TW200945429A - Composition of chemical mechanical polishing - Google Patents

Abstract

The inhibitor composition of the present invention comprises imrdazoline type compound, triazole type compound or their combination; and sarcosine and its salt type compound or their combination. When the inhibitor composition is applied in chemical mechanical polishing, the inhibitor composition is provided with the feature of depressing metal etching while maintaining a high polishing removal rate of the metal layer, thereby being able to reduce polishing defects such as dishing and erosion.

Description

200945429 IX. Description of the invention: [Technical field to which the invention pertains] (4) Inhibitors of chemical mechanical polishing are composed of & flattening effects of the same processed object [Prior Art] ❹u with the f subcomponent Off key size (cHtieai cell (10) (four) is getting smaller and the number of wire layers is increasing rapidly, and the rc time delay will seriously affect the operating speed of the whole circuit. In order to change the metal line width reduction The phase delay and the problem of electron migration reliability are caused. Therefore, a copper wire material with low resistivity and high electron migration resistance is selected instead of aluminum alloy metal. However, since copper metal has a property of being difficult to etch, another mosaic must be adopted. (Damascene) method to form copper metal wires. D The damascene method is different from the traditional metallization process in which a metal pattern is first defined and then filled with a dielectric layer by first filling a flat dielectric. After the trench of the metal line is taken out, the metal layer is filled in, and finally the excess metal is removed to obtain a metal inlaid on the dielectric layer. Flat structure. The inlaid process has the following advantages over the traditional metallization process: (1) can keep the surface of the substrate flat at any time; (2) it can eliminate the disadvantage that the traditional process dielectric material is not easy to fill the gap of the metal wire: 3) It can solve the problem that the etching of metal materials is not easy, especially the steel metal. In addition, in order to overcome the traditional interconnect method, the contact window structure and the wire 200945429 f need to be separately produced, which makes the whole process steps extremely complicated. Another goal is to develop a dual damascene process, which is selectively etched twice after etching the dielectric dielectric (Hne dielectric) and the dielectric dielectric (via dielectric). The barrier layer of the metal layer and the plug is completed once, and the conductive metal is filled into the via window and the interconnect trench at a time to simplify the process steps. In recent years, in order to cope with the development of component size reduction and Copper metal with low resistance constant and high electron transfer resistance has been gradually applied as a material for metal interconnects. Replacing the previous aluminum metal process technology. The inlaid interconnect technology of steel metal not only can reduce the internal wiring and reduce the Rc time delay, but also solve the problem that metal copper etching is not easy, so it has become today The main development trend of multiple interconnects. Whether it is a single damascene or dual damascene copper process, after the completion of the filling of the copper metal, a planarization process is required to remove the excess metal on the dielectric layer. This is usually achieved by a chemical mechanical polishing process. However, in the metal chemical mechanical polishing technique, grinding defects such as dishing and abrasion are still often occurring on the surface of the metal layer. Metal dishing and grinding phenomenon have a great relationship with polishing rate and etching ratio (RR/DER). The lower etching rate ensures low removal rate of pattern depressions, thereby effectively suppressing dish defects, but considering units The grinding rate should also be maintained within the acceptable range under the output of time; in addition, the uniformity of the grinding also has a certain effect on the flatness result, and the poor uniformity requires more grinding of the 200945429 time to completely remove the copper, thus causing more Strict phenomenon ° dish trap and abrasion to take into account the unit output and suppression system will copper-chemical mechanical polishing process, /, trapping and abrasion phenomenon ❹ ❹ at a faster grinding rate will be the majority _ = step. First-order = quantity. In the second stage, the slower grinding is used to increase the unit output. In order to avoid excessive grinding of the copper in the groove, the copper grinding process of the segment needs to be replaced. Usually, the copper grinding requirements of the second stage are different. However, the replacement of the abrasive composition to facilitate the simplification of the process may also result in the addition of the abrasive composition of the waste material. No. 6,679,929 discloses that at least one abrasive grain, at least 10 carbon atoms, and a product are included. Sex components, accelerators, resists (antic〇rr〇siv:), and water, the polishing composition can reduce the etching speed of copper metal: for most copper layers (bu丨kc〇pper) The removal rate also produces an unfavorable = ringing. Further, the publication of U.S. Patent Application Publication No. 2004/0020135 discloses the inclusion of cerium oxide, an oxidizing agent, an amino acid, a triazole compound, and a copper metal polishing composition of water. However, this patent does not disclose the use of a co-inhibitor to slow down the polishing composition for the metal after maintaining a high removal rate, while at the same time applying the first and second stages of copper metal grinding. SUMMARY OF THE INVENTION The main object of the present invention is to provide an inhibitor composition for chemical mechanical polishing 7 200945429, which can improve the buckle of the processed article. The present invention aims to provide a same rate. Chemical mechanical polishing composition of segment metal grinding. At 5 o'clock, it is suitable for the second order. In the present invention, at least the imidazoline compound or the trisalination compound composition, the creatinine and its salt compound or the group thereof are contained. Or a combination thereof, an oxazoline compound or a triazole compound or a group thereof: wherein, the imienotriazole, and the creatinine and a salt compound thereof are considered to be a benzoic acid ("(九)一扑The inhibitor composition system: ^^ The polishing composition can be formed into a layer-protective film during chemical mechanical polishing, and the high-grinding (four) layer can be used to suppress the characteristics of the material, and can be less-H = Means] The turtle of the present invention can be clearly understood by the description of the present invention. Also, #,, 田至学广机械磨的组成物"' The inhibitor composition ^ ^ 3 .; a compound or a triazole compound or a composition thereof, and a muscle and a salt thereof, or a composition thereof, and the composition is a chemical mechanical polishing composition which can be chemically mechanically polished to a processed article. The surface is formed as a layer of protective film to prevent the processing of objects from being improved. Corrosion reduction, the chemical mechanical polishing composition, in addition to the _inhibitor, further comprises: abrasive particles, 8 200945429 oxidizing agent, accelerator, and solvent. ^ Examples of the abrasive particles include, but are not limited to, calcined cerium oxide矽 钠 钠 或 碎 碎 碎 或 或 或 或 或 或 或 或 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解Hybrids of materials and polymer materials. 2 The best is oxidized sand sol. If the amount of abrasive particles is too low, it is not conducive to the mechanical grinding θ method to achieve the desired grinding removal rate; 】A will accelerate the effect of mechanical grinding, increase the barrier layer and insulation oxidation removal rate, it is also prone to surface grinding abrasive defects. In a specific [the stone sol system accounted for the total weight of the composition. 01 to 30 weight %, preferably from 0.1 to 15% by weight. · = For the chemical mechanical polishing composition of the copper layer, it is preferred to use "5 / 2 as the oxidant. Usually - the oxidant is the total weight of the composition. Jiashi accounts for G.5 to 3". Examples of the machine == agent (10) include, but are acid. The accelerator is used to promote histidine, alanine, or glycine, and to dissolve the metal, for example, copper. ", the grinding of the metal layer helps to grind the metal layer from the metal layer. However, the increase of the mortar is not 1 = plus, the amount of addition, will also increase the static _ speed agent 俜 俜 : / Μ Μ Fine polishing. In one embodiment, the total weight of the added composition is _% by weight, preferably Μ to 5% by weight, more preferably 0.3 to 3% by weight. The composition is Under the condition of high grinding removal rate, the static engraving rate of 200945429 is effectively inhibited to be suitable for the first stage and the second stage of the grinding and polishing process, and the imidazoline compound or triazole compound of the present invention or the composition thereof may be 1 -H-benzotriazole (BTA), which is the total weight of the composition. 〇〇1 to 1%, preferably 0.005 to 0.8% of the total weight of the composition'. 〇1 to 0.5% of the total weight of the composition, and the creatinine and its salt compound or composition thereof constitutes 0·0 of the total weight of the composition. 005 to 1%' is preferably the total weight of the composition. 〇〇1 to 〇. 5%, ❾ is better than the total weight of the composition 〇. 〇〇5 to 〇. 1%. Examples of the creatinine and its salts include, but are not limited to, sarcosine,

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

Formula 2 (C15H29N03, CAS 97-78-9) N-acyl sarcosine, cocoyl sarcosine, oleoyl sarcosine, 200945429 Hard Stearoyl sarcosine, and myristoyl sarcosine or its salts, salts, salts, or amine salts, or mixtures thereof; for example, lauric acid, sodium sarcosinate ( Sodium n-Lauroy1 Sarcosinate),

Formula ❹ [CH3(CH2)10CON(CH3)CH2COONa, CAS 137-16-6] Alternatively, sodium cocoyl Sarcosinate

ο Λ © RCON(CH3)CH2CO〇Na5 CAS 61791-59-1) The composition of the present invention may use water as a solvent, and preferably deionized water is used as a solvent for the abrasive 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 present invention. Example 1 according to the table - listed using a slurry comprising anaerobic granules, propylamine 200945429 acid, nitrogen peroxide, lH-benzotriazole, sodium cocoyl sarcosinate and solvent as water The control sample was tested. Oxidizing agent (hydrogen peroxide) (wt%) Accelerator (glycine) (wt%) 1-H-benzotriazole (ppm) Abrasive particles (cerium oxide sol) (wt%) Cocoyl creatinine Sodium (ppm) Comparative Example 1 0.8 0.8 50 0.1 0 Comparative Example 2 0.8 0.8 0 0.1 60 Comparative Example 3 0.8 0.8 25 0.1 60 The first polishing test was carried out according to the following conditions. 〇^ ^ y * Grinding machine: Mirra polisher (Applied Materials) Wafer type: 8 覆 copper film wafer (Ramco Co) Grinding pressure: 1.5 psig and 0 psig Platform speed: 93 rpm Vehicle speed: 87 Rpm Abrasive Pad: IC 1010 (Rodel Inc) a slurry flow rate: 150 ml/min β ❹ The wafer is measured using a 4-point probe to measure the rate of grinding. The results are shown in Table 2: RR@1.5psig (A/min) WIWNU (%) DER@0psig (A/min) RR/DER Comparative Example 1 3349 5.1 1058 3.2 Comparative Example 2 4747 10.4 230 20.6 Comparative Example 3 5030 3.1 262 19.2 Table 2 where RR refers to the removal rate (Removal Rate) ), WIWNU refers to wafer surface uniformity (With-in_wafer-non- 12 200945429

Unif〇mity), and DER refers to the dynamic etching rate. According to the results of Table 2, 'Comparative Example 1 has low grinding removal rate and high engraving rate. The ratio is low; Comparative Example 2 _ has higher RR/臓' but the wafer surface uniformity is not good, and the result is known to be used. The inhibitor composition of the present invention (Comparative Example 3) can maintain the high grinding removal rate of copper', and can effectively reduce the residual rate of copper and increase the _ present value. The second embodiment of the acid, the use of cerium oxide sol particles, propylamine hydrogen peroxide, 1-H-poor _, the agent is the open di-salt, cocoyl-sodium sarcosinate and dissolved gasification agent ( Pervaporated argon) ('vt%) Additive (glycine) (wt%) Abrasive (cerium oxide sol) (wt% sodium cocoyl creatinine (ppm)

The product touches the sample for testing.

Grinding; the inspection is carried out according to the following conditions. The results are recorded in Table IV.

Mirra polisher (Applied Materials) Grinding pressure · q η . rut ± psig, 1. 5 psig and 〇 psig : 93 rpm 13 200945429 Carrier speed: 87 rpm Grinding pad: IC 1010 (Rodel Inc) ' Grinding flow rate: 150 Ml/min. RR @3psig (A/min) RR@1.5psig (A/min) DER (A/min) RR/DER Comparative Example 4 9618 5005 235 38.02 Comparative Example 5 6234 3220 116 53.74 Comparative Example 6 6490 3494 66 98.33 Comparative Example 7 5350 2560 80 66.88 Comparative Example 8 5859 3708 «k- 81 72.33 Table 4 According to the results in Table 4, at the fixed creatinine concentration, the grinding removal rate decreases as the concentration of benzotriazole increases, and a better composition can be obtained ( Comparative Example 6) had a high abrasive removal rate of copper, and a low etch rate with a high RR/DER value. 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 from the present invention based on the disclosure of the present invention. Therefore, the scope of the present invention is not limited by the scope of the invention, and the invention is intended to cover various alternatives and modifications. [Simple description of the diagram] None [Main component representative symbol description]

Claims (1)

200945429 X. Patent Application Range: 1. An inhibitor composition for chemical mechanical polishing, the inhibitor composition comprising at least: a taste compound or a triazole compound or a composition thereof; and a sarcosine And a salt thereof or a composition thereof. 2. The inhibitor composition for chemical mechanical polishing as described in claim 1, wherein the sarcosine and its salt compound include, but are not limited to, sarcosine and arginine (N) -acyl sarcosine), lauroyl sarcosine, cocoyl sarcosine, quercetin 〇C〇Sine, stearin sarcosine (stear) 〇yl sarcosine), and myristyl sarcosine (myrist〇yi sarc〇sine) or a salt, sodium, potassium or amine salt thereof or a combination thereof. 3. The inhibitor composition for chemical mechanical polishing as claimed in claim 1, wherein the sarcosine and a salt thereof are sarcosine. The chemical formula of the creatinine is as shown in the first formula: (CH3NHCH2COOH, CAS = 107-97-1). 4. The inhibitor composition for chemical mechanical polishing 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: 200945429 Ο I Formula 2 (C15H29N〇3, CAS 97-78-9). 5. The inhibitor composition for chemical mechanical polishing according to claim 1, wherein the sarcosine and a salt thereof are sodium laurate myosine salt, and the chemical formula of the sodium laurate myramine salt is as follows. Equation 3: Formula 3 [CH3(CH2)10CON(CH3)CH2COONa, CAS 137-16-6]. 6. The inhibitor composition for chemical mechanical polishing according to claim 1, wherein the sarcosine and a salt thereof are sodium cocoyl sarcosinate, and the coconut oil-based sarcosine The chemical formula is as shown in Equation 4: Equation four. 16 200945429 7. The chemical mechanical polishing composition according to claim 1, wherein the triazole bismuth b is selected from the group consisting of ruthenium, 2, 4 to triazole and an agent _1, 2, 4- Triazole, 3, nitro 2,4-triazole, 3~amino"t 3~aminoazole-5-carboxylic acid, i~H, benzoxazole, and 5-mercapto, i, 1> a group consisting of 2,4-three. '2'3H saliva 8. A chemical mechanical polishing product as claimed in claim 3, wherein the triazole compound may be a 1-H~stuppyrazole 17 preparation Composition 9, as claimed in claim 丨 for chemical mechanical polishing, such as abrasive particles, oxygen, wherein the chemical mechanical polishing composition further comprises a / weathering agent, an accelerator, and a solvent. The apparatus for chemical mechanical polishing according to claim 9, wherein the abrasive grain is selected from the group consisting of calcined cerium oxide; the hydrazine, potassium hydrolysis, or hydrazine hydrolysis and condensation Oxidized cerium oxide or kiln i 锻 calcined alumina; precipitated or calcined dioxide chain; polymer material metal oxide and polymer material mixture (hybrid) 11. The inhibitor composition for chemical mechanical polishing according to claim 9, wherein the abrasive system is a oxidizing agent. 12. The inhibition of poetic chemical mechanical polishing as claimed in claim 9. 01至30百分比。 The composition of the inhibitor for chemical mechanical polishing according to claim 9, wherein the hydrazine oxidant may be hydrogen peroxide. The inhibitor composition for chemical mechanical polishing as described in θ item 9 is 200945429 'where the addition agent is selected from the group consisting of citric acid, oxalic acid, tartaric acid, histidine, alanine' & glycine The inhibitor composition for chemical mechanical polishing as described in claim 9 wherein the affixing agent comprises from 0.01 to 5% by weight of the total composition. 16. For use in chemistry as claimed in claim 9 A mechanically abrasive inhibitor composition wherein the imidazoline compound or triazole compound or a fraction thereof constitutes 〇〇丨裘1% of the total weight of the composition. Π, as recited in claim 9 for chemical machinery Grinding inhibitor composition, wherein the sarcosine and its salt The compound or a composition thereof is 0.001 to 1% by weight based on the total weight of the composition. 18. The inhibitor composition for chemical mechanical polishing according to claim 9, wherein the solvent may be water. 200945429 VII. ·· (1) The representative representative of the case is: No. (2) Simple 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: