U.S. patent application number 16/499216 was filed with the patent office on 2020-04-09 for composition for depositing silicon-containing thin film and method for manufacturing silicon-containing thin film using the same.
The applicant listed for this patent is DNF CO., LTD.. Invention is credited to Se Jin JANG, Myong Woon KIM, Sung Gi KIM, Sam Dong LEE, Sang-Do LEE, Sang Ick LEE, Jeong Joo PARK, Joong Jin PARK, Byeong-il YANG.
Application Number | 20200111665 16/499216 |
Document ID | / |
Family ID | 63876274 |
Filed Date | 2020-04-09 |
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United States Patent
Application |
20200111665 |
Kind Code |
A1 |
KIM; Sung Gi ; et
al. |
April 9, 2020 |
COMPOSITION FOR DEPOSITING SILICON-CONTAINING THIN FILM AND METHOD
FOR MANUFACTURING SILICON-CONTAINING THIN FILM USING THE SAME
Abstract
Provided are a composition containing a silylamine compund and a
method for manufacturing a silicon-containing thin film using the
same, and more particularly, a composition for depositing a
silicon-containing thin film, containing a silylamine compound
capable of forming a silicon-containing thin film having a
significantly excellent water vapor transmission rate to thereby be
usefully used as a precursor of the silicon-containing thin film
and an encapsulant of a display, and a method for manufacturing a
silicon-containing thin film using the same.
Inventors: |
KIM; Sung Gi; (Daejeon,
KR) ; PARK; Jeong Joo; (Daejeon, KR) ; PARK;
Joong Jin; (Daejeon, KR) ; JANG; Se Jin;
(Jeju-si, Jeju-do, KR) ; YANG; Byeong-il;
(Daejeon, KR) ; LEE; Sang-Do; (Daejeon, KR)
; LEE; Sam Dong; (Daejeon, KR) ; LEE; Sang
Ick; (Daejeon, KR) ; KIM; Myong Woon;
(Daejeon, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DNF CO., LTD. |
Daefeon |
|
KR |
|
|
Family ID: |
63876274 |
Appl. No.: |
16/499216 |
Filed: |
March 29, 2018 |
PCT Filed: |
March 29, 2018 |
PCT NO: |
PCT/KR2018/003682 |
371 Date: |
September 27, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C23C 16/36 20130101;
H01L 21/02167 20130101; H01L 21/0214 20130101; C23C 16/325
20130101; C23C 16/50 20130101; C23C 16/45536 20130101; H01L 21/0217
20130101; H01L 21/02219 20130101; C07F 7/10 20130101; C23C 16/345
20130101; H01L 21/02208 20130101; C23C 16/308 20130101; H01L
21/0228 20130101; C23C 16/45542 20130101; H01L 21/02164 20130101;
H01L 21/02271 20130101; H01L 21/02274 20130101; C23C 16/45553
20130101; H01L 21/02126 20130101; C23C 16/401 20130101 |
International
Class: |
H01L 21/02 20060101
H01L021/02; C07F 7/10 20060101 C07F007/10; C23C 16/50 20060101
C23C016/50; C23C 16/455 20060101 C23C016/455; C23C 16/30 20060101
C23C016/30; C23C 16/32 20060101 C23C016/32; C23C 16/34 20060101
C23C016/34; C23C 16/36 20060101 C23C016/36; C23C 16/40 20060101
C23C016/40 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 29, 2017 |
KR |
10-2017-0040078 |
Mar 27, 2018 |
KR |
10-2018-0035166 |
Claims
1. A composition for depositing a silicon-containing thin film, the
composition comprising a silylamine compound represented by the
following Chemical Formula 1: ##STR00011## in Chemical Formula 1,
R.sub.1 to R.sub.4 are each independently hydrogen, C1-C7alkyl, or
C2-C7alkenyl, or R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4 are
each independently linked to each other to form a ring; and R.sub.5
and R.sub.6 are each independently C1-C7alkyl, or
C2-C7)alkenyl.
2. The composition of claim 1, wherein R.sub.5 and R.sub.6 are each
independently C1-C5alkyl.
3. The composition of claim 1, wherein the silylamine compound
represented by Chemical Formula 1 is represented by Chemical
Formula 2 or 3: ##STR00012## in Chemical Formulas 2 and 3, R.sub.11
to R.sub.14 are each independently hydrogen, C1-C5alkyl, or
C2-C5alkenyl; R.sub.5 and R.sub.6 are each independently
C1-C5alkyl, or C2-C5alkenyl; and n and m are each independently an
integer of 1 to 7.
4. The composition of claim 3, wherein R.sub.5 and R.sub.6 are each
independently C1-C5alkyl; and n and m are each independently an
integer of 1 to 4.
5. The composition of claim 1, wherein the silylamine compound is
selected from the following compounds: ##STR00013##
6. A method for manufacturing a silicon-containing thin film, using
a composition comprising a silylamine compound represented by the
following Chemical Formula 1: ##STR00014## in Chemical Formula 1,
R.sub.1 to R.sub.4 are each independently hydrogen, C1-C7alkyl, or
C2-C7alkenyl, or R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4 are
each independently linked to each other to form a ring; and R.sub.5
and R.sub.6 are each independently C1-C7alkyl, or
C2-C7)alkenyl.
7. The method of claim 6, wherein deposition is performed by an
atomic layer deposition method, a chemical vapor deposition method,
a metal-organic chemical vapor deposition method, a low-pressure
chemical vapor deposition method, a plasma-enhanced chemical vapor
deposition method, or a plasma-enhanced atomic layer deposition
method.
8. The method of claim 6, wherein the silicon-containing thin film
is a silicon oxide film, a silicon oxy carbide film, a silicon
nitride film, a silicon oxy nitride film, a silicon carbonitride
film, or a silicon carbide film.
9. The method of claim 6, comprising: a) maintaining a temperature
of a substrate mounted in a chamber at 30 to 500.degree. C.; b)
contacting the composition of any one of claims 1 to 5 with the
substrate to adsorb the composition in the substrate; and c)
injecting a reaction gas into the substrate in which the
composition is adsorbed to form a silicon-containing thin film.
10. The method of claim 9, wherein the reaction gas is supplied
after being activated by generating plasma with a plasma power of
50 to 1000 W.
11. The method of claim 6, wherein R.sub.5 and R.sub.6 are each
independently C1-C5alkyl.
12. The method of claim 6, wherein the silylamine compound
represented by Chemical Formula 1 is represented by Chemical
Formula 2 or 3: ##STR00015## in Chemical Formulas 2 and 3, R.sub.11
to R.sub.14 are each independently hydrogen, C1-C5alkyl, or
C2-C5alkenyl; R.sub.5 and R.sub.6 are each independently
C1-C5alkyl, or C2-C5alkenyl; and n and m are each independently an
integer of 1 to 7.
13. The method of claim 12, wherein R.sub.5 and R.sub.6 are each
independently C1-C5alkyl; and n and m are each independently an
integer of 1 to 4.
14. The method of claim 6, wherein the silylamine compound is
selected from the following compounds:
Description
TECHNICAL FIELD
[0001] The present invention relates to a composition for
depositing a silicon-containing thin film and a method for
manufacturing a silicon-containing thin film using the same, and
more particularly, to a composition for depositing a
silicon-containing thin film, containing a silylamine compound as a
precursor for depositing a thin film, and a method for
manufacturing a silicon-containing thin film using the same.
BACKGROUND ART
[0002] A silicon-containing thin film is manufactured through
various deposition processes in a semiconductor field to thereby be
manufactured in various forms such as a silicon film, a silicon
oxide film, a silicon nitride film, a silicon carbonitride film,
and a silicon oxynitride film, and an application field of the
silicon-containing thin film may be wide.
[0003] Particularly, since the silicon oxide film and the silicon
nitride film have a significantly excellent barrier property and
oxidation resistance, the silicon oxide film and the silicon
nitride film are used as an insulating film, a diffusion barrier, a
hard mask, an etch stop layer, a seed layer, a spacer, a trench
isolation, an intermetallic dielectric material, and a passivation
layer in manufacturing an apparatus.
[0004] Recently, a polycrystalline silicon thin film has been used
in a thin film transistor (TFT), a solar cell, and the like, and an
application field thereof has been gradually diversified.
[0005] As a representative technology for manufacturing a
silicon-containing thin film known in the art, there are a
metal-organic chemical vapor deposition (MOCVD) method for reacting
a gas-type silicon precursor and a reaction gas with each other to
form a film on a surface of a substrate or directly reacting the
gas-type silicon precursor and the reaction gas with each other on
the surface to form a film and an atomic layer deposition (ALD)
method for physically or chemically adsorbing a gas-type silicon
precursor and sequentially injecting a reaction gas to form a film.
Various technologies for manufacturing a thin film such as a
low-pressure chemical vapor deposition (LPCVD) method applying the
above-mentioned method, a plasma-enhanced chemical vapor deposition
(PECVD) method and a plasma-enhanced atomic layer deposition
(PEALD) method capable of performing deposition at a low
temperature, and the like, are applied to processes for
manufacturing next-generation semiconductors and display devices to
thereby be used to form a ultra-fine pattern and deposit an
ultra-thin film having uniform and excellent properties at a
nano-scale thickness.
[0006] Representative examples of a precursor used to form the
silicon-containing thin film may include silane, silane compounds,
aminosilane, and alkoxysilane compounds. Specific examples thereof
may include silane chloride compounds such as dichlorosilane
(SiH.sub.2Cl.sub.2) and hexachlorodisilane (Cl.sub.3SiSiCl.sub.3),
trisilylamine (N(SiH.sub.3).sub.3, bis-diethylaminosilane
(H.sub.2Si(N(CH.sub.2CH.sub.3).sub.2).sub.2),
di-isopropylaminosilane (H.sub.3SiN(i-C.sub.3H.sub.7).sub.2), and
the like. These precursors have been used in mass-production
processes for manufacturing semiconductors and displays.
[0007] However, due to fineness of devices caused by ultra-high
integration of the devices and an increase in aspect ratio, and
diversification of materials of the devices, a technology of
forming an ultra-fin thin film having a uniform and thin thickness
and excellent electrical properties at a low temperature to be
desired has been required. Therefore, a high-temperature process
(600.degree. C. or more) using an existing silicon precursor, a
step coverage, etching properties, and physical and electric
properties of the thin film have become problems, such that the
development of a novel more excellent silicon precursor and a
method for forming a thin film have been studied.
TECHNICAL PROBLEM
[0008] An object of the present invention is to provide a
composition for depositing a silicon-containing thin film,
containing a silylamine compound capable of being used as a
precursor of the silicon-containing thin film.
[0009] Another object of the present invention is to provide a
method for manufacturing a silicon-containing thin film using the
composition for depositing a silicon-containing thin film according
to the present invention.
TECHNICAL SOLUTION
[0010] In one general aspect, there is provided a composition for
depositing a silicon-containing thin film, containing a silylamine
compound having excellent cohesive force, a high deposition rate,
and excellent physical and electrical properties as a precursor for
depositing a silicon-containing thin film, the silylamine compound
being represented by the following Chemical Formula 1.
##STR00001##
[0011] (In Chemical Formula 1, R.sub.1 to R.sub.4 are each
independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R.sub.1
and R.sub.2, and R.sub.3 and R.sub.4 are each independently linked
to each other to form a ring; and R.sub.5 and R.sub.6 are each
independently (C1-C7)alkyl, or (C2-C7)alkenyl.)
[0012] Preferably, in the silylamine compound represented by
Chemical Formula 1 according to the exemplary embodiment of the
present invention, R.sub.5 and R.sub.6 may be each independently
(C1-C5)alkyl.
[0013] Preferably, the silylamine compound represented by Chemical
Formula 1 according to the exemplary embodiment of the present
invention may be represented by the following Chemical Formula 2 or
3.
##STR00002##
[0014] (In Chemical Formula 2 or 3, R.sub.11 to R.sub.14 are each
independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; R.sub.5
and R.sub.6 are each independently (C1-C5)alkyl, or (C2-C5)alkenyl;
and n and m are each independently an integer of 1 to 7.)
[0015] Preferably, in Chemical Formula 2 or 3 according to the
exemplary embodiment of the present invention, R.sub.5 and R.sub.6
may be each independently (C1-C5)alkyl; and n and m may be each
independently an integer of 1 to 4.
[0016] The silylamine compound represented by Chemical Formula 1
according to the exemplary embodiment of the present invention may
be selected from the following compounds but is not limited
thereto.
##STR00003##
[0017] In another general aspect, there is provided a method for
manufacturing a silicon-containing thin film using the composition
for depositing a silicon-containing thin film according to the
exemplary embodiment of the present invention.
[0018] In the method for manufacturing a silicon-containing thin
film, the silicon-containing thin film may be formed by an atomic
layer deposition (ALD) method, a chemical vapor deposition (CVD)
method, a metal-organic chemical vapor deposition (MOCVD) method, a
low-pressure chemical vapor deposition (LPCVD) method, a
plasma-enhanced chemical vapor deposition (PECVD) method, or a
plasma-enhanced atomic layer deposition (PEALD) method, and be a
silicon oxide (SiO.sub.2) film, a silicon oxy carbide (SiOC) film,
a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a
silicon carbonitride (SiCN) film, or a silicon carbide (SiC)
film.
[0019] More specifically, the method for manufacturing a
silicon-containing thin film according to the present invention may
include:
a. maintaining a temperature of a substrate mounted in a chamber at
30 to 500.degree. C.; b. contacting the composition for depositing
a silicon-containing thin film according to the present invention
with the substrate to adsorb the composition for depositing a
silicon-containing thin film according to the present invention in
the substrate; and c. injecting a reaction gas into the substrate
in which the composition for depositing a silicon-containing thin
film is adsorbed to form a silicon-containing thin film.
[0020] In the method for manufacturing a silicon-containing thin
film, the reaction gas may be supplied after being activated by
generating plasma at a plasma power of 50 to 1000 W.
ADVANTAGEOUS EFFECTS
[0021] A composition for depositing a silicon-containing thin film
contains a silylamine which is a liquid at room temperate and has
high volatility and excellent thermal stability as a precursor,
such that a high-quality silicon-containing thin film having high
purity and durability may be provided under lower plasma power and
film formation temperature conditions.
[0022] Further, in a method for manufacturing a silicon-containing
thin film using the composition for depositing a silicon-containing
thin film according to the present invention, an excellent
deposition rate and excellent stress intensity may be implemented
even under a low film formation temperature condition, and in a
silicon-containing thin film manufactured thereby, contents of
impurities such as carbon, oxygen, and hydrogen are minimized, such
that the silicon-containing thin film may have a high purity,
excellent physical and electrical properties, and excellent water
vapor transmission rate.
DESCRIPTION OF DRAWINGS
[0023] FIG. 1 is a view illustrating a result obtained by measuring
a vapor pressure of a bis(dimethylaminomethylsilyl)amine compound
prepared in Example 1.
[0024] FIG. 2 is a view illustrating a thermogravimetric analysis
result of the bis(dimethylaminomethylsilyl)amine compound prepared
in Example 1.
[0025] FIG. 3 is a view illustrating results obtained by performing
infrared spectroscopic analysis on deposited films of
silicon-containing thin films manufactured in Examples 2 to 8 and
Comparative Example 2.
[0026] FIG. 4 is a view illustrating results obtained by performing
infrared spectroscopic analysis on deposited films of
silicon-containing thin films manufactured in Examples 9 to 15.
[0027] FIG. 5 is a result obtained by measuring a water vapor
transmission rate of a silicon-containing thin film prepared in
Example 6.
[0028] FIG. 6 is a result obtained by measuring a water vapor
transmission rate of a silicon-containing thin film prepared in
Example 11.
BEST MODE
[0029] The present invention provides a composition for depositing
a silicon-containing thin film containing a silylamine compound
represented by the following Chemical Formula 1, which is a liquid
at room temperature and has high volatility and excellent thermal
stability to thereby be used as a significantly useful precursor of
forming a silicon-containing thin film, wherein the silylamine
compound is represented by the following Chemical Formula 1.
##STR00004##
[0030] (In Chemical Formula 1, R.sub.1 to R.sub.4 are each
independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R.sub.1
and R.sub.2, and R.sub.3 and R.sub.4 are each independently linked
to each other to form a ring; and R.sub.5 and R.sub.7 are each
independently (C1-C7)alkyl, or (C2-C7)alkenyl.)
[0031] In the silylamine compound contained in the composition for
depositing a silicon-containing thin film, amine has two aminosilyl
functional groups as substituents, such that the silylamine
compound, which is a liquid at room temperature, has high
volatility. Therefore, the silylamine compound may be significantly
usefully used to form the silicon-containing thin film.
[0032] More specifically, the silylamine compound according to the
present invention is a compound having a silazane backbone, but
necessarily has two aminosilyl functional groups
##STR00005##
and only when each silicon atom of the aminosilyl functional groups
necessarily has one hydrogen atom attached thereto, the silylamine
compound may have useful effects as a precursor for depositing a
thin film.
[0033] Preferably, in the silylamine compound represented by
Chemical Formula 1 according to the exemplary embodiment of the
present invention, R5 and R6 may be each independently
(C1-C5)alkyl.
[0034] Preferably, the silylamine compound represented by Chemical
Formula 1 according to the exemplary embodiment of the present
invention may be represented by the following Chemical Formula 2 or
3.
##STR00006##
[0035] (In Chemical Formulas 2 and 3, R.sub.11 to R.sub.14 are each
independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; R.sub.5
and R.sub.6 are each independently (C1-C5)alkyl, or (C2-C5)alkenyl;
and n and m are each independently an integer of 1 to 7.)
[0036] In the silylamine compound according to the present
invention, each silicon atom of two aminosilyl groups in the
silazane backbone necessarily has one hydrogen atom attached
thereto, such that the silylamine compound has a more excellent
effect as the precursor for depositing a silicon-containing thin
film.
[0037] Preferably, in Chemical Formula 2 or 3 according to the
exemplary embodiment of the present invention, R.sub.5 and R.sub.6
may be each independently (C1-C5)alkyl or (C2-C5)alkenyl; and n and
m are each independently an integer of 1 to 4. More preferably,
R.sub.5 and R.sub.6 may be each independently (C1-C5)alkyl; and n
and m are each independently an integer of 1 to 3.
[0038] It is more preferable that the silylamine compound
represented by Chemical Formula 1 is a compound represented by the
following Chemical Formula 4 in which both sides of an NH group are
symmetric to each other in order to have more excellent effect as
the precursor for depositing a silicon-containing thin film.
##STR00007##
[0039] (In Chemical Formula 4, R.sub.1 and R.sub.2 are each
independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R.sub.1
and R.sub.2 is linked to each other to form a ring; and R.sub.5 is
(C1-C7)alkyl or (C2-C7)alkenyl.)
[0040] The silylamine compound represented by Chemical Formula 1
according to the exemplary embodiment of the present invention may
be selected from the following compounds.
##STR00008##
[0041] The composition for depositing a silicon-containing thin
film according to the present invention contains the silylamine
compound represented by Chemical Formula 1 as the precursor for
depositing a thin film, and the silylamine compound in the
composition for depositing a silicon-containing thin film may be
contained in a content range in which the content may be recognized
by those skilled in the art in consideration of film formation
conditions, a thickness, properties, or the like, of the thin
film.
[0042] As used herein, the term "alkyl" means a linear, branched,
and cyclic saturated and unsaturated hydrocarbons having 1 to 7
carbon atoms, preferably, 1 to 5 carbon atoms, and more preferably
1 to 3 carbon atoms, and examples thereof may include methyl,
ethyl, propyl, butyl, isobutyl, pentyl, and the like.
[0043] As used herein, "halogen" refers to a halogen element, and
examples thereof include fluoro, chloro, bromo, iodo.
[0044] As disclosed herein, the term "alkenyl" as a single group or
a part of another group means a straight-chain, branched-chain, or
cyclic hydrocarbon radical having 2 to 7 carbon atoms and one or
more carbon-carbon double bonds. A more preferable alkenyl radical
is a lower alkenyl radical having 2 to 5 carbon atoms. The most
preferable lower alkenyl radical is a lower alkenyl radical having
about 2 to 3 carbon atoms. Further, an alkenyl group may be
substituted at a random usable attachment point. Examples of the
alkenyl radical include ethenyl, propenyl, allyl, butenyl, and
4-methylbutenyl. The terms "alkenyl" and "lower alkenyl" include
radicals having cis and trans orientations or alternatively, E and
Z orientations.
[0045] As used herein, the phrase "R.sub.1 and R.sub.2, and R.sub.3
and R.sub.4 are each independently linked to each other to form a
ring" includes the case in which R.sub.1 and R.sub.2 are linked to
each other to form a ring but R.sub.3 and R.sub.4 do not form a
ring; the case in which on the contrary, R.sub.1 and R.sub.2 do not
form a ring but R.sub.3 and R.sub.4 are linked to each other to
form a ring; and the case in which R.sub.1 and R.sub.2 are linked
to each other to form a ring and R.sub.3 and R.sub.4 are linked to
each other to form a ring, wherein the formed ring may be an
alicyclic or aromatic ring containing N, and preferably, an
alicyclic ring.
[0046] The silylamine compound represented by Chemical Formula 1
according to the exemplary embodiment of the present invention may
be prepared by a method as long as the method may be recognized by
those skilled in the art.
[0047] In addition, the present invention provides a method for
manufacturing a silicon-containing thin film using the composition
for depositing a silicon-containing thin film according to the
present invention.
[0048] In the method for manufacturing a silicon-containing thin
film according to the present invention, the composition for
depositing a silicon-containing thin film according to the present
invention, containing the silylamine compound represented by
Chemical Formula 1 which is a liquid at room temperature and has
high volatility and excellent thermal stability as the precursor is
used, such that the handling may be easy, it is possible to
manufacture various thin films, and it is possible to manufacture a
silicon-containing thin film having a high purity at a high
deposition rate even at a low temperature and a low power.
[0049] Further, a silicon-containing thin film manufactured by the
method according to the present invention has excellent durability
and electric properties, and resistance against hydrogen fluoride
and a water vapor transmission rate are also excellent.
[0050] In the method for manufacturing a silicon-containing thin
film according to the present invention, the silicon-containing
thin film may be formed by any method as long as it may be
recognized by those skilled in the art. However, preferably, the
silicon-containing thin film may be formed by an atomic layer
deposition (ALD) method, a chemical vapor deposition (CVD) method,
a metal-organic chemical vapor deposition (MOCVD) method, a
low-pressure chemical vapor deposition (LPCVD) method, a plasma
enhanced chemical vapor deposition (PECVD) method, or a plasma
enhanced atomic layer deposition (PEALD) method, but PECVD, ALD, or
PEALD is more preferable in order to allow the thin film to be more
easily deposited, and allow the manufactured thin film to have
excellent properties.
[0051] The silicon-containing thin film according to the present
invention may be a silicon oxide (SiO.sub.2) film, a silicon oxy
carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy
nitride (SiON) film, a silicon carbonitride (SiCN) film, or a
silicon carbide (SiC) film, and various thin films having high
quality may be manufactured.
[0052] More specifically, the method for manufacturing a
silicon-containing thin film according to the present invention may
include:
a. maintaining a temperature of a substrate mounted in a chamber at
30 to 500.degree. C.; b. contacting the composition for depositing
a silicon-containing thin film according to the present invention
with the substrate to adsorb the composition for depositing a
silicon-containing thin film in the substrate; and c. injecting a
reaction gas into the substrate in which the composition for
depositing a silicon-containing thin film is adsorbed to form a
silicon-containing thin film.
[0053] More specifically, the method for manufacturing a
silicon-containing thin film according to the present invention may
include:
a. maintaining a temperature of a substrate mounted in a chamber at
30 to 500.degree. C.; b. contacting the composition for depositing
a silicon-containing thin film with the substrate to adsorb the
composition for depositing a silicon-containing thin film in the
substrate; c. purging the remaining composition for depositing a
silicon-containing thin film and by-products; d. injecting a
reaction gas into the substrate in which the composition for
depositing a silicon-containing thin film is adsorbed to form a
silicon-containing thin film; and e. purging the remaining reaction
gas and by-products, wherein the reaction gas in step D) may remove
a ligand of the silylamine compound contained in the composition
for depositing a silicon-containing thin film to form a Si--O
atomic layer.
[0054] Preferably, the reaction gas according to the exemplary
embodiment may be supplied after being activated by generating
plasma at a plasma power of 50 to 1000 W.
[0055] In the method for manufacturing a silicon-containing thin
film according to the exemplary embodiment of the present
invention, deposition conditions may be adjusted depending on a
structure or thermal properties of a desired thin film. Examples of
the deposition condition according to the exemplary embodiment of
the present invention may include an injection flow rate of the
composition for depositing a silicon-containing thin film
containing the silylamine compound, injection flow rates of the
reaction gas and a carrier gas, pressure, RF power, the temperature
of the substrate, and the like. As non-restrictive examples of the
deposition conditions, the injection flow rate of the composition
for depositing a silicon-containing thin film may be adjusted in a
range of 10 to 1000 cc/min, the injection flow rate of the carrier
gas may be adjusted in a range of 10 to 1000 cc/min, the injection
flow rate of the reaction gas may be adjusted in a range of 1 to
1500 cc/min, the pressure may be adjusted in a range of 0.5 to 10
torr, the RF power may be adjusted in a range of 50 to 1000 W,
preferably 400 to 800 W, and the temperature of the substrate may
be adjusted in a range of 30 to 500.degree. C., preferably 50 to
200.degree. C., and more preferably 50 to 100.degree. C., but the
deposition conditions are not limited thereto.
[0056] The reaction gas used in the method for manufacturing a
silicon-containing thin film according to the present invention is
not limited, but may be one selected from hydrogen (H.sub.2),
hydrazine (N.sub.2H.sub.4), ozone (O.sub.3), oxygen (O.sub.2),
nitrous oxide (N.sub.2O) ammonia (NH.sub.3), nitrogen (N.sub.2),
silane (SiH.sub.4), borane (BH.sub.3), diborane (B.sub.2H.sub.6),
and phosphine (PH.sub.3), or a mixed gas of one or more thereof,
and the carrier gas may be one selected from nitrogen (N.sub.2),
argon (Ar), and helium (He), or a mixed gas of two or more
thereof.
[0057] The substrate used in the method for manufacturing a
silicon-containing thin film according to the present invention may
be a substrate containing one or more semiconductor materials
selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a
silicon-on-insulator (SOI) substrate; a quartz substrate; a glass
substrate for a display; or a flexible plastic substrate made of
polyimide, polyethylene terephthalate (PET), polyethylene
naphthalate (PEN), polymethylmethacrylate (PMMA), polycarbonate
(PC), polyethersulfone (PES), polyester, and the like, but is not
limited thereto.
[0058] Further, the silicon-containing thin film may be directly
formed on the substrate. Alternatively, a large number of
conductive layers, dielectric layers, insulating layers, or the
like, may also be formed between the substrate and the
silicon-containing thin film.
[0059] Preferably, the composition for depositing a
silicon-containing thin film according to the exemplary embodiment
of the present invention may be used as an encapsulant of an
organic light emitting diode (OLED).
[0060] The present invention will be described in detail with
reference to the following Examples. The terms and words used in
the present specification and claims should not be interpreted as
being limited to typical meanings or dictionary definitions, but
should be interpreted as having meanings and concepts relevant to
the technical scope of the present invention based on the rule
according to which an inventor can appropriately define the concept
of the term to describe most appropriately the best method he or
she knows for carrying out the present invention.
[0061] Therefore, configurations described in the embodiments and
shown in the drawings of the present specification indicate only
the most preferred example rather than indicating all the technical
ideas of the present invention and therefore, it is to be
understood that various equivalents and modifications that can
replace the above configurations may be present.
[0062] Further, in all the following Examples, deposition was
performed by a plasma enhanced atomic layer deposition (PEALD)
method known in the art using a commercialized 200 mm single wafer
shower head type ALD apparatus (CN1, Atomic Premium). In addition,
deposition was performed by a plasma enhanced chemical vapor
deposition (PECVD) method known in the art using a commercialized
200 mm single wafer shower head type CVD (PECVD) apparatus (CN1,
Atomic Premium).
[0063] A thickness of a deposited silicon-containing thin film was
measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE), and
properties of the thin film were analyzed using infrared
spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optics), X-ray
photoelectron spectroscopy. Further, a water vapor transmission
rate (WVTR) was measured using a WVTR analyzer (MOCON, Aquatran 2),
an amount of nitrogen used in measurement was 20 ml/minAir, and a
WVTR measurement area was set to 50 cm.sup.2. Stress was measured
using a Frontier semiconductor (FSM500TC), a measurement area was
set to 160 mm, and a thickness of a silicon wafer was set to 0.725
.mu.m, such that properties of the thin film were analyzed.
Example 1
Preparation of Bis(dimethylaminomethylsilyl)amine
##STR00009##
[0065] Under an anhydrous and inert atmosphere, after putting
hexamethyl disilazane (((CH.sub.3).sub.3Si).sub.2NH, 250 g (1.55
mol)) and aluminum chloride (AlCl.sub.3, 10 g (0.075 mol)) into a
2000 mL flame-dried flask, dichloro methylsilane
(CH.sub.3SiHCl.sub.2, 713.19 g (6.20 mol)) was slowly added thereto
while stirring the mixture and maintaining a temperature at
25.degree. C. Then, a reaction solution was slowly heated to
40.degree. C. This mixture reaction solution was stirred for 3
hours, aluminum chloride (AlCl.sub.3) was removed therefrom by
filtration, and the formed chlorotrimethylsilane
((CH.sub.3).sub.3SiCl) and excessively added dichloro methylsilane
(CH.sub.3SiHCl) were removed by simple distillation or distillation
under reduced pressure. While stirring a recovered
bis(chloromethylsilyl)amine ((CH.sub.3SiHCl).sub.2NH)) solution and
maintaining a temperature at -15.degree. C., dimethylamine
((CH.sub.3).sub.2NH, 293.47 g (4.2 mol)) was slowly added thereto.
After the addition was completed, the reaction solution was slowly
heated to room temperature and stirred at room temperature for 6
hours. The formed white solid was removed by filtration, thereby
obtaining a filtrate. A solvent was removed from this filtrate
under reduced pressure, followed by distillation under reduced
pressure, thereby obtaining bis(dimethylaminomethylsilyl)amine
(CH.sub.3SiHN(CH.sub.3).sub.2).sub.2NH, 222.54 g (1.16 mol), yield:
75%).
[0066] .sup.1H-NMR (in C.sub.6D.sub.6):.delta. 0.12 (s, 6H,
((CH3SiHN(CH3)2)2NH), 2.47 (s, 12H, ((CH3SiHN(CH3)2)2NH), 4.43 (m,
2H, ((CH3SiHN(CH3)2)2NH), 2.0 (b, 1H, ((CH3SiHN(CH3)2)2NH).
Comparative Example 1
Preparation of Diisopropylaminosilane
##STR00010##
[0068] Diisopropylamine (280.3 g (2.77 mol)) was put into a 3 L of
flame-dried Schlenk flask, and pentane was added thereto and
stirred therewith. While stirring this solution and maintaining a
temperature at -20.degree. C., trichlorosilane (187.60 g (1.38
mol)) was slowly added thereto, and a reaction solution was slowly
heated to room temperature. This mixture reaction solution was
stirred at room temperature for 4 hours, and when a white solid was
formed, the white solid was removed by filtration, thereby
obtaining a filtrate. A solvent was removed from this filtrate
under reduced pressure, and dimethoxymethane (895.89 g (11.77 mol))
was added thereto as a solvent, and lithium hydride (LiH, 27.53 g
(3.46 mol)) was slowly added thereto. After addition, the mixture
was refluxed for about 6 hours while maintaining a temperature of
the flask at 50.degree. C. After reflux, the flask was cooled to
room temperature, and a white solid was removed by filtration,
thereby obtaining a filtrate. A solvent was removed from the
filtrate under reduced pressure, followed by distillation under
reduced pressure, thereby obtaining diisopropylaminosilane (136.5
g, yield: 75%).
[0069] .sup.1H-NMR (in C.sub.6D.sub.6):.delta. 0.93 (d, 6H,
(SiH3(N(CH(CH3)2)), 2.47 (m, 2H, (SiH3(N(CH(CH3)2)), 5.65 (s, 3H,
(SiH3(NCH(CH3))2)
Example 2
Manufacturing of Silicon Oxide Thin Film by PEALD Using
Bis(dimethylaminomethylsilyl)amine
[0070] Film formation was evaluated using the silylamine compound
prepared in Example 1 according to the present invention as a
composition for forming a silicon oxide film in a general plasma
enhanced atomic layer deposition (PEALD) apparatus using a plasma
enhanced atomic layer deposition (PEALD) method known in the art.
As a reaction gas, nitrous oxide was used together with plasma, and
nitrogen corresponding to an inert gas was used for purging. The
film was formed at reaction gas and plasma time of 0.5 seconds. A
specific method for depositing a silicon oxide thin film was
illustrated in Table 1.
[0071] A thickness of a deposited thin film was measured using the
Ellipsometer, formation of the silicon oxide thin film was analyzed
using infrared spectroscopy, and a composition of the silicon oxide
thin film was analyzed using X-ray photoelectron spectroscopy.
Further, stress of the silicon oxide thin film was analyzed using a
stress meter, and in order to measure a water vapor transmission
rate (WVTR) of the thin film, the WVTR analyzer was used, thereby
measuring the WVTR. Specific analysis results of the silicon oxide
thin film were illustrated in Table 2, and a result obtained by
analyzing the deposited film using infrared spectroscopy was
illustrated in FIG. 3.
Examples 3 to 8
Manufacturing of Silicon Oxide Thin Films by PEALD Using
Bis(dimethylaminomethylsilyl)amine
[0072] Film formation was evaluated using the plasma enhanced
atomic layer deposition (PEALD) method known in the art in the same
manner as in Example 2 except that deposition conditions were
changed as illustrated in Table 1 in Example 2. Further, results
obtained by analyzing the deposited films using infrared
spectroscopy were illustrated in a graph of FIG. 3.
[0073] As appreciated in Examples 2 to 8 according to the present
invention, a deposition rate of the silicon oxide thin film
deposited so as to have a thickness of 700 .ANG. at a low
temperature using the composition for depositing a
silicon-containing thin film, containing
bis(dimethylaminomethylsilyl)amine prepared according to the
present invention was 1.87 to 1.97 .ANG./cycle, such that the
deposition rate was significantly excellent.
[0074] More specifically, it may be appreciated that as compared to
Comparative Example 2 in which a composition for depositing a
silicon-containing thin film, containing diisopropylaminosilane as
a precursor of a thin film, in Examples 2 to 8 in which the
composition for depositing a silicon-containing thin film,
containing a silylamine compound according to the present invention
as a precursor was used, the deposition rate of the thin film was
more excellent, and the water vapor transmission rate was also
excellent, which may have a significant influence on increase in
productivity in forming the silicon-containing thin film. As the
results of analyzing the deposited thin films using the infrared
spectroscopy in FIG. 3, it may be appreciated that all the thin
films formed in Examples 2 to 8 were silicon oxide films. Further,
the water vapor transmission rates of the silicon oxide films
formed in Examples 6 were 4.5E-3 (g/[m.sup.2-day]), such that the
silicon oxide films have excellent moisture proof properties.
Therefore, it is judged that the silicon oxide thin films may be
usefully used in entire application fields of the silicon oxide
thin film, particularly, as an encapsulant of an organic light
emitting diode (OLED).
[0075] A result obtained by measuring a water vapor transmission
rate of a silicon-containing thin film prepared in Example 6 was
illustrated in FIG. 5. The water vapor transmission rate was
constantly maintained for a long period of time as illustrated in
FIG. 5. Therefore, it is judged that the compound suggested in the
present invention may be significantly useful in an OLED device in
which an encapsulation technology of blocking oxygen and moisture
is important.
Comparative Example 2
Manufacturing of Silicon Oxide Thin Film by PEALD Using
Diisopropylaminosilane
[0076] Film formation was evaluated using the plasma enhanced
atomic layer deposition (PEALD) method known in the art under the
same deposition conditions as in Example 2 except that
diisopropylaminosilane prepared in Comparative Example 1 was used,
a heating temperature of the precursor was 20.degree. C., and the
number of deposition was 590 cycles as illustrated in the following
Table 1. The deposited thin film was analyzed by the same analysis
method as in Example 2 under the same conditions as in Example 2,
such that analysis results were secured. In order to perform
measurement at the same thickness as those of the thin films formed
in Examples 2 to 8, the number of deposition was changed. A
specific method for depositing a silicon oxide thin film was
illustrated in the following Table 1, and properties of the
deposited thin films were illustrated in Table 2. As illustrated in
Table 2, a deposition rate was 1.19 .ANG./cycle, and a water vapor
transmission rate (WVTR) was 8.0E-2 (g/[m.sup.2-day]), which were
lower than those of the bis(dimethylaminomethylsilyl)amine in
Example 2.
TABLE-US-00001 TABLE 1 Deposition Conditions of Silicon Oxide Thin
Film by PEALD Temper- Reaction Gas and Reaction ature Precursor
Purge Plasma Gas Purge of Heating Injection Flow Flow RF Flow No.
of Process Substrate Temperature Time Rate Time Rate Power Time
Time Rate Deposition Time (.degree. C.) (.degree. C.) (sec) (sccm)
(sec) (sccm) (W) (sec) (sec) (sccm) Cycle (sec) Example 2 90 70 0.1
600 0.4 800 400 0.5 0.1 300 380 418 Example 3 90 70 0.1 600 0.4 800
400 0.7 0.1 300 363 471.9 Example 4 90 70 0.1 600 0.4 800 400 0.9
0.1 300 370 555 Example 5 90 70 0.1 600 0.4 800 400 1.2 0.1 300 370
666 Example 6 90 70 0.1 600 0.4 400 400 0.9 0.1 300 370 555 Example
7 90 70 0.1 600 0.4 1400 400 0.9 0.1 300 370 555 Example 8 90 70
0.1 600 0.4 800 500 0.9 0.1 300 370 555 Comparative 90 20 0.1 600
0.4 800 400 0.5 0.1 300 590 649 Example 2
TABLE-US-00002 TABLE 2 Evaluation of Properties of Silicon Oxide
Thin Film O/Si Deposition Thickness of Refractive Composition Rate
Thin Film Index Ratio Stress of Film WVTR Variable (.ANG./cycle)
(.ANG.) -- -- (MPa) (g/[m.sup.2-day]) Example 2 Plasma 1.87 710
1.46 1.73 -134 Unmeasured Time of 0.5 sec Example 3 Plasma 1.95 723
1.47 1.73 -193 Unmeasured Time of 0.7 sec Example 4 Plasma 1.95 721
1.47 1.73 -149 2.0E-2 Time of 0.9 sec Example 5 Plasma 1.92 711
1.48 1.73 -293 2.5E-2 Time of 1.2 sec Example 6 Reaction 1.97 731
1.48 1.72 -250 4.5E-3 Gas of 400 sccm Example 7 Reaction 1.92 711
1.47 1.73 -120 5.2E-2 Gas of 1400 sccm Example 8 RF Power of 1.95
720 1.48 1.73 -151 1.1E-2 500 W Comparative Plasma 1.19 702 1.48
1.73 -272 8.0E-2 Example 2 Time of 0.5 sec
Example 9
Manufacturing of Silicon Nitride Thin Film by PEALD Using
Bis(dimethylaminomethylsilyl)amine
[0077] Film formation was evaluated using the silylamine compound
prepared in Example 1 according to the present invention as a
composition for forming a silicon nitride film in a general plasma
enhanced atomic layer deposition (PEALD) apparatus using a plasma
enhanced atomic layer deposition (PEALD) method known in the art.
As a reaction gas, nitrogen and ammonia were used together with
plasma as first reaction gas, and nitrogen was used as a second
reaction gas. The nitrogen corresponding to an inert gas was used
for purging. A specific method for depositing a silicon nitride
thin film was illustrated in Table 3.
[0078] A thickness of a deposited thin film was measured using the
Ellipsometer, formation of the silicon nitride thin film was
analyzed using infrared spectroscopy, and a composition of the
silicon nitride thin film was analyzed using X-ray photoelectron
spectroscopy. Further, in order to measure a water vapor
transmission rate (WVTR) of the thin film, the WVTR analyzer was
used, thereby measuring the WVTR. Specific analysis results of the
silicon nitride thin film were illustrated in the following Table
4, and results obtained by analyzing the deposited film using
infrared spectroscopy were illustrated in FIG. 4.
Examples 10 to 15 and Comparative Example 3
Manufacturing of Silicon Nitride Thin Films by PEALD Using
Bis(dimethylaminomethylsilyl)amine or Diisopropylaminosilane
[0079] Film formation was evaluated using a plasma enhanced atomic
layer deposition (PEALD) method known in the art in the same manner
as in Example 9 except for changing deposition conditions as in
Table 3, and the deposited thin film was analyzed by the same
analysis method as in Example 9 under the same conditions as in
Example 9, such that analysis results were secured. A specific
method for depositing a silicon nitride thin film and analysis
results were illustrated in the following Tables 3 and 4. Further,
the deposited films were analyzed using infrared spectroscopy, and
the result was illustrated in FIG. 4. As a result, it may be
appreciated that the thin film manufactured in Examples 10 to 15
were silicon nitride thin films.
[0080] Further, a result obtained by measuring a water vapor
transmission rate of a silicon-containing thin film prepared in
Example 11 was illustrated in FIG. 6. The water vapor transmission
rate was constantly maintained for a long period of time as
illustrated in FIG. 6. Therefore, it is judged that the compound
suggested in the present invention may be significantly usefully
used in an OLED device in which an encapsulation technology of
blocking oxygen and moisture is important.
TABLE-US-00003 TABLE 3 Deposition Conditions of Silicon Nitride
Thin Film by PEALD Temper- Precursor Reaction ature Heating In-
Purge Reaction Gas and Plasma Gas Purge No. of of Temper- jection
Flow Flow RF Flow RF Flow Depo- Process Substrate ature Time Rate
Time Rate Power Time Rate Power Time Time Rate sition Time
(.degree. C.) (.degree. C.) (sec) (sccm) (sec) (sccm) (W) (sec)
(sccm) (W) (sec) (sec) (sccm) Cycle (sec) Example 9 90 65 0.4 6000
0.4 2000 600 0.8 6000 600 2 0.4 6000 486 2139 Example 10 90 65 0.4
6000 0.4 2000 600 1.5 6000 600 2 0.4 6000 547 2789 Example 11 90 65
0.4 6000 0.4 2000 600 1.2 6000 600 3 0.4 6000 500 2900 Example 12
90 65 0.4 6000 0.4 2000 600 0.8 6000 600 4 0.4 6000 480 3068
Example 13 90 65 0.4 6000 0.4 2000 600 1.5 6000 600 4 0.4 6000 604
4284 Example 14 90 65 0.4 6000 0.4 2000 600 1 6000 600 2 0.4 6000
493 2268 Example 15 90 65 0.4 6000 0.4 2000 800 0.6 6000 800 1.3
0.4 6000 432 1512 Comparative 90 20 0.4 6000 0.4 2000 800 0.6 6000
800 1.3 0.4 6000 697 2442 Example 3
TABLE-US-00004 TABLE 4 Evaluation of Properties of Silicon Nitride
Thin Film Thickness N/Si Deposition of Thin Refractive Composition
Rate Film Index Ratio WVTR Variable (.ANG./cycle) (.ANG.) -- --
(g/[m.sup.2-day]) Example Plasma Time 0.72 350 1.82 1.32 1.7E-3 9
of 0.8 sec/2 sec Example Plasma Time 0.64 350 1.87 1.22 2.2E-2 10
of 1.5 sec/2 sec Example Plasma Time 0.7 350 1.88 1.24 2.6E-4 11 of
1.2 sec/3 sec Example Plasma Time 0.73 350 1.89 1.25 1.7E-2 12 of
0.8 sec/4 sec Example Plasma Time 0.58 350 1.93 1.17 3.1E-2 13 of
1.5 sec/4 sec Example Plasma Time 0.71 350 1.83 1.26 4.1E-4 14 of 1
sec/2 sec Example Plasma 0.81 350 1.84 1.18 2.7E-3 15 Power of 800
W Plasma Time of 0.6 sec/1.3 sec Comparative Plasma 0.43 350 1.88
1.24 7.2E-3 Example Power of 3 800 W Plasma Time of 0.6 sec/1.3
sec
* * * * *