Group 4 metal element-containing alkoxy compound, preparing method thereof, precursor composition including the same for film deposition, and method of depositing film using the same
10131680 ยท 2018-11-20
Assignee
Inventors
Cpc classification
C23C16/045
CHEMISTRY; METALLURGY
C07F7/00
CHEMISTRY; METALLURGY
C09D1/00
CHEMISTRY; METALLURGY
C23C16/45553
CHEMISTRY; METALLURGY
International classification
C07F7/00
CHEMISTRY; METALLURGY
C23C16/455
CHEMISTRY; METALLURGY
C09D1/00
CHEMISTRY; METALLURGY
Abstract
The present disclosure provides a Group 4 metal element-containing novel alkoxy compound, a method of preparing the Group 4 metal element-containing alkoxy compound, a precursor composition including the Group 4 metal element-containing alkoxy compound for depositing a film, and a method of depositing a Group 4 metal element-containing film using the precursor composition.
Claims
1. A Group 4 metal element-containing compound, represented by the following Chemical Formula 1: ##STR00025## in the above Chemical Formula 1, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.5 and R.sup.6 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
2. The Group 4 metal element-containing compound of claim 1, wherein M is Ti, Zr or Hf, each of R.sup.5 and R.sup.6 is independently CH.sub.3, C.sub.2H.sub.5 or CH(CH.sub.3).sub.2, and n is an integer of from 1 to 3.
3. The Group 4 metal element-containing compound of claim 2, wherein M is Ti, Zr or Hf, R.sup.5 and R.sup.6 are CH.sub.3, and n is 2.
4. A method of preparing a Group 4 metal element-containing compound represented by the following Chemical Formula 1, comprising reacting a compound represented by the following Chemical Formula 2 with a linear or branched alcohol as R.sup.5OH and/or R.sup.6OH having 1 to 4 carbon atoms: ##STR00026## in the above Chemical Formula 2, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.7 to R.sup.10 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3; ##STR00027## in the above Chemical Formula 1, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.5 and R.sup.6 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
5. A method of preparing a Group 4 metal element-containing compound represented by the following Chemical Formula 1, comprising reacting a compound represented by the following Chemical Formula 3 with MOR.sup.5 and/or MOR.sup.6 as a salt of an alkali metal M of a linear or branched alcohol having 1 to 4 carbon atoms: ##STR00028## in the above Chemical Formula 3, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, X is a halogen, and n is an integer of from 1 to 3; ##STR00029## in the above Chemical Formula 1, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.5 and R.sup.6 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
6. A precursor composition for depositing a film, comprising a Group 4 metal element-containing compound of claim 1.
7. A method of depositing a Group 4 metal element-containing film, comprising forming a Group 4 metal element-containing film using a precursor composition for film depositing a film of claim 6.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
(5)
BEST MODE FOR CARRYING OUT THE INVENTION
(6) Hereinafter, examples of the present disclosure will be described in detail with reference to the accompanying drawings so that the present disclosure may be readily implemented by those skilled in the art. However, it is to be noted that the present disclosure is not limited to the examples but can be embodied in various other ways. In drawings, parts irrelevant to the description are omitted for the simplicity of explanation, and like reference numerals denote like parts through the whole document.
(7) Through the whole document, the term connected to or coupled to that is used to designate a connection or coupling of one element to another element includes both a case that an element is directly connected or coupled to another element and a case that an element is electronically connected or coupled to another element via still another element.
(8) Through the whole document, the term on that is used to designate a position of one element with respect to another element includes both a case that the one element is adjacent to the other element and a case that any other element exists between these two elements.
(9) Further, through the whole document, the term comprises or includes and/or comprising or including used in the document means that one or more other components, steps, operation and/or existence or addition of elements are not excluded in addition to the described components, steps, operation and/or elements unless context dictates otherwise.
(10) Through the whole document, the term about or approximately or substantially is intended to have meanings close to numerical values or ranges specified with an allowable error and intended to prevent accurate or absolute numerical values disclosed for understanding of the present disclosure from being illegally or unfairly used by any unconscionable third party.
(11) Through the whole document, the term step of does not mean step for.
(12) Through the whole document, the term combination(s) of included in Markush type description means mixture or combination of one or more components, steps, operations and/or elements selected from a group consisting of components, steps, operation and/or elements described in Markush type and thereby means that the disclosure includes one or more components, steps, operations and/or elements selected from the Markush group.
(13) Through the whole document, a phrase in the form A and/or B means A or B, or A and B.
(14) Through the whole document, the term alkyl includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, or 1 to 4 carbon atoms and all the possible isomers thereof. For example, the alkyl group may include methyl group (Me), ethyl group (Et), n-propyl group (.sup.nPr), iso-propyl group (.sup.iPr), n-butyl group (.sup.nBu), tert-butyl group (.sup.tBu), iso-butyl group (.sup.iBu), sec-butyl group (.sup.sBu), pentyl group, hexyl group, iso-hexyl group, heptyl group, 4,4-dimethyl pentyl group, octyl group, 2,2,4-trimethyl pentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, but may not be limited thereto.
(15) Through the whole document, the term Group 4 metal element refers to a chemical element belonging to the fourth group in the Periodic Table and may include Ti, Zr or Hf.
(16) Through the whole document, the term Cp is the abbreviation of a cyclopentadienyl group.
(17) Through the whole document, the term halogen or halo refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
(18) In the following description, exemplary embodiments of the present disclosure will be described in detail, but the present disclosure may not be limited thereto.
(19) According to a first aspect of the present disclosure, there is provided a Group 4 metal element-containing compound, represented by the following Chemical Formula 1:
(20) ##STR00006##
(21) in the above Chemical Formula 1, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.5 and R.sup.6 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
(22) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf and each of R.sup.5 and R.sup.6 may be independently methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl, but may not be limited thereto.
(23) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, R.sup.5 and R.sup.6 may be identical to or different to each other.
(24) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf, each of R.sup.5 and R.sup.6 may be independently CH.sub.3, C.sub.2H.sub.5 or CH(CH.sub.3).sub.2, and n may be from 1 to 3, or may be 2, but may not be limited thereto.
(25) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf, R.sup.5 and R.sup.6 may be CH.sub.3, and n may be from 1 to 3, or may be 2, but may not be limited.
(26) In an exemplary embodiment of the present disclosure, the Group 4 metal element-containing compound represented by the above Chemical Formula 1 may include compounds represented as the following structures, but may not be limited thereto:
(27) ##STR00007##
(28) According to a second aspect of the present disclosure, there is provided a method of preparing a Group 4 metal element-containing compound, represented by the following Chemical Formula 1, including reacting a compound represented by the following Chemical Formula 2 with linear or branched alcohol as R.sup.5OH and/or R.sup.6OH having 1 to 4 carbon atoms:
(29) ##STR00008##
(30) in the above Chemical Formula, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.7 to R.sup.10 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3;
(31) ##STR00009##
(32) in the above Chemical Formula 1, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.5 and R.sup.6 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
(33) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf and each of R.sup.5 and R.sup.6 may be independently methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl, but may not be limited thereto.
(34) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, R.sup.5 and R.sup.6 may be identical to or different from each other. For example, if R.sup.5 and R.sup.6 are different to each other, R.sup.5OH and R.sup.6OH may be simultaneously or sequentially added to and reacted with a compound represented by the above Chemical Formula 2.
(35) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf, each of R.sup.5 and R.sup.6 may be independently CH.sub.3, C.sub.2H.sub.5 or CH(CH.sub.3).sub.2, and n may be from 1 to 3, or may be 2, but may not be limited thereto.
(36) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf, R.sup.5 and R.sup.6 may be CH.sub.3, and n may be from 1 to 3, or may be 2, but may not be limited.
(37) In an exemplary embodiment of the present disclosure, a Group 4 metal element-containing compound represented by the above Chemical Formula 1 refers to compounds represented by Chemical Formula 1 and specifically the exemplified compounds therefor in the first aspect of the present disclosure, but may not be limited thereto.
(38) According to a third aspect of the present disclosure, there is provided a method of preparing a Group 4 metal element-containing compound, represented by the following Chemical Formula 1, including reacting a compound represented by the following Chemical Formula 3 with MOR.sup.5 and/or MOR.sup.6 as a salt of an alkali metal M of linear or branched alcohol having 1 to 4 carbon atoms:
(39) ##STR00010##
(40) in the above Chemical Formula 3, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, X is a halogen, and n is an integer of from 1 to 3;
(41) ##STR00011##
(42) in the above Chemical Formula 1, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.5 and R.sup.6 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
(43) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf and each of R.sup.5 and R.sup.6 may be independently methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl, but may not be limited thereto.
(44) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, R.sup.5 and R.sup.6 may be identical to or different from each other. For example, if R.sup.5 and R.sup.6 are different from each other, MOR.sup.5 and MOR.sup.6 may be simultaneously or sequentially added to and reacted with a compound represented by the above Chemical Formula 2.
(45) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf, each of R.sup.5 and R.sup.6 may be independently CH.sub.3, C.sub.2H.sub.5 or CH(CH.sub.3).sub.2, and n may be from 1 to 3 or may be 2, but may not be limited thereto.
(46) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf, R.sup.5 and R.sup.6 may be CH.sub.3, and n may be from 1 to 3 or may be 2, but may not be limited thereto.
(47) In an exemplary embodiment of the present disclosure, a Group 4 metal element-containing compound represented by the above Chemical Formula 1 refers to compounds represented by Chemical Formula 1 and specifically exemplified compounds therefor in the first aspect of the present disclosure, but may not be limited thereto.
(48) In an exemplary embodiment of the present disclosure, each of the alkali metal salts MOR.sup.5 and MOR.sup.6 of the alcohol may be independently, e.g., methoxylithium (LiOMe), ethoxylithium (LiOEt), isopropoxylithium (LiO.sup.iPr), methoxysodium (NaOMe), ethoxysodium (NaOEt), isopropoxysodium (NaO.sup.iPr), methoxypotassium (KOMe), ethoxypotassium (KOEt), or isopropoxypotassium (KO.sup.iPr), but may not be limited thereto.
(49) According to a fourth aspect of the present disclosure, there is provided a precursor composition for depositing a film, including a Group 4 metal element-containing compound according to the first aspect of the present disclosure.
(50) According to a fifth aspect of the present disclosure, there is provided a method of depositing a Group 4 metal element-containing film, including forming a Group 4 metal element-containing film using a precursor composition for depositing a film according to the fourth aspect of the present disclosure.
(51) The Group 4 metal element-containing compound according to the first aspect of the present disclosure and used in the precursor composition for depositing a film according to the fourth aspect of the present disclosure and the method of depositing a Group 4 metal element-containing film according to the fifth aspect of the present disclosure is represented by the following Chemical Formula 1:
(52) ##STR00012##
(53) in the above Chemical Formula 1, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, each of R.sup.5 and R.sup.6 is independently a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
(54) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf and each of R.sup.5 and R.sup.6 may be independently methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl, but may not be limited thereto.
(55) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, R.sup.5 and R.sup.6 may be identical to or different from each other.
(56) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf each of R.sup.5 and R.sup.6 may be independently CH.sub.3, C.sub.2H.sub.5 or CH(CH.sub.3).sub.2, and n may be from 1 to 3, or may be 2, but may not be limited thereto.
(57) In an exemplary embodiment of the present disclosure, in the above Chemical Formula 1, M may be Ti, Zr or Hf, R.sup.5 and R.sup.6 may be CH.sub.3, and n may be from 1 to 3, or may be 2, but may not be limited thereto.
(58) In an exemplary embodiment of the present disclosure, the Group 4 metal element-containing compound represented by the above Chemical Formula 1 may include compounds represented as the following structures, but may not be limited thereto:
(59) ##STR00013##
(60) In an exemplary embodiment of the present disclosure, the precursor composition for depositing a film may be used for deposition of a Group 4 metal element-containing film or thin film. The Group 4 metal element-containing film or thin film may have a thickness of from about 1 nm to several m, but may not be limited thereto.
(61) In an exemplary embodiment of the present disclosure, the Group 4 metal element-containing film or thin film may include a film or thin film containing a metal of Ti, Zr and/or Hf, a film or thin film containing an oxide of Ti, Zr and/or Hf, a film or thin film containing a nitride of Ti, Zr and/or Hf, a film or thin film containing an oxynitride of Ti, Zr and/or Hf, or a film or thin film containing a carbonitride of Ti, Zr and/or Hf, but may not be limited thereto.
(62) In an exemplary embodiment of the present disclosure, the Group 4 metal element-containing film or thin film may be used as a high-k film in a semiconductor device, a catalyst, or the like, but may not be limited thereto.
(63) In an exemplary embodiment of the present disclosure, a method of depositing a Group 4 metal element-containing film or thin film may include forming a Group 4 metal element-containing film or thin film by supplying and depositing the precursor composition to form a Group 4 metal element-containing film or thin film on a substrate positioned in a deposition chamber, but may not be limited thereto. The method of depositing a film may employ a method and an apparatus known in the art and may be performed using one or more additional reaction gases together if necessary. The substrate may employ a silicon semiconductor wafer and a compound semiconductor wafer, but may not be limited thereto. A substrate having a hole or trench may be used, and for example, a porous substrate having a large surface area may be used as a catalyst.
(64) In an exemplary embodiment of the present disclosure, the deposition of a film may be performed by metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but may not be limited thereto. The metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) may be performed using a deposition apparatus, deposition conditions, and additional reaction gases known in the art.
(65) Specifically, according to the precursor composition for depositing a film according to the fourth aspect of the present disclosure and the method of depositing a Group 4 metal element-containing film or thin film according to the fifth aspect of the present disclosure including forming a Group 4 metal element-containing film or thin film using the precursor composition for depositing a film, the Group 4 metal element-containing novel compounds according to an exemplary embodiment of the present disclosure which are included in the precursor composition for depositing a film have high thermal stability and thus can be used as a precursor for atomic layer deposition or chemical vapor deposition to form a Group 4 metal element-containing film and particularly can be used to uniformly form a Group 4 metal element-containing film having a thickness of from several nm to several tens of nm on a substrate having a trench (groove) in its surface or porous substrate. For example, in a substrate having a fine trench (groove) in its surface with an aspect ratio of about 1 or more, 2 or more, 5 or more, 10 or more, 20 or more, 30 or more or 40 or more and a width of about 1 m or less, 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, 100 nm or less, 80 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less or 10 nm or less in its surface, the Group 4 metal element-containing novel compounds have an excellent effect of uniformly forming a Group 4 metal element-containing film having a thickness of from several nm to several tens of nm on the entire surface of the substrate including a surface of the fine trench (groove) including a surface of the deepest portion of the fine trench (groove) and an upper surface of the fine trench (groove). For example, the thickness of from several nm to several tens of nm may be about 50 nm or less, about 40 nm or less, about 30 nm or less, about 20 nm or less, about 10 nm or less, from about 1 nm to about 10 nm, from about 1 nm to about 20 nm, from about 1 nm to about 30 nm, from about 1 nm to about 40 nm, or from about 1 nm to about 50 nm, but may not be limited thereto.
(66) The precursor composition for depositing a film according to the fourth aspect of the present disclosure and the method of depositing a Group 4 metal element-containing film or thin film according to the fifth aspect of the present disclosure including forming a Group 4 metal element-containing film or thin film using the precursor composition for depositing a film can be applied to manufacturing commercial semiconductor devices. Particularly, in order to manufacture a DRAM semiconductor device, it is necessary to form a high-k material to a thickness of several nm on a substrate having a trench with a width of much less than 100 nm or 50 nm and an aspect ratio of 10:1, 20:1, or 30:1, or a deeper and narrower trench. Particularly, it is necessary to form a high-k material having a uniform thickness even at a temperature of about 250 C., 280 C., 300 C., or more, and, thus, a precursor composition with which a film having a uniform thickness can be formed on a very narrow and deep trench by atomic layer deposition (ALD) even at a high temperature is needed and a Ti, Zr, or Hf compound having very high thermal stability is needed to be used as the precursor composition, and therefore, the precursor composition for depositing a film according to the fourth aspect of the present disclosure and the method of depositing a Group 4 metal element-containing film or thin film according to the fifth aspect of the present disclosure including forming a Group 4 metal element-containing film or thin film using the precursor composition for depositing a film can be usefully utilized.
MODE FOR CARRYING OUT THE INVENTION
(67) Hereinafter, the present disclosure will be explained in more detail with reference to Examples. However, the following Examples are illustrative only for better understanding of the present disclosure but do not limit the present disclosure.
EXAMPLES
(68) After 11.2 g (0.462 mol, 3 equivalents) of magnesium and 100 mL of tetrahydrofuran (THF, C.sub.4H.sub.3O) were put into a flame-dried 1 L Schlenk flask, the flask was maintained at room temperature. After 21.8 g (0.154 mol, 1 equivalent) of 3-chloro-propylcyclopentadiene was added to the flask, the obtained reaction solution was stirred for 15 hours while the temperature was slowly increased to 50 C. Then, the temperature of the flask was slowly decreased to room temperature and the reaction solution was filtered through a celite pad and a glass frit to remove excess magnesium, and, thus, Grignard reagent Cp(CH.sub.2).sub.3MgCl was obtained from the obtained filtrate.
(69) After 99 g (0.522 mol, 1 equivalent) of titanium tetrachloride (TiCl.sub.4) and 1,000 mL of toluene (C.sub.6H.sub.5CH.sub.3) were put into a flame-dried 3 L Schlenk flask, the flask was cooled at 10 C. After the Grignard reagent Cp(CH.sub.2).sub.3MgCl (0.522 mol, 1 equivalent) prepared in Preparation Example 1 and 53 g (0.522 mol, 1 equivalent) of triethylamine were diluted in 500 mL of toluene and slowly drop-wisely added to the flask, the obtained reaction solution was refluxed for 15 hours.
(70) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and washing was carried out with 200 mL of n-hexane three times and the reaction product was subject to a reduced pressure to remove the solvent and distilled under a reduced pressure, and, thus, 69 g (yield of 59%) of red solid compound Cp(CH.sub.2).sub.3TiCl.sub.2 represented as the following structure was obtained:
(71) ##STR00014##
(72) The precursor Cp(CH.sub.2).sub.3ZrCl.sub.2 or Cp(CH.sub.2).sub.3HfCl.sub.2 was prepared by the same method as in Preparation Example 2 except that zirconium tetrachloride (ZrCl.sub.4) or hafnium tetrachloride (HfCl.sub.4) was used instead of titanium tetrachloride (TiCl.sub.4) used in Preparation Example 2.
(73) After 277 g (1.044 mol, 2 equivalents) of an n-butyllithium hexane solution was put into a flame-dried 3 L Schlenk flask, the flask was cooled at 40 C. 47 g (1.044 mol, 2 equivalents) of dimethylamine was slowly drop-wisely added to the flask and then stirred at room temperature for 3 hours. After Cp(CH.sub.2).sub.3TiCl.sub.2 (0.522 mol, 1 equivalent) prepared in Preparation Example 2 was slowly drop-wisely added to the flask, the obtained reaction solution was stirred at 40 C. for 4 hours.
(74) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and then extraction was carried out with 500 mL of n-hexane. After the n-hexane extract was filtered through a celite pad and a glass frit, the obtained filtrate was subject to a reduced pressure to remove the solvent and distilled under a reduced pressure, and, thus, 50 g (yield of 40%) of red liquid compound Cp(CH.sub.2).sub.3Ti[N(CH.sub.3).sub.2].sub.2 represented as the following structure was obtained:
(75) ##STR00015##
(76) After 41 g (0.154 mol, 1 equivalent) of tetrakis(dimethylamino)zirconium [Zr(N(CH.sub.3).sub.2).sub.4] and 100 mL of n-hexane (C.sub.6H.sub.14) were put into a flame-dried 1 L Schlenk flask, the flask was maintained at room temperature. After Grignard reagent Cp(CH.sub.2).sub.3MgCl (0.154 mol, 1 equivalent) prepared in Preparation Example 1 was slowly drop-wisely added to the flask, the obtained reaction solution was refluxed for 15 hours.
(77) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and then extraction was carried out with 200 mL of n-hexane. After the n-hexane extract was filtered through a celite pad and a glass frit, the obtained filtrate was subject to a reduced pressure to remove the solvent and distilled under a reduced pressure, and, thus, 27 g (yield of 61%) of pale yellow liquid compound Cp(CH.sub.2).sub.3Zr[N(CH.sub.3).sub.2].sub.2 which is a liquid zirconium compound represented as the following structure was obtained:
(78) ##STR00016##
(79) After 198 g (0.558 mol, 1 equivalent) of tetrakis(dimethylamino)hafnium [Hf(N(CH.sub.3).sub.2).sub.4] and 500 mL of n-hexane were put into a flame-dried 1 L Schlenk flask, the flask was maintained at room temperature. After Grignard reagent Cp(CH.sub.2).sub.3MgCl (0.558 mol, 1 equivalent) prepared in Preparation Example 1 was slowly drop-wisely added to the flask, the obtained reaction solution was refluxed for 15 hours.
(80) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and then extraction was carried out with 1,000 mL of n-hexane. After the n-hexane extract was filtered through a celite pad and a glass frit, the obtained filtrate was subject to a reduced pressure to remove the solvent and distilled under a reduced pressure, and, thus, 108 g (yield of 52%) of pale yellow liquid compound Cp(CH.sub.2).sub.3Hf[N(CH.sub.3).sub.2].sub.2 represented as the following structure was obtained:
(81) ##STR00017##
(82) After 35 g (0.145 mol, 1 equivalent) of Cp(CH.sub.2).sub.3Ti[N(CH.sub.3).sub.2].sub.2 prepared in Preparation Example 4 and 150 mL of n-hexane (C.sub.6H.sub.14) were put into a flame-dried 250 mL Schlenk flask, 9.3 g (0.290 mol, 2.1 equivalents) of methanol was slowly drop-wisely added to the flask and then stirred at room temperature for 2 hours.
(83) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and distilled under reduced pressure, and, thus, 15 g (yield of 50%) of pale yellow liquid compound Cp(CH.sub.2).sub.3Ti(OCH.sub.3).sub.2 represented as the following structure was obtained. A NMR spectrum of the obtained titanium liquid compound was as shown in
(84) ##STR00018##
(85) Boiling point (bp) 80 C. (0.25 torr);
(86) Elemental analysis calcd for C.sub.10H.sub.16O.sub.2Ti: C, 55.52, H, 7.44; found C, 55.58, H, 7.46;
(87) 1H-NMR (400 MHz, C.sub.6D.sub.6, 25): 5.989, 5.956 (m, 4H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 4.045 (s, 6H, OCH.sub.3), 2.520 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 1.566 (m, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 0.887 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2).
(88) After 10 g (0.035 mol, 1 equivalent) of Cp(CH.sub.2).sub.3Zr[N(CH.sub.3).sub.2].sub.2 prepared in Preparation Example 5 and 150 mL of n-hexane were put into a flame-dried 250 mL Schlenk flask, 2.4 g (0.074 mol, 2.1 equivalents) of methanol was slowly drop-wisely added to the flask and then stirred at room temperature for 2 hours.
(89) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and distilled under a reduced pressure, and, thus, 3.6 g (yield of 40%) of pale yellow liquid compound Cp(CH.sub.2).sub.3Zr(OCH.sub.3).sub.2 represented as the following structure was obtained:
(90) ##STR00019##
(91) Boiling point (bp) 102 C. (0.2 torr);
(92) Elemental analysis calcd for C.sub.10H.sub.16O.sub.2Zr: C, 46.29, H, 6.22; found C, 46.28, H, 6.24;
(93) 1H-NMR (400 MHz, C.sub.6D.sub.6, 25): 5.885, 5.869 (m, 4H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 3.878 (s, 6H, OCH3), 2.460 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 1.583 (m, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 0.939 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2).
(94) After 10 g (0.027 mol, 1 equivalent) of Cp(CH.sub.2).sub.3Hf[N(CH.sub.3).sub.2].sub.2 prepared in Preparation Example 6 and 150 mL of n-hexane were put into a flame-dried 250 mL Schlenk flask, 2.4 g (0.056 mol, 2.1 equivalents) of methanol was slowly drop-wisely added to the flask and then stirred at room temperature for 2 hours.
(95) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and distilled under a reduced pressure, and, thus, 3 g (yield of 32%) of yellow liquid compound Cp(CH.sub.2).sub.3Hf(OCH.sub.3).sub.2 represented as the following structure was obtained:
(96) ##STR00020##
(97) Boiling point (bp) 107 C. (0.2 torr);
(98) Elemental analysis calcd for C.sub.10H.sub.16O.sub.2Hf: C, 34.64, H, 4.65; found C, 34.60, H, 4.63;
(99) 1H-NMR (400 MHz, C.sub.6D.sub.6, 25): 5.743, 5.723 (m, 4H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 3.815 (s, 6H, OCH.sub.3), 2.515 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 1.503 (m, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 0.873 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2).
(100) After 68.7 g (0.257 mol, 2 equivalents) of an n-butyllithium hexane solution was put into a flame-dried 1 L Schlenk flask, the flask was cooled at 40 C. 8.3 g (0.257 mol, 2 equivalents) of methanol was slowly drop-wisely added to the flask and then stirred at room temperature for 3 hours. After Cp(CH.sub.2).sub.3ZrCl.sub.2 (0.129 mol, 1 equivalent) prepared in Preparation Example 3 was slowly drop-wisely added to the flask, the obtained reaction solution was stirred at 40 C. for 4 hours.
(101) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and then extraction was carried out with 500 mL of n-hexane. After the n-hexane extract was filtered through a celite pad and a glass frit, the obtained filtrate was subject to a reduced pressure to remove the solvent and distilled under a reduced pressure, and, thus, 14 g (yield of 42%) of yellow liquid compound Cp(CH.sub.2).sub.3Zr(OCH.sub.3).sub.2 represented as the following structure was obtained:
(102) ##STR00021##
(103) After 50 g (0.187 mol, 2 equivalents) of an n-butyllithium hexane solution was put into a flame-dried 1 L Schlenk flask, cooling was carried out at 40 C. 6 g (0.187 mol, 2 equivalents) of methanol was slowly drop-wisely added to the flask and then stirred at room temperature for 3 hours. After Cp(CH.sub.2).sub.3HfCl.sub.2 (0.094 mol, 1 equivalent) prepared in Preparation Example 3 was slowly drop-wisely added to the flask, the obtained reaction solution was stirred at 40 C. for 4 hours.
(104) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and then extraction was carried out with 500 mL of n-hexane. After the n-hexane extract was filtered through a celite pad and a glass frit, the obtained filtrate was subject to a reduced pressure to remove the solvent and distilled under a reduced pressure, and, thus, 11 g (yield of 34%) of yellow liquid compound Cp(CH.sub.2).sub.3Hf(OCH.sub.3).sub.2 represented as the following structure which is the same as that of the compound prepared in Example 3 was obtained:
(105) ##STR00022##
(106) After 35 g (0.145 mol, 1 equivalent) of Cp(CH.sub.2).sub.3Ti[N(CH.sub.3).sub.2].sub.2 prepared in Preparation Example 4 and 150 mL of n-hexane were put into a flame-dried 250 mL Schlenk flask, 17.5 g (0.290 mol, 2.1 equivalents) of isopropanol was slowly drop-wisely added to the flask and then stirred at room temperature for 2 hours.
(107) After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and distilled under a reduced pressure, and, thus, 17.7 g (yield of 45%) of pale yellow liquid compound Cp(CH.sub.2).sub.3Ti[OCH(CH.sub.3).sub.2].sub.2 represented as the following structure was obtained.
(108) ##STR00023##
(109) Boiling point (bp) 90 C. (0.3 torr);
(110) Elemental analysis calcd for C.sub.14H.sub.24O.sub.2Ti: C, 61.77, H, 8.89; found C, 61.78, H, 8.88;
(111) 1H-NMR (400 MHz, C.sub.6D.sub.6, 25 C.): 6.069, 6.022 (m, 4H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 4.573 (m, 2H, OCH(CH.sub.3).sub.2), 2.621 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 1.656 (m, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 1.195 (d, 12H, OCH(CH.sub.3).sub.2), 0.975 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2).
(112) Synthesis I:
(113) After 50 g (0.187 mol, 2 equivalents) of an n-butyllithium hexane solution was put into a flame-dried 1 L Schlenk flask, the flask was cooled at 40 C. 11.3 g (0.187 mol, 2 equivalents) of isopropanol was slowly drop-wisely added to the flask and then stirred at room temperature for 3 hours. After Cp(CH.sub.2).sub.3HfCl.sub.2 (0.094 mol, 1 equivalent) prepared in Preparation Example 3 was slowly drop-wisely added to the flask, the obtained reaction solution was stirred at 40 C. for 4 hours. After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and then extraction was carried out with 500 mL of n-hexane. After the n-hexane extract was filtered through a celite pad and a glass frit, the obtained filtrate was subject to a reduced pressure to remove the solvent and distilled under a reduced pressure, and, thus, 12.5 g (yield of 33%) of yellow liquid compound Cp(CH.sub.2).sub.3Hf[OCH(CH.sub.3).sub.2].sub.2 represented as the following structure was obtained.
(114) Synthesis II: After 10 g (0.035 mol, 1 equivalent) of Cp(CH.sub.2).sub.3Hf[N(CH.sub.3).sub.2].sub.2 prepared in Preparation Example 6 and 150 mL of n-hexane were put into a flame-dried 250 mL Schlenk flask, 4.5 g (0.074 mol, 2.1 equivalents) of isopropanol was slowly drop-wisely added to the flask and then stirred at room temperature for 2 hours. After the reaction was completed, the solvent and volatile by-product were removed under a reduced pressure and distilled under a reduced pressure, and, thus, 4.5 g (yield of 32%) of yellow liquid compound Cp(CH.sub.2).sub.3Hf[OCH(CH.sub.3).sub.2].sub.2 represented as the following structure was obtained.
(115) ##STR00024##
(116) Boiling point (bp) 110 C. (0.3 torr);
(117) Elemental analysis calcd for C.sub.14H.sub.24O.sub.2Hf: C, 41.74, H, 6.01; found C, 41.72, H, 6.00;
(118) 1H-NMR (400 MHz, C.sub.6D.sub.6, 25): 6.183, 6.134 (m, 4H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 4.359 (m, 2H, OCH(CH.sub.3).sub.2), 2.627 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 1.641 (m, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2), 1.197 (d, 12H, OCH(CH.sub.3).sub.2), 0.931 (t, 2H, C.sub.5H.sub.4CH.sub.2CH.sub.2CH.sub.2).
(119) A test for forming a titanium oxide film by atomic layer deposition (ALD) using Cp(CH.sub.2).sub.3Ti(OCH.sub.3).sub.2 prepared in Example 1 as a precursor and ozone (O.sub.3) gas as a reaction gas was conducted. In this case, a silicon (Si) wafer was used as a substrate. The substrate was heated at from 250 C. to 350 C. Further, a precursor compound put in a stainless-steel container was heated at a temperature of 90 C., and the precursor compound was supplied to an ALD reactor for performing atomic layer deposition by allowing argon (Ar) gas to pass through the container at a flow rate of 60 sccm. An internal pressure in the ALD reactor was maintained at 3 torr. An ALD source supply cycle, in which after a gas of the precursor compound was supplied to the ALD reactor for 10 seconds, then, argon gas was supplied for 10 seconds and then, ozone (O.sub.3) gas was supplied for 10 seconds and argon gas was supplied again for 10 seconds, was repeated 200 times. Film growth per source material supply cycle of the titanium oxide thin film formed according to the above-described process was as shown in
(120)
(121) The above description of the present disclosure is provided for the purpose of illustration, and it would be understood by those skilled in the art that various changes and modifications may be made without changing technical conception and essential features of the present disclosure. Thus, it is clear that the above-described examples are illustrative in all aspects and do not limit the present disclosure. For example, each component described to be of a single type can be implemented in a distributed manner. Likewise, components described to be distributed can be implemented in a combined manner.
(122) The scope of the present disclosure is defined by the following claims rather than by the detailed description of the embodiment. It shall be understood that all modifications and embodiments conceived from the meaning and scope of the claims and their equivalents are included in the scope of the present disclosure.