# Patent

## Title
Method for chemical mechanical polishing tungsten

## Abstract

A method for chemical mechanical polishing of a substrate comprising tungsten using a nonselective chemical mechanical polishing composition.

## Background
The present invention relates to a method for chemical mechanical polishing of a substrate comprising tungsten. More particularly, the present invention relates to a method for chemical mechanical polishing of a semiconductor substrate comprising tungsten vias.
Tungsten is widely used in semiconductor manufacturing for the formation of contact vias and holes connecting inter layer metal lines in integrated circuit fabrications. Typically, via holes are etched through an interlevel dielectric (ILD) to interconnection lines or to a semiconductor substrate. A thin adhesion layer of, for example, titanium nitride or titanium may then be formed over the ILD and into the etched via hole. A tungsten film is then blanket deposited over the adhesion layer and into the via. Excess tungsten is then removed by chemical mechanical polishing (CMP) to form the tungsten vias.
The chemical mechanical polishing composition used in the CMP is an important variable in determining the success of the CMP. Depending on the choice of the abrasive and other additives, the chemical mechanical polishing composition can be tailored to provide effective polishing of various layers present at desired polishing rates while minimizing surface imperfections, defects, corrosion, and erosion of the interlevel dielectric adjacent to the tungsten vias. Furthermore, the chemical mechanical polishing composition may be used to provide controlled polishing selectivity to other materials present at the surface of the substrate being polished such as, for example, titanium, titanium nitride, silicon nitride and the like.
Typically, the tungsten CMP process is accomplished using a chemical mechanical polishing composition that includes abrasive particles and a chemical reagent. Conventional polishing compositions for tungsten CMP use alumina (Al2O3) or silica (SiO2) fine particles as an abrasive material in a harsh oxidizing environment. The choice of the oxidizing agent depends on the overall formulation of the polishing composition and the specific requirements of the tungsten CMP integration process. The polishing compositions used are increasingly being formulated with ingredients that are designed to etch tungsten in an effort to enhance the tungsten removal rate exhibited by the composition. In many cases, however, the resulting composition etch tungsten in a manner that chemically etches tungsten from the surface instead of converting the tungsten to a soft oxidized film that is more easily removed from the surface by mechanical abrasion. Due to this enhanced chemical action, such compositions tend to cause recessing of the tungsten plug. Recessed tungsten vias, where the surface of the tungsten in the via is below that of the surrounding interlayer dielectric material can cause electrical contact problems to other areas of the device. Moreover, the recessing in the center of the tungsten vias can lead to increased nonplanarity of the device on subsequent levels of the device. Etching of the tungsten from the center of the vias can also cause undesirable “keyholing”.
One asserted solution for improving the tungsten via formation is disclosed by Grumbine, et al. in U.S. Pat. No. 6,136,711. Grumbine, et al. disclose a chemical mechanical polishing composition comprising: a compound that is capable of etching tungsten; and at least one inhibitor of tungsten etching, wherein the inhibitor of tungsten etching is a compound that includes a nitrogen containing functional group selected from compounds having three or more carbon atoms that form alkylammonium ions, amino alkyls having three or more carbon atoms, amino acids other than sulfur containing amino acids and mixtures thereof.
Use of an oxide buff step following the tungsten polish step provides an alternative means to achieve better tungsten via topography. Such oxide buff steps are becoming increasingly important as the contact size on semiconductor substrates continues to shrink.
Accordingly, there is a continuing need for new chemical mechanical polishing compositions and methods for use as tungsten buff formulations for achieving better topography performance.
The present invention provides a method for chemical mechanical polishing of a substrate, comprising: providing a substrate, wherein the substrate comprises tungsten; providing a chemical mechanical polishing slurry composition comprising (consisting essentially of), as initial components: water; 0.1 to 5 wt % of an abrasive; 0.005 to 0.1 wt % of a diquaternary compound according to formula (I):




wherein each A is independently selected from N and P; wherein R1 is selected from a saturated or unsaturated C1-C15 alkyl group, a C6-C15 aryl group and a C6-C15 aralkyl group; wherein R2, R3, R4, R5, R6 and R7 are each independently selected from selected from a hydrogen, a saturated or unsaturated C1-C15 alkyl group, a C6-C15 aryl group, a C6-C15 aralkyl group and a C6-C15 alkaryl group; and, wherein the anion in formula (I) can be any anion or combination of anions that balance the 2+ charge on the cation in formula (I); 0.001 to 10 wt % of at least one of a phthalic acid, a phthalic anhydride, a phthalate compound and a phthalic acid derivative; and, 0.001 to 10 wt % potassium iodate; wherein the chemical mechanical polishing composition provided has a pH of 1 to 4; wherein the chemical mechanical polishing composition exhibits a tungsten static etch rate of ≦5 Å/min and a tungsten removal rate of ≧100 Å/min; wherein the chemical mechanical polishing composition contains <0.001 wt % per-oxy oxidizer; and, wherein the chemical mechanical polishing composition contains <0.005 wt % corrosion inhibitor agent; providing a chemical mechanical polishing pad with a polishing surface; creating dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate with a down force of 0.69 to 34.5 kPa; and dispensing the chemical mechanical polishing slurry composition onto the chemical mechanical polishing pad at or near the interface between the chemical mechanical polishing pad and the substrate; wherein the substrate is polished; and, wherein some of the tungsten is removed from the substrate.

The present invention also provides a method for chemical mechanical polishing of a substrate, comprising: providing a substrate, wherein the substrate comprises tungsten; providing a chemical mechanical polishing slurry composition comprising (consisting essentially of), as initial components: water; 1.5 to 3.5 wt % of the abrasive, wherein the abrasive is a colloidal silica abrasive having an average particle size of 10 to 100 nm; 0.01 to 0.1 wt % of the diquaternary compound; wherein each A is a N; wherein R1 is a —(CH2)4— group; wherein R2, R3, R4, R5, R6 and R7 are each a —(CH2)3CH3 group; 0.01 to 1 wt % of ammonium hydrogen phthalate; and, 0.01 to 1 wt % potassium iodate; and, wherein the chemical mechanical polishing composition provided has a pH of 2 to 3; wherein the chemical mechanical polishing composition exhibits a tungsten static etch rate of ≦5 Å/min and a tungsten removal rate of ≧100 Å/min; wherein the chemical mechanical polishing composition contains <0.001 wt % per-oxy oxidizer; and, wherein the chemical mechanical polishing composition contains <0.005 wt % corrosion inhibitor agent; providing a chemical mechanical polishing pad with a polishing surface; creating dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate with a down force of 0.69 to 34.5 kPa; and dispensing the chemical mechanical polishing slurry composition onto the chemical mechanical polishing pad at or near the interface between the chemical mechanical polishing pad and the substrate; wherein the substrate is polished; and, wherein some of the tungsten is removed from the substrate.
The present invention also provides a method for chemical mechanical polishing of a substrate, comprising: providing a substrate, wherein the substrate comprises tungsten; providing a chemical mechanical polishing slurry composition comprising (consisting essentially of), as initial components: water; 1.5 to 3.5 wt % of the abrasive, wherein the abrasive is a colloidal silica abrasive having an average particle size of 25 to 75 nm; 0.01 to 0.03 wt % of the diquaternary compound according to formula (I); wherein each A is a N; wherein R1 is a —(CH2)4— group; wherein R2, R3, R4, R5, R6 and R7 are each a —(CH2)3CH3 group; 0.05 to 0.5 wt % of ammonium hydrogen phthalate; and, 0.1 to 0.5 wt % potassium iodate; wherein the chemical mechanical polishing composition provided has a pH of 2 to 3; wherein the chemical mechanical polishing composition exhibits a tungsten static etch rate of ≦5 Å/min and a tungsten removal rate of ≧100 Å/min; wherein the chemical mechanical polishing composition contains <0.001 wt % per-oxy oxidizer; and, wherein the chemical mechanical polishing composition contains <0.005 wt % corrosion inhibitor agent; providing a chemical mechanical polishing pad with a polishing surface; creating dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate with a down force of 0.69 to 34.5 kPa; and dispensing the chemical mechanical polishing slurry composition onto the chemical mechanical polishing pad at or near the interface between the chemical mechanical polishing pad and the substrate; wherein the substrate is polished; wherein some of the tungsten is removed from the substrate; wherein the chemical mechanical polishing composition facilitates a tungsten removal rate of ≧300 Å/min with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polishing pad; and wherein the substrate further comprises Si3N4; wherein at least some of the Si3N4 is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to Si3N4 removal rate selectivity of 2:1 to 1:2 with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polishing pad.


DETAILED DESCRIPTION
The method for chemical mechanical polishing of the present invention is useful for polishing a substrate comprising tungsten, particularly semiconductor wafers comprising tungsten vias. The chemical mechanical polishing composition used in the method of the present invention desirably exhibits a low tungsten static etch rate (≦5 Å/min) in a nonselective tailorable formulation.
The method for chemical mechanical polishing of a substrate of the present invention is useful for chemical mechanical polishing of a substrate comprising tungsten. The method for chemical mechanical polishing of a substrate of the present invention is particularly useful for chemical mechanical polishing of a semiconductor wafer having tungsten vias.
Preferably, the substrate polished using the method of the present invention optionally further comprises an additional material selected from phosphor silicate glass (PSG), boro-phosphor silicate glass (BPSG), undoped silicate glass (USG), spin-on-glass (SOG), tetraethyl orthosilicate (TEOS), plasma-enhanced TEOS (PETEOS), flowable oxide (FOx), high-density plasma chemical vapor deposition (HDP-CVD) oxide, and silicon nitride (Si3N4). Preferably, the substrate polished using the method of the present invention further comprises an additional material selected from TEOS and Si3N4.
Preferably, the water used as an initial component in the chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention is at least one of deionized and distilled to limit incidental impurities.
Abrasives suitable for use in the chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention include, for example, inorganic oxides, inorganic hydroxides, inorganic hydroxide oxides, metal borides, metal carbides, metal nitrides, polymer particles and mixtures comprising at least one of the foregoing. Suitable inorganic oxides include, for example, silica (SiO2), alumina (Al2O3), zirconia (ZrO2), ceria (CeO2), manganese oxide (MnO2), titanium oxide (TiO2) or combinations comprising at least one of the foregoing oxides. Modified forms of these inorganic oxides, such as, organic polymer-coated inorganic oxide particles and inorganic coated particles can also be utilized if desired. Suitable metal carbides, boride and nitrides include, for example, silicon carbide, silicon nitride, silicon carbonitride (SiCN), boron carbide, tungsten carbide, zirconium carbide, aluminum boride, tantalum carbide, titanium carbide, or combinations comprising at least one of the foregoing metal carbides, boride and nitrides. Preferably, the abrasive used is a colloidal silica abrasive. More preferably, the abrasive used is a colloidal silica having an average particle size of 1 to 100 nm (more preferably 10 to 100 nm, most preferably 25 to 75 nm) as determined by well known laser light scattering techniques.
The chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention preferably comprises, as an initial component, 0.1 to 5 wt % (more preferably 1.5 to 3.5 wt %) abrasive. Preferably, the abrasive is a colloidal silica abrasive. Most preferably, the chemical mechanical polishing composition of the present invention comprises, as an initial component, 0.1 to 5 wt % (more preferably 1.5 to 3.5 wt %) of a colloidal silica abrasive having an average particle size of 1 to 100 nm (more preferably 10 to 100 nm, most preferably 25 to 75 nm).
The chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention preferably comprises, as an initial component, a diquaternary substance according to formula (I):




wherein each A is independently selected from N and P, preferably each A is N; wherein R1 is selected from a saturated or unsaturated C1-C15 alkyl group, a C6-C15 aryl group and a C6-C15 aralkyl group (preferably a C2-C10 alkyl group; more preferably a C2-C6 alkyl group; still more preferably a —(CH2)6— group and a —(CH2)4— group; most preferably a —(CH2)4— group); wherein R2, R3, R4, R5, R6 and R7 are each independently selected from a hydrogen, a saturated or unsaturated C1-C15 alkyl group, a C6-C15 aryl group, a C6-C15 aralkyl group and a C6-C15 alkaryl group (preferably a hydrogen and a C1-C6 alkyl group; more preferably a hydrogen and a butyl group; most preferably a butyl group); and, wherein the anion in formula (I) can be any anion or combination of anions that balance the 2+ charge on the cation in formula (I) (preferably the anion(s) in formula (I) is(are) selected from halide anions, hydroxide anions, nitrate anions, sulfate anions and phosphate anions; more preferably halide anions and hydroxide anions; most preferably hydroxide anions). Preferably, the chemical mechanical polishing composition used comprises, as an initial component, 0.005 to 0.1 wt % (more preferably 0.01 to 0.1 wt %, most preferably 0.01 to 0.03 wt %) of a diquaternary substance according to formula (I). Most preferably, the chemical mechanical polishing composition used comprises, as an initial component, 0.005 to 0.1 wt % (more preferably 0.01 to 0.1 wt %, most preferably 0.01 to 0.03 wt %) of a diquaternary substance according to formula (I), wherein each A is N; R1 is a —(CH2)4— group; and, wherein R2, R3, R4, R5, R6 and R7 are each a —(CH2)3CH3 group. Inclusion of the optional diquaternary substance according to formula (I) in the chemical mechanical polishing slurry composition of the present invention provides (under the polishing conditions set forth in the Examples) an increased silicon oxide removal rate, a decreased Si3N4 removal rate and a slightly enhanced tungsten removal rate.

The chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention preferably comprises, as an initial component, 0.001 to 10 wt % (more preferably 0.01 to 1 wt %, most preferably 0.05 to 0.5 wt %) of at least one of a phthalic acid, a phthalic anhydride, a phthalate compound and a phthalic acid derivative. Preferably, phthalic acid is incorporated into the chemical mechanical polishing composition used through the addition of a phthalate compound such as for example, hydrogen potassium phthalate; or through the addition of a phthalic acid derivative such as, for example, ammonium hydrogen phthalate. Most preferably, the chemical mechanical polishing composition used comprises, as an initial component, 0.001 to 10 wt % (more preferably 0.01 to 1 wt %, most preferably 0.05 to 0.5 wt %) of ammonium hydrogen phthalate.
The chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention preferably comprises, as an initial component, 0.001 to 10 wt % (more preferably 0.01 to 1 wt %, most preferably 0.1 to 0.5 wt %) potassium iodate.
The chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention preferably has a pH of 1 to 4 (more preferably 2 to 3). Acids suitable for adjusting the pH of the chemical mechanical polishing composition include, for example, nitric acid, sulfuric acid and hydrochloric acid. Bases suitable for adjusting the pH of the chemical mechanical polishing composition include, for example, ammonium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and bicarbonate; preferably tetramethylammonium hydroxide.
The chemical mechanical polishing composition used in the chemical mechanical polishing method of the present invention optionally further comprises additional additives selected from defoaming agents, dispersants, surfactants and buffers.
The chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention is per-oxy oxidizer free. The term “per-oxy oxidizer” as used herein and in the appended claims means oxidizers selected from hydrogen peroxide, urea hydrogen peroxide, percarbonate salts, benzoyl peroxide, peracetic acid, sodium peroxide, di-tert-butyl peroxide, monopersulfate salts, dipersulfate salts, iron(III) compounds. The term “per-oxy oxidizer free” as used herein and in the appended claims means that the chemical mechanical polishing composition contains <0.001 wt % per-oxy oxidizer. Preferably, the chemical mechanical polishing composition contains <0.0005 wt % (more preferably <0.0001 wt %) per-oxy oxidizer.
The chemical mechanical polishing composition used in the method for chemical mechanical polishing of the present invention is corrosion inhibitor agent free. The term “corrosion inhibitor agent” as used herein and in the appended claims is a component that functions to inhibit the corrosion of tungsten by adsorbing to the surface to be polishing and forming a film thereon. Corrosion inhibitor agents, for example: benzotriazole; 1,2,3-benzotriazole; 5,6-dimethyl-1,2,3-benzotriazole; 1-(1,2-dicarboxyethyl)benzotriazole; 1-[N,N-bis(hydroxylethyl)aminomethyl]benzotrizole; or 1-(hydroxylmethyl)benzotriazole. The term “corrosion inhibitor agent free” as used herein and in the appended claims means that the chemical mechanical polishing composition contains <0.005 wt % corrosion inhibitor agent. Preferably, the chemical mechanical polishing composition contains <0.001 wt % (more preferably <0.0001 wt %) corrosion inhibitor agents.
The method for chemical mechanical polishing of the present invention preferably comprises: providing a substrate, wherein the substrate comprises tungsten (preferably wherein the substrate is a semiconductor wafers comprising tungsten vias); providing a chemical mechanical polishing slurry composition comprising (consisting essentially of), as initial components: water; 0.1 to 5 wt % (preferably 1.5 to 3.5 wt %) of the abrasive (preferably, wherein the abrasive is a colloidal silica abrasive having an average particle size of 10 to 100 nm (preferably 25 to 50 nm)); 0.005 to 0.1 wt % (preferably 0.01 to 0.1 wt %; more preferably 0.01 to 0.03 wt %) of a diquaternary compound according to formula (I):




wherein each A is independently selected from N and P (preferably, wherein each A is a N); wherein R1 is selected from a saturated or unsaturated C1-C15 alkyl group, a C6-C15 aryl group and a C6-C15 aralkyl group (preferably, R1 is a —(CH2)4— group); wherein R2, R3, R4, R5, R6 and R7 are each independently selected from selected from a hydrogen, a saturated or unsaturated C1-C15 alkyl group, a C6-C15 aryl group, a C6-C15 aralkyl group and a C6-C15 alkaryl group (preferably, wherein R2, R3, R4, R5, R6 and R7 are each a —(CH2)3CH3 group); and, wherein the anion in formula (I) can be any anion or combination of anions that balance the 2+ charge on the cation in formula (I); 0.001 to 10 wt % (preferably 0.01 to 1 wt %, more preferably 0.05 to 0.5 wt %) of at least one of a phthalic acid, a phthalic anhydride, a phthalate compound and a phthalic acid derivative (preferably ammonium hydrogen phthalate); and, 0.001 to 10 wt % (preferably 0.01 to 1 wt %; more preferably 0.1 to 0.5 wt %) potassium iodate; wherein the chemical mechanical polishing composition provided has a pH of 1 to 4 (preferably 2 to 3); wherein the chemical mechanical polishing composition exhibits a tungsten static etch rate of ≦5 Å/min (as measured under the conditions set forth in the Examples) and a tungsten removal rate of ≧100 Å/min (preferably ≧300 Å/min) (as measured under the polishing conditions set forth in the Examples); wherein the chemical mechanical polishing composition contains <0.001 wt % per-oxy oxidizer; and, wherein the chemical mechanical polishing composition contains <0.005 wt % corrosion inhibitor agent; providing a chemical mechanical polishing pad with a polishing surface; creating dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate with a down force of 0.69 to 34.5 kPa; and dispensing the chemical mechanical polishing slurry composition onto the chemical mechanical polishing pad at or near the interface between the chemical mechanical polishing pad and the substrate; wherein the substrate is polished; and, wherein some of the tungsten is removed from the substrate. Preferably, wherein the substrate further comprises TEOS, wherein at least some of the TEOS is removed from the substrate, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to TEOS removal rate selectivity (as measured under the polishing conditions set forth in the Examples) of 5:1 to 1:5. Preferably, the substrate further comprises Si3N4, wherein at least some of the Si3N4 is removed from the substrate, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to Si3N4 removal rate selectivity (as measured under the polishing conditions set forth in the Examples) of 2:1 to 1:2.

The method for chemical mechanical polishing of the present invention preferably comprises: providing a substrate, wherein the substrate comprises tungsten (preferably wherein the substrate is a semiconductor wafers comprising tungsten vias); providing a chemical mechanical polishing slurry composition comprising (consisting essentially of), as initial components: water; 1.5 to 3.5 wt % of the abrasive, wherein the abrasive is a colloidal silica abrasive having an average particle size of 25 to 75 nm; 0.01 to 0.03 wt % of the diquaternary compound according to formula (I); wherein each A is a N; wherein R1 is a —(CH2)4— group; wherein R2, R3, R4, R5, R6 and R7 are each a —(CH2)3CH3 group; 0.05 to 0.5 wt % of ammonium hydrogen phthalate; and, 0.1 to 0.5 wt % potassium iodate; wherein the chemical mechanical polishing composition provided has a pH of 2 to 3; wherein the chemical mechanical polishing composition exhibits a tungsten static etch rate of ≦5 Å/min (as measured under the conditions set forth in the Examples) and a tungsten removal rate of ≧100 Å/min (preferably ≧300 Å/min) (as measured under the polishing conditions set forth in the Examples); wherein the chemical mechanical polishing composition contains <0.001 wt % per-oxy oxidizer; and, wherein the chemical mechanical polishing composition contains <0.005 wt % corrosion inhibitor agent; providing a chemical mechanical polishing pad with a polishing surface; creating dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate with a down force of 0.69 to 34.5 kPa; and dispensing the chemical mechanical polishing slurry composition onto the chemical mechanical polishing pad at or near the interface between the chemical mechanical polishing pad and the substrate; wherein the substrate is polished; and, wherein some of the tungsten is removed from the substrate. Preferably, wherein the substrate further comprises TEOS, wherein at least some of the TEOS is removed from the substrate, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to TEOS removal rate selectivity (as measured under the polishing conditions set forth in the Examples) of 5:1 to 1:5. Preferably, the substrate further comprises Si3N4, wherein at least some of the Si3N4 is removed from the substrate, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to Si3N4 removal rate selectivity (as measured under the polishing conditions set forth in the Examples) of 2:1 to 1:2.
Some embodiments of the present invention will now be described in detail in the following Examples.
EXAMPLES
Chemical Mechanical Polishing Compositions
The chemical mechanical polishing compositions (CMPC's) tested are described in Table 1. The chemical mechanical polishing compositions A-F are comparative formulations, which are not within the scope of the claimed invention.















TABLE 1





CMPC
Abrasive A  
Abrasive Bχ
Diquat  
AHP
KIO3
H2O2
Glycine
pH























A
2.4
0.6
—
0.16
0.1
—
—
2.7


B
2.4
0.6
0.02
—
0.1
—
—
2.7


C
2.4
0.6
—
—
0.1
—
0.0033
2.7


D
2.4
0.6
—
—
0.1
—
—
2.7


E
2.4
—
0.015
0.2
0.05
2
—
2.3


F
2.4
0.6
0.03
0.3
0.05
2
—
2.3


1
2
0.4
0.015
0.3
0.5
—
—
2.3


2
2
0.4
0.015
0.3
1
—
—
2.3


3
2
0.4
0.015
0.3
2
—
—
2.3


4
2.4
0.6
0.03
0.3
1
—
—
2.3


5
2.4
0.6
0.02
0.16
0.1
—
—
2.3


6
2.4
0.6
0.02
0.24
0.2
—
—
2.3


7
2.4
0.6
0.02
0.08
0.2
—
—
2.7


8
2.4
0.6
0.02
0.08
0.3
—
—
2.5


9
2.4
0.6
0.02
0.16
0.1
—
—
2.7


10
2.4
0.6
0.02
0.16
0.2
—
—
2.5


11
2.4
0.6
0.02
0.08
0.1
—
—
2.5


12
2.4
0.6
0.02
0.16
0.3
—
—
2.7


13
2.4
0.6
0.02
0.24
0.1
—
—
2.5


14
2.4
0.6
0.02
0.24
0.2
—
—
2.7


15
2.4
0.6
0.02
0.16
0.3
—
—
2.3


16
2.4
0.6
0.02
0.24
0.3
—
—
2.5


17
2.4
0.6
0.02
0.08
0.2
—
—
2.3


18
2.8
0.8
0.02
0.16
0.2
—
—
2.5


19
2.4
0.6
0.02
0.16
0.1
—
—
2.7





 Klebosol TM PL1598-B25 colloidal silica having an average particle size of 25 nm manufactured by AZ Electronic Materials and commercially available from Rohm and Haas Electronic Materials CMP Inc.


χKlebosol ® II 1501-50 colloidal silica having an average particle size of 50 nm manufactured by AZ Electronic Materials and commercially available from Rohm and Haas Electronic Materials CMP Inc.


 HBBAH: N,N,N,N′,N′,N′-hexabutyl-1,4-butanediammonium dihydroxide from Sachem, Inc.” and structure is as below:












Static Etching Tests
Tungsten blanket wafers were separately immersed for 30 minutes in a conventional hydrogen peroxide containing bulk tungsten slurry (Comparative CMPC G), a CMPC according to Example 5 and a CMPC according to Example 7. The static etching rates observed are reported in Table 2.









TABLE 2





CMPC
Total W removal (in Å)
Static Etching Rate (in Å/min)

















G
920
31


5
60
2


7
40
1.5









Polishing Tests
Polishing experiments were performed on tetraethylorthosilicate (TEOS), silicon nitride (Si3N4) and tungsten (W) blanket wafers available from SVTC, Advantiv and SKW Associates Inc., respectively, using the chemical mechanical polishing compositions described in Table 1. The polishing experiments were performed using an Applied Materials, Inc. Mirra® 200 mm polishing machine equipped with an ISRM detector system using an IC1010TM polyurethane polishing pad (commercially available from Rohm and Haas Electronic Materials CMP Inc.) under a 2 psi (13.8 kPa) down force, a chemical mechanical polishing composition flow rate of 200 ml/min, a platen speed of 133 rpm and a carrier speed of 111 rpm. A Diagrid® AD3BG-150855 diamond pad conditioner (commercially available from Kinik Company) was used to condition the polishing pad. The polishing pad was broken in with the conditioner using a down force of 7.0 lbs (3.18 kg) for 20 minutes. The polishing pad was further conditioned ex situ prior to polishing using a down force of 5.2 lbs (2.36 kg). The W removal rate data reported in Table 3 was determined using a Jordan Valley JVX-5200T metrology tool. The Si3N4 and TEOS removal rates reported in Table 3 were determined by measuring the film thickness before and after polishing using a KLA-Tencor FX200 metrology tool. The results of the polishing tests are presented in Table 3.
















TABLE 3






TEOS
W
Si3N4









RR
RR
RR
T:W
W:T
T:S
S:T
W:S
S:W


CMPC
(Å/min)
(Å/min)
(Å/min)
Selec.
Selec.
Selec.
Selec.
Selec.
Selec.
























A
240
110
1070
2.18
0.46
0.22
4.46
0.10
9.73


B
650
130
100
5.00
0.20
6.50
0.15
1.30
0.77


C
160
90
1090
1.78
0.56
0.15
6.81
0.08
12.11


D
160
80
1070
2.00
0.50
0.15
6.69
0.07
13.38


E
246
592
—
0.42
2.41
—
—
—
—


F
334
453
—
0.74
1.36
—
—
—
—


1
214
477
—
0.45
2.23
—
—
—
—


2
187
611
—
0.31
3.27
—
—
—
—


3
159
672
—
0.24
4.23
—
—
—
—


4
224
563
—
0.40
2.51
—
—
—
—


5
421
459
—
0.92
1.09
—
—
—
—


6
338
544
—
0.62
1.61
—
—
—
—


7
396
471
—
0.84
1.19
—
—
—
—


8
360
522
—
0.69
1.45
—
—
—
—


9
374
375
—
1.00
1.00
—
—
—
—


10
307
433
—
0.71
1.41
—
—
—
—


11
366
315
—
1.16
0.86
—
—
—
—


12
251
458
—
0.55
1.82
—
—
—
—


13
244
339
—
0.72
1.39
—
—
—
—


14
193
411
—
0.47
2.13
—
—
—
—


15
224
430
—
0.52
1.92
—
—
—
—


16
187
418
—
0.45
2.24
—
—
—
—


17
232
336
—
0.69
1.45
—
—
—
—


18
266
377
—
0.71
1.42
—
—
—
—


19
460
120
80
3.83
0.26
5.75
0.17
1.50
0.67

## Claims

1. A method for chemical mechanical polishing of a substrate, comprising:
providing a substrate, wherein the substrate comprises tungsten;
providing a chemical mechanical polishing slurry composition comprising, as initial components:
water;
0.1 to 5 wt % of an abrasive;
0.005 to 0.1 wt % of a diquaternary compound according to formula (I):






wherein each A is independently selected from N and P; wherein R1 is selected from a saturated or unsaturated C1-C15 alkyl group, a C6-C15 aryl group and a C6-C15 aralkyl group; wherein R2, R3, R4, R5, R6 and R7 are each independently selected from selected from a hydrogen, a saturated or unsaturated C1-C15 alkyl group, a C6-C15 aryl group, a C6-C15 aralkyl group and a C6-C15 alkaryl group;
and, wherein the anion in formula (I) can be any anion or combination of anions that balance the 2+ charge on the cation in formula (I);
0.001 to 10 wt % of at least one of a phthalic acid, a phthalic anhydride, a phthalate compound and a phthalic acid derivative;
0.001 to 10 wt % potassium iodate; and,
optionally, an acid, wherein the acid is selected from the group consisting of nitric acid, sulfuric acid and hydrochloric acid;
wherein the chemical mechanical polishing composition provided has a pH of 1 to 4; wherein the chemical mechanical polishing composition exhibits a tungsten static etch rate of ≦5 Å/min and a tungsten removal rate of ≧100 Å/min;
wherein the chemical mechanical polishing composition contains <0.001 wt % per-oxy oxidizer; and, wherein the chemical mechanical polishing composition does not contain corrosion inhibitor agent;

providing a chemical mechanical polishing pad with a polishing surface;
creating dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate with a down force of 0.69 to 34.5 kPa; and
dispensing the chemical mechanical polishing slurry composition onto the chemical mechanical polishing pad at or near the interface between the chemical mechanical polishing pad and the substrate;
wherein the substrate is polished; and, wherein some of the tungsten is removed from the substrate.

2. The method of claim 1, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate of ≧300 Å/min.

3. The method of 1, wherein the substrate further comprises tetraethylorthosilicate; wherein at least some of the tetraethylorthosilicate is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to tetraethylorthosilicate removal rate selectivity of 5:1 to 1:5.

4. The method of claim 1, wherein the substrate further comprises Si3N4; wherein at least some of the Si3N4 is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to Si3N4 removal rate selectivity of 2:1 to 1:2.

5. A method for chemical mechanical polishing of a substrate, comprising:
providing a substrate, wherein the substrate comprises tungsten;
providing a chemical mechanical polishing slurry composition, consisting of, as initial components:
water,
1.5 to 3.5 wt % of abrasive, wherein the abrasive is a colloidal silica abrasive having an average particle size of 10 to 100 nm;
0.01 to 0.1 wt % of a diquaternary compound according to formula (I):





wherein each A is a N; wherein each A is a N; whrein R1 is a —(CH2)4— group;
wherein R2, R3, R4, R5, R6 and R7 are each a —(CH2)3CH3 group; an wherein the anion in formula (I) can be any anion or conbination of anions that balanc the 2+ charge on the cation in formula (I);
0.01 to 1 wt % of ammonium hydrogen phthalate;
0.01 to 1 wt % potassium iodate; and,
optionally, an acid, wherein the acid is selected from the group consisting of nitric acid sulfuric acid and hydrochloric acid;
wherein the chemical mechanical polishing composition provided has a pH of 2 to 3; wherein the chemical mechanical polishing composition exhibits a tungsten static etch rate of less than or equal to 5 Å/min and a tungsten removal rate of greater than or equal to 100 Å/min; and, wherein the chemical mechanical polishing composition contains <0.001 wt % per-oxy oxidizer;

providing a chemical mechanical polishing pad with a polishing surface;
creating dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate with a down force of 0.69 to 34.5 kPa; and
dispensing the chemical mechanical polishing slurry composition onto the chemical mechanical polishing pad at or near the interface between the chemical mechanical polishing pad and the substrate;
wherein the substrate is polished; and, wherein some of the tungsten is removed from the substrate.

6. The method of claim 5, wherein the chemical mechanical polishing composition facilitates a titanium removal rate of ≧300 Å/min with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polishing pad.

7. The method of claim 6, wherein the substrate further comprises tetraethylorthosilicate; wherein at least some of the tetraethylorthosilicate is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to tetraethylorthosilicate removal rate selectivity of 5:1 to 1:5 with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polishing pad.

8. The method of claim 6, wherein the substrate further comprises Si3N4; wherein at least some of the Si3N4 is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to Si3N4 removal rate selectivity of 2:1 to 1:2 with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polishing pad.

9. The method of claim 5, wherein the chemical mechanical polishing slurry composition provided, consists of, as initial components:
water;
1.5 to 3.5 wt % of the abrasive, wherein the abrasive is a colloidal silica abrasive having an average particle size of 25 to 75 nm;
0.01 to 0.03 wt % of the diquaternary compound according to formula (I); wherein each A is a N; wherein R1 is a —(CH)4— group; wherein R2, R3, R4, R5, R6 and R7 are each a —(CH2)3CH3 group;
0.05 to 0.5 wt % of ammonium hydrogen phthalate; and,
0.1 to 0.5 wt % potassium iodate;
optionally, an acid, wherein the acid is selected from the group consisting of nitric acid, sulfuric acid a hydrochloric acid.

10. The method of claim 9, wherein the chemical mechanical polishing composition facilitates a tungsten removal rate of ≧300 Å/min with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polishing pad; and wherein the substrate further comprises Si3N4; wherein at least some of the Si3N4 is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to Si3N4 removal rate selectivity of 2:1 to 1:2 with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pd that comprises a polyurethane impregnated nonwoven polishing ad.

11. The method of claim 9, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate of ≧300 Å/min.

12. The method of claim 9, wherein the substrate further comprises tetraethylorthosilicate; wherein at least some of the tetraethylorthosilicate is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to tetraethylorthosilicate removal rate selectivity of 5:1 to 1:5.

13. The method of claim 9, wherein the substrate further comprises Si3N4; wherein at least some of the Si3N4 is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to Si3N4 removal rate selectivity of 2:1 to 1:2.

14. The method of claim 9, wherein the chemical mechanical polishing composition facilitates a titanium removal rate of ≧300 Å/min with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polish pad.

15. The method of claim 14, wherein the substrate further comprises tetraethylorthosilicate; wherein at least some of the tetraethylorthosilicate is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to tetraethylorthosilicate removal rate selectivity of 5:1 to 1:5 with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polishing pad.

16. The method of claim 14, wherein the substrate further comprises Si3N4; wherein at least some of the Si3N4 is removed from the substrate; and, wherein the chemical mechanical polishing composition exhibits a tungsten removal rate to Si3N4 removal rate selectivity of 2:1 to 1:2 with a platen speed of 133 revolutions per minute, a carrier speed of 111 revolutions per minute, a chemical mechanical polishing composition flow rate of 200 ml/min, and a nominal down force of 13.8 kPa on a 200 mm polishing machine using a chemical mechanical polishing pad that comprises a polyurethane impregnated nonwoven polishing pad.