CN113755099A - Sapphire chemical mechanical polishing solution and application thereof - Google Patents
Sapphire chemical mechanical polishing solution and application thereof Download PDFInfo
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- CN113755099A CN113755099A CN202010460641.0A CN202010460641A CN113755099A CN 113755099 A CN113755099 A CN 113755099A CN 202010460641 A CN202010460641 A CN 202010460641A CN 113755099 A CN113755099 A CN 113755099A
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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
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- 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
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
Abstract
The invention discloses a sapphire chemical mechanical polishing solution and application thereof, wherein the polishing solution comprises the following components in percentage by weight: 10-50% of silica sol, 1-10% of pH regulator, 0.1-3% of surfactant, 0.1-5% of manganese-containing complex and the balance of deionized water, wherein the pH value of the polishing solution is 8-12. The polishing solution composition has the characteristics of high polishing rate, good surface quality, easiness in cleaning, good storage stability and the like by adding the manganese-containing complexing agent.
Description
Technical Field
The invention relates to a sapphire planarization technology, in particular to a sapphire chemical mechanical polishing solution composition and application thereof in processing of a sapphire wafer.
Background
Single crystal sapphire (main component is alpha-Al)2O3) Because of its excellent mechanical property, dielectric property, chemical stability, thermal conductivity and high surface smoothness, it is widely used in the technical fields of military, aerospace, information, optics, superconduction, etc., and becomes the best quality substrate and substrate material for preparing high-temperature superconducting thin film, infrared optical material, microelectronic device, etc. At present, the surface processing quality (such as surface roughness, microcracks, scratches and dislocations) and the processing precision of the sapphire window of a military high-performance infrared detector and the substrate of a gallium nitride-based blue LED and a laser diode have a crucial influence on the epitaxial growth quality of materials and the performance of devices. Sapphire materials are typical difficult-to-process materials because of extremely high hardness, the mohs hardness of which reaches 9, which is second to diamond, and the brittleness of the sapphire materials is high. Therefore, in order to meet the important requirements of the defense advanced technology and the electronic information manufacturing industry, the realization of efficient and ultra-precise processing and manufacturing of sapphire is very important.
The processing procedures of the prior industrial production of sapphire comprise crystal bar cutting, double-sided grinding, single-sided grinding, copper polishing, Chemical Mechanical Polishing (CMP) and the like, wherein the CMP is used as the last procedure of substrate processing, and the quality of the polishing quality directly determines the performance and the service life of the product. CMP is widely used in the fields of semiconductors, microelectronics, optoelectronics, and the like, achieves an ultra-smooth surface of a wafer through the synergistic effect of mechanical removal and chemical corrosion, and is currently the only ultra-precision processing technology capable of achieving global planarization.
Chemical Mechanical Polishing (CMP) is a technique that combines chemical polishing and mechanical polishing to process a surface of a material. On the basis of mechanical polishing, corresponding chemical additives are added according to polishing materials so as to achieve the effect of enhancing the polishing efficiency or improving the polishing surface. Chemical mechanical polishing is by far the only global planarization method that can be applied in the mass production of integrated circuit substrates. The polishing yield of sapphire, ceramic and stainless steel and the yield of the next process are directly influenced by the quality of the polishing quality. In chemical mechanical polishing, the polishing liquid is one of the factors directly affecting the polishing effect. The quality of the polishing solution directly affects the service life, polishing efficiency and product yield. A good polishing solution should have high cycling stability, fast polishing rate, and high surface quality. However, the existing polishing solution mainly has the problems of unstable speed, low polishing speed, poor surface quality and the like during the polishing cycle.
Generally, the quality of the polishing solution is directly related to the type, size and concentration of the abrasive. At present, the most common three abrasives for polishing the sapphire substrate are diamond, silica sol and alumina. Diamond is very hard and even if the particles reach the nanometer level, the diamond can cause serious scratch on the surface of the crystal. The diamond powder is mainly applied in the rough grinding stage, and the damage layer on the surface of the substrate is removed mainly through mechanical action. alpha-Al2O3The preparation process needs high-temperature calcination of more than 1000 ℃, which causes the defects of high alumina hardness, poor dispersibility and the like, the abrasive is difficult to stably and uniformly disperse in the polishing solution, so that the abrasive is easy to agglomerate together to scratch a substrate during polishing, and the defects seriously hinder oxygenUse of aluminium oxide for polishing a sapphire substrate. The most commonly used polishing solution for sapphire substrates is a silica sol polishing solution, which is used for rough polishing or grinding of sapphire. The most widely used method in the final chemical mechanical polishing of sapphire is an alkaline silica sol solution, the silica sol used in the final chemical mechanical polishing process is a silica dispersion, and the silica particles are generally synthesized at a low temperature of about 100 ℃ and have far lower hardness than sapphire crystals. Because of low-temperature synthesis, the polishing solution generally does not contain super-large particles, is not easy to scratch the polished surface of a sapphire crystal, has good suspension performance and convenient use, and has low price, but the silica sol polishing solution has the biggest defects of low polishing efficiency and long polishing time; in addition, the silica sol polishing solution is easy to gel when heated in the polishing process, is easy to air-dry on the surface of the sapphire, and is not suitable for subsequent cleaning.
Chinese patent CN101230239B discloses a high-efficiency high-precision sapphire polishing solution, which comprises nano silica sol with the particle size of 15-80 nanometers, complexing agent and surfactant, and the pH value is 10-11. The product has low solid content, high polishing efficiency and strong stability, is not suitable for being deposited on the surfaces of a polishing machine and a polished product, and has unique fluid performance, so that the sapphire surface is not suitable for being air-dried after polishing, and the burden of a subsequent cleaning process is greatly reduced. The patent realizes optimal polishing performance by controlling the conductivity of the polishing solution by adjusting the pH value by using an organic amine compound-free compound. However, this patent does not add an organic base, which makes the pH of the slurry unstable.
Chinese patent application CN106147615A discloses a ceramic polishing solution containing iron catalyst for sapphire polishing, which is characterized in that: comprising 1) water, 2) a hard abrasive having a mohs hardness of greater than 7; 3) an iron-containing catalyst; 4) and the surfactant is used for regulating the pH value to be 12.0-13.5 by using a pH regulator. According to the method, hydration of the sapphire surface is enhanced by using the iron-containing catalyst, the hard sapphire surface is softened, efficient and high-quality sapphire surface polishing is realized, and the polishing solution taking alumina as an abrasive can be redispersed after being air-dried and is recycled without causing scratches. Meanwhile, the aluminum oxide is not chemically bonded with the surface of the sapphire, so that the burden of a subsequent cleaning process is greatly reduced. The ceramic polishing solution adopts alumina as an abrasive and is added with an iron-containing catalyst. However, the alumina powder is not easy to disperse in the polishing solution and is easy to agglomerate together, which causes scratches on the surface and influences the surface quality.
Chinese patent application CN110003797A also discloses a sapphire rough polishing solution, in which Fe ion complexing agent is added. Although the polishing rates of the two prior art patents are improved, the Fe ions have a certain electrophilic neutralization effect on the silica sol with a large amount of negative charges on the surface, so that the long-term stability storage of the polishing solution is influenced, and the sapphire polishing is affected very adversely at a later stage. It is therefore highly desirable to provide a polishing solution that can increase the polishing rate and reduce the crystallization of silica sol to reduce scratching of sapphire substrates, while satisfying the need for long-term storage.
Disclosure of Invention
In view of the above disadvantages of the prior art, an object of the present invention is to provide a chemical mechanical polishing solution for sapphire, which is used to solve the problems of the prior art, such as low polishing efficiency, difficulty in subsequent cleaning process due to easy air drying on the sapphire surface, and poor stability during long-term storage.
In order to achieve the above purpose, the technical scheme adopted by the sapphire chemical mechanical polishing solution composition of the invention is as follows:
the chemical mechanical polishing solution for sapphire is characterized by comprising the following components in percentage by weight:
wherein the silica sol is a dispersion of silica in water, and the content of the silica sol is 20-40%.
Wherein the particle size of the silica sol is 50-150 nm, preferably 80-120 nm.
Wherein, the content of the pH regulator is 3 to 8 percent.
Wherein the pH regulator is selected from one or more of ethylenediamine, hydroxyethyl ethylenediamine or tetramethylammonium hydroxide.
Wherein the pH value of the chemical mechanical polishing solution is 8-12.
Wherein the surfactant is selected from one or more of sodium polyoxyethylene sulfate, polyoxyethylene ether phosphate, alkyl alcohol polyoxyethylene ether or polyvinylpyrrolidone.
Wherein, the content of the manganese-containing complex is 1 to 4 percent.
Wherein, the manganese-containing complex is selected from any one or more of EDTA manganese complex, citric acid manganese complex and diethanolamine manganese complex.
In another aspect, the invention relates to the application of the sapphire chemical mechanical polishing solution in sapphire wafer processing.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the sapphire chemical mechanical polishing solution, the chemical action and the mechanical action are basically balanced when the polishing solution is used through selection of the specific abrasive grain diameter and the silica sol content, the material removal rate is high, and the surface quality is best.
2) According to the sapphire chemical mechanical polishing solution disclosed by the invention, the specific surfactant is added, so that the surface tension of the solution can be reduced, the fluidity of the polishing solution is improved, colloidal particles are uniformly dispersed, and the stability of a colloidal system is improved. The polishing liquid is beneficial to enhancing the lubricating property of the polishing liquid in the polishing process, and the evaporation of water caused by frictional heat is reduced, so that the crystallization speed of silicon dioxide is relieved, the scratch of a sapphire wafer by silicon dioxide crystals is relieved, the crystallization of the polishing liquid on a machine table is also reduced, the time for cleaning the machine table is reduced, and the production efficiency is improved.
3) According to the sapphire chemical mechanical polishing solution, the complexing agent contains oxygen, nitrogen, sulfur and other atoms, lone pair electrons can be provided, the metal ions can provide empty orbitals, and the complexing agent and the metal ions are combined to form a ligand complex. The complex can adsorb free metal ions, and avoid serious damage of the metal ions to the substrate. Because the free metal ions can cause very small debris and broken abrasive particles to clump together, clogging the polishing pad and affecting the polishing performance. On one hand, the complexing agent containing the manganese element can weaken the bond energy of Al-O bonds, so that the sapphire is softened, and the polishing rate is favorably improved; on the other hand, the manganese ions have a catalytic action, and are beneficial to improving the reaction of the aluminum oxide and the alkaline substances, so that the polishing rate is effectively improved; meanwhile, the complexing agent containing manganese is added, so that the electrophilic neutralization performance of Fe ions is weakened, and the long-time storage stability of the polishing solution is improved.
Drawings
FIG. 1 is a graph showing a comparison of polishing performance of sapphire polishing solutions of examples of the present invention and comparative examples.
Detailed Description
The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims.
The chemical mechanical polishing solution for sapphire is characterized by comprising the following components in percentage by weight:
in a preferred embodiment, the silica sol is a dispersion of silica in water, wherein the silica solids content can be tailored as desired, for example, from 40 to 50%, and the polishing liquid abrades the particle size of the silica sol and its weight percentage to affect the polishing rate and surface quality. The weight percentage of the abrasive is within a proper range, the polishing removal rate is increased with the increase of the weight percentage of the abrasive, but the weight percentage of the abrasive cannot be too large, and the viscosity of the polishing solution is too large and the fluidity of the polishing solution is poor after the weight percentage of the abrasive is too large. The content of the silica sol of the present invention is 10% to 50%, such as 10%, 20%, 30%, 40%, 50%, but not limited thereto, and may be 15%, 25%, 35%, 45%, etc.; more preferably 20% to 40%, such as 20%, 30%, 40%, but not limited thereto.
In terms of abrasive grain size, when polishing pressure is constant, the effective contact area between the wafer and the polishing pad is reduced due to the excessively large abrasive grain size, the pressure born by a single abrasive will be increased, the depth of cut of the abrasive is increased, and the surface quality of the wafer is deteriorated. When the abrasive particle size is too small, the mechanical action is weaker than the chemical action, resulting in a decrease in polishing efficiency. The inventors of the present invention have found through creative experiments that, in the polishing composition system of the present invention, the average particle size of the abrasive is selected to be 50 to 150nm, such as 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, or 55nm, 65nm, 75nm, 85nm, 95nm, 105nm, 115nm, 125nm, 135nm, 145nm, but not limited thereto; preferably 80 to 120nm, such as 80nm, 90nm, 100nm, 110nm, 120nm, and may be 85nm, 95nm, 105nm, 115nm, but is not limited thereto. Under the conditions of the abrasive grain size and the silica sol content, in the composite system of the surfactant, the manganese-containing complex, the pH value regulator and the like, the chemical action and the mechanical action are basically balanced, the removal rate of the polished material is high, and the surface quality is best.
In a preferred embodiment, the content of the pH regulator is 3% -8%, and the pH value of the chemical mechanical polishing solution is regulated to be in a range of 8-12. The sapphire has a composition of alpha-Al2O3It is an amphoteric oxide which can react with both acid and base. However, the acidic polishing solution is easy to corrode equipment, and heavy metal ions are introduced in the polishing process, so that the performance and the service life of the LED device are affected. The alkali in the alkaline polishing solution can chemically react with the aluminum oxide, and the stronger the alkali, the faster the chemical reaction rate, and the higher the material removal rate. During the polishing process, the pH value of the polishing solution is gradually reduced along with the increase of the polishing time. The decrease in pH weakens the chemical action of the slurry, resulting in a decrease in polishing rate. The pH regulator is added into the polishing solution, so that the reduction of the pH value can be effectively slowed down, and the stable polishing rate of the polishing solution is ensured. The pH regulator of the present invention is selected from ethylenediamine, hydroxyethylethylenediamine or tetramethylethylenediamineAny one or more of ammonium hydroxide. For example, one of ethylenediamine, hydroxyethylethylenediamine, and tetramethylammonium hydroxide, or a mixture of any two or three of them is selected. Particularly, the invention avoids the influence of metal ions such as Ca, Na and the like in the sapphire crystal lattice in the processing process by adopting inorganic alkali; in contrast, the sapphire chemical mechanical polishing solution system of the invention is added with a specific organic base, so that the pH value of the polishing solution system is more stable.
In a preferred embodiment, the surfactant is selected from any one or more of sodium polyoxyethylene sulfate, polyoxyethylene ether phosphate, alkyl alcohol polyoxyethylene ether or polyvinylpyrrolidone, and the weight percentage is preferably 0.5-2% of the polishing solution. The surfactant is a high molecular substance with one end containing a hydrophilic group and the other end containing a hydrophobic group, and can reduce the surface tension of the solution, improve the fluidity of the polishing solution, uniformly disperse colloidal particles and improve the stability of a colloidal system. The lubricating property of the polishing solution is enhanced in the polishing process, the evaporation of water caused by frictional heating is reduced, and the crystallization speed of silicon dioxide is relieved, so that the scratch of silicon dioxide crystals on sapphire wafers is relieved on one hand, the crystallization of the polishing solution on a machine table is also reduced on the other hand, the time for cleaning the machine table is shortened, and the production efficiency is improved.
In a preferred embodiment, the complexing agent is selected from any one or more of manganese EDTA complex, manganese citrate complex and manganese diethanolamine complex, and the weight percentage of the complexing agent is preferably 1-4% of the polishing solution. The complexing agent contains oxygen, nitrogen, sulfur and other atoms, can provide lone pair electrons, and metal ions can provide empty orbitals, so that the complexing agent and the metal ions are combined to form a ligand complex. The complex can adsorb free metal ions, and avoid serious damage of the metal ions to the substrate. Because the free metal ions can cause very small debris and broken abrasive particles to clump together, clogging the polishing pad and affecting the polishing performance. On one hand, the complexing agent containing the manganese element can weaken the bond energy of Al-O bonds, so that the sapphire is softened, and the polishing rate is favorably improved; on the other hand, the manganese ions have a catalytic action, and are beneficial to improving the reaction of the aluminum oxide and the alkaline substances, so that the polishing rate is effectively improved; in addition, the complexing agent containing manganese is added, so that the electrophilic neutralization performance of Fe ions is weakened, and the long-term storage stability of the polishing solution is improved.
Specifically, the preparation method of the sapphire chemical mechanical polishing solution comprises the following steps: uniformly dispersing a certain solid content of silica sol in half (half of the desired deionized water amount in the sapphire polishing composition) of deionized water, wherein the solution is called A; then slowly adding a complexing agent containing manganese into the other half of deionized water, stirring for 5min, adding a surfactant, stirring for 5min, then adding a proper amount of pH regulator to enable the pH value to be within the range of 8-12, and stirring for 5min, wherein the solution is called B; and slowly adding the solution B into the solution A, and stirring for 30min to obtain the sapphire chemical mechanical polishing solution composition. The appropriate amount of the pH regulator can be selected from pH regulators with different concentrations according to requirements, and the pH value of the composition system is adjusted to 8-12 on the basis of ensuring the content of the pH regulator to be in a target range.
In the chemical mechanical polishing process, a wax-free adsorption pad with the same diameter as the polishing head is attached to the polishing head. The wax-free adsorption pad is provided with three round holes with the diameter of 2 inches, the depth of each round hole is about half of the thickness of the sapphire substrate sheet with the diameter of 2 inches, and the sapphire substrate sheet is adsorbed on the wax-free adsorption pad through the capillary action. The method comprises the steps that a polishing pad of suba600 is attached to the surface of a polishing disc, one surface, attached with a wafer, of a wax-free adsorption pad is placed downwards on the polishing pad, a sapphire substrate sheet and the polishing pad are tightly combined together through the downward pressure of the polishing head and rotate in the same direction at different rotating speeds, and meanwhile, silica sol polishing solution is sprayed on the surface of the polishing pad and is prepared from silica sol and water according to a certain proportion. In the polishing process, polishing liquid is sprayed on the upper surface of the polishing pad, so that the polishing effect is achieved, the cooling effect is achieved, and the temperature of the lower disc surface of the polishing machine is controlled to be 30-40 ℃; and after polishing, taking down the ceramic disc, and washing and cleaning the polishing pad by using a brush.
The reasonable selection of the polishing process parameters has an important influence on the sapphire polishing effect. With the increase of the polishing pressure, the contact area between the polishing pad and the sapphire surface is increased, so that the friction force between the polishing pad and the sapphire surface is increased, the mechanical action is strengthened, and the material removal rate is increased. However, the polishing pressure should not be too high, and the too high pressure will prevent the polishing solution from entering into the gap between the substrate surface and the polishing pad, so that the thickness of the chemical reaction layer is reduced, the chemical reaction process is inhibited, and the material removal rate is reduced.
In addition, as the rotating speed is increased, the friction action between the abrasive and the surface of the sapphire is enhanced, the mechanical action is enhanced, and the material removal rate is increased. However, the excessive rotation speed causes the waste of the polishing solution, the polishing solution cannot react with the substrate sufficiently, i.e., the polishing solution is thrown away from the reaction zone under the action of centrifugal force, the generation of a chemical reaction layer is hindered, and the material removal rate is reduced.
Polishing conditions of the examples of the present invention:
UNIPOL-1200S of automatic Shenyang Kejing grinder of polishing machine
Polishing pad Suba600
Pressure 300g/cm2
Flow rate of polishing solution is 100mL/min
Polishing time 40min
Polishing head/disk rotation speed 60/50rpm
After the sapphire is subjected to chemical mechanical polishing, the thickness difference and the mass difference before and after the sapphire is polished are measured by a thickness gauge and a balance to evaluate the polishing rate, and the sapphire substrate is measured by an atomic force microscope to obtain the roughness Ra value. And the storage stability of the polishing solution is explored by testing the particle size of the polishing solution after the polishing solution is placed for one month at the temperature of 60 ℃, and evaluating the dispersion uniformity of the polishing solution according to the solid contents of the upper layer and the lower layer of the polishing solution. The above testing methods all adopt industry standard processes, and are not described herein.
The technical solution of the present invention will be further described with reference to the following embodiments.
Wherein, the silica sol is purchased from domestic enterprises for producing the silica sol in Hubei longitude and latitude, the purity of other reagents is analytically pure, and the water is deionized water.
Example 1
The sapphire chemical mechanical polishing solution consists of the following components:
40 wt% of silica sol and 80nm of particle size; 3 wt% of hydroxyethyl ethylenediamine; 2 wt% of polyoxyethylene ether phosphate; 2 wt% of EDTA manganese complex; the balance being deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Example 2
The sapphire chemical mechanical polishing solution consists of the following components:
35 wt% of silica sol and 100nm of particle size; 5 wt% of ethylenediamine; sodium polyoxyethylene sulfate 0.5 wt%; manganese citrate complex 0.3 wt%; the balance being deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Example 3
The sapphire chemical mechanical polishing solution consists of the following components:
30 wt% of silica sol and 80nm of particle size; 4.5 wt% of tetramethylammonium hydroxide; polyvinylpyrrolidone 1.5 wt%; 1 wt% of manganese citrate complex; the balance being deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Example 4
The sapphire chemical mechanical polishing solution consists of the following components:
15 wt% of silica sol and 120nm of particle size; 8 wt% of tetramethyl ammonium hydroxide; 3 wt% of alkyl alcohol polyoxyethylene ether; 0.8 wt% of EDTA manganese complex; the balance being deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Example 5
The sapphire chemical mechanical polishing solution consists of the following components:
45 wt% of silica sol and 120nm of particle size; 6 wt% of hydroxyethyl ethylenediamine; polyoxyethylene ether phosphate 0.9 wt%; diethanolamine manganese complex 3 wt%; the balance being deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Example 6
The sapphire chemical mechanical polishing solution consists of the following components:
50 wt% of silica sol and 100nm of particle size; 4 wt% of ethylenediamine; sodium polyoxyethylene sulfate 1.8 wt%; 5 wt% of EDTA manganese complex; the balance being deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Example 7
The sapphire chemical mechanical polishing solution consists of the following components:
30 wt% of silica sol and 100nm of particle size; 10 wt% of hydroxyethyl ethylenediamine; 0.8 wt% of polyvinylpyrrolidone; 1 wt% of EDTA manganese complex; the balance being deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Example 8
The sapphire chemical mechanical polishing solution consists of the following components:
20 wt% of silica sol and 130nm of particle size; 6 wt% of hydroxyethyl ethylenediamine; polyoxyethylene ether phosphate 0.3 wt%; 0.6 wt% of diethanolamine manganese complex and the balance of deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Comparative example 1
The sapphire chemical mechanical polishing solution consists of the following components:
20 wt% of silica sol and 100nm of particle size; 4 wt% of ethylenediamine; sodium polyoxyethylene sulfate 0.4 wt%; the balance being deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Comparative example 2
The sapphire chemical mechanical polishing solution consists of the following components:
20 wt% of silica sol and 120nm of particle size; 8 wt% of tetramethyl ammonium hydroxide; 0.3 wt% of polyvinylpyrrolidone; 0.3 wt% of iron diethanolamine complex and the balance of deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
Comparative example 3
The sapphire chemical mechanical polishing solution consists of the following components:
25 wt% of silica sol and 110nm of particle size; 14 wt% of hydroxyethyl ethylenediamine; 1 wt% of polyoxyethylene ether phosphate; 1 wt% of EDTA iron complex and the balance of deionized water. The removal rate, the roughness, the solid content of the upper layer and the solid content of the lower layer of the polishing solution used in the embodiment were tested according to the polishing conditions and methods of the foregoing embodiments, and the polishing efficiency of the polishing solution was evaluated; and after the polishing solution is placed at the temperature of 60 ℃ for one month, the corresponding parameters are tested again, and the stability of the polishing solution is evaluated.
The polishing performance data of the sapphire polishing solutions of the examples and comparative examples of the present invention are shown in fig. 1. As can be seen from the results of FIG. 1, the sapphire polishing composition of the present invention has a high polishing average rate, a low surface roughness, and good storage stability, which are obtained by combining the components in a specific ratio. As can be seen from the above examples 1 to 8 and comparative example 1, examples 1 to 8 have higher removal rate and lower roughness, indicating that the addition of the manganese-containing complexing agent can significantly increase the polishing rate of the sapphire wafer and reduce the surface roughness. As can be seen from the above examples 1 to 8 and comparative examples 2 and 3, after the examples 1 to 8 were left at 60 ℃ for one month, the difference between the solid content of the upper layer and the solid content of the lower layer was small, and the total had a higher removal rate and a lower roughness, indicating that the addition of the manganese complexing agent had a better polishing effect than the addition of the iron complexing agent and that the long-term stability was more excellent. On the one hand, the manganese ions have a catalytic effect and are beneficial to improving the reaction of alumina and alkaline substances, so that the polishing rate is effectively improved; on the other hand, the addition of the complexing agent containing manganese weakens the electrophilic neutralization performance like Fe ions, and is beneficial to improving the long-term storage stability of the polishing solution.
Compared with the prior art, the polishing solution disclosed by the invention is used in the sapphire polishing process, and after a specific surfactant and a manganese-containing complexing agent are added, the lubricity among materials can be improved, and the loss of water due to friction is reduced, so that the crystallization of silica sol is reduced; the sapphire layer can be softened, the catalytic effect is achieved, the polishing speed is improved, metal ions can be adsorbed, and the damage of the metal ions to the substrate is avoided; but also can reduce the electrophilic neutralization and improve the stability of the polishing performance of the polishing solution stored for a long time.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. The chemical mechanical polishing solution for sapphire is characterized by comprising the following components in percentage by weight:
2. the chemical mechanical polishing solution for sapphire according to claim 1, wherein: the silica sol is a dispersion liquid of silicon dioxide in water, and the content of the silica sol is 20-40%.
3. The sapphire chemical mechanical polishing solution of claim 1 or 2, wherein: the particle size of the silica sol is 50-150 nm.
4. The chemical mechanical polishing solution for sapphire according to claim 1, wherein: the content of the pH regulator is 3-8%.
5. The sapphire chemical mechanical polishing solution of claim 1 or 4, wherein the pH regulator is selected from any one or more of ethylenediamine, hydroxyethylethylenediamine or tetramethylammonium hydroxide.
6. The chemical mechanical polishing solution for sapphire according to claim 5, wherein the pH value of the chemical mechanical polishing solution is in the range of 8 to 12.
7. The sapphire chemical mechanical polishing solution of claim 1, wherein the surfactant is selected from one or more of sodium polyoxyethylene sulfate, polyoxyethylene ether phosphate, alkyl alcohol polyoxyethylene ether, and polyvinylpyrrolidone.
8. The sapphire chemical mechanical polishing solution of claim 1, wherein the manganese-containing complex is present in an amount of 1% to 4%.
9. The sapphire chemical mechanical polishing solution of claim 1 or 8, wherein the manganese-containing complex is selected from any one or more of manganese EDTA complex, manganese citrate complex and manganese diethanolamine complex.
10. Use of the sapphire chemical mechanical polishing solution of any one of claims 1-9 in sapphire wafer processing.
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