CN118255816A - Iron complex, preparation method, composition, slurry and application thereof - Google Patents

Iron complex, preparation method, composition, slurry and application thereof Download PDF

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CN118255816A
CN118255816A CN202211702227.1A CN202211702227A CN118255816A CN 118255816 A CN118255816 A CN 118255816A CN 202211702227 A CN202211702227 A CN 202211702227A CN 118255816 A CN118255816 A CN 118255816A
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slurry
iron complex
metal
acid
composition
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马小舟
金路
刘强
范怡平
张珂
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Huawei Technologies Co Ltd
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Priority to PCT/CN2023/142588 priority patent/WO2024140874A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • C23F3/06—Heavy metals with acidic solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics

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  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

The application discloses an iron complex and a preparation method, a composition, slurry and a flattening method thereof, belonging to the technical field of surface treatment. The iron complex has a chemical formula of Fe (L) x, wherein 0< x <7, and the L group comprises at least one of 1, 1-cyclobutanedicarboxylic acid group, 1-cyclopropyl dicarboxylic acid group, ethylabbreviated malic acid group, benzyl hard acid group, and phenylmorpholino acid group. The iron complex can be used as an oxidant in the slurry, and the iron complex and the metal corrosion inhibitor and the nano particles cooperate, so that the slurry not only has good grinding rate, but also has extremely low metal static corrosion rate, for example, the tungsten static corrosion rate is extremely low, and the corrosion loss of the tungsten metal surface can be effectively inhibited.

Description

Iron complex, preparation method, composition, slurry and application thereof
Technical Field
The present disclosure relates to the field of surface treatment technology, and in particular to iron complexes, methods of making, compositions, slurries and applications thereof.
Background
Chemical Mechanical Polishing (CMP) is typically used to planarize substrates, for example, during the fabrication of chips, which typically involves Polishing of metal tungsten, the planarization efficiency of the metal tungsten layer directly affects the production yield of the chips.
The polishing effect of the chemical mechanical polishing depends on the chemical mechanical polishing composition, and for example, the related art provides a chemical mechanical polishing composition comprising oxidizing tungsten metal to a tungsten oxide film that is more easily removed by allowing hydrogen peroxide and/or ferric nitrate to interact with silicon dioxide or the like as an oxidizing agent, the hydrogen peroxide and/or ferric nitrate synergistically acting, and removing the tungsten oxide film using silicon dioxide as an abrasive.
However, the chemical mechanical polishing composition provided by the related art causes corrosion loss on the surface of tungsten metal, causing pitting corrosion.
BRIEF SUMMARY OF THE PRESENT DISCLOSURE
In view of this, the present disclosure provides an iron complex, a method of preparing the same, a composition, a slurry, and an application thereof, which can solve technical problems existing in the related art.
Specifically, the method comprises the following technical scheme:
In one aspect, an iron complex is provided having the formula Fe (L) x, wherein 0< x <7, the L group includes at least one of a1, 1-cyclobutanedicarboxylic acid group, a1, 1-cyclopropanedicarboxylic acid group, an ethylabbreviated malic acid group, a benzylstearic acid group, a phenylmorpholino group.
The embodiment of the disclosure provides an iron complex, wherein the metal center of the iron complex is ferric iron, and the iron complex has a hexacoordination environment. The ligand is at least one of 1, 1-cyclobutanedicarboxylic acid, 1-cyclopropyl dicarboxylic acid, ethylabbreviated malic acid, benzyl stearic acid and phenylmorpholinic acid, and the ligand is matched with ferric ion to enable the iron complex to have an oxidation effect. For example, the iron complex can be used in the field of metal polishing, which can slowly oxidize a metal surface to form a softened metal oxide layer to reduce corrosion to the metal surface, has a low static corrosion rate of the metal, and at the same time, exhibits excellent polishing selectivity.
In some possible implementations, the iron complex is an oxidizing agent.
The oxidant based on the iron complex provided by the embodiment of the disclosure can be used for grinding slurry, and the oxidant and the metal corrosion inhibitor and the nano particles cooperate, so that the slurry not only has good grinding rate, but also has extremely low metal static corrosion rate, for example, the tungsten static corrosion rate is extremely low, can effectively inhibit the corrosion loss of the tungsten metal surface, and simultaneously, also has excellent polishing selectivity.
In another aspect, there is provided a method of preparing an iron complex, the iron complex being as described in any one of the above, the method comprising:
Providing an aqueous solution of at least one of 1, 1-cyclobutanedicarboxylic acid, 1-cyclopropyldicarboxylic acid, ethylabbreviated malic acid, benzyl stearic acid and phenylmorpholinic acid as an acid liquid raw material;
according to the chemical formula of the iron complex, the acid liquid raw material and ferric nitrate are uniformly mixed according to a set proportion, and the iron complex is obtained after separation.
In yet another aspect, a composition is provided comprising nanoparticles and an adjuvant comprising an iron complex as described above or as prepared by a method of preparing an iron complex as described above.
The compositions provided by embodiments of the present disclosure can be used in chemical mechanical polishing, and can also be considered a chemical mechanical polishing composition. Based on the use of the iron complex as an oxidizing agent and the nanoparticles as an abrasive, the iron complex and the nanoparticles act synergistically, not only can slowly oxidize the metal surface to form a softened metal oxide layer, but also can reduce the corrosion to the metal surface, so that the composition has a good grinding rate and an extremely low static corrosion rate of the metal, for example, the tungsten is extremely low, and can effectively inhibit the corrosion loss of the tungsten metal surface.
In some possible implementations, the composition further includes a metal corrosion inhibitor.
The iron complex, the nano particles and the metal corrosion inhibitor act synergistically, so that the composition not only has good grinding rate, but also has extremely low metal static corrosion rate, and also shows excellent polishing selectivity.
In some possible implementations, the metal corrosion inhibitor includes at least one of an amino acid compound, an aminoalkyl compound, an alkylammonium ion compound.
In some possible implementations, the metal corrosion inhibitor is an amino acid compound.
In some possible implementations, the nanoparticles are selected from at least one of silicon oxide, titanium oxide, aluminum oxide, germanium oxide, zirconium oxide, cerium oxide, silicon carbide.
In some possible implementations, the nanoparticle is colloidal silica.
In some possible implementations, the zeta potential of the colloidal silica in the composition is less than 10mV, which can achieve higher polishing efficiency.
In yet another aspect, a slurry is provided comprising any of the above compositions and water, wherein the hydrogen peroxide is present in the slurry in an amount of less than 500ppm.
The slurry provided by the embodiment of the disclosure can be used for chemical mechanical polishing of metal, and based on the use of the iron complex as an oxidant and the nano particles as an abrasive, the iron complex and the nano particles cooperate to not only slowly oxidize the metal surface to form a softened metal oxide layer, but also reduce the corrosion to the metal surface, so that the composition has a good grinding rate and an extremely low static metal corrosion rate. In some examples, the composition further includes a metal corrosion inhibitor, the iron complex, the nanoparticle, and the metal corrosion inhibitor act synergistically such that the composition not only has a good polishing rate, but also has a very low static corrosion rate of the metal, and also exhibits excellent polishing selectivity.
In some possible implementations, the hydrogen peroxide content in the slurry is less than 100ppm, and further, the hydrogen peroxide content is 0.
In some possible implementations, the composition includes an iron complex, a nanoparticle, and a metal corrosion inhibitor;
the iron complex accounts for 0.1 to 0.5 percent of the mass of the slurry;
The nano particles account for 0.1 to 5 percent of the mass of the slurry;
The metal corrosion inhibitor accounts for 0.001 to 0.5 percent of the mass of the slurry.
In some possible implementations, the slurry further includes a pH adjuster for providing the slurry with a pH in the range of 1 to 4.
The slurry provided by the embodiment of the disclosure is designed to be used for polishing operation under the pH value range of 1-4, so as to achieve the purpose of optimizing the action effect.
In yet another aspect, a planarization method is provided, the planarization method including:
contacting the substrate with the planarizing pad and the slurry, wherein the slurry is located between the substrate and the planarizing pad;
moving the planarizing pad relative to the substrate to planarize the substrate by abrading at least a portion of the substrate based on the slurry;
wherein the slurry is as described in any one of the above.
The planarization method provided by the embodiments of the present disclosure can be used to planarize a surface of a substrate, and in some examples, the planarization method according to the embodiments of the present disclosure is a polishing method, that is, based on the slurry provided by the embodiments of the present disclosure, with which the substrate can be polished. Accordingly, the planarizing pad is a polishing pad and the above-mentioned polishing rates are referred to as polishing rates.
In some possible implementations, the substrate includes a metal layer in contact with the slurry, the metal layer including at least one of tungsten, ruthenium, and molybdenum.
Detailed Description
In order to make the technical solutions and advantages of the present disclosure more apparent, embodiments of the present disclosure will be described in further detail below.
Chemical Mechanical Polishing (CMP) is typically used to planarize substrates, for example, during the fabrication of chips, which typically involves Polishing of metal tungsten, the planarization efficiency of the metal tungsten layer directly affects the production yield of the chips.
In a conventional CMP operation, a substrate to be polished is mounted on a carrier (polishing head), and in turn, on a carrier assembly and positioned in contact with a polishing pad in a polishing tool. The carrier assembly provides a controlled pressure to the substrate to urge the polishing pad against the substrate. The polishing pad is moved relative to the substrate by an external driving force, and the relative motion of the two abrades the surface of the substrate to remove a portion of the material from the substrate surface, thereby polishing the substrate.
The polishing of the substrate may be further aided by a slurry that flows between the substrate and the polishing pad during polishing to form a thin film of liquid. The chemical components in the slurry react with the surface of the substrate to form a relatively easily removable reaction layer, which is removed under polishing pressure to planarize the substrate.
For example, tungsten metal is often used to fabricate tungsten "plug" and "interconnect" structures within a dielectric layer, with tungsten metal filling in openings in the dielectric layer and excess tungsten deposited on the surface of the dielectric layer in a typical tungsten plug and interconnect process. After removal of bulk tungsten, the substrate surface may undergo a buffing step to remove the uneven portions and provide a more uniform topography to the surface.
There is a high demand for the buffing operation because erosion in substrate features (such as tungsten plugs and interconnects), which is the removal of excess metal from the substrate features, must be minimized, resulting in non-planarity.
The related art provides a chemical mechanical polishing composition comprising oxidizing tungsten metal to a tungsten oxide film that is easier to remove by allowing hydrogen peroxide and/or ferric nitrate to interact with silicon dioxide or the like as an oxidizing agent, the hydrogen peroxide and/or ferric nitrate synergistically act, and removing the tungsten oxide film using silicon dioxide as an abrasive. However, the chemical mechanical polishing composition provided by the related art causes corrosion loss on the surface of tungsten metal, causing pitting corrosion.
According to one aspect of embodiments of the present disclosure, there is provided an iron complex having a chemical formula of Fe (L) x, wherein 0< x <7, the L group includes at least one of a1, 1-cyclobutanedicarboxylic acid group, a1, 1-cyclopropanedicarboxylic acid group, an ethylabbreviated acid group, a benzylstearic acid group, a phenylmorpholino group.
The embodiment of the disclosure provides an iron complex, wherein the metal center of the iron complex is ferric iron, and the iron complex has a hexacoordination environment. The ligand is at least one of 1, 1-cyclobutanedicarboxylic acid, 1-cyclopropyl dicarboxylic acid, ethylabbreviated malic acid, benzyl stearic acid and phenylmorpholinic acid, and the ligand is matched with ferric ion to enable the iron complex to have an oxidation effect. For example, the iron complex can be used in the field of metal polishing, which can slowly oxidize a metal surface to form a softened metal oxide layer to reduce corrosion to the metal surface, has a low static corrosion rate of the metal, and at the same time, exhibits excellent polishing selectivity.
For the iron complex Fe (L) x, where x has a value in the range: 0< x <7, in some examples, the value of x includes, but is not limited to, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, etc.
Based on the value range of x, ligand L and ferric ion are chelated with each other in a specific molar ratio, which is beneficial to improving the structural stability.
The ligand L is selected from at least one of 1, 1-cyclobutanedicarboxylic acid, 1-cyclopropyl dicarboxylic acid, ethylabbreviated malic acid, benzyl stearic acid and ferric phenylmorpholinate, namely, the iron complex comprises at least one of 1, 1-cyclobutanedicarboxylic acid, 1-cyclopropyl dicarboxylic acid, ethylabbreviated malic acid, benzyl stearic acid and ferric phenylmorpholinate.
In some examples, the iron complex may be iron 1, 1-cyclobutanedicarboxylate, iron 1, 1-cyclopropyl-dicarboxylate, iron ethyldimaleate, iron benzylstearate, or iron phenylmorpholinate.
The iron complex formed by chelating the above-mentioned kind of carboxylic acid ligand with the iron ion acts synergistically with the metal corrosion inhibitor, and unexpectedly exhibits a strong polishing efficiency and a strong static metal corrosion inhibition effect.
In some examples, the L group further comprises a malonic acid group, malonic acid acting as a ligand in combination with ferric ion, also capable of acting as an oxidizing agent, and ferric malonate in combination with at least one of the above-mentioned iron complexes, capable of achieving a favorable effect of inhibiting metal corrosion.
Embodiments of the present disclosure also provide for the use of an iron complex in an oxidizing agent, e.g., the iron complex is an oxidizing agent.
The oxidant based on the iron complex provided by the embodiment of the disclosure can be used for grinding slurry, and the oxidant and the metal corrosion inhibitor and the nano particles cooperate, so that the slurry not only has good grinding rate, but also has extremely low metal static corrosion rate, for example, the tungsten static corrosion rate is extremely low, can effectively inhibit the corrosion loss of the tungsten metal surface, and simultaneously, also has excellent polishing selectivity.
According to another aspect of embodiments of the present disclosure, there is provided a method of preparing an iron complex, the iron complex being as described above.
An aqueous solution of at least one of 1, 1-cyclobutanedicarboxylic acid, 1-cyclopropanedicarboxylic acid, ethylabbreviated malic acid, benzyl stearic acid, and phenylmorpholinic acid is provided as an acid liquid raw material.
According to the chemical formula of the iron complex, the acid liquid raw material and ferric nitrate are uniformly mixed according to a set proportion, and the iron complex is obtained after separation.
Wherein the molar ratio of the iron atom to the carboxylic acid ligand L is determined according to the chemical formula of the iron complex, and the concentration of the carboxylic acid contained in the acid liquid raw material is combined to determine the respective amounts of the iron nitrate and the acid liquid raw material, wherein the concentration of the carboxylic acid contained in the acid liquid raw material may be 10wt% to 70wt%, for example, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, and the like.
In some examples, the oxidant is prepared by mixing the acid solution raw material with ferric nitrate according to a set proportion at normal temperature (for example, 20-30 ℃), stirring for 10-30 min, and separating. Some suitable separation means include, but are not limited to: recrystallizing, extracting, etc.
In some examples, an aqueous solution of malonic acid may also be provided as an acid feed, and an iron complex ferric malonate may be prepared according to the procedure shown above.
According to still another aspect of embodiments of the present disclosure, there is provided a composition comprising nanoparticles and an auxiliary agent, wherein the auxiliary agent comprises any one of the iron complexes described above or an iron complex prepared by the preparation method of the iron complex described above
Wherein the chemical formula of the iron complex is Fe (L) x, wherein 0< x <7, L is at least one of 1, 1-cyclobutanedicarboxylic acid group, 1-cyclopropyl dicarboxylic acid group, ethylabbreviated malic acid group and benzyl hard acid group. Further, L may also include malonic acid groups.
The compositions provided by embodiments of the present disclosure can be used in chemical mechanical polishing, and can also be considered a chemical mechanical polishing composition. Based on the use of the iron complex as an auxiliary agent (being an oxidizing agent), the nano particles act synergistically with the nano particles, so that not only can the metal surface be oxidized slowly to form a softened metal oxide layer, but also the corrosion to the metal surface can be reduced, and the composition has a good grinding rate, and has an extremely low static corrosion rate of the metal, for example, an extremely low static corrosion rate of tungsten, and can effectively inhibit the corrosion loss of the tungsten metal surface. At the same time, it also exhibits excellent polishing selectivity.
In some examples, the compositions provided by embodiments of the present disclosure further include a metal corrosion inhibitor, iron complex, nanoparticle, metal corrosion inhibitor, acting synergistically such that the compositions not only have good polishing rates, but also have very low static metal corrosion rates, and exhibit excellent polishing selectivity.
In some examples, the composition is free of hydrogen peroxide (referred to as hydrogen peroxide in water), which results in higher metal grinding rates and metal static corrosion rates, while the compositions provided by the embodiments of the present disclosure are free of added hydrogen peroxide, and still have both higher metal grinding rates and very low metal static corrosion rates.
In some examples, the compositions provided by embodiments of the present disclosure include an iron complex, a nanoparticle, and a metal corrosion inhibitor, and the mass ratio of the iron complex, the nanoparticle, and the metal corrosion inhibitor is 1:1 to 50:0.002 to 5.
In embodiments of the present disclosure, the metal corrosion inhibitor acts as a corrosion inhibitor to the metal surface, and in some examples, some of the metal corrosion inhibitors that act as corrosion inhibitors include at least one of amino acid compounds, aminoalkyl compounds, alkylammonium ion compounds.
For amino acid compounds, it is a compound comprising an amino group, for example, this includes, but is not limited to, amino acids, polyamino acids, or other long chain compounds containing an amino group, and the like.
For amino acids, they may be synthetic or naturally occurring, including, for example, but not limited to: histidine, lysine, tyrosine, arginine, glutamine, glutamic acid, glycine, cystine, cysteine, serine, aspartic acid, threonine, and the like.
For polyamino acids, it includes, but is not limited to: polyhistidine, polylysine, polytyrosine, polyarginine, polyglutamine, polyglutamic acid, polyglycine, polycysteine, polyserine, polyaspartic acid, polythreonine, and the like.
For aminoalkyl-based compounds, it includes, but is not limited to, aminopropyl silanol, aminopropyl siloxane, dodecylamine, and the like.
By alkylammonium ion-based compounds, it is meant nitrogen-containing compounds having functional groups that can generate alkylammonium ions in aqueous solutions, including, but not limited to: at least one of cetyltrimethylammonium hydroxide, tetrabutylammonium hydroxide, dodecylamine and tetramethylammonium hydroxide.
In some examples, the metal corrosion inhibitors to which embodiments of the present disclosure relate are amino acid compounds, such as amino acids, polyamino acids, or other long chain compounds containing amino groups, and the like.
The amino acid compound has coordination groups such as amino groups and carboxyl groups (and the polyamino acid also has an amide group), so that the amino acid or the polyamino acid forms bonds with metal on the surface of the protected metal through a plurality of coordination groups of the amino acid or the polyamino acid or is electrostatically adsorbed on the surface of the metal, and a surface passivation layer is further formed on the surface of the metal, thereby inhibiting the contact between an interface and the composition and playing a role of a corrosion inhibitor.
In particular, the metal corrosion inhibitor constituted by the amino acid compound and the oxidizing agent constituted by the above-mentioned iron chelate have at least the following effects: on the basis of ensuring a better grinding rate, the polishing agent has extremely low static corrosion rate and good polishing selectivity, wherein the ratio of the metal grinding rate to the silicon oxide (Ox for short) grinding rate is less than 1.
In some examples, the metal corrosion inhibitor is polylysine and the polylysine comprises 0.001% -0.015% by mass of the slurry, e.g., 0.001% -0.01% by mass, such that the slurry has both a relatively high polishing rate and a very low static etch rate.
In some examples, the metal corrosion inhibitor is lysine and the lysine comprises 0.05% to 0.1% by mass of the slurry, such as 0.05% to 0.01%, so that the slurry has both a relatively high polishing rate and a very low static corrosion rate.
The composition provided by the embodiments of the present disclosure removes the reaction layer by mechanical action of the nanoparticles, that is, the nanoparticles are used as abrasive particles, and some suitable nanoparticles are selected from at least one of silicon oxide, titanium oxide, aluminum oxide, germanium oxide, zirconium oxide, cerium oxide, silicon carbide.
The particle size of the nanoparticle is 10nm to 300nm, for example, 10nm to 200nm, 10nm to 150nm, 10nm to 140nm, 10nm to 130nm, 10nm to 120nm, 10nm to 110nm, 10nm to 100nm, etc., including but not limited to: 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm and the like, thereby effectively preventing scratches on the surface of the substrate on the premise of ensuring high removal rate.
In some examples, the nanoparticle is a silicon oxide, wherein the silicon oxide is prepared by a method including, but not limited to, elemental silicon method, ion exchange method, sol gel method, and the like.
In some examples, the silica is colloidal silica, that is, the silica is present in the form of a silica sol that is soluble in water.
In the embodiment of the disclosure, the charge on the surface of the colloidal silica is extremely low (can be considered as uncharged), so that the absolute value of the Zeta potential on the surface of the colloidal silica is reduced, the like charge repulsion effect of the colloidal silica particles and the surface of the substrate is reduced, the friction force between the nano particles and the substrate in the polishing process is increased, the removal rate is improved, and higher polishing efficiency is obtained.
In some examples, the colloidal silica has a zeta potential of less than 10mV in the composition, which can result in higher polishing efficiency based on the above.
In some examples, the colloidal silica has a particle size (i.e., the particle size of the silica after swelling, corresponding to the secondary particle size) of 30nm to 120nm, including, for example, but not limited to, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, etc., to achieve effective removal of the reaction layer on the substrate.
According to still another aspect provided by embodiments of the present disclosure, there is provided a slurry including any one of the above-described compositions and water, wherein the hydrogen peroxide content of the slurry is less than 500ppm.
The slurry provided by the embodiment of the disclosure can be used for chemical mechanical polishing of metal, and based on the use of the iron complex as an oxidant and the nano particles as an abrasive, the iron complex and the nano particles cooperate to not only slowly oxidize the metal surface to form a softened metal oxide layer, but also reduce the corrosion to the metal surface, so that the composition has good polishing rate and extremely low metal static corrosion rate, and simultaneously shows excellent polishing selectivity.
In some examples, the composition further includes a metal corrosion inhibitor, the iron complex, the nanoparticle, the metal corrosion inhibitor act synergistically to further increase the rate of grinding, reduce the static corrosion rate of the metal, and exhibit more excellent polishing selectivity.
Particularly, the content of hydrogen peroxide in the slurry provided by the embodiment of the disclosure is extremely low, for example, less than 500ppm, 400ppm, 300ppm and 200ppm, further less than 100ppm, and further, the content of hydrogen peroxide is 0.
In the embodiment of the present disclosure, the water contained in the slurry may be at least one of deionized water and distilled water.
In some examples, to make the synergy between the individual components in the slurry more efficient, the nanoparticles may be made to account for 0.1-5% of the mass of the slurry; the metal corrosion inhibitor accounts for 0.001 to 0.5 percent of the mass of the slurry; the oxidant accounts for 0.1 to 0.5 percent of the mass of the slurry.
Wherein the mass percent of the nano particles in the slurry comprises, but is not limited to: 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
The mass percent of the metal corrosion inhibitor in the slurry includes, but is not limited to ：0.001％、0.002％、0.003％、0.004％、0.005％、0.006％、0.007％、0.008％、0.009％、0.01％、0.02％、0.03％、0.04％、0.05％、0.06％、0.07％、0.08％、0.09％、0.1％ and the like.
The mass percent of the oxidant in the slurry includes, but is not limited to ：0.1％、0.11％、0.12％、0.13％、0.14％、0.15％、0.16％、0.17％、0.18％、0.19％、0.2％、0.21％、0.22％、0.23％、0.24％、0.25％、0.26％、0.27％、0.28％、0.29％、0.3％ and the like.
By making 0.1 to 5 percent of nano particles, 0.001 to 0.5 percent of metal corrosion inhibitor and 0.1 to 0.5 percent of oxidant act synergistically, the slurry has at least the following advantages:
(1) On the basis of ensuring better grinding rate, the polishing slurry has extremely low static corrosion rate, and the ratio of the polishing grinding rate to the static corrosion rate to the tungsten is more than 700/1, wherein the static corrosion rate to the tungsten is that
(2) The slurry has good polishing selectivity, and the ratio of the polishing rate of the slurry to metal tungsten to the polishing rate to silicon oxide (Ox for short) is less than 1, so that the desired surface morphology can be obtained by balancing the removal rates of different materials.
In some examples, the slurry provided by embodiments of the present disclosure further includes a pH adjuster for providing the slurry with a pH in the range of 1 to 4.
The slurry provided by the embodiment of the disclosure is designed to be used for polishing operation under the pH value range of 1-4, so as to achieve the purpose of optimizing the action effect.
In some examples, pH modifiers are used to bring the pH of the slurry to a range of 2 to 3, for example to a pH of 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, etc.
The amount of the pH regulator in the slurry is sufficient to make the pH value of the slurry within the range of 1 to 4, and further within the range of 2 to 3.
In some examples, the pH adjuster may be an inorganic acid, including but not limited to nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, etc., or an amine, including but not limited to ammonia, ethanolamine, diethanolamine, triethanolamine, aniline, etc., for example.
The slurry provided by the embodiments of the present disclosure can be used for planarization of metals in integrated circuit manufacturing processes, for example, for planarization of tungsten plugs and tungsten interconnects. The slurry can have extremely low static corrosion rate of metal while maintaining a desired polishing rate by making 0.1% -5% of nano particles, 0.001% -0.5% of metal corrosion inhibitor, 0.1% -0.5% of oxidant and pH regulator act synergistically, thereby effectively inhibiting static corrosion of metal surface.
The processing object to which the slurry provided by the embodiments of the present disclosure is applicable, that is, the metal to be planarized includes, but is not limited to, tungsten, ruthenium, molybdenum, and the like.
It is a further aspect of embodiments of the present disclosure to provide a method of preparing a slurry, wherein the slurry is as described above, i.e., the slurry comprises: nanoparticles, metal corrosion inhibitors, iron complexes, and water; the iron complex, as referred to above in the embodiments of the present disclosure, may be used as an oxidizing agent. Wherein, the nano particles account for 0.1 to 5 percent of the mass of the slurry; the metal corrosion inhibitor accounts for 0.001 to 0.5 percent of the mass of the slurry; the iron complex accounts for 0.1 to 0.5 percent of the mass of the slurry.
The preparation method of the slurry is as follows:
According to the mass percentage of each component in the slurry, the nano particles, the metal corrosion inhibitor and the iron complex are dissolved in water and stirred uniformly, so that the expected slurry can be obtained.
According to the target pH value range of the slurry, adding a proper amount of pH regulator into the slurry to regulate the pH value of the system to the target value.
It is yet another aspect of the disclosed embodiments to provide a planarization method, including:
the substrate is contacted with the planarizing pad and a slurry, wherein the slurry is located between the substrate and the planarizing pad.
The planarizing pad is moved relative to the substrate to abrade at least a portion of the substrate based on the slurry to planarize the substrate.
The slurry provided by the embodiment of the present disclosure is described in any one of the foregoing, so that the planarization method provided by the embodiment of the present disclosure has all the advantages of the slurry described above.
The planarization method provided by the embodiments of the present disclosure can be used to planarize a surface of a substrate, and in some examples, the planarization method according to the embodiments of the present disclosure is a polishing method, that is, based on the slurry provided by the embodiments of the present disclosure, with which the substrate can be polished. Accordingly, the planarizing pad is a polishing pad and the above-mentioned polishing rates are referred to as polishing rates.
For a substrate that includes a metal to be polished, the metal to be polished fills the holes on the substrate and covers the substrate, for example, tungsten can be removed in the substrate and tungsten plugs left in the holes on the substrate using the planarization methods provided by embodiments of the present disclosure.
In some examples, the substrate includes an oxide layer and tungsten coated over the oxide layer to fill the holes thereon, for example, the oxide may be silicon oxide, such as borophosphosilicate glass (BPSG), plasma etched tetraethyl orthosilicate (PETE 0S), thermal oxide, undoped silicate glass, high Density Plasma (HDP) oxide, and the like.
Since the slurry provided by the embodiments of the present disclosure also has good polishing selectivity, the ratio of the polishing rate to metal to the polishing rate to silicon oxide (abbreviated as Ox) is less than 1, so that a desired surface morphology can be obtained by balancing the removal rates of different materials.
For a planarizing pad, it can be any chemical mechanical polishing pad known in the art, and the planarizing pad can be made of any suitable polymer having varying density, hardness, thickness, compressibility, and modulus. Further, preferably, the planarizing pad has at least one of a grooved and perforated polishing surface.
In the planarization method provided by the embodiment of the disclosure, the interface between the planarization pad and the substrate can be dynamically contacted by applying a certain pressure, so that the polishing effect of the slurry between the planarization pad and the substrate is improved.
In some examples, the substrate includes a metal layer in contact with the slurry, the metal layer including at least one of tungsten, ruthenium, and molybdenum.
It should be noted that the cmp process is divided into two steps, the first step is to remove a large amount of metal layer and barrier layer deposited on the dielectric layer, and then the second step is to further polish to achieve surface planarization. The planarization method provided by the embodiment of the disclosure can be used for the second step.
Some implementations of the disclosed embodiments will be described in more detail below, however, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1-example 10
Examples 1-10 each provide a slurry that can be used for chemical mechanical polishing, the formulations of which are shown in table 1:
TABLE 1
Wherein the slurries of examples 1-10 further comprise deionized water and a pH adjuster in an amount such that the pH of the slurries is as shown in table 1, the balance deionized water.
In examples 1 to 10, the colloidal silica was uncharged and had a particle diameter of 120nm (here, a secondary particle diameter, and the corresponding primary particle diameter of silica was about 90 nm).
The number ratio of malonic acid groups to iron atoms of the iron malonate is 6:1; for iron benzyl stearate, the number ratio of benzyl stearate groups to iron atoms is 5:1; for 1, 1-cyclobutanedicarboxylic acid iron, the number ratio of 1, 1-cyclobutanedicarboxylic acid groups to iron atoms is 6:1; for iron 1, 1-cyclopropyl dicarboxylic acid, the number ratio of 1, 1-cyclopropyl dicarboxylic acid groups to iron atoms is 3:1; for ferric ethyldimaleate, the number ratio of ethyldimaleate groups to iron atoms is 3:1, and for ferric phenylmorpholinate, the number ratio of phenylmorpholinate groups to iron atoms is 4:1.
According to the formulation of the slurries provided in examples 1-10, the nanoparticles, the iron complex, and the metal corrosion inhibitor were placed in deionized water and stirred uniformly, and then a specific amount of pH adjustor was added thereto according to the respective pH values, and stirred uniformly, thereby preparing each of the slurries.
Comparative example 1-comparative example 4
Comparative examples 1-4 each provided a slurry for comparison, the formulation of which is shown in table 2:
TABLE 2
Wherein the slurries of comparative examples 1-4 further comprise deionized water and a pH adjuster in an amount such that the pH of the slurries is as shown in table 2, the balance deionized water.
In comparative examples 1 to 4, the colloidal silica was uncharged and the particle size of the colloidal silica was 120nm (here, the secondary particle size, the primary particle size of the corresponding silica was about 90 nm).
Test case
The slurries of examples 1 to 10 and comparative examples 1 to 5 were tested for their chemical mechanical polishing properties, specifically, their metal polishing properties and metal corrosion properties, respectively, using test examples, and are specifically shown below:
(1) Static etch rate of tungsten metal W
A1.5 inch tungsten test piece was immersed in 40g of the slurry at room temperature for one hour, then the tungsten test piece was taken out, the remaining liquid was centrifuged at 4000rpm for 40 minutes, then the supernatant was taken, and the removal mass of W was measured by an inductively coupled plasma emission spectrometer (ICP-OES), and the static etch rate of W was calculated in combination with the initial mass of the tungsten test piece, as shown in Table 3.
(2) Polishing rate of tungsten W and polishing rate of silicon oxide
The substrate is subjected to polishing treatment with a polisher based on each slurry, wherein the substrate includes a silicon oxide layer and metallic tungsten filled in holes of the silicon oxide layer. The polishing rate was calculated by measuring the thickness difference of the metal film layer before polishing and after polishing for a certain period of time.
The polishing conditions are as follows: the polishing pressure was 1.5psi, the polishing platen rotation speed was 60rpm, the polishing head rotation speed was 61 rpm, and the slurry drop rate was 200 ml/min. The polishing rates of the metal tungsten W and the polishing rates of the silicon oxide are shown in table 3, respectively.
(3) Zeta potential of the slurry: the zeta potential of the slurries in example 1 to example 10 and the slurries in comparative example 1 to comparative example 5 were respectively tested using a zeta potential tester.
Wherein, in Table 3, the polishing rate of tungsten W is [ W RR ]Represented by:; polishing rate of silicon oxide [ OX RR ]Represented by:; the ratio of the polishing rate of the metal tungsten W to the polishing rate of the silicon oxide is represented by [ W/OX rate ratio ]; static corrosion Rate of tungsten Metal W [ W static corrosion Rate ]Represented by:; the ratio of the polishing rate of the metal tungsten W to the static etch rate of the metal tungsten W is expressed as [ W RR/W static etch rate ].
TABLE 3 Table 3
As can be seen from Table 3, the slurries provided in examples 1-10 according to the present disclosure, although they do not contain hydrogen peroxide, are still capable of significantly reducing the static etch rate of tungsten WEven smaller than) The ratio of tungsten polishing rate/tungsten static etch rate of these slurries >700, showing higher tungsten polishing rates. And, the polishing rates of W/Ox of the slurries provided in examples 1-10 were all <1, even less than 0.5, showing good polishing selectivity.
In contrast, referring to comparative examples 1 to 4, according to the formulation of the currently known polishing compositions, the static corrosion rates of the metal tungsten are all high, and the ratio of the polishing rates of the metal tungsten W to the static corrosion rates of the metal tungsten W is low, so that undesirable pitting corrosion occurs on the surface of the metal tungsten, and it is difficult to achieve a balance between the polishing rates of the metal tungsten W and the static corrosion rates of the metal tungsten W.
The foregoing is merely for facilitating understanding of the technical solutions of the present disclosure by those skilled in the art, and is not intended to limit the present disclosure. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.

Claims (16)

1. An iron complex having the chemical formula Fe (L) x, wherein 0< x <7, the L group comprises at least one of a1, 1-cyclobutanedicarboxylic acid group, a1, 1-cyclopropanedicarboxylic acid group, an ethylabbreviated acid group, a benzylstearic acid group, a phenylmorpholino group.
2. The iron complex of claim 1, wherein the iron complex is an oxidizing agent.
3. A method of preparing an iron complex according to any one of claims 1-2, comprising:
Providing an aqueous solution of at least one of 1, 1-cyclobutanedicarboxylic acid, 1-cyclopropyldicarboxylic acid, ethylabbreviated malic acid, benzyl stearic acid and phenylmorpholinic acid as an acid liquid raw material;
According to the chemical formula of the iron complex, the acid liquid raw material and ferric nitrate are uniformly mixed according to a set proportion, and the iron complex is obtained after separation.
4. A composition comprising nanoparticles and an auxiliary agent comprising the iron complex of any one of claims 1-2 or prepared by the preparation method of claim 3.
5. The composition of claim 4, wherein the composition further comprises a metal corrosion inhibitor.
6. The composition of claim 5, wherein the metal corrosion inhibitor comprises at least one of an amino acid compound, an aminoalkyl compound, an alkylammonium ion compound.
7. The composition of claim 6, wherein the metal corrosion inhibitor is an amino acid compound.
8. The composition of claim 4, wherein the nanoparticle is selected from at least one of silicon oxide, titanium oxide, aluminum oxide, germanium oxide, zirconium oxide, cerium oxide, silicon carbide.
9. The composition of claim 8, wherein the nanoparticle is colloidal silica.
10. The composition of claim 9, wherein the colloidal silica has a zeta potential of less than 10mV in the composition.
11. A slurry comprising the composition of any one of claims 4-10 and water, wherein the hydrogen peroxide is present in the slurry in an amount of less than 500ppm.
12. The slurry of claim 11, wherein the hydrogen peroxide content of the slurry is less than 100ppm.
13. The slurry of claim 11, wherein the composition comprises an iron complex, nanoparticles, and a metal corrosion inhibitor;
the iron complex accounts for 0.1-0.5% of the mass of the slurry;
The nano particles account for 0.1-5% of the mass of the slurry;
The metal corrosion inhibitor accounts for 0.001-0.5% of the mass of the slurry.
14. The slurry according to any one of claims 11-13, further comprising a pH adjuster for bringing the slurry to a pH value in the range of 1-4.
15. A planarization method, the planarization method comprising:
Contacting a substrate with a planarizing pad and a slurry, wherein the slurry is located between the substrate and the planarizing pad;
moving the planarizing pad relative to the substrate to abrade at least a portion of the substrate based on the slurry to effect planarization of the substrate;
Wherein the slurry is as claimed in any one of claims 11 to 14.
16. The planarization method of claim 15, wherein said substrate comprises a metal layer, said metal layer being in contact with said slurry, said metal layer comprising at least one of tungsten, ruthenium, and molybdenum.
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