WO2014007063A1 - Solution de polissage, solution de préservation et procédé de polissage pour cmp - Google Patents

Solution de polissage, solution de préservation et procédé de polissage pour cmp Download PDF

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Publication number
WO2014007063A1
WO2014007063A1 PCT/JP2013/066862 JP2013066862W WO2014007063A1 WO 2014007063 A1 WO2014007063 A1 WO 2014007063A1 JP 2013066862 W JP2013066862 W JP 2013066862W WO 2014007063 A1 WO2014007063 A1 WO 2014007063A1
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Prior art keywords
polishing
cmp
metal
acid
silica particles
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PCT/JP2013/066862
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English (en)
Japanese (ja)
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友和 嶌田
公二 三嶋
田中　孝明
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日立化成株式会社
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Priority to JP2014523666A priority Critical patent/JPWO2014007063A1/ja
Publication of WO2014007063A1 publication Critical patent/WO2014007063A1/fr

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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
    • 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
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • 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]

Definitions

  • the present invention relates to a CMP polishing liquid used for polishing in a wiring formation process of a semiconductor device, a storage liquid for obtaining the polishing liquid, and a polishing method using the polishing liquid.
  • CMP chemical mechanical polishing
  • the damascene process is used to form the embedded wiring.
  • (1) grooves are formed in the insulating material of the substrate having an insulating material, and (2) a copper-based metal (referred to as copper and a copper alloy; the same applies hereinafter) is deposited as a metal for the wiring portion.
  • a layer of a barrier material is formed in the lower layer of the wiring portion metal to prevent diffusion of the wiring portion metal into the insulating material and to improve the adhesion between the wiring portion metal and the insulating material. Since the barrier material is a conductor, the barrier material other than the wiring portion needs to be removed by CMP.
  • the barrier material is generally harder than the metal for the wiring portion, a sufficient polishing rate cannot be obtained even if polishing is performed using a polishing liquid for removing the metal for the wiring portion. Therefore, a two-step polishing method comprising a first polishing step for polishing the wiring portion metal and a second polishing step for polishing the barrier material has been studied.
  • FIG. 1A shows a schematic cross-sectional view of wiring formation by a general damascene process.
  • FIG. 1A shows a substrate 100 before polishing, and follows an insulating material 1 having a groove formed on the surface of a substrate (not shown) such as a silicon wafer, and the surface irregularities of the insulating material 1. It has the formed barrier material 2 and the wiring portion metal 3 deposited so as to fill the recess.
  • the wiring portion metal 3 is polished with a polishing liquid for polishing the wiring portion metal 3 until the barrier material 2 is exposed, whereby the substrate 200 is obtained.
  • it polishes with the polishing liquid for barrier materials, and the barrier material 2 is removed until the convex part of the insulating material 1 is exposed, and the board
  • over-polishing that removes a part of the insulating material 1 is often performed.
  • the broken line 4 shows the state of the substrate 200 before the barrier material is polished in the second polishing step.
  • low-k material As an insulating material, conversion from a conventionally used material mainly made of silicon dioxide to a low dielectric constant material (hereinafter referred to as “low-k material”) is being attempted. These low-k materials have a lower dielectric constant by using organic compounds as raw materials or by forming vacancies in the film.
  • the porous material has a hollow structure such as a honeycomb structure, it is softer than a material having a dense structure. Therefore, it has weak points such as low mechanical strength, high hygroscopicity, and low plasma and chemical resistance as compared with the silicon dioxide film. For this reason, the second polishing step has new problems such as damage to the low-k material, excessive polishing, and film peeling.
  • FIG. 2 shows an example of a manufacturing process of a device having such a structure.
  • a low-k material 6 and a cap layer 7 made of silicon dioxide are sequentially formed on a silicon substrate 5 to form a laminated structure, and then a raised portion is formed. And a groove part is formed.
  • the barrier material 2 is formed so as to follow the surface ridges and the groove surface, and further, the wiring portion metal 3 is formed so as to fill the groove.
  • the insulating material portion contains silicon dioxide in the cap layer, it is affected by the dielectric constant of silicon dioxide, so the effective relative dielectric constant of the insulating material as a whole is not so low. That is, in this case, the low dielectric constant characteristics of the low-k material cannot be fully utilized. Therefore, it is desirable that the silicon dioxide film as the cap layer is removed at the time of polishing the barrier material so that the insulating material portion is finally made of only a low-k material.
  • polishing is performed from the state of the substrate 110 shown in FIG. 2A to the state of the substrate 210 shown in FIG. Specifically, the wiring part metal 3 is polished with a polishing liquid for polishing the wiring part metal 3 until the barrier material 2 is exposed (first polishing step). Next, the barrier material 2 is polished with a polishing liquid for the barrier material to remove the cap layer 7 of at least silicon dioxide up to the state of the substrate 310 shown in FIG. Polish until exposed (second polishing step). At this time, if necessary, over-polishing may be performed to polish the low-k material excessively.
  • the polishing liquid needs to exhibit a high polishing rate for an insulating material such as silicon dioxide and a low polishing rate for an insulating material such as a low-k material.
  • abrasive grains, metal oxide solubilizer, oxidizer, water and quaternary phosphonium salt are contained, and the abrasive grains have a positive zeta potential in the CMP polishing liquid.
  • a polishing liquid for CMP has been proposed (see, for example, Patent Document 2).
  • the CMP polishing liquid is required to have a characteristic of ensuring the flatness of the polished surface after polishing in addition to having an appropriate polishing rate according to such a polishing target.
  • the flatness from the viewpoint of seam, erosion, etc. is higher than when a substrate with a large wiring interval is polished. It turns out that there is a tendency to get worse.
  • the present invention has been made in view of these various problems of conventional polishing liquids, and is excellent in the polishing rate of metal for a wiring portion, barrier material and silicon dioxide, while suppressing the polishing rate of a low-k material. Further, even when a substrate with a narrow wiring interval is polished, a CMP polishing liquid that can sufficiently ensure the flatness of the surface to be polished, and a storage liquid for obtaining the polishing liquid are provided. It is intended to provide. Another object of the present invention is to provide a polishing method using the CMP polishing liquid.
  • a quaternary phosphonium salt having at least one aromatic ring bonded to a phosphorus atom, and silica particles having specific characteristics as abrasive grains It was found that desired polishing characteristics can be obtained by using in combination.
  • the silica particles when silica particles are used in combination with the quaternary phosphonium salt, the silica particles have (A) silanol group density, (B) aspect ratio and (C) zeta potential, and (D) content of silica particles.
  • the ratio of the quaternary phosphonium salt content was found to be an important factor for any of the above problems.
  • the present invention contains silica particles, a quaternary phosphonium salt having at least one aromatic ring bonded to a phosphorus atom, and water, and the silica particles have a silanol group density of 1.0 to 2.0 / nm. 2 , the aspect ratio is 1.3 or more, the zeta potential in the CMP polishing liquid is +10 mV or more, and the ratio of the silica particle content to the quaternary phosphonium salt content is 750 or more.
  • a polishing liquid for CMP is provided.
  • polishing liquid for CMP capable of polishing the metal for the wiring portion, the barrier material and silicon dioxide at a high speed and further suppressing the polishing rate of the low-k material.
  • the flatness of the polished surface after polishing can be sufficiently ensured.
  • the polishing liquid since the CMP polishing liquid may be used after being stored for a certain period, the polishing liquid is required to have long-term dispersion stability in addition to the above-mentioned various problems.
  • the dispersion stability of abrasive grains tends to deteriorate gradually, so that the settling of abrasive grains is likely to occur, and it was not possible to polish properly after storage for a certain period of time.
  • the quaternary phosphonium salt is preferably a compound represented by the following general formula (1).
  • R represents an alkyl group or an aryl group which may have a substituent
  • X ⁇ represents an anion.
  • silanol groups usually exist at the ends (surfaces) of silica particles contained in the polishing liquid. Since the hydrogen atom in the silanol group hardly dissociates in the acidic region, the zeta potential of ordinary silica particles is slightly positive or shows a value close to zero in the acidic region. However, by setting the silanol group density in a small range of 1.0 to 2.0 / nm 2 , a large positive value (+10 mV or more) zeta potential can be provided in the acidic region.
  • the polishing rate of the low-k material can be suppressed by electrostatic repulsion with silica particles having such zeta potential. Guessed. Further, when the zeta potential of the silica particles in the CMP polishing liquid is +10 mV or more, a CMP polishing liquid having excellent dispersibility of the silica particles is provided.
  • the quaternary phosphonium salt represented by the general formula (1) has, for example, an alkyl group or an aryl group R which is a hydrophobic substituent bonded to a phosphorus atom. Since the low-k material is hydrophobic, there is an affinity between the quaternary phosphonium salt having such a hydrophobic substituent and the low-k material. That is, when the alkyl group or aryl group R of the quaternary phosphonium salt approaches the low-k material surface, the low-k material surface is positively charged. In this way, it is considered that the polishing rate of the low-k material is further suppressed by further positively charging the surface of the low-k material and causing electrostatic repulsion with the silica particles.
  • the silica particles are positively charged by associating with the quaternary phosphonium salt, and also include a metal for a wiring part (for example, copper-based metal. Copper-based metal is copper and copper alloy) (A copper alloy is an alloy containing 50% by mass or more of copper.) The surface is also positively charged. From this, it is considered that the silica particles adsorbed with the quaternary phosphonium salt and the metal for the wiring part are electrostatically repelled.
  • the quaternary phosphonium salt is excessively adsorbed with respect to the silica particles.
  • the polishing rate of the wiring portion metal is suppressed. That is, the smaller the content ratio between the silica particles and the quaternary phosphonium salt, the more the polishing rate of the metal for the wiring portion is suppressed, and hence suitable polishing becomes impossible.
  • the ratio of the content of silica particles to the content of quaternary phosphonium salt is as large as 750 or more, Better polishing rate can be obtained.
  • the quaternary phosphonium salt includes butyltriphenylphosphonium salt, pentyltriphenylphosphonium salt (amyltriphenylphosphonium salt), hexyltriphenylphosphonium salt, n-heptyltriphenylphosphonium salt, tetraphenylphosphonium salt and benzyltriphenylphosphonium. It is preferably at least one selected from the group consisting of salts. According to such a polishing liquid, the hydrophobicity of the quaternary phosphonium salt adsorbed on the silica particles is not so high, so that the aggregation and sedimentation of the silica particles tend to be further suppressed.
  • the content of the quaternary phosphonium salt is preferably 0.0005 parts by mass or more and less than 0.005 parts by mass with respect to 100 parts by mass of the CMP polishing liquid. By making the content within this range, it becomes easy to suppress excessive adsorption of the quaternary phosphonium salt to the silica particles, and therefore aggregation and sedimentation of the silica particles can be further suppressed.
  • the silica particles are preferably colloidal silica particles. According to such a polishing liquid, it is easy to change the values of the silanol group density, aspect ratio, and zeta potential. In addition, various grades can be easily obtained as long as they are colloidal silica particles.
  • the content of the silica particles is preferably 1.0 to 15.0 parts by mass with respect to 100 parts by mass of the polishing slurry for CMP.
  • a polishing slurry for CMP that provides a better polishing rate of the insulating material is provided. Furthermore, it becomes easier to suppress aggregation and sedimentation of silica particles, and as a result, a polishing slurry for CMP having better dispersion stability and storage stability is provided.
  • the polishing slurry for CMP of the present invention preferably has a pH of 6.0 or less from the viewpoint of easily controlling the zeta potential of the silica particles to be positive (+). 5.0 or less is more preferable and 4.5 or less is still more preferable at the point which the grinding
  • the CMP polishing liquid of the present invention preferably further contains a metal dissolving agent. As a result, a better polishing rate can be obtained with respect to metals such as wiring part metals and barrier materials.
  • the CMP polishing liquid of the present invention preferably further contains a metal oxidant. As a result, a CMP polishing liquid that exhibits a higher polishing rate than the wiring portion metal and the barrier material is provided.
  • the CMP polishing liquid of the present invention preferably further contains a metal anticorrosive. As a result, the etching of the metal for the wiring portion is suppressed, and further, it becomes easy to prevent the surface after polishing from becoming rough.
  • the metal anticorrosive is preferably a compound having a triazole skeleton (triazole compound).
  • a metal anticorrosive agent having a triazole skeleton in a polishing liquid containing the silica particles and the quaternary phosphonium salt, it is possible to more effectively suppress the etching of the metal for the wiring portion, and further to the surface after polishing. It becomes easier to prevent roughening.
  • the CMP polishing liquid of the present invention preferably further contains a water-soluble polymer.
  • the CMP polishing liquid of the present invention preferably further contains an organic solvent.
  • an organic solvent preferably an organic solvent.
  • the wettability of the surface to be polished with respect to the CMP polishing liquid is improved, and the polishing rate of silicon dioxide, low-k material, etc. can be adjusted better.
  • dissolution of the component in water can be assisted.
  • the present invention further provides a storage liquid for obtaining the CMP polishing liquid, wherein the CMP polishing liquid can be obtained by dilution with a liquid medium. According to such a storage liquid, the cost related to storage, transportation, storage, etc. of the polishing liquid for CMP can be reduced.
  • the present invention also provides a method for polishing a substrate having a low-k material and silicon dioxide covering at least a part of the low-k material, wherein the polishing is performed by polishing silicon dioxide to expose the low-k material.
  • a polishing method including polishing steps and polishing while supplying the polishing slurry for CMP of the present invention in the polishing step.
  • the polishing liquid can polish silicon dioxide at a high speed and can polish the low-k material at a low polishing rate. , It can be removed preferentially for low-k materials. Further, the flatness of the polished surface after polishing can be sufficiently ensured.
  • the present invention provides a low-k material having a concave portion and a convex portion on one surface, silicon dioxide covering the convex portion of the low-k material, a barrier material covering the low-k material and silicon dioxide, A wiring portion metal that covers the barrier material and fills the concave portion, and a polishing method for polishing the wiring portion metal to expose the barrier material on the convex portion. And polishing the barrier material and silicon dioxide on the convex portion to expose the convex portion, and polishing in the second step while supplying the CMP polishing liquid of the present invention. A polishing method is provided.
  • the metal for the wiring portion, the barrier material and the silicon dioxide can be polished at a high speed, and the polishing can be performed while suppressing the polishing rate of the low-k material. Further, the flatness of the polished surface after polishing can be sufficiently ensured.
  • the wiring part metal is preferably a metal mainly composed of copper.
  • a main component means containing 50 mass% or more of copper. That is, the wiring part metal is preferably copper or a copper alloy containing 50 mass% or more of copper.
  • the barrier material is a barrier conductor material that prevents the metal for the wiring portion from diffusing into the insulating material. Tantalum, tantalum nitride, tantalum alloy, titanium, titanium nitride, titanium alloy, ruthenium, ruthenium alloy, cobalt, cobalt It is preferable to include at least one selected from the group consisting of alloys, manganese and manganese alloys.
  • the polishing rate of the low-k material can be suppressed while the polishing rate of the wiring portion metal, barrier material and silicon dioxide is excellent, and the flatness of the surface to be polished can be sufficiently secured. It is possible to provide a polishing liquid for CMP that can be used, and a storage liquid for obtaining the polishing liquid. Further, according to the present invention, a polishing method using the CMP polishing liquid can be provided.
  • the dispersion stability of the abrasive grains is excellent, and in the second polishing step for polishing the barrier material, the polishing rate of the low-k material under practical polishing conditions is increased. It is possible to provide a polishing slurry for CMP that can be suppressed to about 100 ⁇ / min or less, and that the polishing rate of the barrier material and the silicon dioxide material can be 7 times or more the polishing rate of the low-k material.
  • the polishing slurry for CMP of this embodiment contains silica particles, a quaternary phosphonium salt having at least one aromatic ring bonded to a phosphorus atom, and water, and the silica particles have a silanol group density of 1.0 to 2. 0.0 particles / nm 2 , an aspect ratio of 1.3 or more, a zeta potential in the CMP polishing liquid of +10 mV or more, and the content of silica particles relative to the content of the quaternary phosphonium salt Is a polishing slurry for CMP having a ratio of 750 or more.
  • the CMP polishing liquid according to the embodiment is a polishing liquid that can polish the metal for the wiring portion, the barrier material, and silicon dioxide at high speed, and can suppress the polishing speed of the low-k material. Also, the dispersion stability of the silica particles is good.
  • the quaternary phosphonium salt is not particularly limited as long as it is a compound having at least one aromatic ring bonded to a phosphorus atom, but preferably has two or more aromatic rings bonded to a phosphorus atom and bonded to a phosphorus atom. It is preferable to have three or more aromatic rings. Among these, a compound represented by the following general formula (1) is preferably used.
  • R represents an alkyl group or an aryl group which may have a substituent
  • X ⁇ represents an anion
  • the alkyl group R which may have a substituent is preferably at least one selected from the group consisting of a linear alkyl group and a branched alkyl group.
  • the alkyl group in formula (1) may be linear or branched as described above, and the number of carbon atoms of the alkyl group is preferably 1 or more and 14 or less, more preferably Is 4 or more and 7 or less. When the alkyl group has 14 or less carbon atoms, the storage stability of the CMP polishing liquid is not significantly reduced.
  • the aryl group R which may have a substituent is not particularly limited, and examples thereof include a phenyl group, a benzyl group, a tolyl group, a xylyl group, and a naphthyl group. From the viewpoint of further improving the properties and dispersion stability of silica particles, a phenyl group or a benzyl group is preferred.
  • the anion X ⁇ in the formula (1) is not particularly limited, but is a halogen ion (for example, F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ ), hydroxide ion, nitrate ion, nitrite ion, List chlorite ion, chlorite ion, chlorate ion, perchlorate ion, acetate ion, hydrogen carbonate ion, phosphate ion, sulfate ion, hydrogen sulfate ion, sulfite ion, thiosulfate ion, carbonate ion, etc. Can do. Among these, a halogen ion is preferable.
  • the CMP polishing liquid of the present embodiment contains such a specific quaternary phosphonium salt, thereby suppressing the polishing rate of the low-k material more sufficiently without suppressing the polishing rate of the metal for the wiring portion. it can.
  • the planarization ability of the polishing liquid with respect to the surface to be polished is further improved, and the occurrence of erosion can be more easily suppressed even in the portion where the fine wiring portions are densely packed.
  • the quaternary phosphonium salt contained in the polishing slurry for CMP of the present embodiment includes methyltriphenylphosphonium salt, ethyltriphenylphosphonium salt, triphenylpropylphosphonium salt, isopropyltriphenylphosphonium salt, butyltriphenyl Phenylphosphonium salt, pentyltriphenylphosphonium salt (amyltriphenylphosphonium salt), hexyltriphenylphosphonium salt, n-heptyltriphenylphosphonium salt, triphenyl (tetradecyl) phosphonium salt, tetraphenylphosphonium salt, benzyltriphenylphosphonium salt, (2-hydroxybenzyl) triphenylphosphonium salt, (2-chlorobenzyl) triphenylphosphonium salt, (4-chlorobenzyl) triphenylphosphonium salt (2,4-dichlorobenzy
  • pentyltriphenylphosphonium salt (amyltriphenylphosphonium salt), hexyltriphenylphosphonium salt, n-heptyltriphenylphosphonium salt, tetraphenylphosphonium salt, and benzyltriphenylphosphonium salt More preferably, it is at least one selected from the group consisting of:
  • the content of the quaternary phosphonium salt is preferably 0.0005 parts by mass or more, more preferably 0.0007 parts by mass or more, and 0.0009 parts by mass with respect to 100 parts by mass of the polishing slurry for CMP. More preferably, it is part or more.
  • the content of the quaternary phosphonium salt is preferably less than 0.005 parts by mass, more preferably 0.004 parts by mass or less, with respect to 100 parts by mass of the polishing slurry for CMP. It is further preferably 003 parts by mass or less, particularly preferably 0.002 parts by mass or less, and extremely preferably 0.0015 parts by mass or less.
  • the silica particles are not particularly limited as long as the silanol group density, the aspect ratio, and the zeta potential in the CMP polishing liquid are at desired values.
  • the CMP polishing liquid may contain particles other than silica particles (for example, alumina particles) as abrasive grains.
  • the silica particles used in the CMP polishing liquid according to the embodiment have a silanol group density of 1.0 to 2.0 particles / nm 2 .
  • the CMP polishing liquid of this embodiment can have a zeta potential of +10 mV or more by containing silica particles having a silanol group density in the above range. Thereby, the electrostatic attractive force and repulsive force of the surface to be polished become more remarkable, and the planarization ability is further improved. In addition, it is easy to suppress the occurrence of erosion even in a portion where the fine wiring portions are densely packed.
  • the silanol group density ( ⁇ [number / nm 2 ]) can be measured and calculated by titration as follows. First, 1.5 g of silica particles (A [g]) are weighed and dispersed in an appropriate amount (100 mL or less) of water. Next, the pH is adjusted to 3.0 to 3.5 with 0.1 mol / L hydrochloric acid. Thereafter, 30 g of sodium chloride is added, and ultrapure water is further added to make the total amount 150 g. This is adjusted to pH 4.0 with 0.1 mol / L sodium hydroxide solution to obtain a sample for titration.
  • the amount of silica particles (A [g]) is measured to 1.5 g, and thereafter the same
  • the silanol group density can be measured by the procedure. Further, with respect to the silica particles contained in the CMP polishing liquid, the silica particles can be isolated and washed from the CMP polishing liquid, and thereafter the silanol group density can be measured by the same procedure.
  • the BET specific surface area S BET of the silica particles is determined according to the BET specific surface area method.
  • a sample obtained by sufficiently degassing silica particles at 250 ° C. can be obtained by a one-point method or a multi-point method in which nitrogen gas is adsorbed using a BET specific surface area measuring device.
  • the silica particles are first dried with a vacuum freeze dryer, and the residue is finely crushed with a mortar (magnetic, 100 mL) to obtain a measurement sample, which is a BET specific surface area measuring device manufactured by Yuasa Ionics Co., Ltd.
  • the BET specific surface area S BET is measured using (Product name Autosorb 6).
  • the silica particles used in the CMP polishing liquid according to the embodiment have a relatively good dispersion stability in the CMP polishing liquid, and a biaxial average in that the number of polishing scratches generated by CMP is relatively small.
  • the primary particle diameter is preferably 20 to 80 nm, the lower limit is more preferably 25 nm or more, and the upper limit is more preferably 70 nm or less. Therefore, in the polishing slurry for CMP according to the embodiment, in order to achieve both higher dispersion stability of silica particles and suppression of polishing scratches at a higher level, the biaxial average primary particle diameter is more preferably 25 to 70 nm. Preferably, it is more preferably 35 to 70 nm for the same reason.
  • the biaxial average primary particle diameter (R [nm]) is calculated as follows from the result of observing 20 arbitrary particles with a scanning electron microscope (SEM). That is, for example, when colloidal silica particles having a solid content concentration (solid content) of 5 to 40 wt% are dispersed in water as an example, an appropriate amount of colloidal silica particles is taken and patterned in a container containing the liquid. A chip obtained by cutting a wafer with wiring into 2 cm square is immersed for about 30 seconds, then transferred to a container containing pure water, rinsed for about 30 seconds, and the chip is blown with nitrogen.
  • SEM scanning electron microscope
  • the sample is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, the silica particles are observed at a magnification of 100,000, and an image is taken. Arbitrary 20 silica particles are selected from the obtained image.
  • a rectangle (circumscribed rectangle 11) circumscribing the silica particles 10 and arranged so that the major axis is the longest is drawn.
  • the value of (X + Y) / 2 when the major axis of the circumscribed rectangle 11 is X and the minor axis is Y is calculated as the biaxial average primary particle diameter of one particle.
  • This operation is performed on 20 arbitrary silica particles, and the average value obtained is referred to as a biaxial average primary particle diameter in the present embodiment.
  • the silica particles used in the polishing liquid of the present embodiment have a particle aspect ratio of 1.3 or more in that a preferable polishing rate of silicon dioxide is obtained.
  • the aspect ratio is 1. It is preferably 4 or more, more preferably 1.5 or more, still more preferably 1.6 or more, particularly preferably 1.7 or more, and most preferably 1.8 or more. preferable.
  • the upper limit of the aspect ratio of the silica particles is preferably 3.0 or less, more preferably 2.5 or less, and preferably 2.0 or less from the viewpoint of sufficiently ensuring the dispersion stability of the silica particles. More preferably it is.
  • the aspect ratio is calculated by averaging from the result of observing 20 arbitrary silica particles with a scanning electron microscope (SEM). For example, when the selected silica particles have a shape as shown in FIG. 3, a rectangle (circumscribed rectangle 11) that circumscribes the silica particles 10 and has the longest diameter is drawn. And the value of X / Y when the major axis of the circumscribed rectangle 11 is X and the minor axis is Y is calculated as the aspect ratio of the silica particles. This operation is performed on 20 arbitrary silica particles, and the average value obtained is referred to as an aspect ratio in the present embodiment.
  • SEM scanning electron microscope
  • the silica particles used in the CMP polishing liquid of this embodiment have excellent dispersibility and a zeta potential in the CMP polishing liquid of +10 mV or more in that a good polishing rate can be obtained with respect to silicon dioxide.
  • the zeta potential is preferably +15 mV or more, more preferably +17 mV or more, and further preferably +20 mV or more.
  • the upper limit of the zeta potential is not particularly limited, but about +80 mV or less is sufficient for normal polishing.
  • Examples of the method for setting the zeta potential to +10 mV or higher include a method of adjusting the pH of the CMP polishing liquid, and a method of blending a coupling agent or a water-soluble polymer with the CMP polishing liquid.
  • a water-soluble polymer a water-soluble cationic polymer can be preferably used.
  • the zeta potential ( ⁇ [mV]) is measured using a zeta potential measuring device.
  • the scattering intensity of the measurement sample is 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 cps (where cps means counts per second, that is, count per second, and is a unit of particle counting.
  • the polishing liquid for CMP is diluted with pure water so that it becomes)), put into a cell for measuring zeta potential, and measured.
  • the CMP polishing liquid is diluted so that the silica particles are 1.7 to 1.8 parts by mass with respect to 100 parts by mass of the polishing liquid.
  • silica particles with different silanol group density, biaxial average primary particle diameter, aspect ratio and zeta potential are readily available from several silica particle manufacturers, and these values are also controlled by knowledge from the manufacturer. Is possible.
  • silica particles known ones such as fumed silica particles and colloidal silica particles can be used, but silica having the above silanol group density, biaxial average primary particle diameter, aspect ratio and zeta potential is used. In view of easy availability of the particles, colloidal silica particles are preferable. In the CMP polishing liquid of this embodiment, two or more types of silica particles can be used in combination as long as the above characteristics are satisfied.
  • the content of the silica particles is preferably 1.0 to 15.0 parts by mass with respect to 100 parts by mass of the polishing slurry for CMP.
  • the content of the silica particles having the above characteristics is 1.0 part by mass or more, a better polishing rate for the insulating material tends to be obtained, and from the same viewpoint, 1.5 parts by mass or more is more preferable, 2.0 mass parts or more are still more preferable, and 2.5 mass parts or more are especially preferable.
  • the content is 15.0 parts by mass or less, it becomes easier to suppress the aggregation and sedimentation of particles, and as a result, good dispersion stability and storage stability tend to be obtained.
  • content here is the compounding quantity in the state (Point of Use) prepared to the state which can be used for a CMP grinding
  • the ratio of the content of silica particles to the content of the quaternary phosphonium salt is 750 or more. is there.
  • the content ratio is preferably 750 or more, and more preferably 1000 or more.
  • the upper limit of the content ratio is not particularly limited, but is preferably 30000 or less.
  • the CMP polishing liquid of this embodiment is characterized in that a good polishing rate for the barrier material and silicon dioxide can be obtained, and the polishing rate of the low-k material can be suppressed.
  • the pH (25 ° C.) of the CMP polishing liquid of this embodiment is preferably 6.0 or less.
  • the pH is more preferably 1.5 or more, still more preferably 1.8 or more, and particularly preferably 2.0 or more. In addition, if pH is 2.0 or more, handling will become easy compared with the case where acidity is too strong.
  • the pH is more preferably 5.0 or less, even more preferably 4.5 or less, and 4.0 or less in that a good polishing rate can be obtained for the metal for the wiring portion and the conductor of the barrier material. Particularly preferred is 3.5 or less, and very preferred is 3.0 or less.
  • the pH is preferably in a neutral region.
  • the neutral region is defined as pH: 6.5 to 7.5
  • the acidic region is defined as pH: less than 6.5.
  • the pH of the polishing liquid can be measured with a pH meter (for example, model number PH81 manufactured by Yokogawa Electric Corporation). As pH, after calibrating two points using a standard buffer (phthalate pH buffer: pH 4.01 (25 ° C.), neutral phosphate pH buffer: pH 6.86 (25 ° C.)), The value after the electrode is put in the polishing liquid and stabilized after 2 minutes or more is adopted.
  • a pH meter for example, model number PH81 manufactured by Yokogawa Electric Corporation.
  • a medium for the polishing liquid for CMP is not particularly limited as long as it is a liquid in which silica particles can be dispersed.
  • water is used in this embodiment from the viewpoint of handleability during pH adjustment, safety, reactivity with the surface to be polished, and the like. Is the main component. More specifically, such water is preferably deionized water, ion exchange water, ultrapure water, or the like.
  • an organic solvent other than water may be added as necessary.
  • These organic solvents can be used as a solubilizing agent for components that are difficult to dissolve in water, or can be used for the purpose of improving the wettability of the surface to be polished with the polishing slurry for CMP.
  • the thing which can be mixed with water is preferable and can be used individually by 1 type or in mixture of 2 or more types.
  • polar solvents such as alcohol
  • polar solvents such as alcohol
  • glycols, glycol monoethers, glycol diethers, alcohols, carbonates, lactones, ethers, ketones, phenols, dimethylformamide N-methylpyrrolidone, ethyl acetate, ethyl lactate, sulfolane and the like for example, glycols, glycol monoethers, glycol diethers, alcohols, carbonates, lactones, ethers, ketones, phenols, dimethylformamide N-methylpyrrolidone, ethyl acetate, ethyl lactate, sulfolane and the like.
  • at least one selected from the group consisting of glycol monoethers, alcohols and carbonates is preferable.
  • the content of the organic solvent is preferably 0.1 to 95 parts by mass with respect to 100 parts by mass of the CMP polishing liquid.
  • the content is more preferably 0.2 parts by mass or more, and still more preferably 0.5 parts by mass or more in terms of improving the wettability of the substrate with respect to the CMP polishing liquid.
  • 50 mass parts or less are more preferable at the point which prevents difficulty on a manufacturing process, and 10 mass parts or less are still more preferable.
  • the content of water may be the remainder of the content of other components, and is not particularly limited as long as it is contained.
  • Water is also used as a diluting solution for diluting a concentration-stored polishing slurry for CMP described later to a concentration suitable for use.
  • a metal solubilizer and a metal oxidizer are further contained mainly for obtaining a better polishing rate for the metal for the wiring portion and the barrier material. can do.
  • oxidizer a metal oxidizer
  • the polishing slurry for CMP has a low pH, there is a possibility that the metal for the wiring portion may be etched, and therefore, a metal anticorrosive can be contained for the purpose of suppressing this.
  • these components will be described.
  • the CMP polishing liquid of this embodiment preferably contains a metal dissolving agent in that a better polishing rate can be obtained for metals such as wiring part metals and barrier materials.
  • the metal solubilizer is defined as a substance that contributes to dissolving at least the oxidized wiring portion metal in water, and includes a substance known as a chelating agent or an etching agent.
  • Such a metal solubilizer is used for the purpose of adjusting the pH and dissolving the metal for the wiring part, and is not particularly limited as long as it has the function.
  • examples include acids (however, except for those contained in the following amino acids), organic acid compounds such as organic acid esters and salts of organic acids; inorganic acid compounds such as inorganic acids and salts of inorganic acids; amino acids and the like. Although there is no restriction
  • These metal solubilizers can be used alone or in combination of two or more, and the organic acid, the inorganic acid and the amino acid can be used in combination.
  • the metal solubilizer preferably contains an organic acid compound, more preferably an organic acid, in that the etching rate can be effectively suppressed while maintaining a practical CMP rate.
  • organic acid include formic acid, acetic acid, glyoxylic acid, pyruvic acid, lactic acid, mandelic acid, vinyl acetic acid, 3-hydroxy entangling acid, oxalic acid, maleic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, phthalic acid.
  • Acid tartaric acid, fumaric acid, malic acid, succinic acid, glutaric acid, oxaloacetic acid, citric acid, hemimellitic acid, trimellitic acid, trimesic acid, melittic acid, isocitric acid, aconitic acid, oxalosuccinic acid, propionic acid, butyric acid, iso Butyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, octanoic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, benzoic acid , Cinnamic acid, isophthalic acid, terephthalic acid, furancarboxylic acid, thiophenecarboxylic , Nicotinic acid, isonicotinic acid, glycolic acid, salicylic acid,
  • the metal dissolving agent preferably includes at least one selected from the group consisting of formic acid, malonic acid, malic acid, tartaric acid, citric acid, salicylic acid, and adipic acid. These can be used alone or in combination of two or more.
  • the metal dissolving agent preferably contains an inorganic acid in that a high polishing rate for the wiring portion metal can be easily obtained.
  • monovalent inorganic acids such as hydrochloric acid and nitric acid; sulfuric acid, chromic acid, carbonic acid, molybdic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, telluric acid, tungstic acid, phosphone Divalent acids such as acids; trivalent acids such as phosphoric acid, phosphomolybdic acid, phosphotungstic acid, vanadic acid; tetravalent or higher acids such as silicomolybdic acid, silicotungstic acid, pyrophosphoric acid, tripolyphosphoric acid, etc. Is mentioned. When an inorganic acid is used, nitric acid is preferred. These can be used alone or in combination of two or more.
  • the metal solubilizer preferably contains an amino acid in terms of easy pH adjustment and a high polishing rate with respect to the metal for the wiring part.
  • the amino acid is not particularly limited as long as it is an amino acid that dissolves even in water. Specifically, for example, glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, aspartic acid, glutamic acid, lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, proline, oxyproline, etc. Can be mentioned. These can be used alone or in combination of two or more.
  • the content is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the CMP polishing liquid.
  • the content is more preferably 0.002 parts by mass or more, and still more preferably 0.005 parts by mass or more, from the viewpoint that a good polishing rate can be easily obtained with respect to metals such as wiring part metals and barrier materials.
  • the upper limit is more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, and more preferably 3 parts by mass or less in terms of suppressing etching and preventing the surface to be polished from becoming rough. It is particularly preferred that
  • the polishing slurry for CMP of this embodiment forms a protective film for the metal for the wiring part to suppress the etching of the metal for the wiring part, and further has a function of preventing the surface from being roughened from being roughened. It is preferable to contain.
  • the metal anticorrosive is defined as a substance capable of forming a protective film on the wiring part metal when used alone. Note that it is possible to determine whether a protective film is formed by immersing a sample having a metal for a wiring portion in an aqueous solution of a metal anticorrosive and performing a composition analysis on the surface of the sample. In the polishing using the polishing slurry for CMP according to the present embodiment, the metal for the wiring portion does not necessarily have to be formed with a protective film made of the metal anticorrosive.
  • Such metal anticorrosives include, for example, a triazole compound having a triazole skeleton in the molecule, a pyrazole compound having a pyrazole skeleton in the molecule, a pyrimidine compound having a pyrimidine skeleton in the molecule, and an imidazole in the molecule.
  • examples include imidazole compounds having a skeleton, guanidine compounds having a guanidine skeleton in the molecule, thiazole compounds having a thiazole skeleton in the molecule, and tetrazole compounds having a tetrazole skeleton in the molecule. These can be used alone or in combination of two or more.
  • triazole compounds are preferable.
  • triazole derivatives such as 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole; benzotriazole; 1 -Hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl (-1H-) benzotriazole, 4-carboxyl (-1H-) benzotriazole methyl Ester, 4-carboxyl (-1H-) benzotriazole butyl ester, 4-carboxyl (-1H-) benzotriazole octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl-1-methyl Benzotriazoles such as [1,2,4-triazolyl-1-methyl] [2-ethylhexyl] amine, toly
  • the content of the metal anticorrosive is 0. 0 parts by mass with respect to 100 parts by mass of the polishing slurry for CMP in that etching of the metal for the wiring part is suppressed and it is easy to prevent the surface from being polished.
  • 001 parts by mass or more is preferable, and 0.01 parts by mass or more is more preferable.
  • 10 mass parts or less are preferable at the point which can maintain the grinding
  • 2 parts by mass or less is particularly preferable.
  • the CMP polishing liquid of this embodiment preferably contains a metal oxidizer having the ability to oxidize the wiring portion metal.
  • a metal oxidant include hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, ozone water, and the like, and among these, hydrogen peroxide is preferable. These can be used alone or in combination of two or more. Since hydrogen peroxide is usually available as a hydrogen peroxide solution, when the CMP polishing liquid of this embodiment is used after being concentrated and stored as described later, the hydrogen peroxide solution can be used as a diluent. it can.
  • the substrate is a silicon substrate including an integrated circuit element
  • contamination with alkali metal, alkaline earth metal, halide, or the like is not desirable, and thus an oxidizing agent that does not contain a nonvolatile component is desirable.
  • hydrogen peroxide is the most suitable because ozone water has a rapid compositional change.
  • an oxidizing agent that includes a nonvolatile component may be used.
  • the content of the metal oxidant is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the CMP polishing liquid.
  • the content is more preferably 0.02 parts by mass or more, and still more preferably 0.05 parts by mass or more, from the viewpoint that it is easy to prevent the metal from being insufficiently oxidized and the polishing rate from being lowered.
  • As an upper limit 30 mass parts or less are more preferable, and 10 mass parts or less are still more preferable at the point which can prevent that a surface to be polished becomes rough.
  • hydrogen peroxide when using hydrogen peroxide as an oxidizing agent, it converts so that hydrogen peroxide may finally become the said range, and mix
  • the content of the oxidizing agent is 0 with respect to 100 parts by mass of the CMP polishing liquid in that a better polishing rate for the barrier material can be obtained.
  • a range of 0.01 to 3 parts by mass is preferable.
  • the pH of the polishing slurry for CMP is 1 to 4, the polishing rate for the barrier material tends to become maximum when the content of the oxidizing agent is around 0.15 parts by mass.
  • the oxidizing agent Is preferably 2.5 parts by mass or less, more preferably 2 parts by mass or less, and particularly preferably 1.5 parts by mass or less, with respect to 100 parts by mass of the polishing slurry for CMP.
  • the amount is 1.0 part by mass or less.
  • the CMP polishing liquid of this embodiment can contain a water-soluble polymer.
  • the CMP polishing liquid contains a water-soluble polymer to further improve the leveling ability of the polishing liquid with respect to the surface to be polished, and also suppresses the occurrence of erosion even in areas where fine wiring portions are densely packed. It becomes easy.
  • the weight average molecular weight of the water-soluble polymer is preferably 500 or more, more preferably 1500 or more, and even more preferably 5000 or more, from the viewpoint that a high polishing rate can be expressed.
  • the upper limit is not particularly limited, but is preferably 5 million or less from the viewpoint of solubility in the polishing slurry for CMP.
  • the weight average molecular weight of the water-soluble polymer can be measured by gel permeation chromatography using, for example, a standard polystyrene calibration curve under the following conditions.
  • the water-soluble polymer is not particularly limited, but is an acrylic acid-based polymer (a polymer obtained by polymerizing or copolymerizing a raw material monomer containing a C ⁇ C—COOH skeleton as a monomer component) in terms of excellent planarization characteristics. Preferably there is.
  • the raw material monomer for obtaining the acrylic acid polymer include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, tiglic acid, 2-trifluoromethylacrylic acid, itaconic acid, fumaric acid, Carboxylic acids such as maleic acid, citraconic acid, mesaconic acid and gluconic acid; sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid; esters such as methyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate And salts of these ammonium salts, alkali metal salts, alkylamine salts and the like.
  • the CMP polishing liquid preferably contains a methacrylic acid polymer (a polymer obtained by polymerizing or copolymerizing a raw material monomer containing methacrylic acid as a monomer component).
  • the methacrylic acid polymer is preferably at least one selected from a homopolymer of methacrylic acid and a copolymer of methacrylic acid and a monomer copolymerizable with the methacrylic acid.
  • the ratio of methacrylic acid to the total amount of the monomers is preferably 40 mol% or more, and 70 mol% or more. Is more preferable. Moreover, it is preferable that the said ratio is less than 100 mol%. That is, the ratio is preferably 40 mol% or more and less than 100 mol%, more preferably 70 mol% or more and less than 100 mol%.
  • the blending amount of the methacrylic acid polymer is the total amount of all components of the polishing slurry for CMP in that the flatness can be further improved while suppressing the stability of the silica particles contained in the polishing slurry for CMP from being extremely lowered.
  • 1 mass part or less is preferable with respect to 100 mass parts, 0.5 mass part or less is more preferable, 0.1 mass part or less is still more preferable, 0.05 mass part or less is especially preferable.
  • 0.001 part by mass or more is preferable, 0.05 part by mass or more is more preferable, and 0.01 part by mass with respect to 100 parts by mass of the polishing slurry for CMP in that the flatness can be more effectively improved. Part or more is more preferable.
  • the barrier material and the silicon dioxide material can be polished at high speed even with a relatively small amount of silica particles added, which is advantageous in terms of cost.
  • the amount of silica particles added in the CMP polishing liquid of this embodiment may be small, and the dispersibility of the silica particles is very high.
  • concentration is high. It is possible to concentrate. That is, it is prepared and stored separately as “slurry” containing at least silica particles and one or more “addition liquid” or “dilution liquid” containing components other than silica particles. It can be prepared by mixing.
  • the polishing rate can be adjusted to a more preferable value, but by mixing these in advance in the polishing liquid, the dispersion of silica particles Stability may be reduced.
  • the polishing slurry for CMP of the present embodiment includes an additive solution containing at least the slurry containing the silica particles and a component other than the silica particles (for example, a component that can reduce the dispersion stability of the silica particles). And can be prepared and stored separately.
  • the metal oxidizer and silica particles that may affect the dispersion stability of silica particles can be stored separately. That is, it can be divided into an additive liquid containing a metal oxidizing agent and a slurry containing silica particles, a metal dissolving agent, a metal anticorrosive and water.
  • the silica particles used in the CMP polishing liquid of the present embodiment have the silanol group density, aspect ratio, and zeta potential in the ranges described so far, and the barrier material and the silicon dioxide material can be used at high speed even with a relatively small content. Therefore, it can be contained and dispersed in a medium at a high concentration.
  • Conventional silica particles have a limit of about 10 parts by mass with respect to 100 parts by mass of the medium even when the dispersibility is increased by a known method, and if added more than this, aggregation and sedimentation occur. .
  • the silica particles used in the CMP polishing liquid of the present embodiment can be dispersed in the medium by 10 parts by mass or more, and can be easily contained and dispersed in the medium up to about 15 parts by mass. Moreover, it is possible to contain and disperse up to about 18 parts by mass.
  • the CMP polishing liquid of this embodiment can be stored and transported in a highly concentrated CMP polishing liquid storage liquid, which is extremely advantageous in terms of process. For example, when it is used as a polishing slurry for CMP containing 5 parts by mass of silica particles, it means that it can be concentrated three times during storage and transportation.
  • the CMP polishing liquid of the present embodiment can be stored and transported as a CMP polishing liquid storage liquid concentrated three times or more than in use.
  • a CMP polishing liquid storage liquid containing at least 10 parts by mass of the above silica particles, and an additive liquid containing other components And a dilute solution, and these are mixed immediately before the polishing step, or supplied while adjusting the flow rate so that a desired concentration is obtained during polishing, and used as a desired polishing solution for CMP.
  • the diluent include liquid media such as water, organic solvents, and mixed solvents of water and organic solvents. Further, the diluent may contain components other than silica particles.
  • a stock solution for polishing liquid for CMP a hydrogen peroxide solution as a diluent containing a metal oxidizer, and other components. It is also possible to divide into additive liquids containing components. If there is no problem in dispersion stability without dividing the additive solution and the diluted solution, both solutions may be mixed and used. In addition, in this embodiment, it is preferable to use separately for the storage liquid containing a silica particle and water, the addition liquid containing another component, and a dilution liquid.
  • the CMP polishing liquid of the present embodiment as described above can be applied to a polishing process for manufacturing semiconductor substrates, electronic devices, and the like. More specifically, the present invention can be applied to formation of wiring on a semiconductor substrate. For example, it can be used for CMP polishing of a substrate including a wiring part metal, a barrier material, and an insulating material.
  • so-called over-polishing in which a part of the convex portion of the low-k material is further polished and flattened, can also be performed.
  • the CMP polishing liquid of this embodiment can be prepared in a concentrated state and stored as the CMP polishing liquid storage liquid.
  • a polishing method in this case Low-k material having concave and convex portions on one surface, silicon dioxide material covering the convex portion of the low-k material, barrier material covering the low-k material and silicon dioxide material, and covering the barrier material A wiring portion metal filling the recess, and a polishing method for polishing the wiring portion metal to expose a barrier material on the protrusion, and on the protrusion And polishing the barrier material and the silicon dioxide material to expose the convex portion, and in the second polishing step, the CMP polishing liquid stock solution is diluted or added, or both And a polishing method in which polishing is performed while supplying a polishing slurry for CMP obtained by mixing with the above.
  • a storage solution for the polishing slurry for CMP, a diluting solution, an additive solution, and the like are supplied through separate pipes.
  • polishing process of this is mentioned.
  • a mixing step of preparing a CMP polishing solution by mixing a CMP polishing solution storage solution, a diluent, an additive solution, and the like may be provided.
  • the wiring part metal examples include copper, copper alloys, copper oxides, copper alloys such as copper alloys, tungsten metals such as tungsten, tungsten nitride, and tungsten alloys, silver, and gold.
  • the substance which is a component is mentioned. Among these, the metal which has a copper-type metal as a main component is preferable, and the metal which has copper as a main component is more preferable.
  • the wiring portion metal can be formed by a known sputtering method, plating method or the like.
  • the “main component” refers to a component contained in an amount of 50% by mass or more based on the whole component.
  • Examples of insulating materials include silicon materials and organic polymers. A recess is formed on one surface of the insulating material.
  • silicon-based material examples include silicon oxide (silicon dioxide), fluorosilicate glass, trimethylsilane or dimethoxydimethylsilane, an organosilicate glass or porous organosilicate glass obtained from a starting material, silicon oxynitride, hydrogenated silsesquioxide.
  • silicon oxide silicon dioxide
  • fluorosilicate glass trimethylsilane or dimethoxydimethylsilane
  • organosilicate glass or porous organosilicate glass obtained from a starting material silicon oxynitride
  • hydrogenated silsesquioxide examples include silica-based materials such as oxane, silicon carbide, silicon nitride, and carbon-added silicon oxide (SiOC).
  • organic polymer material examples include low-k materials (low dielectric constant) such as organosilicate glass starting from trimethylsilane and wholly aromatic ring-based low-k materials (fully aromatic low-k dielectric materials). Material).
  • fluorosilicate glass organosilicate glass, porous organosilicate glass, carbon-added silicon oxide (SiOC), etc. are particularly preferably used as the low-k material.
  • These materials are formed by CVD, spin coating, dip coating, or spraying.
  • the barrier material is formed in order to prevent the wiring portion metal from diffusing into the insulating material and to improve the adhesion between the insulating material and the wiring portion metal.
  • barrier materials include titanium-based metals such as titanium, titanium nitride, titanium alloys, and other titanium compounds; tantalum-based metals such as tantalum, tantalum nitride, tantalum alloys, and other tantalum compounds; ruthenium, other Examples include ruthenium-based metals such as ruthenium alloys; cobalt-based metals such as cobalt and other cobalt alloys; manganese-based metals such as manganese and other manganese alloys, and these may be used alone or in combination of two or more. it can.
  • the barrier material can also be a laminated film of two or more layers.
  • an apparatus for polishing for example, when polishing with a polishing cloth, it has a holder that can hold the substrate to be polished, and a surface plate that is connected to a motor or the like that can change the number of rotations and to which the polishing cloth is attached.
  • a general polishing apparatus can be used. There is no restriction
  • the polishing conditions are not limited, but the rotation speed of the surface plate is preferably a low rotation of 200 min ⁇ 1 or less so that the substrate does not jump out.
  • the polishing pressure is preferably 1 to 100 kPa, and there is little variation in the CMP rate within the same substrate (in-plane uniformity of the CMP rate) and the unevenness that existed before polishing is eliminated and flattened. In order to more suitably satisfy the (pattern flatness), it is preferably 5 to 50 kPa.
  • the polishing slurry for CMP is continuously supplied to the polishing cloth by a pump or the like.
  • the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the CMP polishing liquid.
  • the substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the substrate using a spin dryer or the like. That is, it is preferable that a substrate cleaning process is further performed after the polishing process according to the present embodiment is performed.
  • polishing method of the present embodiment will be described in more detail with reference to a specific example of a wiring layer forming process in a semiconductor substrate as shown in FIG. Needless to say, the polishing method of the present embodiment is not limited to this.
  • a low-k material 6 made of organosilicate glass or the like is formed on a silicon substrate 5 and then a cap layer 7 made of silicon dioxide or the like is laminated thereon to obtain a substrate on which an insulating material is formed.
  • the surface of the insulating material is processed using known means such as resist layer formation and etching to obtain a substrate on which concave portions (substrate exposed portions) having a predetermined pattern are formed.
  • a substrate is obtained in which a barrier material 2 made of tantalum or the like that covers the insulating material along the surface irregularities is formed by vapor deposition or CVD. Then, as shown in FIG.
  • the formation thicknesses of the low-k material 6 and the cap layer 7, the barrier material 2, and the wiring portion metal 3 that are insulating materials are preferably about 10 to 2000 nm, 1 to 100 nm, and 10 to 2500 nm, respectively.
  • the wiring portion metal 3 on the surface of the substrate 110 manufactured by the above method has a sufficiently large polishing rate ratio of the wiring portion metal / barrier material (the polishing rate of the wiring portion metal relative to the barrier material).
  • the first polishing step of polishing by CMP is performed using the first polishing slurry for CMP.
  • the barrier material 2 of the convex portion on the substrate is exposed, and the substrate 210 in which the desired conductor pattern in which the metal for wiring portion 3 is left in the concave portion is exposed is obtained. .
  • a slight amount of metal for the wiring portion may remain and a portion of the barrier material of the convex portion may not be exposed (this state is not shown). Since the metal for part can also be polished, there is no problem if most of the metal for wiring is removed.
  • a second polishing step is performed in which the obtained substrate 210 is polished using the CMP polishing liquid (second CMP polishing liquid) of the present embodiment.
  • polishing is performed using a second polishing slurry for CMP capable of polishing the wiring portion metal 3, the barrier material 2, and the low-k material 6 and the silicon dioxide material 7 constituting the insulating material.
  • the exposed barrier material 2 and a part of the wiring portion metal 3 in the concave portion are removed by polishing, whereby all of the silicon dioxide material 7 under the barrier material 2 covering the convex portion is removed.
  • overpolishing for example, when the polishing time until a desired pattern is obtained in the second polishing step is 100 seconds, in addition to this 100 second polishing, 50 seconds
  • the additional polishing is referred to as “over polishing 50%”) to remove the convex silicon dioxide material 7, a part of the low-k material 6 and a part of the concave part wiring metal 3.
  • the substrate 310 after polishing is obtained.
  • the substrate 310 after polishing is embedded with the wiring portion metal 3 to be a metal wiring in a recess, and the boundary between the wiring portion metal 3 and the low-k material 6 is obtained.
  • the cross section of the barrier material 2 is exposed.
  • the CMP polishing liquid of this embodiment can also be used as the first CMP polishing liquid, but can polish the silicon dioxide material at a high speed and suppress the polishing rate for the low-k material.
  • it is preferably used as at least the second CMP polishing liquid.
  • a semiconductor substrate having a desired number of wiring layers is manufactured by forming an insulating material and a second-layer metal wiring on the metal wiring thus formed, and repeating the same process a predetermined number of times. (Not shown).
  • a semiconductor substrate, an electronic device, and the like manufactured using the polishing method are provided.
  • a semiconductor substrate, an electronic device, and the like thus manufactured are excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and high reliability.
  • polishing liquid for CMP (Preparation of stock solution for polishing liquid for CMP) 1.6 parts by mass of malic acid in a container, 0.4 parts by mass of benzotriazole as a metal anticorrosive agent, X parts by mass of ultrapure water were poured into it, and 36 parts of PMAA so that 0.1 part by mass was contained as PMAA. A 0.5% by mass aqueous solution was added, and a part by mass of a quaternary phosphonium salt shown in Tables 1 and 2 was added, and mixed and stirred to dissolve each component.
  • colloidal silica shown in Tables 1 and 2 was prepared, and this was used as silica particles, and an amount corresponding to 12.0 parts by mass in total with respect to 100 parts by mass of the CMP polishing liquid stock solution was added to the container.
  • a “polishing liquid stock solution for CMP” was obtained.
  • X mass part of the said ultrapure water was calculated
  • the PMAA was a copolymer of methacrylic acid and acrylic acid (copolymerization ratio 99/1), and the weight average molecular weight was 7500.
  • Biaxial average primary particle diameter (R [nm])
  • the colloidal silica was dried and an image observed with a scanning electron microscope was obtained. From the obtained image, 20 arbitrary particles were selected. As shown in FIG. 3, a rectangle (circumscribed rectangle) 11 circumscribing the selected particle 10 and arranged so that the major axis is the longest is drawn, where the major axis of the circumscribed rectangle 11 is X and the minor axis is Y ( The biaxial average primary particle diameter of one particle was calculated as X + Y) / 2. This operation was carried out on 20 arbitrary particles, and the average value of the obtained values was determined to obtain the biaxial average primary particle size.
  • BET specific surface area S BET [m 2 / g] The colloidal silica was sufficiently degassed at 250 ° C. and determined by a one-point method using a BET specific surface area measuring device to adsorb nitrogen gas.
  • a sodium hydroxide aqueous solution was added dropwise until the pH of the titration sample reached 9.0, and the amount of sodium hydroxide (B [mol]) required until the pH reached 4.0 to 9.0 was determined.
  • the CMP polishing liquid is diluted so that the scattering intensity of the measurement sample in the device is 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 cps.
  • a measurement sample was prepared. Specifically, a sample obtained by diluting the CMP polishing liquid with pure water so that the colloidal silica particles contained in the CMP polishing liquid is 1.71 parts by mass in 100 parts by mass of the CMP polishing liquid is used as a measurement sample. Measurement was carried out in a zeta potential measurement cell.
  • Polishing and cleaning apparatus CMP polishing machine Reflexion LK (manufactured by Applied Materials) Polishing cloth: Foam polyurethane resin (Product name: VP3100, manufactured by Rohm and Haas) ⁇ Surface plate rotation speed: 93 times / min -Head rotation speed: 87 times / min Polishing pressure: 10 kPa -Supply amount of polishing liquid for CMP: 300 mL / min Polishing time: The blanket substrate (a) was 120 sec, the blanket substrate (b) was 30 sec, the blanket substrate (c) was 60 sec, and the blanket substrate (d) was 90 sec.
  • CMP polishing machine Reflexion LK manufactured by Applied Materials
  • Polishing cloth Foam polyurethane resin (Product name: VP3100, manufactured by Rohm and Haas) ⁇ Surface plate rotation speed: 93 times / min -Head rotation speed: 87 times / min Polishing pressure: 10 kPa -Supply amount of polishing liquid for C
  • the polishing rate was determined as follows. That is, for the blanket substrates (a) and (b), the film thickness before and after polishing was measured using a metal film thickness measuring device (manufactured by Hitachi Kokusai Electric Co., Ltd., model number VR-120 / 08S). I asked for it. On the other hand, for the blanket substrates (c) and (d), the film thickness before and after polishing was measured using a film thickness measuring device RE-3000 (manufactured by Dainippon Screen Mfg. Co., Ltd.), and obtained from the film thickness difference. . The measurement results of each polishing rate are shown in Tables 1 and 2.
  • the CMP polishing liquids of Comparative Examples 1 and 2 contain a quaternary phosphonium salt that is a quaternary phosphonium salt but does not have an aromatic ring bonded to a phosphorus atom. Therefore, it can be seen that the polishing rate of the SiOC film of the blanket substrate (d) is not sufficiently suppressed.
  • polishing slurry for CMP of Comparative Example 3 does not contain the quaternary phosphonium salt, and therefore the polishing rate of the SiOC film of the blanket substrate (d) is not sufficiently suppressed.
  • the polishing liquid for CMP of Comparative Examples 4 and 5 contains silica particles C and D having an aspect ratio of silica particles of less than 1.3, at least the polishing rate of the silicon dioxide film on the blanket substrate (c) is high. It turns out that it is not fully obtained. It can also be seen that the polishing rate of the SiOC film of the blanket substrate (d) is not sufficiently suppressed.
  • the polishing liquids for CMP of Comparative Examples 6 to 8 have silica particles E, F, whose silica particle aspect ratio is less than 1.3, and whose silanol group density is not 1.0 to 2.0 pieces / nm 2. Since G is contained, it can be seen that at least the polishing rate of the SiOC film of the blanket substrate (d) is not suppressed.
  • the ratio of the silica particle content to the quaternary phosphonium salt content is less than 750, so that at least a sufficient polishing rate for the copper film of the blanket substrate (a) can be obtained. You can see that it is not.
  • the polishing liquids for CMP of Examples 1 to 5 contain silica particles and a quaternary phosphonium salt having an aromatic ring bonded to a phosphorus atom, and the silica particles have an aspect ratio of 1.3 or more.
  • the silanol group density is 1.0 to 2.0 / nm 2
  • the zeta potential is +10 mV or more
  • the ratio of the content of silica particles to the content of the quaternary phosphonium salt is 750 or more. is there.
  • the polishing liquid can suppress the polishing rate of the SiOC film. Moreover, in any Example, it was excellent in the dispersion stability (long-term dispersibility of a silica particle) of polishing liquid.
  • polishing liquid for CMP The polishing slurry for CMP of Example 3 prepared in Experiment 1 and Comparative Examples 1, 3, and 6 were used. The polishing conditions were the same as in Experiment 1.
  • a patterned substrate having a diameter of 12 inches (30.5 cm) ( ⁇ ) was prepared. This pattern substrate was produced as follows. First, a 150 nm thick SiOC film was laminated on a silicon substrate. Then, processing was performed using means such as resist layer formation and etching to form a concave portion (trench groove 160 nm) having a predetermined pattern on the surface of the silicon substrate.
  • a tantalum nitride film having a thickness of 10 nm and a tantalum film having a thickness of 10 nm were formed in this order as barrier materials for covering the surface along the unevenness. Further, a wiring substrate metal made of copper was formed to have a thickness of 660 nm so as to fill the concave portion, and a pattern substrate used for the polishing method of Experiment 2 was prepared.
  • the pattern substrate was polished with a known copper polishing abrasive until the barrier material was exposed.
  • the pattern substrate on which the barrier material was exposed under the above polishing conditions was polished while dripping the prepared CMP polishing liquid onto the pad attached to the surface plate of the polishing apparatus.
  • the time when the dishing amount of the copper wiring portion is 100 mm or less was set as the polishing end point.
  • the amount of polishing, erosion, and seam of the insulating material after polishing was evaluated as follows. The evaluation results are shown in Table 3.
  • polishing amount of insulating material (Evaluation of polishing amount of insulating material) In the patterned substrate after polishing, the polishing amount of the insulating material (SiOC film) in the region without the copper wiring was measured with a tabletop optical interference film thickness measuring system Nanospec M5000 (manufactured by Nanometrics).
  • a pattern region (“L / S 13 / 7.5” in the table) having a copper wiring portion having a wiring width of 13 ⁇ m and an insulating material portion having a wiring width of 7.5 ⁇ m, and a wiring width of 13 ⁇ m
  • the amount of erosion was determined by scanning with a contact-type step meter (P-16 manufactured by KLA-Tencor Corporation) and measuring the difference between the film thickness of the insulating material portion and the copper wiring portion.
  • a pattern region (“L / S 100/100” in the table) having a copper wiring portion having a width of 100 ⁇ m and an insulating material portion having a width of 100 ⁇ m, and a copper wiring portion and a wiring width having a wiring width of 13 ⁇ m
  • the seam amount was obtained by scanning with a contact-type step meter (P-16 manufactured by KLA Tencor) and measuring the step amount in which the insulating material portion near the copper wiring was excessively polished.
  • the CMP polishing liquid of Comparative Example 1 is a quaternary phosphonium salt, but contains a quaternary phosphonium salt that does not have an aromatic ring bonded to a phosphorus atom. It can be seen that the amount and the seam amount are increased.
  • the CMP polishing liquid of Comparative Example 3 does not contain the quaternary phosphonium salt, so that the erosion amount and the seam amount are large.
  • polishing slurry for CMP of Comparative Example 6 contains silica particles E having an aspect ratio of less than 1.3 and a silanol group density of 1.0 to 2.0 / nm 2 , SiOC It can be seen that the amount of polishing of the film is large, and the amount of erosion and seam are large.
  • the polishing slurry for CMP of Example 3 contains silica particles A and a quaternary phosphonium salt having at least one aromatic ring bonded to a phosphorus atom, and the silica particles A have an aspect ratio. Since it is 1.3 or more and the silanol group density is 1.0 to 2.0 / nm 2 , the polishing amount of the SiOC film is small and the erosion amount and the seam can be obtained even when polishing a substrate with a narrow wiring interval. It can be seen that the amount is sufficiently suppressed.
  • SYMBOLS 1 Insulating material, 2 ... Barrier material, 3 ... Metal for wiring part, 5 ... Silicon substrate, 6 ... Low-k material (insulating material), 7 ... Cap layer, 10 ... Silica particle, 11 ... circumscribed rectangle, 100, 110, 200, 210, 300, 310... Substrate.

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Abstract

La présente invention concerne une solution de polissage pour CMP, qui comprend des particules de silice, un sel phosphonium quaternaire ayant au moins un cycle aromatique lié à un atome de phosphore et de l'eau, chacune des particules de silice ayant une densité de groupe silanol comprise entre 1,0 et 2,0 /nm2 et un rapport d'aspect de 1,3 ou plus, le potentiel zêta dans la solution de polissage pour CMP étant +10 mV ou plus et le rapport entre contenu des particules de silice et contenu du sel de phosphonium quaternaire étant de 750 ou plus.
PCT/JP2013/066862 2012-07-06 2013-06-19 Solution de polissage, solution de préservation et procédé de polissage pour cmp WO2014007063A1 (fr)

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JP2019501511A (ja) * 2015-10-21 2019-01-17 キャボット マイクロエレクトロニクス コーポレイション ディッシング改善用のコバルトインヒビターの組合せ
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WO2016006631A1 (fr) * 2014-07-09 2016-01-14 日立化成株式会社 Solution et procédé de polissage cmp
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JPWO2016006631A1 (ja) * 2014-07-09 2017-06-01 日立化成株式会社 Ｃｍｐ用研磨液及び研磨方法
JP2017019978A (ja) * 2015-07-15 2017-01-26 株式会社フジミインコーポレーテッド 研磨用組成物、磁気ディスク基板製造方法および磁気ディスク基板
JP2018530909A (ja) * 2015-08-12 2018-10-18 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ コバルトを含む基板の研磨のための化学機械研磨（ｃｍｐ）組成物の使用方法
JP2017068886A (ja) * 2015-09-30 2017-04-06 株式会社フジミインコーポレーテッド 磁気ディスク基板用研磨組成物、磁気ディスク基板の製造方法および磁気ディスク基板
WO2017057478A1 (fr) * 2015-09-30 2017-04-06 株式会社フジミインコーポレーテッド Composition de polissage
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JP6140384B1 (ja) * 2015-09-30 2017-05-31 株式会社フジミインコーポレーテッド 研磨用組成物
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JP2019501511A (ja) * 2015-10-21 2019-01-17 キャボット マイクロエレクトロニクス コーポレイション ディッシング改善用のコバルトインヒビターの組合せ
US11492513B2 (en) 2018-03-30 2022-11-08 Jgc Catalysts And Chemicals Ltd. Dispersion liquid of silica particles, polishing composition, and method for producing dispersion liquid of silica particles
JPWO2019189610A1 (ja) * 2018-03-30 2021-05-13 日揮触媒化成株式会社 シリカ粒子分散液、研磨組成物及びシリカ粒子分散液の製造方法
WO2019189610A1 (fr) * 2018-03-30 2019-10-03 日揮触媒化成株式会社 Dispersion de particules de silice, composition de polissage et procédé de fabrication de dispersion de particules de silice
JP7213234B2 (ja) 2018-03-30 2023-01-26 日揮触媒化成株式会社 シリカ粒子分散液、研磨組成物及びシリカ粒子分散液の製造方法
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WO2022107217A1 (fr) * 2020-11-17 2022-05-27 昭和電工マテリアルズ株式会社 Agent de polissage, agent de polissage multi-liquide et procédé de polissage
JPWO2022107217A1 (fr) * 2020-11-17 2022-05-27
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