U.S. patent application number 10/923315 was filed with the patent office on 2007-06-28 for systems and methods for forming niobium and/or vanadium containing layers using atomic layer deposition.
This patent application is currently assigned to MICRON TECHNOLOGY, INC.. Invention is credited to Garo J. Derderian, Stefan Uhlenbrook, Donald L. Westmoreland.
Application Number | 20070148932 10/923315 |
Document ID | / |
Family ID | 35910155 |
Filed Date | 2007-06-28 |
United States Patent
Application |
20070148932 |
Kind Code |
A9 |
Derderian; Garo J. ; et
al. |
June 28, 2007 |
Systems and methods for forming niobium and/or vanadium containing
layers using atomic layer deposition
Abstract
A method of forming (and an apparatus for forming) a metal
containing layer on a substrate, particularly a semiconductor
substrate or substrate assembly for use in manufacturing a
semiconductor or memory device structure, using one or more
precursor compounds that include niobium and/or vanadium and using
an atomic layer deposition process including a plurality of
deposition cycles.
Inventors: |
Derderian; Garo J.; (Boise,
ID) ; Westmoreland; Donald L.; (Boise, ID) ;
Uhlenbrook; Stefan; (Boise, ID) |
Correspondence
Address: |
MUETING, RAASCH & GEBHARDT, P.A.
P.O. BOX 581415
MINNEAPOLIS
MN
55458
US
|
Assignee: |
MICRON TECHNOLOGY, INC.
Boise
ID
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20060040480 A1 |
February 23, 2006 |
|
|
Family ID: |
35910155 |
Appl. No.: |
10/923315 |
Filed: |
August 20, 2004 |
Current U.S.
Class: |
438/584;
257/E21.018; 257/E21.171; 257/E21.274 |
Current CPC
Class: |
H01L 21/02205 20130101;
H01L 21/0228 20130101; H01L 21/3141 20130101; C23C 16/45553
20130101; H01L 21/02175 20130101; C23C 16/405 20130101; H01L
21/28562 20130101; H01L 21/31604 20130101; H01L 28/90 20130101 |
Class at
Publication: |
438/584 |
International
Class: |
H01L 21/20 20060101
H01L021/20 |
Claims
1. A method of manufacturing a semiconductor structure, the method
comprising: providing a semiconductor substrate or substrate
assembly; providing a vapor comprising at least one precursor
compound of the formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x
(Formula I), wherein: M is selected from the group consisting of
niobium and vanadium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or
(OR.sup.5), each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; and contacting the vapor
comprising the at least one precursor compound of Formula I with
the semiconductor substrate or substrate assembly to form a
metal-containing layer on at least one surface of the semiconductor
substrate or substrate assembly using an atomic layer deposition
process comprising a plurality of deposition cycles.
2. The method of claim 1 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
3. The method of claim 2 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
4. The method of claim 1 wherein the semiconductor substrate or
substrate assembly comprises silicon, borophosphosilicate glass
(BPSG), tetraethylorthosilicate (TEOS) oxide, spin on glass, TiN,
TaN, W, noble metals, or combinations thereof.
5. The method of claim 1 wherein the metal-containing layer is a
metal oxide layer.
6. The method of claim 1 wherein the metal-containing layer is a
dielectric layer.
7. The method of claim 1 wherein the metal-containing layer has a
thickness of about 10 .ANG. to about 100 .ANG..
8. A method of manufacturing a semiconductor structure, the method
comprising: providing a semiconductor substrate or substrate
assembly; providing a vapor comprising at least one precursor
compound of the formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x
(Formula I), wherein: M is selected from the group consisting of
niobium and vanadium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or
(OR.sup.5), each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; providing at least one
reaction gas; and contacting the vapor comprising the at least one
precursor compound of Formula I with the semiconductor substrate or
substrate assembly to form a metal-containing layer on at least one
surface of the semiconductor substrate or substrate assembly using
an atomic layer deposition process comprising a plurality of
deposition cycles.
9. The method of claim 8 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
10. The method of claim 9 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
11. The method of claim 8 wherein the metal-containing layer is a
metal oxide layer.
12. The method of claim 8 wherein the metal-containing layer is a
dielectric layer.
13. The method of claim 8 wherein the at least one reaction gas is
selected from the group consisting of oxygen, water vapor, ozone,
nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,
hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,
organic amine, silane, disilane, higher silanes, diborane, plasma,
air, and combinations thereof.
14. The method of claim 13 wherein the at least one reaction gas is
selected from the group consisting of ozone and oxygen.
15. The method of claim 8 wherein during the atomic layer
deposition process, the metal-containing layer is formed by
alternately introducing the vapor comprising the at least one
precursor compound of Formula I and the at least one reaction gas
during each deposition cycle.
16. A method of manufacturing a semiconductor structure, the method
comprising: providing a semiconductor substrate or substrate
assembly within a deposition chamber; providing a vapor comprising
at least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein: M is
selected from the group consisting of niobium and vanadium, X is
(NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1,
R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is independently an organic
group, x=1 or 2; directing the vapor comprising the at least one
precursor compound of Formula I to the semiconductor substrate or
substrate assembly and allowing the at least one compound to
chemisorb to at least one surface of the semiconductor substrate or
substrate assembly; providing at least one reaction gas; and
directing the at least one reaction gas to the semiconductor
substrate or substrate assembly with the chemisorbed species
thereon to form a metal-containing layer on at least one surface of
the semiconductor substrate or substrate assembly.
17. The method of claim 16 wherein providing a vapor comprising at
least one precursor compound of Formula I, directing the vapor to
the semiconductor substrate or substrate assembly, providing at
least one reaction gas, and directing the at least one reaction gas
to the semiconductor substrate or substrate assembly is repeated at
least once.
18. The method of claim 16 wherein the at least one reaction gas is
selected from the group consisting of oxygen, water vapor, ozone,
nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,
hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,
organic amine, silane, disilane, higher silanes, diborane, plasma,
air, and combinations thereof.
19. The method of claim 18 wherein the at least one reaction gas is
selected from the group consisting of ozone and oxygen.
20. The method of claim 16 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
21. The method of claim 20 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
22. The method of claim 16 wherein the metal-containing layer is a
metal oxide layer.
23. The method of claim 16 wherein the metal-containing layer is a
dielectric layer.
24. The method of claim 16 wherein the metal-containing layer has a
thickness of about 10 .ANG. to about 100 .ANG..
25. The method of claim 16 wherein the temperature of the
semiconductor substrate or substrate assembly is about 25.degree.
C. to about 400.degree. C.
26. The method of claim 16 wherein the atomic layer deposition
chamber containing the semiconductor substrate or substrate
assembly has a pressure of about 10.sup.-4 torr to about 10
torr.
27. The method of claim 16 further comprising purging excess vapor
comprising the at least one precursor compound of Formula I from
the deposition chamber after chemisorption of the compound onto the
semiconductor substrate or substrate assembly.
28. The method of claim 27 wherein purging comprises purging with
an inert gas.
29. The method of claim 28 wherein the inert gas is selected from
the group consisting of nitrogen, helium, argon, and mixtures
thereof.
30. The method of claim 16 further comprising providing a vapor
comprising at least one metal-containing precursor compound that is
different than the precursor compound of Formula I and directing
this vapor to the semiconductor substrate or substrate assembly to
allow the at least one metal-containing compound to chemisorb on
the at least one surface of the semiconductor substrate or
substrate assembly.
31. A method of manufacturing a semiconductor structure, the method
comprising: providing a semiconductor substrate or substrate
assembly; providing a vapor comprising at least one precursor
compound of the formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x
(Formula I), wherein: M is selected from the group consisting of
niobium and vanadium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or
(OR.sup.5), each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; providing a vapor
comprising at least one metal-containing precursor compound
different than M(OR.sub.1).sub.5-x(XR.sup.2O).sub.x (Formula I);
directing the vapor comprising the at least one precursor compound
of Formula I and the vapor comprising the at least one
metal-containing precursor compound different that the precursor
compound of Formula I to the semiconductor substrate or substrate
assembly to form a metal-containing layer on at least one surface
of the semiconductor substrate or substrate assembly using an
atomic layer deposition process comprising a plurality of
deposition cycles.
32. The method of claim 31 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
33. The method of claim 32 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
34. The method of claim 31 wherein the vapor comprising the at
least one precursor compound of Formula I and the vapor comprising
the at least one metal-containing precursor compound different that
the precursor compound of Formula I are directed to the
semiconductor substrate or substrate assembly substantially
simultaneously.
35. The method of claim 31 wherein the metal-containing layer is a
metal oxide layer.
36. The method of claim 31 wherein the metal-containing layer is a
dielectric layer.
37. The method of claim 31 further comprising at least one reaction
gas.
38. The method of claim 37 wherein the at least one reaction gas is
selected from the group consisting of oxygen, water vapor, ozone,
nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,
hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,
organic amine, silane, disilane, higher silanes, diborane, plasma,
air, and combinations thereof.
39. The method of claim 38 wherein the at least one reaction gas is
selected from the group consisting of ozone and oxygen.
40. The method of claim 37 wherein the vapor comprising the at
least one precursor compound of Formula I and the vapor comprising
the at least one metal-containing precursor compound different that
the precursor compound of Formula I are directed to the
semiconductor substrate or substrate assembly prior to directing
the at least one reaction gas to the semiconductor substrate or
substrate assembly.
41. The method of claim 31 wherein the vapor comprising the at
least one precursor compound of Formula I and the vapor comprising
the at least one metal-containing precursor compound different that
the precursor compound of Formula I further comprise a nonreactive
gas.
42. The method of claim 41 wherein the nonreactive gas is selected
from the group consisting of nitrogen, helium, argon, and mixtures
thereof.
43. The method of claim 31 wherein the metal-containing precursor
compound different than Formula I comprises at least one metal
selected from the group consisting of bismuth, tantalum, hafnium,
aluminum, niobium, vanadium, and combinations thereof.
44. A method of forming a niobium oxide layer on a substrate, the
method comprising: providing a substrate; providing a vapor
comprising at least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein: M is
niobium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5),
each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; and contacting the vapor
comprising the at least one precursor compound with the substrate
to form a niobium oxide layer on at least one surface of the
substrate using an atomic layer deposition process comprising a
plurality of deposition cycles.
45. The method of claim 44 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
46. The method of claim 45 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
47. The method of claim 44 wherein the substrate comprises silicon,
borophosphosilicate glass (BPSG), tetraethylorthosilicate (TEOS)
oxide, spin on glass, TiN, TaN, W, noble metals, or combinations
thereof.
48. The method of claim 44 wherein the metal-containing layer is a
dielectric layer.
49. The method of claim 44 wherein the formed niobium oxide layer
has a thickness of about 10 .ANG. to about 100 .ANG..
50. A method of forming a niobium oxide layer on a substrate, the
method comprising: providing a substrate; providing a vapor
comprising at least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein: M is
niobium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5),
each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; providing at least one
reaction gas; and contacting the vapor comprising the at least one
precursor compound with the substrate to form a niobium oxide layer
on at least one surface of the substrate using an atomic layer
deposition process comprising a plurality of deposition cycles.
51. The method of claim 50 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
52. The method of claim 51 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
53. The method of claim 50 wherein the metal-containing layer is a
dielectric layer.
54. The method of claim 50 wherein the at least one reaction gas is
selected from the group consisting of oxygen, water vapor, ozone,
nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,
hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,
organic amine, silane, disilane, higher silanes, diborane, plasma,
air, and combinations thereof.
55. The method of claim 54 wherein the at least one reaction gas is
selected from the group consisting of ozone and oxygen.
56. The method of claim 50 wherein during the atomic layer
deposition process, the niobium oxide layer is formed by
alternately introducing the vapor comprising the at least one
precursor compound and the at least one reaction gas during each
deposition cycle.
57. A method of forming a niobium oxide layer on a substrate, the
method comprising: providing a substrate within a deposition
chamber; providing a vapor comprising at least one precursor
compound of the formula M(OR.sup.1).sub.5-xX(XR.sup.2O).sub.x
(Formula I), wherein: M is niobium, X is (NR.sup.3R.sup.4),
(PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 is independently an organic group, x=1 or 2;
directing the vapor comprising the at least one precursor compound
of Formula I to the substrate and allowing the at least one
compound to chemisorb to at least one surface of the substrate;
providing at least one reaction gas; and directing the at least one
reaction gas to the substrate with the chemisorbed species thereon
to form a niobium oxide layer on at least one surface of the
substrate.
58. The method of claim 57 wherein the at least one reaction gas is
selected from the group consisting of oxygen, water vapor, ozone,
nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,
hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,
organic amine, silane, disilane, higher silanes, diborane, plasma,
air, and combinations thereof.
59. The method of claim 58 wherein the at least one reaction gas is
selected from the group consisting of ozone and oxygen.
60. The method of claim 57 wherein providing a vapor comprising at
least one precursor compound of Formula I, directing the vapor to
the substrate, providing at least one reaction gas, and directing
the at least one reaction gas to the substrate is repeated at least
once.
61. The method of claim 57 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
62. The method of claim 61 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
63. The method of claim 57 wherein the metal-containing layer has a
thickness of about 10 .ANG. to about 100 .ANG..
64. The method of claim 57 wherein the temperature of the substrate
is about 25.degree. C. to about 400.degree. C.
65. The method of claim 57 wherein the atomic layer deposition
chamber containing the substrate has a pressure of about 10.sup.-4
torr to about 10 torr.
66. The method of claim 57 further comprising providing a vapor
comprising at least one metal-containing precursor compound that is
different than the precursor compound of Formula I and directing
this vapor to the substrate to allow the at least one
metal-containing compound to chemisorb on the at least one surface
of the substrate.
67. A method of forming a niobium oxide layer on a substrate, the
method comprising: providing a substrate; providing a vapor
comprising at least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein: M is
niobium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5),
each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; providing a vapor
comprising at least one metal-containing precursor compound
different than M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I);
directing the vapor comprising the at least one precursor compound
of Formula I and the vapor comprising the at least one
metal-containing precursor compound different that the precursor
compound of Formula I to the substrate to form a layer comprising
niobium oxide on at least one surface of the substrate using an
atomic layer deposition process comprising a plurality of
deposition cycles.
68. The method of claim 67 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
69. The method of claim 68 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
70. The method of claim 67 wherein the vapor comprising the at
least one precursor compound of Formula I and the vapor comprising
the at least one metal-containing precursor compound different that
the precursor compound of Formula I are directed to the substrate
substantially simultaneously.
71. The method of claim 67 wherein the metal-containing layer is a
dielectric layer.
72. The method of claim 67 further comprising at least one reaction
gas.
73. The method of claim 72 wherein the at least one reaction gas is
selected from the group consisting of oxygen, water vapor, ozone,
nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,
hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,
organic amine, silane, disilane, higher silanes, diborane, plasma,
air, and combinations thereof.
74. The method of claim 73 wherein the at least one reaction gas
selected from the group consisting of ozone and oxygen.
75. The method of claim 67 wherein the vapor comprising the at
least one precursor compound of Formula I and the vapor comprising
the at least one metal-containing precursor compound different that
the precursor compound of Formula I are directed to the substrate
prior to directing the at least one reaction gas to the
substrate.
76. The method of claim 67 wherein the vapor comprising the at
least one precursor compound of Formula I and the vapor comprising
the at least one metal-containing precursor compound different that
the precursor compound of Formula I further comprise a nonreactive
gas.
77. The method of claim 76 wherein the nonreactive gas is selected
from the group consisting of nitrogen, helium, argon, and mixtures
thereof.
78. The method of claim 67 wherein the metal-containing precursor
compound different than Formula I comprises at least one metal
selected from the group consisting of bismuth, tantalum, hafnium,
aluminum, niobium, vanadium, and combinations thereof.
79. A method of manufacturing a memory device structure, the method
comprising: providing a substrate having a first electrode thereon;
providing at least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein: M is
selected from the group consisting of niobium and vanadium, X is
(NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1,
R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is independently an organic
group, x=1 or 2; vaporizing the at least one precursor compound of
Formula I; contacting the at least one vaporized precursor compound
of Formula I with the substrate to chemisorb the compound on the
first electrode of the substrate; providing at least one reaction
gas; contacting the at least one reaction gas with the substrate
with the chemisorbed compound thereon to form a dielectric layer on
the first electrode of the substrate; and forming a second
electrode on the dielectric layer.
80. The method of claim 79 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
81. The method of claim 80 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
82. The method of claim 79 wherein the at least one reaction gas is
selected from the group consisting of oxygen, water vapor, ozone,
nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,
hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,
organic amine, silane, disilane, higher silanes, diborane, plasma,
air, and combinations thereof.
83. The method of claim 82 wherein the at least one reaction gas is
selected from the group consisting of ozone and oxygen.
84. The method of claim 79 wherein the vapor comprising the at
least one precursor compound of Formula I further comprises a
nonreactive gas.
85. The method of claim 84 wherein the nonreactive gas is selected
from the group consisting of nitrogen, helium, argon, and mixtures
thereof.
86. An atomic layer vapor deposition apparatus comprising: a
deposition chamber having a substrate positioned therein; and at
least one vessel comprising at least one precursor compound of the
formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein:
M is selected from the group consisting of niobium and vanadium, X
is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5), each
R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is independently an
organic group, and x=1 or 2.
87. The apparatus of claim 86 wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are each independently organic groups having
1-10 carbon atoms.
88. The apparatus of claim 86 wherein R.sup.2 is (CH.sub.2).sub.n,
wherein n=1-5.
89. The apparatus of claim 86 further comprising at least one
source of at least one reaction gas.
90. The apparatus of claim 89 wherein the at least one reaction gas
is selected from the group consisting of oxygen, water vapor,
ozone, nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,
hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,
organic amine, silane, disilane, higher silanes, diborane, plasma,
air, and combinations thereof.
91. The apparatus of claim 86 further comprising at least one
source of an inert gas.
92. The apparatus of claim 86 further comprising at least one
vessel comprising at least one metal-containing precursor compound
that is different that the precursor compound of Formula I.
93. The apparatus of claim 92 wherein the at least one
metal-containing precursor compound that is different that the
precursor compound of Formula I comprises a metal selected from the
group consisting of bismuth, tantalum, hafnium, aluminum, niobium,
vanadium, and combinations thereof.
Description
FIELD OF THE INVENTION
[0001] This invention relates to methods of forming a metal
containing layer, such as a metal oxide layer, on a substrate using
one or more precursor compounds using a vapor deposition process.
The precursor compounds and methods are particularly suitable for
the formation of metal containing layers on semiconductor
substrates or substrate assemblies.
BACKGROUND OF THE INVENTION
[0002] In integrated circuit manufacturing, microelectronic devices
such as capacitors are the basic energy storage devices in random
access memory devices, such as dynamic random access memory (DRAM)
devices, static random access memory (SRAM) devices, and
ferroelectric memory (FERAM) devices. Capacitors typically consist
of two conductors, such as parallel metal or polysilicon plates,
which act as the electrodes (i.e., the storage node electrode and
the cell plate capacitor electrode), insulated from each other by a
layer of dielectric material.
[0003] 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
nanometer (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.
[0004] 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.
[0005] High quality thin oxide films of metals, such as ZrO.sub.2,
Ta.sub.2O.sub.5, HfO.sub.2, Al.sub.2O.sub.3, Nb.sub.2O.sub.5, and
YSZ 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.
Additionally, Nb.sub.2O.sub.5, Nb.sub.2O.sub.5 doped/laminated
Al.sub.2O.sub.3, Ta.sub.2O.sub.5, and HfO.sub.2 films have been
shown to be useful for capacitor and gate dielectrics.
Nb.sub.2O.sub.5 doping/laminating has been shown to decrease
leakage and stabilize crystalline phases.
[0006] Efforts have been made 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.
SUMMARY OF THE INVENTION
[0007] In view of the foregoing, and despite improvements in
semiconductor dielectric layers, there remains a need in the
semiconductor art 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. Accordingly, the present invention is directed to
methods of manufacturing a semiconductor structure including at
least one precursor compound including a metal selected from the
group of niobium and vanadium, to methods of forming a niobium
oxide layer on a substrate, and to an atomic layer vapor deposition
apparatus that includes at least one precursor compound including a
metal selected from the group of niobium and vanadium.
[0008] In one aspect, the present invention is directed to a method
of manufacturing a semiconductor structure, the method including:
providing a semiconductor substrate or substrate assembly;
providing a vapor including at least one precursor compound of the
formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein M
is selected from the group consisting of niobium and vanadium, X is
(NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1,
R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is independently an organic
group, x=1 or 2; and contacting the vapor including the at least
one precursor compound of Formula I with the semiconductor
substrate or substrate assembly to form a metal-containing layer on
at least one surface of the semiconductor substrate or substrate
assembly using an atomic layer deposition process including a
plurality of deposition cycles.
[0009] The present invention may also include the use of a reaction
gas in methods for the manufacture of a semiconductor structure.
Thus, in a further aspect, the present invention is also directed
to a method of manufacturing a semiconductor structure, the method
including: providing a semiconductor substrate or substrate
assembly; providing a vapor including at least one precursor
compound of the formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x
(Formula I), wherein M is selected from the group consisting of
niobium and vanadium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or
(OR.sup.5), each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; providing at least one
reaction gas; and contacting the vapor including the at least one
precursor compound of Formula I with the semiconductor substrate or
substrate assembly to form a metal-containing layer on at least one
surface of the semiconductor substrate or substrate assembly using
an atomic layer deposition process including a plurality of
deposition cycles.
[0010] In yet another aspect, the present invention is directed to
a method of manufacturing a semiconductor structure, the method
including: providing a semiconductor substrate or substrate
assembly within a deposition chamber; providing a vapor including
at least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein M is
selected from the group consisting of niobium and vanadium, X is
(NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1,
R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is independently an organic
group, x=1 or 2; directing the vapor including the at least one
precursor compound of Formula I to the semiconductor substrate or
substrate assembly and allowing the at least one compound to
chemisorb to at least one surface of the semiconductor substrate or
substrate assembly; providing at least one reaction gas; and
directing the at least one reaction gas to the semiconductor
substrate or substrate assembly with the chemisorbed species
thereon to form a metal-containing layer on at least one surface of
the semiconductor substrate or substrate assembly.
[0011] In certain applications, it may be advantageous to include
deposition of a metal-containing precursor composition in addition
to, and different from, the precursor composition of Formula I. To
this end the present invention is further directed in yet another
aspect to a method of manufacturing a semiconductor structure, the
method including: providing a semiconductor substrate or substrate
assembly; providing a vapor including at least one precursor
compound of the formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x
(Formula I), wherein M is selected from the group consisting of
niobium and vanadium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or
(OR.sup.5), each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; providing a vapor
including at least one metal-containing precursor compound
different than M(OR.sup.1).sub.5-x(X(R.sup.2O).sub.x (Formula I);
directing the vapor including the at least one precursor compound
of Formula I and the vapor including the at least one
metal-containing precursor compound different that the precursor
compound of Formula I to the semiconductor substrate or substrate
assembly to form a metal-containing layer on at least one surface
of the semiconductor substrate or substrate assembly using an
atomic layer deposition process including a plurality of deposition
cycles.
[0012] It is further recognized that the present invention may be
useful in the formation of a niobium oxide layer on any appropriate
substrate for any application wherein such a layer is desired.
Thus, in another aspect the present invention is directed to a
method of forming a niobium oxide layer on a substrate, the method
including: providing a substrate; providing a vapor including at
least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein M is
niobium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5),
each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; and contacting the vapor
including the at least one precursor compound with the substrate to
form a niobium oxide layer on at least one surface of the substrate
using an atomic layer deposition process including a plurality of
deposition cycles.
[0013] Additionally, the present invention contemplates the
formation of a niobium oxide layer on a substrate including the use
of a reaction gas in the method. Therefore, in yet a further
aspect, the present invention is directed to a method of forming a
niobium oxide layer on a substrate, the method including: providing
a substrate; providing a vapor including at least one precursor
compound of the formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x
(Formula I), wherein M is niobium, X is (NR.sup.3R.sup.4),
(PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 is independently an organic group, x=1 or 2;
providing at least one reaction gas; and contacting the vapor
including the at least one precursor compound with the substrate to
form a niobium oxide layer on at least one surface of the substrate
using an atomic layer deposition process including a plurality of
deposition cycles.
[0014] The present invention, in yet another aspect, is directed to
a method of forming a niobium oxide layer on a substrate, the
method including: providing a substrate within a deposition
chamber; providing a vapor including at least one precursor
compound of the formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x
(Formula I), wherein M is niobium, X is (NR.sup.3R.sup.4),
(PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 is independently an organic group, x=1 or 2;
directing the vapor including the at least one precursor compound
of Formula I to the substrate and allowing the at least one
compound to chemisorb to at least one surface of the substrate;
providing at least one reaction gas; and directing the at least one
reaction gas to the substrate with the chemisorbed species thereon
to form a niobium oxide layer on at least one surface of the
substrate.
[0015] Methods of the present invention are also useful in the
formation of a niobium oxide layer on a substrate where deposition
of an additional metal-containing precursor is desired. To this
end, in a further aspect the present invention is directed to a
method of forming a niobium oxide layer on a substrate, the method
including: providing a substrate; providing a vapor including at
least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein M is
niobium, X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5),
each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group, x=1 or 2; providing a vapor
including at least one metal-containing precursor compound
different than M(OR.sup.1).sub.5-x(X(R.sup.2O).sub.x (Formula I);
directing the vapor including the at least one precursor compound
of Formula I and the vapor including the at least one
metal-containing precursor compound different that the precursor
compound of Formula I to the substrate to form a layer including
niobium oxide on at least one surface of the substrate using an
atomic layer deposition process including a plurality of deposition
cycles.
[0016] Additionally, methods of the present invention may
advantageously be used in the manufacture of memory devices. Thus,
in yet a further aspect, the present invention is also directed to
a method of manufacturing a memory device structure, the method
including: providing a substrate having a first electrode thereon;
providing at least one precursor compound of the formula
M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein M is
selected from the group consisting of niobium and vanadium, X is
(NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1,
R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is independently an organic
group, x=1 or 2; vaporizing the at least one precursor compound of
Formula I; contacting the at least one vaporized precursor compound
of Formula I with the substrate to chemisorb the compound on the
first electrode of the substrate; providing at least one reaction
gas; contacting the at least one reaction gas with the substrate
with the chemisorbed compound thereon to form a dielectric layer on
the first electrode of the substrate; and forming a second
electrode on the dielectric layer.
[0017] Further, the present invention also provides an apparatus
useful for the deposition of precursor compositions as taught
herein. In yet another aspect, therefore, the present invention is
directed to an atomic layer vapor deposition apparatus including: a
deposition chamber having a substrate positioned therein; and at
least one vessel including at least one precursor compound of the
formula M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x (Formula I), wherein M
is selected from the group consisting of niobium and vanadium, X is
(NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5), each R.sup.1,
R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is independently an organic
group, and x=1 or 2.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a perspective view of a vapor deposition coating
system suitable for use in the method of the present invention.
[0019] FIG. 2 is an exemplary capacitor construction formed using
methods of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
[0020] The present invention includes a method of forming metal
containing layers, preferably metal oxide layers, on substrates,
preferably by using an atomic vapor deposition process and using
one or more metal precursor compounds, wherein metal is selected
from the group of niobium and vanadium. The atomic layer deposition
process may, preferably, include a plurality of deposition
cycles.
[0021] The terms "semiconductor substrate" or "substrate assembly"
as used herein refer 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.
[0022] The term "layer" as used herein refers to any
metal-containing 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.
[0023] The terms "deposition process" and "vapor deposition
process" as used herein refer to a process in which a
metal-containing 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
compounds are vaporized and directed to and/or contacted with 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-containing 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.
[0024] The term "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 a typical chemical vapor
deposition (CVD) process wherein the desired layer is deposited in
a single cycle onto the substrate from vaporized metal precursor
compounds (and any reaction gasses used) within a deposition
chamber, 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.
[0025] The term "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 chemisorption. In ALD one or more
appropriate precursor compounds or reaction gasses 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 gasses) 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.
[0026] The present invention includes methods of forming a metal
containing layer, preferably a metal oxide layer such as, for
example, a niobium oxide layer, on a substrate. Further, such metal
containing layer is preferably formed on a semiconductor substrate
or substrate assembly in the manufacture of a semiconductor
structure or another memory device structure. Such layers are
deposited or chemisorbed onto a substrate and form, preferably,
dielectric layers. The methods of the present invention involve
forming a layer on a substrate by using one or more metal precursor
compounds of the formula: M(OR.sup.1).sub.5-x(XR.sup.2O).sub.x
(Formula I) wherein M is selected from niobium and vanadium, X is
(NR.sup.3R.sup.4), (PR.sup.3R.sup.4), or (OR.sup.5), x is 1 or 2,
and each R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is
independently an organic group (as described in greater detail
below). Additionally, the present invention includes methods of
forming a metal containing layer further including using a
precursor compound in addition to and different from the compound
of Formula I. An apparatus useful for atomic layer deposition (ALD,
discussed more fully below) of the disclosed precursor compounds is
also disclosed.
[0027] 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.).
[0028] 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, S, Si,
or F 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.
[0029] In Formula I, M is a metal selected from the group of
niobium and vanadium and X is (NR.sup.3R.sup.4), (PR.sup.3R.sup.4),
or (OR.sup.5), with R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5
of Formula I being each individually an organic group. Preferably,
each of the organic groups of R.sup.1, R.sup.2, R.sup.3, R.sup.4,
and R.sup.5 contain 1-10 carbon atoms, more preferably, 1-6 carbon
atoms, and most preferably, 1-4 carbon atoms. Preferably, R.sup.2
is (CH.sub.2).sub.n, with n=1-5.
[0030] Additionally, each of the organic groups R.sup.1, R.sup.2,
R.sup.3, R.sup.4, and R.sup.5 may optionally include one or more
heteroatoms (e.g., oxygen, nitrogen, fluorine, etc.), or functional
groups (e.g., carbonyl groups, hydroxycarbyl groups, aminocarbyl
groups, alcohols, fluorinated alcohols, etc.). That is, included
within the scope of the compounds of Formula I are compounds
wherein at least one atom in the organic group has been replaced
with, for example, one of a carbonyl group, a hydroxycarbyl group,
an oxygen atom, a nitrogen atom, or an aminocarbyl group. Certain
preferred organic groups, R.sup.1, R.sup.3, R.sup.4, and R.sup.5,
of Formula I include (C1-C4) alkyl groups, which may be linear,
branched, or cyclic groups, as well as alkenyl groups (e.g., dienes
and trienes), or alkynyl groups.
[0031] Examples of precursor compounds of Formula I include
Nb(OEt).sub.4(Me.sub.2NCH.sub.2CH.sub.2O) (also known as niobium
tetraethoxy dimethylaminoethoxide or NbTDMAE), and
Nb(OEt).sub.4(MeOCH.sub.2CH.sub.2O), wherein Me is methyl, and Et
is ethyl.
[0032] In addition to the precursor compositions of Formula I, the
present invention includes methods and apparatus in which a metal
containing precursor compound different that the precursor compound
of Formula I may be used. Such precursors may be
deposited/chemisorbed, for example in an ALD process discussed more
fully below, substantially simultaneously with or sequentially to
the precursor compounds of Formula I. Further, the different
precursor compound may be deposited/chemisorbed in a deposition
cycle either prior to or subsequently to introducing a reaction gas
to the substrate or substrate assembly. These different metal
containing precursor compounds may preferably include at least one
metal selected from the group of bismuth, tantalum, hafnium,
aluminum, niobium, vanadium, and combinations of these metals.
[0033] The precursor compounds of the present invention may be
prepared according to any appropriate method known to one skilled
in the art. For instance, the precursor may be prepared by reacting
a metal alkoxide with one equivalent of an alcohol having an extra
donor function, as illustrated, for example, in the following
reaction:
Nb(OEt).sub.5+(HO)R.sup.1NR.sup.2R.sup.3.fwdarw.Nb(OEt).sub.4OR.sup.1NR.s-
up.2R.sup.3+EtOH
[0034] 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.
[0035] Solvents that are suitable for some embodiments of the
present invention 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.
[0036] The precursor compounds of the present invention can,
optionally, be vaporized and deposited/chemisorbed substantially
simultaneously with, and in the presence of, one or more reaction
gasses. Alternatively, the metal containing layers may be formed by
alternately introducing the precursor compound and the reaction
gas(es) during each deposition cycle. Such reaction gasses may
typically include oxygen, water vapor, ozone, nitrogen oxides,
sulfur oxides, hydrogen, hydrogen sulfide, hydrogen selenide,
hydrogen telluride, hydrogen peroxide, ammonia, organic amine,
silane, disilane and higher silanes, diborane, plasma, air, and any
combination of these gasses. Preferable optional reaction gasses
include oxygen and ozone. A most preferred optional reaction gas is
ozone.
[0037] Additionally, the precursor compounds can be vaporized in
the presence of one or more inert (i.e., nonreactive) carrier
gasses if desired. Such inert carrier gasses may also be used in
purging steps in an ALD process, for example. The inert carrier gas
typically includes, but is not limited to, nitrogen, helium, argon,
and combinations thereof. In the context of the present invention,
an inert carrier gas is understood to be a gas that does not
substantially interfere with the formation of the metal-containing
layer.
[0038] 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, borophosphosilicate glass (BPSG), silicon such as, e.g.,
conductively doped polysilicon, monocrystalline silicon, etc. (for
this invention, appropriate forms of silicon are simply referred to
as "silicon"), for example in the form of a silicon wafer,
tetraethylorthosilicate (TEOS) oxide, spin on glass (i.e., a thin
layer of SiO.sub.2, optionally doped, deposited by a spin on
process), TiN, TaN, W, noble metals, etc. 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.
[0039] For substrates including semiconductor substrates or
substrate assemblies, 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.
[0040] Substrates other than semiconductor substrates or substrate
assemblies can also be used in methods of the present invention.
Any substrate that may advantageously form a metal containing layer
thereon, such as a metal oxide layer, may be used, such substrates
including, for example, fibers, wires, etc.
[0041] A preferred deposition process for the present 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-containing (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 gasses and directed
to and/or contacted with the substrate to form a metal-containing
layer on the 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.
[0042] Chemical vapor deposition (CVD) has been extensively used
for the preparation of metal-containing 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. Typically, the desired precursor
compounds are vaporized and then introduced into a deposition
chamber containing a heated substrate with optional reaction gasses
and/or inert carrier gasses in a single deposition cycle. 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.
[0043] 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.
[0044] Alternatively, and preferably, the vapor deposition process
employed in the methods of the present invention is a multi-cycle
atomic layer deposition (ALD) process. Such a process is
advantageous, in particular advantageous over a CVD process, in
that in provides for improved control of atomic-level thickness and
uniformity to the deposited layer (e.g., dielectric layer) by
providing a plurality of deposition cycles. Further, ALD processes
typically expose the metal precursor compounds to lower
volatilization and reaction temperatures, which tends to decrease
degradation of the precursor as compared to, for example, typical
CVD processes.
[0045] Generally 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.). These
temperatures are generally lower than those presently used in CVD
processes, which typically include deposition temperatures at the
substrate surface 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. 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 gasses,
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 gasses. (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)).
[0046] A typical ALD process includes exposing an initial substrate
to a first chemical species (e.g., a metal precursor compound such
as that 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 is substantially formed on the substrate surface.
Practically, chemisorption may not occur on all portions of the
substrate. Nevertheless, such a partial monolayer is still
understood to be 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.
[0047] The first species is purged from over the substrate and a
second chemical species (e.g., a different precursor compound) 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.
Optionally, 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.
[0048] Thus, the use of ALD provides the ability to improve the
control of thickness and uniformity of metal containing layers on a
substrate. For example, depositing thin layers of precursor
compound in a plurality of cycles provides a more accurate control
of ultimate film thickness. This is particularly advantageous when
the precursor compound is directed to the substrate and allowed to
chemisorb thereon, preferably further including at least one
reaction gas that reacts with the chemisorbed species on the
substrate, and even more preferably wherein this cycle is repeated
at least once.
[0049] Purging of excess vapor of each species following
deposition/chemisorption onto a substrate may involve a variety of
techniques including, but not limited to, contacting the substrate
and/or monolayer with an inert 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 gasses, as discussed above, may include
N.sub.2, Ar, He, etc. Additionally, 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.
[0050] 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.
[0051] Thus, during the ALD process, numerous consecutive
deposition cycles are conducted in the deposition chamber, each
cycle depositing a very thin metal-containing 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 compound(s) into the deposition chamber
containing a substrate, chemisorbing the precursor compound(s) as a
monolayer onto the substrate surfaces, purging the deposition
chamber, then introducing to the chemisorbed precursor compound(s)
precursor compound(s) that may be the same as the first precursor
compound(s) or may be other precursor compound(s) in a plurality of
deposition cycles until the desired thickness of the
metal-containing layer is achieved. Preferred thicknesses of the
metal containing layers of the present invention are at least about
10 angstroms (.ANG.), and preferably no greater than about 100
.ANG..
[0052] The pulse duration of precursor compound(s) and inert
carrier gas(es) is generally of a duration sufficient to saturate
the substrate surface. Typically, the pulse duration is from about
0.1 second to about 5 seconds, preferably from about 0.2 second to
about 3 seconds, and more preferably from about 2 seconds to about
3 seconds.
[0053] In comparison to the predominantly thermally driven CVD, ALD
is predominantly chemically driven. Thus, ALD may advantageously be
conducted at much lower temperatures than CVD. During the ALD
process, the substrate temperature may be 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, on the other hand, may be sufficiently high to
avoid condensation of the precursor compound(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., and more preferably about 250.degree. C. to
about 300.degree. C.), which, as discussed above, is generally
lower than temperatures presently used in typical 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, optionally but 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 considered substantially the same
temperature by providing a reaction rate statistically the same as
would occur at the temperature of the first precursor
chemisorption. Alternatively, chemisorption and subsequent
reactions could instead occur at substantially exactly the same
temperature.
[0054] For a typical ALD process, the pressure inside the
deposition chamber is kept at about 10.sup.-4 torr to about 10
torr, preferably about 10.sup.-4 torr to about 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.
[0055] 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.
[0056] After layer formation on the substrate, an annealing process
may 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.
[0057] 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 gate dielectrics and 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.
[0058] 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. 1. The system includes an
enclosed vapor deposition chamber 10, in which a vacuum may be
created using turbo pump 12 and backing pump 14. One or more
substrates 16 (e.g., semiconductor substrates or substrate
assemblies) are positioned in chamber 10. A constant nominal
temperature is established for substrate 16, which can vary
depending on the process used. Substrate 16 may be heated, for
example, by an electrical resistance heater 18 on which substrate
16 is mounted. Other known methods of heating the substrate may
also be utilized.
[0059] In this process, precursor compound(s) (such as the
precursor compound of Formula I and optionally metal containing
precursor compound(s) different than the precursor compound of
Formula I) 60 and/or 61 are stored in vessels 62. The precursor
compound(s) are vaporized and separately fed along lines 64 and 66
to the deposition chamber 10 using, for example, an inert carrier
gas 68. A reaction gas 70 may be supplied along line 72 as needed.
Also, a purge gas 74, which is often the same as the inert carrier
gas 68, may be supplied along line 76 as needed. As shown, a series
of valves 80-85 are opened and closed as required.
[0060] FIG. 2 shows an example of the ALD formation of niobium
and/or vanadium-containing layers of the present invention as used
in an exemplary capacitor construction. Referring to FIG. 2,
capacitor construction 200 includes substrate 210 having conductive
diffusion area 240 formed therein. Substrate 210 can include, for
example, silicon. An insulating layer 260, such as BPSG, is
provided over substrate 210, with contact opening 280 provided
therein to diffusion area 240. Conductive material 290 fills
contact opening 280, and may include, for example, tungsten or
conductively doped polysilicon. Capacitor construction 200 includes
a first capacitor electrode (a bottom electrode) 220, a dielectric
layer 240 which may be formed by methods of the present invention,
and a second capacitor electrode (a top electrode) 250.
[0061] It is to be understood that FIG. 2 is an exemplary
construction, and methods of the invention are useful for forming
niobium oxide layers and/or vanadium oxide layers on any substrate,
preferably on semiconductor structures, and that 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] Furthermore, a diffusion barrier layer may optionally be
formed over the dielectric layer 240, and may, for example, include
TiN, TaN, metal silicide, or metal silicide-nitride. While the
diffusion barrier layer is described as a distinct layer, it is to
be understood that the barrier layers may include conductive
materials and can accordingly, in such embodiments, be understood
to include at least a portion of the capacitor electrodes. In
certain embodiments that include a diffusion barrier layer, an
entirety of a capacitor electrode can include conductive barrier
layer materials.
[0063] The following examples are offered to further illustrate
various specific embodiments and techniques of the present
invention. It should be understood, however, that many variations
and modifications understood by those of ordinary skill in the art
may be made while remaining within the scope of the present
invention. Therefore, the scope of the invention is not intended to
be limited by the following example. Unless specified otherwise,
all percentages shown in the examples are percentages by
weight.
EXAMPLES
Example 1
Deposition of Nb.sub.2O.sub.5 by Atomic Layer Deposition
[0064] A Nb.sub.2O.sub.5 film was deposited on a TiN bottom
electrode by ALD, as described above, using alternate pulses of
Nb(OEt).sub.4(Me.sub.2NCH.sub.2CH.sub.2O) (NbTDMAE) and ozone
(O.sub.3) at a substrate temperature of 325.degree. C. and a
pressure of 1 Torr. The film was deposited at a rate of 0.35
.ANG./cycle, with each cycle consisting of a 2 second niobium
precursor dose, 4 second purge with the inert gas, a 5 second ozone
dose (O.sub.3: 500 sccm at 15%), and a 15 second purge with the
inert gas. An approximately 72 .ANG. thick Nb.sub.2O.sub.5 film
resulted.
Example 2
Deposition of Ta/Nb Oxide by Atomic Layer Deposition
[0065] Example 1, above, was repeated, with the exception that both
TaTDMAE and NbTDMAE precursors were deposited, the deposition rate
was 0.425 .ANG./cycle, and an 8 second ozone dose was performed.
The niobium appeared to be substantially homogeneously distributed
throughout the resulting Ta/Nb oxide layer.
[0066] 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.
* * * * *