U.S. patent application number 14/326404 was filed with the patent office on 2014-10-30 for processes and systems for engineering a copper surface for selective metal deposition.
The applicant listed for this patent is Lam Research Corporation. Invention is credited to Tiruchirapalli Arunagiri, John Boyd, Yezdi Dordi, Arthur M. Howald, Fritz C. Redeker, William Thie.
Application Number | 20140322446 14/326404 |
Document ID | / |
Family ID | 41136973 |
Filed Date | 2014-10-30 |
United States Patent
Application |
20140322446 |
Kind Code |
A1 |
Dordi; Yezdi ; et
al. |
October 30, 2014 |
PROCESSES AND SYSTEMS FOR ENGINEERING A COPPER SURFACE FOR
SELECTIVE METAL DEPOSITION
Abstract
An integrated system for transferring and processing a substrate
in a controlled environment to enable selective deposition of a
thin layer of a cobalt-alloy material on a copper surface of a
copper interconnect to improve electromigration performance of the
copper interconnect, comprising: a lab-ambient transfer chamber; a
substrate cleaning reactor coupled to the lab-ambient transfer
chamber, wherein the substrate cleaning reactor cleans the
substrate surface to remove metal-organic complex contaminants on
the substrate surface; a vacuum transfer chamber; a vacuum process
module for removing organic contaminants from the substrate
surface; a controlled-ambient transfer chamber filled with an inert
gas; and an electroless cobalt-alloy material deposition process
module used to deposit the thin layer of cobalt-alloy material on
the copper surface of the copper interconnect after the substrate
surface has been removed of metallic contaminants and organic
contaminants, and the copper surface has been removed of copper
oxide.
Inventors: |
Dordi; Yezdi; (Palo Alto,
CA) ; Boyd; John; (Hillsboro, OR) ; Arunagiri;
Tiruchirapalli; (Fremont, CA) ; Redeker; Fritz
C.; (Fremont, CA) ; Thie; William; (Mountain
View, CA) ; Howald; Arthur M.; (Pleasanton,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Lam Research Corporation |
Fremont |
CA |
US |
|
|
Family ID: |
41136973 |
Appl. No.: |
14/326404 |
Filed: |
July 8, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11513634 |
Aug 30, 2006 |
8771804 |
|
|
14326404 |
|
|
|
|
60713494 |
Aug 31, 2005 |
|
|
|
Current U.S.
Class: |
427/294 ;
118/50 |
Current CPC
Class: |
H01L 21/288 20130101;
C23C 18/1893 20130101; H01L 21/76814 20130101; H01L 21/76862
20130101; H01L 21/7684 20130101; H01L 21/76849 20130101; H01L
21/67161 20130101; B05C 13/02 20130101; C23C 18/1851 20130101; H01L
21/02063 20130101; H01L 21/32115 20130101; H01L 21/76843 20130101;
H01L 21/76846 20130101; H01L 21/02068 20130101; B05D 3/002
20130101; H01L 21/28518 20130101; H01L 21/02074 20130101; H01L
21/0206 20130101; C23C 18/1651 20130101; H01L 21/32136 20130101;
H01L 21/67207 20130101; H01L 21/32135 20130101 |
Class at
Publication: |
427/294 ;
118/50 |
International
Class: |
B05C 13/02 20060101
B05C013/02; B05D 3/00 20060101 B05D003/00 |
Claims
1. An integrated system for transferring and processing a substrate
in controlled environment to enable selective deposition of a thin
layer of a cobalt-alloy material on a copper surface of a copper
interconnect to improve electromigration performance of the copper
interconnect, comprising: a lab-ambient transfer chamber capable of
transferring the substrate from a substrate cassette coupled to the
lab-ambient transfer chamber into the integrated system; a
substrate cleaning reactor coupled to the lab-ambient transfer
chamber, wherein the substrate cleaning reactor cleans the
substrate surface to remove metal-organic complex contaminants on
the substrate surface; a vacuum transfer chamber operated under
vacuum at a pressure less than 1 Torr, wherein at least one vacuum
process module is coupled to the vacuum transfer chamber; a vacuum
process module for removing organic contaminants from the substrate
surface; wherein the vacuum process module is one of the at least
one vacuum process module coupled to the vacuum transfer chamber,
and is operated under vacuum at a pressure less than 1 Torr; a
controlled-ambient transfer chamber filled with an inert gas
selected from a group of inert gases, and at least one
controlled-ambient process module coupled to the controlled-ambient
transfer chamber; and an electroless cobalt-alloy material
deposition process module used to deposit the thin layer of
cobalt-alloy material on the copper surface of the copper
interconnect after the substrate surface has been removed of
metallic contaminants and organic contaminants, and the copper
surface has been removed of copper oxide, the electroless
cobalt-alloy material deposition process module being one of the at
least one controlled-ambient process module coupled to the
controlled-ambient transfer chamber and is filled with an inert gas
selected from a group of inert gases and having a fluid delivery
system where process fluids are de-gassed.
2. The integrated system of claim 1, further comprising: a
hydrogen-containing reduction process module used to reduce
residual copper oxide on the copper surface into copper, wherein
the hydrogen-containing reduction process module is coupled to the
vacuum transfer chamber, the hydrogen-containing reduction process
module is operated under vacuum at a pressure less than 1 Torr.
3. The integrated system of claim 1, wherein the substrate cleaning
reactor that cleans the substrate surface to remove metal
contaminants on the substrate surface is a wet clean reactor,
employing a wet clean solution containing TMAH.
4. The integrated system of claim 1, further comprises a second
substrate cleaning reactor coupled to the lab-ambient transfer
chamber, wherein the second substrate cleaning reactor cleans the
substrate surface to remove metal oxides on the substrate surface,
employing a wet clean solution containing one of citric acid,
sulfuric acid, or sulfuric acid with hydrogen peroxide.
5. The integrated system of claim 1, further comprising: a
substrate cleaning process module used to clean the substrate
surface after the copper surface of the substrate has been
deposited with the thin layer of the cobalt-alloy material.
6. The integrated system of claim 5, wherein the substrate cleaning
process module is filled with an inert gas selected from a group of
inert gases and is one of the at least one controlled-ambient
process module coupled to the controlled-ambient transfer
module.
7. The integrated system of claim 1, further comprising: a first
loadlock coupled to the vacuum transfer chamber and the
controlled-ambient transfer chamber, wherein the first loadlock
assists the substrate to be transferred between the vacuum transfer
chamber and the controlled-ambient transfer chamber, the first
loadlock configured to be operated under vacuum at pressure less
than 1 Torr or to be filled with an inert gas selected from a group
of inert gases to operated under the same pressure as the
controlled-ambient transfer module; and a second loadlock coupled
to the vacuum transfer chamber and the lab-ambient transfer
chamber, wherein the second loadlock assists the substrate to be
transferred between the vacuum transfer chamber and the lab-ambient
transfer chamber, the second loadlock configured to be operated
under vacuum at pressure less than 1 Torr or at lab ambient.
8. The integrated system of claim 1, wherein the vacuum transfer
chamber and the at least one vacuum process module coupled to the
vacuum transfer chamber are operated at a pressure less than 1 Torr
to limit the exposure of the substrate to oxygen.
9. The integrated system of claim 1, wherein the controlled-ambient
transfer chamber and the at least one controlled-ambient process
module coupled to the controlled-ambient transfer chamber are
filled with one or more of inert gases selected from the group of
inert gases to limit the exposure of the substrate to oxygen.
10. The integrated system of claim 1, wherein substrate is
transferred and processed in the integrated system to limit a
duration the substrate is exposed to oxygen.
11. The method of claim 10, wherein limiting the exposure of the
substrate surface to oxygen reduces the induction time of the
deposition reaction and enhances the thin layer of the cobalt-alloy
material being selectively deposited on the copper surface.
12. The integrated system of claim 1, wherein the at least one
process module coupled to the controlled-ambient transfer module
enables a dry-in/dry-out processing of the substrate, wherein the
substrate goes in a dry state and comes out in a dry state.
13. The integrated system of claim 12, wherein the electroless
cobalt-alloy material deposition process module is coupled to a
rinse and dry system to enable the dry-in/dry-out processing.
14. An integrated system for transferring and processing a
substrate in a controlled environment to enable selective
deposition of a thin layer of a cobalt-alloy material on a copper
surface of a copper interconnect to improve electromigration
performance of the copper interconnect, comprising: a lab-ambient
transfer chamber capable of transferring the substrate from a
substrate cassette coupled to the lab-ambient transfer chamber into
the integrated system; a substrate cleaning reactor coupled to the
lab-ambient transfer chamber, wherein the substrate cleaning
reactor cleans the substrate surface to remove metal-organic
complex contaminants on the substrate surface; a vacuum transfer
chamber operated under vacuum at a pressure less than 1 Torr,
wherein at least one vacuum process module is coupled to the vacuum
transfer chamber; a vacuum process module for removing organic
contaminants from the substrate surface; wherein the vacuum process
module is one of the at least one vacuum process module coupled to
the vacuum transfer chamber, and is operated under vacuum at a
pressure less than 1 Torr; a controlled-ambient transfer chamber
filled with an inert gas selected from a group of inert gases, and
at least one controlled-ambient process module coupled to the
controlled-ambient transfer chamber; and an electroless
cobalt-alloy material deposition process module used to deposit the
thin layer of cobalt-alloy material on the copper surface of the
copper interconnect after the substrate surface has been removed of
metallic contaminants and organic contaminants, and the copper
surface has been removed of copper oxide, the electroless
cobalt-alloy material deposition process module being one of the at
least one controlled-ambient process module coupled to the
controlled-ambient transfer chamber and is filled with an inert gas
selected from a group of inert gases and having a fluid delivery
system where process fluids are de-gassed; a hydrogen-containing
reduction process module used to reduce residual copper oxide on
the copper surface into copper, wherein the hydrogen-containing
reduction process module is coupled to the vacuum transfer chamber,
the hydrogen-containing reduction process module is operated under
vacuum at a pressure less than 1 Torr; wherein the substrate is
transferred and processed in the integrated system to limit a
duration the substrate is exposed to oxygen; wherein limiting the
exposure of the substrate surface to oxygen reduces the induction
time of the deposition reaction and enhances the thin layer of the
cobalt-alloy material being selectively deposited on the copper
surface; wherein the at least one process module coupled to the
controlled-ambient transfer module enables a dry-in/dry-out
processing of the substrate, wherein the substrate goes in a dry
state and comes out in a dry state.
15. The integrated system of claim 14, wherein the substrate
cleaning reactor that cleans the substrate surface to remove metal
contaminants on the substrate surface is a wet clean reactor,
employing a wet clean solution containing TMAH.
16. The integrated system of claim 14, further comprises a second
substrate cleaning reactor coupled to the lab-ambient transfer
chamber, wherein the second substrate cleaning reactor cleans the
substrate surface to remove metal oxides on the substrate surface,
employing a wet clean solution containing one of citric acid,
sulfuric acid, or sulfuric acid with hydrogen peroxide.
17. The integrated system of claim 14, further comprising: a
substrate cleaning process module used to clean the substrate
surface after the copper surface of the substrate has been
deposited with the thin layer of the cobalt-alloy material.
18. The integrated system of claim 17, wherein the substrate
cleaning process module is filled with an inert gas selected from a
group of inert gases and is one of the at least one
controlled-ambient process module coupled to the controlled-ambient
transfer module.
19. The integrated system of claim 14, further comprising: a first
loadlock coupled to the vacuum transfer chamber and the
controlled-ambient transfer chamber, wherein the first loadlock
assists the substrate to be transferred between the vacuum transfer
chamber and the controlled-ambient transfer chamber, the first
loadlock configured to be operated under vacuum at pressure less
than 1 Torr or to be filled with an inert gas selected from a group
of inert gases to operated under the same pressure as the
controlled-ambient transfer module; and a second loadlock coupled
to the vacuum transfer chamber and the lab-ambient transfer
chamber, wherein the second loadlock assists the substrate to be
transferred between the vacuum transfer chamber and the lab-ambient
transfer chamber, the second loadlock configured to be operated
under vacuum at pressure less than 1 Torr or at lab ambient.
Description
CLAIM OF PRIORITY
[0001] This application claims priority as a continuation of U.S.
application Ser. No. 11/513,634, titled "Processes and Systems for
Engineering a Copper Surface for Selective Metal Deposition," filed
on Aug. 30, 2006, which claims priority of U.S. Provisional
Application Ser. No. 60/713,494, titled "High Rate Electroless
Plating and Integration Flow to Form Cu Interconnects," filed on
Aug. 31, 2005, which is hereby incorporated by reference.
CROSS REFERENCE TO RELATED APPLICATION
[0002] This application is related to U.S. patent application Ser.
No. 11/514,038 (Attorney Docket No. LAM2P568B, now U.S. Pat. No.
8,241,701), entitled "Processes and Systems for Engineering a
Bather Surface for Selective Copper Deposition," and U.S. Pat. No.
8,747,960 (Attorney Docket No. LAM2P568C), entitled "Processes and
Systems for Engineering a Silicon-Type Surface for Selective Metal
Deposition to Form a Metal Silicide," both of which are filed on
the same day as the instant application. The disclosure of these
related applications is incorporated herein by reference in their
entireties for all purposes.
BACKGROUND
[0003] Integrated circuits use conductive interconnects to wire
together the individual devices on a semiconductor substrate, or to
communicate externally to the integrated circuit. Interconnect
metallization for vias and trenches may include aluminum alloys and
copper. Electro-migration (EM) is a well-known reliability problem
for metal interconnects, caused by electrons pushing and moving
metal atoms in the direction of current flow at a rate determined
by the current density. Electro-migration can eventually lead to
the thinning of the metal line, which can result in higher
resistivity or, worst case, a metal line breakage. Fortunately, not
every interconnect metal line on an IC has current moving in the
same direction all the time, as it mostly does in power supply and
ground lines. However, as metal lines get narrower (International
Technology Roadmap for Semiconductors (ITRS) calls for a
.about.0.7.times. reduction in the line width for every technology
node), electro-migration becomes more of an issue.
[0004] In aluminum lines, EM is a bulk phenomenon and is well
controlled by the addition of small amounts of a dopant, such as
copper. EM in copper lines, on the other hand, is a surface
phenomenon. It can occur wherever the copper is free to move,
typically at an interface where there is poor adhesion between the
copper and another material. In today's dual-damascene process,
this happens most often on the top of the copper line where it
interfaces with what is typically a SiC diffusion barrier layer,
but it can also happen at the copper/barrier interface. With each
migration to the next technology node, and resulting increase in
current density, the problem worsens.
[0005] The solution to EM problems, as well as related stress
voids, another common reliability problem, has been a story of
process integration: optimized depositions (i.e. reducing thickness
of barrier and seed layers), pre- and post-deposition wafer
cleanings, surface treatments, etc., all aimed at providing
homogeneous surfaces and good adhesion between layers to minimize
metal atom migration and void propagation. In the dual-damascene
process, trenches and holes (for contacts and vias) are etched in
the dielectric, then lined with a barrier material, such as
tantalum (Ta), tantalum nitride (TaN), or a combination of both
films, followed by the deposition of a copper seed layer, copper
electroplating, copper planarization using CMP and then deposition
of a dielectric stack, such as SiC/low-k/SiC. Since an oxide
readily forms on copper when copper is exposed to air, proper
post-CMP cleaning and removal of the copper oxide before capping
the copper with SiC is required to ensure good adhesion between
copper and SiC. Removal of the copper oxide prior to the SiC
deposition is essential to good EM performance and reducing
resultant metal resistivity.
[0006] Recently, capping Copper with a cobalt-alloy capping layer,
such as CoWP (cobalt tungsten phosphide), CoWB (cobalt tungsten
boride), or CoWBP (cobalt tungsten boro-phosphide), before the SiC
dielectric barrier layer, has been shown to significantly improve
electro-migration, compared to SiC over copper. FIG. 1 shows that
the cobalt-alloy capping layers 20, 30 are deposited over copper
layers 23, 33 and under dielectric capping SiC layers 25, 35,
respectively. Ta and/or TaN barrier layers are illustrated as
layers 24, 34. The cobalt-alloy layers 20, 30 improve the adhesion
between copper 23, 33 and SiC cap layers 25, 35. The cobalt-alloy
layers 20, 30 can also exhibit certain copper diffusion barrier
characteristics. The cobalt-alloy capping layers can be selectively
deposited on copper by electroless deposition. However, the
electroless deposition can be inhibited by thin copper oxide layer,
which can be formed when copper is exposed to air. Further,
contaminants on the copper and dielectric surfaces can cause
pattern-dependent plating effects include pattern-dependent
thickness of the Co alloy, as well as pattern-dependent copper line
thickness loss in part due to etching during the `incubation` time
required to initiate the Co plating reaction. Therefore, it is
important to control the processing environment to limit (or
control) the growth of native copper oxide, and to remove copper
oxide and organic contaminants on the copper surface and organic
and metallic contaminants on the dielectric surface immediately
prior to depositing the metallic capping layer, such as a
cobalt-alloy. Further, to reduce pattern-dependent deposition
variability, the dielectric surface must be controlled to normalize
its influence across structures of different pattern densities.
Engineering the metal-to-metal interface between the copper layers
23, 33, between copper and barrier layers 33 and 34, 23 and 24, and
the adhesion promoting layers (or metallic capping layers), such as
the cobalt-alloy layers 20, 20, is very critical in ensuring good
interfacial adhesion and good EM performance. Further, as metal
lines become narrower, physical vapor deposition (PVD) barrier and
seed films form a larger part of the metal line, increase the
effective resistivity, and hence current density. Thin and
conformal barrier and seed layers can mitigate this trend, with
atomic layer deposition (ALD) barriers (TaN, Ru or hybrid
combinations) providing conformal step coverage and acceptable
barrier properties, and electroless Cu process providing a
conformal seed layer. Until now, however, there is no electroless
Cu seed layer that can adhere to the ALD TaN barrier films
produced.
[0007] In view of the foregoing, there is a need for systems and
processes that produce a metal-to-metal interface with improved
electro-migration performance, low sheet resistance, and improved
interfacial adhesion for copper interconnects.
SUMMARY
[0008] Broadly speaking, the embodiments fill the need by providing
improved processes and systems that produce an improved
metal-to-metal interface, more specifically copper-to-cobalt-alloy
interface, to enhance electro-migration performance, provide lower
metal resistivity, and improve metal-to-metal interfacial adhesion
for copper interconnects. It should be appreciated that the present
invention can be implemented in numerous ways, including as a
solution, a method, a process, an apparatus, or a system. Several
inventive embodiments of the present invention are described
below.
[0009] In one embodiment, a method of preparing a substrate surface
of a substrate to selectively deposit a thin layer of a
cobalt-alloy material on a copper surface of a copper interconnect
of the substrate in an integrated system to improve
electromigration performance of the copper interconnect is
provided. The method includes removing contaminants and metal
oxides from the substrate surface in the integrated system, and
reconditioning the substrate surface using a reducing environment
after removing contaminants and metal oxides in the integrated
system. The method also includes selectively depositing the thin
layer of cobalt-alloy material on the copper surface of the copper
interconnect in the integrated system after reconditioning the
substrate surface.
[0010] In another embodiment, a method of preparing a substrate
surface of a substrate to selectively deposit a layer of a
cobalt-alloy material on a copper surface of a copper interconnect
of the substrate in an integrated system is provided. The method
includes removing metal-organic complex contaminants and metal
oxides from the substrate surface in the integrated system, and
removing organic contaminants from the substrate surface in the
integrated system. The method also includes removing a metallic
barrier overburden of the copper interconnect in the integrated
system, after the metal-organic complex contaminants, metal oxides
and organic contaminants are removed from the substrate surface.
The method further includes selectively depositing the thin layer
of the cobalt-alloy material on the copper surface of the copper
interconnect in the integrated system after removing the metallic
barrier overburden.
[0011] In another embodiment, a method of preparing a substrate
surface to selectively deposit a layer of a cobalt-alloy material
on a copper surface of a copper interconnect of the substrate in an
integrated system to improve electromigration performance of the
copper interconnect is provided. The method includes removing
metal-organic complex contaminants and metal oxides from the
substrate surface in the integrated system, and removing organic
contaminants from substrate surface in the integrated system. The
method also includes removing a thin layer of copper overburden
over a metallic barrier overburden of the copper interconnect in
the integrated system after removing the metal-organic complex
contaminants, the metal oxide, and the organic contaminants from
the substrate surface. The method further includes removing the
metallic barrier overburden in the integrated system after removing
the thin layer of copper overburden, wherein after removing the
metallic barrier overburden the substrate is transferred and
processed in controlled environment to prevent the formation of
copper oxide. In addition, the method includes selectively
depositing the thin layer of the cobalt-alloy material on the
copper surface in the integrated system.
[0012] In another embodiment, an integrated system for transferring
and processing a substrate in controlled environment to enable
selective deposition of a thin layer of a cobalt-alloy material on
a copper surface of a copper interconnect to improve
electromigration performance of the copper interconnect is
provided. The integrated system includes a lab-ambient transfer
chamber capable of transferring the substrate from a substrate
cassette coupled to the lab-ambient transfer chamber into the
integrated system, and a substrate cleaning reactor coupled to the
lab-ambient transfer chamber, wherein the substrate cleaning
reactor cleans the substrate surface to remove metal-organic
complex contaminants on the substrate surface.
[0013] The system also includes a vacuum transfer chamber operated
under vacuum at a pressure less than 1 Torr, wherein at least one
vacuum process module is coupled to the vacuum transfer chamber,
and a vacuum process module for removing organic contaminants from
the substrate surface; wherein the vacuum process module is one of
the at least one vacuum process module coupled to the vacuum
transfer chamber, and is operated under vacuum at a pressure less
than 1 Torr. The system further includes a controlled-ambient
transfer chamber filled with an inert gas selected from a group of
inert gases, and at least one controlled-ambient process module
coupled to the controlled-ambient transfer chamber. In addition,
the system includes an electroless cobalt-alloy material deposition
process module used to deposit the thin layer of cobalt-alloy
material on the copper surface of the copper interconnect after the
substrate surface has been removed of metallic contaminants and
organic contaminants, and the copper surface has been removed of
copper oxide, the electroless cobalt-alloy material deposition
process module being one of the at least one controlled-ambient
process module coupled to the controlled-ambient transfer chamber
and is filled with an inert gas selected from a group of inert
gases and having a fluid delivery system where process fluids are
de-gassed.
[0014] Other aspects and advantages of the invention will become
apparent from the following detailed description, taken in
conjunction with the accompanying drawings, illustrating by way of
example the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The present invention will be readily understood by the
following detailed description in conjunction with the accompanying
drawings, and like reference numerals designate like structural
elements.
[0016] FIG. 1 shows an exemplary cross section interconnects.
[0017] FIGS. 2A-2D show cross sections of an interconnect structure
at various stages of interconnect processing.
[0018] FIG. 3 shows various forms of contaminants on substrate
surface after metal CMP.
[0019] FIG. 4A shows an exemplary process flow to prepare a copper
surface for electrolessly depositing a cobalt-alloy.
[0020] FIG. 4B shows an exemplary system used to process a
substrate through a process flow of FIG. 4A.
[0021] FIGS. 5A-5C show cross sections of an interconnect structure
at various stages of interconnect processing.
[0022] FIG. 6A shows an exemplary process flow to prepare a copper
surface for electrolessly depositing a cobalt-alloy.
[0023] FIG. 6B shows an exemplary system used to process a
substrate through a process flow of FIG. 6A.
[0024] FIGS. 7A-7C show cross sections of an interconnect structure
at various stages of interconnect processing.
[0025] FIG. 8A shows an exemplary process flow to prepare a copper
surface for electrolessly depositing a cobalt-alloy.
[0026] FIG. 8B shows an exemplary system used to process a
substrate through a process flow of FIG. 8A.
[0027] FIGS. 9A-9E show cross sections of a metal line structure at
various stages of processing.
[0028] FIG. 10A shows an exemplary process flow to prepare a
barrier layer surface for electrolessly depositing a copper
layer.
[0029] FIG. 10B shows an exemplary system used to process a
substrate through a process flow of FIG. 10A.
[0030] FIG. 10C shows an exemplary process flow to prepare a
barrier layer surface for electrolessly depositing a copper
layer.
[0031] FIG. 10D shows an exemplary system used to process a
substrate through a process flow of FIG. 10C.
[0032] FIG. 11A shows an exemplary process flow to prepare a
barrier layer surface for electrolessly depositing a copper layer
and to prepare a copper surface for electrolessly depositing a
cobalt-alloy.
[0033] FIG. 11B shows an exemplary system used to process a
substrate through a process flow of FIG. 11A.
[0034] FIGS. 12A-12D show cross sections of an interconnect
structure at various stages of processing.
[0035] FIG. 13A shows an exemplary process flow to prepare a
barrier surface for electroless copper deposition and to prepare a
copper surface for electrolessly depositing a cobalt-alloy.
[0036] FIG. 13B shows an exemplary system used to process a
substrate through a process flow of FIG. 13A.
[0037] FIGS. 14A-14D show cross section of a gate structure at
various stages of forming metal silicide.
[0038] FIG. 15A shows an exemplary process flow to prepare exposed
silicon surface to form a metal silicide.
[0039] FIG. 15B shows an exemplary system used to process a
substrate through a process flow of FIG. 15A.
[0040] FIG. 16 shows a schematic diagram of system integration for
an integrated system with ambient-controlled processing
environments.
DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS
[0041] Several exemplary embodiments for improved metal integration
techniques that modify metal interfaces by removing interfacial
metal oxide by reduction to improve electro-migration metal
resistivity and interface adhesion are provided. It should be
appreciated that the present invention can be implemented in
numerous ways, including a process, a method, an apparatus, or a
system. Several inventive embodiments of the present invention are
described below. It will be apparent to those skilled in the art
that the present invention may be practiced without some or all of
the specific details set forth herein.
[0042] FIG. 2A shows an exemplary cross-section of an interconnect
structure(s) after being patterned by using a dual damascene
process sequence. The interconnect structure(s) is on a substrate
50 and has a dielectric layer 100, which was previously fabricated
to form a metallization line 101 therein. The metallization line is
typically fabricated by etching a trench into the dielectric 100
and then filling the trench with a conductive material, such as
copper.
[0043] In the trench, there is a barrier layer 120, used to prevent
the copper material 122, from diffusing into the dielectric 100.
The barrier layer 120 can be made of PVD tantalum nitride (TaN),
PVD tantalum (Ta), ALD TaN, or a combination of these films. Other
barrier layer materials can also be used. A barrier layer 102 is
deposited over the planarized copper material 122 to protect the
copper material 122 from premature oxidation when via holes 114 are
etched through overlying dielectric materials 104, 106 to the
barrier layer 102. The barrier layer 102 is also configured to
function as a selective etch stop and a copper diffusion barrier.
Exemplary barrier layer 102 materials include silicon nitride (SiN)
or silicon carbide (SiC).
[0044] A via dielectric layer 104 is deposited over the barrier
layer 102. The via dielectric layer 104 can be made of an
organo-silicate glass (OSG, carbon-doped silicon oxide) or other
types of dielectric materials, preferably with low dielectric
constants. Exemplary silicon dioxides can include, a PECVD un-doped
TEOS silicon dioxide, a PECVD fluorinated silica glass (FSG), a HDP
FSG, OSG, porous OSG, etc. and the like. Commercially available
dielectric materials including Black Diamond (I) and Black Diamond
(II) by Applied Materials of Santa Clara, Calif., Coral by Novellus
Systems of San Jose, Aurora by ASM America Inc. of Phoenix, Ariz.,
can also be used. Over the via dielectric layer 104 is a trench
dielectric layer 106. The trench dielectric layer 106 may be a low
K dielectric material, such as a carbon-doped oxide (C-oxide). The
dielectric constant of the low K dielectric material can be about
3.0 or lower. In one embodiment, both the via and trench dielectric
layers are made of the same material, and deposited at the same
time to form a continuous film. After the trench dielectric layer
106 is deposited, the substrate 50 that holds the structure(s)
undergoes patterning and etching processes to form the vias holes
114 and trenches 116 by known art.
[0045] FIG. 2B shows that after the formation of vias holes 114 and
trenches 116, a barrier layer 130 and a copper layer 132 are
deposited to line and fill the via holes 114 and the trenches 116.
The barrier layer 130 can be made of tantalum nitride (TaN),
tantalum (Ta), Ruthenium (Ru), or a hybrid combination of these
films. While these are the commonly considered materials, other
barrier layer materials can also be used. A copper film 132 is then
deposited to fill the via holes 114 and the trenches 116.
[0046] After copper film 132 fills the via holes 114 and trenches
116, substrate 50 is planarized by chemical-mechanical polishing
(CMP) to remove the copper material (or copper overburden) and
barrier layer (or barrier overburden) over the surface of
dielectric 106, as shown in FIG. 2C. The next step is to cap the
copper surface 140 with a copper/SiC interface adhesion promoter
layer 135, such as a cobalt-alloy, as shown in FIG. 2D. Examples of
the cobalt-alloy include: CoWP, CoWB, or CoWBP, which can be
selectively deposited over copper by an electroless process. The
thickness of the adhesion-promoting layer can be as thin as a
monolayer, which is only a few angstroms, such as 5 angstroms, to a
thicker layer, such as 200 to 300 angstroms, which could also serve
as a Cu diffusion barrier, eliminating the need for a dielectric
cap.
[0047] Chemical-mechanical polishing (CMP) of copper often uses
benzotrizole (BTA) as a copper corrosion inhibitor. Copper forms
Cu-BTA complexes with BTA. A substrate that has been processed
through Cu CMP and post-CMP clean can contain copper residues in
the form of a Cu-BTA complex, which is illustrated as open circles
in FIG. 3, on both the Cu lines and the adjacent dielectric. Cu-BTA
complexes on the dielectric need to be removed to prevent increased
current leakage or metal shorting. Further, residues of Ta or other
barrier material, which is illustrated as open triangles in FIG. 3,
may be present in small amounts, in addition to various organic
contaminants, which are illustrated as filled circles in FIG. 3. In
addition to these contaminants, there are various oxides of the
metals present, primarily CuO and CuO.sub.2, which are illustrated
as filled triangles in FIG. 3. Cu-BTA complexes metal oxides, and
organic contaminants are three major surface contaminants that must
be removed from the substrate surface. Preparing a dielectric
surface and a metal surface that are free of organics and
metal-containing compound contaminants is challenging and requires
multiple surface preparation steps that could include both wet and
dry processes.
[0048] Following are several exemplary process flows and systems
that provide surface preparation of an underlying metal to allow an
over-laying metal layer to be deposited on top with good adhesion
properties between the two metal layers. The metal layers deposited
by the exemplary process flows and systems would exhibit improved
EM performance and thus an overall lower metal resistivity.
1. Engineering Copper Surface for Cobalt-Alloy Deposition
CASE I: Metal CMP Stops on Dielectric Layer
[0049] FIG. 4A shows an embodiment of a process flow of surface
preparation for electrolessly depositing a cobalt-alloy over a
post-CMP copper surface 140 of the dual-damascene via-trench
structure shown in FIG. 2C. The substrate(s) used in the process
flow 400 of FIG. 4A have just finished metal CMP processing(s) to
remove copper and bather overburden layers, such as Ta and/or TaN.
As described above in the paragraph related to FIG. 3, there are
various metallic and organic contaminants on the substrate
surface.
[0050] The process starts at step 401 by removing metal-organic
complex contaminants (or complexed metal-organic contaminants),
such as Cu-BTA complex, and metal oxides from the substrate
surface. Although metal contaminants will be removed from both the
copper and dielectric surfaces, the purpose of this step is to
enhance selectivity and improve the Co film morphology by
eliminating potential sources of metal that could later serve as
nucleation sites for the subsequent Co-alloy deposition. Copper-BTA
complex, copper oxide (CuO.sub.x) and other metal oxides, such as
tantalum oxide (TaO.sub.y), are removed from the substrate surface
during this step. The amount of copper oxide to be removed depends
on the contaminant level and depth of metal oxides on the surface.
Metal complex and metal oxide can be removed by an O.sub.2/Ar
sputtering process, or a wet chemical removal process in an 1-step
or a 2-step wet chemical process sequence. The preferred embodiment
uses a wet process to remove the complexed metal and metal oxides.
The wet chemical removal process can use an organic acid, such as
DeerClean offered by Kanto Chemical Co., Inc. of Japan or a
semi-aqueous solvent, such as ESC 5800 offered by DuPont of
Wilmington, Del., an organic base such as tetramethylammonium
chloride (TMAH), complexing amines such as ethylene diamine,
diethylene triamine, or proprietary chemistry such as ELD clean and
Cap Clean 61, provided by Enthone, Inc. of West Haven, Conn.
Removing Cu-BTA from the dielectric surface ensures that copper
from the Cu-BTA complex will not be oxidized to copper oxide and
subsequently reduced to copper during other surface preparation
steps, reducing selectivity and providing nucleation points on the
dielectric surface on which to grow the Co alloy, causing shorts
and increasing the leakage current. Therefore, Cu-BTA removal
process can also reduce yield loss due to metal shorting or current
leakage.
[0051] Cu-BTA complexes and other metal oxide contaminants are two
key metal contaminants to be removed during this step, which can be
done in either a controlled or uncontrolled ambient (or
environment). For example, Cu-BTA can be removed by a wet clean
process that involves a cleaning solution including
tetramethylammonium hydroxide (TMAH), complexing amines such as
ethylene diamine, diethylene triamine, or proprietary cleaning
chemistries such as ELD clean and Cap Clean 61, provided by
Enthone, Inc. of West Haven, Conn. Metal oxides, specifically
copper oxide, can be removed using a weak organic acid such as
citric acid, or other organic or inorganic acids can be used.
Additionally, very dilute (i.e. <0.1%) peroxide-containing
acids, such as sulfuric-peroxide mixtures, can also be used. The
wet clean process can also remove other metal or metal oxide
residues.
[0052] The presence of BTA on the copper lines of different pattern
or feature types, such as small dense, small isolated or wide
copper lines, is a result of passivation of the lines, the amount
of which is related, in part, to the degree of the galvanic effect
occurring on these features. This can result in the formation of
pattern-dependent passivation layers. This dependence can further
influence the Co-alloy deposition characteristics, resulting in
pattern-dependent deposition characteristics, sometimes referred to
as incubation or initiation effects. Removing BTA from the Cu lines
can help eliminate this pattern-dependent deposition effect of
cobalt-alloy (to be deposited at a subsequent step) and allow
uniform cobalt-alloy deposition in the dense and isolated
features.
[0053] The organic contaminants can be removed by an oxidizing
plasma such as an oxygen-containing plasma process in step 403. The
oxygen (O.sub.2) plasma process is preferably conducted at a
relatively low temperature of less than 120.degree. C. High
temperature O.sub.2 plasma process tends to oxidize copper into a
thicker layer, making it harder to reduce later. Therefore, a low
temperature O.sub.2 plasma process is preferred. In one embodiment,
the O.sub.2 plasma process can be a downstream plasma process.
Alternatively, organic residues (or contaminants) can also be
removed by using an O.sub.2/Ar sputtering process to physically
remove the organic contaminants. O.sub.2 plasma process and
O.sub.2/Ar sputtering process are typically operated under less
than 1 Torr.
[0054] Once the substrate surface is free of contaminants, such as
Cu-BTA, metal oxide, and other organic contaminants, the substrate
should be exposed to as little oxygen as possible to protect the
copper surface from oxidation. Copper oxidation is not a
self-limiting process. The amount and duration of oxygen the copper
surface is exposed to should be limited (or controlled) to minimize
the copper oxide formation. Although copper oxide will be reduced
at a later step, thicker layers of copper oxide may not be fully
reduced. Therefore, it is important to limit the exposure of copper
to oxygen to only that needed to remove the organic contaminants.
To achieve controlled and limited exposure to oxygen, the substrate
should be transferred or processes in controlled environments, such
as an environment under vacuum or an environment filled with inert
gas (es).
[0055] To ensure that the copper surface is free of copper oxide,
the substrate surface is reconditioned in a reducing environment to
convert any residual copper oxide into copper at step 405. The
previous pre-clean steps will have removed any metals from the
dielectric layer, and thus metal reduction is performed only on the
copper lines. The copper surface reduction can be achieved by a
hydrogen-containing plasma process to convert copper oxide to
copper (or substantially copper). Exemplary reactive gases that can
be used to generate the hydrogen-containing plasma include hydrogen
(H.sub.2), ammonia (NH.sub.3), and carbon monoxide (CO). For
example, the substrate surface is reduced by a hydrogen-containing
plasma, which is generated by hydrogen (H.sub.2) gas, ammonia
(NH.sub.3) gas, or a combination of both gases, and the substrate
is at an elevated temperature of between 20.degree. C. and
300.degree. C. In one embodiment, the hydrogen plasma process is a
downstream plasma process. Once the substrate goes through a
hydrogen reduction process, the substrate is ready for the
cobalt-alloy deposition. The copper surface needs to be carefully
protected to ensure no copper oxide formation. As described above,
electroless deposition of cobalt-alloy can be inhibited by the
presence of copper oxide. Therefore, it is important to control the
processing and transport environments to minimize the exposure of
the copper surface to oxygen.
[0056] At next process step 407, the cobalt-alloy, such as CoWP,
CoWB or CoWBP, is electrolessly deposited on top of the copper
surface. The electroless deposition of the cobalt-alloy is a wet
process, and deposits on catalytic surfaces, such as copper
surface, only. The cobalt-alloy only deposits selectively on the
copper surface.
[0057] After the electroless deposition of the cobalt-alloy, the
process flow can enter an optional process step 409 of a
post-deposition clean. Post-deposition clean can be accomplished by
using a brush scrub clean with a chemical solution, such as a
solution containing CP72B supplied by Air Products and Chemical,
Inc. of Allentown, Pa. Other substrate surface cleaning processes
can also be used, such as Lam's C3.TM. or P3.TM. cleaning
technology. Other post clean chemicals can include a
hydroxylamine-based chemistry to remove any metal-based
contaminants that might remain on the dielectric surface after
electroless plating.
[0058] As described above, the process and wafer transfer
environment control is very important for preparing the copper
surface for cobalt-alloy deposition, especially after the hydrogen
plasma reduction of the copper surface. FIG. 4B shows a schematic
diagram of an exemplary integrated system 450 that allows minimal
exposure of substrate surface to oxygen at critical steps after
surface treatment. In addition, since it is an integrated system,
the substrate is transferred from one process station immediately
to the next process station, which limits the duration that the
prepared copper surface is exposed to oxygen. The integrated system
450 can be used to process substrate(s) through the entire process
sequence of flow 400 of FIG. 4A.
[0059] As described above, the surface treatments, electroless
deposition of cobalt-alloy and the optional post-cobalt-alloy
deposition process involve a mixture of dry and wet processes. The
wet processes are typically operated near atmosphere, while the dry
O.sub.2 plasma, hydrogen plasma, and O.sub.2/Ar sputtering are all
operated at less than 1 Torr. Therefore, the integrated system
needs to be able to handle a mixture of dry and wet processes. The
integrated system 450 has 3 substrate transfer modules (or
chambers) 460, 470, and 480. Transfer chambers 460, 470 and 480 are
equipped with robots to move substrate 455 from one process area to
another process area. The process area could be a substrate
cassette, a reactor, or a loadlock. Substrate transfer module 460
is operated under lab ambient, which refers to the laboratory (or
factory) environment that is under room temperature, atmospheric
pressure and exposed to air, usually HEPA- or ULPA-filtered to
control particle defects. Module 460 interfaces with substrate
loaders (or substrate cassettes) 461 to bring the substrate 455
into the integrated system or to return the substrate to the
cassette(s) 461 to continue processing outside the system 450.
[0060] As described above in process flow 400, the substrate 455 is
brought to the integrated system 450 to be deposited with a
cobalt-alloy, such as CoWB, CoWP, or CoWBP, after the substrate has
been planarized by metal CMP to remove excess metal from the
substrate surface and leaves the metal only in the metal trenches,
as shown in FIG. 2C. As described in step 401 of process flow 400,
the substrate, surface needs to be removed of surface contaminants
such as Cu-BTA complex and other metal oxide residues. Cu-BTA and
metal oxides can be removed by a wet clean process involving clean
solution, such as a solution containing TMAH or complexing amines
such as, but not limited to, ethylene diamine or diethylamine
triamine. Following BTA-metal complex removal, metal oxides
remaining on the copper and dielectric surfaces can be removed
using a wet clean process involving a clean solution such as a
solution containing citric acid, or other organic acid that can
remove copper oxide more or less selectively to copper. Metal
oxides, specifically copper oxide, can be removed using a weak
organic acid such as citric acid, or other organic or inorganic
acids can be used. Additionally, very dilute (i.e. <0.1%)
peroxide-containing acids, such as sulfuric-peroxide mixtures, can
also be used. The wet clean process can also remove other metal or
metal oxide residues.
[0061] A wet clean reactor 463 can be integrated with the
lab-ambient transfer module 460, which is operated at lab ambient
condition. The wet clean reactor 463 can be used to perform the
1-step or 2-step clean described above at step 401 of FIG. 4A.
Alternatively, an additional wet clean reactor 463' can be
integrated with the lab-ambient transfer module 460 to allow the
first step of the 2-step cleaning process to be performed in
reactor 463 and the second step be performed in reactor 463'. For
example, a cleaning solution containing chemical such as TMAH for
cleaning Cu-BTA is in reactor 463 and a cleaning solution
containing a weak organic acid such as citric acid for cleaning
metal oxide is in reactor 463'.
[0062] A lab ambient condition is under atmosphere and open to air.
Although the wet clean reactor 463 can be integrated with the
lab-ambient transfer module 460 in the process flow 400, this
process step can also be performed right after metal CMP and before
the substrate is brought to the integrated system for cobalt-alloy
deposition. Alternatively, the wet cleaning process can be
performed in a controlled ambient process environment, where the
controlled ambient is maintained during and after the wet cleaning
step.
[0063] Organic residues (or contaminants) not removed by the
previous wet cleans can be removed by a dry oxidizing plasma
process, such as oxygen-containing plasma, O.sub.2/Ar sputter, or
Ar sputter following the removal of Cu-BTA and metal oxides. As
described above, most plasma or sputtering processes are operated
below 1 Torr; therefore, it is desirable to couple such systems (or
apparatus, or chambers, or modules) to a transfer module that is
operated under vacuum at pressure, such as under 1 Torr. If the
transfer module integrated with the plasma process is under vacuum,
substrate transfer is more time efficient and the process module is
maintained under vacuum, since it does not require extended time to
pump down the transfer module. In addition, since the transfer
module is under vacuum, the substrate after cleaning by the plasma
process is exposed to only very low levels of oxygen. Assuming the
O.sub.2 plasma process is selected to clean the organic residues,
the O.sub.2 plasma process reactor 471 is coupled to a vacuum
transfer module 470.
[0064] Since lab-ambient transfer module 460 is operated at
atmosphere and vacuum transfer module 470 is operated under vacuum
(<1 Ton), a loadlock 465 is placed between these two transfer
modules to allow substrate 455 to be transferred between the two
modules, 460 and 470, operated under different pressures. Loadlock
465 is configured to be operated under vacuum at pressure less than
1 Torr, or at lab ambient, or to be filled with an inert gas
selected form a group of inert gases.
[0065] After substrate 455 finishes the oxidizing plasma processing
using O.sub.2, for example, substrate 455 is moved into the
hydrogen-containing reducing plasma reduction chamber (or module)
473. Hydrogen-containing plasma reduction is typically processed at
a low pressure, which is less than 1 Torr; therefore, it is coupled
to the vacuum transfer module 470. Once the substrate 455 is
reduced with hydrogen-containing plasma, the copper surface is
clean and free of copper oxide. In a preferred embodiment, after
substrate 455 finishes the O.sub.2 plasma processing, a H.sub.2 or
H.sub.2/NH.sub.3 plasma reduction step can be performed in-situ,
without removing the wafer from the chamber. In either case, the
substrate is ready for cobalt-alloy deposition after completion of
the reduction process.
[0066] As described above, it is important to control the
processing and transport environments to minimize the exposure of
the copper surface to oxygen after the substrate is reconditioned
by the hydrogen-containing reducing plasma. The substrate 455
should be process under a controlled environment, where the
environment is either under vacuum or filled with one or more inert
gas to limit the exposure of substrate 455 to oxygen. Dotted line
490 outlines the boundary of a part of the integrated system 450 of
FIG. 4B that show the processing systems and transfer modules whose
environment is controlled. Transferring and processing under
controlled environment 490 limits the exposure of the substrate to
oxygen.
[0067] Cobalt-alloy electroless deposition is a wet process that
involves cobalt species in a solution that is reduced by a reducing
agent, which can be phosphorous-based (e.g. hypophosphite),
boron-based (e.g. dimethylamine borane), or a combination of both
phosphorous-based and boron-based. The solution that uses
phosphorous-based reducing agent deposits CoWP. The solution that
uses boron-based reducing agent deposit CoWB. The solution that
uses both phosphorous-based and boron-based reducing agents
deposits CoWBP. In one embodiment, the cobalt-alloy electroless
deposition solution is alkaline-based. Alternatively, cobalt-alloy
electroless deposition solution can also be acidic. Since wet
process is typically conducted under atmospheric pressure, the
transfer module 480 that is coupled to the electroless deposition
reactor should be operated near atmospheric pressure. To ensure the
environment is controlled to be free of oxygen, inert gas (es) can
be used to fill the controlled-ambient transfer module 480.
Additionally, all fluids used in the process are de-gassed, i.e.
dissolved oxygen is removed by commercially available degassing
systems. Exemplary inert gas includes nitrogen (N.sub.2), helium
(He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe).
[0068] In one embodiment, the wet cobalt-alloy electroless
deposition reactor (or apparatus, or system, or module) is coupled
with a rinse and dry system (or apparatus, or module) to allow the
substrate to be transferred into the electroless deposition system
481 under dry condition and to come out of the system 481 in dry
condition (dry-in/dry-out). The dry-in/dry-out requirement allows
the electroless deposition system 481 to be integrated with the
controlled-ambient transfer module 480, and avoids the need of a
wet robotic transfer step to a separate rinse-dry module. The
environment of the electroless deposition system 481 also needs to
be controlled to provide low (or limited) levels of oxygen and
moisture (water vapor). Inert gas can also be used to fill the
system to ensure low levels of oxygen are in the processing
environment.
[0069] Alternatively, cobalt-alloy electroless deposition can also
be conducted in a dry-in/dry-out manner similar to electroless
copper disclosed recently. A dry-in/dry-out electroless copper
process has been developed for copper electroless deposition. The
process uses a proximity process head to limit the electroless
process liquid in contacting with the substrate surface on a
limited region. The substrate surface not under the proximity
process head is dry. Details of such process and system can be
found in U.S. application Ser. No. 10/607, 611, titled "Apparatus
And Method For Depositing And Planarizing Thin Films On
Semiconductor Wafers," filed on Jun. 27, 2003, and U.S. application
Ser. No. 10/879,263, titled "Method and Apparatus For Plating
Semiconductor Wafers," filed on Jun. 28, 2004, both of which are
incorporated herein in their entireties. The electroless plating of
cobalt-alloy can use similar proximity processing head to enable a
dry-in/dry-out process.
[0070] After cobalt-alloy deposition in system 481, the substrate
455 can be sent through an optional post-deposition cleaning
reactor. This can be performed using mechanical assists, such as a
brush scrub using chemistry such as CP72B or hydroxylamine-based
cleaning chemistries or by using other methods, such as immersion
cleaning, spin-rinse cleaning, or C3.TM. proximity technology. A
rinse and dry system must also be integrated with the brush scrub
system to allow substrate 455 to be dry-in/dry-out of the wet
cleaning system 483. Inert gas (es) is used to fill system 483 to
ensure limited (or low) oxygen is present in the system. The system
483 is dotted to illustrate that this system is optional, since the
post-deposition cleaning is optional, as described above in FIG.
4A. Since the post-deposition clean step is the last process that
is to be operated by the integrated system 450, the substrate 455
needs to be brought back into cassette 461 after processing.
Therefore, the cleaning system 483 can alternatively be coupled to
the lab-ambient transfer module 460, as shown in FIG. 4B. If the
cleaning system 483 is coupled to the lab-ambient transfer module
460, the cleaning system 483 is not operated under controlled
environment and inert gas (es) does not need to fill the
system.
[0071] As described above, the Cu-BTA and metal oxide removal
process step(s) can also be performed right after metal CMP and
before the substrate is brought to the integrated system for
cobalt-alloy deposition.
CASE II: Metal CMP Stops on Barrier Layer
[0072] FIGS. 5A-5C show the cross sections of an interconnect
structure at various stages of processing. The copper layer on the
substrate of FIG. 5A has been planarized by CMP. The barrier layer
130 has not been removed, and remains on the substrate surface.
FIG. 6A shows an embodiment of a process flow of surface
preparation for electrolessly depositing a cobalt-alloy over copper
in the dual-damascene metal trench. The substrate(s) used in the
process flow 600 of FIG. 6A have just finished copper CMP
processing(s) to remove copper. Barrier layer still remains on the
substrate surface, as shown in FIG. 5A. The difference between Case
II and Case I is that in Case II the surface of dielectric 106 is
not exposed to Cu-BTA complex or other copper compound residues.
The dielectric surface has higher quality (or less metal
contaminants) in Case II than in Case I. Therefore, process step(s)
aiming at removing copper oxide on the dielectric layer, which is
formed after O.sub.2 plasma used to remove organic contaminants,
can be eliminated.
[0073] The process starts at step 601 of removing metallic
contaminants, such as Cu-BTA or metal oxides, from the substrate
surface. As described above, Cu-BTA complexes and metallic oxides
are two key surface metallic contaminants to be removed. The
processes used to remove metallic contaminants, such as Cu-BTA and
metal oxides, from the substrate surface have been described above.
For example, Cu-BTA and metal oxides, including copper oxides, can
be removed by a wet clean process that involves a cleaning solution
that includes, for example, tetramethylammonium hydroxide (TMAH) or
complexing amines such as ethylenediamine or diethylenetriamine
Removing Cu-BTA eliminates pattern-dependent deposition effect of
cobalt-alloy (to be deposited at a later step) and hence allows
uniform cobalt-alloy deposition in the dense and isolated
features.
[0074] Metal oxides, specifically copper oxide, can be removed
using a weak organic acid such as citric acid, or other organic or
inorganic acids can be used. Additionally, very dilute (i.e.
<0.1%) peroxide-containing acids, such as sulfuric-peroxide
mixtures, can also be used. The wet clean process can also remove
other metal or metal oxide residues.
[0075] The organic contaminants, including remaining BTA on the Cu
and bather surfaces, are removed at step 602. Organic contaminants
can be removed by a process such as a dry oxygen (O.sub.2) plasma
process or other oxidizing plasma processes, such as plasma process
with H.sub.2O, ozone, or hydrogen peroxide vapor. As described
above, the oxygen-containing plasma process is preferably conducted
at a relatively low temperature, below 50.degree. C. and preferably
below 120.degree. C. The oxygen-containing plasma process can be a
downstream plasma process. Alternatively, organic residues (or
contaminants) can also be removed by using an O.sub.2/Ar sputtering
process to physically remove the organic contaminants. As described
above, O.sub.2 plasma process and O.sub.2/Ar sputtering process are
typically operated under less than 1 Torr.
[0076] Once the substrate surface is free of contaminants, such as
Cu-BTA, metal oxides and organic contaminants, the substrate should
be exposed to as little oxygen as possible to protect the copper
surface from further oxidation. After surface contaminants are
removed, at step 603, barrier layer, such as Ta, TaN, Ru, or a
combination of the materials, is removed from substrate surface, as
shown in FIG. 5B. Barrier layer can be removed by processes, such
as CF.sub.4 plasma, O.sub.2/Ar sputtering, CMP, or by a wet
chemical etch. Both CF.sub.4 plasma etch and O.sub.2/Ar sputtering
processes are operated at less than 1 Torr.
[0077] Copper oxide existing at the copper surface 140 of FIG. 5A
and produced during the plasma oxidation step might be completely
removed during the barrier metal removal step 603. Therefore, the
process of using H-containing plasma to reduce copper surface
becomes optional. However, to ensure that the copper surface is
free of copper oxide, the substrate surface can (optionally) be
reduced to convert any residual copper oxide into copper at step
605. The copper surface reduction can be achieved by a
hydrogen-containing plasma process to convert copper oxide to
copper. Process gas (es) and process condition used by the
hydrogen-containing plasma process have been described above in
Case I. Once the substrate went through a hydrogen reduction
process, the substrate is ready for the cobalt-alloy deposition.
The copper surface needs to be carefully protected from oxygen to
ensure no copper oxide formation. As described above, electroless
deposition of cobalt-alloy can be inhibited by the presence of
copper oxide. Therefore, it's important to control the processing
and transport environments to minimize or to eliminate the exposure
of the copper surface to oxygen.
[0078] At next process step 607, the cobalt-alloy, such as CoWP,
CoWB or CoWBP, is electrolessly deposited on the top of the copper
surface. Cobalt-alloy is shown as layer 135 in FIG. 5C. The
electroless deposition of the cobalt-alloy is a selective
deposition and is a wet process. The cobalt-alloy only deposits on
the copper surface.
[0079] As described above for Case I, after the electroless
deposition of the cobalt-alloy, the process flow can enter an
optional process step 609 of a post-deposition clean.
Post-deposition clean can be performed by using a brush scrub clean
with a chemical solution, such as a solution containing CP72B
supplied by Air Products and Chemical, Inc. of Allentown, Pa., or
by hydroxylamine-base chemicals, in order to removal any metal
contaminants on the dielectric surface introduced by the
electroless deposition process. Other substrate surface cleaning
processes can also be used.
[0080] As described above, the environment control is very
important for preparing the copper surface for cobalt-alloy
deposition, especially after the H-containing plasma reduction of
the copper surface. FIG. 6B shows a schematic diagram of an
exemplary integrated system 650 that allows minimal exposure of
substrate surface to oxygen at critical steps after surface
treatment. The integrated system 650 can be used to process
substrate(s) through the entire process sequence of flow 600 of
FIG. 6A.
[0081] Similar to the integrated system 450, the integrated system
650 has 3 substrate transfer modules 660, 670, and 680. Transfer
modules 660, 670 and 680 are equipped with robots to move substrate
655 from one process area to another process area. Substrate
transfer module 660 is operated under lab ambient. Module 660
interfaces with substrate loaders (or substrate cassettes) 661 to
bring the substrate 655 into the integrated system or to return the
substrate to the cassette(s) 661 to continue processing outside the
system 650.
[0082] As described above in process flow 600, the substrate 655 is
brought to the integrated system 650 to be deposited with a
cobalt-alloy, such as CoWB, CoWP, or CoWBP, after the substrate has
been planarized by copper CMP to remove excess copper from the
substrate surface and leaves barrier layer on the dielectric
surface and copper in the metal trenches, as shown in FIG. 5A. As
described in step 601 of process flow 600, the substrate surface
needs to be removed of surface contaminants such as Cu-BTA, metal
oxides and organic residues. Cu-BTA and metal oxides can be removed
by a wet clean process involving clean solution, such as a solution
containing TMAH. A wet clean reactor 663 can be integrated with the
lab-ambient transfer module 660. Although the wet clean reactor 663
can be integrated with the lab-ambient transfer module 660 in the
process flow 600, this process step can also be performed right
after metal CMP and before the substrate is brought to the
integrated system for cobalt-alloy deposition. Alternatively, the
wet cleaning process can be performed in a controlled ambient
process environment, where the controlled ambient is maintained
during and after the wet cleaning step.
[0083] Organic residues (or contaminants) not removed by the wet
clean process 601 performed in reactor 683 can be removed by a dry
plasma process, such as O.sub.2 plasma or O.sub.2/Ar sputter, at
step 602. As described above, most plasma or sputtering processes
are operated below 1 Torr; therefore, it's desirable to couple such
systems to a transfer module that is operated under vacuum at
pressure, such as under 1 Torr. Assuming O.sub.2 plasma process is
selected to clean the organic residue, the O.sub.2 plasma process
reactor 671 is coupled to a vacuum transfer module 670.
[0084] The O.sub.2 plasma process can be a downstream plasma
process. Although the O.sub.2 plasma reactor 671 can be integrated
with the vacuum transfer module 670 in the process flow 600, this
process step can also be performed right after metal CMP and before
the substrate is brought to the integrated system for cobalt-alloy
deposition.
[0085] Since lab-ambient transfer module 660 is operated under
atmosphere and vacuum transfer module 670 is operated under vacuum
(<1 Ton), a loadlock 665 is placed between these two transfer
modules to allow substrate 655 to be transferred between the two
modules, 660 and 670.
[0086] After substrate 655 finishes the O.sub.2 plasma processing,
substrate 655 is moved into a processing system for barrier layer
etch, as shown in step 603. The barrier layer etch chamber (or
module) 673, if a dry barrier plasma etch process is selected, can
be coupled to the vacuum transfer module 670. The dry barrier
plasma process can be a CF.sub.4 plasma process or an O.sub.2/Ar
sputtering process.
[0087] The process following barrier layer etch is an optional
H-containing plasma reduction to ensure no copper oxide remains on
the copper surface. The H.sub.2 plasma reduction can be performed
in a plasma chamber (or module) 674, which is coupled to the vacuum
transfer module 670. Alternatively, hydrogen plasma reduction can
also be performed sequentially in the O.sub.2 plasma reactor 671
used to remove organic residues after purging the chamber of
residual oxygen species.
[0088] As described above, cobalt-alloy electroless deposition is a
wet chemical process. Since a wet process is typically conducted at
atmospheric pressure, the transfer module 680 that is coupled to
the electroless deposition reactor should be operated near
atmospheric pressure. To ensure the environment is controlled to be
free of oxygen, inert gas (es) can be used to fill the
controlled-ambient transfer module 680. Additionally, all fluids
used in the process are de-gassed, i.e. dissolved oxygen is removed
by commercially available degassing systems.
[0089] The wet cobalt-alloy electroless deposition reactor needs to
be coupled with a rinse and dry system to allow the substrate to be
transferred to the electroless deposition system 681 under dry
conditions and to come out of the system 681 in dry condition
(dry-in/dry-out). As described above, the dry-in/dry-out
requirement allows the electroless deposition system 681 to be
integrated with the controlled-ambient transfer module 680. Inert
gas (es) is used to fill system 681 to ensure low (or limited, or
controlled) oxygen levels are maintained in the system.
[0090] After cobalt-alloy deposition in system 681, the substrate
655 can be sent through a post-deposition cleaning reactor 683. A
rinse and dry system also needs to be integrated with the brush
scrub system to allow substrate 655 to be dry-in/dry-out of the wet
cleaning system 683. Inert gas (es) is used to fill system 683 to
ensure no oxygen is present. The system 683 is dotted to illustrate
that this system is optional, since the post-deposition cleaning is
optional, as described above in FIG. 6A. Since the post-deposition
clean step is the last process that is to be operated by the
integrated system 650, the substrate 655 needs to be brought back
into cassette 661 after processing. The cleaning system 683 can
alternatively be coupled to the lab-ambient transfer module
660.
CASE III: Metal CMP Stops on a Thin Copper Layer
[0091] FIGS. 7A-7C show cross sections of an interconnect structure
at various stages of interconnect processing. The substrate in FIG.
7A has just finished copper planarization, but has not fully
cleared the copper from the substrate. A thin copper layer 132
remains on the substrate surface. FIG. 8A shows an embodiment of a
process flow of surface preparation for electrolessly depositing a
cobalt-alloy over copper in the dual-damascene metal trench. The
substrate(s) used in the process flow 800 of FIG. 8A have just
finished copper CMP processing(s) to remove most of the copper
above the barrier layer over dielectric layer. A thin layer of
copper in the range between about 100 angstrom to about 1000
angstrom is left on the barrier surface, as shown in FIG. 7A. The
difference between Case III and both Case I and Case II is that in
Case III a thin layer of copper cover the entire substrate surface;
therefore there is no concern of galvanic corrosion of copper due
to exposed dissimilar materials in the copper CMP solution. Since
the thin copper layer and other surface contaminants present will
be removed in an oxygen-free environment, there is no concern of
copper oxidation. Therefore, no H.sub.2 plasma reduction is needed.
Both Case II and Case III do not have barrier CMP; therefore, metal
CMP processing cost is reduced. The copper surface prepared by this
process allows excellent selectivity of cobalt-alloy on the copper
versus on dielectric layer.
[0092] The process starts at step 801 of removing contaminants,
including organic residues and inorganic metal oxides, from the
substrate surface. The organic contaminants can be removed by an
oxidizing plasma such as a dry oxygen (O.sub.2) plasma process,
H.sub.2O plasma process, H.sub.2O.sub.2 plasma process, or a plasma
with ozone vapor. As described above, the O.sub.2 plasma process is
preferably conducted at a relatively low temperature less than
120.degree. C. The O.sub.2 plasma process can be a downstream
plasma process. Alternatively, organic residues (or contaminants)
can also be removed by using an O.sub.2/Ar sputtering process to
physically remove the organic contaminants. As described above,
O.sub.2 plasma process and O.sub.2/Ar sputtering process are
typically operated under less than 1 Torr.
[0093] Once the substrate surface is free of contaminants, the
substrate should be exposed to as little oxygen as possible to
protect the copper surface from oxidation. After surface
contaminants are removed, at step 803, the thin copper layer over
the barrier layer and dielectric layer is removed. The thin copper
layer can be removed by O.sub.2/Ar sputtering, by
O.sub.2/hexafluoroacetylacetone (HFAC) plasma etch, by a wet
chemical etch using chemicals, such as sulfuric acid and hydrogen
peroxide, or by using complexing chemistries. Both O.sub.2/Ar
sputtering and O.sub.2/HFAC plasma processes are operated under low
pressure, such as below 1 Torr.
[0094] Afterwards, the barrier layer, such as Ta, TaN, or a
combination of both films, is removed from substrate surface at
step 805. The cross-section of the interconnect structure after the
removal of the thin copper and barrier is shown in FIG. 7B. Barrier
layer can be removed by CF.sub.4 plasma, O.sub.2/Ar sputtering,
CMP, or by a wet chemical etch. Both CF.sub.4 plasma etch and
O.sub.2/Ar sputtering processes are operated at below 1 Torr.
[0095] Since the copper surface to selectively deposit the
cobalt-alloy is created by etching the thin copper layer and the
barrier layer above dielectric in controlled-ambient environments,
the step of using H-containing plasma to reduce the copper surface
is mostly not needed. However, to ensure that the copper surface is
free of copper oxide, the substrate surface can optionally be
reduced to convert any residual copper oxide into copper at step
807. The copper surface reduction process has been described above.
Once the substrate went through a hydrogen-containing reduction
process, the substrate is ready for the cobalt-alloy deposition.
The copper surface needs to be carefully protected to prevent
copper oxide formation. At next process step 809, the cobalt-alloy,
such as CoWP, CoWB or CoWBP, is electrolessly deposited on the top
of the copper surface. Cobalt-alloy is shown as layer 135 in FIG.
7C. The electroless deposition of the cobalt-alloy is a selective
deposition and is a wet process. The cobalt-alloy only deposits on
the copper surface.
[0096] As described above for Case I and Case II, after the
electroless deposition of the cobalt-alloy, the process flow can
enter an optional process step 811 of a post-deposition clean.
Post-deposition clean has been described above in Case I and Case
II.
[0097] As described above, the environment control is very
important for preparing the copper surface for cobalt-alloy
deposition, especially after the H-containing plasma reduction of
the copper surface. FIG. 8B shows a schematic diagram of an
exemplary integrated system 850 that allows minimal exposure of
substrate surface to oxygen at critical steps after surface
treatment. The integrated system 850 can be used to process
substrate(s) through the entire process sequence of flow 800 of
FIG. 8A.
[0098] The integrated system 850 has 3 substrate transfer modules
860, 870, and 880. Transfer modules 860, 870 and 880 are equipped
with robots to move substrate 855 from one process area to another
process area. Substrate transfer module 860 is operated under lab
ambient. Module 860 interfaces with substrate loaders (or substrate
cassettes) 861 to bring the substrate 855 into the integrated
system or to return the substrate to the cassette(s) 861 to
continue processing outside the system 850.
[0099] As described above in process flow 800, the substrate 855 is
brought to the integrated system 850 to be deposited with a
cobalt-alloy, such as CoWB, CoWP, or CoWBP, after the substrate has
been planarized by copper CMP to remove excess copper from the
substrate surface and leaves a thin copper layer on the barrier
layer that is over the dielectric surface, as shown in FIG. 7A. As
described in step 801 of process flow 800, the substrate surface
needs to be removed of surface contaminants such organic residues
and non-copper metal oxides. Due to the elimination of the need to
perform a wet Cu-BTA clean, in contrast to Case I and Case II, the
lab-ambient transfer module 860 can possibly be eliminated to allow
cassette holders 861 to be directly coupled to loadlock 865.
[0100] Surface contaminants including organic residues and metal
oxides can be removed by an oxidizing plasma process such as
O.sub.2 plasma or O.sub.2/Ar sputter. As described above, most
plasma or sputtering processes are operated below 1 Torr;
therefore, it's desirable to couple such systems to a transfer
module that is operated under vacuum at pressure, such as under 1
Torr. Assuming O.sub.2 plasma process is selected to clean the
organic residue, the O.sub.2 plasma process reactor 871 is coupled
to a vacuum transfer module 870.
[0101] The O.sub.2 plasma process can be a downstream plasma
process. Although the O.sub.2 plasma reactor 871 can be integrated
with the vacuum transfer module 870 in the process flow 800, this
process step can also be performed right after metal CMP and before
the substrate is brought to the integrated system for cobalt-alloy
deposition.
[0102] Since lab-ambient transfer module 860 is operated under
atmosphere and vacuum transfer module 870 is operated under vacuum
(<1 Ton), a loadlock 865 is placed between these two transfer
modules to allow substrate 855 to be transferred between the two
modules, 860 and 870.
[0103] After substrate 855 finishes the O.sub.2 plasma processing,
substrate 855 is moved into a processing system for copper etch, as
shown in step 803. The copper etch chamber (or module) 873, if a
dry copper plasma etch process is selected, is coupled to the
vacuum transfer module 870. If a wet process is selected, the wet
copper etch reactor can be integrated with a rinse/dry system to
become a wet copper etch system 873' that can be coupled to the
controlled-ambient transfer module 880. To enable the wet copper
etch system 873' to be integrated with the controlled-ambient
transfer module 880, dry-in and dry-out of substrate to the system
873' are required. In one embodiment, a rinse and dry system can be
integrated in the wet copper etch system 873' to meet the
dry-in/dry-out requirement. The environment of system 873' also
needs to be controlled to be free of oxygen. Inert gas can also be
used to fill the system to ensure no oxygen is in the processing
environment.
[0104] Barrier layer etch follows copper etch, as shown in step
805. The barrier layer etch chamber 874, if a dry barrier plasma
etch process is selected, can be coupled to the vacuum transfer
module 870. If a wet barrier etch process is selected, the wet
barrier etch reactor can be integrated with a rinse/dry system to
become a wet barrier etch system 874' that can be coupled to the
controlled-ambient transfer module 880. To enable the wet barrier
etch system 874' to be integrated with the controlled-ambient
transfer module 880, dry-in and dry-out of substrate to the system
874' are required. The environment of system 874' also needs to be
controlled to provide low (or limited, or controlled) levels of
oxygen. Inert gas can also be used to fill the system to ensure low
oxygen levels are achieved in the processing environment.
[0105] The process following barrier layer etch is an optional
H-containing plasma reduction as discussed above. The H.sub.2
plasma reduction can be performed in a plasma chamber 877, which is
coupled to the vacuum transfer module 870.
[0106] As described above, cobalt-alloy electroless deposition is a
wet process. Since wet process is typically conducted under
atmospheric pressure, the transfer module 880 that is coupled to
the electroless deposition reactor should be operated near
atmospheric pressure. To ensure the environment is controlled to
provide low levels of oxygen, inert gas (es) can be used to fill
the controlled-ambient transfer module 880. Additionally, all
fluids used in the process are de-gassed, i.e. dissolved oxygen is
removed by commercially available degassing systems. Exemplary
inert gas includes nitrogen (N.sub.2), helium (He), neon (Ne),
argon (Ar), krypton (Kr), and xenon (Xe).
[0107] The wet cobalt-alloy electroless deposition reactor needs to
be coupled with a rinse and dry system to allow the substrate to go
into the electroless deposition system 881 under dry condition and
to come out of the system 881 in dry condition (dry-in/dry-out).
The dry-in/dry-out requirement allows the electroless deposition
system 881 to be integrated with the controlled-ambient transfer
module 880. Inert gas (es) is used to fill system 881 to ensure a
low oxygen level is present in the system.
[0108] After cobalt-alloy deposition in system 881, the substrate
855 can be sent through a post-deposition cleaning reactor. A rinse
and dry system also need to be integrated with the brush scrub
system to allow substrate 855 to be dry-in/dry-out of the wet
cleaning system 883. Inert gas (es) is used to fill system 883 to
ensure no oxygen is present. The system 883 is dotted to illustrate
that this system is optional, since the post-deposition cleaning is
optional, as described above in FIG. 8A. Since the post-deposition
clean step is the last process that is to be operated by the
integrated system 850, the substrate 855 needs to be brought back
into cassette 861 after processing. The cleaning system 883 can
alternatively be coupled to the lab-ambient transfer module
860.
2. Engineering Barrier Surface for Electroless Copper
Deposition
[0109] The system concept describe above can be used to prepare
barrier surface for copper plating. Barrier layer, such as Ta, TaN
or Ru, if exposed to air for extended period of time, can form
Ta.sub.xO.sub.y (Tantalum oxide), TaO.sub.xN.sub.y (Tantalum
oxynitride), or RuO.sub.2 (Ruthenium oxide). Electroless deposition
of a metal layer on a substrate is highly dependent upon the
surface characteristics and composition of the substrate.
Electroless plating of copper on a Ta, TaN, or Ru surface is of
interest for both seed layer formation prior to electroplating, and
selective deposition of Cu lines within lithographically defined
pattern(s). One concern is the inhibition of the electroless
deposition process by atomically thin native metal oxide layer
formed in the presence of oxygen (O.sub.2).
[0110] In addition, copper film does not adhere to the barrier
oxide layer, such as tantalum oxide, tantalum oxynitride, or
ruthenium oxide, as well as it adheres to the pure barrier metal or
barrier-layer-rich film, such as Ta, Ru, or Ta-rich TaN film. Ta
and/or TaN barrier layers are only used as examples. The
description and concept apply to other types of barrier metals,
such as Ta or TaN capped with a thin layer of Ru. As described
above, poor adhesion can negatively affect the EM performance. In
addition, the formation tantalum oxide or tantalum oxynitride on
the barrier layer surface can increase the resistivity of the
barrier layer. Due to these issues, it is desirable to use the
integrated system to prepare the barrier/copper interface to ensure
good adhesion between the barrier layer and copper and to ensure
low resistivity of the barrier layer.
CASE I: Metal Line Formation
[0111] FIG. 9A shows an exemplary cross-section of a metal line
structure after being patterned by a dielectric etch and being
removed of photoresist. The metal line structure(s) is on a
substrate 900 and has a silicon layer 110, which was previously
fabricated to form a gate structure 105 with a gate oxide 121,
spacers 107 and a contact 125 therein. The contact 125 is typically
fabricated by etching a contact hole into the oxide 103 and then
filling the contact hole with a conductive material, such as
tungsten. Alternative materials may include copper, aluminum or
other conductive materials. The barrier layer 102 is also
configured to function as a selective trench etch stop. The barrier
layer 102 can be made of materials such as silicon nitride (SiN) or
silicon carbide (SiC).
[0112] A metal line dielectric layer 106 is deposited over the
barrier layer 102. The dielectric materials that can be used to
deposit 106 have been described above. After the deposition of
dielectric layer 106, the substrate is patterned and etched to
create metal trenches 106. FIG. 9B shows that after the formation
of metal trenches 116, a metallic barrier layer 130 is deposited to
line metal trench 116. FIG. 9C shows that after the barrier layer
130 is deposited, a copper layer 132 is deposited over the barrier
layer 130. The barrier layer 130 can be made of tantalum nitride
(TaN), tantalum (Ta), Ru, or a combination of these films. A copper
film 132 is then deposited to fill the metal trench 116. In one
embodiment, the copper film 132 includes a thin copper seed layer
131 underneath.
[0113] After using plasma surface pre-treatments to prepare a
catalytic surface for the deposition of a conformal and thin
electroless Cu seed layer 131, and copper film 132 filling trenches
116, substrate 900 is chemically and mechanically polished (CMP) or
wet etched to remove the copper material (or copper overburden) and
bather layer (or barrier overburden) over the surface of dielectric
106, as shown in FIG. 9D. In one embodiment, the thickness of the
thin copper seed layer is between about 5 angstroms to about 300
angstroms. The next step is to cap the copper surface 140 with a
copper/SiC interface adhesion promoter layer 135, such as a
cobalt-alloy, as shown in FIG. 9E. Examples of the cobalt-alloy
include: CoWP, CoWB, or CoWBP, which can be selectively deposited
over copper by an electroless process. The thickness of the
adhesion promoter layer can be as thin as a monolayer, which is
only a few angstroms, such as 5 angstroms, to a thicker layer, such
as 200 angstroms.
[0114] FIG. 10A shows an embodiment of a process flow 1000 of
preparing the barrier (or liner) layer surface for electroless
copper deposition after the trenches have been formed. It should be
noted, however, that the barrier (or liner) layer may be prepared
separately in a non-integrated deposition system, such as an ALD or
PVD deposition reactor. In this case, the surface preparation for
depositing a thin copper seed layer would not include the metal
plug preclean and barrier deposition process steps. At step 1001,
the top surface 124a of the contact plug is cleaned to remove
native metal oxide. Metal oxide can be removed by an Ar sputtering
process, a plasma process using a fluorine-containing gas, such as
NF.sub.3, CF.sub.4, or a combination of both, a wet chemical etch
process, or a reduction process, for example using a
hydrogen-containing plasma. At step 1003, a barrier layer is
deposited. Due to the shrinking metal line and via critical
dimension, the barrier layer may be deposited by atomic layer
deposition (ALD), depending on the technology node. The thickness
of the barrier layer 130 is between about 20 angstroms to about 200
angstroms. As described above, preventing the barrier layer from
exposure to oxygen is critical in ensuring that electroless copper
is being deposited on the barrier layer with good adhesion between
copper and the barrier layer. Once the barrier layer is deposited,
the substrate should be transferred or processed in a
controlled-ambient environment to limit exposure to oxygen. The
barrier layer is hydrogen-plasma treated to produce a metal-rich
surface on the Ta, TaN, or Ru layer at optional step 1005 to
provide a catalytic surface for the subsequent copper seed
deposition step. Whether this step is needed or not depends on how
metal-rich the surface is.
[0115] Afterwards, conformal copper seed is deposited on the
barrier surface at step 1007, followed by a thick copper gap fill
(or bulk fill) process, 1008. In one embodiment, the conformal
copper seed layer can be deposited by an electroless process. The
thick copper bulk fill process can be an electroless deposition
(ELD) process or an electrochemical plating (ECP) process.
Electroless copper deposition and ECP are well-known wet process.
For a wet process to be integrated in a system with controlled
processing and transporting environment, which has been described
above, the reactor needs to be integrated with a rinse/dryer to
enable dry-in/dry-out process capability. In addition, the system
needs to be filled with inert gas to ensure minimal exposure of the
substrate to oxygen. Recently, a dry-in/dry-out electroless copper
process has been developed. Further, all fluids used in the process
are de-gassed, i.e. dissolved oxygen is removed by commercially
available degassing systems.
[0116] The electroless deposition process can be carried out in a
number of ways, such as puddle-plating, where fluid is dispensed
onto a substrate and allowed to react in a static mode, after which
the reactants are removed and discarded, or reclaimed. In another
embodiment, the process uses a proximity process head to limit the
electroless process liquid is only in contact with the substrate
surface on a limited region. The substrate surface not under the
proximity process head is dry. Details of such process and system
can be found in U.S. application Ser. No. 10/607, 611, titled
"Apparatus And Method For Depositing And Planarizing Thin Films Of
Semiconductor Wafers," filed on Jun. 27, 2003, and U.S. application
Ser. No. 10/879,263, titled "Method and Apparatus For Plating
Semiconductor Wafers," filed on Jun. 28, 2004, both of which are
incorporated herein in their entireties. The electroless plating of
cobalt-alloy described earlier can also use similar proximity
processing head to enable a dry-in/dry-out process.
[0117] After copper deposition at steps 1007 and 1008, the
substrate can undergo an optional substrate cleaning at step 1009.
Post-copper-deposition clean can be accomplished by using a brush
scrub clean with a chemical solution, such as a solution containing
CP72B supplied by Air Products and Chemical, Inc. of Allentown, Pa.
Other substrate surface cleaning processes can also be used, such
as Lam's C3.TM. or P3.TM. cleaning technology.
[0118] FIG. 10B shows an embodiment of a schematic diagram of an
integrated system 1050 that allows minimal exposure of substrate
surface to oxygen at critical steps after barrier surface
preparation. In addition, since it is an integrated system, the
substrate is transferred from one process station immediately to
the next process station, limiting the duration that clean copper
surface is exposed to low levels of oxygen. The integrated system
1050 can be used to process substrate(s) through the entire process
sequence of flow 1000 of FIG. 10A.
[0119] As described above, the surface preparation for electroless
deposition of copper and the optional post-cobalt-alloy deposition
processes involves a mixture of dry and wet processes. The wet
processes are typically operated near atmosphere, while the dry
plasma processes are operated at less than 1 Torr. Therefore, the
integrated system needs to be able to handle a mixture of dry and
wet processes. The integrated system 1050 has 3 substrate transfer
modules 1060, 1070, and 1080. Transfer modules 1060, 1070 and 1080
are equipped with robots to move substrate 1055 from one process
area to another process area. The process area could be a substrate
cassette, a reactor, or a loadlock. Substrate transfer module 1060
is operated under lab ambient. Module 1060 interfaces with
substrate loaders (or substrate cassettes) 1061 to bring the
substrate 1555 into the integrated system or to return the
substrate to one of the cassettes 1061.
[0120] As described above in process flow 1000, the substrate 1055
is brought to the integrated system 1050 to deposit barrier layer
and copper layer. As described in step 1001 of process flow 1000,
top tungsten surface 124a of contact 125 is etched to remove native
tungsten oxide. Once the tungsten oxide is removed, the exposed
tungsten surface 124a of FIG. 9A needs to be protected from
exposure to oxygen. If the removal process is an Ar sputtering
process, the reactor 1071 is coupled to the vacuum transfer module
1070. If a wet chemical etching process is selected, the reactor
should be coupled to the controlled-ambient transfer module 1080,
not the lab-ambient transfer module 1060, to limit exposure of the
tungsten surface to oxygen.
[0121] Afterwards, the substrate is deposited with a metallic
barrier layer, such as Ta, TaN, Ru, or a combination of these
films, as described in step 1003 of FIG. 10A. The barrier layer 130
of FIG. 9B can be deposited by an ALD process or a PVD process. In
one embodiment, the ALD process is operated at less than 1 Torr.
The ALD reactor 1073 is coupled to the vacuum transfer module 1070.
In another embodiment, the deposition process is a high pressure
process using supercritical CO.sub.2 and organometallic precursors
to form the metal barrier. In yet another embodiment, the
deposition process is a physical vapor deposition (PVD) process
operating at pressures less than 1 Torr. Details of an exemplary
reactor for a high pressure process using supercritical CO.sub.2 is
described in commonly assigned application Ser. No. 10/357,664,
titled "Method and Apparatus for Semiconductor Wafer Cleaning Using
High-Frequency Acoustic Energy with Supercritical Fluid", filed on
Feb. 3, 2003, which in incorporated herein for reference.
[0122] The substrate can undergo an optional reduction process, for
example using a hydrogen-containing plasma, as described in step
1005 of FIG. 10A. The hydrogen reduction reactor 1074 can be
coupled to the vacuum transfer module 1070. At this stage, the
substrate is ready for electroless copper deposition. The
electroless copper plating can be performed in an electroless
copper plating reactor 1081 to deposit a conformal seed layer.
Following the seed layer deposition, copper bulk fill can be
performed in the same electroless copper deposition reactor 1081
used to deposit the conformal seed layer, but with a different
chemistry to achieve bulk fill. Alternatively, copper bulk fill can
be performed in a separate ECP reactor 1081'.
[0123] Before the substrate leaves the integrated system 1050, the
substrate can optionally undergo a surface cleaning process, which
can clean residues from the previous copper deposition process. For
example, the substrate cleaning process can be brush clean process.
Substrate cleaning reactor 1083 can be integrated with the
controlled-ambient transfer module 1080. Alternatively, substrate
cleaning reactor 1083 can also be integrated with the lab-ambient
transfer module 1060.
[0124] Alternatively, the barrier layer 130 of FIG. 9B can be
deposited in a process chamber before the substrate 900 is brought
into a system for surface treatment and depositing copper. FIG. 10C
shows an embodiment of a process flow 1090 of preparing the barrier
(or liner) layer surface for electroless copper deposition. The
barrier surface is hydrogen-plasma treated to produce a metal-rich
surface on the Ta, TaN, or Ru layer at optional step 1095 to
provide a catalytic surface for the subsequent copper seed
deposition step. Whether this step is needed or not depends on how
metal-rich the surface is.
[0125] Afterwards, conformal copper seed is deposited on the
barrier surface at step 1097, followed by a thick copper gap fill
(or bulk fill) process, 1098. In one embodiment, the conformal
copper seed layer can be deposited by an electroless process. The
thick copper bulk fill process can be an electroless deposition
(ELD) process or an electrochemical plating (ECP) process. After
copper deposition at steps 1097 and 1098, the substrate can undergo
an optional substrate cleaning at step 1099. Post-copper-deposition
clean can be accomplished by using a brush scrub clean with a
chemical solution, such as a solution containing CP72B supplied by
Air Products and Chemical, Inc. of Allentown, Pa. Other substrate
surface cleaning processes can also be used, such as Lam's C3.TM.
or P3.TM. cleaning technology.
[0126] FIG. 10D shows an embodiment of a schematic diagram of an
integrated system 1092 that allows minimal exposure of substrate
surface to oxygen at critical steps after barrier surface
preparation. In addition, since it is an integrated system, the
substrate is transferred from one process station immediately to
the next process station, limiting the duration that clean copper
surface is exposed to low levels of oxygen. The integrated system
1092 can be used to process substrate(s) through the entire process
sequence of flow 1090 of FIG. 10C.
[0127] As described above, the surface preparation for electroless
deposition of copper and the optional post-cobalt-alloy deposition
processes involves a mixture of dry and wet processes. The wet
processes are typically operated near atmosphere, while the dry
plasma processes are operated at less than 1 Torr. Therefore, the
integrated system needs to be able to handle a mixture of dry and
wet processes. The integrated system 1092 has 3 substrate transfer
modules 1060, 1070, and 1080. Transfer modules 1060, 1070 and 1080
are equipped with robots to move substrate 1055 from one process
area to another process area. The process area could be a substrate
cassette, a reactor, or a loadlock. Substrate transfer module 1060
is operated under lab ambient. Module 1060 interfaces with
substrate loaders (or substrate cassettes) 1061 to bring the
substrate 1555 into the integrated system or to return the
substrate to one of the cassettes 1061.
[0128] As described above in process flow 1090, the substrate 1055
is brought to the integrated system 1092 after the barrier layer is
deposited to prepare the barrier surface for electroless copper
deposition. The substrate first undergoes a reduction process, for
example using a hydrogen-containing plasma, as described in step
1095 of FIG. 10C. The hydrogen reduction reactor 1074 can be
coupled to the vacuum transfer module 1070. At this stage, the
substrate is ready for electroless copper deposition. The
electroless copper plating can be performed in an electroless
copper plating reactor 1081 to deposit a conformal seed layer.
Following the seed layer deposition, copper bulk fill can be
performed in the same electroless copper deposition reactor 1081
used to deposit the conformal seed layer, but with a different
chemistry to achieve bulk fill. Alternatively, copper bulk fill can
be performed in a separate ECP reactor 1081'.
[0129] Before the substrate leaves the integrated system 1092, the
substrate can optionally undergo a surface cleaning process, which
can clean residues from the previous copper deposition process. For
example, the substrate cleaning process can be brush clean process.
Substrate cleaning reactor 1083 can be integrated with the
controlled-ambient transfer module 1080. Alternatively, substrate
cleaning reactor 1083 can also be integrated with the lab-ambient
transfer module 1060.
[0130] FIG. 11A shows an embodiment of a process flow of preparing
the bather (or liner) layer surface for electroless copper
deposition and preparing the post-CMP copper surface for
electroless cobalt-alloy deposition. At step 1101, the top surface
124a of the contact plug is cleaned to remove native tungsten
oxide. Metal oxide can be removed by an Ar sputtering process, a
plasma reduction process, a reactive ion etch process, or a wet
chemical etch process. At step 1103, a barrier layer is deposited.
The barrier layer is hydrogen-plasma treated to produce a
metal-rich surface on the Ta, TaN or Ru layer at optional step 1005
to provide a catalytic surface for the subsequent copper seed
deposition step. Whether this step is needed or not depends on how
metal-rich the surface is.
[0131] It should be noted, however, that the barrier (or liner)
layer may be prepared separately in a non-integrated deposition
system, such as an ALD or PVD deposition reactor. In this case, the
surface preparation for depositing a thin copper seed layer would
not include the metal plug preclean and barrier deposition process
steps as described in FIG. 10A, step 1001 and 1003, and FIG. 11A,
steps 1101, 1103. In these cases, the process described would
commence at step 1005 or 1105.
[0132] Afterwards, conformal copper seed is deposited on the
barrier surface at step 1107, followed by a thick copper gap fill
(or bulk fill) process, 1108. In one embodiment, the conformal
copper seed layer can be deposited by an electroless process. The
thick copper bulk fill process can be an electroless deposition
process (ELD) or an electrochemical plating (ECP) process.
Electroless copper deposition and ECP are well-known wet processes.
For a wet process to be integrated in a system with controlled
processing and transporting environment, which has been described
above, the reactor needs to be integrated with a rinse/dryer to
enable dry-in/dry-out process capability. In addition, the system
needs to be filled with inert gas to ensure minimal exposure of the
substrate to oxygen. Recently, a dry-in/dry-out electroless copper
process has been developed. Further, all fluids used in the process
are de-gassed, i.e. dissolved oxygen is removed by commercially
available degassing systems.
[0133] After the substrate is deposited with conformal copper seed
at step 1107, and thick Cu gap fill (bulk fill) by either an
electroless or electro-plating process at step 1108, the copper
layer 132 is removed from the substrate surface above barrier layer
130 over dielectric 106 at step 1109, as shown in FIG. 9D. Barrier
layer is removed afterwards. Both removal processes are performed
in process step 1109 of FIG. 11A. Removing copper from the surface
above barrier layer can be accomplished by CMP, which is a wet
process. Barrier layer can be removed by using a reactive ion etch,
such as CF.sub.4-plasma, O.sub.2/Ar sputtering, CMP, or a wet
chemical etch. These barrier etch processes have been described
previously.
[0134] After barrier layer removal, a cleaning process to remove
Cu-BTA complexes and metal oxides (step 1110) and an organic
contaminants removal process (step 1111) are performed to remove
contaminants from the substrate surface. Details of substrate
surface cleaning using these two steps after metal CMP have been
described above.
[0135] After substrate surface is removed of surface contaminants,
the substrate is treated with a reducing plasma
(hydrogen-containing) to reduce all residual metal oxide into metal
at step 1112. After hydrogen reduction, the copper surface is very
clean and catalytic, and is ready for electroless deposition of the
cobalt-alloy. At step 1113, the substrate undergoes electroless
deposition of cobalt-alloy with a rinse and dry of substrate. The
last process step 1115 is an optional substrate-cleaning step to
clean any residual contaminants from the previous electroless
cobalt-alloy deposition.
[0136] FIG. 11B shows an embodiment of a schematic diagram of an
integrated system 1150 that allows minimal exposure of substrate
surface to oxygen at critical steps after barrier and copper
surface preparation. In addition, since it is an integrated system,
the substrate is transferred from one process station immediately
to the next process station, which limits the duration that clean
copper surface is exposed to low levels of oxygen. The integrated
system 1150 can be used to process substrate(s) through the entire
process sequence of flow 1100 of FIG. 11A.
[0137] The integrated system 1150 has 3 substrate transfer modules
1160, 1170, and 1180. Transfer modules 1160, 1170 and 1180 are
equipped with robots to move substrate 1155 from one process area
to another process area. The process area could be a substrate
cassette, a reactor, or a loadlock. Substrate transfer module 1160
is operated under lab ambient. Module 1160 interfaces with
substrate loaders (or substrate cassettes) 1161 to bring the
substrate 1155 into the integrated system or to return the
substrate to one of the cassettes 1161.
[0138] As described above in process flow 1100 of FIG. 11A, the
substrate 1155 is brought to the integrated system 1150 to deposit
barrier layer, to prepare barrier surface for copper layer
deposition, and to prepare post-CMP copper surface for electroless
cobalt-alloy deposition. As described in step 1101 of process flow
1100, top metal plug surface 124a of contact 125 is etched to
remove native metal oxide. Alternatively, the metal plug surface
oxide can be removed using a reducing plasma, such as a
hydrogen-containing plasma. Once the metal plug surface oxide is
removed, the exposed metal surface 124a of FIG. 9A needs to be
protected from exposure to oxygen. If the removal process is an Ar
sputtering process, the Ar sputtering reactor 1171 is coupled to
the vacuum transfer module 1170. If a wet chemical etching process
is selected, the reactor should be coupled to the
controlled-ambient transfer module 1180, not the lab-ambient
transfer module 1160, to limit the exposure of the clean metal plug
surface to oxygen.
[0139] Afterwards, the substrate is deposited with a metallic
barrier layer, such as Ta, Ru, TaN, or a combination of these
films, as described in a step 1103 of FIG. 11A. The barrier layer
130 of FIG. 9B can be deposited by an ALD process or a PVD process.
In one embodiment, the ALD process is operated at less than 1 Torr.
The ALD reactor 1173 is coupled to the vacuum transfer module 1170.
In another embodiment, the deposition process is a high pressure
process using supercritical CO.sub.2 and organometallic precursors
to form the metal barrier. In yet another embodiment, the
deposition process is a physical vapor deposition (PVD) process
operating at pressures less than 1 Torr. The substrate can undergo
an optional reduction process, for example using a
hydrogen-containing plasma, as described in step 1105 of FIG. 11A.
The hydrogen reduction reactor 1174 can be coupled to the vacuum
transfer module 1170. At this stage, the substrate is ready for
electroless copper deposition. The electroless copper plating can
be performed in an electroless copper plating reactor 1181 to
deposit a conformal seed layer. Following the seed layer
deposition, copper bulk fill can be performed in the same
electroless copper deposition reactor 1181 used to deposit the
conformal seed layer, but with a different chemistry to achieve
bulk fill. Alternatively, copper bulk fill can be performed in a
separate ECP reactor 1181'.
[0140] Afterwards, the substrate is removed of copper overburden
and barrier overburden, as described in step 1109 of FIG. 11A. The
removal of copper overburden and barrier over burden can be
accomplished in one CMP system 1183, or in two CMP systems. In the
embodiment shown in FIG. 11A, only one CMP system 1183 is used.
After CMP removal of copper and barrier overburdens, the substrate
surface needs to be cleaned to remove surface contaminants Wet
clean system 1185 is used to remove copper BTA complexes and metal
oxides. O.sub.2 plasma system 1177 is used to remove organic
contaminants. In one embodiment, O.sub.2 plasma process to remove
organic contaminants can be performed in the hydrogen reduction
chamber 1174.
[0141] After the removal of contaminants, the substrate undergoes a
reduction process, as described in step 1112 of FIG. 11A. The
hydrogen reduction process can occur in the same reduction reactor
1174 used to reduce the bather surface to be Ta-rich. Following
hydrogen reduction treatment, the copper surface is ready for
electroless cobalt-alloy deposition, which can be performed in
reactor 1187.
[0142] Before the substrate leaves the integrated system 1150, the
substrate can optionally undergo a surface cleaning process, which
can clean residues from the previous copper plating process. The
substrate cleaning process can be brush clean process, whose
reactor 1163 can be integrated with the lab-ambient transfer module
1160.
[0143] The wet processing systems described in FIG. 15B, which are
coupled to the controlled-ambient transfer module 1180, all need to
meet the requirement of dry-in/dry-out to allow system
integration.
CASE II: Dual Damascene Interconnect Sequence
[0144] FIG. 12A shows an exemplary cross-section of an interconnect
structure after being patterned by a dual damascene process. The
interconnect structure(s) is on a substrate 1200 and has an oxide
layer 100, which was previously fabricated to form a metallization
line 101 therein. The metallization line is typically fabricated by
etching a trench into the oxide 100 and then filling the trench
with conductive material, such as copper.
[0145] In the trench, there is a barrier layer 120, used to prevent
the copper material 122 from diffusing into the oxide 100. The
barrier layer 120 can be made of tantalum nitride (TaN), tantalum
(Ta), ruthenium (Ru), or a combination of these films. Other
barrier layer materials can also be used. A barrier layer 102 is
deposited over the copper material 122 to provide an etch stop
during the via etch process, and to act as a diffusion barrier
between dielectric layers for the copper. The barrier layer 102 can
be made of materials such as silicon nitride (SiN) or silicon
carbide (SiC) or other materials suitable for integration into the
dual Damascene process flow.
[0146] A via dielectric layer 104 is deposited over the barrier
layer 102. The via dielectric layer 104 can be made of inorganic
dielectric materials such as silicon dioxide, or preferably low-K
dielectric materials. Exemplary dielectrics can include an un-doped
TEOS silicon dioxide, fluorinated silica glass (FSG),
organo-silicate glass (OSG), porous OSG, commercially available
dielectric materials include Black Diamond (I) and Black Diamond
(II), Coral, Aurora. After the via dielectric layer 104 is
deposited, a patterning and etching process is used to form the via
holes 114. The copper surface 122a is protected by the dielectric
barrier layer, such as SiC or Si.sub.3N.sub.4. FIG. 12A shows the
dual Damascene structure after the formation of via holes 114, and
trenches 116. The dielectric barrier layer 102 under via holes 114
has been removed.
[0147] FIG. 12B shows that after the formation of via holes 114 and
trenches 116, a first barrier layer 130.sub.I, a second barrier
layer 130.sub.II, and a copper layer 132 are deposited to line the
via holes 114' and the trenches 116. Both barrier layers 130.sub.I,
130.sub.II can be made of tantalum nitride (TaN), tantalum (Ta), or
ruthenium (Ru). Other barrier layer materials can also be used. In
one embodiment, the first barrier layer 130.sub.k is a thin TaN
layer deposited by ALD and the second barrier layer 130.sub.II is a
very thin Ta layer deposited by flash PVD or Ru layer deposited by
ALD or PVD. In one embodiment, the thickness of the first barrier
layer 130.sub.I is between about 10 angstroms to about 150
angstroms and the thickness of the second bather layer 130.sub.II
is between about 10 angstroms to about 50 angstroms. The thin ALD
TaN layer provides conformal coverage of a barrier layer over the
via 114' and trench 116. The thin PVD Ta or Ru layer provides good
adhesion to the copper film 132 to be deposited over the barrier
layers 130.sub.I and 130.sub.II. Typically, barrier layer deposited
by PVD process does not have good step coverage (or the film is not
conformal). Therefore, an ALD barrier is needed to ensure good
barrier coverage inside via and trench. In another embodiment, the
first barrier layer 130.sub.I and the second barrier layer
130.sub.II is combined into one single layer, which can be
deposited by ALD or by PVD. The material of this single layer
barrier can be tantalum, tantalum nitride, ruthenium, or a
combination of these films.
[0148] After the deposition of the first and second barrier layers
130.sub.I, 130.sub.II, the substrate undergoes previously described
requite surface treatment steps to ensure the barrier surface is
Ta-rich. A copper film 132 is then deposited, either using a PVD
seed 131 or electroless seed 131 followed by a thick gap-fill
copper layer to fill the via holes 114 and the trenches 116.
[0149] After copper film 132 fills the via holes 114 and trenches
116, substrate 1200 is planarized to remove the copper material (or
copper overburden) and barrier layer (or barrier overburden) over
the surface of dielectric 106, as shown in FIG. 12C. The substrate
then undergoes previously described requite surface treatment steps
to ensure the substrate surface is clean and the copper surface is
removed of copper oxide. The next step is to cap the copper surface
140 with a copper/SiC interface adhesion promoter layer 135, such
as a cobalt-alloy, as shown in FIG. 16D. Examples of the
cobalt-alloy include: CoWP, CoWB, or CoWBP, which can be
selectively deposited over copper by an electroless process. The
thickness of the adhesion promoter layer can be as thin as a
monolayer, which is only a few angstroms, to a thicker layer, such
as 200 angstroms.
[0150] FIG. 13A shows an embodiment of a process flow of preparing
the bather (or liner) layer surface for electroless copper
deposition and preparing the post-CMP copper surface for
electroless cobalt-alloy deposition. At step 1301, the top surface
122a of the metal lines 101 is cleaned to remove native copper
oxide. Copper oxide can be removed by an Ar sputtering process or a
wet chemical etch process. At step 1302, a first barrier layer
(130.sub.I of FIG. 12B) is deposited in an ALD system. At step
1303, a second barrier layer (13011 of FIG. 12B) is deposited in a
PVD system. As described above, preventing the barrier layer from
exposure to oxygen is critical in ensuring that electroless copper
is being deposited on the barrier layer with good adhesion between
copper and the barrier layer. Once the barrier layer is deposited,
the substrate should be transferred or processed in a
controlled-ambient environment to limit exposure to oxygen. The
barrier layer is treated by a reducing plasma (i.e.
hydrogen-containing) at step 1305 to produce a metal-rich layer
that will provide a catalytic surface for the subsequent copper
seed deposition step. The reducing plasma treatment is optional,
depending on the composition of the surface.
[0151] Afterwards, a conformal copper seed is deposited on the
barrier surface at step 1307, followed by a thick copper bulk fill
(or gap fill) process, 1308. The conformal copper seed layer can be
deposited by an electroless process. The thick copper bulk fill
(also gap fill) layer can be deposited by an ECP process.
Alternatively, the thick bulk fill (also gap fill) layer can be
deposited by an electroless process in the same electroless system
for conformal copper seed, but with a different chemistry.
[0152] After the substrate is deposited with conformal copper seed
at step 1307, and thick Cu bulk fill by either an electroless or
electro-plating process at step 1308, the copper layer 132 is
removed from the substrate surface above barrier layer 130 over
dielectric 106 at step 1309, as shown in FIG. 11C. Barrier layer is
removed afterwards. Both removal processes are performed in process
step 1309 of FIG. 13A. Removing copper from the surface above
barrier layer can be accomplished by CMP, which is a wet process.
Barrier layer can be removed by using CF.sub.4 plasma, O.sub.2/Ar
sputtering, CMP, or a wet chemical etch. These barrier etch
processes have been described previously.
[0153] After barrier layer removal, a cleaning process to remove
Cu-BTA complexes and metal oxides (step 1310) and an organic
contaminants removal process (step 1311) are performed to remove
contaminants from the substrate surface. Details of substrate
surface cleaning using these two steps after metal CMP have been
described above.
[0154] After substrate surface is removed of surface contaminants,
the substrate is treated with a reducing plasma, for example a
hydrogen-containing plasma, to reduce all residual metal oxide into
metal at step 1312. After hydrogen reduction, the copper surface is
very clean and catalytic, and is ready for electroless deposition
of the cobalt-alloy. At step 1313, the substrate undergoes
electroless deposition of cobalt-alloy with a rinse and dry of
substrate. The last process step 1315 is an optional
substrate-cleaning step to clean any residual contaminants from the
previous electroless cobalt-alloy deposition.
[0155] FIG. 13B shows an embodiment of a schematic diagram of an
integrated system 1350 that allows minimal exposure of substrate
surface to oxygen at critical steps after barrier and copper
surface preparation. In addition, since it is an integrated system,
the substrate is transferred from one process station immediately
to the next process station, which limits the duration that clean
copper surface is exposed to low levels of oxygen. The integrated
system 1350 can be used to process substrate(s) through the entire
process sequence of flow 1300 of FIG. 13A.
[0156] The integrated system 1350 has 3 substrate transfer modules
1360, 1370, and 1380. Transfer modules 1360, 1370 and 1380 are
equipped with robots to move substrate 1355 from one process area
to another process area. The process area could be a substrate
cassette, a reactor, or a loadlock. Substrate transfer module 1360
is operated under lab ambient. Module 1360 interfaces with
substrate loaders (or substrate cassettes) 1361 to bring the
substrate 1355 into the integrated system or to return the
substrate to one of the cassettes 1361.
[0157] As described above in process flow 1300 of FIG. 11A, the
substrate 1355 is brought to the integrated system 1350 to deposit
barrier layer, to prepare barrier surface for copper layer
deposition, and to prepare post-CMP copper surface for electroless
cobalt-alloy deposition. As described in step 1301 of process flow
1300, top copper surface 122a of metal lines 101 is etched to
remove native copper oxide. Once the copper oxide is removed, the
exposed tungsten surface 122a of FIG. 12A needs to be protected
from exposure to oxygen. If the removal process is an Ar sputtering
process, the Ar sputtering reactor 1371 is coupled to the vacuum
transfer module 1370. If a wet chemical etching process is
selected, the reactor should be coupled to the controlled-ambient
transfer module 1380, not the lab-ambient transfer module 1360, to
limit the exposure of the clean tungsten surface to oxygen.
[0158] Afterwards, the substrate is deposited with first and second
barrier layers. The first barrier layer 130.sub.I of FIG. 12B is
deposited by an ALD process, which is a dry process and is operated
at less than 1 Torr. The ALD reactor 1372 is coupled to the vacuum
transfer module 1370. The second barrier layer 130.sub.II of FIG.
12B is deposited by a PVD or ALD process, which is a dry process
and is operated at less than 1 Torr. The PVD reactor 1373 is
coupled to the vacuum transfer module 1370. The substrate can
undergo an optional hydrogen reduction process to ensure the
barrier layer surface is metal-rich for electroless copper
deposition. The hydrogen reduction reactor 1374 can be coupled to
the vacuum transfer module 1370. At this stage, the substrate is
ready for electroless copper deposition. The electroless copper
plating can be performed in an electroless copper plating reactor
1381 to deposit a conformal copper seed layer, as described in step
1307 of FIG. 13A. As described above, the deposition of the gap
fill copper layer at step 1308 of FIG. 13A can be deposited in the
same electroless plating reactor 1381 with different chemistry, or
in a separate ECP reactor 1381'.
[0159] Afterwards, the substrate is removed of copper overburden
and barrier overburden, as described in step 1309 of FIG. 13A. The
removal of copper overburden and barrier over burden can be
accomplished in one CMP system 1383, or in two CMP systems. In the
embodiment shown in FIG. 13A, only one CMP system 1383 is used.
After CMP removal of copper and barrier overburden, the substrate
surface needs to be cleaned to remove surface contaminants. Wet
clean system 1385 is used to remove copper BTA complexes and metal
oxides. O.sub.2 plasma system 1377 is used to remove organic
contaminants. In one embodiment, O.sub.2 plasma process to remove
organic contaminants can be performed in the hydrogen reduction
chamber 1374.
[0160] After the removal of contaminants, the substrate undergoes a
reduction process, as described in step 1312 of FIG. 13A. The
hydrogen reduction process is used to reduce copper oxide to copper
and can occur in the same reduction reactor 1374 used to reduce the
barrier surface to be Ta-rich. Following hydrogen reduction
treatment, the copper surface is ready for electroless cobalt-alloy
deposition, which can be performed in reactor 1387.
[0161] Before the substrate leaves the integrated system 1350, the
substrate can optionally undergoes a surface cleaning process,
which can clean residues from the previous copper plating process.
The substrate cleaning process can be brush clean process, whose
reactor 1163 can be integrated with the lab-ambient transfer module
1360.
[0162] The wet processing systems described in FIG. 13B, which are
coupled to the controlled-ambient transfer module 1380, all need to
meet the requirement of dry-in/dry-out to allow system
integration.
[0163] The apparatus and methods (or processes) described above
apply to preparing metal surface for subsequent metal deposition to
improve metal-to-metal adhesion and EM performance. The inventive
concept can also apply to preparing silicon surface for subsequent
selective metal layer deposition.
3. Engineering a Silicon Surface for Selective Electroless Metal
Deposition to Form Metal Silicide
[0164] The processes described so far are used to improve the EM
performance, metal resistivity, and even yield for copper
interconnects, such as contacts, vias and metal lines. Earlier in
the fabrication sequence of ICs, another metal deposition is
applied on silicon or polysilicon surface to form metal silicide in
the source/drain/gate, resistor, contact-landing regions (such as
resistor contact landing region) of structures, gate region,
capacitor region or inductor region of the device to reduce contact
resistance and provide good ohmic contact.
[0165] FIG. 14A is a cross section of a gate structure 127 that
includes a thin gate oxide 121, a polysilicon layer 105 and a
nitride spacer 107 on a silicon substrate 110. Shallow trench
isolation (STI) 65 is used to separate active devices. On two sides
of the gate structure are source area 61 and drain area 63. On the
source area 61, there is an exposed silicon surface 62. On the
drain area 63, there is an exposed silicon surface 64. On the
polysilicon layer 105, there is an exposed polysilicon 109. Metal
silicide is formed to reduce sheet resistance.
[0166] To form metal silicide, a metal 111, such as nickel (Ni),
titanium (Ti), or cobalt (Co), is first deposited on the silicon
surface, as shown in FIG. 14B. Currently, metal 111 is deposited on
the substrate surface by a PVD process, and is not selective to the
silicon or dielectric regions. The metal is then annealed to form
the metal-silicon alloy (silicide) in regions where the metal is in
contact with the silicon or polysilicon substrate. No silicide is
formed in the dielectric regions. Un-reacted metal is removed
selectively to the silicide, including metal in the dielectric
regions as well as remaining un-reacted metal above the silicided
regions. Electroless metal deposition can be an alternative process
to replace the current Co or Ni deposition process. The advantages
are that the metal-silicide layer can be made thicker and provide
improved etch stop characteristics as well as allow metal-metal
contact formation. To enable electroless metal deposition, the
silicon surface needs to be very clean and free of native silicon
oxide. After metal 111 is selectively deposited on silicon surfaces
62, 64, the substrate is thermally treated at high temperature,
such as between about 800.degree. C. to about 900.degree. C., to
form metal silicide 113, as shown in FIG. 14C. The metal silicide
113 formed can allow contact 125 to electrically communicate with
the drain area 61, as shown in FIG. 14D.
[0167] As describe above, the surface preparation prior to
electroless metal deposition needs to be conducted in a
controlled-ambient environment to ensure the surface on which will
be performed electroless deposition is not exposed to oxygen. FIG.
15A show an embodiment for a process flow 1500 used to form metal
silicide. At step 1501, metal contaminants are removed from all
dielectric surfaces; this can be performed using known methods and
chemistries. Step 1501 is an optional step, which is needed only
when there is concern of surface metal contamination. Organic
contaminants are next removed from substrate surface, step 1502. As
mentioned above, organic contaminants can be removed by either a
variety of dry or wet processes. Afterwards, at step 1503 the
silicon surface is reduced to convert native silicon oxide to
silicon. Native silicon oxide is a self-limiting process;
therefore, the oxide layer is quite thin and does not need an oxide
removal step prior to the reduction process. As described above,
the reduction process can be a hydrogen plasma process.
[0168] After the surface reduction, the silicon surface is ready
for electroless metal deposition. A metal, such as Ni, Ti, or Co,
is selectively deposited over the exposed silicon (including
polysilicon) surface at step 1505. The selective metal deposition
can be accomplished by an electroless process. After electroless
metal deposition, the substrate undergoes an optional substrate
cleaning using known methods and chemistries at step 1507. The
substrate then undergoes a high temperature process (or annealing)
to form metal silicide at step 1509.
[0169] FIG. 15B shows an embodiment of an integrated system 1550
that includes a lab-ambient transfer module 1560, a vacuum transfer
module 1950, and a controlled-ambient transfer module 1580. The
lab-ambient transfer module 1560 is coupled to cassettes 1561 that
hold substrate(s) 1555. In one embodiment, the metal contaminants
are removed by a wet clean process, such as one of the wet clean
processes used to remove metal contaminants described above. The
wet clean can be performed in chamber 1565 coupled to the
lab-ambient transfer module 1560. Since this process step is
optional, chamber 1565 in FIG. 15B is dotted. Following removal of
metal contaminants, organic contaminants are removed.
[0170] In one embodiment, the organic contaminants are removed in
an oxidizing plasma, such as O.sub.2, H2O, or ozone plasma, in
reactor 1571, coupled to the vacuum transfer module 1570, since the
O.sub.2 plasma process is a low pressure dry process, operated at
pressure less than 1 Torr.
[0171] Afterwards, silicon surface reduction at step 1503 of flow
1500 can be performed in reactor 1573. The substrate is then
transferred to the next system to be deposited with the metal used
to form metal silicide (or silicide metal) in an electroless
process reactor 1581. The substrate is transferred from reactor
1573 through vacuum transfer module 1570, loadlock 1575, and
controlled-ambient transfer module 1580, and finally arrives in
reactor 1581 for processing. The electroless metal deposition
reactor 1581 is equipped with a rinse/dry system. The substrate can
undergo an optional substrate cleaning after metal deposition in a
wet clean chamber 1583, as described in process step 1507 of FIG.
15A. After the electroless deposition, the substrate is sent to a
thermal reactor 1576, such as a rapid thermal processing (RTP)
reactor, to form metal silicide.
[0172] The systems described above allow substrate processing that
requires a mixture of low pressure dry process, high pressure
process, and wet processes to be integrated together to limit
oxygen exposure at critical processing steps. FIG. 16 shows a
schematic diagram that shows how different processes are
integrated. The lab-ambient transfer module can integrate with
cassettes, wet process (es), and dry process that do not need to
limit exposure to oxygen (or not-controlled process). The vacuum
transfer module can integrate low-pressure dry processes. The
vacuum transfer module is operated under vacuum, such as less than
1 Torr; therefore, the exposure to oxygen is limited and
controlled. Loadlock I enables substrate transport between the
lab-ambient transfer module and the vacuum transfer module.
Controlled-ambient transfer module can integrate wet processes,
near atmospheric pressure processes, and high-pressure processes.
The term "high pressure" is used to differentiate from low-pressure
process. The pressure of the high-pressure process refers to
pressure greater than atmospheric pressure process, such as the
supercritical CO.sub.2 process described previously. In one
embodiment, there is a loadlock (not shown) between the
high-pressure process chamber and the controlled-ambient transfer
module to enable substrate being efficiently transferred between
the transfer module and the process chamber. Loadlock II enables
substrates to be transferred between the vacuum transfer module and
the controlled-ambient transfer module. The controlled-ambient
transfer module and the reactors coupled to the controlled-ambient
transfer module are filled with inert gas to limit exposure to
oxygen. Loadlock II can be pump down to receive substrate from the
vacuum transfer module. Loadlock II can also be filled with inert
gas to exchange substrate with the controlled-ambient transfer
module.
[0173] While this invention has been described in terms of several
embodiments, it will be appreciated that those skilled in the art
upon reading the preceding specifications and studying the drawings
will realize various alterations, additions, permutations and
equivalents thereof. Therefore, it is intended that the present
invention includes all such alterations, additions, permutations,
and equivalents as fall within the true spirit and scope of the
invention. In the claims, elements and/or steps do not imply any
particular order of operation, unless explicitly stated in the
claims.
* * * * *