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US20040216388A1 - Slurry compositions for use in a chemical-mechanical planarization process - Google Patents

Slurry compositions for use in a chemical-mechanical planarization process Download PDF

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US20040216388A1
US20040216388A1 US10/792,738 US79273804A US2004216388A1 US 20040216388 A1 US20040216388 A1 US 20040216388A1 US 79273804 A US79273804 A US 79273804A US 2004216388 A1 US2004216388 A1 US 2004216388A1
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Prior art keywords
slurry
abrasive
spherical
abrasive particles
cmp
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Abandoned
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US10/792,738
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English (en)
Inventor
Sharad Mathur
Ahmad Moini
Ivan Petrovic
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BASF Catalysts LLC
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Engelhard Corp
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Priority to US10/792,738 priority Critical patent/US20040216388A1/en
Priority to PCT/US2004/007468 priority patent/WO2004083328A2/fr
Priority to EP04719748A priority patent/EP1620517A2/fr
Priority to KR1020057017570A priority patent/KR20050111391A/ko
Priority to JP2006507090A priority patent/JP2007525815A/ja
Assigned to ENGELHARD CORPORATION reassignment ENGELHARD CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MOINI, AHMAD, PETROVIC, IVAN, MATHUR, SHARAD
Publication of US20040216388A1 publication Critical patent/US20040216388A1/en
Assigned to BASF CATALYSTS LLC reassignment BASF CATALYSTS LLC CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: ENGELHARD CORPORATION
Abandoned legal-status Critical Current

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    • 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]
    • 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
    • C09K3/1454—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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/7684—Smoothing; Planarisation
    • 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
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step

Definitions

  • the present invention relates to a novel slurry for chemical-mechanical planarization (CMP).
  • CMP chemical-mechanical planarization
  • the present invention is applicable to manufacturing high speed integrated circuits having submicron design features and high conductivity interconnect structures with high production throughput.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • PECVD plasma-enhanced chemical vapor deposition
  • ECP now electrochemical plating
  • Planarizing a surface is a process where material is removed from the surface of the substrate to form a generally even planar surface. Planarization is useful in removing undesired surface topography and surface defects, such as rough surfaces, agglomerated materials, crystal lattice damage, scratches, and contaminated layers or materials. Planarization is also useful in forming features on a substrate by removing excess deposited material used to fill the features and to provide an even surface for subsequent levels of metallization and processing.
  • CMP chemical mechanical planarization
  • a substrate carrier or polishing head is mounted on a carrier assembly and positioned in contact with a polishing pad in a CMP apparatus.
  • the carrier assembly provides a controllable pressure to the substrate urging the substrate against the polishing pad.
  • the pad is moved relative to the substrate by an external driving force.
  • the CMP apparatus effects polishing or rubbing movement between the surface of the substrate and the polishing pad while dispersing a polishing composition, or slurry, to effect both chemical activity and mechanical activity.
  • the abrasive article can be a fixed abrasive article, such as a fixed abrasive polishing pad, which maybe used with a CMP composition or slurry that does not contain abrasive particles.
  • a fixed abrasive article typically comprises a backing sheet with a plurality of geometric abrasive composite elements adhered thereto.
  • Abrasives which are most extensively used in the semi-conductor CMP process are silica (SiO 2 ), alumina (Al 2 O 3 ), ceria (CeO 2 ), zirconia (ZrO 2 ), and titania (TiO 2 ), which can be produced by a fuming or a sol-gel method, as described in U.S. Pat Nos. 4,959,113; 5,354,490; and 5,516,346 and WO97/40,030.
  • Mn 2 O 3 mangania
  • SiN silicon nitride
  • U.S. Pat. No. 6,508,952 discloses a CMP slurry containing any commercially available abrasive agent in particle form, such as SiO 2 , Al 2 O 3 , ZrO 2 , CeO 2 , SiC, Fe 2 O 3 , TiO 2 , Si 3 N 4 , or a mixture thereof.
  • abrasive particles normally have a high purity, a high surface area, and a narrow particle size distribution, and thus are suitable for use in abrasive compositions as abrasive agents.
  • U.S. Pat. No. 4,549,374 discloses polishing semiconductor wafers with an abrasive slurry prepared by dispersing montmorillonite clay in deionized water. The pH of the slurry is adjusted by adding alkali such as NaOH and KOH.
  • circuit density can be achieved by decreasing the space between the individual pathways. Pathways cannot be too close as electrical spillover can occur across the SiO 2 dielectric (the wafer oxide) effectively shorting out the connection. Recent technological advancements permitting the fabrication of very small, high density circuit patterns on integrated circuits have placed higher demands on isolation structures.
  • US Patent Application Publication 2003/0129838 discloses the following non-plate-like abrasive materials: iron oxide, strontium titanate, apatite, dioptase, iron, brass, fluorite, hydrated iron oxide, and azurite.
  • CMP Chemical Mechanical Polishing
  • polishing is accomplished via the removal of surface features using a liquid chemical slurry and a rotating polymer brush.
  • synergistic relationships between surface etching chemicals, surface protecting chemicals, abrasives in the slurry, and polymer pad physics result in a uniform flat surface.
  • particles having a non-spherical morphology are used as the abrasive in a CMP slurry.
  • FIG. 1 is an example of one modified non-spherical particle of the present invention.
  • FIG. 2 is an example of another modified non-spherical particle of the present invention.
  • FIG. 3 is an example of a partially coated non-spherical particle of the present invention.
  • FIG. 4 is an example of another partially coated non-spherical particle of the present invention.
  • FIG. 5 is an example of another partially coated non-spherical particle of the present invention.
  • FIG. 6 is an example of another partially coated non-spherical particle of the present invention.
  • FIG. 7 is an example of a completely coated non-spherical particle of the present invention.
  • FIG. 8 is an example of another partially coated non-spherical particle of the present invention.
  • FIG. 9 is a depiction of the use of CMP to remove rider from a silicon dioxide layer.
  • FIG. 10 is a depiction of polishing an etched semiconductive wafer.
  • FIG. 11 is a depiction of polishing an etched wafer containing metal.
  • FIG. 12 is a Scanning Electron Micrograph (SEM) of the ultrafine abrasive particles prepared in Example 1 below.
  • FIG. 13 is a graph comparing the removal rate of copper using a CMP slurry containing aluminum oxide and a CMP slurry containing calcined kaolin particles as the abrasive.
  • FIG. 14 is a Scanning Electron Micrograph (SEM) of the ultrafine abrasive particles (Sample A) prepared in Example 3 below.
  • CMP slurry compositions include abrasives for mechanical action and at least one of: oxidizers, acids, bases, complexing agents, surfactants, dispersants, and other chemicals for providing a chemical reaction such as oxidation on the surface to be polished. Certain poisons are typically avoided. Examples include metal ions with high mobilities, such as Na + , or elements that undergo reaction with wafer materials such as fluorine (although HF is sometimes used in post-CMP cleaning).
  • Non-limiting examples of available bases include KOH, NH 4 OH, and R 4 NOH. Acids also can be added, which can be exemplified by H 3 PO 4 , CH 3 COOH, HCl, HF and so on. Available as such supplementary oxidizing agents are H 2 O 2 , KIO3, HNO 3 , H 3 PO 4 , K 2 Fe(CN) 6 , Na 2 Cr 2 O 7 , KOCl, Fe(NO 3 ) 2 , NH 2 OH, and DMSO. Divalent acids, such as oxalic acid, malonic acid, and succinic acid can be used as additives for the polishing composition of the present invention.
  • fluorine-containing compounds may be added to the slurry composition.
  • Suitable fluorine-containing compounds include, for example, hydrogen fluoride, perfluoric acid, alkali metal fluoride salt, alkaline earth metal fluoride salt, ammonium fluoride, tetramethylammonium fluoride, ammonium bifluoride, ethylenediammonium difluoride, diethylenetriammonium trifluoride, and mixtures thereof.
  • Suitable chelating agents that may be added to the slurry composition include, for example, ethylenediaminetetracetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid (NHEDTA), nitrilotriacetic acid (NTA), diethylklenetriaminepentacetic acid (DPTA), ethanoldiglycinate, and mixtures thereof.
  • EDTA ethylenediaminetetracetic acid
  • NHEDTA N-hydroxyethylethylenediaminetriacetic acid
  • NTA nitrilotriacetic acid
  • DPTA diethylklenetriaminepentacetic acid
  • ethanoldiglycinate and mixtures thereof.
  • the chelating agents may aid in the softening of the metallic surface or even help to protect low lying features or surfaces of particular composition. The idea of protection mechanisms may lead to significant improvements.
  • Suitable amines that may be added to the slurry composition include, for example, hydroxylamine, monoethanolamine, diethanolamine, triethanolamine, diethyleneglycolamine, N-hydroxylethylpiperazine, and mixtures thereof.
  • Suitable surfactant compounds that may be added to the slurry composition include, for example, any of the numerous nonionic, anionic, cationic, or amphoteric surfactants known to those skilled in the art.
  • the pH of the slurry is vital to the performance of all slurry components.
  • the acidity level of a solution can control reaction rates at the surface, formation constants of metal complexing agents, rates of surface oxidation, solution ionic strength, aggregation size of slurry particles, and more. Examination of various acids, bases, and pH buffers are a prospective area for CMP development.
  • a CMP slurry in which the abrasive is formed of particles having a morphology wherein at least one dimension (height, length and/or width) is substantially larger than another.
  • a morphology will be described as “non-spherical.”
  • a non-spherical particle morphology may be plate-like, sheet-like, needle-like, capsule-like, laminar-like, or any other of a myriad of shapes having at least one dimension substantially larger than another.
  • Such morphology distinguishes over spherical particles which are substantially round in appearance and do not have noticeable elongated surfaces.
  • Laminar clays such as kaolin, vermiculite and montmorillonite (that can be exfoliated) and modifications of such clays that preserve the clay shape such as acid leached kaolin, mica, talc, graphite flake, glass flake, and synthetic polymer flake are useful as abrasives in the CMP slurries of this invention.
  • non-spherical particles are primary in the slurry.
  • the phrase “non-spherical particle” as used herein does not cover a non-spherical agglomeration of spherical particles.
  • the abrasive particles having a non-spherical morphology provide an advantage over the prior art ceramic oxide materials of spherical shape. It is believed that the pressure of the non-spherical abrasive on the substrate surface is distributed over an area rather than a point of contact as the spherical particles. Accordingly, non-spherical particles provide a gentle polishing action and yet reduce micro-scratching, oxide loss, as well as reduce dishing and erosion compared to the point of contact polishing achieved by the hard ceramic abrasives presently used.
  • kaolin clay particles are preferred as the non-spherical abrasive. While hydrous kaolin can be utilized, it has been found that if the kaolin has been calcined, a better polishing rate results. However, the overall performance of hydrous kaolin is better than calcined kaolin and thus, hydrous kaolin is preferred. Calcination of the kaolin to undergo a strong endothermic reaction associated with dehydroxylation results in metakaolin.
  • Calcination temperatures of 1400-2200° F. can be used to produce a kaolin clay that has been calcined through its characteristic exotherm to spinel form kaolin. At the higher temperatures, e.g. above 1900° F., formation of mullite occurs. Any and all of these forms of kaolin clay can be utilized as the abrasive of this invention. All of these materials are available commercially from the present assignee, Engelhard Corporation, Iselin, N.J.
  • Hydrous kaolin is typically prepared through combination of unit operations that modify the particle size distribution and remove coloring impurities from kaolin. These unit operations are facilitated by using aqueous suspensions of kaolin in water. Examples of unit operations that change the particle size distribution are centrifuges, delamination or milling devices and selective flocculation. Examples of unit operations that result in removal of coloring impurities are flotation and magnetic separation. Further, reductive and/or oxidative bleaching can be used to render coloring impurities colorless. In addition, filtration may be utilized to substantially remove water from kaolin following which the high solids filtration product slurry can be spray dried.
  • the spray dried portion can be added back to the high solids filter product slurry to further raise the solids content of the slurry.
  • the filtration product may not be dispersed and thus the filtercake can be dried and pulverized to obtain what is referred to as acid dried kaolin product in the industry.
  • the kaolin may be modified by thermal or chemical treatments. Typically, the kaolin is pulverized prior to and after the calcinations operation. Treated kaolin can be slurried to further effect modifications to the particle size distribution through the unit operations mentioned above.
  • Such a process may be carried out in various ways, depending on the nature of the components and the desired result.
  • chlorides of the metals involved are not worked with, as they lead to a reaction into clay minerals that is hardly perceptible, if at all.
  • expandable clay platelets 10 that are modified via complexation with other components follows.
  • expandable clay platelets 10 have charged cations 12 such as sodium ions residing in the interlayer space of the clay platelets.
  • the expandable clay platelets 10 are ion exchanged with inorganic clusters 14 such as aluminum oxide hydroxide cation (Al 13 Keggin ion) to replace the cations 12 .
  • Al 13 Keggin ion aluminum oxide hydroxide cation
  • the higher charge density of these resulting clusters yields a stronger interlayer interaction, and the clay layers remain stacked.
  • the resulting material is either used without further modification or heated to elevated temperatures to form a 3-dimensional pillared structure.
  • positively charged platelets, such as hydrotalcite may be intercalated with anionic clusters such as poly-oxometallates of Mo, W, and other transition metals.
  • host non-spherical particle 18 is substantially coated with smaller crystallites 24 .
  • useful smaller crystallites 24 include metal oxide or silica crystallites or non-oxide ceramic phases such as metal carbides and nitrides. Such a coating may be formed by heating to convert the platelets or colloidal particles into a crystalline oxide. Alternatively, the desired phase may be crystallized directly onto the surface of the host non-spherical particle 18 similar to known techniques for forming titanium dioxide coated mica pearlescent pigments.
  • An example of a useful process is disclosed in commonly assigned U.S. Pat. No. 4,038,099 incorporated herein by reference in its entirety.
  • Particle sizes of the non-spherical abrasive regardless of the type utilized will typically have an average diameter less than about 1 micron as measured by commercially used particle measurement techniques. See for example commonly assigned U.S. Pat. No. 4,767,466 teaching that particle sizes are determined with the Sedigraph 5100 particle size analyzer and reported as equivalent spherical diameter on a weight percentage basis.
  • Kaolin particle size for example is measured by x-ray sedimentation, e.g. Sedigraph 5100.
  • the average particle size for kaolin will preferably range from about 0.01 to less than about 1 micron and more preferably range from about 0.01 to about 0.5 micron.
  • a pattern In order to place an electrical circuit on a chip, a pattern must be etched on the wafer surface as in FIG. 10.
  • substrate 34 has been etched to form a series of channels 36 which can be filled with dielectric or conductive metal components.
  • the etched substrate 34 increases the challenge of polishing because the surface is not uniform.
  • the substrate 34 as shown has an etched area of low pattern density (A) and an area of high pattern density (B). Surface removal during polishing tends to be greater in areas (B) where the pattern density is high because the local pressure exerted by the pad is distributed over less surface area. Other defects such as erosion and rounding of sharp corners and features of the pattern must also be minimized.
  • Metal polishing as opposed to oxide polishing, is accomplished using an oxidizing agent in the aqueous solution in order to form a soft oxide layer on the metal surface that can be removed by the mechanical abrasives in the slurry. Again, the use of both chemical and mechanical means are used to polish the surface.
  • the silicon nitride layer is intended to function as a polishing stop that protects the underlying thermally grown oxide layer and silicon substrate from being exposed during CMP processing.
  • the silicon nitride layer is later removed by, for example, dipping the article in an HF acid solution, leaving only the silicon dioxide filled trench to serve as an STI structure. Additional processing is usually then performed to form polysilicon gate structures.
  • the slurry was mixed with 4 pounds per ton of Defloc 411 (ammonium polyacrylate) supplied by Sharpe Specialty Chemicals.
  • the mixture was Netzsch milled at 1.2 gallons per minute (gpm)—2 passes using zirconia beads. After Netzsch milling, 2 pounds per ton of Defloc 411 was again added and the mixture then spray dried in order to keep the slurry from spoiling.
  • the spray dried product was reslurried in a Waring Blender for 5 minutes, then deslimed on the CU5000 (centrifuge) at 40% solids for 26 minutes wide open.
  • Desliming removed the ultrafine fraction of the particulate slurry, which is of interest for the CMP application.
  • the size distribution of the spray dried and the ultrafine product as measured by Sedigraph 5100 are set forth in Table 2.
  • An SEM of the ultrafine product, diluted several times to enhance image quality, is shown in FIG. 12. The SEM was obtained using a field emission electron microscope (Jol 6500F) at 5 kV. TABLE 2 PSD (mass Spray % finer than) Ansilex 93 dried product Ultrafine (microns) Slurry Reslurried Product 2 1 92 94 100 0.5 79 83 99 0.3 46 58 98 0.2 16 31 85 5 17 65
  • Example 1 The ultrafine product of Example 1 was reslurried to 4% solids. The slurry was passed through a Puradisc 25 GD glass filter (25 mm diameter and pore size of 2 microns) to remove oversize particles. A chemical package from a generic Copper CMP slurry was added to the abrasive slurry. The chemical package included an oxidizer (hydrogen peroxide), a passivator (benzotriazole), a complexing/etching agent (citric acid), and a stabilizer (TEA, TX-100). For comparison, a commercial alumina-based CMP slurry (Cabot Microelectronics) was used.
  • a hydrous kaolin spray dried product from Engelhard was used as the starting material.
  • the spray dried product was reslurried in lab in a Waring Blender for 5 minutes to 40% solids, then deslimed on CU5000 centrifuge at 40% solids for 15 minutes wide open (2400 rpms).
  • the ultrafine hydrous kaolin fraction constituting the supernatant at 5% solids from the desliming step was filtered through Whatman filter (25 mm diameter and pore size of 2 ⁇ ) and constituted the abrasive slurry for use in CMP formulation (Sample A).
  • the size distribution of the starting spray dried product and the ultrafine product as measured by Sedigraph 5100 are set forth in Table 4.
  • FIG. 12 An SEM of the ultrafine hydrous kaolin (Sample A), diluted several times to enhance image quality, is shown in FIG. 12.
  • the SEM was obtained using a field emission electron microscope (Jeol 6500F) at 10 kV.
  • Example 2 Chemical package from Example 2 was added to the ultrafine hydrous kaolin slurry (Sample A) from Example 3 to prepare a CMP formulation for planarization of Cu (Example 4).
  • Other CMP formulations were prepared with the same chemical package by using a fumed silica slurry and alumina slurry.
  • the fumed silica used was Aerosil 200 from Degussa (primary particle size of 12 nm and average aggregate size of 170 nm as measured by Microtrac)(Comparative A).
  • the alumina particles were of alpha form and obtained from Polishing Solutions Inc. (Comparative B). The proprietary alumina particles are used in commercial CMP slurries for metal planarization.
  • the CMP slurries were tested on bare 200 mm tetraethylorthosilicate (hereinafter “TEOS”) silica wafers as well as coated with either copper or tantalum to determine the polishing rate to aid in estimating the polishing time for clearing copper on the patterned wafers, as well as determine surface smoothness and selectivity between copper/tanatalum and copper/silica.
  • TEOS tetraethylorthosilicate
  • the CMP slurries were then tested on 200 mm Si wafers provided with copper interconnects and Ta diffusion barrier by the dual damascene process (patterned wafers) to assess the erosion and dishing. Erosion was measured at 70% patterned density while the dishing was measured on 300 micron pitch copper line. The dishing and erosion measurements were done on both the polished and overpolished wafers (20% extra time over polished wafers) to determine sensitivity of these undesirable topographic features to overpolishing.
  • ultrafine hydrous kaolin based CMP slurry resulted in the desired higher selectivity and uniformity than either fumed silica or alumina.
  • the copper material removal rate with the ultrafine hydrous kaolin is comparable to fumed silica and lower than that due to alumina.
  • the Cu/Ta selectivity is more critical than the polishing rate since the expected outcome from the Cu planarization slurry is to stop at the Ta layer.
  • the low Ta planarization rate with the hydrous kaolin formulation precludes from taking advantage of better Ta/TEOS selectivity than silica or alumina based CMP formulation.
  • the ultrafine hydrous kaolin based CMP slurry resulted in significantly lower erosion with no sensitivity to overpolishing compared to silica and alumina. This is consistent with the high selectivity for copper/tantalum and tantalum/TEOS removal rates obtained with the ultrafine hydrous kaolin slurry.
  • the ultrafine hydrous kaolin slurry is expected to result in lower erosion as well as oxide and metal loss.
  • the dishing was similar with all the abrasives indicating a strong role of the chemistry in the formulation compared to the mechanical action of the abrasives.
  • Example B CMP formulations based on ultrafine hydrous kaolin (Sample B) and fumed silica in Example 4 were used with the exception of removal of TX100 and TEA from the chemical package and lowering the slurry pH from 5 to 4 (Comparative C).
  • Example D an alumina-based commercial slurry from Cabot Microelectronics (CCMP) was also used (Comparative D).
  • the CMP slurries were tested on bare 200 mm TEOS wafers as well as coated with either copper or tantalum to determine the polishing rate to aid in estimating the polishing time for the patterned wafers, surface smoothness and selectivity between copper/tanatalum as well as copper/silica.
  • the CMP slurries were then tested on 200 mm Si wafers provided with copper interconnects and Ta diffusion barrier by the dual damascene process (patterned wafers) to assess the erosion and dishing. Erosion was measured at 70% patterned density while the dishing was measured on 150 micron width copper line. The dishing and erosion measurements were done on both the polished and overpolished wafers (20% extra time over polished wafers) to determine sensitivity to overpolishing.
  • Example 4 The testing was done on the same machine as in Example 4 and at a down pressure of 2 psi and platen speed of 90 rpm. Blanket Wafers Abrasive in CMP Material Removal Rate Copper/TEOS slurry (nm/min) WIWNU, % Selectivity Example 5 173 1 1020 Comparative C 224 1 83 Comparative D 127 17 52

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  • Organic Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
US10/792,738 2003-03-17 2004-03-05 Slurry compositions for use in a chemical-mechanical planarization process Abandoned US20040216388A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US10/792,738 US20040216388A1 (en) 2003-03-17 2004-03-05 Slurry compositions for use in a chemical-mechanical planarization process
PCT/US2004/007468 WO2004083328A2 (fr) 2003-03-17 2004-03-11 Compositions en suspension utilisees dans un processus de planarisation chimico-mecanique
EP04719748A EP1620517A2 (fr) 2003-03-17 2004-03-11 Compositions en suspension utilisees dans un processus de planarisation chimico-mecanique
KR1020057017570A KR20050111391A (ko) 2003-03-17 2004-03-11 화학적-기계적 평탄화 방법에서 사용하기 위한 비-구형연마제 입자를 갖는 슬러리 조성물
JP2006507090A JP2007525815A (ja) 2003-03-17 2004-03-11 化学−機械的平面化処理に使用するためのスラリ組成物

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US50944503P 2003-10-08 2003-10-08
US10/792,738 US20040216388A1 (en) 2003-03-17 2004-03-05 Slurry compositions for use in a chemical-mechanical planarization process

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WO2008069781A1 (fr) * 2006-12-04 2008-06-12 Basf Se Composition d'aplanissement pour des surfaces métalliques, comprenant un abrasif d'hydrate d'alumine
US7763577B1 (en) * 2009-02-27 2010-07-27 Uwiz Technology Co., Ltd. Acidic post-CMP cleaning composition
US20100258143A1 (en) * 2009-04-13 2010-10-14 Microchip Technology Incorporated Scrubber clean before oxide chemical mechanical polish (cmp) for reduced microscratches and improved yields
US7919815B1 (en) * 2005-02-24 2011-04-05 Saint-Gobain Ceramics & Plastics, Inc. Spinel wafers and methods of preparation
US8440602B2 (en) 2009-12-22 2013-05-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a divinyl benzene cross-linked styrene polymer
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KR101279971B1 (ko) 2008-12-31 2013-07-05 제일모직주식회사 구리 배리어층 연마용 ｃｍｐ 슬러리 조성물, 이를 이용한 연마 방법, 및 그 연마방법에 의해 제조된 반도체 소자
US8546316B2 (en) 2010-09-21 2013-10-01 The Procter & Gamble Company Liquid detergent composition with natural abrasive particles
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US20160104629A1 (en) * 2012-02-03 2016-04-14 Samsung Electronics Co., Ltd. Apparatus and a method for treating a substrate
US9353337B2 (en) 2010-09-21 2016-05-31 The Procter & Gamble Company Liquid cleaning composition
EP3004304A4 (fr) * 2013-05-31 2016-06-08 Unilever Nv Composition pour le nettoyage de surfaces dures
CN114539813A (zh) * 2020-11-18 2022-05-27 华为技术有限公司 非球形的二氧化硅颗粒及其制备方法和抛光液
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US20050072054A1 (en) * 2003-10-02 2005-04-07 Amcol International Corporation, A Delaware Corporation Chemical-mechanical polishing (CMP) slurry and method of planarizing computer memory disk surfaces
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US7736530B2 (en) * 2006-01-25 2010-06-15 Lg Chem, Ltd. CMP slurry and method for polishing semiconductor wafer using the same
WO2008069781A1 (fr) * 2006-12-04 2008-06-12 Basf Se Composition d'aplanissement pour des surfaces métalliques, comprenant un abrasif d'hydrate d'alumine
US9343330B2 (en) 2006-12-06 2016-05-17 Cabot Microelectronics Corporation Compositions for polishing aluminum/copper and titanium in damascene structures
US20080134585A1 (en) * 2006-12-06 2008-06-12 Cabot Microelectronics Corporation Compositions for polishing aluminum/copper and titanium in damascene structures
US8440604B2 (en) 2008-09-30 2013-05-14 The Procter & Gamble Company Liquid hard surface cleaning composition
US8569223B2 (en) 2008-09-30 2013-10-29 The Procter & Gamble Company Liquid hard surface cleaning composition
US8551932B2 (en) 2008-09-30 2013-10-08 The Procter & Gamble Company Liquid hard surface cleaning composition
KR101279971B1 (ko) 2008-12-31 2013-07-05 제일모직주식회사 구리 배리어층 연마용 ｃｍｐ 슬러리 조성물, 이를 이용한 연마 방법, 및 그 연마방법에 의해 제조된 반도체 소자
US7763577B1 (en) * 2009-02-27 2010-07-27 Uwiz Technology Co., Ltd. Acidic post-CMP cleaning composition
US20100258143A1 (en) * 2009-04-13 2010-10-14 Microchip Technology Incorporated Scrubber clean before oxide chemical mechanical polish (cmp) for reduced microscratches and improved yields
US8680036B2 (en) 2009-12-22 2014-03-25 The Procter & Gamble Company Liquid cleaning composition comprising color-stable polyurethane abrasive particles
US9163200B2 (en) 2009-12-22 2015-10-20 The Procter & Gamble Company Liquid cleaning and/or cleansing composition
US8440602B2 (en) 2009-12-22 2013-05-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a divinyl benzene cross-linked styrene polymer
US8629095B2 (en) 2010-04-21 2014-01-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising polyurethane foam abrasive particles
US9353337B2 (en) 2010-09-21 2016-05-31 The Procter & Gamble Company Liquid cleaning composition
US8546316B2 (en) 2010-09-21 2013-10-01 The Procter & Gamble Company Liquid detergent composition with natural abrasive particles
US8445422B2 (en) 2010-09-21 2013-05-21 The Procter & Gamble Company Liquid cleaning composition
US8440603B2 (en) 2011-06-20 2013-05-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a polylactic acid biodegradable abrasive
US8703685B2 (en) 2011-06-20 2014-04-22 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising polylactic acid abrasives
US8759270B2 (en) 2011-06-20 2014-06-24 The Procter & Gamble Company Liquid detergent composition with abrasive particles
US8852643B2 (en) 2011-06-20 2014-10-07 The Procter & Gamble Company Liquid cleaning and/or cleansing composition
US8470759B2 (en) 2011-06-20 2013-06-25 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a polyhydroxy-alkanoate biodegradable abrasive
US20160104629A1 (en) * 2012-02-03 2016-04-14 Samsung Electronics Co., Ltd. Apparatus and a method for treating a substrate
US9721801B2 (en) * 2012-02-03 2017-08-01 Samsung Electronics Co., Ltd. Apparatus and a method for treating a substrate
US9163201B2 (en) 2012-10-15 2015-10-20 The Procter & Gamble Company Liquid detergent composition with abrasive particles
EP3004304A4 (fr) * 2013-05-31 2016-06-08 Unilever Nv Composition pour le nettoyage de surfaces dures
US11781039B2 (en) * 2016-12-26 2023-10-10 Fujimi Incorporated Polishing composition and polishing method
CN114539813A (zh) * 2020-11-18 2022-05-27 华为技术有限公司 非球形的二氧化硅颗粒及其制备方法和抛光液

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WO2004083328A2 (fr) 2004-09-30
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EP1620517A2 (fr) 2006-02-01

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