KR20210089015A - Yttrium compound, forming method of thin film comprising the same, and semiconductor substrate preapared thereby - Google Patents

Abstract

The present invention relates to an yttrium compound, a method for forming a thin film containing the same, and a semiconductor substrate prepared therefrom, and more particularly, to an yttrium compound represented by a chemical formula 1, which increases crystallinity of the thin film by depositing together with a precursor compound for forming a high-dielectric thin film when manufacturing a high-dielectric thin film, increases efficiency of a deposition process by improving thermal stability, can be applied to a high-temperature process, and can prevent leakage current of the thin film to be manufactured, to a method for forming a thin film containing the same, and a semiconductor substrate prepared therefrom. In the chemical formula 1, R_1, R_2 and R_4 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R_3 is one selected from a group consisting of a ligand having a halogen substituent having 3 to 6 carbon atoms, an alkyl amine having 3 to 6 carbon atoms or a derivative thereof, an alkoxide having 3 to 6 carbon atoms or a derivative thereof, an amidine having 3 to 6 carbon atoms or a derivative thereof, guanidine or a derivative thereof, a cyclic amine having 4 to 6 carbon atoms or a derivative thereof, and a cyclopendadienyl ligand substituted with an alkyl amine having 1 to 4 carbon atoms, and n is an integer of 0 to 4.

Description

Yttrium compound, method of forming a thin film containing the same, and a semiconductor substrate prepared therefrom {YTTRIUM COMPOUND, FORMING METHOD OF THIN FILM COMPRISING THE SAME, AND SEMICONDUCTOR SUBSTRATE PREAPARED THEREBY}

The present invention relates to a yttrium compound, a method for forming a thin film comprising the same, and a semiconductor substrate prepared therefrom, and more particularly, by using a predetermined yttrium compound together in manufacturing a high dielectric thin film to improve and stabilize the crystallinity of the thin film. The present invention relates to a yttrium compound capable of improving the efficiency of a deposition process and preventing leakage current of a high dielectric thin film, a method of forming a thin film including the same, and a semiconductor substrate manufactured therefrom.

Various memory and non-memory semiconductor devices, such as DRAM, logic, and 3D NAND, are manufactured using high-k thin films. However, as the degree of integration of semiconductor devices increases day by day, problems such as step coverage occur in depositing these thin films on a substrate. Since the step coverage of the thin film is an important factor in determining the resistance uniformity of the semiconductor device, it is important to increase the step coverage in terms of the reliability of the semiconductor device. Therefore, preventing leakage current is also an important issue.

When forming by sputtering using a sputter target as a conventional method of forming a metal thin film, the composition of the deposited thin film is determined by the sputter target, so there is a limit to uniformly controlling the composition of the thin film, and large-area deposition As this progresses, the composition and thickness of the thin film become non-uniform, making it difficult to obtain uniform film properties. In addition, when manufacturing by chemical vapor deposition (CVD) instead of sputtering, problems arise in terms of vapor pressure control and film quality reproducibility.

The ALD process is being used because the ALD (atomic layer deposition) process that utilizes a surface reaction is more advantageous than the CVD process that mainly utilizes the gas phase reaction to improve the uniformity of the thin film and increase the step coverage, but 100% There is still a problem for the implementation of step coverage.

Since the ALD process is performed at a high temperature, a high-k precursor compound that can be deposited at a high temperature is used as a thin film forming material. Although zirconium is mainly used as the precursor compound of the high dielectric, thermal stability of the zirconium precursor is not sufficient to be applied to the ALD process, so there is a problem such as thermal decomposition during the thin film formation process.

Therefore, it is necessary to develop a high-dielectric thin film capable of high-temperature deposition such as an ALD process due to improved thermal stability.

Korean Patent Publication No. 2006-0034775

In order to solve the problems of the prior art as described above, the present invention can improve the efficiency of the deposition process by increasing the crystallinity of the thin film and improving thermal stability by depositing it together with a precursor compound for forming a high dielectric thin film when manufacturing a high dielectric thin film. An object of the present invention is to provide a yttrium compound that can be applied to a high-temperature process and can prevent leakage current of a thin film, a method of forming a thin film including the same, and a semiconductor substrate manufactured therefrom.

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 has the following formula 1

[Formula 1]

(In Formula 1, R ₁ , R ₂ and R ₄ are each independently a substituted or unsubstituted C 1 to C 6 alkyl group, and R ₃ is a ligand having a C 3 to C 6 halogen substituent, an alkyl having 3 to 6 carbon atoms. Amine or derivative thereof, alkoxide or derivative thereof having 3 to 6 carbon atoms, amidine or derivative thereof having 3 to 6 carbon atoms, guanidine or derivative thereof, cyclic amine or derivative thereof having 4 to 6 carbon atoms, and alkyl having 1 to 4 carbon atoms An amine is one selected from the group consisting of a substituted cyclopendathienyl ligand, and n is an integer of 0 to 4).

In addition, the present invention provides a method for forming a thin film comprising adsorbing the yttrium compound to a substrate.

In addition, the present invention provides a semiconductor substrate comprising a thin film prepared by the above thin film forming method.

According to the present invention, by depositing together with a precursor compound for forming a high dielectric thin film, the crystallinity of the thin film and thermal stability can be improved to improve the efficiency of the deposition process, can be applied to a high-temperature process, and prevent leakage current of the thin film being manufactured There is an effect of providing a yttrium compound, a method of forming a thin film including the same, and a semiconductor substrate prepared therefrom.

Hereinafter, the yttrium compound of the present invention, a method of forming a thin film including the same, and a semiconductor substrate prepared therefrom will be described in detail.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concepts of the terms to best describe his invention. Based on the principle, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

In the present specification, when a member is said to be positioned 'on' another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

In the present specification, when a part 'includes' a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

Unless otherwise specified herein, 'substituted' or 'unsubstituted' may be substituted or unsubstituted with one or more substituents of hydrogen, a halogen group, an alkyl group, or an aryl group.

Unless otherwise specified herein, the term 'halogen group' or 'halogen atom' means any one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

Unless otherwise specified in the present specification, the 'alkyl group' may be a straight chain, branched chain, or cyclic chain, and may be an alkyl group having 1 to 10 carbon atoms, that is, C1 to C10. The alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an iso-pentyl group, a neo-pentyl group, tert It may be a pentyl group, a hexyl group, an iso-hexyl group, and the like, but is not limited thereto.

Unless otherwise specified herein, 'alkylene' is a divalent atomic group obtained by subtracting two hydrogen atoms from an alkane, and may be represented by the _{general formula -C n} H _{2n -.} The alkanes include linear alkanes and branched alkanes, and include primary alkanes, secondary alkanes and tertiary alkanes.

Ligand herein refers to a chemical unit capable of forming a complex.

The present inventors have been studying a method for improving the thermal stability of a precursor compound for forming a thin film in order to stably manufacture a high-k thin film, and when depositing a yttrium compound of a specific structure together, excellent thermal stability and improved crystallinity even in a high-temperature process The present invention was completed by further concentrating on research based on this.

The yttrium compound of the present invention has the following formula 1

[Formula 1]

(In Formula 1, R ₁ , R ₂ and R ₄ are each independently a substituted or unsubstituted C 1 to C 6 alkyl group, and R ₃ is a ligand having a C 3 to C 6 halogen substituent, an alkyl having 3 to 6 carbon atoms. Amine or derivative thereof, alkoxide or derivative thereof having 3 to 6 carbon atoms, amidine or derivative thereof having 3 to 6 carbon atoms, guanidine or derivative thereof, cyclic amine or derivative thereof having 4 to 6 carbon atoms, and alkyl having 1 to 4 carbon atoms It is one selected from the group consisting of a cyclopendathienyl ligand substituted with an amine, and n is an integer from 0 to 4).

In Formula 1, R ₁ , R ₂ and R ₄ are each independently a substituted or unsubstituted C 1 to C 6 alkyl group, preferably an unsubstituted C 1 to C 3 alkyl group, more preferably a methyl group or an ethyl group, , in this case, the thermal stability of the compound may be improved through the simplification of the compound. Here, R ₄ represents a substituent capable of bonding to the remaining four carbons except for the carbons forming a bond with _{R 1} among the cyclopentadienyl groups of Formula 1 above. Accordingly, n has a range of 0 to 4, and may preferably be 0, 1, or 2, and in this case, the compound may be stabilized according to the structural simplification of the compound.

R ₃ is a ligand having a halogen substituent having 3 to 6 carbon atoms, an alkylamine or derivative thereof having 3 to 6 carbon atoms, an alkoxide or derivative thereof having 3 to 6 carbon atoms, amidine or derivative thereof having 3 to 6 carbon atoms, guanidine or a derivative thereof , a cyclic amine having 4 to 6 carbon atoms or a derivative thereof, and a cyclopendathienyl ligand substituted with an alkyl amine having 1 to 4 carbon atoms. R ₃ is, for example, a cyclopendathienyl ligand substituted with an alkyl amine having 1 to 4 carbon atoms, preferably a cyclopentadienyl ligand substituted with an alkyl amine having 1 or 2 carbon atoms, in this case, the amine of _{R 3} Due to the interaction of the unshared electron pair included in the group with yttrium, a coordination bond is formed and the stability of the compound can be further improved. When used together in the thin film deposition process, thermal stability is improved, thereby improving the process efficiency of the high-temperature deposition process, and There is an excellent effect of improving the film quality of the thin film by improving the crystallinity.

When R ₃ is a cyclopendathienyl ligand substituted with an alkylamine having 1 to 4 carbon atoms, a nitrogen element may be directly substituted in the cyclopentadienyl group, or 1 to carbon atoms between the cyclopentadienyl group and the nitrogen element The alkenyl group of 3 may be linked, and hydrogen, a methyl group or an ethyl group may be substituted for the nitrogen element.

When R ₃ is a cyclopendathienyl ligand substituted with an alkyl amine having 1 to 4 carbon atoms, the yttrium compound may be, for example, represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1, R ₁ , R ₂ , R ₄ and n are as defined in Formula 1 above, R ₅ is, for example, an alkylene group having 0 or 1 to 3 carbon atoms, and R ₆ and R ₇ are, for example, each independently hydrogen, a methyl group or an ethyl group. In this case, the yttrium of the yttrium compound may _{additionally form a coordination bond with the cyclopentadienyl group substituted at the R 3} position, and at the same time, as indicated by the arrow in Formula 1-1, the interaction with the lone pair of the nitrogen element The action may result in the formation of coordination bonds. Accordingly, the stability of the compound is further improved, and when the yttrium compound is used together in the thin film deposition process, the thermal stability is improved, the process efficiency of the high temperature deposition process is improved, and the crystallinity of the thin film is improved, thereby improving the film quality of the thin film. may rise further. In view of the above-described effects, R ₅ may be a methylene group, and R ₆ and R ₇ may each be a methyl group.

In the yttrium compound, as described above, the yttrium element may form a coordination bond with one or two cyclopentadienyl groups. This coordination bond is relatively easy to break compared to other bonds in the compound, so when the yttrium compound is used together in the thin film forming process, the reaction with the reactive gas can be stably progressed, which makes the thin film forming process easy. . At the same time, due to the chemical stability of the compound itself, thermal decomposition is prevented at a temperature of 200° C. or less, thereby providing excellent thermal stability as well as low reactivity at room temperature, so there is no risk of spontaneous ignition and easy handling.

The yttrium compound may be, for example, a liquid at room temperature (25° C.), and a vapor pressure (25° C.) of 10 to 300 mmHg, preferably 50 to 280 mmHg, more preferably 70 to 270 mmHg, in which case the deposition process The deposition rate can be improved because the deposition is performed smoothly. In addition, since deposition is performed smoothly and thermal stability is excellent, process efficiency may be improved when applied to high-temperature deposition processes such as ALD as well as CVD.

The present invention provides a method for forming a thin film comprising injecting the yttrium compound represented by Chemical Formula 1 into a deposition chamber and adsorbing it to the surface of a loaded substrate.

In the thin film formation method of the present invention, the thermal stability of the precursor compound for thin film formation is improved by depositing the yttrium compound together in the deposition process of the precursor compound for thin film formation to produce a high dielectric thin film, and thus applied to a high-temperature deposition process Even so, since thermal decomposition of the precursor compound for forming a thin film is prevented, process efficiency and film quality of the thin film may be improved. In addition, the crystallinity of the thin film formed from the precursor compound for thin film formation is improved, and there is an excellent effect of preventing the leakage current of the finally manufactured thin film.

The thin film may include, for example, a Group 4b metal, specifically, may be at least one selected from the group consisting of Ti, Zr and Hf, and preferably may be Zr, Hf, or a mixture thereof. Group 4b metal is a material capable of forming a high-dielectric thin film. As a precursor compound for thin-film formation, when an organic compound containing a group 4b metal and the yttrium compound of the present invention are deposited together, a high-dielectric thin film can be formed with high efficiency. There is an advantage in that it is possible to prevent leakage current of the thin film.

The organic compound including the group 4b metal may be, for example, in a form in which a ligand including a cyclopentadienyl group is bonded to a group 4b metal. The ligand may preferably include an amine group, and may also include an unsaturated bond, preferably a double bond, between carbon and carbon. In this case, the precursor compound for forming a thin film is further stabilized to improve process stability and improve the process stability of the thin film. There is an advantage of improving the film quality, and the step coverage of the thin film can be further improved.

For example, in the deposition for forming the thin film, the yttrium compound and the precursor compound for forming the thin film may be sequentially deposited on a substrate (wafer) to form a thin film having a multilayer structure. As another example, a thin film having a single layer structure may be formed by simultaneously depositing the yttrium compound and the precursor compound for forming a thin film on a substrate or by depositing a mixed precursor compound in which the yttrium compound and the precursor compound for forming a thin film are mixed.

In the process of forming the thin film, the yttrium compound and/or the precursor compound for forming the thin film may be mixed with a solvent and deposited in the form of a composition, if necessary. In this case, there is an effect of improving the process efficiency of the deposition process because it is easy to control the viscosity and vapor pressure.

The solvent may be, for example, an organic solvent, specifically tetrahydrofuran (THF), dimethoxyethane (DME), dichloromethane (DCM), dichloroethane (DCE), benzene (Benzene), toluene (Toluene) ) and may be one selected from the group consisting of mesitylene, and in this case, there is an advantage in that the viscosity or vapor pressure of the precursor compound can be easily adjusted during thin film deposition.

As another example, the solvent may include a tertiary amine, a cycloalkyl ether, or a mixture thereof. In this case, the viscosity or vapor pressure of the precursor compound can be easily adjusted during thin film deposition. At the same time, the viscosity and volatility of the composition for forming a thin film are appropriately adjusted to facilitate vaporization using the liquid transfer method (LDS), thereby improving the substrate (WAFER) adsorption efficiency and stability of the precursor for forming a thin film, thereby shortening the process time. There is an excellent effect of improving the uniformity and step coverage of the thin film by uniformly applying the composition for forming a thin film. The tertiary amine may be specifically dialkylamine, more specifically dimethylethylamine, and in this case, the residual rate of impurities after the deposition process is low due to excellent volatility, so that the film quality of the thin film can be improved, There is an advantage in that the composition for forming a thin film has improved stability due to excellent miscibility without reacting with the metal precursor for formation. The cycloalkyl ether may be cyclopentylalkyl ether, and more specifically, cyclopentylmethyl ether. In this case, it does not react with the metal precursor for thin film formation and has excellent solubility in organic compounds, thereby improving the stability of the composition. And the composition is maintained uniformly, there is an excellent effect of forming a uniform thin film.

When the yttrium compound and the precursor compound for thin film formation are mixed with a solvent and deposited in the form of a composition, the mixing ratio of the yttrium compound and the precursor compound for thin film formation and the solvent is 5 to 95: 5 to 95 based on the weight ratio. and preferably 10 to 90: 10 to 90, more preferably 10 to 60: 40 to 90, within this range, the generation of impurities is small, resistance and impurity levels in the thin film are reduced, and There is an effect excellent in the step coverage.

The thin film formation method is, for example, chemical vapor deposition (CVD), metal organometallic chemical vapor deposition (MOCVD), low pressure vapor deposition (LPCVD), plasma enhanced vapor deposition (PECVD), atomic layer deposition (ALD), or plasma enhanced atomic layer deposition. It may be carried out by a vapor deposition method (PEALD), and preferably may be carried out by a chemical vapor deposition method or an atomic layer deposition method, but is not limited thereto. The chemical vapor deposition method or the atomic layer deposition method can form a film of uniform thickness even on a surface of a structure having a large aspect ratio by supplying a raw material to a substrate in a gaseous state, for example, and a precursor compound for forming a thin film even on a large area or roll-shaped substrate There is an advantage in that it is possible to form a uniform film by supplying it at a uniform concentration. However, the atomic layer deposition method is more preferable in terms of improving the step coverage of the thin film.

The deposition may be carried out, for example, at a temperature of 200 to 600 °C, preferably 250 to 550 °C, more preferably 300 to 500 °C, and the film quality of the thin film formed within this range is improved and has an excellent step coverage.

Further, the deposition may be carried out, for example, at a pressure in the range of 0.1 to 10 Torr, preferably under a pressure of 0.5 to 5 Torr, more preferably 1 to 3 Torr, and uniformly within this range. There is an effect of obtaining a thin film of thickness.

In the present description, 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.

In a preferred embodiment, the method for forming the thin film includes: i) purging the inside of the ALD chamber with a purge gas first; ii) vaporizing the precursor compound for forming a thin film, the yttrium compound of the present invention, or a composition containing them, and adsorbing them to the surface of the substrate loaded in the ALD chamber; iii) secondary purging of the inside of the ALD chamber with a purge gas; iv) supplying a reaction gas into the ALD chamber; and v) thirdly purging the inside of the ALD chamber with a purge gas.

In step ii), a thin film having a multilayer structure may be formed by sequentially vaporizing the precursor compound for thin film formation and the yttrium compound of the present invention, respectively, if necessary, or may be simultaneously vaporized to form a thin film having a single layer structure.

The method for forming the thin film is, for example, tens or more times, specifically 50 to 1000 times, preferably 100 to 500 times, more preferably, until a thin film having a desired thickness is obtained by performing steps i) to v) as one cycle. It can be repeated 150 to 300 times, the thickness of the thin film is appropriately controlled within the above range, and the desired characteristics of the thin film can be well expressed.

In the method for forming a thin film of the present invention, the method of transferring the deposition material to the deposition chamber is a method of transferring the volatilized gas using a mass flow controller (MFC) method (Vapor Flow Control; VFC) or liquid phase flow control (Liquid Mass Flow Controller; LMFC) method can be used to transfer a liquid in which a metal precursor is dissolved in an organic solvent (Liquid Delivery System; LDS), etc., and preferably an LDS method, in which case a thin film Since the viscosity and volatility of the composition for forming can be easily controlled, process efficiency and film quality of the thin film can be improved.

The purging is preferably 1,000 to 10,000 sccm, more preferably 2,000 to 7,000 sccm, more preferably 2,500 to 6,000 sccm, within this range, the thin film growth rate per cycle is reduced to a preferred range, and process by-products are reduced. .

For the deposition, for example, a time division deposition apparatus for depositing by sequentially supplying deposition raw materials such as the yttrium compound and a precursor compound for forming a thin film may be used.

As another example, a space division deposition apparatus in which a substrate rotates and reciprocates between a space filled with a gas of one raw material and a space filled with another raw gas may be used.

As another example, when the substrate used for deposition is a roll-type polymer substrate, a roll-to-roll deposition apparatus that is wound in a roll shape may be used.

The reaction gas is, for example, water vapor (H ₂ O), hydrogen peroxide (H ₂ O ₂ ), oxygen (O ₂ ), ozone (O ₃ ), hydrogen (H ₂ ), nitrogen (N ₂ ), hydrazine (N ₂ H) ₄ ), ammonia (NH ₃ ), silane (silane), and may include one or more selected from the group consisting of silane-based compounds, but is not limited thereto.

As a specific example, when the deposition of the precursor compound for thin film formation is performed in the presence of an oxidizing reaction gas such as water vapor, oxygen, ozone, and hydrogen peroxide, a metal oxide thin film may be formed, through which a high dielectric thin film used for DRAM, etc. is manufactured There are advantages to being able to In addition, when the deposition of the precursor compound for thin film formation is performed in the presence of a nitrogen-containing reactive gas such as nitrogen, ammonia, or hydrazine, a metal nitride thin film useful for manufacturing a diffusion barrier film or the like may be formed.

In the thin film forming method, the injection time of the yttrium compound, the precursor compound for thin film formation, or a composition containing them may be, for example, 1 to 30 seconds, preferably 1 to 20 seconds, more preferably 2 to 10 seconds, Within this range, the thickness uniformity of the thin film is improved, so that a uniform thin film can be easily manufactured even on a substrate having a complex shape.

In the method for forming the thin film, the injection time of the reactive gas may be, for example, 1 to 40 seconds, preferably 1 to 30 seconds, more preferably 2 to 10 seconds, and within this range, excellent coverage and uniform coating properties are obtained. This has the effect of improving the physical properties of the thin film.

The substrate is, for example, glass, silicon, metallic polyester (Polyester, PE), polyethylene terephthalate (PET), polyethylene naphthalate (Polyethylenenapthalate, PEN), polycarbonate (Polycarbonate, PC), polyetherimide ( Polyetherimide, PEI), polyethersulfone (PES), polyetheretherketone (Polyetheretherketone, PEEK) and polyimide (Polyimide, PI) may include at least one substrate (wafer) selected from the group consisting of, but It is not limited.

As a specific example, when describing the method for forming the thin film,

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

The substrate can be used without any particular limitation as long as it is used for semiconductor manufacturing, specifically, a silicon substrate, a silica substrate (SiO ₂ ), a silicon nitride substrate (SiN), a silicon oxynitride substrate (SiON), a titanium nitride substrate ( TiN), a tantalum nitride substrate (TaN), a tungsten substrate (W), or a noble metal substrate, for example, a platinum substrate (Pt), a palladium substrate (Pd), a rhodium substrate (Rh), or a gold substrate (Au), etc. may be used. have. The substrate may be, for example, a silicon substrate or a silicon oxide substrate.

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

An inert gas is injected into the deposition chamber to purge the inside of the deposition chamber.

In order to deposit a thin film on the substrate positioned in the deposition chamber, a precursor compound for forming a thin film or a composition including the same is prepared. The precursor compound for forming the thin film may be a group 4b metal organic compound as a preferred example.

Thereafter, the prepared composition for forming a thin film is injected into the vaporizer, changed into a vapor phase, transferred to a deposition chamber, and adsorbed on a substrate, and the unadsorbed composition for forming a thin film is purged.

In the present invention, the method of transferring the composition for forming a thin film to the deposition chamber is, for example, a method of transferring a volatilized gas using a gas-phase flow controller (MFC) method (Vapor Flow Control; VFC) or a liquid-phase flow control method A liquid delivery system (LDS) may be used by utilizing a (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 _{argon (Ar), nitrogen (N 2} ), and helium (He) may be used as a transport gas or diluent gas for moving the composition for forming a thin film on the substrate, but is limited no.

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

Next, a reaction gas is supplied. The reaction gas is not particularly limited if it is a reaction gas commonly used in the art to which the present invention belongs, and may preferably include a reducing agent, a nitriding agent or an oxidizing agent, and preferably an oxidizing agent. The reducing agent and the thin film precursor compound adsorbed on the substrate react to form a metal thin film, the nitriding agent forms a metal nitride thin film, and the oxidizing agent forms a metal oxide thin film.

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

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

The method of forming the thin film may further include, for example, depositing the precursor compound for forming the thin film using plasma on the thin film formed on the substrate (wafer). thin film can be obtained. The plasma may be, for example, oxygen plasma, but is not limited thereto.

The present invention provides a semiconductor substrate comprising a thin film manufactured through the above thin film forming method. The semiconductor substrate may be applied to, for example, a DRAM memory (dynamic random access memory, DRAM) device. In this case, leakage current is prevented and device performance can be improved.

The thin film formed by the method of forming the thin film has a thickness of 20 nm or less and a specific resistance value of 0.1 to 400 μΩ·cm as a preferable example, and within this range, the thin film is more easily made thin and the current leakage of the thin film is further improved. It has the advantage of being easy.

The thin film may have a thickness of, for example, 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 1 to 3 nm, and within this range, the thin film properties are excellent.

The thin film has, for example, a resistivity value of 0.1 to 400 μΩ·cm, preferably 50 to 400 μΩ·cm, more preferably 200 to 400 μΩ·cm, even more preferably 300 to 400 μΩ·cm, even more preferably Preferably, it may be 330 to 380 μΩ·cm, and most preferably 340 to 370 μΩ·cm, and there is an excellent effect of thin film properties within this range.

The thin film may have, for example, a single-layer structure or a multi-layer structure, and may be selected as necessary.

Hereinafter, preferred examples are presented to aid the understanding of the present invention, but the following examples are merely illustrative of the present invention and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.

[Synthesis example of yttrium compound]

1. Yttrium compound 1: Cp(CH ₂ ) ₂ N(CH ₃ )Y(NMe ₂ )

1-1. Cp(CH ₂ ) ₂ N(CH ₃ ) Preparation of Y(Cl)

[Scheme 1-1]

[Cp(CH ₂ ) ₂ NH(CH ₃ )] 20 g (162.2 mmol) was added to 100 ml of THF, and after cooling to -20°C or less, 129.6 ml of n-BuLi solution (2.5 M) was added. _{Then, [Cp(CH 2} ) ₂ NH(CH ₃ )]-Li solution prepared by stirring at room temperature for 1 hour _{, YCl 3} 31.6 g (162.2 mmol) was dissolved in 100 ml of THF in a flask containing a solution. It was added slowly and stirred for 3 hours. After the obtained mixture was vacuum-dried, it was added to 300 ml of toluene, stirred at room temperature for 1 hour, the solid produced in this process was filtered off, and the filtered solid product was washed with 100 ml of toluene. The solid product was filtered off and the remaining solution and the solution washed with the solid product were evaporated to dryness under vacuum to obtain 20 g of the compound. (Yield 51%)

1-2. Cp(CH ₂ ) ₂ N(CH ₃ )Y(NMe ₂ ) manufacturing

[Scheme 1-2]

10 g (40.7 mmol) of (Cp(CH ₂ ) ₂ N(CH ₃ ))Y(Cl) prepared in 1-1 was added to 50 ml of THF and cooled to -20°C or less, prepared (NMe ₂ ) -Li 2.1 g (40.7 mmol) was slowly added dropwise to the solution. After stirring at room temperature for 3 hours, the solvent was removed under reduced pressure and dried again under reduced pressure to obtain 6.5 g of a pale yellow compound. (Yield 63%)

2. Yttrium compound 2: (Cp(CH ₂ ) ₃ N(CH ₃ ))Y(NMe ₂ )

2-1. Cp(CH ₂ ) ₃ N(CH ₃ ) Preparation of Y(Cl)

[Scheme 2-1]

[Cp(CH ₂ ) ₃ NH(CH ₃ )] 15 g (109.3 mmol) was added to 75 ml of THF, and then cooled to -20°C or less. _{[Cp(CH 2} ) ₃ NH(CH ₃ )]-Li solution prepared by adding 87.4 ml of n-BuLi solution (2.5 M) to the solution and stirring at room temperature for 2 hours _{, YCl 3} 21.3 g (109.3 mmol) ) was slowly added dropwise to a flask containing a solution dissolved in 80 ml of THF and stirred for 5 hours. After the mixture was vacuum dried, 200 ml of toluene was added and stirred at room temperature for 1 hour. The solid produced in this process was filtered and filtered, and the filtered solid product was washed with 80 ml of toluene. The solid product was filtered off and the remaining solution and the solution washed with the solid product were evaporated to dryness under vacuum to obtain 11 g of the compound. (yield 38.8%)

2-2. (Cp(CH ₂ ) ₃ N(CH ₃ ))Y(NMe ₂ ) manufacturing

[Scheme 2-2]

11 g (42.4 mmol) of (Cp(CH ₂ ) ₃ N(CH ₃ ))Y(Cl) prepared in 2-1 above was added to 60 ml of THF and cooled to -20°C or less, (NMe ₂ ) -Li 2.2 g (42.4 mmol) was slowly added dropwise. After stirring at room temperature for 3 hours, the solvent was removed under reduced pressure and dried under reduced pressure to obtain 6.8 g of a pale yellow compound. (yield 60%)

3. Yttrium compound 3: (Cp(CH ₂ ) ₂ N(CH ₃ ))Y(Cp(CH) ₂ ) ₂ N(CH ₃ ) ₂ )

(Cp(CH ₂ ) ₂ N(CH ₃ ))Y(Cp(CH) ₂ ) ₂ N(CH ₃ ) ₂ ) manufacturing

[Scheme 3]

Cp(CH ₂ ) ₂ N(CH ₃ ) ₂ 5.6 g (40.7 mmol) was added to 50 ml of THF, cooled to -20°C or lower, and 16 ml of n-BuLi solution (2.5 M) was added. _{(Cp(CH 2} ) ₂ N(CH ₃ ) ₂ )-Li solution synthesized by stirring at room temperature for 2 hours, prepared in 1-1 above (Cp(CH ₂ ) ₂ N(CH ₃ )) in THF It was slowly added dropwise to 150 ml of a solution in which Y(Cl) was dissolved and stirred at room temperature overnight. The solvent was removed from the solution under reduced pressure and dried under reduced pressure to obtain 7.7 g of a pale yellow compound. (Yield 55%)

Claims (13)

Formula 1
[Formula 1]

(In Formula 1, R ₁ , R ₂ and R ₄ are each independently a substituted or unsubstituted C 1 to C 6 alkyl group, and R ₃ is a ligand having a C 3 to C 6 halogen substituent, an alkyl having 3 to 6 carbon atoms. Amine or derivative thereof, alkoxide or derivative thereof having 3 to 6 carbon atoms, amidine or derivative thereof having 3 to 6 carbon atoms, guanidine or derivative thereof, cyclic amine or derivative thereof having 4 to 6 carbon atoms, and alkyl having 1 to 4 carbon atoms It is one selected from the group consisting of a cyclopendathienyl ligand substituted with an amine, and n is an integer of 0 to 4.)
Yttrium compound.
The method of claim 1,
In Formula 1, R ₃ is a cyclopendathienyl ligand substituted with an alkyl amine having 1 to 4 carbon atoms.
Yttrium compound.
The method of claim 1,
The compound represented by Formula 1 is a liquid at room temperature (25 ℃), characterized in that the vapor pressure (25 ℃) of 10 to 300 mmHg
Yttrium compound.
Formula 1
[Formula 1]

(In Formula 1, R ₁ , R ₂ and R ₄ are each independently a substituted or unsubstituted C 1 to C 6 alkyl group, and R ₃ is a ligand having a C 3 to C 6 halogen substituent, an alkyl having 3 to 6 carbon atoms. Amine or derivative thereof, alkoxide or derivative thereof having 3 to 6 carbon atoms, amidine or derivative thereof having 3 to 6 carbon atoms, guanidine or derivative thereof, cyclic amine or derivative thereof having 4 to 6 carbon atoms, and alkyl having 1 to 4 carbon atoms It is one selected from the group consisting of an amine-substituted cyclopendathienyl ligand, and n is an integer of 0 to 4.) A yttrium compound represented by ) is injected into the deposition chamber and adsorbed on the surface of the loaded substrate characterized in that it comprises the step of
A method of forming a thin film.
5. The method of claim 4,
The thin film is characterized in that it contains a group 4b metal
A method of forming a thin film.
6. The method of claim 5,
The group 4b metal is characterized in that Zr, Hf or a mixture thereof
A method of forming a thin film.
5. The method of claim 4,
characterized in that the yttrium compound and the precursor compound for forming a thin film are simultaneously deposited
A method of forming a thin film.
5. The method of claim 4,
characterized in that the yttrium compound and the precursor compound for forming a thin film are sequentially deposited
A method of forming a thin film.
5. The method of claim 4,
The deposition is characterized in that chemical vapor deposition (CVD) or atomic layer deposition (ALD)
A method of forming a thin film.
5. The method of claim 4,
The deposition is characterized in that carried out at a temperature of 200 to 600 ℃
A method of forming a thin film.
Claims 4 to 10, characterized in that it comprises a thin film manufactured by the method for forming a thin film according to any one of claims 4 to 10.
semiconductor substrate.
12. The method of claim 11,
The thin film is characterized in that the multi-layer structure
semiconductor substrate.
12. The method of claim 11,
The thin film has a thickness of 20 nm or less and a specific resistance value of 0.1 to 400 μΩ·cm
semiconductor substrate.