TW200821374A - Metal-polishing method - Google Patents

Abstract

The present invention provides a metal-polishing method with a high polishing speed and low dishing, which a metal-polishing liquid is supplied to a polishing pad on a polishing plate, and the polishing pad is contacted with a surface to be polished of an object to be polished and moved relative thereto to carry out polishing, by rotating the polishing plate, wherein the metal-polishing liquid includes polishing particles having a ration of a major axis to a minor axis in the range of 1.2 to 5.0, organic acid containing a secondary nitrogen atom or a tertiary nitrogen atom, and a heterocyclic compound, and the surface to be polished is polished with a contact pressure between the surface to be polished and the polishing pad being in the range of 4,000 Pa to 12,000 Pa and a temperature of the polishing pad surface that contacts the surface to be polished or the temperature of the surface to be polished at least 30 DEG C and less than 75 DEG C.

Description

200821374 IX. Description of the Invention: TECHNICAL FIELD The present invention relates to a manufacturer of a semiconductor device, and more particularly to a method of chemically and mechanically planarizing a wiring step of a semiconductor device. [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, the micro φ refinement and the merging of the wiring in recent years have increased the density. • Highly integrated systems are required. Various techniques such as chemical mechanical polishing (hereinafter referred to as CMP) can be used as such a technique. In the case where the surface of the film to be processed such as the interlayer insulating film is flattened, the pin is formed, or the metal wiring is formed, the CMP is required to smooth the substrate or remove the remaining metal film when the wiring is formed ( For example, refer to U.S. Patent No. 4,944,836). The general method of C Μ P is to attach the honing pad to the circular honing platform φ (Platen), the surface of the honing pad is immersed in the honing fluid, and the surface of the substrate 紧 wafer is pressed. With the honing pad, both the honing platform and the base plate are rotated in a state where a predetermined pressure (honing pressure) is applied from the back surface thereof, and the surface of the base plate is flattened by the mechanical friction generated. The metal honing solution for C Μ P generally contains abrasive grains (e.g., aluminum oxide, cerium oxide) and an oxidizing agent (e.g., hydrogen peroxide, persulfuric acid). The basic mechanism is to oxidize the metal surface with an oxidizing agent, and to honing it by removing the oxide film with abrasive grains, for example, Journal of Electrochemical Society', 1991, vol. 138, No. 11. , 200821374 3460~34 64 recorded on page 1. Metals for wiring Conventionally, tungsten and aluminum have been widely used as interconnection structures. However, in order to further improve the performance, an LSI system using copper having a lower wiring resistance than these metals has been developed. For example, a damascene method described in Japanese Laid-Open Patent Publication No. Hei No. 2-278822 is known. Further, a dual-metal damascene method in which a contact hole and a wiring trench are formed in an interlayer insulating film and the two are buried in a metal is widely used. In the honing of copper metal, since it is a particularly soft metal, a high-precision honing technique is required. At the same time, high-speed metal honing methods capable of high productivity are required. In particular, in recent years, the semiconductor device has been reduced in size and speed, and it has been required to increase the density and height of the wiring in accordance with the miniaturization and stratification of the wiring. The requirements for the concave distortion of the shape and depression are becoming more and more intense. Furthermore, in the introduction of the future Ultra Low-K insulating material (dielectric ratio of 2.3 or less), it is difficult to produce a film peeling honing method even if an insulating material having a weak mechanical φ strength is used, that is, even in the wafer. A method of honing under the condition that the contact pressure of the honing surface and the honing pad and the number of rotations of the platform are low, and obtaining a high honing speed and a low concave distortion are desirable. The technique of performing metal honing under the condition that the contact pressure between the honed surface of the wafer and the honing pad and the number of rotations of the slab are low is disclosed in Japanese Laid-Open Patent Publication No. 2003-289055, A method of high honing speed and reduced scratching. The inventors of the present invention can perform a high-speed honing operation under the condition that the contact pressure of the bedding surface of the wafer and the honing pad and the number of rotations of the platform are low in the C Μ P of the metal wiring step. The reduction in concave distortion is not sufficient in the prior art described above. Disclosure of the Invention Problems to be Solved by the Invention The present invention has been made in view of the above problems, and the object of the present invention is to achieve the object. That is, the object of the present invention is to provide a contact pressure between the honed surface of the honed body and the honing pad and the contact with the honed surface when honing the object to be honed (wafer) The honing of the surface of the gasket or the temperature of the surface to be honed is a very high condition, and it is also possible to form a metal honing method with a high honing speed and a low concave distortion. Means for Solving the Problems As a result of intensive review, the inventors have found that the following method of the present invention can further solve the problems, thereby achieving the above object. (1) A metal honing method characterized by supplying a honing liquid for a metal to a honing pad on a honing platform, and rotating the honing platform to cause the honing pad to be honed a metal honing method in which the honing surface is contacted and relatively moved, and the honing liquid system comprises a ratio of a long diameter to a short diameter (average long diameter/average short diameter) of 1.2 to 5.0. The honing particles, the organic acid containing a 2-stage nitrogen atom or a 3-stage nitrogen atom, and the heterocyclic compound, the contact pressure of the honed surface with the honing pad is 4000 to 12000 Pa, and is contacted in the contact The surface of the honing pad or the temperature of the honed surface is 35 ° C or more and less than 75 ° C under conditions 200821374, honing the honed surface. (2) The metal honing method according to (1), wherein the contact pressure between the honed surface and the honing pad is 7000 to 1000 Pa. (3) The metal honing method according to (1) or (2), wherein the honing particles have an average major axis of 30 to 70 nm. (4) The metal honing method as in (1), wherein the organic acid containing the above-mentioned secondary nitrogen atom or tertiary nitrogen atom is represented by the following general formula (A) or the following general formula (B),

Η

Ra/N, Rb Formula (A) The metal honing method of the formula (1), wherein the heterocyclic ring of the above heterocyclic compound is a triazole ring or a tetrazole ring. (6) The metal honing method according to (1), wherein the above heterocyclic compound is selected from the group consisting of: 1H-tetrazine '5-amino-1H-tetraπ sitting, 5-methyl-1H-four D Sit, 1,2,3-triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole , 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole. (7) The metal honing method according to (1), wherein the above heterocyclic compound is 1 Η _tetrazolium oxime (8), and the metal honing method of (1) further contains an oxidizing agent. (9) The metal honing method according to (1), which further comprises at least one organic acid or amino acid other than the organic acid having a secondary nitrogen atom or a tertiary nitrogen atom. The metal honing method according to any one of (1) to (9), wherein the concentration of the honing particles in the above-mentioned 200821374 is 0.1 to 1. 5 mass% with respect to the metal honing liquid. . In addition, as the above-mentioned object to be polished, the wafer to be formed on the support substrate may be a wafer on which a conductive material film is formed, or an interlayer insulating film provided on the wiring formed on the support substrate. A laminate or the like on which a conductive material film is formed, and all materials that must be planarized in the semiconductor device manufacturing step. Advantageous Effects of Invention According to the present invention, it is possible to provide a contact pressure between a honed surface of a honed body and a honing pad, and contact with a honed surface when honing a honed body (wafer) The honing of the surface of the gasket or the temperature of the surface to be honed is a very high condition, and it is also possible to form a metal honing method with a high honing speed and a low concave distortion. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, specific aspects of the present invention will be described. A metal honing method is characterized in that a metal is supplied with a honing liquid to a honing pad on a honing platform, and the honing platform is rotated to make the honing pad and the honed body The metal honing method for honing the surface in contact with and moving relative to the honing, the ratio of the long diameter to the short diameter (average long diameter / average short diameter) of the metal honing liquid system is 1. 2~5.0 Grinding particles, an organic acid containing a 2-stage nitrogen atom or a 3-stage nitrogen atom, and a heterocyclic compound, the contact pressure of the honed surface with the honing pad is 4000 to 12000 Pa, and is in contact with the honed surface The honed surface is honed under the condition that the temperature of the surface of the honing pad, and/or the temperature of the honed surface 200821374 is 35 ° C or higher and lower than 75 ° C. According to this method, for example, a wafer on which a conductive material film (e.g., a metal layer) is formed as a honed body can be chemically and mechanically planarized. Here, the honing liquid for metal in the present invention is hereinafter referred to simply as "honing liquid". Hereinafter, the present invention will be described in detail. <Metal honing method> φ [honing device] First, an apparatus which can carry out the metal honing method of the present invention will be described. As a honing device which can be applied to the present invention, a support frame (h ο I der) which holds a honed body (semiconductor substrate or the like) having a honed surface, and an attached honing pad can be used. For the general honing device for the honing platform, for example, a FREX300 (荏原株式会社) can be used. [Contact pressure of the honed surface and the honing pad] φ The metal honing method of the present invention is performed by the contact pressure between the honing surface and the honing pad of 4000 to 12000 Pa, preferably 7000~ 1 0 0 0 0 P a is honed. Outside of these ranges, the effect of the present invention is not sufficiently found, i.e., the high honing speed and the low concave distortion are not preferable. [The temperature of the surface of the honing pad contacting the surface to be honed or the temperature of the surface to be honed] The metal honing method of the present invention is the temperature at the surface of the honing pad contacting the surface to be honed, or being honed When the temperature of the surface (hereinafter referred to as "Table 10 - 200821374 surface temperature" is appropriately referred to as "Table 10 - 200821374 surface temperature"), the honing is performed under the conditions of 35 ° C or more and less than 75 ° C. It is not preferable to obtain the effect of the present invention. (Measurement of Surface Temperature) The surface temperature was measured by measuring the radiation temperature of the surface of the honing pad contacting the surface to be honed or the direct radiation temperature of the surface to be honed. Fig. 1(A) and Fig. 1(B) are diagrams showing the mode φ of the device for determining the temperature of the honed surface during honing. The measurement method includes a method of disposing a thermal radiation thermometer on the lower surface of the wafer as shown in FIG. 1(A) or a method of disposing a thermal radiation thermometer on the wafer surface as shown in FIG. 1(B). Any method of honing the device. In the first embodiment, the opening portion 1 for temperature measurement is provided in the honing device 1 3 and the honing table 1 2 in the honing device 1 , so that the opening portion 1 is provided. 4 The honing platform 12 and the honing head 22 are swayed and rotated by providing a portion of the radiation thermometer 16A for each rotation period. The wafer 23 is mounted on the honing head 22, and the honing is performed while supplying the metal φ φ grinding liquid (slurry) 24 from the supply port 26 for the metal honing liquid to the honing pad 13 . When the portion of the radiation portion 16A is provided in the opening portion 14 as described above, the heat radiation temperature of the surface of the crystal circle 23 can be measured by the radiation thermometer 16A. Further, the radiation thermometer 16B can measure the surface temperature of the wafer 23 at a constant cycle during honing, or arrange the wafer 23 to be extruded from the honing pad 13 and from the lower portion. The surface temperature of the wafer 23 was measured. Further, the temperature of the surface of the honing pad 13 can be indirectly measured, but in order to improve the convenience of the experiment, the temperature of the surface of the honing pad 13 can be directly measured. - -11- 200821374 Similarly, as shown in Fig. 1(B), the wafer 23 is placed on the honing head 22 provided below, and the honing pad fixed to the honing stage 12 is provided above. 1 3, the honing pad 13 and the honing stage 1 2 are provided with the opening portion 14 for temperature measurement, and the radiation thermometers 16 6 A and 16 B are disposed above, and the honed surface can be performed as described above. The measurement of the temperature of the surface of the wafer can also be performed in the same manner according to the method. (Method of Controlling Surface Temperature) φ The surface temperature can be controlled by, for example, controlling the temperature of the honing stage, the honing head or the surface to be honed, and the honing speed of the honed body. Further, it can be controlled by adjusting the temperature of the metal honing liquid. Alternatively, it can be controlled by adjusting the content of the honing particles in the honing liquid for the metal, appropriately selecting the kind of the organic acid, and the kind of the heterocyclic compound. Here, it can be used as a honing platform, a honing head or a honed surface, for example, by setting the temperature of the heating element or the cooling mechanism in the honing platform or the honing head, the honing platform The honing head, or the wafer may be controlled by means other than a φ heat exchanger, a cooler, or the like, or provided with a honing system containing a honing device, a slurry, or pure water, such as a honing device. The method of overall temperature control in the room. The method of controlling the honing speed of the honed body can be controlled, for example, by controlling the contact pressure and the number of rotations of the honing head and the surface to be honed. The contact pressure and the number of rotations are increased to increase the frictional heat to increase the surface temperature. The contact pressure and the number of rotations are reduced to suppress the frictional heat and the surface temperature is lowered. The method of controlling the temperature of the honing liquid for metal may be, for example, a method of controlling by a temperature control device such as a supply tank or a liquid supply tube for honing liquid for -12-200821374, or by separately supplying A method of controlling the method in which the honing system is installed in a constant temperature chamber. Further, by controlling the content of the honing particles of the honing liquid for metal, the surface temperature due to the frictional heat of the honing particles and the honed body can be controlled. That is, when the content of the honing particles is increased, the frictional heat of the honed body is increased and the surface temperature is raised, and when the content is reduced, the frictional heat is reduced and the surface temperature is lowered. Further, by appropriately selecting the type of the organic acid and the type of the heterocyclic compound, the surface of the honed body can be adjusted in accordance with the degree of promoting embrittlement caused by oxidation of the honed surface and the formation of a passive film. State, and the frictional heat of the honed surface and the honing pad can be used to control the surface temperature. The surface temperature can be appropriately controlled by the above-described method of maintaining a predetermined temperature while measuring with a non-contact thermometer. Further, the surface temperature can be controlled by experimentally specified conditions. [Method for supplying honing liquid for metal] The present invention can also be used by adding water or an aqueous solution to a honed liquid for concentration in a concentrated metal. The dilution method may be, for example, a pipe for supplying a concentrated metal honing liquid, a pipe for supplying water or an aqueous solution to be mixed and mixed in the middle, and the diluted metal is supplied to the honing liquid with the honing liquid. The method of the gasket, etc. The mixing system in this case can be used: a method of passing a narrow passage in a state of additional pressure to cause the solutions to collide with each other; and repeating the flow of water for clogging a liquid such as a glass tube in a pipe. A method of separating and combining them; a method generally performed by a method of providing a blade that rotates by power in a pipe. -13- 200821374 Further, if it is used as another dilution method, if the piping for supplying the metal honing liquid and the piping for supplying water or the aqueous solution are separately provided, the respective amounts of the liquid are supplied to the honing pad. The method of mixing by honing the relative movement of the gasket and the surface to be honed can also be used in the present invention. Further, 'the amount of the concentrated metal is charged into a container with a honing liquid and water or an aqueous solution, and after mixing to a predetermined concentration, the mixture is supplied to the honing pad. It can also be applied to this issue. In addition to these methods, the component to be contained in the metal honing fluid is classified into at least two constituent components, and when it is used, a method of adding water or an aqueous solution to be diluted and supplied to the honing pad can also be used. this invention. In this case, it is preferred to divide the component into an oxidizing agent and a component containing an acid. For example, an oxidizing agent is used as a constituent component (A), and an acid, an additive, a surfactant, and water are used as a constituent component (B), and when they are used, the constituent component (A) is diluted with water or an aqueous solution. Used in combination with component (B). In the case of Lu, it is necessary to supply three piping systems of component (A), component (B), and water or an aqueous solution, respectively, and that three pipes can be combined with one pipe to be supplied to the honing pad, and The piping is mixed, and it is also possible to combine two pipings and then combine them with one other piping. For example, a constituent component containing an additive which is difficult to dissolve may be mixed with other constituent components, and the mixing route may be elongated to ensure a dissolution time, and then a metal honing liquid may be supplied by a pipe in which water or an aqueous solution is combined. Further, each of the three pipes described above may be guided to the honing pad, and may be mixed and supplied by the relative movement of the honing pad and the surface to be honed, and the three components may be mixed at -14-200821374. After being placed in a container, the mixture is supplied to the honing pad. Further, the metal may be used as a concentrate with the honing liquid, and the dilution water may be separately supplied to the surface to be honed. [Amount of supply of honing liquid for metal] In the metal honing method of the present invention, in order to stabilize the honing speed and the in-plane uniformity in order to supply the supply amount of the metal honing liquid to the honing stage, 50 to 500 ml/min·, more preferably 100 to 300 ml/min·. [Horrying pad] The honing pad used for the metal mechanical honing method of the present invention is not particularly limited, and may be a non-foaming structural gasket or foaming. Construct the gasket. The former is a synthetic resin block material such as a plastic plate which is used for honing gaskets. Further, the latter is a more independent foam (dry foaming system), a continuous foam (wet foaming system), and a two-layer composite (layered system), in particular, a two-layer composite (layered system) ) is better. The foaming system can be uniform or non-uniform. Further, it may be one containing particles for honing (for example, ceria, cerium oxide, aluminum oxide, resin, etc.). Further, each of the hardnesses may be either soft or hard, and any of the layers may be used in different layers for different hardnesses. The material is preferably non-woven fabric, artificial leather, polyamide, polyurethane, polyester, polycarbonate, or the like. Further, in the surface in contact with the honed surface, processing such as a lattice groove/acupoint, a concentric groove, or a spiral groove may be applied. Next, the metal honing liquid will be described. <Metal honing liquid> The metal honing liquid used in the present invention is a heterocyclic compound as an essential component of -15-200821374, and preferably contains an organic acid, an oxidizing agent, and a honing agent. Or the like, usually in the form of a slurry formed by dissolving the honing particles in an aqueous solution composed of the respective components. In the following, each component contained in the honing liquid for metal is described in detail, and each component may be used alone or in combination of two or more. The "metal honing liquid" in the present invention is not only a composition (concentration) honing liquid used for honing, but also a honing concentrate used for dilution as needed in the present invention. It is not specifically limited and is called a honing liquid. When the concentrate is used for honing, it is diluted with water or an aqueous solution, and since it is used for honing, the dilution ratio is generally 1 to 20 times by volume. In the honing liquid for metal according to the present invention, the following is the case where the concentrate is diluted with water to form a use liquid, and the components are mixed in the form of an aqueous solution described in the following paragraphs. The case where it is necessary to add water to dilute into a use liquid, and 3. It is prepared as a use liquid. In the metal honing method of the present invention, the metal honing liquid can be applied in any case. Next, the components of the honing liquid for metal according to the present invention will be described. [honing particles] The honing liquid for metal used in the present invention contains at least one honing particle having a ratio of a long diameter to a short diameter (average long diameter/average short diameter) of the honing particles of 1.2 to 5.0 (hereinafter, Suitable as "specific particles" as a honing particle. The long diameter in the present invention means the largest particle size portion of a specific particle. The short diameter in the present invention means the largest particle diameter portion among the diameters -16 to 200821374 which intersect the long diameter in the vertical direction. In the present invention, the honing particles of the component 'cerium oxide (settlement dioxide, forged dioxide, colloidal silica, synthetic dioxide) are especially due to the honing speed of the copper-containing metal High colloidal cerium oxide or fumed cerium oxide is preferred, especially colloidal cerium oxide. Among them, colloidal cerium oxide having a 茧-shaped shape is more desirable. Here, the "茧 shape" refers to a shape in which the central portion Φ of the honing particles is concave or the end portion is concave or a so-called waist shape. A commercially available product may be used as the specific particle system, and a commercially available product is preferably used, for example, in a colloidal cerium oxide manufactured by Fuso Chemical Co., Ltd., trade name: PL-1SL (long diameter: 15 nm, short diameter: 8 nm, long diameter) / Short diameter: 1·9), PL-2 (long diameter: 25 nm, short diameter: 10 nm, long diameter / short diameter: 2.5), PL-3 (long diameter: 35), short diameter: 11 gates 111, long Trail/Short Trail: 3.1),? 1_-5 (long diameter: 55_, short diameter: 14 nm, long diameter/short diameter: 3 · 8), PL - 7 (long diameter: 70 nm, short diameter: 17 nm, long diameter / short diameter : 4.2), PL -1 0 (long diameter: 1 0 0 nm, short φ diameter: 20 nm, long diameter / short diameter: 5.0), and the like. Further, a method of obtaining honing particles having an average major axis and an average minor axis as defined in the present invention is exemplified by a production method using a sol-gel method or a separation method by centrifugal separation. The average major axis and the average minor axis of the honing particles used in the present invention can be obtained by the following methods. In other words, after the shape of the entire honing particles is grasped by the sweeping electron microscope S48 00 manufactured by Hitachi High-Tech Co., Ltd., the honing particles are observed from the direction in which the long diameter can be confirmed, and any one or more of them are used. In the grinding particles, -17-200821374 determines the long diameter and the short diameter, and obtains the average of the average particles as the "average long diameter" and "average short diameter" of the specific particles in the present invention. The ratio of the major axis to the minor axis (average long diameter/average short diameter) contained in the honing liquid for metal used in the present invention is preferably a preferred average long diameter of the honing particles of 1.2 to 5.0. The range is 1 0 to 2001^1, preferably 30 to 100|1〇1, and 3 0 to 7 0 nm. In the honing liquid for metal used in the present invention, the ratio of the long diameter φ to the short diameter (average long diameter/average short diameter) of the honing particles is preferably from 1.2 to 5.0, relative to the use. The total mass of the metal honing liquid at the time of the use is from 0.01 to 10% by mass, more preferably from 0. 1 to 1 _ 5 mass%. [Organic acid containing a 2-stage nitrogen atom or a 3-stage nitrogen atom] The honing liquid used in the present invention is characterized by containing at least one organic acid having a secondary nitrogen atom or a tertiary nitrogen atom (hereinafter, referred to as In the case of organic acids containing specific nitrogen). In the present invention, a specific nitrogen-containing organic acid is preferable, for example, a compound represented by the following formula (A) or φ and a compound represented by the following formula (B).

Η

Ra/N, Rb General formula (A) General formula (B) In the above formula (A) and the above formula (B), Ra, Rb and rc each represent an alkyl group each independently having a carbon number of 1 to 1 fluorene. The alkyl group is preferably a carbon number of 1 to #, more preferably a carbon number of 2 to 7. Further, the alkyl group may have a substituent or may be unsubstituted, or may be either a straight chain, a branch -1 8 - 200821374 or a ring. The substituent which can be introduced is preferably -OH, -COOH, -CONH2, -S03H, -P03H2, etc. Further, the introduced substituents may be bonded to each other to form a ring structure. Further, the alkyl group also includes a part of the carbon atom constituting the alkyl group substituted by another atom (e.g., a nitrogen atom). Specific examples of the organic acid having a nitrogen atom of the second or third order are exemplified by the following compounds (exemplified compounds (丨_1) to (| - 2 1 )). However, the preferred nitrogen-containing organic acid in the present invention is not limited to the exemplified compounds.

200821374 (Μ) (1-2) (1-3) ΗΝ

/~COOH

-COOH η3ο-ν

Factory COOH

-COOH

Η ^N^COOH (Bu 4) (1-5) (1 -6) HOOC /-COOH HOOC Plant COOH H〇OC〉 N—

H r

XOOH (1-7)

OH

HOOC

(1-8) HOOC

-N

OH

H2NOC

Factory COOH

(1-9) HOOC

Factory COOH

-N

COOH (1-10) Plant COOH ΗΝ ^-〇h

OH OH (1-11) HOOC, hooct (h12) HOOG-^v

COOH

COOH

COOH (M3) (1-14)

COOH

HOOC

Factory COOH

, N

COOH

-COOH

'COOH "COOH

-20- 200821374 (I-16) (1-15) η2〇3ρ-λ η203ρ-^ FactoryΡ〇3Η2 Μ χ-ρ〇3η2 η2ο〆/—Ρ〇3^2 ρο3η2 (1-17) ΗΟΟΟ- ΗΟΟΟ Factory COOH SI Lcooh HOOC〆

H

, N, H

.COOH (1-19)

Plant COOH N ^-COOH plant COOH N --COOH

020) H (1-21) so3h

H〇〇(T

, N〆 H

"COOH Among these specific nitrogen-containing organic acids of the present invention, more preferred are Compounds 3, 丨-5, Bu 7, Bu 10, Bu 2 and the like. Further, the specific nitrogen-containing organic acid in the present invention may be used alone or in combination of two or more. These nitrogen-containing organic acid systems may be commercially available, in addition to the usual methods. In the present invention, the amount of the specific nitrogen-containing organic acid to be added is preferably 0. 00 5 to 0.5 m in the lanthanum metal lanthanum solution for use, and is preferably 0.005 mol to 0.3 mol. Set to O.OImol~ is especially good. That is, the amount of the organic acid containing a specific nitrogen is preferably from 〇. 5 mol or more from the viewpoint of the acceleration rate, and preferably 0.5 m ο 丨 or less from the suppression of the concave point. [Heterocyclic compound] For example, it is preferably used in honing, 0 · 1 m ο I High honing distortion - 21 - 200821374 The metal honing liquid of the present invention contains at least one heterocyclic compound As a compound that forms a passive film in the metal surface of the honing object. Here, the "heterocyclic compound" is a compound having a hetero ring containing one or more hetero atoms. A hetero atom means an atom other than a carbon atom or a hydrogen atom. A heterocyclic ring means a cyclic compound having at least one hetero atom. The hetero atom system means that only the atom of the ring system of the heterocyclic ring is formed, and the progenitor is external to the ring system, and is separated from the ring system by at least one non-conjugated single bond without meaning such as a ring. An atom that is part of an additional substituent. The hetero atom is preferably a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a ruthenium atom, a phosphorus atom, a ruthenium atom, and a boron atom, preferably a nitrogen atom, a sulfur atom, an oxygen atom, and a selenium atom, particularly preferably a nitrogen atom. Atom, sulfur atom, and oxygen atom 'the best nitrogen atom, and sulfur atom. First, the heterocyclic ring that becomes the mother nucleus will be described. The ring number of the heterocyclic ring of the heterocyclic compound used in the present invention is not particularly limited as a monocyclic compound or a polycyclic compound having a condensed ring. The number of members in the case of a single loop is preferably 3 to 8, more preferably 5 to 7, and particularly preferably 5 and 6. Further, the number of rings having a condensed ring is preferably 2 to 4, more preferably 2 or 3. Specifically, such heterocyclic rings are, for example, the following. However, it should not be limited to this. For example, · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Ring, pyridinium ring, pyrimidine ring, anthracene ring, pyrrolidine ring, pyrazole ring, taste 11 sitting 11 ring, isoxazoline ring, isothiazolidine ring, piperidine ring, piperidine ring, - 22- 200821374 porphyrin ring, thiaxoline ring, chroman ring, dihydrobenzothiopyran ring, heterochromone ring, iso-hydrogen thiopyran ring, porphyrin ring, isoporphyrin ring, nitrogen hydrazine Ring, anthracene ring, anthracene ring, carbazole ring, anthracene ring, quinine ring, isoquinoline ring, fluorene ring, naphthalene ring, anthracene ring, quinoxaline ring, quinoxaline ring, Porphyrin ring, butterfly B ring, astringent ring, vomitidine ring, phenanthroline ring, indazole ring, porphyrin ring, phenanthrene ring, anthyrjdjne ring, thiadiazole ring, oxadiazole Ring, triterpene ring, dioxan ring, tetrazole ring, benzimidazole ring, benzoxazole ring, benzoxanthene ring, benzothiadiazole ring, benzo N oxidized oxadiazole ring, naphthalene Imidazole ring, benzodioxin ring, tetracyclic ring, etc. More preferably, for example, a triazole ring or a tetrazole ring. Next, the substituents of the above heterocyclic ring are described. In the context of the present invention, where a particular moiety is referred to as a "base", that moiety is intended to be replaced by one or more (and possibly the most) substituents. For example, "alkyl" means a substituted or unsubstituted alkyl group. The substituent which can be used in the heterocyclic compound used in the present invention is exemplified by, for example, the following. However, it is not limited by these. That is, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or a halogen atom), an alkyl group (a linear, branched or cyclic alkyl group, which may be a polycyclic alkyl group such as a bicyclic ring group) Also containing active methine), alkenyl, alkynyl, aryl, heterocyclic (regardless of the position of the substituent), mercapto, alkoxycarbonyl, aryloxy, heterocyclic hydroxycarbonyl, amine formazan Base (which can be used as a substituted amine group), for example: N-hydroxylamine, N-decylamine, sulfonamide, N-aminoformamide Sulfhydryl, thiamine, chloramine, amine, amine, amine, carboxyl, carboxyl or its salt, oxazide, oxalyl, cyano, carbamide , indenyl, hydroxy, alkoxy (including repeating groups containing ethyleneoxy or alkoxy groups), aryloxy, heterocyclic oxy, decyloxy, (alkoxy or aryloxy)carbonyl Oxyl, amine methyl methoxy, sulfonoxy, amine, (alkyl, aryl, or heterocyclic) amine, guanamine, sulfoximine, ureido, thiourea, N- Ureyl group, quinone imine group, (alkoxy or aryloxy)carbonylamino, aminesulfonylamino, aminoureido, thiomethantido, decyl, ammonium, oxalyl, aryl, N-(alkyl or aromatic Sulfonyl urea group, N-mercaptoureido group, N-decylamine sulfonamide group, hydroxylamine group, nitro group, heterocyclic group containing a 4-stage nitrogen atom (for example, pyridyl group, imidazole key) , quinolinyl, isoquinolinyl), isocyano, imido, thiol, (alkyl, aryl, or heterocyclic) thio, (alkyl, aryl, or heterocyclic) a disulfide, (hospital or aryl) sulfonyl, (homo- or aryl) sulfinyl, sulfo or a salt thereof, an amine sulfonyl group (which can be used as a substituted amine sulfonyl group) For example, N-decylamine sulfonyl, N-sulfonamide sulfonate or a salt thereof, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a sand-alkyl group, etc. . Further, the so-called active methine group means a methine group substituted with two electron attracting groups, and the so-called electron attracting group means, for example, a mercapto group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine. A decyl group, an alkyl sulfonyl group, an aryl sulfonyl group, an amine sulfonyl group, a trifluoromethyl group, a cyano group, a nitro group, a carbene imine group. The two electron attracting groups can be bonded to each other to form a ring structure. Further, the salt system means a cation such as an alkali metal, an alkaline earth metal or a heavy metal, or an organic cation such as an ammonium ion or a scale ion. Preferred substituents among these are, for example, a halogen atom (a fluorine atom, a chloro-24-200821374 atom, a bromine atom, or an iodine atom), an alkyl group (a linear, branched or cyclic alkyl group, which may be For example, a polycycloalkyl group of a bicycloalkyl group may also contain an active methine group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (regardless of the position of the substitution), a fluorenyl group, an anthracene group, an aryl group. Base curtain, heterocyclic ring, amide group, N-mercaptoamine group, N-mercaptoamine group, N-sulfonamide group, N-amine formamide Sulfhydryl, thiamine, sulphate, N-amine, sulphate, sulphate, sulphate, sulphate, cyano, carbamide, carbyl, hydroxy, _ An oxy group (containing a group containing a repeating unit containing an ethyl or alkoxy group), an aryloxy group, a heterocyclic oxy group, a decyloxy group, an (alkoxy or aryloxy)carbonyloxy group, an amine formamidine Alkyl, sulfonyloxy, (alkyl, aryl, or heterocyclic) amine, guanylamino, sulfonylamino, ureido, thioureido, N-hydroxyureido, quinone imine, (alkane) Oxy or aryloxy)carbonylamino, amine sulfonamide , Aminoureido, Thiamine-ureido, Sulfhydryl, Ammonium, Glutamine, N-(Alkyl or aryl)sulfonylurea, N-Mercaptoureido, N-Mercaptoamine a sulfonamide group, a hydroxylamine group, a nitro group, a heterocyclic group containing a nitrogen atom of a 4-stage (for example, pyridyl group, imidazolidinyl group, fluorene iron group, isoindolyl group), an isoamino group, Imino, thiol, (I, aryl, or heterocyclic) thio, (hospital, aryl, or heterocyclic) disulfide, (hospital or aryl) sulfonyl, Sulfhydryl or aryl) sulfinyl, sulfo or its salt, sulfonyl, N-decylamine sulfonyl, N-sulfonylsulfonyl or its salt, phosphino, phosphinyl, A phosphinyloxy group, a phosphinylamino group, a sand compound, and the like. Further, the active methine group referred to herein means a methine group substituted with two electron attracting groups, wherein the so-called electron attracting group is, for example, a fluorenyl group, a oxo group, an aryloxy group. Alkyl, amine-based, carboxylic acid, arylsulfonyl, sulfonyl, trifluoromethyl, cyano, nitro, carbamide-25-200821374 Amino. More preferably, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or a macro atom), a hospital group (a linear, branched or cyclic group, which may be a polycycloalkyl group such as a bicycloalkyl group) 'Can also contain active methine), alkenyl, alkynyl, aryl, heterocyclyl (regardless of the position of the substitution). Further, two of the substituents may form a ring (an aromatic or a non-aromatic hydrocarbon ring or a heterocyclic ring). These may be further combined to form a polycyclic φ condensed ring. For example, a benzene ring may be mentioned, for example. , naphthalene ring, anthracene ring, phenanthrene ring, anthracene ring, di extended base ring, fused tetraphenyl ring, biphenyl ring, brain ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring , pyridinium ring, stagnation ring, samarium trap ring, anthracene ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinine trap ring, quinoline ring, hydrazine trap ring, Naphthalene ring, quinoxaline ring, quinoline quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, oxime ring, phenanthroline ring, thiophene ring, chromene ring, diphenyl And a piper ring, a phenothiazine ring, a phenothiazine ring, a phenanthrene ring). Specific examples of the heterocyclic compound which is particularly preferably used in the present invention are not limited thereto, and the following may be mentioned. Also, 1 H-tetrazole, 5-amino-1 H-tetrazole, 5-methyl-1 H-tetrazole, 1,2,3-triazole, 4-amino-1, 2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3,5 -Diamino-1,2,4-triazole. The heterocyclic compound used in the present invention may be used singly or in combination of two or more. Further, the heterocyclic compound used in the present invention may be synthesized in accordance with a usual method, and a commercially available product may be used. The amount of the heterocyclic compound used in the present invention is the metal honing liquid used for honing as a total amount of -26-200821374 (that is, the diluted metal is diluted with water or an aqueous solution). In the pulverized liquid) 1 liter, 0.0001 to 1. 〇m 〇 l is preferably, more preferably 0.0005 to 0.5 mol, more preferably 0.00 〇 5 to 0.0 5 m ο I. [Oxidant] The metal honing liquid of the present invention preferably contains a compound (oxidizing agent) which can oxidize the metal to be honed. H specifically, for example, hydrogen peroxide, peroxide, nitrate, sulphate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulphate , dichromate, permanganate, ozone water and silver (I 丨) salt, iron (m) salt, and more preferably hydrogen peroxide. The amount of the oxidizing agent to be added is preferably from 0.003 mol to 8 mol, preferably from 0.03 mol to 6 mol, in the case of the metal honing liquid 1L used for honing, and is preferably set to 〇. 1 m ο I~4 m ο I is especially good. That is, the amount of the oxidizing agent added is preferably φ 0.003 mol or more from the point of sufficiently oxidizing the metal and ensuring a high C Μ P speed, and is preferably 8 m 〇 | or less from the viewpoint of preventing the roughness of the honed surface. [Other Organic Acids] The metal honing liquid of the present invention preferably contains at least one organic acid or amino acid other than the specific nitrogen-containing organic acid. The other organic acid referred to herein is not an oxidizing agent for metals, but has an effect of promoting oxidation, adjusting P H , and acting as a buffer. It is desirable that the organic acid be water soluble. It is more appropriate to choose from the following ethnic groups. For example: formic acid, acetic acid, propionic acid, butyric acid, pent-27-200821374 acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methyl Valeric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid Acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, lactic acid, hydroxyethyliminodiacetic acid, imine diacetic acid, dihydroxyethylglycine And salts of such ammonium or alkali metal salts, sulfuric acid, nitric acid, ammonia, ammonium salts, or mixtures thereof. φ In this case, formic acid, malonic acid, malic acid, tartaric acid, citric acid, hydroxyethyliminodiacetic acid, imidodiacetic acid, dihydroxyethylglycine, or the like is suitable. The amino acid is preferably water-soluble. It is more appropriate to choose from the following ethnic groups. Glycine, L-alanine, β-alanine, l-2-aminobutyric acid, L-pentylamine, L-proline, L-leucine, L-positemin, L- Isoleucine, L-isoisoleucine, L-phenylalanine, L-proline, creatinine, l-toxin Φ acid, L_ lysine, taurine, L-filament Amine acid, L-threonine, L-bethuric acid, L-homoserine, tyrosine, 3,5-diiodo-L-tyrosine, diphenylphenyl-L-alanine , l-thyroxine, 4-hydroxy-L-proline, L-cysteine, L-methionine, L-ethylthioacetate, L-lanthiol acid, L cystathionine, L -cystamic acid, L-cysteine acid, L-aspartic acid, L-glutamic acid, S-(carboxymethylcysteine, 4-aminobutyric acid, l-aspartate Acid, L-glutamic acid, diazoacetin, L_arginine, l-guarin, L-citrulline, δ-hydroxy lysine, creatine, L_kyriamine Acid, L-histamine, 1-methyl-L-histidine, 3-methyl-L-histidine, ergothione, L--28- 200821374 Tryptophan, actinomycin C1 Amino acids such as bee neurotoxin, angiotensin I, angiotensin and anti-papaya enzymes. About malic acid, tartaric acid, citric acid, glycine, glycolic acid, β-alanine, hydroxyethylimine diacetic acid, imine diacetic acid, di-vinylglycine, can maintain a practical C Μ Ρ The speed and the point at which the etching rate can be effectively suppressed are preferable. [Interacting Agent/Hydrophilic Polymer] The metal honing liquid of the present invention may further contain other components, and examples thereof include a surfactant and a solvent-soluble polymerization. The honing liquid of the present invention preferably contains a surfactant and a hydrophilic polymer. Both the surfactant and the hydrophilic polymer have a function of lowering the contact angle of the surface to be honed, and have Promoting the effect of uniform honing. The surfactant and hydrophilic polymer used are preferably selected from the group consisting of the following: anionic surfactants such as carboxylates, sulfonates, sulfates, phosphoric acid The ester salt, the cationic surfactant is, for example, an aliphatic amine salt, an aliphatic quaternary salt, a chlorinated ammonium salt, a benzothonium chloride > pyridinium salt, an imidazoline salt, two The surfactants are, for example, a carboxybetaine type, an aminocarboxylate, an imidazolidinyl betaine, a lecithin, an alkylamine oxide, and a nonionic surfactant such as an ether type, an ether ester type, an ester type, Further, the nitrogen-containing type may, for example, be a fluorine-based surfactant. Further, the hydrophilic polymer may, for example, be a polyethylene glycol such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone or alginic acid. A polysaccharide such as -29-200821374 polycarboxylic acid or the like contains a polymer, etc. Further, among the above, the acid or its ammonium salt is not caused by an alkali metal, an alkaline earth metal or a halogen compound. Pollution is what is expected. Among the above exemplified compounds, especially cyclohexanone, ammonium polyacrylate, polyvinyl alcohol, decyl succinate, polyvinyl pyrrolidone, polyethylene glycol, polyoxyethylene polyoxypropylene block polymer Preferably. The weight average molecular weight of these surfactants and hydrophilic polymers is preferably φ 500 to 100000, particularly preferably from 2,000 to 5,000 00. The amount of the surfactant and/or the hydrophilic polymer to be added is preferably 0.001 to 10 g, preferably 0.01 to 5 g, in a total amount of 1 L of the metal honing liquid used for honing. 0.1~3g is especially good. [P Η adjusting agent] In order to adjust to a predetermined ρ Η値 , the metal honing liquid of the present invention may be added as an alkali agent, a buffering agent or an inorganic acid as a cerium adjusting agent. Examples of the alkaline agent (and buffer) include non-organic ammonium hydroxides such as ammonium hydroxide and tetramethylammonium peroxide, diethanolamine, triethanolamine, and triisopropanolamine. An alkali metal hydroxide such as a metal alkali agent, sodium hydroxide, potassium hydroxide or lithium hydroxide; a carbonate such as sodium carbonate or a phosphate such as trisodium phosphate; a borate, a tetraborate or a hydroxybenzoate; . Particularly preferred base agents are ammonium hydroxide, potassium hydroxide, lithium hydroxide and tetramethylammonium hydroxide. The inorganic acid is, for example, sulfuric acid, nitric acid, boric acid, phosphoric acid or the like, and among them, phosphoric acid or sulfuric acid is preferred. The amount of the Ρ Η adjuster can be maintained as long as ρ η is within the ideal range of -30-.200821374, and used in the 1L of the metal honing liquid used for honing, set to 0 · 0 0 01 m ο I 〜1.0 m ο I is better, set to 0 · 0 0 3 m ο I 〜0 · 5 m ο I is preferred. The p lanthanum of the metal honing liquid used for honing is preferably 3 to 12, more preferably 4 to 9, and particularly preferably 5 to 8. Within this range, the metal used in the present invention can exert particularly excellent effects with the honing liquid system. With the above Η Η adjusting agent, ρ Η of the honing liquid can be adjusted to the above preferred range. [chelating agent] φ The metal honing liquid of the present invention may contain a chelating agent (i.e., a hard water softening agent) as needed in order to reduce the adverse effects of the polyvalent metal ions or the like. As the chelating agent, a general hard water softening agent of a potassium or manganese precipitation preventing agent or the like can be used, and two or more kinds thereof can be used as needed. The amount of the chelating agent to be added may be a sufficient amount to block the metal ions such as the polyvalent metal ions to be mixed therein. For example, in the case of honing, the metal φ is used in 1 L of the honing liquid. 〇3mo丨~〇.〇7mol. <Hardted body> Next, the object to be polished (substrate, wafer) to which the honing is applied in the honing method of the present invention will be described. [Wiring Metal Material] The honed system of the present invention has a substrate (wafer) formed of a copper or a copper alloy, and a copper alloy containing silver is particularly suitable for the copper alloy. The silver content contained in the copper alloy is 1 〇 mass. The following effects can be exhibited in an amount of 1% by mass or less, in 〇 〇 〇 〇 〇彳 〇 〇 1 quality. /〇 -31 - 200821374 The range of copper alloys can achieve the best results. [Thickness of Wiring] In the honed body of the present invention, for example, the dram device system preferably has a half pitch, preferably 0. 15 μm or less, more preferably 0. 10 μm 2 or less, and more preferably 0.0 8 . Wiring below μ m is preferred. On the other hand, in the MPU apparatus, it is preferable to have a wiring of 0_12 μΓΤΐ or less, more preferably 0.09 μητι or less, and still more preferably 0.07 μηι or less. The honing liquid system for metal used in the present invention can exhibit particularly excellent effects on the honed body having such wiring. [Bound Metal] In the honed body of the present invention, a barrier layer for preventing copper diffusion is provided between the copper wiring and the insulating film, and the barrier layer is made of a low-resistance metal material such as Ru, TiN, TiW, Ta, TaN, W, and WN are preferred, and Ta and TaN are particularly preferred. [Interlayer insulating film] The interlayer insulating film is preferably a dielectric material having a dielectric constant of 2.6 or less, and examples thereof include a ruthenium-based film and an organic interlayer insulating film. Particularly, a sand-based film made of a miscible carbon is preferable. [Examples] Hereinafter, the present invention will be described based on examples. The present invention is not limited by the embodiments. [Examples 1-4 to 1-4, Comparative Examples 1-1 and 1-2] (Preparation of honing liquid for metal) Honing particles: bismuth-type non-true spherical abrasive particles of colloidal cerium oxide 3 g/L (average The long diameter, the average short diameter and their ratio are shown in Table 1) -32 - 200821374

Organic acids containing specific nitrogen: (compounds shown in Table 1) 0.2 5 m ο I / L

Other organic acids: dihydroxyethylglycine 0.24mol/L

Heterocyclic compound: (compound shown in Table 1) 1.7mmol/L

Oxidizing agent: hydrogen peroxide 9.0 g / L

Contains the full amount of pure water: 1 0 0 0 m LP Η (adjusted with ammonia and sulfuric acid) 6.5 - Particle size control method for honing particles _ Adjustment of average long diameter and average short diameter of honing particles shown in Table 1 It is by a separation method according to centrifugation. (Horse test) Honing was performed under the following conditions, and the honing speed and the concave twist were evaluated. Honing device: FREX300 (荏原制所) honed body (wafer): (1) honing speed calculation; 300mm diameter blanket wafer with a thickness of 1μmτ1 on the 矽 substrate (2) For evaluation of concave distortion; copper wiring wafer with a diameter of 300 mm (pattern wafer: mask pattern 754CMP (ATDF)) honing gasket: IC1400K-XY Groove (NITTA HAAS) honing condition; honing pressure The contact pressure between the honing surface and the honing pad): It is shown in Table 1. The honing liquid supply speed: 200ml/min. The honing platform rotation number: 108rpm The honing head rotation number: 9 5 rpm -33 - 200821374 (Evaluation method ) - Average long diameter and average short diameter of the honing particles - The particles were measured by electron microscopy using a Hitachi Hi-Tech S4800 SEM to obtain the average enthalpy. - Contact pressure - measured by a load cell. - Surface temperature - The surface temperature was measured using a radiation temperature measuring device (NEC Sanyo T Η 7 1 0 2 ). - Honing speed - honing the above (1) blanket wafer for 60 seconds, and calculating the thickness of the metal film before and after honing from the resistance 値 on the wafer surface at 49 intervals. The average value of the enthalpy divided by the honing time is set as the honing speed. - concave twist - In the pattern wafer of the above (2), in addition to the time when the copper of the non-wiring portion is completely honed, an additional honing is performed at 20% of the time, the wire diameter gap (I The height difference of the ineandspace part (line diameter 1 0 0 μ m, gap 1 0 0 μ m) was measured by a contact type differential meter Dektak V320-Si (manufactured by Veeco Co., Ltd.). Further, the surface temperatures of Examples 1-1 to 1-4 and Comparative Examples 1-1 and 1-2 were controlled by adjusting the average major axis and the average minor axis of the honing particles. The results are shown in Table 1. -34- 200821374 [Table 1] Average long diameter (ητη) of honing particles Average short diameter (nm) of honing particles Average long diameter / average short diameter Contact pressure (Pa) surface of organic acid heterocyclic compound containing specific nitrogen Temperature CC) Honing speed (nm/min.) Concave twist (nm) Example 1-1 50 41 1.22 I-5 1H-tetrazole 9000 45 622 47 1 1 Example 1-2 50 20 2.50 I-5 1H-tetrazole 9000 42 698 38 Examples 1-3 50 14 3.57 I-5 1H-tetrazole 9000 50 721 36 Examples 1-4 50 10 5.00 I-5 1H-tetrazole 9000 52 679 44 Comparative Example 1 1 50 47 1.06 I-5 1H-tetrazole 9000 34 313 145 Comparative Example 1-2 50 8 6.25 I-5 1H-tetrazole 9000 75 512 123

As is apparent from Table 1, Examples 1-1 to 1-4 which satisfy the requirements of the present invention are known to exhibit high honing speed and low concave distortion. However, as in Comparative Example 1-1 and Comparative Example 1-2, when the average major axis and the average minor diameter of the honing particles are outside the range specified by the present invention, the honing speed is lowered and the concave distortion is deteriorated. . [Example 2-1, 2-2, Comparative Example 2-1, 2-2] Example 1 was used except that the contact pressure between the honed surface and the honing pad of the wafer was changed to the condition shown in Table 2. The honing test was carried out in the same manner as in Example 1 except for the honing speed and the concave distortion. Further, the surface temperatures of Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2 were controlled by adjusting the contact pressure between the honed surface and the honing pad. The results are shown in Table 2 below. -35- 200821374 [Table 2] Average long diameter (nm) of honing particles Average short diameter (nm) of honing particles Average long diameter / average short diameter Organic acid heterocyclic compound containing specific nitrogen Contact pressure (Pa) Surface Temperature (°c) Honing speed (nm/rnin.) Concave twist (nm) Example 2-1 50 14 3.57 I-5 1H-tetrazole 7000 36 615 33 Example, 1-3 50 14 3.57 I- 5 1H-tetrazole 9000 50 721 36 Example 2-2 50 14 3.57 i-5 1H-tetrazole 10000 65 783 55 Comparative Example 2-1 50 14 3.57 I-5 1H-tetrazole 3000 30 305 120 Comparative Example 2 -2 50 14 3.57 I-5 1H-tetrazazole 13000 78 890 150 It is apparent from Table 2 that Examples 2-1, 2-2 and 1-3 which satisfy the requirements of the present invention are known to exhibit high enthalpy Grinding speed with low concave distortion. However, when the contact pressure was lower than the range specified in the present invention as in Comparative Example 2-1, it was found that the honing speed was lowered and the concave distortion was also deteriorated. Further, as in Comparative Example 2-2, when the contact pressure was higher than the range specified by the present invention, the honing speed showed a high number of enthalpy, and the concave distortion was deteriorated. [Example 3-1, Comparative Examples 3-1 to 3-4] Each of the honing tests was carried out in the same manner as in Example 1 except that the organic acid was changed to the conditions shown in Table 3. The honing speed and the concave distortion were evaluated. Further, the surface temperatures of Example 3-1 and Comparative Examples 3-1 to 3-4 were controlled according to the kind of the organic acid containing a specific nitrogen. The results are shown in Table 3 below. -36- 200821374 [Table 3] Average long diameter (nm) of honing particles Average short diameter (nm) of honing particles Average long diameter / average short diameter Contact pressure of a specific nitrogen-containing organic acid or organic acid heterocyclic compound ( Pa) Surface temperature (°C) Honing speed (nm/min.) Concave twist (nm) Example 1-3 50 14 3.57 I-5 1H-tetrazole 9000 50 721 36 Example 3-1 50 14 3.57 I-7 1H-tetrazole 9000 47 694 42 Comparative Example 3-1 50 47 1.06 Oxalic acid 1H-tetrazole 9000 30 250 250 Comparative Example 3-2 50 8 6.25 Oxalic acid 1H-tetrazine 9000 78 512 355 Comparative Example 3-3 50 14 3.57 Oxalic acid 1H-tetrazole 9000 82 620 263 Comparative Example 3-4 50 14 3.57 Malic acid 1H-tetrazole 9000 79 572 311

As is apparent from Table 3, Examples 彳-3 and 3-1 which satisfy the requirements of the present invention are known to exhibit high honing speed and low concave distortion. However, the honing liquid for metals which does not contain the specific nitrogen-containing organic acid specified in the present invention is known to have a reduced honing speed and a deterioration in concave distortion. [Examples 4 - 1, 4 - 2, Comparative Examples 4 - 1, 4 - 2] Except that the concentration of the honing particles in Example 1 was changed to the amount shown in Table 4, the examples with the examples were彳_3 Modification of the honing liquid in the same manner as in Example 1 Each honing test was carried out in the same manner as in Example 1, and the honing speed and the concave distortion were evaluated. Further, the surface temperatures of Examples 4-1, 4-2 and Comparative Examples 4-1 and 4-2 were controlled by adjusting the content of the honing particles. The results are shown in Table 4 below. -37- 200821374 [Table 4] Average long diameter (nm) of honing particles Average short diameter (nm) of honing particles Average long diameter / average short diameter honing particle concentration repayment %) Organic acid containing specific nitrogen Ring compound contact pressure (Pa) Surface temperature CC) Honing speed (nm/min.) Concave twist (nm) Example 4-1 50 14 3.57 0.5 !-5 1H- Four-portion 9000 36 550 36 Example 1 -3 50 14 3.57 0.8 I-5 1H- Four Wow 9000 50 721 36 Example 4-2 50 14 3.57 1.2 I-5 1H- Four Ports 9000 65 756 58 Comparative Example 4-1 50 14 3.57 0.04 I-5 1H-four-seat 9000 30 285 123 Comparative Example 4-2 50 14 3.57 1.6 I-5 1H- Four π sitting 9000 78 865 154 It is apparent from Table 4 that Examples 4-1, 4- satisfying the requirements of the present invention The 2 and 1-3 known lines show high honing speed and low concave distortion. However, as in Comparative Example 4-1, when the concentration of the honing particles was lower than the range specified in the present invention, it was found that the honing speed was lowered and the concave distortion was also deteriorated. Further, when the concentration of the honing particles is higher than the range specified by the present invention, it is known that the honing speed shows a high number of enthalpy and the concave distortion is deteriorated. That is, it is understood that the effect of the present invention cannot be exhibited when the concentration of the honing particles is in the range of from 0.1 to 1.5% by mass. In each of the experimental items, the temperature of the surface to be honed was measured by the above method. When Tables 1 to 4 are listed, it is understood that the temperature of the surface to be honed which achieves high honing speed and low concave distortion is preferably in the range of 35 ° C or more and less than 75 ° C. -38- 200821374 [Simple description of the drawings] Fig. 1(A) and Fig. 1(B) are diagrams showing the device pattern for measuring the surface temperature of the wafer during honing. [Main component symbol description] 10 Honing device 12 Honing platform 13 Honing gasket

14 Opening 16A Radiation thermometer 1 6 B Radiation thermometer 22 Honing head 23 Wafer 24 Metal honing liquid (slurry) 26 Metal honing liquid supply port

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Claims (1)

200821374 X. Patent application scope: 1. A metal honing method, characterized in that the metal is supplied with a honing liquid to a honing pad on a honing platform, and the honing platform is rotated to make the 硏a metal honing method in which a grinding pad is in contact with a honed surface of a honed body and is relatively moved, and the honing liquid system includes a ratio of a long diameter to a short diameter (average long diameter/average The short diameter) is a honing particle of 1.2 to 5.0, an organic acid containing a 2-stage nitrogen atom or a nitrogen atom of 3, and a heterocyclic compound, and the contact pressure between the surface to be honed and the honing pad is 4000 to 1 2 0 0 0 P a, and the temperature of the surface of the honing pad contacting the honed surface, or the temperature of the honed surface is 35 ° C or higher and lower than 75 ° C , ponder the honed face. 2. The metal honing method according to claim 1, wherein the contact pressure between the honed surface and the honing pad is 7000 to 10000 Pa. 3. The metal honing method according to claim 1, wherein the honing particles have an average major diameter of 30 to 70 nm. 4. The metal honing method according to claim 1, wherein the organic acid containing the above-mentioned secondary nitrogen atom or tertiary nitrogen atom is represented by the following general formula (A) or the following general formula (B); , f Η Ra/N, Rb Formula (B) Ra/N, Rb Formula (A) 5. The metal honing method according to claim 1, wherein the heterocyclic ring of the above heterocyclic-40-200821374 compound It is a triazole ring or a tetrazole ring. 6. The metal honing method according to claim 1, wherein the compound is selected from the group consisting of: 1H-tetrazole, 5·amino-1H·tetrazole, 5·methyl-IH-tetrazole triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-tritriazole, 3-amino-1,2,4-triazole, 3,5- Diamine-1,2,4-: 7 The metal honing method of claim 1, wherein the compound is 1 Η-tetrazole. 8. The method of metal honing according to the scope of the patent application, wherein the oxidizing agent. 9. The metal honing method according to the first aspect of the patent application, wherein the organic acid or amino acid containing a nitrogen atom of a second order or a nitrogen atom is one less. The metal of any one of claims 1 to 9 wherein the concentration of the honing particles is 〇1 to 1.5% by mass relative to the above metal. The above-mentioned heterocyclic ring ^ ' 1,2,3-azole, 1,2,4 - three-seat 〇 The above heterocyclic ring system further contains 丨 《 "included to: other than the f grinding method, I 硏 grinding liquid and -41 -