TW200840861A - Polishing liquid - Google Patents

Abstract

To provide a polishing liquid for polishing a barrier layer that uses solid state abrasive grains in a barrier CMP for polishing a barrier metal material and that can exhibit excellent polishing speed for polishing barrier films and prevent the formation of scratches due to a corrugation of abrasive grains. A polishing liquid for polishing a semiconductor IC barrier layer, comprising a colloidal silica, a compound containing a carboxyl group, a corrosion inhibitor, and a cationic compound represented by general formula (I) or general formula (II), wherein the pH is 2.5 to 5.0. (in general formula (I), R1 represents the same substituent as that selected from the group of hydrocarbon groups having 1 to 18 carbon atoms; and in general formula (II), R2 and R3 each independently represent hydrocarbon groups; and n represents the integer of 1 or larger).

Description

200840861 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a honing fluid used in the process of a semiconductor device, and more particularly to a barrier metal material mainly for planarization of a wiring process of a semiconductor device. The honing of the honing fluid. [Prior Art] In the development of a semiconductor device represented by a semiconductor integrated circuit (hereinafter referred to as LSI), in order to reduce the size and speed of the semiconductor device, in recent years, it has been required to increase the density and increase the thickness of the wiring. Physicalization. As the technique used for this, various techniques such as chemical mechanical polishing (hereinafter referred to as CMP) are used. This CMP is a technique necessary for planarization of a surface of a film to be processed such as an interlayer insulating film, formation of a plug, formation of a buried metal wiring, etc., and smoothing of a substrate or removal of excess metal film at the time of wiring formation. Or the removal of the excess barrier layer on the insulating film. The general method of CMP is to stick the honing pad on a circular honing plate, immersing the surface of the lining pad with honing liquid, and the substrate (wafer). The surface is pressed against the pad, and both the honing plate and the substrate are rotated in a state where a predetermined pressure (honing pressure) is applied from the inner surface thereof, and the surface of the substrate is flattened by the mechanical friction generated. When manufacturing a semiconductor device such as an LSI, a plurality of fine wirings are formed, and when a metal wiring such as Cu is formed in each layer, the wiring material is prevented from being diffused to the interlayer f insulating film or the wiring material is improved in adhesion. Ta or TaN, Ti, TiN, etc. barrier metal. 200840861 In order to form each wiring layer, CMP (hereinafter referred to as metal film CMP) containing a metal film is first performed in one or more stages to remove excess wiring material deposited by plating or the like, and then CMP (hereinafter referred to as The barrier metal (CMP) is used to remove the barrier metal material (barrier metal) that is exposed at the surface. However, due to the metal film CMP, the wiring portion is excessively honed to cause so-called shallow dishing or a problem of erosion. In order to reduce the shallow dishing, in the barrier metal CMP performed after the metal film CMP, it is required to adjust the honing speed of the metal wiring portion and the honing speed of the barrier metal/section, and finally form a height difference such as shallow dishing or etching. Less wiring layer. In other words, in the barrier metal CMP, when the blasting speed of the barrier metal or the interlayer insulating film is relatively small compared with the metal wiring material, the wiring portion is quickly honed or the like, and the dish is etched. The honing speed of the barrier metal or the insulating film layer is moderately large. This is because it has the advantage of increasing the throughput of the barrier metal CMP, and in fact, due to the shallow disc formation of the metal film CMP, for the above reasons, it is required to relatively improve the barrier metal or the insulating layer. The point of speed is also hoped for this. The metal used in I CMP is a honing solution, generally comprising abrasive particles (e.g., aluminum oxide, vermiculite) and an oxidizing agent (e.g., hydrogen peroxide, persulfuric acid). It is believed that the basic mechanism is to oxidize the surface of the metal by an oxidizing agent and to remove the oxide film by abrasive grains. However, if CMP is used to carry out CMP with such solid abrasive grains, honing damage (scratches), honing of the entire surface of the honing surface beyond the need to be honed (thinning), honing the metal surface in the dish The phenomenon of upper bending (shallow disc) and the insulation of the metal wiring compartment exceed the phenomenon that the plurality of wiring metal faces are bent on the 200840861 disc (erosion). Further, by using a honing liquid containing solid abrasive grains, in order to remove the honing liquid remaining on the semiconductor surface after honing, the cleaning step usually performed is complicated, and in order to handle the washed Liquid (waste liquid), solid abrasive grains must be sedimented and separated, and there is a problem in terms of cost. For the honing liquid containing solid abrasive grains as described above, there are various reviews as follows. For example, there are proposals for CMP honing agents and honing methods for high-speed honing f with little honing damage (for example, According to the patent document 1), the honing composition and the honing method (for example, refer to Patent Document 2) for improving the CMP, and the honing composition for preventing the aggregation of the honing abrasive grains (for example, refer to the patent) Literature 3). However, in the honing liquid as described above, it is currently known that a honing liquid is not obtained, which can achieve a high honing speed when honing the barrier layer, and can suppress scratches caused by aggregation of solid abrasive grains. . [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2003-142435 (Patent Document 2) JP-A-2003-142435 [Patent Document 3] JP-A-2000-84 8 3 2 SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The purpose of the invention is to provide a honing liquid using solid abrasive grains for damaging the barrier CMP of the barrier metal material, in order to achieve an excellent honing speed of the barrier film and to suppress scratches caused by agglomeration of the abrasive grains. The barrier layer containing solid abrasive grains is honed. 200840861 Solving the problem

The inventors of the present invention conducted a careful review and found that the above problems can be solved by using the following honing liquid, and finally the problem is finally reached. That is, the present invention is as described in the following Z < 1 > A honing liquid for honing a barrier layer of a semiconductor integrated circuit, which comprises the following general formula (I) or general formula (II) The cationic compound, the compound having a carboxyl group, the corrosion inhibitor, and the zeta potential of the surface in the presence of the cationic compound show a positive colloidal vermiculite (.', and the honing fluid pH is 2.5~5.0, R1

R1—N—R1 Formula (II R1 [In the formula (I), R1 represents the same substitution selected from a hydrocarbon group having 1 to 18 carbon atoms;

R^—Ν

R3 [In the formula (II), R2 and R3 each independently represent a hydrocarbon group. η represents an integer of 1 or more]. &lt;2&gt; The honing liquid according to the above <1>, wherein the compound represented by the above formula (Π) is derived from tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, and tetrapenta The compound of the above formula (Π) 200840861 is a molecular weight of i 〇〇 〜 2, as described in <1> or &lt;2&gt; The honing liquid according to any one of <1> to <3>, wherein the compound having a carboxyl group is a formula (111). The compound shown, R4—〇—R5—cooh General formula (丨丨&quot; [In the formula (III), R4 represents a hydrocarbon group, R5 represents a hydrocarbon group or a mineral group, and R4 and R5 may be bonded to each other to form a ring. The damper liquid for barrier ribs described in <4>, wherein the compound represented by the above formula (III) f'-i is derived from 2-furancarboxylic acid, 2,5-furan. At least one selected from the group consisting of dicarboxylic acid, 3-furancarboxylic acid, 2 stomach tetrahydrofurancarboxylic acid, diglycolic acid, methoxyacetic acid, methoxyphenylacetic acid, and phenoxyacetic acid. The honing liquid according to any one of <1>, wherein the corrosion inhibitor is from 1,2,3-benzotriazole, 5,6-dimethyl -1,2,3-benzotriazole, 1-(1,2-dicarboxyethyl)benzotriazole, l_[N,N-bis(hydroxyethyl)aminemethyl]benzotriazole and At least one compound selected from the group consisting of 1-(hydroxymethyl)benzotriazole. # V Although the effect of the present invention is not clear, it is judged to be caused by the formula in the liquid of pH = 2.5 to 5.0. I) or the presence of the cationic compound represented by the general formula (II) 'The surface of the colloidal vermiculite particles of the abrasive grains shows a positive boundary potential (ζ potential)' due to the surface potential of the particles, and the grinding is appropriately controlled According to the present invention, it is possible to provide a honing agent for a barrier layer containing solid abrasive grains, which is excellent in the adsorption/repellency of the particles on the surface of the barrier film. The honing speed is suppressed and the scratch caused by the aggregation of the abrasive grains -10- 200840861 is suppressed. [Embodiment] The best shape for carrying out the invention The following describes the specific aspect of the invention. The honing liquid of the present invention is a honing liquid for damaging the barrier layer of the semiconductor integrated circuit, and contains (A) a cationic compound represented by the general formula (1) or the general formula (11) as an essential component, (B) a compound having a carboxyl group, (c) a corrosion inhibitor, and (D) a boundary colloidal potential in the presence of the cationic compound exhibiting a positive colloidal vermiculite, and the pH of the honing liquid is 2.5 to 5.0 . Further, the honing liquid of the present invention may further contain other components in addition to the essential components, and examples of the preferred components include an anionic surfactant, an organic acid, and a heteroaromatic ring compound. The above-mentioned components contained in the honing liquid may be one type or two or more types. Further, the case where the damper for the barrier layer of the present invention is simply referred to as a honing fluid is also hereinafter described. The term "honing fluid" as used in the present invention means not only the honing liquid (that is, the honing liquid which is diluted as needed) but also the concentrate of the honing liquid, the concentrated liquid or the concentrated liquid. The honing liquid system means a honing liquid prepared to be higher than the solute concentration of the honing liquid used in the honing, and is used for honing when diluted in water or an aqueous solution when used in honing. The magnification is usually from 1 to 20 volume. The "concentration" and "concentrate" in this manual are used to mean the use of "thick" and "thick liquid". The general term of the physical concentration operation such as evaporation is used in a different manner. -11- 200840861 Each component constituting the honing liquid of the present invention will be described in detail below. First, the characteristic component of the present invention, that is, a cationic compound will be described. (A) a cationic compound represented by the formula (I) or the formula (11): The cationic compound which can be used in the invention is selected from the group consisting of the following formula (I) or formula (11). One or more compounds of the compound. R1 r1—~N—R1 General formula (I) R1

In the above formula (I), R1 represents the same substituent selected from a hydrocarbon group having 1 to 18 carbon atoms. R1 is preferably a hydrocarbon group having 1 to 18 carbon atoms, and examples of the hydrocarbon group herein include an alkyl group, an aryl group, and a phenyl group. Among them, an alkyl group having 1 to 5 carbon atoms is preferable. Specific examples of the compound represented by the formula (I) include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, and tetraamylammonium.

In the above formula (II), R2 and R3 each independently represent a hydrocarbon group, and preferably represent a hydrocarbon group having 1 to 10 carbon atoms. R2 preferably represents a divalent nicotine group having a carbon number of 1 to 10, for example, an alkylene group having 1 to 10 carbon atoms. R3 represents a monovalent smoky group having a carbon number of 1 to 10, for example, a decyl group, an aryl group, a phenyl group having a carbon number of 1 to 1 Å, and the like. R2 and R3 may further have a substituent. Examples of the substituent which may be introduced include an alkyl group, a hydroxyl group, a carboxyl group and the like. η represents an integer of 1 or more. -12- 200840861 That is, the compound represented by the formula (π) is an oligomer or polymer in which the above structural units are connected by n, and the weight average molecular weight is about 100 to 20,000, and the stability of the particles is honed. The point of view is appropriate. Therefore, η indicating the number of bonds of the structural unit in the formula (Π) can be appropriately determined by the substituent which the structural unit has, or the molecular weight thereof and the above preferred weight average molecular weight of the compound. Specific examples of the compound represented by the formula (II) include polyethyleneimine and polypropyleneimine. f ' These (A) cationic compounds may be used alone or in combination of two or more kinds. When two or more kinds of the above-mentioned cationic compounds represented by the formula (I) are used, two or more kinds of the cationic compounds represented by the formula (II) may be used in combination, and The cationic compound represented by the formula (I) and the cationic compound represented by the formula (II) may be used in combination. Due to the presence of the component (A), the zeta potential of the surface of the colloidal vermiculite described later shows a positive enthalpy. That is, if the (Α) component is coexisted with the colloidal particles of the abrasive grains in the honing liquid, the shell component is adsorbed on the surface of the colloidal vermiculite particles, and the surface is (D) by controlling the potential. The boundary potential shows a positive colloidal vermiculite. The amount of the cationic compound represented by the above formula (I) or the formula (II) is from the viewpoint of the stability of the honing particles, and the quality of the honing liquid used in the honing. In other words, 〇0 1 to 1% by mass, more preferably in the range of 0·0 1 to 5 mass%. [(B) Compound having a Carboxyl Group] In the honing liquid of the present invention, it is necessary to contain (B) a compound having a carboxyl group. -13-200840861 The compound having a carboxyl group is not particularly limited as long as it has at least one carboxyl group in the molecule, and from the viewpoint of improving the honing rate, it is preferred to select the following formula (III). ) the compound shown. The number of carboxyl groups present in the molecule is preferably from 1 to 4, and more preferably from 1 to 2 from the viewpoint of being inexpensive to use. R4 - hydrazine - R5 - COOH General formula (III) In the above formula (III), R4 represents a hydrocarbon group, R5 represents a hydrocarbon group or a carbonyl group, and the hydrocarbon group is preferably a carbon number of 1 to 10. R4 and R5 may be bonded to each other to form a ring structure. R4 and R5 may have a more substituent, and examples of the substituent which may be introduced include an alkyl group having 1 to 3 carbon atoms, an aryl group, an alkoxy group, a carboxyl group, and the like, and when a carboxyl group is used as a substituent, The compound is a carboxy group having a complex number. Examples of R4 include an alkyl group having 1 to 1 Å carbon atoms, an aryl group, and a cycloalkyl group. Examples of R5 include an alkylene group having 1 to 1 carbon atom, a carbonyl group, and an aryl group. Examples of the compound represented by the above formula (III) include 2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, and di-glycolic acid. Methoxyacetic acid, methoxyphenylacetic acid, phenoxyacetic acid, etc., wherein diglycolic acid, 2-furancarboxylic acid, 2,5-furandicarboxylate is preferred from the viewpoint of an increase in honing speed. acid. (B) A compound having at least one carboxyl group in the molecule may be used alone or in combination of two or more kinds in the honing liquid. In the honing liquid of the present invention, the amount of the compound (B) having a carboxyl group is preferably 'the amount of the compound represented by the formula (III), and is used for the quality of the honing liquid used in honing. In other words, it is preferably 质量·1 mass% or more and 5 mass-14 to 200840861% or less, more preferably 0.5 mass% or more and 2 mass% or less. That is, the content of the compound having a carboxyl group is preferably 0.1% by mass or more from the viewpoint of achieving a sufficient honing speed, and is preferably 5 from the viewpoint that excessive shallowing does not occur. Below mass%. [(D) The boundary potential of the surface in the presence of the cationic compound shows a positive colloidal chopped cation] The honing liquid of the present invention contains colloidal vermiculite as at least a part of the abrasive particles. / As the colloidal vermiculite, it is more preferably a colloidal vermiculite obtained by hydrolysis of an alkoxysilane without containing an alkali metal or the like inside the particles. On the other hand, a colloidal vermiculite produced by a method of removing alkali from an aqueous solution of a citric acid base may be used. However, in this case, the alkali metal remaining inside the particles is gradually dissolved, which may affect the honing performance. From such a viewpoint, it is more preferable to use a material obtained by hydrolysis of the alkoxysilane as a raw material. The particle size of the colloidal vermiculite of the raw material is suitably selected in accordance with the purpose of use of the abrasive grains, and is generally about 10 to 200 nm. Further, in the present invention, the colloidal vermiculite is adsorbed to the surface by the coexistence of the cationic compound represented by the above formula (I) or the formula (II). The boundary potential of the particle surface shows a positive enthalpy. Such a boundary potential shows a colloidal vermiculite which is suitably referred to as (D) a specific colloidal vermiculite. The boundary of the surface of the (D) specific colloidal vermiculite particles in the honing liquid can be measured, for example, by means of an electrophoresis method or an ultrasonic vibration method. As a specific measuring apparatus, DT-1200 (Japan RUFUTO Co., Ltd.) or the like can be used, and such a measuring device can be used and measured by a usual method. -15- 200840861 Further, the content of (D) specific colloidal vermiculite in the honing liquid of the present invention is used for honing liquid used for honing (that is, honing after dilution with water or an aqueous solution) The mass of the liquid is preferably 1% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 12% by mass, in comparison with the following "synonymous with honing liquid used in honing". Hereinafter, it is particularly preferably 5% by mass or more and 12% by mass or less. SP, (D) The content of the specific colloidal vermiculite is preferably 1% by mass or more from the viewpoint of honing the barrier layer at a sufficient honing speed, and is preferably from the viewpoint of preservation stability. 1 5 or less. f In the honing liquid of the present invention, the abrasive particles other than the above-mentioned (D) specific colloidal vermiculite may be used as long as the effects of the present invention are not impaired. In this case, among all the abrasive grains, the content of the (D) specific colloidal vermiculite is preferably 5% by mass or more, particularly preferably 80% by mass or more. The abrasive particles contained may also be all (D) specific colloidal vermiculite. The honing liquid of the present invention may be exemplified as abrasive grains which can be used for (D) specific colloidal vermiculite, igneous vermiculite, alumina, alumina, titania or the like. The size of the abrasive grains used for these purposes is the same as (A) colloidal vermiculite, or it is V, and preferably 2 times or less. [(C) Corrosion Inhibitor] The honing liquid of the present invention contains a corrosion inhibitor of uranium which is adsorbed on the surface to be honed to form a film and suppress the surface of the metal. The uranium sulphide inhibitor in the present invention preferably has three or more nitrogen atoms in the molecule and contains a heteroaromatic ring compound having a condensed ring structure. Here, the "three or more nitrogen atoms" are preferably atoms which constitute a condensed ring, and as such a heteroaromatic ring compound, benzotriazole and a derivative obtained by introducing various substituents to the benzotriazole are preferred. -16- 200840861 Creature. Examples of the corrosion inhibitor which can be used in the present invention include benzotriazole, 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, and 1 -(1,2·dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl)aminemethyl]benzotriazole, 1-(hydroxymethyl)benzotriazole, etc. Preferably, it is from 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 1-(1,2-dicarboxyethyl)benzotriene One or more compounds selected from azole, 1-[N,N-bis(hydroxyethyl)aminemethyl]benzotriazole and 1-(hydroxymethyl)benzotriazole. (The amount of the (C) corrosion inhibitor added is preferably 质量1% by mass or more and 0.2% by mass or less, more preferably 0.05% by mass, based on the mass of the honing liquid used in honing. In addition, the amount of the heteroaromatic ring compound added is preferably 0.01% by mass or more from the viewpoint of not expanding the shallow dish, and is preferably from the viewpoint of storage stability. 0.2% by mass or less. In the honing liquid of the present invention, the essential components of the above (A) to (D) may be appropriately added according to the purpose. Such an additive component is described. L [Oxidant] The honing liquid of the present invention is preferably used. A compound (oxidizing agent) containing a metal capable of oxidizing the object to be honed. Examples of the oxidizing agent include hydrogen peroxide, a peroxide, a nitrate, an iodate, a periodate, a hypochlorite, and a sub Chlorate, chlorate, perchlorate, persulfate, dichromate, permanganate, ozone water, and silver (II) salt, iron (111) salt, of which peroxidation is preferred Hydrogen. As the iron (III) salt, for example, iron (III) nitrate is preferably used, and chlorination is preferred. (III) -17- 200840861, inorganic iron (III) salts such as iron (III) sulfate and iron (III), and organic wrong salts of iron (III). The amount of oxidant added may follow the initial stage of CMP When the amount of shallow dishing in the initial stage of the barrier CMP is large, that is, when the wiring material is less likely to be honed in the barrier CMP, it is preferable to reduce the amount of the oxidizing agent added. When it is desired to honing the wiring material at a high speed, it is preferable to increase the amount of the oxidizing agent added. Thus, in order to change the amount of the oxidizing agent in accordance with the initial dishing of the barrier CMP, the honing liquid used in the honing is used. In the /1L, it is preferably 〇.〇1 摩尔~1 耳, especially preferably 〇.05 摩尔~〇.6 莫耳. [pH and pH adjuster] The honing liquid of the present invention requires pH 2. 5 to 5.0, preferably in the range of pH 3 to 4. From the viewpoint of achieving a high honing speed, it is preferred to control the pH of the honing liquid within the range. In order to adjust the pH within the above preferred range The alkali/acid or buffer is used. The pH of the honing liquid of the present invention can exhibit excellent effects within this range. The granule is preferably a non-metal alkaline agent such as an organic ammonium hydroxide such as ammonia, ammonium hydroxide or tetramethylammonium hydroxide, or an alkanolamine such as diethanolamine, triethanolamine or triisopropanolamine. An alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide; an inorganic acid such as nitric acid, sulfuric acid or phosphoric acid; a carbonate such as sodium carbonate; a phosphate such as trisodium phosphate; a borate or tetraborate; Salt, hydroxybenzoate, etc. Particularly preferred base agents are ammonium hydroxide 'potassium hydroxide, lithium hydroxide and tetramethylammonium hydroxide.

The amount of the alkali/acid or the buffer to be added may be an amount in which the pH -18 to 200840861 is maintained within a preferred range as long as the conductivity is less than 値, and preferably 1 L of the honing liquid at the time of honing. It is 0.0001 Mo ~ Lo Mo, more preferably 0.003 Mo ~ 0.5 Mo. [Chelating Agent] The honing liquid of the present invention preferably contains a chelating agent (i.e., a hard water softening agent) as needed in order to reduce adverse effects such as polyvalent metal ions to be mixed. The chelating agent is a hard water softening agent or a similar compound which is a general use of a calcium or magnesium precipitation preventing agent, and examples thereof include nitrogen triacetic acid, diethylene glycol triamine f ^ pentaacetic acid, and ethylene diamine tetraacetic acid. N,N,N-trimethylenephosphonic acid, ethylenediamine, hydrazine, hydrazine, hydrazine, Ν'-tetramethylenesulfonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diamine Propane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS body), Ν-(2-carboxylateethyl)-L-aspartate Amine acid, β-alanine diacetic acid, 2-phosphonium butane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-double (2 -Hydroxybenzyl) Ethylenediamine-N,N'-diacetic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and the like. The chelating agent may be used in combination of two or more kinds as needed. ί The amount of the chelating agent to be added may be such as to sufficiently block the amount of metal ions such as polyvalent metal ions mixed therein, for example, in 1 L of the honing liquid at the time of honing, to be 0.0003 mol to 0.07 mol. The way to add. Further, in the component added during the preparation of the concentrate of the honing liquid of the present invention, the amount of the solution having a solubility in water of less than 5% at room temperature is prevented from being cooled to 5 ° C when the concentrate is cooled. From the viewpoint of precipitation, it is preferred that the solubility in water at room temperature is within 2 times, more preferably within 5 times. The honing fluid of the present invention is generally suitable for honing the barrier metal layer, and the barrier metal layer is used to prevent the wiring between the copper metal and/or the copper alloy and the interlayer insulation. The spread of copper. [Bound Metal Material] The material of the barrier metal layer constituting the honing target of the present invention is generally a low-resistance metal material, and particularly preferably τ i N, T i W, T a , TaN, W , WN, which is especially good for Ta, TaN. [Wiring metal material] In the present invention, it is preferable that the object to be polished of the honing object has a wiring made of a copper metal and/or a copper alloy which is applied to a semiconductor device such as LSI. As a raw material of the wiring, it is preferably a copper alloy. Further, among the copper alloys, a copper alloy containing silver is preferred. Further, the content of silver contained in the 'copper alloy is preferably 40% by mass or less, particularly preferably 10% by mass or less, more preferably 1% by mass or less, or less than 0.0% by mass. The copper alloy system exerts the best results. [The thickness of the wiring] In the present invention, the honing body to be honed, for example, used in a DRAM or a device system, preferably has a wiring having a half pitch of 0 · 15 μm or less, more preferably Ο.ΙΟμιη Hereinafter, it is particularly preferably 0.08 μm or less. On the other hand, when the honed body is used in, for example, a U P U device system, it is preferable to have a wiring of 0·12 μm or less, more preferably 0·09 μηι or less, and particularly preferably 0.0 7 μηη or less. The honing liquid of the present invention exhibits particularly excellent effects on the honed body having such wiring. [Horse method] -20- 200840861 The honing liquid of the present invention includes: 1. a concentrated liquid, which is diluted with water or an aqueous solution at the time of use to be used as a use liquid, and 2) each prepared in the form of an aqueous solution described in the following item. The components are mixed, and if necessary, water is added to dilute it to form a use liquid, and 3. The case of using a liquid is prepared. In the honing method using the honing liquid of the present invention, the honing liquid in either case is applicable. The honing method is a method for supplying the honing liquid to the honing pad of the honing plate to make contact with the honed surface of the honed body to make the honed surface and the honing pad f. . % As a device for honing, a bracket having a honed body (for example, a wafer on which a film of a conductive material is formed) for holding a honed surface, and a honing pad can be used (installation) A honing device for a honing plate having a motor with a variable number of revolutions. As the honing pad, a general nonwoven fabric, a foamed polyurethane, a porous fluororesin or the like can be used, and it is not particularly limited. Further, the honing condition is not limited, but it is preferably a low rotation of 200 rpm or less so that the slewing speed of the honing plate does not cause the honed body to fly out. The pressing force of the honed body having the honed surface (the honed film) on the honing pad is preferably 0.6 8 to 3 4 · 5 KP a in order to satisfy the honing speed on the surface of the honed body The inner uniformity and the flatness of the pattern are more preferably 3.40 to 20.7 KPa. During the honing, the honing fluid is continuously supplied to the honing pad by a pump or the like. After the honing, the honed body is sufficiently washed in the running water, and the water droplets adhering to the honed body are shaken off using a rotary dryer or the like to be dried. In the present invention, when the concentrate is diluted as in the above method, an aqueous solution shown below can be used. The aqueous solution contains water containing at least one of an oxidizing agent, an organic acid-21-200840861, an additive, and a surfactant, and the total content of the component contained in the aqueous solution and the component contained in the diluted concentrated liquid is The composition of the honing fluid (use liquid) used in honing. As described above, when the concentrate is diluted with an aqueous solution, it can be blended after the insoluble component is in the form of an aqueous solution, so that a more concentrated concentrate can be prepared. Further, as a method of adding water or an aqueous solution to the concentrate to be diluted, a pipe for supplying the concentrated honing liquid and a pipe for supplying water or an aqueous solution are mixed and mixed in the middle, and the mixed honing liquid is mixed. The method of supplying the liquid to the k honing pad. The mixture of the concentrated liquid and the water or the aqueous solution may be a method in which the liquids are collided and mixed with each other through a narrow passage under a pressure application, and the filling of the glass tube or the like is blocked in the piping to repeat the flow of the liquid. A method of separating and converging separately, a method of providing a blade for power rotation in a pipe, and the like. The supply rate of the honing liquid is preferably from 10 to 100 ml/min, and more preferably from 1 70 to 800 ml/min in order to satisfy the tempering speed in the honed surface and the flatness of the pattern. In addition, as a method of honing the concentrate by diluting the concentrate with water or an aqueous solution or the like, a pipe for supplying the honing liquid and a pipe for supplying water or an aqueous solution are separately provided, and each of the specified amount of liquid is supplied. For the honing pad, the method of honing while mixing the honing pad and the relative movement of the honed surface. Further, it is also possible to use a method in which a predetermined amount of the concentrated liquid, water or a water solution is mixed in one container, and the mixed honing liquid is supplied to the honing pad for honing. Further, as another honing method, the component to be contained in the honing liquid is divided into at least two constituent components, and when it is used, it is diluted with water or an aqueous solution and supplied to the honing plate. The honing pad is a method of honing the surface to be rubbed to make the honed surface and the honing pad move relative to each other. For example, an oxidizing agent may be used as a constituent component (A), an organic acid, an additive, a surfactant, and water may be used as a constituent component (B), and when used, the constituent component (A) and the composition may be diluted with water or an aqueous solution. Used as component (B). Further, an additive having a low solubility is divided into two constituent components (A) and (B). For example, an oxidizing agent, an additive, and a surfactant are used as a constituent component (A) 以' as an organic acid, an additive, a surfactant, And water as a constituent component (B) 'When using this, water or an aqueous solution is added to dilute the component (A) and the component (B). In these cases, the specific colloidal vermiculite (abrasive grains) of the present invention is preferably contained in the constituent component (A). In the case of the above example, three pipes are required for supplying the component (A), the component (B), and water or an aqueous solution, respectively. The dilution mixing method is a method in which three pipes are combined with one pipe for supplying a honing pad, and mixed in the pipe. In this case, it is also possible to combine with two other pipes after combining the two pipes. Specifically, a method of mixing a constituent component containing a hard-to-dissolve additive with other constituent components, lengthening a mixing path to ensure a dissolution time, and then combining a water or an aqueous solution is mixed. The other mixing method may directly guide the three pipes to the honing pad as described above, mix the honing pad with the relative movement of the honed surface, or mix three components in one container, It is a method of supplying a diluted honing fluid to a honing pad. In the honing method, the i constituent components containing the oxidizing agent may be -23-200840861 4 〇 ° C or less, and the other constituent components may be heated from room temperature to l 〇〇 ° c in one constituent component. When mixing with other components, or when diluted with water or an aqueous solution, 'the liquid temperature is 40 ° C or lower. This method is a preferred method for increasing the solubility of a raw material having a low solubility of the honing liquid by using a phenomenon in which the solubility is high at a high temperature. The raw material which is dissolved by heating the above-mentioned other components from room temperature to 1 〇〇 ° C is precipitated in the solution when the temperature is lowered. Therefore, it is necessary to preheat the other components in the low temperature state. In order to dissolve the raw material from which f ' is precipitated. Here, a means for heating the other constituent components in which the raw material is dissolved, a liquid in which the precipitate-containing liquid is stirred in advance, and a liquid is supplied, and the pipe is heated and dissolved. When the temperature of one of the constituent components containing the oxidizing agent is raised to 40 ° C or higher, the oxidizing agent is decomposed. Therefore, the other components which are heated and the oxidizing agent are included. When the components are mixed, it is preferably at most 40 ° C. Thus, in the present invention, the components of the honing liquid may be divided into two or more portions and supplied to the honed surface. In this case, it is preferred to supply the component containing the oxidizing agent separately from the component containing the organic acid. Further, it is also possible to honing the liquid as a concentrate and supplying the diluted water to the surface to be honed. In the present invention, when the component of the honing liquid is divided into two or more and supplied to the honed surface, the supply amount indicates the total amount of supply from each pipe. [Cushion] The honing pad for honing which is applicable to the honing method of the present invention may be a non-foaming structural pad or a foamed structural pad. The former is made of a hard synthetic material such as a plastic sheet -24-200840861 resin block material. In addition, the latter has three types of 'integrated foam (dry foaming)' continuous foam (wet foaming) and two-layer composite (layered). ). Foaming can be uniform or non-uniform. Further, 'the abrasive grains (e.g., alumina, vermiculite, oxidized bromine, resin, etc.) used in general honing may be contained. Further, each of the hardnesses may be either soft or hard, and any of them may be used in the laminate system. The material is preferably non-woven fabric, artificial leather, polyamide, polyurethane, polyester, polycarbonate, or the like. Further, it is also possible to apply a lattice, a groove/acupoint, a concentric groove, a spiral groove, or the like to the surface that is in contact with the surface to be honed. [Wafer] The diameter of the wafer to be polished of the object to be subjected to CMP by the honing liquid of the present invention is preferably 200 mm or more, and particularly preferably 300 mm or more. When the thickness is 300 mm or more, the effects of the present invention are remarkably exhibited. [Mulching device] The device that can perform the honing using the honing liquid of the present invention is not particularly limited, and examples thereof include Mirra Mesa CMP, Reflexion CMP (APPLIED t MATERIALS), FREX 200, and FREX3 00 (荏原株式会社). NPS3301, NPS 2 3 0 1 (NIKON), A-FP-310A, A-FP-210A (Tokyo Precision), 23 00 TERES (LAM RESEARCH), Momentum (Speedfam IPEC), etc. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. &lt;Example 1&gt; -25- 200840861 The honing liquid shown below was prepared and subjected to honing evaluation. (Modulation of honing liquid) The following composition was mixed to prepare a honing liquid. &lt;Composition (1) &gt;

• (D) Colloidal vermiculite (PL3 slurry: manufactured by Fuso Chemical Co., Ltd.) 200g/L (The colloidal vermiculite in the honing fluid is 5 mass in terms of solid content conversion)

• (B) diglycolic acid (made by Wako Pure Chemical Industries, Ltd.) 15g/L

• (C) Heterocyclic compound: BTA (benzotriazole) 0.5 g/L • (A) Cationic compound: tetrabutylammonium nitrate (TBA additive)

Lg/L

• Oxidizer: 30% hydrogen peroxide 1 〇 g / L

• Add pure water to the full amount of 1 0 0 m L pH (adjusted with ammonia water and nitric acid) 3.5 &lt;Measurement of the boundary potential&gt; The (D) contained in the obtained honing liquid was measured under the following conditions. The boundary potential of the surface of a particular colloidal vermiculite particle. As a result, the boundary potential was 12 mV, and it was confirmed that it was positive. Further, when the tetrabutylammonium nitrate of the (A) cationic compound used in Example 1 was not added, the surface boundary potential of the colloidal vermiculite particles was -4 mV. The kinetic potential of Example 1 was measured in a non-concentrated form by DT-1200 manufactured by RUFUTO Co., Ltd., Japan. &lt;Hard object for honing speed evaluation&gt; A 8 Å wafer for test in which a Ta film having a thickness of 100 nm was formed on a ruthenium substrate by sputtering was used. -26- 200840861 &lt;Dressing body (chassis) for scratch evaluation&gt; The TEOS (tetraethoxydecane) substrate is patterned by a lithography step and a reactive ion etching step to form a width 〇·〇 9 to ΙΟΟμηι, a wiring trench and a connection hole having a depth of 600 nm, and a Ta film having a thickness of 20 nm is formed by sputtering, and then a copper film having a thickness of 5 nm is formed by sputtering, and then formed by plating. A total of 8 Å wafers of a copper film having a thickness of 100 nm. (Evaluation method) Using the device "LGP-612" manufactured by LAPMASTER Co., Ltd. as the honing device f = setting, the wafer film was honed while supplying the slurry under the following conditions. Number of revolutions: 64rpm Number of head turns: 6 5 rpm Honing pressure: 13.79kPa Honing pad: IC1400 XY-K-Pad manufactured by Rodel-Nitta Co., Ltd. Supply rate of honing liquid: 200ml/min &lt;honing speed&gt; The honing speed is obtained by measuring the thickness of the giant film before and after CMP and converting V· from the following formula. Honing speed (A / min) = (film thickness before honing - film thickness after honing) / honing time &lt;scratch evaluation&gt; Regarding the scratch performance, the above-mentioned scratch evaluation wafer was used. After honing, the pure water was washed, dried in order, and observed by an optical microscope, and the state of the processed surface after honing was evaluated according to the following evaluation criteria. The evaluation criteria of the scratch performance are as follows. -27- 200840861 〇: The occurrence of scratches is almost no good △: A small number of scratches of 1 μm or more are observed: Most scratches of 1 μm or more are observed, and '〇 and △ are judged to be practical. No problem level. &lt;Examples 1 to 18 and Comparative Examples 2, 2 &gt; The honing conditions are the same as in the case of Example i, and the composition of the honing liquid is composed of the components (A) to (D) in the composition (1). The honing test of Example 2 (~18 and Comparative Example 丨~2) was carried out in the same manner as in Example 1 except that the composition described in Table i was used, and the honing slurry of the five-week system was used. Table 1 and Table The results are shown in 2. L· -28- 200840861 [I嗽Scratch evaluation 〇〇〇〇〇〇〇〇〇〇Ta honing speed (nm/min) in 〇〇VO g (N 00 ov〇 potential of zeta potential ΐ (mV) 1 (N 00 vo 〇 00 CN &lt;N mo oo mm &lt;N m ΙΟ cn oo m in mw &lt; TBA Additive (lg/L), BTA (lg/L) TMA Additive ( Lg/L), BTA (lg/L) PEI Additive (0.05g/L), BTA (lg/L) TPA Additive (lg/L), DCEBTA (lg/L) TBA Additive (lg/L) , HEABTA (lg/L) TMA Additive (lg/L), HMBTA (lg/L) ! TPNA Additive (lg/L) |, HMBTA (lg/L) TEA Additive (lg/L), DBTA ( Lg/L) PEI additive (0.05g/L), DBTA (lg/L) TMPA additive (lg/L), DCEBTA (lg/L) (D) colloidal vermiculite (content) Bl (5 mass ) Bl (2.5 mass%) B-2 (2.5 mass%) B-2 (3 mass%) B-4 (2 mass%) n m_ _ inch - rH \Γ\ 1 1 OQ PQ B-2 (5 mass %) B-3 (5 mass%) B-3 (4 mass%) B-5 (l mass%) Bl (2 mass%) B-2 (3 mass%) B-2 (5 mass%) B- 2 (2 mass ° / 〇) B-3 (3 mass %) (B) compound with carboxyl group (content) Al (15g / L) Al (15g / L) Al (15g / L) Al (15g / L) Al (15g/L) Al (15g/L) Al (15g/L) A-2 (15g/L) A-2 (15g/L) A-2 (15g/L) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 丨6 (N丨200840861 [(Ν撇] Scratch evaluation 〇〇〇〇〇〇〇〇&lt; X Ta honing Velocity (nm/min) 〇oo S oo (N ^T) The zeta potential of the particle (mV) &lt;N 〇CN in &lt;N om 1 PU (N un 3.2 m cn m &lt;N (T) cn 00 ^ 2&lt;ΙΐΙ w 豳, TBA Additive (lg/L), HMBTA (lg/L) TPNA Additive (lg/L), HMBTA (lg/L) TPNA Additive (lg/L), BTA (lg/L) PEI Additive (0.05g/L), DBTA (lg/L) PPI Additive (lg/L), HMABTA (lg/L) PEI Additive (0.05g/L) , DBTA (lg/L) TPNA Additive (lg/L), BTA (lg/L) TEA Additive (lg/L), BTA (lg/L) Glycine (8g/L), BTA (1.0g /L) Glycine (8g / L), BTA (1.0g / L) (D) Colloidal vermiculite (content) Bl (5 mass%) _ _ ® i; ^ (N m vw / one (N 1 1 PQ PQ B-3 (5 mass ° / 〇) B-3 (5 mass%) B-3 (5 mass%) Bl (5 mass%) B-4 (4 mass%) B-5 (l mass % B-3 (5 mass%) Bl (5 mass%) IK _ (N &lt; N (N m 1 1 PQ PQ (B) compound having a carboxyl group (content) A-3 (15 g/L) A -3 (15g/L) A-4 (15g/L) A-4 (15g/L) A-4 (15g/L) A-5 (15g/L) A-6 (15g/L) A-6 (15 g/L) Example 实施 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Comparative Example 1 Comparative Example 2 丨οε — 200840861 The following shows the above-mentioned Tables 1 and 2 The details of the compound. TBA additive = tetrabutylammonium nitrate [(A) component] TMA additive = tetramethylammonium nitrate [(A) component] TEA additive = tetraethylammonium nitrate [(a) component] TPA additive = nitric acid Tetrapropylammonium [(A) component] TPNA additive = tetraamyl ammonium nitrate [(A) component] PEI = polyethyleneimine (weight average molecular weight: 2000) [(A) component] PPI = polypropylene imine (weight average molecular weight: 3000) [(A) component] BTA = 1,2,3-benzotriazole [(C) component] % DBTA = 5,6-Z^*-l,2,3-*- H_[(C^*] 0€£8丁八=1-(1,2-dicarboxyethyl)benzotriazole [((:) ingredient] HEABTA=1-[N,N-double (hydroxyl) Aminomethyl]benzotriazole [(C) component] ΗΜΒΤΑ=1-(hydroxymethyl)benzotriazole [(C) component] Further, (D) abrasive grains described in Tables 1 and 2 The shape, primary particle diameter, and (B) compound having a carboxyl group in the molecule [(A-1) to (A-6)] The compound name is shown in Table 3 and Table 4 below -31 - 200840861 [Table 3] Abrasive grain name [primary particle size / mm, shape] B-1 PL3 [35 nm, silkworm cocoon shape] B-2 PL3L [35mn, Spherical] B-3 PL3H [35nm, condensate] B-4 PL2 [25mn, silkworm cocoon] B-5 PL2L [20nm, spherical] [Table 4] Compound structure A-1 diglycolic acid A-2 2,5-furandicarboxylic acid A-3 2-furancarboxylic acid A-4 ethyl oxalate A-5 methoxy Phenylacetic acid A-6 phenoxyacetic acid-32- 200840861 It can be seen from Table 1 that when the honing liquid for barrier ribs of the present invention, that is, the honing liquids of Examples 1 to 18, the honing speed is high, and the scratches are also On the other hand, in the comparative example in which the compound of the formula (1) or the formula (11) and the boundary potential of the surface of the colloidal vermiculite particle show a negative enthalpy, it is known that Full honing speed. ( •33-

Claims (1)

200840861 X. Patent application scope: 1·- kinds of honing liquid, which is used for honing semiconductor integrated electro-hydraulic liquid, which comprises the following formula (1) or formula (11): compound with residue The boundary potential of the surface under the presence of the hunger inhibitor and the substance indicates that the pH of the positive grip liquid is 2.5 to 5.0, R1 t r1 to the formula (1) I. R1 [In the formula (I), R1 represents carbon a hydrocarbyl group of 1 to 18] Formula (111 [In the formula (II), R2 and R3 each independently represent an integer of c]] 2. The honing liquid according to the first aspect of the patent application, The compound is a compound selected from the group consisting of tetramethylammonium, tetraethylammonium, tetra-P, and tetraamylammonium. 3. The turmeric fluid of the first aspect of the patent application has a molecular weight of 100%. The cationicity of the ruthenium vapor of the barrier layer of the range of 20000 is in the cationic compound [state of vermiculite, and the same thiol group selected by the honing group, η represents 1 or more of the formula (I) Illustrative lysyl ammonium, tetrabutylammonium, d ° μ of the polyethyleneimine represented by the formula (π). -34- 200840861 4. As claimed The honing liquid of the present invention, wherein the compound having a carboxyl group is a compound represented by the following formula (111), R 4 —〇—R 5 —COOH Formula (丨Μ) [In the formula (III), R 4 represents a hydrocarbon group, R5 represents a hydrocarbon group or a carbonyl group, and R4 and R5 may be bonded to each other to form a cyclic structure] 5. The barrier broth for a barrier of the fourth aspect of the invention, wherein the compound represented by the formula (III) From 2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furan 1 carboxylic acid, 2-tetrahydrofurancarboxylic acid, diglycolic acid, methoxyacetic acid, methoxyphenylacetic acid, phenoxyacetic acid At least one selected from the group consisting of 6. The honing liquid of claim 1, wherein the corrosion inhibitor is from 1,2,3-benzotriazole, 5,6-dimethyl- 1,2,3-benzoxazole, 1-(1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl)aminemethyl]benzotriazole and At least one compound selected from the group consisting of 1-(hydroxymethyl)benzotriazole-35- 200840861 VII. Designation of representative drawings: (1) The representative representative of the case is: None. (II) Components of the representative figure Simple description of the symbol: iffi Eight, when the case if the formula, please disclosed invention features most indicative of the formula: