U.S. patent application number 12/554137 was filed with the patent office on 2009-12-31 for methods of manufacturing copper interconnect systems.
This patent application is currently assigned to BECK SEMICONDUCTOR LLC. Invention is credited to James A. Cunningham.
Application Number | 20090321938 12/554137 |
Document ID | / |
Family ID | 33456843 |
Filed Date | 2009-12-31 |
United States Patent
Application |
20090321938 |
Kind Code |
A1 |
Cunningham; James A. |
December 31, 2009 |
Methods of Manufacturing Copper Interconnect Systems
Abstract
An integrated circuit (IC) may include a substrate, a first
dielectric layer adjacent the substrate, and at least one trench in
the first dielectric layer. The IC may also include a metal liner
within the at least one trench, and a first conductive region
including copper within the at least one trench. A cap layer
including metal may be provided on the first conductive region. A
second dielectric layer may be over the first conductive region and
the cap layer. A dielectric etch stop and diffusion barrier layer
may be over the second dielectric layer, and a via may be over the
first conductive region and through the second dielectric layer and
the cap layer. A diffusion barrier layer may be on sidewalls of the
via, and an alloy seed layer including copper and at least one of
tantalum, molybdenum, chromium, and tungsten may be over the
diffusion barrier. The allow seed layer may also be over the
dielectric etch stop and diffusion barrier layer, and the alloy
seed layer may be in contact with the first conductive region.
Inventors: |
Cunningham; James A.;
(Saratoga, CA) |
Correspondence
Address: |
WOODCOCK WASHBURN LLP
CIRA CENTRE, 12TH FLOOR, 2929 ARCH STREET
PHILADELPHIA
PA
19104-2891
US
|
Assignee: |
BECK SEMICONDUCTOR LLC
Las Vegas
NV
|
Family ID: |
33456843 |
Appl. No.: |
12/554137 |
Filed: |
September 4, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12056163 |
Mar 26, 2008 |
7585766 |
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12554137 |
|
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|
11278914 |
Apr 6, 2006 |
7372152 |
|
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12056163 |
|
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|
10803475 |
Mar 18, 2004 |
7026714 |
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11278914 |
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60455496 |
Mar 18, 2003 |
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Current U.S.
Class: |
257/751 ;
257/E23.142 |
Current CPC
Class: |
H01L 21/76886 20130101;
H01L 21/76844 20130101; H01L 21/76831 20130101; H01L 21/76865
20130101; H01L 21/76807 20130101; H01L 21/76858 20130101; H01L
21/76849 20130101; H01L 21/76855 20130101; H01L 21/76864 20130101;
H01L 2924/0002 20130101; H01L 21/76805 20130101; H01L 2924/0002
20130101; H01L 21/76873 20130101; H01L 23/53238 20130101; H01L
21/76843 20130101; H01L 2924/00 20130101 |
Class at
Publication: |
257/751 ;
257/E23.142 |
International
Class: |
H01L 23/522 20060101
H01L023/522 |
Claims
1. An integrated circuit comprising: a substrate; a first
dielectric layer disposed over the substrate; a first conductive
region formed within a first trench in the first dielectric layer;
a metal-based cap layer disposed over the first conductive region,
wherein the cap layer includes at least one of Cobalt, Boron,
Tungsten, Phosphorous, or Ruthenium; a second dielectric layer
disposed over the first dielectric layer; a first diffusion barrier
disposed between the first and second dielectric layers; and a
second diffusion barrier disposed over horizontal surfaces of the
second dielectric layer.
2. The integrated circuit of claim 1 wherein the first diffusion
barrier is formed using at least one of the following materials:
silicon nitride, Si--C, Si--C--N--O, Si--O--N, or Si--C--N.
3. The integrated circuit of claim 1, further comprising a liner
formed of at least one of the following materials: Ta, Ta/TaN,
Ta/TaN/Ta or other combinations thereof, or, an alloy or mixture
comprising Ti added to Ta, Cr, Mo, W, Rh, Ru or Re.
4. The integrated circuit of claim 1 wherein the second diffusion
barrier is a dielectric barrier formed using at least one of the
following materials: Ta, Ta/TaN, Ta/TaN/Ta or other combinations
thereof, or, for adhesion enhancement, an alloy or mixture
comprising Ti added to Ta, Cr, Mo, W, Rh, Ru or Re.
5. The integrated circuit of claim 1 wherein the second diffusion
barrier is formed using at least one of the following materials:
Ta, Ta/TaN, Ta/TaN/Ta, or other combinations thereof, or an alloy
or mixture comprising Ti added to Ta, Cr, Mo, W, Rh, Ru, or Re.
Description
CROSS-REFERENCE
[0001] This application is a continuation of U.S. patent
application Ser. No. 12/056,163, filed Mar. 26, 2008, currently
pending, which is a continuation of U.S. patent application Ser.
No. 11/278,914, filed Apr. 26, 2006, now U.S. Pat. No. 7,372,152,
which is a continuation of U.S. patent application Ser. No.
10/803,475, filed Mar. 18, 2004, now U.S. Pat. No. 7,026,714, which
claims the benefit of U.S. Provisional Application No. 60/455,496,
filed Mar. 18, 2003, the entireties of all of which are
incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to the field of electronics,
and, more particularly, to semiconductor devices including copper
interconnects and related methods. Even more particularly, the
invention relates to reliability improvements for copper
interconnects.
BACKGROUND
[0003] Doped seed layers have been disclosed in the prior art,
their presence directed to various objectives. These include U.S.
Pat. No. 5,969,422 to Ting et al.; U.S. Pat. No. 6,249,055 to
Dubin; U.S. Pat. No. 6,181,012 to Edelstein et al.; U.S. Pat. No.
6,066,892 to Ding et al.; and U.S. Pat. No. 6,462,675 to Paranjpe
et al. But none of these inventions discloses a copper interconnect
system where a copper via to underlying copper interconnect makes a
substantially direct copper to copper connection without the
presence of an intervening diffusion barrier. The presence of such
a barrier tends to degrade the electromigration resistance of the
system.
[0004] Two prior art patents disclose where direct or near direct
copper-to-copper interfaces are formed at the base of a copper via
to an underlying copper interconnect. U.S. Pat. No. 6,169,024 to
Hussein forms a seed layer of varying thicknesses against a
refractory metal diffusion barrier as are common in the industry,
and then etches both refractory metal barrier and the dielectric
cap material at the base of the via with the seed material acting
as a mask. Such a process is inherently extremely difficult to
control, the main problem residing in controlling the required wide
variation in seed layer thicknesses.
[0005] U.S. Pat. No. 6,380,075 to Cabral, Jr. et al. discloses a
process which purports a CVD method wherein the liner thickness is
very thin or nonexistent at the base of the via and yet of
sufficient thickness on the horizontal surfaces under the copper
interconnect regions. Such a process is also inherently extremely
difficult to control. Neither of these prior art references
discloses use of a metal-based cap layer, alloy seed layers, or
methods of improved interface bonding.
[0006] U.S. Patent Application Publication No. 2002/0106895 A1 to
Chung discloses a method to provide direct copper-to-copper contact
at the base of a copper dual-damascene via. But no seed layer is
disclosed, and no methods for improving the adhesion at the various
copper interfaces are disclosed. Upon application of high current
density, any copper interface where weak bonding of the adjoined
film or material is present, tends to degrade the electromigration
and stress induced migration failure rates.
[0007] U.S. Patent Application Publication No. 2003/0190829 A1 to
Brennan also proposes a method to provide direct copper-to-copper
contact at the base of a copper dual-damascene via. But no capping
or seed layers are disclosed, and no methods for improving the
adhesion of the various interfaces are disclosed. The method
requires use of high dielectric constant nitride-based etch stop
and diffusion barriers. This tends to degrade RC delays in the
copper interconnects. A more serious concern is that the patent
discloses no diffusion barriers for the edges of the copper
interconnects.
SUMMARY
[0008] In view of the foregoing background, it is therefore an
object of the present invention to provide a copper interconnect
system which uses a conductive, metal-based cap layer, and
substantially direct copper-to-copper contact at the interface of
the copper via to the underlying copper interconnect. The
invention, with its several embodiments, is focused on damascene
type implementations. Within the dual-damascene structure, doped,
that is, alloy seed layers may be used both against dielectric
(insulating) and metal-based or conductive diffusion barriers. The
resulting structure has improved resistance against
electromigration (EM) and stress induced migration failures.
[0009] The invention provides enhanced adhesion or interfacial
bonding for all critical interfaces including: seed layer to
dielectric diffusion barrier layer; cap layer to main copper
region; conductive trench liner barrier materials to seed layer;
and conductive trench liner barrier materials to main surrounding
inter-level dielectric (ILD). Use of high dielectric insulators may
be minimized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIGS. 1-3 are schematic cross-sectional views of an
integrated circuit during manufacturing thereof in accordance with
a first embodiment of the present invention.
[0011] FIGS. 4-6 are schematic cross-sectional views of an
integrated circuit during manufacturing thereof in accordance with
a second embodiment of the present invention.
[0012] FIGS. 7 and 8 are schematic cross-sectional views of
alternate embodiments of the invention.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
[0013] The present invention now will be described more fully with
reference to the accompanying drawings, in which preferred
embodiments of the invention are shown. This invention may,
however, be embodied in many different forms and should not be
construed as limited to the embodiments set forth herein; rather,
these embodiments are provided so that this disclosure will be
thorough and complete, and will fully convey the scope of the
invention to those skilled in the art.
[0014] The following first embodiment is directed to improving the
various weaknesses of prior art copper interconnect technology as
discussed in detail above. These include weak bonding of the copper
interconnect at the various interfaces present. Among various
improvements, this invention teaches the use of certain metals and
alloys to improve the bonding. This results in greatly reduced
interface diffusion rates. This improves EM resistance, and reduces
stress induced migration failure rates.
[0015] Referring to FIG. 1, a first Damascene-type interconnect
comprising copper 3 is formed in an SiO.sub.2 or low-k type
insulator 1 that, in turn, is on or adjacent a substrate 30. A
liner 4 is formed by PVD, CVD or by (atomic layer deposition) ALD
or by other methods, of Ta, Ta/TaN, Ta/TaN/Ta or other combinations
thereof, or, for adhesion enhancement, an alloy or mixture
comprising Ti added to Ta, Cr, Mo, W, Rh, Ru or R--such alloys
yielding improved adhesion to copper based metal 3. The barriers
may also contain nitrogen or Si. In general, nitrogen tends to
reduce grain boundary diffusion rates, and small concentrations of
Si tend to produce amorphous or more amorphous films. The liner 4
may have a thickness in the range of one monolayer to 200 .ANG..
The added Ti concentration would range from 1 to 30%. Diffusion
barrier liners of rhodium, ruthenium or rhenium may also be used as
disclosed in U.S. Pat. No. 6,441,492, the entire contents of which
are incorporated herein by reference.
[0016] Following the planarization step using CMP, as indicated by
a plane shown by the dashed line 21, a selective metal-based cap 5
is then added to the surface of interconnect 3 as described above.
The cap 5 may be formed using electroless Co-based alloys, such as
Co--W--P or Co--W--B, or may be the Ru system described above, or
another selectively deposited conductive system offering both a
measure of good or improved adhesion to copper and an adequate
diffusion barrier against penetration of copper into the
surrounding interlevel dielectric ILD. (An alternative embodiment
for a Ru-based barrier is described below.)
[0017] Dielectric layer 2 is then formed over the capped
interconnect. Dielectrics used for the ILD may be SiO.sub.2-based
or may be one of various low-k insulators as known in the art.
These include films such as: oxides containing fluoride (FSG),
SiLK.TM., Black Diamond.TM., various spin-on organics, HSQ, various
high-porosity SiO.sub.2-based types, and many others now under
investigation and refinement in the industry.
[0018] Etch stop and dielectric diffusion barriers 6 are then
formed using silicon nitride, Si--C, Si--C--N--O, Si--O--N, or
Si--C--N materials as are known in the art. Dielectric layer 7 and
etch stop and optional diffusion barrier layer 8 are added prior to
the formation of opening 9. Opening 9 is then formed using
photoresist layers, not shown, as is known for the via for the
first dual-damascene process. Differential etch rates for the
dielectric diffusion barriers are not required in this process, so
the materials may be selected for a minimum dielectric constant.
The Co-based barrier system 5 is then removed over the copper 3
using argon bombardment or backsputter cleaning. For a Ru-based
embodiment, the Ru metal may be removed in fluorine-based RIE
plasma chemistry. For a Ru-based cap an alternative is to remove
the cap material upon etching the trench for the interconnect, that
is, etch the film after the via first step. Photoresist is then
added and a trench for interconnect 12 is formed by plasma etching
as is known in the art. Fluorine or chlorine plasma chemistries do
not appreciably attack exposed copper-based metal 3.
[0019] FIG. 1 shows the system at the intermediate step following
opening of the trenches for a second overlying interconnect 12.
FIG. 2 shows the structure following the deposition and anisotropic
etchback of a conductive diffusion barrier 8 which can be of
similar composition to layer 4. Alternately, the barrier may be a
dielectric barrier such as silicon nitride, Si--C--N--O or
Si--C--N. A diffusion barrier is deposited and is anisotropically
etched back leaving edge protection layers 10 (FIG. 2). Materials,
such as those used for layer 8 could be used. Selective plasma
etching chemistries may be employed using chlorine or fluorine or
combinations thereof as are known in the art. The copper material 3
is exposed at the base of the via. The exposed copper at this point
may be cleaned and optionally passivated using displacement plating
with a metal more noble than copper, such as Ag, Pd or Pt. This
film thickness may be one monolayer up to about 50 .ANG.. Following
this optional plating, the surrounding dielectrics nay be cleaned
with chemical complexing agents. The exposed copper 3 may also be
sputter cleaned prior to the formation of layer 11. The passivation
step provides substantially no, or only partial, diffusion barrier
properties at this copper 3 to copper 12 interface.
[0020] FIG. 3 shows the structure after deposition of an alloy seed
layer 11. This alloy comprises copper and Ta, Cr, Mo, or W forming
a mixture or alloy with improved adhesion to dielectric diffusion
layer 6. The dopants Ta and Cr are preferred. The alloy seed layer
11 may be deposited by PVD, or other methods such as CVD, such that
a reasonably conformal film is created. The added refractory metals
may be in atomic concentrations ranging from 1 to 30% or more. Seed
layer 11 is designed to be strongly copper-like and does not
contain sufficient dopant or alloying material such that it behaves
as a diffusion barrier. Copper metal or copper alloy 12 may be then
formed by electroplating or by electroless plating as is known in
the art. A cap 13 is added to the copper or copper alloy layer 12
in like manner to layer 5. The copper or copper-based metal 12
makes direct, or near direct contact, or equivalent direct contact,
or contact without the intervening presence of a substantial or
diffusion-blocking thickness of an immiscible or passive diffusion
barrier, to copper or copper alloy metal 3. This main region copper
12 to lower level copper 3 contact is made through seed layer 11
comprising copper.
[0021] Referring now additionally to FIGS. 4-6, a second embodiment
provides a conductive coating or cap layer on the copper
interconnect surface for the purpose of interface diffusion rate
reduction. The coating is not a robust diffusion barrier, and for
that reason it is covered by a dielectric diffusion barrier. The
coating is etchable in halide-containing anisotropic plasma etching
chemistries (RIE), and may be removed so that overlying copper vias
may make a more direct copper-to-copper connection. This aids the
prevention of copper flux divergence at the base of a via, a
phenomenon which tends to reduce EM resistance. This embodiment
also has no substantial diffusion barrier thickness remaining at
the base of copper vias.
[0022] Following FIG. 4, a copper based interconnect 12 is formed
over substrate 11 by a damascene-type process. The trench is lined
with diffusion barrier 13 as described in the first embodiment
above. The film 23 below the dashed line 22 is an insulating layer
as is known in the art, and is described in the first embodiment
above. After CMP, terminating approximately along the dashed line
22 shown, the exposed copper interconnect 12 is passivated using
palladium or platinum. The Pt or Pd films 14 may be selectively
applied by immersion plating or by electroless plating. A film
ranging in thickness from one monolayer to about 200 .ANG. may be
applied. Following the application of this metal film, the device
may be annealed at 300-500.degree. C. to interdiffuse the plated
metal and copper. Both metals form continuous solid solutions with
copper, and upon annealing, form a hardened surface alloy layer
which retards the surface transport of copper upon elevated
temperature or EM stress. Both metals are plasma etchable in halide
chemistries. Alternately, the heat treatment could be performed
later in the process.
[0023] Following the surface passivation step insulating films 15,
16, 17, 18, and 19 are deposited as is known in the art. Films 16
and 17 are SiO.sub.2-based or may be one of various low-k
insulators as known in the art. These include films listed in the
first embodiment. Films 15, 18 and 19 are etch stop diffusion
barrier layers, such as silicon nitride or Si--C or PECVD Si--C--N
or Si--C--N--O and other "carbide" type films as are known in the
art.
[0024] As shown in FIG. 4, the stack of insulating films is plasma
etched, employing a photoresist layer, not shown, down to etch stop
15, as is known in the art. After applying another PR layer, not
shown, which defines the trench region for a second copper based
interconnect, not shown completed, the trench region 32 is etched,
and film 15 and unreacted or non-interdiffused portions of
passivation film 14 are removed down to the surface of material 12
comprising copper. This may be seen in FIG. 5.
[0025] Following this step, a diffusion barrier 33 is formed as
described in the first embodiment in the form of an edge
spacer.
[0026] An alternative embodiment is etching this barrier film,
which results in edge film 33, to a non-zero thickness of 20 .ANG.
or less such that it is a partial barrier in the horizontal
regions. In this case, the barrier film is electrically
conducting.
[0027] Following this step, an alloy seed layer 34 is formed as
described in the first embodiment. FIG. 6 shows the device
following the formation of alloy seed layer 34.
[0028] It may be noted that the preferred alloying elements Ta and
Cr for the alloy seed layer are carefully selected. They require
two properties to perform optimally in this invention:
[0029] (1) They should be capable of forming strong M-O bonds so
that good adhesion is available against the dielectric barriers
such as layer 18. The Gibbs function free energy per oxygen bond
for metals decreases as:
Ti>Al>Ta.apprxeq.Cr>Si>Mo.apprxeq.W.apprxeq.Co.apprxeq.Re>-
Cu>Ru. The preferred metals also form strong M-N bonds.
[0030] (2) They should be immiscible (passive) with copper so that
negligible interdiffusion occurs from the alloying elements into
the main or thicker copper interconnect region formed above and
onto film 34.
[0031] The main current-carrying copper region above film 34 may be
unalloyed or lightly alloyed with elements which only cause small
increases in resistivity such as, for example, Ag or Cd.
Interdiffusion of substantial concentrations of Ta, Cr, Mo or W
would cause significant increases in the resistivity in the main
current-carrying copper material formed onto the alloy seed layers.
If this were to happen, the system may not be viable. An exemplary
alloy is Ta and copper, with the Ta concentration approximately 5
to 30 at %. A preferred alloy may be 10 to 20 at % Ta in copper. A
preferred method of deposition of the seed alloy is PVD or IPVD
(ionized PVD) as developed by Applied Materials and others. The
sputtering parameters may be adjusted to maximize edge coverage
over bottom coverage. The films may also be applied by CVD.
[0032] Finally, the bulk of the copper based interconnected is
formed onto the seed layer and planarized using CMP as described in
the first embodiment. The bulk copper is typically
electroplated.
[0033] An alternate embodiment for the metal cap layer over copper
is now disclosed. This barrier, in its more robust form, should
both firmly bond to both copper and the overlying oxide insulation
or dielectric, and offer passive diffusion barrier characteristics
as well. An exemplary system is the following material stack:
plated copper/displacement plated silver followed by displacement
palladium/selective electroless plated Ru/light oxidation. This
system requires no overlying dielectric diffusion barrier; thus the
ILD dielectric constant is minimized.
[0034] FIGS. 7 and 8 show the expected metallurgy of the system
upon annealing. A copper interconnect surface such as that of
copper region 3 prior to application of film 5 is represented in
FIG. 7 as electroplated copper 35. Approximately 20 .ANG. of
immersion silver 36, approximately 10 .ANG. of immersion palladium
37, and approximately 100 .ANG. of electroless Ru 38 are applied
over copper layer 35. Upon annealing, at about 400.degree. C. in a
mixture of N.sub.2 and O.sub.2, solid state diffusion and oxidation
of the Ru occurs producing the structure of FIG. 8 represented by
Cu phase 41, Cu+Pd solid solution 42, Ag+Pd solid solution 39, 1-2%
Ru in Pd.sub.2 phase 43, and conductive RuO.sub.2 surface layer 40.
Grain boundaries 44 would contain some oxidized Ru in the remaining
Ru layer derived from Ru 38.
[0035] Upon application of an overlying dielectric such as film 2,
the system provides a firm and strongly bound transition from
copper to diffusion barrier to overlying dielectric.
[0036] Using non-cyanide complexing agents, various solutions may
be prepared for immersion plating bright films of silver to copper.
Silver added to copper has the smallest known effect on resistivity
of all the elements. Since reduction potentials increase as
Cu>Ru>Rh>Ag>Pd>Pt>Au, Pd may be immersion plated
over Ag. Such an action also fills any pinholes in the Ag layer
making the final film more dense.
[0037] Solutions for immersion plating of palladium are known. Ru
may be electroless plated using hydrazine as a reducing agent. The
final film stack may be annealed in N.sub.2 followed by
N.sub.2/O.sub.2 forming a conductive RuO.sub.2 layer and
simultaneously stuffing the grain boundaries of the Ru passive
barrier.
[0038] For the embodiments where the Ru and RuO.sub.2 layer were at
the base of a via, the films could be removed or thinned. Since Ru
forms volatile fluorides, this can be accomplished during the
anisotropic plasma etching through the via ILD. This provides a
more direct Cu to Cu connection from via to interconnect.
[0039] In recent years, Ru based barriers have been under
investigation as diffusion and oxidation barriers for very high-k,
stacked, DRAM capacitor applications.
[0040] Many modifications and other embodiments of the invention
will come to the mind of one skilled in the art having the benefit
of the teachings presented in the foregoing descriptions and the
associated drawings. Therefore, it is to be understood that the
invention is not to be limited to the specific embodiments
disclosed, and that other modifications and embodiments are
intended to be included within the scope of the appended
claims.
* * * * *