CN117821016A - Abrasive particles for chemical mechanical polishing and method for preparing same - Google Patents

Abrasive particles for chemical mechanical polishing and method for preparing same Download PDF

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CN117821016A
CN117821016A CN202311823699.7A CN202311823699A CN117821016A CN 117821016 A CN117821016 A CN 117821016A CN 202311823699 A CN202311823699 A CN 202311823699A CN 117821016 A CN117821016 A CN 117821016A
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abrasive particles
solution
porphyrin
ions
polishing
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苏宏久
陈伟琴
张向阳
杜全心
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Yongjiang Laboratory
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Yongjiang Laboratory
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Abstract

The invention belongs to the field of polishing, and provides an abrasive particle for chemical mechanical polishing and a preparation method thereof, wherein the abrasive particle for chemical mechanical polishing comprises a nanoparticle inner core and a porphyrin structure electrically attracted to the surface of the nanoparticle inner core through a silane coupling agent with amino, and the porphyrin structure isM is an active component ion, R is:x, Y and Z are each independently selected from hydrogen, halogen, sulfonate, carboxyl, or hydroxyl, wherein R is an electrically attractive site. Thus, the abrasive particles have higher catalytic activity,the rate and effect of chemical mechanical polishing can be improved.

Description

Abrasive particles for chemical mechanical polishing and method for preparing same
Technical Field
The invention relates to the field of polishing, in particular to abrasive particles for chemical mechanical polishing and a preparation method thereof.
Background
Chemical mechanical planarization plays an important role in the processing of chips, and its main mode of action is that the surface of the substrate polishing member is in direct contact with the polishing pad and is in rotational motion relative to the polishing pad under a certain pressure. In this process, a polishing liquid containing solid particles is added between the polishing pad and the polishing member, and the surface planarization of the polishing member is achieved by chemical action and mechanical friction action. In abrasive particle-based mechanical polishing, coordination of the friction of the abrasive body and the catalysis of the surface is critical to achieving chemical and mechanical effects.
For example, polishing of metal W (tungsten) is a very important process, and the polishing process is mainly to form metal oxide by oxidation of a polishing liquid (using hydrogen peroxide in a Fenton reaction manner), and then remove the oxide therein by abrasive particles, thereby achieving polishing of metal W. However, the catalytic process of hydrogen peroxide is a complex chemical reaction process, and how to coordinate the relationship between chemical reaction and mechanical action is the key to realize efficient polishing process.
Accordingly, there is a need for improved abrasive particles for chemical mechanical polishing.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent.
In a first aspect of the present invention, there is provided an abrasive particle for chemical mechanical polishing comprising a nanoparticle core and a porphyrin-like structure electrically attracted to the surface of the nanoparticle core by a silane coupling agent having an amino group, the porphyrin-like structure beingM is an active component ion, R is: />X, Y and Z are each independently selected from hydrogen, halogen, sulfonate, carboxyl, or hydroxyl, wherein R is an electrically attractive site. Thus, the invention is used for chemical mechanical polishingThe abrasive particles are electrically attracted to the surface of the inner core through the silane coupling agent with amino and the R group (such as carboxyl) in the porphyrin structure to form a catalytic center, and the catalytic center can well coordinate chemical reaction and mechanical action in the polishing process, so that the abrasive particles have higher catalytic activity and can improve the polishing rate and effect in the chemical mechanical polishing process.
According to an embodiment of the invention, Z is selected from halogen, sulfonate, carboxyl or hydroxyl, X and Y are both hydrogen. Therefore, the porphyrin structure has higher spatial stability, and the polishing effect can be improved.
According to an embodiment of the present invention, M is selected from at least one of iron ion, manganese ion, copper ion, zinc ion, tin ion, cobalt ion, nickel ion, and hydrogen ion. Thus, the active component ions can be complexed with porphyrin, and the problem of pollution of polished samples caused by loss of the active component ions can be reduced.
According to an embodiment of the invention, the abrasive particles have a size of 10nm to 150nm. Thereby, the polishing rate is improved, and the risk of scratching the surface of the polished sample and the surface roughness are reduced.
According to an embodiment of the invention, the abrasive particles comprise solid spherical abrasive particles or solid profiled abrasive particles. Therefore, in the polishing process by using the abrasive particles, the morphology of the abrasive particles can be selected according to the application scene of the polishing piece. For example, more solid anisotropic abrasive particles can be adopted in the rough polishing process so as to improve the polishing rate; and after rough polishing, more solid spherical abrasive particles can be adopted to improve the surface flatness of the polishing piece and reduce scratches on the surface of the polishing piece.
According to an embodiment of the invention, the nanoparticle core comprises at least one of silica, alumina, ceria, zirconia, styrene, phenolic resin, urea-formaldehyde resin, polyurethane and polyacrylate.
In a second aspect of the invention, a method of making the abrasive particles of the first aspect of the invention is provided, comprising the steps of:
(1) Mixing an alkaline solution containing nanoparticles and a silane coupling agent with amino groups and performing first aging to obtain a solution A;
(2) Mixing and reacting the solution A with porphyrin reactant with the structure shown in formula 1 to obtain solution B;
(3) Mixing and second aging the solution B and the solution containing the active component ions to obtain a solution C containing abrasive particles;
(4) Subjecting the solution C to solid-liquid separation to obtain the abrasive particles.
According to the method, a silane coupling agent containing an amino group is introduced into the nano particles to carry out surface modification on the nano particles; then introducing porphyrin reactant, wherein functional groups (such as carboxyl) in the porphyrin reactant are combined with amino through electric attraction; then adding active component ions to complex with porphyrin to form the abrasive particles containing porphyrin structures. Thus, the surface of the inner core of the prepared abrasive particle is electrically attracted to the porphyrin structure to form a catalytic center by introducing the silane coupling agent containing the amino group, and the catalytic center can well coordinate chemical reaction and mechanical action in the polishing process, so that the abrasive particle has higher catalytic activity and can improve the polishing rate and effect in the chemical mechanical polishing process.
According to an embodiment of the present invention, in step (1), the pH of the alkaline solution is 8 to 10.5. Thus, the weakly alkaline conditions further promote surface modification of the nanoparticles.
According to an embodiment of the present invention, in step (1), the concentration of the nanoparticles in the alkaline solution is 2wt% to 10wt%. Thus, the uniform dispersion of the nano particles is facilitated.
According to an embodiment of the present invention, in step (1), the temperature of the first aging is 40 ℃ to 60 ℃ for 1.5h to 3h. Thus, during modification of the nanoparticle: on one hand, the agglomeration of nano particles can be reduced, so that the problem of scratch on the surface of a polishing piece in the later application process is reduced; on the other hand, the silane coupling agent and the nano particles can be bonded better, so that the complexation of active components in the later period is facilitated, and the active component ions can be complexed with porphyrin, so that the porphyrin structure and the inner core particles are tightly combined.
According to an embodiment of the present invention, in the step (1), the mass ratio of the nanoparticle to the silane coupling agent is 1: (0.01-2).
According to an embodiment of the invention, in the step (2), the temperature of the reaction is 70-95 ℃ and the time is 3-6 h. Thereby, the reaction efficiency is advantageously improved. Therefore, in the modification process of the nano particles, on one hand, the agglomeration of the nano particles can be reduced, and further the problem of scratch on the surface of a polishing piece in the later application process is reduced; on the other hand, the silane coupling agent with amino and the R group with porphyrin structure can be better electrically attracted.
According to an embodiment of the present invention, in step (2), the molar ratio of the porphyrin reactant to the silane coupling agent is (0.1-0.9) to 1.
According to an embodiment of the present invention, in step (3), the second aging temperature is 40 ℃ to 60 ℃ and the aging time is 1.5h to 3h. Thus, the active component is better complexed with the porphyrin structure while reducing the cost of preparing the abrasive particles.
According to an embodiment of the present invention, in step (3), the active component ions are provided by a solute including at least one of manganese acetate, ferric chloride, copper sulfate, zinc chloride, zinc sulfate, tin chloride, cobalt sulfate, nickel nitrate and cobalt chloride, and the concentration of the solute is 5wt% to 15wt%.
According to an embodiment of the invention, in step (3), the molar ratio of active component ions to porphyrin reactant is (1.1-1.3) to 1. Thus, the complexing effect of the active component ion (M) with the porphyrin reactant can be improved.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a schematic diagram of a process for preparing abrasive particles according to some embodiments;
FIG. 2 is a scanning electron microscope topography of the abrasive particles of example 1;
FIG. 3 is a scanning electron microscope topography of the abrasive particles of example 4;
fig. 4 is a scanning electron microscope topography of the abrasive particles of comparative example 1.
Detailed Description
Embodiments of the present invention are described in detail below. The embodiments described below are exemplary only for explaining the present invention and are not to be construed as limiting the present invention.
The inventor finds that the chemical oxidation of the metal W is most critical to the chemical mechanical polishing rate of the metal W, however, the Fenton reaction taking the conventional ferric nitrate and hydrogen peroxide as the system as homogeneous reaction can cause that the mechanical actions of abrasive particles are difficult to synchronize, so that the polishing efficiency of the metal W is greatly reduced, and in order to further improve the polishing efficiency, the concentration of the hydrogen peroxide is simply increased to cause corrosion of the metal W, thereby causing defects.
Accordingly, in a first aspect, the present invention provides an abrasive particle for chemical mechanical polishing comprising a nanoparticle core and a porphyrin-like structure electrically attracted to the surface of the nanoparticle core by a silane coupling agent having an amino group, the porphyrin-like structure beingM is an active component ion, R is: />X, Y and Z are each independently selected from hydrogen, halogen, sulfonate, carboxyl, or hydroxyl, wherein R is an electrically attractive site.
The abrasive particle for chemical mechanical polishing of the invention forms a catalytic center on the surface of the inner core through the electric attraction of the silane coupling agent with amino and the group (such as carboxyl) in the R in the porphyrin structure, and the catalytic center can well coordinate the chemical reaction and the mechanical action in the polishing process, so that the abrasive particle has higher catalytic activity and can improve the polishing rate and the polishing effect in the chemical mechanical polishing process. Specifically, based on the coordination of the chemical and mechanical action of the particles during chemical mechanical polishing, porphyrin species on the nanoparticle surface can adsorb oxygen and form linear oxygen, which has an oxidizing effect. In addition, the metal ions complexed by the porphyrin structure have strong catalytic action on polishing solution (such as polishing solution containing hydrogen peroxide), and can further improve the oxidizing capacity of Fenton reaction, so that the oxidizing property in the chemical mechanical polishing process of metal materials such as tungsten, copper and the like can be improved, and the polishing rate is further improved.
In the group R,representing a chemical bond.
In some embodiments, one of X, Y and Z is halogen, sulfonate, carboxyl, or hydroxyl, the remainder are all hydrogen.
Alternatively, Z is selected from halogen, sulfonate, carboxyl, or hydroxyl, and X and Y are both hydrogen. Therefore, the porphyrin structure has higher spatial stability and improves the polishing effect.
As an example, R is
In some embodiments, the abrasive particles have a size of 10nm to 150nm. Preferably 40nm to 80nm. Thereby, the polishing rate is improved, and the risk of scratching the surface of the polished sample and the surface roughness are reduced.
In some embodiments, the abrasive particles comprise solid spherical abrasive particles or solid anisotropic abrasive particles. In the polishing process using the abrasive particles, the morphology of the abrasive particles can be selected according to the application scenario of the polishing member. For example, more solid anisotropic abrasive particles can be adopted in the rough polishing process so as to improve the polishing rate; and after rough polishing, more solid spherical abrasive particles can be adopted to improve the surface flatness of the polishing piece and reduce scratches on the surface of the polishing piece.
In the invention, the selection basis of the active component ion M is as follows: the active component ions can be complexed with porphyrin, so that secondary pollution to a polished sample is avoided as much as possible in the polishing process.
In some embodiments, M is selected from at least one of iron ion, manganese ion, copper ion, zinc ion, tin ion, cobalt ion, nickel ion, and hydrogen ion. The active component ions can be complexed with porphyrin, and the problem of pollution of polished samples caused by loss of the active component ions can be reduced.
Optionally, the active component ion is an iron ion (Fe 3+ ). Thereby Fe (Fe) 3+ Can be used as a catalyst for Fenton reaction in the chemical mechanical polishing process to further catalyze chemical reaction so as to improve the chemical mechanical polishing rate.
Optionally, the active component ion is nickel ion (Ni 2+ )。
In some embodiments, the nanoparticle core comprises at least one of silica, alumina, ceria, zirconia, styrene, phenolic resin, urea-formaldehyde resin, polyurethane, and polymethacrylate. Thus, the kind of the nanoparticle can be selected according to the application scene of the abrasive particle.
Further, the nanoparticle core is silica. Therefore, the nano silicon dioxide surface has abundant hydroxyl groups, is easy to modify, thereby regulating and controlling chemical and physical properties, and the abundant hydroxyl groups are favorable for alkoxy (-OR) in the silane coupling agent 1 ) The hydroxyl groups formed by hydrolysis are condensed, so that the silane coupling agent is firmly bonded, and silicon dioxide is not easy to etch.
In the abrasive particles of the present invention, the electrical attraction by the silane coupling agent having an amino group means that the electrical attraction between the nanoparticle and the porphyrin structure is performed by the amino group and a group (such as a carboxyl group) in R of the porphyrin structure, wherein the bonding between the nanoparticle (such as silica) and the silane coupling agent is condensation between hydroxyl groups, and the porphyrin structure and the metal ion may be in a complexing manner.
In a second aspect of the invention, the invention provides a method of making the abrasive particles of the first aspect of the invention, comprising the steps of:
(1) Mixing an alkaline solution containing nanoparticles and a silane coupling agent with amino groups and performing first aging to obtain a solution A;
(2) Mixing and reacting the solution A with a porphyrin reactant shown in the formula 1 to obtain a solution B;
(3) Mixing and second aging the solution B and the solution containing the active component ions to obtain a solution C containing abrasive particles;
(4) And (3) carrying out solid-liquid separation on the solution C to obtain the abrasive particles.
According to the method, a silane coupling agent containing an amino group is introduced into the nano particles to carry out surface modification on the nano particles; then introducing porphyrin reactant, wherein functional groups (such as carboxyl) in the porphyrin reactant are combined with amino through electric attraction; then adding active component ions to complex with porphyrin to form the abrasive particles containing porphyrin structures. Thus, the surface of the inner core of the prepared abrasive particle is electrically attracted to the porphyrin structure to form a catalytic center by introducing the silane coupling agent containing the amino group, and the catalytic center can well coordinate chemical reaction and mechanical action in the polishing process, so that the abrasive particle has higher catalytic activity and can improve the polishing rate and effect in the chemical mechanical polishing process.
Step (1): the alkaline solution containing the nanoparticles and the silane coupling having an amino group are mixed and first aged to obtain a solution a.
In some embodiments, the first aging is performed under stirring conditions to modify the nanoparticles with the silane coupling agent having an amino group.
Further, the temperature of the first aging is 40℃to 60℃such as 40℃45℃60℃and the like. Thus, during modification of the nanoparticle: on one hand, the agglomeration of nano particles can be reduced, so that the problem of scratch on the surface of a polishing piece in the later application process is reduced; on the other hand, the silane coupling agent and the nano particles can be bonded better, so that the complexation of active components in the later period is facilitated, and the active component ions can be complexed with porphyrin, so that the porphyrin structure and the inner core particles are tightly combined.
Further, the time for the first aging is 1.5h to 3h, for example, 1.5h, 3h, etc.
In some embodiments, step (1) further comprises: the nanoparticles are formulated into a solution having a concentration of 2-10wt%, and the pH of the solution is adjusted to 8-10.5 with an alkaline solution to form an alkaline solution containing nanoparticles.
Alternatively, the alkaline solution is an aqueous solution comprising a base. The base includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, oxazine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethanolamine, triethylenediamine, diethylenetriamine hexamethylenetetramine, hexamethyleneimine, triethylenediamine, cycloethyleneimine, morpholine, piperazine, and cyclohexylamine.
In some embodiments, the silane coupling agent having an amino group has a structure as shown in formula 2 or formula 3:
wherein each R 1 Independently selected from C1-C4 alkyl groups such as methyl, ethyl, n-propyl or isopropyl; n, m and p each independently represent any integer from 1 to 6, such as 1, 2, 3, 4, 5, 6.
As an example, the structure of the silane coupling agent is shown in formula 2-1:
thus, referring to FIG. 1, in the silane coupling agent having an amino groupAlkoxy (-OR) 1 ) Hydrolysis to form hydroxyl groups, which react with hydroxyl groups on the surface of the nanoparticles (e.g., silica) to modify the nanoparticles.
In some embodiments, the silane coupling agent having an amino group includes at least one of aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-aminoethyl gamma-aminopropyl trimethoxysilane, N-aminoethyl gamma-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl methyldimethoxysilane, N-beta- (aminoethyl) gamma-aminopropyl methyldimethoxysilane (KBM-602), N-beta- (aminoethyl) gamma-aminopropyl methyldiethoxysilane, N dimethyl-3-aminopropyl methyldimethoxysilane, N [3- (trimethoxypropyl) propyl ] N-butylamine, 3-ureidopropyl triethoxysilane, 3-ureidopropyl trimethoxysilane, and anilinopropyl trimethoxysilane.
Further, the silane coupling agent having an amino group is aminopropyl triethoxysilane.
In the step (1), the amount of the silane coupling agent may be selected according to the amount of the nanoparticles. Generally, the mass ratio of the nano particles to the silane coupling agent is 1: (0.01-2).
In some embodiments, in step (1), the nanoparticle core comprises at least one of silica, alumina, ceria, zirconia, polystyrene, phenolic resin, urea-formaldehyde resin, polyurethane, and polyacrylate.
Step (2): and mixing and reacting the solution A with porphyrin reactant to obtain solution B. Specifically, referring to fig. 1, the groups (e.g., carboxyl groups) in porphyrin reactant R can be electrically attractively bound to the amino groups of the silane coupling agent.
The structure of the porphyrin reactant is shown as formula 1:
wherein R is as defined in the first aspect of the invention.
In some embodiments, the temperature of the reaction is from 70 ℃ to 95 ℃, e.g., 70 ℃, 85 ℃, 95 ℃, and the like. Therefore, in the modification process of the nano particles, on one hand, the agglomeration of the nano particles can be reduced, and further the problem of scratch on the surface of a polishing piece in the later application process is reduced; on the other hand, the silane coupling agent with amino group and the group (such as carboxyl) in the R of porphyrin structure can be better electrically attracted.
In some embodiments, the reaction time is 3h-6h, e.g., 3h, 4h, 5h, 6h, etc.
In step (2), the amount of porphyrin reactant may be selected according to the amount of silane coupling agent. Typically, the molar ratio of porphyrin reactant to silane coupling agent is (0.1-0.9) to 1.
Optionally, the porphyrin reactant is a benzoic acid-containing porphyrin.
Further, the porphyrin reactant is meta-tetra (4-carboxyphenyl) porphyrin (CAS: 14609-54-2), and the structure is shown as formula 1-1:
step (3): the solution B and the solution containing the active ingredient ions are mixed and second aged to obtain a solution C containing abrasive particles. Specifically, referring to fig. 1, the active component ion is complexed with the porphyrin structure, so as to have a relatively strong catalytic effect on the polishing solution (such as the polishing solution containing hydrogen peroxide), and further improve the oxidizing capability of the Fenton reaction.
In some embodiments, the temperature of the second aging is from 40 ℃ to 60 ℃, e.g., 40 ℃, 45 ℃, 60 ℃, etc. Thus, the active component is better complexed with the porphyrin structure while reducing the cost of preparing the abrasive particles.
In step (3), the second aging time is 1.5h to 3h, for example, 1.5h, 2h, 2.5h, 3h, etc.
In step (3), the solution of active ingredient ions includes a solute, by which the active ingredient ions are provided, which may be, for example, a soluble salt of the active ingredient ions.
Optionally, the solute comprises at least one of manganese acetate, ferric chloride, cupric sulfate, zinc chloride, zinc sulfate, stannic chloride, cobalt sulfate, nickel nitrate, and cobalt chloride.
Alternatively, the concentration of solute is 5wt% to 15wt%.
The amount of solution of the active component ions can be selected based on the amount of porphyrin. Typically, the molar ratio of active component ion to porphyrin reactant is (1.1-1.3) to 1.
Step (4): subjecting the solution C to solid-liquid separation to obtain the abrasive particles.
Optionally, the solid-liquid separation mode comprises centrifugal separation.
In order to obtain a high purity dry product, step (4) further comprises: the solid product obtained by centrifugal separation is washed and dried. The washing may be, for example, ethanol, and the drying temperature may be 40-70 ℃.
As a specific example, a method of preparing the abrasive particles includes:
s1: preparing a solution containing 2-10wt% of nano particles by mass fraction, and regulating the pH of the solution to 8-10.5 by using an alkaline solution to form an alkaline solution containing nano particles;
s2: mixing an alkaline solution containing nanoparticles and a silane coupling agent (with a structure shown as a formula 2-1) with amino groups and performing first aging to obtain a solution A;
s3: mixing and reacting the solution A with a porphyrin reactant shown in the formula 1 to obtain a solution B;
s4: mixing and second aging the solution B and the solution containing the active component ions to obtain a solution C containing abrasive particles;
s5: the solution C is filtered, washed and dried to obtain the abrasive particles.
The following description of the present invention is made by way of specific examples, which are given for illustration of the present invention and should not be construed as limiting the scope of the invention.
Example 1
Weighing 500g of nano (solid) silicon dioxide (Dv 50 of silicon dioxide is 45 nm) solution with the mass concentration of 7wt%, and regulating the pH of the solution to 10 by adopting 5wt% ammonia water to obtain an alkaline solution containing nano particles;
1.04g of aminopropyl triethoxysilane (CAS: 919-30-2) was added to the above alkaline solution at 45℃and then aged for 2 hours to give solution A;
adding 3.32g of meta-tetra (4-carboxyphenyl) porphyrin (with a structure shown as a formula 1-1) into the solution A, and then reacting for 4 hours at 85 ℃ to obtain a solution B;
FeCl with concentration of 10wt% 3 8.32g of aqueous solution was added to the above solution B, followed by aging at 45℃for 2 hours to obtain a solution C containing abrasive grains;
the abrasive particles in the solution C are separated by a centrifugal separation method, washed by methanol and dried at 60 ℃ to obtain the abrasive particles.
Examples 2 to 4
Abrasive particles were prepared as in example 1, except that FeCl 3 The amounts of the aqueous solutions added were 5.44g, 7.48g and 9.72g, respectively.
Example 5
Abrasive particles were prepared as in example 1 except that the silane coupling agent was N- (. Beta. -aminoethyl) -gamma. -aminopropyl triethoxysilane in an amount of 1.25g and m-tetrakis (4-carboxyphenyl) porphyrin in an amount of 4.33g.
Example 6
Abrasive particles were produced in the same manner as in example 1, except that the active component ion solution had a mass concentration of 5% Ni (NO 3 ) 2 The addition amount thereof was 15.29g.
Comparative example 1
Silica nanoparticles having Dv50 of 45nm were used as abrasive particles to prepare an aqueous solution having a concentration of 2 wt%. Adjusting the pH value of the solution to 2.5 by adopting nitric acid with the mass fraction of 2%, adding hydrogen peroxide to prepare a solution with the hydrogen peroxide concentration of 2wt%, adding malonic acid and ferric nitrate into the solution to ensure that the concentration of malonic acid in the polishing solution is 0.2wt% and the concentration of ferric nitrate is 50ppm, and performing polishing test;
TABLE 1
Test case
(1) Content test of active component ion: the particles were tested for active ingredient content using ICP-OES and the results are shown in Table 1 below.
TABLE 1
(2) Morphology characterization of abrasive particles: and analyzing the morphology of the abrasive particles by adopting a scanning electron microscope.
(3) Polishing effect test
1) Preparation of polishing liquid
Polishing solutions of examples 1 to 6 were composed: preparing a polishing solution with the mass fraction of 2% of chemical mechanical polishing abrasive particles by using deionized water, adjusting the pH value of the polishing solution to 2.5 by using nitric acid with the mass fraction of 2%, adding hydrogen peroxide to form the polishing solution with the hydrogen peroxide concentration of 2wt%, and performing polishing test.
2) Silicon wafer scratch detection
Polishing test is carried out on the metal tungsten by using a G & P polishing machine poly500, the polishing pressure is 3.5psi, the polishing pad is IC1000, the rotation speeds of a polishing head and the polishing pad are respectively 60/65rpm, and the flow rate of polishing feeding is 50mL/min; polishing time was 2min, and scratches of the polished silicon wafer were detected.
The above specific test results are shown in table 2.
TABLE 2
As is clear from the above table, the polishing rate of comparative example 1 was lower than that of examples 1 to 6, indicating that the effect of improving the polishing rate was not significant by adding the porphyrin-like structure to the polishing liquid.
Examples 1-4 are slightly less effective than example 2, indicating that the amount of active component ions is lower and that fewer porphyrins are produced, resulting in lower polishing rates for the abrasive particles.
Fig. 2 is a sem morphology of the abrasive particles of example 1, fig. 3 is a sem morphology of the abrasive particles of example 4, and fig. 4 is a sem morphology of the abrasive particles of comparative example 1, from which it can be seen that the abrasive particles are spherical, and that no substantial change in morphology occurs after bonding of the nanoparticles to the porphyrin.
In the description of the present specification, reference to the term "one embodiment," "another embodiment," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. In addition, it should be noted that, in this specification, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (10)

1. An abrasive particle for chemical mechanical polishing, comprising a nanoparticle core and a porphyrin-like structure electrically attracted to the surface of the nanoparticle core by a silane coupling agent having an amino group, wherein the porphyrin-like structure isM is an active component ion, R is: />X, Y and Z are each independently selected from hydrogen, halogen, sulfonate, carboxyl, or hydroxyl, wherein R is an electrically attractive site.
2. Abrasive particles according to claim 1, wherein Z is selected from halogen, sulfonate, carboxyl or hydroxyl groups, and X and Y are both hydrogen.
3. Abrasive particles according to claim 1 or 2, wherein M is selected from at least one of iron ions, manganese ions, copper ions, zinc ions, tin ions, nickel ions, cobalt ions and hydrogen ions.
4. Abrasive particles according to claim 1 or 2, characterized in that the size of the abrasive particles is 10nm-150nm.
5. Abrasive particles according to claim 1 or 2, characterized in that the abrasive particles comprise solid spherical abrasive particles or solid profiled abrasive particles.
6. The abrasive particle of claim 1 or 2, the nanoparticle core comprising at least one of silica, alumina, ceria, zirconia, polystyrene, phenolic resin, urea-formaldehyde resin, polyurethane, and polyacrylate.
7. A method of making the abrasive particle of any one of claims 1-6, comprising the steps of:
(1) Mixing an alkaline solution containing nanoparticles and a silane coupling agent with amino groups and performing first aging to obtain a solution A;
(2) Mixing and reacting the solution A with porphyrin reactant with the structure shown as formula 1 to obtain solution B;
(3) Mixing and second aging the solution B and the solution containing the active component ions to obtain a solution C containing abrasive particles;
(4) Subjecting the solution C to solid-liquid separation to obtain the abrasive particles.
8. The method of claim 7, wherein step (1) satisfies at least one of the following conditions:
the pH of the alkaline solution is 8-10.5;
the concentration of the nano particles in the alkaline solution is 2-10wt%;
the temperature of the first aging is 40-60 ℃ and the time is 1.5-3 h;
the mass ratio of the nano particles to the silane coupling agent is 1:0.01-2.
9. The method according to claim 7 or 8, wherein step (2) satisfies at least one of the following conditions:
the reaction temperature is 70-95 ℃ and the reaction time is 3-6 h;
the molar ratio of porphyrin reactant to silane coupling agent is (0.1-0.9) to 1.
10. The method of claim 7, wherein step (3) satisfies at least one of the following conditions:
the second aging temperature is 40-60 ℃, and the aging time is 1.5-3 h;
in the solution containing active component ions, the active component ions are provided by solutes, and the solutes comprise at least one of manganese acetate, ferric chloride, copper sulfate, zinc chloride, zinc sulfate, stannic chloride, cobalt sulfate, cobalt chloride and nickel nitrate, and the concentration of the solutes is 5-15 wt%;
the mol ratio of the active component ion to the porphyrin reactant is (1.1-1.3) to 1.
CN202311823699.7A 2023-12-27 2023-12-27 Abrasive particles for chemical mechanical polishing and method for preparing same Pending CN117821016A (en)

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