U.S. patent application number 11/168559 was filed with the patent office on 2006-01-26 for electroplated interconnection structures on integrated circuit chips.
This patent application is currently assigned to International Business Machines Corporation. Invention is credited to Panayotis Constantinou Andricacos, Hariklia Deligianni, John Owen Dukovic, Daniel Charles Edelstein, Wilma Jean Horkans, Chao-Kun Hu, Jeffrey Louis Hurd, Kenneth Parker Rodbell, Cyprian Emeka Uzoh, Kwong-Hon Wong.
Application Number | 20060017169 11/168559 |
Document ID | / |
Family ID | 33424844 |
Filed Date | 2006-01-26 |
United States Patent
Application |
20060017169 |
Kind Code |
A1 |
Andricacos; Panayotis Constantinou
; et al. |
January 26, 2006 |
Electroplated interconnection structures on integrated circuit
chips
Abstract
A process is described for the fabrication of submicton
interconnect structures for integrated circuit chips. Void-free and
seamless conductors are obtained by electroplating Cu from baths
that contain additives and are conventionally used to deposit
level, bright, ductile, and low-stress Cu metal. The capability of
this method to superfill features without leaving voids or seams is
unique and superior to that of other deposition approaches. The
electromigration resistance of structures making use of CU
electroplated in this manner is superior to the electromigration
resistance of AlCu structures or structures fabricated using Cu
deposited by methods other than electroplating.
Inventors: |
Andricacos; Panayotis
Constantinou; (Croton-on-Hudson, NY) ; Deligianni;
Hariklia; (Tenafly, NJ) ; Dukovic; John Owen;
(Pleasantville, NY) ; Edelstein; Daniel Charles;
(White Plains, NY) ; Horkans; Wilma Jean;
(Ossining, NY) ; Hu; Chao-Kun; (Somers, NY)
; Hurd; Jeffrey Louis; (Marlboro, NY) ; Rodbell;
Kenneth Parker; (Sandy Hook, CT) ; Uzoh; Cyprian
Emeka; (Hopewell Junction, NY) ; Wong; Kwong-Hon;
(Wappingers Falls, NY) |
Correspondence
Address: |
CONNOLLY BOVE LODGE & HUTZ LLP (IBM YORKTOWN)
1990 M STREET, NW
SUITE 800
WASHINGTON
DC
20036-3425
US
|
Assignee: |
International Business Machines
Corporation
Armonk
NY
|
Family ID: |
33424844 |
Appl. No.: |
11/168559 |
Filed: |
June 29, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10773434 |
Feb 9, 2004 |
6946716 |
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11168559 |
Jun 29, 2005 |
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09348632 |
Jul 6, 1999 |
6709562 |
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10773434 |
Feb 9, 2004 |
|
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08768107 |
Dec 16, 1996 |
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09348632 |
Jul 6, 1999 |
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08670200 |
Jun 21, 1996 |
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08768107 |
Dec 16, 1996 |
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60009538 |
Dec 29, 1995 |
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Current U.S.
Class: |
257/762 ;
257/E21.175; 257/E21.585; 257/E21.589; 438/584; 438/687 |
Current CPC
Class: |
H01L 21/2885 20130101;
C25D 3/38 20130101; C25D 5/022 20130101; H01L 21/76885 20130101;
H01L 21/76877 20130101 |
Class at
Publication: |
257/762 ;
438/584; 438/687 |
International
Class: |
H01L 23/48 20060101
H01L023/48; H01L 21/44 20060101 H01L021/44 |
Claims
1. A structure for use in interconnections on an electronic device
comprising: a dielectric layer having a substantially planar upper
surface and having a pattern of recesses therein, the recesses
having a width at the upper surface less than one micrometer, the
recesses being filled with a conductor material that is seamless
and/or void-free; and wherein the conductor material comprises
substantially copper.
2. The structure of claim 1 wherein the recesses have a depth to
width ratio equal to or greater than 1.
3. The structure of claim 1 further including a metal liner between
the conductive layer and the dielectric layer in the recesses.
4. The structure of claim 1 wherein the copper includes small
amounts of a material in said copper selected from the group
consisting of C (less than 2 weight percent), O (less than 1 weight
percent), N (less than 1 weight percent), S (less than 1 weight
percent), and Cl (less than 1 weight percent).
5. The structure of claim 1 wherein the copper includes specific
film microstructures including large grain size relative to film
thickness and/or randomly oriented grains.
6. The structure of claim 5 wherein the small amounts of material
include atoms and/or molecular fragments.
7. The structure of claim 1 wherein the conductor has an activation
energy for electromigration equal to or greater than 1.0 eV and
further includes specific film microstructures including large
grain size relative to film thickness and/or randomly oriented
grains.
8. The structure of claim 1 wherein the conductor material further
includes positive amounts of atoms and/or molecular fragments
containing atoms selected from the group consisting of C, O, N, S,
and Cl.
9. The structure of claim 8 wherein the electromigration resistance
of the copper is enhanced over pure copper.
10. The structure of claim 1 which comprises a double damascene
structure.
11. The structure of claim 1 wherein each of the recesses has a
bottom surface and side surfaces intersecting the bottom surface,
and wherein the conductor material is deposited on the bottom
surface and side surfaces.
12. The structure of claim 11 wherein the bottom surface of each
recess is substantially horizontal with respect to a major plane of
the substrate.
13. A process for fabricating an interconnect structure on an
electronic device with void-free seamless submicron conductors
comprising the steps of: forming an insulating material on a
substrate, lithographically defining and forming recesses for
submicron lines and/or submicron vias in said insulating material
in which interconnection conductor material will be deposited,
forming a conductive layer in said recesses serving as a plating
base, forming a through-mask, depositing by a through-mask plating
process said conductor material in a seamless and void-free manner
by electroplating from a bath containing additives, said bath
additives causing the plating rate to increase with depth along the
sidewall of a recess, thereby preventing the formation of a seam or
void in a conductor in said recesses, and wherein said conductor
material comprising copper.
14. The process of claim 13 wherein said step of depositing
includes depositing Cu as said conductor material.
15. The process of claim 13 further including the step of adding
additives to said bath for incorporating in said conductor material
positive amounts of atoms and/or molecular fragments containing
atoms selected from the group consisting of C, O, N, S, and Cl.
16. The process of claim 13 further including the step of adding
additives to said bath for inducing in said conductor specific film
microstructures including large grain size relative to film
thickness and/or randomly oriented grains.
17. The process of claim 13 further including the step of adding
additives to said bath for incorporating in said conductor material
molecular fragments containing atoms selected from the group
consisting of C, O, N, S and Cl whereby the electromigration
resistance is enhanced over pure Cu.
18. The process of claim 13 further including the step of adding
additives to said bath for inducing in said conductor specific film
microstructures including large grain size relative to film
thickness and/or randomly oriented grains whereby the
electromigration behavior is enhanced over non-electroplated
Cu.
19. The process of claim 13 wherein the depth to width ratio of a
conductor is equal to or greater than 1.
20. The process of claim 13 wherein the depth to width ratio of a
via exceeds 1.
21. The process of claim 20 wherein the depth to width ratio of a
conductor is equal to or greater than 1.
22. The process of claim 13 wherein said step of depositing further
includes the step of placing the upper surface of said substrate in
contact with the surface of said bath.
23. The process of claim 22 wherein said step of depositing further
includes flowing said bath at said surface of said bath.
24. The process of claim 13 wherein said step of depositing further
includes the step of electroplating using a cup plater.
25. The process of claim 13 further including the step of
electroplating from a plating solution comprising a copper salt, a
mineral acid, and one or more additives selected from the group
consisting of an organic sulfur compound with water solubilizing
groups, a bath-soluble oxygen-containing compound, a bath-soluble
polyether compound, or a bath-soluble organic nitrogen compound
that may also contain at least one sulfur atom.
26. The process of claim 25 wherein said plating solution contains
small amounts of a chloride ion in the range from 10 to 300 parts
per million.
27. The process of claim 25 wherein said Cu salt is cupric
sulfate.
28. The process of claim 25 wherein said mineral acid is sulfuric
acid.
29. The process of claim 30 wherein said organic sulfur compound
carries at least one sulfonic group.
30. The process of claim 25 wherein said organic sulfur compound
has at least two sulfur atoms that are vicinal.
31. The process of claim 31 wherein said organic sulfur compound
has at least two sulfur atoms that are vicinal and carries at least
one terminal sulfonic group.
32. The process of claim 25 wherein said organic sulfur compound is
selected from the group consisting of mercaptopropane sulfonic
acid, thioglycolic acid, mercaptobenzthiozol-S-propansulfonic acid
and ethylenedithiodipropyl sulfonic acid, dithiocarbamic acid,
alkali metal salts of said compounds, and amine salts of said
compounds.
33. The process of claim 25 wherein said organic sulfur compound
has the formula X--R.sub.1--(Sn)--R.sub.2--SO.sub.3H where the R
groups are the same or different and contain at least one carbon
atom, X is selected from the group consisting of a hydrogen and a
sulfonic group, and n is 2-5 inclusive.
34. The process of claim 25 wherein said oxygen-containing compound
is selected from the group consisting of polyethylene glycol, and
carboxymethylcellulose.
35. The process of claim 26 wherein said organic nitrogen compound
is selected from the group containing pyridines and substituted
pyridines, amides, quaternary ammonium salts, imines,
phthalocyanines and substituted phthalocyanines, phenazines, and
lactams.
36. The process of claim 13 wherein said process preferentially
deposits said conductor material in corners at a bottom of said
recesses defined in said insulating material.
37. The process of claim 13 wherein the additives are
polarizing.
38. The process of claim 37 wherein the bottom surface of each
recess intersects the side surfaces at a 90.degree. angle.
39. The process of claim 38 wherein the bottom surface of each
recess is substantially horizontal with respect to a major plane of
the substrate.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation-in-part of
co-pending U.S. patent application Ser. No. 08/670,200, filed Jun.
21, 1996, and entitled "Electroplated Interconnection Structures on
Integrated Circuit Chips" and claims priority to co-pending U.S.
provisional application Ser. No. 60/009,538 filed Dec. 29,
1995.
[0002] This application is cross referenced to U.S. patent
application Ser. No. 08/495,249 filed Jun. 27, 1995, by P.
Andricacos et al., entitled "Copper Alloys for Chip and Package
Interconnections and Method of Making," which is directed to copper
alloys for chip and package interconnections with about 0.01 to
about 10 weight percent of carbon, indium and/or tin.
FIELD OF THE INVENTION
[0003] This invention relates to interconnection wiring on
electronic devices such as on integrated circuit (IC) chips and
more particularly to void-free and seamless submicron structures
fabricated by Cu electroplating from baths that contain additives
conventionally used to produce bright, level, low-stress
deposits.
BACKGROUND OF THE INVENTION
[0004] AlCu and its related alloys are a preferred alloy for
forming interconnections on electronic devices such as integrated
circuit chips. The amount of Cu in AlCu is typically in the range
from 0.3 to 4 percent.
[0005] Replacement of AlCu by Cu and Cu alloys as a chip
interconnection material results in advantages of performance.
Performance is improved because the resistivity of Cu and certain
copper alloys is less than the resistivity of AlCu; thus narrower
lines can be used and higher wiring densities will be realized.
[0006] The advantages of Cu metallization have been recognized by
the entire semi-conductor industry. Copper metallization has been
the subject of extensive research as documented by two entire
issues of the Materials Research Society (MRS) Bulletin, one
dedicated to academic research on this subject in MRS Bulletin,
Volume XVIII, No. 6 (June 1993) and the other dedicated to
industrial research in MRS Bulletin, Volume XIX, No. 8 (August
1994). A 1993 paper by Luther et al., Planar Copper-Polyimide Back
End of the Line Interconnections for ULSI Devices, in PROC. IEEE
VLSI MULTILEVEL INTERCONNECTIONS CONF., Santa Clara, Calif., Jun.
8-9, 1993, p. 15, describes the fabrication of Cu chip
interconnections with four levels of metallization.
[0007] Processes such as Chemical Vapor Deposition (CVD) and
electroless plating are popular methods for depositing Cu. Both
methods of deposition normally produce at best conformal deposits
and inevitably lead to defects (voids or seams) in wiring
especially when trenches have a cross section narrower at the top
than at the bottom as a result of lithographic or reactive ion
etching (RIE) imperfections. Other problems of CVD have been
described by Li et al., Copper-Based Metallization in ULSI
Structures--Part II: Is Cu Ahead of its Time as an On-chip
Material?, MRS BULL., XIX, 15 (1994). In electroless plating, while
offering the advantage of low cost, the evolution of hydrogen
during metal deposition leads to blistering and other defects that
are viewed as weaknesses for industry wide implementation.
[0008] An electroplating process for depositing copper, silver or
gold onto a semiconductor wafer is described in U.S. Pat. No.
5,256,274 ('274), which issued on Oct. 26, 1993, to J. Poris. In
FIG. 1A of '274, a copper conductor is shown with a seam in its
center with the legend "GOOD" and in FIG. 1B a copper conductor is
shown with a void in its center with the legend "tBAD." The plating
bath contained 12 ounces/gallon of water of CuSO.sub.4, 5H.sub.2O,
10% by volume of concentrated sulfuric acid, 50 parts per millions
of chloride ion from hydrochloric acid, and TECHNI-COPPER W
additive 0.4% by volume provided by Technic Inc., P.O. Box 965,
Providence, R.I. 02901. Plating was selectively deposited through
an inert mask.
SUMMARY OF THE INVENTION
[0009] A process is described for fabricating a low cost, highly
reliable Cu interconnect structure for wiring in integrated circuit
chips with void-free seamless conductors of sub-micron dimensions.
The process comprises deposition of an insulating material on a
wafer, lithographically defining and forming sub-micron trenches or
holes in the insulating material into which the conductor will be
deposited to ultimately form lines or vias, depositing a thin
conductive layer serving as a seed layer or plating base,
depositing the conductor by electroplating from a bath containing
additives and planarizing or chemical-mechanical polishing the
resulting structure to accomplish electrical isolation of
individual lines and/or vias.
[0010] The invention further provides a process for fabricating an
interconnect structure on an electronic device comprising the steps
of forming a seed layer on a substrate having insulating regions
and conductive regions, forming a patterned resist layer on the
seed layer, electroplating conductor material on the seed layer not
covered by the patterned resist from a bath containing additives,
and removing the patterned resist.
[0011] The invention further provides a process for fabricating an
interconnect structure on an electronic device with void-free
seamless conductors comprising the steps of forming an insulating
material on a substrate, lithographically defining and forming
lines and/or vias in which interconnection conductor material will
be deposited, forming a conductive layer serving as a plating base,
forming a patterned resist layer on the plating base, depositing
the conductor material by electroplating from a bath containing
additives, and removing the resist.
[0012] The invention further provides a process for fabricating an
interconnect structure on an electronic device comprising the steps
of forming a seed layer on a substrate having insulating regions
and conductive regions, forming a blanket layer of conductor
material on the seed layer from a bath containing additives,
forming a patterned resist layer on the blanket layer, removing the
conductor material where not covered by the patterned resist, and
removing the patterned resist. The invention further provides a
conductor for use in interconnections on an electronic device
comprising Cu including small amounts of a material in the Cu
selected from the group consisting of C (less than 2 weight
percent), O (less than 1 weight percent), N (less than 1 weight
percent), S (less than 1 weight percent), and Cl (less than 1
weight percent) formed by electroplating from a bath containing
additives.
[0013] The interconnection material may be Cu electroplated from
baths that contain additives conventionally used to produce bright,
level, low-stress deposits. The rate of Cu electroplating from such
baths is higher deep within cavities than elsewhere. This plating
process thus exhibits unique superfilling properties and results in
void-free seamless deposits that cannot be obtained by any other
method. Interconnection structures made by Cu electroplated in this
manner, are highly electromigration-resistant with an activation
energy for electromigration equal to or greater than 1.0 eV. The
conductor is composed substantially of Cu and small amounts of
atoms and/or molecular fragments of C (less than 2 weight percent),
O (less than 1 weight percent), N (less than 1 weight percent), S
(less than 1 weight percent), and Cl (less than 1 weight
percent).
[0014] Cu which is highly electromigration-resistant is
electroplated from plating solutions that contain additives
conventionally used to produce bright, ductile, and low-stress
plated deposits.
[0015] It is an object of the present invention to electroplate
conductors of Cu such as interconnect wiring without leaving a seam
or a void in the center of the conductor.
[0016] It is a further object of the present invention to
electroplate conductors of Cu with substantially uniform filling
thickness where the conductors have a difference in widths such as
less than 1 micron and greater than 10 microns. The depth to width
ratio of a conductor may be equal to or greater than 1. The depth
to width ratio of a via may exceed 1.
[0017] It is a further object of the present invention to lower the
manufacturing cost of integrated circuits by the combined effects
of 1) blanket deposition of Cu by electrolytic plating, 2) dual
damascene fabrication (an approach in which two levels of
metallization are fabricated in a single blanket-deposition step),
and 3) the ability to planarize the upper surface by processes such
as chemical mechanical polishing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] These and other features, objects, and advantages of the
present invention will become apparent upon consideration of the
following detailed description of the invention when read in
conjunction with the drawing in which:
[0019] FIGS. 1-5 are cross-sectional views of intermediate
structures illustrating the formation of interconnection
wiring.
[0020] FIG. 6 shows multi-level wiring patterns formed with one
plating step.
[0021] FIG. 7 illustrates early stages of deposition with the
deposition rate deep within the feature being greater than the
deposition rate outside of the features.
[0022] FIG. 8 shows late stages of deposition with the deposition
rate inside of the features being greater than the deposition rate
outside of the features.
[0023] FIG. 9 illustrates early stages of deposition with the
deposition rate inside of the features being slower than the
deposition rate outside of the features.
[0024] FIG. 10 shows late stages of deposition with the deposition
rate inside of the features being slower than the deposition rate
outside of the features.
[0025] FIG. 11 illustrates early stages of deposition with the
deposition rate being the same inside and outside of the
features.
[0026] FIG. 12 shows late stages of deposition with the deposition
rate being the same inside and outside of the features.
[0027] FIG. 13 shows a cross-sectional view of a sequence of
plating profiles.
[0028] FIG. 14 shows a cross-sectional view of a feature plated
electrolytically using a plating bath without additives.
[0029] FIG. 15 shows a cross-sectional view of a feature plated
electrolytically using a plating bath with additives.
[0030] FIG. 16 is a cross-sectional view of a substrate having both
submicron and wide cavities to be plated.
[0031] FIG. 17 is a cross-sectional view of the substrate of FIG.
16 which has been subsequently plated in a wafer immersion-type
plating cell.
[0032] FIG. 18 is a cross-sectional view of the substrate of FIG.
16 which has been subsequently plated in a meniscus-type plating
cell (cup plater) where the wafer surface is brought into contact
with the upper surface or meniscus of the electrolyte.
[0033] FIGS. 19 a-d are a grain orientation map, grain contrast
map, inverse pole figure and (111) pole figure of the same region
for a 1 micron thick plated Cu film. The grain size is
approximately 1.4 microns and the crystallographic texture is
random.
[0034] FIGS. 20 a-d are a grain orientation map, grain contrast
map, inverse pole figure and (111) pole figure of the same region
for a 1 micron thick PVD (physical vapor deposition, magnetron
sputter deposited) Cu film. The grain size is approximately 0.4
microns and this film has a strong (111)/(100) crystallographic
texture.
[0035] FIGS. 21a and 21b show the change in resistance versus time
(hours) for plated Cu versus a) CVD Cu and b) PVC Cu films. The
change in resistance is related to the amount of electromigration
damage in the Cu line. Clearly plated Cu has a much improved
electromigration behavior than either CVD or PVD Cu. The activation
energy for plated Cu is 1.1-1.3 eV while that for PVD Cu is
considerably less (0.7-0.8 eV).
[0036] FIGS. 22-26 are cross-sectional views illustrating
through-mask plating on a planar base.
[0037] FIGS. 27-31 are cross-sectional views illustrating
through-mask plating on an excavated base.
[0038] FIGS. 32-35 are cross-sectional views illustrating blanket
plating followed by pattern etching.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0039] A Damascene plating process is one in which plating is done
over the entire wafer surface and is followed by a planarization
process that isolates and defines the features. Plating is preceded
by the deposition of a plating base over the entire wiring pattern
that has been defined lithographically. Layers that improve
adhesion and prevent conductor/insulator interactions and diffusion
are deposited between the plating base and the insulator. A
schematic representation of the process is shown in FIGS. 1-5. The
insulator layer (Si oxide, polymer) 1 cladded by etch/planarization
layers (Si nitride) 2 and 7 is first deposited on the wafer 8; a
resist pattern 3 is formed on the cladded insulator and transferred
to the insulator; a barrier material 4 and a seed layer (Cu) 5 are
subsequently deposited, and Cu 6 is electroplated so that all
features are filled; the structure is brought to its final shape as
shown in FIG. 5 by planarization. It is possible to define
lithographically multiple levels of patterns onto the insulator as
shown in FIG. 6; in this cost-saving fabrication method, the same
sequence of layer deposition is followed.
[0040] In order to avoid the formation of a void or seam in Cu 6,
the rate of electroplating should be higher at low or deep points
within the feature than elsewhere. This is illustrated in FIGS.
7-12 where three possible cases of metal deposition are described.
In the first case shown in FIGS. 7 and 8, metal deposition within
features 11 by using additives to the plating bath is faster than
outside feature 11 at point 12 and results in void-free and
seamless deposits (superfilling) shown in FIG. 8. The preferential
deposition in the interior of features may be due to lower
transport rates of additives at those locations which in turn leads
to an increase in the local rate of Cu deposition. Specifically at
interior corners, the rate of additive transport is lowest thus the
rate of Copper deposition is highest. In the second case shown in
FIGS. 9 and 10, metal deposition within features 14 is slower than
outside the feature 14 at point 15 and results in voids and
high-resistivity lines or vias because deposition within low points
16 of features 14 is from a bath with higher degree of depletion of
the depositing ion. The higher degree of ion depletion gives rise
to a locally elevated overpotential in the plating bath for the
deposition reaction. In the third case shown in FIGS. 11 and 12,
deposition rates everywhere, inside feature 17 and outside feature
17 at point 18, are equal (conformal filling) because there is no
local ion depletion in the liquid plating bath and because the
additives and their beneficial effects (preferential deposition in
interior features) are missing. Although nearly acceptable deposits
can be obtained by conformal filling, a seam 19 in Cu metal 6 is
inevitable in lines and vias with a high aspect ratio. In a
reentrant profile, conformed filling is not forgiving and will
result in a void. It is evident that plating with superfilling as
shown in FIGS. 7 and 8 is the required and preferred method for
Damascene processing. Electrolytic plating from appropriately
formulated solutions is one of the best ways to accomplish the type
of deposition shown in FIGS. 7 and 8. Superfilling and its
relevance to Cu metallization is totally unknown; for example, in
the publication by Li et al. cited above, Li et al. stated that the
via filling capability of electrolytic Cu plating is
"fair-poor."
[0041] Superfilling by the use of additives in the plating bath
makes it possible to create void-free and seamless lines and vias
even if the lithographic process produces features or cavities 22
in a dielectric layer 1 that are narrower at the top than at the
bottom as shown in FIG. 13. Electroplating according to the
invention herein is one of the best ways by which void-free and
seamless lines and vias can be accomplished. Other methods of
deposition such as CVD which at best generate conformal profiles
inevitably lead to gross defects especially when lithographic
imperfections of this kind are present i.e., features or cavities
22 in a dielectric 1 that are narrower at the top than at the
bottom such that sidewall 23 may form an angle with a vertical
reference line 24 with respect to the top surface 26 in the range
from 0 to 200 as shown by arrow 27.
[0042] Copper plating from solutions incorporating additives
conventionally used to produce level deposits on a rough surface
can be used to accomplish superfilling required to fill sub-micron
cavities. One suitable system of additives is the one marketed by
Enthone-OMI, Inc., of New Haven, Conn. and is known as the SelRex
Cubath M system. The above additives are referred to by the
manufacturer as MHy. Another suitable system of additives is the
one marketed by LeaRonal, Inc., of Freeport, N.Y., and is known as
the Copper Gleam 2001 system. The additives are referred to by the
manufacturer as Copper Gleam 2001 Carrier, Copper Gleam 2001-HTL,
and Copper Gleam 2001 Leveller. And another suitable system of
additives is the one marketed by Atotech USA, Inc., of State Park,
Pa., and is known as the Cupracid HS system. The additives in this
system are referred to by the manufacturer as Cupracid Brightener
and Cupracid HS Basic Leveller.
[0043] Examples of specific additives which may be added to a bath
in the instant invention are described in several patents. U.S.
Pat. No. 4,110,176, which issued on Aug. 29, 1978, to H-G Creutz
deceased et al., entitled "Electrodeposition of Copper" described
the use of additives to a plating bath such as poly alkanol
quaternary-ammonium salt which formed as a reaction product to give
bright, highly ductile, low stress and good leveling copper
deposits from an aqueous acidic copper plating bath which patent is
incorporated herein by reference.
[0044] U.S. Pat. No. 4,376,685, which issued on Mar. 15, 1983, to
A. Watson, entitled "Acid Copper Electroplating Baths Containing
Brightening and Leveling Additives," described additives to a
plating bath such as alkylated polyalkyleneimine which formed as a
reaction product to provide bright and leveled copper
electrodeposits from an aqueous acidic bath which patent is
incorporated herein by reference.
[0045] U.S. Pat. No. 4,975,159, which issued on Dec. 4, 1990, to W.
Dahms, entitled "Aqueous Acidic Bath for Electrochemical Deposition
of a Shiny and Tear-free Copper Coating and Method of Using Same,"
described adding to an aqueous acidic bath combinations of organic
additives including at least one substituted alkoxylated lactam as
an amide-group-containing compound in an amount to optimize the
brightness and ductility of the deposited copper, which patent is
incorporated herein by reference. In U.S. Pat. No. 4,975,159, Table
I lists a number of alkoxylated lactams which may be added to a
bath in the instant invention. Table II lists a number of
sulfur-containing compounds with water-solubilizing groups such as
3-mercaptopropane-1-sulfonic acid which may be added to a bath in
the instant invention. Table III lists organic compounds such as
polyethylene glycol which may be added to a bath as surfactants in
the instant invention.
[0046] U.S. Pat. No. 3,770,598, which issued on Nov. 6, 1973, to
H-G Creutz, entitled "Electrodeposition of Copper from Acid Baths,"
describes baths for obtaining ductile, lustrous copper containing
therein dissolved a brightening amount of the reaction product of
polyethylene imine and an alkylating agent to produce a quaternary
nitrogen, organic sulfides carrying at least one sulfonic group,
and a polyether compound such as polypropylene glycol, which patent
is incorporated herein by reference.
[0047] U.S. Pat. No. 3,328,273, which issued on Jun. 27, 1967, to
H-G Creutz et al., entitled "Electrodeposition of Copper from
Acidic Baths," describes copper sulfate and fluoborate baths for
obtaining bright, low-stress deposits with good leveling properties
that contain organic sulfide compounds of the formula
XR.sub.1--(S.sub.n)--R.sub.2--SO.sub.3H, where R.sub.1 and R.sub.2
are the same or different and are polymethylene groups or alkyne
groups containing 1-6 carbon atoms, X is hydrogen or a sulfonic
group, and n is an integer of 2-5 inclusive, which patent is
incorporated herein by reference. Additionally these baths may
contain polyether compounds, organic sulfides with vicinal sulphur
atoms, and phenazine dyes. In U.S. Pat. No. 3,328,273, Table I
lists a number of polysulfide compounds which may be added to a
bath in the instant invention. Table II lists a number of
polyethers which may be added to a bath in the instant
invention.
[0048] Additives may be added to the bath for accomplishing various
objectives. The bath may include a copper salt and a mineral acid.
Additives may be included for inducing in the conductor specific
film microstructures including large grain size relative to film
thickness or randomly oriented grains. Also, additives may be added
to the bath for incorporating in the conductor material molecular
fragments containing atoms selected from the group consisting of C,
O, N, S and Cl whereby the electromigration resistance is enhanced
over pure Cu. Furthermore, additives may be added to the bath for
inducing in the conductor specific film microstructures including
large grain size relative to film thickness or randomly oriented
grains, whereby the electromigration behavior is enhanced over
non-electroplated Cu.
[0049] FIG. 14 shows a cross-sectional view of the cavity-filling
behavior of a plating solution containing 0.3 M cupric sulfate and
10% by volume sulfuric acid of the prior art. Plating has been
interrupted before complete cavity filling to measure deposit
thickness at various locations of the feature thus determining the
type of filling. It is seen that conformal deposits of Cu 30 are
obtained. However, a deposit obtained by the same solution to which
chloride ion and MHy additive have been added, exhibits
superfilling as shown in FIG. 15. The deposition rate deep within
the feature is higher than elsewhere, and finally the deposit of Cu
36 shown in FIG. 15 will be void-free and seamless due to higher
plating rates inside the feature than outside the feature. MHy
concentrations that produce superfilling are in the range from
about 0.1 to about 2.5 percent by volume. Chloride ion
concentrations are in the range from 10 to 300 ppm.
[0050] Similar superfilling results are obtained from a solution
containing cupric sulfate in the rate from 0.1 to 0.4M, sulfuric
acid in the range from 10 to 20% by volume, chloride in the range
from 10 to 300 ppm, and LeaRonal additives Copper Gleam 2001
Carrier in the range from 0.1 to 1% by volume, Copper Gleam
2001-HTL in the range from 0.1 to 1% by volume, and Copper Gleam
2001 Leveller in the range 0 to 1% by volume. Finally, similar
superfilling results are obtained from a solution containing cupric
sulfate, sulfuric acid, and chloride in the ranges mentioned above
and Atotech additives Cupracid Brightener in the range from 0.5 to
3% by volume and Cupracid HS Basic Leveller in the range from 0.01
to 05% by volume.
[0051] The plating processes described thus far with additives
produce superfilling of submicron, high-aspect-ratio features or
cavities when performed in conventional plating cells, such as
paddle plating cells described in U.S. Pat. Nos. 5,516,412,
5,312,532, which issued on May 17, 1994 to P. Andricacos et al.,
and U.S. Pat. No. 3,652,442. However, a further benefit described
below is realized when the process is performed in a plating cell
in which the substrate surface is held in contact only with the
free surface of the electrolyte, for example a cup plating cell
described in U.S. Pat. No. 4,339,319, which issued Jul. 13, 1982,
to S. Aigo, which is incorporated herein by reference. The benefit
here is the superfilling of wide cavities in the range from 1 to
100 microns, which may be present among the narrow (submicron)
features or cavities.
[0052] In a plating cell in which the substrate is submerged in the
electrolyte, wide features in the range from 1 to 100 microns will
fill more slowly than do narrow features having a width less than 1
micron, such as about 0.1 and above; hence wide features
necessitate both a longer plating time and a longer polishing time
to produce a planarized structure with no dimples or depressions on
the top plated surface.
[0053] In contrast in a cup plating cell, when the substrate
surface to be plated is held in contact with the meniscus of the
electrolyte during plating, cavities of greatly different widths
such as less than 1 micron and greater than 10 microns are filled
rapidly and evenly at the same rate.
[0054] The meniscus of the electrolyte is the curved upper surface
of a column of liquid. The curved upper surface may be convex such
as from capillarity or due to liquid flow such as from an upwelling
liquid.
[0055] FIG. 16 is a cross-sectional view of a substrate 60 which
may have an upper layer of dielectric 61 such as silicon dioxide
having surface features or cavities 62 and 63 formed therein for
damascene wiring. Cavities 62 may have a width less than one micron
and cavity 63 may have a width in the range from 1 to 100 microns.
A liner 64 may provide adhesion to dielectric 61 and provide a
diffusion barrier to metals subsequently plated. Liner 64 may be
conductive to act as a plating base for electroplating or an
additional plating base layer may be added.
[0056] FIG. 17 is a cross-sectional view of substrate 60 having an
electrodeposit of metal 66 sufficient to fill cavities 62 and to
fill the wide cavity 63 which was plated in an immersion-type cell.
In FIG. 17, wide feature 63 fills slower than narrow or submicron
features 62. The upper surface 67 has a dip 68 over feature 63 with
respect to the average height of metal 66.
[0057] In FIGS. 17 and 18, like references are used for functions
corresponding to the apparatus of FIGS. 16 and 17.
[0058] FIG. 18 is a cross-sectional view of substrate 60 having an
electrodeposit of metal 66 which may be Cu sufficient to fill
cavities 62 and to fill wide cavity 63 which was plated in a
meniscus-type cup plating cell. As shown in FIG. 18, the substrate
may be placed in contact with the surface of the bath. The bath may
be flowed at the surface of the bath.
[0059] In FIG. 18, wide feature 63 fills as fast as narrow features
62. The upper surface 69 has a very little dip over feature 63 with
respect to the average height of metal 66. Accordingly, we describe
a mode of the invention in which the plating is done in a cup
plater to achieve even superfilling of narrow and wide features. It
is believed that the superior performance of meniscus plating is
due to the higher concentration and perhaps different orientation
of the surface-active additive molecules at the air-liquid surface.
Though these molecules may begin to redistribute when the substrate
is introduced, residual effects probably persist throughout the
plating period, several minutes in duration.
[0060] The electroplated Cu metal 66 shown in FIGS. 16 and 17
consists substantially of Cu and may also contain small amounts of
atoms and/or molecular fragments of C (less than 2 weight percent),
with O (less than 1 weight percent), N (less than 1 weight
percent), S (less than 1 weight percent), or Cl (less than 1 weight
percent). These additional components apparently originate from the
decomposition of additives and are subsequently incorporated in the
deposit 66 in the probable form of molecular fragments rather than
atoms. Chlorine is co-absorbed due to its synergistic role in
activating additive action. As a result, it is believed that these
inclusions reside in the grain boundaries and in so doing, they do
not affect the resistivity of the plated metal. Indeed,
measurements of the resistivity of the plated Cu yield values lower
than 2 .mu..OMEGA.cm. It is also believed that the same molecules
by virtue of the fact that they reside at grain boundaries of Cu
render the electromigration resistance of electroplated Cu much
better than that of pure Cu that has been deposited by other
processes.
[0061] The grain size of electroplated Cu is generally larger than
that produced by other Cu deposition techniques (see FIGS. 19 a-d
and 20 a-d). FIGS. 19 a-d are, respectively, a grain orientation
map, grain contrast map, inverse pole figure and (111) pole figure
of the same region for a 1 micron thick plated Cu film. The grain
size is approximately 1.4 microns and the crystallographic texture
is random. FIGS. 20 a-d are, respectively, a grain orientation map,
grain contrast map, inverse pole figure and (111) pole figure of
the same region for a 1 micron thick PVD Cu film. The grain size is
approximately 0.4 microns and this film has a strong (111)/(100)
crystallographic texture.
[0062] The crystallographic orientation (also known as texture) of
plated Cu is substantially more random than that of non-plated Cu
films (see FIGS. 19 a-d and 20 a-d). This random orientation is
indicated by the uniform distribution of grains in the inverse pole
figure or the (111) pole figure (see FIGS. 19 a-d). This is
substantially different from that seen for non-plated Cu films. For
example, see FIGS. 20 a-d, where there is substantial (100) and
(111) texture in this PVD Cu film.
[0063] The electromigration resistance of electroplated Cu and pure
Cu is a function of the activation energy as measured by the
methods referred to in MRS Bulletin, Volume XVIII, No. 6 (June
1993), and Volume XIX, No. 8 (August 1994) which are incorporated
herein by reference. The activation energy of electroplated Cu is
equal to or greater than 1.0 eV. In addition, FIGS. 21a and 21b
show a comparison of the drift velocity of plated versus a PVD
film. Clearly, the plated Cu shows little change in resistance over
time whereas the PVD Cu film resistance increases dramatically. The
change in resistance is related to the amount of electromigration
damage in the Cu line. Clearly plated Cu has a much improved
electromigration behavior than does PVC Cu. The activation energy
for plated Cu is 1.1-1.3 eV while that for PVD Cu is considerably
less (0.7-0.8 eV).
[0064] The value of the present invention extends beyond
implementation in damascene structures. The increased resistance to
electromigration, associated with the presence of atoms and/or
molecular fragments containing C, O, N, S, and Cl, is similarly
beneficial in conductor elements that are fabricated by
through-mask plating on a planar base as shown in FIGS. 22-26, by
through-mask plating on an excavated base as shown in FIGS. 22 and
27-31, or by blanket plating followed by patterned etching as shown
in FIGS. 22, 23 and 32-35.
[0065] The process for through-mask plating on a planar base is
shown in FIGS. 22-26. FIG. 22 shows an insulating layer 1. FIG. 23
shows a seed layer (Cu) 5 formed over insulating layer 1. A barrier
material 4 (not shown) may be placed as a layer between insulating
layer 1 and seed layer 5. FIG. 24 shows resist 71 which has been
patterned over seed layer 5. FIG. 25 shows Cu 6 after
electroplating through resist 71. FIG. 26 shows the structure of
FIG. 25 with resist 71 removed and with seed layer 5 removed where
not protected by Cu 6. FIG. 26 shows a patterned layer of Cu 6 over
the patterned seed layer 5.
[0066] The process for through-mask plating on an excavated base is
shown in FIGS. 22 and 27-31. FIG. 22 shows an insulating layer 1.
FIG. 27 shows a channel 72 formed in insulating layer 1. FIG. 28
shows a seed layer (Cu) 5 formed over insulating layer 1. A barrier
material 4 (not shown) may be formed underneath seed layer (Cu) 5.
FIG. 29 shows resist 71 which has been patterned over seed layer 5.
FIG. 30 shows Cu 6 in channel 72 and over seed layer 5 which was
deposited by plating through mask or resist 71. FIG. 31 shows Cu 6
with resist 71 removed and with seed layer S removed where not
protected by Cu 6. It is noted that the superfilling attribute of
the plating process of this invention makes it possible to fill
cavities or features in the excavated base without remnant voids or
seams.
[0067] The process for blanket plating followed by pattern etching
is shown in FIGS. 22, 23 and 32-35 for forming patterned lines on
an insulating layer. FIG. 22 shows an insulating layer 1. FIG. 23
shows a barrier layer 4 formed over insulating layer 1. A seed
layer (Cu) 5 is formed on the upper surface of barrier layer 4. A
blanket layer 76 of Cu is formed as shown in FIG. 32 by
electroplating over seed layer 5. A layer of resist 71 is formed
over blanket layer 76 and lithographically patterned as shown in
FIG. 33. FIG. 34 shows blanket layer 76 patterned by etching or
removing by other processes where not protected by resist 71. FIG.
35 shows the patterned blanket layer 76 with resist 71 removed.
[0068] In FIGS. 2-15 and 22-35, like references are used for
functions corresponding to the apparatus of an earlier Fig. or of
FIG. 1.
[0069] While there has been described and illustrated a process for
fabricating an interconnect structure on an electronic device and a
Cu conductor having electromigration resistance due to atoms and/or
molecular fragments of C, O, N, S, and Cl, and specific
microstructural features such as large grains size relative to film
thickness and a random crystallographic orientation, it will be
apparent to those skilled in the art that modifications and
variations are possible without deviating from the broad scope of
the invention which shall be limited solely by the scope of the
claims appended hereto.
* * * * *