KR101149811B1 - Deposition method of thin film using silicon precursor - Google Patents

Abstract

PURPOSE: A thin film deposition method using silicone precursor compounds is provided to obtain uniform thickness even in case of a relatively thick thin film with a high aspect ratio. CONSTITUTION: A thin film deposition method using silicone precursor compounds comprises the steps of: selecting gas of one or more compounds from the group consisting of TEMAH(Tetrakis(Ethylmethylamino) Hafnium) and TDMAT(Tetrakis(Dimethylamido)Titanium), selecting gas of one or more mixtures among H2O(Water), O2(Oxygen), oxy nitride, H2O2(Hydrogen Peroxide), and O3(Ozone), and simultaneously or alternately contacting the compound gas, gas of organic silicon compound, and the mixture gas to a wafer so that a composite thin film including silicon is deposited on the wafer. The silicon is selected among Hf-Si-O, Zr-Si-O, Ti-Si-O, and Zr-Hf-Si-O.

Description

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

The present invention relates to a method of depositing various thin films including silicon by supplying a silicon precursor compound in a gaseous state.

In semiconductor manufacturing, silicon oxide thin films are used for various purposes. However, the formation of a silicon oxide film by atomic layer deposition (ALD), in which raw material gases are alternately contacted with a substrate to form a film of a desired material, has been relatively recently started. It was difficult to form a silicon oxide film by atomic layer deposition using chemical vapor deposition materials such as silane (SiH ₄ ) or tetraethoxysilane (TEOS, Si (OC ₂ H ₅ ) ₄ ), which are widely used. The silicon oxide film may be formed by atomic vapor deposition by supplying an aminosilicon compound having nitrogen bonded to silicon in a gaseous state. An atomic layer deposition method is also known in which an aminosilane compound is supplied in a gaseous state to form a silicon nitride film. The aminosilane compound can be used not only for atomic layer deposition but also for chemical vapor deposition.

Paper published in 2006 by Kamiyama et al. [Satoshi Kamiyama, Takayoshi Miura and Yasuo Nara, "Comparison between SiO ₂ films deposited by atomic layer deposition with SiH ₂ [N (CH ₃ ) ₂ ] ₂ and SiH [N (CH ₃ ) ₂ ] ₃ precursors "Thin Solid Films, Volume 225 (2006) p.1517] Bisdimethylamino for Silicon Oxide Atomic Layer Deposition Using Aminosilane Compounds and Silicon Oxide Film Growth Thickness per Atom Feed Cycle in Atomic Layer Deposition 0.031-0.118 nm / cycle for silane (BDMAS, SiH ₂ [N (CH ₃ ) ₂ ] ₂ ), 0.021-0.077 for trisdimethylaminosilane (TDMAS, SiH [N (CH ₃ ) ₂ ] ₃ ) as nm / period.

In addition, Korean Patent Application Publication No. 10-2009-0068179 and US Patent Application Publication No. 2009/0209081 disclose silicon oxide atoms using hexakis (ethylamino) disilane (Si ₂ [NH (CH ₂ CH ₃ )] ₆ ) as an aminosilane compound. It is disclosed that the silicon oxide film growth thickness is 0.11 nm / cycle per raw material supply cycle of the layer deposition method and the atomic layer deposition method.

  Published in 2004 by Senzaki et al. [Yoshihide Senzaki, Seung Park, Hood Chatham, Lawrence Bartholomew, and Wesley Nieveen, "Atomic layer deposition of hafnium oxide and hafnium silicate thin films using liquid precursors and ozone" Journal of Vacuum Science & Technology A, Volume 22 (2004) p.1175] discloses a method for forming a composite oxide hafnium silicate thin film by an atomic layer deposition method in which an aminosilane compound and an amino hafnium compound are supplied in a gaseous state.

Conventionally, it is known that a silicon oxide film can be formed by atomic layer deposition or chemical vapor deposition (CVD) using a silane chloride compound such as silane tetrachloride (SiCl ₄ ) or disilane hexachloride (Si ₂ Cl ₆ ). have. However, in such a conventional method, since corrosive hydrogen chloride (HCl) is generated as a by-product, it is difficult to apply to a case where a substance sensitive to hydrogen chloride, such as aluminum metal, is exposed on a substrate.

Therefore, when forming a film containing silicon by atomic layer deposition, chemical vapor deposition, etc. in a semiconductor manufacturing process, the development of a silicon precursor and a deposition method having a high film growth thickness per raw material supply cycle to increase the product production rate per unit time has been developed. It is still required.

It is an object of the present invention to provide a method for producing a thin film of a thin film including silicon.

It is another object of the present invention to provide a thin film manufacturing method having a high growth rate of a thin film including silicon.

It is still another object of the present invention to provide a method for manufacturing a thin film including silicon in a uniform thickness in a high aspect ratio structure.

Still another object of the present application is to provide a method for manufacturing a composite oxide thin film including silicon and another metal.

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

One aspect of the present application includes supplying an organic silicon compound represented by Chemical Formula 1 in a gaseous state and contacting the substrate to deposit a silicon-containing thin film on the substrate at a deposition temperature of about 100 ° C. to about 500 ° C. A thin film deposition method using a silicon precursor compound is provided.

≪ Formula 1 >

In Formula 1, m is an integer of 1 to 4,

은, 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 분자내 탄소-탄소 이중결합을 갖는 탄소수 약 3 내지 약 10의 불포화싸이클릭 아민기; 편재화(localized)되어 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 산소, 황 및 인으로 이루어진 군에서 선택되는 헤테로원소를 1개 이상을 포함하는 탄소수 약 3 내지 약 10의 싸이클릭 아민기;및, 아미노기 외의 위치에 알킬기(alkyl), 퍼플루오르알킬기, 알킬아미노알킬기, 알콕시알킬기, 실릴알킬기, 알콕시실릴알킬기, 사이클로알킬기, 벤질기, 알릴기, 알킬실릴기, 알콕시실릴기, 알콕시알킬실릴기, 및 아미노알킬실릴기로 이루어진 군에서 선택되는 하나 이상의 치환기에 의하여 치환될 수 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기로 이루어진 군에서 선택되는 아민기임.

Silver, a cyclic amine group having about 3 to about 10 carbon atoms; Unsaturated cyclic amine groups having about 3 to about 10 carbon atoms having intramolecular carbon-carbon double bonds; Cyclic amine groups having about 3 to about 10 carbon atoms localized; A cyclic amine group having from about 3 to about 10 carbon atoms containing at least one heteroelement selected from the group consisting of oxygen, sulfur and phosphorus; and an alkyl group, perfluoroalkyl group, alkylaminoalkyl group at a position other than the amino group. , Alkoxyalkyl group, silylalkyl group, alkoxysilylalkyl group, cycloalkyl group, benzyl group, allyl group, alkylsilyl group, alkoxysilyl group, alkoxyalkylsilyl group, and aminoalkylsilyl group An amine group selected from the group consisting of cyclic amine groups having from about 3 to about 10 carbon atoms.

Another aspect of the disclosure is selected from the group consisting of tetrakis (ethylmethylamido) hafnium (TEMAH), tetrakis (ethylmethylamido) zirconium (TEMAZ) and tetrakis (dimethylamido) titanium (TDMAT) Gas of one or more compounds; A gas of an organosilicon compound represented by Formula 1 below; And at least one mixture gas selected from water vapor (H ₂ O), oxygen (O ₂ ), oxygen nitride, hydrogen peroxide (H ₂ O ₂ ) and ozone (O ₃ ) simultaneously or alternately in contact with the substrate to It provides a thin film deposition method using a silicon precursor compound, comprising depositing a composite thin film containing silicon selected from Hf-Si-O, Zr-Si-O, Ti-Si-O and Zr-Hf-Si-O. do.

≪ Formula 1 >

In Formula 1,

m = 1 to 4,

은, 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 분자내 탄소-탄소 이중결합을 갖는 탄소수 약 3 내지 약 10의 불포화싸이클릭 아민기; 편재화(localized)되어 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 산소, 황 및 인으로 이루어진 군에서 선택되는 헤테로원소를 1개 이상을 포함하는 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 및, 아미노기 외의 위치에 알킬기(alkyl), 퍼플루오르알킬기, 알킬아미노알킬기, 알콕시알킬기, 실릴알킬기, 알콕시실릴알킬기, 사이클로알킬기, 벤질기, 알릴기, 알킬실릴기, 알콕시실릴기, 알콕시알킬실릴기, 및 아미노알킬실릴기로 이루어진 군에서 선택되는 하나 이상의 치환기에 의하여 치환될 수 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기로 이루어진 군에서 선택되는 아민기임.

Silver, a cyclic amine group having about 3 to about 10 carbon atoms; Unsaturated cyclic amine groups having about 3 to about 10 carbon atoms having intramolecular carbon-carbon double bonds; Cyclic amine groups having about 3 to about 10 carbon atoms localized; A cyclic amine group having about 3 to about 10 carbon atoms containing at least one heteroelement selected from the group consisting of oxygen, sulfur and phosphorus; And alkyl, perfluoroalkyl, alkylaminoalkyl, alkoxyalkyl, silylalkyl, alkoxysilylalkyl, cycloalkyl, benzyl, allyl, alkylsilyl, alkoxysilyl, alkoxyalkylsilyl groups at positions other than the amino group. And an amine group selected from the group consisting of cyclic amine groups having about 3 to about 10 carbon atoms which may be substituted by one or more substituents selected from the group consisting of aminoalkylsilyl groups.

The silicon precursor according to the present invention may be supplied in a gaseous state to form a thin film including silicon. When the silicon precursor according to the present application is used as a raw material for thin film deposition, a uniform thickness film may be formed even in a structure having a high thickness and high aspect ratio, such as a silicon oxide thin film or a silicon nitride thin film, per raw material supply cycle. In the production of the semiconductor, it is possible to increase the productivity of the silicon oxide thin film or silicon nitride thin film formation process. In particular, the silicon precursor according to the present application has a higher film growth rate than that of other silicon precursors by atomic layer deposition, chemical vapor deposition, or the like. The deposition method using the silicon precursor according to the present application can also be used to form a composite film containing silicon and other metal elements without generating corrosive gas by-products.

1 is a graph showing the results of TG / DSC analysis of trispyrrolidinosilane (SiH [N (C ₄ H ₈ )] ₃ ) prepared according to Example 1 of the present application.
2 is a graph showing the deposition rate of the film according to the supply time of the precursor compound carried out according to Experimental Example 1 of the present application and a graph showing the deposition rate of the film according to the supply time of ozone gas (O ₃ / O ₂ ) of the precursor compound. .
3 is a graph showing the deposition rate of the film according to the substrate temperature change of the precursor compound carried out in accordance with Experimental Example 2 of the present application and a graph showing the leakage current characteristics of the deposited film.
4 is a TEM photograph showing the step coverage of a silicon oxide thin film deposited using a precursor compound carried out in accordance with Experimental Example 2 of the present application.
5 is a graph showing a comparison result of the deposition rate according to the substrate temperature and the leakage current characteristics of the deposited silicon oxide thin film for each of the precursor compound according to the present application and the conventional precursor Si ₂ Cl ₆ according to Experimental Example 2 of the present application.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided to aid the understanding herein. In order to prevent the unfair use of unscrupulous infringers. In addition, throughout this specification, "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

One aspect of the present application includes supplying an organic silicon compound represented by Chemical Formula 1 in a gaseous state and contacting the substrate to deposit a silicon-containing thin film on the substrate at a deposition temperature of about 100 ° C. to about 500 ° C. To provide a thin film deposition method using a silicon precursor compound:

≪ Formula 1 >

In Formula 1, m is an integer of 1 to 4,

은 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 분자내 탄소-탄소 이중결합을 갖는 탄소수 약 3 내지 약 10의 불포화싸이클릭 아민기; 편재화(localized)되어 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 산소, 황 및 인으로 이루어진 군에서 선택되는 헤테로원소를 1개 이상을 포함하는 탄소수 약 3 내지 약 10의 싸이클릭 아민기 ;및, 아미노기 외의 위치에 알킬기(alkyl), 퍼플루오르알킬기, 알킬아미노알킬기, 알콕시알킬기, 실릴알킬기, 알콕시실릴알킬기, 사이클로알킬기, 벤질기, 알릴기, 알킬실릴기, 알콕시실릴기, 알콕시알킬실릴기, 및 아미노알킬실릴기로 이루어진 군에서 선택되는 하나 이상의 치환기에 의하여 치환될 수 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기로 이루어진 군에서 선택되는 아민기일 수 있으나, 이에 제한되는 것은 아니다. 상기 치환기들에 대하여 기재된 "알킬" 및 "알콕시" 부분은 각각 탄소수 약 1 내지 약 4를 가지는 것이며, 상기 사이클로알킬기는 탄소수 약 3 내지 약 6을 가지는 것일 수 있으나, 이에 제한되는 것은 아니다.

A cyclic amine group having about 3 to about 10 carbon atoms; Unsaturated cyclic amine groups having about 3 to about 10 carbon atoms having intramolecular carbon-carbon double bonds; Cyclic amine groups having about 3 to about 10 carbon atoms localized; A cyclic amine group having from about 3 to about 10 carbon atoms containing at least one hetero element selected from the group consisting of oxygen, sulfur and phosphorus; and an alkyl group, perfluoroalkyl group, alkylaminoalkyl group at a position other than the amino group , Alkoxyalkyl group, silylalkyl group, alkoxysilylalkyl group, cycloalkyl group, benzyl group, allyl group, alkylsilyl group, alkoxysilyl group, alkoxyalkylsilyl group, and aminoalkylsilyl group It may be an amine group selected from the group consisting of cyclic amine groups having about 3 to about 10 carbon atoms, but is not limited thereto. The "alkyl" and "alkoxy" moieties described for the substituents each have about 1 to about 4 carbon atoms, and the cycloalkyl group may have about 3 to about 6 carbon atoms, but is not limited thereto.

According to the exemplary embodiment of the present application, the silicon-containing thin film may be a silicon oxide thin film or a silicon nitride thin film, but is not limited thereto.

For example, the deposition temperature may be about 100 ° C. to about 500 ° C., for example about 150 ° C. to about 500 ° C., or about 200 ° C. or about 500 ° C., or about 250 ° C. to about 500 ° C., or about 300 ° C. ℃ to about 500 ℃, but is not limited thereto.

According to the exemplary embodiment of the present invention, a process of depositing a silicon-containing thin film using the organic silicon compound represented by Chemical Formula 1 is not particularly limited, but may be performed by atomic layer deposition or chemical vapor deposition.

As such, the present disclosure may lower the process temperature during deposition by depositing a silicon-containing thin film. In the case of using atomic layer deposition or chemical vapor deposition, the thickness and composition of the thin film can be precisely controlled, so that a silicon-containing 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 deposited. Can be improved.

In this case, when the deposition temperature is less than about 100 ° C., the thin film formation temperature may be low, and thus, the content of carbon contamination and other impurities may be increased due to the formation of an incomplete thin film. Above about 500 ° C., this is undesirable because there is no significant difference from conventional chemical vapor deposition (CVD), where thin films are deposited at significant high temperatures. Accordingly, the deposition temperature may range from about 100 ° C. to about 500 ° C., for example from about 150 ° C. to about 500 ° C., or from about 200 ° C. to about 500 ° C., or from about 250 ° C. to about 500 ° C., or from about 300 ° C. It may be about 500 ℃, but is not limited thereto.

은 5~6각 고리를 형성하고 있는 피롤리딘, 피롤, 피페리딘, 및 모르폴린(morpholine) 중에서 선택될 수 있으며, 예를 들어, 피롤리딘, 또는 피롤일 수 있으나, 이에 제한되는 것은 아니다.According to an embodiment of the present application, in the organosilicon compound represented by Formula 1, an integer of m = 1 to 4,

May be selected from pyrrolidine, pyrrole, piperidine, and morpholine forming a 5-6 hexagonal ring, and may be, for example, pyrrolidine or pyrrole, but is not limited thereto. no.

In the organosilicon compound represented 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 react with highly reactive oxidants to form a silicon oxide thin film (SiO ₂ ) or silicon nitride thin film (SiN) _x , and by such a reaction mechanism a low deposition temperature of about 100 ° C. to about 500 ° C. Deposition is also possible.

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 a high volatility even at low temperatures, and to exist in a liquid state at room temperature to oxidize It can be suitably used as a silicon precursor compound for depositing a silicon thin film or a silicon nitride thin film.

은 5~6각 고리를 형성하고 있는 피롤리딘, 피롤, 피페리딘, 및 모르폴린(morpholine) 중에서 선택될 수 있으며, 예를 들어, 피롤리딘, 또는 피롤일 수 있으나, 이에 제한되는 것은 아니다.According to an embodiment of the present application, m is 3 in the organic silicon compound represented by Chemical Formula 1 used as the silicon precursor compound of the present application,

May be selected from pyrrolidine, pyrrole, piperidine, and morpholine forming a 5-6 hexagonal ring, and may be, for example, pyrrolidine or pyrrole, but is not limited thereto. no.

In the organosilicon compound represented 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 react with highly reactive oxidants to form a silicon oxide thin film (SiO ₂ ) or silicon nitride thin film (SiN) _x , and by such a reaction mechanism a low deposition temperature of about 100 ° C. to about 500 ° C. Deposition is also possible.

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 a high volatility even at low temperatures, and to exist in a liquid state at room temperature to oxidize It can be suitably used as a silicon precursor compound for depositing a silicon thin film or a silicon nitride thin film.

은 5각 고리인 피롤리딘인 하기 화학식 2로 표시되는 유기 실리콘 화합물일 수 있으나, 이에 제한되는 것은 아니다.According to an embodiment of the present application, m is 3 in the organic silicon compound represented by Chemical Formula 1 used as the silicon precursor compound of the present application,

May be an organosilicon compound represented by the following Formula 2, which is a pyrrolidin pentagonal ring, but is not limited thereto.

<Formula 2>

은 5각 고리인 피롤리딘인 하기 화학식 3으로 표시되는 유기 실리콘 화합물일 수 있으나, 이에 제한되는 것은 아니다.According to an embodiment of the present application, m is 2 in the organic silicon compound represented by Chemical Formula 1 used as the silicon precursor compound of the present application,

May be an organosilicon compound represented by the following Chemical Formula 3, which is a pyrrolidin pentagonal ring, but is not limited thereto.

<Formula 3>

The organosilicon compounds used as the silicon precursor compounds herein can be prepared by using and / or modifying various production methods for organosilicon compounds known in the art, for example, under a nonpolar solvent as shown in Scheme 1. The tris or bis halide ligand silicone compound can be easily obtained by adding a cyclic amine compound metallized with an alkyl metal at low temperature, performing an exchange reaction at room temperature, removing salt through filtration, and distilling under reduced pressure. However, it is not limited to this:

[Reaction Scheme 1]

In this Scheme 1, R is alkyl, for example, may be selected from methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, and tert-butyl, M is lithium (Li) or sodium (Na) It may be a metal cation such as, but is not limited thereto.

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

Scheme 2

은 각각 상기 화학식 1에서 표시한 바와 같다.In Scheme 1 and Scheme 2, X is a halide (halide) series, it may be selected from F, Cl, Br, and I,

Are as shown in Formula 1, respectively.

은 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 분자내 탄소-탄소 이중결합을 갖는 탄소수 약 3 내지 약 10의 불포화싸이클릭 아민기; 편재화(localized)되어 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 산소, 황 및 인으로 이루어진 군에서 선택되는 헤테로원소를 1개 이상을 포함하는 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 및, 아미노기 외의 위치에 알킬기(alkyl), 퍼플루오르알킬기, 알킬아미노알킬기, 알콕시알킬기, 실릴알킬기, 알콕시실릴알킬기, 사이클로알킬기, 벤질기, 알릴기, 알킬실릴기, 알콕시실릴기, 알콕시알킬실릴기, 및 아미노알킬실릴기로 이루어진 군에서 선택되는 하나 이상의 치환기에 의하여 치환될 수 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기로 이루어진 군에서 선택되는 아민기일 수 있으나, 이에 제한되는 것은 아니며, 특히, 5~6각 고리를 형성하고 있는 피롤리딘, 피롤, 피페리딘, 및 모르폴린 중에서 선택될 수 있으나, 이에 제한되는 것은 아니다. 상기 치환기들에 대하여 기재된 "알킬" 및 "알콕시" 부분은 각각 탄소수 약 1 내지 약 4를 가지는 것이며, 상기 사이클로알킬기는 탄소수 약 3 내지 약 6을 가지는 것일 수 있으나, 이에 제한되는 것은 아니다.For example,

A cyclic amine group having about 3 to about 10 carbon atoms; Unsaturated cyclic amine groups having about 3 to about 10 carbon atoms having intramolecular carbon-carbon double bonds; Cyclic amine groups having about 3 to about 10 carbon atoms localized; A cyclic amine group having about 3 to about 10 carbon atoms containing at least one heteroelement selected from the group consisting of oxygen, sulfur and phosphorus; And alkyl, perfluoroalkyl, alkylaminoalkyl, alkoxyalkyl, silylalkyl, alkoxysilylalkyl, cycloalkyl, benzyl, allyl, alkylsilyl, alkoxysilyl, alkoxyalkylsilyl groups at positions other than the amino group. , And an amine group selected from the group consisting of cyclic amine groups having about 3 to about 10 carbon atoms which may be substituted by one or more substituents selected from the group consisting of aminoalkylsilyl groups, but is not limited thereto. It may be selected from, but not limited to, pyrrolidine, pyrrole, piperidine, and morpholine, which form a hexagonal ring. The "alkyl" and "alkoxy" moieties described for the substituents each have about 1 to about 4 carbon atoms, and the cycloalkyl group may have about 3 to about 6 carbon atoms, but is not limited thereto.

For example, hexane, pentane, or toluene having a weak polarity may be used as the solvent, but is not limited thereto.

More specifically, the manufacturing method of the organic silicon compound represented by <Formula 2> and <Formula 3> used as the silicon precursor compound in one embodiment of the present application are as follows.

The above-described organosilicon compound of Chemical Formula 2 is lithium pyrroly metallized using normal butyllithium (n-BuLi) in a trichlorosilane compound (HSiCl ₃ ) solution in a hexane solvent which is a non-polar solvent as in Scheme 3 below. After adding the dean compound at low temperature, the reaction is stirred at room temperature, and then, after removing the salt through filtration, it can be obtained by distillation under reduced pressure. In this case, pentane or toluene may be used as the nonpolar solvent, and nitrogen (N ₂ ) or argon (Ar) may be used to effectively remove the salt (LiCl), which is a product during the stirring reaction, and to inhibit the decomposition reaction by moisture or oxygen during the reaction. The reaction can proceed under airflow:

Scheme 3

The above-described organosilicon compound of Formula 3 is metallized 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 in Scheme 4 below. The lithium pyrrolidin compound was added at low temperature, and then stirred at room temperature, followed by filtration to remove salt, followed by distillation under reduced pressure:

Scheme 4

On the other hand, the thin film deposition method using the silicon precursor compound according to the present application, 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 the substrate By contacting a deposition temperature of about 100 ° C. to about 500 ° C., such as, for example, about 150 ° C. to about 500 ° C., or about 200 ° C. to about 500 ° C., or about 250 ° C. to about 500 ° C., or The silicon oxide thin film or the silicon nitride thin film may be deposited at about 300 ° C. to about 500 ° C., but is not limited thereto.

In this case, as the transport gas or the dilution gas, one or more mixtures selected from argon (Ar), nitrogen (N ₂ ), helium (He), and hydrogen (H ₂ ) may be used, but is not limited thereto.

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. For example, the silicon precursor compound may be contained in a bubbler container at a pressure of about 0.1 torr to about 10 torr, and at room temperature to about A bubbling method of bubbling and vaporizing a container with a transport gas in a temperature range of 80 ° C. may be used, but is not limited thereto.

In addition, the silicon precursor compound may be bubbled with argon (Ar) or nitrogen (N ₂ ) gas, thermal energy or plasma, or a bias may be applied to the substrate, but is not limited thereto.

Another aspect of the present disclosure is selected from the group consisting of tetrakis (ethylmethylamido) hafnium (TEMAH), tetrakis (ethylmethylamido) zirconium (TEMAZ) and tetrakis (dimethylamido) titanium (TDMAT) A gas of at least one compound; A gas of an organosilicon compound represented by Formula 1 below; And at least one mixture gas selected from water vapor (H ₂ O), oxygen (O ₂ ), oxygen nitride, hydrogen peroxide (H ₂ O ₂ ) and ozone (O ₃ ) simultaneously or alternately in contact with the substrate to It provides a thin film deposition method using a silicon precursor compound, comprising depositing a composite thin film containing silicon selected from Hf-Si-O, Zr-Si-O, Ti-Si-O and Zr-Hf-Si-O. do.

&Lt; Formula 1 >

In Formula 1, m is an integer of 1 to 4,

은, 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 분자내 탄소-탄소 이중결합을 갖는 탄소수 약 3 내지 약 10의 불포화싸이클릭 아민기; 편재화(localized)되어 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기; 산소, 황 및 인으로 이루어진 군에서 선택되는 헤테로원소를 1개 이상을 포함하는 탄소수 약 3 내지 약 10의 싸이클릭 아민기;및, 아미노기 외의 위치에 알킬기(alkyl), 퍼플루오르알킬기, 알킬아미노알킬기, 알콕시알킬기, 실릴알킬기, 알콕시실릴알킬기, 사이클로알킬기, 벤질기, 알릴기, 알킬실릴기, 알콕시실릴기, 알콕시알킬실릴기, 및 아미노알킬실릴기로 이루어진 군에서 선택되는 하나 이상의 치환기에 의하여 치환될 수 있는 탄소수 약 3 내지 약 10의 싸이클릭 아민기로 이루어진 군에서 선택되는 아민기일 수 있으나, 이에 제한되는 것은 아니다.

Silver, a cyclic amine group having about 3 to about 10 carbon atoms; Unsaturated cyclic amine groups having about 3 to about 10 carbon atoms having intramolecular carbon-carbon double bonds; Cyclic amine groups having about 3 to about 10 carbon atoms localized; A cyclic amine group having from about 3 to about 10 carbon atoms containing at least one heteroelement selected from the group consisting of oxygen, sulfur and phosphorus; and an alkyl group, perfluoroalkyl group, alkylaminoalkyl group at a position other than the amino group. , Alkoxyalkyl group, silylalkyl group, alkoxysilylalkyl group, cycloalkyl group, benzyl group, allyl group, alkylsilyl group, alkoxysilyl group, alkoxyalkylsilyl group, and aminoalkylsilyl group It may be an amine group selected from the group consisting of cyclic amine groups having about 3 to about 10 carbon atoms, but is not limited thereto.

When depositing a composite thin film including silicon, precursors containing Hf, Zr, and Ti, respectively, can be used without particular limitations known in the art. For example, tetrakis (ethylmethylamido) hafnium (TEMAH, Hf [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ) and tetrakis (ethyl as precursors containing Hf, Zr, and Ti, respectively. Methylamido) zirconium (TEMAZ, Zr [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ), tetrakis (dimethylamido) titanium (TDMAT, Ti [N (CH ₃ ) ₂ ] ₄ ), and the like. Can be used, but is not limited thereto.

Hereinafter, a thin film deposition method using a silicon precursor compound according to the present application will be described in more detail with reference to the following Examples and Experimental Examples. However, this is only presented to aid the understanding of the present application, the present invention is not limited to the following examples.

< Example  1>

Trispirolidinosilane of formula 2 (SiH [N ( C ₄ H ₈ )] ₃ Manufacturing

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., then 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 lithium pyrrolidine 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 give 170 g (yield: 79.2%) of trispirolidinosilane, 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>

Bispyrrolidinosilane (SiH) ₂ [N ( C ₄ H ₈ )] ₂ Manufacturing

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., then 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 lithium pyrrolidin salt solution at -78 ° C, and 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 give 85 g (yield: 50%) of bispyrrolidinosilane 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, trispyrrolidinosilane 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 the silicon precursor compound prepared in Example 1 exhibits sufficient volatility to be applied to the chemical vapor deposition method or the atomic layer deposition method to supply the raw material in a gaseous state. In addition, it can be seen that the trispirolidinosilane precursor compound prepared in Example 1 has an equivalent or better thermal stability than the conventional organosilicon compounds. In addition, it was confirmed that the thermal decomposition appeared below 500 ℃ as shown on the DSC curve.

< Experimental Example  2>

Of formula 2 Trispirolidinosilane  Deposition and Characterization of Silicon Oxide Thin Films Used as Silicon Precursors

Formula containing no chlorine ions as prepared in Example 1 A thin silicon oxide thin film was deposited by the ALD method using trispyrrolidinosilane of 2.

Specifically, atomic layer deposition (ALD) experiments were performed using ozone (O ₃ ) as the trispirolidinosilane precursor prepared in Example 1 and the oxygen source (O ₂ ). 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 to 150 ℃ to 500 ℃ and the trispirolidinosilane precursor used as a precursor is put in a bubbler container made of stainless steel and heated to a temperature of 2 torr, 60 ℃ 100 Argon (Ar) gas having a flow rate of sccm was used as a carrier gas of the precursor compound to vaporize the vessel by bubbling. At this time, the supply amount of the precursor into the reactor was 3 × 10 ⁵ L, the flow rate of ozone gas (0 ₃ / O ₂ ) as an oxygen source was adjusted from 9.5 torr to 110 sec.

Deposition Rate Characteristics

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

As it is found in the second ozone gas (O ₃ / O ₂₎ supplied to the time the ozone gas at about 27 sec by about 0.1 nm / cycle of the deposition rate (O ₃ / O ₂₎ deposition rate, depending for example, increasing the supply time of the It can be seen that is maintained almost constant.

The exposure of trispyrrolidinosilane to complete the surface reaction was about 3 × 10 ⁵ L, which is more indicative of the trispirolodinosilane precursor according to the present application compared to the conventional precursor Si ₂ Cl ₆ for saturation of the deposition rate. It shows excellent reactivity.

-Deposition Characteristics According to Temperature-

In order to measure the deposition characteristics according to the substrate temperature of the trispirolidinosilane precursor compound prepared by the method of Example 1, the ALD cycle was fixed to 50 times, and the pulse time of the Si precursor was 10 seconds and oxygen Cause The flow rate of ozone gas (0 ₃ / O ₂ ) was supplied at 9.5 torr in 110 sec, and the growth rate results according to the temperature of the substrate at a substrate temperature of 200 ° C. to 500 ° C. are shown in FIG. 3.

As shown in FIG. 3, the deposition of the silicon oxide thin film was deposited even at a low temperature at 150 ° C. when using the trispirolidinosilane precursor compound, which is lower than the deposition temperature of the conventional precursor Si ₂ Cl ₆ .

The silicon oxide thin film was deposited at a temperature of 150 ° C. to 478 ° C., and the deposition rate was saturated at 404 ° C., resulting in the highest deposition rate of 0.25 nm / cycle for an exposure of 3 × 10 ⁵ L of Si (NC ₄ H ₈ ) ₃ H. The speed is shown. In a high temperature region (404 ℃ to 478 ℃) was measured the leakage current characteristic changes in the silicon oxide thin film (FIG. 3), the higher the quality of the film was decreased, the leakage current at a high temperature region of the substrate, which is a conventional precursor Si ₂ Cl ₆ has excellent electrical properties corresponding to the silicon oxide thin 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. 4. The ALD silicon oxide thin film of this example showed excellent step coverage.

-Comparison with conventional precursor Si ₂ Cl _6-

Comparative results of the deposition rate according to the substrate temperature and the characteristics of the deposited silicon oxide thin film with respect to the tripyrrolidinosilane precursor compound of Example 1 and the conventional precursor Si ₂ Cl ₆ are shown in FIG. 5.

As shown in FIG. 5, low temperature deposition below 300 ° C. was achieved by the trispirolidinosilane precursor compound of Example 1, and the leakage current density was about the same with the two precursors.

< Experimental Example  3>

Of formula 2 Trispirolidinosilane  Deposition of Composite Thin Films Containing Silicon Used as Silicon Precursor

Tetrakis (ethylmethylamido) hafnium (TEMAH, Hf [N (CH ₃ ) (CH ₂ ) was substituted for trispyrrolidinosilane gas on a substrate heated to 280 ° C. using atomic layer deposition as described in Experimental Example 2. CH ₃ )] ₄ ) A hafnium silicon composite oxide (Hf-Si-O) thin film was deposited by an atomic layer deposition method supplying a mixed gas of a gas and a trispirolidinosilane gas.

Tetrakis (ethylmethylamido) zirconium (TEMAH, Hf [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ) gas instead of a mixed gas of trispyrrolidinosilane gas A zirconium silicon composite oxide (Zr-Si-O) thin film was deposited using a mixed gas of (TEMAZ, Zr [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ) gas and trispyrrolidinosilane gas.

Tetrakis (dimethylamido) titanium instead of the mixed gas of the tetrakis (ethylmethylamido) hafnium (TEMAH, Hf [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ) gas and trispyrrolidinosilane gas A titanium silicon composite oxide (Ti-Si-O) thin film was deposited using a mixed gas of (TDMAT, Ti [N (CH ₃ ) ₂ ] ₄ ) gas and trispirolidinosilane gas.

Tetrakis (ethylmethylamido) halfnium (TEMAH, Hf [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ) gas and tetrakis (ethylmethylamido) hafnium instead of a mixed gas of trispyrrolidinosilane gas (TEMAH, Hf [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ) gas and tetrakis (ethylmethylamido) zirconium (TEMAZ, Zr [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ) gas A hafnium zirconium silicon composite oxide (Hf-Zr-Si-O) thin film was deposited using a mixed gas of and trispyrrolidinosilane gas.

To summarize the results of this embodiment, the precursor according to the present application was able to uniformly form the silicon oxide film on the surface having a very high irregularities, such as the aspect ratio 50 at a low temperature of 150 ℃ to 500 ℃. The SiO ₂ film formed at about 400 ° C. or more was as excellent in electrical properties as the silicon oxide film formed by low pressure chemical vapor deposition (LPCVD) at 700 ° C. using a known precursor Si ₂ Cl ₆ as a raw material. Also, the film growth rate was higher (0.25 nm / cycle at about 400 ° C.) in atomic layer deposition than other silicon precursors with silicon-nitrogen bonds.

In addition, the silicon precursor according to the present application may be used to form a composite oxide film including silicon and other metals in addition to silicon oxide.

The silicon precursor according to the present application can be used not only for atomic layer deposition but also for chemical vapor deposition.

 It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

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

Claims (5)

Supplying an organic silicon compound represented by Chemical Formula 2 in a gaseous state and contacting the substrate to deposit a silicon-containing thin film on the substrate at a deposition temperature of 100 ° C. to 500 ° C. Way:
(2)

.
delete delete delete A gas of at least one compound selected from the group consisting of tetrakis (ethylmethylamido) hafnium (TEMAH), tetrakis (ethylmethylamido) zirconium (TEMAZ) and tetrakis (dimethylamido) titanium (TDMAT); A gas of an organosilicon compound represented by Formula 2 below; And at least one mixture gas selected from water vapor (H ₂ O), oxygen (O ₂ ), oxygen nitride, hydrogen peroxide (H ₂ O ₂ ) and ozone (O ₃ ) simultaneously or alternately in contact with the substrate to A thin film deposition method using a silicon precursor compound, comprising depositing a composite thin film containing silicon selected from Hf-Si-O, Zr-Si-O, Ti-Si-O, and Zr-Hf-Si-O:
(2)

.

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