U.S. patent application number 13/302721 was filed with the patent office on 2012-03-15 for copper alloy for wiring, semiconductor device, method for forming wiring, and method for manufacturing semiconductor device.
This patent application is currently assigned to NEC CORPORATION. Invention is credited to Yoshihiro HAYASHI, Masayuki HIROI, Nobuyuki IKARASHI, Makoto UEKI.
Application Number | 20120061844 13/302721 |
Document ID | / |
Family ID | 32500815 |
Filed Date | 2012-03-15 |
United States Patent
Application |
20120061844 |
Kind Code |
A1 |
UEKI; Makoto ; et
al. |
March 15, 2012 |
COPPER ALLOY FOR WIRING, SEMICONDUCTOR DEVICE, METHOD FOR FORMING
WIRING, AND METHOD FOR MANUFACTURING SEMICONDUCTOR DEVICE
Abstract
A wiring metal contains a polycrystal of copper (Cu) as a
primary element and an additional element other than Cu, and
concentration of the additional element is, at crystal grain
boundaries composing the Cu polycrystal and in vicinities of the
crystal grain boundaries, higher than that of the inside of the
crystal grains. The additional element is preferably at least one
element selected from a group consisting of Ti, Zr, Hf, Cr, Co, Al,
Sn, Ni, Mg, and Ag. This Cu wiring is formed by forming a Cu
polycrystalline film, forming an additional element layer on this
Cu film, and diffusing this additional element from the additional
element layer into the Cu film. This copper alloy for wiring is
preferred as metal wiring formed for a semiconductor device.
Inventors: |
UEKI; Makoto; (Tokyo,
JP) ; HIROI; Masayuki; (Tokyo, JP) ; IKARASHI;
Nobuyuki; (Tokyo, JP) ; HAYASHI; Yoshihiro;
(Tokyo, JP) |
Assignee: |
NEC CORPORATION
Tokyo
JP
|
Family ID: |
32500815 |
Appl. No.: |
13/302721 |
Filed: |
November 22, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12426549 |
Apr 20, 2009 |
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13302721 |
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10538306 |
Jun 9, 2005 |
7545040 |
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PCT/JP2003/012080 |
Sep 22, 2003 |
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12426549 |
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Current U.S.
Class: |
257/770 ;
257/E29.139; 420/591 |
Current CPC
Class: |
H01L 2924/0002 20130101;
H01L 2924/0002 20130101; H01L 23/53238 20130101; H01L 21/76883
20130101; H01L 23/53233 20130101; H01L 2924/00 20130101 |
Class at
Publication: |
257/770 ;
420/591; 257/E29.139 |
International
Class: |
H01L 29/43 20060101
H01L029/43 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 9, 2002 |
JP |
2002-356291 |
Claims
1. A polycrystalline copper alloy for wiring comprising a copper
and an additional element, wherein the additional element is at
least one element selected from a group consisting of Ti
(titanium), Zr (zirconium), Hf (hafnium), Cr (chromium), Co
(cobalt), Al (aluminum), Sn (tin), Ni (nickel), and Mg (magnesium),
and concentration of the additional element, at boundaries between
the polycrystalline copper alloy and an insulator films contacting
the polycrystalline copper alloy, is higher than that of inside of
crystal grains.
2. A polycrystalline copper alloy for wiring comprising a copper
and an additional element, wherein the additional element is at
least one element selected from a group consisting of Ti
(titanium), Zr (zirconium), Hf (hafnium), Cr (chromium), Co
(cobalt), AI (aluminum), Sn (tin), Ni (nickel), and Mg (magnesium),
and concentration of the additional element, at grain boundaries of
crystal grains composing the polycrystalline copper alloy and in
vicinities of grain boundaries, is higher than that of the inside
of the crystal grains.
3. The polycrystalline copper alloy for wiring as set forth in
claim 1, wherein an oxide of the additional element is formed at
said grain boundaries and/or in vicinities of said grain
boundaries.
4. The polycrystalline copper alloy for wiring as set forth in
claim 1, wherein a barrier metal in a barrier film that is formed
to surround the polycrystalline copper alloy is not oxidized.
5. The polycrystalline copper alloy for wiring as set forth in
claim 1, concentration of the additional element in the crystal
grains is 0.1 atomic percent or less.
6. The polycrystalline copper alloy for wiring as set forth in
claim 1, wherein at the crystal grain boundaries and/or in the
vicinities of grain boundaries, intermetallic compounds of Cu and
at least one element selected from a group consisting of Ti, Zr,
Hf, Cr, Co, Al, Ni, and Mg are formed.
7. The polycrystalline copper alloy for wiring as set forth in
claim 1, wherein at the crystal grain boundaries and/or in the
vicinities of grain boundaries, oxides of at least one element
selected from a group consisting of Ti, Zr, Fit Cr, Co, Al, Ni, and
Mgare formed.
8. The polycrystalline copper alloy for wiring as set forth in,
claim 1, wherein concentration of the additional element at the
grain boundaries and in the vicinities of grain boundaries is on
the order of 2 to 1000 times the additional element concentration
at the inside of the crystal grains.
9. The polycrystalline copper alloy for wiring as set forth in
claim 1, wherein concentration of the additional element at the
grain boundaries and in the vicinities of grain boundaries is on
the order of 10 to 100 times the additional element concentration
at the inside of the crystal grains.
10. A polycrystalline copper alloy for wiring comprising a copper
and an additional element, wherein the additional element is at
least one element selected from a group consisting of Ti
(titanium), Zr (zirconium), Hf (hafnium), Cr (chromium), Co
(cobalt), Al (aluminum), Sn (tin), Ni (nickel), and Mg (magnesium),
and concentration of the additional element, at the interface
between the polycrystalline copper alloy and a barrier film that is
formed to surround the polycrystalline copper alloy and in
vicinities of said interface, is higher than that of inside of
crystal grains.
11. A semiconductor device comprising a substrate on which a
semiconductor element is formed, and a metal wiring composed of a
polycrystalline copper alloy, said polycrystalline copper alloy
comprising a copper and an additional element, wherein the
additional element is at least one element selected from a group
consisting of Ti (titanium), Zr (zirconium), Hf (hafnium), Cr
(chromium), Co (cobalt), Al (aluminum), Sn (tin), Ni (nickel), and
Mg (magnesium), and concentration of the additional element at
boundaries between the polycrystalline copper alloy and an
insulator films contacting the polycrystalline copper alloy, is
higher than that of inside of crystal grains
12. A semiconductor device comprising a substrate on which a
semiconductor element is formed, and a metal wiring composed of a
polycrystalline copper alloy, said polycrystalline copper alloy
comprising a copper and an additional element, wherein the
additional element is at least one element selected from a group
consisting of Ti (titanium), Zr (zirconium), Hf (hafnium), Cr
(chrotaium), Co (cobalt), Al (aluminum), Sn (tin), Ni (nickel), and
Mg (magnesium), and concentration of the additional element, at
grain boundaries of crystal grains composing the polycrystalline
copper alloy and in vicinities of grain boundaries, is higher than
that of inside of crystal grains.
Description
[0001] This is a divisional of application Ser. No. 12/426,549
filed Apr. 20, 2009, which is a divisional of application Ser. No.
10/538,306 filed Jun. 9, 2005, which is a National Stage entry of
PCT Application No. PCT/JP2003/12080, filed Sep. 22, 2003, which
claims priority from Japanese Patent Application No. 2002-356291,
filed Dec. 9, 2002. The entire disclosures of the prior
applications are considered part of the disclosure of the
accompanying divisional application and are hereby incorporated by
reference.
TECHNICAL FIELD
[0002] The present invention relates to a copper alloy for wiring,
a semiconductor device using said wiring, a method for forming the
wiring, and a method for manufacturing the semiconductor device,
and in particular, to a copper alloy for wiring with an improved
wiring reliability, a semiconductor device using wiring formed of
said copper alloy, a method for forming the wiring, and a method
for manufacturing the semiconductor device.
BACKGROUND ART
[0003] Conventionally, aluminum (Ai) or Al alloy has been widely
used for a wiring material of semiconductor devices. However, with
the progression in miniaturization and high speed operation of
semiconductor devices, copper (Cu) has been used as a wiring
material for an improvement in transmission delay of wiring,
because copper has a lower resistivity. In addition, Cu has a
melting point of 1083.degree. C., which is higher than the melting
point of Al of 660.degree. C., and is generally considered to be
high in electromigration (EM) resistance and also excellent in the
aspect of reliability.
[0004] When wiring is formed of Cu, since processing by dry etching
of Cu is difficult, a damascene method has been generally used for
forming Cu wiring. The damascene method is a method for forming Cu
wiring by forming wiring grooves in an insulating film formed on a
semiconductor substrate, forming a Cu film so as to fill up the
grooves, and polishing the Cu film until the insulating film is
exposed so as to remove an excessive Cu film on the insulating film
excluding that in the wiring grooves, whereby Cu wiring is provided
in a buried manner into wiring grooves.
[0005] In addition, for using Cu as a wiring material, it is
necessary to provide a barrier metal film around Cu in order to
prevent Cu from diffusing into an insulating film and Cu corrosion.
In the following, description will be given of a currently
generally used manufacturing method of a semiconductor device
having Cu wiring while referring to the drawings.
[0006] FIGS. 9(a) through (g) are sectional views showing a
conventional manufacturing method for a semiconductor device. FIG.
9(a) shows lower-layer wiring on which upper-layer wiring is to be
formed. This lower-layer wiring is composed of an insulating film
1a, a barrier metal film 3a, Cu 4a, and a barrier insulating film
8a. This lower-layer wiring part is also formed by use of processes
similar to those of the upper-layer wiring.
[0007] As shown in FIG. 9(b), an insulating film 1b is formed on
this lower-layer wiring, and then as shown in FIG. 9(c), in the
insulating film, wiring grooves and wiring holes are formed by
lithography and anisotropic etching. Thereafter, as shown in FIG.
9(d), a barrier metal film 3b, which is a conductive film, is
formed on the internal surfaces of the wiring grooves and wiring
holes, and as shown in FIG. 9(e), in a manner filling up the wiring
grooves and wiring holes, a Cu film 4b is formed on the insulating
film 1b.
[0008] Next, as shown in FIG. 9(f), by CMP (Chemical Mechanical
Polishing), an excessive Cu film 4b and barrier metal film 3b
excluding the parts buried in the wiring grooves and wiring holes
are removed. Then, as shown in FIG. 9(g), a barrier insulating film
8b, which is an isolator, is formed on the entire surface. In such
a manner, a Cu wiring structure whose lower surface and side
surfaces have been covered with the barrier metal film 3b, which is
a conductor, and whose upper surface has been covered with the
barrier insulating film 8b, which is an insulator, is formed.
[0009] However, in Japanese Published Unexamined Patent Application
No. 2001-298084, there is a description that when a wiring (wiring
groove) width is seven times or more a via (also referred to as a
wiring hole or a contact hole) diameter, a disconnection owing to a
void (cavity) which is generated under and inside the via, and the
disconnection occurs at the most accelerated rate at around
150.degree. C.
[0010] Similarly, in the following publication, there is a
description that, when lower-layer wiring to which vias are
connected has a wide width, there is voiding on the surface of
lower-layer wiring to be a connecting portion, and the
disconnection easily occurs during isothermal storage at
190.degree. C.
"Stress-Induced Voiding Under Vias Connected To Wide Cu Metal
Leads" (Proceeding of IEEE International Reliability Physics
Symposium 2002, USA, The Electron Device Society and The
Reliability Society of the Institute of Electrical and Electronics
Engineers, Inc, Published on Apr. 7, 2002, p 312-321)
[0011] Next, description will be given of a method for
manufacturing a conventional semiconductor device shown in FIGS.
10(a) through (h). This method is a method for forming copper alloy
wiring when an alloy sputter target disclosed in Japanese Published
Unexamined Patent Application No. 2000-150522 and the like is used.
FIG. 10(a) shows lower-layer wiring on which an upper layer is to
be formed. This lower-layer wiring part is also formed by processes
similar to those of the upper layer shown in the following.
[0012] First, as shown in FIG. 10(b), an insulating film 1b is
formed on this lower-layer wiring. Then, as shown in FIG. 10(c), in
the insulating film 1b, wiring grooves and wiring holes are formed
by lithography and anisotropic etching. Then, as shown in FIG.
10(d), a barrier metal film 3b, as a conductive film is formed on
the entire surface including the internal surfaces of the wiring
grooves and wiring holes. Furthermore, an alloy seed layer 10b to
be electrodes when filling up the wiring grooves and wiring holes
is formed on the barrier metal 3b by a sputtering method using a Cu
alloy target. Then, as shown in FIG. 10(e), by a plating method or
a CVD method (Chemical Vapor Deposition Method), a Cu film 4b is
formed on the entire surface so as to fill up the wiring grooves
and wiring holes.
[0013] Next, as shown in FIG. 10(f), an additional element in the
alloy seed layer 10b is diffused into the Cu film 4b by heat
treatment, whereby the Cu film 4b is alloyed to form a Cu alloy
film 6c.
[0014] Next, as shown in FIG. 10(g), an excessive Cu alloy film 6c
and barrier metal film 3b on the surface of the insulating film 1b
excluding the parts buried in the wiring grooves and wiring holes
are removed by CMP, and as shown in FIG. 10(h), a barrier
insulating film 8b, which is an insulator, is formed on the entire
surface. In such a manner, a Cu wiring structure whose lower
surface and side surfaces have been covered with the barrier metal
film 3b, which is a conductor, and whose upper surface has been
covered with the barrier insulating film 8b, which is an insulator,
is formed.
[0015] In addition, in Japanese Published Unexamined Patent
Application No. 2000-208517, when using metal wiring of a
semiconductor device, a technique using a CuSn alloy seed layer has
been disclosed.
[0016] With regard to reliability of Cu wiring formed as shown in
FIG. 9(a) through (g), in addition to EM resistance, void formation
owing to a stress induced migration (SM) has become a crucial
problem. A tensile stress caused by a difference in thermal
expansion coefficients between the Cu and insulating film to be
applied to a Cu wiring portion serves as a driving force of the
void formation.
[0017] Correspondingly, as described in the above-described
Japanese Published Unexamined Patent Application No. 2001-298084
and the above-described publication, a disconnection owing to a
void formation occurs. Such a failure caused by stress is expected
to become more prominent when the via diameter is further reduced
by miniaturization of the element.
In addition, as countermeasures against EM and SM, priorly,
alloying of Cu wiring has been investigated in numerous cases. In
alloying, by changing Cu composition, migration resistance of Cu
can be improved.
[0018] However, as in the above-described Japanese Published
Unexamined Patent Application No. 2000-208517, Cu alloy wiring
formed by the method shown in FIG. 10(a) through (h) has the
following problems. Namely, when an alloy seed layer 10b was
formed, by diffusing an additional element in the alloy seed layer
10b into the Cu film 4b by heat treatment, a Cu alloy is formed. On
the other hand, the additional element in the alloy seed layer 10b
is diffused into the Cu film 4b by heat treatment, and is partly
precipitated on crystal grain boundaries 7b of the Cu alloy film
6c, however, the additional element mostly remains in crystal
grains of the Cu alloy film 6c. Electron scattering occurs under
the influence of this additional element remaining in crystal
grains of the Cu alloy film 6c.
[0019] In addition, under the influence of grain boundary
scattering of electrons as a result of a reduction in the size of
Cu crystal grains by heat treatment, resistivity of the formed Cu
alloy wiring rises.
[0020] Furthermore, although it is ideal that the additional
element in the alloy seed layer 10b uniformly diffuses into the Cu
film 4b, if the diffusion speed of the additional element into the
Cu film 4b is slow, the additional element remains in the alloy
seed layer 10b in large quantity. At this time, under the influence
of the additional element remaining in the alloy seed layer 10b in
large quantity, resistivity of the Cu wiring rises, and also
concentration profiles of the additional element in the bulk Cu
film 6c can change as a result of heat treatment to form wiring of
a more upper layer, therefore, instability occurs with respect to a
heat cycle at the time of multi-layer formation.
[0021] Furthermore, under the influence of the additional element
in the alloy seed layer 10b, growth of the crystal grains of the Cu
film 6c is suppressed. Particularly, in such a case where the
additional element is precipitated on Cu crystal grain boundaries,
pinning of the grain boundaries occurs under the influence of the
precipitated additional element, and growth of the Cu crystal
grains in heat treatment is suppressed. As a result, since the
diameter of Cu crystal grains is reduced, this raises resistivity
of the Cu wiring and also exerts an influence on a decline in
wiring reliability caused by EM and SM and the like.
[0022] In addition, when the Cu alloy seed layer 10b is formed by
sputtering, since Cu filling capability by sputtering is different
depending on the width of the wiring groove and wiring hole,
inconvenience occurs. Namely, with narrow wiring, since sputter
filling capability is deteriorated, the alloy seed layer 10b
deposited on the bottom of the wiring groove has a thin film
thickness. Therefore, concentration of the additional element in
the Cu wire in a narrow-width wiring groove becomes relatively
small compared to that of a wide-width wiring groove. As a result,
the Cu wires in the narrow-width wiring groove has a low
resistivity compared to that of a wide-width wiring groove. As
such, when the alloy seed layer 10b is formed by a sputtering
method, since concentration of the additional element is different
depending on the width of the wiring groove, resistivity of the Cu
wiring varies depending on the width of the wiring groove.
[0023] Furthermore, in the above-described Japanese Published
Unexamined Patent Application 2000-208517, it has been reported
that adhesion between the barrier metal film and the alloy seed
layer is deteriorated when a CuSn alloy seed layer is used. As
such, securing adhesion between the barrier metal layer 3b and
alloy seed layer 10 has also become a crucial problem.
[0024] An object of the present invention is to provide a highly
reliable copper alloy for wiring for which wiring delay has been
improved, which is high in performance, and which is excellent in
SM resistance and EM resistance, a semiconductor device using the
same wiring, a method for forming the wiring, and a method for
manufacturing the semiconductor device.
DISCLOSURE OF THE INVENTION
[0025] A copper alloy for wiring according to the present invention
is composed of a polycrystalline copper alloy consisting of Cu
(copper) as a primarily element and an or a primarily of additional
element(s), wherein the concentration of said additional element
is, at grain boundaries of crystal grains of said polycrystalline
copper alloy and in vicinities of grain boundaries, higher than
that of the inside of the crystal grains.
[0026] According to this invention, by introducing an additional
element into Cu crystal grain boundaries and vicinities of crystal
grains which serve as diffusion paths of SM or EM in wiring at a
high concentration, Cu migration along the Cu crystal grain
boundaries can be suppressed, whereby reliability of a metal for
wiring can be improved. Furthermore, by this invention, a metal for
wiring for which wiring delay has been suppressed and which is high
in performance can be provided.
[0027] In this copper alloy for wiring, it is preferable that the
additional element is at least one element selected from a group
consisting of Ti (titanium), Zr (zirconium), Hf (hafnium), Cr
(chromium), Co (cobalt), Al (aluminum), Sn (tin), Ni (nickel), Mg
(magnesium), and Ag (silver).
[0028] The additional element is an element whose solid solubility
limit in a Cu film is 1 atomic percent or less and whose diffusion
coefficient at Cu crystal grain boundaries is great, and by adding
this additional element to the inside of the Cu film, the
additional element can be introduced into crystal grain boundaries
of the Cu film and vicinities of crystal grain boundaries at a high
concentration. Therefore, Cu migration along the Cu crystal grain
boundaries can be suppressed, whereby reliability of wiring can be
improved.
[0029] In the copper alloy for wiring of the present invention, for
example, at the crystal grain boundaries and/or in the vicinities
of grain boundaries, intermetallic compounds of Cu with at least
one element selected from a group consisting of Ti, Zr, Hf, Cr, Co,
Al, Sn, Ni, Mg, and Ag are formed.
[0030] According to this invention, by forming stable intermetallic
compounds at Cu crystal grain boundaries and in vicinities of
crystal grain boundaries (frontmost surfaces of Cu crystal grains)
which serve as diffusion paths of SM or EM, Cu migration along the
Cu crystal grain boundaries can be suppressed, whereby reliability
of wiring can be improved.
[0031] In addition, in the copper alloy for wiring of the present
invention, for example, at the crystal grain boundaries and/or in
the vicinities of grain boundaries, oxides of at least one element
selected from a group consisting of Ti, Zr, Hf, Cr, Co, Al, Sn, Ni,
Mg, and Ag are formed.
[0032] According to this invention, by forming stable metal oxides
at Cu crystal grain boundaries and in vicinities of crystal grain
boundaries (frontmost surfaces of Cu crystal grains) which serve as
diffusion paths of SM or EM, Cu migration along the Cu crystal
grain boundaries can be suppressed, whereby reliability of wiring
can be improved.
[0033] In the copper alloy for wiring of the present invention, it
is preferable that concentration of the additional element of the
inside of the crystal grains is 0.1 atomic percent or less.
[0034] According to this invention, by providing a construction
wherein an additional element is introduced into Cu crystal grain
boundaries and vicinities of crystal grain boundaries which serve
as diffusion paths of SM or EM at a high concentration, while
inside the crystal grains, an extremely slight amount of the
additional element of 0.1 atomic percent or less is contained, Cu
migration along Cu crystal grain boundaries can be suppressed,
whereby reliability of wiring can be improved.
[0035] A semiconductor device according to the present invention is
characterized in that, on a substrate on which a semiconductor
element has been formed, metal wiring composed of the copper alloy
for wiring as set forth in any one of Claims 1 through 5 of the
present application is formed.
[0036] According to this invention, by introducing an additional
element into Cu crystal grain boundaries and vicinities of crystal
grain boundaries which serve as diffusion paths of SM or EM in
metal wiring of a semiconductor device at a high concentration, Cu
migration along Cu crystal grain boundaries can be suppressed,
whereby reliability of metal wiring can be improved. Furthermore,
by this invention, a semiconductor device having metal wiring for
which wiring delay has been suppressed and which is high in
performance can be provided.
[0037] A forming method for wiring according to the present
invention comprises the steps of: forming a polycrystalline Cu
film; forming a layer formed of an additional element which is to
be added into the Cu film on the polycrystalline Cu film; and
diffusing the additional element from the additional element layer
into the polycrystalline Cu film.
[0038] According to this invention, since crystal grains of a Cu
film are grown in a polycrystalline Cu film forming step and an
additional element is introduced into this polycrystalline Cu film,
no such suppression of Cu crystal grain growth owing to an
influence of an additional element in heat treatment as observed in
a case where a Cu alloy seed layer is formed by use of a sputter
target in which an additional element has been mixed at a few
percent occurs. In addition, since the additional element hardly
exists inside bulk crystal grains, electron scattering in the bulk
crystal grains by the additional element is suppressed, and
resistance of the copper alloy for wiring can be lowered. As a
result, highly reliable wiring for which wiring delay has been
suppressed, which is high in performance, and which is excellent in
SM resistance and EM resistance can be obtained.
[0039] In the forming method for wiring, a heating step of heating
a substrate on which the polycrystalline Cu film has been formed, a
step of forming the additional element layer, and a step of
diffusing the additional element can be simultaneously
performed.
[0040] According to this invention, in addition to the effects as
mentioned above, by simultaneously performing these respective
steps, the wiring forming steps can be simplified by omitting
several steps.
[0041] The additional element is at least one element selected from
a group consisting of Ti, Zr, Hf, Cr, Co, Al, Sn, Ni, Mg, and
Ag.
[0042] Since these additional elements are elements whose solid
solubility limits are 1 atomic percent or less and whose diffusion
coefficients at Cu crystal grain boundaries are great, an
additional element can be introduced into Cu crystal grain
boundaries and vicinities of crystal grain boundaries at a high
concentration. Therefore, Cu migration along Cu crystal grain
boundaries can be suppressed, whereby reliability of wiring can be
improved.
[0043] A method for manufacturing a semiconductor device according
to the present invention comprises the steps of: forming a
polycrystalline Cu film on a substrate on which a semiconductor
element has been formed; forming a layer composed of an additional
element on the polycrystalline Cu film; and diffusing the
additional element from the additional element layer into the
polycrystalline Cu film.
[0044] According to this invention, since Cu crystal grains are
grown in a polycrystalline Cu film forming step and an additional
element is introduced into this polycrystalline Cu film, no such
suppression of Cu crystal grain growth owing to an influence of an
additional element in heat treatment as observed in a case where a
Cu alloy seed layer is formed by use of a sputter target in which
an additional element has been mixed at a few percent occurs. In
addition, since the additional element hardly exists inside bulk Cu
crystal grains, electron scattering in the bulk crystal grains by
the additional element is suppressed, and resistance of the Cu
wiring in a semiconductor device can be lowered. As a result, a
highly reliable metal wiring in which wiring delay has been
suppressed, which is high in performance, and which is excellent in
SM resistance and EM resistance can be obtained.
[0045] Another method for manufacturing a semiconductor device
according to the present invention comprises the steps of: forming
an insulating film on a substrate on which a semiconductor element
has been formed; forming concavities for wiring composed of at
least either grooves or holes in the insulating film; forming a Cu
film on the insulating film so as to fill up the concavities for
wiring; removing an excessive Cu film on the insulating film
excluding parts buried in the concavities for wiring by chemical
mechanical polishing; forming a layer composed of an additional
element on the Cu film; diffusing the additional element from the
additional element layer into the Cu film; and removing an
excessive additional element layer.
[0046] According to this invention, Cu crystal grains are grown in
a polycrystalline Cu film forming step, and an additional element
is introduced into this polycrystalline Cu film. Therefore, no such
suppression of Cu crystal grain growth owing to an influence of an
additional element by heat treatment as observed in a case where a
Cu alloy seed layer is formed by use of a sputter target in which
an additional element has been mixed at a few percent occurs. In
addition, since the additional element hardly exists inside bulk Cu
crystal grains, electron scattering in the bulk Cu crystal grains
by the additional element is suppressed, and resistance of the Cu
wiring in a semiconductor device can be lowered. Furthermore,
according to the present invention, since an additional element is
introduced (diffused into Cu) into a Cu film from an additional
element layer of an upper layer after a Cu film is buried in the
concavities for wiring, such a difference in concentration of the
additional element owing to a difference in Cu filling capability
between respective grooves and respective holes hardly occurs, said
difference has been observed in a case where a Cu alloy seed layer
is formed by use of a sputter target, and the wiring grooves and
wiring holes are filled with Cu. As a result, unevenness in
resistivity of Cu wiring depending on the width of wiring grooves
is eliminated.
[0047] Still another method for manufacturing a semiconductor
device according to the present invention comprises the steps of:
forming an insulating film on a substrate on which a semiconductor
element has been formed; forming concavities for wiring composed of
at least either grooves or holes in the insulating film; forming a
barrier metal to prevent Cu from diffusing on the insulating film
including inner surfaces of the concavities for wiring; forming a
Cu film on the insulating film so as to fill up the same in the
concavities for wiring; removing a Cu film and a barrier metal film
excluding parts buried in the concavities for wiring by chemical
mechanical polishing; forming a layer composed of an additional
element on the Cu film in the concavities for wiring; diffusing the
additional element from the additional element layer into the Cu
film; and removing an excessive additional element layer.
[0048] According to this invention, since Cu crystal grains are
grown in a polycrystalline Cu film forming step, and an additional
element is introduced into this polycrystalline Cu film, no
suppression of Cu crystal grain growth owing to an influence of an
additional element in heat treatment occurs. In addition, since the
additional element hardly exists inside bulk Cu crystal grains,
electron scattering in the bulk Cu crystal grains by the additional
element is suppressed, and resistance of the Cu wiring in a
semiconductor device can be lowered. In addition, since an
additional element is introduced into a Cu film from an additional
element layer of an upper layer after a Cu film is buried, a
difference in concentration of the additional element in Cu wiring
becomes unlikely to occur, thus unevenness in resistivity of Cu
wiring depending on the width of wiring grooves is eliminated.
Furthermore, since a barrier metal is provided between the Cu and
insulating film, diffusion of Cu into the insulating film and
corrosion of Cu can be prevented.
[0049] In the present invention, before a step of removing the
excessive Cu film, a step of forming the additional element layer,
a step of diffusing the additional element, and a step of removing
the excessive additional element layer can be performed.
[0050] According to this invention, as a result of a formation of
stable intermetallic compounds of Cu and an additional element at
Cu crystal grain boundaries and in vicinities of crystal grain
boundaries, EM resistance and SM resistance are improved, whereby
reliability of wiring of an semiconductor device is improved.
[0051] In addition, in the present invention, after a step of
removing the excessive Cu film, a step of forming the additional
element layer, a step of diffusing the additional element, and a
step of removing the excessive additional element layer can be
performed.
[0052] According to the present invention, by performing a step of
forming the additional element layer, a step of diffusing the
additional element, and a step of removing the excessive additional
element layer after a step of removing the excessive Cu film,
stable intermetallic compounds of Cu and an additional element are
formed on the surfaces of Cu crystal grains which are in contact
with a layer formed on the Cu film, which is a metal for wiring. As
a result, adhesion between the Cu of a metal for wiring and upper
layer is improved, whereby reliability of wiring of an
semiconductor device is improved.
[0053] In the method for manufacturing a semiconductor device of
the present invention, a step of heating the substrate, a step of
forming the additional element layer, and a step of diffusing the
additional element can be simultaneously performed.
[0054] According to this invention, in addition to the effects as
mentioned above, by simultaneously performing these respective
steps, manufacturing of a semiconductor device can be simplified by
omitting the severed steps.
[0055] The additional element is at least one element selected from
a group consisting of Ti, Zr, Hf, Cr, Co, Al, Sn, Ni, Mg, and
Ag.
[0056] According to this invention, since the additional element is
an element whose solid solubility limit in Cu is 1 atomic percent
or less and whose diffusion coefficient at Cu crystal grain
boundaries is large, by adding this additional element to a Cu
film, the additional element can be introduced into Cu crystal
grain boundaries and vicinities of crystal grain boundaries at a
high concentration. Therefore, Cu migration along Cu crystal grain
boundaries can be suppressed, whereby reliability of metal wiring
of a semiconductor device can be improved.
BRIEF DESCRIPTION OF DRAWINGS
[0057] FIG. 1 is a sectional view showing a semiconductor device
according to a first embodiment of the present invention.
[0058] FIGS. 2(a) through (j) are sectional views showing a method
for manufacturing a semiconductor device according to the first
embodiment of the present invention in the order of steps.
[0059] FIG. 3 is a sectional view showing a semiconductor device
according to a second embodiment of the present invention.
[0060] FIGS. 4(a) through (j) are sectional views showing a method
for manufacturing a semiconductor device according to the second
embodiment of the present invention in the order of steps.
[0061] FIG. 5 is a sectional view of a semiconductor device
according to a third embodiment of the present invention.
[0062] FIGS. 6(a) through (i) are sectional views showing a method
for manufacturing a semiconductor device according to the third
embodiment of the present invention in the order of steps.
[0063] FIGS. 7(a) through (k) are sectional views showing former
steps in an example of the present invention in the order of
steps.
[0064] FIGS. 8(l) through (s) are similarly sectional views showing
latter steps in an example of the present invention in the order of
steps.
[0065] FIGS. 9(a) through (g) are sectional views explaining a
method for manufacturing a semiconductor device according to the
prior art.
[0066] FIGS. 10(a) through (h) are sectional views explaining
another example of a method for manufacturing a semiconductor
device according to the prior art.
[0067] FIG. 11 is a graph explaining a relationship between the
storage time and relative failure rate of via chains fabricated by
an example and a comparative example.
[0068] FIG. 12 is a graph showing electromigration resistance of
contact holes of via chains fabricated by an example and a
comparative example by a relationship between the cumulative time
and cumulative failure probability.
[0069] FIG. 13 is a graph showing changes in resistivity of Cu
wiring owing to a difference in heat treatment after a Cu layer
formation in blanket wafer samples of an example.
[0070] FIG. 14 is a graph showing distributions of Ti, Cu, and N of
a barrier metal film, a Cu layer, and an additional element layer
in blanket wafer samples of an example.
[0071] FIG. 15 is a graph showing changes in resistivity of Cu
wiring owing to a difference in additional elements and a
difference in heat treatment after an additional element layer
formation in blanket wafer samples of an example.
[0072] FIG. 16 is a graph diagram showing results of a measurement
of oxygen (O) distributions in Cu.
[0073] FIGS. 17(a) and (b) show scanning electron micrographs in
samples shown in FIG. 16.
BEST MODE FOR CARRYING OUT THE INVENTION
[0074] Next, embodiments of the present invention will be described
in detail with reference to the drawings.
First Embodiment
[0075] A Cu wiring structure of a semiconductor device according to
a first embodiment of the present invention will be described with
reference to FIG. 1.
[0076] A Cu wiring structure of a semiconductor device shown in
FIG. 1 has a lower-layer wiring composed of an insulating film 1a,
a barrier metal film 3a, Cu 4a, and a barrier insulating film 8a,
and an upper-layer wiring composed of an insulating film 1b, a
barrier metal film 3b, Cu crystal grains 6b, Cu grain boundaries
and vicinities thereof 7b, and a barrier insulating film 8b. Here,
the Cu 4a of the lower-layer wiring is constructed similarly to the
Cu crystal grains 6b and Cu grain boundaries and vicinities thereof
7b of the upper wiring.
[0077] And, the feature of the first embodiment is a structure
wherein at least any of a large quantity of an additional element,
intermetallic compounds of Cu and an additional element, and oxides
of an additional element have been precipitated on boundaries of Cu
crystal grains 6b and vicinities thereof and interfaces between the
Cu grain grains 6b and the barrier metal film 3b and vicinities
thereof (shown as reference numeral 7b).
[0078] Cu metal wiring is made of a Cu polycrystal doped with a
metallic element other than Cu. The Cu crystal grains 6b composing
the polycrystal are Cu crystal grains whose crystal grain growth is
not restricted and which has an average and appropriate size on the
order of 1 .mu.m to 10 .mu.m.
[0079] And, the Cu crystal grain boundaries 7b and the interfaces
7b between the Cu crystal grains 6b and the barrier metal layer 3b
have a structure wherein the additional element or compounds
containing the additional element (intermetallic compounds with Cu,
oxides or the like) have been precipitated. In addition, there is a
structure wherein, intermetallic compounds of the additional
element with Cu or the like have been formed, in addition to the Cu
crystal grain boundaries and the like, in the vicinities 7b of Cu
crystal grains. Here, the vicinities Cu crystal grain boundaries
herein mentioned indicate positions on the order of 10 nm inward
from the crystal grain surfaces of the Cu crystal grains 6b.
[0080] Although concentration of the additional element at the
grain boundaries of the Cu crystal grains 6b and vicinities 7b of
grain boundaries is not particularly limited, an additional element
of a larger quantity than that of at least the inside of the Cu
crystal grains 6b exists at the grain boundaries of the Cu crystal
grains 6b and vicinities 7b of grain boundaries. Concretely,
concentration of the additional element at the grain boundaries of
the Cu crystal grains 6b and vicinities 7b of grain boundaries is
on the order of 2 to 1000 times the additional element
concentration at the inside of the Cu crystal grains 6b, and
preferably, on the order of 10 to 100 times.
[0081] It is possible to measure additional element concentration
at the Cu crystal grain boundaries and vicinities thereof 7b by,
for example, X-ray spectroscopy. This measuring method is
detectable when the additional element concentration at Cu crystal
grains and vicinities thereof 7b is 0.1 atomic percent
(hereinafter, atomic percent is referred to as atomic %) or
more.
[0082] On the other hand, inside the Cu crystal grains 6b, in other
words, in bulk Cu 6b, only an additional element of 0.1 atomic % or
less exists, which is a nearly pure Cu condition. Here, the inside
of the Cu crystal grains herein mentioned means a part of Cu
crystal grains excluding the aforementioned vicinities of Cu
crystal grain boundaries.
[0083] It is possible to measure additional element concentration
at the inside of the Cu crystal grains 6b by, for example, SIMS
(Secondary Ion Mass Spectroscopy), X-ray spectroscopy or the like.
SIMS can be used when measuring Cu crystal grains have a diameter
greater than a beam diameter (normally, a few tens of micrometers)
used in SIMS. When the Cu crystal grain diameter is smaller than
the same, by determining an average concentration of the additional
element at an area including grain boundaries and the inside of the
Cu crystal grains by SIMS and by determining an additional element
concentration at the aforementioned Cu crystal grain boundaries and
vicinities 7b of grain boundaries, an additional element
concentration at the inside of the Cu crystal grains can be
estimated. In addition, by X-ray spectroscopy from the Cu crystal
surface, additional element concentration can be measured if the
atomic percent is 1 or more. Here, detection sensitivity by X-ray
spectroscopy is on the order of 0.1 atomic percent.
[0084] As such, at positions of the grain boundaries of Cu crystal
grains and vicinities 7b of grain boundaries, concentration
(content) of the additional element is provided higher than that of
the inside of the Cu crystal grains 6b.
[0085] In addition, as the additional element, an element whose
solid solubility limit in Cu is 1 atomic % or less and whose
diffusion coefficient at Cu crystal grain boundaries is great can
be used. A diffusion coefficient of the additional element at Cu
bulk (inside of the Cu crystal grains) does not necessarily have to
be great. As the additional element, in particular, titanium (Ti),
zirconium (Zr), hafnium (Hf), chromium (Cr), and cobalt (Co) are
preferably used. As the additional element, in addition, aluminum
(Al), tin (Sn), nickel (Ni), magnesium (Mg), and silver (Ag) can be
used.
[0086] In such a Cu wiring structure, no such problem in the prior
art that resistivity of Cu wiring is increased under the influence
of electron scattering owing to the additional element remaining in
the bulk Cu 6c and under the influence of boundary scattering of
electrons owing to a reduction in size of crystal grains occurs. In
addition, by such a structure of Cu metal wiring, electron
scattering owing to the additional element in the bulk Cu 6b can be
suppressed, whereby transmission delay of wiring can be improved.
In addition, on Cu crystal grain boundaries and vicinities 7b of
the crystal grain boundaries which serve as diffusion paths of Cu
for void formation, the additional element or compounds including
the additional element are precipitated, whereby Cu diffusion is
suppressed.
[0087] Furthermore, when an element which is higher in reducibility
than Cu and is easily oxidized is used as an additional element,
even if the Cu metal wiring is exposed to oxygen or vapor, the
additional element which is present on the boundaries is first
oxidized, and the oxidized additional element functions as a
barrier to prevent Cu oxidation, therefore, provided is an effect
of a Cu oxidation prevention and erosion prevention. In addition,
by forming a layer of an element which is higher in reducibility
than Cu and is easily oxidized on the Cu surface, provided are an
effect to suppress Cu from oxidizing in heat treatment and a
gettering effect for oxygen and impurities which are present on the
Cu surface and inside Cu. The oxygen which is present on the Cu
surface and in Cu can diffuse during heat treatment and oxidize a
barrier film of a lower layer, and in this case, adhesion between
the Cu and barrier metal is deteriorated, which exerts a harmful
effect on reliability of wiring. Gettering of oxygen which is
present on the Cu surface and in Cu also leads to suppressing
barrier metal from oxidizing, which is effective for an improvement
in reliability of Cu wiring.
[0088] Herein, as Cu migration paths which causes the problem of
reliability of Cu wiring, it has been indicated in a publication
((Electromigration path in Cu thin-film lines), (Applied Physics
Letters, USA, American Institute of Physics, published on May 17,
1999), Vol. 74, p 2945-2947) and the like that, as regards EM,
diffusion at interfaces between the Cu crystal grains and the
barrier insulating films or between the Cu crystal grain boundaries
is more dominant than diffusion in bulk Cu.
[0089] In addition, as regards to SM, as well, since voids owing to
SM are formed at crystal grain boundaries, it is considered that
the Cu crystal grain boundaries serve as diffusion paths.
Therefore, it is considered important for an improvement in
reliability of Cu metal wiring to suppress interfacial and grain
boundary diffusion. Accordingly, it is considered that Cu metal
wiring is improved in reliability by alloying because, as a result
of precipitation of an added impurity element at interfaces between
the Cu crystal grains and the other layers or between the Cu
crystal grain boundaries, Cu diffusion via the interfaces between
the Cu crystal grains and the other layers and between the Cu
crystal grain boundaries is suppressed.
[0090] In the present invention, by suppressing alloying of bulk Cu
and introducing the additional element into only the interfaces
between the Cu crystal grains and the other layers and between the
Cu crystal grain boundaries, a rise in resistance of Cu wiring is
suppressed, thus provision of highly reliable Cu metal wiring with
EM and SM resistance is realized.
[0091] Next, a method for manufacturing a semiconductor device
having Cu wiring of the first embodiment will be described with
reference to FIGS. 2(a) through (j).
[0092] FIG. 2(a) shows lower-layer wiring on which upper-layer
wiring is to be formed. This lower-layer wiring is composed of an
insulating film 1a, a barrier metal film 3a, Cu 4a, and a barrier
insulating film 8a. This lower-layer wiring part is also formed by
use of processes similar to those of the upper-layer wiring shown
in the following.
[0093] As shown in FIG. 2(b), an insulating film 1b is formed on
this lower-layer wiring, and then as shown in FIG. 2(c), in the
insulating film 1b, wiring grooves and wiring holes are formed by
lithography and anisotropic etching. Thereafter, as shown in FIG.
2(d), a barrier metal film 3b is formed on the formed wiring
grooves and wiring holes, and Cu 4b is buried therein. Next, and as
shown in FIG. 2(e), heat treatment for grain growth of Cu is
applied. This heat treatment is performed at a low temperature of
not more than 400.degree. C., and, preferably, not more than
300.degree. C. It is also possible to omit this heat treatment for
Cu grain growth.
[0094] Thereafter, as shown in FIG. 2(f), a layer 5b of an element
to be added to the inside of Cu crystals is formed on the surface
of the Cu 4b. Next, as shown in FIG. 2(g), heat treatment to
diffuse the additional element 5b into the Cu crystals 4b is
applied. The temperature of this heat treatment is set to
300.degree. C. to 500.degree. C., and the time is set to ten
minutes to 1 hour.
Next, as shown in FIG. 2(h), an excessive additional element layer
5b is removed by wet etching. For a removal of the additional
element layer 5b, CMP may be used in place of wet etching.
Subsequently, as shown in FIG. 2(i), an excessive Cu 6b and barrier
metal layer 3b excluding the wiring grooves and wiring holes are
removed by CMP. Next, as shown in FIG. 2(j), a barrier insulating
film 8b to prevent Cu from corroding and diffusing is formed on the
entire front surface.
[0095] By repeating the steps of FIG. 2(b) to FIG. 2(j), wiring of
a more upper layer can be formed.
[0096] In the above manufacturing method, although formation of the
additional element layer 5b (FIG. 2(f)) and diffusion of the
additional element into the Cu polycrystal (FIG. 2(g)) have been
separately performed, it is also possible to simultaneously perform
formation of the additional element layer 5b and diffusion of the
additional element into the Cu polycrystal by forming the
additional element layer 5b at a high temperature. By
simultaneously performing these two steps, the number of steps can
be reduced, thus a semiconductor device having Cu wiring can be
more simply manufactured. Here, temperature and time when the two
steps are simultaneously performed as such may be provided
similarly to those of heat treatment to diffuse the additional
element into Cu crystals. The same applies to respective
embodiments to be described in the following.
[0097] In addition, although, in the present embodiment, Cu has
been buried after the barrier metal film 3b was formed, the barrier
metal film 3b is not an essential construction and may not be
formed. Here, by forming the barrier metal film 3b, diffusion of
the Cu 6b into the insulating film 1b can be suppressed.
[0098] In addition, although, in the above, a description has been
given by use of a dual damascene method for simultaneously forming
wiring grooves and wiring holes, the invention is also similarly
applied to a wiring layer formation when a single damascene method
for forming only wiring grooves or only wiring holes is used. Here,
in the present invention, the wiring grooves and wiring holes are
also collectively referred to as concavities for wiring.
Second Embodiment
[0099] A Cu wiring structure of a semiconductor device according to
a second embodiment of the present invention will be described with
reference to FIG. 3.
[0100] In the Cu wiring structure shown in FIG. 3, in addition to
the construction of the first embodiment, a stable intermetallic
compound layer of Cu with an additional element is formed at
interfaces between the barrier insulating film 8b and Cu crystal
grains 6b. Thereby, adhesion between the Cu 6b, which is a metal
for wiring, and barrier insulating film 8b is improved, thus
reliability of wiring is improved.
[0101] Next, a method for manufacturing a semiconductor device
having Cu wiring of the second embodiment will be described with
reference to FIG. 4(a) through (j).
[0102] Although the manufacturing method of the second embodiment
is different from that of the first embodiment in a point that an
additional element layer 5b is formed after an excessive Cu 6b and
an excessive barrier metal 3b are removed by CMP, others are the
same.
[0103] FIG. 4(a) shows lower-layer wiring on which upper-layer
wiring is to be formed. This lower-layer wiring part is also formed
by use of processes similar to those of the upper-layer wiring
shown in the following.
[0104] As shown in FIG. 4(b), an insulating film 1b is formed on
this lower-layer wiring, and then as shown in FIG. 4(c), in the
insulating film 1b, wiring grooves and wiring holes are formed by
lithography and anisotropic etching. Thereafter, as shown in FIG.
4(d), a barrier metal film 3b is formed, and Cu 4b is buried. Next,
and as shown in FIG. 4(e), heat treatment for grain growth of the
buried Cu is applied. This heat treatment is performed at a low
temperature of not more than 400.degree. C., and, preferably, not
more than 300.degree. C. It is also possible to omit this heat
treatment for Cu grain growth.
[0105] Thereafter, as shown in FIG. 4(f), excessive Cu and an
excessive barrier metal excluding the wiring grooves and wiring
holes are removed by CMP. Next, as shown in FIG. 4(g), a layer 5b
of an element to be added into the Cu is formed on the Cu surface.
Next, as shown in FIG. 4(h), heat treatment to diffuse the
additional element into the Cu is applied. The temperature of this
heat treatment is set on the order of 300.degree. C. to 500.degree.
C., and the time is set on the order of 10 minutes to 1 hour.
[0106] Next, as shown in FIG. 4(i), an excessive additional element
layer 5b is removed by wet etching. For a removal of the additional
element layer 5b, CMP may be used in place of wet etching. Next, as
shown in FIG. 4(j), a barrier insulating film 8b to prevent Cu from
corroding and diffusing is formed on the entire front surface.
[0107] By repeating FIG. 4(b) to FIG. 4(j), wiring of a more upper
layer can be formed.
[0108] In the above manufacturing method, although formation of the
additional element layer 5b (FIG. 4(g)) and diffusion of the
additional element into the Cu polycrystal (FIG. 4(h)) have been
separately performed, it is also possible to simultaneously perform
formation of the additional element layer 5b and diffusion of the
additional element into the Cu polycrystal by forming the
additional element layer 5b under a high-temperature condition. By
simultaneously performing these two steps, the number of steps can
be reduced, thus a semiconductor device having Cu wiring can be
more simply manufactured.
[0109] In addition, although, a description has been given in the
above by use of a dual damascene method for simultaneously forming
wiring grooves and wiring holes, the invention is also similarly
applied to a formation of concavities for wiring when a single
damascene method for forming only wiring grooves or only wiring
holes is used.
Third Embodiment
[0110] A Cu wiring structure of a semiconductor device according to
a third embodiment of the present invention will be described with
reference to FIG. 5.
[0111] The wiring structure of the third embodiment shown in FIG. 5
is different from the structure of the second embodiment in a point
that no barrier insulating film 8b is used. In the third
embodiment, since, by forming a stable intermetallic compound layer
on the Cu surface, oxidation and corrosion of the Cu are prevented,
the barrier insulating film 8b becomes unnecessary. Since an
effective dielectric constant of Cu wiring is lowered by providing
no barrier insulating film 8b, transmission delay can be
improved.
[0112] Next, a method for manufacturing a semiconductor device
having Cu wiring of the third embodiment will be described with
reference to FIG. 6(a) through (i).
[0113] FIG. 6(a) shows a lower-layer wiring on which an upper-layer
wiring is to be formed. This lower-layer wiring part is also formed
by use of processes similar to those of the upper-layer wiring
shown in the following.
[0114] As shown in FIG. 6(b), an insulating film 1b is formed on
this lower-layer wiring, and then as shown in FIG. 6(c), in the
insulating film 1b, wiring grooves and wiring holes are formed by
lithography and anisotropic etching. Thereafter, as shown in FIG.
6(d), a barrier metal film 3b is formed, and Cu 4b is buried. Next,
and as shown in FIG. 6(e), heat treatment for growth of Cu crystal
grains is applied. This heat treatment is performed at a low
temperature of not more than 400.degree. C., and, preferably, not
more than 300.degree. C. It is also possible to omit this heat
treatment for Cu grain growth.
[0115] Thereafter, as shown in FIG. 6(f), an excessive Cu and
barrier metal excluding the wiring grooves and wiring holes are
removed by CMP. Next, as shown in FIG. 6(g), a layer 5b of an
element to be added to the inside of Cu is formed on the Cu
surface. Next, as shown in FIG. 6(h), heat treatment to diffuse the
additional element into Cu is applied. The temperature of this heat
treatment is set to 300.degree. C. to 500.degree. C., and the time
is set to 10 minutes to 1 hour.
[0116] Next, as shown in FIG. 6(i), an excessive additional element
layer 5b is removed by wet etching. For a removal of the additional
element layer 5b, CMP may be used in place of wet etching.
[0117] By repeating FIG. 6(b) to FIG. 6(i), wiring of a more upper
layer can be formed.
[0118] In the above manufacturing method, although formation of the
additional element layer 5b (FIG. 6(g)) and diffusion of the
additional element into the Cu polycrystal (FIG. 6(h)) have been
separately performed, it is also possible to simultaneously perform
formation of the additional element layer 5b and diffusion of the
additional element into the Cu polycrystal by forming the
additional element layer 5b at a high temperature. By
simultaneously performing these two steps, the number of steps can
be reduced, thus a semiconductor device having Cu wiring can be
more simply manufactured.
[0119] In addition, although, a description has been given in the
above by use of a dual damascene method for simultaneously forming
wiring grooves and wiring holes, the invention is also similarly
applied to a formation of concavities for wiring when a single
damascene method for forming only wiring grooves or only wiring
holes is used.
[0120] Hereinafter, characteristics of an example and a comparative
example of the present invention are compared, and effects of the
present invention will be described.
Example
[0121] FIGS. 7(a) through (k) and FIGS. 8(l) through (s) are
sectional views showing a method for manufacturing a semiconductor
device in an example of the present invention in the order of
steps.
[0122] A 1000 nm SiO.sub.2 film (insulating film) 1a was formed on
a silicon substrate (unillustrated), thereon a first wiring layer
(wiring grooves) was formed by a single damascene method, and then,
on the top thereof, by a dual damascene method, a second wiring
layer (wiring grooves) and contact holes (wiring holes) with the
first wiring layer were formed. The details will be described in
the following.
[0123] On the SiO.sub.2 film 1a (FIG. 7(a)), a SiC film (stopper
insulating film) 2a with a thickness of 50 nm to be an etching
stopper was formed, and subsequently, as shown in FIG. 7(b), a
SiO.sub.2 film (insulating film) 1b with a thickness of 350 nm to
insulate wirings each other in the first wiring layer was formed,
and as shown in FIG. 7(c), wiring grooves were formed, by
lithography and etching, in the SiO.sub.2 film 1b. Thereafter, as
shown in FIG. 7(d), a barrier metal film 3a composed of a TaN film
and a Ta film and a 100 nm Cu thin film were formed on the entire
surface of a substrate surface, and while using this Cu film as an
electrode, Cu 4a was buried by an ionization sputtering method.
[0124] Next, as shown in FIG. 7(e), after applying heat treatment
in a nitrogen atmosphere for Cu crystal grain growth, as shown in
FIG. 7(f), a Ti film (additional element layer) 5a with a film
thickness of 20 nm was formed on the entire Cu front surface by
sputtering.
[0125] Subsequently, as shown in FIG. 7(g), a heat treatment at
350.degree. C. for 30 minutes was performed in a nitrogen
atmosphere, whereby Ti was diffused into Cu from the Cu surface.
Here, since Ti is diffused via Cu crystal grain boundaries and is
hardly diffused into bulk, formed is a structure wherein Ti is
contained in large quantity in vicinities 7a of Cu crystal grain
boundaries and Ti is hardly existed in bulk Cu 6a.
[0126] Next, as shown in FIG. 7(h), excessive Ti was removed by
hydrofluoric acid, and subsequently by CMP, respective layers of
excessive Cu, Ta, and TaN were removed. On this entire front
surface, as shown in FIG. 7(i), a SiCN layer (barrier insulating
film) 8a with a thickness of 50 nm was formed by a plasma CVD
method, whereby a first wiring layer was formed.
[0127] Furthermore, as shown in FIG. 7(j), a SiO.sub.2 film
(insulating film) 1c, a SiC film (stopper insulating film) 2b, a
SiO.sub.2 film (insulating film) 1d were formed at thicknesses of
400 nm, 50 nm, and 400 nm, respectively, by a plasma CVD method,
and as shown in FIG. 7(k), by lithography and anisotropic dry
etching, parts of the SiO.sub.2 film 1c, SiC film 2b, and SiO.sub.2
film 1d were removed in order while using the SiCN 8a as an etching
stopper, whereby main parts of contact holes (wiring holes) between
the first wiring layer and second wiring layer were formed.
[0128] Subsequently, as shown in FIG. 8(l), by lithography and
anisotropic etching, while using the SiC film 2b as an etching
stopper, part of the SiO.sub.2 film 1c was removed, whereby main
parts of wiring grooves of the second wiring layer were formed.
Next, as shown in FIG. 8(m), the SiCN film 8a on bottom portions of
the contact holes between the first wiring layer and second wiring
layer and the SiC film 2b on bottom portions of the second wiring
grooves were removed by anisotropic etching, whereby an upper
contact surface of the first wiring layer was exposed.
[0129] Next, by slightly etching the front surface by Ar ions in a
vacuum system, the surface of the first wiring layer exposed from
the bottoms of contact holes between the first wiring layer and
second wiring layer was cleaned.
[0130] Next, while maintaining a vacuum, in order to coat the inner
surfaces of the wiring grooves of the second wiring layer and the
contact holes between the first wiring layer and the second wiring
layer, by procedures similar to those for a first wiring layer
formation, as shown in FIG. 8(n), a barrier metal film 3b provided
by laminating a TaN film and a Ta film in this order and a 100 nm
Cu thin film were formed by an ionization sputtering method, and
while using this Cu thin film as a seed, Cu 4b was buried by an
electrolytic plating method.
[0131] Next, as shown in FIG. 8(o), simultaneously with a first
wiring layer formation, after heat treatment was applied for Cu
crystal grain growth in a nitrogen atmosphere, as shown in FIG.
8(p), a Ti film (additional element layer) 5b with a film thickness
of 20 nm was formed on the entire Cu front surface by sputtering.
Subsequently, as shown in FIG. 8(q), a heat treatment at
350.degree. C. for 30 minutes was performed in a nitrogen
atmosphere, whereby Ti was diffused into Cu from the Cu
surface.
[0132] Next, as shown in FIG. 8(r), excessive Ti was removed by
hydrofluoric acid, and subsequently by CMP, respective layers of
excessive Cu, Ta, and TaN were removed. Thereafter, as shown in
FIG. 8(s), on this entire front surface, a SiCN layer (barrier
insulating film) 8b with a thickness of 50 nm was formed by a
plasma CVD method, and furthermore, a SiO.sub.2 film 9 was formed
as a cover film.
[0133] After opening junctions with the second wiring layer in the
cover film 9 by lithography and etching, Ti film, TiN film, and Al
film were formed by sputtering in order, and an Al/TiN/Ti laminated
film was processed into a pad pattern for electrometry by
lithography and etching.
Comparative Example
[0134] As a comparative example, a conventional semiconductor
device having Cu wiring composed of upper-layer and lower-layer
wiring was fabricated as shown in the foregoing FIG. 9(a) through
(g). The substrate, insulating film, stopper insulating film,
barrier metal film, barrier insulating film, and cover insulating
film were formed, by use of materials similar to those of the
aforementioned embodiment, with similar thicknesses and by a
similar forming method. Here, Ti, which was an additional element
in the embodiment, was not added.
[0135] Results of Evaluation
[0136] FIG. 11 shows failure rates of respective samples fabricated
by the example and comparative example. Namely, respective samples
of a via chain with a chain number (number of vias) of ten
thousand, whose contact hole diameter was 0.2 .mu.m and whose
lower-layer wiring (wiring grooves) width was 10 .mu.m were
fabricated, and failure rates after these were stored for 1000
hours at 150.degree. C. were determined.
[0137] As a result of a sample processing by Focused Ion Beam (FIB)
and an observation by Transmission Electron Spectroscopy (TEM), it
could be confirmed that disconnections in the respective samples
were owed to a void formation as a result of stress induced
migration at the lower-layer wiring portions 4a of contact holes as
reported in the above-described Japanese Published Unexamined
Patent Application No. 2001-298084.
[0138] In samples of the comparative example, open failures were
prominent, and the failure rate was increased with storage time. In
addition, in the samples of the comparative example, presence of Cu
grain boundaries could be confirmed.
[0139] On the other hand, in samples of the example, failure has
been remarkably improved. The failure generation rate after the
samples were stored at 150.degree. C. for 1000 hours was suppressed
to approximately one-fortieth of that of the comparative example.
Furthermore, by optimizing the manufacturing processes, failure
generation could be completely suppressed even after storage for
1000 hours.
[0140] FIG. 12 shows test results for electromigration resistance
of contact holes (contact vias). Concretely, it shows accumulated
failure probabilities with respect to failure time. A test was
performed at 300.degree. C. with a condition of a current density
of 3.2 MA/cm.sup.2, a rise in resistivity of 3% was employed as a
judgement criterion for failure. It could be confirmed that the
samples of the example had an electromigration resistance not less
than two times that of the samples of the comparative example.
[0141] It can be considered that, in the example, since diffusion
of Cu via grain boundaries can be suppressed by introducing Ti into
Cu crystal grain boundaries, stress induced migration resistance
and electromigration resistance have been improved.
[0142] FIG. 13 shows plotted changes in resistivity. Samples used
for this resistivity measurement are blanket wafer samples which
had been fabricated similarly to the procedures of the
above-described embodiment except that a Ta/TaN barrier metal film
3a was formed on a SiO.sub.2 insulating film 1a, a 700 nm Cu layer
was further formed, and a 20 nm Ti additional element layer 5a was
formed. Here, in the blanket wafer samples, no wiring holes and
wiring grooves were formed. In FIG. 13, resistivities at respective
manufacturing stages are shown for three samples of sample 1,
sample 2, and sample 3. Herein, sample 1 has received no heat
treatment after a Cu film formation before a Ti film formation,
sample 2 has received a heat treatment for Cu polycrystallization
at 200.degree. C. for 30 minutes in a nitrogen atmosphere after a
Cu film formation before a Ti film formation and sample 3 has
received a heat treatment for Cu polycrystallization at 350.degree.
C. for 30 minutes.
[0143] In comparison with the resistivities after a heat treatment
for Cu polycrystallization of Sample 3, for which a heat treatment
after a Cu film formation has been sufficiently performed, a rise
in resistivity after performing a heat treatment to diffuse Ti at
350.degree. C. for 30 minutes after a Ti film formation was
suppressed to 3% or less in all samples. As such, a rise in
resistivity as a result of a Ti addition from the Cu surface is
considerably small. This is because Ti which has been added from
the surface diffuses along Cu crystal grain boundaries and is
hardly introduced in Cu bulk.
[0144] FIG. 14 shows results of a measurement, in the
aforementioned fabricated blanket wafer samples, of distributions
of Ti, Cu, and N in Cu by secondary ion mass spectrometry (SIMS).
The horizontal axis of the graph in FIG. 14 shows depth of the
blanket samples. The vertical axis of the graph in FIG. 14 shows
secondary ion intensity measured by SIMS, which corresponds to the
quantity of atoms.
[0145] Ti with a uniform concentration in a depth direction has
been detected in Cu crystals. Since a Ti diffusion coefficient in
bulk Cu is not large in a temperature region on the order of
350.degree. C., it is hardly conceived that Ti has diffused in bulk
Cu to form a uniform distribution as in FIG. 14, and it is
considered that Ti has uniformly diffused up to Cu bottom portions
via crystal grain boundaries and has thereby been added.
Accordingly, it can be considered that Ti has been hardly mixed in
bulk Cu and has been localized at grain boundaries.
[0146] FIG. 15 shows a relationship between resistivities owing to
a difference in additional elements and heat treatment. Samples
used for this resistivity measurement are blanket wafer samples
which had been fabricated similarly to the procedures of the
above-described embodiment except that a Ta/TaN barrier metal film
3a was formed on a SiO.sub.2 insulating film 1a, a 300 nm Cu layer
was further formed, and a Ni additional element layer 5a was
formed. Here, in the blanket wafer samples, no wiring holes and
wiring grooves were formed. Here, a film thickness of the
additional element layer was set so that a Ni concentration in Cu
becomes 3 atomic % when the additional element Ni has uniformly
diffused in Cu. The Ni film was formed by sputtering.
[0147] Similarly, respective blanket wafer samples were fabricated
by respectively forming respective films of additional elements of
Sn, Cr, and Co in place of the additional element Ni. In FIG. 15,
in terms of respective blanket wafer samples with additional
elements of Ni, Sn, Cr, and Co, shown are resistivities at
respective stages after an additional element layer formation,
after a heat treatment at 350.degree. C. for 30 minutes in a
nitrogen atmosphere, and after a heat treatment at 400.degree. C.
for 30 minutes in a nitrogen atmosphere.
[0148] In addition, in FIG. 15, for a comparison, resistivity
values of Cu where additional element concentration becomes 1
atomic % are shown. Here, these values have been extracted from a
publication (authored by C. Kittel, translation supervised by Masao
Doyama, "Quantum Theory of Solids," MARUZEN Co., Ltd., published
1972, p 338).
[0149] As a result, with regard to Sn and Ni, which are easily
solid-solved in Cu, a rise in resistivity was recognized with the
rise in heat treatment temperature. Particularly, with regard to
Sn, when heat treatment was applied at a temperature of 400.degree.
C., a rise in resistivity which is higher than when this was
uniformly mixed in Cu at 1 atomic % could be recognized. In
contrast thereto, with regard to Cr and Co, whose solid solubility
limits in Cu are low and which form precipitated alloys, a rise in
resistivity was hardly recognized with the rise in heat treatment
temperature. When additional elements which are easily solid-solved
in Cu, such as Cr and Co, are used, resistivity rises even if these
are added from the Cu surface. Accordingly, as the element to be
added from the Cu surface, a precipitating type element whose solid
solubility limit in Cu is low is preferable.
[0150] FIG. 16 shows, in terms of a blanket wafer sample which has
received a heat treatment at 350.degree. C. for 30 minutes without
forming a Ti film on the Cu surface after a Cu film formation and a
blanket wafer sample for which Ti film has been formed on the Cu
surface after a Cu film formation and which has received a heat
treatment at 350.degree. C. for 30 minutes, results of a
measurement of oxygen (O) distributions in Cu by SIMS. The
horizontal axis of the graph in FIG. 16 shows sample depth. In
addition, the vertical axis of the graph in FIG. 16 shows secondary
ion intensity measured by SIMS. In the sample which has received a
heat treatment at 350.degree. C. for 30 minutes without forming a
Ti film on the Cu surface after a Cu film formation, an O peak is
recognized in the vicinity of an interface between Cu and Ta,
whereas in the sample for which a Ti film has been formed on the Cu
surface after a Cu film formation and which has received a heat
treatment at 350.degree. C. for 30 minutes, no O peak is recognized
in the vicinity of an interface between Cu and Ta.
[0151] In addition, FIGS. 17(a) and (b) show scanning electron
microscope (SEM) photographs of Ta barrier surfaces after, of the
samples shown in FIG. 16, for a sample on whose surface a Ti film
has been formed, the Ta on the surface has been removed by diluted
hydrofluoric acid, and furthermore, for both samples, Cu has been
removed by nitric acid. As shown in FIG. 17(a), in the sample which
has received a heat treatment at 350.degree. C. for 30 minutes
without forming a Ti film on the Cu surface after a Cu film
formation, a Ta surface at a part where Cu grain boundaries had,
presumedly, existed has bulged, and oxidation of Ta at this part
has been confirmed. In contrast thereto, as shown in FIG. 17(b), in
a sample for which a Ti film has been formed on the Cu surface
after a Cu film formation and which has received a heat treatment
at 350.degree. C. for 30 minutes, the Ta surface is flat and smooth
and no Ta oxidation is recognized. These results correspond to the
results of an SIMS analysis shown in FIG. 16.
[0152] It is considered that the Ta oxidation is due to oxygen on
the Cu surface and in Cu which has been diffused by a heat
treatment at 350.degree. C. and has oxidized Ta. In the case where
a Ti film has been formed on the Cu surface, it is considered that
the Ti getters oxygen on the Cu surface and in Cu during the
following annealing and thereby oxidation of the barrier Ta was
suppressed. Accordingly, effects of the Ti film on the Cu surface
includes an effect to suppress barrier Ta from oxidation by
gettering oxygen in Cu.
MODIFICATIONS OF THE INVENTION
[0153] For the wiring metal for a semiconductor device and
manufacturing method therefor described in the above, the following
modifications may be provided.
[0154] In the above-mentioned embodiments, it has been described
that the lower-layer wiring and upper-layer wiring could be formed
by an identical method, however, lower-layer wiring and upper-layer
wiring may be formed by different methods by a combination of the
above-mentioned respective embodiments.
[0155] As a constituent material of the insulating film 1,
SiO.sub.2 and the like and other insulating materials can be used.
As the constituent material of the insulating film 1, it is
preferable to use a materiel of a lower dielectric constant. The
insulating film 1 is formed by a plasma CVD method or the like.
Although the film thickness of the insulating film 1 is not
particularly limited, the thickness of the insulating film 1a is on
the order of 100 to 3000 nm, the thickness of the insulating film
1b is on the order of 100 to 1000 nm, the thickness of the
insulating film 1c is on the order of 100 to 1000 nm, and the
thickness of the insulating film 1d is on the order of 100 to 1000
nm.
[0156] As a constituent material of the stopper insulating film 2,
insulating materials such as SiC, SiN, SiCN, and the like can be
used. As the constituent material of the stopper insulating film 2,
it is preferable to use a material of a lower dielectric constant.
The stopper insulating film 2 is formed by a plasma CVD method or
the like. Although the film thickness of the stopper insulating
film 2 is not particularly limited, the thickness of the stopper
insulating film 2a is on the order of 10 to 100 nm, and the
thickness of the stopper insulating film 2b is on the order of 10
to 100 nm. In addition, although the stopper insulating film 2 is
used as an etching stopper of concavities for wiring, however, if
the concavities for wiring can be processed in an objective form,
the stopper insulating film 2 is not necessarily used.
[0157] The wiring grooves are formed by lithography and etching
(anisotropic etching) or the like. Although the width of the wiring
grooves is not particularly limited, normally, these are provided
on the order of a diameter of 50 to 20000 nm.
[0158] As a constituent material of the barrier metal 3, a
substance selected from metals such as Ta, Ti, and W, nitrides of
these metals, ternary or quaternary nitrides produced by adding Si
or the like to these nitrides can be used. The barrier metal film 3
is formed by an ionization sputtering method, a CVD method, an
Atomic Layer Deposition (ALD) method or the like. Although the film
thickness of the barrier metal film 3 is not particularly limited,
the barrier metal film 3a is on the order of 5 to 50 nm, and the
barrier metal film 3b is on the order of 5 to 50 nm.
[0159] As a method for forming the metal wiring Cu 4, this can be
formed, after forming a Cu thin film by an ionization sputtering
method, a CVD method, a metal-organic chemical vapor deposition
method (MO-CVD method) or the like, by an electrolytic plating
method while using this Cu thin film as an electrode or by an
MO-CVD method. In addition, it is also possible to directly bury Cu
into wiring grooves by an MO-CVD method without forming a Cu thin
film. The film thickness of the metal wiring Cu 4 is not
particularly limited as long as this is formed to such an extent to
fill up the wiring grooves and wiring holes.
[0160] A heat treatment for Cu crystal grain growth (Cu
polycrystallization) is performed in a reducing atmosphere of
nitrogen, hydrogen or the like. This heat treatment is performed at
400.degree. C. or less, and preferably, at 300.degree. C. or less.
However, this heat treatment step may be omitted.
[0161] As a constituent material of the additional element layer 5,
Ti, Zr, Hf, Cr, Co, Al, Sn, Mg, Ag and the like can be used. The
additional element layer 5 is formed by sputtering or the like.
Although the film thickness of the additional element layer 5 is
not particularly limited, the additional element layer 5a is on the
order of 5 to 100 nm, and the additional element layer 5b is on the
order of 5 to 100 nm.
[0162] A heat treatment to diffuse the additional element into Cu 4
from the additional element layer 5 is performed in an atmosphere
of nitrogen or the like. This heat treatment is performed under a
temperature condition on the order of 300 to 500.degree. C. for 10
minutes to 1 hour.
[0163] Removal of an excessive additional element layer 5 is
performed by wet etching with hydrofluoric acid or by CMP.
[0164] Removal of excessive Cu 4 and an excessive barrier metal
film 3 is performed by CMP.
[0165] As a constituent material of the barrier insulating film 8,
insulating materials having barrier properties against Cu such as
SiCN, SiC, SiN and the like can be used. The barrier insulating
film 8 is formed by a plasma CVD method or the like. Although the
film thickness of the barrier insulating film 8 is not particularly
limited, the barrier insulating film 8a is on the order of 20 to
100 nm, the barrier insulating film 8b is on the order of 20 to 100
nm.
[0166] Wiring holes are formed by lithography and anisotropic dry
etching or the like. Although the width of the wiring holes is not
particularly limited, normally, these are provided on the order of
a diameter of 50 to 1000 nm.
[0167] As a constituent material of the cover insulating film 9,
SiO.sub.2 and the like and other insulating materials can be used.
The cover insulating film 9 is formed by a plasma CVD method or the
like. Although the film thickness of the cover insulating film 9 is
not particularly limited, the cover insulating film 9 is on the
order of 100 to 10000 nm.
[0168] In the above embodiments and example, descriptions have been
given while raising, as an example, a semiconductor device for
which metal wiring composed of a wiring metal containing
polycrystal consisting primarily of Cu and an additional element
other than Cu has been formed on a substrate on which a
semiconductor element has been formed. In the present invention,
wiring metals having the aforementioned structure and wiring metals
manufactured by the aforementioned respective manufacturing methods
are used as metallic materials for wiring for not only
semiconductor devices but also other uses.
* * * * *