TW201422740A - Phosphate surfactant in self-stopping polish - Google Patents

Abstract

The present invention provides a phosphate surfactant in self-stopping polish. The phosphate surfactant can keep a high copper removal rate and reduce dishing and over-polishing of copper line. Some defects, such as contaminants on the surface and corrosion also can be prevented.

Description

Application of a phosphate ester surfactant in self-stop polishing

This invention relates to the use of a phosphate ester surfactant in self-stop polishing.

With the development of semiconductor technology and the miniaturization of electronic components, an integrated circuit contains millions of transistors. In the course of operation, in the integration of such a large number of rapidly switching transistors, the traditional aluminum or aluminum alloy interconnects, the signal transmission speed is reduced, and the current transfer process requires a lot of energy, in a certain sense. It also hindered the development of semiconductor technology. In order to further develop, people began to look for the use of materials with higher electrical properties instead of aluminum. It is well known that copper has low electrical resistance and good electrical conductivity, which speeds up the transmission of signals between transistors in the circuit, and also provides less parasitic capacitance and reduces the sensitivity of the circuit to electromigration. These electrical advantages make copper have a good development prospect in the development of semiconductor technology.

However, in the copper integrated circuit manufacturing process, we found that copper migrates or diffuses into the transistor region of the integrated circuit, thus the electricity for the semiconductor. The performance of the crystal has an adverse effect, so the copper interconnect can only be fabricated by a damascene process, that is, a trench is formed in the first layer, a copper barrier layer and copper are filled in the trench, and a metal wire is formed and covered in the dielectric layer. on. The excess copper/copper barrier on the dielectric layer is then removed by chemical mechanical polishing leaving a single interconnect in the trench. The chemical mechanical polishing process of copper is generally divided into three steps. The first step is to remove a large amount of copper on the surface of the substrate with a high and low pressure at a high and low removal rate. The second step is to approach the barrier layer. When the downforce is lowered, the removal rate is reduced to polish the remaining metal copper and stopped in the barrier layer. In the third step, the barrier layer polishing solution is used to remove the barrier layer and part of the dielectric layer and the metal copper to achieve planarization.

On the one hand, copper polishing should remove excess copper on the barrier layer as soon as possible. On the other hand, the butterfly depression of the polished copper wire should be minimized. Prior to copper polishing, the metal layer is partially recessed above the copper wire. During polishing, the copper on the dielectric material is easily removed (higher) at the bulk pressure, while the copper at the depression is subjected to a lower polishing pressure than the bulk pressure, and the copper removal rate is small. As the polishing progresses, the height difference of the copper is gradually reduced to achieve flattening. However, in the polishing process, if the chemical action of the copper polishing solution is too strong and the static etching rate is too high, the passivation film of copper is easily removed even under a lower pressure (such as a copper line depression), resulting in lowering of planarization efficiency. The polished butterfly-shaped depression increases.

With the development of integrated circuits, on the one hand, in the traditional IC industry, in order to improve integration, reduce energy consumption, shorten delay time, line width is narrower, and the number of layers of wiring is also increasing, in order to ensure The performance and stability of integrated circuits are becoming more and more demanding for copper chemical mechanical polishing. It is required to reduce the polishing pressure while ensuring the removal rate of copper, improve the flattening of the surface of the copper wire, and control surface defects. On the other hand, due to physical limitations, the line width cannot be infinitely reduced. Small, the semiconductor industry is no longer simply relying on integrating more devices on a single die to improve performance, turning to multi-chip packages. Through-via (TSV) technology is widely recognized in the industry as the latest technology for interconnecting between wafers and wafers, and between wafers and wafers to achieve interconnection between wafers. TSV enables wafers to be stacked in the three-dimensional direction with the highest density and smallest form factor, greatly improving wafer speed and low power consumption. The current TSV process combines a conventional IC process to form a copper via that penetrates the substrate, that is, the copper is filled in the TSV opening to achieve conduction, and the excess copper after filling needs to be removed by chemical mechanical polishing to achieve planarization. Unlike the conventional IC industry, the excess copper in the surface after filling is usually several to several tens of micrometers thick due to the deep through hole of the crucible. In order to quickly remove these extra copper. It is usually required to have a high copper removal rate while the surface roughness after polishing is good. In order to make copper better in semiconductor technology, people are constantly trying to improve the new polishing solution.

Chinese patent CN1256765C provides a polishing liquid containing a chelating organic acid buffer system composed of citric acid and potassium citrate. CN1195896C employs a polishing liquid containing an oxidizing agent, a carboxylate such as ammonium citrate, an abrasive slurry, an optional triazole or triazole derivative. CN1459480A provides a copper chemical mechanical polishing liquid comprising a film former and a film forming aid: the film forming agent is composed of a buffer solution composed of a mixture of a strong base and acetic acid, and the film forming aid is a potassium nitrate (sodium) salt. U.S. Patent No. 5,552,742 provides a metal chemical mechanical polishing slurry comprising a surfactant comprising aramid oxime, alkane polyoxyalkylene, polyoxyalkylene ether and copolymers thereof. US Pat. No. 6,821,897 B2 provides a copper chemical mechanical polishing method using a polishing agent containing a polymer complexing agent, which employs a negatively charged polymer including sulfuric acid and its salts, sulfates, phosphoric acid, phosphates, phosphates, and the like. . The US5527423 metal chemical mechanical polishing slurry comprises a surfactant: aramid oxime, polyoxyalkylene, polyoxyalkylene ether and copolymers thereof.

The techniques in the above patents strive to reduce pitting and corrosion of the copper layer and control the static etching rate during the polishing process of copper, thereby better removing the copper layer, increasing the polishing rate of copper, and obtaining good copper. Interconnectivity. The above patent overcomes the problems encountered by the above copper in the polishing process to a certain extent, but the effect is not obvious. After use, there are defects on the copper surface, the flatness is low, and the copper wire has a large dishing after polishing. The window is too narrow; or the polishing rate is not high enough to be applied to processes that require a higher removal rate.

One aspect of the present invention is to provide a use of a phosphate ester surfactant in self-stop polishing. The above phosphate surfactant can maintain a high copper removal rate, improve the dishing and over-polishing of the polished copper wire, and has less defects on the copper surface after polishing, and no corrosion and the like.

The phosphate surfactant has one or more of the following structural formulas: and / or

Wherein X = RO, RO-(CH ₂ CH ₂ O) _n , RCOO-(CH ₂ CH ₂ O) _n ; R is a C ₈ ~ C ₂₂ alkyl group or an alkyl benzene, a glyceryl group (C ₃ H ₅ O ₃ -) Etc.; n = 2~30, M = H, K, NH ₄ , (CH ₂ CH ₂ O) _1~3 NH _3~1 and/or Na. Among them, preferred are compounds having both the above structures (1) and (2). Preferably, the surfactant is a combination of a compound selected from the group consisting of the structure (1) and a compound selected from the structure (2).

Wherein when R is a C ₈ -C ₂₂ alkyl group, the surfactant is a polyoxyethylene ether phosphate or a salt thereof, such as dodecyl polyoxyethylene ether phosphate or dodecyl polyoxyethylene ether phosphate. Potassium salt, octadecyl polyoxyethylene ether phosphate, octadecyl polyoxyethylene ether phosphate potassium salt and the like. When R is an alkylbenzene, the surfactant is an alkylphenol ethoxylate phosphate or a salt thereof, including octylphenol polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether phosphate, octadecane Sodium phenol polyoxyethylene ether phosphate sodium salt and the like. Experiments have shown that the chemical polishing slurry composed of the above surfactants and abrasive particles, complexing agent, oxidizing agent and the like can effectively control the static corrosion rate of copper and alleviate the local corrosion of copper while maintaining a high copper removal rate. Improve the butterfly-shaped depression and over-polishing window of the polished copper wire to obtain a polished surface of a flatter copper.

The invention also provides a synergistic application of the phosphate ester full active agent together with the abrasive particles, the complexing agent, the corrosion inhibitor, and the oxidant group to form a polishing slurry.

Wherein, the content of the phosphate surfactant is 0.0005 to 1% by weight, preferably 0.001 to 0.5% by weight.

Wherein, the abrasive particles are one or more of cerium oxide, aluminum oxide, doped aluminum or aluminum-coated cerium oxide, cerium oxide, titanium dioxide and/or polymer abrasive particles.

Wherein, the abrasive particles have a particle diameter of 20 to 200 nm.

Wherein, the abrasive particles have a specific surface area of 5 to 1000 m ² /g.

Wherein, the content of the abrasive particles is 0.1-20% by weight.

Wherein the complexing agent is an aminocarboxylate compound and a salt thereof, an organic carboxylic acid and One or more of its salts, organic phosphonic acids and salts thereof and/or organic amines.

Wherein the aminocarboxyl compound is selected from the group consisting of glycine, alanine, valine, leucine, valine, phenylalanine, tyrosine, tryptophan, lysine, arginine, group Amino acid, serine, aspartic acid, threonine, glutamic acid, aspartame, glutamine, aminotriacetic acid, ethylenediaminetetraacetic acid, cyclohexanetetraacetic acid, ethylenediamine disuccinic acid One or more of diethylenetriaminepentaacetic acid and triethylenetetramine hexaacetic acid; the organic carboxylic acid is acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, succinic acid, malic acid, lactic acid, no One or more of gallic acid and sulfosalicylic acid; the organic phosphonic acid is 2-phosphonic acid butane-1,2,4-tricarboxylic acid, aminotrimethylidenephosphonic acid, hydroxyethylidene diphosphine a kind of acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriamine pentamethylphosphonic acid, 2-hydroxyphosphonic acid acetic acid, ethylenediaminetetramethylenephosphonic acid and polyaminopolyether methylphosphonic acid Or a plurality of; the organic amine is ethylenediamine, diethylenetriamine, pentamethyldiethylenetriamine, polyethenepolyamine, triethylenetetramine, tetraethylenepentamine; the salt is Salts, sodium and / or ammonium salts.

Wherein, the content of the complexing agent is 0.05-10% by weight. Preferably, the weight percentage is 0.1 to 5%.

Wherein the oxidizing agent is hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, perboric acid, potassium permanganate and ferric nitrate. One or more.

Wherein, the content of the oxidizing agent is 0.05 to 10% by weight.

Wherein, the corrosion inhibitor is one or more of azole, imidazole, thiazole, pyridine and pyrimidine.

Among them, azole compounds include: benzotriazole, 5-methylbenzotriazine Azole, 5-carboxybenzotriazole, 1-hydroxy-benzotriazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1 , 2,4-triazole, 3,5-diamino-1,2,4-triazole, 5-carboxy-3-amino-1,2,4-triazole, 3-amino-5- Mercapto-1,2,4-triazole, 5-acetic acid-1H-tetrazole, 5-methyltetrazole, 5-phenyltetrazolium, 5-amino-1H-tetrazole and 1- Phenyl-5-mercapto-tetrazole. The imidazole compounds include benzimidazole and 2-mercaptobenzimidazole. The thiazole compound includes 2-mercapto-benzothiazole, 2-mercaptothiadiazole and 5-amino-2-mercapto-1,3,4-thiadiazole; the pyridine includes 2,3-di Aminopyridine, 2-aminopyridine and 2-picolinic acid. The pyrimidine is a 2-aminopyrimidine.

Wherein, the content of the corrosion inhibitor is 0.001 to 2% by weight, preferably 0.005 to 1% by weight.

Among them, the pH is 3 to 11, preferably 3 to 9.

Among them, pH adjusting agents, viscosity modifiers, antifoaming agents, bactericides and the like are conventional additives in the art.

The above metal chemical mechanical polishing slurry can prepare a component other than the oxidizing agent into a concentrated sample, which can be diluted with deionized water to the concentration range of the present invention and added with an oxidizing agent before use.

A surfactant containing phosphate as a main component is added to the above polishing slurry, thereby having a self-stopping property in polishing, and improving the flatness of the polished surface of copper while maintaining a high polishing rate of copper. Throw the window to enhance the polishing effect.

Use of the polishing slurry of the present invention in chemical mechanical polishing of a substrate containing copper. The advantages of using the metal chemical mechanical polishing slurry of the present invention are as follows:

1. The metal chemical mechanical polishing slurry of the present invention has a high copper removal rate The rate can also effectively control the corrosion of copper, and the polished copper surface has no corrosion.

2. The metal chemical mechanical polishing slurry of the present invention enhances the polishing effect of copper, and has a self-stopping property after the polishing reaches the end point, thereby improving the butterfly depression and the over-throwing window of the polished copper wire.

3. The polishing liquid of the invention can shorten the polishing time, increase the production capacity, and reduce the production cost.

1A and 1B are scanning electron micrographs of a patterned copper wafer surface polished by the polishing slurry of the present invention; and FIGS. 2A and 2B are schematic copper wafer surface scans polished and immersed using the polishing slurry of the present invention; Electron micrograph; FIG. 3 is a dish-shaped depression after polishing the patterned copper wafer with different polishing time using the polishing slurry of the present invention and the comparative polishing slurry.

The advantages of the present invention are further illustrated by the following specific examples, but the scope of the present invention is not limited only to the following examples.

Examples 1 to 49

Table 1 shows Examples 1 to 49 of the chemical mechanical polishing liquid of the present invention. According to the formulation given in the table, the components other than the oxidizing agent were uniformly mixed, and the mass percentage was made up to 100% with water. Adjust to the desired pH with KOH or HNO ₃ . Add oxidizing agent before use and mix well.

Effect embodiment

Table 2 shows Examples 50 to 71 and Comparative Examples 1 to 6 of the chemical mechanical polishing liquid of the present invention, according to the formulation given in the table, the components other than the oxidizing agent were uniformly mixed, and the mass percentage was made up to 100 by water. %. Adjust to the desired pH with KOH or HNO ₃ . Add oxidizing agent before use and mix well.

The copper (Cu) wafer and the patterned copper wafer are polished using the comparative polishing liquid 1 to 3 and the polishing liquid 50 to 65 of the present invention. The polishing rate of the obtained copper is shown in Table 3. The polishing conditions of the pattern wafer and the dishing value of the copper block are shown in Table 4.

Empty copper wafer polishing conditions: downforce 1~3 psi; polishing disc and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150 ml/min, polishing machine 8" Mirra.

Patterned copper wafer polishing process conditions: polishing disc and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150 ml/min, polishing machine table 8" Mirra. Polished on the polishing disc 1 with corresponding downforce The patterned copper wafer is about 3000A to the residual copper, and then the corresponding downforce will be applied to the polishing disk 2 The residual copper is removed and thrown for 20 seconds. The dishing value of the 80 um*80 um copper block on the patterned copper wafer was measured with an XE-300P atomic force microscope.

The polished pattern wafer was immersed in the polishing liquid for 30 minutes, and the surface condition of the copper wire before and after the immersion was observed with a scanning electron microscope, see FIGS. 1A and 1B and 2A and 2B.

It can be seen from Table 3 that the metal chemical mechanical polishing slurry of the present invention can effectively reduce the removal rate of copper under low pressure compared with the comparative polishing liquid, but has little effect on the removal rate under higher downforce. . This property allows the polishing fluid to achieve a smoother polishing surface while maintaining a higher removal rate, which greatly increases production efficiency and reduces the dishing of the polished copper block. A lower dishing value can also be obtained under conditions close to the removal rate of the comparative polishing liquid 2. (See Table 4)

The SEM images of the patterned wafer after polishing and after polishing and immersion in Example 57 are shown in Figs. 1A to 2B. It can be seen from the figure that the surface of the wafer polished by the polishing liquid has no corrosion and no defects. After immersing in the polishing solution for 30 minutes, the copper wire still has no obvious corrosion and defects, indicating that the polishing liquid of the invention has strong inhibition of metal corrosion. ability.

The empty copper (Cu) wafer, the empty ytterbium oxide wafer, the empty ruthenium wafer, and the patterned copper wafer are polished using the comparative polishing liquid 5 and the polishing liquids 66 to 71 of the present invention. The polishing rate obtained and the dishing value of the copper block are shown in Table 5.

Empty sheet polishing conditions: lower pressure 1~3 psi; polishing disc and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150 ml/min, polishing machine table 8" Mirra.

Patterned copper wafer polishing process conditions: polishing disk and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150ml/min, polishing machine table 8" Mirra. Polished on the polishing plate 1 with 3psi under pressure The patterned copper wafer was left to about 5000 A of residual copper, and then the residual copper was removed by a 2 psi downforce on the polishing pad 2. The patterned copper wafer was measured on a patterned copper wafer by XE-300P atomic force microscope (copper wire/dioxide)碟) The dishing value at the copper wire.

As can be seen from Table 5, the metal chemical mechanical polishing slurry 66 to 68 of the present invention can obtain a flatter polished surface while maintaining a higher removal rate than the comparative polishing liquid 5, by Example 69 As can be seen from ~71, the polishing solution can also provide a higher removal rate of cerium oxide and cerium while the copper removal rate is adjustable. The polishing solution can meet different application needs.

The patterned copper wafer was polished using a comparative polishing liquid 5, 6 and a polishing liquid 66 to 68 of the present invention. Polishing process conditions: polishing disc and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150 ml/min, polishing machine table 8" Mirra. Polished patterned copper wafer was polished on the polishing disc 1 with a pressure of 3 psi to The remaining copper is about 5000 angstroms, and then the remaining copper is removed on the polishing pad 2 with a downforce of 2 psi. Observing the residual copper on the patterned copper wafer after polishing is shown in Table 6.

It can be seen from Table 6 that the phosphoric acid ester surfactant is used alone in the polishing liquid of Comparative Example 6, and the surface of the wafer has copper residue after polishing, and the azole corrosion inhibitor is used alone in the polishing liquid of Comparative Example 5, although there is no copper residue on the surface after polishing, The dish type has a large depression. In Examples 66 to 68, a combination of an azole corrosion inhibitor and a phosphate ester surfactant was used, which was capable of reducing dishing and polishing without copper residue.

The comparative copper slurry and the polishing liquid 72 of the present invention are used to polish the empty copper and the patterned copper wafer on the polishing disk 1 (P1) and the polishing disk 2 (P2) with respective lower pressures. Polishing process conditions: polishing disc and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150 ml/min, polishing machine table 8" Mirra. Empty copper wafer polishing time is 1 minute, patterned copper wafer The thickness of copper is about 10,000 angstroms. The polishing time of the patterned copper wafer on different polishing discs is automatically controlled by the polishing machine to be polished and the polishing disc 2 is thrown for different time. The removal rate of copper on the empty wafer is The polishing time of the patterned copper wafer is shown in Table 7. The dishing at the 80 x 80 micron copper block at different throwing times is shown in Fig. 3.

As can be seen from Table 7 and Figure 3, the polishing liquid 72 of the present invention has a lower dish-shaped depression at a higher polishing rate than the comparative polishing liquid 2, and the dish-shaped depression increases with the elongation of the throwing time. Small, with self-stop performance, over-throwing window width. Moreover, the polishing liquid of the present invention has a short polishing time on the patterned wafer, which is advantageous for increasing productivity and reducing cost.

It should be understood that the wt% of the present invention refers to the mass percentage content.

The specific embodiments of the present invention have been described in detail above, but are merely exemplary, and the invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions to the invention are also within the scope of the invention. Accordingly, equivalents and modifications may be made without departing from the spirit and scope of the invention.

Claims (19)

A phosphate ester surfactant for use in self-stop polishing, wherein the phosphate surfactant comprises at least one or more of the following structural formulas: and / or Where: X = RO, RO-(CH ₂ CH ₂ O) _n , RCOO-(CH ₂ CH ₂ O) _n ; R is C ₈ ~ C ₂₂ alkyl or alkyl benzene, glyceryl (C ₃ H ₅ O ₃ -), n=2~30, M=H, K, NH ₄ , (CH ₂ CH ₂ O) _1~3 NH _3~1 and/or Na. The use of claim 1, wherein the phosphate surfactant comprises two or more of the following structures: and / or , wherein: X = RO, RO-(CH ₂ CH ₂ O) _n , RCOO-(CH ₂ CH ₂ O) _n ; R is C ₈ ~ C ₂₂ alkyl or alkylbenzene, glyceryl (C ₃ H ₅ O ₃ -), n=2~30, M=H, K, NH ₄ , (CH ₂ CH ₂ O) _1~3 NH _3~1 and/or Na. The application of claim 1, wherein the phosphate ester surfactant is used in combination with abrasive particles, a complexing agent, a corrosion inhibitor, and an oxidizing agent-constituting polishing liquid. The application of claim 1, wherein the phosphate surfactant is present in an amount of from 0.0005 to 1% by weight. The application of claim 4, wherein the phosphate surfactant is present in an amount of from 0.001% to 0.5% by weight. The application of claim 3, wherein the abrasive particles are one or more of cerium oxide, aluminum oxide, aluminum-doped or aluminum-coated cerium oxide, cerium oxide, titanium dioxide, and polymer abrasive particles. The application of claim 3, wherein the abrasive particles have a particle size of 20 to 200 nm. The application of claim 3, wherein the abrasive particles have a concentration by weight of 0.1 to 20%. The use according to claim 3, wherein the complexing agent is one or more of an aminocarboxylate compound and a salt thereof, an organic carboxylic acid and a salt thereof, an organic phosphonic acid and a salt thereof, and an organic amine. The application according to claim 9, wherein the aminocarboxy compound is selected from the group consisting of glycine, alanine, valine, leucine, valine, phenylalanine, tyrosine, tryptophan, and lysine. Amino acid, arginine, histidine, serine, aspartic acid, threonine, glutamic acid, aspartame, glutamine, ammonia triacetic acid, ethylenediaminetetraacetic acid, cyclohexane One or more of acetic acid, ethylenediamine disuccinic acid, diethylenetriaminepentaacetic acid and triethylenetetramine hexaacetic acid; the organic carboxylic acid is acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, diced One or more of acid, malic acid, lactic acid, gallic acid and sulfosalicylic acid; the organic phosphonic acid is 2-phosphonic acid butane-1,2,4-tricarboxylic acid, aminotrimethylidene Phosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylene phosphonic acid, diethylenetriamine pentamethylphosphonic acid, 2-hydroxyphosphonic acid, ethylenediaminetetramethylenephosphonic acid and polyaminopolyether One or more of the methylidene phosphonic acids; the organic amines are ethylenediamine, diethylenetriamine, pentamethyldiethylenetriamine, polyethenepolyamine, triethylenetetramine, tetraethylidene Isopentamine; the salt is a potassium salt, a sodium salt and/or an ammonium salt. The application of claim 3, wherein the complexing agent is present in an amount of 0.05 to 10% by weight. The application of claim 11, wherein the complexing agent is preferably present in an amount of from 0.1 to 5% by weight. The application of claim 3, wherein the oxidizing agent is hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, perboric acid, One or more of potassium permanganate and ferric nitrate. The application of claim 3, wherein the oxidizing agent is present in an amount of 0.05 to 10% by weight. The application of claim 3, wherein the corrosion inhibitor is one or more of a azole, an imidazole, a thiazole, a pyridine, and a pyrimidine compound. The use of claim 15, wherein the azole compound is selected from the group consisting of benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, 1-hydroxy-benzo Triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3,5-diamino-1 , 2,4-triazole, 5-carboxy-3-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 5-acetic acid-1H Tetrazolium, 5-methyltetrazolium, 5-phenyltetrazolium, 5-amino-1H-tetrazole and 1-phenyl-5-mercapto-tetrazolium. The imidazole compounds include benzimidazole and 2-mercaptobenzimidazole. The thiazole compound includes 2-mercapto-benzothiazole, 2-mercaptothiadiazole and 5-amino-2-mercapto-1,3,4-thiadiazole; the pyridine is selected from one of the following Or more than: 2,3-diaminopyridine, 2-aminopyridine and 2-picolinic acid. The pyrimidine is a 2-aminopyrimidine. The application of claim 3, wherein the content of the corrosion inhibitor is heavy The percentage of the amount is 0.001~2%. The application of claim 17, wherein the corrosion inhibitor is present in an amount of from 0.005 to 1% by weight. The application of claim 3, wherein the abrasive particles have a specific surface area of from 5 to 1000 m ² /g.