CN111748286A - Metal cobalt polishing solution and application thereof - Google Patents
Metal cobalt polishing solution and application thereof Download PDFInfo
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- CN111748286A CN111748286A CN202010618676.2A CN202010618676A CN111748286A CN 111748286 A CN111748286 A CN 111748286A CN 202010618676 A CN202010618676 A CN 202010618676A CN 111748286 A CN111748286 A CN 111748286A
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Abstract
The invention relates to a metal cobalt polishing solution and application thereof, wherein the polishing solution comprises the following components in percentage by weight: liquid phase carrier 50-80%; 0.1 to 10 percent of abrasive; the oxidant is less than or equal to 10 percent; 0.005-10% of L-aspartic acid; 0.005-10% of glutathione. According to the invention, by adjusting the proportion of the oxidant and the complexing agent and adding glutathione, the obtained polishing solution can inhibit the chemical corrosion of metal cobalt, simultaneously improve the polishing rate and reduce the surface roughness, and simultaneously reduce the galvanic corrosion between Cu and Co, so that the polishing solution has a good application prospect.
Description
Technical Field
The invention belongs to the field of polishing solution, and particularly relates to a metal cobalt polishing solution and application thereof.
Background
As feature sizes have further progressed below 14nm, Cu line resistivity has continued to increase due to increased electron scattering at sidewalls and grain boundaries, perfected by decreasing adhesion/barrier layer thicknesses. Cobalt (Co) has been chosen as one of the most promising barrier metals for IC copper interconnects due to its excellent properties. Co has low resistivity, excellent step coverage, good thermal stability and reliable adhesion with copper, and can effectively prevent copper diffusion. However, as feature sizes shrink further below 7nm, adhesion/barrier layer thicknesses cannot be infinitely reduced, so new interconnect materials must be sought. As a candidate for an alternative metal, Co does not present this problem and also provides seamless filling without voids and provides more room for metal and barrier thickness scaling. Because of these advantages, Co is considered a new type of conductive interconnect material that can replace tungsten (W) and copper in the middle and front metallization layers.
Polishing studies of Co have focused primarily on polishing in a weak acid, weak alkaline environment. Under the acidic condition, the metal Co is easy to be chemically corroded. Co surface will generate Co (OH) under alkaline environment2And Co3O4. These oxides or hydroxides which are hardly soluble in an alkaline solution inhibit the polishing rate of Co, resulting in a low polishing rate of Co. Much research is carried out on the CMP process of Co at home and abroad, but no satisfactory CMP process which is compatible with the polishing rate and inhibits the chemical corrosion of Co per se is found. Therefore, the invention provides the polishing solution capable of improving the polishing rate of Co and reducing galvanic corrosion between Cu and Co.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a metal cobalt polishing solution and application thereof, wherein the polishing solution obtained by regulating the particle size of spherical silicon dioxide particles and the proportion of an oxidant and a complexing agent can inhibit the chemical corrosion of metal cobalt, simultaneously improve the polishing rate, reduce the surface roughness, reduce the galvanic corrosion between Cu and Co, and has good application prospect.
The invention provides a metal cobalt polishing solution which comprises the following components in percentage by weight:
preferably, the liquid phase carrier is deionized water.
The abrasive is silica particles, cerium oxide particles or aluminum oxide particles.
Preferably, the particle size of the silica particles is 5-100 nm.
Preferably, the particle size of the silica particles is a single particle size. The single particle size generally means that the particle size of the silica particles used remains consistent.
Preferably, the silica particles are preferably spherical silica particles or non-spherical silica particles.
Preferably, the oxidant is NaClO, KMnO4、K2Cr2O7And one or more of hydrogen peroxide.
Preferably, the polishing solution is a Chemical Mechanical Polishing (CMP) solution.
Preferably, the adjustment of the acidity and the alkalinity are mainly performed by high-concentration potassium hydroxide and dilute nitric acid, and the pH range is selected from 7.00-12.00.
Advantageous effects
According to the invention, by adjusting the proportion of the oxidant and the complexing agent and adding glutathione, the obtained polishing solution can inhibit the chemical corrosion of metal cobalt, simultaneously improve the polishing rate and reduce the surface roughness, and simultaneously reduce the galvanic corrosion between Cu and Co, so that the polishing solution has a good application prospect.
Drawings
FIG. 1 is a photograph of a Co sheet for polishing.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
Taking 1000mL of sodium type spherical silicon dioxide abrasive with the particle size of 80nm and the solid content of 5 percent, wherein one part is not added with any additive; adding aspartic acid, asparagine, propionic acid, 1,2,3, 4-butanetetracarboxylic acid and arginine into other parts respectively, and stirring uniformly.
Polishing experiment: the polishing experiment used a CP-4 machine with a 2 inch cobalt wafer adhered to the polishing head by wax. The polishing parameters were set as follows: politex for polishing pad; polishing pressure was 3 psi; the polishing pad rotating speed is 90 rpm; the rotating speed of the polishing sheet is 90 rpm; the flow rate of the polishing solution is 125 mL/min; the polishing time was 10 min. And after finishing each polishing, cleaning the polishing pad for 5 minutes by using clear water, ultrasonically cleaning the polished wafer in a cleaning solution for 10 minutes, and drying the wafer by using nitrogen. The results are shown in Table 1.
TABLE 1
| Test sample | Polishing Rate (nm/min) |
| 80nmSiO2,pH＝10 | 13.3 |
| 80nmSiO2+ 0.1% aspartic acid, pH 10 | 42 |
| 80nmSiO2+ 0.1% asparagine, pH 10 | 23 |
| 80nmSiO2+ 0.1% propionic acid, pH 10 | 37 |
| 80nmSiO2+ 0.1% of 1,2,3, 4-butanetetracarboxylic acid, pH 10 | 30 |
| 80nmSiO2+ 0.1% arginine, pH 10 | 19 |
As can be seen from the results in Table 1, when different but equal amounts of complexing agent were added to the polishing slurry, it is evident that the addition of aspartic acid increased the polishing rate of cobalt the most effectively, increasing the polishing rate of cobalt by a factor of three. Second, propionic acid, the polishing rate increased by a factor of 2. Arginine did not significantly increase the cobalt polishing rate.
Example 2
Taking 1000mL of sodium type spherical silicon dioxide abrasive with the particle size of 80nm and the solid content of 5%, and adding 0.1% of H in each part2O2One part is not added with any additive; adding aspartic acid, asparagine, propionic acid, 1,2,3, 4-butanetetracarboxylic acid and arginine into other parts respectively, and stirring uniformly.
Polishing experiment: the polishing experiment used a CP-4 machine with a 2 inch cobalt wafer adhered to the polishing head by wax. The polishing parameters were set as follows: politex for polishing pad; polishing pressure was 3 psi; the polishing pad rotating speed is 90 rpm; the rotating speed of the polishing sheet is 90 rpm; the flow rate of the polishing solution is 125 mL/min; the polishing time was 10 min. And after finishing each polishing, cleaning the polishing pad for 5 minutes by using clear water, ultrasonically cleaning the polished wafer in a cleaning solution for 10 minutes, and drying the wafer by using nitrogen. The results are shown in Table 2.
TABLE 2
| Test sample | Polishing Rate (nm/min) |
| 80nmSiO2,pH＝10 | 13.3 |
| 80nmSiO2+ 0.1% aspartic acid + 0.1% H2O2,pH＝10 | 101 |
| 80nmSiO2+ 0.1% asparagine + 0.1% H2O2,pH＝10 | 62 |
| 80nmSiO2+ 0.1% propionic acid + 0.1% H2O2,pH＝10 | 87 |
| 80nmSiO2+ 0.1% of 1,2,3, 4-butanetetracarboxylic acid + 0.1% of H2O2,pH＝10 | 81 |
| 80nmSiO2+ 0.1% arginine + 0.1% H2O2,pH＝10 | 51 |
As can be seen from the results in Table 2, when different complexing agents were added at 0.1% hydrogen peroxide, it was evident that the highest polishing rate was achieved and that the polishing rate was increased seven-fold by the addition of aspartic acid. Followed by propionic acid, 1,2,3, 4-butanetetracarboxylic acid, asparagine and finally arginine.
Example 3
Taking 1000mL of sodium type spherical silicon dioxide abrasive with the particle size of 80nm and the solid content of 5 percent, wherein one part is not added with any additive; different concentrations of aspartic acid were added to the other portions.
Polishing experiment: the polishing experiment used a CP-4 machine with a 2 inch cobalt wafer adhered to the polishing head by wax. The polishing parameters were set as follows: politex for polishing pad; polishing pressure was 3 psi; the polishing pad rotating speed is 90 rpm; the rotating speed of the polishing sheet is 90 rpm; the flow rate of the polishing solution is 125 mL/min; the polishing time was 10 min. And after finishing each polishing, cleaning the polishing pad for 5 minutes by using clear water, ultrasonically cleaning the polished wafer in a cleaning solution for 10 minutes, and drying the wafer by using nitrogen. The results are shown in Table 3.
TABLE 3
| Test sample | Polishing Rate (nm/min) |
| 80nmSiO2,pH＝10 | 13.3 |
| 80nmSiO2+ 0.1% aspartic acid, pH 10 | 42 |
| 80nmSiO2+ 0.5% aspartic acid, pH 10 | 48 |
As can be seen from the results in Table 3, increasing the concentration of aspartic acid is advantageous for increasing the polishing rate of cobalt.
The other additives will be investigated with 0.5% aspartic acid next.
Example 4
Taking 1000mL of sodium type spherical silicon dioxide abrasive with the particle size of 80nm and the solid content of 5%, and adding 0.5% aspartic acid into each part; hydrogen peroxide with different concentrations is respectively added into other parts.
Polishing experiment: the polishing experiment used a CP-4 machine with a 2 inch cobalt wafer adhered to the polishing head by wax. The polishing parameters were set as follows: politex for polishing pad; polishing pressure was 3 psi; the polishing pad rotating speed is 90 rpm; the rotating speed of the polishing sheet is 90 rpm; the flow rate of the polishing solution is 125 mL/min; the polishing time was 10 min. And after finishing each polishing, cleaning the polishing pad for 5 minutes by using clear water, ultrasonically cleaning the polished wafer in a cleaning solution for 10 minutes, and drying the wafer by using nitrogen. The results are shown in Table 4.
TABLE 4
| Test sample | Polishing Rate (nm/min) | Surface roughness Ra/nm |
| 80nmSiO2,pH＝10 | 13.3 | 2.1 |
| 80nmSiO2+0.5％L-Asp,pH＝10 | 48 | 1.5 |
| 80nmSiO2+0.5％L-Asp+0.1％H2O2,pH＝10 | 101 | 0.2 |
| 80nmSiO2+0.5％L-Asp+0.5％H2O2,pH＝10 | 146 | 2.3 |
| 80nmSiO2+0.5％L-Asp+1.0％H2O2,pH＝10 | 89 | 3.4 |
As can be seen from the results in Table 4, when the same amount of aspartic acid was added, the polishing rate of cobalt was affected differently by adding different amounts of hydrogen peroxide. The polishing rate of cobalt is gradually increased along with the increase of the concentration of hydrogen peroxide. When 1.0% H is added2O2The polishing rate is rather decreased. The surface roughness of cobalt after polishing is also reduced and then increased. Considering that the polishing rate exceeds 100nm/min and the surface quality is good, 0.1% H is selected2O2And carrying out subsequent experimental exploration.
Example 5
Taking 1000mL of sodium type spherical silicon dioxide abrasive with the particle size of 80nm and the solid content of 5%, and adding aspartic acid (L-Asp) and H into each part2O2On the basis of (1), a certain amount of Glutathione (GSH) is added to carry out a polishing experiment.
Polishing experiment: the polishing experiment used a CP-4 machine with a 2 inch cobalt wafer adhered to the polishing head by wax. The polishing parameters were set as follows: politex for polishing pad; polishing pressure was 3 psi; the polishing pad rotating speed is 90 rpm; the rotating speed of the polishing sheet is 90 rpm; the flow rate of the polishing solution is 125 mL/min; the polishing time was 10 min. And after finishing each polishing, cleaning the polishing pad for 5 minutes by using clear water, ultrasonically cleaning the polished wafer in a cleaning solution for 10 minutes, and drying the wafer by using nitrogen. The results are shown in Table 5.
TABLE 5
| Test sample | Polishing Rate (nm/min) |
| 80nmSiO2+0.15％L-Asp+0.1％H2O2,PH＝10 | 48 |
| 80nmSiO2+0.15％L-Asp+0.1％H2O2+0.15％GSH,PH＝10 | 108 |
| 80nmSiO2+0.5％L-Asp+0.1％H2O2,PH＝10 | 101 |
| 80nmSiO2+0.5％L-Asp+0.5％H2O2+0.15％GSH,PH＝10 | 127 |
As can be seen from the results in Table 5, the addition of 0.15% glutathione doubled the polishing rate of cobalt based on the addition of 0.15% aspartic acid to the solution. Then 0.15% glutathione was added to increase the polishing rate of cobalt by 25% based on the addition of 0.5% aspartic acid to the solution. The addition of glutathione is favorable for improving the polishing rate of cobalt.
Example 6
500mL of a solution was prepared, each portion being added with the same mass of aspartic acid and H2O2On the basis of the method, a certain amount of glutathione is added to carry out electrochemical test on copper and cobalt.
Electrochemical experiment, the reference electrode used in the experiment is a silver/silver chloride electrode, and the counter electrode is 10 × 10cm in area2The working electrode is a copper sheet/cobalt sheet, and the working area of the sample in contact with the solution is 1cm2. The solution used in the electrochemical test experiment was a solution containing no silica sol, and was the same as the solution used in the static etching. The scanning speed in the potentiodynamic polarization test is 0.5mV/s, and the potential range is-0.6V.
TABLE 6
| Test sample | Ecorr(mV)(Co) | Ecorr(mV)(Cu) | ΔE(mV) |
| 0.15％L-Asp+0.1％H2O2 | -591 | -221 | 370 |
| 0.15％L-Asp+0.1％H2O2+0.1％GSH | -550 | -209 | 341 |
As is clear from the results in Table 6, only aspartic acid and H were added to the solution2O2The potential difference between copper and cobalt is 370 mV. When 0.1% glutathione was added to the solution, the potential difference between copper-cobalt decreased to 341 mV. The glutathione is shown to be beneficial to reducing the galvanic corrosion between copper and cobalt.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
Claims (7)
1. A metal cobalt polishing solution is characterized in that: comprises the following components in percentage by weight:
2. the polishing solution according to claim 1, wherein: the liquid phase carrier is deionized water.
3. The polishing solution according to claim 1, wherein: the abrasive is silica particles, cerium oxide particles or aluminum oxide particles.
4. The polishing solution according to claim 3, wherein: the particle size of the silicon dioxide particles is 5-100 nm.
5. The polishing solution according to claim 1, wherein: the oxidant is NaClO, KMnO4、K2Cr2O7And one or more of hydrogen peroxide.
6. The polishing solution according to claim 1, wherein: the pH value range of the polishing solution is 3.00-12.00.
7. Use of the metallic cobalt polishing solution according to claim 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100394555C (en) * | 2003-10-22 | 2008-06-11 | Cmp罗姆和哈斯电子材料控股公司 | Method of second step polishing in copper CMP with a polishing fluid containing no oxidizing agent |
| CN101297015A (en) * | 2005-10-24 | 2008-10-29 | 3M创新有限公司 | Polishing fluids and methods for CMP |
| CN104830235A (en) * | 2015-04-29 | 2015-08-12 | 清华大学 | Polishing solution for chemically and mechanically polishing cobalt barrier layer structure and applications thereof |
| CN105295737A (en) * | 2014-07-25 | 2016-02-03 | 气体产品与化学公司 | Chemical mechanical polishing (CMP) of cobalt-containing substrate |
| CN109563375A (en) * | 2016-08-05 | 2019-04-02 | 凯斯科技股份有限公司 | Tungsten barrier polishing slurry composition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100394555C (en) * | 2003-10-22 | 2008-06-11 | Cmp罗姆和哈斯电子材料控股公司 | Method of second step polishing in copper CMP with a polishing fluid containing no oxidizing agent |
| CN101297015A (en) * | 2005-10-24 | 2008-10-29 | 3M创新有限公司 | Polishing fluids and methods for CMP |
| CN105295737A (en) * | 2014-07-25 | 2016-02-03 | 气体产品与化学公司 | Chemical mechanical polishing (CMP) of cobalt-containing substrate |
| CN104830235A (en) * | 2015-04-29 | 2015-08-12 | 清华大学 | Polishing solution for chemically and mechanically polishing cobalt barrier layer structure and applications thereof |
| CN109563375A (en) * | 2016-08-05 | 2019-04-02 | 凯斯科技股份有限公司 | Tungsten barrier polishing slurry composition |
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Application publication date: 20201009 |