TW567551B - Polishing fluid for metallic film and method for producing semiconductor substrate using the same - Google Patents

Abstract

The purpose of the present invention is to provide a polishing fluid for a metallic film which exhibits an etching rate of 10 nm/min or less, a finishing rate at a load of 10 KPa of 200 nm/min or more and a contrast, which means a ratio of the finishing rate to the etching rate, of 20 or more; and a method for producing a semiconductor substrate using the polishing fluid.

Description

567551 Α7 Β7 V. Description of the Invention (1) Technical Field The present invention relates to a honing liquid for a metal film for honing a metal film formed on a semiconductor substrate, and a method for manufacturing a semiconductor substrate using the same. With the rapid advancement of technology, integrated circuit tends to be miniaturized and multilayer wiring. The multilayer wiring of the integrated circuit is an important factor that the unevenness of the semiconductor surface becomes extremely large. It also results in the disconnection, low capacitance, and electromigration caused by the miniaturization of the integrated circuit. The yield decreases, which leads to reliability. Cause of sexual problems. Therefore, to this day, various processing technologies have been developed for the planarization of metal wiring and interlayer insulating films on multilayer wiring substrates. One is C MP (C hemica 1 M echanica 1 Ρ ο 1 ishing: chemical mechanical honing) technology. . The CMP technology is a necessary technology for the planarization of interlayer insulating films, the formation of buried wiring, and the formation of lead pins in semiconductor manufacturing. C MP is a flat wafer usually made of semiconductor materials loaded on a carrier. It is carried out by pressing the wet honing pad with a certain pressure while rotating the carrier and the honing pad. At this time, the honing liquid introduced between the wafer and the honing pad is mainly used for honing the wiring and the convex portion of the insulating film to achieve flatness along with the chemical action. A variety of honing solutions and honing methods have been proposed for honing metal films on semiconductor substrates. For example, Tomi Goro is waiting for "Semiconductor Flattening CMP Technology" (issued in July 1998, issued by the Industrial Survey Committee) ##-(Please read the precautions on the back before filling this page) Order the Ministry of Economic Affairs Printed on the paper of the Intellectual Property Bureau staff consumer cooperative, the paper size is applicable to the Chinese National Standard (CNS) M specification (210X 297 mm) -4- 567551 A7 —_B7 _ V. Description of the invention (2) (Please read the precautions on the back before Fill out this page) Ministry of Economic Affairs, Intellectual Property Bureau, (printed by the Industrial and Consumer Cooperatives, page 2 3 and 5). The metal film is CMP, and the oxidizing agent in the honing liquid inertizes the chemical oxidation on the surface of the metal film. Under the condition of slightly corroding (etching) metal such as acid range, mechanical honing is performed by honing pads and abrasive grains. For example, honing fluids for metal films made of aluminum and the like formed on semiconductor substrates are available. Alumina is abrasive grains, which are dispersed in a nitric acid aqueous solution below ρ Η 3 (U.S. Patent No. 4,702, 792), and abrasive grains made of alumina and silica. , Mixed with acidic aqueous solutions such as sulfuric acid, nitric acid, acetic acid, etc. Honing fluid (U.S. Patent No. 4,944,836), etc. Among them, honing fluid is usually used, such as honing fluid in which alumina is dispersed in hydrogen peroxide and phosphoric acid aqueous solution (U.S. Patent No. 5,209,8 1 6 No.), etc., using alumina or silicon oxide as abrasive grains and dispersing it in an oxidizing solution such as hydrogen peroxide. However, alumina is used as a abrasive grain for flattening a metal film on a semiconductor substrate. Although the α-type has a high honing rate during the conversion, defects such as micro-scratches and orange peel are generated on the surface of the metal film and the insulating film. On the other hand, 7 * type, amorphous alumina or silicon oxide is used. In the case of abrasive grains, although micro scratches on the surface of the metal film and insulating film, orange peel, and other defects can be suppressed, there is a problem that the honing rate cannot be sufficient when honing the metal film. In this way, alumina, oxidation Grinding fluids in which layered particles of silicon and other metal oxides are dispersed in an aqueous solution have problems with surface scratches caused by the poor dispersibility of the abrasive particles. In addition, when using liquid oxidant hydrogen peroxide as described above, Or use metal etchant such as ammonium persulfate (Japanese Unexamined Patent Publication No. 6-3 1 3 1 6 4), dishing due to excessive wet etching (the phenomenon that the center of the metal film is excessively honing compared to the surroundings in FIG. 1D), dents, voids, etc. For the occurrence of defects, etc., this paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 567551 A7 B7 when it is put into practical use. 5. Description of the invention (3) causes problems. (Please read the notes on the back before filling (This page) To improve it, a method for adding a chemical reagent (anti-etching, chelating agent, etc.) that can form a protective film on the surface of a metal film to a honing fluid (Japanese Patent Application Laid-Open No. 8-8 3 7 8 0 , Japanese Patent Application Laid-Open No. 1 1-1 9 5 6 2 8). However, if such a chelating agent is used, the rate of uranium can be suppressed to prevent the occurrence of dishing, etc. However, since the protective film is also formed on the part to be honed, the problem of extremely reduced honing rate is caused. To prevent this, the amounts of etchants and chelating agents can be optimized, but the conditions that meet the performance of the two are difficult to find and are easily affected by the program conditions. Therefore, there is a problem that the results cannot be reproducible. In addition, in order to obtain a honing rate of 200 nanometers / minute or more, there is a person who removes the protective film with a high honing pressure of 20 kPa or more (Japanese Patent Application Laid-Open No. 2000-252242) and becomes the future. The mainstream porous low-dielectric insulating film has problems of film strength and adhesion to the substrate. If excessive stress is applied to the substrate, the insulating film peels off and breaks. In addition, when honing pressure is increased and the honing pad is used for mechanical honing, the honing pad is more susceptible to the surface of the pad during honing. So far, it has been difficult to repair and control the surface state of the pad, and program management has become more difficult. In addition, the consumption of expensive honing pads is accelerated, and the process cost increases. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, polycondensed oxyacids, especially isopolyacids, such as the "Chemistry of Polyacids" edited by the Japanese Chemical Society (issued by the Society Publishing Center in August 1993) is also recorded It has strong acidity and oxidation effect, and its use in the passivation treatment and etching of metals has been disclosed in Special Table No. 9-5105 5 11 and so on. Examples of actual use of heteropolyacids as semiconductor surface etchants, or (Applied Surface Science vol. 135, NO. 1/4, pp 65-70 (1998.10.8)), also try to apply the Chinese standard to this paper standard ( CNS) A4 specification (210X297mm) -6-567551 A7 B7 V. Description of the invention (4) Polyoxylated acid or salt thereof as honing etchant (Japanese Patent Laid-Open No. 2 0 0 0 —1 1 9 6 3 Bulletin 9). (Please read the precautions on the back before filling this page.) In particular, the latter document states that only polycondensed oxyacid or its salt is used as the honing etchant (the first honing liquid composition), and more Two aspects of a conventional abrasive grain (second honing liquid composition) as a honing material. For the first honing liquid composition, because the isomeric acid alone is used as an etchant for honing the metal film, and the heteropoly acid is a liquid oxidant because it is soluble in water, it cannot meet the above honing rate and Dish performance. That is, in order to increase the concentration of the isomeric acid in order to increase the honing rate, the etching is also performed at the same time so that dishing occurs. On the other hand, if the above-mentioned isopoly acid is used as an isopoly acid salt by the action of an alkaline substance such as ammonia, although the etching rate is suppressed, the honing rate also decreases at the same time, and the honing cannot be effectively carried out effectively. Therefore, in order to improve the honing rate, there is a proposal to make the honing material containing the first type of honing liquid composition into the second honing liquid composition. It has a high honing load. Therefore, the object of the present invention for achieving a high honing rate with a low load is not desirable. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, there is also a proposal for the technology of dispersing abrasive particles in a liquid containing isopolyacid to make a chemical mechanical honing water dispersion (EP-A -1 1 2 3 9 5 6 ). However, at this time, in order to suppress the etchability of the dishing cause and obtain a high honing rate of more than 300 nanometers / minute, in fact, a high honing load of about 30 kPa cannot be applied. DISCLOSURE OF THE INVENTION The object of the present invention is to provide a feature that is capable of high speed even under low load. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 567551 Α7 Β7 5. Description of the invention (5) ( (Please read the precautions on the back before filling this page) Honing the metal film on the semiconductor substrate can control the etchability of the dishing cause to a low level, and because it does not contain abrasive particles required for mechanical honing, it can be suppressed Scratches, erosion (the phenomenon that the insulating film 2 around the metal film 4 in FIG. 1D is honed), and other defects on the honing surface are generated, and the metal formed on the semiconductor substrate without the complicated honing pad repair process is required. A honing liquid for film honing, and a method for manufacturing a semiconductor substrate using the same. The present inventors have carefully studied in order to solve the above-mentioned problems. As a result, it has been found that if a specific metal film honing liquid is used for honing, the conventionally difficult etching suppression and the high-speed honing method under a low load can be achieved. The invention is also effective for a metal film on a fragile porous low-dielectric insulating film substrate, and the present invention has finally been completed. That is, the present invention is as follows. (1) Metals with an etching rate below 10 nm / min, a honing rate above 200 nm / min at a load of 10 kPa, and a ratio of the above honing rate to the uranium etching rate above 20 The film was honed. (2) A honing liquid for a metal film containing a polycondensed oxyacid and / or a salt thereof, an aqueous polymer and / or a nonionic interfacial active agent, and water. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (3) The honing liquid for metal film (2) above, which contains complex particles of polyoxygenated acid and / or its salt and nonionic surfactant. (4) The honing liquid for a metal film according to the above (2) or (3), which does not substantially contain abrasive particles. (5) A honing liquid for a metal film according to any one of the above (2) to (4), a polycondensed oxyacid and / or a salt-based heteropolyacid and / or a salt thereof. (6) A honing liquid for a metal film according to any one of (2) to (5) above, wherein η B L of the nonionic surfactant is 5 to 12; This paper size applies to Chinese National Standard (CNS) A4 specification (210'〆297 mm) 8 _ 567551 A7 B7 V. Description of the invention (6) (7) Nonionic surfactants carbon number 8 to The honing fluid for a metal film according to any one of the above (2) to (6) of a polyoxyethylene ether of a saturated local alcohol of 24. (Please read the precautions on the back before filling this page.) (8) Non-ionic surfactant is a honing fluid for metal film according to any one of the above (2) to (7) in a combination of two or more different H L B. (9) A manufacturing method of a semiconductor substrate including a honing process of a metal film formed on a semiconductor substrate, using the honing liquid for a metal film of (1) or (2) above at a load of 15 kPa or less Honed. (1 0) A method for manufacturing a semiconductor substrate including a process of honing a metal film formed on the semiconductor substrate using a honing turntable, using the honing liquid for a metal film of (1) or (2) above, The honing wheel has a relative speed of 40 m / min or more for honing. (1 1) The above (9) or (1 0) method of honing using a honing pad without refurbishing during the honing process. (1 2) In the honing process, any one of the methods (9) to (1 1) described above using a honing pad having an average surface roughness (Ra) of 100 nm or less. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (1 3) in the above honing process, using the honing liquid for metal film (1) or (2) above, honing with an honing pad containing an inorganic honing material The method of (9) or (1 0) above. (1 4) The method of any of the above (9) to (3), in which the permittivity (K) 値 of the insulating film constituting the semiconductor substrate is not more than 2.5. (1 5) Honing liquid for metal film (1) which does not contain abrasive particles. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -9-567551 A7 B7 V. Description of the invention (7 ) Brief description of the drawing (please read the precautions on the back before filling out this page) Figures 1A to 1D are schematic cross-sectional views of examples of metal wiring formation using cMP technology. Element comparison table 1: semiconductor substrate 2 · 'insulating film 3: barrier metal layer 4: metal film BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Industrial Cooperative Cooperative. The term "etch rate" as used in the present invention refers to the thickness of a metal film that disappears within a certain period of time when the substrate on which the metal film is formed is immersed in a honing liquid under strong stirring. Specifically, 80 milliliters of honing liquid was filled into a container having an inner diameter of 5 cm, and a homogenizer ULTRA-TURRAX Τ8 (mandrel S 8 Ν-8 G) manufactured by IKA-WERKE was used at 2 5 0 0 0 In a honing liquid stirred at rpm, immerse a 15 mm square substrate of a Si wafer with a metal film formed on the surface for about 3 minutes, and calculate the metal film that disappears per unit time from the metal film thickness measured before and after. Of thickness. The so-called honing rate in the present invention refers to the thickness of a metal film that has been honed under a specific condition by using a honing apparatus for a general semiconductor substrate under specific conditions. Specifically, using the honing device made by Musashino Electronics Co., Ltd. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -1〇- 567551 A7 B7 V. Description of the invention (8) (Please read the back first Please fill out this page again) MA ~ 3◦0D (diameter of turntable 300 mm), honing pad for RHODEL-NITT A company IC — 1400 (made of foamed polyurethane), substrate for 1 micron thick 4 inch silicon crystal with Cu film, the honing liquid is supplied at a flow rate of 50 ml / min, and the honing is performed at a relative speed of 50 m / min between the substrate and the honing disc under a specific load. The thickness of the Cu film measured before and after was used to calculate the thickness of the metal film that disappeared per unit time. The present inventors have found that when using a honing fluid having the characteristics determined in the above-mentioned standardization within a specific range, high-speed honing can be performed with a low load, and the occurrence of surface defects such as scratches, dishing, and erosion can be suppressed. It also simplifies the program control such as the surface state of the honing pad, suppresses the consumption of the honing pad and reduces the process cost, and other excellent characteristics, and is used for honing the metal film on the semiconductor substrate. First, when using a honing fluid for a metal film with an etching rate of less than 10 nanometers per minute, the corrosion of the metal surface is suppressed, and the dry spots on the metal surface do not expand during honing. Increase. The Honor Workers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the second honing fluid for metal films. When the load is 10 kPa, the honing rate is more than 200 nanometers per minute, and the ratio of the honing rate to the etching rate In the case of 20 or more, the problems required by the CMP process under the low load condition of improving honing performance to prevent dishing and other short honing time can be taken into consideration. The honing fluid having standardized properties in the present invention includes a honing fluid containing polycondensed oxyacid and / or a salt thereof, a water-soluble polymer and / or a nonionic surfactant, and water. The honing fluid of the present invention is within a range not detrimental to the effects of the present invention described later, or as required according to the purpose. It may also contain other commonly used abrasive grains, oxidants and other ingredients. The paper size of the invention is applicable to the Chinese National Standard (CNS) M specification (210X297 mm) -11-567551 A 7 B7 V. Description of the invention (9) Purpose 'Especially does not substantially contain abrasive grains commonly used in conventional honing fluids It is its characteristic. The polyoxygenated acid used in the present invention contains Mo, V, W, T i, (Please read the precautions on the back before filling in this page}

Condensates of oxyacids such as Nb'Ta and other constituents are equivalents of polyacids and isopolyacids. The isopoly acid is a condensation oxy acid containing any of the constituent elements of the polycondensed oxyacid described above, and there are polymolybdic acid, polyvanadic acid, polytungstic acid, polytitanic acid, polyniobic acid, and polybasic acid. Among the present inventions for the purpose of metal honing, from the viewpoint of metal etching (oxidation, dissolution) capabilities, polymolybdic acid, polyvanadic acid and polyhelic acid are preferred. Printed by the Intellectual Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Heteropoly acid is obtained by adding a hetero element as the central element to the homopoly acid. Its composition includes a condensed coordination element, a central element, and oxygen. Here, the condensation coordination element refers to the constituent elements of the above polycondensed oxyacid. Among them, at least one selected from the group consisting of Mo, W, and V is a preferred example, and other elements such as N b and D a may also be contained. . The central element of the isopoly acid is selected from the group consisting of P, Si, As, Ge, Ti, Ce, Mn, Ni, Te, I, Co, Cr, Fe, Ga, B, V, Pt, Be, and Zn. At least one species in a group, and the atomic ratio of the condensed coordination element to the central element (condensed coordination element / central element) is 2.5 to 12. Specific examples of the aforementioned heteropolyacids include phosphomolybdic acid, silicomolybdic acid, phosphovanadic molybdic acid, silovanadic molybdic acid, phosphotungstic molybdic acid, silicotungstic acid 'phosphovanadium tungsten molybdic acid', silicovanadium tungsten molybdate, Phosphate vanadium tungstic acid, sand vanadium tungstic acid, phosphorus molybdenum niobic acid, boromolybdic acid, borotungstic molybdic acid, borovanadic molybdic acid, borovanadic tungstic acid, cobalt molybdate, cobalt vanadium tungstic acid, phosphotungstic acid , Phosphovanadic acid, silicovanadic acid, etc. 'but is not limited thereto. Among the above polycondensed oxyacids, those which are sufficient for etching metal from honing purposes -12- This paper size is applicable to China National Standard (CNS) specifications (male thin) 567551 A7

V. Description of the invention (10 (Please read the notes on the back before filling this page) The viewpoints of acid strength and oxidizing power are based on isopolyacid. Phosphomolybdic acid, sand molybdic acid and more Introducing vanadium phosphorus vanadium molybdic acid, silicon vanadium molybdic acid, etc. are more preferred. Polycondensed oxyacids can be used alone or in combination. The acidity of the honing fluid composition can be adjusted to control the honing performance. It is also possible to add an alkaline substance to these polycondensed oxoacids and use them as polycondensated oxoacids. Polycondensed oxoacids include the salts of the above polycondensed oxyacids and metals, mirrors, and organic amines. The content of the polycondensed oxyacid and / or its salt in the honing liquid of the invention is not particularly limited, but is preferably from 0.1 to 30% by weight, and more preferably from 0.5 to 15% by weight. Less than the above range It may be difficult to obtain a sufficient honing rate, and there is no significant improvement in honing performance beyond the above range. The water-soluble polymer used in the present invention is printed by S Industry Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Ethers such as glycol, polypropylene glycol, polyethylene glycol alkyl ether; polyvinyl alcohol, polyvinylpyrrolidine And vinyl polymers such as polyacryl; polyacrylic acid, polymethacrylic acid, polyacrylamide, polyammonium acid, polyacrylic acid ammonium salts and other polycarboxylic acids and their salts; methyl cellulose, hydroxypropyl fiber Polysaccharides such as cellulose, carboxymethylcellulose, cellulose acetate, nitrocellulose, cellulose sulfate, pectin, etc .; but also gelatin, starch, prion protein, etc., but not limited to these. These water-soluble polymers include Combined with honing fluid composition as a tackifier (Japanese Patent Application Laid-Open No. 8-3 0 2 3 3 8), and as a surfactant C (Japanese Patent Application Laid-Open No. 2 0 0-2 5 2 2 4 2) The purpose of the present invention is different. That is, a combination of a water-soluble polymer and the above-mentioned polycondensed oxyacid can finally maintain a high honing rate at a low load and suppress the progress of etching, and control the occurrence of dishing. Among the above water-soluble polymers, the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applicable from the scale of the etched paper. -13-567551 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) From the standpoints of rapid inhibition and high honing performance under low load, or the dispersibility of the particles produced, the viewpoints of polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, and cellulose derivatives are preferred. As for the added water-soluble polymer, not only the type, but also the molecular weight is strongly related to the performance of the honing fluid. Generally speaking, the larger the molecular weight of the water-soluble polymer added, the higher the etching inhibitory effect, and the dispersibility and honing rate of the particles can be taken into account. There are various results depending on the type of water-soluble polymer. The content of the water-soluble polymer used in the honing fluid of the present invention is not particularly limited. Depending on the kind, the type and amount of the polycondensed oxyacid (the salt) used vary, but it ranges from 0.01 to 50% by weight. Preferably, 0.05 to 30% by weight is more preferred. When it is less than the above range, it is difficult to obtain a sufficient etching suppression effect, and it is sometimes difficult to control the occurrence of dishing. Moreover, if it exceeds the said range, it may become difficult to take it, such as an increase in viscosity. The non-ionic surfactant used in the present invention can be used in combination with the above polycondensed oxyacid to maintain a high honing rate at a low load and to suppress the progress of etching to control the occurrence of dishing. Unexpectedly, this effect is not seen in the use of ionic surfactants, anionic surfactants, and cationic surfactants. Non-ionic surfactants, especially those with H L B in the range of 5 to 12, have obvious effects when used. Here HL Β (hydrophilic-lipophilic balance) is a parameter representing the hydrophilicity of the surfactant. The non-ionic surfactant used in the present invention is in the range of 0 to 20, and the larger the number, the higher the hydrophilicity. . Such non-ionic surfactants can use "Introduction to New Surfactants by Takehiko Fujimoto, Showa 60, January 1, 2010. Sanyo Kasei (Please read the precautions on the back before filling out this page) This paper is for China National Standard (CNS) Α4 Specification (210X297 mm) -14-567551 A7 _____ Β7 V. Description of Invention (12) (Please read the precautions on the back before filling this page) Industrial (stock) company "Page 9 2 Table Polyethylene glycol and polyol nonionic surfactants listed in 2 · 5 · 1. The above polyethylene glycol type non-ionic surfactants are those obtained by adding ethylene oxide to various hydrophobic groups to introduce hydrophilic groups, including higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, and fatty acid ethylene oxide adducts. Products, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid ammonium ethylene oxide adducts, ethylene oxide adducts of fats and oils, polypropylene glycol ethylene oxide adducts, and the like. On the other hand, polyhydric alcohol type non-ionic surfactants are those in which a hydrophobic fatty acid is bonded to a hydrophilic polyhydric alcohol via an ester or amidino group, including fatty acid esters of glycerol, fatty acid esters of pentaerythritol, sorbitol, Among these nonionic surfactants, fatty acid esters of sorbitan, fatty acid esters of sucrose, and fatty acid amides of alkanolamines, among them, HLB of 5 to 12 is more suitable for the present invention. If H L Β is less than 5, the formed abrasive particles become more hydrophobic, and sedimentation and delamination due to poor dispersion may occur. On the other hand, if H L B is larger than 12, the hydrophilicity becomes higher, particles are difficult to form, and the suppression effect of etching is difficult to appear. The non-ionic surfactant of the present invention is printed by the Industrial and Commercial Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and suitable ones are polyoxidation of higher alcohols having 8 to 24 carbon atoms classified as the above-mentioned polyethylene glycol surfactants. Vinyl ether, polyoxyethylene ether of alkyl phenol, and polyoxyethylene ether of polypropylene glycol (Plutonic type), among them, polyoxyethylene ether of higher alcohol having a carbon number of 2 to 4 is preferable. Also, the above-mentioned high-grade polyoxyethylene ethers having 8 to 24 carbon atoms have unsaturated types including carbon-carbon double bonds in molecules containing oleyl groups, and saturated types which do not contain at all. However, the paper size of the saturated gene is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -15-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 567551 A7 ______B7_ 5. Description of the invention (13) Not susceptible to oxidative deterioration Performance deteriorates over time, so polyoxyethylene ethers of saturated higher alcohols are preferred. Such items are, for example, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene 2-ethylhexyl ether, polyoxyethylene tridecane ether , Polyoxyethylene isostearyl ether, polyoxyethylene synthetic alcohol ether (the number of carbon atoms of the synthetic alcohol is 12 to 15), etc. By using one of these nonionic surfactants alone or using two or more different HLBs, the honing fluid of the present invention has excellent properties, such as high dispersibility of the honing particles, low etchability and low High-speed honing under load can be easily implemented. When two or more non-ionic surfactants with different HL Β are used, they can be mixed in advance or each can be mixed with polyoxygenated acid (the salt) at the same time. Condensation of oxyacid (its salt) and mixing with low HL B are beneficial to maintain the high dispersibility of the produced honing particles at the same time, and promote low etching and high speed honing under low load. The content of the non-ionic surfactant used in the present invention is not particularly limited. Depending on the kind, the type and amount of the polycondensed oxyacid (the salt) used vary, but it is usually 0.1 to 50% by weight, preferably It is 0.5 to 25% by weight. Below the above range, there is no etching suppression effect, and the occurrence of dishing cannot be controlled. Above the above range, it is sometimes difficult to obtain it due to an increase in viscosity or the like. The honing fluid of the present invention is characterized by containing a water-soluble polymer and / or a nonionic surfactant, and it is preferable to use a nonionic surfactant in order to obtain a high honing ratio. The honing fluid of the present invention is usually water as a medium. Polycondensed oxyacid (its salt) The paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -16-" (Please read the precautions on the back before filling this page)

567551 Printed by A8 Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7_ V. Description of the invention (14)) 'Soluble or disperse of water-soluble polymers and / or non-ionic surfactants' is usually agitated for homogeneous use It is better to use a fully dispersed method such as an ultrasonic machine, an ultrasonic wave, and a wet media grinder. The honing liquid prepared in this way is based on the interaction between polyoxygenated acid (its salt) and water-soluble polymer and / or non-ionic surfactant, so that polyoxylated acid (its salt) becomes a highly water-soluble component. The complex (microcell particles) of the microcells formed by the molecules and / or non-ionic surfactants is preferably present in water in a highly dispersed state. In particular, nonionic surfactants are preferred because the complex particles are easy to form. The so-called composite can basically be measured by the wet particle size analysis method described later, or the structure can be observed with a transmission electron microscope, and the number average particle size measured by the wet particle size analysis is about 10 nm to 1 micron is preferred. Here, the number average particle diameter is less than about 10 nanometers, or even the fineness of which the viscosity cannot be measured. Although it is included in the scope of the present invention in a highly dispersed state, its composition is generally high in viscosity, and honing is considered. It is better to measure the particle size and observe the structured composite particles. The detailed honing mechanism of the honing fluid of the present invention is unknown, but it should be microcellular particles formed by the interaction of polycondensed oxyacid (its salt) with water-soluble polymers and / or non-ionic surfactants. Honed particles with a chemical honing effect maintain low etching and control the occurrence of dishing, and at the same time, a high honing rate can be achieved under low load. As such, in the present invention, the honing particles are microcellular particles, and the abrasive particles used for mechanical honing are essentially different in characteristics, so the agglomerated abrasive particles are scratched, and the substrate of the substrate is caused by the load during honing. Damage and other problems in conventional mechanical honing can be eliminated. i Paper size applies to China National Standards (CNS) A4 specification (2 丨 〇'〆297mm) "17-" (Please read the precautions on the back before filling this page) 567551 A7 __ B7 V. Description of the invention ( 15) (Please read the precautions on the reverse side before filling out this page) The honing fluid of the present invention can be added to Ruianqian mechanical honing elements in order to increase the honing rate, as long as it does not cause scratches and other problems. The use of abrasive grains is characterized by being substantially free of abrasive grains. The content of abrasive grains is preferably less than 1% by weight. The abrasive grains here include silicon oxide, titanium oxide, hafnium oxide, alumina, and zirconia. Inorganic particles such as magnesium oxide; styrenic copolymers, acrylic copolymers, polyvinyl chloride, polybutyral, saturated polyester, polyamide, polyimide, polycarbonate, phenoxy resin, Organic particles such as polyolefins and olefin-based copolymers; organic particles such as amorphous carbon and carbon black. Inorganic particles with high hardness are usually used for mechanical honing purposes. The present invention is printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 硏Very low etchability of the metal film due to the polishing liquid In general, it is not necessary to use a protective film forming agent, and within a range that does not substantially reduce the honing rate, if necessary, a compound that forms a chelate compound or a complex with a metal film can be added to further suppress the etching. Especially When the metal is copper or copper alloy with copper as the main component, it is effective to add benzotriazole and quinalic acid as chelating agents. Etchant also includes benzotriazole, benzotriazolecarboxylic acid and other benzo Triazole derivatives, cystine, halogenated acetic acid, glucose, dodecanethiol, etc. The addition amount of these resists is below 100 ppm, preferably below 50 ppm, which is used for practice It is sufficient to know that the honing material is very small. Conversely, if the amount of honing material is large, the honing rate will decrease, and the target honing performance must not be poor. The honing liquid of the present invention is to improve the honing rate of the metal film without causing excessive Within the scope of etching, conventional oxidants may also be included. The oxidants included may be known oxidants, such as hydrogen peroxide and other peroxides, perchloric acid, perchlorate, periodate, periodate, peroxide Sulfuric acid, persulfate, nitrate, etc. The honing fluid of the present invention is necessary Can also contain more acid, depending on the type of acid used. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210〆297 mm) -18-567551 Α7 Β7 V. Description of the invention (16) (Please read the note on the back first Please fill in this page again for more details), the honing performance of the p Η 'metal film of the resulting slurry can be controlled. The acids that can be included are known inorganic acids, such as sulfuric acid, phosphoric acid, nitric acid, etc., or known organic acids, For example, oxalic acid, citric acid, malic acid, acetic acid, etc. In the honing composition of the present invention, if necessary, water-soluble alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and glycerol may be added. The prepared honing fluid of the present invention is suitable for honing and flattening a metal film formed on a semiconductor substrate. The metal film system on the semiconductor substrate to be honed is known for wiring, plugging, contacting metal layers, and resistance. The metal film for the barrier metal layer includes, for example, a metal film made of a group of metals selected from the group consisting of aluminum, copper, tungsten, titanium, hafnium, aluminum alloy, copper alloy, titanium nitride, and nitride group. Among them, metal films made of copper and copper alloys with low surface hardness and defects that are prone to damage and dishing are more recommended, but they are also suitable for honing of barrier metals made of metals. When using the honing liquid of the present invention for honing, its maximum performance is the honing method which is characteristic of appliances. The present invention also relates to a method for manufacturing a semiconductor substrate including such a honing process. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The honing load is less than 15 kPa, preferably 10 kPa or less, and more preferably 5 kPa or less. This is because the honing fluid of the present invention can also obtain a high honing rate at such a low load, and it is not necessary to honing with a conventional high load. As a result, the substrate is not subjected to excessive stress during honing, and in the manufacture of semiconductors that have recently been introduced into porous low-dielectric insulating films that are expected to become mainstream, the problem of metal film peeling due to damage to the insulating film can also be avoided. And because the load is low during honing, the surface of the honing pad is not easily affected, and the surface state control of the complicated honing pad can be reduced. In addition, the consumption of honing pads can be suppressed. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -19-567551 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7 V. Description of the invention (17) Various effects such as reducing process costs. The relative speed of the semiconductor substrate and the honing turntable during honing is preferably as high as 40 m / min or more. That is, as in the present invention, if the honing element is extremely low, the honing liquid is brought into contact with the substrate at a high speed, and a higher honing rate can be obtained, which can shorten the honing time. In addition, when using the honing liquid for a metal film according to the present invention, there is a feature that a conventionally required honing pad repair process is not required. The term “refurbishment treatment” used herein refers to the process used to impart the initial sharpness of an unused honing pad, and / or the process of renewing the surface of a used honing pad. If there are foreign objects or burrs on the surface of the polishing pad, there will be scratches and other defects during honing. Most of them need to be slightly repaired. When using the honing fluid of the present invention, it is not necessary to mean the repair of the latter. That is, when using conventional honing fluids containing abrasive particles, a disc or ring processor with micro diamonds embedded on the surface can be used to make the surface of the honing pad fine, so that the abrasive particles in the slurry can be maintained. Between these fine hairs, the desired honing rate is achieved. Therefore, if the fluffing state of the surface of the honing pad is irregularly regulated, the honing performance will be deteriorated. In addition, honing pads have a foaming structure in order to improve the retention of abrasive particles in the slurry. The abrasive particles are buried in these holes with the honing process, which cannot be replaced with new abrasive particles, and the abrasive particle rate gradually decreases. Problem. To prevent this, refurbish the honing pad surface as well. However, since the present invention does not substantially contain abrasive particles, regular renewal for renewal is unnecessary. This not only eliminates the need for complicated repair processes, thereby simplifying the manufacturing process, but also suppressing the consumption of expensive honing pads and reducing manufacturing costs. The method of the present invention uses the average surface roughness (R a) to apply the Chinese National Standard (CNS) A4 specification (210 ×; 297 mm) at this paper size. -20-(Please read the precautions on the back before filling in this Page) 567551 A7 B7 V. Description of the invention (18) (Please read the precautions on the back before filling in this page) A smooth honing pad below 0 0 nm is suitable. In the past, in order to obtain the above-mentioned desired honing rate, the surface of the honing pad was intentionally roughened. However, if a honing pad with poor surface smoothness is used for honing, the surface unevenness may easily cause dishing. The problem of inability to do precision honing. On the other hand, in the present invention, since the honing pad having extremely high flatness of R a below 1,000 nm is used for honing, the characteristics of high honing rate can also be obtained, so it is not necessary Precision honing. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the method of the present invention can also be used as a honing pad with an inorganic honing pad. Generally, the honing pad is a foam of an organic polymer such as polyurethane. When honing a tantalum and a metal film containing a macro compound that is not easily etched, if the honing pad contains an inorganic honing pad, it can be imparted. Efficient honing of mechanical honing elements. A honing pad containing an inorganic honing material can be obtained by adding various kinds of inorganic honing materials to a resin such as polyurethane, and dispersing and forming the shape of the honing pad. Specifically, urethane resins are produced by mixing alcohol components such as diols, polyols, etc., which constitute the urethane resin, and compounds having isocyanate groups of two or more functions. Next, the inorganic resin is added and kneaded to the constituent resin produced in this way, and the inorganic resin is uniformly dispersed. Then, after forming it into the shape of a honing pad, a cross-linking reaction is performed by a method such as heat treatment to produce a honing pad containing an inorganic honing material. The inorganic aggregates used in the present invention include those commonly used as honing abrasive grains, and can be silica, titanium oxide, aluminum oxide, aluminum oxide, zirconia, chromium oxide, iron oxide, tin oxide, zinc oxide, composite At least one of metal oxide, metal hydroxide, silicon nitride, and titanium nitride. When these inorganic fillers are added to the honing pad resin, in order to improve the dispersion state and the affinity of the resin / inorganic filler interface, the organic silicon compound such as a silane coupling agent is used as the surface cover-21-This paper size applies to China National Standard (CNS) A4 Specification (210X297 mm) Intellectual Property Bureau of the Ministry of Economic Affairs 8 Industrial Consumer Cooperatives Printing Disaster 567551 A7 __B7 V. Description of Invention (19) Reprocessing. Such inorganic aggregates may be those having a particle size of 1 nm to 1 Q microns, and those having a particle size of 10 nm to 15 microns are particularly preferred. When the particle size is less than 1 nanometer, it is difficult to obtain a sufficient honing rate, and when it is larger than 10 micrometers, defects such as scratches are liable to occur during honing, which is not good. The amount of the inorganic resin added to the constituent resin is from 0.1 to 10% by volume, and more preferably from 1 to 5% by volume. If the addition amount is low, the effect of adding the inorganic honing material may not be sufficient. Conversely, if the amount is too large, problems may occur in the forming of the honing pad, and the hardness becomes too high, which may cause defects such as scratches during honing. As such a honing pad to which an inorganic material is added, for example, a MH C series manufactured by Rhodel Nitta Company can be used to add cerium oxide to a urethane resin. The present invention can be effectively used for a low-dielectric insulating film having a permittivity (K) 値 2 · 5 or less constituting an insulating film of a semiconductor substrate, and particularly a honing of a porous low-dielectric insulating film which is mechanically fragile. That is, in order to make the K 値 layer of the insulating film close to 1, it is discussed to introduce an air layer into the film to form a multi-layer structure. However, such a structure generally has a brittle film quality, and is a processed C M for a metal film formed thereon. During the P process, the metal film was peeled due to the destruction of the insulating film and insufficient adhesion. Therefore, in the CMP process, it is necessary to perform honing without exerting stress on the substrate as much as possible, and to make honing under low load conditions possible. The present invention meets the requirements of the process. A method for manufacturing a semiconductor substrate will be specifically described below. First, as shown in FIG. 1A, after an insulating film 2 is formed on a semiconductor substrate 1 such as a silicon substrate, a structure for metal wiring or an opening for connecting wiring is formed on the insulating film 2 by photolithography and etching. Secondly, as shown in Figure 1B, the grooves or openings formed in the insulating film 2 are formed by sputtering, CVD, and other methods. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the back (Please fill in this page again)

-22- 567551 A7 B7 V. Description of the invention (2C)) (Please read the precautions on the back before filling this page) to form titanium nitride (T i N), nitrided giant (T a N), etc. Barrier metal layer 3. Next, as shown in FIG. 1C, the metal film 4 for wiring is buried so that the thickness is greater than the height of the groove or opening formed in the insulating film 2. Next, as shown in Fig. 1D, the excess metal film other than the groove or the opening is removed by honing with the honing liquid of the present invention. The above method is repeated as many times as necessary to obtain a semiconductor substrate of an electronic component 'having a multilayer wiring structure. When such a semiconductor substrate is manufactured, the metal film on the semiconductor substrate may be honed by using the honing liquid for a metal film and a method for manufacturing a semiconductor substrate. Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. The evaluation of honing fluid characteristics and honing performance was performed by the following methods: < Particle size measurement > (1) Fine (less than 5 micron) particles · Using a wet particle size analyzer track UP A-9230) measurement. (2) Coarse (5 micron or more) particles: Measured with a wet particle size analyzer Horiba, Ltd. L A-700. Printed by the Intellectual Property of the Ministry of Economic Affairs ^ 7 Employee Consumer Cooperatives The average particle size shown here is the index average particle size. < Evaluation of surface defects (scratch) > After the silicon wafer being honed in the honing rate measurement was washed and dried, the plain surface of the semiconductor wafer was irradiated with local light in a dark room, and the presence of scratches was visually judged. \ \ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 567551 Printed by A7 B7 of the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) < Disc evaluation > Honing a 4-inch patterned wafer (SKW-2 size: oxide film 0 · 8 microns, T a N 25 naphthalene, Cu 1 · 5 microns) with the same load as the above honing rate measurement method An 8-inch wafer is cut into 4 inches.) Lines and gaps at 50-micron intervals are measured with a desktop small probe microscope: Nano pics (manufactured by Seiko Insturments). The C ια embedded in the gaps is measured. The amount of surface dishing. In the dishing evaluation, the measured honing rate is used to obtain the complete honing time for a specific film thickness, and then the honing time is added by 10% of the honing time (10% over honing). < Measurement of surface roughness (R a) of honing pad > The roughness of the surface of the honing pad was measured using a tabletop small probe microscope (Nanopics) used for the above-mentioned dishing measurement. < Honing conditions > Unless specified otherwise, honing is performed on the following conditions. • Honing device: Honing device MA-3 0 0 D made by Musashino Electronics Co., Ltd. • Load: 5 kPa • Relative speed of substrate and honing turntable: 50 m / min • Supply of honing fluid: 50 ml / Minute • Honing pad: 1C — 1400 (made of foamed polyurethane) fixed on a honing turntable, a 4-inch bare wafer with water film stretched, treated at a load of 20 kPa for 1 hour, remove the honing pad first Defects on the surface, such as burrs, (please read the precautions on the back before filling in this page) 丨 «The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) 24-Ministry of Economic Affairs / i ^ 7g ( Printed by the Industrial and Consumer Cooperatives 567551 A7 B7 5. The description of the invention (22) is used for substrate honing. However, the honing rate (PR 1 0) used to identify the honing liquid is under the load of 10 kPa. The following is For example, it is an example of a honing fluid combining a polycondensed oxyacid and a nonionic surfactant. Example 1 A polycondensed oxyacid phosphorus vanadium molybdic acid: PV Μ 〇 (trade name PV Μ — 1-1 1 Japan (Made by Inorganic Chemical Industry Co., Ltd.) 12 grams dissolved in 68 grams of water, add non-ionic interface Polyethylene oxide lauryl ether: SF — 1 (brand name BLAUNON EL — 1 50 0 3 P, HL B = 8. 3, manufactured by Aoki Oil Industry Co., Ltd.) A mixture of 18 g and 102 g of pure water to obtain a metal Honing fluid for film. Characteristics of the honing fluid prepared in this way (ER: Etching rate, PR i: Honing rate at load of 10 kPa, contrast: PR i 〇 / ER, average particle size) and specific 硏The performance evaluation results under the grinding conditions (PR: honing rate, dishing amount, scratch) are shown in Table 10. Example 2 Non-surfactant SF-1 was changed to polyoxyethylene oleyl ether: SF-2 (commodity Except for the name BLAUNON Ν—905, HLB = 8 · 9, manufactured by Aoki Oil & Fats Industry Co., Ltd.), the honing fluid for metal film was obtained in exactly the same manner as in Example 1. The evaluation results are shown in Table 1. Example 3 This paper size applies the Chinese national standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

-25- 567551 A7 B7 V. Description of the invention (23) In the honing composition obtained in Example 2, benzotriazole (BTA) was added to a concentration of 50 PP m to obtain a metal film for a resist with a photoresist. Grinding fluid. The evaluation results are shown in Table 1. Example 4 A honing liquid for a metal film was obtained in the same manner as in Example 1 except that polymolybdic acid containing silicomolybdic acid: S i Μ0 (trade name S M Japan Inorganic Chemical Industry Co., Ltd.) was used. The evaluation results are shown in Table 1. Example 5 Non-surfactant SF-1 was changed to polyethylene oxide lauryl ether: s F — 3 C Trade name BLAUNON EL — 1502.2, HLB = 6 · 3, manufactured by Aoki Oil & Fats Industry Co., Ltd.) 12 g of a mixture with 108 g of pure water Other than that, exactly the same as in Example 1 to obtain a honing liquid for a metal film. The evaluation results are shown in Table 1. Example 6 Dissolve 6 g of polycondensed oxyacid PVMo in 74 g of water, add a mixture of 16 g of non-ionic surfactant SF-16 and 54 g of pure water under stirring in a homogenizer, and then add non-ionic interfacial activity Agent: a mixture of 6 g of s F -3 and 54 g of pure water to obtain a honing liquid for a metal film. The evaluation results are shown in Table 1. Example 7 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297) (please read the precautions on the back before filling this page), -ιτ Printed by the Consumers ’Cooperative of the Intellectual Property Field of the Ministry of Economic Affairs-26- 567551 A7 B7 V. Description of the invention (24) Polyoxymethylene PV Μ 1 12 g dissolved in 68 g of water, and under the stirring of a homogenizer, a non-ionic surfactant polyoxyethylene crotyl ether is added: s F — 4 C Trade name BLAUNON CH— 305, HLB = 9 · 4 'Made by Aoki Oil and Fat Industry Co., Ltd.) 8 g and 5 2 g of pure water' followed by non-ionic surfactant polyethylene oxide 2-ethylhexyl ether: SF-5 (trade name: BLAUNON EH-2, HLB = 8 · 1, manufactured by Aoki Oil & Fats Industry Co., Ltd.) was a mixture of 3 g and 57 g of pure water to obtain a honing liquid for a metal film. The evaluation results are shown in Table 1. Example 8 Non-ionic surfactant SF-4 was changed to polyethylene oxide stearin: s F — 6 C Trade name: BLAUNON SR — 705, HLB = 9.2 (manufactured by Aoki Oil Industry Co., Ltd.), it was exactly the same as the implementation Example 7 A honing liquid for a metal film was obtained. The evaluation results are shown in Table 1. (Please read the precautions on the back before filling in this page)-Example 1 Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Industrial and Consumer Cooperatives, Example 9 Polycondensed oxyacid PV Μ ο 1 2 grams dissolved in 68 grams of water, Add the above non-ionic surfactant ·································································································· ~ Human 1 ^ 〇1 ^ 0 Yet another 20, HLB = 5 · 7, manufactured by Aoki Oil & Fats Industry Co., Ltd.) 2 g and 58 g of pure water were obtained to obtain a honing solution for metal film. The evaluation results are shown in Table 10. This paper size is in accordance with Chinese National Standard (CNS) A4 (21〇X; 297 mm) -27- 567551 A7 B7 V. Description of the invention (%) Example 10 < In the examples Add the benzotriazole (BTA) to the obtained honing liquid to a concentration of 50 ppm to obtain a honing liquid to which a resist is added. The evaluation results are shown in Table 1. Example 11 1 Dissolve 74 g of polyoxymethylene PVOM in water and add a mixture of non-ionic surfactant SF-2 2 4 g and 96 g of pure water under stirring in a homogenizer to obtain Honing fluid for metal film. The evaluation results are shown in Table 1. The honing fluid has a high viscosity. Example 1 2 The honing load was increased to a value other than 2 5 kPa, and honing was evaluated as in Example 1. The results are shown in Table 1. Example 1 3 The relative speed of the substrate and the honing turntable was reduced beyond 19 m / min, and the honing evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. Example 1 4 The honing liquid obtained in Example 1 was used to form a substrate having a porous structure of a methylsesquioxane type insulating film having a permittivity of 2.1 and a Cu film having a thickness of about 0.8 micron. Honing experiment. Honing conditions are the same as in Example 1, with a low load of 5 kPa, and there will be no Cu film peeling or cracking at the end of honing. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). (Please read the precautions on the back before filling out this page.) Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Printing Disaster-28- 567551 Α7 Β7 V. Observations of the Invention (%) 26. The honing fluid containing fine particles thus obtained in the above-mentioned embodiment was dropped on a grid with a carbon supporting film, and was naturally dried into a micro-sample, and accelerated by a transmission electron microscope (HITACHI HF-2000) Voltage 200 kV) Observing the particle structure 'Confirmed the existence of particles with a polycondensed oxyacid embedded in the form of a nonionic surfactant. Although the particle size varies depending on the honing composition, it can be observed that those having a size of about 20 to 50 nm should be a more agglomerated structure. Comparative Example 1 Instead of the non-ionic surfactant, the same amount of anionic surfactant was used instead of sodium dodecylbenzene sulfonate: SF-8, which was exactly the same as in Example 1 to obtain a honing liquid for a metal film. This honing liquid is a homogeneous solution, and the particle size cannot be measured. The evaluation results are shown in Table 1. Comparative Example 2 Instead of the non-ionic surfactant, the same amount of cationic surfactant was used instead of lauryltrimethylammonium chloride: S F-9, which was exactly the same as in Example 1 to obtain a honing liquid for a metal film. The evaluation results are shown in Table 1. Comparative Example 3 12 g of polyoxophosphate vanadium molybdic acid: P V Μ ο was dissolved in 188 g of water and used directly as a honing liquid for a metal film. This honing liquid is in a uniform solution state because it does not contain a surfactant, etc., and the particle size cannot be measured. The evaluation results are shown in Table 1. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperative, -29- 567551 A7 B7 5 Explanation of the invention (27) Comparative Example 4 12 g of polyoxoammonium ammonium molybdate molybdate · · NP Μ 〇 ((N Η 4) 3 [PM〇i2〇4〇] made by Japan Inorganic Chemical Co., Ltd.) is sufficient After crushing, 88 grams of water was added and dispersed in a homogenizer. Next, add 1000 g of colloidal alumina (average particle size: 130 nm, manufactured by Catalyst Co., Ltd.) to the above composition to a concentration of 6% abrasive, and then use a homogenizer for dispersion treatment to obtain alumina-containing particles. Honing liquid for abrasive metal film. The evaluation results are shown in Table 1. Comparative Example 5 6 g of citric acid was dissolved in 62 g of water, 0.4 g of BTA was dissolved in 3 g of ethanol, and 100 g of colloidal alumina (same as above) was added to this honing liquid to make the abrasive grain concentration reach 6 %, And finally add 28 grams of hydrogen peroxide (special grade reagent, 30% aqueous solution) to prepare a honing solution for metal film. The evaluation results are shown in Table 1. Comparative Example 6 Phosphovanadyl molybdic acid CPV Μ) 5 grams dissolved in 195 grams of water, with stirring in a homogenizer, KOH was added to pH 3.5, and colloidal alumina (same as above) was added to honing The concentration of abrasive particles in the liquid reaches 3%, and the honing liquid for metal film is prepared. The evaluation results are shown in Table 1. Comparative Example 7 This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) (Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives -30- 567551 A7 _ B7 V. Description of the invention (28) The weight of the abrasive particles was changed to other than 30 kPa, and the honing evaluation was performed as in Example g. The results are shown in Table 1. Comparative Example 8 Under the honing conditions of Comparative Example 7, as in Examples 1 and 3, a silicon silicon silsesquioxane-type insulating film having a porous structure with a permittivity of 2 · 1 was formed with a thickness of about 0.8 μm. The substrate of the film was subjected to a honing experiment. As a result, Cu is peeled during honing. From Table 1 and the results of the above examples and comparative examples, it can be seen that the relative speed of the honing liquid for a metal film of the present invention, which is a combination of a polycondensed oxyacid and a non-ionic surfactant, is 50 on the substrate and the honing turntable. Under the condition of meters / minute, the copper film also has a very high honing rate of more than 400 nanometers per minute under a load as low as 5 kPa. The lower the load, the better it is to avoid surface defects such as scratches. It is also known that the substrates which are made of fragile porous low-dielectric material for the insulating film can be smoothly polished. If the relative speed between the substrate and the honing disc is reduced, the honing rate tends to decrease, but the honing rate is still as high as about 300 nm / min. It is also known that the honing fluid of the present invention can exert its effect only when it is combined with a non-ionic surfactant, and it cannot be sufficiently combined with other anionic and cationic surfactants. It is also known that when using a honing fluid containing only isopoly acid, the etching property is too high and the desired properties are not satisfactory. On the other hand, if the uranium etching property of isopoly acid is suppressed in the form of ammonium salt and potassium salt, it is simultaneously honed. The performance deteriorates, even under the low load of 5 kPa, even if the abrasive particles are added, the honing rate must not be full. The following is an example of a honing fluid combining a polycondensation oxyacid and an aqueous polymer. This paper size applies to China's National Standards (CNS) A4 specification (210 > < 297 mm) (Please read the precautions on the back before filling out this page) Order printed by the Intellectual Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -31- 567551 A7 B7 Printed by the Intellectual Property of the Ministry of Economic Affairs 笱 Employee Consumer Cooperatives V. Description of Invention (29) Example 1 5 Dissolve polycondensed oxyacid PV 〇6 grams in water 154 grams, add the homogenizer under stirring, add Water-soluble polymer polyvinylpyrrolidone K 3 0: PVP (average molecular weight 40,000, manufactured by Wako Pure Chemical Industries, Ltd.) 6 g of an aqueous solution dissolved in 34 g of pure water to obtain a honing liquid for a metal film. The evaluation results are shown in Table 2. Example 16 6 g of polycondensed oxyacid PVMo was dissolved in 114 g of water, and an aqueous solution of 12 g of water-soluble polymer PVP dissolved in 68 g of pure water was added under stirring in a homogenizer to obtain a metal film for honing. liquid. The evaluation results are shown in Table 2. Example 1 7 6 grams of polycondensed oxyacid PVMo was dissolved in 62 grams of water, and the water-soluble polymer polyethylene glycol 4 0 0: PEG-1 (average molecular weight 3000, and 40 g of an aqueous solution dissolved in 92 g of pure water, to obtain a honing liquid for a metal film. This composition is a homogeneous solution, and the particle size cannot be measured. The evaluation results are shown in Table Example 8 8 6 g of polycondensed oxyacid PVMo was dissolved in 94 g of water 'with the stirring of a homogenizer, water-soluble polymer polyethylene glycol 2 0 0 0 0: this paper size Applicable to China National Standard (CNS) A4 specification (210X297 male thin) -32- (Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by M Industrial Consumer Cooperative 567551 A7 _B7 V. Description of the invention (30) PEG-2 (average molecular weight 20,000, manufactured by Wako Pure Chemical Industries, Ltd.) 30 g of an aqueous solution dissolved in 70 g of pure water to obtain a honing solution for a metal film. This composition is a homogeneous solution, and the particle size cannot be measured. The evaluation results are shown in Table 2. Example 1 9 Dissolve 9 g of polycondensed oxyacid PVMo in 123 g of water, add the water-soluble polymer PEG-115 g in an aqueous solution of 35 g of pure water under stirring in a homogenizer, and then add Non-ionic surfactant, the above-mentioned SF-1 18 grams, to obtain a honing solution for metal films. The evaluation results are shown in Table 2. Example 20 0 B TA was added to the honing composition obtained in Example 18 to a concentration of 50 p p m to obtain a honing solution for a metal film to which a uranium-resistant agent was added. The evaluation results are shown in Table 2. Example 2 1 Substitute non-ionic surfactant S F-1 and replace it with S F-2 Exactly the same as in Example 19 to obtain a honing liquid for a metal film. The evaluation results are shown in Table 2. Example 2 2 Dissolve polycondensed oxyacid PV 〇6g in water 168g, apply Chinese National Standard (CNS) A4 specification (210X297 mm) on the paper size (please read the precautions on the back first) (Fill in this page again)

-33- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial and Consumer Cooperatives, printed 567551, Α7 Β7 V. Description of the invention (31) Add water-soluble polymer PEG-16 grams of water solution dissolved in 14 grams of pure water while stirring the machine. Then, 6 grams of non-ionic surfactant s F-36 was added to obtain a honing solution for metal film. The evaluation results are shown in Table 2. Example 2 3 Dissolve polyoxoacid PV 〇9g in water 1 16g and ethanol 6g, add water-soluble polymer ρ V ρ 9g in pure water 5 1 under stirring in a homogenizer. G of the aqueous solution, and then added non-ionic surfactant SF-19 g, to obtain a honing solution for metal films. The evaluation results are shown in Table 2. Example 2 4 Dissolve 12 g of polycondensed oxyacid PVMo in 178 g of water, add the non-ionic surfactant SF-46 g under the stirring of a homogenizer, and then add the water-soluble polymer hydroxypropyl cellulose: Η PC (150 to 400 mPa · s, manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g of an aqueous solution dissolved in 3.6 g of pure water to obtain a honing liquid for a metal film. The evaluation results are shown in Table 2. Example 2 5 Using the honing fluids obtained in Examples 17 and 22, respectively, on a methylsilsesquioxane-type insulating film having a permittivity of 2.1 · with a porous structure, a thickness of about 0.8 microns was formed. The substrate of Cu film was subjected to honing experiments. Under the same honing conditions, under the load of 5 kPa, there is no Cu film at the end of honing. The paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the note on the back first (Fill in this page again)

-34- Lord of Intellectual Property Bureau, Ministry of Economic Affairs (printed by Industrial and Consumer Cooperatives, 567551 A7 ____ ΒΊ) V. Description of the Invention (32) Observation of peeling and cracking. Comparative Example 9 Add 6 grams of citric acid and 6 grams of water-soluble polymer PVP Dissolve in 60 grams of water, add 100 grams of colloidal alumina (same as above) to a concentration of 6% abrasive particles in the composition, then add 2 8 grams of hydrogen peroxide (special grade reagent, 30% aqueous solution), for the preparation of metal film Honing fluid. The evaluation results are shown in Table 2. From the results in Table 2, it can be seen that when combined with a water-soluble polymer, the polyoxylated acid is also used in combination with a non-ionic surfactant, which can suppress etching. A 1¾ honing rate is obtained. Also, when a polycondensed oxyacid is combined with both a water-soluble polymer and a nonionic surfactant, there is a tendency to obtain a higher honing rate. On the other hand, the polycondensation oxygen The combination of an etchant other than an acid with a water-soluble polymer can not suppress the etching property, and its use in honing will have problems with serious honing performance. The following is used to evaluate the repair operation of the honing pad in the present invention. Examples of the influence of honing performance. 2 6 In order to evaluate the honing fluid of the present invention, the refurbishing operation (the purpose of the refurbishment of the surface of the honing pad is not applied during honing). What effect will the honing performance have on the honing fluid used in Example 9 , Inject the edged honing turntable to fully soak the honed wafer, and hob a 4-inch blank wafer on the honing pad for 1 hour. Gently rinse the wafer with pure water using a nylon brush. The surface of the honing pad is not the entire paper size. Applicable to China National Standard (CNS) A4 (210X 297 mm). (Please read the precautions on the back before filling this page. )

-35- 567551 A7 B7 V. Description of the invention (33) Repair process. The honing performance was evaluated exactly as in Example 9 except that the honing pad was used. The surface roughness (R a) of the honing pad was 4 5 6 nm. The results are shown in Table 3. Example 2 7 The honing performance was evaluated in the same manner as in Example 9 except that the honing pad was a non-foaming honing pad (Ra = 120 nm) made of M F plastic disc with grooves (manufactured by SaMUSINO Electronics Co., Ltd.). The results are shown in Table 3. Comparative Example 10 The honing pad was repaired for 1 hour under a load of 3 kPa using a dresser with No. 100 embedded in diamonds before honing. The honing load was other than 30 kPa, exactly as in the comparative example. 5 Assess honing performance. The results are shown in Table 3. Comparative Example 11 The refurbished honing pad used in Comparative Example 10 was treated as in Example 26, and the honing pad in the unrenewed state was evaluated as in Comparative Example 5. However, the honing load is 30 kPa. It is known from the results in Table 3 that in the present invention, the honing performance equivalent to the initial stage can be obtained even if the honing pad is not frequently renovated in order to renew the honing pad. In addition, when using a honing pad with an extremely smooth surface, the honing rate will not be extremely reduced, and the resistance to dishing will also be improved. In contrast, those who are familiar with honing fluids containing alumina abrasive particles, although the honing rate can be improved, but the honing rate will decrease if the honing rate is not used for renewal during honing. This paper size applies to Chinese national standards (CNS> A4 size (210X297mm) (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Corporation of the Ministry of Economy ^ 7¾

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-36- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperative, 567551 A7 B7 V. Description of the Invention (34) Example 2 8 Using the honing liquid prepared in Example 9, and M HC 1 5 A (in urethane resin) Honing pads containing osmium oxide, manufactured by Rhodel Nitta Co.) Honed pads treated with a dresser No. 400 for 10 minutes, honing copper film, T a N film with a load of 5 kPa, honing The rates are each 580 nm / min and 80 nm / min. When honing the thermal oxide film under the same repair, it is about 1 nm / min, and there is almost no honing. At this time, there were no scratches on the honing surface. Secondly, the honing fluid was used, and the pattern wafer was honed according to the dishing evaluation method for 3 minutes, and the amount of dishing was measured to be about 70 nm. It can be confirmed that the T a N film other than the groove portion has disappeared at this time, and it cannot be measured by the metal film thickness. Comparative Example 1 2 198 g of polycondensed oxyacid was dissolved in 198 g of water to prepare a honing solution composed of polycondensed oxyacid. Except using this honing liquid, the evaluation was performed in the same manner as in Example 28. In other words, the honing rates of the copper film, the T a N film, and the thermal oxidation film were 5200 nm / minute, 30 nm / minute, and 1 nm / minute or less. In addition, the etching rate of the copper film is as high as 110 nm / minute. Next, using this honing liquid, honing patterned wafers to evaluate dishing. After the same honing, the dishing amount was measured after 3 minutes, and an average depression of about 400 nanometers was generated, and the groove part formed a partially etched shape. From the above results, it is known that when the honing liquid for the metal film of the present invention and the honing pad containing an inorganic honing material are used for honing, the copper film can be made up to 5 8 0 even under an extremely low load of 5 kPa. Nanometer / minute honing, and the standard of this paper is China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

-37- 567551 A7 _ —_B7 V. Description of the invention (35) The macro-hard compounds that are difficult to be honed can also have a high honing rate of 80 nm / min. In addition, even if there are different honing rates for copper and T a N, the honing of one of the two can control the dishing to a low honing. This should be because the honing fluid of the present invention has the feature of only honing the parts that are in contact with a certain force or more, even if it can be honed at a high speed compared to T a N film copper, the parts that are over honed are not affected. Load, and honing for this reason. On the other hand, since the honing method of the present invention hardly hones the silicon oxide film, the copper film and the barrier metal can be honed continuously, and the honing can be stopped on the oxide film, which is suitable for semiconductor processes containing complex CMP processes. Simplification contributes a lot. (Please read the notes on the back before filling this page)

Printed by Intellectual Property Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs -38- This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 male thin) 567551

V. Description of Invention (36)

(Qing first read the notes on the back before filling in this purchase

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-39- 567551

AB V. Description of the invention (37) Printed by the Intellectual Property of the Ministry of Economic Affairs of the Employees' Cooperatives ^ ππ Turning scratches 1 Whether there is no deer condensing curtains and subsequent development of the volume [nano] 〇〇to Ον S ID VO MD t—4 1 04 ίο CO 〇〇 &1200; 1200 m μ ~～ S S inch 〇r—Η § 〇 〇 On 〇g inch 〇CO VO 〇S Honing conditions $ long inch inch inch inch C < 1 oo inch inch inch CS 〇〇inch 04 〇〇inch inch refurbishment with or without deer stag condensed stag deer stag deer 丨 relative speed 1 [mifenzhong] load I [kPa] ^) UO honing fluid characteristic average particle size [奈M] 〇〇1 1 〇〇g ί—H 〇CO CO § Comparison PR / ER CN 8 rH r—Η S 8 to 〇cn PR10 [Namifen Clock] 〇inch inch s inch o cn > r ^ ί〇 〇CO 〇VO R VD m ω m CNI 〇; inch cn σ) oo r—H t >; ON inch Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example Example 23 Example 24 Comparative Example 9 (Please read the precautions on the back before filling this page) Order

This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -40- 567551

7 B V. Description of the invention (38) Employees of the Intellectual Property Office of the Ministry of Economic Affairs, printed by the cooperative, I Honing performance scratches ίκ I j \ w Lulu has a small amount of dishes I i [nanometer] IT) VO Os CNl CN | r Ή m ~ m Μ ο ^ Γ) dec CN Honing conditions ^ m r—Η 2660 Whether or not there is 裢 裢 relative speed for reconditioning [m / min] i load i [kPa] average particle size of honing fluid [Nano] S sr—Η, _ < f Η Contrast PR / ER 〇 γ—Η Ο ί 'i 1 ~ < PR10 [Nano / minute] 〇 tri Ο SS m ω meter CS Example 26 Example 27 Comparative Example 10 Comparative Example 11 • Packing-(Please read the notes on the back before filling out this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X 297 mm) -41-567551 A7 B7 5 Explanation of the invention (39) Industrial application possibility Using the honing liquid for metal film of the present invention, it is difficult for the conventional technology to suppress the etching and dishing, and at the same time, the metal film such as copper film can be suppressed under a low load. High-speed honing. Therefore, the honing liquid of the present invention is particularly effective for honing a metal film on a weak substrate such as a porous low-dielectric insulating film substrate. In addition, it also eliminates the need for a complicated honing pad repair process, which can greatly simplify the manufacturing process. As such, the present invention relates to materials having extremely useful properties for a honing tool for a metal film on a semiconductor substrate. The industrial use price is also very high. (Please read the notes on the back before filling this page)

Ministry of Economic Affairs Intellectual Property Gou B (produced by cooperation and industrial printing) This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -42-

Claims (1)

567551 Full I am correcting 0 8 r 8 8 8 8 ABCD Annex 2: VI. Application for Patent Scope No. 90 1 1 1 843 No. 5 Patent Application Chinese Application for Patent Scope Amendment (Please read the precautions on the back before filling this page ) Amendment on October M, 1992 of the Republic of China1. A honing fluid for metal films, characterized by a uranium etch rate of less than 10 nanometers per minute and a honing rate of 200 nanometers at a load of 10 kPa Minutes' and the ratio of the honing rate to the etching rate is 20 or more. 2. A honing fluid for a metal film, comprising a polycondensed oxyacid and / or a salt thereof, an aqueous polymer and / or a non-ionic interfacial active agent, and water. 3. The honing fluid for metal film according to item 2 of the patent application scope, which contains composite particles of polycondensed oxyacid and / or a salt thereof and a nonionic surfactant. 4 · The honing fluid for metal film as described in claim 2 or 3, which does not substantially contain abrasive particles. 5. The honing fluid for a metal film according to item 1 or 2 of the scope of application for a patent, wherein the polycondensed oxyacid and / or its salt is a heteropolyacid and / or its salt. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 · If the metal film honing fluid for item 1 or 2 of the patent application, the non-ionic surfactant Η B L is 5 to 12. 7. The honing liquid for a metal film according to item 1 or 2 of the scope of patent application, wherein the non-ionic surfactant is a polyoxyethylene ether of a saturated higher alcohol having 8 to 24 carbon atoms. 8. The honing fluid for metal film according to item 1 or 2 of the scope of patent application, wherein the nonionic surfactant is a combination of two or more different η L Β. This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 1 -'--- 567551 A8 B8 C8 D8 6. Scope of patent application (please read the precautions on the back before filling this page) 9 · One type contains The manufacturing method of a semiconductor substrate for the honing process of a metal film formed on a semiconductor substrate is characterized by using a honing liquid for a metal film such as the item 1 or 2 of the patent application scope at a load of 15 kPa or less. Honed. 1 〇 · A method for manufacturing a semiconductor substrate including a process for honing a metal film formed on a semiconductor substrate with a honing turret, characterized by using a honing liquid for a metal film as described in the first or second scope of the patent application, The relative speed of the semiconductor substrate and the honing turntable is 40 m / min or more for honing. 1 1 · The method according to item 9 or 10 of the scope of patent application, in which the honing process is performed by using a honing pad without refurbishing. 1 2 · The method of claim 9 or 10 in the scope of patent application, wherein in the above honing process, the average surface roughness of the honing pad (R a) is less than 100 nanometers. mill. 1 3 · The method as claimed in item 9 or 10 of the scope of patent application, wherein in the above honing process, the honing liquid for metal film as in item 1 or 2 of the scope of patent application is used, and the honing solution containing inorganic material is used. The pad is honing. 14. The method according to item 9 or 10 of the scope of patent application, wherein the permittivity (K) of the insulating film printed on the semiconductor substrate by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is less than 2.5. · For example, the honing fluid for metal film in the scope of patent application, which does not substantially contain abrasive particles. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)