U.S. patent application number 15/646602 was filed with the patent office on 2018-01-18 for multi-layer coating with diffusion barrier layer and erosion resistant layer.
The applicant listed for this patent is Applied Materials, Inc.. Invention is credited to David Fenwick, Jennifer Y. Sun, Xiaowei Wu.
Application Number | 20180016678 15/646602 |
Document ID | / |
Family ID | 60941682 |
Filed Date | 2018-01-18 |
United States Patent
Application |
20180016678 |
Kind Code |
A1 |
Fenwick; David ; et
al. |
January 18, 2018 |
MULTI-LAYER COATING WITH DIFFUSION BARRIER LAYER AND EROSION
RESISTANT LAYER
Abstract
A multi-layer coating for a surface of an article comprising a
diffusion barrier layer and an erosion resistant layer. The
diffusion barrier layer may be a nitride film including but not
limited to TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and
TiZr.sub.xN.sub.y. The erosion resistant layer may be a rare oxide
film including but not limited to YF.sub.3, Y.sub.2O.sub.3,
Er.sub.2O.sub.3, Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y,
YO.sub.xF.sub.y, YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and
YZr.sub.xAl.sub.yO.sub.z. The diffusion barrier layer and the
erosion resistant layer may be deposited on the article's surface
using a thin film deposition technique including but not limited
to, ALD, PVD, and CVD.
Inventors: |
Fenwick; David; (Los Altos
Hills, CA) ; Wu; Xiaowei; (San Jose, CA) ;
Sun; Jennifer Y.; (Mountain View, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Applied Materials, Inc. |
Santa Clara |
CA |
US |
|
|
Family ID: |
60941682 |
Appl. No.: |
15/646602 |
Filed: |
July 11, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62362936 |
Jul 15, 2016 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C23C 16/34 20130101;
C23C 16/405 20130101; C23C 14/08 20130101; C23C 16/45525 20130101;
C23C 14/0641 20130101; C23C 16/40 20130101 |
International
Class: |
C23C 16/455 20060101
C23C016/455; C23C 16/34 20060101 C23C016/34; C23C 14/08 20060101
C23C014/08; C23C 16/40 20060101 C23C016/40; C23C 14/06 20060101
C23C014/06 |
Claims
1. A multi-layer coating comprising: a diffusion barrier layer
selected from a group consisting of TiN.sub.x, TaN.sub.x,
Zr.sub.3N.sub.4, and TiZr.sub.xN.sub.y; and an erosion resistant
layer selected from a group consisting of YF.sub.3, Y.sub.2O.sub.3,
Er.sub.2O.sub.3, Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y,
YO.sub.xF.sub.y, YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and
YZr.sub.xAl.sub.yO.sub.z, wherein the erosion resistant layer
covers the diffusion barrier layer.
2. The multi-layer coating of claim 1, wherein the diffusion
barrier layer has a thickness ranging from about 10 nm to about 100
nm, and wherein the erosion resistant layer has a thickness of up
to about 1 micrometer.
3. The multi-layer coating of claim 1, wherein the multi-layer
coating is able to withstand temperature cycling from about
20.degree. C. to about 450.degree. C. without cracking.
4. A method for forming a multi-layer coating, comprising:
depositing a diffusion barrier layer onto a surface of an article,
wherein the diffusion barrier layer is deposited using a first
deposition process selected from a group consisting of atomic layer
deposition (ALD), physical vapor deposition (PVD), and chemical
vapor deposition (CVD), and wherein the diffusion barrier layer is
selected from a group consisting of TiN.sub.x, TaN.sub.x,
Zr.sub.3N.sub.4, and TiZr.sub.xN.sub.y; and depositing an erosion
resistant layer onto the diffusion barrier layer, wherein the
erosion resistant layer is deposited using a second deposition
process selected from the group consisting of ALD, PVD, and CVD,
and wherein the erosion resistant layer is selected from a group
consisting of YF.sub.3, Y.sub.2O.sub.3, Er.sub.2O.sub.3,
Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y, YO.sub.xF.sub.y,
YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and
YZr.sub.xAl.sub.yO.sub.z.
5. The method of claim 4, wherein the first deposition process and
the second deposition process are both ALD, both PVD, or both
CVD.
6. The method of claim 4, wherein the diffusion barrier layer is
TiN.sub.x, and wherein the diffusion barrier layer is deposited via
ALD or CVD from at least one Ti precursor selected from the group
consisting of bis(diethylamido)bis(dimethylamido)titanium(IV),
tetrakis(diethylamido)titanium(IV),
tetrakis(dimethylamido)titanium(IV),
tetrakis(ethylmethylamido)titanium(IV), titanium(IV) bromide,
titanium(IV) chloride, and titanium(IV) tert-butoxide.
7. The method of claim 4, wherein the diffusion barrier layer is
TaN.sub.x, and wherein the diffusion barrier layer is deposited via
ALD or CVD from at least one Ta precursor selected from the group
consisting of pentakis(dimethylamido)tantalum(V), tantalum(V)
chloride, tantalum(V) ethoxide, and
tris(diethylamino)(tert-butylimido)tantalum(V).
8. The method of claim 4, wherein the diffusion barrier layer is
TiZr.sub.xN.sub.y; wherein the diffusion barrier layer is deposited
via ALD or CVD from at least one Ti precursor and from at least one
Zr precursor; wherein the at least one Ti precursor is selected
from the group consisting of
bis(diethylamido)bis(dimethylamido)titanium(IV),
tetrakis(diethylamido)titanium(IV),
tetrakis(dimethylamido)titanium(IV),
tetrakis(ethylmethylamido)titanium(IV), titanium(IV) bromide,
titanium(IV) chloride, and titanium(IV) tert-butoxide; and wherein
the at least one Zr precursor is selected from the group consisting
of zirconium (IV) bromide, zirconium (IV) chloride, zirconium (IV)
tert-butoxide, tetrakis(diethylamido)zirconium (IV),
tetrakis(dimethylamido)zirconium (IV), and
tetrakis(ethylmethylamido)zirconium (IV).
9. The method of claim 4, wherein the erosion resistant layer is
ErAl.sub.xO.sub.y; wherein the erosion resistant layer is deposited
via ALD or CVD from at least one Er precursor and from at least one
Al.sub.3 precursor; wherein the at least one Er precursor is
selected from the group consisting of tris-methylcyclopentadienyl
erbium (III) (Er(MeCp).sub.3), erbium boranamide (Er(BA).sub.3),
Er(TMHD).sub.3, erbium(III)
tris(2,2,6,6-tetramethyl-3,5-heptanedionate), and
tris(butylcyclopentadienyl)erbium(III); and wherein the at least
one Al precursor is selected from the group consisting of
diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, aluminum
sec-butoxide, aluminum tribromide, aluminum trichloride,
triethylaluminum, triisobutylaluminum, trimethylaluminum, and
tris(diethylamido)aluminum.
10. The method of claim 4, wherein the erosion resistant layer is
YAl.sub.xO.sub.y, wherein the erosion resistant layer is deposited
via ALD or CVD from at least one Y precursor and from at least one
Al precursor; wherein the at least one Y.sub.3 precursor is
selected from the group consisting of
tris(N,N-bis(trimethylsilyl)amide)yttrium (III), yttrium
(III)butoxide, tris(cyclopentadienyl)yttrium(III), and Y(thd)3
(thd=2,2,6,6-tetramethyl-3,5-heptanedionato); and wherein the at
least one Al.sub.3 precursor is selected from the group consisting
of diethylaluminum ethoxide, tris(ethylmethylamido)aluminum,
aluminum sec-butoxide, aluminum tribromide, aluminum trichloride,
triethylaluminum, triisobutylaluminum, trimethylaluminum, and
tris(diethylamido)aluminum.
11. The method of claim 4, wherein the erosion resistant layer is
YO.sub.xF.sub.y, wherein the erosion resistant layer is deposited
via ALD or CVD from at least one Y precursor selected from the
group consisting of tris(N,N-bis(trimethylsilyl)amide)yttrium
(III), yttrium (III)butoxide, tris(cyclopentadienyl)yttrium(III),
and Y(thd)3 (thd=2,2,6,6-tetramethyl-3,5-heptanedionato).
12. The method of claim 4, wherein the erosion resistant layer is
YZr.sub.xO.sub.y, wherein the erosion resistant layer is deposited
via ALD or CVD from at least one Y precursor and from at least one
Zr precursor; wherein the at least one Y precursor is selected from
the group consisting of tris(N,N-bis(trimethylsilyl)amide)yttrium
(III), yttrium (III)butoxide, tris(cyclopentadienyl)yttrium(III),
and Y(thd)3 (thd=2,2,6,6-tetramethyl-3,5-heptanedionato); and
wherein the at least one Zr precursor is selected from the group
consisting of zirconium (IV) bromide, zirconium (IV) chloride,
zirconium (IV) tert-butoxide, tetrakis(diethylamido)zirconium (IV),
tetrakis(dimethylamido)zirconium (IV), and
tetrakis(ethylmethylamido)zirconium (IV).
13. The method of claim 4, wherein the erosion resistant layer is
YZr.sub.xAl.sub.yO.sub.z, wherein the erosion resistant layer is
deposited via ALD or CVD from at least one Y precursor, from at
least one Zr precursor, and from at least one Al precursor; wherein
the at least one Y precursor is selected from the group consisting
of tris(N,N-bis(trimethylsilyl)amide)yttrium (III), yttrium
(III)butoxide, tris(cyclopentadienyl)yttrium(III), and Y(thd)3
(thd=2,2,6,6-tetramethyl-3,5-heptanedionato); wherein the at least
one Zr precursor is selected from the group consisting of zirconium
(IV) bromide, zirconium (IV) chloride, zirconium (IV)
tert-butoxide, tetrakis(diethylamido)zirconium (IV),
tetrakis(dimethylamido)zirconium (IV), and
tetrakis(ethylmethylamido)zirconium (IV); and wherein the at least
one Al precursor is selected from the group consisting of
diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, aluminum
sec-butoxide, aluminum tribromide, aluminum trichloride,
triethylaluminum, triisobutylaluminum, trimethylaluminum, and
tris(diethylamido)aluminum.
14. The method of claim 4, wherein the diffusion barrier layer has
a thickness ranging from about 10 nm to about 100 nm, and wherein
the erosion resistant layer has a thickness of up to about 1
micrometer.
15. The method of claim 4, wherein the multi-layer coating is able
to withstand temperature cycling from about 20.degree. C. to about
450.degree. C. without cracking.
16. The method of claim 4, wherein depositing the diffusion barrier
layer comprises depositing a plurality of intact layers using a
plurality of precursors.
17. The method of claim 16, further comprising annealing the
plurality of intact layers to form an interdiffused diffusion
barrier layer.
18. The method of claim 4, wherein depositing the erosion resistant
layer comprises depositing a plurality of intact layers using a
plurality of precursors.
19. The method of claim 18, further comprising annealing the
plurality of intact layer to form an interdiffused erosion
resistant layer.
20. A coated process chamber component comprising: a process
chamber component having a surface; and a multi-layer coating
comprising: a diffusion barrier layer selected from a group
consisting of TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and
TiZr.sub.xN.sub.y; and an erosion resistant layer selected from a
group consisting of YF.sub.3, Y.sub.2O.sub.3, Er.sub.2O.sub.3,
Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y, YO.sub.xF.sub.y,
YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and YZr.sub.xAl.sub.yO.sub.z,
wherein the erosion resistant layer covers the diffusion barrier
layer.
Description
RELATED APPLICATIONS
[0001] This patent application claims the benefit under 35 U.S.C.
.sctn.119(e) of U.S. Provisional Application No. 62/362,936, filed
Jul. 15, 2016, incorporated herein in its entirety.
TECHNICAL FIELD
[0002] Embodiments of the present disclosure relate to multi-layer
coatings acting as a diffusion barrier and as an erosion resistant
coating, a method for forming a multi-layer coating, and a process
chamber component coated with a multi-layer coating.
BACKGROUND
[0003] Various manufacturing processes expose semiconductor process
chamber components to high temperatures, high energy plasma, a
mixture of corrosive gases, high stress, and combinations thereof.
These extreme conditions may erode the chamber components, corrode
the chamber components, lead to diffusion of chamber components'
materials to the substrates, and increase the chamber components'
susceptibility to defects. It is desirable to reduce these defects
and improve the components' erosion, corrosion, and diffusion
resistance in such extreme environments. Coating semiconductor
process chamber components with protective coatings is an effective
way to reduce defects and extend their durability.
SUMMARY
[0004] Some embodiments of the present invention cover a
multi-layer coating. The multi-layer coating may comprise a
diffusion barrier layer selected from a group consisting of
TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and TiZr.sub.xN.sub.y. The
multi-layer coating may further comprise an erosion resistant layer
selected from a group consisting of YF.sub.3, Y.sub.2O.sub.3,
Er.sub.2O.sub.3, A1.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y,
YO.sub.xF.sub.y, YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and
YZr.sub.xAl.sub.yO.sub.z. The erosion resistant layer may cover the
diffusion barrier layer.
[0005] In some embodiments, disclosed herein is a method for
forming a multi-layer coating. The method includes depositing a
diffusion barrier layer onto a surface of an article. The diffusion
barrier layer may be deposited using a first deposition process
selected from a group consisting of atomic layer deposition,
physical vapor deposition, and chemical vapor deposition. The
diffusion barrier layer may be selected from a group consisting of
TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and TiZr.sub.xN.sub.y. The
method further includes depositing an erosion resistant layer onto
the diffusion barrier layer. The erosion resistant layer may be
deposited using a second deposition process selected from the group
consisting of atomic layer deposition, physical vapor deposition,
and chemical vapor deposition. The erosion resistant layer may be
selected from a group consisting of YF.sub.3, Y.sub.2O.sub.3,
Er.sub.2O.sub.3, A1.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y,
YO.sub.xF.sub.y, YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and
YZr.sub.xAl.sub.yO.sub.z.
[0006] In some embodiments, the present invention covers a coated
process chamber component. The coated process chamber component may
comprise a process chamber component having a surface and a
multi-layer coating coated on the surface. In certain embodiments,
the multi-layer coating may comprise a diffusion barrier layer
selected from a group consisting of TiN.sub.x, TaN.sub.x,
Zr.sub.3N.sub.4, and TiZr.sub.xN.sub.y. In certain embodiments, the
multi-layer coating may further comprise an erosion resistant layer
selected from a group consisting of YF.sub.3, Y.sub.2O.sub.3,
Er.sub.2O.sub.3, Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y,
YO.sub.xF.sub.y, YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and
YZr.sub.xAl.sub.yO.sub.z. The erosion resistant layer may cover the
diffusion barrier layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The present disclosure is illustrated by way of example, and
not by way of limitation, in the figures of the accompanying
drawings in which like references indicate similar elements. It
should be noted that different references to "an" or "one"
embodiment in this disclosure are not necessarily to the same
embodiment, and such references mean at least one.
[0008] FIG. 1 depicts a sectional view of one embodiment of a
processing chamber.
[0009] FIG. 2 depicts a deposition mechanism applicable to a
variety of Atomic Layer Deposition (ALD) techniques, in accordance
with embodiments of the present invention.
[0010] FIG. 3 depicts a deposition mechanism applicable to a
variety of Chemical Vapor Deposition (CVD) techniques, in
accordance with embodiments of the present invention.
[0011] FIG. 4 depicts a deposition mechanism applicable to a
variety of Physical Vapor Deposition (PVD) techniques, in
accordance with embodiments of the present invention.
[0012] FIG. 5 illustrates a method for forming a multi-layer
coating on an article according to an embodiment.
[0013] FIG. 6A illustrates a coated chamber component having a
diffusion barrier layer with intact component layers and an erosion
resistant layer with intact component layers, in accordance with
embodiments of the present invention.
[0014] FIG. 6B illustrates a coated chamber component having a
diffusion barrier layer with intact component layers and an
interdiffused erosion resistant layer, in accordance with
embodiments of the present invention.
[0015] FIG. 6C illustrates a coated chamber component having an
interdiffused diffusion barrier layer and an erosion resistant
layer with intact component layers, in accordance with embodiments
of the present invention.
[0016] FIG. 6D illustrates a coated chamber component having an
interdiffused diffusion barrier layer and an interdiffused erosion
resistant layer, in accordance with embodiments of the present
invention.
DETAILED DESCRIPTION OF EMBODIMENTS
[0017] Embodiments are described herein with reference to a
multi-layer coating that includes a nitride layer acting as a
diffusion barrier layer and a rare earth oxide or fluoride layer
acting as a corrosion and/or erosion resistant layer. The layers
may be deposited through thin film deposition techniques such as
ALD, CVD, and PVD. The nitride layer may be formed from
constituents such as TiN, TaN, and Zr.sub.3N.sub.4. The diffusion
barrier layer may prevent diffusion of elements within a chamber
component to a surface of a substrate during the substrate
processing. In some embodiments, the diffusion barrier layer may
prevent diffusion of metals, such as copper, within a chamber
component to a substrate's surface during substrate processing. The
diffusion barrier layer assists in preventing the chemical
constituents of the chamber component from contaminating the
substrate. The erosion or corrosion resistant layer may be a
multi-component layer formed from constituents such as
Al.sub.2O.sub.3, Y.sub.2O.sub.3, ZrO.sub.2, YF.sub.3, and
Er.sub.2O.sub.3. The corrosion and/or erosion resistant layer may
be deposited on the diffusion barrier layer to prevent erosion or
corrosion of the diffusion barrier layer and the underlying chamber
component in the corrosive gas or plasma environment present in the
process chamber. The thin film deposition techniques assist in
obtaining conformal coating of substantially uniform thickness of
chamber components having simple as well as complex geometric
shapes (with holes and large aspect ratios). The multi-layer stack
having a bottom thin film diffusion barrier layer and a top thin
film erosion or corrosion resistant layer may minimize both
diffusion based contamination of processed wafers as well as shed
particle based contamination of the processed wafers. The diffusion
barrier layer may seal the underlying article that is coated from
diffusion of contaminants (for example, metal contaminant such as
copper), while the erosion or corrosion resistant layer may protect
both the article and the diffusion layer from erosion and/or
corrosion by process gases and/or a plasma environment.
[0018] FIG. 1 is a sectional view of a semiconductor processing
chamber 100 having one or more chamber components that are coated
with a multi-layer coating in accordance with embodiments of the
present invention. The processing chamber 100 may be used for
processes in which a corrosive plasma environment having plasma
processing conditions is provided. For example, the processing
chamber 100 may be a chamber for a plasma etcher or plasma etch
reactor, a plasma cleaner, and so forth. Examples of chamber
components that may include a multi-layer coating include chamber
components with complex shapes and holes having large aspect
ratios. Some exemplary chamber components include a substrate
support assembly 148, an electrostatic chuck (ESC) 150, a ring
(e.g., a process kit ring or single ring), a chamber wall, a base,
a gas distribution plate, a showerhead, gas lines, a nozzle, a lid,
a liner, a liner kit, a shield, a plasma screen, a flow equalizer,
a cooling base, a chamber viewport, a chamber lid, and so on. The
multi-layer coating, which is described in greater detail below, is
applied using an ALD process, a CVD process, a PVD process, or
combinations thereof. ALD, CVD, and PVD which are described in
greater detail with reference to FIGS. 2-4, allow for the
application of a conformal thin film coating of relatively uniform
thickness on all types of components including components with
complex shapes and holes with large aspect ratios.
[0019] As illustrated, the substrate support assembly 148 has a
multi-layer coating 136, in accordance with one embodiment.
However, it should be understood that any of the other chamber
components, such as showerheads, gas lines, electrostatic chucks,
nozzles and others, may also be coated with a multi-layer
coating.
[0020] In one embodiment, the processing chamber 100 includes a
chamber body 102 and a showerhead 130 that enclose an interior
volume 106. The showerhead 130 may include a showerhead base and a
showerhead gas distribution plate. Alternatively, the showerhead
130 may be replaced by a lid and a nozzle in some embodiments. The
chamber body 102 may be fabricated from aluminum, stainless steel
or other suitable material. The chamber body 102 generally includes
sidewalls 108 and a bottom 110. Any of the showerhead 130 (or lid
and/or nozzle), sidewalls 108 and/or bottom 110 may include the
multi-layer coating.
[0021] An outer liner 116 may be disposed adjacent the sidewalls
108 to protect the chamber body 102. The outer liner 116 may be
fabricated and/or coated with a multi-layer coating.
[0022] An exhaust port 126 may be defined in the chamber body 102,
and may couple the interior volume 106 to a pump system 128. The
pump system 128 may include one or more pumps and throttle valves
utilized to evacuate and regulate the pressure of the interior
volume 106 of the processing chamber 100.
[0023] The showerhead 130 may be supported on the sidewall 108 of
the chamber body 102. The showerhead 130 (or lid) may be opened to
allow access to the interior volume 106 of the processing chamber
100, and may provide a seal for the processing chamber 100 while
closed. A gas panel 158 may be coupled to the processing chamber
100 to provide process and/or cleaning gases to the interior volume
106 through the showerhead 130 or lid and nozzle. Showerhead 130 is
used for processing chambers used for dielectric etch (etching of
dielectric materials). The showerhead 130 includes a gas
distribution plate (GDP) 133 having multiple gas delivery holes 132
throughout the GDP 133. The showerhead 130 may include the GDP 133
bonded to an aluminum base or an anodized aluminum base. The GDP
133 may be made from Si or SiC, or may be a ceramic such as
Y.sub.2O.sub.3, Al.sub.2O.sub.3, YAG, and so forth.
[0024] For processing chambers used for conductor etch (etching of
conductive materials), a lid may be used rather than a showerhead.
The lid may include a center nozzle that fits into a center hole of
the lid. The lid may be a ceramic such as Al.sub.2O.sub.3,
Y.sub.2O.sub.3, YAG, or a ceramic compound comprising
Y.sub.4Al.sub.2O.sub.9 and a solid-solution of
Y.sub.2O.sub.3--ZrO.sub.2. The nozzle may also be a ceramic, such
as Y.sub.2O.sub.3, YAG, or the ceramic compound comprising
Y.sub.4Al.sub.2O.sub.9 and a solid-solution of
Y.sub.2O.sub.3--ZrO.sub.2. The lid, showerhead base 104, GDP 133
and/or nozzle may all be coated with a multi-layer coating
according to an embodiment.
[0025] Examples of processing gases that may be used to process
substrates in the processing chamber 100 include halogen-containing
gases, such as C.sub.2F.sub.6, SF.sub.6, SiCl.sub.4, HBr, NF.sub.3,
CF.sub.4, CHF.sub.3, CH.sub.2F.sub.3, F, NF.sub.3, Cl.sub.2,
CCl.sub.4, BCl.sub.3 and SiF.sub.4, among others, and other gases
such as O.sub.2, or N.sub.2O. Examples of carrier gases include
N.sub.2, He, Ar, and other gases inert to process gases (e.g.,
non-reactive gases). The substrate support assembly 148 is disposed
in the interior volume 106 of the processing chamber 100 below the
showerhead 130 or lid. The substrate support assembly 148 holds the
substrate 144 during processing. A ring 146 (e.g., a single ring)
may cover a portion of the electrostatic chuck 150, and may protect
the covered portion from exposure to plasma during processing. The
ring 146 may be silicon or quartz in one embodiment.
[0026] An inner liner 118 may be coated on the periphery of the
substrate support assembly 148. The inner liner 118 may be a
halogen-containing gas resistant material such as those discussed
with reference to the outer liner 116. In one embodiment, the inner
liner 118 may be fabricated from the same materials as those of
outer liner 116. Additionally, the inner liner 118 may also be
coated with a multi-layer coating.
[0027] In one embodiment, the substrate support assembly 148
includes a mounting plate 162 supporting a pedestal 152, and an
electrostatic chuck 150. The electrostatic chuck 150 further
includes a thermally conductive base 164 and an electrostatic puck
166 bonded to the thermally conductive base by a bond 138, which
may be a silicone bond in one embodiment. An upper surface of the
electrostatic puck 166 may be covered by the multi-layer coating
136 in the illustrated embodiment. The multi-layer coating 136 may
be disposed on the entire exposed surface of the electrostatic
chuck 150 including the outer and side periphery of the thermally
conductive base 164 and the electrostatic puck 166 as well as any
other geometrically complex parts or holes having large aspect
ratios in the electrostatic chuck. The mounting plate 162 is
coupled to the bottom 110 of the chamber body 102 and includes
passages for routing utilities (e.g., fluids, power lines, sensor
leads, etc.) to the thermally conductive base 164 and the
electrostatic puck 166.
[0028] The thermally conductive base 164 and/or electrostatic puck
166 may include one or more optional embedded heating elements 176,
embedded thermal isolators 174 and/or conduits 168, 170 to control
a lateral temperature profile of the substrate support assembly
148. The conduits 168, 170 may be fluidly coupled to a fluid source
172 that circulates a temperature regulating fluid through the
conduits 168, 170. The embedded isolator 174 may be disposed
between the conduits 168, 170 in one embodiment. The heater 176 is
regulated by a heater power source 178. The conduits 168, 170 and
heater 176 may be utilized to control the temperature of the
thermally conductive base 164. The conduits and heater heat and/or
cool the electrostatic puck 166 and a substrate (e.g., a wafer) 144
being processed. The temperature of the electrostatic puck 166 and
the thermally conductive base 164 may be monitored using a
plurality of temperature sensors 190, 192, which may be monitored
using a controller 195.
[0029] The electrostatic puck 166 may further include multiple gas
passages such as grooves, mesas and other surface features that may
be formed in an upper surface of the puck 166. These surface
features may all be coated with a multi-layer coating according to
an embodiment. The gas passages may be fluidly coupled to a source
of a heat transfer (or backside) gas such as He via holes drilled
in the puck 166. In operation, the backside gas may be provided at
controlled pressure into the gas passages to enhance the heat
transfer between the electrostatic puck 166 and the substrate
144.
[0030] The electrostatic puck 166 includes at least one clamping
electrode 180 controlled by a chucking power source 182. The
electrode 180 (or other electrode disposed in the puck 166 or base
164) may further be coupled to one or more RF power sources 184,
186 through a matching circuit 188 for maintaining a plasma formed
from process and/or other gases within the processing chamber 100.
The sources 184, 186 are generally capable of producing RF signal
having a frequency from about 50 kHz to about 3 GHz and a power of
up to about 10,000 Watts.
[0031] FIG. 2 depicts a deposition process in accordance with a
variety of ALD techniques. Various types of ALD processes exist and
the specific type may be selected based on several factors such as
the surface to be coated, the coating material, chemical
interaction between the surface and the coating material, etc. The
general principle of an ALD process comprises growing or depositing
a thin film layer by repeatedly exposing the surface to be coated
to sequential alternating pulses of gaseous chemical precursors
that chemically react with the surface one at a time in a
self-limiting manner.
[0032] FIG. 2 illustrates an article 210 having a surface 205. Each
individual chemical reaction between a precursor and the surface is
known as a "half-reaction." During each half reaction, a precursor
is pulsed onto the surface for a period of time sufficient to allow
the precursor to fully react with the surface. The reaction is
self-limiting as the precursor will react with a finite number of
available reactive sites on the surface, forming a uniform
continuous adsorption layer on the surface. Any sites that have
already reacted with a precursor will become unavailable for
further reaction with the same precursor unless and/or until the
reacted sites are subjected to a treatment that will form new
reactive sites on the uniform continuous coating. Exemplary
treatments may be plasma treatment, treatment by exposing the
uniform continuous adsorption layer to radicals, or introduction of
a different precursor able to react with the most recent uniform
continuous film layer adsorbed to the surface.
[0033] In FIG. 2, article 210 having surface 205 may be introduced
to a first precursor 260 for a first duration until a first half
reaction of the first precursor 260 with surface 205 partially
forms film layer 215 by forming an adsorption layer 214.
Subsequently, article 210 may be introduced to a second precursor
265 (also referred to as a reactant) that reacts with the
adsorption layer 214 to fully form the layer 215. The first
precursor 260 may be a precursor for yttrium or another metal, for
example. The second precursor 265 may be an oxygen precursor if the
layer 215 is an oxide, a fluorine precursor if the layer 215 is a
fluoride, or a nitrogen precursor if this layer is a nitride. The
article 210 may alternately be exposed to the first precursor 260
and second precursor 265 up to n number of times to achieve a
target thickness for the layer 215. N may be an integer from 1 to
100, for example. Film layer 215 may be uniform, continuous and
conformal. The film layer 215 may also have a very low porosity of
less than 1% in embodiments, less than 0.1% in some embodiments, or
approximately 0% in further embodiments. Subsequently, article 210
having surface 205 and film layer 215 may be introduced to a third
precursor 270 that reacts with layer 215 to partially form a second
film layer 220 by forming a second adsorption layer 218.
Subsequently, article 210 may be introduced to another precursor
275 (also referred to as a reactant) that reacts with adsorption
layer 218 leading to a second half reaction to fully form the layer
220. The article 210 may alternately be exposed to the third
precursor 270 and fourth precursor 275 up to m number of times to
achieve a target thickness for the layer 220. M may be an integer
from 1 to 100, for example. The second film layer 220 may be
uniform, continuous and conformal. The second film layer 220 may
also have a very low porosity of less than 1% in some embodiments,
less than 0.1% in some embodiments, or approximately 0% in further
embodiments. Thereafter, the sequence of introducing the article
210 to precursors 260 and 265 n number of times and then to
precursors 270 and 275 m number of times may be repeated and
performed x number of times. X may be an integer from 1 to 100, for
example. A result of the sequence may be to grow additional layers
225, 230, 235, and 245. The number and thickness of the various
layers may be independently selected based on the targeted coating
thickness and properties. The various layers may remain intact
(i.e. separate) or in some embodiments may be interdiffused.
[0034] The surface reactions (e.g., half-reactions) are done
sequentially. Prior to introduction of a new precursor, the chamber
in which the ALD process takes place may be purged with an inert
carrier gas (such as nitrogen or air) to remove any unreacted
precursors and/or surface-precursor reaction byproducts. At least
two precursors are used. In some embodiments, more than two
precursors may be used to grow film layers having the same
composition (e.g., to grow multiple layers of Y.sub.2O.sub.3 on top
of each other). In other embodiments, different precursors may be
used to grow different film layers having different
compositions.
[0035] ALD processes may be conducted at various temperatures. The
optimal temperature range for a particular ALD process is referred
to as the "ALD temperature window." Temperatures below the ALD
temperature window may result in poor growth rates and non-ALD type
deposition. Temperatures above the ALD temperature window may
result in thermal decomposition of the article or rapid desorption
of the precursor. The ALD temperature window may range from about
200.degree. C. to about 400.degree. C. In some embodiments, the ALD
temperature window is between about 150.degree. C. to about
350.degree. C.
[0036] The ALD process allows for conformal film layers having
uniform film thickness on articles and surfaces having complex
geometric shapes, holes with large aspect ratios, and
three-dimensional structures. Sufficient exposure time of the
precursors to the surface enables the precursors to disperse and
fully react with the surface in its entirety, including all of its
three-dimensional complex features. The exposure time utilized to
obtain conformal ALD in high aspect ratio structures is
proportionate to the square of the aspect ratio and can be
predicted using modeling techniques. Additionally, the ALD
technique is advantageous over other commonly used coating
techniques because it allows in-situ on demand material synthesis
of a particular composition or formulation without the need for a
lengthy and difficult fabrication of source materials (such as
powder feedstock and sintered targets). A first set of layers 215,
220, 225, and 230 may together form a diffusion barrier layer
selected from a group consisting of TiN.sub.x, TaN.sub.x,
Zr.sub.3N.sub.4, and TiZr.sub.xN.sub.y in some embodiments. The
diffusion barrier layers may be deposited from one pair of ALD
precursors or from alternating pairs of ALD precursors used for
forming, for example, a TiN film, TaN film, and a Zr.sub.3N.sub.4
film. In some embodiments, the films formed from alternating
precursors may remain as intact layers. In other embodiments, the
films formed from alternating precursors may be annealed to form an
interdiffused diffusion barrier layer. In some embodiments, each of
the layers 215, 220, 225, and 230 is a nanolayer of the same
material (e.g., of TiN.sub.x, TaN.sub.x or Zr.sub.3N.sub.4) that
together forms a single thicker diffusion barrier layer.
[0037] In some embodiments, a second set of layers 235 and 245 may
together form an erosion resistant layer selected from a group
consisting of YF.sub.3, Y.sub.2O.sub.3, Er.sub.2O.sub.3,
Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y, YO.sub.xF.sub.y,
YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and YZr.sub.xAl.sub.yO.sub.z.
The erosion resistant layer may be deposited from one pair of ALD
precursors or from alternating pairs of ALD precursors used for
forming, for example, an Al.sub.2O.sub.3 film, Y.sub.2O.sub.3 film,
ZrO.sub.2 film, YF.sub.3 film, and/or an Er.sub.2O.sub.3 film. In
some embodiments, the films formed from alternating precursors may
remain as intact layers. In other embodiments, the films formed
from alternating precursors may be annealed to form an
interdiffused erosion resistant layer. In some embodiments, each of
the layers 235 and 245 is a nanolayer of the same material (e.g.,
of Al.sub.2O.sub.3, Y.sub.2O.sub.3, ZrO.sub.2, YF.sub.3, or
Er.sub.2O.sub.3) that together forms a single thicker erosion
resistant layer.
[0038] In some embodiments, the multi-layer coating may be
deposited on a surface of an article via CVD. An exemplary CVD
system is illustrated in FIG. 3. The system comprises a chemical
vapor precursor supply system 305 and a CVD reactor 310. The role
of the vapor precursor supply system 305 is to generate vapor
precursors 320 from a starting material 315, which could be in a
solid, liquid, or gas form. The vapors are then transported into
CVD reactor 310 and get deposited as thin film 325 on article 330
which is positioned on article holder 335.
[0039] CVD reactor 310 heats article 330 to a deposition
temperature using heater 340. In some embodiments, the heater may
heat the CVD reactor's wall (also known as "hot-wall reactor") and
the reactor's wall may transfer heat to the article. In other
embodiments, the article alone may be heated while maintaining the
CVD reactor's wall cold (also known as "cold-wall reactor"). It is
to be understood that the CVD system configuration should not be
construed as limiting. A variety of equipment could be utilized for
a CVD system and the equipment is chosen to obtain optimum
processing conditions that may give a coating with uniform
thickness, surface morphology, structure, and composition.
[0040] The various CVD processes comprise of the following process:
(1) generate active gaseous reactant species (also known as
"precursors") from the starting material; (2) transport the
precursors into the reaction chamber (also referred to as
"reactor"); (3) absorb the precursors onto the heated article; (4)
participate in a chemical reaction between the precursor and the
article at the gas-solid interface to form a deposit and a gaseous
by-product; and (5) remove the gaseous by-product and unreacted
gaseous precursors from the reaction chamber.
[0041] Suitable CVD precursors may be stable at room temperature,
may have low vaporization temperature, can generate vapor that is
stable at low temperature, have suitable deposition rate (low
deposition rate for thin film coatings and high deposition rate for
thick film coatings), relatively low toxicity, be cost effective,
and relatively pure. For some CVD reactions, such as thermal
decomposition reaction (also known as "pyrolysis") or a
disproportionation reaction, a chemical precursor alone may suffice
to complete the deposition. For other CVD reactions, other agents
(listed in Table 1 below) in addition to a chemical precursor may
be utilized to complete the deposition.
TABLE-US-00001 TABLE 1 Chemical Precursors and Additional Agents
Utilized in Various CVD Reactions CVD reaction Chemical Precursor
Additional Agents Thermal Decomposition Halides N/A (Pyrolysis)
Hydrides Metal carbonyl Metalorganic Reduction Halides Reducing
agent Oxidation Halides Oxidizing agent Hydrides Metalorganic
Hydrolysis Halides Hydrolyzing agent Nitridation Halides Nitriding
agent Hydrides Halohydrides Disproportionation Halides N/A
[0042] CVD has many advantages including its capability to deposit
highly dense and pure coatings and its ability to produce uniform
films with good reproducibility and adhesion at reasonably high
deposition rates. Layers deposited using CVD in embodiments may
have a porosity of below 1%, and a porosity of below 0.1% (e.g.,
around 0%). Therefore, it can be used to uniformly coat complex
shaped components and deposit conformal films with good conformal
coverage (e.g., with substantially uniform thickness). CVD may also
be utilized to deposit a film made of a plurality of components,
for example, by feeding a plurality of chemical precursors at a
predetermined ratio into a mixing chamber and then supplying the
mixture to the CVD reactor system.
[0043] The CVD reactor 310 may be used to form a diffusion barrier
layer and/or an erosion resistant layer that is resistant to
erosion and/or corrosion by plasma environments in embodiments.
Layer 325 may form a diffusion barrier layer selected from a group
consisting of TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and
TiZr.sub.xN.sub.y in embodiments. Layer 345 covering diffusion
barrier layer 325 may be an erosion resistant layer selected from a
group consisting of YF.sub.3, Y.sub.2O.sub.3, Er.sub.2O.sub.3,
Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y, YO.sub.xF.sub.y,
YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and YZr.sub.xAl.sub.yO.sub.z, in
some embodiments.
[0044] In some embodiments, the multi-layer coating may be
deposited on a surface of an article via PVD. PVD processes may be
used to deposit thin films with thicknesses ranging from a few
nanometers to several micrometers. The various PVD processes share
three fundamental features in common: (1) evaporating the material
from a solid source with the assistance of high temperature or
gaseous plasma; (2) transporting the vaporized material in vacuum
to the article's surface; and (3) condensing the vaporized material
onto the article to generate a thin film layer. An illustrative PVD
reactor is depicted in FIG. 4 and discussed in more detail
below.
[0045] FIG. 4 depicts a deposition mechanism applicable to a
variety of PVD techniques and reactors. PVD reactor chamber 400 may
comprise a plate 410 adjacent to the article 420 and a plate 415
adjacent to the target 430. Air may be removed from reactor chamber
400, creating a vacuum. Then argon gas may be introduced into the
reactor chamber, voltage may be applied to the plates, and a plasma
comprising electrons and positive argon ions 440 may be generated.
Positive argon ions 440 may be attracted to negative plate 415
where they may hit target 430 and release atoms 435 from the
target. Released atoms 435 may get transported and deposited as a
thin film 425 onto article 420.
[0046] The PVD reactor chamber 400 may be used to form a diffusion
barrier layer and/or an erosion resistant layer in embodiments.
Layer 425 may form a diffusion barrier layer selected from a group
consisting of TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and
TiZr.sub.xN.sub.y in embodiments. Layer 445 covering diffusion
barrier layer 425 may be an erosion resistant layer selected from a
group consisting of YF.sub.3, Y.sub.2O.sub.3, Er.sub.2O.sub.3,
Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y, YO.sub.xF.sub.y,
YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and YZr.sub.xAl.sub.yO.sub.z, in
some embodiments.
[0047] Article 210 in FIG. 2, article 330 in FIG. 3, and article
420 in FIG. 4 may represent various semiconductor process chamber
components including but not limited to substrate support assembly,
an electrostatic chuck (ESC), a ring (e.g., a process kit ring or
single ring), a chamber wall, a base, a gas distribution plate, gas
lines, a showerhead, a nozzle, a lid, a liner, a liner kit, a
shield, a plasma screen, a flow equalizer, a cooling base, a
chamber viewport, a chamber lid, and so on. The articles and their
surfaces may be made from a metal (such as aluminum, stainless
steel), a ceramic, a metal-ceramic composite, a polymer, a polymer
ceramic composite, or other suitable materials, and may further
comprise materials such as AN, Si, SiC, Al.sub.2O.sub.3, SiO.sub.2,
and so on.
[0048] With the ALD, CVD, and PVD techniques, diffusion barrier
films, such as TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and
TiZr.sub.xN.sub.y, and erosion resistant films, such as YF.sub.3,
Y.sub.2O.sub.3, Er.sub.2O.sub.3, Al.sub.2O.sub.3, ZrO.sub.2,
ErAl.sub.xO.sub.y, YO.sub.xF.sub.y, YAl.sub.xO.sub.y,
YZr.sub.xO.sub.y and YZr.sub.xAl.sub.yO.sub.z can be formed. In
some embodiments, the diffusion barrier layer and the erosion
resistant layer may both be deposited using the same technique,
i.e. both may deposited via ALD, both may be deposited via CVD, or
both may be deposited via PVD. In other embodiments, the diffusion
barrier layer may be deposited by one technique and the erosion
resistant layer may be deposited by another technique. If both
layers are deposited via ALD, for example, the diffusion barrier
layer may be adsorbed and deposited by proper sequencing of the
precursors used to adsorb and deposit TiN, TaN, and
Zr.sub.3N.sub.4, and the erosion resistant films may be adsorbed
and deposited by proper sequencing of the precursors used to adsorb
and deposit Y.sub.2O.sub.3, Al.sub.2O.sub.3, YF.sub.3, ZrO.sub.2,
and Er.sub.2O.sub.3, as discussed in more detail below.
[0049] FIG. 5 illustrates a method 500 for forming a multi-layer
coating on an article according to an embodiment. The method may
optionally begin by selecting a composition for the multi-layer
coating (not illustrated in FIG. 5). The composition selection and
method of forming may be performed by the same entity or by
multiple entities. Pursuant to block 505, the method comprises
depositing a diffusion barrier layer onto a surface of an article
using a first deposition process selected from a group consisting
of ALD, CVD, and PVD. The diffusion barrier layer may comprise a
plurality of intact layers. The plurality of intact layers may be
made out of a plurality of precursors, forming a diffusion barrier
layer. The diffusion barrier layer may have a thickness ranging
from about 10 nm to about 100 nm and may be selected from a group
consisting of TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and
TiZr.sub.xN.sub.y.
[0050] Pursuant to block 510, the method optionally further
comprise annealing the diffusion barrier layer. In some
embodiments, the annealing may result in a diffusion barrier layer
comprising an interdiffused solid state phase of the plurality of
components present in the plurality of intact layers. Annealing may
be performed at a temperature ranging from about 800.degree. C. to
about 1800.degree. C., from about 800.degree. C. to about
1500.degree. C., or from about 800.degree. C. to about 1000.degree.
C. The annealing temperature may be selected based on the material
of construction of the article, surface, and film layers so as to
maintain their integrity and refrain from deforming, decomposing,
or melting any or all of these components.
[0051] Pursuant to block 515, the method further comprises
depositing an erosion resistant layer onto the diffusion barrier
layer using a second deposition process selected from a group
consisting of ALD, CVD, and PVD. The erosion resistant layer may
comprise a plurality of intact layers. The plurality of intact
layers may be made out of a plurality of precursors, forming an
erosion resistant layer. The erosion resistant layer may have a
thickness of up to about 1 micrometer, e.g. from about 20 nm to
about 1 micrometer, and may be selected from a group consisting of
YF.sub.3, Y.sub.2O.sub.3, Er.sub.2O.sub.3, Al.sub.2O.sub.3,
ZrO.sub.2, ErAl.sub.xO.sub.y, YO.sub.xF.sub.y, YAl.sub.xO.sub.y,
YZr.sub.xO.sub.y and YZr.sub.xAl.sub.yO.sub.z.
[0052] In some embodiments, the method may optionally further
comprise annealing the erosion resistant layer, pursuant to block
520. In some embodiments, the annealing may result in an erosion
resistant layer comprising an interdiffused solid state phase of
the plurality of components present in the plurality of intact
layers. The annealing temperature may be similar to the annealing
temperature of the diffusion barrier layer listed above.
[0053] In some embodiments, the barrier layer and the erosion
resistant layer may both be annealed and interdiffused (FIG. 6D).
In some embodiments, a single annealing process is performed after
deposition of the erosion resistant layer to anneal and
interdiffuse nanolayers of the diffusion barrier layer and
nanolayers of the erosion resistant layer. In some embodiments, one
of the barrier layer and the erosion resistant layer are annealed
and interdiffused, while the other layer is not annealed. (See FIG.
6B and FIG. 6C). In other embodiments, neither of the barrier layer
or the erosion resistant layer is annealed or interdiffused (FIG.
6A). The various embodiments are illustrated in FIGS. 6A-6D and
discussed in further detail below.
[0054] In some embodiments, the first deposition process of the
diffusion barrier layer and the second deposition process of the
erosion resistant layer may be identical, for example, both
processes may be ALD, both process may be CVD, or both processes
may be PVD. In other embodiments, the first deposition process of
the diffusion barrier layer and the second deposition process of
the erosion resistant layer may vary. Regardless of the deposition
method, the final multi-layer coating may be able to withstand
temperature cycling from about 20.degree. C. to about 450.degree.
C. without cracking.
[0055] When the first or second deposition processes are ALD or
CVD, a proper precursor or a plurality of precursors may be
selected to ultimately form the diffusion barrier layer(s), erosion
resistant layer(s), and multi-layer coating.
[0056] For instance, a TiN.sub.x diffusion barrier layer may be
deposited via ALD or CVD from at least one Ti-containing precursor
selected from the group consisting of
bis(diethylamido)bis(dimethylamido)titanium(IV),
tetrakis(diethylamido)titanium(IV),
tetrakis(dimethylamido)titanium(IV),
tetrakis(ethylmethylamido)titanium(IV), titanium(IV) bromide,
titanium(IV) chloride, and titanium(IV) tert-butoxide.
[0057] A TaN.sub.x diffusion barrier layer may be deposited via ALD
or CVD from at least one Ta precursor selected from the group
consisting of pentakis(dimethylamido)tantalum(V), tantalum(V)
chloride, tantalum(V) ethoxide, and
tris(diethylamino)(tert-butylimido)tantalum(V).
[0058] A TiZr.sub.xN.sub.y diffusion barrier layer may be deposited
via ALD or CVD from at least one Ti precursor and from at least one
Zr precursor. Ti precursors may be selected from the group
consisting of bis(diethylamido)bis(dimethylamido)titanium(IV),
tetrakis(diethylamido)titanium(IV),
tetrakis(dimethylamido)titanium(IV),
tetrakis(ethylmethylamido)titanium(IV), titanium(IV) bromide,
titanium(IV) chloride, and titanium(IV) tert-butoxide. Zr
precursors may be selected from the group consisting of zirconium
(IV) bromide, zirconium (IV) chloride, zirconium (IV)
tert-butoxide, tetrakis(diethylamido)zirconium (IV),
tetrakis(dimethylamido)zirconium (IV), and
tetrakis(ethylmethylamido)zirconium (IV). In some embodiments, the
stoichiometric ratios of the various components may form a
Ti.sub.0.2Zr.sub.0.2N.sub.0.6 diffusion barrier layer.
[0059] A Zr.sub.3N.sub.4 diffusion barrier layer may be deposited
via ALD or CVD from at least one Zr precursor selected from the
group consisting of zirconium (IV) bromide, zirconium (IV)
chloride, zirconium (IV) tert-butoxide,
tetrakis(diethylamido)zirconium (IV),
tetrakis(dimethylamido)zirconium (IV), and
tetrakis(ethylmethylamido)zirconium (IV).
[0060] A ErAl.sub.xO.sub.y erosion resistant layer may be deposited
via ALD or CVD from at least one Er precursor and from at least one
Al precursor. Er precursors may be selected from a group consisting
of tris-methylcyclopentadienyl erbium (III) (Er(MeCp).sub.3),
erbium boranamide (Er(BA).sub.3), Er(TMHD).sub.3, erbium(III)
tris(2,2,6,6-tetramethyl-3,5-heptanedionate), and
tris(butylcyclopentadienyl)erbium(III). Al precursors may be
selected from the group consisting of diethylaluminum ethoxide,
tris(ethylmethylamido)aluminum, aluminum sec-butoxide, aluminum
tribromide, aluminum trichloride, triethylaluminum,
triisobutylaluminum, trimethylaluminum, and
tris(diethylamido)aluminum.
[0061] A YAl.sub.xO.sub.y erosion resistant layer may be deposited
via ALD or CVD from at least one Y precursor and from at least one
Al precursor. Y precursors may be selected from the group
consisting of tris(N,N-bis(trimethylsilyl)amide)yttrium (III),
yttrium (III)butoxide, tris(cyclopentadienyl)yttrium(III), and
Y(thd)3 (thd=2,2,6,6-tetramethyl-3,5-heptanedionato).
[0062] A YO.sub.xF.sub.y erosion resistant layer may be deposited
via ALD or CVD from at least one Y precursor selected from the
group consisting of tris(N,N-bis(trimethylsilyl)amide)yttrium
(III), yttrium (III)butoxide, tris(cyclopentadienyl)yttrium(III),
and Y(thd)3 (thd =2,2,6,6-tetramethyl-3,5-heptanedionato).
[0063] A YZr.sub.xO.sub.y erosion resistant layer may be deposited
via ALD or CVD from at least one Y precursor and from at least one
Zr precursor. Zr precursors may be selected from the group
consisting of zirconium (IV) bromide, zirconium (IV) chloride,
zirconium (IV) tert-butoxide, tetrakis(diethylamido)zirconium (IV),
tetrakis(dimethylamido)zirconium (IV), and
tetrakis(ethylmethylamido)zirconium (IV).
[0064] A YZr.sub.xAl.sub.yO.sub.z erosion resistant layer may be
deposited via ALD or CVD from at least one Y precursor, from at
least one Zr precursor and from at least one Al precursor.
[0065] An Er.sub.2O.sub.3 erosion resistant layer may be deposited
via ALD or CVD from at least one Er precursor selected from a group
consisting of tris-methylcyclopentadienyl erbium (III)
(Er(MeCp).sub.3), erbium boranamide (Er(BA).sub.3), Er(TMHD).sub.3,
erbium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), and
tris(butylcyclopentadienyl)erbium(III).
[0066] An Al.sub.2O.sub.3 erosion resistant layer may be deposited
via ALD or CVD from at least one Al precursor selected from the
group consisting of diethylaluminum ethoxide,
tris(ethylmethylamido)aluminum, aluminum sec-butoxide, aluminum
tribromide, aluminum trichloride, triethylaluminum,
triisobutylaluminum, trimethylaluminum, and
tris(diethylamido)aluminum.
[0067] A Y.sub.2O.sub.3 erosion resistant layer may be deposited
via ALD or CVD from at least one Y precursor selected from the
group consisting of tris(N,N-bis(trimethylsilyl)amide)yttrium
(III), yttrium (III)butoxide, tris(cyclopentadienyl)yttrium(III),
and Y(thd).sub.3 (thd=2,2,6,6-tetramethyl-3,5-heptanedionato).
[0068] A YF.sub.3 erosion resistant layer may be deposited via ALD
or CVD from at least one Y precursor.
[0069] A ZrO.sub.2 erosion resistant layer may be deposited via ALD
or CVD from at least one Zr precursor selected from the group
consisting of zirconium (IV) bromide, zirconium (IV) chloride,
zirconium (IV) tert-butoxide, tetrakis(diethylamido)zirconium (IV),
tetrakis(dimethylamido)zirconium (IV), and
tetrakis(ethylmethylamido)zirconium (IV).
[0070] In some embodiments, precursor gases providing an oxygen
source, such as ozone, water vapor, and oxygen radicals from plasma
may be used in conjunction with any of the precursors listed herein
above. In some embodiments, precursor gases providing a nitrogen
source, such as ammonia, nitrogen, and radicals from nitrogen
plasma may be used in conjunction with any of the precursors listed
herein above. In some embodiments, precursor gases providing a
fluorine source, such as fluorine, HF, and fluorine radicals from a
fluorine plasma may be used in conjunction with any of the
precursors listed herein above. It is to be understood that the
precursors listed herein above are merely illustrative and should
not be construed as limiting.
[0071] FIGS. 6A-6D depict variations of a multi-layer coating
according to different embodiments. FIG. 6A illustrates a
multi-layer coating for an article 610 having a surface 605. For
example, article 610 may include various semiconductor process
chamber components including but not limited to substrate support
assembly, an electrostatic chuck (ESC), a ring (e.g., a process kit
ring or single ring), a chamber wall, a base, a gas distribution
plate, gas lines, a showerhead, a nozzle, a lid, a liner, a liner
kit, a shield, a plasma screen, a flow equalizer, a cooling base, a
chamber viewport, a chamber lid, and so on. The semiconductor
process chamber component may be made from a metal (such as
aluminum, stainless steel), a ceramic, a metal-ceramic composite, a
polymer, a polymer ceramic composite, or other suitable materials,
and may further comprise materials such as AN, Si, SiC,
Al.sub.2O.sub.3, SiO.sub.2, and so on.
[0072] In FIGS. 6A-6D, the multi-layer coating deposited on surface
605 comprises a diffusion barrier layer 615 or 645 selected from a
group consisting of TiN.sub.x, TaN.sub.x, Zr.sub.3N.sub.4, and
TiZr.sub.xN.sub.y and an erosion resistant layer 625 or 635
selected from a group consisting of YF.sub.3, Y.sub.2O.sub.3,
Er.sub.2O.sub.3, Al.sub.2O.sub.3, ZrO.sub.2, ErAl.sub.xO.sub.y,
YO.sub.xF.sub.y, YAl.sub.xO.sub.y, YZr.sub.xO.sub.y and
YZr.sub.xAl.sub.yO.sub.z. The erosion resistant layer covers the
diffusion barrier layer.
[0073] In FIG. 6A, both diffusion barrier layer 615 and erosion
resistant layer 625 comprise a plurality of intact layers 650 and
630, respectively. In FIG. 6B, diffusion barrier layer 615
comprises a plurality of intact layers 650, whereas erosion
resistant layer 635 may be in an interdiffused solid state phase of
the plurality of components composing the erosion resistant layer.
In FIG. 6C, diffusion barrier layer 645 may be in an interdiffused
solid state phase of the plurality of components composing the
diffusion barrier layer, whereas erosion resistant layer 625 may
comprise a plurality of intact layers. In FIG. 6D, both diffusion
barrier layer 645 and erosion resistant layer 635 may be in an
inter-diffused solid state phase of the plurality of components
composing each of the layers. Alternatively, the components of the
diffusion barrier layer 645 may interdiffuse to form multiple
different phases and/or the components of the erosion resistant
layer 635 may interdiffuse to form multiple different phases.
[0074] Although the diffusion barrier layer and the erosion
resistant layer illustrated in FIGS. 6A-6D may seem as having a
similar thickness, these figures should not be construed as
limiting. In some embodiments, the diffusion barrier layer may have
a lesser thickness than the erosion resistant layer. In some
embodiments, the diffusion barrier layer may have a greater
thickness than the erosion resistant layer. In some embodiments,
the thickness of the diffusion barrier layer and of the erosion
resistant layer may be the same. The diffusion barrier layer may
have a thickness ranging from about 10 nm to about 100 nm. The
erosion resistant layer may have a thickness of up to about 1
micrometer, e.g., from about 20 nm to about 1 micrometer.
[0075] The surface roughness of the multi-layer coating may be
similar to the roughness of the semiconductor process chamber
component. In some embodiments, the surface roughness of the
multi-layer coating may range from about 20 to about 45
microinches.
[0076] An aluminum oxide erosion resistant layer deposited by ALD
may have the following properties: a breakdown voltage of about 360
volts at a thickness of about 1 micrometer, a scratch adhesion
failure force based on a 10 micron diamond stylus scratch adhesion
test of about 140 mN at a thickness of about 1 micrometer, a
Vickers hardness of about 12.9-13.5 GPa, and a time to failure of
about 1-28 hours for a one micron thick film based on a bubble
test. A yttrium oxide erosion resistant layer deposited by ALD may
have the following properties: a breakdown voltage of about 475
volts at a thickness of about 1 micrometer, a scratch adhesion
failure force based on a 10 micrometer diamond stylus scratch
adhesion test of 34 mN at a thickness of about 100 nm, a Vickers
hardness of about 11.5 GPa to about 12.9 GPa, and about 14 minutes
time to failure for a one micrometer film based on a bubble
test.
[0077] The preceding description sets forth numerous specific
details such as examples of specific systems, components, methods,
and so forth, in order to provide a good understanding of several
embodiments of the present invention. It will be apparent to one
skilled in the art, however, that at least some embodiments of the
present invention may be practiced without these specific details.
In other instances, well-known components or methods are not
described in detail or are presented in simple block diagram format
in order to avoid unnecessarily obscuring the present invention.
Thus, the specific details set forth are merely exemplary.
Particular implementations may vary from these exemplary details
and still be contemplated to be within the scope of the present
invention.
[0078] Reference throughout this specification to "one embodiment"
or "an embodiment" means that a particular feature, structure, or
characteristic described in connection with the embodiment is
included in at least one embodiment. Thus, the appearances of the
phrase "in one embodiment" or "in an embodiment" in various places
throughout this specification are not necessarily all referring to
the same embodiment. In addition, the term "or" is intended to mean
an inclusive "or" rather than an exclusive "or." When the term
"about" or "approximately" is used herein, this is intended to mean
that the nominal value presented is precise within .+-.10%.
[0079] When the term "porosity" is used herein, it is intended to
describe the amount of empty space within the coating. For example,
a 5% porosity would mean that 5% of the total volume of the coating
is actually empty space.
[0080] When the term "surface roughness" is used herein, it
described a measure of the roughness of a surface using a
profilometer (a needle dragged across the surface).
[0081] When the term "break down voltage" or "BDV" is used herein,
it refers to evaluation of the coating using voltage. The BDV value
is the voltage reached when the coating destructively arcs.
[0082] When the term "adhesion" is used herein, it refers to the
strength of the coating to adhere to an underlying article or
underlying coating.
[0083] When the term "hardness" is used herein, it refers to the
amount of compression that a film can withstand without damage.
[0084] When the term "bubble test" is used herein, it refers to a
test in which the coated article is placed in hydrochloric acid
solution, and the time until the formation of a bubble on the
liquid is measured. The formation of the bubble indicates that the
article itself has reacted and the coating has been penetrated.
[0085] The ability to withstand the temperature cycling means that
the multi-layer coating can be processed through temperature cycles
without experiencing cracking.
[0086] Although the operations of the methods herein are shown and
described in a particular order, the order of the operations of
each method may be altered so that certain operations may be
performed in an inverse order or so that certain operation may be
performed, at least in part, concurrently with other operations. In
another embodiment, instructions or sub-operations of distinct
operations may be in an intermittent and/or alternating manner.
[0087] It is to be understood that the above description is
intended to be illustrative, and not restrictive. Many other
embodiments will be apparent to those of skill in the art upon
reading and understanding the above description. The scope of the
disclosure should, therefore, be determined with reference to the
appended claims, along with the full scope of equivalents to which
such claims are entitled.
* * * * *