WO1999053532A1 - Slurry for chemical-mechanical polishing metal surfaces - Google Patents

Slurry for chemical-mechanical polishing metal surfaces Download PDF

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Publication number
WO1999053532A1
WO1999053532A1 PCT/US1999/007482 US9907482W WO9953532A1 WO 1999053532 A1 WO1999053532 A1 WO 1999053532A1 US 9907482 W US9907482 W US 9907482W WO 9953532 A1 WO9953532 A1 WO 9953532A1
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Prior art keywords
slurry
metal
chemical
mechanical polishing
copper
Prior art date
Application number
PCT/US1999/007482
Other languages
French (fr)
Inventor
John E. Prendergast
Yieshein Her
Suryadevara V. Babu
Yuzhuo Li
Mariappan Hariharaputhiran
Original Assignee
Ferro Corporation
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Priority to US5861898A priority Critical
Priority to US09/058,618 priority
Priority to US27745499A priority
Priority to US09/277,454 priority
Application filed by Ferro Corporation filed Critical Ferro Corporation
Publication of WO1999053532A1 publication Critical patent/WO1999053532A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS OTHER THAN FRENCH POLISH; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/02Polishing compositions containing abrasives or grinding agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/1454Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463Aqueous liquid suspensions
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3205Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321After treatment
    • H01L21/32115Planarisation
    • H01L21/3212Planarisation by chemical mechanical polishing [CMP]

Abstract

The present invention provides a slurry for chemical-mechanical polishing metal surfaces which significantly increases the removal rate and is capable of polishing metals which are inert to most common oxidizing agents. The slurry is particularly useful for polishing metal layers on semiconductor wafer substrates. The slurry includes water, abrasive particles, and an oxidizing solution. In one preferred embodiment, the oxidizing solution comprises one or more water soluble peroxides, one or more amino acids, and one or more metals and/or compounds containing metals selected from the group consisting of chromium, cobalt, copper, iron, lead, nickel, palladium, rhodium, samarium, and scandium, with copper being preferred. In another preferred embodiment, the oxidizing solution comprises one or more water soluble peroxides, one or more organic amines, and optionally one or more metals and/or compounds containing metals.

Description

Title SLURRY FOR CHEMICAL-MECHANICAL POLISHING METAL SURFACES

Background Of The Invention

Field of the Invention

The present invention concerns chemical compositions for use in polishing. The

present invention relates to a polishing slurry for the chemical-mechanical polishing of metal surfaces.

Description of the Related Art

Chemical-mechanical polishing ("CMP") is a technology which has its roots in the pre-

industrial era. In recent years, 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

is typically accomplished by applying pressure with a polishing pad saturated with a metal

polishing slurry to the surface to be polished.

Examples of prior art patents that concern CMP include U.S. Patent No. 4,959, 1 13

issued to Roberts that discloses a slurry for CMP metal surfaces which generally comprises:

(i) water; (ii) abrasive particles; and (iii) a salt. U.S. Patent No. 5,354,490 issued to Yu et

al. discloses a slurry for the CMP of predominantly copper metal surfaces which generally

comprises: (i) water; (ii) abrasive particles; and (iii) a component selected from the group

consisting of HNO3, H2SO4, and AgNO3. U.S. Patent No. 5,527,423 issued to Neville et al.

discloses a slurry for CMP metal surfaces which generally comprises: (i) water; and (ii) high -2- purity fine metal oxide particles. Additionally, U.S. Pat. 5,575,885 issued to Hirabayashi et al. discloses a slurry for CMP copper-based metal surfaces which generally comprises: (i)

water: (ii) an organic acid; and (iii) an oxidizer.

Unfortunately, many prior art slurries for CMP metal surfaces have achieved less than

desired removal rates. Moreover, many prior art slurries for CMP metal surfaces have not

been particularly useful for polishing metals, such as tantalum, which are inert to common

oxidizing agents. Accordingly, 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

which are inert to common oxidizing agents.

Summary Of The Invention

The present invention is directed to a chemical composition or slurry for CMP which

displays superior removal rate when polishing metal surfaces, including metal surfaces which

are inert to common oxidizing agents. A slurry for CMP metal surfaces according to the present invention generally comprises: (i) water; (ii) abrasive particles; and (iii) an oxidizing

solution. In one preferred embodiment, the oxidizing solution (iii) comprises: (a) water

soluble peroxide; (b) one or more amino acids; and (c) one or more metals and/or compounds

containing metals selected from the group consisting of chromium, cobalt, copper, iron, lead,

nickel, palladium, rhodium, samarium, and scandium, with copper being preferred. The use of metals and/or compounds containing metals in combination with water soluble peroxide and amino acid results in the accelerated generation of hydroxyl radicals and yields a much

more effective polishing composition.

In another preferred embodiment, the oxidizing solution (iii) comprises: (a') water soluble peroxide; and (b') organic amine. The use of organic amine in combination with

water soluble peroxide also results in the accelerated generation of hydroxyl radicals. To

further increase the generation of hydroxyl radicals, such oxidizing solution can further optionally comprise one or more metals and/or compounds containing metals selected from

the group consisting of chromium, cobalt, copper, iron. lead, nickel, palladium, rhodium,

samarium, and scandium, with copper being preferred.

These and other aspects and advantages of the present invention will be readily understood and appreciated by those skilled in the art from the following detailed description

of the invention with the best mode contemplated for practicing the invention in view of the

accompanying drawings.

Brief Description Of The Drawings

In the annexed drawings:

FIG. 1 is a graph illustrating that in a slurry of the present invention the rapid

formation of hydroxyl radicals occurs when hydrogen peroxide, glycine and copper nitrate are

present at the same time;

FIG. 2 is a graph illustrating that in a slurry of the present invention the rate of

hydroxyl radical formation varies when other amino acids are substituted for glycine: -4-

FIG. 3 is a graph illustrating that in a slurry of the present invention the rate of

hydroxyl radical formation varies when elemental copper or copper oxide are substituted for

copper nitrate; and

FIG. 4 is a graph illustrating that in a slurry of the present invention the use of copper

nitrate, hydrogen peroxide and glycine in the slurry increases the polish rate of copper.

Detail Description Of The Preferred Embodiments

The present invention provides a chemical composition for use as a CMP slurry which

provides high removal rates when polishing metal surfaces. The slurry contains: (i) water, (ii) abrasive particles; and (iii) an oxidizing solution. In one preferred embodiment, the

oxidizing solution (iii) comprises: (a) water soluble peroxide; (b) an amino acid or mixture

of amino acids; and (c) one or more metals and/or compounds containing metals selected

from the group consisting of chromium, cobalt, copper, iron, lead, nickel, palladium, rhodium,

samarium, and scandium, with copper being preferred. The combination of components (a),

(b) and (c) generates a large amount of hydroxyl radicals (OH ), which is a much stronger oxidizing agent as compared to hydrogen peroxide alone. In another preferred embodiment,

the oxidizing solution (iii) comprises: (a') water soluble peroxide; and (b') organic amine.

The combination of components (a') and (b') also generate a large amount of hydroxyl

radicals. Applicants have found that the presence of a stronger oxidizing agent significantly

improves the removal rate when polishing metal surfaces.

The water (i) used in the slurry is preferably distilled water. More preferably, the

water is doubly distilled water. -5-

The abrasive particles (ii) used in the slurry may comprise any one or a mixture of a

variety of abrasive particles that are conventionally utilized in CMP slurries. Examples of

suitable abrasive particles include alumina, silica, silicon nitride, silicon carbide, ceria, copper

oxide, iron oxide, nickel oxide, manganese oxide, tin oxide, titania. titanium carbide, tungsten

5 oxide, yttria and zirconia. or a combination thereof. The abrasive particles preferably have

a mean size ranging from about 0.02 to about 1.0 micrometers, with a maximum size of less

than about 10 micrometers. 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

o radicals than would otherwise be generated by hydrogen peroxide alone. The applicants have

found that the presence of a relatively large concentration of hydroxyl radicals greatly

enhances the polishing rate of metals, including metals such as tantalum which are inert to most oxidizing agents. In one preferred embodiment, the oxidizing solution (iii) comprises:

(a) one or more water soluble peroxides; (b) an amino acid or mixture of amino acids; and (c)

5 one or more metals and/or compounds containing metals selected from the group consisting

of chromium, cobalt, copper, iron, lead, nickel, palladium, rhodium, samarium, and scandium,

with copper being preferred. In another preferred embodiment, the oxidizing solution (iii)

comprises: (a') one or more water soluble peroxides; (b') one or more organic amines; and

optionally (c') one or more metals and/or compounds containing metals selected from the

0 group consisting of chromium, cobalt, copper, iron, lead, nickel, palladium, rhodium,

samarium, and scandium, with copper being preferred. -6-

The water soluble peroxide (iii)(a) and (iii)(a') may comprise any water soluble

peroxide having the structure R-O-O-H, where R is hydrogen, an aliphatic hydrocarbon, or

an aromatic hydrocarbon. In the most preferred embodiment, the water soluble peroxide is hydrogen peroxide. In another preferred embodiment, the water soluble peroxide is t-butyl-

hydroperoxide. 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.

phenylalanine, and serine. The amino acid is preferably present in the slurry in an amount of from about 0.1 to about 10% by weight.

The metals and/or compounds containing metals (iii)(c) and optionally (iii)(c ) are one

or more selected from the group consisting of chromium, cobalt, copper, iron. lead, nickel,

palladium, rhodium, samarium, and scandium. The metals can be used in the elemental form

or in the form of metal containing compounds, such as water-soluble salts and oxides which

are preferred. Copper is the most preferred metal. Suitable forms of copper for use in the

invention include, for example, copper acetate, copper bromide, copper butyrate. copper

chlorate, copper chloride, copper citrate, copper fluoride, copper formate, copper gluconate.

copper glycinate, copper hexafluorosilicate, copper nitrate, copper oxide powder, copper

hydroxide powder, elemental copper powder, copper perchlorate, copper phenolsulfonate. -7- copper salicylate, copper selenate, copper sulfate, and copper tartrate, or a combination of

the foregoing. Similar forms of chromium, cobalt, iron, lead, nickel, palladium, rhodium,

samarium, and scandium would also be suitable for use in the invention. The metals and/or

compounds containing metals are preferably present in the slurry in an amount of from about

0.1% to about 10% by weight.

The organic amine (iii)(b') used in the slurry may comprise primary amine (RNH2),

secondary amine (R2NH), tertiary amine (R3N), mixtures thereof, and/or an amine containing

all or some of these three types of amine moieties, where R is an aliphatic hydrocarbon or an

aromatic hydrocarbon. In the currently preferred embodiment, the organic amine is

bis(hexamethylene)triamine (H2N(CH2)6NH(CH2)6NH2). The organic amine is preferably

present in the slurry in an amount of from about 0.1% to about 10% by weight.

The slurry according to the present invention effectively polishes metals throughout

a wide pH range. For semiconductor polishing applications, it is generally preferred to polish

the metal layers deposited on the substrate rapidly without etching or polishing the substrate

material at all. It has been found that polishing with a slurry having a pH greater than about

7 will sometimes cause the substrate material to become polished or etched. However, when

the pH of the slurry is adjusted such that it is more acidic, the substrate material will not

become polished or etched. Accordingly, for such applications the slurry is optionally

adjusted to a pH of from about 2 to about 5 by adding common acids such as hydrochloric

acid, nitric acid, sulfiiric acid, acetic acid, phosphoric acid or other conventional acids. The slurry or polishing composition should be formulated so as to give a polishing

slurry having a desirable concentration and viscosity. The desirable viscosity range should

be low enough such that the polishing composition is free flowing. Additives such as ethylene

glycol, nitric acid, potassium hydroxide and propylene glycol may be added to adjust the

viscosity of the slurry. In order to stabilize the polishing slurry against settling, flocculation

and decomposition of the oxidizing component, a variety of additives, such as, for example,

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

surface comprising the steps of providing a polishing slurry composition, contacting the

polishing slurry composition with a metal surface to be polished and polishing the metal

surface. In this method the polishing slurry composition comprises water, abrasive particles,

and an oxidizing solution. In one embodiment, the oxidizing solution comprises one or more

water soluble peroxides, one or more amino acids, and one or more metals or compounds

containing metals selected from the group consisting of chromium, cobalt, copper, iron. lead.

nickel, palladium, rhodium, samarium, and scandium. In another embodiment, the oxidizing

solution comprises one or more water soluble peroxides, one or more organic amines, and

optionally one or more metals and/or compounds containing metals selected from the group

consisting of chromium, cobalt, copper, iron, lead, nickel, palladium, rhodium, samarium, and

scandium. Thus, the method uses the slurry discussed above.

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

pads. Although polishing is usually conducted at room temperature, it will be appreciated

that an increase in the temperature generally results in an increase in the concentration of

hydroxyl radicals formed.

In addition to providing a slurry, the polishing composition of the present invention

may be generated in situ. More particularly, for example, the metals and/or compounds

containing metals (iii)(c) and the amino acids (iii)(b) could be added on the metal surface to

be polished to a solution of water (i), abrasive particles (ii), and water soluble peroxide

(iϋ)(a). Alternatively, for example, a solution of the metals and/or compounds containing

metals (iϋ)(c), amino acids (iii)(b), and water soluble peroxide (iii)(a) could be added on the

polishing surface to a solution of water (i) and abrasive particles (ii). It will be appreciated

that since the order of addition is not per se critical, any number of a multitude of possible

combinations for forming the slurry in situ could be employed. However, because peroxides

decompose rapidly once being mixed with the other components, it is preferable to keep

peroxides from the other components in the slurry formulation until immediately prior to use.

In another aspect of the present invention the polishing slurry of the present invention

may be formed by incorporating a portion of the components of the slurry in a polishing pad.

For example, the amino acids (ϋi)(b), abrasive particles (ii) and the metals and/or compounds

containing metals (iii)(c) could be incorporated directly in the polishing pad, and a solution

of water (i) and water soluble peroxide (iii)(a) could then be added at the polishing surface -10- to form the polishing slurry in situ. It will be appreciated that the components of the polishing slurry composition according to the invention could be combined in various ways to form the

slurry in situ.

Pads that contain one or more components of the polishing slurry are well-known,

such as the pad disclosed in Mayton et al. U.S. Patent No. 5,000,761 and Shukla et al. U.S.

Patent No. 4,576,612. Mayton et al. U.S. Patent No. 5,000,761 and Shukla et al. U.S. Patent No. 4,576,612 are incorporated herein by reference for their teachings of how to produce a pad containing one or more components that serve to form the polishing slurry in situ during

the polishing operation. The CMP slurry provided herein is particularly useful for polishing metal layers on

semiconductor wafer substrates. 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

merely mixing the various components of the formulation. No special mixing techniques or

equipment are required, and the order of addition is not critical. The components are

preferably combined immediately prior to use.

The present invention will now be described in more detail with reference to the following specific nonlimiting examples. -11- Preface to Examples

As noted by Liu, X., DiLabi, G.A., Martin, F., and Li, Y in "Catalytic Formation of

Hydroxyl Radical from Hydrogen Peroxide in the Presence of an Amine", submitted to

J.A.O.S. in 1998, the formation of hydroxyl radicals can be quantitatively analyzed using a

hydroxyl radical trap such as N,N-dimethyl-4-nitrosoaniline (PND A). As the hydroxyl radical is formed, it adds to the PNDA via the reaction described below:

H,C 0 mc 0 H

//

N- [OH] N - - t

/' ./' \ mc H,C 0"

PNDA has a unique and strong absorption in the visible region at 440 nm whereas the

product of the reaction between PNDA and a hydroxyl radical has a weak absorption at 440nm. Thus, the amount of hydroxyl radical formed is detected by the disappearance of

PNDA over time as indicated by subsequent decreasing absorptions at 440nm.

The concentration of hydroxyl radical can be calculated by the rate equation

-d[PNDA]/dt=k'[PNDA][-OH]

When assuming [OH] is in steady state, the above-equation becomes:

-d[PNDA]/dt=k[PNDA] -12- where k=k'[OH], and k' is 1.25 x l O^M^s"1. k is a psuedo first order rate constant and

consequently the slope of ln([PNDA]/[PNDA]0) vs time where [PNDA]0 is the original

concentration of PNDA.

If the conversion of PNDA is near to completion, the absorption of the product of the

reaction between PNDA and a hydroxyl radical at 440nm cannot simply be ignored. The

overall absorption at 440nm should then be expressed as a combined contribution from

PNDA and PNDA-OH product:

A=ε1lc,+ε2lc2

where ε represents the molar absorptivity of PNDA, c, represents the transient concentration

of PNDA and 1 is the optical pathlength. Similarly, ε2 represents the molar absoφtivity of

the product PNDA-OH, and ct represents its corresponding transient concentration.

Considering the fact that, at any given time, C0=c,+c;. then:

[PND^/fPNDAlo^tCε./ε^-l ]-1 x [(ε,/ε2)(A/A0)-l ]

where A is the absorption of the sample at any given time and A^ is the initial absorption of

the sample.

Example 1

The purpose of the series of experiments conducted as Example 1 is to demonstrate

the relative strength of various metal ions in combination with glycine in catalyzing the

formation of hydroxyl radicals. Accordingly, only simple kinetics need to be used. The slope

of ln(Ag/A) will be used for the calculation of a steady state concentration of hydroxyl radical. -13- The various combinations of components discussed below were tested for their effectiveness

in promoting the formation of hydroxyl radical over a thirty minute period The hydroxyl

radical concentration was then calculated for each combination All percents are by weight

unless otherwise stated

In a small vial, 9 0 +/- 0 1 ml doubly distilled H2O was added to 0 6 -t-/- 0 02 ml 30%

H2O2 The solution's pH was regulated to 8 45 +/- 0 05 using small drops of IN NaOH and

IN H2SO4 In a separate container, 0 08 +/- 0 01 ml of 5mM PNDA was added to the solution followed immediately by addition of 0 36 -r/- 0 02ml of a 5mM metal ion solution of

the metals shown in Table 1 below and 0 1% glycine Each reaction solution's intensity at

440nm was measured for 30 minutes in 5 minute intervals at 25 °C Table 1 below sets forth

the steady-state hydroxyl radical concentration for each trial as determined using the kinetics equation discussed above

- 1 H-

Table 1

Ion Source Slope of lnfAn/A r-OHl (M)

Cu copper acetate 0.03590 2 87x10"12

Ag silver nitrate 0 00062 5 02x10"14

Al aluminum nitrate 0 00071 5 68x10"14

Co cobalt nitrate 0 00339 2 71xl0"13

Cr chromium chloride 0 00619 4 95xl0'13

Fe ferric chloride 0 00201 1 ό lxlO"13

Mg magnesium sulfate 0.00077 6 lόxl O'14

Mn manganous chloride 0 00036 2 88xl0"14

Ni nickelous nitrate 0 00124 9 92xl0"14

Pb lead acetate 0 00630 5 04xl 0"13

Ru ruthenιum(III) chloride hydrate 0 00053 4 24xl0"14

Zn zinc chloride anhydrous 0 00071 5 68xl0"14

Pd palladιum(II) nitrate hydrate 0 00352 2 90xl 0-13

Sn stannous chloride 0 00028 2 24xl0"14

Sm samarium dichloride 0.00135 1 08xl0"13

Cd cadmium chloride 0 00081 6 48x10'14

Fe2' iron(II) sulfate 0 00554 4 43xl0"13

Pt potassium chloroplatinate 0 00101 8 08x10"14

Cu2- cupric chloride 0.03220 2 58xl0"12

Sc scandium acetate 0 00139 1 l lxlO"13

Rh rhodium chloride 0 00339 2 71xl0"13

Figure imgf000016_0001
Rh2- rhodium(II) trifluoroacetate dimer 0 00310 2 48x10"13

Table 1 demonstrates that copper (both valences) is far superior as a radical promoter

than any other metal ion tested Copper produces 10 times the amount of hydroxyl radical

as most species Only lead, iron (Fe2"), and chromium (Cr3*) have any comparable results, and their radical production remains less than five times that of copper Chromium, cobalt,

iron, lead, nickel, palladium, rhodium, samarium, and scandium are less effective in promoting

hydroxyl radical than copper, but are still useful for that purpose -15-

Example 2

The solutions shown in Table 2 below were prepared according to the procedures set

forth in Example 1 Each solution's intensity at 440nm was measured for 30 minutes in 5

minute intervals at 25 ° C Table 2 below sets forth the hydroxyl radical concentration for each

trial as determined using the kinetics equation discussed above

Table 2

Components of Trial Slope of \n(AJA) [OH1 (M)

Cu + 0 1% glycine 0 03590 2 87x10"ι:

0 1% bιs(hexamethylene)tπamιne 0 00264 2 1 1x10 Cu + 0 l% bιs(hexamethylene)tπamιne 0 00552 4 42xl 0"13

0 5% bιs(hexamethylene)tπamιne 0 01057 8 46xl0-13

1 0% bιs(hexamethylene)tπamme 0 01436 1 15xl0"12 Fe + 1 0% bιs(hexamethylene)tπamιne 0 01456 1 16xl0"12 Cr + 1 0% bιs(hexamethylene)tπamιne 0 01385 l l lxlO-12

Example 2 demonstrates that as the concentration of bιs(hexamethvlene)tπamιne

approaches 1 0% by weight, it becomes a comparable hydroxyl radical promoter to a 0 1%

glvcine/Cu2' system Example 2 also demonstrates that the addition of metal ions to a

tπarmne solution sometimes increases the effectiveness of the triamme as a hvdroxyl radical

promoter

Example 3

This example demonstrates that each of the components of the invention (I e , for

example, hydrogen peroxide (H202), glycine (NH2CH2COOH). and copper nitrate (Cu(NO3)2))

have to be present at the same time in order to generate large amounts of hvdroxyl radicals

(OH-) -16- More particularly, different aqueous solutions of the following were prepared:

( 1) hydrogen peroxide only; (2) hydrogen peroxide (2% by weight) and glycine (1% by

weight); (3) hydrogen peroxide (2% by weight) and copper nitrate (100 ppm by weight); (4-

6) hydrogen peroxide (2% by weight), glycine (1% by weight), and copper nitrate (three

concentrations utilized in PPM-parts per million). Then, PNDA was added to the solutions

to trap hydroxyl radicals as soon as they are generated.

Fig. 1 shows the plot of the ratio of PNDA concentration remaining in solution versus

the original PNDA concentration (A/A,,) as a function of time. The data clearly show that

rapid formation of hydroxyl radicals, indicated by the rapid reduction in PNDA concentration

(i.e. A/AQ) in the plot, only occurs when each of the components are present at the same time.

Example 4

This example shows that other amino acids besides glycine, when mixed with

hydrogen peroxide and copper nitrate, will also cause the rapid formation of hydroxyl

radicals.

The experiment in Example 3 was repeated except that glycine in the aqueous

solutions was replaced with various other amino acids as indicated in Fig. 2. In all cases, the

concentrations of hydrogen peroxide, amino acid and copper nitrate were 2% bv weight, 1%

by weight and 100 ppm, respectively. More particularly, Fig. 2 illustrates the various

reduction rates of PNDA concentration in aqueous solutions containing hydrogen peroxide,

copper nitrate, and various amino acids. The reduction rate of PNDA is proportional to the

rate of formation of hydroxyl radicals. -17- Example 5

This example demonstrates that copper nitrate can be replaced by other copper

compounds, such as copper oxide (CuO) and elemental copper (Cu), for the purpose of

forming hydroxyl radicals.

The same experiment as in Example 3 was again repeated, except that the copper

nitrate is replaced by copper oxide powder or elemental copper powder. The concentration

of hydrogen peroxide and glycine were 2% by weight and 1% by weight, respectively. The

concentration of copper oxide and copper powders varied from 3 mg/10 ml to 10 mg/10 ml.

The experiment results, as shown in Fig. 3, demonstrate that fast generation of hydroxyl

radicals, as indicated by rapid reduction in PNDA concentration (A/A„), occurs when

hydrogen peroxide, glycine, and copper oxide or element copper are present at the same time.

Example 6

This example shows that removal rate of tantalum (Ta) is significantly increased when

polishing with the disclosed slurry formulation.

A tantalum disc is polished using a Struers polisher and Suba 500 pad, at a pressure

of 6.3 psi, and a rotation speed of 90 φm. Two CMP slurries were used as follows:

Slurry A contains: (1) 3% by weight alumina abrasive particles with a mean

diameter of 0.35 micrometers and maximum diameter of 2.0 micrometers; and

(2) 5% by weight hydrogen peroxide.

Slurry B contains: (1) 3% by weight alumina abrasive particles with a mean

diameter of 0.35 micrometers and maximum diameter of 2.0 micrometers; (2) -18- 5% by weight hydrogen peroxide; (3) 1% by weight glycine; and (4) 1% by

weight copper nitrate.

The removal rates, determined by weight loss method, are summarized as follows:

Slurry Removal Rate (nanometer/min)

A 32.0

B 68.5

Example 7

This example shows that removal rate of copper (Cu) is significantly increased when polishing with the disclosed slurry formulation. A copper disc is polished using Struers polisher and Suba 500 pad at a pressure of 6.3

psi, and a rotation speed of 90 φm, using aqueous solutions containing (1) 5% by weight hydrogen peroxide; (2) 0.1% by weight glycine; and (3) various concentrations of copper

nitrate ranging from 0 to 0.42 mol/liter (M). Figure 4 illustrates the resulting polish rate as

a function of copper nitrate concentration, which clearly shows that the polish rate of copper

is significantly increased only when copper nitrate, hydrogen peroxide and glycine are present

at the same time in the slurry formulation.

Additional advantages and modifications will readily occur to those skilled in the art.

Therefore, the invention in its broader aspects is not limited to the specific details and

illustrated examples shown and described herein. Accordingly, various modifications may be -19- made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

Claims

-20- What is claimed is:
1. A slurry for chemical-mechanical polishing metal surfaces comprising water;
abrasive particles, and an oxidizing solution comprising a water soluble peroxide.
2. The slurry for chemical-mechanical polishing metal surfaces as in claim 1
wherein said abrasive particles are selected from the group consisting of alumina, silica,
silicon nitride, silicon carbide, ceria, copper oxide, iron oxide, nickel oxide, manganese oxide,
tin oxide, titania, titanium carbide, tungsten oxide, yttria, zirconia, and mixtures thereof.
3. The slurry for chemical-mechanical polishing metal surfaces as in claim 1
wherein said abrasive particles have a mean size ranging from about 0.02╬╝m to about 1.O╬╝m
with a maximum size of less than about lO╬╝m.
4. The slurry for chemical-mechanical polishing metal surfaces as in claim 1
wherein said abrasive particles are present in said slurry in an amount of from about 0.1% to
about 60% by weight.
5. The slurry for chemical-mechanical polishing metal surfaces as in claim 1
wherein said water soluble peroxide has the structure R-O-O-H, where R is hydrogen, an
aliphatic hydrocarbon, or an aromatic hydrocarbon.
6. The slurry for chemical-mechanical polishing metal surfaces as in claim 1
wherein said water soluble peroxide is present in said slurry in an amount of from about 0.1%
to about 30%.
7. The slurry for chemical-mechanical polishing metal surfaces as in claim 1
wherein said pH of said slurry is within the range of from about 2 to about 5.
-21- 8. The slurry for chemical-mechanical polishing metal surfaces as in claim 1
wherein said oxidizing solution further comprises one or more amino acids and one or more
metals or compounds containing metals selected from the group consisting of chromium,
cobalt, copper, iron, lead, nickel, palladium, rhodium, samarium, and scandium.
9. The slurry for chemical-mechanical polishing metal surfaces as in claim 8
wherein said amino acids are one or more selected from the group consisting of arginine,
cysteine, glutamine, glutamic acid, glycine, histidine, phenylalanine, serine. and mixtures
thereof.
10. The slurry for chemical-mechanical polishing metal surfaces as in claim 8
wherein said amino acids are one or more selected from the group consisting of amino
carboxylic acid, amino alkyl carboxylic acid, amino phenyl carboxylic acids, the sodium,
potassium, and ammonium salts thereof, and mixtures thereof.
11 The slurry for chemical-mechanical polishing metal surfaces as in claim 8
wherein said amino acids are present in said slurry in an amount of from about 0.1% to about
10% by weight.
12. The slurry for chemical-mechanical polishing metal surfaces as in claim 8
wherein said metals and/or compounds containing metals are one or more selected from the
group consisting of metal-acetate, metal-bromide, metal-butyrate, metal-chlorate, metal-
chloride, metal-citrate, metal-fluoride, metal-formate, metal-gluconate, metal-glycinate, metal-
hexafluorosilicate, metal-nitrate, metal-oxide powder, metal-hydroxide powder, elemental -22- metal powder, metal-perchlorate, metal-phenolsulfonate, metal-salicylate, metal-selenate,
metal-sulfate, metal-tartrate, and combinations thereof.
13. The slurry for chemical-mechanical polishing metal surfaces as in claim 8
wherein said metals and/or compounds containing metals are present in said slurry in an
amount of from about 0.1% to about 10% by weight.
14. The slurry for chemical-mechanical polishing metal surfaces as in claim 8
wherein said abrasive particles comprise alumina having a mean diameter of about 0.35╬╝m
and a maximum diameter of less than about 2. O╬╝m, said abrasive particles being present in
said slurry in the amount of about 3% by weight, said water soluble peroxide comprises
hydrogen peroxide, said water soluble peroxide being present in said slurry in the amount of
up to about 30%) by weight, said oxidizing solution further comprises an amino acid and a
metal containing compound, said amino acid comprising glycine and being present in said
slurry in an amount of up to about 10% by weight, said metal containing compound
comprising copper nitrate and being present in said slurry in an amount of up to about 10%
by weight.
15. The slurry for chemical-mechanical polishing metal surfaces as in claim 1
wherein said oxidizing solution further comprises organic amine.
16. The slurry for chemical-mechanical polishing metal surfaces as in claim 15
wherein said organic amine is one or more selected from the group consisting of primary
amine (RNH2), secondary amine (R2NH), tertiary amine (R3N), amines containing all or some -23- of these three types of amine moieties, and mixtures thereof, where R is an aliphatic
hydrocarbon or an aromatic hydrocarbon.
17. The slurry for chemical-mechanical polishing metal surfaces as in claim 15
wherein said organic amine is present in said slurry in an amount of from about 0.1% to about
10% by weight.
18. The slurry for chemical-mechanical polishing metal surfaces as in claim 15
wherein said oxidizing solution further comprises one or more metals and/or compounds
containing metals selected from the group consisting of chromium, cobalt, copper, iron, lead,
nickel, palladium, rhodium, samarium, and scandium.
19. The slurry for chemical-mechanical polishing metal surfaces as in claim 15
wherein said abrasive particles comprise alumina having a mean diameter of about 0.35╬╝m
and a maximum diameter of less than about 2. O╬╝m, said abrasive particles being present in
said slurry in the amount of about 3% by weight, said water soluble peroxide comprises
hydrogen peroxide, said water soluble peroxide being present in said slurry in the amount of
up to about 30%) by weight, said oxidizing solution further comprises an organic amine, said
organic amine comprising bis(hexamethylene)triamine and being present in said slurry in an
amount of up to about 10% by weight.
20. A method of polishing a metal surface comprising the steps of:
I. providing a metal surface to be polished;
II. providing a polishing pad; -24-
III. contacting said metal surface to be polished with a polishing slurry,
said polishing slurry comprising water, abrasive particles and an oxidizing solution comprising one or more water soluble peroxides, said oxidizing solution further
comprising either: (a) one or more amino acids and one or more metals and/or
compounds containing metals selected from the group consisting of chromium, cobalt,
copper, iron, lead, nickel, palladium, rhodium, samarium, and scandium; or (b) one
or more organic amines and optionally one or more metals and/or compounds containing metals selected from the group consisting of chromium, cobalt, copper,
iron, lead, nickel, palladium, rhodium, samarium, and scandium; and
IV. mechanically polishing said metal surface to be polished using said polishing pad.
PCT/US1999/007482 1998-04-10 1999-04-05 Slurry for chemical-mechanical polishing metal surfaces WO1999053532A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US5861898A true 1998-04-10 1998-04-10
US09/058,618 1998-04-10
US27745499A true 1999-03-26 1999-03-26
US09/277,454 1999-03-26

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2000544000A JP2002511650A (en) 1998-04-10 1999-04-05 Chemical - mechanical metal surface polishing slurry
EP99916387A EP1086484A4 (en) 1998-04-10 1999-04-05 Slurry for chemical-mechanical polishing metal surfaces
KR1020007011294A KR20010042616A (en) 1998-04-10 1999-04-05 Slurry for chemical-mechanical polishing metal surfaces

Publications (1)

Publication Number Publication Date
WO1999053532A1 true WO1999053532A1 (en) 1999-10-21

Family

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Country Status (4)

Country Link
EP (1) EP1086484A4 (en)
JP (1) JP2002511650A (en)
KR (1) KR20010042616A (en)
WO (1) WO1999053532A1 (en)

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US6604987B1 (en) 2002-06-06 2003-08-12 Cabot Microelectronics Corporation CMP compositions containing silver salts
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US6702954B1 (en) 2000-10-19 2004-03-09 Ferro Corporation Chemical-mechanical polishing slurry and method
US6730592B2 (en) 2001-12-21 2004-05-04 Micron Technology, Inc. Methods for planarization of metal-containing surfaces using halogens and halide salts
US6740589B2 (en) 2000-11-30 2004-05-25 Showa Denko Kabushiki Kaisha Composition for polishing semiconductor wafer, semiconductor circuit wafer, and method for producing the same
US6783432B2 (en) 2001-06-04 2004-08-31 Applied Materials Inc. Additives for pressure sensitive polishing compositions
US6830503B1 (en) 2002-01-11 2004-12-14 Cabot Microelectronics Corporation Catalyst/oxidizer-based CMP system for organic polymer films
US6872329B2 (en) 2000-07-28 2005-03-29 Applied Materials, Inc. Chemical mechanical polishing composition and process
US6884723B2 (en) 2001-12-21 2005-04-26 Micron Technology, Inc. Methods for planarization of group VIII metal-containing surfaces using complexing agents
SG119226A1 (en) * 2003-11-20 2006-02-28 Eternal Chemical Co Ltd Chemical mechanical abrasive slurry and method of using the same
US7014669B2 (en) 2002-02-11 2006-03-21 Dupont Air Products Nanomaterials Llc Catalytic composition for chemical-mechanical polishing, method of using same, and substrate treated with same
WO2006049892A2 (en) * 2004-10-27 2006-05-11 Cabot Microelectronics Corporation Metal ion-containing cmp composition and method for using the same
US7049237B2 (en) 2001-12-21 2006-05-23 Micron Technology, Inc. Methods for planarization of Group VIII metal-containing surfaces using oxidizing gases
US7077880B2 (en) 2004-01-16 2006-07-18 Dupont Air Products Nanomaterials Llc Surface modified colloidal abrasives, including stable bimetallic surface coated silica sols for chemical mechanical planarization
US7121926B2 (en) 2001-12-21 2006-10-17 Micron Technology, Inc. Methods for planarization of group VIII metal-containing surfaces using a fixed abrasive article
US7121943B2 (en) 2001-09-26 2006-10-17 Igt Gaming device with an increasing goal advancement game
KR100735787B1 (en) * 2000-04-04 2007-07-06 캐보트 마이크로일렉트로닉스 코포레이션 Method for Polishing a Memory or Rigid Disk with an Amino Acid-Containing Composition
US7402261B2 (en) 2004-08-18 2008-07-22 Samsung Electronics Co., Ltd. Slurry compositions, methods of preparing slurry compositions, and methods of polishing an object using slurry compositions
US7476620B2 (en) 2005-03-25 2009-01-13 Dupont Air Products Nanomaterials Llc Dihydroxy enol compounds used in chemical mechanical polishing compositions having metal ion oxidizers
US7513920B2 (en) 2002-02-11 2009-04-07 Dupont Air Products Nanomaterials Llc Free radical-forming activator attached to solid and used to enhance CMP formulations
US7691287B2 (en) 2007-01-31 2010-04-06 Dupont Air Products Nanomaterials Llc Method for immobilizing ligands and organometallic compounds on silica surface, and their application in chemical mechanical planarization
CN1854236B (en) 2005-04-21 2011-08-03 安集微电子(上海)有限公司 Polished sizing material and its use
CN102373014A (en) * 2010-08-24 2012-03-14 安集微电子(上海)有限公司 Chemical-mechanical polishing solution

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SG97157A1 (en) * 1999-07-28 2003-07-18 Eternal Chemical Co Ltd Chemical-mechanical abrasive composition and method
US7354530B2 (en) 1999-08-13 2008-04-08 Shumin Wang Chemical mechanical polishing systems and methods for their use
US6840971B2 (en) 1999-08-13 2005-01-11 Cabot Microelectronics Corporation Chemical mechanical polishing systems and methods for their use
WO2001012739A1 (en) * 1999-08-13 2001-02-22 Cabot Microelectronics Corporation Chemical mechanical polishing systems and methods for their use
US6520840B1 (en) 1999-10-27 2003-02-18 Applied Materials, Inc. CMP slurry for planarizing metals
SG83822A1 (en) * 1999-10-27 2001-10-16 Applied Materials Inc Cmp slurry for planarizing metals
US6435944B1 (en) 1999-10-27 2002-08-20 Applied Materials, Inc. CMP slurry for planarizing metals
US6544892B2 (en) 1999-12-08 2003-04-08 Eastman Kodak Company Slurry for chemical mechanical polishing silicon dioxide
EP1106663A1 (en) * 1999-12-08 2001-06-13 Clarkson University Slurry for chemical mechanical polishing silicon dioxide
US6468910B1 (en) 1999-12-08 2002-10-22 Ramanathan Srinivasan Slurry for chemical mechanical polishing silicon dioxide
US7091164B2 (en) 1999-12-08 2006-08-15 Eastman Kodak Company Slurry for chemical mechanical polishing silicon dioxide
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US6627107B2 (en) 1999-12-08 2003-09-30 Eastman Kodak Company Slurry for chemical mechanical polishing silicon dioxide
US7087188B2 (en) 1999-12-28 2006-08-08 Intel Corporation Abrasives for chemical mechanical polishing
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US6451697B1 (en) 2000-04-06 2002-09-17 Applied Materials, Inc. Method for abrasive-free metal CMP in passivation domain
WO2002004573A3 (en) * 2000-07-08 2003-08-21 Arch Spec Chem Inc Ready-to-use stable chemical-mechanical polishing slurries
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US6740589B2 (en) 2000-11-30 2004-05-25 Showa Denko Kabushiki Kaisha Composition for polishing semiconductor wafer, semiconductor circuit wafer, and method for producing the same
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US6592742B2 (en) 2001-07-13 2003-07-15 Applied Materials Inc. Electrochemically assisted chemical polish
US7121943B2 (en) 2001-09-26 2006-10-17 Igt Gaming device with an increasing goal advancement game
US7429338B2 (en) 2001-10-15 2008-09-30 Dupont Air Products Nanomaterials Llc Surface modified colloidal abrasives, including stable bimetallic surface coated silica sols for chemical mechanical planarization
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EP1302522A3 (en) * 2001-10-15 2009-06-17 DuPont Air Products NanoMaterials, LLC. Gel-free colloidal abrasive and polishing compositions and methods of using them
US6861353B2 (en) 2001-12-21 2005-03-01 Micron Technology, Inc. Methods for planarization of metal-containing surfaces using halogens and halide salts
US7327034B2 (en) 2001-12-21 2008-02-05 Micron Technology, Inc. Compositions for planarization of metal-containing surfaces using halogens and halide salts
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US6884723B2 (en) 2001-12-21 2005-04-26 Micron Technology, Inc. Methods for planarization of group VIII metal-containing surfaces using complexing agents
WO2003055958A1 (en) * 2001-12-21 2003-07-10 Dynea Canada, Ltd. Abrasive composition containing organic particles for chemical mechanical planarization
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Also Published As

Publication number Publication date
EP1086484A1 (en) 2001-03-28
JP2002511650A (en) 2002-04-16
EP1086484A4 (en) 2003-08-06
KR20010042616A (en) 2001-05-25

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