Yttrium / lanthanum group metal precursor compound, film-forming composition containing the same, and method for forming yttrium / lanthanum group metal-containing film using the same

Abstract

The present application relates to an yttrium / lanthanum group metal precursor compound, a precursor composition for depositing an yttrium / lanthanum group metal-containing film containing the yttrium / lanthanum group metal precursor compound, and a method for depositing an yttrium / lanthanum group metal-containing film using the precursor composition.

Description

[Technical field]

[0001] The present application relates to an yttrium / lanthanum group metal precursor compound, a precursor composition for depositing an yttrium / lanthanum group metal-containing film that includes the yttrium / lanthanum group metal precursor compound, and a method for depositing an yttrium / lanthanum group metal-containing film using the precursor composition. [Background technology]

[0002] Yttrium-containing oxide films or lanthanum group metal-containing oxide films are being considered as gate dielectric materials for field effect transistors in semiconductor devices due to their various characteristics such as a wide bandgap (5.6ev), low leakage current, high breakdown voltage, and good thermal stability. Yttrium-containing oxide films or lanthanum group metal-containing oxide films are also being researched as gate insulating films for DRAMs and high-k dielectric layers for capacitors in semiconductor memory devices, and as insulating films for metal-insulator-metal (MIM) structures in non-volatile resistive switch memory devices.

[0003] Most of the yttrium or lanthanum group metal precursor compounds known to date have low vapor pressures and are solids or liquids with extremely high viscosity, making them disadvantageous for use as precursors in forming oxide films containing yttrium or lanthanum group metals by chemical vapor deposition (CVD) or atomic layer deposition (ALD) in the process of mass-producing semiconductor devices.

[0004] To form yttrium or lanthanum group metal-containing films required for the manufacture of next-generation semiconductor devices by atomic layer deposition, precursor compounds that have lower viscosity or higher vapor pressure than currently known yttrium or lanthanum group metal precursor compounds are required. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Republic of Korea Patent Publication No. 10-2012-0017069 Summary of the Invention [Problem to be solved by the invention]

[0006] The present application aims to provide novel yttrium or lanthanum group metal precursor compounds, precursor compositions for film deposition containing the metal precursor compounds, and methods for forming yttrium or lanthanum group metal-containing films using the precursor compositions.

[0007] In particular, an object of the present invention is to provide a precursor compound having a lower viscosity than those known in the art, a precursor composition for film deposition containing the same, and a method for forming a film using the precursor composition.

[0008] However, the problems to be solved by the present application are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0009] A first aspect of the present application provides an yttrium or lanthanum group metal-containing precursor compound represented by Formula I: [Chemical formula I] (R 1 Cp)2M[(CH3)2CH-NC(CH2CH3)=N-CH(CH3)2]; In said formula I: M is selected from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; R 1 is an n-propyl group ( n Pr) or iso-propyl group ( i Pr), The Cp is a cyclopentadienyl group.

[0010] A second aspect of the present application provides a precursor composition for forming an yttrium or lanthanum group metal-containing film, comprising the yttrium or lanthanum group metal-containing precursor compound according to the first aspect of the present application.

[0011] A third aspect of the present application provides a method for forming an yttrium or lanthanum group metal-containing film, comprising forming an yttrium or lanthanum group metal-containing film using a precursor composition for forming an yttrium or lanthanum group metal-containing film according to the second aspect of the present application. Effect of the Invention

[0012] The novel yttrium compound or lanthanum group metal-containing precursor compound according to the embodiment of the present application is a novel compound not previously known. The novel yttrium compound or lanthanum group metal-containing precursor compound according to the embodiment of the present application is liquid at room temperature and thermally stable.

[0013] The novel yttrium or lanthanum group metal-containing precursor compounds according to embodiments of the present application have lower viscosities than conventionally known yttrium or lanthanum group metal-containing precursor compounds, and when a low-viscosity liquid (solvent) is mixed to reduce the viscosity for use in a liquid delivery device for an ALD or CVD precursor, a mixture with the required viscosity can be produced even with a small amount of low-viscosity liquid (solvent). Thus, the novel yttrium or lanthanum group metal-containing precursor compounds according to embodiments of the present application are suitable for forming yttrium or lanthanum group metal-containing films by ALD or CVD processes.

[0014] The novel yttrium compound or lanthanum group metal-containing precursor compound according to the present embodiment has high thermal stability and can be used as a precursor for vapor phase deposition, for example, by using it as a precursor for atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form an yttrium or lanthanum group metal-containing film.

[0015] The composition containing an yttrium or lanthanum group metal-containing precursor compound according to the embodiment of the present application and the method for forming an yttrium or lanthanum group metal-containing film using the precursor composition can be applied to the manufacture of commercial semiconductor devices. In particular, in order to manufacture a DRAM semiconductor device, it is necessary to form a high dielectric material with a thickness of about 1 nm to about 10 μm on a substrate having a groove with a width of about 10 nm to about 1 μm, or about 100 nm or narrower than about 50 nm, and an aspect ratio of about 1 to about 50, about 10 or more, about 20 or more, about 30 or more, or deeper and narrower than that, and the yttrium or lanthanum group metal-containing precursor compound and the precursor composition containing the same according to the present application can form an yttrium or lanthanum group metal-containing film with a commercially required thickness on such a substrate. In addition, by using the yttrium or lanthanum group metal-containing precursor compound and the precursor composition containing the same according to the embodiment of the present application, in a substrate having fine irregularities (grooves) on its surface with an aspect ratio of about 1 or more and a width of about 1 μm or less, an yttrium or lanthanum group metal-containing film having a uniform thickness of several nm to several tens of nm can be formed on the entire surface of the substrate, including the surface of the fine irregularities (grooves) including the deepest part of the fine irregularities (grooves) and the upper surface of the fine irregularities (grooves).

[0016] In particular, since it is necessary to form a high dielectric material film of uniform thickness even at temperatures of about 280°C, about 300°C, or higher, a precursor composition capable of forming a film of uniform thickness by atomic layer deposition (ALD) on a substrate having a very narrow and deep groove even at high temperatures is required. Therefore, a precursor compound containing yttrium or a lanthanum group metal with very high thermal stability that satisfies the above requirements is required. Thus, the precursor compound containing yttrium or a lanthanum group metal according to the embodiment of the present application can be usefully used as a precursor that satisfies the above required properties.

[0017] The yttrium or lanthanum group metal-containing precursor compound according to the present disclosure has a constant film growth per cycle (GPC) over a wide temperature range, and is therefore more advantageous for depositing an yttrium or lanthanum group metal-containing film that requires fine and uniform thickness control by an ALD process than conventional yttrium or lanthanum group metal-containing precursor compounds that have inconsistent GPC depending on temperature changes.

[0018] The yttrium or lanthanum group metal-containing precursor compound according to the embodiment of the present application has a constant GPC regardless of the precursor supply time, and is therefore more advantageous in forming a film of a constant thickness even when a narrow uneven (groove) structure with a large aspect ratio is present on the substrate, compared to conventional yttrium precursors, which have inconsistent GPC depending on the precursor supply time.

[0019] The yttrium or lanthanum group metal-containing precursor compound according to the present disclosure can be used as a precursor for ALD, CVD, etc., and can provide performance required for manufacturing next-generation devices such as semiconductors, such as improved thermal stability, high volatility, and / or increased deposition rate, and can therefore be usefully used for forming yttrium or lanthanum group metal-containing films or thin films.

[0020] The yttrium compound or lanthanum group metal-containing compound according to the embodiment of the present disclosure may be applied in various fields such as catalysis. [Brief description of the drawings]

[0021] [Figure 1] 1 is a graph showing the viscosity depending on the octane mixing ratio of precursor compounds according to Example 1, Example 2, and Comparative Example 2 of the present application. [Diagram 2] 1 is a graph showing film growth per ALD gas supply cycle as a function of substrate temperature for precursor compounds according to Examples 1 and 3 of the present application. [Diagram 3] 1 is a graph showing film growth per ALD gas supply cycle as a function of precursor supply time for precursor compounds according to Examples 1 and 3 of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Hereinafter, the present application will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present application. However, the present application may be embodied in various different forms and is not limited to the embodiments and examples described herein. In the drawings, in order to clearly explain the present invention, parts that are not related to the description are omitted, and similar parts are designated by similar reference numerals throughout the specification.

[0023] Throughout the specification of this application, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "electrically connected" with another element therebetween.

[0024] Throughout this specification, when a member is said to be "on" another member, this includes not only when the member is in contact with the other member, but also when there is another member between the two members.

[0025] Throughout the specification of this application, when a part is said to "comprise" a certain element, this means that it may further include other elements, but not to the exclusion of other elements, unless specifically stated to the contrary.

[0026] As used herein, terms of degree such as "about," "substantially," and the like are used to mean a numerical value or close to a numerical value when the manufacturing and material tolerances inherent in the recited value are given, and are used to prevent unscrupulous infringers from unfairly taking advantage of the disclosure in which precise or absolute numerical values ​​are recited to aid in the understanding of the present application.

[0027] As used throughout the specification of this application, the terms "a step of" or "a step of" do not mean "a step for."

[0028] Throughout the specification of this application, the term "combination(s) of" contained in a Markush form expression means a mixture or combination of one or more selected from the group of elements set forth in the Markush form expression, and is meant to include one or more selected from the group of elements set forth above.

[0029] Throughout the specification of this application, the statement "A and / or B" means "A or B, or A and B."

[0030] Throughout this specification, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 5 carbon atoms, and all possible isomers thereof. For example, the above alkyl or alkyl groups include methyl (Me), ethyl (Et), n-propyl (N-propyl) groups, etc. n Pr), iso-propyl group ( iso Pr), n-butyl group ( n Bu), iso-butyl group ( iso Bu), tert-butyl group (tert-Bu, t Bu), sec-butyl group (sec-Bu, sec Bu), n-pentyl group ( n Pe), iso-pentyl group ( iso Pe), sec-pentyl group ( sec Pe), tert-pentyl group ( t Pe), neo-pentyl group ( neo Pe), 3-pentyl, n-hexyl, iso-hexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof.

[0031] Throughout this specification, the term "yttrium or lanthanum group metal elements" may include Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0032] Throughout this specification, the term "Cp" is represented as -C5H4 and is an abbreviation for "cyclopentadienyl group."

[0033] Throughout this specification, the term "membrane" means "film or thin film."

[0034] Hereinafter, specific examples of the present application will be described in detail, but the present application is not limited thereto.

[0035] A first aspect of the present application provides an yttrium or lanthanum group metal-containing precursor compound represented by Formula I: [Chemical formula I] (R 1 Cp)2M[(CH3)2CH-NC(CH2CH3)=N-CH(CH3)2]; In the above formula I, M is selected from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; R 1 is an n-propyl group ( n Pr) or iso-propyl group ( i Pr), The above Cp is a cyclopentadienyl group.

[0036] In one embodiment of the present application, the yttrium or lanthanum group metal element-containing precursor compound may be selected from, but is not limited to, the following: ( n PrCp)2Y( i Pr-NC(Et)=N- i Pr), ( n PrCp)2La( i Pr-NC(Et)=N-i Pr)、( n PrCp)2Ce( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Pr( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Nd( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Pm( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Sm( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Eu( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Gd( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Tb( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Dy( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Ho( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Er( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Tm( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Yb( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Lu( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Y( i Pr-NC(Et)=N- iPr)、( i PrCp)2La( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Ce( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Pr( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Nd( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Pm( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Sm( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Eu( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Gd( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Tb( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Dy( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Ho( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Er( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Tm( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Yb( i Pr-NC(Et)=N- i Pr)、and( i PrCp)2Lu( i Pr-NC(Et)=N- i (Pr)。

[0037] In one embodiment of the present application, the yttrium or lanthanum group metal element-containing precursor compound is n PrCp)2Y( i Pr-NC(Et)=N- i Pr), ( n PrCp)2Gd( i Pr-NC(Et)=N- i Pr), ( i PrCp)2Y( i Pr-NC(Et)=N- i Pr), or ( i PrCp)2Gd( i Pr-NC(Et)=N- i Pr).

[0038] A second aspect of the present application provides a precursor composition for forming an yttrium or lanthanum group metal containing film comprising one or more yttrium or lanthanum group metal containing precursor compounds according to the first aspect of the present application.

[0039] Detailed descriptions of parts that overlap with the first aspect of the present application are omitted, but the contents described with respect to the first aspect of the present application may be similarly applied even if the description is omitted in the second aspect of the present application.

[0040] In an embodiment of the present disclosure, the precursor composition for forming an yttrium or lanthanum group metal-containing film may include one or more yttrium or lanthanum group metal-containing precursor compounds selected from, but not limited to, the following: ( n PrCp)2Y( i Pr-NC(Et)=N- i Pr), ( n PrCp)2La( i Pr-NC(Et)=N- i Pr), ( n PrCp)2Ce( i Pr-NC(Et)=N- i Pr), ( n PrCp)2Pr( iPr-NC(Et)=N- i Pr)、( n PrCp)2Nd( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Pm( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Sm( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Eu( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Gd( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Tb( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Dy( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Ho( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Er( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Tm( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Yb( i Pr-NC(Et)=N- i Pr)、( n PrCp)2Lu( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Y( i Pr-NC(Et)=N- i Pr)、( i PrCp)2La( i Pr-NC(Et)=N- i Pr)、( i PrCp)2Ce( iPr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Pr( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Nd( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Pm( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Sm( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Eu( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Gd( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Tb( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Dy( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Ho( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Er( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Tm( i Pr-N-C(Et)=N- i Pr), ([[]] i (PrCp)2Yb( i Pr-N-C(Et)=N- i Pr), and ([[]] i (PrCp)2Lu( i Pr-N-C(Et)=N- i Pr).

[0041] In one embodiment of the present application, the yttrium or lanthanum group metal element-containing precursor compound is ([[]] n (PrCp)2Y(i Pr-NC(Et)=N- i Pr), ( n PrCp)2Gd( i Pr-NC(Et)=N- i Pr), ( i PrCp)2Y( i Pr-NC(Et)=N- i Pr), or ( i PrCp)2Gd( i Pr-NC(Et)=N- i Pr).

[0042] In one embodiment of the present application, the yttrium or lanthanum group metal-containing film may be, but is not limited to, an yttrium or lanthanum group metal film, an yttrium or lanthanum group metal-containing oxide film, an yttrium or lanthanum group metal-containing nitride film, or an yttrium or lanthanum group metal carbide film. In one embodiment of the present application, the yttrium or lanthanum group metal-containing film may be an yttrium or lanthanum group metal-containing oxide film.

[0043] In an embodiment of the present application, the precursor composition for forming a yttrium or lanthanum group metal-containing film may further include one or more nitrogen sources selected from the group consisting of ammonia, nitrogen, hydrazine, and dimethylhydrazine, but is not limited thereto.

[0044] In an embodiment of the present application, the precursor composition for forming a yttrium or lanthanum group metal-containing film may further include one or more oxygen sources selected from the group consisting of water vapor, oxygen, and ozone, but is not limited thereto.

[0045] A third aspect of the present application provides a method for forming an yttrium or lanthanum group metal-containing film, comprising forming an yttrium or lanthanum group metal-containing film using a precursor composition for forming an yttrium or lanthanum group metal-containing film according to the second aspect of the present application.

[0046] Detailed descriptions of parts that overlap with the first and second aspects of the present application are omitted, but the contents described for the first and second aspects of the present application may be similarly applied even if the description is omitted in the third aspect of the present application.

[0047] In one embodiment of the present application, the yttrium or lanthanum group metal-containing film may be, but is not limited to, an yttrium or lanthanum group metal film, an yttrium or lanthanum group metal-containing oxide film, an yttrium or lanthanum group metal-containing nitride film, or an yttrium or lanthanum group metal-containing carbide film. In one embodiment of the present application, the yttrium or lanthanum group metal-containing film may be an yttrium or lanthanum group metal-containing oxide film.

[0048] In one embodiment of the present application, the yttrium or lanthanum group metal-containing film may be deposited by, but is not limited to, chemical vapor deposition (CVD) or atomic layer deposition (ALD). The yttrium or lanthanum group metal-containing film may be deposited by, but is not limited to, metalorganic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD). In one embodiment of the present application, the yttrium or lanthanum group metal-containing film may be deposited by, but is not limited to, atomic layer deposition.

[0049] In addition, the chemical vapor deposition method or atomic layer deposition method may be performed using a deposition apparatus, deposition conditions, and / or additional reactant gases known in the art, but are not limited thereto. Here, when the yttrium or lanthanum group metal-containing oxide film is deposited using the atomic layer deposition method, the process temperature during deposition can be adjusted, and the thickness and composition of the thin film can be accurately controlled, so that a thin film having excellent coverage can be deposited even on a substrate with a complex shape, and the thickness uniformity and physical properties of the thin film can be improved.

[0050] In one embodiment of the present application, the thickness of the yttrium or lanthanum group metal-containing film may be about 1 nm to about 10 μm, and may be variously applied depending on its application, but is not limited thereto. In one embodiment of the present application, the thickness of the yttrium-containing oxide film may be about 1 nm to about 10 μm, and may be variously applied depending on its application, but is not limited thereto. For example, the thickness of the yttrium or lanthanum group metal-containing film may be about 1 nm to about 10 μm, about 1 nm to about 5 μm, about 1 nm to about 1 μm, about 1 nm to about 900 nm, about 1 nm to about 800 nm, about 1 nm to about 700 nm, about 1 nm to about 600 nm, about 1 nm to about 500 nm, about 1 nm to about 400 nm, about 1 nm to about 300 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 50 nm, about 1 nm to about 30 nm, about 1 nm to about 20 nm, about 1 nm ~about 10nm, about 10nm to about 10μm, about 10nm to about 5μm, about 10nm to about 1μm, about 10nm to about 900nm, about 10nm to about 800nm, about 10nm to about 700nm, about 10nm to about 600nm, about 10nm to about 500 nm, approximately 10 nm to approximately 400 nm, approximately 10 nm to approximately 300 nm, approximately 10 nm to approximately 200 nm, approximately 10 nm to approximately 100 nm, approximately 10 nm to approximately 50 nm, approximately 10 nm to approximately 30 nm, approximately 10 nm to approximately 20 nm, approximately 20 nm to approximately 10 μm, Approximately 20nm to approximately 5μm, approximately 20nm to approximately 1μm, approximately 20nm to approximately 900nm, approximately 20nm to approximately 800nm, approximately 20nm to approximately 700nm, approximately 20nm to approximately 600nm, approximately 20nm to approximately 500nm, approximately 20nm to approximately 400nm, approximately 20 nm ~ about 300 nm, about 20 nm - about 200 nm, about 20 nm - about 100 nm, about 20 nm - about 50 nm, about 20 nm - about 30 nm, about 30 nm - about 10 μm, about 30 nm - about 5 μm, about 30 nm - about 1 μm, about 30 nm - about 90 0nm, about 30nm to about 800nm, about 30nm to about 700nm, about 30nm to about 600nm, about 30nm to about 500nm, about 30nm to about 400nm, about 30nm to about 300nm, about 30nm to about 200nm, about 30nm to about 1 00nm, approx. 30nm ~ approx. 50nm, approx. 50nm ~ approx. 10μm, approx. 50nm ~ approx. 5μm, approx. 50nm ~ approx. 1μm, approx. 50nm ~ approx. 900nm, approx.Approximately 50nm to approximately 500nm, approximately 50nm to approximately 400nm, approximately 50nm to approximately 300nm, approximately 50nm to approximately 200nm, approximately 50nm to approximately 100nm, about 100nm to about 10μm, about 100nm to about 5μm, about 100nm to about 1μm, about 100nm to about 900nm, about 10 0nm ~ approx. 800nm, approx. 100nm ~ approx. 700nm, approx. 100nm ~ approx. 600nm, approx. 100nm ~ approx. 500nm, approx. 100nm ~ Approximately 400nm, approximately 100nm to approximately 300nm, approximately 100nm to approximately 200nm, approximately 200nm to approximately 10μm, approximately 200nm to approximately 5μm, Approximately 200nm to approximately 1μm, approximately 200nm to approximately 900nm, approximately 200nm to approximately 800nm, approximately 200nm to approximately 700nm, approximately 200nm ~about 600nm, about 200nm to about 500nm, about 200nm to about 400nm, about 200nm to about 300nm, about 300nm to about 10 μm, about 300nm to about 5μm, about 300nm to about 1μm, about 300nm to about 900nm, about 300nm to about 800nm, about 300n m ~ about 700nm, about 300nm - about 600nm, about 300nm - about 500nm, about 300nm - about 400nm, about 400nm - about 1 0μm, about 400nm to about 5μm, about 400nm to about 1μm, about 400nm to about 900nm, about 400nm to about 800nm, about 400 nm ~ approx. 700 nm, approx. 400 nm ~ approx. 600 nm, approx. 400 nm ~ approx. 500 nm, approx. 500 nm ~ approx. 10 μm, approx. 500 nm ~ approx. 5 μm, approximately 500 nm to approximately 1 μm, approximately 500 nm to approximately 900 nm, approximately 500 nm to approximately 800 nm, approximately 500 nm to approximately 700 nm, approximately 50 0nm to about 600nm, about 600nm to about 10μm, about 600nm to about 5μm, about 600nm to about 1μm, about 600nm to about 900n m, about 600 nm to about 800 nm, about 600 nm to about 700 nm, about 700 nm to about 10 μm, about 700 nm to about 5 μm, about 700 nm to about 1 μm, about 700 nm to about 900 nm, about 700 nm to about 800 nm, about 800 nm to about 10 μm, about 800 nm to about 5 μm, about 800 nm to about 1 μm, about 800 nm to about 900 nm, about 900 nm to about 10 μm, about 900 nm to about 5 μm, about 900 nm to about 1 μm, about 1 μm to about 10 μm, about 1 μm to about 5 μm, or about 5 μm to about 10 μm, but is not limited thereto.

[0051] In an embodiment of the present application, the yttrium or lanthanum group metal-containing film may be formed at a temperature ranging from about 100° C. to about 500° C., but is not limited thereto. For example, the silicon-containing film may be formed at a temperature of about 100°C to about 500°C, about 100°C to about 450°C, about 100°C to about 400°C, about 100°C to about 350°C, about 100°C to about 300°C, about 100°C to about 250°C, about 100°C to about 200°C, about 100°C to about 150°C, about 150°C to about 500°C, about 150°C to about 450°C, about 150°C to about 400°C, about 150°C to about 350°C, about 150°C to about 300°C, about 150°C to about 250°C, about 150°C to about 200°C, about 200°C to about 500°C, about 200°C to about 450°C, about 200°C to about 400°C, about 200°C to about 3 The film may be formed at a temperature range of, but is not limited to, 50°C, about 200°C to about 300°C, about 200°C to about 250°C, about 250°C to about 500°C, about 250°C to about 450°C, about 250°C to about 400°C, about 250°C to about 350°C, about 250°C to about 300°C, about 300°C to about 500°C, about 300°C to about 450°C, about 300°C to about 400°C, about 300°C to about 350°C, about 350°C to about 500°C, about 350°C to about 450°C, about 350°C to about 400°C, about 400°C to about 500°C, about 400°C to about 450°C, or about 450°C to about 500°C.

[0052] In one embodiment of the present application, the yttrium or lanthanum group metal-containing film may be formed on a substrate having an aspect ratio of about 1 to about 100 and an unevenness having a width of about 10 nm to about 1 μm, but is not limited thereto. For example, the aspect ratio is about 1 to about 100, about 1 to about 80, about 1 to about 60, about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 10 to about 100, about 10 to about 80, about 10 to about 60, about 10 to about 50, about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 100, about 20 to about 80, about 20 to about 60, about 20 to about 50 , about 20 to about 40, about 20 to about 30, about 30 to about 100, about 30 to about 80, about 30 to about 60, about 30 to about 50, about 30 to about 40, about 40 to about 100, about 40 to about 80, about 40 to about 60, about 40 to about 50, about 50 to about 80, about 50 to about 60, about 60 to about 100, about 60 to about 80, or about 80 to about 100, but is not limited thereto. For example, the width is from about 10 nm to about 1 μm, from about 10 nm to about 900 nm, from about 10 nm to about 800 nm, from about 10 nm to about 700 nm, from about 10 nm to about 600 nm, from about 10 nm to about 500 nm, from about 10 nm to about 400 nm, from about 10 nm to about 300 nm, from about 10 nm to about 200 nm, from about 10 nm to about 100 nm, from about 10 nm to about 90nm, about 10nm to about 80nm, about 10nm to about 70nm, about 10nm to about 60nm, about 10nm to about 50nm, about 10nm to about 40nm, about 10nm to about 3 0nm, about 10nm to about 20nm, about 20nm to about 1μm, about 20nm to about 900nm, about 20nm to about 800nm, about 20nm to about 700nm, about 20nm to about 6 00nm, about 20nm to about 500nm, about 20nm to about 400nm, about 20nm to about 300nm, about 20nm to about 200nm, about 20nm to about 100nm, about 20 nm ~ approx. 90 nm, approx. 20 nm ~ approx. 80 nm, approx. 20 nm ~ approx. 70 nm, approx. 20 nm ~ approx. 60 nm, approx. 20 nm ~ approx. 50 nm, approx. 20 nm ~ approx. 40 nm, approx. 20 nm ~30nm, approximately 30nm ~ approximately 1μm, approximately 30nm ~ approximately 900nm, approximately 30nm ~ approximately 800nm, approximately 30nm ~ approximately 700nm, approximately 30nm ~ approximately 600nm, approximately 30 nm~about 500nm, about 30nm~about 400nm, about 30nm~about 300nm, about 30nm~about 200nm, about 30nm~about 100nm, about 30nm~about 90nm,about 30nm to about 80nm, about 30nm to about 70nm, about 30nm to about 60nm, about 30nm to about 50nm, about 30nm to about 40nm, about 40nm to about 1μm, about 40nm to about 900nm, about 40nm to about 800nm, about 40nm to about 700nm, about 40nm to about 600nm, about 40nm to about 500nm, about 40nm to about 400nm, about 40nm to about 300nm, about 40nm to about 200nm, about 40nm to about 100nm, about 40nm to about 90nm, about 40nm to about 80nm, about 40nm to about 70nm, about 40nm to about 60nm, about 40nm to about 50nm, about 50nm to about 1μm, about 50nm to about 900nm, about 50nm to about 800nm, about 50nm to about 700nm, about 50nm to about 600nm, about 50nm to about 500nm, about 50nm to about 400nm, about 50nm to about 300nm, about 50nm to about 200nm, about 50nm to about 100nm, about 50nm to about 90nm, about 50nm to about 80nm, about 50nm to about 70nm, about 50nm to about 60nm, about 100nm to about 1μm, about 100nm to about 900nm, about 100nm to about 800nm, about 100nm to about 700nm, about 100nm to about 600nm, about 100nm to about about 500nm, about 100nm to about 400nm, about 100nm to about 300nm, about 100nm to about 200nm, about 200nm to about 1μm, about 200nm to about 900nm, about 200nm to about 800nm, about 200nm to about 700nm, about 200nm to about 600nm, about 200nm to about 500nm, about 200nm to about 400nm, about 200nm to about 300nm, about 300nm to about 1μm, about 300nm to about 900nm, about 300nm to about 800nm, about 300nm to about 700nm, about 300nm to about 600nm, about 300nm to about 500nm, about 300nm to about 400nm, about 400nm to about 1μm, about 400nm to about 900nm, about 400nm to about 800nm, about 400nm to about 700nm, about 400nm to about 600nm, about 400nm to about 500nm, about 500nm to about 1μm, about 500nm to about 900nm, about 500nm to about 800nm, about 500nm to about 700nm, about 500nm to about 600nm, about 600nm to about 1μm, about 600nm to about 900nm, about 600nm to about 800nm, about 600nm to about 700nm, about 700nm to about 1μm, about 700nm to about 900nm, about 700nm to about 800nm,It may be, but is not limited to, about 800 nm to about 1 μm, about 800 nm to about 900 nm, or about 900 nm to about 1 μm.

[0053] According to an embodiment of the present disclosure, a deposition method using a composition containing a yttrium or lanthanum group metal precursor compound includes, but is not limited to, forming an yttrium or lanthanum group metal-containing oxide film by supplying a precursor composition containing yttrium or lanthanum group metal compound in a gaseous state to a substrate located in a deposition chamber. The deposition method of the film may be performed using a method, apparatus, etc. known in the technical field of the present invention, and may be performed together with one or more additional reaction gases as necessary. The substrate may be, but is not limited to, a silicon semiconductor wafer, a compound semiconductor wafer, or a plastic substrate (PI, PET, PES). A substrate having holes or grooves may be used, or a porous substrate with a large surface area may be used.

[0054] The deposition of the yttrium or lanthanum group metal-containing oxide film according to an embodiment of the present disclosure may include, but is not limited to, metalorganic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD). The metalorganic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) may be performed using a deposition apparatus, deposition conditions, additional reaction gases, etc., known in the art.

[0055] In one embodiment of the present application, in the precursor composition for deposition of an oxide film containing yttrium or a lanthanum group metal of the present invention and the deposition method including forming an oxide film containing yttrium or a lanthanum group metal by using the precursor composition for film deposition, the yttrium or lanthanum group metal precursor compound of the present invention contained in the precursor composition for film deposition has low viscosity and high thermal stability, and can be used as a precursor for atomic layer deposition or chemical vapor deposition to form an oxide film containing yttrium or a lanthanum group metal. In particular, the precursor composition for film deposition can be used as a precursor for atomic layer deposition or chemical vapor deposition to form an oxide film containing yttrium or a lanthanum group metal. The present invention has an excellent effect in that an oxide film containing yttrium or a lanthanum group metal can be uniformly formed on a plastic substrate at a temperature range of about 100°C to about 500°C, or about 250°C to about 350°C, with a thickness of several μm to several tens of nm, and the oxide film containing yttrium or a lanthanum group metal can be uniformly formed on the entire surface of the substrate, including the surface of the fine irregularities (grooves) including the deepest part of the fine pattern (grooves) having an aspect ratio of about 1 to about 50, about 1 to about 100, or more and a width of about 1 μm to 10 nm or less, and the surface of the fine irregularities (grooves) including the upper surface of the fine irregularities (grooves).

[0056] In a thin film deposition method using an yttrium or lanthanum group metal precursor compound according to an embodiment of the present application, a substrate is placed in a reaction chamber, and then the yttrium or lanthanum group metal-containing precursor compound is transported onto the substrate using a carrier gas or a dilution gas, and an yttrium or lanthanum group metal-containing oxide film is preferably deposited at a deposition temperature in a wide range of about 100°C to about 500°C, about 150°C to about 450°C, about 200°C to about 400°C, or about 250°C to about 350°C.

[0057] According to an embodiment of the present application, the deposition temperature of the yttrium or lanthanum group metal-containing film is about 250°C to about 350°C because the applicable process temperature range is wide for memory devices and non-memory devices such as logic devices, and therefore the film properties of the yttrium or lanthanum group metal-containing oxide film vary depending on the temperature, and therefore a yttrium or lanthanum group metal precursor compound that can be used in a wide temperature range is required, and therefore the deposition is preferably performed in a deposition temperature range of about 250°C to about 350°C.

[0058] In one embodiment of the present application, the carrier gas or diluent gas is preferably one or more mixed gases selected from argon (Ar), nitrogen (N2), helium (He) or hydrogen (H2).

[0059] In one embodiment of the present application, the yttrium or lanthanum group metal precursor compound can be delivered to the substrate by a variety of supply methods, including a bubbling method in which the precursor is forcibly vaporized using a carrier gas, and a bypass method in which the container is heated to increase the vapor pressure of the precursor and supply the precursor in a gaseous state. When the vapor pressure is low, the bypass method in which the container is heated to vaporize the precursor may be used. The yttrium or lanthanum group metal precursor compound may be placed in a bubbler container or a VFC container, and the precursor may be bubbled or heated using a carrier gas at a vapor pressure of about 0.1 to about 10 torr and at a temperature range of room temperature to about 150° C. to be transported in a gaseous state and supplied into the chamber. Most preferably, the bypass method in which the yttrium or lanthanum group metal precursor compound is heated in a container and supplied in a gaseous state may be used.

[0060] In one embodiment of the present application, the yttrium or lanthanum group metal precursor compound is preferably vaporized by transporting it in argon (Ar) or nitrogen (N2) gas, using thermal energy or plasma, or applying a bias voltage on the substrate.

[0061] In one embodiment of the present disclosure, the thin film may be a composite oxide film containing other metals in addition to yttrium or lanthanum group metals, for example, a composite oxide film containing hafnium or zirconium, but is not limited thereto, having the following composition: Hf-YO, Zr-YO, Hf-Al-YO, Zr-Hf-Al-YO, Zr-Hf-Y-Si-O, Zr-Hf-Al-Y-Si-O, Hf-La-O, Zr-La-O, Hf-Al-La-O, Zr-Hf-Al-La-O, Z r-Hf-La-Si-O, Zr-Hf-Al-La-Si-O, Hf-Gd-O, Zr-Gd-O, Hf-Al-Gd-O, Zr-Hf-Al-Gd-O, Zr-Hf-Gd-Si-O, or Zr-Hf-Al-Gd-Si-O.

[0062] In one embodiment of the present application, in order to deposit the yttrium or lanthanum group metal-containing oxide film or composite oxide film, it is preferable to use one or a mixture of two or more selected from water vapor (HO), oxygen (O), oxygen plasma (O2 plasma), nitric oxide (NO, NO), nitric oxide plasma (NO plasma), hydrogen peroxide (HO), and ozone (O3) as a reactive gas.

[0063] Hereinafter, the present application will be described in more detail with reference to examples. However, the following examples are merely illustrative to aid in understanding the present application, and the contents of the present application are not limited to the following examples.

[0064] [Example] <Production Example 1> Production of N,N'-isopropylpropionimidamide (CH3)2CHNC(CH2CH3)NHCH(CH3)2 In a 500 mL Schlenk flask, 152 g (0.862 mol) of triethyl ortho-propionate and 102 g (1.725 mol) of isopropylamine were added, and 51.8 g (0.862 mol) of acetic acid was slowly added dropwise and refluxed at 170° C. or higher for 20 hours.

[0065] After the reaction was completed, the solvent was removed under reduced pressure, and the residue was extracted with diethylether and 1.1 eq. of aqueous sodium hydroxide (NaOH), the solvent was removed under reduced pressure, and the residue was distilled under reduced pressure to obtain 97.6 g (72%) of a colorless transparent liquid compound.

[0066] <Example 1> Preparation of bis-n-propylcyclopentadienyl-N,N'-isopropyl-ethylamidinate yttrium [Cp(CH2)2CH3]2Y[(CH3)2CHNC(CH2CH3)NCH(CH3)2] Sodium amide was placed in a flame-dried 500 mL Schlenk flask and kept at room temperature. 250 mL of THF and n-propylcyclopentadiene were slowly added dropwise to the flask and stirred at room temperature for 20 hours to produce n-propylcyclopentadienyl sodium.

[0067] In a flame-dried 1 L Schlenk flask, 30 g (0.154 mol) of yttrium(III) chloride and n-hexane (C6H 14 After adding 200 mL of the above-synthesized n-propylcyclopentadienyl sodium to the flask, the flask was slowly dripped with the n-propylcyclopentadienyl sodium, and the reaction solution was stirred and blended at room temperature for 20 hours to react with yttrium(III) chloride and n-propylcyclopentadienyl sodium to produce a tris(n-propylcyclopentadienyl)yttrium(III) solution.

[0068] In a 500 mL flask, 34.2 g (0.123 mol) of n-butyllithium (n-BuLi, 23%) and n-hexane (CH 14) was added, and 19.2 g (0.123 mol) of N,N'-isopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] prepared in Preparation Example 1 was slowly added dropwise, and the reaction solution was stirred at room temperature for 3 hours to synthesize lithium amidinate.

[0069] The lithium amidinate prepared above was slowly added dropwise to the tris(n-propyl-cyclopentadienyl)yttrium(III) prepared above, and the mixture was refluxed for 20 hours.

[0070] After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was distilled under reduced pressure to obtain 47 g (67%) of a yellow liquid compound represented by the following chemical formula 1.

[0071] [ka] 1 H-NMR (400MHz, C6D6, 25℃): δ6.128, 6.057 (m, 8 1 H-NMR (400MHz, C6D6, 25℃): δ6.128, 6.057(m, 8H, C5 H 4-(CH2)2CH3), δ3.351(m, 2H, (CH3)2C H NC(CH2CH3)NC H (CH3)2), δ2.532(t, 4H, C5H4-C H 2CH2CH3), δ1.979(q, 2H, (CH3)2CHNC(C H 2CH3)NCH(CH3)2), δ1.653(m, 4H, C5H4-CH2C H 2CH3), δ1.001(d, 12H, (C H 3) 2CHNC(CH2CH3)NCH(C H 3)2), δ0.969(t, 6H, C5H4-CH2CH2C H 3), δ0.915(t, 3H, (CH3)2CHNC(CH2C H 3)NCH(CH3)2)

[0072] <Example 2> Preparation of bis-n-propylcyclopentadienyl-N,N'-isopropyl-ethylamidinate gadolinium [Cp(CH2)2CH3]Gd[(CH3)2CHNC(CH2CH3)NCH(CH3)2] Sodium amide was placed in a flame-dried 500 mL Schlenk flask and kept at room temperature. 250 mL of THF and n-propylcyclopentadiene were slowly added dropwise to the flask and stirred at room temperature for 20 hours to produce n-propylcyclopentadienyl sodium.

[0073] In a flame-dried 1 L Schlenk flask, add 50 g (0.190 mol) of gadolinium(III) chloride and n-hexane (CH 14 After adding 200 mL of the above-mentioned flask, room temperature was maintained. The synthesized n-propylcyclopentadienyl sodium was slowly added dropwise to the flask, and the reaction solution was stirred at room temperature for 20 hours to prepare a tris(n-propylcyclopentadienyl)gadolinium(III) solution.

[0074] In a 500 mL flask, add 42.3 g (0.152 mol) of n-butyllithium (n-BuLi, 23%) and n-hexane (CH 14 ) was added, and 23.7 g (0.152 mol) of N,N'-isopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] prepared in Preparation Example 1 was slowly added dropwise, and the reaction solution was stirred at room temperature for 3 hours to prepare lithium amidinate.

[0075] The lithium amidinate synthesized above was slowly added dropwise to the synthesized tris(n-propyl-cyclopentadienyl)gadolinium(III), and the mixture was refluxed for 20 hours.

[0076] After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was distilled under reduced pressure to obtain 58.7 g (59.5%) of a yellow liquid compound represented by the following chemical formula 2.

[0077] [ka]

[0078] <Comparative Example 1> Bis-ethylcyclopentadienyl-N,N'-isopropyl-ethylamidinatoyttrium (EtCp)2Y[ i PrNC(Et)N i Production of Pr Sodium amide was placed in a flame-dried 500 mL Schlenk flask and kept at room temperature. 250 mL of THF and 63.7 g (0.676 mol) of ethylcyclopentadiene were slowly added dropwise to the flask and stirred at room temperature for 20 hours to produce ethylcyclopentadienyl sodium.

[0079] In a flame-dried 1 L Schlenk flask, 40 g (0.205 mol) of yttrium(III) chloride and n-hexane (C6H 14 After adding 200 mL of ethylcyclopentadienyl sodium to the flask, room temperature was maintained. The synthesized ethylcyclopentadienyl sodium was slowly added dropwise to the flask, and the reaction solution was stirred at room temperature for 20 hours to prepare a tris(ethylcyclopentadienyl)yttrium(III) solution.

[0080] In another 500 mL flask, add 45.6 g (0.164 mol) of n-butyllithium (n-BuLi, 23%) and n-hexane (C6H 14 After adding 200 mL of N,N'-isopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] prepared in Preparation Example 1 above (0.164 mol) slowly dropwise, the reaction solution was stirred at room temperature for 3 hours to prepare a lithium amidinate solution. The lithium amidinate solution was slowly added dropwise to a tris(ethylcyclopentadienyl)yttrium(III) solution prepared in a 1 L Schlenk flask and refluxed for 20 hours.

[0081] After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was distilled under reduced pressure to obtain 52 g (59%) of a yellow solid compound represented by the following chemical formula 3.

[0082] [ka] Melting point (mp) 36°C (760 torr); 1 H-NMR (400MHz, C6D6, 25℃): δ6.107, 6.057(m, 8H, C5 H 4-CH2CH3), δ3.337(m, 2H, (CH3)2C H NC(CH2CH3)NC H (CH3)2), δ2.552(q, 4H, C5H4-C H 2CH3), δ1.969(q, 2H, (CH3)2CHNC(C H 2CH3)NCH(CH3)2), δ1.237(t, 6H, C5H4-CH2C H 3), δ0.988(d, 12H, (C H 3) 2CHNC(CH2CH3)NCH(C H 3)2), δ0.896(t, 3H, (CH3)2CHNC(CH2C H 3)NCH(CH3)2)

[0083] The yttrium precursor compound of Comparative Example 1 is a solid at room temperature, and is therefore less suitable for use in mass production of semiconductors than the yttrium precursor compound of Example 1.

[0084] <Example 3> Bis-isopropylcyclopentadienyl-N,N'-isopropylethylamidinate yttrium ( i PrCp)2Y[ i PrNC(Et)N i Production of Pr Sodium amide was placed in a flame-dried 500 mL Schlenk flask and kept at room temperature. 250 mL of THF and isopropylcyclopentadiene were slowly added dropwise to the flask and stirred at room temperature for 20 hours to prepare isopropylcyclopentadienyl sodium.

[0085] In a flame-dried 1 L Schlenk flask, 30 g (0.154 mol) of yttrium(III) chloride and n-hexane (C6H 14 After adding 200 mL of isopropylcyclopentadienyl sodium to the flask, room temperature was maintained. The synthesized isopropylcyclopentadienyl sodium was slowly added dropwise to the flask, and the reaction solution was stirred and blended at room temperature for 20 hours to react yttrium(III) chloride and isopropylcyclopentadienyl sodium to prepare tris(isopropylcyclopentadienyl)yttrium(III) solution.

[0086] In a 500 mL flask, 34.2 g (0.123 mol) of n-butyllithium (n-BuLi, 23%) and n-hexane (CH 14) was added, and 19.2 g (0.123 mol) of N,N'-isopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] synthesized in Preparation Example 1 was slowly added dropwise, and the reaction solution was stirred at room temperature for 3 hours to synthesize lithium amidinate.

[0087] The lithium amidinate synthesized above was slowly added dropwise to the synthesized tris(isopropylcyclopentadienyl)yttrium(III), and the mixture was refluxed for 20 hours.

[0088] After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was distilled under reduced pressure to obtain 47.7 g (68%) of a yellow liquid compound represented by the following chemical formula 4.

[0089] [ka] 1 H-NMR (400MHz, C6D6, 25℃): δ6.158, 6.098(m, 8H, C5 H 4-CH(CH3)2), δ3.359(m, 2H, (CH3)2C H NC(CH2CH3)NC H (CH3)2), δ2.960(m, 2H, C5H4-C H (CH3)2), δ1.984(q, 2H, (CH3)2CHNC(C H 2CH3)NCH(CH3)2), δ1.293(d, 12H, C5H4-CH(C H 3)2), δ1.021(d, 12H, (C H 3) 2CHNC(CH2CH3)NCH(C H 3)2), δ0.909(t, 3H, (CH3)2CHNC(CH2C H 3)NCH(CH3)2)

[0090] <Example 4> Bis-isopropylcyclopentadienyl-N,N'-isopropylethylamidinate gadolinium ( iPrCp)2Gd[PrNC(Et)N i Production of Pr Sodium amide was placed in a flame-dried 500 mL Schlenk flask and kept at room temperature. 250 mL of THF and isopropylcyclopentadiene were slowly added dropwise to the flask and stirred at room temperature for 20 hours to prepare isopropylcyclopentadienyl sodium.

[0091] In a flame-dried 1 L Schlenk flask, 30 g (0.114 mol) of gadolinium(III) chloride and n-hexane (C6H 14 After adding 200 mL of isopropylcyclopentadienyl sodium to the flask, room temperature was maintained. The reaction solution was stirred at room temperature for 20 hours to prepare a tris(isopropylcyclopentadienyl)gadolinium(III) solution.

[0092] In a 500 mL flask, add 25.4 g (0.091 mol) of n-butyllithium (n-BuLi, 23%) and n-hexane (C6H 14 200 mL of N,N'-isopropylpropionimidamide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] synthesized in Preparation Example 1 was slowly added dropwise, and the reaction solution was stirred at room temperature for 3 hours to synthesize lithium amidinate.

[0093] The lithium amidinate synthesized above was slowly added dropwise to the synthesized tris(isopropylcyclopentadienyl)gadolinium(III), and the mixture was refluxed for 20 hours.

[0094] After the reaction was completed, the solvent was removed under reduced pressure, and the mixture was distilled under reduced pressure to obtain 36 g (60.8%) of a yellow liquid compound represented by the following chemical formula 5.

[0095] [ka]

[0096] <Comparative Example 2> Bis-isopropylcyclopentadienyl-N,N'-isopropylmethylamidinate yttrium ( i PrCp)2Y[ i PrNC(Me)N i Production of Pr Bis-isopropylcyclopentadienyl-N,N'-isopropylmethylamidinate yttrium ( i PrCp)2Y[ i PrNC(Me)N i Pr] was produced.

[0097] <Experimental Example 1> Comparison of viscosity of precursor compounds The previously known Comparative Example 2 ( i PrCp)2Y( i Pr-NC(Me)=N- i Pr) precursor compound and Example 1 of the present invention ( n PrCp)2Y( i Pr-NC(Et)=N- i Pr), Example 2 ( n PrCp)2Gd( i Pr-NC(Et)=N- i The viscosities of the precursor compounds N,N'-isopropyl-methylamidinate (Pr) are compared in Table 1 below. i Pr-NC(Me)=N- i Precursor compounds containing Pr) ligands ( i PrCp)2Y( i Pr-NC(Me)=N- iPr) (Comparative Example 2) had a measured viscosity of 81 cP, while N,N'-isopropyl-ethyl amidinate ( i Pr-NC(Et)=N- i The precursor compound of the present invention includes a Pr ligand ( n PrCp)2Y( i Pr-NC(Et)=N- i Pr) (Example 1) has a viscosity of 69 cP, ( n PrCp)2Gd( i Pr-NC(Et)=N- i The viscosity of Pr) (Example 2) was measured to be 68 cP.

[0098] [Table 1]

[0099] When a container containing ALD or CVD precursors is heated and vaporized, if the precursor has low vapor pressure and high viscosity, the precursor may remain in the dead space of gas supply pipes or valves. When ALD or CVD precursors are injected in liquid form into a flash evaporator heated to a high temperature and vaporized instantly, clogging of the vaporizer is likely to occur if the viscosity is high. In addition, liquids with too high a viscosity cannot be used in liquid metering pumps that transport liquids.

[0100] In an ALD or CVD apparatus using a liquid transfer device and an instant vaporizer, if the viscosity of the liquid that can be used in the pump that transfers the liquid needs to be reduced, for example, if it needs to be maintained at 9 cP or less, it is necessary to reduce the viscosity by mixing a low-viscosity liquid (solvent) with a high-viscosity precursor. If too much low-viscosity liquid is added, the content of the precursor in the mixture with reduced viscosity becomes relatively low, and the amount of gaseous precursor supplied when vaporizing the same volume of liquid is reduced. Therefore, when it is necessary to adjust the viscosity, it is advantageous to mix a small amount of low-viscosity liquid. The precursor compounds according to Examples 1 and 2 of the present application have a lower viscosity than the precursor of Comparative Example 2, which is already known, and are therefore more advantageous for use as ALD or CVD precursors.

[0101] The mixing ratio of octane required to adjust the viscosity of the mixture to 8.5±0.5 cP when octane is used as a low-viscosity liquid (solvent) is shown in the following [Table 2] and Figure 1. According to Table 2 and Figure 1, the precursor compounds of Examples 1 and 2 can reduce the viscosity of the mixture to 8.5±0.5 cP even when less octane is mixed than the precursor compound of Comparative Example 2.

[0102] [Table 2]

[0103] <Experimental Example 2> Oxide film deposition characteristics of yttrium precursor compounds as a function of substrate temperature Atomic Layer Deposition (ALD) process was carried out using the yttrium precursor compounds prepared by the methods of Examples 1 and 3. O3, an oxygen source, was used as the reactive gas. First, a silicon wafer was immersed in a piranha solution, which is a 4:1 mixture of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2), for 10 minutes, removed, and then immersed in a dilute HF solution for about 2 minutes to remove the oxide film on the silicon surface, and then an yttrium oxide thin film was produced by atomic layer deposition (ALD).

[0104] In order to measure the deposition characteristics according to the substrate temperature, the ALD process was performed by heating the substrate to temperatures of 300°C, 310°C, 320°C, and 340°C. The yttrium precursor compound was placed in a stainless steel container and heated to a temperature of 150°C. The process pressure of the ALD reactor was maintained at 1 torr. Argon (Ar) gas was passed through the stainless steel container containing the yttrium precursor compound at a flow rate of 300 sccm to supply the yttrium precursor compound gas to the ALD reactor. The ALD gas cycle of yttrium precursor supply for 3 seconds, purging for 10 seconds, O3 supply for 10 seconds, and purging for 5 seconds was repeated 100 times to deposit yttrium oxide films at each substrate temperature. The film growth per ALD gas supply cycle (gPC) obtained by measuring the thickness of the oxide film is shown in Figure 2 according to the substrate temperature. All of the yttrium precursors of Examples 1 and 3 exhibited a constant GPC of about 0.3 Å / cycle in the temperature range of 300° C. to 340° C.

[0105] If the GPC is constant over a wide temperature range, the thickness of the deposited film will be constant despite temperature changes, which is advantageous when applying ALD to semiconductor manufacturing. As semiconductor devices continue to be miniaturized, the thickness of the dielectric film of DRAM capacitors is gradually becoming thinner, making it necessary to form a film with a constant thickness over a wide temperature range. Therefore, as can be seen from FIG. 2, the yttrium precursors of Examples 1 and 3 of the present invention have a constant GPC over a wide temperature range, and are therefore more advantageous for depositing yttrium oxide (Y2O3), which requires fine and uniform thickness adjustment by the ALD process, than conventional yttrium precursors, which do not have a constant GPC depending on temperature changes.

[0106] <Experimental Example 3> Oxide film deposition characteristics depending on precursor supply time for yttrium precursor compounds An yttrium oxide film was produced under the same conditions as in Experimental Example 2, except that the substrate temperature was fixed at 300°C and the yttrium precursor supply time during the ALD gas supply cycle was changed from 3 seconds to 1 second, 5 seconds, and 7 seconds. This ALD gas supply cycle was repeated 100 times to deposit an yttrium oxide film and measure the film thickness. The GPC obtained is shown in Figure 3. Under ideal ALD conditions, the GPC should remain constant even if the precursor supply time is increased. If ALD is performed at a temperature where the precursor compound is not thermally stable, the film thickness will increase as the precursor supply time is increased.

[0107] In FIG. 3, it can be seen that the GPC is constant for both the yttrium precursors of Example 1 and Example 3 when the precursor supply time is 3 seconds or more. In order to form a film of a constant thickness on a semiconductor DRAM capacitor with a very large aspect ratio (50 or more), a precursor whose film thickness does not increase even when the precursor supply time is increased is required. When the precursor supply time needs to be extended to supply a sufficient amount of precursor to a substrate with a large aspect ratio and an actual surface area larger than the apparent surface area, if a precursor whose film thickness increases as the precursor supply time increases is used, a film of the same thickness cannot be formed on the top and bottom of a groove with a large aspect ratio. Therefore, as confirmed in FIG. 3, the yttrium precursors of Example 1 and Example 3 of the present invention do not increase the film thickness even when the precursor supply time is increased, and are therefore advantageous for forming a film of a constant thickness on a structure with a large aspect ratio compared to conventional yttrium precursors whose film thickness increases when the precursor supply time is increased, and can be used to form a semiconductor DRAM capacitor.

[0108] The above description of the present application is for illustrative purposes only, and a person having ordinary skill in the art to which the present application pertains should understand that the present application can be easily modified into other specific forms without changing the technical idea or essential features of the present application. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and are not limiting. For example, each component described as a single type may be implemented in a distributed form, and similarly, each component described as a distributed type may be implemented in a combined form.

[0109] The scope of the present application is indicated by the claims set forth below rather than by the above detailed description, and all modifications and variations derived from the meaning and scope of the claims, as well as their equivalent concepts, should be construed as being included within the scope of the present application.

Claims

1. 1. An yttrium or lanthanum group metal-containing precursor compound which is liquid at room temperature and is represented by the following formula I: [Chemical formula I] (R １ Cp) ２ M[(CH ３ ) ２ CH-N-C(CH ２ CH ３ )=N-CH(CH ３ ) ２ ]; In the above formula I, M is Y or Gd; R １ is an n-propyl group ( ｎ Pr) or iso-propyl group ( ｉ Pr), The Cp is a cyclopentadienyl group.

2. 2. The yttrium or lanthanum group metal containing precursor compound of claim 1, wherein the yttrium or lanthanum group metal containing precursor compound is selected from the following: ( ｎ (PrCp) ２ Y( ｉ (a) (b) (c) (d) (e) (f) (g) (h ... ｉ (Pr)、( ｎ (PrCp) ２ Gd( ｉ (a) (b) (c) (d) (e) (f) (g) (h ... ｉ (Pr)、( ｉ (PrCp) ２ Y( ｉ (a) (b) (c) (d) (e) (f) (g) (h ... ｉ (Pr)、( ｉ (PrCp) ２ Gd( ｉ (a) (b) (c) (d) (e) (f) (g) (h ... ｉ Pr)

3. A precursor composition for forming an yttrium or lanthanum group metal containing film comprising one or more yttrium or lanthanum group metal containing precursor compounds according to claim 1 or 2.

4. 4. The precursor composition for forming an yttrium or lanthanum group metal-containing film according to claim 3, comprising one or more yttrium or lanthanum group metal-containing precursor compounds selected from the following: ( ｎ (PrCp) ２ Y( ｉ (a) (b) (c) (d) (e) (f) (g) (h ... ｉ (Pr)、( ｎ (PrCp) ２ Gd( ｉ (a) (b) (c) (d) (e) (f) (g) (h ... ｉ (Pr)、( ｉ (PrCp) ２ Y( ｉ (a) (b) (c) (d) (e) (f) (g) (h ... ｉ (Pr)、( ｉ (PrCp) ２ Gd( ｉ (a) (b) (c) (d) (e) (f) (g) (h ... ｉ Pr)

5. 4. The precursor composition for forming an yttrium or lanthanum group metal-containing film according to claim 3, wherein the yttrium or lanthanum group metal-containing film is an yttrium or lanthanum group metal film, an yttrium or lanthanum group metal-containing oxide film, an yttrium or lanthanum group metal-containing nitride film, or an yttrium or lanthanum group metal-containing carbide film.

6. 4. The yttrium or lanthanum group metal-containing film-forming precursor composition of claim 3, further comprising one or more nitrogen sources selected from ammonia, nitrogen, hydrazine, and dimethylhydrazine.

7. 4. The yttrium or lanthanum group metal-containing film-forming precursor composition of claim 3, further comprising one or more oxygen sources selected from water vapor, oxygen, and ozone.

8. A method for forming an yttrium or lanthanum group metal-containing film, comprising forming an yttrium or lanthanum group metal-containing film by using a film-forming precursor composition according to any one of claims 3 to 7.

9. 9. The method of claim 8, wherein the yttrium or lanthanum group metal-containing film is deposited by chemical vapor deposition or atomic layer deposition.

10. 9. The method for forming an yttrium or lanthanum group metal-containing film according to claim 8, wherein the thickness of the yttrium or lanthanum group metal-containing film is from 1 nm to 10 μm.

11. 9. The method of claim 8, wherein the yttrium or lanthanum group metal containing film is formed at a temperature range of 100°C to 500°C.

12. 9. The method for forming an yttrium or lanthanum group metal-containing film according to claim 8, wherein the yttrium or lanthanum group metal-containing film is formed on a substrate having an aspect ratio of 1 to 100 and including irregularities having widths of 10 nm to 1 μm.

Images