate insulating film 40: oxide semiconductor layer 50: source electrode 60: drain electrode 100: thin film transistor

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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Thin Film Transistor (AREA)
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Abstract

La présente invention concerne un film d'oxynitrure de silicium qui possède d'excellentes caractéristiques d'isolation et est approprié pour l'utilisation en tant que film isolant de grille d'un transistor ; un procédé de production de ce film d'oxynitrure de silicium ; et un transistor. Un film d'oxynitrure de silicium selon la présente invention est produit en utilisant un composé silazane, et le rapport de l'intensité d'absorption attribuée à des liaisons Si-N (ISi-N) par rapport à l'intensité d'absorption attribuée à des liaisons Si-O (ISi-O) dans leur spectre d'absorption, tel qu'il est obtenu par mesure FT-IR, à savoir (ISi-N/ISi-O), est 1,00 ou plus.
PCT/JP2015/052244 2014-02-06 2015-01-28 Film d'oxynitrure de silicium, procédé de production associé et transistor WO2015119001A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019060098A1 (fr) 2017-09-19 2019-03-28 M-I L.L.C. Dégazage et analyse de fluide de forage

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JPH06267835A (ja) * 1993-03-12 1994-09-22 Seiko Instr Inc 薄膜のパターニング方法
JP2005530924A (ja) * 2002-05-29 2005-10-13 インフィネオン テクノロジーズ アクチエンゲゼルシャフト 窒化シリコンまたは酸窒化シリコンを蒸着するためのプラズマ化学蒸着方法、および層構造の製造方法、並びに、層構造
JP2006261616A (ja) * 2005-03-18 2006-09-28 Seiko Epson Corp 成膜方法、半導体装置および電子機器
JP2007324170A (ja) * 2006-05-30 2007-12-13 Yoshimi Shiotani 照射装置及び照射装置を用いた半導体製造装置
JP2012004349A (ja) * 2010-06-17 2012-01-05 Az Electronic Materials Kk シリコンオキシナイトライド膜の形成方法およびそれにより製造されたシリコンオキシナイトライド膜付き基板
JP2013065840A (ja) * 2011-08-31 2013-04-11 Semiconductor Energy Lab Co Ltd 半導体装置、及び半導体装置の作製方法
WO2014112554A1 (fr) * 2013-01-16 2014-07-24 コニカミノルタ株式会社 Méthode et appareil de formation de film fin

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Publication number Priority date Publication date Assignee Title
JPH06267835A (ja) * 1993-03-12 1994-09-22 Seiko Instr Inc 薄膜のパターニング方法
JP2005530924A (ja) * 2002-05-29 2005-10-13 インフィネオン テクノロジーズ アクチエンゲゼルシャフト 窒化シリコンまたは酸窒化シリコンを蒸着するためのプラズマ化学蒸着方法、および層構造の製造方法、並びに、層構造
JP2006261616A (ja) * 2005-03-18 2006-09-28 Seiko Epson Corp 成膜方法、半導体装置および電子機器
JP2007324170A (ja) * 2006-05-30 2007-12-13 Yoshimi Shiotani 照射装置及び照射装置を用いた半導体製造装置
JP2012004349A (ja) * 2010-06-17 2012-01-05 Az Electronic Materials Kk シリコンオキシナイトライド膜の形成方法およびそれにより製造されたシリコンオキシナイトライド膜付き基板
JP2013065840A (ja) * 2011-08-31 2013-04-11 Semiconductor Energy Lab Co Ltd 半導体装置、及び半導体装置の作製方法
WO2014112554A1 (fr) * 2013-01-16 2014-07-24 コニカミノルタ株式会社 Méthode et appareil de formation de film fin

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019060098A1 (fr) 2017-09-19 2019-03-28 M-I L.L.C. Dégazage et analyse de fluide de forage

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