U.S. patent application number 11/008019 was filed with the patent office on 2005-09-22 for photoresist residue remover composition and semiconductor circuit element production process employing the same.
Invention is credited to Ishikawa, Norio, Kawamoto, Hiroshi, Miyasato, Mikie, Oowada, Takuo.
Application Number | 20050209118 11/008019 |
Document ID | / |
Family ID | 34510503 |
Filed Date | 2005-09-22 |
United States Patent
Application |
20050209118 |
Kind Code |
A1 |
Kawamoto, Hiroshi ; et
al. |
September 22, 2005 |
Photoresist residue remover composition and semiconductor circuit
element production process employing the same
Abstract
A photoresist residue remover composition is provided that
removes a photoresist residue formed by a resist ashing treatment
after dry etching in a step of forming, on a substrate surface,
wiring of any metal of aluminum, copper, tungsten, and an alloy
having any of these metals as a main component, the composition
including one or two or more types of inorganic acid and one or two
or more types of inorganic fluorine compound. There is also
provided a process for producing a semiconductor circuit element
wherein, in a step of forming wiring of any metal of aluminum,
copper, tungsten, and an alloy having any of these metals as a main
component, the photoresist residue remover composition is used for
removing a photoresist residue formed by a resist ashing treatment
after dry etching.
Inventors: |
Kawamoto, Hiroshi;
(Kamakura-shi, JP) ; Miyasato, Mikie;
(Yokohama-shi, JP) ; Oowada, Takuo; (Soka-shi,
JP) ; Ishikawa, Norio; (Kasukabe-shi, JP) |
Correspondence
Address: |
L.C. BEGIN & ASSOCIATES, PLLC
510 HIGHLAND AVENUE
PMB 403
MILFORD
MI
48381
US
|
Family ID: |
34510503 |
Appl. No.: |
11/008019 |
Filed: |
December 9, 2004 |
Current U.S.
Class: |
510/175 |
Current CPC
Class: |
H01L 21/02063 20130101;
G03F 7/423 20130101; H01L 21/02071 20130101 |
Class at
Publication: |
510/175 |
International
Class: |
C11D 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 9, 2003 |
JP |
2003-410836 |
Claims
What is claimed is:
1. A photoresist residue remover composition for removing a
photoresist residue formed by a resist ashing treatment after dry
etching in a step of forming, on a substrate surface, wiring of any
metal of aluminum, copper, tungsten, and an alloy having any of
these metals as a main component, the composition comprising one or
two or more types of inorganic acid and one or two or more types of
inorganic fluorine compound, wherein the amount of inorganic acid
added is 30% by mass or less, and the amount of inorganic fluorine
compound added is 0.001 to 0.015% by mass on a hydrofluoric acid
basis, with the proviso that the composition dose not contain
organic acid, quarterly alkyl ammonium, hydrogen peroxide and
ozone.
2. The photoresist residue remover composition according to claim
1, wherein the inorganic aid is selected from the group of sulfuric
acid, nitric acid, hydrochloric acid or phosphoric acid.
3. The photoresist residue remover according to claim 1, wherein
the inorganic fluorine compound is selected from the group of
hydrofluoric acid, ammonium fluoride or ammonium hydrogen
fluoride.
4. The photoresist residue remover composition according to claim
1, wherein the inorganic acid is sulfuric acid.
5. The photoresist residue remover composition according to claim
1, wherein the inorganic fluorine compound is hydrofluoric
acid.
6. The photoresist residue remover composition according to claim
1, wherein further contain a complexing agent.
7. A process for producing a semiconductor circuit element wherein,
in a step of forming wiring of any metal of aluminum, copper,
tungsten, and an alloy having any of these metals as a main
component, the photoresist residue remover composition according to
claim 1 is used for removing a photoresist residue formed by a
resist ashing treatment after dry etching.
8. A process for producing a semiconductor circuit element wherein,
in a step of forming wiring of any metal of aluminum, copper,
tungsten, and an alloy having any of these metals as a main
component, the photoresist residue remover composition according to
claim 2 is used for removing a photoresist residue formed by a
resist ashing treatment after dry etching.
9. A process for producing a semiconductor circuit element wherein,
in a step of forming wiring of any metal of aluminum, copper,
tungsten, and an alloy having any of these metals as a main
component, the photoresist residue remover composition according to
claim 3 is used for removing a photoresist residue formed by a
resist ashing treatment after dry etching.
10. A process for producing a semiconductor circuit element
wherein, in a step of forming wiring of any metal of aluminum,
copper, tungsten, and an alloy having any of these metals as a main
component, the photoresist residue remover composition according to
claim 4 is used for removing a photoresist residue formed by a
resist ashing treatment after dry etching.
11. A process for producing a semiconductor circuit element
wherein, in a step of forming wiring of any metal of aluminum,
copper, tungsten, and an alloy having any of these metals as a main
component, the photoresist residue remover composition according to
claim 5 is used for removing a photoresist residue formed by a
resist ashing treatment after dry etching.
12. A process for producing a semiconductor circuit element
wherein, in a step of forming wiring of any metal of aluminum,
copper, tungsten, and an alloy having any of these metals as a main
component, the photoresist residue remover composition according to
claim 6 is used for removing a photoresist residue formed by a
resist ashing treatment after dry etching.
13. A process for producing a semiconductor circuit element,
wherein the photoresist residue remover composition according to
claim 1 is used for carrying out a pre-treatment or a
post-treatment on multilayer wiring.
14. A process for producing a semiconductor circuit element,
wherein the photoresist residue remover composition according to
claim 2 is used for carrying out a pre-treatment or a
post-treatment on multilayer wiring.
15. A process for producing a semiconductor circuit element,
wherein the photoresist residue remover composition according to
claim 3 is used for carrying out a pre-treatment or a
post-treatment on multilayer wiring.
16. A process for producing a semiconductor circuit element,
wherein the photoresist residue remover composition according to
claim 4 is used for carrying out a pre-treatment or a
post-treatment on multilayer wiring.
17. A process for producing a semiconductor circuit element,
wherein the photoresist residue remover composition according to
claim 5 is used for carrying out a pre-treatment or a
post-treatment on multilayer wiring.
18. A process for producing a semiconductor circuit element,
wherein the photoresist residue remover composition according to
claim 6 is used for carrying out a pre-treatment or a
post-treatment on multilayer wiring.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a photoresist residue
remover composition and, in particular, to a photoresist residue
remover composition for removing a photoresist residue formed by a
resist ashing treatment after dry etching in a step of forming, on
a substrate surface, wiring of any metal of aluminum, copper,
tungsten, and an alloy having any of these metals as a main
component in the production of a semiconductor circuit element, and
a semiconductor circuit element production process employing the
photoresist residue remover composition. More particularly, it
relates to a photoresist residue remover composition containing an
inorganic acid, an inorganic fluorine compound, and water and
containing no hydrogen peroxide, and a semiconductor circuit
element production process employing the photoresist residue
remover composition.
[0002] The photoresist residue referred to here means a photoresist
residue (also called sidewall polymer, sidewall protection film,
rabbit ear) comprising incompletely ashed resist, an organometallic
polymer, a metal oxide, etc., which remains on the substrate
surface after dry etching and then ashing the resist.
DESCRIPTION OF THE RELATED ART
[0003] In the production process of a semiconductor circuit
element, a photoresist residue formed in a step of forming a metal
wiring pattern of aluminum, copper, tungsten, or an alloy having
any of these metals as a main component on a substrate surface, the
step employing a photoresist together with dry etching and ashing,
is usually removed by a photoresist residue remover.
[0004] With regard to a photoresist residue remover used when
forming metal wiring on a substrate surface, for example, in a case
when the wiring is an aluminum alloy, a photoresist residue remover
composition containing ammonium fluoride, an organic acid, and
water has been reported (e.g., JP, A, 6-349785), but the content of
acetic acid, which corresponds to the organic acid, is a high value
of 30 to 90 wt %, and a heavy burden is thus imposed on the
environment; moreover, acetic acid has unpleasant smell, and the
workability is poor.
[0005] Furthermore, in the case when the wiring is any of aluminum,
an aluminum alloy, and tungsten, a photoresist residue remover
composition comprising `fluorine compound+quaternary ammonium
compound+water` or `fluorine compound+quaternary ammonium
compound+organic solvent+water`, and a resist and etching residue
remover composition comprising `hydroxylamine+alkanolamine
(+solvent)` have been proposed (e.g., JP, A, 7-201794 and U.S. Pat.
No. 5,334,332). Although these photoresist residue removers are
less corrosive to the metal and can be used at room temperature, it
takes a long treatment time of 20 to 30 minutes to completely
remove the adhered photoresist residue. Because of this, these
photoresist residue removers cannot be used in a single wafer
cleaning system requiring a short, low temperature treatment, which
has recently been introduced to the photoresist residue removal
step. Furthermore, these photoresist residue removers contain a few
tens or more wt % of an organic compound such as a quaternary amine
or an organic solvent, thus imposing a heavy burden on the
environment.
[0006] In contrast, it has been reported that a composition
comprising `fluoride-containing compound+sulfuric acid+hydrogen
peroxide or ozone+water`, which are all inorganic compounds, can
remove a photoresist residue with a short, low temperature
treatment, and is less corrosive to an aluminum alloy (e.g., JP, A,
11-243085), but since the hydrogen peroxide or ozone decomposes,
the stability over time of the photoresist residue remover itself
is a problem. Furthermore, when used in a single wafer cleaning
system, as shown in Examples of the present invention, corrosion of
a wiring metal such as aluminum cannot be suppressed sufficiently.
As a fluoride-containing compound, only hydrofluoric acid is cited
as an example.
[0007] On the other hand, as a photoresist residue remover for
removing a photoresist residue formed during dry etching when
forming a substrate having no wiring, compositions comprising
`sulfuric acid 5 to 7+hydrofluoric acid 1/400 to 1/1000 (ratio by
volume)` or `sulfuric acid 5 to 7+aqueous hydrogen peroxide
1+hydrofluoric acid 1/400 to 1/1000 (ratio by volume)` have been
reported (e.g., JP, A, 11-135473). As the amount of hydrofluoric
acid added and the amount of hydrogen peroxide added is too small,
the concentration of sulfuric acid is not diluted, and no
consideration was given to the influence on a metal, etc. used for
wiring.
[0008] Furthermore, although it is not a photoresist residue
remover, a composition comprising `0.01 to 1.0 wt % of hydrofluoric
acid+0.001 to 30.0 wt % of an inorganic acid (hydrochloric acid,
sulfuric acid, nitric acid)+water`, etc. has been reported as an
etching composition for a doped silicon oxide film (e.g., JP, A,
2003-45894). These compositions might be able to remove a
photoresist residue containing an inorganic oxide, but the
possibility of the use thereof for removal of a photoresist residue
has not yet been reported. It can perhaps be expected that, since a
composition comprising `hydrofluoric acid+about 10% or greater of
nitric acid+water` (e.g., JP, A, 5-82505), a composition comprising
`hydrofluoric acid 10+nitric acid 250+water 60 (ratio by volume)`
(e.g., JP, A, 6-10161), etc. have been reported as etching
compositions for an aluminum alloy, the above-mentioned
compositions are judged to be highly corrosive to wiring.
[0009] As hereinbefore described, in a step involving forming, on a
substrate surface, wiring of any metal of aluminum, copper,
tungsten, and an alloy having any of these metals as a main
component in a production step for a semiconductor circuit element,
no photoresist residue remover, as a photoresist residue remover
composition for removing a photoresist residue formed by a resist
ashing treatment after dry etching, has so far been disclosed that
is not corrosive to the metal wiring, does not contain a large
amount of an organic compound such as an organic solvent in order
to lessen the burden on the environment, and has excellent storage
stability, and there has been a desire for development of a
photoresist residue remover composition that enables a short, low
temperature treatment to be carried out and can therefore be
employed in the single wafer cleaning system, which has been used
in recent years.
SUMMARY OF THE INVENTION
[0010] It is therefore an object of the present invention to
provide a photoresist residue remover composition that removes a
photoresist residue formed by a resist ashing treatment after dry
etching in a step involving forming, on a substrate surface, wiring
formed from any metal of aluminum, copper, tungsten, and an alloy
having any of these metals as a main component in a production step
for a semiconductor circuit element, the photoresist residue
remover composition having low corrosiveness to the wiring
material, not containing a large amount of an organic compound such
as an organic solvent so as to lessen the burden on the
environment, having excellent storage stability, and enabling a
short, low temperature treatment to be carried out.
[0011] As a result of an intensive investigation by the present
inventors in order to solve the above-mentioned problems, it has
been found that a photoresist residue remover composition
containing an inorganic acid and an inorganic fluorine compound has
sufficiently suppressed corrosiveness to aluminum, copper,
tungsten, and an alloy having any of these metals as a main
component, can remove a photoresist residue with a short, low
temperature treatment, and has excellent storage stability, and the
present invention has thus been accomplished.
[0012] That is, the present invention relates to a photoresist
residue remover composition for removing a photoresist residue
formed by a resist ashing treatment after dry etching in a step of
forming, on a substrate surface, wiring of any metal of aluminum,
copper, tungsten, and an alloy having any of these metals as a main
component, the composition comprising one or two or more types of
inorganic acid and one or two or more types of inorganic fluorine
compound.
[0013] Furthermore, the present invention relates to the
photoresist residue remover composition wherein the amount of
inorganic acid added is 30% by mass or less, and the amount of
inorganic fluorine compound added is 0.001 to 0.015% by mass.
[0014] Moreover, the present invention relates the photoresist
residue remover composition wherein it contains no hydrogen
peroxide.
[0015] Furthermore, the present invention relates to the
photoresist residue remover composition wherein the inorganic acid
is sulfuric acid, and the inorganic fluorine compound is
hydrofluoric acid.
[0016] Moreover, the present invention relates to a process for
producing a semiconductor circuit element wherein, in a step of
forming wiring of any metal of aluminum, copper, tungsten, and an
alloy having any of these metals as a main component, the
photoresist residue remover composition is used to remove a
photoresist residue formed by a resist ashing treatment after dry
etching.
[0017] Furthermore, the present invention relates to a process for
producing a semiconductor circuit element, wherein the photoresist
residue remover composition is used for carrying out a
pre-treatment or a post-treatment on multilayer wiring.
[0018] The photoresist residue remover composition of the present
invention enables the photoresist residue to be removed by a short,
low temperature treatment, and the ratio of the inorganic acid to
the inorganic fluorine compound added is optimized so that
corrosion of aluminum, copper, tungsten, and an alloy having any of
these metals as a main component can be suppressed sufficiently.
Furthermore, since the composition of the present invention
contains only inorganic compounds, the burden on the environment
can be lessened, and the combination of an inorganic acid and an
inorganic fluorine compound exhibits the effect of minimizing the
influence on metal wiring while enhancing resist residue
removability by the short, low temperature treatment, which cannot
be achieved by conventional technology.
[0019] As hereinbefore described, the photoresist residue remover
composition of the present invention is a photoresist residue
remover composition for removing a photoresist residue formed by a
resist ashing treatment after dry etching in a step of forming, on
a substrate surface, wiring of any metal of aluminum, copper,
tungsten, and an alloy having any of these metals as a main
component, the composition enabling the photoresist residue to be
removed by a short, low temperature treatment and sufficiently
suppressing corrosion of the metals.
BRIEF DESCRIPTION OF DRAWINGS
[0020] FIG. 1 is a diagram of a semiconductor circuit element (with
a wiring material film) treated with an organic fluorine
photoresist residue remover.
[0021] FIG. 2 is a diagram of a semiconductor circuit element (with
a wiring material film) treated with the photoresist residue
remover composition of the present invention.
[0022] FIG. 3 is a diagram of a semiconductor circuit element
(multilayer wiring having a damascene structure or a through hole)
treated with the photoresist residue remover composition of the
present invention.
[0023] FIG. 4 is a diagram showing etching behavior of a
semiconductor circuit element treated with an organic fluorine
photoresist residue remover when rinsing with pure water.
[0024] FIG. 5 is a diagram showing etching behavior of a
semiconductor circuit element treated with the photoresist residue
remover composition of the present invention when rinsing with pure
water.
BEST MODE FOR CARRYING OUT THE INVENTION
[0025] Examples of the inorganic acid used in the photoresist
residue remover composition of the present invention include
sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid.
Among these, sulfuric acid is preferable.
[0026] The present inventors have found that, when the amount of
inorganic acid added is increased, the photoresist residue
removability is reduced, and corrosiveness to aluminum, copper,
tungsten, and an alloy having any of these metals as a main
component depends on the type of acid, whereas when the amount of
inorganic acid added is decreased, the photoresist residue
removability improves but corrosiveness to the metals
increases.
[0027] That is, when the amount of inorganic acid added is too
large, photoresist residue removal becomes a problem, and when the
amount thereof added is too small, corrosiveness to the metals
becomes a problem. Although the reason therefor is unclear, it is
surmised that when the amount of inorganic acid added is too large,
dissociation of the inorganic fluorine compound is suppressed,
thereby reducing the photoresist residue removability. The amount
of inorganic acid added is therefore appropriately determined by
the photoresist residue removability and the corrosiveness to the
metals while taking into consideration the amount of inorganic
fluorine compound added, and it is preferably 30% by mass or less,
and more preferably 3 to 15% by mass.
[0028] Furthermore, examples of the inorganic fluorine compound
used in the photoresist residue remover composition of the present
invention include hydrofluoric acid, ammonium fluoride, and
ammonium hydrogen fluoride. Among these, hydrofluoric acid is
preferable.
[0029] The present inventors have found that, when the amount of
inorganic fluorine compound added is increased, the photoresist
residue removability increases and at the same time the
corrosiveness to the metals increases, and when the amount thereof
added is decreased, the photoresist residue removability and the
corrosiveness to the metals are decreased. That is, when the amount
of inorganic fluorine compound added is too large, the
corrosiveness to the metals is a problem, and when the amount
thereof added is too small, the photoresist residue removability
becomes a problem. The amount of inorganic fluorine compound added
is therefore appropriately determined by the photoresist residue
removability and the corrosiveness to the metals while taking into
consideration the amount of inorganic acid added, and is preferably
0.001 to 0.015% by mass, and more preferably 0.005 to 0.011% by
mass.
[0030] Furthermore, it is preferable for the photoresist residue
remover composition of the present invention to contain no hydrogen
peroxide. When hydrogen peroxide is added, corrosion of the metals
is accelerated, and not only is it impossible to ensure sufficient
margin in the treatment conditions, but also there is a possibility
of the stability over time of the photoresist residue remover
composition being degraded due to decomposition of hydrogen
peroxide.
[0031] Moreover, the photoresist residue remover composition of the
present invention may contain a surfactant in order to improve the
removability of particles of an organometallic polymer, etc.
contained in the photoresist residue, or in order to improve the
ease of microfabrication by improving the wettability toward a
substrate.
[0032] Furthermore, the photoresist residue remover composition of
the present invention may further contain a complexing agent in
order to improve the removability of a metal oxide, etc.
[0033] During the process of examining the problems of the present
invention, the present inventors have gained the knowledge that,
when the photoresist residue remover of the present invention
contains 0.001 to 0.015% by mass of the inorganic fluorine
compound, even when it contains 30% by mass or greater of sulfuric
acid, although the removability of the photoresist residue is
degraded, the corrosiveness to metals is suppressed. The
composition of the present invention is therefore a novel
composition that, by adjusting the amount of sulfuric acid added,
can be used not only in a single wafer cleaning system, which
requires a short, low temperature treatment, but also in a
batchwise dipping system involving a long, high temperature
treatment.
[0034] Moreover, use of the photoresist residue remover composition
of the present invention enables a pre-treatment or post-treatment
to be carried out on multilayer wiring. The pre-treatment referred
to here means a pre-treatment for a metal embedding step, that is,
a step of removing a photoresist residue before metal embedding of
multilayer wiring having a damascene structure or a through hole as
shown in FIG. 3. By removing, with the photoresist residue remover
composition of the present invention, residue present on the
damascene or the through hole after dry etching and ashing, it is
possible to prevent corrosion of the metal wiring of a lower layer
or the embedded metal, etc.
[0035] The post-treatment referred to above means a treatment, with
the remover of the present invention, of the resist residue and a
residue such as a reaction product remaining on the wiring sidewall
and the wiring after dry etching and ashing a wiring material film
formed as shown in FIG. 2. The photoresist residue remover
composition of the present invention not only has excellent
removability but also has little influence on the metal, and can
suppress thinning of the wiring and formation of voids.
[0036] The present invention is suitable for the pre-treatment and
the post-treatment of multilayer wiring but can also be used as a
remover for a photoresist residue formed during a dry
etching-ashing treatment of a semiconductor circuit element with no
metal wiring.
EXAMPLES
[0037] The photoresist residue remover composition of the present
invention is now explained further in detail with reference to
Examples and Comparative Examples, but the present invention is not
limited by these Examples.
[0038] 1) Corrosive Evaluation Test Against Al Wiring
[0039] As shown in FIG. 2, films of TiN/Ti, Al, and TiN/Ti were
formed in sequence on a silicon wafer, dry etching was carried out
using as a mask a resist that had been applied to the TiN/T,
exposed, and developed, and after a wiring pattern was thus formed,
the resist was removed by ashing to give a wafer on which a
photoresist residue was formed. This wafer was subsequently
subjected to a dipping treatment in a photoresist residue remover
at 25.degree. C. for 30 to 150 seconds and a rinsing treatment with
running ultrapure water, dried, and then evaluated by electron
microscopy with respect to removability of the photoresist residue
and corrosiveness to Al. The results are given in Table 1.
[0040] 2) Corrosive Evaluation Test Against Cu Wiring
[0041] Films of Cu damascene wiring using Ta as barrier metal, an
interlayer insulating film, etc. were formed in sequence on a
silicon wafer, dry etching was carried out using as a mask a resist
that had been applied to the interlayer insulating film, exposed,
and developed, and after a via hole was thus formed, the resist was
removed by ashing to give a wafer on which a photoresist residue
was formed. This wafer was subsequently subjected to a dipping
treatment in a photoresist residue remover at 25.degree. C. for 30
to 150 seconds and a rinsing treatment with running ultrapure
water, dried, and then evaluated by electron microscopy with
respect to removability of the photoresist residue and
corrosiveness to Cu. The results are given in Table 2.
[0042] 3) Evaluation Test of Amount of Cu or W Film Etched
[0043] A silicon wafer having a Cu or W film formed thereon was
subjected to a dipping treatment in a photoresist residue remover
at 25.degree. C. for 60 minutes and a rinsing treatment with
running ultrapure water, and dried, and the amount of Cu or W
etched was then measured using an X-ray fluorescence film thickness
meter. The results are given in Table 3.
[0044] 4) Evaluation Test of Amount of Etching of AlCu Wiring in
Rinsing Step After Removal of Resist
[0045] As shown in FIG. 1 and FIG. 2, films of TiN/Ti, AlCu, and
TiN/Ti were formed in sequence on a substrate oxide film, dry
etching was carried out using as a mask a resist that had been
applied to the TiN/Ti, exposed, and developed, and after a wiring
pattern was thus formed, the resist was removed by ashing to give a
wafer on which a photoresist residue was formed. This wafer was
subsequently subjected to evaluation by the following method, which
corresponds to the rinsing conditions, in terms of the
corrosiveness to AlCu metal wiring during rinsing with pure water
after removal of the photoresist residue.
[0046] That is, the wafer was subjected to a dipping treatment at
room temperature for 90 seconds in an aqueous solution containing
0.009% by mass of HF and 7.5% by mass of sulfuric acid, which is a
composition of the present invention, and then a dipping treatment
in the above composition diluted with pure water for 60 seconds,
dried, and then subjected to a measurement, using a four-point
probe system sheet resistance meter, of the amount of etching of
AlCu metal wiring. The results are given in FIG. 5. The amount of
etching when the treatment was carried out in the same manner using
a conventionally used fluorine compound and organic
solvent-containing photoresist residue remover (ELM-C30
manufactured by Mitsubishi Gas Chemical Company, Inc.) was also
measured. The results are given in FIG. 4.
1 TABLE 1 Mixing ratio of photoresist residue remover Treatment
composition conditions Evaluation results Composition % by % by %
by Temperature Time Photoresist residue Corrosiveness No. Component
1 mass Component 2 mass Component 3 mass (.degree. C.) (sec.)
removability *1 to Al *2 1 (Comp. Ex.) EKCU.quadrature.265 *3 25 90
C A 2 (Comp. Ex.) ELM-C30 *4 25 90 C A 3 (Ref. Ex.) H.sub.2SO.sub.4
7.50 HF 0.009 H.sub.2O.sub.2 7.50 25 60 A C 4 (Ref. Ex.)
H.sub.2SO.sub.4 7.50 HF 0.009 H.sub.2O.sub.2 7.50 25 90 A C 5 (Ref.
Ex.) H.sub.2SO.sub.4 95.00 HF 0.180 -- -- 25 90 C B 6 (Ref. Ex.)
H.sub.2SO.sub.4 96.00 HF 0.005 -- -- 25 90 C A 7 H.sub.2SO.sub.4
3.75 HF 0.005 -- -- 25 90 A A 8 H.sub.2SO.sub.4 3.75 HF 0.009 -- --
25 60 A A 9 H.sub.2SO.sub.4 3.75 HF 0.009 -- -- 25 90 A A 10
H.sub.2SO.sub.4 3.75 HF 0.015 -- -- 25 90 A A 11 H.sub.2SO.sub.4
7.50 HF 0.005 -- -- 25 90 A A 12 H.sub.2SO.sub.4 7.50 HF 0.009 --
-- 25 60 A A 13 H.sub.2SO.sub.4 7.50 HF 0.009 -- -- 25 90 A A 14
H.sub.2SO.sub.4 7.50 HF 0.015 -- -- 25 90 A A 15 H.sub.2SO.sub.4
15.00 HF 0.009 -- -- 25 90 A A 16 H.sub.2SO.sub.4 15.00 HF 0.015 --
-- 25 90 A A 17 H.sub.3PO.sub.4 7.50 HF 0.009 -- -- 25 90 A A 18
HNO.sub.3 7.50 HF 0.009 -- -- 25 90 A A 19 HCl 7.50 HF 0.009 -- --
25 90 A A *1 A: good, C: photoresist residue remaining *2 A: no
corrosion, B: slight corrosion, C: corroded *3 An
aminoalcohol-containing photoresist residue remover manufactured by
EKC Technology. *4 A fluorine compound and organic
solvent-containing photoresist residue remover manufactured by
Mitsubishi Gas Chemical Company, Inc.
[0047]
2 TABLE 2 Mixing ratio of photoresist residue remover Treatment
composition conditions Evaluation results Composition % by % by %
by Temperature Time Photoresist residue Corrosiveness No. Component
1 mass Component 2 mass Component 3 mass (.degree. C.) (sec.)
removability *1 to Cu *2 20 (Comp. Ex.) EKC-265 *3 25 90 C A 21
(Comp. Ex.) ELM-C3C *4 25 90 C A 22 (Ref. Ex.) H.sub.2SO.sub.4 7.50
HF 0.009 H.sub.2O.sub.2 7.50 25 60 A B 23 (Ref. Ex.)
H.sub.2SO.sub.4 7.50 HF 0.009 H.sub.2O.sub.2 7.50 25 90 A B 24
(Ref. Ex.) H.sub.2SO.sub.4 95.00 HF 0.180 -- -- 25 90 C B 25
H.sub.2SO.sub.4 7.50 HF 0.009 -- -- 25 90 A A 26 H.sub.3PO.sub.4
7.50 HF 0.009 -- -- 25 90 A A 27 HNO.sub.3 7.50 HP 0.009 -- -- 25
90 A A 28 HCl 7.50 HF 0.009 -- -- 25 90 A A *1 A: good, C:
photoresist residue remaining *2 A: no corrosion, B: slight
corrosion, C: corroded *3 An aminoalcohol-containing photoresist
residue remover manufactured by EKC Technology. *4 A fluorine
compound and organic solvent-containing photoresist residue remover
manufactured by Mitsubishi Gas Chemical Company, Inc.
[0048]
3TABLE 3 Mixing ratio of photoresist residue remover Treatment Com-
composition conditions Evaluation results position % by % by % by
Temperature Time Amount of Cu Amount of W No. Component 1 mass
Component 2 mass Component 3 mass (.degree.C.) (sec.) etched (nm)
etched (nm) 29 H.sub.2SO.sub.4 7.50 HF 0.009 -- -- 25 60 5.9
1.0.dwnarw. 30 H.sub.3PO.sub.4 7.50 HF 0.009 -- -- 25 60 4.2
1.0.dwnarw. 31 HNO.sub.3 7.50 HF 0.009 -- -- 25 60 7.0 1.0.dwnarw.
32 HCl 7.50 HF 0.009 -- -- 25 60 6.4 1.0.dwnarw.
[0049] From the above-mentioned results, it has been confirmed that
the photoresist remover compositions of the present invention have
sufficient photoresist removability even in a short, low
temperature treatment and are not corrosive to metals.
[0050] Furthermore, the photoresist remover compositions of the
present invention cause far less etching during the rinsing step
compared with an organic fluorine photoresist residue remover, and
can suppress thinning and void formation in Al wiring.
[0051] In accordance with use of the photoresist residue remover
composition of the present invention, which removes the photoresist
residue formed during a resist ashing treatment after dry etching
in the step of forming, on a substrate surface, wiring of any metal
of aluminum, copper, tungsten, and an alloy having one of these
metals as a main component, the photoresist residue can be removed
by a short, low temperature treatment without corroding the metal
wiring.
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