CN114106706B - Copper interconnection polishing solution with pressure buffering effect and preparation method of abrasive thereof - Google Patents

Copper interconnection polishing solution with pressure buffering effect and preparation method of abrasive thereof Download PDF

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CN114106706B
CN114106706B CN202111594180.7A CN202111594180A CN114106706B CN 114106706 B CN114106706 B CN 114106706B CN 202111594180 A CN202111594180 A CN 202111594180A CN 114106706 B CN114106706 B CN 114106706B
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porous sio
abrasive
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CN114106706A (en
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宋英英
王晗笑
姜鉴哲
付聚三
刘圆
张琳
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Boris Tianjin Electronic Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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Abstract

The invention relates to a copper interconnection polishing solution with pressure buffer effect and a preparation method of an abrasive thereof, wherein the polishing solution comprises the following components: abrasive material, at least one oxidizing agent, at least one surfactant and at least one complexing agent, wherein the abrasive material comprises porous SiO 2 Hollow microspheres, porous SiO 2 The particle size of the hollow microsphere is 80-180nm. Porous SiO is introduced into the polishing solution 2 The hollow microspheres can deform under pressure through the hollow silicon dioxide, so that the pressure on the convex and concave parts is different, the disc shape is eliminated, and the copper surface is flattened.

Description

Copper interconnection polishing solution with pressure buffering effect and preparation method of abrasive thereof
Technical Field
The invention relates to a copper interconnection polishing solution with a pressure buffering effect and a preparation method of an abrasive thereof.
Background
The development of integrated circuit technology has been reflected in the continuous reduction of design line width. Cu has higher grain boundary diffusion activation energy, so that electron migration is not easy to occur, and the application of copper wiring in the manufacturing of chips is wider. The dual damascene process is the only copper patterning process that is mature and has been successfully applied to IC fabrication at present; therefore, cu interconnect CMP has become one of the main contents of the research of CMP technology in the industry.
Since the CMP of Cu in the dual damascene process needs to remove Cu, the barrier material and the dielectric layer, which have great differences in physical and chemical properties, and the simultaneous polishing of these materials with different polishing rates results in the unevenness of the surface of the silicon wafer, which usually occurs in the form of Dishing (dising) of polished copper, erosion (Erosion) of the dielectric layer and ultra-poor uniformity in the polished wafer, as shown in fig. 4. With the increasing size of silicon wafers, the problem of non-uniformity in the silicon wafers is more prominent. Among them, the choice of polishing liquid is very important for these irregularities.
In order to solve the problem of non-uniformity in the copper polishing process, a corrosion inhibitor is generally added into the copper polishing solution to inhibit further corrosion of the copper surface and improve the precision of the polished copper surface. However, these inhibitors all play a chemical role: the polishing agent is easy to be adsorbed on the surface of metal to form a protective film, so that the reaction is prevented or slowed down, and the polishing agent is difficult to clean after polishing; in addition, many corrosion inhibitors have benzene rings, for example, the most commonly used inhibitor is Benzotriazole (BTA) and other triazole group chemicals, and the long-term use of the inhibitor in large quantities is liable to cause adverse effects on the ecological environment.
Therefore, how to reduce or even eliminate the addition of chemical corrosion inhibitors as much as possible while ensuring the flatness and polishing rate is a technical problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a copper interconnection polishing solution with pressure buffering effect and a preparation method of an abrasive thereof, wherein porous SiO is introduced into the polishing solution 2 The hollow microspheres can deform under the pressure of the hollow silicon dioxide, so that the pressure on the concave and convex parts is different, the disc shape is eliminated, and the copper surface is flattened.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a copper interconnection polishing solution with pressure buffering function is characterized in that: the polishing solution comprises the following components: abrasive material, at least one oxidizing agent, at least one surfactant and at least one complexing agent, wherein the abrasive material comprises porous SiO 2 Hollow microspheres, porous SiO 2 The particle size of the hollow microspheres is 80-180nm.
The abrasive further comprises SiO 2 Sol, porous SiO 2 The addition amount of the hollow microspheres is more than that of SiO 2 Of solsAddition amount of porous SiO 2 The mass ratio of the hollow microspheres to the whole abrasive is 60-100%, and SiO 2 The mass proportion of the sol in the whole abrasive is 0-40%; the SiO 2 The particle diameter of the particles in the sol is 30-100nm.
A small amount of corrosion inhibitor is also added into the polishing solution, and the addition amount of the corrosion inhibitor is less than that of the porous SiO-free polishing solution 2 The addition amount of the corrosion inhibitor in the polishing solution composition is small when the hollow microspheres are added.
A copper interconnection polishing solution with a pressure buffering effect comprises the following components in percentage by mass:
grinding: 0.6-25% of silica abrasive materials with different particle sizes which are mixed according to the proportion, wherein the silica abrasive materials comprise: porous SiO 2 Hollow microspheres and SiO 2 Sol;
oxidizing agent: h 2 O 2 ，HNO 3 、KIO 4 2-13% of at least one oxidant in HClO and ozone water; preferably H 2 O 2 (analytically pure, 30% aqueous);
complexing agent: 1-13% of amino acid or its derivative, organic amine or their combination;
corrosion inhibitors: 0 to 3 percent of organic five-membered or six-membered heterocyclic compounds containing nitrogen atoms, oxygen atoms or sulfur atoms or nitrogen atoms, oxygen atoms and sulfur atoms simultaneously and derivatives or organic quaternary ammonium salts thereof;
surfactant (B): 3-15% of cationic surfactant, anionic surfactant, amphoteric surfactant or nonionic surfactant; the balance being water.
More specifically, the specific particle size range of the silica abrasive is 30-180nm, wherein the porous SiO is 2 The hollow microsphere accounts for 60 to 100 percent (the grain diameter is 80 to 180 nm), siO 2 The proportion of the sol is 0-40% (the particle size is 30-100 nm); relatively more porous SiO is added 2 The hollow microspheres can generate enough pressure difference and improve the action capability of eliminating the disc shape.
More specifically, the surfactant is: one or more of betaine, lecithin, amino acid derivatives, alkylphenol ethoxylates, polyacrylic acid, acrylic acid-acrylic acid copolymer, fatty alcohol-polyoxyethylene ether sodium sulfate, isooctanol polyoxyethylene ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alkyl glucoside and polyoxyethylene ether;
complexing agent: hydroxycarboxylic acids and salts thereof, aminocarboxylic acids and salts thereof, and hydroxylamine-based carboxylic acids and salts thereof.
The invention also protects a porous SiO 2 The preparation method of the hollow microsphere abrasive comprises the following steps: 100mL of distilled water, 2.2g of cetyltrimethylammonium bromide (CTAB), was stirred at 45 ℃ for 30 minutes; then adding 2.8mL of ammonia water, 3mL of tetraethyl orthosilicate and 0.85mL of ethyl acetate in turn while stirring, and quickly and continuously stirring the obtained mixed system at 40 ℃ for 12 hours; centrifuging the product, and repeatedly washing with ultrasonic dispersion in hot water to remove CTAB to form SiO 2 The porous hollow structure of (2).
Porous SiO synthesized by the method 2 The hollow microspheres have flexibility and elasticity, and cannot scratch the surface of the wafer; simultaneous SiO 2 The layer can be controlled by the adding amount and the reaction time of tetraethyl orthosilicate and the like, and the thickness of the silicon layer which can meet different requirements is synthesized; thereby achieving the ideal polishing effect.
Compared with the prior art, the invention has the beneficial effects that:
the polishing solution of the invention is introduced with porous SiO 2 The hollow microspheres mainly utilize the physical action of the grinding material when reducing the step height: abrasive porous SiO at high position of wafer 2 The hollow microspheres deform due to the pressure of the polishing head, the tension generated by deformation and the pressure of the polishing head act on the high position of the wafer together, and the generated mechanical pressure is larger; the polishing pressure of the copper at the lower part is smaller than that of the copper at the higher part because the abrasive grains are not greatly extruded, and the polishing speed is relatively lower; thereby reducing the height difference at the high position and the low position. Porous SiO when a small amount of corrosion inhibitor is added 2 Hollow microsphere abrasives are combined with chemical protection of corrosion inhibitors (which react with metals to form molecular protective films)And synergistically slow down the polishing rate at low positions, and finally achieve polishing planarization. Meanwhile, due to the fact that the hollow abrasive material is similar to a spring structure, certain elastic deformation occurs in the process of contacting the substrate, necessary buffering is provided, polishing pressure can act on the surface of the wafer more softly, and therefore indentation depth is reduced, mechanical damage is reduced, and polishing planarization effect is better. Simultaneous porous SiO 2 The mesoporous structure of the hollow microspheres is also beneficial to the adsorption of metal ions and other removal objects, and provides convenience for cleaning the polished wafer. The difficulty that the polishing post-cleaning is increased due to the need of using more corrosion inhibitors in the prior art is avoided, and the adverse effect on the ecological environment is also reduced.
The abrasive used in the present invention is porous SiO 2 Hollow microspheres and small-particle-size SiO 2 The mixed abrasive formed by the sol can effectively increase the contact specific surface area of the abrasive and the wafer, thereby improving the mechanical grinding rate; at the same time, due to porous SiO 2 Due to the elastic action of the hollow microspheres, the roughness of the surface of the wafer can be effectively reduced, and the problems of Dishing (Dishing) of copper, erosion (Erosion) of a dielectric layer, ultra-poor uniformity in a polished wafer and the like are avoided; porous SiO 2 The hollow microspheres have porous/mesoporous channels, can play a role in adsorbing and removing objects, and are beneficial to the post-cleaning effect of CMP.
The porous SiO of the invention 2 The hollow microspheres are of hollow structures, and the polishing head acts on SiO 2 The polishing material is pressed differently due to the difference of deformation, so that the planarization effect is achieved, the use of the hard abrasive material with the core-shell structure is avoided, and the polishing material can be suitable for the chemical mechanical polishing process with the silicon wafer as the substrate.
The hollow abrasive material obtained by the abrasive material preparation method has small particle size and high dispersity, and avoids the problem of scratches caused by agglomeration.
Drawings
FIG. 1: polishing liquid abrasive porous SiO 2 Transmission electron microscope images of hollow microspheres.
FIG. 2 is a schematic diagram: porous SiO 2 N of hollow microspheres 2 Adsorption/desorption isotherms.
FIG. 3: porous SiO in polishing process 2 Elastic action of microspheres and SiO 2 Schematic illustration of sol co-action to reduce dishing, etc.
FIG. 4 is a schematic view of: copper dishing and erosion process map.
Detailed Description
The present invention is further explained with reference to the following examples and drawings, but the scope of the present invention is not limited thereto.
FIG. 3 shows porous SiO during polishing 2 Elastic action of microspheres and reaction with SiO 2 Schematic illustration of the sol co-action to reduce dishing and the like. Based on the chemical mechanical polishing mechanism of elastic-plastic contact mechanics, the hollow microspheres have low hardness, are beneficial to improving the physical contact behavior between particles and the surface of a processed object, and reduce the contact stress and the pressing depth between a single abrasive and a substrate, so that the mechanical force applied to the lower part of the surface of a wafer is relatively small. Porous SiO 2 The hollow structure of the hollow microsphere can generate elastic deformation tension, so that the hollow microsphere has the property similar to a spring, and in the grinding process, at the high part of the surface of a wafer, the grinding material is deformed under the pressure of a polishing head, and at the lower part of the surface of the wafer, the grinding material is extruded to generate deformed porous SiO 2 The hollow microspheres have a larger mechanical action, and the removal rate is higher; the speed difference enables the polishing planarization effect to be better, and can effectively avoid the phenomena of copper Dishing (disking), dielectric layer Erosion (Erosion) and the like. At the same time, porous SiO 2 The property of the hollow microspheres similar to springs can enable the mechanical action force of the abrasive to be applied to the surface of the wafer more softly, and provides necessary buffering for the mechanical action of the abrasive. The method is also beneficial to reducing the indentation depth, increasing the real contact area between the abrasive particles and the wafer to a certain extent, further reducing the mechanical damage and reducing the problem of poor uniformity in the polished wafer.
In summary, porous SiO is present in the copper polishing solution 2 The addition of the hollow microsphere abrasive can effectively inhibit the problems of Dishing (Dishing) of copper, erosion (Erosis) of a dielectric layer, ultra-poor uniformity in a polished wafer and the like, and achieve the planarization effect to a higher degree.
Example 1
The polishing solution of the example comprises the following components in percentage by weight: porous SiO 2 12 percent of hollow microspheres (the particle size is 60-120 nm); h 2 O 2 (30% solution), 6%; 3 percent of ethylenediamine tetraacetic acid; betaine, 3%.
The porous SiO 2 The preparation method of the hollow microsphere abrasive comprises the following steps: 100mL of distilled water, 2.2g of cetyltrimethylammonium bromide (CTAB) were stirred at 45 ℃ for 30 minutes; then, 2.8mL of ammonia water, 3mL of tetraethyl orthosilicate and 0.85mL of ethyl acetate are added in turn while stirring, and the obtained mixed system is rapidly and continuously stirred for 12 hours at the temperature of 40 ℃; centrifugally separating the product, ultrasonically dispersing in hot water, and repeatedly washing to remove CTAB to obtain nano-porous SiO 2 Hollow microspheres. Porous SiO 2 The transmission electron microscope image of the hollow microsphere is shown in FIG. 1, and the particle size is about 120 nm.
FIG. 2 is a view of porous SiO 2 N of hollow microspheres 2 The adsorption/desorption isotherm, which is a type IV hysteresis isotherm, illustrates the porous SiO prepared in this example 2 The silicon shell of the hollow microsphere has the characteristics of porosity and mesopores.
Polishing the surface of the silicon wafer, wherein the corresponding experimental data are as follows: polishing conditions: upper and lower projectile rotation speeds: 97/103rpm; the flow rate of the polishing solution is 300mL/min; polishing pressure: 2.5psi; the removal rate was 6823A/min, and the surface roughness Sq was 2.8nm.
Example 2
The polishing solution of the example comprises the following components in percentage by weight: porous SiO 2 Hollow microsphere (particle diameter of 60-120 nm) and SiO 2 Sol (particle size 30-60 nm), mixed at 2; h 2 O 2 (30% solution), 6%; 3 percent of ethylenediamine tetraacetic acid; 3 percent of betaine.
Corresponding experimental data: polishing conditions: upper and lower throwing head rotating speed: 97/103rpm; the flow rate of the polishing solution is 300mL/min; polishing pressure: 2.5psi; the removal rate was 7739A/min, and the surface roughness Sq was 3.3nm.
Examples3
The polishing solution of the example comprises the following components in percentage by weight: siO 2 2 Sol (particle size of 60-120 nm) and SiO 2 Sol (particle size 30-60 nm), 12% mixed with 2; h 2 O 2 (30% solution), 6%; 3 percent of ethylenediamine tetraacetic acid; 3 percent of betaine.
Corresponding experimental data: polishing conditions: upper and lower throwing head rotating speed: 97/103rpm; the flow rate of the polishing solution is 300mL/min; polishing pressure: 2.5psi; the removal rate was 9334A/min, and the surface roughness Sq was 23.1nm.
Comparing examples 1 to 3, it can be seen that under the same conditions, porous SiO 2 In the presence of hollow microspheres, the surface roughness and SiO can be obviously reduced 2 The introduction of the sol can improve the removal rate, and the removal rate is improved in porous SiO 2 Hollow microspheres and SiO 2 Under the condition of ensuring the removal rate, the polishing sample with lower roughness can be obtained under the condition of proper proportion of the sol.
Example 4
The polishing solution of the example comprises the following components in percentage by weight: siO 2 2 Sol (particle size of 60-120 nm) and SiO 2 Sol (particle size 30-60 nm), 12% mixed with 2; h 2 O 2 (30% solution), 6%; 3 percent of ethylenediamine tetraacetic acid; benzotriazole BTA,2%; 3 percent of betaine.
Corresponding experimental data: polishing conditions: upper and lower throwing head rotating speed: 97/103rpm; the flow rate of the polishing solution is 300mL/min; polishing pressure: 2.5psi; the removal rate was 7152A/min, and the surface roughness Sq was 3.3nm.
As can be seen from comparative examples 2 to 4, siO can be achieved with the addition of a relatively large amount of inhibitor 2 Sol reduced surface roughness, and porous SiO prior to this application 2 The introduction of the hollow microspheres can replace the action of a corrosion inhibitor to achieve almost the same polishing effect.
Example 5
The polishing solution of the example comprises the following components in percentage by weight: porous SiO 2 Hollow microsphere (particle diameter of 60-120 nm) and SiO 2 Sol (particle diameter)30-60 nm), mixed at 2; h 2 O 2 (30% solution), 6%; 3 percent of ethylenediamine tetraacetic acid; benzotriazole, 1%; 3 percent of betaine.
Corresponding experimental data: polishing conditions: upper and lower throwing head rotating speed: 97/103rpm; the flow rate of the polishing solution is 300mL/min; polishing pressure: 2.5psi; the removal rate was 6900A/min, and the surface roughness Sq was 2.1nm.
Comparative example 4 and example 5, incorporating porous SiO 2 Under the synergistic effect of the hollow microspheres and a small amount of corrosion inhibitor, the higher removal efficiency can be ensured and the addition of the corrosion inhibitor is reduced on the premise of improving the surface roughness.
The formula of the polishing solution can introduce porous SiO under the same conditions 2 Under the condition of the hollow microspheres, the roughness is controlled within 3.5nm, the removal rate is over 6800, the requirement on the roughness is met, the higher removal rate is guaranteed, and the pollution to the environment is reduced.
The invention has the following synergistic effect among the formulas: during the polishing process, firstly, all the copper on the surface of the silicon wafer is oxidized by the oxidant, wherein the metal copper on the protruding part is continuously polished and removed while being oxidized (the abrasive porous SiO in the part is polished and removed) 2 The hollow microspheres are deformed and extruded to generate mechanical pressure which is higher than that of the low abrasive material), or react with the complexing agent to generate complex to dissolve. The polishing pressure of the copper at the lower part is smaller than that of the copper at the higher part because the abrasive particles are not greatly extruded, and the polishing speed is relatively lower; or the chemical protection function of the chemical protective film is combined with the chemical protection function of a corrosion inhibitor (the corrosion inhibitor is directly complexed with metal and reacts with the metal to form the molecular protective film, the mechanical acting force is smaller at a low position, and the complexing agent is difficult to enter and is decomplexed with new metal copper at a lower layer due to the steric hindrance of the inhibitor, so the molecular protective film is formed), the polishing speed at the low position is synergistically slowed, and finally the polishing planarization is achieved. Meanwhile, due to the structure that the hollow abrasive material is similar to a spring, certain elastic deformation occurs in the process of contacting the substrate, necessary buffering is provided, and polishing pressure can be applied to the substrate more softlyThe surface of the wafer is beneficial to reducing the indentation depth and further reducing mechanical damage, so that the polishing planarization effect is better.
Nothing in this specification is said to apply to the prior art.

Claims (4)

1. A copper interconnection polishing solution with pressure buffering function is characterized in that: the polishing solution comprises the following components: abrasive material, at least one oxidizing agent, at least one surfactant and at least one complexing agent, wherein the abrasive material comprises porous SiO 2 Hollow microspheres, porous SiO 2 The particle size of the hollow microspheres is 80-180nm;
the porous SiO 2 The preparation process of the hollow microsphere comprises the following steps: stirring 100mL of distilled water and 2.2g of hexadecyl trimethyl ammonium bromide at 45 ℃ for 30 minutes; then, 2.8mL of ammonia water, 3mL of tetraethyl orthosilicate and 0.85mL of ethyl acetate are added in turn while stirring, and the obtained mixed system is rapidly and continuously stirred for 12 hours at the temperature of 40 ℃; centrifugally separating the product, ultrasonically dispersing in hot water, and repeatedly washing to remove CTAB to obtain nano-porous SiO 2 Hollow microspheres.
2. The polishing solution according to claim 1, wherein the abrasive further comprises SiO 2 Sol, porous SiO 2 The addition amount of the hollow microspheres is more than that of SiO 2 Amount of sol added, porous SiO 2 The mass ratio of the hollow microspheres to the whole abrasive is 60-100%, and SiO is 2 The mass proportion of the sol in the whole abrasive is 0-40%; the SiO 2 The particle diameter of the particles in the sol is 30-100nm.
3. A copper interconnection polishing solution with a pressure buffering effect comprises the following components in percentage by mass:
grinding materials: 0.6-25% of silica abrasives of different grain sizes mixed in proportion, which comprises: porous SiO 2 Hollow microspheres and SiO 2 Sol; wherein the porous SiO 2 60-100% of hollow microsphere and SiO 2 The proportion of the sol is 0-40%;
oxidizing agent: h 2 O 2 ，HNO 3 、KIO 4 2% -13% of at least one oxidant in HClO and ozone water;
complexing agent: 1% -13% of hydroxycarboxylic acid and salts thereof, aminocarboxylic acid and salts thereof, and hydroxylamine carboxylic acid and salts thereof;
corrosion inhibitors: 0 to 3 percent of organic five-membered or six-membered heterocyclic compound containing nitrogen atom, oxygen atom or sulfur atom in the structure, and derivatives or organic quaternary ammonium salt thereof, or organic five-membered or six-membered heterocyclic compound containing nitrogen atom, oxygen atom and sulfur atom simultaneously, and derivatives or organic quaternary ammonium salt thereof;
surfactant (b): 3% -15% of cationic surfactant, anionic surfactant, amphoteric surfactant or nonionic surfactant;
the balance of water;
porous SiO 2 The preparation process of the hollow microsphere comprises the following steps: stirring 100mL of distilled water and 2.2g of hexadecyl trimethyl ammonium bromide at 45 ℃ for 30 minutes; then adding 2.8mL of ammonia water, 3mL of tetraethyl orthosilicate and 0.85mL of ethyl acetate in turn while stirring, and quickly and continuously stirring the obtained mixed system at 40 ℃ for 12 hours; centrifugally separating the product, ultrasonically dispersing in hot water, and repeatedly washing to remove CTAB to obtain nano-porous SiO 2 Hollow microspheres.
4. The polishing solution according to claim 3, wherein the specific particle size of the silica abrasive is in the range of 30 to 180nm; porous SiO 2 The particle size of the hollow microsphere is 80-180nm 2 The particle size of the sol is 30-100nm;
the surfactant is: betaine, lecithin, amino acid derivatives, alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether sodium sulfate, isooctanol polyoxyethylene ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alkyl glucoside, and polyoxyethylene ether.
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