U.S. patent application number 15/996693 was filed with the patent office on 2018-10-04 for alkoxide compound, thin film-forming starting material, thin film formation method, and alcohol compound.
This patent application is currently assigned to ADEKA CORPORATION. The applicant listed for this patent is ADEKA CORPORATION. Invention is credited to Masaki ENZU, Masako HATASE, Atsushi SAKURAI, Tomoharu YOSHINO.
Application Number | 20180282358 15/996693 |
Document ID | / |
Family ID | 55263658 |
Filed Date | 2018-10-04 |
United States Patent
Application |
20180282358 |
Kind Code |
A1 |
SAKURAI; Atsushi ; et
al. |
October 4, 2018 |
ALKOXIDE COMPOUND, THIN FILM-FORMING STARTING MATERIAL, THIN FILM
FORMATION METHOD, AND ALCOHOL COMPOUND
Abstract
The alkoxide compound of the present invention is
characteristically represented by the following general formula
(I): ##STR00001##
Inventors: |
SAKURAI; Atsushi; (Tokyo,
JP) ; HATASE; Masako; (Tokyo, JP) ; YOSHINO;
Tomoharu; (Tokyo, JP) ; ENZU; Masaki; (Tokyo,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ADEKA CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
ADEKA CORPORATION
Tokyo
JP
|
Family ID: |
55263658 |
Appl. No.: |
15/996693 |
Filed: |
June 4, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15318755 |
Dec 14, 2016 |
10011623 |
|
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PCT/JP2015/070385 |
Jul 16, 2015 |
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15996693 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07F 15/065 20130101;
C07F 15/06 20130101; C07F 15/045 20130101; C07F 7/10 20130101; C07F
7/081 20130101; C07C 251/08 20130101; C07C 251/76 20130101; C23C
16/45525 20130101; C07F 15/04 20130101; C23C 16/18 20130101 |
International
Class: |
C07F 15/06 20060101
C07F015/06; C07F 7/10 20060101 C07F007/10; C07C 251/08 20060101
C07C251/08; C07C 251/76 20060101 C07C251/76; C23C 16/18 20060101
C23C016/18; C07F 15/04 20060101 C07F015/04; C07F 7/08 20060101
C07F007/08 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 5, 2014 |
JP |
2014-159270 |
Claims
1. An alcohol compound of the following formula (II): ##STR00052##
wherein R.sup.4 and R.sup.5 are each independently a hydrogen atom,
a C.sub.1-12 hydrocarbon group, or a group of any of the following
formulas (Y-1) to (Y-6) or (Y-8); R.sup.6 is a hydrogen atom or a
C.sub.1-3 hydrocarbon group or a group of any of the following
formulas (Y-1) to (Y-6) or (Y-8); however, when R.sup.4 is a methyl
group and R.sup.5 is a methyl group or an ethyl group, R.sup.6 is a
hydrogen atom or a group of any of the following formulas (Y-1) to
(Y-6) or (Y-8), ##STR00053## wherein R.sup.Y1 to R.sup.Y12 are each
independently a hydrogen atom or a C.sub.1-12 hydrocarbon group,
and A.sup.8 to A.sup.10 are each a C.sub.1-6 alkanediyl group.
Description
TECHNICAL FIELD
[0001] The present invention relates to a novel alkoxide compound,
a thin film-forming starting material containing this compound, a
thin film formation method that uses this thin film-forming
starting material, and a novel alcohol compound.
BACKGROUND ART
[0002] Thin film materials containing metal elements exhibit
electrical characteristics, optical characteristics and the like,
and are thus used in a variety of applications. For example, copper
and copper-containing thin films exhibit the properties of a high
electrical conductivity, a high resistance to electromigration, and
a high melting point and as a result are used as LSI interconnect
materials. In addition, nickel and nickel-containing thin films are
used mainly, for example, for electronic component members, e.g.,
resistive films and barrier films, for recording media members,
e.g., magnetic films, and for members for thin-film solar cells,
e.g., electrodes. Moreover, cobalt and cobalt-containing thin films
are used, for example, for electrode films, resistive films,
adhesive films, magnetic tapes, and carbide tool members.
[0003] The methods for producing these thin films can be
exemplified by sputtering methods, ion plating methods, MOD methods
such as coating-pyrolysis methods and sol-gel methods, and chemical
vapor deposition methods. However, chemical vapor deposition (also
referred to hereafter simply as CVD), which includes atomic layer
deposition (ALD), is the optimal production process because it has
a number of advantages, e.g., it offers excellent composition
controllability and an excellent step coverage capability, it
supports mass production, and it enables hybrid integration.
[0004] A large number of diverse starting materials have been
reported for the metal source used in chemical vapor deposition.
For example, Patent Document 1 discloses a tertiary aminoalkoxide
compound of nickel that can be used as a starting material for
forming a nickel-containing thin film by metal-organic chemical
vapor deposition (MOCVD). Also, Patent Document 2 discloses a
tertiary aminoalkoxide compound of cobalt that can be used as a
starting material for forming a cobalt-containing thin film by
MOCVD. Further, Patent Document 3 discloses a tertiary
aminoalkoxide compound of copper that can be used as a starting
material for forming a copper-containing thin film by chemical
vapor deposition. Non-Patent Document 1 discloses tertiary
imidoalkoxide compounds of copper, nickel, cobalt, iron, manganese,
and chromium.
PRIOR ART DOCUMENTS
Patent Documents
[0005] Patent Document 1: Japanese Patent Laid-Open No. 2008-537947
[0006] Patent Document 2: Korean Patent Registration No. 10-0675983
[0007] Patent Document 3: Japanese Patent Laid-Open No.
2006-328019
Non-Patent Documents
[0007] [0008] Non-Patent Document 1: J. Am. Chem. Soc., 2013, 135,
12588-12591
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0009] When a metal-containing thin film is formed on a substrate
surface by vaporizing, for example, a chemical vapor deposition
starting material, in order to minimize damage to the substrate by
the heat applied during thin film formation and in order to
minimize the energy required for thin film formation, a material is
required that can form the thin film by undergoing thermal
decomposition at low temperatures. The material is also required to
not undergo autoignition from a safety standpoint and to have a low
melting point based on transport considerations. In the particular
case of formation of a metal thin film through the vaporization of
a chemical vapor deposition starting material, problems have
occurred when the chemical vapor deposition starting material is
heated to high temperatures, i.e., the film quality of the metal
thin film has deteriorated and the electrical resistance has
assumed high values and the desired electrical properties have not
been obtained. Thus, there has been demand for chemical vapor
deposition starting materials that can form metal thin films by
undergoing thermal decomposition at low temperatures.
[0010] For example, when a metallic copper thin film is formed by
vaporizing, for example, a chemical vapor deposition starting
material, the problem has occurred that the metallic copper thin
film yielded by heating to 200.degree. C. or above ends up having
high electrical resistance values. While the cause of this problem
has not been determined, the hypothesis here is that, due to the
heating to 200.degree. C. or above, the copper particles present in
the obtained thin film assume larger diameters and/or these
particles undergo aggregation. Thus, with regard to chemical vapor
deposition starting materials for the formation of metallic copper
thin films, there has been demand for such a chemical vapor
deposition starting material for the formation of metallic copper
thin films that undergo thermal decomposition at below 200.degree.
C. The conventional alkoxide compounds have not been thoroughly
satisfactory with regard to thermal stability.
[0011] Accordingly, an object of the present invention is to
provide a novel alkoxide compound that does not undergo
autoignition, that has a low melting point, that exhibits a
satisfactory volatility, and that, for example, can undergo thermal
decomposition at below 200.degree. C. in the case of the cobalt
alkoxide compound and the copper alkoxide compound and can undergo
thermal decomposition at not more than 240.degree. C. in the case
of the nickel alkoxide compound. Additional objects of the present
invention are to provide a thin film-forming starting material
containing this alkoxide compound, to provide a thin film formation
method that uses this thin film-forming starting material, and to
provide a novel alcohol compound for producing the alkoxide
compound.
Means for Solving the Problem
[0012] As a result of extensive investigations, the present
inventors discovered that a special alkoxide compound can solve the
problem identified above and thus achieved the present
invention.
[0013] Thus, the present invention relates to an alkoxide compound
represented by the following general formula (I), to a thin
film-forming starting material that contains this alkoxide
compound, and to a thin film formation method that uses this thin
film-forming starting material.
##STR00002##
[0014] (In the formula, R.sup.1 and R.sup.2 each independently
represent a hydrogen atom, a C.sub.1-12 hydrocarbon group, or a
group represented by any of the following general formulas (X-1) to
(X-8). R.sup.3 represents a hydrogen atom or a C.sub.1-3
hydrocarbon group or a group represented by any of the following
general formulas (X-1) to (X-8). However, when R.sup.1 is a methyl
group and R.sup.2 is a methyl group or an ethyl group, R.sup.3
represents a hydrogen atom or a group represented by any of the
following general formulas (X-1) to (X-8). L represents a hydrogen
atom, a halogen atom, a hydroxyl group, an amino group, an azido
group, a phosphido group, a nitrile group, a carbonyl group, a
C.sub.1-12 hydrocarbon group, or a group represented by any of the
following general formulas (L-1) to (L-13). M represents a metal
atom or a silicon atom; n represents an integer equal to or greater
than 1; m represents an integer equal to or greater than 0; and n+m
represents the valence of the metal atom or silicon atom
represented by M.)
##STR00003##
[0015] (In the formulas, R.sup.X1 to R.sup.X12 each independently
represent a hydrogen atom or a C.sub.1-12 hydrocarbon group, and
A.sup.1 to A.sup.3 represent a C.sub.1-6 alkanediyl group.)
##STR00004## ##STR00005##
[0016] (In the formulas, R.sup.L1 to R.sup.L31 each independently
represent a hydrogen atom or a C.sub.1-12 hydrocarbon group and
A.sup.4 to A.sup.7 represent a C.sub.1-6 alkanediyl group. When an
R.sup.L1 to R.sup.L31 is a C.sub.1-12 hydrocarbon group, a hydrogen
atom in the hydrocarbon group may be substituted by a halogen atom
or an amino group.)
[0017] The present invention also relates to an alcohol compound
represented by the following general formula (II).
##STR00006##
[0018] (In the formula, R.sup.4 and R.sup.5 each independently
represent a hydrogen atom, a C.sub.1-12 hydrocarbon group, or a
group represented by any of the following general formulas (Y-1) to
(Y-8). R.sup.6 represents a hydrogen atom or a C.sub.1-3
hydrocarbon group or a group represented by any of the following
general formulas (Y-1) to (Y-8).
[0019] However, when R.sup.4 is a methyl group and R.sup.5 is a
methyl group or an ethyl group, R.sup.6 represents hydrogen or a
group represented by any of the following general formulas (Y-1) to
(Y-8).
##STR00007##
[0020] (In the formulas, R.sup.Y1 to R.sup.Y12 each independently
represent a hydrogen atom or a C.sub.1-12 hydrocarbon group, and
A.sup.8 to A.sup.10 represent a C.sub.1-6 alkanediyl group.)
Effects of the Invention
[0021] The present invention can provide an alkoxide compound that
does not undergo autoignition, that has a low melting point, that
exhibits a satisfactory volatility, and that, for example, can
undergo thermal decomposition at below 200.degree. C. in the case
of the cobalt alkoxide compound and the copper alkoxide compound
and can undergo thermal decomposition at not more than 240.degree.
C. in the case of the nickel alkoxide compound. This alkoxide
compound is particularly suitable as a thin film-forming starting
material for the formation of metal thin films by a CVD method. The
present invention can also provide a novel alcohol compound.
BRIEF DESCRIPTION OF DRAWINGS
[0022] FIG. 1 is a schematic diagram that shows an example of a
chemical vapor deposition apparatus used in the method according to
the present invention for forming a metal-containing thin film.
[0023] FIG. 2 is a schematic diagram that shows another example of
the chemical vapor deposition apparatus used in the method
according to present invention for forming a metal-containing thin
film.
[0024] FIG. 3 is a schematic diagram that shows another example of
the chemical vapor deposition apparatus used in the method
according to the present invention for forming a metal-containing
thin film.
[0025] FIG. 4 is a schematic diagram that shows another example of
the chemical vapor deposition apparatus used in the method
according to the present invention for forming a metal-containing
thin film.
[0026] FIG. 5 is a molecular structure diagram, obtained by
single-crystal X-ray structural analysis, of alkoxide compound No.
49.
[0027] FIG. 6 is a molecular structure diagram, obtained by
single-crystal X-ray structural analysis, of alkoxide compound No.
171.
BEST MODE FOR CARRYING OUT THE INVENTION
[0028] The alkoxide compound of the present invention is
represented by general formula (I); is highly suitable as a
precursor in thin film production methods that have a vaporization
step, e.g., a CVD method and so forth; and can also form a thin
film using an ALD method. The alkoxide compound of the present
invention has a low melting point and is a compound that becomes a
liquid at 30.degree. C. or when subjected to very minor heating.
Since a compound having a low melting point has good transport
characteristics, the alkoxide compound of the present invention is
highly suitable as a precursor in thin film production methods that
have a vaporization step, e.g., CVD methods and so forth.
[0029] R.sup.1 and R.sup.2 in general formula (I) of the present
invention each independently represent a hydrogen atom, a
C.sub.1-12 hydrocarbon group, or a group represented by any of
general formulas (X-1) to (X-8).
[0030] For example, alkyl, alkenyl, cycloalkyl, aryl, and
cyclopentadienyl can be used as the C.sub.1-12 hydrocarbon group
represented by R.sup.1 and R.sup.2.
[0031] The alkyl can be exemplified by methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, amyl,
isoamyl, hexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl,
nonyl, isononyl, decyl, and dodecyl.
[0032] The alkenyl can be exemplified by vinyl, 1-methylethenyl,
2-methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl,
heptenyl, octenyl, and decenyl.
[0033] The cycloalkyl can be exemplified by cyclohexyl,
cyclopentyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl,
methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl,
methylcyclopentenyl, methylcyclohexenyl, and
methylcycloheptenyl.
[0034] The aryl can be exemplified by phenyl, naphthyl,
2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl,
3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl,
4-isobutylphenyl, 4-tertiary-butylphenyl, 4-hexylphenyl, and
4-cyclohexylphenyl.
[0035] The cyclopentadienyl can be exemplified by cyclopentadienyl,
methylcyclopentadienyl, ethylcyclopentadienyl,
propylcyclopentadienyl, isopropylcyclopentadienyl,
butylcyclopentadienyl, sec-butylcyclopentadienyl,
isobutylcyclopentadienyl, tert-butylcyclopentadienyl,
dimethylcyclopentadienyl, and tetramethylcyclopentadienyl.
[0036] R.sup.3 in general formula (I) represents a hydrogen atom or
a C.sub.1-3 hydrocarbon group or a group represented by any of
general formulas (X-1) to (X-8).
[0037] Specific examples of the C.sub.1-3 hydrocarbon groups
represented by R.sup.3 are methyl, ethyl, propyl, isopropyl, vinyl,
1-methylethenyl, 2-methylethenyl, and propenyl.
[0038] In general formulas (X-1) to (X-8), the R.sup.X1 to
R.sup.X12 each independently represent a hydrogen atom or a
C.sub.1-12 hydrocarbon group, and A.sup.1 to A.sup.3 represent a
C.sub.1-6 alkanediyl group.
[0039] The C.sub.1-12 hydrocarbon groups represented by R.sup.X1 to
R.sup.X12 can be specifically exemplified by the same groups as the
groups provided as examples of the C.sub.1-12 hydrocarbon groups
represented by R.sup.1 and R.sup.2.
[0040] The C.sub.1-6 alkanediyl groups represented by A.sup.1 to
A.sup.3 can be exemplified by methylene, ethylene, propylene, and
butylene.
[0041] The group represented by general formula (X-1) can be
exemplified by dimethylaminomethyl, ethylmethylaminomethyl,
diethylaminomethyl, dimethylaminoethyl, ethylmethylaminoethyl, and
diethylaminoethyl.
[0042] The group represented by general formula (X-2) can be
exemplified by methylamino, ethylamino, propylamino,
isopropylamino, butylamino, sec-butylamino, tert-butylamino, and
isobutylamino.
[0043] The group represented by general formula (X-3) can be
exemplified by dimethylamino, diethylamino, dipropylamino,
diisopropylamino, dibutylamino, di-sec-butylamino,
di-tert-butylamino, ethylmethylamino, propylmethylamino, and
isopropylmethylamino.
[0044] Compounds that contribute the group represented by general
formula (X-4) can be exemplified by ethylenediamino,
hexamethylenediamino, and N,N-dimethylethylenediamino.
[0045] The group represented by general formula (X-5) can be
exemplified by di(trimethylsilyl)amino and
di(triethylsilyl)amino.
[0046] The group represented by general formula (X-6) can be
exemplified by trimethylsilyl and triethylsilyl.
[0047] The group represented by general formula (X-7) can be
exemplified by methoxy, ethoxy, propoxy, isopropoxy, butoxy,
sec-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, and
tert-pentoxy.
[0048] The group represented by general formula (X-8) can be
exemplified by hydroxymethyl, hydroxyethyl, hydroxypropyl,
hydroxyisopropyl, and hydroxybutyl.
[0049] In general formula (I), when R.sup.1 is a methyl group and
R.sup.2 is a methyl group or an ethyl group, R.sup.3 represents a
hydrogen atom or a group represented by any of general formulas
(X-1) to (X-8).
[0050] For the case in which thin film formation includes a step of
vaporizing the alkoxide compound, the R.sup.1, R.sup.2, and R.sup.3
in general formula (I) preferably provide a large vapor pressure
and a low melting point. In the particular case of formation of a
metal thin film, they preferably produce thermal decomposition at,
for example, a temperature below 200.degree. C. for the cobalt
alkoxide compound and copper alkoxide compound and a temperature of
not more than 240.degree. C. for the nickel alkoxide compound.
Specifically, R.sup.1 and R.sup.2 are preferably each independently
a hydrogen atom, a C.sub.1-12 hydrocarbon group, or a group
represented by (X-5) because this provides a high vapor pressure,
whereamong at least one of R.sup.1 and R.sup.2 is particularly
preferably C.sub.1-5 alkyl, di(trimethylsilyl)amino, or
di(triethylsilyl)amino because this provides a low melting point.
More particularly, R.sup.1 and R.sup.2 are preferably both ethyl
for the low melting point this provides, and R.sup.1, R.sup.2, and
R.sup.3 are preferably all ethyl for the particularly low melting
point this provides. In the case of a thin film production method
using a MOD method, which is not accompanied by a vaporization
step, R.sup.1, R.sup.2, and R.sup.3 can be freely selected in
accordance with the solubility in the solvent used, the thin film
formation reaction, and so forth.
[0051] The L in general formula (I) of the present invention
represents a hydrogen atom, a halogen, a hydroxyl group, an amino
group, an azido group, a phosphido group, a nitrile group, a
carbonyl group, a C.sub.1-12 hydrocarbon group, or a group
represented by any of general formulas (L-1) to (L-13). R.sup.L1 to
R.sup.L31 in general formulas (L-1) to (L-13) each independently
represent a hydrogen atom or a C.sub.1-12 hydrocarbon group and
A.sup.4 to A.sup.7 represent a C.sub.1-6 alkanediyl group. When an
R.sup.L1 to R.sup.L31 in general formulas (L-1) to (L-13) is a
C.sub.1-12 hydrocarbon group, a hydrogen atom in the hydrocarbon
group may be substituted by a halogen atom or an amino group.
[0052] The C.sub.1-12 hydrocarbon groups represented by R.sup.L1 to
R.sup.L31 can be specifically exemplified by the same groups as the
groups provided as examples of the C.sub.1-12 hydrocarbon groups
represented by R.sup.1 and R.sup.2.
[0053] The C.sub.1-6 alkanediyl groups represented by A.sup.4 to
A.sup.7 can be specifically exemplified by the same groups as the
groups provided as examples of the C.sub.1-6 alkanediyl groups
represented by A.sup.1 to A.sup.3.
[0054] The group represented by general formula (L-1) can be
exemplified by dimethylaminomethyl, ethylmethylaminomethyl,
diethylaminomethyl, dimethylaminoethyl, ethylmethylaminoethyl, and
diethylaminoethyl.
[0055] The group represented by general formula (L-2) can be
exemplified by methylamino, ethylamino, propylamino,
isopropylamino, butylamino, sec-butylamino, tert-butylamino, and
isobutylamino.
[0056] The group represented by general formula (L-3) can be
exemplified by dimethylamino, diethylamino, dipropylamino,
diisopropylamino, dibutylamino, di-sec-butylamino,
di-tert-butylamino, ethylmethylamino, propylmethylamino, and
isopropylmethylamino.
[0057] Compounds that contribute the group represented by general
formula (L-4) can be exemplified by ethylenediamino,
hexamethylenediamino, and N,N-dimethylethylenediamino.
[0058] The group represented by general formula (L-5) can be
exemplified by di(trimethylsilyl)amino and
di(triethylsilyl)amino.
[0059] The group represented by general formula (L-6) can be
exemplified by trimethylsilyl and triethylsilyl.
[0060] The group represented by general formula (L-7) can be
exemplified by methoxy, ethoxy, propoxy, isopropoxy, butoxy,
sec-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, and
tert-pentoxy.
[0061] The group represented by general formula (L-8) can be
exemplified by hydroxymethyl, hydroxyethyl, hydroxypropyl,
hydroxyisopropyl, and hydroxybutyl.
[0062] The group represented by general formula (L-9) can be
exemplified by dimethylaminoethoxy, diethylaminoethoxy,
dimethylaminopropoxy, ethylmethylaminopropoxy, and die
thylaminopropoxy.
[0063] The group represented by general formula (L-10) can be
exemplified by the groups represented by the following chemical
formulas Nos. (L-10-1) to (L-10-5). In chemical formulas Nos.
(L-10-1) to (L-10-5), "Me" represents methyl; "Et" represents
ethyl; "iPr" represents isopropyl; and "tBu" represents
tert-butyl.
##STR00008##
[0064] Organic compounds that provide the group represented by
general formula (L-10) can be exemplified by the following:
acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione,
heptane-2,4-dione, 2-methylheptane-3,5-dione,
2,6-dimethylheptane-3,5-dione, 1,1,1-trifluoropentane-2,4-dione,
1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione,
1,1,1,5,5,5-hexafluoropentane-2,4-dione,
1,3-diperfluorohexylpropane-1,3-dione,
1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione,
2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione,
2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione,
1,1,1-trifluoropentane-2,4-dione,
1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione,
1,1,1,5,5,5-hexafluoropentane-2,4-dione,
1,3-diperfluorohexylpropane-1,3-dione,
1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione,
2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, and
2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione.
[0065] The group represented by general formula (L-11) can be
exemplified by the groups represented by the following chemical
formulas Nos. (L-11-1) to (L-11-3). In chemical formulas Nos.
(L-11-1) to (L-11-3), "Me" represents methyl; "iPr" represents
isopropyl; and "tBu" represents tert-butyl.
##STR00009##
[0066] Organic compounds that provide the group represented by
general formula (L-11) can be exemplified by
N,N'-diisopropylacetamidinato, N,N'-di-t-butylacetamidinato, and
N,N'-diisopropyl-2-t-butylamidinato.
[0067] The group represented by general formula (L-12) can be
exemplified by the groups represented by the following chemical
formulas Nos. (L-12-1) to (L-12-8). In chemical formulas Nos.
(L-12-1) to (L-12-8), "Me" represents methyl; "iPr" represents
isopropyl; and "tBu" represents tert-butyl.
##STR00010##
[0068] Organic compounds that provide the group represented by
general formula (L-12) can be exemplified by the reaction product
of an organic amine compound, as represented by methylamine,
ethylamine, propylamine, isopropylamine, butylamine,
sec-butylamine, tert-butylamine, isobutylamine, dimethylamine,
diethylamine, dipropylamine, diisopropylamine, ethylmethylamine,
propylmethylamine, isopropylmethylamine, ethylenediamine, and
N,N-dimethylethylenediamine, with a diketone compound, as
represented by acetylacetone, hexane-2,4-dione,
5-methylhexane-2,4-dione, heptane-2,4-dione,
2-methylheptane-3,5-dione, 2,6-dimethylheptane-3,5-dione,
1,1,1-trifluoropentane-2,4-dione,
1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione,
1,1,1,5,5,5-hexafluoropentane-2,4-dione,
1,3-diperfluorohexylpropane-1,3-dione,
1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione,
2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, and
2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione.
[0069] The group represented by general formula (L-13) can be
exemplified by the groups represented by the following chemical
formulas Nos. (L-13-1) to (L-13-8). In chemical formulas Nos.
(L-13-1) to (L-13-8), "Me" represents methyl; "iPr" represents
isopropyl; and "tBu" represents tert-butyl.
##STR00011##
[0070] Organic compounds that provide the group represented by
general formula (L-13) can be exemplified by
N-isopropyl-4-(isopropylimino)pent-2-en-2-amine,
N-isopropyl-4-(isopropylimino)-3-methylpent-2-en-2-amine,
N-(tert-butyl)-4-(tert-butylimino)pent-2-en-2-amine,
N-(tert-butyl)-4-(tert-butylimino)-3-methylpent-2-en-2-amine,
N-isopropyl-5-(isopropylimino)-2,6-dimethylhept-3-en-3-amine,
N-isopropyl-5-(isopropylimino)-2,4,6-trimethylhept-3-en-3-amine,
N-(tert-butyl)-5-(tert-butylimino)-2,2,6,6-tetramethylhept-3-en-3-amine,
and
N-(tert-butyl)-5-(tert-butylimino)-2,2,4,6,6-pentamethylhept-3-en-3-a-
mine.
[0071] It is particularly preferred for m in general formula (I) to
be equal to or greater than 1 and for L to be a group represented
by (L-11) and/or a cyclopentadienyl group as typified by
cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl,
and pentamethylcyclopentadienyl, because this provides a high
thermal stability and a higher vapor pressure. In addition, when m
in general formula (I) of the present invention is equal to or
greater than 2, the L's may be the same as each other or may differ
from one another.
[0072] The M in general formula (I) is a metal atom or a silicon
atom. This metal atom is not particularly limited and can be
exemplified by lithium, sodium, potassium, magnesium, calcium,
strontium, barium, radium, scandium, yttrium, titanium, zirconium,
hafnium, vanadium, niobium, tantalum, chromium, molybdenum,
tungsten, manganese, iron, osmium, cobalt, rhodium, iridium,
nickel, palladium, platinum, copper, silver, gold, zinc, cadmium,
aluminum, gallium, indium, germanium, tin, lead, antimony, bismuth,
lanthanum, cerium, praseodymium, neodymium, promethium, samarium,
europium, gadolinium, terbium, dysprosium, holmium, erbium,
thulium, and ytterbium. Among the preceding, M is particularly
preferably copper, iron, nickel, cobalt, or manganese because this
provides a particularly high thermal stability.
[0073] In general formula (I) of the present invention, n
represents an integer equal to or greater than 1; m represents an
integer equal to or greater than 0; and n+m represents the valence
of the metal atom or silicon atom represented by M.
[0074] The alkoxide compound represented by general formula (I) may
in some cases exhibit optical activity; however, the alkoxide
compound of the present invention is not particularly distinguished
with regard to the (R)-compound and (S)-compound and may be either
or may be a mixture of the (R)-compound and (S)-compound in any
proportions. The racemic mixture has low production costs.
[0075] The following general formula (I-A) represents the case in
which the alkoxide compound of the present invention forms a cyclic
structure through the coordination of terminal donor groups in the
ligand to the metal atom or silicon atom. Here, the alkoxide
compound of the present invention, while being represented by
general formula (I), is not to be differentiated from the alkoxide
compound represented by general formula (I-A) and also encompasses
the alkoxide compound represented by general formula (I-A).
##STR00012##
[0076] (In the formula, R.sup.1 and R.sup.2 each independently
represent a hydrogen atom, a C.sub.1-12 hydrocarbon group, or a
group represented by any of the following general formulas (X-1) to
(X-8). R.sup.3 represents a hydrogen atom or a C.sub.1-3
hydrocarbon group or a group represented by any of the following
general formulas (X-1) to (X-8). However, when R.sup.1 is a methyl
group and R.sup.2 is a methyl group or an ethyl group, R.sup.3
represents a hydrogen atom or a group represented by any of the
following general formulas (X-1) to (X-8). L represents a hydrogen
atom, halogen, a hydroxyl group, an amino group, an azido group, a
phosphido group, a nitrile group, a carbonyl group, a C.sub.1-12
hydrocarbon group, or a group represented by any of the following
general formulas (L-1) to (L-13). M represents a metal atom or a
silicon atom; n represents an integer equal to or greater than 1; m
represents an integer equal to or greater than 0; and n+m
represents the valence of the metal atom or silicon atom
represented by M.)
##STR00013##
[0077] (In the formulas, R.sup.X1 to R.sup.X12 each independently
represent a hydrogen atom or a C.sub.1-12 hydrocarbon group, and
A.sup.1 to A.sup.3 represent a C.sub.1-6 alkanediyl group.)
##STR00014## ##STR00015##
[0078] (In the formulas, R.sup.L1 to R.sup.L31 each independently
represent hydrogen or a C.sub.1-12 hydrocarbon group and A.sup.4 to
A.sup.7 represent a C.sub.1-6 alkanediyl group. When an R.sup.L1 to
R.sup.L31 is a C.sub.1-12 hydrocarbon group, a hydrogen atom in the
hydrocarbon group may be substituted by a halogen atom or an amino
group.)
[0079] Preferred specific examples of the alkoxide compound
represented by general formula (I) are, for example, the compounds
represented by the following chemical formulas No. 1 to No. 91 when
M=cobalt. In chemical formulas No. 1 to No. 91, "Me" represents
methyl; "Et" represents ethyl; "iPr" represents isopropyl; "Cp"
represents cyclopentadienyl; "MeCp" represents
methylcyclopentadienyl; "sCp" represents
pentamethylcyclopentadienyl; and "AMD" represents
N,N'-diisopropylacetamidinato.
##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020##
##STR00021## ##STR00022## ##STR00023## ##STR00024##
[0080] Preferred specific examples of the alkoxide compound
represented by general formula (I) are, for example, the compounds
represented by the following chemical formulas No. 173 to No. 263
when M=nickel. In chemical formulas No. 173 to No. 263, "Me"
represents methyl; "Et" represents ethyl; "iPr" represents
isopropyl; "Cp" represents cyclopentadienyl; "MeCp" represents
methylcyclopentadienyl; "sCp" represents
pentamethylcyclopentadienyl; and "AMD" represents
N,N'-diisopropylacetamidinato.
##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029##
##STR00030## ##STR00031## ##STR00032## ##STR00033##
[0081] The alkoxide compound of the present invention is not
particularly limited with regard to its method of production, and
it can be produced by the application of known reactions. Commonly
known methods for the synthesis of alkoxide compounds using the
corresponding alcohol can be applied as the method of producing the
alkoxide compound represented by general formula (I) in which m=0,
for example, as follows for production of the cobalt alkoxide
compound: methods in which an inorganic salt of cobalt, e.g., the
halide or nitrate salt, or a hydrate thereof is reacted with the
corresponding alcohol compound in the presence of a base such as
sodium, sodium hydride, sodium amide, sodium hydroxide, sodium
methylate, ammonia, an amine, and so forth; methods in which an
inorganic salt of cobalt, e.g., the halide or nitrate salt, or a
hydrate thereof is reacted with the alkali metal alkoxide of the
corresponding alcohol compound, e.g., the sodium alkoxide, lithium
alkoxide, potassium alkoxide, and so forth; methods in which an
exchange reaction is run between the corresponding alcohol compound
and an alkoxide compound of cobalt with a low molecular weight
alcohol, e.g., the methoxide, ethoxide, isopropoxide, butoxide, and
so forth; and methods in which an inorganic salt of cobalt, e.g.,
the halide or nitrate salt, is reacted with a derivative that
provides a reactive intermediate to obtain a reactive intermediate
and this is then reacted with the corresponding alcohol compound.
The reactive intermediate can be exemplified by
bis(dialkylamino)cobalt, bis(bis(trimethylsilyl)amino)cobalt, and
amide compounds of cobalt. The method of producing the alkoxide
compound in which m in general formula (I) is equal to or greater
than 1 can be exemplified by methods in which the alkoxide compound
for which m=0 in general formula (I) is produced by a production
method as described above followed by reaction with an organic
compound that contributes the desired ligand or with the alkali
metal salt of such an organic compound.
[0082] The thin film-forming starting material of the present
invention employs the above-described alkoxide compound of the
present invention as a thin film precursor, and its formulation
will vary as a function of the production process in which the thin
film-forming starting material is applied. For example, when a thin
film containing only silicon or a single species of metal is to be
produced, the thin film-forming starting material of the present
invention will not contain a metal compound or semimetal compound
other than the alkoxide compound. When, on the other hand, a thin
film containing two or more species of metal and/or semimetal is to
be produced, the thin film-forming starting material of the present
invention will contain, in addition to the alkoxide compound, a
compound containing the desired metal and/or a compound containing
the desired semimetal (also referred to hereafter as the additional
precursor). The thin film-forming starting material of the present
invention may, as described below, additionally contain an organic
solvent and/or a nucleophilic reagent. Because, as has been
described above, the properties of the precursor alkoxide compound
are well suited to the CVD and ALD methods, the thin film-forming
starting material of the present invention is thus particularly
useful as a chemical vapor deposition starting material (also
referred to hereafter as a CVD starting material).
[0083] When the thin film-forming starting material of the present
invention is a chemical vapor deposition starting material, its
formulation is selected as appropriate as a function of the
techniques, e.g., the transport and supply procedures and so forth,
in the CVD method that is used.
[0084] This transport and supply procedure can be a gas transport
method or a liquid transport method: in the former, the CVD
starting material residing in a container that stores the starting
material (also referred to hereafter simply as a starting material
container) is vaporized into vapor by heating and/or reducing the
pressure and this vapor is introduced, in combination with a
carrier gas used on an optional basis, e.g., argon, nitrogen,
helium, and so forth, into a film-formation chamber in which the
substrate is disposed (also referred to hereafter as the deposition
reaction section); in the latter, the CVD starting material is
transported in a liquid or solution state to a vaporizer and is
vaporized into a vapor at the vaporizer by heating and/or reducing
the pressure and this vapor is then introduced into the
film-formation chamber. In the gas transport method, the alkoxide
compound represented by general formula (I) can itself be used as
the CVD starting material. In the liquid transport method, the
alkoxide compound represented by general formula (I) itself or a
solution provided by dissolving this compound in an organic solvent
can be used as the CVD starting material. These CVD starting
materials may also contain an additional precursor, a nucleophilic
reagent, and so forth.
[0085] In addition, the CVD method with a multicomponent system
includes a method in which each component of the CVD starting
material is independently vaporized and supplied (also referred to
herebelow as the single-source method) and a method in which a
starting material mixture, prepared by preliminarily mixing the
multicomponent starting material in the desired composition, is
vaporized and supplied (also referred to herebelow as the
cocktail-source method). In the case of the cocktail-source method,
the CVD starting material can be a mixture of the alkoxide compound
of the present invention and an additional precursor or can be a
mixed solution provided by dissolving such a mixture in an organic
solvent. This mixture or mixed solution can additionally contain,
for example, a nucleophilic reagent. When only the alkoxide
compound of the present invention is used as the precursor and a
combination of (R)-compound and (S)-compound is used, a CVD
starting material containing the (R)-compound may be vaporized
separately from a CVD starting material containing the (S)-compound
or a CVD starting material containing a mixture of the (R)-compound
and (S)-compound may be vaporized.
[0086] There are no particular limitations on the organic solvent
here, and commonly known organic solvents can be used. This organic
solvent can be exemplified by acetate esters such as ethyl acetate,
butyl acetate, and methoxyethyl acetate; ethers such as
tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether,
diethylene glycol dimethyl ether, triethylene glycol dimethyl
ether, dibutyl ether, and dioxane; ketones such as methyl butyl
ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl
ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and
methylcyclohexanone; hydrocarbons such as hexane, cyclohexane,
methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane,
octane, toluene, and xylene; cyano group-containing hydrocarbons
such as 1-cyanopropane, 1-cyanobutane, 1-cyanohexane,
cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane,
1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and
1,4-dicyanobenzene; and pyridine and lutidine. A single one of
these solvents or a mixed solvent of two or more is used based on
considerations such as the solubility of the solutes, the
relationship between the use temperature and the boiling point and
flash point, and so forth. When an organic solvent is used, the
total amount of the precursor in the CVD starting material, which
in this case is the solution provided by the dissolution of the
precursor in the organic solvent, is preferably 0.01 to 2.0
mol/liter and is particularly preferably 0.05 to 1.0 mol/liter.
Here, "the total amount of the precursor" is the amount of the
alkoxide compound of the present invention when the thin
film-forming starting material of the present invention does not
contain a metal compound or semimetal compound other than the
alkoxide compound of the present invention, and is the sum total
amount of the alkoxide compound of the present invention and the
additional precursor when the thin film-forming starting material
of the present invention contains another metal-containing compound
and/or semimetal-containing compound in addition to the alkoxide
compound.
[0087] In the case of the CVD method with a multicomponent system,
there are no particular limitations on the additional precursor
used in combination with the alkoxide compound of the present
invention, and the commonly known precursors used in CVD starting
materials can be used.
[0088] This additional precursor can be exemplified by one or two
or more compounds of silicon and/or a metal, selected from the
group consisting of compounds having, for example, the following as
a ligand: hydride, hydroxide, halide, azido, alkyl, alkenyl,
cycloalkyl, aryl, alkynyl, amino, dialkylaminoalkyl,
monoalkylamino, dialkylamino, diamine, di(silylalkyl)amino,
di(alkylsilyl)amino, disilylamino, alkoxy, alkoxyalkyl, hydrazido,
phosphido, nitrile, dialkylaminoalkoxy, alkoxyalkyldialkylamino,
siloxy, diketonato, cyclopentadienyl, silyl, pyrazolato,
guanidinato, phosphoguanidinato, amidinato, phosphoamidinato,
ketoiminato, diketiminato, carbonyl, and phosphoamidinato.
[0089] The metal species in the precursor can be exemplified by
magnesium, calcium, strontium, barium, radium, scandium, yttrium,
titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum, tungsten, manganese, iron, osmium, cobalt,
rhodium, iridium, nickel, palladium, platinum, copper, silver,
gold, zinc, cadmium, aluminum, gallium, indium, germanium, tin,
lead, antimony, bismuth, lanthanum, cerium, praseodymium,
neodymium, promethium, samarium, europium, gadolinium, terbium,
dysprosium, holmium, erbium, thulium, and ytterbium.
[0090] These additional precursors are known in this technical
field, and their production methods are also known. In an example
of a production method, and taking the use of an alcohol compound
for the organic ligand as an example, the precursor can be produced
by reacting the alkali metal alkoxide of the alcohol compound with
an inorganic salt of the metal, or a hydrate thereof. Here, the
inorganic salt of the metal or hydrate thereof can be exemplified
by the halide, nitrate salt, and so forth of the metal, and the
alkali metal alkoxide can be exemplified by the sodium alkoxide,
lithium alkoxide, and potassium alkoxide.
[0091] In the case of the single-source method, this additional
precursor preferably is a compound that exhibits a thermal and/or
oxidative decomposition behavior similar to that of the alkoxide
compound of the present invention. In the case of the
cocktail-source method, the additional precursor preferably has a
similar thermal and/or oxidative decomposition behavior while also
not undergoing alteration, e.g., by a chemical reaction, when
mixed.
[0092] Among the additional precursors described above, precursors
containing titanium, zirconium, or hafnium can be exemplified by
compounds represented by the following formulas (II-1) to
(II-5).
##STR00034##
[0093] (In the formulas, M.sup.1 represents titanium, zirconium, or
hafnium; R.sup.a and R.sup.b each independently represent a
C.sub.1-20 alkyl group, which may be substituted by a halogen atom
and which may contain an oxygen atom in the chain; R.sup.c
represents a C.sub.1-8 alkyl group; R.sup.d represents a possibly
branched C.sub.2-18 alkylene group; R.sup.e and R.sup.f each
independently represent a hydrogen atom or a C.sub.1-3 alkyl group;
R.sup.g, R.sup.h, R.sup.k, and R.sup.i each independently represent
a hydrogen atom or a C.sub.1-4 alkyl group; p represents an integer
from 0 to 4; q represents 0 or 2; r represents an integer from 0 to
3; s represents an integer from 0 to 4; and t represents an integer
from 1 to 4.)
[0094] The alkyl group represented by R.sup.a and R.sup.b in
formulas (II-1) to (II-5) can be exemplified by methyl, ethyl,
propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl,
isoamyl, sec-amyl, tert-amyl, hexyl, cyclohexyl,
1-methylcyclohexyl, heptyl, 3-heptyl, isoheptyl, tert-heptyl,
n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, trifluoromethyl,
perfluorohexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl,
2-(2-methoxyethoxy)ethyl, 1-methoxy-1,1-dimethylmethyl,
2-methoxy-1,1-dimethylethyl, 2-ethoxy-1,1-dimethylethyl,
2-isopropoxy-1,1-dimethylethyl, 2-butoxy-1,1-dimethylethyl, and
2-(2-methoxyethoxy)-1,1-dimethylethyl. The alkyl group represented
by R.sup.c can be exemplified by methyl, ethyl, propyl, isopropyl,
butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, sec-amyl,
tert-amyl, hexyl, 1-ethylpentyl, cyclohexyl, 1-methylcyclohexyl,
heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, and
2-ethylhexyl. The alkylene group represented by R.sup.d is a group
provided by a glycol, and this glycol can be exemplified by
1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol,
2,4-hexanediol, 2,2-dimethyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol, 2,2-diethyl-1,3-butanediol,
2-ethyl-2-butyl-1,3-propanediol, 2,4-pentanediol,
2-methyl-1,3-propanediol, and 1-methyl-2,4-pentanediol. The alkyl
group represented by R.sup.e and R.sup.f can be exemplified by
methyl, ethyl, propyl, and 2-propyl, and the alkyl group
represented by R.sup.g, R.sup.h, R.sup.j, and R.sup.k can be
exemplified by methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,
tert-butyl, and isobutyl.
[0095] The titanium-containing precursor can be specifically
exemplified by tetrakisalkoxytitaniums such as
tetrakis(ethoxy)titanium, tetrakis(2-propoxy)titanium,
tetrakis(butoxy)titanium, tetrakis(sec-butoxy)titanium,
tetrakis(isobutoxy)titanium, tetrakis(tert-butoxy)titanium,
tetrakis(tert-amyl)titanium, and
tetrakis(1-methoxy-2-methyl-2-propoxy)titanium;
tetrakis-.beta.-diketonatotitaniums such as
tetrakis(pentane-2,4-dionato)titanium,
(2,6-dimethylheptane-3,5-dionato)titanium, and
tetrakis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium;
bis(alkoxy)bis(.beta.-diketonato)titaniums such as
bis(methoxy)bis(pentane-2,4-dionato)titanium,
bis(ethoxy)bis(pentane-2,4-dionato)titanium,
bis(tert-butoxy)bis(pentane-2,4-dionato)titanium,
bis(methoxy)bis(2,6-dimethylheptane-3,5-dionato)titanium,
bis(ethoxy)bis(2,6-dimethylheptane-3,5-dionato)titanium,
bis(2-propoxy)bis(2,6-dimethylheptane-3,5-dionato)titanium,
bis(tert-butoxy)bis(2,6-dimethylheptane-3,5-dionato)titanium,
bis(tert-amyloxy)bis(2,6-dimethylheptane-3,5-dionato)titanium,
bis(methoxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato) titanium,
bis(ethoxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium,
bis(2-propoxy)bis(2,6,6,6-tetramethylheptane-3,5-dionato)titanium,
bis(tert-butoxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium,
and bis(tert-amyloxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)
titanium; glycoxybis(.beta.-diketonato)titaniums such as
(2-methylpentanedioxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium
and (2-methylpentanedioxy)bis(2,6-dimethylheptane-3,5-dionato)
titanium; (cyclopentadienyl)tris(dialkylamino)titaniums such as
(methylcyclopentadienyl)tris(dimethylamino)titanium,
(ethylcyclopentadienyl)tris(dimethylamino)titanium,
(cyclopentadienyl)tris(dimethylamino)titanium,
(methylcyclopentadienyl)tris(ethylmethylamino)titanium,
(ethylcyclopentadienyl)tris(ethylmethylamino)titanium,
(cyclopentadienyl)tris(ethylmethylamino)titanium,
(methylcyclopentadienyl)tris(diethylamino)titanium,
(ethylcyclopentadienyl)tris(diethylamino)titanium, and
(cyclopentadienyl)tris(diethylamino)titanium; and
(cyclopentadienyl)tris(alkoxy)titaniums such as
(cyclopentadienyl)tris(methoxy)titanium,
(methylcyclopentadienyl)tris(methoxy)titanium,
(ethylcyclopentadienyl)tris(methoxy)titanium,
(propylcyclopentadienyl)tris(methoxy)titanium,
(isopropylcyclopentadienyl)tris(methoxy)titanium,
(butylcyclopentadienyl)tris(methoxy)titanium,
(isobutylcyclopentadienyl)tris(methoxy)titanium,
tert-butylcyclopentadienyl)tris(methoxy)titanium, and
(pentamethylcyclopentadienyl)tris(methoxy)titanium. The
zirconium-containing precursor and the hafnium-containing precursor
can be exemplified by compounds provided by substituting zirconium
or hafnium for the titanium in the compounds provided above as
examples of the titanium-containing precursor.
[0096] Rare earth element-containing precursors can be exemplified
by compounds represented by the following formulas (III-1) to
(III-3).
##STR00035##
[0097] (In the formulas, M.sup.2 represents a rare earth atom;
R.sup.a and R.sup.b each independently represent a C.sub.1-20 alkyl
group, which may be substituted by a halogen atom and which may
contain an oxygen atom in the chain; R.sup.c represents a C.sub.1-8
alkyl group; R.sup.e and R.sup.f each independently represent a
hydrogen atom or a C.sub.1-3 alkyl group; R.sup.g and R.sup.i each
independently represent a C.sub.1-4 alkyl group; p' represents an
integer from 0 to 3; and r' represents an integer from 0 to 2.)
[0098] The rare earth atom represented by M.sup.2 in this rare
earth element-containing precursor can be exemplified by scandium,
yttrium, lanthanum, cerium, praseodymium, neodymium, promethium,
samarium, europium, gadolinium, terbium, dysprosium, holmium,
erbium, thulium, ytterbium, and lutetium. The groups represented by
R.sup.a, R.sup.b, R.sup.c, R.sup.e, R.sup.f, R.sup.g, and R.sup.i
can be exemplified by the groups provided above as examples for the
titanium precursors.
[0099] The thin film-forming starting material of the present
invention may as necessary contain a nucleophilic reagent in order
to impart stability to the alkoxide compound of the present
invention and the additional precursor. This nucleophilic reagent
can be exemplified by ethylene glycol ethers such as glyme,
diglyme, triglyme, and tetraglyme; crown ethers such as 18-crown-6,
dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, and
dibenzo-24-crown-8; polyamines such as ethylenediamine,
N,N'-tetramethylethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine,
1,1,4,7,10,10-hexamethyltriethylenetetramine, and
triethoxytriethyleneamine; cyclic polyamines such as cyclam and
cyclen; heterocyclic compounds such as pyridine, pyrrolidine,
piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine,
N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane,
oxazole, thiazole, and oxathiolane; .beta.-ketoesters such as
methyl acetoacetate, ethyl acetoacetate, and 2-methoxyethyl
acetoacetate; and .beta.-diketones such as acetylacetone,
2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and
dipivaloylmethane. The amount of nucleophilic reagent used per 1
mol of the total amount of the precursor is preferably in the range
from 0.1 mol to 10 mol and more preferably is 1 to 4 mol.
[0100] To the greatest extent possible, the thin film-forming
starting material of the present invention does not contain, other
than its constituent components, metal element impurities, halogen
impurities such as chlorine impurities, and organic impurities. The
metal element impurities are, per element, preferably not more than
100 ppb and more preferably not more than 10 ppb, while the total
amount is preferably not more than 1 ppm and more preferably not
more than 100 ppb. In the particular case of use as an LSI gate
dielectric film, gate film, or barrier layer, the content of alkali
metal elements and alkaline-earth metal elements, which affect the
electrical characteristics of the obtained thin film, must be
minimized. The amount of halogen impurity is preferably not more
than 100 ppm, more preferably not more than 10 ppm, and most
preferably not more than 1 ppm. The total amount of organic
impurity is preferably not more than 500 ppm, more preferably not
more than 50 ppm, and most preferably not more than 10 ppm.
Moisture causes the generation of particles in the chemical vapor
deposition starting material and the generation of particles during
thin film formation and because of this the moisture is desirably
preliminarily removed to the greatest extent possible from the
metal compound, organic solvent, and nucleophilic reagent at the
time of use in order to reduce the moisture in each. The amount of
moisture in each of the metal compound, organic solvent, and
nucleophilic reagent is preferably not more than 10 ppm and more
preferably not more than 1 ppm.
[0101] In order to reduce or prevent particle contamination of the
thin film that is formed, the thin film-forming starting material
of the present invention preferably contains as little particulate
as possible. Specifically, in particle measurement in the liquid
phase using a light-scattering detector for liquid-borne particles,
the number of particles larger than 0.3 .mu.m in 1 mL of the liquid
phase is preferably not more than 100; the number of particles
larger than 0.2 .mu.m in 1 mL of the liquid phase is more
preferably not more than 1,000; and the number of particles larger
than 0.2 .mu.m in 1 mL of the liquid phase is most preferably not
more than 100.
[0102] The thin film production method of the present invention,
which produces a thin film by using the thin film-forming starting
material of the present invention, proceeds according to a CVD
method in which a vapor produced by vaporizing the thin
film-forming starting material of the present invention and a
reactive gas used on an optional basis are introduced into a
film-formation chamber in which a substrate is disposed and a
metal-containing thin film is grown and deposited on a substrate
surface by the decomposition and/or chemical reaction of the
precursor on the substrate. The method for transporting and
supplying the starting material, the deposition method, the
production conditions, the production apparatus, and so forth are
not particularly limited and commonly known conditions and methods
can be used.
[0103] The aforementioned reactive gas used on an optional basis
can be exemplified by oxidizing gases such as oxygen, ozone,
nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide,
formic acid, acetic acid, and acetic anhydride; by reducing gases
such as hydrogen; and by gases that produce nitride, such as
hydrazine, ammonia, and organic amine compounds such as
monoalkylamine, dialkylamine, trialkylamine, and alkylenediamine. A
single one of these may be used or two or more may be used.
[0104] The transport and supply method can be exemplified by the
previously described gas transport method, liquid transport method,
single-source method, and cocktail-source method.
[0105] The deposition method can be exemplified by thermal CVD, in
which a thin film is deposited by causing the starting material
gas, or the starting material gas and a reactive gas, to react only
through the application of heat; plasma CVD, which uses heat and a
plasma; photo-CVD, which uses heat and light; plasma photo-CVD,
which uses heat, light, and a plasma; and ALD, in which deposition
is carried out stepwise at the molecular level by dividing the CVD
deposition reactions into elementary processes.
[0106] The material of the substrate can be exemplified by silicon;
ceramics, e.g., silicon nitride, titanium nitride, tantalum
nitride, titanium oxide, titanium nitride, ruthenium oxide,
zirconium oxide, hafnium oxide, and lanthanum oxide; glasses; and
metals such as ruthenium metal. The shape of the substrate can be
exemplified by plate shaped, spherical, fibrous, and scale shaped,
and the substrate surface may be flat or may assume a
three-dimensional structure, e.g., a trench structure and so
forth.
[0107] The production conditions referenced above are, for example,
the reaction temperature (substrate temperature), reaction
pressure, deposition rate, and so forth. With regard to the
reaction temperature, 100.degree. C. or above--which are
temperatures at which the alkoxide compound of the present
invention is thoroughly reacted--is preferred and 150.degree. C. to
400.degree. C. is more preferred. 150.degree. C. to 250.degree. C.
is particularly preferred because the alkoxide compound of the
present invention can undergo thermal decomposition at below
200.degree. C. In addition, the reaction pressure is preferably
atmospheric pressure to 10 Pa in the case of thermal CVD and
photo-CVD and is preferably 2,000 Pa to 10 Pa when a plasma is
used.
[0108] The deposition rate can be controlled using the conditions
for starting material supply (vaporization temperature,
vaporization pressure), the reaction temperature, and the reaction
pressure. Since a high deposition rate can result in a
deterioration of the characteristics of the obtained thin film and
a low deposition rate can produce productivity issues, the
deposition rate is preferably 0.01 to 100 nm/minute and is more
preferably 1 to 50 nm/minute. With an ALD method, control is
exercised using the number of cycles so as to obtain the desired
film thickness.
[0109] Other production conditions are the temperature and pressure
during production of the vapor by vaporizing the thin film-forming
starting material. The step of producing the vapor by vaporization
of the thin film-forming starting material can be carried out in
the starting material container or in a vaporizer.
[0110] In either case, the thin film-forming starting material of
the present invention is preferably vaporized at 0 to 150.degree.
C. In addition, when a vapor is prepared by vaporizing the thin
film-forming starting material within the starting material
container or a vaporizer, the pressure within the starting material
container or the pressure within the vaporizer is preferably 1 to
10,000 Pa in either case.
[0111] When the thin film formation method of the present invention
uses an ALD method, the following steps may be included in addition
to the starting material introduction step in which a vapor is
produced by vaporizing the thin film-forming starting material and
this vapor is introduced into the film-formation chamber: a
precursor thin film formation step, in which a precursor thin film
is formed on the surface of the substrate by the alkoxide compound
in the vapor; an exhaust step, in which the unreacted alkoxide
compound gas is exhausted; and a step of forming a metal-containing
thin film, in which a metal-containing thin film is formed on the
surface of the substrate by chemical reaction of the precursor thin
film with reactive gas.
[0112] Each of the steps referenced above is described in detail in
the following using the formation of a metal oxide thin film as an
example. The starting material introduction step described above is
carried out first in the case of formation of a metal oxide thin
film using the ALD method. The preferred temperature and pressure
for conversion of the thin film-forming starting material to the
vapor is the same as already described above. The precursor thin
film is then formed on a substrate surface by the alkoxide compound
that has been introduced into the deposition reaction section
(precursor thin film formation step). During this, the application
of heat may be carried out by heating the substrate or by heating
the deposition reaction section. The precursor thin film formed in
this step is a metal oxide thin film, or is a thin film produced by
the decomposition and/or reaction of a portion of the alkoxide
compound, and has a composition different from that of the target
metal oxide thin film. The substrate temperature during the
execution of this step is preferably room temperature to
500.degree. C. and is more preferably 150 to 350.degree. C. The
pressure in the system (within the film-formation chamber) during
the execution of this step is preferably 1 to 10,000 Pa and more
preferably 10 to 1,000 Pa.
[0113] The unreacted alkoxide compound gas and by-product gas are
then exhausted from the deposition reaction section (exhaust step).
Complete exhaust of the unreacted alkoxide compound gas and
by-product gas from the deposition reaction section is the ideal,
but complete exhaust is not necessarily required. The exhaust
method can be exemplified by the following: methods in which the
interior of the system is purged using an inert gas such as
nitrogen, helium, or argon; methods in which exhaust is performed
by reducing the pressure in the system; and methods that combine
the preceding. In the case of pressure reduction, the vacuum is
preferably 0.01 to 300 Pa and is more preferably 0.01 to 100
Pa.
[0114] Then, an oxidizing gas is introduced into the deposition
reaction section and a metal oxide thin film is formed through the
action of the oxidizing gas or through the action of the oxidizing
gas and heat from the precursor thin film obtained in the preceding
precursor thin film formation step (metal oxide-containing thin
film formation step). The temperature in this step when the action
of heat is employed is preferably room temperature to 500.degree.
C. and more preferably 150 to 350.degree. C. The pressure in the
system (within the film-formation chamber) during the execution of
this step is preferably 1 to 10,000 Pa and more preferably 10 to
1,000 Pa. The alkoxide compound of the present invention has an
excellent reactivity with oxidizing gases and can produce metal
oxide thin films.
[0115] When the ALD method as described above is used in the thin
film formation method of the present invention, and taking 1 cycle
to be thin film deposition by a process chain composed of the
previously described starting material introduction step, precursor
thin film formation step, exhaust step, and metal oxide-containing
thin film formation step, this cycle is repeated a plurality of
times until a thin film of the required film thickness is obtained.
In this case, after 1 cycle has been executed, the ensuing cycle is
preferably carried out after exhausting from the deposition
reaction section, proceeding in the same manner as for the exhaust
step, the unreacted alkoxide compound gas and reactive gas (an
oxidizing gas when a metal oxide thin film is being formed) and
also the by-product gas.
[0116] In addition, energy, e.g., plasma, light, voltage, and so
forth, may be applied and a catalyst may be used in the formation
of a metal oxide thin film by the ALD method. The timing of the
application of energy and the timing for catalyst use are not
particularly limited and, for example, may be during the
introduction of the alkoxide compound gas in the starting material
introduction step, during the heating in the precursor thin film
formation step or the metal oxide-containing thin film formation
step, during exhaust of the system interior in the exhaust step,
during the introduction of the oxidizing gas in the metal
oxide-containing thin film formation step, and between these
steps.
[0117] In order to obtain even better electrical characteristics,
thin film deposition in the thin film formation method of the
present invention may be followed by the execution of an annealing
process under an inert atmosphere, an oxidizing atmosphere, or a
reducing atmosphere, while a reflow step may also be implemented
when step coverage is required. The temperature in this case is 200
to 1,000.degree. C. and preferably 250 to 500.degree. C.
[0118] A known chemical vapor deposition apparatus can be used as
the apparatus for producing a thin film using the thin film-forming
starting material of the present invention. Specific examples of
the apparatus are the apparatus shown in FIG. 1, which operates
through the bubbling supply of the precursor, and the apparatus
shown in FIG. 2, which has a vaporizer. Other examples are the
apparatuses shown in FIGS. 3 and 4, which can carry out a plasma
treatment on the reactive gas. There is no limitation to the
single-wafer apparatuses shown in FIGS. 1 to 4, and an apparatus
capable of the simultaneous processing of a plurality of wafers
using a batch furnace can also be used.
[0119] The thin film produced using the thin film-forming starting
material of the present invention can be produced in the desired
species of thin film, e.g., metal, oxide ceramic, nitride ceramic,
glass, and so forth, by the appropriate selection of the additional
precursor, the reactive gas, and the production conditions. These
thin films are known to exhibit, inter alia, various electrical
properties and optical properties and are used in a variety of
applications. For example, copper and copper-containing thin films
exhibit the properties of a high electrical conductivity, a high
resistance to electromigration, and a high melting point and as a
result are used as LSI interconnect materials. In addition, nickel
and nickel-containing thin films are used mainly, for example, for
electronic component members, e.g., resistive films and barrier
films, for recording media members, e.g., magnetic films, and for
members for thin-film solar cells, e.g., electrodes. Cobalt and
cobalt-containing thin films are used, for example, for electrode
films, resistive films, adhesive films, magnetic tapes, and carbide
tool members.
[0120] The alcohol compound of the present invention is represented
by the following general formula (II) and is a compound that is
particularly well suited as a ligand for use in compounds that are
advantageous as precursors in thin film formation methods that have
a vaporization step, e.g., CVD methods and so forth.
##STR00036##
[0121] (In the formula, R.sup.4 and R.sup.5 each independently
represent a hydrogen atom, a C.sub.1-12 hydrocarbon group, or a
group represented by any of the following general formulas (Y-1) to
(Y-8). R.sup.6 represents a hydrogen atom or a C.sub.1-3
hydrocarbon group or a group represented by any of the following
general formulas (Y-1) to (Y-8).
[0122] However, when R.sup.4 is a methyl group and R.sup.5 is a
methyl group or an ethyl group, R.sup.6 represents a hydrogen atom
or a group represented by any of the following general formulas
(Y-1) to (Y-8).)
##STR00037##
[0123] (In the formulas, R.sup.Y1 to R.sup.Y12 each independently
represent a hydrogen atom or a C.sub.1-12 hydrocarbon group, and
A.sup.8 to A.sup.10 represent a C.sub.1-6 alkanediyl group.)
[0124] R.sup.4 and R.sup.5 in general formula (II) each
independently represent a hydrogen atom, a C.sub.1-12 hydrocarbon
group, or a group represented by any of general formulas (Y-1) to
(Y-8).
[0125] For example, alkyl, alkenyl, cycloalkyl, aryl, and
cyclopentadienyl can be used for the hydrocarbon groups represented
by R.sup.4 and R.sup.5.
[0126] The alkyl can be exemplified by methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, amyl,
isoamyl, hexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl,
nonyl, isononyl, decyl, and dodecyl.
[0127] The alkenyl can be exemplified by vinyl, 1-methylethenyl,
2-methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl,
heptenyl, octenyl, and decenyl.
[0128] The cycloalkyl can be exemplified by cyclohexyl,
cyclopentyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl,
methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl,
methylcyclopentenyl, methylcyclohexenyl, and
methylcycloheptenyl.
[0129] The aryl can be exemplified by phenyl, naphthyl,
2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl,
3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl,
4-isobutylphenyl, 4-tertiary-butylphenyl, 4-hexylphenyl, and
4-cyclohexylphenyl.
[0130] The cyclopentadienyl can be exemplified by cyclopentadienyl,
methylcyclopentadienyl, ethylcyclopentadienyl,
propylcyclopentadienyl, isopropylcyclopentadienyl,
butylcyclopentadienyl, sec-butylcyclopentadienyl,
isobutylcyclopentadienyl, tert-butylcyclopentadienyl,
dimethylcyclopentadienyl, and tetramethylcyclopentadienyl.
[0131] R.sup.6 in general formula (II) represents a hydrogen atom
or a C.sub.1-3 hydrocarbon group or a group represented by any of
general formulas (Y-1) to (Y-8).
[0132] Specific examples of the hydrocarbon groups represented by
R.sup.6 are methyl, ethyl, propyl, isopropyl, vinyl,
1-methylethenyl, 2-methylethenyl, and propenyl.
[0133] When R.sup.4 in general formula (II) is a methyl group and
R.sup.5 is a methyl group or an ethyl group, R.sup.6 represents a
hydrogen atom or a group represented by any of general formulas
(Y-1) to (Y-8).
[0134] The C.sub.1-12 hydrocarbon groups represented by R.sup.Y1 to
R.sup.Y12 can be specifically exemplified by the same groups as the
groups provided as examples of the C.sub.1-12 hydrocarbon groups
represented by R.sup.4 and R.sup.5.
[0135] The C.sub.1-6 alkanediyl groups represented by A.sup.8 to
A.sup.10 can be exemplified by methylene, ethylene, propylene, and
butylene.
[0136] The group represented by general formula (Y-1) can be
exemplified by dimethylaminomethyl, ethylmethylaminomethyl,
diethylaminomethyl, dimethylaminoethyl, ethylmethylaminoethyl, and
diethylaminoethyl.
[0137] The group represented by general formula (Y-2) can be
exemplified by methylamino, ethylamino, propylamino,
isopropylamino, butylamino, sec-butylamino, tert-butylamino, and
isobutylamino.
[0138] The group represented by general formula (Y-3) can be
exemplified by dimethylamino, diethylamino, dipropylamino,
diisopropylamino, dibutylamino, di-sec-butylamino,
di-tert-butylamino, ethylmethylamino, propylmethylamino, and
isopropylmethylamino.
[0139] Compounds that contribute the group represented by general
formula (Y-4) can be exemplified by ethylenediamino,
hexamethylenediamino, and N,N-dimethylethylenediamino.
[0140] The group represented by general formula (Y-5) can be
exemplified by di(trimethylsilyl)amino and
di(triethylsilyl)amino.
[0141] The group represented by general formula (Y-6) can be
exemplified by trimethylsilyl and triethylsilyl.
[0142] The group represented by general formula (Y-7) can be
exemplified by methoxy, ethoxy, propoxy, isopropoxy, butoxy,
sec-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, and
tert-pentoxy.
[0143] The group represented by general formula (Y-8) can be
exemplified by hydroxymethyl, hydroxyethyl, hydroxypropyl,
hydroxyisopropyl, and hydroxybutyl.
[0144] Optical isomers may also exist for the alcohol compound of
the present invention, but the alcohol compound of the present
invention is not distinguished with regard to its optical
isomerism.
[0145] Preferred specific examples of the alcohol compound
represented by general formula (II) are, for example, the compounds
represented by the following chemical formulas No. 92 to No. 170.
In the following chemical formulas, "Me" represents methyl; "Et"
represents ethyl; and "iPr" represents isopropyl.
##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042##
##STR00043## ##STR00044## ##STR00045##
[0146] The alcohol compound of the present invention is not
particularly limited with regard to its method of production, and
it can be produced by the application of known reactions.
[0147] The following are examples: a method as shown in the
following reaction formula (1), in which a Grignard reaction is run
between an alkyl compound and an alkyl alkoxycarboxylate compound
using magnesium as a catalyst, and an additional reaction with an
alkylamine is carried out followed by extraction of the reaction
product with a suitable solvent and a drying treatment; a method as
shown in the following reaction formula (2), in which a Grignard
reaction is run between an alkyl compound and an alkoxy ketone
alkyl compound using magnesium as a catalyst, and an additional
reaction with an alkylamine is carried out followed by extraction
of the reaction product with a suitable solvent and a drying
treatment; and a method as shown in the following reaction formula
(3), in which a Grignard reaction is run between an alkyl compound
and a dialkyl diketone compound using magnesium as a catalyst, and
an additional reaction with an alkylamine is carried out followed
by extraction with a suitable solvent and a drying treatment.
##STR00046##
##STR00047##
##STR00048##
[0148] [R.sup.z in reaction formula (1) and reaction formula (2)
represents an alkyl group.]
[0149] The alcohol compound of the present invention can be used as
a ligand in a metal compound used for, inter alia, a thin
film-forming starting material. In addition, the alcohol compound
of the present invention can also be used, for example, as a
synthesis starting material for solvents, fragrances,
agrochemicals, pharmaceuticals, various polymers, and so forth.
EXAMPLES
[0150] The present invention is described in additional detail
below using examples and evaluation examples. However, the present
invention is in no way limited to or by the following examples.
Example 1: Synthesis of Alcohol Compound No. 134
[0151] 22.43 g of 3-dimethoxymethyl-3-pentanol, 40 g of pure water,
and 3.6 g of 36% hydrochloric acid were added under ice cooling to
a reaction flask and stirring was carried out for 5 hours. This was
followed by the dropwise addition of 23.72 g of a 40% aqueous
methylamine solution with ice cooling and reaction for 17 hours.
The pH of the reaction solution at this time was 10 to 11. 32.9 g
of toluene was added; the organic layer was extracted and
separated; and magnesium sulfate was added and drying and
filtration were performed. The solvent was distilled off on an oil
bath at 90.degree. C. under reduced pressure to obtain alcohol
compound No. 134. 7.69 g was obtained for a yield of 43%.
[0152] (Analytic values)
[0153] (1) GC-MS m/z: 129 (M+)
[0154] (3) elementary analysis: C, 65.4 mass %, H, 12.1 mass %, O,
11.2 mass %, N, 11.3 mass % (theoretical values: C, 65.1 mass %, H,
11.7 mass %, O, 12.4 mass %, N, 10.8 mass %)
Example 2: Synthesis of Alcohol Compound No. 140
[0155] A diethyl ether solution of ethylmagnesium bromide
(concentration=21.85 mass %, 277 g) was added to a reaction flask
and was cooled to around 0.degree. C. by stirring on an ice-cooling
bath. A Grignard reaction was carried out by the dropwise addition
to this solution over one hour of methyl dimethoxyacetate (25 g).
This was followed by return to room temperature and reaction for 12
hours. The reaction solution was ice-cooled; 200 g of a saturated
aqueous ammonium chloride solution was added dropwise; and the pH
was subsequently adjusted to around neutrality by the dropwise
addition of 10 mL of a 36% hydrochloric acid solution. The solution
was then transferred to a separatory funnel; the organics were
extracted with 50 g of hexane and separated; and drying was carried
out over an appropriate amount of magnesium sulfate. This hexane
suspension was filtered followed by removal of the solvent on an
oil bath at around 65.degree. C. Distillation was performed under
reduced pressure on an oil bath at around 100.degree. C. to obtain
22.4 g of a transparent and colorless 3-dimethoxymethyl-3-pentanol
(GC purity=96.3%). 10 g of pure water and 1 g of 36% hydrochloric
acid were added under ice cooling to 7 g of the
3-dimethoxymethyl-3-pentanol and stirring was carried out
overnight. After this, 9.5 g of a 33% aqueous ethylamine solution
was added dropwise under ice cooling and a reaction was run for 10
hours. The pH of the reaction solution at this time was 10 to 11.
When stirring was stopped, separation occurred into an aqueous
layer and a small amount of an organic layer, and the organic layer
was determined to be alcohol compound No. 140 according to the NMR
results. 2.7 g of the target was obtained for a yield of 33%.
[0156] (Analytic values)
[0157] (1) GC-MS m/z: 143 (M+)
[0158] (2).sup.1NMR (solvent: deuterobenzene) (chemical shift:
multiplicity: number of H) (7.020: s: 1) (4.379: s: 1)
(3.171-3.193: q: 2) (1.559-1.649: m: 2) (1.310-1.400: m: 2)
(0.979-1.016: t: 3) (0.837-0.874: t: 6)
[0159] (3) elementary analysis: C, 67.5 mass %, H, 12.1 mass %, O,
12.0 mass %, N, 9.6 mass % (theoretical values: C, 67.1 mass %, H,
12.0 mass %, O, 11.2 mass %, N, 9.8 mass %)
Example 3: Synthesis of Alcohol Compound No. 146
[0160] 19.67 g of 3-dimethoxymethyl-3-pentanol, 35 g of pure water,
and 8.9 g of 36% hydrochloric acid were added under ice cooling to
a reaction flask and stirring was performed for 4 hours. 16.67 g of
isopropylamine was then added dropwise under ice cooling and a
reaction was carried out for 18 hours. The pH of the reaction
solution at this time was 10 to 11. 28.8 g of toluene was added;
the organic layer was extracted and separated; and magnesium
sulfate was added and drying and filtration were carried out. The
solvent was distilled off on an oil bath at 90.degree. C. under
reduced pressure to obtain alcohol compound No. 146. 13.48 g was
obtained for a yield of 69%.
[0161] (Analytic values)
[0162] (1) GC-MS m/z: 157 (M+)
[0163] (3) elementary analysis: C, 69.0 mass %, H, 11.9 mass %, O,
11.0 mass %, N, 8.9 mass % (theoretical values: C, 68.7 mass %, H,
12.2 mass %, O, 10.2 mass %, N, 8.9 mass %)
Example 4: Synthesis of Alcohol Compound No. 166
[0164] 2.17 g of magnesium and 118 g of tetrahydrofuran were
introduced into a reaction flask and 11.3 g of 2-bromopropane was
gradually added dropwise to this at a bath temperature of
50.degree. C. After cooling to room temperature and stirring for 2
hours, 10.3 g of pyruvic aldehyde dimethyl acetal was gradually
added dropwise and stirring was performed for 20 hours at room
temperature. Quenching was performed by the addition of 39 g of an
8% aqueous hydrochloric acid solution and 25.3 g of ammonium
chloride. To this was added 26.7 g of hexane and the target
material (intermediate) was extracted into the organic layer and
was dried over sodium sulfate followed by filtration. The hexane
was distilled off at a bath temperature of 85.degree. C. under a
slight pressure reduction and the obtained residue was distilled
under a slight pressure reduction at a column top temperature of
50.degree. C. and a bath temperature of 85.degree. C. to obtain the
intermediate 1,1-dimethoxy-2,3-dimethyl-2-butanol. 18.5 g of
H.sub.2O was added to 6.0 g of the
1,1-dimethoxy-2,3-dimethyl-2-butanol and to this was gradually
added dropwise at room temperature 2.1 g of a 36% aqueous
hydrochloric acid solution. After stirring for 2 hours, 15.3 g of a
33% aqueous ethylamine solution was gradually added dropwise under
water cooling. After stirring for 20 hours at room temperature,
31.2 g of toluene was added and the target material was extracted
into the organic layer. Drying over sodium sulfate was carried out
followed by filtration, and the toluene was distilled off at a bath
temperature of 85.degree. C. under a slightly reduced pressure. The
obtained residue was distilled under a slightly reduced pressure at
a bath temperature of 85.degree. C. to obtain alcohol compound No.
166. 3.6 g (GC purity=92%) was obtained for a yield of 27%.
[0165] (Analytic values)
[0166] (1) GC-MS m/z: 143 (M+)
[0167] (3) elementary analysis: C, 67.4 mass %, H, 12.3 mass %, O,
10.5 mass %, N, 9.4 mass % (theoretical values: C, 67.0 mass %, H,
12.0 mass %, O, 11.2 mass %, N, 9.8 mass %)
Example 5: Synthesis of Alcohol Compound No. 167
[0168] 10.0 g of 1,1-dimethoxy-2,3-dimethyl-2-butanol (90% pure
product) and 10.0 g of H.sub.2O were introduced into a reaction
flask; to this was gradually added dropwise 1.5 g of a 36% aqueous
hydrochloric acid solution with ice cooling; and stirring was
performed for 20 hours at room temperature. 11.5 g of
isopropylamine was gradually added dropwise with ice cooling and,
after warming to room temperature, stirring was performed for 20
hours. 70 g of toluene was added and the target material was
extracted into the organic layer. Drying over sodium sulfate and
filtration were carried out. A toluene solution (3.19 mass %) of
1-isopropylimino-2,3-dimethyl-2-butanol was obtained. The solvent
was distilled off on an oil bath at 90.degree. C. under reduced
pressure to obtain alcohol compound No. 167.
[0169] (Analytic values)
[0170] (1) GC-MS m/z: 157 (M+)
[0171] (3) elementary analysis: C, 69.0 mass %, H, 11.9 mass %, O,
10.6 mass %, N, 8.8 mass % (theoretical values: C, 68.7 mass %, H,
12.2 mass %, O, 10.2 mass %, N, 8.9 mass %)
Example 6: Synthesis of Alkoxide Compound No. 43
[0172] 4.04 g of cobalt (II) chloride and 16 g of tetrahydrofuran
were introduced into a 200-mL four-neck flask and were stirred at
room temperature. To this was added dropwise with ice cooling a
solution prepared by the dilution, with 17 g of tetrahydrofuran, of
8.77 g of the sodium alkoxide prepared from alcohol compound No.
134 (3-methyliminomethyl-3-pentanol). After the completion of the
dropwise addition, stirring was performed for 16 hours at room
temperature followed by filtration. The tetrahydrofuran was removed
from the obtained filtrate and the residue was distilled under
conditions of 60 Pa and 130.degree. C. to obtain 1.34 g of alkoxide
compound No. 43 for a yield of 14.5%.
[0173] (Analytic values)
[0174] (1) Vacuum TG-DTA
[0175] 50% mass loss temperature: 136.2.degree. C. (10 Torr, Ar
flow rate: 50 mL/minute, heating at 10.degree. C./minute)
[0176] (2) elementary analysis: Co: 18.4 mass %, C, 53.6 mass %, H,
8.7 mass %, O, 10.6 mass %, N, 8.6 mass % (theoretical values: Co:
18.7 mass %, C, 53.3 mass %, H, 9.0 mass %, O, 10.1 mass %, N, 8.9
mass %)
Example 7: Synthesis of Alkoxide Compound No. 49
[0177] 13.23 g of cobalt(II) chloride and 48 g of tetrahydrofuran
were introduced into a 200-mL four-neck flask and were stirred at
room temperature. To this was added dropwise with ice cooling a
solution prepared by the dilution, with 50 g of tetrahydrofuran, of
33.04 g of the sodium alkoxide prepared from alcohol compound No.
140 (3-ethyliminomethyl-3-pentanol). After the completion of the
dropwise addition, stirring was performed for 22 hours at room
temperature followed by filtration. The tetrahydrofuran was removed
from the obtained filtrate and the residue was distilled under
conditions of 40 Pa and 125.degree. C. to obtain 28.70 g of
alkoxide compound No. 49 for a yield of 83.5%. The results of
single-crystal X-ray structural analysis of the obtained alkoxide
compound No. 49 are shown in FIG. 5.
[0178] (Analytic values)
[0179] (1) Vacuum TG-DTA
[0180] 50% mass loss temperature: 125.8.degree. C. (10 Torr, Ar
flow rate: 50 mL/minute, heating at 10.degree. C./minute)
[0181] (2) elementary analysis: Co: 16.5 mass %, C, 56.3 mass %, H,
9.5 mass %, O, 9.8 mass %, N, 7.9 mass % (theoretical values: Co:
17.2 mass %, C, 56.0 mass %, H, 9.4 mass %, O, 9.3 mass %, N, 8.2
mass %)
Example 8: Synthesis of Alkoxide Compound No. 55
[0182] 5.75 g of cobalt (II) chloride and 18 g of tetrahydrofuran
were introduced into a 200-mL four-neck flask and were stirred at
room temperature. To this was added dropwise with ice cooling a
solution prepared by the dilution, with 17 g of tetrahydrofuran, of
15.06 g of the sodium alkoxide prepared from alcohol compound No.
146 (3-isopropyliminomethyl-3-pentanol). After the completion of
the dropwise addition, stirring was performed for 29 hours at room
temperature followed by filtration. The tetrahydrofuran was removed
from the obtained filtrate and the residue was distilled under
conditions of 50 Pa and 135.degree. C. to obtain 5.53 g of alkoxide
compound No. 55 for a yield of 35.1%.
[0183] (Analytic values)
[0184] (1) Vacuum TG-DTA
[0185] 50% mass loss temperature: 130.3.degree. C. (10 Torr, Ar
flow rate: 50 mL/minute, heating at 10.degree. C./minute)
[0186] (2) elementary analysis: Co: 15.0 mass %, C, 59.0 mass %, H,
9.7 mass %, O, 8.9 mass %, N, 7.5 mass % (theoretical values: Co:
15.9 mass %, C, 58.2 mass %, H, 9.8 mass %, O, 8.6 mass %, N, 7.5
mass %)
Example 9: Synthesis of Alkoxide Compound No. 75
[0187] 1.52 g of cobalt(II) chloride and 8.22 g of tetrahydrofuran
were introduced into a 100-mL three-neck flask and were stirred at
room temperature. To this was added dropwise with ice cooling a
solution prepared by the dilution, with 7. 95 g of tetrahydrofuran,
of 3.80 g of the sodium alkoxide prepared from alcohol compound No.
166 (1-ethylimino-2,3-dimethyl-2-butanol). After the completion of
the dropwise addition, stirring was performed for 15 hours at room
temperature followed by filtration. The tetrahydrofuran was removed
from the obtained filtrate and the residue was distilled under
conditions of 45 Pa, a bath temperature of 130.degree. C., and a
column top temperature of 90.degree. C. to obtain 1.56 g of
alkoxide compound No. 75 for a yield of 39.3%.
[0188] (Analytic values)
[0189] (1) Vacuum TG-DTA
[0190] 50% mass loss temperature: 123.degree. C. (10 Torr, Ar flow
rate: 50 mL/minute, heating at 10.degree. C./minute)
[0191] (2) elementary analysis: Co: 16.9 mass %, C, 56.2 mass %, H,
9.2 mass %, O, 9.7 mass %, N, 8.3 mass % (theoretical values: Co:
17.2 mass %, C, 56.0 mass %, H, 9.4 mass %, O, 9.3 mass %, N, 8.2
mass %)
Example 10: Synthesis of Alkoxide Compound No. 171
[0192] 32 g of a 3.8 mass % toluene solution of alcohol compound
No. 134 (3-methyliminomethyl-3-pentanol) was added dropwise to 0.59
g of copper(II) methoxide under an argon gas atmosphere.
Dissolution occurred rapidly with the assumption of a purple color,
and stirring was carried out in this condition for 20 hours at room
temperature. The toluene was distilled off under a slightly reduced
pressure at an oil bath temperature of 70.degree. C. and the
residual toluene was then completely distilled off under reduced
pressure at an oil bath temperature of 90.degree. C. The obtained
purple solid was distilled at 100.degree. C. and 40 Pa to obtain
the target. The obtained compound was a solid with a melting point
of 60.degree. C. The yield of this compound was 70%. Single-crystal
X-ray structural analysis was performed on the obtained compound.
The molecular structure provided by single-crystal X-ray structural
analysis is shown in FIG. 6. It could be confirmed from this result
that the obtained compound was alkoxide compound No. 171.
[0193] (Analytic values)
[0194] (1) Vacuum TG-DTA
[0195] 50% mass loss temperature: 120.degree. C. (10 Torr, Ar flow
rate: 50 mL/minute, heating at 10.degree. C./minute)
[0196] (2) elementary analysis: Cu: 19.7 mass %, C, 52.4 mass %, H,
8.9 mass %, O, 10.7 mass %, N, 8.4 mass (theoretical values: Cu:
19.9 mass %, C, 52.6 mass %, H, 8.8 mass %, O, 10.0 mass %, N, 8.8
mass %)
##STR00049##
Example 11: Synthesis of Alkoxide Compound No. 172
[0197] 38 g of a 3.7 mass toluene solution of alcohol compound No.
140 (3-ethyliminomethyl-3-pentanol) was added dropwise to 0.62 g of
copper (II) methoxide under an argon gas atmosphere. Dissolution
occurred rapidly with the assumption of a purple color, and
stirring was carried out in this condition for 18 hours at room
temperature. The toluene was distilled off under a slightly reduced
pressure at an oil bath temperature of 70.degree. C. and the
residual toluene was then completely distilled off under reduced
pressure at an oil bath temperature of 90.degree. C. The obtained
purple liquid was distilled at 100.degree. C. and 40 Pa to obtain
alkoxide compound No. 172 in the form of a purple liquid. The yield
of alkoxide compound No. 172 was 45%.
[0198] (Analytic values)
[0199] (1) Vacuum TG-DTA
[0200] 50% mass loss temperature: 120.degree. C. (10 Torr, Ar flow
rate: 50 mL/minute, heating at 10.degree. C./minute)
[0201] (2) elementary analysis: Cu: 18.4 mass %, C, 54.9 mass %, H,
8.8 mass %, O, 9.0 mass %, N, 8.2 mass (theoretical values: Cu:
18.3 mass %, C, 55.2 mass %, H, 9.3 mass %, O, 9.2 mass %, N, 8.1
mass %)
##STR00050##
Example 12: Synthesis of Alkoxide Compound No. 221
[0202] 4.97 g of hexaamminenickel(II) chloride and 95 g of
tetrahydrofuran were introduced into a 500-mL four-neck flask and
were stirred at room temperature. To this was added dropwise with
ice cooling a solution prepared by the dilution, with 180 g of
tetrahydrofuran, of the sodium alkoxide prepared from 36.0 g of a
17.2 mass % toluene solution of the alcohol
(3-ethyliminomethyl-3-pentanol). After the completion of the
dropwise addition, stirring was carried out with heating to
70.degree. C., followed by removal of the tetrahydrofuran and
toluene. The residue was dissolved in hexane and filtration was
performed. The hexane was removed from the obtained filtrate and
the residue was purified under conditions of 25 Pa and 100.degree.
C. to obtain 2.80 g of compound No. 221 for a yield of 37.8%.
[0203] (Analytic values)
[0204] (1) Vacuum TG-DTA
[0205] 50% mass loss temperature: 134.degree. C. (10 Torr, Ar flow
rate: 50 mL/minute, heating at 10.degree. C./minute)
[0206] (2) elementary analysis: Ni: 17.3 mass %, C, 56.2 mass %, H,
9.2 mass %, O, 9.2 mass %, N, 8.0 mass (theoretical values: Ni:
17.10 mass %, C, 56.01 mass %, H, 9.40 mass %, O, 9.33 mass %, N,
8.16 mass %)
[0207] (3) .sup.1NMR (solvent: deuterobenzene) (chemical shift:
multiplicity: number of H) (6.877: s: 2) (2.745-2.797: q: 4)
(1.328-1.386: m: 8) (1.229-1.266: t: 12) (1.147-1.182: t: 6)
Example 13: Synthesis of Compound No. 247
[0208] 6.88 g of hexaamminenickel(II) chloride and 42.8 g of
tetrahydrofuran were introduced into a 200-mL four-neck flask and
were stirred at room temperature. To this was added dropwise with
ice cooling a solution prepared by the dilution, with 42.8 g of
tetrahydrofuran, of 9.80 g of the sodium alkoxide prepared from the
alcohol (1-ethylimino-2,3-dimethyl-2-butanol). After the completion
of the dropwise addition, stirring was carried out for 14 hours at
room temperature. Heating was carried out under reflux for 2 hours
and, after allowing to cool to room temperature, the
tetrahydrofuran was removed under reduced pressure. 65 g of hexane
was added to the resulting residue and filtration was performed.
The hexane was removed from the obtained filtrate and the residue
was distilled under conditions of 50 Pa and 100.degree. C. to
obtain 2.50 g of compound No. 247 for a yield of 30.70.
[0209] (Analytic values)
[0210] (1) Vacuum TG-DTA
[0211] 50% mass loss temperature: 132.9.degree. C. (10 Torr, Ar
flow rate: 50 mL/minute, heating at 10.degree. C./minute)
[0212] (2).sup.1NMR (solvent: deuterobenzene) (chemical shift:
multiplicity: number of H) (7.030: d: 2) (2.932-2.593: m: 4)
(1.605-1.509: m: 2) (1.661: dd: 12) (1.084-1.117: m: 12)
[0213] (3) elementary analysis: Ni: 17.2 mass %, C, 56.3 mass %, H,
9.0 mass %, O, 9.3 mass %, N, 7.9 mass % (theoretical values: Ni:
17.1 mass %, C, 56.0 mass %, H, 9.40 mass %, O, 9.33 mass %, N,
8.16 mass %)
[0214] [Evaluation of Autoignition Behavior]
[0215] The presence/absence of autoignition of alkoxide compounds
Nos. 43, 49, 55, 75, 171, 172, 221, and 247 was checked by allowing
to stand in the atmosphere. The results are shown in Table 1.
TABLE-US-00001 TABLE 1 presence/absence of evaluation example
compound autoignition Evaluation Example 1-1 compound No. 43 Absent
Evaluation Example 1-2 compound No. 49 Absent Evaluation Example
1-3 compound No. 55 Absent Evaluation Example 1-4 compound No. 75
Absent Evaluation Example 1-5 compound No. 171 Absent Evaluation
Example 1-6 compound No. 172 Absent Evaluation Example 1-7 compound
No. 221 Absent Evaluation Example 1-8 compound No. 247 Absent
[0216] [Evaluation of Thermal Stability]
[0217] The initial thermal decomposition temperature was measured
using a DSC measurement instrument for alkoxide compounds Nos. 43,
49, 55, 75, 171, 172, 221, and 247 and the comparative compounds 1
to 6 shown below. The results are shown in Table 2.
##STR00051##
TABLE-US-00002 TABLE 2 initial thermal decomposition evaluation
example compound temperature Evaluation Example 2-1 compound No. 43
190.degree. C. Evaluation Example 2-2 compound No. 49 170.degree.
C. Evaluation Example 2-3 compound No. 55 190.degree. C. Evaluation
Example 2-4 compound No. 75 170.degree. C. Evaluation Example 2-5
compound No. 171 160.degree. C. Evaluation Example 2-6 compound No.
172 160.degree. C. Evaluation Example 2-7 compound No. 221
200.degree. C. Evaluation Example 2-8 compound No. 247 230.degree.
C. Comparative Example 1 comparative compound 1 220.degree. C.
Comparative Example 2 comparative compound 2 210.degree. C.
Comparative Example 3 comparative compound 3 230.degree. C.
Comparative Example 4 comparative compound 4*.sup.1 160.degree. C.
Comparative Example 5 comparative compound 5*.sup.2 190.degree. C.
Comparative Example 6 comparative compound 6 290.degree. C.
*.sup.1The melting point was 160.degree. C. or above, and thermal
decomposition occurred without going through a liquid state.
*.sup.2The melting point was 185.degree. C., and a stable liquid
state could not be maintained.
[0218] A comparison of the results in Table 2 for alkoxide
compounds Nos. 43, 49, 55, 75, 171, and 172 with those for
comparative compounds 1 to 3 and a comparison of the results for
alkoxide compounds Nos. 221 and 247 with those for comparative
compound 6 demonstrated that alkoxide compounds Nos. 43, 49, 55,
75, 171, and 172 could undergo thermal decomposition at
temperatures lower than for comparative compounds 1 to 3 and that
alkoxide compounds Nos. 221 and 247 could undergo thermal
decomposition at temperatures lower than for comparative compound
6. In addition, it was shown that alkoxide compounds Nos. 43, 49,
55, 75, 171, 172, and 221 had thermal decomposition temperatures of
not more than 200.degree. C., while alkoxide compounds Nos. 43, 49,
55, 75, 171, and 172 underwent thermal decomposition at
temperatures below 200.degree. C. It was also shown that
comparative compound 4, while having a low initial thermal
decomposition temperature, also had a melting point that was higher
than its initial thermal decomposition temperature and thus could
not support a liquid state. It was shown that comparative compound
5, while having a low initial thermal decomposition temperature
just like comparative compound 4, had a melting point at a
temperature very near its initial thermal decomposition temperature
and was thus unable to maintain a stable liquid state. Alkoxide
compound No. 171, which was evaluated in Evaluation Example 2-5,
was a compound with a low initial thermal decomposition temperature
and a melting point of 60.degree. C., and alkoxide compound No.
172, which was evaluated in Evaluation Example 2-6, was a compound
that had a low initial thermal decomposition temperature and that
was in the liquid state at 30.degree. C. Compounds that have a low
melting point and a large temperature difference between their
melting point and initial thermal decomposition temperature, can be
easily maintained in the liquid state and require little energy for
transport and are thus well suited as chemical vapor deposition
starting materials.
Example 14: Production of Metallic Cobalt Thin Films by ALD
Method
[0219] Metallic cobalt thin films were produced on silicon wafers
using alkoxide compounds Nos. 43, 49, 55, and 75 as the chemical
vapor deposition starting materials and using an ALD method under
the conditions indicated below using the apparatus shown in FIG. 2.
When the obtained thin films were submitted to measurement of the
film thickness by X-ray reflectivity and identification of the thin
film structure and thin film composition by X-ray diffraction and
X-ray photoelectron spectroscopy, the film thickness was 2 to 4 nm,
the film composition was metallic cobalt (identification by the Co
2p peak by XPS analysis), and the carbon content was less than the
0.1 atom % lower detection limit. The film thickness obtained per 1
cycle was 0.02 to 0.04 nm.
[0220] (Conditions)
[0221] reaction temperature (wafer temperature): 300.degree. C.;
reactive gas: hydrogen gas
[0222] (Process)
[0223] The process chain composed of the following (1) to (4) was 1
cycle, and 100 cycles were performed.
[0224] (1) The chemical vapor deposition starting material is
vaporized using conditions of a vaporizer temperature of
110.degree. C. and a vaporizer pressure of 50 Pa, and the resulting
vapor is introduced and deposition is carried out for 30 seconds at
a system pressure of 50 Pa.
[0225] (2) The unreacted starting material is removed by an argon
purge for 5 seconds.
[0226] (3) The reactive gas is introduced and a reaction is carried
out for 30 seconds at a system pressure of 50 Pa.
[0227] (4) The unreacted starting material is removed by an argon
purge for 5 seconds.
Example 15: Production of Metallic Copper Thin Films by ALD
Method
[0228] Metallic copper thin films were produced on silicon wafers
using alkoxide compounds Nos. 171 and 172 as the chemical vapor
deposition starting materials and using a PEALD method under the
conditions indicated below using a plasma deposition apparatus
shown in FIG. 3. When the obtained thin films were submitted to
measurement of the film thickness by X-ray reflectivity and
identification of the thin film structure and thin film composition
by X-ray diffraction and X-ray photoelectron spectroscopy, the film
thickness was 2 to 4 nm, the film composition was metallic copper
(identification by the Cu 2p peak by XPS analysis), and the carbon
content was less than the 0.1 atom % lower detection limit. The
film thickness obtained per 1 cycle was 0.02 to 0.04 nm.
[0229] (Conditions)
[0230] reaction temperature (wafer temperature): 60.degree. C.;
reactive gas: hydrogen gas; plasma output: 50 W
[0231] (Process)
[0232] The process chain composed of the following (1) to (4) was 1
cycle, and 100 cycles were performed.
[0233] (1) The chemical vapor deposition starting material is
vaporized using conditions of a heating temperature of 60.degree.
C. for the starting material container and a pressure within the
starting material container of 50 Pa, and the resulting vapor is
introduced and deposition is carried out for 30 seconds at a system
pressure of 50 Pa.
[0234] (2) The unreacted starting material is removed by an argon
purge for 5 seconds.
[0235] (3) The reactive gas and plasma are introduced and a
reaction is carried out for 30 seconds at a system pressure of 50
Pa.
[0236] (4) The unreacted starting material is removed by an argon
purge for 5 seconds.
Example 16: Production of Metallic Nickel Thin Films by ALD
Method
[0237] Metallic nickel thin films were produced on silicon wafers
using each of alkoxide compounds Nos. 221 and 247 as the chemical
vapor deposition starting material and using a thermal ALD method
under the conditions indicated below using the apparatus shown in
FIG. 1. When the obtained thin films were submitted to measurement
of the film thickness by X-ray reflectivity and identification of
the thin film structure and thin film composition by X-ray
diffraction and X-ray photoelectron spectroscopy, in each case the
film thickness was 20 to 40 nm, the film composition was metallic
nickel (identification by the Ni 2p peak by XPS analysis), and the
carbon content and nitrogen content were less than the 0.1 atom %
lower detection limit. The film thickness obtained per 1 cycle was
0.02 to 0.04 nm.
[0238] (Conditions)
[0239] reaction temperature (wafer temperature): 230.degree. C.;
reactive gas: hydrogen gas
[0240] (Process)
[0241] The process chain composed of the following (1) to (4) was 1
cycle, and 1,000 cycles were performed.
[0242] (1) The chemical vapor deposition starting material is
vaporized using conditions of a vaporizer temperature of 70.degree.
C. and a vaporizer pressure of 50 Pa, and the resulting vapor is
introduced and deposition is carried out for 30 seconds at a system
pressure of 50 Pa.
[0243] (2) The unreacted starting material is removed by an argon
purge for 5 seconds.
[0244] (3) The reactive gas is introduced and a reaction is carried
out for 30 seconds at a system pressure of 50 Pa.
[0245] (4) The unreacted starting material is removed by an argon
purge for 5 seconds.
Example 17: Production of Metallic Nickel Thin Films by ALD
Method
[0246] Metallic nickel thin films were produced on silicon wafers
using each of alkoxide compounds Nos. 221 and 247 as the chemical
vapor deposition starting material and using a PEALD method under
the conditions indicated below using the plasma deposition
apparatus shown in FIG. 3. When the obtained thin films were
submitted to measurement of the film thickness by X-ray
reflectivity and identification of the thin film structure and thin
film composition by X-ray diffraction and X-ray photoelectron
spectroscopy, in each case the film thickness was 50 to 70 nm, the
film composition was metallic copper (identification by the Ni 2p
peak by XPS analysis), and the carbon content and nitrogen content
were less than the 0.1 atom % lower detection limit. The film
thickness obtained per 1 cycle was 0.05 to 0.07 nm.
[0247] (Conditions)
[0248] reaction temperature (wafer temperature): 70.degree. C.;
reactive gas: hydrogen gas; plasma output: 50 W
[0249] (Process)
[0250] The process chain composed of the following (1) to (4) was 1
cycle, and 1,000 cycles were performed.
[0251] (1) The chemical vapor deposition starting material is
vaporized using conditions of a heating temperature of 70.degree.
C. for the starting material container and a pressure within the
starting material container of 50 Pa, and the resulting vapor is
introduced and deposition is carried out for 30 seconds at a system
pressure of 50 Pa.
[0252] (2) The unreacted starting material is removed by an argon
purge for 5 seconds.
[0253] (3) The reactive gas and plasma are introduced and a
reaction is carried out for 30 seconds at a system pressure of 50
Pa.
[0254] (4) The unreacted starting material is removed by an argon
purge for 5 seconds.
* * * * *