WO2016107409A1 - 一种化学机械抛光液及其应用 - Google Patents
一种化学机械抛光液及其应用 Download PDFInfo
- Publication number
- WO2016107409A1 WO2016107409A1 PCT/CN2015/097557 CN2015097557W WO2016107409A1 WO 2016107409 A1 WO2016107409 A1 WO 2016107409A1 CN 2015097557 W CN2015097557 W CN 2015097557W WO 2016107409 A1 WO2016107409 A1 WO 2016107409A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polishing liquid
- chemical mechanical
- mechanical polishing
- liquid according
- silicon
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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
Definitions
- the invention relates to a chemical mechanical polishing liquid and an application thereof, in particular to a chemical mechanical polishing liquid for improving the polishing rate of silicon dioxide and an application thereof.
- CMP chemical mechanical polishing
- CMP Chemical mechanical polishing
- It usually consists of a polishing table with a polishing pad and a polishing head for carrying the chip.
- the polishing head holds the chip and then presses the front side of the chip against the polishing pad.
- the polishing head moves linearly on the polishing pad or in the same direction of motion as the polishing table.
- the slurry containing the abrasive particles is dropped onto the polishing pad and laid flat on the polishing pad by centrifugation.
- the surface of the chip achieves global planarization under both mechanical and chemical effects.
- the chemical mechanical polishing liquid used is mainly classified into an acidic and an alkaline slurry.
- the stability of the alkaline slurry is relatively good, but there is no suitable oxidizing agent, and the problem of surface cloud point and slight scratching is easily caused during the polishing process.
- Acidic pastes have shown certain advantages in this regard. It can achieve a higher polishing rate with lower abrasive particles.
- the size of the abrasive particles in the acid slurry gradually grows under the action of the chemical components in the slurry as the storage time increases. When the particle size is larger than 120 nm, sedimentation will occur. Layering and other phenomena, seriously affecting the quality of polishing, resulting in product failure. Therefore, controlling the growth of the abrasive particles and prolonging the service life are problems that the acidic slurry is eager to solve.
- abrasive particles used in chemical mechanical polishing fluids typically employ silica, including colloidal silica and fumed silica. They are solids themselves, but they are uniformly dispersed in aqueous solution, do not settle, and can even maintain long-term stability of 1 to 3 years.
- the stability of the abrasive particles in the aqueous phase can be explained by the electric double layer theory - since each particle surface carries the same charge, they repel each other and do not agglomerate.
- the Stern model when the colloidal ions move, a Zeta potential is generated on the shear plane.
- Zeta potential is an important indicator of colloidal stability because the stability of the colloid is closely related to the electrostatic repulsion between the particles.
- the decrease in Zeta potential reduces the electrostatic repulsion, resulting in an attractive van der Waals attraction between the particles, causing colloid accumulation and settling.
- the level of ionic strength is an important factor affecting the Zeta potential.
- the stability of the colloid is affected by many other factors in addition to the zeta potential. For example, due to the influence of temperature, at higher temperatures, the irregular thermal motion of the particles is intensified, and the probability of collision with each other increases, which accelerates aggregation; for example, it is more stable than neutral in strong alkaline and strong acidic conditions due to pH. Among them, the most alkaline is the most stable, and the pH range of 4-7 is the most unstable; for example, some surfactants can act as a dispersing agent to improve the stability, while some surfactants reduce the nanometer by the surfactant type. The surface charge of the particles reduces electrostatic repulsion and accelerates sedimentation.
- anionic surfactants contribute to the stability of the nanoparticles, while cationic surfactants tend to reduce stability; for example, depending on the molecular weight of the additives, too long long chains of polymers sometimes entangle Nanoparticles increase the viscosity of the dispersion and accelerate particle agglomeration. Therefore, the stability of silica sol is affected by many factors.
- a polishing liquid containing a silane coupling agent and a polishing method are disclosed in U.S. Patent No. 6, 142, 706 and U.S. Patent No. 09,609, 882.
- the silane coupling agent serves to change the polishing speed of various materials and to improve the surface roughness.
- These two patents have not found that at high ionic strength (>0.1 mol/Kg), the silane coupling agent can act to counteract high ionic strength and stabilize the nanoparticles. Because usually When a very high ionic strength is contained (for example, containing more than >0.2 mol/Kg of potassium ion), the electric double layer of the silica sol particles is greatly compressed, the electrostatic repulsion force is reduced, and gelation and precipitation are rapidly formed.
- the technical problem to be solved by the present invention is how to increase the polishing rate of silica and maintain the stability and dispersion of the abrasive particles in the chemical mechanical polishing liquid at high ionic strength.
- the present invention discloses a method of using a silicon-containing organic compound, and there is a significant synergistic effect between the silicon-containing compound and other surfactants, which greatly increases the polishing rate of the silica.
- it is possible to stabilize the abrasive particles and improve the pH stability of the polishing liquid, that is, to maintain the set pH of the abrasive particles without changing.
- An aspect of the present invention provides a polishing liquid comprising a silicon-containing compound, an amphoteric surfactant, silica abrasive particles, and water.
- the silicon-containing organic compound can be represented by the following formula:
- R is a non-hydrolyzable substituent, usually an alkyl group, having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, of which 2 to 10 carbon atoms are most preferred; The carbon atoms can continue to be replaced by other atoms such as oxygen, nitrogen, sulfur, phosphine, halogen, silicon, and the like.
- D is an organic functional group attached to R, and may be an amino group, a ureido group, a thiol group, an epoxy group, an acryl group or the like.
- A, B are the same or different hydrolyzable substituents or hydroxyl groups; C may be a hydrolyzable group or a hydroxyl group, or may be A non-hydrolyzable alkyl substituent; A, B and C are usually a chloro group, a methoxy group, an ethoxy group, a methoxyethoxy group, an acetoxy group, a hydroxyl group, etc., and these groups form a silanol upon hydrolysis ( Si(OH)3), combined with an inorganic substance, forms a siloxane.
- D is a vinyl group, an amino group, an epoxy group, an acryloyloxy group, a fluorenyl group or a ureido group. These reactive groups can be combined with an organic substance to react.
- a representative silicon-containing organic compound is a silane coupling agent such as the following structure:
- the silicon-containing organic compound can be added to the polishing liquid through various ways. 1: The abrasive particles are bonded to the silicon-containing compound before the preparation of the polishing liquid (commonly known as particle surface modification, surface treatment), and then the surface is modified. The post abrasive particles are added to the polishing liquid. 2: The silicon-containing organic compound is mixed with the abrasive particles and other components at the time of producing the polishing liquid. 3: the silicon-containing organic compound may be completely hydrolyzed or partially hydrolyzed to form a Si-OH group, and then added to the polishing liquid, in which the Si-OH group and the particle surface Si-OH are completely bonded or Partial bonding. Therefore, the silicon-containing organic compound used in the present invention may have various forms such as free, bonded, partially hydrolyzed, and completely hydrolyzed during polishing.
- the concentration of the silicon-containing organic compound is 0.001% to 1% by mass, preferably 0.01% to 0.5% by mass.
- the concentration of the silica abrasive particles is 2% to 10% by mass.
- the particle diameter is 20 to 200 nm, preferably 20 to 120 nm.
- the amphoteric surfactant is preferably a betaine type, an ammonium oxide type and/or an imidazoline amphoteric surfactant, preferably dodecyl ethoxy sulfobetaine or dodecyl hydroxypropyl sulfonate.
- an imidazoline amphoteric surfactant preferably dodecyl ethoxy sulfobetaine or dodecyl hydroxypropyl sulfonate.
- a base a tetradecylamide propyl hydroxypropyl sulfobetaine, an alkyl dimethyl hydroxypropyl phosphate betaine, a lauramide propyl ammonium oxide, an imidazoline amphoteric surfactant
- the content of the amphoteric surfactant is preferably from 0.01 to 1.5% by mass, more preferably from 0.05 to 0.5% by mass.
- An electrolyte ion having an ionic strength of 0.1 mol/Kg or more may be added to the polishing liquid.
- the electrolyte ions are metal ions and/or non-metal ions. More preferably, the electrolyte ions are potassium ions.
- the balance in the polishing liquid is water.
- the polishing solution can work at an acidic pH or an alkaline pH.
- the pH of the polishing liquid is between 1 and 7. Within this range, the pH is preferably greater than or equal to 2 and less than or equal to 6.
- the most preferred pH of the polishing composition is 3-5.
- the slurry may also contain an inorganic or organic pH adjuster to lower the pH of the slurry to an acidic pH or to increase the pH to an alkaline pH.
- Suitable inorganic pH reducing agents include, for example, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, or a combination comprising at least one of the foregoing inorganic pH reducing agents.
- Suitable pH enhancers include one of the following: a metal hydroxide, ammonium hydroxide or a nitrogen-containing organic base, or a combination of the above-described pH increasing agents.
- the present invention achieves the problem of dispersion stability of a chemical mechanical polishing liquid at a high ionic strength by an organic compound containing silicon.
- a highly concentrated chemical mechanical polishing liquid can be prepared by this method.
- the polishing liquid was prepared according to the ingredients of the respective examples in Table 1 and the comparative examples and the ratio thereof, and uniformly mixed, and the mass percentage was made up to 100% with water. Adjust to the desired pH with KOH, HNO3 or a pH adjuster.
- the polishing conditions were as follows: the polishing machine was a Mirra machine, a Fujibo polishing pad, a 200 mm Wafer, a down pressure of 1.5 psi, and a polishing droplet acceleration of 150 ml/min.
- Comparative Example 1 showed that at a very high ionic strength, the removal rate of silica was only 350 A/min, and the polishing liquid was unstable and rapidly destratified.
- Comparative Example 3 and Comparative Example 1 showed that at a very high ionic strength, the addition of a silane coupling agent increased the removal rate of silica by 220 A/min, and the polishing liquid was stable, and the average particle size of the abrasive particles ( Particle mean size) does not increase.
- Comparative Example 2 showed that the addition of lauramide propyl ammonium oxide increased the polishing rate of silica by 525 A/min, but the polishing solution was unstable and rapidly precipitated in layers.
- Example 1 shows that the addition of a silane coupling agent in the presence of lauramide propyl ammonium oxide, the removal rate of silica is lower than that without lauryl propyl methoxide and without a silane coupling agent.
- An increase of 860 A/min is greater than the sum of the contributions of both the silane coupling agent (220 A/min) and the lauramide propyl ammonium oxide (525 A/min), indicating: silane coupling agent and lauramide propyl ammonium oxide
- the synergy between other amphoteric surfactants can greatly increase the polishing speed of silica.
- Comparative Examples 1 to 2 no silane coupling agent was added, and the polishing liquid was unstable.
- Examples 1 to 14 there was a silane coupling agent, the polishing liquid was relatively stable, and the removal rate of silica was remarkably improved.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
Claims (18)
- 一种化学机械抛光液,其包括含硅化合物、两性表面活性剂、二氧化硅研磨颗粒以及水。
- 如权利要求2所述的化学机械抛光液,其特征在于,所述含硅的有机化合物中R为烷基,且所述烷基碳链上的碳原子被氧、氮、硫、膦、卤素、硅等其他原子继续取代;A,B和C分别为氯基、甲氧基、乙氧基、甲氧基乙氧基、乙酰氧基或羟基。
- 如权利要求1所述的化学机械抛光液,其特征在于,所述含硅的有机化合物为硅烷偶联剂。
- 如权利要求4所述的化学机械抛光液,其特征在于,所述含硅的有机化合物为3-氨基丙基三乙氧基硅烷(商品名KH-550),γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(商品名KH-560),γ-(甲基丙烯酰氧)丙基三甲氧基硅 烷(商品名KH-570),γ-巯丙基三乙氧基硅烷(商品名KH-580),γ-巯丙基三甲氧基硅烷(商品名KH-590),N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷(商品名KH-602),γ-氨乙基氨丙基三甲氧基硅烷(商品名KH-792)中的一种或多种。
- 如权利要求1所述的化学机械抛光液,其中,所述含硅的有机化合物的浓度为质量百分比0.001%~1%。
- 如权利要求6所述的化学机械抛光液,其中,所述含硅的有机化合物的浓度为质量百分比0.01%~0.5%。
- 如权利要求1所述的化学机械抛光液,其中,所述二氧化硅研磨颗粒的浓度为质量百分比2%~10%。
- 如权利要求1所述的化学机械抛光液,其中,所述二氧化硅研磨颗粒的粒径为20~200nm。
- 如权利要求9所述的化学机械抛光液,其中,所述二氧化硅研磨颗粒的粒径为20~120nm。
- 如权利要求1所述的化学机械抛光液,其中,所述两性表面活性剂为甜菜碱型、氧化铵型和/或咪唑啉两性表面活性剂。
- 如权利要求11所述的化学机械抛光液,其中,所述两性表面活性剂为十二烷基乙氧基磺基甜菜碱、十二烷基羟丙基磺基甜菜碱、十四烷基酰胺丙基羟丙基磺基甜菜碱、烷基二甲基羟丙基磷酸酯甜菜碱、月桂酰胺丙基氧化铵、咪唑啉两性表面活性剂中的一种或多种。
- 如权利要求1所述的化学机械抛光液,其中,所述两性表面活性剂的含量为质量百分比0.01~1.5%。
- 如权利要求13所述的化学机械抛光液,其中,所述两性表面活性剂的含量为质量百分比0.05~0.5%。
- 如权利要求1所述的化学机械抛光液,其中,所述化学机械抛光液进一步含有大于或等于0.1mol/Kg的离子强度的电解质离子。
- 如权利要求15所述的化学机械抛光液,其中,所述电解质离子是金属离子和/或非金属离子。
- 如权利要求1所述的化学机械抛光液,其中,所述化学机械抛光液的pH范围是1-7。
- 如权利要求1所述的化学机械抛光液,其中,所述化学机械抛光液还包括pH调节剂。
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CN201410842110.2 | 2014-12-29 | ||
CN201410842110.2A CN105802507A (zh) | 2014-12-29 | 2014-12-29 | 一种化学机械抛光液及其应用 |
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CN108250975A (zh) * | 2016-12-28 | 2018-07-06 | 安集微电子科技(上海)股份有限公司 | 一种化学机械抛光液及其应用 |
US11043396B2 (en) * | 2018-07-31 | 2021-06-22 | Taiwan Semiconductor Manufacturing Company, Ltd. | Chemical mechanical polish slurry and method of manufacture |
CN114479674B (zh) * | 2022-03-01 | 2023-04-07 | 北京通美晶体技术股份有限公司 | 一种用于锗晶片化学机械抛光的精抛光液和精抛光方法 |
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CN1809620A (zh) * | 2003-04-21 | 2006-07-26 | 卡伯特微电子公司 | 用于cmp的涂覆金属氧化物颗粒 |
US20070075292A1 (en) * | 2005-09-26 | 2007-04-05 | Planar Solutions, Llc | Ultrapure colloidal silica for use in chemical mechanical polishing applications |
CN101338082A (zh) * | 2007-07-06 | 2009-01-07 | 安集微电子(上海)有限公司 | 改性二氧化硅溶胶及其制备方法和应用 |
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CN1809620A (zh) * | 2003-04-21 | 2006-07-26 | 卡伯特微电子公司 | 用于cmp的涂覆金属氧化物颗粒 |
US20070075292A1 (en) * | 2005-09-26 | 2007-04-05 | Planar Solutions, Llc | Ultrapure colloidal silica for use in chemical mechanical polishing applications |
CN101338082A (zh) * | 2007-07-06 | 2009-01-07 | 安集微电子(上海)有限公司 | 改性二氧化硅溶胶及其制备方法和应用 |
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