U.S. patent application number 10/577481 was filed with the patent office on 2007-03-29 for unsaturated dicarboxylic acid and ethylene urea containing formulation for cleaning semiconductor and cleaning method.
This patent application is currently assigned to NISSAN CHEMICAL INDUSTRIES, LTD. Invention is credited to Yoichiro Fujita, Ichiro Kobayashi, Tomoe Miyazawa.
Application Number | 20070072782 10/577481 |
Document ID | / |
Family ID | 34550005 |
Filed Date | 2007-03-29 |
United States Patent
Application |
20070072782 |
Kind Code |
A1 |
Miyazawa; Tomoe ; et
al. |
March 29, 2007 |
Unsaturated dicarboxylic acid and ethylene urea containing
formulation for cleaning semiconductor and cleaning method
Abstract
A semiconductor wafer cleaning formulation comprising an
unsaturated dicarboxylic acid and ethylene urea, and a cleaning
method are provided. The formulation comprises an unsaturated
dicarboxylic acid and ethylene urea as essential components, and is
used for removing residues in semiconductor fabrication. As the
unsaturated dicarboxylic acid, maleic acid is particularly
preferable. The preferred formulation comprises an unsaturated
dicarboxylic acid, ethylene urea, at least one organic carboxylic
acid except unsaturated dicarboxylic acid, at least one basic
compound except ethylene urea and water. The formulation can
optionally comprise at least one selected from the group consisting
of an organic solvent, a chelating agent, a surfactant, and
phosphonic acid and/or phosphinic acid.
Inventors: |
Miyazawa; Tomoe;
(Funabashi-shi, JP) ; Fujita; Yoichiro;
(Funabashi-shi, JP) ; Kobayashi; Ichiro;
(Chiyoda-ku, JP) |
Correspondence
Address: |
OLIFF & BERRIDGE, PLC
P.O. BOX 19928
ALEXANDRIA
VA
22320
US
|
Assignee: |
NISSAN CHEMICAL INDUSTRIES,
LTD
TOKYO
JP
|
Family ID: |
34550005 |
Appl. No.: |
10/577481 |
Filed: |
October 27, 2004 |
PCT Filed: |
October 27, 2004 |
PCT NO: |
PCT/JP04/15935 |
371 Date: |
August 7, 2006 |
Current U.S.
Class: |
510/175 |
Current CPC
Class: |
C11D 7/265 20130101;
C11D 1/662 20130101; C23G 1/24 20130101; C11D 7/3272 20130101; G03F
7/422 20130101; C11D 11/0047 20130101; H01L 21/31116 20130101; H01L
21/02063 20130101; C11D 3/2082 20130101; C11D 3/2044 20130101; C11D
3/323 20130101 |
Class at
Publication: |
510/175 |
International
Class: |
C11D 7/32 20060101
C11D007/32 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 30, 2003 |
US |
10/695,773 |
Claims
1. A semiconductor wafer cleaning formulation for use in
semiconductor fabrication comprising an unsaturated dicarboxylic
acid, and ethylene urea.
2. The cleaning formulation according to claim 1, wherein the
formulation is an aqueous solution.
3. The cleaning formulation according to claim 2, comprising 1-9%
by weight of an unsaturated dicarboxylic acid; and 1-20% by weight
of ethylene urea.
4. The cleaning formulation according to claim 2, further
comprising at least one organic carboxylic acid except unsaturated
dicarboxylic acid, and at least one basic compound except ethylene
urea.
5. The cleaning formulation according to claim 4, comprising 1-9%
by weight of an unsaturated dicarboxylic acid; 1-20% by weight of
ethylene urea; 1-20% by weight of at least one organic carboxylic
acid except unsaturated dicarboxylic acid; 0.1-50% by weight of at
least one basic compound except ethylene urea; and 20-90% by weight
of water.
6. The cleaning formulation according to claim 4, wherein the
unsaturated dicarboxylic acid is selected from the group consisting
of maleic acid and citraconic acid.
7. The cleaning formulation according to claim 4, wherein the
unsaturated dicarboxylic acid is maleic acid.
8. The cleaning formulation according to claim 4, wherein the
organic carboxylic acid is selected from the group consisting of:
formic acid (FA), acetic acid (AA), and propionic acid (PA).
9. The cleaning formulation according to claim 4, wherein the basic
compound is selected from the group consisting of:
hydroxyethylpiperazine (HEP), hydroxypropylpiperazine (HPP),
aminoethylpiperazine (AEP), aminopropylpiperazine (APP),
hydroxyethylmorpholine (HEM), hydroxypropylmorpholine (HPM),
aminoethylmorpholine (AEM), aminopropylmorpholine (APM),
triethanolamine (TEA), pentamethyldiethylenetriamine (PMDETA),
dimethylaminoethoxyethanol (DMAEE), aminoethoxyethanol (AEE),
trimethylaminoethylethanolamine (TMAEEA),
trimethylaminopropylethanolamine (TMAPEA),
N-(2-cyanoethyl)ethylenediamine (CEEDA),
N-(2-cyanopropyl)ethylenediamine (CPEDA), and ammonia
(NH.sub.3).
10. The cleaning formulation according to claim 4, further
comprising at least one selected from the group consisting of: an
organic solvent, a chelating agent, a surfactant, and phosphonic
acid and/or phosphinic acid.
11. The cleaning formulation according to claim 10, wherein 1-20%
by weight of the organic solvent, 0.01-5% by weight of the
chelating agent, 0.01-0.2% by weight of the surfactant, and 0.5-5%
by weight of phosphonic acid and/or phosphinic acid are
contained.
12. The cleaning formulation according to claim 10, wherein the
organic solvent is selected from the group consisting of:
1,4-butanediol (1,4-BD), 1,3-butanediol (1,3-BD), ethylene glycol
(EG), propylene glycol (PG), N-methylpyrrolidone (NMP),
.gamma.-butyrolactone (GBL), propylene glycol monomethylether
(PGME), and propylene glycol monomethylether acetate (PGMEA).
13. The cleaning formulation according to claim 10, wherein the
chelating agent is selected from the group consisting of: ascorbic
acid, gluconic acid, mannitol, sorbitol, and boric acid.
14. The cleaning formulation according to claim 10, wherein the
surfactant is a C.sub.1-10alkyl glucoside.
15. A method for cleaning a semiconductor wafer comprising:
cleaning the wafer by using a chemical formulation comprising an
unsaturated dicarboxylic acid, and ethylene urea in semiconductor
fabrication.
16. The method according to claim 15, wherein the formulation is an
aqueous solution.
17. The method according to claim 16, wherein the formulation
comprises 1-9% by weight of an unsaturated dicarboxylic acid; and
1-20% by weight of ethylene urea.
18. The method according to claim 16, wherein the formulation
further comprises: at least one organic carboxylic acid except
unsaturated dicarboxylic acid, and at least one basic compound
except ethylene urea.
19. The method according to claim 18, wherein the formulation
comprises: 1-9% by weight of an unsaturated dicarboxylic acid;
1-20% by weight of ethylene urea; 1-20% by weight of at least one
organic carboxylic acid except unsaturated dicarboxylic acid;
0.1-50% by weight of at least one basic compound except ethylene
urea; and 20-90% by weight of water.
20. The method according to claim 18, wherein the unsaturated
dicarboxylic acid is selected from the group consisting of maleic
acid and citraconic acid.
21. The method according to claim 18, wherein the unsaturated
dicarboxylic acid is maleic acid.
22. The method according to claim 18, wherein the organic
carboxylic acid is selected from the group consisting of: formic
acid (FA), acetic acid (AA), and propionic acid (PA).
23. The method according to claim 18, wherein the basic compound is
selected from the group consisting of: hydroxyethylpiperazine
(HEP), hydroxypropylpiperazine (HPP), aminoethylpiperazine (AEP),
aminopropylpiperazine (APP), hydroxyethylmorpholine (HEM),
hydroxypropylmorpholine (HPM), aminoethylmorpholine (AEM),
aminopropylmorpholine (APM), triethanolamine (TEA),
pentamethyldiethylenetriamine (PMDETA), dimethylaminoethoxyethanol
(DMAEE), aminoethoxyethanol (AEE), trimethylaminoethylethanolamine
(TMAEEA), trimethylaminopropylethanolamine (TMAPEA),
N-(2-cyanoethyl)ethylenediamine (CEEDA),
N-(2-cyanopropyl)ethylenediamine (CPEDA), and ammonia
(NH.sub.3).
24. The method according to claim 18, wherein the formulation
further comprises at least one selected from the group consisting
of: an organic solvent, a chelating agent, a surfactant, and
phosphonic acid and/or phosphinic acid.
25. The method according to claim 24, wherein 1-20% by weight of
the organic solvent, 0.01-5% by weight of the chelating agent,
0.01-0.2% by weight of the surfactant, and 0.5-5% by weight of
phosphonic acid and/or phosphinic acid are contained.
26. The method according to claim 24, wherein the organic solvent
is selected from the group consisting of: 1,4-butanediol (1,4-BD),
1,3-butanediol (1,3-BD), ethylene glycol (EG), propylene glycol
(PG), N-methylpyrrolidone (NMP), .gamma.-butyrolactone (GBL),
propylene glycol monomethylether (PGME), and propylene glycol
monomethylether acetate (PGMEA).
27. The method according to claim 24, wherein the chelating agent
is selected from the group consisting of: ascorbic acid, gluconic
acid, mannitol, sorbitol, and boric acid.
28. The method according to claim 24, wherein the surfactant is a
C.sub.1-10alkyl glucoside.
29. A method for cleaning a semiconductor wafer comprising:
cleaning the wafer by using a chemical formulation comprising an
unsaturated dicarboxylic acid, and ethylene urea, in a cleaning
process after a following process: (i) making via hole; (ii) making
trench; (iii) punching of etch stopper layer; or (iv) CMP (chemical
mechanical polishing) process.
30. The method according to claim 29, wherein the formulation is an
aqueous solution.
31. The method according to claim 30, wherein the formulation
comprises 1-9% by weight of an unsaturated dicarboxylic acid; and
1-20% by weight of ethylene urea.
32. The method according to claim 30, wherein the formulation
further comprises: at least one organic carboxylic acid except
unsaturated dicarboxylic acid, and at least one basic compound
except ethylene urea.
33. The method according to claim 32, wherein the formulation
comprises: 1-9% by weight of an unsaturated dicarboxylic acid;
1-20% by weight of ethylene urea; 1-20% by weight of at least one
organic carboxylic acid except unsaturated dicarboxylic acid;
0.1-50% by weight of at least one basic compound except ethylene
urea; and 20-90% by weight of water.
34. The method according to claim 32, wherein the unsaturated
dicarboxylic acid is selected from the group consisting of maleic
acid and citraconic acid.
35. The method according to claim 32, wherein the unsaturated
dicarboxylic acid is maleic acid.
36. The method according to claim 32, wherein the organic
carboxylic acid is selected from the group consisting of: formic
acid (FA), acetic acid (AA), and propionic acid (PA).
37. The method according to claim 32, wherein the basic compound is
selected from the group consisting of: hydroxyethylpiperazine
(HEP), hydroxypropylpiperazine (HPP), aminoethylpiperazine (AEP),
aminopropylpiperazine (APP), hydroxyethylmorpholine (HEM),
hydroxypropylmorpholine (HPM), aminoethylmorpholine (AEM),
aminopropylmorpholine (APM), triethanolamine (TEA),
pentamethyldiethylenetriamine (PMDETA), dimethylaminoethoxyethanol
(DMAEE), aminoethoxyethanol (AEE), trimethylaminoethylethanolamine
(TMAEEA), trimethylaminopropylethanolamine (TMAPEA),
N-(2-cyanoethyl)ethylenediamine (CEEDA),
N-(2-cyanopropyl)ethylenediamine (CPEDA), and ammonia
(NH.sub.3).
38. The method according to claim 32, wherein the formulation
further comprises at least one selected from the group consisting
of: an organic solvent, a chelating agent, a surfactant, and
phosphonic acid and/or phosphinic acid.
39. The method according to claim 38, wherein 1-20% by weight of
the organic solvent, 0.01-5% by weight of the chelating agent,
0.01-0.2% by weight of the surfactant, and 0.5-5% by weight of
phosphonic acid and/or phosphinic acid are contained.
40. The method according to claim 38, wherein the organic solvent
is selected from the group consisting of: 1,4-butanediol (1,4-BD),
1,3-butanediol (1,3-BD), ethylene glycol (EG), propylene glycol
(PG), N-methylpyrrolidone (NMP), .gamma.-butyrolactone (GBL),
propylene glycol monomethylether (PGME), and propylene glycol
monomethylether acetate (PGMEA).
41. The method according to claim 38, wherein the chelating agent
is selected from the group consisting of: ascorbic acid, gluconic
acid, mannitol, sorbitol, and boric acid.
42. The method according to claim 38, wherein the surfactant is a
C.sub.1-10alkyl glucoside.
Description
BACKGROUND OF INVENTION
[0001] The present invention relates generally to a chemical
formulation used in semiconductor wafer fabrication and
particularly to a chemical formulation that is utilized to remove
residue from wafers following plasma ashing of a photoresist. More
specifically, the present invention relates to a chemical
formulation for removal of residue from semiconductor wafers
containing chemically delicate copper interconnect and low-k or
ultra low-k interlayer insulator layers.
BACKGROUND ART
[0002] As semiconductor wafer designs recently become smaller,
semiconductor wafers are being developed by using copper
interconnect material for reducing wiring resistance and by using
low-k interlayer insulator layers (low-k film) or ultra low-k
interlayer insulator layers (ultra low-k film) having a k-value of
3.0 or less for reducing interconnect capacity. Representative
wafers include single damascene or dual damascene wafers.
[0003] Pattern formation by use of interconnect material,
interlayer insulator layer material or the like is mainly carried
out by dry etching by utilizing a photoresist as a mask and then
plasma ashing for removal of the photoresist.
[0004] The prior art tells the utilization of various chemical
formulations to remove residue and clean wafers following a plasma
ashing process. Most of these prior art chemical formulations are
based on alkaline amines (for example, see Patent Document 1) and
fluorine compounds (for example, see Patent Document 2). Still
other chemical formulations are based on organic carboxylic acids
(for example, see Patent Document 3).
Patent Document 1: U.S. Pat. No. 5,334,332
Patent Document 2: EP patent No. 662705
Patent Document 3: US publication No. 2003/0143495 A1
DISCLOSURE OF THE INVENTION
Problem to be Solved by the Invention
[0005] These various prior art chemical formulations have drawbacks
that often include unwanted removal of wiring metal such as copper
or low-k and ultra low-k insulator layers. There is therefore a
need for chemical formulations that effectively remove residue
following a resist ashing process and do not affect on wiring metal
and low-k and ultra low-k interlayer insulator layers.
Means for Solving the Problem
[0006] The present invention relates generally to a chemical
formulation used in semiconductor wafer fabrication and
particularly to a chemical formulation that is utilized to remove
residue from wafers following a plasma ashing process of
photoresist. Namely, the present invention relates to the following
invention [1] to [12]:
[1] A semiconductor wafer cleaning formulation for use in
semiconductor fabrication comprising (a) an unsaturated
dicarboxylic acid, and (b) ethylene urea (2-imidazolidone);
[2] The cleaning formulation as described in [1], further
comprising (c) at least one organic carboxylic acid except
unsaturated dicarboxylic acid, (d) at least one basic compound
except ethylene urea, and (e) water;
[3] The cleaning formulation as described in [2], further
comprising at least one selected from the group consisting of (e an
organic solvent, (g) a chelating agent, (h) a surfactant, and (i)
phosphonic acid and/or phosphinic acid;
[0007] [4] The cleaning formulation as described in [1]-[3],
comprising each component (a) to (i) in the following amount shown
in percentage by weight based on total weight of the formulation:
TABLE-US-00001 (a) an unsaturated dicarboxylic acid 1-9% by weight
(b) ethylene urea 1-20% by weight (c) at least one organic
carboxylic acid except 1-20% by weight unsaturated dicarboxylic
acid (d) at least one basic compound except ethylene 0.1-50% by
weight urea (e) water 2-90% by weight (f) an organic solvent 1-20
by weight (g) a chelating agent 0.01-5% by weight (h) a surfactant
0.01-0.2% by weight (i) phosphonic acid and/or phosphinic acid
0.5-5% by weight;
[5] A method for cleaning a semiconductor wafer comprising cleaning
the wafer by using a semiconductor wafer cleaning formulation
comprising (a) an unsaturated dicarboxylic acid, and (b) ethylene
urea, in semiconductor fabrication; [6] The method for cleaning a
semiconductor wafer described in [5], wherein the semiconductor
wafer cleaning formulation further comprising (c) at least one
organic carboxylic acid except unsaturated dicarboxylic acid, (d)
at least one basic compound except ethylene urea, and (e) water is
used; [7] The method for cleaning a semiconductor wafer described
in [6], wherein the semiconductor wafer cleaning formulation
further comprising at least one selected from the group consisting
of (f) an organic solvent, (g) a chelating agent, (h) a surfactant,
and (i) phosphonic acid and/or phosphinic acid is used;
[0008] [8] The method for cleaning a semiconductor wafer described
in [5]-[7], wherein the semiconductor wafer cleaning formulation
comprising each component (a) to (i) in the following amount shown
in percentage by weight based on total weight of the formulation is
used: TABLE-US-00002 (a) an unsaturated dicarboxylic acid 1-9% by
weight (b) ethylene urea 1-20% by weight (c) at least one organic
carboxylic acid 1-20% by weight except unsaturated dicarboxylic
acid (d) at least one basic compound except ethylene 0.1-50% by
weight urea (e) water 2-90% by weight (f) an organic solvent 1-20
by weight (g) a chelating agent 0.01-5% by weight (h) a surfactant
0.01-0.2% by weight (i) phosphonic acid and/or phosphinic acid
0.5-5% by weight;
[9] A method for cleaning a semiconductor wafer comprising cleaning
the wafer by using a semiconductor wafer cleaning formulation
comprising (a) an unsaturated dicarboxylic acid, and (b) ethylene
urea, in (1) a cleaning process after making via hole, (2) a
cleaning process after making trench, (3) a cleaning process after
punching of etch stopper layer, or (4) a cleaning process after CMP
(chemical mechanical polishing) among semiconductor fabrication;
[10] The method for cleaning a semiconductor wafer described in
[9], wherein the semiconductor wafer cleaning formulation further
comprising (c) at least one organic carboxylic acid except
unsaturated dicarboxylic acid, (d) at least one basic compound
except ethylene urea, and (e) water is used; [11] The method for
cleaning a semiconductor wafer described in [9], wherein the
semiconductor wafer cleaning formulation further comprising at
least one selected from the group consisting of (f) an organic
solvent, (g) a chelating agent, (h) a surfactant, and (i)
phosphonic acid and/or phosphinic acid is used;
[0009] [12] The method for cleaning a semiconductor wafer described
in [9]-[11], wherein the semiconductor wafer cleaning formulation
comprising each component (a) to (i) in the following amount shown
in percentage by weight based on total weight of the formulation is
used: TABLE-US-00003 (a) an unsaturated dicarboxylic acid 1-9% by
weight (b) ethylene urea 1-20% by weight (c) at least one organic
carboxylic acid except 1-20% by weight unsaturated dicarboxylic
acid (d) at least one basic compound except ethylene 0.1-50% by
weight urea (e) water 2-90% by weight (f) an organic solvent 1-20
by weight (g) a chelating agent 0.01-5% by weight (h) a surfactant
0.01-0.2% by weight (i) phosphonic acid and/or phosphinic acid
0.5-5% by weight.
[0010] The chemical formulation of the present invention is
effective for removing residues from wafers formed in semiconductor
wafer fabrication, particularly for removing all residue from
wafers following a plasma ashing process. Especially, these
formulations are effective in the cleaning of dual damascene wafer.
Fabrication processes of dual damascene structure wafer are as
follows: (i) after depositions of interlayer insulator layer, etch
stopper layer and photoresist, and son on, a via hole is
constructed by dry etching and plasma ashing; (ii) filling a
photoresist or other material in the via hole, and trench structure
is constructed by the same process as above; (iii) etch stopper
layer is removed by punching; and (iv) after filling copper into
the via hole and trench together, overfilled copper is polished by
CMP (chemical mechanical polishing). After each of (i) to (iv)
processes, cleaning processes are carried out. The formulation of
the present invention is effective in all of the cleaning
processes.
[0011] That is, it is an advantage of the formulation of the
present invention that it effectively removes residue following a
plasma ashing process.
[0012] It is another advantage of the formulation that it can
effectively remove especially etch stopper layer punching residues.
Generally, the etch stopper layer punching residues are often
difficult to be completely removed without any damage on copper and
low-k and ultra low-k interlayer insulator layers. But the
formulation can remove such etch residues without any damage
thereon.
[0013] It is a further advantage of the formulation that it
effectively removes metal oxide like copper oxide or metal halides
like copper fluoride following plasma ashing.
[0014] It is a further advantage of the formulation that it
effectively removes metal oxide like copper oxide remaining after
CMP (chemical mechanical polishing).
[0015] It is yet another advantage of the formulation that it
provides residue removal performance with less corrosivity on
copper than conventional acidic cleaning solutions.
[0016] It is yet a further advantage of the formulation that it
provides residue removal performance with less corrosivity on low-k
and ultra low-k interlayer insulator layers than conventional
amine-based and ammonium fluoride-based cleaning solutions.
[0017] It is yet another advantage of the formulation that it
provides residue removal performance with lower temperature than
conventional amine-based and ammonium fluoride-based cleaning
solutions.
[0018] It is yet a further advantage of the formulation that it
provides residue removal performance with shorter treatment time
than conventional amine-based and ammonium fluoride-based
chemicals.
[0019] These and other features and advantages of the formulation
will become understood to those of ordinary skill in the art upon
review of the following detailed description of the preferred
embodiments.
BEST MODE FOR CARRYING OUT THE INVENTION
[0020] The present invention relates to a chemical formulation that
is suitable for removing residues originating from dry etching and
plasma ashing, or the like in semiconductor wafer fabrication. The
formulation comprises (a) an unsaturated dicarboxylic acid, and (b)
ethylene urea, as essential components. Among (a) the unsaturated
dicarboxylic acids, maleic acid is particularly preferable. The
composition preferably comprises (a) an unsaturated dicarboxylic
acid, (b) ethylene urea, (c) at least one organic carboxylic acid
except unsaturated dicarboxylic acid, (d) at least one basic
compound except ethylene urea, and (e) water. In addition, the
preferable composition may contain at least one selected from the
group consisting of (f) an organic solvent, (g) a chelating agent,
(h) a surfactant, and (i) phosphonic acid and/or phosphinic
acid.
[0021] The amount shown in percentage by weight (based on total
weight of the formulation) of each component of the formulation is
suitably determined depending on the object to be removed, but the
following amount is preferable:
(a) an unsaturated dicarboxylic acid 1-9% by weight
(b) ethylene urea 1-20% by weight
(c) at least one organic carboxylic acid except unsaturated
dicarboxylic acid 1-20% by weight
(d) at least one basic compound except ethylene urea 0.1-50% by
weight
(e) water 2-90% by weight
(f) an organic solvent 1-20 by weight
(g) a chelating agent 0.01-5% by weight
(h) a surfactant 0.01-0.2% by weight
(i) phosphonic acid and/or phosphinic acid 0.5-5% by weight
[0022] Preferable unsaturated dicarboxylic acids (a) are
(a-1) maleic acid, and
(a-2) citraconic acid, particularly preferable unsaturated
dicarboxylic acids (a) is
(a-1) maleic acid.
[0023] Preferable organic carboxylic acids (c) are
(c-1) formic acid (FA),
(c-2) acetic acid (AA), and
(c-3) propionic acid (PA).
[0024] Preferable basic compounds (d) are
(d-1) hydroxyethylpiperazine (HEP),
(d-2) hydroxypropylpiperazine (HPP),
(d-3) aminoethylpiperazine (AEP),
(d-4) aminopropylpiperazine (APP),
(d-5) hydroxyethylmorpholine (HEM),
(d-6 hydroxypropylmorpholine (HPM),
(d-7) aminoethylmorpholine (AEM),
(d-8) aminopropylmorpholine (APM),
(d-9) triethanolamine (TEA),
(d-10) pentamethyldiethylenetriamine (PMDETA),
(d-11) dimethylaminoethoxyethanol (DMAEE),
(d-12) aminoethoxyethanol (AEE),
(d-13) trimethylaminoethylethanolamine (TMAEEA),
(d-14) trimethylaminopropylethanolamine (TMAPEA),
(d-15) N-(2-cyanoethyl)ethylenediamine (CEEDA),
(d-16) N-(2-cyanopropyl)ethylenediamine (CPEDA). and
(d-17) ammonia (NH.sub.3).
[0025] Preferable organic solvents (f) are
(f-1) 1,4-butanediol (1,4-BD),
(f-2) 1,3-butanediol (1,3-BD),
(f-3) ethylene glycol (EG),
(f-4) propylene glycol (PG),
(f-5) N-methylpyrrolidone (NMP),
(f-6) .gamma.-butyrolactone (GBL),
(f-7) propylene glycol monomethylether (PGME), and
(f-8) propylene glycol monomethylether acetate (PGMEA).
[0026] Preferable chelating agents (g) are
(g-1) ascorbic acid,
(g-2) gluconic acid,
(g-3) mannitol,
(g-4) sorbitol, and
(g-5) boric acid.
[0027] Preferable surfactants (h) are
(h-1) C.sub.1-10alkyl glucosides.
[0028] Each component in the formulation included in the present
invention can be arbitrarily combined. Combinations of each
component include for example those shown in the following table.
In the meantime, the table is shown for purposes of illustration,
and the present invention is not limited to these combinations.
TABLE-US-00004 (a) (b) (c) (d) (e) (a-1) (b) (c-1) (d-1) (e) (a-1)
(b) (c-1) (d-2) (e) (a-1) (b) (c-1) (d-3) (e) (a-1) (b) (c-1) (d-4)
(e) (a-1) (b) (c-1) (d-5) (e) (a-1) (b) (c-1) (d-6) (e) (a-1) (b)
(c-1) (d-7) (e) (a-1) (b) (c-1) (d-8) (e) (a-1) (b) (c-1) (d-9) (e)
(a-1) (b) (c-1) (d-10) (e) (a-1) (b) (c-1) (d-11) (e) (a-1) (b)
(c-1) (d-12) (e) (a-1) (b) (c-1) (d-13) (e) (a-1) (b) (c-1) (d-14)
(e) (a-1) (b) (c-1) (d-15) (e) (a-1) (b) (c-1) (d-16) (e) (a-1) (b)
(c-1) (d-17) (e) (a-1) (b) (c-2) (d-1) (e) (a-1) (b) (c-2) (d-2)
(e) (a-1) (b) (c-2) (d-3) (e) (a-1) (b) (c-2) (d-4) (e) (a-1) (b)
(c-2) (d-5) (e) (a-1) (b) (c-2) (d-6) (e) (a-1) (b) (c-2) (d-7) (e)
(a-1) (b) (c-2) (d-8) (e) (a-1) (b) (c-2) (d-9) (e) (a-1) (b) (c-2)
(d-10) (e) (a-1) (b) (c-2) (d-11) (e) (a-1) (b) (c-2) (d-12) (e)
(a-1) (b) (c-2) (d-13) (e) (a-1) (b) (c-2) (d-14) (e) (a-1) (b)
(c-2) (d-15) (e) (a-1) (b) (c-2) (d-16) (e) (a-1) (b) (c-2) (d-17)
(e) (a-1) (b) (c-3) (d-1) (e) (a-1) (b) (c-3) (d-2) (e) (a-1) (b)
(c-3) (d-3) (e) (a-1) (b) (c-3) (d-4) (e) (a-1) (b) (c-3) (d-5) (e)
(a-1) (b) (c-3) (d-6) (e) (a-1) (b) (c-3) (d-7) (e) (a-1) (b) (c-3)
(d-8) (e) (a-1) (b) (c-3) (d-9) (e) (a-1) (b) (c-3) (d-10) (e)
(a-1) (b) (c-3) (d-11) (e) (a-1) (b) (c-3) (d-12) (e) (a-1) (b)
(c-3) (d-13) (e) (a-1) (b) (c-3) (d-14) (e) (a-1) (b) (c-3) (d-15)
(e) (a-1) (b) (c-3) (d-16) (e) (a-1) (b) (c-3) (d-17) (e) (a-1) (b)
(c-1) (d-1)(d-2) (e) (a-1) (b) (c-1) (d-1)(d-3) (e) (a-1) (b) (c-1)
(d-1)(d-4) (e) (a-1) (b) (c-1) (d-1)(d-5) (e) (a-1) (b) (c-1)
(d-1)(d-6) (e) (a-1) (b) (c-1) (d-1)(d-7) (e) (a-1) (b) (c-1)
(d-1)(d-8) (e) (a-1) (b) (c-1) (d-1)(d-9) (e) (a-1) (b) (c-1)
(d-1)(d-10) (e) (a-1) (b) (c-1) (d-1)(d-11) (e) (a-1) (b) (c-1)
(d-1)(d-12) (e) (a-1) (b) (c-1) (d-1)(d-13) (e) (a-1) (b) (c-1)
(d-1)(d-14) (e) (a-1) (b) (c-1) (d-1)(d-15) (e) (a-1) (b) (c-1)
(d-1)(d-16) (e) (a-1) (b) (c-1) (d-1)(d-17) (e) (a-1) (b) (c-1)
(d-2)(d-1) (e) (a-1) (b) (c-1) (d-2)(d-3) (e) (a-1) (b) (c-1)
(d-2)(d-4) (e) (a-1) (b) (c-1) (d-2)(d-5) (e) (a-1) (b) (c-1)
(d-2)(d-6) (e) (a-1) (b) (c-1) (d-2)(d-7) (e) (a-1) (b) (c-1)
(d-2)(d-8) (e) (a-1) (b) (c-1) (d-2)(d-9) (e) (a-1) (b) (c-1)
(d-2)(d-10) (e) (a-1) (b) (c-1) (d-2)(d-11) (e) (a-1) (b) (c-1)
(d-2)(d-12) (e) (a-1) (b) (c-1) (d-2)(d-13) (e) (a-1) (b) (c-1)
(d-2)(d-14) (e) (a-1) (b) (c-1) (d-2)(d-15) (e) (a-1) (b) (c-1)
(d-2)(d-16) (e) (a-1) (b) (c-1) (d-2)(d-17) (e) (a-1) (b) (c-1)
(d-3)(d-1) (e) (a-1) (b) (c-1) (d-3)(d-2) (e) (a-1) (b) (c-1)
(d-3)(d-4) (e) (a-1) (b) (c-1) (d-3)(d-5) (e) (a-1) (b) (c-1)
(d-3)(d-6) (e) (a-1) (b) (c-1) (d-3)(d-7) (e) (a-1) (b) (c-1)
(d-3)(d-8) (e) (a-1) (b) (c-1) (d-3)(d-9) (e) (a-1) (b) (c-1)
(d-3)(d-10) (e) (a-1) (b) (c-1) (d-3)(d-11) (e) (a-1) (b) (c-1)
(d-3)(d-12) (e) (a-1) (b) (c-1) (d-3)(d-13) (e) (a-1) (b) (c-1)
(d-3)(d-14) (e) (a-1) (b) (c-1) (d-3)(d-15) (e) (a-1) (b) (c-1)
(d-3)(d-16) (e) (a-1) (b) (c-1) (d-3)(d-17) (e) (a-1) (b) (c-1)
(d-4)(d-1) (e) (a-1) (b) (c-1) (d-4)(d-2) (e) (a-1) (b) (c-1)
(d-4)(d-3) (e) (a-1) (b) (c-1) (d-4)(d-5) (e) (a-1) (b) (c-1)
(d-4)(d-6) (e) (a-1) (b) (c-1) (d-4)(d-7) (e) (a-1) (b) (c-1)
(d-4)(d-8) (e) (a-1) (b) (c-1) (d-4)(d-9) (e) (a-1) (b) (c-1)
(d-4)(d-10) (e) (a-1) (b) (c-1) (d-4)(d-11) (e) (a-1) (b) (c-1)
(d-4)(d-12) (e) (a-1) (b) (c-1) (d-4)(d-13) (e) (a-1) (b) (c-1)
(d-4)(d-14) (e) (a-1) (b) (c-1) (d-4)(d-15) (e) (a-1) (b) (c-1)
(d-4)(d-16) (e) (a-1) (b) (c-1) (d-4)(d-17) (e) (a-1) (b) (c-1)
(d-5)(d-1) (e) (a-1) (b) (c-1) (d-5)(d-2) (e) (a-1) (b) (c-1)
(d-5)(d-3) (e) (a-1) (b) (c-1) (d-5)(d-4) (e) (a-1) (b) (c-1)
(d-5)(d-6) (e) (a-1) (b) (c-1) (d-5)(d-7) (e) (a-1) (b) (c-1)
(d-5)(d-8) (e) (a-1) (b) (c-1) (d-5)(d-9) (e) (a-1) (b) (c-1)
(d-5)(d-10) (e) (a-1) (b) (c-1) (d-5)(d-11) (e) (a-1) (b) (c-1)
(d-5)(d-12) (e) (a-1) (b) (c-1) (d-5)(d-13) (e) (a-1) (b) (c-1)
(d-5)(d-14) (e) (a-1) (b) (c-1) (d-5)(d-15) (e) (a-1) (b) (c-1)
(d-5)(d-16) (e) (a-1) (b) (c-1) (d-5)(d-17) (e) (a-1) (b) (c-1)
(d-6)(d-1) (e) (a-1) (b) (c-1) (d-6)(d-2) (e) (a-1) (b) (c-1)
(d-6)(d-3) (e) (a-1) (b) (c-1) (d-6)(d-4) (e) (a-1) (b) (c-1)
(d-6)(d-5) (e) (a-1) (b) (c-1) (d-6)(d-7) (e) (a-1) (b) (c-1)
(d-6)(d-8) (e) (a-1) (b) (c-1) (d-6)(d-9) (e) (a-1) (b) (c-1)
(d-6)(d-10) (e) (a-1) (b) (c-1) (d-6)(d-11) (e) (a-1) (b) (c-1)
(d-6)(d-12) (e) (a-1) (b) (c-1) (d-6)(d-13) (e) (a-1) (b) (c-1)
(d-6)(d-14) (e) (a-1) (b) (c-1) (d-6)(d-15) (e) (a-1) (b) (c-1)
(d-6)(d-16) (e) (a-1) (b) (c-1) (d-6)(d-17) (e) (a-1) (b) (c-1)
(d-7)(d-1) (e) (a-1) (b) (c-1) (d-7)(d-2) (e) (a-1) (b) (c-1)
(d-7)(d-3) (e) (a-1) (b) (c-1) (d-7)(d-4) (e) (a-1) (b) (c-1)
(d-7)(d-5) (e) (a-1) (b) (c-1) (d-7)(d-6) (e) (a-1) (b) (c-1)
(d-7)(d-8) (e) (a-1) (b) (c-1) (d-7)(d-9) (e) (a-1) (b) (c-1)
(d-7)(d-10) (e) (a-1) (b) (c-1) (d-7)(d-11) (e) (a-1) (b) (c-1)
(d-7)(d-12) (e) (a-1) (b) (c-1) (d-7)(d-13) (e) (a-1) (b) (c-1)
(d-7)(d-14) (e) (a-1) (b) (c-1) (d-7)(d-15) (e) (a-1) (b) (c-1)
(d-7)(d-16) (e) (a-1) (b) (c-1) (d-7)(d-17) (e) (a-1) (b) (c-1)
(d-8)(d-1) (e) (a-1) (b) (c-1) (d-8)(d-2) (e) (a-1) (b) (c-1)
(d-8)(d-3) (e) (a-1) (b) (c-1) (d-8)(d-4) (e) (a-1) (b) (c-1)
(d-8)(d-5) (e) (a-1) (b) (c-1) (d-8)(d-6) (e) (a-1) (b) (c-1)
(d-8)(d-7) (e) (a-1) (b) (c-1) (d-8)(d-9) (e) (a-1) (b) (c-1)
(d-8)(d-10) (e) (a-1) (b) (c-1) (d-8)(d-11) (e) (a-1) (b) (c-1)
(d-8)(d-12) (e) (a-1) (b) (c-1) (d-8)(d-13) (e) (a-1) (b) (c-1)
(d-8)(d-14) (e) (a-1) (b) (c-1) (d-8)(d-15) (e) (a-1) (b) (c-1)
(d-8)(d-16) (e) (a-1) (b) (c-1) (d-8)(d-17) (e) (a-1) (b) (c-1)
(d-9)(d-1) (e) (a-1) (b) (c-1) (d-9)(d-2) (e) (a-1) (b) (c-1)
(d-9)(d-3) (e) (a-1) (b) (c-1) (d-9)(d-4) (e) (a-1) (b) (c-1)
(d-9)(d-5) (e) (a-1) (b) (c-1) (d-9)(d-6) (e) (a-1) (b) (c-1)
(d-9)(d-7) (e) (a-1) (b) (c-1) (d-9)(d-8) (e) (a-1) (b) (c-1)
(d-9)(d-10) (e) (a-1) (b) (c-1) (d-9)(d-11) (e) (a-1) (b) (c-1)
(d-9)(d-12) (e) (a-1) (b) (c-1) (d-9)(d-13) (e) (a-1) (b) (c-1)
(d-9)(d-14) (e) (a-1) (b) (c-1) (d-9)(d-15) (e) (a-1) (b) (c-1)
(d-9)(d-16) (e) (a-1) (b) (c-1) (d-9)(d-17) (e) (a-1) (b) (c-1)
(d-10)(d-1) (e) (a-1) (b) (c-1) (d-10)(d-2) (e) (a-1) (b) (c-1)
(d-10)(d-3) (e) (a-1) (b) (c-1) (d-10)(d-4) (e) (a-1) (b) (c-1)
(d-10)(d-5) (e) (a-1) (b) (c-1) (d-10)(d-6) (e) (a-1) (b) (c-1)
(d-10)(d-7) (e) (a-1) (b) (c-1) (d-10)(d-8) (e) (a-1) (b) (c-1)
(d-10)(d-9) (e) (a-1) (b) (c-1) (d-10)(d-11) (e) (a-1) (b) (c-1)
(d-10)(d-12) (e) (a-1) (b) (c-1) (d-10)(d-13) (e) (a-1) (b) (c-1)
(d-10)(d-14) (e) (a-1) (b) (c-1) (d-10)(d-15) (e) (a-1) (b) (c-1)
(d-10)(d-16) (e) (a-1) (b) (c-1) (d-10)(d-17) (e) (a-1) (b) (c-1)
(d-11)(d-1) (e) (a-1) (b) (c-1) (d-11)(d-2) (e) (a-1) (b) (c-1)
(d-11)(d-3) (e) (a-1) (b) (c-1) (d-11)(d-4) (e) (a-1) (b) (c-1)
(d-11)(d-5) (e) (a-1) (b) (c-1) (d-11)(d-6) (e) (a-1) (b) (c-1)
(d-11)(d-7) (e) (a-1) (b) (c-1) (d-11)(d-8) (e) (a-1) (b) (c-1)
(d-11)(d-9) (e) (a-1) (b) (c-1) (d-11)(d-10) (e) (a-1) (b) (c-1)
(d-11)(d-12) (e) (a-1) (b) (c-1) (d-11)(d-13) (e) (a-1) (b) (c-1)
(d-11)(d-14) (e) (a-1) (b) (c-1) (d-11)(d-15) (e) (a-1) (b) (c-1)
(d-11)(d-16) (e) (a-1) (b) (c-1) (d-11)(d-17) (e) (a-1) (b) (c-1)
(d-12)(d-1) (e) (a-1) (b) (c-1) (d-12)(d-2) (e) (a-1) (b) (c-1)
(d-12)(d-3) (e) (a-1) (b) (c-1) (d-12)(d-4) (e) (a-1) (b) (c-1)
(d-12)(d-5) (e) (a-1) (b) (c-1) (d-12)(d-6) (e) (a-1) (b) (c-1)
(d-12)(d-7) (e) (a-1) (b) (c-1) (d-12)(d-8) (e) (a-1) (b) (c-1)
(d-12)(d-9) (e) (a-1) (b) (c-1) (d-12)(d-10) (e) (a-1) (b) (c-1)
(d-12)(d-11) (e) (a-1) (b) (c-1) (d-12)(d-13) (e) (a-1) (b) (c-1)
(d-12)(d-14) (e) (a-1) (b) (c-1) (d-12)(d-15) (e) (a-1) (b) (c-1)
(d-12)(d-16) (e)
(a-1) (b) (c-1) (d-12)(d-17) (e) (a-1) (b) (c-1) (d-13)(d-1) (e)
(a-1) (b) (c-1) (d-13)(d-2) (e) (a-1) (b) (c-1) (d-13)(d-3) (e)
(a-1) (b) (c-1) (d-13)(d-4) (e) (a-1) (b) (c-1) (d-13)(d-5) (e)
(a-1) (b) (c-1) (d-13)(d-6) (e) (a-1) (b) (c-1) (d-13)(d-7) (e)
(a-1) (b) (c-1) (d-13)(d-8) (e) (a-1) (b) (c-1) (d-13)(d-9) (e)
(a-1) (b) (c-1) (d-13)(d-10) (e) (a-1) (b) (c-1) (d-13)(d-11) (e)
(a-1) (b) (c-1) (d-13)(d-12) (e) (a-1) (b) (c-1) (d-13)(d-14) (e)
(a-1) (b) (c-1) (d-13)(d-15) (e) (a-1) (b) (c-1) (d-13)(d-16) (e)
(a-1) (b) (c-1) (d-13)(d-17) (e) (a-1) (b) (c-1) (d-14)(d-1) (e)
(a-1) (b) (c-1) (d-14)(d-2) (e) (a-1) (b) (c-1) (d-14)(d-3) (e)
(a-1) (b) (c-1) (d-14)(d-4) (e) (a-1) (b) (c-1) (d-14)(d-5) (e)
(a-1) (b) (c-1) (d-14)(d-6) (e) (a-1) (b) (c-1) (d-14)(d-7) (e)
(a-1) (b) (c-1) (d-14)(d-8) (e) (a-1) (b) (c-1) (d-14)(d-9) (e)
(a-1) (b) (c-1) (d-14)(d-10) (e) (a-1) (b) (c-1) (d-14)(d-11) (e)
(a-1) (b) (c-1) (d-14)(d-12) (e) (a-1) (b) (c-1) (d-14)(d-13) (e)
(a-1) (b) (c-1) (d-14)(d-15) (e) (a-1) (b) (c-1) (d-14)(d-16) (e)
(a-1) (b) (c-1) (d-14)(d-17) (e) (a-1) (b) (c-1) (d-15)(d-1) (e)
(a-1) (b) (c-1) (d-15)(d-2) (e) (a-1) (b) (c-1) (d-15)(d-3) (e)
(a-1) (b) (c-1) (d-15)(d-4) (e) (a-1) (b) (c-1) (d-15)(d-5) (e)
(a-1) (b) (c-1) (d-15)(d-6) (e) (a-1) (b) (c-1) (d-15)(d-7) (e)
(a-1) (b) (c-1) (d-15)(d-8) (e) (a-1) (b) (c-1) (d-15)(d-9) (e)
(a-1) (b) (c-1) (d-15)(d-10) (e) (a-1) (b) (c-1) (d-15)(d-11) (e)
(a-1) (b) (c-1) (d-15)(d-12) (e) (a-1) (b) (c-1) (d-15)(d-13) (e)
(a-1) (b) (c-1) (d-15)(d-14) (e) (a-1) (b) (c-1) (d-15)(d-16) (e)
(a-1) (b) (c-1) (d-15)(d-17) (e) (a-1) (b) (c-1) (d-16)(d-1) (e)
(a-1) (b) (c-1) (d-16)(d-2) (e) (a-1) (b) (c-1) (d-16)(d-3) (e)
(a-1) (b) (c-1) (d-16)(d-4) (e) (a-1) (b) (c-1) (d-16)(d-5) (e)
(a-1) (b) (c-1) (d-16)(d-6) (e) (a-1) (b) (c-1) (d-16)(d-7) (e)
(a-1) (b) (c-1) (d-16)(d-8) (e) (a-1) (b) (c-1) (d-16)(d-9) (e)
(a-1) (b) (c-1) (d-16)(d-10) (e) (a-1) (b) (c-1) (d-16)(d-11) (e)
(a-1) (b) (c-1) (d-16)(d-12) (e) (a-1) (b) (c-1) (d-16)(d-13) (e)
(a-1) (b) (c-1) (d-16)(d-14) (e) (a-1) (b) (c-1) (d-16)(d-15) (e)
(a-1) (b) (c-1) (d-16)(d-17) (e) (a-1) (b) (c-1) (d-17)(d-1) (e)
(a-1) (b) (c-1) (d-17)(d-2) (e) (a-1) (b) (c-1) (d-17)(d-3) (e)
(a-1) (b) (c-1) (d-17)(d-4) (e) (a-1) (b) (c-1) (d-17)(d-5) (e)
(a-1) (b) (c-1) (d-17)(d-6) (e) (a-1) (b) (c-1) (d-17)(d-7) (e)
(a-1) (b) (c-1) (d-17)(d-8) (e) (a-1) (b) (c-1) (d-17)(d-9) (e)
(a-1) (b) (c-1) (d-17)(d-10) (e) (a-1) (b) (c-1) (d-17)(d-11) (e)
(a-1) (b) (c-1) (d-17)(d-12) (e) (a-1) (b) (c-1) (d-17)(d-13) (e)
(a-1) (b) (c-1) (d-17)(d-14) (e) (a-1) (b) (c-1) (d-17)(d-15) (e)
(a-1) (b) (c-1) (d-17)(d-16) (e)
[0029] The formulation has pH of 1 to 5, preferably 2 to 4.
[0030] Treatment temperature of the formulation is not specifically
limited while it could remove residue completely. For example, the
treatment temperature of 21-40.degree. C. affords sufficient
effect.
[0031] Treatment time of the formulation is not specifically
limited while it could remove residue completely. For example, the
treatment time of 1-5 min affords sufficient effect.
[0032] Treatment procedure of the formulation is not specifically
limited while it contact to the wafer containing residues. The
formulation can be suitably applied to batch process or single
wafer process.
[0033] In addition, the formulation can be used for residue removal
of wafers in semiconductor fabrication, for example it is useful
for (1) a cleaning process after making via hole, (2) a cleaning
process after making trench, (3) a cleaning process after punching
of etch stopper layer, or (4) a cleaning process after CMP
(chemical mechanical polishing).
EXAMPLES
[0034] The present invention is explained with some examples
described below, but this invention is not limited to these
examples.
(1) Copper Oxide Removal Test
[0035] Copper blanket wafers were treated with O2 plasma
(250.degree. C., 120 sec) and the resulting copper oxide wafers
were used for test. Each wafer was immersed into any one of
formulations of Examples 1-15 and Comparative Examples 1-6 at
40.degree. C. for 2 min. After that each wafer was rinsed with
deionized water and air-dried. Copper oxide removal ability was
determined with optical microscopic observation and a qualitative
analysis of oxidization state of copper on wafer surface measured
with X-ray photoelectron spectroscopy (XPS; Shimadzu
ESCA-3200).
[0036] The components of Examples 1-15 and Comparative Example 1-6,
and the test results are shown in Tables 1-3. And copper oxide
removal ability were estimated as follows:
.largecircle.: Yellow colored surface of wafer (from optical
microscopic observation), no Cu.sup.2+ peaks in XPS spectra.
[0037] X: Red colored surface of wafer (from optical microscopic
observation), remain of Cu.sup.2+ peaks in XPS spectra.
TABLE-US-00005 TABLE 1 (Each value shows % by weight based on the
total formulation) Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Water 55 55 55 55 55 55 55 55 55 55 55 55 55 78.8 78.8 Maleic acid
5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Ethylene urea 5 5 20 5 5 5 5 5 5 5 5
5 5 5 5 Formic acid 10 10 10 10 10 10 10 10 10 10 10 10 10 4.2 4.2
1,4-Buthanediol -- -- -- -- -- 5 5 -- -- -- -- -- -- -- -- Ethylene
glycol -- -- -- -- -- -- -- 5 5 -- -- -- -- -- -- TEA 20 20 5 -- --
-- -- 15 15 15 15 20 20 5 5 TMAEEA -- -- -- 20 20 15 15 -- -- -- --
-- -- -- -- AEM 5 -- 5 5 -- 5 -- 5 -- 5 5 5 5 -- -- AEP -- 5 -- --
5 -- 5 -- 5 -- -- -- -- -- -- NH.sub.3 -- -- -- -- -- -- -- -- --
-- -- -- -- 1.2 1.2 Gluconic acid -- -- -- -- -- -- -- -- -- 5 --
-- -- -- Mannitol -- -- -- -- -- -- -- -- -- -- 5 -- -- -- --
Methyl glucoside -- -- -- -- -- -- -- -- -- -- -- 0.15 -- -- --
Decyl glucoside -- -- -- -- -- -- -- -- -- -- -- -- 0.15 -- --
Phosphonic acid -- -- -- -- -- -- -- -- -- -- -- -- -- 0.8 --
Phosphinic acid -- -- -- -- -- -- -- -- -- -- -- -- -- -- 0.8
Copper oxide .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. removal
[0038] TABLE-US-00006 TABLE 2 (Each value shows % by weight based
on the total formulation) Comparative Example 1 2 3 4 Water 55 55
55 55 Maleic acid -- -- 5 10 Malonic acid 5 -- -- -- Acrylic acid
-- 5 -- -- Ethylene urea 5 5 -- 5 Formic acid 10 10 -- 5 TEA 20 20
20 20 AEM 5 5 15 5 Copper oxide x x x x removal
[0039] TABLE-US-00007 TABLE 3 (Each value shows % by weight based
on the total formulation) Comparative Example 5 6 Water 29 --
NH.sub.4F 1 -- Dimethylacetamide 60 -- Diethylene glycol- 10 --
monomethylether Monoethanolamine -- 30 Dimethylsulfoxide -- 70
Copper oxide x x removal
(2) Removal Test for Punching Residue of Low-k and Ultra Low-k
Interlayer Insulator Layer and Etch Stopper Layer
[0040] Wafers for cleaning evaluation of dual damascene or single
damascene structure having punching residue of etch stopper layer
were used for evaluation of the formulation of the present
invention. The wafers were immersed into any one of the
formulations at 40.degree. C. for 5 min. After each wafer was
rinsed with deionized water and air-dried, removal ability of
punching residue of the etch stopper layer and corrosivity of
copper, or low-k or ultra low-k interlayer insulator layer were
determined with scanning electron microscopic (SEM)
observation.
[0041] Preferable formulations of the present invention could
completely remove punching residue of etch stopper layer without
any damage on copper, or low-k or ultra low-k interlayer insulator
layer. Further, etching residue of low-k or ultra low-k interlayer
insulator layer could also be completely removed. The preferable
formulations indicate the most excellent results, and have
comparable performance each other when they are evaluated based on
both removable ability and low corrosivity as a whole.
[0042] While the present invention has been described with
reference to certain preferred embodiments, it will be understood
by those skilled in the art that various alternations and
modifications may be made therein without departing from the true
spirit and scope of the invention. It is therefore intended that
the following claims cover all such alternations and modifications,
which nevertheless include the true spirit and scope of the
invention.
* * * * *