U.S. patent application number 09/733188 was filed with the patent office on 2001-05-10 for method and materials for through-mask electroplating and selective base removal.
Invention is credited to Andricacos, Panayotis Constantinou, Cabral, Cyril JR., Carruthers, Roy, Grill, Alfred, Saenger, Katherine Lynn.
Application Number | 20010000926 09/733188 |
Document ID | / |
Family ID | 25191485 |
Filed Date | 2001-05-10 |
United States Patent
Application |
20010000926 |
Kind Code |
A1 |
Andricacos, Panayotis Constantinou
; et al. |
May 10, 2001 |
Method and materials for through-mask electroplating and selective
base removal
Abstract
Multilayer metal materials are selected so that the materials
will alloy or intermix under rapid thermal annealing conditions.
The individual materials of the multilayers are preferably chosen
such that at least one of the materials may be selectively etched
with respect to the other material by wet chemical or
electrochemical etching. For electroplating applications, the
alloyed plating base material will assume some of the etch
resistance of the original electrodeposit material such that a
selective wet etch of the plating base can be performed without
substantial undercutting. Furthermore, the graded composition alloy
will exhibit other advantageous physical and chemical properties
for electrode formation and use. The alloying or intermixing may be
accomplished before or after patterning of the materials, for the
instance wherein the materials deposited as blanket layers.
Similarly, the alloying or intermixing may be accomplished before
or after plating base removal for structures deposited by
through-mask plating.
Inventors: |
Andricacos, Panayotis
Constantinou; (Croton-on-Hudson, NY) ; Cabral, Cyril
JR.; (Ossining, NY) ; Carruthers, Roy;
(Stormville, NY) ; Grill, Alfred; (White Plains,
NY) ; Saenger, Katherine Lynn; (Ossining,
NY) |
Correspondence
Address: |
Anne Vachon Dougherty
3173 Cedar Road
P.O. Box 218
Yorktown Heights
NY
10598
US
|
Family ID: |
25191485 |
Appl. No.: |
09/733188 |
Filed: |
December 9, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09733188 |
Dec 9, 2000 |
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08805403 |
Feb 24, 1997 |
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6188120 |
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Current U.S.
Class: |
257/762 ;
257/306; 257/763; 257/768; 257/E21.011; 257/E21.021; 257/E21.175;
438/637; 438/656; 438/672; 438/678 |
Current CPC
Class: |
H01L 28/60 20130101;
H01L 21/2885 20130101; H01L 28/75 20130101 |
Class at
Publication: |
257/762 ;
257/306; 257/763; 257/768; 438/637; 438/656; 438/672; 438/678 |
International
Class: |
H01L 027/108; H01L
029/94; H01L 023/48; H01L 021/4763; H01L 029/40; H01L 031/119; H01L
021/44; H01L 029/76 |
Claims
Having thus described our invention, what we claim as new and
desire to secure by Letters Patent is:
1. A method for electroplating onto a substrate to provide a
pattern of conductive features thereon comprising the steps of:
depositing a blanket layer of first conducting material onto said
substrate; applying a mask material to said blanket layer;
patterning said mask material to provide exposed areas of said
blanket layer in said pattern of features and regions of first
conducting material between said features, which regions remain
covered by said mask material; depositing onto said exposed areas
of said blanket layer a second conducting material which is
different from said first conducting material to form said pattern
of conductive features; removing said mask material; combining said
first and said second conducting materials; and selectively etching
said first conducting material in said regions of first conducting
material between said features.
2. The method of claim 1 wherein said combining comprises alloying
said materials.
3. The method of claim 2 wherein said alloying comprises exposing
said materials to a high temperature anneal.
4. The method of claim 1 wherein said combining comprises
intermixing said materials.
5. The method of claim 1 further comprising applying at least one
additional layer to said substrate prior to deposition of said
blanket layer.
6. The method of claim 1 wherein said selective etching comprises
selective wet chemical etching.
7. The method of claim 1 wherein said selective etching comprises
selective electroetching.
8. A method for providing a pattern of metal features on a
substrate comprising the steps of: depositing a blanket layer of a
first conducting material onto said substrate; applying a mask
material to said blanket layer; patterning said mask material to
provide exposed areas of said blanket layer in said pattern of
metal features and regions of said first conducting material
between said features, which regions remain covered by said mask
material; depositing a second conducting material to said exposed
areas of said blanket layer, said second conducting material being
different from said first conducting material and selected to
combine with said first conducting material; removing said mask
material; and selectively etching said first conducting material in
said regions between said features.
9. The method of claim 8 further comprising the step of combining
said first and said second conducting materials.
10. The method of claim 9 wherein said combining comprises alloying
said materials.
11. The method of claim 10 wherein said alloying comprises exposing
said materials to a high temperature anneal.
12. The method of claim 9 wherein said combining comprises
intermixing said materials.
13. The method of claim 8 further comprising applying at least one
additional layer to said substrate prior to deposition of said
blanket layer.
14. The method of claim 8 wherein said selective etching comprises
selective wet chemical etching.
15. The method of claim 8 wherein said selective etching comprises
selective electroetching.
16. A method for providing a pattern of metal features on a
substrate comprising the steps of: depositing a first blanket layer
of a first noble metal onto said substrate; depositing a second
blanket layer of a second noble metal onto said first blanket
layer, wherein said second noble metal differs from said first
noble metal; patterning said second blanket layer of said second
noble metal to provide second noble metal in said pattern of metal
features and exposed areas of said first blanket layer between said
features; selectively etching said exposed areas of said first
blanket layer between said features.
17. The method of claim 16 further comprising the step of combining
said first and said second conducting materials.
18. The method of claim 17 wherein said combining comprises
annealing.
19. A method for providing a pattern of electrodes on a substrate
comprising the steps of: providing a structure on said substrate
comprising a blanket layer of a first conducting material on the
top surface of said substrate and a plurality of features on said
blanket layer, said features comprising second conducting material
features in said pattern; combining said first and said second
conducting materials to form said electrodes comprising at least
one alloy material formed from said first and said second
conducting materials; and removing said first conducting material
from said top surface of said substrate between said
electrodes.
20. The method of claim 19 wherein said combining comprises
annealing.
21. A method for providing a pattern of electrodes on a substrate
comprising the steps of: providing a pattern of features on said
substrate, each of said features comprising a first conducting
material on the top surface of said substrate and a second
conducting material on the top surface of said first conducting
material; combining said first and said second conducting materials
to form said electrodes comprising at least one alloy material
formed from said first and said second conducting materials.
22. The method of claim 21 wherein said providing of said pattern
of features on said substrate comprises the steps of: depositing a
blanket layer of said first conducting material onto said
substrate; applying a mask material to said blanket layer;
patterning said mask material to provide exposed areas of said
blanket layer in said pattern of features and regions of said first
conducting material between said features, which regions remain
covered by said mask material; depositing said second conducting
material to said exposed areas of said blanket layer, said second
conducting material being different from said first conducting
material and selected to combine with said first conducting
material; removing said mask material; and selectively etching said
first conducting material in said regions between said
features.
23. The method of claim 21 wherein said providing of said pattern
of features on said substrate comprises the steps of: depositing a
blanket layer of said first conducting material onto said
substrate; depositing a blanket layer of said second conducting
material onto said first conducting material; patterning said
second conducting material to provide second conducting material in
said pattern of features and regions of said first conducting
material between said features; and selectively etching said first
conducting material in said regions between said features.
24. The method of claim 21 wherein said combining comprises
annealing said first and said second conducting materials.
25. The method of claim 22 wherein said combining comprises
annealing said first and said second conducting materials.
26. The method of claim 23 wherein said combining comprises
annealing said first and said second conducting materials.
27. A method for providing a pattern of metallization on a
substrate comprising the steps of: depositing a pattern of
dielectric material on said substrate, including exposed regions of
said substrate between features of said pattern; depositing a first
conducting material conformally on said pattern of dielectric
material and said exposed regions of said substrate; depositing a
second conducting material over said first conducting material; and
combining said first and said second conducting materials.
28. The method of claim 27, further comprising the steps of
removing said second and said first conducting materials deposited
over said pattern of dielectric material.
29. The method of claim 27 further comprising the step of
conformally depositing at least one additional layer to said
pattern of dielectric material and said exposed regions of said
substrate prior to said deposition of said first conducting
material.
30. The method of claim 27 wherein said deposition of said second
conducting material is accomplished by plating.
31. A patterned conductive structure formed on a substrate, said
structure comprising: a first portion formed on said substrate,
said first portion comprising at least one alloy of a first
conducting material; and a second portion positioned over said
first portion, said second portion comprising second conducting
material, wherein said at least one alloy comprises an in-situ
formed alloy of said first and said second conducting
materials.
32. The structure of claim 31 wherein said first conducting
material is selected from the group consisting of Pt, Pd, Ir, Rh,
Re, Ru, Os, Au, Ag, Cu, Ni, Sn, Fe, Mo, Ta, In, Ti, Zn, W, or
alloys of those metals.
33. The structure of claim 31 wherein said second conducting
material is selected from the group consisting of Pt, Pd, Ir, Rh,
Re, Ru, Os, Au, Ag, Cu, Ni, Sn, Fe, Mo, Ta, In, Ti, Zn, W, and
alloys of those metals.
34. The structure of claim 31 wherein said second conducting
material is Cu and wherein said first conducting material is
selected from the group consisting of Ni, Fe, Zn, Sn, Mo, Ta, In,
Ti, W, alloys of those metals and Cu alloys.
35. The structure of claim 31 wherein said alloy comprises two or
more of materials selected from the group consisting of Pd, Pt, Ir,
Rh, Ru, Re, Au, Ag, Os, Cu, Ni, Sn, Fe, Mo, Ta, In, Ti, Zn, W, Si
and Ge.
36. A capacitor structure formed on a substrate having a conductive
contact region, said capacitor structure comprising: a first
electrode comprising a first portion formed on said substrate over
said contact region, said first portion comprising at least one
alloy of a first conducting material; and a second portion
positioned over said first portion, said second portion comprising
second conducting material, wherein said at least one alloy
comprises an in-situ formed alloy of said first and said second
conducting materials; a layer of insulating material in contact
with said first electrode; and a second electrode in contact with
said layer of insulating material.
37. A capacitor structure formed on a substrate having a conductive
contact region comprising: a first electrode formed on said
substrate over said contact region; a layer of insulating material
in contact with said first electrode; and a second electrode in
contact with said layer of insulating material, said second
electrode comprising a first portion formed on said substrate, said
first portion comprising at least one alloy of a first conducting
material; and a second portion positioned over said first portion,
said second portion comprising second conducting material, wherein
said at least one alloy comprises an in-situ formed alloy of said
first and said second conducting materials.
38. A capacitor structure formed on a substrate having a conductive
contact region comprising: a first electrode formed on said
substrate over said contact region comprising a first portion
formed on said substrate, said first portion comprising at least
one alloy of a first conducting material and a second portion
positioned over said first portion, said second portion comprising
second conducting material, wherein said at least one alloy
comprises an in-situ formed alloy of said first and said second
conducting materials.; a layer of insulating material in contact
with said first electrode; and a second electrode in contact with
said layer of insulating material, said second electrode comprising
a third portion formed on said substrate, said third portion
comprising at least one alloy of a third conducting material; and a
fourth portion positioned over said third portion, said fourth
portion comprising fourth conducting material, wherein said at
least one alloy comprises an in-situ formed alloy of said third and
said fourth conducting materials.
39. The structure of claim 36 wherein said insulating material is
selected from the group consisting of perovskites, ferroelectrics
and high permittivity materials having dielectric constants
>10.
40. The structure of claim 37 wherein said insulating material is
selected from the group consisting of perovskites, ferroelectrics
and high permittivity materials having dielectric constants
>10.
41. The structure of claim 38 wherein said insulating material is
selected from the group consisting of perovskites, ferroelectrics
and high permittivity materials having dielectric constants >10.
Description
FIELD OF THE INVENTION
1. This invention relates to multilayer metal deposition and
patterning processes and more particularly to a post-deposition
method for selectively removing a conductive plating base from the
regions between patterned electrodeposits, which electrodeposits
have been selectively alloyed.
BACKGROUND OF THE INVENTION
2. In the field of processing semiconductor memory devices,
through-mask electroplating is a method for forming the noble metal
electrodes expected to be required for devices incorporating high
permittivity dielectric or ferroelectric materials. Such electrode
plating is done selectively with the plated deposits being grown in
defined areas of a conductive plating base layer on a substrate,
which areas have been defined by lithography. While, for
consistency of description, both the background of the invention
and the description of the invention will be detailed with specific
reference to through-mask electroplating of electrodes for
semiconductor memory devices, it is not intended that the
applicability of the invention be limited solely to those
processes. It will be apparent to one having skill in the art that
the current invention has applicability for multilayer metal
deposition for other applications as well.
3. Through-mask plating of noble metals (and for non-noble metals
as applicable), is illustrated in FIGS. 1(a) through 1(e).
Reference is made to Assignee's copending application entitled
"Plating of Noble Metal Electrodes for DRAM and FRAM", of
Andricacos, et al, Docket No. YO995-127, Ser. No. 08/636,456, filed
on Apr. 23, 1996, the teachings of which are herein incorporated by
reference. Through-mask plating is generally conducted in
accordance with a process flow that begins with the deposition of a
blanket layer of a conductive plating base, 1 of FIG. 1(a),
deposited over the substrate, 2, on which the electrode deposits
are to be grown. The plating base layer is typically thin, of the
order of 20-100 nm. One or more layers may be deposited on
substrate 2 prior to deposition of the plating base, to improve
adhesion or to act as barriers to interlayer reactions. After the
blanket layer of the plating base has been deposited, a layer of
mask material, 3, is deposited on the plating base layer, followed
by patterning of the mask material to expose areas of the plating
base layer where plating is desired. As shown in FIG. 1(b), the
mask material remains over the regions of the surface which are not
to be plated. The thickness of the mask material should be greater
than or equal to the thickness of the desired electrodeposit. The
mask material, such as organic photoresists or diamond-like carbon
(DLC), should be insulating and compatible with the plating
solution. Next, the entire patterned surface is exposed to a
plating step, whereby the chosen electrode plating material, 4, is
selectively grown on the exposed conductive regions of the sample,
as shown in FIG. 1(c). After electroplating, the mask material is
removed from the areas of the plating base layer which have not
been plated, leaving the structure illustrated in FIG. 1(d); and,
finally the plating base is removed from those areas having no
electrodeposited material, yielding the structure of FIG. 1(e).
4. Plating base removal is typically done by etching. The etchant
and etch method may be selective or non-selective with respect to
the electrode plating material, with selective etches clearly being
preferred, so as to preserve the plated electrode during the
plating base removal process. A complication frequently encountered
is that the materials chosen for the plating base and the plated
electrode are so similar that they respond similarly to a given
etchant or etch process.
5. Furthermore, the etching process may be anisotropic (e.g,
including so-called dry etching processes such as reactive ion
etching) or isotropic (e.g., including so-called "wet" etching such
as a bath of chemical solution). Wet etches are generally not
preferred for plating base removal when fine features are present,
since the wet isotropic etches do give rise to the aforementioned
risk of removal of some or all of the plating base under the
electrode. What is typically encountered with isotropic etching for
plating base removal is partial removal of the plating base at the
edges of the plated electrode feature, an effect known as
"undercutting," as illustrated in the structure of FIG. 2(a). The
amount of undercutting is dependent upon the duration of the etch
process, with the minimum amount of undercut generally about equal
to the thickness of the plating base which is being removed. If the
lateral dimensions of the plated feature are large compared to the
plating base thickness, an undercut of that thickness on each side
of the feature may be tolerable. However, wet etching may be
problematic for the sub-micron dimension electrode structures of
interest for memory device applications, even with plating base
thicknesses of 30-50 nm, since plating base undercutting may expose
underlying contacts or degrade electrodeto-substrate adhesion.
6. As a result of the foregoing concerns, anisotropic (typically
dry) etch processes are preferred for plating base removal from a
device structure having fine-featured electrodeposits. If the dry
etch is selective, it will only remove the plating base which had
been covered by the mask material. If the dry etch is
non-selective, it will remove the plating base and a small amount
of the electrodeposit (i.e., the electrode plating material) at the
top surface of the plated structure. Since the thickness of the
electrodeposit is much greater than the thickness of the plating
base layer, the sacrifice of a small amount of the electrodeposit
from the top surface is acceptable. A disadvantage of using a
physical dry etch process, such as rf-sputtering or ion beam
sputtering, is that the surfaces of the plated electrode structures
may become contaminated with residue from the etching process,
including redeposits of sputtered material comprised of the plating
base material and the underlying surface material, as shown in the
structure of FIG. 2(b). This results in degradation of the
electrical properties of the electrode structure and of a
subsequently-deposited cell dielectric.
7. What is desired, therefore, is a selective etching process which
is not subject to any of the foregoing disadvantages.
8. It is therefore an objective of this invention to provide a
selective etching process for the removal of a conductive noble
metal plating base material from the regions between patterned
electrodeposits of a noble metal material which differs from the
noble metal plating base material.
9. It is another objective of the invention to improve the
properties of layered structures comprised of a plurality of layers
of two or more different conducting materials.
10. It is still another objective of the invention to improve the
properties of layered electrodeposit-on-plating-base structures
intended for microelectronic or micromechanical applications.
11. Yet another objective of the invention is to provide a method
and materials for a through-mask electroplating process which
permits the plating base to be removed from the regions between the
patterned electrodeposits by a wet chemical etch which is selective
and anisotropic.
12. Still another objective is to provide a multilayer metal
structure having improved oxidation resistance.
SUMMARY OF THE INVENTION
13. These and other objectives of the invention are realized by the
present invention whereby multilayer metal materials are selected
so that the materials will alloy or intermix under annealing
conditions. The alloying or intermixing may be accomplished before
or after patterning of the materials for the case where the
materials are deposited as blanket layers. Likewise, the annealing
or intermixing may be accomplished before or after plating base
removal for structures deposited by through-mask plating. The
individual materials of the multilayers are preferably chosen so
that at least one of the materials may be selectively etched with
respect to the other materials by wet chemical or electrochemical
etch. For electroplating applications, the alloyed plating base
material will assume some of the etch resistance of the original
electrodeposit material such that a selective wet etch of the
plating base can be performed without substantial undercutting.
BRIEF DESCRIPTION OF THE DRAWINGS
14. The invention will now be described in further detail with
reference to the Figures in which:
15. FIGS. 1(a) through 1(e) provide schematic illustrations of the
through-mask plating process.
16. FIGS. 2(a) and 2(b) schematically illustrate two structures
exhibiting deleterious effects of plating base removal
processes.
17. FIGS. 3(a) through 3(c) schematically illustrate the process
flow for one embodiment of the present invention.
18. FIGS. 4(a) through 4(c) provide schematic cross-sectional views
of two capacitors having at least one electrode formed in
accordance with the present invention.
19. FIGS. 5(a) through 5(h) schematically illustrate the process
flow for a Damascene version of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
20. With reference to FIGS. 3(a) through 3(c), the present
invention will be described for noble metal electroplating which is
a potentially desirable process for fabricating electrodes for
semiconductor memory cells. FIG. 3(a) illustrates the structure
including a substrate, 2, having a blanket layer of plating base
material, 1, onto which has been electrodeposited a feature
comprising noble metal, 4, which is different from the metal of the
base plating layer. As detailed with reference to the prior art
electroplating processes, the noble metal electrodeposit may have
been electroplated through a mask, which was subsequently removed.
Alternatively, the top metal layer may have been blanket deposited
and then patterned to yield the structure of FIG. 3 (a). The
inventive step comprises subjecting the blanket plating base
layer/electrodeposit structure to a high temperature anneal which
causes the plating base material and the electrodeposit to alloy,
as shown in the structure of FIG. 3(b). It should be understood
that the terms "to alloy," "alloying," and "alloy formation" used
here and elsewhere include the processes of forming metal compounds
as well as solid solutions or two-phase mixtures of metal phases.
Alloy formation in the plating base layer is localized in the
region below the electrodeposit, preferably alloying all of the
plating base material and some of the electrodeposit, as indicated
by the presence of the alloy, 6, and by the decreased depth of pure
metal in the electrodeposit, 4.
21. Next, the unalloyed plating base in the regions between
features is removed with a selective etch to form the structure of
FIG. 3(c). While the FIG. 3(c) structure is illustrated with all of
the underlying alloyed plating base, 6, intact, it is conceivable
that some undercutting may still be encountered depending upon the
materials chosen, the degree of alloying and the etch process used;
however, the degree of undercutting in the inventive structure will
be significantly reduced from that seen in earlier structures, if
not totally eliminated.
22. The anneal step should be long enough to obtain good mixing,
yet short enough to avoid excessive plating base enrichment at the
edges of the electrodeposit and to avoid excessive lateral
diffusion of the electrodeposit into the plating base region
between features. It should be noted that even a partial plating
base/electrodeposit annealing will reap a substantial benefit,
since even a moderate decrease in the etch rate of the plating base
material located underneath the electrodeposit will greatly reduce
undercutting. As will be discussed with reference to FIGS. 4(a) and
4(b), there are additional benefits to alloying the plating base
with the electrodeposit, even if the anneal is conducted after the
plating base material has been removed in the regions between
features.
23. For the illustrated structure, the electrodeposit and the
plating base materials are two different conductive materials. For
example, the electrodeposit and plating base materials may both be
noble metals selected from the group consisting of Ir, Pt, Pd, Rh,
Re, Ru, Os, Ag, Au, or alloys thereof. In one preferred embodiment,
the plating base comprises 30-50 nm of Pd and the electrodeposit
comprises 100-500 nm Pt or Ir. An anneal in the range of
600-750.degree.C. for a period of 1-15 minutes provides sufficient
intermixing of the materials to increase the etch resistance of the
plating base Pd. A suitable selective etch for the Pd plating
base/Pt electrodeposit structure would be a 10:1 mixture of
H.sub.2O.sub.2:H.sub.2SO.sub.4 at a temperature of 65.degree.C.
This etch readily removes Pd but does not attack Pt. Similar
selectivity would be expected for Pd relative to most of the other
noble metals. If plating base enrichment of the electrodeposit is
of particular concern, outweighing the disadvantages of plating
base undercutting, the alloy anneal may be deferred until after
plating base removal. While the anneal cannot then change the
undercut profile of ;Le electrode feature, the resulting alloying
will serve to protect such structures from oxidation during
exposure to the oxidizing environment of subsequent processing.
Pd-Pt alloys will be much more resistant to thermal oxidation than
would pure Pd, which tends to form highly resistive palladium
oxide, thereby degrading the electrical characteristics of the
electrode structures.
24. The plating base and electrodeposit materials for the disclosed
process of plating base removal by self-aligned alloying and
selective etching may be noble metals or non-noble metals. All that
is required is that the plating base be selectively etchable with
respect to the electrodeposit and that some intermixing of plating
base and electrodeposit occur during annealing. Typically, these
conditions can be satisfied with a plating base material selected
to be "less noble" than the overlying electrodeposit. Plating base
and electrodeposit materials can be selected from the group of
metals consisting of: noble metals such as Pt, Pb, Ir, Re, Rh, Ru,
Au, Ag, Os; non-noble metals such as Cu, Ni, Mo, Ta, In, Sn, Nb,
Fe, W, Ti, etc.; and, alloys or combinations of those metals. As an
example, a structure may be fabricated using Cu as the
electrodeposit material and Sn as the plating base. These two
materials readily alloy and form an alloy which can withstand
selective etching of the Sn. An enhanced material results from the
addition of the Sn to the Cu, since the alloying greatly improves
the electromigration resistance of Cu structures which are used for
thin film wiring. This invention thus allows patterned alloy
structures to be formed by plating, without the need for directly
depositing an alloy.
25. For the above example of the Cu-based wiring structure, such
structures might form one or more wiring or via levels in
back-end-of-the-line (BEOL) interconnects or packaging.
Through-mask plating with plating base removal by selective etching
before or after an alloying anneal may be applied to produce a
variety of structures. In the alternative, the plating need not be
through-mask, as discussed further below with reference to FIGS.
5(a) through 5(h). The disclosed process might be used to form the
electrode structures for one or more capacitors or memory elements
in a semiconductor device or package incorporating high-epsilon
dielectric or ferroelectric materials. Cross-sectional schematic
views of exemplary capacitor structures are provided in FIGS. 4(a)
through 4(c). The capacitors shown are approximately cylindrical,
and built on a dielectric layer, 7, containing an embedded
conductive plug, 8, connected to conductive contact regions of
device elements in the substrate (not shown). An optional
conductive diffusion barrier, 9, can be positioned above the
conductive plug. In FIG. 4 (a), the bottom electrode, 10, is formed
by the disclosed process for providing an electrode structure which
is at least partially alloyed. When a high epsilon or ferroelectric
material, 11, is disposed between the bottom electrode, 10, and the
counterelectrode, 12, the bottom electrode material does not
undergo oxidation, nor does the capacitor experience the resulting
degraded performance attendant to electrode oxidation. FIG. 4(b)
illustrates a structure wherein the bottom electrode, 13, is formed
by conventional means, but the counterelectrode is formed by the
disclosed process. FIG. 4(c) illustrates a capacitor structure in
which both top and bottom electrodes are fabricated in accordance
with the present invention, which would necessitate the use of a
sacrificial fill material to maintain the gap between the
electrodes during electrode processing, followed by removal of that
fill material, and filling of the gap with the high-epsilon
material.
26. With reference to FIGS. 5(a) through 5(h), the invention may be
implemented using a Damascene processing flow. FIG. 5(a) shows a
substrate comprising a conductive contact, 15, embedded in
dielectric material, 7. A dielectric layer, 16, is deposited, as
shown in FIG. 5(b), and patterned to form a cavity, 17, for the
wiring metallurgy, as shown in 5(c). The resulting structure is
then coated with a conductive plating base layer, 18, to form the
structure of FIG. 5(d). Layer 18 might be, for example, a layer of
Sn, from 1-50 nm in thickness. If needed, one or more layers (not
shown) may be deposited on the structure of FIG. 5(c) prior to
plating base deposition in order to improve adhesion or to act as
barriers to interlayer reactions. The metal-lined cavity is next
filled with a conductive material, 19, as shown in FIG. 5(e). The
conductive material may be, for example, cu electroplated onto the
plating base layer. The structure of FIG. 5(e) is then planarized
by a process such as chemical mechanical polishing (CMP) to form
the structure of FIG. 5(f). After annealing to form the alloyed
metal structure, shown in FIG. 5(g) to include the alloyed
metallurgy 20, the unreacted plating base may be removed by a
process such as selective wet etching, yielding the structure of
FIG. 5(h). Alloyed metallurgy 20 may alternatively be formed by
first removing the exposed plating base from the structure of FIG.
5(f) by a process such as CMP or wet etching, followed by the
annealing step.
27. Compositionally inhomogeneous alloy electrodes for one or more
capacitors or memory elements in a semiconductor device or package
may also be formed by depositing one or more layers of two or more
conductive materials, by a process such as physical vapor
deposition (PVD), chemical vapor deposition (CVD), or electrolytic
or electroless plating. After deposition, the process flow includes
partial or total intermixing or alloying of the layers by a heating
process such as rapid thermal annealing, where the intermixing or
alloying can be performed before, during or after electrode
patterning. The intermixing or annealing step incorporated into a
method for producing alloyed electrodes may also be applied to the
formation of structural elements other than electrodes for
semiconductor memory devices, for example to fabricate
micromechanical devices. Furthermore, the inventive process is not
limited to materials deposited by plating. For example, a blanket
bilayer of Pt over Pd might be deposited, patterned, and then
annealed. The individual layers may be pure metals, or metals
alloyed with metals or non-metals, forming alloys which comprise
two or more of the following materials: Pd, Pt, Ir, Rh, Ru, Re, Au,
Ag, Os, Cu, Ni, Sn, Fe, Mo, Ta, In, Ti, Zn, W, Si and Ge. Alloy
electrodes produced in this way would be expected to have
characteristically inhomogeneous compositions that would differ
from those of electrodes initially deposited as alloys.
Inhomogeneous or graded-composition materials might be desirable in
cases where the surface or top portion of a structural element is
preferably enriched in one alloy component (e.g., a noble metal
such as Pt which does not easily oxidize) while the bottom portion
of the structural element must be enriched in the other alloy
component for reasons of, for example, stress relief, adhesion
enhancement, or chemical inertness with respect to substrate
reactions (e.g., Ti for adhesion, Ir for resistance to silicide
formation when deposited on a silicon-containing substrate, etc.).
Therefore, incorporation of the annealing step of the present
invention to provide in-situ formation of an alloy provides a
structure having a superior geometric profile after plating base
removal, a structure having favorable physical and chemical
properties for withstanding subsequent processing, and a structure
comprised of a graded material formed by relatively simple
processing over prior art bi-layer or alloy deposits.
* * * * *