CN109554119B - Silicon carbide chemical mechanical polishing solution with improved pH stability and application thereof - Google Patents

Silicon carbide chemical mechanical polishing solution with improved pH stability and application thereof Download PDF

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CN109554119B
CN109554119B CN201811303460.6A CN201811303460A CN109554119B CN 109554119 B CN109554119 B CN 109554119B CN 201811303460 A CN201811303460 A CN 201811303460A CN 109554119 B CN109554119 B CN 109554119B
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polishing solution
alumina
silicon carbide
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mechanical polishing
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CN109554119A (en
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窦文涛
宗艳民
梁庆瑞
王含冠
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Shandong Tianyue Advanced Technology Co Ltd
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SICC Science and Technology Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

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Abstract

The invention provides a silicon carbide chemical mechanical polishing solution with improved pH stability, which comprises: the abrasive material comprises an oxidizing agent, a high-hardness abrasive material and a pH stabilizing agent, wherein the pH stabilizing agent is aluminum nitrate. The polishing solution disclosed by the invention can well keep the stability of the pH value in the chemical mechanical polishing process, and the polishing solution has good dispersion stability and is uniformly dispersed. According to the invention, the pH stabilizer aluminum nitrate is added into the polishing solution, so that the pH stability of the polishing solution is stronger in the chemical mechanical polishing process, and the polishing solution is not easy to generate hard agglomeration. The polishing solution of the invention has no pollution to the environment and can be used in a circulating feeding mode.

Description

Silicon carbide chemical mechanical polishing solution with improved pH stability and application thereof
Technical Field
The invention relates to the technical field of chemical mechanical polishing, in particular to a silicon carbide chemical mechanical polishing solution with stable pH value and application thereof.
Background
The polishing rate of current CMP slurries using alkaline hydrogen peroxide-silicon oxide is very low due to the high hardness (9.5) and strong chemical inertness of silicon carbide: (<50nm/hr), for two reasons: firstly, the hardness of silicon oxide is small (6-7); secondly, the chemical action of the oxidant under alkaline conditions is weak. Therefore, alpha-Al having a hardness second to that of silicon carbide is used2O3Acidity (pH) of abrasive<7, especially pH<4) Silicon carbide chemical mechanical polishing solutions are the mainstream.
To improve chemical oxidation, potassium permanganate is the most widely used oxidant, but potassium permanganate consumes H during oxidation+The pH of the polishing solution increases, the stability of the abrasive decreases, and agglomeration and sedimentation occur, which causes instability of the polishing solution and easily causes scratches, thereby affecting the polishing quality, and therefore, it is critical to stabilize the pH of the polishing solution.
Cabot corporation discloses a continuous silicon carbide CMP slurry that can ensure that the pH of the CMP slurry before use is within a reasonable range using potassium permanganate as the oxidizing agent and a conventional pH buffer system, but it is difficult to ensure that the CMP slurry is always within an acidic range during use. The Sinmat company uses potassium permanganate as the oxidizing agent, pH 4, and core (silica or alumina) -shell (manganese oxide) particles as the abrasive, the shell of which has a low hardness (<6) and is not suitable for chemical mechanical polishing of silicon carbide. ASAHI GLASS company CMP polishing solution takes potassium permanganate as an oxidant, and acidic silicon oxide or cerium oxide as an abrasive, and in the use process of the polishing solution, the pH value cannot be controlled, and the abrasive hardness is low, so that ASAHI GLASS company CMP polishing solution has low polishing efficiency on silicon carbide.
In view of the difficulty in ensuring the stability of the pH value of the silicon carbide CMP polishing solution in the chemical mechanical polishing process in the prior art, the invention adopts the specific acidic surface modifier and the pH stabilizer, and can ensure that the pH value of the CMP polishing solution is always in a proper range in the chemical mechanical polishing process of the silicon carbide.
Disclosure of Invention
At present, potassium permanganate becomes a mainstream oxidant of high-speed and high-efficiency SiC chemical mechanical polishing solution, but a large amount of hydrogen ions are consumed in the oxidation process of potassium permanganate, so that the pH value of the polishing solution is increased, the grinding materials are irreversibly agglomerated, and the control of the pH value of the polishing solution becomes very important, while the pH buffer system widely mentioned in the patent cannot control the pH value of the polishing solution to be 3.5-4, has a single function, only plays a role of a pH buffer agent, and has no effect or adverse effect on the stability of the polishing solution; the aluminum nitrate can play a role in stabilizing and buffering pH on one hand, and Al on the other hand3+Can simultaneously stabilize the oxidation of the chips thrown off in the polishing process and the potassium permanganate to form manganese oxide (such as MnO)2) Therefore, the influence of impurities formed in the polishing process on the stability of the polishing solution is reduced, and the polishing solution can be recycled.
The control of aggregation and agglomeration of abrasive particles is the key to ensure polishing quality, and the widely used dispersion stabilizer at present is surfactant or polymer, although surfactant or polymer dispersion stabilizer is also used in the above patent, in practice, these conventional dispersion stabilizers do not play a role in stabilizing in the presence of potassium permanganate during the experiment, and even destroy the stability of the polishing solution. However, the use of core-shell (inorganic/organic or inorganic/inorganic) abrasive particles has the disadvantages of complicated preparation process and difficult quality control. Therefore, water-soluble small molecular acid (such as acetic acid, propionic acid and the like) which resists the oxidation of potassium permanganate is adopted to modify the surface of the alumina, so that a soft layer is provided on one hand, and the aggregation and agglomeration of the alumina are inhibited on the other hand.
In order to solve the problem of poor pH value stability of the existing silicon carbide chemical mechanical polishing solution, the invention provides a silicon carbide chemical mechanical polishing solution with stable pH value, which comprises the following components: the abrasive material comprises an oxidizing agent, a high-hardness abrasive material and a pH stabilizing agent, wherein the pH stabilizing agent is aluminum nitrate. Because the pH stabilizer aluminum nitrate is added into the polishing solution, the pH stability of the polishing solution is stronger in the process of carrying out chemical mechanical polishing, and the polishing solution is not easy to generate hard agglomeration.
In one aspect, the present invention provides a silicon carbide chemical mechanical polishing solution with improved pH stability, the polishing solution comprising: the abrasive material comprises an oxidizing agent, a high-hardness abrasive material and a pH stabilizing agent, wherein the pH stabilizing agent is aluminum nitrate.
Further, the oxidizing agent is selected from one or more of hydrogen peroxide, potassium persulfate, periodate and potassium permanganate. Preferably, the oxidizing agent is selected from potassium permanganate.
Further, the high-hardness abrasive is selected from one or more of alumina, carborundum, diamond, boron carbide and silicon carbon. Preferably, the high hardness abrasive is selected from alumina. More preferably, the high hardness abrasive is selected from acidic alumina dispersions. More preferably, the alumina can be high hardness alpha-alumina (Mohs hardness 9.0) and can also be one or more of transition phase alumina such as theta-alumina, gamma-alumina, kappa-alumina and-alumina.
Further, the polishing solution also comprises a surface modifier of a high-hardness abrasive, wherein the surface modifier can be an organic acid selected from one or more of acetic acid, propionic acid, citric acid, malic acid, itaconic acid, maleic acid, malonic acid, crotonic acid, gluconic acid, glycolic acid, lactic acid and mandelic acid; preferably, acetic acid and/or propionic acid. The surface of the alumina is modified by adopting water-soluble micromolecular acid (such as acetic acid, propionic acid and the like) which resists the oxidation of potassium permanganate, so that a soft layer is provided, the aggregation and agglomeration of the alumina can be inhibited, and the dispersion effect of alumina particles and the stability of dispersion liquid are improved.
Further, the final concentration of the aluminum nitrate is 0.01-5%. Preferably, the final concentration of the aluminum nitrate is 0.05-1%.
Further, the final concentration of the oxidant is 0.01-10%. Preferably, the final concentration of the oxidant is 0.1-4%.
Further, the polishing solution also comprises a surfactant, a corrosion inhibitor, a defoaming agent, a brightening agent, a viscosity regulator or a polymer dispersing agent.
Furthermore, the surfactant can be one or more of sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, tween 20, cetyl trimethyl ammonium bromide, polyethylene glycol and glycerol.
The corrosion inhibitor can be an inorganic corrosion inhibitor or an organic corrosion inhibitor; preferably, the inorganic corrosion inhibitor can be one or more of sodium nitrite and copper sulfate pentahydrate, and the organic corrosion inhibitor can be one or more of monoethanolamine benzoate, hexamethylenetetramine (urotropin), rhodine (di-o-toluenethiourea), hexamethylenetetramine, polyaspartic acid, benzotriazole, urea and corrosion inhibitors containing azolyl and keto;
the brightener is one or more of salicylic acid, sulfosalicylic acid, propiolic alcohol, benzoic acid, cellulose ether, gelatin, saccharin, sulfonic acid and glucose;
the viscosity regulator is selected from one or more of glycerol, polyethylene glycol, gelatin and bone glue;
the dispersant can be an inorganic dispersant or an organic dispersant; preferably, the inorganic dispersant can be sodium hexametaphosphate, and the organic dispersant can be a micromolecular organic dispersant and a polymer-based dispersant; more preferably, the small-molecule organic dispersant can be one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and coconut diethanolamide, and the polymer-based dispersant can be one or more of polyacrylic acid, sodium polyacrylate, polyethylene glycol 4000, carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylate, polymethacrylic acid, polymethacrylate, polymaleic acid, polymaleate, acrylic acid copolymer, acrylic acid salt copolymer, polyaspartic acid and polyaspartic acid salt.
Furthermore, the high-hardness abrasive is acidic alumina dispersion liquid with the concentration of 10-30%, and the dosage of the surface modifier is 0.5-2.0% of the weight of alumina. Preferably, the high-hardness abrasive is acidic alumina dispersion liquid with the concentration of 15-25%, and the dosage of the surface modifier is 1.0-1.5% of the weight of alumina. More preferably, the high-hardness abrasive is an acidic alumina dispersion with a concentration of 20%, and the amount of the surface modifier is 1.2-1.3% of the weight of alumina.
Further, the acidic alumina dispersion can be acidic alumina dispersion of saint gobain, and can also be self-prepared acidic alumina dispersion by adopting alumina powder;
further, the preparation method of the acidic alumina dispersion comprises the steps of dispersing 15-25 g of alumina powder with the particle size of 100nm in 100ml of water, adjusting the pH value to 0-1 by using nitric acid, and grinding for 4-6 hours by using a star-shaped ball mill to prepare the acidic alumina dispersion with the pH value of 3.5-4.
Further, the polishing solution is prepared by the following method:
(1) providing an acidic alumina dispersion;
(2) surface modification is carried out on the acidic alumina dispersion liquid by adopting a surface modifier;
(3) adjusting the pH value to 3.5-4, adding a pH value stabilizer, stirring and dispersing;
(4) adding an oxidant to prepare the silicon carbide chemical mechanical polishing solution with improved pH stability.
Further, the polishing solution is prepared by the following preparation method:
(1) providing an acidic alumina dispersion: dispersing 10-30 g of alumina powder with the particle size of 100nm in 100ml of water, adjusting the pH value to 0-1 by using nitric acid, and grinding for 4-6 hours by using a star-shaped ball mill to prepare an acidic alumina dispersion liquid with the pH value of 3.5-4;
(2) carrying out surface modification on the acidic alumina dispersion liquid by adopting organic acid through ball milling dispersion: adding 0.5-2% (based on the weight of alumina) of organic acid into the acidic alumina dispersion, and continuing to disperse for 2-4 hours by using a ball mill to obtain a modified acidic alumina dispersion;
(3) diluting the modified aluminum oxide dispersion liquid to 0.5-2%, adding nitric acid to adjust the pH value to 3.5-4, adding 0.05-1% of aluminum nitrate, and stirring and dispersing for 1-2 hours;
(4) and adding 0.1-4% of potassium permanganate as an oxidant to prepare the silicon carbide chemical mechanical polishing solution with stable pH value.
Further, the polishing solution is prepared by the following preparation method:
(1) providing an acidic alumina dispersion: dispersing 20 g of alumina powder with the particle size of 50-100nm in 100ml of water, adjusting the pH value to 0-1 by using nitric acid, and grinding for 4-6 hours by using a star-shaped ball mill to prepare an acidic alumina dispersion liquid with the pH value of 3.5-4;
(2) carrying out surface modification on the acidic alumina dispersion liquid by adopting acetic acid and/or propionic acid through ball milling dispersion: adding 0.5-2% (based on the weight of the alumina) of acetic acid and/or propionic acid into the acidic alumina dispersion liquid, and continuing to disperse for 2-4 hours by using a ball mill to obtain a modified acidic alumina dispersion liquid;
(3) diluting the modified aluminum oxide dispersion liquid to 0.5-2%, adding nitric acid to adjust the pH value to 3.5-4, adding 0.05-1% of aluminum nitrate, and stirring and dispersing for 1-2 hours;
(4) and adding 0.1-4% of potassium permanganate as an oxidant to prepare the silicon carbide chemical mechanical polishing solution with improved pH stability.
Further, the step (1) and the step (2) are combined, and the specific steps are as follows: dispersing aluminum oxide in water, adjusting the pH value to 0-1 by using nitric acid, adding a surface modifier organic acid, dispersing by using a ball mill, and simultaneously completing ball milling dispersion and surface modification.
On the other hand, the invention also provides application of the silicon carbide chemical mechanical polishing solution with improved pH stability in silicon carbide polishing.
The polishing solution has very high removal rate to the Si surface and the C surface of the SiC monocrystal, the Si surface is 0.5-1.5 mu m/hr, the C surface is 3.5-6 mu m/hr, the roughness Ra of 10 multiplied by 10 mu m is detected by an atomic force microscope to be less than 0.1nm, the pH of the polishing solution is changed from 3.6 to 3.9, and the pH of the polishing solution without adding aluminum nitrate is changed to 5.6.
The invention has the following beneficial effects:
1. the inorganic aluminum nitrate is used as the pH stabilizer and can play a role of a dispersion stabilizer, so that the polishing solution can well keep the stability of the pH value in the chemical mechanical polishing process, and the polishing solution has good dispersion stability and uniform dispersion.
2. The aluminum nitrate can play a role in stabilizing and buffering pH on one hand, and Al on the other hand3+Can simultaneously stabilize the oxidation of the chips thrown off in the polishing process and the potassium permanganate to form manganese oxide (such as MnO)2) Thereby reducing the influence of 'impurities' formed in the polishing process on the stability of the polishing solution.
3. According to the invention, the organic acid is used for carrying out surface modification on the abrasive particles, so that the abrasive particles only undergo soft agglomeration, the hard agglomeration of the particles is reduced, and the dispersion uniformity and stability of the alumina abrasive particles are enhanced.
4. The polishing solution of the invention has no pollution to the environment and can be used in a circulating feeding mode.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows the morphology of a silicon carbide surface polished by a polishing solution without aluminum nitrate;
FIG. 2 shows the surface morphology of a silicon carbide surface polished by the polishing solution with aluminum nitrate added according to the present invention;
FIG. 3 is an atomic force microscope image of silicon carbide polished using a polishing solution with added aluminum nitrate in accordance with the present invention;
FIG. 4 is a graph of alumina stability over time after the addition of silica without the addition of aluminum nitrate;
FIG. 5 is a graph of alumina stability over time after the addition of silica with the addition of aluminum nitrate in accordance with the present invention;
FIG. 6 shows the variation of the alumina particle size with the silica concentration before and after the addition of aluminum nitrate according to the present invention, (a)20nm and (b)4 nm;
FIG. 7 is a graph of the alumina particle size and potential as a function of ascorbic acid concentration after ascorbic acid addition without aluminum nitrate addition;
FIG. 8 is a TSI change for the alumina system after addition of ascorbic acid without addition of aluminum nitrate;
FIG. 9 is a graph of the alumina particle size and zeta potential as a function of ascorbic acid concentration for aluminum nitrate in accordance with the alumina-manganese oxide system of the present invention;
FIG. 10 is a graph of the change in TSI of the alumina-manganese oxide system of the present invention after the addition of aluminum nitrate.
Detailed Description
In order to more clearly illustrate the overall concept of the present invention, the following detailed description is given with reference to the following specific examples, but not to limit the scope of the present invention.
Example 1:
a pH stable silicon carbide chemical mechanical polishing solution, the polishing solution comprising: 100ml of an acidic alumina dispersion having a concentration of 15%, 0.5% (based on the weight of alumina) of a surface-modifying organic acid, 0.05% (final concentration) of the pH stabilizer aluminum nitrate and 0.1% (final concentration) of the oxidizing agent potassium permanganate.
Example 2:
a pH stable silicon carbide chemical mechanical polishing solution, the polishing solution comprising: 100ml of an acidic alumina dispersion having a concentration of 25%, 2.0% (based on the weight of alumina) of a surface-modifying organic acid, 1.0% (final concentration) of the pH stabilizer aluminum nitrate and 4.0% (final concentration) of the oxidizing agent potassium permanganate.
Example 3:
a pH stable silicon carbide chemical mechanical polishing solution, the polishing solution comprising: 100ml of an acidic alumina dispersion having a concentration of 20%, 1.0% (based on the weight of alumina) of a surface-modifying organic acid, 0.08% (final concentration) of the pH stabilizer aluminum nitrate and 2.5% (final concentration) of the oxidizing agent potassium permanganate.
Example 4:
a pH stable silicon carbide chemical mechanical polishing solution, the polishing solution comprising: 100ml of an acidic alumina dispersion with a concentration of 22%, 1.2% (based on the weight of alumina) of a surface-modifying organic acid, 0.08% (final concentration) of the pH stabilizer aluminum nitrate and 1.5% (final concentration) of the oxidizing agent potassium permanganate.
Example 5:
the preparation method of the silicon carbide chemical mechanical polishing solution with stable pH value comprises the following steps:
(1) providing an acidic alumina dispersion: dispersing 15 g of alumina powder with the particle size of 100nm in 100ml of water, adjusting the pH value to 0.5 by using nitric acid, and grinding for 5 hours by using a star-shaped ball mill to prepare an acidic alumina dispersion liquid with the pH value of 3.8;
(2) carrying out surface modification on the acidic alumina dispersion liquid by adopting organic acid through ball milling dispersion: adding 0.5% (based on the weight of alumina) of organic acid into the acidic alumina dispersion, and continuing to disperse for 3 hours by using a ball mill to obtain a modified acidic alumina dispersion;
(3) diluting the modified alumina dispersion liquid to 1.0%, adding nitric acid to adjust the pH value to 3.8, adding 0.05% of aluminum nitrate, and stirring and dispersing for 1.5 hours;
(4) adding 0.1 percent of potassium permanganate as an oxidant to prepare the silicon carbide chemical mechanical polishing solution with stable pH value.
Example 6:
a method for chemically-mechanically polishing a silicon carbide single crystal using a pH-stabilized silicon carbide chemical-mechanical polishing liquid, the polishing method comprising the steps of:
the polishing parameters were set to 30rpm for the polishing pad, 25rpm for the polishing head, 2 for the polishing pressure of 1.7kg/cm, and 4.5L/min for the polishing slurry flow rate. And (3) mixing the potassium permanganate solution with the alumina dispersion liquid in equal volume, and polishing the silicon carbide material for 30 min.
And detecting the morphology of the polished silicon carbide surface by using an optical surface measuring instrument and a surface defect detector, representing the surface roughness of the polished silicon carbide by using an atomic force microscope, and calculating the material removal rates of the Si surface and the C surface of the silicon carbide.
FIG. 1 shows the surface morphology of silicon carbide polished with a polishing solution without aluminum nitrate; FIG. 2 shows the surface morphology of silicon carbide polished with a polishing solution with added aluminum nitrate; figure 3 shows an atomic force microscope image of silicon carbide polished using a polishing solution with added aluminum nitrate. As seen from FIG. 1, aluminum nitrate is not added into the polishing solution, and the polished silicon carbide surface has obvious and many deep scratches; as seen from FIG. 2, the addition of aluminum nitrate to the polishing slurry resulted in a polished silicon carbide surface with few scratches and uniformity; as shown in fig. 3, when aluminum nitrate was added to the polishing liquid, the surface roughness of the polished silicon carbide was small.
Example 7:
the method for testing the influence of silicon oxide adsorption on the stability of aluminum oxide comprises the following steps:
preparing a silicon oxide solution with the concentration of 0.002 wt% -0.2 wt% and the particle size of 20nm, adjusting the pH value of the silicon oxide solution to 3-4 by using nitric acid, carrying out ultrasonic treatment, mixing the silicon oxide solution with 0.2 wt% of aluminum oxide solution in equal volume, standing, and observing the influence of the silicon oxide concentration on the system stability;
and (2) adding 0.4-4 wt% of aluminum nitrate solution into 0.4 wt% of aluminum oxide solution in an equal volume, stirring for 30min, mixing with the silicon oxide solution with the pH value of 3-4 in an equal volume, shaking for 3min, standing, and observing the influence of the added aluminum nitrate on the stability of the aluminum oxide-silicon oxide system.
FIG. 4 shows the stability of alumina over time after addition of silica without addition of aluminum nitrate, with the silica mass concentrations from left to right being 0, 0.001%, 0.003%, 0.005%, 0.008%, 0.01%, 0.03%, 0.05%, 0.08%, and 0.1%, respectively. The results show that, without the addition of aluminum nitrate, precipitation started after 15 minutes of adding silica to the alumina. In the range of low-concentration silicon oxide, silicon oxide is negatively charged, aluminum oxide is positively charged and mutually attracted, silicon oxide particles are adsorbed on the surfaces of aluminum oxide particles, the surface potential of the aluminum oxide is reduced, so that the electrostatic repulsion among the aluminum oxide particles is not enough to overcome the van der Waals attraction, the particles are aggregated, the adsorption quantity of the silicon oxide is increased along with the increase of the concentration of the silicon oxide, the surface potential of the aluminum oxide is reversed, the particles are negatively charged, the repulsion force is increased, and the particles are stably dispersed.
Fig. 5 shows the stability of alumina over time after addition of silica with addition of aluminum nitrate, with the silica mass concentrations from left to right being 0, 0.001%, 0.003%, 0.005%, 0.008%, 0.01%, 0.03%, 0.05%, 0.08%, and 0.1%, in that order. The results show that no significant precipitation was observed within 24 hours of the addition of alumina to silica after the addition of aluminum nitrate. The stability of an alumina-silica system can be obviously improved by adding the aluminum nitrate, the stability of the 20nm silica system is more obvious, and the system can be kept stable within 24 hours by adding the aluminum nitrate; and the particle size of the system is greatly reduced by adding the aluminum nitrate. When the aluminum nitrate is not added, when the concentration of the silicon oxide is 0.003 to 0.01 weight percent, the particles are quickly aggregated, and the particle size of the system cannot be measured by dynamic light scattering, but when 0.1 weight percent of the aluminum nitrate is added, the system can be stably dispersed within 24 hours, and the stability is obviously improved. The TSI after the aluminum nitrate is added can be obviously reduced by measuring the system instability index TSI after the aluminum nitrate is added by a stability analyzer, which shows that the dispersion stability of the alumina-silica system is greatly improved by adding the aluminum nitrate. For the reason that aluminum nitrate can improve the stability of the system, aluminum nitrate is adsorbed on the surface of silica particles, and the surface charge of silica is neutralized or reversed, thereby reducing the electrostatic attraction between silica and alumina, and thus enabling the particles to be stably dispersed.
Example 8:
a method for testing the influence of the generation of a manganese compound on the stability of a system (a reducing agent ascorbic acid is added to simulate the oxidation of potassium permanganate in a polishing process), which comprises the following steps:
and (1) mixing 0.2 wt% of alumina and 0.02M potassium permanganate in equal volume, adding a small amount of ascorbic acid into the mixture, carrying out redox reaction on the ascorbic acid and the potassium permanganate to generate a Mn compound, and observing the influence of the addition of the acid-resistant ascorbic acid and the generation of a manganese oxide on the stability of an alumina system.
Step (2), mixing 0.4 wt% of aluminum oxide solution and 0.4 wt% of aluminum nitrate solution for 30min in equal volume, mixing with 0.02M potassium permanganate solution in equal volume, adding a small amount of ascorbic acid by using a 25 mu l pipette, and controlling the concentration of ascorbic acid in the final system to be 1X 10-8M、5×10-8M、1×10-7M、5×10-7M、1×10-6M, pH 3.5-4, the experiment was performed at room temperature. The effect of the addition of aluminum nitrate on the stability of the alumina-manganese oxide system was observed.
In the system, aluminum nitrate is not added, and the change of the particle size and the potential of the alumina after adding the ascorbic acid along with the concentration of the ascorbic acid, the TSI (instability index) of the alumina system after adding the ascorbic acid and the sedimentation observation of the alumina system after adding the ascorbic acid are studied, wherein the concentration of the ascorbic acid is 10 respectively-8M、5×10-8M、10-7M、5×10-7M and 10-6And M. Fig. 7 shows the particle size and potential of alumina as a function of ascorbic acid concentration after ascorbic acid addition, and fig. 8 shows the TSI of the alumina system after ascorbic acid addition. It is found from experiments that the amount of manganese oxide formed increases with the increase in the concentration of ascorbic acid, the particle size of alumina gradually increases, and the system stability gradually decreases. When the concentration of ascorbic acid is 10-7At M, the particle size sharply increased and significant sedimentation was observed after 1 hour. 0.01M potassium permanganate did not cause precipitation of alumina particles, whereas the ascorbic acid concentration was only 10 after addition of ascorbic acid-7And when M is used, the alumina can be precipitated within 4 hours, which shows that the reaction of the ascorbic acid and the potassium permanganate generates manganese oxide to cause the precipitation of alumina particles. According to the potential, the generated manganese oxide is negatively charged and can be adsorbed on the surface of the alumina to shield the surface charge of the alumina, so that the particles are aggregated.
Adding aluminum nitrate into the system, and studying the change of the particle size and zeta potential of aluminum oxide with the concentration of ascorbic acid after adding ascorbic acid, adding ascorbic acidTSI (instability index) of the post-alumina system and sedimentation of the alumina system after addition of ascorbic acid, wherein the concentration of ascorbic acid is 10 in each case-8M、5×10-8M、10-7M、5×10-7M、10- 6M、5×10-6M、10-5M、5×10-5M、10-4M、5×10-4And M. After mixing aluminum oxide and aluminum nitrate, the mixed solution was mixed with potassium permanganate in equal volume, ascorbic acid was added thereto, and the influence of the addition of aluminum nitrate on the system stability was observed. FIG. 9 is a plot of alumina particle size and zeta potential as a function of ascorbic acid concentration for an alumina-manganese oxide system with aluminum nitrate added, and FIG. 10 is a plot of TSI for an alumina-manganese oxide system with aluminum nitrate added. It was found that as the concentration of ascorbic acid increased, the alumina particle size gradually increased, the potential gradually decreased (but always positive, see fig. 9), and the TSI gradually increased, indicating a gradual decrease in system stability. However, compared with the solution without the aluminum nitrate, the particle size of the solution added with the aluminum nitrate is reduced and the TSI is reduced under the condition of the same ascorbic acid concentration, which shows that the stability of the system is obviously improved by adding the aluminum nitrate. As can be seen from the results of the sedimentation, when the ascorbic acid concentration was 10-6In the case of M, precipitation appeared after half an hour in the system without adding aluminum nitrate, while no precipitation was found within 6 hours after adding aluminum nitrate. After adding aluminum nitrate, the ascorbic acid concentration was 10-4M, precipitation occurred, two orders of magnitude higher than without the addition of aluminum nitrate solution (see figure 10).
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only an example of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims (10)

1. A silicon carbide chemical mechanical polishing solution with improved pH stability, the polishing solution comprising: the polishing solution comprises an oxidant, a high-hardness abrasive, a surface modifier of the high-hardness abrasive and a pH stabilizer, wherein the oxidant is potassium permanganate, the high-hardness abrasive is acidic alumina dispersion liquid with the concentration of 10-30%, the surface modifier is acetic acid and/or propionic acid, the pH stabilizer is aluminum nitrate, the removal rate of the polishing solution to the Si surface of the SiC single crystal is 0.5-1.5 mu m/hr, and the removal rate of the polishing solution to the C surface of the SiC single crystal is 3.5-6 mu m/hr; wherein the final concentration of the aluminum nitrate is 0.01-5%, the final concentration of the oxidant is 0.01-10%, and the dosage of the surface modifier is 0.5-2.0% of the weight of the aluminum oxide; the pH value of the polishing solution is 3.5-4.
2. The silicon carbide chemical mechanical polishing solution of claim 1, wherein the high hardness abrasive has a Zeta potential greater than +30 mv.
3. The silicon carbide chemical mechanical polishing solution according to claim 1, wherein the alumina is high-hardness alpha-alumina having a mohs hardness of 9.0, or transition phase alumina.
4. The silicon carbide chemical mechanical polishing solution according to claim 3, wherein the transition phase alumina is one or more of theta-alumina, gamma-alumina, kappa-alumina and alumina.
5. The silicon carbide chemical mechanical polishing solution according to claim 1, wherein the final concentration of the aluminum nitrate is 0.05 to 1%.
6. The silicon carbide chemical mechanical polishing solution according to claim 1, wherein the final concentration of the oxidizing agent is 0.1 to 4%.
7. The silicon carbide chemical mechanical polishing solution of claim 1, wherein the polishing solution further comprises a surfactant, a corrosion inhibitor, a defoaming agent, a brightening agent, a viscosity modifier or a polymer dispersant.
8. The silicon carbide chemical mechanical polishing solution according to claim 1, wherein the high hardness abrasive is an acidic alumina dispersion having a concentration of 15 to 25%, and the surface modifier is used in an amount of 1.0 to 1.5% by weight based on the weight of alumina.
9. The silicon carbide chemical mechanical polishing solution according to claim 1, wherein the polishing solution is prepared by the following method: (1) providing an acidic alumina dispersion; (2) surface modification is carried out on the acidic alumina dispersion liquid by adopting a surface modifier; (3) adjusting the pH value to 3.5-4, adding a pH value stabilizer, stirring and dispersing; (4) adding an oxidant to prepare the silicon carbide chemical mechanical polishing solution with improved pH stability.
10. Use of the silicon carbide chemical mechanical polishing solution with improved pH stability of any one of claims 1-9 in silicon carbide polishing.
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