KR20230039475A - Agent for enhancing film characteristics, method for forming thin film and semiconductor substrate prepared therefrom - Google Patents

Abstract

The present invention relates to an agent for enhancing film characteristics, a method for forming a thin film and a semiconductor substrate manufactured therefrom. In a thin film deposition process, a reaction gas is supplied in a plasma state while using an agent for enhancing film characteristics having a predetermined structure. Thus, the present invention has the effect of greatly improving the step coverage and thickness uniformity of the thin film even when the thin film of 10 nm or less is formed on a substrate having a complicated structure, reducing corrosion or deterioration, and improving electrical properties of the thin film by improving the crystallinity of the thin film.

Description

Film quality improver, method for forming a thin film using the same, and semiconductor substrate manufactured therefrom

The present invention relates to a film quality improver, a method for forming a thin film using the same, and a semiconductor substrate manufactured therefrom. The present invention relates to a film quality improving agent that greatly improves coverage and thickness uniformity of a thin film, thereby greatly improving electrical characteristics of the thin film, a thin film forming method using the same, and a semiconductor substrate manufactured therefrom.

The degree of integration of memory and non-memory semiconductor devices is increasing day by day, and as the structure becomes increasingly complex, fine and complex structures are used to deposit various thin films on substrates, such as using substrates with holes or trenches. The importance of step coverage, which evenly and uniformly forms an Edo thin film, is gradually increasing.

The semiconductor thin film is made of metal nitride, metal oxide, metal silicide, and the like. Examples of the metal nitride thin film include titanium nitride (TiN), tantalum nitride (TaN), and zirconium nitride (ZrN). It is used as a diffusion barrier with copper (Cu) and the like. However, when depositing a tungsten (W) thin film on a substrate, it is used as an adhesion layer. In addition, the metal nitride thin film is specifically applied to semiconductor devices such as barrier layers (diffusion prevention films) of NAND flash and upper/lower electrodes of memory devices.

In order to obtain excellent and uniform physical properties of a thin film deposited on a substrate, high step coverage of the formed thin film is essential. Therefore, the ALD (atomic layer deposition) process that utilizes surface reaction is preferred over the CVD (chemical vapor deposition) process that mainly utilizes gas phase reaction, but it still does not reach the desired level of step coverage.

In addition, in the case of titanium tetrachloride (TiCl ₄ ) used to deposit typical titanium nitride (TiN) among the metal nitrides, process by-products such as chloride remain in the thin film, causing corrosion of metals such as aluminum. In addition, non-volatile by-products are generated, resulting in deterioration of membrane quality.

On the other hand, with the high integration of semiconductor devices, the diameter (width) and depth of trenches or via holes are getting narrower. When a barrier layer is formed on the surface of the trench or via hole, both vertical surfaces Since the barrier layer is formed in the trench, the width of the trench is narrowed by twice the thickness of the barrier layer. At this time, since the electrode is formed on the barrier layer, as the device is miniaturized, the margin of the trench width that can be given to the electrode formation inevitably decreases, and accordingly, to secure the minimum electrical conductivity for driving the device A problem arises. Therefore, in order to secure the maximum trench width margin, it is advantageous to form a thin film such as a barrier layer as thinly as possible.

However, as the thickness of the thin film becomes thinner, nano-sized protrusions are generated on the thin film, and these protrusions are continuously formed to form an island grown film, resulting in deterioration of the film quality. Moreover, as the thickness of the thin film becomes thinner, the size of the protrusion becomes relatively prominent, so it is important to improve the uniformity of the thickness in forming the ultra-thin film.

Therefore, it is possible to form a uniform thin film even on a substrate with a complex structure, uniformly and continuously form an ultra-thin film with a smaller thickness, and develop a thin film formation method that does not corrode interlayer wiring materials and semiconductor substrates manufactured therefrom This is what is needed.

Korean Patent Publication No. 2006-0037241

In order to solve the problems of the prior art as described above, the present invention reduces process by-products by suppressing side reactions while forming a uniform thin film from the beginning of deposition, even when forming an ultra-thin film of 10 nm or less on a substrate having a complicated structure. An object of the present invention is to provide a film quality improving agent that greatly improves step coverage and thickness uniformity of a thin film, a method of forming a thin film using the same, and a semiconductor substrate manufactured therefrom.

An object of the present invention is to improve the density and electrical properties of a thin film by improving the crystallinity of the thin film.

The above and other objects of the present invention can all be achieved by the present invention described below.

In order to achieve the above object, the present invention i) vaporizing the thin film precursor compound and adsorbing it onto the surface of the loaded substrate in the ALD chamber; and ii) supplying a reaction gas in a plasma state into the ALD chamber; wherein, before or after step i), the film quality improver represented by Chemical Formula 1 is evaporated and adsorbed on the surface of the substrate loaded in the ALD chamber. It provides a thin film forming method characterized in that it comprises the step.

[Formula 1]

AnBmXoYiZj

(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1, where i and j are integers from 0 to 3.)

The method of forming the thin film may include evaporating the film quality improver and adsorbing the film quality improver onto a surface of a loaded substrate in an ALD chamber; firstly purging the inside of the ALD chamber with a purge gas; vaporizing the thin film precursor compound and adsorbing it onto the surface of the loaded substrate in the ALD chamber; secondarily purging the inside of the ALD chamber with a purge gas; supplying a reaction gas into the ALD chamber; and thirdly purging the inside of the ALD chamber with a purge gas; a total of 1 to 500 unit cycles may be performed.

The thin film forming method may include vaporizing a thin film precursor compound and adsorbing it to the surface of a substrate loaded in an ALD chamber; firstly purging the inside of the ALD chamber with a purge gas; evaporating the film quality improving agent and adsorbing it to the surface of the substrate loaded in the ALD chamber; secondarily purging the inside of the ALD chamber with a purge gas; supplying a reaction gas into the ALD chamber; and thirdly purging the inside of the ALD chamber with a purge gas; a total of 1 to 500 unit cycles may be performed.

The reaction gas may be supplied in a plasma state in cycles of 1/15 to 1/3 of the total number of cycles.

The reactive gas supplied in the plasma state may preferably be introduced between cycles at a point of 1/2 of the total cycle in the first cycle, and more preferably 1/15 to 1/3 of the total cycle in the first cycle. It can be continuously injected until the cycle point of

The plasma may be formed under a plasma power of 20 to 1,000 W.

In the method of forming the thin film, the thickness of the thin film formed after an initial 10 cycles may be 5 Å or more.

The film quality improver and the thin film precursor compound may be transferred into the ALD chamber using a VFC method, a DLI method, or an LDS method.

A ratio of the amount (mg/cycle) of the film quality improving agent and the precursor compound injected into the ALD chamber may range from 1:1.5 to 1:20.

In addition, the present invention provides a semiconductor substrate characterized in that it is manufactured by the thin film forming method.

The thin film may have a thickness of 10 nm or less.

The thin film may have a surface roughness of less than 500 pm.

The thickness uniformity of the thin film may be 50% or less.

The thin film may include a titanium nitride film.

In addition, the present invention provides a film quality improving agent characterized in that it is a compound represented by the following formula (1).

[Formula 1]

AnBmXoYiZj

(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1, where i and j are integers from 0 to 3.)

The compound represented by Formula 1 may be a compound represented by Formula 2 below.

[Formula 2]

(A is carbon or silicon, R ₁ , R ₂ and R ₃ are independently C1-3 alkyl groups, X is fluorine (F), chlorine (Cl), bromine (Br) and iodine ( I) is one or more of them.)

At least one of R ₁ , R ₂ and R ₃ may have 1 carbon atom.

At least one of R ₁ , R ₂ and R ₃ may have 2 or 3 carbon atoms.

The X may be iodine.

The X may be fluorine, chlorine or bromine.

According to the present invention, even in the case of forming an ultra-thin film with a thickness of 10 nm or less, the thin film is uniformly formed from the beginning of deposition, so that step coverage and thickness uniformity of the thin film are greatly improved, thereby greatly improving the electrical characteristics of the thin film. There is an effect of providing a thin film forming method capable of forming a thin film.

1 shows the results of XPS (X-ray photoelectron spectroscopy) depth profile analysis of thin films prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 of the present invention.
2 is an atomic force microscope (AFM) mapping image obtained by scanning the surface roughness of thin films prepared according to Examples 1 to 3 and Comparison 1 to 3 of the present invention.

Hereinafter, the film quality improver of the present substrate, a method of forming a thin film using the same, and a semiconductor substrate manufactured therefrom will be described in detail.

The present inventors adsorbed a halogen-substituted branched compound having a predetermined structure on the surface of a substrate loaded into an ALD chamber before or after adsorption of a thin film precursor compound, and supplying a reaction gas in a plasma state at the initial stage of deposition, resulting in a uniform thin film from the beginning of deposition. It was confirmed that even in the case of forming an ultra-thin film with a thickness of 10 nm or less, the step coverage and thickness uniformity were greatly improved, and based on this, further research was conducted to complete the present invention.

The thin film formation method of the present invention is i) vaporizing the thin film precursor compound and adsorbing it onto the surface of the loaded substrate in the ALD chamber; and ii) supplying a reaction gas in a plasma state into the ALD chamber; wherein, before or after step i), the film quality improver represented by Chemical Formula 1 is evaporated and adsorbed on the surface of the substrate loaded in the ALD chamber. In this case, even when forming an ultra-thin film with a thickness of 10 nm or less, the thin film is uniformly formed from the beginning of deposition, so that the step coverage, the thickness uniformity of the thin film, and the electrical properties of the thin film are greatly improved. .

[Formula 1]

AnBmXoYiZj

In Formula 1, A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, and X is selected from among fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). At least one, wherein Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, and o is an integer of 1 or more , m is 0 to 2n + 1, and i and j are integers from 0 to 3.

B is preferably hydrogen or methyl, n is preferably an integer from 2 to 15, more preferably an integer from 2 to 10, still more preferably an integer from 2 to 6, even more preferably an integer from 4 to 6, Within this range, the effect of removing process by-products is high and the step coverage is excellent.

In Formula 1, X is preferably at least one of bromine (Br) and iodine (I), and more preferably iodine. In this case, crystallinity of the thin film is improved and side reactions are suppressed to reduce process by-products. It has an effective removal effect.

In another example, the X may be fluorine, chlorine or bromine, preferably chlorine or bromine, and within this range, there is an advantage that is more effective in reducing process by-products and improving step coverage.

In Formula 1, o may be preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2, and within this range, the effect of reducing the deposition rate is large. There is an advantage of being more effective in improving step coverage.

The m is preferably 1 to 2n + 1, more preferably 3 to 2n + 1, and within this range, the effect of removing process by-products is high and the step coverage is excellent.

Preferably, Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, and fluorine, and are not the same.

The i and j are not both 0 in a preferred embodiment, and may be an integer of 1 to 3 as a specific example.

The compound represented by Formula 1 may preferably be a branched, cyclic or aromatic compound, and specific examples include tert-butyl bromide, 1-methyl-1-bromocyclohexane, 1-iodopropane, 1-iodobutane, 1-iodo -2-methyl propane, 1-iodo-1-isopropylcyclohexane, 1-iodo-4-nitrobenzene, 1-iodo-4-methoxybenzene, 1-iodo-2-methylpentane, 1-iodo-4-trifuloromethylbenzene, tert-butyl child tert-butyl iodide and 1-methyl-1-iodocyclohexane, 1-bromo-4-chlorobenzene, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1 -At least one member selected from the group consisting of -bromohexane, 1-bromo-2-methylpropane, 1-bromooctance, 1-bromonaphthalene, 1-bromo-4-iodobenzene and 1-bromo-4-nitrobenzene, in which case the process by-product removal effect is large and has excellent step coverage improvement and film quality improvement effect.

The compound represented by Formula 1 may be a compound represented by Formula 2 below as a preferred example.

[Formula 2]

In Formula 2, A and X are each as defined in Formula 1, and R ₁ , R ₂ and R ₃ are independently an alkyl group having 1 to 3 carbon atoms.

At least one of R ₁ , R ₂ and R ₃ may have a carbon number of 1, preferably all of R ₁ , R ₂ and R ₃ may have a carbon number of 1, in which case a thin film is uniformly formed from the initial deposition When forming an ultra-thin film, there is an advantage of superior thickness uniformity.

In another example, at least one of R ₁ , R ₂ and R ₃ may have 2 or 3 carbon atoms, preferably at least one of R ₁ , R ₂ and R ₃ may have 2 carbon atoms, in which case there is a step difference. There is an advantage that the covering property is superior.

The compound represented by Formula 2 is a halogen-substituted tertiary alkyl compound, and specific examples include 2-iodo-2-methylpropane (tert-butyl iodide), 2-iodo-2methylbutane, and 2-iodo. -2methylpentane, 3-iodo-3methylpentane, 3-iodo-3methylhexane, 3-iodo-3ethylpentane, 3-iodo-3ethylhexane, 4-iodo-4methylheptane, 4-iodo-4ethylheptane, 4-iodo-4propylheptane, 2-chloro-2methylpropane, 2-chloro-2methylbutane, 2-chloro-2methylpentane, 3-chloro-3methylpentane, 3-chloro-3methylhexane, 3-chloro-3ethylpentane, 3-chloro-3ethylhexane, 4-chloro-4methylheptane, 4-chloro-4ethylheptane, 4-chloro-4propylheptane, 2- Bromo-2methylpropane, 2-bromo-2methylbutane, 2-bromo-2methylpentane, 3-bromo-3methylpentane, 3-bromo-3methylhexane, 3-bromo-3ethyl Pentane, 3-bromo-3ethylhexane, 4-bromo-4methylheptane, 4-bromo-4ethylheptane, 4-bromo-4propylheptane, 2-fluoro-2methylpropane, 2-fluoro Rho-2methylbutane, 2-fluoro-2methylpentane, 3-fluoro-3methylpentane, 3-fluoro-3methylhexane, 3-fluoro-3ethylpentane, 3-fluoro-3ethylhexane , 4-fluoro-4methylheptane, 4-fluoro-4ethylheptane, and at least one selected from the group consisting of 4-fluoro-4propylheptane, preferably 2-iodo-2-methylpropane and It is at least one selected from the group consisting of 2-iodo-2methylbutane, and in this case, there is an advantage in that the effect of removing process by-products is high and the effect of improving step coverage and film quality is excellent.

The compound represented by Formula 1 is preferably used in an atomic layer deposition (ALD) process, and in this case, it effectively protects the surface of the substrate as a film quality improver without interfering with the adsorption of the thin film precursor compound and removes process by-products. It has the advantage of effectively removing it.

The compound represented by Formula 1 is preferably a liquid at room temperature (22°C), has a density of 0.8 to 2.5 g/cm ³ or 0.8 to 1.5 g/cm ³ , and has a vapor pressure (20°C) of 0.1 to 300 mmHg or 1 to 300 mmHg, and the solubility in water (25° C.) may be 200 mg/L or less, and within this range, there is an excellent effect in improving step coverage, thickness uniformity of the thin film, and film quality.

More preferably, the compound represented by Formula 1 has a density of 0.75 to 2.0 g/cm ³ or 0.8 to 1.3 g/cm ³ , a vapor pressure (20° C.) of 1 to 260 mmHg, and a solubility in water (25 ℃) may be 160 mg/L or less, and within this range, there are excellent effects in step coverage, thickness uniformity of the thin film, and film quality improvement.

As a specific example, the method for forming a thin film of the present invention includes vaporizing the film quality improving agent and adsorbing it to the surface of a substrate loaded in an ALD chamber; firstly purging the inside of the ALD chamber with a purge gas; vaporizing the thin film precursor compound and adsorbing it onto the surface of the loaded substrate in the ALD chamber; secondarily purging the inside of the ALD chamber with a purge gas; supplying a reaction gas into the ALD chamber; and thirdly purging the inside of the ALD chamber with a purge gas; as a unit cycle, and the cycle may be repeated 1 to 500 times in total.

As a specific example, the thin film formation method of the present invention includes the steps of vaporizing a thin film precursor compound and adsorbing it to the surface of a substrate loaded in an ALD chamber; firstly purging the inside of the ALD chamber with a purge gas; evaporating the film quality improving agent and adsorbing it to the surface of the substrate loaded in the ALD chamber; secondarily purging the inside of the ALD chamber with a purge gas; supplying a reaction gas into the ALD chamber; and thirdly purging the inside of the ALD chamber with a purge gas; as a unit cycle, and the cycle may be repeated 1 to 500 times in total.

In the thin film formation method of the present invention, a process of adsorbing the film quality improver and purging the unadsorbed film quality improver is performed before or after performing the process of adsorbing the thin film precursor compound on the substrate and purging the unadsorbed film precursor compound as described above. At this time, at least one cycle or more is characterized in that the reaction gas is supplied in a plasma state.

The reaction gas may be supplied in a plasma state at cycles of 1/15 to 1/3 of the total number of cycles, for example. The reactive gas supplied in the plasma state may preferably be introduced between cycles at a point of 1/2 of the total cycle in the first cycle, and more preferably 1/15 to 1/3 of the total cycle in the first cycle. It can be continuously injected until the cycle point of

More specifically, when the total number of repetitions of the unit cycle is k, in the initial cycle of 1 to k / q (where k is at least twice as large as q), the reaction gas supply step converts the reaction gas into a plasma state supply, and can be supplied in a non-plasma state after the k/qth cycle. In this case, the thin film is uniformly formed from the beginning of deposition, and the thin film is deposited at an excessively high speed due to plasma enhancement treatment, so that the film quality is deteriorated. problem can be prevented, and there is an advantage in that the thickness uniformity of the thin film is greatly improved. Here, k is an integer from 1 to 500, and q is an integer from 3 to 15. The k may be preferably 5 to 400, more preferably 10 to 200, still more preferably 15 to 100, even more preferably 20 to 70, and 25 to 50 as a specific example. The q may be preferably 3 to 12, more preferably 5 to 10.

In the present description, when the k/q value has a value below the decimal point, the value from which the value below the decimal point is deleted corresponds to the k/q th cycle.

In general, a thin film deposition process includes the steps of adsorbing a thin film precursor on a substrate, purging unadsorbed thin film precursors by supplying a purge gas, supplying a reaction gas, and purging unreacted substances by supplying a purge gas. As a cycle, the thin film is deposited by repeating the unit cycle dozens of times or more until a thin film having a desired thickness is obtained. At this time, in the initial cycle, for example, the 1st to 10th cycles, there occurs a phenomenon in which no or little thin film is deposited on the substrate, and this is referred to as an incubation cycle.

As a preferred example, the present invention includes the step of adsorbing the film quality improver before or after adsorption of the thin film precursor within one cycle, and at the same time, supplying the reaction gas in a plasma state in the initial cycle to form a thin film precursor on the substrate from the beginning of deposition without a latency cycle. It may be an incubation cycle-free process in which the compound is deposited. In this case, the thin film is deposited stably from the beginning of the deposition, so that a thin film with significantly improved uniformity can be formed, and the uniformity is excellent over a wide deposition temperature range. There is an advantage of forming an ultra-thin film.

In the thin film forming method, for example, the thickness of the thin film formed after the initial 10th cycle may be 5 Å or more, preferably 6 Å or more, and more preferably 7 Å or more. In this case, there is an advantage in obtaining an ultra-thin film with excellent uniformity.

In the thin film formation method, for example, when performing a process of adsorbing the film quality improver and purging the unadsorbed film quality improver before or after performing a process of adsorbing the thin film precursor compound on a substrate and purging the unadsorbed film precursor compound. , The above cycle can be repeated 1 to 500 times, preferably 5 to 400 times, more preferably 10 to 200 times, still more preferably 15 to 100 times, still more preferably 20 to 70 times, specific For example, it can be repeated 25 to 50 times, and within this range, there is an effect that the desired thin film characteristics are well expressed.

The plasma may be formed under, for example, a plasma power of 20 to 1,000 W, and the plasma power is preferably 30 to 700 W, more preferably 50 to 500 W, still more preferably 60 to 300 W, even more preferably. It may be 80 to 200 W, in a specific example, 80 to 150 W, and the desired effect can be sufficiently expressed within this range.

The plasma is, for example, He, Ne, Ar, Kr, H ₂ , N ₂ , NO, NO ₂ , NH ₃ , CO, CO ₂ and O ₂ Plasma-treated under an atmosphere containing one or more selected from the group consisting of It may be, preferably formed under an atmosphere containing at least one selected from the group consisting of He, Ne, Ar and Kr, more preferably under an Ar atmosphere, in which case the thin film uniformity is more There are great advantages. As a specific example, in the case of depositing a metal nitride film such as a TiN thin film, the plasma may be obtained by plasma-processing a mixed gas of N ₂ , H ₂ and N ₂ or NH ₃ as a reactive gas under an argon atmosphere.

When the film quality improver is first adsorbed onto the substrate and then the thin film precursor compound is adsorbed, or when the film quality improver is adsorbed after the thin film precursor compound is first adsorbed, the ALD in the step of purging the unadsorbed film quality improver The amount of purge gas injected into the chamber is not particularly limited as long as it is sufficient to remove the unadsorbed film quality improver, but may be, for example, 10 to 100,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times. Within this range, unadsorbed film quality improving agents are sufficiently removed to form a thin film evenly and to prevent deterioration of film quality. Here, the input amounts of the purge gas and the film quality improver are based on one cycle, respectively, and the volume of the film quality improver means the volume of the film quality improver that has been introduced.

As a specific example, the membrane quality improver is injected (per cycle) at a flow rate of 1.66 mL/s and an injection time of 0.5 sec, and in the step of purging the unadsorbed membrane quality improver, a purge gas is supplied at a flow rate of 166.6 mL/s and an injection time of 3 sec. In the case of injection (per cycle), the injection amount of the purge gas is 602 times the injection amount of the film quality improver.

In addition, in the step of purging the unadsorbed thin film precursor compound, the amount of purge gas injected into the ALD chamber is not particularly limited as long as it is an amount sufficient to remove the unadsorbed thin film precursor compound. For example, the amount of purge gas introduced into the ALD chamber It may be 10 to 10,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times based on the volume of the thin film precursor compound, and within this range, unadsorbed thin film precursor compounds are sufficiently removed to form a thin film evenly. formed, and deterioration of the film quality can be prevented. Here, the input amounts of the purge gas and the thin film precursor compound are based on one cycle, respectively, and the volume of the thin film precursor compound means the volume of the thin film precursor compound that is given an opportunity.

In addition, in the purging step performed immediately after the reactant gas supply step, the amount of purge gas introduced into the ALD chamber may be 10 to 10,000 times the volume of the reactant gas introduced into the ALD chamber, and preferably 50 to 50,000 times, more preferably 100 to 10,000 times, and within this range, desired effects can be sufficiently obtained. Here, the input amounts of the purge gas and the reactive gas are each based on one cycle.

The film quality improver and the thin film precursor compound may be preferably transferred into the ALD chamber by a VFC method, a DLI method or an LDS method, and more preferably transferred into the ALD chamber by an LDS method.

The input amount (mg/cycle) ratio of the film quality improver and the precursor compound in the ALD chamber may be preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, and still more preferably 1:2 to 1:12, more preferably 1:2.5 to 1:10, and within this range, the effect of improving step coverage and reducing process by-products is great.

The thin film precursor compound is not particularly limited when it is a thin film precursor compound commonly used in ALD (atomic layer deposition method), but is preferably a metal film precursor compound, a metal oxide film precursor compound, a metal nitride film precursor compound, and a silicon nitride film precursor compound. may include one or more selected from the group consisting of, and the metal is preferably tungsten, cobalt, chromium, aluminum, hafnium, vanadium, niobium, germanium, lanthanide, actinium, gallium, tantalum, zirconium, ruthenium, It may include at least one selected from the group consisting of copper, titanium, nickel, iridium, and molybdenum.

The metal film precursor, metal oxide film precursor, and metal nitride film precursor are, for example, a metal halide, a metal alkoxide, an alkyl metal compound, a metal amino compound, a metal carbonyl compound, and a substituted or unsubstituted cyclopentadienyl metal compound. It may be one or more selected from, but is not limited thereto.

As a specific example, the metal film precursor, metal oxide film precursor, and metal nitride film precursor are tetrachlorotitanium, tetrachlorogemanium, tetrachlorotin, tris (isopropyl) ethylmethylamino germanium, respectively. (isopropyl)ethylmethyl aminogermanium), tetraethoxylgermanium, tetramethyl tin, tetraethyl tin, bisacetylacetonate tin, trimethylaluminum, tetrakis( dimethylamino) germanium (tetrakis(dimethylamino)germanium), bis(n-butylamino) germanium (bis(n-butylamino) germanium), tetrakis(ethylmethylamino) tin (tetrakis(ethylmethylamino) tin), tetrakis(dimethyl amino) tin (tetrakis(dimethylamino)tin), Co ₂ (CO) ₈ (dicobalt octacarbonyl), Cp2Co (biscyclopentadienylcobalt), Co(CO) ₃ (NO) (cobalt tricarbonyl nitrosyl), and CpCo(CO) ₂ (cabalt dicarbonyl) cyclopentadienyl) and the like, but is not limited thereto.

The silicon nitride film precursor is, for example, SiH ₄ , SiCl ₄ , SiF ₄ , SiCl ₂ H ₂ , Si ₂ Cl ₆ , TEOS, DIPAS, BTBAS, (NH ₂ )Si(NHMe) ₃ , (NH ₂ )Si(NHEt) ₃ , (NH ₂ )Si(NH ⁿ Pr) ₃ , (NH ₂ )Si(NH ⁱ Pr) ₃ , (NH ₂ )Si(NH ⁿ Bu) ₃ , (NH ₂ )Si(NH ⁱ Bu) ₃ , (NH ₂ )Si(NH ^t Bu) ₃ , (NMe ₂ )Si(NHMe) ₃ , (NMe ₂ )Si(NHEt) ₃ , (NMe ₂ )Si(NH ⁿ Pr) ₃ , (NMe ₂ )Si( NH ⁱ Pr) ₃ , (NMe ₂ )Si(NH ⁿ Bu) ₃ , (NMe ₂ )Si(NH ⁱ Bu) ₃ , (NMe ₂ )Si(NH ^t Bu) ₃ , (NEt ₂ )Si(NHMe) ₃ , (NEt ₂ )Si(NHEt) ₃ , (NEt ₂ )Si(NH ⁿ Pr) ₃ , (NEt ₂ )Si(NH ⁱ Pr) ₃ , (NEt ₂ )Si(NH ⁿ Bu) ₃ , (NEt ₂ )Si(NH ⁱ Bu) ₃ , (NEt ₂ )Si(NH ^t Bu) ₃ , (N ⁿ Pr ₂ )Si(NHMe) ₃ , (N ⁿ Pr ₂ )Si(NHEt) ₃ , (N ⁿ Pr ₂ )Si(NH ⁿ Pr) ₃ , (N ⁿ Pr ₂ )Si(NH ⁱ Pr) ₃ , (N ⁿ Pr ₂ )Si(NH ⁿ Bu) ₃ , (N ⁿ Pr ₂ )Si(NH ⁱ Bu) ₃ , (N ⁿ Pr ₂ )Si(NH ^t Bu) ₃ , (N ⁱ Pr ₂ )Si(NHMe) ₃ , (N ⁱ Pr ₂ )Si(NHEt) ₃ , (N ⁱ Pr ₂ )Si(NH ⁿ Pr) ₃ , (N ⁱ Pr ₂ )Si(NH ⁱ Pr) ₃ , (N ⁱ Pr ₂ )Si(NH ⁿ Bu) ₃ , (N ⁱ Pr ₂ )Si(NH ⁱ Bu) ₃ , (N ⁱ Pr ₂ )Si(NH ^t Bu) ₃ , (N ⁿ Bu ₂ )Si(NHMe) ₃ , (N ⁿ Bu ₂ )Si(NHEt) ₃ , (N ⁿ Bu ₂ )Si(NH ⁿ Pr) ₃ , (N ⁿ Bu ₂ )Si(NH ⁱ Pr) ₃ , (N ⁿ Bu ₂ )Si(NH ⁿ Bu) ₃ , (N ⁿ Bu ₂ )Si(NH ⁱ Bu) ₃ , (N ⁿ Bu ₂ )Si(NH ^t Bu) ₃ , (N ⁱ Bu ₂ )Si(NHMe) ₃ , (N ⁱ Bu ₂ )Si(NHEt) ₃ , (N ⁱ Bu ₂ )Si(NH ⁿ Pr) ₃ , ( N ⁱ Bu ₂ )Si(NH ⁱ Pr) ₃ , (N ⁱ Bu ₂ )Si(NH ⁿ Bu) ₃ , (N ⁱ Bu ₂ )Si(NH ⁱ Bu) ₃ , (N ⁱ Bu ₂ )Si(NH ^t Bu) ₃ , (N ^t Bu ₂ )Si(NHMe) ₃ , (N ^t Bu ₂ )Si(NHEt) ₃ , (N ^t Bu ₂ )Si(NH ⁿ Pr) ₃ , (N ^t Bu ₂ )Si (NH ⁱ Pr) ₃ , (N ^t Bu ₂ )Si(NH ⁿ Bu) ₃ , (N ^t Bu ₂ )Si(NH ⁱ Bu) ₃ , (N ^t Bu ₂ )Si(NH ^t Bu) ₃ , ( NH ₂ ) ₂ Si(NHMe) ₂ , (NH ₂ ) ₂ Si(NHEt) ₂ , (NH ₂ ) ₂ Si(NH ⁿ Pr) ₂ , (NH ₂ ) ₂ Si(NH ⁱ Pr) ₂ , (NH ₂ ) ₂ Si(NH ⁿ Bu) ₂ , (NH ₂ ) ₂ Si(NH ⁱ Bu) ₂ , (NH ₂ ) ₂ Si(NH ^t Bu) ₂ , (NMe ₂ ) ₂ Si(NHMe) ₂ , (NMe ₂ ) ₂ Si(NHEt) ₂ , (NMe ₂ ) ₂ Si(NH ⁿ Pr) ₂ , (NMe ₂ ) ₂ Si(NH ⁱ Pr) ₂ , (NMe ₂ ) ₂ Si(NH ⁿ Bu) ₂ , (NMe _{2 )} ) ₂ Si(NH ⁱ Bu) ₂ , (NMe ₂ ) ₂ Si(NH ^t Bu) ₂ , (NEt ₂ ) ₂ Si(NHMe) ₂ , (NEt ₂ ) ₂ Si(NHEt) ₂ , (NEt ₂ ) ₂ Si(NH ⁿ Pr) ₂ , (NEt ₂ ) ₂ Si(NH ⁱ Pr) ₂ , (NEt ₂ ) ₂ Si(NH ⁿ Bu) ₂ , (NEt ₂ ) ₂ Si(NH ⁱ Bu) ₂ , ( NEt ₂ ) ₂ Si(NH ^t Bu) ₂ , (N ⁿ Pr ₂ ) ₂ Si(NHMe) ₂ , (N ⁿ Pr ₂ ) ₂ Si(NHEt) ₂ , (N ⁿ Pr ₂ ) ₂ Si(NH ⁿ Pr ) ₂ , (N ⁿ Pr ₂ ) ₂ Si(NH ⁱ Pr) ₂ , (N ⁿ Pr ₂ ) ₂ Si(NH ⁿ Bu) ₂ , (N ⁿ Pr ₂ ) ₂ Si(NH ⁱ Bu) ₂ , (N ⁿ Pr ₂ ) ₂ Si(NH ^t Bu) ₂ , (N ⁱ Pr ₂ ) ₂ Si(NHMe) ₂ , (N ⁱ Pr ₂ ) ₂ Si(NHEt) ₂ , (N ⁱ Pr ₂ ) ₂ Si(NH ⁿ Pr) ₂ , (N ⁱ Pr ₂ ) ₂ Si(NH ⁱ Pr) ₂ , (N ⁱ Pr ₂ ) ₂ Si(NH ⁿ Bu) ₂ , (N ⁱ Pr ₂ ) ₂ Si(NH ⁱ Bu) ₂ , ( N ⁱ Pr ₂ ) ₂ Si(NH ^t Bu) ₂ , (N ⁿ Bu ₂ ) ₂ Si(NHMe) ₂ , (N ⁿ Bu ₂ ) ₂ Si(NHEt) ₂ , (N ⁿ Bu ₂ ) ₂ Si(NH ⁿ Pr) ₂ , (N ⁿ Bu ₂ ) ₂ Si(NH ⁱ Pr) ₂ , (N ⁿ Bu ₂ ) ₂ Si(NH ⁿ Bu) ₂ , (N ⁿ Bu ₂ ) ₂ Si(NH ⁱ Bu) ₂ , (N ⁿ Bu ₂ ) ₂ Si(NH ^t Bu) ₂ , (N ⁱ Bu ₂ ) ₂ Si(NHMe) ₂ , (N ⁱ Bu ₂ ) ₂ Si(NHEt) ₂ , (N ⁱ Bu ₂ ) ₂ Si( NH ⁿ Pr) ₂ , (N ⁱ Bu ₂ ) ₂ Si(NH ⁱ Pr) ₂ , (N ⁱ Bu ₂ ) ₂ Si(NH ⁿ Bu) ₂ , (N ⁱ Bu ₂ ) ₂ Si(NH ⁱ Bu) ₂ , (N ⁱ Bu ₂ ) ₂ Si(NH ^t Bu) ₂ , (N ^t Bu ₂ ) ₂ Si(NHMe) ₂ , (N ^t Bu ₂ ) ₂ Si(NHEt) ₂ , (N ^t Bu ₂ ) ₂ Si (NH ⁿ Pr) ₂ , (N ^t Bu ₂ ) ₂ Si(NH ⁱ Pr) ₂ , (N ^t Bu ₂ ) ₂ Si(NH ⁿ Bu) ₂ , (N ^t Bu ₂ ) ₂ Si(NH ⁱ Bu) ₂ , (N ^t Bu ₂ ) ₂ Si(NH ^t Bu) ₂ , Si(HNCH ₂ CH ₂ NH) ₂ , Si(MeNCH ₂ CH ₂ NMe) ₂ ,Si(EtNCH ₂ CH ₂ NEt) ₂ , Si( ⁿ PrNCH ₂ CH ₂ N ⁿ Pr) ₂ , Si( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr) ₂ , Si( ⁿ BuNCH ₂ CH ₂ N ⁿ Bu) ₂ , Si ( ⁱ BuNCH ₂ CH ₂ N ⁱ Bu) ₂ , Si( ^t BuNCH ₂ CH ₂ N ^t Bu) ₂ , Si(HNCHCHNH) ₂ , Si(MeNCHCHNMe) ₂ , Si(EtNCHCHNEt) ₂ , Si( ⁿ PrNCHCHN ⁿ Pr) ₂ , Si( ⁱ PrNCHCHN ⁱ Pr) ₂ , Si( ⁿ BuNCHCHN ⁿ Bu) ₂ , Si( ⁱ BuNCHCHN ⁱ Bu) ₂ , Si( ^t BuNCHCHN ^t Bu) ₂ , (HNCHCHNH)Si(HNCH ₂ CH ₂ NH), (MeNCHCHNMe)Si(MeNCH ₂ CH ₂ NMe), (EtNCHCHNEt)Si(EtNCH ₂ CH ₂ NEt), ( ⁿ PrNCHCHN ⁿ Pr)Si( ⁿ PrNCH ₂ CH ₂ N ⁿ Pr), ( ⁱ PrNCHCHN ⁱ Pr)Si( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr), ( ⁿ BuNCHCHN ⁿ Bu)Si( ⁿ BuNCH ₂ CH ₂ N ⁿ Bu), ( ⁱ BuNCHCHN ⁱ Bu)Si( ⁱ BuNCH ₂ CH ₂ N ⁱ Bu), ( ^t BuNCHCHN ^t Bu)Si( ^t BuNCH ₂ CH ₂ N ^t Bu), (NH ^t Bu) ₂ Si(HNCH ₂ CH ₂ NH), (NH ^t Bu) ₂ Si(MeNCH ₂ CH ₂ NMe), (NH ^t Bu) ₂ Si(EtNCH ₂ CH ₂ NEt), (NH ^t Bu) ₂ Si( ⁿ PrNCH ₂ CH ₂ N ⁿ Pr), (NH ^t Bu) ₂ Si( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr), (NH ^t Bu) ₂ Si( ⁿ BuNCH ₂ CH ₂ N ⁿ Bu), (NH ^t Bu) ₂ Si( ⁱ BuNCH ₂ CH ₂ N ⁱ Bu), (NH ^t Bu) ₂ Si( ^t BuNCH ₂ CH ₂ N ^t Bu), ( NH ^t Bu) ₂ Si(HNCHCHNH), (NH ^t Bu) ₂ Si(MeNCHCHNMe) _, (NH ^t Bu) ₂ Si(EtNCHCHNEt), (NH ^t Bu) ₂ Si( ⁿ PrNCHCHN ⁿ Pr), (NH ^t Bu) ₂ Si( ⁱ PrNCHCHN ⁱ Pr), (NH ^t Bu) ₂ Si( ⁿ BuNCHCHN ⁿ Bu), (NH ^t Bu) ₂ Si( ⁱ BuNCHCHN ⁱ Bu), (NH ^t Bu) ₂ Si( ^t BuNCHCHN ^t Bu), ( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr)Si(NHMe) ₂ , ( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr)Si(NHEt) ₂ , ( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr)Si(NH ⁿ Pr) ₂ , ( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr)Si(NH ⁱ Pr) ₂ , ( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr)Si(NH ⁿ Bu) ₂ , ( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr)Si(NH ⁱ Bu) ₂ , ( ⁱ PrNCH ₂ CH ₂ N ⁱ Pr)Si(NH ^t Bu) ₂ , ( ⁱ PrNCHCHN ⁱ Pr)Si(NHMe) ₂ , ( ⁱ PrNCHCHN ⁱ Pr)Si(NHEt) ₂ , ( ⁱ PrNCHCHN ⁱ Pr)Si (NH ⁿ Pr) ₂ , ( ⁱ PrNCHCHN ⁱ Pr)Si(NH ⁱ Pr) ₂ , ( ⁱ PrNCHCHN ⁱ Pr)Si(NH ⁿ Bu) ₂ , ( ⁱ PrNCHCHN ⁱ Pr)Si(NH ⁱ Bu) ₂ and ( ⁱ PrNCHCHN ⁱ Pr)Si(NH ^t Bu) ₂ It may be one or more selected from the group consisting of, but is not limited thereto.

ⁿ Pr means n-propyl, ⁱ Pr means iso-propyl, ⁿ Bu means n-butyl, ⁱ Bu means iso-butyl, ^{and t} Bu means tert -butyl.

In a preferred embodiment, the thin film precursor compound is TiCl ₄ , (Ti(CpMe ₅ )(OMe) ₃ ), Ti(CpMe ₃ )(OMe) ₃ , Ti(OMe) ₄ , Ti(OEt) ₄ , Ti(OtBu) ) ₄ , Ti(CpMe)(OiPr) ₃ , TTIP(Ti(OiPr) ₄ , TDMAT (Ti(NMe ₂ ) ₄ ), and at least one selected from the group consisting of Ti(CpMe){N(Me ₂ ) ₃ } It may include, and in this case, the effect to be achieved in the present invention can be sufficiently obtained.

The titanium tetrahalide may be used as a metal precursor of a composition for forming a thin film. The tetrahalide titanium may be, for example, at least one selected from the group consisting of TiF ₄ , TiCl ₄ , TiBr ₄ and TiI ₄ , and for example, TiCl ₄ is preferable in view of economic efficiency, but is not limited thereto.

For example, since the titanium tetrahalide has excellent thermal stability and exists in a liquid state without decomposition at room temperature, it can be usefully used as a precursor for ALD (atomic layer deposition) to deposit a thin film.

For example, the thin film precursor compound may be mixed with a non-polar solvent and introduced into the chamber. In this case, there is an advantage in that the viscosity or vapor pressure of the thin film precursor compound can be easily adjusted.

The non-polar solvent may preferably be at least one selected from the group consisting of alkanes and cycloalkanes, and in this case, even if the deposition temperature is increased when forming a thin film, the step coverage ( There is an advantage that step coverage is improved.

As a more preferred example, the non-polar solvent may include a C1 to C10 alkane or a C3 to C10 cycloalkane, preferably a C3 to C10 cycloalkane, in which case the reactivity and It has the advantage of low solubility and easy water management.

In this description, C1, C3, etc. mean the number of carbon atoms.

The cycloalkane may preferably be a C3 to C10 monocycloalkane, and among the monocycloalkanes, cyclopentane is a liquid at room temperature and has the highest vapor pressure, so it is preferable in a vapor deposition process, but is not limited thereto.

The non-polar solvent has, for example, a solubility in water (25° C.) of 200 mg/L or less, preferably 50 to 200 mg/L, more preferably 135 to 175 mg/L, and within this range, the thin film precursor compound It has the advantage of low reactivity and easy water management.

In the present description, solubility is not particularly limited when it is based on a measurement method or standard commonly used in the technical field to which the present invention belongs, and for example, a saturated solution can be measured by an HPLC method.

The non-polar solvent may preferably include 5 to 95% by weight, more preferably 10 to 90% by weight, and more preferably 40 to 95% by weight based on the total weight of the thin film precursor compound and the non-polar solvent. It may contain 90% by weight, and most preferably 70 to 90% by weight.

If the content of the non-polar solvent is added in excess of the upper limit, impurities are induced to increase resistance and impurity levels in the thin film, and if the content of the organic solvent is added to be less than the lower limit, step coverage is improved due to the addition of the solvent. There is a disadvantage that the reduction effect of impurities such as effect and chlorine (Cl) ion is small.

In the thin film forming method, for example, the thin film growth rate per cycle (Å/Cycle) reduction rate calculated by Equation 1 below is -5% or less, preferably -10% or less, more preferably -20% or less, and It is preferably -30% or less, even more preferably -40% or less, and most preferably -45% or less, and within this range, the step coverage and film thickness uniformity are excellent.

[Equation 1]

Thin film growth rate decrease per cycle (%) = [(Film growth rate per cycle when film quality improver is used - Thin film growth rate per cycle when film quality improver is not used) / Thin film growth rate per cycle when film quality improver is not used] Ⅹ 100

In Equation 1, the thin film growth rate per cycle with and without the film quality improver means the thin film deposition thickness per cycle (Å/Cycle), that is, the deposition rate, and the deposition rate is, for example, ellipsometery. After measuring the final thickness of , the average deposition rate can be obtained by dividing by the total number of cycles.

In Equation 1, "when no film quality improver is used" means a case in which a thin film is produced by adsorbing only a thin film precursor compound onto a substrate in a thin film deposition process. This refers to a case in which the thin film is formed by omitting the step of purging the unadsorbed film quality improving agent.

In the thin film formation method, the residual halogen intensity (c / s) in a thin film based on a thin film thickness of 100 Å, measured based on SIMS, is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000 or less, and even more preferably 10,000 or less In a preferred embodiment, it may be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800, and the effect of preventing corrosion and deterioration within this range is excellent.

Purging in the present substrate is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, still more preferably 2,500 to 15,000 sccm, and within this range, the thin film growth rate per cycle is appropriately controlled, It is deposited as an atomic mono-layer or close to it, so there is an advantage in terms of film quality.

The ALD (atomic layer deposition process) is very advantageous in manufacturing an integrated circuit (IC) requiring a high aspect ratio, and in particular, excellent conformality and uniform coverage due to a self-limiting thin film growth mechanism (uniformity) and precise thickness control.

The thin film formation method can be carried out at a deposition temperature in the range of 50 to 800 ° C., preferably at a deposition temperature in the range of 300 to 700 ° C., more preferably at a deposition temperature in the range of 400 to 650 ° C. , More preferably, it is carried out at a deposition temperature in the range of 400 to 600 ° C, and even more preferably, it is carried out at a deposition temperature in the range of 430 to 600 ° C. has the effect of growing into

The thin film formation method may be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.1 to 10 Torr. Preferably, it is carried out at a deposition pressure in the range of 1 to 7 Torr, and there is an effect of obtaining a thin film with a uniform thickness within this range.

In the present disclosure, the deposition temperature and the deposition pressure may be measured as the temperature and pressure formed in the deposition chamber or the temperature and pressure applied to the substrate in the deposition chamber.

The method of forming the thin film may preferably include raising the temperature in the chamber to a deposition temperature before introducing the film quality improver into the chamber; and/or purging by injecting an inert gas into the chamber before introducing the film quality improver into the chamber.

In addition, the present invention is an ALD chamber, a first vaporizer for vaporizing the film quality improver, a first transfer means for transferring the vaporized film quality improver into the ALD chamber, and a vaporizer for vaporizing the thin film precursor. 2 It may include a thin film manufacturing apparatus including a vaporizer and a second transfer means for transferring the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and transfer means are not particularly limited in the case of vaporizers and transfer means commonly used in the technical field to which the present invention belongs.

As a specific example, if the thin film formation method is described,

First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of atomic layer deposition.

The substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

The substrate may further have a conductive layer or an insulating layer formed thereon.

In order to deposit a thin film on a substrate placed in the deposition chamber, the above-described film quality improving agent, a thin film precursor compound, or a mixture of the non-polar solvent and the mixture are prepared.

Thereafter, the prepared film quality improver is injected into a vaporizer, changed into a vapor phase, transferred to a deposition chamber, adsorbed on a substrate, and purged to remove unadsorbed film quality improvers.

Next, the prepared thin film precursor compound or a mixture of it and a non-polar solvent (composition for forming a thin film) is injected into a vaporizer, converted into a vapor phase, transferred to a deposition chamber, and adsorbed on a substrate, thereby forming an unadsorbed thin film precursor compound/thin film. The composition is purged.

In the present substrate, a step of adsorbing the film quality improver on a substrate and then purging to remove unadsorbed film quality improver; and adsorbing the thin film precursor compound on the substrate and purging to remove the unadsorbed thin film precursor compound; the order may be changed if necessary.

In the present substrate, the method of delivering the film quality improver and the thin film precursor compound (composition for forming a thin film) to the deposition chamber is, for example, a method of transporting volatilized gas using a mass flow controller (MFC) method (vapor A liquid delivery system (LDS) may be used by using a flow control (VFC) or liquid mass flow controller (LMFC) method, and preferably the LDS method is used.

At this time, one or a mixture of two or more selected from the group consisting of argon (Ar), nitrogen (N ₂ ), and helium (He) may be used as a transport gas or diluent gas for moving the film quality improver and the thin film precursor compound on the substrate. It can, but is not limited.

In the present description, an inert gas may be used as the purge gas, for example, and the transport gas or dilution gas may be preferably used.

Next, a reactive gas is supplied. The reaction gas is not particularly limited when it is a reaction gas commonly used in the art to which the present invention pertains, and may preferably include a reducing agent, a nitriding agent, or an oxidizing agent. A metal thin film is formed by reacting the reducing agent with the thin film precursor compound adsorbed on the substrate, a metal nitride thin film is formed by the nitriding agent, and a metal oxide thin film is formed by the oxidizing agent.

Preferably, the reducing agent may be ammonia gas (NH ₃ ) or hydrogen gas (H ₂ ), and the nitriding agent may be nitrogen gas (N ₂ ), hydrazine gas (N ₂ H ₄ ), or a mixture of nitrogen gas and hydrogen gas. It may be a mixture, and the oxidizing agent may be at least one selected from the group consisting of H ₂ O, H ₂ O ₂ , O ₂ , O ₃ and N ₂ O.

The reaction gas may be ammonia gas (NH ₃ ) in a preferred embodiment.

Next, the unreacted residual reaction gas is purged using an inert gas. Accordingly, it is possible to remove not only the excess reaction gas but also the generated by-products.

As described above, the thin film forming method includes, for example, adsorbing the film quality improver on the substrate, purging the unadsorbed film quality improver, adsorbing the thin film precursor compound/thin film forming composition on the substrate, and unadsorbed thin film. The step of purging the precursor compound/film-forming composition, the step of supplying the reaction gas, and the step of purging the remaining reaction gas are a unit cycle, and the unit cycle may be repeated to form a thin film having a desired thickness.

In another example, the thin film forming method includes adsorbing the thin film precursor compound/thin film forming composition on a substrate, purging the unadsorbed thin film precursor compound/thin film forming composition, adsorbing a film quality improver on the substrate, Purging the unadsorbed film quality improving agent, supplying the reaction gas, and purging the remaining reaction gas are performed as a unit cycle, and the unit cycle may be repeated to form a thin film having a desired thickness.

The unit cycle may be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and still more preferably 100 to 2,000 times, and within this range, desired thin film properties This effect is well expressed.

The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film formation method of the present description, and in this case, the step coverage of the thin film and the thickness uniformity of the thin film are greatly excellent, and the thickness of the thin film is excellent. It has excellent density and electrical properties and can provide an ultra-thin film with a thickness of 10 nm or less, which is particularly suitable for highly integrated substrates.

The thin film may be an ultra-thin film having a thickness of, for example, 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and more specifically, 0.1 to 10 nm, preferably 0.5 to 5 nm, more preferably 3 nm or less. Preferably it may be 0.8 to 3 nm, more preferably 0.9 to 2.8 nm, and there is an effect of providing a thin film with excellent film quality within this range.

The thin film may have, for example, a surface roughness of less than 500 pm, preferably less than 300 pm, more preferably less than 200 pm, even more preferably less than 100 pm, and even more preferably less than 90 pm. 10 to 500 pm, preferably 20 to 300 pm, more preferably 20 to 200 pm, still more preferably 30 to 100 pm, even more preferably 40 to 90 pm, within this range the thin film There is an effect of providing a thin film with high uniformity and excellent film quality.

In the present description, surface roughness can be measured, for example, by irradiation of a laser on the surface of a target thin film by diffuse reflection intensity, and the lower this value is, the flatter and smoother the surface is, which indirectly indicates the thickness uniformity of the thin film. can be viewed as indicators. The surface roughness may be measured in a non-contact manner for an area of 5 Х 5 μm ² using, for example, a scanning probe microscope (AFM).

For example, the thickness uniformity of the thin film may be 50% or less, preferably 0.5 to 50%, more preferably 0.5 to 35%, still more preferably 0.8 to 30%, and still more preferably 0.8 to 25%. %, and in a preferred embodiment, 1 to 20%, more preferably 2 to 18%, and within this range, the uniformity of the thin film is high, and there is an effect of providing a thin film with excellent film quality.

In the present substrate, the thickness uniformity of the thin film is calculated by calculating the standard deviation and average value from the thickness values obtained by measuring the thickness of 9 random points at regular intervals from the central part of the thin film deposited on a wafer having a diameter of 300 mm, for example, and calculating the following equation 2 can be obtained using

[Equation 2]

Thickness uniformity (%) = (thickness standard deviation / average thickness) × 100

The thin film has, for example, a specific resistance value based on a thin film thickness of 5 nm of 1 to 400 μΩ cm, preferably 3 to 300 μΩ cm, more preferably 5 to 290 μΩ cm, and even more preferably 7 to 280 μΩ. · cm, and within this range, there is an effect of excellent thin film properties.

The thin film may have a halogen content of preferably 1,000 ppm or less, or 1 to 1,000 ppm, more preferably 5 to 500 ppm, and even more preferably 10 to 100 ppm, and within this range, the thin film properties are excellent and the metal There is an effect of reducing corrosion of the wiring material. Here, the halogen remaining in the thin film may be, for example, Cl ₂ , Cl, or Cl ⁻ , and the lower the residual amount of halogen in the thin film, the better the quality of the film.

The thin film has, for example, a step coverage of 80% or more, preferably 90% or more, and more preferably 92% or more. There are applicable benefits.

The prepared thin film is, for example, a titanium nitride film (Ti _x N _y , where 0<x≤1.2, 0<y≤1.2, preferably 0.8≤x≤1, 0.8≤y≤1, more preferably 1 day each may include) and titanium oxide film (TiO ₂ ) may include one or two types from the group consisting of, and preferably may include a titanium nitride film, in which case a diffusion prevention film, an etch stop film or wiring of a semiconductor device ( electrode).

The thin film may have, for example, a multilayer structure of two or three layers as needed. The multilayer film of the two-layer structure may have a lower film-middle layer structure as a specific example. As a specific example, the multilayer film having the three-layer structure may have a lower film-middle layer-upper layer structure.

The lower layer film is, for example, Si, SiO ₂ , MgO, Al ₂ O ₃ , CaO, ZrSiO ₄ , ZrO ₂ , HfSiO ₄ , Y ₂ O ₃ , HfO ₂ , LaLuO ₂ , Si ₃ N ₄ , SrO, La ₂ O ₃ , Ta ₂ O ₅ , BaO, TiO ₂ It may be made of including one or more selected from the group consisting of.

The intermediate layer may include, for example, Ti _x N _y , preferably TiN.

The upper layer film may include, for example, one or more selected from the group consisting of W and Mo.

Hereinafter, preferred embodiments and drawings are presented to aid understanding of the present invention, but the following embodiments and drawings are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention to those skilled in the art. It is obvious in this regard, and it is natural that such variations and modifications fall within the scope of the appended claims.

[Example]

Example 1

Tert-butyl iodide as a film quality improver and TiCl ₄ as a thin film precursor compound were prepared, respectively. The prepared film quality improver was put in a canister and supplied to a vaporizer heated to 150° C. at a flow rate of 0.05 g/min using a liquid mass flow controller (LMFC) at room temperature. The film quality improver vaporized in the vaporizer was introduced into the deposition chamber loaded with the substrate for 1 second, and then argon gas was supplied at 5000 sccm for 2 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr. Next, the prepared TiCl ₄ was put in a separate canister and supplied to a separate vaporizer heated to 150° C. at a flow rate of 0.05 g/min using a Liquid Mass Flow Controller (LMFC) at room temperature. After TiCl ₄ vaporized in a vaporizer was introduced into the deposition chamber for 1 second, argon gas was supplied at 5000 sccm for 2 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr. Next, 1000 sccm of ammonia as a reaction gas was introduced into the reaction chamber for 3 seconds, followed by argon purging for 3 seconds. At this time, the substrate on which the metal thin film is to be formed was heated to 460°C.

This process was repeated a total of 25 times to form a TiN thin film as a self-limiting atomic layer with a thickness of 13 Å.

In the first to fifth cycles of the beginning of deposition, when the reaction gas was injected, ammonia gas was plasma treated under an argon atmosphere with a plasma generator output of 100 W and supplied as NH ₃ plasma, and from the 6th cycle, ammonia gas was supplied without plasma treatment.

Example 2

In Example 1, a TiN thin film as a self-limiting atomic layer was formed in the same manner as in Example 1, except that the number of deposition cycles was changed to 50.

Example 3

In Example 1, a TiN thin film as a self-limiting atomic layer was formed in the same manner as in Example 1, except that the substrate heating temperature was changed to 550°C.

Comparative Example 1

In Example 1, except that the film quality improver was not supplied and the step of purging the unadsorbed film quality improver was omitted accordingly, the number of deposition cycles was changed to 50, and NH ₃ plasma was supplied when the reaction gas was supplied in all cycles. Then, a TiN thin film as a self-limiting atomic layer was formed in the same manner as in Example 1.

Comparative Example 2

In Example 1, a TiN thin film as a self-limiting atomic layer was formed in the same manner as in Example 1, except that the film quality improver was not supplied and the step of purging the unadsorbed film quality improver was omitted.

Comparative Example 3

In Example 1, a TiN thin film as a self-limiting atomic layer was formed in the same manner as in Example 1, except that the number of deposition cycles was changed to 50 and ammonia gas was supplied without plasma treatment when the reaction gas was supplied in all cycles. did

[Experimental example]

1) Thin film thickness

For the manufactured thin film, the thickness of the thin film was measured with an ellipsometer, a device that can measure optical properties such as thickness or refractive index of the thin film using the polarization characteristics of light, and the results are shown in Table 2 below. showed up

2) Thickness uniformity

The standard deviation and the average value are obtained from the 9 thickness data obtained by measuring the thickness by the thin film thickness measurement method at 9 random points at regular intervals from the center of the manufactured thin film (wafer diameter 300 mm), and then substituting them into Equation 2 below To obtain the thickness uniformity, the results are shown in Table 2 below.

[Equation 2]

Thickness uniformity (%) = (thickness standard deviation / average thickness) × 100

3) Ti element content in the thin film

For the prepared thin film, the depth profile was analyzed by photoelectron spectroscopy (XPS). Specifically, X-ray scans from 0 to 1,200 eV to detect signals of N, O, Si, C, Ti, Cl, and Ni elements in the thin film, where the signal values of Si and O elements are erased, and the remaining Using the sum of the signals of the elements as the standard (1), the elemental ratio (atomic %) of Ti detected in Ti2p was obtained.

Then, after sputtering an argon ion beam on the thin film substrate and infiltrating it in the depth direction of the thin film for 0.2 minutes at a rate of about 0.2 nm/min, the process of scanning by irradiating X-rays again is repeated 30 times (6 minutes in total). The results are shown in Table 2 and FIG. 1 below.

In FIG. 1 below, since the reliability of data may be lowered due to the influence of excited ions in an unstable state at the beginning of sputtering, the data after a certain point in time is Ti2p element ratio, and in this experimental example, Ti2p at 1 minute time point Elemental ratios were analyzed as valid data.

4) Surface roughness

On the surface of the prepared thin film, an area of 5 μm (25 μm ² ) in each of the X-axis and Y-axis directions was scanned and mapped in a non-contact method with a scanning probe microscope (AFM), and the results are shown in Table 2 and FIG. 2 below. .

As a reference, the illuminance of the silicon wafer used in the present disclosure before thin film deposition was confirmed to be 50 to 60 pm.

division membrane improver Reaction gas input method deposition temperature
(℃) number of deposition cycles
(episode) Example 1 tert-butyl iodide 1st ~ ^5th cycle: NH ₃ plasma
6 to ^25th cycle: NH ₃ 460 25 Example 2 tert-butyl iodide 1st ~ ^5th cycle: NH ₃ plasma
6 to ⁵⁰ cycles: NH ₃ 460 50 Example 3 tert-butyl iodide 1st ~ ^5th cycle: NH ₃ plasma
6 to ⁵⁰ cycles: NH ₃ 550 50 Comparative Example 1 - all cycles: NH ₃ plasma 460 50 Comparative Example 2 - 1st ~ ^5th cycle: NH ₃ plasma
6 to ⁵⁰ cycles: NH ₃ 460 50 Comparative Example 3 tert-butyl iodide all cycles: NH ₃ 460 50

division thin film thickness
(Å) thickness uniformity
(%) XPS elemental content
(Ti2p, atom% @1min) AFM surface roughness
(pm) Example 1 13 5.8 0.6756 70 Example 2 17 9.6 2.0723 62 Example 3 22 14.5 2.1562 80 Comparative Example 1 10 56.9 0.1001 250 Comparative Example 2 14 59.8 - 180 Comparative Example 3 17 29.9 - 178

As shown in Tables 1 and 2, the thin films of Examples 1 to 3 manufactured according to the present invention have a thin film thickness of 22 Å or less and a thickness uniformity of 15% or less, and thus have high uniformity even at a thin thickness. formation was confirmed. In addition, the thin films of Examples 1 to 3 had a high titanium element ratio and a low surface roughness of 80 pm or less, confirming that the thin film precursor compounds were stably deposited and the thin films were formed evenly and uniformly. This shows that in the case of Examples 1 to 3 of the present invention, unlike Comparative Examples 1 to 3, thin films with excellent uniformity were formed stably from the beginning of deposition without an initial incubation cycle.

On the other hand, in the case of Comparative Examples 1 to 3, which deviated from the present invention, the thickness uniformity and surface roughness were considerably high and the titanium element ratio was low, and it could be confirmed that the film quality was deteriorated compared to Examples 1 to 3.

Claims (19)

i) vaporizing the thin film precursor compound and adsorbing it onto the surface of the loaded substrate in the ALD chamber; and
ii) supplying a reaction gas in a plasma state into the ALD chamber;
Vaporizing the film quality improving agent represented by Formula 1 before or after step i) and adsorbing it to the surface of the substrate loaded in the ALD chamber.
thin film formation method.
[Formula 1]
AnBmXoYiZj
(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1, where i and j are integers from 0 to 3.)
According to claim 1,
evaporating the film quality improving agent and adsorbing it to the surface of the substrate loaded in the ALD chamber;
firstly purging the inside of the ALD chamber with a purge gas;
vaporizing the thin film precursor compound and adsorbing it onto the surface of the loaded substrate in the ALD chamber;
secondarily purging the inside of the ALD chamber with a purge gas;
supplying a reaction gas into the ALD chamber; and
Thirdly purging the inside of the ALD chamber with a purge gas; as a unit cycle, characterized in that the total number of cycles is 1 to 500
thin film formation method.
According to claim 1,
vaporizing the thin film precursor compound and adsorbing it onto the surface of the loaded substrate in the ALD chamber;
firstly purging the inside of the ALD chamber with a purge gas;
evaporating the film quality improving agent and adsorbing it to the surface of the substrate loaded in the ALD chamber;
secondarily purging the inside of the ALD chamber with a purge gas;
supplying a reaction gas into the ALD chamber; and
Thirdly purging the inside of the ALD chamber with a purge gas; as a unit cycle, characterized in that the total number of cycles is 1 to 500
thin film formation method.
According to claim 2 or 3,
The reaction gas, when the total cycle number is k, is initially 1 to k / q (where k is an integer from 1 to 500, q is an integer from 3 to 15, and k is at least twice or more than q And, if the k / q value has a value below the decimal point, the value below the decimal point is omitted) is supplied in a plasma state in the cycle, and is supplied in a non-plasma state in the cycle after the k / q cycle.
thin film formation method.
According to claim 1,
Characterized in that the plasma is formed under a plasma power of 20 to 1,000 W
thin film formation method.
According to claim 1,
Characterized in that the thickness of the thin film formed after the initial 10 cycles is 5 Å or more
thin film formation method.
According to claim 1,
Characterized in that the film quality improver and thin film precursor compound are transferred into the ALD chamber by VFC method, DLI method or LDS method
thin film formation method.
According to claim 1,
Characterized in that the input amount (mg / cycle) ratio of the film quality improver and the precursor compound in the ALD chamber is 1: 1.5 to 1: 20
thin film formation method.
Characterized in that it is produced by the thin film forming method according to claim 1
semiconductor substrate.
According to claim 9,
The thin film is characterized in that the thickness is less than 10 nm
semiconductor substrate.
According to claim 9,
The thin film is characterized in that the surface roughness is less than 500 pm
thin film formation method.
According to claim 9,
The thin film Characterized in that the thickness uniformity is 50% or less
thin film formation method.
According to claim 9,
The thin film is characterized in that it comprises a titanium nitride film
semiconductor substrate.
Used to form ultra-thin films,
Formula 1 below
[Formula 1]
AnBmXoYiZj
(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n + 1, wherein i and j are integers from 0 to 3).
membrane improver.
According to claim 14,
The compound represented by Formula 1 below is Formula 2
[Formula 2]

(A is carbon or silicon, R ₁ , R ₂ and R ₃ are independently C1-3 alkyl groups, X is fluorine (F), chlorine (Cl), bromine (Br) and iodine ( It is one or more of I).) Characterized in that the compound represented by
membrane improver.
According to claim 15,
At least one of R ₁ , R ₂ and R ₃ is characterized in that the number of carbon atoms is 1
membrane improver.
According to claim 15,
wherein at least one of R ₁ , R ₂ and R ₃ has 2 or 3 carbon atoms
membrane improver.
According to claim 14,
Wherein X is iodine
membrane improver.
According to claim 14,
Wherein X is fluorine, chlorine or bromine
membrane improver.

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