U.S. patent application number 15/577913 was filed with the patent office on 2018-06-14 for group 4 metal element-containing compound, method of preparing the same, precursor composition including the same for depositing film, and method of depositing film using the same.
The applicant listed for this patent is UP CHEMICAL CO., LTD.. Invention is credited to Won Seok HAN, Wonyong KOH, Myeong-Ho PARK.
Application Number | 20180162882 15/577913 |
Document ID | / |
Family ID | 59500964 |
Filed Date | 2018-06-14 |
United States Patent
Application |
20180162882 |
Kind Code |
A1 |
HAN; Won Seok ; et
al. |
June 14, 2018 |
GROUP 4 METAL ELEMENT-CONTAINING COMPOUND, METHOD OF PREPARING THE
SAME, PRECURSOR COMPOSITION INCLUDING THE SAME FOR DEPOSITING FILM,
AND METHOD OF DEPOSITING FILM USING THE SAME
Abstract
The present disclosure provides a Group 4 metal
element-containing novel compound, a method of preparing the Group
4 metal element-containing compound, a precursor composition
including the Group 4 metal element-containing compound for
depositing a film, and a method of depositing a Group 4 metal
element-containing film using the precursor composition.
Inventors: |
HAN; Won Seok;
(Pyeongtaek-si, Gyeonggi-do, KR) ; KOH; Wonyong;
(Daejeon, KR) ; PARK; Myeong-Ho; (Suwon-si,
Gyeonggi-do, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
UP CHEMICAL CO., LTD. |
Pyeongtaek-si, Gyeonggi-do |
|
KR |
|
|
Family ID: |
59500964 |
Appl. No.: |
15/577913 |
Filed: |
February 3, 2017 |
PCT Filed: |
February 3, 2017 |
PCT NO: |
PCT/KR2017/001161 |
371 Date: |
November 29, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07F 17/00 20130101;
C23C 16/405 20130101; C07F 7/28 20130101; C23C 16/18 20130101; C23C
16/45553 20130101; C07F 7/00 20130101 |
International
Class: |
C07F 7/00 20060101
C07F007/00; C07F 7/28 20060101 C07F007/28; C23C 16/18 20060101
C23C016/18; C23C 16/455 20060101 C23C016/455 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 3, 2016 |
KR |
10-2016-0013203 |
Claims
1. A Group 4 metal element-containing compound, represented by the
following Chemical Formula 1: ##STR00018## in the above Chemical
Formula 1, M is Ti, Zr or Hf, L is NR.sup.5R.sup.6 or a halogen,
each of R.sup.1 to R.sup.4 is independently hydrogen or a linear or
branched alkyl group having 1 to 4 carbon atoms, each of R.sup.5
and R.sup.6 is independently a linear or branched alkyl group
having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
2. The compound of claim 1, wherein the Group 4 metal
element-containing compound is represented by the following
Chemical Formula 2: ##STR00019## in the above Chemical Formula 2, M
is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently
hydrogen or a linear or branched alkyl group having 1 to 4 carbon
atoms, each of R.sup.5 and R.sup.6 is independently a linear or
branched alkyl group having 1 to 4 carbon atoms, and n is an
integer of from 1 to 3.
3. (canceled)
4. The compound of claim 1, wherein the Group 4 metal
element-containing compound is represented by the following
Chemical Formula 4: ##STR00020## in the above Chemical Formula 4, M
is Ti, Zr or Hf, each of R.sup.1 to R.sup.4 is independently
hydrogen or a linear or branched alkyl group having 1 to 4 carbon
atoms, X is a halogen, and n is an integer of from 1 to 3.
5. The compound of claim 1, wherein M is Ti, Zr or Hf, L is
N(CH.sub.3).sub.2, N(C.sub.2H.sub.5).sub.2,
N(CH.sub.3)(C.sub.2H.sub.5) or Cl, and n is an integer of from 1 to
3.
6. A method of preparing a Group 4 metal element-containing
compound represented by the following Chemical Formula 1,
comprising reacting a compound represented by ML.sub.4 with a
Grignard reagent: ##STR00021## in the above Chemical Formula, M is
Ti, Zr or Hf, L is NR.sup.5R.sup.6 or a halogen, each of R.sup.1 to
R.sup.4 is independently hydrogen or a linear or branched alkyl
group having 1 to 4 carbon atoms, each of R.sup.5 and R.sup.6 is
independently a linear or branched alkyl group having 1 to 4 carbon
atoms, and n is an integer of from 1 to 3.
7. The method of claim 6, wherein the Grignard reagent includes a
material represented as Chemical Formula Cp(CH.sub.2).sub.n+1MgX,
and in the above Chemical Formula, Cp(CH.sub.2).sub.n+1 represents
##STR00022## each of R.sup.1 to R.sup.4 is independently hydrogen
or a linear or branched alkyl group having 1 to 4 carbon atoms, n
is an integer of from 1 to 3, and X is a halogen.
8. The method of claim 7, wherein the material represented as
Cp(CH.sub.2).sub.n+1MgX is prepared by reacting
Cp(CH.sub.2).sub.n+1X with Mg, and in the Cp(CH.sub.2).sub.n+1X,
Cp(CH.sub.2).sub.n+1 represents ##STR00023## each of R.sup.1 to
R.sup.4 is independently hydrogen or a linear or branched alkyl
group having 1 to 4 carbon atoms, n is an integer of from 1 to 3,
and X is a halogen.
9. A method of preparing a Group 4 metal element-containing
compound represented by the following Chemical Formula 1',
comprising reacting a compound represented by the following
Chemical Formula 4 with M'NR.sup.5R.sup.6 as an alkali metal salt
of a dialkylamine, wherein M' is an alkali metal and each of
R.sup.5 and R.sup.6 is independently a linear or branched alkyl
group having 1 to 4 carbon atoms: ##STR00024## in the above
Chemical Formula 4, M is Ti, Zr or Hf, each of R.sup.1 to R.sup.4
is independently hydrogen or a linear or branched alkyl group
having 1 to 4 carbon atoms, X is a halogen, and n is an integer of
from 1 to 3; ##STR00025## in the above Chemical Formula 1', M is
Ti, Zr or Hf, L' is NR.sup.5R.sup.6, each of R.sup.1 to R.sup.4 is
independently hydrogen or a linear or branched alkyl group having 1
to 4 carbon atoms, each of R.sup.5 and R.sup.6 is independently a
linear or branched alkyl group having 1 to 4 carbon atoms, and n is
an integer of from 1 to 3.
10. A precursor composition for depositing a film, comprising a
Group 4 metal element-containing compound of claim 1.
11. A method of depositing a Group 4 metal element-containing film,
comprising forming a Group 4 metal element-containing film using a
precursor composition for depositing a film of claim 10.
Description
TECHNICAL FIELD
[0001] The present disclosure relates to a Group 4 metal
element-containing novel compound, a method of preparing the Group
4 metal element-containing compound, a precursor composition
including the Group 4 metal element-containing compound for
depositing a film, and a method of depositing a Group 4 metal
element-containing film using the precursor composition.
BACKGROUND
[0002] A compound containing a Group 4 metal element such as Ti,
Zr, and Hf, e.g., a film of an oxide or nitride containing a Group
4 metal element, e.g., a zirconium oxide film, a titanium nitride
film, etc., is used as a high dielectric material, an electrode,
etc. to manufacture a semiconductor device. To form a film
containing a Group 4 metal element by chemical vapor deposition
(CVD) or atomic layer deposition (ALD), various Group 4 metal
compounds are used. Further, a compound containing a Group 4 metal
element is also used as a catalyst for polymer synthesis [Korean
Patent No. 10-0852234]. However, there is still a need for
developing a Group 4 metal element-containing novel compound which
can be usefully utilized as a precursor for forming a uniform film,
particularly for forming a Group 4 metal element-containing uniform
film or thin film on the entire surface of a substrate having a
trench (groove) or parous substrate.
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0003] The present disclosure is conceived to provide a Group 4
metal element-containing novel compound, a method of preparing the
Group 4 metal element-containing compound, a precursor composition
including the Group 4 metal element-containing compound for
depositing a film, and a method of depositing a Group 4 metal
element-containing film using the precursor composition.
[0004] However, problems to be solved by the present disclosure are
not limited to the above-described problems. Although not described
herein, other problems to be solved by the present disclosure can
be clearly understood by those skilled in the art from the
following description.
Means for Solving the Problems
[0005] According to a first aspect of the present disclosure, there
is provided a Group 4 metal element-containing compound,
represented by the following Chemical Formula 1:
##STR00001##
[0006] in the above Chemical Formula 1, M is Ti, Zr or Hf, L is
NR.sup.5R.sup.6, OR.sup.7 or a halogen, each of R.sup.1 to R.sup.7
is independently hydrogen or a linear or branched alkyl group
having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
[0007] According to a second aspect of the present disclosure,
there is provided a method of preparing a Group 4 metal
element-containing compound, represented by the following Chemical
Formula 1, including reacting a compound represented by ML.sub.4
with a Grignard reagent:
##STR00002##
[0008] in the above Chemical Formula, M is Ti, Zr or Hf, L is
NR.sup.5R.sup.6, OR.sup.7 or a halogen, each of R.sup.1 to R.sup.7
is independently hydrogen or a linear or branched alkyl group
having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
[0009] According to a third aspect of the present disclosure, there
is provided a method of preparing a Group 4 metal
element-containing compound, represented by the following Chemical
Formula 1', including reacting a compound represented by the
following Chemical Formula 4 with M'NR.sup.5R.sup.6 as an alkali
metal salt of a dialkylamine or M'OR.sup.7 as an alkali metal salt
of an alcohol, wherein in each of the M'NR.sup.5R.sup.6 and
M'OR.sup.7, M' is an alkali metal and each of R.sup.5 to R.sup.7 is
independently hydrogen or a linear or branched alkyl group having 1
to 4 carbon atoms:
##STR00003##
[0010] in the above Chemical Formula 4, M is Ti, Zr or Hf, each of
R.sup.1 to R.sup.4 is independently hydrogen or a linear or
branched alkyl group having 1 to 4 carbon atoms, X is a halogen,
and n is an integer of from 1 to 3;
##STR00004##
[0011] in the above Chemical Formula 1', M is Ti, Zr or Hf, L' is
NR.sup.5R.sup.6 or OR.sup.7, each of R' to R.sup.7 is independently
hydrogen or a linear or branched alkyl group having 1 to 4 carbon
atoms, and n is an integer of from 1 to 3.
[0012] According to a fourth aspect of the present disclosure,
there is provided a precursor composition for depositing a film,
including a Group 4 metal element-containing compound according to
the first aspect of the present disclosure.
[0013] According to a fifth aspect of the present disclosure, there
is provided a method of depositing a Group 4 metal
element-containing film, including forming a Group 4 metal
element-containing film using a precursor composition for
depositing a film according to the fourth aspect of the present
disclosure.
Effects of the Invention
[0014] According to an exemplary embodiment of the present
disclosure, a Group 4 metal element-containing novel compound has a
structure in which a carbon directly bonded to a Group 4 central
metal is connected to a cyclopentadienyl group coordinated at the
central metal through an alkylene chain and is a novel compound
which has not been conventionally known in the art. The Group 4
metal element-containing novel compounds according to an exemplary
embodiment of the present disclosure have high thermal stability
and thus can be used as a precursor for atomic layer deposition or
chemical vapor deposition to form a Group 4 metal
element-containing film and particularly can be used to uniformly
form a Group 4 metal element-containing film having a thickness of
several nm to several tens of nm on a substrate having a trench
(groove) in its surface or porous substrate. For example, in a
substrate having a fine trench (groove) with an aspect ratio of
about 1 or more and a width of about 1 .mu.m or less in its
surface, the Group 4 metal element-containing novel compounds have
an excellent effect of uniformly forming a Group 4 metal
element-containing film having a thickness of several nm to several
tens of nm on the entire surface of the substrate including a
surface of the fine trench (groove) including a surface of the
deepest portion of the fine trench (groove) and an upper surface of
the fine trench (groove). According to an exemplary embodiment of
the present disclosure, a method of preparing a Group 4 metal
element-containing film can be applied to manufacturing commercial
semiconductor devices. Particularly, in order to manufacture a DRAM
semiconductor device, it is necessary to form a high dielectric
material to a thickness of several nm on a substrate having a
trench with a width of much less than 100 nm or 50 nm and an aspect
ratio of 10:1, 20:1, or 30:1, or a deeper and narrower trench.
Particularly, it is necessary to form a high dielectric material
having a uniform thickness even at a temperature of 280.degree. C.,
300.degree. C., or more, and, thus, a precursor composition with
which a film having a uniform thickness can be formed on a very
narrow and deep trench by atomic layer deposition (ALD) even at a
high temperature is needed and thus a Ti, Zr, or Hf compound having
very high thermal stability is needed to be used as the precursor
composition.
[0015] The Group 4 metal element-containing compounds according to
an exemplary embodiment of the present disclosure can be used as a
precursor used for ALD, CVD, and the like and thus can provide
properties, e.g., improved thermal stability, high volatility
and/or increased deposition rate, required for manufacturing
next-generation devices such as semiconductors and therefore can be
usefully utilized for forming a Group 4 metal element-containing
film or thin film.
[0016] Further, the Group 4 metal element-containing compounds
according to an exemplary embodiment of the present disclosure can
be applied in various fields such as catalyst and the like.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a H-HMR spectrum of a zirconium-containing
compound prepared in accordance with an example of the present
disclosure.
[0018] FIG. 2 is a thermogravimetric analysis graph for each of the
zirconium-containing compound prepared in accordance with an
example of the present disclosure and a compound according to a
comparative example.
[0019] FIG. 3 is a H-HMR spectrum of a hafnium-containing compound
prepared in accordance with an example of the present
disclosure.
[0020] FIG. 4 is a H-HMR spectrum of a titanium-containing compound
prepared in accordance with an example of the present
disclosure.
[0021] FIG. 5 is a H-HMR spectrum of a titanium-containing compound
prepared in accordance with an example of the present
disclosure.
[0022] FIG. 6 shows film growth by atomic layer deposition using
the zirconium-containing compound prepared in accordance with an
example of the present disclosure and film growth according to a
comparative example, depending on a substrate temperature.
[0023] FIG. 7 shows a transmission electron microscope (TEM)
observation result of a cross section of a film formed using the
zirconium-containing compound prepared in accordance with an
example of the present disclosure on a substrate including a narrow
trench.
[0024] FIG. 8 shows film growth by atomic layer deposition using
the hafnium-containing compound prepared in accordance with an
example of the present disclosure, depending on a substrate
temperature.
[0025] FIG. 9 shows a transmission electron microscope (TEM)
observation result of a cross section of a film formed using the
hafnium-containing compound prepared in accordance with an example
of the present disclosure on a substrate including a narrow
trench.
BEST MODE FOR CARRYING OUT THE INVENTION
[0026] Hereinafter, examples of the present disclosure will be
described in detail with reference to the accompanying drawings so
that the present disclosure may be readily implemented by those
skilled in the art. However, it is to be noted that the present
disclosure is not limited to the examples but can be embodied in
various other ways. In drawings, parts irrelevant to the
description are omitted for the simplicity of explanation, and like
reference numerals denote like parts through the whole
document.
[0027] Through the whole document, the term "connected to" or
"coupled to" that is used to designate a connection or coupling of
one element to another element includes both a case that an element
is "directly connected or coupled to" another element and a case
that an element is "electronically connected or coupled to" another
element via still another element.
[0028] Through the whole document, the term "on" that is used to
designate a position of one element with respect to another element
includes both a case that the one element is adjacent to the other
element and a case that any other element exists between these two
elements.
[0029] Further, through the whole document, the term "comprises or
includes" and/or "comprising or including" used in the document
means that one or more other components, steps, operation and/or
existence or addition of elements are not excluded in addition to
the described components, steps, operation and/or elements unless
context dictates otherwise.
[0030] Through the whole document, the term "about or
approximately" or "substantially" is intended to have meanings
close to numerical values or ranges specified with an allowable
error and intended to prevent accurate or absolute numerical values
disclosed for understanding of the present disclosure from being
illegally or unfairly used by any unconscionable third party.
[0031] Through the whole document, the term "step of" does not mean
"step for".
[0032] Through the whole document, the term "combination(s) of"
included in Markush type description means mixture or combination
of one or more components, steps, operations and/or elements
selected from a group consisting of components, steps, operation
and/or elements described in Markush type and thereby means that
the disclosure includes one or more components, steps, operations
and/or elements selected from the Markush group.
[0033] Through the whole document, a phrase in the form "A and/or
B" means "A or B, or A and B".
[0034] Through the whole document, the term "alkyl" includes linear
or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10
carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, or 1 to 4
carbon atoms and all the possible isomers thereof. For example, the
alkyl group may include methyl group (Me), ethyl group (Et),
n-propyl group (.sup.nPr), iso-propyl group (.sup.iPr), n-butyl
group (.sup.nBu), tert-butyl group (.sup.tBu), iso-butyl group
(.sup.tBu), sec-butyl group (.sup.tBu), pentyl group, hexyl group,
iso-hexyl group, heptyl group, 4,4-dimethyl pentyl group, octyl
group, 2,2,4-trimethyl pentyl group, nonyl group, decyl group,
undecyl group, dodecyl group, and isomers thereof, but may not be
limited thereto.
[0035] Through the whole document, the term "Group 4 metal element"
refers to a chemical element belonging to the fourth group in the
Periodic Table and may include Ti, Zr or Hf.
[0036] Through the whole document, the term "Cp" is the
abbreviation of a "cyclopentadienyl" group.
[0037] Through the whole document, the term "Grignard reagent"
refers to a reagent for mediating a Grignard reaction and may
include alkyl, vinyl, or aryl-magnesium halide, but may not be
limited thereto. The Grignard reaction refers to a metal organic
chemical reaction in which the Grignard reagent is added to a
carbonyl group of aldehyde or ketone.
[0038] Through the whole document, the term "halogen" or "halo"
refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine
(I).
[0039] In the following description, exemplary embodiments of the
present disclosure will be described in detail, but the present
disclosure may not be limited thereto.
[0040] According to a first aspect of the present disclosure, there
is provided a Group 4 metal element-containing compound,
represented by the following Chemical Formula 1:
##STR00005##
[0041] in the above Chemical Formula 1, M is Ti, Zr or Hf, L is
NR.sup.5R.sup.6, OR.sup.7 or a halogen, each of R.sup.1 to R.sup.7
is independently hydrogen or a linear or branched alkyl group
having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
[0042] In an exemplary embodiment of the present disclosure, the
Group 4 metal element-containing compound may be a compound
represented by any one of the following Chemical Formulas 2 to 4,
but may not be limited thereto:
##STR00006##
[0043] in the above Chemical Formulas, M is Ti, Zr or Hf, each of
R.sup.1 to R.sup.7 is independently hydrogen or a linear or
branched alkyl group having 1 to 4 carbon atoms, X is a halogen,
and n is an integer of from 1 to 3.
[0044] In an exemplary embodiment of the present disclosure, in the
above Chemical Formula 1, M may be Ti, Zr or Hf, L may be
N(CH.sub.3).sub.2, N(C.sub.2H.sub.5).sub.2,
N(CH.sub.3)(C.sub.2H.sub.5), OCH.sub.3, OC.sub.2H.sub.5, or Cl, and
n may be from 1 to 3 or n may be 2, but may not be limited
thereto.
[0045] In an exemplary embodiment of the present disclosure, the
Group 4 metal element-containing compound represented by the above
Chemical Formula 1 or any one of the above Chemical Formulas 2 to 4
may include compounds represented as the following structures, but
may not be limited thereto:
##STR00007##
[0046] According to a second aspect of the present disclosure,
there is provided a method of preparing a Group 4 metal
element-containing compound represented by the following Chemical
Formula 1, including reacting a compound represented by ML.sub.4
with a Grignard reagent:
##STR00008##
[0047] in the above Chemical Formula, M is Ti, Zr or Hf, L is
NR.sup.5OR.sup.6, OR.sup.7 or a halogen, each of R.sup.1 to R.sup.7
is independently hydrogen or a linear or branched alkyl group
having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
[0048] A Group 4 metal element-containing represented by the above
Chemical Formula 1 refers to compounds described in the first
aspect of the present disclosure and refers to, for example,
compounds represented by any one of the above Chemical Formulas 2
to 4 as described in the first aspect of the present disclosure and
specifically exemplified compounds therefor.
[0049] In an exemplary embodiment of the present disclosure, the
Grignard reagent includes a material represented as
Cp(CH.sub.2).sub.n+1MgX, and in the above Chemical Formula, n may
be an integer of from 1 to 3 and X may be a halogen, but may not be
limited thereto.
[0050] In an exemplary embodiment of the present disclosure, the
method of preparing a Group 4 metal element-containing compound may
include a reaction as shown in the following Reaction Formula 1,
but may not be limited thereto:
ML.sub.4+Cp(CH.sub.2).sub.n+1MgX.fwdarw.Cp(C.sub.2).sub.n+1)ML.sub.2+LMg-
X. [Reaction Formula 1]
[0051] In the above Reaction Formula 1, M, L, and n are the same as
defined with respect to the above Chemical Formula 1, and X is a
halogen element selected from the group consisting of Cl, Br and
I.
[0052] In an exemplary embodiment of the present disclosure, the
ML.sub.4 may be, e.g., tetrakis(dimethylamino)zirconium
[Zr(NMe.sub.2).sub.4], tetrakis(diethylamino)zirconium
[Zr(NEt.sub.2).sub.4], tetrakis(ethylmethylamino)zirconium
[Zr(NEtMe).sub.4], tetramethoxy zirconium [Zr(OMe).sub.4],
tetraethoxy zirconium [Zr(OEt).sub.4], zirconium tetrachloride
(ZrCl.sub.4), tetrakis(dirnethylamino)hafnium
[Hf(NMe.sub.2).sub.4], tetrakis(diethylamino)hafnium
[Hf(NEt.sub.2).sub.4], tetrakis(ethylmethylamino)hafnium
[H.sub.f(NEtMe).sub.4], tetramethoxy hafnium [Hf(OMe).sub.4],
tetraethoxy hafnium [Hf(OEt).sub.4], hafnium tetrachloride
(HfCl.sub.4), tetrakis(dimethylamino)titanium
[Ti(NMe.sub.2).sub.4], tetrakis(diethylamino)titanium
[Ti(NEt.sub.2).sub.4], tetrakis(ethylmethylamino)titanium
[Ti(NEtMe).sub.4], tetramethoxy titanium [Ti(OMe).sub.4],
tetraethoxy titanium [Ti(OEt).sub.4], or titanium tetrachloride
(TiCl.sub.4), but may not be limited thereto.
[0053] In an exemplary embodiment of the present disclosure, the
Grignard reagent represented as C.sub.p(CH.sub.2).sub.n+1MgX may be
prepared by reacting C.sub.p(CH.sub.2).sub.n+1X with magnesium (Mg)
metal as shown in the following Reaction Formula 2, but may not be
limited thereto:
Cp(CH.sub.2).sub.n+1X+Mg.fwdarw.Cp(CH.sub.2).sub.n+1MgX. [Reaction
Formula 2]
[0054] According to a third aspect of the present disclosure, there
is provided a method of preparing a Group 4 metal
element-containing compound represented by the following Chemical
Formula 1', including reacting a compound represented by the
following Chemical Formula 4 with M'NR.sup.5R.sup.6 as an alkali
metal salt of a dialkylamine or M'OR.sup.7 as an alkali metal salt
of an alcohol, and herein, M' is an alkali metal and each of
R.sup.5 to R.sup.7 is independently hydrogen or a linear or
branched alkyl group having 1 to 4 carbon atoms:
##STR00009##
[0055] in the above Chemical Formula 4, M is Ti, Zr or Hf, each of
R.sup.1 to R.sup.4 is independently hydrogen or a linear or
branched alkyl group having 1 to 4 carbon atoms, X is a halogen,
and n is an integer of from 1 to 3;
##STR00010##
[0056] in the above Chemical Formula 1', M is Ti, Zr or Hf, L' is
NR.sup.5R.sup.6 or OR.sup.7, each of R.sup.1 to R.sup.7 is
independently hydrogen or a linear or branched alkyl group having 1
to 4 carbon atoms, and n is an integer of from 1 to 3.
[0057] A Group 4 metal element-containing represented by the above
Chemical Formula 1' refers to compounds represented by Chemical
Formula 2 or 3 and specifically the exemplified compounds therefor
among compounds represented by Chemical Formula 1 in the first
aspect of the present disclosure.
[0058] In an exemplary embodiment of the present disclosure, the
M'NR.sup.5R.sup.6 as an alkali metal salt of a dialkylamine may be,
e.g., dimethylaminolithiurn (LiNMe.sub.2), diethylaminolithium
(LiNEt.sub.2), ethylmethylaminolithium (LiNEtMe),
dimethylaminosodium (NaNMe.sub.2), diethylaminosodium
(NaNEt.sub.2), ethylmethylaminosodium (NaNEtMe),
dimethylaminopotassium (KNMe.sub.2), diethylaminopotassium
(KNEt.sub.2), or ethylmethylaminopotassium (KNEtMe), but may not be
limited thereto.
[0059] In an exemplary embodiment of the present disclosure, the
M'OR.sup.7 as an alkali metal salt of an alcohol may be, e.g.,
methoxylithium (LiOMe), ethoxylithium (LiOEt), isopropoxylithium
(LiO.sup.iPr), methoxysodium (NaOMe), ethoxysodium (NaOEt),
isopropoxysodium (NaO.sup.iPr), methoxypotassium (KOMe),
ethoxypotassium (KOEt), or isopropoxypotassium (KO.sup.iPr), but
may not be limited thereto.
[0060] According to a fourth aspect of the present disclosure,
there is provided a precursor composition for depositing a film,
including a Group 4 metal element-containing compound according to
the first aspect of the present disclosure.
[0061] In an exemplary embodiment of the present disclosure, the
precursor composition for depositing a film may be used for
depositing a Group 4 metal element-containing film or thin film.
The Group 4 metal element-containing film or thin film may have a
thickness of from about 1 nm to several .mu.m, but may not be
limited thereto.
[0062] The Group 4 metal element-containing compound according to
the first aspect of the present disclosure is represented by the
following Chemical Formula 1:
##STR00011##
[0063] in the above Chemical Formula 1, M is Ti, Zr or Hf, L is
NR.sup.5R.sup.6, OR.sup.7 or a halogen, each of R.sup.1 to R.sup.7
is independently hydrogen or a linear or branched alkyl group
having 1 to 4 carbon atoms, and n is an integer of from 1 to 3.
[0064] In an exemplary embodiment of the present disclosure, the
Group 4 metal element-containing compound may be a compound
represented by the following Chemical Formulas 2 to 4, but may not
be limited thereto:
##STR00012##
[0065] in the above Chemical Formulas, M is Ti, Zr or Hf, each of
R.sup.1 to R.sup.7 is independently hydrogen or a linear or
branched alkyl group having 1 to 4 carbon atoms, X is a halogen,
and n is an integer of from 1 to 3.
[0066] In an exemplary embodiment of the present disclosure, in the
above Chemical Formula 1, M may be Ti, Zr or Hf, L may be
N(CH.sub.3).sub.2, N(C.sub.2H.sub.5).sub.2,
N(CH.sub.3)(C.sub.2H.sub.5), OCH.sub.3, OC.sub.2H.sub.5, or Cl, and
n may be from 1 to 3, or n may be 2, but may not be limited
thereto.
[0067] In an exemplary embodiment of the present disclosure, the
Group 4 metal element-containing compound represented by the above
Chemical Formula 1 or any one of the above Chemical Formulas 2 to 4
may include compounds represented as the following structures, but
may not be limited thereto:
##STR00013##
[0068] According to a fifth aspect of the present disclosure, there
is provided a method of depositing a Group 4 metal
element-containing film, including forming a Group 4 metal
element-containing film using a precursor composition for
depositing a film according to the fourth aspect of the present
disclosure.
[0069] In an exemplary embodiment of the present disclosure, the
Group 4 metal element-containing film or thin film may have a
thickness of from about 1 nm to several .mu.m, but may not be
limited thereto.
[0070] In an exemplary embodiment of the present disclosure, the
Group 4 metal element-containing film or thin film may be used as a
high dielectric film in a semiconductor device, a catalyst, or the
like, but may not be limited thereto.
[0071] In an exemplary embodiment of the present disclosure, a
method of depositing a Group 4 metal element-containing film or
thin film may include forming a Group 4 metal element-containing
film or thin film by supplying and depositing the precursor
composition to form a Group 4 metal element-containing film or thin
film on a substrate positioned in a deposition chamber, but may not
be limited thereto. The method of depositing a film may employ a
method and an apparatus known in the art and may be performed using
one or more additional reaction gases together if necessary. The
substrate may employ a silicon semiconductor wafer and a compound
semiconductor wafer, but may not be limited thereto. A substrate
having a hole or trench may be used, and for example, a porous
substrate having a large surface area may be used as a
catalyst.
[0072] In an exemplary embodiment of the present disclosure,
depositing the film may be performed by metal organic chemical
vapor deposition (MOCVD) or atomic layer deposition (ALD), but may
not be limited thereto. The metal organic chemical vapor deposition
(MOCVD) or atomic layer deposition (ALD) may be performed using a
deposition apparatus, deposition conditions, and additional
reaction gases known in the art.
[0073] Specifically, according to the precursor composition for
depositing a film according to the fourth aspect of the present
disclosure and the method of depositing a Group 4 metal
element-containing film or thin film according to the fifth aspect
of the present disclosure including forming a Group 4 metal
element-containing film or thin film using the precursor
composition for depositing a film, the Group 4 metal
element-containing novel compound according to an exemplary
embodiment of the present disclosure which is included in the
precursor composition for depositing a film has high thermal
stability and thus can be used as a precursor for atomic layer
deposition or chemical vapor deposition to form a Group 4 metal
element-containing film and particularly can be used to uniformly
form a Group 4 metal element-containing film having a thickness of
several nm to several tens of nm on a substrate having a trench
(groove) in its surface or porous substrate. For example, in a
substrate having a fine trench (groove) with an aspect ratio of
about 1 or more, 2 or more, 5 or more, 10 or more, 20 or more, 30
or more or 40 or more and a width of about 1 .mu.m or less, 500 nm
or less, 400 nm or less, 300 nm or less, 200 nm or less, 100 nm or
less, 80 nm or less, 60 nm or less, 50 nm or less, 40 nm or less,
30 nm or less, 20 nm or less or 10 nm or less in its surface, the
Group 4 metal element-containing novel compounds have an excellent
effect of uniformly forming a Group 4 metal element-containing film
having a thickness of from several nm to several tens of nm on the
entire surface of the substrate including a surface of the fine
trench (groove) including a surface of the deepest portion of the
fine trench (groove) and an upper surface of the fine trench
(groove).
[0074] The precursor composition for depositing a film according to
the fourth aspect of the present disclosure and the method of
depositing a Group 4 metal element-containing film or thin film
according to the fifth aspect of the present disclosure including
forming a Group 4 metal element-containing film or thin film using
the precursor composition for depositing a film can be applied to
manufacturing commercial semiconductor devices. Particularly, in
order to manufacture a DRAM semiconductor device, it is necessary
to form a high dielectric material to a thickness of several nm on
a substrate having a groove with a width of much less than 100 nm
or 50 nm and an aspect ratio of 10:1, 20:1, or 30:1, or a deeper
and narrower groove. Particularly, it is necessary to form a high
dielectric material having a uniform thickness even at a
temperature of 280.degree. C., 300.degree. C., or more, and, thus,
a precursor composition with which a film having a uniform
thickness can be formed on a very narrow and deep groove by atomic
layer deposition (ALD) even at a high temperature is needed and a
Ti, Zr, or Hf compound having very high thermal stability is needed
to be used as the precursor composition, and therefore, the
precursor composition for depositing a film according to the fourth
aspect of the present disclosure and the method of depositing a
Group 4 metal element-containing film or thin film according to the
fifth aspect of the present disclosure including forming a Group 4
metal element-containing film or thin film using the precursor
composition for depositing a film can be usefully utilized.
MODE FOR CARRYING OUT THE INVENTION
[0075] Hereinafter, the present disclosure will be explained in
more detail with reference to Examples. However, the following
Examples are illustrative only for better understanding of the
present disclosure but do not limit the present disclosure.
EXAMPLES
<Preparation Example 1> Preparation of
Cp(CH.sub.2).sub.3MgCl
[0076] After 11.2 g (0.462 mol, 3 equivalents) of magnesium and 100
mL of tetrahydrofuran (THF, C.sub.4H.sub.3O) were put into a
flame-dried 1 L Schlenk flask, the flask was maintained at room
temperature. After 21.8 g (0.154 mol, 1 equivalent) of
3-chloro-propylcyclopentadiene was added to the flask, the obtained
reaction solution was stirred for 15 hours while the temperature
was slowly increased to 50.degree. C. Then, the temperature of the
flask was slowly decreased to room temperature and the reaction
solution was filtered through a celite pad and a glass frit to
remove excess magnesium, and, thus Grignard reagent
Cp(CH.sub.2).sub.3MgCl was obtained from the obtained filtrate.
<Example 1> Preparation of
Cp(CH.sub.2).sub.3Zr[N(CH.sub.3).sub.2].sub.2
[0077] After 41 g (0.154 mol, 1 equivalent) of
tetrakis(dimethylamino)zirconium [Zr(N(CH.sub.3).sub.2).sub.4] and
100 mL of n-hexane (C.sub.6H.sub.14) were put into a flame-dried 1
L Schlenk flask, the flask was maintained at room temperature.
After the Grignard reagent Cp(CH.sub.2).sub.3MgCl (0.154 mol, 1
equivalent) prepared in Preparation Example 1 was slowly
drop-wisely added to the flask, the obtained reaction solution was
refluxed for 15 hours.
[0078] After the reaction was completed, the solvent and volatile
by-product were removed under a reduced pressure and extraction was
carried out with 200 mL of n-hexane. After the n-hexane extract was
filtered through a celite pad and a glass frit, the obtained
filtrate was subject to a reduced pressure to remove the solvent
and distilled under a reduced pressure, and, thus 27 g (yield of
61%) of pale yellow liquid compound
Cp(CH.sub.2).sub.3Zr[N(CH.sub.3).sub.2].sub.2 which is a liquid
zirconium compound represented as the following structure was
obtained.
##STR00014##
[0079] Boiling point (bp) 100.degree. C. (0.3 torr);
[0080] Elemental analysis calcd for Cl.sub.2H.sub.22N.sub.2Zr: C,
50.48, H, 7.77, N, 9.81; found C, 50.39, H, 7.81, N, 9.79;
[0081] 1H-NMR (400 MHz, C.sub.6D.sub.6, 25.degree. C.): .delta.
6.013, 5.923 (m, 4H, C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2),
.delta. 2.958 (s, 12H, N(CH.sub.3).sub.2), .delta. 2.469 (t, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2), .delta. 1.576 (m, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2) .delta. 0.920 (t, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2).
[0082] A H-HMR spectrum of the zirconium-containing compound
according to the present Example is as shown in FIG. 1. Further, a
thermogravimetric analysis result for each of the
zirconium-containing compound according to the present Example and
CpZr[N(CH.sub.3).sub.2].sub.3 according to Comparative Example is
as shown in FIG. 2.
[0083] As can be seen from the thermogravimetric analysis result
shown in FIG. 2, T.sub.1/2 of the liquid zirconium compound
according to the present Example was 211.degree. C. and T.sub.1/2
of the liquid zirconium compound according to Comparative Example
was 180.degree. C. Therefore, it can be confirmed that the liquid
zirconium compound according to the present Example had a
remarkably high T.sub.1/2 as compared with the compound according
to Comparative Example, and the residue amount was about 3%
according to the thermogravimetric analysis, and, thus, it can be
confirmed that the liquid zirconium compound according to the
present Example had higher thermal stability and also had excellent
thermal decomposition characteristics. These excellent
characteristics demonstrate that the liquid zirconium compound
according to the present Example is very advantageous to be used as
a precursor for forming a film (thin film).
<Example 2> Preparation of
Cp(CH.sub.2).sub.3Zr[N(C.sub.2H.sub.5).sub.2].sub.2 and
Cp(CH.sub.2).sub.3Zr[N(CH.sub.3)(C.sub.2H.sub.5)].sub.2
[0084] A precursor material
Cp(CH.sub.2).sub.3Zr[N(C.sub.2H.sub.5).sub.2].sub.2 or
Cp(CH.sub.2).sub.3Zr[N(CH.sub.3)(C.sub.2H.sub.5)].sub.2 was
prepared by the same method as in Example 1 except that
tetrakis(diethylamino)zirconium [Zr(N(C.sub.2H.sub.5).sub.2).sub.4]
or tetrakis(ethylmethylamino)zirconium
[Zr(N(CH.sub.3)(C.sub.2H.sub.5)).sub.4] was used instead of
tetrakis(dimethylamino)zirconium [Zr(N(CH.sub.3).sub.2).sub.4] used
in Example 1.
<Example 3> Preparation of
Cp(CH.sub.2).sub.3Hf[N(CH.sub.3).sub.2].sub.2
[0085] After 198 g (0.558 mol, 1 equivalent) of
tetrakis(dimethylamino)hafnium [Hf(N(CH.sub.3).sub.2).sub.4] and
500 mL of n-hexane were put into a flame-dried 1 L Schlenk flask,
the flask was maintained at room temperature. After the Grignard
reagent Cp(CH.sub.2).sub.3MgCl 0.558 mol, 1 equivalent) prepared in
Preparation Example 1 was slowly drop-wisely added to the flask,
the obtained reaction solution was refluxed for 15 hours.
[0086] After the reaction was completed, the solvent and volatile
by-product were removed under a reduced pressure and extraction was
carried out with 1000 of n-hexane. After the n-hexane extract was
filtered through a celite pad and a glass frit, the obtained
filtrate was subject to a reduced pressure to remove the solvent
and distilled under a reduced pressure, and, thus, 108 g (yield of
52%) of pale yellow liquid compound
Cp(CH.sub.2).sub.3Hf[N(CH.sub.3).sub.2].sub.2 represented as the
following structure was obtained. A H-HMR spectrum of the liquid
hafnium compound obtained as above is shown in FIG. 3.
##STR00015##
[0087] Boiling point (bp) 100.degree. C. (0.3 torr);
[0088] Elemental analysis calcd for C.sub.12H.sub.22N.sub.2Hf: C,
38.66, H, 5.95, N, 7.51; found C, 38.56, H, 5.99, N, 7.49;
[0089] 1H-NMR (400 MHz, C.sub.6D.sub.6, 25.degree. C.): .delta.
5.985, 5.901 (m, 4H, C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2),
.delta. 2.991 (s, 12H, N(CH.sub.3).sub.2), .delta. 2.489 (t, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2), .delta. 1.545 (m, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2), .delta. 0.908 (t, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2)
<Example 4> Preparation of
Cp(CH.sub.2).sub.3Hf[N(C.sub.2H.sub.5).sub.2].sub.2 and
Cp(CH.sub.2).sub.3Hf[N(CH.sub.3)(C.sub.2H.sub.5)].sub.2
[0090] The precursor
Cp(CH.sub.2).sub.3Hf[N(C.sub.2H.sub.5).sub.2].sub.2 or
Cp(CH.sub.2).sub.3Hf[N(CH.sub.3)(C.sub.2H.sub.5)].sub.2 was
prepared by the same method as in Example 3 except that
tetrakis(diethylamino)hafnium [Hf(N(C.sub.2H.sub.5).sub.2).sub.4]
or tetrakis(ethylmethylamino)hafnium
[Hf(N(CH.sub.3)(C.sub.2H.sub.5)).sub.4] was used instead of
tetrakis(dimethylamino)hafnium [Hf(N(CH.sub.3).sub.2).sub.4] used
in Example 3.
<Example 5> Preparation of Cp(CH.sub.2).sub.3TiCl.sub.2
[0091] After 99 g (0.522 mol, 1 equivalent) of titanium
tetrachloride (TiCl.sub.4) and 1000 mL of toluene
(C.sub.6H.sub.5--CH.sub.3) were put into a flame-dried 3 L Schlenk
flask, the flask was cooled at -10'C. After the Grignard reagent
Cp(CH.sub.2).sub.3MgCl (0.522 mol, 1 equivalent) prepared in
Preparation Example 1 and 53 g (0.522 mol, 1 equivalent) of
triethylamine were diluted in 500 mL of toluene and slowly
drop-wisely added to the flask. The obtained reaction solution was
refluxed for 15 hours.
[0092] After the reaction was completed, the solvent and volatile
by-product were removed under a reduced pressure and washing was
carried out with 200 mL of n-hexane three times and the reaction
product was subject to a reduced pressure to remove the solvent and
distilled under a reduced pressure, and, thus, 69 g (yield of 59%)
of red solid compound Cp(CH.sub.2).sub.3TiCl.sub.2 represented as
the following structure was obtained. A H-HMR spectrum of the
above-described solid compound is as shown in FIG. 4:
##STR00016##
[0093] Elemental analysis calcd for C.sub.12H.sub.22N.sub.2Ti: C,
42.72, H, 4.48; found C, 42.73, H, 4.46;
[0094] 1H-NMR (400 MHz, C.sub.6D.sub.5, 25.degree. C.): .delta.
5.996, 5.723 (m, 4H, C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2),
.delta. 2.725 (t, 2H, C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2),
.delta. 1.484 (t, 2H, C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2),
.delta. 0.841 (m, 2H, C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2)
<Example 6> Preparation of Cp(CH.sub.2).sub.3ZrCl.sub.2 and
Cp(CH.sub.2).sub.3HfCl.sub.2
[0095] The precursor Cp(CH.sub.2).sub.3ZrCl.sub.2 or
Cp(CH.sub.2).sub.3HfCl.sub.2 was prepared by the same method as in
Example 5 except that zirconium tetrachloride (ZrCl.sub.4) or
hafnium tetrachloride (HfCl.sub.4) was used instead of titanium
tetrachloride (TiCl.sub.4) used in Example 5.
<Example 7> Preparation of
Cp(CH.sub.2).sub.3Ti[N(CH.sub.3).sub.2].sub.2
[0096] After 277 g (1.044 mol, 2 equivalents) of n-butyllithium was
put into a flame-dried 3 L Schlenk flask, the flask was cooled at
-40.degree. C. 47 g (1.044 mol, 2 equivalents) of dimethylamine was
slowly drop-wisely added to the flask and then stirred at room
temperature for 3 hours. After Cp(CH.sub.2).sub.3TiCl.sub.2 (0.522
mol, 1 equivalent) prepared in Example 3 was slowly drop-wisely
added to the flask, the obtained reaction solution was stirred at
40.degree. C. for 4 hours.
[0097] After the reaction was completed, the solvent and volatile
by-product were removed under a reduced pressure and then
extraction was carried out with 500 mL of n-hexane. After the
n-hexane extract was filtered through a celite pad and a glass
frit, the obtained filtrate subject to a reduced pressure to remove
the solvent and distilled under a reduced pressure, and thus 50 g
(yield of 40%) of red liquid compound
Cp(CH.sub.2).sub.3Ti[N(CH.sub.3).sub.2].sub.2 represented as the
following structure was obtained. A H-HMR spectrum of the liquid
compound prepared as above is as shown in FIG. 5:
##STR00017##
[0098] Boiling point (bp) 100.degree. C. (0.3 torr);
[0099] Element analysis calcd for C.sub.12H.sub.22N.sub.2Ti: C,
59.51, H, 9.16, N, 11.57; found C, 59.48, H, 9.17, N, 11.58;
[0100] 1H-NMR (400 MHz, C.sub.6D.sub.6, 25.degree. C.): .delta.
5.894, 5.805 (m, 4H, C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2),
.delta. 3.120 (s, 12H, N(CH.sub.3).sub.2), .delta. 2.432 (t, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2), .delta. 1.586 (m, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2), .delta. 0.943 (t, 2H,
C.sub.5H.sub.4--CH.sub.2CH.sub.2CH.sub.2)
<Example 8> Preparation of
Cp(CH.sub.2).sub.3Ti(OCH.sub.3).sub.2,
Cp(CH.sub.2).sub.3Zr(OCH.sub.3).sub.2 and
Cp(CH.sub.2).sub.3Hf(OCH.sub.3).sub.2
[0101] The precursor Cp(CH.sub.2).sub.3Ti(OCH.sub.3).sub.2 was
prepared by the same method as in Example 7 except that methanol
was used instead of dimethylamine used in Example 7.
[0102] Further, the precursor material
Cp(CH.sub.2).sub.3Zr(OCH.sub.3).sub.2 or
Cp(CH.sub.2).sub.3Hf(OCH.sub.3).sub.2 was prepared by the same
method as in Example 7 except that Cp(CH.sub.2).sub.3ZrCl.sub.2 or
Cp(CH.sub.2).sub.3HfCl.sub.2 was used instead of
Cp(CH.sub.2).sub.3TiCl.sub.2 used in Example 7 and methanol was
used instead of dimethylamine.
<Example 9> Formation of Zirconium Oxide Film by Atomic Layer
Deposition Using Cp(CH.sub.2).sub.3Zr[N(CH.sub.3).sub.2].sub.2
Compound and Ozone (O.sub.3) Gas
[0103] A test for forming a zirconium oxide film by atomic layer
deposition (ALD) using
Cp(CH.sub.2).sub.3Zr[N(CH.sub.3).sub.2].sub.2 prepared in Example 1
as a precursor was conducted. In this case, a silicon (Si) wafer
having a fine groove (trench) with a width of about 55 nm and an
aspect ratio of about 10:1 was used as a substrate. The substrate
was heated at 290.degree. C. to 350.degree. C. Further, a precursor
compound put in a stainless-steel container was heated at a
temperature of 100.degree. C., and the precursor compound was
supplied to an ALD reactor for performing atomic layer deposition
by allowing argon (Ar) gas to pass through the container at a flow
rate of 60 sccm. An internal pressure in the ALD reactor was
maintained at 3 torr. An ALD source supply cycle, in which a gas of
the precursor compound was supplied to the ALD reactor for 5
seconds, then, argon gas was supplied for 5 seconds, and then,
ozone (O.sub.3) gas was supplied for 5 seconds and argon gas was
supplied again for 5 seconds, was repeated 200 times. Film growth
per source supply cycle of the zirconium oxide thin film formed
according to the above-described process was as shown in FIG. 6. As
shown in FIG. 6, it was observed that film growth per ALD source
supply cycle was uniform in the range of the substrate temperature
of from 290.degree. C. to 350.degree. C.
[0104] FIG. 7 shows a transmission electron microscope (TEM)
observation result of a cross section of a film formed by heating a
substrate including a very narrow trench(groove) with an aspect
ratio of 10:1 at 300.degree. C. and repeating the above-described
ALD source supply cycle 80 times. It can be confirmed that a film
having a uniform thickness of about 7 nm was formed on the entire
surface of the substrate including a surface of the deepest portion
of the trench in the substrate and an upper surface of the
trench.
<Comparative Example 1> Formation of Zirconium Oxide Film by
Atomic Layer Deposition Using CpZr[N(CH.sub.3).sub.2].sub.3
Compound and Ozone (O.sub.3) Gas
[0105] A zirconium oxide film was formed under the same conditions
as in Example 9 except that CpZr[N(CH.sub.3).sub.2].sub.3 was used
instead of Cp(CH.sub.2).sub.3Zr[N(CH.sub.3).sub.2].sub.2 and
CpZr[N(CH.sub.3).sub.2].sub.3 put in a stainless-steel container
was heated at a temperature of 90.degree. C. Film growth per ALD
source supply cycle of the zirconium oxide thin film formed
according to the above-described process was as shown in FIG. 6. It
was observed that when a temperature of the silicon (Si) substrate
was 300.degree. C. or more, film growth per source supply cycle was
increased as the temperature was increased. Particularly, when the
temperature of the substrate was 350.degree. C., film growth per
ALD source supply cycle was increased almost 2 times compared with
film growth at 290.degree. C. and 300.degree. C. This was due to
thermal decomposition of CpZr[N(CH.sub.3).sub.2], and if the
thermal decomposition is carried out as such, a zirconium oxide
film having a uniform thickness cannot be formed on a substrate
having a trench with a high aspect ratio by atomic layer
deposition.
[0106] It can be seen from Example 9 and Comparative Example 1 that
atomic layer deposition using a Zr compound of the present
disclosure is more advantageous in forming a zirconium oxide film
to a uniform thickness on the entire surface of a substrate having
a trench (groove) and including a surface of the deepest portion of
the trench and an upper surface of the trench at a higher
temperature than atomic layer deposition using a
CpZr[N(CH.sub.3).sub.2].sub.3 gas and ozone gas conventionally
known in the art.
<Example 10> Formation of Hafnium Oxide Film by Atomic Layer
Deposition Using Cp(CH.sub.2).sub.3Hf[N(CH.sub.3).sub.2].sub.2
Compound and Ozone (O.sub.3) Gas
[0107] A test for forming a hafnium oxide film by atomic layer
deposition (ALD) using
Cp(CH.sub.2).sub.3Hf[N(CH.sub.3).sub.2].sub.2 prepared in Example 3
as a precursor was conducted. In this case, a silicon (Si) wafer
having a fine trench with a width of about 55 nm and an aspect
ratio of about 10:1 was used as a substrate. The substrate was
heated at 290.degree. C. to 350.degree. C. Further, a precursor
compound put in a stainless-steel container was heated at a
temperature of 100.degree. C., and the precursor compound was
supplied to an ALD reactor for performing atomic layer deposition
by allowing argon (Ar) gas to pass through the container at a flow
rate of 60 sccm. An internal pressure in the ALD reactor was
maintained at 3 torr. An ALD source supply cycle, in which a gas of
the precursor compound was supplied to the ALD reactor for 5
seconds, then, argon gas was supplied for 5 seconds, and then,
ozone (O.sub.3) gas was supplied for 5 seconds and argon gas was
supplied again for 5 seconds, was repeated 200 times. Film growth
per source supply cycle of the hafnium oxide thin film formed
according to the above-described process is shown in FIG. 8. As
shown in FIG. 8, it was observed that film growth per ALD source
supply cycle was uniform in the range of substrate temperature of
from 290.degree. C. to 350.degree. C.
[0108] FIG. 9 shows a transmission electron microscope (TEM)
observation result of a cross section of a film formed by heating a
substrate including fine trenches with a width of about 55 nm and
an aspect ratio of about 10:1 at 300.degree. C. and repeating 61
times of the above-described ALD source supply cycle. It can be
seen that a film having a uniform thickness of about 5 nm was
formed on the entire surface of the substrate including a surface
of the deepest portion of the trench and an upper surface of the
trench in the substrate.
[0109] The above description of the present disclosure is provided
for the purpose of illustration, and it would be understood by
those skilled in the art that various changes and modifications may
be made without changing technical conception and essential
features of the present disclosure. Thus, it is clear that the
above-described examples are illustrative in all aspects and do not
limit the present disclosure. For example, each component described
to be of a single type can be implemented in a distributed manner.
Likewise, components described to be distributed can be implemented
in a combined manner.
[0110] The scope of the present disclosure is defined by the
following claims rather than by the detailed description of the
embodiment. It shall be understood that all modifications and
embodiments conceived from the meaning and scope of the claims and
their equivalents are included in the scope of the present
disclosure.
* * * * *