yttrium or lanthanide metal precursor compounds, film-forming compositions comprising the same, and methods of forming yttrium or lanthanide metal-containing films using the same

Abstract

The present application relates to yttrium / lanthanide metal precursor compounds, precursor compositions comprising the yttrium / lanthanide metal precursor compounds for depositing yttrium / lanthanide metal-containing films, and methods of depositing yttrium / lanthanide metal-containing films using the precursor compositions.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 202080077919.4, filed on December 24, 2020, entitled "Yttrium or Lanthanide Metal Precursor Compounds, Film-forming Compositions Containing the Same, and Method of Using the Same to Form a Film Containing Yttrium or Lanthanide Metals". Technical Field

[0002] This application relates to yttrium / lanthanide metal precursor compounds, precursor compositions comprising the yttrium / lanthanide metal precursor compounds for depositing yttrium / lanthanide metal-containing films, and methods for depositing yttrium / lanthanide metal-containing films using the precursor compositions. Background Technology

[0003] Because yttrium-containing oxide films or lanthanide-containing oxide films possess a wide bandgap (5.6 eV), low leakage current, high breakdown voltage, and good thermal stability, their use as gate dielectric materials for field-effect transistors in semiconductor devices is currently under investigation. Furthermore, in semiconductor memory devices, the use of yttrium-containing oxide films or lanthanide-containing oxide films as gate insulating films for DRAMs and high-k dielectric layers for capacitors is being studied. Moreover, the use of yttrium-containing oxide films or lanthanide-containing oxide films as insulating films in metal-insulator-metal (MIM) structures for non-volatile resistive switching memory devices is also being investigated.

[0004] Most known yttrium or lanthanide metal precursor compounds have low vapor pressures and are either solids or highly viscous liquids, making them unsuitable as precursors in the mass production of semiconductor devices when forming yttrium or lanthanide metal oxide films via chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0005] In order to form yttrium or lanthanide metal films required for the fabrication of next-generation semiconductor devices by atomic layer deposition, the precursor compounds need to have lower viscosity or higher vapor pressure compared to previously known yttrium precursor compounds or lanthanide metals.

[0006] [Technical Documents]

[0007] Korean Patent Application Publication No. 10-2012-0017069 Summary of the Invention

[0008] [Technical Issues]

[0009] The purpose of this application is to provide novel yttrium or lanthanide metal precursor compounds, precursor compositions for film deposition containing the metal precursor compounds, and methods for forming yttrium or lanthanide metal films using the precursor compositions.

[0010] In particular, the purpose of this application is to provide a precursor compound having a lower viscosity than previously known precursor compounds, a precursor composition comprising the precursor compound for film deposition, and a method for forming a film using the precursor composition.

[0011] However, the technical problems to be solved by this application are not limited to the above-mentioned technical problems, and those skilled in the art can clearly understand other technical problems not mentioned from the following description.

[0012] [Technical Solution]

[0013] The first aspect of this application provides yttrium or lanthanide metal precursor compounds represented by the following chemical formula I: [Chemical Formula I] (R 1 Cp)2M[(CH3)2CH-NC(CH2CH3)=N-CH(CH3)2]; In the chemical 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 n-propyl ( n Pr) or isopropyl ( i Pr), The Cp mentioned above is cyclopentadienyl.

[0014] The second aspect of this application provides a precursor composition for forming a yttrium or lanthanide metal-containing film, comprising a yttrium or lanthanide metal-containing precursor compound according to the first aspect of this application.

[0015] A third aspect of this application provides a method for forming a film containing yttrium or lanthanides, comprising forming the film using a precursor composition for forming a film containing yttrium or lanthanides according to a second aspect of this application.

[0016] [Beneficial Effects]

[0017] The novel yttrium compounds or lanthanide-containing precursor compounds according to embodiments of this application are novel compounds not previously known. The novel yttrium compounds or lanthanide-containing precursor compounds according to embodiments of this application are liquid at room temperature and thermally stable.

[0018] The novel yttrium or lanthanide metal precursor compounds according to embodiments of this application have lower viscosity than existing known yttrium or lanthanide metal precursor compounds, and when a low-viscosity liquid (solvent) is mixed to reduce viscosity for use in an ALD or CVD precursor liquid delivery device, even a small amount of low-viscosity liquid (solvent) can be mixed to prepare a mixture with the desired viscosity, thus making it suitable for forming yttrium or lanthanide metal films by ALD or CVD processes.

[0019] The novel yttrium compounds or lanthanide-containing precursor compounds according to embodiments of this application have high thermal stability and can therefore be used as precursors for vapor deposition, such as atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form yttrium or lanthanide-containing films.

[0020] The compositions containing yttrium or lanthanide metal precursor compounds according to embodiments of this application, and the methods for forming yttrium or lanthanide metal films using the precursor compositions, can be applied to the manufacture of commercial semiconductor devices. Specifically, for the manufacture of DRAM semiconductor devices, 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 width of about 10 nm to about 1 μm, or less than about 100 nm or about 50 nm and an aspect ratio of about 1 to about 50, about 10 or greater, about 20 or greater, or about 30 or greater, or deeper and narrower. The yttrium or lanthanide metal precursor compounds and the precursor compositions containing the precursor compounds according to embodiments of this application enable the formation of yttrium or lanthanide metal films with commercially viable thicknesses on the aforementioned substrates. Furthermore, the use of yttrium- or lanthanide metal precursor compounds and precursor compositions containing such precursor compounds according to embodiments of this application can provide the following excellent effects: for a substrate having fine irregularities (grooves) on its surface with an aspect ratio of about 1 or greater and a width of about 1 μm, it is possible to form a film of yttrium- or lanthanide metal with a uniform thickness of several nm to tens of nm on the entire surface of the substrate (including the surface of the fine irregularities (grooves), which includes the deepest surface of the fine irregularities (grooves) and the upper surface of the fine irregularities (grooves)).

[0021] In particular, since a high-dielectric material film of uniform thickness needs to be formed even at temperatures of approximately 280°C, approximately 300°C, or higher, a precursor composition is needed that can form a film of uniform thickness on a substrate with very narrow and deep grooves via atomic layer deposition (ALD), even at high temperatures. Therefore, a yttrium- or lanthanide metal-containing precursor compound with very high thermal stability is needed to meet the above requirements. For this purpose, the yttrium- or lanthanide metal-containing precursor compound according to the embodiments of this application can be effectively used as a precursor to meet the aforementioned desired properties.

[0022] Because the yttrium or lanthanide precursor compounds according to embodiments of this application have constant growth per cycle (GPC) over a wider temperature range, they are more advantageous for depositing yttrium or lanthanide films requiring fine and uniform thickness control according to the ALD process compared to existing yttrium or lanthanide precursor compounds whose GPC is not constant with temperature variations.

[0023] The yttrium or lanthanide precursor compounds according to embodiments of the present invention have a constant GPC that is independent of the precursor supply time. Therefore, even if there are uneven (grooved) structures with a large aspect ratio and small width on the substrate, it is more advantageous to form a film with constant thickness than existing yttrium precursors that do not have a constant GPC with the precursor supply time.

[0024] The yttrium or lanthanide metal precursor compounds described in the embodiments of this application, when used as precursors for ALD, CVD, etc., can provide the performance required for manufacturing next-generation devices such as semiconductors, such as improved thermal stability, higher volatility and / or increased deposition rate, and are therefore effectively used to form films or thin films containing yttrium or lanthanides metals.

[0025] The yttrium compounds or lanthanide-containing compounds described in the embodiments of this application can be applied to a variety of fields, such as catalysts. Attached Figure Description

[0026] Figure 1 This is a graph showing the viscosity of the precursor compounds according to the octane mixing ratio of Examples 1, 2 and Comparative Example 2 of this application.

[0027] Figure 2 This is a graph showing the film growth of the precursor compounds according to Examples 1 and 3 of this application for each ALD gas supply cycle according to the substrate temperature.

[0028] Figure 3 This is a graph showing the membrane growth of the precursor compounds of Examples 1 and 3 according to the present application for each ALD gas supply cycle based on the precursor supply time. Detailed Implementation

[0029] In the following, embodiments and examples of this application will be described in detail with reference to the accompanying drawings to enable those skilled in the art to readily implement them. However, this application can be implemented in many different forms and is not limited to the embodiments and examples described herein. In the drawings, parts unrelated to the description have been omitted in order to clearly illustrate the invention, and similar reference numerals are used throughout the specification for similar parts.

[0030] Throughout the instruction manual, when referring to a part being "connected" to another part, it includes not only cases of "direct connection" but also cases of "electrical connection" formed by other devices between them.

[0031] Throughout the specification, when it is mentioned that a component is "on" another component, it includes not only the case where the component is in contact with the other component, but also the case where there is another component between the two components.

[0032] Throughout the specification of this application, when a part “includes” an element, it means that other elements may be included rather than excluded, unless otherwise stated.

[0033] As for degree-related terms such as “about” and “basically” used in this specification, when given manufacturing and material tolerances specific to the meaning mentioned, they are used to indicate the value or approximate the value, and to prevent unscrupulous infringers from improperly using the disclosure that mentions accurate or absolute values ​​to aid in the understanding of this application.

[0034] As used throughout the specification of this application, the degree-related terms "performing the ~ step" or "~ step" do not mean "for the ~ step".

[0035] Throughout this application, the term "themselves (or combinations thereof" included in the Markus-type description refers to one or more mixtures or combinations of the group of elements selected from the Markus-type description, meaning that it includes at least one of the group of said elements.

[0036] Throughout the description of this application, the phrase “A and / or B” means “A or B, or A and B”.

[0037] Throughout this application, the term "alkyl" or "alkyl group" includes straight-chain 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, as well as their possible isomers. For example, the alkyl or alkyl group may include methyl (Me), ethyl (Et), n-propyl (... n Pr), isopropyl ( iso Pr), n-butyl ( n Bu), isobutyl ( iso Bu), tert-Bu, t Bu), sec-Bu, sec Bu), n-pentyl ( n Pe), isopentyl ( iso Pe), secondary pentyl ( sec Pe), tert-amyl ( tPe), neopentyl ( neo Pe), 3-pentyl, n-hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl and their isomers, etc., but not limited thereto.

[0038] Throughout this application, the term "yttrium or lanthanide metals" may include Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0039] Throughout this application, the term “Cp” stands for -C5H4, which is an abbreviation for “cyclopentadienyl”.

[0040] Throughout this application, the term "membrane" means "membrane or thin film".

[0041] The embodiments of this application are described in detail below, but this application is not limited thereto.

[0042] The first aspect of this application provides yttrium or lanthanide metal precursor compounds represented by the following chemical formula I: [Chemical Formula I] (R 1 Cp)2M[(CH3)2CH-NC(CH2CH3)=N-CH(CH3)2]; In the chemical 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 n-propyl ( n Pr) or isopropyl ( i Pr), The Cp is cyclopentadienyl.

[0043] In one embodiment of this application, the yttrium or lanthanide metal 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), ( nPrCp)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- i Pr)、( 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).

[0044] In one embodiment of this application, the yttrium- or lanthanide-containing precursor compound may be ( n PrCp)2Y( iPr-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).

[0045] The second aspect of this application provides a precursor composition for forming a yttrium- or lanthanide-containing film, comprising at least one of the yttrium- or lanthanide-containing precursor compounds according to the first aspect of this application.

[0046] Although detailed descriptions that overlap with the first aspect of this application have been omitted, such descriptions are equally applicable to the second aspect of this application, even if the descriptions relating to the first aspect of this application are omitted in the second aspect.

[0047] In one embodiment of this application, the precursor composition for forming a yttrium- or lanthanide-containing film may include, but is not limited to, one or more yttrium- or lanthanide-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( 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- i Pr)、( 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)、( iPrCp)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).

[0048] In one embodiment of this application, the yttrium- or lanthanide-containing precursor compound may be ( 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).

[0049] In one embodiment of this application, the yttrium or lanthanide metal-containing film is a yttrium or lanthanide metal film, a yttrium or lanthanide metal-containing oxide film, a yttrium or lanthanide metal-containing nitride film, or a yttrium or lanthanide metal-containing carbide film, but is not limited thereto. In one embodiment of this application, the yttrium or lanthanide metal-containing film may be a yttrium or lanthanide metal-containing oxide film.

[0050] In one embodiment of this application, the precursor composition for forming a yttrium or lanthanide metal-containing film may further comprise one or more nitrogen sources selected from ammonia, nitrogen, hydrazine and dimethylhydrazine, but is not limited thereto.

[0051] In one embodiment of this application, the precursor composition for forming a yttrium or lanthanide metal-containing film may further include one or more oxygen sources selected from water vapor, oxygen, and ozone, but is not limited thereto.

[0052] A third aspect of this application provides a method for forming a yttrium or lanthanide metal-containing film, comprising forming the yttrium or lanthanide metal-containing film using a precursor composition for forming a yttrium or lanthanide metal-containing film according to a second aspect of this application.

[0053] Although detailed descriptions of portions that overlap with the first and second aspects of this application have been omitted, such descriptions are equally applicable to the third aspect of this application, even if they are omitted from the descriptions of the first and second aspects of this application.

[0054] In one embodiment of this application, the yttrium or lanthanide metal-containing film may be a yttrium or lanthanide metal film, a yttrium or lanthanide metal-containing oxide film, a yttrium or lanthanide metal-containing nitride film, or a yttrium or lanthanide metal-containing carbide film, but is not limited thereto. In one embodiment of this application, the yttrium or lanthanide metal-containing film may be a yttrium or lanthanide metal-containing oxide film.

[0055] In one embodiment of this application, the yttrium- or lanthanide-containing film can be deposited using chemical vapor deposition (CVD) or atomic layer deposition (ALD), but is not limited thereto. The yttrium- or lanthanide-containing film can also be deposited using metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but is not limited thereto. In one embodiment of this application, the yttrium- or lanthanide-containing film can be deposited using atomic layer deposition.

[0056] Furthermore, the chemical vapor deposition or atomic layer deposition method can be performed using deposition equipment, deposition conditions, and / or other reactive gases known in the art, but is not limited thereto. Here, if atomic layer deposition is used to deposit yttrium or lanthanide metal oxide films, the process temperature can be controlled during deposition, and the thickness and composition of the film can be precisely controlled. Therefore, films with excellent coatability can be deposited even on substrates with complex shapes, and the thickness uniformity and physical properties of the film can be improved.

[0057] In one embodiment of this application, the thickness of the yttrium or lanthanide metal-containing film can be from about 1 nm to about 10 μm, and can be applied differently depending on the application, but is not limited thereto. In one embodiment of this application, the thickness of the yttrium-containing oxide film can be from about 1 nm to about 10 μm, and can be applied differently depending on the application, but is not limited thereto. For example, the thickness of the yttrium or lanthanide metal-containing film can be from about 1 nm to about 10 μm, from about 1 nm to about 5 μm, from about 1 nm to about 1 μm, from about 1 nm to about 900 nm, from about 1 nm to about 800 nm, from about 1 nm to about 700 nm, from about 1 nm to about 600 nm, from about 1 nm to about 500 nm, from about 1 nm to about 400 nm, from about 1 nm to about 300 nm, from about 1 nm to about 200 nm, from about 1 nm to about 100 nm, from about 1 nm to about 50 nm, from about 1 nm to about 30 nm, from about 1 nm to about 20 nm, from about 1 nm to about 10 nm, from about 10 nm to about 10 μm, from about 10 nm to about 5 μm, 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. m, approximately 10nm to approximately 400nm, approximately 10nm to approximately 300nm, approximately 10nm to approximately 200nm, approximately 10nm to approximately 100nm, approximately 10nm to approximately 50nm, approximately 10nm to approximately 30nm, approximately 10nm to approximately 20nm, approximately 20nm to approximately 10µm, 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 20nm to approximately 300nm, approximately 20nm to approximately 200nm, approximately 20nm to approximately 100nm, approximately 20nm to approximately 50nm, approximately 20nm to approximately 30nm, approximately 30nm to approximately 10μm, approximately 30nm to approximately 5μm, approximately 30nm to approximately 1μm, approximately 3 0nm to 900nm, approximately 30nm to 800nm, approximately 30nm to 700nm, approximately 30nm to 600nm, approximately 30nm to 500nm, approximately 30nm to 400nm, approximately 30nm to 300nm, approximately 30nm to 200nm, approximately 30nm to 100nm, approximately 30nm to 50nm, approximately 50nm to 10μm, approximately 50nm to 5μm, approximately 50nm to 1µm, approximately 50nm to 900nm, approximately 50nm to 800nm, approximately 50nm to 700nm, approximately 50nm to 600nm, approximately 50nm to 500nm, approximately 50nm to 400nm, approximately 50nm to 300nm, approximately 50nm to 200nm,Approximately 50nm to approximately 100nm, approximately 100nm to approximately 10μm, approximately 100nm to approximately 5μm, approximately 100nm to approximately 1μm, approximately 100nm to approximately 900nm, approximately 100nm to approximately 800nm, approximately 100nm to approximately 700nm, approximately 100nm to approximately 600nm, approximately 100nm to approximately 500nm, approximately 100nm to 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 8μm 00nm, approximately 200nm to approximately 700nm, approximately 200nm to approximately 600nm, approximately 200nm to approximately 500nm, approximately 200nm to approximately 400nm, approximately 200nm to approximately 300nm, approximately 300nm to approximately 10μm, approximately 300nm to approximately 5μm, approximately 300nm to approximately 1μm, approximately 300nm to approximately 900nm, approximately 300nm to approximately 800nm, approximately 300nm to approximately 700nm, approximately 300nm to approximately 600nm, approximately 300nm to approximately 500nm, approximately 300nm to approximately 400nm, approximately 400nm to approximately 10μm, approximately 400nm to approximately 5μm, approximately 400nm to approximately 1μm, approximately 400nm to approximately 900nm, approximately 400nm to approximately 800nm, approximately 400nm to approximately 700nm, approximately 400nm to approximately 600nm, approximately 400nm to approximately 500nm, approximately 500nm to approximately 10μm, approximately 500nm to approximately 5μm, approximately 500nm to approximately 1μm, approximately 500nm to approximately 900nm, approximately 500nm to approximately 800nm, approximately 500nm to approximately 700nm, approximately 500nm to approximately 600nm, approximately 600nm to approximately 10μm, approximately 600nm to approximately 5μm, approximately 600nm to approximately 1μm, approximately 600nm to approximately 900nm nm, approximately 600 nm to approximately 800 nm, approximately 600 nm to approximately 700 nm, approximately 700 nm to approximately 10 μm, approximately 700 nm to approximately 5 μm, approximately 700 nm to approximately 1 μm, approximately 700 nm to approximately 900 nm, approximately 700 nm to approximately 800 nm, approximately 800 nm to approximately 10 μm, approximately 800 nm to approximately 5 μm, approximately 800 nm to approximately 1 μm, approximately 800 nm to approximately 900 nm, approximately 900 nm to approximately 10 μm, approximately 900 nm to approximately 5 μm, approximately 900 nm to approximately 1 μm, approximately 1 μm to approximately 10 μm, approximately 1 μm to approximately 5 μm, or approximately 5 μm to approximately 10 μm, but not limited to these.

[0058] In one embodiment of this application, the yttrium or lanthanide metal-containing film can be formed in a temperature range of about 100°C to about 500°C, but is not limited thereto. For example, the yttrium or lanthanide metal-containing film can be at temperatures ranging from about 100°C to about 500°C, from about 100°C to about 450°C, from about 100°C to about 400°C, from about 100°C to about 350°C, from about 100°C to about 300°C, from about 100°C to about 250°C, from about 100°C to about 200°C, from about 100°C to about 150°C, from about 150°C to about 500°C, from about 150°C to about 450°C, from about 150°C to about 400°C, from about 150°C to about 350°C, from about 150°C to about 300°C, from about 150°C to about 250°C, from about 150°C to about 200°C, from about 200°C to about 500°C, from about 200°C to about 450°C, from about 200°C to about 4 ... Formed within the range of 350°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, but not limited thereto.

[0059] In one embodiment of this application, the yttrium or lanthanide metal-containing film can be formed on a substrate having an aspect ratio of about 1 to about 100 and a width of about 10 nm to about 1 μm, but is not limited thereto. For example, the aspect ratio can be 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 Approximately 50, approximately 20 to approximately 40, approximately 20 to approximately 30, approximately 30 to approximately 100, approximately 30 to approximately 80, approximately 30 to approximately 60, approximately 30 to approximately 50, approximately 30 to approximately 40, approximately 40 to approximately 100, approximately 40 to approximately 80, approximately 40 to approximately 60, approximately 40 to approximately 50, approximately 50 to approximately 100, approximately 50 to approximately 80, approximately 50 to approximately 60, approximately 60 to approximately 100, approximately 60 to approximately 80, or approximately 80 to approximately 100, but not limited to these. Furthermore, for example, the width can be approximately 10 nm to approximately 1 μm, approximately 10 nm to approximately 900 nm, approximately 10 nm to approximately 800 nm, approximately 10 nm to approximately 700 nm, approximately 10 nm to approximately 600 nm, approximately 10 nm to approximately 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 90 nm, approximately 10 nm to approximately 80 nm, approximately 10 nm to approximately 70 nm, approximately 10 nm to approximately 60 nm, approximately 10 nm to approximately 50 nm, approximately 10 nm to approximately 40 nm, approximately 10 nm to approximately 30 nm, approximately 10 nm to approximately 20 nm, approximately 20 nm to approximately 1 μm, approximately 20 nm to approximately 900 nm, approximately 20 nm to approximately 800 nm, approximately 20 nm to approximately 700 nm, approximately 20 nm to approximately 60 ...1 μm, approximately 20 nm to approximately 1 μm, approximately 20 nm to approximately 1 μm, approximately 20 nm to approximately 1 μm, approximately 20 nm to approximately 1 μm, approximately 20 nm to approximately 1 μm, approximately Approximately 500nm, approximately 20nm to approximately 400nm, approximately 20nm to approximately 300nm, approximately 20nm to approximately 200nm, approximately 20nm to approximately 100nm, approximately 20nm to approximately 90nm, approximately 20nm to approximately 80nm, approximately 20nm to approximately 70nm, approximately 20nm to approximately 60nm, approximately 20nm to approximately 50nm, approximately 20nm to approximately 40nm, approximately 20nm to approximately 30nm, approximately 30nm to approximately 1μm, approximately 30nm to approximately 900nm, approximately 30nm to approximately 800nm, approximately 30nm to approximately 700nm, approximately 30nm to approximately 600nm, approximately 30nm to approximately 500nm, approximately 30nm to approximately 400nm, approximately 30nm to approximately 300nm, approximately 30nm to approximately 200nm, approximately 30nm to approximately 100nm, approximately 30nm to approximately 90nm, approximately 30nm to approximately 80nm, approximately 30nm to approximately 70nm,Approximately 30nm to approximately 60nm, approximately 30nm to approximately 50nm, approximately 30nm to approximately 40nm, approximately 40nm to approximately 1μm, approximately 40nm to approximately 900nm, approximately 40nm to approximately 800nm, approximately 40nm to approximately 700nm, approximately 40nm to approximately 600nm, approximately 40nm to approximately 500nm, approximately 40nm to approximately 400nm, approximately 40nm to approximately 300nm, approximately 40nm to approximately 200nm, approximately 40nm to approximately 100nm, approximately 40nm to approximately 90nm, approximately 40nm to approximately 80nm, approximately 40nm to approximately 70nm, approximately 40nm to approximately 60nm, approximately 40nm to approximately 50nm, approximately 50nm to approximately 1μm, approximately 50nm to approximately 900nm, approximately 50nm to approximately 800nm, approximately 50nm to approximately 700nm, approximately 50nm to approximately 600nm, 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, approximately 50nm to approximately 90nm, approximately 50nm to approximately 80nm, approximately 50nm to approximately 70nm, approximately 50nm to approximately 60nm, approximately 100nm to approximately 1μm, approximately 100nm to approximately 900nm, approximately 100nm to approximately 800nm, approximately 100nm to approximately 700nm, approximately 100nm to approximately 600nm, approximately 100nm to approximately 500nm, approximately 100nm to approximately 400nm, approximately 100nm to approximately 300nm, approximately 100nm to approximately 200nm, approximately 200nm to approximately 1μm, approximately 200nm m to approximately 900nm, approximately 200nm to approximately 800nm, approximately 200nm to approximately 700nm, approximately 200nm to approximately 600nm, approximately 200nm to approximately 500nm, approximately 200nm to approximately 400nm, approximately 200nm to approximately 300nm, approximately 300nm to approximately 1μm, approximately 300nm to approximately 900nm, approximately 300nm to approximately 800nm, approximately 300nm to approximately 700nm, approximately 300nm to approximately 600nm, approximately 300nm to approximately 500nm, approximately 300nm to approximately 400nm, approximately 400nm to approximately 1μm, approximately 400nm to approximately 900nm, approximately 400nm to approximately 800nm Approximately 400nm to approximately 700nm, approximately 400nm to approximately 600nm, approximately 400nm to approximately 500nm, approximately 500nm to approximately 1μm, approximately 500nm to approximately 900nm, approximately 500nm to approximately 800nm, approximately 500nm to approximately 700nm, approximately 500nm to approximately 600nm, approximately 600nm to approximately 1μm, approximately 600nm to approximately 900nm, approximately 600nm to approximately 800nm, approximately 600nm to approximately 700nm, approximately 700nm to approximately 1μm, approximately 700nm to approximately 900nm, approximately 700nm to approximately 800nm, approximately 800nm ​​to approximately 1μm, approximately 800nm ​​to approximately 900nmOr approximately 900 nm to approximately 1 μm, but not limited to this.

[0060] A deposition method according to one embodiment of this application using a composition comprising a yttrium or lanthanide metal precursor compound may include, but is not limited to, forming a yttrium or lanthanide metal oxide film by supplying the precursor composition comprising the yttrium or lanthanide metal precursor compound in a gaseous state to a substrate located in a deposition chamber. The film deposition method may use methods, apparatus, etc., known in the art of the invention, and may, if desired, simultaneously use one or more additional reactive gases. As the substrate, silicon semiconductor wafers, compound semiconductor wafers, and plastic substrates (PI, PET, PES) may be used, but are not limited to these. Substrates with holes or grooves may be used, and porous substrates with a large surface area may be used.

[0061] When using yttrium or lanthanide precursor compounds according to embodiments of this application to deposit yttrium or lanthanide oxide films, the deposition may include, but is not limited to, metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD). The MOCVD or ALD may be performed using deposition equipment, deposition conditions, and other reaction gases known in the art.

[0062] In one embodiment of this application, in the precursor composition for depositing yttrium or lanthanide metal oxide films of the present invention as described above, and in the deposition method comprising using the precursor composition for film deposition to form yttrium or lanthanide metal oxide films, the yttrium or lanthanide metal precursor compound of the present invention contained in the precursor composition for film deposition has the following excellent effects due to its low viscosity and high thermal stability: it can be used as a precursor for atomic layer deposition or chemical vapor deposition to form yttrium or lanthanide metal oxide films, especially even on substrates with patterned (grooved) surfaces or porous substrates. On a substrate or plastic substrate, an oxide film containing yttrium or lanthanide metals with a thickness of several μm to tens of nm can be uniformly formed in a temperature range of about 100°C to about 500°C or about 250°C to about 350°C. Moreover, an oxide film containing yttrium or lanthanide metals with a thickness of several μm to several nm or less can be uniformly formed on the entire surface of the substrate (including the surface of fine bumps (grooves), which includes the deepest surface of fine patterns (grooves) with an aspect ratio of about 1 to about 50, about 1 to about 100 or greater and a width of 1 μm to 10 nm or less, and the upper surface of the fine bumps (grooves).

[0063] In a thin film deposition method using a yttrium or lanthanide metal precursor compound according to one embodiment of this application, preferably, after the substrate is contained in a reaction chamber, the yttrium or lanthanide metal precursor compound is delivered onto the substrate using a transport gas or dilution gas, and then an oxide film containing yttrium or lanthanide metal is deposited at a wide range of deposition temperatures, from about 100°C to about 500°C, from about 150°C to about 450°C, from about 200°C to about 400°C, or from about 250°C to about 350°C.

[0064] According to one embodiment of this application, the deposition temperature of the yttrium or lanthanide metal-containing film is from about 250°C to about 350°C. Since the process temperature range applicable to devices such as memory devices and non-memory devices such as logic is wide, its applicability in a variety of fields is significant. Furthermore, because the film properties of the yttrium or lanthanide metal-containing oxide film vary with temperature, there is a need for yttrium or lanthanide metal precursor compounds that can be used over a wide temperature range; therefore, deposition is preferably performed within a deposition temperature range of about 250°C to about 350°C.

[0065] In one embodiment of this application, it is preferred to use one or more mixed gases selected from argon (Ar), nitrogen (N2), helium (He) or hydrogen (H2) as the transport gas or dilution gas.

[0066] In one embodiment of this application, various supply methods can be employed to deliver the yttrium or lanthanide metal precursor compound onto the substrate, including a bubbling method using a delivery gas to force vaporization of the precursor and a bypass method supplying it in a gaseous state by heating the container to increase the vapor pressure of the precursor. However, when the vapor pressure is low, a bypass method using a heated container for vaporization can be used. The yttrium or lanthanide metal precursor compound can be placed in a bubbling device or a VFC container, and then the precursor can be gaseously delivered and supplied to the chamber by bubbling with a delivery gas at a vapor pressure of about 0.1 to about 10 Torr and a temperature range of room temperature to about 150°C. Most preferably, a bypass method using a heated container to supply the yttrium or lanthanide metal precursor compound in a gaseous state can be used.

[0067] In one embodiment of this application, in order to vaporize the yttrium or lanthanide metal precursor compound, it is more preferable to use argon (Ar) or nitrogen (N2) for transport, or to use thermal energy or plasma, or to apply a bias voltage to the substrate.

[0068] In one embodiment of this application, the thin film may be a composite oxide film containing metals other than yttrium or lanthanides. For example, it may be a composite oxide film containing hafnium or zirconium with the following composition, but is not limited thereto: 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, Zr-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.

[0069] In one embodiment of this application, in order to deposit the yttrium- or lanthanide-containing oxide film or composite oxide film, it is preferred to use one or more of water vapor (H2O), oxygen (O2), oxygen plasma (O2 Plasma), nitrogen oxides (NO, N2O), nitrogen oxide plasma (N2O Plasma), hydrogen peroxide (H2O2), and ozone (O3).

[0070] Methods of implementing the invention

[0071] In the following description, embodiments will be used to illustrate the present application in more detail. However, the embodiments are merely examples to help understand the present application, and the content of the present application is not limited to the embodiments described below.

[0072] [Example]

[0073] <Preparation Example 1> Preparation of N,N'-isopropylpropionylimide amide (CH3)2CHNC(CH2CH3)NHCH(CH3)2

[0074] Place 152 g (0.862 mol) of triethyl orthopropionate and 102 g (1.725 mol) of isopropylamine in a 500 mL Schlenk flask, then slowly add 51.8 g (0.862 mol) of acetic acid, and reflux at above 170°C for 20 hours.

[0075] After the above reaction was completed, the solvent was removed under reduced pressure, and the mixture was extracted with a 1.1 equivalent aqueous solution of diethyl ether and sodium hydroxide (NaOH). The solvent was removed under reduced pressure, and the mixture was distilled under reduced pressure to obtain 97.6 g (72%) of a colorless and transparent liquid compound.

[0076] <Example 1> Bis-n-propylcyclopentadienyl-N,N'-isopropyl-ethylamidinyl yttrium [Cp(CH2)2CH3]2Y[(CH3)2CHNC(CH2CH3)NCH(CH3)2]

[0077] 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 the mixture was stirred at room temperature for 20 hours to prepare n-propyl-cyclopentadienylsodium.

[0078] 30 g (0.154 mol) of yttrium(III) chloride and 200 mL of n-hexane (C6H) 14 The solution was placed in a 1L Schlenk flask that had been flame-dried and then kept at room temperature. The synthesized n-propylcyclopentadienyl sodium was slowly added dropwise to the flask, and then stirred at room temperature for 20 hours to mix the reaction solution, so that yttrium(III) chloride reacted with n-propylcyclopentadienyl sodium to prepare a tris(n-propylcyclopentadienyl)yttrium(III) solution.

[0079] 34.2 g (0.123 mol) of n-butyllithium (n-BuLi, 23%) and 200 mL of n-hexane (C6H) were added. 14 After placing the mixture into a 500 mL flask, 19.2 g (0.123 mol) of N,N'-isopropylpropionylimide amide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] prepared in Preparation Example 1 was slowly added dropwise. The reaction solution was then stirred at room temperature for 3 hours to synthesize lithium amidinate.

[0080] The prepared lithium amidinate was slowly added dropwise to the prepared tris(n-propylcyclopentadienyl)yttrium(III) 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 47 g (67%) of a yellow liquid compound represented by the following chemical formula 1.

[0082] [Chemical Formula 1] ; 1H-NMR (400 MHz, C6D6, 25℃): δ 6.128, 6.057 (m, 8 1 H-NMR (400 MHz, C6D6, 25℃): δ6.128, 6.057 (m, 8H, C5 H 4-(CH2)2CH3), δ 3.351 (m, 2H, (CH3)2C H NC(CH2CH3)NC H (CH3)2), δ2.532 (t, 4H, C5H4-C H 2CH2CH3), δ 1.979 (q, 2H, (CH3)2CHNC(C H 2CH3)NCH(CH3)2), δ 1.653 (m, 4H, C5H4-CH2C H 2CH3), δ 1.001 (d, 12H, (C H 3)2CHNC(CH2CH3)NCH(C H 3)2), δ 0.969 (t, 6H, C5H4-CH2CH2C H 3), δ 0.915 (t, 3H, (CH3)2CHNC(CH2C H 3)NCH(CH3)2) <Example 2> Bis-n-propylcyclopentadienyl-N,N'-isopropyl-ethylamidinylgadolinium[Cp(CH2)2CH3]2Gd[(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 the mixture was stirred at room temperature for 20 hours to prepare n-propyl-cyclopentadienylsodium.

[0083] 50 g (0.190 mol) of gadolinium(III) chloride and 200 mL of n-hexane (C6H) 14 The solution was placed in a 1L Schlenk flask that had been flame-dried and then kept at room temperature. 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.

[0084] 42.3 g (0.152 mol) of n-butyllithium (n-BuLi, 23%) and 200 mL of n-hexane (C6H) were mixed. 14 After placing the mixture into a 500 mL flask, 23.7 g (0.152 mol) of N,N'-isopropylpropionylimide amide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] prepared in Preparation Example 1 was slowly added dropwise. The reaction solution was then stirred at room temperature for 3 hours to prepare lithium amidinate.

[0085] The synthesized lithium amidinate was slowly added dropwise to the synthesized tris(n-propylcyclopentadienyl)gadolinium(III) and refluxed for 20 hours.

[0086] 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.

[0087] [Chemical Formula 2] .

[0088] <Comparative Example 1> Bis-ethylcyclopentadienyl-N,N'-isopropyl-ethylamidinyl yttrium (EtCp)2Y[ i PrNC(Et)N i Preparation of Pr]

[0089] 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 the mixture was stirred at room temperature for 20 hours to prepare ethyl-cyclopentadienyl sodium.

[0090] 40 g (0.205 mol) of yttrium(III) chloride and 200 mL of n-hexane (C6H) 14 The solution was placed in a 1L Schlenk flask that had been flame-dried and then kept at room temperature. 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 tri(ethylcyclopentadienyl)yttrium(III) solution.

[0091] 45.6 g (0.164 mol) of n-butyllithium (n-BuLi, 23%) and 200 mL of n-hexane (C6H) were mixed. 14 After placing the solution into another 500 mL flask, 25.6 g (0.164 mol) of N,N'-isopropylpropionylimide amide [(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 a lithium amidinate solution. The lithium amidinate solution was then slowly added dropwise to a tris(ethylcyclopentadienyl)yttrium(III) solution prepared in a 1 L Schlenk flask and refluxed for 20 hours.

[0092] 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.

[0093] [Chemical Formula 3] ; Melting point (mp) 36℃ (760 torr); 1 H-NMR (400 MHz, C6D6, 25℃): δ 6.107, 6.057 (m, 8H, C5 H 4-CH2CH3), δ 3.337 (m, 2H, (CH3)2C H NC(CH2CH3)NC H (CH3)2), δ 2.552 (q, 4H, C5H4-C H 2CH3), δ 1.969 (q, 2H, (CH3)2CHNC(C H 2CH3)NCH(CH3)2), δ 1.237 (t, 6H, C5H4-CH2C H 3) δ 0.988 (d, 12H, (C) H 3)2CHNC(CH2CH3)NCH(C H 3)2), δ 0.896 (t, 3H, (CH3)2CHNC(CH2C H 3)NCH(CH3)2) Since the yttrium precursor compound of Comparative Example 1 is a solid at room temperature, it is less suitable for use in large-scale semiconductor production compared to the yttrium precursor compound of Example 1.

[0094] <Example 3> Bis-isopropylcyclopentadienyl-N,N'-isopropyl-ethylamidinyl yttrium (i PrCp)2Y[ i PrNC(Et)N i Preparation of P]

[0095] 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 the mixture was stirred at room temperature for 20 hours to prepare isopropylcyclopentadienylsodium.

[0096] 30 g (0.154 mol) of yttrium(III) chloride and 200 mL of n-hexane (C6H) 14 The solution was placed in a 1L Schlenk flask that had been flame-dried and then kept at room temperature. The synthesized isopropylcyclopentadienyl sodium was slowly added dropwise to the flask, and then stirred at room temperature for 20 hours to mix the reaction solution, so that yttrium(III) chloride reacted with isopropylcyclopentadienyl sodium to prepare a tris(isopropylcyclopentadienyl)yttrium(III) solution.

[0097] 34.2 g (0.123 mol) of n-butyllithium (n-BuLi, 23%) and 200 mL of n-hexane (C6H) were mixed. 14 After placing the mixture into a 500 mL flask, 10.2 g (0.123 mol) of N,N'-isopropylpropionylimide amide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] prepared in Preparation Example 1 was slowly added dropwise. The reaction solution was then stirred at room temperature for 3 hours to synthesize lithium amidinate.

[0098] The synthesized lithium amidinate was slowly added dropwise to the synthesized tris(isopropylcyclopentadienyl)yttrium(III) and refluxed for 20 hours.

[0099] 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.

[0100] [Chemical Formula 4] ; 1H-NMR (400 MHz, C6D6, 25℃): δ 6.158, 6.098 (m, 8H, C5 H 4-CH(CH3)2), δ3.359(m, 2H, (CH3)2C H NC(CH2CH3)NC H (CH3)2), δ 2.960 (m, 2H, C5H4-C H (CH3)2), δ 1.984 (q, 2H, (CH3)2CHNC(C H 2CH3)NCH(CH3)2), δ 1.293 (d, 12H, C5H4-CH(C H 3)2), δ 1.021 (d,12H, (C) H 3)2CHNC(CH2CH3)NCH(C H 3)2), δ 0.909 (t, 3H, (CH3)2CHNC(CH2C H 3)NCH(CH3)2) <Example 4> Bis-isopropylcyclopentadienyl-N,N'-isopropyl-ethylamidinylgadolinium ( i PrCp)2Gd[ i PrNC(Et)N i Preparation 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 the mixture was stirred at room temperature for 20 hours to prepare isopropylcyclopentadienylsodium.

[0101] 30 g (0.114 mol) of gadolinium(III) chloride and 200 mL of n-hexane (C6H) 14 The solution was placed in a 1L Schlenk flask that had been dried by flame and kept at room temperature. The synthesized isopropylcyclopentadienyl sodium was slowly added dropwise to the flask, and the reaction solution was stirred at room temperature for 20 hours to prepare a tris(isopropylcyclopentadienyl)gadolinium(III) solution.

[0102] 25.4 g (0.091 mol) of n-butyllithium (n-BuLi, 23%) and 200 mL of n-hexane (C6H) were mixed. 14 After placing the mixture into a 500 mL flask, 14.2 g (0.091 mol) of N,N'-isopropylpropionylimide amide [(CH3)2CHNC(CH2CH3)NHCH(CH3)2] prepared in Preparation Example 1 was slowly added dropwise. The reaction solution was then stirred at room temperature for 3 hours to synthesize lithium amidinate.

[0103] The synthesized lithium amidinate was slowly added dropwise to the synthesized tris(isopropylcyclopentadienyl)gadolinium(III) and refluxed for 20 hours.

[0104] 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.

[0105] [Chemical Formula 5] .

[0106] <Comparative Example 2> Di-isopropylcyclopentadienyl-N,N'-isopropyl-methylamidinyl yttrium ( i PrCp)2Y[ i PrNC(Me)N i Preparation of Pr]

[0107] Di-isopropylcyclopentadienyl-N,N′-isopropyl-methylamidinyl yttrium was prepared using the same synthesis method as in Example 3. i PrCp)2Y[ i PrNC(Me)N i The difference is that N,N′-isopropylmethylamidine is replaced with methyl instead of ethyl.

[0108] <Experimental Example 1> Comparison of the viscosity of precursor compounds

[0109] The precursor compounds of Comparative Example 2 are compared in the following [Table 1] ( i PrCp)2Y( i Pr-NC(Me)=N- i Pr) and the precursor compound of Example 1 of the present invention ( n PrCp)2Y( i Pr-NC(Et)=N- i Pr) and the precursor compound of Example 2 ( n PrCp)2Gd( i Pr-NC(Et)=N-i The viscosity of Pr. Contains the ligand N,N'-isopropyl-methylamidinyl ( i Pr-NC(Me)=N- i Precursor compounds of Pr i PrCp)2Y( i Pr-NC(Me)=N- i The viscosity of Pr (Comparative Example 2) was measured to be 81 cP, while the viscosity of the ligand N,N′-isopropyl-ethylamidinyl ( i Pr-NC(Et)=N- i The precursor compound of the present invention (Pr) n PrCp)2Y( i Pr-NC(Et)=N- i The measured viscosity of Pr (Example 1) was 69 cP, and ( n PrCp)2Gd( i Pr-NC(Et)=N- i The viscosity of Pr (Example 2) was measured to be 68 cP.

[0110] [Table 1]

[0111] When used by heating and vaporizing a container carrying ALD or CVD precursors, if the precursor has a low vapor pressure and high viscosity, it may remain in the dead space of the gas supply line or valve. When performing instantaneous vaporization by injecting liquid ALD or CVD precursors into a flash evaporator heated to a high temperature, high viscosity can easily lead to clogging of the flash evaporator. Furthermore, liquids with excessively high viscosity cannot be used in liquid metering pumps.

[0112] For example, if it is necessary to reduce the viscosity of the liquid used in pumps for conveying liquids in ALD or CVD units employing liquid delivery devices and flash evaporators, for instance, to keep it below 9 cP, then a lower viscosity liquid (solvent) needs to be mixed into a higher viscosity precursor to reduce the viscosity. If a larger amount of the lower viscosity liquid is mixed, the precursor content in the viscosity-reduced mixture is relatively small, and the precursor gas supply is reduced when the same volume of liquid is vaporized. Therefore, when viscosity adjustment is required, it is advantageous to reduce the amount of the lower viscosity liquid mixed. The precursor compounds of Examples 1 and 2 of this application are more advantageous for use as ALD or CVD precursors because they have lower viscosities compared to the precursor of Comparative Example 2, which is already known.

[0113] The following [Table 2] and Figure 1The table shows the required octane mixing ratio when using octane as a low-viscosity liquid (solvent) to adjust the viscosity of the mixture to 8.5 ± 0.5 cP. (Based on Table 2 and...) Figure 1 Even when the precursor compounds of Examples 1 and 2 are mixed with less octane than the precursor compound of Comparative Example 2, the viscosity of the mixture can be reduced to 8.5 ± 0.5 cP.

[0114] [Table 2]

[0115] <Experimental Example 2> Oxide film deposition characteristics of yttrium precursor compounds based on substrate temperature

[0116] Atomic Layer Deposition (ALD) was performed using yttrium precursor compounds prepared according to the methods of Examples 1 and 3. Oxygen source O3 was used as the reaction gas. First, a silicon wafer was immersed in a piranha solution composed of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2) in a 4:1 ratio for 10 minutes, then removed and immersed in a diluted HF solution for about 2 minutes to remove the oxide film on the silicon wafer surface. A yttrium oxide film was then prepared by atomic layer deposition (ALD).

[0117] To measure the deposition characteristics at different substrate temperatures, an ALD process was performed by heating the substrate to 300°C, 310°C, 320°C, and 340°C. The yttrium precursor compound was placed in a stainless steel container and then heated to 150°C for use. The process pressure of the ALD reactor was maintained at 1 Torr. The yttrium precursor compound gas was supplied to the ALD reactor by flowing argon (Ar) gas at a flow rate of 300 sccm through the stainless steel container containing the yttrium precursor compound. The ALD gas cycle (consisting of 3 seconds of yttrium precursor supply, 10 seconds of purging, 10 seconds of O3 supply, and 5 seconds of purging) was repeated 100 times at each substrate temperature to deposit a yttrium oxide film. Figure 2 The figure shows film growth (GPC) per ALD gas supply cycle determined by measuring the thickness of the oxide film, assuming substrate temperature. The yttrium precursors of Examples 1 and 3 both exhibited a constant GPC of approximately 0.3 Å / cycle in the temperature range of 300°C to 340°C.

[0118] When GPC remains constant over a wide temperature range, the deposited film thickness remains constant even with temperature variations, thus facilitating the application of ALD in semiconductor manufacturing. As semiconductor devices continue to miniaturize and the dielectric film thickness of DRAM capacitors gradually decreases, it becomes necessary to form films with constant thickness over a wide temperature range. Therefore, as... Figure 2As shown, since the yttrium precursors of Examples 1 and 3 of the present invention have a constant GPC over a wide temperature range, they are more advantageous for yttrium oxide (Y2O3) with fine and uniform thickness adjustment according to the deposition requirements of the ALD process compared to existing yttrium precursors with GPC that are not constant with temperature.

[0119] <Experimental Example 3> Based on the precursor supply time of yttrium precursor compounds, the oxide film deposition characteristics

[0120] Yttrium oxide films were prepared under the same conditions as in Experimental Example 2, wherein the substrate temperature was fixed at 300°C, and the yttrium precursor supply time in the ALD gas supply cycle was changed from 3 seconds to 1 second, 5 seconds, and 7 seconds, respectively. This ALD gas supply cycle was repeated 100 times to deposit the yttrium oxide film. The GPC obtained by measuring the oxide film thickness is then shown in [the figure]. Figure 3 In ideal ALD conditions, GPC needs to remain constant even with increased precursor supply time. When ALD is performed at temperatures where the precursor compound is not thermally stable, film thickness increases with increasing precursor supply time.

[0121] exist Figure 3 As can be seen, the yttrium precursors of Examples 1 and 3 both exhibit constant GPC when the precursor supply time is 3 seconds or more. To form a film of constant thickness on a semiconductor DRAM capacitor with a very large aspect ratio (50 or greater), a precursor whose thickness does not increase even with an increased precursor supply time is required. When it is necessary to extend the precursor supply time to supply a sufficient amount of precursor to a substrate with a larger actual surface area than apparent surface area due to the large aspect ratio, if a precursor whose thickness increases with the precursor supply time is used, it is impossible to form a film of the same thickness at the top and bottom of a groove with a large aspect ratio. Therefore, as... Figure 3 As shown, even with an increase in precursor supply time, the yttrium precursors of Embodiments 1 and 3 of the present invention do not lead to an increase in film thickness. Therefore, compared with existing yttrium precursors (where film thickness increases with increasing precursor supply time), they are more advantageous for forming films of constant thickness on structures with a large aspect ratio and can be used to form capacitors for semiconductor DRAM.

[0122] The foregoing description of this application is for illustrative purposes only, and those skilled in the art will understand that it can be easily modified into other specific forms without altering the technical spirit or essential features of this application. Therefore, it should be understood that the above embodiments are illustrative in all respects and not restrictive. For example, elements described as a single form can also be implemented in a distributed manner, and similarly, multiple elements described as distributed can also be implemented in a combined form.

[0123] The scope of this application is set forth by the appended claims rather than by the detailed description above, and all variations or modifications derived from the meaning and scope of the claims and the concept of their equivalents shall be construed as being included within the scope of this application.

Claims

1. A precursor compound containing yttrium or a lanthanide metal, represented by the following chemical formula I: [Chemical Formula I] (R 1 Cp)2M[(CH3)2CH-N-C(CH2CH3)=N-CH(CH3)2]; In the chemical 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 n-propyl ( n Pr) or isopropyl ( i Pr), The Cp is cyclopentadienyl.

2. The yttrium- or lanthanide metal precursor compound according to claim 1, wherein the yttrium- or lanthanide metal precursor compound is a liquid at room temperature.

3. The yttrium- or lanthanide metal-containing precursor compound according to claim 1, wherein the yttrium- or lanthanide metal-containing precursor compound is selected from 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- i Pr)、( 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-N-C(Et)=N- i (Pr) as well as( i (PrCp)2Lu( i Pr-N-C(Et)=N- i (Pr).

4. A precursor composition for forming a yttrium or lanthanide metal-containing film, comprising a yttrium or lanthanide metal-containing precursor compound according to any one of claims 1 to 3.

5. The precursor composition for forming a yttrium- or lanthanide-containing film according to claim 4, wherein the precursor composition for forming a yttrium- or lanthanide-containing film comprises one or more yttrium- or lanthanide-containing precursor compounds selected from: ( 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- i Pr)、( 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-N-C(Et)=N- i Pr) and i (PrCp)2Lu i Pr-N-C(Et)=N- i Pr).

6. The precursor composition for forming a yttrium or lanthanide metal-containing film according to claim 4, wherein the yttrium or lanthanide metal-containing film is a yttrium or lanthanide metal film, a yttrium or lanthanide metal-containing oxide film, a yttrium or lanthanide metal-containing nitride film, or a yttrium or lanthanide metal-containing carbide film.

7. The precursor composition for forming a yttrium or lanthanide metal-containing film according to claim 4 further comprises one or more nitrogen sources selected from ammonia, nitrogen, hydrazine and dimethylhydrazine.

8. The precursor composition for forming a yttrium or lanthanide metal-containing film according to claim 4 further comprises one or more oxygen sources selected from water vapor, oxygen, and ozone.

9. A method for forming a film containing yttrium or a lanthanide metal, comprising: The yttrium or lanthanide metal film is formed using the precursor composition for forming a yttrium or lanthanide metal film according to any one of claims 4 to 8.

10. The method for forming a film containing yttrium or lanthanide metals according to claim 9, wherein the film containing yttrium or lanthanide metals is deposited by chemical vapor deposition or atomic layer deposition.

11. The method for forming a film containing yttrium or lanthanide metals according to claim 9, wherein the thickness of the film containing yttrium or lanthanide metals is from 1 nm to 10 μm.

12. The method for forming a film containing yttrium or lanthanide metals according to claim 9, wherein the film containing yttrium or lanthanide metals is formed in a temperature range of 100°C to 500°C.

13. The method of forming a yttrium or lanthanide metal film according to claim 9, wherein the yttrium or lanthanide metal film is formed on a substrate having an aspect ratio of 1 to 100 and a width of 10 nm to 1 μm.

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