KR20120053454A - Deposition method of thin film using silicon precursor - Google Patents

Abstract

The present invention relates to a thin film deposition method for depositing a silicon precursor compound by an atomic layer deposition method to form a silicon oxide thin film or a silicon nitride thin film, or a silicon oxynitride thin film, and a heterocyclic amine having a ring strain. Silicon precursor compound having heterocyclic amine and atomic layer deposition method can easily form a thin film, can be deposited at low deposition temperature of 100 ~ 500 ℃, precise control of thickness and composition, substrate of complex shape Also, it is expected that excellent coating properties and a uniform composition can be formed, thereby improving the characteristics of the semiconductor device.

Description

Thin film deposition method using silicon precursor compound {DEPOSITION METHOD OF THIN FILM USING SILICON PRECURSOR}

The present disclosure relates to a thin film deposition method using a silicon precursor compound, and more particularly, to deposit a silicon oxide thin film or a silicon nitride thin film applied to a semiconductor device by atomic layer deposition (ALD) using a silicon precursor compound. It relates to a thin film deposition method using a silicon precursor compound, including.

In recent years, semiconductor devices have been continuously scaled down to improve productivity and quality, and in this process, excellent coating properties for high step ratios, new materials, and new process developments are required. In addition, the physical properties of the deposited thin films, such as thickness control reliability at thin thickness, deposition properties for existing materials at low temperatures, compositions, coating properties are becoming increasingly important.

Representative methods of depositing thin films on substrates include chemical vapor deposition (CVD) and atomic layer deposition (ALD).

Chemical vapor deposition is the most commonly used method. The chemical vapor deposition method is a method in which a precursor of molecules or atomic units is simultaneously injected into a reaction chamber to form a thin film, and the coating property and growth rate of the formed thin film are excellent.

However, the chemical vapor deposition method needs to be heated to a temperature where precursors can chemically react to form a thin film on the substrate, and because the gas phase reaction between the precursor and the reactant gas and the chemical reaction on the substrate occur simultaneously in the reaction chamber, It has the disadvantage of generating a lot of impurities.

On the other hand, Atomic Layer Deposition (ALD) method separates the reaction gases separately and supplies them into the chamber in the form of a pulse so that no gas phase reaction occurs, and the thin film is self-limiting only on the substrate. Since the deposition is performed at a low temperature, the thickness and the composition can be precisely controlled, and even in a complicated shape of the substrate, there is an advantage of forming a uniform composition and a step coverage close to 100%.

Meanwhile, silicon oxide (SiO ₂ ) is the most widely used material as a dielectric material in semiconductor integrated circuit processes. In the process of forming transistors, silicon oxide thin films are formed through thermal oxidation at a high temperature of 900 ° C. or higher. Or a thin film is formed through a low pressure chemical vapor deposition (LPCVD) method at 700 ° C. or higher.

However, such a method is a deposition process performed at a high temperature, and according to the ultra miniaturization of semiconductor devices, there is an increasing need to form a high quality silicon oxide thin film at a lower temperature.

Therefore, the present inventors confirmed that the silicon precursor compound can be applied to an atomic layer deposition method capable of depositing at a low temperature, and a method of depositing a silicon oxide thin film, a silicon nitride thin film, or a silicon oxynitride thin film by the atomic layer deposition method. At one end, the present invention was completed.

The present application is to solve the above problems,

A silicon precursor compound which deposits a silicon precursor compound by atomic layer deposition method, which is highly volatile, exists in a liquid state at room temperature, can be deposited at low temperature, and deposits a silicon oxide thin film, a silicon nitride thin film, or a silicon oxynitride thin film. It is an object of the present invention to provide a thin film deposition method.

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

The present invention to achieve the above object,

Contacting an organic silicon compound defined by Formula 1 with a substrate and depositing a silicon oxide thin film, a silicon nitride thin film or a silicon oxynitride thin film on the substrate at a deposition temperature of 100 ° C. to 500 ° C. by atomic layer deposition. A thin film deposition method using a silicon precursor compound is provided.

<Formula 1>

은 탄소수 3 내지 10의 싸이클릴 아민, 분자내 2중결합을 갖는 불포화싸이클릭 아민, 편재화(localized)되어 있는 싸이클릭 아민, 산소, 황, 인 등을 1개 또는 그 이상을 포함하고 있는 싸이클릭 아민 중에서 선택되거나, 아민 이외의 위치에 탄소수 1에서 4까지의 알킬기(alkyl), 퍼플루오르알킬기, 알킬아미노알킬기, 알콕시알킬기, 실릴알킬기, 알콕시실릴알킬기, 사이클로알킬기, 벤질기, 알릴기, 알킬실릴기, 알콕시실릴기, 알콕시알킬실릴기, 아미노알킬실릴기가 치환되어 있는 싸이클릭 아민 중에서 선택되어진다.In Formula 1, m is an integer of 1 to 4,

Cyclic amines containing 3 to 10 carbon atoms, unsaturated cyclic amines having double bonds in the molecule, cyclic amines localized, oxygen, sulfur, phosphorus, etc. An alkyl group, perfluoroalkyl group, alkylaminoalkyl group, alkoxyalkyl group, silylalkyl group, alkoxysilylalkyl group, cycloalkyl group, benzyl group, allyl group, alkyl selected from a click amine, or in a position other than the amine It is selected from the cyclic amine which the silyl group, the alkoxy silyl group, the alkoxy alkyl silyl group, and the aminoalkyl silyl group substituted.

As described above, the thin film deposition method using the silicon precursor according to the present application uses an atomic layer deposition method, and by using an organosilicon compound having a high list rain, it is possible to accurately control the thickness and composition while lowering the process temperature, It is possible to form an excellent coating property and a uniform composition even in the substrate, and thus the properties of the semiconductor device can be deposited as an improved silicon oxide thin film, silicon nitride thin film or silicon oxynitride thin film, and particularly excellent properties and coating at a very thin thickness It can be used as a spacer of a gate for which a castle is required.

The silicon precursor used in the thin film deposition method using the silicon precursor according to the present invention is advantageous for making a composite oxide thin film of silicon and another metal, and does not generate corrosive byproducts such as HCl. In addition, SiO ₂ may be deposited even at a low temperature of 100 ° C. or 150 ° C., and a film having a constant thickness may be formed on a surface with high unevenness. The SiO ₂ film formed at 404 ° C. or higher is as excellent in electrical properties as the SiO ₂ film formed by ALD or LPCVD using a precursor Si ₂ Cl ₆ as a raw material. In addition, ALD film growth rate is higher than other silicon precursors with silicon-nitrogen bonds.

1 is a diagram showing the results of TG / DSC analysis of trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] prepared by Example 1 of the present application.
2 is a view showing the deposition characteristics according to the temperature of the precursor compound carried out by Experimental Example 2 of the present application.
3 is a view showing a result of the thickness change of the thin film according to the supply time of the precursor compound carried out by Experimental Example 2 of the present application.
4 is a view showing the results of the thickness change of the thin film according to the supply time of ozone gas (O ₃ / O ₂ ) of the precursor compound carried out by Experimental Example 2 of the present application.
5 is a view showing a thin film thickness change with the temperature change of the precursor compound carried out by Experimental Example 2 of the present application.
6 is a view showing the leakage current characteristics of the thin film of the precursor compound carried out by Experimental Example 2 of the present application.
7 is a view showing the deposition rate of the film according to the supply time of the precursor compound carried out in Example 3 of the present application and the deposition rate of the film according to the supply time of ozone gas (O ₃ / O ₂ ) of the precursor compound .
8 is a view showing the deposition rate of the film according to the substrate temperature change of the precursor compound carried out by Example 3 of the present application and the leakage current characteristics of the deposited film.
FIG. 9 is a TEM photograph showing the step coverage of a silicon oxide foil deposited using a precursor compound carried out in Example 3 of the present application. FIG.
10 is a view showing a comparison result of the deposition rate according to the substrate temperature and the leakage current characteristics of the deposited silicon oxide film for each of the precursor compound according to the present application and the conventional precursor Si ₂ Cl _{6 in} Example 3 of the present application.

Hereinafter, a thin film deposition method using the silicon precursor compound of the present application will be described in more detail.

The present invention relates to a method for depositing a silicon oxide thin film, a silicon nitride thin film or a silicon oxynitride thin film applied to a semiconductor device, wherein the silicon precursor compound is contacted with a substrate to form a silicon oxide thin film, a silicon nitride thin film or While depositing a silicon oxynitride thin film, the deposition temperature is characterized in that 100 ~ 500 ℃.

In one embodiment, the deposition temperature may be 100 to 500 ° C, or 150 to 500 ° C, or 200 to 500 ° C, or 250 to 500 ° C, or 300 to 500 ° C, but is not limited thereto.

As such, the present application may lower the process temperature during deposition by depositing a silicon oxide thin film, a silicon nitride thin film, or a silicon oxynitride thin film using an atomic layer deposition method. In addition, since the thickness and composition of the thin film can be precisely controlled, a thin film having excellent coating properties can be deposited even on a complicated substrate, and the thickness uniformity and physical properties of the thin film can be improved.

At this time, when the deposition temperature is less than 100 ℃, less than 150 ℃, less than 200 ℃, or less than 300 ℃ the film formation temperature is low due to the formation of an incomplete thin film may increase the content of carbon contamination and other impurities, sufficient film formation rate It is not economical because it cannot be obtained, and conversely, if the deposition temperature exceeds 500 ° C., it is not preferable because there is no significant difference from the conventional chemical vapor deposition method (CVD) in which the thin film is deposited at a considerable temperature. Therefore, the deposition temperature may be 100 to 500 ° C., or 150 to 500 ° C., or 200 to 500 ° C., or 250 to 500 ° C., or 300 to 500 ° C., but is not limited thereto.

 At this time, the silicon precursor compound used in the present invention is preferably to use an organic silicon compound defined by the formula (1).

은 탄소수 3 내지 10의 싸이클릴 아민, 분자내 2중결합을 갖는 불포화싸이클릭 아민, 편재화(localized)되어 있는 싸이클릭 아민, 산소, 황, 인 등을 1개 또는 그 이상을 포함하고 있는 싸이클릭 아민 중에서 선택되는 하나이거나, 아민 이외의 위치에 탄소수 1에서 4까지의 알킬기(alkyl), 퍼플루오르알킬기, 알킬아미노알킬기, 알콕시알킬기, 실릴알킬기, 알콕시실릴알킬기, 사이클로알킬기, 벤질기, 알릴기, 알킬실릴기, 알콕시실릴기, 알콕시알킬실릴기, 아미노알킬실릴기가 치환되어 있는 싸이클릭 아민 중에서 선택되는 하나일 수 있다.In Formula 1, m is an integer of 1 to 4,

Cyclic amines containing 3 to 10 carbon atoms, unsaturated cyclic amines having double bonds in the molecule, cyclic amines localized, oxygen, sulfur, phosphorus, etc. One selected from click amines, or alkyl, perfluoroalkyl, alkylaminoalkyl group, alkoxyalkyl group, silylalkyl group, alkoxysilylalkyl group, cycloalkyl group, benzyl group, allyl group having 1 to 4 carbon atoms at positions other than the amine. , Alkylsilyl group, alkoxysilyl group, alkoxyalkylsilyl group, aminoalkyl silyl group may be one selected from cyclic amine substituted.

은 5~6각 고리를 형성하고 있는 피롤리딘, 피롤, 피페리딘, 및 모르폴린(morpholine) 중에서 선택되는 것이 더욱 바람직하며, 이중에서도 피롤리딘, 또는 피롤인 것이 더 바람직하다.More preferably, in the organosilicon compound defined by Formula 1, an integer of m = 1 to 4,

Is more preferably selected from pyrrolidine, pyrrole, piperidine, and morpholine forming a 5 to 6 hexacyclic ring, and more preferably pyrrolidin or pyrrole.

In the organosilicon compound defined by Formula 1, since the amine bonded to Si is a heterocyclic amine in which a cyclic strain is present, the amine is easily separated from the Si atom by the ring strain. It is thus advantageous to form a silicon oxide thin film (SiO 2) or a silicon nitride thin film (SiN) x by reacting with a highly reactive oxidant, and by this reaction mechanism 100-500 ° C., or 150-500 ° C., or 200 Deposition is possible even at low deposition temperatures of ˜500 ° C., or 250-500 ° C., or 300-500 ° C.

In addition, since it does not have direct carbon bonds, it is possible to effectively lower the carbon content in the metal thin film, to reduce the deterioration of physical properties due to the inclusion of carbon impurities, to have high volatility even at low temperatures, and to exist in a liquid state at room temperature to atom It can be suitably used as a silicon precursor compound for depositing a silicon oxide thin film and a silicon oxynitride thin film or a silicon nitride thin film by a layer deposition method.

 The organosilicon compound may be suitably used as a silicon precursor compound for depositing a silicon oxide thin film and a silicon oxynitride thin film or a silicon nitride thin film by atomic layer deposition by being in a liquid state at room temperature.

은 5각 고리 화합물 피롤리딘인 하기 화학식 2로 표현되는 유기 실리콘 화합물인 것이 바람직하다.In addition, m is 3 in the organosilicon compound defined by Formula 1 used as the silicon precursor compound of the present application,

It is preferable that it is an organosilicon compound represented by following formula (2) which is a pentagonal ring compound pyrrolidine.

은 5각 고리 화합물 피롤리딘인 하기 화학식 3으로 표현되는 유기 실리콘 화합물인 것이 바람직하다.In addition, m is 2 in the organosilicon compound defined by Formula 1 used as the silicon precursor compound of the present application,

It is preferable that it is an organosilicon compound represented by following formula (3) which is a pentagonal ring compound pyrrolidine.

As described above, the organosilicon compound used as the silicon precursor compound represented by Chemical Formula 1 may be prepared by various methods. Preferably, the alkyl metal is formed on the tris or bis halide ligand silicone compound in a nonpolar solvent as shown in Scheme 1. The metallized cyclic amine compound may be added at low temperature, exchanged at room temperature, removed through salt filtration, and then distilled under reduced pressure.

Scheme 1

In this Scheme 1, R is alkyl, and is selected from methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, and tert-butyl, and M means lithium (Li) or sodium (Na) metal cation. .

In addition, as shown in Scheme 2, the organosilicon compound of Formula 1 is added to the tris or bis halide ligand silicone compound in an excess of two or more equivalents at low temperature, and then exchanged at room temperature, followed by filtration. It can also be easily obtained by removing the salt in the form of the amine salt via distillation under reduced pressure.

Scheme 2

은 각각 화학식 1에서 정의한 바와 같으며, 특히

은 탄소수 3 내지 10의 싸이클릭 아민, 분자내 2중결합을 갖는 불포화싸이클릭 아민, 편재화(localized)되어 있는 싸이클릭 아민, 산소, 황, 인 등을 1개 또는 그 이상을 포함하고 있는 싸이클릭 아민 중에서 선택되는 것이 보다 바람직하고, 더욱 바람직하게는 5~6각 고리를 형성하고 있는 피롤리딘, 피롤, 피페리딘, 모르폴린중에서 선택될 수 있으며, 이중에서도 피롤리딘, 또는 피롤 중에서 선택되는 것에 더욱 바람직하다. In Scheme 1 and Scheme 2, X is a halide (halide) series, it may be selected from F, Cl, Br, I,

Are as defined in formula 1, and in particular,

Is a cyclic amine having 3 to 10 carbon atoms, an unsaturated cyclic amine having a double bond in a molecule, a localized cyclic amine, oxygen, sulfur, phosphorus, etc. More preferably, it is selected from the click amine, More preferably, it may be selected from pyrrolidine, pyrrole, piperidine, and morpholine which form a 5-6 hexagonal ring, and among them, pyrrolidine or pyrrole It is more preferable to select from among.

In addition, as the solvent, hexane (hexane), pentane, or toluene having a weak polarity may be preferably used.

More specifically, the manufacturing method of the organic silicon compound represented by <Formula 2> to <Formula 3> used as the silicon precursor compound in the present invention is as follows.

The above-described organosilicon compound of Chemical Formula 2 is a lithium blood metallized using normal butyllithium (n-BuLi) in a trichlorosilane compound (HSiCl ₃ ) solution in a hexane solvent which is a non-polar solvent as shown in Scheme 3 below. After the addition of the lollidine compound at low temperature, the reaction is stirred at room temperature, followed by filtration to remove the salt, followed by distillation under reduced pressure. In this case, pentane, toluene, etc. may be used as the non-polar solvent, and nitrogen (N ₂ ) or argon (Ar It is preferable to proceed with the reaction under the air stream.

Scheme 3

The above-described organosilicon compound of <Chemical Formula 3> is a metal using normal butyllithium (n-BuLi) in a dichlorosilane compound (H ₂ SiCl ₂ ) solution in a hexane (hexane) solvent which is a nonpolar solvent as shown in Scheme 4 below. After the oxidized lithium pyrrolidine compound is added at low temperature, the reaction is stirred at room temperature, and then, the salt is removed by filtration and then distilled under reduced pressure.

Scheme 4

In addition, the thin film deposition method using the silicon precursor compound according to the present invention more specifically, after receiving the substrate in the reaction chamber, using a transport gas or dilution gas to transfer the gas of the silicon precursor compound onto the substrate to contact the substrate By depositing a silicon oxide thin film, a silicon nitride thin film, or a silicon oxynitride thin film at the above-mentioned deposition temperature of 100 to 500 ° C, 150 to 500 ° C, or 200 to 500 ° C, or 250 to 500 ° C, or 300 to 500 ° C. It is to let.

At this time, it is preferable to use one or more mixtures selected from argon (Ar), nitrogen (N ₂ ), helium (He) or hydrogen (H ₂ ) as the transport gas or diluent gas.

In addition, the method of transferring the silicon precursor compound onto the substrate using a bubbling method to vaporize and a liquid delivery system (LDS) to be deposited by vaporizing through a vaporizer by supplying the liquid phase at room temperature and using the vapor pressure of the precursor Various supply methods including a VFC (vapor flow controller) method of supplying directly may be applied, but most preferably, the silicon precursor compound is transported in a temperature range of 0.1 to 10 torr and room temperature to 80 ° C. in a bubbler container. A bubbling manner may be used in which the vessel is bubbled by gas and vaporized.

Further, in order to vaporize the silicon precursor compound, it is more preferable to bubble with argon (Ar) or nitrogen (N ₂ ) gas, use thermal energy or plasma, or apply a bias on the substrate.

More specifically, the present application is a gas and water vapor (H ₂ O), oxygen (O ₂ ), oxygen nitride (NO, N ₂ O, N ₂ O ₂ ), hydrogen peroxide (H ₂ ) of the organosilicon compound defined by Formula 1 One or two or more mixture gases selected from O ₂ ) and ozone (O ₃ ) are brought into contact with the substrate simultaneously or alternately to form silicon oxide or Hf-Si-O, Zr-Si-O, Ti-Si-O Hf on the substrate. A composite oxide thin film containing silicon such as -Al-Si-O, Zr-Al-Si-O, TiAlSiOx, Zr-Hf-Si-O, Zr-Hf-Al-Si-O may be deposited.

In addition, the silicon nitride or Hf-Si-N Zr-Si-N on the substrate by contacting the substrate of the organic silicon compound defined by the formula (1) and one or more mixture gases selected from ammonia and hydrazine simultaneously or alternately with the substrate , Ti-Si-N, Hf-Al-Si-N, Zr-Al-Si-N, Ti-Al-Si-N, Zr-Hf-Si-N, Zr-Al-Si-N, Ti-Al It is also possible to deposit a thin film of composite nitride containing silicon such as -Si-N.

Hereinafter, a thin film deposition method using a silicon precursor compound according to the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present application, and the present invention is limited to the following examples. no.

< Example  1>

Of formula 2 Tris Pyrrolidino  Silanes [HSi {N ( C ₄ H ₈ )} ₃ Manufacture of

105.88 mL (0.27 mol, 2.5 M in hexane) of n-butyllithium (n-BuLi) was diluted in 200 mL of hexane, and then 22.33 mL (0.27 mol) of pyrrolidine (HN (C ₄ H ₈ )) was added to the solution. Was added dropwise at −78 ° C., and then the mixed solution was slowly raised to room temperature with stirring, followed by stirring for 12 hours to form a metallized lithium pyrrolidine salt. 67.12 mL (0.9 mol) of trichlorosilane was slowly added dropwise to the formed lithium pyrrolidin salt solution at -78 ° C, and then the mixed solution was raised to room temperature with stirring, followed by stirring for 12 hours. After completion of the reaction, the salt produced during the reaction was removed by filtration and the solvent and volatile side reactions were removed by distillation under reduced pressure to obtain a colorless liquid compound. The liquid compound was distilled under reduced pressure to obtain 170 g (yield: 79.2%) of trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] as a colorless liquid compound:

b.p: 94 ° C. at 0.58 torr.

¹ H-NMR (C ₆ D ₆ ): δ 1.605 (CH ₂ , bs, 12H)

δ 3.056 (NCH ₂ , bs, 12H)

δ 4.821 (SiH, s, 1H).

< Example  2>

Of formula 3 Vis Pyrrolidino  Silane [H ₂ Si {N ( C ₄ H ₈ )} ₂ Manufacture of

105.88 mL (0.27 mol, 2.5 M in hexane) of n-butyllithium (n-BuLi) is diluted in 200 mL of hexane, and then 22.33 mL (0.27 mol) of pyrrolidine (HN (C ₄ H ₈ )) is added to this solution. Was added dropwise at −78 ° C., and then the mixed solution was slowly raised to room temperature with stirring, followed by stirring for 12 hours to form a metallized lithium pyrrolidine salt. 13.63 g (0.135 mol) of dichlorosilane was slowly added dropwise to the formed lithium pyrrolidin salt solution at -78 ° C, and then the mixed solution was raised to room temperature with stirring, followed by stirring for 12 hours. After completion of the reaction, the salt produced during the reaction was removed by filtration and the solvent and volatile side reactions were removed by distillation under reduced pressure to obtain a colorless liquid compound. This liquid compound was distilled under reduced pressure to obtain 85 g (yield: 50%) of bispyrrolidino silane [H ₂ Si {N (C ₄ H ₈ )} ₃ ] as a colorless liquid compound.

b.p: 62 ° C. at 0.4 torr.

¹ H-NMR (C ₆ D ₆ ): δ 1.612 (CH ₂ , bs, 8H)

δ 3.128 (NCH ₂ , bs, 8H)

δ 4.851 (SiH, s, 2H)

< Experimental Example  1>

In order to analyze the basic thermal characteristics of the organosilicon compound prepared in Example 1, that is, the trispyrrolidino silane precursor compound, TG & DSC analysis was performed, and the results are shown in FIG. 1.

As can be seen in Figure 1 it can be seen that all the silicon precursor compound prepared in Example 1 exhibits sufficient volatility to apply to the atomic layer deposition method. In addition, it can be seen that the trispyrrolidino silane precursor compound prepared in Example 1 has thermal stability equal to or higher than that of conventional organic silicon compounds. In addition, it was confirmed that the thermal decomposition appeared below 500 ℃ as shown on the DSC curve.

< Experimental Example  2>

Trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] precursor prepared in Example 1 and atomic layer deposition (ALD) experiments were performed using ozone (O ₃ ) as the oxygen source (O ₂ ). It was. First, sulfuric acid (H ₂ SO ₄ ) After dipping the silicon wafer for 10 minutes in a piranha solution mixed with 4: 1 hydrogen peroxide (H ₂ O ₂ ), and then immersing in dilute HF solution for 2 minutes to form a pure silicon surface. A silicon oxide thin film was prepared by the deposition method (ALD). At this time, the temperature of the substrate was heated from 300 ° C to 500 ° C and the trispyrrolidino silane precursor [HSi {N (C ₄ H ₈ )} ₃ ] used as a precursor was placed in a bubbler container made of stainless steel. It was vaporized by bubbling the vessel using argon (Ar) gas having a flow rate of 100 sccm as a carrier gas of the precursor compound while heating the vessel at a temperature of 2 torr and 60 ° C. At this time, the supply amount of the precursor into the reactor was 1.5 × 10 ⁶ L, the oxygen flow rate ozone gas (0 ₃ / O ₂ ) flow rate was adjusted to 110sec at 9.5 torr.

-Deposition Characteristics According to Temperature-

The ALD cycle was fixed to 25 cycles in order to measure the deposition characteristics of the trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] precursor compound according to the method of Example 1, and the precursor was 1.5 × 10 ⁶ L, the oxygen source ozone gas (0 ₃ / O ₂ ) flow rate is supplied in 110 sec at 9.5 torr and the results of the growth rate (growth rate) according to the temperature at 300 ~ 500 ℃ is shown in FIG.

As can be seen in Figure 2, the deposition started from 300 ℃, it can be seen that the highest deposition rate at 450 ℃.

Deposition Rate Characteristics

In order to check the thickness change of the thin film according to the supply time of the Si precursor prepared by the method in Example 1, the ALD cycle was fixed at 50 times and the oxygen-causing ozone gas (0 ₃ / O ₂ ) flow rate was from 9.5 torr to 110 sec. Deposition thickness characteristics measured at 450 ° C. by feeding are shown in FIG. 3. It was shown that the pulse time of Si precursor rapidly increased up to 10 seconds and then decreased gradually with increasing supply time. As can be seen in Figure 3 it was confirmed that the supply time of the precursor is suitable for 10 sec.

In order to check the thickness change of the thin film according to the supply time of ozone gas (O ₃ / O ₂ ) of the Si precursor prepared by the method of Example 1, the ALD cycle was fixed to 50 times and the pulse time of the Si precursor was fixed. The deposition thickness characteristics measured at 450 ° C. by supplying this for 10 seconds are shown in FIG. 4.

As can be seen in Figure 4, the supply time of ozone gas (O ₃ / O ₂ ) was confirmed that the growth rate is saturated at 110 sec.

-Thin Film Thickness Change with Temperature-

The thickness change of the thin film according to the temperature change in the conditions saturated with the supply time of the Si precursor prepared by the method in Example 1 and the supply time of ozone gas (O ₃ / O ₂ ) is shown in FIG. 5. The ALD cycle was fixed at 50 cycles, the precursor was supplied at 10 sec, and the oxygen source ozone gas (0 ₃ / O ₂ ) was supplied at 110 ses.

As can be seen in Figure 5 it was confirmed that the ALD reaction is activated to the maximum thickness at 450 ℃.

-Leakage current characteristic change-

ALD SiO ₂ thin film was deposited in the range of 300 ° C. to 500 ° C. of the Si precursor prepared by the method in Example 1, and the leakage current characteristics thereof were measured and shown in FIG. 6.

As can be seen in Figure 6 as the temperature of the substrate is increased the quality of the thin film to increase the leakage current, the thin film formed at 500 ℃ was deposited at 550 ℃ and the thin film formed at 550 ℃ using HCD (Si ₂ Cl ₆ ) It can be seen that the same characteristics as the LPCVD thin film.

< Example  3>

Of formula 2 Tris Pyrrolidino  Silanes [HSi {N ( C ₄ H ₈ )} ₃ Deposition and characterization of silicon oxide films using silicon precursor

Formula containing no chlorine ions as prepared in Example 1 A silicon oxide film was deposited by the ALD method using trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ].

Specifically, atomic layer deposition (ALD) using trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] precursor prepared in Example 1 and ozone (O ₃ ) as the oxygen source (O ₂ ). The experiment was performed. First, sulfuric acid (H ₂ SO ₄ ) After dipping the silicon wafer for 10 minutes in a piranha solution mixed with 4: 1 hydrogen peroxide (H ₂ O ₂ ), and then immersing in dilute HF solution for 2 minutes to form a pure silicon surface. A silicon oxide thin film was prepared by the deposition method (ALD). At this time, the temperature of the substrate was heated from 150 ℃ to 500 ℃ and the trispyrrolidino silane precursor [HSi {N (C ₄ H ₈ )} ₃ ] used as a precursor is placed in a bubbler container made of stainless steel. It was vaporized by bubbling the vessel using argon (Ar) gas having a flow rate of 100 sccm as a carrier gas of the precursor compound while heating the vessel at a temperature of 2 torr and 60 ° C. At this time, the supply amount of the precursor into the reactor was adjusted to 3 × 10 ⁵ L, the oxygen flow ozone gas (0 ₃ / O ₂ ) flow rate was adjusted from 9.5 torr to 110 sec.

Deposition Rate Characteristics

In order to check the thickness change of the thin film according to the pulse time of the Si precursor prepared by the method of Example 1, the ALD cycle was fixed at 50 times and the oxygen-causing ozone gas (0 ₃ / O ₂ ) flow rate was 9.5 torr. Deposition thickness characteristics measured at 280 ° C. and supplied at 110 sec are shown in FIG. 7. The deposition time of the Si precursor was rapidly increased to about 0.1 nm / cycle until the pulse time was 10 seconds, and the deposition rate was almost constant according to the supply time.

In order to check the thickness change of the thin film according to the supply time of ozone gas (O ₃ / O ₂ ) of the Si precursor prepared by the method of Example 1, the ALD cycle was fixed to 50 times and the pulse time of the Si precursor was fixed. The deposition thickness characteristics measured at 280 ° C. by supplying 10 seconds are shown in FIG. 7.

As can be seen in Figure 7. The ozone gas (O ₃ / O ₂₎ feed time is deposited in accordance with Example increasing the supply time of the deposition rate increases to about 0.1 nm / cycle at about 27 sec ozone gas (O ₃ / O ₂₎ to the You can see that the speed remains almost constant.

The exposure of the trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] to complete the surface reaction was about 3 × 10 ⁵ L, which was applied to the conventional precursor Si ₂ Cl ₆ for saturation of the deposition rate. In comparison, the trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] precursor according to the present application is more responsive.

-Deposition Characteristics According to Temperature-

In order to measure the deposition characteristics according to the substrate temperature of the trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] precursor compound prepared by the method of Example 1, the ALD cycle was fixed to 50 times, and the Si The precursor's pulse time is 10 seconds and the oxygen source ozone gas (0 ₃ / O ₂ ) flow rate is supplied from 9.5 torr to 110 sec to increase the deposition rate according to the substrate temperature at 200-500 ℃. rate) results are shown in FIG. 8.

As shown in FIG. 8, the deposition of the silicon oxide film was also carried out at a low temperature at 150 ° C. using the trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] precursor compound, which is a conventional precursor Si _2. Lower than the deposition temperature of Cl ₆ .

The silicon oxide film was deposited at a temperature of 150 ℃ to 478 ℃, the deposition rate was saturated at 404 ℃ maximal deposition rate of 0.25 nm / cycle for the exposure 3 × 10 ⁵ L of Si (NC ₄ H ₈ ) ₃ H Indicated. In a high temperature region (404 ℃ to 478 ℃) were measured for the silicon oxide film, leakage current characteristics change (FIG. 8), in a high temperature region of the substrate, the higher the quality of the film was decreased, the leakage current, which is Si ₂ Cl ₆ conventional precursor It has excellent electrical properties corresponding to the silicon oxide film by LPCVD and ALD.

Step Coverage Analysis

Step coverage was analyzed using TEM using a hole pattern having an aspect ratio of 50 and is shown in FIG. 9. The ALD silicon oxide film of this example showed excellent step coverage.

-Comparison with conventional precursor Si ₂ Cl ₆

Comparison of the Deposition Rate According to the Substrate Temperature and the Properties of the Deposited Silicon Oxide Film with respect to the Trispyrrolidino Silane [HSi {N (C ₄ H ₈ )} ₃ ] Precursor Compound of Example 1 and the Precursor Si ₂ Cl ₆ The experimental results are shown in FIG. 10.

As shown in FIG. 10, low temperature deposition below 300 ° C. was achieved by the trispyrrolidino silane [HSi {N (C ₄ H ₈ )} ₃ ] precursor compound of Example 1, and leakage current density was Almost similar when using the precursor.

Summarizing the results of this example, the precursors according to the present application are advantageous for making composite oxide thin films of silicon and other metals, and no corrosive byproducts such as HCl are produced. In addition, it is possible to deposit SiO ₂ even at a low temperature of 150 ° C., and to form a film having a constant thickness on a surface with high unevenness. The SiO ₂ film formed at 404 ° C. or higher is as excellent in electrical properties as the SiO ₂ film formed by ALD or LPCVD using a precursor Si ₂ Cl ₆ as a raw material. In addition, ALD film growth rate is higher (0.25 nm / cycle at 404 ° C.) than other silicon precursors with silicon-nitrogen bonds.

Thus, the thin film deposition method according to the present invention was able to confirm that the silicon precursor compound can be deposited as a silicon oxide thin film or a silicon nitride thin film or a silicon oxynitride thin film by the atomic layer deposition method, the process temperature through the thin film deposition method of the present application The thickness and composition can be precisely controlled while lowering, and even a complex substrate can be formed with excellent coating properties and uniform composition. Therefore, a semiconductor device can be formed by a silicon oxide thin film or a silicon nitride thin film or a silicon oxynitride thin film deposited thereon. It is expected to be able to improve the characteristics of, and it will be very effective in the spacer of gate, STI, ONO stack, passivation layer and other fields, which require excellent physical property and coating property at very thin thickness. It is expected.

As described above, the present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the above embodiments and embodiments, and may be modified in various forms, and within the technical spirit of the present application, common knowledge in the art. It is obvious that many variations are possible by the possessor.

Claims (6)

Contacting an organic silicon compound defined by Formula 1 with a substrate and depositing a silicon oxide thin film, a silicon nitride thin film or a silicon oxynitride thin film on the substrate at a deposition temperature of 100 ° C. to 500 ° C. by atomic layer deposition. Thin film deposition using silicon precursor compound:
<Formula 1>

In Chemical Formula 1,
m = 1 to 4,

Silver cyclyl amine having 3 to 10 carbon atoms; Unsaturated cyclic amines having intramolecular double bonds; Cyclic amines that are localized; And a cyclic amine containing one or more of oxygen, sulfur, phosphorus and the like, or an alkyl group having 1 to 4 carbon atoms, perfluoroalkyl group, alkylaminoalkyl group, alkoxy at a position other than the amine. Selected from cyclic amines substituted with an alkyl group, silylalkyl group, alkoxysilylalkyl group, cycloalkyl group, benzyl group, allyl group, alkylsilyl group, alkoxysilyl group, alkoxyalkylsilyl group, or aminoalkylsilyl group.
The method according to claim 1,
The organosilicon compound defined by Chemical Formula 1 is an integer of m = 1 to 4,

Silver is a thin film deposition method using a silicon precursor compound that is selected from pyrrolidin, pyrrole, piperidine, and morpholine forming a 5-6 hexagonal ring.
The method according to claim 2,
In the organosilicon compound defined by Formula 1, m is an integer of 3,

A thin film deposition method using a silicon precursor compound, which is an organosilicon compound represented by the following Chemical Formula 2, wherein the silver pentacyclic compound is pyrrolidin:
<Formula 2>

The method according to claim 2,
In the organosilicon compound defined by Formula 1, m is an integer of 2,

A thin film deposition method using a silicon precursor compound, which is an organosilicon compound represented by the following Chemical Formula 3, which is a pentagonal ring compound pyrrolidine:
<Formula 3>

The method according to claim 1,
Gas and water vapor (H ₂ O), oxygen (O ₂ ), oxygen nitride (NO, N ₂ O, N ₂ O ₂ ), hydrogen peroxide (H ₂ O ₂ ) and ozone of the organosilicon compound defined by Chemical Formula 1 One or two or more mixture gases selected from (O ₃ ) are brought into contact with the substrate simultaneously or alternately to form silicon oxide or Hf-Si-O, Zr-Si-O, Ti-Si-O Hf-Al-Si- on the substrate. A silicon precursor compound comprising depositing a composite oxide thin film comprising silicon selected from O, Zr-Al-Si-O, TiAlSiOx, Zr-Hf-Si-O, and Zr-Hf-Al-Si-O Thin film deposition method using.
The method according to claim 1,
Silicon nitride or Hf-Si-N Zr-Si-N, Ti on the substrate by contacting the substrate of the organic silicon compound defined by Formula 1 with one or more mixture gases selected from ammonia and hydrazine simultaneously or alternately -Si-N, Hf-Al-Si-N, Zr-Al-Si-N, Ti-Al-Si-N, Zr-Hf-Si-N, Zr-Al-Si-N, Ti-Al-Si A thin film deposition method using a silicon precursor compound, comprising depositing a composite nitride thin film containing silicon selected from -N.

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