Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
• • 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
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
  • H10P52/40—Chemomechanical polishing [CMP]
  • H10P52/403—Chemomechanical polishing [CMP] of conductive or resistive materials

Definitions

• the present invention concerns chemical compositions for use in polishing.
• the present invention concerns chemical compositions for use in polishing.
• present invention relates to a polishing slurry for the chemical-mechanical polishing of metal surfaces.
• CMP Chemical-mechanical polishing
• CMP has become the technology of choice among semiconductor chip fabricators to polish or planarize the surface of semiconductor chips after
• each metal containing circuit pattern layer is laid down.
• CMP technology is well-known, and
• polishing slurry to the surface to be polished
• a slurry for CMP metal surfaces which generally comprises: (i) water; and (ii) high -2- purity fine metal oxide particles.
• U.S. Pat. 5,575,885 issued to Hirabayashi et al. discloses a slurry for CMP copper-based metal surfaces which generally comprises: (i)
• a slurry for CMP metal surfaces is needed which provides significant improvement in terms of removal rates as compared to the prior art slurries. Moreover, a slurry for CMP metal surfaces is needed which is useful for polishing metals
• the present invention is directed to a chemical composition or slurry for CMP which
• a slurry for CMP metal surfaces according to the present invention generally comprises: (i) water; (ii) abrasive particles; and (iii) an oxidizing
• the oxidizing solution (iii) comprises: (a) water
• metals selected from the group consisting of chromium, cobalt, copper, iron, lead,
• the oxidizing solution (iii) comprises: (a') water soluble peroxide; and (b') organic amine.
• organic amine in combination with
• such oxidizing solution can further optionally comprise one or more metals and/or compounds containing metals selected from
• FIG. 1 is a graph illustrating that in a slurry of the present invention the rapid
• FIG. 2 is a graph illustrating that in a slurry of the present invention the rate of
• FIG. 3 is a graph illustrating that in a slurry of the present invention the rate of
• FIG. 4 is a graph illustrating that in a slurry of the present invention the use of copper
• the present invention provides a chemical composition for use as a CMP slurry which
• the slurry contains: (i) water, (ii) abrasive particles; and (iii) an oxidizing solution.
• the slurry contains: (i) water, (ii) abrasive particles; and (iii) an oxidizing solution.
• oxidizing solution (iii) comprises: (a) water soluble peroxide; (b) an amino acid or mixture
• chromium from the group consisting of chromium, cobalt, copper, iron, lead, nickel, palladium, rhodium,
• the oxidizing solution (iii) comprises: (a') water soluble peroxide; and (b') organic amine.
• the water (i) used in the slurry is preferably distilled water. More preferably, the
• the abrasive particles (ii) used in the slurry may comprise any one or a mixture of a
• suitable abrasive particles include alumina, silica, silicon nitride, silicon carbide, ceria, copper
• the abrasive particles preferably have
• a mean size ranging from about 0.02 to about 1.0 micrometers, with a maximum size of less
• the abrasive particles are preferably present in the slurry in an amount of from about 0.1 to about 60% by weight of the slurry.
• the oxidizing solution (iii) used in the slurry must rapidly generate more hydroxyl
• the oxidizing solution (iii) comprises:
• chromium 0 group consisting of chromium, cobalt, copper, iron, lead, nickel, palladium, rhodium,
• the water soluble peroxide (iii)(a) and (iii)(a') may comprise any water soluble peroxide (iii)(a) and (iii)(a') may comprise any water soluble peroxide (iii)(a) and (iii)(a') may comprise any water soluble peroxide (iii)(a) and (iii)(a') may comprise any water soluble peroxide (iii)(a) and (iii)(a') may comprise any water soluble
• R peroxide having the structure R-O-O-H, where R is hydrogen, an aliphatic hydrocarbon, or
• the water soluble peroxide is hydrogen peroxide. In another preferred embodiment, the water soluble peroxide is t-butyl-
• the water soluble peroxide is preferably present in the slurry by weight from about 0.1% to about 30%.
• the amino acid (iii)(b) is selected from amino carboxylic acid, amino alkyl carboxylic acid, amino phenyl carboxylic acids and the sodium, potassium, and ammonium salts thereof, or a combination of the foregoing. Examples of specific amino acids suitable for use in the
• present invention include arginine, cysteine, glutamine, glutamic acid, glycine. histidine.
• the amino acid is preferably present in the slurry in an amount of from about 0.1 to about 10% by weight.
• metals and/or compounds containing metals (iii)(c) and optionally (iii)(c ) are one
• chromium or more selected from the group consisting of chromium, cobalt, copper, iron. lead, nickel,
• the metals can be used in the elemental form
• metal containing compounds such as water-soluble salts and oxides which
• Copper is the most preferred metal. Suitable forms of copper for use in the
• inventions include, for example, copper acetate, copper bromide, copper butyrate.
• hydroxide powder elemental copper powder, copper perchlorate, copper phenolsulfonate.
• compounds containing metals are preferably present in the slurry in an amount of from about
• the organic amine (iii)(b') used in the slurry may comprise primary amine (RNH 2 ),
• R is an aliphatic hydrocarbon or an
• the organic amine is N-(2-aminoethyl)-2-aminoethyl amine
• the organic amine is preferably
• present in the slurry in an amount of from about 0.1% to about 10% by weight.
• polishing For semiconductor polishing applications, it is generally preferred to polish
• the metal layers deposited on the substrate rapidly without etching or polishing the substrate
• the pH of the slurry is adjusted such that it is more acidic, the substrate material will not
• the slurry is optionally
• the slurry or polishing composition should be formulated so as to give a polishing
• glycol nitric acid, potassium hydroxide and propylene glycol may be added to adjust the
• surfactant polymeric stabilizers or other surface active dispersing agents can be used.
• Another aspect of the present invention relates to a method for polishing a metal
• polishing slurry composition with a metal surface to be polished and polishing the metal
• the polishing slurry composition comprises water, abrasive particles,
• the oxidizing solution comprises one or more
• water soluble peroxides one or more amino acids, and one or more metals or compounds
• metals selected from the group consisting of chromium, cobalt, copper, iron. lead.
• solution comprises one or more water soluble peroxides, one or more organic amines, and
• chromium consisting of chromium, cobalt, copper, iron, lead, nickel, palladium, rhodium, samarium, and
• the polishing method of the present invention is carried out by contacting the aqueous
• polishing composition or slurry with the metal to be polished normally at room temperature -9-
• the metal surface is then polished with the composition using a felt or other polishing pad.
• Typical pads include Rodel Suba 500 pads, IC 1000 pads or similar commercially available
• polishing is usually conducted at room temperature, it will be appreciated
• polishing composition of the present invention In addition to providing a slurry, the polishing composition of the present invention
• the metals and/or compounds may be generated in situ. More particularly, for example, the metals and/or compounds
• the polishing pad may be formed by incorporating a portion of the components of the slurry in a polishing pad.
• Pads that contain one or more components of the polishing slurry are well-known,
• the CMP slurry provided herein is particularly useful for polishing metal layers on
• Metal layers which may be polished using the CMP slurry disclosed herein include aluminum, copper, tantalum, tantalum nitride, titanium, tungsten, titanium nitride, titanium tungsten, and alloys or mixtures thereof.
• the slurry of the present invention may be prepared in a conventional manner by
• hydroxyl radical trap such as N,N-dimethyl-4-nitrosoaniline (PND A).
• PND A N,N-dimethyl-4-nitrosoaniline
• PNDA has a unique and strong absorption in the visible region at 440 nm whereas the
• the concentration of hydroxyl radical can be calculated by the rate equation
• ⁇ represents the molar absorptivity of PNDA
• c represents the transient concentration
• ⁇ 2 represents the molar abso ⁇ tivity of
• A is the absorption of the sample at any given time and A ⁇ is the initial absorption of
• Example 1 The purpose of the series of experiments conducted as Example 1 is to demonstrate
• Table 1 demonstrates that copper (both valences) is far superior as a radical promoter
• iron, lead, nickel, palladium, rhodium, samarium, and scandium are less effective in promoting
• Example 1 Each solution's intensity at 440nm was measured for 30 minutes in 5
• Example 2 demonstrates that as the concentration of b ⁇ s(hexamethvlene)t ⁇ am ⁇ ne
• Example 2 also demonstrates that the addition of metal ions to a
• Fig. 1 shows the plot of the ratio of PNDA concentration remaining in solution versus
• Example 3 The experiment in Example 3 was repeated except that glycine in the aqueous
• concentrations of hydrogen peroxide, amino acid and copper nitrate were 2% bv weight, 1%
• Fig. 2 illustrates the various components
• nitrate is replaced by copper oxide powder or elemental copper powder.
• concentration of copper oxide and copper powders varied from 3 mg/10 ml to 10 mg/10 ml.
• a tantalum disc is polished using a Struers polisher and Suba 500 pad, at a pressure
• Slurry A contains: (1) 3% by weight alumina abrasive particles with a mean
• Slurry B contains: (1) 3% by weight alumina abrasive particles with a mean

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Treatment Of Semiconductor (AREA)

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• 1999
  • 1999-04-05 KR KR1020007011294A patent/KR20010042616A/ko not_active Withdrawn
  • 1999-04-05 JP JP2000544000A patent/JP2002511650A/ja not_active Withdrawn
  • 1999-04-05 WO PCT/US1999/007482 patent/WO1999053532A1/en not_active Ceased
  • 1999-04-05 EP EP99916387A patent/EP1086484A4/de not_active Withdrawn

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