U.S. patent number RE46,427 [Application Number 14/595,758] was granted by the patent office on 2017-06-06 for antioxidants for post-cmp cleaning formulations.
This patent grant is currently assigned to Entegris, Inc.. The grantee listed for this patent is ADVANCED TECHNOLOGY MATERIALS, INC.. Invention is credited to David Angst, Jeffrey Barnes, Karl Boggs, Emanuel Cooper, Prerna Sonthalia, Peng Zhang.
United States Patent |
RE46,427 |
Angst , et al. |
June 6, 2017 |
Antioxidants for post-CMP cleaning formulations
Abstract
An cleaning composition and process for cleaning post-chemical
mechanical polishing (CMP) residue and contaminants from a
microelectronic device having said residue and contaminants
thereon. The cleaning compositions include novel corrosion
inhibitors. The composition achieves highly efficacious cleaning of
the post-CMP residue and contaminant material from the surface of
the microelectronic device without compromising the low-k
dielectric material or the copper interconnect material.
Inventors: |
Angst; David (New Tripoli,
PA), Zhang; Peng (Montvale, NJ), Barnes; Jeffrey
(Bethlehem, CT), Sonthalia; Prerna (Mumbai, IN),
Cooper; Emanuel (Scarsdale, NY), Boggs; Karl (Hopewell
Junction, NY) |
Applicant: |
Name |
City |
State |
Country |
Type |
ADVANCED TECHNOLOGY MATERIALS, INC. |
Danbury |
CT |
US |
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|
Assignee: |
Entegris, Inc. (Billerica,
MA)
|
Family
ID: |
41089521 |
Appl.
No.: |
14/595,758 |
Filed: |
January 13, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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PCT/US2007/079044 |
Sep 20, 2007 |
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PCT/US2008/063885 |
May 16, 2008 |
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60846306 |
Sep 21, 2006 |
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60938591 |
May 17, 2007 |
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Reissue of: |
12409267 |
Mar 23, 2009 |
8685909 |
Apr 1, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D
3/0084 (20130101); C11D 7/3281 (20130101); C11D
7/267 (20130101); C11D 7/3209 (20130101); C11D
11/0047 (20130101); C11D 3/0078 (20130101); C11D
3/0073 (20130101); C11D 7/32 (20130101); C11D
11/0047 (20130101); C11D 3/0073 (20130101); C11D
7/32 (20130101); C11D 3/0084 (20130101); C11D
7/265 (20130101) |
Current International
Class: |
C11D
7/50 (20060101); C11D 11/00 (20060101); C11D
3/00 (20060101); C11D 7/32 (20060101) |
References Cited
[Referenced By]
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Other References
Xiang-Bin, Chang, et al.; "A Comparatice Study on the Anodic
Behaviour of Adenine, Adenosine, and 5'-AMP at Carbon Paste
Electrode," Acta Chimica Sinica, 1989, English Abstract is on Last
Page. cited by applicant .
Chinese Office Action Mar. 2, 2015. cited by applicant .
European Office Action dated Jul. 7, 2014. cited by applicant .
Japanese Office Action dated Jun. 23, 2014. cited by applicant
.
Korean Office Action dated May 26, 2014. cited by applicant .
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during Wet Processes in FEOL and BEOL for 45nm Node and beyond,"
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|
Primary Examiner: Xu; Ling
Attorney, Agent or Firm: Entegris, Inc. Legal Dept. Kissoon;
Nidhi G.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of PCT Application No.
PCT/US07/79044, filed Sep. 20, 2007 in the name of David Angst et
al., which claims priority to U.S. Provisional Patent Application
No. 60/846,306, filed on Sep. 21, 2006 in the name of David Angst,
and this application is also a continuation-in-part of PCT
Application No. PCT/US08/63885, filed May 16, 2008 in the name of
Peng Zhang et al., which claims priority to U.S. Provisional Patent
Application No. 60/938,591, filed on May 17, 2007 in the name of
Peng Zhang et al., all of which are incorporated by reference in
their respective entirety herein.
Claims
What is claimed is:
1. A method of removing post-chemical mechanical polishing (CMP)
residue from a microelectronic device having said post-CMP residue
thereon, said method comprising contacting the microelectronic
device with a cleaning composition for sufficient time to at least
partially clean said post-CMP residue from the microelectronic
device, wherein the cleaning composition .[.includes at least one
solvent.]. .Iadd.consists of water.Iaddend., at least one corrosion
inhibitor, .Iadd.at least one quaternary base.Iaddend., and at
least one amine, wherein the .Iadd.at least one .Iaddend.corrosion
inhibitor .[.comprises a species.]. .Iadd.is .Iaddend.selected from
the group consisting of .[.barbituric acid and derivatives
thereof,.]. glucuronic acid, squaric acid, .[.alpha-keto acids,.].
adenosine and derivatives thereof, .[.guanine, hypoxanthine,
xanthine, theobromine, caffeine, isoguanine,
phenanthroline/ascorbic acid, nicotinamide and derivatives
thereof,.]. flavonols and derivatives thereof, anthocyanins and
derivatives thereof, .[.flavonol/anthocyanin,.]. and combinations
thereof.Iadd., wherein the at least one amine is selected from the
group consisting of aminoethylethanolamine, N-methylaminoethanol,
aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine,
N-methyldiethanolamine, monoethanolamine, triethanolamine,
1-amino-2-propanol, 2-amino-1-butanol, isobutanolamine,
triethylenediamine, other C.sub.1-C.sub.8 alkanolamines and
combinations thereof, and wherein the at least one quaternary base
is selected from the group consisting of tetraethylammonium
hydroxide (TEAH), tetramethyammonium hydroxide (TMAH),
tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide
(TBAH), tributylmethylammonium hydroxide (TBMAH),
benzyltrimethylammonium hydroxide (BTMAH), and combinations
thereof.Iaddend..
.[.2. The method of claim 1, wherein the cleaning composition
further comprises at least one quaternary base..].
3. The method of claim 1, wherein said contacting comprises
conditions selected from the group consisting of: time of from
about 1 second to about 20 minutes; temperature in a range of from
about 20.degree. C. to about 90.degree. C.; and combinations
thereof.
4. The method of claim 1, wherein the microelectronic device
comprises an article selected from the group consisting of
semiconductor substrates, flat panel displays, phase change memory
devices, solar panels .[.and other products including.]..Iadd.,
.Iaddend.solar substrates, photovoltaics, and
microelectromechanical systems (MEMS).
5. The method of claim 1, further comprising diluting the cleaning
composition with diluent at or before a point of use, wherein the
composition is diluted in a range from about 5:1 to about
200:1.
6. The method of claim .[.4.]. .Iadd.5.Iaddend., wherein said
diluent comprises water.
7. The method of claim 1, further comprising rinsing the
microelectronic device with deionized water following contact with
the cleaning composition.
.[.8. The method of claim 1, wherein the cleaning composition
further comprises at least one additional component selected from
the group consisting of: at least one quaternary base; at least one
complexing agent; at least one surfactant; at least one reducing
agent; at least one dispersing agent; at least one sulfonic
acid-containing hydrocarbon; at least one alcohol; and combinations
thereof..].
.[.9. The method of claim 1, wherein the cleaning composition
further comprises at least one embodiment (i) through (viii): (i)
at least one quaternary base, and optionally at least one reducing
agent; (ii) at least one quaternary base, and at least one
complexing agent; (iii) at least one surfactant, and optionally at
least one reducing agent; (iv) at least one reducing agent,
optionally at least one surfactant, and optionally at least one
quaternary base; (v) at least one quaternary base, at least one
reducing agent, and optionally at least one surfactant; (vi) at
least one quaternary base and uric acid; (vii) at least one
quaternary base, uric acid, and at least one alcohol; and (viii) at
least one quaternary base and at least one alcohol..].
.[.10. The method of claim 1, wherein the solvent comprises
water..].
11. The method of claim 1, wherein the pH of the cleaning
composition is in a range from about 8.5 to about 11.5.
.[.12. The method of claim 1, wherein the cleaning composition is
substantially devoid of oxidizing agent, fluoride source, and/or
abrasive material prior to removal of residue material from the
microelectronic device..].
.[.13. The method of claim 1, wherein the cleaning composition
further comprises at least one additional corrosion inhibitor,
wherein the at least one additional corrosion inhibitor comprises a
species selected from the group consisting of ascorbic acid,
L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives,
benzotriazole, citric acid, ethylenediamine, gallic acid, oxalic
acid, tannic acid, ethylenediaminetetraacetic acid (EDTA), uric
acid, 1,2,4-triazole (TAZ), tolyltriazole, 5-phenyl-benzotriazole,
5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole,
1-amino-1,2,4-triazole, hydroxybenzotriazole,
2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole,
1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole,
3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole,
5-phenylthiol-benzotriazole, halo-benzotriazoles (halo=F, Cl, Br or
I), naphthotriazole, 2-mercaptobenzimidazole (MBI),
2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole,
2-mercaptothiazoline, 5-aminotetrazole,
5-amino-1,3,4-thiadiazole-2-thiol,
2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine,
methyltetrazole, 1,3-dimethyl-2-imidazolidinone,
1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole,
diaminomethyltriazine, imidazoline thione, mercaptobenzimidazole,
4-methyl-4H-1,2,4-triazole-3-thiol,
5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl
phosphate, imidazole, indiazole, benzoic acid, ammonium benzoate,
catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid,
barbituric acid and derivatives such as 1,2-dimethylbarbituric
acid, alpha-keto acids such as pyruvic acid, adenine, purine,
phosphonic acid and derivatives thereof, glycine/ascorbic acid, and
combinations thereof..].
.[.14. The method of claim 1, wherein the at least one amine has
the general formula NR.sup.1R.sup.2R.sup.3, where R.sup.1, R.sup.2
and R.sup.3 may be the same as or different from one another and
are selected from the group consisting of hydrogen,
straight-chained C.sub.1-C.sub.6 alkyl, branched C.sub.1-C.sub.6
alkyl, straight-chained C.sub.1-C.sub.6 alcohol, and branched
C.sub.1-C.sub.6 alcohol..].
.[.15. The method of claim 2, wherein the at least one quaternary
base has the formula NR.sup.1R.sup.2R.sup.3R.sup.4OH, wherein
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be the same as or
different from one another and are selected from the group
consisting of hydrogen, straight-chained C.sub.1-C.sub.6 alkyl,
branched C.sub.1-C.sub.6 alkyl, substituted C.sub.6-C.sub.10 aryl,
and unsubstituted C.sub.6-C.sub.10 aryl..].
.[.16. The method of claim 8, comprising at least one alcohol,
wherein the at least one alcohol comprises straight-chained or
branched C.sub.1-C.sub.6 alcohols..].
.[.17. The method of claim 14, wherein the at least one amine
comprises a species selected from the group consisting of
aminoethyletholamine, N-methylaminoethanol, aminoethoxyethanol,
dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine,
monoethanolamine, triethanolamine, 1-amino-2-propanol,
2-amino-1-butanol, isobutanolamine, triethylenediamine, other
C.sub.i-C.sub.8 alkanolamines and combinations thereof..].
.[.18. The method of claim 15, wherein the at least one quaternary
base comprises a species selected from the group consisting of
tetraethylammonium hydroxide (TEAH), tetramethyammonium hydroxide
(TMAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium
hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH),
benzyltrimethylammonium hydroxide (BTMAH), and combinations
thereof..].
19. The method of claim 1, wherein the at least one corrosion
inhibitor .[.comprises.]. .Iadd.is selected from the group
consisting of .Iaddend.adenosine .[.and.]..Iadd.,
.Iaddend.derivatives thereof.Iadd., and combinations
thereof.Iaddend..
Description
FIELD
The present invention relates generally to compositions including
antioxidants for cleaning residue and/or contaminants from
microelectronic devices having same thereon.
DESCRIPTION OF THE RELATED ART
Microelectronic device wafers are used to form integrated circuits.
The microelectronic device wafer includes a substrate, such as
silicon, into which regions are patterned for deposition of
different materials having insulative, conductive or
semi-conductive properties.
In order to obtain the correct patterning, excess material used in
forming the layers on the substrate must be removed. Further, to
fabricate functional and reliable circuitry, it is important to
prepare a flat or planar microelectronic wafer surface prior to
subsequent processing. Thus, it is necessary to remove and/or
polish certain surfaces of a microelectronic device wafer.
Chemical Mechanical Polishing or Planarization ("CMP") is a process
in which material is removed from a surface of a microelectronic
device wafer, and the surface is polished (more specifically,
planarized) by coupling a physical process such as abrasion with a
chemical process such as oxidation or chelation. In its most
rudimentary form, CMP involves applying slurry, e.g., a solution of
an abrasive and an active chemistry, to a polishing pad that buffs
the surface of a microelectronic device wafer to achieve the
removal, planarization, and polishing processes. It is not
desirable for the removal or polishing process to be comprised of
purely physical or purely chemical action, but rather the
synergistic combination of both in order to achieve fast, uniform
removal. In the fabrication of integrated circuits, the CMP slurry
should also be able to preferentially remove films that comprise
complex layers of metals and other materials so that highly planar
surfaces can be produced for subsequent photolithography, or
patterning, etching and thin-film processing.
Recently, copper has been increasingly used for metal interconnects
in integrated circuits. In copper damascene processes commonly used
for metallization of circuitry in microelectronic device
fabrication, the layers that must be removed and planarized include
copper layers having a thickness of about 1-1.5 .mu.m and copper
seed layers having a thickness of about 0.05-0.15 .mu.m. These
copper layers are separated from the dielectric material surface by
a layer of barrier material, typically about 50-300 .ANG. thick,
which prevents diffusion of copper into the oxide dielectric
material. One key to obtaining good uniformity across the wafer
surface after polishing is to use a CMP slurry that has the correct
removal selectivities for each material.
The foregoing processing operations, involving wafer substrate
surface preparation, deposition, plating, etching and chemical
mechanical polishing, variously require cleaning operations to
ensure that the microelectronic device product is free of
contaminants that would otherwise deleteriously affect the function
of the product, or even render it useless for its intended
function. Often, particles of these contaminants are smaller than
0.3 .mu.m.
One particular issue in this respect is the residues that are left
on the microelectronic device substrate following CMP processing.
Such residues include CMP material and corrosion inhibitor
compounds such as benzotriazole (BTA). If not removed, these
residues can cause damage to copper lines or severely roughen the
copper metallization, as well as cause poor adhesion of post-CMP
applied layers on the device substrate. Severe roughening of copper
metallization is particularly problematic, since overly rough
copper can cause poor electrical performance of the product
microelectronic device.
Another residue-producing process common to microelectronic device
manufacturing involves gas-phase plasma etching to transfer the
patterns of developed photoresist coatings to the underlying
layers, which may consist of hardmask, interlevel dielectric (ILD),
and etch stop layers. Post-gas phase plasma etch residues, which
may include chemical elements present on the substrate and in the
plasma gases, are typically deposited on the back end of the line
(BEOL) structures and if not removed, may interfere with subsequent
silicidation or contact formation. Conventional cleaning
chemistries often damage the ILD, absorb into the pores of the ILD
thereby increasing the dielectric constant, and/or corrode the
metal structures.
The microelectronics industry therefore continues to seek
improvement in cleaning formulations for copper-metallized
substrates, and in compositions for processing of microelectronic
device structures, including compositions variously useful for
post-etching cleaning, post-ashing cleaning and post-chemical
mechanical polishing cleaning of microelectronic device wafers.
SUMMARY
The present invention generally relates to a composition and
process for cleaning residue and/or contaminants from
microelectronic devices having said residue and contaminants
thereon. The cleaning compositions described herein include at
least one novel antioxidant as a corrosion inhibitor. The residue
may include post-CMP, post-etch, or post-ash residue.
In one aspect, a cleaning composition comprising at least one
solvent, at least one corrosion inhibitor, and at least one amine
is described, wherein the corrosion inhibitor comprises a species
selected from the group consisting of: cyanuric acid; barbituric
acid and derivatives thereof; glucuronic acid; squaric acid;
alpha-keto acids; adenosine and derivatives thereof; purine
compounds and derivatives thereof; phosphonic acid derivatives;
phenanthroline/ascorbic acid; glycine/ascorbic acid; nicotinamide
and derivatives thereof; flavonols and derivatives thereof;
anthocyanins and derivatives thereof; flavonol/anthocyanin; and
combinations thereof, wherein the cleaning composition is effective
for the removal of residue from a microelectronic device having
said residue thereon. The cleaning composition may further comprise
at least one additional component selected from the group
consisting of: at least one quaternary base; at least one
complexing agent; at least one surfactant; at least one reducing
agent; at least one dispersing agent; at least one sulfonic
acid-containing hydrocarbon; uric acid; at least one alcohol; and
combinations thereof.
In another aspect, a cleaning composition comprising at least one
solvent, at least one surfactant, at least one dispersing agent, at
least one sulfonic-acid containing hydrocarbon, and at least one
corrosion inhibitor is described, wherein the corrosion inhibitor
comprises a species selected from the group consisting of: cyanuric
acid; barbituric acid and derivatives thereof; glucuronic acid;
squaric acid; alpha-keto acids; adenosine and derivatives thereof;
purine compounds and derivatives thereof; phosphonic acid
derivatives; phenanthroline/ascorbic acid; glycine/ascorbic acid;
nicotinamide and derivatives thereof; flavonols and derivatives
thereof; anthocyanins and derivatives thereof;
flavonol/anthocyanin; and combinations thereof, wherein the
cleaning composition is effective for the removal of residue from a
microelectronic device having said residue thereon.
In yet another aspect, the invention relates to removal composition
comprising at least one amine, at least one quaternary base, at
least one antioxidant, optionally at least one alcohol and
optionally at least one additional corrosion inhibitor, wherein
said removal composition is suitable for removing residue and
contaminants from a microelectronic device having said material
thereon.
Yet another aspect relates to a removal composition comprising at
least one amine, at least one quaternary base, at least one
antioxidant, at least one alcohol and at least one additional
organic acid antioxidant, wherein said removal composition is
suitable for removing residue and contaminants from a
microelectronic device having said material thereon. Preferably,
the at least one antioxidant comprises uric acid.
In another aspect, a kit is described, said kit comprising, in one
or more containers, one or more of the following reagents for
forming a cleaning composition, said one or more reagents selected
from the group consisting of: at least one corrosion inhibitor; at
least one quaternary base; at least one organic amine; at least one
complexing agent; at least one surfactant; at least one reducing
agent; at least one dispersing agent; at least one sulfonic
acid-containing hydrocarbon; at least one amine; uric acid; at
least one alcohol; and combinations thereof. The at least one
corrosion inhibitor preferably comprises at least one species
selected from the group consisting of squaric acid, adenosine and
derivatives thereof, phenanthroline/ascorbic acid, nicotinamide and
derivatives thereof, flavonoids, anthocyanins,
flavonol/anthocyanins, quercitin and derivatives thereof,
glucuronic acid, quercitin/anthocyanins, and combinations
thereof.
In yet another aspect, a method of removing residue and
contaminants from a microelectronic device having said residue and
contaminants thereon is described, said method comprising
contacting the microelectronic device with a cleaning composition
for sufficient time to at least partially clean said residue and
contaminants from the microelectronic device, wherein the cleaning
composition includes at least one solvent, at least one corrosion
inhibitor and at least one amine, wherein the corrosion inhibitor
comprises a species selected from the group consisting of
consisting of: cyanuric acid; barbituric acid and derivatives
thereof; glucuronic acid; squaric acid; alpha-keto acids; adenosine
and derivatives thereof; purine compounds and derivatives thereof;
phosphonic acid derivatives; phenanthroline/ascorbic acid;
glycine/ascorbic acid; nicotinamide and derivatives thereof;
flavonols and derivatives thereof; anthocyanins and derivatives
thereof; flavonol/anthocyanin; and combinations thereof. The
cleaning composition may further comprise at least one additional
component selected from the group consisting of: at least one
quaternary base; at least one complexing agent; at least one
surfactant; at least one reducing agent; at least one dispersing
agent; at least one sulfonic acid-containing hydrocarbon; uric
acid; at least one alcohol; and combinations thereof.
Another aspect relates to a method of identifying an endpoint of a
cleaning composition, said method comprising: contacting a
microelectronic device having residue thereon with a cleaning
composition, wherein the cleaning composition includes at least one
antioxidant (i.e., corrosion inhibitor), wherein the antioxidant is
in a first state, signifying that the cleaning composition is
useful to substantially remove said residue from the
microelectronic device; and monitoring the cleaning composition,
wherein a transition of the antioxidant to a second state signifies
an endpoint of the cleaning composition, wherein the first state of
the antioxidant may be colorless or a first color in the visible
spectrum, the second state of the of the antioxidant may be
colorless or a second color in the visible spectrum, and the first
state and the second state are not the same.
In another aspect, a method of removing post-CMP residue and
contaminants from a microelectronic device having same thereon is
described, said method comprising: polishing the microelectronic
device with a CMP slurry; contacting the microelectronic device
with a cleaning composition comprising at least one corrosion
inhibitor, for a sufficient time to remove post-CMP residue and
contaminants from the microelectronic device to form a post-CMP
residue-containing composition; and continuously contacting the
microelectronic device with the post-CMP residue-containing
composition for a sufficient amount of time to effect substantial
cleaning of the microelectronic device, wherein the at least one
corrosion inhibitor comprises a species selected from the group
consisting of consisting of: cyanuric acid; barbituric acid and
derivatives thereof; glucuronic acid; squaric acid; alpha-keto
acids; adenosine and derivatives thereof; purine compounds and
derivatives thereof; phosphonic acid derivatives;
phenanthroline/ascorbic acid; glycine/ascorbic acid; nicotinamide
and derivatives thereof; flavonols and derivatives thereof;
anthocyanins and derivatives thereof; flavonol/anthocyanin; and
combinations thereof.
In a further aspect, a method of manufacturing a microelectronic
device is described, said method comprising contacting the
microelectronic device with a cleaning composition described herein
for sufficient time to at least partially clean post-CMP residue,
post-etch residue, post-ash residue and/or contaminants from the
microelectronic device having said residue and contaminants
thereon.
Yet another aspect relates to improved microelectronic devices, and
products incorporating same, made using the methods described
herein comprising cleaning of post-CMP residue, post-etch residue,
post-ash residue and/or contaminants from the microelectronic
device having said residue and contaminants thereon, using the
methods and/or compositions described herein, and optionally,
incorporating the microelectronic device into a product.
Another aspect relates to an article of manufacture comprising a
cleaning composition, a microelectronic device wafer, and material
selected from the group consisting of residue, contaminants and
combinations thereof, wherein the cleaning composition comprises at
least one solvent, at least one corrosion inhibitor and at least
one amine, wherein the at least one corrosion inhibitor comprises a
species selected from the group consisting of cyanuric acid;
barbituric acid and derivatives thereof; glucuronic acid; squaric
acid; alpha-keto acids; adenosine and derivatives thereof; purine
compounds and derivatives thereof; phosphonic acid derivatives;
phenanthroline/ascorbic acid; glycine/ascorbic acid; nicotinamide
and derivatives thereof; flavonols and derivatives thereof;
anthocyanins and derivatives thereof; flavonol/anthocyanin; and
combinations thereof, and wherein the residue comprises at least
one of post-CMP residue, post-etch residue and post-ash
residue.
Other aspects, features and advantages of the invention will be
more fully apparent from the ensuing disclosure and appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1a is a scanning electron micrograph (SEM) of the control
wafer (post-CMP) at 6,000 times magnification; showing residues
from the CMP process and slurry particles.
FIG. 1b is a SEM of the control wafer of FIG. 1a following cleaning
with a 20:1 dilution of concentrate A according to the method
described herein.
FIG. 1c is a SEM of the control wafer of FIG. 1a following cleaning
with a 20:1 dilution of concentrate D according to the method
described herein.
FIG. 2a is a Partial Image atomic force micrograph (AFM) of the
copper surface following cleaning with a 20:1 dilution of
concentrate A according to the method described herein.
FIG. 2b is a Partial Image atomic force micrograph (AFM) of the
copper surface following cleaning with a 20:1 dilution of
concentrate D according to the method described herein.
DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS THEREOF
The present invention relates generally to compositions useful for
the removal of residue and contaminants from a microelectronic
device having such material(s) thereon. The compositions are
particularly useful for the removal of post-CMP, post-etch or
post-ash residue.
For ease of reference, "microelectronic device" corresponds to
semiconductor substrates, flat panel displays, phase change memory
devices, solar panels and other products including solar
substrates, photovoltaics, and microelectromechanical systems
(MEMS), manufactured for use in microelectronic, integrated
circuit, or computer chip applications. Solar substrates include,
but are not limited to, silicon, amorphous silicon, polycrystalline
silicon, monocrystalline silicon, CdTe, copper indium selenide,
copper indium sulfide, and gallium arsenide on gallium. The solar
substrates may be doped or undoped. It is to be understood that the
term "microelectronic device" is not meant to be limiting in any
way and includes any substrate that will eventually become a
microelectronic device or microelectronic assembly.
As used herein, "residue" corresponds to particles generated during
the manufacture of a microelectronic device including, but not
limited to, plasma etching, ashing, chemical mechanical polishing,
wet etching, and combinations thereof.
As used herein, "contaminants" correspond to chemicals present in
the CMP slurry, reaction by-products of the polishing slurry,
chemicals present in the wet etching composition, reaction by
products of the wet etching composition, and any other materials
that are the by-products of the CMP process, the wet etching, the
plasma etching or the plasma ashing process.
As used herein, "post-CMP residue" corresponds to particles from
the polishing slurry, e.g., silica-containing particles, chemicals
present in the slurry, reaction by-products of the polishing
slurry, carbon-rich particles, polishing pad particles, brush
deloading particles, equipment materials of construction particles,
copper, copper oxides, organic residues, and any other materials
that are the by-products of the CMP process.
As defined herein, "low-k dielectric material" corresponds to any
material used as a dielectric material in a layered microelectronic
device, wherein the material has a dielectric constant less than
about 3.5. Preferably, the low-k dielectric materials include
low-polarity materials such as silicon-containing organic polymers,
silicon-containing hybrid organic/inorganic materials,
organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG),
silicon dioxide, and carbon-doped oxide (CDO) glass. It is to be
appreciated that the low-k dielectric materials may have varying
densities and varying porosities.
As defined herein, "complexing agent" includes those compounds that
are understood by one skilled in the art to be complexing agents,
chelating agents and/or sequestering agents. Complexing agents will
chemically combine with or physically hold the metal atom and/or
metal ion to be removed using the compositions described
herein.
As defined herein, the term "barrier material" corresponds to any
material used in the art to seal the metal lines, e.g., copper
interconnects, to minimize the diffusion of said metal, e.g.,
copper, into the dielectric material. Preferred barrier layer
materials include tantalum, titanium, ruthenium, hafnium, tungsten,
and other refractory metals and their nitrides and silicides.
As defined herein, "post-etch residue" corresponds to material
remaining following gas-phase plasma etching processes, e.g., BEOL
dual damascene processing, or wet etching processes. The post-etch
residue may be organic, organometallic, organosilicic, or inorganic
in nature, for example, silicon-containing material, carbon-based
organic material, and etch gas residue such as oxygen and
fluorine.
As defined herein, "post-ash residue," as used herein, corresponds
to material remaining following oxidative or reductive plasma
ashing to remove hardened photoresist and/or bottom anti-reflective
coating (BARC) materials. The post-ash residue may be organic,
organometallic, organosilicic, or inorganic in nature.
"Substantially devoid" is defined herein as less than 2 wt. %,
preferably less than 1 wt. %, more preferably less than 0.5 wt. %,
and most preferably less than 0.1 wt. %.
As used herein, "about" is intended to correspond to .+-.5% of the
stated value.
As used herein, "suitability" for cleaning residue and contaminants
from a microelectronic device having said residue and contaminants
thereon corresponds to at least partial removal of said
residue/contaminants from the microelectronic device. Cleaning
efficacy is rated by the reduction of objects on the
microelectronic device. For example, pre- and post-cleaning
analysis may be carried out using an atomic force microscope. The
particles on the sample may be registered as a range of pixels. A
histogram (e.g., a Sigma Scan Pro) may be applied to filter the
pixels in a certain intensity, e.g., 231-235, and the number of
particles counted. The particle reduction may be calculated
using:
.times..times..times..times..times..times..times..times..times..times..-
times..times..times..times..times..times..times..times..times..times.
##EQU00001## Notably, the method of determination of cleaning
efficacy is provided for example only and is not intended to be
limited to same. Alternatively, the cleaning efficacy may be
considered as a percentage of the total surface that is covered by
particulate matter. For example, AFM's may be programmed to perform
a z-plane scan to identify topographic areas of interest above a
certain height threshold and then calculate the area of the total
surface covered by said areas of interest. One skilled in the art
would readily understand that the less area covered by said areas
of interest post-cleaning, the more efficacious the cleaning
composition. Preferably, at least 75% of the residue/contaminants
are removed from the microelectronic device using the compositions
described herein, more preferably at least 90%, even more
preferably at least 95%, and most preferably at least 99% of the
residue/contaminants are removed.
The cleaning compositions described herein must possess good metal
compatibility, e.g., a low etch rate on the interconnect metal
and/or interconnector metal silicide material. Metals of interest
include, but are not limited to, copper, tungsten, cobalt,
aluminum, tantalum, titanium, ruthenium, and silicides thereof.
Compositions described herein may be embodied in a wide variety of
specific formulations, as hereinafter more fully described.
In all such compositions, wherein specific components of the
composition are discussed in reference to weight percentage ranges
including a zero lower limit, it will be understood that such
components may be present or absent in various specific embodiments
of the composition, and that in instances where such components are
present, they may be present at concentrations as low as 0.001
weight percent, based on the total weight of the composition in
which such components are employed.
The cleaning compositions include at least one antioxidant
component (i.e., "corrosion inhibitor") where the antioxidant
component is added to the cleaning composition to lower the
corrosion rate of metals, e.g., copper, aluminum, as well as
enhance the cleaning performance. Antioxidants (also referred to as
"corrosion inhibitors" herein) contemplated include, but are not
limited to: cyanuric acid; barbituric acid and derivatives such as
1,2-dimethylbarbituric acid; glucuronic acid; squaric acid;
alpha-keto acids such as pyruvic acid; adenosine and derivatives
thereof; purine compounds such as adenine, purine, guanine,
hypoxanthine, xanthine, theobromine, caffeine, uric acid, and
isoguanine, and derivatives thereof; phosphonic acid and
derivatives thereof; phenanthroline/ascorbic acid; glycine/ascorbic
acid; nicotinamide and derivatives thereof such as nicotinamide
ascorbate; flavonoids such as flavonols and anthocyanins and
derivatives thereof; flavonol/anthocyanin; and combinations
thereof. For example, the flavonols may include quercitin and
derivatives thereof such as quercetin glucosides, quercitrin
(quercetinrhamnoside) and rutin (quercetin rutinoside). The
combination of anthocyanins and flavonols increases the solubility
of flavonols in water. Particularly preferred antioxidants include
purine compounds, squaric acid, adenosine and derivatives thereof,
phenanthroline/ascorbic acid, nicotinamide and derivatives thereof,
flavonoids, anthocyanins, flavonol/anthocyanins, quercitin and
derivatives thereof, and glucuronic acid.
In one aspect, a cleaning composition is described, wherein said
cleaning composition comprises at least one solvent and at least
one antioxidant (i.e., corrosion inhibitor) selected from the group
consisting of cyanuric acid; barbituric acid and derivatives such
as 1,2-dimethylbarbituric acid; glucuronic acid; squaric acid;
alpha-keto acids such as pyruvic acid; adenosine and derivatives
thereof; purine compounds such as adenine, purine, guanine,
hypoxanthine, xanthine, theobromine, caffeine, uric acid, and
isoguanine, and derivatives thereof; phosphonic acid and
derivatives thereof; phenanthroline/ascorbic acid; glycine/ascorbic
acid; nicotinamide and derivatives thereof such as nicotinamide
ascorbate; flavonoids such as flavonols and anthocyanins and
derivatives thereof; flavonol/anthocyanin; and combinations
thereof. Preferably the solvent comprises water, preferably
deionized water.
Embodiments of the cleaning compositions of this aspect include
compositions selected from the group consisting of (i)-(ix),
wherein the antioxidant (i.e., corrosion inhibitor) is selected
from the group consisting of cyanuric acid; barbituric acid and
derivatives such as 1,2-dimethylbarbituric acid; glucuronic acid;
squaric acid; alpha-keto acids such as pyruvic acid; adenosine and
derivatives thereof; purine compounds such as adenine, purine,
guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid,
and isoguanine, and derivatives thereof; phosphonic acid and
derivatives thereof; phenanthroline/ascorbic acid; glycine/ascorbic
acid; nicotinamide and derivatives thereof such as nicotinamide
ascorbate; flavonoids such as flavonols and anthocyanins and
derivatives thereof; flavonol/anthocyanin; and combinations
thereof, (i) a composition comprising at least one quaternary base,
at least one organic amine, at least one antioxidant, water, and
optionally at least one reducing agent; (ii) a composition
comprising at least one quaternary base, at least one organic
amine, at least one antioxidant, at least one complexing agent, and
water; (iii) a composition comprising at least one amine, at least
one antioxidant and water; (iv) a composition comprising at least
one amine, at least one antioxidant, at least one surfactant,
water, and optionally at least one reducing agent; (v) a
composition comprising at least one amine, at least one
antioxidant, at least one reducing agent, water, optionally at
least one surfactant, and optionally at least one quaternary base;
(vi) a composition comprising at least one amine, at least one
antioxidant, at least one quaternary base, at least one reducing
agent, water, and optionally at least one surfactant; (vii) a
composition comprising at least one quaternary base, at least one
amine, uric acid, water, and at least one antioxidant; (viii) a
composition comprising at least one quaternary base, at least one
amine, uric acid, at least one alcohol, water, and at least one
antioxidant; and (ix) a composition comprising at least one
surfactant, at least one dispersing agent, at least one
sulfonic-acid containing hydrocarbon, water, and at least one
antioxidant; Particularly preferred antioxidants include purine
compounds, squaric acid, adenosine and derivatives thereof,
phenanthroline/ascorbic acid, nicotinamide and derivatives thereof,
flavonoids, anthocyanins, flavonol/anthocyanins, quercitin and
derivatives thereof, and glucuronic acid.
In a particularly preferred embodiment, the cleaning composition
comprises at least one quaternary base, at least one organic amine,
at least one antioxidant, and water, wherein the antioxidant (i.e.,
corrosion inhibitor) is selected from the group consisting of
cyanuric acid; barbituric acid and derivatives such as
1,2-dimethylbarbituric acid; glucuronic acid; squaric acid;
alpha-keto acids such as pyruvic acid; adenosine and derivatives
thereof; purine compounds such as adenine, purine, guanine,
hypoxanthine, xanthine, theobromine, caffeine, uric acid, and
isoguanine, and derivatives thereof; phosphonic acid and
derivatives thereof; phenanthroline/ascorbic acid; glycine/ascorbic
acid; nicotinamide and derivatives thereof such as nicotinamide
ascorbate; flavonoids such as flavonols and anthocyanins and
derivatives thereof; flavonol/anthocyanin; and combinations
thereof. The cleaning composition may optionally further comprise
at least one reducing agent, at least one complexing agent, at
least one surfactant, residue material, or combinations
thereof.
The cleaning composition is particularly useful for cleaning
residue and contaminants, e.g., post-CMP residue, post-etch
residue, post-ash residue, and contaminants from a microelectronic
device structure. Regardless of the embodiment, the cleaning
compositions are preferably substantially devoid of oxidizing
agent, fluoride source, and abrasive material prior to removal of
residue material from the microelectronic device. When the cleaning
composition includes glucoronic acid, the pH of the composition
should be greater than or equal to 6.
The pH of the cleaning compositions of this aspect may be varied to
produce a composition optimized for the intended end use. In
general, the pH will be basic, e.g., greater than about 8.5 and
less than about 11.5. For example, concentrated cleaning
compositions described herein have a higher pH, e.g., about 11 to
about 11.5, and following dilution as described herein, the pH of
the diluted composition will decrease to about 9 to about 10,
respectively. Preferably, diluted cleaning compositions have pH in
a range from about 8.5 to 9.5.
In yet another preferred embodiment, the cleaning compositions of
this aspect further include residue and/or contaminants. The
residue and contaminants may be dissolved and/or suspended in the
compositions. Preferably, the residue includes post-CMP residue,
post-etch residue, post-ash residue, contaminants, or combinations
thereof.
In a further embodiment of this aspect, the cleaning composition
may comprise, consist of, or consist essentially of a cleaning
composition selected from the group consisting of (i)-(ix), wherein
the at least one antioxidant (i.e., corrosion inhibitor) comprises
a species selected from the group consisting of cyanuric acid;
barbituric acid and derivatives such as 1,2-dimethylbarbituric
acid; glucuronic acid; squaric acid; alpha-keto acids such as
pyruvic acid; adenosine and derivatives thereof; purine compounds
such as adenine, purine, guanine, hypoxanthine, xanthine,
theobromine, caffeine, uric acid, and isoguanine, and derivatives
thereof; phosphonic acid and derivatives thereof;
phenanthroline/ascorbic acid; glycine/ascorbic acid; nicotinamide
and derivatives thereof such as nicotinamide ascorbate; flavonoids
such as flavonols and anthocyanins and derivatives thereof;
flavonol/anthocyanin; and combinations thereof. Particularly
preferred antioxidants include purine compounds, squaric acid,
adenosine and derivatives thereof, phenanthroline/ascorbic acid,
nicotinamide and derivatives thereof, flavonoids; anthocyanins;
flavonol/anthocyanins; quercitin and derivatives thereof; and
glucuronic acid.
The cleaning compositions may further include additional corrosion
inhibitors, in addition to the antioxidants enumerated above,
including, but not limited to, ascorbic acid, L(+)-ascorbic acid,
isoascorbic acid, ascorbic acid derivatives, benzotriazole, citric
acid, ethylenediamine, gallic acid, oxalic acid, tannic acid,
ethylenediaminetetraacetic acid (EDTA), uric acid, 1,2,4-triazole
(TAZ), tolyltriazole, 5-phenyl-benzotriazole,
5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole,
1-amino-1,2,4-triazole, hydroxybenzotriazole,
2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole,
1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole,
3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole,
5-phenylthiol-benzotriazole, halo-benzotriazoles (halo=F, Cl, Br or
I), naphthotriazole, 2-mercaptobenzimidazole (MBI),
2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole,
2-mercaptothiazoline, 5-aminotetrazole,
5-amino-1,3,4-thiadiazole-2-thiol,
2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine,
methyltetrazole, 1,3-dimethyl-2-imidazolidinone,
1,5-pentamethylenetetrazole, 1 -phenyl-5-mercaptotetrazole,
diaminomethyltriazine, imidazoline thione, mercaptobenzimidazole,
4-methyl-4H-1,2,4-triazole-3-thiol,
5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl
phosphate, imidazole, indiazole, benzoic acid, ammonium benzoate,
catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid,
barbituric acid and derivatives such as 1,2-dimethylbarbituric
acid, alpha-keto acids such as pyruvic acid, adenine, purine,
phosphonic acid and derivatives thereof, glycine/ascorbic acid, and
combinations thereof. For example, the cleaning compositions may
include the combination of phenanthroline and ascorbic acid or
glycine and ascorbic acid.
Illustrative amines (i.e., organic amines) that may be useful in
specific compositions include species having the general formula
NR.sup.1R.sup.2R.sup.3, wherein R.sup.1, R.sup.2 and R.sup.3 may be
the same as or different from one another and are selected from the
group consisting of hydrogen, straight-chained or branched
C.sub.1-C.sub.6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl,
and hexyl) and straight-chained or branched C.sub.1-C.sub.6 alcohol
(e.g., methanol, ethanol, propanol, butanol, pentanol, and
hexanol). Most preferably, at least one of R.sup.1, R.sup.2 and
R.sup.3 is a straight-chained or branched C.sub.1-C.sub.6 alcohol.
Examples include, without limitation, aminoethylethanolamine,
N-methylaminoethanol, aminoethoxyethanol,
dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine,
monoethanolamine, triethanolamine, 1-amino-2-propanol,
2-amino-1-butanol, isobutanolamine, triethylenediamine, other
C.sub.1-C.sub.8 alkanolamines and combinations thereof.
Quaternary bases contemplated herein include compounds having the
formula NR.sup.1R.sup.2R.sup.3R.sup.4OH, wherein R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 may be the same as or different from one
another and are selected from the group consisting of hydrogen,
straight-chained or branched C.sub.1-C.sub.6 alkyl (e.g., methyl,
ethyl, propyl, butyl, pentyl, and hexyl), and substituted or
unsubstituted C.sub.6-C.sub.10 aryl, e.g., benzyl.
Tetraalkylammonium hydroxides that are commercially available
include tetraethylammonium hydroxide (TEAH), tetramethyammonium
hydroxide (TMAH), tetrapropylammonium hydroxide (TPAH),
tetrabutylammonium hydroxide (TBAH), tributylmethylammonium
hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), and
combinations thereof, may be used. Tetraalkylammonium hydroxides
which are not commercially available may be prepared in a manner
analogous to the published synthetic methods used to prepare TMAH,
TEAH, TPAH, TBAH, TBMAH, and BTMAH, which are known to one ordinary
of skill in the art. Another widely used quaternary ammonium base
is choline hydroxide.
Reducing agent(s) contemplated herein include species selected from
the group consisting of ascorbic acid, L(+)-ascorbic acid,
isoascorbic acid, ascorbic acid derivatives, gallic acid, glyoxal,
and combinations thereof.
Illustrative alcohols include straight-chained or branched
C.sub.1-C.sub.6 alcohols (e.g., methanol, ethanol, propanol,
butanol, pentanol, and hexanol), diols and triols. Preferably, the
alcohol comprises isopropanol (IPA).
Illustrative surfactants for use in the compositions described
herein include, but are not limited to, amphoteric salts, cationic
surfactants, anionic surfactants, fluoroalkyl surfactants,
non-ionic surfactants, and combinations thereof including, but not
limited to, SURFONYL.RTM. 104, TRITON.RTM. CF-21, ZONYL.RTM. UR,
ZONYL.RTM. FSO-100, ZONYL.RTM. FSN-100, 3M Fluorad
fluorosurfactants (i.e., FC-4430 and FC-4432),
dioctylsulfosuccinate salt, 2,3-dimercapto-1-propanesulfonic acid
salt, dodecylbenzenesulfonic acid, polyethylene glycols,
polypropylene glycols, polyethylene or polypropylene glycol ethers,
carboxylic acid salts, R.sub.1 benzene sulfonic acids or salts
thereof (where the R.sub.1 is a straight-chained or branched
C.sub.8-C.sub.18 alkyl group), amphiphilic fluoropolymers,
polyethylene glycols, polypropylene glycols, polyethylene or
polypropylene glycol ethers, carboxylic acid salts,
dodecylbenzenesulfonic acid, polyacrylate polymers, dinonylphenyl
polyoxyethylene, silicone or modified silicone polymers, acetylenic
diols or modified acetylenic diols, alkylammonium or modified
alkylammonium salts, as well as combinations comprising at least
one of the foregoing surfactants, sodium dodecyl sulfate,
zwitterionic surfactants, aerosol-OT (AOT) and fluorinated
analogues thereof, alkyl ammonium, perfluoropolyether surfactants,
2-sulfosuccinate salts, phosphate-based surfactants, sulfur-based
surfactants, and acetoacetate-based polymers. In a preferred
embodiment, the surfactant includes an alkyl benzene sulfonic acid,
more preferably dodecylbenzenesulfonic acid.
The dispersing agent, when used in the compositions described
herein, is included to increase dispersancy and minimize
redeposition of the removed residue and contaminants at the surface
of the microelectronic device wafer. Dispersing agents contemplated
herein include organic polymers containing acrylic acid or salts
thereof having an average molecular weight of less than 15,000,
hereinafter referred to as low molecular weight acrylic
acid-containing polymer. The low molecular weight acrylic
acid-containing polymer has an average molecular weight of less
than 15,000, preferably from about 3,000 to about 10,000. The low
molecular weight acrylic acid-containing polymer may be either a
homopolymer or a copolymer including the essential acrylic acid or
acrylic acid salt monomer units. Copolymers may include essentially
any suitable other monomer units including modified acrylic,
fumaric, maleic, itaconic, aconitic, mesaconic, citraconic, and
methylenemalonic acid or their salts, maleic anhydride, alkylene,
vinylmethyl ether, styrene and any mixtures thereof. Preferred
commercially available low molecular weight acrylic acid containing
homopolymers include those sold under the tradename Acusol 445
(Rohm and Haas, Philadelphia, Pa., USA).
The sulfonic acid-containing hydrocarbons contemplated herein
include straight chain and branched C.sub.1-C.sub.6 alkane, e.g.,
methane, ethane, propane, butane, pentane, hexane, sulfonic acids,
straight chain and branched C.sub.2-C.sub.6 alkene, e.g., ethane,
propene, butane, pentene, hexane, sulfonic acids, and substituted
or unsubstituted C.sub.6-C.sub.14 aryl sulfonic acids, and salts
thereof, e.g., sodium, potassium, etc. Sulfonic acid-containing
hydrocarbons include methanesulfonic acid, ethanesulfonic acid,
propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid,
hexanesulfonic acid, ethenesulfonic acid, toluenesulfonic acid, and
combinations thereof.
The optional complexing agents contemplated herein include, but are
not limited to, acetic acid, acetone oxime, acrylic acid, adipic
acid, alanine, arginine, asparagine, aspartic acid, betaine,
dimethyl glyoxime, formic acid, fumaric acid, gluconic acid,
glutamic acid, glutamine, glutaric acid, glyceric acid, glycerol,
glycolic acid, glyoxylic acid, histidine, iminodiacetic acid,
isophthalic acid, itaconic acid, lactic acid, leucine, lysine,
maleic acid, maleic anhydride, malic acid, malonic acid, mandelic
acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic
acid, proline, propionic acid, pyrocatecol, pyromellitic acid,
quinic acid, serine, sorbitol, succinic acid, tartaric acid,
terephthalic acid, trimellitic acid, trimesic acid, tyrosine,
valine, xylitol, salts and derivatives thereof, and combinations
thereof.
With regards to compositional amounts, the weight percent ratios of
each component in each embodiment of this aspect described herein
is as follows: embodiment (i): about 0.1:1 to about 10:1 quaternary
base to corrosion inhibitor, preferably about 0.5:1 to about 5:1,
and even more preferably about 1:1 to about 2:1; about 0.1:1 to
about 10:1 organic amine to corrosion inhibitor, preferably about
0.5:1 to about 5:1, and even more preferably about 2:1 to about
3:1; embodiment (ii): about 1:1 to about 5:1 quaternary base to
complexing agent, preferably about 2:1 to about 3.5:1; about 1:1 to
about 10:1 organic amine to complexing agent, preferably about 3:1
to about 7:1; about 0.001:1 to about 0.5:1 corrosion inhibitor to
complexing agent, preferably about 0.01:1 to about 0.1:1;
embodiment (iii): about 0.1:1 to about 10:1 organic amine to
corrosion inhibitor, preferably about 1:1 to about 3:1; embodiment
(iv): about 0.1:1 to about 10:1 organic amine to corrosion
inhibitor, preferably about 1:1 to about 3:1; about 0.001:1 to
about 0.5:1 surfactant to corrosion inhibitor, preferably about
0.01:1 to about 0.1:1; embodiment (v): about 0.1:1 to about 15:1
organic amine to corrosion inhibitor, preferably about 1:1 to about
10:1; about 0.1 to about 10:1 reducing agent to corrosion
inhibitor, preferably about 1:1 to about 8:1; embodiment (vi):
about 1:1 to about 10:1 organic amine to corrosion inhibitor,
preferably about 2:1 to about 7:1; about 0.5:1 to about 8:1
quaternary base to corrosion inhibitor, preferably about 1:1 to
about 4:1; about 0.1:1 to about 6:1 reducing agent to corrosion
inhibitor, preferably about 0.5:1 to about 3:1; about 0.001:1 to
about 0.1:1 surfactant (when present) to corrosion inhibitor;
embodiment (vii): about 1:1 to about 10:1 amine to corrosion
inhibitor, preferably about 2:1 to about 7:1; about 0.5:1 to about
8:1 quaternary base to corrosion inhibitor, preferably about 1:1 to
about 4:1; about 0.1:1 to about 6:1 reducing agent to corrosion
inhibitor, preferably about 0.5:1 to about 3:1; embodiment (viii):
about 1:1 to about 10:1 amine to corrosion inhibitor, preferably
about 2:1 to about 7:1; about 0.5:1 to about 8:1 quaternary base to
corrosion inhibitor, preferably about 1:1 to about 4:1; about 0.1:1
to about 6:1 uric acid to corrosion inhibitor, preferably about
0.5:1 to about 3:1; about 0.5:1 to about 8:1 alcohol to corrosion
inhibitor, preferably about 1:1 to about 4:1; embodiment (ix):
about 10:1 to about 100:1 corrosion inhibitor to surfactant,
preferably about 30:1 to about 70:1; about 0.01:1 to about 5:1
dispersing agent to surfactant, preferably about 0.05:1 to about
1:1; about 1:1 to about 10:1 sulfonic acid-containing hydrocarbon
to surfactant, preferably about 3:1 to about 7:1.
In another aspect, the cleaning compositions are aqueous
compositions including uric acid and at least one alcohol, which
are present in the composition in relative amounts imparting to the
composition an effectiveness for cleaning for which the composition
is used. In another embodiment, the cleaning compositions are
aqueous compositions including at least one amine, at least one
base, and uric acid. In another embodiment, the cleaning
compositions are aqueous compositions including at least one amine,
at least one quaternary base, at least one alcohol, and uric acid.
In still another embodiment, the cleaning compositions are aqueous
compositions including at least one amine, at least one quaternary
base, uric acid, and at least one additional corrosion inhibitor.
In yet another embodiment, the cleaning compositions are aqueous
compositions including at least one amine, at least one quaternary
base, at least one alcohol, uric acid, and at least one additional
corrosion inhibitor. As defined herein, "uric acid" also covers
derivatives of uric acid.
In the broad practice of this aspect, the cleaning compositions may
comprise, consist of, or consist essentially of: (i) at least one
amine and at least one alcohol; (ii) at least one amine, at least
one base, and uric acid; (iii) at least one amine, at least one
quaternary base, at least one alcohol, and uric acid; (iv) at least
one amine, at least one quaternary base, uric acid, and at least
one additional corrosion inhibitor or (v) at least one amine, at
least one quaternary base, at least one alcohol, uric acid, and at
least one additional corrosion inhibitor. In general, the specific
proportions and amounts of components, in relation to each other,
may be suitably varied to provide the desired removal action of the
composition for the post-CMP, post-etch and/or post-ash residue
and/or processing equipment, as readily determinable within the
skill of the art without undue effort. The water is preferably
deionized.
The amine(s), base(s), alcohol(s) and additional corrosion
inhibitor(s) correspond to those described hereinabove. The range
of weight percent ratios of the components of the cleaning
composition of this aspect is about 0.3 to about 0.8 quaternary
base(s) relative to amine(s), preferably about 0.4 to about 0.7,
and most preferably about 0.5 to about 0.6; about 0.3 to about 0.8
alcohol(s) (when present) relative to amine(s), preferably about
0.4 to about 0.7, and most preferably about 0.5 to about 0.6; about
0.01 to about 0.50 uric acid relative to amine(s), preferably about
0.1 to about 0.45, and most preferably about 0.15 to about 0.4; and
about 0.01 to about 0.5 additional corrosion inhibitor(s) (when
present) relative to amine(s), preferably about 0.1 to about 0.4,
and most preferably about 0.2 to about 0.3.
In a specific aspect, the cleaning compositions may be formulated
to be substantially devoid of hydrogen peroxide and other oxidizing
agents, cyclic ethers, metal corrosion inhibiting metal halides,
and abrasive material prior to removal of residue material from the
microelectronic device.
The pH of the cleaning compositions of this aspect may be varied to
produce a composition optimized for the intended end use. In
general, the pH will be basic, e.g., greater than about 8.5 and
less than about 11.5. For example, concentrated cleaning
compositions described herein have a higher pH, e.g., about 11 to
about 11.5, and following dilution as described herein, the pH of
the diluted composition will decrease to about 9 to about 10,
respectively. Preferably, diluted cleaning compositions have pH in
a range from about 8.5 to 9.5.
In various preferred embodiments, concentrates of the cleaning
composition of this aspect may have the following weight percent
ratios of one component relative to another component: Concentrate
A: wt. % ratio of TMAH relative to 1-amino-2-propanol of 0.56; wt.
% ratio of uric acid relative to 1-amino-2-propanol of 0.39; wt. %
ratio of IPA relative to 1-amino-2-propanol of 0.56; wt. % ratio of
oxalic acid relative to 1-amino-2-propanol of 0.22 Concentrate B:
wt. % ratio of TMAH relative to 1-amino-2-propanol of 0.56; wt. %
ratio of uric acid relative to 1-amino-2-propanol of 0.056; wt. %
ratio of IPA relative to 1-amino-2-propanol of 0.56; wt. % ratio of
oxalic acid relative to 1-amino-2-propanol of 0.056 Concentrate C:
wt. % ratio of TMAH relative to 1-amino-2-propanol of 0.56; wt. %
ratio of uric acid relative to 1-amino-2-propanol of 0.167; wt. %
ratio of IPA relative to 1-amino-2-propanol of 0.56; wt. % ratio of
oxalic acid relative to 1-amino-2-propanol of 0.22
Concentrates A-C may diluted with water at the manufacturer or at
the fab to produce the following Concentrates D-F, wherein all
percentages are by weight, based on the total weight of the
formulation: Concentrate D: 5 wt. % TMAH; 9 wt. %
1-amino-2-propanol; 3.5 wt. % uric acid; 5 wt. % IPA; 2 wt. %
oxalic acid; 75.5 wt. % water Concentrate E: 5 wt. % TMAH; 9 wt. %
1-amino-2-propanol; 0.5 wt. % uric acid; 5 wt. % IPA; 0.5 wt. %
oxalic acid; 80.0 wt. % water Concentrate F: 5 wt. % TMAH; 9 wt. %
1-amino-2-propanol; 1.5 wt. % uric acid; 5 wt. % IPA; 2 wt. %
oxalic acid; 77.5 wt. % water Concentrates D-F may be further
diluted described herein. For example, Concentrates D-F may be
diluted in a ratio of 20:1 diluent to concentrate, as described
herein.
The cleaning compositions provide at least one of the following
benefits: an alkaline pH to maximize particle repulsion from the
surface; solubilization of organic and inorganic residues;
surfactant properties and solubility enhancement via the alcohol;
and the minimization of corrosion of metal layers in the
microelectronic device structure. Furthermore, dielectric material,
including low-k dielectric material, on the microelectronic device
is not compromised by the cleaning composition. Preferably, the
etch rate of metal material is in a range from about 0.01 .ANG.
min.sup.-1 to about 10 .ANG. min.sup.-1, and most preferably about
0.01 .ANG. min.sup.-1 to about 5 .ANG. min.sup.-1.
In a particularly preferred embodiment, the cleaning composition of
this aspect is aqueous and comprises, consists of, or consists
essentially of TMAH, 1-amino-2-propanol, uric acid, IPA, and oxalic
acid.
In another embodiment, the cleaning compositions of this aspect
further include post-CMP, post-etch, and/or post-ash residue
material. The residue material may be dissolved and/or suspended in
the cleaning composition. Accordingly, in another particularly
preferred embodiment, the cleaning composition is aqueous and
comprises, consists of, or consists essentially of TMAH,
1-amino-2-propanol, uric acid, IPA, oxalic acid, and residue
material.
Compositions of both aspects described herein are stable in
character and do not degrade in the manner of formulations of the
prior art. Thus, the compositions are storage stable, without loss
of efficacy, and resistant to oxygen-mediated degradation, so that
they may be used in ambient air environments, without loss of
effectiveness. Furthermore, because the oxidizable components have
relatively good air stability as compared to other antioxidant
species, the compositions described herein may be recirculated in
batch or single wafer processing tools.
The range of weight percent ratios of the components will cover all
possible concentrated or diluted embodiments described herein.
Towards that end, in one embodiment, a concentrated cleaning
composition is provided that can be diluted for use as a cleaning
solution. A concentrated composition, or "concentrate,"
advantageously permits a user, e.g. CMP process engineer, to dilute
the concentrate to the desired strength and pH at the point of use.
Dilution of the concentrated cleaning composition may be in a range
from about 1:1 to about 2500:1, preferably about 5:1 to about
200:1, wherein the cleaning composition is diluted at or just
before the tool with solvent, e.g., deionized water. It is to be
appreciated by one skilled in the art that following dilution, the
range of weight percent ratios of the components disclosed herein
should remain unchanged.
The compositions described herein may have utility in applications
including, but not limited to, post-etch residue removal, post-ash
residue removal surface preparation, post-plating cleaning and
post-CMP residue removal.
The cleaning compositions described herein are easily formulated by
simple addition of the respective ingredients and mixing to
homogeneous condition. Furthermore, the compositions may be readily
formulated as single-package formulations or multi-part
formulations that are mixed at or before the point of use, e.g.,
the individual parts of the multi-part formulation may be mixed at
the tool or in a storage tank upstream of the tool. The
concentrations of the respective ingredients may be widely varied
in specific multiples of the composition, i.e., more dilute or more
concentrated, and it will be appreciated that the compositions
described herein can variously and alternatively comprise, consist
or consist essentially of any combination of ingredients consistent
with the disclosure herein.
Accordingly, another aspect relates to a kit including, in one or
more containers, one or more components adapted to form the
compositions described herein. The kit may include, in one or more
containers, at least one corrosion inhibitor, any of the components
in the embodiments introduced herein, and optionally at least one
additional corrosion inhibitor, for combining with additional
solvent, e.g., water, at the fab or the point of use. The
containers of the kit must be suitable for storing and shipping
said cleaning compositions, for example, NOWPak.RTM. containers
(Advanced Technology Materials, Inc., Danbury, Conn., USA). The one
or more containers which contain the components of the cleaning
composition preferably include means for bringing the components in
said one or more containers in fluid communication for blending and
dispense. For example, referring to the NOWPak.RTM. containers, gas
pressure may be applied to the outside of a liner in said one or
more containers to cause at least a portion of the contents of the
liner to be discharged and hence enable fluid communication for
blending and dispense. Alternatively, gas pressure may be applied
to the head space of a conventional pressurizable container or a
pump may be used to enable fluid communication. In addition, the
system preferably includes a dispensing port for dispensing the
blended cleaning composition to a process tool.
Substantially chemically inert, impurity-free, flexible and
resilient polymeric film materials, such as high density
polyethylene, are preferably used to fabricate the liners for said
one or more containers. Desirable liner materials are processed
without requiring co-extrusion or barrier layers, and without any
pigments, UV inhibitors, or processing agents that may adversely
affect the purity requirements for components to be disposed in the
liner. A listing of desirable liner materials include films
comprising virgin (additive-free) polyethylene, virgin
polytetrafluoroethylene (PTFE), polypropylene, polyurethane,
polyvinylidene chloride, polyvinylchloride, polyacetal,
polystyrene, polyacrylonitrile, polybutylene, and so on. Preferred
thicknesses of such liner materials are in a range from about 5
mils (0.005 inch) to about 30 mils (0.030 inch), as for example a
thickness of 20 mils (0.020 inch).
Regarding the containers for the kits, the disclosures of the
following patents and patent applications are hereby incorporated
herein by reference in their respective entireties: U.S. Pat. No.
7,188,644 entitled "APPARATUS AND METHOD FOR MINIMIZING THE
GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS;" U.S. Pat. No.
6,698,619 entitled "RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID
STORAGE AND DISPENSING CONTAINER SYSTEM;" U.S. Patent Application
No. 60/916,966 entitled "SYSTEMS AND METHODS FOR MATERIAL BLENDING
AND DISTRIBUTION" filed on May 9, 2007 in the name of John E. Q.
Hughes, and PCT/US08/63276 entitled "SYSTEMS AND METHODS FOR
MATERIAL BLENDING AND DISTRIBUTION" filed on May 9, 2008 in the
name of Advanced Technology Materials, Inc.
Proposed kits include, in one container, at least one amine, at
least one quaternary base, at least one antioxidant, at least one
alcohol (when present), and at least one additional corrosion
inhibitor (when present), and optionally water, for combining with
the diluent, e.g., water, at the fab or the point of use. In the
alternative, the kit may include two containers, one container
including the at least one amine, at least one quaternary base, at
least one alcohol (when present), and some water, and the other
container including at least one antioxidant, at least one
additional corrosion inhibitor (when present), and water. In
another alternative, the kit may include three containers, one
container including the at least one amine, at least one quaternary
base, at least one alcohol (when present), and some water, a second
container including at least one antioxidant, and water, and a
third container including at least one additional corrosion
inhibitor and water. In yet another alternative, each component is
present in its own container wherein additional water is present in
the at least one antioxidant and the at least one additional
corrosion inhibitor (when present) containers. Water may optionally
be added to the at least one amine, the at least one quaternary
base, and the at least one alcohol (when present) containers. In
each case, additional water may be added directly to the container
system and/or at a subsequent blending/dilution vessel.
As applied to microelectronic manufacturing operations, the
cleaning compositions described herein are usefully employed to
clean post-CMP residue and/or contaminants from the surface of the
microelectronic device. The cleaning compositions do not damage
low-k dielectric materials or corrode metal interconnects on the
device surface. Preferably the cleaning compositions remove at
least 85% of the residue present on the device prior to residue
removal, more preferably at least 90%, even more preferably at
least 95%, and most preferably at least 99%.
In residue removal application, the composition is applied in any
suitable manner to the device to be cleaned, e.g., by spraying the
composition on the surface of the device to be cleaned, by dipping
(in a volume of the composition) the device to be cleaned, by
contacting the device to be cleaned with another material, e.g., a
pad, or fibrous sorbent applicator element, that is saturated with
the composition, or by any other suitable means, manner or
technique by which the composition is brought into removal contact
with the device to be cleaned. Further, batch or single wafer
processing is contemplated herein. In post-CMP residue and
contaminant cleaning application, the cleaning composition may be
used with a large variety of conventional cleaning tools such as
megasonics and brush scrubbing, including, but not limited to,
Verteq single wafer megasonic Goldfinger, OnTrak systems DDS
(double-sided scrubbers), SEZ or other single wafer spray rinse,
Applied Materials Mirra-Mesa.TM./Reflexion.TM./Reflexion LK.TM.,
and Megasonic batch wet bench systems.
In use of the compositions described herein for cleaning post-CMP
residue, post-etch residue, post-ash residue and/or contaminants
from microelectronic devices having same thereon, the cleaning
composition typically is contacted with the device for a time of
from about 5 sec to about 10 minutes, preferably about 1 sec to 20
min, preferably about 5 sec to about 10 min at temperature in a
range of from about 20.degree. C. to about 90.degree. C.,
preferably about 20.degree. C. to about 50.degree. C. Such
contacting times and temperatures are illustrative, and any other
suitable time and temperature conditions may be employed that are
efficacious to at least partially clean the post-CMP
residue/contaminants from the device, within the broad practice of
the method. "At least partially clean" and "substantial removal"
both correspond to at removal of at least 85% of the residue
present on the device prior to residue removal, more preferably at
least 90%, even more preferably at least 95%, and most preferred at
least 99%
Following the achievement of the desired cleaning action, the
cleaning composition may be readily removed from the device to
which it has previously been applied, as may be desired and
efficacious in a given end use application of the compositions
described herein. Preferably, the rinse solution includes deionized
water. Thereafter, the device may be dried using nitrogen or a
spin-dry cycle.
Advantageously, some of the antioxidants introduced herein undergo
visible color changes as they are consumed, which provides a way
for the user to monitor the efficacy of the cleaning composition
bath. Monitoring means include, but are not limited to, visual and
spectrophotometric means. As defined herein, an "endpoint"
corresponds to a range whereby the cleaning composition is no
longer efficiently and productively removing the materials to be
removed from the microelectronic device, e.g., post-CMP residue.
The endpoint can be the result of many different factors including,
but not limited to, a saturated (e.g., loaded) cleaning
composition, and/or the exhaustion of one or more components of the
cleaning composition.
Accordingly, another aspect includes a method of identifying an
endpoint of a cleaning composition, said method comprising:
contacting a microelectronic device having residue thereon with a
cleaning composition, wherein the cleaning composition includes at
least one antioxidant (i.e., corrosion inhibitor), wherein the
antioxidant is in a first state, signifying that the cleaning
composition is useful to substantially remove said residue from the
microelectronic device; and monitoring the cleaning composition,
wherein a transition of the antioxidant to a second state signifies
an endpoint of the cleaning composition. It is to be appreciated by
one skilled in the art that the first state of the antioxidant may
be colorless or a first color in the visible spectrum, the second
state of the of the antioxidant may be colorless or a second color
in the visible spectrum, and the first state and the second state
are not the same.
Yet another aspect relates to the improved microelectronic devices
made according to the methods described herein and to products
containing such microelectronic devices.
Another aspect relates to a recycled cleaning composition, wherein
the cleaning composition may be recycled until residue and/or
contaminant loading reaches the maximum amount the cleaning
composition may accommodate, as readily determined by one skilled
in the art.
A still further aspect relates to methods of manufacturing an
article comprising a microelectronic device, said method comprising
contacting the microelectronic device with a cleaning composition
for sufficient time to clean post-CMP residue and contaminants from
the microelectronic device having said residue and contaminants
thereon, and incorporating said microelectronic device into said
article, using a cleaning composition described herein.
In still another aspect, a method of cleaning semiconductor tool
parts is described, said method comprising contacting said tool
parts with a composition for sufficient time to clean said parts,
wherein the composition includes at least one amine, at least one
quaternary base, at least one antioxidant, optionally at least one
alcohol, and optionally at least one additional corrosion
inhibitor. In cleaning application, the composition is applied in
any suitable manner to the tool part to be cleaned, e.g., by
spraying the composition on the surface of the tool part to be
cleaned, by dipping (in a volume of the composition) the tool part
to be cleaned, by contacting the tool part to be cleaned with
another material, e.g., a pad, or fibrous sorbent applicator
element, that is saturated with the composition, or by any other
suitable means, manner or technique by which the composition is
brought into removal contact with the tool part to be cleaned.
Typically, tool parts include many of the same residual and
particulate material that is to be removed from the microelectronic
device, e.g., post-CMP residue and contaminants, post-etch residue,
post-ash residue, and combinations thereof.
The features and advantages are more fully shown by the
illustrative examples discussed below.
Example 1
Blanketed PVD copper wafers were immersed in solutions including a
basic solution comprising TMAH, 1-amino-2-propanol, and different
antioxidants and the corrosion rate of copper determined using a
potentiostat where the PVD Cu is the working electrode, Pt mesh is
the counter electrode, and an Ag/AgCl electrode is the reference
electrode. The copper anodic corrosion rates were calculated at
anodic voltage biases from 0.1 to 1.0 V versus open circuit
potentials. The results are summarized in Table 1 below.
TABLE-US-00001 Corrosion Antioxidant Solution rate/.ANG. min.sup.-1
Control (TMAH + 1- 12.28 amino-2-propanol) 15.03 Ascorbic acid 12
mL of 3500 ppm ascorbic acid in 2.72 200 g basic solution 18 mL of
3500 ppm ascorbic acid in 2.62 200 g basic solution 24 mL of 3500
ppm ascorbic acid in 2.99 200 g basic solution uric acid 22 mL of
3500 ppm uric acid in 300 g 17.47 basic solution 22 mL of 3500 ppm
uric acid in 300 g 13.43 basic solution 25 mL of 35000 ppm uric
acid in 300 7.57 g basic solution Uric acid + oxalic 25 mL of 35000
ppm uric 6.94 acid (2% oxalic in 300 g basic solution) 25 mL of
35000 ppm uric 6.18 (2% oxalic in 300 g basic solution) succinic
acid 25 mL of 3500 ppm succinic acid in 15.05 300 g basic solution
25 mL of 3500 ppm succinic acid in 20.49 300 g basic solution
adenosine 800 ppm adenosine in the basic 2.36 solution 800 ppm
adenosine in the basic 2.40 solution 800 ppm adenosine + 800 ppm
3.18 ascorbic acid in the basic solution butylated 3.38 wt. % in
the basic solution 14.40 hydroxytoluene methylene 3.62 wt. % in the
basic solution 16.80 diphosphonic acid 2-amino-ethyl- 2.6 wt. % in
the basic solution 21.50 phosphonic acid
It can be seen that adenosine significantly reduced the corrosion
rate of copper. Additional advantages include, but are not limited
to, minimization of copper roughness and the stabilization of the
copper (I) oxide surface subsequent to residue removal.
Example 2
Compositions were employed for post-CMP cleaning of Sematech 854
pattern wafers having dried slurry and other PCMP residues on their
surface. The wafer in each instance was cleaned on a Laurell
Technologies Corporation (North Wales, Pa., USA) single wafer spin
processor at 23.degree. C. for 90 sec at 150 rpm using diluted
removal concentrates A or D (concentrate D includes 5 wt. % TMAH; 9
wt. % 1-amino-2-propanol; 3.5 wt. % uric acid; 5 wt. % IPA; and
77.5 wt. % water), 30 sec at 150 rpm using deionized water, and 30
sec at 2500 rpm to spin dry the wafer. The cleaning compositions
used were diluted 20 parts diluent (water) to 1 part removal
concentrate prior to wafer processing.
Following treatment, each wafer was subjected to atomic force
microscopic (AFM) imaging (Digital Instruments Dimension 5000
Scanning Probe Microscope, Woodbury, N.Y., USA) to evaluate surface
roughening. For each wafer sample, three random copper pads located
towards the center of the wafer piece were selected for AFM
analysis. At each copper pad location, a 20 .mu.m.times.20 .mu.m
region was scanned in tapping mode at a pixel density of
512.times.512 and a scan rate of 1.0 Hz.
The AFM images provide two RMS surface roughness measurements--one
with the slurry particles which is indicate of the slurry
contamination (Full Image) and one that excludes slurry particles
and thus is indicative of the copper surface roughness (Partial
Image).
Referring to FIGS. 1a, 1b, and 1c, which are scanning electron
micrographs (SEM) at 6,000 times magnification of the control
wafer, the wafer cleaned with formulation A, and the wafer cleaned
with formulation D, respectively, it can be seen that the wafer
following cleaning with diluted concentrate A and the wafer
following cleaning with diluted concentrate D shows little
difference. The post-CMP residue was substantially removed in both
cases.
The AFM micrographs shown in FIGS. 2a and 2b, corresponding to the
Partial Image of the wafer following cleaning with diluted
concentrate A and diluted concentrate D, respectively, reveal that
the addition of the second organic acid antioxidant compound (FIG.
3a--RMS roughness=0.443) provides the benefit of decreased copper
surface roughening as compared to the formula without the second
organic acid antioxidant compound (FIG. 3b--RMS
roughness=0.778).
Although the invention has been variously disclosed herein with
reference to illustrative embodiments and features, it will be
appreciated that the embodiments and features described hereinabove
are not intended to limit the invention, and that other variations,
modifications and other embodiments will suggest themselves to
those of ordinary skill in the art, based on the disclosure herein.
The invention therefore is to be broadly construed, as encompassing
all such variations, modifications and alternative embodiments
within the spirit and scope of the claims hereafter set forth.
* * * * *