TWI307356B - Method for processing a substrate - Google Patents

Description

1307356 IX DISCLOSURE OF THE INVENTION [Technical Field of Composition of the Invention of the Invention] <> Remove conductive material from the substrate [Previous technology street] Generation i = ground manufacturing sub-half micron and smaller features for semiconductor components new close / body circuit (Ruchuan and Xiao large integrated circuit (ULSD key Technology. While expanding the limitations of circuit technology, the shrinking size of interconnects in vtjSI and U]:SI technology will have more requirements for process capability. The formation of interconnects for VLSI and ULSI Success and added circuit density and subsequent results in improving the quality of individual substrates and wafers are of paramount importance. Interconnection lines are formed by forming features on the surface of the substrate using techniques of continuous deposition and removal of materials. When continuously deposited and removed, the surface at the top of the substrate may become uneven on the entire surface and needs to be planarized before further processing. Flattening or "grinding" The planarization of the material surface to form a substantially flat, flat surface helps to remove excess deposited material and remove unwanted surface topography and surface defects (eg, rough surfaces, agglomerated materials) , lattice damage scratches and contaminated layers or materials) to provide a flat surface for subsequent lithography and processing. Electrochemical mechanical p〇nshing (ECMP) is a method for flattening the surface of a substrate. The ECMp is dissolved by an electrochemical "anode" while a conductive material (such as copper) is self-contained from the surface of the substrate by a chemical mechanical substrate (Chemical 1307356. mechanical planarization, CMP). The shifting & receiving system comprises a substrate holder and is arranged in the polishing composition for the alpha primary electrode. The substrate is in electrical contact with one of the electrodes, and the effect is made in the A material-removed electrode that is ionized by a metal atom on the surface of a material from a potential source (eg, a voltage source connected to two electrodes). The metal ion is dissolved into the abrasive composition. However, it has been observed The ECMP method generally has a lower removal rate compared to conventional chemical methods and has been shown to be a modification of the processing conditions (eg, improved substrate and research). The padding force and the increase of the grinding time) 'do not increase the removal rate in some cases, the substrate surface will have more dishing and more damage. For example, it has been observed that it contains low mediation. The large abrasive pressure on the substrate of the k dielectric material can cause a large shear force or trace to the defect due to the deposition of the material, for example, due to the large grinding pressure. Therefore, there is a need for a conductive material that can be removed from the substrate. A method of grouping materials which minimizes substrate damage during planarization. SUMMARY OF THE INVENTION The present invention provides a composition and method for electrochemically grinding a technical material, in one aspect, a combination The system provides for the removal of at least one electrically conductive material from the surface, the composition comprising two processes of acid milling to grind the ECMP of the crucible, and the current causes the grinding of the substrate around the substrate to promote the satisfactory satisfaction between the movements. , ® 曲磨I: Constant (deposition of the material in the low material and the removal of the artefact is guided by the substrate system electrolyte 1307356. The day is replaced (more) is replacing the page today, what? The patent, in January, revised the system '~ one or more chelating agents, one or more corrosion inhibitors, one or more inorganic or organic acid salts, one or more providing a pH between about 3 and about 10 The pH adjuster' is selected from the group consisting of abrasive particles, one or more oxidizing agents, and combinations thereof, and a grinding promotion material and a solvent. Further, the composition is a method for treating a substrate, the method comprising disposing a substrate having a layer of a conductive material formed thereon in a processing apparatus including a first electrode and a second electrode, wherein the substrate is made Electrically contacting the second electrode 'provides the composition between the first electrode and the substrate, applies a bias between the first electrode and the second electrode' and removes the conductive material from the layer of conductive material. [Embodiment] In general, the present invention provides a composition and method for removing at least one electrically conductive material from a surface of a substrate. The method of planarization of the present invention for removing conductive material from the surface of a substrate by electrochemical mechanical polishing (ECMp) technology will be described below.

, unless otherwise defined, the words and phrases used in this document shall be the general and customary meanings given to them by those skilled in the art. Chemical milling should be broadly interpreted and includes, but is not limited to, the use of chemical activity to planarize the surface of the substrate. Electro-grinding should be widely disintegrated and include, without limitation, applying electrochemical activity to planarize the substrate. Electrochemical mechanical research (ECMP) should be interpreted broadly and includes, but is not limited to, the application of electrochemical

Mechanical removal, or combination of electrochemical and mechanical work. I 8 1307356 <^>^**i?^"M^MMM**^*M^****^**"^— I" I ι·_ _ ·· _ (more) positively or indirectly applying the anode to the anodic dissolution enthalpy, gamma: ** and including, but not limited to, the removal of the substrate surface to the surrounding bias will cause the conductive material to be released from the substrate And package cut, 'and in the compound. The abrasive composition should broadly resolve the percentage or weight: The volume of the electrolyte component in the polishing composition, -, V. The knife ratio is the percentage based on the volume of the liquid composition component and the percentage based on the weight of the solid composition component. Device: &_Electric implementation 丨 Figure 1 shows a cross-sectional view of a specific embodiment of a "face_down" processing bath 200. The process 200 typically includes #204 and a polishing head 202. The substrate 208 is snapped into the polishing head 2〇2 and then lowered to the disk 2〇4 in a face-down (e.g., back-up) direction during processing. The electrolyte (as described herein) flows into the disk 204 in contact with the substrate surface and the polishing pad assembly 222 while the polishing head 202 contacts the substrate 208 with the polishing pad assembly 222. The disk 204 includes a polishing pad assembly 222, a bottom portion 244, and side walls 246 that define a container that can receive the polishing pad assembly 222. Side wall 246 includes a weir 2 1 8 formed through the sidewall on the sidewall to permit the abrasive composition to exit the tray 204. A port 218 is attached to the valve 220 to selectively vent or leave the abrasive composition in the tray 204. The substrate 208 and the polishing pad assembly 222 disposed in the disk 204 are moved relative to each other to produce a polishing action (or an action that enhances the uniformity of the plating layer). The grinding action is usually among many other actions, including at least one of orbital, rotational, linear or curved, or a combination thereof. 9 1307356

哆 史 史 » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » - or both are moved simultaneously to complete. The grinding head 202 can be stationary or driven to provide at least a portion of the relative movement between the disk 204 and the substrate 208 sandwiched by the polishing head 202. The specifics described in Figure 1 In an embodiment, the abrading head 202 is coupled to a drive system 2丨0. The drive system 210 moves the polishing head 202 in at least one of a rotational motion, an orbital motion, a sweep motion, or a combination thereof.

The polishing head 02 will typically hold the substrate 208 during processing. In one embodiment, the abrading head 202 includes a housing 214 that encloses the bladder 216. When the bladder 216 is in contact with the substrate, the gas in the bladder can be withdrawn to create a vacuum between the two' thereby holding the substrate firmly against the polishing head 2〇2. In addition, the bladder 216 can be inflated to compress the substrate into contact with the abrasive integrated assembly 222 that is fastened to the tray 2〇4. Buckle 238 and outer cover 214 are joined together to confine substrate 208 to prevent the substrate from slipping out of polishing head 202 during processing. One type of grinding head that can be used to obtain the benefits of the present invention is ΤΙΤΑΝ ηεαε > τμ carrier head' is commercially available from Applied Materiais (in Santa Clara' Cahforma). A further example of a grinding head that can be used to obtain the benefits of the present invention is described in U.S. Patent No. 5,079, issued toK. The tray 204 is usually made of plastic (for example, gas polymer, teFL〇n® polymer, perfluoroalkoxy resin (pFA, _ 曰 (7) A), polyethylene bake (PE), sulfonated Polyphenylether oxime (PES) or other materials that are compatible or non-reactive with Ketian's abrasive composition for electroplating or electrogrinding. The disk 204 is rotated over the pedestal 206 by bearings 234. Hybrid / % 236 236 is connected to the disc 204 10 1307356

And rotating the disk 204 during processing, the receiving disk 228 is disposed on the base 206 and confining the disk 204 to collect working fluid flowing out through the opening 218 of the disk 204 after processing and/or processing, such as The composition is ground. The abrasive composition delivery system 232 is typically disposed adjacent to the tray 204. The abrasive composition delivery system 203 includes a nozzle or outlet 230 that is coupled to the abrasive composition supply 242. The outlet 230 causes the abrasive composition or other working fluid to flow from the abrasive composition supply 242 into the tray 204. During processing, the abrasive composition typically provides an electrical path to bias the substrate 20 8 and drive an electrochemical process to remove and/or deposit material on the substrate 208. Alternatively, the abrasive composition delivery system can provide a polishing composition through the treatment tank bottom 244 to allow the abrasive composition to flow through the polishing pad assembly to contact the abrasive crucible and the substrate or a recovery system can be used to recover and reuse the abrasive composition. This recycling system can be used to extend the effective manufacturing life of the abrasive composition of the same or other processing steps. As shown in Fig. 1, the processing may be performed at a position close to the disk 204 as needed to periodically process or regenerate the polishing pad level 222. In general, the treatment limb device 250 includes an arm 252 that is coupled to the post 254 that is adjusted to the & i position so that the processing element 258 can be fully swept through the grinding pad and the 222 外 _ external element 258 is coupled to arm 252 by shaft 256 to allow clearance between side walls 246 of arms 252 "2〇4 when 70 pieces 258 are lowered to contact polishing pad assembly 222. The processing element 258 is typically a tantalum carbide disk. The disk can be patterned to cause the surface of the polishing pad assembly 222 w, - to become a predetermined surface condition/state that enhances processing uniformity. A processing element 258 that can be used to obtain the benefits of the present invention is described in U.S. Patent Application Serial No. 9/676,280, filed on Sep. 28, 2000. In this article, the bow is not inconsistent with the features and specifications of this article. 4 The power source 224 is connected to the grinding board 2 2 2 by electrical wires 223a, 223B. The power supply 2 2 4 applies an electrical bias to the polishing pad assembly 2 2 2 to drive the electrochemical procedure detailed in the column. The 223A, 223B pass through a slip ring 226 disposed below the disk 2. Slip ring 226 facilitates a continuous electrical connection between power source 22 and polishing pad assembly 222 as disk 204 rotates. Conductor 223A, which may be a metal wire, tape or other conductor compatible with the working fluid, or county A\ has a coating or coating that protects the wire from damage by the working fluid. Examples of materials that can be used for wires 223A, 223B are among the many other materials, including insulated copper, graphite, titanium, platinum, gold, and HASTELOY®. The coating deposited around the wire may comprise a polymer such as fluorocarbon, polyethylene (PVC), polyamine or the like. The polishing pad assembly 222 includes an element consisting of both an anode and a cathode of an electrochemical cell. Both the anode and the cathode can be removed from the disk 204 by simply using the used polishing pad assembly 222. Pad assembly 222 and new electrical components and branch assemblies are embedded in disk 204 while being replaced. The polishing pad assembly 222 includes a conductive crucible 203 that is coupled to the pad 2〇7. Pad 207 can be connected to electrode 209. A dielectric implant (not shown) may be disposed between the conductive pad 203 and the pad 207 or the electrode 2〇9 to adjust the flow of the electrolyte through all or a portion of the conductive pad. Conductive pad 203 is used to apply a uniform bias to the surface of the substrate without the use of conventional biasing means (e.g., edge contact). Electrode 2 〇9 is typically biased to the cathode via a wire (eg, wire 12 1307356 '. . . . ' ' I M. ----:, 223 A) connected to power source 224 And the conductive pad 2〇3 and the substrate are biased to become the anode in the 纟ECMp(4) which causes the anode to dissolve. Typically, the conductive pad 203, the pad 2〇7, and, if desired, the dielectric insert and the electrode 209 can be brought together to form a polishing pad combination that is easily removed and replaced from the disk 2〇4. Unit body of 222. In general, the conductive pads 203, pads 207, and, if desired, the dielectric insert and electrode 209 can be bonded or combined with one another. Or the conductive pad 2〇3, pad 2〇7 by other methods including stitching, bonding, heat staking, riveting, locking and clamping, or a combination thereof among other numerous methods. 'The dielectric insert and electrode 209 can be combined as needed. An example of a conductive pad 203 is more fully disclosed in U.S. Patent Application Serial No. 10/03,732, filed on Dec. The characteristics and disclosures of the claims are contrary. The face-down grinding device is more fully disclosed in U.S. Patent Application Serial No. 1/151,538 [Patent Agent File Number No. 6906], filed on May 16, 2002, the name of which is The "Method and Apparatus for Substrate Grinding" was transferred to American Applied Materials. The 25th to 81st paragraphs of this case are incorporated herein by reference. 'The degree of citation is not to the extent of the claims and the contents of the description. Related information. Similar to face-up grinding, the case provides relative motion between the substrate and the electrode and/or polishing pad. The treatment tank 200 can be configured on a grinding platform (e.g., a Reflexion® CMP system, a MirraTM CMP system, and a MirraTM Mesa CMP system available from Santa Clara, Calif.). In addition, it is advantageous to use 13 l3 〇 7356 for electrochemical & chemistries using the methods or compositions described herein. 1 Composition and method In one aspect of the invention, it is provided that a metal (for example, a composition, the abrasive composition comprises an acid:), an electric mill, or a plurality of chelating agents, one or more corrosion inhibitors, System, inorganic or organic acid salt, one or more pH adjusting agents between pH values or cherries, selected from abrasive particles, - dilute, 10 .. 4 oxidant 5 # Materials and solvents.埤1s has an ECMp process with flattened and smooth surface after grinding. What is the abrasive composition of i|j'f * 1 to promote improved grinding and conductivity rejection. The material has been transferred. Although the abrasive composition is particularly useful for removing steel, the abrasive group δ can also be used to remove other conductive materials, such as aluminum, ', 玛, 钦, 钛化钛' buttons. Niobium nitride, cobalt, gold, silver, and combinations thereof. Other materials used to form features of the conductive material on the surface of the substrate (including barrier layer materials, such as buttons, nitride groups, chin and nitrite) can be removed and mechanically ground by the methods described herein (eg, The polishing pad and/or abrasive contact can be used to improve, and the removal of conductive and conductive materials' can also be used to remove...: Heterocarbon cerium oxide and doped or undoped bismuth carbide Dielectric material. 〃 The abrasive composition comprises an acid based electrolyte for providing electrical conductivity. A suitable acid-based electrolyte system includes, for example, a sulfuric acid-based electrolyte, a bismuth citrate electrolyte, a pervaporic acid-based electrolyte, an acetic acid-based electrolyte, and an acid-based electrolyte system including an acid electrolyte such as phosphoric acid. And sulfuric acid, and acid electrolyte derivatives, including ammonium salts and potassium salts thereof. The acid based electrolyte system can also buffer the composition to maintain the desired pH of the treated substrate. Examples of suitable acid-based electrolytes include compounds containing phosphate (ΡΟ/) such as phosphoric acid, potassium phosphate (K3P〇4), copper phosphate, diammonium phosphate (νη4η2ρ〇4), diammonium hydrogen phosphate ((ΝΗ4) 2Ηρ〇4), and a compound of citrate (S〇43·), such as sulfuric acid, diammonium hydrogen sulfate ((Νί14) 2ΗΡ04), copper sulfate, or a combination thereof. The invention is also intended to utilize the methods described herein, as well as known or unknown electrolytes to form the compositions described herein. Alternatively, an acid based electrolyte system may be provided at a level between about 1 and about 30 weight percent (wt%) or volume percent (vol%) of the composition to provide suitable conductivity for practicing the methods described herein. For example, ammonium monohydrogen phosphate and/or diammonium phosphate can be present in the composition in an amount of between about 15 and about 25 by weight or volume percent. Phosphoric acid may be present at a concentration of, for example, between about 2% and about 6% by weight. A λ/ΛΓ' chelating agent on a conductive material (such as a steel ion) can also be used to bond "rate removal rate' and depreciate. Buffering or conditioning the composition to maintain the desired base of the treated substrate, the guanamine group, the y:y'- and the sulphate, the dicarboxylic acid group, the tricarboxylic acid group, the hydroxyl group, the sea carboxylate mixture and Combining the group or species of chelating agent #叮 spoon "%-based compound. n phantom may also include the integration of 15.1307356 described herein except that the metal material (such as copper) is combined with the functional group. Or afterwards, it may be present in any oxidation state (eg, 0, 1 or 2.) The abrasive composition may comprise a concentration of between about 0.1% by volume and about 15% by volume or between about 0.1% by weight and about 1%. Between 5 wt%, such as between about 0.1% and about 4% by volume or between about 0.1% and about 4% by weight of one or more chelating agents. For example, about 2% by volume or about can be used. 2% by weight of ethylenediamine as a chelating agent. Examples of suitable chelating agents include compounds containing one or more amine and guanamine functional groups, such as ethylenediamine, diethylenetriamine, diethylenetriamine Derivative, hexamethylenediamine, amino acid, B Amine tetraacetic acid, methyl decylamine or a combination thereof. Examples of suitable chelating agents containing one or more rebels include citric acid, tartaric acid, succinic acid, oxalic acid, and combinations thereof. Others containing one or more carboxyl groups Suitable acids include acetic acid, adipic acid, butyric acid, citric acid, caproic acid, caprylic acid, glutaric acid, glycolic acid, formic acid, fumaric acid, lactic acid, lauric acid, malic acid, maleic acid, Malonic acid, myristic acid, palmitic acid, phthalic acid, propionic acid, pyruvic acid, stearic acid, valeric acid or a combination thereof. In any of the specific embodiments described herein, the inorganic or organic acid salt As a chelating agent, the abrasive composition may comprise a concentration of between about 0.1% by volume and about 15% by volume of the composition or between about 0.1% by weight and about 15% by weight of the composition. For example, between about 0.1% by volume and about 6% by volume or between about 0.1% by weight and about 6% by weight of one or more inorganic or organic acid salts. For example, about 2 can be used in the abrasive composition. 5% by volume or about 2% by weight of ammonium citrate. 1307356 Examples of suitable inorganic or organic acid salts include ammonium and potassium salts of organic acids such as ammonium oxalate, ammonium citrate, ammonium succinate, potassium dihydrogen citrate, dipotassium hydrogen citrate, tripotassium citrate, potassium tartrate, Tartaric acid, potassium succinate, potassium oxalate, and combinations thereof. In addition, the ammonium carboxylate and potassium salts described herein can also be used as the organic acid salt in the compositions described herein. In one example, the corrosion inhibitor can prevent oxidation or rot of the metal surface by forming a layer of material that reduces or reduces the chemical interaction between the material deposited on the surface of the substrate and the surrounding electrolyte. To a minimum, the layer of material formed by the corrosion inhibitor isolates the surface and surrounding electrolyte, thereby inhibiting or minimizing electrochemical current from the surface of the substrate while limiting electrochemical deposition and/or dissolution. The abrasive composition can comprise between about 0.001% and about 5.0% by weight, such as between about 0.2% and about 0.4% by weight, of an azole-containing organic compound. The one or more corrosion inhibitors may comprise an organic compound containing one or more sial groups. Examples of the azole group-containing organic compound include benzotriazole, decyl benzotriazole, 5-methyl-1-benzotriazole, and combinations thereof. Other suitable corrosion inhibitors include film formers which are cyclic compounds such as imidazole, benzimidazole, triazole, and combinations thereof. Derivatives of benzotriazole, imidazole, benzimidazole and triazole having a substituent of a hydroxyl group, an amine group, an imido group, a carboxyl group, a mercapto group, a nitro group and an alkyl group can also be used as the corrosion inhibitor. Among other corrosion inhibitors, other corrosion inhibitors also contain urea and sulfur. Alternatively, the amount may be between about 0.002% by volume of the composition and about 17 1307356 months (more) positive replacement page 1.0% by volume or between about 0.002% by weight and about 1.% by weight of the composition. An intervening polymer inhibitor (such as a non-limiting example, such as polyalkyl aryl ether phosphate or nonylphenol oxyethylene ether ammonium sulphate) is substituted or combined with an azole group-containing sulphur inhibitor. The one or more pH adjusting agents provide pH adjustment of the abrasive composition. The polishing composition preferably has a pH between about 2 and about 10, such as between about 4 and about 6. The abrasive composition can comprise up to about 70% by weight of one or more p-quinone modifiers, for example between about 0.2% and about 25% by volume or between about 0.2% and about 25% by weight. One or more pH adjusting agents. Different compounds may provide different pH values for known concentrations, for example, the composition may comprise between about 0.1% and about 10% by volume of a base (such as potassium hydroxide, ammonium hydroxide or Combined) to provide the desired pH. The one or more pH adjusting agents may be organic acids (eg, carboxylic acids such as acetic acid, citric acid, oxalic acid), phosphate containing components (including phosphoric acid, ammonium phosphate, potassium phosphate, and combinations thereof), or combinations thereof. Inorganic acids such as strong acids such as sulfuric acid, nitric acid, and combinations thereof can also be used in the abrasive composition. The one or more pH adjusting agents can also be assayed, such as potassium hydroxide, ammonium hydroxide, or a combination thereof. The amount of base used in the abrasive composition is generally the amount required to adjust the pH of the composition to a desired value between about 2 and about 10. Alternatively, the abrasive composition may comprise a base and a compound selected from the group consisting of acetic acid, citric acid, oxalic acid, phosphoric acid, ammonium phosphate, potassium phosphate or combinations thereof. In a composition comprising a combination of a compound selected from the same group as described above, the composition of the composition may comprise about 〇% by volume and about 10%. Between 5% by volume of alkali and between about 0.2% by volume and about 25% by volume or between about 3% by weight and 25% by weight, selected from the group consisting of acetic acid, citric acid, oxalic acid, phosphoric acid, phosphoric acid, potassium phosphate or Combining the grouped compounds. The abrasive composition comprises one or more abrasive-promoting materials comprising abrasive particles, one or more oxidizing agents, and combinations thereof.

Abrasive particles can be used to increase the rate of removal or removal of conductive material from the surface of the substrate during the grinding process. The abrasive particles can reach about 35 weight V of the abrasive composition during processing. . Abrasive particles having a concentration of between about 〇1 wt0/〇 and about 5% by weight can be used in the abrasive composition. Suitable abrasive particles comprise inorganic abrasives, polymeric abrasives, and combinations thereof. Inorganic abrasives useful in the electrolyte include, but are not limited to, cerium oxide, aluminum oxide, oxidized oxidized, titanium oxide, cerium oxide, gallium oxide or any other known or unknown metal oxide abrasive having an approximate The average size between 20 nm and approximately 1000 nm. In general, suitable inorganic abrasives have a Mohs hardness of more than 6 and the present invention contemplates the use of abrasives having a lower Mohs hardness in the abrasive composition. The polymeric abrasives described herein may also be referred to as r organic polymeric particulate abrasives, "organic abrasives" or "organic particles." The polymeric abrasive can comprise an abrasive polymeric material. Examples of polymeric abrasive materials include poly(indenyl) methacrylate, polymethyl acrylate, polystyrene, poly(fluorenyl) acrylonitrile, and combinations thereof. The polymeric abrasive has a Hardness Shore D between about 60 and about 8 Torr and can be changed to have a higher or lower hardness. The polymeric abrasive is also softer than the inorganic particles described herein and can be studied in 19 1307356

Month A repair (more) is replacing: the grinding object can be reduced to or possibly more than the polishing pad polymerization change, for example, the generation is more than about the poly-pair wants to have an affinity energy base, for example, if the mass gives it a degree of affinity The organic polymerization mixture) is present before the combination of Ge. The genus material bond is further characterized by the fact that the abrasive is capable of with or without a small amount of friction between the substrate and the number and severity of defects and other surface defects compared to the inorganic particles. The polymeric abrasive material used in any abrasive pad material is harder to provide better abrasive performance than when only the material is used. The hardness of the abrasive can be achieved by controlling the degree of cross-linking in the abrasive, such as a higher degree of cross-linking, resulting in a harder polymer due to the hard abrasive. The polymeric abrasive typically forms spherical beads having an average diameter of between 1 micron and about 20 microns or less. The abrasive may be modified to have a functional group, such as one or more kinds of conductive materials or conductive materials that are removed from the substrate or composition, that is, the ionic force of the conductive material or the conductive material. It can cause the conductive material to be removed from the surface of the substrate during processing. To remove copper during the grinding process, the organic polymeric particles may be modified with an amine group, a carboxylic acid group, a pyridyl 'hydroxyl group, a copper with a high ligand or a combination thereof to facilitate copper removal. Bonding, the particles are added or substituted with a chemically active agent in the composition (for example, a chelate type. The metal material to be removed (for example, copper) can be in any oxidation state with, in, or after the functional group (for example) The ruthenium, 1 or 2) functional group can be removed from the surface of the substrate by metallization formed on the surface of the substrate during processing. The polymeric abrasive has desirable chemical properties, such as a wide range of pH of the polymerization. The values are stable and are not easily agglomerated with one another, so that the I-abrasive can be used in the composition with less surfactant surfactant or without a dispersing agent. 20 1307356

Alternatively, inorganic particles coated with the polymeric materials described herein can be used with the abrasive composition. The abrasive used in the composition may be a combination of a polymeric abrasive, a polymeric abrasive-coated inorganic abrasive, depending on the desired abrasive properties and results. The present invention may use one or more oxidizing agents to enhance the removal or removal rate of the electrically conductive material from the surface of the substrate. The oxidizing agent used in the present invention is typically a reagent which accepts electrons from a single layer or layers of a substrate to be ground to oxidize the material on the substrate to more effectively remove the material. For example, an oxidizing agent can be used to oxidize the metal layer to a relative oxide or hydroxide, such as copper to copper oxide. There is already oxidized steel containing Cul+ ions which can be further oxidized to a higher oxidation state, such as Cu2+ ions, which can be further reacted with a chelating agent. The oxidizing agent may be between about 0.01% by volume and about 90% by volume or between about 0.001% by weight and about 9% by weight, for example between about 0.1% by volume and about 20% by volume or About 20% by weight of the weight. /. The content between them is present in the abrasive composition. In the abrasive composition, the specific embodiment t' is present in the abrasive composition between about 〇_1% by volume to about 15% by volume or between about 〇"% by weight to about 5% by weight. Hydrogen peroxide. Examples of suitable oxidizing agents include peroxides, such as compounds which can be dissociated by hydroxyl radicals (for example hydrogen peroxide) and their adducts (including hydrogen peroxide glands, percarbonates) and organic peroxides, for example Peroxyalkyl, cyclic peroxide or peroxylated aryl, peroxybenzol, peroxyacetic acid and di-t-butyl peroxide. It is also possible to use sulphate or sulphate derivatives (eg 21 1307356 I Green?

'I monopersulfate and dipersulfate salt' includes, for example, peroxydisulfate, potassium peroxydisulfate, ammonium persulfate and potassium persulfate. Peroxide salts such as sodium percarbonate and sodium peroxide can also be used. The oxidizing agent may also be an inorganic compound or a compound containing an element of the highest oxidation state. Examples of inorganic compounds or compounds containing the highest oxidation state include, but are not limited to, moth molybdic acid, molybdate, odorous acid, perbromate, peroxyacid, peroxyacid, perboric acid Nitrate (such as lanthanum nitrate, ferric nitrate, nitric acid), perborate and permanganate. Other oxidizing agents include bromates, chlorates, chromates, iodates, iodic acid and cerium (IV) compounds such as cerium nitrate. The remainder or remainder of the above abrasive composition is a solvent such as a polar solvent (containing water, preferably deionized water), and an organic solvent (e.g., an alcohol or a glycol). In addition, the amount and type of components of the abrasive composition, such as the residual inhibitor and oxidant, can be adjusted to achieve the desired rate of removal. For example, a smaller amount of corrosion inhibitor increases the rate of removal compared to a composition containing a higher proportion of the rot-inhibitor; a smaller amount of oxidant reduces the shift compared to a composition containing more oxidant. In addition to the rate. Examples of the abrasive compositions described herein contain about 2% by volume of ethylenediamine, about 2% by weight of ammonium citrate, about 0.3% by weight of benzotriazole, between about 0% to 1% by volume and about Between 3 vol% or between about 〇. 丨 wt% and about 3 wt. Between /〇, for example, about 0.45% hydrogen peroxide, and/or between 0. 01% by weight and about 1% by weight, for example, 〇·15% by weight of abrasive particles' and about 6% by volume Phosphoric acid. The composition has a ρ η value of about 22 l3 〇 7356 兮 5 ', for example, by allowing the composition to additionally contain potassium hydroxide which can adjust the pH to a preferred range. The remainder of the abrasive composition is divided into deionized water.

Alternatively, the abrasive composition may additionally contain an electrolyte additive comprising a suppressant, a promoter, a leveling agent, a brightening agent, a stabilizer, and a release agent to enhance the effectiveness of the abrasive composition when the surface of the substrate is ground. For example, certain additives may reduce the ionization rate of the metal atoms and therefore inhibit the dissolution process, while other additives may form a fine, shiny substrate surface. The additive can reach about 15 weights. /. Or a concentration of about 15% by volume is present in the abrasive composition and can vary depending on the desired result after milling.

For example, one or more surfactants can be used in the abrasive composition. Surfactants can be used to enhance the dissolution or solubility of materials such as metal and metal ions or by-products from processing, reduce any potential agglomeration of abrasive particles in the abrasive composition, improve chemical stability and reduce abrasive composition. Decomposition of ingredients. The one or more surfactants can have an approximate volume of the abrasive composition. A concentration of between about 1% by volume or between about 0.001% by weight and about 1% by weight. In one embodiment of the abrasive composition, the concentration can be used to be between about 〇 1 volume 〇 / 〇 and about 2 vol% or between about 〇 1% by weight and about 2 weight. Between / / ’, for example, between about 0.1 volume. /. The surfactant is between about 1% by volume or between about 0.1% by weight and about 1% by weight. The one or more surfactants may comprise a nonionic surfactant and an ionic active agent, comprising an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and an ionic interface having more than one ionic functional group 23 1307356 --- --------一—日修 (illusion active agent' such as zwitterionic boundary, the main alpha surfactant. The dispersant is regarded as a sexual agent, which is used as the boundary here. The formulation containing the polymeric abrasive is in a wide range of pH values to be stabilized and difficult to polymerize with each other. This property allows the polymeric abrasive to have less surfactant or no interface in the composition. The active agent, "used in the presence of a dispersing agent. Other examples of additives include a combination of three or more leveling agents, which are broadly defined herein as additives that inhibit the current flow on the substrate surface 4. The agent inhibits the dissolution current by adhering to a conductive material such as & ^ „ inhibiting the electrochemical reaction between the electrolyte and the conductive material and/or forming a depolarizing agent that limits the electrical reaction. The concentration is between about 0.005 vol. 0 and about 10 vol% of the electrolyte, or between about 0.005 wt% and about 1 GW% of the electrolyzed concentrate + I from the liquid phase 'for example, between about the electrolyte. QG5 vol% and about 2 vol. / between about 5% by weight and about 2% by weight of the leveling agent of the electrolyte. The leveling agent includes (but is not limited to) polyethylene Alcohols and Polyethylene Glycol Derivatives. Other leveling agents useful in the methods described herein include any of those useful in the art of electricity, such as polyamines, polyamines, and polyimines, such as polyethyleneimine. , polyglycine, 2-amino-i-naphthalenesulfonic acid, 3-amino-propanesulfonic acid, 4•amino-based methyl-2-acid. Inhibitors (eg, electrical resistance additives that reduce the conductivity of the abrasive composition) The composition may be added to the composition towel in an amount between about 0.005 vol% and about 2 vol% of the composition or between about 005 5% by weight and about 2% by weight of the composition. The inhibitor comprises poly Acrylamide, polyacrylic acid polymer, polycarboxylic acid copolymer, diethanolamine cocoamine From the acid diethanolamine, B 24 1307356 ~9Τ*^Τ2 ~~- 曰月曰修(more) replacement > sterol decylamine derivative or a combination thereof. The one or more stabilizers can be fully produced An amount of measurable improvement effect of the stability of the composition is present. The one or more stabilizers may be present in an amount ranging from about 100 ppm to about 5.0 weight percent (wt%). Preferred non-limiting examples of stabilizers include (but not limited to) amine tris(arylene), transethylidene-4_disc, hexamethylenediaminetetramethylene acid, diethylenetetramine pentamethylene Phosphoric acid and salts derived therefrom. The promoter is another example of an additive that may be included in the abrasive composition. The promoter promotes the electrochemical reaction of the deposited metal on the surface of the substrate to accelerate metal removal. The composition may comprise one or more promoters at a concentration of between about 5% by volume and about 1% by volume or between about 3% by weight and about 1% by weight. The promoter may comprise a sulfur containing compound such as a sulfite or a disulfate. Other examples of such abrasive composition additives are more fully described in U.S. Patent Application Serial No. 10/141,459, filed on Jan. 5, s. The degree does not contradict the features and disclosures claimed in this article. The substrate that has been raked is to be considered to have a better surface finish (including less surface defects such as dishing, erosion). The dielectric traces around the metal features 1 and □ and better flatness. And treatment: due to the bias between the electrode and the substrate can be removed ', sub-electric materials, because 25 1307356 bucket in the processing In the case of the tank (such as the above-mentioned tank 2), the square-shaped right-hand bamboo power is applied to the substrate having the upper or the conductive material layer. In one example of the grinding method, the substrate 208 is a household千千·>, τ is the Φ ^ ^ of the polishing head 202 used in the planarization method as shown in Fig. 1. A. The polishing head 202 is in contact with the polishing pad assembly 222 so as to be about 1 Λ. '〇1 The pressure in the range between psi and about PS1, for example, between about 〇· psi盥® βη ^ PSi, is applied to the substrate to be electrochemically mechanically polished. The polishing pad assembly 222 is configured in the text. The electrolyte of the human body is in the tray. The substrate 208 is in contact with the abrasive composition, 卄b Any of the ceramics is in electrical contact with the conductive pad 203. A bias from the power source 224 is then applied between the substrate 2〇8 and the conductive germanium 203. This bias is typically provided at a current of approximately ι mA. Density and comprising a treated substrate of up to about 3 Å (for example, for a 200 mm substrate, a current density of between about 〇ι and about 4 〇 mA W <), producing a conductive material from The anode of the substrate surface is dissolved. The bias voltage may vary depending on the power and distribution mode, depending on the user's requirements for material removal from the substrate surface. It can also be biased by an electrical pulse modulation technique. The technique applies a constant current density or a constant voltage during the first time period, and then applies a constant reverse current density or a constant reverse voltage during the second time period, repeating the first and second steps as described in 2〇 U.S. Patent No. 6,379,223, issued to the U.S. Patent No. 6,379,223, the entire disclosure of which is incorporated herein by reference. Special Point and reveal the content. 26 1307356 This bias is typically applied to the surface of the substrate in contact with the abrasive composition, approximately 1 M00 person/min (eg, between approximately 1 A/min and approximately 15, _ / min) The copper-containing material is removed at a rate of. In the present invention - the specific embodiment of the copper material to be removed has a thickness of less than 5, and the cap A can be applied to provide a removal rate of between about 100 A/min and about 5 The voltage of 0 A/min. The substrate is contacted with the abrasive composition and distributed over a period of time sufficient to remove at least some or all of the desired material deposited on the substrate. . Although the exact mechanism for flattening the substrate is not known, the flatness is as follows. Forming due to the surface of the substrate and the corrosion inhibitor or other material capable of forming a passivation film or a barrier film with the material to be removed (for example, a chelating agent capable of forming an oxidizing "oxidizing agent and/or forming a chelate layer") Attenuating: and/or electrically isolating the passivation layer on the surface of the substrate. Applying a bias voltage to the anode

〉 Valley solution removes the material from the surface of the substrate; 隹A 1 π is called 咏 咏 及 and promotes the removal of conductive materials (such as copper-containing materials). The passivation layer isolates or inhibits the anodic dissolution current, while providing mechanical grinding between the substrate and the permeable disk, by the contact area between the permeable disk and the substrate (eg, by surface formation on the over deposited substrate or The tip of the next topography is removed) the passivation layer is removed to expose the underlying copper-containing material. The passivation layer will remain in the area with minimal or no contact, such as a recess or valley in the surface of the substrate. (4) The exposed steel-containing material is electrically connected to the electrolyte, and the material can be removed by anodic dissolution. With respect to the removal of the conductive material under the passivation layer, the purification layer is selectively removed from the tip by contact with the abrasive object (eg, under the application of a bias voltage 27 1307356 months '' repair (more) replacement The copper-containing material of the page has no surface on the surface of the substrate: m + 'make too much white for the purification of the fraction with more. The copper-containing material without the purification layer is formed above or is removed" so that the tip formed above the substrate: There are more cuts in the solution and color valley, which leads to the substrate table: the flatness of the full weight on the substrate. In addition, the grinding pressure is reduced by grinding and anode transfer. (ie, about 2. Allows grinding of the surface of the substrate. Smaller _ ^ Μ or smaller) to rub the force, making this method suitable for flatness == shear force and frictional contact-sensitive foundation The surface of the material (for example, grinding low-k 塾: has less or at least the result of grinding), and it has been observed that the smaller shear and friction are reduced in the grinding or Make appearance defects (such as concave makeup red ^ to a minimum. U such as concave twist Grinding and Scratching Formations The following non-limiting examples are provided to further illustrate the specific embodiments of the present invention. However, these examples are not intended to be used in all or to limit the scope of the invention described herein. 1 : The following grinding composition was purchased from American Applied Materials (to add

Clara, California) Reflected on the Reflecti〇n® system, the iron steel wafer was ground and flattened. Α 28 1307356 ί π . : ' ! ί 片 replacing fl ] ί about 6 vol% phosphoric acid; about 2 vol% ethylenediamine; about 2 wt% ammonium citrate; about 〇. 3 wt% benzo Triazole; between about 2% by volume and about 6% by volume of potassium hydroxide to provide a pH of about 5; about 0.45% by volume of hydrogen peroxide; and deionized water. Example 2: The copper plated wafer was ground and planarized using a modified composition of the following abrasive composition in a modified cell from the Reflection® system available from Applied Materials, Inc. (Santa Clara, California). About 6% by volume of phosphoric acid; about 2% by volume of ethylenediamine; about 2% by weight of ammonium citrate; about 0.3% by weight of stupid triazole; between about 2% by volume and about 6 by volume. /. The potassium hydroxide is used to provide a pH of about 5; about 5% 5% by volume of hydrogen peroxide; about 0.15% by weight of cerium oxide (SiO 2 ) abrasive; and deionized water. 29 1307356 n ^-r22 Example 3: The key copper wafer was ground and planarized in a modified tank from the Reflection® system available from Applied Materials, Inc. (Santa Clara, Calif.) using the following abrasive composition . About 6% by volume of phosphoric acid; about 2% by volume of ethylenediamine, about 2% by weight of citric acid; about 3% by weight of benzotriene; between about 2% by volume and about 6 by volume Between the %, potassium hydroxide is used to provide a pH of about 6; a large, force 11% by weight of a dioxide (Si〇2) abrasive; and deionized water. Further embodiments of the invention are not limited by the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS In order to achieve and understand in detail the present invention, the present invention has been briefly described. It should be noted, however, that the by-laws' should not be construed as merely a representative embodiment of the present invention. The present invention allows for a cross-sectional view of one embodiment of a polishing process station. [Simplified Description of Component Symbols] 200 Processing Tank 202 Grinding Head 203 Conductive Pad 204 Disk 206 Base 207 Pad 208 Substrate 209 Electrode 210 ' 23 6 Drive System 214 Cover 216 Cap 218 Port 220 Valve 222 Grinding 塾 Combination 223A ' 223B inlet wire 224 power supply 226 slip ring 228 receiving disk 230 out σ 232 conveying system 234 bearing 238 buckle 242 grinding composition supply 244 bottom 246 side wall 250 processing device 252 arm 254 post 256 shaft 258 processing element

31

Claims (1)

1307356月/$曰修(更)本本|10. Patent application scope: 1. A method for processing a substrate, comprising: disposing a substrate having a layer of conductive material formed thereon with a first electrode a processing apparatus with a second electrode, wherein the substrate is electrically contacted with the second electrode; an abrasive composition is provided between the first electrode and the substrate, wherein the abrasive composition comprises: An acid-based electrolyte system; one or more chelating agents having at least one amino functional group, a guanylamino S-energy group, or a combination thereof; one or more antiseptic inhibitors; one or more organic acid salts; one or more Providing an alkaline rhodium modifier having a pH value between 4 and 6; grinding particles; one or more oxidizing agents; and a solvent; hydrazine; 13⁄4 being ground into a 44» upper layer. The conductive abrasive article contacts to remove at least one passivation layer of the 八-u knife, wherein the conductive abrasive article is in contact with the first electrode; and between the first electrode and the first electrode a bias, and The method of claim 1, wherein the biasing is between 0.01 mA/cm 2 and 100 amps / / 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The current density between cm2 is applied to the substrate to initiate an anodic dissolution. The method of claim 1, wherein the acid electrolyte system is selected from the group consisting of a phosphoric acid electrolyte and a sulfuric acid system. The method of the electrolyte, the perchloric acid electrolyte, the acetic acid electrolyte, and the combination thereof. The method of claim 1, wherein the one or more chelating agents further comprise one or more A compound of a group consisting of a free carboxylic acid group, a dicarboxylic acid group, a tricarboxylic acid group, and a combination thereof. 5. The method of claim 1, wherein the one or more chelating agents are selected from the group consisting of The group consisting of ethylenediamine, hexamethylenediamine, amino acid, mercaptomethylamine, and combinations thereof. 6. The method of claim 1, wherein the one or more corrosion inhibitors have one or more Salivation. The method of item 6, wherein the one or more corrosion inhibitors are selected from the group consisting of benzotriazole, imidazole, benzimidazole, triazole, and having a hydroxyl group, an amine group, an imido group, a carboxyl group, a thiol group, a nitro group And a combination of a strepto-triazole, an imidazole, a benzimidazole, a derivative of a triazole, and a combination thereof, and a combination of 33 1307356. 8. The method of claim 1, wherein the one or The organic acid salt comprises an organic acid ammonium salt, an organic acid potassium salt or a combination thereof. 9. The method of claim 8, wherein the one or more organic acid salts are selected from the group consisting of ammonium oxalate, ammonium citrate, and succinic acid. A group consisting of ammonium, potassium dihydrogen citrate, dipotassium hydrogen citrate, tripotassium citrate, potassium tartrate, ammonium tartrate, potassium succinate, potassium oxalate, and combinations thereof. 10. The method of claim 1, wherein the one or more pH adjusting agents comprise: one or more assays selected from the group consisting of oxidizing, oxidizing, and combinations thereof. 11. The method of claim 1, wherein the abrasive particles comprise an inorganic abrasive, a polymeric abrasive, or a combination thereof. 12. The method of claim 1, wherein the one or more oxidizing agents are selected from the group consisting of peroxides, peroxide salts, organic peroxides, sulfates, sulfate derivatives, and elements having the highest oxidation state. a group of compounds and combinations thereof. 34. The method of claim 1, wherein the composition comprises: phosphoric acid; ethylenediamine; benzotriazole; ammonium citrate; potassium hydroxide to provide a pH of 5;矽 abrasive; and deionized water. 14. The method of claim 1, wherein the composition comprises: phosphoric acid; ethylenediamine; benzotriazole; ammonium citrate; potassium hydroxide to provide a pH of 5; hydrogen peroxide; Deionized water. 15. The method of claim 1, wherein the electrically conductive abrasive article is electrically coupled to the second electrode. 16. The method of claim 1, wherein the abrasive article and the substrate 35 1307356 are contacted by a grinding force between 0.0 1 p s i and 1 p s i . 17. The method of claim 1, further comprising providing relative motion between the abrasive article and the substrate. 18. The method of claim 4, wherein the one or more chelating agents are selected from the group consisting of amino acids, ethylenediaminetetraacetic acid, citric acid, tartaric acid, succinic acid, oxalic acid, acetic acid, adipic acid, Butyric acid, capric acid, caproic acid, caprylic acid, glutaric acid, glycolic acid, formic acid, fumaric acid, lactic acid, lauric acid, malic acid, maleic acid, malonic acid, myristic acid, soft fat A group consisting of acid, phthalic acid, propionic acid, pyruvic acid, stearic acid, valeric acid, and combinations thereof. 19. A method of processing a substrate, comprising: disposing a substrate having a layer of conductive material formed thereon in a processing apparatus comprising a first electrode and a second electrode, wherein the substrate is The second electrode is electrically contacted; an abrasive composition is provided between the first electrode and the substrate, wherein the abrasive composition comprises: phosphoric acid; ethylenediamine; benzotriazole; ammonium citrate; 36 1307356 hydrogen a potassium oxide for providing a pH of 5; a cerium oxide abrasive; hydrogen peroxide; and deionized water; contacting the substrate with a conductive abrasive article in the abrasive composition; at the first electrode and the first A bias is applied between the two electrodes; and the conductive material is removed from the layer of electrically conductive material. 20. The method of claim 19, wherein the bias is applied to the substrate at a current density of between 0.01 mA/cm2 and 100 mA/cm2 to initiate an anodic dissolution. The conductive abrasive article and the substrate are contacted by a grinding pressure between 0.01 psi and 1 psi. 21. The method of claim 19, wherein the electrically conductive abrasive article is electrically coupled to the second electrode. 22. The method of claim 19, further comprising providing relative motion between the electrically conductive abrasive article and the substrate. 37