U.S. patent application number 10/229473 was filed with the patent office on 2005-06-23 for systems and methods for forming metal oxides using alcohols.
This patent application is currently assigned to MICRON TECHNOLOGY, INC.. Invention is credited to Vaartstra, Brian A..
Application Number | 20050136689 10/229473 |
Document ID | / |
Family ID | 31976227 |
Filed Date | 2005-06-23 |
United States Patent
Application |
20050136689 |
Kind Code |
A9 |
Vaartstra, Brian A. |
June 23, 2005 |
Systems and methods for forming metal oxides using alcohols
Abstract
A method of forming (and an apparatus for forming) a metal oxide
layer on a substrate, particularly a semiconductor substrate or
substrate assembly, using a vapor deposition process, one or more
alcohols, and one or more metal-containing precursor compounds.
Inventors: |
Vaartstra, Brian A.; (Nampa,
ID) |
Correspondence
Address: |
MUETING, RAASCH & GEBHARDT, P.A.
P.O. BOX 581415
MINNEAPOLIS
MN
55458
US
|
Assignee: |
MICRON TECHNOLOGY, INC.
Boise
ID
83707-0006
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 0043632 A1 |
March 4, 2004 |
|
|
Family ID: |
31976227 |
Appl. No.: |
10/229473 |
Filed: |
August 28, 2002 |
Current U.S.
Class: |
438/785;
257/E21.274; 257/E21.29 |
Current CPC
Class: |
C23C 16/45553 20130101;
F17C 11/00 20130101; H01L 21/02271 20130101; C23C 16/40 20130101;
C23C 16/405 20130101; H01L 21/02186 20130101; H01L 21/02205
20130101; H01L 21/02194 20130101; H01L 21/02175 20130101; H01L
21/31683 20130101; H01L 21/31604 20130101; H01L 21/0228
20130101 |
Class at
Publication: |
438/785 |
International
Class: |
H01L 021/31 |
Claims
What is claimed is:
1. A method of manufacturing a semiconductor structure, the method
comprising: providing a semiconductor substrate or substrate
assembly; providing at least one alcohol of the formula R(OH).sub.r
wherein R is an organic group and r is 1 to 3; providing at least
one metal-containing precursor compound of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3- ).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II, wherein: M.sup.1 and M.sup.2 are each independently a metal;
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently
hydrogen or an organic group; w is 0 to 4; z is 1 to 8; q is 1 to
5; and w, z, and q are dependent on the oxidation states of the
metals; and contacting the precursor compounds to form a metal
oxide layer on one or more surfaces of the semiconductor substrate
or substrate assembly using a vapor deposition process.
2. The method of claim 1 wherein the semiconductor substrate or
substrate assembly is a silicon wafer.
3. The method of claim 1 wherein the metal oxide layer is a
dielectric layer.
4. The method of claim 3 wherein the metal oxide dielectric layer
comprises two or more different metals.
5. The method of claim 4 wherein the two or more different metals
are in the form of alloys, solid solutions, or nanolaminates.
6. The method of claim 1 wherein M.sup.1 and M.sup.2 are each
independently selected from the group of metals consisting of
Groups 3, 4, 5, 6, 7, 13, 14, and the lanthanides.
7. The method of claim 6 wherein M.sup.1 and M.sup.2 are each
independently selected from the group of metals consisting of Y,
La, Pr, Nd, Gd, Ti, Zr, Hf, Nb, Ta, Al, and Si.
8. The method of claim 1 wherein the metal oxide layer has a
thickness of about 30 .ANG. to about 80 .ANG..
9. The method of claim 1 wherein each R is independently a (C1-C10)
organic group.
10. The method of claim 1 wherein R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 are each independently hydrogen or a (C1-C6) organic
group.
11. The method of claim 1 wherein w is 0 to 2 and z is 2 to 6.
12. The method of claim 1 wherein q is 2 to 3.
13. The method of claim 1 wherein the metal oxide layer comprises
one metal.
14. The method of claim 1 wherein the metal oxide layer comprises
anatase TiO.sub.2.
15. A method of manufacturing a semiconductor structure, the method
comprising: providing a semiconductor substrate or substrate
assembly within a deposition chamber; providing at least one
alcohol of the formula R(OH).sub.r wherein R is an organic group
and r is 1 to 3; providing at least one metal-containing precursor
compound of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II, wherein: M.sup.1 and M.sup.2 are each independently a metal;
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently
hydrogen or an organic group; w is 0 to 4; z is 1 to 8; q is 1 to
5; and w, z, and q are dependent on the oxidation states of the
metals; vaporizing the precursor compounds to form vaporized
precursor compounds; and directing the vaporized precursor
compounds to the semiconductor substrate or substrate assembly to
form a metal oxide dielectric layer on one or more surfaces of the
semiconductor substrate or substrate assembly.
16. The method of claim 15 wherein the precursor compounds are
vaporized in the presence of an inert carrier gas.
17. The method of claim 15 wherein M.sup.1 and M.sup.2 are each
independently selected from the group of metals consisting of
Groups 3, 4, 5, 6, 7, 13, 14, and the lanthanides.
18. The method of claim 15 wherein vaporizing and directing the
precursor compounds is accomplished using a chemical vapor
deposition process.
19. The method of claim 18 wherein the temperature of the
semiconductor substrate or substrate assembly is about 100.degree.
C. to about 600.degree. C.
20. The method of claim 18 wherein the semiconductor substrate or
substrate assembly is in a deposition chamber having a pressure of
about 0.1 torr to about 10 torr.
21. The method of claim 18 wherein vaporizing and directing the
precursor compounds is accomplished using an atomic layer
deposition process comprising a plurality of deposition cycles.
22. The method of claim 21 wherein during the atomic layer
deposition process the metal-containing layer is formed by
alternately introducing the precursor compounds during each
deposition cycle.
23. The method of claim 21 wherein the temperature of the
semiconductor substrate or substrate assembly is about 25.degree.
C. to about 400.degree. C.
24. The method of claim 21 wherein the semiconductor substrate or
substrate assembly is in a deposition chamber having a pressure of
about 10.sup.-4 torr to about 1 torr.
25. The method of claim 15 wherein the metal oxide layer comprises
one metal.
26. A method of forming a metal oxide layer on a substrate, the
method comprising: providing a substrate; providing at least one
alcohol of the formula R(OH).sub.r wherein R is an organic group
and r is 1 to 3; providing at least one metal-containing precursor
compound of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II, wherein: M.sup.1 and M.sup.2 are each independently a metal;
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently
hydrogen or an organic group; w is 0 to 4; z is 1 to 8; q is 1 to
5; and w, z, and q are dependent on the oxidation states of the
metals; and contacting the precursor compounds to form a metal
oxide layer on the substrate using a vapor deposition process.
27. The method of claim 26 wherein the substrate is a silicon
wafer.
28. The method of claim 26 wherein M.sup.1 and M.sup.2 are each
independently selected from the group of metals consisting of
Groups 3, 4, 5, 6, 7, 13, 14, and the lanthanides.
29. The method of claim 28 wherein M.sup.1 and M.sup.2 are each
independently selected from the group of metals consisting of Y,
La, Pr, Nd, Gd, Ti, Zr, Hf, Nb, Ta, Al, and Si.
30. The method of claim 26 wherein the metal oxide layer has a
thickness of about 30 .ANG. to about 80 .ANG..
31. The method of claim 26 wherein each R is independently a
(C1-C10) organic group.
32. The method of claim 26 wherein R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 are each independently hydrogen or a (C1-C6) organic
group.
33. The method of claim 26 wherein w is 0 to 2 and z is 2 to 6.
34. The method of claim 26 wherein q is 2 to 3.
35. The method of claim 26 wherein the metal oxide comprises one
metal.
36. The method of claim 26 wherein the metal oxide layer comprises
anatase TiO.sub.2.
37. A method of forming a metal oxide layer on a substrate, the
method comprising: providing a substrate; providing at least one
alcohol of the formula R(OH).sub.r wherein R is an organic group
and r is 1 to 3; providing at least one metal-containing precursor
compound of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II, wherein: M.sup.1 and M.sup.2 are each independently a metal;
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently
hydrogen or an organic group; w is 0 to 4; z is 1 to 8; q is 1 to
5; and w, z, and q are dependent on the oxidation states of the
metals; vaporizing the precursor compounds to form vaporized
precursor compounds; and directing the vaporized precursor
compounds to the substrate to form a metal oxide layer on the
substrate.
38. The method of claim 37 wherein vaporizing and directing the
precursor compounds is accomplished using a chemical vapor
deposition process.
39. The method of claim 37 wherein vaporizing and directing the
precursor compounds is accomplished using an atomic layer
deposition process comprising a plurality of deposition cycles.
40. The method of claim 37 wherein the metal oxide layer comprises
one metal.
41. A method of manufacturing a memory device structure, the method
comprising: providing a substrate having a first electrode thereon;
providing at least one alcohol of the formula R(OH).sub.r wherein R
is an organic group and r is 1 to 3; providing at least one
metal-containing precursor compound of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3- ).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II, wherein: M.sup.1 and M.sup.2 are each independently a metal;
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently
hydrogen or an organic group; w is 0 to 4; z is 1 to 8; q is 1 to
5; and w, z, and q are dependent on the oxidation states of the
metals; vaporizing the precursor compounds to form vaporized
precursor compounds; directing the vaporized precursor compounds to
the substrate to form a metal oxide dielectric layer on the first
electrode of the substrate; and forming a second electrode on the
dielectric layer.
42. The method of claim 41 wherein vaporizing and directing the
precursor compounds is accomplished using a chemical vapor
deposition process.
43. The method of claim 41 wherein vaporizing and directing the
precursor compounds is accomplished using an atomic layer
deposition process comprising a plurality of deposition cycles.
44. The method of claim 41 wherein the metal oxide dielectric layer
comprises two or more different metals.
45. The method of claim 44 wherein the two or more different metals
are in the form of alloys, solid solutions, or nanolaminates.
46. The method of claim 41 wherein the metal oxide dielectric layer
comprises one or more of ZrO.sub.2, HfO.sub.2, Ta.sub.2O.sub.3,
Al.sub.2O.sub.3, TiO.sub.2, and an oxide of a lanthanide.
47. A vapor deposition apparatus comprising: a vapor deposition
chamber having a substrate positioned therein; one or more vessels
comprising one or more alcohols of the formula R(OH).sub.r wherein
R is an organic group and r is 1 to 3; and one or more vessels
comprising one or more precursor compounds of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II, wherein: M.sup.1 and M.sup.2 are each independently a metal;
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently
hydrogen or an organic group; w is 0 to 4; z is 1 to 8; q is 1 to
5; and w, z, and q are dependent on the oxidation states of the
metals.
48. The apparatus of claim 47 wherein the substrate is a silicon
wafer.
49. The apparatus of claim 47 further comprising one or more
sources of an inert carrier gas for transferring the precursors to
the vapor deposition chamber.
Description
FIELD OF THE INVENTION
[0001] This invention relates to methods of forming a metal oxide
layer on a substrate using one or more alcohols and one or more
metal-containing precursor compounds during a vapor deposition
process. The precursor compounds and methods are particularly
suitable for the formation of a metal oxide layers on semiconductor
substrates or substrate assemblies.
BACKGROUND OF THE INVENTION
[0002] The continuous shrinkage of microelectronic devices such as
capacitors and gates over the years has led to a situation where
the materials traditionally used in integrated circuit technology
are approaching their performance limits. Silicon (i.e., doped
polysilicon) has generally been the substrate of choice, and
silicon dioxide (SiO.sub.2) has frequently been used as the
dielectric material with silicon to construct microelectronic
devices. However, when the SiO.sub.2 layer is thinned to 1 nm
(i.e., a thickness of only 4 or 5 molecules), as is desired in the
newest micro devices, the layer no longer effectively performs as
an insulator due to the tunneling current running through it.
[0003] Thus, new high dielectric constant materials are needed to
extend device performance. Such materials need to demonstrate high
permittivity, barrier height to prevent tunneling, stability in
direct contact with silicon, and good interface quality and film
morphology. Furthermore, such materials must be compatible with the
gate material, electrodes, semiconductor processing temperatures,
and operating conditions.
[0004] High quality thin oxide films of metals, such as ZrO.sub.2,
HfO.sub.2, Al.sub.2O.sub.3, and YSZ I deposited on semiconductor
wafers have recently gained interest for use in memories (e.g.,
dynamic random access memory (DRAM) devices, static random access
memory (SRAM) devices, and ferroelectric memory (FERAM) devices).
These materials have high dielectric constants and therefore are
attractive as replacements in memories for SiO.sub.2 where very
thin layers are required. These metal oxide layers are
thermodynamically stable in the presence of silicon, minimizing
silicon oxidation upon thermal annealing, and appear to be
compatible with metal gate electrodes. Specifically, for gate
dielectrics, La.sub.2O.sub.3, HfO.sub.2, and ZrO.sub.2 are also
promising as they possess relatively high values for permittivity
and bandgap.
[0005] This discovery has led to an effort to investigate various
deposition processes to form layers, especially dielectric layers,
based on metal oxides. Such deposition processes have included
vapor deposition, metal thermal oxidation, and high vacuum
sputtering. Vapor deposition processes, which includes chemical
vapor deposition (CVD) and atomic layer deposition (ALD), are very
appealing as they provide for excellent control of dielectric
uniformity and thickness on a substrate. But vapor deposition
processes typically involve the co-reaction of reactive metal
precursor compounds with an oxygen source such as oxygen or water,
either of which can cause formation of an undesirable SiO.sub.2
interfacial layer. Thus, an effort is underway to develop water-
and oxygen-free vapor deposition processes.
[0006] Ritala et al., "Atomic Layer Deposition of Oxide Thin Films
with Metal Alkoxides as Oxygen Sources," SCIENCE, 288:319-321
(2000) describe a chemical approach to ALD of thin oxide films. In
this approach, a metal alkoxide, serving as both a metal source and
an oxygen source, reacts with another metal compound such as a
metal chloride or metal alkyl to deposit a metal oxide on silicon
without creating an interfacial silicon oxide layer. However,
undesirable chlorine residues can also be formed. Furthermore,
zirconium and hafnium alkyls are generally unstable and not
commercially available. They would also likely leave carbon in the
resultant films.
[0007] Despite these continual improvements in semiconductor
dielectric layers, there remains a need for a vapor deposition
process utilizing sufficiently volatile metal precursor compounds
that can form a thin, high quality oxide layer, particularly on a
semiconductor substrate using a vapor deposition process.
SUMMARY OF THE INVENTION
[0008] This invention provides methods of vapor depositing a metal
oxide layer on a substrate. These vapor deposition methods involve
forming the layer by combining one or more alcohols with one or
more metal organo-amine precursor compounds (e.g., alkylamines or
alkylimines-alkylamines) and/or metal alkyl precursor compounds.
Significantly, the methods of the present invention do not require
the use of water or a strong oxidizer, thus reducing (and typically
avoiding) the problems of producing an undesirable interfacial
oxide layer between the desired metal oxide layer and the
substrate, and oxidizing other layers beneath the top layer.
Typically and preferably, the layer is a dielectric layer.
[0009] The methods of the present invention involve forming a metal
oxide layer on a substrate, such as a semiconductor substrate or
substrate assembly in the manufacturing of a semiconductor
structure. Such methods include: providing a substrate (preferably,
a semiconductor substrate or substrate assembly); providing at
least one alcohol of the formula R(OH).sub.r wherein R is an
organic group and r is 1 to 3; providing at least one
metal-containing precursor compound of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II; and contacting the precursor compounds to form a metal oxide
layer on one or more surfaces of the substrate using a vapor
deposition process. In Formulas I and II: M.sup.1 and M.sup.2 are
each independently a metal (which is used herein to include
metalloids or semimetals); R.sup.1, R.sup.2, R.sup.3, and R.sup.4
are each independently hydrogen or an organic group; w is 0 to 4; z
is 1 to 8; q is 1 to 5; and w, z, and q are dependent on the
oxidation states of the metals.
[0010] In a preferred embodiment of the invention, a method is
provided that includes: providing a substrate (preferably, a
semiconductor substrate or substrate assembly) within a deposition
chamber; providing at least one alcohol of the formula R(OH).sub.r
wherein R is an organic group and r is 1 to 3; providing at least
one metal-containing precursor compound of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula H), or Lewis Base adducts of Formula
II; vaporizing the precursor compounds to form vaporized precursor
compounds; and directing the vaporized precursor compounds to the
substrate to form a metal oxide dielectric layer on one or more
surfaces of the substrate. In Formulas I and II: M.sup.1 and
M.sup.2 are each independently a metal; R.sup.1, R.sup.2, R.sup.3,
and R.sup.4 are each independently hydrogen or an organic group; w
is 0 to 4; z is 1 to 8; q is 1 to 5; and w, z, and q are dependent
on the oxidation states of the metals.
[0011] In another preferred embodiment of the invention, a method
of manufacturing a memory device structure is provided. The method
includes: providing a substrate having a first electrode thereon;
providing at least one alcohol of the formula R(OH).sub.r wherein R
is an organic group and r is 1 to 3; providing at least one
metal-containing precursor compound of the formula
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II; vaporizing the precursor compounds to form vaporized precursor
compounds; directing the vaporized precursor compounds to the
substrate to form a metal oxide dielectric layer on the first
electrode of the substrate; and forming a second electrode on the
dielectric layer. In Formulas I and II: M.sup.1 and M.sup.2 are
each independently a metal; R.sup.1, R.sup.2, R.sup.3, and R.sup.4
are each independently hydrogen or an organic group; w is 0 to 4; z
is 1 to 8; q is 1 to 5; and w, z, and q are dependent on the
oxidation states of the metals.
[0012] Also provided is a vapor deposition apparatus that includes:
a vapor deposition chamber having a substrate positioned therein;
one or more vessels comprising one or more alcohols of the formula
R(OH).sub.r wherein R is an organic group and r is 1 to 3; one or
more vessels comprising one or more precursor compounds of the
formula M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II. In Formulas I and II: M.sup.1 and M.sup.2 are each
independently a metal; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are
each independently hydrogen or an organic group; w is 0 to 4; z is
1 to 8; q is 1 to 5; and w, z, and q are dependent on the oxidation
states of the metals.
[0013] The methods of the present invention can utilize a chemical
vapor deposition (CVD) process, which can be pulsed, or an atomic
layer deposition (ALD) process (a self-limiting vapor deposition
process that includes a plurality of deposition cycles, typically
with purging between the cycles). Preferably, the methods of the
present invention use ALD. For certain ALD processes, the precursor
compounds can be alternately introduced into a deposition chamber
during each deposition cycle.
[0014] "Semiconductor substrate" or "substrate assembly" as used
herein refers to a semiconductor substrate such as a base
semiconductor layer or a semiconductor substrate having one or more
layers, structures, or regions formed thereon. A base semiconductor
layer is typically the lowest layer of silicon material on a wafer
or a silicon layer deposited on another material, such as silicon
on sapphire. When reference is made to a substrate assembly,
various process steps may have been previously used to form or
define regions, junctions, various structures or features, and
openings such as capacitor plates or barriers for capacitors.
[0015] "Layer" as used herein refers to any metal oxide layer that
can be formed on a substrate from the precursor compounds of this
invention using a vapor deposition process. The term "layer" is
meant to include layers specific to the semiconductor industry,
such as "barrier layer," "dielectric layer," and "conductive
layer." (The term "layer" is synonymous with the term "film"
frequently used in the semiconductor industry.) The term "layer" is
also meant to include layers found in technology outside of
semiconductor technology, such as coatings on glass.
[0016] "Precursor compound" as used herein refers to an alcohol or
a metal-containing compound capable of forming, either alone or
with other precursor compounds, a metal oxide layer on a substrate
in a vapor deposition process.
[0017] "Deposition process" and "vapor deposition process" as used
herein refer to a process in which a metal oxide layer is formed on
one or more surfaces of a substrate (e.g., a doped polysilicon
wafer) from vaporized precursor compound(s). Specifically, one or
more metal precursor (i.e., metal-containing precursor) compounds
are vaporized and directed to one or more surfaces of a heated
substrate (e.g., semiconductor substrate or substrate assembly)
placed in a deposition chamber. These precursor compounds form
(e.g., by reacting or decomposing) a non-volatile, thin, uniform,
metal oxide layer on the surface(s) of the substrate. For the
purposes of this invention, the term "vapor deposition process" is
meant to include both chemical vapor deposition processes
(including pulsed chemical vapor deposition processes) and atomic
layer deposition processes.
[0018] "Chemical vapor deposition" (CVD) as used herein refers to a
vapor deposition process wherein the desired layer is deposited on
the substrate from vaporized metal precursor compounds (and any
optional reaction gases used) within a deposition chamber with no
effort made to separate the reaction components. In contrast to a
"simple" CVD process that involves the substantial simultaneous use
of the precursor compounds and any reaction gases, "pulsed" CVD
alternately pulses these materials into the deposition chamber, but
does not rigorously avoid intermixing of the precursor and reaction
gas streams, as is typically done in atomic layer deposition or ALD
(discussed in greater detail below).
[0019] "Atomic layer deposition" (ALD) as used herein refers to a
vapor deposition process in which numerous consecutive deposition
cycles are conducted in a deposition chamber. Typically, during
each cycle the metal precursor is chemisorbed to the substrate
surface; excess precursor is purged out; a subsequent precursor
and/or reaction gas is introduced to react with the chemisorbed
layer; and excess reaction gas (if used) and by-products are
removed. As compared to the one cycle chemical vapor deposition
(CVD) process, the longer duration multi-cycle ALD process allows
for improved control of layer thickness by self-limiting layer
growth and minimizing detrimental gas phase reactions by separation
of the reaction components. The term "atomic layer deposition" as
used herein is also meant to include the related terms "atomic
layer epitaxy" (ALE), molecular beam epitaxy (MBE), gas source MBE,
organometallic MBE, and chemical beam epitaxy when performed with
alternating pulses of precursor compound(s), reaction gas(es), and
purge (i.e., inert carrier) gas.
[0020] "Chemisorption" as used herein refers to the chemical
adsorption of vaporized reactive precursor compounds on the surface
of a substrate. The adsorbed species are irreversibly bound to the
substrate surface as a result of relatively strong binding forces
characterized by high adsorption energies (e.g., >30 kcal/mol),
comparable in strength to ordinary chemical bonds. The chemisorbed
species typically form a mononolayer on the substrate surface. (See
"The Condensed Chemical Dictionary", 10th edition, revised by G. G.
Hawley, published by Van Nostrand Reinhold Co., New York, 225
(1981)). The technique of ALD is based on the principle of the
formation of a saturated monolayer of reactive precursor molecules
by cherisorption. In ALD one or more appropriate precursor
compounds or reaction gases are alternately introduced (e.g.,
pulsed) into a deposition chamber and chemisorbed onto the surfaces
of a substrate. Each sequential introduction of a reactive compound
(e.g., one or more precursor compounds and one or more reaction
gases) is typically separated by an inert carrier gas purge. Each
precursor compound co-reaction adds a new atomic layer to
previously deposited layers to form a cumulative solid layer. The
cycle is repeated, typically for several hundred times, to
gradually form the desired layer thickness. It should be understood
that ALD can alternately utilize one precursor compound, which is
chemisorbed, and one reaction gas, which reacts with the
chemisorbed species.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIGS. 1-3 are exemplary capacitor constructions.
[0022] FIG. 4 is a perspective view of a vapor deposition coating
system suitable for use in the method of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
[0023] The present invention provides methods of forming a metal
oxide layer on a substrate (preferably a semiconductor substrate or
substrate assembly) using one or more alcohols of the formula
R(OH).sub.r wherein r is 1 to 3 (preferably, I) and one or more
metal-containing precursor compounds of the formulas
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I),
M.sup.2R.sup.4.sub.q (Formula II), or Lewis Base adducts of Formula
II. In Formulas I and II: M.sup.1 and M.sup.2 are each
independently any metal (main group, transition metal, lanthamide);
each of R.sup.1, R.sup.2, and R.sup.3 is independently hydrogen or
an organic group; w is 0 to 4 (preferably, 0 to 2); z is 1 to 8
(preferably, 2 to 6); q is 1 to 5 (preferably, 2 to 3); and w, z,
and q are dependent on the oxidation states of the metals.
[0024] The metal oxide layer may include one or more different
metals and is typically of the formula M.sub.nO.sub.m (Formula
III), wherein M can be one or more of M.sup.1 and M.sup.2 as
defined above (i.e., the oxide can be a single metal oxide or a
mixed metal oxide). Optionally, the metal oxide layer is a mixed
metal oxide (i.e., it includes two or more metals). More
preferably, the metal oxide layer includes only one metal.
[0025] The metal oxide layer (particularly if it is a dielectric
layer) preferably includes one or more of ZrO.sub.2, HfO.sub.2,
Ta.sub.2O.sub.3, Al.sub.2O.sub.3, TiO.sub.2, and an oxide of a
lanthamide. A particularly preferred metal oxide layer includes
TiO.sub.2, which is preferably in the anatase phase.
[0026] If the metal oxide layer includes two or more different
metals, the metal oxide layer can be in the form of alloys, solid
solutions, or nanolaminates. Preferably, these have dielectric
properties.
[0027] The substrate on which the metal oxide layer is formed is
preferably a semiconductor substrate or substrate assembly. Any
suitable semiconductor material is contemplated, such as for
example, conductively doped polysilicon (for this invention simply
referred to as "silicon"). A substrate assembly may also contain a
layer that includes platinum, iridium, rhodium, ruthenium,
ruthenium oxide, titanium nitride, tantalum nitride,
tantalum-silicon-nitride, silicon dioxide, aluminum, gallium
arsenide, glass, etc., and other existing or to-be-developed
materials used in semiconductor constructions, such as dynamic
random access memory (DRAM) devices and static random access memory
(SRAM) devices, for example.
[0028] Substrates other than semiconductor substrates or substrate
assemblies can be used in methods of the present invention. These
include, for example, fibers, wires, etc. If the substrate is a
semiconductor substrate or substrate assembly, the layers can be
formed directly on the lowest semiconductor surface of the
substrate, or they can be formed on any of a variety of the layers
(i.e., surfaces) as in a patterned wafer, for example.
[0029] The precursor compounds described herein may include a wide
variety of metals. As used herein, "metal" includes all metals of
the periodic table (including main group metals, transition metals,
lanthamides, actinides) as well as metalloids or semimetals. For
certain methods of the present invention, preferably, each metal M
is selected from the group of metals of Groups IIIB (Sc, Y), IVB
(Ti, Zr, Hf), VB (V, Nb, Ta), VIB (Cr, Mo, W), VIIB (Mn, Tc, Re),
IIIA (Al, Ga, In, TI), UVA (Si, Ge, Sn, Pb), and the lanthamides
(La, Ce, Pr, etc.), which are also referred to as Groups 3-7, 13,
14, and the lanthamides of the Periodic Chart. More preferably,
each metal M is selected from the group of metals of Groups IIIB
(Sc, Y), UVB (Ti, Zr, Hf), VB (V, Nb, Ta), VIB (Cr, Mo, W), VIIB
(Mn, Tc, Re), IVA (Si, Ge, Sn, Pb), and the lanthamides (La, Ce,
Pr, etc.), which are also referred to as Groups 3-7, 14, and the
lanthamides of the Periodic Chart. Even more preferably, each metal
M is selected from the group of metals of Groups IIIB (Sc, Y), IVB
(Ti, Zr, Hf), VB (V, Nb, Ta), VIB (Cr, Mo, W), VIIB (Mn, Tc, Re),
and the lanthamides (La, Ce, Pr, etc.), which are also referred to
as Groups 3-7 and the lanthamides of the Periodic Chart.
[0030] For certain embodiments, a preferred group of metals for
M.sup.1 or M.sup.2 is selected from the group of Y, La, Pr, Nd, Gd,
Ti, Zr, Hf, Nb, Ta, Si, and Al. For certain other embodiments, a
preferred group of metals for M.sup.2 is Y, La, Pr, Nd, Gd, Ti, Zr,
Hf, Nb, Ta, and Si, and a more preferred group of metals for
M.sup.2 is Y, La, Pr, Nd, Gd, Ti, Zr, Hf, Nb, and Ta.
[0031] Each R in the precursor compounds (i.e., the alcohols and
the metalcontaining precursor compounds of the formulas
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.sup.3).sub.z (Formula I) and
M.sup.2R.sup.4.sub.q (Formula II)) are each independently hydrogen
or an organic group, preferably an organic group. As used herein,
the term "organic group" is used for the purpose of this invention
to mean a hydrocarbon group that is classified as an aliphatic
group, cyclic group, or combination of aliphatic and cyclic groups
(e.g., alkaryl and aralkyl groups). In the context of the present
invention, suitable organic groups for precursor compounds of this
invention are those that do not interfere with the formation of a
metal oxide layer using vapor deposition techniques. In the context
of the present invention, the term "aliphatic group" means a
saturated or unsaturated linear or branched hydrocarbon group. This
term is used to encompass alkyl, alkenyl, and alkynyl groups, for
example. The term "alkyl group" means a saturated linear or
branched monovalent hydrocarbon group including, for example,
methyl, ethyl, n-propyl, isopropyl, t-butyl, amyl, heptyl, and the
like. The term "alkenyl group" means an unsaturated, linear or
branched monovalent hydrocarbon group with one or more olefinically
unsaturated groups (i.e., carbon-carbon double bonds), such as a
vinyl group. The term "alkynyl group" means an unsaturated, linear
or branched monovalent hydrocarbon group with one or more
carbon-carbon triple bonds. The term "cyclic group" means a closed
ring hydrocarbon group that is classified as an alicyclic group,
aromatic group, or heterocyclic group. The term "alicyclic group"
means a cyclic hydrocarbon group having properties resembling those
of aliphatic groups. The term "aromatic group" or "aryl group"
means a mono- or polynuclear aromatic hydrocarbon group. The term
"heterocyclic group" means a closed ring hydrocarbon in which one
or more of the atoms in the ring is an element other than carbon
(e.g., nitrogen, oxygen, sulfur, etc.).
[0032] As a means of simplifying the discussion and the recitation
of certain terminology used throughout this application, the terms
"group" and "moiety" are used to differentiate between chemical
species that allow for substitution or that may be substituted and
those that do not so allow for substitution or may not be so
substituted. Thus, when the term "group" is used to describe a
chemical substituent, the described chemical material includes the
unsubstituted group and that group with nonperoxidic O, N, Si, F,
or S atoms, for example, in the chain as well as carbonyl groups or
other conventional substituents. Where the term "moiety" is used to
describe a chemical compound or substituent, only an unsubstituted
chemical material is intended to be included. For example, the
phrase "alkyl group" is intended to include not only pure open
chain saturated hydrocarbon alkyl substituents, such as methyl,
ethyl, propyl, t-butyl, and the like, but also alkyl substituents
bearing further substituents known in the art, such as hydroxy,
alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino,
carboxyl, etc. Thus, "alkyl group" includes ether groups,
haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls,
etc. On the other hand, the phrase "alkyl moiety" is limited to the
inclusion of only pure open chain saturated hydrocarbon alkyl
substituents, such as methyl, ethyl, propyl, t-butyl, and the
like.
[0033] For all the precursor compounds (both metal-containing and
alcohols) of this invention, each R is independently and preferably
hydrogen or an organic group, more preferably a (C1-C10) organic
group, even more preferably a (C1-C8) organic group, even more
preferably a (C1-C6) organic group, and even more preferably a
"lower" (i.e., C1-C4) organic group. Even more preferably, each of
these organic groups is an alkyl group. Most preferably, each
organic group is an organic moiety, and preferably, an alkyl
moiety.
[0034] In certain embodiments, the carbon atoms of the R groups of
the alcohol precursor compounds can be substituted with fluorine
atoms. Preferred alcohols include ethanol, isopropyl alcohol,
n-propyl alcohol, n-butanol, and ethylene glycol monomethyl
ether.
[0035] In certain embodiments, the carbon atoms of the R groups of
the metalcontaining precursor compounds are optionally replaced by
or substituted with silicon, fluorine, oxygen, and/or nitrogen
atoms or groups containing such atoms. Thus, silylated amines and
silylated imine-amines are within the scope of Formula I.
[0036] For the compounds of Formula I,
M.sup.1(NR.sup.1).sub.w(NR.sup.2R.s- up.3).sub.z, R.sup.1, R.sup.2,
and R.sup.3 are each preferably a (C1-C6) organic group. Examples
of suitable precursor compounds include tetrakis(dimethylamino)
titanium, tetrakis(dimethylamino) hafnium,
tetrakis(ethylmethylamino) hafnium, and
Al(NMe.sub.2).sub.2(N(Me)CH.sub.2- CH.sub.2NMe.sub.2) (wherein
Me=methyl). Such compounds are either commercially available from
sources such as Strem Chemical Co., or they can be prepared using
standard techniques (e.g., by reacting metal chlorides with the
corresponding lithium dialkyl amides).
[0037] For the compounds of Formula II, M.sup.2R.sup.4.sub.q and
Lewis Base adducts thereof, each R.sup.4 is preferably hydrogen or
a (C1-C4) organic group. Preferably, the compounds of Formula II do
not include compounds in which all R.sup.4 groups are methyl
(particularly when M.sup.2 is aluminum). Examples of suitable
precursor compounds include AlH.sub.3, AlMe.sub.3, AlHMe.sub.2,
ZnEt.sub.2 and AlH.sub.3NMe.sub.3. Such compounds are either
commercially available from sources such as Sigma-Aldrich, or they
can be prepared using standard techniques (e.g., by reacting
Grignard Reagents with metal halides).
[0038] Various precursor compounds can be used in various
combinations, optionally with one or more organic solvents
(particularly for CVD processes), to form a precursor composition.
The precursor compounds may be liquids or solids at room
temperature (preferably, they are liquids at the vaporization
temperature). Typically, they are liquids sufficiently volatile to
be employed using known vapor deposition techniques. However, as
solids they may also be sufficiently volatile that they can be
vaporized or sublimed from the solid state using known vapor
deposition techniques. If they are less volatile solids, they are
preferably sufficiently soluble in an organic solvent or have
melting points below their decomposition temperatures such that
they can be used in flash vaporization, bubbling, microdroplet
formation techniques, etc. Herein, vaporized precursor compounds
may be used either alone or optionally with vaporized molecules of
other precursor compounds or optionally with vaporized solvent
molecules, if used. As used herein, "liquid" refers to a solution
or a neat liquid (a liquid at room temperature or a solid at room
temperature that melts at an elevated temperature). As used herein,
"solution" does not require complete solubility of the solid but
may allow for some undissolved solid, as long as there is a
sufficient amount of the solid delivered by the organic solvent
into the vapor phase for chemical vapor deposition processing. If
solvent dilution is used in deposition, the total molar
concentration of solvent vapor generated may also be considered as
a inert carrier gas.
[0039] For metal-containing precursors, solvents can be used if
desired. The solvents that are suitable for this application
(particularly for a CVD process) can be one or more of the
following: aliphatic hydrocarbons or unsaturated hydrocarbons
(C3-C20, and preferably C5-C10, cyclic, branched, or linear),
aromatic hydrocarbons (C5-C20, and preferably C5-C10), halogenated
hydrocarbons, silylated hydrocarbons such as alkylsilanes,
alkylsilicates, ethers, polyethers, thioethers, esters, lactones,
ammonia, amides, amines (aliphatic or aromatic, primary, secondary,
or tertiary), polyamines, nitrites, cyanates, isocyanates,
thiocyanates, silicone oils, alcohols, or compounds containing
combinations of any of the above or mixtures of one or more of the
above. The compounds are also generally compatible with each other,
so that mixtures of variable quantities of the precursor compounds
will not interact to significantly change their physical
properties.
[0040] For this invention, preferably no reaction gas is employed
to minimize oxidation of the substrate (typically silicon) to its
oxide (typically silicon dioxide). That oxidizing process can also
cause detrimental oxidation to other substrates such as metal
electrodes or nitride barriers. Also, as is known in the art some
layers can be pervious to oxidizing gases and cause detrimental
oxidation of a layer below the top substrate layer.
[0041] The precursor compounds can be vaporized in the presence of
an inert carrier gas if desired. Additionally, an inert carrier gas
can be used in purging steps in an ALD process. The inert carrier
gas is typically selected from the group consisting of nitrogen,
helium, argon, and combinations thereof. In the context of the
present invention, an inert carrier gas is one that does not
interfere with the formation of the metal oxide layer. Whether done
in the presence of a inert carrier gas or not, the vaporization is
preferably done in the absence of oxygen to avoid oxygen
contamination of the layer (e.g., oxidation of silicon to form
silicon dioxide).
[0042] The deposition process for this invention is a vapor
deposition process. Vapor deposition processes are generally
favored in the semiconductor industry due to the process capability
to quickly provide highly conformal layers even within deep
contacts and other openings. Chemical vapor deposition (CVD) and
atomic layer deposition (ALD) are two vapor deposition processes
often employed to form thin, continuous, uniform, metal oxide
(preferably dielectric) layers onto semiconductor substrates. Using
either vapor deposition process, typically one or more precursor
compounds are vaporized in a deposition chamber and optionally
combined with one or more reaction gases to form a metal oxide
layer onto a substrate. It will be readily apparent to one skilled
in the art that the vapor deposition process may be enhanced by
employing various related techniques such as plasma assistance,
photo assistance, laser assistance, as well as other
techniques.
[0043] The final layer (preferably, a dielectric layer) formed
preferably has a thickness in the range of about 10 .ANG. to about
500 .ANG.. More preferably, the thickness of the metal oxide layer
is in the range of about 30 .ANG. to about 80 .ANG..
[0044] In most vapor deposition processes, the precursor
compound(s) are typically reacted with an oxidizing or reducing
reaction gas at elevated temperatures to form the metal oxide
layer. However, in the practice of this invention, no such reaction
gas is needed because the alcohol provides the oxygen for the film
formed. However, oxidizing gases, such as O.sub.2, O.sub.3,
H.sub.2O, H.sub.2O.sub.2, and N.sub.2O can be used if desired.
[0045] Chemical vapor deposition (CVD) has been extensively used
for the preparation of metal oxide layers, such as dielectric
layers, in semiconductor processing because of its ability to
provide highly conformal and high quality dielectric layers at
relatively fast processing times. The desired precursor compounds
are vaporized and then introduced into a deposition chamber
containing a heated substrate with optional reaction gases and/or
inert carrier gases. In a typical CVD process, vaporized precursors
are contacted with reaction gas(es) at the substrate surface to
form a layer (e.g., dielectric layer). The single deposition cycle
is allowed to continue until the desired thickness of the layer is
achieved.
[0046] Typical CVD processes generally employ precursor compounds
in vaporization chambers that are separated from the process
chamber wherein the deposition surface or wafer is located. For
example, liquid precursor compounds are typically placed in
bubblers and heated to a temperature at which they vaporize, and
the vaporized liquid precursor compound is then transported by an
inert carrier gas passing over the bubbler or through the liquid
precursor compound. The vapors are then swept through a gas line to
the deposition chamber for depositing a layer on substrate
surface(s) therein. Many techniques have been developed to
precisely control this process. For example, the amount of
precursor material transported to the deposition chamber can be
precisely controlled by the temperature of the reservoir containing
the precursor compound and by the flow of an inert carrier gas
bubbled through or passed over the reservoir.
[0047] Preferred embodiments of the precursor compounds described
herein are particularly suitable for chemical vapor deposition
(CVD). The deposition temperature at the substrate surface is
preferably held at a temperature in a range of about 100.degree. C.
to about 600.degree. C., more preferably in the range of about
200.degree. C. to about 500.degree. C. The deposition chamber
pressure is preferably maintained at a deposition pressure of about
0.1 torr to about 10 torr. The partial pressure of precursor
compounds in the inert carrier gas is preferably about 0.001 torr
to about 10 torr.
[0048] Several modifications of the CVD process and chambers are
possible, for example, using atmospheric pressure chemical vapor
deposition, low pressure chemical vapor deposition (LPCVD), plasma
enhanced chemical vapor deposition (PECVD), hot wall or cold wall
reactors or any other chemical vapor deposition technique.
Furthermore, pulsed CVD can be used, which is similar to ALD
(discussed in greater detail below) but does not rigorously avoid
intermixing of percursor and reactant gas streams. Also, for pulsed
CVD, the deposition thickness is dependent on the exposure time, as
opposed to ALD, which is self-limiting (discussed in greater detail
below).
[0049] A typical CVD process may be carried out in a chemical vapor
deposition reactor, such as a deposition chamber available under
the trade designation of 7000 from Genus, Inc. (Sunnyvale, Calif.),
a deposition chamber available under the trade designation of 5000
from Applied Materials, Inc. (Santa Clara, Calif.), or a deposition
chamber available under the trade designation of Prism from
Novelus, Inc. (San Jose, Calif.). However, any deposition chamber
suitable for performing CVD may be used.
[0050] Alternatively, and preferably, the vapor deposition process
employed in the methods of the present invention is a multi-cycle
ALD process. Such a process is advantageous (particularly over a
CVD process) in that in provides for optimum control of
atomic-level thickness and uniformity to the deposited layer (e.g.,
dielectric layer) and to expose the metal precursor compounds to
lower volatilization and reaction temperatures to minimize
degradation. Typically, in an ALD process, each reactant is pulsed
sequentially onto a suitable substrate, typically at deposition
temperatures of about 25.degree. C. to about 400.degree. C.
(preferably about 150.degree. C. to about 300.degree. C.), which is
generally lower than presently used in CVD processes. Under such
conditions the film growth is typically self-limiting (i.e., when
the reactive sites on a surface are used up in an ALD process, the
deposition generally stops), insuring not only excellent
conformality but also good large area uniformity plus simple and
accurate thickness control. Due to alternate dosing of the
precursor compounds and/or reaction gases, detrimental vapor-phase
reactions are inherently eliminated, in contrast to the CVD process
that is carried out by continuous coreaction of the precursors
and/or reaction gases. (See Vehkamaki et al, "Growth of SrTiO.sub.3
and BaTiO.sub.3 Thin Films by Atomic Layer Deposition,"
Electrochemical and Solid-State Letters, 2(10):504-506 (1999)).
[0051] A typical ALD process includes exposing an initial substrate
to a first chemical species (e.g., a precursor compound of Formula
I) to accomplish chemisorption of the species onto the substrate.
Theoretically, the chemisorption forms a monolayer that is
uniformly one atom or molecule thick on the entire exposed initial
substrate. In other words, a saturated monolayer. Practically,
chemisorption might not occur on all portions of the substrate.
Nevertheless, such an imperfect monolayer is still a monolayer in
the context of the present invention. In many applications, merely
a substantially saturated monolayer may be suitable. A
substantially saturated monolayer is one that will still yield a
deposited layer exhibiting the quality and/or properties desired
for such layer.
[0052] The first species is purged from over the substrate and a
second chemical species (e.g., a different precursor compound of
Formula I or a precursor compound of Formula II) is provided to
react with the first monolayer of the first species. The second
species is then purged and the steps are repeated with exposure of
the second species monolayer to the first species. In some cases,
the two monolayers may be of the same species. As an option, the
second species can react with the first species, but not chemisorb
additional material thereto. That is, the second species can cleave
some portion of the chemisorbed first species, altering such
monolayer without forming another monolayer thereon. Also, a third
species or more may be successively chemisorbed (or reacted) and
purged just as described for the first and second species.
Optionally, the second species (or third or subsequent) can include
at least one reaction gas if desired.
[0053] Purging may involve a variety of techniques including, but
not limited to, contacting the substrate and/or monolayer with a
carrier gas and/or lowering pressure to below the deposition
pressure to reduce the concentration of a species contacting the
substrate and/or chemisorbed species. Examples of carrier gases
include N.sub.2, Ar, He, etc. Purging may instead include
contacting the substrate and/or monolayer with any substance that
allows chemisorption by-products to desorb and reduces the
concentration of a contacting species preparatory to introducing
another species. The contacting species may be reduced to some
suitable concentration or partial pressure known to those skilled
in the art based on the specifications for the product of a
particular deposition process.
[0054] ALD is often described as a self-limiting process, in that a
finite number of sites exist on a substrate to which the first
species may form chemical bonds. The second species might only bond
to the first species and thus may also be self-limiting. Once all
of the finite number of sites on a substrate are bonded with a
first species, the first species will often not bond to other of
the first species already bonded with the substrate. However,
process conditions can be varied in ALD to promote such bonding and
render ALD not self-limiting. Accordingly, ALD may also encompass a
species forming other than one monolayer at a time by stacking of a
species, forming a layer more than one atom or molecule thick.
[0055] The described method indicates the "substantial absence" of
the second precursor (i.e., second species) during chemisorption of
the first precursor since insignificant amounts of the second
precursor might be present. According to the knowledge and the
preferences of those with ordinary skill in the art, a
determination can be made as to the tolerable amount of second
precursor and process conditions selected to achieve the
substantial absence of the second precursor.
[0056] Thus, during the ALD process, numerous consecutive
deposition cycles are conducted in the deposition chamber, each
cycle depositing a very thin metal oxide layer (usually less than
one monolayer such that the growth rate on average is from about
0.2 to about 3.0 Angstroms per cycle), until a layer of the desired
thickness is built up on the substrate of interest. The layer
deposition is accomplished by alternately introducing (i.e., by
pulsing) precursor compounds into the deposition chamber containing
a semiconductor substrate, chemisorbing the precursor compound(s)
as a monolayer onto the substrate surfaces, and then reacting the
chemisorbed precursor compound(s) with the other co-reactive
precursor compound(s). The pulse duration of precursor compound(s)
and inert carrier gas(es) is sufficient to saturate the substrate
surface. Typically, the pulse duration is from about 0.1 to about 5
seconds, preferably from about 0.2 to about 1 second.
[0057] In comparison to the predominantly thermally driven CVD, ALD
is predominantly chemically driven. Accordingly, ALD is often
conducted at much lower temperatures than CVD. During the ALD
process, the substrate temperature is maintained at a temperature
sufficiently low to maintain intact bonds between the chemisorbed
precursor compound(s) and the underlying substrate surface and to
prevent decomposition of the precursor compound(s). The temperature
is also sufficiently high to avoid condensation of the precursor
compounds(s). Typically the substrate temperature is kept within
the range of about 25.degree. C. to about 400.degree. C.
(preferably about 150.degree. C. to about 300.degree. C.), which is
generally lower than presently used in CVD processes. Thus, the
first species or precursor compound is chemisorbed at this
temperature. Surface reaction of the second species or precursor
compound can occur at substantially the same temperature as
chemisorption of the first precursor or, less preferably, at a
substantially different temperature. Clearly, some small variation
in temperature, as judged by those of ordinary skill, can occur but
still be a substantially same temperature by providing a reaction
rate statistically the same as would occur at the temperature of
the first precursor chemisorption. Chemisorption and subsequent
reactions could instead occur at exactly the same temperature.
[0058] For a typical ALD process, the pressure inside the
deposition chamber is kept at about 10.sup.-4 torr to about 1 torr,
preferably about 10.sup.-4 torr to about 0.1 torr. Typically, the
deposition chamber is purged with an inert carrier gas after the
vaporized precursor compound(s) have been introduced into the
chamber and/or reacted for each cycle. The inert carrier gas(es)
can also be introduced with the vaporized precursor compound(s)
during each cycle.
[0059] The reactivity of a precursor compound can significantly
influence the process parameters in ALD. Under typical CVD process
conditions, a highly reactive compound may react in the gas phase
generating particulates, depositing prematurely on undesired
surfaces, producing poor films, and/or yielding poor step coverage
or otherwise yielding non-uniform deposition. For at least such
reason, a highly reactive compound might be considered not suitable
for CVD. However, some compounds not suitable for CVD are superior
ALD precursors. For example, if the first precursor is gas phase
reactive with the second precursor, such a combination of compounds
might not be suitable for CVD, although they could be used in ALD.
In the CVD context, concern might also exist regarding sticking
coefficients and surface mobility, as known to those skilled in the
art, when using highly gas-phase reactive precursors, however,
little or no such concern would exist in the ALD context.
[0060] After layer formation on the substrate, an annealing process
can be optionally performed in situ in the deposition chamber in a
nitrogen atmosphere or oxidizing atmosphere. Preferably, the
annealing temperature is within the range of about 400.degree. C.
to about 1000.degree. C. Particularly after ALD, the annealing
temperature is more preferably about 400.degree. C. to about
750.degree. C., and most preferably about 600.degree. C. to about
700.degree. C. The annealing operation is preferably performed for
a time period of about 0.5 minute to about 60 minutes and more
preferably for a time period of about 1 minute to about 10 minutes.
One skilled in the art will recognize that such temperatures and
time periods may vary. For example, furnace anneals and rapid
thermal annealing may be used, and further, such anneals may be
performed in one or more annealing steps.
[0061] As stated above, the use of the complexes and methods of
forming films of the present invention are beneficial for a wide
variety of thin film applications in semiconductor structures,
particularly those using high dielectric materials. For example,
such applications include capacitors such as planar cells, trench
cells (e.g., double sidewall trench capacitors), stacked cells
(e.g., crown, V-cell, delta cell, multi-fingered, or cylindrical
container stacked capacitors), as well as field effect transistor
devices.
[0062] A specific example of where a dielectric layer is formed
according to the present invention is a capacitor construction.
Exemplary capacitor constructions are described with reference to
FIGS. 1-3. Referring to FIG. 1, a semiconductor wafer fragment 10
includes a capacitor construction 25 formed by a method of the
present invention. Wafer fragment 10 includes a substrate 12 having
a conductive diffusion area 14 formed therein. Substrate 12 can
include, for example, monocrystalline silicon. An insulating layer
16, typically borophosphosilicate glass (BPSG), is provided over
substrate 12, with a contact opening 18 provided therein to
diffusion area 14. A conductive material 20 fills contact opening
18, with material 20 and oxide layer 18 having been planarized as
shown. Material 20 might be any suitable conductive material, such
as, for example, tungsten or conductively doped polysilicon.
Capacitor construction 25 is provided atop layer 16 and plug 20,
and electrically connected to node 14 through plug 20.
[0063] Capacitor construction 25 includes a first capacitor
electrode 26, which has been provided and patterned over node 20.
Examplary materials include conductively doped polysilicon, Pt, Ir,
Rh, Ru, RuO.sub.2, IrO.sub.2, RhO.sub.2. A capacitor dielectric
layer 28 is provided over first capacitor electrode 26. The
materials of the present invention can be used to form the
capacitor dielectric layer 28. Preferably, if first capacitor
electrode 26 includes polysilicon, a surface of the polysilicon is
cleaned by an in situ HF dip prior to deposition of the dielectric
material. An exemplary thickness for layer 28 in accordance with
256 Mb integration is 100 Angstroms.
[0064] A diffusion barrier layer 30 is provided over dielectric
layer 28. Diffusion barrier layer 30 includes conductive materials
such as TiN, TaN, metal silicide, or metal silicide-nitride, and
can be provided by CVD, for example, using conditions well known to
those of skill in the art. After formation of barrier layer 30, a
second capacitor electrode 32 is formed over barrier layer 30 to
complete construction of capacitor 25. Second capacitor electrode
32 can include constructions similar to those discussed above
regarding the first capacitor electrode 26, and can accordingly
include, for example, conductively doped polysilicon. Diffusion
barrier layer 30 preferably prevents components (e.g., oxygen) from
diffusing from dielectric material 28 into electrode 32. If, for
example, oxygen diffuses into a silicon-containing electrode 32, it
can undesirably form SiO.sub.2, which will significantly reduce the
capacitance of capacitor 25. Diffusion barrier layer 30 can also
prevent diffusion of silicon from metal electrode 32 to dielectric
layer 28.
[0065] FIG. 2 illustrates an alternative embodiment of a capacitor
construction. Like numerals from FIG. 1 have been utilized where
appropriate, with differences indicated by the suffix "a". Wafer
fragment 10a includes a capacitor construction 25a differing from
the construction 25 of FIG. 2 in provision of a barrier layer 30a
between first electrode 26 and dielectric layer 28, rather than
between dielectric layer 28 and second capacitor electrode 32.
Barrier layer 30a can include constructions identical to those
discussed above with reference to FIG. 1.
[0066] FIG. 3 illustrates yet another alternative embodiment of a
capacitor construction. Like numerals from FIG. 1 are utilized
where appropriate, with differences being indicated by the suffix
"b" or by different numerals. Wafer fragment 10b includes a
capacitor construction 25b having the first and second capacitor
plate 26 and 32, respectively, of the first described embodiment.
However, wafer fragment 10b differs from wafer fragment 10 of FIG.
2 in that wafer fragment 10b includes a second barrier layer 40 in
addition to the barrier layer 30. Barrier layer 40 is provided
between first capacitor electrode 26 and dielectric layer 28,
whereas barrier layer 30 is between second capacitor electrode 32
and dielectric layer 28. Barrier layer 40 can be formed by methods
identical to those discussed above with reference to FIG. 1 for
formation of the barrier layer 30.
[0067] In the embodiments of FIGS. 1-3, the barrier layers are
shown and described as being distinct layers separate from the
capacitor electrodes. It is to be understood, however, that the
barrier layers can include conductive materials and can
accordingly, in such embodiments, be understood to include at least
a portion of the capacitorr electrodes. In particular embodiments
an entirety of a capacitor electrode can include conductive barrier
layer materials.
[0068] A system that can be used to perform vapor deposition
processes (chemical vapor deposition or atomic layer deposition) of
the present invention is shown in FIG. 4. The system includes an
enclosed vapor deposition chamber 110, in which a vacuum may be
created using turbo pump 112 and backing pump 114. One or more
substrates 116 (e.g., semiconductor substrates or substrate
assemblies) are positioned in chamber 110. A constant nominal
temperature is established for substrate 116, which can vary
depending on the process used. Substrate 116 may be heated, for
example, by an electrical resistance heater 118 on which substrate
116 is mounted. Other known methods of heating the substrate may
also be utilized.
[0069] In this process, precursor compounds 160 (e.g., a refractory
metal precursor compound and an ether) are stored in vessels 162.
The precursor compounds are vaporized and separately fed along
lines 164 and 166 to the deposition chamber 110 using, for example,
an inert carrier gas 168. A reaction gas 170 may be supplied along
line 172 as needed. Also, a purge gas 174, which is often the same
as the inert carrier gas 168, may be supplied along line 176 as
needed. As shown, a series of valves 180-185 are opened and closed
as required.
[0070] The following examples are offered to further illustrate the
various specific and preferred embodiments and techniques. It
should be understood, however, that many variations and
modifications may be made while remaining within the scope of the
present invention, so the scope of the invention is not intended to
be limited by the examples. Unless specified otherwise, all
percentages shown in the examples are percentages by weight.
EXAMPLES
Example 1
Pulsed Chemical Vapor Deposition of TiO.sub.2
[0071] A chamber of configuration shown in FIG. 4 was set up with
pneumatic valves under computer control to pulse the valves open in
sequential manner. Two reservoirs connected to the chamber
contained Ti(NMe.sub.2).sub.4 (Strem Chemical, Newburyport, Mass.)
and isopropyl alcohol (General Chemical, Parsippany, N.J.). The
substrate was a silicon wafer having doped poly-silicon as a top
layer and was maintained at 220.degree. C. for the deposition.
[0072] Each cycle involved a 5-second pulse of Ti(NMe.sub.2).sub.4
and a 5-second pulse of isopropyl alcohol, each separated by a
5-second purge with argon and a 5-second pump down under dynamic
vacuum. The precursors were introduced without helium carrier gas,
using only a mass flow controller downstream of the isopropyl
alcohol reservoir set at 50 sccm. After 400 cycles a TiO.sub.2 film
1750 .ANG. thick was obtained. The film contained only titanium and
oxygen based on x-ray photoelectron spectroscopy (XPS) analysis,
and had no detectable nitrogen or carbon. X-ray diffraction
analysis of the film revealed the anatase crystal phase had been
formed as-deposited.
Example 2
Atomic Layer Deposition of HfO.sub.2
[0073] A chamber of configuration shown in FIG. 4 was set up with
pneumatic valves under computer control to pulse the valves open in
sequential manner. Two reservoirs connected to the chamber
contained Hf(NMe.sub.2).sub.4 (Strem Chemical, Newburyport, Mass.)
and isopropyl alcohol (General Chemical, Parsippany, N.J.). The
Hf(NMe.sub.2).sub.4 precursor was heated to 40.degree. C. while the
isopropyl alcohol remained at ambient. The substrate was a silicon
wafer having doped poly-silicon as a top layer and was maintained
at 215.degree. C. for the deposition.
[0074] Each cycle involved a 2-second pulse of Hf(NMe.sub.2).sub.4
and a 1-second pulse of isopropyl alcohol, each separated by a
5-second purge with argon and a 5-second pump down under dynamic
vacuum. The precursors were introduced without helium carrier gas,
using only a mass flow controller downstream of the isopropyl
alcohol reservoir set at 25 sccm. After 400 cycles a HfO.sub.2 film
250 .ANG. thick was obtained. The film contained only hafnium and
oxygen based on x-ray photoelectron spectroscopy (XPS) analysis,
and had no detectable nitrogen or carbon within the HfO.sub.2
layer. X-ray diffraction analysis revealed an amorphous film had
been formed as-deposited, but after a 600.degree. C. rapid thermal
process (RTP) under nitrogen for 1 min the film was crystalline
HfO.sub.2.
[0075] The complete disclosures of the patents, patent documents,
and publications cited herein are incorporated by reference in
their entirety as if each were individually incorporated. Various
modifications and alterations to this invention will become
apparent to those skilled in the art without departing from the
scope and spirit of this invention. It should be understood that
this invention is not intended to be unduly limited by the
illustrative embodiments and examples set forth herein and that
such examples and embodiments are presented by way of example only
with the scope of the invention intended to be limited only by the
claims set forth herein as follows.
* * * * *