TW200413489A - Process for reducing dishing and erosion during chemical mechanical planarization - Google Patents

Abstract

This invention is directed to a slurry system and process of metal removal from a substrate. This invention is useful for polishing a microelectronic device. This invention is especially useful for chemical mechanical planarization of a semiconductor wafer. The slurry system of the present invention includes a first slurry and a second slurry, wherein the first slurry has a higher abrasive concentration than the second slurry. The process of the present invention includes a first polish with the first slurry to partially remove metal from the substrate, and a second polish with the second slurry to further remove metal from the substrate.

Description

200413489 (1) Description of the invention: I: Technical field of the inventors 3 Field of the invention The present invention is directed to a method for removing metal from a substrate. The present invention 5 can be used for polishing a microelectronic device. The invention is particularly useful for chemical mechanical planarization of semiconductor wafers.

Background of the Invention This patent application claims the priority of US Patent Application No. 60 / 401,109 filed on August 5, 2002, the entirety of which is incorporated herein by reference. SUMMARY OF THE INVENTION The present invention is directed to a method for removing metal from a substrate. The invention 15 can be used for polishing a microelectronic device. The invention is particularly useful for chemical mechanical planarization of semiconductor wafers. Microelectronic devices such as semiconductor wafers are typically manufactured using copper interconnects. These copper interconnects are produced by a multi-step metal damascene method, which includes indenting trenches in a dielectric material, such as stone dioxide, inlaying a barrier film, such as tantalum, into the trench, and then Trenches are filled with electroplated copper. Generally, a thick copper overlay is placed on top of a filled trench. The application of this cover layer generally does not result in a flat surface. Conversely, the cover layer has a lower area corresponding to the filled trench below, and a raised area corresponding to the space bounded between the trenches (ie, "step-height topography" )). In order to place another interconnect layer on a microelectronic device, the copper overlay must be removed. Chemical mechanical planarization (,, CMP ,,) is a known technique for removing copper overlays. During the CMP process, the copper overlay is removed from the surface of the microelectronic device to reveal the actual interconnection pattern. In a typical chemical mechanical polishing method, the sub-device is in contact with the polishing pad. Make the throw = pure rotation, while applying a force to the back of the microelectronic device. An abrasive-containing chemical reaction solution, commonly referred to as a "slurry," is applied to the I light pad during polishing. Generally, CMP polishing slurries contain abrasive materials such as silicon oxide, aluminum oxide, hafnium oxide, or mixtures thereof. The polishing process can be enhanced by the movement of the polishing stage relative to the substrate when the slurry is supplied to the device / pad interface. The polishing process continues until the desired film thickness is removed. Depending on the choice of abrasives and other additives, a polishing solution can be formulated to provide effective polishing of the metal layer at the desired polishing rate, while minimizing surface defects, defects, and decay scales. Methods of using abrasive slurries to remove steel coatings are known in the art. Disadvantages of these conventional methods include the tendency of the ink power of the polishing pads to press the abrasive particles onto the surface of the substrate, which can lead to the occurrence of the pattern in the trench and the pattern on the substrate. In this technical field, it is desirable to minimize this and the wear and tear. Therefore, there is a need in the conventional technical field for a method for effectively removing the steel clad layer and minimizing the surface depression in the trench and the abrasion effect of the pattern on the substrate. And Zhuang Si 疋, the singular form used in the specification of the present invention and the appended patent application scope ,,,,, (,,,,,,,,,,,) and ,,,,, and "this ,," ("the") "Unless the reference clearly and explicitly refers to an object, it includes the plural. In the description of the present invention, it should be understood that, in all cases, unless otherwise specified, the money, sun and moon books and towels should be exclusively The values surrounding measurements such as composition, reaction conditions, etc. can be modified by the words ,, about, and _. Therefore, unless there is a contrary expression 'in the following description and the appended claims, the numerical parameters in the patent range are approximate, It can be changed according to the ideal properties sought to be obtained by the present invention. At least it is not intended to limit the application of equality theory to the scope of patent applications. Every numerical parameter should be based at least on the presented number and by Use the general rounding technique to explain. The numerical ranges and parameters described in the broad scope of the present invention are approximate values, and the numerical values described in specific embodiments are recorded as accurately as possible. The numerical value of Ren Zhu contains certain errors caused by the standard deviation caused by individual experimental measurements.... The characteristics that show the characteristics of the present invention are specifically indicated in the scope of the patent application which is part of the inner valley of the disclosure of the present invention. These and other features of the present invention, the operational advantages of the present invention, and the specific objects obtainable by the uses of the present invention will be more fully understood by the following detailed description and operating examples. In the first polishing step, it is better to remove the step height topography (step_height topography) of the steel cover layer before the entire cover layer is removed, so that the second step can be performed to substantially clear the relatively non-step P orientation. The remaining cover layer of step-height topography. The present invention includes a slurry system comprising: 200413489 (a) a first slurry containing an abrasive for partially removing metal from a substrate; and (b) a second Slurry, wherein the abrasive concentration of the first slurry is higher than the second slurry. 5 The present invention further includes a method comprising using the first The slurry and a polishing pad perform a first polishing step. The first polishing step can remove a part of the metal from the substrate. After the first polishing step is completed, the residual metal remains on the substrate. In a non-limiting specific embodiment, The residual metal can at least partially form a layer or film. In the second polishing 10 step using the second slurry and the polishing pad, the substrate can be further polished with the second slurry, which has less abrasive than the first slurry. The second polishing step at least partially removes metal residues remaining on the substrate after the first polishing step. The first polishing step may be terminated before all metal is removed from the substrate. When the first polishing step is terminated, the residual metal remains in the 15 In a non-limiting embodiment, the metal may include copper, tantalum, silicon dioxide, or a mixture thereof. In a non-limiting embodiment, the metal is copper. It can be expected that in the first step of the polishing process, the use of an abrasive slurry for the removal of copper has a tendency to favor the high areas in the step height topography 20 (steP_height topography), and thereby leave behind Residual copper can then be removed by a second slurry with less abrasive. In a specific embodiment of the present invention, the second slurry may be free of abrasive. The first slurry of the present invention includes a liquid and an abrasive. Suitable abrasives for use in the present invention may include metal oxides. Non-limiting examples of metal oxides may include, but are not limited to, alumina, oxygen-emulsified titanium, germanium, silicon oxide, hafnium oxide, and mixtures thereof. 1. Oxidation Nongdi_filling liquid The dosage can be widely changed according to the selected abrasive. 7 / 子 的 磨 In specific embodiments, the amount of the abrasive present is a non-limiting ratio, or 0.5 to 12.0 weight percent. The weight of the abrasive can be oxidized stone.纟 Another-In the specific embodiment, the method of researching η port V hole 1 is known. Suitable oxides for use in the present invention can be selected from a wide variety of known techniques. In a non-limiting specific implementation, it can be the oxidation of Shendian ... It is known to those skilled in the art of Shendian oxygen. In another-non-limiting, four-billion-dollar project, Qizhiyang may be selected from those described in US Patent Nos. 嶋 2,549 and 嶋 2,548. The two applications are == 20 (^ June 14, 2014) The relevant part of the application that is still pending in the US Patent and Trademark Office Examination H2 is incorporated in this specification for reference.〉 In another non-limiting specific embodiment, the abrasive of the present invention includes The oxidized stone of the main particle aggregates, the average of the main particles is only at least 7 nanometers, wherein the size of the aggregates of the aggregates is at least 1 mm, and the hydroxyl content per nanometer of the nanoparticles is at least 7 hydroxyl groups. Silicon can be made by a wide variety of methods known in the art. Generally speaking, silicon oxide can be made by combining a water-soluble and a metal silicate with a soluble metal silicate. The soluble metal silicate can include a Basic jinxi runic salts, such as, but not limited to, sodium oxalate or potassium oxalate. Suitable acids can include inorganic, organic, and carbon dioxide. Silicate / acid slurries can be aged 'as well as Add acid or test to silicate / acid slurry. Oxidation obtained The granules can be separated from the liquid portion of the mixture. The separated oxidized stone can be washed with water, and the wet silica can be dried and the dried oxidized stone can be washed by conventional washing, drying and separation techniques, and Separation from the residues of other reaction products. In a non-limiting embodiment, the oxidized stone used in the present invention can be processed by particle size reduction technology. Conventional techniques are known to make Techniques for breaking aggregates into smaller aggregates. In a non-limiting embodiment, including but not limited to wet milling and fluid energy milling. In another non-limiting specific embodiment The double-jet cell process disclosed in WO 00/39056 and US Patent No. 5,720,551 can be used to reduce the aggregates of the main particles of silicon oxide; the relevant parts of these patent documents are This specification is incorporated by reference. As mentioned above, the first slurry of the present invention includes an abrasive and a liquid. In a non-limiting embodiment, the first The abrasive liquid can be prepared according to the methods described in US Patent Application Serial Nos. 09 / 882,549 and 09 / 882,548 filed with the US Patent and Trademark Office on June 14, 2001. In the review, the relevant part of the inner valley system is incorporated in this specification for reference. In another non-limiting specific embodiment, the liquid may be water. In addition to the abrasive and water, the slurry may include an oxidant and an Complexing agent. The oxidant present in the slurry can be used to oxidize the substrate metal layer to its corresponding oxide, hydroxide or ion. In a non-limiting specific embodiment 200413489, the oxidant can be used to oxidize titanium to oxidation Titanium oxidizes tungsten to tungsten oxide, copper to copper oxide, and aluminum to aluminum oxide. Oxidizer-containing slurry can be used for polishing metals and metal-based components, including but not limited to titanium, titanium nitride, buttons, nitride buttons, copper, tungsten, tungsten nitride, 5 aluminum, such as aluminum / copper Aluminum alloy, gold, silver, platinum, ruthenium and various mixtures and compositions thereof. A wide range of oxidants can be used in the first slurry of the present invention. Suitable oxidants may include inorganic and organic per-compounds (per-compounds), and compounds containing an element in a higher oxidation state or the highest oxidation state. As used in this specification and in the scope of patent applications, the term "per-compounds" means compounds containing at least one peroxy group (_〇_〇_). Non-limiting examples containing at least one peroxy group may include hydrogen peroxide and adducts thereof such as urea peroxide and percarbonate, organic peroxides such as benzene peroxide, peracetic acid, and di- Third butyl peroxo 15 compound, monopersulfate (S05), dipersulfate (S200), sodium peroxide and mixtures thereof. Non-limiting examples of oxidants containing an element with a higher oxidation state may include brook acid 'desert salt, chloric acid, chlorate salt, complex acid salt, arsenic acid, iodate salt, peroxy acid, peroxy acid Carbonate, over-acid, per-acid salt, perchloric acid, 20 perchloric acid, rotten acid, over-supplement salt, per-acid salt, (^) compound

Substances such as, but not limited to, ammonium sulphate, such as iron salts, sulfates, iron salts of coffee A and citrate, potassium ferricyanide, dioxin and its analogs, and aluminum salts. In another non-limiting specific embodiment, the oxidant may be hydrogen peroxide 11 hydrogen peroxide or a mixture thereof. In another non-limiting embodiment, the oxidant may be hydrogen peroxide. The oxidant present in the first mash may vary widely depending on the particular oxidant selected. In general, the amount should be sufficient to oxidize the substrate metal layer to its corresponding oxide, hydroxide or ion. In another non-limiting specific embodiment, the oxidant may be present in an amount of 0.001% by weight or more, or 0.01% by weight or more, or 200% by weight or less, or 17.0% by weight. Or less, or 100 weight percent or less. Suitable complexing agents for use in the present invention may include organic acids and organic hydroxy 10 acids. Non-limiting examples of organic acids may include, but are not limited to, dicarboxylic acids, dicarboxylic acids and polycarboxylic acids, gluconic acid, lactic acid, citric acid, tartaric acid, unsuccinic succinic acid, glycolic acid, malonic acid Acid, oxalic acid, succinic acid and phthalic acid. Non-limiting examples of organic hydroxy acids may include, but are not limited to, dicarboxylic acid & L, dicarboxylic acid and polyweiyl acid. 15 Further non-limiting examples of suitable complexing agents may include, for example, amino acids of glycine, histidine, alanine, and aspartic acid; for example, picolinic acid, dipicolinic acid, quinolinic acid, 2- Nitrogen-containing heterocyclic carboxylic acids of pyridocarboxylic acid, galanic acid, and 2-oxaoxalinic acid; and organic double ligands such as bipyridine derivatives. The dosage of the complex used in the present invention can be widely changed depending on the selected complex. In a non-limiting specific embodiment, glycine can be used as a complexing agent, and its content is from 0 to 5 weight percent of the slurry, or from 0.5 to ^ weight percent. In another non-limiting specific embodiment, picolinic acid can be used as a complexing agent in an amount of 0.1 to 5 weight percent, or 0.5 to 1 weight percent of the slurry. 12 200413489 In other non-limiting specific embodiments, the first slurry of the present invention may include one or more of the following additives: polyvalent cation chelator, resist, thickener, inhibitor, static money Static etch controllers, accelerators, metal halide compounds, stabilizers and metal chelate. In another non-limiting embodiment, the slurry of the present invention may include a polyvalent cation chelator. Suitable polyvalent cation chelating agents for use in the present invention may include a variety of different known compounds that bind, complex or chelate with polyvalent metal cations. Non-limiting examples of multivalent cation chelating agents include carboxylic acids and polycarboxylic acids, amino acids, dipeptides and polyamino acids, polyimines, phosphoric acids, and polyphosphoric acids. Other non-limiting examples may include glycine, histidine, aspartic acid, phytic acid, thermal polyaspartate, r-amino-n-butyric acid, / 5-alanine, L_asparagine, 2-aminoisobutyric acid, citric acid, N- (phosphinofluorenylmethyl) imine diacetic acid, poly (di 15 methylsiloxane) -graft-polyacrylic acid, 4 , 5 4,5-_azoledicarboxylic acid, aminotris

Polyacrylic acid moieties commercially available from B.F. Goodrich under the trade name 20 GOOD-RITE K-700, and mixtures thereof. In a non-limiting embodiment, CarbOOl or ππγλτλ can be used ------

Dyeing and instability, or handling problems. In addition, the specific examples of rotten rice, rotten rice, and non-limiting examples 13 200413489, the slurry consisting mainly of oxidized stone contains polyvalent cationic chelating agents greater than 0 to 5 weight percent based on the composition of the slurry. , Or ⑽〇1 到! Weight percent. In another non-limiting embodiment, the slurry of the present invention may include an anti-corrosive agent or a residual inhibitor. Rotten inhibitors for use in the present invention may include a variety of different known compounds that inhibit the rate of copper spoilage or static rate, such as, but not limited to, polylin, polyamino acid, amino acid, imine , Pyrrole, carboxylated pyrrole and thiol. Non-limiting examples of suitable corrosion inhibitors include benzotriazole, each carboxybenzotriazole, 5-carboxybenzo10diazole, thermal polyaspartate, histidine, mercaptobenzotriazole Phytic acid, crosslinked polyacrylic acid commercially available from BF Goodrich under the trade name Carbopol, commercially available polyacrylic acid ester commercially available from BFG〇drich under the trade name GOOD_RITEK-70. , And its mixtures. In a non-limiting embodiment, phytic acid can be used in the present invention in different amounts. In another non-limiting specific embodiment, the amount of phytic acid is based on the slurry, which may be at least 0.001 weight percent, or at least 0.05 weight percent, or from 0.05 to 0.001 weight. Percent, or less than 0.2 weight percent. Non-limiting examples of suitable commercially available phytates include water-soluble corrosion inhibitors, which are commercially available from King Industries, Incorporated under the trade names CDI 4302, 4303, and 4304, And CDX 2128 and 2165. In a non-limiting specific embodiment, the presence of a corrosion inhibitor can appropriately reduce static etching, corrosion, and pitting, but does not excessively reduce the copper polishing rate, and does not excessively increase the oxide oxide dispersion. Liquid dyeing and instability, excessive cost or handling problems. In a specific embodiment, the corrosion inhibitor used in the present invention can be used as a passivation film forming agent, which forms a passivation layer on the surface of a substrate to be polished. The corrosion inhibitor forms a passivation layer on the surface of the electrical substrate layer. 5-Denier passivation layer formation 'may then be followed by spreading the passivation layer to obtain-an ideal polishing rate. The corrosion inhibitor can include a compound or a combination of compounds that can accelerate the formation of a metal passivation layer and a dissolution inhibiting layer on the surface of the metal layer. The passivation of the metal surface layer of the substrate can prevent the metal surface from being wetted. Such film-forming agents include nitrogen-containing heterocyclic compounds, wherein the compound comprises at least H) a 5- or 6-membered heterocyclic ring having nitrogen as a-part of the ring. Examples of such gas-containing 5- and cyclic compounds include CDS, SAW, benzotrifluorene, benzo miso, and benzofluorene, and the like having a hydroxyl group, an amine group, an imine group, Derivatives of hetero, vinyl, and radical-substituted groups, veins, thioureas, and mixtures thereof. In a specific embodiment of the present invention, pure

Triazole (,, BTA ,,), 1,2,3-triazole,

On the surface of the metal layer of the substrate, the formation of a metal suppression layer can effectively minimize the formation of a metal's purified layer and wet etching by dissolving or preventing the wet etching of the metal surface. In another non-limiting embodiment, the slurry of the present invention may include a thickening agent. Suitable thickeners may include thickeners that are widely known in the art. In general, suitable thickeners include substances that stabilize a slurry based on silica 5 to prevent settling. Non-limiting examples may include, but are not limited to, polyvinyl alcohol, polyacrylic acid, polyether, ethyl cellulose and modified ethyl cellulose, polyvinyl glycol, polypropylene glycol, polyethylene, and Copolymers of polypropylene glycol, calcined polyethylene and polypropylene glycol, polyethyleneimine, polyurethane, polypropylene, and polyamide. Non-limiting examples of such 10 suitable anionic polymers may include cross-linked polyacrylic acid commercially available from BF Goodrich under the trade name Carbopol; polyacrylates commercially available from BF Goodrich , Trade name GOOD_RITEK-700; KelzanAR Sanxan polysaccharide commercially available from CPKelco; 15 Natrosol 250 MMR hydroxyethyl cellulose commercially available from Hercules; Airvol commercially available from Air Products 523 polyvinyl alcohol; and PolyOX 3333 polyethylene oxide, or a mixture thereof, commercially available from Union Carbide. The presence of the thickening agent can appropriately reduce the sedimentation rate, but the viscosity should not be excessively increased, so that pumpability and filterability can be compromised, or heat generated during polishing can be detrimental to slurry performance. The amount of thickener used can vary depending on the selected thickener. In another non-limiting specific embodiment, the thickener can be present in an amount of greater than 0 to 5 weight percent, or from o.ooi to 1 weight percent. In another non-limiting embodiment, Carbopol can be present as a thickener in an amount of less than 0.5% by weight. 16 200413489 In another non-limiting specific embodiment, the slave can be shear stable. In the present specification and the scope of the patent application, the term "shear-determined" is used to mean that under the action of polishing shear, the viscosity of the thinner will be reduced substantially (such as with The viscosity before polishing is reduced by no more than%). In another non-limiting specific embodiment of the present invention, the particle size of the purely negligible and / or small oxygen-cut particles is reduced as described above. 'Or when grinding the oxide stone and / or reducing the particles of the oxide stone, the multivalent cationic chelating agent, the residue inhibitor, and the cercifying agent as needed may be added to the oxide stone. 10 Inventive-non-limiting specific embodiment, a polyvalent cation phonogen, a corrosion inhibitor, and a chemical agent as needed, may be added to the reading solution. In another non-limiting specific embodiment, the 'multivalent cation Chelating agents, corrosion inhibitors and / or thickeners are combined under mild agitation and then added to the mash. 15 In another non-limiting embodiment, the slurry of the invention may include at least one blocking compound This blocking compound can interact with the metal layer of the substrate, Interlayer, and / or dielectric layer interaction, and suppress the removal rate of the layer under the polishing layer. As a result, the first layer of the substrate can be polished by the slurry, and the polishing layer can be prevented on the first layer by 20ϊτΐτ. The second layer below. Suitable blocking compounds for use in the present invention may include a wide variety of species known in the art, such as, but not limited to, polar compounds or polymers containing polar moieties such as hydroxyl, amine, nitrogen-containing Heterocyclic, carboxyl, carbonyl, ether, sulfonyl, or phosphonyl moieties. Non-limiting examples may include polyvinyl alcohol, polyvinyl alcohol ratio 17, polyisocyanate, polyethylenoxide, fixed, poly% oxygen Ethyl alcohol, diols or polyglycols, polycarboxylates, such as polyacrylic acid polymethacrylate. The term "substantially impeded," as used in this specification and in the claims, refers to a polishing composition Or, the polishing selectivity of the first layer relative to the second layer of the slurry is about 5: 1, or until J is 10: 1, or 100: 1. The choice of blocking compound may depend on chemical stability, interaction with other ingredients in the slurry, and its effect on the colloidal stability of any abrasive particles used. In a non-limiting specific embodiment, the amount of the abrasive in the slurry of the present invention may be 0 to 20.0 weight percent, the amount of the resist may be 0 to 1 weight percent, and the amount of the blocking compound may be 0 to 1 weight percent. In another non-limiting embodiment, the slurry may include a dispersant. Non-limiting examples of suitable dispersants include polycarboxylic acids such as polyacrylic acid, crosslinked polyacrylic acid, and polymethacrylic acid; phosphonic acids, 15 such as, but not limited to, alkylphosphonic acid, arylphosphonic acid , Polyphosphonic acid, and alkylaminophosphonic acid; polyamino acids, such as, but not limited to, polyaspartic acid. In another non-limiting embodiment, the slurry may include a surfactant. Suitable surfactants for use in the present invention may include cationic, anionic, and nonionic surfactants. Suitable cationic surfactants may include, but are not limited to, aliphatic amines and aliphatic ammonium salts. Non-limiting examples of anionic surfactants can include carboxylic acids, such as but not made from fatty acid soaps, alkyl ether carboxylates; alkyl and aryl sulfonates, such as from benzene benzene% acid, Alkyl naphthoic acid and salts of Λ_ene nicotinic acid. Non-limiting examples of dangerous ionic surfactants may include, but are not limited to, 18 200413489 such as higher alcohol esters, novolac ethers and acid salts, and polyoxyethylene alkyl phenyl mysteries The salt of lutein acid. In a non-limiting specific embodiment, the anionic surfactant may include salts of acetic acid vinegar, which includes, but is not limited to, benzyl phosphate and aryl phosphate. Non-limiting examples of surfactants in the nonionic world may include, but are not limited to, bonds such as the class of Polyethylene Gyizaki, the class of polyoxyethylene ethers such as glycerol, and glycerides and Esters of sorbitan esters. In a non-limiting embodiment, the filling solution of the present invention may include a stabilizer. Suitable stabilizers may include acetanilide, tin oxide, and free radical inhibitors such as, but not limited to, inorganic and organic nitrogen oxides. Suitable dispersants include, for example, polyacrylic acid, crosslinked polyacrylic acid, and polycarboxylic acids of polymethacrylic acid; such as, but not limited to, alkylphosphonic acid, arylphosphonic acid, polyphosphonic acid, and alkylaminophosphine Phosphonic acids of acids; and polyamino acids such as polyaspartic acid. 15 In a non-limiting embodiment, the oxidant and other non-abrasive components may be mixed into a liquid medium such as deionized water or distilled water, which is performed under shear conditions until the non-abrasive component Dissolve sufficiently in this mediator. Silicon oxide can then be added to the medium. In a non-limiting embodiment, the silicon oxide may be a silicon oxide of Shendian. The composition is then dispersible in a liquid such as water to prepare a slurry of the present invention. In the present invention, in the first polishing step using the first slurry, the amount of copper removed can be widely changed depending on the composition of the first slurry, the length of the polishing time, and the polishing conditions. In a non-limiting embodiment, the first slurry can remove less than 100% of copper, so that residual copper can be retained. In another 19 200413489 non-limiting embodiment, the first slurry can remove 10% to 95% copper, or 20% to 90% copper, or 25% to 85% copper from the substrate. In another non-limiting embodiment, the residual copper may be at least partially in the form of a layer or a film. 5 In the first step, the removal rate of copper can be widely changed according to the composition of the first slurry, the length of the polishing time and the polishing conditions. In another non-limiting specific embodiment, the copper removal rate in the first step may be at least 2,500 Angstroms / minute, or less than 10,000 Angstroms / minute, at least 5,000 Angstroms / minute 'Or less than 8,000 Angstroms / minute. 10 The static etch rate in the first polishing step can vary widely. In a non-limiting embodiment, the static etch rate may be 0% to 20% of the copper removal rate, or 0.1% to 15% of the copper removal rate, or 1% to 10% of the copper removal rate. In the present invention, after the first polishing step is substantially terminated, the second slurry can be used in the second 15 polishing step. In a non-limiting specific embodiment, the first polishing using the first slurry can be terminated and the second polishing using the second varnish can be started before the first liquid is removed from the substrate and / or the polishing pad. 0 The various grinding agents used in the first slurry of the present invention described in the foregoing and their preparation methods can be applied to the second slurry. In a non-limiting specific embodiment, the abrasive concentration in the second slurry may be less than the abrasive concentration in the first night. In another non-limiting specific embodiment, the abrasive concentration in the second slurry, based on the weight of the second slurry, may be 0% or higher, or 10% or lower, or 0.1% or Higher, or 1% or higher, 20 200413489 or 5% or lower. In another non-limiting specific embodiment, various oxidants, complexing agents, and other additives used in the first slurry of the present invention are inserted into the second slurry, as described above. In a limited embodiment, the composition of the second slurry may be the same as that of the first slurry except that the concentration of the first abrasive is less than the concentration of the abrasive in the first slurry. Abrasive in the embodiment. The second slurry can be free of grinding 10 15 20 The second slurry without a step can be used to remove the remaining residue on the substrate after the first polishing step is terminated. The polishing degree of Lai polishing pads and the copper removal rate from the first polishing step: removing the residual abrasive from Yang. Copper is used in a non-limiting implementation of the second slurry to remove residual copper in the water solution. It can be less than the copper removal rate of Lizhong Liquid. In another-non-limiting specific embodiment, the copper removal rate of the second slurry to remove residual copper is less than the ★ ★ The copper removal rate of one slurry, or less than 35%. The first two removal rate 'or less than 25% of the copper removal rate using the first liquid, or less than 10% of the copper removal rate using the first slurry. The static etchant rate of the second polishing step using the second liquid It may be less than the quietness rate of using the first slurry. In another non-limiting embodiment, the quietness rate of the second test may be the static rate of the first polymerization solution from G to the dove, or A static etching rate of at least 20% using the first poly 21 200413489 fluid, or a static etching rate of at least 20% using the first slurry, or a static etching rate of less than 70% using the first slurry. In specific embodiments, the slurry of the present invention can be used for chemical mechanical planarization (CMP) of substrates such as semiconductor wafers. In this 5 specific embodiment, the first slurry of the present invention can be applied to wafer substrates, and crystals The circle may be polished by using conventional polishing equipment and polishing equipment known in the art. Suitable CMP equipment for use in the present invention may include, but is not limited to, IPEC 472, Applied Materials Mirra Mesa or Reflexion, Speedfa m 676, Novellus Momentum, Lam Terres 10 and Nikon CMP system NPS 2301. Furthermore, the choice of polishing pads can include Rodel's IC1400, IC1000 stacked on SUBA IV, Polytex or PPG's Fast pads. In a non-limiting specific implementation For example, the first slurry of the present invention can polish copper at high speed, while exhibiting a low polishing rate for buttons and other adhesion layers, dielectric layers or 15 metal layers. The second slurry can then be applied to a partially polished substrate. The second slurry can polish copper at a lower rate while exhibiting a higher polishing rate for tantalum and other adhesion layers, dielectric layers or metal layers. We can expect that choosing one or more additives can control the desired removal rate at the desired high or low rate when polishing a specific metal layer, adhesion layer or oxide layer. After Wu Cheng uses the slurry polishing process of the present invention, the substrate may be cleaned with deionized water or other solvents for removing the polishing slurry from the substrate. In a non-limiting embodiment, the washing step may be completed before the second slurry is used. After the second polishing step is completed, the substrate may be cleaned with deionized water or other solvents for removal of the second slurry from the substrate, and the substrate may be ready for further processing. In the second polishing step, the polishing slurry can be applied directly to the substrate, directly to the polishing pad, or during substrate polishing, in a controlled manner to both the 5 substrate and the polishing pad. In a non-limiting embodiment, the slurry may be applied to a polishing pad, the polishing pad may then be placed against the substrate, and the polishing pad may be moved relative to the substrate to complete the polishing of the substrate. The slurry and method of the present invention can be used to provide effective polishing at a desired polishing rate while minimizing surface incompleteness and defects. Furthermore, the slurry and method of the present invention are particularly useful when providing a high material removal rate during polishing while maintaining a low static etchant rate to minimize the surface depression and abrasion effects of embedded feature structures. . t EMBODIMENT; J Example 15 In the experiment, a copper disc with a diameter of 2.4 cm was used as the metal sample. The average weight loss of the disc was used to calculate the copper removal rate. The discs to be polished are weighed before polishing. After polishing, the disc was weighed again and the difference between the two weighing values was used to calculate the weight loss due to polishing. The average weight loss of the three discs was used to calculate the copper removal rate. The average weight per minute is 20%. The weight loss is calculated by dividing the average weight loss by the average polishing time (varies in minutes. The cross-sectional area of the disc and the density of copper are used to convert the average weight loss per minute into Removal rate (in nanometers / minutes or angstroms / minute. 23 200413489 Stuers LabPol-V TM polisher is used to polish the disc. Both the conveyor and the polishing table are rotated counterclockwise and the speed is maintained at 60 rpm. The disc system consists of 30 N (approximately 9.8 psi) is held down. The slurry used for disc polishing is supplied at a fixed flow rate and is supplied to the polisher located in the center of the disc. All polishing experiments were performed using a polyurethane 5 pad .

The term "pad adjustment" used in this specification is used to remove the remaining slurry and polishing products on the polishing pad. With padless adjustment, the polishing rate is reduced due to the mosaic effect. Various adjustment techniques known in the art can be used. 10 Use a SUBATM 500 polishing pad and adjust the polishing pad. throw

The light pad adjustment sequence consists of the following steps: washing with deionized water for 1 minute, hydrogen peroxide for 30 seconds, washing with deionized water for 1 minute, citric acid for 30 seconds, and washing with deionized water for 1 minute. . In these experiments, 200-mm copper blanket wafers and patterned 15 wafers were used to polish the wafers using a Westech 372M rotary CMP tool with a Rodel IC1400-A2 polishing pad. Between each wafer polishing, the polishing pad is adjusted (ex-situ adjustment) using deionized water and diamond adjustment wheels.

Copper blanket wafers from International Sematech or Montco Silicon Technologies, Inc. are used as rate monitors. Sematech 20 854-006 patterned wafers are used for the evaluation of topographic maps. All chemicals are ACS reagent grade. All solutions were prepared with deionized water. The film thickness and the contour of the copper wafer were measured using a Prometrix® RS-35 four-point probe measurement tool and a profilometer equipped with a 2.5 micron tip needle. 24 2040013 Example 1 A liquid sample containing benzotrimethylene oxide, glycine, and nitrogen peroxide (without added oxidized stone), sample port 1 and, in addition to changing the concentration of oxidized stone, have Comparison of plasma and liquid phases of the same composition. At a slurry feed rate of 60 ml / min, a 5-light disc was thrown for 3 minutes. The data confirmed that the copper removal rate was higher in the samples containing oxidized stone than in the samples without oxidized stone. The removal rate of steel for polished copper discs is shown in Table i. It was confirmed that the copper removal rate shown by the watchmaker did not decrease linearly with the increase in the concentration of the oxide. We believe that the relationship between the concentration of oxidized stone and the rate of copper removal in this example is at least partly due to a change in pH in the sample. Table 1

Example 2 A slurry 'Sample 1' containing benzo,> sial, glycine, and hydrogen peroxide (without added oxidized stone) was compared with a slurry 25 containing a similar solution with increased silicon concentration in gasification 1 . The disc was polished at a feed rate of 100 liters / minute for 丨 minutes. As in the previous examples, the data confirms that the steel removal rate of samples containing silicon oxide is higher than the copper removal rate of samples without silicon oxide. The copper removal rate of polished copper discs is shown in Table 2. It was confirmed that the copper removal rate shown in Table 丨 did not decrease linearly with increasing silicon oxide concentration. I believe that in this example it was confirmed that the relationship between the silicon oxide concentration and the copper removal rate is due at least in part to a change in pH in the sample. Furthermore, the copper removal rate proved to decrease as the slurry flow rate increased. Table 2 -----

Sample oxidized fragment 1 0.0 6.08 2 0.1 6.34 3 0.2 6.49 4 0.3 6.65 5 0.5 6.79 6 1.0 7.02 7 2.0 7.14 8 3.0 7.21 9 4.0 7.25 10 5.0 7.39 Example 3 The slurry system in this example is the same as in the previous example 2. The slurry is similar, except that when there is no silicon oxide, the concentration of hydrogen peroxide (3% to 5% by weight) is increased to reduce the copper removal rate. A solution 'Sample 1' containing benzotrisialyl, glycine and peroxo 10, 103489 vaporized oxygen (without added oxidized dreams) was compared with a slurry containing a similar solution with increased silica concentration. The disc was polished for 3 minutes at a liquid feed rate of 60 ml / min. The data confirmed that the rate of steel removal was higher in the samples containing silicon oxide than in the samples without silicon oxide. ': In addition to 5, there is no significant difference in the copper removal rate of the copper oxide removal rate disk containing only 1 weight percent of the oxide stone oxide slurry. The copper removal rate of polished copper discs is described in Table 3. Table 3 Sample 1 2 3 4 5 6 7 8 9 Stone oxide (weight 1 2 3 4 5 6 7 8 PH4〇g [H30 +] 5.67 6.39 6.61 6.71 6.67 6.81 6.74 6.72 6.68 Copper removal rate of hydrogenated BTA i ,%) (MM) (nm / min) 5

5 5 5 5 5 5 5 1 1 1 1 1 1 1 1 1 94 400 351 332 291 279 302 325 390

Example 4 10 The slurry in this example was prepared according to the actual pH #W ^ Example 1 except that the constant value was adjusted and maintained. The pH of sodium is used. Prepare the entire system. Sulfuric acid or oxazole (1 millifluorene, U weight percent), benzotrioxide oxidation > peroxy _ (3 weight percent). The effect of different anode concentrations on copper removal rate was evaluated by polishing the copper discs at a slurry feed rate of 60 ml 27 200413489 / min for 1 minute. The results confirm that for a particular silicon oxide concentration, the copper removal rate varies with the pH concentration. Table 4 The results are shown in Table 4. Silicon oxide (wt%) Copper removal rate (person / min) pH 3 pH 4 pH 5 pH 6 0 259 106 176 151 1 434 488 412 342 2 597 537 483 393 3 705 617 528 451 4 801 644 565 520 5 Examples 5 Two-stage copper polishing of 200 mm copper blanket wafers. These wafers consist of silicon metal wafers with thin film layer stacks. The stack consists of a thermal oxide layer (5,000 persons) on Shixi Metal, a tantalum metal layer (250A) on thermal oxide, and a copper layer (15,000 persons) on top. In each example, the wafers in the first stage were made using silicon oxide (8 weight percent), benzotriazole (1 mmol), glycine (1 weight percent), and hydrogen peroxide (3 weight percent). ) The slurry aqueous solution (200 ml / min) was polished for 60 seconds. After the first stage of polishing, stop the slurry flow and use deionized water or contain benzotriazole (1 millimolar), glycine 15 acid (1 weight percent) and hydrogen peroxide (3 weight percent) but not The aqueous solution of the oxidized stone is continuously polished. All polishing was performed using a downward force of 4 psig, a back pressure of a 1 psig conveyor, and a polishing table speed of 60 rpm. Table 5 shows the average value of the 49 measured values of the copper ::: Γ using a 28-point 4-point probe. These :: ^ And in the 2nd stage ', a very small amount is removed by continuous polishing with water. =, The copper removal rate of ρr ^ is polished by a chemical solution without an abrasive, and this significant copper removal rate is dependent on the residual abrasive on the slot in the younger stage. Addiction Table 5

Example 6 Two-stage copper polishing was performed on a 200 mm copper blanket wafer. These 10-day Japanese yen consist of a shiyu metal wafer with a thin-film layer stack. The stack consists of a thermal oxide layer (5,000 A) on silicon metal, a button metal layer (250,000 people) on thermal oxide, and a copper layer on the top (side in). In each example, the wafers used in the first stage contained silicon oxide (11% by weight), benzotriazole (1 millimolar), glycine (丨 weight percent 15%), and thorium peroxide ( 5 weight percent) of the slurry aqueous solution was polished for 60 seconds. After the first stage of polishing, the slurry flow is stopped, and polishing is continued using deionized water or an aqueous solution containing benzotriazole, glycine and hydrogen peroxide, but without silica. The silicon oxide-free chemical group used in the second-stage solution is shown in Table 6. Throughout the two polishing stages, the polishing conditions and the pH value of the body are maintained at a fixed value (downforce 4 psig, polishing table speed 70 rpm, conveyor speed 68 rpm, conveyor back pressure 0 pSig, slurry flow rate 19 ml / min And pH 5). The copper 5 removal rate 'was measured using a prometrix rs_35tm 4-point probe and is shown in Table 6 as the average of 49 measured values from the wafer diameter passed. These results confirm that in this embodiment, in the second stage, continuous polishing under the absence of oxidized stones does not significantly increase the amount of additional copper removal. The results also confirm that the copper removal in the second stage (i.e., the second polishing step)

The rate change may be independent of the copper removal rate in the first stage (first polishing step). Table 6 Polishing time of the second stage of the product (seconds) Glycine (wt%) Hydrogen peroxide (wt%) ΒΤΑ (mM) Copper removal rate of deionized water copper removal (A) 1 Sleep---6023 2 60--100% 6485 462 3 60 1 5 1 main body 9314 3291 4 60 1 5 3 main body 8569 2546 5 60 1 8 1 main body 9488 3465 6 60 1 8 3 main body 7815 1792 7 60 1 6.5 2 main body 8287 2264 Example 7 Two-stage copper polishing of 200 mm copper blanket wafers. These wafers consist of silicon metal wafers with thin film layer stacks. Stack 15 consists of a thermal oxide layer on silicon metal (5,00〇Λ), a tantalum metal layer on thermal oxide (250A), and a copper layer on the top (5,000,000) Group 30 200413489 ^ In the mother_example, the wafer in the first stage is based on the use of oxidized stone (%), benzotrisial (1 mmol), glycine (100% and over Polishing aqueous solution of hydrogen oxide (5% by weight) mash solution 5, and "." After the first stage of polishing, the slurry flow was terminated, and the use of reading containing benzene 5 Gan Jian and the county minus but not oxygen cutting read Lai ', >. The chemical composition of the solution used in the second stage without oxidized stone is shown in Table 7. Throughout the second polishing stage, the polishing conditions and the pH of the liquid were maintained at a constant value (downforce 3 psig , Polishing table speed 70 rpm, conveyor speed 68 rpm, conveyor back pressure 0 psig, slurry flow rate 190 mi / min _ 10 and PH5). The steel removal rate was measured using a Prometrix RS-35TM 4-point probe and passed through The average value of the 49 measured values of the wafer diameter is recorded in the table. This result is confirmed in the second stage. Copper removal rate of change (i.e., a second polishing step) is probably not related to the first stage (first polishing step) of copper removal rate. Table 7 15 ^ k bta acid Deionized too '

• U throw: ^ (weight%) (weight%) (mM) water (person) 2 3 4 5 60 60 60 60 5 8 8 6.5 3 2 5122 main body 6250 main body 7383 main body 6022 main body 6209 1128 2261 880 1087 31 200413489 Example 8 a.

Two-stage copper polishing of 200 mm copper blanket wafers. These wafers consist of a second metal wafer with a thin film stack. The stack consists of a thermal oxide layer (5,00A) on silicon metal, a group of metal layers (250 persons) on thermal oxide, and a copper layer (15,000A) on top. In each example, the wafers in the first stage were made of oxidized stone (U weight percent), benzotrimethylene (1 mmol), glycine (1 weight percent), and hydrogen peroxide (5 weight Percent) of the aqueous slurry solution was polished for 60 seconds. After the first stage of polishing, stop the slurry flow, and use deionized 10 water or contain benzotrimethylene (3 mmol), glycine (1 weight percent) and hydrogen peroxide (8 weight percent) but not Oxidation; the aqueous solution of May is continuously polished. Throughout the polishing phase, the polishing conditions and the pH of the liquid are maintained at a constant value (downforce of 3 psig, polishing table speed of 70 rpm, conveyor speed of 68 rpm, conveyor back pressure of 0 psig, slurry flow rate of 190 ml / min, and PH 5). 15 Polish individual wafers during each second stage time interval. The copper removal rate was measured using a prometrix RS_35 ™ 4-point probe, and is shown in Table 8 as the average of 49 measured values from the wafer diameter. These data show that under the polishing conditions of the first P Baifeng (that is, the first polishing step), a sufficient amount of abrasive is left, so that the phase can be maintained in the second stage (that is, the second polishing step). For a fixed removal rate of at least 4 minutes. 32 Table 8 Copper removal (A) 5122 6002 6972 7707 8537 Second stage time (minutes) 5 ----0 1 2 3 4 Increased copper removal (A / min) 880 925 862 854 33 200413489 Table 9 5 —5 10—10—20—20—50—50—001—00 Feature structure copper line width—oxide line width (μηι) ~ S U63 15ΐΓϋ5ΓϋΤΤ ~ Βπ Standard deviation of surface depression (A) 316 379 379 609 869

Example 10

• U The abrasive used in this example is silicon oxide, which undergoes surface modification by reacting with dichlorodimethylsulfite. The 5 SEMATECH 854 patterned wafer was polished with a slurry for 95 seconds. The slurry was surface-modified silicon oxide (11 weight percent), hydrogen peroxide (5 weight percent), glycine (1 weight percent), and benzo. Triazole (i millimolar). Using a liquid for an additional 275 seconds, the liquid system consists of hydrogen peroxide (8 weight percent), glycine (1 weight percent), and benzotriazole (3 mmol), but does not include surface modification. Quality silicon oxide. Visual inspection results showed that the copper overlay was removed from the wafer by more than 95%. Surface depressions are determined from several characteristic structures of nine individual grains across the diameter of the wafer surface. The average surface depression values of these characteristic structures are described in Table 10. The results confirm that the use of surface-modified abrasives in the first stage of steel polishing can further reduce the line surface depression when compared with similar polishing using non-modified abrasives. Data obtained on a 50-50 micron feature on a die in the middle of the wafer radius indicates that after polishing for 215 seconds in the second liquid-only stage, the surface depression is approximately 52% of the final value after 275 seconds. These data imply that the multi-stage method has a wide over-polished window. 34 200413489 Table 10 Characteristics 5 IΓ " ^ — Γο 20—20 50—50 100—100 Copper line width — oxide line width (μηι) — — — average surface depression (person) 697 887 830 1001 1611 surface deviation standard deviation (person ) 372 320 342 543 785

J Example 11 10 Sematech 854 patterned wafer was polished with a slurry solution and a downward force of 4.5 psig for 105 seconds. The slurry solution was composed of oxidized stone (η weight percent) and hydrogen peroxide (4 weight percent). , Glycine (1% by weight) and benzotriazole (1mmol). Using the same slurry aqueous solution and a downward force of 1 psig, the polishing was continued for another 90 seconds. The results of the visual inspection showed that more than 95% of the copper coating was removed from the wafer. Surface_ is determined from several characteristic structures of 3 individual grains across the diameter of the wafer surface. The average surface depression values of these characteristic structures are described in Table 丨 丨. These results show that the two-stage polishing removes feeding, and the towel gradually relaxes only by reducing the mechanical force. However, in the process of health light, the test containing oxygen cutting is used to produce a high surface depression. . ^ 35 200413489 Table 11 Unprocessed Features Jiefu-10 ~ 10 50 ~ 50 100-100 Copper Wire Width_Oxide Line Width (μπι) 丨-… — · Average Surface Depression (Α) 2915 2982 3227 Standard Deviation of Surface Depression ( A) 321 633 587 Example 12 The abrasive used in this example is oxidized chopping, which is surface modified by reaction with dichlorodimethylsilicon. Polish a SEMATECH 854 patterned wafer with a slurry solution and 3.5 5 Psis downward force for 90 seconds. The slurry solution is a surface modified silicon oxide (U weight percentage), hydrogen peroxide (5 weight percentage), glycine Acid (1 weight percent) and benzotriazole (1 mmol). Using the same slurry solution and downward force of psig for an additional 120 seconds. The results of visual inspection showed that more than 95% of the copper coating was removed from the crystal 10 circle. Surface depressions are determined from several characteristic structures of three individual grains across the diameter of the wafer surface. The average surface depression values of these characteristic structures are described in Table 12. This result confirms that the copper cover layer is removed by polishing again. Its towel only gradually reduces the polishing conditions by reducing the mechanical force, but a polymer solution containing oxidized stone 15 is used throughout the polishing process to produce a higher surface depression. . 36 200413489 Table 12 Characteristic structure 10—10 50—50 100—100 Copper wire width_oxide line width (μιη) ¥ ^ Surface depression 265ΓΤ152 2824 ~ Standard deviation of surface depression (person) 932 870 1265 Used in the slurry of the polishing example Also the static rate of Example 13 5 will include the pH of hydrogen peroxide (8 weight percent), hydrogen peroxide (4 weight percent), glycine (1 weight percent) and benzotriazole (1 mmol) 5 of the slurry (400 ml) was poured into a glass dish (30x22X6 cm). The slurry was stirred with a magnetic rod and heated with a heatable stir plate purchased from Thermolyne Company Nm > vaTM. The temperature was adjusted and allowed to equilibrate at 23 ° C when measured with a thermometer 10 (range -100 ° C to 100 ° C). Stop stirring the slurry. A 200 mm blanket copper wafer was pre-weighed on a TR-2102TM scale previously purchased from Denver Instruments and placed into the slurry. After maintaining for 20 minutes, the wafer was removed from the slurry, rinsed with deionized water, rinsed with isopropanol, dried, and weighed again on the same scale. The weight loss was determined by the weight difference between wafer pre-weighing and reweighing. Wafer weight loss was 140 mg, which corresponds to a copper thickness loss of 250 A / min. Example 14 A slurry of pH 5 (400 containing silicon oxide (11% by weight), hydrogen peroxide (4% by weight), glycine (1% by weight), and benzotriazole (1mmol) was used. Ml) into a glass dish (30x22x6 cm). The slurry was transferred using a magnetic bar and heated using a heatable stir plate purchased from Thermolyne Company Nuova ™. The temperature is adjusted and allowed to equilibrate at 55 ° C when measured with a thermometer (range -10 ° C to 100 ° C). Stop stirring the slurry. 5 200 mm blanket copper wafers were pre-weighed on a TR-2102TM scale previously purchased from Denver Instruments and placed into the slurry. After 5 minutes, the wafer was removed from the slurry, rinsed with deionized water, rinsed with isopropanol, dried, and weighed again on the same scale. Weight loss is determined by the weight difference between wafer pre-weighing and reweighing. Wafer weight loss was 100 mg, 10 which corresponds to a copper thickness loss of 710 persons / min. Example 15 A slurry (400 ml) of hydrogen peroxide (8% by weight), glycine (1% by weight), and benzotriazole (3 millimoles) at pH 5 was poured into a glass dish (30x22x6 cm) in. The slurry was agitated with a magnetic bar and heated using a heatable stir plate purchased from Thermolyne Company Nuova ™. The temperature was adjusted and allowed to equilibrate at 23 ° C when measured with a thermometer (-10. (Range from 3 to 100). Stop stirring the slurry. 200 mm blanket-coated copper wafers were purchased from Denver Instruments in advance at TR Pre-weighed on the -2102TM scale and placed in the slurry. After maintaining for 20 minutes, remove the wafer from the slurry, rinse with 20 deionized water, rinse with isopropanol, dry, and weigh again on the same scale Weight loss is determined by the weight difference between wafer pre-weighing and re-weighing. Wafer weight loss is 10 mg, which corresponds to 18 A / mini copper thickness loss. 38 200413489 Example 16 will include hydrogen peroxide (8% by weight), glycine (1% by weight) and benzotriazole (1 mmol) at pH 5 (400 ml) were poured into a glass dish (30x22x6 cm). Stir with a magnetic rod The slurry was heated using a heatable stir plate purchased from 5 Thermolyne Company NuovaTM. The temperature was adjusted and allowed to equilibrate at 55 ° C when measured with a thermometer (-HTC to 10 (TC range). Stop stirring the slurry. Cover the 200 mm blanket Copper wafers are pre-purchased from Denver Instruments Pre-weighed on the TR-2102 ™ scale and placed in the slurry. After maintaining for 5 minutes, remove the wafer from the slurry, rinse with deionized water 10, rinse with isopropanol, dry, and weigh again on the same scale Weight. The weight loss was determined by the weight difference between the wafer pre-weighing and re-weighing. The wafer weight loss was 10 mg 'which corresponds to a copper thickness loss of 71 people per liter. [Figure ^ Jiancui ^ Ming]: • Dian 15 [List of Symbols for the Main Components of 囷] ·· 39

Claims (1)

200413489 Scope of patent application: 1. A slurry system for removing metal from a substrate, comprising: (a) a first slurry containing an abrasive and capable of partially removing the metal from the substrate; and 5 (b) A second slurry for further removing the metal from the substrate, wherein the abrasive concentration of the first slurry is higher than the second slurry. 2. The slurry system according to item 1 of the patent application scope, wherein the metal is selected from copper, button, silicon dioxide or a mixture thereof. 10 3. The slurry system according to item 1 of the patent application scope, wherein the metal is copper. 4. The slurry system according to item 1 of the patent application scope, wherein the second slurry contains no abrasive. 5. The slurry system according to item 1 of the patent application scope, wherein the abrasive is selected from the group consisting of oxide, titanium oxide, oxide, germanium oxide, stone oxide, 15 hafnium oxide, or a mixture thereof. 6. The slurry system as claimed in claim 3, wherein the abrasive is oxidized stone. 7. The slurry system according to item 4 of the patent application, wherein the abrasive is precipitated silica. 20 8. The slurry system according to item 1 of the scope of patent application, wherein the abrasive is present in an amount of 0.1 to 30% by weight based on the first slurry. 9. The slurry system according to item 4 of the patent application, wherein the silica has aggregates of primary particles, and the average diameter of the primary particles is at least 7 40 200413489 nanometers, wherein the size of the aggregates is less than 1 micron, And the hydroxyl content is at least 7 hydroxyl / division nanometer. 10. The slurry system according to item 1 of the patent application scope, wherein at least one of the first slurry and the second slurry further comprises an oxidant. 5 11. The slurry system according to item 8 of the application, wherein the oxidant is selected from the group consisting of inorganic and organic per-compounds, shed acids, chloric acids, nitrates, sulfates, or mixtures thereof. 12. The slurry system according to claim 8 in which the oxidant is selected from the group consisting of hydrogen peroxide, vein-hydrogen peroxide, or a mixture thereof. 10 13. The slurry system according to item 1 of the patent application scope, wherein at least one of the first slurry and the second slurry further comprises a compound selected from a complexing agent, an anticorrosive agent, a blocking compound, a polyvalent cation chelating agent, and a thickener. Substance or mixture of substances. 14. The slurry system according to item 1 of the patent application scope, wherein at least one of the first slurry 15 and the second slurry further comprises an acid selected from the group consisting of picolinic acid, aramidic acid, gadolinic acid and mixtures thereof. 15. The slurry system according to item 1 of the patent application scope, wherein at least one of the first slurry and the second slurry further comprises a polyvalent cation chelating agent and an anticorrosive agent. 20 16. The slurry system according to item 1 of the patent application scope, wherein at least one of the first slurry and the second slurry further comprises a polyvalent cation chelating agent, an anticorrosive agent, and a thickening agent. 17. The slurry system of claim 1 in the patent application scope, wherein the first slurry has residual metal left on the substrate. Shoulder m 41 200413489 5 10 15 20 18. The slurry system according to item 3 of the patent application, wherein the first slurry has residual copper left on the substrate. 19. The slurry system of claim 17 in which the second slurry removes residual metal at least partially from the substrate. 20. The slurry system of claim 18, wherein the second slurry removes residual copper from the substrate at least partially. 21. A method for removing copper, comprising the following steps: (a) applying a first paddle liquid containing an abrasive to a substrate; (b) applying a second slurry on the substrate; wherein the first slurry The concentration of the abrasive is higher than the second slurry. 22. The method of claim 21, wherein the first slurry removes a portion of copper from the substrate and leaves a residual copper on the substrate. 23. The method of claim 21, wherein the second slurry removes the residual copper from the substrate at least partially. 24. A method for polishing a microelectronic substrate, comprising: (a) performing a first polishing using a first slurry and a polishing pad, wherein the first slurry includes an abrasive; and (b) using a second slurry and a polishing pad A second polishing is performed, wherein the abrasive concentration of the first slurry is higher than the second slurry. 25. The method of claim 24, wherein the first polishing provides a partial removal of metal from the substrate and leaves a residual portion of the metal in the · 〇 Kang on the substrate. 26. The method of claim 25, wherein the second polishing provides removal of the residual metal at least partially from the substrate. 42 200413489 27. The method of claim 25, wherein the metal is selected from the group consisting of copper, group, and silicon dioxide. 28. The method of claim 24, wherein the first polishing is completed before the second slurry is applied. 5 29. The method of claim 24, further comprising the steps of: cleaning the substrate after completing the first polishing and before starting the second polishing. Λ Reference 43 200413489 柒 Designated representative map: (1) The designated representative map in this case is: None (II) The component representative symbols of this representative map are simply explained: Wu Yang J. If there is a chemical formula in this case, please disclose the one that best shows the characteristics of the invention Chemical formula: