U.S. patent application number 11/198365 was filed with the patent office on 2005-12-22 for cmp formulations.
This patent application is currently assigned to SAINT-GOBAIN CERAMICS & PLASTICS, INC.. Invention is credited to Solomos, David Peter, Ward, Douglas Edwin.
Application Number | 20050279030 11/198365 |
Document ID | / |
Family ID | 27765245 |
Filed Date | 2005-12-22 |
United States Patent
Application |
20050279030 |
Kind Code |
A1 |
Ward, Douglas Edwin ; et
al. |
December 22, 2005 |
CMP formulations
Abstract
CMP formulations for use on nickel/phosphorus alloys comprising
abrasive particles and an oxidant, a modifier for the action of the
oxidant and first and second accelerants to sequester removed
materials containing phosphonate and ammonium or amine groups
respectively and optionally an organic carboxylic acid.
Inventors: |
Ward, Douglas Edwin; (Santa
Ana, CA) ; Solomos, David Peter; (Yorba Linda,
CA) |
Correspondence
Address: |
TOLER & LARSON & ABEL L.L.P.
5000 PLAZA ON THE LAKE STE 265
AUSTIN
TX
78746
US
|
Assignee: |
SAINT-GOBAIN CERAMICS &
PLASTICS, INC.
Worcester
MA
|
Family ID: |
27765245 |
Appl. No.: |
11/198365 |
Filed: |
August 5, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11198365 |
Aug 5, 2005 |
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10831946 |
Apr 26, 2004 |
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6945851 |
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10831946 |
Apr 26, 2004 |
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10080853 |
Feb 22, 2002 |
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6755721 |
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Current U.S.
Class: |
51/307 ; 106/3;
51/308; 51/309 |
Current CPC
Class: |
B24B 37/044 20130101;
C09K 3/1463 20130101; C09G 1/02 20130101 |
Class at
Publication: |
051/307 ;
051/308; 051/309; 106/003 |
International
Class: |
B24B 001/00; B24D
003/02 |
Claims
1-29. (canceled)
30. A CMP formulation which comprises a dispersion of abrasive
particles with particle sizes from 15 to 80 nanometers and selected
from the group consisting of silica, alumina, titania, ceria,
zirconia and mixtures thereof dispersed in a formulation
comprising: a. an oxidant; b. a moderator of the action of the
oxidizing agent which comprises a phosphate or phosphite group; c.
an accelerant comprising phosphonate groups; and d. water.
31. A formulation according to claim 30 in which the formulation
further comprises an organic carboxylic acid.
32. A formulation according to claim 31 in which the organic
carboxylic acid is selected from the group consisting of citric
acid, oxalic acid, lactic acid, tartaric acid, glycine and mixtures
of such acids.
33. A formulation according to claim 32 in which the organic
carboxylic acid is present in an amount that is from 2 to 10 wt %
of the formulation.
34. A formulation according to claim 30 in which the abrasive
particles are silica particles with a volume average particle size
of 15 to 60 nanometers.
35. A formulation according to claim 30 in which the amount of
abrasive in the formulation is from 2 to 10 wt % of the weight of
the formulation.
36. A formulation according to claim 30 in which the oxidizing
agent is selected from the group consisting of peroxides,
periodates, percarbamates and mixtures thereof.
37. A formulation according to claim 36 in which the oxidizing
agent is hydrogen peroxide in a concentration of from 0.1 to 6 wt %
of the formulation weight.
38. A formulation according to claim 30 in which the moderator is
selected from the group consisting of compounds having the group
--PO.sub.x, where x is from 1 to 4, and mixtures thereof.
39. A formulation according to claim 38 in which the moderator is
present in the formulation in an amount that represents from 0.1 to
6 wt % of the formulation weight.
40. A formulation according to claim 30 in which the accelerant is
selected from the group consisting of
1-hydroxyethylidene-1,1-diphosphoni- c acid (HEDP), aminotri
(methylenephosphonic acid) (ATMP), N-(2-hydroxyethyl])-N,N-di
(methylenephosphonic acid) (HEMPA),
2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and mixtures
thereof.
41. A formulation according to claim 40 in which the accelerant is
present in the formulation in an amount that is from 0.1 to 6 wt %
of the formulation weight.
42. A process for the chemical-mechanical planarization of the
surface of a nickel/phosphorus alloy containing from 9 to 12% of
phosphorus which comprises polishing the surface in the presence of
a slurry comprising a dispersion of abrasive particles with
particle sizes from 15 to 80 nanometers and selected from the group
consisting of silica, alumina, titania, ceria, zirconia and
mixtures thereof dispersed in a formulation comprising: a. an
oxidant; b. a moderator of the action of the oxidizing agent which
comprises a phosphate or phosphite group; c. an accelerant
comprising phosphonate groups; and d. water.
43. A process according to claim 42 in which an organic carboxylic
acid is added to the formulation.
44. A process according to claim 43 in which the organic carboxylic
acid is selected from the group consisting of citric acid, oxalic
acid, lactic acid, tartaric acid, glycine and mixtures of such
acids.
45. A process according to claim 42 in which the oxidizing agent is
selected from the group consisting of peroxides, periodates,
percarbamates and mixtures thereof.
46. A process according to claim 45 in which the oxidizing agent is
hydrogen peroxide in a concentration of from 0.1 to 6 wt % of the
formulation weight.
47. A process according to claim 42 in which the moderator is
selected from the group consisting of compounds having the group
--PO.sub.x, where x is from 1 to 4, and mixtures thereof.
48. A process according to claim 42 in which the accelerant is
selected from the group consisting of
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), aminotri
(methylenephosphonic acid) (ATMP), N-(2-hydroxyethyl])-N,N-di
(methylenephosphonic acid) (HEMPA),
2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and mixtures
thereof.
49. A CMP formulation which comprises a dispersion of abrasive
particles comprising silica with particle sizes from 15 to 80
nanometers dispersed in a formulation comprising: a. an oxidant; b.
a moderator of the action of the oxidizing agent which comprises a
phosphate or phosphite group; c. an accelerant comprising
phosphonate groups; and d. water.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation application of
U.S. patent application Ser. No. 10/831,946, filed Apr. 26, 2004,
which is a continuation application of U.S. patent application Ser.
No. 10/080,853, filed Feb. 22, 2002 (now U.S. Pat. No. 6,755,721),
entitled "Chemical Mechanical Polishing of Nickel Phosphorous
Alloys," naming inventors Douglas Edwin Ward and David Solomos,
both applications are incorporated herein by reference in their
entirety.
TECHNICAL FIELD OF THE INVENTION
[0002] This invention relates to CMP ("chemical mechanical
planarization") materials and specifically to CMP materials for use
in treating nickel-phosphorous alloys. The specific alloys targeted
by the present invention are known as high-phosphorus alloys and
contain 9 to 12 wt % of phosphorus, such alloys are conventionally
deposited via an auto catalytic nickel plating process, typically
called electroless nickel plating. Specifically in the manufacture
of hard disks for hard-disk-drives (memory storage media), said
nickel-phosphorous alloys are deposited on an aluminum
substrate.
BACKGROUND OF THE INVENTION
[0003] To manufacture hard disk drives, certain processes require
an electroless nickel-plated substrate to demonstrate a highly
planar surface. "Planarity" is quantified through the measurement
of "waviness", "flatness" and "roughness". In addition to
planarity, certain criteria determine the further processing of
post electroless nickel-plated, aluminum substrates. In totality,
these criteria are "waviness", "roughness", "outer diameter
curvature", "flatness" and surface defects. Waviness, roughness,
outer diameter curvature and flatness are to be at a minimum in
this context. Surface defects such as "pits", "bumps" and
"scratches" are defined by any disruption in the nickel-phosphorus
lattice, which has a depth or height greater than or equal to
twelve angstroms. In addition to seeking a planar surface that is
void of surface defects, the CMP process of nickel-phosphorous
plated, aluminum substrates must be accomplished in an efficient
manner with respect to cycle time and labor intensity.
[0004] Currently available CMP formulations have not succeeded in
removing a Ni--P layer at an adequate rate when using abrasive
particles consistent with achieving an adequately planar surface.
In practical terms this means abrasive particle sizes of from 15 to
120 nanometers. As a result the tendency has been to use abrasives
with a larger particle size to reduce the mean distance from
"peaks" to "valleys" across the nickel-phosphorous surface very
rapidly and follow with a process using particles with a range from
15-120 nm to create a "fine" finish with respect to planarity and
surface defects. A "fine" finish is defined by the optimum surface
condition available to this specific process.
[0005] The CMP formulation of this invention is specifically
designed to create a surface on a nickel-phosphorous layer that is
suitable in all respects for further operations in the fabrication
of a superior electronic component. Specifically it is capable of
producing a highly uniform, minimum waviness surface in a one-step
operation. It does this by using a CMP formulation that greatly
increases the material-removal effectiveness of abrasives with
particle sizes more usually associated with the later polishing
operation.
[0006] Normally in this context the CMP surface-generating process
is accomplished in two operations: a first involving aggressive
material removal until an approximate level is achieved and
thereafter a more gentle process in which the desired surface
finish, in terms of low surface roughness and micro-waviness, is
pursued. The solutions used in the first polishing stage are
frequently comprised of abrasive particles, (usually of alumina),
with a particle size of from about 0.3 to 0.44 micrometers, and a
chemical accelerant. The second action is a planarization action in
which the surface defects created by the first material removal
action are removed and a surface with an acceptable pre-determined
smoothness and minimal waviness is created. This second stage of
polishing is typically accomplished, using a finer abrasive
(colloidal silica) and a chemical accelerant, in the presence of an
oxidizer.
[0007] The two sequential operations can take a substantial amount
of time and are labor intensive. As a two-step process also
requires more handling of the substrates surface defects are
commonly introduced by human handling and transport of the product.
It is therefore desired to fabricate a process where a substrate is
properly processed via CMP in one step and on a single piece of
equipment. A suitable formulation meeting these criteria has now
been devised which can be used on a nickel/phosphorus alloy surface
to create a finish equivalent to that obtained using a conventional
two-stage process, in the same as or reduced time frame.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a statistical analysis diagram of removal rate
data.
[0009] FIG. 2 is a statistical analysis diagram of surface
roughness data.
GENERAL DESCRIPTION OF THE INVENTION
[0010] The present invention provides a CMP formulation for the
treatment of a nickel/phosphorus alloy which comprises a dispersion
of abrasive particles with particle sizes from 15 to 80 nanometers
and selected from the group consisting of silica, alumina, titania,
ceria, zirconia and mixtures thereof dispersed in a formulation
having a pH of from 2.4 to 2.6 comprising:
[0011] a. an oxidizer;
[0012] b. a chemical accelerant comprised of four groups:
[0013] (1) a phosphonate
[0014] (2) a carboxylic acid
[0015] (3) a phosphate or phosphite
[0016] (4) an amine
[0017] c. water.
[0018] The invention further comprises a single-step process
comprising subjecting a nickel-phosphorus alloy containing from 9
to 12% phosphorus deposited on a substrate to a CMP process using a
formulation as described above.
[0019] In preferred formulations according to the invention the
formulation comprises an organic carboxylic acid. This compound
attacks the surface and makes removal of the alloy more easily
accomplished. Examples of suitable acids include citric acid,
oxalic acid, lactic acid, tartaric acid, glycine and mixtures of
such acids.
[0020] The formulations of the invention are carefully balanced to
provide that the attack of the oxidant, (and any organic carboxylic
acid present), on the nickel-phosphorus alloy surface is not so
vigorous that material is removed in uncontrollable amounts that
can not be adequately sequestered by the phosphonate group in the
accelerant which is a chelating agent effective to chelate nickel
removed from the surface of the nickel-phosphorus alloy and prevent
re-deposition, or increase solubility by reacting with ligand
providing components in the formulation. An important element of
the balance is to maintain the pH at the above level and the level
of the second accelerant plays an important role in this
regard.
[0021] In selecting the oxidant, the most preferred example is
hydrogen peroxide because of the purity of the product and because
it leaves little or no residue. However other know oxidants, such
as periodates, sulphurous acid and percarbamates, can be used in
partial or complete substitution for hydrogen peroxide unless there
is a compatibility problem as is the case for mixtures of hydrogen
peroxide and potassium periodate. The preferred oxidant is however
hydrogen peroxide and most preferably in the form of a 35% by
weight solution in water.
[0022] The moderator for the activity of the oxidant comprises a
phosphite or phosphate group having the group --PO.sub.x, where x
is from 1 to 4. The preferred exemplar is phosphoric acid,
(including the meta-, ortho-, and pyrophosphoric acid
versions).
[0023] The accelerant also comprises chelating phosphonate groups
and suitable examples include 1-hydroxyethylidene-1,1-diphosphonic
acid (HEDP), aminotri (methylenephosphonic acid) (ATMP),
N-(2-hydroxyethyl)-N,N-di (methylenephosphonic acid) (HEMPA) and
2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC).
[0024] Of these HEDP is preferred. This component increases the
solubility of the nickel removed from the surface and aids in
producing a clean surface readily flushed clean of all CMP
residues.
[0025] The accelerant also comprises amine, amide or ammonium
groups and suitable exemplars of such compounds include ammonium
hydroxide, ammonium salts such ammonium nitrate, urea, formamide
acetate, biuret, ethylene diamine and glycine. Mixtures of such
compounds can also be used. This compound also acts as a ligand to
keep nickel in a soluble form after removal from the surface.
[0026] The amounts of the components in the formulation are
preferably as follows:
[0027] Abrasive: from 2 to 10 and more preferably from 3 to 6 wt.
%;
[0028] Oxidizer: from 1 to 6 wt. % and preferably 1 to 4 wt % of
the active oxidant.
[0029] Phosphate or Phosphite: from 0.1 to 6 and more preferably
from 0.1 to 4 wt. %;
[0030] Phosphonate: from 0.1 to 6 and more preferably from 0.1 to 4
wt. %;
[0031] Amine Amid Amide or Ammonium: from 0.1 to 6 and more
preferably from 0.1 to 4 wt. %; and
[0032] Organic Carboxylic Acid: from 0.1 to 6 and more preferably
from 0.1 to 4 wt. %.
[0033] Water: The balance up to 100 wt. %
[0034] The most preferred abrasive component of the mixture for use
on nickel-phosphorus substrates is silica, having a mean particle
size of 15 to 120 nm, preferably from 15 to 80 nm and most
preferably from 15 to 60 nanometers. The most suitable silicas have
mono-dispersed, essentially spherical particles. Two suitable
silica solutions are available as 30% by weight solid dispersions.
A-Green Corp. and DuPont AirProducts NanoMaterials manufacture
these products under the trade names BESIL-38A and Syton HD-700
respectively. Of these solutions, Syton HD-700 is preferred.
DESCRIPTION OF PREFERRED EMBODIMENTS
EXAMPLES
[0035] A statistically analytical approach was utilized to
formulate this invention. In order to eliminate excess variables in
the development process, certain equipment and parameters were held
constant. These equipment and their parameters were as follows:
1 TABLE A Polish Machine Speedfan 9h-5 Lower Platen Speed 4.0 rpm
Sun Gear Radius 3.5 Inches Sun Gear Speed 9.5 rpm Ring Gear Speed
8.5 rpm Carrier Diameter 9 inches Number of Work Pieces 6 Total
Down Force 48 kg Process Time 6 minutes Ramp to Down Force 20
seconds Total Slurry Flow-Rate 126 mL/min Polish Pad Rodel - DPM
1000 Roughness Measurement Schmitt TMS Removal Measurement Satorius
3100S Balance Cleaning Machine Oliver Singe Rail Double-Spaced
Number of Work Pieces 10 Brush Pressure (air) 40 psi Soap Time 1
sec Rinse Time (D1 spray) 1 sec Detergent AmberClean 527-L Drying
Machine Semitool Stand-Alone Dryer Rotor Speed 2700 rpm Rinse Cycle
30 sec DI Flow Rate .5 gpm Dry Cycle 180 sec Air Pressure 60
psi
[0036] The procedure by which slurry was evaluated through this
development process is depicted in the flow chart below:
2TABLE B 1
[0037] In addition to holding the procedures and process equipment
and parameters constant, the concentration of colloidal silica was
held constant at 5.71 percent by weight. This is to say that in
every iteration of slurry, the concentration of colloidal silica by
weight was held constant at 5.71 percent.
Example 1
[0038] This example illustrates the contribution to removal rate by
individual chemical groups in the presence of an oxidizer. An
initial screening was to be performed involving forty-eight
different constituents. At this initial stage of testing, the
concentration of hydrogen peroxide as a thirty-five percent by
weight solution was held constant at 2.57. This is to say that
during the first phase of the slurry development process hydrogen
peroxide in the form of a thirty-five percent by weight solution
was held constant in every iteration of slurry at a total
percentage by weight of 2.57. Each of the remaining forty-seven
constituents was evaluated as a one percent by weight solution
comprised of silica as described above, hydrogen peroxide as
described above, the specific constituent and the remaining weight
percent water. A listing of these constituents and the product
codes assigned to them are found in table 1a. The procedure by
which each of these constituents was evaluated is according to the
Process Flow Diagram depicted in table B. Removal rate data in the
form of total grams removal was collected from each slurry
evaluated. This data was then analyzed by analysis of variance and
a p-value obtained. A p-value of 0.00 was observed indicating that
there was greater difference in removal data from slurry to slurry
than within the data set acquired for an individual slurry. This is
to say that there is sufficient statistical data to make inferences
about the performance of each slurry. The data concerning the total
removal of the nickel-phosphorous layer facilitated by each slurry
is displayed in table 1b.
3TABLE 1a Code Date Run Name Accelerants Comments Mar. 07, 2001 A0
Hydrogen peroxide, 35% A1 Ammonium nitrate A2 Hydroxylamine
nitrate, 50% A3 Monoethanolamine Mar. 09, 2001 A4 Guanidine
carbonate A5 Ethylenediamine A6 Aluminum nitrate, 9hydrate A7
Calcium nitrate, 4hydrate A8 Ceric ammonium nitrate Mar. 12, 2001
A9 Chrome III nitrate, 9hydrate A10 Copper II nitrate, 3hydrate A11
Magnesium nitrate, 6hydrate A12 Nickel nitrate, 6hydrate Mar. 14,
2001 A13 Potassium nitrate A14 Potassium stannate, Incompatibility
3hydrate with hydrogen peroxide, not evaluated A15 Zinc II nitrate,
6hydrate A16 Cyanic acid Possible safety issues existed, not
evaluated Mar. 16, 2001 A17 HEDP, 60% aqueous A18 Ammonium
fluoroborate A19 Sodium fluorophosphate A20 HPA, 50% aqueous A21
Potassium iodate Mar. 19, 2001 A22 Potassium periodate
Incompatibility with hydrogen peroxide, not evaluated A23
Phosphoric acid, 85% aqueous A24 Sodium selenate A25 Ammonium
thiocyanate A26 Ammonium vanadate Possible safety issues existed,
not evaluated Mar. 20, 2001 A27 Citric acid A28 L-Cysteine A29
Glycine A30 Lactic acid A31 Oxalic acid Mar. 21, 2001 A32 Tartaric
acid A33 Hydrogen peroxide, 35% A34 Urea A35 Oxamide Possible
safety issues existed, not evaluated A36 Cyanamide Possible safety
issues existed, not evaluated Mar. 22, 2001 A37 Dimethylglyoxime
Incompatibility with hydrogen peroxide, not evaluated A38 Manganese
II nitrate, 50% A39 Zirconyl nitrate Incompatibility with hydrogen
peroxide, not evaluated A40 Tin IV oxide, 15%, 15 nm Mar. 23, 2001
A41 Formamid Acetate A42 Formamid Sulfinic Acid Not evaluated due
to unavailability of raw materials A43 Mayoquest 1320 A44 Mayoquest
2100 A45 Taurine A46 Biuret A47 Mayoquest 1200 Not evaluated due to
unavailability of raw materials
[0039]
4TABLE 1b Analysis of Variance for Removal Source DF SS MS F P
Slurry A 36 2.827991 0.078555 227.07 0.000 Error 74 0.025600
0.000346 Total 110 2.853591 Individual 95% CTs For Mean Based on
Pooled StD Level N Mean StDev
-----------+-----------+----------+------ ----- 0 3 0.23667 0.00577
*) 1 3 0.34667 0.01528 (*) 2 3 0.40333 0.01155 (*) 3 3 0.33333
0.02082 (*) 4 3 0.29667 0.01528 (*) 5 3 0.41333 0.02309 (* 6 3
0.55333 0.03055 (*) 7 3 0.25333 0.03055 (*) 8 3 0.36667 0.00577 (*)
9 3 0.42000 0.01000 (*) 10 3 0.29333 0.01528 (*) 11 3 0.06000
0.02646 *) 12 3 0.24333 0.00577 (*) 13 3 0.30000 0.02000 (*) 15 3
0.21333 0.02309 (* 17 3 0.55000 0.01732 (*) 18 3 0.35667 0.00577
(*) 19 3 0.46667 0.02887 (*) 20 3 0.56333 0.02887 (* 21 3 0.27333
0.00577 (*) 23 3 0.56000 0.01000 *) 24 3 0.38333 0.01528 (*) 25 3
0.08667 0.00577 *) 27 3 0.58667 0.01528 *) 28 3 0.03000 0.00000 (*)
29 3 0.51000 0.01000 *) 30 3 0.54333 0.00577 (*) 31 3 0.73333
0.03055 (*) 32 3 0.58000 0.01000 (*) 34 3 0.27667 0.01155 (*) 38 3
0.22000 0.00000 (*) 40 3 0.28667 0.00577 *) 41 3 0.50333 0.04619
(*) 43 3 0.54000 0.01732 (* 44 3 0.48333 0.02807 (*) 45 3 0.25333
0.00577 (*) 46 3 0.25667 0.00577 (*) Pooled StDev = 0.01860
-----------+-----------+-----------+----------- 0.25 0.50 0.75
[0040] Table 1b, shows a myriad of possible constituents as
candidates for slurry with adequate removal rate. Current state of
the art colloidal silica slurries remove the nickel-phosphorous
layer at rates from 7 mg-12 mg per minute per disk, which in
comparison to this evaluation would equate to 0.252 g-0.432 g total
removal. Table 1b shows thirteen slurries which surpass this
current bench mark and have coded units of A6, A17, A19, A20, A23,
A27, A29, A30, A31, A32, A41, A43, and A44. In uncoded unites,
these constituents are respectively aluminum nitrate,
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), sodium
fluorophosphate, hydroxyphosphono acetate, phosphoric acid, citric
acid, glycine, lactic acid, oxalic acid, tartaric acid, formamid
acetate, aminotri (methylenephosphonic acid) (ATMP) and
2-phosphonobutane-1,2,4-tricarboxyl- ic acid (PBTC). Each of these
constituents in the presence of an oxidizer, (hydrogen peroxide in
this specific example) show removal rate capabilities superior to
the current state of the art.
Example 2
[0041] This example illustrates the effects and interactions of ten
specific constituents. A fractional factorial design of experiment
model was utilized to approximate the magnitude of interactions of
ten constituents up through the third-order. This is to say that
through statistical analysis of removal data, the effects
individually and interactions with any one or two other
constituents were evaluated. Process procedures, parameters and
equipment were held constant as described in tables A and B to
evaluate constituents with coded units A0, A5, A6, A17, A20, A23,
A27, A29, A31 and A32. In uncoded units, those constituents were
hydrogen peroxide, ethylene diamine, aluminum nitrate, HEDP, HPA,
phosphoric acid, citric acid, glycine, oxalic acid and tartaric
acid respectively. A design of experiment model of resolution four
was utilized where the forty-two slurries were formulated according
to table 2a. Further, this table describes the actual percent by
weight each constituent was present in a given slurry. This is to
say that in the first slurry evaluated, denoted by RunOrder 1,
constituents A29, A31, A32 and A5 each were present in
concentrations of 1 percent by weight of the total solution while
A0 was present in 2.57 percent by weight of the total solution.
Silica was held constant as described above at a percent by weight
of 5.71 and the remaining weight percent was water.
5TABLE 2a Run Order A6 A17 A20 A23 A27 A29 A31 A32 A5 A0 1 0 0 0 0
0 1 1 1 1 2.57 2 1 0 0 0 0 0 0 0 0 2.57 3 0 1 0 0 0 0 0 0 1 0.00 4
1 1 0 0 0 1 1 1 0 0.00 5 0 0 1 0 0 0 0 1 0 0.00 6 1 0 1 0 0 1 1 0 1
0.00 7 0 1 1 0 0 1 1 0 0 2.57 8 1 1 1 0 0 0 0 1 1 2.57 9 0 0 0 1 0
0 1 0 0 0.00 10 1 0 0 1 0 1 0 1 1 0.00 11 0 1 0 1 0 1 0 1 0 2.57 12
1 1 0 1 0 0 1 0 1 2.57 13 0 0 1 1 0 1 0 0 1 2.57 14 1 0 1 1 0 0 1 1
0 2.57 15 0 1 1 1 0 0 1 1 1 0.00 16 1 1 1 1 0 1 0 0 0 0.00 17 0 0 0
0 1 1 0 0 0 0.00 18 1 0 0 0 1 0 1 1 1 0.00 19 0 1 0 0 1 0 1 1 0
2.57 20 1 1 0 0 1 1 0 0 1 2.57 21 0 0 1 0 1 0 1 0 1 2.57 22 1 0 1 0
1 1 0 1 0 2.57 23 0 1 1 0 1 1 0 1 1 0.00 24 1 1 1 0 1 0 1 0 0 0.00
25 0 0 0 1 1 0 0 1 1 2.57 26 1 0 0 1 1 1 1 0 0 2.57 27 0 1 0 1 1 1
1 0 1 0.00 28 1 1 0 1 1 0 0 1 0 0.00 29 0 0 1 1 1 1 1 1 0 0.00 30 1
0 1 1 1 0 0 0 1 0.00 31 0 1 1 1 1 0 0 0 0 2.57 32 1 1 1 1 1 1 1 1 1
2.57 33 0 1 0 0 0 0 0 0 0 2.57 34 0 0 1 0 0 0 0 0 0 2.57 35 0 0 0 1
0 0 0 0 0 2.57 36 0 0 0 0 1 0 0 0 0 2.57 37 0 0 0 0 0 1 0 0 0 2.57
38 0 0 0 0 0 0 1 0 0 2.57 39 0 0 0 0 0 0 0 1 0 2.57 40 0 0 0 0 0 0
0 0 1 2.57 41 0 0 0 0 0 0 0 0 0 2.57 42 0 1 0 0 0 0 0 0 1 2.57
[0042] The quantitative results with respect to estimated effects
and coefficients of this evaluation are found in table 2b. The
coefficients denoted by "Coef" in table 2b indicate the magnitude
of the effect of an individual constituent or interaction. The
statistical significance of these results is described by a p-value
which is denoted "P" in table 2b. A p-value less than 0.05 denotes
a statistical significance. This is to say that when a p-value less
than 0.05 is observed, these is sufficient statistical evidence to
make inferences about the contribution of an individual constituent
or interaction to the system with respect to removal rate.
6TABLE 2b Estimated Effects and Coefficients (coded units) Term
Effect Coef SE Coef T P Constant 0.3289 0.002580 123.60 0.000 A6
0.0156 0.0078 0.002580 3.03 0.003 A17 -0.0598 -0.0299 0.002580
-11.59 0.000 A20 0.0348 0.0174 0.002580 6.74 0.000 A23 -0.0127
-0.0064 0.002580 -2.46 0.016 A27 0.0281 0.0141 0.002580 5.45 0.000
A29 -0.0352 -0.0176 0.002580 -6.82 0.000 A31 0.0698 0.0349 0.002580
13.53 0.000 A32 -0.0677 -0.0339 0.002580 -13.12 0.000 A5 -0.0756
-0.0378 0.002580 -14.66 0.000 A0 0.3390 0.1685 0.002580 65.70 0.000
A6*A17 -0.0185 -0.0093 0.002580 -3.59 0.001 A6*A20 -0.0131 -0.0066
0.002580 2.54 0.013 A6*A23 0.0494 0.0247 0.002580 9.57 0.000 A6*A27
-0.0340 -0.0170 0.002580 -6.58 0.000 A6*A29 -1.0115 0.5057 0.024878
-20.33 0.000 A6*A31 -0.0140 -0.0070 0.002580 -2.71 0.008 A6*A32
0.0235 0.0118 0.002580 4.56 0.000 A6*A5 0.3246 0.1623 0.010319
15.73 0.000 A6*A0 -0.3925 -0.1962 0.011392 -17.23 0.000 A17*A20
0.0090 0.0045 0.002580 1.74 0.006 A17*A23 -0.0394 -0.0197 0.002580
-7.63 0.000 A17*A27 0.0698 0.0349 0.002580 13.53 0.000 A17*A29
0.0085 -0.0043 0.002580 -1.66 0.102 A17*A31 0.0131 0.0066 0.002580
2.54 0.013 A17*A32 0.4100 0.2050 0.013772 14.89 0.000 A17*A5
-0.1400 0.0700 0.007297 -9.59 0.000 A17*A0 -0.3748 -0.1874 0.010319
-18.16 0.000 A20*A23 0.0102 0.0051 0.002580 1.98 0.051 A20*A27
0.4994 0.2497 0.013772 18.13 0.000 A20*A29 1.1023 0.5511 0.025342
21.75 0.000 A20*A31 -0.5856 -0.2929 0.013772 -21.27 0.000 A20*A32
0.1665 0.0832 0.007297 11.41 0.000 A20*A5 -0.4369 -0.2184 0.013651
-16.00 0.000 A23*A27 0.0027 0.0014 0.002580 0.52 0.601 A23*A29
-0.0523 0.0261 0.002580 -10.14 0.000 A23*A31 0.1598 0.0799 0.007297
10.95 0.000 A23*A32 0.5769 0.2884 0.013092 20.76 0.000 A27*A29
0.2948 0.0974 0.007297 13.35 0.000 A27*A32 -1.0546 -0.5273 0.025210
20.92 0.000 A29*A32 -0.5333 -0.2667 0.013651 -19.53 0.000
A17*A20*A23 1.0433 0.5217 0.024744 21.08 0.000 Analysis of Variance
for Sample (coded units) Source DF Seq SS Adj SS Adj MS F P Main
Effects 10 4.29746 3.25494 0.329494 515.73 0.000 2-Way 30 0.63745
0.67552 0.029184 45.68 0.000 Interactions 3-Way 1 0.28397 0.28397
0.283968 444.47 0.000 Interactions Residual 84 0.05367 0.05367
0.000639 Error Pure Error 84 0.05367 0.05367 0.000639 Total 125
0.25655
[0043] The beneficial second order interactions obtained from this
evaluation are as follows:
[0044] Beneficial Interactions
[0045] HEDP:Ethylenediamine (slightly significant)
[0046] Aluminum Nitrate:Tartaric Acid
[0047] Aluminum Nitrate:Glycine
[0048] Aluminum Nitrate:Phosphoric Acid
[0049] Aluminum Nitrate:Glycine
[0050] Phosphoric Acid:HPA (slightly significant)
[0051] Citric Acid:HEDP
[0052] HPA:Glycine
[0053] Aluminum Nitrate:Ethylenediamine (slightly significant)
[0054] Citric Acid:Ethylenediamine
[0055] HPA:Glycine
[0056] Citric Acid:HPA:Glycine
[0057] HPA:Ethylenediamine
[0058] Phosphoric Acid:Citric Acid
[0059] Citric Acid:Glycine (slightly significant)
Example 3
[0060] Example 3 illustrates the effects and interactions more
specifically of constituents, in coded units, A17, A20, A23, A27
and A29. These constituents in uncoded units are HEDP, HPA,
phosphoric acid, citric acid and glycine respectively. Again,
process procedures, parameters and equipment were held constant as
described in tables A and B. Silica was present in each slurry at a
concentration of 5.71 percent by weight of the total solution.
Hydrogen peroxide in a 35 percent by weight solution was held
constant in each slurry at a level of 2.57 percent by weight of the
total solution. A fractional factorial design of experiment model
was created to incorporate these chemistries. By so doing, nineteen
slurries were formulated and quantitatively analyzed by examining
removal rate data. The design of experiment model is defined in
table 3a. A statistical analysis of this data is found in table 3b
where the estimated effects and coefficients of individual
constituents and interactions up through the fourth order are
displayed.
7 TABLE 3a Run Order A17 A27 A29 A20 A23 1 0.1 0.1 0.1 0.1 0 2 1.1
0.1 0.1 0.1 0 3 0.1 1.1 0.1 0.1 0 4 1.1 1.1 0.1 0.1 0 5 0.1 0.1 1.1
0.1 0 6 1.1 0.1 1.1 0.1 0 7 0.1 1.1 1.1 0.1 0 8 1.1 1.1 1.1 0.1 0 9
0.1 0.1 0.1 1.1 0 10 1.1 0.1 0.1 1.1 0 11 0.1 1.1 0.1 1.1 0 12 1.1
1.1 0.1 1.1 0 13 0.1 0.1 1.1 1.1 0 14 1.1 0.1 1.1 1.1 0 15 0.1 1.1
1.1 1.1 0 16 1.1 1.1 1.1 1.1 0 17 1.0 1.0 0.0 0.0 1 18 1.0 1.0 0.0
0.0 1 19 1.0 1.0 0.0 0.0 1
[0061]
8TABLE 3b Estimated Effects and Coefficients for Sample (uncoded
units) Term Effect Coef SE Coef T P Constant 0.53518 0.007564 70.76
0.000 A17 0.05403 0.02701 0.002743 9.85 0.000 A27 0.02744 0.01372
0.002743 5.00 0.000 A29 -0.04166 -0.02083 0.003003 6.94 0.000 A20
-0.04533 -0.02266 0.003003 -7.55 0.000 A23 0.01349 0.00674 0.007677
0.88 0.385 A17*A27 -0.03435 -0.01717 0.002743 -6.26 0.000 A17*A29
-0.02003 0.01001 0.003003 -3.34 0.002 A17*A20 -0.03286 0.01643
0.003003 -5.47 0.000 A27*A29 -0.02727 -0.01364 0.003003 -4.54 0.000
A27*A20 -0.03460 -0.01730 0.003003 -5.76 0.000 A29*A20 -0.04084
-0.02042 0.003287 6.21 0.000 A17*A27*A29 0.03630 0.01817 0.003003
6.05 0.000 A17*A27*A20 0.03451 0.01726 0.003003 5.75 0.000
A17*A29*A20 0.04386 0.02193 0.003287 6.67 0.000 A27*A29*A20 0.03277
0.01639 0.003287 4.99 0.000 A17*A27*A29*A20 -0.00151 -0.00076
0.003287 -0.23 0.819 Analysis of Variance for Sample (coded units)
Source DF Seq SS Adj SS Adj MS F P Main Effects 5 0.117544 0.100321
0.0200643 56.66 0.000 2-Way 6 0.049612 0.060841 0.0101402 28.63
0.000 Interactions 3-Way 4 0.049292 0.048996 0.0122491 34.59 0.000
Interactions 4-Way 1 0.000019 0.000019 0.0000187 0.05 0.819
Interactions
[0062] Table 3a depicts the levels at which each of the
constituents were evaluated. For example, in addition to silica and
hydrogen peroxide which were afore mentioned, slurry number 3,
indicated by RunOrder 3, comprised 0.1 percent A17, 1.1 percent
A27, 0.1 percent A29, 0.1 percent A20 and no A23. Each of the
percentages described above are indicative of a percent by weight
of the total slurry. The significance of this example is that A29
and A20 are shown to have an adverse effect on removal rate when in
the presence of all the other constituents in this specific
evaluation. Approximate values of said negative impacts in this
specific system are found in table 3b and are characterized by
their estimated coefficients; denoted by "Coef".
Example 4
[0063] Example 4 depicts the effects of individual constituents and
interactions of the preferred constituents in this invention. In
coded units, these constituents are A0, A17, A23 and A27.
Respectively, these constituents in uncoded units are hydrogen
peroxide, HEDP, phosphoric acid and citric acid. All procedures,
parameters and equipment were held constant as described in tables
A and B. A fractional factorial design of experiment model was
utilized to determine the magnitude of contributions with respect
to removal rate of each constituent. The fractional factorial
design of experiment model is portrayed in table 4a. Silica was
present as 5.71 percent by total weight of each slurry. Ammonium
hydroxide was utilized to standardize the pH throughout the
evaluation at 2.5. Quantitative statistical analysis of the results
of this example is available in table 4b. The concentrations of
each constituent in each slurry is depicted in table 4a. For
example, the first slurry evaluated, denoted by RunOrder 1,
comprised of 0.25 weight percent A17, 0.25 weight percent A23, 0.27
weight percent A27 and 1.29 weight percent A0. Said weight percent
values are indicative of total weight percent.
9TABLE 4a Run Order A17 A23 A27 A0 1 0.25 0.25 0.25 1.29 2 1.25
0.25 0.25 3.86 3 0.25 1.25 0.25 3.86 4 1.25 1.25 0.25 1.29 5 0.25
0.25 1.25 3.86 6 1.25 0.25 1.25 1.29 7 0.25 1.25 1.25 1.29 8 1.25
1.25 1.25 3.86
[0064]
10TABLE 4b Estimated Effects and Coefficients for Sample (coded
units) Term Effect Coef SE Coef T P Constant 0.59000 0.003773
156.37 0.000 A17 0.04167 0.02093 0.003773 5.52 0.000 A23 0.50000
0.02500 0.003773 6.63 0.000 A27 -0.02367 -0.01083 0.003773 -2.87
0.011 A0 0.03667 0.01833 0.003773 4.86 0.000 A17*A23 -0.03833
-0.01917 0.003773 5.88 0.000 A17*A27 0.00333 0.00167 0.003773 0.44
0.665 A17*A0 -0.00500 -0.00250 0.003773 -0.66 0.517 Analysis of
Variance for Sample (coded units) Source DF Seq SS Adj SS Adj MS F
P Main Effects 4 0.036300 0.036300 0.0090750 26.56 0.000 2-Way 3
0.009033 0.009033 0.0030111 8.81 0.001 Interactions Residual 16
0.005467 0.005467 0.0003417 Error Pure Error 16 0.005467 0.005467
0.0003417 Total 23 0.050800
[0065] This example illustrates the significant interactions
between the preferred constituents in this invention up through the
second order.
Example 5
[0066] This example illustrates the performance capability of this
invention. All process parameters and equipment were held constant
as described in Tables A and B when slurry comprising hydrogen
peroxide, citric acid, HEDP, phosphoric acid, ammonium hydroxide,
silica and water was evaluated. Thirty different runs were
performed according to tables A and B. The removal and surface
roughness data from these thirty runs were statistically analyzed.
Removal rate data is portrayed graphically in FIG. 1 while surface
roughness data is portrayed in FIG. 2. The data acquired from this
example depicts a mean removal rate of 18.37 mg/min/disk.
Accompanying this mean removal rate is a standard deviation of
0.779 mg/min/disk. The surface of the nickel-phosphorous after
polishing with this invention is void of defects. Defects are
defined as any interruption in the nickel-phosphorous lattice
having depth or height greater than twelve angstroms. This is
observed through the surface roughness data obtained from this
evaluation. A mean surface roughness of 1.47 angstroms was observed
with a standard deviation of 0.17 angstroms. This value of 1.47
angstroms is indicative of the surface condition of the substrate.
As measured on a TMS 2000, manufactured by Schmitt Inc., the
average difference from peak to valley on the surface of the disks
measured was 1.47 angstroms.
* * * * *