WO2016067799A1 - Method for producing metal oxide semiconductor film, metal oxide semiconductor film, thin film transistor and electronic device - Google Patents
Method for producing metal oxide semiconductor film, metal oxide semiconductor film, thin film transistor and electronic device Download PDFInfo
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- WO2016067799A1 WO2016067799A1 PCT/JP2015/077296 JP2015077296W WO2016067799A1 WO 2016067799 A1 WO2016067799 A1 WO 2016067799A1 JP 2015077296 W JP2015077296 W JP 2015077296W WO 2016067799 A1 WO2016067799 A1 WO 2016067799A1
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- WIPO (PCT)
- Prior art keywords
- oxide semiconductor
- metal oxide
- film
- semiconductor film
- metal
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 199
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- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 183
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- 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
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/1201—Manufacture or treatment
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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
- H01L21/02112—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
- H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
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- 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
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
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- 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
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- 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
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- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
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Definitions
- the present invention relates to a method for manufacturing a metal oxide semiconductor film, and a metal oxide semiconductor film, a thin film transistor, and an electronic device.
- a metal oxide film as an oxide semiconductor film or an oxide conductor film has been put into practical use in production by a vacuum film forming method, and is currently attracting attention.
- it is required to form a metal oxide semiconductor film at a low temperature. Therefore, research and development have been actively conducted on the production of an oxide semiconductor film by a liquid phase process for the purpose of forming an oxide semiconductor film having high semiconductor characteristics at low temperature and easily under atmospheric pressure. ing.
- Recently, a method for manufacturing a thin film transistor (TFT) having high transport properties at a low temperature of 150 ° C. or lower by applying a solution on a substrate and using ultraviolet rays has been reported (see Non-Patent Document 1). ).
- the thin film containing the precursor of the metal oxide semiconductor is formed by heating at about 150 ° C. to volatilize the solvent, and then in the presence of oxygen.
- a method of manufacturing a metal oxide semiconductor by irradiating with ultraviolet light has been disclosed (see Patent Document 1).
- Non-Patent Document 1 only the one containing indium in the metal oxide semiconductor film showed high transport characteristics, and the transistor operation was confirmed in the Zn—Sn—O system containing no indium. I reported that I could't. Patent Document 1 only describes a metal oxide semiconductor containing indium.
- Non-Patent Document 2 reports an attempt to apply an annealing process combined with ultraviolet irradiation in the production of a Zn—Sn—O-based thin film that is a metal oxide semiconductor containing no indium.
- Non-Patent Document 2 in order to realize a good transistor operation, an annealing treatment in combination with ultraviolet irradiation is performed, followed by an annealing treatment in a vacuum. It is necessary to apply. Therefore, there is a problem that the production cost increases.
- An object of the present invention is to solve such problems of the prior art, and can be formed easily, at a low temperature, and under atmospheric pressure using an inexpensive material that does not contain indium, which is a rare metal.
- An object of the present invention is to provide a metal oxide semiconductor film manufacturing method capable of forming an oxide semiconductor film having high semiconductor characteristics, and a metal oxide semiconductor film, a thin film transistor, and an electronic device.
- the present inventor applied a solution containing zinc and tin as a solvent and metal components on a substrate to form a metal oxide semiconductor precursor film.
- the total metal component in the semiconductor precursor film is zinc and tin, and the composition ratio of zinc and tin is 0.7 ⁇ Sn / (Sn + Zn) ⁇ 0.9, whereby indium
- an oxide semiconductor film that can be easily formed at low temperature and under atmospheric pressure and has high semiconductor characteristics can be formed using an inexpensive material that does not include the present invention, and the present invention has been completed. That is, it has been found that the above object can be achieved by the following configuration.
- [3] The method for producing a metal oxide semiconductor film according to [1] or [2], wherein the temperature of the substrate during ultraviolet irradiation is maintained at 250 ° C. or lower in the conversion step.
- [4] The metal oxide according to any one of [1] to [3], wherein in the conversion step, the ultraviolet ray irradiated to the metal oxide semiconductor precursor film has an illuminance with a wavelength of 300 nm or less of 30 mW / cm 2 or more.
- a method for manufacturing a semiconductor film [5] The method for producing a metal oxide semiconductor film according to any one of [1] to [4], wherein the conversion step is performed in an atmosphere containing 1% by volume or more of oxygen.
- [6] The method for producing a metal oxide semiconductor film according to any one of [1] to [5], wherein 95% or more of all metal components in the metal oxide semiconductor precursor film are zinc and tin.
- [7] The method for producing a metal oxide semiconductor film according to any one of [1] to [6], wherein the solution is obtained by dissolving a metal salt or metal halide of zinc and tin in a solvent.
- [8] The method for producing a metal oxide semiconductor film according to any one of [1] to [7], wherein the solvent is methanol, methoxyethanol, or water.
- an oxide having high semiconductor characteristics that can be easily formed at a low temperature and under atmospheric pressure using an inexpensive material that does not contain indium which is a rare metal.
- a metal oxide semiconductor film manufacturing method capable of forming a semiconductor film, and a metal oxide semiconductor film, a thin film transistor, and an electronic device can be provided.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the effect of improving the characteristics of the metal oxide semiconductor film by the ultraviolet irradiation treatment can be made extremely high by appropriately selecting the composition ratio of zinc and tin. Specifically, by appropriately selecting the composition ratio of zinc and tin, grain boundary formation and surface roughness increase accompanying crystallization of the metal oxide semiconductor film can be suppressed, and the carrier density can be appropriately set. Since the range can be controlled, the effect of improving the characteristics of the metal oxide semiconductor film by the ultraviolet irradiation treatment can be made extremely high.
- a metal oxide semiconductor film having high electron transfer characteristics can be obtained at a low temperature process of 250 ° C. or less under atmospheric pressure using a material that does not contain indium which is a rare metal. .
- the manufacturing method of the present invention can manufacture a metal oxide semiconductor film under atmospheric pressure, it is not necessary to use a large vacuum apparatus.
- an inexpensive resin substrate with low heat resistance can be used.
- An inexpensive material that does not contain indium, which is a rare metal, can be used. Accordingly, the manufacturing cost of the metal oxide semiconductor film can be significantly reduced.
- a flexible electronic device such as a flexible display can be manufactured at low cost.
- Metal oxide semiconductor precursor film forming step First, a solution (metal oxide semiconductor precursor solution) containing tin as a main component and at least zinc as a solvent and a metal component is prepared and applied onto a substrate to form a metal oxide semiconductor precursor film.
- a solution metal oxide semiconductor precursor solution
- 80% or more of all metal components in the film are zinc and tin, and zinc and tin
- the composition ratio is 0.7 ⁇ Sn / (Sn + Zn) ⁇ 0.9.
- the structure of the substrate may be a single layer structure or a laminated structure.
- the substrate is not particularly limited, and for example, an inorganic substrate such as YSZ (Yttria-Stabilized Zirconia), glass, a resin substrate, or a composite material thereof can be used.
- an inorganic substrate such as YSZ (Yttria-Stabilized Zirconia), glass, a resin substrate, or a composite material thereof can be used.
- a resin substrate and a composite material thereof are preferable in terms of light weight and flexibility.
- 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 to the lower electrode, and the like.
- the thickness of the substrate in the present invention is not particularly limited, but is preferably 50 ⁇ m or more and 500 ⁇ m or less.
- the thickness of the substrate is 50 ⁇ m or more, the flatness of the substrate itself is further improved.
- 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.
- the metal oxide semiconductor precursor solution contains tin as a main component as a solvent and a metal component, and contains at least zinc.
- the main component in the present invention means that 50% or more of the total metal components in the solution are occupied by tin, and may contain a small amount of other metal components as necessary.
- the component ratio in the total metal components of zinc and tin is preferably 90% or more, and more preferably 95% or more.
- the said solution may contain a small amount of indium of less than 5%, and 1% or less is more preferable.
- the metal component in the solution is basically the same as the metal component in the metal oxide semiconductor precursor film. Therefore, in the present invention, the composition ratio of zinc and tin in the above solution is 0.7 ⁇ Sn / (Sn + Zn) ⁇ 0.9.
- the solution in the present invention is obtained by weighing a solute as a raw material so that the solution has a desired concentration, and stirring and dissolving in a solvent.
- the time for stirring and the temperature of the solution during stirring are not particularly limited as long as the solute is sufficiently dissolved.
- the concentration of the metal component in the metal oxide semiconductor precursor solution can be arbitrarily selected according to the viscosity and the desired film thickness, but is 0.01 mol / L or more from the viewpoint of the flatness and productivity of the thin film. It is preferable that it is 1.0 mol / L or less.
- the metal oxide semiconductor precursor solution After the metal oxide semiconductor precursor solution is applied on the substrate, it may be naturally dried to form a metal oxide semiconductor precursor film. However, the coating film is dried by heat treatment to obtain a metal oxide semiconductor precursor film. It is preferable. By drying, the fluidity of the coating film can be reduced, and the flatness of the finally obtained metal oxide semiconductor film can be improved. In addition, by selecting an appropriate drying temperature (35 ° C. or more and 100 ° C. or less), it is easy to finally obtain a metal oxide semiconductor film having higher electron transfer characteristics.
- the method for the heat treatment is not particularly limited, and can be selected from hot plate heating, electric furnace heating, infrared heating, microwave heating, and the like.
- the metal oxide semiconductor precursor film is converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment in a state where the metal oxide semiconductor precursor film is heated.
- 80% or more of all metal components in the film are zinc and tin, and the composition ratio of zinc and tin is 0.7 ⁇ Sn / (Sn + Zn). ) ⁇ 0.9, the effect of improving the characteristics of the metal oxide semiconductor film can be extremely enhanced by ultraviolet irradiation treatment at atmospheric pressure and at a low temperature of 250 ° C. or lower.
- the substrate temperature in the conversion step into the metal oxide semiconductor film is preferably 250 ° C. or lower, and more preferably higher than 120 ° C. If the substrate temperature in the conversion step is 250 ° C. or less, an increase in thermal energy can be suppressed to reduce the manufacturing cost, and application to a resin substrate with low heat resistance can be facilitated. In addition, when the temperature is higher than 120 ° C., a metal oxide semiconductor film having high electron transfer characteristics can be obtained in a shorter time. Moreover, from the viewpoint of manufacturing cost and the viewpoint of application to a resin substrate, more than 120 ° C. and 200 ° C. or less are more preferable.
- the heating means for the substrate in the conversion step is not particularly limited, and may be selected from hot plate heating, electric furnace heating, infrared heating, microwave heating, and the like.
- the ultraviolet ray applied to the metal oxide semiconductor precursor film preferably has an illuminance with a wavelength of 300 nm or less of 30 mW / cm 2 or more, and more preferably 50 mW / cm 2 .
- the illuminance is set to 30 mW / cm 2 or more, a metal oxide semiconductor film having high electron transfer characteristics can be obtained.
- the upper limit of illumination intensity is 500 mW / cm ⁇ 2 > or less from a viewpoint of apparatus cost.
- the ultraviolet irradiation in the conversion process may be performed until the metal oxide semiconductor precursor film is converted into the metal oxide semiconductor film.
- the ultraviolet irradiation time is preferably 5 minutes or more and 120 minutes or less from the viewpoint of productivity.
- the conversion step can be performed in the atmosphere under atmospheric pressure, and is preferably performed in an atmosphere containing 1% by volume or more of oxygen.
- an atmosphere containing oxygen a metal oxide semiconductor film having high electron transfer characteristics can be easily obtained.
- atmosphere is preferable from a viewpoint of production cost.
- SIMS is known as an analytical method that can detect an element constituting an object with very high sensitivity, and collides beam-like ions (primary ions) with the object to be analyzed, and forms the object by collision. Ions are ionized (secondary ions). A constituent element and its amount are detected by mass analysis of the secondary ions.
- the metal component in the metal oxide semiconductor film produced by the production method of the present invention is basically the same as the metal component in the metal oxide semiconductor precursor film. Therefore, 80% or more of all metal components in the metal oxide semiconductor film are zinc and tin, and the composition ratio of zinc and tin is 0.7 ⁇ Sn / (Sn + Zn) ⁇ 0.9.
- the ratio of zinc and tin to the total metal components in the metal oxide semiconductor film, and the composition ratio of zinc and tin are determined by XPS measurement (X-ray photoelectron spectroscopy) on the surface of the metal oxide semiconductor film. The number of atoms of such metals can be measured and calculated as the ratio of zinc and tin, and the composition ratio of zinc and tin.
- the metal oxide semiconductor film can be segmented and the ratio of zinc to tin and the composition ratio can be calculated by EDX measurement (energy dispersive X-ray spectroscopy) of a cross-sectional TEM (transmission electron microscope) of the film. .
- a metal oxide semiconductor film manufactured using the manufacturing method of the present invention is used as an active layer of a thin film transistor.
- the manufacturing method of the metal oxide semiconductor film of this invention and the metal oxide semiconductor film manufactured by it are not limited to the active layer of TFT.
- the element structure of the TFT according to the present invention is not particularly limited, and is either a so-called reverse stagger structure (also referred to as a bottom gate type) or a stagger structure (also referred to as a top gate type) based on the position of the gate electrode. Also good.
- a so-called reverse stagger structure also referred to as a bottom gate type
- a stagger structure also referred to as a top gate type
- either a so-called top contact type or bottom contact type may be used.
- the top gate type is a form in which a gate electrode is disposed on the upper side of the gate insulating film and an active layer is formed on the lower side of the gate insulating film when the substrate on which the TFT is formed is the lowermost layer.
- the bottom gate type is a form in which a gate electrode is disposed below the gate insulating film and an active layer is formed above the gate insulating film.
- the bottom contact type is a mode in which the source / drain electrodes are formed before the active layer and the lower surface of the active layer is in contact with the source / drain electrodes.
- the top contact type is the type in which the active layer is the source / drain. In this embodiment, the upper surface of the active layer is in contact with the source / drain electrodes.
- FIG. 1 is a schematic diagram showing an example of a top contact type TFT according to the present invention having a top gate structure.
- the above-described oxide semiconductor film is stacked as an active layer 14 on one main surface of the substrate 12.
- a source electrode 16 and a drain electrode 18 are disposed on the active layer 14 so as to be spaced apart from each other, and a gate insulating film 20 and a gate electrode 22 are sequentially stacked thereon.
- FIG. 2 is a schematic view showing an example of a bottom contact type TFT according to the present invention having a top gate structure.
- the source electrode 16 and the drain electrode 18 are disposed on one main surface of the substrate 12 so as to be separated from each other. Then, the above-described oxide semiconductor film, the gate insulating film 20, and the gate electrode 22 are sequentially stacked as the active layer.
- FIG. 3 is a schematic view showing an example of a TFT according to the present invention having a bottom gate structure and a top contact type.
- the gate electrode 22, the gate insulating film 20, and the above-described oxide semiconductor film as the active layer 14 are sequentially stacked on one main surface of the substrate 12.
- a source electrode 16 and a drain electrode 18 are spaced apart from each other on the surface of the active layer 14.
- FIG. 4 is a schematic view showing an example of a bottom contact type TFT according to the present invention having a bottom gate structure.
- the gate electrode 22 and the gate insulating film 20 are sequentially stacked on one main surface of the substrate 12.
- a source electrode 16 and a drain electrode 18 are disposed on the surface of the gate insulating film 20 so as to be spaced apart from each other, and the above-described oxide semiconductor film is stacked thereon as the active layer 14.
- the top gate type thin film transistor 10 shown in FIG. 1 will be mainly described.
- the thin film transistor of the present invention is not limited to the top gate type and may be a bottom gate type thin film transistor.
- the metal oxide semiconductor film is formed on the substrate 12 through the above-described metal oxide semiconductor precursor film forming step and conversion step, and the metal oxide semiconductor film is used as an active layer. Pattern to the shape.
- a metal oxide semiconductor precursor film having an active layer pattern is formed in advance by any of the above-described inkjet method, dispenser method, letterpress printing method, and intaglio printing method, and converted to a metal oxide semiconductor film. Is preferred.
- a protective film (not shown) on the active layer 14 for protecting the active layer 14 when the source / drain electrodes 16 and 18 are etched.
- the protective film may be formed continuously with the metal oxide semiconductor film, or may be formed after patterning of the metal oxide semiconductor film.
- the protective film may be a metal oxide layer or an organic material such as a resin. The protective layer may be removed after forming the source / drain electrodes.
- Source / drain electrodes 16 and 18 are formed on the active layer 14.
- Source / drain electrodes are made of high conductivity so as to function as electrodes, respectively, such as Al, Mo, Cr, Ta, Ti, Au, Ag, etc., Al—Nd, Ag alloy, tin oxide, zinc oxide
- a metal oxide conductor thin film such as indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or In—Ga—Zn—O can be used.
- the source / drain electrodes 16 and 18 are formed by, for example, a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method.
- the film may be formed according to a method appropriately selected in consideration of suitability with the material to be used.
- the film thickness of each electrode is preferably 10 nm or more and 1000 nm or less, and more preferably 50 nm or more and 100 nm or less in consideration of film forming properties, patterning properties by etching or lift-off methods, conductivity, and the like.
- the source / drain electrodes 16 and 18 may be formed by patterning into a predetermined shape by an etching or lift-off method, or may be directly formed by an inkjet method or the like. At this time, it is preferable to pattern all layers of the source / drain electrodes 16 and 18 and wirings connected to these electrodes simultaneously.
- the gate insulating film 20 After forming the source / drain electrodes 16 and 18 and the wiring, the gate insulating film 20 is formed.
- the gate insulating film 20 preferably has a high insulating property.
- an insulating film such as SiO 2 , SiNx, SiON, Al 2 O 3 , Y 2 O 3 , Ta 2 O 5 , HfO 2 , or a compound thereof is at least used. It may be an insulating film including two or more, and may have a single layer structure or a laminated structure.
- the gate insulating film 20 is a material used from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as CVD or plasma CVD method.
- the film can be formed according to a method appropriately selected in consideration of the suitability of
- the gate insulating film 20 needs to have a thickness for reducing leakage current and improving voltage resistance. On the other hand, if the gate insulating film 20 is too thick, the driving voltage is increased.
- the thickness of the gate insulating film 20 is preferably 10 nm to 10 ⁇ m, more preferably 50 nm to 1000 nm, and particularly preferably 100 nm to 400 nm.
- the gate electrode 22 is a material used from, for example, a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method.
- the film is formed according to a method appropriately selected in consideration of the suitability of
- the film thickness of the gate electrode 22 is preferably 10 nm or more and 1000 nm or less, and more preferably 50 nm or more and 200 nm or less in consideration of film forming properties, patterning properties by etching or lift-off methods, conductivity, and the like.
- the gate electrode 22 may be formed by patterning into a predetermined shape by an etching or lift-off method, or the pattern may be directly formed by an inkjet method or the like. At this time, it is preferable to pattern the gate electrode 22 and the wiring connected to the gate electrode 22 simultaneously.
- the use of the thin film transistor of the present invention described above is not particularly limited, but exhibits high transport characteristics. Therefore, for example, an electro-optical device (for example, a liquid crystal display device, an organic EL (Electro Luminescence) display device, an inorganic EL display device, etc.) In a display device, etc.), and a flexible display formed on a resin substrate having low heat resistance. Furthermore, the thin film transistor of the present invention is suitably used as a driving element (driving circuit) in various electronic devices such as various sensors such as an X-ray sensor and MEMS (Micro Electro Mechanical System).
- driving element driving circuit
- various electronic devices such as various sensors such as an X-ray sensor and MEMS (Micro Electro Mechanical System).
- FIG. 5 shows a schematic sectional view of a part of an example of a liquid crystal display device using the thin film transistor of the present invention
- FIG. 6 shows a schematic configuration diagram of electrical wiring.
- the liquid crystal display device 100 of the present embodiment includes a plurality of gate wirings 113 that are parallel to each other and data wirings 114 that are parallel to each other and intersect the gate wirings 113.
- the gate wiring 113 and the data wiring 114 are electrically insulated.
- the TFT 10 is provided in the vicinity of the intersection between the gate wiring 113 and the data wiring 114.
- the gate electrode 22 of the TFT 10 is connected to the gate wiring 113, and the source electrode 16 of the TFT 10 is connected to the data wiring 114.
- the drain electrode 18 of the TFT 10 is connected to the pixel lower electrode 104 through a contact hole 116 provided in the gate insulating film 20 (a conductor is embedded in the contact hole 116).
- the pixel lower electrode 104 forms a capacitor 118 together with the grounded counter upper electrode 106.
- FIG. 7 shows a schematic sectional view of a part of an example of an active matrix organic EL display device using the thin film transistor of the present invention
- FIG. 8 shows a schematic configuration diagram of electric wiring.
- the upper electrode 210 may be a top emission type using a transparent electrode, or the bottom electrode 208 and each TFT electrode may be a transparent electrode.
- FIG. 9 shows a schematic sectional view of a part of an example of an X-ray sensor using the thin film transistor of the present invention
- FIG. 10 shows a schematic configuration diagram of its electric wiring.
- the X-ray sensor 300 of this embodiment includes the TFT 10 and the capacitor 310 formed on the substrate 12, the charge collection electrode 302 formed on the capacitor 310, the X-ray conversion layer 304, and the upper electrode 306. Composed.
- a passivation film 308 is provided on the TFT 10.
- the capacitor 310 has a structure in which an insulating film 316 is sandwiched between a capacitor lower electrode 312 and a capacitor upper electrode 314.
- the capacitor upper electrode 314 is connected to one of the source electrode 16 and the drain electrode 18 (the drain electrode 18 in FIG. 9) of the TFT 10 through a contact hole 318 provided in the insulating film 316.
- the charge collection electrode 302 is provided on the capacitor upper electrode 314 in the capacitor 310 and is in contact with the capacitor upper electrode 314.
- the X-ray conversion layer 304 is a layer made of amorphous selenium, and is provided so as to cover the TFT 10 and the capacitor 310.
- the upper electrode 306 is provided on the X-ray conversion layer 304 and is in contact with the X-ray conversion layer 304.
- X-rays enter from the upper electrode 306 side in FIG. 9 and generate electron-hole pairs in the X-ray conversion layer 304.
- the generated charge is accumulated in the capacitor 310 and read out by sequentially scanning the TFT 10.
- a TFT having a top gate structure is provided in the liquid crystal display device 100, the organic EL display device 200, and the X-ray sensor 300 of the above embodiment.
- the TFT is not limited to this, and FIGS. A TFT having the structure shown in FIG.
- a metal oxide semiconductor precursor film is formed by applying the following solution on the substrate to form a metal oxide semiconductor precursor film, and then irradiating the metal oxide semiconductor precursor film with ultraviolet rays in a heated state.
- a metal oxide semiconductor film was formed by converting to a metal oxide semiconductor film.
- substrate A p-type silicon substrate with a thermal oxide film was used as the substrate.
- the thermal oxide film of this substrate was used as the gate insulating film of the TFT.
- the prepared solution was spin-coated on a p-type silicon 1 inch ⁇ 1 inch substrate with a thermal oxide film at a rotational speed of 5000 rpm for 30 seconds, and then dried on a hot plate heated to 60 ° C. for 5 minutes.
- Ultraviolet illuminance with a peak wavelength of 254 nm at the sample position is measured using a UV integrating light meter (manufactured by Hamamatsu Photonics Co., Ltd., controller C9536, sensor head H9536-254, having spectral sensitivity in the range of over 200 nm to about 300 nm). It was 51 mW / cm 2 when measured.
- a source / drain electrode was formed on the metal oxide semiconductor film obtained above by vapor deposition, thereby producing a simple TFT.
- the source / drain electrodes were formed by pattern film formation using a metal mask, and Ti was formed to a thickness of 50 nm.
- the source / drain electrode size was 1 mm ⁇ 1 mm, respectively, and the distance between the electrodes was 0.2 mm.
- Example 2 The solution was prepared by setting the mixing ratio of the tin chloride solution and the zinc acetate solution to 7: 3, and the composition ratio Sn / (Sn + Zn) of zinc and tin of the metal oxide semiconductor precursor film was set to 0.7.
- a simple TFT was fabricated by forming a metal oxide semiconductor film in the same manner as in Example 1.
- Example 3 A simple TFT was produced by forming a metal oxide semiconductor film in the same manner as in Example 1 except that the substrate temperature during the ultraviolet irradiation treatment in the conversion step was 230 ° C.
- Example 4 A simple TFT was produced by forming a metal oxide semiconductor film in the same manner as in Example 1 except that the ultraviolet light illuminance during the ultraviolet irradiation treatment in the conversion step was 80 mW / cm 2 .
- Example 5 A simple TFT was produced by forming a metal oxide semiconductor film in the same manner as in Example 1 except that the metal oxide semiconductor precursor solution shown below was used.
- Gallium nitrate (Ga (NO 3 ) 3 xH 2 O, 5N, manufactured by Kojundo Chemical Laboratory Co., Ltd.) and indium nitrate (In (NO 3 ) 3 xH 2 O, 4N, manufactured by Kojundo Chemical Laboratory Co., Ltd.) )
- 2-methoxyethanol (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare 0.3 mol / L gallium nitrate solution and indium nitrate solution, and then gallium nitrate solution and nitric acid solution
- the gallium indium mixed solution was prepared by mixing the indium solution at a ratio of 1: 4.
- the metal oxide semiconductor precursor is prepared by mixing the solution of the zinc / tin composition ratio Sn / (Sn + Zn) 0.9 used in Example 1 and the gallium indium mixed solution in a ratio of 4: 1.
- a body solution was prepared. That is, in the above solution, the ratio of zinc and tin is 80%, and the composition ratio Sn / (Sn + Zn) between zinc and tin is 0.9.
- Example 6 Except that the mixing ratio of the zinc / tin composition ratio Sn / (Sn + Zn) 0.9 used in Example 1 and the gallium indium mixed solution was 9: 1, the same procedure as in Example 5 was performed. A metal oxide semiconductor precursor solution was prepared, a metal oxide semiconductor film was formed, and a simple TFT was produced. That is, in the above solution, the ratio of zinc and tin is 90%, and the composition ratio Sn / (Sn + Zn) between zinc and tin is 0.9.
- Example 2 The solution was prepared by setting the mixing ratio of the tin chloride solution and the zinc acetate solution to 6: 4, except that the composition ratio Sn / (Sn + Zn) of zinc and tin of the metal oxide semiconductor precursor film was 0.6.
- a simple TFT was fabricated by forming a metal oxide semiconductor film in the same manner as in Example 1.
- Example 3 A simple TFT was fabricated by forming a metal oxide semiconductor film in the same manner as in Example 1 except that no ultraviolet irradiation was performed in the conversion step.
- the simple TFT of the example provided with the metal oxide semiconductor film manufactured by the manufacturing method of the present invention has a large linear mobility and high semiconductor characteristics as compared with the simple TFT of the comparative example.
- the composition ratio of zinc and tin of the metal oxide semiconductor precursor film is in the range of 0.7 ⁇ Sn / (Sn + Zn) ⁇ 0.9. It can be seen that the linear mobility can be increased. Moreover, it can be seen from the comparison between Example 1 and Examples 5 and 6 that the higher the ratio of tin and zinc in all metal components, the greater the linear mobility.
- linear mobility does not change even if the illumination intensity of the ultraviolet-ray in a conversion process is enlarged from the comparison with Example 1 and Example 4.
- FIG. This shows that it is sufficient to irradiate ultraviolet rays having sufficient illuminance to convert the metal oxide semiconductor precursor film. It can also be seen from Examples 1 to 4 that the linear mobility can be increased even by heating at a low temperature of 250 ° C. or lower.
- Comparative Example 1 and Comparative Example 4 both show the behavior of the conductor, but Comparative Example 4 in which ultraviolet irradiation is not performed is more than Comparative Example 1 in which ultraviolet irradiation is performed. It can be seen that the electron transfer characteristics are higher. From this, it can be seen that in order to obtain the effect of the ultraviolet irradiation treatment, it is necessary to appropriately select the range of the composition ratio of zinc and tin. From the above, the effects of the present invention are clear.
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Abstract
Description
また、耐熱性の低い樹脂基板へ金属酸化物半導体を形成するため、低温で金属酸化物半導体膜を形成することが求められている。
そこで、低温で、かつ、簡便に、大気圧下で高い半導体特性を有する酸化物半導体膜を形成することを目的とした、液相プロセスによる酸化物半導体膜の作製に関して研究開発が盛んに行われている。最近では、溶液を基板上に塗布し、紫外線を用いることで150℃以下の低温で高い輸送特性を有する薄膜トランジスタ(TFT:Thin Film Transistor)を製造する手法が報告されている(非特許文献1参照)。 A metal oxide film as an oxide semiconductor film or an oxide conductor film has been put into practical use in production by a vacuum film forming method, and is currently attracting attention.
In addition, in order to form a metal oxide semiconductor on a resin substrate having low heat resistance, it is required to form a metal oxide semiconductor film at a low temperature.
Therefore, research and development have been actively conducted on the production of an oxide semiconductor film by a liquid phase process for the purpose of forming an oxide semiconductor film having high semiconductor characteristics at low temperature and easily under atmospheric pressure. ing. Recently, a method for manufacturing a thin film transistor (TFT) having high transport properties at a low temperature of 150 ° C. or lower by applying a solution on a substrate and using ultraviolet rays has been reported (see Non-Patent Document 1). ).
また、特許文献1には、インジウムを含む金属酸化物半導体が記載されるのみである。 Here, in Non-Patent Document 1, only the one containing indium in the metal oxide semiconductor film showed high transport characteristics, and the transistor operation was confirmed in the Zn—Sn—O system containing no indium. I reported that I couldn't.
Patent Document 1 only describes a metal oxide semiconductor containing indium.
そのため、インジウムを含まない金属酸化物半導体を、液相プロセスにより作製することが研究されている。
例えば、非特許文献2には、インジウムを含まない金属酸化物半導体である、Zn-Sn-O系薄膜の作製において、紫外線照射を併用したアニール処理を適用する試みが報告されている。 Indium is a rare metal with a limited production volume, and in the future, the supply amount is expected to be tight and the raw material price is expected to rise. Therefore, a material that does not use indium is required as a metal oxide semiconductor material.
Therefore, it has been studied to produce a metal oxide semiconductor containing no indium by a liquid phase process.
For example, Non-Patent Document 2 reports an attempt to apply an annealing process combined with ultraviolet irradiation in the production of a Zn—Sn—O-based thin film that is a metal oxide semiconductor containing no indium.
すなわち、以下の構成により上記目的を達成することができることを見出した。 As a result of intensive studies to achieve the above object, the present inventor applied a solution containing zinc and tin as a solvent and metal components on a substrate to form a metal oxide semiconductor precursor film. A body film forming step and a conversion step of converting the metal oxide semiconductor precursor film into a metal oxide semiconductor film by irradiating with ultraviolet rays while the metal oxide semiconductor precursor film is heated. 80% or more of the total metal component in the semiconductor precursor film is zinc and tin, and the composition ratio of zinc and tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9, whereby indium It has been found that an oxide semiconductor film that can be easily formed at low temperature and under atmospheric pressure and has high semiconductor characteristics can be formed using an inexpensive material that does not include the present invention, and the present invention has been completed.
That is, it has been found that the above object can be achieved by the following configuration.
金属酸化物半導体前駆体膜を加熱した状態で紫外線照射を行うことにより、金属酸化物半導体前駆体膜を金属酸化物半導体膜に転化させる転化工程とを有し、
金属酸化物半導体前駆体膜中の全金属成分の80%以上が亜鉛およびスズであり、亜鉛とスズとの組成比が、0.7≦Sn/(Sn+Zn)≦0.9である金属酸化物半導体膜の製造方法。
[2] 金属酸化物半導体前駆体膜中におけるインジウムの成分比が5%未満である[1]に記載の金属酸化物半導体膜の製造方法。
[3] 転化工程において、紫外線照射中の基板の温度を250℃以下に保持する[1]または[2]に記載の金属酸化物半導体膜の製造方法。
[4] 転化工程において、金属酸化物半導体前駆体膜に照射される紫外線は、波長300nm以下の照度が30mW/cm2以上である[1]~[3]のいずれかに記載の金属酸化物半導体膜の製造方法。
[5] 転化工程は、酸素を1体積%以上含む雰囲気中で行われる[1]~[4]のいずれかに記載の金属酸化物半導体膜の製造方法。
[6] 金属酸化物半導体前駆体膜中の全金属成分の95%以上が亜鉛およびスズである[1]~[5]のいずれかに記載の金属酸化物半導体膜の製造方法。
[7] 溶液が、亜鉛及びスズの金属塩または金属ハロゲン化物を溶媒に溶解してなるものである[1]~[6]のいずれかに記載の金属酸化物半導体膜の製造方法。
[8] 溶媒が、メタノール、メトキシエタノール、または、水である[1]~[7]のいずれかに記載の金属酸化物半導体膜の製造方法。
[9] 溶液中の金属成分の濃度が、0.01mol/L~1.0mol/Lである[1]~[8]のいずれかに記載の金属酸化物半導体膜の製造方法。
[10] [1]~[9]のいずれかに記載の金属酸化物半導体膜の製造方法を用いて作製された金属酸化物半導体膜。
[11] 二次イオン質量分析法による膜中の炭素濃度が1×1019atoms/cm3以上1×1020atoms/cm3以下である[10]に記載の金属酸化物半導体膜。
[12] 二次イオン質量分析法による膜中の水素濃度が2×1022atoms/cm3以上4×1022atoms/cm3以下である[10]または[11]に記載の金属酸化物半導体膜。
[13] [10]~[12]のいずれかに記載の金属酸化物半導体膜を含む活性層と、ソース電極と、ドレイン電極と、ゲート絶縁膜と、ゲート電極とを有する薄膜トランジスタ。
[14] [13]に記載の薄膜トランジスタを備える電子デバイス。 [1] A metal oxide semiconductor precursor film forming step of forming a metal oxide semiconductor precursor film by applying a solution containing zinc and tin as a solvent and a metal component on a substrate;
A conversion step of converting the metal oxide semiconductor precursor film into a metal oxide semiconductor film by performing ultraviolet irradiation while the metal oxide semiconductor precursor film is heated,
Metal oxide in which 80% or more of all metal components in the metal oxide semiconductor precursor film are zinc and tin, and the composition ratio of zinc and tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9 A method for manufacturing a semiconductor film.
[2] The method for producing a metal oxide semiconductor film according to [1], wherein a component ratio of indium in the metal oxide semiconductor precursor film is less than 5%.
[3] The method for producing a metal oxide semiconductor film according to [1] or [2], wherein the temperature of the substrate during ultraviolet irradiation is maintained at 250 ° C. or lower in the conversion step.
[4] The metal oxide according to any one of [1] to [3], wherein in the conversion step, the ultraviolet ray irradiated to the metal oxide semiconductor precursor film has an illuminance with a wavelength of 300 nm or less of 30 mW / cm 2 or more. A method for manufacturing a semiconductor film.
[5] The method for producing a metal oxide semiconductor film according to any one of [1] to [4], wherein the conversion step is performed in an atmosphere containing 1% by volume or more of oxygen.
[6] The method for producing a metal oxide semiconductor film according to any one of [1] to [5], wherein 95% or more of all metal components in the metal oxide semiconductor precursor film are zinc and tin.
[7] The method for producing a metal oxide semiconductor film according to any one of [1] to [6], wherein the solution is obtained by dissolving a metal salt or metal halide of zinc and tin in a solvent.
[8] The method for producing a metal oxide semiconductor film according to any one of [1] to [7], wherein the solvent is methanol, methoxyethanol, or water.
[9] The method for producing a metal oxide semiconductor film according to any one of [1] to [8], wherein the concentration of the metal component in the solution is 0.01 mol / L to 1.0 mol / L.
[10] A metal oxide semiconductor film produced using the method for producing a metal oxide semiconductor film according to any one of [1] to [9].
[11] The metal oxide semiconductor film according to [10], wherein the carbon concentration in the film by secondary ion mass spectrometry is 1 × 10 19 atoms / cm 3 or more and 1 × 10 20 atoms / cm 3 or less.
[12] The metal oxide semiconductor according to [10] or [11], wherein the hydrogen concentration in the film by secondary ion mass spectrometry is 2 × 10 22 atoms / cm 3 or more and 4 × 10 22 atoms / cm 3 or less. film.
[13] A thin film transistor having an active layer including the metal oxide semiconductor film according to any one of [10] to [12], a source electrode, a drain electrode, a gate insulating film, and a gate electrode.
[14] An electronic device comprising the thin film transistor according to [13].
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
本発明の金属酸化物半導体膜の製造方法(以下、「本発明の製造方法」ともいう)は、溶媒及び金属成分としてスズを主成分とし、少なくとも亜鉛を含む溶液を基板上に塗布して金属酸化物半導体前駆体膜を形成する金属酸化物半導体前駆体膜形成工程と、金属酸化物半導体前駆体膜を加熱した状態で紫外線照射を行うことにより金属酸化物半導体前駆体膜を金属酸化物半導体膜に転化させる転化工程とを有し、金属酸化物半導体前駆体膜中の全金属成分の80%以上が亜鉛およびスズであり、亜鉛とスズとの組成比が0.7≦Sn/(Sn+Zn)≦0.9であることを特徴とする。 <Method for producing metal oxide semiconductor film>
The method for producing a metal oxide semiconductor film of the present invention (hereinafter also referred to as “the method of production of the present invention”) is a method in which a solution containing at least zinc as a solvent and a metal component as a main component and at least zinc is applied onto a substrate. A metal oxide semiconductor precursor film forming step for forming an oxide semiconductor precursor film, and the metal oxide semiconductor precursor film is converted into a metal oxide semiconductor by performing ultraviolet irradiation while the metal oxide semiconductor precursor film is heated. A conversion step of converting into a film, wherein 80% or more of all metal components in the metal oxide semiconductor precursor film are zinc and tin, and the composition ratio of zinc and tin is 0.7 ≦ Sn / (Sn + Zn ) ≦ 0.9.
具体的には、亜鉛とスズとの組成比を適切に選択することで、金属酸化物半導体膜の結晶化に伴う粒界形成および表面粗さの増大を抑制し、かつ、キャリア密度を適切な範囲に制御可能となるので、紫外線照射処理による金属酸化物半導体膜の特性向上効果を極めて高くすることができる。
本発明の製造方法を用いることで、レアメタルであるインジウムを含まない材料を用いて、大気圧下、250℃以下の低温プロセスで、高い電子伝達特性を有する金属酸化物半導体膜を得ることができる。 According to the study by the present inventors, it has been found that the effect of improving the characteristics of the metal oxide semiconductor film by the ultraviolet irradiation treatment can be made extremely high by appropriately selecting the composition ratio of zinc and tin. .
Specifically, by appropriately selecting the composition ratio of zinc and tin, grain boundary formation and surface roughness increase accompanying crystallization of the metal oxide semiconductor film can be suppressed, and the carrier density can be appropriately set. Since the range can be controlled, the effect of improving the characteristics of the metal oxide semiconductor film by the ultraviolet irradiation treatment can be made extremely high.
By using the manufacturing method of the present invention, a metal oxide semiconductor film having high electron transfer characteristics can be obtained at a low temperature process of 250 ° C. or less under atmospheric pressure using a material that does not contain indium which is a rare metal. .
また、耐熱性の低い安価な樹脂基板に適用できることからフレキシブルディスプレイ等のフレキシブル電子デバイスを安価に作製することが可能となる。 Since the manufacturing method of the present invention can manufacture a metal oxide semiconductor film under atmospheric pressure, it is not necessary to use a large vacuum apparatus. In addition, since it can be manufactured by a low-temperature process of 250 ° C. or less, an inexpensive resin substrate with low heat resistance can be used. An inexpensive material that does not contain indium, which is a rare metal, can be used. Accordingly, the manufacturing cost of the metal oxide semiconductor film can be significantly reduced.
In addition, since it can be applied to an inexpensive resin substrate having low heat resistance, a flexible electronic device such as a flexible display can be manufactured at low cost.
まず、溶媒及び金属成分としてスズを主成分として少なくとも亜鉛を含む溶液(金属酸化物半導体前駆体溶液)を用意し、基板上に塗布して金属酸化物半導体前駆体膜を形成する。
ここで、本発明においては、金属酸化物半導体前駆体膜形成工程で形成される金属酸化物半導体前駆体膜は、膜中の全金属成分の80%以上が亜鉛およびスズであり、亜鉛とスズとの組成比が、0.7≦Sn/(Sn+Zn)≦0.9である。 [Metal oxide semiconductor precursor film forming step]
First, a solution (metal oxide semiconductor precursor solution) containing tin as a main component and at least zinc as a solvent and a metal component is prepared and applied onto a substrate to form a metal oxide semiconductor precursor film.
Here, in the present invention, in the metal oxide semiconductor precursor film formed in the metal oxide semiconductor precursor film forming step, 80% or more of all metal components in the film are zinc and tin, and zinc and tin The composition ratio is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
基板の形状、構造、大きさ等については特に制限はなく、目的に応じて適宜選択することができる。基板の構造は単層構造であってもよいし、積層構造であってもよい。 (substrate)
There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the objective. The structure of the substrate may be a single layer structure or a laminated structure.
上記金属酸化物半導体前駆体溶液は、溶媒及び金属成分としてスズを主成分とし、少なくとも亜鉛を含む。ここで、本発明における主成分とは、上記溶液中の全金属成分の50%以上をスズで占めることを意味し、必要に応じて少量の他の金属成分を含んでいてもよい。
また、形成される金属酸化物半導体膜の半導体特性の観点から、亜鉛およびスズの全金属成分中の成分比は、90%以上が好ましく、95%以上がより好ましい。
また、上記溶液は、5%未満の少量のインジウムを含んでいてもよく、1%以下がより好ましい。
ここで、上記溶液中の金属成分は、基本的に、金属酸化物半導体前駆体膜中の金属成分と同じである。従って、本発明においては、上記溶液の亜鉛とスズとの組成比は、0.7≦Sn/(Sn+Zn)≦0.9である。 (solution)
The metal oxide semiconductor precursor solution contains tin as a main component as a solvent and a metal component, and contains at least zinc. Here, the main component in the present invention means that 50% or more of the total metal components in the solution are occupied by tin, and may contain a small amount of other metal components as necessary.
In addition, from the viewpoint of semiconductor characteristics of the metal oxide semiconductor film to be formed, the component ratio in the total metal components of zinc and tin is preferably 90% or more, and more preferably 95% or more.
Moreover, the said solution may contain a small amount of indium of less than 5%, and 1% or less is more preferable.
Here, the metal component in the solution is basically the same as the metal component in the metal oxide semiconductor precursor film. Therefore, in the present invention, the composition ratio of zinc and tin in the above solution is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
なお、本発明における溶液は、溶液中に金属酸化物粒子等の不溶物を含まない溶液を用いることが好ましい。溶液中に金属酸化物粒子等の不溶物を含まない溶液を用いることで金属酸化物半導体膜を形成した際の表面粗さが小さくなり、面内均一性に優れた金属酸化物半導体膜を形成することが出来る。 The metal oxide semiconductor precursor solution is obtained by dissolving a compound containing zinc and tin, and it is preferable to use a metal salt or metal halide of zinc and tin. By using a metal salt or a metal halide, it is possible to easily dissolve the solute in various solvents, and it is easy to obtain high electron transfer characteristics. Examples of the metal salt include sulfate, phosphate, carbonate, acetate, oxalate, and examples of the metal halide include chloride, iodide, bromide and the like.
In addition, it is preferable to use the solution which does not contain insoluble matters, such as a metal oxide particle, in the solution in this invention. By using a solution that does not contain insoluble materials such as metal oxide particles in the solution, the surface roughness when forming the metal oxide semiconductor film is reduced, and a metal oxide semiconductor film with excellent in-plane uniformity is formed. I can do it.
上記金属酸化物半導体膜前駆体溶液を基板上に塗布する方法としては、例えば、スプレーコート法、スピンコート法、ブレードコート法、ディップコート法、キャスト法、ロールコート法、バーコート法、ダイコート法、ミスト法、インクジェット法、ディスペンサー法、スクリーン印刷法、凸版印刷法、及び凹版印刷法等が挙げられる。特に、微細パターンを容易に形成する観点から、インクジェット法、ディスペンサー法、凸版印刷法、及び凹版印刷法から選択される少なくとも一種の塗布法を用いることが好ましい。 (Application)
Examples of the method for applying the metal oxide semiconductor film precursor solution onto the substrate include spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, and die coating. Mist method, ink jet method, dispenser method, screen printing method, relief printing method, intaglio printing method and the like. In particular, from the viewpoint of easily forming a fine pattern, it is preferable to use at least one coating method selected from an inkjet method, a dispenser method, a relief printing method, and an intaglio printing method.
上記金属酸化物半導体前駆体溶液を基板上に塗布した後、自然乾燥して金属酸化物半導体前駆体膜としてもよいが、加熱処理によって塗布膜を乾燥させ、金属酸化物半導体前駆体膜を得ることが好ましい。乾燥によって、塗布膜の流動性を低減させ、最終的に得られる金属酸化物半導体膜の平坦性を向上させることが出来る。又、適切な乾燥温度(35℃以上100℃以下)を選択することにより、最終的に、より電子伝達特性の高い金属酸化物半導体膜を得られやすい。加熱処理の方法は特に限定されず、ホットプレート加熱、電気炉加熱、赤外線加熱、マイクロ波加熱等から選択することができる。 (Dry)
After the metal oxide semiconductor precursor solution is applied on the substrate, it may be naturally dried to form a metal oxide semiconductor precursor film. However, the coating film is dried by heat treatment to obtain a metal oxide semiconductor precursor film. It is preferable. By drying, the fluidity of the coating film can be reduced, and the flatness of the finally obtained metal oxide semiconductor film can be improved. In addition, by selecting an appropriate drying temperature (35 ° C. or more and 100 ° C. or less), it is easy to finally obtain a metal oxide semiconductor film having higher electron transfer characteristics. The method for the heat treatment is not particularly limited, and can be selected from hot plate heating, electric furnace heating, infrared heating, microwave heating, and the like.
また、乾燥を行う時間には特に制限はないが、膜の均一性、生産性の観点から15秒以上10分以下であることが好ましい。
また、乾燥における雰囲気には特に制限はないが、製造コスト等の観点から大気圧下、大気中で行うことが好ましい。 The drying is preferably started within 5 minutes after applying the solution on the substrate from the viewpoint of keeping the flatness of the film uniform.
The drying time is not particularly limited, but is preferably 15 seconds or longer and 10 minutes or shorter from the viewpoint of film uniformity and productivity.
Moreover, there is no restriction | limiting in particular in the atmosphere in drying, but it is preferable to carry out in air | atmosphere under atmospheric pressure from viewpoints, such as manufacturing cost.
次いで、上記金属酸化物半導体前駆体膜を加熱した状態で紫外線照射処理を行うことで金属酸化物半導体前駆体膜を金属酸化物半導体膜へと転化する。
ここで、上述のとおり、金属酸化物半導体前駆体膜は、膜中の全金属成分の80%以上が亜鉛およびスズであり、亜鉛とスズとの組成比が、0.7≦Sn/(Sn+Zn)≦0.9であるので、大気圧下で、かつ、250℃以下の低温での紫外線照射処理で、金属酸化物半導体膜の特性向上効果を極めて高くすることが可能である。 [Conversion process]
Next, the metal oxide semiconductor precursor film is converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment in a state where the metal oxide semiconductor precursor film is heated.
Here, as described above, in the metal oxide semiconductor precursor film, 80% or more of all metal components in the film are zinc and tin, and the composition ratio of zinc and tin is 0.7 ≦ Sn / (Sn + Zn). ) ≦ 0.9, the effect of improving the characteristics of the metal oxide semiconductor film can be extremely enhanced by ultraviolet irradiation treatment at atmospheric pressure and at a low temperature of 250 ° C. or lower.
上記金属酸化物半導体膜への転化工程における基板温度は250℃以下とすることが好ましく、120℃超とすることが好ましい。転化工程における基板温度を250℃以下とすれば、熱エネルギーの増大を抑制して製造コストを低く抑えることができ、また、耐熱性の低い樹脂基板への適用が容易となる。また、120℃超とすれば、より短時間で高い電子伝達特性の金属酸化物半導体膜を得ることが出来る。
また、製造コストの観点および樹脂基板への適用の観点から、120℃超、200℃以下がより好ましい。
転化工程における基板に対する加熱手段は特に限定されず、ホットプレート加熱、電気炉加熱、赤外線加熱、マイクロ波加熱等から選択すればよい。 (Heat treatment)
The substrate temperature in the conversion step into the metal oxide semiconductor film is preferably 250 ° C. or lower, and more preferably higher than 120 ° C. If the substrate temperature in the conversion step is 250 ° C. or less, an increase in thermal energy can be suppressed to reduce the manufacturing cost, and application to a resin substrate with low heat resistance can be facilitated. In addition, when the temperature is higher than 120 ° C., a metal oxide semiconductor film having high electron transfer characteristics can be obtained in a shorter time.
Moreover, from the viewpoint of manufacturing cost and the viewpoint of application to a resin substrate, more than 120 ° C. and 200 ° C. or less are more preferable.
The heating means for the substrate in the conversion step is not particularly limited, and may be selected from hot plate heating, electric furnace heating, infrared heating, microwave heating, and the like.
転化工程において、上記金属酸化物半導体前駆体膜に照射する紫外線は波長300nm以下の照度が30mW/cm2以上であることが好ましく、50mW/cm2であることがより好ましい。照度を30mW/cm2以上とすることで高い電子伝達特性の金属酸化物半導体膜を得ることが出来る。なお、照度の上限は、装置コストの観点から500mW/cm2以下であることが好ましい。 (UV irradiation)
In the conversion step, the ultraviolet ray applied to the metal oxide semiconductor precursor film preferably has an illuminance with a wavelength of 300 nm or less of 30 mW / cm 2 or more, and more preferably 50 mW / cm 2 . By setting the illuminance to 30 mW / cm 2 or more, a metal oxide semiconductor film having high electron transfer characteristics can be obtained. In addition, it is preferable that the upper limit of illumination intensity is 500 mW / cm < 2 > or less from a viewpoint of apparatus cost.
なお、金属酸化物半導体膜中の水素濃度および炭素濃度は、二次イオン質量分析法(SIMS(Secondary Ion Mass Spectroscopy))により測定した値である。SIMSは対象物を構成する元素を非常に高感度で検出することができる分析法として知られており、分析対象物にビーム状のイオン(一次イオン)を衝突させ、衝突により対象物を構成する物質をイオン化(二次イオン)させる。この二次イオンを質量分析することで構成元素とその量を検出するものである。 Here, the carbon concentration contained in the metal oxide semiconductor film formed by the conversion step is preferably 1 × 10 19 atoms / cm 3 or more and 1 × 10 20 atoms / cm 3 or less, and the hydrogen concentration is 2 × 10. It is preferably 22 atoms / cm 3 or more and 4 × 10 22 atoms / cm 3 or less. When the concentration is within the above range, high electron transfer characteristics are easily obtained.
Note that the hydrogen concentration and the carbon concentration in the metal oxide semiconductor film are values measured by secondary ion mass spectrometry (SIMS (Secondary Ion Mass Spectroscopy)). SIMS is known as an analytical method that can detect an element constituting an object with very high sensitivity, and collides beam-like ions (primary ions) with the object to be analyzed, and forms the object by collision. Ions are ionized (secondary ions). A constituent element and its amount are detected by mass analysis of the secondary ions.
金属酸化物半導体膜中の全金属成分に対する亜鉛およびスズの比率、ならびに、亜鉛とスズとの組成比は、XPS測定(X線光電子分光測定)により、金属酸化物半導体膜の表面における亜鉛、スズ等の金属の原子数を測定し、亜鉛およびスズの比率、亜鉛とスズとの組成比として算出することができる。あるいは、金属酸化物半導体膜を切片化加工し、膜の断面TEM(透過電子顕微鏡)のEDX測定(エネルギー分散型X線分光法)によって、亜鉛とスズの比率、組成比を算出することができる。 Moreover, the metal component in the metal oxide semiconductor film produced by the production method of the present invention is basically the same as the metal component in the metal oxide semiconductor precursor film. Therefore, 80% or more of all metal components in the metal oxide semiconductor film are zinc and tin, and the composition ratio of zinc and tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9.
The ratio of zinc and tin to the total metal components in the metal oxide semiconductor film, and the composition ratio of zinc and tin are determined by XPS measurement (X-ray photoelectron spectroscopy) on the surface of the metal oxide semiconductor film. The number of atoms of such metals can be measured and calculated as the ratio of zinc and tin, and the composition ratio of zinc and tin. Alternatively, the metal oxide semiconductor film can be segmented and the ratio of zinc to tin and the composition ratio can be calculated by EDX measurement (energy dispersive X-ray spectroscopy) of a cross-sectional TEM (transmission electron microscope) of the film. .
本発明の製造方法により作製された金属酸化物半導体膜は高い電子伝達特性を示すことから、薄膜トランジスタ(TFT)の活性層に好適に用いることができる。 <Thin film transistor>
Since the metal oxide semiconductor film manufactured by the manufacturing method of the present invention exhibits high electron transfer characteristics, it can be suitably used for an active layer of a thin film transistor (TFT).
本実施形態の薄膜トランジスタ10を製造する場合、まず基板12上に上述した金属酸化物半導体前駆体膜形成工程及び転化工程を経て金属酸化物半導体膜を形成し、上記金属酸化物半導体膜を活性層の形状にパターンニングする。パターンニングは上述したインクジェット法、ディスペンサー法、凸版印刷法、及び凹版印刷法のいずれかによって予め活性層のパターンを有する金属酸化物半導体前駆体膜を形成して金属酸化物半導体膜に転化することが好ましい。 (Active layer)
When manufacturing the
上記活性層14上にソース・ドレイン電極16、18を形成する。ソース・ドレイン電極はそれぞれ電極として機能するように高い導電性を有するものを用い、Al,Mo,Cr,Ta,Ti,Au,Ag等の金属、Al-Nd、Ag合金、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫(ITO)、酸化亜鉛インジウム(IZO)、In-Ga-Zn-O等の金属酸化物導電体薄膜等を用いて形成することが出来る。 (Source / drain electrodes)
Source /
ソース・ドレイン電極16、18及び配線を形成した後、ゲート絶縁膜20を形成する。ゲート絶縁膜20は高い絶縁性を有するものが好ましく、例えばSiO2、SiNx、SiON、Al2O3,Y2O3,Ta2O5,HfO2等の絶縁膜、又はこれらの化合物を少なくとも二つ以上含む絶縁膜としてもよく、単層構造であっても積層構造であってもよい。
ゲート絶縁膜20は、印刷方式、コーティング方式等の湿式方式、真空蒸着法、スパッタリング法、イオンプレーティング法等の物理的方式、CVD、プラズマCVD法等の化学的方式等の中から使用する材料との適性を考慮して適宜選択した方法に従って成膜することができる。 (Gate insulation film)
After forming the source /
The
ゲート絶縁膜20を形成した後、ゲート電極22を形成する。ゲート電極22は高い導電性を有するものを用い、例えばAl,Mo,Cr,Ta,Ti,Au,Ag等の金属、Al-Nd,Ag合金、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫(ITO)、酸化亜鉛インジウム(IZO)、IGZO等の金属酸化物導電膜等を用いて形成することができる。ゲート電極22としてはこれらの導電膜を単層構造又は2層以上の積層構造として用いることが出来る。 (Gate electrode)
After forming the
ゲート電極22の膜厚は成膜性、エッチングやリフトオフ法によるパターンニング性、導電性等を考慮すると、10nm以上1000nm以下とすることが好ましく、50nm以上200nm以下とすることがより好ましい。
成膜後、エッチング又はリフトオフ法により所定の形状にパターンニングして、ゲート電極22を形成してもよく、インクジェット法等により直接パターン形成してもよい。この際、ゲート電極22及びゲート電極22に接続される配線を同時にパターンニングすることが好ましい。 The
The film thickness of the
After the film formation, the
更に本発明の薄膜トランジスタは、X線センサー等の各種センサー、MEMS(Micro Electro Mechanical System)等、種々の電子デバイスにおける駆動素子(駆動回路)として、好適に用いられる。 The use of the thin film transistor of the present invention described above is not particularly limited, but exhibits high transport characteristics. Therefore, for example, an electro-optical device (for example, a liquid crystal display device, an organic EL (Electro Luminescence) display device, an inorganic EL display device, etc.) In a display device, etc.), and a flexible display formed on a resin substrate having low heat resistance.
Furthermore, the thin film transistor of the present invention is suitably used as a driving element (driving circuit) in various electronic devices such as various sensors such as an X-ray sensor and MEMS (Micro Electro Mechanical System).
本発明の薄膜トランジスタを用いる液晶表示装置の一例について、図5にその一部分の概略断面図を示し、図6に電気配線の概略構成図を示す。 <Liquid crystal display device>
FIG. 5 shows a schematic sectional view of a part of an example of a liquid crystal display device using the thin film transistor of the present invention, and FIG. 6 shows a schematic configuration diagram of electrical wiring.
本発明の薄膜トランジスタを用いるアクティブマトリックス方式の有機EL表示装置の一例について、図7に一部分の概略断面図を示し、図8に電気配線の概略構成図を示す。 <Organic EL display device>
FIG. 7 shows a schematic sectional view of a part of an example of an active matrix organic EL display device using the thin film transistor of the present invention, and FIG. 8 shows a schematic configuration diagram of electric wiring.
本発明の薄膜トランジスタを用いるX線センサの一例について、図9にその一部分の概略断面図を示し、図10にその電気配線の概略構成図を示す。 <X-ray sensor>
FIG. 9 shows a schematic sectional view of a part of an example of an X-ray sensor using the thin film transistor of the present invention, and FIG. 10 shows a schematic configuration diagram of its electric wiring.
X線変換層304はアモルファスセレンからなる層であり、TFT10およびキャパシタ310を覆うように設けられている。
上部電極306はX線変換層304上に設けられており、X線変換層304に接している。 The
The
The
<金属酸化物半導体膜の作製>
以下に示す溶液を基板上に塗布して金属酸化物半導体前駆体膜を形成し、この金属酸化物半導体前駆体膜を加熱した状態で紫外線照射を行うことにより、金属酸化物半導体前駆体膜を金属酸化物半導体膜に転化させて金属酸化物半導体膜を作製した。 [Example 1]
<Production of metal oxide semiconductor film>
A metal oxide semiconductor precursor film is formed by applying the following solution on the substrate to form a metal oxide semiconductor precursor film, and then irradiating the metal oxide semiconductor precursor film with ultraviolet rays in a heated state. A metal oxide semiconductor film was formed by converting to a metal oxide semiconductor film.
(溶液)
塩化第二スズ(SnCl4・xH2O、3N、株式会社高純度化学研究所製)及び酢酸亜鉛(Zn(CH3COO)2・2H2O、株式会社高純度化学研究所製)をそれぞれ2-メトキシエタノール(試薬特級、和光純薬工業株式会社製)中に溶解させ、0.3mol/Lの濃度の塩化スズ溶液及び酢酸亜鉛溶液を調製し、その後、塩化スズ溶液と酢酸亜鉛溶液とを9:1の割合で混合することで、金属酸化物半導体前駆体溶液を調製した。
すなわち、上記溶液は、亜鉛及びスズの割合が100%であり、亜鉛とスズとの組成比Sn/(Sn+Zn)が0.9である。 [Metal oxide semiconductor precursor film forming step]
(solution)
Stannic chloride (SnCl 4 · xH 2 O, 3N, manufactured by Kojundo Chemical Laboratory Co., Ltd.) and zinc acetate (Zn (CH 3 COO) 2 · 2H 2 O, manufactured by Kojundo Chemical Laboratory Co., Ltd.), respectively Dissolve in 2-methoxyethanol (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a tin chloride solution and a zinc acetate solution with a concentration of 0.3 mol / L. Were mixed at a ratio of 9: 1 to prepare a metal oxide semiconductor precursor solution.
That is, in the above solution, the ratio of zinc and tin is 100%, and the composition ratio Sn / (Sn + Zn) between zinc and tin is 0.9.
基板として熱酸化膜付p型シリコン基板を用いた。この基板の熱酸化膜をTFTのゲート絶縁膜として用いる構成とした。 (substrate)
A p-type silicon substrate with a thermal oxide film was used as the substrate. The thermal oxide film of this substrate was used as the gate insulating film of the TFT.
熱酸化膜付p型シリコン1inch×1inch基板上に、調製した溶液を5000rpmの回転速度で30秒スピンコートした後、60℃に加熱されたホットプレート上で5分間乾燥を行った。 (Coating / Drying)
The prepared solution was spin-coated on a p-type silicon 1 inch × 1 inch substrate with a thermal oxide film at a rotational speed of 5000 rpm for 30 seconds, and then dried on a hot plate heated to 60 ° C. for 5 minutes.
得られた金属酸化物半導体前駆体膜を、下記条件で金属酸化物半導体膜への転化を行った。
装置としては低圧水銀ランプを備えたVUVドライプロセッサ(株式会社オーク製作所社製、VUE-3400-F)を用いた。 [Conversion process]
The obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film under the following conditions.
As a device, a VUV dry processor (VUE-3400-F, manufactured by Oak Manufacturing Co., Ltd.) equipped with a low-pressure mercury lamp was used.
5分間の待機後、装置内のシャッターを開け、30分間で250℃まで昇温し、250℃到達後、60分間温度を保持しながら紫外線照射処理を行うことで金属酸化物半導体膜を得た。加熱処理下での紫外線照射処理の間、20L/minの乾燥空気を常にフローさせた。
試料位置での波長254nmをピーク波長とする紫外線照度を、紫外線積算光量計(浜松ホトニクス株式会社製、コントローラーC9536、センサヘッドH9536-254、200nm超300nm程度の範囲に分光感度を持つ)を用いて測定したところ、51mW/cm2であった。 The sample was set on an unheated hot plate in the apparatus and waited for 5 minutes. During this time, 20 L / min of dry air was flowed into the apparatus processing chamber.
After waiting for 5 minutes, the shutter inside the apparatus was opened, the temperature was raised to 250 ° C. in 30 minutes, and after reaching 250 ° C., an ultraviolet irradiation treatment was performed while maintaining the temperature for 60 minutes to obtain a metal oxide semiconductor film. . During the ultraviolet irradiation treatment under heat treatment, dry air of 20 L / min was always flowed.
Ultraviolet illuminance with a peak wavelength of 254 nm at the sample position is measured using a UV integrating light meter (manufactured by Hamamatsu Photonics Co., Ltd., controller C9536, sensor head H9536-254, having spectral sensitivity in the range of over 200 nm to about 300 nm). It was 51 mW / cm 2 when measured.
上記得られた金属酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜し、簡易型TFTを作製した。ソース・ドレイン電極成膜はメタルマスクを用いたパターン成膜にて作製し、Tiを50nm成膜した。ソース・ドレイン電極サイズは各々1mm×1mmとし、電極間距離は0.2mmとした。 [Production of TFT]
A source / drain electrode was formed on the metal oxide semiconductor film obtained above by vapor deposition, thereby producing a simple TFT. The source / drain electrodes were formed by pattern film formation using a metal mask, and Ti was formed to a thickness of 50 nm. The source / drain electrode size was 1 mm × 1 mm, respectively, and the distance between the electrodes was 0.2 mm.
塩化スズ溶液と酢酸亜鉛溶液との混合の割合を7:3として溶液を調製し、金属酸化物半導体前駆体膜の亜鉛とスズとの組成比Sn/(Sn+Zn)を0.7とした以外は、実施例1と同様にして金属酸化物半導体膜を形成して、簡易型TFTを作製した。 [Example 2]
The solution was prepared by setting the mixing ratio of the tin chloride solution and the zinc acetate solution to 7: 3, and the composition ratio Sn / (Sn + Zn) of zinc and tin of the metal oxide semiconductor precursor film was set to 0.7. A simple TFT was fabricated by forming a metal oxide semiconductor film in the same manner as in Example 1.
転化工程における紫外線照射処理の際の基板温度を230℃とした以外は実施例1と同様にして金属酸化物半導体膜を形成して、簡易型TFTを作製した。 [Example 3]
A simple TFT was produced by forming a metal oxide semiconductor film in the same manner as in Example 1 except that the substrate temperature during the ultraviolet irradiation treatment in the conversion step was 230 ° C.
転化工程における紫外線照射処理の際の紫外線光照度を80mW/cm2とした以外は実施例1と同様にして金属酸化物半導体膜を形成して、簡易型TFTを作製した。 [Example 4]
A simple TFT was produced by forming a metal oxide semiconductor film in the same manner as in Example 1 except that the ultraviolet light illuminance during the ultraviolet irradiation treatment in the conversion step was 80 mW / cm 2 .
下記に示す金属酸化物半導体前駆体溶液を用いた以外は実施例1と同様にして金属酸化物半導体膜を形成して、簡易型TFTを作製した。 [Example 5]
A simple TFT was produced by forming a metal oxide semiconductor film in the same manner as in Example 1 except that the metal oxide semiconductor precursor solution shown below was used.
すなわち、上記溶液は、亜鉛及びスズの割合が80%であり、亜鉛とスズとの組成比Sn/(Sn+Zn)が0.9である。 Gallium nitrate (Ga (NO 3 ) 3 xH 2 O, 5N, manufactured by Kojundo Chemical Laboratory Co., Ltd.) and indium nitrate (In (NO 3 ) 3 xH 2 O, 4N, manufactured by Kojundo Chemical Laboratory Co., Ltd.) ) In 2-methoxyethanol (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare 0.3 mol / L gallium nitrate solution and indium nitrate solution, and then gallium nitrate solution and nitric acid solution The gallium indium mixed solution was prepared by mixing the indium solution at a ratio of 1: 4. Then, the metal oxide semiconductor precursor is prepared by mixing the solution of the zinc / tin composition ratio Sn / (Sn + Zn) 0.9 used in Example 1 and the gallium indium mixed solution in a ratio of 4: 1. A body solution was prepared.
That is, in the above solution, the ratio of zinc and tin is 80%, and the composition ratio Sn / (Sn + Zn) between zinc and tin is 0.9.
実施例1で用いた亜鉛とスズとの組成比Sn/(Sn+Zn)が0.9の溶液と、ガリウムインジウム混合溶液との混合割合を9:1とした以外は、実施例5と同様にして金属酸化物半導体前駆体溶液を調製して、金属酸化物半導体膜を形成し、簡易型TFTを作製した。
すなわち、上記溶液は、亜鉛及びスズの割合が90%であり、亜鉛とスズとの組成比Sn/(Sn+Zn)が0.9である。 [Example 6]
Except that the mixing ratio of the zinc / tin composition ratio Sn / (Sn + Zn) 0.9 used in Example 1 and the gallium indium mixed solution was 9: 1, the same procedure as in Example 5 was performed. A metal oxide semiconductor precursor solution was prepared, a metal oxide semiconductor film was formed, and a simple TFT was produced.
That is, in the above solution, the ratio of zinc and tin is 90%, and the composition ratio Sn / (Sn + Zn) between zinc and tin is 0.9.
溶液として塩化スズ溶液を用いて、金属酸化物半導体前駆体膜の亜鉛とスズとの組成比Sn/(Sn+Zn)を1とした以外は、実施例1と同様にして金属酸化物半導体膜を形成して、簡易型TFTを作製した。 [Comparative Example 1]
A metal oxide semiconductor film is formed in the same manner as in Example 1 except that a tin chloride solution is used as a solution and the composition ratio Sn / (Sn + Zn) of zinc and tin of the metal oxide semiconductor precursor film is set to 1. Thus, a simple TFT was produced.
塩化スズ溶液と酢酸亜鉛溶液との混合の割合を6:4として溶液を調製し、金属酸化物半導体前駆体膜の亜鉛とスズとの組成比Sn/(Sn+Zn)を0.6とした以外は、実施例1と同様にして金属酸化物半導体膜を形成して、簡易型TFTを作製した。 [Comparative Example 2]
The solution was prepared by setting the mixing ratio of the tin chloride solution and the zinc acetate solution to 6: 4, except that the composition ratio Sn / (Sn + Zn) of zinc and tin of the metal oxide semiconductor precursor film was 0.6. A simple TFT was fabricated by forming a metal oxide semiconductor film in the same manner as in Example 1.
転化工程において紫外線の照射を行わない以外は、実施例1と同様にして金属酸化物半導体膜を形成して、簡易型TFTを作製した。 [Comparative Example 3]
A simple TFT was fabricated by forming a metal oxide semiconductor film in the same manner as in Example 1 except that no ultraviolet irradiation was performed in the conversion step.
転化工程において紫外線の照射を行わない以外は、比較例1と同様にして金属酸化物半導体膜を形成して、簡易型TFTを作製した。 [Comparative Example 4]
A simple TFT was produced by forming a metal oxide semiconductor film in the same manner as in Comparative Example 1 except that no ultraviolet irradiation was performed in the conversion step.
実施例1および比較例3で作製した金属酸化物半導体膜について、SIMS分析(二次イオン質量分析法)により、膜中の水素濃度および炭素濃度を求めた。
測定装置は、アルバック・ファイ株式会社製 PHI ADEPT-1010を用いた。
測定条件としては、一次イオン種はCs+、一次加速電圧は1.0kV、検出領域は140μm×140μmとした。
SIMS分析によって見積もられた水素および炭素の濃度を表1に示す。なお、深さ方向で濃度に違いが生じたため濃度範囲として示す。 <SIMS analysis>
About the metal oxide semiconductor film produced in Example 1 and Comparative Example 3, the hydrogen concentration and carbon concentration in the film were determined by SIMS analysis (secondary ion mass spectrometry).
As a measuring apparatus, PHI ADEPT-1010 manufactured by ULVAC-PHI Co., Ltd. was used.
As measurement conditions, the primary ion species was Cs + , the primary acceleration voltage was 1.0 kV, and the detection region was 140 μm × 140 μm.
Table 1 shows the hydrogen and carbon concentrations estimated by SIMS analysis. In addition, since a difference in density occurs in the depth direction, the density range is shown.
<トランジスタ特性>
作製した各簡易型TFTについて、半導体パラメータ・アナライザー4156C(アジレントテクノロジー株式会社製)を用い、トランジスタ特性Vg-Idを測定し、線形移動度を求めた。
トランジスタ特性Vg-Idの測定は、ドレイン電圧(Vd)を+20Vに固定し、ゲート電圧(Vg)を-15V~+30Vの範囲内で変化させ、各ゲート電圧におけるドレイン電流(Id)を測定することにより行った。
なお、比較例1に関してはオンオフ動作が確認できず、導体の振る舞いを示した。
また、比較例3に関しては電気伝導性を示さず、絶縁体の振る舞いを示した。
評価結果を表2に示す。また、実施例1、2および比較例1、2のトランジスタ特性Vg-Idのグラフを図11に示す。また、比較例1、4のトランジスタ特性Vg-Idのグラフを図12に示す。 [Evaluation]
<Transistor characteristics>
For each simplified TFT fabricated using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies Inc.), to measure the transistor characteristics V g -I d, it was determined linear mobility.
The transistor characteristics V g -I d are measured by fixing the drain voltage (V d ) to +20 V, changing the gate voltage (V g ) within a range of −15 V to +30 V, and drain current (I d at each gate voltage ). ) Was measured.
In Comparative Example 1, the on / off operation could not be confirmed, and the behavior of the conductor was shown.
Further, Comparative Example 3 did not show electrical conductivity and showed the behavior of the insulator.
The evaluation results are shown in Table 2. Further, a graph of the transistor characteristic V g -I d of Examples 1 and 2 and Comparative Examples 1 and 2 in Figure 11. Further, FIG. 12 shows a graph of the transistor characteristic V g -I d of Comparative Examples 1 and 4.
ここで、実施例1、2および比較例1、2の対比から、金属酸化物半導体前駆体膜の亜鉛とスズとの組成比を0.7≦Sn/(Sn+Zn)≦0.9の範囲とすることで線形移動度を大きくできることがわかる。
また、実施例1と実施例5、6との対比から、全金属成分中のスズおよび亜鉛の割合が高いほど線形移動度を大きくできることがわかる。
また、実施例1と実施例4との対比から、転化工程における紫外線の照度を大きくしても線形移動度はかわらないことがわかる。このことから、金属酸化物半導体前駆体膜の転化に必要十分な照度の紫外線を照射すればよいことがわかる。
また、実施例1~4から250℃以下の低温の加熱でも線形移動度を大きくできることがわかる。 As shown in Table 2, the simple TFT of the example provided with the metal oxide semiconductor film manufactured by the manufacturing method of the present invention has a large linear mobility and high semiconductor characteristics as compared with the simple TFT of the comparative example. You can see that
Here, from the comparison of Examples 1 and 2 and Comparative Examples 1 and 2, the composition ratio of zinc and tin of the metal oxide semiconductor precursor film is in the range of 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9. It can be seen that the linear mobility can be increased.
Moreover, it can be seen from the comparison between Example 1 and Examples 5 and 6 that the higher the ratio of tin and zinc in all metal components, the greater the linear mobility.
Moreover, it turns out that linear mobility does not change even if the illumination intensity of the ultraviolet-ray in a conversion process is enlarged from the comparison with Example 1 and Example 4. FIG. This shows that it is sufficient to irradiate ultraviolet rays having sufficient illuminance to convert the metal oxide semiconductor precursor film.
It can also be seen from Examples 1 to 4 that the linear mobility can be increased even by heating at a low temperature of 250 ° C. or lower.
以上より本発明の効果は明らかである。 In addition, as shown in FIG. 12, Comparative Example 1 and Comparative Example 4 both show the behavior of the conductor, but Comparative Example 4 in which ultraviolet irradiation is not performed is more than Comparative Example 1 in which ultraviolet irradiation is performed. It can be seen that the electron transfer characteristics are higher. From this, it can be seen that in order to obtain the effect of the ultraviolet irradiation treatment, it is necessary to appropriately select the range of the composition ratio of zinc and tin.
From the above, the effects of the present invention are clear.
12 基板
14 活性層(酸化物半導体層)
16 ソース電極
18 ドレイン電極
20 ゲート絶縁膜
22 ゲート電極
30、40、50 薄膜トランジスタ
100 液晶表示装置
102、202、216 パッシベーション層
104 画素下部電極
106 対向上部電極
108 液晶層
110 カラーフィルタ
112a、112b 偏光板
113、220、320 ゲート配線
114、222、322 データ配線
116、318 コンタクトホール
118、310 キャパシタ
200 有機EL表示装置
208 下部電極
210、306 上部電極
212 有機発光層
214 有機EL発光素子
224 駆動配線
300 X線センサ
302 電荷収集用電極
304 X線変換層
308 パッシベーション膜
312 キャパシタ用下部電極
314 キャパシタ用上部電極
316 絶縁膜 10
16
Claims (14)
- 溶媒及び金属成分として亜鉛とスズとを含む溶液を基板上に塗布して金属酸化物半導体前駆体膜を形成する金属酸化物半導体前駆体膜形成工程と、
前記金属酸化物半導体前駆体膜を加熱した状態で紫外線照射を行うことにより、前記金属酸化物半導体前駆体膜を金属酸化物半導体膜に転化させる転化工程とを有し、
前記金属酸化物半導体前駆体膜中の全金属成分の80%以上が亜鉛およびスズであり、亜鉛とスズとの組成比が、0.7≦Sn/(Sn+Zn)≦0.9であることを特徴とする金属酸化物半導体膜の製造方法。 A metal oxide semiconductor precursor film forming step of forming a metal oxide semiconductor precursor film by applying a solution containing zinc and tin as a solvent and a metal component on a substrate;
A conversion step of converting the metal oxide semiconductor precursor film into a metal oxide semiconductor film by performing ultraviolet irradiation while the metal oxide semiconductor precursor film is heated,
80% or more of all metal components in the metal oxide semiconductor precursor film are zinc and tin, and the composition ratio of zinc and tin is 0.7 ≦ Sn / (Sn + Zn) ≦ 0.9. A method for manufacturing a metal oxide semiconductor film. - 前記金属酸化物半導体前駆体膜中におけるインジウムの成分比が5%未満である請求項1に記載の金属酸化物半導体膜の製造方法。 The method for producing a metal oxide semiconductor film according to claim 1, wherein a component ratio of indium in the metal oxide semiconductor precursor film is less than 5%.
- 前記転化工程において、紫外線照射中の前記基板の温度を250℃以下に保持する請求項1または2に記載の金属酸化物半導体膜の製造方法。 The method for producing a metal oxide semiconductor film according to claim 1 or 2, wherein in the conversion step, the temperature of the substrate during ultraviolet irradiation is maintained at 250 ° C or lower.
- 前記転化工程において、前記金属酸化物半導体前駆体膜に照射される紫外線は、波長300nm以下の照度が30mW/cm2以上である請求項1~3のいずれか1項に記載の金属酸化物半導体膜の製造方法。 The metal oxide semiconductor according to any one of claims 1 to 3, wherein, in the conversion step, the ultraviolet ray irradiated to the metal oxide semiconductor precursor film has an illuminance with a wavelength of 300 nm or less of 30 mW / cm 2 or more. A method for producing a membrane.
- 前記転化工程は、酸素を1体積%以上含む雰囲気中で行われる請求項1~4のいずれか1項に記載の金属酸化物半導体膜の製造方法。 The method for producing a metal oxide semiconductor film according to any one of claims 1 to 4, wherein the conversion step is performed in an atmosphere containing 1% by volume or more of oxygen.
- 前記金属酸化物半導体前駆体膜中の全金属成分の95%以上が亜鉛およびスズである請求項1~5のいずれか1項に記載の金属酸化物半導体膜の製造方法。 The method for producing a metal oxide semiconductor film according to any one of claims 1 to 5, wherein 95% or more of all metal components in the metal oxide semiconductor precursor film are zinc and tin.
- 前記溶液が、亜鉛及びスズの金属塩または金属ハロゲン化物を溶媒に溶解してなるものである請求項1~6のいずれか1項に記載の金属酸化物半導体膜の製造方法。 The method for producing a metal oxide semiconductor film according to any one of claims 1 to 6, wherein the solution is obtained by dissolving a metal salt or metal halide of zinc and tin in a solvent.
- 前記溶媒が、メタノール、メトキシエタノール、または、水である請求項1~7のいずれか1項に記載の金属酸化物半導体膜の製造方法。 The method for producing a metal oxide semiconductor film according to any one of claims 1 to 7, wherein the solvent is methanol, methoxyethanol, or water.
- 前記溶液中の金属成分の濃度が、0.01mol/L~1.0mol/Lである請求項1~8のいずれか1項に記載の金属酸化物半導体膜の製造方法。 The method for producing a metal oxide semiconductor film according to any one of claims 1 to 8, wherein the concentration of the metal component in the solution is 0.01 mol / L to 1.0 mol / L.
- 請求項1~9のいずれか1項に記載の金属酸化物半導体膜の製造方法を用いて作製された金属酸化物半導体膜。 A metal oxide semiconductor film produced using the method for producing a metal oxide semiconductor film according to any one of claims 1 to 9.
- 二次イオン質量分析法による膜中の炭素濃度が1×1019atoms/cm3以上1×1020atoms/cm3以下である請求項10に記載の金属酸化物半導体膜。 The metal oxide semiconductor film according to claim 10, wherein the carbon concentration in the film by secondary ion mass spectrometry is 1 × 10 19 atoms / cm 3 or more and 1 × 10 20 atoms / cm 3 or less.
- 二次イオン質量分析法による膜中の水素濃度が2×1022atoms/cm3以上4×1022atoms/cm3以下である請求項10または11に記載の金属酸化物半導体膜。 12. The metal oxide semiconductor film according to claim 10, wherein a hydrogen concentration in the film by secondary ion mass spectrometry is 2 × 10 22 atoms / cm 3 or more and 4 × 10 22 atoms / cm 3 or less.
- 請求項10~12のいずれか1項に記載の金属酸化物半導体膜を含む活性層と、ソース電極と、ドレイン電極と、ゲート絶縁膜と、ゲート電極とを有する薄膜トランジスタ。 A thin film transistor having an active layer including the metal oxide semiconductor film according to any one of claims 10 to 12, a source electrode, a drain electrode, a gate insulating film, and a gate electrode.
- 請求項13に記載の薄膜トランジスタを備える電子デバイス。
An electronic device comprising the thin film transistor according to claim 13.
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