CN116144323A - Composite microsphere with mesoporous core-shell structure for copper CMP, preparation method thereof, chemical mechanical polishing solution and application thereof - Google Patents

Composite microsphere with mesoporous core-shell structure for copper CMP, preparation method thereof, chemical mechanical polishing solution and application thereof Download PDF

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CN116144323A
CN116144323A CN202211613769.1A CN202211613769A CN116144323A CN 116144323 A CN116144323 A CN 116144323A CN 202211613769 A CN202211613769 A CN 202211613769A CN 116144323 A CN116144323 A CN 116144323A
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sio
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晏金灿
石宁
韩生
陈亚莉
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Shanghai Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract

The invention relates to a composite microsphere with a mesoporous core-shell structure for copper CMP, a preparation method thereof, a chemical mechanical polishing solution and application thereof. The composite microsphere uses mesoporous SiO 2 As nuclei, ceO 2 Is a shell. When in preparation, the template agent and the silicon source are firstly utilized to prepare mesoporous SiO by a template method 2 Microspheres as the core of the core-shell structure; then, cerium source and precipitant are utilized to disperse and synthesize SiO with mesoporous core-shell structure for copper CMP 2 /CeO 2 Composite microspheres. The chemical mechanical polishing solution comprises SiO for copper CMP with mesoporous core-shell structure 2 /CeO 2 Composite microsphere, corrosion inhibitor, oxidant and complexing agent. The polishing solution is applied to copper chemical mechanical polishing. Compared with the prior art, the composite microsphere prepared by the invention has uniform surface coating, good monodispersity and simple preparation process, and can be used in the fields of copper sheet chemical mechanical polishing and the like.

Description

Composite microsphere with mesoporous core-shell structure for copper CMP, preparation method thereof, chemical mechanical polishing solution and application thereof
Technical Field
The invention relates to the field of nano material preparation, in particular to a composite microsphere with a mesoporous core-shell structure for copper CMP, a preparation method thereof, a chemical mechanical polishing solution and application thereof, and belongs to the field of preparation technology of polishing abrasive particles for copper surface precision polishing.
Background
With the rapid development of Integrated Circuits (ICs), copper, which has low resistivity and high electron mobility resistance and other electrical characteristics, has gradually replaced aluminum as a wiring layer metal for very large scale integrated circuits (VLSI). Consequently, achieving global planarization of copper has become a new challenge for integrated circuit development. Chemical Mechanical Polishing (CMP) is currently the only method that can simultaneously achieve global planarization. The abrasive is one of the important parameters of CMP, and has an important influence on polishing quality and polishing efficiency.
The polishing abrasive material reported at present comprises SiO 2 、Al 2 O 3 、CeO 2 、Fe 3 O 4 Etc., while copper-based abrasives are reported to be less (e.g., CN 105800664A). As single abrasives have failed to meet the increasing demands for ultra-precise surface polishing. Therefore, the abrasive with composite properties mainly comprising a core-shell structure is a key to improving polishing effect. In SiO form 2 As nuclei, ceO 2 The core-shell structure of the shell has the characteristics of high biocompatibility, high stability, high polishing efficiency and the like, and has remarkable advantages compared with single abrasive. The abrasive applications are currently focused mainly on nanocomposite particle dispersion, adsorptivity, etc., and while applied in the CMP field (e.g., CN 107129762A,CN 106987229A), there is a clear interest in copper substrates.
Disclosure of Invention
The invention aims to overcome at least one of the defects in the prior art and provide a composite microsphere with a mesoporous core-shell structure for copper CMP, a preparation method thereof, a chemical mechanical polishing solution and application thereof, wherein the composite microsphere can effectively reduce the surface roughness of copper substrate polishing, improve the surface defects and help to improve the polishing rate.
The aim of the invention can be achieved by the following technical scheme:
SiO for copper CMP with mesoporous core-shell structure 2 /CeO 2 Composite microsphere with mesoporous SiO 2 As nuclei, ceO 2 Is a shell.
Such asThe SiO for copper CMP with the mesoporous core-shell structure 2 /CeO 2 The preparation method of the composite microsphere comprises the steps of preparing mesoporous SiO by a template method by using a template agent and a silicon source 2 Microspheres as the core of the core-shell structure; then, cerium source and precipitant are utilized to disperse and synthesize SiO with mesoporous core-shell structure for copper CMP 2 /CeO 2 Composite microspheres.
Further, the method comprises the steps of:
dispersing a template agent in a solvent, dripping a precipitator to obtain a solution A, stirring the solution A, and adding a silicon source to obtain a solution B;
centrifuging the solution B, washing, drying and calcining to obtain mesoporous SiO 2 A microsphere;
mesoporous SiO 2 Dispersing the microspheres in a solvent, and obtaining a solution C after ultrasonic treatment and/or stirring;
dispersing a cerium source and a precipitator in a solvent, carrying out ultrasonic treatment and/or stirring to obtain a solution D, adding the solution D into the solution C, and carrying out stirring reaction to obtain a solution E;
centrifuging the solution E, washing, drying, calcining, grinding and sieving to obtain SiO with mesoporous core-shell structure for copper CMP 2 /CeO 2 Composite microspheres.
Further, the dosage ratio of the template agent, the precipitant and the silicon source is (0.4-0.8) g (1-2) ml (1-3) ml;
the mesoporous SiO 2 The mass ratio of the microsphere to the cerium source to the precipitator is (0.4-1): 0.6-1.2): 0.96-1.92;
the template agent comprises Cetyl Trimethyl Ammonium Bromide (CTAB), and the precipitant comprises ammonia (NH) 3 ·H 2 O) or Hexamethylenetetramine (HMT), said silicon source comprising tetraethyl orthosilicate (TEOS), said cerium source comprising cerium nitrate hexahydrate [ Ce (NO) 3 ) 3 ·6H 2 O]The solvent comprises water and/or alcohol;
the stirring speed is 300-800r/min, and the stirring time is 2-6h; the rotational speed of the centrifugation is 8000-10000r/min, and the time is 5-10min;
the drying temperature is 55-65 ℃, the time is 12-24h, the calcining temperature is 450-650 ℃, and the heat preservation time is 2-4h;
the ultrasonic treatment time is 10-15min, and the washing adopts alcohol and water to separate washing.
Further, the precipitant in solution A is ammonia (NH) 3 ·H 2 O), the precipitant in the solution D is Hexamethylenetetramine (HMT), the solvent in the solution A is a mixture of water and alcohol, the solvent in the solution C is alcohol, and the solvent in the solution C is water; the ammonia water is commercial 25-28wt% strong ammonia water.
The stirring speed in the solution A is 350-800r/min, the time is 2-4h, and the temperature is normal temperature; the stirring speed in the solution E is 300-600r/min, the time is 3-6h, and the temperature is 60-75 ℃;
the number of times of washing is not less than 3, and the alcohol includes ethanol.
Further, the volume ratio of water to alcohol in the solution A is (150-200): 40-60.
A chemical mechanical polishing solution comprises the SiO for copper CMP with a mesoporous core-shell structure 2 /CeO 2 Composite microsphere, corrosion inhibitor, oxidant and complexing agent.
Further, in the polishing solution, the mass content of the composite microsphere is 0.5-10%, the mass content of the corrosion inhibitor is 0.001-0.5%, the mass content of the oxidant is 0.5-5%, the mass content of the complexing agent is 0.05-5%, and the balance is solvent;
the corrosion inhibitor comprises a nitrogen azole compound, the oxidant comprises a strong acid compound, the complexing agent comprises an aminocarboxylic compound, and the solvent comprises water.
Further, in the polishing solution, the mass content of the composite microsphere is 1-5%, the mass content of the corrosion inhibitor is 0.01-0.05%, the mass content of the oxidant is 0.5-2%, and the mass content of the complexing agent is 0.5-1%;
the nitrogen azole compound comprises benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 5-methyltetrazole, 5-phenyl-1, 2, 4-triazole or 1-hydroxybenzotriazole;
the strong acid compound comprises peroxide compounds such as hydrogen peroxide, peroxyformic acid, persulfates, percarbonates and the like, and periodic acid, perchloric acid, perboric acid or potassium permanganate;
the aminocarboxylic compound comprises glycine, alanine, valine, leucine, proline, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, serine, aspartic acid, threonine, glutamic acid, asparagine, glutamine, nitrilotriacetic acid, ethylenediamine tetraacetic acid or cyclohexanediamine tetraacetic acid.
The application of the chemical mechanical polishing solution is that the polishing solution is applied to copper chemical mechanical polishing, the pH of the chemical mechanical polishing solution is regulated to 8-8.5 during polishing, and the polishing process conditions comprise: the polishing pressure is 1-3.4psi, the rotation speed of the sample loading disc is 60-90r/min, the rotation speed of the polishing disc is 90-120r/min, the feeding flow of the polishing liquid is 60-120ml/min, and the polishing time is 1-5min.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts a template method to prepare mesoporous SiO 2 The SiO with core-shell coating structure is prepared by introducing cerium source into the core 2 /CeO 2 Composite microspheres. The material has a mesoporous structure, and the lower elastic modulus can reduce mechanical damage caused by polishing.
(2) The invention has low production cost, simple preparation process, strong experimental repeatability and application value in improving the polishing effect of the copper substrate;
(3) The composite microsphere prepared by the invention has uniform surface coating, good monodispersity and simple preparation process, and can be used in the fields of copper sheet chemical mechanical polishing and the like.
Drawings
FIG. 1 is a mesoporous SiO prepared in example 1 2 /CeO 2 Scanning electron microscope pictures of the composite microspheres;
FIG. 2 is a mesoporous SiO prepared in example 1 2 /CeO 2 Nitrogen adsorption curve graph of composite microsphere;
FIG. 3 is a mesoporous SiO prepared in example 1 2 /CeO 2 Pore size distribution curve of the composite microsphere;
FIG. 4 shows mesoporous SiO prepared in example 1 2 /CeO 2 An atomic force microscope two-dimensional morphology graph of the surface of the copper sheet after the composite microsphere is polished;
FIG. 5 shows mesoporous SiO prepared in example 1 2 /CeO 2 And (3) an atomic force microscope three-dimensional morphology graph of the surface of the copper sheet after the composite microsphere is polished.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the following embodiments. Unless otherwise specified, all% herein are mass%.
SiO for copper CMP with mesoporous core-shell structure 2 /CeO 2 The preparation method of the composite microsphere adopts Cetyl Trimethyl Ammonium Bromide (CTAB) as a template agent and Tetraethoxysilane (TEOS) as a silicon source, and mesoporous SiO is prepared by a template method 2 Microspheres as the core of the core-shell structure; then cerium nitrate hexahydrate Ce (NO) 3 ) 3 ·6H 2 O is cerium source, hexamethylenetetramine (HMT), ammonia (NH) 3 ·H 2 O) is a precipitator, and is dispersed and synthesized in an ethanol-deionized water system. Centrifuging the solution, washing with deionized water and ethanol to obtain a centrifugal product, and vacuum drying and calcining to obtain the core-shell structure, wherein the method comprises the following steps of:
step one, CTAB is taken and dispersed in a mixed solution of deionized water and ethanol, ammonia water is dripped into the mixed solution to obtain a solution A, constant-temperature magnetic stirring is carried out on the solution A, TEOS is dripped into the solution A dropwise to obtain a solution B; CTAB addition amount is 0.4-0.8g, NH 3 ·H 2 The addition amount of O is 1-2ml, and the addition amount of TEOS is 1-3ml. The temperature is 25 ℃, the magnetic stirring speed is 350-800r/min, and the reaction time is 2-4h.
Step two, after centrifuging the solution B, washing with ethanol and deionized water respectively, vacuum drying, calcining to remove the template to obtainTo mesoporous SiO 2 A microsphere; the centrifugal speed of the solution B is 10000 revolutions per minute, and the time is 5 minutes; the washing method is to wash 3 times with ethanol and deionized water respectively, the centrifugal speed is 8000 rpm, and the time is 5 minutes. The vacuum drying temperature is 60 ℃, the drying time is 12-24h, the calcining temperature is 450-650 ℃, and the heat preservation time is 2-4h.
Step three, taking mesoporous SiO 2 Dispersing the microspheres in ethanol, performing ultrasonic treatment to obtain a solution C, and performing constant-temperature magnetic stirring on the solution C; mesoporous SiO 2 The added amount of the microspheres is 0.4-1g, and the solution C is subjected to ultrasonic treatment for 10-15 minutes.
Step four, ce (NO) 3 ) 3 ·6H 2 Dispersing O and HMT in deionized water, performing ultrasonic treatment to obtain a solution D, dropwise adding the solution D into the solution C to obtain a solution E, and performing constant-temperature magnetic stirring reaction on the solution E; ce (NO) 3 ) 3 ·6H 2 The addition amount of O is 0.6-1.2g, the addition amount of HMT is 0.96-1.92g, and the solution D is subjected to ultrasonic treatment for 10-15 minutes. The temperature is 60-75 ℃, the magnetic stirring speed is 300-600r/min, and the reaction time is 3-6h.
Step five, centrifuging the solution E, washing with deionized water and ethanol, vacuum drying, calcining, grinding and sieving to obtain the nano mesoporous SiO with a core-shell structure 2 /CeO 2 Composite microspheres. The centrifugal speed of the solution E is 10000 revolutions per minute, and the time is 10 minutes; the washing method is to wash 3 times with ethanol and deionized water respectively, the centrifugal speed is 8000 rpm, and the time is 5 minutes. The vacuum drying temperature is 60 ℃, the drying time is 12-24h, the calcining temperature is 450-650 ℃, and the heat preservation time is 2-4h.
A chemical mechanical polishing liquid comprises SiO with mesoporous core-shell structure 2 /CeO 2 Composite microsphere, corrosion inhibitor, oxidant and complexing agent. SiO (SiO) 2 /CeO 2 The content of the composite microsphere is 0.5-10%. The corrosion inhibitor is benzotriazole compounds such as benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 5-methyltetrazole, 5-phenyl-1, 2, 4-triazole, 1-hydroxybenzotriazole and the like. The content of the corrosion inhibitor is 0.001-0.5%. The oxidant is peroxide compounds such as hydrogen peroxide, peroxyformic acid, persulfate and percarbonate, and strong acid compounds such as periodic acid, perchloric acid, perboric acid and potassium permanganate. The content of the oxidant is 0.5-5%. The complexing agent is glycine, alanine, valine, leucine, proline, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, serine, aspartic acid, threonine, glutamic acid, asparagine, glutamine, nitrilotriacetic acid, ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid and other aminocarboxylic compounds. The content of complexing agent is 0.05-5%.
SiO for copper CMP with mesoporous core-shell structure 2 /CeO 2 The preparation method of the composite microsphere is applied to copper chemical mechanical polishing. SiO with mesoporous core-shell structure is prepared 2 /CeO 2 The composite microsphere is prepared into polishing liquid, and polishing test is carried out through an automatic precise grinding and polishing machine.
The preparation process of the polishing solution comprises the following steps: dispersing the composite microspheres into deionized water to prepare uniform emulsion, adding a corrosion inhibitor, an oxidant and a complexing agent, then regulating the pH to 8-8.5 by using sodium hydroxide (NaOH), and uniformly stirring by using ultrasonic magnetic force to obtain the polishing solution. The polishing process conditions include: the polishing pressure is 1-3.4psi, the rotation speed of the sample loading disc is 60-90r/min, the rotation speed of the polishing disc is 90-120r/min, the feeding flow of the polishing liquid is 60-120ml/min, and the polishing time is 1-5min.
Compared with CN106987229A, the abrasive prepared by the invention is used for polishing silicon wafers, the polishing solution has different additive components and proportions, and the copper substrate polishing solution has more components and different effects. The polishing method is similar to the polishing method for different polishing substrates, but the emphasis is different, and the polishing solution for copper sheet chemical mechanical polishing is firstly used for forming a passivation film and a composite layer film on the copper surface by chemical reaction, and then mechanically removing the passivation film and the composite layer film by an abrasive.
Copper substrates are softer and lower in elastic modulus (20 ℃ copper 105GPa vs 20 ℃ silicon 190 GPa) than silicon wafers, silicon carbide, sapphire, glass and other substrates. The selection of the abrasive is more specific, the composite abrasive shell layer used in the method is coated with cerium oxide (softer than the core layer silicon oxide), so that mechanical scratches generated on the copper surface by the abrasive can be reduced, and the chemical reaction layer can be well removed through the supporting effect provided by the core layer.
Example 1
A composite microsphere with a mesoporous core-shell structure for copper CMP, a preparation method thereof, a chemical mechanical polishing solution and application thereof, and the specific operation is as follows:
step one, taking 0.42g of CTAB, dispersing the CTAB in a flask filled with a mixed solution of 160ml of deionized water and 50ml of absolute ethyl alcohol, dropwise adding 2ml of ammonia water to obtain a solution A, placing the solution A in an oil bath pot set at 25 ℃, stirring for 30min at a magnetic stirring rate of 350r/min, dropwise adding a mixed solution of 2.5ml of TEOS dissolved in 40ml of absolute ethyl alcohol to obtain a solution B, and continuously stirring for 2h;
step two, centrifugally separating the obtained solution after the reaction is finished, washing the solution with deionized water and ethanol for 3 times respectively, transferring the solution into a vacuum drying oven for drying for 12 hours, placing the solution into a tubular furnace with the temperature of 550 ℃ for calcining to remove a template, preserving heat for 3 hours, and taking out the solution after the solution is naturally cooled to the room temperature to obtain mesoporous SiO 2 And (3) microspheres.
Step three, 0.62g of mesoporous SiO is taken 2 Dispersing the microspheres in a flask filled with 60ml of ethanol, and performing ultrasonic treatment for 10min to obtain a solution C;
step four, 1.06g Ce (NO) 3 ) 3 ·6H 2 O and 1.42g HMT are dispersed in a beaker filled with 100ml deionized water, ultrasonic treatment is carried out for 15min to obtain solution D, the solution D is dropwise added into solution C through a separating funnel to obtain solution E, the solution E is placed in an oil bath pot set at 75 ℃ and stirred for 4h at a magnetic stirring rate of 600 r/min;
step five, centrifugally separating the obtained solution after the reaction is finished, washing the solution with deionized water and ethanol for 3 times respectively, transferring the solution into a vacuum drying oven for drying for 24 hours, placing the solution into a tubular furnace with the temperature of 550 ℃ for calcining for 3 hours, grinding and sieving to obtain the yellowish mesoporous SiO with a core-shell structure 2 /CeO 2 Composite microspheres.
FIG. 1 is a mesoporous SiO prepared in example 1 2 /CeO 2 And (5) a transmission electron microscope picture of the composite microsphere. As can be seen, the prepared mediumHole SiO 2 /CeO 2 The particles are in regular sphere shape, and the shell layer of the composite microsphere can be clearly seen to be uniformly covered with a layer of CeO 2 The core-shell coating structure is typical. Particle size analysis and test are carried out by Nano-Measurer software, the average particle size of the prepared inner core is about 275nm, and the particle size of the shell is about 21nm.
FIGS. 2 and 3 show mesoporous SiO prepared in example 1 2 /CeO 2 Nitrogen adsorption curve and pore size distribution curve of the composite microsphere. It can be seen that the prepared mesoporous SiO 2 /CeO 2 The nitrogen adsorption curve of the particles accords with an IV type isotherm, and the specific surface area is about 919.53m through calculation and analysis 2 And/g, the pore size distribution is narrow, and the average pore diameter is about 2.87nm.
Dispersing the composite microspheres prepared by the technological parameters in the embodiment 1 into deionized water to prepare an emulsion with the mass concentration of 2%, adding 0.01% of benzotriazole as a corrosion inhibitor, 1% of hydrogen peroxide as an oxidant and 0.5% of glycine as a complexing agent, regulating the pH to 8.5 by NaOH, and uniformly stirring by ultrasonic magnetic force to obtain the polishing solution.
Under the following polishing process conditions, the polishing pressure is 3psi, the rotation speed of the sample loading disc is 75r/min, the rotation speed of the polishing disc is 90r/min, the feeding flow of the polishing liquid is 90ml/min, and the polishing time is 3min, and the copper sheet is polished by an automatic precise polishing machine.
FIGS. 4 and 5 show mesoporous SiO prepared in example 1 2 /CeO 2 And an atomic force microscope two-dimensional morphology graph and a three-dimensional morphology graph of the surface of the copper sheet after the composite microsphere is polished. Analyzing the polished surface by NanoScope Analysis software, wherein the average value of the surface roughness of the polished copper sheet is about 0.496nm; the mass loss of the copper sheets before and after polishing was calculated, and the polishing rate obtained by the material removal formula was 223nm/min.
In CN106987229a, the prepared polishing liquid contains: mesoporous silica/ceria composite particles (SiO 2 /CeO 2 ) Deionized water (DIW), sodium Dodecyl Benzene Sulfonate (SDBS), sodium hydroxide (NaOH), abrasive, solvent, dispersant, pH adjuster, respectively. Acting on silicon wafer substrates with emphasis onAnd mechanically removing, namely dispersing the abrasive in the polishing solution by SDBS, adjusting the pH value to prevent corrosion caused by acidity, forming a combined mode of the abrasive and the silicon bottom, and mechanically removing by the abrasive. The polishing liquid cannot be applied to a copper substrate because no component can react with the surface of the copper substrate to perform chemical mechanical polishing.
Whereas the polishing liquid of the present application is exemplified in example 1, the composition is as follows: mesoporous silica/ceria composite particles (SiO 2 /CeO 2 ) Deionized water (DIW), hydrogen peroxide (H) 2 O 2 ) The Benzotriazole (BTA), glycine (GLY) and sodium hydroxide (NaOH) are respectively an abrasive, a solvent, an oxidant, a corrosion inhibitor, a complexing agent and a pH regulator. Wherein, the copper substrate firstly needs to react with hydrogen peroxide in the polishing solution to form a film, and Cu is further dissociated by OH groups 2+ Ions, at this time, an oxide film is formed first; further GLY and BTA are respectively in Cu 2+ And forming chelate and complex by ion combination, forming a composite layer, and finally mechanically removing the surface composite layer through abrasive particles to form a new dishing-free copper layer. Although both are CMP, the added components are different and the mechanism of action is different. CN106987229a cannot be used in communication with the polishing liquid of the present application.
Example 2
This embodiment is substantially identical to the procedure of embodiment 1 described above, except that: in the first step, the addition amount of CTAB is 0.78g, the magnetic stirring speed is 600r/min, and the addition amount of TEOS is 2ml; setting the temperature of the tube furnace to 650 ℃, and preserving heat for 2 hours; step three mesoporous SiO 2 The addition amount of the microspheres is 1.02g; ce (NO) in step four 3 ) 3 ·6H 2 The addition amount of O is 1.58g, the addition amount of HMT is 1.92g, the temperature of the oil bath is 65 ℃, and the magnetic stirring speed is 450r/min; and fifthly, setting the temperature of the tube furnace to 650 ℃, and preserving heat for 2 hours.
Dispersing the composite microspheres prepared by the process parameters in the embodiment 2 into deionized water to prepare emulsion with the mass concentration of 1%, adding 0.05% of 1,2, 4-triazole as a corrosion inhibitor, 1% of hydrogen peroxide as an oxidant and 0.5% of glycine as a complexing agent, and then regulating the pH value to 8.0 by using sodium hydroxide, and uniformly stirring to obtain polishing solution;
under the following polishing process conditions, the polishing pressure is 3psi, the rotation speed of the sample loading disc is 87r/min, the rotation speed of the polishing disc is 93r/min, the feeding flow of the polishing liquid is 90ml/min, and the polishing time is 5min, and the copper sheet is polished by an automatic precise polishing machine.
Example 3
This embodiment is substantially identical to the procedure of embodiment 1 described above, except that: in the first step, the addition amount of CTAB is 0.41g, the magnetic stirring speed is 400r/min, and the addition amount of TEOS is 1ml; setting the temperature of the tube furnace to 550 ℃, and preserving heat for 4 hours; step three mesoporous SiO 2 The addition amount of the microspheres is 0.42g; ce (NO) in step four 3 ) 3 ·6H 2 The addition amount of O is 0.66g, the addition amount of HMT is 0.99g, the temperature of the oil bath is 70 ℃, and the magnetic stirring speed is 450r/min; setting the temperature of the tube furnace to 550 ℃ in the fifth step, and preserving the heat for 4 hours.
Dispersing the composite microsphere prepared by the technological parameters of example 3 into deionized water to prepare emulsion with the mass concentration of 3%, and adding 0.02% of benzotriazole as a corrosion inhibitor and 1% of H 2 O 2 As an oxidant, valine with the concentration of 1% is used as a complexing agent, then sodium hydroxide is used for regulating the pH value to 8.0, and the polishing solution is obtained after uniform stirring;
under the following polishing process conditions, the polishing pressure is 1psi, the rotation speed of the sample loading disc is 60r/min, the rotation speed of the polishing disc is 90r/min, the feeding flow of the polishing liquid is 80ml/min, and the polishing time is 3min, and the copper sheet is polished by an automatic precise polishing machine.
Example 4
This embodiment is substantially identical to the procedure of embodiment 1 described above, except that: in the first step, the addition amount of CTAB is 0.50g, the magnetic stirring speed is 750r/min, and the addition amount of TEOS is 3ml; setting the temperature of the tube furnace to 500 ℃ in the second step, and preserving heat for 3 hours; step three mesoporous SiO 2 The addition amount of the microspheres is 0.80g; ce (NO) in step four 3 ) 3 ·6H 2 The addition amount of O is 1.21g, the addition amount of HMT is 1.80g, the temperature of the oil bath pot is 70 ℃, and the magnetic stirring is carried outThe speed is 550r/min; and fifthly, setting the temperature of the tube furnace to 500 ℃, and preserving heat for 3 hours.
Dispersing the composite microsphere prepared by the technological parameters of example 4 into deionized water to prepare emulsion with the mass concentration of 5%, and adding 0.01% of benzotriazole as corrosion inhibitor and 1% of H 2 O 2 As an oxidant, 0.5% glycine is used as a complexing agent, then sodium hydroxide is used for regulating the pH value to 8.5, and the polishing solution is obtained after uniform stirring;
under the following polishing process conditions, the polishing pressure is 1psi, the rotation speed of the sample loading disc is 90r/min, the rotation speed of the polishing disc is 105r/min, the feeding flow of the polishing liquid is 100ml/min, and the polishing time is 3min, and the copper sheet is polished by an automatic precise polishing machine.
Table 1 shows mesoporous SiOs prepared in examples 1 to 4 2 /CeO 2 The composite microsphere is prepared into polishing solution, and then the average value and the polishing rate of the surface roughness of the copper substrate after CMP polishing are achieved. Table 2 shows polishing conditions of the usual examples in which the change in composition was made on the basis of example 1.
TABLE 1
Figure BDA0004001247610000101
TABLE 2
Figure BDA0004001247610000102
In tables 1-2, the pH is controlled within the alkaline range of 8-8.5, and the pH and alkalinity are not considered.
Firstly, the types of components in polishing solution are developed in the directions of less types and less concentrations, and the concentration of abrasive particles is generally 1-40%, but the precision polishing is realized by the aid of literature review and continuous perfection of the polishing solution, so that the concentration ratio is as small as possible; the oxidizing agent is usually the second most as an additive component, but a proportion of more than 5% causes great side effects on the polishing liquid, such as corrosion of the substrate, failure to effectively promote forward progress of the reaction, and is usually controlled to be less than the concentration of the abrasive and greater than the addition amount of other components; complexing agents and corrosion inhibitors are generally used as a third ratio species, and act as complexation in the polishing slurry.
Since numerous influencing factors exist, the polishing rate and polishing effect caused by the type and the amount of the polishing agent are still continuously explored, and meanwhile, how to balance the polishing rate and the polishing effect is also a research difficulty, and is not a conventional choice, for example, examples 1 and 4 are the influences on the polishing after the concentration change of different abrasive particles, and the polishing efficiency is increased due to the fact that the mechanical removal speed is gradually increased due to the increase of the concentration, but the surface roughness is not reduced, but is improved. Examples 2 and 3 are discussed with respect to the effect of various corrosion inhibitors and complexing agents on copper CMP, and it should be noted that benzotriazole and 1,2, 4-triazole, glycine and valine are all of the same type.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. SiO for copper CMP with mesoporous core-shell structure 2 /CeO 2 The composite microsphere is characterized in that the composite microsphere adopts mesoporous SiO 2 As nuclei, ceO 2 Is a shell.
2. A SiO for copper CMP having a mesoporous core-shell structure according to claim 1 2 /CeO 2 The preparation method of the composite microsphere is characterized in that the method firstly utilizes a template agent and a silicon source to prepare mesoporous SiO by a template method 2 Microspheres as the core of the core-shell structure; dispersing by using cerium source and precipitantSiO for synthesizing copper CMP with mesoporous core-shell structure 2 /CeO 2 Composite microspheres.
3. The SiO for copper CMP having a mesoporous core-shell structure according to claim 2 2 /CeO 2 The preparation method of the composite microsphere is characterized by comprising the following steps:
dispersing a template agent in a solvent, dripping a precipitator to obtain a solution A, stirring the solution A, and adding a silicon source to obtain a solution B;
centrifuging the solution B, washing, drying and calcining to obtain mesoporous SiO 2 A microsphere;
mesoporous SiO 2 Dispersing the microspheres in a solvent, and obtaining a solution C after ultrasonic treatment and/or stirring;
dispersing a cerium source and a precipitator in a solvent, carrying out ultrasonic treatment and/or stirring to obtain a solution D, adding the solution D into the solution C, and carrying out stirring reaction to obtain a solution E;
centrifuging the solution E, washing, drying, calcining, grinding and sieving to obtain SiO with mesoporous core-shell structure for copper CMP 2 /CeO 2 Composite microspheres.
4. The SiO for copper CMP having a mesoporous core-shell structure according to claim 3 2 /CeO 2 The preparation method of the composite microsphere is characterized in that the dosage ratio of the template agent, the precipitator and the silicon source is (0.4-0.8) g (1-2) ml (1-3) ml;
the mesoporous SiO 2 The mass ratio of the microsphere to the cerium source to the precipitator is (0.4-1): 0.6-1.2): 0.96-1.92;
the template agent comprises cetyl trimethyl ammonium bromide, the precipitant comprises ammonia water or hexamethylenetetramine, the silicon source comprises tetraethoxysilane, the cerium source comprises cerium nitrate hexahydrate, and the solvent comprises water and/or alcohol;
the stirring speed is 300-800r/min, and the stirring time is 2-6h; the rotational speed of the centrifugation is 8000-10000r/min, and the time is 5-10min;
the drying temperature is 55-65 ℃, the time is 12-24h, the calcining temperature is 450-650 ℃, and the heat preservation time is 2-4h;
the ultrasonic treatment time is 10-15min, and the washing adopts alcohol and water to separate washing.
5. The SiO for copper CMP having a mesoporous core-shell structure according to claim 4 2 /CeO 2 The preparation method of the composite microsphere is characterized in that the precipitator in the solution A is ammonia water, the precipitator in the solution D is hexamethylenetetramine, the solvent in the solution A is a mixture of water and alcohol, the solvent in the solution C is alcohol, and the solvent in the solution C is water;
the stirring speed in the solution A is 350-800r/min, the time is 2-4h, and the temperature is normal temperature; the stirring speed in the solution E is 300-600r/min, the time is 3-6h, and the temperature is 60-75 ℃;
the number of times of washing is not less than 3, and the alcohol includes ethanol.
6. The SiO for copper CMP having a mesoporous core-shell structure according to claim 5 2 /CeO 2 The preparation method of the composite microsphere is characterized in that the volume ratio of water to alcohol in the solution A is (150-200) (40-60).
7. A chemical mechanical polishing liquid comprising the SiO for copper CMP having a mesoporous core-shell structure according to claim 1 2 /CeO 2 Composite microsphere, corrosion inhibitor, oxidant and complexing agent.
8. The chemical mechanical polishing solution according to claim 7, wherein the polishing solution comprises 0.5-10% of composite microspheres, 0.001-0.5% of corrosion inhibitor, 0.5-5% of oxidant, 0.05-5% of complexing agent and the balance solvent;
the corrosion inhibitor comprises a nitrogen azole compound, the oxidant comprises a strong acid compound, the complexing agent comprises an aminocarboxylic compound, and the solvent comprises water.
9. The chemical mechanical polishing solution according to claim 8, wherein the polishing solution comprises 1-5% of composite microspheres, 0.01-0.05% of corrosion inhibitor, 0.5-2% of oxidant and 0.5-1% of complexing agent by mass;
the nitrogen azole compound comprises benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 5-methyltetrazole, 5-phenyl-1, 2, 4-triazole or 1-hydroxybenzotriazole;
the strong acid compound comprises peroxide compounds such as hydrogen peroxide, peroxyformic acid, persulfates, percarbonates and the like, and periodic acid, perchloric acid, perboric acid or potassium permanganate;
the aminocarboxylic compound comprises glycine, alanine, valine, leucine, proline, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, serine, aspartic acid, threonine, glutamic acid, asparagine, glutamine, nitrilotriacetic acid, ethylenediamine tetraacetic acid or cyclohexanediamine tetraacetic acid.
10. Use of a chemical mechanical polishing solution according to any one of claims 7 to 9 for copper chemical mechanical polishing, wherein the pH of the chemical mechanical polishing solution is adjusted to 8-8.5 during polishing, and the polishing process conditions comprise: the polishing pressure is 1-3.4psi, the rotation speed of the sample loading disc is 60-90r/min, the rotation speed of the polishing disc is 90-120r/min, the feeding flow of the polishing liquid is 60-120ml/min, and the polishing time is 1-5min.
CN202211613769.1A 2022-12-15 2022-12-15 Composite microsphere with mesoporous core-shell structure for copper CMP, preparation method thereof, chemical mechanical polishing solution and application thereof Pending CN116144323A (en)

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