WO2022121822A1 - Chemical-mechanical polishing solution and method for using same - Google Patents
Chemical-mechanical polishing solution and method for using same Download PDFInfo
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- WO2022121822A1 WO2022121822A1 PCT/CN2021/135630 CN2021135630W WO2022121822A1 WO 2022121822 A1 WO2022121822 A1 WO 2022121822A1 CN 2021135630 W CN2021135630 W CN 2021135630W WO 2022121822 A1 WO2022121822 A1 WO 2022121822A1
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- Prior art keywords
- mechanical polishing
- chemical mechanical
- polishing liquid
- polishing
- cerium oxide
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- 238000005498 polishing Methods 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000035945 sensitivity Effects 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 30
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000006174 pH buffer Substances 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- RRUDCFGSUDOHDG-UHFFFAOYSA-N acetohydroxamic acid Chemical compound CC(O)=NO RRUDCFGSUDOHDG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001171 acetohydroxamic acid Drugs 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- VSNHCAURESNICA-NJFSPNSNSA-N 1-oxidanylurea Chemical compound N[14C](=O)NO VSNHCAURESNICA-NJFSPNSNSA-N 0.000 claims description 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 2
- DRDVJQOGFWAVLH-UHFFFAOYSA-N tert-butyl n-hydroxycarbamate Chemical compound CC(C)(C)OC(=O)NO DRDVJQOGFWAVLH-UHFFFAOYSA-N 0.000 claims description 2
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 150000002443 hydroxylamines Chemical class 0.000 abstract 1
- 229910052684 Cerium Inorganic materials 0.000 description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- XXYNZSATHOXXBJ-UHFFFAOYSA-N 4-hydroxyisoindole-1,3-dione Chemical class OC1=CC=CC2=C1C(=O)NC2=O XXYNZSATHOXXBJ-UHFFFAOYSA-N 0.000 description 1
- DRAJWRKLRBNJRQ-UHFFFAOYSA-N Hydroxycarbamic acid Chemical compound ONC(O)=O DRAJWRKLRBNJRQ-UHFFFAOYSA-N 0.000 description 1
- VSNHCAURESNICA-UHFFFAOYSA-N Hydroxyurea Chemical compound NC(=O)NO VSNHCAURESNICA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960001330 hydroxycarbamide Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CCBCHURBDSNSTJ-UHFFFAOYSA-N n-hydroxybutanamide Chemical compound CCCC(=O)NO CCBCHURBDSNSTJ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
Definitions
- the invention relates to the field of chemical mechanical polishing, in particular to a chemical mechanical polishing liquid and a method for using the same.
- the polishing rate of silicon oxide usually increases with the increase of polishing pressure, and the relationship between polishing rate and polishing pressure can be Described by the Preston equation.
- the polishing rate of TEOS is very sensitive to polishing pressure. With an increase of 0.5 psi (from 1.5 psi to 2.0 psi), the TEOS rate increased by nearly 1000 A/min. The polishing rate is sensitive to pressure, making the polishing process difficult to control. Therefore, there is a need to reduce the sensitivity of the TEOS polishing rate to pressure.
- an auto-stop method is usually used to reduce the sensitivity of the polishing rate to pressure, but the auto-stop means that the polishing rate is reduced, which usually cannot meet production requirements. Therefore, there is an urgent need in the art for a polishing solution that can effectively reduce the sensitivity of the polishing rate to the pressure, while ensuring an appropriate polishing rate.
- the present invention provides a chemical mechanical polishing liquid, which can effectively reduce the sensitivity of the polishing rate to the pressure, while maintaining an appropriate polishing rate, and has a good application prospect in the field.
- the present invention provides a chemical mechanical polishing liquid, which contains cerium oxide abrasive particles, hydroxylamine and its derivatives, and a pH adjuster.
- the chemical mechanical polishing solution includes a pH buffer.
- the pH buffer is benzoic acid.
- the particle size of the cerium oxide abrasive particles is 45nm-75nm.
- the concentration of the cerium oxide abrasive particles is 0.1%-0.5% by mass.
- the concentration of the hydroxylamine and its derivatives is 50 ppm to 3000 ppm by mass.
- hydroxylamine and its derivatives are:
- R 1 and R 2 are H or other functional groups, and the functional groups contain C, H, N, and O elements.
- hydroxylamine and its derivatives are selected from acetohydroxamic acid, N-hydroxysuccinimide, ethyl acetohydroxamic acid, acetone oxime, hydroxyurea, tert-butyl N-hydroxycarbamate and N-hydroxycarbamate - one or more of hydroxyphthalimides.
- the pH value of the chemical polishing solution is 3.0-6.0.
- Another aspect of the present invention provides a method for using a chemical mechanical polishing liquid, wherein any of the above chemical mechanical polishing liquids is used to reduce the sensitivity of the TEOS polishing rate to pressure.
- the chemical mechanical polishing liquid in the present invention can effectively reduce the sensitivity of the polishing rate to the pressure, and at the same time maintain the polishing rate of the chemical mechanical polishing liquid.
- the chemical mechanical polishing solutions of Examples 1 to 6 and Comparative Examples 1 to 3 were respectively prepared, and nitric acid or potassium hydroxide was used as a pH adjuster to adjust the pH value of the cleaning solution to the desired value.
- Numerical value is required.
- the light scattering particle size of ceria-1 is around 180 nm.
- the particle size of the light-scattering cerium oxide-2 is about 160 nm.
- the particle sizes of cerium oxide particles measured by the specific surface area (BET) method are: cerium oxide-1: 60 nm, cerium oxide-2: 60 nm, cerium oxide-3: 30 nm. In the present invention, the particle size is based on the specific surface method.
- cerium oxide-1 and cerium oxide-3 are not surface-treated, and when pH ⁇ 6, the surfaces of the cerium oxide particles without surface treatment are positively charged, and the zeta potential is greater than 20mV.
- Cerium oxide-2 is a cerium oxide particle after surface treatment, its surface is negatively charged, and the zeta potential is less than -20mV.
- polishing liquids in Examples 1 to 6 and Comparative Examples 1 to 3 were used to perform polishing tests on TEOS blank wafers respectively, and the sensitivity of the polishing rate to the pressure value was measured.
- Corresponding polishing conditions include: IC1010 polishing pad, Platten and Carrier rotation speeds of 93 rpm and 87 rpm, respectively, polishing pressure: 1.5 psi, 2 psi, 3 psi, 4 psi and 5 psi, polishing fluid flow rate of 150 mL/min, and polishing time of 60 seconds.
- the TEOS film thickness was measured with a NanoSpec film thickness measurement system (NanoSpec 6100-300, Shanghai Nanospec Technology Corporation). Starting at 3mm from the edge of the wafer, measure 49 points at equal intervals on the diameter line. The polishing rate is an average of 49 points. The corresponding measured polishing rates and calculated values are shown in Table 2.
- the polishing rate of the polishing liquid has a certain reduction in the sensitivity to pressure, and at the same time A suitable polishing rate is guaranteed.
- the chemical mechanical polishing liquids in Examples 7 to 16 were prepared according to the components and contents described in Table 3, and the pH value of the polishing liquid was adjusted to the required value. Cerium oxide was used in Examples 7 to 16. -1 as abrasive particles. In Examples 7 and 8, benzoic acid was further used as the pH buffer.
- Example 7 and Example 8 it can be seen that adding 1000ppm of hydroxyurea can reduce the polishing slope of TEOS/pressure more effectively than 100ppm, and the slope of rate versus pressure is reduced from 337.5A/min/psi to 34A/min/psi. Comparing Example 4 and Example 8, it can be seen that, under the same conditions of other components and conditions, adding benzoic acid as a pH buffer can further reduce the sensitivity of polishing rate to pressure, and maintain a suitable polishing rate. Moreover, in actual use scenarios, the pH buffer can maintain the pH value of the polishing solution without major fluctuations, so that the performance of the polishing solution remains stable, which is more suitable for actual production needs.
- the polishing liquid in the present invention can effectively reduce the sensitivity of the polishing rate of the polishing liquid to pressure, and at the same time the polishing liquid can maintain a suitable polishing rate. .
- the polishing liquid in the present invention can be applied to different kinds of cerium oxide abrasive particles. Therefore, the polishing liquid in the present invention can be applied to more general production conditions, has excellent polishing effect, and has broad application prospects in the field of mechanical polishing.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The present invention provides a chemical-mechanical polishing solution and a method for using same. The chemical-mechanical polishing solution comprises a cerium oxide abrasive particle, a hydroxylamine derivative, and a pH regulator. The chemical-mechanical polishing solution in the present invention can effectively reduce the sensitivity of the polishing rate to pressure, and can also ensure a proper polishing rate.
Description
本发明涉及化学机械抛光领域，尤其涉及一种化学机械抛光液及其使用方法。The invention relates to the field of chemical mechanical polishing, in particular to a chemical mechanical polishing liquid and a method for using the same.
在化学机械抛光(CMP)过程中，如若使用氧化铈作为研磨颗粒，氧化硅的(氧化物或者TEOS)的抛光速率通常随着抛光的压力增加而增加，抛光速率与抛光压力之间的关系可以通过Preston方程描述。现有技术中，如若使用正电荷(zeta电位>20mV)，颗粒粒径>30nm的氧化铈作为研磨颗粒，在pH＜6抛光液中，TEOS的抛光速率对抛光压力十分敏感，比如：当压力增加0.5psi(从1.5psi增加至2.0psi)，TEOS速率增加近1000A/min。而抛光速率对压力敏感使得抛光过程难以控制。所以，需要降低TEOS抛光速率对压力的敏感性。In the chemical mechanical polishing (CMP) process, if cerium oxide is used as abrasive particles, the polishing rate of silicon oxide (oxide or TEOS) usually increases with the increase of polishing pressure, and the relationship between polishing rate and polishing pressure can be Described by the Preston equation. In the prior art, if positive charge (zeta potential>20mV) and cerium oxide with particle size>30nm are used as abrasive particles, in pH<6 polishing liquid, the polishing rate of TEOS is very sensitive to polishing pressure. With an increase of 0.5 psi (from 1.5 psi to 2.0 psi), the TEOS rate increased by nearly 1000 A/min. The polishing rate is sensitive to pressure, making the polishing process difficult to control. Therefore, there is a need to reduce the sensitivity of the TEOS polishing rate to pressure.
现有技术中，通常采用自动停止(auto stop)的方法降低抛光速率对压力的敏感程度，但自动停止意味着抛光速率降低，通常不能满足生产需求。因此，本领域亟需一种能够有效降低抛光速率对压力的敏感性，同时能够保证适当的抛光速率的抛光液。In the prior art, an auto-stop method is usually used to reduce the sensitivity of the polishing rate to pressure, but the auto-stop means that the polishing rate is reduced, which usually cannot meet production requirements. Therefore, there is an urgent need in the art for a polishing solution that can effectively reduce the sensitivity of the polishing rate to the pressure, while ensuring an appropriate polishing rate.
发明内容SUMMARY OF THE INVENTION
为解决上述问题，本发明提供一种化学机械抛光液，可以有效降低抛光速率对压力的敏感性，同时保持适当的抛光速率，在本领域具有良好的应用前景。In order to solve the above problems, the present invention provides a chemical mechanical polishing liquid, which can effectively reduce the sensitivity of the polishing rate to the pressure, while maintaining an appropriate polishing rate, and has a good application prospect in the field.
具体的，本发明提供一种化学机械抛光液，含有氧化铈研磨颗粒，羟胺及其衍生物和pH调节剂。Specifically, the present invention provides a chemical mechanical polishing liquid, which contains cerium oxide abrasive particles, hydroxylamine and its derivatives, and a pH adjuster.
优选的，所述化学机械抛光液包括pH缓冲剂。Preferably, the chemical mechanical polishing solution includes a pH buffer.
优选的，所述pH缓冲液为苯甲酸。Preferably, the pH buffer is benzoic acid.
优选的，所述氧化铈研磨颗粒的粒径为45nm-75nm。Preferably, the particle size of the cerium oxide abrasive particles is 45nm-75nm.
优选的，所述氧化铈研磨颗粒的浓度为质量百分比0.1％-0.5％。Preferably, the concentration of the cerium oxide abrasive particles is 0.1%-0.5% by mass.
优选的，所述羟胺及其衍生物的浓度为质量百分比50ppm～3000ppm。Preferably, the concentration of the hydroxylamine and its derivatives is 50 ppm to 3000 ppm by mass.
优选的，所述羟胺及其衍生物为：Preferably, the hydroxylamine and its derivatives are:
优选的，其中所述羟胺及其衍生物选自乙酰氧肟酸、N-羟基丁二酰亚胺、乙酰羟肟酸乙酯、丙酮肟、羟基脲、N-羟基氨基甲酸叔丁酯和N-羟基苯邻二甲酰亚胺中的一种或多种。Preferably, wherein the hydroxylamine and its derivatives are selected from acetohydroxamic acid, N-hydroxysuccinimide, ethyl acetohydroxamic acid, acetone oxime, hydroxyurea, tert-butyl N-hydroxycarbamate and N-hydroxycarbamate - one or more of hydroxyphthalimides.
优选的，所述化学抛光液的pH值为3.0-6.0。Preferably, the pH value of the chemical polishing solution is 3.0-6.0.
本发明的另一方面，提供一种化学机械抛光液的使用方法，将任一上述化学机械抛光液用于减少TEOS抛光速率对压力的敏感性。Another aspect of the present invention provides a method for using a chemical mechanical polishing liquid, wherein any of the above chemical mechanical polishing liquids is used to reduce the sensitivity of the TEOS polishing rate to pressure.
本发明中的化学机械抛光液可以有效降低抛光速率对压力的敏感性，并同时保持化学机械抛光液的抛光速率。The chemical mechanical polishing liquid in the present invention can effectively reduce the sensitivity of the polishing rate to the pressure, and at the same time maintain the polishing rate of the chemical mechanical polishing liquid.
下面结合具体实施例，详细阐述本发明的优势。The advantages of the present invention will be described in detail below with reference to specific embodiments.
依照表1所示的组分及其含量分别配置实施例1～6与对比例1～3化学机械抛光液，并使用硝酸或氢氧化钾作为pH调节剂，将清洗液的pH值调节至所需数值。氧化铈-1的光散射的颗粒尺寸是180nm左右。所述氧化铈-2的光散射的颗粒尺寸160nm左右。通过比表面(BET)方法测得氧化铈颗粒粒径分别为：氧化铈-1:60nm，氧化铈-2:60nm，氧化铈-3：30nm。本发明中，颗粒尺寸以比表面方法为准。所述氧化铈-1和氧化铈-3均未进行表面处理，在pH＜6时，未经表面处理的氧化铈颗粒表面均带有正电荷，zeta电位大于20mV。氧化铈-2为经过表面处理后的氧化铈颗粒，其表面带有负电荷，zeta电位小于-20mV。According to the components and their contents shown in Table 1, the chemical mechanical polishing solutions of Examples 1 to 6 and Comparative Examples 1 to 3 were respectively prepared, and nitric acid or potassium hydroxide was used as a pH adjuster to adjust the pH value of the cleaning solution to the desired value. Numerical value is required. The light scattering particle size of ceria-1 is around 180 nm. The particle size of the light-scattering cerium oxide-2 is about 160 nm. The particle sizes of cerium oxide particles measured by the specific surface area (BET) method are: cerium oxide-1: 60 nm, cerium oxide-2: 60 nm, cerium oxide-3: 30 nm. In the present invention, the particle size is based on the specific surface method. The cerium oxide-1 and cerium oxide-3 are not surface-treated, and when pH<6, the surfaces of the cerium oxide particles without surface treatment are positively charged, and the zeta potential is greater than 20mV. Cerium oxide-2 is a cerium oxide particle after surface treatment, its surface is negatively charged, and the zeta potential is less than -20mV.
表1实施例1～6与对比例1～3的化学机械抛光液组分Table 1 Chemical mechanical polishing liquid components of Examples 1-6 and Comparative Examples 1-3
使用实施例1～6与对比例1～3中的抛光液，采用Mirra抛光机台分别对TEOS空白晶圆进行抛光测试，测量抛光速率对压力值的敏感性。对应抛光条件包括：IC1010抛光垫，Platten和Carrier转速分别为93rpm和87rpm，抛光压力：1.5psi，2psi，3psi，4psi和5psi，抛光液流速为150mL/min，抛光时间为60秒。TEOS膜厚是用NanoSpec膜厚测量系统(NanoSpec6100-300,Shanghai Nanospec Technology Corporation)测出的。从晶圆边缘3mm开始，在直径线上以同等间距测49个点。抛光速率是49点的平均值。相应测得的抛光速率及计算值如表2所示。Using the polishing liquids in Examples 1 to 6 and Comparative Examples 1 to 3, a Mirra polishing machine was used to perform polishing tests on TEOS blank wafers respectively, and the sensitivity of the polishing rate to the pressure value was measured. Corresponding polishing conditions include: IC1010 polishing pad, Platten and Carrier rotation speeds of 93 rpm and 87 rpm, respectively, polishing pressure: 1.5 psi, 2 psi, 3 psi, 4 psi and 5 psi, polishing fluid flow rate of 150 mL/min, and polishing time of 60 seconds. The TEOS film thickness was measured with a NanoSpec film thickness measurement system (NanoSpec 6100-300, Shanghai Nanospec Technology Corporation). Starting at 3mm from the edge of the wafer, measure 49 points at equal intervals on the diameter line. The polishing rate is an average of 49 points. The corresponding measured polishing rates and calculated values are shown in Table 2.
表2实施例1～6与对比例1～3中化学机械抛光液的抛光测试结果Table 2 The polishing test results of chemical mechanical polishing solutions in Examples 1-6 and Comparative Examples 1-3
由表2所示的测试结果可知，对比例1的速率/压力的斜率数值高达783A/min/psi，意味着对比例1的化学机械抛光液的抛光速率对压力表现出很强的敏感性。对比例2中，由于氧化铈-2表面带有负电荷，其抛光速率明显减低，在压力为2psi时，抛光速率低于700A/min；并且抛光速率/压力的斜率值依旧很高，即，该抛光液的抛光速度对压力仍然较为敏感。对比例3中，虽然氧化铈-3表面带有正电荷，但是其颗粒粒径为30nm，抛光液的抛光速率受到了极大的影响：在压力为3psi时，抛光速率低于100A/min，远低于～2000A/min的目标抛光速率。From the test results shown in Table 2, it can be seen that the slope value of the rate/pressure of Comparative Example 1 is as high as 783 A/min/psi, which means that the polishing rate of the chemical mechanical polishing solution of Comparative Example 1 shows a strong sensitivity to pressure. In Comparative Example 2, due to the negative charge on the surface of cerium oxide-2, the polishing rate was significantly reduced. When the pressure was 2 psi, the polishing rate was lower than 700A/min; and the slope value of polishing rate/pressure was still high, that is, The polishing speed of the polishing liquid is still relatively sensitive to pressure. In Comparative Example 3, although the surface of cerium oxide-3 has a positive charge, its particle size is 30nm, and the polishing rate of the polishing solution is greatly affected: when the pressure is 3psi, the polishing rate is lower than 100A/min, Well below the target polishing rate of ~2000A/min.
观察实施例1～实施例6可知，在抛光液中加入羟胺及其衍生物可以有效改善抛光速率对压力的敏感性。比较对比例1与实施例1：在其他条件相同的情况下，实施例1中加入200ppm乙酰氧肟酸，其抛光液的抛光速率相对于压力的斜率从783A/min/psi降低至590A/min/psi，并且同时具有高效的抛光速率，远超过目标抛光速率～2000A/min。观察实施例1～实施例6中的数据，在抛光液中使用本发明中所述的不同类型的羟胺及其衍生物，其抛光液的抛光速率对于压力的敏感性均有一定的降低，同时保证了合适的抛光速率。Observing Examples 1 to 6, it can be seen that adding hydroxylamine and its derivatives into the polishing solution can effectively improve the sensitivity of polishing rate to pressure. Comparing Comparative Example 1 with Example 1: Under the same other conditions, adding 200 ppm of acetylhydroxamic acid in Example 1, the slope of the polishing rate of the polishing liquid relative to the pressure was reduced from 783A/min/psi to 590A/min /psi, and at the same time has an efficient polishing rate, far exceeding the target polishing rate of ~2000A/min. Observing the data in Examples 1 to 6, when different types of hydroxylamine and its derivatives described in the present invention are used in the polishing liquid, the polishing rate of the polishing liquid has a certain reduction in the sensitivity to pressure, and at the same time A suitable polishing rate is guaranteed.
依照表3中所述的组分及含量配制实施例7～实施例16中的化学机械抛光液，将抛光液的pH值调节至所需数值，实施例7～实施例16中均使用氧化铈-1作为研磨颗粒。实施例7、8中进一步使用苯甲酸作为pH缓冲液。The chemical mechanical polishing liquids in Examples 7 to 16 were prepared according to the components and contents described in Table 3, and the pH value of the polishing liquid was adjusted to the required value. Cerium oxide was used in Examples 7 to 16. -1 as abrasive particles. In Examples 7 and 8, benzoic acid was further used as the pH buffer.
表3实施例7～实施例16的化学机械抛光液组分Table 3 Chemical Mechanical Polishing Fluid Components of Examples 7 to 16
依照上述相同的测试步骤，对实施例7～实施例16的抛光液的抛光性能进行测试，测试所得的数据如表4所示。According to the same test procedure as above, the polishing properties of the polishing liquids of Examples 7 to 16 were tested, and the data obtained from the test are shown in Table 4.
表4实施例7～实施例16化学机械抛光液的抛光测试结果Table 4 Polishing test results of chemical mechanical polishing liquids in Examples 7 to 16
对比实施例7、实施例8可知，加入1000ppm羟基脲，能够比100ppm更加有效地减低TEOS/压力的抛光斜率，速率对压力的斜率从337.5A/min/psi减低到34A/min/psi。对比实施例4、实施例8可知，在其他组分及条件相同的情况下，加入苯甲酸作为pH缓冲剂可进一步的降低抛光速率对压力的敏感性，并且保持合适的抛光速率。并且，在实际使用情景下，pH缓冲剂能够维持抛光液的pH值不会出现较大的波动，使抛光液的性能保持稳定，更加适合实际生产需求。Comparing Example 7 and Example 8, it can be seen that adding 1000ppm of hydroxyurea can reduce the polishing slope of TEOS/pressure more effectively than 100ppm, and the slope of rate versus pressure is reduced from 337.5A/min/psi to 34A/min/psi. Comparing Example 4 and Example 8, it can be seen that, under the same conditions of other components and conditions, adding benzoic acid as a pH buffer can further reduce the sensitivity of polishing rate to pressure, and maintain a suitable polishing rate. Moreover, in actual use scenarios, the pH buffer can maintain the pH value of the polishing solution without major fluctuations, so that the performance of the polishing solution remains stable, which is more suitable for actual production needs.
因此，综合上述实施例可知，本发明中在含有氧化铈的抛光液中加入羟胺及其衍生物，能够有效降低抛光液的抛光速率对压力的敏感性，并且同时抛光液能够保持合适的抛光速率。除此之外，本发明中的抛光液能够适用于不同种类的氧化铈研磨颗粒。因此，本发明中的抛光液能够适用于更加普遍的生产条件，并具有优异的抛光效果，在机械抛光领域具有广泛的应用前景。Therefore, based on the above examples, it can be seen that adding hydroxylamine and its derivatives to the polishing liquid containing cerium oxide in the present invention can effectively reduce the sensitivity of the polishing rate of the polishing liquid to pressure, and at the same time the polishing liquid can maintain a suitable polishing rate. . Besides, the polishing liquid in the present invention can be applied to different kinds of cerium oxide abrasive particles. Therefore, the polishing liquid in the present invention can be applied to more general production conditions, has excellent polishing effect, and has broad application prospects in the field of mechanical polishing.
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。The specific embodiments of the present invention have been described above in detail, but they are only used as examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be included within the scope of the present invention.
Claims (10)
- 一种化学机械抛光液，其特征在于，含有氧化铈研磨颗粒，羟胺及其衍生物和pH调节剂。A chemical mechanical polishing liquid is characterized in that it contains cerium oxide abrasive particles, hydroxylamine and its derivatives and a pH adjuster.
- 如权利要求1所述的化学机械抛光液，其特征在于，进一步包括PH缓冲液。The chemical mechanical polishing liquid of claim 1, further comprising a pH buffer.
- 如权利要求2所述的化学机械抛光液，其特征在于，所述pH缓冲液为苯甲酸。The chemical mechanical polishing liquid of claim 2, wherein the pH buffer is benzoic acid.
- 如权利要求1所述的化学机械抛光液，所述氧化铈研磨颗粒的粒径为45nm-75nm。The chemical mechanical polishing liquid according to claim 1, wherein the particle size of the cerium oxide abrasive particles is 45nm-75nm.
- 如权利要求1所述的化学机械抛光液，所述氧化铈研磨颗粒的浓度为质量百分比0.1％-0.5％。The chemical mechanical polishing liquid according to claim 1, wherein the concentration of the cerium oxide abrasive particles is 0.1%-0.5% by mass.
- 如权利要求1所述的化学机械抛光液，所述羟胺及其衍生物的浓度为质量百分比50ppm～3000ppm。The chemical mechanical polishing liquid according to claim 1, wherein the concentration of the hydroxylamine and its derivatives is 50 ppm to 3000 ppm by mass.
- 如权利要求1所述的化学机械抛光液，所述羟胺及其衍生物其中，R 1和R 2为H或者其他官能团，所述官能团含有C、H、N、O元素。 chemical mechanical polishing liquid as claimed in claim 1, described hydroxylamine and derivatives thereof
Wherein, R 1 and R 2 are H or other functional groups, and the functional groups contain C, H, N, and O elements. - 如权利要求6所述的化学机械抛光液，其中所述羟胺及其衍生物选自乙酰氧肟酸、N-羟基丁二酰亚胺、乙酰羟肟酸乙酯、丙酮肟、羟基脲、N-羟基氨基甲酸叔丁酯和N-羟基苯邻二甲酰亚胺中的一种或多种。The chemical mechanical polishing liquid according to claim 6, wherein the hydroxylamine and its derivatives are selected from the group consisting of acetylhydroxamic acid, N-hydroxysuccinimide, ethyl acetylhydroxamate, acetone oxime, hydroxyurea, N - One or more of tert-butyl hydroxycarbamate and N-hydroxyphthalimide.
- 如权利要求1所述的化学机械抛光液，所述化学抛光液的pH值为3.0-6.0.chemical mechanical polishing liquid as claimed in claim 1, the pH value of described chemical polishing liquid is 3.0-6.0.
- 一种化学机械抛光液的使用方法，其特征在于，将如权利要求1～9任一所述的化学机械抛光液用于减少TEOS抛光速率对压力的敏感性。A method for using a chemical mechanical polishing liquid, characterized in that the chemical mechanical polishing liquid according to any one of claims 1 to 9 is used to reduce the sensitivity of the TEOS polishing rate to pressure.
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