KR20170044156A - Germanium chemical mechanical polishing - Google Patents

Abstract

A planarizing / polishing method of germanium is described. The method includes abrading the surface of a substrate comprising germanium using an aqueous chemical-mechanical polishing (CMP) composition comprising an oxidizing agent, a particulate abrasive, and a germanium etch inhibitor. Germanium etch inhibitors are selected from the group consisting of water soluble polymers, amino acids with non-acidic side chains, bis-pyridine compounds, and combinations of two or more thereof. The polymer may be a cationic or nonionic polymer comprising a basic nitrogen group, an amide group or a combination thereof.

Description

Germanium Chemical Mechanical Polishing {GERMANIUM CHEMICAL MECHANICAL POLISHING}

<Cross reference with related application>

This application claims priority to U.S. Patent Application Serial No. 14 / 308,587 filed on June 18, 2014. The contents of this priority application are incorporated herein by reference in their entirety.

<Technical Field>

The present invention relates to chemical mechanical polishing (CMP) compositions and methods. More specifically, the present invention relates to a method for removing CMP of germanium.

Compositions and methods for CMP of the surface of a substrate are well known in the art. Compositions (also known as polishing slurries, CMP slurries, and CMP compositions) for chemical mechanical polishing / planarization of semiconductor substrates in various substrates, such as integrated circuit fabrication, typically contain abrasives, various additive compounds, and the like.

In conventional CMP techniques, a substrate carrier or polishing head is mounted on a carrier assembly and placed in contact with a polishing pad in a CMP apparatus. The carrier assembly provides a controllable pressure to the substrate to press the substrate against the polishing pad. The pad and the carrier to which the substrate is attached move relative to each other. The relative movement of the pad and substrate serves to abrade the surface of the substrate, thereby removing a portion of the material from the substrate surface, thereby polishing the substrate. The polishing of the substrate surface is typically further assisted by the chemical activity of the polishing composition (e.g. by oxidizing agent, acid, base or other additives present in the CMP composition) and / or the mechanical activity of the polishing agent suspended in the polishing composition do. Typical abrasive materials include silicon dioxide, cerium oxide, aluminum oxide, zirconium oxide and tin oxide.

Germanium has been used in advanced metal oxide semiconductor (MOS) transistor structures for integrated circuits (IC), for example due to shallow trench isolation (&quot; STI) technology. &Lt; / RTI &gt; Planarization of germanium under oxidizing conditions is required to produce acceptable MOS structures under current integrated circuit design parameters. Unfortunately, germanium oxide is highly soluble, resulting in a high static etch rate (SER) in the presence of an oxidizing agent such as hydrogen peroxide. The high SER eventually results in dishing problems when planarizing germanium using CMP compositions comprising hydrogen peroxide or other oxidants, which can severely limit the choice for advanced IC designs using germanium. Cationic surfactants have so far been evaluated as germanium etch inhibitors; These materials cause foaming problems during CMP, which severely limits its practical usefulness.

The method described herein provides for the use of a specific germanium etch inhibitor material in a CMP slurry to provide a suitably low roughness surface for advanced germanium IC applications with minimal dishing without experiencing the foaming problem of cationic surfactants, Related etching and dishing problems.

A planarizing / polishing method of germanium is described. The process may be carried out in the presence of an oxidizing agent (e.g., about 0.5 to about 4 wt% hydrogen peroxide), a particulate abrasive such as colloidal silica (e.g., about 0.1 to about 5 wt%, preferably about 0.5 to about 3 wt%), and an aqueous CMP composition comprising a germanium etch inhibitor to abrade the surface of the substrate comprising germanium. Germanium etch inhibitors are selected from the group consisting of water soluble polymers, amino acids with non-acidic side chains, bis-pyridine compounds, and combinations of two or more thereof.

The water soluble polymer may be a cationic or nonionic polymer comprising a basic nitrogen group, an amide group or a combination thereof. These groups can be substituents located along the polymer backbone (e. G., Hydrocarbon, ester, amide or ether backbone) or can form part of the polymer backbone (as in some polyimides, for example) . In some embodiments, the polymer is a polymer having a primary amino group, a secondary amino group, a tertiary amino group, a quaternary amino group and a combination of two or more thereof and / or a basic nitrogen heterocyclic group such as pyridine, imidazole, Or a quaternized form thereof. In some other embodiments, the polymer typically comprises at least one member selected from the group consisting of -C (= O) NH ₂ , -C (= O) NHR, -C (= = O) NR &lt; ₂ &gt; and combinations of two or more thereof, wherein each R is independently a hydrocarbon moiety (e.g., Lower alkyl such as methyl, ethyl, propyl, etc.). In another embodiment, the polymer may comprise an amide group and a basic nitrogen group.

Polyacrylamide-type nonionic polymers having -C (= O) NH ₂ and / or -C (= O) NHR amide groups are preferred nonionic polymers for use in the compositions and methods described herein. Non-limiting examples of such materials include polyacrylamide (PAM), poly (N-isopropylacrylamide) (PNIPAM), PAM copolymers and the like.

Useful cationic polymers include poly (diallyldimethylammonium) halides such as poly (diallyldimethylammonium) chloride (poly DADMAC), poly (methacryloyloxyethyltrimethylammonium) halides such as poly (methacryloyloxyethyl Trimethylammonium) chloride (poly MADQUAT), poly (dimethylamine-co-epichlorohydrin-co-ethylenediamine) (poly DEE), and the like. In some embodiments, the cationic polymer can include both amide groups and basic nitrogen groups, such as, for example, in acrylamide (AAm) and copolymers of DADMAC, such as poly AAm-co-DADMAC. In some preferred embodiments, the polymer is present in the CMP composition at a concentration in the range of from about 10 to about 2000 parts per million (ppm).

Amino acid-based germanium etch inhibitors are amino acids with non-acidic side chains. In some cases, the amino acid preferably has a basic side chain, hydrophobic side chains, and / or has an isoelectric point of 6 or more. Nonlimiting examples of such amino acids are lysine, arginine, histidine, glycine, beta-alanine, valine and N- (2-hydroxy-1,1-bis (hydroxymethyl) ethyl) glycine) ). Preferably, the amino acid is present in the composition in a concentration ranging from about 50 to about 5000 ppm.

Bis-pyridine-type Ge etch inhibitors are compounds that comprise two pyridine groups linked together through a covalent bond (i.e., a bipyridyl compound) or through one to three carbon linking groups. In some embodiments, the Ge etch inhibitor is 4,4'-trimethylenedipyridine, 1,2-bis (4-pyridyl) ethane, 2,2'-bipyridyl and 1,2- Dile) ethylene. &Lt; / RTI &gt; Preferably, the bis-pyridine compound, when used, is present in the composition in a concentration ranging from about 50 to about 5000 ppm.

In one embodiment, the particulate abrasive, such as colloidal silica, is present in the CMP composition in a concentration ranging from about 0.5 to about 3 wt%, and the polymer is present in a concentration from about 10 to about 1000 ppm. In another embodiment, the CMP composition comprises from about 0.5 to about 3 wt% abrasive (e.g., colloidal silica), and from about 50 to about 5000 ppm amino acid. In another embodiment, the CMP composition comprises from about 0.5 to about 3 wt% abrasive (e.g., colloidal silica), from about 10 to about 1000 ppm polymer, and from about 50 to about 5000 ppm amino acid.

The process described herein is suitable for planarizing Ge and Si _x Ge _(1-x) (where x = about 0.1 to about 0.9) material, and surprisingly does not cause foaming problems during the CMP process, Providing excellent germanium removal rates and low surface roughness.

Figure 1 provides a graph comparing the observed Ge static etch rate (SER) for CMP compositions containing various polymer-type Ge etch inhibitor compounds.
Figure 2 provides a graph of selectivity for Ge / Ox and removal rates for Ge and silicon oxides (Ox), as well as the Ge SER observed for CMP compositions containing various concentrations of poly MADQUAT (ALCO 4773).
Figure 3 provides a graph comparing the observed Ge static etch rate (SER) for CMP compositions containing various amino acids and pyridine Ge etch inhibitor compounds.

CMP compositions useful in the methods described herein can be prepared by adding to the aqueous carrier an oxidizing agent such as hydrogen peroxide, a particulate abrasive such as colloidal silica, and a germanium etch inhibitor such as a water soluble nonionic polymer, An amino acid, a bis-pyridine compound, or a combination of two or more thereof).

Oxidizing agents useful in the compositions and methods described herein include, for example, hydrogen peroxide, ammonium persulfate, potassium permanganate, and the like. Hydrogen peroxide is the preferred oxidizing agent. Preferably, the oxidizing agent, e.g., hydrogen peroxide, is added to the composition at a concentration in the range of from about 0.1 to about 4 wt%, more preferably from about 0.5 to about 3.5 wt%, at the time of use (i.e., diluted for use in the polishing process) Lt; / RTI &gt;

The term "water-soluble" as used herein means a polymer that is dissolved in water or dispersed in water to form a substantially clear and transparent dispersion. The water soluble polymer may be a cationic or nonionic polymer comprising a basic nitrogen group, an amide group or a combination thereof. In some embodiments, the polymer is a polymer having a primary amino group, a secondary amino group, a tertiary amino group, a quaternary amino group, and a combination of two or more thereof and / or a basic nitrogen heterocyclic group such as pyridine, imidazole , Or a quaternized form thereof. In some other embodiments, the polymer typically comprises at least one member selected from the group consisting of -C (= O) NH ₂ , -C (= O) NHR, -C (= = O) NR _2, and comprises a polyamide selected from the group consisting of a combination of two or more thereof, and (e. g., a polyacrylamide compound), wherein each R is independently a hydrocarbon moiety (e. g., lower alkyl Such as methyl, ethyl, propyl, etc.). In another embodiment, the polymer may comprise a carbon amide group and a basic nitrogen group.

Polyacrylamide-type nonionic polymers having -C (= O) NH ₂ and / or -C (= O) NHR amide groups are preferred nonionic water soluble polymers for use in the compositions and methods described herein. Non-limiting examples of such materials include polyacrylamide (PAM), poly (N-isopropylacrylamide) (PNIPAM), PAM copolymers and the like.

Cationic polymers useful as germanium etch inhibitors in the compositions and methods described herein include homopolymers of cationic monomers such as poly (diallyldimethylammonium) halides such as poly (diallyldimethylammonium) chloride (poly DADMAC), poly (Methacryloyloxyethyltrimethylammonium) halide such as poly (methacryloyloxyethyltrimethylammonium) chloride (polyMADQUAT), and the like. The cationic polymer may also be a copolymer of cationic and nonionic monomers such as alkyl acrylates, alkyl methacrylates, acrylamides, styrenes, etc., such as poly (acrylamide-co-diallyldimethylammonium) chloride (PolyAm-DADMAC) and poly (dimethylamine-co-epichlorohydrin-co-ethylenediamine) (poly DEE). Some other non-limiting examples of such cationic polymers include polyethyleneimine, ethoxylated polyethyleneimine, poly (diallyldimethylammonium) halide, poly (amidoamine), poly (methacryloyloxyethyldimethylammonium) chloride, Poly (vinylpyrrolidone), poly (vinylimidazole), poly (vinylpyridine), and poly (vinylamine). Preferred cationic polymers for use in the CMP compositions of the present invention are poly (methacryloyloxyethyltrimethylammonium) halides (e.g., chlorides), also known as poly MADQUAT, such as Alco Chemical Inc., Lt; RTI ID = 0.0 &gt; ALCO &lt; / RTI &gt;

Alternatively, or in addition, the cationic polymer comprises a nitrogen-heteroaryl or quaternised nitrogen-heteroaryl group, i. E. At least one nitrogen in the aromatic ring, optionally substituted on the heteroaryl ring Aromatic heteroatom having at least one nitrogen atom in the alkylated ring in order to impart a type positive charge. Preferably, the heteroaryl group is attached to the aromatic ring directly or via an alkylene spacer group (e. G., Methylene (e. G., Methylene) (Such as, for example, quaternized poly (vinylimidazole) polymers) via carbon-nitrogen bonds through the carbon-nitrogen bond (CH ₂ ) or ethylene (CH ₂ CH ₂ ) groups. Quaternized nitrogen positive charges are balanced by counter anions which can be any combination of, for example, a halide (e.g., chloride), nitrate, methyl sulfate, or an anion. In some embodiments, the cationic polymer is selected from the group consisting of poly (vinyl-N-alkylpyridinium) polymers such as poly (2-vinyl-N-alkylpyridinium) Vinyl-N-alkylpyridinium copolymers, poly (N1-vinyl-N3-alkylimidazolium) polymers, and the like, or consist essentially of, or consist of these.

The polymer is preferably present in the CMP composition at a concentration of from about 10 to about 2000 ppm (more preferably from about 10 to about 1000) at the time of use in the polishing process described herein.

Typically, the polymer has a weight average molecular weight of at least about 5 kDa (e.g., at least about 10 kDa, at least about 20 kDa, at least about 30 kDa, at least about 40 kDa, at least about 50 kDa, 60 kDa or more) cationic polymer. The polishing composition preferably comprises a polymer having a molecular weight of about 100 kDa or less (e.g., about 80 kDa or less, about 70 kDa or less, about 60 kDa or less, or about 50 kDa or less). Preferably, the polishing composition comprises a polymer having a molecular weight from about 5 kDa to about 100 kDa (e.g., from about 10 kDa to about 80 kDa, from about 10 kDa to about 70 kDa, or from about 15 kDa to about 70 kDa) do.

Amino acids useful as germanium etch inhibitors in the compositions and methods described herein include amino acids having non-acidic side chains. In some preferred embodiments, the amino acid comprises basic side chains such as lysine, arginine, and histidine. In another embodiment, the amino acid has a hydrophobic side chain (e.g., alanine, leucine, isoleucine, valine, phenylglycine). In another embodiment, the amino acid is selected from amino acids having an isoelectric point of 6 or more (e.g., lysine, arginine, histidine, glycine, beta-alanine, valine, etc.). Preferably, the amino acid does not comprise a sulfur-containing side chain (e.g., methionine, cysteine or cystine). Examples of some preferred amino acids include, for example, lysine, arginine, histidine, glycine, beta-alanine, tricine and valine. Preferably, the amino acid is present in the composition in a concentration ranging from about 50 to about 5000 ppm.

Bis-pyridine-type Ge etch inhibitors include compounds comprising two pyridine groups linked together via a covalent bond (i. E., A bipyridyl compound) or through one to three carbon linking groups, for example a group of the formula Pyr-R'-Pyr (Wherein Pyr is a pyridine group which may be substituted or unsubstituted (e.g., by an alkyl group)). Each Pyr is independently attached to R ' at position 2, 3 or 4 of the pyridine ring. R 'may be covalently bonded (in this case, the compound is bipyridyl compound Im), (CH ₂₎ n or CH = CH (wherein, n is 1, 2 or 3). When R 'is CH = CH, the Pyr group can be attached to CH = CH in E or Z orientation. Non-limiting examples of bis-pyridine-type Ge etch inhibitors include, for example, 4,4'-trimethylenedipyridine, 1,2-bis (4-pyridyl) ethane, 2,2'- 1,2-bis (2-pyridyl) ethylene, and the like. Preferably, the bis-pyridine compound, when used, is present in the composition in a concentration ranging from about 50 to about 5000 ppm.

The particulate abrasive may comprise any abrasive material suitable for use in CMP of semiconductor and integrated circuit materials. Examples of such materials include, for example, silica, ceria, zirconia and titania. A preferred particulate abrasive is silica (e.g., colloidal silica). Preferably, the particulate abrasive has an average particle size of from about 20 to about 200 nm. Preferred colloidal silicas have an average particle size of from about 60 to about 150 nm (e.g., about 120 nm). Preferably, the abrasive (e.g., colloidal silica) is present in the CMP composition at a concentration of from about 0.2 to about 3 wt% (e.g., from about 0.4 to about 2 wt%) at the time of use. The colloidal silica particles may have any shape. In some embodiments, the colloidal silica particles are generally spherical, cocoon-shaped, or a combination thereof. Optionally, the colloidal silica may include additional cationic material (e.g., quaternary amine) on the surface of the silica particles to impart zeta potential to the surface.

The CMP compositions of the present invention may have any pH, but preferably have a pH in the range of from about 1.5 to about 9 (e.g., from about 2 to about 5). The pH of the composition may be achieved and / or maintained by the inclusion of buffering materials well known to those of ordinary skill in the chemical arts.

The polishing composition of the present invention may optionally also contain one or more other additive materials generally included in the polishing composition such as metal complexing agents, dispersants, corrosion inhibitors, viscosity modifiers, biocides, inorganic salts, and the like . For example, the composition may include biocides such as KATHON, KORDEK or NEOLONE biocides; Complexing agents such as acetic acid, picolinic acid, tartaric acid, iminodiacetic acid, benzoic acid, nitrilotriacetic acid (NTA) and the like; And / or corrosion inhibitors such as benzotriazole (BTA), 1,2,3-triazole, 1,2,4-triazole, tetrazole, 5-aminotetrazole, 3-amino- -Triazole, phenylphosphonic acid, methylphosphonic acid, and the like.

The aqueous carrier may be any aqueous solvent, such as water, aqueous methanol, aqueous ethanol, combinations thereof, and the like. Preferably, the aqueous carrier comprises predominantly demineralised water.

The polishing compositions used in the methods described herein can be prepared by any suitable technique, many of which are well known to those of ordinary skill in the art. The polishing composition may be prepared by batch or continuous process. Generally, a polishing composition can be prepared by combining its components in any order. The term "component" as used herein includes any combination of components, as well as individual components (e.g., abrasives, polymers, amino acids, buffers, etc.). For example, the abrasive may be dispersed in water, combined with the etch inhibitor component, and mixed by any method capable of introducing the component into the polishing composition. Typically, no oxidizing agent is added to the polishing composition until the composition is ready for use in a CMP process. For example, the oxidizing agent may be added just before the start of polishing. The pH can be further adjusted at any appropriate time by adding an acid, base or buffer as needed.

The polishing composition of the present invention may also be provided as a concentrate intended to be diluted with an appropriate amount of an aqueous solvent (e. G., Water) prior to use. In such embodiments, the abrasive composition concentrate is prepared by diluting the concentrate with an appropriate amount of an aqueous solvent, in an amount such that each component of the abrasive composition is present in the polishing composition in an amount within the proper range for use And may contain various components dispersed or dissolved.

The compositions and methods of the present invention surprisingly provide a low surface roughness and a significant reduction in SER (e.g., greater than 80% reduction in SER) as compared to similar CMP slurry formulations that do not contain an etch inhibitor material.

The CMP method of the present invention is preferably carried out using a chemical-mechanical polishing apparatus. Typically, the CMP apparatus moves during use and includes a platen with a velocity that is generated from orbits, linear and / or circular motions, a polishing pad that moves relative to the platen when in contact with and operates with the platen, And a carrier for holding the substrate to be polished by movement. Polishing of the substrate is performed by placing the substrate in contact with the polishing pad and the polishing composition of the present invention, and then moving the polishing pad relative to the substrate to abrade at least a portion of the substrate to polish the substrate.

The following examples further illustrate certain aspects of the invention, but of course should not be construed as limiting the scope of the invention in any way. The concentrations reported in parts per million (ppm) or% by weight (wt%), as used herein and in the examples and claims below, are based on the weight of the active ingredient of interest divided by the weight of the composition and are on a point of use basis.

Example 1

This example illustrates the effect of selected cationic and non-ionic polymers on Ge SER and removal rate.

(100) Ge blanket wafer (100) with a preferred orientation using an aqueous CMP slurry (at a pH of about 2.3) containing about 2 wt% colloidal silica, 2 wt% hydrogen peroxide, and various polymer additives at a concentration of 100 ppm Was flattened. The Ge removal rate (RR) and the static etch rate (SER) were evaluated. A platen speed of about 60 rpm, a carrier speed of about 63 rpm, a downward force of about 1.5 psi, and a slurry flow rate of about 100 mL / min using an IC1010 branded polishing pad; Planarization was performed on a POLI 500 brand polishing machine with a polishing time of 60 seconds. The wafers were immersed in a slurry at 35 占 폚 and 45 占 폚 in the presence of an oxidizing agent for 2 minutes to measure the SER.

In one evaluation, the effect of various polymers on Ge SER was measured. The characteristics of the slurry are listed in Table 1 along with the SER values and the SER results are reported in Figure 1 and reported as a normalized SER as a percentage of the SER obtained using a slurry without any polymer additives. The normalized SER was set at 100% for a composition that did not contain any etch inhibitor components.

<Table 1>

As is apparent from Figure 1, all of the polymers surprisingly provided a Ge SER reduction in the range of about 84 to 94%.

In a further evaluation, 2 wt% of commercially available colloidal silica (cocoon-shaped particles, primary particle size of about 30-35 nm, secondary particle size of about 70 nm, cationic surface-modified) Ge removal rate and SER were evaluated for a slurry containing 2 wt% hydrogen peroxide, and 0-1000 ppm poly MADQUAT. The slurry was also evaluated for the rate of PETEOS silicon oxide removal and for the selectivity of Ge: Ox (Ge removal vs. silicon oxide removal). A platen speed of about 60 rpm, a carrier speed of about 63 rpm, a downward force of about 1.5 psi, and a slurry flow rate of about 100 mL / min using an IC1010 branded polishing pad; Planarization was performed on a POLI 500 brand polishing machine with a polishing time of 60 seconds. The wafers were immersed in a slurry at 35 占 폚 and 45 占 폚 in the presence of an oxidizing agent for 2 minutes to measure the SER. The results are shown in Fig.

The results of FIG. 2 indicate that the effect of poly MADQUAT was flattened after a polymer concentration of about 100 ppm and there was a significant selectivity for Ge removal versus oxide removal of > 12 at polymer concentrations ranging from 100 to 1000 ppm.

Example 2

This example illustrates the effect of various amino acids and pyridine compounds on Ge SER.

2 wt% of commercially available colloidal silica (cocoon-shaped particles, primary particle size of about 30-35 nm, secondary particle size of about 70 nm, cationic surface-modified), 2 wt% hydrogen peroxide , And various amino acids and pyridine additives, i.e., 1000 ppm lysine, D, L-methionine, arginine, histidine, and 4,4'-trimethylene dipyridine; And 100 ppm of glycine, beta-alanine, valine, aspartic acid, glutamic acid, phenylalanine and N- (2-hydroxy-1,1-bis (hydroxymethyl) ethyl) glycine (100) Ge blanket wafers with the preferred orientation were planarized using a CMP slurry containing A platen speed of about 60 rpm, a carrier speed of about 63 rpm, a downward force of about 1.5 psi, and a slurry flow rate of about 100 mL / min using an IC1010 branded polishing pad; Planarization was performed on a POLI 500 brand polishing machine with a polishing time of 60 seconds. The wafers were immersed in a slurry at 35 占 폚 and 45 占 폚 in the presence of an oxidizing agent for 2 minutes to measure the SER. The SER results are provided in FIG. 3 and reported as a normalized SER as a percentage of the SER obtained using a slurry without any polymer additive.

The data in Figure 3 clearly show that amino acids with pyridine compounds and non-acidic side chains provided significant Ge SER reduction. Acidic amino acids such as aspartic acid and glutamic acid were ineffective while methionine and phenylglycine provided some inhibition of SER but were significantly less effective than other non-acidic amino acids. Lysine, arginine, histidine, glycine, beta-alanine and valine are all reported to have an isoelectric point, pI, of 6 or more, while methionine, phenylglycine, acidic amino acids have a pI of less than 6. Thus, in some embodiments, the preferred amino acid-type Ge etch inhibitor has an isoelectric point of 6 or greater.

Example 3

This example illustrates the effect of lysine, arginine and poly MADQUAT on Ge elimination (RR) and Ge SER.

Ge blanket wafers having a (100) preferred orientation were planarized using an aqueous CMP slurry (at a pH of about 2.3) containing various combinations of colloidal silica, hydrogen peroxide, and poly MADQUAT (ALCO 4773), lysine and arginine. The Ge removal rate (RR) and the static etch rate (SER) were evaluated. A platen speed of about 60 rpm, a carrier speed of about 63 rpm, a downward force of about 1.5 psi, and a slurry flow rate of about 100 mL / min using an IC1010 branded polishing pad; Planarization was performed on a POLI 500 brand polishing machine with a polishing time of 60 seconds. The wafers were immersed in a slurry at 35 占 폚 and 45 占 폚 in the presence of an oxidizing agent for 2 minutes to measure the SER. Table 2 provides a summary of the colloidal silica material and silica concentration used, amino acid and its concentration, polymer concentration, and hydrogen peroxide concentration as well as the observed germanium SER and RR used. Preferred targets SER and RR were < 100 A / min and 200-2000 A / min, respectively.

<Table 2>

As is evident from the data in Table 2, the combination of amino acid and polyMADQUAT is within the preferred range of < 100 A / min, while maintaining the Ge removal rate within the desired target range of 200 to 2000 ANGSTROM / min SER values were provided.

All references, including publications, patent applications, and patents, cited herein, are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and are hereby expressly incorporated herein by reference.

The use of the terms "a" and "an" and "the" and similar directives in the context of describing the invention (in particular in the context of the following claims), is not otherwise indicated herein or clearly contradicted by context Unless otherwise indicated, but are to be construed as including both singular and plural. The terms " comprising, "" having," " including, "and" containing "are to be construed as being open-ended unless the context clearly dictates otherwise. The term " consisting of "and" consisting of "should be construed as closed terms that limit any compositions or methods to the components or steps listed respectively in the claims or portions of the specification. Also, due to its open nature, the term "comprising" is intended to mean " consisting essentially of "or " consisting essentially " of the specified components or steps, as well as compositions and methods comprising other components or steps beyond those enumerated in a given claim or section. "Consisting" of &lt; / RTI &gt; The enumeration of ranges of values herein is for the purpose of acting as a shorthand method of referring individually to each individual value that falls within a range only, unless otherwise indicated herein, . All numerical values (e.g., weight, concentration, physical dimensions, removal rate, flow rate, etc.) obtained by the measurement should not be construed as an absolutely correct number, and regardless of whether the term " Should be considered to include values within known limits of measurement techniques commonly used in the related art. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all embodiments or example language (e.g., "an example &quot;) provided herein is merely to better illustrate certain aspects of the present invention and, unless otherwise claimed, It does not raise restrictions on. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

Preferred embodiments of the present invention are described herein, including the best mode known to the inventors for carrying out the present invention. Modifications of the preferred embodiments may become apparent to those skilled in the art upon reading the foregoing description. The inventors contemplate that such variations will be used where appropriate by the skilled artisan, and the inventors contemplate that the invention may be practiced otherwise than as specifically described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, any combination of the above elements in all possible variations thereof is included in the present invention, unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims (17)

(CMP) composition comprising an oxidizing agent, a particulate abrasive, and a germanium etch inhibitor selected from the group consisting of water soluble polymers, amino acids with non-acid side chains, bis-pyridine compounds, and combinations of two or more thereof Wherein the water-soluble polymer comprises a cationic or non-ionic polymer comprising a basic nitrogen group, an amide group, or a combination thereof. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt; The method according to claim 1, wherein the water-soluble polymer comprises a nitrogen group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary amino group, and a combination of two or more thereof. The composition of claim 1, wherein the water soluble polymer comprises an amide group selected from the group consisting of -C (= O) NH ₂ , -C (= O) NHR, -C (= O) NR ₂ , , Wherein each R is independently a hydrocarbon moiety. The process of any one of claims 1 to 3, wherein the CMP composition comprises a polyacrylamide nonionic polymer comprising a -C (= O) NH ₂ amide group. The method of claim 1, wherein the CMP composition comprises a cationic polymer. 6. The composition of claim 5 wherein the cationic polymer is selected from the group consisting of poly (diallyldimethylammonium) chloride (poly DADMAC), poly (methacryloyloxyethyltrimethylammonium) chloride (polyMADQUAT), poly (dimethylamine- (Poly-DEE), and copolymers of acrylamide and DADMAC. &Lt; RTI ID = 0.0 &gt; 7. The method according to any one of claims 1 to 6, wherein the CMP composition comprises an amino acid having a basic side chain. 7. The method according to any one of claims 1 to 6, wherein the CMP composition comprises an amino acid having a hydrophobic side chain. 9. The method according to any one of claims 1 to 8, wherein the CMP composition comprises an amino acid having an isoelectric point (pI) of 6 or more. 7. The method according to any one of claims 1 to 6, wherein the CMP composition comprises an amino acid selected from the group consisting of lysine, arginine, histidine, glycine, beta-alanine, tricine and valine. 11. The composition according to any one of claims 1 to 10, wherein the CMP composition comprises a bis-pyridine compound of the formula Pyr-R'-Pyr wherein each Pyr is independently selected from the 2, 3 or 4 positions of the pyridine group A pyridine group attached to R '; R 'is a covalent bond, (CH ₂₎ n or a CH = CH; and n is 1, 2 or 3. 12. The process of claim 11, wherein the bis-pyridine compound is selected from the group consisting of 4,4'-trimethylenedipyridine, 1,2-bis (4-pyridyl) ethane, 2,2'- -Pyridyl) ethylene. &Lt; / RTI &gt; 13. The method of any one of claims 1 to 12, wherein the amino acid is present in the composition in a concentration ranging from about 50 to about 5000 parts per million (ppm). 14. The process of any one of claims 1 to 13, wherein the water soluble polymer is present in the CMP composition in a concentration ranging from about 10 to about 2000 ppm. 15. The method according to any one of claims 1 to 14, wherein the bis-pyridine compound is present in the composition in a concentration ranging from about 50 to about 5000 ppm. 16. The method of any one of claims 1 to 15, wherein the particulate abrasive comprises colloidal silica at a concentration in the range of from about 0.5 to about 3.5 weight percent (wt%). 17. The method of any one of claims 1 to 16, wherein the oxidizing agent comprises hydrogen peroxide in a concentration ranging from about 0.5 to about 4 wt%.

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