Precursor composition for thin film deposition, method for manufacturing thin film, thin film manufacturing using same, and electronic device including thin film

Abstract

The present disclosure provides: a precursor composition for depositing a thin film including a liquid indium precursor, a liquid gallium precursor, and a liquid zinc precursor; a method for manufacturing a thin film by using the precursor composition; a thin film manufactured by using the precursor composition; and an electronic device including the thin film.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0128286, filed on September 23, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to precursor compositions for depositing thin films, methods for manufacturing thin films, thin films manufactured using the same, and electronic devices including thin films. Background Technology

[0004] Materials containing various types of metal atoms (such as indium and zinc atoms) are used in oxide semiconductors, and thin films of oxide semiconductors are fabricated through processes such as sputtering, atomic layer deposition (ALD), pulsed laser deposition (PLD), and chemical vapor deposition (CVD).

[0005] Recently, crystalline oxide semiconductors known as indium gallium zinc oxide (IGZO) (composite oxide films of indium, gallium, and zinc) are being used in thin-film transistors (TFTs). TFTs incorporating IGZO composite oxide films are suitable for large-area displays with high resolution. Summary of the Invention

[0006] The purpose of this disclosure is to provide a precursor composition for depositing thin films, a method for manufacturing thin films, thin films manufactured using the same, and electronic devices including thin films.

[0007] The purpose of this disclosure is not limited to the foregoing, and other purposes not described herein should be clearly understood by those skilled in the art from the detailed description.

[0008] According to one aspect of this disclosure, the precursor composition for depositing thin films may include liquid indium precursor, liquid gallium precursor, and liquid zinc precursor.

[0009] According to embodiments of the present disclosure, the molar ratio of indium:gallium:zinc in the precursor composition for depositing thin films can be 0.1 to 10:0.1 to 10:0.1 to 10.

[0010] According to embodiments of this disclosure, the liquid indium precursor may be one or more selected from triethylindium, triisopropylindium, and tri(tert-butyl)indium.

[0011] According to embodiments of this disclosure, the precursor composition for depositing thin films may not include solvents.

[0012] According to embodiments of this disclosure, all liquid indium precursors, liquid gallium precursors, and liquid zinc precursors may be alkyl precursors.

[0013] According to another aspect of this disclosure, a method for manufacturing a thin film is provided, which may include: i) obtaining a precursor composition for depositing a thin film by mixing a liquid indium precursor, a liquid gallium precursor and a liquid zinc precursor, and ii) forming a thin film on a substrate in a chamber using the precursor composition.

[0014] According to embodiments of the present disclosure, indium, gallium, and zinc in the precursor composition for depositing thin films can be mixed in a molar ratio of 0.1 to 10: 0.1 to 10: 0.1 to 10.

[0015] According to embodiments of this disclosure, the liquid indium precursor may be one or more selected from triethylindium, triisopropylindium, and tritert-butylindium.

[0016] According to embodiments of this disclosure, the precursor composition for depositing a thin film may not involve the use of a solvent, for example, it may not include a solvent.

[0017] According to embodiments of the present disclosure, thin films can be formed by using a precursor composition for depositing thin films via atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0018] According to embodiments of this disclosure, the temperature at which the thin film is formed can be between 100°C and 300°C.

[0019] According to embodiments of this disclosure, the manufacturing method may further include: evaporating the precursor composition using an evaporator before forming a thin film.

[0020] According to embodiments of this disclosure, the manufacturing method may further include: after forming a thin film, performing a first purging of the chamber using an inert gas.

[0021] According to embodiments of this disclosure, the manufacturing method may further include: after a first purging, oxidizing the thin film using a reactive gas.

[0022] According to embodiments of this disclosure, the flow rate of the reactive gas can be from 50 sccm to 500 sccm, and the supply time of the reactive gas can be from 0.1 seconds to 60 seconds.

[0023] According to embodiments of this disclosure, the manufacturing method may further include: after oxidizing the thin film, a second purging of the chamber using an inert gas.

[0024] According to another aspect of this disclosure, a thin film is provided that is formed on a substrate in a chamber using a precursor composition comprising a liquid indium precursor, a liquid gallium precursor, and a liquid zinc precursor for thin film deposition. The thin film is a single amorphous layer comprising indium, gallium, and zinc.

[0025] According to embodiments of the present disclosure, thin films can be formed by using a precursor composition for depositing thin films via atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0026] According to embodiments of this disclosure, the indium content in the thin film can be greater than or equal to 10 wt%.

[0027] According to embodiments of this disclosure, the thin film may have a refractive index of 1.5 to 2.5 for light with a wavelength of 630 nm.

[0028] According to aspects of this disclosure, an electronic device may include a thin film formed using a precursor composition comprising a liquid indium precursor, a liquid gallium precursor, and a liquid zinc precursor. The thin film is a single amorphous layer comprising indium, gallium, and zinc.

[0029] According to embodiments of this disclosure, the electronic device may be one of the following: flat panel display, curved display, television, billboard, computer monitor, medical monitor, head-mounted display (HMD), indoor light, outdoor light, signal light, wearable device, foldable device, rollable device, bendable device, flexible device, curved device, electronic notebook computer, e-book, portable multimedia player (PMP), personal digital assistant (PDA), laser printer, telephone, cellular phone, tablet computer, portable terminal, notebook computer, laptop computer, digital camera, viewfinder, camcorder, 3D display, virtual reality display, augmented reality display, video wall containing multiple displays spliced ​​together, vehicle, outdoor display device, theater screen, stadium screen, and signboard.

[0030] According to embodiments of this disclosure, it is possible to provide: a method for manufacturing a thin film using a mixed liquid precursor composition for depositing a thin film, having a simplified manufacturing process and a shortened manufacturing process time; a thin film with advanced physical properties manufactured using a mixed liquid precursor composition for depositing a thin film; and an electronic device including the thin film.

[0031] However, the effects of this disclosure are not limited to those described above, but can be extended to the extent that they do not depart from the idea and scope of this disclosure. Attached Figure Description

[0032] These and / or other features will become apparent and more readily understood from the following description of the embodiments in conjunction with the accompanying drawings, wherein:

[0033] Figure 1 (a) A conceptual illustration of an apparatus for fabricating thin films by providing a conventional source for depositing IGZO thin films, and Figure 1 (b) A schematic illustration of a separate process for fabricating thin films by sequentially providing three types of conventional sources for depositing IGZO thin films using the apparatus;

[0034] Figure 2 (a) A conceptual explanation of an apparatus for manufacturing thin films is provided by means of a liquid delivery system (LDS) for depositing IGZO thin films according to embodiments of the present disclosure, comprising a liquid tri-category mixed precursor composition; and gaseous indium, gallium, and zinc precursors evaporated by an evaporator are simultaneously provided on a substrate. Figure 2 (b) A schematic illustration of a separate process for manufacturing thin films using the apparatus to provide a mixed precursor composition of three categories for depositing IGZO thin films;

[0035] Figure 3 For the purposes of using embodiments according to this disclosure Figure 2 (a) Explanation of the speeds in each process of the liquid delivery system (LDS) of the apparatus shown in the diagram to form an IGZO thin film by atomic layer deposition;

[0036] Figure 4 This is a conceptual illustration of an apparatus for manufacturing thin films that provides a mixed precursor composition of three categories for depositing IGZO thin films by a bypass method according to embodiments of the present disclosure and sequentially provides evaporated gaseous indium precursor, gallium precursor and zinc precursor on a substrate according to vapor pressure.

[0037] Figure 5 (a) A schematic cross-sectional view of a thin-film transistor according to an embodiment of the present disclosure, comprising an IGZO thin film formed by using a mixed precursor composition of three categories for depositing an IGZO thin film, and Figure 5 (b) is a schematic top view of a thin-film transistor;

[0038] Figure 6 and Figure 7 This explanation illustrates the application of electronic devices including thin-film display devices according to embodiments of the present disclosure;

[0039] Figure 8 (a) to Figure 8 (c) A graph showing the results of nuclear magnetic resonance (NMR) measurements of each source after synthesizing sources of gallium precursor, indium precursor and zinc precursor for manufacturing mixed precursor compositions of three categories for depositing IGZO thin films according to an embodiment of the present disclosure.

[0040] Figure 9 (a) Figure 9 (b) and Figure 9 (c) A graph showing the NMR results of the composition after manufacturing a mixed precursor composition of three categories for depositing IGZO thin films according to an embodiment of the present disclosure.

[0041] Figure 10 (a) Figure 10 (b) and Figure 10 (c) An explanation of the NMR analysis results of triethylindium, an indium precursor, as an embodiment of the present disclosure;

[0042] Figure 11 For illustration of gas chromatography-mass spectrometry (GC / MS) results of three categories of mixed precursor compositions for depositing IGZO thin films according to embodiments of the present disclosure;

[0043] Figure 12A , Figure 12B , Figure 12C , Figure 12D , Figure 12E and Figure 12F To illustrate the interpretation of gas chromatography-mass spectrometry (GC / MS) results of each component in a three-category mixed precursor composition for depositing IGZO thin films according to embodiments of the present disclosure;

[0044] Figure 13 This is an explanation of the results of thermogravimetric analysis (TGA) using the thermal stability and decomposition temperature of liquid indium precursor, liquid gallium precursor and / or liquid zinc precursor in a mixed precursor composition of three categories for depositing IGZO thin films according to embodiments of the present disclosure.

[0045] Figure 14 A scanning electron microscope (SEM) image obtained by taking a cross-section of an IGZO thin film formed by atomic layer deposition according to an embodiment of the present disclosure;

[0046] Figure 15 A graph showing the X-ray diffraction (XRD) results of an IGZO thin film formed by atomic layer deposition according to an embodiment of the present disclosure;

[0047] Figure 16 (a) A graph showing the growth rate (GPC) of an IGZO thin film formed by atomic layer deposition according to an embodiment of the present disclosure, and the thickness measured using an ellipsometer. Figure 16(b) A graph showing the growth rate (GPC) of an IGZO thin film formed by atomic layer deposition according to an embodiment of the present disclosure at the deposition temperature per cycle.

[0048] Figure 17 (a) and Figure 17 (b) An explanation of the compositional proportions of the film components obtained by means of X-ray photoelectron spectroscopy (XPS) for forming a film using a mixed precursor composition of three categories for depositing IGZO thin films according to embodiments of the present disclosure via atomic layer deposition.

[0049] Figure 18 (a) and Figure 18 Each of (b) is a surface mapping image and a sectional mapping image obtained by scanning electron microscopy / energy dispersive X-ray spectroscopy (SEM-EDS) analysis of the components of a thin film formed by atomic layer deposition according to an embodiment of the present disclosure.

[0050] Figure 19 (a) and Figure 19 Each of (b) is an illustration of the refractive index and absorptivity of a thin film formed by atomic layer deposition according to an embodiment of the present disclosure;

[0051] Figure 20 (a) A graph showing the O1s peak of a thin film obtained by using photoelectron spectroscopy (XPS) to depict a thin film formed by atomic layer deposition according to an embodiment of the present disclosure, and Figure 20 (b) A graph showing the peaks of the O1s peak after deconvolution into three peaks;

[0052] Figure 21 and Figure 22 Atomic force microscopy (AFM) interpretation of the growth behavior and root mean square surface roughness of IGZO thin films according to embodiments of the present disclosure, using both three-dimensional and two-dimensional particle morphologies.

[0053] Figure 23 A transfer curve is shown to illustrate the reliability assessment results of the IGZO thin film according to an embodiment of the present disclosure. Detailed Implementation

[0054] Specific embodiments illustrated in the accompanying drawings will now be discussed in detail with reference to examples thereof, wherein the same reference numerals denote the same elements throughout. Embodiments may take many forms and variations, but this disclosure should in no way be construed as limiting itself to the described embodiments. Rather, this disclosure should be construed as encompassing all forms, variations, equivalents, and alternatives covered by the technical concept and scope of this disclosure. Accordingly, embodiments are described below with reference only to the figures to explain the features of this disclosure.

[0055] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. However, in the event of any inconsistency between these meanings, the description (including definitions) of this disclosure shall prevail.

[0056] For example, the terms "first" and "second" can be used to describe various elements, but the elements mentioned above should not be limited by these terms. The terms can be used to distinguish one element from another simply. For example, without departing from the scope of the claims of this disclosure, a first element may be referred to as a second element, and vice versa. Unless expressly used otherwise, any singular form may include the meaning of the plural form. The term "and / or" should include a combination of or any one of the listed items.

[0057] When a component is described as "set on another component," "placed on another component," "arranged on another component," "connected to," or "attached to" another component, it should be understood that the component is directly set on, placed on, arranged on, connected to, or attached to another component, and there may also be another component between them. On the other hand, if a component is described as "directly set on another component," "directly placed on another component," "directly arranged on another component," "directly connected to," or "directly attached to" another component, it should be understood that there are no other components between them.

[0058] In this disclosure, expressions such as “comprising” or “including” are intended to identify features, quantities, steps, operations, elements, parts, or combinations thereof, and should not be construed as excluding the possibility of the presence or addition of one or more other features, quantities, steps, operations, elements, parts, or combinations thereof.

[0059] When a component is described as being set "on" (or below) a component or "above" (or below) a component, it should be interpreted as meaning that not only can the component be set directly on (or below) that component, but there may also be another component between them.

[0060] Any reference to “and / or” should be interpreted as including one or more combinations that can be defined by the relevant elements.

[0061] For convenience, the dimensions and thickness of each configuration shown in the figures are given as examples, and this disclosure is not limited thereto.

[0062] As used herein, alkyl groups may have straight or branched chains. The number of carbon atoms in an alkyl group may be 1 to 30, 1 to 20, or 1 to 10. Specific examples include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.

[0063] Specific embodiments illustrated in the accompanying drawings will now be discussed in detail with reference to examples thereof.

[0064] Precursor composition for thin film deposition

[0065] Figure 1 (a) A conceptual illustration of an apparatus for fabricating thin films by providing a conventional source for depositing IGZO thin films, and Figure 1 (b) A schematic illustration of a separate process for fabricating thin films by using an apparatus to sequentially provide three types of conventional sources for depositing IGZO thin films.

[0066] according to Figure 1 (a) and Figure 1 (b) Because each of the indium (In), gallium (Ga), and zinc (Zn) sources is provided separately, the process time for depositing IGZO thin films using conventional sources increases, requiring 16 steps in one cycle to form the film via atomic layer deposition. In particular, there is the disadvantage that each step of providing each source requires a separate purging step, and the time spent on purging is increased.

[0067] The precursor composition for thin film deposition according to this disclosure is a liquid precursor composition (hereinafter also referred to as a "cocktail") containing a mixture of liquid indium precursor, liquid gallium precursor, and liquid zinc precursor. The liquid precursor composition for deposition can be evaporated using an evaporator, and as... Figure 2 As shown in (a), the evaporated precursor composition of the three categories for depositing thin films can be introduced (i.e., pulsed input) into the chamber.

[0068] The precursor composition for thin film deposition according to one aspect of this disclosure may include a liquid indium precursor, a liquid gallium precursor, and a liquid zinc precursor.

[0069] All indium, gallium, and zinc precursors are alkyl precursors, which are suitable for easy mixing and flow rate regulation without side reactions and have similar evaporation temperatures, but this disclosure is not limited thereto.

[0070] Conventional halogen precursors have the following drawbacks: due to their high thermal stability, conventional halogen precursors need to be deposited at temperatures of 300°C or higher, and are difficult to mix in a liquid state.

[0071] The precursor composition for thin film deposition according to this disclosure is an alkyl precursor. Because it does not contain halogens, the alkyl precursor is not contaminated by halogens and has excellent thermal stability, making it easy to form thin films at low temperatures. However, this disclosure is not limited thereto.

[0072] The molar ratio of indium:gallium:zinc in the precursor composition for depositing thin films can be 0.1 to 10:0.1 to 10:0.1 to 10, but this disclosure is not limited thereto. The molar ratio of indium:gallium:zinc in IGZO thin films manufactured using the precursor composition for depositing thin films is suitably 0.1 to 10:0.1 to 10:0.1 to 10, more suitably 1 to 5:1 to 5:1 to 5, even more suitably 1 to 3:1 to 3:1 to 3, even more suitably 1 to 2:1 to 2:1 to 2, and most suitably 1:1:1, but this disclosure is not limited thereto. The reactivity of each element precursor can be different, such that when a film is formed using a mixed precursor composition of three categories for depositing IGZO thin films via a single-cycle process, the molar ratio of indium:gallium:zinc in the IGZO thin film can be different. In particular, gallium is relatively less reactive than indium or zinc. Accordingly, compared to the molar concentration of indium or zinc in the precursor composition, the molar concentration of gallium, which has lower reactivity, in the precursor composition can be increased. Although this disclosure is not limited thereto, the molar ratio of indium:gallium:zinc in the precursor composition for depositing the thin film can be from 1:1:1 to 1:3:1. Furthermore, the proportions of elements included in the thin film can be appropriately controlled by adjusting the process conditions used to form the thin film.

[0073] Although this disclosure is not limited thereto, the liquid indium precursor may be at least one selected from triethylindium, triisopropylindium, and tritert-butylindium. Triethylindium, triisopropylindium, and tritert-butylindium are shown in Formulas 1 to 3 below.

[0074] Formula 1

[0075]

[0076] Formula 2

[0077]

[0078] Formula 3

[0079]

[0080] Although this disclosure is not limited thereto, triethylindium, as a precursor of liquid indium, is suitable for improving the electron mobility and reliability of films in the three categories due to its excellent reactivity and suitability for indium deposition.

[0081] Although this disclosure is not limited thereto, the liquid gallium precursor may be trimethylgallium or triethylgallium, and trimethylgallium may be suitable for improving the reliability of thin films in three categories.

[0082] Although this disclosure is not limited thereto, the liquid zinc precursor may be diethylzinc or dimethylzinc, and diethylzinc may be suitable for improving the reliability of three-classified films.

[0083] Although this disclosure is not limited thereto, the precursor compositions may not include solvents. All precursor compositions according to this disclosure may be liquid, making them readily applicable to liquid delivery systems (LDS) even without solvents.

[0084] According to the configuration described above in this disclosure, a thin film can be formed by a single cycle supply of a mixed precursor composition of three categories for depositing IGZO thin films via evaporation. Accordingly, this is economically advantageous for the process used to manufacture the thin film, as the process of this disclosure is simpler and the overall process time can be significantly reduced compared to conventional techniques, such as... Figure 1 As shown, each element of the precursor composition for depositing thin films is supplied through three to four cycles, and each source of each composition precursor is purged during each supply.

[0085] The following text is for reference only. Figure 2 This disclosure will be described in more detail below.

[0086] Figure 2 (a) A conceptual illustration of an apparatus for manufacturing a thin film by providing a liquid tri-classified mixed precursor composition for depositing an IGZO thin film according to an embodiment of the present disclosure via a liquid delivery system (LDS), and simultaneously providing gaseous indium precursor, gallium precursor and zinc precursor evaporated by an evaporator on a substrate. Figure 2 (b) A schematic illustration of a separate process for manufacturing thin films by using the apparatus to provide a mixed precursor composition of three categories for depositing IGZO thin films.

[0087] according to Figure 2(a) An apparatus for manufacturing an oxide semiconductor thin film according to an embodiment of the present disclosure may include: a chamber 30 configured to hold a substrate 50 for forming an oxide semiconductor thin film (e.g., an IGZO thin film); and a supply system for source materials for depositing the thin film, configured to supply a gaseous precursor composition for depositing the thin film into the chamber 30.

[0088] The source material supply system may include: a precursor composition container 10, wherein a precursor composition 20 for deposition is stored; a carrier gas supply unit 12; valves 14 and 16; and a precursor composition supply unit 18.

[0089] The precursor composition container 10 may be configured to store a liquid tri-category mixed precursor composition 20 for depositing IGZO thin films, and may also be referred to as a tank. A carrier gas supply unit 12 may be configured to supply carrier gas to the precursor composition container 10. A precursor composition supply unit 18 may be configured to supply the precursor composition from the precursor composition container 10 to a chamber 30. The carrier gas supply unit 12 and the precursor composition supply unit 18 may be connected to valves 14 and 16, respectively, which are configured to control the flow rate by opening and closing valves 14 and 16. The composition for film deposition supplied by the precursor composition supply unit 18 may be evaporated into a gaseous state through an evaporator 40, and the evaporator 40 may be heated to 30°C to 80°C by a heater 44, thereby allowing the temperature of the substrate 50 to be heated to 100°C to 350°C by an additional heater (not shown).

[0090] Although this disclosure is not limited thereto, a mixture of liquid indium precursor, liquid gallium precursor, and liquid zinc precursor can be supplied to a substrate via a liquid delivery system (LDS) that delivers the mixture at room temperature and evaporates it using an evaporator for deposition. Various supply methods, including liquid mass flow controller (LMFC) methods, can be applied.

[0091] The chamber 30 provides space for forming oxide semiconductor thin films (such as IGZO thin films). A stage 32 may be provided at the bottom of the inner surface of the chamber 30, on which a substrate 50 may be placed to form an oxide semiconductor thin film (such as an IGZO thin film). A spray head 42 may be arranged on the upper side of the inner surface of the chamber 30 and configured to supply a mixed precursor composition of gaseous tripartite components for depositing IGZO thin films.

[0092] Although this disclosure is not limited thereto, chamber 30 may be provided with at least one plasma supply device (not shown), and at least one plasma supply device may be arranged along the transport direction of the substrate. The plasma supply device may convert argon and / or helium into plasma comprising positive ions and electrons to form high-energy electrons to deposit a thin film on the substrate by converting a discharge gas (e.g., ozone filled into chamber 30) into a plasma state.

[0093] Additionally, refer to Figure 2 (b) One cycle of depositing the thin film may include four steps, which include: a process of providing the IGZO mixture in a gaseous state to the chamber 30 through the spray head 42 to form an IGZO thin film on the substrate in the chamber 30; a purging process using an inert gas; an oxidation process using O2 plasma; and a purging process using an inert gas.

[0094] Thin film manufacturing methods

[0095] The method for manufacturing a thin film according to this disclosure may include: i) obtaining a precursor composition for depositing a thin film by mixing a liquid indium precursor, a liquid gallium precursor and a liquid zinc precursor, for example, manufacturing a precursor composition for depositing a thin film; ii) forming a thin film on a substrate in a chamber by using the precursor composition for depositing a thin film; iii) purging the chamber with a first inert gas; iv) oxidizing the thin film by using a reactive gas; and v) purging the chamber with a second inert gas.

[0096] The following section describes each step in detail.

[0097] Step i) is a step of obtaining a precursor composition for depositing thin films by mixing liquid indium precursor, liquid gallium precursor and liquid zinc precursor.

[0098] All liquid indium precursors, liquid gallium precursors, and liquid zinc precursors are alkyl precursors, which are suitable for easy mixing and flow rate regulation without side reactions and have similar evaporation temperatures, but this disclosure is not limited thereto.

[0099] Conventional halogen precursors have the following drawbacks: due to their high thermal stability, the deposition of conventional halogen precursors requires temperatures of 300°C or higher, and conventional halogen precursors are difficult to mix in a liquid state.

[0100] The precursor composition for thin film deposition according to this disclosure is an alkyl precursor that does not contain halogens and therefore does not cause contamination, and has excellent thermal stability, making it easy to form a thin film at low temperatures.

[0101] The indium, gallium, and zinc in the precursor composition for depositing the thin film in step i) may have a molar ratio of 0.1 to 10:0.1 to 10:0.1 to 10, but this disclosure is not limited thereto.

[0102] The elemental composition of an IGZO thin film manufactured using the precursor composition for thin film deposition according to the present disclosure may have the following indium:gallium:zinc molar ratio: suitably 0.1 to 10:0.1 to 10:0.1 to 10, more suitably 1 to 5:1 to 5:1 to 5, even more suitably 1 to 3:1 to 3:1 to 3, and even more suitably 1 to 2:1 to 2:1 to 2, and most suitably 1:1:1.

[0103] The reactivity of the precursors for each element can vary, therefore the molar ratio of indium:gallium:zinc in the IGZO film can differ when a mixed precursor composition of three categories for depositing IGZO films is used to form a film via a single-cycle process. Specifically, gallium is relatively less reactive than indium or zinc. Accordingly, the molar concentration of gallium, which has low reactivity, in the precursor composition can be controlled to be higher than the molar concentrations of indium and zinc. The molar ratio of indium:gallium:zinc in the precursor composition for film deposition can be between 1:1:1 and 1:3:1, but this disclosure is not limited thereto. Furthermore, the proportions of elements included in the film can be controlled by adjusting the process conditions used to form the film.

[0104] The liquid indium precursor may be selected from at least one of triethylindium, triisopropylindium, and tritert-butylindium, but this disclosure is not limited thereto. Triethylindium, triisopropylindium, and tritert-butylindium are shown in Formulas 1 to 3 below.

[0105] Formula 1

[0106]

[0107] Formula 2

[0108]

[0109] Formula 3

[0110]

[0111] Although this disclosure is not limited thereto, triethylindium, as a precursor of liquid indium, is suitable for improving the electron mobility and reliability of films in the three categories due to its excellent reactivity and suitability for indium deposition.

[0112] Although this disclosure is not limited thereto, the liquid gallium precursor may be trimethylgallium or triethylgallium, and trimethylgallium may be suitable for improving the reliability of thin films in three categories.

[0113] Although this disclosure is not limited thereto, the liquid zinc precursor may be diethylzinc or dimethylzinc, and diethylzinc may be suitable for improving the reliability of three-classified films.

[0114] Although this disclosure is not limited thereto, the liquid precursor compositions for depositing thin films may not include solvents. All precursors according to this disclosure may be liquid, so that they can be easily delivered by a liquid delivery system (LDS) even without a solvent.

[0115] Hereinafter, step ii) is the step of forming a thin film on a substrate in chamber 30 by using a precursor composition for depositing a thin film.

[0116] Although not limited thereto, in step ii), the precursor composition for depositing the thin film can be used to form the thin film by atomic layer deposition (ALD) or chemical vapor deposition (CVD). Although not limited thereto, the precursor composition for depositing the thin film can also be used to form the thin film by plasma-enhanced atomic layer deposition (PEALD) or metal-organic chemical vapor deposition (MOCVD).

[0117] Although not limited to this, thin films can be formed at temperatures between 100°C and 300°C using the precursor composition for thin film deposition via atomic layer deposition (ALD) or chemical vapor deposition. Although not limited to this, the temperature used for thin film formation in step ii) may suitably be between 100°C and 300°C to form thin films with excellent film quality. When the temperature used for thin film formation is below 100°C, the precursor cannot be sufficiently activated, resulting in a reduced film deposition rate. When the temperature used for thin film formation is above 300°C, indium, zinc, or gallium precursors may thermally degrade and are therefore unsuitable.

[0118] Although not limited thereto, in step ii), a thin film can be formed by evaporating the precursor composition for film deposition using an evaporator. Although this disclosure is not limited thereto, a mixture of liquid indium precursor, liquid gallium precursor, and liquid zinc precursor can be transferred to a substrate using a liquid delivery system (LDS) that transfers the liquid mixture of liquid indium precursor, liquid gallium precursor, and liquid zinc precursor at room temperature, and then evaporated by an evaporator for deposition. Various supply methods can be implemented, such as direct liquid injection (DLI) for direct spraying, vapor flow controller (VFC) for direct supply using the vapor pressure of the precursor, or liquid mass flow controller (LMFC).

[0119] Figure 2 (a) A conceptual illustration of an apparatus for manufacturing thin films as described below: providing a mixed precursor composition of three categories for depositing IGZO thin films according to embodiments of the present disclosure via a liquid delivery system (LDS) and simultaneously providing indium precursor, gallium precursor, and zinc precursor evaporated by an evaporator on a substrate. Figure 3 For the implementation of the embodiments according to this disclosure Figure 2 The liquid delivery system of the apparatus shown in (a) is illustrated based on the rate of change in each step of forming an IGZO thin film via atomic layer deposition. While not limited thereto, Figure 2 The apparatus for manufacturing thin films shown in (a) can be used by... Figure 3 The steps shown in the figure form a thin film.

[0120] Figure 2 (b) A schematic illustration of a separate process for manufacturing thin films using the apparatus to provide a mixed precursor composition of three categories for depositing IGZO thin films. Reference Figure 2 (b) One cycle for depositing a thin film can be completed in four steps, wherein a mixed precursor composition of gaseous three-group classification for depositing an IGZO thin film, injected from a spray head 42, is deposited on a substrate 50 and purged with an inert gas, and then the thin film is oxidized by plasma and purged again with an inert gas.

[0121] As described above, in step ii), the precursor composition for film deposition is evaporated by an evaporator, such that the precursor composition can be provided to chamber 30 in a gaseous state.

[0122] refer to Figure 3 and Figure 4 The precursor composition 20, manufactured and stored in the precursor composition container 10 in step i), can be transported via the precursor composition supply unit 18 to the evaporator (see [see [see evaporator name]) by the carrier gas supplied by the carrier gas supply unit 12. Figure 3 (Step 1 in the process). Although not limited to this, the precursor composition can be provided at a rate between 0.01 g / min and 0.20 g / min for 1.0 seconds and 7.0 seconds.

[0123] The tri-classified mixed precursor composition for depositing IGZO thin films, transported by the precursor composition supply unit 18, can be evaporated by the evaporator 40 heated to between 30°C and 80°C by the heater 44, so that the gaseous tri-classified mixed precursor composition for depositing IGZO thin films can be provided to the chamber 30, and the temperature of the substrate 50 can be heated to between 100°C and 350°C.

[0124] When a liquid tri-component mixed precursor composition for depositing IGZO thin films is provided into chamber 30, the uniformity of the film can be negatively affected. Therefore, it is suitable to evaporate the liquid tri-component mixed precursor composition for depositing IGZO thin films and provide it into the chamber. Furthermore, when the evaporator 40 configured to evaporate the liquid tri-component mixed precursor composition for depositing IGZO thin films and the heater 44 configured to heat the evaporator 40 are provided outside chamber 30, the temperature of chamber 30 can be unaffected by the heater 44, making it easy to control the temperature of chamber 30. The gaseous tri-component mixed precursor composition for depositing IGZO thin films introduced into chamber 30 can be injected towards substrate 50 through spray head 42 for deposition on substrate 50. Here, the indium precursor, gallium precursor, and zinc precursor included in the gaseous tri-component mixed precursor composition for depositing IGZO thin films can be uniformly mixed and deposited on substrate 50.

[0125] As described above, when a mixed precursor composition of three categories for depositing IGZO thin films is simultaneously provided via a liquid delivery system (LDS) for thin film deposition, indium, gallium, and zinc precursors can be simultaneously injected onto the substrate to form a mixed monolayer film. Furthermore, large quantities of indium, gallium, and zinc precursors can be introduced over a large area, allowing the precursor composition to be supplied at a uniform concentration during deposition to form a uniform film.

[0126] Step iii) is the first purging step with inert gas (see...). Figure 3 (Step 2 in the original text). The first purging is a step of supplying an inert gas to chamber 30 to remove gaseous precursor composition not deposited on substrate 50. Although not limited thereto, the inert gas may be, for example, argon, helium, nitrogen, or neon. Although not limited thereto, the flow rate of the inert gas may be between 1 sccm and 2,000 sccm. Although not limited thereto, the first purging may be performed between 1.0 second and 60.0 seconds. During the first purging, remaining impurities, including the mixed precursor composition of the three categories used for depositing the IGZO film, may be removed.

[0127] Step iv) is the step of oxidizing the thin film using a reactive gas (see...). Figure 3(Step 3 in the text). Although not limited to this, oxygen plasma can be used for the oxidation of the thin film. Although not limited to this, oxygen can be supplied at a power between 50 W and 500 W and a supply flow rate between 50 sccm and 500 sccm to implement the plasma process. Although not limited to this, oxidation steps between 0.1 seconds and 60.0 seconds can be implemented. Although not limited to this, in the first stage (between 1 second and 7 seconds) of supplying O2 source material into the reaction chamber, O2 source material is supplied into the reaction chamber without forming plasma in the reaction chamber. Accordingly, an atmosphere of O2 source material can be formed inside the reaction chamber, and the O2 source material can be attached to the mixed precursor composition of the three categories used for depositing the IGZO thin film.

[0128] Furthermore, in the second stage of supplying O2 source material into the reaction chamber, an O2 source can be supplied to the reaction chamber to form plasma. Although not limited to this, argon gas can be supplied in both the first and second stages of supplying O2 source material into the reaction chamber, and the argon gas flow rate can be between 50 sccm and 500 sccm, or between 100 sccm and 300 sccm. As described above, when plasma is generated in the reaction chamber, O2 atoms can be ionized, thereby forming more bonds with indium-gallium-zinc atoms on the substrate surface, and the O2 source material can react on the substrate surface to deposit IGZO-type thin films. Although not limited to this, the flow rate of the O2 source material can be between 100 sccm and 300 sccm, the supply time can be between 3 seconds and 10 seconds, and the plasma power can be between 100 W and 300 W. The amount of O2 source material supplied to the reaction chamber can be controlled by controlling the plasma switching time.

[0129] In step iv), the flow rate of the reactive gas can be between 50 sccm and 500 sccm, and the supply time of the reactive gas can be between 0.1 seconds and 60.0 seconds.

[0130] Step v) is the second purging step using inert gas (see...) Figure 3 Step 4). In step v), the reactive gas from step iv) is removed by using an inert gas. Although not limited thereto, the second purging can be performed by supplying an inert gas at a rate between 1 sccm and 2,000 sccm for 1.0 seconds and 60.0 seconds. The second purging can remove impurities, including, for example, residual O2 source material in the reaction chamber.

[0131] Although not limited to this, performing one cycle of deposition, including steps ii) to v), for 200 to 600 cycles, more appropriately for 200 to 500 cycles, or even more appropriately for 200 to 400 cycles, can be suitable for producing thin films of excellent quality. However, when the number of deposition cycles is less than 200, the film deposition may be insufficient. When the number of deposition cycles is greater than 600, the thickness of the IGZO film can become thicker. A thicker film thickness can affect the characteristics of the thin-film transistor (TFT) channel and is therefore unsuitable.

[0132] When conventional precursor compositions for depositing IGZO thin films are deposited using a bypass method, indium, gallium, and zinc precursors are sequentially released onto the substrate based on evaporation pressure, resulting in a process requiring 16 steps. In contrast, when the liquid tri-category mixed precursor composition for depositing IGZO thin films according to embodiments of the present disclosure is used for deposition via a liquid delivery system (LDS), the process can be reduced to 4 steps.

[0133] Figure 4 This is a conceptual illustration of an apparatus for manufacturing thin films that provides a mixed precursor composition of three categories for depositing IGZO thin films via a bypass method and sequentially provides evaporated gaseous indium, gallium, and zinc precursors on a substrate according to the evaporation pressure, according to embodiments of the present disclosure.

[0134] refer to Figure 4 An apparatus for manufacturing oxide semiconductor thin films according to embodiments of the present disclosure may include: a chamber 130 configured to hold a substrate 150 on which an oxide semiconductor thin film (such as an IGZO thin film) is to be formed; and a supply system for source materials for depositing the thin film, configured to supply a gaseous tri-classified mixed precursor composition for depositing the IGZO thin film into the chamber 130.

[0135] The source material supply system may include a precursor composition container 110, a carrier gas supply unit 112, valves 114 and 116, a precursor composition supply unit 118, and a precursor composition 120 for deposition.

[0136] The precursor composition container 110 may be configured to store a liquid tri-category mixed precursor composition for depositing IGZO thin films, and may also be referred to as a tank. A carrier gas supply unit 112 may be configured to supply carrier gas to the precursor composition container 110. A precursor composition supply unit 118 may be configured to supply a gaseous precursor composition generated by heating the precursor composition 120 via a heater 111 located outside the precursor composition container 110 to a chamber 130. Valves 114 and 116 may be connected to the carrier gas supply unit 112 and the precursor composition supply unit 118, respectively, and are configured to control the opening of flow paths to control fluid flow.

[0137] The chamber 130 may provide space for forming oxide semiconductor thin films (such as IGZO thin films), and a stage 132 for placing a substrate 150 may be provided on the bottom side of the chamber 130 for forming oxide semiconductor thin films (such as IGZO thin films). A spray head 142 may be provided on the upper side of the chamber 130, which is configured to provide a gaseous three-part mixed precursor composition for depositing IGZO thin films on the substrate 150 by injection.

[0138] According to the system with the above configuration, indium precursor, gallium precursor and zinc precursor in a liquid tri-category mixed precursor composition for depositing GIZO thin film can be released sequentially according to the evaporation pressure to form IGZO mixed thin film.

[0139] When depositing using a liquid tri-classified precursor composition for depositing IGZO thin films according to embodiments of the present disclosure via a liquid delivery system (LDS) method, the process can be reduced to four steps, and more uniformly mixed monolayer films can be deposited compared to bypass processes, and amorphous multi-element oxide films can be deposited.

[0140] film

[0141] According to another aspect of this disclosure, the thin film may be a thin film formed on a substrate in chamber 30 using a precursor composition for depositing a thin film, comprising a liquid indium precursor, a liquid gallium precursor and a liquid zinc precursor, and the thin film may be a single layer comprising a mixture of indium, gallium and zinc and be amorphous.

[0142] Although this disclosure is not limited thereto, the thin film may be a thin film formed by atomic layer deposition or chemical vapor deposition using a precursor composition for depositing the thin film. Although this disclosure is not limited thereto, the thin film may be a thin film formed by metal-organic chemical vapor deposition.

[0143] Although this disclosure is not limited thereto, the elemental composition of the IGZO thin film formed using the precursor composition for thin film deposition has the following indium:gallium:zinc molar ratio: suitably 0.1 to 10:0.1 to 10:0.1 to 10, more suitably 1 to 5:1 to 5:1 to 5, even more suitably 1 to 3:1 to 3:1 to 3, even more suitably 1 to 2:1 to 2:1 to 2, and most suitably 1:1:1. Although this disclosure is not limited thereto, the molar ratio of indium, gallium, and zinc can be controlled during the manufacture of the precursor composition for thin film deposition, or the proportion of elements included in the thin film can be suitably controlled by controlling the conditions of the process for forming the thin film.

[0144] Although this disclosure is not limited thereto, the indium content in the thin film may be greater than or equal to 10 wt%. According to the above configuration, there is an advantage that the electron mobility of the thin film increases with increasing indium content.

[0145] Thin films can be formed by using a precursor composition for film deposition via atomic layer deposition or chemical vapor deposition, but this disclosure is not limited thereto. Although this disclosure is not limited thereto, thin films formed by atomic layer deposition according to embodiments of this disclosure have fewer voids and therefore have a higher density compared to thin films formed by PVD (sputtering).

[0146] Although this disclosure is not limited thereto, thin films formed by atomic layer deposition according to embodiments of this disclosure may have a smaller root mean square surface roughness than thin films formed by PVD (sputtering). Although this disclosure is not limited thereto, when the thickness of the thin film is between 30 nm and 50 nm, the root mean square surface roughness (RMS) of the thin film formed by atomic layer deposition according to embodiments of this disclosure may be 1.20 nm or less.

[0147] For light with a wavelength of 630 nm, the thin film formed by atomic layer deposition according to embodiments of the present disclosure can have an excellent refractive index between 1.5 and 2.5 or between 1.7 and 2.2.

[0148] Electronic devices including thin films

[0149] Figure 5 (a) A schematic cross-sectional view of a thin-film transistor according to an embodiment of the present disclosure, comprising an IGZO thin film formed by using a mixed precursor composition of three categories for depositing an IGZO thin film, and Figure 5 (b) is a schematic top view of a thin-film transistor.

[0150] refer to Figure 5(a) Using a highly doped silicon substrate GS on which a SiO2 buffer layer BF with a thickness of 100 nm is formed, an active layer ACT is formed by depositing an IGZO thin film on the SiO2 buffer layer BF, and a thin-film transistor including a source electrode S and a drain electrode D disposed opposite to each other on the active layer ACT is fabricated. The circuit layer CL may include the buffer layer BF, the active layer ACT, the gate insulating layer GI, the gate electrode GAT, the interlayer insulating layer ILD, the source electrode S, the drain electrode D, and the via insulating layer VIA.

[0151] The substrate GS may comprise various materials, such as glass, metal, or plastic. According to embodiments of this disclosure, the substrate GS may comprise a flexible material. Herein, a flexible material may be one that is easily bent, folded, rolled, or shaped. For example, a flexible material may comprise ultrathin glass, metal, or plastic.

[0152] A lower metal layer (BML) may be disposed on a substrate (GS). A buffer layer (BF) may be disposed on the lower metal layer (BML), and an active layer (ACT) may be disposed on the buffer layer (BF). The lower metal layer (BML) may at least partially overlap with a thin-film transistor disposed on top of the lower metal layer (BML). More specifically, the lower metal layer (BML) may at least partially overlap with the active layer (ACT) disposed on top of the lower metal layer (BML).

[0153] When the active layer ACT comprises an oxide semiconductor material, the active layer ACT may exhibit characteristics susceptible to light influence. Since the lower metal layer BML is disposed beneath the active layer ACT, photocurrent caused by external light incident from the substrate side onto the active layer ACT can be prevented, thereby minimizing variations in the device characteristics of the thin-film transistor.

[0154] The gate insulating layer GI can be disposed on the active layer ACT, and the gate electrode GAT can be disposed on the gate insulating layer GI. Additionally, the interlayer insulating layer ILD can be disposed on the gate electrode GAT. For example, the interlayer insulating layer ILD can be disposed to cover the components disposed underneath.

[0155] The via insulating layer VIA can be disposed on the interlayer insulating layer ILD, and the pixel electrode AN can be disposed on the via insulating layer VIA.

[0156] The pixel electrode AN can be electrically connected to the source electrode S through a via defined in the via insulating layer VIA.

[0157] The pixel electrode AN can be a (semi-)transmissive electrode or a reflective electrode. In embodiments, the pixel electrode AN may provide a reflective layer, for example, formed of Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, or compounds thereof, and a transparent or semi-transparent electrode layer formed on the reflective layer. The transparent or semi-transparent electrode layer may provide at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium oxide (In2O3), indium gallium oxide (IGO), and zinc aluminum oxide (AZO). For example, the pixel electrode AN may be ITO / Ag / ITO.

[0158] The pixel-defining film (PDL) can be disposed on the pixel electrode (AN). The PDL can be formed, for example, by spin coating, using at least one organic insulating material selected from the group consisting of polyimide, polyamide, acrylic resin, benzocyclobutene, and phenolic resin.

[0159] In one embodiment, the source electrode S can be electrically connected to the lower metal layer BML through a first contact hole CNT1 defined in the buffer layer BF and the interlayer insulating layer ILD.

[0160] In one embodiment, the source electrode S and the drain electrode D can be electrically connected to the active layer ACT through a second contact hole CNT2 defined in the interlayer insulating layer ILD.

[0161] The active layer ACT may include at least one of oxide semiconductor materials and silicon semiconductor materials. When the active layer ACT includes an oxide semiconductor material, it may include an oxide material selected from at least one material selected from the group consisting of indium (In), gallium (Ga), tin (Sn), zirconium (Zr), vanadium (V), hafnium (Hf), cadmium (Cd), germanium (Ge), chromium (Cr), titanium (Ti), aluminum (Al), cesium (Ce), and zinc (Zn). For example, the active layer ACT may include, for example, In-Ga-Zn-OIG(ZO), In-Sn-Zn-O(ITZO), or In-Ga-Sn-Zn-O(IGTZO) containing a metal (such as indium (In), gallium (Ga), and tin (Sn)) in zinc oxide (ZnO). In this disclosure, the active layer ACT may suitably include In-Ga-Zn-O(IGZO).

[0162] The gate insulating layer GI formed on the active layer ACT may include silicon oxide (SiO2). 2) silicon nitride (SiN) X ), silicon nitride oxide (SiON), aluminum oxide (Al2O3), titanium oxide (TiO2), tantalum oxide (Ta2O5), hafnium oxide (HfO2), and zinc oxide (ZnO) XAt least one of the following. In this document, zinc oxide (ZnO) X It can be zinc oxide (ZnO) and / or zinc peroxide (ZnO2).

[0163] The gate electrode (GAT) may include at least one of aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg), gold (Au), nickel (Ni), neodymium (Nd), iridium (Ir), chromium (Cr), lithium (Li), calcium (Ca), molybdenum (Mo), titanium (Ti), tungsten (W), and copper (Cu), and may be formed from a single layer or multiple layers comprising one or more materials.

[0164] Although this disclosure is not limited thereto, the interlayer insulating layer (ILD) may include silicon oxide (SiO2) and silicon nitride (SiN). X ), silicon nitride oxide (SiON), aluminum oxide (Al2O3), titanium oxide (TiO2), tantalum oxide (Ta2O5), hafnium oxide (HfO2), and zinc oxide (ZnO) X At least one of the following. Here, zinc oxide (ZnO) X It can be zinc oxide (ZnO) and / or zinc peroxide (ZnO2).

[0165] refer to Figure 5 (b) A thin-film transistor can be formed with a width W of 800 μm and a length L of 40 μm.

[0166] Figure 6 and Figure 7 The present disclosure provides an explanation of an electronic device including a display device with thin-film transistors, which is an application of the embodiments described herein.

[0167] refer to Figure 6 The first electronic device ECD1 is defined as a tablet computer including a first display device DDa. The second electronic device ECD2 is defined as a portable terminal including a second display device DDb. The third electronic device ECD3 is defined as a laptop computer including a third display device DDc. The fourth electronic device ECD4 is defined as a television including a fourth display device DDd. The fifth electronic device ECD5 is defined as a head-mounted display device including a fifth display device DDe. The sixth electronic device ECD6 is defined as a digital watch including a sixth display device DDf.

[0168] refer to Figure 7 The seventh electronic device ECD7 is illustrated as a vehicle comprising the seventh display device DDg to the tenth display device DDj. While the seventh electronic device ECD7 is exemplarily illustrated as a vehicle, this disclosure is not limited to what is shown in the figures. The seventh electronic device ECD7 can be various means of transportation, such as bicycles, motorcycles, trains, ships, or airplanes.

[0169] refer to Figure 5 (a) Figure 6 and Figure 7 According to another aspect of this disclosure, the first electronic device ECD1 to the seventh electronic device ECD7 may include a substrate GS and a circuit layer CL disposed on the substrate GS and including transistors. The transistors may include an active layer ACT, and the active layer ACT may be a thin film formed by using a precursor composition for depositing a thin film, including a liquid indium precursor, a liquid gallium precursor, and a liquid zinc precursor.

[0170] Apart from Figure 6 and Figure 7 In addition to the electronic devices shown in the figures, the electronic devices according to the embodiments are not limited to those shown in the figures, and can be applied to a variety of electronic devices, such as flat panel displays, curved displays, televisions, billboards, computer monitors, medical monitors, head-mounted displays (HMDs), indoor lights, outdoor lights, signal lights, wearable devices, foldable devices, rollable devices, bendable devices, flexible devices, curved devices, electronic notebook computers, e-books, portable multimedia players (PMPs), personal digital assistants (PDAs), laser printers, telephones, cellular phones, tablet computers, portable terminals, notebook computers, laptop computers, digital cameras, viewfinders, camcorders, 3D displays, virtual reality displays, augmented reality displays, video walls containing multiple displays spliced ​​together, vehicles, outdoor display devices, theater screens, stadium screens, and signs.

[0171] The following describes embodiments and comparative examples of the present disclosure. Specifically, a precursor composition according to embodiments, a method for manufacturing a film using the precursor composition, a film manufactured using the manufacturing method, and an electronic device including the film will be described. However, the embodiments shown below are for illustrative purposes only and are not intended to limit the scope of the disclosure.

[0172] Example

[0173] Example 1: Fabrication of thin films using a mixed precursor composition of three categories for depositing IGZO thin films.

[0174] Liquid indium precursor, liquid gallium precursor, and liquid zinc precursor are mixed to prepare a three-part precursor composition for depositing IGZO thin films. Here, to prepare the mixed three-part precursor composition for depositing IGZO thin films, the indium precursor may be triethylindium, the gallium precursor may be trimethylgallium (TMG), and the zinc precursor may be diethylzinc (DEZ). Triethylindium, trimethylgallium, and diethylzinc are mixed in a 1:1:1 molar ratio to prepare the IGZO precursor composition. The mixed three-part precursor composition for depositing IGZO thin films is provided via a liquid delivery system (LDS) by simultaneously providing gaseous indium, gallium, and zinc precursors evaporated from an evaporator onto a substrate to prepare the thin film.

[0175] Comparative Example 1

[0176] The film was manufactured in essentially the same manner as in Example 1, except that (3-dimethylaminopropyl)dimethylindium (DADI) was used as the indium precursor.

[0177] Comparative Example 2

[0178] The thin film was manufactured in essentially the same manner as in Example 1, except that trimethylindium (TMI) was used as the indium precursor.

[0179] The types of indium precursors used in Example 1, Comparative Examples 1 and 2, and the indium composition ratios of the films manufactured in Example 1, Comparative Examples 1 and 2 are shown in Table 1.

[0180] Table 1

[0181] category Types of indium precursors (indium sources) Indium composition ratio in IGZO thin films Comparative Example 1 (3-Dimethylaminopropyl)dimethylindium (DADI) 2wt% Comparative Example 2 Trimethylindium (TMI) 0wt% Example 1 Triethylin (TEI) 15wt%

[0182] According to Table 1 above, when triethylindium (TEI) was used as the indium precursor in Example 1, the indium composition ratio in the film was 15 wt%, which is greater than the indium composition ratio in Comparative Example 1 where the indium precursor was DADI and Comparative Example 2 where the indium precursor was TMI. Accordingly, using triethylindium (TEI) as the indium precursor is suitable for forming a film using a liquid-mixed precursor composition.

[0183] Example 2: Fabrication of thin films using a mixed precursor composition of three categories for depositing IGZO thin films.

[0184] The steps for manufacturing a thin film using a mixed precursor composition of three categories for depositing IGZO thin films include steps 1 through 4. In step 1 (step 1), the temperature of the substrate provided inside the reaction chamber is heated to 100°C, the phase change of the mixed precursor composition of three categories for depositing IGZO thin films manufactured in Example 1 is performed by evaporation to a gas, and the mixed precursor composition of three categories for depositing IGZO thin films is provided on the substrate at a rate of 0.05 g / min for 1 second. The standard pressure in step 1 (step 1) is 0.005 Torr, while the process pressure is 0.5 Torr. In step 2 (step 2), argon gas (100 sccm) is provided as a purge gas into the reaction chamber for 5 seconds to perform a first purging process. In step 3 (step 3), O2 source material is provided into the reaction chamber at 100 sccm for 1 second. Subsequently, in step 4, argon gas (100 sccm) is supplied to the reaction chamber as a purge gas for 5 seconds to perform the second purging process.

[0185] Example 3: Fabrication of thin films using a mixed precursor composition of three categories for depositing IGZO thin films.

[0186] The steps for fabricating the thin film using the tri-category mixed precursor composition for depositing IGZO thin films are essentially the same as in Example 2, except for the conditions of the following steps. In step 1 (step 1), the temperature of the substrate provided inside the reaction chamber is heated to 200°C. The standard pressure in step 1 (step 1) is 0.005 Torr, while the process pressure is 1.0 Torr. The tri-category precursor composition for depositing IGZO thin films is provided on the substrate for 1 second at a rate of 0.10 g / min. In step 2 (step 2), argon gas (100 sccm) is provided as a purge gas into the reaction chamber for 30 seconds for a first purging process. In step 3 (step 3), O2 plasma source material is provided into the reaction chamber at 200 sccm for 5 seconds. Subsequently, in step 4 (step 4), argon gas (100 sccm) is provided as a purge gas into the reaction chamber for 30 seconds for a second purging process.

[0187] Example 4: Fabrication of thin films using a mixed precursor composition of three categories for depositing IGZO thin films.

[0188] The steps for manufacturing the film using the three-category mixed precursor composition for depositing IGZO film are essentially the same as in Example 3, except that the three-category mixed precursor composition for depositing IGZO film is supplied to the substrate at a rate of 0.10 g / min for 3 seconds.

[0189] The process conditions for manufacturing thin films using the three categories of mixed precursor compositions for depositing IGZO thin films in Examples 2 to 4 above are shown in Table 2.

[0190] Table 2

[0191]

[0192]

[0193] Experimental Example

[0194] Example 1: Physical property analysis of a liquid tri-classified mixed precursor composition for depositing IGZO thin films.

[0195] When the indium:gallium:zinc mixing molar ratio in the liquid tri-classified mixed precursor composition used for depositing IGZO thin films is 1:1:1, the measurement methods, apparatus and analytical results used to obtain physical property analysis are shown in Table 3.

[0196] Table 3

[0197]

[0198] Example 2: NMR analysis of a liquid tri-classified mixed precursor composition for depositing IGZO thin films.

[0199] Figure 8 , Figure 9 and Figure 10 NMR analysis of the three categories of mixed precursor compositions prepared in Example 2 for depositing IGZO thin films is shown.

[0200] Figure 8 (a) to Figure 8 (c) A graph showing the NMR results of measuring each source after synthesizing gallium precursor sources, indium precursor sources, and zinc precursor sources for manufacturing mixed precursor compositions of three categories for depositing IGZO thin films, according to an embodiment of the present disclosure.

[0201] refer to Figure 8 (a) Figure 8 (b) and Figure 8 (c) As can be confirmed by the peaks shown in the graph, the gallium precursor, indium precursor and zinc precursor used to manufacture the three categories of mixed precursor compositions for depositing thin films are trimethylgallium, triethylindium and diethylzinc, respectively.

[0202] Figure 9 (a) Figure 9 (b) and Figure 9(c) A graph showing the results of NMR measurements of a mixture of three categories of precursor compositions after manufacturing a mixed precursor composition for depositing an IGZO thin film according to an embodiment of the present disclosure.

[0203] refer to Figure 9 The molar ratio of triethylin, trimethylgallium (TMG), and diethylzinc can be controlled to be 1:1:1 or 3:1:3. It has been confirmed that when the molar ratio of trimethylgallium decreases, the peak intensity of gallium (Ga) decreases.

[0204] Figure 10 (a) Figure 10 (b) and Figure 10 (c) An explanation of the NMR analysis results of the indium precursor triethylin according to embodiments of the present disclosure.

[0205] refer to Figure 10 The peaks can be confirmed to completely correspond to the ethyl and methyl groups of the synthesized and refined triethylindium.

[0206] Example 3: Gas chromatography-mass spectrometry (GC / MS) analysis of a liquid tri-classified mixed precursor composition for depositing IGZO thin films.

[0207] Figure 11 and Figures 12A to 12F The results of gas chromatography-mass spectrometry (GC / MS) of the three categories of mixed precursor compositions prepared in Example 2 for depositing IGZO thin films are shown.

[0208] Figure 11 This is an interpretation of the gas chromatography-mass spectrometry (GC / MS) results of a three-category mixed precursor composition for depositing IGZO thin films according to embodiments of the present disclosure.

[0209] Figure 11 The graph shows the signal intensity curves along the time axis for mixed precursor compositions classified into three groups for depositing IGZO thin films. (Reference) Figure 11 It can be confirmed that the peak shown first is that of the analytical solvent, and the individual components of the three categories of mixed precursor compositions used for depositing IGZO films can be identified from the peaks at 4 minutes, 6 minutes and 8 minutes respectively. Figure 11 and Figures 12A to 12F To illustrate the interpretation of gas chromatography-mass spectrometry (GC / MS) results of each component in a three-category mixed precursor composition for depositing IGZO thin films according to embodiments of the present disclosure. Reference Figure 11 and Figures 12A to 12FIt can be confirmed that triethylindium, trimethylgallium (TMG), and diethylzinc are mixed in the molar ratio of each element in a three-category mixed precursor composition for depositing IGZO thin films. The above figure can be used as a reference library of gas chromatography-mass spectrometry (GC / MS) data for the three-category mixed precursor compositions for depositing IGZO thin films.

[0210] Experimental Example 4: TGA Analysis of Liquid Tri-classified Mixed Precursor Compositions for IGZO Thin Film Deposition

[0211] Figure 13 The results of TGA analysis of the three categories of mixed precursor compositions prepared in Example 1 for depositing IGZO thin films are shown.

[0212] Figure 13 This is to illustrate the interpretation of the analytical results obtained by thermogravimetric analysis (TGA) using a mixed precursor composition of three categories for depositing IGZO thin films according to embodiments of the present disclosure, which measures the thermal stability and decomposition temperature of liquid indium precursor, liquid gallium precursor and / or liquid zinc precursor.

[0213] refer to Figure 13 It can be confirmed that the mass of the indium precursor triethylin and the zinc precursor diethylzinc according to embodiments of the present disclosure decreases by about 50 wt% at a temperature of about 250°C. This demonstrates the excellent thermal stability of the triethylin and diethylzinc of the present disclosure.

[0214] refer to Figure 13 The mass of the gallium precursor trimethylgallium according to embodiments of the present disclosure decreases by about 45 wt% at a temperature of about 320°C. This demonstrates the excellent thermal stability of the trimethylgallium of the present disclosure.

[0215] Experimental Example 5: Side Reaction Analysis Based on the Molar Ratio of Liquid Tri-classified Mixed Precursor Compositions Used for IGZO Thin Film Deposition

[0216] Table 4 shows whether side reactions occur under conditions based on the molar ratio of each element when manufacturing mixed precursor compositions of three categories for depositing IGZO thin films.

[0217] Table 4

[0218] In Ga Zn 0.1mol X X X 0.5mol X X X 1.0 mol X X X 2.0 mol X X X 3.0 mol X X X 5.0 mol X X X 10.0 mol X X X

[0219] *X: No side reactions occurred.

[0220] Referring to Table 4, no undesirable side reactions occur when the molar ratio of indium:gallium:zinc in the precursor composition used for thin film deposition is 1:1:1 (where the amounts of indium, gallium, and zinc in the precursor composition used for thin film deposition are 0.1 mol, 0.5 mol, 1.0 mol, 2.0 mol, 3.0 mol, 5.0 mol, or 10.0 mol, respectively).

[0221] Experimental Example 6: Analysis of Side Reactions Based on Mixing Conditions of a Liquid Tri-classified Mixed Precursor Composition for IGZO Thin Film Deposition

[0222] Table 5 shows whether side reactions or floating matter, color changes, and temperature changes occurred based on the mixing conditions (RPM and mixing time) of the mixed precursor compositions used in the three categories for manufacturing IGZO thin films.

[0223] Table 5

[0224]

[0225] *X: No side reactions occurred, no floating matter appeared, no color change, and no temperature change.

[0226] Referring to Table 5, the indium precursor, gallium precursor, and zinc precursor were mixed at 100 RPM, 300 RPM, 600 RPM, 800 RPM, and 1,000 RPM for 10 minutes, 20 minutes, 30 minutes, and 60 minutes, respectively. Undesirable side reactions, the appearance of floating matter, color changes, and temperature changes are not shown.

[0227] Experimental Example 7: Evaluation of the Physical Properties of Thin Films

[0228] Thin films were fabricated using a mixed precursor composition of three categories for depositing IGZO thin films, and the physical properties of the films were evaluated.

[0229] Figure 14 This is a SEM image obtained by photographing a cross-section of an IGZO thin film formed by atomic layer deposition according to an embodiment of the present disclosure. Figure 15 A graph showing the XRD results of an IGZO thin film formed by atomic layer deposition according to an embodiment of the present disclosure.

[0230] refer to Figure 14 and Figure 15When a mixed precursor composition of liquid tri-category for depositing IGZO thin films is provided at room temperature using a liquid delivery system (LDS), evaporated using an evaporator, and deposited to form a thin film, it has been confirmed that the formed film has a smooth surface, excellent film quality, and an amorphous IGZO thin film structure similar to that of films deposited by PVD. The use of precursor compositions comprising liquid indium precursors, liquid gallium precursors, and liquid zinc precursors for depositing thin films via atomic layer deposition according to embodiments of this disclosure results in thin films exhibiting an amorphous phase, enabling the film to exhibit very superior electron mobility and improved electrical properties.

[0231] Figure 16 (a) An explanation of the growth amount (GPC) per cycle of the IGZO thin film formed by atomic layer deposition according to the embodiment and the thickness measured by using an ellipsometry. Figure 16 (b) An explanation of the growth rate (GPC) of an IGZO thin film formed by atomic layer deposition according to an embodiment of the present disclosure, based on the deposition temperature per cycle.

[0232] refer to Figure 16 (a) It can be confirmed that, according to the growth per cycle (GPC) based on the number of atomic layer depositions according to the embodiment, since the cycle and thickness curves have a positive slope, the substrate thickness increases uniformly with the increase of cycles. Accordingly, cycles can be selected to deposit the desired thickness required by the apparatus, and the thickness can be appropriately controlled by adjusting the cycles.

[0233] In addition, considering that the film growth can be slightly faster due to the high growth per cycle (GPC) phenomenon in the early stages of deposition, the number of deposition cycles can be adjusted appropriately according to the deposition thickness.

[0234] Although this disclosure is not limited thereto, based on the thickness of the atomic layer deposition according to the embodiment following the growth per cycle (GPC), approximately [amount] is deposited per cycle in the early stages of deposition. The thickness, and in the later stages of deposition (500 cycles or more), approximately [amount missing] per cycle. The thickness is adjusted accordingly, allowing for the deposition of the desired thickness.

[0235] exist Figure 16 In (b), the ALD window is determined by measuring the growth rate at different temperatures used for the atomic layer deposition (ALD) process. Figure 16(b) shows an ALD window with a constant growth rate when the deposition temperature is between 100°C and 250°C. Since approximately [amount missing] are deposited per cycle within the above deposition temperature range... The thickness of the film is such that ALD deposition of the film proceeds well within this range. However, when the deposition temperature is above 300°C, the growth rate increases sharply. This indicates that the tri-category mixed precursor composition for depositing IGZO films cannot be used to deposit IGZO films due to thermal decomposition. Therefore, although this disclosure is not limited thereto, the deposition temperature for atomic layer deposition according to embodiments of this disclosure may suitably be between 100°C and 300°C, and suitably between 100°C and 250°C.

[0236] Figure 17 (a) and Figure 17 (b) An explanation of the compositional proportions of the film components for forming a film by means of a liquid tri-classified mixed precursor composition for depositing IGZO thin films according to embodiments of the present disclosure by means of atomic layer deposition using X-ray photoelectron spectroscopy (XPS) patterns.

[0237] Figure 17 (a) and Figure 17 (b) Shows the atomic composition ratios in the thin films when the molar ratios of indium:gallium:zinc in the precursor compositions used for film deposition are 3:1.1:3 and 3:3:3, respectively. Reference Figure 17 (a), Figure 17 (a) shows the atomic composition proportions in a film formed by mixing indium:gallium:zinc in a precursor composition for film deposition at a molar ratio of 3:1.1:3. The atomic percentages (at%) of indium and zinc in the film are shown to be between approximately 15 at% and 25 at%, and the atomic percentage (at%) of gallium in the film is shown to be 10 at% or lower, which is the lowest and quite different from the atomic percentages of the other atoms. However, reference... Figure 17 (b), Figure 17 (b) The atomic composition ratio of the film formed by mixing indium:gallium:zinc in a precursor composition for film deposition of 3:3:3 is shown, confirming that the atomic percentage of each of indium, gallium and zinc in the film is uniformly distributed between about 10 at% and 20 at%.

[0238] When a thin film is formed in a single process using a mixed precursor composition of three categories for depositing IGZO thin films, the actual proportion of atoms deposited can vary due to differences in the reactivity of each precursor atom. In particular, gallium is relatively less reactive than indium or zinc. Therefore, the molar concentration of gallium, which has lower reactivity, can be adjusted to a larger value than the molar concentrations of indium and zinc to control the proportion of each element included in the thin film. Furthermore, the process conditions during thin film formation can be controlled to appropriately control the proportion of atoms included in the thin film.

[0239] Figure 18 (a) and Figure 18 (b) are surface and cross-sectional mapping images of the components of a thin film formed by atomic layer deposition according to an embodiment of the present disclosure, analyzed by SEM_EDS, wherein each atom in the thin film is distinguished by color. Reference Figure 18 This confirms that the atoms in the IGZO thin film are uniformly distributed.

[0240] Figure 19 (a) and Figure 19 (b) An explanation illustrating the refractive index and absorption coefficient of a thin film formed by atomic layer deposition according to embodiments of the present disclosure. Reference Figure 19 It can be confirmed that the IGZO thin film has a refractive index n of approximately 2 and an absorption coefficient k approaching 0 in the wavelength range between 400 nm and 1600 nm. In particular, the refractive index n is 2.04 relative to the wavelength of 630 nm in the visible light range (400 nm and 800 nm), and the absorption coefficient k is close to 0.

[0241] Figure 20 (a) Interpretation of the O1s peak of a thin film formed by atomic layer deposition according to an embodiment of the present disclosure using X-ray photoelectron spectroscopy (XPS) pattern. Reference Figure 20 (a) It can be confirmed that in Examples 5 to 10, under different conditions of oxygen flow rate and plasma power, there was a slight shift in the peak at the binding energy of approximately 532 eV. Table 6 shows... Figure 20 (a) shows the conditions for argon supply, oxygen supply, supply time, and plasma power in Examples 5 to 10.

[0242] Table 6

[0243]

[0244]

[0245] Figure 20 (b) A graph showing the peaks after deconvolving the O1s peak into three peaks. (Reference) Figure 20(b) An O1s peak was detected at 532 eV, and the detection position of the peak shifted depending on the bonding with another atom. Table 7 shows each peak, the bonding, and the integral size of the peak.

[0246] Table 7

[0247] peak bonded to atoms Integral size of the peak Peak A Metal-oxide bonding [MO, metal-oxide] 81.66％ Peak B Oxygen vacancy binding [O-Ov, oxide-oxygen vacancy] 16.22％ Peak C Oxygen-hydrogen combination [OH, oxide-hydrogen] 2.12％

[0248] Referring to Table 7, peak A shows a metal-oxide bond with an integral size of 81.66%, peak B shows an oxygen vacancy bond with an integral size of 16.22%, and peak C shows an oxygen-hydrogen bond with an integral size of 2.12%. Accordingly, it can be confirmed that metal-oxide bonds are most abundant in the IGZO thin film according to the embodiments of this disclosure.

[0249] Figure 21 and Figure 22 Atomic force microscopy (AFM) illustration of the growth behavior and root mean square surface roughness of IGZO thin films according to embodiments of the present disclosure, showing the three-dimensional and two-dimensional particle morphologies.

[0250] Figure 21 and Figure 22 The root mean square surface roughness (RMS) of an IGZO thin film according to an embodiment of the present disclosure is shown in two and three dimensions using AFM. Reference Figure 21 When the film thickness is 45 nm, the RMS values ​​in two-dimensional and three-dimensional planes are 1.17 nm and 1.13 nm, respectively. (Reference) Figure 22 When the film thickness is 45 nm, the RMS in two dimensions and three dimensions are 1.20 nm and 1.10 nm, respectively. Accordingly, it can be confirmed that when the film thickness is 45 nm, a monolayer continuous IGZO film is formed to maintain a uniform root mean square surface roughness, and its root mean square surface roughness is kept below 1.20 nm.

[0251] Experiment Example 8: Evaluation of Thin Film Transistor Characteristics

[0252] Thin films are manufactured by using a mixed precursor composition of three categories for depositing IGZO thin films, and thin-film transistors are manufactured including the manufactured thin films as active layers (ACT). Electronic devices ECD1 to ECD7 including thin-film transistors are available.

[0253] Figure 5 (a) A schematic cross-sectional view of a thin-film transistor according to an embodiment of the present disclosure, comprising an IGZO thin film formed by using a mixed precursor composition of three categories for depositing an IGZO thin film, and Figure 5 (b) is a schematic top view of a thin-film transistor.

[0254] refer to Figure 5 (a) Using a highly doped silicon substrate GS on which a SiO2 buffer layer BF with a thickness of 100 nm is formed, an active layer ACT is formed by depositing an IGZO thin film on the SiO2 buffer layer BF, and a thin film transistor comprising a source electrode S and a drain electrode D disposed opposite to each other on the active layer ACT is fabricated.

[0255] refer to Figure 5 (b) The width W and length L of the thin-film transistor are 800 μm and 40 μm, respectively.

[0256] Figure 23 The transfer curve is shown to illustrate the reliability assessment results of the IGZO thin film according to the embodiments of this disclosure.

[0257] refer to Figure 23 IGZO thin-film transistors exhibit exceptional stability and durability because the threshold voltage variation due to photovoltage or voltage stress is less than 1V. Accordingly, by using a liquid tri-classified mixed precursor composition for depositing IGZO thin films according to embodiments of the present disclosure, process time can be reduced while maintaining the characteristics of the thin-film transistor. By using the tri-classified mixed precursor composition for depositing IGZO thin films according to embodiments of the present disclosure, thin films can be fabricated, and thin-film transistors comprising the fabricated thin film as an active layer ACT can be used as switching or driving devices in pixels of displays (i.e., active-matrix displays, such as liquid crystal displays or organic light-emitting diode displays), and can be applied to flat panel displays (such as next-generation active-matrix liquid crystal displays (AMLCDs) and active-matrix organic light-emitting diodes (AMOLEDs)) to provide ultra-high-definition (UHD) images. In addition to the above, it can also be applied to other electronic devices, such as storage devices and logic devices for various purposes.

[0258] Although specific embodiments of this disclosure have been described, it should be understood by any person skilled in the art to which this disclosure pertains that various modifications and variations may be made to this disclosure without departing from the technical concept and scope defined in the claims.

[0259] Therefore, the technical scope of this disclosure should be interpreted by the scope of the claims, rather than by the limitations of the description disclosed in the detailed description.

Claims

1. A precursor composition for depositing thin films, comprising: Liquid indium precursor; Liquid gallium precursor; and Liquid zinc precursor.

2. The precursor composition for depositing the thin film as claimed in claim 1, wherein, The molar ratio of indium:gallium:zinc in the precursor composition used for depositing the thin film is 0.1 to 10:0.1 to 10:0.1 to 10.

3. The precursor composition for depositing the thin film as described in claim 1, wherein, The liquid indium precursor is selected from at least one of triethylindium, triisopropylindium, and tritert-butylindium.

4. The precursor composition for depositing the thin film as claimed in claim 1, wherein, The precursor composition used for depositing the thin film does not include a solvent.

5. The precursor composition for depositing the thin film as claimed in claim 1, wherein, All of the liquid indium precursor, liquid gallium precursor, and liquid zinc precursor are alkyl precursors.

6. A method for manufacturing a thin film, comprising: The precursor composition for depositing the thin film as described in any one of claims 1 to 5 is obtained by mixing liquid indium precursor, liquid gallium precursor and liquid zinc precursor; as well as The thin film is formed on a substrate in a chamber using the precursor composition.

7. The method for manufacturing a thin film as described in claim 6, wherein, The thin film is formed by using the precursor composition for depositing the thin film via atomic layer deposition or chemical vapor deposition.

8. The method for manufacturing a thin film as described in claim 6, wherein, The temperature at which the thin film is formed is between 100°C and 300°C.

9. The method for manufacturing a thin film as described in claim 6, further comprising: Before forming the film, the precursor composition is evaporated using an evaporator.

10. The method for manufacturing a thin film as claimed in claim 6, further comprising: After the film is formed, the chamber is purged with an inert gas for the first time.

11. The method for manufacturing a thin film as described in claim 10, further comprising: After the first purging, the film is oxidized by using a reactive gas.

12. The method for manufacturing a thin film as described in claim 11, wherein, The flow rate of the reactive gas is between 50 sccm and 500 sccm, and The supply time of the reactive gas is between 0.1 seconds and 60 seconds.

13. The method for manufacturing a thin film as claimed in claim 11, further comprising: After the film is oxidized, a second purging with inert gas is performed in the chamber.

14. An electronic device comprising: The film formed by the film manufacturing method according to any one of claims 6 to 13, The thin film is a single amorphous layer comprising indium, gallium, and zinc.

15. The electronic device of claim 14, wherein, The electronic device is one of the following: flat panel display, curved display, television, billboard, computer monitor, medical monitor, head-mounted display, indoor light, outdoor light, signal light, wearable device, foldable device, rollable device, bendable device, flexible device, curved device, electronic notebook computer, e-book, portable multimedia player, personal digital assistant, laser printer, telephone, cellular phone, tablet computer, portable terminal, notebook computer, laptop computer, digital camera, viewfinder, camcorder, 3D display, virtual reality display, augmented reality display, video wall containing multiple displays spliced ​​together, vehicle, outdoor display device, theater screen, stadium screen, and signboard.

16. The electronic device of claim 14, wherein, The indium content in the film is greater than or equal to 10 wt%.

17. The electronic device of claim 14, wherein, For light with a wavelength of 630 nm, the thin film has a refractive index between 1.5 and 2.5.

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