Method for forming thin film using two types of silicon precursor compounds

Abstract

The present application relates to a method for manufacturing a silicon thin film using two types of silicon precursor compounds and, specifically, to a method for manufacturing a silicon thin film, which has excellent thin film characteristics and can control morphology according to the precursor, through atomic layer deposition (ALD) even at low temperatures.

Description

Method for forming a thin film using two types of silicon precursor compounds

[0001] The present invention relates to a method for forming a silicon thin film with excellent properties through atomic layer deposition (ALD) even at low temperatures using two types of silicon precursors.

[0002] Recent silicon-containing thin films can be manufactured into various forms through various processes in the semiconductor industry. In particular, silicon oxide and silicon nitride films, due to their excellent barrier properties and oxidation resistance, can be used as insulating films, diffusion barriers, hard masks, etch-stop layers, seed layers, spacers, trench isolation, intermetallic dielectric materials, or protective layers in device manufacturing. Recently, polycrystalline silicon thin films have been utilized in thin film transistors (TFTs) and solar cells, and their applications are increasingly diversifying.

[0003] Representative technologies known for manufacturing thin films containing silicon include atomic layer deposition (ALD), in which a gaseous precursor is physically or chemically adsorbed onto the substrate surface and then a film is formed by sequentially introducing a reaction gas; metalorganic chemical vapor deposition (MOCVD), in which a mixed gaseous organometallic precursor and a reaction gas react to form a film on the substrate surface or react directly on the surface to form a film; and various thin film manufacturing technologies such as low-pressure chemical vapor deposition (LPCVD) that apply this, plasma-enhanced chemical vapor deposition (PECVD) that enables deposition at low temperatures, and atomic layer deposition (PEALD) are being applied to the manufacturing processes of devices such as next-generation semiconductors, and are being used for forming ultra-fine patterns and depositing thin films with uniform and excellent properties in nano-scale thicknesses.

[0004] In particular, thin films used in semiconductor devices must be controlled at the atomic level and possess excellent step coverage characteristics. Atomic Layer Deposition (ALD) is a technology applicable to this purpose. As the development of highly directional thin film deposition methods capable of controlling thickness at the nanoscale becomes increasingly crucial, ALD is gaining attention as the most promising deposition technique for numerous applications in nanoscale devices. ALD is expected to address issues arising from device miniaturization, such as high leakage currents. Beyond the deposition of single high-k materials, ALD also offers the additional advantage of being able to deposit thin films with atomic-level compositional variations. The principle of ALD is that individual reactants separated by an inert gas (such as Ar or N2) are supplied onto a wafer, depositing a single atomic layer. This process is repeated to achieve the desired thickness. After one reactant undergoes chemical adsorption on the substrate, a second or third gas is introduced, causing further chemical adsorption on the substrate, forming a thin film. The reactants used are simple elements or compounds, and these reactants must be highly volatile, stable, and highly reactive.

[0005] However, when using precursors used in the existing atomic layer deposition method, a high temperature process of 600°C or higher is required, and at the same time, there is a problem that the reactants decompose in the high temperature process, causing defects, and the physical and electrical properties of the thin film, such as step coverage and etching characteristics, deteriorate.

[0006] Accordingly, the need for a process that enables low-temperature behavior of the deposition process, adhesion of thin films, excellent step coating properties, and thickness control at the atomic layer level is increasing.

[0007] As a result, there is a need to develop a method for manufacturing a thin film that is capable of atomic layer deposition even at low temperatures, has excellent step coating properties, and has excellent thin film properties.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] (Patent Document 1) Republic of Korea Publication Patent No. 2021-0024673

[0011] (Patent Document 2) Republic of Korea Publication Patent No. 2015-0102725

[0012] The present invention aims to provide a method for efficiently manufacturing a thin film at low temperatures using two types of silicon precursors and a thin film with excellent properties manufactured through the method.

[0013] In particular, the existing silicon thin film deposition method, low pressure chemical vapor deposition (LPCVD), formed a silicon thin film containing defects, and thus, a polycrystalline silicon (poly-Si) thin film with a small grain boundary size was formed during high-temperature crystallization.

[0014] Accordingly, the present invention aims to provide a method for manufacturing a thin film that can secure ALD behavior even at low temperatures below 500°C and enable conformal deposition even on patterns with a high aspect ratio by applying two types of silicon precursors to the atomic layer deposition method that utilizes thermal energy instead of the existing plasma.

[0015] However, the problems that the present invention seeks to solve are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0016] One aspect of the present invention comprises a first injection step of injecting a first precursor compound into a chamber; and

[0017] A second injection step of injecting a second precursor compound into the chamber is repeated to deposit a thin film,

[0018] The above first precursor compound is represented by the following chemical formula 1 or 2,

[0019] The above second precursor compound is represented by the following chemical formula 1 or 2:

[0020] A method for manufacturing a thin film can be provided.

[0021] (However, if the first precursor compound is a compound represented by the following chemical formula 1, the second precursor compound is a compound represented by the following chemical formula 2,

[0022] When the first precursor compound is a compound represented by the following chemical formula 2, the second precursor compound is a compound represented by the following chemical formula 1.

[0023]

[0024] [Chemical Formula 1]

[0025] Si x (R1) y H (2x+2-y)

[0026]

[0027] [Chemical Formula 2]

[0028] Si(NR2R3) z H (4-z)

[0029]

[0030] In the above chemical formulas 1 and 2,

[0031] R1 is any one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I),

[0032] R2 and R3 are each independently one selected from a group consisting of linear or branched hydrocarbons having 1 to 4 carbon atoms,

[0033] x is an integer from 1 to 3,

[0034] y is an integer from 1 to 7,

[0035] z is an integer from 1 to 3.

[0036] The method for manufacturing a thin film of this invention has the effect of efficiently manufacturing a silicon thin film with excellent properties.

[0037] Specifically, the present invention enables an atomic layer deposition process even at a low temperature of 500°C or lower by introducing two types of silicon precursor compounds, uses the precursor compounds as a source and a reactant, and can deposit an amorphous or nanocrystalline thin film depending on the type of the precursor compound.

[0038] In particular, by depositing an amorphous silicon thin film, a polycrystalline silicon thin film with a large grain boundary size can be manufactured during crystallization.

[0039] That is, the method for manufacturing a thin film of the present invention uses two types of silicon precursor compounds to enable uniform thin film deposition with excellent properties even at low temperatures, thereby ensuring excellent thin film properties, thickness, and step coverage, and controlling the morphology and crystallinity of the deposited thin film.

[0040] In addition, the thin film with excellent properties manufactured by the method for manufacturing the thin film of the present invention can be used as a dielectric, display, next-generation memory, non-memory semiconductor, etc. of various electronic devices.

[0041] Figure 1 (a) is a graph showing the change in thin film deposition rate according to the injection time of the first precursor compound (DIS) of Manufacturing Example 1 of the present application, and (b) is a graph showing the change in thin film deposition rate according to the injection time of the first precursor compound (TCDS) of Manufacturing Example 2 of the present application.

[0042] Figure 2 is a graph showing the change in thin film deposition rate according to the injection time of the second precursor compound (DIPAS) of Manufacturing Example 1 of the present invention.

[0043] Figure 3 (a) is a graph showing the change in deposition rate according to the process temperature of Manufacturing Example 1 of the present invention, and (b) is a graph showing the change in deposition rate according to the process temperature of Manufacturing Example 2 of the present invention.

[0044] Figure 4 (a) is a photograph showing the grain size of a thin film manufactured at a process temperature of 400°C in Manufacturing Example 1 of the present application measured using a scanning electron microscope (SEM), and Figure 4 (b) is a photograph showing the grain size of a thin film manufactured at a process temperature of 480°C in Manufacturing Example 1 of the present application measured using a scanning electron microscope.

[0045] Figure 5 (a) is a photograph showing the morphological characteristics of a thin film manufactured at a process temperature of 410°C in Manufacturing Example 2 of the present application, analyzed using an atomic force microscope (AFM), and Figure 5 (b) is a photograph showing the morphological characteristics of a thin film manufactured at a process temperature of 450°C in Manufacturing Example 2 of the present application, analyzed using an atomic force microscope.

[0046] Figure 6 (a) is a photograph showing the roughness of a thin film manufactured at a process temperature of 410°C in Manufacturing Example 2 of the present application measured using a scanning electron microscope, and Figure 6 (b) is a photograph showing the roughness of a thin film manufactured at a process temperature of 410°C in Manufacturing Example 3 of the present application measured using a scanning electron microscope.

[0047] Figure 7 (a) is a graph showing the morphological characteristics of a thin film manufactured at a process temperature of 410°C in Manufacturing Example 2 of the present application, measured using X-ray diffraction (XRD), and (b) is a graph showing the morphological characteristics of a thin film manufactured at a process temperature of 410°C in Manufacturing Example 2 of the present application, measured using X-ray diffraction.

[0048] Hereinafter, the functions and effects of the invention will be described in more detail through specific examples. However, these examples are provided merely as examples of the invention and do not define the scope of the invention.

[0049] Prior to this, the terms and words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present application based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0050] Accordingly, the configuration of the embodiments described in this specification is only one of the most preferred embodiments of the present application and does not represent all of the technical ideas of the present application, so it should be understood that various equivalents and modified examples that can replace them may exist at the time of filing this application.

[0051] In this specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise," "include," or "have" should be understood to indicate the presence of a feature, number, step, component, or combination thereof, but not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0052] In this specification, “a to b” and “a~b” indicating a numerical range are defined as “a to” and “~” as ≥ a and ≤ b.

[0053]

[0054] A method for manufacturing a thin film according to one aspect of the present invention comprises: a first injection step of injecting a first precursor compound into a chamber; and

[0055] A second injection step of injecting a second precursor compound into the chamber is repeated to deposit a thin film,

[0056] The above first precursor compound may be represented by the following chemical formula 1 or 2,

[0057] The above second precursor compound can be represented by the following chemical formula 1 or 2.

[0058] (However, if the first precursor compound is a compound represented by the following chemical formula 1, the second precursor compound may be a compound represented by the following chemical formula 2,

[0059] When the first precursor compound is a compound represented by the following chemical formula 2, the second precursor compound may be a compound represented by the following chemical formula 1.

[0060]

[0061] [Chemical Formula 1]

[0062] Si x (R1) y H (2x+2-y)

[0063]

[0064] [Chemical Formula 2]

[0065] Si(NR2R3) z H (4-z)

[0066]

[0067] In the above chemical formulas 1 and 2,

[0068] R1 is any one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I),

[0069] R2 and R3 are each independently one selected from a group consisting of linear or branched hydrocarbons having 1 to 4 carbon atoms,

[0070] x is an integer from 1 to 3,

[0071] y is an integer from 1 to 7,

[0072] z is an integer from 1 to 3.

[0073]

[0074] For example, the precursor compounds represented by the above chemical formula 1 or 2 may be injected in different orders.

[0075] That is, when the first precursor compound is a compound represented by the chemical formula 1, the second precursor compound is a compound represented by the chemical formula 2, and when the first precursor compound is a compound represented by the chemical formula 2, the second precursor compound may be a compound represented by the chemical formula 1.

[0076] For example, when the first precursor compound is diiodosilane (DIS), the second precursor compound may be diisopropyl aminosilane (DIPAS), and when the first precursor compound is diisopropyl aminosilane (DIPAS), the second precursor compound may be diiodosilane (DIPAS).

[0077] Additionally, when the first precursor compound is tetrachlorodisilane (TCDS), the second precursor compound may be diisopropyl aminosilane (DIPAS), and when the first precursor compound is diisopropyl aminosilane (DIPAS), the second precursor compound may be tetrachlorodisilane (TCDS).

[0078]

[0079] For example, the above R1 may be any one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), and preferably chlorine (Cl) or iodine (I).

[0080] For example, the above R2 and R3 can each independently be a linear or branched hydrocarbon having 1 to 2, 1 to 3, 1 to 4, 2 to 3, 2 to 4, and 3 to 4.

[0081] For example, x in the above chemical formula 1 can be 1, 2, or 3.

[0082] For example, y in the above chemical formula 1 may be 1 to 3 when x is 1, 1 to 5 when x is 2, and 1 to 7 when x is 3.

[0083] For example, z in the above chemical formula 2 can be 1, 2, or 3.

[0084]

[0085] In one embodiment, R1 of the chemical formula 1 is chlorine (Cl) or iodine (I),

[0086] x is 1 or 2,

[0087] y can be 2 or 4.

[0088]

[0089] In one embodiment, R2 and R3 of the above chemical formula 2 are each independently one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group,

[0090] z can be 1 or 2.

[0091]

[0092] In one embodiment, between the first injection step and the second injection step, a first purge step of injecting a first purge gas into the chamber; and

[0093] After the second injection step, a second purge step of injecting a second purge gas into the chamber may be further included.

[0094]

[0095] The method for manufacturing the above thin film may be atomic layer deposition (ALD) and chemical vapor deposition (CVD), and is preferably atomic layer deposition (ALD), but is not limited thereto.

[0096] In atomic layer deposition, the reactants must be highly volatile, stable, and highly reactive. In atomic layer deposition, reactant materials are supplied separately. During a single deposition cycle, a thin film less than a monolayer thick is grown through surface reaction. The ligands of the reactant materials adsorbed on the substrate are removed through a chemical reaction with other reactant materials supplied later. When heating precursor compounds, which are reactants for atomic layer deposition, in a liquid state can be significantly more advantageous in terms of reaction rate and process efficiency than in a solid state.

[0097] In one embodiment, the first and second purge gases may be inert gases such as argon (Ar), nitrogen (N2), or helium (He).

[0098] In one embodiment of the present invention, if the second precursor compound is not included, ALD behavior may not be smooth at low temperatures of 500°C or lower, and the morphology characteristics of the deposited thin film may deteriorate.

[0099] Additionally, in one embodiment of the present invention, the first precursor compound is a compound containing silicon (Si) atoms and may be a colorless liquid at room temperature.

[0100]

[0101] In one embodiment, the compound represented by the above chemical formula 1 is fluoro silane, chloro silane, bromo silane, iodo silane, difluoro silane, dichloro silane, dibromo silane, diiodo silane, trifluoro silane, trichloro silane, tribromo silane, triiodo silane, tetrafluoro silane, tetrachloro silane, tetrabromo silane, tetraiodo silane, fluorodisilane, chloro It can be chloro disilane, bromo disilane, iodo disilane, difluoro disilane, dichloro disilane, dibromo disilane, diiodo disilane, trifluoro disilane, trichloro disilane, tribromo disilane, triiodo disilane, tetrafluoro disilane, tetrachloro disilane, tetrabromo disilane, tetraiodo disilane.

[0102] For example, the precursor compound represented by the above chemical formula 1 may be any one selected from the group consisting of diiodosilane (DIS) and tetrachloro disilane (TCDS), but is not limited thereto.

[0103] In one embodiment, the compound represented by the above chemical formula 2 may be any one of dimethyl aminosilane, diethyl aminosilane, diisopropyl aminosilane, dibutyl aminosilane, diisobutyl aminosilane, dimethylethylsilane diamine, dimethylpropylsilane diamine, and bis(diethylamino)silane.

[0104] For example, the compound represented by the above chemical formula 2 may be any one selected from the group consisting of diisopropyl aminosilane (DIPAS) and bis(diethylamino)silane (BDEAS), but is not limited thereto.

[0105]

[0106] In one embodiment, the manufacturing method may have a process temperature of 350°C or more and 500°C or less.

[0107] For example, the process temperature is 350℃ or more and 500℃ or less, 360℃ or more and 500℃ or less, 370℃ or more and 500℃ or less, 380℃ or more and 500℃ or less, 390℃ or more and 500℃ or less, 400℃ or more and 500℃ or less, 370℃ or more and 490℃ or less, 390℃ or more and 485℃ or less, 395℃ or more and 480℃ or less, 400℃ or more and 475℃ or less, 360℃ or more and 480℃ or less, 370℃ or more and 460℃ or less, 380℃ or more and 440℃ or less, 390℃ or more and 430℃ or less, 400℃ or more and 420℃ or less, 350℃ or more and 490℃ or less, 350℃ or more and 480℃ or less, 350℃ or more and 470℃ or less, It can be 350℃ or more but 460℃ or less, 350℃ or more but 450℃ or less, 350℃ or more but 440℃ or less, 350℃ or more but 430℃ or less, 350℃ or more but 420℃ or less, 350℃ or more but 410℃ or less, 350℃ or more but 400℃ or less, 360℃ or more but 450℃ or less, 370℃ or more but 450℃ or less, 380℃ or more but 450℃ or less, 390℃ or more but 450℃ or less, 400℃ or more but 450℃ or less, 410℃ or more but 450℃ or less, 420℃ or more but 450℃ or less, 430℃ or more but 450℃ or less, 440℃ or more but 450℃ or less.

[0108]

[0109] In one embodiment, when the manufacturing method of the present invention is used to sequentially inject the first precursor and the second precursor of the present invention, a section (ALD window) in which the deposition rate is constant regardless of the process temperature can be confirmed at 350°C or higher and 500°C or lower.

[0110] Specifically, when the first precursor compound is diiodosilane (DIS), the process temperature may be 350°C or more and 500°C or less, preferably 400°C or more and 500°C or less, and more preferably 400°C or more and 450°C or less.

[0111] In addition, when the first precursor compound is tetrachloro disilane (TCDS), the process temperature may be 390°C or more and 450°C or less, preferably 400°C or more and 450°C or less, and more preferably 400°C or more and 420°C or less.

[0112]

[0113] Meanwhile, when producing a thin film according to the present invention at a low temperature below 350°C, proper deposition may not occur. This is because the reaction rate is insufficient, further slowing the deposition rate. Furthermore, the second precursor compound may not diffuse sufficiently, which may lead to defects or uniformity issues in the material and thin film, resulting in instability of the substrate or thin film.

[0114] Additionally, when producing a thin film according to the present invention at a high temperature exceeding 500°C, deposition may not occur properly. This may be due to the reaction rate being too fast, which may result in the generation of impurities, and the precursor or reactant gas may decompose, making it difficult to form a thin film.

[0115]

[0116] In one embodiment, when the first precursor compound is DIS and the second precursor compound is DIPAS, the thin film deposition rate (Growth rate per cycle GPC) by the manufacturing method may be 0.5 to 2.0 Å / cycle at a process temperature in the range of 400 to 500°C.

[0117] For example, when the first precursor compound is DIS, the thin film deposition rate by the above manufacturing method at a process temperature in the range of 400 to 500°C may be 0.5 to 2.0 Å cycle, 0.6 to 2.0 Å / cycle, 0.7 to 2.0 Å / cycle, 0.8 to 2.0 Å / cycle, 0.9 to 2.0 Å / cycle, 1.0 to 2.0 Å / cycle, 1.1 to 2.0 Å / cycle, 1.2 to 2.0 Å / cycle, 1.2 to 1.9 Å / cycle, 1.2 to 1.8 Å / cycle, 1.2 to 1.7 Å / cycle, 1.2 to 1.6 Å / cycle, 1.2 to 1.5 Å / cycle, 1.2 to 1.4 Å / cycle.

[0118]

[0119] In one embodiment, when the first precursor compound is TCDS and the second precursor compound is DIPAS, the thin film deposition rate by the manufacturing method may be 0.1 to 0.3 Å / cycle at a process temperature in the range of 400 to 450°C.

[0120] For example, when the first precursor compound is TCDS, the thin film deposition rate by the above manufacturing method at a process temperature in the range of 400 to 450°C may be 0.1 to 0.3 Å / cycle, 0.12 to 0.28 Å / cycle, 0.14 to 0.26 Å / cycle, 0.16 to 0.24 Å / cycle, 0.18 to 0.24 Å / cycle, 0.19 to 0.24 Å / cycle, 0.20 to 0.24 Å / cycle, 0.215 to 0.24 Å / cycle, 0.18 to 0.22 Å / cycle, 0.19 to 0.22 Å / cycle, 0.20 to 0.22 Å / cycle, 0.215 to 0.22 Å / cycle.

[0121]

[0122] In one embodiment, the temperature of the canister of the first precursor compound may be 0°C or more and 50°C or less.

[0123]

[0124] For example, the temperature of the canister of the first precursor compound may be 0°C or more and 50°C or less, 5°C or more and 45°C or less, 10°C or more and 40°C or less, 15°C or more and 35°C or less, 20°C or more and 25°C or less, 20°C or more and 30°C or less, 25°C or more and 30°C or less, 5°C or more and 30°C or less, 10°C or more and 30°C or less, or 15°C or more and 30°C or less.

[0125]

[0126] Additionally, the canister temperature of the second precursor compound may be 10°C or higher and 100°C or lower.

[0127] For example, the temperature of the canister of the second precursor compound may be 10°C or more and 100°C or less, 20°C or more and 100°C or less, 30°C or more and 100°C or less, 40°C or more and 100°C or less, 50°C or more and 100°C or less, 60°C or more and 100°C or less, 70°C or more and 100°C or less, 10°C or more and 90°C or less, 10°C or more and 80°C or less, 10°C or more and 70°C or less, 10°C or more and 60°C or less, 10°C or more and 50°C or less, or 10°C or more and 40°C or less.

[0128]

[0129] A canister is used to supply source gases and reaction gases into a chamber for reaction in a thin film manufacturing method. Typically, the canister vaporizes a precursor compound to generate source gases and reaction gases, which are then supplied into the chamber.

[0130] If the temperature of the canister is outside the above range, the uniformity of the thickness of the thin film manufactured through the method for manufacturing the thin film may be significantly reduced.

[0131] This is because, below the minimum temperature range, the supply of the precursor compound to the chamber is insufficient, and above the maximum temperature range, it may be difficult to obtain a uniform film due to deterioration caused by thermal energy or excessive supply of the precursor compound to the chamber.

[0132]

[0133] In one embodiment, the injection time of the first precursor compound may be 1 second or more and 30 seconds or less, and the injection time of the second precursor compound may be 1 second or more and 30 seconds or less, preferably, the injection time of the first precursor compound may be 1 second or more and 15 seconds or less, and the injection time of the second precursor compound may be 1 second or more and 15 seconds or less.

[0134]

[0135] For example, the injection time of the first precursor compound is 1 second or more and 20 seconds or less, 1 second or more and 15 seconds or less, 2 seconds or more and 15 seconds or less, 3 seconds or more and 15 seconds or less, 4 seconds or more and 15 seconds or less, 5 seconds or more and 15 seconds or less, 2 seconds or more and 10 seconds or less, 3 seconds or more and 10 seconds or less, 4 seconds or more and 10 seconds or less, 5 seconds or more and 10 seconds or less, 1 second or more and 10 seconds or less, 1 second or more and 8 seconds or less, 1 second or more and 6 seconds or less, 1 second or more and 5 seconds or less,

[0136] The injection time of the second precursor compound may be 1 second or more and 20 seconds or less, 1 second or more and 15 seconds or less, 2 seconds or more and 15 seconds or less, 3 seconds or more and 15 seconds or less, 4 seconds or more and 15 seconds or less, 5 seconds or more and 15 seconds or less, 2 seconds or more and 10 seconds or less, 3 seconds or more and 10 seconds or less, 4 seconds or more and 10 seconds or less, 5 seconds or more and 10 seconds or less, 1 second or more and 10 seconds or less, 1 second or more and 8 seconds or less, 1 second or more and 6 seconds or less, or 1 second or more and 5 seconds or less.

[0137]

[0138] If the process is performed while exceeding or falling short of the injection time of the first precursor compound and the second precursor compound as described above, it may be difficult to form an appropriate thin film.

[0139] Specifically, if the injection time of the first precursor compound falls short of the above range, the reactants necessary for forming the thin film may be insufficient, preventing the formation of a thin film of an appropriate thickness. On the other hand, if the injection time of the first precursor compound exceeds the above range, the composition ratio of the thin film produced may become inconsistent due to impurities resulting from the residual compound after the reaction.

[0140] Additionally, the injection time of the second precursor compound may vary depending on the type of the first precursor compound.

[0141] For example, when the first precursor compound is Diiodo silane (DIS), the injection time of the second precursor compound may be 1 second or more and 20 seconds or less, 2 seconds or more and 19 seconds or less, 3 seconds or more and 18 seconds or less, 4 seconds or more and 17 seconds or less, and preferably 5 seconds or more and 15 seconds or less.

[0142] For example, when the first precursor compound is tetrachloro disilane (TCDS), the injection time of the second precursor compound may be 1 second or more and 15 seconds or less, 2 seconds or more and 15 seconds or less, 3 seconds or more and 15 seconds or less, 4 seconds or more and 15 seconds or less, preferably 5 seconds or more and 15 seconds or less, and more preferably 10 seconds.

[0143] For example, when the first precursor compound is diisopropyl aminosilane (DIPAS), the injection time of the second precursor compound may be 1 second or more and 15 seconds or less, 2 seconds or more and 15 seconds or less, 3 seconds or more and 15 seconds or less, 4 seconds or more and 15 seconds or less, preferably 2 seconds or more and 10 seconds or less, and more preferably 5 seconds.

[0144]

[0145] If the injection time of the second precursor compound is less than 1 second, the residual amount of the first precursor compound, which is a reactant, may increase, resulting in an improper reaction and the generation of impurities, which may cause the thin film layer to be deposited unevenly. On the other hand, if the injection time of the second precursor compound exceeds 30 seconds, impurities due to the second precursor compound may be generated.

[0146]

[0147] In one embodiment, the purge gas injection time of the first purge step may be 1 second or more and 1 minute or less, and the purge gas injection time of the second purge step may be 1 second or more and 1 minute or less.

[0148]

[0149] In one embodiment, the first purge gas injection time of the first purge step is 1 second or more and 60 seconds or less, 1 second or more and 50 seconds or less, 1 second or more and 40 seconds or less, 1 second or more and 30 seconds or less, 1 second or more and 20 seconds or less, 1 second or more and 15 seconds or less, 1 second or more and 10 seconds or less,

[0150] The purge gas injection time of the second purge step may be 1 second or more and 60 seconds or less, 1 second or more and 50 seconds or less, 1 second or more and 40 seconds or less, 1 second or more and 30 seconds or less, 1 second or more and 20 seconds or less, 1 second or more and 15 seconds or less, or 1 second or more and 10 seconds or less.

[0151] If the injection time of the first or second purge gas is less than the above range, the residual amount of the first or second precursor compound may increase, causing an improper reaction, and impurities may not be purged, causing the thin film layer to be deposited unevenly.

[0152]

[0153] In one embodiment, the thin film may be in any one of an amorphous state, a mixed state of an amorphous state and a nanocrystalline state, and a nanocrystalline state.

[0154] Typically, atomic layer deposition (ALD) results in a disordered arrangement of atoms and molecules without a regular pattern. This typically occurs during rapid cooling or certain chemical processes, when there is insufficient time for the crystal structure to form.

[0155] Thin films in amorphous state can be produced by atomic layer deposition processes, and materials in this state generally have directionally constant thermal, mechanical, and electrical properties.

[0156] Nanocrystalline materials are materials with nanometer-scale crystal structures. Nanocrystalline materials possess unique physical properties due to their minute size and high surface-to-volume ratio. Materials in this state can exhibit electrical, optical, and mechanical properties distinct from those of amorphous materials. Nanocrystalline thin films can be manufactured using atomic layer deposition.

[0157] In the deposition process of a thin film, the morphology of the thin film can be determined during the deposition process under conditions such as specific temperature, pressure, and deposition time, or by crystallization treatment after deposition of the thin film.

[0158] The present invention can control the surface morphology of a thin film by the types of the first precursor compound and the second precursor compound.

[0159] In addition, according to the manufacturing method of the present invention, a thin film in a nano-crystalline state and amorphous state mixed with nano-crystalline state can be obtained without performing a separate additional heat treatment after deposition.

[0160] In one embodiment, the thin film manufactured by the above manufacturing method may be a pure silicon (Si) thin film. However, carbon (C) or oxygen (O) may be detected in the thin film due to oxidation or contamination of the thin film surface.

[0161]

[0162] In one embodiment, the grain size of the thin film manufactured by the above manufacturing method, as measured by SEM, may be 30 nm or more and 50 nm or less.

[0163] For example, the grain size may be 30 nm or more and 50 nm or less, 30.5 nm or more and 49 nm or less, 31 nm or more and 48 nm or less, 31 nm or more and 46 nm or less, 31.7 nm or more and 45.2 nm or less, or 37.3 nm or more and 47.6 nm or less.

[0164]

[0165] In one embodiment, the roughness of the thin film manufactured by the above manufacturing method, as measured by AFM, may have an Rq value of 0.1 nm or more and 0.5 nm or less at a scan size of 5 μm.

[0166] For example, the Rq value may be 0.1 nm to 0.5 nm, 0.15 nm to 0.4 nm, 0.15 nm to 0.3 nm, 0.2 nm to 0.25 nm, 0.2 nm to 0.3 nm, 0.2 nm to 0.35 nm, 0.2 nm to 0.4 nm, 0.21 nm to 0.39 nm, 0.22 nm to 0.36 nm, 0.3 nm to 0.5 nm, 0.31 nm to 0.49 nm, 0.32 nm to 0.48 nm, 0.33 nm to 0.46 nm, or 0.34 nm to 0.45 nm.

[0167]

[0168] In one embodiment, the roughness of the thin film manufactured by the above manufacturing method, as measured by AFM, may have an Ra value of 0.1 nm or more and 0.4 nm or less at a scan size of 5 μm.

[0169] For example, the Ra value may be 0.1 nm or more and 0.4 nm or less, 0.12 nm or more and 0.35 nm or less, 0.14 nm or more and 0.3 nm or less, 0.15 nm or more and 0.29 nm or less, 0.17 nm or more and 0.28 nm or less, 0.17 nm or more and 0.3 nm or less, 0.17 nm or more and 0.35 nm or less, 0.17 nm or more and 0.4 nm or less, 0.2 nm or more and 0.4 nm or less, 0.21 nm or more and 0.39 nm or less, 0.22 nm or more and 0.38 nm or less, 0.23 nm or more and 0.36 nm or less, or 0.24 nm or more and 0.35 nm or less.

[0170] Hereinafter, the present invention will be described in more detail using a manufacturing example, but the present invention is not limited thereto.

[0171]

[0172] [Manufacturing example]

[0173] A thin film was fabricated using the first precursor compound and the second precursor compound using an atomic layer deposition (ALD) device.

[0174] The substrate used in this experiment was a p-type Si(100) wafer with a resistivity of 0.02 Ω·cm. Prior to deposition, the p-type Si wafer was ultrasonically cleaned in acetone, ethanol, and deionized water (DI water) for 10 minutes each. The native oxide film on the Si wafer was removed after immersing it in a 10% HF solution (HF:H2O=1:9) for 10 seconds. The HF-cleaned Si wafer was immediately transferred to the atomic layer deposition (ALD) chamber.

[0175] In addition, as shown in Table 1 below, the first precursor compound and the second precursor compound used in the production of the thin film are any one of diiodosilane (DIS), tetrachlorodisilane (TCDS), and diisopropyl aminosilane (DIPAS).

[0176] The temperature of the canister of the first precursor compound was maintained at 25°C for Manufacturing Example 1 and at room temperature (21-23°C) for Manufacturing Examples 2 and 3.

[0177] The first precursor compound - argon (Ar) - second precursor compound - argon (Ar) were supplied in this order, and this constituted one cycle.

[0178]

[0179] In the case of Manufacturing Example 1, the injection time of the first precursor compound (DIS) was adjusted to 3 to 10 seconds, in the case of Manufacturing Example 2, the injection time of the first precursor compound (TCDS) was adjusted to 2 to 10 seconds, and in the case of Manufacturing Example 3, the injection time of the first precursor compound (DIPAS) was adjusted to 1 to 10 seconds.

[0180] At this time, the injection amount of the first precursor compound was 200 sccm for DIS of Manufacturing Example 1, 200 sccm for TCDS of Manufacturing Example 2, and 100 sccm for DIPAS of Manufacturing Example 3, and the process pressure was 3.2 to 4.0 Torr.

[0181] The injection time of the second precursor compound used in Manufacturing Examples 1 to 3 was adjusted to 5 to 15 seconds for DIPAS of Manufacturing Example 1, 1 to 10 seconds for DIPAS of Manufacturing Example 2, and 2 to 10 seconds for TCDS of Manufacturing Example 3. The injection amount was adjusted to 100 sccm for Manufacturing Examples 1 and 2 by controlling the on / off of the pneumatic valve, and 200 sccm for Manufacturing Example 3.

[0182] The injection amount of argon (Ar) for purging the second precursor compound was set to 100 sccm.

[0183] The process temperature range was 400°C to 500°C for Manufacturing Example 1, and 400°C to 450°C for Manufacturing Examples 2 and 3, the reactor pressure was 3.0 to 4.0 torr, and the number of cycles was 180 times for Manufacturing Example 1, and 200 times for Manufacturing Examples 2 and 3.

[0184]

[0185] Table 1 below shows the process conditions for manufacturing thin films according to each manufacturing example.

[0186] Precursor system 1 Precursor system 2 Precursor injection time (seconds) 1st purge time (seconds) 2nd precursor injection time (seconds) 2nd purge time (seconds) Process temperature (℃) Cycles (times) Manufacturing example 1 DIS DIPAS 3~10 10 5~15 10 400~500 180 Manufacturing example 2 TC DSP DIPAS 2~10 10 1~10 10 400~450 200 Manufacturing example 3 DIPAST CDS 1~10 10 2~10 10 400~450 200

[0187]

[0188] In Table 1 above, DIS is diiodosilane, TCDS is tetrachlorodisilane, and DIPAS is diisopropyl aminosilane.

[0189]

[0190] [Evaluation Example 1 - Change in thin film deposition rate according to injection time of first precursor compound]

[0191] Under the process conditions described in Table 1 above, the injection time of the first precursor compound was changed in the range of 3 to 10 seconds for Manufacturing Example 1 and 2 to 10 seconds for Manufacturing Example 2, and a thin film was manufactured according to the above Manufacturing Example. The deposition rate (Growth rate per cycle, GPC) of the thin film was measured, and the deposition rate of Manufacturing Example 1 is shown in Figure 1(a), and the deposition rate of Manufacturing Example 2 is shown in Figure 1(b).

[0192]

[0193] Below, the deposition rates of evaluation examples 1 to 3 were calculated using the following mathematical formula 1.

[0194]

[0195] [Mathematical Formula 1]

[0196] Deposition rate (Å / cycle) = deposition thickness / number of ALD cycles

[0197]

[0198] The deposition thickness of the above mathematical expression 1 was measured using an ellipsometer and confirmed using a field emission scanning electron microscope (FE-SEM).

[0199]

[0200] At a process temperature of 480°C, an atomic layer deposition (ALD) process was performed according to the manufacturing methods of Manufacturing Examples 1 and 2. During the process, the first precursor injection time (Source feeding time), which indicates a constant thin film deposition rate, was measured to confirm a self-limiting reaction.

[0201] As shown in Fig. 1(a), a constant thin film deposition rate is observed in the range of 5 to 10 seconds when the first precursor compound (DIS) of Manufacturing Example 1 is injected.

[0202] In addition, as shown in Fig. 1(b), a constant thin film deposition rate is shown in the range of 5 to 10 seconds when the first precursor compound (TCDS) of Manufacturing Example 2 is injected.

[0203]

[0204] [Evaluation Example 2 - Change in thin film deposition rate according to the injection time of the second precursor compound]

[0205] A thin film was manufactured according to the manufacturing example above by changing the injection time of the second precursor compound of Manufacturing Example 1 in the range of 5 to 15 seconds under the process conditions described in Table 1 above, and the deposition rate of the thin film was measured, and the deposition rate of Manufacturing Example 1 is shown in Figure 2.

[0206] At a process temperature of 480°C, an atomic layer deposition (ALD) process was performed according to the manufacturing method of Manufacturing Example 1, using the first precursor compound of Manufacturing Example 1 as a source and the second precursor compound as a reactant. During the process, the second precursor injection time, which exhibited a constant thin film deposition rate, was measured to confirm a self-limiting reaction.

[0207] As shown in Fig. 2, the second precursor compound (DIPAS) of Manufacturing Example 1 shows a constant thin film deposition rate in the injection time range of 10 to 15 seconds.

[0208] Meanwhile, under the process conditions described in Table 1 above, the second precursor injection time of Manufacturing Example 2 was changed in the range of 1 to 10 seconds to manufacture a thin film according to the above Manufacturing Example, and the deposition rate of the thin film was measured.

[0209] At a process temperature of 410°C, an atomic layer deposition (ALD) process was performed according to the manufacturing method of Manufacturing Example 2, using the first precursor compound of Manufacturing Example 2 as a source and the second precursor compound as a reactant. During the process, the second precursor injection time, which exhibited a constant thin film deposition rate, was measured to confirm a self-limiting reaction.

[0210] As a result of the measurement, the second precursor compound (DIPAS) of Manufacturing Example 2 showed a constant thin film deposition rate of 0.2 Å / cycle in the injection time range of 5 to 10 seconds.

[0211]

[0212] [Evaluation Example 3 - Change in thin film deposition rate according to process temperature]

[0213] In the process conditions described in Table 1 above, the process temperature was changed in the range of 400°C to 500°C for Manufacturing Example 1 and 400°C to 450°C for Manufacturing Example 2, and a thin film was manufactured according to the manufacturing example, and the deposition rate of the thin film was measured. The deposition rate of Manufacturing Example 1 is shown in Fig. 3(a), and the deposition rate of Manufacturing Example 2 is shown in Fig. 3(b).

[0214] As shown in Fig. 3(a), when the first precursor compound (DIS) of Manufacturing Example 1 was used as a source and the second precursor compound (DIPAS) used was injected as a reactant, it was confirmed that the deposition rate was maintained at a process temperature of 400 to 480°C.

[0215] As shown in Fig. 3(b), when the first precursor compound (TCDS) of Manufacturing Example 2 was used as a source and the second precursor compound (DIPAS) used was injected as a reactant, it was confirmed that the deposition rate was maintained at a process temperature of 400 to 420°C.

[0216] That is, in the case of Manufacturing Example 1, it was confirmed that the temperature range of the atomic layer deposition section (ALD Window) was 400 to 480°C, and in the case of Manufacturing Example 2, the temperature range of the atomic layer deposition section was 400 to 420°C.

[0217]

[0218] [Evaluation Example 4 - Grain Size Analysis of Manufacturing Example 1]

[0219] The grain size of the case where DIS was used as the first precursor compound and DIPAS was used as the second precursor compound in Manufacturing Example 1 was analyzed using a scanning electron microscope (SEM).

[0220] Fig. 4(a) is an SEM photograph of a thin film manufactured according to Manufacturing Example 1 at a process temperature of 400°C, and Fig. 4(b) is an SEM photograph of a thin film manufactured according to Manufacturing Example 1 at a process temperature of 480°C.

[0221] As shown in Fig. 4(a), the SEM analysis of the surface of a thin film manufactured by the atomic layer deposition method using DIS as the first precursor compound and DIPAS as the second precursor compound at 400°C showed that the average grain size of 10 randomly selected grains within a sample with an area of ​​2 cm X 2 cm was 9.5 nm (5.5 nm to 11.9 nm).

[0222] As shown in Fig. 4(b), the SEM analysis of the surface of a thin film manufactured by the atomic layer deposition method using DIS as the first precursor compound and DIPAS as the second precursor compound at 480°C showed that the average grain size of 10 randomly selected grains within a sample with an area of ​​2 cm X 2 cm was 38.9 nm (31.7 nm to 45.2 nm).

[0223] That is, when DIS was used as the first precursor in Manufacturing Example 1 and DIPAS was used as the second precursor compound, it was confirmed that an amorphous thin film was formed as the process temperature was lowered, and a thin film in a nano-crystal state was formed as the process temperature was higher.

[0224] Meanwhile, as examined in Evaluation Example 6 below, it was confirmed that in the case of Manufacturing Example 2, an amorphous thin film was formed in which no diffraction peaks due to crystals were observed as a result of X-ray diffraction analysis (X-Ray Diffraction, XRD).

[0225]

[0226] [Evaluation Example 5 - AFM Analysis Results of Manufacturing Examples 2 and 3]

[0227] The morphology of a thin film manufactured using TCDS as the first precursor compound of Manufacturing Example 2 and DIPAS as the second precursor compound and of a thin film manufactured using DIPAS as the first precursor compound of Manufacturing Example 3 and TCDS as the second precursor compound was analyzed using atomic force microscopy (AFM).

[0228] Fig. 5(a) is an AFM photograph of a thin film manufactured according to Manufacturing Example 2 at a process temperature of 410°C, and Fig. 5(b) is an AFM photograph of a thin film manufactured according to Manufacturing Example 2 at a process temperature of 450°C.

[0229] As shown in Fig. 5(a), the results of AFM analysis of the surface of a thin film manufactured by the atomic layer deposition method using TCDS as the first precursor compound and DIPAS as the second precursor compound at 410°C are as shown in Table 2 below.

[0230] Scan size(μm)Rq(nm)Ra(nm)1 x 10.3840.2975 x 50.3540.27510 x 100.3190.252

[0231]

[0232] In Table 2 above, Rq represents the mean square peak height, and Ra represents the average two-dimensional surface roughness.

[0233]

[0234] As shown in Fig. 5(b), the results of AFM analysis of the surface of a thin film manufactured by atomic layer deposition using TCDS as the first precursor compound and DIPAS as the second precursor compound at 450°C are as shown in Table 3 below.

[0235] Scan size(μm)Rq(nm)Ra(nm)1 x 10.4420.3475 x 50.3700.29210 x 100.3330.262

[0236]

[0237] In Table 3 above, Rq represents the mean square peak height, and Ra represents the average two-dimensional surface roughness.

[0238]

[0239] Meanwhile, the results of AFM analysis of the surface of a thin film manufactured by the atomic layer deposition method using DIPAS as the first precursor compound and TCDS as the second precursor compound according to Manufacturing Example 3 at a process temperature of 410°C are as shown in Table 4 below.

[0240] Scan size(μm)Rq(nm)Ra(nm)2 x 20.2650.2045 x 50.2240.17210 x 100.1850.142

[0241]

[0242] In Table 4 above, Rq represents the mean square peak height, and Ra represents the average two-dimensional surface roughness.

[0243]

[0244] That is, when TCDS was used as the first precursor compound of Manufacturing Example 2 and DIPAS was used as the second precursor compound, it was confirmed that the lower the process temperature, the smaller the Rq and Ra values ​​of the manufactured thin film, and the higher the process temperature, the larger the Rq and Ra values ​​of the manufactured thin film.

[0245]

[0246] Meanwhile, the surface roughness of the thin films of Manufacturing Examples 2 and 3, which were manufactured by changing the injection order of the precursor compounds, was confirmed using a scanning electron microscope.

[0247] Fig. 6(a) is an SEM photograph of a thin film manufactured according to Manufacturing Example 2 at a process temperature of 410°C, and Fig. 6(b) is an SEM photograph of a thin film manufactured according to Manufacturing Example 3 at a process temperature of 410°C, but with a different injection order of precursor compounds from Manufacturing Example 2.

[0248]

[0249] That is, as shown in FIG. 6(a) and FIG. 6(b) and in Tables 2 and 4 above, it was confirmed that the surface roughness of the thin film (FIG. 6(a)) manufactured by the atomic layer deposition method using TCDS as the first precursor compound of Manufacturing Example 2 and DIPAS as the second precursor compound at a process temperature of 410°C, and the surface of the thin film (FIG. 6(b)) manufactured by the atomic layer deposition method using DIPAS as the first precursor compound of Manufacturing Example 3 and TCDS as the second precursor compound, among the surfaces of the thin film (FIG. 6(b)) manufactured by first injecting DIPAS of Manufacturing Example 3, was improved.

[0250]

[0251] [Evaluation Example 6 - X-ray diffraction analysis (XRD) results of Manufacturing Example 2]

[0252] The morphology of the thin film manufactured using TCDS as the first precursor compound and DIPAS as the second precursor compound in Manufacturing Example 2 was analyzed using X-ray diffraction analysis.

[0253] Figure 7(a) is a graph showing the results of X-ray diffraction analysis of a thin film manufactured according to Manufacturing Example 2 at a process temperature of 410°C.

[0254] Figure 7(b) is a graph showing the results of X-ray diffraction analysis of a thin film manufactured according to Manufacturing Example 2 at a process temperature of 450°C.

[0255] As shown in Fig. 7(a) and Fig. 7(b), when a thin film manufactured by the atomic layer deposition method using TCDS as the first precursor compound and DIPAS as the second precursor compound of Manufacturing Example 2 was subjected to X-ray diffraction analysis, no diffraction peaks with strong intensity were observed.

[0256] That is, it was confirmed that an amorphous silicon thin film was formed according to Manufacturing Example 2 of the present invention.

[0257]

[0258] Through the above thin film manufacturing, it was confirmed that a silicon thin film with excellent properties can be formed by atomic layer deposition even at a low temperature of 500°C or less by the manufacturing method using the first precursor compound and the second precursor compound of Manufacturing Examples 1 to 3.

[0259]

[0260] The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

[0261] The method for manufacturing a thin film of this invention has the effect of efficiently manufacturing a silicon thin film with excellent properties.

[0262] Specifically, the present invention enables an atomic layer deposition process even at a low temperature of 500°C or lower by introducing two types of silicon precursor compounds, uses the precursor compounds as a source and a reactant, and can deposit an amorphous or nanocrystalline thin film depending on the type of the precursor compound.

[0263] In particular, by depositing an amorphous silicon thin film, a polycrystalline silicon thin film with a large grain boundary size can be manufactured during crystallization.

[0264] That is, the method for manufacturing a thin film of the present invention uses two types of silicon precursor compounds to enable uniform thin film deposition with excellent properties even at low temperatures, thereby ensuring excellent thin film properties, thickness, and step coverage, and controlling the morphology and crystallinity of the deposited thin film.

[0265] In addition, the thin film with excellent properties manufactured by the method for manufacturing the thin film of the present invention can be used as a dielectric, display, next-generation memory, non-memory semiconductor, etc. of various electronic devices.

Claims

1. A first injection step of injecting a first precursor compound into the chamber; and A second injection step of injecting a second precursor compound into the chamber is repeated to deposit a thin film, The above first precursor compound is represented by the following chemical formula 1 or 2, The above second precursor compound is represented by the following chemical formula 1 or 2: Method for manufacturing thin films. (However, if the first precursor compound is a compound represented by the following chemical formula 1, the second precursor compound is a compound represented by the following chemical formula 2, When the first precursor compound is a compound represented by the following chemical formula 2, the second precursor compound is a compound represented by the following chemical formula 1. [Chemical Formula 1] You x (R1) y H (2x+2-y) [Chemical Formula 2] Si(NR2R3) z H (4-z) In the above chemical formulas 1 and 2, R1 is any one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), R2 and R3 are each independently one selected from a group consisting of linear or branched hydrocarbons having 1 to 4 carbon atoms, x is an integer from 1 to 3, y is an integer from 1 to 7, z is an integer from 1 to 3.

2. In paragraph 1, R1 in the above chemical formula 1 is chlorine (Cl) or iodine (I), x is 1 or 2, y is 2 or 4 Method for manufacturing thin films.

3. In paragraph 1, R2 and R3 in the above chemical formula 2 are each independently one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group, z is 1 or 2, Method for manufacturing thin films.

4. In paragraph 1, Between the first injection step and the second injection step, a first purge step for injecting a first purge gas into the chamber; and After the second injection step, a second purge step is further included for injecting a second purge gas into the chamber. Method for manufacturing thin films.

5. In paragraph 1, The compound represented by the above chemical formula 1 is fluoro silane, chloro silane, bromo silane, iodo silane, difluoro silane, dichloro silane, dibromo silane, diiodo silane, trifluoro silane, trichloro silane, tribromo silane, triiodo silane, tetrafluoro silane, tetrachloro silane, tetrabromo silane, tetraiodo silane, fluorodisilane, chloro disilane, bromo Any one selected from the group consisting of disilane (bromo disilane), iodo disilane, difluoro disilane, dichloro disilane, dibromo disilane, diiodo disilane, trifluoro disilane, trichloro disilane, tribromo disilane, triiodo disilane, tetrafluoro disilane, tetrachloro disilane, tetrabromo disilane and tetraiodo disilane, Method for manufacturing thin films.

6. In paragraph 1, The compound represented by the above chemical formula 2 is any one selected from the group consisting of dimethyl aminosilane, diethyl aminosilane, diisopropyl aminosilane, dibutyl aminosilane, diisobutyl aminosilane, dimethylethylsilane diamine, dimethylpropylsilane diamine, and bis(diethylamino)silane. Method for manufacturing thin films.

7. In paragraph 1, The process temperature is 350℃ or higher and 500℃ or lower, Method for manufacturing thin films.

8. In paragraph 1, The above thin film is in one of an amorphous state, a mixed state of an amorphous state and a nanocrystalline state, and a nanocrystalline state. Method for manufacturing thin films.

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