WO2021145661A2 - Precursor compound for atomic layer deposition (ald) or chemical vapor deposition (cvd), and ald/cvd method using same - Google Patents

Abstract

The present invention relates to a precursor compound and, more specifically, to: a precursor compound comprising a metal of Group 13 of the Periodic Table and available for thin film deposition through atomic layer deposition (ALD) or chemical vapor deposition (CVD); and a method for manufacturing a thin film by using same.　

Description

Atomic layer deposition (ALD), chemical vapor deposition (CVD) precursor compound and ALD/CVD deposition method using the same

The present invention relates to a novel precursor compound, and more particularly, a precursor compound capable of depositing a thin film through atomic layer deposition (ALD) and chemical vapor deposition (CVD), and ALD/CVD using the same It relates to vapor deposition.

The Al ₂ O ₃ thin film is mainly applied to the semiconductor industry in fields requiring chemical inertness and high thermal conductivity.

They are used in the manufacture of liquid crystal displays, electroluminescent displays, solar cells, bipolar devices and silicon on insulator (SOI) devices. In addition, Al ₂ O ₃ is also used as a wear-resistant and corrosion-resistant coating material used in the tool manufacturing industry.

_{In particular, the recent method of manufacturing an Al 2} O ₃ thin film using the ALD/CVD process is applied to prevention of corrosion and moisture blocking of metal materials due to moisture, which is a difficult problem in organic electronic devices, intermediate insulators, and passivation of solar cells. It is considered a possible technology.

Al ₂ O ₃ thin film manufacturing process has a low deposition temperature has been required as Al ₂ O ₃ thin film for preparing the precursor using conventional ALD / CVD process is widely used in the _{TMA (trimethylaluminium, Al (CH 3} ) 3).

TMA has an ideal ALD thin film deposition rate, but has a fatal flaw, autoignition. Therefore, research on precursors that are safe even for large-volume manufacturing on an industrial scale is ongoing.

On the other hand, as a study related to non-incendive precursor compounds including aluminum (Al) as a group 13 metal, the literature (Plasma-enhanced and thermal atomic layer deposition of Al ₂ O ₃ using dimethylaluminum isopropoxide, [Al(CH ₃ ) ₂ (μ-O) ⁱ Pr)] ₂ , as an alternative aluminum precursor, J.Vac.Sci.Technol.A, 2012, 30(2), 021505-1) in [Al(CH ₃ ) ₂ (μ-O ⁱ Pr)] ₂ Although the manufacturing method of (DMAI, ⁱ Pr=isopropyl) has been disclosed, there is a disadvantage in that the density of the _{Al 2} O _{3 thin film after the ALD process is low.}

Another aluminum-containing non-flammable precursor, amine-alane, has the disadvantages of short shelf life, high viscosity and low vapor pressure.

Therefore, there is a need to develop a novel aluminum precursor compound that is nonpyrophoric applicable to ALD/CVD processes, has thermal stability, and has high reactivity with various oxidizing agents, nitriding agents, or reducing agents.

In addition, there is a continuing demand for a precursor that is in a liquid state at room temperature, has a sufficient vapor pressure, and can obtain a uniform film.

Accordingly, it would be desirable to develop precursors having some, or preferably all, of the above properties.

[Prior art literature]

[Patent Literature]

(Patent Document 1) Korean Patent No. 10-1787204 (Registration Date: 2017.10.11)

Accordingly, in order to solve the above problems, an object of the present application is to provide a novel precursor compound applicable to atomic layer deposition (ALD) and chemical vapor deposition (CVD), and a method for manufacturing a thin film on which the precursor compound is deposited.

That is, the novel precursor compound of the present application includes a group 13 metal, is not pyrophoric, and can implement high thermal stability and reactivity.

In addition, the precursor compound of the present application can obtain a thin film of excellent quality through atomic layer deposition (ALD) or chemical vapor deposition (CVD) together with various reactive gases.

However, the problem to be solved by the present application is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present application provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

M is a metal of group 13 on the periodic table,

R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each is hydrogen, a substituted or unsubstituted linear or branched hydrocarbon having 1 to 4 carbon atoms, or an isomer thereof,

R ₃ is a substituted or unsubstituted linear or branched hydrocarbon having 4 to 6 carbon atoms or an isomer thereof.

Another aspect of the present application provides a precursor comprising the compound represented by Formula 1 above.

Another aspect of the present application provides a method for manufacturing a thin film comprising introducing a precursor including the compound represented by Formula 1 into a reactor.

In another aspect of the present application, the thin film prepared by the method for manufacturing a thin film using a precursor containing the compound represented by Formula 1 has a surface roughness (Ra) of 1.4 Å or less, and a density of 3 g/cm ³ or more. to provide.

Another aspect of the present application provides an electronic device including the thin film.

According to the present application, it is possible to prepare a novel precursor compound including a metal of Group 13 (Al: aluminum, Ga: gallium, In: indium, etc.). The precursor compound does not spontaneously ignite in the atmosphere and has high thermal stability and reactivity.

In addition, the precursor compound of the present application can obtain a thin film of excellent quality through atomic layer deposition (ALD) or chemical vapor deposition (CVD) together with various reactive gases.

1 is a graph showing the results of differential scanning calorimetry (DSC) analysis of the novel precursor compound of the present application.

2 is a graph showing the results of thermogravimetric (TG) analysis of the novel precursor compound of the present application.

3 is a graph of the measurement result of the evaporation rate of the novel precursor compound of the present application.

4 is a graph showing changes in component content in _{Al 2} O ₃ thin films according to process temperature using X-ray Photoelectron Spectroscopy (XPS).

5 is a graph showing the change in density _{of the Al 2} O ₃ thin film according to the process temperature using X-ray reflectivity (XRR).

6 is a graph showing the surface roughness _{of the Al 2} O ₃ thin film according to the change in process temperature measured with an atomic force microscope (AFM).

7 is an image illustrating a change in step coverage according to a process temperature in a trench structure using a transmission electron microscopy (TEM). The aspect ratio (AR) of the trench structure is 40:1.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms, and is not limited to the embodiments described herein.

Prior to this, the terms used in this specification should not be construed as being limited to conventional or dictionary meanings, and the principle that the inventor can appropriately define the concept of the term to describe his invention in the best way It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the

In this specification, the singular expression includes the plural expression unless the context clearly dictates otherwise. It should also be understood that the term "comprises" and the like does not preclude the possibility of adding or adding one or more other features or numbers, steps, elements, or combinations thereof.

Where ranges of numerical values are given herein, all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value are specifically disclosed, regardless of whether the range is separately disclosed. should be understood as

The compound according to the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

M is a metal of group 13 on the periodic table,

R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each is hydrogen, a substituted or unsubstituted linear or branched hydrocarbon having 1 to 4 carbon atoms, or an isomer thereof,

R ₃ is a substituted or unsubstituted linear or branched hydrocarbon having 4 to 6 carbon atoms or an isomer thereof.

M in Formula 1 may be one selected from the group consisting of Al, In, and Ga.

_{R 3} of Formula 1 may be one selected from the group consisting of n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, and isomers thereof, preferably R _{3 of Formula 1} may be a sec-butyl group or a tert-butyl group.

Also, R ₁ , R ₂ , R ₄ and R ₅ may be the same or different and each may be a methyl group or an ethyl group.

The compound of the present invention is prepared by a method for preparing a compound comprising reacting an aluminum compound with an organic diamine compound serving as a ligand in the presence of a solvent and separating the synthesized compound from the reaction mixture.

The aluminum compound starting material used in the preparation of the compound may be selected from various compounds known in the art. The aluminum compound may be, for example, Al(CH ₃ ) ₃ , Al(CH ₃ ) ₂ H, Al(CH ₃ CH ₂ ) ₃ , Al(CH ₃ CH ₂ ) ₂ (CH ₃ ), Al(CH ₃ CH _{2 )} ) ₂ H, Al(CH ₃ CH ₂ CH ₂ ) ₃ and the like.

The organic diamine compound starting material used for preparing the compound includes a substituted or unsubstituted linear or branched hydrocarbon having 4 to 6 carbon atoms corresponding to _{the R 3 substituent of Formula 1 or an isomer substituent thereof.}

The solvent used for the preparation of the compound includes any saturated and unsaturated hydrocarbons, aromatic hydrocarbons, aromatic heterocycles, alkyl halides, silylated hydrocarbons, ethers, polyethers, thioethers, esters, thioesters, lactones, amides, amines, polyamines. , nitriles, silicone oils, other aprotic solvents, or mixtures of one or more of the foregoing; More preferably, diethyl ether, pentane or dimethoxyethane; Most preferably, it may be hexane or toluene. Any suitable solvent that does not significantly oppose and do not interfere with the intended reaction may be used. If desired, mixtures of one or more different solvents may be used.

The compounds of the present invention may be purified through recrystallization, more preferably through extraction and chromatography of the reaction residue (eg hexane), most preferably through sublimation and distillation.

The compounds of the present invention are preferably in the liquid state at room temperature (20° C.).

The precursor according to the present invention comprises the above compound.

The method for producing a thin film according to the present invention includes introducing the precursor into a reactor.

In addition, the method may further include depositing at a process temperature of 150° C. or higher. The process temperature may be preferably 230°C or higher, and more preferably 300°C or higher.

The method of manufacturing a thin film of the present invention may include the step of using an oxidizing agent, a nitriding agent, or a reducing agent to prepare an oxide film, a nitride film, or a metal thin film.

The manufacturing method of the thin film may be by vapor deposition or may be performed in the presence of other gas components. The deposition of the thin film may be carried out in the presence of one or more inert carrier gases. Inert carrier gases include, for example, nitrogen, argon, helium, as well as other gases that do not react with the precursors of the present invention under process conditions.

In addition, the thin film deposition of the present invention can be carried out in the presence of one or more reactive gases. The reactive gas that can be used may be an oxidizing agent, a nitriding agent, a reducing agent and the like. Examples include, but are not limited to, hydrazine, air, oxygen, oxygen enriched air, ozone, hydrogen, nitrogen, nitric oxide, nitrogen dioxide, nitrous oxide, water vapor, organic vapor, ammonia, and the like.

In particular, the presence of oxidizing gases such as air, oxygen, oxygen enriched air, ozone, water vapor, nitrous oxide or vapors of oxidizable organic compounds, as is known in the art, is advantageous for the formation of thin metal oxide films.

The deposition of the present invention can be performed to form a thin film containing a single metal or a thin film containing multiple types of metals.

In addition, the thin film prepared through the deposition of the present invention may have a surface roughness (Ra) of 1.4 Å or less and a density of 3 g/cm ^{3 or} more.

The thin film of the present invention may be used in various electronic devices, particularly semiconductors, displays, solar cells, and the like.

The precursors of the present invention can be formed into thin films by atomic layer deposition (ALD), which sequentially exposes a substrate to alternating pulses of precursor, reactant gas and inert gas flows.

In other words, atomic layer deposition is a technology that forms a thin film by a self-limiting reaction by alternately supplying elements necessary for thin film formation, and can deposit a very thin film, and the desired thickness and composition can be precisely controlled. . It can form a film of uniform thickness even on a large-area substrate, and exhibits excellent step coverage even at a high aspect ratio. In addition, it has the advantage that there are few impurities in the thin film.

For example, in one ALD cycle, the substrate may sequentially comprise: a) an inert carrier gas carrying the precursor; b) an inert gas; c) reactive gases (eg oxidizing agents, reducing agents, nitriding agents, etc.), or inert gases and reactive gases and d) inert gases.

In general, each step can be as short as the equipment allows (eg, milliseconds), and as long as the process requires (eg, seconds or minutes). The length of one cycle may be as short as several milliseconds and as long as several minutes. The cycle repeats over a period that can range from minutes to hours.

The precursor of the present invention can be used to prepare a film comprising a single aluminum, a thin film comprising a single aluminum oxide, a single aluminum nitride, and the like. In addition, mixed thin films such as mixed metal oxide, nitride thin films and the like may also be deposited.

Such thin films can be prepared using, for example, several organometallic precursors. Metal films may also be prepared without the use of, for example, carrier gases, vapors or other reactive gas sources.

Hereinafter, the present application will be described in more detail using Examples, Experimental Examples and Preparation Examples, but the present application is not limited thereto.

[Example 1]

Ligand (N ¹ -(tert-butyl)-N ² ,N ² -dimethylethane-1,2-diamine) synthesis

A method of synthesizing the ligand is shown in Formula 1 below.

[Equation 1]

(In Formula 1, tBu is a tert-butyl group)

Specifically, _{2-Chloro-N,N-dimethylethylamine hydrochloride was added to a flask containing H 2} O and stirred to prepare a transparent aqueous solution, tert-butylamine was added to the prepared aqueous solution, and the flask was placed in a constant temperature water bath at 20 ° C ( water bath) for about 24 hours.

Then, the flask was moved to an ice bath, cooled aqueous NaOH aqueous solution was added, stirred for 10 minutes, extracted with hexane, and the solvent was removed under reduced pressure, N ¹ -(tert-butyl)-N ² , N ² -dimethylethane-1,2-diamine is obtained.

The yield of the ligand N ¹ -(tert-butyl)-N ² ,N ² -dimethylethane-1,2-diamine is 17-32 %, and it is a colorless liquid at room temperature.

[Example 2]

Synthesis of precursor compound (Al(CH ₃ ) ₂ [(CH ₃ ) ₂ NCH ₂ CH ₂ NtBu])

A method of synthesizing the precursor compound is shown in Formula 2 below.

[Equation 2]

(In Formula 2, tBu is a tert-butyl group)

^{Specifically, 1 equivalent of N 1} -(tert-butyl)-N ² ,N ² -dimethylethane-1,2-diamine, which is the ligand synthesized in Example 1, 1M Al(CH) dissolved in hexane or heptane at -78°C ₃ ) Add to _{1 equivalent of 3} , gradually raise the temperature to room temperature, and then stir for about 24 hours. The reaction is complete and the solvent is removed under vacuum.

The yield of the reaction is 90 to 97%, and the obtained compound is in a pale yellow liquid state at room temperature.

Subsequent vacuum distillation purification (45-50℃@300 mTorr) Thus, a colorless liquid precursor compound Al(CH ₃ ) ₂ [(CH ₃ ) ₂ NCH ₂ CH ₂ NtBu] is obtained. The purification yield is 71-80%.

¹ H NMR of the obtained precursor compound is as follows.

¹ H NMR (C ₆ D ₆ ):

δ 2.77 Al(CH ₃ ) ₂ [(CH ₃ ) ₂ NCH ₂ CH ₂ NtBu], t, 2H)

δ 2.11 Al(CH ₃ ) ₂ [(CH ₃ ) ₂ NCH ₂ CH ₂ NtBu], t, 2H)

δ 1.66 Al(CH ₃ ) ₂ [(CH ₃ ) ₂ NCH ₂ CH ₂ NtBu], s, 6H)

δ 1.33 Al(CH ₃ ) ₂ [(CH ₃ ) ₂ NCH ₂ CH ₂ NtBu], s, 9H)

δ -0.47 Al(CH ₃ ) ₂ [(CH ₃ ) ₂ NCH ₂ CH ₂ NtBu], s, 6H)

Aluminum synthesized through Example 2 The precursor compound was subjected to differential scanning calorimetry analysis, viscosity measurement, thermogravimetric analysis and evaporation rate measurement as follows to confirm physical properties.

[Experimental Example 1] Differential Scanning Calorimetry (DSC) analysis

Differential runner calorimetry analysis of the aluminum precursor compound was performed. At this time, about 7.8 mg of each sample was weighed, put into an alumina crucible, and measured from 35° C. to 500° C. at a temperature increase rate of 10° C./min, and the measured results are shown in FIG. 1 .

Referring to FIG. 1 , it was confirmed that the thermal decomposition temperature of the aluminum precursor compound was about 245°C.

[Experimental Example 2] Viscosity measurement

The viscosity (measured at 25° C.) of the aluminum precursor compound was measured in a glove box.

It was confirmed that the average viscosity of the aluminum precursor compound averaged by measuring a total of 5 times was 4.78 cP.

[Experimental Example 3] Thermogravimetric (TG) analysis

aluminum Thermogravimetric analysis of the precursor compound was performed.

The instrument used for thermogravimetric analysis was Mettler Toledo's TGA/DSC 1 STAR System, and an alumina crucible with a capacity of 50 μL was used. The amount of all samples was 10 mg, measured from 30°C to 400°C, and the temperature was increased at a rate of 10°C/min.

As shown in FIG. 2(a), the half-life [T _1/2 (°C)] of the aluminum precursor compound measured through thermogravimetric analysis was 161.9°C.

In addition, it was confirmed that the residual amount was 0.8 wt% at 200 °C and 0.2 wt% at 300 °C .

In addition, as shown in FIG. 2(b), iso thermogravimetric analysis of the aluminum precursor compound was performed.

The temperature was raised at a rate of 20 °C/min, and iso-thermogravimetric analysis was performed while maintaining the temperature at 80 °C, 100 °C, 120 °C and 150 °C for 2 hours, respectively.

As a result of performing iso-thermogravimetric analysis, the residual amount was about 80% when maintained at 80° C. for 2 hours, and when maintained at 100° C. for 2 hours, the residual amount was about 40%.

When the temperature was further increased and maintained at 100° C. for 2 hours, almost no residual amount was measured after about 85 minutes, and when the temperature was maintained at 150° C. for 2 hours, almost no residual amount was measured after about 30 minutes.

[Experimental Example 4] Evaporation rate measurement

The evaporation rate of the aluminum precursor compound was measured.

As shown in Fig. 3(a), it was found that the evaporation rate increased as the temperature increased.

Specifically, an evaporation rate of about 0.02 mg/min·cm ² was measured at 80° C., an evaporation rate of about 0.06 mg/min·cm ² was measured at 120° C., and the evaporation rate increased significantly at 150° C. to about 0.26 mg/min·cm 2 The evaporation rate of cm ^{2 was measured.}

In addition, the evaporation rate was measured as a rate constant k at a temperature T (T is an absolute temperature) and expressed as ln(k), which is a linear function of 1/T, and is shown in FIG. 3(b).

The evaporation rate of the aluminum precursor compound was measured to have an ln(k) value of about -4.0 mg/min·cm ² at 353 K, and an ln(k) value of about -2.5 mg/min·cm ² at 423 K.

[Preparation Example 1] Film formation through atomic layer deposition (ALD) process

Aluminum synthesized as in Example 2 Film formation was performed by atomic layer deposition (ALD) of the precursor compound. Ozone was used as the oxidizing agent, and argon, an inert gas, was used for the purpose of purging. Precursor (20 sec), argon (10 sec), ozone (5 sec) and argon (10 sec) were injected in one cycle, and deposition was performed on a Si (silicon) wafer, and the deposition temperature was 150° C. to 340° C. to form an Al ₂ O ₃ thin film.

_{For the thin film prepared by Preparation Example 1, an Al 2} O ₃ thin film deposited under different deposition temperatures using ozone as an oxidizing agent in the ALD process of an aluminum precursor compound as a film formation evaluation item Deposition through XPS (X-ray photoelectron spectroscopy) analysis Aluminum (Al), oxygen (O), carbon (C), nitrogen (N) content and ratio of O/Al in the thin film, density through X-ray reflectivity (XRR) analysis, and atomic force microscope (AFM) analysis Surface roughness and step coverage were evaluated through transmission electron microscope (TEM) analysis.

[Preparation Example 2] X-ray Photoelectron Spectroscopy (XPS) analysis

In the ALD process using ozone as an aluminum precursor compound and an oxidizing agent as in Preparation Example 1, changes in element content (Atomic %) and element ratio (Atomic ratio, O/Al ratio) according to process temperature change were measured by XPS (X-ray It was measured through photoelectron spectroscopy) analysis.

As shown in Figure 4, when the process temperature range was 230 °C to 340 °C, _{the content of the quantitative Al 2} O ₃ thin film according to the change in the process temperature was confirmed.

As shown in Table 1 below, when the process temperature was 230°C, 300°C, and 340°C, impurities such as C (carbon) and N (nitrogen) were not present, and Al (aluminum) and O (oxygen) It was confirmed that the content and the ratio of O/Al were kept constant.

process temperature	concentration, at%				O/Al ratio
	Al	O	C	N
230℃	39.9	59.9	0.0	0.2	1.50
300℃	40.2	59.8	0.0	0.0	1.49
340℃	40.2	59.8	0.0	0.0	1.49

[Preparation Example 3] X-ray reflectivity (XRR) analysis

In the ALD process using an aluminum precursor compound and ozone as an oxidizing agent as in Preparation Example 1, the change in the density of the thin film according to the process temperature was measured through X-ray reflectivity (XRR) analysis.

As shown in FIG. 5 and Table 2 below, it was confirmed that the density of the thin film tends to increase as the process temperature increases.

	process temperature
	230℃	300℃	340℃
density (g/cm 3 )	3.00	3.1	3.18

Bulk density: 3.95 g/cm ³

[Preparation Example 4] Atomic Force Microscope (AFM) analysis

In the ALD process using an aluminum precursor compound and ozone as an oxidizing agent as in Preparation Example 1, the surface roughness of the thin film according to the process temperature change was measured using an atomic force microscope (AFM). As shown in FIG. 6 and Table 3 below, as the process temperature range increased from 230°C to 340°C, the surface roughness (Ra) of the thin film generally decreased.

	process temperature
	230℃	300℃	340℃
surface roughness (Å)	1.37	1.08	1.10

[Preparation Example 5] Transmission electron microscopy (TEM) analysis

In the ALD process using ozone as an aluminum precursor compound and an oxidizing agent as in Preparation Example 1, the step coverage of the trench structure according to the process temperature was confirmed through TEM (Transmission electron microscopy) analysis. . The process temperature ranged from 230°C to 340°C, and the trench structure aspect ratio was 40:1.

As shown in FIG. 7 and Table 4 below, when the process temperature was 230 ° C., the floor step coverage was 84%, and when the process temperature was 300 ° C. and 340 ° C., the floor step coverage was 95% or more. It was. Accordingly, it was confirmed that the aluminum precursor compound had excellent step coverage in a wide process temperature range.

step coverage	process temperature
	230℃	300℃	340℃
side	89%	93%	97%
floor	84%	95%	96%

The above description of the present application is for illustration, and those of ordinary skill in the art to which the present application pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

The scope of the present application is indicated by the following claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims, and their equivalents should be construed as being included in the scope of the present application. .

According to the present application, it is possible to prepare a novel precursor compound including a metal of Group 13 (Al: aluminum, Ga: gallium, In: indium, etc.). The precursor compound does not spontaneously ignite in the atmosphere and has high thermal stability and reactivity.

In addition, the precursor compound of the present application can obtain a thin film of excellent quality through atomic layer deposition (ALD) or chemical vapor deposition (CVD) together with various reactive gases.

Claims (13)

1. A compound represented by the following formula (1):

   [Formula 1]

   

   In Formula 1,

   M is a metal of group 13 on the periodic table,

   R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each is hydrogen, a substituted or unsubstituted linear or branched hydrocarbon having 1 to 4 carbon atoms, or an isomer thereof,

   R ₃ is a substituted or unsubstituted linear or branched hydrocarbon having 4 to 6 carbon atoms or an isomer thereof.
2. According to claim 1,

   M in Formula 1 is a compound, characterized in that one selected from the group consisting of Al, In, and Ga.
3. According to claim 1,

   _{R 3} of Formula 1 is a compound, characterized in that one selected from the group consisting of n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, and isomers thereof.
4. 4. The method of claim 3,

   The R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each represents a methyl group or an ethyl group.
5. A precursor comprising the compound of any one of claims 1 to 4.
6. A method for producing a thin film comprising the step of introducing a precursor comprising the compound of any one of claims 1 to 4 into a reactor.
7. 7. The method of claim 6,

   The manufacturing method is a thin film manufacturing method comprising atomic layer deposition (ALD) or chemical vapor deposition (CVD).
8. 7. The method of claim 6,

   Method for producing a thin film further comprising the step of depositing at a process temperature of 150 ℃ or higher.
9. 7. The method of claim 6,

   The method of manufacturing a thin film further comprising the step of using any one of the group consisting of an oxidizing agent, a nitriding agent, or a reducing agent.
10. 7. The method of claim 6,

    The thin film is an oxide film, a nitride film, or a method of manufacturing a thin film comprising a metal thin film.
11. The surface roughness (Ra) manufactured by the manufacturing method of claim 6 is 1.4 A thin film of less than Å and a density of 3 g/cm ^{3 or more.}
12. An electronic device comprising the thin film of claim 11 .
13. 13. The method of claim 12,

    The electronic device is any one selected from the group consisting of a semiconductor, a display, and a solar cell.

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