Method for designing atomic layer deposition process for manufacturing amorphous oxide semiconductor material film and amorphous IGZO material film manufactured using same

Abstract

Provided is a method for designing an atomic layer deposition process for manufacturing an amorphous oxide semiconductor material film. The method for designing an atomic layer deposition process comprises: a step in which a first unit process for providing an indium (In) precursor and a first reactant on a substrate is performed to form a first material film obtained by a reaction of the indium (In) precursor and the first reactant; a step in which a second unit process for providing a gallium (Ga) precursor and a second reactant on the first material film is performed to form a second material film obtained by a reaction of the gallium (Ga) precursor and the second reactant; and a step in which a third unit process for providing a zinc (Zn) precursor and a third reactant on the second material film is performed to form a third material film obtained by a reaction of the zinc (Zn) precursor and the third reactant, wherein the first unit process to the third unit process are each repeated multiple times. The method may comprise controlling the crystallinity of an IGZO material film including the first to third material films by controlling the number of repetitions of each of the first unit process to the third unit process.

Description

Design method of an atomic layer deposition process for manufacturing an amorphous oxide semiconductor material film and an amorphous IGZO material film manufactured using the same

[0001] The present invention relates to a design method for an atomic layer deposition (ALD) process for manufacturing an amorphous oxide semiconductor material film.

[0002] Memory is essential to most electronic devices used in modern life, and the related market is growing along with the increasing demand for memory. Among these, NAND flash memory has been steadily used for large-capacity data storage due to its scalability and low power consumption. To meet the demand for high integration, NAND flash memory has evolved from a planar structure to a three-dimensional structure, increasing the number of layers to increase integration per unit area. However, various limitations have been presented in device operation due to issues such as high leakage current of poly-Si channel material, threshold voltage dispersion, cost, and dispersion during face-to-face processing.

[0003] Oxide semiconductors are a candidate channel material to solve the above-mentioned problems. Unlike Si-based materials, oxide semiconductors exhibit excellent electron transport properties even in an amorphous state, resulting in advantages such as high mobility, low leakage current, and excellent large-area uniformity. Furthermore, unlike homogeneous structures, heterogeneous structures composed of high- and low-conductivity materials can enhance TFT characteristics through the formation of multiple channels. However, when heterogeneous oxide semiconductors are formed through atomic layer deposition, a polycrystalline structure is generated depending on the composition design, which deteriorates device characteristics.

[0004] Therefore, even with identical compositions, research is needed to resolve the polycrystalline structure through composition distribution design, thereby achieving an amorphous structure or oriented crystal structure. Such process improvements are expected to alleviate the problems associated with poly-Si channels in existing memory devices.

[0005] The technical problem to be solved by the present invention is to provide a method for manufacturing an amorphous oxide semiconductor material film.

[0006] Another technical problem to be solved by the present invention is to provide a method for manufacturing an oxide semiconductor material film having a heterogeneous structure.

[0007] Another technical problem to be solved by the present invention is to provide a method for manufacturing an amorphous IGZO material film.

[0008] Another technical problem to be solved by the present invention is to provide a method for manufacturing an IGZO material film having a heterogeneous structure.

[0009] Another technical problem to be solved by the present invention is to provide a method for designing an atomic layer deposition process for manufacturing an oxide semiconductor material film having an amorphous and heterogeneous structure.

[0010] Another technical problem to be solved by the present invention is to provide a method for designing an atomic layer deposition process for manufacturing an IGZO material film having an amorphous and heterogeneous structure.

[0011] The technical problems to be solved by the present invention are not limited to those described above.

[0012] To solve the above-described technical problems, the present invention provides a design method for an atomic layer deposition process for manufacturing an amorphous oxide semiconductor material film.

[0013] According to one embodiment, the design method of the atomic layer deposition process includes performing a first unit process of providing an indium (In) precursor and a first reactant on a substrate, thereby forming a first material film in which the indium precursor and the first reactant are reacted, performing a second unit process of providing a gallium (Ga) precursor and a second reactant on the first material film, thereby forming a second material film in which the gallium precursor and the second reactant are reacted, and performing a third unit process of providing a zinc (Zn) precursor and a third reactant on the second material film, thereby forming a third material film in which the zinc precursor and the third reactant are reacted, wherein the first unit process to the third unit process are each repeatedly performed a plurality of times, and the number of repetitions of each of the first unit process to the third unit process is controlled to control crystallinity of the IGZO material film including the first to third material films.

[0014] According to one embodiment, the number of repetitions of the first unit process: the number of repetitions of the second unit process: the number of repetitions of the third unit process may be controlled in a ratio of (5:3:2) x n (n is an integer greater than or equal to 1 and less than or equal to 2), thereby forming the IGZO material film into an amorphous state.

[0015] According to one embodiment, the thickness of each of the first material film to the third material film may be controlled as the number of repetitions of each of the first unit process to the third unit process is controlled.

[0016] According to one embodiment, the method may include forming the IGZO material film in an amorphous state by controlling the thickness of the first material film to 2 nm or less.

[0017] According to one embodiment, the method may include forming the IGZO material film in an amorphous state by controlling the sum of the thickness of the first material film and the thickness of the third material film to 2 nm or less.

[0018] According to one embodiment, the first unit process may include a step of providing the indium precursor on the substrate and a step of providing the first reactant on the substrate on which the indium precursor is provided, the second unit process may include a step of providing the gallium precursor on the first material film and a step of providing the second reactant on the first material film on which the gallium precursor is provided, and the third unit process may include a step of providing the zinc precursor on the second material film and a step of providing the third reactant on the second material film on which the zinc precursor is provided.

[0019] According to another embodiment, the design method of the atomic layer deposition process includes performing a first unit process of providing an indium (In) precursor and a first reactant on a substrate, thereby forming a first material film in which the indium precursor and the first reactant are reacted, performing a second unit process of providing a gallium (Ga) precursor and a second reactant on the first material film, thereby forming a second material film in which the gallium precursor and the second reactant are reacted, and performing a third unit process of providing a zinc (Zn) precursor and a third reactant on the second material film, thereby forming a third material film in which the zinc precursor and the third reactant are reacted, wherein the first unit process to the third unit process are each repeatedly performed a plurality of times, and the number of repetitions of at least one unit process among the first unit process and the third unit process is divided to form an IGZO material film including the first to third material films in an amorphous state.

[0020] According to another embodiment, the method may include forming the IGZO material film into an amorphous state by dividing the number of repetitions of at least one of the first unit process and the third unit process, thereby controlling the sum of the thickness of the first material film and the thickness of the third material film to be 2 nm or less.

[0021] According to another embodiment, the first unit process may include a 1-1 unit process that is repeatedly performed A times and a 1-2 unit process that is repeatedly performed B times, and the sum of the A times and the B times may be equal to X times, which is the number of times the first unit process is repeatedly performed.

[0022] According to another embodiment, the 1-1 unit process may be performed before the 2nd unit process, and the 1-2 unit process may be performed after the 2nd unit process and before the 3rd unit process.

[0023] According to another embodiment, the first unit process may include a 1-1 unit process that is repeatedly performed A times, a 1-2 unit process that is repeatedly performed B times, and a 1-3 unit process that is repeatedly performed C times, and the third unit process may include a 3-1 unit process that is repeatedly performed D times, and a 3-2 unit process that is repeatedly performed E times, wherein the sum of the A times, the B times, and the C times is equal to X times, which is the number of times the first unit process is repeated, and the sum of the D times and the E times is equal to Z times, which is the number of times the third unit process is repeated.

[0024] According to another embodiment, the 1-1 unit process may be performed before the 2nd unit process, the 1-2 unit process may be performed after the 2nd unit process and before the 3-1 unit process, the 1-3 unit process may be performed after the 3-1 unit process and before the 3-2 unit process, the 2nd unit process may be performed after the 1-1 unit process and before the 1-2 unit process, the 3-1 unit process may be performed after the 1-2 unit process and before the 1-3 unit process, and the 3-2 unit process may be performed after the 1-3 unit process.

[0025]

[0026] To solve the above-described technical problems, the present invention provides an IGZO material film.

[0027] According to one embodiment, in an IGZO material film including a first material film including indium (In), a second material film including gallium (Ga), and a third material film including zinc (Zn), a sum of the thickness of the first material film and the thickness of the third material film may be 2 nm or less, and may include having an amorphous structure.

[0028] According to one embodiment, an interface may be formed between adjacent material films.

[0029] A design method of an atomic layer deposition process according to an embodiment of the present invention includes a step of performing a first unit process of providing an indium (In) precursor and a first reactant on a substrate to form a first material film in which the indium precursor and the first reactant are reacted, a step of performing a second unit process of providing a gallium (Ga) precursor and a second reactant on the first material film to form a second material film in which the gallium precursor and the second reactant are reacted, and a step of performing a third unit process of providing a zinc (Zn) precursor and a third reactant on the second material film to form a third material film in which the zinc precursor and the third reactant are reacted, wherein the first unit process to the third unit process are each repeatedly performed a plurality of times, and the number of repetitions of each of the first unit process to the third unit process is controlled so that the sum of the thickness of the first material film and the thickness of the third material film becomes 2 nm or less, or at least one unit process among the first unit process and the third unit process is repeatedly performed. The number of times can be divided. Accordingly, an oxide semiconductor material film with an amorphous structure (e.g., an IGZO material film) can be manufactured.

[0030] FIG. 1 is a flowchart for explaining a design method of an atomic layer deposition process according to a first embodiment of the present invention.

[0031] FIG. 2 is a drawing for explaining an IGZO material film manufactured through a design method of an atomic layer deposition process according to a first embodiment of the present invention.

[0032] FIG. 3 is a drawing for more specifically explaining the sequence of an atomic layer deposition process according to the first embodiment of the present invention.

[0033] FIG. 4 is a drawing for explaining an example of an atomic layer deposition process according to a second embodiment of the present invention.

[0034] FIG. 5 is a drawing for explaining another example of an atomic layer deposition process according to a second embodiment of the present invention.

[0035] FIG. 6 is a drawing for explaining the GIWAXS analysis results of a homogenous IGZO material film according to Experimental Example 1 of the present invention.

[0036] FIG. 7 is a drawing for explaining the GIWAXS analysis results of a heterogeneous IGZO material film according to Experimental Example 2 of the present invention.

[0037] FIG. 8 is a drawing for explaining the electrical characteristics of a TFT to which a homogenous IGZO material film according to Experimental Example 1 of the present invention is applied.

[0038] FIG. 9 is a drawing for explaining the electrical characteristics of a TFT to which a heterogeneous IGZO material film according to Experimental Example 1 of the present invention is applied.

[0039] FIG. 10 is a drawing for explaining the reliability of a TFT to which a homogenous IGZO material film according to Experimental Example 1 of the present invention is applied.

[0040] Fig. 11 is a drawing for explaining the reliability of a TFT to which a heterogeneous IGZO material film is applied according to Experimental Example 1 of the present invention.

[0041] Fig. 12 is a drawing for explaining the results of confirming the oscillation pattern of the IGZO material film according to Experimental Examples 2-1 to 2-4 of the present invention.

[0042] Figure 13 is a schematic diagram of a TFT to which an IGZO material film is applied according to Experimental Examples 2-1 to 2-4 of the present invention.

[0043] FIG. 14 and FIG. 15 are drawings for explaining the electrical characteristics of a TFT to which an IGZO material film according to experimental examples 2-1 to 2-4 of the present invention is applied.

[0044] Fig. 16 is a drawing for explaining the results of crystallinity evaluation of IGZO material films according to experimental examples 2-1 to 2-4 of the present invention.

[0045] Figure 17 is a drawing for explaining the results of crystallinity evaluation of IGZO material films according to Experimental Examples 3-1 to 3-3 of the present invention.

[0046] Figure 18 is a TEM image of an IGZO material film according to Experimental Examples 3-1 to 3-3 of the present invention.

[0047] FIG. 19 is a drawing for explaining the results of crystallinity evaluation of an IGZO material film according to experimental examples 4-1 and 4-2 of the present invention.

[0048] Figure 20 is a TEM image of an IGZO material film according to Experimental Examples 4-1 and 4-2 of the present invention.

[0049] Figure 21 is a schematic diagram of a TFT to which an IGZO material film is applied according to experimental examples 4-1 and 4-2 of the present invention.

[0050] FIG. 22 is a drawing for explaining the electrical characteristics of a TFT to which an IGZO material film is applied according to Experimental Examples 4-1 and 4-2 of the present invention.

[0051] Figure 23 is a drawing for explaining the reliability of a TFT to which an IGZO material film is applied according to experimental examples 4-1 and 4-2 of the present invention.

[0052] FIG. 24 is a drawing comparing the growth rate, XPS analysis results, XPS analysis results, and composition of IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0053] Figure 25 is a drawing for explaining the results of crystallinity evaluation of IGZO material films according to experimental examples 5-1 to 5-3 of the present invention.

[0054] Figure 26 is a drawing for explaining the difference in density of IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0055] Figure 27 is a drawing comparing the surface roughness of IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0056] Figure 28 is a drawing for explaining the XPS O 1s analysis results of the IGZO material film according to Experimental Examples 5-1 to 5-3 of the present invention.

[0057] FIG. 29 is a drawing comparing the O 1s sub-peak area ratios of IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0058] Figure 30 is a schematic diagram of a TFT to which an IGZO material film is applied according to Experimental Examples 5-1 to 5-3 of the present invention.

[0059] FIG. 31 and FIG. 32 are drawings for explaining the electrical characteristics of a TFT to which an IGZO material film according to experimental examples 5-1 to 5-3 of the present invention is applied.

[0060] FIG. 33 and FIG. 34 are drawings for explaining the reliability of a TFT to which an IGZO material film is applied according to experimental examples 5-1 to 5-3 of the present invention.

[0061] Figure 35 is a drawing for more specifically comparing the crystallinity of IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0062] Figure 36 is a drawing to explain why the sum of the thicknesses of the In material film and the Zn material film is more important than the sum of the thicknesses of the In material film and the Ga material film in order to implement an amorphous IGZO material film.

[0063] Figure 37 is a drawing for explaining another atomic layer deposition process design method for implementing an amorphous IGZO material film.

[0064] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. However, the technical concept of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to sufficiently convey the spirit of the present invention to those skilled in the art.

[0065] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. In addition, in the drawings, the thicknesses of films and regions are exaggerated for the purpose of effectively explaining the technical contents.

[0066] Also, although terms such as first, second, and third have been used to describe various components in various embodiments of this specification, these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiments. Also, the term "and / or" has been used herein to mean including at least one of the components listed before and after.

[0067] In the specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to specify the presence of a feature, number, step, component, or combination thereof described in the specification, and should not be construed as excluding the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. In addition, in the present specification, "connection" is used to mean both indirectly connecting multiple components and directly connecting them.

[0068] In addition, when describing the present invention below, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

[0069]

[0070] The present invention provides a design method for an atomic layer deposition process for manufacturing an amorphous oxide semiconductor (e.g., IGZO) material film and an amorphous oxide semiconductor material film manufactured thereby. In addition, the present invention provides a design method for an atomic layer process for manufacturing an oxide semiconductor material film having a heterogeneous structure. In describing the present invention, a heterogeneous structure means a structure in which different material films are stacked to form a single material film, wherein an interface is formed between the material films. For example, an IGZO material film having a heterogeneous structure means an IGZO material film in which a first material film containing indium (In), a second material film containing gallium (Ga), and a third material film containing zinc (Zn) are stacked, wherein an interface is formed between the first to third material films. In contrast, a homogeneous structure means a structure in which no interface is formed between the material films. For example, an IGZO material film having a homogeneous structure means a structure in which indium (In), gallium (Ga), zinc (Zn), and oxygen (O) are mixed without forming an interface between the material films. In addition, in the following description of the present invention, the thickness of the material film means the thickness of a 'single layer'. For example, in a material film in which a first material film-a second material film-a third material film are sequentially and alternately repeatedly laminated, the thickness of the first material film means the thickness of the first material film single layer, not the sum of the thicknesses of the plurality of first material films.

[0071]

[0072] Design method for an atomic layer deposition process according to the first embodiment

[0073] FIG. 1 is a flowchart for explaining a design method of an atomic layer deposition process according to a first embodiment of the present invention, FIG. 2 is a drawing for explaining an IGZO material film manufactured through a design method of an atomic layer deposition process according to a first embodiment of the present invention, and FIG. 3 is a drawing for explaining in more detail the sequence of an atomic layer deposition process according to the first embodiment of the present invention.

[0074] Referring to FIGS. 1 to 3, a substrate (S) may be prepared. In one embodiment, the substrate (S) may be a silicon semiconductor substrate. Alternatively, in another embodiment, the substrate (S) may be any one of a compound semiconductor substrate, a glass substrate, or a plastic substrate. The type of the substrate (S) is not limited.

[0075] An indium precursor (In precursor) and a first reactant (1) are formed on the above substrate (S). st By providing a reactant, the indium precursor and the first reactant can form a first material film (110) reacted with each other (S110). Accordingly, the first material film (110) can include indium oxide. For example, the first material film (110) can include In2O3.

[0076] According to one embodiment, the first material film (110) may be formed by a PEALD (Plasma Enhanced Atomic Layer Deposition) process. More specifically, the step of forming the first material film (110) may include a step (S111) of providing the indium precursor on the substrate (S), a purge step (S112), a step (S113) of providing the first reactant on the substrate (S) on which the indium precursor is provided, and a purge step (S114), as illustrated in FIG. 3. For example, the indium precursor may include DADI ((3-Dimethylaminopropyl)dimethylindium).For example, the above indium precursors are TMI(Trimethyl indium), TEI(Triethyl indium), InCA-1(Bis(trimethysilyl)amidodiethyl indium), CpIn(Cyclopentadienylindium), In(tmhd)3((Tris(2,2,6,6-tetramethyl-3,5-heptandionato) indium(III)), In(acac)3((Indium(III) acetylacetonate), DATI((dimethylbutylamino)trimethylindium), Me2In(EDPA)(dimethyl(Nethoxy-2,2-dimethylpropanamido)indium), InEtCp(ethylcyclopentadienyl indium), TMION(Trimethyl[N-(2-methoxyethyl)-2-methylpropan-2-amine]indium), DMION(Dimethyl[N-(tert-butyl)-2-methoxy-2-methylpropan-1-amine]indium), DMITN(Dimethyl[N1-(tert-butyl)-N2,N2-dimethylethane-1,2-diamine]indium), [In[(i Pr)2CNEt2]3](tris-(N,N-diisopropyl-2-diethylamido-guanidinato)- indium(III)), [In[(i Pr)2CNMe2]3](tris-(N,N), Et2InN(SiMe3)2(diethyl[bis(trimethylsilyl)amido]indium), In(dmamp)3(tris(1-dimethylamino-2-methyl-2-propoxy)indium), and tris((N,N'-diisopropylacetamidinato)indium(III)) can be included.Additionally, the first reactant may further include argon (Ar).

[0077] The above indium precursor providing step (S111) - purge step (S112) - the first reactant providing step (S113) - purge step (S114) is the first unit process (1 st The first unit process (U10) can be defined as a first unit process (U10). The first unit process (U10) can be repeated multiple times. Accordingly, the thickness of the first material film (110) can be controlled.

[0078] A gallium precursor (Ga precursor) and a second reactant (2) are formed on the first material film (110). nd By providing a reactant, the gallium precursor and the second reactant can form a second material film (120) in which they react (S120). Accordingly, the second material film (120) can include gallium oxide. For example, the second material film (120) can include Ga2O3.

[0079] According to one embodiment, the second material film (120) may be formed by a PEALD (Plasma Enhanced Atomic Layer Deposition) process. More specifically, the step of forming the second material film (120) may include a step (S121) of providing the gallium precursor on the first material film (110), a purge step (S122), a step (S123) of providing the second reactant on the first material film (110) on which the gallium precursor is provided, and a purge step (S124), as illustrated in FIG. 3. For example, the gallium precursor may include TMGa (trimethylgallium). For another example, the gallium precursor is TEGa(Triethyl gallium), Ga(acac)3(Gallium acetylacetonate), [(CH3)2GaNH2]3(dimethylgallium amide), Ga2(NMe2)6(hexakis(dimethylamido)digallium), Me2GaOiPr(dimethylgallium isopropoxide), Ga(OiPr)3(gallium) tri-isopropoxide), [Ga(TMHD)3]([tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gallium(III)]), GaCp (pentamethylcyclopentadienyl gallium), [Ga(thd)3](gallium 2,2,6,6-tetramethyl-3,5-heptanedionate), TMGON (Trimethyl[N-(2-methoxyethyl)-2-methylpropan-2-amine]gallium), It may include either DMGON (Dimethyl[N-(tert-butyl)-2-methoxy-2-methylpropan-1-amine]gallium), or DMGTN (Dimethyl[N1-(tert-butyl)-N2,N2-dimethylethane-1,2-diamine]gallium).For example, the second reactant may include oxygen plasma (O2plasma). Additionally, the second reactant may further include argon (Ar).

[0080] The above gallium precursor providing step (S121) - purge step (S122) - the second reactant providing step (S123) - purge step (S124) is the second unit process (2 nd The second unit process (U20) can be defined as a second unit process (U20). The second unit process (U20) can be repeated multiple times. Accordingly, the thickness of the second material film (120) can be controlled.

[0081] A zinc precursor (Zn precursor) and a third reactant (3) are formed on the second material film (120). rd By providing a reactant, a third material film (130) in which the zinc precursor and the third reactant are reacted can be formed (S130). Accordingly, the third material film (130) may include zinc oxide. For example, the third material film (130) may include ZnO.

[0082] According to one embodiment, the third material film (130) may be formed by a PEALD (Plasma Enhanced Atomic Layer Deposition) process. More specifically, the step of forming the third material film (130) may include a step (S131) ​​of providing the zinc precursor on the second material film (120), a purge step (S132), a step (S133) of providing the third reactant on the second material film (120) on which the zinc precursor is provided, and a purge step (S134), as illustrated in FIG. 3. For example, the zinc precursor may include DEZ (diethylzinc). For another example, the zinc precursor may include any one of dimethylzinc (DMZ), zinc chloride (ZnCl2), zinc acetate (Zn(CH3COO)2), bis[4-((2-ethoxyethyl)imino)-pent-2-en-2-olate]zinc (Zn(eeki)2), and bis-3-(N,N-dimethylamino)propyl zinc (BDMPZ). For example, the third reactant may include oxygen plasma (O2plasma). Additionally, the reactant may further include argon (Ar).

[0083] The above zinc precursor providing step (S131) ​​- purge step (S132) - the third reactant providing step (S133) - purge step (S134) is the third unit process (3 rd The third unit process (U30) can be defined as a third unit process. The third unit process (U30) can be repeated multiple times. Accordingly, the thickness of the third material film (130) can be controlled.

[0084] As the first to third material films (110, 120, 130) are formed, an IGZO material film (100) in which the first to third material films (110, 120, 130) are laminated can be formed. That is, the IGZO material film (100) can be formed on the substrate (S) through a PEALD process.

[0085] According to one embodiment, the first unit process (U10) - the second unit process (U20) - the third unit process (U30) may be defined as a total process. The total process may be repeated multiple times. Accordingly, the thickness of the IGZO material film (100) may be controlled.

[0086] According to one embodiment, the sum of the thicknesses of the first material film (110) and the third material film (130) may be controlled to be 2 nm or less, thereby forming the IGZO material film (100) in an amorphous state. In addition, in order to control the sum of the thicknesses of the first material film (110) and the third material film (130) to be 2 nm or less, the number of repetitions of the first unit process: the number of repetitions of the second unit process: the number of repetitions of the third unit process may be controlled in a ratio of (5:3:2) x n (n is an integer greater than or equal to 1 and less than or equal to 2). That is, by controlling the number of repetitions of the first unit process: the number of repetitions of the second unit process: the number of repetitions of the third unit process to 5:3:2 or 10:6:4, the sum of the thicknesses of the first material film (110) and the third material film (130) can be controlled to 2 nm or less, whereby the IGZO material film (100) can have an amorphous structure. In contrast, when the sum of the thicknesses of the first material film (110) and the third material film (130) exceeds 2 nm, the IGZO material film (100) can have a crystalline structure.

[0087]

[0088] Design method for an atomic layer deposition process according to the second embodiment

[0089] The design method of the atomic layer deposition process according to the second embodiment of the present invention is the same as the design method of the atomic layer deposition process according to the first embodiment, but the number of repetitions of at least one unit process among the first unit process (U10) and the third unit process (U30) is divided so that the IGZO material film (100) including the first to third material films (110, 120, 130) can be formed in an amorphous state.

[0090] FIG. 4 is a drawing for explaining an example of an atomic layer deposition process according to a second embodiment of the present invention, and FIG. 5 is a drawing for explaining another example of an atomic layer deposition process according to a second embodiment of the present invention.

[0091] Referring to FIG. 4, the number of repetitions of the first unit process (U10) may be divided. According to one embodiment, the first unit process (U10) is divided into a 1-1 unit process (1-1 unit process, U11) that is repeated A times and a 1-2 unit process (1-2 unit process, U12) that is repeated B times, wherein the sum of the A times and the B times may be equal to X times, which is the number of repetitions of the first unit process (U10). For example, the first unit process (U10) that is repeated 48 times may be divided into a 1-1 unit process (U11) that is repeated 24 times and a 1-2 unit process (U12) that is repeated 24 times.

[0092] As described above, when the first unit process (U10) is divided into the 1-1 unit process (U11) and the 1-2 unit process (U12), the 1-1 unit process (U11) may be performed before the 2nd unit process (U20), and the 1-2 unit process (U12) may be performed after the 2nd unit process (U20) and before the 3rd unit process (U30).

[0093] According to one embodiment, the 1-1 unit process (U11) may include a first indium precursor providing step (S111a) - a purge step (S112a) - a 1-1 reactant providing step (S113a) - a purge step (S114a). Alternatively, the 1-2 unit process (U12) may include a second indium precursor providing step (S111b) - a purge step (S112b) - a 1-2 reactant providing step (S113b) - a purge step (S114b).

[0094] That is, the IGZO material film (100) can be formed through the steps of forming the first material film (110) - forming the second material film (120) - forming the first material film (110) - forming the third material film (130).

[0095] As described above, by dividing the number of repetitions of the first unit process (U10), the thickness of the first material film (110) can be relatively reduced, and thus the crystallinity of the IGZO material film (100) can be relatively reduced, so that the formation of an amorphous structure can be easily achieved.

[0096] For example, compared to an IGZO material film formed by controlling the number of repetitions of the first unit process: the number of repetitions of the second unit process: the number of repetitions of the third unit process to be 48:3:3, an IGZO material film formed by controlling the number of repetitions of the first unit process: the number of repetitions of the second unit process: the number of repetitions of the first unit process: the number of repetitions of the third unit process to be 24:3:24:3 may have a relatively reduced thickness of the first material film (110) and may also have reduced crystallinity.

[0097] Referring to FIG. 5, the number of repetitions of the first unit process (U10) and the third unit process (U30) can be divided. According to one embodiment, the first unit process (U10) is divided into a 1-1 unit process (1-1 unit process, U11) that is repeated A times, a 1-2 unit process (1-2 unit process, U12) that is repeated B times, and a 1-3 unit process (1-3 unit process, U13) that is repeated C times, wherein the sum of the A times, the B times, and the C times can be equal to X times, which is the number of repetitions of the first unit process (U10). For example, the first unit process (U10) that is repeated 27 times can be divided into a 1-1 unit process (U11) that is repeated 9 times, a 1-2 unit process (U12) that is repeated 9 times, and a 1-3 unit process (U13) that is repeated 9 times. In contrast, the third unit process (U30) is divided into a 3-1 unit process (3-1 unit process, U31) that is repeatedly performed D times, and a 3-2 unit process (3-2 unit process, U32) that is repeatedly performed E times, wherein the sum of the D times and the E times may be equal to Z times, which is the number of repetitions of the third unit process (U30). For example, the third unit process (U30) that is repeatedly performed twice may be divided into a 3-1 unit process (U31) that is repeatedly performed once, and a 3-2 unit process (U32) that is repeatedly performed once.

[0098] As described above, when the first unit process (U10) is divided into the 1-1 to 1-3 unit processes (U11, U12, U13), and the third unit process (U30) is divided into the 3-1 and 3-2 unit processes (U31, U32), the 1-1 unit process (U11) is performed before the 2nd unit process (U20), the 1-2 unit process (U12) is performed after the 2nd unit process (U20) and before the 3-1 unit process (U31), the 1-3 unit process (U13) is performed after the 3-1 unit process (U31) and before the 3-2 unit process (U32), the 2nd unit process (U20) is performed after the 1-1 unit process (U11) and before the 1-2 unit process (U12), and the 3-1 unit process (U31) is performed The 1-2 unit process (U12) may be performed before the 1-3 unit process (U13), and the 3-2 unit process (U32) may be performed after the 1-3 unit process (U13).

[0099] According to one embodiment, the 1-1 unit process (U11) may include a first indium precursor providing step (S111a) - a purge step (S112a) - a 1-1 reactant providing step (S113a) - a purge step (S114a). Alternatively, the 1-2 unit process (U12) may include a second indium precursor providing step (S111b) - a purge step (S112b) - a 1-2 reactant providing step (S113b) - a purge step (S114b). Alternatively, the 1-3 unit process (U13) may include a third indium precursor providing step (S111c) - a purge step (S112c) - a 1-3 reactant providing step (S113c) - a purge step (S114c).

[0100] According to one embodiment, the 3-1 unit process (U31) may include a first zinc precursor providing step (S131a) - a purge step (S132a) - a 3-1 reactant providing step (S133a) - a purge step (S134a). Alternatively, the 3-2 unit process (U32) may include a second zinc precursor providing step (S131b) - a purge step (S132b) - a 3-2 reactant providing step (S133b) - a purge step (S134b).

[0101] That is, the IGZO material film (100) can be formed through the steps of forming the first material film (110) - forming the second material film (120) - forming the first material film (110) - forming the third material film (130) - forming the first material film (110) - forming the third material film (130).

[0102] As described above, by dividing the number of repetitions of the first unit process (U10) and the third unit process (U20), the sum of the thicknesses of the first material film (110) and the third material film (130) can be relatively reduced (e.g., reduced to 2 nm or less), and thus the crystallinity of the IGZO material film (100) can be relatively reduced, so that formation of an amorphous structure can be easily achieved.

[0103] For example, compared to an IGZO material film formed by controlling the number of repetitions of the first unit process: the number of repetitions of the second unit process: the number of repetitions of the third unit process to 27:1:2, an IGZO material film formed by controlling the number of repetitions of the first unit process: the number of repetitions of the second unit process: the number of repetitions of the first unit process: the number of repetitions of the third unit process: the number of repetitions of the first unit process: the number of repetitions of the third unit process to 9:1:9:1:9:1 may have a relatively reduced thickness of the first material film (110) and the third material film (130), and may also have a reduced crystallinity.

[0104]

[0105] Above, the design method for an atomic layer deposition process according to embodiments of the present invention has been described. Below, specific experimental examples and characteristic evaluation results for the design method for an atomic layer deposition process according to embodiments of the present invention are described.

[0106] Experimental Example 1: Comparison of Homogeneous IGZO and Heterogeneous IGZO

[0107] Homogeneous IGZO material films and heterogeneous IGZO material films were prepared. Specifically, the homogeneous IGZO material film was manufactured by a PEALD method in which an indium precursor (DADI), a gallium precursor (TMGa), a zinc precursor (DEZ), and oxygen plasma (O2plasma) were simultaneously injected. In contrast, the heterogeneous IGZO material film was manufactured by a PEALD method using an indium precursor (DADI), a gallium precursor (TMGa), a zinc precursor (DEZ), and oxygen plasma (O2plasma), but was manufactured at a ratio of In:Ga:Zn=5:3:2. The ratio of In:Ga:Zn=5:3:2 means that the number of repetitions of the first unit process described with reference to FIGS. 1 to 3: the number of repetitions of the second unit process: the number of repetitions of the third unit process were performed at a ratio of 5:3:2.

[0108] FIG. 6 is a drawing for explaining the GIWAXS analysis results of a homogenous IGZO material film according to Experimental Example 1 of the present invention, and FIG. 7 is a drawing for explaining the GIWAXS analysis results of a heterogenous IGZO material film according to Experimental Example 2 of the present invention.

[0109] Referring to FIGS. 6 and 7, the crystallinity is shown through the GIWAX analysis results of the homogenous IGZO material film and the heterogenous IGZO material film. In addition, the compositions of the homogenous IGZO material film and the heterogenous IGZO material film were analyzed, and the analysis results are summarized in below.

[0110] at%InGaZnHomogenous IGZO31.232.636.3Heterogenous IGZO32.533.034.5

[0111] As can be seen in , the compositions of the homogenous IGZO material film and the heterogenous IGZO material film are substantially the same.

[0112] In addition, as can be seen in Fig. 6, the homogenous IGZO material film exhibits crystalline characteristics, whereas as can be seen in Fig. 7, the heterogenous IGZO material film exhibits amorphous characteristics. In particular, as can be seen in the enlarged drawing of the oscillation region, unlike the homogenous IGZO material film, a peak according to the 5:3:2 design appears in the heterogenous IGZO material film.

[0113] FIG. 8 is a drawing for explaining the electrical characteristics of a TFT to which a homogenous IGZO material film according to Experimental Example 1 of the present invention is applied, and FIG. 9 is a drawing for explaining the electrical characteristics of a TFT to which a heterogenous IGZO material film according to Experimental Example 1 of the present invention is applied.

[0114] Referring to FIGS. 8 and 9, the electrical characteristics of a TFT (Thin Film Transistor) having a top gate bottom contact structure in which a homogenous IGZO material film or a heterogenous IGZO material film is applied as a channel are measured and shown. The measured results are summarized in below.

[0115] 400℃ 3h airHomogenous IGZOHeterogenous IGZOV th (V)-4.28 ± 0.32-0.56 ± 0.03μ lin (cm 2 / Vs)6.47 ± 0.9936.1 ± 5.71μ sat (cm 2 / Vs)4.95 ± 0.4539.1 ± 2.49SS (V / decade)0.23 ± 0.060.07 ± 0.01Hysteresis (V)0.04 ± 0.010.00 ± 0.00

[0116] As can be seen in FIG. 8, FIG. 9, and , the electrical characteristics of the TFT to which the heterogeneous IGZO material film is applied are significantly higher than those of the TFT to which the homogeneous IGZO material film is applied.

[0117] FIG. 10 is a drawing for explaining the reliability of a TFT to which a homogenous IGZO material film is applied according to Experimental Example 1 of the present invention, and FIG. 11 is a drawing for explaining the reliability of a TFT to which a heterogenous IGZO material film is applied according to Experimental Example 1 of the present invention.

[0118] Referring to (a) of FIG. 10, the PBTS result of a top gate bottom contact structure TFT to which a homogenous IGZO material film is applied as a channel is shown, and referring to (b) of FIG. 10, the NBTS result of a top gate bottom contact structure TFT to which a homogenous IGZO material film is applied as a channel is shown, and referring to (a) of FIG. 11, the PBTS result of a top gate bottom contact structure TFT to which a heterogenous IGZO material film is applied as a channel is shown, and referring to (b) of FIG. 11, the NBTS result of a top gate bottom contact structure TFT to which a heterogenous IGZO material film is applied as a channel is shown.

[0119] As can be seen in FIGS. 10 and 11, it can be confirmed that the reliability of the TFT to which the heterogeneous IGZO material film is applied is higher compared to the TFT to which the homogenous IGZO material film is applied.

[0120]

[0121] Experimental Example 2: Comparison of Manufacturing Process Designs for Heterogeneous IGZO Films

[0122] Heterogeneous IGZO material films were manufactured by the PEALD method using an indium precursor (DADI), a gallium precursor (TMGa), a zinc precursor (DEZ), and oxygen plasma (O2plasma), with different In:Ga:Zn ratios. The In:Ga:Zn ratio refers to the ratio of the number of repetitions of the first unit process described with reference to FIGS. 1 to 3: the number of repetitions of the second unit process: the number of repetitions of the third unit process. Specifically, the IGZO material film manufactured at a ratio of In:Ga:Zn=5:3:2, In:Ga:Zn=10:6:4, In:Ga:Zn=15:9:6, and In:Ga:Zn=20:12:8 is defined as Experimental Example 2-1 (Ex 2-1), the IGZO material film manufactured at a ratio of In:Ga:Zn=10:6:4 is defined as Experimental Example 2-2 (Ex 2-2), the IGZO material film manufactured at a ratio of In:Ga:Zn=15:9:6 is defined as Experimental Example 2-3 (Ex 2-3), and the IGZO material film manufactured at a ratio of In:Ga:Zn=20:12:8 is defined as Experimental Example 2-4 (Ex 2-4).

[0123] In:Ga:Zn ratioEx 2-15:3:2Ex 2-210:6:4Ex 2-315:9:6Ex 2-420:12:8

[0124] Fig. 12 is a drawing for explaining the results of confirming the oscillation pattern of the IGZO material film according to Experimental Examples 2-1 to 2-4 of the present invention.

[0125] Referring to (a) to (d) of FIG. 12, the results of confirming the oscillation pattern through XRR for each of the IGZO material films (Ex 2-1, Ex 2-2, Ex 2-3, Ex 2-4) according to the above experimental examples 2-1 to 2-4 are shown. In addition, the composition and individual film thickness were measured for each of the IGZO material films (Ex 2-1, Ex 2-2, Ex 2-3, Ex 2-4) according to the above experimental examples 2-1 to 2-4, and the measured results are summarized in and below.

[0126] Classification In (at%)Ga (at%)Zn (at%)Total Thickness (nm)Ex 2-131.232.636.30.96Ex 2-232.431.136.51.94Ex 2-333.330.236.52.90Ex 2-430.830.738.53.88

[0127] ClassificationIn material film (nm)Ga material film (nm)Zn material film (nm)Ex 2-10.370.260.33Ex 2-20.740.530.67Ex 2-31.110.791.00Ex 2-41.481.061.34

[0128] As can be seen in , it can be confirmed that the IGZO material film manufactured in the ratio of In:Ga:Zn=(5:3:2) x n (n is an integer from 1 to 4) has a composition that is substantially constant (within 4.3% error) regardless of the ratio of In:Ga:Zn.

[0129] In addition, as can be confirmed in FIG. 12 and , the IGZO material films according to Experimental Example 2-1 (Ex 2-1) and Experimental Example 2-2 (Ex 2-2) in which the sum of the thicknesses of the In material film and the Zn material film is 2 nm or less exhibit amorphous characteristics, whereas the IGZO material films according to Experimental Example 2-3 (Ex 2-3) and Experimental Example 2-4 (Ex 2-4) in which the sum of the thicknesses of the In material film and the Zn material film is more than 2 nm exhibit crystalline characteristics.

[0130] Accordingly, when forming an IGZO material film by the atomic layer deposition method, it can be seen that by controlling the ratio of In:Ga:Zn to (5:3:2) x n (n is an integer greater than or equal to 1 and less than or equal to 2), the sum of the thicknesses of the In material film and the Zn material film can be controlled to 2 nm or less, and thus the IGZO material film can be formed in an amorphous state.

[0131] FIG. 13 is a schematic diagram of a TFT to which an IGZO material film is applied according to Experimental Examples 2-1 to 2-4 of the present invention, and FIGS. 14 and 15 are drawings for explaining the electrical characteristics of a TFT to which an IGZO material film is applied according to Experimental Examples 2-1 to 2-4 of the present invention.

[0132] Referring to FIG. 13, a schematic diagram of a TFT having a bottom gate top contact structure in which an IGZO material film (Ex 2-1, Ex 2-2, Ex 2-3, Ex 2-4) according to Experimental Examples 2-1 to 2-4 is applied as a channel is shown, and referring to FIG. 14 and FIG. 15, the results of measuring the electrical characteristics of the above-described TFT are shown.

[0133] As can be seen in FIGS. 14 and 15, in the case of the TFT to which the IGZO material film (Ex 2-3, Ex 2-4) according to Experimental Examples 2-3 and 2-4 is applied, it can be seen that the electrical characteristics are significantly lower compared to the TFT to which the IGZO material film (Ex 2-1, Ex 2-2) according to Experimental Examples 2-1 and 2-2 is applied.

[0134] Fig. 16 is a drawing for explaining the results of crystallinity evaluation of IGZO material films according to experimental examples 2-1 to 2-4 of the present invention.

[0135] Referring to FIG. 16, the results of crystallinity evaluation through XRD analysis are shown for each of the IGZO material films (Ex 2-1, Ex 2-2, Ex 2-3, Ex 2-4) according to Experimental Examples 2-1 to 2-4. As can be seen in FIG. 16, it can be confirmed that the crystallinity shape changes sharply in the IGZO material films (Ex 2-3, Ex 2-4) according to Experimental Examples 2-3 and 2-4. That is, when the IGZO material film is manufactured by controlling the ratio of In:Ga:Zn to (5:3:2) x n (n is an integer of 1 to 4), the IGZO material film is formed amorphously when n is an integer range of 1 to 2, but it can be confirmed that the IGZO material film is formed to have crystallinity when n is an integer range of 3 to 4.

[0136]

[0137] Experimental Example 3: Comparison of Single Material Film Thickness in Heterogeneous IGZO Material Films

[0138] Heterogeneous IGZO material films were manufactured by the PEALD method using an indium precursor (DADI), a gallium precursor (TMGa), a zinc precursor (DEZ), and oxygen plasma (O2plasma), with different In:Ga:Zn ratios. The In:Ga:Zn ratio refers to the ratio of the number of repetitions of the first unit process described with reference to FIGS. 1 to 3: the number of repetitions of the second unit process: the number of repetitions of the third unit process. Specifically, the IGZO material film manufactured at a ratio of In:Ga:Zn=16:1:1, In:Ga:Zn=32:2:2, and In:Ga:Zn=48:3:3 is defined as Experimental Example 3-1 (Ex 3-1), the IGZO material film manufactured at a ratio of In:Ga:Zn=32:2:2 is defined as Experimental Example 3-2 (Ex 3-2), and the IGZO material film manufactured at a ratio of In:Ga:Zn=48:3:3 is defined as Experimental Example 3-3 (Ex 3-3).

[0139] In:Ga:Zn ratioEx 3-116:1:1Ex 3-232:2:2Ex 3-348:3:3

[0140] FIG. 17 is a drawing for explaining the crystallinity evaluation results of the IGZO material film according to Experimental Examples 3-1 to 3-3 of the present invention, and FIG. 18 is a TEM image of the IGZO material film according to Experimental Examples 3-1 to 3-3 of the present invention.

[0141] Referring to Fig. 17, the results of crystallinity evaluation through XRD analysis are shown for each of the IGZO material films (Ex 3-1, Ex 3-2, Ex 3-3) according to the above experimental examples 3-1 to 3-3. As can be seen in Fig. 17, as the number of repetitions of the In material film manufacturing cycle (first unit process) increases (Ex 3-1 -> Ex 3-3), it can be confirmed that the crystallinity peak close to cubic-In2O3(222) appears higher.

[0142] Referring to (a) to (c) of FIG. 18, TEM (Transmission Electron Microscopy) images are shown for each of the IGZO material films (Ex 3-1, Ex 3-2, Ex 3-3) according to the experimental examples 3-1 to 3-3.

[0143] As can be seen in (a) to (c) of Fig. 18, the IGZO material film (Ex 3-1) according to the experimental example 3-1 exhibits amorphous characteristics, whereas the IGZO material films (Ex 3-2, Ex 3-3) according to the experimental examples 3-2 and 3-3 exhibit crystalline characteristics.

[0144] In addition, the film thickness was calculated based on the GPC (growth per cycle) during single film growth for each of the IGZO material films (Ex 3-1, Ex 3-2, Ex 3-3) according to the above experimental examples 3-1 to 3-3, and the calculated results are summarized in below.

[0145] ClassificationIn material film (nm)Ga material film (nm)Zn material film (nm)Ex 3-11.280.130.20Ex 3-22.560.260.40Ex 3-33.840.390.60

[0146] As can be seen in , when the sum of the thicknesses of the In material film and the Zn material film is 2 nm or less, the IGZO material film is formed in an amorphous state, but when it exceeds 2 nm, it is formed to have crystallinity.

[0147]

[0148] Experimental Example 4: Confirming Characteristic Changes According to Cycle Division

[0149] Heterogeneous IGZO material films were manufactured by the PEALD method using an indium precursor (DADI), a gallium precursor (TMGa), a zinc precursor (DEZ), and oxygen plasma (O2plasma), and the ratios of In:Ga:Zn were different. The ratio of In:Ga:Zn refers to the ratio of the number of repetitions of the first unit process described with reference to FIGS. 1 to 3: the number of repetitions of the second unit process: the number of repetitions of the third unit process. Specifically, the films were manufactured at ratios of In:Ga:Zn=48:3:3 and In:Ga:In:Zn=24:3:24:3, and the IGZO material film manufactured at the ratio of In:Ga:Zn=48:3:3 is defined as Experimental Example 4-1 (Ex 4-1), and the IGZO material film manufactured at the ratio of In:Ga:In:Zn=24:3:24:3 is defined as Experimental Example 4-2 (Ex 4-2).

[0150] Cycle ratio Ex 4-1 In:Ga:Zn=48:3:3 Ex 4-2 In:Ga:In:Zn=24:3:24:3

[0151] FIG. 19 is a drawing for explaining the crystallinity evaluation results of the IGZO material film according to Experimental Examples 4-1 and 4-2 of the present invention, and FIG. 20 is a TEM image of the IGZO material film according to Experimental Examples 4-1 and 4-2 of the present invention.

[0152] Referring to Fig. 19, the crystallinity evaluation results through XRD analysis are shown for each of the IGZO material films (Ex 4-1, Ex 4-2) according to Experimental Examples 4-1 and 4-2, and referring to Fig. 20, the TEM (Transmission Electron Microscopy) images are shown for each of the IGZO material films (Ex 4-1, Ex 4-2) according to Experimental Examples 4-1 and 4-2. As can be seen in Figs. 19 and 20, it can be confirmed that the crystallinity significantly decreases as the In cycle is divided (Ex 4-1 -> Ex 4-2).

[0153] In addition, the composition and film thickness of each IGZO material film (Ex 4-1, Ex 4-2) according to the above experimental examples 4-1 and 4-2 were confirmed, and the confirmation results are summarized in below.

[0154] ClassificationEx 4-1Ex 4-2XRF CompositionIn (at%)72.773.0Ga (at%)15.515.1Zn (at%)11.811.9Film thicknessIn material film (nm)3.841.92Ga material film (nm)0.390.39Zn material film (nm)0.600.60

[0155] As can be seen in , the composition of the IGZO material film remains substantially constant despite the division of the In cycle. In addition, it can be confirmed that the thickness of the In material film is significantly reduced as the In cycle is divided.

[0156] FIG. 21 is a schematic diagram of a TFT to which an IGZO material film is applied according to Experimental Examples 4-1 and 4-2 of the present invention, FIG. 22 is a diagram for explaining the electrical characteristics of a TFT to which an IGZO material film is applied according to Experimental Examples 4-1 and 4-2 of the present invention, and FIG. 23 is a diagram for explaining the reliability of a TFT to which an IGZO material film is applied according to Experimental Examples 4-1 and 4-2 of the present invention.

[0157] Referring to Fig. 21, a schematic diagram of a TFT having a top gate bottom contact structure in which an IGZO material film (Ex 4-1, Ex 4-2) according to Experimental Examples 4-1 and 4-2 is applied as a channel is shown, Fig. 22 shows the mobility measurement results of the above-described TFT, and Fig. 23 shows the PBTS results of the above-described TFT.

[0158] As can be seen in Fig. 22, as the In cycle is divided (Ex 4-1, Ex 4-2), the mobility of the TFT improves (30.4 cm 2 / Vs -> 41.9 cm 2 / Vs) can be confirmed. In addition, as can be confirmed in Fig. 23, it can be confirmed that the reliability of the TFT improves as the In cycle is divided.

[0159]

[0160] Experimental Example 5: Confirmation of Characteristic Changes According to In Cycle and Zn Cycle Splitting

[0161] Heterogeneous IGZO material films were manufactured by the PEALD method using an indium precursor (DADI), a gallium precursor (TMGa), a zinc precursor (DEZ), and oxygen plasma (O2plasma), with different In:Ga:Zn ratios. The In:Ga:Zn ratio refers to the ratio of the number of repetitions of the first unit process described with reference to FIGS. 1 to 3: the number of repetitions of the second unit process: the number of repetitions of the third unit process. Specifically, the IGZO material film manufactured at a ratio of In:Ga:Zn=27:1:2, In:Ga:In:Zn=13:1:14:2, In:Ga:In:Zn:In:Zn=9:1:9:1:9:1 is defined as Experimental Example 5-1 (Ex 5-1), the IGZO material film manufactured at a ratio of In:Ga:In:Zn=13:1:14:2 is defined as Experimental Example 5-2 (Ex 5-2), and the IGZO material film manufactured at a ratio of In:Ga:In:Zn:In:Zn=9:1:9:1:9:1 is defined as Experimental Example 5-3 (Ex 5-3).

[0162] Cycle ratio Ex 5-1 In:Ga:Zn=27:1:2 Ex 5-2 In:Ga:In:Zn=13:1:14:2 Ex 5-3 In:Ga:In:Zn:In:Zn=9:1:9:1:9:1

[0163] FIG. 24 is a drawing comparing the growth rate, XPS analysis results, XPS analysis results, and composition of IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0164] Referring to (a) of Fig. 24, the growth rate (GR) and refractive index (RI) of the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to the experimental examples 5-1 to 5-3 are compared. As can be seen in (a) of Fig. 24, as the number of cycle divisions increases (Ex 5-1 -> Ex 5-3), the growth rate decreases while the refractive index slightly increases.

[0165] Referring to (b) of FIG. 24, the XPS analysis results of the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to the experimental examples 5-1 to 5-3 are shown, and referring to (c) of FIG. 24, the XPS C1 peak analysis results of the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to the experimental examples 5-1 to 5-3 are shown.

[0166] As can be seen in (b) and (c) of Fig. 24, it can be confirmed that the peak distributions of the XPS analysis results of the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to the experimental examples 5-1 to 5-3 are similar.

[0167] Referring to (d) of Fig. 24, the compositions of the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to Experimental Examples 5-1 to 5-3 are compared and shown. As can be confirmed in (d) of Fig. 24, the compositions of the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to Experimental Examples 5-1 to 5-3 are substantially the same.

[0168] FIG. 25 is a drawing for explaining the crystallinity evaluation results of the IGZO material film according to Experimental Examples 5-1 to 5-3 of the present invention, and FIG. 26 is a drawing for explaining the density difference of the IGZO material film according to Experimental Examples 5-1 to 5-3 of the present invention.

[0169] Referring to FIG. 25, the results of crystallinity evaluation through XRD analysis are shown for each of the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to Experimental Examples 5-1 to 5-3, and referring to FIG. 26, the experimentally measured density (Experimental) and the simulated density (Simulated) are compared for each of the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to Experimental Examples 5-1 to 5-3. As can be seen in FIG. 25 and FIG. 26, it can be confirmed that the crystallinity and density decrease as the number of cycle divisions increases (Ex 5-1 -> Ex 5-3). In particular, it can be confirmed that the IGZO material film (Ex 5-3) according to Experimental Example 5-3 exhibits amorphous characteristics.

[0170] In addition, the composition and film thickness of each IGZO material film (Ex 5-1, Ex 5-2, Ex 5-3) according to the above experimental examples 5-1 to 5-3 were confirmed, and the confirmation results are summarized in below.

[0171] ClassificationEx 5-1Ex 5-2Ex 5-3XRF CompositionIn (at%)57.760.763.5Ga (at%)31.330.530.0Zn (at%)10.08.86.5Film thicknessIn material film (nm)3.511.69~1.821.17Ga material film (nm)0.080.080.08Zn material film (nm)0.340.340.17

[0172] As can be seen in , the composition of the IGZO material film remains substantially constant despite the division of the cycle. In addition, it can be confirmed that the thickness of the In material film and the Zn material film decreases as the In cycle and Zn cycle are divided.

[0173] In addition, as can be seen in FIGS. 25 to 26 and , in the case of the IGZO material film (Ex 5-1) according to Experimental Example 5-1, the thickness of the In material film is 2 nm or more (3.51 nm), in the case of the IGZO material film (Ex 5-2) according to Experimental Example 5-2, the sum of the thicknesses of the In material film and the Zn material film is 2 nm or more (2.16 nm), and in the case of the IGZO material film (Ex 5-3) according to Experimental Example 5-3, both the single thickness of the In material film and the sum of the thicknesses of the In material film and the Zn material film are 2 nm or less. Based on the increase in peak intensity of XRD and the increase in density (0.1) measured by XRR, microcrystallinity begins to appear when the sum of the thicknesses of the In material film and the Zn material film exceeds 2 nm. In the case of Experimental Example 5-1 (Ex 5-1) where the thickness of the In material film is 3.51 nm, the intensity increases relatively greatly and the increase in density (0.25) is also relatively higher, so it can be estimated that microcrystallinity appears more greatly.

[0174] Figure 27 is a drawing comparing the surface roughness of IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0175] Referring to (a) of FIG. 27, the surface roughness measured using AFM for the IGZO material film (Ex 5-1) according to the experimental example 5-1 is shown, and referencing (b) of FIG. 27, the surface roughness measured using AFM for the IGZO material film (Ex 5-2) according to the experimental example 5-2 is shown, and referencing (c) of FIG. 27, the surface roughness measured using AFM for the IGZO material film (Ex 5-3) according to the experimental example 5-3 is shown.

[0176] As can be seen in (a) to (c) of Fig. 27, the more cycle divisions are made (Ex 5-1 -> Ex 5-2 -> Ex 5-3), the higher the surface roughness (R q) can also be confirmed to decrease (0.153 nm -> 0.146 nm -> 0.100 nm).

[0177] FIG. 28 is a drawing for explaining the XPS O 1s analysis results of the IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention, and FIG. 29 is a drawing for comparing the O 1s sub-peak area ratios of the IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0178] As can be confirmed in FIGS. 28 and 29, it can be confirmed that the IGZO material films (Ex 5-1, Ex 5-2, Ex 5-3) according to the experimental examples 5-1 to 5-3 have substantially constant XPS O 1s analysis results and O 1s sub-peak area ratios.

[0179] FIG. 30 is a schematic diagram of a TFT to which an IGZO material film is applied according to Experimental Examples 5-1 to 5-3 of the present invention, FIGS. 31 and 32 are drawings for explaining the electrical characteristics of a TFT to which an IGZO material film is applied according to Experimental Examples 5-1 to 5-3 of the present invention, and FIGS. 33 and 34 are drawings for explaining the reliability of a TFT to which an IGZO material film is applied according to Experimental Examples 5-1 to 5-3 of the present invention.

[0180] Referring to FIG. 30, a schematic diagram of a TFT having a bottom gate top contact structure in which an IGZO material film (Ex 5-1, Ex 5-2, Ex 5-3) according to Experimental Examples 5-1 to 5-3 is applied as a channel is shown, and referring to FIGS. 31 and 32, the results of electrical characteristic measurements of the above-described TFT are shown, and referring to FIG. 33, the results of PBTS of the above-described TFT are shown, and referring to FIG. 34, the results of NBTS of the above-described TFT are shown.

[0181] As can be seen in FIGS. 31 to 34, when the sum of the thicknesses of the In material film and the Zn material film is 2 nm or less (Ex 5-3), it can be seen that the electrical characteristics and reliability are relatively improved compared to when the sum exceeds 2 nm (Ex 5-1, Ex 5-2).

[0182] Figure 35 is a drawing for more specifically comparing the crystallinity of IGZO material films according to Experimental Examples 5-1 to 5-3 of the present invention.

[0183] Referring to (a) of FIG. 35, the cubic (222) peak area ratio and the amorphous area ratio in the IGZO material film (Ex 5-1) according to the experimental example 5-1 are shown, and referring to (b) of FIG. 35, the cubic (222) peak area ratio and the amorphous area ratio in the IGZO material film (Ex 5-2) according to the experimental example 5-2 are shown, and referring to (c) of FIG. 35, the cubic (222) peak area ratio and the amorphous area ratio in the IGZO material film (Ex 5-3) according to the experimental example 5-3 are shown.

[0184] CategoryCubic (222)(peak area ratio, %)Amorphous(peak area ratio, %)Ex 5-155.944.1Ex 5-242.557.5Ex 5-3-100

[0185] As can be confirmed in Fig. 35 and , it can be confirmed once again that the IGZO material film according to Experimental Example 5-3 has an amorphous structure.

[0186] Figure 36 is a drawing to explain why the sum of the thicknesses of the In material film and the Zn material film is more important than the sum of the thicknesses of the In material film and the Ga material film in order to implement an amorphous IGZO material film.

[0187] Referring to (a) of Fig. 36, the crystallinity of the In material film (In2O3) in the IGZO material film is shown, referencing (b) of Fig. 36, the crystallinity of the Ga material film (Ga2O3) in the IGZO material film is shown, and referencing (c) of Fig. 36, the crystallinity of the Zn material film (ZnO) in the IGZO material film is shown. In addition, the red and blue lines in the drawings represent the measurement results for material films formed at different deposition temperatures.

[0188] As can be seen in (a) to (c) of Fig. 36, the Ga material film has an amorphous characteristic based on a single film, whereas the In material film and the Zn material film have crystalline characteristics. Therefore, in order to implement an amorphous IGZO material film, it can be seen that the sum of the thicknesses of the In material film and the Zn material film is more important than the sum of the thicknesses of the In material film and the Ga material film.

[0189] Figure 37 is a drawing for explaining another atomic layer deposition process design method for implementing an amorphous IGZO material film.

[0190] Referring to FIG. 37, various characteristics of IGZO material films manufactured based on indium precursor (DADI), gallium precursor (TMGa), and zinc precursor (DEZ) are shown.

[0191] More specifically, the upper table shows a single film (In, Ga, ZnO x) shows an example of a composition that can be designed through a super-cycle when the GPC and density according to the ALD process are determined. The thickness, molecule, and composition were calculated based on the information, and judging based on this, in the case of 36:1:1, the single thickness of the In material film is 2 nm or more, and in the case of 15:10:10, the combined thickness of the In material film and the Zn material film is 2 nm or more, so it can be expected that polycrystallinity will appear. In contrast, even when the composition, GPC, and density are given, the thickness of each layer can be obtained based on the conventional super-cycle standard.

[0192] The table below shows the super-cycle design differences to reduce the single thickness of the In material film within the same composition to less than 2 nm. When applying the process, In 0.91 Ga 0.02 Zn 0.07 Within the compositional region of O, it can be expected that a near-amorphous thin film will be obtained.

[0193]

[0194] While the present invention has been described in detail using preferred embodiments, the scope of the present invention is not limited to the specific embodiments described above, and should be interpreted in accordance with the appended claims. Furthermore, those skilled in the art will appreciate that numerous modifications and variations are possible without departing from the scope of the present invention.

[0195] The present invention can be used in the semiconductor industry.

Claims

1. In a design method of an atomic layer deposition process for manufacturing an amorphous oxide semiconductor material film, the design method of the atomic layer deposition process is: A step of performing a first unit process of providing an indium (In) precursor and a first reactant on a substrate, thereby forming a first material film in which the indium precursor and the first reactant are reacted; A step of performing a second unit process of providing a gallium (Ga) precursor and a second reactant on the first material film to form a second material film in which the gallium precursor and the second reactant are reacted; and A step of performing a third unit process of providing a zinc (Zn) precursor and a third reactant on the second material film to form a third material film in which the zinc precursor and the third reactant are reacted, The above first unit process to the above third unit process are each performed repeatedly multiple times, A design method for an atomic layer deposition process, comprising controlling the crystallinity of an IGZO material film including the first to third material films by controlling the number of repetitions of each of the first to third unit processes.

2. In paragraph 1, A design method for an atomic layer deposition process, comprising forming an amorphous IGZO material film by controlling the number of repetitions of the first unit process: the number of repetitions of the second unit process: the number of repetitions of the third unit process in a ratio of (5:3:2) x n (n is an integer greater than or equal to 1 and less than or equal to 2).

3. In paragraph 1, A design method for an atomic layer deposition process, comprising controlling the thickness of each of the first material film to the third material film as the number of repetitions of each of the first unit process to the third unit process is controlled.

4. In paragraph 3, A design method for an atomic layer deposition process, comprising forming an amorphous IGZO material film by controlling the thickness of the first material film to 2 nm or less.

5. In paragraph 3, A design method for an atomic layer deposition process, comprising forming an amorphous IGZO material film by controlling the sum of the thickness of the first material film and the thickness of the third material film to 2 nm or less.

6. In paragraph 1, The first unit process includes a step of providing the indium precursor on the substrate and a step of providing the first reactant on the substrate on which the indium precursor is provided. The second unit process includes a step of providing the gallium precursor on the first material film and a step of providing the second reactant on the first material film on which the gallium precursor is provided. A design method for an atomic layer deposition process, wherein the third unit process includes a step of providing the zinc precursor on the second material film and a step of providing the third reactant on the second material film on which the zinc precursor is provided.

7. In a design method of an atomic layer deposition process for manufacturing an amorphous oxide semiconductor material film, the design method of the atomic layer deposition process is: A step of performing a first unit process of providing an indium (In) precursor and a first reactant on a substrate, thereby forming a first material film in which the indium precursor and the first reactant are reacted; A step of performing a second unit process of providing a gallium (Ga) precursor and a second reactant on the first material film to form a second material film in which the gallium precursor and the second reactant are reacted; and A step of performing a third unit process of providing a zinc (Zn) precursor and a third reactant on the second material film to form a third material film in which the zinc precursor and the third reactant are reacted, The above first unit process to the above third unit process are each performed repeatedly multiple times, A design method for an atomic layer deposition process, comprising forming an IGZO material film including the first to third material films in an amorphous state by dividing the number of repetitions of at least one unit process among the first unit process and the third unit process.

8. In paragraph 7, A design method for an atomic layer deposition process, comprising: dividing the number of repetitions of at least one unit process among the first unit process and the third unit process, thereby controlling the sum of the thickness of the first material film and the thickness of the third material film to 2 nm or less, thereby forming the IGZO material film in an amorphous state.

9. In paragraph 7, The above first unit process includes a 1-1 unit process that is repeated A times and a 1-2 unit process that is repeated B times, A design method for an atomic layer deposition process, wherein the sum of the above times A and B is equal to X times, which is the number of times the first unit process is repeated.

10. In paragraph 9, The above 1-1 unit process is performed before the above 2nd unit process, A design method for an atomic layer deposition process, wherein the first and second unit processes are performed after the second unit process and before the third unit process.

11. In paragraph 7, The above first unit process includes a 1-1 unit process that is repeated A times, a 1-2 unit process that is repeated B times, and a 1-3 unit process that is repeated C times. The above 3rd unit process includes a 3-1 unit process that is repeatedly performed D times, and a 3-2 unit process that is repeatedly performed E times. The sum of the above times A, B, and C is equal to X times, which is the number of repetitions of the first unit process. A design method for an atomic layer deposition process, wherein the sum of the above D times and the above E times is equal to Z times, which is the number of repetitions of the third unit process.

12. In paragraph 11, The above 1-1 unit process is performed before the above 2nd unit process, The above 1-2 unit process is performed after the 2nd unit process and before the 3-1 unit process, The above 1-3 unit process is performed after the 3-1 unit process and before the 3-2 unit process, The above second unit process is performed after the above 1-1 unit process and before the above 1-2 unit process, The above 3-1 unit process is performed after the 1-2 unit process and before the 1-3 unit process, A design method for an atomic layer deposition process, wherein the above-mentioned 3-2 unit process is performed after the above-mentioned 1-3 unit process.

13. In an IGZO material film including a first material film containing indium (In), a second material film containing gallium (Ga), and a third material film containing zinc (Zn), An IGZO material film, wherein the sum of the thickness of the first material film and the thickness of the third material film is 2 nm or less, and has an amorphous structure.

14. In paragraph 13, An IGZO material film, which includes an interface formed between adjacent material films.

Images