Thermally stable ruthenium precursor composition and method for forming a ruthenium-containing film

Abstract

The present application relates to a thermally stable film-forming ruthenium precursor compound, a film-forming precursor composition containing the ruthenium precursor compound, and a method for forming a ruthenium-containing film using the film-forming precursor.

Description

Technical Field

[0001] The present application relates to a ruthenium precursor compound for film formation having high thermal stability, a precursor composition for film formation containing the ruthenium precursor compound, and a method for forming a ruthenium-containing film using the precursor for film formation.

Background Art

[0002] Ruthenium (Ru) metal can be used as a wiring material for semiconductor devices because it conducts electricity well like copper (Cu), tungsten (W), and cobalt (Co). As the integration of semiconductor devices progresses and the width of the metal wiring becomes narrower, the resistance of the metal wiring increases. When ruthenium metal is used for the wiring of semiconductor devices, when the width of the metal wiring is very narrow, such as 40 nm or less, the resistance increases slightly more than that of copper or cobalt. Therefore, the ruthenium (Ru) metal is being studied as a next-generation wiring material. In order to fill the narrow grooves required for the wiring of next-generation semiconductor devices with ruthenium metal, it is advantageous to supply a gaseous ruthenium compound to the substrate surface by chemical vapor deposition (CVD) or atomic layer deposition (ALD) to form a ruthenium metal film.

[0003] For the above purpose, several ruthenium precursor compositions that can be used in CVD or ALD are known. However, in order to use the ruthenium (Ru) metal in the manufacture of semiconductor devices, a thermally stable ruthenium precursor composition whose composition does not change at the temperature at which the precursor composition is vaporized is required.

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

[0005] This application aims to provide a ruthenium precursor compound for film formation with high thermal stability, a film-forming precursor composition containing the ruthenium precursor compound, and a method for forming a ruthenium-containing film using the film-forming precursor.

[0006] However, the problems that this application aims to solve are not limited to those mentioned above, and other problems not mentioned should be clearly understandable to an average engineer from the following description. [Means for solving the problem]

[0007] The first aspect of this application provides a ruthenium precursor compound represented by the following chemical formula I. [ka] In the above chemical formula I, R 1 ~R 6 Each is independently of hydrogen; substituted or unsubstituted linear or branched C 1-10 Alkyl alkyl group; or substituted or unsubstituted C 3-10 It is a cycloalkyl group, and when the alkyl group or cycloalkyl group is substituted, linear or branched C 1-3 It is substituted with an alkyl group.

[0008] A second aspect of this application provides a film-forming precursor composition comprising one or more ruthenium precursor compounds according to the first aspect.

[0009] A third aspect of this application provides a method for forming a ruthenium-containing film, which includes forming a ruthenium-containing film using a film-forming precursor composition comprising a ruthenium precursor compound according to the first aspect. [Effects of the Invention]

[0010] In the case of Ru precursor compositions with low thermal stability, the proportion of dissimilar materials changes during vaporization. However, according to the embodiment of the present invention, the ruthenium-containing film formation method using the ruthenium precursor composition of the present invention is advantageous for forming a ruthenium film with consistent properties because the composition of the vaporized precursor composition does not change during use, and can be used in the manufacturing process of semiconductor devices.

[0011] According to the embodiment of this invention, a ruthenium-containing film with a thickness of several nanometers to several micrometers can be uniformly formed on substrates with surface patterns (grooves), porous substrates, or plastic substrates, even within a wide range of temperatures.

[0012] According to the embodiment of this application, the ruthenium-containing film utilizing the ruthenium precursor composition of this application can be applied in various ways depending on the application. [Brief explanation of the drawing]

[0013] [Figure 1a] This is a transmission electron microscope (TEM) image of a ruthenium-containing film formed using a mixture of oxygen (O2) and nitrogen (N2) gases in a ratio of 70 sccm:140 sccm, respectively, as the reaction gases. [Figure 1b]This is a transmission electron microscope (TEM) image of a ruthenium-containing film formed using a mixture of oxygen (O2) and nitrogen (N2) gases in a ratio of 100 sccm:100 sccm, respectively, as the reaction gases. [Figure 1c] This is a transmission electron microscope (TEM) image of a ruthenium-containing film formed using a mixture of oxygen (O2) and nitrogen (N2) gases in a ratio of 200 sccm:0 sscm, respectively, as the reaction gases. [Figure 2] This shows the film composition based on Ru thickness measured by Auger electron spectroscopy. [Modes for carrying out the invention]

[0014] In the following, with reference to the attached drawings, embodiments and examples of the present invention will be described in detail so that those with ordinary skill in the art to which the present invention pertains can easily implement it. However, the present invention can be embodied in a variety of different forms and is not limited to the embodiments and examples described herein. Furthermore, in order to clearly illustrate the present invention, parts unrelated to the description have been omitted from the drawings, and similar parts throughout the specification are denoted by similar reference numerals.

[0015] Throughout the specification of this application, when a part is described as being "connected" to another part, this includes not only cases where they are "directly connected," but also cases where they are "electrically connected" with other elements in between.

[0016] Throughout the specification of this application, when a member is described as being "on top of" another member, this includes not only cases where the member is in contact with another member, but also cases where there is yet another member between the two members.

[0017] Throughout the specification of the present application, when a certain part states that a certain component "includes" something, this means that, unless otherwise stated to the contrary, it does not exclude other components, but may further include other components.

[0018] As used in this specification, terms such as "about" and "substantially" are used in the sense of that numerical value or a value close thereto when manufacturing and material tolerances inherent to the recited meaning are presented, and are used to prevent unscrupulous infringers from improperly using disclosure content where an exact or absolute numerical value is recited to aid in the understanding of the present application.

[0019] Throughout the specification of the present application, the term "step of ~" or "step of ~" does not mean "step for ~".

[0020] Throughout the specification of the present application, the term "these combinations" included in the Markush-type expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-type expression, and means including one or more selected from the group consisting of the said components.

[0021] Throughout the specification of the present application, the description of "A and / or B" means "A or B, or A and B".

[0022] Throughout the specification of the present application, 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 said alkyl or alkyl group is a methyl group (Me), an ethyl group (Et), an n-propyl group ( n Pr), an iso-propyl group ( i Pr), an n-butyl group ( n Bu), an iso-butyl group ( i Bu), a tert-butyl group (tert-Bu, t Bu), a 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 Examples include, but are not limited to, Pe, 3-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, 4,4-dimethylpentyl group, octyl group, 2,2,4-trimethylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof.

[0023] Throughout the specification of this application, the term "film" means "film" or "thin film."

[0024] The following will provide a detailed explanation of examples of the present application, but the present application is not limited to these examples.

[0025] The first aspect of this application provides a ruthenium precursor compound represented by the following chemical formula I. [ka] In the above chemical formula I, R 1 ~R 6 Each is independently of hydrogen; substituted or unsubstituted linear or branched C 1-10 Alkyl alkyl group; or substituted or unsubstituted C 3-10 It is a cycloalkyl group, and when the alkyl group or cycloalkyl group is substituted, linear or branched C 1-3 It is substituted with an alkyl group.

[0026] In one embodiment of the present application, R 1 , R 2 , R 5 and R 6 One or more of these are substituted or unsubstituted linear or branched C 1-10 Alkyl alkyl group; or substituted or unsubstituted C 3-10 It may also be a cycloalkyl group. In one embodiment of the present application, the ruthenium compound is R 1 , R2 , R 5 and R 6 This excludes the case where all of them are hydrogen.

[0027] In one embodiment of the present application, the linear or branched C 1-10 Alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group, neo-pentyl group, 3-pentyl group, n-hexyl group, iso-hexyl group, sec-hexyl group, tert-hexyl group, neo-hexyl group, n-heptyl group, iso-heptyl group, sec-heptyl group, te The group may include, but is not limited to, rt-heptyl group, neo-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, tert-octyl group, neo-octyl group, n-nonyl group, iso-nonyl group, sec-nonyl group, tert-nonyl group, neo-nonyl group, n-decyl group, iso-decyl group, sec-decyl group, tert-decyl group, neo-decyl group, and isomorphs thereof. In one embodiment of the present application, the linear or branched C 1-10 The alkyl group may be a methyl group, an ethyl group, an n-propyl group, or an iso-propyl group.

[0028] In one embodiment of the present application, the C 3-10 The cycloalkyl group may include, but is not limited to, a group selected from the group consisting of a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and isomers thereof. In one embodiment of the present application, the C 3-10 The cycloalkyl group may be, but is not limited to, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group.

[0029] In the case of p-cymene (p-cymene)[CH2=C(CH3)CH=C(CH3)2]Ru(MeC-cymene) H=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[EtCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ n PrCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ i PrCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ n BuCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ i BuCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ sec BuCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ t BuCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)(CH3CH=CH-CH=CHCH3)Ru、(p-cymene)(Me2C=CH-CH=CHCH3)Ru、(p-cymene)(EtMeC=CH-CH=CHCH3)Rumene)(p n PrMeC=CH-CH=CHCH3)Ru、(p-cymene)( i PrMeC=CH-CH=CHCH3)Ru、(p-cymene)( n BuMeC=CH-CH=CHCH3)Ru、(p-cymene)( i BuMeC=CH-CH=CHCH3)Ru、(p-cymene)( sec BuMeC=CH-CH=CHCH3)Ru、(p-cymene)( t BuMeC=CH-CH=CHCH3)Ru、(p-cymene)(CH2=CHCH=CHCH2CH3)Ru、(p-cymene)(MeCH=CHCH=CHCH2CH3)Ru、(p-cymene)(EtCH=CHCH=CHCH2CH3)Ru、(p-cymene) n PrCH=CHCH=CHCH2CH3)Ru、(p-cymene)( i PrCH=CHCH=CHCH2CH3)Ru、(p-cymene)( nBuCH=CHCH=CHCH2CH3)Ru, (p-cymene)( i BuCH=CHCH=CHCH2CH3)Ru, (p-cymene)( sec BuCH=CHCH=CHCH2CH3)Ru, and (p-cymene)( t It may be selected from BuCH=CHCH=CHCH2CH3)Ru, but is not limited to this.

[0030] In one embodiment of the present invention, the ruthenium precursor compound may be selected from the following formulas 1 to 3. [ka]

[0031] A second aspect of this application provides a film-forming precursor composition comprising one or more ruthenium precursor compounds according to the first aspect.

[0032] While detailed explanations have been omitted for parts that overlap with the first aspect of this application, the content explained in the first aspect of this application can be similarly applied to the second aspect of this application even if the explanation is omitted.

[0033] In one embodiment of the present application, R 1 , R 2 , R 5 and R 6 One or more of these are substituted or unsubstituted linear or branched C 1-10 Alkyl alkyl group; or substituted or unsubstituted C 3-10 It may also be a cycloalkyl group. In one embodiment of the present application, the ruthenium compound is R 1 , R 2 , R 5 and R 6 This excludes the case where all of them are hydrogen.

[0034] In one embodiment of the present application, the linear or branched C 1-10Alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group, neo-pentyl group, 3-pentyl group, n-hexyl group, iso-hexyl group, sec-hexyl group, tert-hexyl group, neo-hexyl group, n-heptyl group, iso-heptyl group, sec-heptyl group, te The group may include, but is not limited to, rt-heptyl group, neo-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, tert-octyl group, neo-octyl group, n-nonyl group, iso-nonyl group, sec-nonyl group, tert-nonyl group, neo-nonyl group, n-decyl group, iso-decyl group, sec-decyl group, tert-decyl group, neo-decyl group, and isomorphs thereof. In one embodiment of the present application, the linear or branched C 1-10 The alkyl group may be a methyl group, an ethyl group, an n-propyl group, or an iso-propyl group.

[0035] In one embodiment of the present application, the C 3-10 The cycloalkyl group may include, but is not limited to, a group selected from the group consisting of a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and isomers thereof. In one embodiment of the present application, the C 3-10 The cycloalkyl group may be, but is not limited to, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group.

[0036] In one embodiment of the present invention, the film-forming precursor composition may be a mixture containing one or more of the following ruthenium precursor compounds.

[0037] (p-cymene)[CH2=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[MeCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[EtCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ n PrCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ i PrCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ n BuCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ i BuCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ sec BuCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)[ t BuCH=C(CH3)CH=C(CH3)2]Ru、(p-cymene)(CH3CH=CH-CH=CHCH3)Ru、(p-cymene)(Me2C=CH-CH=CHCH3)Ru、(p-cymene)(EtMeC=CH-CH=CHCH3)Ru、(p-cymene)( n PrMeC=CH-CH=CHCH3)Ru、(p-cymene)( i PrMeC=CH-CH=CHCH3)Ru、(p-cymene)( n BuMeC=CH-CH=CHCH3)Ru、(p-cymene)( i BuMeC=CH-CH=CHCH3)Ru、(p-cymene)( sec BuMeC=CH-CH=CHCH3)Ru、(p-cymene)( t BuMeC=CH-CH=CHCH3)Ru、(p-cymene)(CH2=CHCH=CHCH2CH3)Ru、(p-cymene)(MeCH=CHCH=CHCH2CH3)Ru、(p-cymene)(EtCH=CHCH=CHCH2CH3)Ru、(p-cymene)( n PrCH=CHCH=CHCH2CH3)Ru、(p-cymene)( i PrCH=CHCH=CHCH2CH3)Ru、(p-cymene)( nBuCH=CHCH=CHCH2CH3)Ru, (p-cymene)( i BuCH=CHCH=CHCH2CH3)Ru, (p-cymene)( sec BuCH=CHCH=CHCH2CH3)Ru, and (p-cymene)( t (IbCH=CHCH=CHCH2CH3)Ru

[0038] In one embodiment of the present invention, the ruthenium precursor compound may contain one or more compounds selected from the following: [ka]

[0039] In one embodiment of the present invention, the film may be one or more selected from a ruthenium metal film, a ruthenium-containing oxide film, a ruthenium-containing nitride film, a ruthenium-containing carbide film, and combinations thereof, but is not limited thereto.

[0040] In one embodiment of the present invention, the ruthenium-containing oxide film or the ruthenium-containing nitride film may be applied in various ways in semiconductors, non-semiconductors, and display elements, depending on their application, but is not limited thereto.

[0041] In one embodiment of the present application, the film-forming precursor composition may further contain, but is not limited to, one or more nitrogen sources selected from ammonia, nitrogen, hydrazine, and dimethylhydrazine.

[0042] In one embodiment of the present invention, the film-forming precursor composition may further contain, but is not limited to, one or more oxygen sources selected from water vapor, oxygen, and ozone.

[0043] A third aspect of this application provides a method for forming a ruthenium-containing film, which includes forming a ruthenium-containing film using a film-forming precursor composition comprising a ruthenium precursor compound according to the first aspect.

[0044] While detailed explanations have been omitted for portions that overlap with the first and second aspects of this application, the content explained for the first and second aspects of this application can be similarly applied to the third aspect of this application, even if such explanations are omitted.

[0045] In one embodiment of the present invention, the ruthenium precursor compound contained in the film-forming precursor composition may include one or more compounds selected from the following: [ka]

[0046] In one embodiment of the present invention, the ruthenium-containing film may be deposited by chemical vapor deposition (CVD) or atomic layer deposition (ALD), but is not limited thereto.

[0047] In one embodiment of the present invention, the composition of one or more ruthenium precursor compounds contained in the film-forming precursor composition may be maintained during the process of heating and vaporizing the film-forming precursor composition. In one embodiment of the present invention, the composition of one or more ruthenium precursor compounds contained in the film-forming precursor composition may be maintained at about 70% or more, about 80% or more, about 90% or more, or about 95% or more during the process of heating and vaporizing the film-forming precursor composition.

[0048] In one embodiment of the present application, the ruthenium-containing film may be deposited by metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but is not limited thereto. In one embodiment of the present application, the chemical vapor deposition or atomic layer deposition may be carried out using deposition apparatus, deposition conditions, and one or more additional reaction gases known in the art, but is not limited thereto.

[0049] In one embodiment of the present invention, the reaction gas used in the ALD and CVD method may be a gas used in semiconductor processes, such as hydrogen (H2) gas, ammonia (NH3) gas, oxygen (O2) gas, or ozone (O3) gas, to form a ruthenium-containing film, but is not limited thereto. For example, when hydrogen gas and / or ammonia gas are used to form a film in the ALD and CVD method, a ruthenium-containing film with fewer impurities can be formed. For example, when oxygen gas or ozone gas is used to form a film, a ruthenium oxide film can be formed, but is not limited thereto.

[0050] In one embodiment of the present invention, the ruthenium-containing film formation method includes, but is not limited to, supplying a film-forming precursor composition containing a ruthenium precursor compound in a gaseous state onto a substrate located in a deposition chamber to form a ruthenium-containing film on the surface of the substrate.

[0051] In one embodiment of the present application, the ruthenium-containing film may be formed in a temperature range of room temperature to about 400°C, but is not limited thereto. For example, the ruthenium-containing film may be formed in a temperature range of room temperature to about 400°C, room temperature to about 350°C, room temperature to about 250°C, room temperature to about 200°C, room temperature to about 150°C, room temperature to about 100°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 400°C, about 150°C to about 350°C, about 150°C to about 400°C, about 150°C to about 350°C, and about 150°C to The ruthenium-containing film may be formed in a temperature range of approximately 300°C, approximately 150°C to approximately 250°C, approximately 150°C to approximately 200°C, approximately 200°C to approximately 400°C, approximately 200°C to approximately 350°C, approximately 200°C to approximately 300°C, approximately 200°C to approximately 250°C, approximately 250°C to approximately 400°C, approximately 250°C to approximately 350°C, approximately 250°C to approximately 300°C, approximately 300°C to approximately 400°C, approximately 300°C to approximately 350°C, or approximately 350°C to approximately 400°C, but is not limited thereto. In one embodiment of the present application, the ruthenium-containing film may be formed in a temperature range of approximately 200°C to approximately 400°C, or approximately 300°C to approximately 400°C.

[0052] In one embodiment of the present application, the ruthenium-containing film may be formed in a thickness range of approximately 1 nm to approximately 500 nm, but may be applied in various ways depending on the application, and is not limited thereto. For example, the ruthenium-containing film may be approximately 1 nm to approximately 500 nm, approximately 1 nm to approximately 400 nm, approximately 1 nm to approximately 300 nm, approximately 1 nm to approximately 200 nm, approximately 1 nm to approximately 100 nm, approximately 1 nm to approximately 50 nm, approximately 1 nm to approximately 40 nm, approximately 1 nm to approximately 30 nm, approximately 1 nm to approximately 20 nm, approximately 1 nm to approximately 10 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, and approximately 10 nm ~ about 100 nm, about 10 nm - about 50 nm, about 10 nm - about 40 nm, about 10 nm - about 30 nm, about 10 nm - about 20 nm, about 20 nm - about 500 nm, about 20 nm - about 400 nm, about 20 nm - about 30 0nm, about 20nm to about 200nm, about 20nm to about 100nm, about 20nm to about 50nm, about 20nm to about 40nm, about 20nm to about 30nm, about 30nm to about 500nm, about 30nm to about 400nm, about 3 0nm to about 300nm, about 30nm to about 200nm, about 30nm to about 100nm, about 30nm to about 50nm, about 30nm to about 40nm, about 40nm to about 500nm, about 40nm to about 400nm, about 40nm Approximately 300nm, approximately 40nm to approximately 200nm, approximately 40nm to approximately 100nm, approximately 40nm to approximately 50nm, approximately 50nm to approximately 500nm, approximately 50nm to approximately 400nm, approximately 50nm to approximately 300nm, approximately 50nm to approximately 200 The ruthenium-containing film may be formed in a thickness range of approximately 1 nm to 50 nm, approximately 50 nm to 100 nm, approximately 100 nm to 500 nm, approximately 100 nm to 400 nm, approximately 100 nm to 300 nm, approximately 100 nm to 200 nm, approximately 200 nm to 500 nm, approximately 200 nm to 400 nm, approximately 200 nm to 300 nm, approximately 300 nm to 500 nm, approximately 300 nm to 400 nm, or approximately 400 nm to 500 nm, but is not limited thereto. In one embodiment of the present application, the ruthenium-containing film may be formed in a thickness range of approximately 1 nm to 50 nm.

[0053] In one embodiment of the present invention, the ruthenium-containing film may be formed on one or more substrates selected from ordinary silicon semiconductor wafers, compound semiconductor wafers, and plastic substrates (PI, PET, PES, and PEN), but is not limited thereto. Furthermore, substrates with holes or grooves may be used, or porous substrates with a large surface area may be used, but is not limited thereto. Moreover, the ruthenium-containing film may be formed simultaneously or sequentially on the entire substrate or a portion thereof on a substrate in which two or more different types of substrates are in contact or connected, but is not limited thereto.

[0054] In one embodiment of the present invention, the ruthenium-containing film may be formed on a substrate containing irregularities (grooves) 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. The irregularities (grooves) may be in the shape of holes or trenches. For example, the aspect ratio is approximately 1 or more, approximately 10 or more, approximately 30 or more, approximately 50 or more, approximately 1 to approximately 100, approximately 1 to approximately 90, approximately 1 to approximately 80, approximately 1 to approximately 70, approximately 1 to approximately 60, approximately 1 to approximately 50, approximately 1 to approximately 40, approximately 1 to approximately 30, approximately 1 to approximately 20, approximately 1 to approximately 10, approximately 10 to approximately 100, approximately 10 to approximately 90, approximately 10 to approximately 80, approximately 10 to approximately 70, approximately 10 to approximately 60, approximately 10 to approximately 50, approximately 10 to approximately 40, approximately 10 to approximately 30, approximately 10 to approximately 30, approximately 10 to approximately 20, approximately 20 to approximately 100, approximately 20 to approximately 90, approximately 20 to approximately 80, approximately 20 to approximately 70, approximately 20 to approximately 60, approximately 20 to approximately 50, approximately 20 to approximately 40, approximately 20 to approximately 30, approximately 30 to approximately 1 00, approximately 30-90, approximately 30-80, approximately 30-70, approximately 30-60, approximately 30-50, approximately 30-40, approximately 40-100, approximately 40-90, approximately 40-80, approximately 40-70, approximately 40-60, approximately 40-50, approximately 50-100, approximately 50-90, approximately 50-80, approximately 50-70, approximately 50-60, approximately 60-100, approximately 60-90, approximately 60-80, approximately 60-70, approximately 70-100, approximately 70-90, approximately 70-80, approximately 80-100, approximately 80-90, or approximately 90-100, but are not limited to these. Furthermore, for example, the widths are approximately 10 nm to 1 μm, 10 nm to 900 nm, 10 nm to 800 nm, 10 nm to 700 nm, 10 nm to 600 nm, 10 nm to 500 nm, 10 nm to 400 nm, 10 nm to 300 nm, 10 nm to 200 nm, 10 nm to 100 nm, 10 nm to 90 nm, 10 nm to 80 nm, 10 nm to 70 nm, and 10 nm to 60 nm. , about 10 to about 50nm, about 10nm to about 40nm, about 10nm to about 30nm, about 10nm to about 20nm, about 20nm to about 1μm, about 20nm to about 900nm, about 20nm to about 800nm, about 20nm to about 70 0nm, about 20nm to about 600nm, 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 20nm to about 90nm,Approximately 20nm~80nm, approximately 20nm~70nm, approximately 20nm~60nm, approximately 20nm~50nm, approximately 20nm~40nm, approximately 20nm~30nm, approximately 30nm~1μm, approximately 30nm~900nm, approximately 30nm~800nm, approximately 30nm~700nm, approximately 30nm~600nm, approximately 30nm~500nm, approximately 30nm~400nm, approximately 30nm~300nm, approximately 30nm~200nm, approximately 30nm~100nm, approximately 30nm~90nm, approximately 30nm~80nm, approximately 30nm~70nm, approximately 30nm~60nm Approximately 30-50nm, approximately 30nm-40nm, approximately 40nm-1μm, approximately 40nm-900nm, approximately 40nm-800nm, approximately 40nm-700nm, approximately 40nm-600nm, approximately 40nm-500nm, approximately 40nm-400nm, approximately 40nm-300nm, approximately 40nm-200nm, approximately 40nm-100nm, approximately 40nm-90nm, approximately 40nm-80nm, approximately 40nm-70nm, approximately 40nm-60nm, approximately 40-50nm, approximately 50nm-1μm, approximately 50nm-900nm, approximately 50nm-800nm, approximately 50nm~approx. 700nm, approx. 50nm~approx. 600nm, approx. 50nm~approx. 500nm, approx. 50nm~approx. 400nm, approx. 50nm~approx. 300nm, approx. 50nm~approx. 200nm, approx. 50nm~approx. 100nm, approx. 50nm~approx. 90nm, approx. 50nm~approx. 80nm, approx. 50nm~approx. 70nm, approx. 50nm~approx. 60nm, approx. 100nm~approx. 1μm, approx. 100nm~approx. 900nm, approx. 100nm~approx. 800nm, approx. 100nm~approx. 700nm, approx. 100nm~approx. 600nm, approx. 100nm~approx. 500nm, approx. 100nm~approx. 400nm, approx. 100nm~approx. 300nm Approximately 100nm to approximately 200nm, approximately 200nm to approximately 1μm, approximately 200nm 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.The wavelength ranges may be approximately 400nm to 800nm, 400nm to 700nm, 400nm to 600nm, 400nm to 500nm, 500nm to 1μm, 500nm to 900nm, 500nm to 800nm, 500nm to 700nm, 500nm to 600nm, 600nm to 1μm, 600nm to 900nm, 600nm to 800nm, 600nm to 700nm, 700nm to 1μm, 700nm to 900nm, 700nm to 800nm, 800nm ​​to 1μm, 800nm ​​to 900nm, or 900nm to 1μm, but are not limited to these ranges.

[0055] In one embodiment of the present application, the ruthenium precursor compound of the present invention contained in the film-forming precursor composition has low density and high thermal stability, allowing it to be used as a precursor for atomic layer deposition or chemical vapor deposition to form a ruthenium-containing film. In particular, it can uniformly form a ruthenium-containing film with a thickness of several nanometers to several micrometers on substrates with surface patterns (grooves), porous substrates, or plastic substrates in temperature ranges of room temperature to about 400°C, about 200°C to about 400°C, or about 300°C to about 400°C.

[0056] In one embodiment of the present invention, the ruthenium-containing film formation method preferably involves placing a substrate in a reaction chamber, then using a transport gas or diluent gas to transfer the ruthenium precursor compound onto the substrate, and depositing a ruthenium-containing oxide thin film or nitride thin film at a wide deposition temperature range of room temperature to about 400°C, or about 200°C to about 400°C, but is not limited thereto.

[0057] In one embodiment of the present application, the transport gas or diluent gas is preferably a mixture of one or more gases selected from argon (Ar), nitrogen (N2), helium (He), or hydrogen (H2), but is not limited thereto.

[0058] In one embodiment of the present invention, various supply methods may be applied to transfer the ruthenium precursor compound onto the substrate, including a bubbling method in which the precursor is forcibly vaporized using a transport gas, a liquid delivery system (LDS) in which the precursor is supplied in liquid form at room temperature and vaporized via a vaporizer, and a vapor flow controller (VFC) method in which the precursor is supplied directly using its vapor pressure. When the vapor pressure is high, the VFC method can be used, and when the vapor pressure is low, a bypass method in which the container is heated to vaporize the precursor can be used. The ruthenium precursor compound can be placed in a bubbler container or a VFC container and supplied to a chamber using bubbling with a transport gas at a temperature range of about 0.1 torr to about 10 torr and room temperature to about 100°C, or by transporting it using a high vapor pressure. Most preferably, the LDS method in which the ruthenium precursor compound is supplied in liquid form at room temperature and vaporized via a vaporizer can be used, but the invention is not limited thereto.

[0059] In one embodiment of the present invention, it is more preferable, but not limited to, transporting the ruthenium precursor compound with argon (Ar) or nitrogen (N2) gas, utilizing thermal energy or plasma, or applying a bias to the substrate in order to vaporize it.

[0060] In one embodiment of the present invention, the fact that the deposition temperature is room temperature to about 400°C, or about 200°C to about 400°C, allows for a wide range of process temperatures applicable to memory elements, logic elements, and display elements, thus offering high applicability to various fields. Furthermore, because the film properties of the ruthenium-containing oxide thin film or nitride thin film differ, and a ruthenium precursor compound usable over a wide temperature range is required, deposition is preferably carried out in a deposition temperature range of room temperature to about 400°C, or about 200°C to about 400°C, but is not limited thereto.

[0061] In one embodiment of the present application, when a ruthenium-containing oxide film is formed during the deposition of the ruthenium-containing film, it is preferable to use one or more mixtures selected from water vapor (H2O), oxygen (O2), oxygen plasma (O2Plasma), nitrogen oxide (NO, N2O), nitrogen oxide plasma (N2O Plasma), oxygen nitride (N2O2), hydrogen peroxide (H2O2), and ozone (O3) as the reaction gas. However, the present application is not limited thereto.

[0062] In one embodiment of the present invention, it is preferable to use ammonia (NH3), ammonia plasma (HN3Plasma), hydrazine (N2H4), or nitrogen plasma (N2Plasma) as reaction gases for depositing the ruthenium-containing nitride film during the deposition of the ruthenium-containing film. However, the invention is not limited thereto.

[0063] The present invention will be described in more detail below through embodiments of this application, but the embodiments described below are for illustrative purposes only to aid in understanding this application, and the content of this application is not limited to the embodiments described below. [Examples]

[0064] <Example 1> Preparation of (p-Cymene)(2,4-Dimethyl-1,3-pentadiene)Ru: [CH3C6H4CH(CH3)2][CH2=C(CH3)CH=C(CH3)2]Ru [ka] In a flame-dried 1000 ml L Schlenk flask, 288.5 g (0.144 mol) of [RuCl2(p-cymene)] and 91.8 g (0.867 mol) of Na2CO3 were mixed with 400 mL of 2-propanol to prepare a suspension. 25 g (0.260 mol) of 2,4-dimethyl-1,3-pentadiene was slowly added to the suspension, and the mixture was refluxed for 12 hours to complete the reaction. After the reaction was complete, the solvent and volatile by-reactants were removed under reduced pressure, and the mixture was extracted using 500 mL of n-hexane. The n-hexane extract was filtered through a Celite pad and glass frit. The obtained filtrate was then desoldered under reduced pressure and distilled under reduced pressure to obtain 52.2 g (50.1% yield) of the orange liquid compound [(p-cymene)(2,4-dimethyl-1,3-pentadiene)Ru] represented by the formula 2. Boiling point: 92℃ (0.3torr) Density: 1.25g / mL (25℃)

[0065] 1 H-NMR (400MHz, C6D6, 25℃): δ4.981(d, 1H, [CH3C6 H 4CH(CH3)2]-Ru), δ4.656(d, 1H, [CH3C6 H 4CH(CH3)2]-Ru), δ4.596(d, 1H, [CH3C6 H 4CH(CH3)2]-Ru), δ4.384(s, 1H, [CH2=C(CH3)C H =C(CH3)2]-Ru), δ4.359(d, 1H, [CH3C6 H 4CH(CH3)2]-Ru), δ2.431(q, 1H, [CH3C6H4C H (CH3)2]-Ru), δ1.933(s, 3H, [C H 3C6H4CH(CH3)2]-Ru), δ1.878(s, 1H, [C H 2=C(CH3)CH=C(CH3)2]-Ru), δ1.824(s, 3H, [CH2=C(C H3)CH=C(CH3)2]-Ru), δ1.533(s, 1H, [C H 2=C(CH3)CH=C(CH3)2]-Ru), δ1.479(s, 3H, [CH2=C(CH3)CH=C(C H 3)2]-Ru), δ1.264(s, 3H, [CH2=C(CH3)CH=C(C H 3)2]-Ru), δ1.186(m, 6H, [CH3C6H4CH(C H 3)2]-Ru)

[0066] <Example 2> Preparation of a mixed composition of (p-cymene)(2,4-hexadiene)Ru and (p-cymene)(1,3-hexadiene)Ru: [CH3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru + [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru [ka] In a flame-dried 1000 mL Schlenk flask, 230 g (0.048 mol) of [RuCl2(p-cymene)] and 30.5 g (0.288 mol) of Na2CO3 were mixed with 400 mL of 2-propanol to prepare a suspension. 16.6 g (0.192 mol) of 2,4-hexadiene was slowly added to the suspension, and the mixture was refluxed for 40 hours to complete the reaction. After the reaction was complete, the solvent and volatile by-reactants were removed under reduced pressure, and the mixture was extracted using 500 mL of n-hexane. The n-hexane extract was filtered through a Celite pad and glass frit. The resulting filtrate was then desoldered under reduced pressure, and distilled under reduced pressure to obtain 22 g (62.8% yield) of the orange liquid mixture represented by formula 3 [(p-cymene)(2,4-hexadiene)Ru and (p-cymene)(1,3-hexadiene)Ru].

[0067] From the NMR spectrum of the aforementioned liquid, it was determined that it was a mixture of (p-cymene)(2,4-hexadiene)Ru and (p-cymene)(1,3-hexadiene)Ru in a ratio of 6:4.

[0068] An isomerization reaction is known in which a hydrogen atom bonded to a double-bonded carbon coordinated to the Ru central metal moves to another carbon [YMWuu et al, Inorganic Chemistry 1988, 27(17), 3039~3044, doi:10.1021 / ic00290a028]. It is presumed that some of the 2,4-hexadiene used as a starting material was converted to 1,3-hexadine through such an isomerization reaction. The two isomers had nearly identical boiling points, and the 6:4 ratio was maintained even after vacuum distillation. Boiling point: 86℃ (0.3torr) Density: 1.32g / mL (25℃) 1 1H-NMR (700MHz, C6D6, 25℃)

[0069] Isomer 1. Chemical 2: (p-cymene)(2,4-hexadiene)Ru, [CH3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru δ4.668(m, 4H, [CH3C6 H 4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ4.330(m, 2H, [CH3C6H4CH(CH3)2](CH3CH=C H -C H =CHCH3)Ru), δ2.338(m, 1H, [CH3C6H4C H (CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ2.013(s, 3H, [C H 3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ1.371(d, 6H, [CH3C6H4CH(CH3)2](C H 3CH=CH-CH=CHCH3)Ru), δ1.147(d, 6H, [CH3C6H4CH(C H3) 2]((CH3CH=CH-CH=CHCH3)Ru), δ 0.739 (m, 2H, [CH3C6H4CH(CH3)2](CH3C H =CH-CH=CHCH3)Ru)

[0070] Isomer 2, Chemical Shift 3: (p-cymene)(1,3-hexadiene)Ru, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru δ 4.983 (m, 1H, [CH3C6 H 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru), δ 4.835 (m, 2H, [CH3C6 H 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru), δ 4.727 (m, 1H, [CH3C6 H 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru), δ 4.603 (m, 1H, [CH3C6H4CH(CH3)2](CH2=C H CH=CHCH2CH3)Ru), δ 4.418 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHC H =CHCH2CH3)Ru), δ 2.302 (m, 1H, [CH3C6H4C H (CH3)2](CH2=CHCH=CHCH2CH3)Ru), δ 1.969 (s, 3H, [C H 3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru), δ 1.758 (d, 1H, [CH3C6H4CH(CH3)2](C H 2=CHCH=CHCH2CH3)Ru), δ 1.703 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHC H 2CH3)Ru), δ 1.401 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHC H 2CH3)Ru), δ 1.120 (t, 3H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2C H 3)Ru), δ 1.098 (m, 6H, [CH3C6H4CH(C H3)2](CH2=CHCH=CHCH2CH3)Ru), δ0.726(m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=C H CH2CH3)Ru), δ0.194(d, 1H, [CH3C6H4CH(CH3)2](C H 2=CHCH=CHCH2CH3)Ru)

[0071] <Experimental Example 1> Evaluation of the thermal stability of the Ru precursor composition according to Example 1 Four sealed stainless steel containers were each filled with 2 g of the composition containing the Ru precursor compound (Chemical Formula 1) synthesized in Example 1, and heated at 110°C and 120°C for 7, 14, and 28 days, respectively.

[0072] The NMR spectra before and after heating were measured, and their respective purities are shown in Table 1 below. The purity remained almost unchanged even after 28 days of heating, and no new NMR peaks appeared. Therefore, it can be confirmed that the Ru precursor composition [(p-cymene)(2,4-dimethyl-1,3-pentadiene)Ru] of Example 1 maintains a constant proportion without decomposition during vaporization by heating at 110°C and 120°C.

[0073] [Table 1]

[0074] <Experimental Example 2> Evaluation of the thermal stability of the Ru precursor composition according to Example 2 Two g each of the Ru precursor composition [(p-cymene)(2,4-hexadiene)Ru(Chemical Formula 2) and (p-cymene)(1,3-hexadiene)Ru(Chemical Formula 3)] synthesized in Example 2 was placed in four sealed stainless steel containers and heated at 110°C and 120°C for 7 and 14 days, respectively.

[0075] The proportions of isomers measured by NMR before and after heating are shown in Table 2 below. The proportions of isomers remained almost unchanged even after 14 days of heating, and no new NMR peaks appeared. Therefore, it can be confirmed that the proportions of isomers remained constant while the Ru precursor composition of Example 2 was heated to 110°C and 120°C, respectively, and vaporized.

[0076] [Table 2]

[0077] In the case of Ru precursor compositions with low thermal stability, the proportion of the composition of dissimilar substances changes during vaporization, whereas in the Ru precursor composition of the present invention, the proportion of the composition is maintained constant during heating and vaporization.

[0078] <Experimental Example 3> Deposition of ruthenium film using (p-cymene)(2,4-dimethyl-1,3-pentadiene)Ru A Ru metal film was formed using a precursor composition consisting of a (p-cymene)(2,4-dimethyl-1,3-pentadiene)Ru compound, manufactured by the method of Example 1, via a plasma-enhanced atomic layer deposition (PEALD) process. The Ru precursor composition was placed in a stainless steel container, heated to 100°C, and vaporized by flowing argon carrier gas at a flow rate of 200 sccm. The vaporized Ru precursor composition was then supplied to the PEALD reactor. The process pressure of the PEALD reactor was maintained at 1 torr to 1.2 torr. A silicon wafer piece heated to 300°C was used as the substrate for the PEALD process. The (O2+N2) plasma generated by applying a pulse of 200W of RF power each time a mixed gas of oxygen and nitrogen was supplied was used as the reaction gas. The ALD supply cycle, consisting of a 10-second supply of Ru precursor composition, a 10-second purge of Ar gas, a 10-second supply of (O2+N2) plasma reaction gas, and a 10-second purge of Ar gas, was repeated 200 times.

[0079] The mixing ratio of oxygen (O2) and nitrogen (N2) gases used as reaction gases was adjusted to 70 sccm:140 sccm, 100 sccm:100 sccm, and 200 sccm:0 sccm. The surface resistance of the Ru film formed in each case was measured, and the resistivity calculated by measuring the film thickness with a transmission electron microscope (TEM) is shown in Table 3 below. Furthermore, the film composition at different thicknesses, as measured by Auger electron spectroscopy, is shown in Figure 2.

[0080] [Table 3]

[0081] The experimental results above show that a Ru metal film with good electrical conductivity was formed, with a film thickness of approximately 150 Å to 400 Å and a resistivity of approximately 20 μΩ·cm to 30 μΩ·cm.

[0082] The above description of the present application is illustrative, and a person with ordinary skill in the art to which the present application pertains should understand that it can be easily modified into other specific forms without altering the technical idea or essential features of the present application. Therefore, the above-described embodiments should be understood to be illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a dispersed manner, and similarly, components described as dispersed may be implemented in a combined form.

[0083] The scope of this application is defined by the claims, which are set forth below rather than by the detailed description above, and all modified or altered forms derived from the meaning and scope of the claims, as well as the concept of equivalents thereof, should be interpreted as being included within the scope of this application.

Claims

1. A ruthenium precursor compound represented by the following chemical formula I. 【Chemistry 1】 In the above chemical formula I, R １ ~R4 are each independently hydrogen; substituted or unsubstituted linear or branched C １－１０ Alkyl alkyl group; or substituted or unsubstituted C ３－１０ It is a cycloalkyl group, R5 and R6 are each independently a substituted or unsubstituted linear or branched C1-10 alkyl group; or a substituted or unsubstituted C3-10 cycloalkyl group. When the alkyl group or cycloalkyl group is substituted, linear or branched C １－３ It is substituted with an alkyl group.

2. R １ and R ２ One or more of these are substituted or unsubstituted linear or branched C １－１０ Alkyl alkyl group; or substituted or unsubstituted C ３－１０ The ruthenium precursor compound according to claim 1, wherein it is a cycloalkyl group.

3. The ruthenium precursor compound according to claim 1, wherein the ruthenium precursor compound is selected from the following compounds. (p-cymene)[CH ２ =C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[MeCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[EtCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｎ PrCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｉ PrCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｎ BuCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｉ BuCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｓｅｃ BuCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｔ BuCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru。

4. The ruthenium precursor compound according to claim 1, wherein the ruthenium precursor compound is the following compound. 【Chemistry 2】

5. A ruthenium precursor compound represented by the following formula I, or A film-forming precursor composition comprising a mixture of ruthenium precursor compounds represented by the following chemical formulas II and III. 【Transformation 3】 In the above chemical formula I, R １ ~R4 are each independently hydrogen; substituted or unsubstituted linear or branched C １－１０ Alkyl alkyl group; or substituted or unsubstituted C ３－１０ It is a cycloalkyl group, R5 and R6 are each independently a substituted or unsubstituted linear or branched C1-10 alkyl group; or a substituted or unsubstituted C3-10 cycloalkyl group. When the alkyl group or cycloalkyl group is substituted, linear or branched C １－３ It is substituted with an alkyl group.

6. R １ and R ２ One or more of these are substituted or unsubstituted linear or branched C １－１０ Alkyl alkyl group; or substituted or unsubstituted C ３－１０ The film-forming precursor composition according to claim 5, wherein the precursor is a cycloalkyl group.

7. The film-forming precursor composition according to claim 5, wherein the ruthenium precursor compound represented by formula I above comprises one or more compounds selected from the following compounds. (p-cymene)[CH ２ =C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[MeCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[EtCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｎ PrCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｉ PrCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｎ BuCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｉ BuCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｓｅｃ BuCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru、(p-cymene)[ ｔ BuCH=C(CH ３ )CH=C(CH ３ ) ２ ]Ru。

8. The film-forming precursor composition according to claim 5, wherein the ruthenium precursor compound represented by the above formula I is the following compound. 【Chemistry 4】

9. The film-forming precursor composition according to claim 5, wherein the film is one or more selected from a ruthenium metal film, a ruthenium-containing oxide film, a ruthenium-containing nitride film, a ruthenium-containing carbide film, and combinations thereof.

10. The film-forming precursor composition according to claim 5, further comprising one or more nitrogen sources selected from ammonia, nitrogen, hydrazine, and dimethylhydrazine.

11. The film-forming precursor composition according to claim 5, further comprising one or more oxygen sources selected from water vapor, oxygen, and ozone.

12. A method for forming a ruthenium-containing film, comprising forming a ruthenium-containing film using a film-forming precursor composition comprising a ruthenium precursor compound represented by the following formula I, or a mixture of ruthenium precursor compounds represented by the following formulas II and III. 【Transformation 5】 In the above chemical formula I, R １ ~R4 are each independently hydrogen; substituted or unsubstituted linear or branched C １－１０ Alkyl alkyl group; or substituted or unsubstituted C ３－１０ It is a cycloalkyl group, R5 and R6 are each independently a substituted or unsubstituted linear or branched C1-10 alkyl group; or a substituted or unsubstituted C3-10 cycloalkyl group. When the alkyl group or cycloalkyl group is substituted, linear or branched C １－３ It is substituted with an alkyl group.

13. The ruthenium-containing film forming method according to claim 12, wherein the ruthenium precursor compound represented by the above-mentioned chemical formula I contained in the film-forming precursor composition is the following compound. 【Transformation 6】

14. The ruthenium-containing film formation method according to claim 12, wherein the ruthenium-containing film is deposited by chemical vapor deposition or atomic layer deposition.

15. The ruthenium-containing film formation method according to claim 14, wherein the composition of one or more ruthenium precursor compounds contained in the film-forming precursor composition is maintained during the process of heating and vaporizing the film-forming precursor composition.

16. The method for forming a ruthenium-containing film according to claim 12, wherein the ruthenium-containing film is formed in a temperature range of room temperature to 400°C.

17. The method for forming a ruthenium-containing film according to claim 12, wherein the ruthenium-containing film is formed in a thickness range of 1 nm to 500 nm.

18. The method for forming a ruthenium-containing film according to claim 12, wherein the ruthenium-containing film is formed on a substrate having irregularities (grooves) with an aspect ratio of 1 to 100 and a width of 10 nm to 1 μm.

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