TW200925326A - Sarcosine compound for using as corrosion inhibitor - Google Patents

Abstract

A sarcosine compound for using as a corrosion inhibitor of the present invention is sarcosine and its salt compound. The corrosion inhibitor is applied to a chemical mechanical grinding composition or a post-grinding cleaning agent. A protective film can be formed on the surface of the processed object during the chemical mechanical grinding process so as to prevent the processed object from being corroded. And the defect that residues formed on the surface of the processed object while using the conventional corrosion inhibitor (e.g. benzotriazole; BTA) may be overcome. Alternatively, the surface of the processed object is protected during the post CMP cleaning process and is prevented from being corroded.

Description

200925326 IX. Description of the Invention: [Technical Field] The present invention relates to a creatinine or a sarcosine compound as a corrosion inhibitor, and aims to provide a corrosion inhibitor for chemical mechanical polishing of a composition, which can be improved The corrosion resistance of the processed object does not leave any residue on the surface of the abrasive article, or protects the surface of the workpiece from corroded corrosion inhibitor when the CMp is clean. ® [Prior Art] ’

Ik's critical dimension of electronic components (Critical Dimensi〇n) is getting more and more J and 'the rapid increase of the number of layers, resistance / capacitance time delay (10) Ti = Delay) will affect the operating speed of the overall circuit. In order to improve the time delay caused by the reduction of the line width of the f metal and the electron migration, the copper wire material having a low resistivity and high electron migration resistance is selected to replace the alloy metal. However, since copper metal has a property of being difficult to etch, it is necessary to adopt another Damascene method to form a copper metal wire. The damascene method is different from the conventional metallization method in which a metal pattern is first defined and then filled with a dielectric layer by etching a trench of a metal line on a flat dielectric. The metal layer is filled in, and finally the excess metal is removed, and a flat, inlaid process having a metal inlay in the dielectric layer has the following advantages over the conventional metallization process: =) the substrate surface can be made anytime (2) It can eliminate the shortcomings of "the electrical material is not easy to fill the gap of the metal wire in the traditional process: (3) can solve the problem of difficult etching of the metal material, especially the etching of copper metal. 200925326 = external 'to overcome the traditional In the process of connecting the wire, the contact window structure and the wire f file are not made, which makes the whole process step extremely complicated. In addition, the other is to display a dual damascene process, which is carried out twice. Selective etching, respectively, after the wire dielectric and the dielectric (viadieiec1: ric) are opened, the second = the barrier layer of the metal layer and the plug, and the conductive metal is once Filling in the vias and interconnect trenches to achieve a simplification of the process steps. In recent years, Ο ❹ ^ need to be equipped with n], the hair (4) and the need to improve the material operating speed have low resistance constant and high Electron migration resistance of copper and gold is gradually being applied as a material for metal interconnects, replacing the previous process technology. The inlaid interconnect technology of steel metal can not only achieve line reduction and reduce time delay, but also The solution, the problem is not easy. Therefore, it has become the copper process of today's multiple internal companies. Whether it is a single- or dual-function copper process, after the completion of the copper charging, a flattening process is required to remove the excess on the dielectric layer. Gold h. Currently, this is usually achieved by a chemical mechanical polishing process. The copper-chemical mechanical polishing process is usually divided into two steps. The second stage is the faster grinding rate. Copper removal, ^ plus 2 output. The second stage is to use a slower grinding rate to remove the multiplication: the next small J copper 'to avoid excessive grinding of the copper in the groove ^ two stages Copper grinding process, need to replace different groups Grinding: 'To meet the needs of different stages of copper grinding.,, the general 'General' metal layer (copper) chemical mechanical grinding is carried out in the acidic range of about 200925326 4 (with dielectric layer In the same basic) and chemical mechanical polishing composition usually adds less ', but under the ruthenium oxide' to increase the polishing rate. However, due to the corrosion of the steel gasification agent (such as corrosion and extremely easy to oxidize, and copper can not Like aluminum will form a layer of self-eviability, so after the grinding under such conditions, the final tempering is corroded, thus seriously affecting the product of the interconnect. "The name is to solve the above problem." The prior art is Abrasive inhibitors in the grinding process, such as benzotriazole (1H-benz〇triaz〇le; two plus one ruthenium-free copper metal or its alloys under the acid f. ^ 'In order to avoid the benzotriazine, the surface of the workpiece (the wafer is ground and the residue is not easily removed by a cleaning agent such as deionized water, so that the read plus = and the sheet) is formed by the residue to form an uneven surface object ( The subsequent process of the crystal (wafer). The main object of the present invention is to provide a corrosion inhibitor for the composition of the trench, which can improve the suppression of the processed article 'grinding and not grinding A corrosion inhibitor of residue remains on the surface of the object. In order to achieve the above, the muscle chelating compound as a corrosion inhibitor in the present invention is sarcosine and a salt thereof, and the rotatory button inhibitor is used for In the chemical mechanical polishing composition, a protective film may be formed on the surface during chemical mechanical polishing to avoid corrosion of the processed article. Second, it is preferred to use a corrosion inhibitor (such as benzotriazole; BTA). ', , can be modified to form a residue residue on the surface.; Force 200925326 Another object of the present invention is that the corrosion inhibitor can also be used in a post CMP clean agent to protect The surface of the workpiece is free from, for example, the aggressive nature of the cleaning solution, oxidation, post-cleaning corrosion, chemically induced current erosion, or photo-induced erosion. [Embodiment] The features of the present invention can be referred to the drawings and the details of the embodiments. According to the present invention, the "creatinine compound as a corrosion inhibitor" is a creatinine compound such as sarcosine and a salt compound thereof, or the s The inhibitor is used in the chemical mechanical polishing composition, and can form a layer of protection on the surface of the processed object during chemical mechanical polishing to avoid corrosion of the processed object, and can improve the inhibition of the processed object. Corrosion inhibitors, further improved: abrasive particles, oxidizing agents, accelerators, inhibitors, and solvents. Sodium sulphate: Examples include, but are not limited to, calcined cerium oxide; self-gelling; Dicalcium oxide and condensed molecular materials: calcined alumina; precipitated or calcined titanium dioxide; high preferred And hybrids of polymer materials. Grinding, can not be far-reaching "^ gluten. If the amount of abrasive particles is too low, it is not conducive to the mechanical removal rate is expected to be the highest removal rate; The removal rate of the granular layer, the effect of the rapid mechanical grinding, the addition of the barrier layer and the example of the insulating oxidation, the grinding defects of the surface abrasion are easy to be diagnosed. The specific weight of the composition is in a specific Λ / compound. 〇1 to 3〇% by weight, which is 0.1 to 15% by weight of the 200925326. For the chemical mechanical polishing composition of the ground copper layer, it is preferred to use hydrogen peroxide as the oxidizing agent. Usually, the oxidizing agent accounts for The total weight of the composition is from 0.25 to 5% by weight, preferably from 0.5 to 3% by weight. Examples of the additive for the chemical mechanical polishing composition include, but are not limited to, citric acid, oxalic acid, tartaric acid, group Amino acid, alanine, or glycine. The accelerator is used to promote dissolution of the metal to be ground, such as copper. Increasing the amount of accelerator added to the abrasive composition contributes to the grinding of the metal layer. The grinding removal rate is suitable for the first stage of metal layer grinding. However, increasing the amount of accelerator added in the polishing composition also increases the rate of static etching', which is not conducive to the fine polishing of the first stage. In one embodiment, the accelerator is 〇 至 1 to 1 〇 by weight, preferably from 1 to 5% by weight, more preferably from 0.3 to 3% by weight. 5 Hai chemical mechanical polishing composition of the corrosion inhibitor and inhibitor, under the condition of high grinding removal rate 'effectively suppress the static etching rate, suitable for the first stage and the second stage of the grinding and polishing process, the corrosion of the present invention The inhibitory tincture may be a sarcosine compound such as sarcosine and a salt thereof, and examples of the creatinine and salts thereof include, but are not limited to, sarcosine (SarC〇Sine),

Formula 1 (CH3NHCH2COOH > CAS= 107-97-1) Laurel sarcosine, 200925326

(C15H29N〇3 > CAS 97-78-9)

N-acyl sarcosine, cocoyl sarcosine, oleoyl sarcosine, stearoyl sarcosine, and meat stalks Myristoyl sarcosine or its lithium, sodium, potassium, or amine salt or the like; or a mixture thereof; for example, sodium serotonin sodium salt (Sodium n-Lauroyl Sarcosinate)

Ο [CH3(CH2)i〇CON(CH3)CH2COONa, CAS 137-16-6] In general, the residual inhibitor is 〇〇〇〇5 to 1% of the total weight of the composition, 敉隹The total weight of the composition is 〇. 001 to the total weight of the composition. 〇〇5 to 〇. 1%. Examples of such inhibitors include, but are not limited to, compounds; azole compounds and derivatives thereof, such as triazoles, 3-amines; 10 200925326 triazole-5-carboxylic acid, iH-benzotriazole, or 5-quinone Base-1,2,3-benzotrisole. 005至0. 8%,更优选的总总总重量重量。 The total weight of the composition of the composition of the total weight of the composition. 〇〇〇1 to 1%, preferably the total weight of the composition of 0. 005 to 0. 8%, better than the total weight of the composition 01至0. 5%。 0. 01 to 0. 5%. The composition of the present invention may use water as a solvent. It is preferred to use deionized water as a solvent for the polishing composition. The features of the present invention are further illustrated by the specific embodiments, but are not intended to limit the scope of the invention.实施 Example 1 according to Table 1 'Use of cerium oxide sol particles including an average particle size of about 90 nm, alanine, hydrogen peroxide, 1,2,4-triazole (inhibitor), cocoyl Sodium sarcosinate (corrosion inhibitor) and a control sample of the slurry slurry composition in which the solvent is water were tested. Wherein, the chemical formula of the sodium citrate sodium sarcosinate is as shown in the formula:

Formula 4 (RCON(CH3)CH2COONa, CAS 61791-59-1) 10 cases 1 Control oxidant (hydrogen peroxide) · (wt%) 0.7JJ l/f Accelerator (alanine) (wt%) Inhibitor ( Wt%) Abrasive (cerium oxide sol) (wt%) Corrosion inhibitor ppm 2.4 ~2Λ ~ΪΛ 0.025 0. 025

0.1 TT 200925326 I Comparative Example 4 I 0.7 1 2.4 I 0 I 0.1 I 50 Table 1 The grinding test was carried out according to the following conditions, and the average values of the removal rate (RR) and the etching rate (Etch Rate) were recorded in the table. Grinding machine: Mirra polisher (Applied Materials) Wafer type: 8吋 Copper film wafer (Ramco Co) Grinding pressure: 2 psig © Platform speed: 90 rpm 'Car speed: 85 rpm Grinding pad: IC 1010 (Rohm and Haas) Slurry flow rate: 200 ml/min. --------- Cu RR@ 1.5psi Cu RR@ 3psi Last Name Rate, A/min 4930 9790 915 Control 2 2257 7729 319 Comparative Example 3 7458 >15425 3023 Comparative Example 4 1470 >15425 578 Table II

Example 1 According to the results of Table 2, in Comparative Example 1 and Comparative Example 2, the copper removal removal rate and the etching rate of the control solution were larger than that of the control example 2, and the control example was the copper polishing removal of the comparative example 3 in the comparative example 4 The rate and etching rate are as follows. For example, if you use cocoyl sarcosine as the rot, the inhibitor will greatly reduce the copper removal rate and the engraving rate. Capability 'can effectively avoid 12 200925326 Examples According to Table 3, Comparative Example 5 uses cerium oxide sol particles, hydrogen peroxide, potassium hydroxide, benzotriazole including an average particle size of about 9.9 〇 (10). (Corrosion Inhibitor), while Comparative Example 6 uses cerium oxide sol abrasive particles having an average particle diameter of about 9 Å, hydrogen peroxide, potassium cerium oxide, sodium cocoyl sarcosinate (corrosion inhibitor), and Solvent is water slurry composition oxidant (hydrogen peroxide) (wt%) abrasive particles (cerium oxide sol) (wt%) ΒΤΑ ppm Team mouth J ✓ only _J corrosion inhibitor Ppm (four) ° KOH (wt %) pH Comparative Example 5 0.5 30.0 50 0 0.1 1 Factory Comparative Example 6. 0.5 30.0 0 50 0.1 11 Table 3研磨 The grinding test was carried out according to the following conditions. The average value of the polishing removal rate (Rein〇val Rate 'RR) is shown in Table 4. Grinding machine: Applied Material Mirra Polisher, (San Jose, CA) 晶圆 Wafer type: 8 覆 copper, TEOS, button film wafer grinding pressure: 2 psig platform speed: 70 rpm vehicle speed: 65 rpm polishing pad: IC 1010 (R〇hm and Haas) slurry flow rate: 200 ml/min p

Ox grinding removal rate (A/min) Cu grinding removal rate (A/min) Ta grinding removal rate (A/min) Comparative Example 5 1244 657 633 Comparative Example 6 1223 556 601 13 200925326 Root #表曰的结果' The copper polishing removal rate and the group (Ta) polishing removal rate of Example 5 were larger than that of the fresh light example 6. From the results, it was found that the use of coconut oil-based creatinine as a blister (tetra) agent greatly reduced the grinding of copper and surface (Ta). The removal rate is so that the coconut oil can be used as a serotonin inhibitor to improve the ability of the car to inhibit the surface of the rot (compared to benzotriazine as a rot-inhibitor), which can effectively avoid processing objects. Corroded. & Each of the above examples shows that the sclerosine acid compound of the present invention (such as the scorpion scorpion and its Wei compound) acts as a corrosion inhibitor in the chemical mechanical polishing composition, and has a stupid and sedative (1H_benz〇triaz〇). Ie; bta) As a succulent preparation, it has the ability to suppress the corrosion of the button, avoiding the addition of the rot and not leaving a crucible peak on the surface of the abrasive article. In addition, the antiseptic inhibitor of the present invention can also be used for post-grinding cleaning of the qi ' 该 该 四 四 四 四 四 四 四 四 四 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物The erosion property of the liquid, the oxidation, the current known by the post-cleaning chemistry, or the light-induced intrusion. Although CMP can effectively planarize the surface of the workpiece, this process of contaminants remains on the surface of the object and must be removed after application to remove such > dyeable residue. The purpose of cleaning is to remove the residue left by the CMP step from the addition of genus, genus, residual deposits on the surface, or contaminants to the workpiece J, (e.g., carbon). In addition, it is desirable to protect the surface of the object from the surface of the 200925326. The corrosion of the different mechanisms is ideal, such as chemical button etching, chemical susceptibility or photo-induced corrosion. Corrosion on the surface of the workpiece causes metal recesses and thins the wire. Acidic cleaning solutions are generally quite effective at removing organic contaminants from the surface of the workpiece and misaligning the residual copper. It would therefore be desirable to have a cleaner that is effective at moderate to low pH values. Acidic chemistry is typically used in a scrubbing box or ultrasonic cleaning unit for post CMp cleaning. Therefore, the post-grinding cleaning agent may comprise an acidifying agent and a corrosion inhibiting agent, and the acidic compound may be citric acid, oxalic acid, phytic acid, aminotrimethylphosphoric acid, 1-hydroxyethylidene 1,1- Diphosphate, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, 1,4-hexamethyl-(tetradecyl) ι, 4-phosphoric acid, 1,5-phosphoric acid - Diethylene triamine pentadecyl, hydrazine, 5 phosphate - hexamethylethylene triamine pentadecyl, malonic acid, lactic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, succinic acid, adipic acid , malic acid, maleic acid, tartaric acid, methyl acid, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triglycine, N- (hydroxyethyl) ethylenediaminetriacetic acid ruthenium or a combination thereof, and the corrosion inhibitor may be a sarcosine compound such as sarcosine and a salt thereof, and examples of the sarcosine and salts thereof include Not limited to sarcosine, N-acyl sarcosine, lauroyl sarcosine, cocoyl sarcosine, oil 醯Oleoyl sarcosine, stearoyl sarcosine, and myristoyl sarcosine or a lithium salt, a sodium salt, a potassium salt, or an amine salt thereof, or a mixture thereof. 15 200925326 EXAMPLES According to Table 5, after using the components of Comparative Examples 7 to 9 to grind the detergent, perform a post-grinding cleaning test, and compare the wafers in each of the comparative examples - citric acid (wt %) Oxalic acid (wt%) Laurel Creatine ppm ppm Cocoyl creatinine ppm Comparative Example 7 0.2 0.2 0 0 Comparative Example 8 0.2 0.2 20 0 Comparative Example 9 0.2 0.2 0 20 Table 5 ν ❹ Post-grinding cleaning test The results of the copper loss analysis using TXRF (total reflection X-ray glory spectroscopy) are shown in Table 6. Wafer cracking: 2 2000A thick copper wafer cleaning equipment: Ontrak post CMP brush box (Lam

Research, CA USA) Cleaning agent flow rate: 300 ml/min

Cu loss rate (A/min) Comparative Example 7 21.66 Comparative Example 8 16.47 Comparative Example 9 13.34 Table 6 ❹ According to the results of Table 6, the copper loss rate of the Comparative Examples 8 and 9 was smaller than that of the control ^7, so the laurel muscle was added. Grinding the cleaning agent after the amine acid or the oleic acid thioglycolic acid can effectively suppress the loss of copper. 200925326 Example 4 According to Table VII, after the composition of Comparative Examples 7 to 9 was used, the cleaning agent was ground, and the post-CMP cleaning test was performed, and the loss rate of copper on the wafer surface in each of the comparative examples was compared. Citric acid (wt%) dodecylbenzene benzoate sodium cocoyl creatinine ppm (wt%) Comparative Example 10 0.25 0.0085 0 Comparative Example 11 0.25 0.0085 10 Table VII

The post-grinding cleaning test was carried out according to the following conditions, and the average value of the copper loss (copper loss) analyzed by TXRF (total reflection X-ray fluorescence spectroscopy) is shown in Table 8. Wafer type: 2 sheets of 2000A thick copper wafer cleaning unit: Ontrack post CMP brush box (Lam Research, CA USA) Cleaning agent flow rate: 300 ml/min Cleaning time: 50 seconds copper loss rate average A/min Example 10 13.92 Comparative Example 11 11.71 Table 8 According to the results of Table 8, the copper loss rate of the comparative example 11 is smaller than that of the control example 10. Therefore, the grinding detergent can effectively inhibit the copper mussels after the addition of sodium cocoyl-sodium sarcosinate. Consumption. It can be seen from the above Examples 3 and 4 that the present invention utilizes the sarcosine compound 17 200925326 (such as sarcosine and its salt compound) as a corrosion inhibitor in the subsequent abrasive cleaning agent, which can protect the surface of the processed article from being cleaned, for example. The cleaning agent additive is ground after the erosion properties of the solution, oxidation, post-cleaning corrosion, chemically induced current erosion, or light induced intrusion. The technical content and technical features of the present invention are disclosed above, but those skilled in the art can still make various substitutions and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the present invention should be construed as being limited by the scope of the appended claims [Simple description of the diagram] [Description of main components representative symbols] Benefits Ο 18

Claims (1)

200925326 X. Patent application scope: 1. A creatinine compound as a corrosion inhibitor, which is used in a chemical mechanical polishing composition, wherein the corrosion inhibitor is sarcosine and a salt thereof. Or a composition thereof. 2. The sarcosine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof include, but are not limited to, sarcosine and N-mercaptocreatine (N- Acyl sarcosine), lauroyl sarcosine, cocoamine sarcosine, oleoyl sarcosi.'ne stearoyl sarcosine, And myristoyl sarcosine or a lithium salt, a sodium salt thereof, a potassium salt, or an amine salt < combination thereof. 3. The creatinine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof are sarcosine, and the chemical formula of the sarcosine is as shown in the formula 1: (CH3NHCH2COOH, CAS = 107-97-1). 4. The creatinine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof are lauric acid, and the chemical formula of the lauric acid is as follows: 19 200925326 (C丨5H29N〇3 ’ CAS 97-78-9). The creatinine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof may be sodium laurate and sodium citrate, the sodium lauric acid The chemical formula is as shown in Equation 3: [CH3(CH2)10CON(CH3)CH2COONa, CAS 137-16-6]. 6. The creatinine η as a residual inhibitor as claimed in claim 1, wherein the sarcosine and a salt thereof are sodium cocoyl sarcosinate, the cocoyl sarcosine The chemical formula of sodium is as shown in Equation 4: 7. The creatinine compound 20 200925326 as claimed in claim 1, wherein the chemical mechanical polishing composition further comprises: abrasive particles, an oxidizing agent, an accelerator, an inhibitor, and a solvent. 8. The creatinine compound as a septic inhibitor according to claim 7, wherein the abrasive granule is selected from the group consisting of calcined cerium oxide; hydrolyzed by sodium citrate or potassium citrate, or hydrolyzed and condensed by decane. a cerium oxide sol; precipitated or calcined alumina; precipitated or calcined titanium dioxide; a polymer material; a group of metal oxides and a mixture of polymer materials. 9. The creatinine compound as a rot #inhibitor as claimed in claim 7, wherein the abrasive granule may be a cerium oxide sol. 01至30百分比。 The creatinine compound as a corrosion inhibitor, wherein the abrasive particles accounted for 0.1 to 30% of the total weight of the composition. 11. The creatinine compound as a rot #inhibitor as claimed in claim 7, wherein the oxidizing agent is hydrogen peroxide. 12. The creatinine compound as a rot #inhibitor according to claim 7, wherein the accelerator is selected from the group consisting of citric acid, oxalic acid, tartaric acid, histidine, alanine, and glycine. 01至5%。 The creatinine compound as described in claim 7 as a residual inhibitor of the creatinine compound, wherein the accelerator is from 0.1 to 5% of the total weight of the composition. 14. The creatinine compound as a sacrificial inhibitor according to claim 7, wherein the inhibitor is selected from the group consisting of an imidazoline compound and a triazole compound. 15. The sarcosine compound as a rot of money as claimed in claim 14, wherein the triazole compound is selected from the group consisting of 1,2,4-triazole and 3-amino-1,2,4-triazole , 3-nitro-1,2,4-triazole, 3-amino-1H-1,2,4-triazole-5-carboxylic acid, H-benzotriazole, and 5-indenyl- 1, 2, 3-benzotriazole 21 200925326 The group consisting of. 16. The creatinine compound as a corrosion inhibitor according to claim 7, wherein the inhibitor is in the total weight of the composition. Q 〇〇 1 to 1%. The creatinine compound as a corrosion inhibitor according to claim 7, wherein the corrosion inhibitor accounts for 总1 to 总1 of the total weight of the composition. 18. The creatinine compound as a corrosion inhibitor according to claim 7, wherein the solvent system is water. Mouth 19, a creatinine compound as a corrosion inhibitor, the corrosion inhibits The formulation is for use in a post-milling detergent wherein the antiseptic inhibitor is = aminic acid and a salt thereof or a combination thereof. 20. The myosinated person as a corrosion inhibitor according to claim 19, wherein the creatinine and a salt thereof include, but are not limited to, saixoxine, Ν-mercaptocreatine (N -acyl sarc〇sine), lauroyl sarcosine, cocyl sarcosine, oleoline sarc〇sine, stearin muscle Amino acid (stearoyl sarcosine), and myristoyl sarcosine (myristoyl sarcosine) or its lithium salt, sodium salt, potassium salt, or amine guanidine, or the creatinine of the water π 'The creatinine and its salts can be π Μ sarcosine, the chemical formula of sarcosine is as follows. (CH3NHCH2COOH > CAS= 107-97-1) 〇22 200925326 22. The creatinine compound as a rot of money as described in claim 19, wherein the acid and its compound can be (iv) leucine The chemical formula of lauric acid creatinine is as shown in formula 2. ^ (C15H29N03 ‘ CAS 97-78-9). 23. The creatinine compound as a corrosion inhibitor according to claim 19, wherein the sarcosine and a salt thereof are sodium laurate [CH3(CH2)10CON(CH3)CH2COONa, CAS 137_16_6]. 24. The sarcosine compound as a ship inhibitor according to claim 19, wherein the sarcosine and a salt thereof are sodium cocoyl-sodium sarcosinate, and the chemical formula of the cocoyl-sodium sarcosinate As in Equation IV. 23 200925326 25, as claimed in the item ig, wherein the post-grinding cleansing _2 卩 卩 之 肌 肌 on on on step includes: acidic compounds. 2 6. For example, in March, 25 syllabus & ρ * At, - . . , A i as a corrosion inhibitor, myosinated J 乂 is tannic acid, oxalic acid, phosphoric acid, amino dimethyl hydrazine , 1 -hydroxyethylidene u_diphosphate, 2 -phosphonic acid butane] '2, 4-trimethylene, aminotrimethylenephosphonic acid, glutamic acid hexamethyl-(tetramethyl) 1,4 lin Acid, 1,5-phosphoric acid-diethylenetriamine pentamethyl, 5-phosphate-mercaptoethylenediamine pentamethyl, malonic acid, lactic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, amber Acid, adipic acid, malic acid, maleic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, ethylenediaminetetraacetic acid, ethylenediamine pentaacetic acid, Triglycine, N-(ethyl)ethylamine monoamine diacetic acid or a combination thereof. 24 200925326 . VII. Designation of Representative Representatives: (1) The representative representative of the case is: (No). (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 200925326 HO & 日修(更)正fj ——·~----——J - Formula 2 (C15H29NO3 5 CAS 97-78-9) N-acyl sarcosine, coconut oil Cocoyl sarcosine, oleoyl sarcosine, stearoyl sarcosine, and myristoyl sarcosine or its salts, sodium salts , potassium salt, or amine salt, etc. or mixtures thereof; for example, Sodium n-Lauroyl Sarcosinate ° [CH3(CH2)lflC0N(CH3)CM:0〇Na,CAS 137-16-6] Generally, the corrosion inhibitor accounts for 0·0005 to 1% of the total weight of the composition. 005至〇. 1%。 001至〇. 5%, more preferably the total weight of the composition of 0. 005 to 〇. 1%. In general, the inhibitor is 0. 0001 to 1% of the total weight of the composition, preferably 占5 to 〇. (10), and more preferably 0% of the total weight of the composition. 01 to L. 200925326 • Speaking on July 7th, repairing (more) is replacing page j. Two saliva-5-several acid, 丨 stupid #一 , , --- --———— ί Wow. A ########################################################################################### Deionized water is used as a solvent for the abrasive composition. Ο Columns are based on the specific embodiments of the limbs, and are not intended to limit the scope of the invention. According to Table 1, according to Table 1, a silica sol-containing abrasive particle comprising an average particle diameter of about 90 nm, alanine, hydrogen peroxide, u, 4_tris-salt (inhibitor), cocoon-based Sodium sarcosinate (corrosion inhibitor) and a control sample of the slurry slurry composition in which the solvent is water were tested. Among them, the chemical formula of sodium cocoyl-sodium sarcosinate is as shown in the formula: ❾ 四 (RCON(CH3)CH2COONa, CAS 61791-59-1) - —— oxidant (hydrogen peroxide) (wt%) accelerator (Alanine) (wt%) Inhibitor (wt%) Abrasive granules (wt bismuth sol) (wt%) Antiseptic inhibitor ppm Comparative Example θ 0.7 1 2.4 0.025 0.1 0 Comparative Example 0.7 2.4 0.025 0.1 50 Comparative Example 3 0.7 2.4 0 0.1 0 200925326 Nothing to do.) Page i _ i The composition of the present invention may use water as a solvent, and preferably deionized water is used as a solvent for the polishing composition. The features and effects of the present invention are further illustrated by the following specific examples, but are not intended to limit the scope of the invention. Example 1 According to Table 1, a cerium oxide sol comprising an average particle diameter of about 90 nm, alanine, hydrogen peroxide, 1,2,4-triazole (inhibitor), sputum sputum muscle Sodium alginate (corrosion inhibitor) and a control sample of the slurry slurry composition in which the solvent is water were tested. Wherein, the chemical formula of the sodium citrate sodium sarcosinate is as shown in the formula: Ο Ηα+ Ο Formula IV (RCON(CH3)CH2COONa, CAS 61791-59-1) Oxidizing agent (hydrogen peroxide) (wt%) Accelerator (alanine) (wt%) Inhibitor (wt%) Abrasive particles (cerium oxide sol) (wt%) rot #inhibitor ppm Comparative Example 1 0.7 2.4 0.025 0.1 0 Comparative Example 2 0.7 2.4 0.025 0.1 50 Comparative Example 3 0.7 2.4 0 0.1 0 Comparative Example 4 0.7 2.4 0 0.1 50 Table 1 The grinding test was carried out according to the following conditions. The average value of the removal rate (RR) and the Etch Rate is recorded in the table. 200925326 Grinding machine: Mirra polisher (Applied Materials) Wafer type: 8吋 copper film wafer (Ramco Co) Grinding pressure: 2psig Platform turning: 90 rpm Vehicle turning: 85 rpm Grinding art: IC 1010 (RohmandHaas) 研 Mortar flow rate: 200 ml/min. , Cu RR@ 1.5psi Cu RR@ 3psi surname rate, A/min Comparative Example 1, 4930 9790 915 *4 2. W^iiTT- _ 3257 7729 319 _, 7458 >15425 3023, 1470 >15425 578 In the case of Comparative Example 1 and Comparative Example 2, the control 3 and the polishing removal rate and the etching rate were larger than that of Comparative Example 2, and the comparative example was in the Example 4, The copper removal rate and etching rate of Example 3 are mostly corrosion inhibition. It can be seen that if the sodium citrate is used as the corrosion agent, the copper removal rate and the etching rate are greatly reduced. The material can provide better corrosion inhibition ability, and can effectively avoid the application of the second embodiment according to the reference = nm I 氡 〜 〜 , , , , 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照 对照Hydrogen peroxide, potassium hydroxide, stupid and three doses), while Comparative Example 6 used to include an average particle size of about 9 〇. 修修(more) 正%^ 200925326 nm One of the gasified cerium sol abrasive particles, hydrogen peroxide, potassium hydroxide, sulfonium sulfhydryl sarcosinate (corrosion inhibitor) and the solvent is water slurry composition 11 The control sample was tested under the environment. Comparative Example 5 Oxidizing agent (perhydrogenated hydrogen) (wt%, abrasive particles (cerium oxide sol) (wt%) BTA ppm corrosion inhibitor ppm KOH (wt%) pH 30.0 50 0 0.1 11 Comparative Example 6 0.5 30.0 0 50 0.1 11 Table 3 The grinding test was carried out according to the following conditions. The average value of the removal rate (RR) is shown in Table 4. Grinding machine: Applied Material Mirra Polisher, (San Jose, CA) Wafer type: 8覆 覆 ,, TEOS, 钽 film wafer grinding pressure: 2psig platform speed: 70 rpm vehicle speed: 65rpm polishing pad: IC 1010 (R〇hm and Haas) research flow rate: 200 ml / min. Ox grinding removal Rate (A/min) Cu Abrasive removal rate (A/min) Ta Abrasive removal rate (A/min) Comparative Example 5 1244 657 633 Comparative Example 6 1223 556 601 Table 4 According to the results of Table 4, the copper of Comparative Example 5 The polishing removal rate and the group (Ta) polishing removal rate are larger than that of the comparative example 6'. As a result, it can be seen that if sodium cocoyl-sodium sarcosinate is used as a corrosion inhibitor, the copper and the button are greatly reduced. 13 曰修(more) is replacing the grinding removal rate of 200925326 (Ta), so the use of coconut glutamic acid sarcosinate as a rot money inhibitor can provide better corrosion inhibition ability (compared to the original two-degree sitting as a rot The surname inhibitor) can effectively prevent the processed objects from being corroded. As can be seen from the above examples, the present invention utilizes myosinating substances (such as sarcosine and its salt compounds) as corrosion inhibitors in chemical mechanical polishing compositions, and the use of benzotriazole (IH-benzotriazole). BTA) As a corrosion inhibitor, it has better corrosion-inhibiting ability, which can prevent the workpiece from being corroded and will not cause residue on the surface of the abrasive article. In addition, the corrosion inhibitor of the present invention can also be used in a post-grinding cleaning agent, which can also be a sarcosine compound such as sarcosine and a salt compound thereof or a mixture thereof, which can protect the surface of the processed article from the surface. For example, erosion properties of the cleaning solution, oxidation, post-cleaning corrosion, chemically induced current erosion, or light-induced erosion. While CMP can effectively planarize the surface of a workpiece, this procedure leaves the contaminants on the surface of the workpiece. A cleaning agent must be applied after application to remove such contaminating residues. The purpose of cleaning is to remove the residue left by the CMP step from the surface of the workpiece, without significantly etching the metal, depositing deposits on the surface, or applying significant organic (eg, carbon) to the workpiece. ) Contaminants. In addition, it is desirable to protect the surface of the workpiece from corrosion by a variety of different mechanisms, such as chemical etching, chemical galvanic or photo-induced corrosion. Corrosion of the surface of the workpiece causes metal recesses and thins the metal lines. The acidic cleaning solution is usually phased from the removal of organic contaminants from the surface of the two parts of the process and is mismatched with the residual copper: there is a gynecological repair (more j xiangxiang page 200925326 efficiency. Therefore, it is obtained at a moderate to low pH value It would be desirable to have an effective cleaner. Acidic chemistry is typically used in a scrubbing box or ultrasonic cleaning unit for post-CMP cleaning. Therefore, the post-grinding cleaner can contain acidic compounds. The acidic compound may be citric acid, oxalic acid, phosphoric acid, aminotrimethylphosphoric acid, 1-hydroxyethylidene 1, diphosphoric acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, aminotriamide Methylphosphonic acid, hexamethyl-(tetramethyl) 1,4-phosphate, 1,5-phosphoric acid-diethylenetriamine pentadecyl, 1,5-phosphate-hexamethylethenetriamine Sulfhydryl, malonic acid, lactic acid, acetic acid 'propionic acid, butyric acid, citric acid, caproic acid, succinic acid, adipic acid, malic acid, maleic acid, tartaric acid, sulfonic acid, benzenesulfonate, toluenesulfonic acid , dodecylbenzenesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triglycine, N-(hydroxyethyl Ethylenediaminetriacetic acid or a combination thereof, and the corrosion inhibitor may be a sarcosine compound such as sarcosine and a salt thereof, and examples of the creatinine and salts thereof include, but are not limited to, sarcosine ( Sarcosine), N-acyl sarcosine, lauroyl sarcosine, cocoyl sarcosine, oleoyl sarcosine, Stearoyl sarcosine, and myristoyl sarcosine or its sulphate, sodium, potassium, or amine salt, or the like, or mixtures thereof. After the composition of Comparative Examples 7 to 9 was used, the cleaning agent was ground, a post-grinding cleaning test was performed, and the loss rate of copper on the wafer surface in each of the comparative examples was compared. 15 200925326 Citric acid (wt%) Oxalic acid (wt%) Laurel creatinine PPm oleic acid creatinine ppm Comparative Example 7 0.2 0.2 0 0 Comparative Example 8 0.2 0.2 20 0 Comparative Example 9 0.2 0.2 0 20 , Table 5 The post-grinding cleaning test was carried out according to the following conditions, and the copper loss (copper loss) analysis by TXRF (total reflection X-ray fluorescence spectroscopy) was recorded in Table 6. 〇 Wafer type: 2 2000A thick copper wafer cleaning equipment: Ontrak post CMP brush box (Lam Research, CA USA) Cleaning agent flow rate: 300 ml / min Cleaning time: 50 seconds Cu loss rate (A / min) Comparative Example 7 21.66 Comparative Example 8 16.47 Comparative Example 9 13.34 〇 Table 6 According to the results of Table 6, it can be seen that the copper loss rate of Comparative Examples 8 and 9 is smaller than that of Comparative Example 7, so that lauric acid or eucalyptus muscle is added. Grinding the cleaning agent after the amine acid can effectively suppress the loss of copper. Example 4 According to Table 7, the post-CMP cleaning test was carried out by using the components of Comparative Examples 7 to 9 and the post-CMP cleaning test was carried out. I compared the loss rate of copper on the wafer surface in each of the comparative examples. 200925326 Midday (6th whip) Citric acid (wt%) Dodecylbenzenesulfonic acid (wt%) Cocoyl-sodium sarcosinate ppm Comparative Example 10 0.25 0.0085 0 Comparative Example 11 0.25 0.0085 10 Table 7 post-grinding The cleaning test was carried out according to the following conditions, and the average value of copper loss by copper TX (total reflection X-ray fluorescence spectroscopy) was recorded in Table 8. Wafer type: 2 sheets of 2000A thick copper clad wafer cleaning unit: Ontrack post CMP brush box (Lam Research, CA USA) Cleaning agent flow rate: 300 ml/min Cleaning time: 50 seconds copper loss rate average A/min Comparative Example 10 13.92 Comparative Example 11 11.71 Table 8 According to the results of Table 8, it can be seen that the copper loss rate of Comparative Example 11 is smaller than that of Comparative Example 10, so that the grinding detergent can effectively suppress the loss of copper after adding coconut oil-based creatinine. . It can be seen from the above Examples 3 and 4 that the present invention utilizes a creatinine compound (such as sarcosine and a salt thereof) as a corrosion inhibitor in a post-grinding detergent to protect the surface of the processed article from, for example, a cleaning solution. Grinding detergent additives after invasive nature, oxidation, post-cleaning, chemical intrusion, or photo-induced erosion. The price of the month 1 & 9 repairs) 200925326 The technical content and technical features of the present invention are disclosed above, but those skilled in the art may still make various substitutions and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the present invention should be construed as being limited by the scope of the appended claims. [Simple diagram description] None 0 [Description of main component representative symbols] Benefits 18 (S ) 200925326 1^——**"-^""**丨I _1丨·-1, a creatinine compound as a corrosion-inducing agent, which is used in chemical mechanical polishing compositions, wherein The corrosion inhibitor is sarcosine and a salt thereof or a combination thereof. 2. The creatinine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof include, but are not limited to, sarcosine and N-acyl sarcosine. ), lauroyl sarcosine, cocoyl sarcosine, oleoyl sarcosine, stearoyl sarcosirie, and meat Myristoyl sarcosine or a salt, sodium, potassium or amine salt thereof or a combination thereof. 3. The creatinine compound as a rot #inhibitor according to claim 1, wherein the sarcosine and a salt thereof may be sarcosine, and the formula of the sarcosine is as shown in the formula 1: (CH3NHCH2COOH) CAS=107-97-1) 〇4. The creatinine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof may be lauric acid, the laurel The chemical formula of levyomylin is as shown in formula II: 200925326 Japanese repair (more) is replacing Bay: | (C15H29N〇3, CAS 97-78-9). 5. The creatinine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof are sodium salina citrate, and the chemical formula of the sodium laurate Equation 3: Equation 3 [CH3(〇i2)n) CON(CH3)CH2COONa, CAS 137-16-6]. 6. The sarcosine compound as a sedative inhibitor according to claim 1, wherein the sarcosine and a salt thereof are sodium cocoyl-sodium sarcosinate, and the cocoyl-sodium sarcosinate The chemical formula is as shown in Equation 4: Equation 4 [RCON(CH3)CH2COONa, CAS 61791 -59-1]. 20 200925326 Equation 2 (C15H29N03, CAS 97-78-9). Ο 5. The creatinine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof may be sodium lauric acid, and the chemical formula of the sodium laurate Equation 3: [CH3(CH2)1()CON(CH3)CH2COONa, CAS 137-16-6]. The creatinine compound as a corrosion inhibitor according to claim 1, wherein the sarcosine and a salt thereof may be sodium cocoyl sarcosinate, the cocoyl sarcosine The chemical formula of sodium is as shown in Formula 4: Formula 4 [RCON(CH3)CH2COONa, CAS 61791-59-1] 20 200925326 · « 7. The creatinine compound as a corrosion inhibitor as described in claim 1, wherein the chemical mechanical polishing The composition further comprises: abrasive particles, an oxidizing agent, an accelerator, an inhibitor, and a solvent. 8. The creatinine compound as a corrosion inhibitor according to claim 7, wherein the abrasive granule is selected from the group consisting of calcined cerium oxide; hydrolyzed by sodium citrate or potassium citrate, or hydrolyzed and condensed by decane. a cerium oxide sol; a precipitated or calcined alumina; a precipitated or calcined titanium dioxide; a polymer; a material; a mixture of a metal oxide and a polymer material hybrid. A creatinine compound as a curric acid inhibitor according to claim 7, wherein the abrasive granule may be a cerium oxide sol. 10. The creatinine compound as a septic inhibitor as claimed in claim 7, wherein the abrasive granules comprise from 0.01 to 30% by weight based on the total weight of the composition. 11. The creatinine compound as a corrosion inhibitor according to claim 7, wherein the oxidizing agent is cerium peroxide. 12. The sarcosine compound as a rotatory inhibitor according to claim 7, wherein the accelerator is selected from the group consisting of citric acid, oxalic acid, tartaric acid, histidine, Q alanine, and glycine. . 01至5%。 The creatinine compound as described in claim 7 as the inhibitor of the creatinine compound, wherein the accelerator is 0. 01 to 5% of the total weight of the composition. 0001至1%。 The creatinine compound as a rot # inhibitor, as described in claim 7 wherein the inhibitor is from 0.0001 to 1% of the total weight of the composition. 0001至1百分比。 The creatinine compound as a rot # inhibitor, as described in claim 7 wherein the rot of the rot of the total weight of the composition is from 0.0001 to 1%. 16. The creatinine compound as a corrosion inhibitor according to claim 7, wherein the solvent system is leeches 21 200925326 π, a formulation is used for The corrosion inhibitor is called aminic acid amine acid and its salt neck compound or a combination thereof. 18. The method of claim 17, wherein the sarcosine and its salts include (sarcosine), N- _ and its _ compounds including, but not limited to, sarcosine sarcosine (N-acyl sarcosine) ), lauroyl sarcosine, cocoyl sarcosine, creatinine (〇ie〇yi sarc〇sine), stearic acid glutamine (stearoyl sarc〇) Sine), and myristoyl sarcosine or a lithium, sodium, potassium or amine salt thereof or a combination thereof. 19. The creatinine compound as a corrosion inhibitor according to claim 17, wherein the sarcosine and a salt thereof are sarcosine, and the formula of the sarcosine is as shown in the formula 1: 〇(CH3NHCH2COOH*CAS=107-97-1) 〇20, the creatinine compound as a corrosion inhibitor according to claim 17, wherein the sarcosine and a salt thereof may be lauric acid, The chemical formula of lauric acid in laurel is as follows: 200925326 Formula (C15H29N〇3, CAS 97-78-9). The creatinine compound as a corrosion inhibitor according to claim 17, wherein the sarcosine and a salt thereof are sodium laurate, and the chemical formula of the sodium laurate Three: Να+ Ο Three [CH3(CH2)10CON(CH3)CH2COONa, CAS 137-16-6]. 2, the creatinine compound as a septic inhibitor as claimed in claim 17, wherein the sarcosine and a salt thereof may be sodium cocoyl sarcosinate, the cocoyl sulphate The chemical formula is as shown in Equation 4: ❹ Equation 4 [RCON(CH3)CH2COONa, CAS 61791-59-1]. 23. The creatinine compound as a rot #inhibitor according to claim 17, wherein the post-milling detergent further comprises: an acidic compound. 24. The creatinine compound as a septic inhibitor as claimed in claim 23, wherein the acidic compound may be citric acid, oxalic acid, phosphoric acid, amino group 23 200925326 Month > repair (more) positive · % i-K >t HMHaJ Equation 4 [RCON(CH3)CH2COONa, CAS 61791-59-1]. 25. The creatinine compound as a corrosion inhibitor according to claim 19, wherein the post-milling detergent further comprises: an acidic compound. ® 2 6. The creatinine compound as a rot #inhibitor as described in claim 2, wherein the acidic compound may be citric acid, oxalic acid, phosphoric acid, aminotrimercaptophosphoric acid, 1-hydroxyethylidene 1, 1-diphosphoric acid, butane-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, hexamethyl-(tetradecyl) 1,4 phosphate, 1, 5-phosphoric acid-diethylenetriamine pentadecyl, 1,5-phosphate-hexamethylethylene triamine pentamethyl, malonic acid, lactic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acesulfonic acid, Adipic acid, malic acid, maleic acid, tartaric acid, formazanic acid, benzoic acid, hydrazine acid, eleven alkylbenzene acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triglyceride Amine acid, N-(hydroxyethyl)ethylenediaminetriacetic acid or a combination thereof. 24 200925326 Trimethylphosphoric acid, 1-hydroxyethylidene 1,1-diphosphate, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, 1,4-amino acid Methyl-(tetramethyl) 1,4-phosphate, 1,5-phospho-diethylenetriamine pentamethyl, 1,5-phosphate-hexamethylethylene triamine pentamethyl, malonic acid, lactic acid 'acetic acid, C Acid, butyric acid, valeric acid, caproic acid, succinic acid, adipic acid, malic acid, maleic acid, tartaric acid, sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, ethylenediamine Tetraacetic acid, diethylenetriaminepentaacetic acid, triglycine, N-(hydroxyethyl)ethylamine triacetic acid or a combination thereof. 〇〇24 200925326 % mm Month 3 repair (more) is being replaced: VII. Designated representative week: (1) The representative representative of the case is: (None) Figure (2) The symbol of the representative figure is simple: No eight If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: Formula 2 0 Equation 4 4