TWI583755B - Aqueous polishing composition and process for chemically mechanically polishing substrates containing silicon oxide dielectric and polysilicon films - Google Patents

Description

Aqueous polishing composition and method for chemical mechanical polishing of substrate containing cerium oxide dielectric and polycrystalline germanium film

The present invention relates to a novel aqueous polishing composition which is particularly suitable for polishing a semiconductor substrate comprising a yttria dielectric and a polycrystalline germanium film, optionally containing a tantalum nitride film.

Furthermore, the present invention relates to a novel method of polishing substrates for the manufacture of electrical, mechanical and optical devices comprising yttria and a polycrystalline germanium film, optionally containing a tantalum nitride film.

Citation

The documents cited in the present application are hereby incorporated by reference in their entirety.

Chemical mechanical planarization or polishing (CMP) is the primary method for achieving local and complete flatness of integrated circuit (IC) devices. This technique typically applies a CMP composition or slurry containing abrasives and other additives as active chemicals between the surface of the rotating substrate and the polishing pad under external load. Thus, CMP methods incorporate physical methods such as milling and chemical methods such as oxidation or chelation. It is not desirable that the removal or polishing of the substrate material contains only physical effects or only chemical effects, but rather a synergistic combination of the two in order to achieve rapid uniform removal.

In this way, the substrate material is removed until the desired flatness is achieved or the barrier underlayer or stopping film is exposed. A flat, defect-free surface is ultimately obtained which allows for the fabrication of suitable multilayer IC devices using subsequent photolithography, patterning, etching, and thin film processes.

Shallow trench isolation (STI) is a specific CMP application that typically requires selective removal of germanium dioxide to expose tantalum nitride on the patterned wafer substrate. In this case, the etched trench is overfilled with a dielectric material such as cerium oxide, which is polished using a tantalum nitride barrier film as a stop film. The CMP method ends with the removal of germanium dioxide from the barrier film while minimizing the removal of exposed tantalum nitride and trenched germanium dioxide.

This requires the CMP slurry to achieve a higher relative ratio of the cerium oxide material removal rate MRR to the cerium nitride removal rate MRR, which is also referred to in the art as the selectivity of the oxide relative to the nitride.

Recently, polycrystalline germanium films have also been used as barrier films or electrode materials (see U.S. Patent No. 6,626,968 B2). Therefore, it has become highly desirable to use a CMP slurry and method that allows a substrate containing a ruthenium oxide dielectric and a polycrystalline germanium film to be completely planarized. This requires the CMP slurry to exhibit a higher selectivity for the oxide relative to the polycrystalline germanium.

There is a greater need for useful CMP slurries and methods that allow for the complete planarization of substrates containing additional tantalum nitride films.

In this case, the selectivity of the oxide relative to the nitride should not be too high to avoid bulging and other on the fully planarized heterogeneous patterned surface containing the regions of cerium oxide, tantalum nitride and polycrystalline germanium. Damage and defects. However, the selectivity of tantalum nitride relative to polycrystalline germanium should also be high.

In STI applications, ruthenium oxide-based CMP slurry has been considerably large due to its ability to achieve a relatively high selectivity of oxides relative to nitrides due to the higher chemical affinity of yttrium oxide and cerium oxide. Concerned, it is also known in the art as the chemical tooth action of cerium oxide.

Nonetheless, the selectivity of the cerium oxide-based CMP slurry relative to the polysilicon must be modified by "tailoring" the selective additive.

A number of attempts have been made to adapt the selectivity of cerium oxide-based CMP slurries.

Thus, Jae-Don Lee et al., Journal of the Electrochemical Society, 149(8), G477-G481, 2002, disclose nonionic surfactants having different hydrophilic-lipophilic balance (HLB) values (such as polyethylene oxide). The effect of the alkane, ethylene oxide-propylene oxide copolymer and ethylene oxide-propylene oxide-ethylene oxide triblock copolymer on the selectivity of the oxide relative to polycrystalline germanium during CMP. However, fumed ceria is used as an abrasive and does not address the selectivity of the oxide relative to the nitride.

US Patent Application No. US 2002/0034875 A1 and U.S. Patent No. 6,626,968 B2 disclose a cerium oxide-based CMP slurry containing a surfactant, a pH adjuster (such as potassium hydroxide, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid). And polymers containing hydrophilic functional groups and lipophilic functional groups (such as polyvinyl methyl ether (PVME), polyethylene glycol (PEG), polyoxyethylene 23 lauryl ether (POLE), polypropionic acid (PPA), polyacrylic acid (PM) and polyether glycol bis ether (PEGBE). The CMP slurry based on cerium oxide enhances the selectivity of the oxide relative to polycrystalline germanium.

US Pat. No. 6,645,051 B2 discloses a cerium oxide-based CMP slurry for polishing a hard disk substrate of a memory, which contains at least one selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether and polyoxyethylene polyoxypropylene copolymer. A group of nonionic surfactants.

US Patent Application No. US 2003/0228762 A1 discloses a CMP slurry for polishing a substrate containing a low-k dielectric film, the CMP slurry containing:

- an abrasive selected from the group consisting of alumina, ceria, titania, yttria, zirconia, yttria, magnesia and co-formed products thereof;

An amphiphilic nonionic surfactant having at least one lipophilic head group and at least one hydrophilic tail group.

Suitable head groups according to US 2003/0228762 A1 include polyoxyalkylenes, tetra-C _1-4 -alkyl decynes, saturated or partially unsaturated C _6-30 alkyl groups, polyoxypropylene groups, C _6-12 Alkylphenyl or alkylcyclohexyl and polyvinyl. Suitable tail groups include polyoxyethylene groups. Thus, the amphiphilic nonionic surfactant may be selected from the group consisting of polyoxyethylene alkyl ethers or esters.

U.S. Patent Application No. US 2006/0124594 A1 discloses a cerium oxide-based CMP slurry having a viscosity of at least 1.5 cP and comprising a viscosity increasing agent comprising a nonionic polymer such as polyethylene glycol (PEG). A cerium oxide-based CMP slurry is believed to have a higher selectivity for oxide relative to nitride and results in a lower-wafer non-uniformity WIWNU.

US Patent Application No. US 2006/0216935 A1 discloses a cerium oxide-based CMP slurry comprising protein, lysine and/or arginine and pyrrolidone compounds, such as polyvinylpyrrolidone (PVP), N -octyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-butyl-2 - pyrrolidone, N-hexyl-2-pyrrolidone, N-mercapto-2-pyrrolidone, N-octadecyl-2-pyrrolidone and N-hexadecyl-2-pyrrolidine ketone. Further, the cerium oxide-based CMP slurry may contain a dispersing agent such as polyacrylic acid, a diol, and a polyglycol. Specific examples use valine, polyvinylpyrrolidone or N-octyl-2-pyrrolidone, PPO/PEO block copolymers and glutaraldehyde. It is believed that the cerium oxide-based CMP slurry does not aggressively remove the trenched cerium oxide, allowing for extended polishing beyond the endpoint without substantially increasing the minimum step height.

U.S. Patent Application US 2007/0077865 A1 discloses CMP slurries of cerium oxide as a main, preferably containing freely available BASF Pluronic ^TM family of polyethylene oxide / polypropylene oxide copolymer. In addition, the cerium oxide-based CMP slurry may contain an amino alcohol such as 2-dimethylamino-2-methyl-1-propanol (DMAMP), 2-amino-2-ethyl-1-propene Alcohol (AMP), 2-(2-aminoethylamino)ethanol, 2-(isopropylamino)ethanol, 2-(methylamino)ethanol, 2-(diethylamino)ethanol, 2-(2) -dimethylamino)ethoxy)ethanol, 1,1'-[[3-(dimethylamino)propyl]imino]-bis-2-propanol, 2-(2-butylamino) Ethyl alcohol, 2-(t-butylamino)ethanol, 2-(diisopropylamino)ethanol, and N-(3-aminopropyl)morpholine. The cerium oxide-based CMP slurry may further contain a fourth ammonium compound (such as tetramethylammonium hydroxide), a film former (such as an alkylamine, an alkanolamine, a hydroxylamine, a phosphate, a sodium lauryl sulfate, a fatty acid, Polyacrylates, polymethacrylates, polyvinyl phosphonates, polymalates, polystyrene sulfonates, polysulfates, benzotriazoles, triazoles, and benzimidazoles) and complexing agents (such as Acetylacetone, acetate, glycolate, lactate, gluconate, gallic acid, oxalate, phthalate, citrate, succinate, tartrate, apple Acid salt, ethylenediaminetetraacetic acid, ethylene glycol, catechol, pyrogallol, citric acid, cerium salt and phosphonic acid). It is believed that cerium oxide-based CMP slurry provides good selectivity for cerium oxide and/or cerium nitride relative to polycrystalline germanium.

US Patent Application No. US 2007/0175104 A1 discloses a cerium oxide-based CMP slurry comprising a polycrystalline cerium polishing inhibitor selected from N-monosubstituted or N substituted with any member selected from the group consisting of: , water-soluble polymer of N-disubstituted skeleton: acrylamide, methacrylamide and its α-substituted derivative; polyethylene glycol; polyvinylpyrrolidone; alkoxylated linear aliphatic alcohol and An ethylene oxide adduct based on an acetylene diol. The cerium oxide-based CMP slurry may contain other water-soluble polymers such as polysaccharides such as alginic acid, pectic acid ester, carboxymethyl cellulose, agar, curdlan and pullulan; Polycarboxylic acids such as polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polyimidic acid, polymaleic acid, polyitaconic acid ), poly-fumaric acid, poly(p-styrenecarboxylic acid), polyacrylic acid, polypropylene decylamine, amine-based polyacrylamide, polyglyoxylic acid and salts thereof; and vinyl polymers such as polyvinyl alcohol And polyacrylaldehyde. The CMP slurry based on cerium oxide is considered to be more selective in cerium oxide than in polycrystalline cerium.

US Patent Application No. US 2008/0085602 A1 and US 2008/0124913 A1 disclose a cerium oxide-based CMP slurry containing 0.001% by weight to 0.1% by weight selected from ethylene oxide-propylene oxide-epoxy B. The alkane triblock copolymer and the nonionic surfactant of polyacrylic acid act as a dispersing agent. A cerium oxide-based slurry is considered to be more selective for cerium oxide and cerium nitride than polycrystalline cerium.

U.S. Patent Application No. US 2008/0281486 discloses a cerium oxide-based CMP slurry having a nonionic surfactant having a hydrophilic-lipophilic balance (HLB) value in the range of 12 to 17. The nonionic surfactant is selected from the group consisting of polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxygen Ethylene isooctyl phenyl ether and mixtures thereof. The CMP slurry is believed to have a higher selectivity for cerium oxide than for polycrystalline cerium.

The manufacture of electrical devices, in particular semiconductor integrated circuits (ICs), requires high precision methods involving particularly high selectivity CMP.

Although the prior art ruthenium oxide-based CMP slurry can have satisfactory oxide selectivity relative to polysilicon and can have, for example, in-wafer non-uniformity (WIWNU) and inter-wafer non-uniformity (WTWNU). The polished wafers with good full and partial flatness are exemplified, but the ever-decreasing size of the IC architecture (specifically, LSI (large-scale integrated) or VLSI (very large integrated IC)) needs to be continuously improved with yttrium oxide. The CMP slurry is designed to meet the increasing technical and economic requirements of integrated circuit device manufacturers.

However, this urgent need to continuously improve the prior art bismuth oxide-based CMP slurry is not only applicable to the field of integrated circuit devices, but also to the polishing and planarization effects in the manufacture of other electrical devices (such as liquid crystal panels, organic electroluminescent panels, Printed circuit boards, micromachines, DNA wafers, micro plants, photovoltaic cells and magnetic heads) as well as high-precision mechanical devices and optical devices (specifically, optical glass (such as light masks, lenses and cymbals), inorganic Conductive film (such as indium tin oxide (ITO)), optical integrated circuit, optical conversion element, optical waveguide, optical single crystal (such as optical fiber and end face of scintillator), solid laser single crystal, blue laser LED The field of sapphire substrates, semiconductor single crystals, and glass substrates for magnetic disks also needs to be improved. The manufacture of such electrical, mechanical, and optical devices also requires high precision CMP process steps.

Japanese Patent Application No. 2001-240850 A discloses a CMP slurry containing alumina, zirconia or tantalum carbide as an abrasive, an alkylene oxide-ethylene oxide block or a random copolymer as a dispersing agent and sodium phosphate or Sodium polyphosphate is used as an "anti-rust".

The alkylene oxide-ethylene oxide copolymer has the general formula:

Z-[{(AO) _n /(EO) _m }R ¹ ] _p ,

Wherein the index and the variable have the following meanings: p is an integer from 1 to 6; n is an integer having an average value of from 10 to 200; m is an integer having an average value of from 1 to 300; E is an exoethyl group; 1,2-butylene, 2,3-butylene, 1,3-butylene or 1,4-butylene; Z is a residue of a polyol; and R ¹ is a hydrogen atom, having 1 to An alkyl group of 18 carbon atoms or a fluorenyl group having 2 to 24 carbon atoms.

CMP slurry is used to polish tantalum wafers, glass, aluminum, ceramics, synthetic cerium oxide, quartz and sapphire. It is not disclosed that the selectivity to cerium oxide and/or cerium nitride is superior to that of polycrystalline germanium.

A CMP slurry based on cerium oxide, which contains at least one such as, for example, Japanese Patent Application No. 2001-240850 A, U.S. Patent Application Serial No. 61/380,719, filed on Sep. US 2007/0077865 A1, US 2006/0124594 A1 and US 2008/0124913 A1, US Patent US 2006/0213780 A1 and BASF Corporation's company brochure "Piuronic ^TM & Tetronic ^TM Block Copolymer Surfactants, 1996" are selected from A water-soluble polymer of a group consisting of linear and branched alkylene oxide homopolymers and copolymers. Further, the cerium oxide-based CMP slurry contains at least one anionic phosphate dispersant. The cerium oxide-based CMP slurry exhibits excellent selectivity of the oxide relative to polycrystalline germanium and higher selectivity of the nitride relative to polycrystalline germanium and advantageous selectivity of the oxide relative to the nitride.

The prior European Patent Application No. 10186886.7, filed on October 7, 2010, describes a cerium oxide-based CMP slurry containing at least one amphiphilic agent selected from the group consisting of water-soluble or water-dispersible surfactants. a nonionic surfactant, the amphiphilic nonionic surfactant having at least one lipophilic group (b1) selected from the group consisting of branched alkyl groups of 5 to 20 carbon atoms; and at least one selected from a hydrophilic group (b2) comprising a group consisting of an ethylene oxide monomer unit (b21) and a polyalkylene oxide group of at least one type of substituted alkylene oxide monomer unit (b22), wherein the substituent group Selected from the group consisting of alkyl, cycloalkyl or aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl; The oxyalkyl group contains monomer units (b21) and (b22) which are randomly, alternately, gradiently and/or block-likely distributed. The CMP slurry exhibits higher selectivity for cerium oxide, cerium nitride and copper than ultra low k dielectric materials.

The object of the invention

Accordingly, it is an object of the present invention to provide a novel aqueous polishing composition (specifically, a novel chemical mechanical polishing (CMP) composition that no longer exhibits the disadvantages and drawbacks of prior art polishing compositions, particularly yttrium oxide based Novel CMP slurry).

In particular, novel aqueous polishing compositions (specifically, novel chemical mechanical polishing (CMP) compositions, especially novel CMP slurries based on cerium oxide) should exhibit significantly improved selectivity for oxides relative to polycrystalline germanium and A polished wafer having excellent full and partial flatness as exemplified by in-wafer non-uniformity (WIWNU) and inter-wafer non-uniformity (WTWNU) is produced. Therefore, it should be excellently applied to the manufacture of an IC architecture (specifically, an LSI (large integrated body) or a VLSI (very large integrated IC) having a structure having a size of 50 nm or less.

In particular, the novel CMP slurry based on cerium oxide should also exhibit, in particular, a favorable selectivity of the nitride relative to the polysilicon and a favorable selectivity of the oxide to the nitride.

In addition, the novel aqueous polishing composition (specifically, the novel chemical mechanical polishing (CMP) composition and especially the novel CMP slurry based on cerium oxide) should not be particularly suitable for use in the field of integrated circuit devices, but should also be most effective. And is advantageously suitable for the manufacture of other electrical devices (such as liquid crystal panels, organic electroluminescent panels, printed circuit boards, micromachines, DNA wafers, microdevices and magnetic heads) as well as high-precision mechanical devices and optical devices (specifically, optical glass ( Such as light masks, lenses and ruthenium, inorganic conductive films (such as indium tin oxide (ITO)), optical integrated circuits, optical conversion elements, optical waveguides, optical single crystals (such as optical fibers and end faces of scintillators), The field of solid laser single crystal, blue laser LED sapphire substrate, semiconductor single crystal and magnetic glass substrate.

Another object of the present invention is to provide a novel method for polishing substrates for mechanical, electrical and optical devices comprising a cerium oxide dielectric and a polycrystalline germanium film, optionally containing a tantalum nitride film.

Thus, a novel aqueous polishing composition has been discovered which comprises:

(A) at least one type of abrasive comprising or consisting of cerium oxide;

(B) at least one amphiphilic nonionic surfactant selected from the group consisting of water-soluble and water-dispersible, linear and branched polyalkylene oxide block copolymers of the formula I:

R[(B1) _m /(B2) _n Y] _p (I),

Wherein the index and the variable have the following meanings: m is an integer greater than or equal to 1; n is an integer greater than or equal to 1; p is an integer greater than or equal to 1; R is a hydrogen atom or a straight line having 5 to 20 carbon atoms a monovalent or polyvalent organic residue other than a chain and a branched alkyl group; (B1) is a block consisting essentially of ethylene oxide monomer units; (B2) is an epoxy substantially substituted by at least one type a block composed of alkane monomer units, wherein the substituent is selected from the group consisting of at least two methyl groups, an alkyl group having at least two carbon atoms, and a cycloalkyl group, an aryl group, an alkyl-cycloalkyl group, An alkyl-aryl group, a cycloalkyl-aryl group, and an alkyl-cycloalkyl-aryl group; and Y is a hydrogen atom or a monovalent organic residue other than a linear or branched alkyl group having 5 to 20 carbon atoms The limitation is that when (B) contains more than one block (B1) or (B2), two blocks of the same type are separated from each other by another type of block.

Hereinafter, the novel aqueous polishing composition is referred to as "the composition of the present invention".

In addition, novel methods for polishing substrates for mechanical, electrical, and optical devices have been discovered by contacting the substrate material with the compositions of the present invention at least once and polishing the substrate material until the desired flatness is achieved.

Hereinafter, a novel method for polishing a substrate material for mechanical, electrical, and optical devices is referred to as "the method of the present invention."

Advantages of the invention

In view of the prior art, it has been surprising and unanticipated by those skilled in the art that the objects of the present invention can be solved by the compositions of the present invention and the methods of the present invention.

It is especially surprising that the compositions of the present invention exhibit significantly improved selectivity for oxides relative to polysilicon and result in excellent characterizations such as in-wafer non-uniformity (WIWNU) and inter-wafer non-uniformity (WTWNU). Fully and partially flat polished wafers. Therefore, it is excellently suited for manufacturing an IC structure, specifically an LSI (large integrated body) or a VLSI (very large integrated form) IC having a structure of 50 nm or less.

The compositions of the invention also show, inter alia, the selectivity of the advantageous nitride relative to the polysilicon and the selectivity of the advantageous oxide to the nitride.

In addition, the compositions of the present invention are stable during long-term transport and storage, and their stability significantly improves logistics and program management.

In addition, the composition of the present invention is not only particularly suitable for use in the field of integrated circuit devices, but also most effectively and advantageously applied to the manufacture of other electrical devices (such as liquid crystal panels, organic electroluminescent panels, printed circuit boards, micromachines, DNA wafers, Microdevices and magnetic heads) as well as high-precision mechanical devices and optical devices (specifically, optical glass (such as light masks, lenses and cymbals), inorganic conductive films (such as indium tin oxide (ITO)), optical integrated circuits, optics The field of conversion elements, optical waveguides, optical single crystals (such as end faces of optical fibers and scintillators), solid laser single crystals, sapphire substrates of blue laser LEDs, glass substrates of semiconductor single crystals and magnetic disks.

Thus, the compositions of the invention are most particularly suitable for use in the process of the invention. The method of the present invention can be most advantageously used for polishing (specifically, chemical mechanical polishing) substrates for power supply devices such as liquid crystal panels, organic electroluminescent panels, printed circuit boards, micromachines, DNA wafers, micro devices, and magnetic heads. Materials and high-precision mechanical devices and optical devices (specifically, optical glass (such as light masks, lenses and enamels), inorganic conductive films (such as indium tin oxide (ITO)), optical integrated circuits, optical conversion elements, A substrate material for an optical waveguide, an optical single crystal (such as an end face of an optical fiber and a scintillator), a solid laser single crystal, a blue laser LED sapphire substrate, a semiconductor single crystal, and a magnetic glass substrate.

However, the method of the present invention is most particularly well suited for polishing semiconductor wafers containing a yttria dielectric and a polysilicon film and optionally a tantalum nitride film. The method of the present invention produces polished wafers having excellent full and partial flatness and balance as exemplified by in-wafer non-uniformity (WIWNU) and inter-wafer non-uniformity (WTWNU) without bulging, concave or hot spots . Therefore, it is excellently suited for the manufacture of an IC architecture (specifically, an LSI (large integrated body) or a VLSI (very large integrated IC) having a structure having a size of 50 nm or less.

The composition of the present invention is an aqueous composition. This means that it contains water (specifically, ultrapure water) as the main solvent and dispersant. Nonetheless, the compositions of the present invention may contain at least one water-miscible organic solvent, however, only a small amount that does not alter the aqueous properties of the compositions of the present invention.

The composition of the present invention preferably contains water in an amount of from 60% by weight to 99.95% by weight, more preferably from 70% by weight to 99.9% by weight, even more preferably from 80% by weight to 99.9% by weight, and most preferably from 90% by weight to 99.9% by weight. The weight percentages are based on the total weight of the composition of the invention.

"Water-soluble" means that the relevant component or component of the composition of the invention is soluble in the aqueous phase at the molecular level.

By "water-dispersible" is meant that the relevant components or ingredients of the compositions of the present invention are dispersible in the aqueous phase and form a stable emulsion or suspension.

The first essential component of the composition of the present invention is at least one (preferably one) type of abrasive (A) comprising or consisting of cerium oxide.

The average particle size of the abrasive (A) can vary widely and thus can be most advantageously adapted to the particular needs of the established compositions and methods of the present invention. The average particle diameter as measured by dynamic laser light scattering is preferably from 1 nm to 2000 nm, preferably from 1 nm to 1000 nm, more preferably from 1 nm to 750 nm, most preferably from 1 nm to 500 nm, especially from 10 nm to 250. In the range of nm (for example, 80 nm to 200 nm).

The particle size distribution of the abrasive (A) may be monomodal, bimodal or multimodal. The particle size distribution is preferably a single peak in order to have an easily reproducible characteristic profile of the abrasive (A) and conditions which are easily reproducible during the process of the invention.

Further, the particle size distribution of the abrasive (A) may be narrower or wider. The particle size distribution is preferably narrow and has only a small amount of smaller particles and larger particles in order to have an easily reproducible characteristic profile of the abrasive (A) and conditions which are easily reproducible during the process of the invention.

The abrasive (A) can have various shapes. Thus, it can have one or substantially one type of shape. However, it is also possible that the abrasive (A) has a different shape. In particular, two types of different shaped abrasives (A) may be present in the intended compositions of the present invention. Regarding its own shape, it may be a cube, a cube with chamfered edges, an octahedron, an icosahedron, a nodule, and a sphere with or without protrusions or indentations. The shape is preferably a sphere having no protrusions or indentations or only a few protrusions or indentations. This shape is generally preferred because it generally increases the resistance to the mechanical forces experienced by the abrasive (A) during the CMP process.

The abrasive containing cerium oxide (A) may contain a small amount of other rare earth metal oxides.

The abrasive (A) composed of yttria may have a hexagonal, cubic or face-centered lattice.

The cerium oxide-containing abrasive (A) is preferably a composite particle (A) comprising at least one other abrasive material different from cerium oxide (specifically, alumina, ceria, titania, zirconia, zinc oxide, and the like) a mixture) or a core composed of at least one other abrasive material than cerium oxide.

Such composite particles (A) are known, for example, from WO 2005/035688 A1, US 6,110,396, US 6,238,469 B1, US 6,645,265 B1, KS Choi et al., Mat. Res. Soc. Symp. Proa, Vol. 671, 200.1 Materials Research Society, M5.8.1 to M5.8.10, S.-H. Lee et al., J. Mater. Res., Vol. 17, No. 10 (2002), pp. 2744 to 2749, A. Jindal Et al, Journal of the Electrochemical Society, 150 (5), G314-G318 (2003), Z. Lu, Journal of Materials Research, Vol. 18, No. 10, October 2003, Materials Research Society or S. Hedge Et al, Electrochemical and Solid-State Letters, 7 (12), G316-G318 (2004).

The composite particles (A) are preferably raspberry-type coated particles comprising a core having a core size of 20 nm to 100 nm selected from the group consisting of alumina, ceria, titania, zirconia, zinc oxide, and mixtures thereof. Wherein the core is coated with cerium oxide particles having a particle size below 10 nm.

The amount of abrasive (A) used in the compositions of the present invention can vary widely and thus can be most advantageously adapted to the particular needs of the established compositions and methods of the present invention. The composition of the present invention preferably contains 0.005 wt% to 10 wt%, more preferably 0.01 wt% to 8 wt%, and most preferably 0.01 wt% to 6 wt% of the abrasive (A) (by weight of the total weight of the composition of the present invention) meter).

The second essential component of the composition of the present invention is at least one (preferably one) amphiphilic nonionic surfactant (B) selected from the group consisting of water solubility and water dispersibility of Formula I. (preferably water soluble) linear and branched (preferably linear) polyalkylene oxide block copolymers:

R[(B1) _m /(B2) _n Y] _p .

In the formula I, the indices m and n are each independently an integer equal to or greater than 1, preferably an integer of from 1 to 10, more preferably from 1 to 5 and most preferably from 1 to 3.

The index p of the formula I is an integer equal to or greater than 1, preferably an integer of from 1 to 100, more preferably from 1 to 50, even more preferably from 1 to 25 and most preferably from 1 to 10.

The variable R represents a hydrogen atom or a monovalent or polyvalent organic residue other than a linear and branched alkyl group having 5 to 20 carbon atoms.

The monovalent or polyvalent organic residue R is preferably selected from the group consisting of an alkyl group having 1 to 4 and 21 to 30 carbon atoms and a cycloalkyl group, an aryl group, an alkyl-cycloalkyl group, an alkyl group. - aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl.

More preferably, the monovalent or polyvalent organic residue R is derived from a monohydroxy group and a polyhydroxy compound R'.

Examples of suitable monohydroxy compounds R' are methanol, ethanol, propanol, isopropanol, n-butanol, second butanol and third butanol, derived from linear and branched chains of hexadecane, twenty-two Alkanes, tricosane, tetracosane, dipentadecane, hexadecane, heptacosane, octacosane, octadecane and triacontane monool, cyclohexanol, benzyl alcohol And phenol and a phenol having an alkyl group of 4 to 16 carbon atoms at the 4-position.

Examples of suitable dihydroxy compounds R' are ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, ethyl propylene glycol, and Ethyl propylene glycol, ethyl dipropylene glycol, 1,2-dihydroxycyclohexane, 1,3-dihydroxycyclohexane and 1,4-dihydroxycyclohexane, and benzene and bisphenol A and bisphenol F .

Examples of suitable trihydroxy compounds R' are glycerol, 1,2,3-trihydroxy-n-butane, trimethylolpropane, 1,2,3-trihydroxycyclohexane, 1,2,4-tri Hydroxycyclohexane and 1,3,5-trihydroxycyclohexane and benzene.

Examples of suitable polyhydroxy compounds R' are pentaerythritol, 1,2,3,4-tetrahydroxycyclohexane, 1,2,3,5-tetrahydroxycyclohexane and 1,2,4,5-tetrahydroxyl Cyclohexane and benzene, polyvinyl alcohol, poly(hydroxystyrene), alditol, cyclitol, dimers and oligomers of carbohydrates and glycerol, trimethylolpropane, Pentaerythritol, alditol and cyclic sugar alcohol.

Examples of suitable alditol R' are butanol, pentitol, hexitol, heptitol and octitol, in particular erythritol, threitol, arabitol, ribitol, Xylitol, galactitol, mannitol, sorbitol, allitol, altitol, and iditol.

Examples of suitable dimers R' are dimers of glycerol, trimethylolpropane, erythritol, threitol and pentaerythritol, maltitol, isomaltose and lactitol, in particular triglycerol, Tetraglycerin, pentaglycerin, hexapolyglycerol, heptaglycerol, octaglycerol, nonapolyglycerol, decaglycerin, eleven polyglycerol and dodecaglycerin, trimeric trimethylolpropane, tetrapolytrihydroxy Methylpropane, pentapolytrimethylolpropane, hexatrimethylolpropane, heptatrimethylolpropane, octapolytrimethylolpropane, nonapolytrimethylolpropane, decapolytrimethylol Propane, eleven polymethylolpropane and dodecapolytrimethylolpropane, trimeric erythritol, tetrameric erythritol, pentaerythritol, hexaerythritol, heptameric Alginitol, octaerythritol, octameric erythritol, decamer erythritol, eleven polyerythritol, dodecamar erythritol, trimeric threitol, tetramerization Threitol, pentaerythritol, hexacositol, heptacositol, octacositol, octadecitol, decameritol, eleventhitol and twelfth Su Alcohol and tripentaerythritol, pentaerythritol tetramers, pentamers pentaerythritol, pentaerythritol hexamers, seven-pentaerythritol, eight-pentaerythritol, nine-pentaerythritol, ten-pentaerythritol, eleven-pentaerythritol and 12-pentaerythritol.

Examples of suitable cyclic sugar alcohols R' are 1,2,3,4,5-pentahydroxycyclohexane and inositol, specifically muscle myositol, scyllo-inositol, musculositol, and palm muscle. Alcohol, neoinositol, isoinositol, epicretin and cisinositol.

Examples of suitable carbohydrates R' are monosaccharides, disaccharides, oligosaccharides, polysaccharides, deoxy sugars and amino sugars, in particular monosaccharides.

Examples of suitable monosaccharides R' are allose, altrose, glucose, mannose, idose, galactose and talose.

Residue R other than a hydrogen atom may carry at least one inert substituent. "Inert" means that the substituent does not initiate the polymerization of ethylene oxide and alkylene oxide and the decomposing and/or precipitation of components such as the compositions of the present invention after long-term storage and during the process of the present invention. Examples of suitable inert substituents are halogen atoms (specifically fluorine and chlorine atoms), nitro groups, nitrile groups and alkyl groups, cycloalkyl and aryl groups, carboxyl groups bonded to the residue R via an oxygen or sulfur atom, Thioxy, sulfonate, carboxylate, sulfonate and phosphonate or urethane groups. The inert substituent is used in an amount that does not adversely affect the hydrophilic-lipophilic balance (HLB) value of the surfactant (B). Substituents preferably do not carry such inert substituents.

The residue R is preferably a hydrogen atom.

The two pharmaceutically active nonionic surfactants (B) of the formula I contain at least one block (B1) and at least one block (B2), with the proviso that when (B) contains more than one block (B1) and In the case of block (B2), two blocks of the same type are separated from each other by other types of blocks.

Thus, the amphiphilic nonionic surfactant (B) may contain various general block-like structures such as:

- B1-B2;

- B1-B2-B1;

- B2-B1-B2;

- B1-B2-B1-B2;

- B1-B2-B1-B2-B1;

- B2-B1-B2-B1-B2;

- B1-B2-B1-B2-B1-B2;

- B1-B2-B1-B2-B1-B2-B1 and

- B2-B1-B2-B1-B2-B1-B2.

If two or more blocks (B1) are present, they may have the same or substantially the same composition, molecular weight and HLB value or they may differ from one another. The same applies to the block (B2).

The amphiphilic nonionic surfactant (B) preferably contains a general block-like structure B1-B2, B1-B2-B1 or B2-B1-B2.

The block (B1) consists essentially of ethylene oxide monomer units. "Consisting essentially of" means that the block (B1) consists entirely of ethylene oxide monomer units or contains small amounts of propylene oxide monomer units and/or alkylene oxide monomer units (also That is, the monomer unit of the block (B2). "minor amount" means that the concentration of the monomer unit other than the ethylene oxide monomer unit is as low as not adversely affecting, but is advantageous for improving the block (B1) produced by the ethylene oxide monomer unit. Chemical and physicochemical properties (specifically hydrophilic).

Independent of the average degree of polymerization of the block (B2), the average degree of polymerization of the block (B1) can vary widely and thus can be most advantageously adapted to the particular needs of the established compositions and methods of the present invention. The average degree of polymerization is preferably in the range of 5 to 100, more preferably 5 to 75, and most preferably 5 to 50.

The block (B2) consists essentially of at least one (preferably one) type of substituted alkylene oxide monomer unit, wherein the substituent is selected from the group consisting of at least two methyl groups, having at least two carbons Alkyl and cycloalkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl.

"Consisting essentially of" means that the block (B2) consists entirely of the alkylene oxide monomer units or contains small amounts of propylene oxide and/or ethylene oxide monomer units. "Small amount" means that the concentration of ethylene oxide and/or propylene oxide monomer units is as low as not adversely affecting the chemical and physical chemistry of the block (B2) produced by the alkylene oxide monomer units. Characteristics (specifically, lipophilic).

The alkylene oxide monomer unit of block (B2) is preferably derived from a substituted ethylene oxide wherein the substituent is selected from the group consisting of at least two methyl groups and an alkyl group having at least two carbon atoms. And cycloalkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl.

More preferably, the substituent is selected from the group consisting of at least two methyl groups, an alkyl group having 2 to 10 carbon atoms, a spiro ring having 5 to 10 carbon atoms, an out-of-loop and/or an annealed configuration ( Annealed configuration of a cycloalkyl group, an aryl group having 6 to 10 carbon atoms, an alkyl-cycloalkyl group having 6 to 20 carbon atoms, an alkyl-aryl group having 7 to 20 carbon atoms, having 11 a cycloalkyl-aryl group to 20 carbon atoms and an alkyl-cycloalkyl-aryl group having 12 to 30 carbon atoms.

Examples of suitable alkyl groups are two methyl and ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl, 2,2-dimethylpropan-1- Base, n-hexyl, 2-methylpentan-1-yl, 3-methylpent-1-yl and 4-methylpent-1-yl, 2,2-dimethylbut-1-yl and 3, 3-dimethylbut-1-yl, n-heptyl, 2,3-dimethylpent-1-yl, 2,3,3-trimethylbutan-1-yl, n-octyl, isooctyl , 2-ethylhexyl, n-decyl, 2-ethyl-3,4-dimethylpentan-1-yl and n-decyl; preferably methyl, ethyl, propyl, isopropyl, positive Butyl, n-pentyl and n-hexyl.

Examples of suitable cycloalkyl groups are cyclopentyl, cyclohexyl, cyclopentane-1,1-diyl, cyclopentane-1,2-diyl, cyclohexane-1,1-diyl and cyclohexane. -1,2-diyl.

Examples of suitable aryl groups are phenyl and 1-naphthyl and 2-naphthyl.

Examples of suitable alkyl-cycloalkyl groups are cyclopentylmethyl and cyclohexylmethyl, 2-cyclopentyleth-1-yl and 2-cyclohexylethyl-1-yl, 3-cyclopentylpropan-1 a group and a 3-cyclohexylpropan-1-yl group and a 4-cyclopentyl-n-butan-1-yl group and a 4-cyclohexyl-n-butan-1-yl group.

Examples of suitable alkyl-aryl groups are phenylmethyl, 2-phenyleth-1-yl, 3-phenylprop-1-yl and 4-phenyl-n-butan-1-yl.

Examples of suitable cycloalkyl-aryl groups are 4-phenyl-cyclohex-1-yl, 4-cyclohexyl-phenyl-1-yl and 2,3-dihydroindole-1,2-diyl.

Examples of suitable alkyl-cycloalkyl-aryl groups are cyclohexyl-phenyl-methyl and 2-cyclohexyl-2-phenyl-eth-1-yl.

Examples of particularly preferred substituted ethylene oxides are ethyl oxirane, 2,2-dimethyloxirane and 2,3-dimethyloxirane, 2,2,3- Trimethyl oxirane, 2,2,3,3-tetramethyloxirane, 2-methyl-3-ethyloxirane, 2,2-diethyloxirane, 2,3-diethyl oxirane, n-propyl oxirane, 2-methyl-3-n-propyl oxirane, n-butyl oxirane, n-pentyl oxirane , n-hexyl oxirane, n-heptyl oxirane, n-octyl oxirane, n-decyl oxirane, n-decyl oxirane, cyclopentyl oxirane, cyclohexyl Ethylene oxide, phenyl oxirane and naphthyl oxirane; 1,2-epoxy-cyclohexane and 1,2-epoxy-cyclopentane; 1-oxa-3-spiro[ 3.4]-heptane and 1-oxa-3-spiro[3.5]-octane; and 1,2-epoxy-2,3-dihydroindole.

The substituted ethylene oxide is preferably selected from the group consisting of 2-ethyloxirane, 2,3-dimethyloxirane, and 2,2-dimethyloxirane. Particularly preferred are 2-ethyloxirane and 2,3-dimethyloxirane.

Therefore, the alkylene oxide monomer unit used is particularly preferably selected from the group consisting of oxy-butyl-1,2-yl, -CH(C ₂ H ₅ )-CH ₂ -O- and oxy-butyl-2,3-yl, -CH(CH ₃ )-CH(CH ₃ )-O-.

Independent of the average degree of polymerization of the block (B1), the average degree of polymerization of the block (B2) can vary widely and thus can be most advantageously adapted to the particular needs of the compositions and methods of the present invention. The average degree of polymerization is preferably in the range of 5 to 100, more preferably 5 to 75, and most preferably 5 to 50.

The variable Y represents a hydrogen atom or a monovalent organic residue other than a linear and branched alkyl group having 5 to 20 carbon atoms.

The monovalent organic residue Y is preferably selected from the group consisting of an alkyl group having 1 to 4 and 21 to 30 carbon atoms and a cycloalkyl group, an aryl group, an alkyl-cycloalkyl group, an alkyl-aryl group. , cycloalkyl-aryl and alkyl-cycloalkyl-aryl.

The monovalent residue Y is more preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl and t-butyl, linear and branched behenyl Base, behenyl, behenyl, tetracosyl, dipentadecyl, hexadecyl, hexadecyl, octadecyl, octadecyl and A triphenyl group, a cyclohexyl group, a benzyl group, and a phenyl group, and a phenyl group having an alkyl group of 4 to 16 carbon atoms at the 4-position.

The monovalent residue Y is preferably a hydrogen atom.

The hydrophilic-lipophilic balance (HLB) values of the amphiphilic nonionic surfactant (B) can vary widely and thus can be most advantageously adapted to the particular needs of the established compositions and methods of the present invention. The HLB value is preferably in the range of 3 to 20 and most preferably 4 to 18.

The surface tension of the amphiphilic nonionic surfactant (B) can also vary widely and thus can be most advantageously adapted to the particular needs of the established compositions and methods of the present invention. The surface tension is preferably from 20 dynes/cm to 60 dynes/cm at 25 ° C, more preferably 25 dynes/cm to 55 dynes/cm, and most preferably from 25 dynes/cm to 50 dynes/cm. Inside.

The weight average molecular weight of the amphiphilic nonionic surfactant (B) can also vary widely and thus can be most advantageously adapted to the particular needs of the established compositions and methods of the present invention. The weight average molecular weight is preferably in the range of from 1000 Daltons to 10,000 Daltons and most preferably from 1100 Daltons to 8000 Daltons, especially from 1100 Daltons to 3500 Daltons.

The preparation of the amphiphilic nonionic surfactant (B) does not provide chemical and methodological details, but it can be carried out according to conventional and known methods, such as the use of the above monohydroxy and polyhydroxy compounds R' as starting molecules or without such The anion ring-opening polymerization of the starting molecule suitable for ethylene oxide or the polycondensation of epichlorohydrin.

The concentration of the two affinic nonionic surfactants (B) in the compositions of the present invention can vary widely and thus can be most advantageously adapted to the particular needs of the established compositions and methods of the present invention. The composition of the present invention preferably contains from 0.001% by weight to 5% by weight, more preferably from 0.005% by weight to 2.5% by weight, even more preferably from 0.0075% by weight to 1% by weight and most preferably from 0.0075% by weight to 0.5% by weight of the two parents A random nonionic surfactant (B).

The composition of the present invention may contain at least one functional component (D) different from the components or components (A), (B) and (C).

The functional component (D) is preferably selected from the group of compounds conventionally used in CMP slurries based on cerium oxide. Examples of such compounds (D) are disclosed, for example, in YN Prasad et al, Electrochemical and Solid-State Letters, 9(12), G337-G339 (2006), Hyun-Goo Kang et al, Journal of Material Research, Vol. 22, No. 3, 2007, pp. 777-787, S. Kim et al., Journal of Colloid and Interface Science, 319 (2008), pp. 48-52, SV Babu et al., Electrochemical And Solid-State Letters, 7(12), G327-G330 (2004), Jae-Dong Lee et al, Journal of the Electrochemical Society, 149(8), G477-G481, 2002, US Patent 5,738,800, US 6,042,741, US 6,132,637, US 6,218,305 B, US 5,759,917, US 6,689,692 B1, US 6,984,588 B2, US 6,299,659 B1, US 6,626,968 B2, US 6,436,835 B1, US 6,491,843 B1, US 6,544,892 B2, US 6,627,107 B2, US 6,616,514 B1 and US 7,071,105 B2 US Patent Application US 2002/0034875 A1, US 2006/0144824 A1, US 2006/0207188 A1, US 2006/0216935 A1, US 2007/0077865 A1, US 2007/0175104 A1, US 2007/0191244 A1 and US 2007/0218811 A1 and Japanese Patent Application JP 2005-336400 A.

Further, the functional component (D) is selected from the group consisting of organic, inorganic and hybrid organic-inorganic abrasives different from the particles (D), materials having a low critical solution temperature LCST or an upper critical solution temperature UCST, An oxidizing agent, a passivating agent, a charge reversing agent, an organic polyol having at least 3 hydroxyl groups which are non-dissociable in an aqueous medium, formed of at least one monomer having at least 3 hydroxyl groups which are non-dissociable in an aqueous medium. Oligomers and polymers, complexing or chelating agents, abrasives, stabilizers, rheological agents, surfactants, metal cations, antimicrobials or biocides, and organic solvents.

Suitable organic abrasives (D) and their effective amounts are known, for example, from US Patent Application No. US 2008/0254628 A1, page 4, paragraph [0054] or from the international application WO 2005/014753 A1, which discloses the disclosure of melamine And such as 2,4-diamine-6-methyl-1,3,5-triazine (acetoguanamine), 2,4-diamine-6-phenyl-1,3,5-triazine A solid particle composed of a benzoguanamine and a melamine derivative of dicyandiamide.

Suitable inorganic abrasives (D) and their effective amounts are, for example, from International Patent Application No. WO 2005/014753 A1, page 12, lines 1 to 8; or US Patent 6,068,787, column 6, line 41 to Line 7 and line 65 are known.

Suitable hybrid organic-inorganic abrasives (D) and their effective amounts are for example from US Patent Application US 2008/0254628 A1, page 4, paragraph [0054] or US 2009/0013609 A1, page 3 [0047] Paragraphs to page 6 [0087] are known.

Suitable oxidizing agents (D) and their effective amounts are, for example, from European Patent Application EP 1 036 836 A1, page 8 [0074] and [0075] or US Pat. No. 6,068,787, col. 4, line 40 to Line 7 and line 45 or US 7,300,601 B2, column 4, line 18 to line 34 are known. Organic and inorganic peroxides are preferred, and inorganic peroxides are more preferred. In particular, hydrogen peroxide is used.

Suitable passivating agents (D) and their effective amounts are, for example, from U.S. Patent No. 7,300,601 B2, at col. 3, line 59 to col. 4, line 9; or US Patent Application No. US 2008/0254628 A1, across page 4 See paragraph [0058] on page 5.

a suitable complexing agent or chelating agent (D) (which is sometimes also referred to as a friction agent) (see US Patent Application No. US 2008/0254628 A1, page 5, paragraph [0061]) or an etching agent or An etchant (see U.S. Patent Application No. US 2008/0254628 A1, page 4, paragraph [0054]) and its effective amount is, for example, from U.S. Patent No. 7,300,601 B2, col. 4, line 35 to 48 Know the line. Very particular preference is given to using amino acids (specifically glycine) and dicyandiamide and further comprising at least one, preferably two and more preferably three primary amine groups Such as melamine and water-soluble guanamine, especially melamine, 2,4-diamine-1,3,5-triazine (formoguanamine), 2,4-diamine-6-methyl-1,3,5-triazine And 2,4-diamino-6-ethyl-1,3,5-three .

Suitable stabilizers (D) and their effective amounts are known, for example, from U.S. Patent No. 6,068,787, at col. 8, line 4 to line 56.

Suitable rheological agents (D) and their effective amounts are known, for example, from U.S. Patent Application No. US 2008/0254628 A1, page 5, paragraph [0065] to page 6, paragraph [0069].

Suitable surfactants (D) and their effective amounts are, for example, from International Patent Application WO 2005/014753 A1, page 8, line 23 to page 10, line 17; or US Patent 7,300,601 B2, column 5 Line 4 to Column 6 and Line 8 are known.

Preferred surfactants (D) are nonionic surfactants selected from the group consisting of linear and branched alkylene oxides, preferably ethylene oxide and propylene oxide homopolymers and copolymers.

The preferred ethylene oxide-propylene oxide copolymer (D) may be a random copolymer, an alternating copolymer or a block copolymer containing a polyethylene oxide block and a polypropylene oxide block.

In the ethylene oxide-propylene oxide block copolymer (D), the polyethylene oxide block preferably has a hydrophilic-lipophilic balance (HLB) value of 10 to 15. The polypropylene oxide block can have an HLB value of from 28 to about 32.

Preferred surfactants (D) are conventional and known, commercially available materials and are described in European Patent EP 1 534 795 B1, page 3, paragraph [0013] to page 4, paragraph [0023], Japanese Patent Application JP 2001-240850 A, Patent Application No. 2 and paragraphs [0007] to [0014], US Patent Application US 2007/0077865 A1, page 1 [0008] to page 2 [0010] U.S. Patent Application No. US 2006/0124594 A1, page 3, paragraphs [0036] and [0037], and U.S. Patent Application No. US 2008/0124913 A1, page 3, paragraph [0031] to [ Paragraph No. 0033] and in the scope of claim 14 or as evidenced by BASF Corporation's company brochure "Piuronic ^TM & Tetronic ^TM Block Copolymer Surfactants, 1996" or US Patent US 2006/0213780 A1 by BASF and BASF SE trademark Pluronic ^TM, Tetronic ^TM and Basensol ^TM for sale.

Polyethylene glycol (PEG) is most preferably used as the nonionic surfactant (D).

Suitable polyvalent metal ions (D) and their effective amounts are known, for example, from European Patent Application EP 1 036 836 A1, page 8, paragraph [0076] to page 9, paragraph [0078].

Suitable organic solvents (D) and their effective amounts are, for example, from U.S. Patent No. 7,361,603 B2, at column 7, line 32 to line 48; or US Patent Application No. US 2008/0254628 A1, page 5, page [0059 The paragraph is known.

Suitable antimicrobial agents or biocides (D) are N-substituted diazenium dioxides and N'-hydroxy-diazenium oxide salts. ).

Suitable materials (D) showing a low critical solution temperature LCST or an upper critical solution temperature UCST are described, for example, in H. Mori, H. Iwaya, A. Nagai and T. Endo, Controlled synthesis of thermoresponsive polymers derived from L-proline via RAFT polymerization. , Chemical Communication, 2005, 4872-4874 article or D. Schmaljohann, Thermo- and pH-responsive polymers and drug delivery, Advanced Drug Delivery Reviews, Vol. 58 (2006), 1655-1670 or US Patent Application US 2002/0198328 A1, US 2004/0209095 A1, US 2004/0217009 A1, US 2006/0141254 A1, US 2007/0029198 A1, US 2007/0289875 A1, US 2008/0249210 A1, US 2008/0050435 A1 or US 2009/ U.S. Patent No. 5,057,560, US Pat. No. 5,788,82, and US Pat. No. 6,682,642 B2, International Patent Application No. WO 01/60926 A1, WO 2004/029160 A1, WO 2004/0521946 A1, WO 2006/093242 A2 or WO 2007/012763 A1 European Patent Application No. EP 0 583 814 A1, EP 1 197 587 B1 and EP 1 942 179 A1 or German Patent Application No. DE 26 10 705.

In principle, any charge reversal agent (D) known to be used in the field of CMP can be used. The charge reversal agent (D) is preferably selected from the group consisting of monomers having at least one anionic group selected from the group consisting of carboxylate, sulfinate, sulfate, phosphonate and phosphate groups, Poly and polymeric compounds.

An anionic phosphate dispersant (specifically, a water-soluble condensed phosphate) is preferably used as the charge reversal agent (D).

Examples of suitable water-soluble condensed phosphates (D) are salts, in particular ammonium metaphosphate, sodium and potassium salts of the formula I:

[M _n (PO ₃ ) _n ](I);

And ammonium, sodium and potassium polyphosphates of the general formula II and the general formula III:

M _n+2 P _n O _3n+1 (II);

M _n H ₂ P _n O _3n+1 (III);

Wherein M is an ammonium, sodium or potassium cation and the index n is from 2 to 10,000.

Examples of particularly suitable water-soluble condensed phosphates (D) are Graham's salt (NaPO ₃ ) _40-50 , Calgon ^TM (NaPO ₃ ) _15-20 , Kurrol's salt (NaPO _{3 ) n} (where n = about 5000) and ammonium hexametaphosphate, sodium hexametaphosphate and potassium hexametaphosphate.

The concentration of the water-soluble anionic phosphate dispersant (D) in the compositions of the present invention can vary widely and thus can be most advantageously adapted to the particular needs of the established compositions and methods of the present invention. The anionic phosphate dispersing agent (D) is preferably used in an amount of from 10 to 2,000, and more preferably from 20 to 1,000, by weight of the cerium oxide (A) to the anionic phosphate dispersing agent (D).

If present, it may contain varying amounts of functional component (D). The total amount of (D) is preferably not more than 10 wt.% ("wt.%" means "% by weight"), more preferably not more than 2 wt.%, and most preferably not based on the total weight of the corresponding CMP composition. More than 0.5 wt.%, especially not more than 0.1 wt.%, such as not more than 0.01 wt.%. The total amount of (D) is preferably at least 0.0001 wt.%, more preferably at least 0.001 wt.%, most preferably at least 0.008 wt.%, especially at least 0.05 wt.%, based on the total weight of the respective composition. For example, it is at least 0.3 wt.%.

The composition of the invention may optionally contain at least one pH adjusting agent or buffer (E) which is substantially different from ingredients (A), (B) and (C).

Suitable pH adjusting agents or buffers (E) and their effective amounts are, for example, from European Patent Application EP 1 036 836 A1, page 8, paragraphs [0080], [0085] and [0086] International Patent Application No. WO 2005/014753 A1, page 12, line 19 to line 24, US Patent Application No. US 2008/0254628 A1, page 6, paragraph [0073] or US Patent US 7,300,601 B2, Column 5, line 33 to line 63 are known. Examples of the pH adjuster or buffer (E) are potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide (TMAH), nitric acid and sulfuric acid.

If present, it may contain varying amounts of pH adjusters or buffers (E). The total amount of (E) is preferably not more than 20 wt.%, more preferably not more than 7 wt.%, most preferably not more than 2 wt.%, especially not more than 0.5 wt.%, based on the total weight of the corresponding CMP composition. For example, no more than 0.1 wt.%. The total amount of (E) is preferably at least 0.001 wt.%, more preferably at least 0.01 wt.%, most preferably at least 0.05 wt.%, especially at least 0.1 wt.%, based on the total weight of the respective composition. For example, it is at least 0.5 wt.%.

Preferably, the pH of the composition of the invention is preferably set between 3 and 10, more preferably between 3 and 8, even more preferably between 3 and 7, and preferably 5 with the pH adjusting agent (E). Between 7.

The preparation of the composition of the present invention does not present any details, but can be dissolved or dispersed in an aqueous medium by using the above components (A), (B) and (C) and optionally (D) and/or (E). (Specific deionized water) is carried out. For this purpose, conventional and standard mixing methods and mixing devices such as agitation tanks, in-line dissolvers, high shear impellers, ultrasonic mixers, homogenizer nozzles or counterflow mixers can be used. The composition of the present invention thus obtained can preferably be filtered through a filter having a suitable mesh pore size to remove coarse particles (such as solid binders or aggregates) and finely disperse the abrasive (A).

The compositions of the invention are excellently suited for use in the process of the invention.

In the method of the invention, the substrate of the electrical, mechanical and optical device (specifically the electrical device, preferably the integrated circuit device) is contacted with the composition of the invention at least once and polished (specifically chemical and mechanical polishing) until Achieve the required flatness.

The method of the present invention exhibits particular advantages in CMP of a germanium semiconductor wafer having at least one dielectric barrier film composed of at least one (preferably one) yttria dielectric material and at least one thin film composed of polysilicon.

The yttria dielectric material is preferably selected from the group consisting of cerium oxide and low-k and ultra-low-k cerium oxide materials.

The germanium semiconductor wafer optionally has at least one tantalum nitride film.

Suitable cerium oxide materials can be used by low pressure and high pressure plasma chemical vapor deposition (LDP CVD or HDP CVD) as described, for example, in U.S. Patent Application No. US 2007/0175104 A1, page 7, paragraph [0092]. The preparation is described by monodecane-oxygen or tetraethyl ortho-ruthenium (TEOS)-oxygen plasma.

Suitable low-k or ultra-low-k materials for the preparation of insulating dielectric films and suitable methods are described in, for example, U.S. Patent Application No. US 2005/0176259 A1, page 2, paragraphs [0025] to [0027], US 2005 /0014667 A1, page 1, paragraph [0003], US 2005/0266683 A1, page 1 [0003] and page 2, paragraph [0024] or US 2008/0280452 A1, paragraph [0024] To [0026] or U.S. Patent 7,250,391 B2, col. 1, line 49 to line 54 or European Patent Application EP 1 306 415 A2, page 4, paragraph [0031].

The method of the present invention is particularly useful for shallow trench isolation (STI) that requires selective removal of a dielectric yttria material on a patterned wafer substrate rather than a polysilicon. In this method, the etched trench is overfilled with a dielectric yttria material such as cerium oxide, and the dielectric yttria material is polished using a polysilicon film as a barrier or stop film. In the preferred embodiment, the method of the present invention ends with the removal of germanium dioxide from the barrier film while minimizing the removal of exposed polysilicon and trenched germanium dioxide.

In addition, the method of the present invention is also particularly well suited for shallow trench isolation (STI) in which a tantalum nitride film is also present because the composition of the present invention not only exhibits a higher oxide selectivity relative to polycrystalline germanium, but also exhibits The selectivity of the advantageous nitride relative to the polysilicon and the selectivity of the advantageous oxide to the nitride.

The method of the present invention does not present any details, but it can be used in methods and apparatus conventionally used for CMP in the fabrication of IC semiconductor wafers.

As is known in the art, a typical apparatus for CMP consists of a rotating platen covered with a polishing pad. The wafer is placed on a carrier or chuck with the upper side facing downward toward the polishing pad. The carrier secures the wafer to a horizontal position. This particular configuration of the polishing and holding device is also referred to as a hard plate design. The carrier may retain a carrier pad between the holding surface of the carrier and the surface on which the wafer is not intended to be polished. This pad can act as a cushion for the wafer.

Below the carrier, the larger diameter platen is also typically placed horizontally and provides a surface that is parallel to the surface of the wafer to be polished. During the planarization process, its polishing pad contacts the wafer surface. During the CMP process of the present invention, the compositions of the present invention are applied to the polishing pad in the form of a continuous fluid or in a drop-wise manner.

The carrier and the platen are rotated about respective axes of rotation that extend perpendicularly from the carrier and the platen. The rotating shaft of the carrier in rotation can be fixed in position relative to the rotating platen, or can oscillate horizontally relative to the platen. The direction of rotation of the carrier is typically (but not necessarily) the same as the direction of rotation of the platen. The rotational speed of the carrier and the platen is usually (but not necessarily) set to a different value.

Typically, the temperature of the platen is set to a temperature between 10 ° C and 70 ° C.

For further details, please refer to International Patent Application No. WO 2004/063301 A1, in particular paragraph 16 [0036] to page 18 [0040] and Figure 1.

By the method of the present invention, an IC semiconductor wafer including a patterned polycrystalline germanium and a dielectric yttria thin film (specifically, a cerium oxide thin film) having excellent flatness can be obtained. Therefore, a copper damascene pattern which also has excellent flatness is obtained and an excellent electrical function is obtained in the completed IC.

Example or comparative experiment

Example 1

Preparation of aqueous polishing composition 1 to 9 containing amphiphilic nonionic surfactant (B) and aqueous polishing composition 10 containing no amphiphilic nonionic surfactant (B)

In order to prepare the aqueous polishing compositions 1 to 10, cerium oxide (as measured by dynamic laser light scattering, average particle diameter d ₅₀ is 120 nm to 180 nm) and sodium hexametaphosphate (PP; weight ratio of cerium oxide to PP = 200:1, designated as PP _{200 below} , dispersed or dissolved in ultrapure water.

For the preparation of the aqueous polishing compositions 1 to 9, the two affinic nonionic surfactants (B) listed in Table 1 were additionally added.

For the preparation of the aqueous polishing composition 10, the amphiphilic nonionic surfactant (B) was not added.

The amounts of the components of the aqueous polishing composition are compiled in Table 2.

Table 1: Amphiphilic nonionic surfactants used (B)

a) a polyethylene oxide-poly-1,2-butylene oxide-polyethylene oxide block copolymer;

b) a polyethylene oxide-poly-2,3-butylene oxide block copolymer;

c) Method B: 100 g of a 5 wt% aqueous solution of sodium chloride containing 1 g of a surfactant;

Method E: 25 g of a 25 wt% aqueous solution of diethylene glycol butyl ether containing 5 g of a surfactant;

d) The surface tension at 4 ° C is 45.3 dynes/cm.

Table 2: Composition of aqueous polishing composition 1 to 10

The aqueous polishing compositions 1 to 9 are excellently suited for the STI process.

Examples 2 to 9 and Comparative Experiment C1

CMP of germanium dioxide, tantalum nitride and polycrystalline germanium films on semiconductor wafers

The aqueous polishing compositions 1 to 9 of Example 1 were used for Examples 2 to 9.

The aqueous polishing composition 10 of Example 1 was used for Comparative Experiment C1.

A 200 mm blanket-type ruthenium wafer with a high-density plasma deposition (HDP) ruthenium dioxide film, a 200 mm blanket-type ruthenium wafer with a LPCVD tantalum nitride film, and a non-aqueous polishing composition 1 to 10 The 200 mm blanket-type germanium wafer of the crystalline polycrystalline germanium film is chemically mechanically polished under the following conditions:

- Polishing instrument: AMAT Mirra (rotation type);

- Platen speed: 93 rpm;

- Carrier speed: 87 rpm;

- Polishing pad: IC1010-k groove pad;

- pad adjustment: in situ;

- Regulator: 3MA166;

- Adjust the downforce: 5 lbf (22.24 N);

- Slurry flow rate: 160 ml/min;

- Polishing down pressure: 3.5 psi (205 mbar);

- Polishing time: 60 seconds.

The material removal rate MRR was determined by measuring the thickness of HDP ceria, tantalum nitride, and polysilicon film on a semiconductor substrate using a Thermawave Optiprobe 2600 before and after CMP.

The MRR and calculated oxide selectivity relative to polycrystalline germanium, nitride versus polycrystalline germanium and oxide versus nitride are compiled in Table 3.

Table 3: MRR and oxides of HDP cerium oxide (HDP), cerium nitride (SiN) and polycrystalline germanium (PSi) of Examples 1 to 9 and Comparative Experiment C1 versus polycrystalline germanium and nitrides relative to polycrystalline germanium

The results of Table 3 show that the amphiphilic nonionic surfactant (B) in the aqueous polishing compositions 1 to 9 of Example 1 acts as an excellent polysilicon inhibitor and furthermore does not adversely affect the nitride relative to The selectivity of polycrystalline germanium.

Claims (16)

An aqueous polishing composition comprising: (A) at least one type of abrasive comprising or consisting of cerium oxide in an amount of from 0.005% by weight to 6% by weight based on the total weight of the polishing composition; and (B) Between 0.001% by weight and 0.5% by weight of at least one amphiphilic nonionic surfactant selected from the group consisting of water-soluble and water-dispersible, linear and branched polyalkylene oxide block copolymers of the formula I The weight percentages are based on the total weight of the composition: R[(B1) _m /(B2) _n Y] _p (I), wherein the indices and variables have the following meanings: m is greater than or equal to 1. An integer; n is an integer greater than or equal to 1; p is an integer greater than or equal to 1; R is a hydrogen atom or a monovalent or polyvalent organic residue other than a linear or branched alkyl group having 5 to 20 carbon atoms (B1) is a block consisting essentially of ethylene oxide monomer units; (B2) is a block consisting essentially of at least one type of substituted alkylene oxide monomer units, wherein the substituents are Selected from the group consisting of at least two methyl groups, an alkyl group having at least two carbon atoms, and a cycloalkyl group or Alkyl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl; and Y is a hydrogen atom or a linear chain having 5 to 20 carbon atoms and a monovalent organic residue other than a branched alkyl group; the constraint is that when (B) contains more than one block (B1) or (B2), two blocks of the same type are separated from each other by another type of block, and wherein The pH of the composition was set between 5 and 7. The aqueous polishing composition of claim 1, wherein the alkylene oxide monomer units of the block (B2) are derived from substituted ethylene oxide, wherein the substituents are selected from the group consisting of Group: at least two methyl groups and an alkyl group having at least two carbon atoms and a cycloalkyl group, an aryl group, an alkyl-cycloalkyl group, an alkyl-aryl group, a cycloalkyl-aryl group, and an alkyl-cycloalkane group Base-aryl. The aqueous polishing composition of claim 2, wherein the substituents are selected from the group consisting of at least two methyl groups, an alkyl group having 2 to 10 carbon atoms, and 5 to 10 carbon atoms. a cycloalkyl group in a spiro ring, an out-of-loop and/or an annealing configuration, an aryl group having 6 to 10 carbon atoms, an alkyl-cycloalkyl group having 6 to 20 carbon atoms, having 7 An alkyl-aryl group to 20 carbon atoms, a cycloalkyl-aryl group having 11 to 20 carbon atoms, and an alkyl-cycloalkyl-aryl group having 12 to 30 carbon atoms. The aqueous polishing composition of claim 3, wherein the substituted ethylene oxide is selected from the group consisting of 2-ethyloxirane and 2,3-dimethyloxirane. And 2,2-dimethyloxirane. The aqueous polishing composition according to any one of claims 1 to 4, wherein the amphiphilic nonionic surfactant (B) has an HLB value of from 3 to 20. Water-based polishing as in any of items 1 to 4 of the patent application scope The composition wherein the average degree of polymerization of the blocks (B1) and (B2) is independently from 5 to 100. The aqueous polishing composition according to any one of claims 1 to 4, wherein the amphiphilic nonionic surfactant (B) has a weight average molecular weight of from 1,000 Daltons to 10,000 Daltons. The aqueous polishing composition according to any one of claims 1 to 4, which contains at least one functional component (D) different from the components (A) and (B). The aqueous polishing composition of claim 8, wherein the functional component (D) is selected from the group consisting of organic, inorganic and hybrid organic-inorganic abrasives different from the particles (A), a material having a low critical solution temperature LCST or an upper critical solution temperature UCST, an oxidizing agent, a passivating agent, a charge reversing agent, an organic polyol having at least two hydroxyl groups which are non-dissociable in an aqueous medium, having at least one of at least two in water An oligomer formed from a monomer of a non-dissociable hydroxyl group in a medium, a polymer, a complexing agent or a chelating agent, a friction agent, a stabilizer, a rheological agent, a surfactant, a metal cation, an antimicrobial agent, and an organic solvent. The aqueous polishing composition of claim 8, wherein the functional component (D) is a charge reversal agent conventionally used in the field of CMP. The aqueous polishing composition of claim 8, wherein the functional component (D) is a charge reversal agent selected from the group consisting of at least one selected from the group consisting of carboxylate, sulfinate, sulfate, and phosphine. A monomer, oligomeric, and polymeric compound of an anionic group of a group consisting of an acid group and a phosphate group. The aqueous polishing composition of claim 8, wherein the functional component (D) is a charge reversal agent which is a water-soluble condensed phosphate. A method of polishing a substrate for an electrical, mechanical, and optical device by contacting the substrate with an aqueous polishing composition at least once and polishing the substrate material until a desired flatness is achieved, characterized by use of a patent application The aqueous polishing composition according to any one of items 1 to 12. The method of claim 13, wherein the substrate comprises at least one film comprising at least one cerium oxide dielectric material or a film composed of at least one cerium oxide dielectric material and at least one film comprising or consisting of polycrystalline germanium. The method of claim 14, wherein the substrate material additionally comprises at least one film comprising or consisting of tantalum nitride. The method of any one of the preceding claims, wherein the electrical device is an integrated circuit device liquid crystal panel, an organic electroluminescent panel, a printed circuit board, a micromachine, a DNA wafer, or a micro device ( Micro plant) and magnetic head; the mechanical devices are high-precision mechanical devices; and the optical devices are optical glass (selected from a light mask, a lens and a crucible), and an inorganic conductive film (selected from indium tin oxide (ITO)) , optical integrated circuit, optical conversion element, optical waveguide, optical single crystal (selected from the end face of optical fiber and scintillator), solid laser single crystal, sapphire substrate of blue laser LED, semiconductor single crystal and magnetic disk glass substrate.