CN106062931A - Cmp method for suppression of titanium nitride and titanium/titanium nitride removal - Google Patents

Abstract

A chemical mechanical polishing (CMP) method for removal of a metal layer deposited over a titanium nitride (TiN) or titanium/titanium nitride (Ti/TiN) barrier layer is described herein. The method comprises abrading the metal layer with an acidic CMP composition to expose the underlying TiN or Ti/TiN layer, wherein the TiN or Ti/N layer is polished at a low rate due to the presence of a surfactant inhibitor. The acidic CMP composition comprises a particulate abrasive (e.g., silica, alumina) suspended in a liquid carrier containing a surfactant selected from the group consisting of an anionic surfactant, a nonionic surfactant, cation surfactants, and a combination thereof.

Description

For the cmp method suppressing titanium nitride and titanium/titanium nitride to remove

Technical field

The present invention relates to chemically-mechanicapolish polish (CMP) compositions and method.More particularly, the present invention relate to suppression CMP method that titanium nitride and titanium/titanium nitride barrier layer remove and for this CMP composition.

Background technology

In manufacturing advanced semiconductor device (both memory device and logical device), some Integrated Solution needs choosing Selecting property remove metal (such as Cu, CuMn, Ta, TaN, Al, AlCo, Co, CoMo, Ru, RuTa, RuTiN, Mn, TiN (self-stopping technology), W, Pt) or (such as PR, SOG type oxidation of electrolyte (such as Si oxide, silicon nitride, carborundum, polysilicon) or polymer Thing), wherein, stop when arriving barrier layer removing (commonly referred to " on obstacle, stopping (stop on barrier) ").For Compositions and the method for the chemically mechanical polishing (CMP) of substrate surface are known in the art.For semiconductor substrate surface Polishing composition (also known as polishing slurries, CMP slurry and the CMP composition) allusion quotation of CMP (such as IC manufacturing) Type ground is containing grinding agent, various additive compound and fellow thereof.On barrier layer by titanium nitride (TiN) and titanium/titanium nitride (Ti/TiN) in the case of being formed, the technique that obstacle stops can be difficulty, because typical CMP composition is for relatively Remove upper metal-clad in TiN or Ti/TiN layer and not there is special selectivity.

The application-specific stopping technology on described obstacle is to be formed for tungsten (W) grid, and it relates to being arranged at W layer on barrier layer above oxide substrate carries out CMP and removes.Depression in oxide substrate is lined with of barrier layer Divide and be filled with W metal.During polishing, remove W layer by CMP, reach down to the planar section on barrier layer.Then, pass through Etching removes a part of the W in depression to form grid structure.On described obstacle, in stopping technology is the most tired Difficulty is removing departing from desired of the planar section on barrier layer, and it may result in relatively low gate height or other problem.Often, The selectivity of CMP composition is not enough to the shifting of reliably and consistently (consistently) stopping material when exposing barrier layer Remove.

In view of the difficulty encountered in the metal removed on TiN or Ti/TiN obstacle, exist at suppression Ti/ TiN obstacle realizes the CMP composition effectively removed of metal and the lasting needs of method while removing.Side described herein Method and compositions solve this needs.

Summary of the invention

Described herein a kind of for removing metal, electrolyte or the polymeric layer being deposited on TiN or Ti/TiN barrier layer Chemically mechanical polishing (CMP) method.The method includes by acid CMP composition (such as with the polishing pad in CMP planarization device Grind away together) metal (such as Cu, CuMn, Ta, TaN, Al, AlCo, Co, CoMo, Ru, RuTa, RuTiN, Mn, TiN (automatic stop Only), W, Pt) or electrolyte (such as Si oxide, silicon nitride, carborundum, polysilicon) or polymer (such as PR, SOG type oxygen Compound).Described CMP composition comprises and is suspended in containing selected from anionic surfactant, cationic surface active agent, non- Particulate abrasive (such as silicon dioxide, oxygen in the liquid carrier of the surfactant of ionic surfactant and combinations thereof Change aluminum).The method is particularly well-suited to comprise on the obstacle of the substrate on TiN or Ti/TiN barrier layer stopping polishing (stop-on- barrier polishing).Surprisingly, surfactant helps removing of TiN and Ti/TiN of suppression not disturb gold Removing of genus, electrolyte or polymer.

In some embodiments, described CMP composition comprises the particulate abrasive of 0.001-10 weight % (wt%).Grain Some examples of shape grinding agent include that silica sol that mean diameter is 10 to 300 and mean diameter are the oxygen of 10 to 300 Change aluminum.The pH of described CMP composition is preferably in the range of 2 to 7.Surfactant can be such as with 10-50,000 PPM (part-per-million；Ppm) concentration in the range of is present in CMP composition.

In some preferred implementations, described CMP composition comprises oxidant (such as hydrogen peroxide) further, citing For, the hydrogen peroxide of 0-5wt%.

In some embodiments, surfactant can comprise anionic surfactant, and such as sulphonate surface is lived Property agent, sulfate surfactant, phosphonate surfactant (such as alkyl phosphonate) and phosphate surfactant active is (such as Alkylphosphonic monoesters or diester or the alkylphosphonic of ethoxylation).Selectively, or additionally, surfactant can Comprise nonionic surfactant, such as acetylenic glycols surfactant.Some preferred anionic surfactanies include, Such as, Anionic sulphonate surfactant, such as alkylaryl sulfonate (such as alkylbenzenesulfonate, such as dodecyl Benzene sulfonate), monoalkyl sulfosuccinate and dialkyl sulfosuccinate.

In a preferred embodiment, the dioxy of the 0.001-10wt% during described CMP composition is included in aqueous supporting agent SiClx or alumina abrasive, 10-50, the sulfosalt surfactant of 000ppm and the hydrogen peroxide of 0-5wt%, in scope It is under the pH of 2 to 7.Sulfosalt surfactant preferably comprises alkyl benzene sulfonate surfactant (such as detergent alkylate sulphur Hydrochlorate) and/or the sulfo-succinic acid salt surfactant of monoalkyl or dialkyl group.

In another preferred embodiment, two of the 0.001-10wt% during described CMP composition is included in aqueous supporting agent Silicon oxide or alumina abrasive, 10-50, the nonionic surfactant of 000ppm and the hydrogen peroxide of 0-5wt%, Scope is under the pH of 2 to 7.Nonionic surfactant preferably comprises acetylenic glycols surfactant (such as acetylenic glycol, its second Epoxide compound, its ethoxylate-propoxylate or aforementioned in the combination of two or more).

Compositions as herein described and method advantageously provide the excellence for removing metal relative to TiN and Ti/TiN Selectivity.Specifically, anionic surfactant and nonionic surfactant surprisingly help suppress TiN and Ti/TiN removes and still allows for acceptable metal removal rate simultaneously.

Accompanying drawing explanation

Fig. 1 provides and is combining with the CMP comprising different anions type surfactant and nonionic surfactant The TiN observed during thing polishing TiN blanket wafers removes the figure of speed (RR) suppression (%).

Fig. 2 provides pH and is 2.3 and comprises 0.025 weight % (wt%) silica sol and 0.162wt% malonic acid The TiN of the CMP composition of the 750ppm iron ion of chelating and the different surfaces activating agent of 1000ppm (activity concentration) moves The figure of removal rates.

Fig. 3 provides having (w/) and not having under being used in different silica solids level concentration (SC%) There is the CMP composition the comprising silica sol polishing TiN blanket of (w/o) 1000ppm DBSA surfactant The figure of the TiN RR observed when covering formula wafer and TiN RR suppression (%).

Fig. 4 provides having (w/) and not having (w/o) 1000ppm ten under being used in different composition pH The CMP composition polishing TiN blanket wafers comprising 0.025wt% silica sol of dialkyl benzene sulfonic acids surfactant Time the TiN RR that observed and TiN RR suppression (%) figure.

Fig. 5 provides to be had (w/) in use and does not has (w/o) 1000ppm DBSA surfactant The TiN RR observed during the CMP composition polishing TiN blanket wafers comprising 0.025wt% difference grinding agent and TiN RR The figure of suppression (%).

Detailed description of the invention

CMP composition be applicable to method described herein is included in the particulate abrasive aqueous supporting agent and surface activity Agent.Described compositions surprisingly results in: suppression TiN and Ti/TiN remove speed and still provide simultaneously metal (such as Cu, CuMn, Ta, TaN, Al, AlCo, Co, CoMo, Ru, RuTa, RuTiN, Mn, TiN (self-stopping technology), W, Pt) or electrolyte (such as silicon Oxide, silicon nitride, carborundum, polysilicon) or acceptable removing of removing of polymer (such as PR, SOG type oxide) Speed.

The surface active agent composition of described CMP composition can comprise anionic surfactant, cationic is lived Property agent, nonionic surfactant or combinations thereof.As described herein, said composition can comprise single surface and live Property agent, kinds of surface activating agent from single kind (or subclass) surfactant, or optionally can comprise from difference The combination of two or more surfactants of kinds of surfactants (or subclass).Surfactant is in the composition Concentration can be at least 10ppm, such as, at least 25ppm, at least 50ppm, at least 100ppm, at least 500ppm, at least 1000ppm or at least 2,000ppm.It addition, the concentration that surfactant is in the composition can be less than 50,000ppm, Such as 40,000ppm, 30,000ppm, 20,000ppm, 10,000ppm or 5,000ppm.Typically, surfactant is with 10- Concentration in the range of 50,000ppm, preferred 50-5000ppm is present in described CMP composition.

Preferably, anionic surfactant is lived selected from the phosphonate surfactant of general classes, phosphate surface Property agent, sulfosalt surfactant and sulfate surfactant." phosphonate ", " phosphate ", " sulphur as the term is employed herein Hydrochlorate " and " sulfate " refer to surfactant ionizing (anion) form (it includes at least one anion oxygen) and The sour form (it includes at least one acid OH group) of surfactant.As known in the art, many based on sulfur and base Acid in the surfactant of phosphorus be typically in the form of highly acidic and even under relatively low pH value (such as pH is 2 to 3) Tend to ionizing.Therefore, the anionic surfactant in the CMP composition of the present invention generally by main with anion Form exists, regardless of whether be to add in a salt form or as the acid in surfactant extremely described compositions.

The subclass of the limiting examples being applicable to the sulfosalt surfactant of CMP composition as herein described includes alkane Arylsulphonate (such as alkylbenzenesulfonate, such as dodecyl benzene sulfonate), alkylsulfonate (such as alkenyl sulphonate, Such as alpha-alkene sulfonate, alkyl glycerol sulfonated ester, alkylether sulfonate and alkyl sulfoacetate), sulfosuccinate (such as monoalkyl sulfosuccinate and dialkyl sulfosuccinate), acyl taurine salt (acyl taurate) and acyl group Isethionate.

Alkylaryl sulfonate is the anionic surfactant of a preferred classes.Alkyl can be relative to sulfonic acid group Any position be connected to aryl (such as benzene) part.Alkyl be typically included the carbon atom more than 6 and can be straight chain or Side chain.Branched alkyl can be connected to aryl moiety via primary carbon (such as methylene), secondary carbon or tertiary carbon.Preferably alkaryl sulphur Hydrochlorate is dodecyl benzene sulfonate, and wherein, dodecyl can be any alkyl having and amounting to 12 carbon, and therefore can be Straight or branched.Branched dodecyl can be connected to benzene part via primary carbon (such as methylene), secondary carbon or tertiary carbon.Preferably Ground, dodecyl comprises and connects via secondary carbon (i.e., inwardly along dodecyl chain rather than at the end of this chain) Straight chain dodecyl chain to phenyl.

Those of ordinary skill in chemical field will be apparent from, and the surfactant in given CMP composition leads to The most stable by being selected under the storage pH of CMP composition.Accordingly, it is preferred that anionic surfactant classification is phosphine (i.e., wherein the hydrophobic parts of surfactant is bonded to hydrophilic by C-S or C-P bond for hydrochlorate and sulfosalt surfactant The surfactant of S or the P group of property), with phosphate and sulfate on the contrary, it is due to the hydrophobic parts of surfactant And ester bond between hydrophilic parts and there is stability problem the most at acidic.Additionally, it is preferred that sulfonate and phosphonic acids Salt surfactant is such material, and within this material, hydrophobic parts includes the sourest stable key (that is, C-C key ether And amide, and it is carboxylate group in some cases).Some examples of the sourest stable sulfonate include such as alkane virtue Base sulfonate, alkenyl sulphonate, alkylether sulfonate, acyl taurine salt, monoalkyl sulfosuccinate and dialkyl sulfosuccinate Succinate.

Preferably nonionic surfactant includes that alkylaryl alcohol, alkynol and acetylenic glycols (are generally also known as acetylenic glycol Surfactant), including such as 2,5,8,11-tetramethyl-6-dodecyne-5,8-glycol, 2,4,7,9-tetramethyl-5-decine- The acetylenic glycols material of 4,7-glycol and fellow thereof, and ethoxylated acetylenic glycols and ethoxylated-propoxylated acetylenic glycols.Lift For example, acetylenic glycols surfactant can be represented by with following formula I and Formula II, wherein R¹And R⁴For comprising the straight of 3 to 10 carbon atoms Chain or branched alkyl chain；R²And R³For H or the alkyl chain that comprises 1 to 5 carbon atom, and m, n, p and q are that meansigma methods is at 0 to 20 model Enclose interior numeral.The example of such acetylenic glycols surfactant and preparation thereof is described in the United States Patent (USP) of such as Zhang et al. In No. 6,641,896.

Particulate abrasive can be any grinding agent being suitable for CMP application, such as SiO₂(silicon dioxide), Al₂O₃(oxygen Change aluminum), CeO₂(ceria), ZnO₂(zirconium oxide) or MnO₂.Grinding agent can have any applicable mean diameter (i.e., averagely Particle diameter).The mean diameter of grinding agent can be 4nm or bigger, 10nm or bigger, 15nm or bigger, 20nm or bigger or 25nm or bigger.Selectively, or additionally, the mean diameter of grinding agent can be 300nm or less, 150nm or less, 120nm or less, 110nm or less, 100nm or less, 90nm or less, 80nm or less, 70nm or less, 60nm or more Little, 50nm or less or 40nm or less.Therefore, grinding agent can have average by limit with any two of upper extreme point Particle diameter.For aspherical particle, the size of granule is the diameter of the smallest sphere surrounding this granule.In some preferred implementations In, grinding agent is selected from silicon dioxide (such as silica sol) and aluminium oxide.Preferably, the mean diameter of particulate abrasive is 10-300nm.Preferably the mean diameter of colloidal silica abrasive is in the range of 10-300nm, preferred 10-150nm.Dioxy Silicon carbide particle may generally be spherical, oblate spheroid, dumb-bell shape or cocoon shape.Preferably the mean diameter of alumina abrasive is 10- 300nm, more preferably 10-150nm.

Described polishing composition can contain 0.001wt.% or more, 0.1wt.% or more, 0.25wt.% or more, Or 0.5wt.% or more grinding agent.Selectively, or additionally, described polishing composition can be containing 10wt.% or more Low, 5wt.% or lower, 4wt.% or lower, the grinding agent of 3wt.% or lower or 2wt.% or lower.Therefore, described Polishing composition can comprise the grinding agent having by for the amount limited with any two in upper extreme point cited by grinding agent. Grinding agent is typically present in CMP composition with the concentration in the range of 0.001-10wt%, preferred 0.001-5wt%.Excellent Selection of land, grinding agent is present in CMP composition with the concentration of 0.001-10wt% (such as 0.001-5wt%).In institute such as herein At use point during the finishing method stated, grinding agent preferably exists with the concentration of 0.001-5wt% (such as 0.001-2wt%) In CMP composition.

Desirably, silica abrasive will have the ζ more than 0mV 2.3 times at pH in described polishing composition Current potential.The zeta potential of granule refers to the electric charge of circumgranular ion and bulk solution (such as liquid carrier and appointing of wherein dissolving What its component) electric charge between difference.

The compositions of the present invention has acid pH, i.e. pH is less than 7.In some embodiments, pH can be 2 until the model of 7 In enclosing, such as 2 to 6, such as 3 to 5.Preferably, pH is in the range of 2 to 5.The pH of described compositions can include acid by including in The padded coaming of property component (it can comprise any inorganic or organic acid) is reached and/or maintains.Preferably, acid pH is by bag Maintain containing having the organic or inorganic buffer agent being adapted for carrying out the amount of desired pH and the alkalescence of ratio and acidic components.Acid Property buffer agent is well-known to the ordinarily skilled artisan in chemical field.

In some preferred implementations, described CMP composition comprises oxidant, such as hydrogen peroxide further, optionally Ground combines with metal ion (such as iron ion).Described polishing composition can be containing the oxidant of any suitable amount.Described polishing Compositions can contain 0.05wt.% or higher, 0.1wt.% or higher or 0.25wt.% or higher oxidant.Optional Ground, or additionally, described polishing composition can contain 5wt.% or lower, 2.5wt.% or lower, 1wt.% or lower, The oxidant of 0.8wt.% or lower or 0.6wt.% or lower.Therefore, described polishing composition can comprise have by for The oxidant of the amount limited with any two in upper extreme point cited by oxidant.In some embodiments, described CMP group Compound is using the hydrogen peroxide comprising 0-5wt% at point.

In conventional CMP technique, substrate carrier or rubbing head be arranged on carrier module and be positioned to in CMP device Polishing pad contact.Carrier module provides controllable pressure to substrate, promotes that substrate offsets with polishing pad.Described pad and carrier And the substrate connected is moved relative to.Described pad is used for grinding base plate surface with from substrate table with the relative movement of substrate Face removes a part for material, thus polishes substrate.The polishing of substrate surface is typically via the chemism of polishing composition (such as by the oxidant being present in CMP composition, acid, alkali or other additive) and/or be suspended in polishing composition The mechanical activation of particulate abrasive and assisted further.

The polishing composition of the present invention optionally may also include the appropriate one being typically included in polishing composition or Other additive material multiple, such as metal chelating agent, dispersant, stabilizer, corrosion inhibitor, viscosity modifier, biocidal Agent, cationic surface active agent, nonionic surfactant, inorganic salt and fellow thereof.For example, described compositions Biocide can be included, such asOrBiocide；Chelating agent, such as acetic acid, group ammonia Acid, lysine, glycine, pyridine carboxylic acid, tartaric acid, iminodiacetic acid, alanine, benzoic acid, complexon I (NTA), glutamic acid, 1,3-propanedicarboxylic acid, Beta-alanine, aspartic acid, ornithine or proline；Corrosion inhibitor, such as benzotriazole (BTA), 1,2,3-triazoles, 1,2,4-triazoles, tetrazolium (that is, 5-Aminotetrazole), 3-amino-1,2,4-triazole, phenyl-phosphonic acid, first Base phosphonic acids；And fellow.In some embodiments, described CMP composition can include water soluble salt, such as ammonium nitrate, uses In profile control and electric conductivity (conductivity).For example, described compositions can include the water solublity of 50-2000ppm Salt.Described CMP composition may also include and can optionally be bound to Si oxide relative to silicon nitride with further auxiliary silicon Nitride removes selective cationic surface active agent.

Aqueous supporting agent can be any aqueous solvent, such as water, aqueous methanol, aquiferous ethanol, a combination thereof and fellow thereof.Excellent Selection of land, aqueous supporting agent comprises water, more preferably deionized water, is substantially made up of water, more preferably deionized water, or by water, more Preferably deionized water composition.

Polishing composition used in method described herein can be prepared by any applicable technology, and many of which technology is Well known by persons skilled in the art.Described polishing composition can technique be prepared in batches or continuously.It is said that in general, described polishing group Compound can be prepared by combining its component in any order." component " includes single composition (example as the term is employed herein Such as grinding agent, polymer, chelating agen, buffer agent and fellow thereof) and any combination of composition.For example, ceria Grinding agent is dispersed among in water and polymers compositions is combined and can described component be incorporated in polishing composition by any Method mixes.Typically, when using oxidant, until compositions prepares just to add oxidant to throwing when CMP Light compositions, such as, just can add oxidant before starting polishing.Can be in any applicable moment by adding as required Acid adding or alkali regulate pH further.

The polishing composition of the present invention can also provide with concentration form, and it is used for before the use with appropriate aqueous Solvent (such as water) is diluted.In such embodiment, polishing composition concentrate can include dividing with following amount The various components dissipated or be dissolved in aqueous solvent, described amount makes when diluting concentrate with appropriate aqueous solvent, polishing Amount in proper range for application is present in polishing composition by each component of compositions.

The CMP method of the present invention is preferably used chemical mechanical polishing apparatus and realizes.Typically, CMP device includes: pressing plate, It is in use in motion and has by track, the linear and/or speed of circular motion generation；Polishing pad, itself and pressing plate Contact and move relative to pressing plate when motion；And carrier, its fixing treats the surface by contact polishing pad and relative to polishing The substrate being polished is moved on the surface of pad.The polishing of substrate is carried out by following steps: put into by substrate and polishing pad And the polishing composition of the present invention contacts and then makes polishing pad move relative to substrate, in order to abrade at least some of of substrate To polish substrate.

Following example further illustrate certain aspects of the invention, but certainly should not be construed in any way as limiting it Category.As used by herein and in following example and claims, it is reported to PPM (ppm) or weight % (wt%) concentration is the weight based on the active component the paid close attention to weight divided by compositions.

There is provided following non-limiting example with further illustrate compositions as herein described and method some aspect and Feature.

Embodiment 1

This embodiment illustrates different surfaces activating agent and TiN is removed the impact of speed suppression.

Grinding agent used in this embodiment and following example is summarized in table 1.

Table 1

Grinding agent	Grinding agent type	Shape	Zeta potential under pH 2.3	Mean diameter
					A	Aluminium oxide	Spherical	-15.1	100nm
B	Silica sol	Cocoon shape	4.83	25nm
					C	Silica sol	Cocoon shape	3.82	35nm
D	Silica sol	Cocoon shape	6.4	50nm
					E	Silica sol	Cocoon shape	12.1	70nm
F	Silica sol	Spherical	1.19	50nm
					G	Silica sol	Spherical	5.1	70nm
H	Silica sol	Cocoon shape	7.35	50nm
					I	Silica sol	Cocoon shape	38.4	35nm
J	Silica sol	Cocoon shape	50.9	50nm

Prepare pH to be 2.3 and comprise 0.025 weight % (wt%) silica sol (the grinding agent J, Fuso from table 1 Chemical Co.Ltd.), live in listed various surfaces in the table 1 of 0.5wt% hydrogen peroxide and 1000ppm (activity concentration) Property agent, remaining be the aqueous CMP composition of water.Use FujiboH7000 polishing pad and following burnishing parameters by various combinations Thing to TiN blanket wafers polishing 60 seconds: 111rpm bearer rate, the pressing plate speed of 113rpm, the downward force of 1.5psi and The slurry flow of 150mL.By use the TiN removal quantity that observes of each compositions with having the base identical with testing compositions This formula but do not have the surfactant of any interpolation comparison CMP composition (tester) polishing TiN blanket wafers time The TiN removal quantity observed compares.TiN removes speed (RR) suppression and deducts test combination by the speed that removes of tester The speed that removes of thing calculates and described difference table is shown as the percentage ratio of tester.

Fig. 1 provides the TiN RR of various anionic surfactanies and the nonionic surfactant observed to press down The figure of system (%).Surface activity agent inhibitor and the assessment table of various on-surface-active agent addition agent (such as aminoacid and triazole) Bright on-surface-active agent addition agent is not suitable for providing desired TiN RR to suppress.In some cases, especially for sulfur Hydrochlorate, sulfonate, phosphate, alkylaryl alcohol, amide and acetylenic glycols surfactant, observe the TiN RR suppression more than 80% (see for example the SINONATE 1105SF (5) in Fig. 1, SINONATE 290MH (6), ZETASPERSE 2300 (7), DBS (16)、OLFINE WE-001(18)、OLFINE WE-003(19)、SURFYNOL 604(23)、SURFYNOL 707P(24)、 SINOPOL 9620P (25), poly-(acrylamide) (34) and the result of RHODAFAC RS710 (26)).

Table 2

Table 2 (Continued)

Table 2 (Continued)

The most in table 2: the Chemical Abstracts Service accession designation number of CAS=active component.

Brand is that the surfactant of SURFYNOL and ZETASPERSE is purchased from Air Products and Chemicals, Inc.；Brand is that the surfactant of SINOPOL and SINONATE is purchased from Sino-Japan Chemical Co.Ltd.；Brand Surfactant for OLFINE is purchased from Shin-Etsu Chemical Co.；Brand is that the surfactant of RHODAFAC is purchased from Rhodia；Brand is that the surfactant of ADEKA is purchased from Adeka Corp., and brand is that the surfactant of DOWFAX is purchased from Dow Chemical Co；And the surfactant that brand is ALCOSPERSE is purchased from AkzoNobel Surface Chemistry, LLC。

Embodiment 2

This embodiment explanation iron ion is as the TiN RR of the oxidant CMP composition to comprising different surfaces activating agent Impact.

Prepare pH to be 2.3 and comprise 0.025 weight % (wt%) silica sol (the grinding agent J, Fuso from table 1 Chemical Co.Ltd.), 750ppm ferric nitrate and 0.162wt% malonic acid, additionally contain 1000ppm (with activity concentration Meter) the aqueous CMP composition of different surfaces activating agent.Use following burnishing parameters by polishing pad (Fujibo) and described TiN blanket wafers is polished 60 seconds by CMP composition.The bearer rate of 111rpm, the pressing plate speed of 113rpm, 1.5psi to Exert oneself and the slurry flow of 150ml.Fig. 2 provides various groups compared with the Similar Composite Systems thing without surface activity agent inhibitor The TiN of compound removes the figure of speed.

Result in Fig. 2 shows: minimum TiN removes speed (TiN RR suppression the highest i.e.) and passes through detergent alkylate The mixing of sulfonic acid (DBS) and (C10-C14) alkylbenzenesulfonate and ethoxylation (C6-C12) alcohol (ZETASPERSE 2300) Thing obtains, and both of which is alkyl benzene sulfonate surfactant.

Embodiment 3

This embodiment explanation abrasive solid concentration is to having and do not have DBSA (DBS) surfactant The CMP composition comprising colloidal silica abrasive TiN RR suppression impact.

(come with different abrasive solid concentration (SC%) preparations colloidal silica abrasive that comprises under pH 2.3 From grinding agent J, the Fuso Chemical Co. of table 1) and 0.5wt% hydrogen peroxide, have and do not have 1000ppm DBS's Aqueous polishing slurries, and by using Fujibo H7000 polishing pad and following burnishing parameters that TiN blanket wafers is polished 60 Second is estimated: the bearer rate of 111rpm, the pressing plate speed of 113rpm, the downward force of 1.5psi and the slurry flow of 150mL. Polish results is showed in Fig. 3 to graphically.

Data in Fig. 3 show: TiN RR suppression in the range of the solid concentration of 0.025wt% to 10wt% somewhat (somewhat) it is distributed in changeably in the range of 38% to 100%, wherein, under the polishing condition of this assessment, TiN RR remains less thanUntil the solid concentration of 2.5wt%.It addition, described result shows: even if causing higher polishing Under the high solid concentration (10%) of speed, TiN RR suppression is still high (71%).

Embodiment 4

This embodiment explanation pH comprises colloid two to having and do not have DBSA (DBS) surfactant The impact of the TiN RR suppression of the CMP composition of silica abrasive.

Prepare under the integer pH value of 2 to 7 and comprise colloidal silica abrasive (from grinding of table 1 under pH 2.3 Grinding agent J, Fuso Chemical Co.Ltd.) and 0.5wt% hydrogen peroxide, have and do not have 1000ppm DBS containing water throwing Light slurry.By using following burnishing parameters that the polishing of TiN blanket wafers was assessed CMP composition in 60 seconds: Fujibo H7000 polishing pad, the bearer rate of 111rpm, the pressing plate speed of 113rpm, the downward force of 1.5psi and the stream of slurry of 150mL Amount.Polish results is showed in Fig. 4 to graphically.

Result in Fig. 4 shows: obtains the highest TiN RR pH 2 and 3 times and suppresses level.

Embodiment 5

The different grinding-material of this embodiment explanation is to having and do not have DBSA (DBS) surfactant The impact of the TiN RR suppression of CMP composition.

Preparation comprising in 0.025wt% table 1 under pH 2.3 listed grinding agent and 0.5wt% hydrogen peroxide, have And not there is the aqueous polishing slurries of 1000ppm DBS.By using following burnishing parameters that TiN and W blanket wafers is polished Within 60 seconds, assess CMP composition: Fujibo H7000 polishing pad, the bearer rate of 111rpm, the pressing plate speed of 113rpm, The downward force of 1.5psi and the slurry flow of 150mL.TiN polish results is showed in Fig. 5 to graphically.

Result in Fig. 5 shows, for having the process of surfactant, all grinding agents after tested all show non- The highest TiN RR suppression, wherein, actual TiN RR value is less than under evaluation conditionDescribed result it is also shown that For not having the process of surfactant, TiN RR changes in a wide range, such as, fromExtremely

All references, including publication, patent application and patent the most also Entering herein, this quotes degree just as individually and specifically indicating each list of references to be herein incorporated by reference and illustrating in full The most general.

Unless otherwise indicated herein or context is clearly contradicted, the most in the description of the invention in the context (the most especially In the context of claims) term " " that uses is interpreted as with " one " and " being somebody's turn to do " and similar indicant Contain odd number and plural number.Unless otherwise indicated, otherwise term " comprises ", " having ", " including " and " containing " are all construed to open Formula term (i.e., it is meant that " including, but are not limited to ").Term " Consists of " and " by ... constitute " should be interpreted that closed art Listed in language, its given claim that any compositions or method are limited to respectively this specification or part specify Component or step.It addition, and due to its open nature, term " comprises " to be contained widely substantially by specified component or step The rapid compositions forming or being made up of specified component or step and method, except including the given power beyond this specification Profit requires or outside those components listed in part or other component of step or the compositions of step and method.Unless this In literary composition otherwise indicated, the scope of the value enumerated the most herein is intended only to serve as to be mentioned individually and belongs to each independent values in the range of this Stenography method, and each independent values the most individually enumerates such as it and generally incorporates in this specification.The institute obtained by measurement Numerical value (such as weight, concentration, physical size, remove speed, flow and fellow thereof) is had to should not be construed as absolute precise figures, And should be regarded as the value containing in the known limits of measurement technology conventional in the art, regardless of whether term is expressly recited " about ".Unless otherwise indicated herein or additionally context is clearly contradicted, and all methods the most as herein described can be with any suitable Conjunction order performs.Unless additionally advocated, any and all embodiment the most provided in this article or exemplary language are (such as " all As ") use be intended only to preferably illustrate certain aspects of the invention and do not limit the scope of the invention.In this specification Any language should be construed as indicating the key element putting into practice any failed call essential to the invention protection.

The preferred embodiment of the present invention described herein, it includes that the present inventor becomes known for carrying out the optimal mould of the present invention Formula.When reading described above, the change of these preferred implementations can become bright for those of ordinary skills Clear.The inventors expect that those skilled in the art suitably use such change, and the present inventor is intended to be different from herein The mode of middle specific descriptions implements the present invention.Therefore, if the allowed by law words being suitable for, the present invention includes claims The all modifications of theme cited in book and equivalent.Additionally, the unless otherwise indicated herein or other obvious lance of context Shield, otherwise the present invention contain above-mentioned key element with its combination in any of likely version.

Claims (24)

1. a polishing comprises the chemically mechanical polishing of substrate on titanium nitride (TiN) or titanium/titanium nitride (Ti/TiN) barrier layer (CMP) method, the method includes making this substrate and comprises the acid CMP composition of the particulate abrasive being suspended in liquid carrier Contact, this liquid carrier comprises selected from anionic surfactant, cationic surface active agent, non-ionic surfactant The surfactant of agent and combinations thereof.

2. the process of claim 1 wherein that this particulate abrasive comprises silica sol.

3. the process of claim 1 wherein that this particulate abrasive comprises aluminium oxide.

4. the process of claim 1 wherein that this particulate abrasive comprises the combination of silica sol and aluminium oxide.

5. the process of claim 1 wherein that this particulate abrasive is present in this CMP with the concentration of 0.001-10 weight % (wt%) In compositions.

6. the process of claim 1 wherein that this surfactant is deposited with 10-50, the concentration in the range of 000 PPM (ppm) It is in this CMP composition.

7. the process of claim 1 wherein that this surfactant comprises acetylenic glycols nonionic surfactant.

8. the process of claim 1 wherein that this surfactant comprises sulfonate anionic type surfactant.

9. the method for claim 8, wherein this anionic surfactant comprises alkylaryl sulfonate.

10. the method for claim 9, wherein this alkylaryl sulfonate comprises alkylbenzenesulfonate.

The method of 11. claim 10, wherein this alkylbenzenesulfonate comprises dodecyl benzene sulfonate.

The method of 12. claim 8, wherein this anionic surfactant comprises monoalkyl sulfosuccinate, dialkyl group Sulfosuccinate or a combination thereof.

13. the process of claim 1 wherein that this surfactant comprises lives selected from sulfosalt surfactant, sulfate surface Property agent, phosphonate surfactant and at least one anionic surfactant of phosphate surfactant active.

14. the process of claim 1 wherein that the pH of this CMP composition is in the range of 2 to 7.

15. the process of claim 1 wherein that this CMP composition comprises oxidant further.

The method of 16. claim 15, wherein this oxidant comprises hydrogen peroxide.

The method of 17. claim 16, wherein this hydrogen peroxide is present in this CMP combination with the concentration in the range of 0.01-5wt% In thing.

18. the process of claim 1 wherein together with the polishing pad in CMP planarization device complete abrade.

19. the process of claim 1 wherein that this CMP composition is included in the 0.001-under the pH of 2 to 7, in aqueous supporting agent 10wt% grinding agent, 10-50,000ppm sulfosalt surfactant and 0.01-5wt% hydrogen peroxide.

The method of 20. claim 19, wherein this sulfosalt surfactant comprises alkylbenzenesulfonate.

The method of 21. claim 20, wherein this alkylbenzenesulfonate comprises dodecyl benzene sulfonate.

The method of 22. claim 19, wherein this sulfosalt surfactant comprises monoalkyl sulfosuccinate, dialkyl group sulphur Base succinate or a combination thereof.

23. the process of claim 1 wherein that this CMP composition is included in the 0.001-under the pH of 2 to 7, in aqueous supporting agent 10wt% grinding agent, 10-50,000ppm nonionic surfactant and 0-5wt% hydrogen peroxide.

The method of 24. claim 23, wherein this nonionic surfactant comprises acetylenic glycols.