CA2324151A1 - Chemical mechanical polishing slurry useful for copper substrates - Google Patents

Chemical mechanical polishing slurry useful for copper substrates Download PDF

Info

Publication number
CA2324151A1
CA2324151A1 CA002324151A CA2324151A CA2324151A1 CA 2324151 A1 CA2324151 A1 CA 2324151A1 CA 002324151 A CA002324151 A CA 002324151A CA 2324151 A CA2324151 A CA 2324151A CA 2324151 A1 CA2324151 A1 CA 2324151A1
Authority
CA
Canada
Prior art keywords
chemical mechanical
mechanical polishing
slurry
polishing slurry
abrasive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002324151A
Other languages
French (fr)
Inventor
Vlasta Brusic Kaufman
Rodney C. Kistler
Shumin Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2324151A1 publication Critical patent/CA2324151A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321After treatment
    • H01L21/32115Planarisation
    • H01L21/3212Planarisation by chemical mechanical polishing [CMP]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/02Polishing compositions containing abrasives or grinding agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/1454Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463Aqueous liquid suspensions

Abstract

A chemical mechanical polishing slurry comprising an oxidizing agent, a complexing agent, an abrasive, and an optional surfactant, as well as a method for using the chemical mechanical polishing slurry to remove copper alloy, titanium, titanium nitride, tantalum and tantalum nitride containing layers from a substrate. The slurry does not include a separate film-forming agent.

Description

WO 99/47618 _ 1 _ PC1'/US99/05968 TITLE
CHEMICAL MECHANICAL POLISHING SLURRY
USEFUL FOR COPPER SUBSTRATES
s BACKGROUND OF THE INVENTION
(1) Field of the Invention.
1o This invention concerns a chemical mechanical polishing slurry including a complexing agent, at least one oxidizer, and at least one abrasive. The slurry is notable in that it does not include a film-forming agent. The amounts and types of oxidizers and complexing agents are selected to maximize polishing while minimizing the depth of any passivation layer on the substrate surface. The chemical mechanical polishing 15 slurry of this invention is useful for polishing metal layers and thin-films associated with semiconductor manufacturing. More particularly this invention concerns three component chemical mechanical polishing slurries that are especially formulated to polish multiple metal layers and thin-films where one of the layers or films is comprised of copper or a copper containing alloy.
(2) Description of the Art.
Integrated circuits are made up of millions of active devices formed in or on a silicon substrate. The active devices, which are initially isolated from one another, are interconnected to form fi~nctional circuits and components. The devices are interconnected through the use of well-known multilevel interconnections.
Interconnection structures normally have a first layer of metallization, an interconnection layer, a second level of metallization, and sometimes a third and subsequent level of metallization. Interlevel dielectrics, such as doped and undoped silicon dioxide (Si02), are used to electrically isolate the different levels of 3o metallization in a silicon substrate or well. The electrical connections between different interconnection levels are made through the use of metallized vias.
U.S.
Patent No. 4,789,648, which is incorporated herein by reference, describes a method for preparing multiple metallized layers and metallized vias in insulator films. In a similar manner, metal contacts are used to form electrical connections between interconnection levels and devices formed in a well. The metal vias and contacts may be filled with various metals and alloys including titanium (Ti), titanium nitride (TiN), tantalum (Ta), aluminum copper (Al-Cu), aluminum silicon (Al-Si), copper (Cu), tungsten (W), and combinations thereof. The metal vias and contacts generally employ an adhesion layer such as titanium nitride (TiN) and/or titanium (Ti) to adhere the metal layer to the Si02 substrate. At the contact level, the adhesion layer acts as a diffusion barrier to prevent the filled metal and Si02 from reacting.
to In one semiconductor manufacturing process, metallized vias or contacts are formed by a blanket metal deposition followed by a chemical mechanical polish (CMP) step. In a typical process, via holes are etched through an interlevel dielectric (ILD) to interconnection lines or to a semiconductor substrate. Next, a thin adhesion layer such as titanium nitride and/or titanium is generally formed over the ILD and is directed into the etched via hole. Then, a metal film is blanket deposited over the adhesion layer and into the via hole. Deposition is continued until the via hole is filled with the blanket deposited metal. Finally, the excess metal is removed by chemical mechanical polishing, (CMP) to form metal vias. Processes for manufacturing and/or CMP of vias are disclosed in U.S. Patent Nos. 4,671,851, 4,910,155 and 4,944,836.
2o In a typical chemical mechanical polishing process, the substrate is placed in direct contact with a rotating polishing pad. A carrier applies pressure against the backside of the substrate. During the polishing process, the pad and table are rotated while a downward force is maintained against the substrate back. An abrasive and chemically reactive solution, commonly referred to as a "slurry" is applied to the pad during polishing. The slurry initiates the polishing process by chemically reacting with the film being polished. The polishing process is facilitated by the rotational movement of the pad relative to the substrate as slurry is provided to the wafer/pad interface.
Polishing is continued in this manner until the desired film on the insulator is removed.
The slurry composition is an important factor in the CMP step. Depending on the 3o choice of the oxidizing agent, the abrasive, and other useful additives, the polishing slurry can be tailored to provide effective polishing to metal layers at desired polishing _3_ rates while minimizing surface imperfections, defects, corrosion and erosion.
Furthermore, the polishing slurry may be used to provide controlled polishing selectivities to other thin-film materials used in current integrated circuit technology such as titanium, titanium nitride and the like.
s Typically CMP polishing slurries contain an abrasive material, such as silica or alumina, suspended in an oxidizing, aqueous medium. For example, U. S. patent No.
5,244,534 to Yu et al. reports a slurry containing alumina, hydrogen peroxide, and either potassium or ammonium hydroxide that is useful to remove tungsten at predictable rates with little removal of the underlying insulating layer. U.S.
Patent l0 5,209,816 to Yu et al. discloses a slurry comprising perchloric acid, hydrogen peroxide and a solid abrasive material in an aqueous medium that is useful for polishing aluminum. U.S. Patent 5,340,370 to Cadien et al. discloses a tungsten polishing slurry comprising approximately O.1M potassium ferricyanide, approximately 5 weight percent silica and potassium acetate. Acetic acid is added to buffer the pH at 1 s approximately 3 . 5.
U.S. Patent No. 4,789,648 to Beyer et al. discloses a slurry formulation using alumina abrasives in conjunction with sulfuric, nitric, and acetic acids and deionized water. U.S. Patent Nos. 5,391,258 and 5,476,606 disclose slurries for polishing a composite of metal and silica which includes an aqueous medium, abrasive particles 2o and an anion which controls the rate of silica removal. Other polishing slurries for use in CMP applications are described in U.S. Patent No. 5,527,423 to Neville et al., U.S.
Patent No. 5,354,490 to Yu et al., U.S. Patent No. 5,157,876 to Medellin, U.S.
Patent No. 5,137,544 to Medellin, and U.S. Patent No. 4,956,313 to Cote et al.
There are various mechanisms disclosed in the prior art by which metal surfaces 25 can be polished with slurries. The metal surface may be polished using a slurry in which a surface film is not formed in which case the process proceeds by mechanical removal of metal particles and their dissolution in the slurry. In such a mechanism, the chemical dissolution rate should be slow in order to avoid wet etching. A more preferred mechanism is, however, one where a thin abradable layer is continuously 3o formed by reaction between the metal surface and one or more components in the slurry such as a complexing agent and/or a film forming layer. The thin abradable layer _4-is then removed in a controlled manner by mechanical action. Once the mechanical polishing process has stopped a thin passive film remains on the surface and controls the wet etching process. Controlling the chemical mechanical polishing process is much easier when a CMP slurry polishes using this mechanism.
Efforts to develop copper CMP slurries are disclosed in the literature. The RPI
effort (J. M. Steigerwald et al, Electrochemical Potential Measurements during the Chemical Mechanical Polishing of C.'opper Thin Films, Mat. Res. Soc. Symp.
337, 133 (1994)) is focused on the use of ammonium compounds (ammonium nitrate, chloride, hydroxide), nitric acid, and alumina abrasive. Copper dissolution of 2 nm/min (as measured electrochemically) is assumed to proceed from a film-free surface.
Polishing rates, however, are reported to be in excess of 400 nm/min. The discrepancy is explained by importance given to the mechanical action, forming Cu debris, which is then dissolved by solution. Selectivity factors are not given.
Q. Luo et al, Chemical Mechanical Polishing ~f Copper in Acidic Media, Proceedings - First International Chemical-Mechanical Polish (CMP) for VLSI/LSl Multilevel Interconnection Conference (CMP-MIC), Santa Barbara, Feb. 22-23, (1996) discloses using a CMP slurry including a very aggressive etchant, Fe-nitrate, pH
1-2, in combination with an inhibitor (benzotriazole), a slurry stabilizing surfactant (poly-ethylene-glycol) and alumina. The chemical reaction is apparently controlled by 2o a formation of a corrosion inhibiting film, namely Cu-BTA, with surfactant undermining its protectiveness. Selectivity to oxide is given as 15:1 to 45:1.
CMP electrochemical work at Sematech laboratories is disclosed in R. Carpio et al, Initial Study On Copper CMP Slurry Chemistries, Thin Solid Films, 262 (1995).
The reference explores the use of electrochemistry in the fundamental characterization 2s of plausible slurries. In addition to several others, potassium permanganate is used as a slurry oxidizer.
H. Hirabayashi et al, Chemical Mechanical Polishing of C.'opper (Icing A
Slurry Composed of Glycine and Hydrogen Peroxide, Proceedings - First International Chemical-Mechanical Polish (CMP) for VLSI/LSI Multilevel Interconnection 3o Conference (CMP-MIC), Santa Barbara, Feb. 22-23, (1996), and Japanese Kokai Patent Application No. 8 (1996) 83780 disclose a mixture of glycine, hydrogen _5_ , peroxide and silica, with or without benzotriazole, for the CMP process of Cu with a low corrosion rate and defect level. The references disclose that CMP slurries incorporating a chemical agent, such as benzotriazole and n-benzoyl-n-phenylhydroxylamine form a protective film on copper. The removal rate varies, depending on the concentration of slurry components. An optimized rate of 120 nm/min was reported, with TiN rate of 30 nm/min and dishing of 200 nm across the 15 um wide structures.
In the course of polishing substrates using slurries including passivating agents such as benzotriazole (BTA), it has been discovered that reaction of BTA with the to copper surface during polishing produces a surface film which is very resistant to the mechanical action of the abrasive, making removal of the surface film difficult.
Furthermore, the degree of passivation is time dependent and not easy to control making automation of substrate polishing processes difi7cult. In addition, BTA
undergoes oxidative degradation. Thus, a slurry containing BTA and an oxidizer has a short useful pot life that limits manufacturing usefulness. These properties of passivating agents, such as BTA, make it difl-icult to use machines to polish passivated substrates in a reproducible manner.
Despite the desirability of using passivating agents in a film forming mechanism in CMP process, there remains problems with formulating CMP slurries that are able to 2o control the thickness of the passivating layer of film formed as well as problems ensuring that the film formed is abradable. These problems can result in film forming CMP slurries that exhibit unacceptably low polishing rates or poor polishing results.
Thus, a need remains for a CMP slurry that is capable of forming a removable thin passive layer on a substrate surface, and more particularly on the surface of a copper alloy containing substrate. A desirable CMP slurry will exhibit good thin film polishing selectivities and simultaneously give polished substrates with minimal dishing and low defectivity.

_6_ , _ SUMMARY OF THE INVENTION
The present invention is directed to a chemical mechanical polishing slurry that is able to polish metal containing substrates at reproducible and acceptable rates.
In addition, the chemical mechanical polishing slurries of this invention have low insulator polishing selectivities while exhibiting high polishing selectivities towards copper and copper alloy containing metal layers.
Furthermore, this invention is directed to methods for using a single chemical 1o mechanical polishing slurry to polish metal layers and particularly copper or copper alloy containing layers in an integrated circuit.
In one embodiment, this invention is a chemical mechanical polishing slurry.
The slurry includes an abrasive, at least one oxidizer, and a complexing agent selected from the group of compounds including citric acid, lactic acid, tartaric acid, succinic acid, malonic acid, oxalic acids, amino acids and salts thereof. The slurry does not include a film forming agent.
In another embodiment, this invention is a chemical mechanical polishing slurry.
The slurry includes an abrasive, an oxidizing agent selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, and mixtures thereof, and tartaric acid.
2o The chemical mechanical polishing slurry has a pH of from about 5.0 to about 9.0, however, no film-forming agent is present in the slurry.
In still another embodiment, this invention is a method for polishing a substrate including at least one metal layer. Polishing is accomplished by admixing, from about 1.0 to about 15.0 weight percent of an abrasive, from about 0.3 to about I5.0 weight 2, percent of an oxidizer, from about 0.5 to about 5.0 weight percent of at least one complexing agent, and deionized water to give a chemical mechanical polishing slurry.
No film-forming agent is added to the slurry. Next, the chemical mechanical polishing slurry is applied to the substrate and at least a portion of the metal layer is removed from the substrate by bringing a pad into contact with the substrate and moving the 3o pad in relation to the substrate.

t In yet another embodiment, this invention is a mufti-package system useful for preparing a chemical mechanical polishing slurry. The mufti-package system includes a first container including a complexing agent and a second container comprising an oxidizing agent. An abrasive material may be located in a container selected from the group consisting of the first container, the second container, or a third container.
DESCRIPTION OF THE CURRENT EMBODIMENT
The present invention relates to a chemical mechanical polishing .composition to precursor and to a chemical mechanical polishing slurry that is effective even without a film-forming agent. The chemical mechanical polishing slurry comprises an abrasive and the precursor. The precursor includes at least one oxidizer and a complexing agent wherein the oxidizer and complexing agent are selected and formulated in amounts su~cient to inhibit dissolution of the surface of the substrate being polished.
1s The chemical mechanical polishing slurry is useful for polishing metals, especially copper and copper alloy containing metal layers associated with a substrate selected from the group including integrated circuits, thin films, multiple level semiconductors, and wafers.
Before describing the details of the various preferred embodiments of this 2o invention, some of the terms that are used herein will be defined. The chemical mechanical polishing slurry, ("CMP slurry"), is a useful product of this invention that comprises an oxidizer, an abrasive, a complexing agent, and other optional ingredients.
However, the CMP slurry does not include a film forming agent. The CMP slurry is useful for polishing a multiple level metallizations which may include but are not 25 limited to, semi-conductor thin-films, integrated circuit thin-films, and for any other films and surfaces where CMP processes are useful. The terms "copper" and "copper containing alloys" are used interchangeably herein as it is within the understanding of one of skill in the art that the terms include, but are not limited to, substrates comprising layers of pure copper, copper aluminum alloys, and Ti/TiN/Cu, and 3o Ta/TaN/Cu mufti-layer substrates.
The CMP slurry of this invention includes at least one oxidizer. The oxidizer aids in oxidizing the substrate metal layer or layers to their corresponding oxide, _g_ hydroxide, or ions. For example, in the present invention, the oxidizer may be used to oxidize a metal layer to its corresponding oxide or hydroxide, e.g. , titanium to titanium oxide, tungsten to tungsten oxide, copper to copper oxide, tantalum to tantalum oxide, and aluminum to aluminum oxide. The oxidizing agent is useful when incorporated into a CMP slurry to polish metals and metal based components including titanium, titanium nitride, tantalum, tantalum nitride, copper, tungsten, aluminum, and aluminum alloys such as aluminum/copper alloys, and various mixtures and combinations thereof by mechanically polishing the metals to remove the respective oxide layer.
The oxidizer used in the CMP slurry of this invention may be selected from 1o compounds, which, upon reduction, form hydroxyl radicals. Such oxidizers exhibit good polishing selectivity towards metal and metal containing substrate layers and particularly towards copper alloy layers. Non-exclusive examples of metal oxidizing compounds that, upon reduction, form hydroxyl radicals include peracetic acid, urea-hydrogen peroxide, urea peroxide, and hydrogen peroxide and mixtures thereof, with hydrogen peroxide, urea hydrogen peroxide, and mixtures thereof being preferred oxidizers.
The oxidizer may be present in the chemical mechanical polishing slurry in an amount ranging from about 0.3 to about 30.0 weight percent. It is preferred that the oxidizer is present in the CMP slurry of this invention in an amount ranging from about 0.3 to about 17.0 weight percent and most preferably from about 1.0 to about 12.0 weight percent.
In another embodiment, the oxidizer is urea hydrogen peroxide. Because urea hydrogen peroxide is 34.5 wt % hydrogen peroxide and 65.5 wt % urea, a greater amount by weight of urea hydrogen peroxide must be included in CMP slurries of this 2s invention to achieve the desired oxidizer loading set forth above. For example, a range of 1.0 to 12.0 weight percent oxidizer corresponds to a urea hydrogen peroxide weight three times as great or from 3.0 to 36.0 weight percent.
A CMP slurry comprising urea hydrogen peroxide can be formulated by a number of methods including combining urea peroxide with water, and by combining 3o urea and hydrogen peroxide in an aqueous solution in a mole ratio range of from about 0.75:1 to about 2:1 to give a urea hydrogen peroxide oxidizer.

-9_ " _ The CMP slurry of this invention differentiates itself from other CMP
slurries, and especially from CMP slurries useful for polishing copper layers, in that it does not include a separate film forming agent in addition to the oxidizing agent.
Examples of such separate film-forming agents that are omitted from the compositions of this invention include cyclic compounds such as imidazole, benzotriazole, benzimidazole and benzothiazole. A separate film forming agent is omitted from the precursor and slurry compositions of this invention in order to avoid difficulties encountered in controlling the depth of and subsequently removing the corrosion inhibiting layers formed by separate film-forming agents.
Io During chemical mechanical polishing, it is important to inhibit dissolution of the substrate surface layer in order to minimize surface defectively. One class of compounds found to be useful in combination with oxidizing agents to control surface dissolution are complexing agents. Useful complexing agents include, but are not limited to, acids such as citric, lactic, tartaric, succinic, acetic, malonic oxalic and other acids and salts thereof such as ammonium tartarate, as well as amino acid and amino sulfuric acids and their salts. Preferred complexing agents are tartaric acid, citric acid, malonic acid, and mixtures thereof with tartaric acid being most preferred.
The complexing agents serve to form a complex with the oxidized metal and not the underlying unoxidized metal thereby limiting the depth of the oxidized layer.
2o The complexing agent will be present in the CMP slurry of this invention in an amount ranging from about 0.1 to about 5.0 weight percent, and preferably in an amount ranging from about 0.5 to about 3.0 weight percent.
It is desirable to maintain the pH of the CMP slurry of this invention within a range of from about 2.0 to about 12.0, preferably between from about 5.0 to about 9.0 2; and most preferably from about 6.5 to about 7.5 in order to facilitate control of the CMP process. Slurry handling problems and substrate polishing quality problems are encountered when the pH of the CMP slurry of this invention is too low, e.g., less than 2. When tartaric acid is selected as the complexing agent, the CMP slurry will have a pH of about 2.0 and pH adjustment to a higher level is necessary.
3o The pH of the CMP slurries of this invention may be adjusted using any known acid, base, or amine. However, the use of an acid or base that contains no metal ions, -10- ' -such as ammonium hydroxide and amines, or nitric, phosphoric, sulfuric, or organic acids are preferred to avoid introducing undesirable metal components into the CMP
slurry of this invention.
In order to promote stabilization of a CMP slurry of this invention against settling, flocculation, and decomposition, a variety of optional CMP slurry additives, such as surfactants, stabilizers, or dispersing agents, can be used. If a surfactant is added to the CMP slurry, then it may be an anionic, cationic, nonionic, or amphoteric surfactant or a combination of two or more surfactants can be employed.
Furthermore, it has been found that the addition of a surfactant may be useful to 1o reduce the within-wafer-non-uniformity (WIWNU) of the wafers, thereby improving the surface of the wafer and reducing wafer defects.
In general, the amount of optional additives such as a surfactant that are used in the present invention should be sufficient to achieve effective stabilization of the slurry and will typically vary depending on the particular surfactant selected and the nature of the surface of the metal oxide abrasive. For example, if not enough of a selected surfactant is used, it will have little or no effect on CMP slurry stabilization.
On the other hand, too much surfactant in the CMP slurry may result in undesirable foaming and/or flocculation in the slurry. As a result, stabilizers such as surfactants should generally be present in the slurry of this invention in an amount ranging from 2o about 0.001% to about 0.2% by weight, and preferably from about 0.001 to about 0.1 weight percent. Furthermore, the additive may be added directly to the slurry or treated onto the surface of the metal oxide abrasive utilizing known techniques. In either case, the amount of additive is adjusted to achieve the desired concentration in the polishing slurry. Preferred surfactants include dodecyl sulfate sodium salt, sodium lauryl sulfate, dodecyl sulfate ammonium salt, and mixtures thereof. Examples of useful surfactants include TRITON°~' DF-16 manufactured by Union Carbide, and SURFYNOL~' manufactured by Air Products and Chemicals.
The CMP slurry of this invention includes an abrasive. The abrasive is typically a metal oxide abrasive. The metal oxide abrasive may be selected from the group 3o including alumina, titania, zirconia, germania, silica, ceria and mixtures thereof. The CMP slurry of this invention preferably includes from about 1.0 to about 15.0 weight percent or more of an abrasive. It is more preferred, however, that the CMP
slurry of this invention includes from about 2.0 to about 6.0 weight percent abrasive.
The metal oxide abrasive may be produced by any techniques known to those skilled in the art. Metal oxide abrasives can be produced using any high temperature process such as sol-gel, hydrothermal or plasma process, or by processes for manufacturing fumed or precipitated metal oxides. Preferably, the metal oxide is a fumed or precipitated abrasive and more preferably it is a fumed abrasive such as fumed silica or fumed alumina. For example, the production of fumed metal oxides is a well-known process which involves the hydrolysis of suitable feedstock vapor (such as 1o aluminum chloride for an alumina abrasive) in a flame of hydrogen and oxygen.
Molten particles of roughly spherical shapes are formed in the combustion process, the diameters of which are varied through process parameters. These molten spheres of alumina or similar oxide, typically referred to as primary particles, fuse with one another by undergoing collisions at their contact points to form branched, three dimensional chain-like aggregates. The force necessary to break aggregates is considerable. During cooling and collecting, the aggregates undergo further collision that may result in some mechanical entanglement to form agglomerates.
Agglomerates are thought to be loosely held together by van der Waals forces and can be reversed, i. e. , de-agglomerated, by proper dispersion in a suitable media.
2o Precipitated abrasives may be manufactured by conventional techniques such as by coagulation of the desired particles from an aqueous medium under the influence of high salt concentrations, acids or other coagulants. The particles are filtered, washed, dried and separated from residues of other reaction products by conventional techniques known to those skilled in the art.
A preferred metal oxide will have a surface area, as calculated from the method of S. Brunauer, P.H. Emmet, and I. Teller, J. Am. Chemical Society, Volume 60, Page 309 (1938) and commonly referred to as BET, ranging from about 5 mz/g to about m2/g and preferably from about 30m2/g to about 170 m2/g. Due to stringent purity requirements in the IC industry, the preferred metal oxide should be of a high purity.
High purity means that the total impurity content, from sources such as raw material -12_ impurities and trace processing contaminants, is typically less than 1 % and preferably less than 0.01 % (i. e., 100 ppm).
The metal oxide abrasive useful in the slurry of this invention may consist of metal oxide aggregates or individual single sphere particles. The term "particle" as it is used herein refers to both aggregates of more than one primary particle and to individual single particles.
It is preferred that the metal oxide abrasive consists of metal oxide particles having a size distribution less than about 1.0 micron, (i. e., all particles are less than 1.0 micron in diameter), a mean particle diameter less than about 0.4 micron and a force Io sufl'lcient to repel and overcome the van der Waals forces between abrasive aggregates themselves. Such metal oxide abrasive has been found to be effective in minimizing or avoiding scratching, pit marks, divots and other surface imperfections during polishing.
The particle size distribution in the present invention may be determined utilizing known techniques such as transmission electron microscopy (TEM). The mean la particle diameter refers to the average equivalent spherical diameter when using TEM
image analysis, i. e. , based on the cross-sectional area of the particle. By force is meant that either the surface potential or the hydration force of the metal oxide particles must be sufficient to repel and overcome the van der Waals attractive forces between the particles.
2o In another preferred embodiment, the metal oxide abrasive may consist of discrete, individual metal oxide particles having a primary particle diameter less than 0.4 micron (400nm) and a surface area ranging from about 10 mz/g to about 250 m2/g.
Preferably, the metal oxide abrasive is incorporated into the aqueous medium of the polishing slurry as a concentrated aqueous dispersion of metal oxides, 25 comprising from about 3% to about 45% solids, and preferably between 10%
and 20%
solids. The aqueous dispersion of metal oxides may be produced utilizing conventional techniques, such as slowly adding the metal oxide abrasive to an appropriate media, for example, deionized water, to form a colloidal dispersion. The dispersion is typically achieved by subjecting the aqueous solution of metal oxide to high shear mixing 3o conditions known to those skilled in the art. The pH of the dispersion may be adjusted away from the isoelectric point to a pH of about 4.0 in order to maximize colloidal stability. The dispersion is typically diluted with deionized water and other slurry ingredients during CMP slurry preparation. A most preferred metal oxide abrasive is SEMI-SPERSE~ W-A3 S 5 fumed alumina dispersion manufactured by Cabot Corporation. W-A355 is a 9 wt% fumed alumina dispersion having a pH of about 4Ø
Although the CMP slurry of this invention may be used to'polish any type of metal layer, the chemical mechanical polishing slurry of this invention has been found to have a high copper, titanium, titanium nitride, and tantalum nitrate and acceptable tantalum polishing rates. In addition, the chemical mechanical polishing slurry exhibits desirable low polishing rates towards the dielectric insulating Iayer.
to The CMP slurry of this invention may be produced using conventional techniques known to those skilled in the art. Typically, the oxidizing agent and other non-abrasive components, are mixed into an aqueous medium, such as deionized or distilled water, at pre-determined concentrations under low shear conditions until such components are completely dissolved in the medium. A concentrated dispersion of the metal oxide abrasive, such as fumed alumina, is added to the medium and diluted to the desired loading level of abrasive in the final CMP slurry.
The CMP slurries of the present invention may be supplied as one package system (oxidizing agent, abrasive, and complexing agent in a stable aqueous medium).
To avoid possible CMP slurry degradation, it is preferred that at least a two package 2o system is used where the first package comprises the compiexing agent, abrasive dispersion, and any optional additives, and the second package comprises an oxidizer.
Other two-container combinations of the ingredients of the CMP slurry of this invention are within the knowledge of one having ordinary skill in the art.
CMP slurries of this invention can be formulated by combining one or more complexing agents with one or more metal oxide abrasives and deionized water to give a oxidizer free containing CMP precursor. Formulating CMP slurries of this invention from a slurry precursor eliminates stability, shipping and safety concerns associated with hydrogen peroxide containing slurries. This is because the oxidizer free CMP
precursor can also be prepared and shipped to the location where it will be used and 3o then mixed with an oxidizing agent such as hydrogen peroxide on site to give a CMP
slurry.

WO 99!47618 PCT/US99/05968 An optional slurry precursor of this invention will comprise an aqueous mixture of urea, at least one complexing agent, and at least one metal oxide abrasive.
Additional ingredients, other than a film forming agent, may be incorporated into the urea containing slurry precursor.
s A most preferred slurry precursor of this invention includes an aqueous dispersion of fumed alumina, a complexing agent selected from ammonium oxalate, tartaric acid, ammonium tartarate or mixtures thereof, and preferably tartaric acid, and a surfactant in quantities disclosed above. The slurry precursor or mixtures thereof, will preferably have a pH of from about 5.0 to about 9Ø
1o A mufti-package CMP slurry system may be used with any standard polishing equipment appropriate for use on the desired metal layer of the wafer. The multi-package system includes one or more CMP slurry components in, where appropriate, aqueous or dry form in two or more containers. The mufti-package system is used by combining the components from the various containers in the desired amounts to give 1s a CMP slurry comprising at least one oxidizing agent, a complexing agent, and at least one abrasive in the amounts described above, prior to or at the time of the slurry to a substrate. The preferred package system comprises a first container including a CMP
slurry precursor comprising alumina, urea, a complexing agent selected from ammonium oxalate, tartaric acid, ammonium tartarate and mixtures thereof, and a 2o surfactant at a pH from about s.0 to about 8.0 and a second container including hydrogen peroxide. At the polishing location, a preselected amount of the CMP
precursor and a selected amount of hydrogen peroxide are combined at the time of polishing to give a CMP slurry of this invention.
The CMP slurry of the present invention does not significantly increase the 25 silicon dioxide polishing rate. However, the CMP slurry of this invention polishes copper, titanium, titanium nitride, tantalum, and tantalum nitride layers at good rates under controllable conditions. Thus, the CMP slurry of this invention is ei~ective in controlling polishing selectivities of titanium, copper, titanium nitride , tantalum, and tantalum nitride layers. The polishing slurry of the present invention may be used 3o during the various stages of semiconductor integrated circuit manufacture to provide _ WO 99/47618 PCT/US99/05968 effective polishing at desired polishing rates while minimizing surface imperfections and defects.
EXAMPLES
We have discovered that a film-forming-agent-free CMP slurry including at least one abrasive, at least one oxidizer, and complexing agent of specific types and amounts is capable of polishing multiple metal layers comprising copper alloys, titanium, and titanium nitride, tantalum and tantalum nitride at high rates while 1o exhibiting good selectivity towards dielectric layers.
The following examples illustrate preferred embodiments of this invention as well as preferred methods for using compositions of this invention.
EXAMPLE I
is This Example evaluates the dissolution and corrosion of copper in the presence of CMP slurries with and without the film forming agent BTA. The rate of Cu dissolution during the CMP process is deducted from electrochemical measurements.
Most of the electrochemical data are obtained ex situ (i.e. not on the polishing table) 2o using a device consisting of a Cu rotating disk electrode (with a rotator by Pine) and 273 Pontentiostat with Corrosion Software (by EG&G, PAR). A platinum mesh electrode serves as an auxiliary electrode, and a saturated mercurous sulfate electrode (MSE) is used as the reference electrode. Electrochemical data are obtained with a preselected electrode rotation of 500 rpm (or 19.94 m/sec., maximum) with the rotator 2s and the electrode in a contact with an abrasive pad (with a down force of 1.2 kg or 5.9 psi) or raised above the pad.
The device can measure the metal dissolution as the metal surface is abraded (or polished on the polishing tool) as well as after abrasion. The abrasion value is considered to be an approximate measure of the chemical rate during polishing, while 3o the measurements following abrasion give the corrosion rate of the metal in a given slurry. Typically, electrochemical data are recorded as potentiodynamic polarization WO 99J47618 PC'T/US99/05968 curves, with the potential swept from about -0.25 V cathodic to the open circuit potential to some anodic potential, by a rate of 10 mV/sec.
Each of the slurries evaluated had a pH of 7Ø The alumina used in the slurnes was SEMI-SPERSE~ W-A355 fumed alumina dispersion, manufactured by Cabot s Corporation and diluted to the desired loading level. The copper dissolution rate, measured with the device as a current density, was re-calculated in terms of /min and is listed for several slurries in Table I.
Table I
Slurry Cu Dissolution rate Cu corrosion with abrasion, ~ /min rate (after abrasion) /min 3% alumina, 2% H202, 1 ppm Triton DF-16 and 4.8 0.2 0.04%

BTA

2 Same as 1 but w/o 24 4.8 BTA

3 % alumina, 2% HZOz, 3 amm. oxalate, 50 ppm 96 1.4 Triton DF-16 and 0.04% BTA
4 Same as 3 but w/o 2,400 60 BTA

3% alumina, 2% H202, 1%

tartaric acid, 3.65% 96 1.1 urea, 50 ppm Triton DF-16 and 0.04%

BTA _ 6 Same as in 5 but w/o 240 24 BTA

to The results show that the rate of Cu dissolution during and after abrasion is relatively low using slurries containing only H202 (and a surfactant), as the Cu surface is passivated with Cu-oxide (slurry 2). Additions of BTA to Hz02 result in additional surface film with Cu dissolution rate with and without abrasion in a single digits (slurry ua 1). Upon additions of a strong complexing agent, such as ammonium oxalate to the slurries, Cu dissolution rate with abrasion is 100 times higher (compare slurry 2 and 4) than in peroxide alone, while Cu corrosion rate increases from about 5 to 60 /min.
The use of a film forming agent such as BTA, decreases the Cu dissolution rate to 96 /min with abrasion and 1.4 t~/min after abrasion, respectively. With tartaric acid, 20 slurries 5 and 6, the dissolution rate of Cu with or without abrasion, with or without BTA, is still relatively low. Thus, with this complexing agent, the passivation ability of the oxidizer is not significantly effected, and the film forming agent, BTA, is not needed to limit the Cu corrosion rate.
EXAMPLE II
This Example evaluates the ability of CMP slurries with and without 0.04wt%
BTA film forming agent fo polish various substrate layers. Each slurry included 2.0 wt HZO2, 1.0 wt % tartaric acid, 3.0 wt % of SEMI-SPERSE~ W-A355 fumed alumina 1o dispersion manufactured by Cabot Corporation, and 50 ppm Triton DF-IG. The pH of each slurry was adjusted to 7.0 using NHaOH prior to use.
Each CMP slurry was applied to PVD copper wafers having a Ti, TiN or Ta underlayer on and IPEC 472 polisher and polished using a perforated IV pad stack manufactured by Rodel, Inc. at 3 psi down force, a table speed of 55 rpm and a spindle speed of 30 rpm and a back pressure of 0.8 psi. The polishing data are reported in Table II below.

_18_ . _ Table II
WITH BTA WITHOUT BTA
Performance PerformancePerformance PerformancePerformance Parameter w/TiN_ w/Ta w/TiN w/Ta Cu Polishing 3000-8000 3000-8000 3639 /min 5600 t~/min rate /min /min Cu WIWNU 4.7 (15%) 5.6% 7.9%

Selectively 1.~ and 1.8:1 to Ti hi er Selectively 1.5:1 1.5:1 to TiN

Selectively 13:1 12: I
to Ta Selectivel 7:1 8:1 to TaN

Selectively > 100:1 > 100:1 > 100:1 > 100:1 to Si02 Dishin (150 1145 t~
m) Dishing (100pm) 2900 A (1~% 850 ~ 1100 A

ove olishin ) Dishin (~0 650 ~ 1200 /A
) Dishin (20 577 ~
) Dishin ( 1 290 290A
~ m) Erosion 483 ~ 1250A (IS% 255 400It ove olish) Post CMP particle 0 count (no particle/wafer oxide buffing) (with 0.2 micron threshold) Cu (in E 10) nd to 80 on PETEOS

PETEOS surface < 0.30 nm rms rou hness (usin AFM) Time to clear <4 min patterned wafer with 1.6 Cu The results show that the polishing performance in the slurries with and without BTA is comparable, and slightly improved in the slurry without BTA
when dishing and erosion are considered.
EXAMPLE III

Removal rates of Cu, Ta and glass were determined in this Example using slurries with different concentrations of H202 and tartaric acid, at pH 7Ø
The WO 99_/47618 PCT/US99/05968 -19- ' abrasive used in each slurry was SEMI-SPERSE~ W-A355 fumed alumina dispersion manufactured by Cabot Corporation. The polishing results are reported in Table 3.
PVD Cu wafers were polished using an IPEC 472 tool at a down force of 3 psi, a back pressure of 0.6 psi, a platen speed of 55 rpm, and a carrier speed of 30 rpm.
Table III
Slurry Cu removal Ta removal PETEOS
rate rate Almin t~/min removal rate t~/min 3 % alumina, 2.5 H20z, 1.25%
tartaric 1 acid, 3.65% 2396 434 77 urea, 50 m Triton DF-16 5 % alumina, H~O2, 0.7% tartaric 2 acid, 3.65% 102 432 78 urea, 50 m Triton DF-16 2% alumina, 5%

H20~, 0.3% tartaric 3 acid, 3.65% 807 408 135 urea, 50 ppm Triton DF-16 The results set forth in Table III show that the higher the weight ratio of the peroxide to tartaric acid, the smaller the Cu removal rate (i.e. the better the 1o passivation).
The present invention is a CMP slurry precursor and slurry manufactured therefrom that has no film-forming agent, and, instead comprises an abrasive, at least one oxidizing agent, and at least one complexing agent. CMP slurries of this invention are able to polish metal layers in a controlled manner by forming a reproducibly thin passivating layer. As a result, less variability is introduced into the polishing process, the polishing performance of the slurry is more consistent and controllable, the polishing results are good, and the shelf life of the product is increased.
While the present invention has been described by means of specific embodiments, it will be understood that modifications may be made without 2o departing from the spirit of the invention. The scope of the invention is not to be _ WO 99147618 PCT/US99/05968 -20_ considered as limited by the description of the invention set forth in the specification and examples, but rather as defined by the following claims.
What we claim is:

Claims (33)

-21-
1. A chemical mechanical polishing slurry comprising:
an abrasive;
at least one oxidizer; and from about 0.1 to 5.0 wt % of a complexing agent selected from the group of compounds including citric acid, lactic acid, tartaric acid, malonic acid, succinic acid, oxalic acids, amino acids, salts thereof and mixtures thereof wherein the slurry has a pH of from about 5 to about 9, and wherein the slurry does not include a film-forming agent.
2. The chemical mechanical polishing slurry of claim 1 wherein the complexing agent is tartaric acid.
3. The chemical mechanical polishing slurry of claim 2 wherein the tartaric acid is present in an amount ranging from 0.5 to about 3.0 weight percent.
4. The chemical mechanical polishing slurry of claim 1 wherein the oxidizer is a compound that forms hydroxyl radicals upon reduction.
5. The chemical mechanical polishing slurry of claim 4 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide and combinations thereof.
6. The chemical mechanical polishing slurry of claim 5 wherein the hydrogen peroxide is present in an amount ranging from about 0.3 to about 17 weight percent.
7. A chemical mechanical polishing slurry comprising:
an abrasive;
an oxidizing agent selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, and mixtures thereof; and tartaric acid, wherein the chemical mechanical polishing slurry has a pH of from to 9, wherein the slurry does not include a film-forming agent.
8. The chemical mechanical polishing slurry of claim 7 wherein the oxidizing agent is hydrogen peroxide.
9. The chemical mechanical polishing slurry of claim 7 wherein the oxidizing agent is urea hydrogen peroxide.
10. The chemical mechanical polishing slurry of claim 7 wherein the tartaric acid is present in the slurry in an amount ranging from about 0.5 to about 3.0 weight percent.
11. The chemical mechanical polishing slurry of claim 7 wherein the abrasive is at least one metal oxide.
12. The chemical mechanical polishing slurry of claim 11 wherein the metal oxide abrasive is selected from the group including alumina, ceria, germania, silica, titania, zirconia, and mixtures thereof.
13. The chemical mechanical polishing slurry of claim 7 wherein the abrasive is an aqueous dispersion of a metal oxide.
14. The chemical mechanical polishing slurry of claim 11 wherein the metal oxide abrasive consists of metal oxide aggregates having a size distribution less than about 1.0 micron and a mean aggregate diameter less than about 0.4 micron.
15. The chemical mechanical polishing slurry of claim 11 wherein the metal oxide abrasive consists of discrete, individual metal oxide spheres having a primary particle diameter less than 0.4 micron and a surface area ranging from about 10 m2/g to about 250 m2/g.
16. The chemical mechanical polishing slurry of claim 7 wherein the abrasive has a surface area ranging from about 5 m2/g to about 430 m2/g.
17. The chemical mechanical polishing slurry of claim 7 wherein the abrasive has a surface area of from about 30 m2/g to about 170 m2/g.
18. The chemical mechanical polishing slurry of claim 7 wherein the abrasive is selected from the group consisting of precipitated abrasives or fumed abrasives.
19. A chemical mechanical polishing slurry comprising:
from about 1.0 to about 15.0 weight percent of an alumina abrasive;
from about 1.0 to about 12.0 weight percent hydrogen peroxide; and from about 0.5 to about 3.0 weight percent tartaric acid, wherein the composition has been adjusted to a pH of from about 5 to about 9, and wherein the slurry does not include a film-forming agent.
20. The chemical mechanical polishing slurry of claim 19 including at least one surfactant.
21. A method for polishing a substrate including at least one metal layer comprising the steps of:
(a) admixing, from about 1.0 to about 15.0 weight percent of an abrasive, from about 0.3 to about 17.0 weight percent of an oxidizer, from about 0.1 to about 5.0 weight percent of at least one complexing agent, and deionized water to give a chemical mechanical polishing slurry wherein the slurry does not contain a film-forming agent;
(b) adjusting the pH of the slurry to a range of from about 5 to about 9;
(c) applying the chemical mechanical polishing slurry to the substrate; and (d) removing at least a portion of the metal layer from the substrate by bringing a pad into contact with the substrate and moving the pad in relation to the substrate.
22. The method of claim 21 wherein the substrate includes a copper alloy containing layer.
23. The method of claim 21 wherein the substrate further includes a titanium and titanium nitride layer wherein at least a portion of the titanium and titanium nitride layer is removed in step (c).
24. The method of claim 21 wherein the chemical mechanical polishing slurry is applied to the pad before the pad is placed into contact with the substrate.
25. The method of claim 21 wherein the oxidizer is hydrogen peroxide, urea hydrogen peroxide and mixtures thereof.
26. The method of claim 21 wherein complexing agent is tartaric acid.
27. The method of claim 21 wherein the chemical mechanical polishing slurry has a pH of from about 5.0 to about 9Ø
28. The method of claim 21 wherein the abrasive is a metal oxide.
29. The method of claim 28 wherein the metal oxide abrasive is selected from the group including alumina, ceria, germania, silica, titania, zirconia, and mixtures thereof.
30. The method of claim 21 wherein the abrasive is an aqueous dispersion of a metal oxide.
31. The method of claim 30 wherein the metal oxide abrasive is selected from the group consisting of precipitated alumina, fumed alumina, precipitated silica, fumed silica, and mixtures thereof.
32. A method for polishing a substrate including a copper alloy layer, a titanium layer and a titanium nitride layer comprising:
(a) admixing from about 1.0 to about 15.0 weight percent of alumina, from about 1.0 to about 12.0 weight percent hydrogen peroxide, from about 0.5 to about 3.0 weight percent tartaric acid, and deionized water to give a chemical mechanical polishing slurry wherein the copper alloy to titanium polishing selectivity [Cu:Ti] is less than about 4.
(b) adjusting the chemical mechanical polishing slurry pH to from about 5.0 to about 9.0;
(c) applying the chemical mechanical polishing slurry to the substrate; and (d) removing at least a portion of the copper alloy layer and at least a portion of the titanium layer and at least a portion of the titanium nitride layer by bringing a pad into contact with the substrate and moving the pad in relation to the substrate.
33. A multi-package system useful for preparing a chemical mechanical polishing slurry comprising:
(a) a first container including a complexing agent;
(b) a second container comprising an oxidizing agent; and (c) an abrasive located in a container selected from the group consisting of the first container, the second container, or a third container.
CA002324151A 1998-03-18 1999-03-18 Chemical mechanical polishing slurry useful for copper substrates Abandoned CA2324151A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/040,630 US6432828B2 (en) 1998-03-18 1998-03-18 Chemical mechanical polishing slurry useful for copper substrates
US09/040,630 1998-03-18
PCT/US1999/005968 WO1999047618A1 (en) 1998-03-18 1999-03-18 Chemical mechanical polishing slurry useful for copper substrates

Publications (1)

Publication Number Publication Date
CA2324151A1 true CA2324151A1 (en) 1999-09-23

Family

ID=21912052

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002324151A Abandoned CA2324151A1 (en) 1998-03-18 1999-03-18 Chemical mechanical polishing slurry useful for copper substrates

Country Status (12)

Country Link
US (3) US6432828B2 (en)
EP (1) EP1064338B1 (en)
JP (3) JP2002506915A (en)
KR (1) KR100594561B1 (en)
CN (1) CN1157450C (en)
AU (1) AU3100499A (en)
CA (1) CA2324151A1 (en)
DE (1) DE69933015T2 (en)
ID (1) ID27122A (en)
IL (1) IL138483A0 (en)
TW (1) TWI256966B (en)
WO (1) WO1999047618A1 (en)

Families Citing this family (106)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6126853A (en) * 1996-12-09 2000-10-03 Cabot Microelectronics Corporation Chemical mechanical polishing slurry useful for copper substrates
US6432828B2 (en) * 1998-03-18 2002-08-13 Cabot Microelectronics Corporation Chemical mechanical polishing slurry useful for copper substrates
JP4608925B2 (en) * 1998-12-25 2011-01-12 日立化成工業株式会社 Additive for CMP abrasives
DE19927286B4 (en) * 1999-06-15 2011-07-28 Qimonda AG, 81739 Use of a grinding solution for the chemical mechanical polishing of a precious metal surface
US6419554B2 (en) * 1999-06-24 2002-07-16 Micron Technology, Inc. Fixed abrasive chemical-mechanical planarization of titanium nitride
CA2378771A1 (en) * 1999-08-13 2001-02-22 Cabot Microelectronics Corporation Chemical mechanical polishing systems and methods for their use
TWI254070B (en) * 1999-08-18 2006-05-01 Jsr Corp Aqueous dispersion for chemical mechanical polishing
US6347978B1 (en) 1999-10-22 2002-02-19 Cabot Microelectronics Corporation Composition and method for polishing rigid disks
JP2001187877A (en) * 1999-12-28 2001-07-10 Nec Corp Slurry for chemical mechanical polishing
JP3602393B2 (en) * 1999-12-28 2004-12-15 Necエレクトロニクス株式会社 Slurry for chemical mechanical polishing
US6443811B1 (en) * 2000-06-20 2002-09-03 Infineon Technologies Ag Ceria slurry solution for improved defect control of silicon dioxide chemical-mechanical polishing
US7134934B2 (en) * 2000-08-30 2006-11-14 Micron Technology, Inc. Methods and apparatus for electrically detecting characteristics of a microelectronic substrate and/or polishing medium
US7074113B1 (en) 2000-08-30 2006-07-11 Micron Technology, Inc. Methods and apparatus for removing conductive material from a microelectronic substrate
US7112121B2 (en) * 2000-08-30 2006-09-26 Micron Technology, Inc. Methods and apparatus for electrical, mechanical and/or chemical removal of conductive material from a microelectronic substrate
US7153195B2 (en) * 2000-08-30 2006-12-26 Micron Technology, Inc. Methods and apparatus for selectively removing conductive material from a microelectronic substrate
US7078308B2 (en) * 2002-08-29 2006-07-18 Micron Technology, Inc. Method and apparatus for removing adjacent conductive and nonconductive materials of a microelectronic substrate
US7220166B2 (en) * 2000-08-30 2007-05-22 Micron Technology, Inc. Methods and apparatus for electromechanically and/or electrochemically-mechanically removing conductive material from a microelectronic substrate
US7192335B2 (en) * 2002-08-29 2007-03-20 Micron Technology, Inc. Method and apparatus for chemically, mechanically, and/or electrolytically removing material from microelectronic substrates
US7160176B2 (en) 2000-08-30 2007-01-09 Micron Technology, Inc. Methods and apparatus for electrically and/or chemically-mechanically removing conductive material from a microelectronic substrate
US7129160B2 (en) * 2002-08-29 2006-10-31 Micron Technology, Inc. Method for simultaneously removing multiple conductive materials from microelectronic substrates
US7153410B2 (en) * 2000-08-30 2006-12-26 Micron Technology, Inc. Methods and apparatus for electrochemical-mechanical processing of microelectronic workpieces
US7094131B2 (en) * 2000-08-30 2006-08-22 Micron Technology, Inc. Microelectronic substrate having conductive material with blunt cornered apertures, and associated methods for removing conductive material
KR100370160B1 (en) * 2000-10-27 2003-01-30 주식회사 하이닉스반도체 method for forming W plug of semiconductor device
DE10060343A1 (en) * 2000-12-04 2002-06-06 Bayer Ag Polishing slurry for the chemical mechanical polishing of metal and dielectric structures
US6540935B2 (en) * 2001-04-05 2003-04-01 Samsung Electronics Co., Ltd. Chemical/mechanical polishing slurry, and chemical mechanical polishing process and shallow trench isolation process employing the same
US6632259B2 (en) * 2001-05-18 2003-10-14 Rodel Holdings, Inc. Chemical mechanical polishing compositions and methods relating thereto
US6783432B2 (en) * 2001-06-04 2004-08-31 Applied Materials Inc. Additives for pressure sensitive polishing compositions
US20040011991A1 (en) * 2001-06-13 2004-01-22 Markle Richard J. Use of a gettering agent in a chemical mechanical polishing and rinsing operation and apparatus therefor
US6627546B2 (en) * 2001-06-29 2003-09-30 Ashland Inc. Process for removing contaminant from a surface and composition useful therefor
US6589099B2 (en) * 2001-07-09 2003-07-08 Motorola, Inc. Method for chemical mechanical polishing (CMP) with altering the concentration of oxidizing agent in slurry
US6953389B2 (en) * 2001-08-09 2005-10-11 Cheil Industries, Inc. Metal CMP slurry compositions that favor mechanical removal of oxides with reduced susceptibility to micro-scratching
TW591089B (en) * 2001-08-09 2004-06-11 Cheil Ind Inc Slurry composition for use in chemical mechanical polishing of metal wiring
DE60225171T2 (en) * 2001-10-26 2008-06-05 AGC Seimi Chemical Co., Ltd., Chigasaki-shi POLISHING MATERIAL, METHOD FOR THE PRODUCTION AND POLISHING METHOD
WO2003038883A1 (en) 2001-10-31 2003-05-08 Hitachi Chemical Co., Ltd. Polishing fluid and polishing method
KR100442962B1 (en) * 2001-12-26 2004-08-04 주식회사 하이닉스반도체 Method for manufacturing of metal line contact plug of semiconductor device
US7025659B2 (en) 2002-01-14 2006-04-11 Hitachi Global Storage Technologies Netherlands B.V. Simultaneous planarization of pole piece and coil materials for write head applications
TWI282360B (en) * 2002-06-03 2007-06-11 Hitachi Chemical Co Ltd Polishing composition and polishing method thereof
US6858531B1 (en) * 2002-07-12 2005-02-22 Lsi Logic Corporation Electro chemical mechanical polishing method
JP4083502B2 (en) * 2002-08-19 2008-04-30 株式会社フジミインコーポレーテッド Polishing method and polishing composition used therefor
JP3981616B2 (en) * 2002-10-02 2007-09-26 株式会社フジミインコーポレーテッド Polishing composition
US20040074517A1 (en) * 2002-10-22 2004-04-22 Texas Instruments Incorporated Surfactants for chemical mechanical polishing
US6899597B2 (en) * 2003-01-29 2005-05-31 Infineon Technologies Ag Chemical mechanical polishing (CMP) process using fixed abrasive pads
US7964005B2 (en) * 2003-04-10 2011-06-21 Technion Research & Development Foundation Ltd. Copper CMP slurry composition
US20040259366A1 (en) * 2003-06-20 2004-12-23 Kim Seong Han Method and composition for the chemical-vibrational-mechanical planarization of copper
KR101072342B1 (en) * 2003-06-30 2011-10-11 동우 화인켐 주식회사 Slurry compositions for chemical mechanical polishing of copper
US7112122B2 (en) * 2003-09-17 2006-09-26 Micron Technology, Inc. Methods and apparatus for removing conductive material from a microelectronic substrate
US20070176140A1 (en) * 2003-09-30 2007-08-02 Tsuyoshi Matsuda Polishing composition and polishing method
US20060172526A1 (en) * 2003-10-16 2006-08-03 United Microelectronics Corp. Method for preventing edge peeling defect
US20050085163A1 (en) * 2003-10-16 2005-04-21 United Microelectronics Corp. Method for preventing edge peeling defect
US20050136671A1 (en) * 2003-12-22 2005-06-23 Goldberg Wendy B. Compositions and methods for low downforce pressure polishing of copper
US7153777B2 (en) * 2004-02-20 2006-12-26 Micron Technology, Inc. Methods and apparatuses for electrochemical-mechanical polishing
JP2005244123A (en) * 2004-02-27 2005-09-08 Fujimi Inc Polishing composition
JP2005268666A (en) * 2004-03-19 2005-09-29 Fujimi Inc Abrasive composition
JP2005268664A (en) * 2004-03-19 2005-09-29 Fujimi Inc Abrasive composition
JP4316406B2 (en) * 2004-03-22 2009-08-19 株式会社フジミインコーポレーテッド Polishing composition
US7497967B2 (en) * 2004-03-24 2009-03-03 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Compositions and methods for polishing copper
JP4644434B2 (en) * 2004-03-24 2011-03-02 株式会社フジミインコーポレーテッド Polishing composition
US20050211950A1 (en) * 2004-03-24 2005-09-29 Cabot Microelectronics Corporation Chemical-mechanical polishing composition and method for using the same
US7253111B2 (en) * 2004-04-21 2007-08-07 Rohm And Haas Electronic Materials Cmp Holding, Inc. Barrier polishing solution
US20050279964A1 (en) * 2004-06-17 2005-12-22 Ming-Tseh Tsay Chemical mechanical polishing slurry for polishing copper layer on a wafer
US7384871B2 (en) * 2004-07-01 2008-06-10 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing compositions and methods relating thereto
US7303993B2 (en) * 2004-07-01 2007-12-04 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing compositions and methods relating thereto
US7566391B2 (en) * 2004-09-01 2009-07-28 Micron Technology, Inc. Methods and systems for removing materials from microfeature workpieces with organic and/or non-aqueous electrolytic media
JP2006086462A (en) * 2004-09-17 2006-03-30 Fujimi Inc Polishing composition and manufacturing method of wiring structure using the same
US7524347B2 (en) 2004-10-28 2009-04-28 Cabot Microelectronics Corporation CMP composition comprising surfactant
JP2006135072A (en) * 2004-11-05 2006-05-25 Fujimi Inc Polishing method
US7435356B2 (en) * 2004-11-24 2008-10-14 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Abrasive-free chemical mechanical polishing compositions and methods relating thereto
US7086935B2 (en) * 2004-11-24 2006-08-08 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Cellulose-containing polishing compositions and methods relating thereto
US7427362B2 (en) * 2005-01-26 2008-09-23 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Corrosion-resistant barrier polishing solution
JP4469737B2 (en) * 2005-02-10 2010-05-26 株式会社東芝 Manufacturing method of semiconductor device
CN1854234B (en) 2005-04-21 2013-03-20 安集微电子(上海)有限公司 Polished sizing material, its use and using method
JP2006339594A (en) * 2005-06-06 2006-12-14 Seimi Chem Co Ltd Abrasive agent for semiconductor
US7718536B2 (en) * 2005-06-16 2010-05-18 United Microelectronics Corp. Planarization process for pre-damascene structure including metal hard mask
JP5026710B2 (en) * 2005-09-02 2012-09-19 株式会社フジミインコーポレーテッド Polishing composition
KR101278666B1 (en) * 2005-09-02 2013-06-25 가부시키가이샤 후지미인코퍼레이티드 Polishing composition
US7435162B2 (en) * 2005-10-24 2008-10-14 3M Innovative Properties Company Polishing fluids and methods for CMP
US20070179072A1 (en) * 2006-01-30 2007-08-02 Rao Madhukar B Cleaning formulations
SG139699A1 (en) * 2006-08-02 2008-02-29 Fujimi Inc Polishing composition and polishing process
US20080029126A1 (en) * 2006-08-07 2008-02-07 Thomas Terence M Compositions and methods for improved planarization of copper utilizing inorganic oxide abrasive
US8057561B2 (en) * 2006-09-11 2011-11-15 Cabot Microelectronics Corporation Polyoxometalate compositions and methods
KR101050136B1 (en) * 2006-11-20 2011-07-19 주식회사 엘지화학 Method for producing cerium oxide powder using organic solvent and CPM slurry containing the powder
JP2009164186A (en) * 2007-12-28 2009-07-23 Fujimi Inc Polishing composition
JP2009164188A (en) * 2007-12-28 2009-07-23 Fujimi Inc Polishing composition
US7922926B2 (en) 2008-01-08 2011-04-12 Cabot Microelectronics Corporation Composition and method for polishing nickel-phosphorous-coated aluminum hard disks
CN101235255B (en) * 2008-03-07 2011-08-24 大连理工大学 Polishing liquid for chemo-mechanical polishing semiconductor wafer
JP5819036B2 (en) * 2008-03-25 2015-11-18 三井金属鉱業株式会社 Cerium-based abrasive slurry
CN101302403B (en) * 2008-07-03 2011-10-19 大连理工大学 Polishing solution for ultra-precise low-damage polish of large size diamond wafer and preparation thereof
US8506661B2 (en) * 2008-10-24 2013-08-13 Air Products & Chemicals, Inc. Polishing slurry for copper films
JP5449397B2 (en) * 2008-12-20 2014-03-19 キャボット マイクロエレクトロニクス コーポレイション Wire saw cutting method
TWI371481B (en) * 2009-04-02 2012-09-01 Uwiz Technology Co Ltd Slurry composition and method of fabricating damascene structure using the same
US8551887B2 (en) 2009-12-22 2013-10-08 Air Products And Chemicals, Inc. Method for chemical mechanical planarization of a copper-containing substrate
JP5587620B2 (en) * 2010-01-25 2014-09-10 株式会社フジミインコーポレーテッド Polishing composition and polishing method using the same
CN102373014A (en) * 2010-08-24 2012-03-14 安集微电子(上海)有限公司 Chemical-mechanical polishing solution
JP2012121086A (en) * 2010-12-07 2012-06-28 Yokkaichi Chem Co Ltd Additive for polishing and high dispersive polishing slurry
CN102559057A (en) * 2010-12-16 2012-07-11 安集微电子(上海)有限公司 Organic acidic matter-containing chemical mechanical polishing solution
CN102533122B (en) * 2010-12-28 2016-01-20 安集微电子(上海)有限公司 A kind of polishing slurries for polishing titaniferous base material
TWI605112B (en) * 2011-02-21 2017-11-11 Fujimi Inc Polishing composition
US8980122B2 (en) 2011-07-08 2015-03-17 General Engineering & Research, L.L.C. Contact release capsule useful for chemical mechanical planarization slurry
WO2013033173A1 (en) 2011-08-29 2013-03-07 Massachusetts Institute Of Technology METHODS AND SYSTEMS FOR CARRYING OUT A pH-INFLUENCED CHEMICAL AND/OR BIOLOGICAL REACTION
US9567678B2 (en) 2011-08-29 2017-02-14 Massachusetts Institute Of Technology Methods and systems for carrying out a pH-influenced chemical and/or biological reaction
US9039914B2 (en) 2012-05-23 2015-05-26 Cabot Microelectronics Corporation Polishing composition for nickel-phosphorous-coated memory disks
US9752057B2 (en) * 2014-02-05 2017-09-05 Cabot Microelectronics Corporation CMP method for suppression of titanium nitride and titanium/titanium nitride removal
CN105320782B (en) * 2014-06-16 2019-06-21 复旦大学 A kind of characteristic size grade CMP process emulation mode for considering polishing fluid and influencing
WO2016054519A1 (en) * 2014-10-03 2016-04-07 Massachusetts Institute Of Technology Methods and systems for carrying out a ph-influenced chemical and/or biological reaction
CN104312441B (en) * 2014-10-29 2017-11-10 安阳方圆研磨材料有限责任公司 Silicon cerium polishing fluid and preparation method thereof
JP7057662B2 (en) * 2017-12-26 2022-04-20 ニッタ・デュポン株式会社 Polishing composition and method for adjusting polishing speed

Family Cites Families (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385682A (en) 1965-04-29 1968-05-28 Sprague Electric Co Method and reagent for surface polishing
GB1198312A (en) 1967-07-22 1970-07-08 Geigy Uk Ltd Corrosion Inhibiting Chemical Compositions
JPS49109223A (en) 1973-02-21 1974-10-17
SE400581B (en) 1974-12-13 1978-04-03 Nordnero Ab BATH FOR CHEMICAL POLISHING OF COPPER AND ITS ALLOYS
DE2847267C2 (en) 1978-10-31 1993-12-23 Decker Gmbh & Co Kg Geb Stabilizer for an aqueous solution for pickling and / or chemical shining of objects made of copper or copper alloys in a multi-stage process and use of the stabilizer
US4789648A (en) 1985-10-28 1988-12-06 International Business Machines Corporation Method for producing coplanar multi-level metal/insulator films on a substrate and for forming patterned conductive lines simultaneously with stud vias
US4944836A (en) 1985-10-28 1990-07-31 International Business Machines Corporation Chem-mech polishing method for producing coplanar metal/insulator films on a substrate
US4671851A (en) 1985-10-28 1987-06-09 International Business Machines Corporation Method for removing protuberances at the surface of a semiconductor wafer using a chem-mech polishing technique
US4956313A (en) 1987-08-17 1990-09-11 International Business Machines Corporation Via-filling and planarization technique
US4910155A (en) 1988-10-28 1990-03-20 International Business Machines Corporation Wafer flood polishing
US5244523A (en) 1990-02-07 1993-09-14 Tollini Dennis R Bandage for replaceable dressing and method of fabrication thereof
US5137544A (en) 1990-04-10 1992-08-11 Rockwell International Corporation Stress-free chemo-mechanical polishing agent for II-VI compound semiconductor single crystals and method of polishing
US5157876A (en) 1990-04-10 1992-10-27 Rockwell International Corporation Stress-free chemo-mechanical polishing agent for II-VI compound semiconductor single crystals and method of polishing
US5209816A (en) 1992-06-04 1993-05-11 Micron Technology, Inc. Method of chemical mechanical polishing aluminum containing metal layers and slurry for chemical mechanical polishing
US5225034A (en) 1992-06-04 1993-07-06 Micron Technology, Inc. Method of chemical mechanical polishing predominantly copper containing metal layers in semiconductor processing
US5575837A (en) * 1993-04-28 1996-11-19 Fujimi Incorporated Polishing composition
US5391258A (en) 1993-05-26 1995-02-21 Rodel, Inc. Compositions and methods for polishing
US5407526A (en) 1993-06-30 1995-04-18 Intel Corporation Chemical mechanical polishing slurry delivery and mixing system
US5340370A (en) 1993-11-03 1994-08-23 Intel Corporation Slurries for chemical mechanical polishing
US5575885A (en) * 1993-12-14 1996-11-19 Kabushiki Kaisha Toshiba Copper-based metal polishing solution and method for manufacturing semiconductor device
JP3397501B2 (en) 1994-07-12 2003-04-14 株式会社東芝 Abrasive and polishing method
US5527423A (en) * 1994-10-06 1996-06-18 Cabot Corporation Chemical mechanical polishing slurry for metal layers
US5478435A (en) 1994-12-16 1995-12-26 National Semiconductor Corp. Point of use slurry dispensing system
US6046110A (en) * 1995-06-08 2000-04-04 Kabushiki Kaisha Toshiba Copper-based metal polishing solution and method for manufacturing a semiconductor device
US5700383A (en) 1995-12-21 1997-12-23 Intel Corporation Slurries and methods for chemical mechanical polish of aluminum and titanium aluminide
US5858813A (en) * 1996-05-10 1999-01-12 Cabot Corporation Chemical mechanical polishing slurry for metal layers and films
US5993686A (en) 1996-06-06 1999-11-30 Cabot Corporation Fluoride additive containing chemical mechanical polishing slurry and method for use of same
US6117783A (en) 1996-07-25 2000-09-12 Ekc Technology, Inc. Chemical mechanical polishing composition and process
JP3507628B2 (en) * 1996-08-06 2004-03-15 昭和電工株式会社 Polishing composition for chemical mechanical polishing
US6033596A (en) * 1996-09-24 2000-03-07 Cabot Corporation Multi-oxidizer slurry for chemical mechanical polishing
US5783489A (en) * 1996-09-24 1998-07-21 Cabot Corporation Multi-oxidizer slurry for chemical mechanical polishing
US6039891A (en) * 1996-09-24 2000-03-21 Cabot Corporation Multi-oxidizer precursor for chemical mechanical polishing
US5958288A (en) * 1996-11-26 1999-09-28 Cabot Corporation Composition and slurry useful for metal CMP
US6068787A (en) * 1996-11-26 2000-05-30 Cabot Corporation Composition and slurry useful for metal CMP
US6309560B1 (en) 1996-12-09 2001-10-30 Cabot Microelectronics Corporation Chemical mechanical polishing slurry useful for copper substrates
US5735963A (en) 1996-12-17 1998-04-07 Lucent Technologies Inc. Method of polishing
US5922091A (en) 1997-05-16 1999-07-13 National Science Council Of Republic Of China Chemical mechanical polishing slurry for metallic thin film
US6432828B2 (en) * 1998-03-18 2002-08-13 Cabot Microelectronics Corporation Chemical mechanical polishing slurry useful for copper substrates
US6063306A (en) 1998-06-26 2000-05-16 Cabot Corporation Chemical mechanical polishing slurry useful for copper/tantalum substrate

Also Published As

Publication number Publication date
CN1301288A (en) 2001-06-27
ID27122A (en) 2001-03-01
EP1064338A1 (en) 2001-01-03
KR20010041962A (en) 2001-05-25
US6432828B2 (en) 2002-08-13
EP1064338B1 (en) 2006-08-30
JP2002506915A (en) 2002-03-05
DE69933015D1 (en) 2006-10-12
IL138483A0 (en) 2001-10-31
CN1157450C (en) 2004-07-14
JP5539934B2 (en) 2014-07-02
KR100594561B1 (en) 2006-06-30
WO1999047618A1 (en) 1999-09-23
AU3100499A (en) 1999-10-11
DE69933015T2 (en) 2006-12-14
JP2012004588A (en) 2012-01-05
US6620037B2 (en) 2003-09-16
US20020168923A1 (en) 2002-11-14
US20040009671A1 (en) 2004-01-15
TWI256966B (en) 2006-06-21
US20010049910A1 (en) 2001-12-13
JP2007150341A (en) 2007-06-14
US7381648B2 (en) 2008-06-03

Similar Documents

Publication Publication Date Title
US7381648B2 (en) Chemical mechanical polishing slurry useful for copper substrates
EP1559762B1 (en) Chemical mechanical polishing slurry useful for copper substrates
US6593239B2 (en) Chemical mechanical polishing method useful for copper substrates
US6362106B1 (en) Chemical mechanical polishing method useful for copper substrates
EP1098948B1 (en) Chemical mechanical polishing slurry useful for copper/tantalum substrate
US5783489A (en) Multi-oxidizer slurry for chemical mechanical polishing
EP1090083B1 (en) Chemical mechanical polishing slurry useful for copper/tantalum substrates
US6039891A (en) Multi-oxidizer precursor for chemical mechanical polishing
US6033596A (en) Multi-oxidizer slurry for chemical mechanical polishing

Legal Events

Date Code Title Description
FZDE Discontinued