U.S. patent application number 16/398209 was filed with the patent office on 2019-09-19 for compositions and processes for depositing carbon-doped silicon-containing films.
This patent application is currently assigned to Versum Materials US, LLC. The applicant listed for this patent is Versum Materials US, LLC. Invention is credited to Haripin Chandra, Bing Han, Eugene Joseph Karwacki, Xinjian Lei, Mark Leonard O'Neill, Ronald Martin Pearlstein, Manchao Xiao.
Application Number | 20190287798 16/398209 |
Document ID | / |
Family ID | 46276000 |
Filed Date | 2019-09-19 |
United States Patent
Application |
20190287798 |
Kind Code |
A1 |
Xiao; Manchao ; et
al. |
September 19, 2019 |
Compositions and Processes for Depositing Carbon-Doped
Silicon-Containing Films
Abstract
Described herein are compositions for depositing a carbon-doped
silicon containing film comprising: a precursor comprising at least
one compound selected from the group consisting of: an
organoaminosilane having a formula of R.sup.8N(SiR.sup.9LH).sub.2,
wherein R.sup.8, R.sup.9, and L are defined herein. Also described
herein are methods for depositing a carbon-doped silicon-containing
film using the composition wherein the method is one selected from
the following: cyclic chemical vapor deposition (CCVD), atomic
layer deposition (ALD), plasma enhanced ALD (PEALD) and plasma
enhanced CCVD (PECCVD).
Inventors: |
Xiao; Manchao; (Tempe,
AZ) ; Lei; Xinjian; (Tempe, AZ) ; Pearlstein;
Ronald Martin; (Tempe, AZ) ; Chandra; Haripin;
(Tempe, AZ) ; Karwacki; Eugene Joseph; (Tempe,
AZ) ; Han; Bing; (Tempe, AZ) ; O'Neill; Mark
Leonard; (Tempe, AZ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Versum Materials US, LLC |
Tempe |
AZ |
US |
|
|
Assignee: |
Versum Materials US, LLC
Tempe
AZ
|
Family ID: |
46276000 |
Appl. No.: |
16/398209 |
Filed: |
April 29, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15233018 |
Aug 10, 2016 |
10319584 |
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16398209 |
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14122825 |
Jun 4, 2014 |
9447287 |
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15233018 |
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61493031 |
Jun 3, 2011 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07F 7/10 20130101; C07F
7/0896 20130101; C23C 16/45553 20130101; H01L 21/0228 20130101;
H01L 21/02126 20130101; C23C 16/345 20130101; H01L 21/02211
20130101; C09D 7/63 20180101; C23C 16/401 20130101; C09D 5/00
20130101; C23C 16/30 20130101 |
International
Class: |
H01L 21/02 20060101
H01L021/02; C09D 7/63 20060101 C09D007/63; C07F 7/10 20060101
C07F007/10; C07F 7/08 20060101 C07F007/08; C23C 16/455 20060101
C23C016/455; C23C 16/40 20060101 C23C016/40; C23C 16/34 20060101
C23C016/34; C23C 16/30 20060101 C23C016/30; C09D 5/00 20060101
C09D005/00 |
Claims
1. A composition for depositing a carbon-doped silicon containing
film comprising: a precursor comprising at least one compound
selected from the group consisting of: an organoaminosilane having
a formula of R.sup.8N(SiR.sup.9LH).sub.2, wherein R.sup.8 is
selected from the group consisting of a C.sub.1 to C.sub.10 linear
or branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group,
a linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; R.sup.9 selected from the group consisting of
hydrogen, C.sub.1 to C.sub.10 linear or branched alkyl, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group; and L is
selected from the group consisting of Cl, Br, and I.
2. The composition of claim 1 wherein R.sup.8 is selected from the
group consisting of Me, Et, .sup.nPr, .sup.iPr, .sup.nBu, .sup.iBu,
.sup.sBu, .sup.tBu, isomers of pentyl, vinyl, phenyl, and alkyl
substituted phenyl.
3. The composition of claim 1 wherein R.sup.9 is selected from the
group consisting of hydrogen, Me, Et, .sup.nP, .sup.iPr, .sup.nBu,
.sup.iBu, .sup.sBu, .sup.tBu, isomers of pentyl, vinyl, phenyl, and
alkyl substituted phenyl.
4. A method of forming a carbon-doped silicon nitride film via an
atomic layer deposition process, the method comprising the steps
of: a. providing a substrate in a reactor; b. introducing into the
reactor a precursor comprising at least one organoaminosilane
having a formula of R.sup.8N(SiR.sup.9LH).sub.2, wherein R.sup.8 is
selected from the group consisting of a C.sub.1 to C.sub.10 linear
or branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group,
a linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; R.sup.9 selected from the group consisting of
hydrogen, C.sub.1 to C.sub.10 linear or branched alkyl, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group; and L is
selected from the group consisting of Cl, Br, and I; c. purging the
reactor with a purge gas; d. introducing a nitrogen source into the
reactor wherein the nitrogen source is selected from the group
consisting of ammonia, hydrazine, monoalkylhydrazine,
dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma,
nitrogen plasma, nitrogen/hydrogen plasma, and mixture thereof; and
e. purging the reactor with a purge gas, wherein steps b through e
are repeated until a desired thickness of the film is obtained.
5. A method of forming a carbon-doped silicon oxide film via an
atomic layer deposition process, the method comprising the steps
of: a. providing a substrate in a reactor; b. introducing into the
reactor at least one compound selected from the group consisting
of: an organoaminosilane having a formula of
R.sup.9N(SiR.sup.9LH).sub.2, wherein R.sup.9 is selected from the
group consisting of a C.sub.1 to C.sub.10 linear or branched alkyl
group, a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or
branched C.sub.2 to C.sub.10 alkenyl group, a linear or branched
C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic
group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; R.sup.9 selected from the group consisting of
hydrogen, C.sub.1 to C.sub.10 linear or branched alkyl, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group; and L is
selected from the group consisting of Cl, Br, and I; c. purging the
reactor with a purge gas; d. introducing an oxygen source into the
reactor wherein the oxygen source is selected from the group
consisting of water, water plasma, oxygen, peroxide, oxygen plasma,
ozone, NO, NO.sub.2, carbon monoxide, carbon dioxide, and
combinations thereof; and e purging the reactor with a purge gas,
wherein steps b through e are repeated until a desired thickness of
the film is obtained.
6. A film deposited by the method of claim 4.
7. A film deposited by the method of claim 5.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation application of U.S.
application Ser. No. 15/233,018, filed Aug. 10, 2016, which in turn
claims priority to U.S. application Ser No. 14/122,825, filed Jun.
4, 2014, which in turn claims priority to U.S. Application No.
61/493,031, filed on Jun. 3, 2011, the disclosures of which are
hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] Precursor(s), particularly organoaminosilane precursors,
that can be used for the deposition of silicon containing films,
including but not limited to, silicon oxide films, silicon nitride
films, or silicon oxynitride films which further comprise carbon
(referred to collectively herein as carbon-doped silicon-containing
films) are described herein. In yet another aspect, described
herein is the use of the organoaminosilane precursor(s) for
depositing silicon-containing in the fabrication of devices, such
as, but not limited to, integrated circuit devices. In these or
other aspects, the organoaminosilane precursor(s) may be used for a
variety of deposition processes, including but not limited to,
atomic layer deposition ("ALD"), chemical vapor deposition ("CVD"),
plasma enhanced chemical vapor deposition ("PECVD"), low pressure
chemical vapor deposition ("LPCVD"), and atmospheric pressure
chemical vapor deposition.
[0003] Several classes of compounds can be used as precursors for
carbon-doped silicon-containing films. Examples of these compounds
suitable for use as precursors include silanes, chlorosilanes,
polysilazanes, aminosilanes, and azidosilanes. Inert carrier gas or
diluents such as, but not limited, helium, hydrogen, nitrogen,
etc., are also used to deliver the precursors to the reaction
chamber.
[0004] Some important characteristics of a carbon-doped
silicon-containing film are wet etch resistance and hydrophobicity.
Generally speaking, the introduction of carbon to a
silicon-containing film helps decrease the wet etch rate and
increases the hydrophobicity. Additional advantages of adding
carbon to a silicon containing film is to lower the dielectric
constant or provide improvements to other electrical or physical
attributes of the film.
[0005] Further examples of precursors and processes for depositing
carbon-doped silicon-containing films are provided in the following
references. Applicants' patents, U.S. Pat. Nos. 7,875,556;
7,875,312; and 7,932,413, described classes of aminosilanes which
are used for the deposition of dielectric films, such as, for
example, silicon oxide and silicon carbonitride films in a chemical
vapor deposition or atomic layer deposition process.
[0006] Japanese Publ. No. JP 2010/275602 describes a material for
chemical vapor deposition for depositing a silicon-containing thin
film that is represented by the formula
HSiMe(R.sup.1)(NR.sup.2R.sup.3) (R.sup.1.dbd.NR.sup.4R.sup.5, C1-5
alkyl; R.sup.2, R.sup.4.dbd.H, C1-5 alkyl; R.sup.3,
R.sup.5.dbd.C1-5 alkyl). The silicon-containing thin film is formed
by temperatures ranging from 300-500.degree. C.
[0007] US Publ. No. 2008/0124946A1 describes a process for
depositing a carbon containing silicon oxide film, or a carbon
containing silicon nitride film having enhanced etch resistance.
The process comprises using a structure precursors containing
silicon, a dopant precursor containing carbon, and mixing the
dopant precursors with the structure precursor to obtain a mixture
having a mixing ratio of Rm (% weight of the dopant precursor added
to the structure precursor) between 2% and 85%; and a flow rate of
Fm; providing a chemical modifier having a flow rate of Fc; having
a flow ratio R2 defined as R2=Fm/Fc between 25% and 75%; and
producing the carbon containing silicon containing film or the
carbon containing silicon oxide film having enhanced etch
resistance wherein the etch resistance is increased with increasing
incorporation of the carbon.
[0008] US Publ. No. 2006/0228903 describes a process for
fabricating a carbon doped silicon nitride layer using a first
precursor which provides a source of silicon and a second precursor
which adds carbon to the film. Examples of first precursor
described in the '903 publication include halogenated silanes and
disilanes, aminosilanes, cyclodisilazanes, linear and branched
silizanes, azidosilanes, substituted versions of
1,2,4,5-tetraaza-3,6-disilacyclohexane, and silyl hydrazines.
Examples of the second precursor described in the '903 publication
are alkyl silanes that have the general formula SiR.sub.4 where R
is any ligand including but not limited to hydrogen, alkyl and aryl
(all R groups are independent), alkyl polysilanes, halogenated
alkyl silanes, carbon bridged silane precursors; and silyl
ethanes/ethylene precursors.
[0009] US Publ. No. 2005/0287747A1 describes a process for forming
a silicon nitride, silicon oxide, silicon oxynitride or silicon
carbide film that includes adding at least one non-silicon
precursor (such as a germanium precursor, a carbon precursor, etc.)
to improve the deposition rate and/or makes possible tuning of
properties of the film, such as tuning of the stress of the
film.
[0010] U.S. Pat. No. 5,744,196A discloses the process comprises (a)
heating a substrate upon which SiO.sub.2 is to be deposited to
approximately 150-500 Deg in a vacuum maintained at approximately
50-750 m torr; (b) introducing into the vacuum an
organosilane-containing feed and an O-containing feed, the
organosilane contg.-feed consisting essentially of >=1 compds.
having the general formula
R.sup.1Si(H.sub.2)C.sub.x(R.sup.4).sub.2Si(H.sub.2)R.sup.2, where
R.sup.1, R.sup.2.dbd.C1-6 alkyl, alkenyl, alkynyl, or aryl, or
R.sup.1 and R.sup.2 are combined to form an alkyl chain
Cx(R.sup.3).sub.2; R.sup.3.dbd.H, C.sub.xH.sub.2x+1; x=1-6; R.sup.4
50 H, C.sub.yH.sub.2y+1; and y=1-6; and (c) maintaining the
temperature and vacuum, thereby causing a thin film of SiO.sub.2 to
deposit on the substrate.
[0011] Precursors and processes that are used in depositing
carbon-doped silicon oxide films generally deposit the films at
temperatures greater than 550.degree. C. The trend of
miniaturization of semiconductor devices and low thermal budget
requires lower process temperatures and higher deposition rates.
Further, there is a need in the art to provide novel precursors or
combinations of precursors that may allow for more effective
control of the carbon content contained in the carbon-doped silicon
containing film. Accordingly, there is a continuing need in the art
to provide compositions of precursors for the deposition of
carbon-doped silicon-containing films which provide films that
exhibit one or more of the following attributes: lower relative
etch rates, greater hydrophobicity, higher deposition rates, higher
density, compared to films deposited using the individual
precursors alone.
BRIEF SUMMARY OF THE INVENTION
[0012] Described herein are precursor compositions and methods
using same for forming films comprising carbon-doped silicon
(referred to herein as silicon containing films), such as, but not
limited to, carbon-doped stoichiometric or non-stoichiometric
silicon oxide, carbon-doped stoichiometric or non-stoichiometric
silicon nitride, silicon oxynitride, silicon oxycarbide, silicon
carbonitride, and combinations thereof onto at least a portion of a
substrate. In certain embodiments, the carbon-doped
silicon-containing can have a carbon content of 2.times.10.sup.19
carbon atom/cc or less of carbon as measured by measured by dynamic
Secondary Ions Mass Spectrometry (SIMS). In alternative
embodiments, the carbon-doped silicon-containing films can have a
carbon content that ranges from about 2.times.10.sup.19 carbon
atom/cc to 2.times.10.sup.22 carbon atom/cc as measured by dynamic
SIMS.
[0013] Also described herein are the methods to form carbon-doped
silicon containing films or coatings on an object to be processed,
such as, for example, a semiconductor wafer. In one embodiment of
the method described herein, a layer comprising silicon, carbon and
oxygen is deposited onto a substrate using the precursor
composition described herein and an oxidizing agent in a deposition
chamber under conditions for generating a carbon-doped silicon
oxide layer on the substrate. In another embodiment of the method
described herein, a layer comprising silicon, carbon, and nitrogen
is deposited onto a substrate using the precursor composition
described herein and an nitrogen containing precursor in a
deposition chamber under conditions for generating a carbon-doped
silicon nitride layer on the substrate. In certain embodiments, the
deposition method for depositing the carbon-doped
silicon-containing film using the precursor composition described
herein is selected from the group consisting of cyclic chemical
vapor deposition (CCVD), atomic layer deposition (ALD), plasma
enhanced ALD (PEALD) and plasma enhanced CCVD (PECCVD).
[0014] In one aspect, there is provided a composition for
depositing a carbon-doped silicon containing film comprising:
[0015] (a) a first precursor comprising at least one selected from
the group consisting of: [0016] (i) an organoaminoalkylsilane
having a formula of R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x
wherein x=1, 2, 3; [0017] (ii) an organoalkoxyalkylsilane having a
formula of R.sup.6Si(OR.sup.7).sub.xH.sub.3-x wherein x=1, 2, 3;
[0018] (iii) an organoaminosilane having a formula of
R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sub.2; [0019] (iv) an
organoaminosilane having a formula of R.sup.8N(SiR.sup.9LH).sub.2;
and combinations thereof; wherein R.sup.3, R.sup.4, and R.sup.7 are
each independently selected from the group consisting of a C.sub.1
to C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; R.sup.5 and
R.sup.6 are each independently selected from the group consisting
of a C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group, and a
halide atom; R.sup.8 and R.sup.9 are each independently selected
from the group consisting of hydrogen, C.sub.1 to C.sub.10 linear
or branched alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a
linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and R.sup.10 and R.sup.11 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group, and L=Cl, Br,
or I; wherein R.sup.3 and R.sup.4 can form a cyclic ring or an
alkyl-substituted cyclic ring; and wherein R.sup.10 and R.sup.11
can form a cyclic ring or an alkyl-substituted cyclic ring; and
[0020] (b) optionally a second precursor comprising an
organoaminosilane having a formula Si(NR.sup.1R.sup.2)H.sub.3
wherein R.sup.1 and R.sup.2 are each independently selected from
the group consisting of a C.sub.1 to C.sub.10 linear or branched
alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or
branched C.sub.2 to C.sub.10 alkenyl group, a linear or branched
C.sub.3 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic
group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group and wherein R.sup.1 and R.sup.2 can form a
cyclic ring or an alkyl-substituted cyclic ring.
[0021] In a further aspect, there is provided a composition for
depositing a carbon-doped silicon containing film comprising:
[0022] a first precursor comprising at least one selected from the
group consisting of: [0023] an organoaminoalkylsilane having a
formula of R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1,
2, 3; [0024] an organoalkoxyalkylsilane having a formula of
R.sup.6Si(OR.sup.7).sub.xH.sub.3-x wherein x=1, 2, 3; [0025] an
organoaminosilane having a formula of
R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sub.2; [0026] an
organoaminosilane having a formula of R.sup.8N(SiR.sup.9LH).sub.2;
and combinations thereof; wherein R.sup.3, R.sup.4, and R.sup.7 are
each independently selected from the group consisting of a C.sub.1
to C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; R.sup.5 and
R.sup.6 are each independently selected from the group consisting
of a C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group, and a
halide atom; R.sup.8 and R.sup.9 are each independently selected
from the group consisting of hydrogen, C.sub.1 to C.sub.10 linear
or branched alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a
linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and R.sup.10 and R.sup.11 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group, and L=Cl, Br,
or I; wherein R.sup.3 and R.sup.4 can form a cyclic ring or an
alkyl-substituted cyclic ring; and wherein R.sup.10 and R.sup.11
can form a cyclic ring or an alkyl-substituted cyclic ring; and
[0027] optionally a second precursor comprising an
organoaminosilane having a formula of
R.sup.12Si(NR.sup.13R.sup.14)).sub.xH.sub.3-x wherein x=0, 1, 2, 3,
and 4, wherein R.sup.12, R.sup.13, and R.sup.14 are each
independently selected from the group consisting of H, a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group and wherein
R.sup.13 and R.sup.14 can form a cyclic ring or an
alkyl-substituted cyclic ring.
[0028] In another aspect, there is provided a composition for
depositing a carbon-doped silicon containing film comprising: a
first precursor comprising an organoaminoalkylsilane having a
formula of R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1,
2, 3 wherein R.sup.3 and R.sup.4 are each independently selected
from the group consisting of a C.sub.1 to C.sub.10 linear or
branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group, a
linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; R.sup.5 is selected from the group consisting
of a C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group, and a
halide atom, and wherein R.sup.3 and R.sup.4 can form a cyclic ring
or an alkyl-substituted cyclic ring. In this or other embodiments,
the composition further comprises a second precursor comprising an
organoaminosilane having a formula Si(NR.sup.1R.sup.2)H.sub.3
wherein R.sup.1 and R.sup.2 are each independently selected from
the group consisting of a C.sub.1 to C.sub.10 linear or branched
alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or
branched C.sub.2 to C.sub.10 alkenyl group, a linear or branched
C.sub.3 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic
group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group and wherein R.sup.1 and R.sup.2 can form a
cyclic ring or an alkyl-substituted cyclic ring.
[0029] In a further aspect, there is provided a composition for
depositing a carbon-doped silicon containing film comprising: a
first precursor comprising: an organoalkoxyalkylsilane having a
formula of R.sup.6Si(OR.sup.7).sub.xH.sub.3-x wherein x=1, 2, 3 and
wherein R.sup.7 is independently selected from the group consisting
of a C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group; and
R.sup.6 is independently selected from the group consisting of a
C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3 to
C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group, and a
halide atom; R.sup.8 and R.sup.9 are each independently selected
from the group consisting of hydrogen, C.sub.1 to C.sub.10 linear
or branched alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a
linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group. In this or other embodiments, the composition
further comprises a second precursor comprising an
organoaminosilane having a formula Si(NR.sup.1R.sup.2)H.sub.3
wherein R.sup.1 and R.sup.2 are each independently selected from
the group consisting of a C.sub.1 to C.sub.10 linear or branched
alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or
branched C.sub.2 to C.sub.10 alkenyl group, a linear or branched
C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic
group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group and wherein R.sup.1 and R.sup.2 can form a
cyclic ring or an alkyl-substituted cyclic ring.
[0030] In yet another aspect, there is provided a composition for
depositing a carbon-doped silicon containing film comprising: a
first precursor comprising: an organoaminosilane having a formula
of R.sup.8N(SiR.sup.9(NR.sup.10 R.sup.11)H).sub.2 wherein R.sup.8
and R.sup.9 are each independently selected from the group
consisting of hydrogen, C.sub.1 to C.sub.10 linear or branched
alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or
branched C.sub.2 to C.sub.10 alkenyl group, a linear or branched
C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic
group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and R.sup.10 and R.sup.11 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; and wherein
R.sup.10 and R.sup.11 can form a cyclic ring or an
alkyl-substituted cyclic ring. In this or other embodiments, the
composition further comprises a second precursor comprising an
organoaminosilane having a formula Si(NR.sup.1R.sup.2)H.sub.3
wherein R.sup.1 and R.sup.2 are each independently selected from
the group consisting of a C.sub.1 to C.sub.10 linear or branched
alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or
branched C.sub.2 to C.sub.10 alkenyl group, a linear or branched
C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic
group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group and wherein R.sup.1 and R.sup.2 can form a
cyclic ring or an alkyl-substituted cyclic ring.
[0031] In another aspect, there is provided a method of forming a
carbon-doped silicon oxide film via an atomic layer deposition
process, the method comprising the steps of:
[0032] a. providing a substrate in a reactor;
[0033] b. introducing into the reactor a first precursor comprising
at least one compound selected from the group consisting of: [0034]
(i) an organoaminoalkylsilane having a formula of
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1, 2, 3; [0035]
(ii) an organoalkoxyalkylsilane having a formula of
R.sup.6Si(OR.sup.7).sub.xH.sub.3-x wherein x=1, 2, 3; [0036] (iii)
an organoaminosilane having a formula of
R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sub.2; [0037] (iv) an
organoaminosilane having a formula of R.sup.8N(SiR.sup.9LH).sub.2
and combinations thereof;
[0038] wherein R.sup.3, R.sup.4, and R.sup.7 are each independently
selected from the group consisting of a C.sub.1 to C.sub.10 linear
or branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group,
a linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; R.sup.5 and R.sup.6 are each independently
selected from the group consisting of a C.sub.1 to C.sub.10 linear
or branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group,
a linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.3 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group and a halide atom; R.sup.8 and R.sup.9 are each
independently selected from the group consisting of hydrogen,
C.sub.1 to C.sub.10 linear or branched alkyl, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; and R.sup.10
and R.sup.11 are each independently selected from the group
consisting of a C.sub.1 to C.sub.10 linear or branched alkyl group,
a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or branched
C.sub.2 to C.sub.10 alkenyl group, a linear or branched C.sub.2 to
C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a
C.sub.3 to C.sub.10 saturated or unsaturated heterocyclic group;
L=Cl, Br, or I and wherein R.sup.3 and R.sup.4 can form a cyclic
ring or an alkyl-substituted cyclic ring; and wherein R.sup.10 and
R.sup.11 can form a cyclic ring or an alkyl-substituted cyclic
ring;
[0039] c. purging the reactor with a purge gas;
[0040] d. introducing an oxygen source into the reactor;
[0041] e. introducing into the reactor a second precursor having
the following formula Si(NR.sup.1R.sup.2)H.sub.3 wherein R.sup.1
and R.sup.2 are each independently selected from the group
consisting of a C.sub.1 to C.sub.10 linear or branched alkyl group,
a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or branched
C.sub.2 to C.sub.10 alkenyl group, a linear or branched C.sub.2 to
C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a
C.sub.3 to C.sub.10 saturated or unsaturated heterocyclic group and
wherein R.sup.1 and R.sup.2 can form a cyclic ring or an
alkyl-substituted cyclic ring;
[0042] f. purging the reactor with a purge gas;
[0043] g. introducing an oxygen source into the reactor;
[0044] h. purging the reactor with a purge gas; and
[0045] i. repeating the steps b through h until a desired thickness
of the film is obtained. In one particular embodiment of the method
described herein, the precursor in step (b) comprises an
organoaminoalkylsilane described herein as (i). More particularly,
the precursor in step (b) comprises the organaoaminoalkylsilane
2,6-dimethylpiperidinomethylsilane.
[0046] In another aspect, there is provided a method of forming a
carbon-doped silicon nitride film via an atomic layer deposition
process, the method comprising the steps of:
[0047] a. providing a substrate in a reactor;
[0048] b. introducing into the reactor a first precursor comprising
at least one compound selected from the group consisting of: [0049]
(i) an organoaminoalkylsilane having a formula of
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1, 2, 3; [0050]
(ii) an organoalkoxyalkylsilane having a formula of
R.sup.6Si(OR.sup.7).sub.xH.sub.3-x wherein x=1, 2, 3; [0051] (iii)
an organoaminosilane having a formula of
R.sup.8N(SiR.sup.9(NR.sup.10 R.sup.11)H).sub.2; [0052] (iv) an
organoaminosilane having a formula of R.sup.8N(SiR.sup.9LH).sub.2
and combinations thereof; wherein R.sup.3, R.sup.4, and R.sup.7 are
each independently selected from the group consisting of a C.sub.1
to C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; R.sup.5 and
R.sup.6 are each independently selected from the group consisting
of a C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.3 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group and a
halide atom; R.sup.8 and R.sup.9 are each independently selected
from the group consisting of hydrogen, C.sub.1 to C.sub.10 linear
or branched alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a
linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and R.sup.10 and R.sup.11 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; L=Cl, Br, or
I and wherein R.sup.3 and R.sup.4 can form a cyclic ring or an
alkyl-substituted cyclic ring; and wherein R.sup.10 and R.sup.11
can form a cyclic ring or an alkyl-substituted cyclic ring;
[0053] c. purging the reactor with a purge gas;
[0054] d. introducing a nitrogen source into the reactor;
[0055] e. introducing into the reactor a second precursor having
the following formula Si(NR.sup.1R.sup.2)H.sub.3 wherein R.sup.1
and R.sup.2 are each independently selected from the group
consisting of a C.sub.1 to C.sub.10 linear or branched alkyl group,
a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or branched
C.sub.2 to C.sub.10 alkenyl group, a linear or branched C.sub.2 to
C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a
C.sub.3 to C.sub.10 saturated or unsaturated heterocyclic group and
wherein R.sup.1 and R.sup.2 can form a cyclic ring or an
alkyl-substituted cyclic ring
[0056] f. purging the reactor with a purge gas;
[0057] g. introducing a nitrogen source into the reactor;
[0058] h. purging the reactor with a purge gas; and
[0059] i. repeating the steps b through h until a desired thickness
of the film is obtained. In one particular embodiment of the method
described herein, the precursor in step (b) comprises an
organoaminoalkylsilane described herein as (i). More particularly,
the precursor in step (b) comprises the organaoaminoalkylsilane
2,6-dimethylpiperidinomethylsilane.
[0060] In another aspect, there is provided a method of forming a
carbon-doped silicon oxide film via an atomic layer deposition
process, the method comprising the steps of:
[0061] a. providing a substrate in a reactor;
[0062] b. introducing into the reactor a first precursor comprising
at least one compound selected from the group consisting of: [0063]
(v) an organoaminoalkylsilane having a formula of
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1, 2, 3; [0064]
(vi) an organoalkoxyalkylsilane having a formula of
R.sup.6Si(OR.sup.7).sub.xH.sub.3-x wherein x=1, 2, 3; [0065] (vii)
an organoaminosilane having a formula of
R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sub.2; [0066] (viii) an
organoaminosilane having a formula of R.sup.8N(SiR.sup.9LH).sub.2
and combinations thereof; wherein R.sup.3, R.sup.4, and R.sup.7 are
each independently selected from the group consisting of a C.sub.1
to C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; R.sup.5 and
R.sup.6 are each independently selected from the group consisting
of a C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.3 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group and a
halide atom; R.sup.8 and R.sup.9 are each independently selected
from the group consisting of hydrogen, C.sub.1 to C.sub.10 linear
or branched alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a
linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and R.sup.10 and R.sup.11 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; L=Cl, Br, or
I and wherein R.sup.3 and R.sup.4 can form a cyclic ring or an
alkyl-substituted cyclic ring; and wherein R.sup.10 and R.sup.11
can form a cyclic ring or an alkyl-substituted cyclic ring;
[0067] c. purging the reactor with a purge gas;
[0068] d. introducing an oxygen source into the reactor;
[0069] e. introducing into the reactor a second precursor having a
formula of R.sup.12.sub.Si(NR.sup.13R.sup.14).sub.xH.sub.3-x
wherein x=0, 1, 2, 3, and 4, wherein R.sup.12, R.sup.13, and
R.sup.14 are each independently selected from the group consisting
of H, a C.sub.1 to C.sub.10 linear or branched alkyl group, a
C.sub.3 to C.sub.10 cyclic alkyl group, a linear or branched
C.sub.2 to C.sub.10 alkenyl group, a linear or branched C.sub.2 to
C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a
C.sub.3 to C.sub.10 saturated or unsaturated heterocyclic group and
wherein R.sup.13 and R.sup.14 can form a cyclic ring or an
alkyl-substituted cyclic ring;
[0070] f. purging the reactor with a purge gas;
[0071] g. introducing an oxygen source into the reactor;
[0072] h. purging the reactor with a purge gas; and
[0073] i. repeating the steps b through h until a desired thickness
of the film is obtained. In one particular embodiment of the method
described herein, the precursor in step (b) comprises an
organoaminoalkylsilane described herein as (i). More particularly,
the precursor in step (b) comprises the organaoaminoalkylsilane
2,6-dimethylpiperidinomethylsilane.
[0074] In another aspect, there is provided a method of forming a
carbon-doped silicon nitride film via an atomic layer deposition
process, the method comprising the steps of:
[0075] a. providing a substrate in a reactor;
[0076] b. introducing into the reactor a first precursor comprising
at least one compound selected from the group consisting of: [0077]
(v) an organoaminoalkylsilane having a formula of
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1, 2, 3; [0078]
(vi) an organoalkoxyalkylsilane having a formula of
R.sup.6Si(OR.sup.7).sub.xH.sub.3-x wherein x=1, 2, 3; [0079] (vii)
an organoaminosilane having a formula of
R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sup.2; [0080] (viii) an
organoaminosilane having a formula of R.sup.8N(SiR.sup.9LH).sub.2
and combinations thereof; wherein R.sup.3, R.sup.4, and R.sup.7 are
each independently selected from the group consisting of a C.sub.1
to C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; R.sup.5 and
R.sup.6 are each independently selected from the group consisting
of a C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.3 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group and a
halide atom; R.sup.8 and R.sup.9 are each independently selected
from the group consisting of hydrogen, C.sub.1 to C.sub.10 linear
or branched alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a
linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and R.sup.10 and R.sup.11 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; L=Cl, Br, or
I and wherein R.sup.3 and R.sup.4 can form a cyclic ring or an
alkyl-substituted cyclic ring; and wherein R.sup.10 and R.sup.11
can form a cyclic ring or an alkyl-substituted cyclic ring;
[0081] c. purging the reactor with a purge gas;
[0082] d. introducing a nitrogen source into the reactor;
[0083] e. introducing into the reactor a second precursor having a
formula of R.sup.12Si(NR.sup.13R.sup.14).sub.xH.sub.3-x wherein
x=0, 1, 2, 3, and 4, wherein R.sup.12, R.sup.13, and R.sup.14 are
each independently selected from the group consisting of H, a
C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3 to
C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.2 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group and wherein
R.sup.13 and R.sup.14 can form a cyclic ring or an
alkyl-substituted cyclic ring;
[0084] f. purging the reactor with a purge gas;
[0085] g. introducing a nitrogen source into the reactor;
[0086] h. purging the reactor with a purge gas; and
[0087] i. repeating the steps b through h until a desired thickness
of the film is obtained. In one particular embodiment of the method
described herein, the precursor in step (b) comprises an
organoaminoalkylsilane described herein as (i). More particularly,
the precursor in step (b) comprises the organaoaminoalkylsilane
2,6-dimethylpiperidinomethylsilane.
BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
[0088] FIG. 1 provides the mass spectroscopy (MS) spectrum of
2,6-dimethylpiperidinomethylsilane described in Example 1.
[0089] FIG. 2 provides the thermal gravimetric analysis (TGA) and
differential scanning calorimetry (DCS) analysis of
2,6-dimethylpiperidinomethylsilane.
[0090] FIG. 3 provides an IR spectra comparison of films deposited
using 2,6-dimethylpiperidinosilane and
2,6-dimethylpiperidinomethylsilane at a temperature of 100.degree.
C.
[0091] FIG. 4 provides an IR spectra comparison of films deposited
using 2,6-dimethylpiperidinomethylsilane at different temperatures
(e.g., 100.degree. C., 150.degree. C., and 300.degree. C.).
DETAILED DESCRIPTION OF THE INVENTION
[0092] Described herein are compositions comprising one or more
precursors and processes for depositing a carbon-doped
silicon-containing film via atomic layer deposition (ALD), cyclic
chemical vapor deposition (CCVD) or plasma enhanced ALD (PEALD) or
plasma enhanced CCVD (PECCVD) using the precursor compositions. The
compositions described herein are comprised of, consist essentially
of, or consist of, a first precursor comprising at least one
compound selected from the group of compounds having the following
formulas: (i) R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x; (ii)
R.sup.6Si(OR.sup.7).sub.xH.sub.3-x; (iii) an organoaminosilane
having a formula of R.sup.8N(SiR.sup.9(NR.sup.10 R.sup.11)H).sub.2;
and combinations of (i), (ii), and (iii) wherein R.sup.3, R.sup.4,
and R.sup.7 are each independently selected from the group
consisting of a C.sub.1 to C.sub.10 linear or branched alkyl group,
a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or branched
C.sub.2 to C.sub.10 alkenyl group, a linear or branched C.sub.3 to
C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a
C.sub.3 to C.sub.10 saturated or unsaturated heterocyclic group;
R.sup.5 and R.sup.6 are each independently selected from the group
consisting of a C.sub.1 to C.sub.10 linear or branched alkyl group,
a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or branched
C.sub.2 to C.sub.10 alkenyl group, a linear or branched C.sub.3 to
C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a
C.sub.3 to C.sub.10 saturated or unsaturated heterocyclic group and
a halide atom; R.sup.8 and R.sup.9 are each independently selected
from the group consisting of hydrogen, C.sub.1 to C.sub.10 linear
or branched alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a
linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.3 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and R.sup.10 and R.sup.11 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.3 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; and x=1, 2,
or 3, and wherein R.sup.3 and R.sup.4 can form a cyclic ring or an
alkyl-substituted cyclic ring; and wherein R.sup.10 and R.sup.11
can form a cyclic ring or an alkyl-substituted cyclic ring. In
certain embodiments, the composition further comprises a second
precursor comprising an organoaminosilane having a formula
Si(NR.sup.1R.sup.2)H.sub.3 wherein R.sup.1 and R.sup.2 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.3 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group and wherein
R.sup.1 and R.sup.2 can form a cyclic ring or an alkyl-substituted
cyclic ring.
[0093] The precursors in the composition described herein are
typically high purity volatile liquid precursor chemical that are
vaporized and delivered to a deposition chamber or reactor as a gas
to deposit a silicon containing film via CVD or ALD processes for
semiconductor or other devices. The selection of precursor
materials for deposition depends upon the desired resultant
dielectric material or film. For example, a precursor material may
be chosen for its content of chemical elements, its stoichiometric
ratios of the chemical elements, and/or the resultant silicon
containing film or coating that are formed under CVD. The precursor
material used in the compositions may also be chosen for various
other characteristics such as cost, relatively low toxicity,
handling characteristics, ability to maintain liquid phase at room
temperature, volatility, molecular weight, and/or other
considerations. In certain embodiments, the precursors in the
composition described herein can be delivered to the reactor system
by any number of means, preferably using a pressurizable stainless
steel vessel fitted with the proper valves and fittings, to allow
the delivery of liquid phase precursor to the deposition chamber or
reactor.
[0094] The precursors in the compositions described herein exhibits
a balance of reactivity and stability that makes them ideally
suitable as CVD or ALD precursors. With regard to reactivity,
certain precursors may have boiling points that are too high to be
vaporized and delivered to the reactor to be deposited as a film on
a substrate. Precursors having higher relative boiling points
require that the delivery container and lines need to be heated at
or above the boiling point of the precursor to prevent condensation
or particles from forming in the container, lines, or both. With
regard to stability, other organosilane precursors may form silane
(SiH.sub.4) as they degrade. Silane is pyrophoric at room
temperature or it can spontaneously combust which presents safety
and handling issues. Moreover, the formation of silane and other
by-products decreases the purity level of the precursor and changes
as small as 1 to 2% in chemical purity may be considered
unacceptable for reliable semiconductor manufacture. In certain
embodiments, the precursors in the compositions described herein
comprise less than 2% by weight, or less than 1% by weight, or less
than 0.5% by weight of by-product (such as the corresponding
bis-silane byproduct) after being stored for a 6 months or greater,
or one year or greater time period which is indicative of being
shelf stable. In addition to the foregoing advantages, in certain
embodiments, such as for depositing a silicon oxide or silicon
nitride film using an ALD or PEALD deposition method, the
organoaminosilane precursor described herein may be able to deposit
high density materials at relatively low deposition temperatures,
e.g., 500.degree. C. or less, or 400.degree. C. or less,
300.degree. C. or less, 200.degree. C. or less, 100.degree. C. or
less, or 50.degree. C. or less. In certain embodiments, the
composition described herein can deposit the carbon-doped silicon
containing film at a deposition temperature of about 250.degree. C.
or less, 200.degree. C. or less, 100.degree. C. or less, or
50.degree. C. or less.
[0095] The compositions described herein are used to deposit
carbon-doped silicon-containing film that exhibit a higher wet etch
resistance and a lower hydrophobicity compared to
silicon-containing films that do not contain carbon. Not being
bound by theory, the introduction of carbon to a silicon-containing
film, particularly in lower alkyl forms (e.g., Me, Et, Pr, groups),
helps decrease the wet etch rate and increases the hydrophobicity.
Selective etching is particularly important in semiconductor
patterning process. Additional advantages of adding carbon to a
silicon containing film is to lower the dielectric constant or
other electrical or physical attributes of the film. It is believed
that the strength of the Si--C bond formed from the lower alkyl
substituents on silicon, particularly the silicon-methyl bond, is
sufficient for it to remain at least partially intact during film
formation according to the processes described in this invention.
The residual organic carbon in the silicon-containing film imparts
reduced dielectric constant and enhances hydrophobicity and also
reduces the etch rate using dilute aqueous hydrofluoric acid.
[0096] As previously discussed, the compositions described herein
contain at least one precursors comprising an organic group, a
nitrogen atom and a silicon atom. The first precursor is comprised
of at least one compound selected from the compounds having the
following formulas: (i) R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x,
(ii) R.sup.6Si(OR.sup.7).sub.xH.sub.3-x, (iii)
R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sub.2 and combinations
thereof. In certain embodiments, the precursors described herein
alone or in combination, are delivered via a liquid injection
apparatus. The carbon content in the resulting films can be
adjusted by one or more of the following: the amount of carbon
contained in the precursor, the type of carbon contained in the
precursor, deposition conditions, in certain embodiments, the
number of cycles of the first precursor relative to the number of
cycles of the second precursor in a cyclic CVD or ALD process, in
certain embodiments, the ratio of first precursor to second
precursor in the composition, or combinations thereof.
[0097] In one embodiment, the composition for depositing a
carbon-doped silicon containing film comprises a first precursor(s)
comprising an organoaminoalkylsilane having a formula of
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1, 2, 3 and
wherein R.sup.3, R.sup.4, and R.sup.7 are each independently
selected from the group consisting of a C.sub.1 to C.sub.10 linear
or branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group,
a linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; R.sup.5 is selected from the group consisting
of a C.sub.1 to C.sub.10 linear or branched alkyl group, a C.sub.3
to C.sub.10 cyclic alkyl group, a linear or branched C.sub.2 to
C.sub.10 alkenyl group, a linear or branched C.sub.3 to C.sub.10
alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3
to C.sub.10 saturated or unsaturated heterocyclic group and a
halide atom; and wherein R.sup.3 and R.sup.4 can form a cyclic ring
or an alkyl-substituted cyclic. In certain embodiments of the
organoaminoalkylsilane having a formula of
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x, R.sup.3 and R.sup.4 can
be combined to form a cyclic group. In these embodiments, the
cyclic group may be a carbocyclic or heterocyclic group. The cyclic
group can be saturated or, alternatively, unsaturated. In other
embodiments of the oragnoaminoalkylsilane having a formula of
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x, R.sup.3 and R.sup.4 are
not combined to form a cyclic group.
[0098] In another embodiment, the composition for depositing a
carbon-doped silicon containing film comprises a first precursor(s)
comprising an organoalkoxyalkylsilane having a formula of
R.sup.6Si(OR.sup.7).sub.xH.sub.3-x wherein x=1, 2, 3 and wherein
R.sup.7 is selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.3 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; and R.sup.6
is selected from the group consisting of a C.sub.1 to C.sub.10
linear or branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl
group, a linear or branched C.sub.2 to C.sub.10 alkenyl group, a
linear or branched C.sub.3 to C.sub.10 alkynyl group, a C.sub.5 to
C.sub.10 aromatic group, and a C.sub.3 to C.sub.10 saturated or
unsaturated heterocyclic group, and a halide atom.
[0099] In a further embodiment, the composition for depositing a
carbon-doped silicon containing film comprises a first precursor(s)
comprising an organoaminosilane having a formula of
R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sub.2 wherein R.sup.8 and
R.sup.9 are each independently selected from the group consisting
of hydrogen, C.sub.1 to C.sub.10 linear or branched alkyl group, a
C.sub.3 to C.sub.10 cyclic alkyl group, a linear or branched
C.sub.2 to C.sub.10 alkenyl group, a linear or branched C.sub.3 to
C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a
C.sub.3 to C.sub.10 saturated or unsaturated heterocyclic group;
R.sup.10 and R.sup.11 are each independently selected from the
group consisting of a C.sub.1 to C.sub.10 linear or branched alkyl
group, a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or
branched C.sub.2 to C.sub.10 alkenyl group, a linear or branched
C.sub.3 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic
group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and wherein R.sup.10 and R.sup.11 can form a
cyclic ring or an alkyl-substituted cyclic ring. In certain
embodiments of the organoaminosilane having a formula of
R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sub.2, R.sup.10 and
R.sup.11 can be combined to form a cyclic group. In these
embodiments, the cyclic group may be a carbocyclic or heterocyclic
group. The cyclic group can be saturated or, alternatively,
unsaturated. In other embodiments of the organoaminosilane having a
formula of R.sup.8N(SiR.sup.9(NR.sup.10.sub.R.sup.11)H).sub.2,
R.sup.10 and R.sup.11 are not combined to form a cyclic group.
[0100] In another embodiment, the first precursor comprises an
organoaminosilane with a formula of R.sup.8N(SiR.sup.9LH).sub.2
wherein R.sup.8 and R.sup.9 are independently selected from the
group consisting of hydrogen, C.sub.1 to C.sub.10 linear or
branched alkyl, a C.sub.3 to C.sub.10 cyclic alkyl group, a linear
or branched C.sub.2 to C.sub.10 alkenyl group, a linear or branched
C.sub.3 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic
group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; and L is a halide selected from the group
consisting of Cl, Br, I.
[0101] In certain embodiments, the composition for depositing a
carbon-doped silicon containing film further comprises a second
precursor comprising an organoaminosilane having a formula
Si(NR.sup.1R.sup.2)H.sub.3 wherein R.sup.1 and R.sup.2 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.3 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group and wherein
R.sup.1 and R.sup.2 can form a cyclic ring or an alkyl-substituted
cyclic ring. In certain embodiments of the organoaminosilane having
formula Si(NR.sup.1R.sup.2)H.sub.3, R.sup.1 and R.sup.2 can be
linked together to form a ring. In these or other embodiments, the
ring comprises a heterocyclic ring. The ring, or alternatively,
heterocyclic ring, may be saturated or unsaturated. In alternative
embodiments of the organoaminosilane having formula
Si(NR.sup.1R.sup.2)H.sub.3, R.sup.1 and R.sup.2 are not linked
together to form a ring.
[0102] In an alternative embodiment, the optional second precursor
can comprise an organoaminoalkylsilane having a formula of
R.sup.12Si(NR.sup.13R.sup.14).sub.xH.sub.3-x wherein x=0, 1, 2, 3,
and 4, wherein R.sup.12, R.sup.13, and R.sup.14 are each
independently selected from the group consisting of H, a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group. In certain
embodiments of having formula, R.sup.13 and R.sup.14 can be linked
together to form a ring. In these or other embodiments, the ring
comprises a heterocyclic ring. The ring, or alternatively,
heterocyclic ring, may be saturated or unsaturated. In alternative
embodiments of the organoaminosilane having formula, R.sup.13 and
R.sup.14 are not linked together to form a ring.
[0103] In the foregoing formulas for the first and second
precursors and throughout the description, the term "alkyl" denotes
a linear or branched functional group having from 1 to 10, or 3 to
10, or 1 to 6 carbon atoms. Exemplary linear alkyl groups include,
but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and
hexyl groups. Exemplary branched alkyl groups include, but are not
limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, iso-pentyl,
tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the
alkyl group may have one or more functional groups such as, but not
limited to, an alkyl group, an alkoxy group, a dialkylamino group
or combinations thereof, attached thereto. In other embodiments,
the alkyl group does not have one or more functional groups
attached thereto. The alkyl group may be saturated or,
alternatively, unsaturated.
[0104] In the foregoing formulas and throughout the description,
the term "cyclic alkyl" denotes a cyclic group having from 3 to 10
or 5 to 10 atoms. Exemplary cyclic alkyl groups include, but are
not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl
groups. In certain embodiments, the cyclic alkyl group may have one
or more C.sub.1 to C.sub.10 linear, branched substituents, or
substituents containing oxygen or nitrogen atoms. In this or other
embodiments, the cyclic alkyl group may have one or more linear or
branched alkyls or alkoxy groups as substituents, such as, for
example, a methylcyclohexyl group or a methoxycyclohexyl group
[0105] In the foregoing formulas and throughout the description,
the term "aryl" denotes an aromatic cyclic functional group having
from 5 to 10 carbon atoms or from 6 to 10 carbon atoms. Exemplary
aryl groups include, but are not limited to, phenyl, benzyl,
chlorobenzyl, tolyl, and o-xylyl.
[0106] In the foregoing formulas and throughout the description,
the term "alkenyl group" denotes a group which has one or more
carbon-carbon double bonds and has from 2 to 20 or from 2 to 10 or
from 2 to 6 carbon atoms.
[0107] In the foregoing formulas and throughout the description,
the term "alkynyl group" denotes a group which has one or more
carbon-carbon triple bonds and has from 2 to 20 or from 2 to 10 or
from 2 to 6 carbon atoms.
[0108] In the foregoing formulas and through the description, the
term "unsaturated" as used herein means that the functional group,
substituent, ring or bridge has one or more carbon double or triple
bonds. An example of an unsaturated ring can be, without
limitation, an aromatic ring such as a phenyl ring. The term
"saturated" means that the functional group, substituent, ring or
bridge does not have one or more double or triple bonds.
[0109] In certain embodiments, the term "carbocyclic or
heterocyclic ring" denotes a carbocyclic or heterocyclic ring.
Exemplary cyclic or alkyl substituted cyclic ring groups include,
but not limited to, cyclohexyl, cyclopentyl, pyrrolidino,
piperidino, morpholino, 2,5-dimethylpyrrolidino,
2,6-dimethylpiperidino, or other alkyl-substituted derivatives.
[0110] In certain embodiments, one or more of the alkyl group,
alkenyl group, alkynyl group, aryl group, and/or aromatic group in
the foregoing formulas may be substituted or have one or more atoms
or group of atoms substituted in place of, for example, a hydrogen
atom. Exemplary substituents include, but are not limited to,
oxygen, sulfur, halide atoms (e.g., F, Cl, I, or Br), nitrogen, and
phosphorous. In other embodiments, one or more of the alkyl group,
alkenyl group, alkynyl group, alkoxyalkyl group, alkoxy group,
alkylaminoalkyl group, aromatic and/or aryl group in the foregoing
formulas may be unsubstituted.
[0111] Some specific examples of methyl-substituted compounds which
can be used as the first precursor in the compositions described
herein include, without limitation,
bis(diemethylamino)methylsilane, diethylaminomethylsilane,
t-butylaminomethylsilane, and isopropylaminomethylsilane.
[0112] In certain embodiments, the first precursor, second
precursor, or both having the foregoing formulas has one or more
substituents comprising oxygen atoms. In these embodiments, the
need for an oxygen source during the deposition process may be
avoided. In other embodiments, the first precursor, second
precursor, or both having the foregoing formulas have one or more
substituents comprising oxygen atoms also uses an oxygen
source.
[0113] In certain embodiments, the composition described herein
comprises a first precursor or organoaminoalkylsilane having the
formula R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1, 2, 3
and R.sup.3, R.sup.4, and R.sup.5 are the substituents described
herein. The organoaminoalkylsilane having the formula
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x can be prepared by
reacting an alkyl amine, R.sup.3R.sup.4NH, with a halosilane or an
aminosilane in an organic solvent or solvent mixture with removal
of hydrogen halide, or amine. The hydrogen halide may be
conveniently removed by precipitation upon adding a tertiary amine
and forming the corresponding amine hydrochloride salt. In one
embodiment, an organoaminoalkylsilane having the formula
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1 and
R.sup.5.dbd.Cl can be prepared, for example, in the reaction
represented by Equation (1) below and R.sup.3, R.sup.4are the
substituents described herein:
[0114] In certain embodiments, the composition described herein
comprises a first precursor or organoaminoalkylsilane having the
formula R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1, 2, 3
and R.sup.3, R.sup.4, and R.sup.5 are the substituents described
herein. The organoaminoalkylsilane having the formula
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x can be prepared by
reacting an alkyl amine, R.sup.3R.sup.4NH, with a halosilane or an
aminosilane in an organic solvent or solvent mixture with removal
of hydrogen halide or amine. The hydrogen halide may be
conveniently removed by precipitation upon adding a tertiary amine
and forming the corresponding amine hydrochloride salt. In one
embodiment, an organoaminoalkylsilane having the formula
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1 and
R.sup.5.dbd.Cl can be prepared, for example, in the reaction
represented by Equation (1) below and R.sup.3, R.sup.4are the
substituents described herein:
##STR00001##
[0115] Another organoaminoalkylsilane having the formula,
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1 and R.sup.5
is a C.sub.1 to C.sub.10 linear or branched alkyl can be prepared,
for example, in the reaction represented by Equation (2) below and
R.sup.3, R.sup.4, and R.sup.5 are the substituents described
herein:
##STR00002##
[0116] In another embodiment, the composition described herein
comprises a first precursor having the formula
R.sup.8N(SiR.sup.9(NR.sup.10 R.sup.11)H).sub.2 wherein R.sup.8,
R.sup.9, R.sup.10 and R.sup.11 are substituent described herein. In
one particular embodiment of the foregoing formula, R.sup.9 is
hydrogen, and the compound can be prepared, for example, in a
method described in the following Equation 3 and 4 below and
wherein R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are substituent
described herein:
##STR00003##
[0117] In yet another embodiment, the first precursor comprises an
organoaminosilane having a formula of R.sup.8N(SiR.sup.9LH).sub.2
wherein R.sup.8 and R.sup.9 are the substituents described herein
and L=Cl, Br, I. In one particular embodiment of the foregoing
formula wherein L=Cl, the organoaminosilanes can be prepared, for
example, in a method described in following Equation 5 below and
wherein R.sup.8 and R.sup.9 are substituent described herein:
##STR00004##
[0118] In embodiments wherein the composition comprises a first and
second precursor, the first precursor the second precursor have
similar boiling points (b.p.) or the difference between the b.p. of
the first precursor and the b.p. of the second precursor is
40.degree. C. or less, 30.degree. C. or less, or 20.degree. C. or
less, or 10.degree. C. Alternatively, the difference between the
boiling of the first and second precursors ranges from any one or
more of the following end-points: 0, 10, 20, 30, or 40.degree. C.
Examples of suitable ranges of b.p. difference include without
limitation, 0 to 40.degree. C., 20.degree. to 30.degree. C., or
10.degree. to 30.degree. C. In these embodiments, the first and the
second precursors can be delivered via direct liquid injection,
vapor draw or bubbling while still keeping the same liquid ratio in
the gas phase.
[0119] In embodiments wherein the composition comprises a first and
second precursor, the amount of first precursor in the composition,
by weight percentage of the overall composition, ranges from 0.5%
by weight to 99.5% or from 10% by weight to 75% with the balance
being the second precursor or any additional precursors added
thereto. In these or other embodiments, the amount of second
precursor in the composition by weight percentage ranges from 0.5%
by weight to 99.5% or from 10% by weight to 75% with the balance
being the first precursor(s) or any additional precursors. In an
alternative embodiment, the composition comprises 100% of the first
precursor.
[0120] One embodiment of the present invention is related to a
precursor formulation consisting of an organoaminosilane with a
formula of Si(NR.sup.1R.sup.2)H.sub.3 and an organoaminoalkylsilane
with a formula of R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein
R.sup.1-4 are selected from the group consisting of C.sub.1 to
C.sub.10 linear or branched alkyl, alkyl containing other elements
such as oxygen or nitrogen, cyclic alkyl, alkenyl, alkynyl,
aromatic hydrocarbon; R.sup.5 is selected from the group consisting
of C.sub.1 to C.sub.10 linear or branched alkyl, alkyl containing
oxygen or nitrogen, cyclic alkyl, alkenyl, alkynyl, aromatic
hydrocarbon, Cl, Br, and I; r.sup.1 and R.sup.2 can form a cyclic
or alkyl substituted cyclic ring; R.sup.3 and R.sup.4 can also form
a cyclic or alkyl substituted cyclic ring; x=1, 2, 3. Preferably,
R.sup.1-2 and R.sup.3-4 are independently selected from the same
C.sub.1 to C.sub.10 linear or branched alkyls.
[0121] Table I provides exemplary compositions comprising both
first and second precursors wherein the first precursor comprises
an organoaminoalkylsilane of the formula
R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x wherein x=1, 2, 3 and
wherein Me (methyl), Et (ethyl), .sup.nPr (normal propyl), .sup.iPr
(iso-propyl), .sup.nBu (normal butyl), .sup.iBu (iso-butyl),
.sup.sBu (secondary butyl), and .sup.1Bu (tertiary butyl) and the
optional second precursor comprises an organoaminosilane having the
following general formula Si(NR.sup.1R.sup.2)H.sub.3. In these or
other embodiments, the exemplary compositions may be provided in a
stainless steel vessel, such as without limitation, a pressurizable
vessel for storage and delivery to the reactor. In this or other
embodiments, the vessel is fitted with the proper valves and
fittings to allow the delivery of the first and second precursor to
the reactor for a CVD or an ALD process. In certain embodiments,
such vessels can also have means for mixing the first and optional
second precursors, if present, or can be premixed. Alternatively,
the first and optional second precursors can be maintained in
separate vessels or in a single vessel having separation means for
maintaining the precursors in the composition separate during
storage.
TABLE-US-00001 TABLE I Exemplary Precursor Compositions No. First
Precursor Optional Second Precursor 1.
(.sup.iPr.sub.2N)R.sup.5SiH.sub.2 wherein R.sup.5 is selected
(.sup.iPr.sub.2N)SiH.sub.3 from the group consisting of Me
(methyl), Et (ethyl), .sup.nPr (normal propyl), .sup.iPr
(iso-propyl), .sup.nBu (normal butyl), .sup.iBu (iso-butyl),
.sup.sBu (secondary butyl), .sup.tBu (tertiary butyl), isomers of
pentyl, vinyl, phenyl, and alkyl substituted phenyl 2.
(.sup.sBu.sub.2N)R.sup.5SiH.sub.2 wherein R.sup.5 is selected
(.sup.sBu.sub.2N)SiH.sub.3 from the group consisting of Me, Et,
.sup.nPr, .sup.iPr, .sup.nBu, .sup.iBu, .sup.sBu, .sup.tBu, isomers
of pentyl, vinyl, phenyl, and alkyl substituted phenyl 3.
(2,6-dimethylpiperidino)R.sup.5SiH.sub.2 (2,6- wherein R.sup.5 is
selected from the group dimethylpiperidino)SiH.sub.3 consisting of
Me, Et, .sup.nPr, .sup.iPr, .sup.nBu, .sup.iBu, .sup.sBu, .sup.tBu,
isomers of pentyl, vinyl, phenyl, and alkyl substituted phenyl 4.
(phenylmethylamino)R.sup.5SiH.sub.2 wherein
(phenylmethylamino)SiH.sub.3 R.sup.5 is selected from the group
consisting of Me, Et, .sup.nPr, .sup.iPr, .sup.nBu, .sup.iBu,
.sup.sBu, .sup.tBu, isomers of pentyl, vinyl, phenyl, and alkyl
substituted phenyl
[0122] The method used to form the silicon-containing silicon
containing films or coatings are deposition processes. Examples of
suitable deposition processes for the method disclosed herein
include, but are not limited to, cyclic CVD (CCVD), MOCVD (Metal
Organic CVD), thermal chemical vapor deposition, plasma enhanced
chemical vapor deposition ("PECVD"), high density PECVD, photon
assisted CVD, plasma-photon assisted ("PPECVD"), cryogenic chemical
vapor deposition, chemical assisted vapor deposition, hot-filament
chemical vapor deposition, CVD of a liquid polymer precursor,
deposition from supercritical fluids, and low energy CVD (LECVD).
In certain embodiments, the metal containing films are deposited
via atomic layer deposition (ALD), plasma enhanced ALD (PEALD) or
plasma enhanced cyclic CVD (PECCVD) process. As used herein, the
term "chemical vapor deposition processes" refers to any process
wherein a substrate is exposed to one or more volatile precursors,
which react and/or decompose on the substrate surface to produce
the desired deposition. As used herein, the term "atomic layer
deposition process" refers to a self-limiting (e.g., the amount of
film material deposited in each reaction cycle is constant),
sequential surface chemistry that deposit films of materials onto
substrates of varying compositions. Although the precursors,
reagents and sources used herein may be sometimes described as
"gaseous", it is understood that the precursors can be either
liquid or solid which are transported with or without an inert gas
into the reactor via direct vaporization, bubbling or sublimation.
In some case, the vaporized precursors can pass through a plasma
generator. In one embodiment, the silicon containing film is
deposited using an ALD process. In another embodiment, the silicon
containing film is deposited using a CCVD process. In a further
embodiment, the silicon containing film is deposited using a
thermal CVD process. The term "reactor" as used herein, includes
without limitation, reaction chamber or deposition chamber.
[0123] In certain embodiments, the method disclosed herein avoids
pre-reaction of the precursors by using ALD or CCVD methods that
separate the precursor(s) prior to and/or during the introduction
to the reactor. In this connection, deposition techniques such as
ALD or CCVD processes are used to deposit the carbon-doped silicon
containing film. In one embodiment, the film is deposited via an
ALD process by exposing the substrate surface alternatively to the
one or more the first precursor, oxygen source if an oxide film,
nitrogen-containing source if a nitride film, second precursor, or
other precursor or reagent. Film growth proceeds by self-limiting
control of surface reaction, the pulse length of each precursor or
reagent, and the deposition temperature. However, once the surface
of the substrate is saturated, the film growth ceases.
[0124] As previously mentioned, in certain embodiments, such as for
depositing a carbon-doped silicon containing film such as a silicon
oxide or a silicon nitride film using an ALD, CCVD (PECCVD), or
PEALD deposition method, the compositions described herein may be
able to deposit films at relatively low deposition temperatures,
e.g., of 500.degree. C. or less, or 400.degree. C. or less,
300.degree. C. or less, 200.degree. C. or less, 100.degree. C. or
less, or 50.degree. C. or less or room temperature. In these or
other embodiments, the substrate (deposition) temperature ranges
from any one or more of the following end-points: 0, 25, 50, 100,
200, 300, 400, or 500.degree. C. Examples of these ranges are,
without limitation, 0 to 100.degree. C., 25 to 50.degree. C.,
100.degree. to 300.degree. C., or 100.degree. C. to 500.degree. C.
In one particular embodiment, the deposition temperature is below
200.degree. C. which allows carbon to be incorporated into the
resulting films, providing films such as carbon doped silicon oxide
with low etching rate.
[0125] Depending upon the deposition method, in certain
embodiments, the one or more silicon-containing precursors may be
introduced into the reactor at a predetermined molar volume, or
from about 0.1 to about 1000 micromoles. In this or other
embodiments, the silicon-containing and/or organoaminosilane
precursor may be introduced into the reactor for a predetermined
time period. In certain embodiments, the time period ranges from
about 0.001 to about 500 seconds.
[0126] In certain embodiments, the silicon containing films
deposited using the methods described herein is formed in the
presence of oxygen using an oxygen source, reagent or precursor
comprising oxygen. An oxygen source may be introduced into the
reactor in the form of at least one oxygen source and/or may be
present incidentally in the other precursors used in the deposition
process. Suitable oxygen source gases may include, for example,
water (H.sub.2O) (e.g., deionized water, purifier water, and/or
distilled water), water plasma, oxygen (O.sub.2), peroxide
(O.sub.3), oxygen plasma, ozone (O.sub.3), NO, NO.sub.2, carbon
monoxide (CO), carbon dioxide (C.sub.2) and combinations thereof.
In certain embodiments, the oxygen source comprises an oxygen
source gas that is introduced into the reactor at a flow rate
ranging from about 1 to about 2000 square cubic centimeters (sccm)
or from about 1 to about 1000 sccm. The oxygen source can be
introduced for a time that ranges from about 0.1 to about 100
seconds. In one particular embodiment, the oxygen source comprises
water having a temperature of 10.degree. C. or greater. In
embodiments wherein the film is deposited by an ALD or a cyclic CVD
process, the precursor pulse can have a pulse duration that is
greater than 0.01 seconds, and the oxygen source can have a pulse
duration that is less than 0.01 seconds, while the water pulse
duration can have a pulse duration that is less than 0.01 seconds.
In yet another embodiment, the purge duration between the pulses
that can be as low as 0 seconds or is continuously pulsed without a
purge in-between. The oxygen source or reagent is provided in a
molecular amount less than a 1:1 ratio to the silicon precursor, so
that at least some carbon is retained in the as deposited silicon
containing film.
[0127] In certain embodiments, the silicon containing films
comprise silicon and nitrogen. In these embodiments, the silicon
containing films deposited using the methods described herein are
formed in the presence of nitrogen-containing source. A
nitrogen-containing source may be introduced into the reactor in
the form of at least one nitrogen source and/or may be present
incidentally in the other precursors used in the deposition
process. Suitable nitrogen-containing source gases may include, for
example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine,
nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma,
nitrogen/hydrogen plasma, and mixture thereof. In certain
embodiments, the nitrogen-containing source comprises an ammonia
plasma or hydrogen/nitrogen plasma source gas that is introduced
into the reactor at a flow rate ranging from about 1 to about 2000
square cubic centimeters (sccm) or from about 1 to about 1000 sccm.
The nitrogen-containing source can be introduced for a time that
ranges from about 0.1 to about 100 seconds. In embodiments wherein
the film is deposited by an ALD or a cyclic CVD process, the
precursor pulse can have a pulse duration that is greater than 0.01
seconds, and the nitrogen-containing source can have a pulse
duration that is less than 0.01 seconds, while the water pulse
duration can have a pulse duration that is less than 0.01 seconds.
In yet another embodiment, the purge duration between the pulses
that can be as low as 0 seconds or is continuously pulsed without a
purge in-between.
[0128] The deposition methods disclosed herein may involve one or
more purge gases. The purge gas, which is used to purge away
unconsumed reactants and/or reaction byproducts, is an inert gas
that does not react with the precursors. Exemplary purge gases
include, but are not limited to, argon (Ar), nitrogen (N.sub.2),
helium (He), neon, hydrogen (H.sub.2), and mixtures thereof. In
certain embodiments, a purge gas such as Ar is supplied into the
reactor at a flow rate ranging from about 10 to about 2000 sccm for
about 0.1 to 1000 seconds, thereby purging the unreacted material
and any byproduct that may remain in the reactor.
[0129] The respective step of supplying the precursor(s), oxygen
source, the nitrogen-containing source, and/or other precursors,
source gases, and/or reagents may be performed by changing the time
for supplying them to change the stoichiometric composition of the
resulting silicon containing film.
[0130] Energy is applied to the at least one of the precursor,
nitrogen-containing oxygen-containing source, reducing agent, other
precursors or combination thereof to induce reaction and to form
the silicon containing film or coating on the substrate. Such
energy can be provided by, but not limited to, thermal, plasma,
pulsed plasma, helicon plasma, high density plasma, inductively
coupled plasma, X-ray, e-beam, photon, remote plasma methods, and
combinations thereof. In certain embodiments, a secondary RF
frequency source can be used to modify the plasma characteristics
at the substrate surface. In embodiments wherein the deposition
involves plasma, the plasma-generated process may comprise a direct
plasma-generated process in which plasma is directly generated in
the reactor, or alternatively a remote plasma-generated process in
which plasma is generated outside of the reactor and supplied into
the reactor.
[0131] The organoaminosilane precursors and/or other
silicon-containing precursors may be delivered to the reaction
chamber such as a CVD or ALD reactor in a variety of ways. In one
embodiment, a liquid delivery system may be utilized. In an
alternative embodiment, a combined liquid delivery and flash
vaporization process unit may be employed, such as, for example,
the turbo vaporizer manufactured by MSP Corporation of Shoreview,
MN, to enable low volatility materials to be volumetrically
delivered, which leads to reproducible transport and deposition
without thermal decomposition of the precursor. In liquid delivery
formulations or compositions, the precursors described herein may
be delivered in neat liquid form, or alternatively, may be employed
in solvent formulations or compositions comprising same. Thus, in
certain embodiments the precursor formulations may include solvent
component(s) of suitable character as may be desirable and
advantageous in a given end use application to form a film on a
substrate.
[0132] In another embodiment, a vessel for depositing a silicon
containing film comprising the composition comprising, consisting
essentially of, or consisting of, the first and optionally second
precursors are described herein. In one particular embodiment, the
vessel comprises at least one pressurizable vessel (preferably of
stainless steel) fitted with the proper valves and fittings to
allow the delivery of the first and second precursor to the reactor
for a CVD or an ALD process. In this or other embodiments, the
first and optionally second precursors are provided in a
pressurizable vessel comprised of stainless steel and the purity of
the precursor is 98% by weight or greater or 99.5% or greater which
is suitable for the majority of semiconductor applications. In
certain embodiments, such vessels can also have means for mixing
the first and optional second precursors, if present, or can be
premixed. Alternatively, the first and optional second precursors
can be maintained in separate vessels or in a single vessel having
separation means for maintaining the precursors in the composition
separate during storage.
[0133] As previously mentioned, the purity level of the
precursor(s) in the composition is sufficiently high enough to be
acceptable for reliable semiconductor manufacturing. In certain
embodiments, the precursors described herein comprise less than 2%
by weight, or less than 1% by weight, or less than 0.5% by weight
of one or more of the following impurities: free amines, halides,
and higher molecular weight species. Higher purity levels of the
precursors described herein can be obtained through one or more of
the following processes: purification, adsorption, and/or
distillation.
[0134] In certain embodiments, the gas lines connecting from the
precursor canisters to the reaction chamber are heated to one or
more temperatures depending upon the process requirements and the
container or containers (depending upon whether the first and
optionally second precursors (in certain embodiments) are delivered
separately or together) is kept at one or more temperatures for
bubbling. In other embodiments, a solution comprising the first and
optionally second precursor (depending upon whether the first and,
if present optionally second, precursors are delivered separately
or together) is injected into a vaporizer kept at one or more
temperatures for direct liquid injection.
[0135] A flow of argon and/or other gas may be employed as a
carrier gas to help deliver the vapor of the precursors to the
reaction chamber during the precursor pulsing. In certain
embodiments, the reaction chamber process pressure is about 1
Torr.
[0136] In a typical ALD or CCVD process, the substrate such as a
silicon oxide substrate is heated on a heater stage in a reaction
chamber that is exposed to the silicon-containing precursor
initially to allow the complex to chemically adsorb onto the
surface of the substrate.
[0137] A purge gas such as argon purges away unabsorbed excess
complex from the process chamber. After sufficient purging, a
nitrogen-containing source may be introduced into reaction chamber
to react with the absorbed surface followed by another gas purge to
remove reaction by-products from the chamber. The process cycle can
be repeated to achieve the desired film thickness.
[0138] In this or other embodiments, it is understood that the
steps of the methods described herein may be performed in a variety
of orders, may be performed sequentially or concurrently (e.g.,
during at least a portion of another step), and any combination
thereof. The respective step of supplying the precursors and the
nitrogen-containing source gases may be performed by varying the
duration of the time for supplying them to change the
stoichiometric composition of the resulting silicon containing
film.
[0139] In certain embodiments, the method to deposit the
carbon-doped silicon-containing film is an ALD or cyclic CVD method
and the composition comprises a first and second precursor. In
these or other embodiments, the order of the first and second
precursor can be delivered in any one or more of the following
manners wherein A refers to the delivery of the first precursor and
B refers to the delivery of the second precursor: ABABABAB . . .
wherein the first and second precursors are alternated until the
desired number of cycles are completed; AAAAABBBBB . . . wherein
the first precursor is introduced for the first half of the process
cycles and the second precursor is introduced for the second half
of the process cycles; and combinations thereof. In these or other
embodiments, the number of process cycles of the first precursor
relative to the second precursor can be optimized to allow for a
gradient of carbon within the carbon-containing silicon film.
[0140] The method disclosed herein forms the carbon doped silicon
oxide films using a precursor composition and an oxygen source. In
one particular embodiment, the method comprises the following
steps: [0141] Step 1. Contacting vapors generated from a
composition comprising an first precursor comprising an
organoalkoxyalkylsilane, and optionally a second precursor
comprising an organoaminosilane, with a substrate to chemically
sorb the precursors on the heated substrate; [0142] Step 2. Purging
away any unsorbed precursors; [0143] Step 3. Introducing an oxygen
source on the heated substrate to react with the sorbed precursors;
and, [0144] Step 4. Purging away any unreacted oxygen source.
[0145] The steps 1 through 4 are repeated until a desired thickness
is achieved.
[0146] In another embodiment, the method comprises the following
steps: [0147] Step 1. Contacting vapors generated from a first
precursor with a substrate to chemically sorb the precursor on the
heated substrate, the first precursor which is at least one
compound selected from the compounds having the following
formulas:
[0148] (a) R.sup.5Si(NR.sup.3R.sup.4).sub.xH.sub.3-x
[0149] (b) R.sup.6Si(OR.sup.7).sub.xH.sub.3-x
[0150] (c) R.sup.8N(SiR.sup.9(NR.sup.10R.sup.11)H).sub.2
wherein R.sup.3, R.sup.4, and R.sup.7 are each independently
selected from the group consisting of a C.sub.1 to C.sub.10 linear
or branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group,
a linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group; R.sup.5 and R.sup.6 are each independently
selected from the group consisting of a C.sub.1 to C.sub.10 linear
or branched alkyl group, a C.sub.3 to C.sub.10 cyclic alkyl group,
a linear or branched C.sub.2 to C.sub.10 alkenyl group, a linear or
branched C.sub.2 to C.sub.10 alkynyl group, a C.sub.5 to C.sub.10
aromatic group, and a C.sub.3 to C.sub.10 saturated or unsaturated
heterocyclic group, and a halide atom; R.sup.8 and R.sup.9 are each
independently selected from the group consisting of hydrogen,
C.sub.1 to C.sub.10 linear or branched alkyl, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group; and R.sup.10
and R.sup.11 are each independently selected from the group
consisting of a C.sub.1 to C.sub.10 linear or branched alkyl group,
a C.sub.3 to C.sub.10 cyclic alkyl group, a linear or branched
C.sub.2 to C.sub.10 alkenyl group, a linear or branched C.sub.2 to
C.sub.10 alkynyl group, a C.sub.5 to C.sub.10 aromatic group, and a
C.sub.3 to C.sub.10 saturated or unsaturated heterocyclic group;
wherein R.sup.3 and R.sup.4 can form a cyclic ring or an
alkyl-substituted cyclic ring; and wherein R.sup.10 and R.sup.11
can form a cyclic ring or an alkyl-substituted cyclic ring; L=Cl,
Br, I; [0151] Step 2. Purging away any unsorbed precursors; [0152]
Step 3. Introducing an oxygen source on the heated substrate to
react with the sorbed silicon precursor; [0153] Step 4. Purging
away any unreacted oxygen source; [0154] Step 5. Optionally
contacting vapors generated from an optional second precursor with
a substrate to chemically sorb the second precursor on the heated
substrate, wherein the second precursor compound has the formula
Si(NR.sup.1R.sup.2)H.sub.3 wherein R.sup.1 and R.sup.2 are each
independently selected from the group consisting of a C.sub.1 to
C.sub.10 linear or branched alkyl group, a C.sub.3 to C.sub.10
cyclic alkyl group, a linear or branched C.sub.2 to C.sub.10
alkenyl group, a linear or branched C.sub.2 to C.sub.10 alkynyl
group, a C.sub.5 to C.sub.10 aromatic group, and a C.sub.3 to
C.sub.10 saturated or unsaturated heterocyclic group and wherein
R.sup.1 and R.sup.2 can form a cyclic ring or an alkyl-substituted
cyclic ring; [0155] Step 6. Purging away any unsorbed precursors;
[0156] Step 7. Introducing an oxygen source on the heated substrate
to react with the sorbed silicon precursor; [0157] Step 8. Purging
away any unreacted oxygen source. [0158] The steps 1 through 8 are
repeated until a desired thickness is achieved.
[0159] In certain embodiments, the carbon-doped silicon containing
films described herein have a dielectric constant of 6 or less. In
these or other embodiments, the films can a dielectric constant of
about 5 or below, or about 4 or below, or about 3.5 or below.
However, it is envisioned that films having other dielectric
constants (e.g., higher or lower) can be formed depending upon the
desired end-use of the film. An example of the carbon-doped silicon
containing film that is formed using the precursor compositions and
processes described herein has the formulation
Si.sub.xO.sub.yC.sub.zN.sub.vH.sub.w wherein Si ranges from about
10% to about 40%; 0 ranges from about 0% to about 65%; C ranges
from about 0% to about 75% or from about 0% to about 50%; N ranges
from about 0% to about 75% or from about 0% to 50%; and H ranges
from about 0% to about 50% atomic percent weight % wherein
x+y+z+v+w=100 atomic weight percent, as determined, for example, by
XPS or other means.
[0160] As mentioned previously, the method described herein may be
used to deposit a carbon-doped silicon-containing film on at least
a portion of a substrate. Examples of suitable substrates include
but are not limited to, silicon, SiO.sub.2, Si.sub.3N.sub.4, OSG,
FSG, silicon carbide, hydrogenated silicon carbide, silicon
nitride, hydrogenated silicon nitride, silicon carbonitride,
hydrogenated silicon carbonitride, boronitride, antireflective
coatings, photoresists, organic polymers, porous organic and
inorganic materials, metals such as copper and aluminum, and
diffusion barrier layers such as but not limited to TiN, Ti(C)N,
TaN, Ta(C)N, Ta, W, or WN and transparent amorphous oxide
semiconductor (TAOS) or metal oxide materials include a-IGZO
(amorphous gallium indium zinc oxide), zinc oxide. The films are
compatible with a variety of subsequent processing steps such as,
for example, chemical mechanical planarization (CMP) and
anisotropic etching processes.
[0161] The deposited films have applications, which include, but
are not limited to, computer chips, optical devices, magnetic
information storages, coatings on a supporting material or
substrate, microelectromechanical systems (MEMS),
nanoelectromechanical systems, thin film transistor (TFT), and
liquid crystal displays (LCD).
[0162] The following examples illustrate the method for preparing
organoaminosilane precursors as well as deposited
silicon-containing films described herein and are not intended to
limit it in any way.
EXAMPLES
Example 1
Preparation of 2,6-dimethylpiperidino(methyl)silane
[0163] 2,6-dimethylpiperidino(chloro)silane was prepared by
dissolving 0.052 Nm.sup.3 of dichlorosilane in 4.36 L of hexanes in
a 6L stirred reactor at -20.degree. C. under a nitrogen atmosphere.
To this solution was added 244 g of triethylamine and then 260 g of
cis-2,6-dimethylpiperidine was added slowly with continuous
agitation while maintaining the temperature at -20.degree. C. Once
the addition was complete, the mixture was allowed to warm to
20.degree. C. and stirred for 16 h. A voluminous white precipitate
formed, which was removed by filtration. The precipitate was rinsed
with hexane. The filtrate combined with the rinses contained
2,6-dimethylpiperidino(chloro)silane, which was isolated by
stripping at reduced pressure to remove the hexanes. Further
purification was obtained by simple distillation of the residue at
100.degree. C. under reduced pressure. The identity of
2,6-dimethylpiperidino(chloro)silane was determined by mass
spectrometry which showed peaks at 177 (M+), 162 (M-CH.sub.3) which
are consistent with the molecular weight (177.75) of
2,6-dimethylpiperidino(chloro)silane.
[0164] A 130 g of 2,6-dimethylpiperidino(chloro)silane prepared as
described above was dissolved in 386 g of tetrahydrofuran and
placed in a 2 L reactor under an inert atmosphere. The solution was
chilled to -20.degree. C. and then 247 g of 3 molar methylmagnesium
chloride solution in tetrahydrofuran was added gradually with
stirring over 60 minutes while maintaining the temperature at
-20.degree. C. The mixture was then allowed to warm to 20.degree.
C. over 30 minutes and then allowed to stir at that temperature for
18 h. A heavy white precipitate was observed. The mixture was
filtered and the precipitate was rinsed with an additional 100 mL
of tetrahydrofuran. The tetrahydrofuran from these combined
filtrates was removed by simple distillation at reduced pressure.
The resulting yellow slurry was extracted with 400 mL of hexanes
and the solids were removed by filtration and rinsed with two
portions of 50 mL of hexanes. The hexanes were stripped from this
combined filtrate to produce crude product that was further
purified by simple distillation to provide 70.4 g of product. The
identity of the material was determined by mass spectrometry (see
FIG. 2), which showed peaks at 157 (M+), 142 (M-CH.sub.3 and are
consistent with the molecular weight (157.33) of
2,6-dimethylpiperidinomethylsilane. Gas chromatography with thermal
conductivity detection indicates a purity of approximately 97% by
weight. The boiling point was measured by DSC to be
.about.173.degree. C. at atmospheric pressure (see FIG. 2).
[0165] Three 10 cc stainless steel containers were carefully washed
and baked out at 175.degree. C. prior to use. Each was loaded with
an ampoule containing a 2 ml sample of
2,6-dimethylpiperidinomethylsilane. The ampoules were then stored
in constant temperature environments using laboratory ovens pre-set
at 100.degree. C..+-.2.degree. C. for three days. The samples were
evaluated by gas chromatography (GC) to determine the extent of
degradation and the results are shown in FIG. 2. The average purity
after heating showed virtually no change, demonstrating it has
excellent thermal stability and can be employed as a suitable
precursor for reliable semi-conductor processes.
Example 2
Atomic Layer Deposition of Silicon-Containing Films
[0166] Atomic layers depositions of silicon-containing films were
conducted using the following precursors:
2,6-dimethylpiperidinosilane and
2,6-dimethylpiperidinomethylsilane. The depositions were performed
on a laboratory scale ALD processing tool. All gases (e.g., purge
and reactant gas or precursor and oxygen source) were preheated to
100.degree. C. prior to entering the deposition zone. Gases and
precursor flow rates were controlled with ALD diaphragm valves
having high speed actuation. The substrates used in the deposition
were 12 inch length silicon strips having thermocouples attached on
a sample holder to confirm the substrate temperature. Depositions
were performed using ozone as the oxygen source gas and the process
parameters of the depositions are provided in Table II.
TABLE-US-00002 TABLE II Process for Atomic Layer Deposition of
Silicon-containing Films with Ozone Step 1 6 seconds Nitrogen Purge
of Flow 1.5 slpm N.sub.2 Purges out unreacted (sec) Reactor
chemical from reactor Step 2 6 sec Chamber evacuation <100 mT
Prepare the reactor for the precursor dose Step 3 2 sec Close
throttle valve Increases precursor resonance time Step 4 Variable
Dose Reactor pressure Organoaminosilane typically <1 T during
Precursor dose Step 5 6 sec Nitrogen Purge of Flow 1.5 slpm N.sub.2
Purges out unreacted Reactor chemical from reactor Step 6 6 sec
Chamber evacuation <100 mT Prepare the reactor for the
organoaminosilane precursor dose Step 7 2 sec Close throttle valve
Increases the organoaminosilane precursor resonance time Step 8 4
sec Dose Ozone O.sub.3 at 18-20% post generator, P = <8 T
[0167] The resultant silicon-containing films were characterized
for deposition rate and refractive index. Thickness and refractive
indices of the films was measured using a FilmTek 2000SE
ellipsometer by fitting the reflection data from the film to a
pre-set physical model (e.g., the Lorentz Oscillator model).
[0168] Wet etch rate was performed using 1% solution of 49%
hydrofluoric (HF) acid in deionized water. Thermal oxide wafers
were used as reference for each test. Films thickness of both
samples and comparative silicon oxide reference were measured with
ellipsometer before and after etch. Silicon oxide films with carbon
dopant have lower wet etch rate than silicon oxide films.
[0169] Film composition was analyzed with dynamic secondary ions
mass spectrometry (SIMS) technique. Fourier Transform Infrared
(FTIR) spectrometry is used to confirm film structure. Absorbance
in IR spectra is normalized with film thickness for comparison.
Table III is summary of the deposition temperature, deposition
rate, refractive index, wet etch rate and carbon content measured
by the Dynamic Secondary Ion Mass Spectroscopy (SIMS). The
silicon-containing films were deposited using the following methods
described below.
[0170] Method (a) describes the formation of silicon-containing
films using 2,6-dimethylpiperidinosilane at three different
substrate temperatures: 300.degree. C., 150.degree. C. and
100.degree. C. using the following process steps: [0171] Step 1.
Contacting vapors of 2,6-dimethylpiperidinosilane [0172] Step 2.
Purging away any unsorbed 2,6-dimethylpiperidinosilane [0173] Step
3. Introducing ozone to react with the sorbed
2,6-dimethylpiperidinosilane [0174] Step 4. Purging away any
unreacted ozone [0175] The above steps for Method (a) were repeated
500 times. The deposited films do not show any significant C--H
signatures at 2800-2960 cm.sup.-1 or Si--CH.sub.3 peak at
.about.1250 cm.sup.-1, as confirmed with FTIR.
[0176] Method (b) describes the formation of silicon-containing
films using 2,6-dimethylpiperidinomethylsilane at three different
substrate temperatures: 300.degree. C., 150.degree. C. and
100.degree. C. using the following process steps: [0177] Step 1.
Contacting vapors of 2,6-dimethylpiperidinomethylsilane [0178] Step
2. Purging away any unsorbed 2,6-dimethylpiperidinomethylsilane
[0179] Step 3. Introducing ozone to react with the sorbed
2,6-dimethylpiperidinomethylsilane [0180] Step 4. Purging away any
unreacted ozone [0181] The steps were repeated for 500 cycles. Film
deposited at 300.degree. C. showed a very similar IR signature as
the 2,6-dimethylpiperidinosilane in Method (a) (e.g., no C--H
signatures at 2800-2960cm.sup.-1 and Si--CH.sub.3 signature at
.about.1250 cm.sup.-1). Both C--H and Si--CH.sub.3 absorbance peaks
occurred in films deposited at 150.degree. C. and stronger at
100.degree. C.
[0182] Method (c) describes the formation of silicon-containing
films using alternating doses of the first precursor
2,6-dimethylpiperidinomethylsilane and the second precursor
2,6-dimethylpiperidinosilane at a substrate temperature of
100.degree. C.; [0183] Step 1. Contacting vapors of
2,6-dimethylpiperidinosilane [0184] Step 2. Purging away any
unsorbed 2,6-dimethylpiperidinosilane [0185] Step 3. Introducing
ozone to react with the sorbed 2,6-dimethylpiperidinosilane [0186]
Step 4. Purging away any unreacted ozone [0187] Step 5. Contacting
vapors of 2,6-dimethylpiperidinomethylsilane [0188] Step 6. Purging
away any unsorbed 2,6-dimethylpiperidinomethylsilane; [0189] Step
7. Introducing ozone to react with the sorbed
2,6-dimethylpiperidinomethylsilane [0190] Step 8. Purging away any
unreacted ozone [0191] The steps were repeated for 250 times.
TABLE-US-00003 [0191] TABLE III Summary of Resulting
Silicon-containing Films using Methods (a) through (c) Wet Carbon
Deposition Deposition etch Content temperature rate Refractive rate
(# of Precursor (.degree. C.) (.ANG./cycle) index (.ANG./min)
atoms/cc) 2,6-dimethylpiperidinosilane 300 1.86 1.455 5.43 2
.times. 10.sup.19 (Method (a)) 2,6-dimethylpiperidinosilane 150
1.96 1.464 5.25 6 .times. 10.sup.19 (Method (a))
2,6-dimethylpiperidinosilane 100 1.90 1.465 5.78 1 .times.
10.sup.20 (Method (a)) 2,6- 300 1.24 1.473 5.13 2 .times. 10.sup.19
dimethylpiperidinomethylsilane (Method (b)) 2,6- 150 0.58 1.513
3.07 3 .times. 10.sup.21 dimethylpiperidinomethylsilane (Method
(b)) 2,6- 100 0.57 1.517 1.18 2 .times. 10.sup.22
dimethylpiperidinomethylsilane (Method (b))
2,6-dimethylpiperidinosilane 100 1.57 1.464 2.43 6 .times.
10.sup.21 and 2,6- dimethylpiperidinomethylsilane (Method (c))
[0192] Referring to Table III, the wet etch rates for
silicon-containing films using 2,6-dimethylpiperidinosilane showed
no improvement regardless of deposition temperatures which is
consistent with no carbon incorporation into the films. However,
unexpectedly, silicon-containing films deposited at 300.degree. C.
using 2,6-dimethylpiperidinomethylsilane shows very similar IR
signature as the films from 2,6-dimethylpiperidinosilane, i.e. no
C--H signatures at 2800-2960cm.sup.-land Si--CH.sub.3 signature at
.about.1250 cm.sup.-1, although it was hoped that the Si--CH.sub.3
group in 2,6-dimethylpiperidinomethylsilane would be incorporated
into the resulting silicon-containing films. Further, both C--H and
Si--CH.sub.3 absorbance peaks occurred in films deposited at
150.degree. C. and were stronger at 100.degree. C. in films
deposited with dimethylpiperidinomethylsilane. The wet etch rate is
directly correlated with the amount of carbon incorporated into the
films, i.e. the higher the carbon content, the lower the wet etch
rate. The carbon content in the films deposited at 300.degree. C.
using either 2,6-dimethylpiperidinosilane or
2,6-dimethylpiperidinomethylsilane deposited were very similar at
2.times.10.sup.19 atoms/cc, indicating that the ozone effectively
oxidized the Si--CH.sub.3 group in
2,6-dimethylpiperidinomethylsilane. However, lowering the
deposition temperature from 300.degree. C. to 150.degree. C. or
100.degree. C. increased the carbon incorporation into films due to
less effective oxidation of organoaminosilanes. Importantly, the
effect is more pronounced for films deposited from 2,6
dimethylpiperidinomethylsilane at temperature of 100.degree. C.,
showing two orders of magnitude more carbon atoms. Additionally,
not to be bound by theory, it is speculated that the amount of
carbon in the films can also be adjusted by several other methods
such as decreasing ozone pulse time, decreasing ozone
concentration, alternating layers of carbon doped silicon
containing film as well as co-depositing carbon doped silicon
containing layer with non-carbon doped silicon containing
films.
[0193] FIG. 3 shows the IR spectra comparison between
2,6-dimethylpiperidinosilane and 2,6-dimethylpiperidinomethylsilane
deposited at 100.degree. C. FIG. 5 provides a comparison among
2,6-dimethylpiperidinomethylsilane films deposited at different
temperatures. This example demonstrates that the carbon content of
the silicon-containing can be tuned via varying deposition
temperature or using two different organoaminosilanes.
* * * * *