TW200919568A - Set for preparation of aqueous dispersion for chemical mechanical polishing and method for preparing aqueous dispersion for chemical mechanical polishing - Google Patents

Abstract

Disclosed is a set for preparation of an aqueous dispersion for chemical mechanical polishing, which comprises a first composition containing a colloidal silica and a basic compound and having a pH of not less than 8 but not more than 10, and a second composition containing a poly(meth)acrylate and a basic compound and having a pH of not less than 11 but not more than 13.5. The set for preparation of an aqueous dispersion may further comprise a third composition containing an oxidizing agent.

Description

200919568 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for preparing a chemical mechanical polishing aqueous dispersion preparation kit and a chemical mechanical polishing aqueous dispersion. [Prior Art] In recent years, with the high integration of the semiconductor I and the multi-layer trimming, the planarization technology by chemical mechanical polishing has attracted attention. In the chemical mechanical polishing aqueous dispersion (hereinafter also referred to as "slurry" used in the chemical mechanical polishing #, abrasive grains are usually blended as an abrasive. In the gas phase described in Japanese Patent Laid-Open No. 2 () g3_289〇55 2, the gas phase described in the publication: fumedsiliGa, colloidal dioxide, emulsification, and inorganic particles of oxidized material; Particles such as methyl vinegar, etc.; organic or inorganic composites that combine these physical or chemical properties: The slurry contains not only abrasive particles, but also other components such as organic acids and surfactants. . Therefore, it is known that the long-term preservation of the θ 2 is caused by the agglomeration of the abrasive grains and the like. In this way, the abrasive granules are used to grind the m slurry to make the chemical machine. For example, since the wiring portion is excessively polished, it is called "dishing" or "invading button". In addition, there is also a scratch-like surface defect in the so-called "to the mark". In particular, in the case of providing a chemical mechanical polishing water regime in a concentrated state, such a problem becomes remarkable and it is expected to improve. In addition, if chemical processing is carried out on a metal film such as copper or copper alloy, mechanical grinding, 97127579 200919568, there is a so-called "corrosive QrrQsiQn". Generally, benzene is added to the slurry, and "" corrosion is caused by this corrosion inhibitor. It is a biodegradable anti-corrosive agent for prostitutes. However, the problem of the charging liquid of the agent. Because two = to process the containing material. The temple is happy to produce a slurry containing no anti-money agent. [Invention] The object of the present invention is to provide a surface to be grounded by JI2. +θ /. , and mechanical polishing of the chemical body: The chemical mechanical polishing of the surface defects of the intrusion = the corrosion of the water system and the long-term accompanying method in the concentrated state, the grinding water dispersion (4) is used for the set. Μ化予机械 The chemical mechanical polishing water system of the present invention: the first composition, which contains the #体广/3D system kit

The ruthenium oxide and the basic compound are 8 to η, and the pH is 8 or more and 10 or less; and the second composition contains a dilute acid salt and an organic compound, and the pH is 4u or more and 3 or less. earth)

In the chemical mechanical polishing aqueous dispersion preparation of the present invention, the second composition may further contain a surfactant. In the chemical mechanical polishing aqueous dispersion preparation kit of the present invention, the surfactant may be at least one selected from the group consisting of acetylene- acetylene, ethylene oxide adduct of acetylene alcohol, and at least acetylene alcohol. 1 species. In the chemical mechanical polishing aqueous dispersion preparation kit of the present invention, the second composition may further contain an acidic compound. In the chemical mechanical polishing aqueous dispersion preparation kit of the present invention, the acidic compound may be selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, maleic acid, 97127579 200919568 malonic acid, citric acid, and malic acid. At least one. In the chemical mechanical polishing of the octagonal colloidal cerium oxide bismuth in the chemical mechanical polishing, the squadron of the squadron can be 30mn~l〇0nm. The chemical mechanical polishing of the present invention, f jujube In the rwi, 呷靥 water-based dispersion preparation kit, the above K methyl) acrylate acid salt is above 500, 000~3, 000, 000. The average molecular weight can be used for the chemical mechanical polishing of the present invention. One cow and the person in the p > spear, knife release body modulation kit, can improve the third composition of the third preparation 3 with oxidant. The machine:: the preparation method of the grinding water dispersion * has colloidal two The oxidized second and the test compound dilute acid salt and the basic compound are pulverized into a substance containing a poly(methyl) propylene to have a pH of 8 or more and 12 to the heart and 13.5 or less and to adjust the r < Mechanically Grinding Water Dispersion. The preparation of the mechanical polishing water dispersion: The progress can be improved to the third έ 札 μ μ θ 10, 刎 3 composition containing oxidizing agent, and the pH is adjusted to 8 or less. The chemical mechanical polishing aqueous dispersion is used. According to the present invention, the ith composition and the second component can be separately stored. The agglutination of the steroid dioxin contained in the first composition is stopped. The L and the adult system are excluded from the components causing colloidal silica dioxide agglutination, and the pH is adjusted to 8 to 1 by adding an inspecting compound. If the pH is in the HO range, the reaction between the colloidal dioxin and the test compound is inhibited, and the number of the sulphuric acid base calculated from the signal area of the W spectrum can be maintained at an appropriate value, etc., and the colloidal body can be prevented. The oxidized stone is deteriorated. Therefore, even in the state where the first composition is shrunk, the long-term stability of the colloidal dioxygen 97127579 200919568 fossil can be ensured. Addition: The range of PH is 1H3.5: 2. And the composition of the product, the preparation of the composition of the composition of the composition of the composition of the composition of the second group of metal I: the two aqueous dispersions because of the testability, it can inhibit η,: raw 'do not need to add benzene Three saliva _. The flat class: the sudden: the agglomeration or deterioration of the phlegm is less, so the surface is missing: the surface can be suppressed by shallow disc, invading or scratching [Embodiment] The chemical mechanical polishing water of the present invention is prepared by dispersing: the first composition, which contains a handsome exhibition Set harness

The compound of 8 or more and the test compound, the p- enoate and the base drop, and the compound thereof contain a poly(meth) propylene sulfonium salt and a basic compound, and the pH is 11 or more and 13 5 or less. Good implementation, detailed description 1. The first composition of physicochemical two: ^ ^ composition ' contains colloidal silica dioxide and test mouth 4, and the liquid phase of the product from the (four) body dioxide dream From a point of view, it is adjusted to be weakly alkaline at pH 8 to 10. The components are described in detail. 1. Colloidal cerium oxide as the colloidal cerium oxide used in the first composition, for example, the colloidal dioxin synthesized by the inorganic colloid method for removing impurities, and the like, the average of the steroids of the steroids - 97127579 8 200919568 The wire diameter is preferably 幺25 to 35 nm. Further, the above-mentioned colloidal cerium oxide is more preferably 30 to 100 nm, more preferably 4 " 〇 nm 卜: colloidal silica having a preferred particle diameter of the human particles, and the equilibrium of the flatness in the range can be achieved. A good surface to be ground and ground Γ Non-confined colloidal dioxin particles are randomly drawn): The diameter of the observation is expressed as the average value. For each particle, the average of two seconds of colloidal oxidation seconds: the number of particles can be = dynamic first scattered secondary particles. When colloidal M = Z particles aggregate and form a grinding action, secondary particles are usually formed. The sub-broken surface was calculated from the signal area of the colloidal dioxygen 29Si-NMR spectrum contained in the first composition. The number of decyl alcohol groups is the spectrum contained in the first composition, and may be obtained by containing a cerium dioxide containing cerium oxide or cerium oxide, or a chemical mechanical polishing water 2 = grinding water dispersion filtration, etc. The dispersion of the erroneously centrifuged or super-membrane recovered by the known method, the oxidized hair granule 2: the teaching component, and the oxidized second particle can be obtained by measuring the thus obtained method. The calculation formula of the following formula (1) is used to calculate the signal area of the nine-phase, i, and i, by the 97127579 200919568 spectrum by the exaggeration separation process for the peak ^ body of the oxidized stone, the _ light atom is set to 〇 _ The chemical position; will be set to (1) as the signal area of the tetramethyl Qianshi Xi'i:, the peak value of Qing is judged to be the signal area judgment is set to a2, and the peak of 2: is judged as 卯' The signal area is judged to be two = Yes, and the signal area judgment is set to 3 to judge the peak value of the rhyme: 二: Two '1^^ sub-adjacent TM coordination number is -- (4) The formula is the number of bits For the 2 stone eve atom, the atomic argon atom can be assigned to the atomic ~. It is considered that Q3=2=Sl〇_' is a W sub-quantity with a number of bits, and the formula of the atomic atom adjacent to the atom is called..., and the quantity is (four) 81丄, and the composition is expressed as scratch. The formula 2 = two points "signal,", a-, and one alcohol base number can be in accordance with the following general-style particle inclusions (number 1)

Here, Να represents the Yafotian constant: 6 〇 22xi〇u. The above-mentioned colloidal dioxy-cutting alcohol base number is preferably ^; 23. 97127579 10 200919568 or more and 4. 〇χ 1 〇 23 / g or less, more preferably 36 乂 1 〇 23 3.8 X l Q 23 / g or less. In the case where the number of tearing cells from the signal area of the spectrum is within the above range, since the dioxotomy:::, the strength of the dioxo prior particles is increased, a sufficient speed f is obtained, and A moderate amount of the alcohol base number is stabilized by the action of the aqueous dispersion medium, and the dioxide particles are chemically dispersed in the chemical mechanical: ^ dispersion, which does not become a defect original during grinding; When the number of alcohol groups exceeds the above range, there is a case where the dioxogranules are deteriorated, and the defects such as sufficient polishing speed and scratches are not obtained, which is not preferable. When the number of bases is less than the above range, _I stanol is dispersed in water. Zhao (4):: Poor;: =: Mechanical grinding is caused by defects such as marks on the object to be polished, which is not preferable. The polishing is carried out and, as will be described later, in the first fine. It is known that the test compound and the thiol group which protrudes from the additive compound will cause the exchange of the glycerol of the surface of the saponin, and the interaction of the metamorphic bond of the colloidal oxidized silica will occur. Because of the surface defect of the grinding surface. If the colloid is oxidized :=, the upper ― can be reduced, and the gel can be suppressed. The gel used in the first composition is recognized as the first! The mass of the composition is preferably: 3 〇 ^ ^ addition amount, relative amount %. If the colloidal silica dioxide is added with ^, preferably 10 to 20, with a chemical speed of π/ 2 shells with a sufficient grinding rate of 1%, the water dispersion of the sub-mechanical polishing cannot be obtained, and the 97127579 200919568 is not used. . On the other hand, when the amount of the colloidal cerium oxide added exceeds 2% by weight, the aggregate of the colloidal cerium oxide is likely to be formed in the first composition, and the surface defects of the surface to be polished or the like may occur. . 1. 2 Assay compound The basic compound used in the first composition is an essential component for maintaining the liquidity of the second composition in a weakly basic (ΡΗ8 to 10). η ο The basic compound used as the first composition may, for example, be an organic test or an inorganic base. The organic base may, for example, be tetra. As the inorganic test, for example, ammonia or gas oxygen can be cited. Among the compounds, it is preferably inorganic or ammonia-decomposed, and particularly preferably hydrogen peroxide. The amount of the test compound used in the composition of the ii is added to the liquidity of the first and first compositions to be inspective (pH 8 to (1) is required to be 'special.' = Dispersing medium, for example, a mixed medium of water, water and alcohol, and a mixed medium containing water/water-compatible organic solvent: Gui: two water or a mixed medium of water and alcohol, particularly preferably a mixture of two components When the pH is unstable, there is a case where the polishing property is hindered. If the pH exceeds 1 〇, there is a case where the first composition is contained in the first composition, and the 29th_NMR photo stanol is contained in the first composition. The base number is added to the number of noses and the addition of colloids to the emulsified stone eve, but there is a situation in which the original organic energy cannot be sent. 2. The second composition = real & The second composition ' contains a poly(meth)acrylic acid:: compound. The liquid structure of the 帛2 composition is composed of a mixture of the composition: 2, and 2, the chemical mechanical polishing aqueous dispersion of the composition Keep it as a point of sexuality' and adjust it to ΡΗ11~13. 5 testability. Described in detail.

2·1 poly(meth)acrylate straw Due to the addition of poly(methyl)propionate to the » 2 composition, a larger process range can be obtained (even if the chemical polishing machine is used to greatly exceed the optimum polishing time) A chemical mechanical polishing aqueous dispersion in which the surface of the polished surface does not deteriorate in the performance of the aqueous dispersion. The counter cation contained in the poly(fluorenyl) acrylate may, for example, be an ammonium ion, an alkylammonium ion, a potassium ion or a sodium ion. Among them, ammonium poly(meth)acrylate or potassium poly(meth)acrylate is particularly preferred. The weight average molecular weight of the I (meth) acrylate is a polyethylene glycol-equivalent value measured by gel permeation chromatography using water as a developing solvent, and is preferably 500,000 to 3,000. 〇〇, more preferably 1' 000, 000~2, 000, 000. By using a weight-averaged molecule in this range, a chemical mechanical polishing aqueous dispersion is prepared for a larger process. When the weight average molecular weight is less than 500,000, for example, the polishing rate of the insulating film such as the PETE〇s film is remarkably lowered, and it is difficult to achieve flattening of the surface to be polished. On the other hand, if it exceeds 3,000,000, although the polishing rate for the insulating film is sufficient, it is difficult to manufacture in the production of 97127579 13 200919568 because the molecular weight is too large, and it is not practical. The amount of the poly(fluorenyl) acrylate to be added is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass based on the mass of the second composition. By setting the content in this range, a dispersion for chemical mechanical polishing in a large process range can be obtained. For example, the poly(meth)acrylate is ammonium poly(indenyl)acrylate having a weight average molecular weight in the range of 1,000,000 to 2, _,000, and the addition amount = Γ Ο relative to the weight of the second composition In the case of 5·5 to 3 mass%, it is possible to obtain a chemical mechanical polishing aqueous dispersion which can surely achieve a large process range. 2. 2 Detective compound * The test compound used in the second composition is a component necessary for maintaining the liquidity of the second site to be alkaline (ρ Η 11 to 13.5). The test compound to be used as the second composition may, for example, be the same organic base or inorganic base as the work composition. The organic base may, for example, be tetramethylammonium hydroxide or triethylamine. As an inorganic test, ammonia, potassium hydroxide, sodium hydroxide, etc. are mentioned, for example. Among these test compounds, ammonia or potassium hydroxide is preferred, and potassium hydroxide is particularly preferred. The basic compound contained in the second composition is preferably the same as the basic compound contained in the first composition. By using the same alkalinization = when the ith composition and the second composition are mixed to prepare the aqueous dispersion of the chemical machine 2, the second composition of the colloidal silica dioxide condensate can be suppressed as much as possible. The amount of the basic compound to be used is not particularly limited as long as the liquidity of the composition is kept to be alkaline (10) and 13 5). 2. 3 Dispersing medium The dispersing medium may, for example, be a mixed medium of water, water and alcohol, or a mixed medium containing water and an organic solvent compatible with water. Among these, it is preferred to use water or a mixed medium of water and alcohol, and it is particularly preferable to use water. 2·4 Other Additives In the second composition, in addition to the above components, a surfactant, an acidic compound, or the like may be added. 2.4.1 Surfactant As a surfactant, a cationic surfactant, an anionic I* surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used. Among these, an anionic surfactant or a nonionic surfactant is preferably used, and a nonionic surfactant is more preferably used. The nonionic surfactant may, for example, be a polyethylene glycol type surfactant, acetylene glycol, an ethylene oxide adduct of acetylene glycol or acetylene alcohol. Among these, a compound having a triple bond in the molecule is preferred, and examples thereof include an acetylene glycol, an ethylene oxide adduct of acetylene glycol, and an acetylene alcohol. The anionic surfactant may, for example, be a carboxylate, a sulfonium sulfonate, a sulfate salt, a phosphoric acid vinegar or a fluorine-containing surfactant. The carboxylic acid = may, for example, be a fatty acid soap or an alkyl ether carboxylate. Examples of the sulfonate include an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, and an α-olefinsulfonate. Examples of the sulfate salt include a higher alcohol sulfate salt and an alkyl ether sulfate. Polyoxyethylene phenyl sulfonium sulfate and the like. As the acid salt, for example, an alkyl phosphate salt or the like can be exemplified. The fluorine-containing surfactant may, for example, be a total of 97127579 200919568 fluoroalkyl compound or the like. Among these anionic surfactants, a gas-containing surfactant is particularly preferred. These surfactants may be used alone or in combination of two or more. The amount of the surfactant to be added is preferably 0.01 to 5% by mass, preferably 0.05 to 2% by mass, particularly preferably % by mass based on the mass of the second composition. When the amount of the interface active agent added is within the above range, an appropriate polishing rate and a good surface to be polished can be achieved. 2 · 4. 2 Acid compound As the acidic compound, an organic acid having 4 or more carbon atoms is preferably used. Among the organic acids having 4 or more carbon atoms, 'the organic acid having a carbon number of 4 or more and the organic acid having a hetero ring are more preferable. The aliphatic organic acid having 4 or more carbon atoms is preferably an aliphatic polycarboxylic acid having 4 or more carbon atoms or a hydroxy acid having 4 or more carbon atoms. The aliphatic polybasic carboxylic acid having 4 or more carbon atoms may, for example, be a ternary organic acid such as maleic acid, succinic acid, fumaric acid, glutaric acid or adipic acid. Examples of the transbasic acid having a carbon number of 4 or more include citric acid, malic acid, tartaric acid and the like. The organic acid having a hetero ring may, for example, be quinolinecarboxylic acid, pyridinecarboxylic acid, pyridinedicarboxylic acid or pyridincarboxylic acid. Among these, more preferred are quinolinic acid (for example, 2-quinolinecarboxylic acid), quinolinic acid (for example, acid), and 2-valent organic acid (for example, cis-butanic acid, two:) = acid (for example). , malic acid, malonic acid), particularly preferably quinolinecarboxylic acid, quinolinic acid. The amount of the acidic compound added is more than (four) 0.0 5% by mass, and more preferably 0.05 to 2% by mass based on the mass of the second composition. If this is the addition amount of the standard 97127579 16 200919568, the polishing rate and the uniformity of the surface to be polished can be achieved. The acidic compound is selected from the group consisting of quinoline carboxylic acid and quinoline bismuth: Acid (in which 啥 酸 acid is added, the amount of addition is more preferably 0.05~2#%. Therefore, (10)1 holds the grinding speed and is better preserved from quinoline carboxylic acid, quinolinic acid, cis-# ", at least the kind of hazelnut acid, ... Τ:, malonic acid, citric acid and frequency) / 1 kind of addition I is particularly preferably 0.05 to 2% by mass. Therefore, y is more favorable (four) grinding speed and Goodly ground acidic compounds can be used alone or in combination of two or more types 4

2.5 pH The pH of the second composition is preferably ^ or more and (1) is 12 or less and 13.5 or less, and particularly preferably Μ or more and 135 or less of the second composition is less than u, and the ith composition and the first component are mixed. In the case of the right composition, a neutralization reaction occurs. Therefore, the occurrence of heat and colloidal emulsification are unstable and agglomerate. When the second composition is more than 13.5, the colloidal composition is unstable and aggregated when the second composition and the second composition are mixed. In any case, if it exceeds the above range, agglomerates of colloidal cerium oxide may be formed in the chemical mechanical polishing aqueous dispersion obtained by mixing the first composition and the second composition. This is a cause of surface defects such as scratches on the surface to be polished, which is not preferable. , J, 3. Other additives 3.1 Oxidizing agent 97127579 17 200919568 In the first composition or the second composition, for example, oxygen may be added to the surface to be polished, and g is oxidized. Metal, so the copper film is not easy to enter due to the surface oxidation of copper which is rich or ductile, and the copper film can be made into a copper oxide film by an oxidizing agent to increase the polishing speed. The ',, and the oxime agent' may, for example, be persulfate, peroxidation, peroxide, or a polyvalent metal salt. As a perrhenate, a second, an acid, and the like. Examples of the organic if-acid include, for example, tartaric acid, sulfonium-A.., and hydrazine, and examples thereof include peracetic acid, perbenzoic acid, and hydrogen peroxide. The polyvalent metal salt may, for example, be a perchloric acid compound or a dichromic acid compound. Specifically, the substrate may be, for example, subjected to acid detachment or the like, and may be referred to as a potassium hydride or the like. For example, heavy chrome is 'persulfate and inorganic acid'. Ο Ο 里 里 0 0 0. Relative to the second έ and 赤铷 = good. % by mass, more (four) average amount. = two quantities 'can achieve the polishing rate and the well-balanced consumption of the composition of the present embodiment or the second group of exhaustive == separately prepare the third composition containing the oxidant, and the chemical mechanical polishing water system The dispersion is prepared by modulating the composition of the first composition or the second composition to deteriorate oxygen. At this time, if the third other set including the oxidizing agent is prepared, deterioration of the oxidizing agent function can be prevented. , ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The amount is 〇·〇1 to 5, and when it is converted to hydrogen peroxide, it is balanced by a well-polished surface. In the first composition or the second composition, the first composition or the second composition can be more reliably controlled, and the peak of the first composition is controlled, and the peak is added, that is, the control is 1 to 13.5. The chemical mechanical polishing of the second composition was carried out, and the second composition was mixed (ΡΗ8 to 12). The palpitations remain alkaline Ρ 12) Therefore, it is possible to suppress the anti-silver agent which is required to be inferior to the first composition or the day + the eclipse. Adding benzotrisamine or its derivative to the product 4. Preparation method of chemical mechanical polishing aqueous dispersion f by ^ above! The composition and the second composition may be prepared as a chemical mechanical polishing aqueous dispersion with the above-mentioned younger brothers, and the resultant or pure water. The compounding amount of each composition is in the form of a desired concentration in each composition, which is obtained by comparing the total mass of the chemical mechanical polishing water hydrazine dispersion obtained by the combination with the ^^^^^^^^ Decide. The air knife is specifically referred to as the total mass of the chemical mechanical polishing water dispersion obtained by the mixing, and the content of the colloidal cerium oxide is 0. 0 b 10% by mass, and the content of poly(fluorenyl) acrylate The content of the surfactant is 〇·001~2 mass%, the content of the acidic compound is 〇. 〇1~5 mass%, and the oxidant content is 〇〇〇5~5 mass. In the case of %, the mixing amount of the above-mentioned 97127579 19 200919568 first composition, the above second composition, the above-mentioned third composition, and pure water may be determined. 5. Chemical mechanical polishing method 5. Chemical mechanical polishing device Fig. 1 shows a schematic view of a chemical mechanical polishing device. As shown in Fig. 1, the chemical mechanical polishing apparatus 100 supplies a chemical mechanical polishing aqueous dispersion (slurry crucible 6) from the feed supply nozzle 12, and rotates the rotary rotary table to which the polishing cloth 18 is attached. The top ring of the semiconductor substrate 1 is held in contact with the X to be abutted, and the water supply nozzle i 4 and the trimmer 24 合并 are also shown in FIG. 1 , and the grinding load of the ring 22 can be selected within the range, preferably 3 〇~5〇〇gf/cm2(2. 94~49kf^). Further, the number of rotations of the = σ 20 and the top ring 22 can be appropriately selected within the range of 1Q to 4 rpm, preferably 30 to 15 rpm. The flow rate of the slurry 16 supplied from the slurry supply nozzle 12 can be selected within a range of 1 (M, 〇〇〇ml/min: I, preferably 5 0 to 4 0 0 m 1 /min. When the chemical mechanical polishing aqueous dispersion obtained by the chemical mechanical polishing aqueous dispersion preparation kit of the present invention is subjected to polishing by the polishing side, a commercially available chemical mechanical polishing apparatus can be used. Specifically, δ can be used. The company's type ΕΡ0-112", "ΕΡΟ-222", Lapmaster SFT's model 2 "LGP-51G", "LGP-552", Applied Materials' "Mirra", etc., according to the specified grinding conditions 5.2. Preparation of chemical mechanical polishing aqueous dispersion 97127579 20 200919568 The chemical mechanical polishing aqueous dispersion of the present invention is adjusted == it: the first composition and the second composition, and if necessary, ^ The third composition may be a preparation-dispersion. As such a mixing method, the following first embodiment and the second composition may be used, and if necessary, a steroid-containing composition: First to modulate chemical mechanical polishing Fraction r 2: The chemical mechanical polishing aqueous dispersion is supplied from the slurry to the rotary table 2 from the slurry, and the second composition can be used in advance. The third component containing the oxidizing agent is mixed, and the composition of each of the components is supplied from the slurry supply nozzle 12i and the money transfer table 2G, respectively, and the mixture is mixed on the rotary table. The second group of filaments and the oxidant containing the first, the oxidizing agent are supplied to the rotating table 2 from the aggregate supply nozzle 12, and are mixed with the yoke on the turntable. "Mixed" means blending, mixing, and mixing in addition to the method of grinding the composition on the turntable 20, and mixing it on the turntable 20, for example, blending In the tank, the pH of the chemical system polishing slash system is preferably 8~j2, which is prepared by the mixing method of mixing the medium with the respective components to (3). Inside, the metal film can be suppressed. The right PH is the corrosion of the upper j metal crucible, and even for the Any of the film, the barrier metal film, and the insulating film, and the 'attribute energy. The seed film may also have a good polishing. 97127579 200919568 5 · 3 chemical mechanical polishing method The chemical mechanical polishing water dispersion preparation kit of the present invention, It can be applied to a wide range of chemical mechanical polishing steps for fabricating semiconductor devices, and is particularly suitable for use in forming metal damascene wiring using copper as a wiring material. The metal-intercalation wiring forming step using copper as a wiring material is based on $ is a step of forming a barrier metal film on the insulating film (including the trench portion) in which the trench is formed, and then depositing copper of the wiring material, removing the remaining beryllium copper (the second polishing process step), and removing the trench portion The step of the barrier metal film other than the barrier (second polishing treatment step)' is further performed by a step of polishing the insulating film portion (third polishing step) to obtain a flat gold f-inserted wiring. The chemical mechanical polishing aqueous dispersion preparation kit of the present invention may be applied to any of the first to third polishing treatment steps, wherein the copper refers to pure copper, copper and aluminum, and the cerium includes copper content. The concept of 95% or more. Further, the above-mentioned "barrier metal film" means, for example, a button, titanium nitride, or a nitrided crane. Listening to I Titanium 6. Example 6.1 Preparation of aqueous dispersion containing colloidal cerium oxide particles (a) Preparation of aqueous dispersion of colloidal silica dioxide cation particle C1 Ammonium water of 25% by mass of Hancheng 7 〇 mass parts, Ion exchange water 4 〇 mass, 170% by weight of the knife and 4 parts of the tetraethoxy material were filled into the flask, and the temperature was raised to 8 (TC) while stirring at a rotation speed of 18 〇. The temperature is maintained at ah and the mixture is allowed to mix for 2 hours, then cooled to room temperature. 97127579 22 200919568 By this, 'to get the colloidal bismuth oxime to the evaporator, repeat the number - the big side of the Chiang " dispersion. Secondly, use the spin t And adding the ion exchange water edge - maintaining the temperature of the dispersion to a temperature of 2 ^ to remove the alcohol. By this operation, the door wind 3 has a different amount of colloid 2 the body of the water dispersion t 2 t ^ of aqueous dispersion. The secondary particle size is 25 nm, the average secondary particle; the average particle size of the stone particle C1 - - rn λν 1 y nm 'the average degree of convergence is 1.6. The modulation of the water dispersion of the ΛΛγ particle C2 65 parts by mass of ammonia water 65 parts by mass, ion hydrazine, ethanol 1 75 皙昜 / eight " 卞乂 change water 40 罝. ., A knife and tetraethoxy decane 25 parts by mass, fill in f to 焯: medium, rotate at a speed of ~ to the side of the mixing: = burn to maintain the temperature at 8 (continued for 2 hours at rc to 8 °c) Thereby, an alcohol dispersion of colloidal silica dioxide granules is obtained. Two to ^When. =; r is added several times while adding the obtained π π C sub-addition of ion-exchanged water, a reed at 80 to prepare 20 Quality =: rain. By this operation, the 月Berry/0 colloid-emulsified cerium particle C2 "the 二 dispersion contained in the colloidal silica dioxide celite particle C2 has a monthly diameter of 35 nm, and the average secondary particle diameter 7Gn, ^1 (c) colloidal silica dioxide 曰 initial 曰 σ degree is 2. 测定. Determination method of the material (four) - wire diameter and average secondary particle size, 隹 = · (ΤΕΜ) (Hitachi Manufacturing Co., Ltd. ), the type "H-7500 cloth 2, the average secondary particle size is a dynamic light scattering type -" Gossip (Hiroshima Co., Ltd., type "_0") for i 97127579 23 200919568 The colloidal characteristics obtained by the method are shown in Table 1. The two gasified cerium particles C1 to C2 (Table 1) The type of colloidal cerium oxide 25 mass% ammonia water usage Parts by mass) Ethyl alcohol used (parts by mass) Tetraethoxy decane used (parts by mass) Content in aqueous dispersion (% by mass) - 1 - 70 2. Average primary particle size (nm) Average secondary particles Diameter (nm) (a) An aqueous solution containing polyacrylate pi is prepared by filling an ion-exchanged water crucible, _ and a 5 mass% aqueous solution of ammonium persulfate, 4 g of an internal volume of 2 liters of the container, under reflux - While stirring, a 20% by mass aqueous solution of bupropion acid (5 〇〇^) was uniformly dropped over 10 hours. After completion of the dropwise addition, the mixture was further kept under reflux for 2 hours to obtain an aqueous solution of a polyacrylate having a weight average molecular weight (Mw) of 1,500,0 Å. The aqueous solution of pH 7.5 containing polyacrylate P1 (weight average molecular weight (Mw) 1,500,000 potassium polyacrylate) was prepared by adding a 10% by mass aqueous solution of potassium hydroxide to be neutralized. . (b) An aqueous solution containing polyacrylic acid salt P2 is prepared by charging an aqueous solution of ion-exchanged water of 1,000 g and a 5% by mass aqueous ammonium persulfate solution 97127579 24 200919568 〇.6g in a container of 2 liters under reflux. While mixing, - 10 〇〇g of 20% by mass aqueous acrylic acid solution was uniformly dropped for 10 hours. After completion of the dropwise addition, the mixture was further kept under reflux for 2 hours, whereby an aqueous solution of a polyacrylate having a weight average molecular weight (Mw) of 1,300,000 was obtained. A 10% by mass aqueous potassium hydroxide solution was slowly added thereto for neutralization, and δ 周% of a polyacrylate P2 (weight average molecular weight (Mw) of 1,300,000 potassium polyacrylate) was prepared at δ 周%. Aqueous solution. (c) The preparation of the aqueous solution containing polyacrylic acid hydride 3 is prepared by filling an ion exchanged water crucible, 00 〇 2 and 5 mass % ammonium persulfate aqueous solution 〇 8 g of an internal volume of 2 liters of the container under reflux. On the other hand, 500 g of a 20% by mass aqueous acrylic acid solution was dropped evenly over 10 hours. After completion of the dropwise addition, the mixture was further kept under reflux for 2 hours, whereby an aqueous solution containing a polyacrylate having a weight average molecular weight (Mw) of 1,050 and hydrazine was obtained. A 25% by mass aqueous ammonia solution was gradually added thereto for neutralization, and an aqueous solution of pH 7.5 containing 10% by mass of polyacrylate salt P3 (weight average molecular weight υ (Mw) 1, 050,000 ammonium polyacrylate) was prepared. . (d) Method for determination of weight average molecular weight of polyacrylates Weight average molecular weight (molecular weight in terms of polyethylene glycol) and molecular weight distribution by gel permeation chromatography (device name; Waters Corporation & The group-1"' detector was used to measure the "410 type differential refractometer" manufactured by Waters Co., Ltd. The column was made of "/Sink-Μ" manufactured by Tohs Co., Ltd., and the eluent was NaC 1 aqueous solution / acetonitrile. Mixture. Further, the characteristics of the polyacrylates P1 to P3 obtained by the above method are all 97127579 25 200919568 (Table 2) The type of polyacrylic acid P1 P2 P3 The amount of ammonium persulfate (g) 0. 02 0. 03 0. 04 Type of agent KOH KOH NHs Weight average molecular weight (Mw) 1,500, 000 1,300, 000 1,050, 000 6. 3 Chemical mechanical polishing test 6. 3. 1 Evaluation of grinding speed p Chemical mechanical polishing device (Mirra, manufactured by Appl ied Materials Co., Ltd.), a porous polyurethane polishing pad (model "IC1000" manufactured by Rodel Nitta Co., Ltd.) is supplied, and a predetermined chemical mechanical polishing aqueous dispersion is supplied. Each of the following polishing rate measuring substrates "grinding was performed for 1 minute under the above-described polishing conditions, and the polishing rate was nose-dried by the following method. (a) Substrate for polishing rate measurement • A copper film having a film thickness of 15 Å is placed on a substrate of 8 吋 with a thermal oxide film. • On the 矽 substrate with 8 吋 thermal oxide film, the film thickness of 2, 〇〇〇 之 button film is set. ' • On the 矽 substrate of the 8 吋 thermal oxide film, the film thickness is set to 2, 〇〇 () 埃 : : nitride button film. '• On the 矽 substrate of the 8 吋 thermal oxide film, a PETEOS film with a film thickness of 1 〇, 〇〇 () Å is provided. • On the 矽 substrate with 8 吋 thermal oxide film, a film thickness of 1 〇, 〇〇〇 之 low "electric coefficient insulating film (Appiie (j Materials, product 97127579 26 200919568 "Black Diamond") (b) Grinding conditions • Grinding head rotation number: 8 rpm • Rotating table rotation number: 85 rpm • Grinding head weight: 15 〇 gf/cm 2 • Chemical mechanical polishing water dispersion supply speed: 20 〇 1111/min In this case, the supply rate of the chemical mechanical polishing aqueous dispersion refers to the total amount of supply of (,, ''cardiac feed solution divided by the value per unit time. 6·3· 2 Calculation of polishing rate for copper film The film and the nitride film were measured using an electrically conductive film thickness measuring device (manufactured by KUlencor Co., Ltd., type "〇MNIMApRS75"), and the film thickness was measured, and the film thickness was reduced by chemical mechanical polishing. Thickness and grinding time, nose grinding speed. * For PETEQS film and low dielectric constant insulating film, use light diffraction type, thick measuring device (Nanometrics japan, type Nan〇spec6100), after grinding treatment Film thickness The film thickness and the polishing time reduced by the mechanical polishing were calculated. 6·3· 3 Evaluation of the scratches Using an optical microscope, in a dark field, randomly observe the range of 2〇〇•12〇#mxl20#m unit area, The number I of the scratch-prone unit area was measured as the number of scratches. In the following examples, the unit of "unit/200 area" was added to this value. 6· 3. 4 Evaluation of corrosion for the area of copper of lcm X lcm Using the defect inspection device 97127579 27 200919568 (KLA-Tencor, model "2351"), the number of defects of 1 〇 nm 2 to 1 〇〇 nm 2 was evaluated. In Table 7, 〇 indicates that the number of corrosion is 〇 〜 1 The best state of 〇 is △ indicates a slightly better state of 〜1~1〇〇. X indicates that there are more than 101 rot #, and it is judged that the polishing performance is poor. 6. 3. 5 Evaluation of average secondary particle diameter The average secondary particle diameter of the colloidal cerium oxide in the aqueous dispersion was measured by a laser scattering type measuring device (manufactured by Otsuka Electronics Co., Ltd., the form "LPA610". 乂 6. 3. 6 colloidal oxidation Quantification of stanol groups in 矽 ▼... The first composition The colloidal cerium oxide contained was dried in a vacuum dryer for 2 days. The dried colloidal dioxotomy was used to fully pulverize the pulverized colloidal silica dioxide in the form of a solid-state nuclear magnetic resonance spectrometer, manufactured by Bruker. The form "AVANCE3()〇" is performed by the dd_mas method.

The Si臓 spectrum is 敎 and is performed using the peak separation software core

: The signal area of the state of Q Bu Q2, q3, and Q4 is obtained by Knife, and the number of stanol groups is calculated according to the above general formula (1). 6. 4 Example 1 and Comparative Example 1 6 · 4 · 1 Example 1 (a) Modification of the first composition The above "6.1 (a) contains colloid-label, body-emulsified cerium particles Cl The aqueous dispersion containing the colloid-oxygen is prepared by dragging the aqueous dispersion of the bismuth bismuth particles Cl, and the inorganic particles are replaced by the granules of the granules. The amount of % is added after "], and the potassium oxide is added to pH 詷敕%. The person who is assigned is called _ θ a ° and the whole is 8. 8 . Then, after the ion exchange water was added in such a manner that the total composition of the total boring tool became 1 〇〇 mass%, the Μ 97127579 28 200919568 hole was filtered from the filter of 1 # m to obtain an aqueous dispersion (a). . Further, the colloidal ceria C1 in the first composition (A) was uniformly dispersed, and its average primary particle diameter was 45 run. (b) Preparation of the second composition: quinolinic acid equivalent to 1.2% by mass and citric acid equivalent to 12% by mass are dissolved in ion-exchanged water, and acetylene glycol type equivalent to 〇6 mass% is added. Ionic surfactant "% 忖郯〇 1465" (A product (manufactured by Products japan), and then polyacrylate-containing preparation prepared by the above-mentioned "6.2 (b) Preparation of aqueous solution containing polyacrylate P2" The amount of the aqueous solution is equivalent to 2, 4% by mass in terms of the weight of the polymer, and J force if #·1 5 knives| After the addition, the gas oxidizing and unloading is adjusted to a $. The combined measurement becomes 100 mass. After adding 乂'7 in % mode, the filter with the wrong pore size of 0.45/zm is used to reduce the aqueous solution (B). For the example, the product is expected to be integrated, and the integration is shown in Table 3. The composition of the brother 1 and the second group are used. U The chemical mechanical polishing water prepared by using the water dispersion (4) and the just-adjusted/gluten solution (β) immediately after the preparation is adjusted. The evaluation performance of the π water-repellent dispersion is as follows. Water, according to the weight ratio _ after the completion of the aqueous solution (8)% of the quality of hydrogen peroxide water (Group 3 thereafter, will When the amount of mass % is added, hydrogen peroxide is added as an aqueous dispersion (Α+Β). This chemical D is used for mechanical polishing of the machine + Dii & : Body U+B) π-milling aqueous dispersion (Α+β), 97127579 29 200919568 Various tests were carried out according to the test methods described in the above “6.3 Chemical Mechanical Polishing Test”. The results are shown in Table 4. = Evaluation of dispersive grinding performance of chemical mechanical polishing water prepared by dissolving the aqueous dispersion (A) after half a year of preparation and the aqueous solution (8) prepared for half a year: 糸 dispersion (4) and aqueous solution (8) are placed in a closed container, It is stored in a warm bath for half a year. The water-dispersed particles after standing for half a year are saved. Colloid: The oxygen-cut particles C1 are uniformly dispersed, and the average is twice (10). The pH of the body (A) 125 on the other hand 'the pH of the aqueous solution (8) after standing for half a year is the water dispersion after the use of the static storage for half a year: the latter aqueous solution (8), and using the above "...(6) to make == water body ( A) and the chemistry prepared by the aqueous solution (8) Various evaluations were carried out in the same manner as in the evaluation of the polishing performance of the machine-grinding blade. The water-based dispersion (4) after storage for six months was used to store the aqueous solution (8) after storage for + year. The chemical mechanical polishing used in the preparation of the chemical mechanical polishing has the same polishing performance as that of the chemical mechanical polishing aqueous dispersion prepared by using the aqueous dispersion (Α) immediately after the preparation and the aqueous solution (8) after the preparation. Knife 6.4.2 Comparative Example 1 (8) and pure water 'mixed at a weight ratio of 2:1:3, modulating 97127579 30 200919568 Mechanical mechanical grinding water system is divided into m, Λ, n, , / knife loose body ( a+b). The chemical mechanical polishing water is used, and the body (10) is placed in a closed container ♦, and stored in a hunger thermostat for half a year. Dispersion of chemical mechanical grinding water after continuous storage in the years

The body (A+B) confirms the precipitation of the (4) I J colloidal cerium oxide particles Cl and separates into two layers. Determination of colloidal dioxide # τ & Ma Yi Xi Muzi average particle size of the Cl, the results of Ma about 1 bOnm. In addition, only six of them are aware that the pH of the chemical mechanical polishing aqueous dispersion (A+B) after storage of the harvest is &

C. The chemical mechanical polishing aqueous dispersion jA+B) which has been stored for half a year after the static storage is used, and is prepared by using the above-mentioned "6·4.1 (c) using the freshly prepared aqueous dispersion (A) and the aqueous solution (8). Various tests were carried out in the same manner as in the evaluation of the polishing performance of the chemical mechanical polishing water system. The results are shown in Table 4. / From the result D, the water dispersion (A+B) is mechanically ground, compared with the aqueous dispersion (A) after half a year of standing storage and the aqueous solution after storage for six months (8). Modulated chemistry: I) Mechanically ground water dispersion, the number of scratches is significantly increased. This is due to the formation of agglomerates of colloidal ceria C1 contained in the chemical mechanical polishing aqueous dispersion (A+B) after six months of standing storage.夕97127579 31 200919568 (CO5 Comparative Example 7 Mass % CD cd Potassium Hydroxide Hydroxide (N1 OJ OJ 1 - Η CO o* LQ CO ezi ytmc ι-Η 檬酸酸t## Acid acetylene glycol type non-ion过 过 cd cd cd 1 LO 卜 · - J cm ' argon oxidation clock eva τ - Η 1 - Η CD <= ί LO cd OJ CZ5 species r - Η 〇〇 CU citric acid t##酸m S·叫I!屮j4/ 4B1. ^ m tO毋hydrogen peroxide than car exchange example 5 mass% 1—^ C3 cd potassium hydroxide CNI barium argon oxide (ΝΪ rH CN1 1 —Η CO CZ> to CV3 CZ5 Type 1 * citric acid si 1& ^ >1 tf jir κ3 毋 hydrogen peroxide Comparative Example 4 mass % 〇〇> cd potassium hydroxide 1 LO cd inch oi hydroxide Cvl (N3 t CO CZ5 LO Bu·(N1 CD vane .tfhit ^Η (N1 CU citrate ' 1 ji, Mi bag ό ^ hydrogen peroxide Example 3 mass % Ο LO Hydroxide 彳 1 ° Ο CO Potassium hydroxide oi Cvl 1—H ς〇C=5 CO c^i CO 〇 species OJ ε malonic acid cis-butadiene si M屮>d/ 4lkL m t0 hydrogen peroxide Example 2 mass % 〇CZ5 CO Hydroxide 1 LO 〇〇* 0〇potassium hydroxide 1—Η cxi esi ,.* oo cd i—H LO <〇 type a: cis-butene 2 ig·disc ff tO毋hydrogen peroxide Example 1 Quality % cd potassium hydroxide 1 〇〇〇〇CQ argon #Ubif CM i—Η CM T_ ( CO ο ΙΛ oi τ1· "H CM cz> vane .lfr.il Citric acid: acid m il屮Mi miscondensation o ^ Hydrogen peroxide composition name dioxane test f bio-compound other additive composition name polymethacrylate salt biochemical material do not acidify know not interface active agent oxidant extinction τ-· 03 City CO domain 哒#

Vi 61SLZ\L6 200919568 (Table 4)

Example 1 Comparative Example 1 6 months after the preparation of the storage period 6 months 6 months The composition of the first composition AA slurry (A + B) Static storage pH 8.8 8.8 Average secondary particle size (nm) 45 45 Internal Amount of stanol group (xlO23/g) 3. 72 3. 72 Composition of the second component BB pH 12.5 12.5 Slurry (Α+Β) pH 8.9 8.9 8.6 Average secondary particle size (nm) 77 77 160 Grinding Speed (A/min) Copper film 560 560 560 Nitride button film 550 550 510 PEHOS film 610 610 580 BD film 98 98 110 Number of scratches (number / area) 0 0 28 97127579 33 200919568 6· 5 Example 2 and comparison Example 2 6· 5. 1 Example 2 (a) Preparation of the first composition, the above 6. 1 (b) colloid: oxidized 11 particles G2 in the form of an aqueous dispersion: "The prepared colloidal dioxide The aqueous dispersion of 矽C2 was changed, and the inorganic particles were added in an amount corresponding to 16.g f %, and the pH was adjusted to 8.5 by adding emulsified potassium. Then, ion-exchanged water was added so that the total amount of the total components was 100% by mass, and then filtered by a filter of pore size _ to obtain an aqueous dispersion (〇. Further, the i-th composition: (6) colloidal oxidation The Shixi C2 system is uniformly dispersed, and its average secondary particle size is 78nm 〇(b) The second composition is prepared, and is prepared in an amount of 1.2% by mass of quinolinic acid and equivalent to 24% by mass; The 贞τ-ene acid is dissolved in the ion-exchanged water, and the non-ionic interface activity equivalent to 〇·贝 acetylene glycol is added to the “SWynoMM” (manufactured by Απ Products japan), and then the above “6 2 (a) Preparation of an aqueous solution containing polyacrylate P1" The aqueous solution containing the polyacrylic acid salt prepared by adding "approximately 18 mass% of the weight of the polymer is added, stirred for 15 minutes, and then added with hydrogen peroxide. Potassium was adjusted to a pH of 13.0. Then, the total amount of the total constituents was 1% by mass of the force: after entering the ion-exchanged water, the filter was passed through a hole of (45).45//m. Aqueous solution (D). For the ith composition and the second brother used in Example 2 The composition and integration are shown in Table 3. (c) Using the water-based dispersion (c) immediately after preparation and the water after the preparation of the water 97127579 34 200919568 solution (8) prepared by the chemical mechanical research month & evaluation ruler knife body The abrasiveness will be ru ruined by the water dispersion (c) and adjusted with pure water, by weight ratio 2: i /, two π moxibustion aqueous solution (D) 3 〇 mass% of hydrogen peroxide water (the first ^Mixed. After that, the amount of the equivalent amount of 0.5% by weight is diversified into hydrogen peroxide as an aqueous dispersion (C+D). This chemistry; Eryan: used for chemical mechanical polishing

C

L ^ pH λ 9 S ^ a , the mechanical grinding water dispersion (C+D) has a pH of 9_3. Use this chemical machine according to the above "6.3 chemical mechanical polishing: various tests are carried out. The results are shown in Table 5. =) The evaluation of the polishing performance of the aqueous dispersion after half a year of preparation is used. It is 86nm. Also, quietly in the Lord, you - U / ,

In the case of pH 13.0 of the leeches dispersion (C) after standing and storing for 5 years, the aqueous solution (8) after standing for half a year is used to store the aqueous dispersion (c) and the stationary storage half after half a year of use. / After the aqueous solution (D), evaluation of the polishing performance of the chemical mechanical polishing aqueous dispersion prepared by using the aqueous dispersion (c) and the aqueous solution (D) immediately after the preparation of the above r6.5 l (c) Various tests were carried out in the same manner. The results are shown in Table 5. 97127579 35 200919568 From this, it is known that the aqueous dispersion (C) which has been stored for six months after standing and the chemical mechanical polishing aqueous dispersion prepared by the aqueous solution (9) which has been left for half a year after storage, has been prepared and used immediately after preparation. The water-based dispersion ((the same as the chemical mechanical polishing aqueous dispersion prepared by the aqueous solution (D) immediately after preparation) has the same polishing performance. 6 · 5. 2 Comparative Example 2 〇 Immediately after the preparation of the aqueous dispersion (〇) The aqueous solution (D) and the hydrophobic water immediately after preparation are mixed at a ratio of weight ratio of 2: j: 3 to prepare a water-based dispersion ((10)). The dispersion (C+D) is placed in a closed container. The chemical mechanical polishing water dispersion after it is stored in a muscle thermostat ((10) is indeed a colloidal dioxotomy. : After the average secondary particle size of the shifting body of the dioxide dioxide C2, the knot two (two uses: m half, the chemical mechanical grinding water dispersion dispersion. 々.i (c) using the freshly prepared water system Table 5, "The door sample into the various tests. The results are shown in the results of the season Body (6) Chemical mechanical polishing water dispersion after six months of standing storage (6) and static storage with a static storage for half a year after the water system of the mechanical separation of the water system (9) prepared by the chemical machine file release, IL group _PETE〇 Rapid growth of s film 97127579 36 200919568 Reduced, the number of scratches increased significantly. This is due to the colloidal ceria C2 contained in the chemical mechanical polishing water dispersion (C+D) after six months of standing storage. ί 97127579 37 200919568 (Table 5) Example 2 Comparative Example 2 6 months after the completion of the storage period 6 months 6 months Composition of the first composition CC name slurry (C+D) Static storage pH 8.5 8.5 Average Secondary particle size (nm) 78 78 Internal stanol group amount (xlO23/g) 3.70 3.70 Second composition composition name DD pH 13. 0 13.0 Slurry (C+D) pH 9.3 9.3 9.1 Average secondary particle Diameter (nm) 86 86 180 Grinding speed (A/min) Copper film 500 500 500 Nitride button film 530 530 490 PETE0S Film 510 510 430 BD film 70 70 90 Number of scratches (number / area) 0 0 32

97127579 38 200919568 6. 6 Example 3 and Comparative Example 3 6·6· 1 Example 3 (a) Preparation of the first composition 4 Colloid: Water dispersion of oxygen-cut particles G2 = 2: Modulated content The aqueous dispersion of colloidal dioxygen C2 was added in an amount corresponding to 15.0% by mass of the inorganic particles, and the pH was adjusted to 9.0. Then, ion-exchanged water was added so as to add 100% by mass of the total constituent components, and then the pores were passed through; and the aqueous dispersion (8) was obtained. Further, in the colloidal dioxide dioxide C2 system in the above ^ (E), the average secondary particle size is 75 nm ° (b) The modulation of the second composition is equivalent to the amount of U mass %. Butic acid and malonic acid equivalent to 24% = f are dissolved in ion-exchanged water' plus acetylene- and non-ionic surfactants equivalent to 〇6 Berry% "like kiss (10)

The product containing the polyacrylic acid salt (3) prepared by the above-mentioned "6. The preparation of the water-soluble (four) of the acrylate 2 acrylate P3" is equivalent to 3 〇 in terms of the weight of the polymer. The mass % = is added in the mixture, and after stirring for 5 minutes, potassium hydroxide is added to adjust the Qiu to 12.8. Then, the total amount of the total constituents becomes the mass % = the formula is added to the ion after the father changes the water' by the aperture G·45 # m The m was carried out to obtain an aqueous solution (8). The ith composition and the second composition according to Example 3 are collectively shown in Table 3. (4) Using the water-based dispersion (8) immediately after preparation and the 97127579 39 200919568 water solution (F) immediately after preparation, the grindability of the chemical mechanical polishing aqueous dispersion can be evaluated. Water, according to the weight ratio of 2:], (乂, after the preparation of the aqueous solution (F) 30 f # ° / ^. ratio of mixing. Thereafter, will

0 Berry, hydrogen peroxide water (Group 3, two-Z aqueous dispersion (10)). This:::1 is made into chemical mechanical polishing ^ dH , p 1 is converted to mechanical grinding water dispersion (E+F)

粑垆上,:f. "The test method described in this chemical mechanical polishing aqueous dispersion (E + F), 丄 6.3 chemical mechanical polishing test" was used to carry out various tests. The results are shown in Table 6. (d) an aqueous dispersion (E) prepared by modulating the polishing performance of the aqueous solution (F) after half a year after preparation, and a water-based knife (E) prepared by dispersing the semi-chemical mechanical polishing aqueous dispersion The aqueous solution (F) was placed in a closed container, and the temperature was kept at 1 251 for half a year. The colloidal dioxide dioxide in the pure water (8) of the semi-fourth (4) is uniformly dispersed, and its average secondary particle diameter is 75 nm. In addition, the water dispersion after quiescent storage for half a year was 9.0. On the other hand, the aqueous solution (1?) after standing for six months was 12.8. The aqueous dispersion after half a year of storage and the aqueous solution (F) after half a year of standing storage are used, and the aqueous dispersion (E) and the aqueous solution (F) which have just been prepared after using the above r6.61 (c) are used. Various tests were carried out in the same manner as in the evaluation of the polishing performance of the prepared chemical mechanical polishing aqueous dispersion. The results are shown in Table 6. 97127579 40 200919568 From this result, it can be seen that the aqueous dispersion of the chemical mechanical polishing prepared by using the aqueous dispersion (8) after standing for half a year and the aqueous solution (7) after standing for half a year has the same meaning as the aqueous dispersion after the preparation. (8) The polishing performance equivalent to the chemical mechanical polishing aqueous dispersion prepared by the aqueous solution (F) immediately after the preparation. 6. 6. 2 Comparative Example 3 The water-based dispersion (E) immediately after preparation and the freshly prepared water (F) and pure water were mixed at a weight ratio of 2:::3 to prepare a chemical mechanical polishing water. System dispersion (please). The chemical mechanical polishing 用水 dispersion (E+F) was placed in a closed container, and it was stored in a hunger bath for half a year. After half a year of standing and storage, the chemical mechanical mortar water dispersion (E+F) confirmed the sinking of the sputum dioxo C2 and separated it into two reeds. After the average secondary particle diameter of the colloidal silica dioxide C2 is measured, the result is about two = half a year after the chemical mechanical polishing water dispersion second dispersion 0. 0. UCB is more than just after the preparation of the water system is divided into two bodies (8) The chemical mechanical polishing water-based dispersion prepared by the aqueous solution (F) = the evaluation of the pure product can be evaluated. The results are shown in the results. It is confirmed that the chemical mechanical polishing water is dispersed after half a year of standing storage, compared with the water system after half a year of using the static storage, and the aqueous solution after half a year of standing storage (F) The prepared chemical and full-grinding water dispersion, the nitriding (four) or the (10) film grinding = 97127579 41 200919568 reduced, the number of scratches increased significantly. This is due to the formation of agglomerates of colloidal ceria C2 contained in the chemical mechanical polishing aqueous dispersion (E+F) after standing for six months.

C 97127579 42 200919568 (Table 6) Example 3 Comparative Example 3 6 months after the preparation of the storage period 6 months and 6 months The composition of the first composition EE slurry (E + F) was allowed to stand for pH 9.0 9.0 average twice Particle size (nm) 75 75 Internal stanol group amount (xlO23/g) 3. 75 3.75 Second composition composition name FF pH 12.8 12.8 Slurry (E+F) pH 9.1 9.1 9.4 Average secondary particle size ( Nm) 82 82 175 Grinding speed (A/min) Copper film 480 480 480 Tantalum nitride film 500 500 450 PETE0S Film 490 490 410 BD film 85 85 90 Scratch number (number / area) 0 0 40

L 97127579 43 200919568 6. 7 Comparative Example 4 The pH of the second composition was set to be substantially different from the point at which the example j 疋 was 7.5. (a) Modification % of the first composition: the bismuth-containing hydrogen hydride prepared by the 'modulation' of the aqueous dispersion of the upper bismuth (4) colloidal cerium oxide particle ci is regarded as an inorganic particle equivalent to T6 0 The water-based dispersion of C1 was added in such a manner that the pH was adjusted to be changed by potassium hydroxide, and the amount of the amount of niobium added was 100% by mass. Then, the filter is removed by the total amount of the total constituent components, and the colloidal dispersion (6) in the pores 1 P (6) is obtained by the work of the exchange of water. Further, the water system was dispersed to 45 nm. Is uniformly dispersed in the amount of the average secondary particle size (b) of the composition of the composition of the 2nd composition of the C content of the leaching acid and the equivalent of "% by mass of the knowledge of the acid dissolved in the ion '% of B Block triol type non-ionic hydrazine change water 'additional equivalent to 0.6 mass C / p H ', I surface 'tongue agent 'Surfyn〇i465' (Air

Products japan company). y "The preparation of the aqueous solution of (4) r enoate P2, the description of 6, 2 (b) aqueous solution containing polyacrylic acid" is added to the polyacrylic acid salt of the polymer weight, added, and mixed for 15 minutes, The amount of the field was 2.4, and the pH was adjusted to 7.5 with the total constituent potassium. After ion-exchanged water, the aqueous solution (8) is added by means of pore size. The filter for Comparative Example / =1 was subjected to enthalpy to obtain a product, and the integration is shown in Table 3. The first composition to be used and the second stage 97127579 44 200919568 (C) The polishing property of the chemical mechanical polishing aqueous dispersion prepared by using the water-based dispersion (G) and the fresh water (8) immediately after preparation: After the aqueous dispersion (6) and the preparation and pure water, 30% by mass of hydrogen peroxide water (third composition) is mixed at a weight ratio of 2:1:3 to be exchanged: when the amount of t〇·2 is fine Add, modulate into a chemical machine = aqueous dispersion (4)). The pH of the chemical mechanical polishing aqueous dispersion was 8.9, which was the same as the chemical mechanical polishing used in the Example: Sanqing. Further, this chemical mechanical polishing water is dispersed in hydrazine. Two: contains, the average of the colloidal cerium oxide π 2 with, with the application! The chemical mechanical polishing aqueous dispersion (A + B) used was the same particle diameter. This test was carried out according to the test method described in the above-mentioned "6.3 Chemical Mechanical Polishing Test" using the air-through technique + ... 1 "Mechanical Grinding Water Dispersion ((4))". The results are shown in Table 7. From the result of the cancer, it was recognized that the number of scratches in the chemical mechanical polishing after the preparation of the octahedron (G+H) was significantly higher than that of the chemical mechanical polishing water immediately after the preparation = dispersion U+B) . This is because the pH of the crude product is as high as 10. 5, and the internal decane of colloidal cerium oxide is 4,20 χ 1 023 /g, thus causing scratches. In the middle of the case, the comparative example 5 was compared with the embodiment, the poly(methyl) acrylate was added to the W-th product, and the poly(methyl) propyl group was not added to the second composition. The points of the dilute acid salt are quite different. 97127579 45 200919568 (a) Modification of the first composition The water dispersion of the colloidal cerium oxide C1 containing the water dispersion of the oxygen dispersion particle C1 prepared by the above-mentioned "6.1 (a) combined modulation" is dispersed. The body is replaced by I';;: Lithium is added in an amount equivalent to 16.0% by mass, and the aqueous solution prepared by the preparation of the aqueous solution of the upper diacrylate P2 is converted into an aqueous solution of Ρθ2 The weight of the polymer is quite

The spleen and the mussels were added to the %. After (15 minutes), the pH was adjusted to 8 8 by adding potassium hydroxide. The water dispersion (i) > After the water-repellent ionic father changed the water, the pore diameter of 1/zm was used to obtain the colloidal silica dioxide in the aqueous dispersion (I)c, and the C1 system was uniformly dispersed by 130 nm. (b) Modification of the composition of the younger brother 2 The amount of quinolinic acid in the amount of 1.2% by mass and the equivalent of "% by mass

C A large amount of citric acid is dissolved in ion-exchanged water, and the equivalent of 0.6 is added. Acetylene monool type nonionic surfactant "-(10)5" (...

Products Japan company).立%,) Then, add potassium sulphate to adjust the pH, and add the ion exchange 尨# n, 里 4 n 错 wrong aperture 0.45" in a total mass of the total constituents. The passer is carried out: repeatedly, passed to the aqueous solution (1). For the comparative example 5 and the second composition, the integration is shown in Table 3. Further, i, and 成 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (7) Place the closed solution so that the trap can be stored in the constant temperature tank. “Solid month. Static storage: Do not separate the solid body (1) and confirm that the colloidal silica dioxide π 之 之 = = = = = = 且 且 且 且 且 且 且 且 。 。 In the case of the colloidal silica dioxide, the diameter of the colloidal stone is 2 dragons. It can be seen that the colloidal silica dioxide has a lower π:if: the lower the performance. The above-mentioned 'aqueous dispersion (1) has a difference of 4 and cannot be performed. The evaluation test of the grinding. The dispersion of the centrifugation dispersion (1) was 88. The storage of the aqueous solution of water after one month (7) was followed by the comparison of the comparative example 6 /, ,, and . In the comparative example 6, the pH of the second composition is set to 7.5, the pH of the second composition is set to be the same, and the first composition is used as the flute 9; the points are greatly different. The potassium hydroxide in the dispersion, the material household: the 5-week chemical mechanical research is the same in Comparative Example 6. The & According to the preparation of the first embodiment and the first composition of the above (a), the colloidal dioxygen/water prepared by the above-mentioned "6.1 (a) colloidal oxidation preparation" is regarded as an inorganic particle. ^ The aqueous dispersion is adjusted to a pH of 75 by the change of potassium hydroxide. The amount of addition is 100% by mass, and the total amount of the components is the total amount of the filter. After passing through the ion exchange water, the pores in the pore size _ body (1) are oxidized; the dispersion is (1) and the water system is dispersed at 4 〇 nm. The oxidized eve C1 system is uniformly dispersed, and the average is twice. Particle size 97127579 47 200919568 (b) Preparation of the second composition The amount of quinolinic acid equivalent to 1.2% by mass and citric acid equivalent to 1.2% by mass are dissolved in ion-exchanged water, and the equivalent amount is added. 6 mass% of the block-alcohol type nonionic surfactant "Surfyn〇i465" (Air

The product of the polyacrylate p2 prepared by the preparation of the above-mentioned "6-2 (b) preparation of an aqueous solution containing polyacrylate P2" is equivalent to 2. The amount of 4% by mass was added, and after 15 minutes of dropping, the pH was adjusted to 13.5 by adding chlorine oxidation. Then, ion-exchanged water was added so that the total amount of the total constituent components became 1% by mass, and then the mixture was passed through a crucible having a pore diameter of .45 Am to obtain an aqueous solution α). The ith composition and the second plant used in Comparative Example 6 are collectively shown in Table 3. (c) using the polishing performance of the chemical mechanical polishing water dispersion prepared by the 匕 』 』 衣 & & & 糸 糸 糸 糸 糸 糸 糸 糸 κ κ κ κ 刚 刚 刚 刚 刚 刚 刚

U and aqueous solution α) 30% by mass of hydrogen peroxide water (third composition) is added in an amount of 0.2% by mass in excess of f, and is adjusted to be an aqueous dispersion (1) L). The pH for chemical mechanical polishing is 9.5. Using this chemical mechanical polishing: two: body (_ According to the "6.3 metal chemical polishing test" described above, various tests were carried out. The results are shown in Table 7. The lack of test method, confirmed from the results, just modulated After the completion of 97127579 ^ mechanical grinding water system 200919568 bulk α + L), compared to the chemical mechanical polishing water dispersion (A + B) just after the preparation of the copper film grinding speed is reduced. This is because the pH of the J-th composition is too low relative to the pH of the chemical mechanical polishing aqueous dispersion (K + L), so that the pH immediately after the preparation is unstable. The point of the pH value of 3.5 is greatly different from the case of the example of the present invention. (a) Preparation of the first composition The first composition is the aqueous dispersion (A) prepared by the above-mentioned "6.4. 1 (modulation of the second composition). (b) The modulation of the second composition will be equivalent. The amount of quinolinic acid in an amount of 1.2% by mass and citric acid equivalent to 12 masses are dissolved in ion-exchanged water, and an acetylene glycol-type nonionic surfactant corresponding to 6% by mass of cerium is added. "Surfyn〇1465 (Air

Products made by japan, Inc., 'The polyacrylate-containing aqueous solution prepared by the above-mentioned "6. 2 (b) Preparation of aqueous solution containing polypropylene sulphate P2" is equivalent to the weight of the polymer. The amount of 2.4% by mass was added and stirred for 15 minutes. Next, ion-exchanged water was added in such a manner that the total amount of the total constituent components was 1% of mussels, and then (4) was carried out by filtration 11 having a pore diameter of 0.45 / / m to obtain an aqueous solution (M). 5。 The pH of the aqueous solution (M) is 3.5. The first composition and the second composition used in Comparative Example 7 are collectively shown in Table 3. (:) Grinding performance of a chemical mechanical polishing aqueous dispersion using the water dispersion (1) immediately after preparation and the water 'liquid (M) immediately after preparation 97127579 49 200919568 Evaluation will be just after preparation k with pure water 'by weight ratio 2:·,} 'loose body (A) and the prepared aqueous solution (M) 3?, hydrogen peroxide water (the ratio of the third group = equivalent to 〇 · 2 mass %%%~, change to hydrogen peroxide as aqueous dispersion (A+M). However, ^ add '/week for chemical mechanical polishing

After the preparation of the gel, the colloidal research occurs: the water dispersion ((4)) The dispersion stability is low, and it is known that the colloidal dioxide (10) forms agglomerate, which is divided into small parts, and the chemical mechanical polishing water dispersion (A+ M) The state difference is two. The grinding 5 parity test is performed. This is due to the presence of colloidal cerium oxide particles in the acidic region in the presence of an (acetylene glycol-type non-ionic) surfactant, which causes immediate aggregation. Therefore, it is known that the pH of the second composition must exist in the alkaline region. 97127579 50 200919568 α嵴) Comparative Example 7 Immediately after preparation, 〇〇〇〇LO inch CO LO CO 1 1 cannot be implemented, cannot be implemented, cannot be implemented, cannot be implemented, cannot be implemented, cannot be implemented, Comparative Example 6, just after finishing, LO Bu· ο 1 LO CO LO ai 卜 CZ> 03 inch ◦ LO LO CI3 Τ—Η CD 〇〇α: CD 〇Comparative example 5 1 month later 16 1 CO oo 〇〇" 1050 Unable to implement cannot be implemented Unable to implement cannot be implemented Implementation cannot be implemented Comparative Example 4 Immediately after preparation Ο LO C3 Τ'··"Ί LO inch 4. 20 LO 卜 ' CD od Bu Bu CO LO ◦ LO LO 〇CO 〇0 CJ5 LO 〇Example 1 Just modulated After completion 〇〇 od LO CO 卜 CO LO οά r—Η CT5 oo c— 〇 〇 CO LO <〇LO LO Ό CO 〇0 05 <0 组成 Composition during the storage period CU Average secondary particle size (nm) Internal stanol group amount (Χίο23 pieces/g) Composition name a Average secondary particle diameter (nm) Copper film tantalum nitride film PETE0S Film BD film scratch number (number/region) Corrosion evaluation 1 First composition second Composition mixing slurry 啭.5 -61SLUL6 200919568 [Simple diagram BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a chemical mechanical polishing apparatus of the present embodiment. [Main component symbol description] 10 Semiconductor substrate 12 Slurry supply nozzle 14 Water supply nozzle 16 Slurry 18 Grinding cloth 20 Rotary table 22 Top ring 24 Dresser 100 Chemical mechanical polishing device 97127579 52

Claims (1)

200919568 Ten patent application scope: 1. A chemical mechanical polishing aqueous dispersion preparation kit, comprising: a first composition comprising colloidal cerium oxide and a basic compound, having a pH of 8 or more and 1 〇 or less; The second composition contains a poly(indenyl)acrylate and a basic compound, and has a pH of 11 or more and 13 5 or less. 2. The chemical mechanical polishing water dispersion preparation kit according to the scope of the patent application, wherein the second composition is a step active agent. 1 3. For the chemical mechanical polishing water dispersion preparation for the Scope of Patent Application No. 2, pots Φ, Bu; X, Cry; Sheep & Shiyan A ^ wherein the above surfactant is selected from At least one of acetylene glycol, an ethylene bromide adduct of an acetophenone alcohol, and an acetylene alcohol. ^ If you apply for a patent range! The chemical mechanical polishing water-based dispersion preparation kit, in the pot, the above-mentioned second and private compounds. The composition of the chemical shirt polishing body according to the fourth aspect of the patent application, wherein the acidification is the same as the acidification, and the D is selected from the group consisting of quinolin. Porphyrin carboxylic acid, quinolinate, maleic acid, malonic acid, spoiled species. At least 1 of the body 0 owing and frequency acid. 6. The chemical body modulation kit of the scope of the patent application s Wherein, the above colloidal dioxide is used: 9 乂 is 30 nm 〜 l 〇〇 nm. Sentence primary particle size 7 · Chemical mechanical polishing water dispersion according to claim 1 of the scope of the patent item 97127579 53 200919568 Body 5 week system set, basin In the middle, the weight of the average weight of the poly (meth) acrylate is 500, 〇〇〇~3, 000, 000. 8. If the application scope is 帛i The chemical mechanical polishing water-based dispersion preparation kit, wherein the third embodiment containing the oxidizing agent is further provided. • 9 · A chemical mechanical polishing aqueous dispersion preparation method, and the following composition of 3 persons To modulate a chemical machine having a pH of 8 or more and 12 or less; The ith composition contains a colloidal silica dioxide and a compound having a pH of 8 or more and 1 Torr or less; and the second composition contains a poly(meth) acrylate and a basic compound, and pIi is 丨丨3. The following is a method for preparing a chemical mechanical polishing water according to claim 9 of the ninth aspect of the invention, wherein the oxidizing agent is further mixed with the first: an oxidizing agent to prepare a pH of 8 or more and 12 or less. Chemical machinery ^ composition of the dispersion. Honing water system \ J 97127579 54