TW201229164A - Aqueous polishing composition and process for chemically mechanically polishing substrates having patterned of unpatterned low-k dielectric layers - Google Patents

Abstract

An aqueous polishing composition comprising (A) abrasive particles and (B) an amphiphilic nonionic surfactant selected from the group consisting of water-soluble or water-dispersible surfactants having (b1) hydrophobic groups selected from the group consisting of branched alkyl groups having 10 to 18 carbon atoms; and (b2) hydrophilic groups selected from the group consisting of polyoxyalkylene groups comprising (b21) oxyethylene monomer units and (b22) substituted oxyalkylene monomer units wherein the substituents are selected from the group consisting of alkyl, cycloalkyl, or aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl groups, the said polyoxyalkylene group containing the monomer units (b21) and (b22) in random, alternating, gradient and/or blocklike distribution; a CMP process for substrates having patterned or unpatterned low-k or ultra-low-k dielectric layers making use of the said aqueous polishing composition; and the use of the said aqueous polishing composition for manufacturing electrical, mechanical and optical devices.

Description

201229164 VI. INSTRUCTIONS: The Moon is a new type of water-based abrasive composition #, which is especially suitable for grinding, red-patterned or unpatterned low-k or ultra-low-k dielectric substrates. The present invention relates to a novel method for chemical mechanical polishing of substrates having a patterned or unpatterned low k or ultra low k dielectric layer. Citation of documents cited in the present application is incorporated by reference in its entirety. BACKGROUND OF THE INVENTION Chemical mechanical planarization or polishing (CMP) is the primary method for achieving integrated circuit (IC), localized σ, and full flatness. This technique typically applies a CMp composition or slurry containing abrasives and other additives as active chemical agents between the surface of the rotating substrate and the polishing pad under application of a load. Thus, CMP methods combine physical methods such as milling with chemical methods such as oxidation or chelation. The removal or polishing of the substrate material should not include only physical effects or only chemical interactions, but should include a synergistic combination of the two to achieve rapid and uniform removal. Therefore, the substrate material is removed until the desired flatness or barrier sublayer or termination layer exposure is achieved. A flat, defect-free surface is finally obtained which allows for the fabrication of a suitable multilayer (1) device by subsequent photolithography, patterning, etching, and thin film processing. " gradual reduction of the feature size of circuit components in a large-scale integration (LSI) 戋 super 4 201229164 very large-scale integration (VLSI) integrated circuit (IC) device The need to planarize the complete surface of the various film layers constituting ic by CMP is increased. Typically, CMP involves removing a film such as: - copper for conductive wiring, - used as a diffusion barrier to prevent copper from diffusing into tantalum nitride, button/tantalum nitride or titanium in the dielectric material, and - a dioxide dioxide used as an insulating dielectric material between conductive wirings. Therefore, it is necessary to be able to grind the different layers at the desired rate to obtain the desired defect-free surface as described in, for example, U.S. Patent Application No. US 2005/0076578 AU US 7, 153' 335 B2) and US 2009/03 1 1864 A1. Therefore, typical CMP slurries for barrier CMP require different components to increase and suppress the removal rate (MRR) to achieve the desired selectivity. Therefore, the tantalum nitride MRR can be adjusted by an oxidizing agent such as hydrogen peroxide and a cerium nitride enhancer such as malonic acid, which is a film forming agent for interrupting the formation of cerium oxide. The MRR of cerium oxide (especially TEOS) can be inhibited by selective adsorption onto a polyol-rich surface. The MRR of copper can be adjusted by using a combination of an enhancer such as L-group amine acid and a passivating agent such as benzotriazole (BTA). In the semiconductor industry, CMp slurries for inter-metal dielectric layers based on germanium are particularly well developed and the chemical and mechanical properties of the rubbing and polishing of germanium-based dielectrics are well understood. However, a problem with germanium-based dielectric materials is that their dielectric constant is relatively high, depending on factors such as the residual moisture content of 201229164, which is about 3·9 or more. Therefore, the capacitance between the conductive layers is relatively high, which in turn limits the speed or frequency at which the IC can operate. Secondly, strategies for reducing capacitance include (1) incorporating metals with lower resistivity values (such as copper), and (2) using insulating materials with lower dielectric constant than cerium oxide (ie, low-k and ultra-low-k dielectrics). Electrical material) provides electrical insulation. The low-k and ultra-low-k dielectric materials include organic polymeric materials, inorganic and organic porous dielectric materials, and blended or composite organic and inorganic materials, which may be porous or non-porous, such as carbon doped Oxidized crushed material. It is highly desirable to incorporate such low-k and ultra-low-k dielectric materials into the 1C structure while still being able to polish the surface of the dielectric material using conventional CMp slurry during semiconductor wafer processing." In particular, it is highly desirable compared to low k and ultra-low k materials (such as carbon dioxide-doped ash dioxide) achieve high selectivity for dioxotomy (especially TE 〇s). This high selectivity is extremely important to maintain ultra-low k integrity, especially for 45 nm nodes and under 45 nm nodes and novel complementary metal oxide semiconductor (CMOS) generation. U.S. Patent Application Serial No. 2,200, filed to U.S. Pat. a group of ruthenium, osmium oxide, ruthenium oxide, oxidized towns, and co-formed products thereof; and - an amphoteric nonionic surfactant having at least one hydrophobic head group and at least one hydrophilic tail group. According to US 2003/0228762 A1, suitable head groups include polyoxyalkylene, tetra-C, .4 alkyl decyne, saturated or partially unsaturated G w alkyl 'polyoxy 6 201229164 propylene group, C6·, 2 alkylphenyl or alkylcyclohexyl and polyethylene groups. Appropriate mouth. The oxime group includes a polyoxyethylene group. Therefore, the amphoteric anionic surfactant may be selected from the group consisting of polyoxyethylene alkyl ethers or esters. However, according to the embodiment of US 2003/0228762 Α1, the low-k dielectric MRR caused by the disclosed amphoteric nonionic surfactant is reduced by no more than 75%, and compared to low-k dielectric nitridation. The selectivity of the button is no more than 3 for PETEOS compared to the low-k dielectric. A CMP slurry for grinding a metal layer containing a nonionic polyoxyethylene-polypropylene-based surfactant is disclosed in the patent application EP 1 150341 A1. However, the number of carbon atoms in the alkyl group and the distribution of the oxyethyl and propyl propyl monomer units are not precisely defined. In addition, the European patent application remains silent on CMp low-k and ultra-low-k materials using CMp slurries containing such surfactants. US Patent Application US 2008/0124913 AU| shows a slurry of a nonionic polyoxyethylene polyoxypropylene alkyl ether surfactant of the formula: CH3-(CH2)n.(CH(CH3)CH2〇)y (CH2CH20)x-

And X wherein the subscript has the following meaning: η = 3-22, y = 1-30, 3〇, wherein x+y is preferably at least 5, which is a polysilicon inhibitor. US Patent No. 6,645,051 揭示 2 discloses a CMP slurry for polishing a hard disk substrate of a memory comprising a polyoxyethylene-polyoxypropylene bismuth diacyl surfactant, % of carbon atoms in the alkyl group. And the distribution of the oxy-extension ethyl group: the oxy-propanyl monomer mono- oxime is not precisely regulated. In addition, U.S. patents remain silent on the use of CMP destructive liquids CMlM & k and ultra low 201229164 k materials containing such surfactants. The object of the present invention is to clarify that its CMP^ # provides - (iv) aqueous abrasive composition, or 3 5; is very suitable for chemical mechanical polishing with a dielectric constant of 3 · · under the pattern or not Patterned or super-substrate, especially semiconductor wafers. Electric Potential 4 More specifically, the new water-based abrasive composition should be extremely suitable for the barrier of substrate materials other than the low-k and ultra-low-k dielectric layers (such as metal layers, barrier layers and ruthenium dioxide layers). cMp. 〃The novel water-based abrasive composition, especially the new CMp decomposing liquid, should preferably remove the oxidized layer and maintain the integrity of the low-k and ultra-low-k materials, that is, compared to the low-k and ultra-low-k materials. It has a particularly high selectivity for cerium oxide in terms of MRR. The novel CMP slurry preferably does not affect the MRR of the metal layer and the barrier layer (when present). In particular, when a metal layer, a barrier layer, and a ceria layer are present in the substrate to be polished, the novel aqueous abrasive composition should exhibit as many combinations of the following characteristics: (a) a high MRR of the metal layer, (b) The MRR of the barrier layer is high (M), and the high MRR of '(d) is superior to the low-k and ultra-low-k materials in terms of MRR. High selectivity to metal layers in terms of MRR compared to low-k and ultra-low-k materials and (f) high selectivity to barrier layers in MRR compared to low-k and ultra-low-k materials. More specifically, when the copper layer, the tantalum nitride layer, and the dioxide layer are present in the substrate to be polished, the 'new water-based abrasive composition should exhibit as many combinations as possible: (a') high copper , (b,) high MRR of tantalum nitride, high MRR '(d') of (c') cerium oxide compared to low-k and ultra-low k 8 201229164 material in terms of MRR High selectivity, (e' and ultra-low k materials are highly selective and low for steel in MRR & MKR) compared to low k (f·) compared to k and ultra low k materials in terms of MRR High selectivity to tantalum nitride. In addition, one aspect of the present invention provides a chemical mechanical polishing substrate having a patterned and unpatterned low-k or ultra-low k" electrical layer having an electrical constant of 3.5 or less; A novel approach to semiconductor wafers. More special. The novel method should be well suited for barrier CMP of substrate materials other than the low-k and ultra-low-k electrical layers, such as metal layers, barrier layers, and hafnium oxide layers. The novel method should preferably remove the ruthenium dioxide layer and maintain the integrity of the low-k and ultra-low-k materials, that is, it should be particularly high in terms of mrr for oxidized slag compared to low-k and ultra-low-k materials. Selectivity. Preferably, the new method should not affect the MRR of the metal layer and the barrier layer (when present). Summary of the Invention thus, a novel aqueous abrasive composition is found which comprises: (A) at least one abrasive particle, and (B) at least one amphoteric nonionic surfactant selected from the group consisting of water soluble below Or a group of water-dispersible surfactants: (bl) at least one hydrophobic group selected from the group consisting of branched alkyl groups having 5 to 2 carbon atoms; and (b2) at least one hydrophilic group a group selected from the group consisting of polyoxyalkylene groups: (b21) anoxyethyl monomer unit, and (b22) at least one substituted oxy-based monomer unit, wherein 201229164 The substituent is selected from the group consisting of: alkane, also & cycloalkyl or aryl, alkyl-cycloalkyl, aryl-aryl & cycloalkyl-aryl and leuko The polyoxyalkylene group contains monomer units (b21) and (b22) which are randomly distributed, alternately distributed, gradient-distributed, and/or block-likely distributed. Hereinafter, the new water-abrasive polishing composition is referred to as "the composition of the present invention". A substrate having a dielectric constant of 3.5 or 3.5 for a dielectric or ultra-low k layer. In addition, a novel method of patterning or unpatterning low k under a chemical mechanical polishing tool is found. The method includes the following steps (1) The substrate material is contacted with the aqueous abrasive composition comprising at least one of the following: (A) at least one abrasive particle, and (Ba) at least one amphoteric nonionic surfactant selected from the group consisting of a group consisting of the following water-soluble or water-dispersible surfactants: (bla) at least one hydrophobic group 'selected from a linear alkyl group and a branched alkyl group having 5 to 2 carbon atoms ( Bl) the group consisting of; and

(b2) at least one hydrophilic group selected from the group consisting of: a (b21) oxyethyl monomer unit, and (b22) at least one substituted oxyalkylene group a monomer unit wherein the substituent is selected from the group consisting of alkyl, cycloalkyl or aryl, '-cycloalkyl, alkyl-aryl' cycloalkyl-aryl and alkyl-cycloalkane The polyoxyalkylene group contains monomeric units (b2i) and (b22) which are randomly distributed, alternately distributed, and have a gradient of eight cloths and/or a block-like distribution. 10 201229164 () Chemistry under 疋' severity The substrate is mechanically ground for a certain period of time until the desired complete flatness is achieved; and (3) the substrate is removed from contact with the aqueous abrasive composition of the present invention. In the following, a novel method of chemically and mechanically polishing a substrate having a patterned and unpatterned low-k and ultra-low-k dielectric layer having a dielectric constant of 35 or less is referred to as "the method of the present invention". Last but not least, the novel use of the compositions of the invention for the manufacture of electrical, mechanical and optical devices has been found, which is hereinafter referred to as "the use of the invention". Advantages of the Invention It has been surprisingly discovered and skilled in the art that the object of the present invention can be solved by the compositions, methods and uses of the present invention. In particular, it has been found that the composition of the present invention is highly suitable for chemical mechanical polishing of substrates having a patterned or unpatterned low-k or ultra-low-k dielectric layer having a dielectric constant of 3.5 or less, especially semiconductor crystals. circle. It has been particularly surprisingly found that the compositions of the present invention are highly suitable for barrier CMP of substrate materials in which other materials (e.g., metal layers, barrier layers, and hafnium oxide layers) exist in addition to the low-k and ultra-low-k dielectric layers. It has been surprisingly found that the compositions of the present invention are also well suited for use in the present invention, i.e., the fabrication of electrical, mechanical, and optical devices in which high precision grinding steps are required. In the method of the present invention, 'the composition of the present invention preferably removes the layer of the dioxide and maintains the integrity of the low-k and ultra-low-k layers', that is, compared to the low-resistance and 11 201229164 ultra-low-k materials, It has a particularly high selectivity for cerium oxide in terms of MRR. The composition of the present invention preferably does not affect the MRR of the metal layer and the barrier layer (when present). Furthermore, the method of the present invention is most suitable for chemical mechanical polishing of substrates, particularly semiconductor wafers, having a patterned or unpatterned low k or ultra low k dielectric layer having a dielectric constant of 3.5 or less. More specifically, the method of the present invention is most suitable for barrier CMP of substrates other than low-k and ultra-low-k dielectric layers, such as metal layers, barrier layers, and dioxide layers. The method of the present invention preferably removes the ruthenium dioxide layer and maintains a low k and ultra low quality for the material, i.e., compared to low k and ultra low k materials, which has a particularly high selectivity for ruthenium oxide in terms of mrr Sex. The composition of the present invention preferably does not have the MRR of the metal layer and the barrier layer (when present). DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention is an aqueous composition. This means that it contains water, especially = pure water as the main solvent and dispersant. However, the composition of the present invention may contain at least one water-miscible organic solvent, but only in a small amount so as not to change the aqueous properties of the composition of the present invention. The composition of the present invention preferably contains from 6 to 99.95% by weight, more preferably from 7 to 99.9% by weight, even more preferably from 80 to 99.9 weight%. And an optimum amount of water of from 90 to 99.9% by weight, based on the total weight of the composition of the present invention. By "water soluble" it is meant that at the molecular level, the relevant components or components of the compositions of the invention are soluble in the aqueous phase. Waterjet dispersibility means that the relevant component or component of the composition of the present invention can be dispersed in the aqueous phase and form a stable emulsion or suspension. "Oligomer" or "aggregation" means that the composition of the present invention and the relevant component of the alkylene oxide of the surfactant (B) group are composed of 3 to one bonded monomer structural unit. "Polymer" or "polymerized" means that the composition of the present invention and the related component of the epoxy group of the surfactant (B) are composed of more than one bonded monomer structural unit. The first main component of the composition of the present invention is at least one, preferably one, abrasive particle (A). The average particle size of the abrasive particles (A) can vary widely, and thus can be most advantageously adjusted in accordance with the specific requirements of the intended compositions and methods of the present invention. The average particle size is preferably in the range of i to 2 Å as measured by dynamic laser light scattering, preferably in the range of i to 1000 nm, more preferably! Up to 75 〇 (10) and best in the i i 500 nm range. The primary particles can also aggregate to form secondary aggregates. The particle size distribution of the abrasive particles (A) may be monomodal, bimodal or multimodal. The particle size distribution is preferably unimodal 'to make the abrasive particles (A) have characteristics of easy reproduction properties and during the method of the invention Obtaining conditions for easy reproduction. m 'abrasive particles' < π 乍 乍 乂 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Features and ease of reproduction conditions are obtained between the present invention. It may have a shape in which the abrasive particles (A) may have various shapes. Therefore, or substantially one shape. However, the abrasive particles (A) are also 13 201229164: In particular, 'two different shapes of abrasive particles (a) may exist on both sides, "identify the shape of the body, which can be cubes, chamfered... icosahedron, irregular spheres and with or without protrusions or depressions The sphere. The shape is preferably a sphere with no or only a few protrusions or depressions. This shape is generally preferred because it generally increases the resistance to the mechanical forces experienced by the abrasive particles (A) of the method (10). β In principle, any type of abrasive particles (A) can be used for the composition of the present invention as long as it has the above characteristics. Therefore, the abrasive particles (4) may be organic or inorganic particles or organic-inorganic hybrid particles. The abrasive particles (A) are preferably inorganic particles. The inorganic abrasive particles (A) are more preferably selected from the group consisting of oxidized, oxidized stone, oxidized, oxidized, cerium oxide, oxidized, co-formed products, and mixtures thereof. Separately used as the abrasive particles (A). The amount of abrasive particles (A) used in the compositions of the present invention can vary widely' and thus can be most advantageously adjusted in accordance with the particular requirements of the established compositions and methods of the present invention. The composition of the present invention preferably contains 0.00% by weight, more preferably 0.01% to 8% by weight, and by weight, based on the most preferred 0.01 to 6% by weight of the abrasive particles (A) of the composition of the present invention. Weight meter. A main component is at least one, preferably one water-soluble or water-dispersible (B). Preferably, the water-soluble amphoteric nonionic surfactant comprises at least one hydrophobic active agent (B) which may have a amphoteric nonionic surfactant (B) group (bl). This means that the amphoteric nonionic interface 14 201229164 or more hydrophobic groups (b 1 ), for example, two (bl ), which are composed of at least one of the following hydrophilic groups of three or more groups (b2) Separate. The hydrophobic group (b1) is selected from the group consisting of 5 to 20, preferably 7 to 16, and most preferably 8 to. The branched alkane of 1 to 5 carbon atoms preferably has an average degree of branching of the branched alkyl group (bl) of from 5 to 5, more preferably from 1 to 4 and most preferably from 1 to 3. Suitable for branch chain bases (bl) derived from iso-institutions, neodymium and branched hexane, heptane, octane, decane, decane, eleven &, dodecane, tridecane, fourteen Alkane, pentadecane, hexadecane, heptadecane, nonadecane and eicosane isomers. The amphoteric nonionic surfactant (B) contains at least one hydrophilic group (b2). This means that the amphoteric nonionic surfactant (B) contains more than one group (b2) 'for example 2, 3 or more groups (b2) separated from each other by a hydrophobic group (b 1 ) . Therefore, the amphoteric nonionic surfactant (B) may have a different block-like structure. Examples of such block-like structures are ··1 -b2 9 _bl-b2_bl , "b2-bl-b2 9 •b2-b1-b2-b 1, -bl-b2-bl-b2-bl , And -b2-bl-b2-bl-b2. The hydrophilic group (b2) is selected from the group consisting of polyoxyl 15 201229164 based on oligo or polymeric groups. The hydrophilic group (b2) comprises an oxyethyl monomer unit (in addition, the hydrophilic group (b2) comprises at least one of the alkyl group units (10)), wherein the substituent is selected from the group consisting of a group consisting of aryl groups. The methicyloxy-based monomer unit (b22) is preferably derived from a substituted alkyl group, wherein the substituent is selected from the group consisting of a group, a cycloalkyl group and an aryl group: the wind substituent itself may also have an inert substitution The base, that is, the substituent of the copolymerization of the epoxy group and the surface active of the amphoteric nonionic surfactant (B). Examples of such inert substituents are a gas atom, a stone group and a nitrile group. In the case of substitution, it is used in such an amount that it does not adversely affect the interface agent (type of hydrophilicity-hydrophobic balance. The substituent preferably does not carry such inert substituents. The substituent of ethylene oxide is preferably selected Free radicals consisting of the following groups of to 10 carbon atoms; spiro, extracyclic and/or cyclic (in the fine (4) configuration: cycloalkyl having 5 to 10 carbon atoms; having 6 to 1 〇 An aryl group of a carbon atom; an alkyl-cycloalkyl group having 6 to 20 carbon atoms; a aryl group having 7 carbon atoms; a naphthenic earth group having 11 to 2 carbon atoms; and having 12 to 30 Alkyl-cycloalkyl-aryl groups of one carbon atom. Examples of suitable alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl-butyl, tert-butyl, n-pentyl, 2_ and 3_methylindenyl, U-mercaptopropyl, n-hexyl, 2-, 3- and 4-methylpentyl, 2,2_ and 3,3-di-tert-butyl-heptyl, 2,3-Dimercaptopentyl, 2,3,3-tridecylbutyl, n-octyl, isooctyl, 2-ethylhexyl 'n-decyl, 2-ethyl·34_^yl 16 201229164 A pentyl group and a n-decyl group, preferably a decyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, N-pentyl and n-hexyl. Examples of suitable cycloalkyl groups are cyclopentyl, cyclohexyl, cyclopentane-1,1-diyl, cyclopentane-1,2-diyl, cyclohexane-diyl and Cyclohexane-1,2-diyl. Examples of suitable aryl groups are phenyl and 1- and 2-naphthyl. Examples of suitable alkyl-cycloalkyl groups are cyclopentyl- and cyclohexylfluorenyl, 2- Cyclopentyl- and 2-cyclohexylethyl-1-yl, 3-cyclopentyl- and 3-cyclohexylpropanyl-yl, and 4-cyclopentyl- and 4-cyclohexyl-n-butyl-indole Examples of suitable alkyl-aryl groups are phenylmethyl, 2-phenylethyl, 3-phenylpropan-1-yl and 4-phenyl-n-butyl-1-yl. Suitable for cycloalkyl-aryl Examples of the group are 4-phenyl-cyclohex-1-yl, 4-cyclohexyl-phenyl-1-yl and 2,3-dihydroindole-i,2-diyl. Suitable alkyl-cycloalkyl- Examples of the aryl group are a cyclohexyl-phenyl-methyl group and a 2-cyclohexyl-2.phenylethanyl-1-yl group. Particularly preferred examples of the substituted ethylene oxide are a methyl group, an ethyl group, and 2, 2_ and 2'3-dimethyl, 2,2,3-trimethyl, 2,2,3,3-tetramethyl, 2-methyl-3-ethyl, 2'2 and 2,3- Diethyl, n-propyl, 2 methyl-3-n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, Octyl, n-decyl, n-decyl, cyclopentyl, cyclohexyl, phenyl and naphthyl epoxy; U-epoxycyclohexane and -% pentane, 1-oxa-3-spiro[ 3.4]-heptane, 1_oxa_3_spiro[35]_octane; and 1,2-epoxy-2,3_dihydrogen. It is especially preferred to use methyl epoxy bromide (ring Isopropyl oxime ethyl oxirane (cyclobutane). The hydrophilic group (b2) is preferably composed of monomer units (b2l) and (b22) 17 201229164. Polyoxyalkylene groups contain random distribution Monomer units (b2 1 ) and (b22 ) with alternating distribution, gradient distribution and/or block-like distribution. This means that a hydrophobic group (b2) can have only one distribution, ie - random: ...-b21-b21-b22-b21-b22-b22-b22-b21-b22-..; :...-b21-b22-b21-b22-b21-....; - Gradient: ...b21-b21-b21-b22-b21-b21-b22-b22-b21-b22-b22-b22- ...; or - block-like: ...-b21-b21-b21-b21-b22-b22-b22-b22-.... Alternatively, the hydrophilic group (b2) may contain at least two distributions, such as oligomeric or polymeric segments having a random distribution and oligomeric or polymeric segments having alternating distribution. The hydrophilic group (b2) preferably has only one distribution. The distribution is best as random or block-like distribution. The molar ratio of the oxyethyl monomer unit (b21) to the oxyalkylene monomer unit (b22) can vary widely, and thus can be most advantageously adjusted in accordance with the specific requirements of the compositions, methods and uses of the present invention. Mohr ratio (b2 1 ) · (b22) is preferably 1 〇〇:1 to ι:1, more preferably 6 〇: 丨 to 1 5:1 and most preferably 50:1 to 1.5:1. The degree of polymerization of the agglomerated and polymerized polyoxyalkylene groups (b2) can also vary widely, and thus can be most advantageously adjusted in accordance with the particular requirements of the compositions, methods and uses of the present invention. The degree of polymerization is preferably in the range of 5 to 丨00, preferably in the range of 5 to 90 and most preferably in the range of 5 to 8 Å. The amphoteric nonionic surfactant (B) is a conventional and known material and is commercially available from BASF SE under the trademark PlurafacTM 18 201229164. The concentration of the amphoteric nonionic surfactant (B) in the composition of the present invention can be varied widely, and thus can be most advantageously adjusted according to the specific requirements of the compositions, methods and uses of the present invention. The concentration is preferably in the range of i ρριη to 〇.丨0/〇, preferably in the range of 10 ppm to 〇.〇9 wt%, even more preferably in the range of 1 〇〇ppm to 〇.〇8 wt%, And preferably in the range of from 2 〇〇 ppm to 〇〇 8% by weight, the weight specification is based on the total weight of the composition of the invention. The composition of the present invention may additionally contain at least one component different from the components (A) and (B) (c > preferably at least two functional components (C) are used. (C) is more preferably selected from the group consisting of: an amphoteric nonionic surfactant other than the surfactant (B), a 7° alcohol having at least two hydroxyl groups, a minimum critical solution temperature LCST or a highest criticality A solution, a oxidizing agent, a passivating agent, a charge reversing agent, a cleavage agent or a chelating agent, a friction suppressing agent, a stabilizer, a pH adjusting agent, a nitriding group enhancer, a buffer, and a flow. Varnishes, surfactants, metal cations and organic solvents. Examples of suitable amphoteric nonionic surfactants (c) are described, for example, in European Patent EP 1 534 795 m 帛 3 pages [Deleted 3] to [0023] In the paragraph ▲, the township alcohol (C) is a diol, such as ethylene glycol and propylene glycol; triol, gentleman glycerol, pentaerythritol, alditol, cyclic alcohol, and glycerol, trimethylolpropane,: pentane Dimers and oligomers of tetraol, alditol and cyclic alcohol. _ Qi I ( C ) and its The amount is described, for example, by European Patent Application No. 19 201229164 1 036 836 A1, page 8, paragraphs [0074] and [0075], or US Patent 6, 6,068,787, column 4, line 40 to column 7, line 45 or Us 7 3〇 〇,6〇1 B2 Column 4, lines 18 to 34 are known. It is preferred to use organic and inorganic peroxides, and more preferably inorganic peroxides. Especially hydrogen peroxide can be used. Suitable for passivating agent (C) Also known as corrosion inhibitors, and their effective amounts are described, for example, in U.S. Patent No. 7,300,601 B2, No. 3, line 59 to column 4, line 9, U.S. Patent Application No. US 2008/0254628, A1, pages 4 and 5. Paragraph [〇〇58] or European Patent EP 1 534 795 B1, page 5, paragraph [0031] is suitable for the wrong agent or chelating agent (c) (which is sometimes also referred to as friction reducing agent (see US patent) Shen singer US 2008/0254628 A1, page 5, paragraph [0061] or I insect engraving agent (see US Patent Application No. US 2008/0254628 A1, page 4, paragraph [0054]) and its effective amount is for example U.S. Patent 7,300,601 B2, col. 4, lines 35 to 48, or European Patent Ε ι 534795 B1, page 5, paragraph [0029]. It is especially preferred to use amino acids (especially glycine and L_). Histidine acids and carboxylic acids such as malonic acid. Suitable stabilizers (C) and effective amounts thereof are known, for example, from US Pat. No. 6,068,787, column 8, lines 4 to 56. Suitable pH adjusters and buffers (c And an effective amount thereof, for example, from European Patent Application EP 1 036 836 A1, page 8, paragraph [〇〇8〇], paragraph [0085], and paragraph [0086], International Patent Application No. 2005/014753 A1 Page 12, lines 19 to 24; U.S. Patent Application No. 2008/0254628 A1, page 6, paragraph [0073] or U.S. Patent 7,300, 601 B2, fifth block, lines 33 to 63, are known. 20 201229164 Suitable for cerium nitride enhancer (c) is a low molecular weight carboxylic acid such as acetic acid, oxalic acid and malonic acid, especially malonic acid. Suitable rheological agents (C) 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 (C) and their effective amounts are, for example, from International Patent Application No. WO 2005/01475 3 A1, page 8, line 23 to page 10, line 17, or US Patent 7,300,601 B2, column 5, line 4 to Line 8 is known as line 8. Suitable polyvalent metal ions (C) and their effective amounts are known, for example, from European Patent Application EP 1 03 6 836 A1, page 8, paragraph [0076] to page 9, paragraph [0078].

Suitable organic solvents (C) and their effective amounts are known, for example, from U.S. Patent No. 7,361,603 B2, at column 7, lines 32 to 48, or from US Patent Application No. US 2008/0254628 A1, page 5, paragraph [〇〇59]. Suitable materials (C) exhibiting a minimum critical solution temperature LCST or a maximum 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 Al, US 2004/0209095 A1, US 2004 /0217009 A1, US 21 201229164 2006/0141254 A1, US 2007/0029198 A1, US 2007/0289875 A1, US 2008/0249210 A1, US 2008/0050435 A1 or US 2009/0013609 A1; US Patent US 5,057,560, US 5,788, 82 and US 6,682,642 B2; International Patent Application No. 01/60926 A1, W02004/029 160 A, WO 2004/0521946 A, WO 2006/093242 A2 or WO 2007/012763 A1; European Patent Application ep 〇 583 814 A1, EP 1 197 5 87 B1 and EP 1 942 179 A1; or German patent application DE 26 10 705. In principle, any known charge reversal agent (C) commonly used in the field of CMP can be used. The charge reversal agent (C) is preferably selected from the group consisting of monomers - oligomerization and polymerization containing at least one anion group selected from the group consisting of carboxylate, sulfonate, sulfate and phosphonate groups. Compound. Preferably, the pH of the composition of the present invention is preferably set between 8 and 12 using the above pH adjusting agent (c). The preparation of the composition of the present invention does not exhibit any particularity, but can be carried out by dissolving or dispersing the above components (A) and (B) and optionally (c) in an aqueous medium, especially deionized water. For this purpose, customary and standard mixing methods and mixing equipment can be used, such as agitating vessels, in-line diversifiers, high shear impellers, ultrasonic mixers, homogenous nozzles (h〇m〇genizer) Nozzle) or countercurrent mixer. The composition of the invention thus obtained can preferably be filtered through a filter of a suitable mesh size to remove coarse particles, such as agglomerates or aggregates of solid finely dispersed abrasive particles (A). In accordance with the use of the present invention, the compositions of the present invention are highly suitable for the fabrication of electrical, mechanical, and optical devices, in which high precision grinding steps are required in the process of making earth and earth. For example, the electrical device is an ic device, an oil product 4c, a clothing liquid crystal panel, an organic electroluminescence panel, a printed circuit board, a micro-computer test, a ηχΤ A曰μ soil state: a state, a DMA chip, a micro factory, and a magnetic head. 'Mechanical devices are still precision mechanical equipment Jin. b stop wind and strong m called Na瑕, and the first learning device is optical glass (such as mask, lens and enamel), inorganic conductive film (such as oxidized sulphur tin (ITO)) , optical integrated circuit, optical conversion element, optical waveguide, optical single crystal (such as optical fiber and scintillator end face), solid laser single crystal, blue laser LED sapphire substrate, Fengdao a 丞 plate bovine conductor early crystal And the glass substrate of the disk. 1C devices, especially LSI and VLSI 1C 奘筈 杜 人士 人士 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳The compositions of the present invention are most suitable for the method of the present invention. In the method of the invention 'substrate a substrate having a patterned and unpatterned low-k dielectric layer having a dielectric constant of 3.5 or less, in particular a semiconductor: a round, more specifically, a stone or a stone alloy A semiconductor wafer (such as a Shihua wrong wafer), the aqueous abrasive composition below the package 3 is contacted at least once: (A) at least one of the above-described abrasive particles, and) to a kind of amphoteric nonionic surfactant, It is selected from the group consisting of water-soluble or water-dispersible surfactants: (bU) at least one hydrophobic group selected from the group consisting of linear alkyl groups having the above-described carbon atoms And a branched chain alkyl group (1)), and to: a hydrophilic group selected from the group consisting of the above polyoxyalkylene oxides, the polyalkylene alkyl groups comprising random distribution, alternating Sub- 23 201229164 Distribution, gradient distribution and/or block-like distribution of an oxy-ethyl formo unit (b2i) and at least one substituted oxyalkyl unit (b22). The substrate having the patterned and unpatterned low-k dielectric layer used in the above method of the present invention has a dielectric constant of 3 5 or less, preferably 3 3 or 3. 3 is preferably 3 or less. The optimum is 2.8 or less, for example, 2 4 or less. With respect to the substrate having the patterned and unpatterned low-k electrical layer used in the above method of the present invention, the dielectric constant of the low-k dielectric layer is preferably v 0.01 ', more preferably at least 〇1 Preferably, it is at least 〇3, for example at least 2.0. Suitable straight chain alkyl groups having 5 to 20 carbon atoms are derived from pentane, hexane, heptane, octane, oxime & decane, undecane, dodecane, thirteen, ten Four burned, +; Songding Ding Wukeng, hexadecane, heptadecane, nonadecane and twenty burning. Thereafter, the substrate is chemically mechanically ground at a predetermined temperature for a certain period of time to sufficiently achieve the desired complete and partial flatness. Then, the substrate is removed from contact with the aqueous abrasive composition. The method of the present invention exhibits particular advantages in CMP semiconductor wafers having patterned layers consisting of low-k or ultra-low-k oxidized oxide dielectric as a dielectric layer, and a hard mask of sulphur dioxide A layer, a nitride button as a termination layer or a barrier layer, and a conductive copper wire. Suitable methods for low-k or ultra-low-k dielectric materials and for preparing insulating dielectric layers are described, for example, in U.S. Patent Application No. 2〇〇5/〇l76259 ai, page 2, paragraphs [0025] to [0027], Us 2 〇〇5/〇〇14667 A1 page i, paragraph 24, 201229164, US 2005/0266683 A1, page 1, page [0003] and page 2, paragraph [〇〇24] or US 2008/0280452 A1, paragraph [0024] To [0026]; U.S. Patent 7,250,391 B2, col. 1, lines 49 to 54; European Patent Application Ep 1 306415 A2, page 4, paragraph [0031]; European Patent EPi 534 795 B1, page 5, [0026] In the paragraph. Carbon doped cerium oxide (CD0) is best used as a low-k or ultra-low-k dielectric material. For example, use BlackDiamondTM (from AppUed

Materials) as a low-k or ultra-low-k dielectric material. BiackDiam〇ndTM (from Applied Materials) has a dielectric constant of about 3 〇. The method of the present invention is particularly suitable for a barrier CMp process which requires selective removal of germanium dioxide without affecting the integrity of the low k or ultra low k dielectric layer on the patterned semiconductor wafer. Therefore, in the method of the present invention, it is required to have the same selectivity for cerium dioxide in terms of dirt compared to a low-k or ultra-low-k dielectric material. The MRR of the tantalum nitride or button' nitride layer and the copper layer (when present) are preferably unaffected. A particular advantage of the process of the present invention is that the dielectric material exhibits a selectivity to > 3, preferably > 5, compared to low or ultra low. The geotechnical of the present invention exhibits specificity and can be carried out by a method and apparatus commonly used for manufacturing CMP having a Japanese yen. It is known in honing that the typical equipment used for CMP is covered by the upper side ===. The wafer is mounted on a carrier or chuck to make the holding and holding device 2 . The carrier secures the wafer to a horizontal position. The carrier cushion is developed and the A^ & configuration is also referred to as a hard plate design. The carrier is protected between the holding surface of the carrier and the surface on which the wafer is not intended to be grounded 25 201229164. This pad acts as a buffer for the wafer. Below the carrier, the larger diameter is pressed against the surface of the wafer surface that is parallel to the surface.塾Contact the wafer surface. The application of the present invention in a continuous flow or drop-wise manner is also generally horizontally disposed and provided for use in the polishing pad during the polishing CMP process during the planarization process. The carrier and the platen are rotated about respective axes of rotation extending perpendicularly from the carrier and the platen. The rotating carrier shaft can be held in place 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 platen. The rotational speed of the carrier and the platen is substantially (but not necessarily) set to a different value. Usually, the temperature of the platen is set to 10. (: Temperature with 7〇r. For other details, see International Patent Application W〇2〇〇4/〇633(7) A1, especially page 16 [0036] to page 18 [〇〇4〇 Sections, and Figures Through the method of the present invention, a semiconductor wafer having a 1C comprising a patterned low-k and ultra-low-k material layer (especially a carbon-doped cerium oxide layer) and having excellent flatness can be obtained. Therefore, a copper damascene pattern which also has excellent flatness and excellent electrical function (in the completed 1C) can be obtained. Examples and comparative experiments Examples 1 to 2 and comparative experiments C 1 to C2 CMP sputum u2 (implementation The preparation of the CMP liquids 2, C1 and C2 were prepared by dissolving and dispersing the components in ultrapure water. The composition of the CMP slurry was compiled by the preparation of the comparative experiments C1 and C2. 26 201229164 Table 1: Composition of CMP Slurry 1 to 2 (Examples 1 to 2) and ci to C2 (Comparative Experiments Cl and C2) a) Example or Comparative Experiment No. cerium oxide abrasive a) ( % by weight Histamine (% by weight) BTAb) (ft%) Malonic acid (% by weight) Propylene glycol (% by weight) Amphoteric nonionic interface Active agent (% by weight) KOH (% by weight) C1 4 0.0375 0.0289 0.648 0.642 1.925 C2 4 0.0375 0.0289 0.648 0.642 TritonTM DF16c) 0.06 1.925 1 4 ] 0.0375 0.0289 0.648 0.642 Ad) 0.06 1.925 2 4 0.0375 0.0289 0.648 0.642 Be) 0.06 1.925 a) average primary particle size d 1 : 35 nm; average secondary particle size d2 : 70 nm; aggregate ratio d2/dl ·· 2 ·' (FUSOTM PL_3 from Fuso Chemical); b) benzotriene Oxazole; c) nonionic polyoxyethylene-polyoxypropylene alkylate surfactant (from DOW) 'which is a mixture of molecules containing an alkyl group having 8, 9 or 10 carbon atoms on average, and As shown in the 1H_NMR spectrum, it is a linear alkyl polyoxyethylene-polyoxypropylene polymer; d) A = nonionic polyoxyethylene-polyoxybutylene alkyl ether surfactant' which is an average containing block a mixture of molecules having a branched chain alkyl group of 9, 1 or 1 carbon atom and 7 molecules of an ethylenic ethylenic monomer unit and a 1-5 oxybutylene monomer unit; e) Β = nonionic polyoxyethylene/polyoxypropylene alkyl ether surfactant' which is average a randomly distributed mixture of a branched alkyl group having 13, 14 or 15 carbon atoms and 16 molecules of an oxyethyl group and 4 groups of oxy-extensions; 27 201229164 4 kg of 31% by weight hydrogen peroxide was added per 100 kg of each CMP slurry. Chemically mechanically grind 200 _ blanket-type Shi Xi wafers with CMP poly-liquids 1, 2, C1, and C2 under the following conditions, and these blanket-covered Shixi wafers have 胄15, _ 1500 nm) initial thickness TE〇s layer, 15 v8 v iduu πm j initial thickness of copper layer or 2000 A (200 nm) initial thickness of nitrided button layer or 10,000 A (1000 nm) initial thickness Low M-doped carbon dioxide layer (Black DiamondTM BD1 'Applied Materials). - Grinding equipment - Platen speed - Carrier speed AM AT Mirra (rotary); 1 30 rpm; 83 rpm; - Grinding 塾: Fujibo ; -塾 adjustment: spot (inmysitu) - slurry flow rate: 200 ml / min; - adjustment down pressure: 5 lbf ( 22.24 N); - number of dummy wafers: 4, - grinding pressure: 3 psi (205 mbar (mbar)); - Buckle pressure: 3 psi (205 mbar); - Inner tube pressure: 2_5 psi (171 mbar) - Grinding time: 60 seconds. The MRR is determined by weighing the wafer before and after grinding. The grinding results are discarded in Table 2. 28 201229164

Table 2: TEOS, Nitrided Group, Copper and Black DiamondTM MRR CMP Slurry Numbers obtained from CMP Slurry 1, 2, Cl and C2. TE0S MRR (Aim) Nitrided Giant MRR CA/m) Copper MRR (Small Child) Black DiamondTM MRR (A/min) Compared to Black DiamondTM for TE0S4ijt#lt compared to Black DiamondTM for Eucalyptus than Black DiamondTM for copper selectivity C1 541 1100 436 586 0.92 1.B7 0.747 C2 543 1058 451 199 2.73 5.31 2.26 1 502 998 466 130 3.86 7.67 3.58 2 532 1067 377 94 5.66 11.35 4 The results from Table 2 are evident in the selectivity to cerium oxide, tantalum nitride and copper compared to ultra-low-k dielectric materials. It can significantly improve 'and does not adversely affect the MRR of cerium oxide, tantalum nitride and copper. This conclusion can also be significantly reduced from the ultra low k dielectric material MRR from 586 (comparative experiment Cl) to 94 (Example 2), ie, a reduction of about 84%. Therefore, the CMP liquids 1 to 2 of Examples 1 to 2 are suitable for the barrier CMP method. [Simple description of the diagram] None [Key component symbol description] None 29

Claims (1)

201229164 VII. Patent Application Range: 1 · An aqueous abrasive composition comprising: (A) at least one abrasive particle, and (B) at least one amphoteric nonionic surfactant selected from the group consisting of water soluble or water having the following a group consisting of a dispersing surfactant: (bl) at least one hydrophobic group selected from the group consisting of branched alkyl groups having from $ to μ carbon atoms; and (b2) at least one hydrophilic group 'Selected from the group consisting of polyoxyalkylene groups comprising: (b21) oxyethylidene monomer units, and (b22) at least one substituted oxyalkylene monomer unit, wherein the substituent is selected from a group consisting of: an alkyl group, a cycloalkyl group or an aryl group; an alkyl-cycloalkyl group, an alkyl-aryl group, a cycloalkyl-aryl group, and an alkylcycloalkyl group, an aryl group; The base contains randomly distributed, alternating, gradient, and/or block-like distributions of the monomer units (b21) and (b22). 2. The aqueous abrasive composition of claim 1, wherein the hydrophobic group (b 1 ) is selected from the group consisting of branched alkyl groups having 8 to 15 carbon atoms. 3. The aqueous abrasive composition of claim 1 or 2, wherein the oxyalkylene monomer unit (b22) is derived from a substituted epoxicone wherein the substituent is selected from the group consisting of The group consisting of alkyl, cycloalkyl or aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cyclo-aryl. 201229164 4. The aqueous abrasive composition according to claim 3, wherein the substituents are selected from the group consisting of an alkyl group having from 丨 to 1 carbon atom, a spiro ring, and an outer ring. And/or a cycloalkyl group having 5 to 1 carbon atoms in the ring configuration; an aryl group having 6 to 10 carbon atoms; an alkyl-cycloalkyl group having 6 to 2 carbon atoms; having 7 to An alkyl group of 2 carbon atoms - an aryl group; a cycloalkyl-aryl group having 11 to 20 carbon atoms; and an alkyl-cycloalkyl-aryl group having 12 to "carbon atoms. The water-based grinding composition of the fourth aspect of the patent (4), characterized in that the molar ratio of the monomer single it (b21) to the monomer unit (b22) is (10): ι to 6. as in the scope of the application patent item! An aqueous abrasive composition according to any one of the preceding claims, characterized in that the degree of polymerization of the polyoxyl extension groups is from 5 to 1 Å. 7. The water-based grinding of any of the items in the application of the patents @i to 6 The composition is characterized in that the concentration of the surfactant (B) is from - to 0.1% by weight, and the weight specifications are based on the total weight of the composition. The aqueous abrasive composition of any one of items [i] to [7], wherein the abrasive particles (A) are selected from the group consisting of: oxidized, oxidized, oxidized cerium oxide The oxidative oxidizing agent, the cerium oxide, the magnesium oxide, the co-formed product thereof, and the mixture thereof. The aqueous abrasive composition according to any one of the items of the present invention, characterized in that it contains at least one different from The additional functional components (匸) of the components (A) and (B) 10. The chemical mechanical polishing has a dielectric constant of 3 5 or less (4) cased or unpatterned low k Or the substrate of the ultra-low-k dielectric layer 31 201229164 method, comprising the steps of: (" contacting the substrate material with at least one of the following aqueous polishing compositions: (A) at least one abrasive particle, and (Ba At least one amphoteric nonionic surfactant selected from the group consisting of water-soluble or water-dispersible surfactants: (bla) at least one hydrophobic group selected from the group consisting of 5 to 2 Linear alkyl group and fraction of carbon atoms a group consisting of an alkyl group (b丨); and (b2) at least one hydrophilic group selected from the group consisting of polyoxyalkylene groups having the following groups: (b21) an oxy-ethyl monomer unit, And (b22) at least one substituted oxyalkylene monomer unit, wherein the substituent is selected from the group consisting of alkyl, cycloalkyl or aryl, alkyl-alkyl, alkyl-3 a cycloalkyl-aryl group and a alkyl group-cycloalkyl group aryl group; the polyoxyalkylene group has a random distribution, an alternating distribution, a gradient distribution, and/or a block-like distribution of the monomer units (b21) and (b22). (2) chemically grinding the substrate at a certain temperature for a certain period of time to sufficiently achieve the desired complete flatness; and (3) removing the substrate from contact with the aqueous polishing composition. 11. The method of claim 10, wherein the low-k and ultra-low-k dielectric layer material is selected from the group consisting of porous and non-porous organically modified bismuth glass and organic polymers. 32 201229164 12. The method of claim 4, wherein the modified Shishi glass is doped with carbon dioxide (Cd〇). 13. The method of claim 2, wherein the substrate further comprises at least one layer selected from the group consisting of dielectric layers and barrier layers other than the low-k and ultra-k dielectric layers. And gold layers. The method of claim 13, wherein the dielectric layer is an oxide layer. 15. The method of claim 14, characterized in that it has a selectivity to cerium oxide in terms of material removal rate (mrr) compared to low-k and ultra-low-k dielectric f'. 16. The use of a water-based abrasive composition according to any one of claims 1 to 9 for the manufacture of electrical, mechanical and optical devices. Eight, schema: None 33