Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
• • 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
• • 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
  • C09K3/1436—Composite particles, e.g. coated particles
• • 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
  • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
  • C09K3/1463—Aqueous liquid suspensions
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
  • H10P52/40—Chemomechanical polishing [CMP]
  • H10P52/403—Chemomechanical polishing [CMP] of conductive or resistive materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
  • H10P95/06—Planarisation of inorganic insulating materials
  • H10P95/062—Planarisation of inorganic insulating materials involving a dielectric removal step

Definitions

• the present invention relates to a slurry composition for chemical-mechanical polishing, and more particularly, to a slurry composition for chemical-mechanical polishing which is easy to be stored for a long time because the pH change with time is small in an acidic atmosphere.
• the metal film since the metal film has high strength and is not easily polished, in order to effectively polish the metal film, the metal film needs to be oxidized to a relatively low strength metal oxide, followed by polishing.
• the metal film when silica is used as the abrasive, the longer the storage period of the slurry composition in the acidic region, such as an increase in particle size or pH may occur, and thus stability (Shelf life) time can cause problems.
• the present invention is an abrasive; 0.000006 to 0.01 weight percent aluminum; And it provides a slurry composition for chemical-mechanical polishing comprising water. It is preferable that the number of silanol groups and the aluminum content on the surface of the abrasive satisfy the condition of the following equation (1).
• S is the number of silanol groups present on the abrasive surface 1 nm 2 (unit: nm / nm 2 ) and C is the aluminum content (% by weight) in the slurry composition.
• Slurry composition according to the present invention is excellent in stability, due to changes in pH in the acidic region over time, the polishing performance of the slurry is lowered to prevent the problem of increased scratches or changing the polishing rate, stability (shelf life time) It is improved and easy to store for a long time.
• the slurry composition for chemical-mechanical polishing according to the present invention has excellent polishing rate, low scratch generation, and excellent stability, and can be stored for a long time, and includes abrasive, aluminum, and water.
• the abrasive is for polishing the film to be polished, and silica-based abrasives such as fumed silica, colloidal silica, and mixtures thereof are used.
• the particle size of the abrasive is 5 to 200 nm, specifically 10 to 150 nm, and the content of the abrasive is 0.001 to 20% by weight, specifically 0.01 to 10% by weight, more specifically based on the total slurry composition. Is 0.1 to 5% by weight. If the particle size of the abrasive is too small or the content is too small, the polishing rate of the metal film may be lowered, and if the particle size is too large or too much, scratches on the metal film and the silicon oxide film may occur excessively.
• Silica-based abrasive surface silanol group are Si-OH or Si-O of - meaning a functional group, and the more abrasive surface on the number of silanol groups, it was confirmed that an excellent polishing rate. If the silanol group having chemical activity on the surface of the abrasive is large, the polishing rate is expected to increase as the abrasive is easily bonded to the hydroxyl group on the surface of the oxide film and the oxide film surface is easily removed by physical friction. In addition, the more silanol groups, the lower the degree of condensation of Si-O-Si, and physical friction does not occur excessively, thus reducing scratches.
• the slurry composition according to the present invention preferably has a silanol group number on the surface of the abrasive of 1 to 10 / nm 2 , more preferably 1 to 8 / nm 2 , more preferably 2 to 5 / nm 2
• a silanol group number on the surface of the abrasive of 1 to 10 / nm 2 , more preferably 1 to 8 / nm 2 , more preferably 2 to 5 / nm 2
• the polishing rate is too low to increase the nonuniformity, there is a problem that the scratch is increased, if the number of silanol groups exceeds 10 / nm 2 of the polishing rate While the synergistic effect decreases, the activation surface of the abrasive is so high that dispersion stability is lowered, and there is a fear that aggregation and precipitation occur.
• Aluminum used in the chemical-mechanical polishing slurry composition of the present invention acts as a kind of pH stabilizer that suppresses changes in pH and the like during long-term storage of the slurry composition, thereby improving stability of the slurry composition.
• the aluminum includes aluminum salts, and may be made of aluminum salts as necessary.
• the aluminum salt may be chloride (Cl), sulfate (SO 4 ), ammonium salt (NH 4 ), potassium salt (K), hydroxide (OH), methylate (CH 3 ), phosphide (P), and mixtures thereof.
• it may include chloride (Cl), sulfate (SO 4 ), potassium (K) and mixtures thereof, and the like, for example, aluminum chloride (AlCl 3 ), aluminum sulfate, Al 2 (SO 4 ) 3 ), ammonium aluminum sulfate, (NH 4 ) Al (SO 4 ) 2 ), aluminum potassium sulfate, KAl (SO 4 ) 2 ), aluminum hydroxide , Al (OH) 3 ), trimethyl aluminum (C 6 H 18 Al 2 ), aluminum phosphide (AlP) and mixtures thereof, specifically aluminum chloride, aluminum sulfate, ammonium aluminum sulfate, sulfuric acid Potassium aluminum and mixtures thereof, more specifically aluminum chloride, aluminum sulfate, potassium aluminum sulfate and As a mixture, and most specifically is selected from aluminum chloride, aluminum sulfate and mixtures thereof.
• AlCl 3 aluminum chloride
• Al 2 (SO 4 ) 3 Al sulfate
• the aluminum may be present in the slurry composition in the form of aluminum ions and / or in combination with an aluminum salt and / or abrasive. That is, in the composition of the present invention, the aluminum may be present in one or more conditions selected from the group consisting of a type and aluminum ions (Al + 3) adsorbed to aluminum salts, aluminum atoms abrasive surface.
• the aluminum content is 0.000006 to 0.01% by weight, specifically, 0.0001 to 0.005% by weight. If the aluminum content is too small, the effect of inhibiting pH change over time may not be sufficient, and if too large, a problem of increasing particle size may occur. That is, when the content of aluminum in the slurry in the acidic region exceeds 0.01% by weight, regardless of the number of silanol groups on the silica surface, the electric double layer is compressed and the aggregation occurs to increase the particle size (particle size) was confirmed. The higher the ion concentration, the higher the valence of the ions, the more the electrical double layer is compressed, causing aggregation. Therefore, according to the present invention, only a small amount of aluminum salt can be included to effectively stabilize the pH without increasing the particle size. In addition, excessive use of aluminum is undesirable because it may contaminate the semiconductor process.
• the pH change during the long-term storage of the slurry composition is more effectively suppressed, and the slurry composition Is stabilized.
• S is the number of silanol groups present on the abrasive surface 1 nm 2 (unit: nm / nm 2 ) and C is the aluminum content (% by weight) in the slurry composition.
• the silanol group number is measured by nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), titration, etc. In the present invention, it was measured by a titration method using NaOH.
• the number of silanol groups (S) on the surface of the abrasive is greater than a certain amount of aluminum, the thickness of the electric double layer is compressed and the dispersibility is sharply lowered. Therefore, depending on the number of silanol groups on the surface of the abrasive, the inclusion of excess aluminum results in lower dispersion stability due to an increase in particle size. That is, according to the number of silanol groups on the surface of the abrasive, it is necessary to include an appropriate amount of aluminum that satisfies Equation 1 to obtain a pH stabilization effect without increasing the particle size.
• the remaining components constituting the chemical-mechanical polishing slurry composition according to the present invention may be water, deionized water, distilled water, or the like.
• the content of the water is expressed in weight percent, the water content is, for example, 79.95 to 99 weight percent, specifically 89.95 to 99 weight percent.
• the remaining component of the slurry composition is water, except that the composition of the present invention includes the abrasive, the aluminum component and, if necessary, other additives, except for the abrasive, the aluminum component and the additive used as needed. It means that the component is water.
• the pH of the slurry composition for chemical-mechanical polishing according to the present invention is 1 to 6, specifically 1 to 4, and when the pH of the slurry composition is too high, oxide film formation may not be sufficient, and the polishing rate may be lowered.
• the slurry composition for chemical-mechanical polishing according to the present invention may further include a pH adjusting agent and / or a biocide, if necessary.
• the pH adjusting agent serves to adjust the pH of the slurry composition to 1 to 6, specifically 1 to 4, pH regulators (acids, bases) used in conventional slurry compositions can be used without limitation, for example
• acids such as nitric acid, hydrochloric acid, sulfuric acid, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and the like
• bases such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide, and mixtures thereof are used alone. Or it can mix and use.
• the content of the pH regulator is 0.0005 to 5% by weight, specifically 0.001 to 1% by weight based on the total sludge composition.
• the content of the pH adjuster is out of the range, it may be difficult to adjust the pH of the slurry composition, and may act as a metal impurity to cause wafer contamination and defects.
• the bioside is to prevent the chemical-mechanical polishing slurry composition from being contaminated by microorganisms such as bacteria and molds, and may be used as a commonly used product, and specifically, isothiazolinone or its Derivatives may be used, for example, methyl isothiazolinone (MIT, MI), chloromethyl isothiazolinone (CMIT, CMI, MCI), benzisothiazolinone (BIT) ), Octylisothiazolinone (OIT, OI), dichlorooctylisothiazolinone (DCOIT, DCOI), butylbenzisothiazolinone (BBIT), and the like.
• MIT methyl isothiazolinone
• CMIT chloromethyl isothiazolinone
• CMIT chloromethyl isothiazolinone
• BIT benzisothiazolinone
• OIT Octylisothiazolinone
• DCOIT dichlorooct
• the content of the bioside is 0.0001 to 0.05% by weight, specifically 0.001 to 0.01% by weight based on the entire slurry composition. If the content of the bioside is too small, the effect of inhibiting microorganisms may be less, if too much, the dispersibility of the slurry composition may be lowered.
• the slurry composition according to the present invention may be used to polish the metal film and the insulating film (SiO 2 ), and when the polishing target is a metal film such as tungsten (W), aluminum (Al), copper (Cu), an oxidizing agent (oxidizing agent) may be further included.
• the oxidant is to facilitate the polishing of the metal film by quickly forming an oxide film on the surface of the metal film, and can be used without limitation, conventional oxidants used in the slurry composition for chemical-mechanical polishing, specifically, hydrogen peroxide, iodic acid Potassium and mixtures thereof can be used.
• the oxidant oxidizes metal films, such as wafers and substrates, to the corresponding oxides.
• the content of the oxidant is 0.005 to 10% by weight, specifically 0.2 to 5% by weight, based on the entire slurry composition. If the content of the oxidizing agent is too small, the polishing rate of the metal film may be lowered, and if it is too large, the polishing efficiency may be lowered.
• the polishing target is a tungsten metal film
• it may further include a catalyst.
• the catalyst can be used without limitation, the catalyst usually used in the slurry composition for chemical-mechanical polishing, specifically, nano-ferrosilicon (FeSi), iron salt compounds (for example, iron nitrate, iron chloride, iron sulfate, Iron acetate, etc.) can be used.
• the content of the catalyst is 0.00001 to 0.5% by weight, specifically 0.001 to 0.05% by weight based on the entire slurry composition. If the content of the catalyst is too small, the polishing rate of the metal film may be lowered. If the content of the catalyst is too high, the reactivity may be excessively increased and the polishing rate may be uneven.
• the slurry composition for chemical-mechanical polishing according to the present invention can be prepared by mixing and stirring 0.001 to 20% by weight of abrasive, 0.000006 to 0.01% by weight of aluminum and the rest of water, if necessary, from 0.0005 to 5% by weight of It may further comprise a pH adjuster, 0.0001 to 0.05% by weight of bioside, 0.005 to 10% by weight of oxidant and 0.00001 to 0.1% by weight of catalyst.
• abrasive pH stabilizer catalyst pH Silica Content (% by weight) kindss Content (% by weight) Aluminum content (% by weight) Kinds Content (% by weight)
• Example 1 Colloidal silica 5 Aluminum chloride 0.0001 0.000006 - - 3
• Example 2 Colloidal silica 5 Aluminum chloride 0.01 0.002 - - 3
• Example 3 Colloidal silica 5 Aluminum chloride 0.05 0.01 - - 3
• Example 6 Colloidal silica 5 Ammonium Sulfate 0.01 0.001 - - 3
• Example 7 Fumed silica 5 Aluminum chloride 0.01 0.002 Nano ferrosilicon 0.003 3
• Example 8 Fumed silica 5 Potassium aluminum sulfate 0.01 0.0006 Nano ferrosilicon 0.003 3
• Comparative Example 4 if the aluminum content is more than 0.01% by weight, as shown in Comparative Example 4 can be confirmed that the particle size (particle size) is increased rather than Comparative Example 1, it is necessary to use the appropriate content so as not to change over time It can be seen that it is effective.
• the hydrogen peroxide is mixed with the slurry composition and then decomposed if hydrogen peroxide is used as the oxidizing agent, it is mixed before polishing.
• the IC pressure, RR pressure, EC pressure, and UC pressure of Table 4 are Inter Chamber Pressure, Retainer Ring Pressure, External Chamber Pressure, and Upper Chamber Pressure, respectively.
• a pH adjuster nitric acid or tetramethylammonium hydroxide
• the measurement of the silanol group number was carried out as follows using a titration method.
• an appropriate amount of solution (X [ml]) is prepared by preparing an appropriate amount (100 ml or less) of a solution so that the total area of silica is 90 m 2 in the analysis vessel.
• the pH of the slurry composition is adjusted to 3 using 0.1 M HNO 3 aqueous solution, and sufficiently stabilized until the pH change amount is 0.01 or less.
• Obtain Obtain Obtain Obtain Obtain Obtain Obtain Obtain Obtain Obtain Obtain a (B [mol / L]) (B Y / X) - Here, divided by the initial amount (X [ml]) in the sample for a proper adsorption to silica particles [OH].
• the silanol group density which silica particle has was computed from following formula (2).
• N A [dog / mol] is the avogadro number
• S BET [m 2 / g] is the specific surface area of the silica particles
• Cp [g / L] is the concentration of the silica particles, respectively.
• the insulating film (PE-TEOS) blanket wafer (polish) was polished for 60 seconds, and then the number of scratches formed on the wafer was measured using Negevtech defect inspection equipment.
• the SiO 2 insulating film polishing rate of the slurry composition and the pH change amount before and after storage for 30 days at room temperature were measured and shown in Table 7 together.
• colloidal silica having a surface silanol group number as shown in Table 8
• the composition was prepared.
• the pH change and particle size change over time of the prepared slurry composition were measured and shown in Table 9.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Composite Materials (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Mechanical Treatment Of Semiconductor (AREA)
• Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

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• 2017
  • 2017-05-17 JP JP2018560761A patent/JP7032327B2/ja active Active
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