THE MAIN TEA ETA AITOAUS 20170362466A1 MAIMARIANA MATAT AN ( 19) United States (12 ) Patent Application Publication ( 10) Pub . No. : US 2017/ 0362466 A1 Shi et al. (43 ) Pub . Date : Dec . 21 , 2017 (54 ) CHEMICAL MECHANICAL POLISHING Publication Classification (CMP ) OF COBALT -CONTAINING (51 ) Int . Ci. SUBSTRATE C09G 1 /02 ( 2006 .01 ) B24B 37 /04 (2012 .01 ) ( 71 ) Applicant: Versum Materials US , LLC , C09K 3 / 14 (2006 . 01) Allentown, PA (US ) C23F 3 /04 ( 2006 .01 ) ( 72 ) Inventors : Xiaobo Shi, Chandler , AZ (US ); HOIL 21 /321 (2006 . 01 ) Joseph Rose , Chandler , AZ (US ) ; HOIL 21/ 768 (2006 . 01) Timothy Joseph Clore , Chandler , AZ 2 ) U . S . CI. (US ) ; James Allen Schlueter , Phoenix , CPC ...... C09G 1 /02 ( 2013 . 01 ) ; C23F 3 / 04 AZ (US ) ; Malcolm Grief , Phoenix , AZ ( 2013 . 01 ) ; HOIL 21 /3212 ( 2013 .01 ) ; B24B (US ) ; Mark Leonard O 'Neill , Queen 37 /044 ( 2013 .01 ) ; C09K 3 / 1409 ( 2013 .01 ) ; Creek , AZ (US ) HOIL 21 /7684 ( 2013 .01 ) ( 73 ) Assignee : Versum Materials US, LLC , (57 ) ABSTRACT Allentown , PA (US ) Chemicalmechanical polishing (CMP ) compositions, meth ods and systems for polish cobalt or cobalt - containing (21 ) Appl. No. : 15 / 615, 236 substrates are provided . The CMP compositions comprise a - alanine , abrasive particles , a salt of phosphate , corrosion (22 ) Filed : Jun . 6 , 2017 inhibitor , oxidizer and water. The cobalt chemicalmechani cal polishing compositions provide high removal rate of Co Related U . S . Application Data aswell as very high selectivity of Co film vs . dielectric film , (60 ) Provisional application No .62 / 350 ,844 , filed on Jun . such as TEOS, SixNy ( with 1 . 0 < x < 3 . 0 , 1 .33 < y < 4 . 0 ) , low - k , 16 , 2016 . and ultra low -k films. Patent Application Publication Dec . 21 , 2017 US 2017 / 0362466 A1

CO RR vs Phosphate Added 2000

CORR(A/30sec)

20 40 60 80 100 Ammonium Phosphate Dibasic (ppm )

Figure 1 US 2017 /0362466 A1 Dec . 21, 2017

CHEMICAL MECHANICAL POLISHING with pH 10 , a passivation layer is formed on cobalt surface (CMP ) OF COBALT -CONTAINING and cobalt - copper galvanic corrosion is minimized . SUBSTRATE [ 0009 ] “ The Effect of H2O2 and 2 -MT on the Chemical Mechanical Polishing of Cobalt Adhesion Layer in Acid CROSS REFERENCE TO RELATED PATENT Slurry , " Hai- Sheng Lu et al. , Electrochem . and Solid - State APPLICATIONS Letters , Vol. 15 , Issue 4 , pp . H97 - H100 ( 2012 ) demonstrates that H2O2 greatly increases the static etch rate (SER ) and [0001 ] The present patent application claims the benefit of removal rate (RR ) of cobalt . The 2 -Mercaptothiazoline U .S . Provisional Patent Application Ser . No . 62/ 350 ,844 ( 2 -MT ) is very efficient at inhibiting cobalt corrosion and filed Jun . 16 , 2016 . reducing the SER and RR of cobalt in the acid slurry . In the glycine based slurry at pH = 5 , by using 2 -MT , the corrosion BACKGROUND OF THE INVENTION potential difference between Co and Cu can be reduced to a [0002 ] The present invention relates generally to chemical very small value . mechanical polishing ( CMP ) of semiconductor substrates. [0010 ] “ Cobalt Polishing with Reduced Galvanic Corro [0003 ] As industry standards trend toward smaller device sion at Copper/ Cobalt Interface Using Hydrogen Peroxide as features , there is a continuous developing need for new types an Oxidizer in Colloidal Silica - Based Slurries , " B . C . of metalmaterials that can be used to replace tungsten ( W ) Peethala et al. , Journal of the Electrochemical Society , Vol. or copper (Cu ) as new electrical conducting interconnection 159 , Issue 6 , pp . H582 -H588 ( 2012 ) used colloidal silica materials in IC chip fabrication and integration , specifically, based slurry with 1 wt. % H , O , as the oxidizer and 0 . 5 wt for 16 nm technology nodes and beyond applications. Cobalt % arginine as the complexing agent for CMP on cobalt ; this (Co ) has been considered and tested as one of the promising slurry showed superior performance (better post -polish sur new type of metal interconnection material in IC chip face quality and no pit formation ) at pH 10 compared to pH integration . CMP of cobalt interconnect requires polishing 6 and 8 . At PH 10 , there is no measurable dissolution of Co of cobalt layer at high removal rates and provide high degree and an open circuit potential (E . c) difference of about 20 mV of planarity without introducing corrosion defects . Cobalt between Cu and Co, suggestive of reduced galvanic corro interconnect polishing requires removal rates in excess of sion . The results also suggest that , during polishing , the Co 1000 Angstroms/ minute (> 1000 Å /min ) , which requires film surface was covered with a passive film , possibly of Co slurry compositions which are chemically aggressive to ( III ) oxides . Addition of 5 mM BTA to this slurry inhibited cobalt and yet not cause any corrosion issues. Cu dissolution rates and yielded a Co / Cu removal rate ratio [ 0004 ] Unfortunately , existing slurries for polishing of of about 1 . 2 while further reducing the E difference copper or tungsten cannot be used to give satisfactory CMP between Cu and Co to about 10 mV, both very desirable performance for cobalt interconnect structures . Without attributes. being limited to any theory , this may be due to cobalt being [0011 ] Thus , there is a strong need for the development of chemically reactive with the existing polishing slurries, innovative Co CMP polishing compositions that can provide resulting in cobalt dissolution , which in turn leads to a high high , tunable Co film removal rates, low Co film static etch defect count. rates, low barrier film and dielectric film removal rates , high [ 0005 ] Most of the prior art on cobalt CMP relates to and desirable selectivity of Co vs . barrier films and Co vs . polishing thin cobalt barrier liners underneath the copper dielectric films, and minimize or eliminate the possible interconnects . The requirement of cobalt barrier polishing is galvanic corrosion at Co / Cu interface . quite different from cobalt interconnect polishing . Cobalt barrier polish requires cobalt removal rates typically less BRIEF SUMMARY OF THE INVENTION than 500 Angstroms/min ( < 500 Å / min ) . [0012 ] The needs are satisfied by using the disclosed [0006 ] US Patent Applications 2016108286 , compositions, methods, and planarization systems for CMP 20130186850 teach slurry compositions for chemical of cobalt- containing substrate . mechanical polishing of a cobalt interconnect or a cobalt [0013 ] In one aspect , CMP polishing compositions are barrier layer. provided for CMP of cobalt -containing substrate . The CMP [0007 ] US Patent Application 20130140273 teaches slurry polishing composition comprises: for chemical mechanical polishing of Co . The slurry com 10014 ] an abrasive ; prises components by weight as follows, inhibitor 0 .01 - 2 % , [0015 ] alanine comprising a - amino group ; oxidant 0 - 5 % , abrasive 0 . 1 - 10 % , complexing agent 0 .001 [0016 ] phosphate compound comprising H2PO4 , 10 % , and the rest of water. The pH value of the slurries is HPO - 2 - , or PO 4 3 - ; adjusted to 3 -5 by a pH value adjustor. The inhibitor is [ 0017 ] corrosion inhibitor ; chosen from one or more kinds of five -membered hetero 10018 ] oxidizer ; cycle compound containing S and N atoms or containing S [ 0019 ] water ; and or N atom . The oxidant is one or more chosen from H2O2, 10020 ] optionally (NH2 ) , S , O , KIOA, and KC105. The abrasive is one or more [0021 ] an amine compound ; chosen from SiO2, CeO2, and A1203 . The complexing agent [0022 ] a chelating agent; is one or more chosen from amino acid and citric acid . The [0023 ] a pH adjusting agent; slurry can effectively prevent Co over corrosion and reduce [0024 ] biocide ; and the polishing rate of Co in the polishing process . [0025 ] a surfactant; [0008 ] “ Fundamental Study of Chemical -Mechanical Pol [0026 ] wherein the chemical mechanical polishing ishing Slurry of Cobalt Barrier Metal for Next -Generation (CMP ) polishing composition having a pH from 2 .0 to Interconnect Process , ” Hideak Nishizawa et al. , Jpn . J . Appl. about 12 ; preferably from 6 . 0 to 10 . 0 ; and more pref Phys. , Vol. 49, 05FC03 (2 pages ), 2010 show that in slurries erably from 7 . 0 to 9 .0 ; most preferably from 7. 5 to 8 . 5 . US 2017 /0362466 A1 Dec . 21, 2017

[0027 ] In another aspect, a method of using the Co CMP [0060 ) biocide ; and polishing composition is provided for CMP of cobalt -con [0061 ] a surfactant; taining substrate . The method comprises steps of: [ 0062 ] wherein the chemical mechanical polishing [ 0028 ] a ) providing a semiconductor substrate having a (CMP ) polishing composition having a pH from 2 . 0 surface containing a first material and at least one to about 12 ; preferably from 6 . 0 to 10 . 0 ; and more second material; preferably from 7 . 0 to 9 . 0 ; most preferably from 7 . 5 to 8 . 5 ) ; [0029 ] b ) wherein the first material is Co and the second [ 0063 ] wherein at least a portion of the surface is in material is selected from the group consisting of dielec contact with both the polishing pad and the chemical tric film , low - k and ultra low - k film , and barrier film ; mechanical polishing composition . [0030 ] c ) providing a polishing pad ; [0064 ] The chemicalmechanical polishing (CMP ) polish [0031 ] d ) providing a chemical mechanical polishing ing compositions comprise from 0 . 005 wt. % to 25 wt. % ; composition comprises : preferably from 0 . 05 wt. % to 5 wt. % , and more preferably [0032 ] an abrasive ; from 0 . 1 wt. % to 2 . 5 wt. % of abrasive . [0033 ] alanine comprising a - amino group ; 100651. The abrasive includes, but is not limited to nano [0034 ] phosphate compound comprising H2PO4 , sized colloidal silica or high purity colloidal silica particles ; HPO42- , or PC - ; nano - sized inorganic metal oxide particles selected from the [0035 ] corrosion inhibitor ; group consisting of alumina , titania , zirconia , ceria and [ 0036 ] oxidizer ; combinations thereof ; nano - sized diamond particles ; nano 10037 ] water ; and sized silicon nitride particles ; mono -modal , bi-modal , or [0038 ] optionally multi- modal colloidal abrasive particles ; organic polymer [0039 ] an amine compound ; based soft abrasives ; surface - coated or modified abrasives [0040 ] a chelating agent; such as ceria coated silica particles and combinations [0041 ] a pH adjusting agent; thereof. [0042 ] biocide ; and 100661. The chemicalmechanical polishing (CMP ) polish 10043 ] a surfactant ; ing compositions comprise from 0 . 05 wt. % to 5 wt. % ; [ 0044 ] wherein the chemical mechanical polishing preferably from 0 . 1 wt. % to 2 .50 wt. % ; more preferably ( CMP) polishing composition having a pH from 2 . 0 from 0 . 5 wt. % to 2 wt. % ; and most preferably from 0 . 825 to about 12 ; preferably from 6 . 0 to 10 . 0 ; and more wt. % to 1 .65 wt. % of alanine comprising a - amino group . preferably from 7 .0 to 9 . 0 ; most preferably from 7 .5 [0067 ] Alanine may comprise different optical isomers to 8 . 5 ; such as D - Alanine , L -alanine and their racemic mixture and DL - alanine . [0045 ] e) polishing the surface of the semiconductor [0068 ] The chemical mechanical polishing (CMP ) polish substrate to selectively remove the first material ; ing compositions comprise from 2 ppm to 100 ppm , pref wherein at least a portion of the surface is in contact erably 2 ppm to 50 ppm , more preferably 5 ppm to 20 ppm with both the polishing pad and the chemicalmechani of a phosphate compound ( compound comprising H2PO4 ' - , cal polishing composition ; and ratio of removal rate of HPO 2 - or PO43 - group ). the first material to removal rate of the second material [ 0069] Phosphate may exist in phosphate ion ( tribasic ), is equal or greater than 1 ; preferably 10 , more prefer hydrogen phosphate ion ( dibasic ), dihydrogen phosphate ably greater than 50 , and most preferably greater than (mono -basic ) , or trihydrogen phosphate ( acid form ) depend 100 . ing upon pH of the slurry . The phosphate compound may be [ 0046 ] In yet another aspect , a CMP system is provided for inorganic salt of phosphoric acid or an organophosphate CMP of cobalt - containing substrate . The CMP system com compound . Useful phosphate compounds may also include prises : pyrophosphate compounds formed by condensing phos phates . Preferred phosphate compounds are inorganic phos 100471 a semiconductor substrate having a surface con phate compounds such as ammonium phosphate or potas taining a first material and at least one second material; sium phosphate in either r monobasic , dibasic or tribasic wherein the firstmaterial is Co and the second material forms. is selected from the group consisting of dielectric films [0070 ] The chemical mechanical polishing ( CMP ) polish ( such as TEOS, SixNy ( with 1 . 0 < x < 3 . 0 , 1 .33 < y < 4 . 0 ) , ing compositions comprise from 0 .0005 wt. % to 0 .5 wt. % low - k and ultra low - k films, and barrier films (such as preferably from 0 . 0025 wt. % to 0 . 25 wt. % and more Ta, TaN , Ti , and TiN films) ; preferably from 0 .05 wt. % to 0 .15 wt. % of corrosion [0048 ] a polishing pad ; and inhibitor. The corrosion inhibitor includes, but is not limited [0049 ] a chemical mechanical polishing composition to 1 , 2 , 4 - triazole and its derivatives, benzotriazole and its comprises: derivatives , 1 , 2 , 3 - triazole and its derivatives , pyrazole and [0050 ] an abrasive; its derivatives , imidazole and its derivatives , benzimidazole [0051 ] alanine comprising a -amino group ; and its derivatives , isocyanurate and its derivatives , and [ 0052 ] phosphate compound comprising PO 3 - ; combinations thereof. [0053 ] corrosion inhibitor ; [0071 ] The chemicalmechanical polishing (CMP ) polish [ 0054 ] oxidizer ; ing compositions optionally comprise a chelating agent [0055 ] water; and ranging from 0. 01 wt. % to 10 wt. % , preferably from 0. 1 wt. [0056 ] optionally % to 5 wt. % , more preferably from 0 . 5 wt. % to 2 wt. % , [ 0057 ] an amine compound ; and most preferably from 0 . 825 wt. % to 1 . 65 wt. % . [0058 ] a chelating agent; 10072 ] The chelating agent includes but is not limited to [ 0059 ] a pH adjusting agent; glycine, serine, proline , histidine , isoleucine, leucine , lysine , US 2017 /0362466 A1 Dec . 21, 2017 methionine, phenylalanine , threonine , tryptophan , valine , [0079 ] The chemical mechanical polishing (CMP ) polish arginine , asparagine , aspartic acid , cystein , glutamic acid , ing compositions optionally comprise from 0 . 0005 wt. % to glutamine , ornithine, picolinic acid , selenocystein , tyrosine , 0 .15 wt. % , preferably from 0 .001 wt. % to 0 .05 wt. % , and sarcosine , bicine , tricine, aceglutamide, n -acetylaspartic more preferably from 0 .0025 wt. % to 0 .025 wt. % of a acid , acetylcarnitine , acetylcysteine , n -acetylglutamic acid , surfactant. The surfactant includes, but is not limited to acetylleucine , acivicin , s -adenosyl - 1 -homocysteine , agari non - ironic surfactants , such as acetylenic diol type of sur tine , alanosine , aminohippuric acid , l - arginine ethyl ester , factants and ethoxylate / propyloxylate surfactants , anionic aspartame, aspartylglucosamine , benzylmercapturic acid , surfactants , such as sulfonic acids/ salts , carboxylates , phos biocytin , brivanib alaninate , carbocisteine , n (6 ) -carboxym phates , cationic surfactants , such as most quaternary ammo ethyllysine , carglumic acid , cilastatin , citiolone , coprine, nium based surfactants , and amphoteric surfactants , such as dibromotyrosine , dihydroxyphenylglycine , eflornithine , fen betaines and amino acid derivatives based surfactants . clonine , 4 - fluoro - l -threonine , n - formylmethionine , gamma [0080 ] The chemical mechanical polishing (CMP ) polish 1 - glutamyl- l - cysteine , 4 -( y -glutamylamino )butanoic acid , ing compositions optionally comprise from 0 .0001 wt. % t glutaurine , glycocyamine, hadacidin , hepapressin , lisinopril , to 0 .20 wt. % ; preferably from 0 .0010 wt. % to 0 .10 wt. % , lymecycline, n -methyl -d -aspartic acid , n -methyl - l- glutamic and more preferably from 0 .0025 wt. % to 0 . 050 wt. % of an acid , milacemide , nitrosoproline , nocardicin a , nopaline , amine compound . The amine compound includes , but is not octopine, ombrabulin , opine, orthanilic acid , oxaceprol, limited to ethylene diamine, propylene diamine, organic polylysine , remacemide, salicyluric acid , silk amino acid , amine compound containing multi amino groups in the same stampidine, tabtoxin , tetrazolylglycine , thiorphan , thymec molecular , and combinations thereof. tacin , tiopronin , tryptophan tryptophylquinone, valaciclovir , 10081] The ratio of removal rate of the first material to the valganciclovir and combinations thereof. removal rate of the second material wherein the second [0073 ] The preferred chelating agents are glycine, pico material is dielectric film is equal or greater than 1; prefer linic acid , and combinations thereof. ably 10 , more preferably 50 , and most preferably 100 . [0074 ] The chemical mechanical polishing (CMP ) polish [0082 ] With disclosed compositions, the Co bulk CMP ing compositions optionally comprise from 0 . 005 wt. % to polishing compositions are able to provide desirable high 10 wt. % ; preferably from 0 .25 wt. % to 3 wt. % , and more and tunable Co film removal rates; low barrier film and preferably from 0 . 5 % to 1 . 5 % oxidizer. The oxidizer dielectric film removal rates ; reduced Co film static etch includes, but is not limited to periodic acid , hydrogen rates (SER ) for better Co film corrosion protection ; high and peroxide , potassium iodate , potassium permanganate , desirable removal selectivity of cobalt vs. dielectric films ammonium persulfate , ammonium molybdate, ferric nitrate , such as TEOS , SixNy (with 1 . 0 < x < 3 . 0 , 1 . 33 < y < 4 . 0 ) , SICO , nitric acid , potassium nitrate , and mixtures thereof; wherein low - k , and ultra low - k films. the preferred oxidizer is hydrogen peroxide . 10083 ] Other aspects , features and embodiments of the [0075 ] The chemical mechanical polishing (CMP ) polish invention will be more fully apparent from the ensuing ing compositions have pH from about 2 . 0 to about 12 ; disclosure and appended claims. preferably from 6 . 0 to 10 . 0 ; more preferably from 7 . 0 to 9 . 0 ; and most preferably from 7 . 5 to 8 . 5 . BRIEF DESCRIPTION OF SEVERAL VIEWS OF [0076 ] The chemical mechanical polishing (CMP ) polish ing compositions optionally comprise from 0 .01 wt. % to 0 . 5 THE DRAWINGS wt. % ; preferably from 0 . 05 wt. % to 0 . 15 wt. % pH [0084 ] FIG . 1 shows the cobalt removal rates with phos adjusting agent . The pH adjusting agent includes , but is not phate doping compositions limited to nitric acid , hydrochloric acid , sulfuric acid , phos phoric acid , sodium hydride, potassium hydroxide, ammo DETAILED DESCRIPTION OF THE nium hydroxide, tetraalkylammonium hydroxide , organic INVENTION amines, and mixtures thereof; wherein the preferred pH adjusting agent is nitric acid . [0085 ] Chemical mechanical polishing (CMP ) composi [0077 ] The chemical mechanical polishing (CMP ) polish tions (or CMP slurries ) , methods and system for polish ing compositions optionally comprise from 0 .00001 wt. % to cobalt or cobalt -containing substrates are disclosed herein . 0 .10 wt. % , preferably from 0 .0001 wt. % to 0 .005 wt. % , [ 0086 ] The cobalt bulk CMP polishing compositions dis and more preferably from 0. 00015 wt. % to 0 .0025 wt. % of closed herein comprises abrasive , alpha - alanine , phosphate a biocide . compound , corrosion inhibitors , water, and other selected [0078 ] The biocide includes but is not limited to tetram suitable chemical additive such as complexing agents or ethylammonium chloride , tetraethylammonium chloride , chelating agents , oxidizers ; biological preservatives or bio tetrapropylammonium chloride, alkylbenzyldimethylammo cide ; surfactants or surface wetting agents for better surface nium chloride , and alkylbenzyldimethylammonium hydrox wetting and surface tension reduction ; pH adjusting agents ide , wherein the alkyl chain ranges from 1 to about 20 to optimize pH operation window for the optimized polish carbon atoms, sodium chlorite , sodium hypochlorite , isothi performances . azolinone compounds such as methylisothiazolinone, meth [0087 ] With disclosed compositions, the Co bulk CMP ylchloroisothiazolinone and benzisothiazolinone . Some of polishing compositions are able to provide desirable high the commercially available preservatives include and tunable Co film removal rates; low barrier film and KATHONTM and NEOLENETM product families from Dow dielectric film removal rates; reduced Co film static etch Chemicals and Prevento1TM family from Lanxess . The pre rates (SER ) for better Co film corrosion protection ; high and ferred biocides are isothiozilone compounds such as meth desirable removal selectivity of cobalt vs . dielectric films ylisothiazolinone , methylchloroisothiazolinone and ben such as TEOS , SixNy (with 1 . 0 < x < 3 . 0 , 1 . 33 < y < 4 . 0 ) , SiCO , zisothiazolinone low - k , and ultra low - k films . US 2017 /0362466 A1 Dec . 21, 2017

[0088 ] The chemical mechanical polishing (CMP ) polish inorganic salt of phosphoric acid or an organophosphate ing compositions have pH from about 2 . 0 to about 12 ; compound . Useful phosphate compounds may also include preferably from 6 .0 to 10 . 0 ;more preferably from 7 .0 to 9. 0 ; pyrophosphate compounds formed by condensing phos and most preferably from 7 . 5 to 8 .5 . phates . Examples of inorganic phosphate compounds [0089 ] Method for polishing involves providing a semi include salts of phosphoric acid with sodium , potassium , conductor substrate having a surface containing a first rubidium , cesium , ammonium or quaternary ammonium material and at least one second material; wherein the first hydroxides . Organic phosphates could include esters of material comprises Co and the second material is selected phosphoric acids . The organic phosphate compounds may from the group consisting of dielectric films ( such as TEOS, also comprise other functional groups such as halides , thiols , SixNy ( with 1 . 0 < x < 3 . 0 , 1 . 33 < y < 4 . 0 ) , SiC , low - k and ultra carbonyls , amines, amides, ketones , aldehydes, carboxylic low - k films ) and barrier films ( such as Ti, TiN , Ta , TaN ) . group , etc . Examples of organophosphate compounds [0090 ] The Co bulk CMP polishing compositions contain include dimethyl phosphate , trimethyl phosphate , 0 , 0 - Di 0 .005 wt. % to 25 wt. % abrasives ; preferably from 0 . 05 wt. ethyl thiophosphate potassium salt, butyl acid phosphate , % to 5 wt. % ; and more preferably from 0 . 1 wt. % to 2 . 5 wt. Tris (2 - chloroethyl) phosphate , Isopropyl phosphate , tributyl % . phosphates , etc . Preferred compounds are monobasic or [ 0091] Abrasive used for Co CMP polishing compositions dibasic or tribasic phosphates or mixtures thereof with are nano - sized particles include , but are not limited to , ammonium or potassium counter - ions . nano - sized colloidal silica or high purity colloidal silica (0100 ] The CMP polishing compositions contain 0 .0005 particles; nano -sized inorganic metal oxide particles , such as wt. % to 0 . 5 wt. % corrosion inhibitor; preferably from alumina , titania , zirconia , ceria , and combinations thereof; 0 . 0025 wt. % to 0 .25 wt. % ; and more preferably from 0 .05 nano -sized diamond particles ; nano - sized silicon nitride wt. % to 0 . 15 wt. % . particles ; mono -modal , bi- modal , or multi -modal colloidal 0101 ] Corrosion inhibitors used for the cobalt bulk CMP abrasive particles ; organic polymer -based soft abrasives; slurry include , but are not limited to , 1 , 2 , 4 - triazole and its surface - coated or modified abrasives ; and combinations derivatives, benzotriazole and its derivatives , 1 , 2 , 3 - triazole thereof. and its derivatives , pyrazole and its derivatives , imidazole [0092 ] The surface - coated or modified abrasives include and its derivatives , benzimidazole and its derivatives , iso but are not limited to the colloidal silica particles doped by cyanurate and its derivatives , and combinations thereof. other metal oxide within lattice of the colloidal silica , such [0102 ] The CMP polishing compositions comprise 0 . 005 as alumina doped silica particles, colloidal aluminum oxide , wt . % to 10 wt . % oxidizer ; preferably from 0 . 25 wt . % to which include alpha -, beta -, and gamma- types of aluminum 3 wt. % , and more preferably from 0 .5 wt. % to 1. 5 wt. % . oxides , colloidal and photoactive titanium dioxide , cerium f0103 ] Oxidizers used for the CMP polishing composi oxide, colloidal cerium oxide, nano - sized diamond particles , tions include , but are not limited to , periodic acid , hydrogen nano -sized silicon nitride particles, mono -modal , bi- modal , peroxide , potassium iodate , potassium permanganate , multi- modal colloidal abrasive particles , zirconium oxide , ammonium persulfate, ammonium molybdate , ferric nitrate , organic polymer- based soft abrasives, surface -coated or nitric acid , potassium nitrate , and mixtures thereof . The modified abrasives , and mixtures thereof. preferred oxidizer is hydrogen peroxide . 10093 ]. The nano - sized particles have narrow or broad [0104 ] The CMP polishing compositions may optionally particle size distributions , various sizes and various shapes . comprise organic and amino acids as chelating or complex The various shapes of the abrasives include spherical shape, ing agents . cocoon shape , aggregate shape and other shapes . [0105 ] The chelating agent ranges from 0 .01 wt. % to 10 [0094 ] The chemical mechanical polishing (CMP ) polish wt. % , preferably from 0 . 1 wt. % to 5 wt. % , more preferably ing compositions comprise from 0 .05 wt. % to 5 wt. % ; from 0 . 5 wt. % to 2 wt. % , and most preferably from 0 .825 preferably from 0 . 1 wt. % to 2 . 5 wt. % ; more preferably wt. % to 1 .65 wt. % . from 0 . 5 wt. % to 2 wt. % ; and most preferably from 0 .825 [0106 ] The chelating agent includes but is not limited to wt. % to 1 .65 wt . % of alanine comprising a -amino group . glycine , serine , proline , histidine , isoleucine, leucine , lysine , [0095 ] Alanine having a - amino group is an a -alanine methionine , phenylalanine , threonine, tryptophan , valine , wherein the amino group is at the a - position from the arginine, asparagine, aspartic acid , cystein , glutamic acid , carboxylate group . glutamine , ornithine , picolinic acid , selenocystein , tyrosine , 0096 ] The a - alanine comprises D - alanine , L - alanine . The sarcosine, bicine , tricine, aceglutamide, n - acetylaspartic “ L ” refers to the “ left -handed ” chemical form (or the L acid , acetylcarnitine , acetylcysteine, n -acetylglutamic acid , isomer ) of the alpha - alanine molecule . The “ D ” refers to the acetylleucine , acivicin , s - adenosyl- 1- homocysteine , agari " right- handed ” chemical form ( or the D isomer ) of the tine, alanosine, aminohippuric acid , l- arginine ethyl ester , molecule . The L and D forms are mirror - images of each aspartame, aspartylglucosamine , benzylmercapturic acid , other. biocytin , brivanib alaninate , carbocisteine, n ( 6 ) -carboxym [0097 ] The a -alanine comprises D -alanine , L - alanine , and ethyllysine, carglumic acid , cilastatin , citiolone , coprine , DL -alanine which is a racemic mixture of D - and L - alanine . dibromotyrosine , dihydroxyphenylglycine , eflornithine, fen [ 0098 ] The CMP polishing compositions comprise from 2 clonine , 4 - fluoro - 1 - threonine , n - formylmethionine , gamma ppm to 100 ppm , preferably 2 ppm to 50 ppm , more l - glutamyl- 1 - cysteine, 4 - ( y - glutamylamino )butanoic acid , preferably 5 ppm to 20 ppm of a phosphate compound glutaurine , glycocyamine , hadacidin , hepapressin , lisinopril, ( compound comprising H2PO4 ' -, HPO42 -, or PO43 - group ) . lymecycline , n -methyl - d - aspartic acid , n -methyl - l - glutamic [0099 ] Phosphate may exist in phosphate ion ( tribasic ) or acid , milacemide , nitrosoproline , nocardicin a , nopaline , hydrogen phosphate ion (dibasic ) or dihydrogen phosphate octopine , ombrabulin , opine , orthanilic acid , oxaceprol , (mono -basic ) or trihydrogen phosphate (acid form ) depend polylysine , remacemide, salicyluric acid , silk amino acid , ing upon pH of the slurry . The phosphate compound may be stampidine , tabtoxin , tetrazolylglycine , thiorphan , thymec US 2017 /0362466 A1 Dec . 21, 2017

tacin , tiopronin , tryptophan tryptophylquinone , valaciclovir , thiazolinone . Some of the commercially available preserva valganciclovir , and combinations thereof. tives include KATHONTM and NEOLENETM product [ 0107] The preferred chelating agent are glycine, picolinic families from Dow Chemicals and PreventolTM family from acid , and combinations thereof. Lanxess . [0108 ] The CMP polishing compositionsmay contain 0 .01 [0119 ] The preferred biocides are isothiozilone com wt. % to 0 . 5 wt. % ; and preferably from 0 .05 wt. % to 0 . 15 pounds such as methylisothiazolinone , methylchloroisothi wt. % of pH adjusting agent. azolinone and benzisothiazolinone [ 0109] pH adjusting agents used for the CMP polishing 10120 ] In certain embodiments, the slurry components compositions include, but are not limited to , nitric acid , may have concentrated by reducing water in the formulation hydrochloric acid , sulfuric acid , phosphoric acid , various and be subsequently diluted at point of use with water inorganic and organic acids , and mixtures thereof. addition . Slurry formulation may be split into two or more [ 0110 ] pH adjusting agents also include that basic pH components , that are mixed at the point of use to help with adjusting agents , such as sodium hydride, potassium any issues such as particle stability , chemical stability , hydroxide, ammonium hydroxide , tetraalkyl hydroxide, peroxide stability . organic amines , and other chemical reagents that can be used [0121 Formulations of this invention are useful for pol to adjust pH towards more alkaline direction . The preferred ishing cobalt containing films including pure cobalt and pH adjusting agent is nitric acid . alloys of cobalt at high removal rates . In certain embodi [ 0111] The chemical mechanical polishing ( CMP ) polish ments the cobalt films can be polished at a removal rates ing compositions optionally comprise from 0 .0001 wt. % t greater than 500 Angstroms/ min or more preferably greater to 0 . 20 wt. % ; preferably from 0 .0010 wt. % to 0 . 10 wt. % , than 750 Angstroms/ min or most preferably more than 1000 and more preferably from 0 . 0025 wt. % to 0 .050 wt. % of an Angstroms/ min . amine compound ; [0122 ] Further, the polishing compositions of this inven [ 0112 ] The amine compounds are used to boost cobalt film tion can be used to polish cobalt films selectively compared removal rates . The amine compounds may include, but are to a second film serving as a different function such as not limited to ethylene diamine, propylene diamine , other barrier, liner or dielectric . In certain embodiments , the organic diamine compounds , and organic amine compounds removal rate selectivity between cobalt and the second film containing multi amino groups in the same molecular frame is greater than 10 or more preferably greater than 25 or most work . preferably greater than 50 . [0113 ] The CMP polishing compositions may contain 0 .0005 wt. % to 0 . 15 wt. % surfactants ; the preferred WORKING EXAMPLES concentration of surfactants ranges from 0 .001 wt. % to 0 .05 [0123 ] The features and advantages of the invention are wt. % . The more preferred concentration of surfactants more fully shown by the following non -limiting examples . ranges from 0 . 0025 wt. % to 0 .025 wt. % . [0114 ] Surfactants or surface wetting agents used for the Experimental Section CMP polishing compositions include , but are not limited to , non - ironic surfactants , such as dynol type of surfactants and [0124 ] Polishing Pad : Dow ' s IC1010 Pad was used during tergitol type of surfactants ; anionic surfactants , such as CMP, supplied by Dow Chemicals Corp . dodecyl sulfate sodium salts or potassium salts ; cationic [0125 ] Parameters : surfactants, such as most quaternary ammonium based sur Å : angstrom ( s ) — a unit of length factants ; and amphoteric surfactants , such as betaines and BP : back pressure, in psi units amino acid derivatives based surfactants . CMP: chemical mechanical planarization = chemical [0115 ] The CMP polishing compositions often require mechanical polishing additives to prevent bacterial and fungal growth during CS: carrier speed storage. The CMP polishing compositions optionally contain DF: Down force: pressure applied during CMP, unit : psi a biocide ranging from 0 . 00001 wt. % to 0 . 10 wt. % , min : minute ( s ) preferably from 0 . 0001 wt. % to 0 . 005 wt. % , and more ml: milliliter ( s ) preferably from 0 .00015 wt. % to 0 .0025 wt. % to prevent mV: millivolt ( s ) bacterial and fungal growth during storage . psi: pounds per square inch [0116 ] The biocide includes but is not limited to quater PS : platen rotational speed of polishing tool, in rpm ( revo nary ammonium compounds and chlorine compounds, iso lution ( s ) per minute ) thiazolone compounds, tetramethylammonium chloride , tet SF : polishing composition flow , ml/min raethylammonium chloride, tetrapropylammonium chloride ; [0126 ] Removal Rates and combinations thereof. [0127 ] Cobalt removal rate (CO RR ) was measured at 1 .5 [0117 ] Some of the additives to control biological growth psi down pressure of the CMP tool are disclosed in U . S . Pat. No . 5 , 230 ,833 ( Romberger et al. ) and US Patent Application No . US 20020025762 . Working Examples [ 0118 ] Biological growth inhibitors include but are not limited to tetramethylammonium chloride, tetraethylammo [0128 ] The features and advantages of the invention are nium chloride, tetrapropylammonium chloride, alkylben more fully shown by the following non - limiting examples . zyldimethylammonium chloride , and alkylbenzyldimethyl ammonium hydroxide , wherein the alkyl chain ranges from Experimental Section 1 to about 20 carbon atoms, sodium chlorite , sodium [0129 ] Parameters : hypochlorite , isothiazolinone compounds such as methyl- Å : angstrom ( s ) — a unit of length isothiazolinone , methylchloroisothiazolinone and benziso - BP : back pressure , in psi units US 2017 /0362466 A1 Dec . 21, 2017

CMP: chemical mechanical planarization = chemical [ 0137 ] DL - alanine powder was purchased from mechanical polishing Musashino Chemical Laboratories Ltd ., located at 1 - 1 - 1 , CS : carrier speed Yaesudai Bld . 7F , Kyobashi, Chuo -ku , Tokyo , 104 -0031 , DF : Down force : pressure applied during CMP, units psi Japan . min : minute ( s ) [0138 ] B - alanine powder was purchased from Yuki Gosei ml: milliliter ( s ) Kogyo Co ., LTD . mV: millivolt( s) psi: pounds per square inch Example 1 PS : platen rotational speed of polishing tool, in rpm (revo [0139 ] The Musashino DL - alanine powder was prepared lution ( s ) per minute ) for Ion Chromatography ( IC ) analysis . SF : polishing composition flow , ml/min [0140 ] The powder was analyzed for fluoride , chloride , [0130 ] In the examples to be presented , CMP experiments nitrite , sulfate , bromide , nitrate , phosphate , and ammonium were run using the procedures and experimental conditions concentration by IC (Dionex ICS- 2100 ) , and results were given below . given in Table 1. TABLE 1 IC Results of DL - alanine Powder Fluoride Chloride Nitrite Sulfate Bromide Nitrate Phosphate Ammonium ( ppm ) (ppm ) (ppm ) (ppm ) ( ppm ) (ppm ) (ppm ) (ppm ) ND 4 . 1 ND BD ND ND ND BD

[0131 ] The CMP tool that was used in the examples is a [0141 ] ND indicated that there was no peak detected ; and Mirra® , manufactured by Applied Materials , 3050 Boweres BD indicated that the detected peak intensity was not high Avenue, Santa Clara , Calif. , 95054. An IC1010 pad , sup enough to quantify as the data , i . e . , below detection limit plied by Dow Chemical Co ., Ltd ., was used on the platen for ( likely < 1 ppm ). Both ND and BD thus indicated that the the blanket wafer polishing studies. Pads were broken - in by phosphate was at least < 1 ppm . polishing ten dummy Cu wafers. To qualify the tool settings [0142 ] The data in Table 1 has shown that DL - alanine did and the pad break - in , one Cu monitors was polished with not have any phosphate detected . Cu4545 , supplied by Planarization Platform of Air Products Chemicals Inc . , at baseline conditions. Polishing experi Example 2 ments were conducted using blanket PVD cobalt wafer with [0143 ] DL - alanine (Musashino ) dilution in DIW was pre 5K Angstroms in thickness . These blanket wafers were pared for High Performance Liquid Chromatography purchased from Silicon Valley Microelectronics, 1150 (HPLC ) analysis . Campbell Ave, CA , 95126 . [0144 ] The dilution was prepared at 1 . 0 wt % DL - alanine 10132 ] The associated methods described herein entail use and 1 . 0 wt % H2O , as oxidizing agent. The rest of the of the composition for chemical mechanical planarization of composition was DIW . The pH value for the composition substrates comprised of cobalt. In the methods, a substrate was not adjusted . The composition was not used for polish ( e . g . , a wafer with Co surface or Co plug ) was placed ing Co . face - down on a polishing pad which was fixedly attached to 101451. The dilution was analyzed for DL - alanine concen a rotatable platen of a CMP polisher. In this manner, the tration by HPLC (Waters e2695 HPLC ) before H2O2 addi substrate to be polished and planarized was placed in direct tion (Day 0 ), one day after H2O2 addition , and seven days contact with the polishing pad . A wafer carrier system or polishing head was used to hold the substrate in place and to after H2O2 addition , with result listed in Table 2 . apply a downward pressure against the backside of the substrate during CMP processing while the platen and the TABLE 2 substrate were rotated . The polishing composition ( slurry ) Degradation Measurement of 1 . 0 wt. % DL - alanine Solutions was applied (usually continuously ) on the pad during CMP in DIW with 1 . 0 wt. % H , O , ( HPLC Analysis) processing for effective removal of material and planarizing Normalized DL - alanine the substrate. Concentration ( % ) vs Days with H , O , [0133 ] All Cobalt removal rates (Co RR ) are measured at Composition Day Day 1 Day 7 1. 5 psi down pressure of the CMP tool, unless otherwise indicated . DL - alanine 99. 9 100 . 1 100 . 6 [0134 ] All percentages are weight percentages unless oth erwise indicated . [ 0146 ] The data showed in Table 2 has demonstrated that 10135 ] Other experimental polishing parameters include a Musashino DL - alanine composition was stable for at least 7 table speed of 90 . 0 RPM , head speed of 84 RPM , slurry flow days, with a change in concentration of DL -alanine of 1 .2 of 200 mL /min , conditioner force of 7 . 0 lb , in - situ condi wt. % or less . tioning for 60 seconds , and 30 seconds of polishing time. [0136 ] The polishing composition and associated methods Example 3 described herein are effective for CMP of a wide variety of [ 0147 ] Three CMP polishing compositions were prepared substrates . using the supplier of DL - alanine , and compositions were US 2017 /0362466 A1 Dec . 21, 2017 doped with dipotassium phosphate (potassium phosphate increased the Co RR . Furthermore, this boosting effect can dibasic ) or ammonium phosphate dibasic . The composition be precisely controlled with the amount of phosphate ion not doped was used as the control. that is doped in the cobalt bulk CMP polishing composi [0148 ] All compositions comprised of 0 .6210 wt. % high tions . purity colloidal silica particles having Mean Particle Size (MPS ) about 70 nm as measured by Dynamic Light Scat Example 5 tering (DLS ) technique ; 0 .0002 wt. % Kathon II as biocide ; [0157 ] The composition comprised of 0 .6210 wt. % high 0 .002 wt. % ethylene diamine ; 0 .00025 wt. % 1, 3 , 5 - Tris (2 purity colloidal silica particles having MPS about 70 nm ; hydroxyethyl ) isocyanurate ; 0 .0946 wt. % 3 - amino - 1 , 2 , 4 0 .0002 wt. % Kathon II as biocide ; 0 . 002 wt. % ethylene triazole ; 1 . 10 wt. % DL - alanine ; potassium hydroxide as pH diamine ; 0 .00025 wt. % 1 , 3, 5 - Tris ( 2 -hydroxyethyl ) isocya adjusting agent; and 1 . 0 wt % H2O2 as oxidizing agent . nurate; 0 .0946 wt. % 3 - amino - 1 , 2 , 4 - triazole ; 1 . 10 wt. % [0149 ] One composition comprised 0 .0010 wt. / % ( 10 ppm ) DL -alanine ; potassium hydroxide as pH adjusting agent; and dipotassium phosphate , and another composition comprised 1 . 0 wt % H , O , as oxidizing agent, and different concentra 0 .0008 wt. % (8 ppm ) ammonium phosphate dibasic . tions of ammonium phosphate dibasic , as shown in Table 5 . [0150 ] The rest of the compositions was DI Water . The pH The rest of the compositions was DI Water . The pH value of value of the compositions was approximately 8 . 0 . the compositions was approximately 8 . 0 . [ 0151] The removal rates (RR ) (Å / 30 s) of Co were shown [0158 ] The removal rates (RR ) ( Å / 30 s ) of Co were shown in Table 3 . in Table 5 . [0159 ] The results have shown that with 1 ppm phosphate TABLE 3 dopant concentration in the polishing composition , there CO RR Doped with Ammonium Phosphate vs Potassium Phosphate was no apparent Co removal rate boosting observed . [0160 ] The Co removal rate started to rise when the Composition Co Removal in 30 s ( 8 ) phosphate dopant concentrations were > 2 ppm . DL -alanine , no Phosphate ( control) 328 DL -alanine + 8 ppm Ammonium Phosphate 1039 TABLE 5 DL - alanine + 10 ppm Potassium Phosphate 1066 Co RR Doped with Ammonium Phosphate vs Potassium Phosphate [0152 ] The results in Table 3 demonstrated that Co RR Ammonium Phosphate ( ppm ) Co Removal in 30 s (8 ) boosting effect was achieved with approximately equal little 296 molar amounts of ammonium phosphate dibasic or potas 250 sium phosphate dibasic doped into the compositions. 300 348 Example 4 373 322 [ 0153] Two cobalt bulk CMP polishing compositions were 424 prepared by doping ammonium phosphate and potassium 655 939 phosphate into compositions not having any alanine . OOvuAWNO 1033 [0154 ] More specifically , the two compositions both com 1154 prised of 0 .6210 wt % high purity colloidal silica particles 1632 having MPS about 70 nm ; 0 .0002 wt % Kathon II as biocide ; 0 .002 wt % ethylene diamine ; 0 . 00025 wt % 1 , 3 , 5 - Tris ( 2 hydroxyethyl) isocyanurate ; 0 .0946 wt % 3 - amino - 1 , 2 ,4 - tri Example 6 azole ; 0 .0010 wt. % ( 10 ppm ) ammonium phosphate dibasic or 0 . 0020 wt. % (20 ppm ) potassium phosphate dibasic ; [0161 ] Eighteen cobalt bulk CMP polishing compositions potassium hydroxide as pH adjusting agent; and 1 . 0 wt % were prepared using DL -alanine (Musashino ) and doped H2O , as oxidizing agent. The rest of the composition was with varying concentrations of ammonium phosphate diba DIW . The pH value of the compositions was approximately sic . 8 .0 . [0162 ] Eighteen compositions all comprised of 0 .6210 wt [0155 ] The removal rates (RR ) (Å /30 s) of Co were shown % high purity colloidal silica particles having MPS about 70 in Table 4 . nm ; 0 . 0002 wt % Kathon II as biocide; 0 . 002 wt % ethylene diamine ; 0 . 00025 wt % 1 , 3 , 5 - Tris ( 2 - hydroxyethyl ) isocya TABLE 4 nurate ; 0 .0946 wt % 3 -amino - 1 , 2 , 4 - triazole ; 1 . 10 wt % DL -alanine ; between 0 .00005 wt. % (0 . 5 ppm ) and 0 .010 wt. Co RR of Phosphate Doped Compositions without Alanine % ( 100 ppm ) ammonium phosphate dibasic ; potassium hydroxide as pH adjusting agent; and 1 . 0 wt % H , O , as Composition Co Removal in 30 s ( Å ) oxidizing agent. The rest of the composition was DIW . The No Alanine + 10 ppm Ammonium Phosphate 110 pH value of the compositions was approximately 8 . 0 . No Alanine + 20 ppm Potassium Phosphate 126 [0163 ] The polishing results of these samples were shown in FIG . 1 . [0156 ] The results in Table 4 demonstrated that within the [0164 ] The results in FIG . 1 demonstrated that the correct doping levels of phosphate , the phosphate alone did not concentration of phosphate enabled an increase in Co RR by enable the Co RR boosting. This result coupled with the as much as 575 % . The CMP compositions comprised with previous result in Examples 3 have shown that the combi- DL - alanine showed an increase in Co RR when doped with nation of DL -alanine and phosphate has synergistically between 2 and 25 ppm ammonium phosphate dibasic , with US 2017 /0362466 A1 Dec . 21, 2017 a maximum Co RR of 1808 Å /30 s occurring at 15 ppm . At tives, the disclosed chemical mechanical polishing (CMP ) concentrations of 25 ppm and higher of ammonium phos compositions and methods provided desirable high and phate dibasic , the Co RR was shut down and matches the tunable Co film removal rates . low Co RR of the un - doped compositions made using [0176 ] The foregoing examples and description of the Musashino DL -alanine . preferred embodiments should be taken as illustrating , rather than as limiting the present invention as defined by the Example 7 claims. As will be readily appreciated , numerous variations [0165 ] The composition comprised of 0 .6210 wt. % high and combinations of the features set forth above can be purity colloidal silica particles having MPS about 70 nm ; utilized without departing from the present invention as set 0 .0002 wt. % Kathon II as biocide; 0 . 002 wt. % ethylene forth in the claims. Such variations are not regarded as a diamine ; 0 .00025 wt. % 1, 3 ,5 - Tris ( 2 -hydroxyethyl ) isocya departure from the spirit and scope of the invention , and all nurate ; 0 .0946 wt. % 3 - amino - 1 , 2 , 4 - triazole ; 1 . 10 wt. % such variations are intended to be included within the scope DL - alanine; potassium hydroxide as pH adjusting agent; and of the following claims. 1 . 0 wt % H2O , as oxidizing agent, and 0 .0010 wt. / % ( 10 1 . A chemical mechanical polishing ( CMP) polishing ppm ) ammonium phosphate dibasic . The rest of the com composition for cobalt - containing substrate , comprising : positions was DIW . The pH value of the compositions was 0 . 005 wt. % to 25 wt. % of abrasive ; approximately 8 . 0 . 0 . 05 wt. % to 5 wt. % of a - alanine ; [ 0166 ) Under the same polishing conditions , the removal from 2 ppm to 100 ppm of phosphate compound com rate (RR ) ( Å / 30 s ) of Co was > 1100 Å / 30 s and the removal prising H , PO -, HPO 2- , or PO 3 -; rate (RR ) ( Å / 30 s ) of TiN was 7 Å /min . 0 .0005 wt. % to 0 . 25 wt. % of corrosion inhibitor; [ 01671. The selectivity for Co RR : TIN RR for the compo 0 . 005 wt. % to 10 wt. % of oxidizer ; and water ; sition was > 150 . wherein the chemical mechanical polishing (CMP ) pol ishing composition having a pH from 2 . 0 to about 12 . Example 8 2 . The chemical mechanical polishing ( CMP ) polishing [0168 ] The Co slurries using different alanine were stud composition for cobalt - containing substrate of claim 1 , ied . The alanine being tested were DL - Alanine (Musashino ), further comprises at least one of: Beta - alanine ( Yuki Gosei Kogyo Co. ) . 0 .0001 wt. % t to 0 . 20 wt. % of amine compound ; 10169] Beta - or B -alanine comprises a beta amino group , 0 .01 wt. % to 10 wt. % of chelating agent; i . e ., the amino group is at the B -position from the carboxy 0 .01 wt. % to 0 .5 wt. % of pH adjusting agent; late group . 0 . 00001 wt. % to 0 . 10 wt. % of biocide ; and 0170 ] Alpha - alanine and beta -alanine are having different 0 .0005 wt. % to 0 . 15 wt. % of surfactant. chemical structures . 3 . The chemical mechanical polishing (CMP ) polishing [0171 ] The composition comprised of 0 .6210 wt. % high composition for cobalt - containing substrate of claim 1 , purity colloidal silica particles having MPS about 70 nm ; wherein the abrasive is selected from the group consisting of 0 .0002 wt. % Kathon II as biocide; 0 .002 wt. % ethylene nano - sized colloidal silica or high purity colloidal silica diamine; 0 . 00025 wt. % 1 , 3 , 5 - Tris ( 2 -hydroxyethyl ) isocya particles ; nano - sized inorganic metal oxide particles selected nurate ; 0 . 0946 wt. % 3 - amino - 1 , 2 ,4 - triazole ; 1 . 10 wt. % from the group consisting of alumina , titania , zirconia , ceria alanine; potassium hydroxide as pH adjusting agent; and 1 . 0 and combinations thereof; nano - sized diamond particles ; wt % H2O2 as oxidizing agent, and 0 . 0015 wt. / % ( 15 ppm ) nano - sized silicon nitride particles ; mono -modal , bi- modal , ammonium phosphate dibasic . The rest of the compositions or multi -modal colloidal abrasive particles; organic poly was DIW . The pH value of the compositions was approxi mer -based soft abrasives; surface -coated or modified abra mately 8 . 0 . sives ; and combinations thereof; and ranges from 0 .05 wt. % [ 0172 ] The Co formulations containing no phosphate dop to 5 wt. % ; ant were used as reference sample . the alanine is selected from the group consisting of [0173 ] The Co RR from the formulations were shown in D - Alanine , L - Alanine , DL - Alanine, and combinations Table 6 . thereof; and ranges from 0 . 5 wt. % to 2 wt. % ; the phosphate compound comprising H2PO4' -, HPO 4 2 -, TABLE 6 or PO - is in a form selected from the group consisting of phosphate ion ( tribasic ), hydrogen phosphate ion Co Removal Rates with Different Chelators (dibasic ) , dihydrogen phosphate (mono -basic ) , trihy Sample Conductivity (US ) CO RR ( A /min . ) drogen phosphate (acid ), and combinations thereof; and 1 . 1 % DL - Alanine , no Dopant 162. 3 139 ranges from 2 ppm to 50 ppm ; 1 . 1 % DL - Alanine , 15 ppm 197 . 3 1266 the corrosion inhibitor is selected from the group consist Phosphate as Dopant ing of 1 , 2 , 4 - triazole and its derivatives , benzotriazole 1 . 1 % Beta - Alanine , no Dopant 119 . 1 and its derivatives , 1 , 2 , 3 - triazole and its derivatives, 1 . 1 % Beta - Alanine , 15 ppm 108 . 3 pyrazole and its derivatives, imidazole and its deriva Phosphate as Dopant tives, benzoimidazole and its derivatives , benzoimida zole and its derivatives , isocyanurate and its deriva [0174 ] It 's evident from table 6 that compositions using tives, and combinations thereof; and ranges from DL -Alanine with a dopant had shown an unexpected result 0 . 0025 wt. % to 0 .25 wt. % ; of boosting cobalt removal rate . the oxidizing agent is selected from the group consisting [ 0175 ] The forgoing working examples had demonstrated of periodic acid , hydrogen peroxide , potassium iodate , that with the combination of the different phosphate addi potassium permanganate , ammonium persulfate , US 2017 /0362466 A1 Dec . 21, 2017

ammonium molybdate , ferric nitrate , nitric acid , potas group consisting of secondary alkane sulfonates , dode sium nitrate , and mixtures thereof; cyl sulfate , sodium salt , lauryl sulfate , potassium salt , and ranges from 0 . 25 wt. % to 3 wt. % ; and and combinations thereof; cationic surfactant selected the chemicalmechanical polishing (CMP ) polishing com from the group consisting of quaternary ammonium position having a pH from 6 . 0 to about 10 . based surfactant; and amphoteric surfactant selected 4 . The chemical mechanical polishing (CMP ) polishing from the group consisting of betaine and amino acid composition for cobalt - containing substrate of claim 3 , derivatives based surfactant; and combinations thereof. further comprises at least one of 5 . The chemical mechanical polishing (CMP ) polishing the chelating agent ranges from 0 . 1 wt. % to 5 wt. % and composition for cobalt - containing substrate of claim 3 , is selected independently from the group consisting of wherein the phosphate compound is an inorganic salt of glycine, serine, proline , histidine, isoleucine, leucine , phosphoric acid or an organophosphate compound . lysine, methionine , phenylalanine , threonine , trypto 6 . The chemical mechanical polishing ( CMP ) polishing phan , valine , arginine , asparagine , aspartic acid , cys composition for cobalt - containing substrate of claim 1 com tein , glutamic acid , glutamine , ornithine , picolinic acid , prises 0 . 1 wt. % to 2 . 5 wt. % of nano - sized colloidal silica selenocystein , tyrosine , sarcosine, bicine, tricine , ace or high purity colloidal silica particles ; 0 .825 wt. % to 1. 65 glutamide , n - acetylaspartic acid , acetylcarnitine , ace wt. % of alanine selected from the group consisting of tylcysteine , n -acetylglutamic acid , acetylleucine , acivi D -Alanine , L - Alanine , DL - Alanine, and combinations cin , s -adenosyl - 1 -homocysteine , agaritine, alanosine, thereof; 5 ppm to 20 ppm of ammonium phosphate or aminohippuric acid , l - arginine ethyl ester, aspartame, potassium phosphate in monobasic , dibasic or tribasic form ; aspartylglucosamine , benzylmercapturic acid , biocytin , 0 .05 wt. % to 0 . 15 wt. % of 1 , 2 ,4 - triazole and its derivatives, brivanib alaninate , carbocisteine , n ( 6 ) - carboxymeth benzotriazole and its derivatives , 1 , 2 ,3 - triazole and its yllysine , carglumic acid , cilastatin , citiolone , coprine, derivatives, pyrazole and its derivatives, imidazole and its dibromotyrosine , dihydroxyphenylglycine, eflornith derivatives, benzoimidazole and its derivatives , benzoimi ine , fenclonine , 4 - fluoro - l- threonine , n - formylmethio dazole and its derivatives , isocyanurate and its derivatives, nine , gamma -l - glutamyl- 1- cysteine , 4 - ( y - glutamy and combinations thereof; 0 .5 wt. % to 1. 5 wt. % of periodic lamino )butanoic acid , glutaurine , glycocyamine , acid , hydrogen peroxide, potassium iodate , potassium per hadacidin , hepapressin , lisinopril , lymecycline , manganate , ammonium persulfate , ammonium molybdate , n -methyl - d -aspartic acid , n -methyl - 1- glutamic acid , ferric nitrate , nitric acid , potassium nitrate , and mixtures milacemide , nitrosoproline, nocardicin a , nopaline , thereof; and the chemical mechanical polishing ( CMP ) octopine , ombrabulin , opine , orthanilic acid , oxaceprol, polishing composition having a pH from 7 .0 to about 9 .0 . polylysine , remacemide, salicyluric acid , silk amino 7 . The chemical mechanical polishing ( CMP) polishing acid , stampidine , tabtoxin , tetrazolylglycine , thiorphan , composition for cobalt- containing substrate of claim 6 , thymectacin , tiopronin , tryptophan tryptophylquinone , further comprises at least one of valaciclovir , valganciclovir, and combinations thereof; 0 . 5 wt. % to 2 wt. % of glycine , picolinic acid , and the amine compound ranges from 0 . 0010 wt. % to 0 . 10 combinations thereof; wt. % , and is selected independently from the group 0 .0025 wt. % to 0 .050 wt. % of ethylene diamine , consisting of ethylene diamine , propylene diamine , propylene diamine , organic amine compound contain organic amine compound containing multi amino ing multi amino groups in the same molecular, and groups in the same molecular, and combinations thereof; combinations thereof; the pH adjusting agent ranges from 0 .05 wt. % to 0 . 15 wt. 0 .05 wt. % to 0 .15 wt. % of nitric acid , hydrochloric acid , % , and is selected from the group consisting of nitric sulfuric acid , phosphoric acid , sodium hydride , potas acid , hydrochloric acid , sulfuric acid , phosphoric acid , sium hydroxide, ammonium hydroxide , tetraalkylam sodium hydride , potassium hydroxide , ammonium monium hydroxide , and mixtures thereof; hydroxide, tetraalkylammonium hydroxide , organic 0 .00015 wt. % to 0 .0025 wt. % of isothiozilone selected amines, and mixtures thereof; from the group consisting of methylisothiazolinone , the biocide ranges from 0 . 0001 wt. % to 0 .005 wt. % , and methylchloroisothiazolinone , benzisothiazolinone , and is selected from the group consisting of methylisothi combinations thereof ; and azolinone ; methylchloroisothiazolinone; quaternary 0 . 0025 wt. % to 0 .025 wt. % of the surfactant. ammonium compound selected from the group consist 8 . The chemical mechanical polishing (CMP ) polishing ing of tetramethylammonium chloride , tetraethylam composition for cobalt - containing substrate of claim 6 com monium chloride, tetrapropylammonium chloride , prises high purity colloidal silica particles ; DL -Alanine , alkylbenzyldimethylammonium chloride and alkylben ammonium phosphate or potassium phosphate in monoba zyldimethylammonium hydroxide; wherein the alkyl sic , dibasic or tribasic form ; 3 -amino - 1 , 2 , 4 - triazole , 1 , 3 , 5 chain ranges from 1 to about 20 carbon atoms; chloro Tris ( 2 -hydroxyethyl ) isocyanurate, or combinations of containing compound selected from the group consist 3 - amino - 1 , 2 , 4 - triazole and 1 , 3 , 5 - Tris ( 2 -hydroxyethyl ) iso ing of chlorite and sodium hypochlorite ; biguanide ; cyanurate , hydrogen peroxide , and ethylene diamine . aldehyde ; ethylene oxide ; metallic salt , isothiazoli 9 . A method of a selective chemicalmechanical polishing none ; indophor ; and combinations thereof; and comprising : the surfactant ranges from 0 .001 wt. % to 0 .05 wt. % , and a ) providing a semiconductor substrate having a surface is selected from the group consisting of non - ionic containing a first material and at least one second surfactant selected from the group consisting of alcohol material; wherein the firstmaterial is Co and the second ethoxylates, acetylenic diol surfactants, and combina material is selected from the group consisting ofdielec tions thereof; anionic surfactant selected from the tric film , low - k and ultra low - k film , and barrier film ; US 2017 /0362466 A1 Dec . 21, 2017 10

b ) providing a polishing pad ; ammonium molybdate , ferric nitrate , nitric acid , potas providing a chemical mechanical polishing composi sium nitrate , and mixtures thereof; and ranges from tion comprising 0 . 25 wt. % to 3 wt. % ; 0 .005 wt. % to 25 wt. % of abrasive ; the chemicalmechanical polishing (CMP ) polishing com 0 . 05 wt. % to 5 wt. % of a -alanine ; position having a pH from 6 .0 to about 10 ; from 2 ppm to 100 ppm of phosphate compound and optionally comprising H2PO4' -, HPO 2- , or PO 3 - ; the chelating agent range from 0 . 1 wt. % to 5 wt. % and 0 . 0005 wt. % to 0 . 25 wt. % of corrosion inhibitor, is selected independently from the group consisting of 0 .005 wt. % to 10 wt. % of oxidizer ; glycine , serine , proline, histidine , isoleucine , leucine, water ; and lysine , methionine , phenylalanine , threonine, trypto the chemical mechanical polishing (CMP ) polishing phan , valine, arginine , asparagine , aspartic acid , cys composition having a pH from 2 .0 to about 12 ; tein , glutamic acid , glutamine , ornithine , picolinic acid , and optionally 0 . 0001 wt. % tto 0 . 20 wt. % of amine selenocystein , tyrosine, sarcosine, bicine , tricine , ace compound; glutamide , n -acetylaspartic acid , acetylcarnitine , ace tylcysteine , n - acetylglutamic acid , acetylleucine, acivi 0 .01 wt. % to 10 wt. % of chelating agent; cin , s -adenosyl - 1 - homocysteine , agaritine, alanosine, 0 .01 wt. % to 0 . 5 wt. % of pH adjusting agent; aminohippuric acid , l - arginine ethyl ester, aspartame, 0 .00001 wt. % to 0 . 10 wt. % of biocide ; and aspartylglucosamine , benzylmercapturic acid , biocytin , 0 .0005 wt. % to 0 . 15 wt. % of surfactant; brivanib alaninate , carbocisteine , n ( 6 ) -carboxymeth and yllysine, carglumic acid , cilastatin , citiolone , coprine , c ) polishing the surface of the semiconductor substrate to dibromotyrosine , dihydroxyphenylglycine , eflornith selectively remove the first material ; ine , fenclonine , 4 -fluoro - 1- threonine , n - formylmethio wherein at least a portion of the surface is in contact nine , gamma - 1 - glutamyl- 1 - cysteine , 4 - ( y - glutamy with both the polishing pad and the chemical lamino )butanoic acid , glutaurine , glycocyamine , mechanical polishing composition ; and ratio of hadacidin , hepapressin , lisinopril, lymecycline, removal rate of the first material to removal rate of n -methyl - d - aspartic acid , n -methyl - 1 - glutamic acid , the second material is equal or greater than 50 . milacemide, nitrosoproline , nocardicin a , nopaline , 10 . The method of a selective chemical mechanical pol octopine , ombrabulin , opine , orthanilic acid , oxaceprol, ishing of claim 9 , wherein the second material is selected polylysine , remacemide , salicyluric acid , silk amino from the group consisting of TEOS , SixNy (with 1 . 0 < x < 3 . 0 , acid , stampidine , tabtoxin , tetrazolylglycine, thiorphan , 1 .33 < y < 4 .0 ), Ta , TaN , Ti , and TiN . thymectacin , tiopronin , tryptophan tryptophylquinone , 11 . The method of a selective chemical mechanical pol valaciclovir , valganciclovir, and combinations thereof; ishing of claim 9 , wherein the chemical mechanical polish the amine compound ranges from 0 .0010 wt. % to 0 . 10 ing composition comprises wt. % , and is selected independently from the group the abrasive is selected from the group consisting of consisting of ethylene diamine , propylene diamine , nano -sized colloidal silica orhigh purity colloidal silica organic amine compound containing multi amino particles ; nano - sized inorganic metal oxide particles groups in the same molecular, and combinations selected from the group consisting of alumina, titania , thereof; zirconia , ceria and combinations thereof; nano -sized the pH adjusting agent ranges from 0 .05 wt. % to 0 .15 wt. diamond particles ; nano - sized silicon nitride particles; % , and is selected from the group consisting of nitric mono -modal , bi- modal , or multi -modal colloidal abra acid , hydrochloric acid , sulfuric acid , phosphoric acid , sive particles; organic polymer- based soft abrasives ; sodium hydride, potassium hydroxide , ammonium surface -coated or modified abrasives; and combina hydroxide , tetraalkylammonium hydroxide , organic tions thereof; and ranges from 0 .05 wt. % to 5 wt. % ; amines , and mixtures thereof; the alanine is selected from the group consisting of the biocide ranges from 0 .0001 wt. % to 0 .005 wt. % , and D - Alanine , L - Alanine, DL - Alanine , and combinations is selected from the group consisting of methylisothi thereof; and ranges from 0 . 5 wt. % to 2 wt . % ; azolinone ; methylchloroisothiazolinone; quaternary the phosphate compound comprising H2PO4' - , HPO42 - , ammonium compound selected from the group consist or PO43 - is in a form selected from the group consisting ing of tetramethylammonium chloride, tetraethylam of phosphate ion ( tribasic ), hydrogen phosphate ion monium chloride , tetrapropylammonium chloride , (dibasic ) , dihydrogen phosphate (mono -basic ) , trihy alkylbenzyldimethylammonium chloride and alkylben drogen phosphate (acid ), and combinations thereof; and zyldimethylammonium hydroxide ; wherein the alkyl ranges from 2 ppm to 50 ppm ; chain ranges from 1 to about 20 carbon atoms; chloro the corrosion inhibitor is selected from the group consist containing compound selected from the group consist ing of 1 , 2 , 4 - triazole and its derivatives, benzotriazole ing of chlorite and sodium hypochlorite ; biguanide; and its derivatives , 1 , 2 , 3 - triazole and its derivatives , aldehyde ; ethylene oxide ; metallic salt , isothiazoli pyrazole and its derivatives , imidazole and its deriva none ; indophor; and combinations thereof; tives, benzoimidazole and its derivatives, benzoimida the surfactant ranges from 0 . 001 wt. % to 0 .05 wt. % , and zole and its derivatives, isocyanurate and its deriva is selected from the group consisting of non - ionic tives , and combinations thereof; and ranges from surfactant selected from the group consisting of alcohol 0 .0025 wt. % to 0 .25 wt. % ; ethoxylates , acetylenic diol surfactants , and combina the oxidizing agent is selected from the group consisting tions thereof; anionic surfactant selected from the of periodic acid , hydrogen peroxide, potassium iodate , group consisting of secondary alkane sulfonates, dode potassium permanganate , ammonium persulfate , cyl sulfate , sodium salt, lauryl sulfate , potassium salt, US 2017 /0362466 A1 Dec . 21, 2017 11

and combinations thereof; cationic surfactant selected a semiconductor substrate having a surface containing a from the group consisting of quaternary ammonium first material and at least one second material; based surfactant; and amphoteric surfactant selected wherein the first material is Co and the second material is from the group consisting of betaine and amino acid selected from the group consisting of dielectric films derivatives based surfactant ; and combinations thereof . (such as TEOS , SixNy (with 1 . 0 < x < 3 . 0 , 1 . 33 < y < 4 . 0 ) , 12 . The method of a selective chemical mechanical pol low - k and ultra low - k films, and barrier films ( such as ishing of claim 11 , wherein the phosphate compound is an Ta , Tan , Ti, and Tin films) ; inorganic salt of phosphoric acid or an organophosphate a polishing pad ; compound . a chemicalmechanical polishing composition comprising 13 . The method of a selective chemical mechanical pol 0 .005 wt. % to 25 wt. % of abrasive ; ishing of claim 9 , wherein the chemical mechanical polish 0 . 05 wt. % to 5 wt. % of a - alanine; ing ( CMP) polishing comprises 0 .1 wt. % to 2. 5 wt. % of from 2 ppm to 100 ppm of phosphate compound nano - sized colloidal silica or high purity colloidal silica comprising H2PO4 , HPO42 -, or PO 3 -; particles ; 0 . 825 wt. % to 1 .65 wt. % of alanine selected from 0 .0005 wt. % to 0 .25 wt. % of corrosion inhibitor ; the group consisting of D - Alanine, L - Alanine, DL - Alanine , 0 . 005 wt. % to 10 wt. % of oxidizer ; and combinations thereof; 5 ppm to 20 ppm of ammonium water ; phosphate or potassium phosphate in monobasic , dibasic or the chemical mechanical polishing (CMP ) polishing tribasic form ; 0 .05 wt. % to 0 . 15 wt. % of 1 , 2 ,4 - triazole and composition having a pH from 2 . 0 to about 12 ; its derivatives, benzotriazole and its derivatives, 1 , 2 , 3 - triaz and optionally : ole and its derivatives , pyrazole and its derivatives , imida 0 .0001 wt. % t to 0 . 20 wt. % of amine compound ; zole and its derivatives , benzoimidazole and its derivatives , 0 .01 wt. % to 10 wt. % of chelating agent ; benzoimidazole and its derivatives , isocyanurate and its 0 .01 wt. % to 0 . 5 wt. % of pH adjusting agent ; derivatives, and combinations thereof; 0 . 5 wt. % to 1 .5 wt. 0 .00001 wt. % to 0 . 10 wt. % of biocide ; and % of periodic acid , hydrogen peroxide , potassium iodate , 0 . 0005 wt. % to 0 . 15 wt. % of surfactant; potassium permanganate, ammonium persulfate , ammo and nium molybdate , ferric nitrate , nitric acid , potassium nitrate , wherein at least a portion of the surface is in contact with and mixtures thereof; and the chemicalmechanical polishing both the polishing pad and the chemical mechanical ( CMP) polishing composition having a pH from 7 . 0 to about polishing composition . 9 .0 ; 17 . The chemical mechanical polishing (CMP ) system of and optionally claim 16 , wherein the chemical mechanical polishing com 0 . 5 wt. % to 2 wt. % of glycine , picolinic acid , and position comprises combinations thereof; the abrasive is selected from the group consisting of 0 . 0025 wt. % to 0 . 050 wt. % of ethylene diamine , nano - sized colloidal silica or high purity colloidal silica propylene diamine, organic amine compound contain particles ; nano -sized inorganic metal oxide particles ing multi amino groups in the same molecular, and selected from the group consisting of alumina , titania , combinations thereof; zirconia , ceria and combinations thereof; nano -sized 0 .05 wt. % to 0 . 15 wt. % of nitric acid , hydrochloric acid , diamond particles ; nano - sized silicon nitride particles ; sulfuric acid , phosphoric acid , sodium hydride , potas mono -modal , bi- modal , or multi -modal colloidal abra sium hydroxide , ammonium hydroxide , tetraalkylam sive particles ; organic polymer- based soft abrasives ; monium hydroxide , and mixtures thereof; surface - coated or modified abrasives , and combina 0 .00015 wt. % to 0 . 0025 wt. % of isothiozilone selected tions thereof; and ranges from 0 . 05 wt. % to 5 wt. % ; from the group consisting of methylisothiazolinone , the alanine is selected from the group consisting of methylchloroisothiazolinone , benzisothiazolinone , and D - Alanine, L -Alanine , DL - Alanine, and combinations combinations thereof; and thereof; and ranges from 0 .5 wt. % to 2 wt. % ; 0 . 0025 wt. % to 0 .025 wt. % of the surfactant. the phosphate compound comprising H2PO4 ' -, HPO42 - , 14 . The method of a selective chemical mechanical pol or PO 3- is in a form selected from the group consisting ishing of claim 13 , wherein the chemical mechanical pol of phosphate ion ( tribasic ), hydrogen phosphate ion ishing (CMP ) polishing composition comprises high purity ( dibasic ) , dihydrogen phosphate (mono -basic ) , trihy colloidal silica particles; DL - Alanine, ammonium phosphate drogen phosphate ( acid ) , and combinations thereof ; and or potassium phosphate in monobasic , dibasic or tribasic ranges from 2 ppm to 50 ppm ; form ; 3 - amino - 1 , 2 , 4 - triazole , 1 , 3 , 5 - Tris ( 2 -hydroxyethyl ) the corrosion inhibitor is selected from the group consist isocyanurate , or combinations of 3 -amino - 1 , 2 , 4 - triazole and ing of 1 , 2 , 4 - triazole and its derivatives, benzotriazole 1 , 3 , 5 - Tris ( 2 -hydroxyethyl ) isocyanurate , hydrogen peroxide , and its derivatives, 1 , 2 , 3 -triazole and its derivatives , and ethylene diamine . pyrazole and its derivatives , imidazole and its deriva 15 . The method of a selective chemical mechanical pol tives, benzoimidazole and its derivatives , benzoimida ishing of claim 14 , wherein at least a portion of the surface zole and its derivatives , isocyanurate and its deriva is in contact with both the polishing pad and the chemical tives, and combinations thereof; and ranges from mechanical polishing composition ; the second material is 0 .0025 wt. % to 0 . 25 wt. % ; selected from the group consisting of TEOS , SixNy (with the oxidizing agent is selected from the group consisting 1 . 0 < x < 3 . 0 , 1 . 33 < y < 4 . 0 ) , Ta , Tan , Ti, and TiN ; and ratio of of periodic acid , hydrogen peroxide , potassium iodate , removal rate of the first material to removal rate of the potassium permanganate , ammonium persulfate , second material is equal or greater than 100 . ammonium molybdate , ferric nitrate , nitric acid , potas 16 . A chemicalmechanical polishing (CMP ) system com sium nitrate , and mixtures thereof; and ranges from prising : 0 . 25 wt. % to 3 wt. % ; US 2017 /0362466 A1 Dec . 21, 2017 12

the chemical mechanical polishing (CMP ) polishing com group consisting of secondary alkane sulfonates , dode position having a pH from 6 . 0 to about 10 ; cyl sulfate , sodium salt , lauryl sulfate , potassium salt , and optionally and combinations thereof; cationic surfactant selected the chelating agent ranges from 0 . 1 wt. % to 5 wt. % and from the group consisting of quaternary ammonium is selected independently from the group consisting of based surfactant; and glycine , serine , proline , histidine , isoleucine , leucine , amphoteric surfactant selected from the group consisting lysine, methionine , phenylalanine , threonine , trypto of betaine and amino acid derivatives based surfactant ; phan , valine , arginine , asparagine , aspartic acid , cys and combinations thereof. tein , glutamic acid , glutamine , ornithine, picolinic acid , 18 . The chemical mechanical polishing (CMP ) system of selenocystein , tyrosine, sarcosine , bicine, tricine, ace claim 17 , wherein the , wherein the phosphate compound is glutamide, n - acetylaspartic acid , acetylcarnitine , ace an inorganic salt of phosphoric acid or an organophosphate tylcysteine, n - acetylglutamic acid , acetylleucine , acivi compound . cin , s -adenosyl - 1 -homocysteine , agaritine , alanosine, 19 . The chemical mechanical polishing (CMP ) system of aminohippuric acid , l - arginine ethyl ester , aspartame, claim 16 , wherein the chemical mechanical polishing (CMP ) aspartylglucosamine , benzylmercapturic acid , biocytin , polishing comprises 0 . 1 wt. % to 2 . 5 wt. % of nano -sized brivanib alaninate , carbocisteine, n ( 6 ) - carboxymeth colloidal silica or high purity colloidal silica particles ; 0 . 825 yllysine, carglumic acid , cilastatin , citiolone, coprine , wt. % to 1. 65 wt. % of alanine selected from the group dibromotyrosine, dihydroxyphenylglycine, eflornith consisting of D - Alanine , L - Alanine , DL - Alanine , and com ine , fenclonine, 4 - fluoro - 1- threonine , n - formylmethio binations thereof; 5 ppm to 20 ppm of ammonium phosphate nine , gamma- l - glutamyl- l -cysteine , 4 -( y - glutamy or potassium phosphate in monobasic , dibasic or tribasic lamino )butanoic acid , glutaurine , glycocyamine , form ; 0 .05 wt. % to 0 . 15 wt. % of 1 , 2 , 4 - triazole and its hadacidin , hepapressin , lisinopril , lymecycline , derivatives, benzotriazole and its derivatives, 1, 2 , 3 - triazole n -methyl - d -aspartic acid , n -methyl - l - glutamic acid , and its derivatives , pyrazole and its derivatives , imidazole milacemide , nitrosoproline, nocardicin a , nopaline , and its derivatives , benzoimidazole and its derivatives , ben octopine , ombrabulin , opine , orthanilic acid , oxaceprol, zoimidazole and its derivatives, isocyanurate and its deriva polylysine , remacemide , salicyluric acid , silk amino tives , and combinations thereof; 0 . 5 wt. % to 1 .5 wt. % of acid , stampidine , tabtoxin , tetrazolylglycine , thiorphan , periodic acid , hydrogen peroxide , potassium iodate, potas thymectacin , tiopronin , tryptophan tryptophylquinone , sium permanganate , ammonium persulfate , ammonium valaciclovir , valganciclovir , and combinations thereof ; molybdate , ferric nitrate , nitric acid , potassium nitrate , and the amine compound ranges from 0 .0010 wt. % to 0 . 10 mixtures thereof; and the chemical mechanical polishing wt. % , and is selected independently from the group (CMP ) polishing composition having a pH from 7 . 0 to about consisting of ethylene diamine , propylene diamine , 9 . 0 ; organic amine compound containing multi amino and optionally groups in the same molecular, and combinations 0 . 5 wt. % to 2 wt. % of glycine, picolinic acid , and thereof; combinations thereof; the pH adjusting agent ranges from 0 .05 wt. % to 0 . 15 wt. 0 .0025 wt. % to 0 .050 wt. % of ethylene diamine , % , and is selected from the group consisting of nitric propylene diamine , organic amine compound contain acid , hydrochloric acid , sulfuric acid , phosphoric acid , ing multi amino groups in the same molecular , and sodium hydride , potassium hydroxide , ammonium combinations thereof; hydroxide , tetraalkylammonium hydroxide , organic 0 .05 wt. % to 0 . 15 wt. % of nitric acid , hydrochloric acid , amines, and mixtures thereof. sulfuric acid , phosphoric acid , sodium hydride , potas the biocide ranges from 0 .0001 wt. % to 0 .005 wt. % , and sium hydroxide , ammonium hydroxide , tetraalkylam is selected from the group consisting of methylisothi azolinone; methylchloroisothiazolinone ; quaternary monium hydroxide , and mixtures thereof; ammonium compound selected from the group consist 0 . 00015 wt. % to 0 .0025 wt. % of isothiozilone selected ing of tetramethylammonium chloride , tetraethylam from the group consisting of methylisothiazolinone, monium chloride , tetrapropylammonium chloride , methylchloroisothiazolinone , benzisothiazolinone, and alkylbenzyldimethylammonium chloride and alkylben combinations thereof; and zyldimethylammonium hydroxide ; wherein the alkyl 0 .0025 wt. % to 0 .025 wt. % of the surfactant. chain ranges from 1 to about 20 carbon atoms; chloro 20 . The chemical mechanical polishing ( CMP) system of containing compound selected from the group consist claim 19 , wherein the chemical mechanical polishing (CMP ) ing of chlorite and sodium hypochlorite ; biguanide ; polishing composition comprises high purity colloidal silica aldehyde; ethylene oxide; metallic salt, isothiazoli particles ; DL - Alanine , ammonium phosphate or potassium none ; indophor ; and combinations thereof; phosphate in monobasic , dibasic or tribasic form ; 3 -amino the surfactant ranges from 0 .001 wt . % to 0 . 05 wt. % , and 1 , 2 , 4 - triazole , 1 , 3 , 5 - Tris ( 2 - hydroxyethyl) isocyanurate , or is selected from the group consisting of non - ionic combinations of 3 -amino - 1 , 2 , 4 - triazole and 1 , 3 , 5 - Tris ( 2 surfactant selected from the group consisting of alcohol hydroxyethyl) isocyanurate , hydrogen peroxide, and ethyl ethoxylates, acetylenic diol surfactants , and combina ene diamine. tions thereof ; anionic surfactant selected from the * * * * *