Method for forming thin film by using two silicon precursor compounds

Abstract

The present invention relates to a method for manufacturing a silicon thin film using two types of silicon precursor compounds, and more specifically, to a method for manufacturing a silicon thin film, which has excellent thin film characteristics and can be adjusted according to the form of a precursor, even at low temperatures by atomic layer deposition (ALD).

Description

TECHNICAL FIELD

[0001] The present application relates to a method of forming a silicon thin film having excellent properties at a low temperature by atomic layer deposition (ALD) using two silicon precursors. BACKGROUND

[0002] Recently, silicon-containing thin films can be manufactured in various forms by various processes in the semiconductor field. In particular, silicon oxide films and silicon nitride films have very excellent barrier and oxidation resistance, and thus can be used as insulating films, diffusion prevention films, hard masks, etching stop layers, seed layers, spacers, shallow trench isolation, intermetallic dielectric materials, or protective film layers in device manufacturing, and in recent years, the application fields of polycrystalline silicon thin films have gradually diversified, and they are used in thin film transistors (TFTs), solar cells, and the like.

[0003] Representative technologies disclosed for the manufacture of silicon-containing thin films include atomic layer deposition (ALD), in which a precursor in a gas form is physically or chemically adsorbed on the surface of a substrate, and then a film is formed by the injection of a reaction gas; metal organic chemical vapor deposition (MOCVD), in which an organic metal precursor in a mixed gas form is reacted with a reaction gas to form a film on the surface of a substrate or directly on the surface; and low pressure chemical vapor deposition (LPCVD) or plasma-enhanced atomic layer deposition (PEALD) using a chemical vapor deposition method (PECVD) that can deposit plasma at a low temperature, among various thin film manufacturing technologies applied to the manufacturing process of next-generation semiconductors and the like, and the deposition of thin films having uniformity and excellent properties in the formation of ultrafine patterns and in the thickness of nanometers.

[0004] In particular, a thin film applied to a semiconductor device needs to be controlled in atomic units and have excellent characteristics of single-time coverage. A technology applicable thereto is an atomic layer deposition method (ALD). The atomic layer deposition method has attracted attention as a deposition technology having potential in many applications of nanoscale devices, as the development of a high-isotropy thin film deposition method that can adjust a nanoscale thickness is a very important factor. The atomic layer deposition method is expected to solve problems caused by the refinement of devices such as high leakage current, and in addition to deposition of a single high-dielectric substance, the atomic layer deposition method further has the advantage of being able to deposit a thin film having atomic-level composition variation. The principle of the atomic layer deposition method is to provide each reactant separated by an inert gas (Ar, N2, etc.) to a wafer to deposit one atomic layer, and to repeat the deposition for the thickness required for deposition. After chemical adsorption of one reactant on a substrate for thin film deposition, a second or third gas enters the substrate to chemically adsorb on the substrate again, thereby forming a reaction of a thin film. The reactants are single elements or compounds, and these reactants need to be highly volatile, stable in substance, and highly reactive.

[0005] However, when using a precursor used in the existing atomic layer deposition method, there is a problem that a high-temperature process of 600°C or more is required, and the reactants are decomposed at the high-temperature process to cause defects, and physical and electrical characteristics of a thin film such as step coverage, etching, etc. are deteriorated.

[0006] Therefore, there is a necessity to simultaneously improve low-temperature activity for a deposition process, adhesion of a thin film, excellent step coverage, and an adjustable thickness process in atomic layer levels.

[0007] As a result, there is an urgent need to develop a thin film manufacturing method that can perform an atomic layer deposition process at a low temperature, has excellent step coverage, and has excellent thin film characteristics.

[0008] [Related Art Documents]

[0009] [Patent Documents]

[0010] (Patent Document 1) Korean Registered Patent Gazette No. 10-1436564 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] The present document aims to provide a method of effectively manufacturing a silicon thin film at a low temperature using two silicon precursors, and a thin film having excellent characteristics manufactured by the method.

[0013] In particular, in the conventional thin film deposition method, a silicon thin film containing defects is formed by a low pressure chemical vapor deposition (LPCVD), and thus, when crystallized at a high temperature, a poly-Si thin film having a small grain boundary size is formed.

[0014] To address this, the present application aims to provide a thin film manufacturing method that uses a thermal energy atomic layer deposition (ALD) process, rather than a conventional plasma, in combination with the use of two silicon precursors, so that ALD mobility is ensured at a low temperature of 500°C or less, and conformal deposition is possible for a pattern having a high aspect ratio.

[0015] However, the technical problems to be solved by the present application are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

[0016] However, the technical problems to be solved by the present application are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

[0017] A thin film manufacturing method,

[0018] The first cycle is repeated to deposit a thin film, the first cycle including:

[0019] a first injection step of injecting a first precursor compound into the cavity; and

[0020] a second injection step of injecting a second precursor compound into the cavity,

[0021] The first precursor compound is represented by the following Chemical Formula 1,

[0022] The first precursor compound is represented by the following Chemical Formula 2.

[0023] [Chemical Formula 1]

[0024] Si(R1) x H (4-x)

[0025] [Chemical Formula 2]

[0026] Siy(R2) z H (2y+2-z)

[0027] In the Chemical Formulas 1 and 2,

[0028] R1and R2are each independently any one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I),

[0029] x is an integer of 1 to 4,

[0030] when y is equal to 1, z is an integer of 0 to 4,

[0031] when y is equal to 2 or 3, z is an integer of 0 to 6.

[0032] Effects of the Invention

[0033] The thin film manufacturing method herein has the effect of efficiently manufacturing a silicon thin film with excellent characteristics.

[0034] Specifically, two kinds of silicon precursor compounds are introduced herein, and an atomic layer deposition process can be performed at a low temperature of 500°C or less, using the precursor compounds as a source material and a reaction body, and amorphous or nanocrystalline thin films can be deposited depending on the kind of the precursor compounds.

[0035] In particular, by depositing an amorphous silicon thin film, a polycrystalline silicon thin film having a large grain boundary size when crystallization is performed can be manufactured.

[0036] That is, the thin film manufacturing method herein uses two kinds of silicon precursor compounds, and uniform thin film deposition with excellent characteristics can be achieved at a low temperature, so that excellent thin film characteristics, thickness, and step coverage according thereto can be ensured, and the morphology and crystallinity of the deposited thin film can be adjusted.

[0037] In addition, the thin film with excellent characteristics manufactured based on the thin film manufacturing method of the present invention can be applied to a dielectric of various electronic devices, a display, a next-generation memory, a non-memory semiconductor, etc. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is a schematic view of the manufacturing of a silicon seed layer and an oxidation or nitridation process on the silicon seed layer.

[0039] Figure 2 is a schematic view of the manufacturing of a silicon thin film and an oxidation or nitridation process on the silicon thin film. DETAILED DESCRIPTION

[0040] Hereinafter, the effects and advantages of the present invention will be further described through specific examples of the invention and the accompanying drawings. However, such examples are presented only as an example of the present invention, and do not limit the scope of the invention claimed by the present invention.

[0041] The terms or words used herein and in the claims should not be interpreted as being limited to commonly used meanings or meanings in dictionaries, but should be interpreted based on the judicial precedent which is appropriate, considering the knowledge of those skilled in the art to which such inventive concept belong, that the inventor is able to define the concepts of the terms as appropriate for best explaining the present invention.

[0042] Therefore, it should be understood that the structure of the embodiments described in the specification is only one of the preferred embodiments of the present invention, and does not represent all the technical spirits of the present invention, and various equivalent substitutions and modifications can be made with respect to the present application.

[0043] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be understood that the terms "comprises," "comprising," "includes," "including," or "has," "having," as used herein, specify the presence of the stated feature, integer, step, element, component, or combination thereof, but do not preclude the presence or addition of one or more other features, integers, steps, elements, components, or combinations thereof.

[0044] In this document, where a variety of parameters are given as enumeration of ranges, preferred ranges, or preferred upper and lower limit values, all ranges formed by any upper limit value or preferred value of any one pair, and any lower limit value or preferred value of any other pair, are specifically disclosed, regardless of whether the ranges are individually disclosed.

[0045] When a numerical range is mentioned herein, unless otherwise specified, the range is intended to include the endpoints and all integers and fractions within the range.

[0046] The scope of the present invention is intended to be not limited to the specific values mentioned in defining the ranges.

[0047] In this specification, "to" and "~" in "a to b" and "a~b" indicating a numerical range are defined as ≥a, and ≤b.

[0048] The thin film manufacturing method according to the first aspect herein can include repeating a first cycle to deposit a thin film, the first cycle including a first injection step of injecting a first precursor compound within a cavity; and a second injection step of injecting a second precursor compound within the cavity, the first precursor compound being represented by the following Chemical Formula 1, and the second precursor compound being represented by the following Chemical Formula 2.

[0049] [Chemical Formula 1]

[0050] Si(R1) x H (4-x)

[0051] [Chemical Formula 2]

[0052] Siy(R2) zH (2y+2-z)

[0053] In the Chemical Formula 1 and 2,

[0054] R1 and R2 are each independently any one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I),

[0055] x is an integer of 1 to 4,

[0056] When y is equal to 1, z is an integer of 0 to 4,

[0057] When y is equal to 2 or 3, z can be an integer of 0 to 6.

[0058] At this time, when the number after the atom is 0, it can be explained that the atom is not included.

[0059] In addition, the Chemical Formula 2 can be the same as the Chemical Formula 1, or can be different.

[0060] In this context, the chamber can refer to the internal space of the reactor formed by the thin film deposition process.

[0061] The first cycle can be 1 or more, 1000 or less. For example, it can be 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more.

[0062] In one implementation example herein, R1 of the Chemical Formula 1 is iodine (I), and x can be 2.

[0063] For example, the first precursor compound can be SiI2H2.

[0064] In one implementation example herein, R2 of the Chemical Formula 2 is chlorine (Cl), y is 2, and z can be 4 or 5.

[0065] For example, the second precursor compound can be Si2Cl4H2 or Si2Cl5H.

[0066] On the other hand, when the second precursor compound is not included, the operation of ALD can not be smooth at a low temperature of 500℃ or less, and the form characteristics of the deposited thin film can be degraded.

[0067] The thin film manufacturing method can be atomic layer deposition (ALD), chemical vapor deposition (CVD), or a combination thereof, and preferably can be atomic layer deposition (ALD), but is not limited thereto.

[0068] Atomic layer deposition is a deposition method in which the following steps are repeated: a step of adsorbing a precursor onto a substrate, a step of purging a remaining precursor with a purge gas, a step of reacting using a reaction gas, and a step of purging a remaining reaction gas with a purge gas. With atomic layer deposition, a thinner film can be formed, and a film with high uniformity can be formed. In addition, by repeating each step of atomic layer deposition, a thin film can be formed on a substrate to a desired thickness.

[0069] In atomic layer deposition, a reactant needs to have high volatility, material stability, and high reactivity. In atomic layer deposition, a monolayer or less of a thin film is grown by surface reaction when a cycle is deposited in a manner in which reaction materials are separately supplied, and a ligand of a reaction material adsorbed on a substrate can be removed by a subsequent supply of another reaction material and a chemical reaction. In order to perform atomic layer deposition, a liquid phase has an advantage over a solid phase in terms of reaction speed and process when a reactant precursor compound is heated.

[0070] The first precursor compound described herein is a compound including a silicon (Si) atom, which can be a colorless liquid at room temperature.

[0071] In an implementation example herein, between the first injection step and the second injection step, a first purge step of injecting a first purge gas into the cavity can be further included, and a second purge step of injecting a second purge gas into the cavity after the second injection step can be further included.

[0072] At this time, the first and second purge gases can each be hydrogen (H2), argon (Ar), nitrogen (N2), helium (He), a noble gas, an inert gas, or a combination thereof, used alone.

[0073] In an implementation example herein, hydrogen gas (H2) can be simultaneously injected in the first injection step and / or the second injection step to adjust the hydrogen (H) content of the thin film, and the impurity concentration of a halogen atom can be adjusted.

[0074] In addition, hydrogen gas (H2) can be simultaneously injected in the first purge step and / or the second purge step to adjust the hydrogen (H) content of the thin film, and the impurity concentration of a halogen atom can be adjusted.

[0075] In an implementation example herein, the compound represented by the Chemical Formula 1 can be any one or more selected from the group consisting of fluoro silane, chloro silane, bromo silane, iodo silane, difluoro silane, dichloro silane, dibromo silane, diiodo silane (DIS, SiI2H2), trifluoro silane, trichloro silane, tribromo silane, triiodo silane, tetrafluoro silane, tetrachloro silane, tetrabromo silane, and tetraiodo silane.

[0076] For example, the precursor compound represented by the Chemical Formula 1 can be diiodo silane (DIS), but is not limited thereto.

[0077] In an implementation example herein, the compound represented by the chemical formula 2 can be selected from silane (SiH4), fluoro silane, chloro silane, bromo silane, iodo silane, difluoro silane, dichloro silane, dibromo silane, diiodo silane (DIS, SiI2H2), trifluoro silane, trichloro silane, tribromo silane, triiodo silane, tetrafluoro silane, tetrachloro silane, tetrabromo silane, tetraiodo silane, disilane (Si2H6), fluoro disilane, 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 (TCDS, Si2Cl4H2), tetrabromo disilane, tetraiodo disilane, pentafluoro disilane, pentachloro disilane (PCDS, Si2Cl4H2), hexafluoro disilane, hexachloro disilane, hexabromo disilane, hexaiodo disilane, heptafluoro disilane, heptachloro disilane, heptabromo disilane, heptaiodo disilane, octafluoro disilane, octachloro disilane, octabromo disilane, octaiodo disilane, nonafluoro disilane, nonachloro disilane, nonabromo disilane, nonaiodo disilane, decafluoro disilane, decachloro disilane, decabromo disilane, decaiodo disilane, undecafluoro disilane, undeca chloro disilane, undecabromo disilane, undecaiodo disilane, dodecafluoro disilane, dodecachloro disilane, dodecabromo disilane, dodecaiodo disilane, trisilane (Si3H8), fluoro trisilane, chloro trisilane, bromo trisilane, iodo trisilane, difluoro trisilane, dichloro trisilane, dibromo trisilane, diiodo trisilane, trifluoro trisilane, trichloro trisilane, tribromo trisilane, triiodo trisilane, tetrafluoro trisilane, tetrachloro trisilane, tetrabromo trisilane, tetraiodo trisilane, pentafluoro trisilane, pentachloro trisilane, pentabromo trisilane, pentaiodo trisilane, hexafluoro trisilane, hexachloro trisilane, hexabromo trisilane, hexaiodo trisilane, heptafluoro trisilane, heptachloro trisilane, heptabromo trisilane, heptaiodo trisilane, octafluoro trisilane, octachloro trisilane, octabromo trisilane, octaiodo trisilane, nonafluoro trisilane, nonachloro trisilane, nonabromo trisilane, nonaiodo trisilane, decafluoro trisilane, decachloro trisilane, decabromo trisilane, decaiodo trisilane, undecafluoro trisilane, undeca chloro trisilane, undecabromo trisilane, undecaiodo trisilane, dodecafluoro trisilane, dodecachloro trisilane, dodecabromo trisilane, dodecaiodo trisilane,Si2Cl5H), pentabromo disilane, pentaiodo disilane, hexafluoro disilane, hexachloro disilane, hexabromo disilane, hexaiodo disilane, trisilane (Si3H8), fluoro trisilane, chloro trisilane, bromo trisilane, iodo trisilane, difluoro trisilane, dichloro trisilane, dibromo trisilane, diiodo trisilane, tri fluoro trisilane, trichloro trisilane, tribromo trisilane, triiodo trisilane, tetrafluoro trisilane, tetrachloro trisilane, tetrabromo trisilane, tetraiodo trisilane, pentafluoro trisilane, pentachloro trisilane, pentabromo trisilane, pentaiodo trisilane, hexafluoro trisilane, hexachloro trisilane, hexabromo trisilane, and hexaiodo trisilane.

[0078] For example, the compound represented by the Chemical Formula 2 can be any one selected from the group consisting of tetrachloro disilane (TCDS) and pentachloro disilane (PCDS), but is not limited thereto.

[0079] In an implementation example herein, the process temperature of the method of manufacturing the thin film can be 350°C or more and 500°C or less.

[0080] For example, the process temperature can be 350°C or more and 500°C or less, 360°C or more and 500°C or less, 370°C or more and 500°C or less, 380°C or more and 500°C or less, 390°C or more and 500°C or less, 400°C or more and 500°C or less, 370°C or more and 490°C or less, 390°C or more and 485°C or less, 395°C or more and 480°C or less, 400°C or more and 475°C or less, 360°C or more and 480°C or less, 370°C or more and 460°C or less, 380°C or more and 440°C or less, 390°C or more and 430°C or less, 400°C or more and 420°C or less, 350°C or more and 490°C or less, 350°C or more and 480°C or less, 350°C or more and 470°C or less, 350°C or more and 460°C or less, 350°C or more and 450°C or less, 350°C or more and 440°C or less, 350°C or more and 430°C or less, 350°C or more and 420°C or less, 350°C or more and 410°C or less, 350°C or more and 400°C or less, 360°C or more and 450°C or less, 370°C or more and 450°C or less, 380°C or more and 450°C or less, 390°C or more and 450°C or less, 400°C or more and 450°C or less, 410°C or more and 450°C or less, 420°C or more and 450°C or less, 430°C or more and 450°C or less, 440°C or more and 450°C or less.

[0081] Specifically, when the first precursor compound is diiodo silane (DIS), the process temperature can 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.

[0082] On the other hand, when the thin film according to the present disclosure is manufactured at a low temperature of less than 350°C, the deposition can not be performed normally. This can be because the reaction speed is not sufficient, resulting in further slow deposition speed. In addition, the second precursor compound can not be sufficiently diffused, which can cause material and thin film transmission defects or uniformity problems, thereby making the substrate or the thin film unstable.

[0083] In addition, when the thin film according to the present disclosure is manufactured at a high temperature of more than 500°C, the deposition can not be performed normally. This is because the reaction speed can be too fast to generate impurities, and decomposition of the precursor or the reaction gas can cause difficulty in forming the thin film.

[0084] In an embodiment, when the first precursor compound is diiodosilane and the second precursor compound is tetrachlorodisilane, the growth rate per cycle (GPC) based on the manufacturing method can be / cycle at the process temperature in the range of 400 to 450°C. That is, the growth rate per cycle based on the manufacturing method can be / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C, / cycle at the process temperature in the range of 400 to 450°C.

[0085] In an embodiment, when the first precursor compound is diiodosilane and the second precursor compound is pentachlorodisilane, the growth rate per cycle (GPC) based on the manufacturing method can be / cycle at the process temperature in the range of 420 to 450°C. That is, the growth rate per cycle based on the manufacturing method can be / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C, / cycle at the process temperature in the range of 420 to 450°C,

[0086] / cycle at the process temperature in the range of 420 to 450°C.

[0087] In an embodiment, the canister temperature of the first precursor compound can be 0°C or higher and 50°C or lower.

[0088] For example, the temperature of the storage tank of the first precursor compound can 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, 15°C or more and 30°C or less.

[0089] In addition, the temperature of the storage tank of the second precursor compound can be 0°C or more and 30°C or less.

[0090] For example, the temperature of the storage tank of the second precursor compound can be 0°C or more and 30°C or less, 0°C or more and 25°C or less, 0°C or more and 25°C or less, 0°C or more and 20°C or less, 5°C or more and 25°C or less, 5°C or more and 20°C or less, 5°C or more and 15°C or less, 10°C or more and 30°C or less, 10°C or more and 25°C or less, 10°C or more and 20°C or less, 10°C or more and 15°C or less, 15°C or more and 30°C or less, 15°C or more and 25°C or less, 15°C or more and 20°C or less.

[0091] The storage tank is used to supply source gas and reaction gas into a chamber for reaction in a method of manufacturing a thin film. Generally, the storage tank vaporizes a precursor compound to generate source gas and reaction gas, and then supplies the gas into the chamber.

[0092] When the temperature of the storage tank exceeds the range, the uniformity of the thickness of the thin film manufactured by the method of manufacturing a thin film is greatly reduced.

[0093] This is because, when the temperature is below the minimum temperature range, the amount of the precursor compound supplied into the chamber is insufficient, and when the temperature exceeds the maximum temperature range, the quality of the film can be non-uniform due to thermal energy deterioration or excessive supply of the precursor compound into the chamber.

[0094] In an embodiment, the injection time of the first precursor compound can be 1 second or more and 30 seconds or less, and the injection time of the second precursor compound can be 1 second or more and 30 seconds or less. Preferably, the injection time of the first precursor compound can be 1 second or more and 15 seconds or less, and the injection time of the second precursor compound can be 1 second or more and 15 seconds or less.

[0095] For example, the injection time of the first precursor compound can 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, 1 second or more and 5 seconds or less,

[0096] The injection time of the second precursor compound can 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, 1 second or more and 5 seconds or less.

[0097] If the injection time of the first and second precursor compounds is not within the above range, it can be difficult to form a proper thin film.

[0098] Specifically, if the injection time of the first precursor compound is not within the above range, it can be difficult to form a thin film of a proper thickness due to a lack of reactants required to form the thin film. In contrast, if the injection time of the first precursor compound exceeds the above range, the composition ratio of the thin film can not be constant due to impurities caused by residual compounds after the reaction.

[0099] In addition, the injection time of the second precursor compound can vary depending on the type of the first precursor compound.

[0100] For example, when the first precursor compound is diiodo silane (DIS), the injection time of the second precursor compound can 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.

[0101] When the injection time of the second precursor compound is less than 1 second, an increase in the amount of residual reactants of the first precursor compound can cause an improper reaction, and the formation of impurities can cause the deposition of the thin film layer to be non-uniform. However, when the injection time of the second precursor compound exceeds 30 seconds, impurities caused by the second precursor compound can occur.

[0102] In an embodiment, the injection time of the release gas of the first release step can be 1 second or more and 1 minute or less, and the injection time of the release gas of the second release step can be 1 second or more and 1 minute or less.

[0103] In an embodiment, the first injection time of the first release gas of the first release step can 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, 1 second or more and 10 seconds or less,

[0104] The injection time of the second release gas can 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.

[0105] When the injection time of the first or second release gas is less than the above range, the increase of the residual amount of the first or second precursor compound can cause an inappropriate reaction, and impurities can not be released, resulting in non-uniform deposition of the thin film layer.

[0106] In an embodiment, when the first cycle is repeated 1 time or more and 70 times or less, the manufactured thin film can be a silicon seed layer. At this time, the silicon seed layer can form a nucleation island, and the nucleation island can be formed randomly.

[0107] In addition, after the nucleation island is formed, when a film is further formed, the film can grow around the nucleation island.

[0108] The first cycle can be repeated, for example, 65 times or less, 60 times or less, 55 times or less, 50 times or less, 45 times or less, 40 times or less, 35 times or less, 30 times or less, 25 times or less, 20 times or less, 15 times or less, or 10 times or less.

[0109] Figure 1 Each sequence of the first injection step, the first release step, the second injection step, and the second release step of the first cycle is shown in FIG. 1.

[0110] In an embodiment, after the silicon seed layer is formed, a third injection step of injecting a compound containing hydrogen (H), nitrogen (N), oxygen (O), or a combination thereof into the cavity can be further included.

[0111] Figure 1 Each sequence of the third injection step and the third release step is shown in FIG. 2. When the third injection step and the third release step are required for nitridation or oxidation of the silicon seed layer, they can be selectively performed. When the third injection step and the third release step are not performed, the third injection step 160 and the third release step 170 of FIG. 2 can be omitted and terminated 180. Figure 1

[0112] The compound of the third injection step can specifically refer to hydrogen (H2), nitrogen (N2), ammonia (NH3), oxygen (O2), ozone (O3), or a combination thereof, and when the third injection step is further included, the silicon seed layer can be nitridated or oxidized.

[0113] ​For example, the silicon seed layer can be a silicon nitride film or a doped silicon nitride film, and the oxide film can be a silicon oxide film or a doped silicon oxide film.

[0114] In an embodiment, after the third implantation step, a third release gas can be injected into the cavity. At this time, the third release gas can be hydrogen (H2), argon (Ar), nitrogen (N2), helium (He), a rare gas, an inert gas, or a combination thereof.

[0115] In an embodiment, the third release gas injection time of the third release step can 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.

[0116] If the third release gas injection time is less than the range, an increase in the residual amount of the compound injected in the third implantation step can cause an inappropriate reaction, and impurities cannot be released, resulting in uneven deposition of the thin film layer.

[0117] In an embodiment, after the silicon seed layer is formed, a second cycle can be further repeated to form a silicon thin film, the second cycle including a first implantation step of injecting the first precursor compound on the silicon seed layer, and a second implantation step of injecting the second precursor compound.

[0118] That is, it means that the silicon thin film can be formed by repeating the first cycle one or more times and 70 times or less, and further repeating the second cycle.

[0119] The number of repetitions of the second cycle can be one or more times and 500 times or less. For example, 400 times or less, 300 times or less, 200 times or less, or 100 times or less.

[0120] At this time, the silicon seed layer can be a silicon seed layer without the third implantation step or a nitrided or oxidized silicon seed layer further including the third implantation step. In addition, the silicon seed layer means a seed layer formed by injecting the third release gas after the third implantation step.

[0121] Figure 2 Each sequence of the first implantation step, the first release step, the second implantation step, and the second release step of the second cycle is shown in Table 1.

[0122] In an embodiment, the silicon thin film formed on the silicon seed layer can be any one of an amorphous state, a mixed state of an amorphous state and a nano crystalline state, and a nano crystalline state.

[0123] Generally, according to the atomic layer deposition method, the arrangement of atoms or molecules is disordered and has no regularity. This typically occurs in a rapid cooling process or a specific chemical process, when there is not enough time to form a crystalline structure.

[0124] The thin film in an amorphous state can be produced in the atomic layer deposition process, and the thermal, mechanical, and electrical properties of the substance in this state are generally constant in the direction.

[0125] The nanocrystalline state refers to a substance having a crystalline structure of nanometer scale. The nanocrystalline has unique physical properties due to its small size and high surface-to-volume ratio. The substance in this state can exhibit different characteristics from the substance in the amorphous state in terms of electrical, optical, mechanical properties, etc. The thin film in the nanocrystalline state can be manufactured by the atomic layer deposition process.

[0126] In the deposition process of the thin film, the morphology of the thin film can be determined during the deposition process under specific conditions of temperature, pressure, deposition time, etc., or after the deposition of the thin film, a crystallization treatment is performed to determine.

[0127] The surface shape of the thin film can be adjusted by the kind of the first precursor compound and the second precursor compound herein.

[0128] In addition, according to the manufacturing method herein, the thin film in the nanocrystalline state and the amorphous state and the mixed state of the nanocrystalline state can be obtained without an additional heat treatment after deposition.

[0129] In an embodiment, the silicon thin film can be a pure amorphous silicon (Si) thin film containing no carbon (C) and / or nitrogen (N). However, carbon (C), nitrogen (N), and / or oxygen (O) can be detected in the thin film due to oxidation or contamination of the surface of the thin film.

[0130] In an embodiment, the grain size of the thin film manufactured using the manufacturing method herein can be 30 nm or more and 50 nm or less as measured by SEM.

[0131] For example, the grain size can 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, 37.3 nm or more and 47.6 nm or less.

[0132] In an embodiment, the amorphous silicon thin film formed by the manufacturing method herein can be further heat-treated to form a crystallized silicon thin film.

[0133] At this time, hydrogen (H2) can be simultaneously injected in the first injection step, the second injection step, the third injection step, the first release step, the second release step, the third release step, the fourth injection step, the fourth release step, or a combination thereof to adjust the hydrogen (H) content of the thin film, and by adjusting the hydrogen (H) content within the thin film, the crystallized silicon thin film particle size can be adjusted.

[0134] In one embodiment, the roughness of the thin film manufactured using the manufacturing method can have an Rq value of 0.1 nm or more and 0.5 nm or less in a scan size of 5 μm as measured by AFM.

[0135] For example, the Rq value can be 0.1 nm or more and 0.5 nm or less, 0.15 nm or more and 0.4 nm or less, 0.15 nm or more and 0.3 nm or less, 0.2 nm or more and 0.25 nm or less, 0.2 nm or more and 0.3 nm or less, 0.2 nm or more and 0.35 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 0.36 nm or less, 0.3 nm or more and 0.5 nm or less, 0.31 nm or more and 0.49 nm or less, 0.32 nm or more and 0.48 nm or less, 0.33 nm or more and 0.46 nm or less, or 0.34 nm or more and 0.45 nm or less.

[0136] In one embodiment, the roughness of the thin film manufactured using the manufacturing method can have an Ra value of 0.1 nm or more and 0.4 nm or less in a scan size of 5 μm as measured by AFM.

[0137] For example, the Ra value can 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.

[0138] In one embodiment, after the formation of the silicon, a fourth implantation step of injecting a compound including hydrogen (H), nitrogen (N), oxygen (O), or a combination thereof into the cavity can be further included. The compound of the fourth implantation step can specifically refer to hydrogen (H2), nitrogen (N2), ammonia (NH3), oxygen (O2), ozone (O3), or a combination thereof, and the silicon seed layer can be nitrided or oxidized when the third implantation step is further included.

[0139] For example, the silicon seed layer can be a silicon nitride film or a doped silicon nitride film, and the oxide film can be a silicon oxide film or a doped silicon oxide film.

[0140] In one embodiment, a fourth release gas can be injected into the cavity after the fourth implantation step. At this time, the fourth release gas can use hydrogen (H2), argon (Ar), nitrogen (N2), helium (He), a noble gas, an inert gas, or a combination thereof.

[0141] Figure 2 Each sequence of the fourth implantation step and the fourth release step is illustrated in FIG. 4. The fourth implantation step and the fourth release step can be selectively performed when the nitridation or oxidation of the silicon thin film is required. When the fourth implantation step and the fourth release step are not performed, the fourth implantation step 260 and the fourth release step 270 of FIG. 4 can be omitted and terminated 280. Figure 2

[0142] In one embodiment, the fourth release gas injection time of the fourth release step can 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.

[0143] If the fourth release gas injection time is less than the range, the increase in the residual amount of the compound injected in the fourth implantation step can cause an inappropriate reaction, and impurities can not be released, resulting in uneven deposition of the thin film layer.

[0144] Hereinafter, the present disclosure will be further described using manufacturing examples, but the present disclosure is not limited thereto.

[0145] [Manufacturing Example]

[0146] A thin film was manufactured using an atomic layer deposition (ALD) apparatus using the first precursor compound and the second precursor compound.

[0147] ​The substrate used in this experiment was a p-type SiO2(110 nm) wafer with a resistance of 0.02 Ωcm. Prior to deposition, the p-type Si wafer was cleaned by ultrasonic treatment in acetone-ethanol-deionized water (DI water) for 10 minutes each. The native oxide film on the Si wafer was removed by immersion in a solution of HF 1% (HF:H2O = 1:100) for 10 seconds. The HF-cleaned Si wafer was immediately transferred to an atomic layer deposition (ALD) chamber.

[0148] In addition, as shown in Table 1 below, the first precursor compound used in the manufacture of the thin film was diiodosilane (DIS).

[0149] Among the second precursor compounds, tetrachloro disilane (TCDS) and pentachloro disilane (PCDS) were used, respectively.

[0150] If the storage canister temperature of the first precursor compound was maintained at 25°C in Manufacturing Example 1, it was maintained at 5°C in Manufacturing Example 2.

[0151] The supply was performed in the order of first precursor compound-argon (Ar)-second precursor compound-argon (Ar), and this was repeated as one cycle.

[0152] The cycle was repeated 70 times in Manufacturing Example 1 and 180 times in Manufacturing Example 2.

[0153] The injection time of the first precursor compound (DIS) was adjusted to 3-10 seconds. At this time, the injection amount of the first precursor compound (DIS) was 100 sccm, and the process pressure was 3.2-4.0 Torr.

[0154] The injection time of the second precursor compound used in Manufacturing Examples 1 and 2 was adjusted to 5-15 seconds for injection. At this time, the injection amount of the second precursor compound was 100 sccm, and the process pressure was 3.0-4.0 Torr.

[0155] The cycle was repeated 70 times in Manufacturing Example 3 and 200 times in Manufacturing Example 4.

[0156] The injection time of the first precursor compound (DIS) was adjusted to 3-10 seconds. At this time, the injection amount of the first precursor compound (DIS) was 100 sccm, and the process pressure was 3.2-4.0 Torr.

[0157] The injection time of the second precursor compound used in Manufacturing Examples 3 and 4 was adjusted to 5 to 15 seconds for injection. At this time, the injection amount of the second precursor compound was 100 seem, and the process pressure was 3.0 to 4.0 torr.

[0158] That is, in Manufacturing Example 1 and Manufacturing Example 3, the third injection step and the third release step in Figure 1 were not performed, but the first injection step, the first release step, the second injection step, and the second release step were sequentially repeated 70 times to manufacture the silicon seed layer.

[0159] In addition, in Manufacturing Example 2 and Manufacturing Example 4, the third injection step and the third release step in Figure 1 were not performed, but the first injection step, the first release step, the second injection step, and the second release step were sequentially repeated 70 times to manufacture the silicon seed layer, and then the first injection step, the first release step, the second injection step, and the second release step were sequentially repeated 110 times and 130 times, respectively, on the silicon seed layer to manufacture the silicon thin film. Figure 2

[0160] The process conditions for thin film manufacturing according to each manufacturing example are shown in Table 1 below.

[0161] [Table 1]

[0162]

[0163] In the table 1, DIS is diiodo silane, TCDS is tetrachlorodisilane, and PCDS is pentachlorodisilane.

[0164] Manufacturing Example 5 is based on the silicon thin film manufactured in Manufacturing Example 2. Further, ammonia (NH3) - argon (Ar) was sequentially provided.

[0165] Manufacturing Example 6 is based on the silicon thin film manufactured in Manufacturing Example 2, and further, ozone (O3) - argon (Ar) was sequentially provided.

[0166] Manufacturing Example 7 is based on the silicon thin film manufactured in Manufacturing Example 4, and further, ammonia (NH3) - argon (Ar) was sequentially provided.

[0167] Manufacturing Example 8 is based on the silicon thin film manufactured in Manufacturing Example 4, and further, ozone (O3) - argon (Ar) was sequentially provided.

[0168] That is, in Manufacturing Examples 5 to 8, the first injection step, the first release step, the second injection step, and the second release step in Figure 2 ​The fourth injection step and the fourth release step of the fourth deposition step and the fourth release step are performed to oxidize or nitride the silicon thin film.

[0169] The process conditions for the silicon thin film manufacturing according to the manufacturing examples 5 to 8 are shown in the following Table 2.

[0170]

Table 2

[0171]

[0172]

[0173] [Example 1 - Change in thin film deposition rate according to injection time of first precursor compound]

[0174] Under the process conditions described in the Table 1, after changing the injection time of the first precursor compound in the range of 3 to 10 seconds, each thin film was manufactured according to the manufacturing examples, and the growth rate per cycle (GPC) of the thin film was measured.

[0175] The growth rate of the evaluation examples 1 to 3 was calculated by the following mathematical formula 1.

[0176] [mathematical formula 1]

[0177]

[0178] The deposition thickness of the mathematical formula 1 was measured by an ellipsometer, and was confirmed using a field emission scanning electron microscope (FE-SEM).

[0179] The atomic layer deposition (ALD) process according to the manufacturing examples 2 and 4 was performed at a process temperature of 430°C. In the process, the self-limiting reaction was confirmed by measuring the source feeding time indicating a certain thin film growth rate.

[0180] [Example 2 - Change in thin film deposition rate according to injection time of second precursor compound]

[0181] Under the process conditions described in the Table 1, after changing the injection time of the second precursor compound of the manufacturing example 2 in the range of 5 to 15 seconds, the silicon thin film was manufactured according to the manufacturing examples, and the growth rate of the thin film was measured.

[0182] An atomic layer deposition (ALD) process was performed according to the manufacturing method of Manufacturing Example 2, in which the first precursor compound was used as a source and the second precursor compound was used as a reactant, at a process temperature of 430°C. In the process, a self-limiting reaction was confirmed by measuring the second precursor injection time indicating a certain thin film deposition rate.

[0183] On the other hand, under the process conditions described in Table 1, after changing the second precursor injection time of Manufacturing Example 4 in the range of 5 to 15 seconds, a thin film was manufactured according to the manufacturing example and the deposition rate of the thin film was measured.

[0184] An atomic layer deposition (ALD) process was performed according to the manufacturing method of Manufacturing Example 4, in which the first precursor compound was used as a source and the second precursor compound was used as a reactant, at a process temperature of 430°C. In the process, a self-limiting reaction was confirmed by measuring the second precursor injection time indicating a certain thin film deposition rate.

[0185] [Example 3 - Change in thin film deposition rate according to process temperature]

[0186] Under the process conditions described in Table 1, after changing the process temperature to the range of 400 to 450°C in Manufacturing Example 2 and 420 to 450°C in Manufacturing Example 4, a thin film was manufactured according to the manufacturing example and the deposition rate of the silicon thin film was measured.

[0187] [Example 4 - Grainsize analysis of Manufacturing Example 2 and Manufacturing Example 4]

[0188] The grain of Manufacturing Example 2 when using DIS as the first precursor compound and TCDS as the second precursor compound was analyzed by scanning electron microscopy (SEM).

[0189] The grain of Manufacturing Example 4 when using DIS as the first precursor compound and PCDS as the second precursor compound was analyzed by scanning electron microscopy (SEM).

[0190] [Example 5 - AFM analysis of Manufacturing Example 2, Manufacturing Example 4, Manufacturing Example 5 to Manufacturing Example 8]

[0191] The thin film morphology of Manufacturing Example 2 when using DIS as the first precursor compound and TCDS as the second precursor compound was analyzed by atomic force microscopy (AFM).

[0192] The film morphology of the film of Manufacturing Example 4, in which DIS was used as the first precursor compound and PCDS was used as the second precursor compound, was analyzed by atomic force microscopy (AFM).

[0193] The film morphology of the film of Manufacturing Example 5, in which ammonia (NH3) was used as the third implantation step compound, was analyzed by atomic force microscopy (AFM) in the film manufactured in Manufacturing Example 2.

[0194] The film morphology of the film of Manufacturing Example 6, in which ozone (O3) was used as the third implantation step compound, was analyzed by atomic force microscopy (AFM) in the film manufactured in Manufacturing Example 2.

[0195] The film morphology of the film of Manufacturing Example 7, in which ammonia (NH3) was used as the third implantation step compound, was analyzed by atomic force microscopy (AFM) in the film manufactured in Manufacturing Example 4.

[0196] The film morphology of the film of Manufacturing Example 8, in which ozone (O3) was used as the third implantation step compound, was analyzed by atomic force microscopy (AFM) in the film manufactured in Manufacturing Example 4.

[0197] [Example 6 - X-ray Diffraction (XRD) analysis of Manufacturing Example 2, Manufacturing Example 4, Manufacturing Example 5 to Manufacturing Example 8] ​

[0198] The film morphology of the film of Manufacturing Example 2, in which DIS was used as the first precursor compound and TCDS was used as the second precursor compound, was analyzed by X-ray diffraction analysis.

[0199] The film morphology of the film of Manufacturing Example 4, in which DIS was used as the first precursor compound and PCDS was used as the second precursor compound, was analyzed by X-ray diffraction analysis.

[0200] The film morphology of the film of Manufacturing Example 5, in which ammonia (NH3) was used as the third implantation step compound, was analyzed by X-ray diffraction analysis in the film manufactured in Manufacturing Example 2.

[0201] The film morphology of the film of Manufacturing Example 6, in which ozone (O3) was used as the third implantation step compound, was analyzed by X-ray diffraction analysis in the film manufactured in Manufacturing Example 2.

[0202] The film morphology of the film of Manufacturing Example 7, in which ammonia (NH3) was used as the third implantation step compound, was analyzed by X-ray diffraction analysis in the film manufactured in Manufacturing Example 4.

[0203] The film manufactured in Manufacturing Example 4 was analyzed by X-ray diffraction analysis to analyze the film morphology of the film of Manufacturing Example 8 in which ozone (O3) was used as the third injection step compound.

[0204] It was confirmed from the film manufacturing that when the manufacturing method of the first precursor compound and the second precursor compound of Manufacturing Examples 2 and 4 was used, a silicon film having excellent properties could be formed by atomic layer deposition at a low temperature process of 500°C or less.

[0205] The scope of the present document is specified by the following claims, and all variations or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as included in the scope of the present document.

[0206] Explanation of symbols

[0207] 110: first injection step of first cycle

[0208] 120: first release step of first cycle

[0209] 130: second injection step of first cycle

[0210] 140: first release step of first cycle

[0211] 150: step of determining whether to repeat first cycle

[0212] 160: third injection step

[0213] 170: third release step

[0214] 180: termination of silicon seed layer manufacturing

[0215] 210: first injection step of second cycle

[0216] 220: first release step of second cycle

[0217] 230: second injection step of second cycle

[0218] 240: second release step of second cycle

[0219] 250: step of determining whether to repeat second cycle

[0220] 260: fourth injection step

[0221] 270: fourth release step

[0222] 280: termination of silicon film manufacturing

Claims

1. A method of manufacturing a thin film, characterized by, comprising the steps of: repeating a first cycle to deposit a thin film, the first cycle comprising the steps of: a first injection step of injecting a first precursor compound into a cavity; and a second injection step of injecting a second precursor compound into the cavity, the first precursor compound is represented by the following Chemical Formula 1, the second precursor compound is represented by the following Chemical Formula 2, [Chemical Formula 1] Si(R1) x H (4-x) [Chemical Formula 2] Siy(R2) z H (2y+2-z) in the Chemical Formulas 1 and 2, R1 and R2 are each individually any one selected from the group consisting of fluorine, chlorine, bromine, and iodine, x is an integer of 1 to 4, when y is equal to 1, z is an integer of 0 to 4, when y is equal to 2 or 3, z is an integer of 0 to 6.

2. The method of manufacturing a thin film according to claim 1, wherein between the first injection step and the second injection step, the method further comprises: a first release step of injecting a first release gas into the cavity; and after the second injection step, a second release step of injecting a second release gas into the cavity.

3. The method of manufacturing a thin film according to claim 2, wherein further injecting hydrogen in the first injection step, the second injection step, the first release step, the second release step, or in a combination thereof.

4. The method of manufacturing a thin film according to claim 1, wherein the compound represented by the Chemical Formula 1 is any one or more selected from the group consisting of fluorosilane, chlorosilane, bromosilane, iodosilane, difluorosilane, dichlorosilane, dibromosilane, diiodosilane, trifluorosilane, trichlorosilane, tribromosilane, triiodosilane, tetrafluorosilane, tetrachlorosilane, tetrabromosilane, and tetraiodosilane.

5. The method of manufacturing a thin film according to claim 1, wherein the compound represented by the Chemical Formula 2 is any one or more selected from the group consisting of silane, fluorosilane, chlorosilane, bromosilane, iodosilane, difluorosilane, dichlorosilane, dibromosilane, diiodosilane, trifluorosilane, trichlorosilane, tribromosilane, triiodosilane, tetrafluorosilane, tetrachlorosilane, tetrabromosilane, tetraiodosilane, disilane, difluorodisilane, dichlorodisilane, dibromodisilane, diiododisilane, trifluorodisilane, trichlorodisilane, tribromodisilane, triiododisilane, tetrafluorodisilane, tetrachlorodisilane, tetrabromodisilane, tetraiododisilane, pentafluorodisilane, pentachlorodisilane, pentabromodisilane, pentaiododisilane, hexafluorodisilane, hexachlorodisilane, hexabromodisilane, hexaiododisilane, trisilane, fluorotrisilane, chlorotrisilane, bromotrisilane, iodotrisilane, difluorotrisilane, dichlorotrisilane, dibromotrisilane, diiodotrisilane, trifluorotrisilane, trichlorotrisilane, tribromotrisilane, triiodotrisilane, tetrafluorotrisilane, tetrachlorotrisilane, tetrabromotrisilane, tetraiodotrisilane, pentafluorotrisilane, pentachlorotrisilane, pentabromotrisilane, pentaiodotrisilane, hexafluorotrisilane, hexachlorotrisilane, hexabromotrisilane, and hexaiodotrisilane.

6. The method of manufacturing a thin film according to claim 1, wherein the process temperature is 350°C or higher and 500°C or lower.

7. The method of manufacturing a thin film according to claim 1, wherein The first cycle is 1 or more to 70 times or less, The thin film manufactured by repeating the first cycle is a silicon seed layer.

8. The method of manufacturing a thin film according to claim 7, wherein The method further comprises: a third implantation step of implanting a compound containing hydrogen, nitrogen, oxygen, or a combination thereof into the cavity, wherein the silicon seed layer is nitrided or oxidized.

9. The method of claim 8, wherein after the third implantation step, the method comprises: a third release step of releasing a third release gas into the cavity.

10. The method of any one of claims 7 to 9, wherein a second cycle is further repeated to form a silicon thin film, the second cycle comprising: a first implantation step of implanting the first precursor compound onto the silicon seed layer; and a second implantation step of implanting the second precursor compound, the silicon thin film formed on the silicon seed layer is any one of an amorphous state, a mixture of an amorphous state and a nanocrystalline state, and a nanocrystalline state.

11. The method of claim 10, wherein the silicon thin film is nitrided or oxidized.

12. The method of claim 10, wherein The method further comprises: a fourth implantation step of implanting a compound containing hydrogen, nitrogen, oxygen, or a combination thereof into the cavity.

13. The method of claim 12, wherein after the fourth implantation step, the method comprises: a fourth release step of releasing a fourth release gas into the cavity.

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