Method for producing metal oxynitride film

Abstract

The invention relates to a method for manufacturing a metal oxynitride film. Provided is a method for forming a metal oxynitride film by epitaxial growth at a low temperature. This method for producing a metal oxynitride film comprises a step for epitaxially growing a metal oxynitride film by sputtering using an oxide target containing zinc by introducing a gas containing a nitrogen gas onto a single-crystal substrate, the substrate being 80-400 DEG C (inclusive) when the metal oxynitride film is formed, and the thickness of the substrate being 1-10 [mu] m. The flow rate of the nitrogen gas is 50% or more and 100% or less of the total flow rate of the gas.

Description

This application is a divisional application of the Chinese patent application with application number 201980039953.X, application date June 24, 2019, and invention name “Method for manufacturing metal oxynitride film”. Technical Field

[0001] One embodiment of the present invention relates to a metal oxynitride film and a method for producing the metal oxynitride film. Another embodiment of the present invention relates to a light-emitting element, a lighting device, a display device, an electronic device, and a semiconductor device using the metal oxynitride film.

[0002] Note that in this specification, etc., semiconductor devices refer to all devices that can operate by utilizing semiconductor characteristics. In addition to semiconductor components such as transistors, semiconductor circuits, computing devices, or storage devices are also a form of semiconductor devices. Display devices (liquid crystal display devices, light-emitting display devices, etc.), projection devices, lighting devices, electro-optical devices, power storage devices, storage devices, semiconductor circuits, camera devices, electronic devices, etc. sometimes include semiconductor devices.

[0003] Note that one embodiment of the present invention is not limited to the above-mentioned technical field. One embodiment of the invention disclosed in this specification, etc., relates to an object, method, or manufacturing method. In addition, one embodiment of the present invention relates to a process, machine, product, or composition of matter. Background Art

[0004] Metal oxynitrides containing metal, oxygen and nitrogen are known as pigments or photocatalytic materials. Metal oxynitrides are also attracting attention as semiconductor materials and insulating materials for semiconductor devices, etc. Patent Document 1 discloses a semiconductor material including metal oxynitrides containing indium, gallium and zinc.

[0005] In addition, as one of the methods for forming an in-plane oriented thin film (also referred to as a single crystal thin film), an epitaxial growth method is known. Here, in-plane orientation refers to the regularity of the crystal orientation in the direction horizontal to the substrate. Patent document 2 discloses a method for forming a single crystal InGaO3(ZnO)5 thin film by a reactive solid phase epitaxial growth method. [Prior technical literature] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2015-18929 [Patent Document 2] Japanese Patent Application Publication No. 2004-103957 Summary of the invention Technical problem to be solved by the invention

[0007] The state of the metal oxynitride disclosed in Patent Document 1 is an amorphous state in which the bonding between atoms is disordered. Since the metal oxynitride in the amorphous state has voids or low-density regions, the stability of the metal oxynitride is low. Therefore, the metal oxynitride used for semiconductor devices and the like preferably has high crystallinity. In particular, the metal oxynitride is preferably oriented in-plane.

[0008] In addition, the reactive solid phase epitaxial growth method disclosed in Patent Document 2 requires the following high temperature treatment: heating the substrate to above 1000°C before forming the InGaO3(ZnO)5 thin film; performing a heat diffusion treatment at a temperature above 1300°C after forming the thin film; etc. In addition, in order to form a single crystal InGaO3(ZnO)5 thin film, it is necessary to provide an epitaxially grown ZnO thin film on the substrate. Thus, when using the prior art to form an epitaxially grown thin film, there are various limitations. Note that in this specification, "high temperature" refers to, for example, a temperature above 700°C, and "low temperature" refers to, for example, a temperature below 600°C.

[0009] Therefore, one of the objects of one embodiment of the present invention is to provide a method for forming a metal oxynitride film by epitaxial growth at low temperature. Another object of one embodiment of the present invention is to provide a method for forming a metal oxynitride film by epitaxial growth without performing high temperature treatment before or after forming the metal oxynitride film. Another object of one embodiment of the present invention is to provide a semiconductor device etc. using a metal oxynitride film formed by epitaxial growth.

[0010] Note that the recording of these purposes does not prevent the existence of other purposes. Note that one mode of the present invention does not need to achieve all of the above purposes. Purposes other than the above purposes are obvious from the description of the specification, drawings, claims, etc., and can be extracted from the description. Solutions to technical problems

[0011] One embodiment of the present invention is a method for manufacturing a metal oxynitride film, comprising the following steps: introducing a gas containing nitrogen gas onto a single crystal substrate, and epitaxially growing the metal oxynitride film by sputtering using an oxide target, wherein the oxide target contains zinc, the substrate temperature when forming the metal oxynitride film is above 80°C and below 400°C, and the flow rate of the nitrogen gas is above 50% and below 100% of the total flow rate of the gas.

[0012] In addition, one embodiment of the present invention is a method for manufacturing a metal oxynitride film, comprising the following steps: introducing a gas containing nitrogen gas onto a single crystal substrate, and forming an in-plane oriented film by sputtering using an oxide target, wherein the oxide target contains zinc, the substrate temperature when forming the metal oxynitride film is above 80°C and below 400°C, and the flow rate of the nitrogen gas is above 50% and below 100% of the total flow rate of the gas.

[0013] In the above-mentioned method for producing a metal oxynitride film, the oxide target preferably contains at least one of indium and gallium.

[0014] In the above-mentioned method for manufacturing the metal oxynitride film, it is preferred that the substrate is an yttria-stabilized zirconia (YSZ) substrate, and the surface orientation of the substrate is (111). In addition, it is preferred that the substrate is an A-plane sapphire substrate, and the surface orientation of the substrate is (110).

[0015] In the above-mentioned method for producing a metal oxynitride film, the crystal structure of the metal oxynitride film is preferably a wurtzite structure.

[0016] In the above-mentioned method for manufacturing the metal oxynitride film, preferably, when the metal oxynitride film is subjected to pole measurement, a diffraction peak indicating six-fold symmetry is observed in a φ scan of the (101) plane of the crystal of the metal oxynitride film in the pole measurement.

[0017] In addition, in the above-mentioned method for manufacturing the metal oxynitride film, it is preferred that a first spot and a second spot are observed in the wide-angle reciprocal space diagram of the metal oxynitride film, the peak of the first spot is located at an angle 2θ of at least 30° and at most 35° and near an angle ψ of 0°, and the half-width of the first spot is less than 2°, the peak of the second spot is located at an angle 2θ of at least 33° and at most 37° and at least 61° and at most 65°, and the half-width of the second spot is less than 2°. Effects of the Invention

[0018] According to one embodiment of the present invention, a method for forming a metal oxynitride film by epitaxial growth at low temperature can be provided. In addition, according to one embodiment of the present invention, a method for forming a metal oxynitride film by epitaxial growth without performing high temperature treatment before or after forming the metal oxynitride film can be provided. In addition, according to one embodiment of the present invention, a semiconductor device using a metal oxynitride film formed by epitaxial growth can be provided.

[0019] Note that the description of these effects does not prevent the existence of other effects. One mode of the present invention does not need to have all of the above effects. Effects other than the above can be naturally known and derived from the description of the specification, drawings, claims, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] [Figure 1] Figure 1A A diagram illustrating a metal oxynitride film epitaxially grown on a substrate. Figure 1B It is a diagram for explaining the crystal planes of crystals included in the metal oxynitride film. Figure 1C This is a diagram illustrating the atomic configuration of the crystal. [ Figure 2 ] Figure 2 This is a diagram for explaining the atomic number ratio range of metals constituting an oxide target. [Figure 3] Figure 3A and Figure 3B It is a schematic diagram explaining a sputtering device. [ Figure 4 ] Figure 4 This is a diagram of the experimental configuration in wide-angle reciprocal space mapping and pole measurement. [Figure 5] Figure 5A It is a diagram illustrating a polar figure. Figure 5B and Figure 5C is a diagram illustrating the intensity distribution obtained by pole point measurement. [Figure 6] Fig. 6A and Figure 6B is a diagram showing a structural example of a light emitting element. [Figure 7] Fig. 7A and Figure 7B This is a diagram showing a lighting device according to one embodiment of the present invention. [Figure 8] FIG. 8A to FIG. 8C is a diagram showing a structural example of a display device. [Figure 9] 9A to 9E is a diagram showing a configuration example of an electronic device. [Figure 10] Fig. 10A 3 is a diagram showing a wide-angle reciprocal space image of Sample 1 in the example. Fig. 10B and Fig. 10C 3 is a diagram showing a wide-angle reciprocal space map obtained in a simulation. [Figure 11] Fig.11A and Fig. 11B This is a diagram showing the results of pole point measurement of Sample 1 in the example. [Figure 12] Fig. 12A 3 is a diagram showing a wide-angle reciprocal space image of Sample 2 in the example. Fig. 12B and Fig. 12C 3 is a diagram showing a wide-angle reciprocal space map obtained in a simulation. [Figure 13] Fig.13A and Fig. 13B This is a diagram showing the results of pole point measurement of Sample 2 in the example. [Figure 14] Fig.14A3 is a diagram showing a wide-angle reciprocal space image of Sample 3 in the example. Fig. 14B and Fig. 14C 3 is a diagram showing a wide-angle reciprocal space map obtained in a simulation. [Figure 15] Fig.15A and Fig. 15B This is a diagram showing the results of pole point measurement of Sample 3 in the example. [Figure 16] Fig.16A 3 is a diagram showing a wide-angle reciprocal space image of Sample 4 in the example. Fig. 16B and Fig. 16C 3 is a diagram showing a wide-angle reciprocal space map obtained in a simulation. [Figure 17] Fig.17A and Fig. 17B This is a diagram showing the results of pole point measurement of Sample 4 in the example. [Figure 18] Fig.18A 3 is a diagram showing a wide-angle reciprocal space image of Sample 5 in the example. Fig.18B and Fig. 18C 3 is a diagram showing a wide-angle reciprocal space map obtained in a simulation. [Figure 19] Fig.19A and Fig.19B This is a diagram showing the results of pole point measurement of Sample 5 in the example. [Figure 20] Fig. 20A 3 is a diagram showing a wide-angle reciprocal space image of Sample 6 in the example. Fig. 20B and Fig. 20C 3 is a diagram showing a wide-angle reciprocal space map obtained in a simulation. [Figure 21] Fig.21A and Fig. 21B This is a diagram showing the results of pole point measurement of Sample 6 in the example. [Figure 22] Fig.22A 3 is a diagram showing a wide-angle reciprocal space image of Sample 7 in the example. Fig. 22B and Fig. 22C 3 is a diagram showing a wide-angle reciprocal space map obtained in a simulation. [Figure 23] Fig.23A and Fig. 23B This is a diagram showing the results of pole point measurement of Sample 7 in the Example. Modes for Carrying Out the Invention

[0021] The following describes the embodiments with reference to the accompanying drawings. It should be noted that a person skilled in the art can easily understand that the embodiments can be implemented in a plurality of different forms, and the methods and details can be transformed into various forms without departing from the purpose and scope of the present invention. Therefore, the present invention should not be interpreted as being limited to the contents described in the embodiments shown below.

[0022] In the drawings, the size, thickness of a layer or an area are sometimes exaggerated for the sake of clarity. Therefore, the present invention is not limited to the dimensions in the drawings. In addition, in the drawings, ideal examples are schematically shown, so the present invention is not limited to the shapes or numerical values ​​shown in the drawings. For example, in an actual manufacturing process, a layer or a resist mask is sometimes unintentionally etched due to a process such as etching, but this is sometimes not reflected in the drawings for ease of understanding. In addition, in the drawings, the same reference numerals are sometimes used in common between different drawings to represent the same parts or parts with the same function, and their repeated descriptions are omitted. In addition, when representing parts with the same function, the same hatching is sometimes used without specifically adding a reference numeral.

[0023] In addition, in order to facilitate understanding of the invention, in particular, in a top view (also called a plan view) or a perspective view, description of some components may be omitted. In addition, description of some hidden lines may be omitted.

[0024] In this specification, for convenience, words and phrases such as "upper" and "lower" are used to indicate the positional relationship of the components with reference to the drawings. In addition, the positional relationship of the components is appropriately changed according to the direction in which each component is described. Therefore, the words and phrases described in the specification are not limited, and the words and phrases can be appropriately changed according to the situation.

[0025] For example, in this specification, when it is clearly stated that "X is connected to Y", it means the following: X is electrically connected to Y; X is functionally connected to Y; X is directly connected to Y. Therefore, the connection relationship is not limited to the connection relationship shown in the drawings or the text, and the connection relationship other than the connection relationship shown in the drawings or the text is also disclosed in the drawings or the text. Here, X and Y are objects (for example, devices, elements, circuits, wiring, electrodes, terminals, conductive films, layers, etc.).

[0026] In this specification, etc., a transistor refers to a component including at least three terminals: a gate, a drain, and a source. The transistor has a region (hereinafter also referred to as a channel formation region) where a channel is formed between the drain (drain terminal, drain region, or drain electrode) and the source (source terminal, source region, or source electrode), and current can flow between the source and the drain through the channel formation region. Note that in this specification, etc., the channel formation region refers to a region where current mainly flows.

[0027] In addition, the functions of the source and the drain may be interchanged when transistors with different polarities are used or when the direction of current changes during circuit operation. Therefore, in this specification, the source and the drain may be interchanged.

[0028] Note that in this specification, etc., “insulator” may be referred to as “insulating film” or “insulating layer”. Also, “conductor” may be referred to as “conductive film” or “conductive layer”. Also, “semiconductor” may be referred to as “semiconductor film” or “semiconductor layer”.

[0029] In this specification, etc., "parallel" refers to a state where the angle formed by two straight lines is greater than -10° and less than 10°. Therefore, a state where the angle is greater than -5° and less than 5° is also included. "Approximately parallel" refers to a state where the angle formed by two straight lines is greater than -30° and less than 30°. In addition, "perpendicular" refers to a state where the angle formed by two straight lines is greater than 80° and less than 100°. Therefore, a state where the angle is greater than 85° and less than 95° is also included. "Approximately perpendicular" refers to a state where the angle formed by two straight lines is greater than 60° and less than 120°.

[0030] In addition, in this specification, the Miller index is used to represent the crystal plane. The Miller index is represented by three integers in parentheses. In addition, the arrangement direction of the crystal plane (the direction perpendicular to the crystal plane) is called the crystal orientation. The crystal orientation is represented by three integers in square brackets. For example, it is recorded as (111) when representing the crystal plane and as

[111] when representing the crystal orientation. In addition, in the case of a hexagonal crystal system, a record called the Miller-Bravais index is sometimes used. Specifically, four integers (h, k, i, l) are used to represent the face index of the hexagonal lattice (hkil). Here, i = -(h+k). The index i can be calculated from the values ​​of the index h and the index k, so in this specification, the crystal plane of the hexagonal crystal system is also represented by the Miller index (hkl) using three integers.

[0031] In this specification, a crystal plane appearing on the surface of a single crystal substrate may be referred to as a plane orientation of the single crystal substrate.

[0032] In this specification, lattice points in the reciprocal lattice corresponding to a crystal plane (also referred to as reciprocal points) are indicated as indices without parentheses. For example, the reciprocal point 111 shown as a spot observed in the wide-angle reciprocal space map corresponds to the crystal plane (111).

[0033] In addition, in the Miller index, when indicating a negative direction, a horizontal line is attached to the number indicating the index, but in this specification, for convenience, a negative sign is attached before the number indicating the index. In addition, as a surface equivalent to (111), there are (-111), (1-11), (11-1), etc. In this specification, when (111) is written, (111) sometimes includes equivalent surfaces such as (-111), (1-11), (11-1), etc.

[0034] (Implementation Method 1) In this embodiment, a method for manufacturing a metal oxynitride film which is one embodiment of the present invention is described.

[0035] Metal oxynitrides containing metal, oxygen, and nitrogen have attracted attention as semiconductor materials or insulating materials for semiconductor devices. Preferably, the metal oxynitride used for semiconductor devices has few impurities and defects and high stability. Here, "high stability of the metal oxynitride" means: it is not easy to react with the material in contact with the metal oxynitride due to heat generated by the operation of the semiconductor device, etc.; the crystallinity of the metal oxynitride remains unchanged; no defects are generated in the metal oxynitride; etc. By using a metal oxynitride with few impurities and defects and high stability for a semiconductor device, the reliability of the semiconductor device can be improved.

[0036] Impurities in metal oxynitrides refer to components other than the main components constituting the metal oxynitrides, for example. For example, in metal oxynitrides, elements whose concentration is less than 0.1 atomic % can be said to be impurities. Examples of such elements include hydrogen, silicon, boron, phosphorus, carbon, and transition metals other than the main components constituting the metal oxynitrides. In addition, defects in metal oxynitrides are lattice defects, such as point defects such as oxygen vacancies and nitrogen vacancies, line defects such as dislocations, and surface defects such as grain boundaries. In addition, as defects in metal oxynitrides, there are void defects such as voids.

[0037] In addition, from the perspective of crystallinity, thin films include in-plane oriented thin films, oriented thin films, non-oriented thin films (polycrystalline thin films), amorphous thin films, etc. An oriented thin film is a thin film in which at least one crystal axis of the crystal contained in the thin film is aligned in a specific direction. In addition, an in-plane oriented thin film is a thin film in which three crystal axes of the crystal contained in the thin film are aligned in a specific direction.

[0038] The thin film of metal oxynitride used for semiconductor devices is preferably a thin film of metal oxynitride with orientation, and more preferably a thin film of metal oxynitride oriented in a plane. The thin film of metal oxynitride oriented in a plane has few impurities and defects and has a dense structure. Therefore, by using a thin film of metal oxynitride oriented in a plane for a semiconductor device, the reliability of the semiconductor device can be improved.

[0039] Epitaxial growth is known as a method for forming an in-plane oriented thin film. Epitaxial growth means that the crystals constituting the thin film grow on a single crystal substrate with a specific crystal orientation relationship. Note that the growth of crystals having the same lattice constant as the crystals contained in the substrate on a single crystal substrate using the same material as the substrate is called homoepitaxial growth. In addition, the growth of crystals on a single crystal substrate using a material different from the substrate or a material having a lattice constant different from the crystals contained in the substrate is called heteroepitaxial growth. Heteroepitaxial growth can be performed as follows: selecting a material with a small lattice mismatch relative to the crystals contained in the substrate; providing a layer that alleviates lattice distortion (also called a buffer layer) between the substrate and the thin film; etc.

[0040] As epitaxial growth methods, there are solid phase epitaxy (SPE: Solid Phase Epitaxy) method, liquid phase epitaxy (LPE: Liquid Phase Epitaxy) method, and vapor phase epitaxy (VPE: Vapor Phase Epitaxy) method.

[0041] The SPE method is a method in which a thin film is formed on the surface of a substrate; the thin film is heated by electron beam irradiation or the like; so that the crystal structure of the thin film becomes the same as the crystal structure of the crystal contained in the substrate. In addition, the LPE method is a method in which a crystalline part is precipitated from a supersaturated solution onto the surface of a substrate. In addition, the VPE method is a method in which components in the gas phase are deposited onto the surface of a substrate. The VPE method includes the pulsed laser deposition (PLD: Pulsed Laser Deposition) method, the atomic layer deposition (ALD: Atomic Layer Deposition) method, the molecular beam epitaxy (MBE: Molecular Beam Epitaxy) method, and the like. The MBE method is a method in which an element constituting the target crystal or a material containing the element is heated and evaporated in an ultra-high vacuum to deposit a crystal on the heated substrate.

[0042] In the prior art, there are various restrictions on epitaxial growth of thin films. Examples of such restrictions include: forming the thin film at a high temperature; performing heat treatment at a high temperature (e.g., above 1000°C) after forming the thin film; performing a flattening treatment on the substrate surface before forming the thin film; providing one or more buffer layers on the substrate; selecting a substrate with a similar lattice constant and thermal expansion coefficient; etc. As a flattening treatment on the substrate surface, for example, heat treatment of the substrate at a high temperature is performed.

[0043] Therefore, one embodiment of the present invention is a method for manufacturing a metal oxynitride film by epitaxially growing the metal oxynitride film at a low temperature. Specifically, the manufacturing method is a method for epitaxially growing the metal oxynitride film on a single crystal substrate by sputtering by introducing a gas into a reaction chamber. Since one embodiment of the present invention is a manufacturing method for forming an in-plane oriented film by epitaxial growth, the film epitaxially grown in the manufacturing method is an in-plane oriented film.

[0044] The crystal structure of the metal oxynitride film for epitaxial growth is preferably a hexagonal crystal structure. Among the hexagonal crystal structures, the wurtzite structure is particularly preferred. The wurtzite structure has a crystal orientation relationship that enables epitaxial growth of cubic crystals (e.g., diamond structure, fluorite structure, sphalerite structure, etc.). For example,

[111] of the cubic crystal and

[001] of the wurtzite structure are crystal orientation relationships that enable epitaxial growth. Therefore, it is easy to epitaxially grow a metal oxynitride film having a hexagonal crystal structure on a single crystal substrate having a crystal structure such as a cubic crystal system and a hexagonal crystal system. In addition, it is easy to epitaxially grow materials having a crystal structure such as a cubic crystal system and a hexagonal crystal system on the metal oxynitride film.

[0045] As the substrate of the above-mentioned single crystal, an insulating substrate such as a sapphire substrate, a stabilized zirconia substrate (yttria-stabilized zirconia (YSZ) substrate, etc.) can be used. When the crystal structure of the metal oxynitride is a wurtzite structure, as the above-mentioned substrate, for example, a YSZ substrate whose plane orientation is (111) or an A-plane sapphire substrate whose plane orientation is (110) is preferably used. By using a YSZ substrate or an A-plane sapphire substrate as the above-mentioned substrate, it is easy to form a metal oxynitride thin film containing crystals having a wurtzite structure and oriented in the plane. In addition, a semiconductor substrate made of silicon, germanium, silicon carbide, gallium nitride, gallium arsenide, indium phosphide, or zinc oxide can also be used.

[0046] The difference between the lattice constant of the crystal of the epitaxially grown thin film and the lattice constant of the crystal of the substrate (also called lattice mismatch) is preferably small. By reducing the lattice mismatch, a thin film can be easily epitaxially grown on a single crystal substrate.

[0047] One method for evaluating the degree of lattice mismatch is the lattice mismatch degree. The lattice mismatch degree Δa is calculated from the lattice constant a of the crystal of the epitaxially grown thin film. e , the lattice constant a of the substrate crystal s And calculated by the following formula (1).

[0048] [Formula 1]

[0049] The lattice mismatch between the epitaxially grown metal oxynitride film and the single crystal substrate is preferably 15% or less, more preferably 10% or less. This makes it easy to epitaxially grow the metal oxynitride film on the single crystal substrate.

[0050] Note that when a metal oxynitride film including crystals having a wurtzite structure is epitaxially grown on a cubic single crystal substrate, for example, the crystal orientation of the substrate surface is

[111] and the crystal orientation of the metal oxynitride film surface is

[001] , so that the crystal orientations of the substrate and the metal oxide film are different. s The lattice mismatch can be calculated by setting the value to √2 / 2 times the lattice constant of the crystal of the substrate. Specifically, when a YSZ substrate with a lattice constant of about 0.51 nm in the a-axis direction is used as the substrate of the single crystal, the minimum distance between the nearest atoms when the YSZ substrate is viewed from the

[111] direction is about 0.36 nm. Therefore, according to the preferred range of the lattice mismatch, the lattice constant in the a-axis direction of the crystal of the metal oxynitride film is preferably greater than 0.31 nm and less than 0.41 nm, and more preferably greater than 0.32 nm and less than 0.40 nm.

[0051] Figure 1A It is a schematic diagram of a structure including an epitaxially grown metal oxynitride film on a single crystal substrate. Figure 1A FIG. 1 is a schematic diagram of a structure in which a metal oxynitride film 20 is formed on a single crystal substrate 10 . Figure 1A The case where the metal oxynitride film 20 includes a crystal 30 having a wurtzite structure is shown. By the manufacturing method of one embodiment of the present invention, the metal oxynitride film 20 is epitaxially grown in such a manner that the c-axis (

[001] ) direction of the crystal 30 having a wurtzite structure coincides with the normal direction of the surface of the single crystal substrate 10. Here, since the c-axis (

[001] ) direction of the crystal included in the film epitaxially grown by the manufacturing method of one embodiment of the present invention coincides with the normal direction of the surface of the single crystal substrate, the film epitaxially grown by the manufacturing method of one embodiment of the present invention is sometimes referred to as a c-axis epitaxial film.

[0052] Reference Figure 1B Illustrate the crystal planes of the wurtzite structure. Figure 1B Typical crystal planes ((001) plane and (101) plane) of a wurtzite structure are shown. Figure 1B The (001) plane of the zincite structure shown is parallel to the surface of the substrate 10 of the single crystal.

[0053] Figure 1C Shown is the atomic configuration in the wurtzite structure. Figure 1CThe configuration X1 in is the configuration of metal atoms, and the configuration X2 is the configuration of oxygen atoms or nitrogen atoms. Note that the configuration X1 can be the configuration of oxygen atoms or nitrogen atoms, and the configuration X2 can also be the configuration of metal atoms.

[0054] The sputtering target used in the above-mentioned sputtering method is preferably an oxide target containing zinc, and more preferably an oxide target containing at least one of indium and gallium and zinc. As the oxide target, for example, a zinc oxide target, an indium zinc oxide (In-Zn oxide) target, a gallium zinc oxide (Ga-Zn oxide) target, an indium gallium zinc oxide (In-Ga-Zn oxide) target, etc. can be used. In particular, as the oxide target, an indium gallium zinc oxide target is preferably used. The crystal structures of indium nitride, gallium nitride, and zinc oxide are all wurtzite structures. Thus, by forming a film using the oxide target, it is easy to form a metal oxynitride thin film containing crystals having a wurtzite structure and oriented in a plane.

[0055] Reference Figure 2 A preferred range of the atomic number ratio of the metal constituting the above-mentioned oxide target will be described. Figure 2 is a graph showing the atomic ratio of indium, gallium, and zinc contained in the above oxide target. Figure 2 In the above, the atomic ratio of oxygen is not described. In addition, each of the atomic ratios of indium, gallium, and zinc contained in the oxide target is referred to as [In], [Ga], and [Zn], respectively.

[0056] exist Figure 2 In the figure, the dotted lines represent the atomic number ratio of [In]:[Ga]:[Zn]=(1+α):(1-α):1 (α is a real number greater than -1 and less than 1), the atomic number ratio of [In]:[Ga]:[Zn]=(1+α):(1-α):2, the atomic number ratio of [In]:[Ga]:[Zn]=(1+α):(1-α):3, and the atomic number ratio of [In]:[Ga]:[Zn]=(1+α):(1-α):4.

[0057] In addition, the dotted lines represent the atomic number ratio of [In]:[Ga]:[Zn]=4:1:β (β is a real number greater than 0), the atomic number ratio of [In]:[Ga]:[Zn]=2:1:β, the atomic number ratio of [In]:[Ga]:[Zn]=1:1:β, the atomic number ratio of [In]:[Ga]:[Zn]=1:2:β, and the atomic number ratio of [In]:[Ga]:[Zn]=1:4:β.

[0058] Figure 2The region A shown shows an example of a preferred range of the atomic ratio of indium, gallium, and zinc contained in the above-mentioned oxide target. Region A includes In-Ga-Zn oxide targets of [In]: [Ga]: [Zn] = 4:2:4.1 and [In]: [Ga]: [Zn] = 1:1:1, In-Zn oxide targets of [In]: [Ga]: [Zn] = 2:0:1 ([In]: [Zn] = 2:1), and zinc oxide targets of [In]: [Ga]: [Zn] = 0:0:1.

[0059] Note that the sputtering target used in the above-mentioned sputtering method is not limited to an oxide target, but may also be an oxynitride target. As the oxynitride target, for example, an indium gallium zinc oxynitride (In-Ga-Zn oxynitride) target, an indium gallium oxynitride (In-Ga oxynitride) target, an indium zinc oxynitride (In-Zn oxynitride) target, etc. may be used.

[0060] The substrate temperature when forming the metal oxynitride film is preferably room temperature (25° C.) or higher and 500° C. or lower, more preferably 80° C. or higher and 400° C. or lower, and further preferably 100° C. or higher and 250° C. or lower. Since the film is formed at a substrate temperature of 500° C. or lower, the productivity of semiconductor devices and the like using the metal oxynitride film can be improved.

[0061] As the gas introduced into the reaction chamber when forming the metal oxynitride film, a gas containing nitrogen gas is preferably used. For example, as the gas, nitrogen gas, a mixed gas of nitrogen gas and oxygen gas, or a mixed gas of nitrogen gas and a rare gas (argon, helium, etc.) is preferably used. Here, the flow rate of the nitrogen gas is preferably more than 50% and less than 100% of the total flow rate of the gas. In addition, by adjusting the flow rate ratio of the nitrogen gas relative to the flow rate of the gas, the composition of the obtained metal oxynitride film can be adjusted.

[0062] By the manufacturing method as described above, a metal oxynitride film can be epitaxially grown without providing a buffer layer between the substrate and the thin film.

[0063] <Sputtering device> Next, refer to Figure 3A and Figure 3B A sputtering apparatus for a method of manufacturing a metal oxynitride film according to one embodiment of the present invention will be described. Figure 3A is a cross-sectional view illustrating a film forming chamber 41 included in the sputtering device, Figure 3B It is a plan view of the magnet unit 54a and the magnet unit 54b included in the sputtering device.

[0064] Figure 3AThe film forming chamber 41 shown includes a target rack 52a, a target rack 52b, a pad 50a, a pad 50b, a sputtering target 70a, a sputtering target 70b, a member 58, and a substrate rack 62. The sputtering target 70a is arranged on the pad 50a. The pad 50a is arranged on the target rack 52a. The magnet unit 54a is arranged under the sputtering target 70a via the pad 50a. The sputtering target 70b is arranged on the pad 50b. The pad 50b is arranged on the target rack 52b. The magnet unit 54b is arranged under the sputtering target 70b via the pad 50b.

[0065] like Figure 3A and Figure 3B As shown, the magnet unit 54a includes a magnet 54N1, a magnet 54N2, a magnet 54S, and a magnet holder 56. In the magnet unit 54a, the magnet 54N1, the magnet 54N2, and the magnet 54S are arranged on the magnet holder 56. The magnet 54N1 and the magnet 54N2 are arranged in a manner spaced apart from the magnet 54S. The magnet unit 54b has the same structure as the magnet unit 54a. When the substrate 60 is carried into the film forming chamber 41, the substrate 60 contacts the substrate holder 62.

[0066] The sputtering target 70a, the backing plate 50a and the target holder 52a are separated from the sputtering target 70b, the backing plate 50b and the target holder 52b by a member 58. The member 58 is preferably an insulator. Note that the member 58 may also be a conductor or a semiconductor. In addition, the member 58 may also be a member in which the surface of the conductor or semiconductor is covered by an insulator.

[0067] The target holder 52a and the backing plate 50a are fixed by screws (bolts, etc.) and the same potential is applied to them. The target holder 52a has the function of supporting the sputtering target 70a through the backing plate 50a. The target holder 52b and the backing plate 50b are fixed by screws (bolts, etc.) and the same potential is applied to them. The target holder 52b has the function of supporting the sputtering target 70b through the backing plate 50b.

[0068] The backing plate 50a has a function of fixing the sputtering target 70a. The backing plate 50b has a function of fixing the sputtering target 70b.

[0069] exist Figure 3A , magnetic force lines 64a and magnetic force lines 64b formed by the magnet unit 54a are shown.

[0070] like Figure 3B As shown, the magnet unit 54a adopts a structure in which a square or substantially square magnet 54N1, a square or substantially square magnet 54N2, and a square or substantially square magnet 54S are fixed to a magnet frame 56. Figure 3BAs shown by the arrow, the magnet unit 54a can be swung in the left-right direction. For example, the magnet unit 54a can be swung at a beat (also known as rhythm, beat, pulse, frequency, period or cycle, etc.) of 0.1 Hz or more and 1 kHz or less.

[0071] The magnetic field on the sputtering target 70a changes with the swing of the magnet unit 54a. Since the area with a strong magnetic field becomes a high-density plasma area, the sputtering phenomenon of the sputtering target 70a is likely to occur near it. The same is true for the magnet unit 54b.

[0072] exist Figure 3A and Figure 3B In the embodiment, an example using a parallel plate sputtering device is shown, but the method for forming the metal oxynitride described in this embodiment is not limited to this. For example, the metal oxynitride may also be formed using an opposing target sputtering device.

[0073] Since the sputtering method can form a film at a low temperature, the productivity of semiconductor devices and the like using the metal oxynitride film can be improved.

[0074] According to one embodiment of the present invention, a method for forming a metal oxynitride film by epitaxial growth at low temperature can be provided. In addition, according to one embodiment of the present invention, a method for forming a metal oxynitride film by epitaxial growth without performing high temperature treatment before or after forming the metal oxynitride film can be provided. In addition, according to one embodiment of the present invention, a semiconductor device using a metal oxynitride film formed by epitaxial growth can be provided. In addition, according to one embodiment of the present invention, the productivity of a semiconductor device using a metal oxynitride film can be improved.

[0075] <Evaluation Method of Crystallinity and Orientation of Thin Film> The evaluation of epitaxial growth may be performed during or after the thin film is formed, depending on the evaluation method.

[0076] Examples of methods for evaluating epitaxial growth performed when forming a thin film include reflection high energy electron diffraction (RHEED) and surface photoabsorption (SPA).

[0077] In addition, the epitaxial growth (crystallinity and orientation) of the formed thin film can be evaluated by combining transmission electron microscopy (TEM), reciprocal space mapping in X-ray diffraction (XRD: X-ray Diffraction), wide-angle reciprocal space mapping (WRSM: Wide-angle Reciprocal Space Mapping), pole measurement, Out-of-Plane measurement, In-Plane measurement, etc.

[0078] The following describes a measurement method that can be used to evaluate the crystallinity and orientation of a thin film.

[0079] <Wide-angle reciprocal space mapping> Illustrate wide-angle reciprocal space mapping.

[0080] Reciprocal space is a space composed of the basic vectors of reciprocal space (also called reciprocal lattice vectors), which reflects the periodicity of real space. j and the fundamental vector a in the real space lattice i The relationship is as follows: i，j is the Kronecker function. In other words, the surface defined in the crystal in real space is regarded as a lattice point in the reciprocal lattice.

[0081] [Formula 2] a i b j =2πδ i，j (2)

[0082] In an epitaxially grown thin film, the crystal orientation inhomogeneity of the crystals constituting the thin film is small, that is, the orientation is high. Therefore, when the reciprocal space diagram of the epitaxially grown thin film is obtained, the observed spot intensity is high and the half width of the spot is small. On the other hand, when the reciprocal space diagram of a thin film with large crystal orientation inhomogeneity, that is, low orientation, is obtained, the observed spot intensity is low and the half width of the spot is large. As described above, by obtaining the reciprocal space diagram, the crystallinity and orientation of the thin film can be evaluated.

[0083] Reference Figure 4 The wide-angle reciprocal space mapping using an X-ray analysis device is described. Figure 4As shown, the direction in which the X-ray source source, sample sample and detector are arranged in a row when the X-ray analysis device is viewed from the top surface is defined as the ψ axis. In addition, the direction perpendicular to the ψ axis when the X-ray analysis device is viewed from the top surface is defined as the θ axis. In addition, the direction perpendicular to the ψ axis and the θ axis is defined as the φ axis. In other words, the φ axis is parallel to the direction in which the X-ray analysis device is viewed from the top surface. Note that sometimes the axis defined as the ψ axis in this specification is defined as the χ axis depending on the device. Therefore, the ψ axis may also be referred to as the χ axis. Similarly, sometimes the axis defined as the θ axis in this specification is defined as the ω axis depending on the device. Therefore, the θ axis may also be referred to as the ω axis.

[0084] In wide-angle reciprocal space mapping, a two-dimensional detector is used as a detector. The two-dimensional detector has position information for the 2θ and ψ directions on the detection surface. Note that Figure 4 The detector shown imitates a two-dimensional detector.

[0085] like Figure 4 As shown, when the X-ray source source is fixed, wide-angle reciprocal space mapping is performed by driving the sample sample and the detector detector. Here, the detector detector can be tilted in the 2θ direction, and the sample sample can be tilted in the θ direction, the φ direction, and the ψ direction. Wide-angle reciprocal space mapping is a measurement method that performs 2θ / θ scanning at each ψ position (angle) while gradually tilting the sample sample in the ψ direction. In this way, a reciprocal space map with a wider range in the reciprocal space as the measurement object can be obtained. In addition, when the X-ray source source is movable, wide-angle reciprocal space mapping is performed by driving the X-ray source source, the sample sample, and the detector detector. Here, the X-ray source source can be tilted in the θ direction. Note that, unless otherwise specified, CuKα line (wavelength: 0.15418nm) is used as the X-ray source in this specification.

[0086] In addition, a simulation of a wide-angle reciprocal space map is performed to analyze the intensity distribution appearing in the wide-angle reciprocal space map obtained above. As a simulation of a wide-angle reciprocal space map, for example, the software "SMAP / forCross Sectional XRD-RSM" provided by Bruker Japan can be used. By inputting the parameters of the crystal structure, lattice constant, and orientation into the software, a wide-angle reciprocal space map corresponding to the input values ​​is output. By comparing the wide-angle reciprocal space map output in the simulation with the wide-angle reciprocal space map obtained in the measurement, the intensity distribution appearing in the wide-angle reciprocal space map obtained by the measurement can be analyzed.

[0087] When the crystal structure in the metal oxynitride film is a wurtzite structure with a (001) orientation, spots corresponding to the reciprocal point 002, the reciprocal point 101, etc. are observed in the wide-angle reciprocal space diagram of the metal oxynitride film. Here, the peak of the spot corresponding to the reciprocal point 002 is preferably located at an angle 2θ of 30° to 35° and near an angle ψ of 0°. In addition, the peak of the spot corresponding to the reciprocal point 101 is preferably located at an angle 2θ of 33° to 37° and an angle ψ of 61° to 65°. In addition, the half-width of the spots corresponding to the reciprocal point 002 and the reciprocal point 101 is preferably less than 2°. Therefore, it can be used as one of the indicators to judge that the metal oxynitride film has been epitaxially grown in a manner that the c-axis direction of the crystal contained in the metal oxynitride film is consistent with the normal direction of the substrate surface of the single crystal.

[0088] <Pole measurement> Pole measurement is a method of measuring the distribution of diffraction intensity by rotating the sample in various directions while keeping the X-ray source and detector positions (angles) fixed. In this specification, a two-dimensional detector is used as a detector in pole measurement. Specifically, while the detector is fixed at a detection angle (2θ) and the sample is tilted in the θ direction and the ψ direction, the lattice plane that is rotated to the in-plane direction (φ direction) and tilted in various directions is measured. The diffraction intensity obtained from the pole measurement can be used to evaluate the crystallinity and orientation of the film. Note that the detector used for pole measurement is not limited to a two-dimensional detector, and a zero-dimensional detector can also be used.

[0089] use FIG. 5A to FIG. 5C The diffraction intensity obtained in the pole measurement is shown in the pole figure. Figure 5A The polar diagram is shown. Figure 5A As shown in FIG. 1 , the angle ψ of the center P0 of the pole figure is 0°, and the angle ψ of the periphery P1 of the pole figure is 90°. In addition, the straight line extending from the center P0 of the pole figure to the top of the periphery P1 of the pole figure (at Figure 5A The angle φ between the straight line represented by the dotted line P0-P2 in the figure and the straight line extending from the center P0 of the pole figure to the periphery P1 of the pole figure (in Figure 5A The angle formed by the straight line represented by the dotted line P0-P3 in the figure is angle φ. Figure 5A In the figure, the angle φ is shown to increase when rotating in the counterclockwise direction, but the present invention is not limited to this. Depending on the device, the angle φ may increase when rotating in the clockwise direction. In addition, depending on the range of the ψ scan, the angle of the pole figure obtained by the pole measurement may not be obtained within the range of 0° to 90°.

[0090] Figure 5B and Figure 5CIt is a schematic diagram of the diffraction intensity obtained in pole figure measurement. Figure 5B It is a schematic diagram of the diffraction intensity when a spotty intensity distribution is observed on a concentric circle at an angle ψ (a circle indicated by a dotted line in the drawing). Figure 5C It is a schematic diagram of the diffraction intensity when an annular intensity distribution is observed.

[0091] For example, the (101) plane of the wurtzite-type structure has six-fold symmetry. That is, when performing pole figure measurement on a c-axis epitaxial film containing a crystal with a wurtzite-type structure, as Figure 5B shown, a spotty intensity distribution (diffraction peak) is observed at six locations on a concentric circle at a certain angle ψ. Therefore, when a thin film containing a crystal with a wurtzite-type structure is epitaxially grown on the c-axis, in the φ scan of the (101) plane of the crystal of the thin film in pole figure measurement, a diffraction peak indicating six-fold symmetry is observed. Specifically, diffraction peaks are observed at intervals of approximately 60° for the angle φ on a concentric circle at an angle ψ of approximately 62°.

[0092] On the other hand, when performing pole figure measurement on a non-epitaxially grown thin film, an annular intensity distribution as Figure 5C shown is observed, or no diffraction peak is observed. Therefore, by analyzing the intensity distribution observed in pole figure measurement, it is possible to evaluate whether the thin film is epitaxially grown.

[0093] In addition, in the φ scan of the (111) plane of a single crystal YSZ substrate in pole figure measurement, a diffraction peak indicating three-fold symmetry is observed. Specifically, diffraction peaks are observed at intervals of approximately 120° for the angle φ on a concentric circle at an angle ψ of approximately 70°. Also, in the φ scan of the (104) plane of a single crystal A-plane sapphire substrate in pole figure measurement, a diffraction peak indicating two-fold symmetry is observed. Specifically, diffraction peaks are observed at intervals of approximately 180° for the angle φ on a concentric circle at an angle ψ of approximately 58°.

[0094] <Out-of-plane measurement and In-plane measurement> As measurements using the XRD method, there are Out-of-plane measurement and In-plane measurement. Out-of-plane measurement is a method for evaluating a crystal plane parallel to the surface of the thin film, and In-plane measurement is a method for evaluating a crystal plane perpendicular to the surface of the thin film. In Out-of-plane measurement and In-plane measurement, a zero-dimensional detector can also be used as the detector.

[0095] As described above, the structures, methods, etc. shown in this embodiment can be used in appropriate combination with the structures, methods, etc. shown in other embodiments and examples.

[0096] (Implementation Method 2) In this embodiment, uses of the epitaxially grown metal oxynitride film described in the above embodiment will be described.

[0097] The metal oxynitride film can be used in, for example, a light emitting element, a light receiving element, a semiconductor device, etc. In particular, it can be used in a light emitting element (also called a photodiode or LED).

[0098] Reference Fig. 6A and Figure 6B A structural example of a light-emitting element using the above-mentioned metal oxynitride film is described. In this embodiment, a light-emitting element having a double heterojunction is described. Note that one embodiment of the present invention is not limited to this, and a light-emitting element having a quantum well junction may also be used.

[0099] Fig. 6A and Figure 6B FIG. 1 is a light emitting element 100 using a metal oxynitride film according to one embodiment of the present invention. Fig. 6A and Figure 6B As shown, the light emitting element 100 includes a substrate 102 , an n-type cladding layer 104 , an active layer 106 , a p-type cladding layer 108 , an n-type electrode 110 , and a p-type electrode 112 .

[0100] The active layer 106 is sandwiched between the n-type cladding layer 104 and the p-type cladding layer 108. In the active layer 106, electrons and holes are combined to emit light. That is, the active layer 106 can also be called a light-emitting layer. The stacked structure including the n-type cladding layer 104, the active layer 106 and the p-type cladding layer 108 is formed in a manner that emits red, yellow, green, blue, etc. light. For example, gallium-phosphorus compounds, gallium-arsenic compounds, gallium-aluminum-arsenic compounds, aluminum-gallium-indium-phosphorus compounds, gallium nitrides, indium-gallium nitride compounds, selenium-zinc compounds, etc. can be used for the stacked structure.

[0101] By appropriately selecting the atomic ratio of the metal constituting the metal oxynitride film according to one embodiment of the present invention, the flow rate of nitrogen gas introduced into the reaction chamber during formation, etc., the conductivity (or insulation), band gap, light transmittance, etc. of the metal oxynitride film can be adjusted. For example, there is a tendency that the conductivity of the film increases as the flow rate of nitrogen gas increases. Therefore, by adjusting the conductivity of the metal oxynitride film, the metal oxynitride film can be used for Fig. 6A The n-type cladding layer 104 or Figure 6B An n-type electrode 110 is shown.

[0102] In addition, the metal oxynitride film can also be used for Figure 6B The n-type electrode 110 and the n-type cladding layer 104 are shown. When the metal oxynitride film is used for Figure 6BWhen the n-type electrode 110 and the n-type cladding layer 104 are formed, the metal oxynitride film can be continuously formed by adjusting the nitrogen gas flow rate. Figure 6B An n-type electrode 110 and an n-type cladding layer 104 are shown.

[0103] Furthermore, the metal oxynitride film can be used as a buffer layer for epitaxially growing a thin film on the film. Therefore, the crystallinity of the n-type cladding layer 104 or active layer 106 formed on the metal oxynitride film can be improved. Note that the crystal structure of the metal oxynitride film is a hexagonal system, especially a wurtzite crystal structure. Therefore, as the n-type cladding layer 104 or active layer 106 formed on the metal oxynitride film, it is preferred to use a material that forms a wurtzite crystal structure, such as gallium nitride, indium-gallium nitride compound, etc.

[0104] As described above, the metal oxynitride film is used as a base (buffer layer) for growing hexagonal crystals, and is used as an n-type electrode or an n-type cladding layer. By using the metal oxynitride film for the n-type electrode 110 or the n-type cladding layer 104, it is easy to epitaxially grow the n-type cladding layer 104 or the active layer 106, thereby improving the crystallinity of the n-type cladding layer 104 or the active layer 106. Therefore, the characteristics of the light-emitting element such as luminous efficiency and durable life can be improved.

[0105] This embodiment mode can be combined with other embodiment modes and examples as appropriate.

[0106] (Implementation 3) In this embodiment, refer to Fig. 7A and Figure 7B Examples of using the light-emitting element of one embodiment of the present invention in various lighting devices will be described. By using the light-emitting element of one embodiment of the present invention, a lighting device with high light emission efficiency and reliability can be manufactured.

[0107] Fig. 7A This is an example of using a light-emitting element for an indoor lighting device. By using a plurality of light-emitting elements, a large-area lighting device 8501 and a curved lighting device 8502 can be formed. In addition, a large lighting device 8503 can also be installed on the indoor wall. In addition, a touch sensor can also be installed in the lighting device 8501, the lighting device 8502, and the lighting device 8503 to start or turn off the power.

[0108] In addition, by using the light-emitting element on the surface side of the table, a lighting device 8504 having the function of a table can be provided. In addition, by using the light-emitting element on a part of other furniture, a lighting device having the function of furniture can be provided.

[0109] Furthermore, a light-emitting device to which the light-emitting element of one embodiment of the present invention is applied can be used for automobile lighting, and the lighting is provided on, for example, an instrument panel, a windshield, a ceiling, or the like.

[0110] Figure 7B FIG. 7 shows the appearance of a car 7900. The car 7900 includes a body 7901, wheels 7902, a front windshield 7903, lamps 7904, fog lamps 7905, and the like. The light-emitting element of one embodiment of the present invention can be used, for example, Figure 7B The lamp 7904 and the fog lamp 7905 are shown. In addition, although not shown in the figure, for example, it can be used for side turn signals, reverse lights, door lights, etc.

[0111] As described above, by applying the light-emitting element of one embodiment of the present invention, a lighting device can be obtained. Note that the present invention is not limited to the lighting device described in this embodiment, and the present invention can be applied to lighting devices in various fields.

[0112] The structure described in this embodiment mode can be used in combination with the structures described in other embodiment modes and examples as appropriate.

[0113] (Implementation 4) In this embodiment, refer to FIG. 8A to FIG. 8C A structural example of a display device using the light-emitting element described in the above embodiment mode will be described.

[0114] The display device of this embodiment has a function of displaying an image using a light-emitting element. In this embodiment, an example in which a micro light-emitting diode (hereinafter also referred to as Micro LED) is used as a light-emitting element is described.

[0115] By using Micro LED as a display element, the power consumption of the display device can be reduced. In addition, the display device can be made thinner and lighter. In addition, the display device using Micro LED as a display element has a high contrast and a wide viewing angle, so the display quality can be improved.

[0116] The area of ​​the light emitting region of the Micro LED is preferably 1 mm 2 Below, more preferably 10000 μm 2 Below, more preferably 3000 μm 2 Below, more preferably 700 μm 2 the following.

[0117] Fig. 8A A configuration example of a display device 400 using a light-emitting element is shown. The display device 400 includes a pixel portion 401 , a driver circuit 402 , and a driver circuit 403 .

[0118] The pixel unit 401 is composed of a plurality of pixels pix. Each pixel pix is ​​connected to a wiring SL and a wiring GL. Each wiring GL is connected to a driving circuit 402, and each wiring SL is connected to a driving circuit 403. A selection signal is supplied to the wiring GL, and an image signal is supplied to the wiring SL.

[0119] The driving circuit 402 has a function of supplying a selection signal to the pixel pix. Specifically, the driving circuit 402 has a function of supplying a selection signal to the wiring GL, and the wiring GL has a function of transmitting the selection signal output from the driving circuit 402 to the pixel pix. In addition, the driving circuit 402 may also be referred to as a gate side driving circuit or a gate driver, and the wiring GL may be referred to as a selection signal line, a gate line, or the like.

[0120] The driving circuit 403 has a function of supplying an image signal to the pixel pix. Specifically, the driving circuit 403 has a function of supplying an image signal to the wiring SL, and the wiring SL has a function of transmitting the image signal output from the driving circuit 403 to the pixel pix. In addition, the driving circuit 403 may also be referred to as a source side driving circuit or a source driver, and the wiring SL may be referred to as an image signal line, a source line, or the like.

[0121] Figure 8B A structural example of a pixel pix using a light-emitting element as a display element is shown. Figure 8B The pixel pix shown includes a transistor Tr31, a transistor Tr32, a capacitor C31, and a light emitting element LE. In addition, here, the transistor Tr31 and the transistor Tr32 are n-channel types, but the polarity of the transistor can be changed appropriately. The light emitting element described in the above embodiment can be used for the light emitting element LE.

[0122] The gate of the transistor Tr31 is connected to the wiring GL, one of the source and the drain of the transistor Tr31 is connected to the gate of the transistor Tr32 and one electrode of the capacitor C31, and the other of the source and the drain of the transistor Tr31 is connected to the wiring SL. One of the source and the drain of the transistor Tr32 is connected to the other electrode of the capacitor C31 and one electrode of the light emitting element LE, and the other of the source and the drain of the transistor Tr32 is connected to the wiring supplied with the potential Va. The other electrode of the light emitting element LE is connected to the wiring supplied with the potential Vc. The node connected to one of the source and the drain of the transistor Tr31, the gate of the transistor Tr32, and one electrode of the capacitor C31 is referred to as a node N31. In addition, the node connected to one of the source and the drain of the transistor Tr32, the other electrode of the capacitor C31, and one electrode of the light emitting element LE is referred to as a node N32.

[0123] Here, a case where the potential Va is a high power supply potential and the potential Vc is a low power supply potential is described. The potential Va and the potential Vc may be common potentials in a plurality of pixels pix. The capacitor C31 is used as a storage capacitor for holding the potential of the node N31.

[0124] The transistor Tr31 has a function of controlling the potential of the wiring SL supplied to the node N31. Specifically, by controlling the potential of the wiring GL, the transistor Tr31 is turned on, and the potential of the wiring SL corresponding to the image signal is supplied to the node N31, thereby writing to the pixel pix. Then, by controlling the potential of the wiring GL, the transistor Tr31 is turned off, thereby maintaining the potential of the node N31.

[0125] The amount of current flowing between the source and drain of transistor Tr32 is controlled according to the voltage between node N31 and node N32, so that the light emitting element LE emits light with a brightness corresponding to the amount of current. Therefore, the grayscale of pixel pix can be controlled. In addition, it is preferred that transistor Tr32 operates in a saturation region.

[0126] Here, the transistor Tr31 and the transistor Tr32 may be arranged on the same layer or in a stacked manner. By arranging the transistor Tr31 and the transistor Tr32 on the same layer, the transistor Tr31 and the transistor Tr32 may be manufactured at the same time, and the manufacturing process of the display device may be reduced. In addition, by arranging the transistor Tr31 and the transistor Tr32 in a stacked manner, the integration of the display device may be improved.

[0127] In addition, if Figure 8B In the preferred embodiment, two transistors (Tr31 and Tr32) are included in the pixel pix. However, one embodiment of the present invention is not limited to this, and the pixel pix may include three or more transistors.

[0128] Figure 8C Shown with Figure 8B A different example is a structural example of a pixel pix using a light-emitting element as a display element. Figure 8C The pixel pix shown includes a transistor Tr31, a transistor Tr32, a transistor Tr33, a capacitor C31 and a light emitting element LE. In other words, Figure 8C The pixel pix shown is Figure 8B The pixel pix shown has a pixel in which a transistor Tr33 for monitoring the amount of current flowing through the transistor Tr32 is added.

[0129] The gate of the transistor Tr31 is connected to the wiring GL, one of the source and the drain of the transistor Tr31 is connected to the gate of the transistor Tr32 and one electrode of the capacitor C31, and the other of the source and the drain of the transistor Tr31 is connected to the wiring SL. One of the source and the drain of the transistor Tr32 is connected to the other electrode of the capacitor C31, one electrode of the light emitting element LE, and one of the source and the drain of the transistor Tr33, and the other of the source and the drain of the transistor Tr32 is connected to the wiring supplied with the potential Va. The other electrode of the light emitting element LE is connected to the wiring supplied with the potential Vc. The gate of the transistor Tr33 is connected to the wiring GL, and the other of the source and the drain of the transistor Tr33 is connected to the monitoring line ML. The node connected to one of the source and the drain of the transistor Tr31, the gate of the transistor Tr32, and one electrode of the capacitor C31 is referred to as a node N31. In addition, a node connected to one of the source and the drain of the transistor Tr32, the other electrode of the capacitor C31, one electrode of the light emitting element LE, and one of the source and the drain of the transistor Tr33 is referred to as a node N32.

[0130] By sequentially performing the above operations for each wiring GL, the image of the first frame can be displayed.

[0131] When the wiring GL is selected, either a progressive scanning method or an interlaced scanning method can be used. In addition, when the image signal is supplied to the wiring SL, either a dot sequential drive in which the image signal is sequentially supplied to the wiring SL can be used, or a line sequential drive in which the image signal is simultaneously supplied to all the wirings SL can be used. In addition, the image signal can also be sequentially supplied in units of a plurality of wirings SL.

[0132] Then, in the second frame period, an image is displayed by the same operation as in the first frame period, thereby rewriting the image displayed on the pixel portion 401 .

[0133] As semiconductors used for transistors in pixel pix, elements of Group XIV such as silicon and germanium, compound semiconductors such as gallium arsenide, organic semiconductors, metal oxides, etc. can be used. In addition, the semiconductor can be a non-single-crystal semiconductor (amorphous semiconductor, microcrystalline semiconductor, polycrystalline semiconductor, etc.) or a single-crystal semiconductor.

[0134] The transistor in the pixel pix preferably contains an amorphous semiconductor in the channel formation region, especially hydrogenated amorphous silicon (a-Si:H). Transistors using amorphous semiconductors are more easily compatible with large substrate areas, and can simplify the manufacturing process when manufacturing a large-screen display device that can support 4K2K broadcasting or 8K4K broadcasting, for example.

[0135] As the transistor included in the pixel pix, a transistor (OS transistor) containing a metal oxide in the channel formation region may also be used. The field effect mobility of the OS transistor is higher than that of a transistor using hydrogenated amorphous silicon. In addition, the crystallization step required in forming a transistor using polycrystalline silicon is not required in the process of forming the OS transistor.

[0136] Since the off-state current of the OS transistor is extremely small, when the OS transistor is used as the transistor Tr31, the image signal can be maintained in the pixel pix for a very long period of time. As a result, the update frequency of the image signal can be set to be extremely low during the period when the image displayed by the pixel unit 401 does not change or changes to a certain value or less. As the update frequency of the image signal, for example, it can be set to less than once in 0.1 seconds, less than once in 1 second, or less than once in 10 seconds. In particular, when multiple pixels pix are set for 4K2K broadcasting or 8K4K broadcasting, power consumption can be effectively reduced by omitting the update of the image signal.

[0137] This embodiment mode can be combined with the description of other embodiment modes and examples as appropriate.

[0138] (Implementation 5) In this embodiment, an electronic device which is one embodiment of the present invention and uses the display device described in the above embodiment will be described with reference to the drawings.

[0139] Electronic devices include, for example, television sets, desktop or notebook personal computers, displays for computers, etc., digital signage, large-scale game consoles such as pinball machines, and other electronic devices with larger screens, as well as digital cameras, digital video cameras, digital photo frames, mobile phones, portable game consoles, portable information terminals, sound reproduction devices, and the like.

[0140] An electronic device of one embodiment of the present invention may also include an antenna. By receiving a signal through the antenna, an image or data may be displayed on the display unit. Note that since the display unit may be composed of a display device, the display unit may be referred to as a display device. In addition, when the electronic device includes an antenna and a secondary battery, the antenna may be used for contactless power transmission.

[0141] An electronic device of one embodiment of the present invention may also include a sensor (the sensor has the function of measuring the following factors: force, displacement, position, speed, acceleration, angular velocity, rotation speed, distance, light, liquid, magnetism, temperature, chemical substance, sound, time, hardness, electric field, current, voltage, electricity, radiation, flow, humidity, inclination, vibration, odor or infrared).

[0142] An electronic device of one embodiment of the present invention may have various functions. For example, it may have the following functions: a function of displaying various information (static images, dynamic images, text images, etc.) on a display unit; a function of a touch panel; a function of displaying a calendar, date, or time, etc.; a function of executing various software (programs); a function of wireless communication; a function of reading programs or data stored in a storage medium; etc.

[0143] Fig.9A 100 shows an example of a television set. In a television set 7100, a display portion 7000 is incorporated in a housing 7101. Here, a structure in which the housing 7101 is supported by a stand 7103 is shown.

[0144] The display device according to one embodiment of the present invention can be used for the display portion 7000 .

[0145] The operation can be performed by using the operation switch provided in the housing 7101 or the remote control operation machine 7111 provided separately. Fig.9A In addition, the display unit 7000 may be provided with a touch sensor, and the television set 7100 may be operated by touching the display unit 7000 with a finger, a stylus pen, or the like. In addition, the remote control unit 7111 may be provided with a display unit for displaying data output from the remote control unit 7111. By using the operation keys or the touch panel provided in the remote control unit 7111, the channel and volume can be operated, and the image displayed on the display unit 7000 can be operated.

[0146] In addition, the television device 7100 has a receiver and a modem, etc. The receiver can be used to receive general television broadcasts. Furthermore, the television device is connected to a wired or wireless communication network through a modem to perform one-way (from a sender to a receiver) or two-way (between a sender and a receiver or between receivers, etc.) information communication.

[0147] Fig. 9B A notebook personal computer 7200 is shown. The notebook personal computer 7200 includes a housing 7211 , a keyboard 7212 , a pointing device 7213 , an external connection port 7214 , and the like. A display portion 7000 is incorporated in the housing 7211 .

[0148] The display device according to one embodiment of the present invention can be used for the display portion 7000 .

[0149] Fig. 9C and Fig.9D An example of digital signage is shown.

[0150] Fig. 9CThe digital signage 7300 shown includes a housing 7301, a display unit 7000, a speaker 7303, etc. In addition, an LED lamp, operation keys (including a power switch or an operation switch), a connection terminal, various sensors, a microphone, etc. may be included.

[0151] Fig.9D The digital signage 7400 is shown to be disposed on a cylindrical pillar 7401. The digital signage 7400 includes a display unit 7000 disposed along a curved surface of the pillar 7401.

[0152] exist Fig. 9C and Fig.9D In the embodiment of the present invention, the display device according to one embodiment of the present invention can be used for the display portion 7000 .

[0153] The larger the display unit 7000 is, the more information can be provided at one time. The larger the display unit 7000 is, the easier it is to attract people's attention, for example, the advertising effect can be improved.

[0154] By using a touch panel for the display unit 7000, not only can a static image or a dynamic image be displayed on the display unit 7000, but the user can also intuitively operate it, which is preferred. In addition, when used for providing information such as route information or traffic information, the ease of use can be improved through intuitive operation.

[0155] like Fig. 9C and Fig.9D As shown, the digital signage 7300 or the digital signage 7400 can be linked with the information terminal device 7311 or the information terminal device 7411 such as a smartphone carried by the user preferably through wireless communication. For example, the advertising information displayed on the display unit 7000 can be displayed on the screen of the information terminal device 7311 or the information terminal device 7411. In addition, by operating the information terminal device 7311 or the information terminal device 7411, the display of the display unit 7000 can be switched.

[0156] In addition, the game can be executed on the digital signage 7300 or the digital signage 7400 using the screen of the information terminal device 7311 or the information terminal device 7411 as an operation unit (controller). Thus, an unspecified number of users can participate in the game at the same time and enjoy the game.

[0157] Furthermore, the display device according to one embodiment of the present invention can be assembled along a curved surface of an inner wall or an outer wall of a house or a building, or an interior or exterior of a vehicle. Fig.9E An example in which a display device according to one embodiment of the present invention is mounted on a vehicle is described.

[0158] Fig.9EFIG. 5 shows a configuration example of a vehicle having a display unit 5001. As the display unit 5001, a display device according to one embodiment of the present invention can be used. Note that Fig.9E The example in which the display unit 5001 is installed in a right-hand drive vehicle is shown, but the present invention is not limited thereto and the display unit 5001 may also be installed in a left-hand drive vehicle. Fig.9E The configuration of the structure shown is interchanged left and right.

[0159] exist Fig.9E 5002, a steering wheel 5003, and a front windshield 5004 are shown in the figure. The display unit 5001 is arranged at a predetermined position of the instrument panel 5002 (specifically, around the driver) and has a substantially T-shaped shape. Fig.9E 2 shows an example in which a display unit 5001 formed by using a plurality of display panels 5007 (display panels 5007a, 5007b, 5007c, and 5007d) is provided along an instrument panel 5002; however, the display unit 5001 may be configured in a manner divided into a plurality of locations.

[0160] The plurality of display panels 5007 may also be flexible. In this case, the display unit 5001 may be processed into a complex shape, thereby realizing a structure in which the display unit 5001 is arranged along a curved surface of the instrument panel 5002 or the like, and a structure in which the display area of ​​the display unit 5001 is not arranged on the connecting portion of the steering wheel, the display portion of the instrument, the air outlet 5006 or the like.

[0161] In addition, a camera 5005 for photographing the side and rear conditions may also be provided outside the vehicle. Fig.9E Although an example in which the camera 5005 is provided instead of the rearview mirror is shown, both a rearview mirror and a camera may be provided.

[0162] A CCD camera or a CMOS camera can be used as the camera 5005. In addition, an infrared camera can be used in combination with the above-mentioned cameras. Since the output level of the infrared camera increases as the temperature of the subject increases, a living body such as a human or an animal can be detected or extracted.

[0163] The image captured by the camera 5005 can be output to any one or more of the display panels 5007a, 5007b, 5007c, and 5007d. The display unit 5001 is mainly used to assist the driving of the vehicle. By using the camera 5005 to capture a wide-angle image of the rear and displaying the image on the panel 5007, the driver can see the blind spot area and prevent accidents.

[0164] In addition, the distance image sensor may be provided on the roof of the car, etc., and the image obtained by using the distance image sensor may be displayed on the display unit 5001. As the distance image sensor, an image sensor or a laser radar (LIDAR: Light Detection and Ranging) etc. may be used. By displaying both the image obtained by using the image sensor and the image obtained by using the distance image sensor on the display unit 5001, more information may be provided to the driver to assist driving.

[0165] The display unit 5001 may also have the function of displaying map information, traffic information, TV images, DVD images, etc. For example, the display panels 5007a, 5007b, 5007c, and 5007d may be used as one display screen to display large-size map information. Note that the number of display panels 5007 may be increased according to the images to be displayed.

[0166] The images displayed by the display panels 5007a, 5007b, 5007c and 5007d can be freely set according to the driver's preference. For example, a TV image or a DVD image can be displayed on the display panel 5007d on the left, map information can be displayed on the display panel 5007b in the center, an instrument can be displayed on the display panel 5007c on the right, and audio information can be displayed on the display panel 5007a near the gear lever (between the driver's seat and the front passenger seat). In addition, by combining multiple display panels 5007, a fail-safe function can be added to the display unit 5001. For example, even if a display panel 5007 fails for some reason, other display panels 5007 can be used for display by changing the display area.

[0167] This embodiment mode can be combined with the description of other embodiment modes and examples as appropriate. [Example]

[0168] In this embodiment, the results of evaluating the crystallinity and orientation of the metal oxynitride film manufactured by the method described in the above embodiment are described. Specifically, a plurality of samples (samples 1 to 7) in which the metal oxynitride film is formed on a substrate by the method described in the above embodiment are prepared, and wide-angle reciprocal space mapping, pole measurement, out-of-plane measurement, in-plane measurement, etc. are performed on each sample.

[0169] <Sample Manufacturing Method> First, the manufacturing methods of Samples 1 to 7 will be described.

[0170] Samples 1 to 7 are manufactured using the method for manufacturing a metal oxynitride film described in Embodiment 1. Specifically, a single crystal substrate is prepared, and a metal oxynitride film is formed on the substrate by introducing a gas into a reaction chamber and using an oxide target by sputtering. Note that the substrate is not pre-treated by atmospheric annealing, vacuum annealing, or the like before the metal oxynitride film is formed on the substrate. In addition, the formed metal oxynitride film is not heat-treated.

[0171] As the film formation conditions of the gold oxynitride film common to Samples 1 to 7, the film formation pressure was set to 0.4 Pa, the film formation power was set to 200 W, and the distance between the oxide target and the substrate was set to 130 mm.

[0172] The single crystal substrate used for manufacturing each sample is described. In samples 1 to 6, an yttria-stabilized zirconia (YSZ) substrate is prepared as a single crystal substrate. The surface orientation of the YSZ substrate is (111). In addition, in sample 7, an A-plane sapphire substrate is prepared as a single crystal substrate. The surface orientation of the A-plane sapphire substrate is (110).

[0173] Next, the oxide target used for manufacturing each sample is described. In Sample 1, Sample 5, Sample 6, and Sample 7, an In-Ga-Zn oxide target with In:Ga:Zn=4:2:4.1 [atomic ratio] is used as an oxide target. Therefore, the metal oxynitride film of Sample 1, Sample 5, Sample 6, and Sample 7 is an In-Ga-Zn oxynitride film. In addition, in Sample 2, an In-Zn oxide target with In:Zn=2:1 [atomic ratio] is used as an oxide target. Therefore, the metal oxynitride film of Sample 2 is an In-Zn oxynitride film. In addition, in Sample 3, zinc oxide is used as an oxide target. Therefore, the metal oxynitride film of Sample 3 is an oxynitride zinc film. In addition, in Sample 4, an In-Ga-Zn oxide target with In:Ga:Zn=1:1:1 [atomic ratio] is used as an oxide target. Therefore, the metal oxynitride film of Sample 4 is an In—Ga—Zn oxynitride film.

[0174] Next, the gas introduced into the reaction chamber (also referred to as film-forming gas) is described. In samples 1, 2, 3, 4, 6, and 7, 45 sccm of nitrogen gas (N2) is used as the film-forming gas. In sample 5, a mixed gas of 45 sccm of nitrogen gas (N2) and 45 sccm of argon gas (Ar) is used as the film-forming gas.

[0175] Next, the substrate temperature when forming the metal oxynitride film is described. In Sample 1, Sample 2, Sample 3, Sample 4, Sample 5, and Sample 7, the substrate temperature was set to 200° C. In Sample 6, the substrate temperature was set to 100° C.

[0176] Samples 1 to 7 were manufactured as described above. Table 1 shows a summary of the processing conditions of each sample.

[0177] [Table 1]

[0178] Wide-angle reciprocal space mapping, pole measurement, out-of-plane measurement, in-plane measurement, etc. were performed on each of the manufactured samples 1 to 7. As an apparatus for performing wide-angle reciprocal space mapping, pole measurement, out-of-plane measurement, and in-plane measurement, an X-ray diffraction apparatus D8 DOSCOVER manufactured by Bruker Japan was used, and as a detector, a wide-angle reciprocal space mapping and pole measurement were used. A two-dimensional detector is used for the Out-of-plane measurement and the In-plane measurement. Note that the Out-of-plane measurement and the In-plane measurement are mainly performed to estimate the lattice constant used as the input value of the simulation of the wide-angle reciprocal space map as described below. Therefore, in this embodiment, the results of the Out-of-plane measurement and the In-plane measurement are omitted.

[0179] In wide-angle reciprocal space mapping, a two-dimensional detector ( Figure 4 The detector in the sample is aimed at the angle 2θ, and the angle θ is scanned at each angle ψ to perform the measurement. Figure 4 The sample in the two-dimensional detector ( Figure 4The distance between the detectors in the detector is set to 150 mm. In addition, the angle 2θ is set to 40°, and the range of the angle 2θ being greater than 20° and less than 60° is recorded. In addition, the angle θ is scanned within the range of greater than 10° and less than 30°. In addition, the angle ψ is set every 5° (a total of 18 steps) within the range of greater than 0° and less than 85°. The incident X-ray diameter is set to 0.3 mmφ using a collimator, the X-ray source uses CuKα line (wavelength: 0.15418 nm), and the output of the X-ray is set to 50 kV and 100 mA. The X-ray exposure time for each step is set to 60 seconds. Wide-angle reciprocal space mapping is performed on each sample to obtain a wide-angle reciprocal space map of each sample. Note that in each of the figures showing the wide-angle reciprocal space map, the horizontal axis represents the angle 2θ [°] and the vertical axis represents the angle ψ [°]. In addition, the intensity at each point of the wide-angle reciprocal space map is shown in a manner corresponding to the stick represented on the right side of the wide-angle reciprocal space map. Specifically, the higher the intensity, the darker (darker) the color is expressed, and the lower the intensity, the whiter (lighter) the color is expressed.

[0180] The simulation of the wide-angle reciprocal space map corresponding to each sample uses the software "SMAP / forCross Sectional XRD-RSM" of Bruker Japan. In addition, it is assumed that the crystal structure of the metal oxynitride included in each sample is a wurtzite structure, and the lattice constant is set to the lattice constant estimated from the scanning results of the Out-of-plane measurement, In-plane measurement and other reciprocal lattice points. Note that in the case of comparing the wide-angle reciprocal space maps of crystalline structures having the same symmetry (or space group) and different lattice constants, the positions of the peaks of the spots appearing in the wide-angle reciprocal space maps (angle 2θ, angle ψ) are sometimes observed in a staggered manner.

[0181] The simulated wide-angle reciprocal space diagram shows all spots that would be observed in the crystal assumed in the simulation. Therefore, since the wide-angle reciprocal space diagram of the epitaxially grown thin film and the in-plane oriented crystal orientation in the simulated wide-angle reciprocal space diagram may differ depending on the angle φ, the observed spots may be different.

[0182] In this embodiment, the wide-angle reciprocal space mapping is performed by adjusting the angle φ so that the crystal plane corresponding to the reciprocal lattice point observed in the wide-angle reciprocal space image corresponds to the crystal plane observed in the pole measurement. Specifically, in samples 1 to 6, it is preferred to adjust the angle φ to perform the wide-angle reciprocal space mapping in such a manner that the (101) plane of the metal oxynitride film included in each sample and the (111) plane of the substrate included in each sample are simultaneously observed in the wide-angle reciprocal space image. In addition, in sample 7, it is preferred to adjust the angle φ to perform the wide-angle reciprocal space mapping in such a manner that the (101) plane of the metal oxynitride film included in sample 7 and the (104) plane of the substrate included in sample 7 are simultaneously observed in the wide-angle reciprocal space image.

[0183] In addition, the results of the pole point measurement shown in this embodiment are expressed as pole figures.

[0184] <Evaluation of Sample 1> Fig. 10A is the wide-angle reciprocal space image of sample 1. In addition, Fig. 10B and Fig. 10C is the wide-angle reciprocal space diagram obtained by simulation. Fig. 10B is a wide-angle reciprocal space image of the substrate corresponding to the single crystal of sample 1, Fig. 10C This is a wide-angle reciprocal space image of crystals included in the metal oxynitride film corresponding to sample 1.

[0185] exist Fig. 10A By comparing the observed multiple spots and Fig. 10B and Fig. 10C From the spots shown, it can be seen that: the spot whose peak is located at an angle 2θ of about 35° and an angle ψ of about 62° corresponds to the (101) plane of the wurtzite structure; the spot whose peak is located at an angle 2θ of about 44° and an angle ψ of about 44° corresponds to the (102) plane of the wurtzite structure.

[0186] then, Fig.11A and Fig. 11B The results of pole measurement on sample 1 are shown. Fig.11A This is the result of the (111) surface of the single crystal substrate of sample 1. Fig. 11B This is the result of the (101) plane of the metal oxynitride film of sample 1.

[0187] like Fig.11A As shown by the solid circle in , spot-like intensity distribution is observed at three locations on the concentric circles with an angle ψ of about 70°. The spots are three-fold symmetric spots derived from the (111) plane of yttria-stabilized zirconia (YSZ). Fig. 11BAs shown by the solid circle in , spot-like intensity distribution is observed at six locations on concentric circles with an angle ψ of about 62°. That is, it can be seen that the (101) plane of the metal oxynitride film of sample 1 has six-fold symmetry, and the metal oxynitride film of sample 1 is oriented in the plane. In addition, since the angle formed by the (002) plane and the (101) plane in the wurtzite structure is about 62°, it can be seen that the crystals contained in the metal oxynitride film of sample 1 have a wurtzite structure. In addition, from Fig.11A and Fig. 11B It is found that the metal oxide film of Sample 1 is a c-axis epitaxial film that does not include a crystal domain in which the crystal orientation is rotated within the film plane.

[0188] As described above, it can be seen that the metal oxynitride film of Sample 1 has a wurtzite structure and grows epitaxially.

[0189] <Evaluation of Sample 2> Fig. 12A is the wide-angle reciprocal space image of sample 2. In addition, Fig. 12B and Fig. 12C is the wide-angle reciprocal space diagram obtained by simulation. Fig. 12B is a wide-angle reciprocal space image of the substrate corresponding to the single crystal of sample 2, Fig. 12C This is a wide-angle reciprocal space image of crystals included in the metal oxynitride film corresponding to sample 2.

[0190] exist Fig. 12A By comparing the observed multiple spots and Fig. 12B and Fig. 12C From the spots shown, it can be seen that: the spot whose peak is located at an angle 2θ of about 34° and an angle ψ of about 62° corresponds to the (101) plane of the wurtzite structure; the spot whose peak is located at an angle 2θ of about 44° and an angle ψ of about 44° corresponds to the (102) plane of the wurtzite structure.

[0191] then, Fig.13A and Fig. 13B The results of pole measurement on sample 2 are shown. Fig.13A This is the result of the (111) surface of the single crystal substrate of sample 2. Fig. 13B This is the result of the (101) plane of the metal oxynitride film of sample 2.

[0192] like Fig.13A As shown by the solid circle in , spot-like intensity distribution is observed at three locations on concentric circles with an angle ψ of about 70°. Fig. 13BAs shown by the solid circle in , spot-like intensity distribution is observed at six locations on concentric circles with an angle ψ of about 62°. That is, it can be seen that the (101) plane of the metal oxynitride film of sample 2 has six-fold symmetry, and the metal oxynitride film of sample 2 is oriented in the plane. In addition, since the angle formed by the (002) plane and the (101) plane in the wurtzite structure is about 62°, it can be seen that the crystals contained in the metal oxynitride film of sample 2 have a wurtzite structure. In addition, from Fig.13A and Fig. 13B It is found that the metal oxide film of Sample 2 is a c-axis epitaxial film that does not include a crystal domain in which the crystal orientation is rotated within the film plane.

[0193] As described above, it can be seen that the metal oxynitride film of Sample 2 has a wurtzite structure and grows epitaxially.

[0194] <Evaluation of Sample 3> Fig.14A is the wide-angle reciprocal space image of sample 3. In addition, Fig. 14B and Fig. 14C is the wide-angle reciprocal space diagram obtained by simulation. Fig. 14B is a wide-angle reciprocal space image of the substrate corresponding to the single crystal of sample 3, Fig. 14C This is a wide-angle reciprocal space image of crystals included in the metal oxynitride film corresponding to Sample 3.

[0195] exist Fig.14A By comparing the observed multiple spots and Fig. 14B and Fig. 14C From the spots shown, it can be seen that: the spot whose peak is located at an angle 2θ of about 36° and an angle ψ of about 62° corresponds to the (101) plane of the wurtzite structure; the spot whose peak is located at an angle 2θ of about 47° and an angle ψ of about 42° corresponds to the (102) plane of the wurtzite structure.

[0196] then, Fig.15A and Fig. 15B The results of pole point measurement on sample 3 are shown. Fig.15A This is the result of the (111) surface of the single crystal substrate of sample 3. Fig. 15B This is the result of the (101) plane of the metal oxynitride film of sample 3.

[0197] like Fig.15A As shown by the solid circle in , spot-like intensity distribution is observed at three locations on concentric circles with an angle ψ of about 70°. Fig. 15BAs shown by the solid circle in , spot-like intensity distribution is observed at six locations on concentric circles with an angle ψ of about 62°. That is, it can be seen that the (101) plane of the metal oxynitride film of sample 3 has six-fold symmetry, and the metal oxynitride film of sample 3 is oriented in the plane. In addition, since the angle formed by the (002) plane and the (101) plane in the wurtzite structure is about 62°, it can be seen that the crystals contained in the metal oxynitride film of sample 3 have a wurtzite structure. In addition, from Fig.15A and Fig. 15B It is found that the metal oxide film of Sample 3 is a c-axis epitaxial film that does not include a crystal domain in which the crystal orientation is rotated within the film plane.

[0198] As described above, it can be seen that the metal oxynitride film of Sample 3 has a wurtzite structure and grows epitaxially.

[0199] <Evaluation of Sample 4> Fig.16A is the wide-angle reciprocal space image of sample 4. In addition, Fig. 16B and Fig. 16C is the wide-angle reciprocal space diagram obtained by simulation. Fig. 16B is a wide-angle reciprocal space image of the substrate corresponding to the single crystal of sample 4, Fig. 16C This is a wide-angle reciprocal space image of the crystals included in the metal oxynitride film corresponding to Sample 4.

[0200] exist Fig.16A By comparing the observed multiple spots and Fig. 16B and Fig. 16C From the spots shown, it can be seen that: the spot whose peak is located at an angle 2θ of about 35° and an angle ψ of about 62° corresponds to the (101) plane of the wurtzite structure; the spot whose peak is located at an angle 2θ of about 44° and an angle ψ of about 44° corresponds to the (102) plane of the wurtzite structure.

[0201] then, Fig.17A and Fig. 17B The results of pole measurement on sample 4 are shown. Fig.17A This is the result of the (111) surface of the single crystal substrate of sample 4. Fig. 17B This is the result of the (101) plane of the metal oxynitride film of sample 4.

[0202] like Fig.17A As shown by the solid circle in , spot-like intensity distribution is observed at three locations on concentric circles with an angle ψ of about 70°. Fig. 17BAs shown by the solid circle in , spot-like intensity distribution is observed at six locations on concentric circles with an angle ψ of about 62°. That is, it can be seen that the (101) plane of the metal oxynitride film of sample 4 has six-fold symmetry, and the metal oxynitride film of sample 4 is oriented in the plane. In addition, since the angle formed by the (002) plane and the (101) plane in the wurtzite structure is about 62°, it can be seen that the crystals contained in the metal oxynitride film of sample 4 have a wurtzite structure. In addition, from Fig.17A and Fig. 17B It is found that the metal oxide film of Sample 4 is a c-axis epitaxial film that does not include a crystal domain whose crystal orientation is rotated within the film plane.

[0203] As described above, it can be seen that the metal oxynitride film of Sample 4 has a wurtzite structure and grows epitaxially.

[0204] <Evaluation of Sample 5> Fig.18A is the wide-angle reciprocal space image of sample 5. In addition, Fig.18B and Fig. 18C is the wide-angle reciprocal space diagram obtained by simulation. Fig.18B is a wide-angle reciprocal space image of the substrate corresponding to the single crystal of sample 5, Fig. 18C This is a wide-angle reciprocal space image of crystals included in the metal oxynitride film corresponding to Sample 5.

[0205] exist Fig.18A By comparing the observed multiple spots and Fig.18B and Fig. 18C From the spots shown, it can be seen that: the spot whose peak is located at an angle 2θ of about 35° and an angle ψ of about 62° corresponds to the (101) plane of the wurtzite structure; the spot whose peak is located at an angle 2θ of about 44° and an angle ψ of about 44° corresponds to the (102) plane of the wurtzite structure.

[0206] then, Fig.19A and Fig.19B The results of pole point measurement on sample 5 are shown. Fig.19A This is the result of the (111) surface of the single crystal substrate of sample 5. Fig.19B This is the result of the (101) plane of the metal oxynitride film of sample 5.

[0207] like Fig.19A As shown by the solid circle in , spot-like intensity distribution is observed at three locations on concentric circles with an angle ψ of about 70°. Fig.19BAs shown by the solid circle in , spot-like intensity distribution is observed at six locations on concentric circles with an angle ψ of about 62°. That is, it can be seen that the (101) plane of the metal oxynitride film of sample 5 has six-fold symmetry, and the metal oxynitride film of sample 5 is oriented in the plane. In addition, since the angle formed by the (002) plane and the (101) plane in the wurtzite structure is about 62°, it can be seen that the crystals contained in the metal oxynitride film of sample 5 have a wurtzite structure. In addition, from Fig.19A and Fig.19B It is found that the metal oxide film of Sample 5 is a c-axis epitaxial film that does not include a crystal domain in which the crystal orientation is rotated within the film plane.

[0208] As described above, it can be seen that the metal oxynitride film of Sample 5 has a wurtzite structure and grows epitaxially.

[0209] <Evaluation of Sample 6> Fig. 20A is the wide-angle reciprocal space image of sample 6. In addition, Fig. 20B and Fig. 20C is the wide-angle reciprocal space diagram obtained by simulation. Fig. 20B is a wide-angle reciprocal space image of the substrate corresponding to the single crystal of sample 6, Fig. 20C This is a wide-angle reciprocal space image of the crystals included in the metal oxynitride film corresponding to Sample 6.

[0210] exist Fig. 20A By comparing the observed multiple spots and Fig. 20B and Fig. 20C From the spots shown, it can be seen that: the spot whose peak is located at an angle 2θ of about 35° and an angle ψ of about 62° corresponds to the (101) plane of the wurtzite structure; the spot whose peak is located at an angle 2θ of about 44° and an angle ψ of about 44° corresponds to the (102) plane of the wurtzite structure.

[0211] then, Fig.21A and Fig. 21B The results of pole point measurement on sample 6 are shown. Fig.21A This is the result of the (111) surface of the single crystal substrate of sample 6. Fig. 21B This is the result of the (101) plane of the metal oxynitride film of sample 6.

[0212] like Fig.21A As shown by the solid circle in , spot-like intensity distribution is observed at three locations on concentric circles with an angle ψ of about 70°. Fig. 21BAs shown by the solid circle in , spot-like intensity distribution is observed at six locations on concentric circles with an angle ψ of about 62°. That is, it can be seen that the (101) plane of the metal oxynitride film of sample 6 has six-fold symmetry, and the metal oxynitride film of sample 6 is oriented in the plane. In addition, since the angle formed by the (002) plane and the (101) plane in the wurtzite structure is about 62°, it can be seen that the crystals contained in the metal oxynitride film of sample 6 have a wurtzite structure. In addition, from Fig.21A and Fig. 21B It is found that the metal oxide film of Sample 6 is a c-axis epitaxial film that does not include a crystal domain in which the crystal orientation is rotated within the film plane.

[0213] As described above, it can be seen that the metal oxynitride film of Sample 6 has a wurtzite structure and grows epitaxially.

[0214] <Evaluation of Sample 7> Fig.22A is the wide-angle reciprocal space image of sample 7. In addition, Fig. 22B and Fig. 22C is the wide-angle reciprocal space diagram obtained by simulation. Fig. 22B is a wide-angle reciprocal space image of the substrate corresponding to the single crystal of sample 7, Fig. 22C This is a wide-angle reciprocal space image of the crystals included in the metal oxynitride film corresponding to Sample 7.

[0215] exist Fig.22A By comparing the observed multiple spots and Fig. 22B and Fig. 22C From the spots shown, it can be seen that: the spot whose peak is located at an angle 2θ of about 35° and an angle ψ of about 62° corresponds to the (101) plane of the wurtzite structure; the spot whose peak is located at an angle 2θ of about 44° and an angle ψ of about 44° corresponds to the (102) plane of the wurtzite structure.

[0216] then, Fig.23A and Fig. 23B The results of pole point measurement on sample 7 are shown. Fig.23A This is the result of the (104) surface of the single crystal substrate of sample 7. Fig. 23B This is the result of the (101) plane of the metal oxynitride film of sample 7.

[0217] like Fig.23A As shown by the solid circle in the figure, a spot-like intensity distribution is observed at two locations on the concentric circles with an angle ψ of about 58°. The spot is a twice symmetrical spot originating from the (104) plane of the A-plane sapphire. Fig. 23BAs shown by the solid circle in , spot-like intensity distribution is observed at six locations on concentric circles with an angle ψ of about 62°. That is, it can be seen that the (101) plane of the metal oxynitride film of sample 7 has six-fold symmetry, and the metal oxynitride film of sample 7 is oriented in the plane. In addition, since the angle formed by the (002) plane and the (101) plane in the wurtzite structure is about 62°, it can be seen that the crystals contained in the metal oxynitride film of sample 7 have a wurtzite structure. In addition, from Fig.23A and Fig. 23B It is found that the metal oxide film of Sample 7 is a c-axis epitaxial film that does not include a crystal domain in which the crystal orientation is rotated within the film plane.

[0218] As described above, it can be seen that the metal oxynitride film of Sample 7 has a wurtzite structure and grows epitaxially.

[0219] At least a part of the structure, method, etc. described in this embodiment can be implemented in combination with other embodiment modes described in this specification as appropriate. [Explanation of symbols]

[0220] 10: substrate, 20: metal oxynitride film, 30: crystallization, 41: film forming chamber, 50a: pad, 50b: pad, 52a: target rack, 52b: target rack, 54a: magnet unit, 54b: magnet unit, 54N1: magnet, 54N2: magnet, 54S: magnet, 56: magnet rack, 58: component, 60: substrate, 62: substrate rack, 64a: magnetic field line, 64b: magnetic field line, 70a: sputtering target, 70b : sputtering target, 100: light emitting element, 102: substrate, 104: cladding layer, 106: active layer, 108: cladding layer, 110: n-type electrode, 112: p-type electrode, 400: display device, 401: pixel unit, 402: drive circuit, 403: drive circuit, 5001: display unit, 5002: instrument panel, 5003: steering wheel, 5004: windshield, 5005: camera, 5006: air outlet, 5 007: Display panel, 5007a: Display panel, 5007b: Display panel, 5007c: Display panel, 5007d: Display panel, 7000: Display unit, 7100: Television device, 7101: Housing, 7103: Stand, 7111: Remote control unit, 7200: Notebook personal computer, 7211: Housing, 7212: Keyboard, 7213: Pointing device, 7214: External connection port, 730 0: digital signage, 7301: housing, 7303: speaker, 7311: information terminal device, 7400: digital signage, 7401: pillar, 7411: information terminal device, 7900: automobile, 7901: vehicle body, 7902: wheel, 7903: windshield, 7904: lamp, 7905: fog lamp, 8501: lighting device, 8502: lighting device, 8503: lighting device, 8504: lighting device

Claims

1. A metal oxynitride film, wherein the metal oxynitride film is formed on a single crystal substrate, The metal oxynitride film contains zinc, indium and gallium, Furthermore, the metal oxynitride film is an in-plane oriented film.

2. A metal oxynitride film, in, The metal oxynitride film is formed on a single crystal substrate. The metal oxynitride film contains zinc, indium and gallium, And the metal oxynitride film is an in-plane oriented film grown by c-axis epitaxial growth and having regularity of crystal orientation in a direction horizontal to a single crystal substrate.

3. The metal oxynitride film according to claim 1 or 2, The substrate of the single crystal is a yttria-stabilized zirconia substrate. And the surface orientation of the yttria-stabilized zirconia substrate is (111).

4. The metal oxynitride film according to claim 1 or 2, The single crystal substrate is a sapphire substrate. And the surface orientation of the sapphire substrate is (110).

5. The metal oxynitride film according to claim 1 or 2, The crystal structure of the metal oxynitride film is a wurtzite structure.

6. The metal oxynitride film according to claim 1 or 2, When the metal oxynitride film is subjected to a pole measurement, a diffraction peak indicating a six-fold symmetry is observed in a φ scan performed on a (101) plane of a crystal of the metal oxynitride film in the pole measurement.

7. The metal oxynitride film according to claim 1 or 2, In the wide-angle reciprocal space image of the metal oxynitride film, a first spot and a second spot are observed. The peak of the first spot is located where the angle 2θ is 30° or more and 35° or less and the angle ψ is near 0°. The half width of the first spot is less than 2°, The peak of the second spot is located at a position where the angle 2θ is greater than or equal to 33° and less than or equal to 37° and the angle ψ is greater than or equal to 61° and less than or equal to 65°, And the half width of the second spot is less than 2°.

8. The metal oxynitride film according to claim 1 or 2, When a pole measurement is performed on the single crystal substrate, a diffraction peak representing a cubic symmetry is observed in a φ scan of the (111) plane, or a diffraction peak representing a bi-quadrant symmetry is observed in a φ scan of the (104) plane.

9. A display device, comprising: A light-emitting element comprising the metal oxynitride film according to claim 1 or 2; as well as A transistor electrically connected to the light emitting element.

10. A metal oxynitride film, wherein the metal oxynitride film is formed on a surface of a single crystal substrate, The metal oxynitride film contains zinc, indium and gallium, Furthermore, the metal oxynitride film is a c-axis epitaxial film in which the c-axis direction of the crystal is consistent with the normal direction of the surface of the single crystal substrate.

11. The metal oxynitride film according to claim 10, The substrate of the single crystal is a yttria-stabilized zirconia substrate. And the surface orientation of the yttria-stabilized zirconia substrate is (111).

12. The metal oxynitride film according to claim 10, The single crystal substrate is a sapphire substrate. And the surface orientation of the sapphire substrate is (110).

13. The metal oxynitride film according to claim 10, The crystal structure of the metal oxynitride film is a wurtzite structure.

14. The metal oxynitride film according to claim 10, When the metal oxynitride film is subjected to a pole measurement, a diffraction peak indicating a six-fold symmetry is observed in a φ scan performed on a (101) plane of a crystal of the metal oxynitride film in the pole measurement.

15. The metal oxynitride film according to claim 10, In the wide-angle reciprocal space image of the metal oxynitride film, a first spot and a second spot are observed. The peak of the first spot is located where the angle 2θ is 30° or more and 35° or less and the angle ψ is near 0°. The half width of the first spot is less than 2°, The peak of the second spot is located at a position where the angle 2θ is greater than or equal to 33° and less than or equal to 37° and the angle ψ is greater than or equal to 61° and less than or equal to 65°, And the half width of the second spot is less than 2°.

16. A display device, comprising: A light-emitting element comprising the metal oxynitride film according to claim 10; as well as A transistor electrically connected to the light emitting element.

17. A display device comprising: A light emitting element including a metal oxynitride film formed on a surface of a single crystal substrate, wherein the metal oxynitride film comprises zinc, indium and gallium, The metal oxynitride film is a c-axis epitaxial film in which the c-axis direction of the crystal coincides with the normal direction of the surface of the single crystal substrate. And the crystal structure of the metal oxynitride film is a wurtzite structure.

Images