BACKGROUND OF THE IN VENTION

[0001] Chemical mechanical polishing (CMP) compositions and methods for polishing (or planarizing) the sari ace of a substrate are well known in the art. Polishing compositions (also known as polishing slurries, CMP slurries, and. CMP compositions) for polishing metal layers (such as tungsten) on a semiconductor substrate may include abrasive particles suspended in an aqueous solution and chemical accelerators such as oxidizers, chelating agents, catalysis, and the like.

} ^' Θ0Θ2 In a conventional CMP operation, the substrate (wafer) to be polished is mounted on a carrier (polishing head) which is in turn mounted on a carrier assembly and positioned in contact with a polishing pad in a CMP apparatus (polishing tool). The carrier assembly provides a controllable pressure to the substrate, pressing the substrate against the polishing pad. The substrate and pad are moved relative to one another by an external driving force. The relative motion of the substrate and pad abrades and removes a portion of the material from the surface of the substrate, thereby polishing the substrate. The polishing of the substrate by the relative movement of the pad and the substrate may be further aided by the chemical activit of the polishing composition (e.g., by an oxidizing agent and other chemical compounds present in the CMP composition) and/or the mechanical activity of an abrasive suspended in the polishing composition.

[Θ003] In typical tungsten plug and interconnect processes, tungsten is deposited over a dielectric and within openings formed therein. The excess tungsten over the dielectric layer is then removed during a CMP operation to form tungsten plugs and interconnects within the dielectric. As semiconductor device feature sizes continue to shrink, meeting local and global platiamy requirements has become more difficult in CMP operations (e.g., in tungsten CMP operations). Array erosion (also referred to as oxide erosion), plug and line recessing, and tungsten etching defects are known to compromise planarity and overall device integrity. For example, excessive arra erosion may lead to difficulties in subsequent lithography steps as well as cause electrical contact problems that can degrade electrical performance.

Tungsten etching/corrosion and plug and line recessing may also degrade electrical performance or even cause device failure.

|0604] Commercially available tungsten CMP slurries commonly make use of a hydrogen peroxide oxidizer. While there are many advantages to the use of hydrogen peroxide, it is known to cause excessive tungsten etching in certain CMP operations. In such operations it may be advantageous to reduce the rate at which tungsten etches (corrodes) in the CMP composition. Thus, there is a .need in the industry for tungsten CMP slurri.es (or

compositions} that are less corrosive towards tungsten (i.e., in which tungsten etches at a lower rate).

BRIEF SUMMARY OF THE INVENTION

[0005] A chemical mechanical polishing composition for polishing a substrate having a tungsten layer is disclosed, in one embodiment, the polishing composition includes a water based liquid carrier, a colloidal silica abrasive dispersed in the liquid carrier and having a permanent positive charge of at least 6 mV, an amine containing polymer in solution in the liquid carrier, and an iron containing accelerator. A method lor chemical mechanical polishing a substrate including a tungsten layer is further disclosed. The method may include contacting the substrate with the above described polishing composition, moving the polishing compositio relative to the substrate, and abrading the substrate to remove a portion of the tungsten from the substrate and thereby polish the substrate.

DETAILED DESCRIPTION OF THE INVENTION

[0006] A chemical mechanical polishing composition for polishing a substrate having a tungsten layer is disclosed. The polishing composition includes a water based, liquid carrier, a colloidal silica abrasive dispersed in the liquid carrier and having a permanent positive charge of at least 6 mV, and an amine compound in solution in the liquid carrier. The amine compound may include substantially any suitable amine compound, for example, an amine compound including an alky! group having 12 or more carbon atoms, a polycationic amine compound, and/or an amine containing polymer. The polishing composition may further optionally include an iron containing accelerator, such as an iron containing catalyst, a stabilizer bound to the iron containing accelerator, a hydrogen peroxide oxidizer, and/or a pH in a range from 2.0 to 3.5. The colloidal silica may also be treated with an aminosilane compound.

[0007] The polishing composition contains an abrasive including colloidal silica particles which are desirably suspended in a liquid carrier (e.g., water). As used herein the term colloidal silica particles refers to silica particles that are prepared via a wet process rather than a pyrogeme or flame hydrolysis process which produces structurally different particles. The colloldai silica particles may be aggregated or non-aggregated. on-aggrega ed particles are individually discrete particles that may be spherical or nearly spherical in shape, but can have other shapes as well (such as generally elliptical, square, or rectangular cross-sections). Aggregated particles are particles in which multiple discrete particles are clustered or bonded together to form aggregates having generally irregular shapes.

[Θ008] Preferably, the colloidal silica is precipitated or condensation-polymerized silica, which may be prepared using any met hod known to those of ordinary skill in the art, such as by the sol gel method or by silicate ion-exchange. Condensation-polymerized silica particles are often prepared by condensing Si(OH) ₄ to form substantially spherical particles. The precursor SHOH may be obtaioed, for example, by hydrolysis of high purity alkoxysilan.es, or by acidification of aqueous silicate solutions. Such abrasi v e particles may be prepared, for example, in accordance with U.S. Pat. No. 5,230,833 or may be obtained as any of various commercially available products such as the BiNDZIL 50/80, 30/3.1 , and 40/130 products from E A Chemicals, the Fuso PL- 1 , PL-2, PL-3, and PL-3H products, and the Naieo

Ι Θ34Α, 1050, 2327, and 2329 products, as well as other similar products available from

'DuPont, Bayer, Applied Research, Nissan Chemical (the SNOWTEX products), and Clariant \0W9] The particle size of a particle is the diameter of the smallest sphere that encompasses the particle. The abrasive particles may have any suitable particle size. The abrasive particles may have an average particle size of 5 run or more (e.g. , 1 ran or more, 15 nm or more, 20 nm or more, or 30 am or more). The abrasive particles may have average particle size of 150 nm or less (e.g., 130 nm or less, 80 nm or less, 50 nm or less, or 30 nm or less). Accordingly, the abrasive particles may have an average particle size in a range from 1 nm to 150 nm. (e.g., from 20 nm to 1.30 nm, from. 55 am to 100 nm, from 20 nm to 80 nm, or from 20 nm to 60 nm).

JOOIO] The polishing composition may include any suitable amount of colloidal silica particles. The polishing composition typically includes 0.01 wt. % or more colloidal silica (e.g., 0.05 wt, % or more). More typically, the polishing composition, ma include 0...I wt. % or more (e.g., 1 wt. % or more, 5 wt. % or more, 7 wt. % or more, 10 wt. % or more, or 12 wt. % or more) colloidal silica particles. The amount of colloidal silica particles in the polishing composition is typically 30 wt. % or less, and more typically 20 wt. % or less (e.g., 15 wt % or less, 10 wt. % or less, 5 wt. % or less, 3 wt. % or less, or 2 wt. % or less).

Preferably, the amount of colloidal silica particles in the polishing composition is in a range from 0.01 wt. % to 20 wt. %, and more preferably from 0,05 wt. % to 15 wt. % (e.g. , from 0.1 wt % to 10 wt. %, from 0.1 wt, % io 4 wt. %, from 0, 1 wt % to 3 wt. %, from 0.1 wt % to 2 wt %, or from 0.2 wt. % to 2 wt. %). {0011] The liquid carrier is ^' used to facilitate the application of the abrasive and any optional chemical additives to the surface of a suitable substrate io be polished (e.g., piaiiarized). The liquid carrier may be any suitable carrier (e.g., a solvent) including lower alcohols (e.g., methanol, ethanoi, etc.), ethers (e.g., dioxane, tetrahydrofuran, etc.), water, and mixtures thereof. Preferably, the liquid carrier comprises, consists essentially of. or consists of water, more preferably deioiiized water.

[0012] The colloidal silica particles have a positive charge of at least 6 mV in the polishing composition. The charge on dispersed particles such as colloidal silica particles is commonly referred to in the art as the zeta potential (or the e!ectrokinetic potential). The zeia potential of a particle refers to the electrical potential difference between the electrical charge of the ions surrounding the particle and the electrical charge of the bulk solution of the polishing composition (e.g., the liquid carrier and. any other components dissolved therein). The zeta potential is typically dependent on the pH of the aqueous medium. For a given polishing composition, the isoelectric point of the particles is defined as the pH at which the zeta potential is zero. As the pH is increased or decreased away from the isoelectric point, the surface charge (and hence the zeta potential) is correspondingly decreased or increased (to negative or positive zeta potential values). The zeta potential of a dispersion such as a polishing composition may be obtained using commercially available instrumentation such as the Zetasizer available from Malvern instruments, the ZetaPios Zeta Potential Analyzer available from Brookhaven Instruments, and an electro-acoustic spectrometer available from Dispersion Technologies, Inc.

{0013] The colloidal silic particles in the polishing composition have a permanent positive charge of 6 mV or more (e.g., 1.0 mV or more. 15 mV or more, 20 mV or more, 25 mV or more, or 30 mV or more). The colloidal silica particles in the polishing composition may have a permanent positive charge of 50 mV or less (e.g., 45 mV or less, 40 raV or less, or 35 mV or less). Preferably, the colloidal silica particles have a permanent positive charge in a range from 6 mV to 50 mV (e.g., 10 mV to 45 m V, 1 mV to 40 mV, or 20 i V to 40 raV).

{0014] By permanent positive charge it is meant thai the positive charge on the silica particles is not readily reversible, for example, via Hushing, dilution, filtration, and the like. A permanent positive charge may be the result, for example, of covalentiy bonding a cationic compound with the colloidal silica. A permanent positive charge is in contrast to a reversible pos tive charge that may be the result, for example, of an electrostatic interaction between a cationic compound and the colloidal silica.

(0015) Notwithstanding, as used herein, a permanent positive charge of at least 6 mV means that the zeta potential of the coiioidal silica, particles remains above 6 mV after the following three step ultrafiltration test. A volume of the polishing composition (e.g., 200 ml) is passed through a Millipore Ultraceii regenerated cellulose ultrafiltration disk (e.g., having a MW cutoff of l 00,000 Daltons and a pore size of 6.3 nm). The remaining dispersion (the dispersion that is retained by the ultrafiltration disk) is collected and replenished to the original volume with pH adjusted deionized water, ^" The deionized water is pH adjusted to the original pH of the polishing composition using a suitable inorganic acid such as nitric acid. This procedure is repeaied for a total of three ultrafiltration cycles (each of which includes an ultrafiltration step and a replenishing step). The zeta-poteotial of the triply ultra-filtered and replenished polishing composition is then measured and compared with the ¾eta potential of the original polishing composition. This three step ultrafiltration test is further illustrated below by way of example (in Example 5),

[0016] While not wishing to be bound by theory, it is believed that the dispersion retained by the ultrafiltration disk (the retained dispersion) inciudes the colloidal silica pariicles and any chemical compounds (e.g., cationic compounds) that may be associated with the surface of the particles (e.g., bonded or attached to or electrostatically interacting with the particle surface). At least, a portion of the liquid carrier and the chemical compounds dissolved therein pass through the ultrafiltration disk. Replenishing the retained dispersion to the original volume is believed to upset the equilibrium in the original polishing composition such that the chemical compounds associated with the particle surface may tend towards a new equilibrium. Compounds that are strongly associated (e.g., covale ly bonded) with the particle surface remain on the surface such thai there tends to be little if any change in the positi ve zeta potential of the particle. In contrast, a portion of compounds that have a weaker association (e.g., an electrostatic interaction) with the particle surface may return to the solution as the system tends towards the new equilibrium thereby resulting in a reduction in the positi e zeta potential Repeating this process for a total of three ultrafiltration and replenishing cycles is believed to amplify the above described effect.

[Θ0Π] it is preferred that after correcting for ionic strength differences there is little ior no) difference between the zet potential of the colloidal si lica particles in the original polishing composition and the particles in. the triply ultra-filtered and replenished polishing composition obtained from the above described three step ultrafiltration test !i will be understood that prior to correcting for ionic strength differences, the measured zeta potential may be observed to increase due to the reduced ionic strength (owing to dilation) of the triply ultra-filtered and replenished polishing composition. After correcting for ionic strength differences, it is preferred that any reduction in the positive charge (reduction in ihe positive zeta potential) on the particles resulting from the aforementioned three step ultrafiltration lest is less than 10 mV (e.g., less than 7 mV, less than 5 mV, or even less than 2mV).

[0018] The polishing composition is generally acidic having a pH of less than 7. The polishing composition typically has a pH of 1 or more (e.g., 1.5 or more, or 2 or more). Preferably, the polishing composition has a pH of 6 or less (e.g., 5 or less, or 4 or less). More preferably, the polishing composition has a pH in a range from 1 to 6 (e.g., from 1.5 to 5, or from 2 to 4, or from 2 to 3.5). The pH of the polishing composition may be achieved and/or maintained by any suitable means. The polishing composition may include substantially any suitable pH adjusting agents or btvffering systems. For example, suitable pH adjusting agents .may include nitric acid, sulfuric acid, phosphoric acid, phthalic acid, citric acid, adipic acid, oxalic acid, malonic acid, tnaleic acid, ammonium hydroxide, and the like while suitable buffering agents may include phosphates, sulfates, acetates, malonates, oxalates, borates, ammonium salts, and the like.

[001 ] Colloidal silica particles having a permanent positive charge in the polishing composition may ^' be achieved, for example, via treating the particles with at least one aminosilane compound. Such compounds include primary aminostlan.es, secondary ami nosi lanes, tertiary aminosilanes. quaternary arainosilanes, and multi-podal (e.g., dipodal) aminosilanes. The aminosilane compound can be any suitable aminosilane, such as bis(2- hydroxyethyl ^' )-3-arai.noprop 4 trialkoxysilane, diethylaminomethyltrialkoxysilane, (N, ~ diethyl'3~am.rnopropyl)trialkoxysi.lane), 3^N~styiylmethyl-2-ajt»moethylaminopropyl trialkoxysilane, aminopropyl trialkoxysilane, (2-N-ben¾!:ylarainoethyl)-3-aminopropyl trialkoxysilane), trialkoxysilyl propyl-N,N,N-trimethyl ammonium chloride, N- (trialkoxysilylethyl)be«xyl- , , -trimethyl ammonium chloride,

(his{memyJdialkoxysilylpropyl)-N-methy ^' l amine, bis(trialkoxysilylptopyl)nrea, bis(3- (trialkoxysilyl)propyl)-ethylenediamine, bis(trialkoxysilylpropyl)amine,

bis(irialkoxysilylpropyi)ainine, and mixtures thereof.

[0020j Any suitable method of treating the colloidal silica particles, many of which are known to those of ordinary skill in the art may be used. For example, the colloidal silica particles may be treated with the aminosilane compound before mixing with the other components of the polishing composition or the aminosilane and the colloidal silica particles may be added simultaneously to the other components of the polishing composition.

[0021 The aminosilane compound may be present in the polishing composition in any suitable amount. The amount of aminosilane utilized may depend on several factors, for example, including the particle size, the surface area of the particle, the particular

aminosilane compound used, and the desired charge on the particle. In general the amount of aminosilane used increases with decreasing particle size (and therefore increasing surface area) and increasing charge on the particle. For example, to achieve a permanent positive charge of 25 mV or more, 20 ppm or more of aminosilane may be used for a dispersion having a particle size of 1 10 nm, 7 ppm or more of aminosilane may be used for a dispersion having a particle size of 75 nm. and 130 ppm or more of aminosilane may be used for a dispersion, having a particle size of 55 nm. Thus the polishing composition, may include 5 ppm or more (e.g., 10 ppm or more, 15 ppm or more, or 20 ppm. or more) of the aminosilane compound. The polishing composition preferably includes an amount of aminosilane sufficient to provide the desired permanent positive charge without using an excess. Thus the polishing composition may include 500 ppm or less (e.g., 300 ppm or less, or 200 ppm or less, or 1 50 ppm or less) of the aminosilane compound. Preferably, the polishing composition includes a range from 5 ppm to 500 ppm (e.g.. from 1.0 ppm to 300 ppm, from 15 ppm to 200 ppm, or from 2 ppm to 150 ppm) of the aminosilane compound. {002 J Optional embodiments of the polishing composition may further include an iron containing accelerator. An iron containing accelerator as used herein is an iron containing chemical, compound that increases the removal rate of tungsten during a tungsten CMP operation. For example, the iron containing accelerator may include an iron containing catalyst such as is disclosed in U.S. Patents 5,958,288 and 5,980/775. Such an iron containing catalyst may be soluble in the liquid carrier and may include, for example, ferric (iron ill) or ferrous (iron 11) compounds such as iron nitrate, iron sulfate, iron haikles, including fluorides, chlorides, bromides, and iodides, as well as perchlorates, perbroraates and perioda.es, and organic iron compounds such as iron acetates, acety!acetonates, citrates, gluconates, malonates, oxalates, phthalates, and succinates, and mixtures thereof.

[Θ023] An iron containing accelerator may also include an iron containing activator (e.g., a free radical producing compound) or an iron containing catalyst associated with (e.g., coated or bonded to) the surface of the colloidal silica particle such as is disclosed in U.S. Patents 7,029,508 and 7,077,880. For example, the iron containing accelerator may be bonded with the sitenol groups on the surface of the colloidal surface particle. In one embodiment the iron containing acceleraior may include a boron containing stabilizer and an iron containing catalyst. In such embodiments the stabilizer and catalyst may occupy substantially any percentage of the available surface sites on the colloidal silica particles, for example, greater than 1%, greater than 50%, or greater than.80% of the available surface sites.

J0024] The amount of iron containing accelerator in the polishing composition may be varied depending upon the oxidizing agent used and the chemical form of the accelerator. When the preferred o idizing agen hydrogen peroxide (or its analogs) is used and a soluble iron containing catalyst is used {such as ferric nitrate), the catalyst may be present in the composition in an amount sufficient: to provide a range from I. to 3000 ppm Fe based on the total weight of the composition. Hie polishing composition preferably includes 1 ppm Fe or more (e.g., 5 ppm or more, 10 ppra or more, or 20 ppm or more). The polishing composition preferably includes 500 ppm Fe or less (e.g., 200 ppm or less, 100 ppm or less, or SO ppm or less). The polishing composition may thus include a range from 1 to 500 ppm Fe (e.g., from 3 to 200 ppm, from 5 to 100 ppm, or from 10 to 50 ppm),

[Θ025] Embodiments of the polishing composition including an iron containing accelerator may further include a stabilizer. Without such a stabilizer, the iron containing accelerator and the oxidizing agent ma react in a manner that degrades the oxidizing agent rapidly over time. The addition of a stabilizer tends to reduce the effectiveness of the iron containing accelerator such that the choice of the type and amount of stabilizer added to the polishing composition may have a significant impact on CMP performance. The addition of a stabilizer may lead to the formation of a stabilizer/accelerator complex that inhibits the acceleraior from reacting with the oxidizing agent while at the same time allowing the accelerator to remain sufficiently active so as to promote rapid tungsten polishing rates. j0<)26] Useful stabilizers include phosphoric acid, organic acids, phosphonate compounds, nirriles, and other ligands which bind to the metal and reduce its reactivity toward hydrogen peroxide decomposition and mixture thereof. The acid stabilizers may be used in their conjugate form, e.g., the carboxylate can be used instead of the carboxyltc acid. For purposes of this application the term "acid" as it is used to describe useful stabilizers also means the conjugate base of the acid stabilizer. For example the term "adipic acid" means adipic acid and its conjugate base. Stabilizers can be used, alone or in combination and significantly decrease the rate at which oxidizing agents such as hydrogen peroxide decomposes.

[Θ027] Preferred stabilizers include phosphoric acid, phthalic acid, citric acid, adipic acid, oxaiic acid, malonic acid, aspartic acid, succinic acid, giutaric acid, pimelic acid, suberic acid, aze!aic acid, sebaeic acid, malek acid, giatacoase acid, mnconic acid,

eil ylenediamineteiraacetic acid (EDTA), propyl enedia metetraacetic acid (PDT.4), and mixtures thereof. The preferred stabilizers may be added to the compositions and slurries of this invention in an amount ranging from 1 equivalent per iron containing accelerator to 3.0 weight percent or more. As used herein, die term, "equivalent per iron containing accelerator" means one molecule of stabilizer per iron ion in the composition. For example 2 eq«ivalents per iron containing accelerator means two molecules of stabilizer for each catalys t ion.

[0028} The polishing composition may further include an oxidizing agent. The oxidizing agent may be added to the polishing composition during the shirry manufacturing process or just prior to the CMP operation (e.g., in a tank located at the semiconductor imbrication facility). Preferable oxidizing agents include inorganic or organic per-compounds. A per- compoun as defined by Hawley's Condensed Chemical Dictionary is a compound containing at least one peroxy group (-0--0-) or a compound containing an element in its highest oxidation state. Examples of compounds containing at least one peroxy group include but are not limited to hydrogen peroxide and its adducts such as urea hydrogen peroxide and percarbonates, organic peroxides such as benzoyl peroxide, peracetie acid, and di~t-butyl peroxide, monopersulfat.es (SOs ^" ), dipersuliates (S2O , and sodium peroxide. Exampies of compounds containing an element in i s highest oxidation state include but are not limited to periodic acid, periodate salts, perbromic acid, perbromate salts, perchloric acid, perchlorate salts, perhoric acid, and perborate salts and permanganates. The most preferred oxidizing agents is hydrogen peroxide.

[0029} The oxidizing agent may be present in the polishing composition in an amount ranging, for example, from 0.1 to 10 weight percent. In preferred embodiments in which a hydrogen peroxide oxidizer and a soluble iron containing accelerator are used, the oxidizer may be present in the polishing composition in an amount ranging from 0.1 to weight- percent (e.g., from 0.2 to 5 weight percent, from 0.5 to 4 weight percent, or from i to 3 weight percent).

[0039 The polishing composition further includes an amine compound in solution in the liquid carrier. The amine compound may include substantially any amine compound that inhibits tungsten etching (i.e., reduces tungsten etch rates) in the presence of an oxidizer such as hydrogen peroxide. The addition of an amine compound may also have a negative impact on CMP performance. Thus the amine compound may be selected such that it

advantageously inhibits tungsten etching while at the same time allowing for high tungsten removal rates during the CMP operation. The amine compound (or compounds) may include a primary amine, a secondary amine, a tertiary amine, or a quaternary amine. The amine compound may further include a monoamine, a diamine, a triamine, a tetramine, or an amine based polymer having a large number of repeating amine groups (e.g., 4 or more amine groups).

[Θ031 j in certain embodiments of the polishing compound the amine compound may include a king chain atkyl group. By long chain alky group it is meant that the amine compound includes an alky! group having at least 10 carbon atoms (e.g., at least 12 carbon atoms or at least. 14 carbon atoms}. Such amine compounds may include, for example, dodecylamine, tetradeeyl amine, hexadecylamine. octadecylaraioe, oleyiamine, - methyldioctyiaraine, N-methyloctadecylamine, cocamidopropy!amine oxide,

benzyldimethylhexadecylammouiurn chloride, hen/alkonium chloride.

cocoalkylmethyl[polyoxyethylene (15)] ammonium chloride,

octadecylmethylj olyoxyethylene (15)] ammonium chloride, cetyitnmethylamirionium bromide, and the like.

(0932] In cert ain embodiments of the polishing composit ion the amine compound may include a polyeationic amine. A polyeationic amine (as the term is used herein) is an amine compound having multiple (two or more) amine groups in which each of the amine groups is cationic (i.e., has a positive charge). Thus the po!ycationic amine may include a

polyquaiemary amine. By poiyquaferaary amine it is meant that the amine compound includes from 2 to 4 quaternary ammonium groups such that the polyquatemary amine is a cUqoaternary amine, a triquaternary amine, or a tetraquaternary amine compound.

Diquaiernary amine compounds may include, for example, ,N ^! - meihylenebis(dimethyltetradecylammonium bromide), 1 , i ,4,4-te{rabuty!pipera¾inedi turn dibromide, ,Ν,Ν',Ν'^ -pentamethyl-N-iallow-l _s 3-pTopane-diammonium die loride, Ν,Ν'- hexamethylenebis(tributy1ammoniam hydroxide), decamethonium bromide, didodecyi- teiramethyl- 1 ,4-butanediamimum diiodide, 1 ,5-dimefhyl- 1 ,5-diazoniabicyclo(3.2,2)nonane dibromide, and the like. Triquaternary amine compounds may include, for example, N(1 ),N(6)-didoecyl-N(l ),N(l),N(6X (6Hetramethyl-l,6-h.exanediamimum diiodide. Tetraquaternary amine compounds may include, for example,

methanetetrayltetrakis(tetramethy1ammonium bromide). The polyqua ternary amine compound may further include a long chain alkyl group (e.g., having 1 or more carbon atoms). For example, a poiyqyatemary amine compound having a long chain aJkyl group may include Ν,Ν'-methylenebis (dimemyhetradecylannnoniom bromide), N. ,N ^! , \N'- pentamethyl-N-iallow- I ,3-propane-diammonium dichloride, didodecyl-tetramethyl- 1 ,4- butanediaminium diiodide, and N(l),N{6)-didodecyl-N( 1 ),N( 1 ),N(6), {6)-tetrametbyl- 1 ,6- hexanedianunium diiodide.

[0033J A po!ycatiomc amine may also be polycaiionic in that each of the amine groups is protonated (and therefore has a positive charge). For example, a dicationic amine such as telrametbyl-p-phenylenediamme includes two tertiary amine groups that may be protonated (and therefore positively charged) at -polishing composition pH values less than the p a of the amine compound.

|Θ034] In certain embodiments of the poli shing composition the amine compound may include an amine based polymer. Such a polymer includes four or more amine groups. The amine based polymer may include, for example, iriethylenetetramine,

tetraethyienepentamiiie, pentaethyienehexamine, and polymers including the following amine containing functional groups methaeryioyl o -ethyl trimethyi ammonium methylsul ate, diallyl dimethyl ammonium chloride, and methaeryla ido-propy! trimethyi ammonium chloride.

(0035] It will be understood that the amine compound does not include a heterocyclic polyarame. Heterocyclic poiyamines are amine compounds having multiple amine groups in which at least one of the amine groups is located in a ring (e.g., a ring including 3, 4, 5, 6, 7, or 8 members). Such heterocyclic amine compounds include, ior example, certai pyridine, pyridylanmie, pyrimidme, and azoie compounds. While such heterocyclic poiyamines (such as benzotriazole) are known inhibitors of copper etching, their utility in inhibiting tungsten etching tends to be limited. As such, they are not particularly useful in the disclosed tungsten CMP compositions.

|0636] The polishing composition may include substantially any suitable concentration of the amine compound, in general the concentration is desirably high enough to provide adequate etch inhibition, but Sow enough so that the compound is soluble and so as not to reduce tungsten polishing rates below acceptable levels. By soluble it is meant that the compound is fully dissolved in the liquid carrier or that it forms micelles in the liquid carrier or is carried in micelles. It may be necessary to vary the concentration of the amine

compound depending upon numerous various factors, for example, including the solubility of the amine compound, the number of amine groups in the amine compound, the length of an alkyl group in the amine compound, the relationship between etch rate inhibition and polishing rate inhibition, the oxidizing agent used, the concentration of the oxidizing agent, and so on. In certain desirable embodiments, the concentration of the amine compound in the polishing composition is in a range from 0.1 μΜ to 10 mM (i.e., from 10" to ΗΓ ^' molar). For example, in embodiments utilizing an amine based polymer having a high molecular weight, the concentration may he on the lower end of the range (e.g., from 10 ^"' to IO ^"4 molar). In other embodiments utilizing a comparatively simple amine compound (having fewer amine groups and a lower molecular weight), the concentration may be on the higher end of the range (e.g., from 1 ^"5 to 10 ^" " molar).

10037] The polishing composition may optionally further include a biocide. The biockie may include any suitable biocide, for example an isothiazoiinone biocide. The amount of hiocide in the polishing composition typically is in a range from 1 ppra to 50 pprn. and preferably from 1 ppm t 20 pprn.

[0038} The polishing composition may be prepared using any suitable techniques, many of which are known to those skilled in the art. The polishing composition may be prepared in a batch or continuous process. Generally, the polishing composition may he prepared by combining the components thereof in an order. The term, "component" as used herein includes the individual ingredients (e.g., the colloidal silica, the iron containing accelerator, the amine compound, etc.),

[0039] For example, the silica may be dispersed in the aqueous liquid carrier. The silica may then be treated, for example, with an amhiosilane so as to produce generate a colloidal silica having a permanent positive charge of at least 6 mV. Other components such as an iron containing accelerator, a stabilizer, and the amine compound may then be added and mixed by any method that is capable of incorporating the components into the polishing

composition. The oxidizing agent may be added at any time during the preparation of the polishing composition. For example, the polishing composition may be prepared prior to use, with one or more components, such as the oxidizing agent, being added just prior to the CMP operation (e.g., within I minute, or within 10 minutes, or within 1 hour, or within I day, or within 1 week of the CMP operation). The polishing composition also may also he prepared by mixing the components at the surface of the substrate (e.g., on the polishing pad) during the CMP operation.

[0040] The polishing composition may be supplied as one-package system comprising colloidal silica having a permanent positive charge of at least 6 mV, an amine compound, an optional iron containing accelerator and stabilizer, an optional biocide, and water. The oxidizing agent desirably is supplied separately from the other components of the polishing composition and is combined, e.g., by the end-user, wiih the other components of the polishing composition shortly before use (e.g., 1 week or less prior to use, 1 day or less prior to use, 1 hour or less prior to use, 10 minutes or less prior to use, or i minute or less prior to use). Various other two-container, or three- or more-container, combinations of the

components of the polishing composition are within the knowledge of one of ordinary skill in the art.

JiM l ] The polishing composition, of th invention may also be provided as a concentrate- which is intended to be diluted with an appropriate amount of water prior to use. In such an embodiment, the polishing composition concentrate may include the colloidal silica having a permanent positive charge of at least 6 mV. the amine compound, the optional iron containing accelerator and stabilizer, the optional biocide, and water, with or without tire oxidizing agent, in amounts such that, upon dilution of the concentrate with an appropriate amount of water, and the oxidizing agen if not already present in an appropriate amount, each component, of the polishing composition will he present in. the polishing composition in an amount within the appropriate range recited above for each, component. For example, the colloidal silica having a permanent positive charge of at least 6 mV, the amine compound., the optional iron containing accelerator and the stabilizer, may each he present, i.u the

po.Hshi.ng composition in an amount that is 2 times (e.g., 3 times, 4 times, 5 times, or even 10 times) greater than the concentration recited above for each component so that, when the concentrate is diluted with an equal volume of (e.g., 2 equal volumes of water, 3 equal volumes of water, 4 equal volumes of water, or even 9 equal volumes of water respectively), along with the oxidizing agent in a suitable amount, each component will be present in the polishing composition in an amount within the ranges set forth above for each component. Furthermore, as wilt be understood by those of ordinary skill in the art, the concentrate may contain an appropriate fraction of the water present in the final polishing composition in order to ensure that other components are at least partially or fully dissolved in the concentrate. }f)042] Although the polishing composition of the in e tion may be used to polish any substrate, the polishing composition is particularly useful in the polishing of a substrate comprising at least one metal including tungsten and at least one dielectric material. The tungsten layer may be deposited over one or more barrier layers, for example, including titanium and/or titanium nitride (ΉΝ). The dielectric layer may be a metal oxide such as a silicon oxide layer derived from, teiraethylorihosi licate (TEOS), porous metal oxide, porous or non-porous carbon doped silicon oxide, fluorine-doped silicon oxide, glass, organic polymer, fluorinated organic polymer, or any other suitable high or !ow-k insulating layer.

[0043J The polishing method of the invention is particularly suited for use in conjunction with a chemical mechanical polishing (CMP) apparatus. Typically, the apparatus includes platen, which, when in use, is in motion and has a velocity that results from orbital, linear, or circular motion, a polishing pad in contact with the platen and moving with the platen when in. motion, and a carrier that holds a substrate to be polished by contacting and moving relative to the surface of the polishing pad. The polishing of the sobstrate takes place by the substrate being placed in contact with the polishing pad and the polishing composition of the invention and then the polishing pad moving relative to the sobstrate, so as to abrade at least a portion of the substrate (such as tungsten, titanium, titanium nitride, and/or a dielectric material as described herein) to polish the substrate.

ju044| A sobstrate can be pianarized or polished with the chemical mechanical polishing composition with any suitable polishing pad (e.g., polishing surface). Suitable polishing pads include, for example, woven and non-woven polishing pads. Moreover, suitable polishing pads can comprise any suitable polymer of varying density, hardness, thickness, compressibility, ability to rebound upon compression, and compression modulus. Suitable polymers include, for example, polyvinylfluoride, nylon, fluorocarbon, polycarbonate, polyester, polyacrylate, polyetlter, polyethylene, polyamide, polyurethane, polystyrene, polypropylene, cof armed products thereof, and mixtures thereof.

j ⁽ H 5j The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.

EXAMPLE 1

[0046] A number of polishing compositions were prepared in order to evaluate various performance metrics of the compositions. A standard, composition was used as a. base composition for all formulations with only the amount and type of amine compound varied. The standard composition was prepared as follows: [0047] A dispersion was prepared including 3.0 weight percent colloidal silica and 0.01 weight percent (1 0 ppm) of bis-(gamma-i ^' rimetJhoxysilylpropyl.)amine (an aminosilane). The dispersion was prepared by mixing a concentrated colloidal silica dispersion having a mean particle size of 75 nm (such as are commercially available from Akso Nobel, Fuso, and Nalco as listed above) with the aminosilane and water. The dispersion was mixed for a number of hours to adequately treat the colloidal silica with the ami nosilane. The treated colloidal silica dispersion was then added to a mixture including malonic acid, ferric nitrate, and water such that the final concentrations in the composition were as follows: 2.0 weight percent treated colloidal silica, 0.0031. weight percent ferric nitrate, and 0.067 weight percent malonic acid. The pH of the mixture was then adjusted to 2.4 using nitric acid. This mixture was used as a stock solution in which various amine compounds were dissolved prior to performing zeta potential measurements, static etch tests, and CMP tests as described in more detail in the subsequent examples.

EXAMPLE 2

|0648] The tungsten etch rate and zeta potential of the colloidal silica were evaluated in this example for various polishing compositions. This example demonstrates the effect of various amine compounds as a function of the longest a kyl chain length in the amine compound. To obtain the tungsten etch rate for each polishing composition, the composition was first heated to 45 degrees C after which hydrogen peroxide was added to a concentration of 2 percent. After waiting 5 minutes for th temperature to return to 45 degrees, a two-inch wafer having a tungsten layer was submersed in the polishing compositions for 5 minutes. Tungsten removal rates were determined via resistivity measurements made before and after immersion in the polishing compositions. The zeta potential measurements were obtained using a DTI 200 electro-acoustic spectrometer available from Dispersion. Technologies, Inc. The polishing compositioas (Controls A and B and inventive compositions 2A through 2M) were obtained by adding an appropriate amount of the indicated, amine compound to a sample of the stock solution described above in Example 1. The alkyl chain length (in number of carbon atoms), the concentration of the amine compound, the tungsten etch, rate, and the zeta potential of the colloidal silica particles are indicated in Table 1. Control A included no inhibitor and control B included glycine. Inventive samples 2A through 2M included the following amine compounds: (2A) octadecylmethyijpolyoxyethyiene ( 15)] ammonium chloride, (2B) cocoaIkylmemyl|polyoxyemyiene (1.5)] ammonium chloride, (2C)

benzalkonium chloride, (2D) hexadecylamine, (2E) benzyklimethylhexadecylammoniom chloride, (2F) tetradecylararae, (2G) dodecylamme, (2H) decylaraiiie, (21) octylarnine, cocamidopropylaraine oxide, (2K) henzyltribinyiammoniura chloride, and (2L)

tetrabut ylammom urn hydr oxde.

(0949] As is apparent from the results set. forth m Table 1 , compositions 2A-2G, which included amine compounds having an alkyi chain length greater than 10 ( 12, 14, 16, and 18} exhibited W etch rates of one-tenth or less that of control A (no inhibitor) and one-seventh or less that of control B (glycine).

EXAMPLE 3

[0050] The tungsten etch rate and zeta potential of the colloidal silica were evaluated i this example for various other polishing compositions. This example demonstrates the effect of various amine containing polymers (3A-3E). The tungsten etch rates and zeta potential measurements were obtained using the same methodologies as described in Example 2. The polishing compositions (controls A and B and inventive compositions 3A through 3E) were obtained by adding an appropriate amount of the indicated amine compound to a sample of the stock solution described above h Example 1. The alky! chain length (in number of carbon atoms), the concentration of the amine coinpoiind, the tungsten etch rate, and the zeia potential of the colloidal silica are indicated in Table 2. Control A included no inhibitor and control B included glycine, inventive samples 3A through 3E included the following amine compounds: (3A) Merquat 280 which is a polymer having alternating diallyl dimethyl ammonium chloride and acrylic acid groups and having a molecular weight of 450,000, (3B) Merquat ! 06 which is a polymer having repeating dimethyl ammonium chloride groups and a molecular weight of 1.5,000, (3C) peniaeihylenehexamine, (3D) tetraethylenepentamine, and (3.B) pentamethyldiethylenetriamine.

Table 2

jOOSl ] As is apparen from the results set forth, in Table 2, compositions 3 A, 3B, 3C, and 3D exhibited W etch rates significantly less than that of the controls. The eich rate of composition 3E was similar to that of control A (no inhibitor),

EXAMPLE 4

[0052] The tungsten etch rate and zeta potential of the colloidal Silica were evaluated in this example for still other polishing compositions. This example demonstrates the effect of various polycationic amine containing compounds (4A-4 ), The tungsten etch rates and zeta potential, measurements were obtained using the same methodologies as described in Example 2, The polishing compositions (controls A and B and. inventive compositions 4A through 4K) were obtained by adding an appropriate amount of the indicated amine compound to a sample of the stock solution described above in Example 1. The alky! chain length (in number of carbon atoms), the concentration of the amine compound, the tungsten etch rate, and the /eta potential of the colloidal silica are indicated in Table 3. Control A included no inhibitor and control B included glycine, inventive samples A through 4K included the following amine compounds: (4A) N,N'-methyle}iebis

(dimethyltetradecylammoniuin bromide), (4B) 1 , 1 ₅ 4,44ettabutylpiperazinediuffi dibromide, (4C) N,N, ^N^N'-pe«tatneUryl- -tal!ow-l "propaae4iiammonjum dicliloride. (4D) 1 ,5- dimethyl- \ ,5-dia/onjabicyclo(3.2.2)nonane dibromide, (4E) N(.l },N(6)~didoecyS~

N( 1 ),N{ 1 ), {6), (6)-teti'aniethyl- 1 ,6-bexanediaminiiim diiodide, (4F) decamethonkrm bromide. (AG) methanetetrayltetrakis(tetrainetliylaittnioumm bromide), (4H) hexamethonium chloride, (41) tetramethyl-p-phenylenedia ine, (4J ) didodecyl-tetramethyl~l,4~

butanedianjinium diiodide, and (4K) ( l ), N ^' ( ^' S ), N(3}-i:ribui. ~N(3)-{3- [dibutyl(raethyl)ammomo;|propyl-N(I ), N(3)-dimethyl-i^-propanediammiura triiodide.

Table 3

[Θ053] As is apparent from the results .set forth in Table 3, compositions 4A, 4C, 4D, 4E, 4J, and 4 may exhibit W etch rates significant less than that of the controls (depending on the concentration of the inhibitor). EXAMPLE 5

[MS4] The tungsten etch rate and zeta potential of the colloidal silica were evaluated in this example for various other polishing compositions. This example demonstrates the effect of various heterocyclic polyam ne compounds. The tungsten etch rates and zeta potential measurements were obtained using the same methodologies as described in Example 2. The polishing compositions (controls A and 8 and compositions 5A through 5F) were obtained by adding an appropriate amount of the indicated amine compound to a sample of the stock solution described above in Example 1 . The aSkyl chain length (in number of carbon atoms), the concentration of the amine compound, the tungsten etch rate, and the zeta potential of the colloidal silica are indicated in Table 4. Control A included, no inhibitor and control B included glycine. Samples 5 A through 5F included the following amine compounds: (5A) 2- (arainomethy)pyridine, (SB) 2,2'dipyridylamHie, (5C) benzotriazole, (5D) 2-aminopyrimidie, (5E) 4-anjmopyridi.ne, and (5F) 5-aniinoteirazole.

Table 4

10055] As is apparent from the results set forth in Table 4, none of compositions 5A through 5 F exhibited a W etch rate of less than that of the gl cine control. All but composition SB exhibited W etch rates about equal to or greater than the control including no inhibitor,

EXAMPLE 6

}t)056| Zeta potential measurements and conductivity measurements were obtained for treated silic samples before and after filtration. A 200 ml volume of each composition was filtered through a MilKpore IJIixaeell regenerated cellulose ultrafiltration disk (having a MW cutoff of 100,000 Dal tons and a pore size of 6.3 run). The remaining dispersion, (the dispersion that was retained by the ultrafiltration disk) was collected and replenished to the original 200 ml volume using deionized water adjusted to pH 2.6 with nitric acid. This procedure was repeated for a total of three ulttafiltration cycles (each of which includes an ultrafiltration step and a replenishing step). The zeta-poteniial and electrical conductivity of the polishing composition were measured before and after the ultrafiltration procedure (i.e., on the original polishing composition and the triply ultra-filtered and replenished polishing composition). Table 5 shows the measured zeta potential and. conductivity for polishing compositions 6A and 6S. Polishing composition 6A contained a 55 nm colloidal siiica treated with 3-{aminopropyi)trini.ethoxylsiIa.ne while polishing composition 68 contained a 55 nra colloidal silica treated with tetrabutylaroroonium hydroxide. As described above, the zeta potential and electrical conductivity of the original compositions were measured before and after above described ultrafiltration procedure. Corrected zeta-potential values of the triply ultra-filtered and replenished polishing composition (corrected for ionic strength differences as indicated by the conductivity change) are also shown.

j0057] As is apparent from the results set forth in Table 5, the zeta potential of sample 6A is not changed by filtration indicating that the colloidal silica has a permanent positive charge of 41 mV . The zeta potential of sample 6B decreased from 10 to 3 mV indicating that the positive charge colloidal silica was not permanent.

EXAMPLE ?

[Θ0581 Both the tungsten etch rate and the tungsten polishing rate were evaluated in this example for various polishing compositions. This example demonstrates the effect of various amine compounds on the tungsten etch rates and tungsten polishing rates for the

corresponding polishing com osition . The CMP compositions were obtained using the procedure described in Example 1. The compositions were similar to those described above with the exception that they included the following final concentrations; 1.5 weight percent treated colloidal silica, 0.0012 weight percent ferric nitrate, 0.0267 weight percent raalonic acid, and 0.5 percent hydrogen peroxide.

[0059] The tungsten etch rates were obtained using the same methodology described in Example 2. The tungsten polishing rates were obtained usi g a Mirra.® CMP Tool (available from Applied Materials). Eight inch wafers having a tungsten layer deposited on a surface- thereof were polished on an iClOiO polishing pad at a down-force of 1 .5 psi, a platen speed of 100 rpm, and a slurry flow rate of 150 ml/miri. The polishing compositions (the control and compositions 6A through 1) were obtained by adding an appropriate amount of the indicated amine compound to a sample of the stock solution described above in Example 1. The alkyl chain length (in number of carbon atoms), the concentrati on of the amine

compound (in ppm by weight), the tungsten etch rate, and the tungsten polishing rate are indicated in Table 6. The control included gl cine. Samples 6A through 61 included the following amine compounds (6 A) N^.N ^{^} ^N'^Tetrabutyi-l^hexanediaraine, (6B) cetyltrimethylammonium bromide, (6C) Di(hydrogenated Taliowaiky) quaternary amine, ( 6D) I ,Ν,Ν',Ν' , '-pentamethy I -N-tallow- 1 -propane-diammoni am dichiori de, (6 E) poly{ ( 3 - (methacryloylaniino)-propyl]trimemylammoni«m chloride, acrylamine and acrylic acid, (6F) an ampho!ytic terpo!ymer of memac-ryl-midopropyl trimethyl ammonium chloride, acrylamide and acrylic acid, (6G) polyethyleiniine» (6H) Peniatnetlrvldiethylenetriamine, and (61) ^' i.- Bis 3-(dimethylamino)proyljamino|-propano1.

Table 6

JO060] As is apparent from the results set forth in Table 6 _S compositions 6B and 6D exhibit etch rates significantly less than the control and W polishing rate only marginally less than the control. Compositions 6€ (high concentration) and 6G exhibit both etch rates and W polishing rates that are significantly less than the control.

(Θ061) it will be understood that the recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value failing within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited .herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplar)' language (e.g.. "such as") provided herein, is intended merely to better illuminate the invention and does not pose a {imitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating an non-claimed element as essential to the practice of the invention.

(0962] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.